Thiophene compound, liquid-crystalline medium and liquid-crystal display comprising the same

Abstract

A liquid-crystalline medium, preferably having a nematic phase and dielectric anisotropy of 0.5 or more, which comprises one or more compounds of formula T

##STR00001## in which

##STR00002##

denotes

##STR00003##

and the use thereof in an electro-optical display, particularly in an active-matrix display based on the IPS or FFS effect, to displays of this type which contain a liquid-crystalline medium of this type, and to the compounds of formula T and their use for the improvement of the transmission and/or response times of a liquid-crystalline medium which contains one or more additional mesogenic compounds.

Claims

1. A liquid-crystalline medium comprising one or more compounds of formula T ##STR00294## in which ##STR00295## denotes ##STR00296## and each ##STR00297## independently of each other, denotes ##STR00298## wherein the rings optionally may each be substituted by one or two alkyl groups, n denotes 1 or 2, R.sup.S denotes alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy, wherein one CH.sub.2 group may be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclo-pentenylene, cyclopentylene, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, wherein one CH.sub.2 group may be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,3-cyclo-pentenylene, and X.sup.S denotes F, Cl, CN, NCS fluorinated alkyl, fluorinated alkenyl, fluorinated alkoxy or fluorinated alkenyloxy.

2. The liquid-crystalline medium according to claim 1, further comprising one or more compounds S of formulae T-1 and/or T-2: ##STR00299## in which R.sup.S denotes alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, and X.sup.S denotes F, Cl, CN, NCS, fluorinated alkyl, fluorinated alkenyl, fluorinated alkoxy or fluorinated alkenyloxy.

3. The liquid-crystalline medium according to claim 2, comprising one or more compounds of formula T-1.

4. The liquid-crystalline medium according to claim 1, further comprising one or more compounds of formulae II and III: ##STR00300## in which R.sup.2 denotes alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, ##STR00301## and ##STR00302## on each appearance, independently of one another, denote ##STR00303## L.sup.21 and L.sup.22 denote H or F, X.sup.2 denotes halogen, halogenated alkyl or alkoxy having 1 to 3 C atoms or halogenated alkenyl or alkenyloxy having 2 or 3 C atoms, m denotes 0, 1, 2 or 3, R.sup.3 denotes alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms ##STR00304## on each appearance, independently of one another, are ##STR00305## L.sup.31 and L.sup.32, independently of one another, denote H or F, X.sup.3 denotes halogen, halogenated alkyl or alkoxy having 1 to 3 C atoms or halogenated alkenyl or alkenyloxy having 2 or 3 C atoms, F, Cl, OCF.sub.3, OCHF.sub.2, OCH.sub.2CF.sub.3, OCHCF.sub.2, OCHCH.sub.2 or CF.sub.3, Z.sup.3 denotes CH.sub.2CH.sub.2, CF.sub.2CF.sub.2, COO, trans-CHCH, trans-CFCF, CH.sub.2O or a single bond, and n denotes 0, 1, 2 or 3.

5. The liquid-crystalline medium according to claim 1, further comprising one or more compounds of formulae IV and/or V: ##STR00306## in which R.sup.41 and R.sup.42, independently of one another, are alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, ##STR00307## independently of one another and, if ##STR00308## occurs twice, also these independently of one another, denote ##STR00309## Z.sup.41 and Z.sup.42, independently of one another and, if Z.sup.41 occurs twice, also these independently of one another, denote CH.sub.2CH.sub.2, COO, trans-CHCH, trans-CFCF, CH.sub.2O, CF.sub.2O, CC or a single bond, p denotes 0, 1 or 2, R.sup.51 and R.sup.52, independently of one another, are alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, ##STR00310## if present, each, independently of one another, denote ##STR00311## Z.sup.51 to Z.sup.53 each, independently of one another, denote CH.sub.2CH.sub.2, CH.sub.2O, CHCH, CC, COO or a single bond, and i and j each, independently of one another, denote 0 or 1.

6. The liquid-crystalline medium according to claim 5, further comprising one or more compounds of formulae VI to IX: ##STR00312## wherein R.sup.61 denotes an unsubstituted alkyl radical having 1 to 7 C atoms, an unsubstituted alkenyl radical having 2 to 7 C atoms, an unsubstituted alkoxy radical having 1 to 6 C atoms or an unsubstituted alkenyloxy radical having 2 to 6 C atoms, R.sup.62 denotes an unsubstituted alkyl radical having 1 to 7 C atoms, an unsubstituted alkoxy radical having 1 to 6 C atoms or an unsubstituted alkenyloxy radical having 2 to 6 C atoms, and I denotes 0 or 1, R.sup.71 denotes an unsubstituted alkyl radical having 1 to 7 C atoms, or an unsubstituted alkenyl radical having 2 to 7 C atoms, R.sup.72 denotes an unsubstituted alkyl radical having 1 to 7 C atoms, an unsubstituted alkoxy radical having 1 to 6 C atoms or an unsubstituted alkenyloxy radical having 2 to 6 C atoms, ##STR00313## denotes ##STR00314## R.sup.81 denotes an unsubstituted alkyl radical having 1 to 7 C atoms, or an unsubstituted alkenyl radical having 2 to 7 C atoms, R.sup.82 denotes an unsubstituted alkyl radical having 1 to 7 C atoms, an unsubstituted alkoxy radical having 1 to 6 C atoms or an unsubstituted alkenyloxy radical having 2 to 6 C atoms, preferably having 2, 3 or 4 C atoms, ##STR00315## denotes ##STR00316## Z.sup.8 denotes (CO)O, CH.sub.2O, CF.sub.2O or CH.sub.2CH.sub.2, o denotes 0 or 1, R.sup.91 and R.sup.92 independently of one another have the meaning given for R.sup.72 above, ##STR00317## denotes ##STR00318## p and q independently of each other denote 0 or 1.

7. The liquid-crystalline medium according to claim 1, further comprising one or more compounds of formula I ##STR00319## in which ##STR00320## denotes ##STR00321## denotes ##STR00322## n denotes 0 or 1, R.sup.11 and R.sup.12 independently of each other denote alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy, preferably having 1 to 7 C atoms, wherein one CH.sub.2 group may be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclo-pentenylene, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, wherein one CH.sub.2 group may be replaced by cyclo-propylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclo-pentenylene, and R.sup.11 alternatively denotes R.sup.1 and R.sup.12 alternatively denotes X.sup.1, R.sup.1 denotes alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy wherein one CH.sub.2 group may be replaced by cyclo-propylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclo-pentenylene, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, wherein one CH.sub.2 group may be replaced by cyclo-propylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclo-pentenylene, and X.sup.1 denotes F, Cl, fluorinated alkyl, fluorinated alkenyl, fluorinated alkoxy or fluorinated alkenyoxy.

8. The liquid-crystalline medium according to claim 7, having a total concentration of the compounds of formula S in the medium of 1% to 60%.

9. The liquid-crystalline medium according to claim 1, additionally comprising one or more chiral compounds.

10. An electro-optical display or electro-optical component, comprising a liquid-crystalline medium according to claim 1.

11. The electro-optical display according to claim 10, operating in IPS-, FFS, HB-FFS or XB-FFS mode.

12. The electro-optical display according to claim 10, containing an active-matrix addressing device.

13. The electro-optical display according to claim 10, that is a mobile display.

14. A process for the preparation of a liquid-crystalline medium according to claim 1, comprising mixing one or more compounds of formula S with one or more additional mesogenic compounds.

