LIQUID CRYSTAL DISPLAY DEVICE AND DISPLAY UNIT

Abstract

The liquid crystal display device of the disclosure has: a first substrate; a plurality of pixel electrodes formed on the first substrate; a second substrate; a counter electrode formed on the second substrate and facing the pixel electrode; a liquid crystal layer including a liquid crystal composition between the pixel electrode and the counter electrode; and an alignment control layer formed of a polymer containing an alignable monomer that is one component of the liquid crystal composition, in which the alignment control layers are each formed on a side of the first substrate and on a side of the second substrate. The alignable monomer is a polymerizable polar compound having a mesogen moiety formed of at least one ring, and a polar group.

Claims

1. A liquid crystal display device, comprising: a first substrate; a plurality of pixel electrodes formed on the first substrate; a second substrate; a counter electrode formed on the second substrate and facing the pixel electrode; a liquid crystal layer including a liquid crystal composition between the pixel electrode and the counter electrode; and an alignment control layer formed of a polymer containing an alignable monomer that is one component of the liquid crystal composition, in which the alignment control layers are each formed on a side of the first substrate and on a side of the second substrate; wherein the alignable monomer is a polymerizable polar compound having a mesogen moiety formed of at least one ring, and a polar group.

2. The liquid crystal display device according to claim 1, wherein the mesogen moiety includes a cyclohexane ring.

3. The liquid crystal display device according to claim 1, wherein the alignable monomer is a compound represented by formula (1): ##STR03725## wherein, in formula (1), R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; MES is a mesogen group having at least one ring; Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and R.sup.2 is a group represented by formula (1a), (1b) or (1c): ##STR03726## wherein, in formulas (1a), (1b) and (1c), Sp.sup.2 and Sp.sup.3 are independently a single bond or alkyl ene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; S.sup.1 is >CH or >N; S.sup.2 is >C< or >Si<; and X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.3, N(R.sup.3).sub.2, formula (x1), COOH, SH, B(OH).sub.2 or Si(R.sup.3).sub.3, in which R.sup.3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen, and w in formula (x1) is 1, 2, 3 or 4 ##STR03727##

4. The liquid crystal display device according to claim 1, wherein the alignable monomer is a compound represented by formula (1): ##STR03728## wherein, in formula (1), R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; MES is a mesogen group having at least one ring; Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; and R.sup.2, M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, halogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

5. The liquid crystal display device according to claim 1, wherein the alignable monomer is a compound represented by formula (1): ##STR03729## wherein, in formula (1), R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen or alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, S or NH, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen; n is independently 0, 1 or 2; ring A.sup.4 is cyclohexylene, cyclohexenylene, phenylene, naphthalene, decahydronaphthalene, tetrahydronaphthalene, tetrahydropyran, 1,3-dioxane, pyrimidine or pyridine, and ring A.sup.1 and ring A.sup.5 are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl or pyridine-2-yl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; Z.sup.1 and Z.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; a and b are independently 0, 1, 2, 3 or 4, and a sum of a and b is 1, 2, 3 or 4; c, d and e are independently 0, 1, 2, 3 or 4; a sum of c, d and e is 2, 3 or 4; and P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1): ##STR03730## wherein, in formula (P-1), M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and R.sup.4 is a group selected from groups represented by formulas (1a), (1b) and (1c): ##STR03731## wherein, in formulas (1a), (1b) and (1c), Sp.sup.5 and Sp.sup.6 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; S.sup.1 is >CH or >N; S.sup.2 is >C< or >Si<; and X.sup.1 is independently a group represented by OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3, in which R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen.

6. The liquid crystal display device according to claim 1, wherein the alignable monomer is a compound represented by formula (1-1): ##STR03732## wherein, in formula (1-1), R.sup.1 is alkyl having 1 to 15 carbons, and in R.sup.1, at least one CH.sub.2 may be replaced by O or S, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen; ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; a is 0, 1, 2, 3 or 4; Z.sup.1 is a single bond or alkylene having 1 to 6 carbons, and in Z.sup.1 at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by fluorine or chlorine; and Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.1, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen, and in the groups, at least one hydrogen is replaced by a group selected from groups represented by formula (1a): ##STR03733## wherein, in formula (1a), Sp.sup.12 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.12, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen; M.sup.11 and M.sup.12 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; R.sup.12 is alkyl having 1 to 15 carbons, and in R.sup.12, at least one CH.sub.2 may be replaced by O or S, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen; and in formula (1-1), P.sup.11 is a group selected from groups represented by formulas (1e) and (1f): ##STR03734## wherein, in formulas (1e) and (1f), Sp.sup.13 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.13, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; Sp.sup.14 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.14, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen; M.sup.13 and M.sup.14 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; X.sup.1 is OH, NH.sub.2, OR.sup.15, N(R.sup.15).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.15).sub.3; and in OR.sup.15, N(R.sup.15).sub.2 and Si(R.sup.15).sub.3, R.sup.15 is hydrogen or alkyl having 1 to 10 carbons, and in R.sup.15, at least one CH.sub.2 may be replaced by O, at least one CH.sub.2CH.sub.2 may be replaced by CHCH, and at least one hydrogen may be replaced by halogen.

7. The liquid crystal display device according to claim 1, wherein the alignable monomer is a compound represented by formula (1):
R.sup.1-MES-Sp.sup.1-P.sup.1(1) wherein, in formula (1), R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; MES is a mesogen group having at least one ring; and Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen, and in the groups, at least one hydrogen is replaced by a group selected from groups represented by formulas (1a), (1b), (1c) and (1d): ##STR03735## wherein, in formulas (1a), (1b), (1c) and (1d), Sp.sup.2 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; R.sup.2 is hydrogen or alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; and in formula (1), P.sup.1 is a group selected from groups represented by formulas (1e) and (1f): ##STR03736## wherein, in formulas (1e) and (1f), Sp.sup.3 is a single bond or alkylene having 1 to 10 carbons, and in the alkyl ene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; M.sup.3 and M.sup.4 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; X.sup.1 is OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3; and R.sup.3 is a group selected from groups represented by formulas (1g), (1h) and ##STR03737## wherein, in formulas (1g), (1h) and (1i), Sp.sup.4 and Sp.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; S.sup.1 is >CH or >N; S.sup.2 is >C< or >Si<; and X.sup.1 is OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3; and in OR.sup.5, N(R.sup.5).sub.2 and Si(R.sup.5).sub.[[2]]3, R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen.

8. The liquid crystal display device according to claim 1, wherein the polymer containing the alignable monomer is a copolymer with a reactive monomer.

9. The liquid crystal display device according to claim 1, wherein the alignment control layer has a thickness of 10 to 100 nanometers.

10. The liquid crystal display device according to claim 1, wherein at least one liquid crystal compound contained in the liquid crystal composition has negative dielectric anisotropy.

11. The liquid crystal display device according to claim 1, wherein molecular alignment of the liquid crystal compound contained in the liquid crystal composition is vertical alignment relative to a surface of the substrate by the alignment control layer, and an angle of the vertical alignment to the substrate is 9010 degrees.

12. The liquid crystal display device according to claim 1, wherein the molecular alignment of the liquid crystal compound contained in the liquid crystal composition is divided as aligned for every pixel.

13. The liquid crystal display device according to claim 1, having no alignment film.

14. A display unit, comprising: the liquid crystal display device according to claim 1; and a backlight.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0035] FIG. 1 is a schematic view showing device 11 in a state in which polymerizable polar compound 5 as an alignable monomer is arranged on color filter substrate 1 and array substrate 2 by interaction of a polar group with a substrate surface (an electrode layer is not shown), in which an alignment control layer is formed by a polymerization reaction.

[0036] FIG. 2 is a schematic view showing device 12 in a state in which polymerizable polar compound 5 as an alignable monomer is arranged on color filter substrate 1 and array substrate 2 by interaction between a polar group and a substrate surface (an electrode layer is not shown), in which an alignment control layer is formed by incorporating polymerizable compound 6 as a reactive monomer by polymerization reaction.

[0037] FIG. 3 is a schematic view of conventional device 21 having an alignment film and containing a polymerizable compound (an electrode layer is not shown).

DESCRIPTION OF EMBODIMENTS

[0038] The present application is based on Japanese Patent Application No. 2016-153266 filed on Aug. 3, 2016 in Japan, and is hereby incorporated by reference in its entirety in the present application. The invention can be further completely understood by the following detailed description. A further application scope of the invention will become apparent by the detailed description described below. However, the detailed description and a specific embodiment are desirable embodiments of the invention, and described only for illustrative purposes because various possible changes and modifications will be apparent to those having ordinary skill in the art on the basis of the detailed description within spirit and the scope of the invention. The applicant has no intention to dedicate to the public any described embodiment, and among the modifications and alternatives, those which may not literally fall within the scope of the present claims constitute a part of the invention in the sense of the doctrine of equivalents.

[0039] Usage of terms herein is as described below. Terms liquid crystal composition and liquid crystal display device may be occasionally abbreviated as composition and device, respectively. A term liquid crystal display device is a generic term for a liquid crystal display panel and a liquid crystal display module. A term liquid crystal compound is a generic term for a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a compound having no liquid crystal phase but to be mixed with the composition for the purpose of adjusting characteristics such as a temperature range of the nematic phase, viscosity and dielectric anisotropy. The compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has rod-like molecular structure. Polymerizable compound is a compound to be added for the purpose of forming a polymer in the composition. Polar compound aids a polar group to cause interaction a substrate surface, thereby causing arrangement of liquid crystal molecules.

[0040] The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. A proportion (content) of the liquid crystal compounds is expressed in terms of weight percent (% by weight) based on the weight of the liquid crystal composition. An additive such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, the polymerizable compound, a polymerization initiator, a polymerization inhibitor and a polar compound is added to the liquid crystal composition when necessary. A proportion (amount of addition) of the additive is expressed in terms of weight percent (% by weight) based on the weight of the liquid crystal composition in a manner similar to the proportion of the liquid crystal compounds. Weight parts per million (ppm) may be occasionally used. A proportion of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

[0041] A compound represented by formula (1) may be occasionally abbreviated as compound (1). Compound (1) means one compound, a mixture of two compounds or a mixture of three or more compounds represented by formula (1). A same rule applies also to at least one compound selected from the group of compounds represented by formula (2), or the like. A symbol such as B.sup.1, C.sup.1 and F surrounded by a hexagonal shape corresponds to ring B.sup.1, ring C.sup.1 and ring F, respectively. The hexagonal shape represents a six-membered ring such as a cyclohexane ring and a benzene ring or a fused ring such as a naphthalene ring. An oblique line crossing one the hexagonal shape represents that arbitrary hydrogen on the ring may be replaced by a group such as -Sp.sup.1-P.sup.1. A subscript such as e represents the number of groups subjected to replacement. When the subscript is 0, such replacement is not performed.

[0042] A symbol of terminal group R.sup.11 is used in a plurality of component compounds. In the compounds, two groups represented by two pieces of arbitrary R.sup.11 may be identical or different. For example, in one case, R.sup.11 of compound (2) is ethyl and R.sup.11 of compound (3) is ethyl. In another case, R.sup.11 of compound (2) is ethyl and R.sup.11 of compound (3) is propyl. A same rule applies also to a symbol of any other terminal group, a ring, a bonding group or the like. In formula (8), when i is 2, two of ring D.sup.1 exists. In the compound, two groups represented by two of ring D.sup.1 may be identical or different. A same rule applies also to two of arbitrary ring D.sup.1 when i is larger than 2. A same rule applies also to a symbol of any other ring, a bonding group or the like.

[0043] An expression at least one A means that the number of A is arbitrary. An expression at least one A may be replaced by B means that, when the number of A is 1, a position of A is arbitrary, and also when the number of A is 2 or more, positions thereof can be selected without restriction. A same rule applies also to an expression at least one A is replaced by B. An expression at least one A may be replaced by B, C or D means including a case where at least one A is replaced by B, a case where at least one A is replaced by C, and a case where at least one A is replaced by D, and also a case where a plurality of pieces of A are replaced by at least two pieces of B, C and D. For example, alkyl in which at least one CH.sub.2 (or (CH.sub.2).sub.2) may be replaced by O (or CHCH) includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl and alkenyloxyalkyl. In addition, a case where two pieces of consecutive CH.sub.2 are replaced by O to form OO is not preferred. In alkyl or the like, a case where CH.sub.2 of a methyl part (CH.sub.2H) is replaced by O to form OH is not preferred, either.

[0044] Halogen means fluorine, chlorine, bromine or iodine. Preferred halogen is fluorine or chlorine. Further preferred halogen is fluorine. Alkyl is straight-chain alkyl or branched-chain alkyl, but includes no cyclic alkyl. In general, straight-chain alkyl is preferred to branched-chain alkyl. A same rule applies also to a terminal group such as alkoxy and alkenyl. With regard to a configuration of 1,4-cyclohexylene, trans is preferred to cis for increasing the maximum temperature of the nematic phase. Then, 2-fluoro-1,4-phenylene means two divalent groups described below. In a chemical formula, fluorine may be leftward (L) or rightward (R). A same rule applies also to an asymmetrical divalent group formed by removing two hydrogens from a ring, such as tetrahydropyran-2,5-diyl.

##STR00006##

[0045] The liquid crystal display device of the invention includes, in the liquid crystal composition, a polymerizable polar compound that functions as an alignable monomer and has a mesogen moiety formed of at least one ring, and a polar group. At least one ring is preferably a cyclohexane ring. The polymerizable polar compound is referred to as compound (1) herein. Further, in a case of referring to structure in detail or the like, when necessary, the polymerizable polar compound is separately referred to as compound (1), compound (1), compound (1), compound (1) or compound (1).

[0046] Compound (1) will be described in sections 1. Example of compound (1), 2. Form of compound (1), 3. Synthesis of compound (1), 4. Example of compound (1), 5. Form of compound (1), 6. Synthesis of compound (1), 7. Example of compound (1), 8. Form of compound (1), 9. Synthesis of compound (1), 10. Example of compound (1), 11. Form of compound (1), 12. Synthesis of compound (1), 13. Example of compound (1), 14. Form of compound (1) and 15. Synthesis of compound (1);

[0047] a composition containing compound (1) will be described in section 16. Liquid crystal composition; and

[0048] a device including the composition will be described in section 17. Liquid crystal display device in the order thereof.

1. Example of Compound (1)

[0049] Compound (1) will be described as an example in the following items.

[0050] Item 1. A compound, represented by formula (1):

##STR00007##

wherein, in formula (1),

[0051] R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0052] MES is a mesogen group having at least one ring;

[0053] Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0054] M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and

[0055] R.sup.2 is a group represented by formula (1a), (1b) or (1c):

##STR00008##

wherein, in formulas (1a), (1b) and (1c),

[0056] Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0057] S.sup.1 is >CH or >N;

[0058] S.sup.2 is >C< or >Si<; and

[0059] X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.3, N(R.sup.3).sub.2, formula (x1), COOH, SH, B(OH).sub.2 or Si(R.sup.3).sub.3, in which R.sup.3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen, and w in formula (x1) is 1, 2, 3 or 4.

##STR00009##

[0060] Item 2. The compound according to item 1, represented by formula (1-1):

##STR00010##

wherein, in formula (1-1),

[0061] R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0062] ring A.sup.1 and ring A.sup.4 are independent 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0063] Z.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0064] Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0065] M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen;

[0066] a is 0, 1, 2, 3 or 4; and

[0067] R.sup.2 is a group represented by formula (1a) or (1b):

##STR00011##

wherein, in formulas (1a) and (1b),

[0068] Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0069] S.sup.1 is >CH or >N; and

[0070] X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.3, N(R.sup.3).sub.2, formula (x1), COOH, SH, B(OH).sub.2 or Si(R.sup.3).sub.3, in which R.sup.3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen, and w in formula (x1) is 1, 2, 3 or 4.

##STR00012##

[0071] Item 3. The compound according to item 1 or 2, represented by formula (1-2):

##STR00013##

wherein, in formula (1-2),

[0072] R.sup.1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0073] ring A.sup.1 and ring A.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0074] Z.sup.1 is a single bond, (CH.sub.2).sub.2, CHCH, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF;

[0075] Sp.sup.1 and Sp.sup.2 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO or OCO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0076] M.sup.1 and M.sup.2 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine; and

[0077] X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.3, N(R.sup.3).sub.2, formula (x1), COOH, SH, B(OH).sub.2 or Si(R.sup.3).sub.3, in which R.sup.3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine, and w in formula (x1) is 1, 2, 3 or 4:

##STR00014##

wherein a is 0, 1, 2, 3 or 4.

[0078] Item 4. The compound according to any one of items 1 to 3, represented by any one of formulas (1-3) to (1-6):

##STR00015##

wherein, in formulas (1-3) to (1-6),

[0079] R.sup.1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0080] ring A.sup.1, ring A.sup.2, ring A.sup.3 and ring A.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 7 carbons, alkenyl having 2 to 7 carbons or alkoxy having 1 to 6 carbons;

[0081] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond, (CH.sub.2).sub.2, CHCH, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF;

[0082] Sp.sup.1 and Sp.sup.2 are independently a single bond or alkylene having 1 to 7 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO or OCO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine;

[0083] M.sup.1 and M.sup.2 are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl; and

[0084] X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.3, N(R.sup.3).sub.2, formula (x1) or Si(R.sup.3).sub.3, in which R.sup.3 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine, and w in formula (x1) is 1, 2, 3 or 4.

##STR00016##

[0085] Item 5. The compound according to any one of items 1 to 4, represented by any one of formulas (1-7) to (1-10):

##STR00017##

wherein, in formulas (1-7) to (1-10),

[0086] R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0087] ring A.sup.1, ring A.sup.2, ring A.sup.3 and ring A.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons or alkoxy having 1 to 4 carbons;

[0088] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond, (CH.sub.2).sub.2 or CHCH;

[0089] Sp.sup.1 is a single bond or alkylene having 1 to 7 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH;

[0090] Sp.sup.2 is alkylene having 1 to 7 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O; and

[0091] X.sup.1 is OH, NH.sub.2 or N(R.sup.3).sub.2, in which R.sup.3 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine.

[0092] Item 6. The compound according to any one of items 1 to 5, represented by any one of formulas (1-11) to (1-14):

##STR00018##

wherein, in formulas (1-11) to (1-14),

[0093] R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0094] ring A.sup.1, ring A.sup.2, ring A.sup.3 and ring A.sup.4 are independently 1,4-cyclohexylene, 1,4-phenylene, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbons;

[0095] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond or (CH.sub.2).sub.2;

[0096] Sp.sup.1 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0097] Sp.sup.2 is alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O; and

[0098] X.sup.1 is OH, NH.sub.2 or N(R.sup.3).sub.2, in which R.sup.3 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine.

[0099] Item 7. The compound according to any one of items 1 to 6, represented by any one of formulas (1-15) to (1-31):

##STR00019## ##STR00020## ##STR00021##

wherein, in formulas (1-15) to (1-31),

[0100] R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0101] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond or (CH.sub.2).sub.2;

[0102] Sp.sup.1 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0103] Sp.sup.2 is alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0104] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9 and L.sup.10 are independently hydrogen, fluorine, methyl or ethyl;

[0105] Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 are independently hydrogen or methyl; and

[0106] X.sup.1 is OH, NH.sub.2 or N(R.sup.3).sub.2, in which R.sup.3 is hydrogen or alkyl having 1 to 4 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and in the groups, at least one hydrogen may be replaced by fluorine.

[0107] Item 8. The compound according to any one of items 1 to 7, represented by any one of formulas (1-32) to (1-43):

##STR00022## ##STR00023##

wherein, in formulas (1-32) to (1-43),

[0108] R.sup.1 is alkyl having 1 to 10 carbons;

[0109] Sp.sup.1 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and in the groups, at least one hydrogen may be replaced by fluorine;

[0110] Sp.sup.2 is alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0111] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8 and L.sup.9 are independently hydrogen, fluorine, methyl or ethyl;

[0112] Y.sup.1 and Y.sup.2 are independently hydrogen or methyl; and

[0113] X.sup.1 is OH, NH.sub.2 or N(R.sup.3).sub.2, in which R.sup.3 is hydrogen or alkyl having 1 to 4 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O.

[0114] Item 9. The compound according to any one of items 1 to 8, represented by any one of formulas (1-44) to (1-63):

##STR00024## ##STR00025## ##STR00026## ##STR00027##

wherein, in formulas (1-44) to (1-63),

[0115] R.sup.1 is alkyl having 1 to 10 carbons;

[0116] Sp.sup.1 is a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and in the groups, at least one hydrogen may be replaced by fluorine;

[0117] Sp.sup.2 is alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0118] L.sup.1, L.sup.2, L.sup.3, L.sup.4 and L.sup.5 are independently hydrogen, fluorine, methyl or ethyl;

[0119] Y.sup.1 and Y.sup.2 are independently hydrogen or methyl; and

[0120] R.sup.3 is hydrogen, methyl or ethyl.

2. Form of Compound (1)

[0121] Compound (1) has features of having a mesogen moiety formed of at least one ring, and an acryloyloxy group in which replacement by a polar group such as a hydroxyalkyl group is made. Compound (1) is useful because the polar group noncovalently interacts with a substrate surface. One of applications is as an additive for the liquid crystal composition used in the liquid crystal display device. Compound (1) is added for the purpose of controlling alignment of liquid crystal molecules. Such an additive preferably has high chemical stability under conditions in which the additive is sealed in the device, high solubility in the liquid crystal composition, and a large voltage holding ratio when the composition is used in the liquid crystal display device. Compound (1) satisfies such characteristics to a significant extent.

[0122] Preferred examples of compound (1) will be described. Preferred examples of R.sup.1, MES, Sp.sup.1, R.sup.2, M.sup.1 or M.sup.2 in compound (1) are also applied to a subordinate formula of formula (1) for compound (1). In compound (1), characteristics can be arbitrarily adjusted by suitably combining kinds of the groups. Compound (1) may contain a larger amount of isotope such as .sup.2H (deuterium) and .sup.13C than an amount of natural abundance because no significant difference exists in the characteristics of the compound.

##STR00028##

[0123] In formula (1), R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0124] In formula (1), preferred R.sup.1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons. Further preferred R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons. Particularly preferred R.sup.1 is alkyl having 1 to 10 carbons.

[0125] In formula (1), MES is a mesogen group having at least one ring. The mesogen group is well known by those skilled in the art. The mesogen group means a part that contributes to formation of a liquid crystal phase when the compound has the liquid crystal phase (mesophase). Preferred examples of compound (1) include compound (1-1).

##STR00029##

[0126] In formula (1-1), preferred ring A.sup.1 or ring A.sup.4 is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine. Further preferred ring A.sup.1 or ring A.sup.4 is 1,4-cyclohexylene, 1,4-phenylene, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbons. Particularly preferred ring A.sup.1 or ring A.sup.4 is 1,4-cyclohexylene, 1,4-phenylene or perhydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, for example, as in 1-methyl-1,4-cyclohexylene, 2-ethyl-1,4-cyclohexylene and 2-fluoro-1,4-phenylene, at least one hydrogen may be replaced by fluorine, methyl or ethyl.

[0127] In formula (1-1), Z.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0128] In formula (1-1), preferred Z.sup.1 is a single bond, (CH.sub.2).sub.2, CHCH, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF. Further preferred Z.sup.1 is a single bond, (CH.sub.2).sub.2 or CHCH. Particularly preferred Z.sup.1 is a single bond.

[0129] In formula (1-1), a is 0, 1, 2, 3 or 4. Preferred a is 0, 1, 2 or 3. Further preferred a is 0, 1 or 2.

[0130] In formula (1), Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0131] In formula (1), preferred Sp.sup.1 is a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.1 is a single bond, alkylene having 1 to 3 carbons, or alkylene having 1 to 3 carbons in which one CH.sub.2 is replaced by O.

[0132] In formula (1), M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred M.sup.1 or M.sup.2 is hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Further preferred M.sup.1 or M.sup.2 is hydrogen.

[0133] In formula (1), R.sup.2 is a group represented by formula (1a), (1b) or (1c). Preferred R.sup.2 is a group represented by formula (1a) or (1b). Further preferred R.sup.2 is a group represented by formula (1a).

##STR00030##

[0134] In formulas (1a), (1b) and (1c), Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0135] In formulas (1a), (1b) and (1c), preferred Sp.sup.2 or Sp.sup.3 is alkylene having 1 to 7 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.2 or Sp.sup.3 is alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Particularly preferred Sp.sup.2 or Sp.sup.3 is CH.sub.2.

[0136] In formulas (1a), (1b) and (1c), S.sup.1 is >CH or >N; and S.sup.2 is >C< or >Si<. Preferred S.sup.1 is >CH or >N, and preferred S.sup.2 is >C<. Formula (1b) is preferred to formula (1c).

[0137] In formulas (1a), (1b) and (1c), X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.3, N(R.sup.3).sub.2, formula (x1), COOH, SH, B (OH).sub.2 or Si(R.sup.3).sub.3, in which R.sup.3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen, and w in formula (x1) is 1, 2, 3 or 4.

##STR00031##

[0138] In formulas (1a), (1b) and (1c), preferred X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.3, N(R.sup.3).sub.2, formula (x1) or Si(R.sup.3).sub.3, in which R.sup.3 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine, and w in formula (x1) is 1, 2, 3 or 4. Further preferred X.sup.1 is OH, NH.sub.2 or N(R.sup.3).sub.2. Particularly preferred X.sup.1 is OH.

##STR00032##

3. Synthesis of Compound (1)

[0139] Synthesis methods of compound (1) will be described. Compound (1) can be synthesized by suitably combining methods in publicly-known synthetic organic chemistry. The synthesis methods may be applied with reference to books such as Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Shin Jikken Kagaku Koza in Japanese) (Maruzen Co., Ltd.).

4. Example of Compound (1)

[0140] Compound (1) will be described as an example in the following items.

[0141] Item 21. A compound, represented by formula (1):

##STR00033##

wherein, in formula (1),

[0142] R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0143] MES is a mesogen group having at least one ring;

[0144] Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; and

[0145] R.sup.2, M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, halogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0146] Item 22. The compound according to item 21, represented by formula (1-1):

##STR00034##

wherein, in formula (1-1),

[0147] R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0148] ring A.sup.1 and ring A.sup.4 are independent 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0149] Z.sup.1 is a single bond or alkylene having 1 to 4 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0150] Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0151] R.sup.2, M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, halogen or alkyl having 1 to 8 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; and

[0152] a is 0, 1, 2, 3 or 4; and

[0153] when a is 0 and ring A.sup.4 is 1,4-cyclohexylene or 1,4-phenylene, R.sup.1 is alkyl having 5 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; and

[0154] when a is 0 and ring A.sup.4 is perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, M.sup.1 is halogen or alkyl having 1 to 8 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0155] Item 23. The compound according to item 21 or 22, represented by any one of formulas (1-3) to (1-6):

##STR00035##

wherein, in formulas (1-3) to (1-6),

[0156] R.sup.1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0157] ring A.sup.1, ring A.sup.2, ring A.sup.3 and ring A.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 7 carbons, alkenyl having 2 to 7 carbons or alkoxy having 1 to 6 carbons;

[0158] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond, (CH.sub.2).sub.2, CHCH, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF;

[0159] Sp.sup.1 is a single bond or alkylene having 1 to 7 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO or OCO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine; and

[0160] R.sup.2, M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen or alkyl having 1 to 8 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; and

[0161] in formula (1-3), when ring A.sup.4 is 1,4-cyclohexylene or 1,4-phenylene, R.sup.1 is alkyl having 5 to 15 carbons, alkenyl having 5 to 15 carbons, alkoxy having 4 to 14 carbons or alkenyloxy having 4 to 14 carbons, and in the groups, at least one hydrogen may be replaced by fluorine; and

[0162] in formula (1-3), when ring A.sup.4 is perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, M.sup.1 is alkyl having 1 to 8 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0163] Item 24. The compound according to any one of items 21 to 23, represented by any one of formulas (1-3) to (1-6):

##STR00036##

wherein, in formulas (1-3) to (1-6),

[0164] M.sup.2 and M.sup.3 are hydrogen;

[0165] R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons;

[0166] ring A.sup.1, ring A.sup.2, ring A.sup.3 and ring A.sup.4 are independently 1,4-cyclohexylene, 1,4-phenylene, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbons;

[0167] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond or (CH.sub.2).sub.2;

[0168] Sp.sup.1 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O; and

[0169] M.sup.1 and R.sup.2 are independently hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O; and

[0170] in formula (1-3), when ring A.sup.4 is 1,4-cyclohexylene or 1,4-phenylene, R.sup.1 is alkyl having 5 to 10 carbons, alkenyl having 5 to 10 carbons or alkoxy having 4 to 9 carbons; and

[0171] in formula (1-3), when ring A.sup.4 is perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, M.sup.1 is alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O.

[0172] Item 25. The compound according to any one of items 21 to 24, represented by any one of formulas (1-7) to (1-20):

##STR00037##

wherein, in formulas (1-7) to (1-20),

[0173] R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons;

[0174] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond or (CH.sub.2).sub.2;

[0175] Sp.sup.1 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0176] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11, L.sup.12, L.sup.13 and L.sup.14 are independently hydrogen, fluorine, methyl or ethyl;

[0177] Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 are independently hydrogen or methyl, and M.sup.1 is hydrogen or alkyl having 1 to 5 carbons;

[0178] M.sup.4 is alkyl having 1 to 5 carbons; and

[0179] R.sup.2 is hydrogen, methyl or ethyl.

[0180] Item 26. The compound according to any one of items 21 to 24, represented by any one of formulas (1-21) to (1-29):

##STR00038## ##STR00039##

wherein, in formulas (1-21) to (1-29),

[0181] R.sup.1 is alkyl having 1 to 10 carbons;

[0182] Sp.sup.1 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0183] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11 and L.sup.12 are independently hydrogen, fluorine, methyl or ethyl;

[0184] Y.sup.1 and Y.sup.2 are independently hydrogen or methyl, and

[0185] M.sup.1 is hydrogen, methyl or ethyl;

[0186] M.sup.4 is methyl or ethyl; and

[0187] R.sup.2 is hydrogen or methyl.

[0188] Item 27. The compound according to any one of items 21 to 24, represented by any one of formulas (1-30) to (1-36):

##STR00040##

wherein, in formulas (1-30) to (1-36),

[0189] R.sup.1 is alkyl having 1 to 10 carbons;

[0190] Sp.sup.1 is a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0191] L.sup.1, L.sup.2, L.sup.3, L.sup.4 and L.sup.5 are independently hydrogen, fluorine, methyl or ethyl;

[0192] Y.sup.1 and Y.sup.2 are independently hydrogen or methyl; and

[0193] R.sup.2 is hydrogen or methyl.

5. Form of Compound (1)

[0194] Compound (1) has features of having a mesogen moiety formed of at least one ring, and an acrylamide group. Compound (1) is useful because a polar group noncovalently interacts with a substrate surface. One of applications is as an additive for the liquid crystal composition used in the liquid crystal display device. Compound (1) is added for the purpose of controlling alignment of liquid crystal molecules. Such an additive preferably has high chemical stability under conditions in which the additive is sealed in the device, high solubility in the liquid crystal composition, and the large voltage holding ratio when the liquid crystal composition is used in the liquid crystal display device. Compound (1) satisfies such characteristics to a significant extent.

[0195] Preferred examples of compound (1) will be described. Preferred examples of R.sup.1, MES, Sp.sup.1, M.sup.1, R.sup.2, M.sup.2 or M.sup.3 in compound (1) are also applied to a subordinate formula of formula (1) for compound (1). In compound (1), characteristics can be arbitrarily adjusted by suitably combining kinds of the groups. Compound (1) may contain a larger amount of isotope such as .sup.2H (deuterium) and .sup.13C than an amount of natural abundance because no significant difference exists in the characteristics of the compound.

##STR00041##

[0196] In formula (1), R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0197] In formula (1), preferred R.sup.1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons. Further preferred R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons. Particularly preferred R.sup.1 is alkyl having 1 to 10 carbons.

[0198] In formula (1), MES is a mesogen group having at least one ring. The mesogen group is well known by those skilled in the art. The mesogen group means the part that contributes to formation of the liquid crystal phase when the compound has the liquid crystal phase (mesophase). Preferred examples of compound (1) include compound (1-1).

##STR00042##

[0199] In formula (1-1), preferred ring A.sup.1 or ring A.sup.4 is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine. Further preferred ring A.sup.1 or ring A.sup.4 is 1,4-cyclohexylene, 1,4-phenylene, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbons. Particularly preferred ring A.sup.1 or ring A.sup.4 is 1,4-cyclohexylene, 1,4-phenylene or perhydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, methyl or ethyl.

[0200] In formula (1-1), Z.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0201] In formula (1-1), preferred Z.sup.1 is a single bond, (CH.sub.2).sub.2, CHCH, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF. Further preferred Z.sup.1 is a single bond, (CH.sub.2).sub.2 or CHCH. Particularly preferred Z.sup.1 is a single bond.

[0202] In formula (1-1), a is 0, 1, 2, 3 or 4. Preferred a is 0, 1, 2 or 3. Further preferred a is 0, 1 or 2.

[0203] In formula (1), Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0204] In formula (1), preferred Sp.sup.1 is a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.1 is a single bond, alkylene having 1 to 3 carbons, or alkylene having 1 to 3 carbons in which one CH.sub.2 is replaced by O.

[0205] In formula (1), M.sup.2 and M.sup.3 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred M.sup.2 or M.sup.3 is hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Further preferred M.sup.2 or M.sup.3 is hydrogen.

[0206] In formula (1), R.sup.2 is hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred R.sup.2 is hydrogen, methyl and ethyl. Further preferred R.sup.2 is hydrogen.

[0207] In formula (1), M.sup.1 is hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred M.sup.1 is hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Further preferred M.sup.1 is methyl.

6. Synthesis of Compound (1)

[0208] Synthesis methods of compound (1) will be described. Compound (1) can be synthesized by suitably combining methods in publicly-known synthetic organic chemistry. The synthesis methods may be applied with reference to books such as Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Shin Jikken Kagaku Koza in Japanese) (Maruzen Co., Ltd.).

7. Example of Compound (1)

[0209] Compound (1) will be described as an example in the following items.

[0210] Item 41. A compound, represented by formula (1):

##STR00043##

wherein, in formula (1),

[0211] R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen or alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, S or NH, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen;

[0212] n is independently 0, 1 or 2;

[0213] ring A.sup.4 is cyclohexylene, cyclohexenylene, phenylene, naphthalene, decahydronaphthalene, tetrahydronaphthalene, tetrahydropyran, 1,3-dioxane, pyrimidine or pyridine, and ring A.sup.1 and ring A.sup.5 are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl or pyridine-2-yl, and

[0214] in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0215] Z.sup.1 and Z.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0216] Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0217] a and b are independently 0, 1, 2, 3 or 4, and a sum of a and b is 1, 2, 3 or 4;

[0218] c, d and e are independently 0, 1, 2, 3 or 4;

[0219] a sum of c, d and e is 2, 3 or 4; and

[0220] P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1):

##STR00044##

wherein, in formula (P-1),

[0221] M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and

[0222] R.sup.4 is a group selected from the group of groups represented by formulas (1a), (1b) and (1c):

##STR00045##

wherein, in formulas (1a), (1b) and (1c),

[0223] Sp.sup.5 and Sp.sup.6 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0224] S.sup.1 is >CH or >N;

[0225] S.sup.2 is >C< or >Si<; and

[0226] X.sup.1 is independently a group represented by OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3, in which R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen.

[0227] Item 42. The compound according to item 41, wherein, in formula (P-1), R.sup.4 is a group represented by formula (1a) or (1b).

[0228] Item 43. The compound according to item 41 or 42, wherein, in formula (1), R.sup.4 is represented by formula (1a), c, d and e are 0, 1, 2 or 3, and a sum of c, d and e is 2, 3 or 4.

[0229] Item 44. The compound according to any one of items 41 to 43, represented by any one of formulas (1-1) to (1-6):

##STR00046##

wherein, in formulas (1-1) to (1-6),

[0230] R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0231] ring A.sup.1, ring A.sup.2, ring A.sup.3, ring A.sup.4, ring A.sup.5 and ring A.sup.6 are independently cyclohexylene, cyclohexenylene, phenylene, naphthalene, tetrahydropyran or 1,3-dioxane, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0232] Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.5 and Z.sup.6 are independently a single bond or alkylene having 1 to 8 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO or OCO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0233] Sp.sup.1, Sp.sup.2, Sp.sup.3 and Sp.sup.4 are independently a single bond or alkylene having 1 to 8 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO or OCO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0234] c, d, e and f are independently 0, 1, 2 or 3, and a sum of c, d, e and f is 2, 3 or 4, in which, in formulas (1-1) to (1-3), d is 2 or 3; and

[0235] P.sup.1, P.sup.2, P.sup.3 and P.sup.4 are independently a polymerizable group represented by formula (P-1):

##STR00047##

wherein, in formula (P-1),

[0236] M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 4 carbons, or alkyl having 1 to 4 carbons in which at least one hydrogen is replaced by halogen;

[0237] Sp.sup.5 is a single bond or alkylene having 1 to 8 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO or OCO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; and

[0238] X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2 or Si(R.sup.5).sub.3, in which R.sup.5 is hydrogen or alkyl having 1 to 8 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen.

[0239] Item 45. The compound according to item 44, wherein, in formulas (1-1) to (1-6),

[0240] R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0241] ring A.sup.1, ring A.sup.2, ring A.sup.3, ring A.sup.4, ring A.sup.5 and ring A.sup.6 are independently cyclohexylene, cyclohexenylene, phenylene, naphthalene or tetrahydropyran, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 6 carbons, alkenyl having 2 to 6 carbons or alkoxy having 2 to 5 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0242] Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.5 and Z.sup.6 are independently a single bond or alkylene having 1 to 6 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO or OCO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be alternatively replaced by fluorine;

[0243] Sp.sup.1, Sp.sup.2, Sp.sup.3 and Sp.sup.4 are independently a single bond or alkylene having 1 to 6 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine;

[0244] c, d, e and f are independently 0, 1, 2 or 3, and a sum of c, d, e and f is 2, 3 or 4, in which, in formulas (1-1) to (1-3), d is 2 or 3; and

[0245] P.sup.1, P.sup.2, P.sup.3 and P.sup.4 are independently a polymerizable group represented by formula (P-1):

##STR00048##

wherein, in formula (P-1),

[0246] M.sup.1 and M.sup.2 are independently hydrogen, alkyl having 1 to 3 carbons, or alkyl having 1 to 3 carbons in which at least one hydrogen is replaced by halogen; and

[0247] Sp.sup.5 is a single bond or alkylene having 1 to 6 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine, and

[0248] X.sup.1 is a group represented by OH and NH.sub.2.

