CHIRAL COMPOUNDS

Abstract

The invention relates to chiral compounds of formula I

##STR00001##

wherein the parameters have the meaning given in claim 1, to liquid crystal mixtures comprising at least one chiral compound of formula I, to chiral linear or crosslinked liquid crystal polymers obtainable by polymerizing a polymerizable mixture comprising at least one chiral compound of formula I, to the use of chiral compound of formula I and mixtures and polymers obtained thereof in liquid crystal displays, active and passive optical elements, adhesives, synthetic resins with anisotropic mechanical properties, cosmetic and pharmaceutical compositions, diagnostics, liquid crystal pigments, for decorative and security applications, nonlinear optics, optical information storage or as chiral dopants, and to a liquid crystal display comprising a mixture comprising at least one chiral compound of formula I.

Claims

1. Chiral compound of formula I ##STR00263## wherein L.sup.11, L.sup.21 each, identically or differently, denote F, Cl, Br, I, CN, SCN, SF.sub.5, straight chain or branched alkyl with up to 25 C atoms which may be unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, it being also possible for one or more non-adjacent CH.sub.2 groups to be replaced, in each case independently from one another, by O, S, NH, NR.sup.0, CO, C(O)O, OC(O), OC(O)O, SC(O), C(O)S, CH?CH or C?C in such a manner that O and/or S atoms are not linked directly to one another, a polymerizable group, or cycloalkyl or aryl with up to 20 C atoms that is optionally mono- or polysubstituted by L.sup.31 or by a polymerizable group, R.sup.0 is H or alkyl with 1 to 4 C atoms, one of M.sup.1 and M.sup.2 is Z.sup.31-A.sup.31-(Z.sup.32-A.sup.32).sub.m-R.sup.31 and the other is R.sup.41 or A.sup.41, or both of M.sup.1 and M.sup.2 are, identically or differently, Z.sup.3-A.sup.31-(Z.sup.32-A.sup.32).sub.m-R.sup.31, or ##STR00264## U.sup.1 and U.sup.2 each, identically or differently, denote CH.sub.2, CF.sub.2, O, S, CO or CS, V.sup.1 and V.sup.2 each, identically or differently, denote a single bond or (CH.sub.2).sub.n, wherein up to three non-adjacent CH.sub.2-groups may be replaced by O and/or S, Z.sup.11, Z.sup.12, Z.sup.21, Z.sup.22, Z.sup.31 and Z.sup.32 each, identically or differently, denote O, S, CO, COO, OCO, OCOO, CONR.sup.0, NR.sup.0CO, OCH.sub.2, CH.sub.2O, SCH.sub.2, CH.sub.2S, CF.sub.2O, OCF.sub.2, CF.sub.2S, SCF.sub.2, CH.sub.2CH.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CF.sub.2CF.sub.2, CH?N, N?CH, N?N, CH?CH, CF?CH, CH?CF, CF?CF, C?C, CH?CHCOO, OCOCH?CH or a single bond, A.sup.11, A.sup.12, A.sup.21, A.sup.22, A.sup.31, A.sup.32, and A.sup.41 each, identically or differently, denote 1,4-phenylene in which, in addition, one or more CH groups may be replaced by N, 1,4-cyclohexylene in which, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by O and/or S, 1,3-dioxolane-4,5-diyl, 1,4-cyclohexenylene, 1,4-bicyclo[2,2,2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, it being possible for all these groups to be unsubstituted, mono- or polysubstituted with L.sup.31, L.sup.31 each, identically or differently, denote halogen or a cyano, nitro, alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 7 C atoms, wherein one or more H atoms may be substituted by F or Cl, R.sup.11, R.sup.21 R.sup.31 and R.sup.41 each, identically or differently, denote H, F, Cl, Br, I, CN, SCN, OH, SF.sub.5, straight chain or branched alkyl with up to 25 C atoms which may be unsubstituted, mono- or polysubstituted by F, Cl, Br, I or CN, it being also possible for one or more non-adjacent CH.sub.2 groups to be replaced, in each case independently from one another, by O, S, NH, NR.sup.0, CO, C(O)O, OC(O), OC(O)O, SC(O), C(O)S, CH?CH or C?C in such a manner that O and/or S-atoms are not linked directly to one another, or a polymerizable group, m is 0, 1 or 2, m1, m2 each, identically or differently, is 0, 1, 2 or 3, n is an integer from 1 to 7, r1, r2 each, identically or differently, denote 0, 1, 2, 3, 4 or 5, and s denotes 0 or 1.