15. A compound of formula T ##STR00323## in which ##STR00324## denotes ##STR00325## independently of each other, denote ##STR00326## wherein the rings optionally may each be substituted by one or two alkyl groups, n denotes 1 or 2, R.sup.S denotes alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy, wherein one CH.sub.2 group may be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclo-pentenylene, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, wherein one CH.sub.2 group may be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclo-pentenylene, and X.sup.S denotes Cl, CN, NCS fluorinated alkyl, fluorinated alkenyl, fluorinated alkoxy or fluorinated alkenyloxy, and, in case at least one of the phenyl rings present bears an alkyl group and/or at least one of the the phenyl rings present bears two or more F atoms and/or n is 2 and both phenyl rings bear one or more F atoms X.sup.S, alternatively may denote F.

16. A process for the preparation of a compound of formula T according to claim 15, comprising coupling a fluorinated biphenyl halogenide to a polar thiophene boronic acid or an ester of a thiophene boronic acid.

Description

EXAMPLES

[0458] The following examples explain the present invention without restricting it in any way. However, the physical properties make it clear to the person skilled in the art what properties can be achieved and in what ranges they can be modified. In particular, the combination of the various properties which can preferably be achieved is thus well defined for the person skilled in the art.

[0459] The following abbreviations are used in the synthetic examples of the present application: [0460] BuLi n-Butyllithium, [0461] MTB ether tert-Butyl methyl ether, [0462] THF Tetrahydrofuran, and [0463] dist. Distilled.

Synthesis Example 1 (PUS-3-T)

Synthesis of 2-[2,6-difluoro-4-(4-propylphenyl)phenyl]-5-(trifluoro-methyl)thiophene

[0464] ##STR00246##

Step 1.1: 1,3-Difluoro-5-(4-propylphenyl)benzene

[0465] ##STR00247##

[0466] A mixture of (4-propylphenyl)boronic acid (1) (7.0 g, 42 mmol), 1-bromo-3,5-difluoro-benzene (2) (8.1 g, 40 mmol), bis(dibenzylideneacetone)-palladium(0) (50 mg, 0.87 mol) and tris-(o-tolyl)phosphine (130 mg, 42 mol) in acetone (120 mL) is heated to reflux under nitrogen atmosphere, followed by dropwise addition of a sodium hydroxide solution (2 N, 42 mL, 84 mmol). The reaction mixture is heated at reflux temperature for 2 h. Then it is allowed to cool to ambient temperature and diluted with MTB ether and dist. water. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with dist. water and brine, dried over sodium sulfate and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent heptane) to give 1,3-difluoro-5-(4-propylphenyl)benzene (3) as a colorless oil.

Step 1.2: 2-Bromo-1,3-difluoro-5-(4-propylphenyl)benzene

[0467] ##STR00248##

[0468] BuLi (26.0 mL, 15% in n-hexane, 41 mmol) is slowly added to a solution of 1,3-difluoro-5-(4-propylphenyl)benzene (3) (8.3 g, 35 mmol) in THF (60 mL) at 70 C. under a nitrogen atmosphere. The reaction mixture is stirred at 70 C. for 1 h. Then bromine (6.5 g, 40 mmol) is slowly added via syringe at 70 C. The reaction mixtures is allowed to warm up to room temperature after 30 min. The reaction is quenched by addition of aqueous sodium hydrogen sulfite solution. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with dist. water and brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent heptane) to give 2-bromo-1,3-difluoro-5-(4-propylphenyl)benzene (4) as a colorless oil.

Step 1.3: 2-[2,6-difluoro-4-(4-propylphenyl)phenyl]-5-(trifluoromethyl)thiophene

[0469] ##STR00249##

[0470] A mixture of 2-bromo-1,3-difluoro-5-(4-propylphenyl)benzene (4) (2.3 g, 7.4 mmol), potassium carbonate (1.7 g, 12 mmol), tris(dibenzylidene-acetone)-dipalladium(0) (35 mg, 38 mol) and CataCXium A (25 mg, 69 mol) in THF (40 ml) and dist. water (8 ml) is heated to reflux under a nitrogen atmosphere, followed by dropwise addition of a solution of [5-(trifluoromethyl)-2-thienyl]boronic acid (5) (CAS 958451-91-7) (1.5 g, 7.7 mmol) in THF (10 mL). The reaction mixture is heated at reflux temperature for 90 min. Then it is allowed to cool to room temperature and diluted with MTB ether and dist. water. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with dist. water and brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent heptane). Subsequent recrystallization of the crude product from isopropyl alcohol and heptane results in colorless crystals of 2-[2,6-difluoro-4-(4-propylphenyl)phenyl]-5-(trifluoromethyl)thiophene (6).

[0471] Compound (6) has the following phase characteristics:

[0472] K 39 C. SmA 137 C. I.

Synthesis Example 2 (PUS-3-F)

Synthesis of 2-[2,6-difluoro-4-(4-propylphenyl)phenyl]-5-fluoro-thiophene

[0473] ##STR00250##

Step 2.1: 2-[2,6-Difluoro-4-(4-propylphenyl)phenyl]-5-fluoro-thiophene

[0474] ##STR00251##

[0475] A mixture of 2-bromo-1,3-difluoro-5-(4-propylphenyl)benzene (4) (5.3 g, 17 mmol), potassium carbonate (3.5 g, 25 mmol), tris(dibenzylidene-acetone)-dipalladium(0) (80 mg, 87 mol) and CataCXium A (55 mg, 153 mol) in THF (80 mL) and dist. water (18 mL) is heated to reflux under nitrogen atmosphere, followed by dropwise addition of a solution of 2-(5-fluoro-2-thienyl)-4,4,5,5-tetramethyl-1,3-dioxaborolane (7) (4.1 g, 18 mmol) in THF (20 ml). The reaction mixture is heated at reflux temperature for 2 h. Then it is allowed to cool to ambient temperature and diluted with MTB ether and dist. water. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with dist. water and brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent heptane). Subsequent recrystallization of the crude product from isopropyl alcohol and heptane results in colorless crystals of 2-[2,6-difluoro-4-(4-propylphenyl)phenyl]-5-fluoro-thiophene (8). Compound (8) has the following phase characteristics:

[0476] K 67 C. S.sub.A 76 C. N 102 C. I.

Synthesis Example C-1 (LB(S)-3-OT)

Synthesis of 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethoxy-dibenzothiophene:

[0477] ##STR00252##

Step C-1.1: 3,2,3-Trifluoro-4-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-ol

[0478] ##STR00253##

[0479] A mixture of 6-bromo-2-fluoro-3-trifluoromethoxyphenol (2, CAS 1805580-01-1) (68.0 g, 0.25 mol), potassium carbonate (50.0 g, 0.36 mol), tris(dibenzylideneacetone)-dipalladium(0) (1.2 g, 1.25 mmol) and CataCXium A (1.4 g, 3.71 mmol) in THF (500 mL) and distilled water (100 mL) is heated to reflux under nitrogen atmosphere, followed by dropwise addition of a solution of 2,3-difluoro-4-(4-propyl-cyclohex-1-enyl)-phenylboronic acid (1, CAS 947607-78-5) (70.6 g, 0.25 mol) in THF (200 mL). The reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. Throughout this application, unless explicitly stated otherwise, room temperature and ambient temperature are used synonymously and signify a temperature of about 20 C., typically (201) C. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent 1-chlorobutane/heptane 1:1). 3,2,3-Trifluoro-4-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-ol (3) is isolated as a brown solid.

Step C-1.2: Trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-yl ester

[0480] ##STR00254##

[0481] Trifluoromethanesulfonic anhydride (31 mL, 0.19 mol) is slowly added to a solution of 3,2,3-trifluoro-4-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-ol (3) (66 g, 0.15 mol), TEA (32 mL, 0.23 mol) and DMAP (560 mg, 4.58 mmol) in dichloromethane (500 mL) at 5 C. under nitrogen atmosphere. The solution is stirred at room temperature overnight. The reaction mixture is purified by silica gel chromatography (solvent dichlormethane) to give trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-yl ester (4) as a brown oil.