[0249] Item 46. The compound according to any one of items 41 to 45, represented by any one of formulas (1-7) to (1-21):

##STR00049##

wherein, in formulas (1-7) to (1-21),

[0250] R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen, alkyl having 1 to 8 carbons, alkenyl having 2 to 8 carbons, alkoxy having 1 to 7 carbons or alkenyloxy having 2 to 7 carbons;

[0251] ring A.sup.1, ring A.sup.2, ring A.sup.3, ring A.sup.4 and ring A.sup.5 are independently cyclohexylene, cyclohexenylene or phenylene, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons or alkoxy having 1 to 4 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0252] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.7, L.sup.8, L.sup.10, L.sup.12, L.sup.13, L.sup.15, L.sup.16, L.sup.17, L.sup.18, L.sup.19 and L.sup.20 are independently fluorine, methyl or ethyl;

[0253] Sp.sup.1, Sp.sup.2, Sp.sup.3 and Sp.sup.4 are independently a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0254] c, d, e and f are independently 0, 1 or 2, and a sum of c, d, e and f is 2, 3 or 4, in which, in formulas (1-7) to (1-9), d is 2; and

[0255] P.sup.1, P.sup.2, P.sup.3 and P.sup.4 are independently a polymerizable group represented by formula (P-1):

##STR00050##

wherein, in formula (P-1),

[0256] M.sup.1 and M.sup.2 are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl;

[0257] Sp.sup.5 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O; and

[0258] X.sup.1 is a group represented by OH and NH.sub.2.

[0259] Item 47. In formulas (1-7) to (1-21), R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen, alkyl having 1 to 8 carbons, alkenyl having 2 to 8 carbons, alkoxy having 1 to 7 carbons or alkenyloxy having 2 to 7 carbons;

[0260] ring A.sup.1, ring A.sup.2, ring A.sup.3, ring A.sup.4 and ring A.sup.5 are independently cyclohexylene, cyclohexenylene or phenylene, and in the rings, at least one hydrogen may be replaced by fluorine, alkyl having 1 to 3 carbons, alkenyl having 2 to 3 carbons or alkoxy having 1 to 2 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0261] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.7, L.sup.8, L.sup.10, L.sup.12, L.sup.13, L.sup.15, L.sup.16, L.sup.17, L.sup.18, L.sup.19 and L.sup.20 are independently fluorine, methyl or ethyl;

[0262] Sp.sup.1, Sp.sup.2, Sp.sup.3 and Sp.sup.4 are independently a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0263] c, d, e and f are independently 0, 1 or 2, and a sum of c, d, e and f is 2, 3 or 4, in which, in formulas (1-7) to (1-9), d is 2; and

[0264] P.sup.1, P.sup.2, P.sup.3 and P.sup.4 are independently a polymerizable group represented by formula (P-1):

##STR00051##

wherein, in formula (P-1),

[0265] M.sup.1 and M.sup.2 are independently hydrogen, fluorine, methyl or ethyl;

[0266] Sp.sup.5 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O; and

[0267] X.sup.1 is a group represented by OH and NH.sub.2.

[0268] Item 48. The compound according to any one of items 41 to 47, represented by any one of formulas (1-22) to (1-34):

##STR00052##

wherein, in formulas (1-22) to (1-34),

[0269] R.sup.1 and R.sup.2 are alkyl having 1 to 7 carbons, alkenyl having 2 to 7 carbons, alkoxy having 1 to 6 carbons or alkenyloxy having 2 to 6 carbons;

[0270] L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11, L.sup.13, L.sup.15, L.sup.16, L.sup.17, L.sup.18, L.sup.19, L.sup.20, L.sup.21, L.sup.22 and L.sup.23 are independently hydrogen, fluorine, methyl or ethyl;

[0271] Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O; and

[0272] P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1):

##STR00053##

wherein, in formula (P-1),

[0273] M.sup.1 and M.sup.2 are independently hydrogen, fluorine or methyl; and

[0274] Sp.sup.5 is a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O.

8. Form of Compound (1)

[0275] Compound (1) has features of having a mesogen moiety formed of at least one ring, and a plurality of polar groups. Compound (1) is useful because the polar group noncovalently interacts with a substrate surface. One of applications is as an additive for the liquid crystal composition used in the liquid crystal display device. Compound (1) is added for the purpose of controlling alignment of liquid crystal molecules. Such an additive preferably has high chemical stability under conditions in which the additive is sealed in the device, high solubility in the liquid crystal composition, and the large voltage holding ratio when the liquid crystal composition is used in the liquid crystal display device. Compound (1) satisfies such characteristics to a significant extent.

[0276] Preferred examples of compound (1) will be described. Preferred examples of R.sup.1, R.sup.2, R.sup.2, R.sup.3, Z.sup.1, Z.sup.2, Z.sup.3, A.sup.1, A.sup.4, A.sup.5, Sp.sup.1, Sp.sup.2, Sp.sup.3, P.sup.1, P.sup.2 or P.sup.3 are also applied to a subordinate formula of formula (1) for compound (1). In compound (1), characteristics can be arbitrarily adjusted by suitably combining kinds of the groups. Compound (1) may contain a larger amount of isotope such as .sup.2H (deuterium) and .sup.13C than an amount of natural abundance because no significant difference exists in the characteristics of the compound.

##STR00054##

[0277] In formula (1), R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0278] In formula (1), preferred R.sup.1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons. Further preferred R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons. Particularly preferred R.sup.1 is alkyl having 1 to 10 carbons.

[0279] In formula (1), ring A.sup.1, ring A.sup.4 and ring A.sup.5 are independently cyclohexylene, cyclohexenylene, phenylene, naphthalene, decahydronaphthalene, tetrahydronaphthalene, tetrahydropyran, 1,3-dioxane, pyrimidine or pyridine, and in the rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen.

[0280] In formula (1), preferred ring A.sup.1, ring A.sup.4 or ring A.sup.5 is cyclohexylene, cyclohexenylene, phenylene, naphthalene, tetrahydropyran or 1,3-dioxane, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 5 carbons or alkoxy having 1 to 4 carbons. Further preferred ring A.sup.1, ring A.sup.4 or ring A.sup.5 is cyclohexylene, phenylene, phenylene in which at least one hydrogen is replaced by fluorine, or phenylene in which at least one hydrogen is replaced by alkyl having 1 to 3 carbons. Particularly preferred ring A.sup.1, ring A.sup.4 or ring A.sup.5 is cyclohexylene, phenylene, phenylene in which at least one hydrogen is replaced by a methyl group, or phenylene in which at least one hydrogen is replaced by an ethyl group.

[0281] In formula (1), Z.sup.1 and Z.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0282] In formula (1), preferred Z.sup.1 or Z.sup.5 is a single bond, (CH.sub.2).sub.2, CHCH, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF. Further preferred Z.sup.1 or Z.sup.5 is a single bond.

[0283] In formula (1), Sp.sup.1, Sp.sup.2 or Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0284] In formula (1) r preferred Sp.sup.1, Sp.sup.2 or Sp.sup.3 is a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.1, Sp.sup.2 or Sp.sup.3 is a single bond, alkylene having 1 to 3 carbons, or alkylene having 1 to 3 carbons in which one CH.sub.2 is replaced by O. Particularly preferred Sp.sup.1, Sp.sup.2 or Sp.sup.3 is CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3 or O(CH.sub.2).sub.2.

[0285] In formula (1), P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1).

##STR00055##

[0286] In formula (P-1), M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred M.sup.1 or M.sup.2 is hydrogen or methyl for increasing reactivity. Further preferred M.sup.1 or M.sup.2 is hydrogen.

[0287] In formula (P-1), R.sup.4 is a group represented by a group represented by formulas (1a), (1b) and (1c). Preferred R.sup.4 is a group represented by formula (1a) or (1b). Further preferred R.sup.4 is a group represented by formula (1a).

##STR00056##

[0288] In formulas (1a), (1b) and (1c), Sp.sup.5 and Sp.sup.6 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0289] In formulas (1a), (1b) and (1c), preferred Sp.sup.5 and Sp.sup.6 are a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.4 or Sp.sup.5 is a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Particularly preferred Sp.sup.5 and Sp.sup.6 are a single bond, CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3 or O(CH.sub.2).sub.2.

[0290] In formulas (1a), (1b) and (1c), S.sup.1 is >CH or >N; and S.sup.2 is >C< or >Si<. Preferred S.sup.1 is >CH or >N, and preferred S.sup.2 is >C<. S.sup.1 is preferred to S.sup.2.

[0291] In formulas (1a), (1b) and (1c), X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.3, N(R.sup.3).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.3).sub.3, in which R.sup.3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0292] In formulas (1a), (1b) and (1c), preferred X.sup.1 is a group represented by OH, NH.sub.2 or Si(R.sup.3).sub.3, in which R.sup.3 is alkyl having 1 to 5 carbons or alkoxy having 1 to 4 carbons. Further preferred X.sup.1 is OH, NH.sub.2, Si(OCH.sub.3).sub.3 or Si(OC.sub.2H.sub.5).sub.3. Particularly preferred X.sup.1 is OH.

[0293] In formula (1), a and b are independently 0, 1, 2, 3 or 4, and a sum of a and b is 1, 2, 3 or 4. A preferred combination of a and b includes (a=1, b=0), (a=0, b=1), (a=2, b=0), (a=1, b=1), (a=0, b=2), (a=3, b=0), (a=2, b=1), (a=1, b=2) or (a=0, b=3). A further preferred combination of a and b includes (a=1, b=0), (a=2, b=0), (a=1, b=1), (a=3, b=0), (a=2, b=1) or (a=1, b=2). A particularly preferred combination of a and b includes (a=1, b=0) or (a=2, b=0).

[0294] In formula (1) r d is 0, 1, 2, 3 or 4. Preferred d is 2 or 3, and further preferred d is 2.

[0295] In formula (1), c and e are independently 0, 1, 2, 3 or 4. Preferred c or e is 0.

9. Synthesis of Compound (1)

[0296] Synthesis methods of compound (1) will be described. Compound (1) can be synthesized by suitably combining methods in publicly-known synthetic organic chemistry. The synthesis methods may be applied with reference to books such as Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Shin Jikken Kagaku Koza in Japanese) (Maruzen Co., Ltd.).

[0297] 10. Example of Compound (1)

[0298] Compound (1) will be described as an example in the following items.

[0299] Item 61, A compound, represented by formula (1-1):

##STR00057##

wherein, in formula (1-1),

[0300] R.sup.1 is alkyl having 1 to 15 carbons, and in R.sup.1, at least one CH.sub.2 may be replaced by O or S, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen;

[0301] ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0302] a is 0, 1, 2, 3 or 4;

[0303] Z.sup.1 is a single bond or alkylene having 1 to 6 carbons, and in Z.sup.1, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by fluorine or chlorine; and

[0304] Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.1, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen, and in the groups, at least one hydrogen is replaced by a group selected from the group of groups represented by formula (1a):

##STR00058##

wherein, in formula (1a),

[0305] Sp.sup.12 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.12, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen;

[0306] M.sup.11 and M.sup.12 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and

[0307] R.sup.12 is alkyl having 1 to 15 carbons, and in R.sup.12, at least one CH.sub.2 may be replaced by O or S, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen: and

in formula (1-1),

[0308] P.sup.11 is a group selected from the group of groups represented by formulas (1e) and (1f):

##STR00059##

wherein, in formulas (1e) and (1f),

[0309] Sp.sup.13 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.13, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0310] Sp.sup.14 are independently a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.14, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen;

[0311] M.sup.13 and M.sup.14 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and

[0312] X.sup.1 is OH, NH.sub.2, OR.sup.15, N(R.sup.15).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.15).sub.3; and

[0313] in OR.sup.15, N(R.sup.15).sub.2 and Si(R.sup.15).sub.3,

[0314] R.sup.15 is hydrogen or alkyl having 1 to 10 carbons, and in R.sup.15, at least one CH.sub.2 may be replaced by O, at least one CH.sub.2CH.sub.2 may be replaced by CHCH, and at least one hydrogen may be replaced by halogen.

[0315] Item 62. The compound according to item 61, represented by formulas (1-2) to (1-21):

##STR00060## ##STR00061## ##STR00062##

wherein, in formulas (1-2) to (1-21),

[0316] R.sup.1 is alkyl having 1 to 10 carbons;

[0317] Z.sup.1, Z.sup.12 and Z.sup.13 are independently a single bond, CH.sub.2CH.sub.2 or (CH.sub.2).sub.4;

[0318] Sp.sup.12, Sp.sup.13 and Sp.sup.14 are independently a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0319] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11 and L.sup.12 are independently hydrogen, fluorine, methyl or ethyl; and

[0320] l is 1, 2, 3, 4, 5 or 6.

11. Form of Compound (1)

[0321] Compound (1) is adsorbed onto a substrate surface by action of a polar group to control alignment of liquid crystal molecules. Compound (1) is required to have high compatibility with a liquid crystal compound in order to obtain a desired effect. Compound (1) has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has rod-like molecular structure, and moreover has a branched structure in one end of the molecular structure, and is considered that compatibility can be improved, and therefore is optimum for the purpose above. Compound (1) is polymerized to give a polymer. The polymer stabilizes the alignment of the liquid crystal molecules, and therefore the response time of the device is shortened and the image persistence is improved.

[0322] A preferred form of compound (1) will be described. In formula (1-1), X.sup.1 is a polar group. Compound (1-1) is added to the composition, and therefore is preferably stable. When compound (1) is added to the composition, the compound preferably does not decrease the voltage holding ratio of the device. Compound (1-1) preferably has low volatility. Preferred molar mass is 130 g/mol or more. Further preferred molar mass is in the range from 150 g/mol to 700 g/mol. Preferred compound (1) has a polymerizable group such as acryloyloxy (OCOCHCH.sub.2) and methacryloyloxy (OCO(CH.sub.3)CCH.sub.2).

[0323] In formula (1-1), X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.15, N(R.sup.15).sub.2 or Si(R.sup.15).sub.3, in which R.sup.15 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one CH.sub.2CH.sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine. From a viewpoint of high solubility in the liquid crystal composition, X.sup.1 is particularly preferably OH or NH.sub.2. Then, OH has high anchor force, and therefore is preferred to O, CO or COO. A group containing a plurality of hetero atoms (nitrogen, oxygen) is particularly preferred. A compound having such a polar group is effective even at a low concentration.

[0324] In formula (1-1), R.sup.1 is alkyl having 1 to 15 carbons, and in R.sup.1, at least one CH.sub.2 may be replaced by O or S, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen.

[0325] In formula (1-1), ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred ring A.sup.1 or ring A.sup.2 is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-2,6-diyl or 3-ethyl-1,4-phenylene.

[0326] In formula (1-1), Z.sup.1 is a single bond or alkylene having 1 to 6 carbons, and in Z.sup.1, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z.sup.1 is a single bond, CH.sub.2CH.sub.2, CH.sub.2O, OCH.sub.2, COO or OCO. Further preferred Z.sup.1 is a single bond.

[0327] In formula (1-1), Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.1, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen, and in the groups, at least one hydrogen is replaced by a group selected from the group of groups represented by formula (1a):

##STR00063##

wherein, in formula (1a), Sp.sup.12 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.12, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen; and

[0328] in formula (1a), M.sup.11 and M.sup.12 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and

[0329] in formula (1a), R.sup.12 is alkyl having 1 to 15 carbons, and in R.sup.12, at least one CH.sub.2 may be replaced by O or S, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen. Preferred Sp.sup.1 is a single bond.

[0330] In formula (1-1), P.sup.11 is a group selected from the group of groups represented by formulas (1e) and (1f):

##STR00064##

wherein, in formulas (1e) and (1f),

[0331] Sp.sup.13 is a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.13, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0332] Sp.sup.14 are independently a single bond or alkylene having 1 to 10 carbons, and in Sp.sup.14, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and at least one hydrogen may be replaced by halogen;

[0333] M.sup.13 and M.sup.14 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and

[0334] X.sup.1 is OH, NH.sub.2, OR.sup.15, N(R.sup.15).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.15).sub.3; and

[0335] in OR.sup.15, N(R.sup.15).sub.2 and Si(R.sup.15).sub.3,

[0336] R.sup.15 is hydrogen or alkyl having 1 to 10 carbons, and in R.sup.15, at least one CH.sub.2 may be replaced by O, at least one CH.sub.2CH.sub.2 may be replaced by CHCH, and at least one hydrogen may be replaced by halogen.

[0337] In formula (1-1), a is 0, 1, 2, 3 or 4. Preferred a is 0, 1 or 2.

[0338] In formulas (1-2) to (1-21),

[0339] R.sup.1 is alkyl having 1 to 10 carbons;

[0340] Z.sup.1, Z.sup.12 and Z.sup.13 are independently a single bond, CH.sub.2CH.sub.2 or (CH.sub.2).sub.4; Sp.sup.12, Sp.sup.13 and Sp.sup.14 are independently a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O; and

[0341] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11 and L.sup.12 are independently hydrogen, fluorine, methyl or ethyl.

[0342] Preferred compound (1) includes compound (1-2) to compound (1-21) described in item 62. In the compounds, at least one of the alignable monomers preferably includes compound (1-2), compound (1-3), compound (1-4), compound (1-11), compound (1-19) or compound (1-21). At least two of the alignable monomers preferably include a combination of compound (1-2) and compound (1-3) or a combination of compound (1-3) and compound (1-4).

12. Synthesis of Compound (1)

[0343] A method for synthesizing compound (1) is described in a section of Examples.

13. Example of Compound (1)

[0344] Compound (1) will be described as an example in the following items.

[0345] Item 81. A compound, represented by formula (1):

R.sup.1-MES-Sp.sup.1-P.sup.1(1)

wherein, in formula (1),

[0346] R.sup.1 is alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0347] MES is a mesogen group having at least one ring; and

[0348] Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen, and in the groups, at least one hydrogen is replaced by a group selected from the group of groups represented by formulas (1a), (1b), (1c) and (1d):

##STR00065##

wherein, in formulas (1a), (1b), (1c) and (1d),

[0349] Sp.sup.2 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0350] M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and

[0351] R.sup.2 is hydrogen or alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; and

in formula (1),

[0352] P.sup.1 is a group selected from the group of groups represented by formulas (1e) and (1f):

##STR00066##

wherein, in formulas (1e) and (1f),

[0353] Sp.sup.3 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0354] M.sup.3 and M.sup.4 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; X.sup.1 is OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3; and

[0355] R.sup.3 is a group selected from the group of groups represented by formulas (1g), (1h) and (1i):

##STR00067##

wherein, in formulas (1g), (1h) and (1i),

[0356] Sp.sup.4 and Sp.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0357] S.sup.1 is >CH or >N;

[0358] S.sup.2 is >C< or >Si<; and

[0359] X.sup.1 is OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3; and

[0360] in OR.sup.5, N(R.sup.5).sub.2 and N(R.sup.5).sub.2,

[0361] R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen.

[0362] Item 82. The compound according to item 81, represented by formula (1-1):

##STR00068##

wherein, in formula (1-1),

[0363] R.sup.1 is alkyl having 1 to 12 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine;

[0364] ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0365] a is 0, 1, 2, 3 or 4;

[0366] Z.sup.1 is a single bond or alkylene having 1 to 6 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; and

[0367] Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine, and in the groups, at least one hydrogen is replaced by a polymerizable group represented by formula (1a):

##STR00069##

wherein, in formula (1a),

[0368] Sp.sup.2 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0369] M.sup.1 and M.sup.2 are independently hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine; and

[0370] R.sup.2 is hydrogen or alkylene having 1 to 15 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; and

[0371] in formula (1-1),

[0372] P.sup.1 is a group selected from the group of groups represented by formulas (1e) and (1f):

##STR00070##

wherein, in formulas (1e) and (1f),

[0373] Sp.sup.3 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0374] M.sup.3 and M.sup.4 are independently hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine;

[0375] X.sup.1 is OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH or Si(R.sup.5).sub.3; and

[0376] R.sup.3 is a group selected from the group of groups represented by formulas (1g) and (1h):

##STR00071##

wherein, in formulas (1g) and (1h),

[0377] Sp.sup.4 and Sp.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0378] S.sup.1 is >CH or >N; and

[0379] X.sup.1 is OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH or Si(R.sup.5).sub.3; and

[0380] in OR.sup.5, N(R.sup.5).sub.2 and Si(R.sup.5).sub.3,

[0381] R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0382] Item 83. The compound according to item 82, wherein, in formula (1-1),

[0383] Z.sup.1 is a single bond, (CH.sub.2).sub.2, (CH.sub.2).sub.4, CHCH, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF; and

[0384] in formula (1a),

[0385] M.sup.1 and M.sup.2 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine; and

[0386] in formula (1e),

[0387] M.sup.3 and M.sup.4 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine; and

[0388] R.sup.3 is a group represented by formula (1g).

[0389] Item 84. The compound according to item 82 or 83, wherein, in formula (1-1),

[0390] ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine; and

[0391] Sp.sup.1 is a single bond or alkylene having 1 to 8 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine, and in the groups, at least one hydrogen is replaced by a group represented by formula (1a):

##STR00072##

wherein, in formula (1a),

[0392] Sp.sup.2 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0393] M.sup.1 and M.sup.2 are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl; and

[0394] R.sup.2 is hydrogen or alkylene having 1 to 8 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine; and

[0395] in formula (1-1),

[0396] P.sup.1 is a group selected from the group of groups represented by formulas (1e) and (1f):

##STR00073##

wherein, in formulas (1e) and (1f),

[0397] Sp.sup.3 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine;

[0398] M.sup.3 and M.sup.4 are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl;

[0399] X.sup.1 is OH, NH.sub.2 or N(R.sup.5).sub.2; and

[0400] R.sup.3 is a group represented by formula (1g):

-Sp.sup.4-X.sup.1 (1g)

wherein, in formulas (1g),

[0401] Sp.sup.4 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine; and

[0402] X.sup.1 is OH, NH.sub.2 or N(R.sup.5).sub.2; and

[0403] in N(R.sup.5).sub.2,

[0404] R.sup.5 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine.

[0405] Item 85. The compound according to item 81, represented by formula (1-2) or (1-3):

##STR00074##

wherein, in formulas (1-2) and (1-3),

[0406] R.sup.1 is alkyl having 1 to 12 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine;

[0407] ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, alkyl having 1 to 8 carbons, alkenyl having 2 to 8 carbons, alkoxy having 1 to 7 carbons or alkenyloxy having 2 to 7 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0408] a is 0, 1, 2, 3 or 4;

[0409] l is 1, 2, 3, 4, 5 or 6, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine;

[0410] Sp.sup.2 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine;

[0411] M.sup.1 and M.sup.2 are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl;

[0412] R.sup.2 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine;

[0413] Sp.sup.3 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO or COO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine;

[0414] M.sup.3 and M.sup.4 are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl;

[0415] Sp.sup.4 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO or COO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine; and

[0416] X.sup.1 is OH or N(R.sup.5).sub.2; and

[0417] in N(R.sup.5).sub.2,

[0418] R.sup.5 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine.

[0419] Item 86. The compound according to item 85, wherein, in formulas (1-2) and (1-3),

[0420] R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine;

[0421] ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbons;

[0422] a is 0, 1, 2, 3 or 4;

[0423] Z.sup.1 is a single bond, (CH.sub.2).sub.2, (CH.sub.2).sub.4, CHCH, CF.sub.2O, OCF.sub.2, CH.sub.2O or OCH.sub.2;

[0424] Sp.sup.2 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH;

[0425] M.sup.1 and M.sup.2 are independently hydrogen, methyl or ethyl;

[0426] R.sup.2 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be alternatively replaced by O, and at least one (CH.sub.2).sub.2 may be alternatively replaced by CHCH;

[0427] Sp.sup.3 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH;

[0428] M.sup.3 and M.sup.4 are independently hydrogen, fluorine, methyl or ethyl;

[0429] Sp.sup.4 is a single bond or alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH; and

[0430] X.sup.1 is OH or N(R.sup.5).sub.2; and

[0431] in N(R.sup.5).sub.2,

[0432] R.sup.5 is hydrogen or alkyl having 1 to 3 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O.

[0433] Item 87. The compound according to item 85, wherein, in formulas (1-2) and (1-3),

[0434] R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons;

[0435] ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-phenylene or naphthalene-2,6-diyl, and in the rings, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbons;

[0436] a is 0, 1, 2 or 3;

[0437] Z.sup.1 is a single bond, (CH.sub.2).sub.2 or (CH.sub.2).sub.4;

[0438] Sp.sup.2 is a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0439] M.sup.1 and M.sup.2 are independently hydrogen or methyl;

[0440] R.sup.2 is hydrogen or alkyl having 1 to 5 carbons, and in the alkyl, at least one CH.sub.2 may be alternatively replaced by O;

[0441] Sp.sup.3 is a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0442] M.sup.3 and M.sup.4 are independently hydrogen or methyl;

[0443] Sp.sup.4 is a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O; and

[0444] X.sup.1 is OH.

[0445] Item 88. The compound according to item 81, represented by any one of formulas (1-4) to (1-41):

##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080##

wherein, in formulas (1-4) to (1-41),

[0446] R.sup.1 is alkyl having 1 to 10 carbons;

[0447] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond, (CH.sub.2).sub.2 or (CH.sub.2).sub.4;

[0448] Sp.sup.2, Sp.sup.3 and Sp.sup.4 are independently alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0449] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11 and L.sup.12 are independently hydrogen, fluorine, methyl or ethyl; and

[0450] l is 1, 2, 3, 4, 5 or 6.

[0451] Item 89. The compound according to item 81, represented by any one of formulas (1-42) to (1-60):

##STR00081## ##STR00082## ##STR00083##

wherein, in formulas (1-42) to (1-60),

[0452] R.sup.1 is alkyl having 1 to 10 carbons;

[0453] Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond, (CH.sub.2).sub.2 or (CH.sub.2).sub.4;

[0454] Sp.sup.2, Sp.sup.3 and Sp.sup.4 are independently alkylene having 1 to 5 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0455] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11 and L.sup.12 are independently hydrogen, fluorine, methyl or ethyl; and

[0456] l is 1, 2, 3, 4, 5 or 6.

[0457] Item 90. The compound according to item 81, represented by any one of formulas (1-61) to (1-98):

##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089##

wherein, in formulas (1-61) to (1-98),

[0458] R.sup.1 is alkyl having 1 to 10 carbons;

[0459] Sp.sup.2 and Sp.sup.3 are independently alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0460] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11 and L.sup.12 are independently hydrogen, fluorine or methyl; and

[0461] l is 1, 2, 3 or 4, and in the alkylene, at least one CH.sub.2 may be replaced by O.

[0462] Item 91. The compound according to item 81, represented by any one of formulas (1-99) to (1-117):

##STR00090## ##STR00091## ##STR00092##

wherein, in formulas (1-99) to (1-117),

[0463] R.sup.1 is alkyl having 1 to 10 carbons;

[0464] Sp.sup.2 and Sp.sup.3 are independently alkylene having 1 to 3 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O;

[0465] L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8, L.sup.9, L.sup.10, L.sup.11 and L.sup.12 are independently hydrogen, fluorine or methyl; and

[0466] l is 1, 2, 3 or 4, and in the alkylene, at least one CH.sub.2 may be replaced by O.

14. Form of Compound (1)

[0467] Compound (1) of the invention has features of having a mesogen moiety formed of at least one ring, and a plurality of polar groups. Compound (1) is useful because the polar group noncovalently interacts with a substrate surface of glass (or metal oxide). One of applications is as an additive for the liquid crystal composition used in the liquid crystal display device. Compound (1) is added for the purpose of controlling alignment of liquid crystal molecules. Such an additive preferably has high chemical stability under conditions in which the additive is sealed in the device, high solubility in the liquid crystal composition, and the large voltage holding ratio when the liquid crystal composition is used in the liquid crystal display device. Compound (1) satisfies such characteristics to a significant extent.

[0468] Preferred examples of compound (1) will be described. Preferred examples of a symbol such as R.sup.1, MES, Sp.sup.1 and P.sup.1 in compound (1) are also applied to a subordinate formula of formula (1) for compound (1). In compound (1), characteristics can be arbitrarily adjusted by suitably combining kinds of the groups. Compound (1) may contain a larger amount of isotope such as .sup.2H (deuterium) and .sup.13C than an amount of natural abundance because no significant difference exists in the characteristics of the compound.

R.sup.1-MES-Sp.sup.1-P.sup.1(1)

[0469] In formula (1), R.sup.1 is hydrogen or alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, S or NH, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen.

[0470] In formula (1), preferred R.sup.1 is hydrogen, alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine. Further preferred R.sup.1 is hydrogen, alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine. Particularly preferred R.sup.1 is alkyl having 1 to 10 carbons.

[0471] In formula (1), MES is a mesogen group having at least one ring. The mesogen group is well known by those skilled in the art. The mesogen group means the part that contributes to formation of the liquid crystal phase when the compound has the liquid crystal phase (mesophase). Preferred examples of compound (1) include compound (1-1).

##STR00093##

[0472] In formula (1-1), preferred ring A.sup.1 or ring A.sup.2 is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine. Further preferred ring A.sup.1 or ring A.sup.2 is 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 5 carbons. Particularly preferred ring A.sup.1 or ring A.sup.2 is 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl or perhydrocyclopenta[a]phenanthrene-3,17-diyl, and in the rings, at least one hydrogen may be replaced by fluorine, methyl or ethyl.

[0473] In formula (1-1), Z.sup.1 is a single bond or alkylene having 1 to 4 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0474] In formula (1-1), preferred Z.sup.1 is a single bond, (CH.sub.2).sub.2, CHCH, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF. Further preferred Z.sup.1 or Z.sup.2 is a single bond, (CH.sub.2).sub.2, COO or OCO. Particularly preferred Z.sup.1 or Z.sup.2 is a single bond.

[0475] In formula (1-1), a is 0, 1, 2, 3 or 4. Preferred a is 0, 1, 2 or 3. Further preferred a is 0, 1 or 2. Particularly preferred a is 1 or 2.

[0476] In formula (1-1), Sp.sup.1 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen, and in the groups, at least one or more hydrogen is replaced by a polymerizable group represented by formula (1a):

##STR00094##

wherein, in formula (1a),

[0477] Sp.sup.2 is a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0478] M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and

[0479] R.sup.2 is hydrogen or alkyl having 1 to 15 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O or S, and at least one (CH.sub.2).sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen.

[0480] In formula (1-1), preferred Sp.sup.1 is alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.1 is alkylene having 1 to 3 carbons, or alkylene having 1 to 3 carbons in which one CH.sub.2 is replaced by O, and in the groups, at least one hydrogen is replaced by a polymerizable group represented by formula (1a).

[0481] In formula (1a), preferred Sp.sup.2 is a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.1 is a single bond, alkylene having 1 to 3 carbons, or alkylene having 1 to 3 carbons in which one CH.sub.2 is replaced by O.

[0482] In formula (1a), preferred R.sup.2 is hydrogen, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred R.sup.2 is hydrogen, alkylene having 1 to 3 carbons, or alkylene having 1 to 3 carbons in which one CH.sub.2 is replaced by O. Particularly preferred R.sup.2 is hydrogen or methyl. When R.sup.2 is CH.sub.2OH, vertical alignment in low-concentration addition is expected by an effect in which two hydroxyl groups exist in a molecule.

[0483] In formula (1a), M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred M.sup.1 or M.sup.2 is hydrogen or methyl for increasing reactivity. Further preferred M.sup.1 or M.sup.2 is hydrogen.

[0484] In formula (1), P.sup.1 is a group selected from the group of groups represented by formulas (1e) and (1f):

##STR00095##

wherein, in formula (1e), R.sup.3 is a group selected from the group of groups represented by formulas (1g), (1h) and (1i).

##STR00096##

[0485] In formulas (1e) and (1f), preferred Sp.sup.3 is alkylene having 1 to 7 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.3 is alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Particularly preferred Sp.sup.3 is CH.sub.2.

[0486] In formula (1e), M.sup.3 and M.sup.4 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred M.sup.3 or M.sup.4 is hydrogen or methyl for increasing reactivity. Further preferred M.sup.3 or M.sup.4 is hydrogen.

[0487] In formula (1e), preferred R.sup.3 is a group selected from the group of polar groups represented by formulas (1g), (1h) and (1i). Preferred R.sup.3 is a polar group represented by formula (1g) or (1h). Further preferred R.sup.3 is a polar group represented by formula (1g).

[0488] In formulas (1g), (1h) and (1i), preferred Sp.sup.4 or Sp.sup.5 is alkylene having 1 to 7 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Further preferred Sp.sup.4 or Sp.sup.5 is alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one CH.sub.2 is replaced by O. Particularly preferred Sp.sup.4 or Sp.sup.5 is CH.sub.2.

[0489] In formulas (1g) and (1i), S.sup.1 is >CH or >N, and S.sup.2 is >C< or >Si<. Preferred S.sup.1 is >CH, and preferred S.sup.2 is >C<.

[0490] In formulas (1f), (1g) and (1i), X.sup.1 is OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3, in which R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one CH.sub.2 may be replaced by O, and at least one (CH.sub.2).sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0491] Preferred X.sup.1 is OH, NH.sub.2 or N(R.sup.5).sub.2, in which R.sup.5 is alkyl having 1 to 5 carbons or alkoxy having 1 to 4 carbons. Further preferred X.sup.1 is OH, NH.sub.2 or N(R.sup.5).sub.2. Particularly preferred X.sup.1 is OH.

15. Synthesis of Compound (1)

[0492] Synthesis methods of compound (1) will be described. Compound (1) can be synthesized by suitably combining methods in synthetic organic chemistry. Any compounds whose synthetic methods are not described are prepared according to methods described in books such as Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Shin Jikken Kagaku Koza in Japanese) (Maruzen Co., Ltd.).

[0493] Formation of a Bonding Group

[0494] An example of a method for forming a bonding group in compound (1) is as described in a scheme below. In the scheme, MSG.sup.1 (or MSG.sup.2) is a monovalent organic group having at least one ring. Monovalent organic groups represented by a plurality of MSG.sup.1 (or MSG.sup.2) may be identical or different. Compounds (1A) to (1G) correspond to compound (1) or an intermediate of compound (1).

##STR00097## ##STR00098##

(I) Formation of a Single Bond

[0495] Compound (1A) is prepared by allowing aryl boronic acid (21) to react with compound (22) in the presence of a carbonate and a tetrakis(triphenylphosphine)palladium catalyst. Compound (1A) is also prepared by allowing compound (23) to react with n-butyllithium and subsequently with zinc chloride, and further with compound (22) in the presence of a dichlorobis(triphenylphosphine)palladium catalyst.

(II) Formation of COO and OCO

[0496] Carboxylic acid (24) is obtained by allowing compound (23) to react with n-butyllithium and subsequently with carbon dioxide. Compound (1B) having COO is prepared by dehydration of carboxylic acid (24) and phenol (25) derived from compound (21) in the presence of 1,3-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP). A compound having OCO is also prepared according to the method.

(III) Formation of CF.sub.2O and OCF.sub.2

[0497] Compound (26) is obtained by sulfurizing compound (1B) with a Lawesson's reagent. Compound (1C) having CF.sub.2O is prepared by fluorinating compound (26) with a hydrogen fluoride-pyridine complex and N-bromosuccinimide (NBS). Refer to M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) is also prepared by fluorinating compound (26) with (diethylamino)sulfur trifluoride (DAST). Refer to W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. A compound having OCF.sub.2 is also prepared according to the method.

(IV) Formation of CHCH

[0498] Aldehyde (27) is obtained by allowing compound (22) to react with n-butyllithium and subsequently with N,N-dimethylformamide (DMF). Compound (1D) is prepared by allowing phosphorus ylide generated by allowing phosphonium salt (28) to react with potassium t-butoxide to react with aldehyde (27). A cis isomer may be generated depending on reaction conditions, and therefore the cis isomer is isomerized into a trans isomer according to a publicly-known method when necessary.

(V) Formation of CH.sub.2CH.sub.2

[0499] Compound (1E) is prepared by hydrogenating compound (1D) in the presence of a palladium on carbon catalyst.

(VI) Formation of CC

[0500] Compound (29) is obtained by allowing compound (23) to react with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper iodide and then performing deprotection of the resulting compound under basic conditions. Compound (1F) is prepared by allowing compound (29) to react with compound (22) in the presence of a catalyst of dichlorobis (triphenylphosphine)palladium and copper halide.

(VII) Formation of CH.sub.2O and OCH.sub.2

[0501] Compound (30) is obtained by reducing compound (27) with sodium borohydride. Compound (31) is obtained by brominating the obtained compound with hydrobromic acid. Compound (1G) is prepared by allowing compound (25) to react with compound (31) in the presence of potassium carbonate. A compound having OCH.sub.2 is also prepared according to the method.

(VIII) Formation of CFCF

[0502] Compound (32) is obtained by treating compound (23) with n-butyllithium and then allowing the treated compound to react with tetrafluoroethylene. Compound (1H) is prepared by treating compound (22) with n-butyllithium and then allowing the treated compound to react with compound (32).

[0503] Formation of Ring A.sup.2

[0504] A starting material is commercially available or a synthetic method is well known with regard to a ring such as 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl and pyridine-2,5-diyl.

Synthesis Example

[0505] An example of a method for preparing compound (1) is as described below. In the compounds, definitions of R.sup.1, MES, M.sup.1 and M.sup.2 are identical to definitions described in item 81.

[0506] Compounds (1-51) and (1-52) in which R.sup.2 is a group represented by formula (1a), Sp.sup.4 is CH.sub.2, and X.sup.1 is OH can be prepared according to a method described below.

[0507] Compound (52) is obtained by allowing compound (51) to react in the presence of formaldehyde and 1,4-diazabicyclo[2.2.2]octane (DABCO). Compound (53) is obtained by allowing compound (52) to react in the presence of pyridinium p-toluenesulfonate (PPTS) and 3,4-dihydro-2H-pyran.

[0508] Compound (1-51) can be obtained by allowing compound (54) to react in the presence of triethylamine (Et.sub.3N) and methacryloyl chloride. Compound (55) is obtained by allowing compound (1-51) to react with compound (53) in the presence of DCC and DMAP, and then compound (1-52) can be derived by performing deprotection of compound (55) by using tetrabutylammonium fluoride (PPTS).

##STR00099##

[0509] Compounds (1-53) in which R.sup.2 is a group represented by formula (1a), Sp.sup.4 is (CH.sub.2).sub.2, and X.sup.1 is OH can be prepared according to a method described below. Compound (56) is obtained by allowing phosphorus tribromide to act on compound (1-52). Next, compound (1-53) can be derived by allowing indium to act on compound (57) and then allowing the resulting compound to react with formaldehyde.

##STR00100##

[0510] Compounds (1-54) in which R.sup.2 is a group represented by formula (1a), Sp.sup.4 is CH.sub.2, and X.sup.1 is OH can be prepared according to a method described below.

##STR00101##

16. Liquid Crystal Composition

[0511] The liquid crystal composition contains compound (1) that functions as the alignable monomer, more specifically, contains at least one polymerizable polar compound of compounds (1), (1), (1), (1) and (1) as component A. Compound (1) noncovalently interacts with a substrate of a device, and thus can control alignment of liquid crystal molecules.

[0512] The composition contains compound (1) as component A, and preferably further contains a liquid crystal compound selected from components B, C, D and E described below.