2. Chiral compound according to claim 1, wherein M.sup.1 denotes H, M.sup.2 denotes Z.sup.31-A.sup.31-(Z.sup.32-A.sup.32).sub.m-R.sup.31 and m is 0 or 1.

3. Chiral compound according to claim 1, wherein ##STR00265## and m is 0 or 1.

4. Chiral compound according to claim 1, selected from the group of compounds of the following formulae ##STR00266## wherein A.sup.11, A.sup.12, A.sup.21, A.sup.22 each, identically or differently, denote 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl, it being possible for all these groups to be unsubstituted, mono- or polysubstituted with L.sup.31, R.sup.11, R.sup.21, R.sup.31 and R.sup.41 each, identically or differently, denote H, F, Cl, CN, straight chain or branched alkyl with up to 7 C atoms which may be unsubstituted, mono- or polysubstituted by F, Cl, or CN, it being also possible for one or more non-adjacent CH.sub.2 groups to be replaced, in each case independently from one another, by O, CO, C(O)O, OC(O), OCOO, SC(O), C(O)S, CH?CH or C?C in such a manner that O and/or S atoms are not linked directly to one another, or a polymerizable group. Z.sup.11, Z.sup.12, Z.sup.21 and Z.sup.22 each, identically or differently, denote O, CO, C(O)O, OC(O), OC(O)O, OCH.sub.2, CH.sub.2O, CF.sub.2O, OCF.sub.2, CH.sub.2CH.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CF.sub.2CF.sub.2, CH?CH, CF?CH, CH?CF, CF?CF, C?C, or a single bond, Z.sup.31 each, identically or differently, denote O, OC(O), OCH.sub.2, CH.sub.2CH.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CF.sub.2CF.sub.2 or a single bond, L.sup.11, L.sup.21, L.sup.31 each, identically or differently, denote F, Cl, or alkyl or alkoxy with 1 to 7 C atoms, wherein one or more H atoms may be substituted by F or Cl. m1, m2 each, identically or differently, is 0, 1, 2 or 3, r1, r2, s1 each, identically or differently, are 0, 1 or 2, and s denotes 0 or 1.

5. Chiral compound according to claim 1, wherein at least one of R.sup.11, R.sup.21 and R.sup.31 denotes or comprises a polymerizable group.

6. Liquid crystal mixture, characterised in that it comprises one or more chiral compounds of formula I according to claim 1.

7. Liquid crystal mixture according to claim 6, characterised in that it exhibits a cholesteric phase.

8. Liquid crystal mixture according to claim 6, characterised in that it exhibits a Blue Phase.

9. Polymerizable liquid crystal mixture comprising one or more compounds of formula I according to claim 1 and at least one polymerizable mesogenic compound, which can be said compound of formula I and/or an additional polymerizable mesogenic compound.

10. Chiral linear or crosslinked liquid crystal polymer obtainable by polymerizing a mixture according to claim 9.

11. A liquid crystal display of the Blue Phase, STN, TN, AMD-TN, temperature compensation, ferroelectric, guest-host, phase change or surface stabilized or polymer stabilized cholesteric texture (SSCT, PSCT) display type; an active or passive optical element, an adhesive, synthetic resin with anisotropic mechanical properties, cosmetic or pharmaceutical composition, a liquid crystal pigment, nonlinear optics, optical information storage or chiral dopants comprising a chiral compound according to claim 1.

12. Liquid crystal display comprising a liquid crystal mixture according to claim 6.

13. Liquid crystal display according to claim 12, characterised in that it contains a polymer stabilised Blue Phase.

14. Liquid crystal display of claim 12, wherein the liquid crystal mixture is cholesteric and the display is of the SSCT type.

15. Colour filter, broadband reflective polarizer, patterned film or security marking obtained from a polymerizable mixture according to claim 9.

16. Process, characterised in that a compound of the formula ##STR00267## is transformed into a compound of formula I by alkylation or acetalisation, wherein the occurring groups are defined as indicated in claim 1.

Description

EXAMPLES

[0254] In the following examples the invention is described in grater detail without delimiting it in any way.