Step C-1.3: 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethoxy-dibenzothiophene

[0482] ##STR00255##

[0483] This reaction is performed as a one-pot reaction. In the first step, a solution of trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-ylester (4) (87 g, 0.15 mol), 3-mercapto-propionic acid 2-ethylhexyl ester (45 mL, 0.19 mol), N-ethyldiisopropylamine (40 mL, 0.24 mol) and toluene (350 mL) is degassed with Argon for 1 h. Tris(dibenzylideneacetone)dipalladium(0) (1.5 g, 1.56 mmol) and (oxydi-2,1-phenylene)bis(diphenylphosphine) (1.6 g, 2.91 mmol) are quickly added to the solution, and the reaction mixture is heated at reflux temperature overnight. Then it is allowed to cool to room temperature. In the second step, a solution of potassium tent-butylate (22 g, 0.20 mol) in THF (200 mL) is added to the reaction mixture containing intermediate (5) in situ. The reaction mixture is heated at reflux temperature overnight, followed by addition of a second portion of a solution of potassium tent-butylate (11 g, 0.1 mol) in THF (100 mL). The reaction mixture is heated again at reflux temperature overnight. Then it is cooled to room temperature, quenched with distilled water and hydrochloric acid (25%) at 0 C. and diluted with MTB ether. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent heptane) to give 4,6-difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethoxy-dibenzothiophene (6) as white crystals.

[0484] Compound (6) has the following phase characteristics: [0485] K 66 C. SmA 181 C. I.

Synthesis Example C-2 (LB(S)-3-T)

Synthesis of 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethyl-dibenzothiophene:

[0486] ##STR00256##

Step C-2.1: 3,2,3-Trifluoro-4-trifluoromethyl-biphenyl-2-ol

[0487] ##STR00257##

[0488] A mixture of 6-bromo-2-fluoro-3-trifluoromethylphenol (2, CAS 1804908-52-8) (100 g, 0.38 mol), potassium carbonate (80 g, 0.58 mol), tris(dibenzylideneacetone)-dipalladium(0) (1.9 g, 2.0 mmol) and CataCXium A (2.2 g, 5.8 mmol) in THF (500 mL) and distilled water (200 mL) is heated to reflux under nitrogen atmosphere, followed by dropwise addition of a solution of 2,3-difluoro-4-phenylboronic acid (1, CAS 121219-16-7) (70 g, 0.43 mol) in THF (300 mL). The reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. Throughout this application, unless explicitly stated otherwise, room temperature and ambient temperature are used synonymously and signify a temperature of about 20 C., typically (201) C. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent dichloromethane). 3,2,3-Trifluoro-4-trifluoromethyl-biphenyl-2-ol (3) is isolated as a brown solid.

Step C-2.2: Trifluoromethanesulfonic acid 3,2,3-trifluoro-4-trifluoromethyl-biphenyl-2-yl ester

[0489] ##STR00258##

[0490] Trifluoromethanesulfonic anhydride (30.0 mL, 0.18 mol) is slowly added to a solution of 3,2,3-trifluoro-4-trifluoromethyl-biphenyl-2-ol (3) (46.8 g, 0.15 mol), TEA (32 mL, 0.23 mol) and DMAP (600 mg, 4.9 mmol) in dichloromethane (300 mL) at 5 C. under nitrogen atmosphere. The solution is stirred at room temperature overnight. The reaction mixture is purified by silica gel chromatography (solvent dichlormethane) to give trifluoromethanesulfonic acid 3,2,3-trifluoro-4-trifluoromethyl-biphenyl-2-yl ester (4) as a yellow oil.

Step C-2.3: 4,6-Difluoro-3-trifluoromethyl-dibenzothiophene

[0491] ##STR00259##

[0492] This reaction is performed as a one-pot reaction. In the first step, a solution of trifluoromethanesulfonic acid 3,2,3-trifluoro-4-trifluoromethyl-biphenyl-2-yl ester (4) (66 g, 0.15 mol) and ethyl 3-mercaptopropionate (24 mL, 0.18 mol) in toluene (500 mL) is heated under nitrogen atmosphere to 80 C. Potassium carbonate (50 g, 0.36 mol), tris(dibenzylideneacetone)dipalladium(0) (7.0 g, 7.3 mmol) and (oxydi-2,1-phenylene)bis(diphenylphosphine) (8.0 g, 14.6 mmol) are quickly added to the solution, and the reaction mixture is heated at reflux temperature overnight. Then it is allowed to cool to room temperature. In the second step, a solution of potassium tert-butylate (18 g, 0.16 mol) in THF (150 mL) is added to the reaction mixture containing intermediate (5) in situ. The reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature, quenched with distilled water and hydrochloric acid (25%) at 0 C. and diluted with MTB ether. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent heptane) to give 4,6-difluoro-3-trifluoromethyl-dibenzothiophene (6) as yellow crystals.

Step C-2.4: 1-(4,6-Difluoro-7-trifluoromethyl-dibenzothiophen-3-yl)-4-propyl-cyclohexanol

[0493] ##STR00260##

[0494] Lithiumdiisopropylamide (6 mL, 2 M in cyclohexane/ethylbenzene/THF, 12 mmol) is added to a solution of 4,6-difluoro-3-trifluoromethyl-dibenzothiophene (6) (3.2 g, 10 mmol) in THF (100 mL) at 70 C. under nitrogen atmosphere. A solution of 4-propylcyclohexanone (1.7 g, 12 mmol) in THF (10 mL) is added after 1 h, and the reaction mixture is stirred for 2 h at 70 C. Then it is allowed to warm to room temperature and is stirred overnight. The reaction is quenched with distilled water and hydrochloric acid (25%) at 0 C. and diluted with MTB ether. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent dichlormethane) to give 1-(4,6-difluoro-7-trifluoromethyl-dibenzothiophen-3-yl)-4-propyl-cyclohexanol (7) as yellow crystals.

Step C-2.5: 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethyl-dibenzothiophene

[0495] ##STR00261##

[0496] A mixture of 1-(4,6-difluoro-7-trifluoromethyl-dibenzothiophen-3-yl)-4-propyl-cyclohexanol (7) (1.2 g, 2.5 mmol) and toluene-4-sulfonic acid monohydrate (50 mg, 0.3 mmol) in toluene (50 mL) is heated in a Dean Stark trap at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent 1-chlorobutane). Subsequent recrystallization of the crude product from heptane results in colorless crystals of 4,6-difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethyl-dibenzothiophene.

[0497] Compound (7) has the following phase characteristics: [0498] K 121 C. SmA 162 C. I.

Synthesis Example C-3 (CB(S)-3-T)

Synthesis of 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethyl-dibenzothiophene:

[0499] ##STR00262##

Step 3.1: 3,2,3-Trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-ol

[0500] ##STR00263##

[0501] A mixture of 6-bromo-2-fluoro-3-trifluoromethylphenol (2, CAS 1804908-52-8) (7.1 g, 26.9 mmol), potassium carbonate (5.6 g, 40.5 mmol), tris(dibenzylideneacetone)-dipalladium(0) (130 mg, 0.14 mmol) and CataCXium A (150 mg, 0.40 mmol) in THF (50 mL) and distilled water (15 mL) is heated to reflux under nitrogen atmosphere, followed by dropwise addition of a solution of 2,3-difluoro-4-(4-propyl-cyclohexyl)-phenylboronic acid (1, CAS 183438-45-1) (7.8 g, 27.2 mmol) in THF (25 mL). The reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. Throughout this application, unless explicitly stated otherwise, room temperature and ambient temperature are used synonymously and signify a temperature of about 20 C., typically (201) C. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent 1-chlorobutane/heptane 1:1). 3,2,3-Trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-ol (3) is isolated as a yellow solid.