[0513] Component B includes compounds (2) to (4).

[0514] Component C includes compounds (5) to (7).

[0515] Component D includes compound (8).

[0516] Component E includes compounds (9) to (15).

[0517] The composition may contain any other liquid crystal compound different from compounds (2) to (15). When the composition is prepared, components B, C, D and E are preferably selected by considering magnitude of positive or negative dielectric anisotropy, or the like. A composition in which components thereof are suitably selected has high maximum temperature, low minimum temperature, small viscosity, suitable optical anisotropy (more specifically, large optical anisotropy or small optical anisotropy), large positive or negative dielectric anisotropy, large specific resistance, stability to heat or ultraviolet light and a suitable elastic constant (more specifically, a large elastic constant or a small elastic constant).

[0518] Compound (16) that functions as a reactive monomer may be added to the composition for the purpose of increasing reactivity (polymerizability).

[0519] A preferred proportion of compound (1) is about 0.01% by weight or more for maintaining high stability to ultraviolet light, and about 5% by weight or less for dissolution in the liquid crystal composition. A further preferred proportion is in the range of about 0.05% by weight to about 2% by weight. A most preferred proportion is in the range of about 0.05% by weight to about 1% by weight.

[0520] In addition, a preferred proportion of compound (1) or (1) is about 0.05% by weight or more, and about 10% by weight or less for preventing poor display in the device. A further preferred proportion is in the range of about 0.1% by weight to about 7% by weight. A particularly preferred proportion is in the range of about 0.5% by weight to about 5% by weight.

[0521] In addition, a preferred proportion when adding compound (16) is in the range of 0.01% by weight to 1.0% by weight.

[0522] Component B includes a compound in which two terminal groups are alkyl or the like. Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19) and compounds (4-1) to (4-7). In a compound of component B, R.sup.11 and R.sup.12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or the alkenyl, at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine.

##STR00102## ##STR00103## ##STR00104## ##STR00105##

[0523] Component B has a small absolute value of dielectric anisotropy, and therefore is a compound close to neutrality. Compound (2) is mainly effective in decreasing the viscosity or adjusting optical anisotropy. Compounds (3) and (4) are effective in extending the temperature range of the nematic phase by increasing the maximum temperature, or in adjusting the optical anisotropy.

[0524] As a content of component B is increased, the dielectric anisotropy of the composition is decreased, but the viscosity is decreased. Thus, as long as a desired value of threshold voltage of the device is met, the content is preferably as large as possible. When a composition for an IPS mode, a VA mode or the like is prepared, the content of component B is preferably 30% by weight or more, and further preferably 40% by weight or more, based on the weight of the liquid crystal composition.

[0525] Component C is a compound having a halogen-containing group or a fluorine-containing group at a right terminal. Preferred examples of component C include compounds (5-1) to (5-16), compounds (6-1) to (6-113) and compounds (7-1) to (7-57). In a compound of component C, R.sup.13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; and X.sup.11 is fluorine, chlorine, OCF.sub.3, OCHF.sub.2, CF.sub.3, CHF.sub.2, CH.sub.2F, OCF.sub.2CHF.sub.2 or OCF.sub.2CHFCF.sub.3.

##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129##

[0526] Component C has positive dielectric anisotropy, and superb stability to heat, light and so forth, and therefore is used when a composition for the IPS mode, an FFS mode, an OCB mode or the like is prepared. A content of component C is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and further preferably in the range of 40% by weight to 95% by weight, based on the weight of the liquid crystal composition. When component C is added to a composition having negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on the weight of the liquid crystal composition. Addition of component C allows adjustment of the elastic constant of the composition and adjustment of a voltage-transmittance curve of the device.

[0527] Component D is compound (8) in which a right-terminal group is CN or CCCN. Preferred examples of component D include compounds (8-1) to (8-64). In a compound of component D, R.sup.14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; and X.sup.12 is CN or CCCN.

##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137##

[0528] Component D has positive dielectric anisotropy and a value thereof is large, and therefore is mainly used when a composition for a TN mode or the like is prepared. Addition of component D can increase the dielectric anisotropy of the composition. Component D is effective in extending the temperature range of the liquid crystal phase, adjusting the viscosity or adjusting the optical anisotropy. Component D is also useful for adjustment of the voltage-transmittance curve of the device.

[0529] When the composition for the TN mode or the like is prepared, a content of component D is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and further preferably in the range of 40% by weight to 95% by weight, based on the weight of the liquid crystal composition. When component D is added to a composition having negative dielectric anisotropy, the content of component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. Addition of component D allows adjustment of the elastic constant of the composition and adjustment of the voltage-transmittance curve of the device.

[0530] Component E includes compounds (9) to (15). The compounds have phenylene in which hydrogen in lateral positions are replaced by two halogens, such as 2,3-difluoro-1,4-phenylene. Preferred examples of component E include compounds (9-1) to (9-8), compounds (10-1) to (10-17), compound (11-1), compounds (12-1) to (12-3), compounds (13-1) to (13-11), compounds (14-1) to (14-3) and compounds (15-1) to (15-3). In a compound of component E, R.sup.15 and R.sup.16 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; and R.sup.17 is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine.

##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144##

[0531] Component E has large negative dielectric anisotropy. Component E is used when a composition for the IPS mode, the VA mode, a PSA mode or the like is prepared. As a content of component E is increased, the dielectric anisotropy of the composition is negatively increased, but the viscosity is increased. Thus, as long as a desired value of threshold voltage of the device is met, the content is preferably as small as possible. When considering the dielectric anisotropy at a degree of 5, the content is preferably 40% by weight or more in order to allow a sufficient voltage driving.

[0532] Among types of component E, compound (9) is a bicyclic compound, and therefore is mainly effective in decreasing the viscosity, adjusting the optical anisotropy or increasing the dielectric anisotropy. Compounds (10) and (11) are a tricyclic compound, and therefore are effective in increasing the maximum temperature, the optical anisotropy or the dielectric anisotropy. Compounds (12) to (15) are effective in increasing the dielectric anisotropy.

[0533] When a composition for the IPS mode, the VA mode, the PSA mode or the like is prepared, the content of component E is preferably 40% by weight or more, and further preferably in the range of 50% by weight to 95% by weight, based on the weight of the liquid crystal composition. When component E is added to a composition having positive dielectric anisotropy, the content of component E is preferably 30% by weight or less based on the weight of the liquid crystal composition. Addition of component E allows adjustment of the elastic constant of the composition and adjustment of the voltage-transmittance curve of the device.

[0534] The liquid crystal composition satisfying at least one of characteristics such as high maximum temperature, low minimum temperature, small viscosity, suitable optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat and a large elastic constant can be prepared by suitably combining components B, C, D and E described above. Any other liquid crystal compound different from components B, C, D and E may be added thereto when necessary.

[0535] The liquid crystal composition is prepared according to a publicly-known method. For example, the component compounds are mixed and dissolved in each other by heating. According to an application, an additive may be added to the composition. Specific examples of the additives include the polymerizable compound other than formula (1) and formula (16), the polymerization initiator, the polymerization inhibitor, the optically active compound, the antioxidant, the ultraviolet light absorber, a light stabilizer, a heat stabilizer and the antifoaming agent. Such additives are well known to those skilled in the art, and described in literature.

[0536] The polymerizable compound other than formula (16) or formula (16) is added for the purpose of forming the polymer in the liquid crystal composition. The polymerizable compound and compound (1) are copolymerized by irradiation with ultraviolet light while voltage is applied between electrodes, and thus the polymer is formed in the liquid crystal composition. On the occasion, compound (1) is fixed in a state in which the polar group noncovalently interacts with a substrate surface. Thus, capability of controlling alignment of liquid crystal molecules is further improved, and at the same time, the polar compound no longer leaks into the liquid crystal composition. Moreover, suitable pretilt can be obtained even in the substrate surface, and therefore a liquid crystal display device in which a response time is shortened and the voltage holding ratio is large can be obtained. Specific examples of a preferred polymerizable compound include acrylate, methacrylate, a vinyl compound, a vinyloxy compound, propenyl ether, an epoxy compound (oxirane, oxetane) and vinyl ketone. Further preferred examples include a compound having at least one acryloyloxy and a compound having at least one methacryloyloxy. Still further preferred examples also include a compound having both acryloyloxy and methacryloyloxy.

[0537] In a composition containing compound (1), still further preferred examples include compounds (M-1) to (M-17). In compounds (M-1) to (M-17), R.sup.25 to R.sup.31 are independently hydrogen or methyl; s, v and x are independently 0 or 1; t and u are independently an integer from 1 to 10; and L.sup.21 to L.sup.26 are independently hydrogen or fluorine, and L.sup.27 and L.sup.28 are independently hydrogen, fluorine or methyl.

##STR00145## ##STR00146## ##STR00147##

[0538] In a composition containing compound (1) or compound (1), still further preferred examples include compounds (16-1-1) to (16-16). In compounds (16-1-1) to (16-16), R.sup.25 to R.sup.31 are independently hydrogen or methyl; v and x are independently 0 or 1; t and u are independently an integer from 1 to 10; and L.sup.31 to L.sup.36 are independently hydrogen or fluorine, and L.sup.37 and L.sup.38 are independently hydrogen, fluorine or methyl.

##STR00148## ##STR00149## ##STR00150## ##STR00151##

[0539] The polymerizable compound can be rapidly polymerized by adding the polymerization initiator. An amount of a remaining polymerizable compound can be decreased by optimizing a reaction temperature. Specific examples of a photoradical polymerization initiator include TPO, 1173 and 4265 from Darocur series of BASF SE, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850 and 2959 from Irgacure series thereof.

[0540] Additional examples of the photoradical polymerization initiator include 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, a benzophenone-Michler's ketone mixture, a hexaarylbiimidazole-mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, a mixture of 2,4-diethylxanthone and methyl p-dimethylaminobenzoate, and a mixture of benzophenone and methyltriethanolamine.

[0541] After the photoradical polymerization initiator is added to the liquid crystal composition, polymerization can be performed by irradiation with ultraviolet light while an electric field is applied. However, an unreacted polymerization initiator or a decomposition product of the polymerization initiator may cause a poor display such as image persistence in the device. In order to prevent such an event, photopolymerization may be performed with no addition of the polymerization initiator. A preferred wavelength of irradiation light is in the range of 150 nanometers to 500 nanometers. A further preferred wavelength is in the range of 250 nanometers to 450 nanometers, and a most preferred wavelength is in the range of 300 nanometers to 400 nanometers.

[0542] Upon storing the polymerizable compound, the polymerization inhibitor may be added thereto for preventing polymerization. The polymerizable compound is ordinarily added to the composition without removing the polymerization inhibitor. Specific examples of the polymerization inhibitor include hydroquinone, a hydroquinone derivative such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol and phenothiazine.

[0543] The optically active compound is effective in inducing a helical structure in liquid crystal molecules to give a required twist angle, and thereby preventing a reverse twist. A helical pitch can be adjusted by adding the optically active compound. Two or more optically active compounds may be added for the purpose of adjusting temperature dependence of the helical pitch. Specific examples of a preferred optically active compound include compounds (Op-1) to (Op-18) described below. In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R.sup.28 is alkyl having 1 to 10 carbons.

##STR00152## ##STR00153## ##STR00154##

[0544] The antioxidant is effective for maintaining the large voltage holding ratio. Specific examples of a preferred antioxidant include compounds (AO-1) and (AO-2); and IRGANOX 415, IRGANOX 565, IRGANOX1010, IRGANOX 1035, IRGANOX 3114 and IRGANOX 1098 (trade names: BASF SE). The ultraviolet light absorber is effective for preventing a decrease of the maximum temperature. Specific examples of a preferred ultraviolet light absorber include a benzophenone derivative, a benzoate derivative and a triazole derivative. Specific examples include compounds (AO-3) and (AO-4); TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328 and TINUVIN 99-2 (trade names: BASF SE); and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0545] The light stabilizer such as an amine having steric hindrance is preferred for maintaining the large voltage holding ratio. Specific examples of a preferred light stabilizer include compounds (AO-5) and (AO-6); and TINUVIN 144, TINUVIN 765 and TINUVIN 770DF (trade names: BASF SE). The heat stabilizer is also effective for maintaining the large voltage holding ratio, and preferred examples include IRGAFOS 168 (trade name: BASF SE). The antifoaming agent is effective for preventing foam formation. Specific examples of a preferred antifoaming agent include dimethyl silicone oil and methylphenyl silicone oil.

##STR00155##

[0546] In compound (AO-1), R.sup.40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, COOR.sup.41 or CH.sub.2CH.sub.2COOR.sup.41, in which R.sup.41 is alkyl having 1 to 20 carbons. In compounds (AO-2) and (AO-5), R.sup.42 is alkyl having 1 to 20 carbons. In compound (AO-5), R.sup.43 is hydrogen, methyl or O. (oxygen radical), ring G is 1,4-cyclohexylene or 1,4-phenylene, and z is 1, 2 or 3.

17. Liquid Crystal Display Device

[0547] The liquid crystal composition can be used in a liquid crystal display device having an operating mode such as a PC mode, the TN mode, an STN mode, the OCB mode and the PSA mode, and driven by an active matrix mode. The composition can also be used in a liquid crystal display device having an operating mode such as the PC mode, the TN mode, the STN mode, the OCB mode, the VA mode and the IPS mode, and driven by a passive matrix mode. The devices can be applied to any of a reflective type, a transmissive type and a transflective type.

[0548] The composition can also be used in a nematic curvilinear aligned phase (NCAP) device prepared by microencapsulating a nematic liquid crystal, and a polymer dispersed liquid crystal display device (PDLCD) and a polymer network liquid crystal display device (PNLCD) in which a three-dimensional network-polymer is formed in the liquid crystal. When an amount of adding the polymerizable compound (total amount of compound (1), compound (16) and polymerizable compounds other than the compounds) is about 10% by weight or less based on the weight of the liquid crystal composition, the liquid crystal display device having the PSA mode can be prepared. A preferred proportion is in the range of about 0.1% by weight to about 2% by weight. A further preferred proportion is in the range of about 0.2% by weight to about 1.0% by weight. The device having the PSA mode can be driven by the driving mode such as the active matrix mode and the passive matrix mode. Such a device can also be applied to any of the reflective type, the transmissive type and the transflective type. A device having a polymer dispersed mode can also be prepared by increasing the amount of adding the polymerizable compound.

[0549] In the polymer sustained alignment mode device, the polymer contained in the composition aligns liquid crystal molecules. The polar compound helps alignment of liquid crystal molecules. More specifically, the polar compound can be used in place of an alignment film. One example of a method for producing such a device is as described below. The device having two substrates referred to as an array substrate and a color filter substrate is prepared. The substrates have no alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. The polymerizable compound and the polar compound are added to the composition. An additive may be further added thereto when necessary. The composition is injected into the device. The device is irradiated with light while voltage is applied to the device. Ultraviolet light is preferred. The polymerizable compound is polymerized by irradiation with light. A composition containing the polymer is formed by the polymerization, and a device having the PSA mode is prepared.

[0550] In the above procedure, the polar group interacts with the substrate surface, and therefore the polar compound is aligned on a substrate. The polar compound aligns liquid crystal molecules. When voltage is applied, the alignment of the liquid crystal molecules is further promoted by action of an electric field. The polymerizable compound is also aligned according to the alignment. The polymerizable compound is polymerized by ultraviolet light in the above state, and therefore a polymer maintaining the alignment is formed. The alignment of the liquid crystal molecules is additionally stable by an effect of the polymer, and therefore the response time of the device is shortened. The image persistence is caused due to poor operation in the liquid crystal molecules, and therefore the persistence is also simultaneously improved by the effect of the polymer. In particular, compound (1) used in the invention is a polymerizable polar compound, and therefore aligns liquid crystal molecules, and is subjected to homopolymerization or copolymerized with a reactive monomer as any other polymerizable compound. Thus, in the invention, the polar compound no longer leaks into the liquid crystal composition, and therefore the liquid crystal display device in which the voltage holding ratio is large can be obtained.

[0551] FIG. 1 shows device 11 in a state in which compound (1) that functions as alignable monomer 5 is arranged on color filter substrate 1 and array substrate 2 by interaction of a polar group with a substrate surface. An alignment control layer is formed by polymerization of compound (1). FIG. 2 shows device 12 in a state in which compound (1) that functions as alignable monomer 5 is arranged on color filter substrate 1 and array substrate 2 by interaction of a polar group with a substrate surface. The alignment control layer is formed by copolymerization of compound (1) with compound (16) that functions as reactive monomer 6. FIG. 3 is a schematic view of device 21 having a conventional alignment film and including the polymerizable compound.

[0552] In addition, the liquid crystal display device of the invention is not limited to the device with a structure having two substrates such as array substrate 2 and color filter substrate 1 as shown in FIG. 1 to FIG. 2, and for example, may be a device with a color filter on array (COA) structure having a color filter (CF) formed on a TFT substrate, or understandably may be a device with a structure other than above.

[0553] Compound (1) aligned on the substrate is polymerized by irradiation with ultraviolet light to form the alignment control layer on each substrate. Thickness of one layer (only one side) of the alignment control layer is 10 to 100 nanometers, preferably 10 to 80 nanometers, and further preferably 20 to 80 nanometers. If the thickness is 10 nanometers or more, electric characteristics can be maintained, and therefore such a case is preferred. If the thickness is 100 nanometers or less, driving voltage can be suitably decreased, and therefore such a case is preferred.

[0554] Thus, the liquid crystal display device of the application can form the alignment control layer, and therefore the liquid crystal compounds are vertically aligned to a substrate surface. Then, an angle (more specifically, pretilt angle) of the liquid crystal compound to the substrate surface is 9010 degrees, preferably 905 degrees, and further preferably 903 degrees. If the angle is 9010 degrees, such a case is preferred from a viewpoint of optical characteristics.

[0555] If the pretilt angle can be given to the liquid crystal compound by using the alignment control layer, combination with pixel electrodes having a slit and subjected to pixel division can achieve a wide viewing angle by the pixel division.

[0556] In a vertical alignment (VA) mode liquid crystal display device as one embodiment of the invention, a direction of alignment of liquid crystal molecules during no voltage application is substantially vertically aligned relative to the substrate surface. In order to vertically align the liquid crystal molecules, as shown in FIG. 3, vertical alignment films such as a polyimide alignment film, a polyamide alignment film and a polysiloxane alignment film are ordinarily each arranged between color filter substrate 1 and liquid crystal layer 3 and between array substrate 2 and liquid crystal layer 3, but the liquid crystal display device of the invention does not require such an alignment film.

EXAMPLES

[0557] The invention will be described in greater detail by way of Examples (including Synthesis Examples). However, the invention is not limited by the Examples. The invention includes a mixture of composition (i) and composition (ii). The invention also includes a mixture prepared by mixing at least two of the compositions.

1. Measuring Method

[0558] Unless otherwise specified, reaction was performed under a nitrogen atmosphere. Compound (1) was prepared according to procedures shown in Synthesis Examples and so forth. The thus prepared compound was identified by a method such as an NMR analysis. Characteristics of compound (1), a liquid crystal compound, a composition and a device were measured by methods described below.

[0559] NMR analysis: For measurement, DRX-500 made by Bruker BioSpin Corporation was used. In .sup.1H-NMR measurement, a sample was dissolved in a deuterated solvent such as CDCl.sub.3, and measurement was carried out under conditions of room temperature, 500 MHz and 16 times of accumulation. Tetramethylsilane was used as an internal standard. In .sup.19F-NMR measurement, CFCl.sub.3 was used as an internal standard, and measurement was carried out under conditions of 24 times of accumulation. In explaining nuclear magnetic resonance spectra obtained, s, d, t, g, quin, sex and m stand for a singlet, a doublet, a triplet, a quartet, a quintet, a sextet and a multiplet, and br being broad, respectively.

[0560] Gas chromatographic analysis: For measurement, GC-2010 Gas Chromatograph made by Shimadzu Corporation was used. As a column, a capillary column DB-1 (length 60 m, bore 0.25 mm, film thickness 0.25 m) made by Agilent Technologies, Inc. was used. As a carrier gas, helium (1 mL/minute) was used. A temperature of a sample vaporizing chamber and a temperature of a detector (FID) part were set to 300 C. and 300 C., respectively. A sample was dissolved in acetone and prepared to be a 1 weight % solution, and then 1 microliter of the solution obtained was injected into the sample vaporizing chamber. As a recorder, GC Solution System made by Shimadzu Corporation or the like was used.

[0561] HPLC analysis: For measurement, Prominence (LC-20AD; SPD-20A) made by Shimadzu Corporation was used. As a column, YMC-Pack ODS-A (length 150 mm, bore 4.6 mm, particle diameter 5 m) made by YMC Co., Ltd. was used. As an eluate, acetonitrile and water were appropriately mixed and used. As a detector, a UV detector, an RI detector, a CORONA detector or the like was appropriately used. When the UV detector was used, a detection wavelength was set at 254 nanometers. A sample was dissolved in acetonitrile and prepared to be a 0.1 weight % solution, and then 1 microliter of the solution was injected into a sample chamber. As a recorder, C-R7Aplus made by Shimadzu Corporation was used.

[0562] Ultraviolet-visible spectrophotometry: For measurement, PharmaSpec UV-1700 made by Shimadzu Corporation was used. A detection wavelength was adjusted in the range of 190 nanometers to 700 nanometers. A sample was dissolved in acetonitrile and prepared to be a 0.01 mmol/L solution, and measurement was carried out by putting the solution in a quartz cell (optical path length: 1 cm).

[0563] Sample for measurement: Upon measuring phase structure and a transition temperature (a clearing point, a melting point, a polymerization starting temperature or the like), a compound itself was used as a sample.

[0564] Measuring method: Characteristics were measured according to methods described below. Most of the measuring methods are applied as described in the Standard of Japan Electronics and Information Technology Industries Association (hereinafter abbreviated as JEITA) (JEITA ED-2521B) discussed and established by JEITA, or modified thereon. No thin film transistor (TFT) was attached to a TN device used for measurement.

(1) Phase Structure

[0565] A sample was placed on a hot plate in a melting point apparatus (FP-52 Hot Stage made by Mettler-Toledo International Inc.) equipped with a polarizing microscope. A state of phase and a change thereof were observed with the polarizing microscope while the sample was heated at a rate of 3 C. per minute, and a kind of the phase was specified.

(2) Transition Temperature ( C.)

[0566] For measurement, a scanning calorimeter, Diamond DSC System, made by PerkinElmer, Inc., or a high sensitivity differential scanning calorimeter, X-DSC7000, made by SII NanoTechnology Inc. was used. A sample was heated and then cooled at a rate of 3 C. per minute, and a starting point of an endothermic peak or an exothermic peak caused by a phase change of the sample was determined by extrapolation, and thus a transition temperature was determined. A melting point and a polymerization starting temperature of a compound were also measured using the apparatus. Temperature at which a compound undergoes transition from a solid to a liquid crystal phase such as the smectic phase and the nematic phase may be occasionally abbreviated as minimum temperature of the liquid crystal phase. Temperature at which the compound undergoes transition from the liquid crystal phase to liquid may be occasionally abbreviated as clearing point.

[0567] A crystal was expressed as C. When kinds of the crystals were distinguishable, each of the crystals was expressed as C.sub.1 or C.sub.2. The smectic phase or the nematic phase was expressed as S or N. When smectic A phase, smectic B phase, smectic C phase or smectic F phase was distinguishable among the smectic phases, the phases were expressed as S.sub.A, S.sub.B, S.sub.C or S.sub.F, respectively. A liquid (isotropic) was expressed as I. A transition temperature was expressed as C 50.0 N 100.0 I, for example. The expression indicates that a transition temperature from the crystals to the nematic phase is 50.0 C., and a transition temperature from the nematic phase to the liquid is 100.0 C.

(3) Maximum Temperature of Nematic Phase (T.SUB.NI .or NI; C.)

[0568] A sample was placed on a hot plate in a melting point apparatus equipped with a polarizing microscope and heated at a rate of 1 C. per minute. Temperature when part of the sample began to change from the nematic phase to an isotropic liquid was measured. A maximum temperature of the nematic phase may be occasionally abbreviated as maximum temperature. When the sample was a mixture of compound (1) and the base liquid crystal, the maximum temperature was expressed in terms of a symbol T.sub.NI. When the sample was a mixture of compound (1) and a compound such as components B, C and D, the maximum temperature was expressed as a symbol NI.

(4) Minimum Temperature of Nematic Phase (T.SUB.C.; C.)

[0569] Samples each having the nematic phase were kept in freezers at temperatures of 0 C., 10 C., 20 C., 30 C. and 40 C. for 10 days, and then liquid crystal phases were observed. For example, when the sample maintained the nematic phase at 20 C. and changed to crystals or the smectic phase at 30 C., T.sub.C was expressed as T.sub.C20 C. A minimum temperature of the nematic phase may be occasionally abbreviated as minimum temperature.

(5) Viscosity (Bulk Viscosity; ; Measured at 20 C.; mPa.Math.s)

[0570] For measurement, a cone-plate (E type) rotational viscometer made by Tokyo Keiki Inc. was used.

(6) Optical Anisotropy (Refractive Index Anisotropy; Measured at 25 C.; n)

[0571] Measurement was carried out by an Abbe refractometer with a polarizing plate mounted on an ocular, using light at a wavelength of 589 nanometers. A surface of a main prism was rubbed in one direction, and then a sample was added dropwise onto the main prism. A refractive index (n) was measured when a direction of polarized light was parallel to a direction of rubbing. A refractive index (n) was measured when the direction of polarized light was perpendicular to the direction of rubbing. A value of optical anisotropy (n) was calculated from an equation: n=nn.

(7) Specific resistance (; measured at 25 C.; cm)

[0572] Into a vessel equipped with electrodes, 1.0 milliliter of sample was injected. A direct current voltage (10 V) was applied to the vessel, and a direct current after 10 seconds was measured. Specific resistance was calculated from the following equation: (specific resistance)={(voltage)(electric capacity of a vessel)}/{(direct current)*(dielectric constant of vacuum)}.

[0573] Measurement methods of characteristics in a sample having positive dielectric anisotropy may be occasionally different from measurement methods of characteristics in a sample having negative dielectric anisotropy. Measurement methods of the sample having positive dielectric anisotropy were described in sections (8a) to (12a). Measurement methods of the sample having negative dielectric anisotropy were described in sections (8b) to (12b).

(8a) Viscosity (rotational viscosity; 1; measured at 25 C.; mPa.Math.s)

[0574] Positive dielectric anisotropy: Measurement was carried out according to a method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a TN device in which a twist angle was 0 degrees and a distance (cell gap) between two glass substrates was 5 micrometers. Voltage was applied stepwise to the device in the range of 16 V to 19.5 V at an increment of 0.5 V. After a period of 0.2 second with no voltage application, voltage was repeatedly applied under conditions of only one rectangular wave (rectangular pulse; 0.2 second) and no voltage application (2 seconds). A peak current and a peak time of transient current generated by the applied voltage were measured. A value of rotational viscosity was obtained from the measured values and calculation equation (8) described on page 40 of the paper presented by M. Imai et al. A value of dielectric anisotropy required for the calculation was determined using the device by which the rotational viscosity was measured and by a method described below.

(8b) Viscosity (rotational viscosity; 1; measured at 25 C.; mPa.Math.s)

[0575] Negative dielectric anisotropy: Measurement was carried out according to a method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a VA device in which a distance (cell gap) between two glass substrates was 20 m. Voltage was applied stepwise to the device in the range of 39 V to 50 V at an increment of 1 V. After a period of 0.2 second with no voltage application, voltage was repeatedly applied under conditions of only one rectangular wave (rectangular pulse; 0.2 second) and no voltage application (2 seconds). A peak current and a peak time of transient current generated by the applied voltage were measured. A value of rotational viscosity was obtained from the measured values and calculation equation (8) described on page 40 of the paper presented by M. Imai et al. In dielectric anisotropy required for the calculation, a value measured according to items of dielectric anisotropy as described below was used.

(9a) Dielectric Anisotropy (; Measured at 25 C.)

[0576] Positive dielectric anisotropy: A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 micrometers and a twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a major axis direction was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a minor axis direction was measured. A value of dielectric anisotropy was calculated from an equation: =.

(9b) Dielectric Anisotropy (; Measured at 25 C.)

[0577] Negative dielectric anisotropy: A value of dielectric anisotropy was calculated from an equation: =. A dielectric constant ( and ) was measured as described below.

[0578] (1) Measurement of dielectric constant (): An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. After rotating the glass substrate with a spinner, the glass substrate was heated at 150 C. for 1 hour. A sample was put in a VA device in which a distance (cell gap) between two glass substrates was 4 micrometers, and the device was sealed with an ultraviolet-curable adhesive. Sine waves (0.5V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a major axis direction was measured.

[0579] (2) Measurement of dielectric constant (): A polyimide solution was applied to a well-cleaned glass substrate. After calcining the glass substrate, rubbing treatment was applied to the alignment film obtained. A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 micrometers and a twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a minor axis direction was measured.

(10a) Elastic Constant (K; Measured at 25 C.; pN)

[0580] Positive dielectric anisotropy: For measurement, HP4284A LCR Meter made by Yokogawa-Hewlett-Packard Co. was used. A sample was put in a horizontal alignment device in which a distance (cell gap) between two glass substrates was 20 micrometers. An electric charge of 0 V to 20 V was applied to the device, and electrostatic capacity and applied voltage were measured. The measured values of electrostatic capacity (C) and applied voltage (V) were fitted to equation (2.98) and equation (2.101) on page 75 of Liquid Crystal Device Handbook (Ekisho Debaisu Handobukku in Japanese; Nikkan Kogyo Shimbun, Ltd.), and values of K.sub.11 and K.sub.33 were obtained from equation (2.99). Next, K.sub.22 was calculated using the previously determined values of K.sub.11 and K.sub.33 in equation (3.18) on page 171. Elastic constant K was expressed in terms of a mean value of the thus determined K.sub.11, K.sub.22 and K.sub.33.

(10b) Elastic Constant (K.sub.11 and K.sub.33; Measured at 25 C.; pN)

[0581] Negative dielectric anisotropy: For measurement, Elastic Constant Measurement System Model EC-1 made by TOYO Corporation was used. A sample was put in a vertical alignment device in which a distance (cell gap) between two glass substrates was 20 micrometers. An electric charge of 20 V to 0 V was applied to the device, and electrostatic capacity and applied voltage were measured. The measured values of electrostatic capacity (C) and applied voltage (V) were fitted to equation (2.98) and equation (2.101) on page 75 of Liquid Crystal Device Handbook (Ekisho Debaisu Handobukku, in Japanese; Nikkan Kogyo Shimbun, Ltd.), and values of elastic constant were obtained from equation (2.100).

(11a) Threshold Voltage (Vth; Measured at 25 C.; V)

[0582] Positive dielectric anisotropy: For measurement, an LCD5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A sample was put in a normally white mode TN device in which a distance (cell gap) between two glass substrates was 0.45/n (m) and a twist angle was 80 degrees. A voltage (32 Hz, rectangular waves) to be applied to the device was stepwise increased from 0 V to 10 V at an increment of 0.02 V. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponds to 100% transmittance and the minimum amount of light corresponds to 0% transmittance. A threshold voltage is expressed in terms of a voltage at 90% transmittance.

(11b) Threshold Voltage (Vth; Measured at 25 C.; V)

[0583] Negative dielectric anisotropy: For measurement, an LCD5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A sample was put in a normally black mode VA device in which a distance (cell gap) between two glass substrates was 4 micrometers and a rubbing direction was anti-parallel, and the device was sealed with an ultraviolet-curable adhesive. A voltage (60 Hz, rectangular waves) to be applied to the device was stepwise increased from 0 V to 20 V at an increment of 0.02 V. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponds to 100% transmittance and the minimum amount of light corresponds to 0% transmittance. A threshold voltage is expressed in terms of a voltage at 10% transmittance.

(12a) Response Time (; Measured at 25 C.; ms)

[0584] Positive dielectric anisotropy: For measurement, an LCD5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A low-pass filter was set to 5 kHz. A sample was put in a normally white mode TN device in which a distance (cell gap) between two glass substrates was 5.0 micrometers and a twist angle was 80 degrees. A voltage (rectangular waves; 60 Hz, 5 V, 0.5 second) was applied to the device. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. The maximum amount of light corresponds to 100% transmittance, and the minimum amount of light corresponds to 0% transmittance. A rise time (r; millisecond) was expressed in terms of time required for a change from 90% transmittance to 10% transmittance. A fall time (f; millisecond) was expressed in terms of time required for a change from 10% transmittance to 90% transmittance. A response time was expressed by a sum of the rise time and the fall time thus obtained.

(12b) Response Time (; Measured at 25 C.; ms)

[0585] Negative dielectric anisotropy: For measurement, an LCD5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A low-pass filter was set to 5 kHz. A sample was put in a normally black mode PVA device in which a distance (cell gap) between two glass substrates was 3.2 micrometers and a rubbing direction was anti-parallel. The device was sealed with an ultraviolet-curable adhesive. Voltage having a degree of slightly exceeding threshold voltage was applied to the device for 1 minute, and then the device was irradiated with ultraviolet light of 23.5 mW/cm.sup.2 for 8 minutes while voltage of 5.6V was applied to the device. A voltage (rectangular waves; 60 Hz, 10 V, 0.5 second) was applied to the device. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. The maximum amount of light corresponds to 100% transmittance, and the minimum amount of light corresponds to 0% transmittance. A response time was expressed in terms of time required for a change from 90% transmittance to 10% transmittance (fall time; millisecond).

(13) Voltage Holding Ratio

[0586] The polymerizable compound was polymerized by irradiating the device with ultraviolet light using a black light, F40T10/BL (peak wavelength of 369 nm) made by EYE GRAPHICS CO., LTD. The device was charged by applying a pulse voltage (60 microseconds at 1 V) at 60 C. A decaying voltage was measured for 1.67 seconds with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was determined. Area B is an area without decay. A voltage holding ratio is expressed in terms of a percentage of area A to area B.

Raw Material

[0587] Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%), and was purchased from Japan Alcohol Trading Co., Ltd.

2. Synthesis Example of Compound (1)

Synthesis Example 1: Synthesis of Compound (1-4-2)

[0588] ##STR00156##

First Step

[0589] Compound (T-1) (25.0 g), acrylic acid (7.14 g), DMAP (1.21 g) and dichloromethane (300 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (125 mL) solution of DCC (24.5 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=2:1 in a volume ratio). The residue was further purified by recrystallization from Solmix (registered trademark) A-11 to obtain compound (T-2) (11.6 g; 38%).

Second Step

[0590] Paraformaldehyde (2.75 g), DABCO (4.62 g) and water (40 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 15 minutes. A THF (90 mL) solution of compound (T-2) (6.31 g) was added dropwise thereto, and the resulting mixture was stirred at room temperature for 72 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=5:1 in a volume ratio). The residue was further purified by recrystallization from a mixed solvent of heptane and toluene (1:1 in a volume ratio) to obtain compound (1-4-2) (1.97 g; 29%).

[0591] An NMR analysis value of the resulting compound (1-4-2) was as described below.

[0592] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.23 (s, 1H), 5.79 (d, J=1.2 Hz, 1H), 4.79-4.70 (m, 1H), 4.32 (d, J=6.7 Hz, 2H), 2.29 (t, J=6.7 Hz, 1H), 2.07-2.00 (m, 2H), 1.83-1.67 (m, 6H), 1.42-1.18 (m, 8H), 1.18-0.91 (m, 9H), 0.91-0.79 (m, 5H).

[0593] Physical properties of compound (1-4-2) were as described below.

[0594] Transition temperature: C 40.8 S.sub.A 109 I.

Synthesis Example 2: Synthesis of Compound (1-4-22)

[0595] ##STR00157##

First Step

[0596] Compound (T-4) (42.5 g; 65%) was obtained by using compound (T-3) (50.0 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 1.

Second Step

[0597] Compound (T-4) (42.5 g), imidazole (24.5 g) and dichloromethane (740 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (110 mL) solution of t-butyldimethylsilyl chloride (54.1 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=10:1 in a volume ratio) to obtain compound (T-5) (79.8 g; 100%).

Third Step

[0598] Compound (T-5) (79.8 g), THF (640 mL), methanol (160 mL) and water (80 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Lithium hydroxide monohydrate (27.4 g) was added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and 6 N hydrochloric acid (15 mL) was slowly added thereto to acidify the resulting mixture, and then an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-6) (60.6 g; 86%).

Fourth Step

[0599] Compound (T-7) (2.83 g), compound (T-6) (2.98 g), DMAP (0.140 g) and dichloromethane (80 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (40 mL) solution of DCC (2.84 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=2:1 in a volume ratio) to obtain compound (T-8) (3.22 g; 63%).

Fifth Step

[0600] Compound (T-8) (3.22 g), p-toluenesulfonic acid monohydrate (PTSA, 0.551 g), acetone (50 mL) and water (3.5 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 1 hour. Next, pyridine (0.30 mL) was added thereto, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=2:1 in a volume ratio). The residue was further purified by recrystallization from a mixed solvent of heptane and toluene (1:1 in a volume ratio) to obtain compound (1-4-22) (2.05 g; 86%).

[0601] An NMR analysis value of the resulting compound (1-4-22) was as described below.

[0602] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.23 (d, J=8.6 Hz, 2H), 7.03 (d, J=8.6 Hz, 2H), 6.50 (s, 1H), 6.03 (d, J=1.0 Hz, 1H), 4.44 (d, J=6.7 Hz, 2H), 2.47 (tt, J=12.2 Hz, J=3.3 Hz, 1H), 2.24 (t, J=6.6 Hz, 1H), 1.93-1.83 (m, 4H), 1.48-1.37 (m, 2H), 1.37-1.18 (m, 9H), 1.10-0.98 (m, 2H), 0.90 (t, J=7.2 Hz, 3H).

[0603] Physical properties of compound (1-4-22) were as described below.

[0604] Transition temperature: C 67.6 S.sub.C 84.4 S.sub.A 87.7 N 89.8 I.

Synthesis Example 3: Synthesis of Compound (1-4-27)

[0605] ##STR00158##

First Step

[0606] Compound (T-7) (4.00 g), potassium carbonate (4.49 g), tetrabutylammonium bromide (TBAB) (1.05 g) and DMF (60 mL) were put in a reaction vessel, and the resulting mixture was stirred at 80 C. for 1 hour. A DMF (20 mL) solution of compound (T-9) (5.27 g) prepared according to a technique described in JP 2011-21118 A was slowly added dropwise thereto, and the resulting mixture was further stirred at 80 C. for 2 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=2:1 in a volume ratio) to obtain compound (T-10) (4.00 g; 72%).

Second Step

[0607] Compound (1-4-27) (1.81 g; 42%) was obtained by using compound (T-10) (4.00 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 1.

[0608] An NMR analysis value of the resulting compound (1-4-27) was as described below.