[0255] Examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

1. Synthesis

Example 1: 12,15-Di(naphthalen-2-yl)-5-(4-pentylcyclohexyl)-5,6-dihydro-4H-dinaphtho[2,1-f:1,2-h][1,5]dioxonine

1.1 7-Methoxy-2-trifluoromethanesulfonyloxy naphthalene

[0256] ##STR00236##

[0257] To a mixture of 7-methoxy-2-naphthol (25.0 g, 144 mmol) and DMAP (0.70 g, 5.7 mmol) in CH.sub.2Cl.sub.2 (400 mL), triethylamine (30 mL) is added. The yellow reaction mixture is cooled to 0? C. At this temperature trifluoromethane sulfonic acid anhydride (33 mL, 200 mmol) is added dropwise. The solution is allowed to warm to room temperature and stirred for 20 h. The resulting mixture is poured into ice water and extracted with CH.sub.2Cl.sub.2. The combined organic layers are washed with water (1?200 mL), dried with NaSO.sub.4 and concentrated under reduced pressure. The product is purified by column chromatography (heptane/toluene 1:1) and crystallized from heptane.

1.2 7-Methoxy-2,2-binaphthyl

[0258] ##STR00237##

[0259] A flask is flushed with nitrogen and charged with a mixture of 7-methoxy-2-trifluoromethanesulfonyloxy naphthalene (60.0 g, 195.9 mmol), 2-naphthylboronic acid (41.70 g, 235.1 mmol) and THF (700 mL). Then NaBO.sub.2.4H.sub.2O (41.34 g, 293.9 mmol), 180 mL water, PdCl.sub.2(PPh.sub.3).sub.2 (2.75 g, 3.9 mmol) and 2-3 drops of hydrazinium hydroxide are added. The mixture is stirred at 60? C. for 20 h, cooled to room temperature, diluted with water (300 mL) and extracted with MTB ether (600 mL). The organic phases are washed with water (1?400 mL), dried with NaSO.sub.4 and concentrated under reduced pressure. The product is purified by column chromatography (heptane/toluene 1:1) and crystallized from heptane.

1.3 7-Hydroxy-2,2-binaphthyl

[0260] ##STR00238##

[0261] To a solution of 7-methoxy-2,2-binaphthyl (1.50 g, 5.2 mmol) in CH.sub.2Cl.sub.2 (30 mL) at 5? C. BBr.sub.3 (0.75 mL, 7.9 mmol) is added. The solution is allowed to warm to room temperature and stirred for 20 h. The excess of BBr.sub.3 is decomposed by the dropwise addition of water. The resulting mixture is diluted with water and extracted with CH.sub.2Cl.sub.2 (100 mL). The organic phase is washed with saturated NaHCO.sub.3 (2?50 mL), water (1?50 mL) and dried with NaSO.sub.4. The solvent is removed under reduced pressure and the product is purified by crystallization from toluene.

1.4 2,2-Dihydroxy-7,7-dinaphthyl-1,1-binaphthyl

[0262] ##STR00239##

[0263] 7-Hydroxy-2,2-binaphthyl (1.00 g, 3.7 mmol) is added to a mixture of CuCl(OH)-TMEDA (20 mg, 0.04 mmol) in CH.sub.2Cl.sub.2 (40 mL) and the whole is stirred at room temperature for 20 h exposed to air. The solvent is removed under reduced pressure and purified by column chromatography (toluene/ethylacetate 9:1). Crystallization from toluene gives 2,2-dihydroxy-7,7-dinaphthyl-1,1-binaphthyl as a white solid.

1.5 12,15-Di(naphthalen-2-yl)-5-(4-pentylcyclohexyl)-5,6-dihydro-4H-dinaphtho[2,1-f:1,2-h][1,5]dioxonine