Step C-3.2: Trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-yl ester

[0502] ##STR00264##

[0503] Trifluoromethanesulfonic anhydride (2.8 mL, 17.0 mmol) is slowly added to a solution of 3,2,3-trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-ol (3) (5.5 g, 13.2 mmol), TEA (2.8 mL, 20.2 mmol) and DMAP (50 mg, 0.41 mmol) in dichloromethane (50 mL) at 5 C. under nitrogen atmosphere. The solution is stirred at room temperature overnight. The reaction mixture is purified by silica gel chromatography (solvent dichlormethane) to give trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-yl ester (4) as a yellow oil.

Step C-3.3: 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethyl-dibenzothiophene

[0504] ##STR00265##

[0505] This reaction is performed as a one-pot reaction. In the first step, a solution of trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-yl ester (4) (7.3 g, 13.1 mmol) and ethyl 3-mercaptopropionate (2.2 mL, 16.7 mmol) in toluene (70 mL) is quickly heated under nitrogen atmosphere to 80 C. Potassium carbonate (5.0 g, 36.2 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.7 g, 0.73 mmol) and (oxydi-2,1-phenylene)bis(diphenylphosphine) (0.8 g, 1.46 mmol) are quickly added to the solution, and the reaction mixture is heated at reflux temperature overnight. Then it is allowed to cool to room temperature. In the second step, a solution of potassium tert-butylate (1.8 g, 16.0 mmol) in THF (20 mL) is added to the reaction mixture containing intermediate (5) in situ. The reaction mixture is heated at reflux temperature overnight, followed by addition of a second portion of a solution of potassium tent-butylate (1.8 g, 16.0 mmol) in THF (20 mL). The reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature, quenched with distilled water and hydrochloric acid (25%) at 0 C. and diluted with MTB ether. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent heptane) to give 4,6-difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethyl-dibenzothiophene (6) as yellowish crystals.

[0506] Compound (6) has the following phase characteristics: [0507] K 150 C. N (139 C.) I

Synthesis Example C-3a (CB(S)-3-T)

[0508] Alternatively, 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethyl-dibenzothiophene is obtained by hydrogenation of 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethyl-dibenzothiophene:

##STR00266##

Synthesis Example C-4 (CB(S)-3-OT)

[0509] Synthesis of 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethoxy-dibenzothiophene:

##STR00267##

Step C-4.1: 3,2,3-Trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-ol

[0510] ##STR00268##

[0511] A mixture of 6-bromo-2-fluoro-3-trifluoromethoxyphenol (2, CAS 1805580-01-1) (33.0 g, 0.12 mol), potassium carbonate (25.0 g, 0.18 mol), tris(dibenzylideneacetone)-dipalladium(0) (600 mg, 0.6 mmol) and CataCXium A (700 mg, 1.9 mmol) in THF (250 mL) and distilled water (75 mL) is heated to reflux under nitrogen atmosphere, followed by dropwise addition of a solution of 2,3-difluoro-4-(4-propyl-cyclohexyl)-phenylboronic acid (1, CAS 183438-45-1) (34.4 g, 0.12 mol) in THF (100 mL). The reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. Throughout this application, unless explicitly stated otherwise, room temperature and ambient temperature are used synonymously and signify a temperature of about 20 C., typically (201) C. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent 1-chlorobutane/heptane 1:1). 3,2,3-Trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-ol (3) is isolated as a yellow solid.

Step C-4.2: Trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-yl ester

[0512] ##STR00269##

[0513] Trifluoromethanesulfonic anhydride (6.0 mL, 36.4 mmol) is slowly added to a solution of 3,2,3-trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-ol (3) (12.6 g, 29.0 mmol), TEA (6.3 mL, 45.4 mmol) and DMAP (110 mg, 0.9 mmol) in dichloromethane (100 mL) at 5 C. under nitrogen atmosphere. The solution is stirred at room temperature overnight. The reaction mixture is purified by silica gel chromatography (solvent dichlormethane) to give trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-yl ester (4) as a yellow oil.

Step C-4.3: 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethoxy-dibenzothiophene

[0514] ##STR00270##

[0515] This reaction is performed as a one-pot reaction. In the first step, a solution of trifluoromethanesulfonic acid 3,2,3-trifluoro-4-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-yl ester (4) (16.3 g, 28.1 mmol) and ethyl 3-mercaptopropionate (5.0 mL, 37.9 mmol) in toluene (150 mL) is quickly heated under nitrogen atmosphere to 80 C. Potassium carbonate (10 g, 72.4 mmol), tris(dibenzylidene-acetone)dipalladium(0) (1.4 g, 1.5 mmol) and (oxydi-2,1-phenylene)bis(diphenylphosphine) (1.6 g, 2.9 mmol) are quickly added to the solution, and the reaction mixture is heated at reflux temperature overnight. Then it is allowed to cool to room temperature. In the second step, a solution of potassium tert-butylate (3.5 g, 31.2 mmol) in THF (50 mL) is added to the reaction mixture containing intermediate (5) in situ. The reaction mixture is heated at reflux temperature overnight, followed by addition of a second portion of a solution of potassium tert-butylate (3.5 g, 31.2 mmol) in THF (50 mL). The reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature, quenched with distilled water and hydrochloric acid (25%) at 0 C. and diluted with MTB ether. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent heptane) to give 4,6-difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethoxy-dibenzothiophene (6) as colorless crystals.

[0516] Compound (6) has the following phase characteristics:

[0517] K 108 C. SmA 141 C. N 169 C. I

Synthesis Example C-4a (CB(S)-3-OT)

[0518] Alternatively, 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethoxy-dibenzothiophene is obtained by hydrogenation of 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethoxy-dibenzothiophene:

##STR00271##

Compound Examples

[0519] Exemplary compounds having a high dielectric constant perpendicular to the director (.sub.) and a high average dielectric constant (.sub.av.) are exemplified in the following compound examples.

Compound Examples 1 to 6

[0520] Compounds of formula T are e.g.

##STR00272##

[0521] This compound (PGS-3-T) has a melting point of 61 C., a clearing point of 172 C., a phase range of K 61 C. S.sub.B 98 C. N 172 C. I and a of +13.7.

##STR00273##

[0522] This compound (PYS-3-T) has a melting point of 63 C., a clearing point of 146 C., a phase range of K 63 C. S.sub.A 146 C. I and a of +7.7.

##STR00274##

[0523] This compound (PUS-3-T) has a melting point of 67 C., a clearing point of 102 C., a phase range of K 67 C. N 102 C. I and a of +17.4.

##STR00275##

[0524] This compound (PUS-3-F) has a melting point of 67 C., a clearing point of 102 C., a phase range of K 67 C. Sa 76 C. N 102 C. I and a of +10.6.

##STR00276##

[0525] This compound (PS-3-T) has a melting point of 69 C., an extrapolated clearing point of 62 C., a phase range of K 69 C. I and a of +9.1 (extrapolated from 5% solution).

##STR00277##

[0526] This compound (YS-20-T) has a melting point of 68 C., an extrapolated clearing point of 36 C., a phase range of K 66 C. I and a of +5.5.