[0609] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.13 (d, J=8.6 Hz, 2H), 6.84 (d, J=8.7 Hz, 2H), 6.29 (s, 1H), 5.85 (d, J=1.2 Hz, 1H), 4.52 (t, J=4.8 Hz, 2H), 4.33 (d, J=6.7 Hz, 2H), 4.21 (t, J=4.8 Hz, 2H), 2.41 (tt, J=12.3 Hz, J=3.0 Hz, 1H), 2.26 (t, J=6.6 Hz, 1H), 1.90-1.81 (m, 4H), 1.46-1.17 (m, 11H), 1.09-0.98 (m, 2H), 0.89 (t, J=7.3 Hz, 3H).

[0610] Physical properties of compound (1-4-27) were as described below.

[0611] Transition temperature: C 40.4 S.sub.A 69.9 I.

Synthesis Example 4: Synthesis of Compound (1-5-31)

[0612] ##STR00159##

First Step

[0613] Compound (T-11) (10.7 g) prepared according to a technique described in WO 2008/105286A, allyl alcohol (3.3 mL), palladium acetate (0.107 g), sodium hydrogencarbonate (5.99 g), TBAB (8.42 g) and DMF (110 mL) were put in a reaction vessel, and the resulting mixture was stirred at 40 C. for 8 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene). The residue was further purified by recrystallization from a mixed solvent of heptane and toluene (1:1 in a volume ratio) to obtain compound (T-12) (6.93 g; 77%).

Second Step

[0614] Sodium borohydride (0.723 g) and methanol (110 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A THF (30 mL) solution of compound (T-12) (6.93 g) was slowly added thereto, and the resulting mixture was stirred for 2 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=5:1 in a volume ratio). The residue was further purified by recrystallization from a mixed solvent of heptane and toluene (1:1 in a volume ratio) to obtain compound (T-13) (5.73 g; 82%).

Third Step

[0615] Compound (T-14) (3.36 g; 47%) was obtained by using compound (T-13) (4.73 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 2.

Fourth Step

[0616] Compound (T-14) (2.36 g) and THF (50 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. TBAF (1.00 M; THF solution; 4.5 mL) was slowly added thereto, and the resulting mixture was stirred for 1 hour while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=5:1 in a volume ratio). The residue was further purified by recrystallization from a mixed solvent of heptane and toluene (1:1 in a volume ratio) to obtain compound (1-5-31) (1.47 g; 77%).

[0617] An NMR analysis value of the resulting compound (1-5-31) was as described below.

[0618] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.48 (d, J=8.2 Hz, 2H), 7.31-7.14 (m, 5H), 6.25 (s, 1H), 5.84 (d, J=1.2 Hz, 1H), 4.34 (d, J=6.4 Hz, 2H), 4.24 (t, J=6.4 Hz, 2H), 2.78 (t, J=7.5 Hz, 2H), 2.51 (tt, J=12.1 Hz, J=3.2 Hz, 1H), 2.20 (t, J=6.5 Hz, 1H), 2.10-2.20 (m, 2H), 1.96-1.84 (m, 4H), 1.54-1.42 (m, 2H), 1.38-1.20 (m, 9H), 1.13-1.01 (m, 2H), 0.90 (t, J=7.2 Hz, 3H).

[0619] Physical properties of compound (1-5-31) were as described below.

[0620] Transition temperature: S.sub.A 115 I.

Synthesis Example 5: Synthesis of Compound (1-3-1)

[0621] ##STR00160##

First Step

[0622] Compound (T-16) (3.56 g; 24%) was obtained by using compound (T-15) (10.0 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 2.

Second Step

[0623] Compound (1-3-1) (2.34 g; 82%) was obtained by using compound (T-16) (3.56 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 4.

[0624] An NMR analysis value of the resulting compound (1-3-1) was as described below.

[0625] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.23 (s, 1H), 5.79 (d, J=1.1 Hz, 1H), 4.87-4.76 (m, 1H), 4.32 (d, J=6.6 Hz, 2H), 2.26 (t, J=6.5 Hz, 1H), 1.97 (dt, J=12.6 Hz, J=3.2 Hz, 1H), 1.90-1.72 (m, 3H), 1.69-0.81 (m, 38H), 0.70-0.61 (m, 4H).

[0626] Physical properties of compound (1-3-1) were as described below.

[0627] Transition temperature: C 122 I.

Synthesis Example 6: Synthesis of Compound (1-4-82)

[0628] ##STR00161##

First Step

[0629] Compound (T-4) (50.0 g) was used as a raw material, imidazole (28.7 g) and dichloromethane (800 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (110 mL) solution of t-butyldiphenylchlorosilane (116.1 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=10:1 in a volume ratio) to obtain compound (T-17) (127.4 g; 90%).

Second Step

[0630] Compound (T-18) (63.6 g; 54%) was obtained by using compound (T-17) (127.4 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 2.

Third Step

[0631] Compound (T-19) (5.00 g), compound (T-18) (8.29 g), DMAP (1.0 g) and dichloromethane (80 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (40 mL) solution of DCC (5.00 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=1:1 in a volume ratio) to obtain compound (T-20) (8.66 g; 75%).

Fourth Step

[0632] Compound (T-20) (8.66 g) and THF (50 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. TBAF (1.00 M; THF solution; 18 mL) was slowly added thereto, and the resulting mixture was stirred for 1 hour while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (1-4-82) (4.43 g; 88%).

[0633] An NMR analysis value of the resulting compound (1-4-82) was as described below.

[0634] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.11 (s, 4H), 6.26 (s, 1H), 5.82 (d, J=1.1 Hz, 1H), 4.92-4.87 (m, 1H), 4.34 (d, J=6.4 Hz, 2H), 2.58-2.48 (m, 3H), 2.34-2.33 (m, 1H), 2.15-2.13 (m, 2H), 1.98-1.93 (m, 2H), 1.65-1.52 (m, 6H), 1.37-1.25 (m, 4H), 0.89 (t, J=6.8 Hz, 3H).

[0635] Physical properties of compound (1-4-82) were as described below.

[0636] Transition temperature: C 44.0 (S.sub.A 40.0) I

Synthesis Example 7: Synthesis of Compound (1-4-41)

[0637] ##STR00162##

First Step

[0638] Compound (T-22) (9.13 g; 78%) was obtained by using compound (T-21) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Second Step

[0639] Compound (T-22) (9.13 g) and THF (50 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Pyridinium p-toluenesulfonate (4.89 g) and TBAF (1.00 M; THF solution; 19 mL) were slowly added thereto, and the resulting mixture was stirred for 1 hour while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio). The residue was further purified by recrystallization from a mixed solvent of heptane and toluene (1:1 in a volume ratio) to obtain compound (1-4-41) (4.53 g; 86%).

[0640] An NMR analysis value of the resulting compound (1-4-41) was as described below.

[0641] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.60 (d, J=8.7 Hz, 2H), 7.48 (d, J=8.1 Hz, 2H), 7.25 (d, J=8.1 Hz, 2H), 7.18 (d, J=8.7 Hz, 2H), 6.54 (s, 1H), 6.06 (d, J=0.8 Hz, 1H), 4.46 (d, J=6.5 Hz, 2H), 2.64 (t, J=7.6 Hz, 2H), 2.28-2.26 (m, 1H), 1.66-1.63 (m, 2H), 1.36-1.33 (m, 4H), 0.90 (t, J=6.8 Hz, 3H).

[0642] Physical properties of compound (1-4-41) were as described below.

[0643] Transition temperature: C 66.7 S.sub.A 135.1 I.

Synthesis Example 8: Synthesis of Compound (1-6-121)

[0644] ##STR00163##

First Step

[0645] Decyltriphenylphosphonium bromide (50.0 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 30 C. Potassium t-butoxide (11.9 g) was slowly added thereto, and the resulting mixture was stirred at 30 C. for 1 hour. A THF (50 mL) solution of compound (T-23) (19.3 g) prepared according to a technique described in WO 2012/058187 A was added thereto. The resulting mixture was stirred for 5 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=4:1 in a volume ratio) to obtain compound (T-24) (23.9 g; 82%).

Second Step

[0646] Compound (T-24) (23.9 g), toluene (400 mL) and IPA (400 mL) were put in a reaction vessel, Pd/C (0.38 g) was added thereto, and the resulting mixture was stirred at room temperature for 12 hours under a hydrogen atmosphere. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=4:1 in a volume ratio) to obtain compound (T-25) (22.8 g; 95%).

Third Step

[0647] Compound (T-25) (22.8 g) and dichloromethane (300 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. Boron tribromide (1.00 M; dichloromethane solution; 76 mL) was added thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene. The residue was further purified by recrystallization from heptane to obtain compound (T-26) (18.8 g; 86%).

Fourth Step

[0648] Compound (T-26) (18.8 g) and cyclohexane (400 mL) were put in an autoclave, and the resulting mixture was stirred at 70 C. for 6 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-27) (17.1 g; 90%).

Fifth Step

[0649] Lithium aluminum hydride (1.21 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. A THF (200 mL) solution of compound (T-27) (17.1 g) was slowly added thereto, and the resulting mixture was stirred for 2 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (T-28) (14.2 g; 83%).

Sixth Step

[0650] Compound (T-29) (10.1 g; 84%) was obtained by using compound (T-28) (6.0 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Seventh Step

[0651] Compound (1-6-121) (5.48 g; 86%) was obtained by using compound (T-29) (10.1 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0652] An NMR analysis value of the resulting compound (1-6-121) was as described below.

[0653] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.23 (s, 1H), 5.79 (d, J=0.8 Hz, 1H), 4.77-4.71 (m, 1H), 4.32 (d, J=6.5 Hz, 2H), 2.31 (t, J=6.6 Hz, 1H), 2.04-2.02 (m, 2H), 1.80-1.68 (m, 6H), 1.39-1.25 (m, 18H), 1.13-0.80 (m, 14H).

[0654] Physical properties of compound (1-6-121) were as described below.

[0655] Transition temperature: C 79.8 S.sub.A 122.0 I.

Synthesis Example 9: Synthesis of Compound (1-4-4)

[0656] ##STR00164##

First Step

[0657] Compound (T-31) (8.84 g; 80%) was obtained by using compound (T-30) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Second Step

[0658] Compound (1-4-4) (4.26 g; 81%) was obtained by using compound (T-31) (8.84 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0659] An NMR analysis value of the resulting compound (1-4-4) was as described below.

[0660] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 1H), 5.82 (d, J=1.1 Hz, 1H), 4.33 (d, J=6.6 Hz, 2H), 3.99 (d, J=6.5 Hz, 2H), 2.33 (t, J=6.7 Hz, 1H), 1.80-1.62 (m, 9H), 1.32-0.80 (m, 22H).

[0661] Physical properties of compound (1-4-4) were as described below.

[0662] Transition temperature: C 51.9 S.sub.A 72.5 I.

Synthesis Example 10: Synthesis of Compound (1-4-108)

[0663] ##STR00165##

First Step

[0664] Compound (T-33) (4.13 g; 82%) was obtained by using compound (T-32) (5.00 g) as a raw material in a manner similar to the technique in the fifth step in Synthesis Example 8.

Second Step

[0665] Compound (T-34) (7.10 g; 80%) was obtained by using compound (T-33) (4.13 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Third Step

[0666] Compound (1-4-108) (3.65 g; 85%) was obtained by using compound (T-34) (7.10 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0667] An NMR analysis value of the resulting compound (1-4-108) was as described below.

[0668] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.22 (s, 1H), 5.79 (d, J=1.1 Hz, 1H), 4.79-4.73 (m, 1H), 4.31 (d, J=6.7 Hz, 2H), 2.32 (t, J=6.5 Hz, 1H), 2.02-1.99 (m, 2H), 1.82-1.79 (m, 2H), 1.72-1.70 (m, 4H), 1.42-0.98 (m, 19H), 0.89-0.80 (m, 7H).

[0669] Physical properties of compound (1-4-108) were as described below.

[0670] Transition temperature: C 46.1 S.sub.A 122 I.

Synthesis Example 11: Synthesis of Compound (1-4-5)

[0671] ##STR00166##

First Step

[0672] Compound (T-36) (8.60 g; 80%) was obtained by using compound (T-35) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Second Step

[0673] Compound (1-4-5) (4.21 g; 81%) was obtained by using compound (T-36) (8.60 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0674] An NMR analysis value of the resulting compound (1-4-5) was as described below.

[0675] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.24 (s, 1H), 5.82 (d, J=1.1 Hz, 1H), 4.33 (d, J=6.6 Hz, 2H), 4.21 (t, J=6.8 Hz, 2H), 2.29-2.26 (m, 1H), 1.78-1.67 (m, 8H), 1.60-1.55 (m, 2H), 1.31-1.07 (m, 10H), 1.00-0.79 (m, 13H).

[0676] Physical properties of compound (1-4-5) were as described below.

[0677] Transition temperature: C 69.4 S.sub.A 124.6 I.

Synthesis Example 12: Synthesis of Compound (1-4-6)

[0678] ##STR00167##

First Step

[0679] Then, (1,3-dioxolan-2-yl)methyltriphenylphosphonium bromide (19.5 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 30 C. Potassium t-butoxide (5.09 g) was added thereto, and the resulting mixture was stirred at 30 C. for 1 hour. Compound (T-37) (10.0 g) was added thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-38) (11.4 g; 90%).

Second Step

[0680] Compound (T-38) (11.4 g), Pd/C (0.18 g), IPA (200 mL) and toluene (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 12 hours under a hydrogen atmosphere. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-39) (10.6 g; 92%).

Third Step

[0681] Compound (T-39) (10.6 g), formic acid (14.5 g) and toluene (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at 100 C. for 4 hours. An insoluble matter was filtered off, and then the resulting material was neutralized with a sodium hydrogencarbonate aqueous solution, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-40) (8.11 g; 88%).

Fourth Step

[0682] Sodium borohydride (0.62 g) and ethanol (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. An ethanol (100 mL) solution of compound (T-40) (8.11 g) was added dropwise thereto. The resulting mixture was stirred for 4 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (T-41) (6.37 g; 78%).

Fifth Step

[0683] Compound (T-42) (8.67 g; 65%) was obtained by using compound (T-41) (6.37 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Sixth Step

[0684] Compound (1-4-6) (4.52 g; 85%) was obtained by using compound (T-42) (8.67 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0685] An NMR analysis value of the resulting compound (1-4-6) was as described below.

[0686] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 1H), 5.82 (d, J=0.9 Hz, 1H), 4.33 (d, J=6.7 Hz, 2H), 4.15 (t, J=6.7 Hz, 2H), 2.27 (t, J=6.5 Hz, 1H), 1.76-1.62 (m, 10H), 1.32-1.06 (m, 12H), 1.02-0.79 (m, 13H).

[0687] Physical properties of compound (1-4-6) were as described below.

[0688] Transition temperature: C 53.6 S.sub.A 113 I.

Synthesis Example 13: Synthesis of Compound (1-4-26)

[0689] ##STR00168##

First Step

[0690] Compound (T-44) (11.2 g; 88%) was obtained by using compound (T-43) (10.0 g) as a raw material in a manner similar to the technique in the first step in Synthesis Example 12.

Second Step

[0691] Compound (T-45) (10.1 g; 90%) was obtained by using compound (T-44) (11.2 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 12.

Third Step

[0692] Compound (T-46) (7.44 g; 85%) was obtained by using compound (T-45) (10.1 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 12.

Fourth Step

[0693] Compound (T-47) (6.07 g; 81%) was obtained by using compound (T-46) (7.44 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 12.

Fifth Step

[0694] Compound (T-48) (9.38 g; 73%) was obtained by using compound (T-47) (6.07 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Sixth Step

[0695] Compound (1-4-26) (3.32 g; 58%) was obtained by using compound (T-48) (9.38 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0696] An NMR analysis value of the resulting compound (1-4-26) was as described below.

[0697] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.13 (d, J=8.2 Hz, 2H), 7.10 (d, J=8.2 Hz, 2H), 6.23 (s, 1H), 5.82 (d, J=1.1 Hz, 1H), 4.32 (d, J=6.7 Hz, 2H), 4.20 (t, J=6.4 Hz, 2H), 2.68 (t, J=7.3 Hz, 2H), 2.43 (tt, J=12.2 Hz, J=3.2 Hz, 1H), 2.21 (t, J=6.8 Hz, 1H), 2.04-1.98 (m, 2H), 1.88-1.84 (m, 4H), 1.46-1.38 (m, 2H), 1.35-1.19 (m, 9H), 1.07-0.99 (m, 2H), 0.89 (t, J=7.2 Hz, 3H).

[0698] Physical properties of compound (1-4-26) were as described below.

[0699] Transition temperature: C 41.4 I.

Synthesis Example 14: Synthesis of Compound (1-6-122)

[0700] ##STR00169##

First Step

[0701] Compound (T-49) (15.0 g) and triphenyl phosphine (24.8 g) were put in a reaction vessel, and the resulting mixture was stirred at 100 C. for 6 hours. The resulting product was filtrated and washed with heptane cooled with ice to obtain compound (T-50) (16.4 g; 52%).

Second Step

[0702] Compound (T-51) (10.0 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 70 C. N-butyllithium (1.63M; hexane solution; 25 mL) was slowly added thereto, and the resulting mixture was stirred for 1 hour. DMF (4.0 mL) was slowly added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-52) (6.37 g; 77%).

Third Step

[0703] Compound (T-50) (14.3 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 30. Potassium t-butoxide (3.21 g) was slowly added thereto, and the resulting mixture was stirred at 30 C. for 1 hour. A THF (100 mL) solution of compound (T-52) (6.37 g) was slowly added thereto, and the resulting mixture was stirred for 4 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-53) (7.50 g; 85%).

Fourth Step

[0704] Compound (T-53) (7.50 g), Pd/C (0.11 g), IPA (200 mL) and toluene (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 12 hours under a hydrogen atmosphere. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-54) (7.21 g; 95%).

Fifth Step

[0705] Compound (T-54) (7.21 g), formic acid (9.70 g) and toluene (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at 100 C. for 4 hours. An insoluble matter was filtered off, and then the resulting material was neutralized with a sodium hydrogencarbonate aqueous solution, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-55) (5.65 g; 90%).

Sixth Step

[0706] Lithium aluminum hydride (0.43 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. A THF (100 mL) solution of compound (T-55) (5.65 g) was slowly added thereto, and the resulting mixture was stirred for 2 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (T-56) (4.83 g; 85%).

Seventh Step

[0707] Compound (T-57) (8.41 g; 84%) was obtained by using compound (T-56) (4.83 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Eighth Step

[0708] Compound (1-6-122) (3.22 g; 62%) was obtained by using compound (T-57) (8.41 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0709] An NMR analysis value of the resulting compound (1-6-122) was as described below.

[0710] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.13 (d, J=8.2 Hz, 2H), 7.10 (d, J=8.2 Hz, 2H), 6.26 (s, 1H), 5.82 (d, J=1.1 Hz, 1H), 4.92-4.87 (m, 1H), 4.34 (d, J=6.7 Hz, 2H), 2.60 (t, J=7.3 Hz, 2H), 2.54-2.49 (m, 1H), 2.31 (t, J=6.5 Hz, 1H), 2.15-2.04 (m, 4H), 1.98-1.96 (m, 2H), 1.66-1.52 (m, 8H).

[0711] Physical properties of compound (1-6-122) were as described below.

[0712] Transition temperature: C 62.0 I.

Synthesis Example 15: Synthesis of Compound (1-6-123)

[0713] ##STR00170##

First Step

[0714] Compound (T-59) (7.74 g; 70%) was obtained by using compound (T-58) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Second Step

[0715] Compound (1-6-123) (3.82 g; 83%) was obtained by using compound (T-59) (7.74 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0716] An NMR analysis value of the resulting compound (1-6-123) was as described below.

[0717] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.22 (s, 1H), 5.79 (s, 1H), 4.77-4.71 (m, 1H), 4.31 (d, J=6.5 Hz, 2H), 2.29-2.26 (m, 1H), 2.04-2.01 (m, 2H), 1.80-1.68 (m, 6H), 1.39-1.24 (m, 10H), 1.13-0.80 (m, 14H).

[0718] Physical properties of compound (1-6-123) were as described below.

[0719] Transition temperature: C 59.1 S.sub.A 114 I.

Synthesis Example 16: Synthesis of Compound (1-4-3)

[0720] ##STR00171##

First Step

[0721] Compound (T-61) (8.49 g; 79%) was obtained by using compound (T-60) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Second Step

[0722] Compound (1-4-3) (3.54 g; 69%) was obtained by using compound (T-61) (8.49 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0723] An NMR analysis value of the resulting compound (1-4-3) was as described below.

[0724] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.22 (s, 1H), 5.79 (d, J=1.1 Hz, 1H), 4.76-4.72 (m, 1H), 4.31 (d, J=6.8 Hz, 2H), 2.29-2.26 (m, 1H), 2.04-2.01 (m, 2H), 1.80-1.68 (m, 6H), 1.40-1.25 (m, 12H), 1.16-0.80 (m, 14H).

[0725] Physical properties of compound (1-4-3) were as described below.

[0726] Transition temperature: C 60.9 S.sub.A 109 I.

Synthesis Example 17: Synthesis of Compound (1-6-124)

[0727] ##STR00172##

First Step

[0728] Compound (T-63) (8.39 g; 58%) was obtained by using compound (T-62) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Second Step

[0729] Compound (1-6-124) (3.85 g; 89%) was obtained by using compound (T-63) (8.39 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0730] An NMR analysis value of the resulting compound (1-6-124) was as described below.

[0731] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.22 (s, 1H), 5.80 (d, J=1.1 Hz, 1H), 4.78-4.72 (m, 1H), 4.31 (s, 2H), 2.74 (s, 1H), 2.02-1.98 (m, 2H), 1.82-1.79 (m, 2H), 1.42-1.16 (m, 11H), 1.07-0.97 (m, 2H), 0.88 (t, J=6.8 Hz, 3H).

[0732] Physical properties of compound (1-6-124) were as described below.

[0733] Transition temperature: <50.0 I.

Synthesis Example 18: Synthesis of Compound (1-6-125)

[0734] ##STR00173##

First Step

[0735] Compound (T-64) (10.0 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Methylmagnesiumbromide (1.00 M; THF solution; 48 mL) was slowly added thereto, and the resulting mixture was stirred for 6 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-65) (4.58 g; 43%).

Second Step

[0736] Compound (T-65) (4.58 g), triethylamine (2.87 mL) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Acryloylchloride (1.68 mL) was slowly added thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=3:2 in a volume ratio) to obtain compound (T-66) (3.20 g; 58%).

Third Step

[0737] Compound (1-6-125) (1.12 g; 32%) was obtained by using compound (T-66) (3.20 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 1.

[0738] An NMR analysis value of the resulting compound (1-6-125) was as described below.

[0739] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.15 (s, 1H), 5.73 (d, J=1.2 Hz, 1H), 4.28 (d, J=6.6 Hz, 2H), 2.34-2.32 (m, 1H), 2.13-2.11 (m, 2H), 1.76-1.67 (m, 8H), 1.54 (s, 3H), 1.32-1.03 (m, 13H), 0.97-0.80 (m, 7H).

[0740] Physical properties of compound (1-6-125) were as described below.

[0741] Transition temperature: C 66.5 S.sub.A 81.1 I.

Synthesis Example 19: Synthesis of Compound (1-6-126)

[0742] ##STR00174## ##STR00175##

First Step

[0743] Compound (T-67) (25.0 g) and triphenyl phosphine (43.9 g) were put in a reaction vessel, and the resulting mixture was stirred at 90 C. for 6 hours. The resulting product was filtrated and washed with heptane to obtain compound (T-68) (22.8 g; 42%).

Second Step

[0744] Compound (T-69) (20.0 g), triethyl phosphonoacetate (22.5 g) and toluene (300 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Sodium ethoxide (20% ethanol solution) (34.2 g) was slowly added thereto, and the resulting mixture was stirred for 6 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-70) (23.3 g; 90%).

Third Step

[0745] Compound (T-70) (23.3 g), toluene (400 mL) and IPA (400 mL) were put in a reaction vessel, Pd/C (0.40 g) was added thereto, and the resulting mixture was stirred at room temperature for 12 hours under a hydrogen atmosphere. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-71) (21.5 g; 92%).

Fourth Step

[0746] Lithium aluminum hydride (1.57 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. A THF (200 mL) solution of compound (T-71) (21.5 g) was slowly added thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=4:1 in a volume ratio) to obtain compound (T-72) (14.3 g; 77%).

Fifth Step

[0747] Compound (T-72) (14.3 g) and dichloromethane (300 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. Dess-Martin Periodinane (27.1 g) was slowly added thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-73) (9.93 g; 70%).

Sixth Step

[0748] Compound (T-68) (21.7 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 30. Potassium t-butoxide (5.01 g) was slowly added thereto, and the resulting mixture was stirred at 30 C. for 1 hour. A THF (100 mL) solution of compound (T-73) (9.93 g) was slowly added thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-74) (6.97 g; 54%).

Seventh Step

[0749] Compound (T-74) (6.97 g), Pd/C (0.10 g), IPA (100 mL) and toluene (100 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 12 hours under a hydrogen atmosphere. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-75) (6.31 g; 90%).

Eighth Step

[0750] Compound (T-76) (4.96 g; 90%) was obtained by using compound (T-75) (6.31 g) as a raw material in a manner similar to the technique in the fifth step in Synthesis Example 14.

Ninth Step

[0751] Compound (T-77) (4.24 g; 85%) was obtained by using compound (T-76) (4.96 g) as a raw material in a manner similar to the technique in the sixth step in Synthesis Example 14.

Tenth Step

[0752] Compound (T-78) (5.40 g; 62%) was obtained by using compound (T-77) (4.24 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Eleventh Step

[0753] Compound (1-6-126) (2.37 g; 90%) was obtained by using compound (T-78) (4.24 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0754] An NMR analysis value of the resulting compound (1-6-126) was as described below.

[0755] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 1H), 5.81 (d, J=0.8 Hz, 1H), 4.79-4.73 (m, 1H), 4.34 (d, J=6.7 Hz, 2H), 2.32-2.29 (m, 1H), 2.12-2.03 (m, 4H), 1.82-1.72 (m, 6H), 1.57-1.49 (m, 2H), 1.44-1.35 (m, 4H), 1.22-0.84 (m, 11H).

[0756] Physical properties of compound (1-6-126) were as described below.

[0757] Transition temperature: C 72.0 S.sub.A 81.1 I.

Synthesis Example 20: Synthesis of Compound (1-6-127)

[0758] ##STR00176##

First Step

[0759] Compound (T-80) (6.40 g; 64%) was obtained by using compound (T-79) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Second Step

[0760] Compound (1-6-127) (2.02 g; 50%) was obtained by using compound (T-80) (6.40 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0761] An NMR analysis value of the resulting compound (1-6-127) was as described below.

[0762] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.24 (s, 1H), 5.82 (d, J=1.3 Hz, 1H), 4.33 (d, J=5.5 Hz, 2H), 4.15 (t, J=6.8 Hz, 2H), 2.39-2.37 (m, 1H), 1.73-1.66 (m, 10H), 1.32-1.09 (m, 18H), 0.91-0.80 (m, 11H).

[0763] Physical properties of compound (1-6-127) were as described below.

[0764] Transition temperature: C 110 I.

Synthesis Example 21: Synthesis of Compound (1-6-128)

[0765] ##STR00177##

First Step

[0766] Compound (T-82) (5.94 g; 60%) was obtained by using compound (T-81) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Second Step

[0767] Compound (1-6-128) (2.64 g; 70%) was obtained by using compound (T-82) (5.94 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0768] An NMR analysis value of the resulting compound (1-6-128) was as described below.

[0769] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.12-7.08 (m, 4H), 6.23 (s, 1H), 5.80 (d, J=1.0 Hz, 1H), 4.78-4.74 (m, 1H), 4.32 (d, J=6.6 Hz, 2H), 2.55 (t, J=7.6 Hz, 2H), 2.41 (tt, J=12.1 Hz, J=3.3 Hz, 1H), 2.28 (t, J=6.5 Hz, 1H), 2.07-2.04 (m, 2H), 1.93-1.90 (m, 2H), 1.85-1.82 (m, 4H), 1.61-1.57 (m, 2H), 1.44-1.30 (m, 8H), 1.20-1.13 (m, 6H), 0.88 (t, J=6.8 Hz, 3H).

[0770] Physical properties of compound (1-6-128) were as described below.

[0771] Transition temperature: C 85.0 I.

Synthesis Example 22: Synthesis of Compound (1-6-129)

[0772] ##STR00178##

First Step

[0773] Magnesium (turnings) (3.67 g) and THF (50 mL) were put in a reaction vessel, a THF (50 mL) solution of l-bromo-2-hexaethylene (29.1 g) was slowly added dropwise thereto, and the resulting mixture was stirred at 30 C. for 1 hour. A THF (100 mL) solution of compound (T-83) (30.0 g) was slowly added dropwise thereto, and the resulting mixture was stirred at room temperature for 6 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=4:1 in a volume ratio) to obtain compound (T-84) (8.88 g; 20%).

Second Step

[0774] Compound (T-84) (8.88 g), p-toluenesulfonic acid monohydrate (0.47 g), ethylene glycol (1.87 g) and toluene (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at 90 C. for 5 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-85) (8.00 g; 95%).

Third Step

[0775] Compound (T-85) (8.00 g), Pd/C (0.12 g), IPA (200 mL) and toluene (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 14 hours under a hydrogen atmosphere. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-86) (7.48 g; 93%).

Fourth Step

[0776] Compound (T-87) (5.72 g; 88%) was obtained by using compound (T-86) (7.48 g) as a raw material in a manner similar to the technique in the fifth step in Synthesis Example 14.

Fifth Step

[0777] Sodium borohydride (0.45 g) and ethanol (50 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. An ethanol (50 mL) solution of compound (T-87) (5.72 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 6 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-88) (2.65 g; 46%).

Sixth Step

[0778] Compound (T-89) (3.72 g; 67%) was obtained by using compound (T-88) (2.65 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Seventh Step

[0779] Compound (1-6-129) (1.60 g; 70%) was obtained by using compound (T-89) (3.72 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0780] An NMR analysis value of the resulting compound (1-6-129) was as described below.

[0781] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.22 (s, 1H), 5.79 (d, J=1.0 Hz, 1H), 4.77-4.71 (m, 1H), 4.31 (d, J=6.5 Hz, 2H), 2.31 (d, J=6.7 Hz, 1H), 2.04-2.01 (m, 2H), 1.80-1.68 (m, 6H), 1.39-0.92 (m, 20H), 0.90-0.80 (m, 8H).

[0782] Physical properties of compound (1-6-129) were as described below.

[0783] Transition temperature: C<50.0 I.

Synthesis Example 23: Synthesis of Compound (1-5-53)

[0784] ##STR00179## ##STR00180##

First Step

[0785] Compound (T-90) (21.1 g), tetrakis(triphenylphosphine)palladium (0.74 g), potassium carbonate (17.7 g), tetrabutylammonium bromide (8.3 g), 4-bromo-2-ethyl-1-iodobenzene (20.0 g), toluene (200 mL), IPA (150 mL) and H2O (50 mL) were put in a reaction vessel, and the resulting mixture was stirred at 80 C. for 6 hours. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=4:1 in a volume ratio) to obtain compound (T-91) (22.6 g; 85%).

Second Step

[0786] Compound (T-91) (22.6 g) and THF (200 mL) were put in a reaction vessel, the resulting mixture was cooled down to 70 C., and butyllithium (1.60 M; hexane solution; 41 mL) was slowly added dropwise thereto, and the resulting mixture was stirred at 70 C. for 1 hour. DMF (6.35 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-92) (16.1 g; 81%).

Third Step

[0787] Then, (1,3-dioxolan-2-yl)methyltriphenylphosphonium bromide (22.8 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 30 C. Potassium t-butoxide (5.90 g) was added thereto, and the resulting mixture was stirred at 30 C. for 1 hour. Compound (T-92) (16.1 g) was added thereto, and the resulting mixture was stirred for 6 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-93) (16.5 g; 86%).

Fourth Step

[0788] Compound (T-94) (14.9 g; 90%) was obtained by using compound (T-93) (16.5 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 12.

Fifth Step

[0789] Compound (T-95) (11.7 g; 88%) was obtained by using compound (T-94) (14.9 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 12.

Sixth Step

[0790] Compound (T-96) (9.41 g; 80%) was obtained by using compound (T-95) (11.7 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 12.

Seventh Step

[0791] Compound (T-97) (6.37 g; 70%) was obtained by using compound (T-96) (5.00 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 6.

Eighth Step

[0792] Compound (1-5-53) (3.40 g; 80%) was obtained by using compound (T-97) (6.37 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 6.

[0793] An NMR analysis value of the resulting compound (1-5-53) was as described below.

[0794] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.23-7.19 (m, 4H), 7.13-7.10 (m, 2H), 7.05-7.03 (m, 1H), 6.25 (s, 1H), 5.84 (d, J=1.1 Hz, 1H), 4.33 (d, J=6.7 Hz, 2H), 4.25 (t, J=6.6 Hz, 2H), 2.74 (t, J=7.3 Hz, 2H), 2.58 (q, J=7.5 Hz, 2H), 2.50 (tt, J=12.1 Hz, J=3.3 Hz, 1H), 2.22 (t, J=6.7 Hz, 1H), 2.10-2.04 (m, 2H), 1.96-1.87 (m, 4H), 1.52-1.44 (m, 2H), 1.33-1.21 (m, 9H), 1.11-1.02 (m, 5H), 0.90 (t, J=6.9 Hz, 3H).

[0795] Physical properties of compound (1-5-53) were as described below.

[0796] Transition temperature: C 40.0 I.

Synthesis Example 24: Synthesis of Compound (1-6-130)

[0797] ##STR00181##

[0798] Compound (1-4-2) (3.00 g), diethylamine (1.30 g) and cyclohexane (100 mL) were put in a reaction vessel, and the resulting mixture was stirred at 75 C. for 12 hours. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio) to obtain compound (1-6-130) (0.52 g; 15%).

[0799] An NMR analysis value of the resulting compound (1-6-130) was as described below.

[0800] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.18 (s, 1H), 5.74 (s, 1H), 4.74-4.67 (m, 1H), 3.23 (s, 2H), 2.50 (g, J=7.1 Hz, 4H), 2.03-2.01 (m, 2H), 1.78-1.68 (m, 6H), 1.37-0.80 (m, 28H).

[0801] Physical properties of compound (1-6-130) were as described below.

[0802] Transition temperature: C 14.1 S.sub.A 58.9 I.

[0803] Synthesis Example: Synthesis of comparative compound (S-1) Compound (S-1) was prepared as a comparative compound, and characteristics were measured. The reason is that the compound is described in WO 2014/090362 A, and similar to the compound of the invention.

##STR00182##

[0804] An NMR analysis value of the resulting comparative compound (S-1) was as described below.

[0805] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.57-7.52 (m, 2H), 7.45-7.42 (m, 2H), 7.36-7.30 (m, 1H), 7.04-6.95 (m, 2H), 4.75 (d, 6.0 Hz, 2H), 2.62 (t, J=7.8 Hz, 2H), 1.75-1.64 (m, 3H), 0.98 (t, J=7.4 Hz, 3H).

3. Example 1, Comparative Example 1

[0806] Comparison was made on vertical alignability and a voltage holding ratio (VHR) between compound (1-4-22) and comparative compound (S-1). In addition, composition (i) and polymerizable compound (M-1-1) were used for evaluation.

[0807] A proportion of a component of composition (i) was expressed in terms of % by weight.

##STR00183##

[0808] Polymerizable compound (M-1-1) is shown below.

##STR00184##

[0809] Vertical Alignability

[0810] Polymerizable compound (M-1-1) was added to composition (i) in a proportion of 0.4% by weight. Compound (1-4-22) or comparative compound (S-1) was added thereto in a proportion of 3.5% by weight. The resulting mixture was injected into a device having no alignment film in which a distance (cell gap) between two glass substrates was 3.5 micrometers, which were applied as Example 1 and Comparative Example 1. The device was set to a polarizing microscope, and irradiated with light from below, and presence or absence of light leakage was observed. When liquid crystal molecules were sufficiently aligned and no light passed through the device, the vertical alignability was judged to be Good. When light passing through the device was observed, the vertical alignability was represented as Poor.

[0811] Voltage Holding Ratio (VHR)

[0812] The polymerizable compound was polymerized by irradiating the device prepared as described above with ultraviolet light (30 J) using a black light, F40T10/BL (peak wavelength of 369 nm) made by EYE GRAPHICS CO., LTD. The device was charged by applying a pulse voltage (60 microseconds at 1 V) at 60 C. A decaying voltage was measured for 1.67 seconds with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was determined. Area B is an area without decay. A voltage holding ratio is expressed in terms of a percentage of area A to area B.

TABLE-US-00002 TABLE 2 Table 2: Physical properties of compound (1-4-22) and comparative compound (S-1) Example 1 Comparative Example 1 Compound Comparative compound (1-4-22) (S-1) Vertical alignability Good Good Voltage holding ratio 80.30% 23.79% (VHR)

[0813] Physical properties of compound (1-4-22) in Synthesis Example 2 and comparative compound (S-1) are summarized in Table 2. Both the compounds exhibited good vertical alignability in the device having no alignment film. On the other hand, the voltage holding ratio in use of compound (1-4-22) was higher than the voltage holding ratio in use of comparative compound (S-1). The reason is that a polar compound having a OH group as in comparative compound (S-1) significantly reduces the voltage holding ratio of the device, but the compound is provided with polymerizability as in compound (1-4-22), and the polar compound was incorporated into the polymer formed of the polymerizable compound to suppress reduction of the voltage holding ratio. Accordingly, compound (1-4-22) is reasonably a superior compound exhibiting the good vertical alignability without reducing the voltage holding ratio of the device.

4. Example 2, Example 3, Comparative Example 2

[0814] Comparison of a voltage holding ratio (VHR) was made on compound (1-4-2) and comparative compound (S-1). In addition, composition (ii) and polymerizable compound (M-1-3) were used for evaluation.

[0815] The compounds in the composition were represented using symbols according to definitions in Table 3 described below. In Table 3, the configuration of 1,4-cyclohexylene is trans. A parenthesized number next to a symbolized compound corresponds to the number of the compound. A symbol (-) means any other liquid crystal compound. A proportion (percentage) of the liquid crystal compound is expressed in terms of weight percent (% by weight) based on the weight of the liquid crystal composition. Values of the characteristics of the liquid crystal composition were summarized in the last part. The characteristics were measured according to the methods described above, and measured values are directly described (without extrapolation).