[0264] ##STR00240##

[0265] A mixture of 2,2-dihydroxy-7,7-dinaphthyl-1,1-binaphthyl (1.50 g, 2.48 mmol) and K.sub.2CO.sub.3 (0.38 g, 2.73 mmol) in 30 mL DMF is stirred at 80? C. At this temperature a solution of 2-(4-n-pentylcyclohexyl)propane-1,3-diolditosylate (1.64 g, 2.97 mmol) in 20 mL DMF is added dropwise to the reaction mixture. The reaction is stirred for 20 h at 80? C. After cooling to room temperature, the reaction mixture is poured onto water and extracted with MTB ether (100 mL). The organic phase was washed with water (1?50 mL) and dried with NaSO.sub.4. The solvent is removed under reduced pressure and the product is purified by column chromatography (heptane/toluene 1:1). The racemic product is separated into enantiomers by chiral HPLC on ChiralPak IA. 12,15-Di(naphthalen-2-yl)-5-(4-pentylcyclohexyl)-5,6-dihydro-4H-dinaphtho[2,1-f:1,2-h][1,5]dioxonine is obtained as colorless solid, mp. 113? C.

[0266] This standard procedure (SP-1) is also used for the reaction between 2,2-Dihydroxy-7,7-dinaphthyl-1,1-binaphthyl and the following ditosylates to give Examples 2 to 5.

##STR00241##

Example 5: 2,2-Methylenedioxy-7,7-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene

5.1 7-(4-(4-propylcyclohexyl)phenyl)naphthalen-2-ol

[0267] ##STR00242##

[0268] A flask is flushed with nitrogen and charged with a mixture of 7-bromo-2-naphthol (10.5 g, 46.6 mmol), (4-(4-propylcyclohexyl)benzene)boronic acid (13.77 g, 55.92 mmol) and THF (100 mL). Then NaBO.sub.2.4H.sub.2O (9.83 g, 69.9 mmol), 30 mL water, PdCl.sub.2(PPh.sub.3).sub.2(1.64 g, 2.33 mmol) and 2-3 drops of hydrazinium hydroxide are added. The mixture is stirred at 60? C. for 5 h. The mixture is cooled to room temperature, diluted with water (250 mL), extracted with MTB ether (300 mL) and filtered through a pad of celite. The organic phases are is washed with water (1?100 mL), dried with NaSO.sub.4 and concentrated under reduced pressure. The product is purified by crystallization from heptane/ethylacetate 10:1.

5.2 7,7-bis(4-(4-propylcyclohexyl)phenyl)-[1,1-binaphthalene]-2,2-diol

[0269] ##STR00243##

[0270] 7-(4-(4-propylcyclohexyl)phenyl)naphthalen-2-ol (1.00 g, 2.9 mmol) is added to a mixture of CuCl(OH)-TMEDA (14 mg, 0.04 mmol) in CH.sub.2Cl.sub.2 (50 mL) and the reaction is stirred at room temperature for 4 h exposed to air. The solvent is removed under reduced pressure and purified by column chromatography (toluene/ethylacetate 95:5). Crystallization from a mixture of heptane/ethyl acetate/toluene 5:4:1 gives 7,7-bis(4-(4-propyl-cyclohexyl)phenyl)-[1,1-binaphthalene]-2,2-diol as a white solid.

5.3 2,2-Methylenedioxy-7,7-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene

[0271] ##STR00244##

[0272] A mixture of 7,7-bis(4-(4-propylcyclohexyl)phenyl)-[1,1-binaphthalene]-2,2-diol (2.00 g, 2.90 mmol), diiodomethane (2.33 g, 8.71 mmol) and K.sub.2CO.sub.3 (1.73 g, 17.42 mmol) in 50 mL DMF is stirred at 80? C. under nitrogen for 20 h. After cooling to room temperature, the reaction mixture is poured onto water (100 mL) and extracted with MTB ether (200 mL). The organic phase is washed with water (1?100 mL) and dried with NaSO.sub.4. The solvent is removed under reduced pressure and the product is purified by column chromatography (toluene). The racemic product is separated into enantiomers by chiral HPLC on ChiralCel OD-H to give optically active 2,2-Methylenedioxy-7,7-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene as colorless crystals, m.p 125? C.

Example 6: 5-(4-pentylcyclohexyl)-12,15-bis(4-(4-propylcyclohexyl)-phenyl)-5,6-dihydro-4H-dinaphtho[2,1-f:1,2-h][1,5]dioxonine

[0273] ##STR00245##

[0274] From 7,7-bis(4-(4-propylcyclohexyl)phenyl)-[1,1-binaphthalene]-2,2-diol (step 5.2) example 6 is synthesized using the standard procedure SP-1 described above. The racemic product is separated into enantiomers by chiral HPLC on ChiralPak AD-H.