[0527] Analogously the following compounds of formula T-1-1 are prepared

##STR00278##

TABLE-US-00007 R.sup.S X.sup.S Phase range CH.sub.3 F C.sub.2H.sub.5 F C.sub.3H.sub.7 F C.sub.4H.sub.9 F C.sub.5H.sub.11 F C.sub.6H.sub.13 F C.sub.7H.sub.15 F CH.sub.2CH F CH.sub.2CHCH.sub.2 F CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3CH.sub.2CH F CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3 OCF.sub.3 C.sub.2H.sub.5 OCF.sub.3 C.sub.3H.sub.7 OCF.sub.3 C.sub.4H.sub.9 OCF.sub.3 C.sub.5H.sub.11 OCF.sub.3 C.sub.6H.sub.13 OCF.sub.3 C.sub.7H.sub.15 OCF.sub.3 CH.sub.2CH OCF.sub.3 CH.sub.2CHCH.sub.2 OCF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3CH.sub.2CH OCF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3 CF.sub.3 C.sub.2H.sub.5 CF.sub.3 C.sub.3H.sub.7 CF.sub.3 C.sub.4H.sub.9 CF.sub.3 C.sub.5H.sub.11 CF.sub.3 C.sub.6H.sub.13 CF.sub.3 C.sub.7H.sub.15 CF.sub.3 CH.sub.2CH CF.sub.3 CH.sub.2CHCH.sub.2 CF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3 CH.sub.3CH.sub.2CH CF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3

[0528] Analogously the following compounds of formula T-1-2 are prepared

##STR00279##

TABLE-US-00008 R.sup.S X.sup.S Phase range CH.sub.3 F C.sub.2H.sub.5 F C.sub.3H.sub.7 (see above) F K 64 S.sub.? 81 S.sub.A 139 I 7.4 C.sub.4H.sub.9 F C.sub.5H.sub.11 F C.sub.6H.sub.13 F C.sub.7H.sub.15 F CH.sub.2CH F CH.sub.2CHCH.sub.2 F CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3CH.sub.2CH F CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3 OCF.sub.3 C.sub.2H.sub.5 OCF.sub.3 C.sub.3H.sub.7 OCF.sub.3 C.sub.4H.sub.9 OCF.sub.3 C.sub.5H.sub.11 OCF.sub.3 C.sub.6H.sub.13 OCF.sub.3 C.sub.7H.sub.15 OCF.sub.3 CH.sub.2CH OCF.sub.3 CH.sub.2CHCH.sub.2 OCF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3CH.sub.2CH OCF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3 CF.sub.3 C.sub.2H.sub.5 CF.sub.3 C.sub.3H.sub.7 (see above) CF.sub.3 K 61 S.sub.B 98 S.sub.A 172 I 13.7 C.sub.4H.sub.9 CF.sub.3 C.sub.5H.sub.11 CF.sub.3 C.sub.6H.sub.13 CF.sub.3 C.sub.7H.sub.15 CF.sub.3 CH.sub.2CH CF.sub.3 CH.sub.2CHCH.sub.2 CF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3 CH.sub.3CH.sub.2CH CF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3

[0529] Analogously the following compounds of formula T-1-3 are prepared

##STR00280##

TABLE-US-00009 R.sup.S X.sup.S Phase range CH.sub.3 F C.sub.2H.sub.5 F C.sub.3H.sub.7 F C.sub.4H.sub.9 F C.sub.5H.sub.11 F C.sub.6H.sub.13 F C.sub.7H.sub.15 F CH.sub.2CH F CH.sub.2CHCH.sub.2 F CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3CH.sub.2CH F CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3 OCF.sub.3 C.sub.2H.sub.5 OCF.sub.3 C.sub.3H.sub.7 OCF.sub.3 C.sub.4H.sub.9 OCF.sub.3 C.sub.5H.sub.11 OCF.sub.3 C.sub.6H.sub.13 OCF.sub.3 C.sub.7H.sub.15 OCF.sub.3 CH.sub.2CH OCF.sub.3 CH.sub.2CHCH.sub.2 OCF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3CH.sub.2CH OCF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3 CF.sub.3 C.sub.2H.sub.5 CF.sub.3 C.sub.3H.sub.7 (see above) CF.sub.3 K 63 S.sub.A 146 I 7.7 C.sub.4H.sub.9 CF.sub.3 C.sub.5H.sub.11 CF.sub.3 C.sub.6H.sub.13 CF.sub.3 C.sub.7H.sub.15 CF.sub.3 CH.sub.2CH CF.sub.3 CH.sub.2CHCH.sub.2 CF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3 CH.sub.3CH.sub.2CH CF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3

[0530] Analogously the following compounds of formula T-1-4 are prepared

##STR00281##

TABLE-US-00010 R.sup.S X.sup.S Phase range CH.sub.3 F C.sub.2H.sub.5 F C.sub.3H.sub.7 (see above) F K 67 SA 76 N 102 I 10.6 C.sub.4H.sub.9 F C.sub.5H.sub.11 F C.sub.6H.sub.13 F C.sub.7H.sub.15 F CH.sub.2CH F CH.sub.2CHCH.sub.2 F CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3CH.sub.2CH F CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3 OCF.sub.3 C.sub.2H.sub.5 OCF.sub.3 C.sub.3H.sub.7 OCF.sub.3 C.sub.4H.sub.9 OCF.sub.3 C.sub.5H.sub.11 OCF.sub.3 C.sub.6H.sub.13 OCF.sub.3 C.sub.7H.sub.15 OCF.sub.3 CH.sub.2CH OCF.sub.3 CH.sub.2CHCH.sub.2 OCF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3CH.sub.2CH OCF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3 CF.sub.3 C.sub.2H.sub.5 CF.sub.3 C.sub.3H.sub.7 (see above) CF.sub.3 K 39 S.sub.A 137 I 17.4 C.sub.4H.sub.9 CF.sub.3 K 56 S.sub.A 128 I 16.0 C.sub.5H.sub.11 CF.sub.3 K 51 S.sub.A 122 I 16.0 C.sub.6H.sub.13 CF.sub.3 C.sub.7H.sub.15 CF.sub.3 CH.sub.2CH CF.sub.3 CH.sub.2CHCH.sub.2 CF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3 CH.sub.3CH.sub.2CH CF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3

[0531] Analogously the following compounds of formula T-2-2 are prepared

##STR00282##

TABLE-US-00011 R.sup.S X.sup.S Phase range CH.sub.3 F C.sub.2H.sub.5 F C.sub.3H.sub.7 F C.sub.4H.sub.9 F C.sub.5H.sub.11 F C.sub.6H.sub.13 F C.sub.7H.sub.15 F CH.sub.2CH F CH.sub.2CHCH.sub.2 F CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3CH.sub.2CH F CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 F CH.sub.3 Cl C.sub.2H.sub.5 Cl K 46 N 82.7 I C.sub.3H.sub.7 Cl C.sub.4H.sub.9 Cl C.sub.5H.sub.11 Cl C.sub.6H.sub.13 Cl C.sub.7H.sub.15 Cl CH.sub.2CH Cl CH.sub.2CHCH.sub.2 Cl CH.sub.2CH[CH.sub.2].sub.2 Cl CH.sub.3CH.sub.2CH Cl CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 Cl CH.sub.3 OCF.sub.3 C.sub.2H.sub.5 OCF.sub.3 C.sub.3H.sub.7 OCF.sub.3 C.sub.4H.sub.9 OCF.sub.3 C.sub.5H.sub.11 OCF.sub.3 C.sub.6H.sub.13 OCF.sub.3 C.sub.7H.sub.15 OCF.sub.3 CH.sub.2CH OCF.sub.3 CH.sub.2CHCH.sub.2 OCF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3CH.sub.2CH OCF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 OCF.sub.3 CH.sub.3 CF.sub.3 C.sub.2H.sub.5 CF.sub.3 C.sub.3H.sub.7 CF.sub.3 C.sub.4H.sub.9 CF.sub.3 C.sub.5H.sub.11 CF.sub.3 C.sub.6H.sub.13 CF.sub.3 C.sub.7H.sub.15 CF.sub.3 CH.sub.2CH CF.sub.3 CH.sub.2CHCH.sub.2 CF.sub.3 CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3 CH.sub.3CH.sub.2CH CF.sub.3 CH.sub.3CH.sub.2CH[CH.sub.2].sub.2 CF.sub.3

Further Compound Examples

[0532] ##STR00283##

[0533] Comparative, Additional Compounds 1 to 6

[0534] Compounds of formula I-S-1are e.g.