TABLE-US-00003 TABLE 3 Table 3 Method for description of compounds using symbols R(A.sub.1)Z.sub.1 .Math. .sub..Math. .sub..Math. Z.sub.n(A.sub.n)R Symbol 1) Left-terminal group R C.sub.nH.sub.2n+1 n- C.sub.nH.sub.2n+1O nO C.sub.mH.sub.2m+1OC.sub.nH.sub.2n mOn CH.sub.2CH V C.sub.nH.sub.2n+1CHCH nV CH.sub.2CHC.sub.nH.sub.2n Vn C.sub.mH.sub.2m+1CHCHC.sub.nH.sub.2n mVn CF.sub.2CH VFF CF.sub.2CHC.sub.nH.sub.2n VFFn 2) Right-terminal group R C.sub.nH.sub.2n+1 -n OC.sub.nH.sub.2n+1 On COOCH.sub.3 EMe CHCH.sub.2 V CHCHC.sub.nH.sub.2n+1 Vn C.sub.nH.sub.2nCHCH.sub.2 nV C.sub.mH.sub.2mCHCHC.sub.nH.sub.2n+1 mVn CHCF.sub.2 VFF F F Cl CL OCF.sub.3 OCF3 OCF.sub.2H OCF2H CF.sub.3 CF3 OCHCHCF.sub.3 OVCF3 CN C 3) Bonding group Z.sub.n C.sub.nH.sub.2n n COO E CHCH V CH.sub.2O 1O OCH.sub.2 O1 CF.sub.2O X CC T 4) Ring structure A.sub.n [00185] H [00186] B [00187] B(F) [00188] B(2F) [00189] B(F,F) [00190] B(2F,5F) [00191] B(2F,3F) [00192] Py [00193] G [00194] ch 5) Examples of description Example 1 3-HB-CL [00195] Example 2 5-HHBB(F,F)-F [00196] Example 3 3-HB-02 [00197] Example 4 3-HBB(F,F)-F [00198]

[0816] A proportion of a component of composition (ii) was expressed in terms of % by weight.

TABLE-US-00004 3-HB(2F,3F)-O2 (2-1) 18% 3-HHB(2F,3F)-O2 (2-6) 9% 2-HBB(2F,3F)-O2 (2-10) 6% 3-HBB(2F,3F)-O2 (2-10) 10% 4-HBB(2F,3F)-O2 (2-10) 8% 2-HH-3 (3-1) 25% 3-HH-4 (3-1) 10% 1-BB-3 (3-3) 5% 3-HBB-2 (3-6) 9%

[0817] NI=76.1 C.; =16.1 mPa.Math.s; n=0.100; =2.5; Vth=2.4 V.

Example 2

[0818] Compound (1-4-2) was added to composition (ii) in a proportion of 3% by weight.

##STR00199##

[0819] Compound (M-1-3) was further added thereto in a proportion of 0.3% by weight. The composition was injected into a device having no alignment film in which a distance (cell gap) between two glass substrates was 3.5 micrometers to prepare a device, and the polymerizable compound was polymerized by irradiating the device prepared as described above with ultraviolet light (40 J) using a black light, F40T10/BL (peak wavelength of 369 nm) made by EYE GRAPHICS CO., LTD, which was applied as Example 2.

##STR00200##

Example 3

[0820] Compound (1-4-2) was added to composition (ii) in a proportion of 3% by weight. The composition was injected into a device having no alignment film in which a distance (cell gap) between two glass substrates was 3.5 micrometers to prepare a device, and the polymerizable compound was polymerized by irradiating the device prepared as described above with ultraviolet light (60 J) using a black light, F40T10/BL (peak wavelength of 369 nm) made by EYE GRAPHICS CO., LTD, which was applied as Example 3.

##STR00201##

Comparative Example 2

[0821] Comparative compound (S-1) used in Comparative Example 1 was added to composition (ii) in a proportion of 3.5% by weight. Compound (M-1-3) was further added thereto in a proportion of 0.4% by weight. The composition was injected into a device having no alignment film in which a distance (cell gap) between two glass substrates was 3.5 micrometers to prepare a device, and the polymerizable compound was polymerized by irradiating the device prepared as described above with ultraviolet light (40 J) using a black light, F40T10/BL (peak wavelength of 369 nm) made by EYE GRAPHICS CO., LTD, which was applied as Comparative Example 2.

##STR00202##

[0822] A voltage holding ratio (VHR) of each device in Examples 2 to 3 and Comparative Example 2 was measured.

TABLE-US-00005 TABLE 4 Table 4: Voltage holding ratio (VHR) Liquid Polar compound Polymerizable compound crystal Amount of Amount of VHR/1 V, 0.3 Hz 60 C. (%) composition Compound addition Compound addition 0 h 250 h 500 hr Example 2 Composition 1-4-2 3 wt % M-1-3 0.3 wt % 96.3 95.8 94.9 (ii) Example 3 Composition 1-4-2 3 wt % 93.7 92.4 90.2 (ii) Comparative Composition S-1 3.5 wt % M-1-3 0.4 wt % 72.9 Example 2 (ii)

[0823] The voltage holding ratio in use of compound (1-4-2) was higher than the voltage holding ratio in use of comparative compound (S-1) in Comparative Example 2. The reason is that a polar compound having a OH group as in comparative compound (S-1) significantly reduced the voltage holding ratio of the device, but in the polymerizable polar compound as in compound (1-4-2), the polar compound was incorporated into the polymer formed to suppress reduction of the voltage holding ratio. Accordingly, compound (1-4-2) is reasonably a superior compound without reducing the voltage holding ratio of the device.

[0824] Moreover, in each device in Examples 2 and 3, when the voltage holding ratio after the device was allowed to be left on the backlight for a predetermined period of time was measured, a high value thereof was maintained as shown in Table 4.

5. Synthesis Example of Compound (1)

Synthesis Example 1: Synthesis of Compound (1-4-3)

[0825] ##STR00203##

First Step

[0826] Compound (T-1) (25.0 g), triethylamine (16.65 mL) and THF (300 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Acrylic chloride (9.7 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 6 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-2) (16.4 g; 54%).

Second Step

[0827] Sodium hydride (2.57 g) and THF (300 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A THF solution (100 mL) solution of compound (T-2) (16.4 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 1 hour. Methyl iodide (3.7 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 3 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=4:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (1-4-3) (14.2 g; 83%).

[0828] An NMR analysis value of the resulting compound (1-4-3) was as described below.

[0829] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.56 (m, 1H), 6.27 (t, 1H), 5.65 (t, 1H), 4.45 (m, 1H), 2.90 (s, 3H), 1.83-1.52 (m, 8H), 1.43-1.20 (m, 8H), 1.18-0.92 (m, 9H), 0.89-0.80 (m, 5H).

[0830] Physical properties of compound (1-4-3) were as described below.

[0831] Transition temperature: C 56.9 I.

Synthesis Example 2: Synthesis of Compound (1-4-45)

[0832] ##STR00204##

First Step

[0833] Compound (T-3) (25.0 g), triethylamine (16.0 mL) and THF (300 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Acrylic chloride (9.28 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 6 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-4) (15.6 g; 51%).

Second Step

[0834] Sodium hydride (2.55 g) and THF (300 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A THF solution (100 mL) solution of compound (T-4) (15.6 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 1 hour. Methyl iodide (3.6 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 3 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=4:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (1-4-45) (13.0 g; 80%).

[0835] An NMR analysis value of the resulting compound (1-4-45) was as described below.

[0836] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.51 (m, 4H), 7.23 (m, 4H), 6.54 (m, 1H), 6.25 (t, 1H), 5.63 (t, 1H), 2.95 (s, 3H), 2.62 (t, 2H), 1.67-1.62 (m, 2H), 1.37-1.33 (m, 4H), 0.90 (s, 3H).

[0837] Physical properties of compound (1-4-45) were as described below.

[0838] Transition temperature: C 58.0 I.

6. Example 11, Comparative Example 11

[0839] Comparison was made on vertical alignability and a voltage holding ratio (VHR) between compound (1-4-3) and comparative compound (S-1). Composition (i) and polymerizable compound (M-1-1) were used for evaluation. In addition, comparative compound (S-1), composition (i) and polymerizable compound (M-1-1) are identical thereto used in Example 1.

[0840] Vertical Alignability

[0841] Polymerizable compound (M-1-1) was added to composition (i) in a proportion of 0.4% by weight. Compound (1-4-3) or comparative compound (S-1) was added thereto in a proportion of 3.0% by weight. The resulting mixture was injected into a device having no alignment film in which a distance (cell gap) between two glass substrates was 3.5 micrometers, which were applied as Example 11 and Comparative Example 11. The device was set to a polarizing microscope, and irradiated with light from below, and presence or absence of light leakage was observed. When liquid crystal molecules were sufficiently aligned and no light passed through the device, the vertical alignability was judged to be Good. When light passing through the device was observed, the vertical alignability was represented as Poor.

[0842] Voltage Holding Ratio (VHR)

[0843] The device prepared as described above was charged by applying a pulse voltage (60 microseconds at 1 V) at 60 C. A decaying voltage was measured for 0.0167 second with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was determined. Area B is an area without decay. A voltage holding ratio is expressed in terms of a percentage of area A to area B.

TABLE-US-00006 TABLE 5 Table 5: Physical properties of compound (1-4-3) and comparative compound (S-1) Example 11 Comparative Example 11 Compound Comparative compound (1-4-3) (S-1) Vertical alignability Good Good Voltage holding ratio 95.2% 47.7% (VHR)

[0844] Physical properties of compound (1-4-3) in Synthesis Example 1 and comparative compound (S-1) are summarized in Table 5. Both the compounds exhibited good vertical alignability in the device having no alignment film. On the other hand, the voltage holding ratio in use of compound (1-4-3) was higher than the voltage holding ratio in use of comparative compound (S-1). The reason is that a polar compound having a OH group as in comparative compound (S-1) significantly reduces the voltage holding ratio of the device, but an acrylamide group causes no reduction of the voltage holding ratio. Accordingly, compound (1-4-3) is reasonably a superior compound exhibiting the good vertical alignability without reducing the voltage holding ratio of the device.

7. Examples 12 to 13, Comparative Example 12

[0845] Examples as the device will be described below.

Raw Material

[0846] A composition to which a polar compound having a (meth)acrylamide group represented by formula (1) was added was injected into a device having no alignment film. After the device was irradiated with ultraviolet light, vertical alignment of liquid crystal molecules in the device was examined. A raw material will be described first. As the raw material, compositions (iii) and (iv), polar compound (1-4-3) having the (meth)acrylamide group and polymerizable compound (M-1-1) were used.

[0847] A proportion of a component of composition (iii) was expressed in terms of % by weight.

TABLE-US-00007 3-HB(2F,3F)-O2 (2-1) 10% 5-HB(2F,3F)-O2 (2-1) 7% 2-BB(2F,3F)-O2 (2-4) 7% 3-BB(2F,3F)-O2 (2-4) 7% 3-B(2F,3F)B(2F,3F)-O2 (2-5) 3% 2-HHB(2F,3F)-O2 (2-6) 5% 3-HHB(2F,3F)-O2 (2-6) 10% 2-HBB(2F,3F)-O2 (2-10) 8% 3-HBB(2F,3F)-O2 (2-10) 10% 2-HH-3 (3-1) 14% 3-HB-O1 (3-2) 5% 3-HHB-1 (3-5) 3% 3-HHB-O1 (3-5) 3% 3-HHB-3 (3-5) 4% 2-BB(F)B-3 (3-8) 4%

[0848] NI=73.2 C.; Tc<20 C.; n=0.113; =4.0; Vth=2.18 V; g=22.6 mPa.Math.s.

[0849] A proportion of a component of composition (iv) was expressed in terms of % by weight.

TABLE-US-00008 V-HB(2F,3F)-O2 (2-1) 10% V2-HB(2F,3F)-O2 (2-1) 10% 2-H1OB(2F,3F)-O2 (2-3) 3% 3-H1OB(2F,3F)-O2 (2-3) 3% 2O-BB(2F,3F)-O2 (2-4) 3% V2-BB(2F,3F)-O2 (2-4) 8% V2-HHB(2F,3F)-O2 (2-6) 5% 2-HBB(2F,3F)-O2 (2-10) 3% 3-HBB(2F,3F)-O2 (2-10) 3% V-HBB(2F,3F)-O2 (2-10) 6% V-HBB(2F,3F)-O4 (2-10) 8% V-HHB(2F,3Cl)-O2 (2-12) 7% 3-HH-4 (3-1) 14% V-HHB-1 (3-5) 10% 3-HBB-2 (3-6) 7%

[0850] NI=75.9 C.; Tc<20 C.; n=0.114; =3.9; Vth=2.20 V; g=24.7 mPa.Math.s.

[0851] The alignable monomer is polar compound (1-4-3) having a (meth)acrylamide group. In addition, when the monomer has hydrogen directly bonded with nitrogen, more specifically, only when M.sup.1 in formula (1) is hydrogen, in order to define a structure of the (meth)acrylamide group, NH was designated in a structural formula.

##STR00205##

[0852] The polymerizable compound is polymerizable compound (M-1-1).

##STR00206##

Vertical Alignment of Liquid Crystal Molecules

Example 12

[0853] Polar compound (1-4-3) having a (meth) acrylamide group was added to composition (iii) in a proportion of 5% by weight. The resulting mixture was injected, on a hot stage at 100 C., into a device having no alignment film in which a distance (cell gap) between two glass substrates was 4.0 micrometers. Polar compound (1-4-3) having the (meth)acrylamide group was polymerized by irradiating the device with ultraviolet light (28J) using an ultra-high pressure mercury lamp USH-250-BY (made by Ushio, Inc.). The device was set to a polarizing microscope in which a polarizer and an analyzer were orthogonally arranged, and irradiated with light from below, and presence or absence of light leakage was observed. When liquid crystal molecules were sufficiently aligned and no light passed through the device, the vertical alignment was judged to be Good. When light passing through the device was observed, the vertical alignment was represented as Poor.

Example 13, Comparative Example 12

[0854] In Example 13, a device having no alignment film was prepared by using a mixture prepared by adding a polar compound having a (meth)acrylamide group to a composition. Presence or absence of light leakage was observed in a manner similar to Example 12. The results are summarized in the table. In Example 13, polymerizable compound (M-1-1) was also added in a proportion of 0.5% by weight. In Comparative Example 12, polar compound (S-1) was selected for comparison. The reason is that the compound has no polymerizable group, and therefore is different from compound (1).

##STR00207##

TABLE-US-00009 TABLE 6 Table 6: Vertical alignability of molecules Polar Polymerizable compound compound Liquid crystal (5% by (0.5% by Vertical composition weight) weight) alignment Example 12 Composition 1-4-3 Good (iii) Example 13 Composition 1-4-3 M-1-1 Good (iv) Comparative Composition S-1 Poor Example 12 (iii)

8. Synthesis Example of Compound (1)

Synthesis Example 1: Synthesis of Compound (1-2-7)

[0855] ##STR00208##

First Step

[0856] Paraformaldehyde (60.0 g), DABCO (56.0 g) and water (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 15 minutes. A THF (40 mL) solution of compound (T-1) (50.0 g) was added dropwise thereto, and the resulting mixture was stirred at room temperature for 72 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=2:1 in a volume ratio) to obtain compound (T-2) (44.1 g; 68%).

Second Step

[0857] Compound (T-2) (44.1 g), imidazole (25.0 g) and dichloromethane (400 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane solution (200 mL) of t-butyldimethylchlorosilane (53 g) was added dropwise thereto, and the resulting mixture was stirred for 4 hours while raising temperature to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-3) (105 g; 84%).

Third Step

[0858] Compound (T-3) (105 g), THF (600 mL), methanol (150 mL) and water (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Lithium hydroxide monohydrate (17.4 g) was added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and 6 N hydrochloric acid (20 mL) was slowly added thereto to acidify the resulting mixture, and then an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-4) (34.0 g; 35%).

##STR00209##

Fourth Step

[0859] Compound (T-5) (7.5 g), tetrakis(triphenylphosphine)palladium (1.3 g), TBAB (tetrabutylammonium bromide) (1.5 g), potassium carbonate (6.4 g), l-bromo-3,5-dimethoxybenzene (5 g), toluene (200 mL), IPA (2-propanol) (80 mL) and pure water (20 mL) were put in a reaction vessel, and the resulting mixture was stirred at 90 C. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio), and further purified by recrystallization from a mixed solvent of heptane and toluene (1:1 in a volume ratio) to obtain compound (T-6) (7.18 g; 85%).

Fifth Step

[0860] Compound (T-6) (7.18 g) and dichloromethane (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 50 while being stirred. Boron tribromide (2.1 mL) was added dropwise thereto, and the resulting mixture was stirred for 5 hours while raising temperature to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio) to obtain compound (T-7) (5.3 g; 80%).

Sixth Step

[0861] Compound (T-7) (5.3 g), ethylene carbonate (3.0 g), potassium carbonate (6.5 g) and DMF (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at 100 C. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio) to obtain compound (T-8) (5.5 g; 83%).

Seventh Step

[0862] Compound (T-8) (5.3 g), compound (T-4) (5.9 g), DMAP (1.52 g) and dichloromethane (150 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. while being stirred. A dichloromethane solution (50 mL) of DCC (7.7 g) was added dropwise thereto, and the resulting mixture was stirred for 5 hours while raising temperature to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=1:1 in a volume ratio) to obtain compound (T-9) (8.3 g; 81%).

Eighth Step

[0863] Compound (T-9) (8.3 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. while being stirred. TBAF (2.9 g) was added dropwise thereto, and the resulting mixture was stirred for 3 hours while raising temperature to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio), and further purified by recrystallization from heptane to obtain compound (1-2-7) (4.5 g; 75%).

[0864] An NMR analysis value of the resulting compound (1-2-7) was as described below.

[0865] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.48-7.46 (m, 2H), 7.27-7.26 (m, 2H), 6.75 (d, J=2.3 Hz, 2H), 6.47-6.46 (m, 1H), 6.30 (s, 2H), 5.86 (d, J=1.1 Hz, 2H), 4.54 (t, J=4.4 Hz, 4H), 4.33 (s, 4H), 4.27-4.25 (m, 4H), 2.52-2.47 (m, 1H), 2.34 (s, 2H), 1.90 (t, J=14 Hz, 4H), 1.51-1.44 (m, 2H), 1.35-1.20 (m, 9H), 1.09-1.02 (m, 2H), 0.90 (t, J=6.9 Hz, 3H).

[0866] Physical properties of compound (1-2-7) were as described below.

[0867] Transition temperature: C 58.8

Synthesis Example 2: Synthesis of Compound (1-5-2)

[0868] ##STR00210## ##STR00211##

First Step

[0869] Compound (T-10) (10.0 g), 4-methoxyphenylboronic acid (19.1 g), tetrakis(triphenylphosphine)palladium (1.9 g), potassium carbonate (15.8 g), TBAB (3.7 g), toluene (200 mL), IPA (80 mL) and pure water (20 mL) were put in a reaction vessel, and the resulting mixture was stirred at 90 C. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio), and further purified by recrystallization from a mixed solvent of heptane and toluene (1:1 in a volume ratio) to obtain compound (T-11) (14.9 g; 82%).

Second Step

[0870] Hexyltriphenylphosphonium bromide (22.0 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was stirred while being cooled down to 30 C. Potassium t-butoxide (5.7 g) was added thereto, and the resulting mixture was stirred at 30 C. for 1 hour. A THF solution (100 mL) of compound (T-11) (14.9 g) was added dropwise thereto, and the resulting mixture was stirred for 4 hours while raising temperature to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (T-12) (16.2 g; 90%).

Third Step

[0871] Compound (T-12) (16.2 g), Pd/C (0.2 g), toluene (100 mL) and IPA (100 mL) were put in a reaction vessel, and the resulting mixture was stirred for 10 hours under a hydrogen atmosphere. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (T-13) (15.5 g; 95%).

Fourth Step

[0872] Compound (T-13) (15.5 g) and dichloromethane (200 mL) were put in a reaction vessel, and the resulting mixture was stirred while being cooled down to 50 C. Boron tribromide (22.0 g) was added dropwise thereto, and the resulting mixture was stirred for 5 hours while raising temperature to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=8:2 in a volume ratio) to obtain compound (T-14) (13.0 g; 90%).

Fifth Step

[0873] Compound (T-14) (13.0 g), ethylene carbonate (9.5 g), potassium carbonate (15.0 g) and DMF (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at 100 C. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=8:2 in a volume ratio) to obtain compound (T-15) (13.6 g; 84%).

Sixth Step

[0874] Compound (T-15) (13.6 g), compound (T-4) (14.4 g), DMAP (1.85 g) and dichloromethane (350 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. while being stirred. A dichloromethane solution (150 mL) of DCC (18.8 g) was added dropwise thereto, and the resulting mixture was stirred for 5 hours while raising temperature to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-16) (19.2 g; 75%).

Seventh Step

[0875] Compound (T-16) (19.2 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. while being stirred. TBAF (6.5 g) was added dropwise thereto, and the resulting mixture was stirred for 3 hours while raising temperature to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio), and further purified by recrystallization from heptane to obtain compound (1-5-2) (9.8 g; 70%).

[0876] An NMR analysis value of the resulting compound (1-5-2) was as described below.

[0877] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.65-7.55 (m, 2H), 7.45 (d, J=1.6 Hz, 1H), 7.39 (dd, J=7.8 Hz, J=1.8 Hz, 1H), 7.25-7.22 (m, 3H), 7.13 (d, J=8.6 Hz, 2H), 6.98-6.93 (m, 4H), 6.84 (d, J=8.7 Hz, 2H), 6.29 (s, 1H), 5.85 (d, J=1.2 Hz, 1H), 4.52 (t, J=4.8 Hz, 2H), 4.33 (d, J=6.7 Hz, 2H), 4.21 (t, J=7.8 Hz, J=1.8 Hz, 1H), 6.27 (d, J=3.5 Hz, 2H), 5.85 (s, 1H), 4.35-4.28 (m, 8H), 4.06-4.04 (m, 4H), 2.62 (t, J=7.8 Hz, 2H), 2.30 (s, 2H), 1.93-1.92 (m, 8H), 1.58-1.48 (m, 2H), 1.26-1.17 (m, 8H), 0.84 (t, 6.9 Hz, 3H).

[0878] Physical properties of compound (1-5-2) were as described below.

[0879] Transition temperature: C 44.0 I.

9. Example 21, Comparative Example 21

[0880] Comparison was made on vertical alignability between compound (1-2-7) and comparative compound (S-1). Composition (i) and polymerizable compound (M-1-1) were used for evaluation. In addition, comparative compound (S-1), composition (i) and polymerizable compound (M-1-1) are identical thereto used in Example 1.

[0881] Vertical Alignability

[0882] Polymerizable compound (M-1-1) was added to composition (i) in a proportion of 0.4% by weight. Compound (1-2-7) or comparative compound (S-1) was added thereto in a proportion of 0.5% to 3.0%. The resulting mixture was injected into a device having no alignment film in which a distance (cell gap) between two glass substrates was 3.5 micrometers, which were applied as Example 21 and Comparative Example 21. The device was set to a polarizing microscope, and irradiated with light from below, and presence or absence of light leakage was observed. When liquid crystal molecules were sufficiently aligned and no light passed through the device, the vertical alignability was judged to be Good. When light passing through the device was observed, the vertical alignability was represented as Poor.

TABLE-US-00010 TABLE 7 Table 6: Alignability of compound (1-2-7) and comparative compound (S-1) Addition Example 21 Comparative Example 21 concentration Compound Comparative compound (%) (1-2-7) (S-1) 0.5 Good Poor 1.0 Good Poor 2.0 Good Poor 3.0 Good Good

[0883] The vertical alignability of compound (1-2-7) and comparative compound (S-1) were summarized in Table 7. In comparative compound (S-1), the vertical alignability was confirmed in 3.0%. On the other hand, when compound (1-2-7) was used, the vertical alignability was confirmed in addition of 0.5%, and the good vertical alignability was exhibited at a lower concentration in comparison with comparative compound (S-1). The reason is that the vertical alignability was increased by compound (1-2-7) having a plurality of OH groups to induce vertical alignment. Accordingly, compound (1-2-7) is reasonably a superior compound exhibiting the good vertical alignability at a lower concentration.

10. Examples 22 to 23, Comparative Example 22

[0884] Examples as the device will be described below.

Raw Material

[0885] A composition to which a polar compound was added was injected into a device having no alignment film. After the device was irradiated with ultraviolet light, vertical alignment of liquid crystal molecules in the device was examined. A raw material will be described first. As the raw material, compositions (iii) and (iv), polar compounds (1-2-7) and (1-5-2) and polymerizable compound (M-1-1) were used. In addition, compositions (iii) and (iv) and polymerizable compound (M-1-1) are identical thereto used in Example 12.

[0886] The alignable monomer is polar compounds (1-2-7) and (1-5-2).

##STR00212##

[0887] The polymerizable compound is polymerizable compound (M-1-1).

##STR00213##

Vertical Alignment of Liquid Crystal Molecules

Example 22

[0888] Polar compound (1-2-7) was added to composition (iii) in a proportion of 5% by weight. The resulting mixture was injected, on a hot stage at 100 C., into a device having no alignment film in which a distance (cell gap) between two glass substrates was 4.0 micrometers. Polar compound (1-2-7) was polymerized by irradiating the device with ultraviolet light (28J) using an ultra-high pressure mercury lamp USH-250-BY (made by Ushio, Inc.). The device was set to a polarizing microscope in which a polarizer and an analyzer were arranged to directly go, and irradiated with light from below, and presence or absence of light leakage was observed. When no light passed through the device, the vertical alignment was judged to be Good. The reason is that liquid crystal molecules were presumed to be sufficiently aligned. When light passing through the device was observed, the vertical alignment was represented as Poor.

Example 23, Comparative Example 22

[0889] A device having no alignment film was prepared by using a mixture prepared by adding a polar compound having a polymerizable group to a composition. Presence or absence of light leakage was observed in a manner similar to Example 22. The results are summarized in Table 8. In Example 23, polymerizable compound (M-1-1) was also added in a proportion of 0.5% by weight. In Comparative Example 22, polar compound (S-2) was selected for comparison. The reason is that the compound has no polymerizable group, and therefore is different from compound (1).

##STR00214##

TABLE-US-00011 TABLE 8 Table 8: Vertical alignability of molecules Polar Polymerizable compound compound Liquid crystal (5% by (0.5% by Vertical composition weight) weight) alignment Example 22 Composition 1-2-7 Good (iii) Example 23 Composition 1-5-2 M-1-1 Good (iv) Comparative Composition S-2 Poor Example 22 (iii)

11. Synthesis Example of Compound (1)

Synthesis Example 1: Synthesis of Compound (1-1-1)

[0890] In addition, compound (1-1-1) is identical to compound (1-6-1).

##STR00215##

First Step

[0891] Compound (T-1) (40.0 g), triethyl phosphonoacetate (40.7 g) and toluene (800 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Sodium ethoxide (20% ethanol solution) (61.8 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio) to obtain compound (T-2) (42.0 g; 83%).

Second Step

[0892] Compound (T-2) (42.0 g), toluene (400 mL) and isopropyl alcohol (400 mL) were put in a reaction vessel, Pd/C (0.7 g) was added thereto, and the resulting mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio) to obtain compound (T-3) (40.1 g; 95%).

Third Step

[0893] Compound (T-3) (40.1 g) and THF (400 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 60 C. Lithium diisopropylamide (LDA) (1.13 M; THF solution; 142 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 1 hour. Methyl chloroformate (11.0 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio) to obtain compound (T-4) (30.5 g; 65%).

Fourth Step

[0894] Lithium aluminum hydride (1.7 g) and THF (300 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. A THF (600 mL) solution of compound (T-4) (30.5 g) was slowly added thereto, and the resulting mixture was stirred for 3 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (T-5) (20.1 g; 80%).

Fifth Step

[0895] Compound (T-5) (20.1 g), triethylamine (10.3 mL) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Methacryloyl chloride (6.0 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 4 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (1-1-1) (7.7 g; 32%).

[0896] An NMR analysis value of the resulting compound (1-1-1) was as described below.

[0897] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.11 (s, 1H), 5.58 (s, 1H), 4.29-4.26 (m, 1H), 4.14-4.11 (m, 1H), 3.60-3.57 (m, 1H), 3.50-3.47 (m, 1H), 1.98-1.95 (m, 5H), 1.78-1.67 (m, 8H), 1.32-1.11 (m, 12H), 0.99-0.81 (m, 13H)

[0898] Physical properties of compound (1-1-1) were as described below.

[0899] Transition temperature: C 65.0 I.

Synthesis Example 25: Synthesis of Compound (1-1-2)

[0900] In addition, compound (1-1-2) is identical to compound (1-2-1).

##STR00216##

First Step

[0901] Paraformaldehyde (30.0 g), 1,4-diazabicyclo[2.2.2]octane (DABCO) (56.0 g) and water (600 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 15 minutes. A THF (1200 mL) solution of compound (T-6) (50.0 g) was added dropwise thereto, and the resulting mixture was stirred at room temperature for 72 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=4:1 in a volume ratio) to obtain compound (T-7) (43.2 g; 65%).

Second Step

[0902] Compound (T-7) (42.2 g) was used as a raw material, imidazole (26.3 g) and dichloromethane (800 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (100 mL) solution of t-butyldiphenylchlorosilane (TBDPSCl) (106.4 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=10:1 in a volume ratio) to obtain compound (T-8) (107.0 g; 90%).

Third Step

[0903] Compound (T-8) (107.0 g), THF (800 mL), methanol (200 mL) and water (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Lithium hydroxide monohydrate (24.3 g) was added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and 6 N hydrochloric acid (100 mL) was slowly added thereto to acidify the resulting mixture, and then an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by recrystallization from heptane to obtain compound (T-9) (47.4 g; 48%).

Fourth Step

[0904] Compound (1-1-1) (7.7 g), compound (T-9) (8.0 g), DMAP (1.0 g) and dichloromethane (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (60 mL) solution of N,N-dicyclohexylcarbodiimide (DCC) (4.8 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=19:1 in a volume ratio) to obtain compound (T-10) (9.8 g; 70%).

Fifth Step

[0905] Compound (T-10) (9.8 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Tetra-n-butylammonium fluoride (TBAF) (1.00 M; THF solution; 16.5 mL) was slowly added thereto, and the resulting mixture was stirred for 1 hour while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (1-1-2) (3.1 g; 47%).

[0906] An NMR analysis value of the resulting compound (1-1-2) was as described below.

[0907] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 1H), 6.10 (s, 1H), 5.85 (s, 1H), 5.57 (s, 1H), 4.33 (d, J=4.5 Hz, 2H), 4.27-4.16 (m, 2H), 4.13-4.08 (m, 2H), 2.31 (s, 1H), 2.26-2.22 (m, 1H), 1.94 (s, 3H), 1, 81-1.61 (m, 8H), 1.32-1.08 (m, 12H), 1.00-0.79 (m, 13H).

[0908] Physical properties of compound (1-1-2) were as described below.

[0909] Transition temperature: C 49.6 I.

Synthesis Example 35: Synthesis of Compound (1-1-3)

[0910] In addition, compound (1-1-3) is identical to compound (1-2-2).

##STR00217## ##STR00218##

First Step

[0911] Compound (T-11) (15.0 g), N, N-dimethyl-4-aminopyridine (DMAP) (9.33 g), Meldrum's acid (9.54 g) and dichloromethane (250 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. N,N-dicyclohexylcarbodiimide (DCC) (15.7 g) was slowly added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure. The residue and ethanol (250 mL) were put in a reaction vessel, and the resulting mixture was stirred at 70 C. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into brine, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=1:1 in a volume ratio) to obtain compound (T-12) (10.2 g; 55%).

Second Step

[0912] Lithium aluminum hydride (0.6 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. A THF (100 mL) solution of compound (T-12) (10.2 g) was slowly added thereto, and the resulting mixture was stirred for 3 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio) to obtain compound (T-13) (7.35 g; 81%).

Third Step

[0913] Compound (T-13) (7.35 g), triethylamine (3.75 mL), N,N-dimethyl-4-aminopyridine (DMAP) (0.27 g) and dichloromethane (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. TIPSCl (triisopropylsilyl chloride) (5.05 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 24 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=19:1 in a volume ratio) to obtain compound (T-14) (6.50 g; 60%).

Fourth Step

[0914] Compound (T-14) (6.50 g), triethylamine (3.77 mL) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Methacryloyl chloride (2.00 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 4 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=1:1 in a volume ratio) to obtain compound (T-15) (4.70 g; 63%).

Fifth Step

[0915] Compound (T-15) (4.70 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. TBAF (1.00 M; THF solution; 10.3 mL) was slowly added thereto, and the resulting mixture was stirred for 1 hour while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-16) (1.50 g; 45%).

Sixth Step

[0916] Compound (T-17) (1.51 g; 55%) was obtained by using compound (T-16) (1.50 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 25.

Seventh Step

[0917] Compound (1-1-3) (0.45 g; 45%) was obtained by using compound (T-17) (1.51 g) as a raw material in a manner similar to the technique in the fifth step in Synthesis Example 25.

[0918] An NMR analysis value of the resulting compound (1-1-3) was as described below.

[0919] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 1H), 6.09 (s, 1H), 5.82 (d, J=1.1 Hz, 1H), 5.55 (s, 1H), 5.22-5.17 (m, 1H), 4.32-4.26 (m, 3H), 4.17-4, 12 (m, 3H), 2.50 (s, 1H), 2.03-1.89 (m, 5H), 1.83-1.58 (m, 9H), 1.41-1.08 (m, 11H), 0.96-0.78 (m, 13H).

[0920] Physical properties of compound (1-1-3) were as described below.

[0921] Transition temperature: C 61.2 I.

12. Examples 31 to 33, Comparative Example 31

[0922] Examples as the device will be described below.

Raw Material

[0923] A composition to which a polar compound was added was injected into a device having no alignment film. After the device was irradiated with ultraviolet light, vertical alignment of liquid crystal molecules in the device was examined. A raw material will be described first. As the raw material, compositions (iii) to (v), polar compounds (1-1-1) and (1-1-5) and polymerizable compound (M-1-1) were used. In addition, compositions (iii) and (iv) and polymerizable compound (M-1-1) are identical thereto used in Example 12.

[0924] A proportion of a component of composition (v) was expressed in terms of % by weight.

TABLE-US-00012 3-HB(2F,3F)-O2 (2-1) 7% 3-HB(2F,3F)-O4 (2-1) 8% 3-H2B(2F,3F)-O2 (2-2) 8% 3-BB(2F,3F)-O2 (2-4) 10% 2-HHB(2F,3F)-O2 (2-6) 4% 3-HHB(2F,3F)-O2 (2-6) 7% 3-HHB(2F,3F)-1 (2-6) 6% 2-HBB(2F,3F)-O2 (2-10) 6% 3-HBB(2F,3F)-O2 (2-10) 6% 4-HBB(2F,3F)-O2 (2-10) 5% 5-HBB(2F,3F)-O2 (2-10) 4% 3-HEB(2F,3F)B(2F,3F)-O2 (2-11) 3% 3-H1OCro(7F,8F)-5 (2-14) 3% 3-HDhB(2F,3F)-O2 (2-16) 5% 3-HH-O1 (3-1) 5% 1-BB-5 (3-3) 4% V-HHB-1 (3-5) 4% 5-HB(F)BH-3 (3-12) 5%

[0925] NI=81.1 C.; Tc<30 C.; n=0.119; =4.5; Vth=1.69 V; g=31.4 mPa.Math.s.

[0926] The alignable monomer is polar compounds (1-1-1) and (1-1-5).

##STR00219##

[0927] The polymerizable compound is polymerizable compound (M-1-1).

##STR00220##

Vertical Alignment of Liquid Crystal Molecules

Example 31

[0928] Polar compound (1-1-1) was added to composition (iii) in a proportion of 5 parts by weight. The resulting mixture was injected, on a hot stage at 100 C., into a device having no alignment film in which a distance (cell gap) between two glass substrates was 4.0 micrometers. Polar compound (1-1-1) was polymerized by irradiating the device with ultraviolet light (28J) using an ultra-high pressure mercury lamp USH-250-BY (made by Ushio, Inc.). The device was set to a polarizing microscope in which a polarizer and an analyzer were arranged to directly go, and irradiated with light from below, and presence or absence of light leakage was observed. When liquid crystal molecules were sufficiently aligned and no light passed through the device, the vertical alignment was judged to be Good. When light passing through the device was observed, the vertical alignment was represented as Poor.

Examples 32 to 33, Comparative Example 31

[0929] A device having no alignment film was prepared by using a mixture in which the composition and the polar compound were combined. Presence or absence of light leakage was observed in a manner similar to Example 31. The results are summarized in Table 9. In Example 33, polymerizable compound (M-1-1) was also added in a proportion of 0.5 part by weight. In Comparative Example 31, polar compound (S-3) described in Patent literature No. 5 was selected for comparison. The compound has no branching structure from a molecular terminal, and therefore is different from compound (1-1).

##STR00221##

TABLE-US-00013 TABLE 9 Table 9: Vertical alignability of molecules Polar Polymerizable compound compound Liquid crystal (5 parts by (0.5 part by Vertical composition weight) weight) alignment Example 31 Composition 1-1-1 Good (iii) Example 32 Composition 1-1-5 Good (v) Example 33 Composition 1-1-5 M-1-1 Good (iv) Comparative Composition S-3 Poor Example 31 (iii)

[0930] As shown in Table 9, in Examples 31 to 33, a kind of the composition or the polar compound and a concentration of the polar compound were changed, but no light leakage was observed. The above results indicate that the vertical alignment was good even without the alignment film in the device, and the liquid crystal molecules were stably aligned. In Example 33, polymerizable compound (M-1-1) was further added thereto, and the same results were obtained.

[0931] On the other hand, in Comparative Example 31, light leakage was observed. The above results indicate that the vertical alignment was poor.

Compatibility of Polar Compound

[0932] In a state at room temperature, stability of the mixture of the liquid crystal composition and the polar compound as obtained in Examples 31 to 33 was evaluated. After mixing thereof, the mixture was allowed to be isotropic at 100 C. and to be cooled down to 25 C. When presence or absence of precipitation was confirmed a half day later at room temperature, precipitation of the mixture in Examples 31 to 33 was not confirmed, and compatibility of the polar compound was good. On the other hand, precipitation of the mixture in Comparative Example 31 was confirmed, and compatibility of the polar compound was poor.

13. Synthesis Example of Compound (1)

Synthesis Example 1: Synthesis of Compound (1-6-1)

[0933] ##STR00222##

First Step

[0934] Compound (T-1) (40.0 g), triethyl phosphonoacetate (40.7 g) and toluene (800 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Sodium ethoxide (20% ethanol solution) (61.8 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio) to obtain compound (T-2) (42.0 g; 83%).

Second Step

[0935] Compound (T-2) (42.0 g), toluene (400 mL) and isopropanol (400 mL) were put in a reaction vessel, Pd/C (0.7 g) was added thereto, and the resulting mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio) to obtain compound (T-3) (40.1 g; 95%).

Third Step

[0936] Compound (T-3) (40.1 g) and THF (400 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 60 C. Lithium diisopropylamide (LDA) (1.13 M; THF solution; 142 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 1 hour. Methyl chloroformate (11.0 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio) to obtain compound (T-4) (30.5 g; 65%).

Fourth Step

[0937] Lithium aluminum hydride (1.7 g) and THF (300 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. A THF (600 mL) solution of compound (T-4) (30.5 g) was slowly added thereto, and the resulting mixture was stirred for 3 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (T-5) (20.1 g; 80%).