Example 7: 2,2-Methylenedioxy-7,7-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene

7.1 7-(4-(4-propylcyclohexyl)phenyl)naphthalen-2-ol

[0275] ##STR00246##

[0276] A flask is flushed with nitrogen and charged with a mixture of 7-bromo-2-naphthol (10.50 g, 46.6 mmol), (4-(4-propylcyclohexyl)phenyl)boronic acid (13.77 g, 55.92 mmol) and THF (100 mL). Then NaBO.sub.2. 4H.sub.2O (9.83 g, 69.9 mmol), 30 mL water, PdCl.sub.2(PPh.sub.3).sub.2(1.64 g, 2.33 mmol) and 2-3 drops of hydrazinium hydroxide are added. The mixture is stirred at 60? C. for 5 h. The mixture is cooled to room temperature, diluted with water (250 mL), extracted with MTB ether (300 mL) and filtered through a pad of celite. The organic phases are washed with water (1?100 mL), dried with NaSO.sub.4 and concentrated under reduced pressure. The product is purified by crystallization from heptane/ethyl acetate (10:1).

7.2 7,7-bis(4-(4-propylcyclohexyl)phenyl)-[1,1-binaphthalene]-2,2-diol

[0277] ##STR00247##

[0278] 7-(4-(4-propylcyclohexyl)phenyl)naphthalen-2-ol (1.00 g, 2.9 mmol) is added to a mixture of CuCl(OH)-TMEDA (14 mg, 0.04 mmol) in CH.sub.2Cl.sub.2 (50 mL) and the whole is stirred at room temperature for 4 h in open air. The solvent is removed under reduced pressure and purified by column chromatography (toluene/ethyl acetate 95:5). Crystallization from a mixture of heptane/ethyl acetate/toluene 5:4:1 gives 7,7-bis(4-(4-propyl-cyclohexyl)phenyl)-[1,1-binaphthalene]-2,2-diol as a white solid.

7.3 2,2-Methylenedioxy-7,7-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene

[0279] ##STR00248##

[0280] A mixture of 7,7-bis(4-(4-propylcyclohexyl)phenyl)-[1,1-binaphthalene]-2,2-diol (2.00 g, 2.90 mmol), diiodomethane (2.33 g, 8.71 mmol), K.sub.2CO.sub.3 (1.73 g, 17.42 mmol) and 50 mL DMF is stirred at 80? C. under nitrogen for 20 h. After cooling to room temperature, the reaction mixture is poured into water (100 mL) and extracted with MTB ether (200 mL). The organic phase is washed with water (1?100 mL) and dried with NaSO.sub.4. The solvent is removed under reduced pressure and the product is purified by column chromatography (toluene). Crystallization from heptane gives 2,2-methylenedioxy-7,7-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene as a colorless solid. The racemic product is separated into enantiomers by chiral HPLC on ChiralCel OD-H to give optically active 2,2-Methylenedioxy-7,7-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene as colorless solid, mp. 113? C.

[0281] From 7,7-bis(4-(4-propylcyclohexyl)phenyl)-[1,1-binaphthalene]-2,2-diol (step 7.2) and according to general procedure SP-1 above, the following examples 8, 9 an 10 are obtained.

##STR00249##

[0282] In analogy to example 1 the compounds of the formula

##STR00250##

[0283] are obtained:

TABLE-US-00007 Example R.sup.11 R.sup.21 R.sup.31 11 H H CH.sub.3 12 H H C.sub.2H.sub.5 13 H H n-C.sub.3H.sub.7 14 H H n-C.sub.4H.sub.9 1 H H n-C.sub.5H.sub.11 15 CH.sub.3 CH.sub.3 CH.sub.3 16 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 17 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 18 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 19 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 20 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 21 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 22 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 23 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 24 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 25 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 26 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 27 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 28 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 29 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 30 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 31 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 32 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 33 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 34 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 35 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 36 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 37 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 38 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 39 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0284] In analogy to example 2 the compounds of the formula

##STR00251##

[0285] are obtained:

TABLE-US-00008 Example R.sup.11 R.sup.21 R.sup.31 40 H H CH.sub.3 41 H H C.sub.2H.sub.5 2 H H n-C.sub.3H.sub.7 42 H H n-C.sub.4H.sub.9 43 H H n-C.sub.5H.sub.11 44 CH.sub.3 CH.sub.3 CH.sub.3 45 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 46 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 47 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 48 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 49 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 50 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 51 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 52 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 53 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 54 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 55 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 56 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 57 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 58 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 59 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 60 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 61 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 62 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 63 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 64 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 65 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 66 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 67 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 68 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0286] In analogy to example 3 the compounds of the formula

##STR00252##

[0287] are obtained:

TABLE-US-00009 Example R.sup.11 R.sup.21 R.sup.31 69 H H CH.sub.3 70 H H C.sub.2H.sub.5 3 H H n-C.sub.3H.sub.7 71 H H n-C.sub.4H.sub.9 72 H H n-C.sub.5H.sub.11 73 CH.sub.3 CH.sub.3 CH.sub.3 74 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 75 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 76 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 77 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 78 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 79 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 80 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 81 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 82 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 83 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 84 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 85 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 86 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 87 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 88 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 89 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 90 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 91 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 92 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 93 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 94 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 95 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 96 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 97 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0288] In analogy to example 4 the compounds of the formula

##STR00253##

[0289] are obtained:

TABLE-US-00010 Example R.sup.11 R.sup.21 R.sup.31 98 H H CH.sub.3 99 H H C.sub.2H.sub.5 4 H H n-C.sub.3H.sub.7 100 H H n-C.sub.4H.sub.9 101 H H n-C.sub.5H.sub.11 102 CH.sub.3 CH.sub.3 CH.sub.3 103 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 104 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 105 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 106 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 107 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 108 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 109 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 110 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 111 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 112 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 113 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 114 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 115 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 116 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 117 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 118 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 119 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 120 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 121 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 122 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 123 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 124 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 125 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 126 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0290] In analogy to example 5 the compounds of the formula

##STR00254##

[0291] are obtained:

TABLE-US-00011 Example R.sup.11 R.sup.21 R.sup.31 127 H H H 128 H H CH.sub.3 129 H H C.sub.2H.sub.5 130 H H n-C.sub.3H.sub.7 131 H H n-C.sub.4H.sub.9 132 H H n-C.sub.5H.sub.11 133 CH.sub.3 CH.sub.3 H 134 CH.sub.3 CH.sub.3 CH.sub.3 135 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 136 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 137 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 138 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 139 C.sub.2H.sub.5 C.sub.2H.sub.5 H 140 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 141 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 142 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 143 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 144 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 5 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 145 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 146 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 147 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 148 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 149 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 150 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 151 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 152 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 153 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 154 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 155 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 156 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 157 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 158 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 159 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 160 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 161 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0292] In analogy to example 6 the compounds of the formula

##STR00255##

[0293] are obtained:

TABLE-US-00012 Example R.sup.11 R.sup.21 R.sup.31 162 H H CH.sub.3 163 H H C.sub.2H.sub.5 164 H H n-C.sub.3H.sub.7 165 H H n-C.sub.4H.sub.9 166 H H n-C.sub.5H.sub.11 167 CH.sub.3 CH.sub.3 CH.sub.3 168 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 169 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 170 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 171 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 172 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 173 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 174 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 175 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 176 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 177 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 178 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 179 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 180 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 6 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 181 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 182 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 183 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 184 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 185 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 186 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 187 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 188 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 189 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 190 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0294] In analogy to example 7 the compounds of the formula

##STR00256##

[0295] are obtained:

TABLE-US-00013 Example R.sup.11 R.sup.21 R.sup.31 191 H H H 192 H H CH.sub.3 193 H H C.sub.2H.sub.5 194 H H n-C.sub.3H.sub.7 195 H H n-C.sub.4H.sub.9 196 H H n-C.sub.5H.sub.11 197 CH.sub.3 CH.sub.3 H 198 CH.sub.3 CH.sub.3 CH.sub.3 199 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 200 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 201 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 202 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 203 C.sub.2H.sub.5 C.sub.2H.sub.5 H 204 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 205 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 206 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 207 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 208 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 209 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 210 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 211 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 212 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 213 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 214 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 215 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 216 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 217 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 218 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 219 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 220 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 221 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 222 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 223 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 224 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 225 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0296] In analogy to example 8 the compounds of the formula