##STR00284##

[0535] This compound (LB(S)-3-F) has a melting point of 133 C., a clearing point of 155.3 C., a phase range of K 133 C. N 155.3 C. I and a of +1.3.

##STR00285##

[0536] This compound (LB(S)-3-OT), the compound of synthesis example 2, has a melting point of 66 C., a clearing point of 181 C., a phase range of K 66 C. S.sub.A 181 C. I and a of +4.7.

##STR00286##

[0537] Compounds of formula I-S-2 are e.g.

[0538] This compound (LB(S)-3-T) has a melting point of 121 C., a clearing point of 162 C., a phase range of 121 C. S.sub.A 162 C. I and a of +7.8.

##STR00287##

[0539] This compound (CB(S)-3-F) has a melting point of 157 C., a clearing point of 170.3 C., a phase range of K 157 C. N 170.3 I.

##STR00288##

[0540] This compound (CB(S)-3-OT), the compound of synthesis example 2, has a melting point of 108 C., a clearing point of 168.5 C., a phase range of K 108 C. S.sub.A 141 C. N 168.5 C. I and a of +4.5.

##STR00289##

[0541] This compound (CB(S)-3-T) has a melting point of 150 C., a (monotropic) clearing point of 138.8 C., a phase range of K 150 C. N (138.8 C.) I and a of +8.1.

[0542] Analogously the following compounds of formula I comprising a dibenzopheneone moiety are prepared

##STR00290##

[0543] This compound (DB(S)-3-OT) has a melting point of 153 C., a clearing point of 174.1 C. and a phase range of K 153 C. S.sub.A 165 C. N 174.1 C. I.

##STR00291##

[0544] This compound (DB(S)-3-OT) has a melting point of 146 C., a clearing point of 168 C. and a phase range of K 146 C. S.sub.A 168 C. I.

[0545] Further comparative, additional compound examples

##STR00292## ##STR00293##

Mixture Examples

[0546] In the following are exemplary mixtures disclosed.

Example 1

[0547] The following mixture (M-1) is prepared and investigated.

TABLE-US-00012 Mixture 1 Composition Compound Concentration/ No. Abbreviation % by weight 1 PUS-3-T 9.0 2 LB-3-T 14.0 3 CC-3-V 45.5 4 CC-3-V1 8.0 5 CLP-V-1 7.0 6 CCVC-3-V 5.0 7 CDU-2-F 3.0 8 PPGU-3-F 0.5 9 APUQU-2-F 3.0 10 APUQU-3-F 5.0 100.0 Physical properties T(N, I) = 79.5 C. n.sub.e (20 C., 589 nm) = 1.5870 n(20 C., 589 nm) = 0.1051 .sub.||(20 C., 1 kHz) = 8.4 .sub.(20 C., 1 kHz) = 4.2 (20 C., 1 kHz) = 4.2 .sub.av. (20 C., 1 kHz) = 5.6 .sub.1 (20 C.) = 61 mPa .Math. s k.sub.11 (20 C.) = 16.1 pN k.sub.33 (20 C.) = 13.7 pN V.sub.0 (20 C.) = 2.06 V .sub./(20 C.) = 1.00 .sub.1/k.sub.11 (20 C.) = 3.79* Remark: all values (except clearing point) at 20 C. and *[mPa .Math. s/pN] and

[0548] This mixture, mixture M-1, is characterized by a good transmission in an FFS display and shows a short response time.

Example 2

[0549] The following mixture (M-2) is prepared and investigated.

TABLE-US-00013 Mixture 2 Composition Compound Concentration/ No. Abbreviation % by weight 1 PUS-3-T 4.0 2 LB-3-T 10.0 3 LB(S)-3-OT 10.0 4 CC-3-V 47.5 5 CC-3-V1 7.5 6 CLP-V-1 7.0 7 CLP-3-T 3.0 8 PPGU-3-F 0.5 9 APUQU-2-F 2.5 10 APUQU-3-F 5.0 11 CDUQU-3-F 3.0 100.0 Physical properties T(N, I) = 81.5 C. n.sub.e(20 C., 589 nm) = 1.5872 n(20 C., 589 nm) = 0.1055 .sub.||(20 C., 1 kHz) = 8.3 .sub.(20 C., 1 kHz) = 4.3 (20 C., 1 kHz) = 4.2 .sub.av.(20 C., 1 kHz) 5.5 .sub.1 (20 C.) = 65 mPa .Math. s k.sub.11 (20 C.) = 128.8 pN k.sub.33 (20 C.) = 14.8 pN V.sub.0 (20 C.) = 2.16 V .sub./(20 C.) = 1.02 .sub.1/k.sub.11(20 C.) = 5.08* Remark: all values (except clearing point) at 20 C. and *[mPa .Math. s/pN] and

[0550] This mixture, mixture M-2, is characterized by a good transmission in an FFS display and shows a short response time.

Example 3

[0551] The following mixture (M-3) is prepared and investigated.

TABLE-US-00014 Mixture 3 Composition Compound Concentration/ No. Abbreviation % by weight 1 PUS-3-T 9.0 2 CY-2-O2 5.0 3 CPY-3-O2 7.0 4 CC-3-V 37.0 5 CC-3-V1 8.0 6 CCP-V-1 11.0 7 CCP-3-OT 8.0 8 APUQU-2-F 0.5 9 APUQU-3-F 5.0 100.0 Physical properties T(N, I) = 81.0 C. n.sub.e (20 C., 589 nm) = 1.5895 n(20 C., 589 nm) = 0.1072 .sub.||(20 C., 1 kHz) = 8.4 .sub.(20 C., 1 kHz) = 3.8 (20 C., 1 kHz) = 4.6 .sub.av. (20 C., 1 kHz) = 5.3 .sub.1 (20 C.) = 63 mPa .Math. s k.sub.11 (20 C.) = 14.7 pN k.sub.33 (20 C.) = 14.7 pN V.sub.0 (20 C.) = 1.90 V .sub./(20 C.) = 0.83 .sub.1/k.sub.11 (20 C.) = 4.29* Remark: all values (except clearing point) at 20 C. and *[mPa .Math. s/pN] and

[0552] This mixture, mixture M-3, is characterized by a good transmission in an FFS display and shows a short response time.

Example 4

[0553] The followina mixture (M-4) is prepared and investiaated.

TABLE-US-00015 Mixture 4 Composition Compound Concentration/ No. Abbreviation % by weight 1 PUS-3-T 15.0 2 CC-3-V 51.0 3 CC-3-V1 6.0 4 CLP-V-1 10.0 5 PP-1-2V1 2.0 6 PGP-1-2V 3.0 7 PGP-2-2V 8.0 8 CLP-3-T 4.0 9 PPGU-3-F 1.0 100.0 Physical properties T(N, I) = 77.5 C. n.sub.e (20 C., 589 nm) = 1.6081 n(20 C., 589 nm) = 0.1181 .sub.||(20 C., 1 kHz) = 5.7 .sub.(20 C., 1 kHz) = 2.7 (20 C., 1 kHz) = 3.0 .sub.av. (20 C., 1 kHz) = 3.7 .sub.1 (20 C.) = t.b.d. mPa .Math. s k.sub.11 (20 C.) = 17.1 pN k.sub.33 (20 C.) = 14.4 pN V.sub.0 (20 C.) = 2.51 V .sub./(20 C.) = 0.90 .sub.1/k.sub.11 (20 C.) = t.b.d.* Remark: all values (except clearing point) at 20 C., *[mPa .Math. s/pN] and t.b.d.: to be determined.

[0554] This mixture, mixture M-4, is characterized by a good transmission in an FFS display and shows a short response time.