Fifth Step

[0938] Compound (T-5) (20.1 g), triethylamine (10.3 mL) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Methacryloyl chloride (6.0 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 4 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (1-6-1) (7.7 g; 32%).

[0939] An NMR analysis value of the resulting compound (1-6-1) was as described below.

[0940] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.11 (s, 1H), 5.58 (s, 1H), 4.29-4.26 (m, 1H), 4.14-4.11 (m, 1H), 3.60-3.57 (m, 1H), 3.50-3.47 (m, 1H), 1.98-1.95 (m, 5H), 1.78-1.67 (m, 8H), 1.32-1.11 (m, 12H), 0.99-0.81 (m, 13H)

[0941] Physical properties of compound (1-6-1) were as described below.

[0942] Transition temperature: C 65.0 I.

Synthesis Example 2: Synthesis of Compound (1-2-1)

[0943] ##STR00223##

First Step

[0944] Paraformaldehyde (30.0 g), DABCO (56.0 g) and water (600 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 15 minutes. A THF (1200 mL) solution of compound (T-6) (50.0 g) was added dropwise thereto, and the resulting mixture was stirred at room temperature for 72 hours. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=4:1 in a volume ratio) to obtain compound (T-7) (43.2 g; 65%).

Second Step

[0945] Compound (T-7) (42.2 g) was used as a raw material, imidazole (26.3 g) and dichloromethane (800 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (100 mL) solution of t-butyldiphenylchlorosilane (106.4 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=10:1 in a volume ratio) to obtain compound (T-8) (107.0 g; 90%).

Third Step

[0946] Compound (T-8) (107.0 g), THF (800 mL), methanol (200 mL) and water (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Lithium hydroxide monohydrate (24.3 g) was added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and 6 N hydrochloric acid (100 mL) was slowly added thereto to acidify the resulting mixture, and then an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by recrystallization from heptane to obtain compound (T-9) (47.4 g; 48%).

Fourth Step

[0947] Compound (1-6-1) (7.7 g), compound (T-9) (8.0 g), DMAP (1.0 g) and dichloromethane (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (60 mL) solution of DCC (4.8 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=19:1 in a volume ratio) to obtain compound (T-10) (9.8 g; 70%).

Fifth Step

[0948] Compound (T-10) (9.8 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. TBAF (1.00 M; THF solution; 16.5 mL) was slowly added thereto, and the resulting mixture was stirred for 1 hour while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (1-2-1) (3.1 g; 47%).

[0949] An NMR analysis value of the resulting compound (1-2-1) was as described below.

[0950] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 1H), 6.10 (s, 1H), 5.85 (s, 1H), 5.57 (s, 1H), 4.33 (d, J=4.5 Hz, 2H), 4.27-4.16 (m, 2H), 4.13-4.08 (m, 2H), 2.31 (s, 1H), 2.26-2.22 (m, 1H), 1.94 (s, 3H), 1, 81-1.61 (m, 8H), 1.32-1.08 (m, 12H), 1.00-0.79 (m, 13H).

[0951] Physical properties of compound (1-2-1) were as described below.

[0952] Transition temperature: C 49.6 I.

Synthesis Example 3: Synthesis of Compound (1-2-2)

[0953] ##STR00224## ##STR00225##

First Step

[0954] Compound (T-11) (15.0 g), DMAP (9.33 g), Meldrum's acid (9.54 g) and dichloromethane (250 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. DCC (15.7 g) was slowly added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure. The residue and ethanol (250 mL) were put in a reaction vessel, and the resulting mixture was stirred at 70 C. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into brine, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:toluene=1:1 in a volume ratio) to obtain compound (T-12) (10.2 g; 55%).

Second Step

[0955] Lithium aluminum hydride (0.6 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled with ice. A THF (100 mL) solution of compound (T-12) (10.2 g) was slowly added thereto, and the resulting mixture was stirred for 3 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio) to obtain compound (T-13) (7.35 g; 81%).

Third Step

[0956] Compound (T-13) (7.35 g), triethylamine (3.75 mL), N,N-dimethyl-4-aminopyridine (DMAP) (0.27 g) and dichloromethane (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. TIPSCl (triisopropylsilyl chloride) (5.05 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 24 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=19:1 in a volume ratio) to obtain compound (T-14) (6.50 g; 60%).

Fourth Step

[0957] Compound (T-14) (6.50 g), triethylamine (3.77 mL) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Methacryloyl chloride (2.00 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 4 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=1:1 in a volume ratio) to obtain compound (T-15) (4.70 g; 63%).

Fifth Step

[0958] Compound (T-15) (4.70 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. TBAF (1.00 M; THF solution; 10.3 mL) was slowly added thereto, and the resulting mixture was stirred for 1 hour while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-16) (1.50 g; 45%).

Sixth Step

[0959] Compound (T-17) (1.51 g; 55%) was obtained by using compound (T-16) (1.50 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 2.

Seventh Step

[0960] Compound (1-2-2) (0.45 g; 45%) was obtained by using compound (T-17) (1.51 g) as a raw material in a manner similar to the technique in the fifth step in Synthesis Example 2.

[0961] An NMR analysis value of the resulting compound (1-2-2) was as described below.

[0962] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 1H), 6.09 (s, 1H), 5.82 (d, J=1.1 Hz, 1H), 5.55 (s, 1H), 5.22-5.17 (m, 1H), 4.32-4.26 (m, 3H), 4.17-4, 12 (m, 3H), 2.50 (s, 1H), 2.03-1.89 (m, 5H), 1.83-1.58 (m, 9H), 1.41-1.08 (m, 11H), 0.96-0.78 (m, 13H).

[0963] Physical properties of compound (1-2-2) were as described below.

[0964] Transition temperature: C 61.2 I.

Synthesis Example 4: Synthesis of Compound (1-9-1)

[0965] ##STR00226##

First Step

[0966] Compound (T-18) (20.0 g) and THF (200 mL) were put in a reaction vessel, the resulting mixture was cooled down to 70 C., and Lithium diisopropylamide (LDA) (1.10M; THF solution; 68.0 mL) was slowly added dropwise thereto, and the resulting mixture was stirred for 1 hour. Methyl chloroformate (7.00 g) was slowly added thereto, and the resulting mixture was stirred for 4 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=9:1 in a volume ratio) to obtain compound (T-19) (19.4 g; 82%).

Second Step

[0967] Lithium aluminium hydride (1.93 g) and THF (200 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A THF (100 mL) solution of compound (T-19) (19.4 g) was slowly added thereto, and the resulting mixture was stirred for 3 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio) to obtain compound (T-20) (6.0 g; 38%).

Third Step

[0968] Compound (T-20) (6.0 g), triethylamine (3.2 mL) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Methacryloyl chloride (1.8 mL) was slowly added thereto, and the resulting mixture was stirred for 5 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (1-9-1) (2.5 g; 34%).

[0969] An NMR analysis value of the resulting compound (1-9-1) was as described below.

[0970] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.10 (s, 1H), 5.57 (d, J=1.1 Hz, 1H), 4.38 (dd, J=11.4 Hz, J=4.3 Hz, 1H), 4.23 (dd, J=11.3 Hz, J=6.7 Hz, 1H), 3.71-3.68 (m, 1H), 3.63-3.60 (m, 1H), 1.97 (s, 1H), 1.94 (s, 3H), 1.82-1.62 (m, 9H), 1.41-1.18 (m, 7H), 1.14-0.79 (m, 16H).

[0971] Physical properties of compound (1-9-1) were as described below.

[0972] Transition temperature: C 68.4 S.sub.A 89.3 I.

Synthesis Example 5: Synthesis of Compound (1-9-2)

[0973] ##STR00227##

First Step

[0974] Compound (T-7), 3,4-dihydro-2H-pyran (23.3 g) and pyridinium p-toluenesulfonate (PPTS) (5.80 g) were put in a reaction vessel, and the resulting mixture was stirred at 50 C. for 10 hours. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=2:1 in a volume ratio) to obtain compound (T-21) (39.5 g; 80%).

Second Step

[0975] Compound (T-21) (39.5 g), THF (400 mL) and water (400 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Lithium hydroxide monohydrate (15.4 g) was added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The resulting reaction mixture was poured into water, and 6 N hydrochloric acid (60 mL) was slowly added thereto to acidify the resulting mixture, and then an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-22) (32.6 g; 95%).

Third Step

[0976] Compound (1-9-1) (2.0 g), compound (T-22) (1.18 g), DMAP (0.32 g) and dichloromethane (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (60 mL) solution of DCC (1.30 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=19:1 in a volume ratio) to obtain compound (T-23) (2.37 g; 82%).

Fourth Step

[0977] Compound (T-23) (2.37 g), pyridinium p-toluenesulfonate (PPTS) (0.54 g), THF (50 mL) and methanol (50 mL) were put in a reaction vessel, and the resulting mixture was stirred at 50 C. for 5 hours. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (1-9-2) (1.50 g; 75%).

[0978] An NMR analysis value of the resulting compound (1-9-2) was as described below.

[0979] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.24 (s, 1H), 6.09 (s, 1H), 5.84 (s, 1H), 5.57 (s, 1H), 4.33-4.27 (m, 4H), 4.20-4.16 (m, 2H), 2.34-2.31 (m, 1H), 1.97-1.90 (m, 4H), 1.82-1.67 (m, 8H), 1.43-1.39 (m, 1H), 1.31-1.18 (m, 6H), 1.15-0.75 (m, 16H).

[0980] Physical properties of compound (1-9-2) were as described below.

[0981] Transition temperature: C 66.5 I.

Synthesis Example 6: Synthesis of Compound (1-9-3)

[0982] ##STR00228##

First Step

[0983] Compound (T-24) (30.0 g), ethanol (14.4 mL), potassium phosphate (53.6 g), copper iodide (1.60 g), ethyl acetoacetate (32.8 g) and dimethyl sulfoxide (DMSO) (500 mL) were put in a reaction vessel, and the resulting mixture was stirred at 80 C. for 6 hours. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio) to obtain compound (T-25) (19.5 g; 73%).

Second Step

[0984] Compound (T-26) (16.2 g; 70%) was obtained by using compound (T-25) (19.5 g) as a raw material in a manner similar to the technique in the first step in Synthesis Example 4E.

Third Step

[0985] Compound (T-27) (6.0 g; 45%) was obtained by using compound (T-26) (16.2 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 4.

Fourth Step

[0986] Compound (1-9-3) (2.3 g; 31%) was obtained by using compound (T-27) (6.0 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 4E.

[0987] An NMR analysis value of the resulting compound (1-9-3) was as described below.

[0988] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.18-7.17 (m, 4H), 6.09 (s, 1H), 5.57 (s, 1H), 4.47-4.38 (m, 2H), 3.91-3.85 (m, 2H), 3.19-3.14 (m, 1H), 2.44 (tt, J=12.2 Hz, J=3.0 Hz, 1H), 1.93-1.86 (m, 8H), 1.48-1.38 (m, 2H), 1.34-1.19 (m, 9H), 1.07-0.99 (m, 2H), 0.89 (t, J=6.8 Hz, 3H).

[0989] Physical properties of compound (1-9-3) were as described below.

[0990] Transition temperature: C 36.1 I.

Synthesis Example 7: Synthesis of Compound (1-9-4)

[0991] ##STR00229##

First Step

[0992] Compound (T-28) (2.2 g; 76%) was obtained by using compound (1-9-3) (2.0 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 5.

Second Step

[0993] Compound (1-9-4) (1.3 g; 70%) was obtained by using compound (T-28) (2.2 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 5.

[0994] An NMR analysis value of the resulting compound (1-9-4) was as described below.

[0995] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.17-7.16 (m, 4H), 6.21 (s, 1H), 6.07 (s, 1H), 5.81 (d, J=1.0 Hz, 1H), 5.55 (s, 1H), 4.46-4.39 (m, 4H), 4.27 (d, J=6.2 Hz, 2H), 3.42-3.37 (m, 1H), 2.44 (tt, J=12.2 Hz, J=3.1 Hz, 1H), 2.22-2.21 (m, 1H), 1.95 (s, 3H), 1.87-1.85 (m, 4H), 1.46-1.38 (m, 2H), 1.34-1.19 (m, 9H), 1.07-0.99 (m, 2H), 0.89 (t, J=7.0 Hz, 3H).

[0996] Physical properties of compound (1-9-4) were as described below.

[0997] Transition temperature: C 52.3 I.

Synthesis Example 8: Synthesis of Compound (1-9-5)

[0998] ##STR00230##

First Step

[0999] Compound (T-29) (30.0 g), triethyl phosphonoacetate (33.0 g) and toluene (500 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. Sodium ethoxide (20% ethanol solution) (50.1 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 6 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio) to obtain compound (T-30) (32.8 g; 85%).

Second Step

[1000] Compound (T-30) (32.8 g), toluene (300 mL), IPA (300 mL) and Pd/C (0.55 g) were put in a reaction vessel, and the resulting mixture was stirred for 12 hours under a hydrogen atmosphere. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=4:1 in a volume ratio). The residue was further purified by recrystallization from heptane to obtain compound (T-31) (16.8 g; 51%).

Third Step

[1001] Compound (T-32) (14.1 g; 71%) was obtained by using compound (T-31) (16.8 g) as a raw material in a manner similar to the technique in the first step in Synthesis Example 4.

Fourth Step

[1002] Compound (T-33) (6.0 g; 52%) was obtained by using compound (T-32) (14.1 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 4.

Fifth Step

[1003] Compound (1-9-5) (2.3 g; 32%) was obtained by using compound (T-33) (6.0 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 4.

[1004] An NMR analysis value of the resulting compound (1-9-5) was as described below.

[1005] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.14-7.10 (m, 4H), 6.12 (s, 1H), 5.59 (s, 1H), 4.43-4.40 (m, 1H), 4.28-4.25 (m, 1H), 3.75-3.64 (m, 2H), 2.55 (t, J=7.6 Hz, 2H), 2.47-2.42 (m, 1H), 2.14 (s, 1H), 1.96-1.91 (m, 7H), 1.74-1.69 (m, 1H), 1.62-1.22 (m, 11H), 0.88 (t, J=6.8 Hz, 3H).

[1006] Physical properties of compound (1-9-5) were as described below.

[1007] Transition temperature: C<50.0 I.

Synthesis Example 9: Synthesis of Compound (1-9-6)

[1008] ##STR00231##

First Step

[1009] Compound (T-34) (1.9 g; 68%) was obtained by using compound (1-9-5) (2.0 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 5.

Second Step

[1010] Compound (1-9-6) (1.2 g; 75%) was obtained by using compound (T-34) (1.9 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 5.

[1011] An NMR analysis value of the resulting compound (1-9-6) was as described below.

[1012] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.13-7.10 (m, 4H), 6.27 (s, 1H), 6.11 (s, 1H), 5.86 (s, 1H), 5.58 (s, 1H), 4.40-4.32 (m, 4H), 4.25-4.20 (m, 2H), 2.56 (t, J=7.6 Hz, 2H), 2.45 (tt, J=12.1 Hz, J=2.9 Hz, 1H), 2.35-2.32 (m, 1H), 2.04-1.91 (m, 7H), 1.62-1.26 (m, 12H), 0.88 (t, J=6.8 Hz, 3H).

[1013] Physical properties of compound (1-9-6) were as described below.

[1014] Transition temperature: C 35.8 I.

Synthesis Example 10: Synthesis of Compound (1-9-7)

[1015] ##STR00232##

First Step

[1016] Then, 2-(1,3-dioxan-2-yl)ethyltriphenylphosphonium bromide (103.7 g) and THF (500 mL) were put in a reaction vessel, the resulting mixture was cooled down to 30 C., and potassium t-butoxide (25.4 g) was added thereto, and the resulting mixture was stirred for 1 hour. A THF (300 mL) solution of compound (T-35) (50.0 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 6 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=1:1 in a volume ratio) to obtain compound (T-36) (63.0 g; 92%).

Second Step

[1017] Compound (T-36) (63.0 g), toluene (500 mL), IPA (500 mL) and Pd/C (0.55 g) were put in a reaction vessel, and the resulting mixture was stirred for 16 hours under a hydrogen atmosphere. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane=1:1 in a volume ratio) to obtain compound (T-37) (60.1 g; 95%).

Third Step

[1018] Compound (T-37) (60.1 g), formic acid (75.8 g) and toluene (1000 mL) were put in a reaction vessel, and the resulting mixture was stirred at 100 C. for 6 hours. An insoluble matter was filtered off, and then the resulting material was neutralized with a sodium hydrogencarbonate aqueous solution, and an aqueous layer was subjected to extraction with toluene. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-38) (45.0 g; 89%).

Fourth Step

[1019] Compound (T-38) (45.0 g), potassium peroxymonosulfate (OXONE) (108.3 g) and DMF (1000 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 8 hours. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-39) (28.5 g; 60%).

Fifth Step

[1020] Compound (T-39) (28.5 g), sulfuric acid (0.5 mL) and methanol (500 mL) were put in a reaction vessel, and the resulting mixture was stirred at 60 C. for 5 hours. An insoluble matter was filtered off, and then the resulting material was concentrated, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-40) (22.3 g; 75%).

Sixth Step

[1021] Compound (T-41) (18.3 g; 70%) was obtained by using compound (T-40) (22.3 g) as a raw material in a manner similar to the technique in the first step in Synthesis Example 4E.

Seventh Step

[1022] Compound (T-42) (5.9 g; 38%) was obtained by using compound (T-41) (18.3 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 4E.

Eighth Step

[1023] Compound (1-9-7) (2.4 g; 34%) was obtained by using compound (T-42) (5.9 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 4E.

[1024] An NMR analysis value of the resulting compound (1-9-7) was as described below.

[1025] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.11 (s, 1H), 5.81 (s, 1H), 4.31-4.28 (m, 1H), 4.17-4.14 (m, 1H), 3.63-3.58 (m, 1H), 3.54-3.49 (m, 1H), 1.98-1.95 (m, 4H), 1.84-1.69 (m, 9H), 1.41-1.18 (m, 10H), 1.15-1.06 (m, 4H), 1.02-0.80 (m, 13H).

[1026] Physical properties of compound (1-9-7) were as described below.

[1027] Transition temperature: C 33.6 S.sub.A 101 I.

Synthesis Example 11: Synthesis of Compound (1-9-8)

[1028] ##STR00233##

First Step

[1029] Compound (T-43) (2.1 g; 74%) was obtained by using compound (1-9-7) (2.0 g) as a raw material in a manner similar to the technique in the third step in Synthesis Example 5.

Second Step

[1030] Compound (1-9-8) (1.3 g; 72%) was obtained by using compound (T-43) (2.1 g) as a raw material in a manner similar to the technique in the fourth step in Synthesis Example 5E.

[1031] An NMR analysis value of the resulting compound (1-9-8) was as described below.

[1032] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 1H), 6.10 (s, 1H), 5.85 (d, J=1.1 Hz, 1H), 5.57 (s, 1H), 4.33 (d, J=6.5 Hz, 2H), 4.24-4.11 (m, 4H), 2.28 (t, J=6.6 Hz, 1H), 2.09-2.03 (m, 1H), 1.94 (s, 3H), 1.75-1.67 (m, 8H), 1.44-1.39 (m, 2H), 1.32-1.18 (m, 8H), 1.15-1.06 (m, 4H), 1.02-0.79 (m, 13H).

[1033] Physical properties of compound (1-9-8) were as described below.

[1034] Transition temperature: C 71.4 I.

Synthesis Example 12: Synthesis of Compound (1-10-1)

[1035] ##STR00234##

First Step

[1036] Compound (T-20) (2.0 g), compound (T-22) (2.63 g), DMAP (0.78 g) and dichloromethane (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 0 C. A dichloromethane (60 mL) solution of DCC (2.92 g) was slowly added dropwise thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 in a volume ratio) to obtain compound (T-44) (2.83 g; 68%).

Second Step

[1037] Compound (T-44) (2.83 g), pyridinium p-toluenesulfonate (PPTS) (1.09 g), THF (50 mL) and methanol (50 mL) were put in a reaction vessel, and the resulting mixture was stirred at 50 C. for 8 hours. An insoluble matter was filtered off, and then the resulting reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 in a volume ratio) to obtain compound (1-10-1) (1.47 g; 70%).

[1038] An NMR analysis value of the resulting compound (1-10-1) was as described below.

[1039] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.24 (s, 2H), 5.82 (s, 2H), 4.35-4.31 (m, 6H), 4.22-4.19 (m, 2H), 2.36 (s, 2H), 1.97-1.91 (s, 1H), 1.82-1.63 (m, 8H), 1.43-1.18 (m, 7H), 1.15-0.79 (m, 16H).

[1040] Physical properties of compound (1-10-1) were as described below.

[1041] Transition temperature: C 102 I.

Synthesis Example 13: Synthesis of Compound (1-10-2)

[1042] ##STR00235##

First Step

[1043] Compound (T-45) (2.7 g; 64%) was obtained by using compound (T-27) (2.0 g) as a raw material in a manner similar to the technique in the first step in Synthesis Example 12.

Second Step

[1044] Compound (1-10-2) (1.3 g; 65%) was obtained by using compound compound (T-45) (2.7 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 12.

[1045] An NMR analysis value of the resulting compound (1-10-2) was as described below.

[1046] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.20-7.16 (m, 4H), 6.26 (s, 2H), 5.83 (d, J=0.8 Hz, 2H), 4.46 (d, J=6.6 Hz, 4H), 4.28 (d, J=6.3 Hz, 4H), 3.44-3.39 (m, 1H), 2.44 (tt, J=12.2 Hz, J=3.1 Hz, 1H), 2.16-2.13 (m, 2H), 1.87-1.85 (m, 4H), 1.46-1.19 (m, 11H), 1.07-0.99 (m, 2H), 0.89 (t, J=6.8 Hz, 3H).

[1047] Physical properties of compound (1-10-2) were as described below.

[1048] Transition temperature: C 65.8 I.

Synthesis Example 14: Synthesis of Compound (1-10-3)

[1049] ##STR00236##

First Step

[1050] Compound (T-46) (2.5 g; 59%) was obtained by using compound (T-33) (2.0 g) as a raw material in a manner similar to the technique in the first step in Synthesis Example 12.

Second Step

[1051] Compound (1-10-3) (1.1 g; 60%) was obtained by using compound compound (T-46) (2.7 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 12.

[1052] An NMR analysis value of the resulting compound (1-10-3) was as described below.

[1053] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.14-7.10 (m, 4H), 6.27 (s, 2H), 5.87 (d, J=1.1 Hz, 2H), 4.39-4.33 (m, 6H), 4.27-4.20 (m, 2H), 2.57-2.54 (m, 2H), 2.45 (tt, J=12.2 Hz, J=3.1 Hz, 1H), 2.38-2.35 (m, 2H), 2.05-1.91 (m, 5H), 1.63-1.1.26 (m, 11H), 0.88 (t, J=6.8 Hz, 3H).

[1054] Physical properties of compound (1-10-3) were as described below.

[1055] Transition temperature: C 65.6 I.

Synthesis Example 15: Synthesis of Compound (1-10-4)

[1056] ##STR00237##

First Step

[1057] Compound (T-47) (2.7 g; 67%) was obtained by using compound (T-42) (2.0 g) as a raw material in a manner similar to the technique in the first step in Synthesis Example 12.

Second Step

[1058] Compound (1-10-4) (1.3 g; 64%) was obtained by using compound compound (T-47) (2.7 g) as a raw material in a manner similar to the technique in the second step in Synthesis Example 12.

[1059] An NMR analysis value of the resulting compound (1-10-4) was as described below.

[1060] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 6.25 (s, 2H), 5.85 (d, J=1.1 Hz, 2H), 4.33 (d, J=6.3 Hz, 4H), 4.25-4.22 (m, 2H), 4.18-4.14 (m, 2H), 2.30-2.28 (m, 2H), 2.11-2.06 (m, 1H), 1.75-1.67 (m, 8H), 1.44-1.39 (m, 2H), 1.32-0.79 (m, 25H).

[1061] Physical properties of compound (1-10-4) were as described below.

[1062] Transition temperature: C 85.7 S.sub.A 125 I.

14. Example of Compound (1)

[1063] According to the synthesis methods described in Synthesis Examples, compounds (1-3-1) to (1-3-40), compounds (1-4-1) to (1-4-120), compounds (1-5-1) to (1-5-140) and compounds (1-6-1) to (1-6-260) shown below can be prepared.

TABLE-US-00014 No. 1-3-1 [00238] 1-3-2 [00239] 1-3-3 [00240] 1-3-4 [00241] 1-3-5 [00242] 1-3-6 [00243] 1-3-7 [00244] 1-3-8 [00245] 1-3-9 [00246] 1-3-10 [00247] 1-3-11 [00248] 1-3-12 [00249] 1-3-13 [00250] 1-3-14 [00251] 1-3-15 [00252] 1-3-16 [00253] 1-3-17 [00254] 1-3-18 [00255] 1-3-19 [00256] 1-3-20 [00257] 1-3-21 [00258] 1-3-22 [00259] 1-3-23 [00260] 1-3-24 [00261] 1-3-25 [00262] 1-3-26 [00263] 1-3-27 [00264] 1-3-28 [00265] 1-3-29 [00266] 1-3-30 [00267] 1-3-31 [00268] 1-3-32 [00269] 1-3-33 [00270] 1-3-34 [00271] 1-3-35 [00272] 1-3-36 [00273] 1-3-37 [00274] 1-3-38 [00275] 1-3-39 [00276] 1-3-40 [00277] 1-4-1 [00278] 1-4-2 [00279] 1-4-3 [00280] 1-4-4 [00281] 1-4-5 [00282] 1-4-6 [00283] 1-4-7 [00284] 1-4-8 [00285] 1-4-9 [00286] 1-4-10 [00287] 1-4-11 [00288] 1-4-12 [00289] 1-4-13 [00290] 1-4-14 [00291] 1-4-15 [00292] 1-4-16 [00293] 1-4-17 [00294] 1-4-18 [00295] 1-4-19 [00296] 1-4-20 [00297] 1-4-21 [00298] 1-4-22 [00299] 1-4-23 [00300] 1-4-24 [00301] 1-4-25 [00302] 1-4-26 [00303] 1-4-27 [00304] 1-4-28 [00305] 1-4-29 [00306] 1-4-30 [00307] 1-4-31 [00308] 1-4-32 [00309] 1-4-33 [00310] 1-4-34 [00311] 1-4-35 [00312] 1-4-36 [00313] 1-4-37 [00314] 1-4-38 [00315] 1-4-39 [00316] 1-4-40 [00317] 1-4-41 [00318] 1-4-42 [00319] 1-4-43 [00320] 1-4-44 [00321] 1-4-45 [00322] 1-4-46 [00323] 1-4-47 [00324] 1-4-48 [00325] 1-4-49 [00326] 1-4-50 [00327] 1-4-51 [00328] 1-4-52 [00329] 1-4-53 [00330] 1-4-54 [00331] 1-4-55 [00332] 1-4-56 [00333] 1-4-57 [00334] 1-4-58 [00335] 1-4-59 [00336] 1-4-60 [00337] 1-4-61 [00338] 1-4-62 [00339] 1-4-63 [00340] 1-4-64 [00341] 1-4-65 [00342] 1-4-66 [00343] 1-4-67 [00344] 1-4-68 [00345] 1-4-69 [00346] 1-4-70 [00347] 1-4-71 [00348] 1-4-72 [00349] 1-4-73 [00350] 1-4-74 [00351] 1-4-75 [00352] 1-4-76 [00353] 1-4-77 [00354] 1-4-78 [00355] 1-4-79 [00356] 1-4-80 [00357] 1-4-81 [00358] 1-4-82 [00359] 1-4-83 [00360] 1-4-84 [00361] 1-4-85 [00362] 1-4-86 [00363] 1-4-87 [00364] 1-4-88 [00365] 1-4-89 [00366] 1-4-90 [00367] 1-4-91 [00368] 1-4-92 [00369] 1-4-93 [00370] 1-4-94 [00371] 1-4-95 [00372] 1-4-96 [00373] 1-4-97 [00374] 1-4-98 [00375] 1-4-99 [00376] 1-4-100 [00377] 1-4-101 [00378] 1-4-102 [00379] 1-4-103 [00380] 1-4-104 [00381] 1-4-105 [00382] 1-4-106 [00383] 1-4-107 [00384] 1-4-108 [00385] 1-4-109 [00386] 1-4-110 [00387] 1-4-111 [00388] 1-4-112 [00389] 1-4-113 [00390] 1-4-114 [00391] 1-4-115 [00392] 1-4-116 [00393] 1-4-117 [00394] 1-4-118 [00395] 1-4-119 [00396] 1-4-120 [00397] 1-5-1 [00398] 1-5-2 [00399] 1-5-3 [00400] 1-5-4 [00401] 1-5-5 [00402] 1-5-6 [00403] 1-5-7 [00404] 1-5-8 [00405] 1-5-9 [00406] 1-5-10 [00407] 1-5-11 [00408] 1-5-12 [00409] 1-5-13 [00410] 1-5-14 [00411] 1-5-15 [00412] 1-5-16 [00413] 1-5-17 [00414] 1-5-18 [00415] 1-5-19 [00416] 1-5-20 [00417] 1-5-21 [00418] 1-5-22 [00419] 1-5-23 [00420] 1-5-24 [00421] 1-5-25 [00422] 1-5-26 [00423] 1-5-27 [00424] 1-5-28 [00425] 1-5-29 [00426] 1-5-30 [00427] 1-5-31 [00428] 1-5-32 [00429] 1-5-33 [00430] 1-5-34 [00431] 1-5-35 [00432] 1-5-36 [00433] 1-5-37 [00434] 1-5-38 [00435] 1-5-39 [00436] 1-5-40 [00437] 1-5-41 [00438] 1-5-42 [00439] 1-5-43 [00440] 1-5-44 [00441] 1-5-45 [00442] 1-5-46 [00443] 1-5-47 [00444] 1-5-48 [00445] 1-5-49 [00446] 1-5-50 [00447] 1-5-51 [00448] 1-5-52 [00449] 1-5-53 [00450] 1-5-54 [00451] 1-5-55 [00452] 1-5-56 [00453] 1-5-57 [00454] 1-5-58 [00455] 1-5-59 [00456] 1-5-60 [00457] 1-5-61 [00458] 1-5-62 [00459] 1-5-63 [00460] 1-5-64 [00461] 1-5-65 [00462] 1-5-66 [00463] 1-5-67 [00464] 1-5-68 [00465] 1-5-69 [00466] 1-5-70 [00467] 1-5-71 [00468] 1-5-72 [00469] 1-5-73 [00470] 1-5-74 [00471] 1-5-75 [00472] 1-5-76 [00473] 1-5-77 [00474] 1-5-78 [00475] 1-5-79 [00476] 1-5-80 [00477] 1-5-81 [00478] 1-5-82 [00479] 1-5-83 [00480] 1-5-84 [00481] 1-5-85 [00482] 1-5-86 [00483] 1-5-87 [00484] 1-5-88 [00485] 1-5-89 [00486] 1-5-90 [00487] 1-5-91 [00488] 1-5-92 [00489] 1-5-93 [00490] 1-5-94 [00491] 1-5-95 [00492] 1-5-96 [00493] 1-5-97 [00494] 1-5-98 [00495] 1-5-99 [00496] 1-5-100 [00497] 1-5-101 [00498] 1-5-102 [00499] 1-5-103 [00500] 1-5-104 [00501] 1-5-105 [00502] 1-5-106 [00503] 1-5-107 [00504] 1-5-108 [00505] 1-5-109 [00506] 1-5-110 [00507] 1-5-111 [00508] 1-5-112 [00509] 1-5-113 [00510] 1-5-114 [00511] 1-5-115 [00512] 1-5-116 [00513] 1-5-117 [00514] 1-5-118 [00515] 1-5-119 [00516] 1-5-120 [00517] 1-5-121 [00518] 1-5-122 [00519] 1-5-123 [00520] 1-5-124 [00521] 1-5-125 [00522] 1-5-126 [00523] 1-5-127 [00524] 1-5-128 [00525] 1-5-129 [00526] 1-5-130 [00527] 1-5-131 [00528] 1-5-132 [00529] 1-5-133 [00530] 1-5-134 [00531] 1-5-135 [00532] 1-5-136 [00533] 1-5-137 [00534] 1-5-138 [00535] 1-5-139 [00536] 1-5-140 [00537] 1-6-1 [00538] 1-6-2 [00539] 1-6-3 [00540] 1-6-4 [00541] 1-6-5 [00542] 1-6-6 [00543] 1-6-7 [00544] 1-6-8 [00545] 1-6-9 [00546] 1-6-10 [00547] 1-6-11 [00548] 1-6-12 [00549] 1-6-13 [00550] 1-6-14 [00551] 1-6-15 [00552] 1-6-16 [00553] 1-6-17 [00554] 1-6-18 [00555] 1-6-19 [00556] 1-6-20 [00557] 1-6-21 [00558] 1-6-22 [00559] 1-6-23 [00560] 1-6-24 [00561] 1-6-25 [00562] 1-6-26 [00563] 1-6-27 [00564] 1-6-28 [00565] 1-6-29 [00566] 1-6-30 [00567] 1-6-31 [00568] 1-6-32 [00569] 1-6-33 [00570] 1-6-34 [00571] 1-6-35 [00572] 1-6-36 [00573] 1-6-37 [00574] 1-6-38 [00575] 1-6-39 [00576] 1-6-40 [00577] 1-6-41 [00578] 1-6-42 [00579] 1-6-43 [00580] 1-6-44 [00581] 1-6-45 [00582] 1-6-46 [00583] 1-6-47 [00584] 1-6-48 [00585] 1-6-49 [00586] 1-6-50 [00587] 1-6-51 [00588] 1-6-52 [00589] 1-6-53 [00590] 1-6-54 [00591] 1-6-55 [00592] 1-6-56 [00593] 1-6-57 [00594] 1-6-58 [00595] 1-6-59 [00596] 1-6-60 [00597] 1-6-61 [00598] 1-6-62 [00599] 1-6-63 [00600] 1-6-64 [00601] 1-6-65 [00602] 1-6-66 [00603] 1-6-67 [00604] 1-6-68 [00605] 1-6-69 [00606] 1-6-70 [00607] 1-6-71 [00608] 1-6-72 [00609] 1-6-73 [00610] 1-6-74 [00611] 1-6-75 [00612] 1-6-76 [00613] 1-6-77 [00614] 1-6-78 [00615] 1-6-79 [00616] 1-6-80 [00617] 1-6-81 [00618] 1-6-82 [00619] 1-6-83 [00620] 1-6-84 [00621] 1-6-85 [00622] 1-6-86 [00623] 1-6-87 [00624] 1-6-88 [00625] 1-6-89 [00626] 1-6-90 [00627] 1-6-91 [00628] 1-6-92 [00629] 1-6-93 [00630] 1-6-94 [00631] 1-6-95 [00632] 1-6-96 [00633] 1-6-97 [00634] 1-6-98 [00635] 1-6-99 [00636] 1-6-100 [00637] 1-6-101 [00638] 1-6-102 [00639] 1-6-103 [00640] 1-6-104 [00641] 1-6-105 [00642] 1-6-106 [00643] 1-6-107 [00644] 1-6-108 [00645] 1-6-109 [00646] 1-6-110 [00647] 1-6-111 [00648] 1-6-112 [00649] 1-6-113 [00650] 1a-6-114 [00651] 1-6-115 [00652] 1-6-116 [00653] 1-6-117 [00654] 1-6-118 [00655] 1-6-119 [00656] 1a-6-120 [00657] 1-6-121 [00658] 1-6-122 [00659] 1-6-123 [00660] 1-6-124 [00661] 1-6-125 [00662] 1-6-126 [00663] 1-6-127 [00664] 1-6-128 [00665] 1-6-129 [00666] 1-6-130 [00667] 1-6-131 [00668] 1-6-132 [00669] 1-6-133 [00670] 1-6-134 [00671] 1-6-135 [00672] 1-6-136 [00673] 1-6-137 [00674] 1-6-138 [00675] 1-6-139 [00676] 1-6-140 [00677] 1-6-141 [00678] 1-6-142 [00679] 1-6-143 [00680] 1-6-144 [00681] 1-6-145 [00682] 1-6-146 [00683] 1-6-147 [00684] 1-6-148 [00685] 1-6-149 [00686] 1-6-150 [00687] 1-6-151 [00688] 1-6-152 [00689] 1-6-153 [00690] 1-6-154 [00691] 1-6-155 [00692] 1-6-156 [00693] 1-6-157 [00694] 1-6-158 [00695] 1-6-159 [00696] 1-6-160 [00697] 1-6-161 [00698] 1-6-162 [00699] 1-6-163 [00700] 1-6-164 [00701] 1-6-165 [00702] 1-6-166 [00703] 1-6-167 [00704] 1-6-168 [00705] 1-6-169 [00706] 1-6-170 [00707] 1-6-171 [00708] 1-6-172 [00709] 1-6-173 [00710] 1-6-174 [00711] 1-6-175 [00712] 1-6-176 [00713] 1-6-177 [00714] 1-6-178 [00715] 1-6-179 [00716] 1-6-180 [00717] 1-6-181 [00718] 1-6-182 [00719] 1-6-183 [00720] 1-6-184 [00721] 1-6-185 [00722] 1-6-186 [00723] 1-6-187 [00724] 1-6-188 [00725] 1-6-189 [00726] 1-6-190 [00727] 1-6-191 [00728] 1-6-192 [00729] 1-6-193 [00730] 1-6-194 [00731] 1-6-195 [00732] 1-6-196 [00733] 1-6-197 [00734] 1-6-198 [00735] 1-6-199 [00736] 1-6-200 [00737] 1-6-201 [00738] 1-6-202 [00739] 1-6-203 [00740] 1-6-204 [00741] 1-6-205 [00742] 1-6-206 [00743] 1-6-207 [00744] 1-6-208 [00745] 1-6-209 [00746] 1-6-210 [00747] 1-6-211 [00748] 1-6-212 [00749] 1-6-213 [00750] 1-6-214 [00751] 1-6-215 [00752] 1-6-216 [00753] 1-6-217 [00754] 1-6-218 [00755] 1-6-219 [00756] 1-6-220 [00757] 1-6-221 [00758] 1-6-222 [00759] 1-6-223 [00760] 1-6-224 [00761] 1-6-225 [00762] 1-6-226 [00763] 1-6-227 [00764] 1-6-228 [00765] 1-6-229 [00766] 1-6-230 [00767] 1-6-231 [00768] 1-6-232 [00769] 1-6-233 [00770] 1-6-234 [00771] 1-6-235 [00772] 1-6-236 [00773] 1-6-237 [00774] 1-6-238 [00775] 1-6-239 [00776] 1-6-240 [00777] 1-6-241 [00778] 1-6-242 [00779] 1-6-243 [00780] 1-6-244 [00781] 1-6-245 [00782] 1-6-246 [00783] 1-6-247 [00784] 1-6-248 [00785] 1-6-249 [00786] 1-6-250 [00787] 1-6-251 [00788] 1-6-252 [00789] 1-6-253 [00790] 1-6-254 [00791] 1-6-255 [00792] 1-6-256 [00793] 1-6-257 [00794] 1-6-258 [00795] 1-6-259 [00796] 1-6-260 [00797]

15. Example of Compound (1)

[1064] According to the synthesis methods described in Synthesis Examples, compounds (1-3-1) to (1-3-82), compounds (1-4-1) to (1-4-244), compounds (1-5-1) to (1-5-296) and compounds (1-6-1) to (1-6-258) shown below can be prepared.