##STR00257##

[0297] are obtained

TABLE-US-00014 Example R.sup.11 R.sup.21 R.sup.31 226 H H CH.sub.3 227 H H C.sub.2H.sub.5 228 H H n-C.sub.3H.sub.7 229 H H n-C.sub.4H.sub.9 230 H H n-C.sub.5H.sub.11 231 CH.sub.3 CH.sub.3 H 232 CH.sub.3 CH.sub.3 CH.sub.3 233 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 234 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 235 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 236 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 237 C.sub.2H.sub.5 C.sub.2H.sub.5 H 238 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 239 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 240 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 241 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 242 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 243 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 244 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 245 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 8 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 246 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 247 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 248 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 249 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 250 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 251 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 252 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 253 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 254 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 255 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 256 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 257 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 258 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 259 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0298] In analogy to example 9 the compounds of the formula

##STR00258##

[0299] are obtained.

TABLE-US-00015 Example R.sup.11 R.sup.21 R.sup.31 260 H H CH.sub.3 261 H H C.sub.2H.sub.5 262 H H n-C.sub.3H.sub.7 263 H H n-C.sub.4H.sub.9 264 H H n-C.sub.5H.sub.11 265 CH.sub.3 CH.sub.3 H 266 CH.sub.3 CH.sub.3 CH.sub.3 267 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 268 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 269 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 270 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 271 C.sub.2H.sub.5 C.sub.2H.sub.5 H 272 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 273 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 274 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 275 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 276 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 277 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 278 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 279 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 9 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 280 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 281 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 282 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 283 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 284 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 285 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 286 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 287 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 288 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 289 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 290 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 291 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 292 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 293 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

[0300] In analogy to example 10 the compounds of the formula

##STR00259##

[0301] are obtained:

TABLE-US-00016 Example R.sup.11* R.sup.21* R.sup.31 294 H H CH.sub.3 295 H H C.sub.2H.sub.5 296 H H n-C.sub.3H.sub.7 297 H H n-C.sub.4H.sub.9 298 H H n-C.sub.5H.sub.11 299 CH.sub.3 CH.sub.3 H 300 CH.sub.3 CH.sub.3 CH.sub.3 301 CH.sub.3 CH.sub.3 C.sub.2H.sub.5 10 CH.sub.3 CH.sub.3 n-C.sub.3H.sub.7 302 CH.sub.3 CH.sub.3 n-C.sub.4H.sub.9 303 CH.sub.3 CH.sub.3 n-C.sub.5H.sub.11 304 C.sub.2H.sub.5 C.sub.2H.sub.5 H 305 C.sub.2H.sub.5 C.sub.2H.sub.5 CH.sub.3 306 C.sub.2H.sub.5 C.sub.2H.sub.5 C.sub.2H.sub.5 307 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.3H.sub.7 308 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.4H.sub.9 309 C.sub.2H.sub.5 C.sub.2H.sub.5 n-C.sub.5H.sub.11 310 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 311 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 CH.sub.3 312 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 C.sub.2H.sub.5 313 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 314 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 315 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 316 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 317 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 CH.sub.3 318 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 C.sub.2H.sub.5 319 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 320 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 321 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 322 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 323 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 CH.sub.3 324 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 C.sub.2H.sub.5 325 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 326 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 327 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

Example 328: 2,2-Methylenedioxy-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene

[0302] The starting material, 2,2-Methylenedioxy-7,7-dibromo[1,1]binaphthalene is described in the literature [CAS-No. 263339-97-5].

328.1 2,2-Methylenedioxy-7-bromo-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene

[0303] ##STR00260##

[0304] 7.00 g (15.3 mmol) 2,2-methylenedioxy-7,7-dibromo[1,1]binaphthalene and 4-(4-propyl-cyclohexyl)benzene boronic acid are dissolved in 150 ml of THF and after addition of 3.24 g (23.0 mmol) sodium metaborate-tetrahydrate, 1.08 g (1.54 mmol) bis(triphenylphosphine) palladium(II)chloride and 7 ?l of hydrazinium hydrate, the reaction is heated at reflux overnight. The reaction is poured onto water, the aqueous layer is extracted with ether and the combined org. layers are washed with brine and dried over sodium sulfate. The solvent is evaporated and the residue is purified by chromatography to give 2,2-methylenedioxy-7-bromo-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene as a colourless solid.