Example 5

[0555] The following mixture (M-5) is prepared and investigated.

TABLE-US-00016 Mixture 5 Composition Compound Concentration/ No. Abbreviation % by weight 1 PUS-3-T 4.0 2 CC-3-V 49.0 3 CC-3-V1 4.0 4 CLP-V-1 10.0 5 PP-1-2V1 12.0 6 PGP-1-2V 8.0 7 PGP-2-2V 10.0 8 PPGU-3-F 1.0 9 DGUQU-4-F 2.0 100.0 Physical properties T(N, I) = 74.0 C. n.sub.e (20 C., 589 nm) = 1.6212 n(20 C., 589 nm) = 0.1248 .sub.||(20 C., 1 kHz) = 4.3 .sub.(20 C., 1 kHz) = 2.6 (20 C., 1 kHz) = 1.6 .sub.av. (20 C., 1 kHz) = 3.1 .sub.1 (20 C.) = t.b.d. mPa .Math. s k.sub.11 (20 C.) = 15.1 pN k.sub.33 (20 C.) = 14.5 pN V.sub.0 (20 C.) = 3.20 V .sub./(20 C.) = 0.52 .sub.1/k.sub.11 (20 C.) = t.b.d.* Remark: all values (except clearing point) at 20 C., *: [mPa .Math. s/pN] and t.b.d.: to be determined.

[0556] This mixture, mixture M-5, is characterized by a good transmission in an FFS display and shows a short response time.

Example 6

[0557] The following mixture (M-6) is prepared and investigated.

TABLE-US-00017 Mixture 6 Composition Compound Concentration/ No. Abbreviation % by weight 1 PUS-3-T 9.0 2 CC-3-V 48.0 3 CC-3-V1 7.0 4 CLP-V-1 12.0 5 PP-1-2V1 8.0 6 PGP-1-2V 7.0 7 PGP-2-2V 8.0 8 PPGU-3-F 1.0 100.0 Physical properties T(N, I) = 76.5 C. n.sub.e (20 C., 589 nm) = 1.6180 n(20 C., 589 nm) = 0.1235 .sub.||(20 C., 1 kHz) = 4.4 .sub.(20 C., 1 kHz) = 2.6 (20 C., 1 kHz) = 1.8 .sub.av. (20 C., 1 kHz) = 3.2 .sub.1 (20 C.) = t.b.d. mPa .Math. s k.sub.11 (20 C.) = 16.1 pN k.sub.33 (20 C.) = 14.7 pN V.sub.0 (20 C.) = 3.14 V .sub./(20 C.) = 0.56 .sub.1/k.sub.11 (20 C.) = t.b.d.* Remark: all values (except clearing point) at 20 C., *[mPa .Math. s/pN] and t.b.d.: to be determined.

[0558] This mixture, mixture M-6 is characterized by a good transmission in an FFS display and shows a short response time.

Example 7

[0559] The following mixture (M-7) is prepared and investigated.

TABLE-US-00018 Mixture 7 Composition Compound Concentration/ No. Abbreviation % by weight 1 PUS-3-F 4.0 2 CGS-3-2 10.0 3 CC-3-V 50.0 4 CC-3-V1 6.5 5 PGP-1-2V 4.0 6 PGP-2-2V 8.0 7 PGU-2-F 4.0 8 CLP-3-T 6.5 9 PPGU-3-F 1.0 10 PGUQU-3-F 3.0 11 PGUQU-4-F 3.0 100.0 Physical properties T(N, I) = 77.5 C. n.sub.e (20 C., 589 nm) = 1.6086 n(20 C., 589 nm) = 0.1179 .sub.||(20 C., 1 kHz) = 6.2 .sub.(20 C., 1 kHz) = 2.8 (20 C., 1 kHz) = 1.8 .sub.av. (20 C., 1 kHz) = 3.4 .sub.1 (20 C.) = t.b.d. mPa .Math. s k.sub.11 (20 C.) = 16.1 pN k.sub.33 (20 C.) = 13.7 pN V.sub.0 (20 C.) = 2.18 V .sub./(20 C.) = 0.82 .sub.1/k.sub.11 (20 C.) = t.b.d.* Remark: all values (except clearing point) at 20 C., *[mPa .Math. s/pN] and t.b.d.: to be determined.

[0560] This mixture, mixture M-7, is characterized by a good transmission in an FFS display and shows a short response time.

Example 8

[0561] The following mixture (M-8) is prepared and investigated.

TABLE-US-00019 Mixture 8 Composition Compound Concentration/ No. Abbreviation % by weight 1 PUS-3-F 4.0 2 CGS-3-2 16.0 3 CC-3-V 52.5 4 CC-3-V1 7.5 5 PGP-2-2V 3.0 6 CLP-3-T 6.5 7 DPGU-4-F 3.0 8 PPGU-3-F 1.5 9 PGUQU-3-F 3.0 10 PGUQU-4-F 3.0 100.0 Physical properties T(N, I) = 78.5 C. n.sub.e (20 C., 589 nm) = 1.5934 n(20 C., 589 nm) = 0.1061 .sub.||(20 C., 1 kHz) = 6.1 .sub.(20 C., 1 kHz) = 2.7 (20 C., 1 kHz) = 3.3 .sub.av. (20 C., 1 kHz) = 3.8 .sub.1 (20 C.) = t.b.d. mPa .Math. s k.sub.11 (20 C.) = 14.9 pN k.sub.33 (20 C.) = 14.1 pN V.sub.0 (20 C.) = 2.22 V .sub./(20 C.) = 0.82 .sub.1/k.sub.11 (20 C.) = t.b.d.* Remark: all values (except clearing point) at 20 C., *[mPa .Math. s/pN] and t.b.d.: to be determined.

[0562] This mixture, mixture M-8, is characterized by a good transmission in an FFS display and shows a short response time.

Example 9

[0563] The following mixture (M-9) is prepared and investigated.

TABLE-US-00020 Mixture 9 Composition Compound Concentration/ No. Abbreviation % by weight 1 PS-3-T 10.0 2 CC-3-V 28.4 3 CC-3-V1 5.8 4 CCP-3-3 5.4 5 CCP-V-1 10.8 6 CCP-V2-1 10.8 7 CPGP-5-2 1.8 8 PP-1-2V1 4.5 9 PUQU-3-F 18.0 10 APUQU-2-F 4.5 100.0 Physical properties T(N, I) = 62.0 C. n.sub.e (20 C., 589 nm) = 1.5895 n(20 C., 589 nm) = 0.1003 .sub.||(20 C., 1 kHz) = 9.4 .sub.(20 C., 1 kHz) = 3.3 (20 C., 1 kHz) = 6.1 .sub.av. (20 C., 1 kHz) = 5.3 .sub.1 (20 C.) = 55 mPa .Math. s k.sub.11 (20 C.) = 11.6 pN k.sub.33 (20 C.) = 12.3 pN V.sub.0 (20 C.) = 1.46 V .sub./(20 C.) = 0.54 .sub.1/k.sub.11 (20 C.) = 4.74* Remark: all values (except clearing point) at 20 C., *[mPa .Math. s/pN] and t.b.d.: to be determined.

[0564] This mixture, mixture M-9, is characterized by a good transmission in an FFS display and shows a short response time.

Example 10

[0565] The following mixture (M-10) is prepared and investigated.