TABLE-US-00015 No. 1-3-1 [00798] 1-3-2 [00799] 1-3-3 [00800] 1-3-4 [00801] 1-3-5 [00802] 1-3-6 [00803] 1-3-7 [00804] 1-3-8 [00805] 1-3-9 [00806] 1-3-10 [00807] 1-3-11 [00808] 1-3-12 [00809] 1-3-13 [00810] 1-3-14 [00811] 1-3-15 [00812] 1-3-16 [00813] 1-3-17 [00814] 1-3-18 [00815] 1-3-19 [00816] 1-3-20 [00817] 1-3-21 [00818] 1-3-22 [00819] 1-3-23 [00820] 1-3-24 [00821] 1-3-25 [00822] 1-3-26 [00823] 1-3-27 [00824] 1-3-28 [00825] 1-3-29 [00826] 1-3-30 [00827] 1-3-31 [00828] 1-3-32 [00829] 1-3-33 [00830] 1-3-34 [00831] 1-3-35 [00832] 1-3-36 [00833] 1-3-37 [00834] 1-3-38 [00835] 1-3-39 [00836] 1-3-40 [00837] 1-3-41 [00838] 1-3-42 [00839] 1-3-43 [00840] 1-3-44 [00841] 1-3-45 [00842] 1-3-46 [00843] 1-3-47 [00844] 1-3-48 [00845] 1-3-49 [00846] 1-3-50 [00847] 1-3-51 [00848] 1-3-52 [00849] 1-3-53 [00850] 1-3-54 [00851] 1-3-55 [00852] 1-3-56 [00853] 1-3-57 [00854] 1-3-58 [00855] 1-3-59 [00856] 1-3-60 [00857] 1-3-61 [00858] 1-3-62 [00859] 1-3-63 [00860] 1-3-64 [00861] 1-3-65 [00862] 1-3-66 [00863] 1-3-67 [00864] 1-3-68 [00865] 1-3-69 [00866] 1-3-70 [00867] 1-3-71 [00868] 1-3-72 [00869] 1-3-73 [00870] 1-3-74 [00871] 1-3-75 [00872] 1-3-76 [00873] 1-3-77 [00874] 1-3-78 [00875] 1-3-79 [00876] 1-3-80 [00877] 1-3-81 [00878] 1-3-82 [00879] 1-4-1 [00880] 1-4-2 [00881] 1-4-3 [00882] 1-4-4 [00883] 1-4-5 [00884] 1-4-6 [00885] 1-4-7 [00886] 1-4-8 [00887] 1-4-9 [00888] 1-4-10 [00889] 1-4-11 [00890] 1-4-12 [00891] 1-4-13 [00892] 1-4-14 [00893] 1-4-15 [00894] 1-4-16 [00895] 1-4-17 [00896] 1-4-18 [00897] 1-4-19 [00898] 1-4-20 [00899] 1-4-21 [00900] 1-4-22 [00901] 1-4-23 [00902] 1-4-24 [00903] 1-4-25 [00904] 1-4-26 [00905] 1-4-27 [00906] 1-4-28 [00907] 1-4-29 [00908] 1-4-30 [00909] 1-4-31 [00910] 1-4-32 [00911] 1-4-33 [00912] 1-4-34 [00913] 1-4-35 [00914] 1-4-36 [00915] 1-4-37 [00916] 1-4-38 [00917] 1-4-39 [00918] 1-4-40 [00919] 1-4-41 [00920] 1-4-42 [00921] 1-4-43 [00922] 1-4-44 [00923] 1-4-45 [00924] 1-4-46 [00925] 1-4-47 [00926] 1-4-48 [00927] 1-4-49 [00928] 1-4-50 [00929] 1-4-51 [00930] 1-4-52 [00931] 1-4-53 [00932] 1-4-54 [00933] 1-4-55 [00934] 1-4-56 [00935] 1-4-57 [00936] 1-4-58 [00937] 1-4-59 [00938] 1-4-60 [00939] 1-4-61 [00940] 1-4-62 [00941] 1-4-63 [00942] 1-4-64 [00943] 1-4-65 [00944] 1-4-66 [00945] 1-4-67 [00946] 1-4-68 [00947] 1-4-69 [00948] 1-4-70 [00949] 1-4-71 [00950] 1-4-72 [00951] 1-4-73 [00952] 1-4-74 [00953] 1-4-75 [00954] 1-4-76 [00955] 1-4-77 [00956] 1-4-78 [00957] 1-4-79 [00958] 1-4-80 [00959] 1-4-81 [00960] 1-4-82 [00961] 1-4-83 [00962] 1-4-84 [00963] 1-4-85 [00964] 1-4-86 [00965] 1-4-87 [00966] 1-4-88 [00967] 1-4-89 [00968] 1-4-90 [00969] 1-4-91 [00970] 1-4-92 [00971] 1-4-93 [00972] 1-4-94 [00973] 1-4-95 [00974] 1-4-96 [00975] 1-4-97 [00976] 1-4-98 [00977] 1-4-99 [00978] 1-4-100 [00979] 1-4-101 [00980] 1-4-102 [00981] 1-4-103 [00982] 1-4-104 [00983] 1-4-105 [00984] 1-4-106 [00985] 1-4-107 [00986] 1-4-108 [00987] 1-4-109 [00988] 1-4-110 [00989] 1-4-111 [00990] 1-4-112 [00991] 1-4-113 [00992] 1-4-114 [00993] 1-4-115 [00994] 1-4-116 [00995] 1-4-117 [00996] 1-4-118 [00997] 1-4-119 [00998] 1-4-120 [00999] 1-4-121 [01000] 1-4-122 [01001] 1-4-123 [01002] 1-4-124 [01003] 1-4-125 [01004] 1-4-126 [01005] 1-4-127 [01006] 1-4-128 [01007] 1-4-129 [01008] 1-4-130 [01009] 1-4-131 [01010] 1-4-132 [01011] 1-4-133 [01012] 1-4-134 [01013] 1-4-135 [01014] 1-4-136 [01015] 1-4-137 [01016] 1-4-138 [01017] 1-4-139 [01018] 1-4-140 [01019] 1-4-141 [01020] 1-4-142 [01021] 1-4-143 [01022] 1-4-144 [01023] 1-4-145 [01024] 1-4-146 [01025] 1-4-147 [01026] 1-4-148 [01027] 1-4-149 [01028] 1-4-150 [01029] 1-4-151 [01030] 1-4-152 [01031] 1-4-153 [01032] 1-4-154 [01033] 1-4-155 [01034] 1-4-156 [01035] 1-4-157 [01036] 1-4-158 [01037] 1-4-159 [01038] 1-4-160 [01039] 1-4-161 [01040] 1-4-162 [01041] 1-4-163 [01042] 1-4-164 [01043] 1-4-165 [01044] 1-4-166 [01045] 1-4-167 [01046] 1-4-168 [01047] 1-4-169 [01048] 1-4-170 [01049] 1-4-171 [01050] 1-4-172 [01051] 1-4-173 [01052] 1-4-174 [01053] 1-4-175 [01054] 1-4-176 [01055] 1-4-177 [01056] 1-4-178 [01057] 1-4-179 [01058] 1-4-180 [01059] 1-4-181 [01060] 1-4-182 [01061] 1-4-183 [01062] 1-4-184 [01063] 1-4-185 [01064] 1-4-186 [01065] 1-4-187 [01066] 1-4-188 [01067] 1-4-189 [01068] 1-4-190 [01069] 1-4-191 [01070] 1-4-192 [01071] 1-4-193 [01072] 1-4-194 [01073] 1-4-195 [01074] 1-4-196 [01075] 1-4-197 [01076] 1-4-198 [01077] 1-4-199 [01078] 1-4-200 [01079] 1-4-201 [01080] 1-4-202 [01081] 1-4-203 [01082] 1-4-204 [01083] 1-4-205 [01084] 1-4-206 [01085] 1-4-207 [01086] 1-4-208 [01087] 1-4-209 [01088] 1-4-210 [01089] 1-4-211 [01090] 1-4-212 [01091] 1-4-213 [01092] 1-4-214 [01093] 1-4-215 [01094] 1-4-216 [01095] 1-4-217 [01096] 1-4-218 [01097] 1-4-219 [01098] 1-4-220 [01099] 1-4-221 [01100] 1-4-222 [01101] 1-4-223 [01102] 1-4-224 [01103] 1-4-225 [01104] 1-4-226 [01105] 1-4-227 [01106] 1-4-228 [01107] 1-4-229 [01108] 1-4-230 [01109] 1-4-231 [01110] 1-4-232 [01111] 1-4-233 [01112] 1-4-234 [01113] 1-4-235 [01114] 1-4-236 [01115] 1-4-237 [01116] 1-4-238 [01117] 1-4-239 [01118] 1-4-240 [01119] 1-4-241 [01120] 1-4-242 [01121] 1-4-243 [01122] 1-4-244 [01123] 1-5-1 [01124] 1-5-2 [01125] 1-5-3 [01126] 1-5-4 [01127] 1-5-5 [01128] 1-5-6 [01129] 1-5-7 [01130] 1-5-8 [01131] 1-5-9 [01132] 1-5-10 [01133] 1-5-11 [01134] 1-5-12 [01135] 1-5-13 [01136] 1-5-14 [01137] 1-5-15 [01138] 1-5-16 [01139] 1-5-17 [01140] 1-5-18 [01141] 1-5-19 [01142] 1-5-20 [01143] 1-5-21 [01144] 1-5-22 [01145] 1-5-23 [01146] 1-5-24 [01147] 1-5-25 [01148] 1-5-26 [01149] 1-5-27 [01150] 1-5-28 [01151] 1-5-29 [01152] 1-5-30 [01153] 1-5-31 [01154] 1-5-32 [01155] 1-5-33 [01156] 1-5-34 [01157] 1-5-35 [01158] 1-5-36 [01159] 1-5-37 [01160] 1-5-38 [01161] 1-5-39 [01162] 1-5-40 [01163] 1-5-41 [01164] 1-5-42 [01165] 1-5-43 [01166] 1-5-44 [01167] 1-5-45 [01168] 1-5-46 [01169] 1-5-47 [01170] 1-5-48 [01171] 1-5-49 [01172] 1-5-50 [01173] 1-5-51 [01174] 1-5-52 [01175] 1-5-53 [01176] 1-5-54 [01177] 1-5-55 [01178] 1-5-56 [01179] 1-5-57 [01180] 1-5-58 [01181] 1-5-59 [01182] 1-5-60 [01183] 1-5-61 [01184] 1-5-62 [01185] 1-5-63 [01186] 1-5-64 [01187] 1-5-65 [01188] 1-5-66 [01189] 1-5-67 [01190] 1-5-68 [01191] 1-5-69 [01192] 1-5-70 [01193] 1-5-71 [01194] 1-5-72 [01195] 1-5-73 [01196] 1-5-74 [01197] 1-5-75 [01198] 1-5-76 [01199] 1-5-77 [01200] 1-5-78 [01201] 1-5-79 [01202] 1-5-80 [01203] 1-5-81 [01204] 1-5-82 [01205] 1-5-83 [01206] 1-5-84 [01207] 1-5-85 [01208] 1-5-86 [01209] 1-5-87 [01210] 1-5-88 [01211] 1-5-89 [01212] 1-5-90 [01213] 1-5-91 [01214] 1-5-92 [01215] 1-5-93 [01216] 1-5-94 [01217] 1-5-95 [01218] 1-5-96 [01219] 1-5-97 [01220] 1-5-98 [01221] 1-5-99 [01222] 1-5-100 [01223] 1-5-101 [01224] 1-5-102 [01225] 1-5-103 [01226] 1-5-104 [01227] 1-5-105 [01228] 1-5-106 [01229] 1-5-107 [01230] 1-5-108 [01231] 1-5-109 [01232] 1-5-110 [01233] 1-5-111 [01234] 1-5-112 [01235] 1-5-113 [01236] 1-5-114 [01237] 1-5-115 [01238] 1-5-116 [01239] 1-5-117 [01240] 1-5-118 [01241] 1-5-119 [01242] 1-5-120 [01243] 1-5-121 [01244] 1-5-122 [01245] 1-5-123 [01246] 1-5-124 [01247] 1-5-125 [01248] 1-5-126 [01249] 1-5-127 [01250] 1-5-128 [01251] 1-5-129 [01252] 1-5-130 [01253] 1-5-131 [01254] 1-5-132 [01255] 1-5-133 [01256] 1-5-134 [01257] 1-5-135 [01258] 1-5-136 [01259] 1-5-137 [01260] 1-5-138 [01261] 1-5-139 [01262] 1-5-140 [01263] 1-5-141 [01264] 1-5-142 [01265] 1-5-143 [01266] 1-5-144 [01267] 1-5-145 [01268] 1-5-146 [01269] 1-5-147 [01270] 1-5-148 [01271] 1-5-149 [01272] 1-5-150 [01273] 1-5-151 [01274] 1-5-152 [01275] 1-5-153 [01276] 1-5-154 [01277] 1-5-155 [01278] 1-5-156 [01279] 1-5-157 [01280] 1-5-158 [01281] 1-5-159 [01282] 1-5-160 [01283] 1-5-161 [01284] 1-5-162 [01285] 1-5-163 [01286] 1-5-164 [01287] 1-5-165 [01288] 1-5-166 [01289] 1-5-167 [01290] 1-5-168 [01291] 1-5-169 [01292] 1-5-170 [01293] 1-5-171 [01294] 1-5-172 [01295] 1-5-173 [01296] 1-5-174 [01297] 1-5-175 [01298] 1-5-176 [01299] 1-5-177 [01300] 1-5-178 [01301] 1-5-179 [01302] 1-5-180 [01303] 1-5-181 [01304] 1-5-182 [01305] 1-5-183 [01306] 1-5-184 [01307] 1-5-185 [01308] 1-5-186 [01309] 1-5-187 [01310] 1-5-188 [01311] 1-5-189 [01312] 1-5-190 [01313] 1-5-191 [01314] 1-5-192 [01315] 1-5-193 [01316] 1-5-194 [01317] 1-5-195 [01318] 1-5-196 [01319] 1-5-197 [01320] 1-5-198 [01321] 1-5-199 [01322] 1-5-200 [01323] 1-5-201 [01324] 1-5-202 [01325] 1-5-203 [01326] 1-5-204 [01327] 1-5-205 [01328] 1-5-206 [01329] 1-5-207 [01330] 1-5-208 [01331] 1-5-209 [01332] 1-5-210 [01333] 1-5-211 [01334] 1-5-212 [01335] 1-5-213 [01336] 1-5-214 [01337] 1-5-215 [01338] 1-5-216 [01339] 1-5-217 [01340] 1-5-218 [01341] 1-5-219 [01342] 1-5-220 [01343] 1-5-221 [01344] 1-5-222 [01345] 1-5-223 [01346] 1-5-224 [01347] 1-5-225 [01348] 1-5-226 [01349] 1-5-227 [01350] 1-5-228 [01351] 1-5-229 [01352] 1-5-230 [01353] 1-5-231 [01354] 1-5-232 [01355] 1-5-233 [01356] 1-5-234 [01357] 1-5-235 [01358] 1-5-236 [01359] 1-5-237 [01360] 1-5-238 [01361] 1-5-239 [01362] 1-5-240 [01363] 1-5-241 [01364] 1-5-242 [01365] 1-5-243 [01366] 1-5-244 [01367] 1-5-245 [01368] 1-5-246 [01369] 1-5-247 [01370] 1-5-248 [01371] 1-5-249 [01372] 1-5-250 [01373] 1-5-251 [01374] 1-5-252 [01375] 1-5-253 [01376] 1-5-254 [01377] 1-5-255 [01378] 1-5-256 [01379] 1-5-257 [01380] 1-5-258 [01381] 1-5-259 [01382] 1-5-260 [01383] 1-5-261 [01384] 1-5-262 [01385] 1-5-263 [01386] 1-5-264 [01387] 1-5-265 [01388] 1-5-266 [01389] 1-5-267 [01390] 1-5-268 [01391] 1-5-269 [01392] 1-5-270 [01393] 1-5-271 [01394] 1-5-272 [01395] 1-5-273 [01396] 1-5-274 [01397] 1-5-275 [01398] 1-5-276 [01399] 1-5-277 [01400] 1-5-278 [01401] 1-5-279 [01402] 1-5-280 [01403] 1-5-281 [01404] 1-5-282 [01405] 1-5-283 [01406] 1-5-284 [01407] 1-5-285 [01408] 1-5-286 [01409] 1-5-287 [01410] 1-5-288 [01411] 1-5-289 [01412] 1-5-290 [01413] 1-5-291 [01414] 1-5-292 [01415] 1-5-293 [01416] 1-5-294 [01417] 1-5-295 [01418] 1-5-296 [01419] 1-6-1 [01420] 1-6-2 [01421] 1-6-3 [01422] 1-6-4 [01423] 1-6-5 [01424] 1-6-6 [01425] 1-6-7 [01426] 1-6-8 [01427] 1-6-9 [01428] 1-6-10 [01429] 1-6-11 [01430] 1-6-12 [01431] 1-6-13 [01432] 1-6-14 [01433] 1-6-15 [01434] 1-6-16 [01435] 1-6-17 [01436] 1-6-18 [01437] 1-6-19 [01438] 1-6-20 [01439] 1-6-21 [01440] 1-6-22 [01441] 1-6-23 [01442] 1-6-24 [01443] 1-6-25 [01444] 1-6-26 [01445] 1-6-27 [01446] 1-6-28 [01447] 1-6-29 [01448] 1-6-30 [01449] 1-6-31 [01450] 1-6-32 [01451] 1-6-33 [01452] 1-6-34 [01453] 1-6-35 [01454] 1-6-36 [01455] 1-6-37 [01456] 1-6-38 [01457] 1-6-39 [01458] 1-6-40 [01459] 1-6-41 [01460] 1-6-42 [01461] 1-6-43 [01462] 1-6-44 [01463] 1-6-45 [01464] 1-6-46 [01465] 1-6-47 [01466] 1-6-48 [01467] 1-6-49 [01468] 1-6-50 [01469] 1-6-51 [01470] 1-6-52 [01471] 1-6-53 [01472] 1-6-54 [01473] 1-6-55 [01474] 1-6-56 [01475] 1-6-57 [01476] 1-6-58 [01477] 1-6-59 [01478] 1-6-60 [01479] 1-6-61 [01480] 1-6-62 [01481] 1-6-63 [01482] 1-6-64 [01483] 1-6-65 [01484] 1-6-66 [01485] 1-6-67 [01486] 1-6-68 [01487] 1-6-69 [01488] 1-6-70 [01489] 1-6-71 [01490] 1-6-72 [01491] 1-6-73 [01492] 1-6-74 [01493] 1-6-75 [01494] 1-6-76 [01495] 1-6-77 [01496] 1-6-78 [01497] 1-6-79 [01498] 1-6-80 [01499] 1-6-81 [01500] 1-6-82 [01501] 1-6-83 [01502] 1-6-84 [01503] 1-6-85 [01504] 1-6-86 [01505] 1-6-87 [01506] 1-6-88 [01507] 1-6-89 [01508] 1-6-90 [01509] 1-6-91 [01510] 1-6-92 [01511] 1-6-93 [01512] 1-6-94 [01513] 1-6-95 [01514] 1-6-96 [01515] 1-6-97 [01516] 1-6-98 [01517] 1-6-99 [01518] 1-6-100 [01519] 1-6-101 [01520] 1-6-102 [01521] 1-6-103 [01522] 1-6-104 [01523] 1-6-105 [01524] 1-6-106 [01525] 1-6-107 [01526] 1-6-108 [01527] 1-6-109 [01528] 1-6-110 [01529] 1-6-111 [01530] 1-6-112 [01531] 1-6-113 [01532] 1-6-114 [01533] 1-6-115 [01534] 1-6-116 [01535] 1-6-117 [01536] 1-6-118 [01537] 1-6-119 [01538] 1-6-120 [01539] 1-6-121 [01540] 1-6-122 [01541] 1-6-123 [01542] 1-6-124 [01543] 1-6-125 [01544] 1-6-126 [01545] 1-6-127 [01546] 1-6-128 [01547] 1-6-129 [01548] 1-6-130 [01549] 1-6-131 [01550] 1-6-132 [01551] 1-6-133 [01552] 1-6-134 [01553] 1-6-135 [01554] 1-6-136 [01555] 1-6-137 [01556] 1-6-138 [01557] 1-6-139 [01558] 1-6-140 [01559] 1-6-141 [01560] 1-6-142 [01561] 1-6-143 [01562] 1-6-144 [01563] 1-6-145 [01564] 1-6-146 [01565] 1-6-147 [01566] 1-6-148 [01567] 1-6-149 [01568] 1-6-150 [01569] 1-6-151 [01570] 1-6-152 [01571] 1-6-153 [01572] 1-6-154 [01573] 1-6-155 [01574] 1-6-156 [01575] 1-6-157 [01576] 1-6-158 [01577] 1-6-159 [01578] 1-6-160 [01579] 1-6-161 [01580] 1-6-162 [01581] 1-6-163 [01582] 1-6-164 [01583] 1-6-165 [01584] 1-6-166 [01585] 1-6-167 [01586] 1-6-168 [01587] 1-6-169 [01588] 1-6-170 [01589] 1-6-171 [01590] 1-6-172 [01591] 1-6-173 [01592] 1-6-174 [01593] 1-6-175 [01594] 1-6-176 [01595] 1-6-177 [01596] 1-6-178 [01597] 1-6-179 [01598] 1-6-180 [01599] 1-6-181 [01600] 1-6-182 [01601] 1-6-183 [01602] 1-6-184 [01603] 1-6-185 [01604] 1-6-186 [01605] 1-6-187 [01606] 1-6-188 [01607] 1-6-189 [01608] 1-6-190 [01609] 1-6-191 [01610] 1-6-192 [01611] 1-6-193 [01612] 1-6-194 [01613] 1-6-195 [01614] 1-6-196 [01615] 1-6-197 [01616] 1-6-198 [01617] 1-6-199 [01618] 1-6-200 [01619] 1-6-201 [01620] 1-6-202 [01621] 1-6-203 [01622] 1-6-204 [01623] 1-6-205 [01624] 1-6-206 [01625] 1-6-207 [01626] 1-6-208 [01627] 1-6-209 [01628] 1-6-210 [01629] 1-6-211 [01630] 1-6-212 [01631] 1-6-213 [01632] 1-6-214 [01633] 1-6-215 [01634] 1-6-216 [01635] 1-6-217 [01636] 1-6-218 [01637] 1-6-219 [01638] 1-6-220 [01639] 1-6-221 [01640] 1-6-222 [01641] 1-6-223 [01642] 1-6-224 [01643] 1-6-225 [01644] 1-6-226 [01645] 1-6-227 [01646] 1-6-228 [01647] 1-6-229 [01648] 1-6-230 [01649] 1-6-231 [01650] 1-6-232 [01651] 1-6-233 [01652] 1-6-234 [01653] 1-6-235 [01654] 1-6-236 [01655] 1-6-237 [01656] 1-6-238 [01657] 1-6-239 [01658] 1-6-240 [01659] 1-6-241 [01660] 1-6-242 [01661] 1-6-243 [01662] 1-6-244 [01663] 1-6-245 [01664] 1-6-246 [01665] 1-6-247 [01666] 1-6-248 [01667] 1-6-249 [01668] 1-6-250 [01669] 1-6-251 [01670] 1-6-252 [01671] 1-6-253 [01672] 1-6-254 [01673] 1-6-255 [01674] 1-6-256 [01675] 1-6-257 [01676] 1-6-258 [01677]

16. Example of Compound (1)

[1065] According to the synthesis methods described in Synthesis Examples, compounds (1-1-1) to (1-1-80), compounds (1-2-1) to (1-2-225), compounds (1-3-1) to (1-3-100), compounds (1-4-1) to (1-4-70), compounds (1-5-1) to (1-5-75) and compounds (1-6-1) to (1-6-60) shown below can be prepared.

TABLE-US-00016 No. 1-1-1 [01678] 1-1-2 [01679] 1-1-3 [01680] 1-1-4 [01681] 1-1-5 [01682] 1-1-6 [01683] 1-1-7 [01684] 1-1-8 [01685] 1-1-9 [01686] 1-1-10 [01687] 1-1-11 [01688] 1-1-12 [01689] 1-1-13 [01690] 1-1-14 [01691] 1-1-15 [01692] 1-1-16 [01693] 1-1-17 [01694] 1-1-18 [01695] 1-1-19 [01696] 1-1-20 [01697] 1-1-21 [01698] 1-1-22 [01699] 1-1-23 [01700] 1-1-24 [01701] 1-1-25 [01702] 1-1-26 [01703] 1-1-27 [01704] 1-1-28 [01705] 1-1-29 [01706] 1-1-30 [01707] 1-1-31 [01708] 1-1-32 [01709] 1-1-33 [01710] 1-1-34 [01711] 1-1-35 [01712] 1-1-36 [01713] 1-1-37 [01714] 1-1-38 [01715] 1-1-39 [01716] 1-1-40 [01717] 1-1-41 [01718] 1-1-42 [01719] 1-1-43 [01720] 1-1-44 [01721] 1-1-45 [01722] 1-1-46 [01723] 1-1-47 [01724] 1-1-48 [01725] 1-1-49 [01726] 1-1-50 [01727] 1-1-51 [01728] 1-1-52 [01729] 1-1-53 [01730] 1-1-54 [01731] 1-1-55 [01732] 1-1-56 [01733] 1-1-57 [01734] 1-1-58 [01735] 1-1-59 [01736] 1-1-60 [01737] 1-1-61 [01738] 1-1-62 [01739] 1-1-63 [01740] 1-1-64 [01741] 1-1-65 [01742] 1-1-66 [01743] 1-1-67 [01744] 1-1-68 [01745] 1-1-69 [01746] 1-1-70 [01747] 1-1-71 [01748] 1-1-72 [01749] 1-1-73 [01750] 1-1-74 [01751] 1-1-75 [01752] 1-1-76 [01753] 1-1-77 [01754] 1-1-78 [01755] 1-1-79 [01756] 1-1-80 [01757] 1-2-1 [01758] 1-2-2 [01759] 1-2-3 [01760] 1-2-4 [01761] 1-2-5 [01762] 1-2-6 [01763] 1-2-7 [01764] 1-2-8 [01765] 1-2-9 [01766] 1-2-10 [01767] 1-2-11 [01768] 1-2-12 [01769] 1-2-13 [01770] 1-2-14 [01771] 1-2-15 [01772] 1-2-16 [01773] 1-2-17 [01774] 1-2-18 [01775] 1-2-19 [01776] 1-2-20 [01777] 1-2-21 [01778] 1-2-22 [01779] 1-2-23 [01780] 1-2-24 [01781] 1-2-25 [01782] 1-2-26 [01783] 1-2-27 [01784] 1-2-28 [01785] 1-2-29 [01786] 1-2-30 [01787] 1-2-31 [01788] 1-2-32 [01789] 1-2-33 [01790] 1-2-34 [01791] 1-2-35 [01792] 1-2-36 [01793] 1-2-37 [01794] 1-2-38 [01795] 1-2-39 [01796] 1-2-40 [01797] 1-2-41 [01798] 1-2-42 [01799] 1-2-43 [01800] 1-2-44 [01801] 1-2-45 [01802] 1-2-46 [01803] 1-2-47 [01804] 1-2-48 [01805] 1-2-49 [01806] 1-2-50 [01807] 1-2-51 [01808] 1-2-52 [01809] 1-2-53 [01810] 1-2-54 [01811] 1-2-55 [01812] 1-2-56 [01813] 1-2-57 [01814] 1-2-58 [01815] 1-2-59 [01816] 1-2-60 [01817] 1-2-61 [01818] 1-2-62 [01819] 1-2-63 [01820] 1-2-64 [01821] 1-2-65 [01822] 1-2-66 [01823] 1-2-67 [01824] 1-2-68 [01825] 1-2-69 [01826] 1-2-70 [01827] 1-2-71 [01828] 1-2-72 [01829] 1-2-73 [01830] 1-2-74 [01831] 1-2-75 [01832] 1-2-76 [01833] 1-2-77 [01834] 1-2-78 [01835] 1-2-79 [01836] 1-2-80 [01837] 1-2-81 [01838] 1-2-82 [01839] 1-2-83 [01840] 1-2-84 [01841] 1-2-85 [01842] 1-2-86 [01843] 1-2-87 [01844] 1-2-88 [01845] 1-2-89 [01846] 1-2-90 [01847] 1-2-91 [01848] 1-2-92 [01849] 1-2-93 [01850] 1-2-94 [01851] 1-2-95 [01852] 1-2-96 [01853] 1-2-97 [01854] 1-2-98 [01855] 1-2-99 [01856] 1-2-100 [01857] 1-2-101 [01858] 1-2-102 [01859] 1-2-103 [01860] 1-2-104 [01861] 1-2-105 [01862] 1-2-106 [01863] 1-2-107 [01864] 1-2-108 [01865] 1-2-109 [01866] 1-2-110 [01867] 1-2-111 [01868] 1-2-112 [01869] 1-2-113 [01870] 1-2-114 [01871] 1-2-115 [01872] 1-2-116 [01873] 1-2-117 [01874] 1-2-118 [01875] 1-2-119 [01876] 1-2-120 [01877] 1-2-121 [01878] 1-2-122 [01879] 1-2-123 [01880] 1-2-124 [01881] 1-2-125 [01882] 1-2-126 [01883] 1-2-127 [01884] 1-2-128 [01885] 1-2-129 [01886] 1-2-130 [01887] 1-2-131 [01888] 1-2-132 [01889] 1-2-133 [01890] 1-2-134 [01891] 1-2-135 [01892] 1-2-136 [01893] 1-2-137 [01894] 1-2-138 [01895] 1-2-139 [01896] 1-2-140 [01897] 1-2-141 [01898] 1-2-142 [01899] 1-2-143 [01900] 1-2-144 [01901] 1-2-145 [01902] 1-2-146 [01903] 1-2-147 [01904] 1-2-148 [01905] 1-2-149 [01906] 1-2-150 [01907] 1-2-151 [01908] 1-2-152 [01909] 1-2-153 [01910] 1-2-154 [01911] 1-2-155 [01912] 1-2-156 [01913] 1-2-157 [01914] 1-2-158 [01915] 1-2-159 [01916] 1-2-160 [01917] 1-2-161 [01918] 1-2-162 [01919] 1-2-163 [01920] 1-2-164 [01921] 1-2-165 [01922] 1-2-166 [01923] 1-2-167 [01924] 1-2-168 [01925] 1-2-169 [01926] 1-2-170 [01927] 1-2-171 [01928] 1-2-172 [01929] 1-2-173 [01930] 1-2-174 [01931] 1-2-175 [01932] 1-2-176 [01933] 1-2-177 [01934] 1-2-178 [01935] 1-2-179 [01936] 1-2-180 [01937] 1-2-181 [01938] 1-2-182 [01939] 1-2-183 [01940] 1-2-184 [01941] 1-2-185 [01942] 1-2-186 [01943] 1-2-187 [01944] 1-2-188 [01945] 1-2-189 [01946] 1-2-190 [01947] 1-2-191 [01948] 1-2-192 [01949] 1-2-193 [01950] 1-2-194 [01951] 1-2-195 [01952] 1-2-196 [01953] 1-2-197 [01954] 1-2-198 [01955] 1-2-199 [01956] 1-2-200 [01957] 1-2-201 [01958] 1-2-202 [01959] 1-2-203 [01960] 1-2-204 [01961] 1-2-205 [01962] 1-2-206 [01963] 1-2-207 [01964] 1-2-208 [01965] 1-2-209 [01966] 1-2-210 [01967] 1-2-211 [01968] 1-2-212 [01969] 1-2-213 [01970] 1-2-214 [01971] 1-2-215 [01972] 1-2-216 [01973] 1-2-217 [01974] 1-2-218 [01975] 1-2-219 [01976] 1-2-220 [01977] 1-2-221 [01978] 1-2-222 [01979] 1-2-223 [01980] 1-2-224 [01981] 1-2-225 [01982] 1-3-1 [01983] 1-3-2 [01984] 1-3-3 [01985] 1-3-4 [01986] 1-3-5 [01987] 1-3-6 [01988] 1-3-7 [01989] 1-3-8 [01990] 1-3-9 [01991] 1-3-10 [01992] 1-3-11 [01993] 1-3-12 [01994] 1-3-13 [01995] 1-3-14 [01996] 1-3-15 [01997] 1-3-16 [01998] 1-3-17 [01999] 1-3-18 [02000] 1-3-19 [02001] 1-3-20 [02002] 1-3-21 [02003] 1-3-22 [02004] 1-3-23 [02005] 1-3-24 [02006] 1-3-25 [02007] 1-3-26 [02008] 1-3-27 [02009] 1-3-28 [02010] 1-3-29 [02011] 1-3-30 [02012] 1-3-31 [02013] 1-3-32 [02014] 1-3-33 [02015] 1-3-34 [02016] 1-3-35 [02017] 1-3-36 [02018] 1-3-37 [02019] 1-3-38 [02020] 1-3-39 [02021] 1-3-40 [02022] 1-3-41 [02023] 1-3-42 [02024] 1-3-43 [02025] 1-3-44 [02026] 1-3-45 [02027] 1-3-46 [02028] 1-3-47 [02029] 1-3-48 [02030] 1-3-49 [02031] 1-3-50 [02032] 1-3-51 [02033] 1-3-52 [02034] 1-3-53 [02035] 1-3-54 [02036] 1-3-55 [02037] 1-3-56 [02038] 1-3-57 [02039] 1-3-58 [02040] 1-3-59 [02041] 1-3-60 [02042] 1-3-61 [02043] 1-3-62 [02044] 1-3-63 [02045] 1-3-64 [02046] 1-3-65 [02047] 1-3-66 [02048] 1-3-67 [02049] 1-3-68 [02050] 1-3-69 [02051] 1-3-70 [02052] 1-3-71 [02053] 1-3-72 [02054] 1-3-73 [02055] 1-3-74 [02056] 1-3-75 [02057] 1-3-76 [02058] 1-3-77 [02059] 1-3-78 [02060] 1-3-79 [02061] 1-3-80 [02062] 1-3-81 [02063] 1-3-82 [02064] 1-3-83 [02065] 1-3-84 [02066] 1-3-85 [02067] 1-3-86 [02068] 1-3-87 [02069] 1-3-88 [02070] 1-3-89 [02071] 1-3-90 [02072] 1-3-91 [02073] 1-3-92 [02074] 1-3-93 [02075] 1-3-94 [02076] 1-3-95 [02077] 1-3-96 [02078] 1-3-97 [02079] 1-3-98 [02080] 1-3-99 [02081] 1-3-100 [02082] 1-4-1 [02083] 1-4-2 [02084] 1-4-3 [02085] 1-4-4 [02086] 1-4-5 [02087] 1-4-6 [02088] 1-4-7 [02089] 1-4-8 [02090] 1-4-9 [02091] 1-4-10 [02092] 1-4-11 [02093] 1-4-12 [02094] 1-4-13 [02095] 1-4-14 [02096] 1-4-15 [02097] 1-4-16 [02098] 1-4-17 [02099] 1-4-18 [02100] 1-4-19 [02101] 1-4-20 [02102] 1-4-21 [02103] 1-4-22 [02104] 1-4-23 [02105] 1-4-24 [02106] 1-4-25 [02107] 1-4-26 [02108] 1-4-27 [02109] 1-4-28 [02110] 1-4-29 [02111] 1-4-30 [02112] 1-4-31 [02113] 1-4-32 [02114] 1-4-33 [02115] 1-4-34 [02116] 1-4-35 [02117] 1-4-36 [02118] 1-4-37 [02119] 1-4-38 [02120] 1-4-39 [02121] 1-4-40 [02122] 1-4-41 [02123] 1-4-42 [02124] 1-4-43 [02125] 1-4-44 [02126] 1-4-45 [02127] 1-4-46 [02128] 1-4-47 [02129] 1-4-48 [02130] 1-4-49 [02131] 1-4-50 [02132] 1-4-51 [02133] 1-4-52 [02134] 1-4-53 [02135] 1-4-54 [02136] 1-4-55 [02137] 1-4-56 [02138] 1-4-57 [02139] 1-4-58 [02140] 1-4-59 [02141] 1-4-60 [02142] 1-4-61 [02143] 1-4-62 [02144] 1-4-63 [02145] 1-4-64 [02146] 1-4-65 [02147] 1-4-66 [02148] 1-4-67 [02149] 1-4-68 [02150] 1-4-69 [02151] 1-4-70 [02152] 1-5-1 [02153] 1-5-2 [02154] 1-5-3 [02155] 1-5-4 [02156] 1-5-5 [02157] 1-5-6 [02158] 1-5-7 [02159] 1-5-8 [02160] 1-5-9 [02161] 1-5-10 [02162] 1-5-11 [02163] 1-5-12 [02164] 1-5-13 [02165] 1-5-14 [02166] 1-5-15 [02167] 1-5-16 [02168] 1-5-17 [02169] 1-5-18 [02170] 1-5-19 [02171] 1-5-20 [02172] 1-5-21 [02173] 1-5-22 [02174] 1-5-23 [02175] 1-5-24 [02176] 1-5-25 [02177] 1-5-26 [02178] 1-5-27 [02179] 1-5-28 [02180] 1-5-29 [02181] 1-5-30 [02182] 1-5-31 [02183] 1-5-32 [02184] 1-5-33 [02185] 1-5-34 [02186] 1-5-35 [02187] 1-5-36 [02188] 1-5-37 [02189] 1-5-38 [02190] 1-5-39 [02191] 1-5-40 [02192] 1-5-41 [02193] 1-5-42 [02194] 1-5-43 [02195] 1-5-44 [02196] 1-5-45 [02197] 1-5-46 [02198] 1-5-47 [02199] 1-5-48 [02200] 1-5-49 [02201] 1-5-50 [02202] 1-5-51 [02203] 1-5-52 [02204] 1-5-53 [02205] 1-5-54 [02206] 1-5-55 [02207] 1-5-56 [02208] 1-5-57 [02209] 1-5-58 [02210] 1-5-59 [02211] 1-5-60 [02212] 1-5-61 [02213] 1-5-62 [02214] 1-5-63 [02215] 1-5-64 [02216] 1-5-65 [02217] 1-5-66 [02218] 1-5-67 [02219] 1-5-68 [02220] 1-5-69 [02221] 1-5-70 [02222] 1-5-71 [02223] 1-5-72 [02224] 1-5-73 [02225] 1-5-74 [02226] 1-5-75 [02227] 1-6-1 [02228] 1-6-2 [02229] 1-6-3 [02230] 1-6-4 [02231] 1-6-5 [02232] 1-6-6 [02233] 1-6-7 [02234] 1-6-8 [02235] 1-6-9 [02236] 1-6-10 [02237] 1-6-11 [02238] 1-6-12 [02239] 1-6-13 [02240] 1-6-14 [02241] 1-6-15 [02242] 1-6-16 [02243] 1-6-17 [02244] 1-6-18 [02245] 1-6-19 [02246] 1-6-20 [02247] 1-6-21 [02248] 1-6-22 [02249] 1-6-23 [02250] 1-6-24 [02251] 1-6-25 [02252] 1-6-26 [02253] 1-6-27 [02254] 1-6-28 [02255] 1-6-29 [02256] 1-6-30 [02257] 1-6-31 [02258] 1-6-32 [02259] 1-6-33 [02260] 1-6-34 [02261] 1-6-35 [02262] 1-6-36 [02263] 1-6-37 [02264] 1-6-38 [02265] 1-6-39 [02266] 1-6-40 [02267] 1-6-41 [02268] 1-6-42 [02269] 1-6-43 [02270] 1-6-44 [02271] 1-6-45 [02272] 1-6-46 [02273] 1-6-47 [02274] 1-6-48 [02275] 1-6-49 [02276] 1-6-50 [02277] 1-6-51 [02278] 1-6-52 [02279] 1-6-53 [02280] 1-6-54 [02281] 1-6-55 [02282] 1-6-56 [02283] 1-6-57 [02284] 1-6-58 [02285] 1-6-59 [02286] 1-6-60 [02287]

17. Example of Compound (1)

[1066] According to the synthesis methods described in Synthesis Examples, compounds (1-1-1) to (1-1-13) shown below can be prepared.