328.2 2,2-Methylenedioxy-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene

[0305] ##STR00261##

[0306] 2,2-Methylenedioxy-7-bromo-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene is hydrogenated in THF on palladium-C (5%) catalyst until one equivalent of hydrogen is consumed. The catalyst is filtered off, the filtrate is evaporated and the residue is purified by chromatography to give 2,2-Methylenedioxy-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1]binaphthalene as colourless crystals, m.p. 152? C.

2. HTP Measurements

[0307] A nematic Host N1 for HTP measurements is prepared as follows

TABLE-US-00017 CPG-3-F 7.50% Clp. 60? C. CPG-5-F 7.50% PZG-2-F 9.50% PZG-2-F 10.00% PGP-2-3 8.00% PGU-2-F 9.00% PGU-3-F 9.00% PGUQU-3-F 9.50% PGUQU-4-F 9.50% PGUQU-5-F 9.50% PUQU-2-F 5.50% PUQU-3-F 5.50%

[0308] The HTP values are measured as described above and are listed in table 1.

TABLE-US-00018 TABLE 1 Compound Example HTP [?m.sup.?1] .sup.[1] HTP [?m.sup.?1] .sup.[2] R-5011 c.s. 95 145 1 1 119 N/A 2 2 103 N/A 3 3 100 N/A 4 4 120 N/A 5 5 128 200 6 6 146 271 7 7 141 201 8 8 124 204 9 9 137 220 10 10 129 208 c.s.: comparative substance 1 .sup.[1] measured in MLC-6260 .sup.[2] measured in N1

[0309] As shown in table 1, compounds of examples 1 to 10 exhibit significantly higher HTP values than R-5011 from the state of the art.

3. Mixture Examples

Comparative Example 1

[0310] A cholesteric mixture C1 contains 96.98% of a nematic component N2:

TABLE-US-00019 TABLE 1 Nematic Host N2 CC-5-O1 7.0% Kp. 86 CCZC-3-3 3.0% CCZC-3-5 3.0% ?n 0.0645 CCZC-4-3 3.0% n.sub.e 1.5325 CCU-2-F 7.0% CCU-3-F 5.0% ?? +10.2 CCZU-2-F 6.0% CCZU-3-F 15.0% CCZU-5-F 6.0% CDU-2-F 9.0% CDU-3-F 9.0% CDU-5-F 16.0% CC-3-T 7.0% CC-5-T 8.0% CCZPC-3-4 3.0% CCZPC-3-3 3.0%

[0311] and 3.02% of chiral dopant R-5011 of formula

##STR00262##

[0312] The mixture C1 shows a reflection wavelength of ?=400 nm.

Mixture Example M1

[0313] A cholesteric mixture M1 is prepared from nematic host N2 above and the compound of synthesis example 1.

TABLE-US-00020 TABLE 2 Cholesteric mixture M1 Mass % N2 97.59 Example 1 2.41

Mixture Example M2

[0314] A cholesteric mixture M2 is prepared from nematic host N2 above and the compound of synthesis example 6.

TABLE-US-00021 TABLE 3 Cholesteric mixture M2 Mass % N2 98.19 Example 6 1.81

Mixture Example M3

[0315] A nematic Host N3 is prepared as follows:

TABLE-US-00022 TABLE 4 Nematic Host N3 GUQGU-3-F 8.00% Kp. 72.5 GUQGU-4-F 6.00% GUQGU-5-F 4.00% ?n 0.1929 GUUQU-3-N 6.00% n.sub.e 1.6811 GUQU-3-F 7.00% n.sub.o 1.4882 GUQU-4-F 6.00% GUQGU-2-T 12.00% ?? 202.1 GUQGU-3-T 12.00% ?.sub.? 213.6 GUQGU-4-T 12.00% ?.sub.? 11.5 GUQGU-5-T 12.00% DPGU-4-F 8.00% PGU-5-T 3.00% PGU-4-T 4.00%

[0316] A Blue Phase mixture M3 is prepared from the nematic host mixture N3 above and the compound of synthesis example 6:

TABLE-US-00023 TABLE 5 Blue Phase mixture M3 Mass % N3 97.2 Example 6 2.8