TABLE-US-00021 Mixture 10 Composition Compound Concentration/ No. Abbreviation % by weight 1 YS-2O-T 10.0 2 CC-3-V 28.4 3 CC-3-V1 5.8 4 CCP-3-3 5.4 5 CCP-V-1 10.8 6 CCP-V2-1 10.8 7 PP-1-2V1 4.5 8 CPGP-5-2 1.8 9 PUQU-3-F 18.0 10 APUQU-2-F 4.5 100.0 Physical properties T(N, I) = 67.5 C. n.sub.e (20 C., 589 nm) = 1.5897 n(20 C., 589 nm) = 0.1027 .sub.||(20 C., 1 kHz) = 9.7 .sub.(20 C., 1 kHz) = 3.8 (20 C., 1 kHz) = 5.8 .sub.av. (20 C., 1 kHz) = 5.7 .sub.1 (20 C.) = 59 mPa .Math. s k.sub.11 (20 C.) = 12.2 pN k.sub.33 (20 C.) = 12.9 pN V.sub.0 (20 C.) = 1.53 V .sub./(20 C.) = 0.66 .sub.1/k.sub.11 (20 C.) = 4.84* Remark: all values (except clearing point) at 20 C., *[mPa .Math. s/pN] and t.b.d.: to be determined.

[0566] This mixture, mixture M-10, is characterized by a good transmission in an FFS display and shows a short response time.

Comparative Example A

[0567] The following mixture (CE-A) is prepared and investigated.

TABLE-US-00022 Mixture CE-A Composition Compound Concentration/ No. Abbreviation % by weight 1 CC-3-V 31.5 2 CC-3-V1 6.5 3 CCP-3-3 6.0 4 CCP-V-1 12.0 5 CCP-V2-1 12.0 6 PP-1-2V1 5.0 7 CPGP-5-2 2.0 8 PUQU-3-F 20.0 9 APUQU-2-F 5.0 100.0 Physical properties T(N, I) = 78.5 C. n.sub.e (20 C., 589 nm) = 1.5876 n(20 C., 589 nm) = 0.1001 .sub.(20 C., 1 kHz) = 3.0 (20 C., 1 kHz) = 6.0 .sub.av. (20 C., 1 kHz) = 5.0 .sub.1 (20 C.) = 64 mPa .Math. s k.sub.11 (20 C.) = 13.3 pN k.sub.33 (20 C.) = 15.5 pN V.sub.0 (20 C.) = 1.58 V V.sub.10 (20 C.) = 2.13 V .sub./ = 0.50 .sub.1/k.sub.11 = 4.81* Remark: all values (except clearing point) at 20 C., *: [mPa .Math. s/pN] and t.b.d.: to be determined.

[0568] This comparative mixture, mixture A, has a dielectric ratio (.sub./) of 0.50, a ratio of (.sub.1/k.sub.11) of 4.81 mPa.Math.s/pN and is characterized a moderately good transmission in an FFS display and shows an at best acceptable short response time.

TABLE-US-00023 TABLE 1 Example CE-A A-1 A-2 A-3 Composition Cpd. None PGS-3-T PYS-3-T PUS-3-T c (Cpd.)/% 0.0 10.0 10.0 10.0 c (CE-A)/% 100.0 90.0 90.0 90.0 Properties T (N, I)/ C. 78.5 80.5 78.0 77.8 n.sub.e (589 nm) 1.5875 t.b.d. 1.6025 1.6030 n (589 nm) 0.1001 t.b.d. 0.1135 0.1141 .sub.|| (1 kHz) 9.0 t.b.d. 9.5 10.4 .sub. (1 kHz) 3.0 t.b.d. 3.4 3.2 (1 kHz) 6.0 t.b.d. 6.1 7.2 .sub.av. (1 kHz) 5.0 t.b.d. 5.4 5.6 .sub.1/mPa .Math. s 64 t.b.d. 68 65 k.sub.11/pN 13.3 t.b.d. 14.3 14.2 k.sub.33/pN 15.5 t.b.d. 14.4 14.5 .sub. / 0.50 t.b.d. 0.73 0.44 .sub.1/k.sub.11* 4.81 t.b.d. 4.76 4.58 V.sub.0/V 1.77 t.b.d. 1.59 1.47 Example CE-A A-4 A-5 A-6 Composition Cpd. None PGS-3-F PUS-3-F GGS-2-CI c (Cpd.)/% 0.0 10.0 10.0 10.0 c (CE-A)/% 100.0 90.0 90.0 90.0 Properties T (N, I)/ C. 78.5 85.0 82.0 83.0 n.sub.e (589 nm) 1.5875 t.b.d. t.b.d. t.b.d. n (589 nm) 0.1001 t.b.d. t.b.d. t.b.d. .sub.|| (1 kHz) 9.0 t.b.d. t.b.d. t.b.d. .sub. (1 kHz) 3.0 t.b.d. t.b.d. t.b.d. (1 kHz) 6.0 t.b.d. t.b.d. t.b.d. .sub.av. (1 kHz) 5.0 t.b.d. t.b.d. t.b.d. .sub.1/mPa .Math. s 64 t.b.d. t.b.d. t.b.d. k.sub.11/pN 13.3 t.b.d. t.b.d. t.b.d. k.sub.33/pN 15.5 t.b.d. t.b.d. t.b.d. .sub. / 0.50 t.b.d. t.b.d. t.b.d. .sub.1/k.sub.11* 4.81 t.b.d. t.b.d. t.b.d. V.sub.0/V 1.77 t.b.d. t.b.d. t.b.d. Example CE-A A-7 A-8 A-9 Composition Cpd. None PS-3-T YS-2O-F YS-2O-T c (Cpd.)/% 0.0 10.0 10.0 10.0 c (CE-A)/% 100.0 90.0 90.0 90.0 Properties T (N, I)/ C. 78.5 t.b.d. t.b.d. t.b.d. n.sub.e (589 nm) 1.5875 t.b.d. t.b.d. t.b.d. n (589 nm) 0.1001 t.b.d. t.b.d. t.b.d. .sub.|| (1 kHz) 9.0 t.b.d. t.b.d. t.b.d. .sub. (1 kHz) 3.0 t.b.d. t.b.d. t.b.d. (1 kHz) 6.0 t.b.d. t.b.d. t.b.d. .sub.av. (1 kHz) 5.0 t.b.d. t.b.d. t.b.d. .sub.1/mPa .Math. s 64 t.b.d. t.b.d. t.b.d. k.sub.11/pN 13.3 t.b.d. t.b.d. t.b.d. k.sub.33/pN 15.5 t.b.d. t.b.d. t.b.d. .sub. / 0.50 t.b.d. t.b.d. t.b.d. .sub.1k.sub.11* 4.81 t.b.d. t.b.d. t.b.d. V.sub.0/V 1.77 t.b.d. t.b.d. t.b.d. Example A-10 A-11 A-12 A-13 Composition Cpd. PUS-3-F PUS-3-T PUS-4-T PUS-5-T c (Cpd.)/% 20.0 20.0 20.0 20.0 c (CE-A)/% 80.0 80.0 80.0 80.0 Properties T (N, I)/ C. 81.0 77.0 76.0 78.0 n.sub.e (589 nm) 1.6309 1.6203 1.6173 1.6173 n (589 nm) 0.1350 0.1302 0.1266 0.1271 .sub.|| (1 kHz) 10.1 11.9 11.5 11.3 .sub. (1 kHz) 3.2 3.3 3.3 3.3 (1 kHz) 6.9 8.6 8.2 8.0 .sub.av. (1 kHz) 5.5 6.2 6.0 8.0 .sub.1/mPa .Math. s t.b.d. t.b.d. t.b.d. t.b.d. k.sub.11/pN 14.7 15.9 15.4 15.5 k.sub.33/pN 15.7 14.1 13.4 14.0 .sub. / 0.46 0.38 0.40 0.41 .sub.1/k.sub.11* t.b.d. t.b.d. t.b.d. t.b.d. V.sub.0/V 1.53 1.43 1.44 1.46 Remarks: all values (except clearing point) at 20 C., *[mPa .Math. s/pN] and t.b.d.: to be determined.

[0569] The preceding 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.

[0570] From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.