TABLE-US-00017 No. 1-1-1 [02288] 1-1-2 [02289] 1-1-3 [02290] 1-1-4 [02291] 1-1-5 [02292] 1-1-6 [02293] 1-1-7 [02294] 1-1-8 [02295] 1-1-9 [02296] 1-1-10 [02297] 1-1-11 [02298] 1-1-12 [02299] 1-1-13 [02300]

18. Example of Compound (1)

[1067] According to the synthesis methods described in Synthesis Examples, compounds (1-1-1) to (1-1-20), compounds (1-2-1) to (1-2-180), compounds (1-3-1) to (1-3-140), compounds (1-4-1) to (1-4-134) and (1-5-1) to (1-5-20), compounds (1-6-1) to (1-6-180), compounds (1-7-1) to (1-7-140), compounds (1-8-1) to (1-8-134), compounds (1-9-1) to (1-9-40), compounds (1-10-1) to (1-10-200), compounds (1-11-1) to (1-11-140) and compounds (1-12-1) to (1-12-100) shown below can be prepared.

TABLE-US-00018 No. 1-1-1 [02301] 1-1-2 [02302] 1-1-3 [02303] 1-1-4 [02304] 1-1-5 [02305] 1-1-6 [02306] 1-1-7 [02307] 1-1-8 [02308] 1-1-9 [02309] 1-1-10 [02310] 1-1-11 [02311] 1-1-12 [02312] 1-1-13 [02313] 1-1-14 [02314] 1-1-15 [02315] 1-1-16 [02316] 1-1-17 [02317] 1-1-18 [02318] 1-1-19 [02319] 1-1-20 [02320] 1-2-1 [02321] 1-2-2 [02322] 1-2-3 [02323] 1-2-4 [02324] 1-2-5 [02325] 1-2-6 [02326] 1-2-7 [02327] 1-2-8 [02328] 1-2-9 [02329] 1-2-10 [02330] 1-2-11 [02331] 1-2-12 [02332] 1-2-13 [02333] 1-2-14 [02334] 1-2-15 [02335] 1-2-16 [02336] 1-2-17 [02337] 1-2-18 [02338] 1-2-19 [02339] 1-2-20 [02340] 1-2-21 [02341] 1-2-22 [02342] 1-2-23 [02343] 1-2-24 [02344] 1-2-25 [02345] 1-2-26 [02346] 1-2-27 [02347] 1-2-28 [02348] 1-2-29 [02349] 1-2-30 [02350] 1-2-31 [02351] 1-2-32 [02352] 1-2-33 [02353] 1-2-34 [02354] 1-2-35 [02355] 1-2-36 [02356] 1-2-37 [02357] 1-2-38 [02358] 1-2-39 [02359] 1-2-40 [02360] 1-2-41 [02361] 1-2-42 [02362] 1-2-43 [02363] 1-2-44 [02364] 1-2-45 [02365] 1-2-46 [02366] 1-2-47 [02367] 1-2-48 [02368] 1-2-49 [02369] 1-2-50 [02370] 1-2-51 [02371] 1-2-52 [02372] 1-2-53 [02373] 1-2-54 [02374] 1-2-55 [02375] 1-2-56 [02376] 1-2-57 [02377] 1-2-58 [02378] 1-2-59 [02379] 1-2-60 [02380] 1-2-61 [02381] 1-2-62 [02382] 1-2-63 [02383] 1-2-64 [02384] 1-2-65 [02385] 1-2-66 [02386] 1-2-67 [02387] 1-2-68 [02388] 1-2-69 [02389] 1-2-70 [02390] 1-2-71 [02391] 1-2-72 [02392] 1-2-73 [02393] 1-2-74 [02394] 1-2-75 [02395] 1-2-76 [02396] 1-2-77 [02397] 1-2-78 [02398] 1-2-79 [02399] 1-2-80 [02400] 1-2-81 [02401] 1-2-82 [02402] 1-2-83 [02403] 1-2-84 [02404] 1-2-85 [02405] 1-2-86 [02406] 1-2-87 [02407] 1-2-88 [02408] 1-2-89 [02409] 1-2-90 [02410] 1-2-91 [02411] 1-2-92 [02412] 1-2-93 [02413] 1-2-94 [02414] 1-2-95 [02415] 1-2-96 [02416] 1-2-97 [02417] 1-2-98 [02418] 1-2-99 [02419] 1-2-100 [02420] 1-2-101 [02421] 1-2-102 [02422] 1-2-103 [02423] 1-2-104 [02424] 1-2-105 [02425] 1-2-106 [02426] 1-2-107 [02427] 1-2-108 [02428] 1-2-109 [02429] 1-2-110 [02430] 1-2-111 [02431] 1-2-112 [02432] 1-2-113 [02433] 1-2-114 [02434] 1-2-115 [02435] 1-2-116 [02436] 1-2-117 [02437] 1-2-118 [02438] 1-2-119 [02439] 1-2-120 [02440] 1-2-121 [02441] 1-2-122 [02442] 1-2-123 [02443] 1-2-124 [02444] 1-2-125 [02445] 1-2-126 [02446] 1-2-127 [02447] 1-2-128 [02448] 1-2-129 [02449] 1-2-130 [02450] 1-2-131 [02451] 1-2-132 [02452] 1-2-133 [02453] 1-2-134 [02454] 1-2-135 [02455] 1-2-136 [02456] 1-2-137 [02457] 1-2-138 [02458] 1-2-139 [02459] 1-2-140 [02460] 1-2-141 [02461] 1-2-142 [02462] 1-2-143 [02463] 1-2-144 [02464] 1-2-145 [02465] 1-2-146 [02466] 1-2-147 [02467] 1-2-148 [02468] 1-2-149 [02469] 1-2-150 [02470] 1-2-151 [02471] 1-2-152 [02472] 1-2-153 [02473] 1-2-154 [02474] 1-2-155 [02475] 1-2-156 [02476] 1-2-157 [02477] 1-2-158 [02478] 1-2-159 [02479] 1-2-160 [02480] 1-2-161 [02481] 1-2-162 [02482] 1-2-163 [02483] 1-2-164 [02484] 1-2-165 [02485] 1-2-166 [02486] 1-2-167 [02487] 1-2-168 [02488] 1-2-169 [02489] 1-2-170 [02490] 1-2-171 [02491] 1-2-172 [02492] 1-2-173 [02493] 1-2-174 [02494] 1-2-175 [02495] 1-2-176 [02496] 1-2-177 [02497] 1-2-178 [02498] 1-2-179 [02499] 1-2-180 [02500] 1-3-1 [02501] 1-3-2 [02502] 1-3-3 [02503] 1-3-4 [02504] 1-3-5 [02505] 1-3-6 [02506] 1-3-7 [02507] 1-3-8 [02508] 1-3-9 [02509] 1-3-10 [02510] 1-3-11 [02511] 1-3-12 [02512] 1-3-13 [02513] 1-3-14 [02514] 1-3-15 [02515] 1-3-16 [02516] 1-3-17 [02517] 1-3-18 [02518] 1-3-19 [02519] 1-3-20 [02520] 1-3-21 [02521] 1-3-22 [02522] 1-3-23 [02523] 1-3-24 [02524] 1-3-25 [02525] 1-3-26 [02526] 1-3-27 [02527] 1-3-28 [02528] 1-3-29 [02529] 1-3-30 [02530] 1-3-31 [02531] 1-3-32 [02532] 1-3-33 [02533] 1-3-34 [02534] 1-3-35 [02535] 1-3-36 [02536] 1-3-37 [02537] 1-3-38 [02538] 1-3-39 [02539] 1-3-40 [02540] 1-3-41 [02541] 1-3-42 [02542] 1-3-43 [02543] 1-3-44 [02544] 1-3-45 [02545] 1-3-46 [02546] 1-3-47 [02547] 1-3-48 [02548] 1-3-49 [02549] 1-3-50 [02550] 1-3-51 [02551] 1-3-52 [02552] 1-3-53 [02553] 1-3-54 [02554] 1-3-55 [02555] 1-3-56 [02556] 1-3-57 [02557] 1-3-58 [02558] 1-3-59 [02559] 1-3-60 [02560] 1-3-61 [02561] 1-3-62 [02562] 1-3-63 [02563] 1-3-64 [02564] 1-3-65 [02565] 1-3-66 [02566] 1-3-67 [02567] 1-3-68 [02568] 1-3-69 [02569] 1-3-70 [02570] 1-3-71 [02571] 1-3-72 [02572] 1-3-73 [02573] 1-3-74 [02574] 1-3-75 [02575] 1-3-76 [02576] 1-3-77 [02577] 1-3-78 [02578] 1-3-79 [02579] 1-3-80 [02580] 1-3-81 [02581] 1-3-82 [02582] 1-3-83 [02583] 1-3-84 [02584] 1-3-85 [02585] 1-3-86 [02586] 1-3-87 [02587] 1-3-88 [02588] 1-3-89 [02589] 1-3-90 [02590] 1-3-91 [02591] 1-3-92 [02592] 1-3-93 [02593] 1-3-94 [02594] 1-3-95 [02595] 1-3-96 [02596] 1-3-97 [02597] 1-3-98 [02598] 1-3-99 [02599] 1-3-100 [02600] 1-3-101 [02601] 1-3-102 [02602] 1-3-103 [02603] 1-3-104 [02604] 1-3-105 [02605] 1-3-106 [02606] 1-3-107 [02607] 1-3-108 [02608] 1-3-109 [02609] 1-3-110 [02610] 1-3-111 [02611] 1-3-112 [02612] 1-3-113 [02613] 1-3-114 [02614] 1-3-115 [02615] 1-3-116 [02616] 1-3-117 [02617] 1-3-118 [02618] 1-3-119 [02619] 1-3-120 [02620] 1-3-121 [02621] 1-3-122 [02622] 1-3-123 [02623] 1-3-124 [02624] 1-3-125 [02625] 1-3-126 [02626] 1-3-127 [02627] 1-3-128 [02628] 1-3-129 [02629] 1-3-130 [02630] 1-3-131 [02631] 1-3-132 [02632] 1-3-133 [02633] 1-3-134 [02634] 1-3-135 [02635] 1-3-136 [02636] 1-3-137 [02637] 1-3-138 [02638] 1-3-139 [02639] 1-3-140 [02640] 1-4-1 [02641] 1-4-2 [02642] 1-4-3 [02643] 1-4-4 [02644] 1-4-5 [02645] 1-4-6 [02646] 1-4-7 [02647] 1-4-8 [02648] 1-4-9 [02649] 1-4-10 [02650] 1-4-11 [02651] 1-4-12 [02652] 1-4-13 [02653] 1-4-14 [02654] 1-4-15 [02655] 1-4-16 [02656] 1-4-17 [02657] 1-4-18 [02658] 1-4-19 [02659] 1-4-20 [02660] 1-4-21 [02661] 1-4-22 [02662] 1-4-23 [02663] 1-4-24 [02664] 1-4-25 [02665] 1-4-26 [02666] 1-4-27 [02667] 1-4-28 [02668] 1-4-29 [02669] 1-4-30 [02670] 1-4-31 [02671] 1-4-32 [02672] 1-4-33 [02673] 1-4-34 [02674] 1-4-35 [02675] 1-4-36 [02676] 1-4-37 [02677] 1-4-38 [02678] 1-4-39 [02679] 1-4-40 [02680] 1-4-41 [02681] 1-4-42 [02682] 1-4-43 [02683] 1-4-44 [02684] 1-4-45 [02685] 1-4-46 [02686] 1-4-47 [02687] 1-4-48 [02688] 1-4-49 [02689] 1-4-50 [02690] 1-4-51 [02691] 1-4-52 [02692] 1-4-53 [02693] 1-4-54 [02694] 1-4-55 [02695] 1-4-56 [02696] 1-4-57 [02697] 1-4-58 [02698] 1-4-59 [02699] 1-4-60 [02700] 1-4-61 [02701] 1-4-62 [02702] 1-4-63 [02703] 1-4-64 [02704] 1-4-65 [02705] 1-4-66 [02706] 1-4-67 [02707] 1-4-68 [02708] 1-4-69 [02709] 1-4-70 [02710] 1-4-71 [02711] 1-4-72 [02712] 1-4-73 [02713] 1-4-74 [02714] 1-4-75 [02715] 1-4-76 [02716] 1-4-77 [02717] 1-4-78 [02718] 1-4-79 [02719] 1-4-80 [02720] 1-4-81 [02721] 1-4-82 [02722] 1-4-83 [02723] 1-4-84 [02724] 1-4-85 [02725] 1-4-86 [02726] 1-4-87 [02727] 1-4-88 [02728] 1-4-89 [02729] 1-4-90 [02730] 1-4-91 [02731] 1-4-92 [02732] 1-4-93 [02733] 1-4-94 [02734] 1-4-95 [02735] 1-4-96 [02736] 1-4-97 [02737] 1-4-98 [02738] 1-4-99 [02739] 1-4-100 [02740] 1-4-101 [02741] 1-4-102 [02742] 1-4-103 [02743] 1-4-104 [02744] 1-4-105 [02745] 1-4-106 [02746] 1-4-107 [02747] 1-4-108 [02748] 1-4-109 [02749] 1-4-110 [02750] 1-4-111 [02751] 1-4-112 [02752] 1-4-113 [02753] 1-4-114 [02754] 1-4-115 [02755] 1-4-116 [02756] 1-4-117 [02757] 1-4-118 [02758] 1-4-119 [02759] 1-4-120 [02760] 1-4-121 [02761] 1-4-122 [02762] 1-4-123 [02763] 1-4-124 [02764] 1-4-125 [02765] 1-4-126 [02766] 1-4-127 [02767] 1-4-128 [02768] 1-4-131 [02769] 1-4-132 [02770] 1-4-133 [02771] 1-4-134 [02772] 1-5-1 [02773] 1-5-2 [02774] 1-5-3 [02775] 1-5-4 [02776] 1-5-5 [02777] 1-5-6 [02778] 1-5-7 [02779] 1-5-8 [02780] 1-5-9 [02781] 1-5-10 [02782] 1-5-11 [02783] 1-5-12 [02784] 1-5-13 [02785] 1-5-14 [02786] 1-5-15 [02787] 1-5-16 [02788] 1-5-17 [02789] 1-5-18 [02790] 1-5-19 [02791] 1-5-20 [02792] 1-6-1 [02793] 1-6-2 [02794] 1-6-3 [02795] 1-6-4 [02796] 1-6-5 [02797] 1-6-6 [02798] 1-6-7 [02799] 1-6-8 [02800] 1-6-9 [02801] 1-6-10 [02802] 1-6-11 [02803] 1-6-12 [02804] 1-6-13 [02805] 1-6-14 [02806] 1-6-15 [02807] 1-6-16 [02808] 1-6-17 [02809] 1-6-18 [02810] 1-6-19 [02811] 1-6-20 [02812] 1-6-21 [02813] 1-6-22 [02814] 1-6-23 [02815] 1-6-24 [02816] 1-6-25 [02817] 1-6-26 [02818] 1-6-27 [02819] 1-6-28 [02820] 1-6-29 [02821] 1-6-30 [02822] 1-6-31 [02823] 1-6-32 [02824] 1-6-33 [02825] 1-6-34 [02826] 1-6-35 [02827] 1-6-36 [02828] 1-6-37 [02829] 1-6-38 [02830] 1-6-39 [02831] 1-6-40 [02832] 1-6-41 [02833] 1-6-42 [02834] 1-6-43 [02835] 1-6-44 [02836] 1-6-45 [02837] 1-6-46 [02838] 1-6-47 [02839] 1-6-48 [02840] 1-6-49 [02841] 1-6-50 [02842] 1-6-51 [02843] 1-6-52 [02844] 1-6-53 [02845] 1-6-54 [02846] 1-6-55 [02847] 1-6-56 [02848] 1-6-57 [02849] 1-6-58 [02850] 1-6-59 [02851] 1-6-60 [02852] 1-6-61 [02853] 1-6-62 [02854] 1-6-63 [02855] 1-6-64 [02856] 1-6-65 [02857] 1-6-66 [02858] 1-6-67 [02859] 1-6-68 [02860] 1-6-69 [02861] 1-6-70 [02862] 1-6-71 [02863] 1-6-72 [02864] 1-6-73 [02865] 1-6-74 [02866] 1-6-75 [02867] 1-6-76 [02868] 1-6-77 [02869] 1-6-78 [02870] 1-6-79 [02871] 1-6-80 [02872] 1-6-81 [02873] 1-6-82 [02874] 1-6-83 [02875] 1-6-84 [02876] 1-6-85 [02877] 1-6-86 [02878] 1-6-87 [02879] 1-6-88 [02880] 1-6-89 [02881] 1-6-90 [02882] 1-6-91 [02883] 1-6-92 [02884] 1-6-93 [02885] 1-6-94 [02886] 1-6-95 [02887] 1-6-96 [02888] 1-6-97 [02889] 1-6-98 [02890] 1-6-99 [02891] 1-6-100 [02892] 1-6-101 [02893] 1-6-102 [02894] 1-6-103 [02895] 1-6-104 [02896] 1-6-105 [02897] 1-6-106 [02898] 1-6-107 [02899] 1-6-108 [02900] 1-6-109 [02901] 1-6-110 [02902] 1-6-111 [02903] 1-6-112 [02904] 1-6-113 [02905] 1-6-114 [02906] 1-6-115 [02907] 1-6-116 [02908] 1-6-117 [02909] 1-6-118 [02910] 1-6-119 [02911] 1-6-120 [02912] 1-6-121 [02913] 1-6-122 [02914] 1-6-123 [02915] 1-6-124 [02916] 1-6-125 [02917] 1-6-126 [02918] 1-6-127 [02919] 1-6-128 [02920] 1-6-129 [02921] 1-6-130 [02922] 1-6-131 [02923] 1-6-132 [02924] 1-6-133 [02925] 1-6-134 [02926] 1-6-135 [02927] 1-6-136 [02928] 1-6-137 [02929] 1-6-138 [02930] 1-6-139 [02931] 1-6-140 [02932] 1-6-141 [02933] 1-6-142 [02934] 1-6-143 [02935] 1-6-144 [02936] 1-6-145 [02937] 1-6-146 [02938] 1-6-147 [02939] 1-6-148 [02940] 1-6-149 [02941] 1-6-150 [02942] 1-6-151 [02943] 1-6-152 [02944] 1-6-153 [02945] 1-6-154 [02946] 1-6-155 [02947] 1-6-156 [02948] 1-6-157 [02949] 1-6-158 [02950] 1-6-159 [02951] 1-6-160 [02952] 1-6-161 [02953] 1-6-162 [02954] 1-6-163 [02955] 1-6-164 [02956] 1-6-165 [02957] 1-6-166 [02958] 1-6-167 [02959] 1-6-168 [02960] 1-6-169 [02961] 1-6-170 [02962] 1-6-171 [02963] 1-6-172 [02964] 1-6-173 [02965] 1-6-174 [02966] 1-6-175 [02967] 1-6-176 [02968] 1-6-177 [02969] 1-6-178 [02970] 1-6-179 [02971] 1-6-180 [02972] 1-7-1 [02973] 1-7-2 [02974] 1-7-3 [02975] 1-7-4 [02976] 1-7-5 [02977] 1-7-6 [02978] 1-7-7 [02979] 1-7-8 [02980] 1-7-9 [02981] 1-7-10 [02982] 1-7-11 [02983] 1-7-12 [02984] 1-7-13 [02985] 1-7-14 [02986] 1-7-15 [02987] 1-7-16 [02988] 1-7-17 [02989] 1-7-18 [02990] 1-7-19 [02991] 1-7-20 [02992] 1-7-21 [02993] 1-7-22 [02994] 1-7-23 [02995] 1-7-24 [02996] 1-7-25 [02997] 1-7-26 [02998] 1-7-27 [02999] 1-7-28 [03000] 1-7-29 [03001] 1-7-30 [03002] 1-7-31 [03003] 1-7-32 [03004] 1-7-33 [03005] 1-7-34 [03006] 1-7-35 [03007] 1-7-36 [03008] 1-7-37 [03009] 1-7-38 [03010] 1-7-39 [03011] 1-7-40 [03012] 1-7-41 [03013] 1-7-42 [03014] 1-7-43 [03015] 1-7-44 [03016] 1-7-45 [03017] 1-7-46 [03018] 1-7-47 [03019] 1-7-48 [03020] 1-7-49 [03021] 1-7-50 [03022] 1-7-51 [03023] 1-7-52 [03024] 1-7-53 [03025] 1-7-54 [03026] 1-7-55 [03027] 1-7-56 [03028] 1-7-57 [03029] 1-7-58 [03030] 1-7-59 [03031] 1-7-60 [03032] 1-7-61 [03033] 1-7-62 [03034] 1-7-63 [03035] 1-7-64 [03036] 1-7-65 [03037] 1-7-66 [03038] 1-7-67 [03039] 1-7-68 [03040] 1-7-69 [03041] 1-7-70 [03042] 1-7-71 [03043] 1-7-72 [03044] 1-7-73 [03045] 1-7-74 [03046] 1-7-75 [03047] 1-7-76 [03048] 1-7-77 [03049] 1-7-78 [03050] 1-7-79 [03051] 1-7-80 [03052] 1-7-81 [03053] 1-7-82 [03054] 1-7-83 [03055] 1-7-84 [03056] 1-7-85 [03057] 1-7-86 [03058] 1-7-87 [03059] 1-7-88 [03060] 1-7-89 [03061] 1-7-90 [03062] 1-7-91 [03063] 1-7-92 [03064] 1-7-93 [03065] 1-7-94 [03066] 1-7-95 [03067] 1-7-96 [03068] 1-7-97 [03069] 1-7-98 [03070] 1-7-99 [03071] 1-7-100 [03072] 1-7-101 [03073] 1-7-102 [03074] 1-7-103 [03075] 1-7-104 [03076] 1-7-105 [03077] 1-7-106 [03078] 1-7-107 [03079] 1-7-108 [03080] 1-7-109 [03081] 1-7-110 [03082] 1-7-111 [03083] 1-7-112 [03084] 1-7-113 [03085] 1-7-114 [03086] 1-7-115 [03087] 1-7-116 [03088] 1-7-117 [03089] 1-7-118 [03090] 1-7-119 [03091] 1-7-120 [03092] 1-7-121 [03093] 1-7-122 [03094] 1-7-123 [03095] 1-7-124 [03096] 1-7-125 [03097] 1-7-126 [03098] 1-7-127 [03099] 1-7-128 [03100] 1-7-129 [03101] 1-7-130 [03102] 1-7-131 [03103] 1-7-132 [03104] 1-7-133 [03105] 1-7-134 [03106] 1-7-135 [03107] 1-7-136 [03108] 1-7-137 [03109] 1-7-138 [03110] 1-7-139 [03111] 1-7-140 [03112] 1-8-1 [03113] 1-8-2 [03114] 1-8-3 [03115] 1-8-4 [03116] 1-8-5 [03117] 1-8-6 [03118] 1-8-7 [03119] 1-8-8 [03120] 1-8-9 [03121] 1-8-10 [03122] 1-8-11 [03123] 1-8-12 [03124] 1-8-13 [03125] 1-8-14 [03126] 1-8-15 [03127] 1-8-16 [03128] 1-8-17 [03129] 1-8-18 [03130] 1-8-19 [03131] 1-8-20 [03132] 1-8-21 [03133] 1-8-22 [03134] 1-8-23 [03135] 1-8-24 [03136] 1-8-25 [03137] 1-8-26 [03138] 1-8-27 [03139] 1-8-28 [03140] 1-8-29 [03141] 1-8-30 [03142] 1-8-31 [03143] 1-8-32 [03144] 1-8-33 [03145] 1-8-34 [03146] 1-8-35 [03147] 1-8-36 [03148] 1-8-37 [03149] 1-8-38 [03150] 1-8-39 [03151] 1-8-40 [03152] 1-8-41 [03153] 1-8-42 [03154] 1-8-43 [03155] 1-8-44 [03156] 1-8-45 [03157] 1-8-46 [03158] 1-8-47 [03159] 1-8-48 [03160] 1-8-49 [03161] 1-8-50 [03162] 1-8-51 [03163] 1-8-52 [03164] 1-8-53 [03165] 1-8-54 [03166] 1-8-55 [03167] 1-8-56 [03168] 1-8-57 [03169] 1-8-58 [03170] 1-8-59 [03171] 1-8-60 [03172] 1-8-61 [03173] 1-8-62 [03174] 1-8-63 [03175] 1-8-64 [03176] 1-8-65 [03177] 1-8-66 [03178] 1-8-67 [03179] 1-8-68 [03180] 1-8-69 [03181] 1-8-70 [03182] 1-8-71 [03183] 1-8-72 [03184] 1-8-73 [03185] 1-8-74 [03186] 1-8-75 [03187] 1-8-76 [03188] 1-8-77 [03189] 1-8-78 [03190] 1-8-79 [03191] 1-8-80 [03192] 1-8-81 [03193] 1-8-82 [03194] 1-8-83 [03195] 1-8-84 [03196] 1-8-85 [03197] 1-8-86 [03198] 1-8-87 [03199] 1-8-88 [03200] 1-8-89 [03201] 1-8-90 [03202] 1-8-91 [03203] 1-8-92 [03204] 1-8-93 [03205] 1-8-94 [03206] 1-8-95 [03207] 1-8-96 [03208] 1-8-97 [03209] 1-8-98 [03210] 1-8-99 [03211] 1-8-100 [03212] 1-8-101 [03213] 1-8-102 [03214] 1-8-103 [03215] 1-8-104 [03216] 1-8-105 [03217] 1-8-106 [03218] 1-8-107 [03219] 1-8-108 [03220] 1-8-109 [03221] 1-8-110 [03222] 1-8-111 [03223] 1-8-112 [03224] 1-8-113 [03225] 1-8-114 [03226] 1-8-115 [03227] 1-8-116 [03228] 1-8-117 [03229] 1-8-118 [03230] 1-8-119 [03231] 1-8-120 [03232] 1-8-121 [03233] 1-8-122 [03234] 1-8-123 [03235] 1-8-124 [03236] 1-8-125 [03237] 1-8-126 [03238] 1-8-127 [03239] 1-8-128 [03240] 1-8-131 [03241] 1-8-132 [03242] 1-8-133 [03243] 1-8-134 [03244] 1-9-1 [03245] 1-9-2 [03246] 1-9-3 [03247] 1-9-4 [03248] 1-9-5 [03249] 1-9-6 [03250] 1-9-7 [03251] 1-9-8 [03252] 1-9-9 [03253] 1-9-10 [03254] 1-9-11 [03255] 1-9-12 [03256] 1-9-13 [03257] 1-9-14 [03258] 1-9-15 [03259] 1-9-16 [03260] 1-9-17 [03261] 1-9-18 [03262] 1-9-19 [03263] 1-9-20 [03264] 1-9-21 [03265] 1-9-22 [03266] 1-9-23 [03267] 1-9-24 [03268] 1-9-25 [03269] 1-9-26 [03270] 1-9-27 [03271] 1-9-28 [03272] 1-9-29 [03273] 1-9-30 [03274] 1-9-31 [03275] 1-9-32 [03276] 1-9-33 [03277] 1-9-34 [03278] 1-9-35 [03279] 1-9-36 [03280] 1-9-37 [03281] 1-9-38 [03282] 1-9-39 [03283] 1-9-40 [03284] 1-10-1 [03285] 1-10-2 [03286] 1-10-3 [03287] 1-10-4 [03288] 1-10-5 [03289] 1-10-6 [03290] 1-10-7 [03291] 1-10-8 [03292] 1-10-9 [03293] 1-10-10 [03294] 1-10-11 [03295] 1-10-12 [03296] 1-10-13 [03297] 1-10-14 [03298] 1-10-15 [03299] 1-10-16 [03300] 1-10-17 [03301] 1-10-18 [03302] 1-10-19 [03303] 1-10-20 [03304] 1-10-21 [03305] 1-10-22 [03306] 1-10-23 [03307] 1-10-24 [03308] 1-10-25 [03309] 1-10-26 [03310] 1-10-27 [03311] 1-10-28 [03312] 1-10-29 [03313] 1-10-30 [03314] 1-10-31 [03315] 1-10-32 [03316] 1-10-33 [03317] 1-10-34 [03318] 1-10-35 [03319] 1-10-36 [03320] 1-10-37 [03321] 1-10-38 [03322] 1-10-39 [03323] 1-10-40 [03324] 1-10-41 [03325] 1-10-42 [03326] 1-10-43 [03327] 1-10-44 [03328] 1-10-45 [03329] 1-10-46 [03330] 1-10-47 [03331] 1-10-48 [03332] 1-10-49 [03333] 1-10-50 [03334] 1-10-51 [03335] 1-10-52 [03336] 1-10-53 [03337] 1-10-54 [03338] 1-10-55 [03339] 1-10-56 [03340] 1-10-57 [03341] 1-10-58 [03342] 1-10-59 [03343] 1-10-60 [03344] 1-10-61 [03345] 1-10-62 [03346] 1-10-63 [03347] 1-10-64 [03348] 1-10-65 [03349] 1-10-66 [03350] 1-10-67 [03351] 1-10-68 [03352] 1-10-69 [03353] 1-10-70 [03354] 1-10-71 [03355] 1-10-72 [03356] 1-10-73 [03357] 1-10-74 [03358] 1-10-75 [03359] 1-10-76 [03360] 1-10-77 [03361] 1-10-78 [03362] 1-10-79 [03363] 1-10-80 [03364] 1-10-81 [03365] 1-10-82 [03366] 1-10-83 [03367] 1-10-84 [03368] 1-10-85 [03369] 1-10-86 [03370] 1-10-87 [03371] 1-10-88 [03372] 1-10-89 [03373] 1-10-90 [03374] 1-10-91 [03375] 1-10-92 [03376] 1-10-93 [03377] 1-10-94 [03378] 1-10-95 [03379] 1-10-96 [03380] 1-10-97 [03381] 1-10-98 [03382] 1-10-99 [03383] 1-10-100 [03384] 1-10-101 [03385] 1-10-102 [03386] 1-10-103 [03387] 1-10-104 [03388] 1-10-105 [03389] 1-10-106 [03390] 1-10-107 [03391] 1-10-108 [03392] 1-10-109 [03393] 1-10-110 [03394] 1-10-111 [03395] 1-10-112 [03396] 1-10-113 [03397] 1-10-114 [03398] 1-10-115 [03399] 1-10-116 [03400] 1-10-117 [03401] 1-10-118 [03402] 1-10-119 [03403] 1-10-120 [03404] 1-10-121 [03405] 1-10-122 [03406] 1-10-123 [03407] 1-10-124 [03408] 1-10-125 [03409] 1-10-126 [03410] 1-10-127 [03411] 1-10-128 [03412] 1-10-129 [03413] 1-10-130 [03414] 1-10-131 [03415] 1-10-132 [03416] 1-10-133 [03417] 1-10-134 [03418] 1-10-135 [03419] 1-10-136 [03420] 1-10-137 [03421] 1-10-138 [03422] 1-10-139 [03423] 1-10-140 [03424] 1-10-141 [03425] 1-10-142 [03426] 1-10-143 [03427] 1-10-144 [03428] 1-10-145 [03429] 1-10-146 [03430] 1-10-147 [03431] 1-10-148 [03432] 1-10-149 [03433] 1-10-150 [03434] 1-10-151 [03435] 1-10-152 [03436] 1-10-153 [03437] 1-10-154 [03438] 1-10-155 [03439] 1-10-156 [03440] 1-10-157 [03441] 1-10-158 [03442] 1-10-159 [03443] 1-10-160 [03444] 1-10-161 [03445] 1-10-162 [03446] 1-10-163 [03447] 1-10-164 [03448] 1-10-165 [03449] 1-10-166 [03450] 1-10-167 [03451] 1-10-168 [03452] 1-10-169 [03453] 1-10-170 [03454] 1-10-171 [03455] 1-10-172 [03456] 1-10-173 [03457] 1-10-174 [03458] 1-10-175 [03459] 1-10-176 [03460] 1-10-177 [03461] 1-10-178 [03462] 1-10-179 [03463] 1-10-180 [03464] 1-10-181 [03465] 1-10-182 [03466] 1-10-183 [03467] 1-10-184 [03468] 1-10-185 [03469] 1-10-186 [03470] 1-10-187 [03471] 1-10-188 [03472] 1-10-189 [03473] 1-10-190 [03474] 1-10-191 [03475] 1-10-192 [03476] 1-10-193 [03477] 1-10-194 [03478] 1-10-195 [03479] 1-10-196 [03480] 1-10-197 [03481] 1-10-198 [03482] 1-10-199 [03483] 1-10-200 [03484] 1-11-1 [03485] 1-11-2 [03486] 1-11-3 [03487] 1-11-4 [03488] 1-11-5 [03489] 1-11-6 [03490] 1-11-7 [03491] 1-11-8 [03492] 1-11-9 [03493] 1-11-10 [03494] 1-11-11 [03495] 1-11-12 [03496] 1-11-13 [03497] 1-11-14 [03498] 1-11-15 [03499] 1-11-16 [03500] 1-11-17 [03501] 1-11-18 [03502] 1-11-19 [03503] 1-11-20 [03504] 1-11-21 [03505] 1-11-22 [03506] 1-11-23 [03507] 1-11-24 [03508] 1-11-25 [03509] 1-11-26 [03510] 1-11-27 [03511] 1-11-28 [03512] 1-11-29 [03513] 1-11-30 [03514] 1-11-31 [03515] 1-11-32 [03516] 1-11-33 [03517] 1-11-34 [03518] 1-11-35 [03519] 1-11-36 [03520] 1-11-37 [03521] 1-11-38 [03522] 1-11-39 [03523] 1-11-40 [03524] 1-11-41 [03525] 1-11-42 [03526] 1-11-43 [03527] 1-11-44 [03528] 1-11-45 [03529] 1-11-46 [03530] 1-11-47 [03531] 1-11-48 [03532] 1-11-49 [03533] 1-11-50 [03534] 1-11-51 [03535] 1-11-52 [03536] 1-11-53 [03537] 1-11-54 [03538] 1-11-55 [03539] 1-11-56 [03540] 1-11-57 [03541] 1-11-58 [03542] 1-11-59 [03543] 1-11-60 [03544] 1-11-61 [03545] 1-11-62 [03546] 1-11-63 [03547] 1-11-64 [03548] 1-11-65 [03549] 1-11-66 [03550] 1-11-67 [03551] 1-11-68 [03552] 1-11-69 [03553] 1-11-70 [03554] 1-11-71 [03555] 1-11-72 [03556] 1-11-73 [03557] 1-11-74 [03558] 1-11-75 [03559] 1-11-76 [03560] 1-11-77 [03561] 1-11-78 [03562] 1-11-79 [03563] 1-11-80 [03564] 1-11-81 [03565] 1-11-82 [03566] 1-11-83 [03567] 1-11-84 [03568] 1-11-85 [03569] 1-11-86 [03570] 1-11-87 [03571] 1-11-88 [03572] 1-11-89 [03573] 1-11-90 [03574] 1-11-91 [03575] 1-11-92 [03576] 1-11-93 [03577] 1-11-94 [03578] 1-11-95 [03579] 1-11-96 [03580] 1-11-97 [03581] 1-11-98 [03582] 1-11-99 [03583] 1-11-100 [03584] 1-11-101 [03585] 1-11-102 [03586] 1-11-103 [03587] 1-11-104 [03588] 1-11-105 [03589] 1-11-106 [03590] 1-11-107 [03591] 1-11-108 [03592] 1-11-109 [03593] 1-11-110 [03594] 1-11-111 [03595] 1-11-112 [03596] 1-11-113 [03597] 1-11-114 [03598] 1-11-115 [03599] 1-11-116 [03600] 1-11-117 [03601] 1-11-118 [03602] 1-11-119 [03603] 1-11-120 [03604] 1-11-121 [03605] 1-11-122 [03606] 1-11-123 [03607] 1-11-124 [03608] 1-11-125 [03609] 1-11-126 [03610] 1-11-127 [03611] 1-11-128 [03612] 1-11-129 [03613] 1-11-130 [03614] 1-11-131 [03615] 1-11-132 [03616] 1-11-133 [03617] 1-11-134 [03618] 1-11-135 [03619] 1-11-136 [03620] 1-11-137 [03621] 1-11-138 [03622] 1-11-139 [03623] 1-11-140 [03624] 1-12-1 [03625] 1-12-2 [03626] 1-12-3 [03627] 1-12-4 [03628] 1-12-5 [03629] 1-12-6 [03630] 1-12-7 [03631] 1-12-8 [03632] 1-12-9 [03633] 1-12-10 [03634] 1-12-11 [03635] 1-12-12 [03636] 1-12-13 [03637] 1-12-14 [03638] 1-12-15 [03639] 1-12-16 [03640] 1-12-17 [03641] 1-12-18 [03642] 1-12-19 [03643] 1-12-20 [03644] 1-12-21 [03645] 1-12-22 [03646] 1-12-23 [03647] 1-12-24 [03648] 1-12-25 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1-12-88 [03712] 1-12-89 [03713] 1-12-90 [03714] 1-12-91 [03715] 1-12-92 [03716] 1-12-93 [03717] 1-12-94 [03718] 1-12-95 [03719] 1-12-96 [03720] 1-12-97 [03721] 1-12-98 [03722] 1-12-99 [03723] 1-12-100 [03724]