JPH0769992A - 4-(4-substituted cyclohexylidene)cyclohexanol derivative and its production - Google Patents

Abstract

PURPOSE:To produce a new liquid crystal compound having a low index of birefringence and having a bicyclic cyclohexylidenecyclohexane skeleton in its mesogen skeleton. CONSTITUTION:A 4-(4-substituted cyclohexylidene)cyclohexanol derivative of formula I [R is an alkyl; Ar is a (substituted) aromatic group; X and Y are each O, COO; (m) and (n) are each 0, 1; Q* is an optically active alkyl having an asymmetric carbon atom], e.g. 4-(4-octoxycyclohexylidene)cyclohexyl 4-[(S)-2- fluoro-2-methyl]hexanoyloxybenzoate. This compound can be produced by introducing a long-chain alkyl into 4(4-hydroxycyclohexylidene)cyclohexanol of formula II according to the alkoxyalkylation method, etc., to synthesize a compound of formula III and condensing an optically active carboxylic acid of formula IV therewith.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel liquid crystal compound
The present invention relates to a-(4-substituted cyclohexylidene) cyclohexanol derivative and a method for producing the same.

[0002]

Bicyclic compounds are widely used as mesogenic skeletons of liquid crystals. It is also known that the optical characteristics and electric field response characteristics of liquid crystals can be adjusted by mixing compounds having various skeletons. On the other hand, in order to make the display of the liquid crystal display easier to see, it is effective to eliminate the coloring of the display itself. Further, since the light transmittance of a cell filled with a liquid crystal compound depends on the product of the cell thickness and the birefringence of the liquid crystal compound, a liquid crystal compound having a low birefringence is required under the condition of ensuring a constant light transmittance. It is also known that the cell thickness can be increased by using. Since the cell thickness of a liquid crystal device has a lower limit in terms of production technology, a liquid crystal compound having a low birefringence is required to obtain specific optical characteristics and electric field response characteristics.

Examples of the mesogenic skeleton that imparts low birefringence to liquid crystals include a cyclohexylbenzene skeleton and a bicyclohexane skeleton (Japanese Patent Laid-Open No. 2-153316).

[0004]

However, with the cyclohexylbenzene skeleton, it is difficult to sufficiently lower the birefringence of the liquid crystal compound obtained, and with the bicyclohexane skeleton, the birefringence of the obtained liquid crystal compound is reduced. Although it is possible to lower the birefringence, there is a drawback that the viscosity becomes high.

[0005]

[Means for Solving the Problems] In order to solve the above-mentioned drawbacks, the present inventors have made various investigations, and as a result, as a result, the cyclohexylidenecyclohexane skeleton which is bicyclic in the mesogenic bone nucleus

[Chemical 5] It was found that a novel liquid crystal compound having the above-mentioned compound overcomes the above-mentioned drawbacks, and completed the present invention.

That is, the present invention has the general formula (I)

[Chemical 6] [In the general formula (I), R represents an alkyl group which may have a branch, Ar represents an aromatic group which may have a substituent,
X and Y each independently represent O or COO, m and n each independently represent 0 or 1, and Q * represents an optically active alkyl group having an asymmetric carbon atom. ] Represented by 4
-(4-Substituted cyclohexylidene) cyclohexanol derivative is provided.

The present invention also provides a process for producing the compound of the above general formula (I). The compound of general formula (I) has the formula (II)

[Chemical 7] 4- (4-hydroxycyclohexylidene) represented by
Introducing a long-chain alkyl group into cyclohexanol by alkoxyalkylation or alkylesterification to give formula (III)

[Chemical 8] [In the formula (III), R represents an alkyl group which may have a branch, and X represents O or COO. ] The optically active carboxylic acid of formula (IV)

HOOC- (Ar) m- (Y) n-Q * (IV) [In the formula (IV), Ar represents an aromatic group which may have a substituent, and Y represents O or COO. In the formula, m and n each independently represent 0 or 1, and Q * represents an optically active alkyl group having an asymmetric carbon atom. ] Can be condensed and manufactured.

As R (alkyl group which may have a branch) in the formula (I) or the formula (III) of the present invention, an alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group,
Examples thereof include propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridodecyl group and the like, and branched isomers thereof.

A in formula (I) or formula (IV) of the present invention
Examples of r (aromatic group which may have a substituent) include the following groups.

[Chemical 10]

4- (4-hydroxycyclohexylidene) cyclohexanol of the formula (II) used in the present invention is 4
-Hydroxycyclohexanone can be obtained by condensation reaction in the presence of low-valent titanium. Also 1,4-
Cyclohexanediol is converted to monobenzoyl and oxidized to 4-benzoyloxycyclohexanone, which is reacted with hydrazine to give 4,4'-dibenzirochiazine, and hydrogen sulfide is added to give 4,4'-dibenzoyloxythiazolidine. , Oxidized to 4,4'-dibenzoyloxythiazoline, pyrolyzed to 4,4'-dibenzyloxythiirane, desulfurized to 4- (4-benzoyloxycyclohexylidene) cyclohexanebenzoate, and finally Can also be obtained by eliminating the benzoyl group

There are two methods for introducing a long chain alkyl group into 4- (4-hydroxycyclohexylidene) cyclohexanol of the formula (II) by alkoxyalkylation. The first method is a method of protecting one hydroxyl group of the formula (II) with an acylating agent, alkylating the other hydroxyl group, and subjecting this to an alkali treatment to remove the protective group,
The second method is a method of directly alkylating without protecting the hydroxyl group.

In the first method, the protective group for the hydroxyl group is an acetyl group, a propanoyl group, an isopropanoyl group, a butanoyl group, a pentanoyl group, a benzoyl group, or a p-group.
An acyl group such as a nitrobenzoyl group is used. When alkylating a hydroxyl group, the hydroxyl group is converted to a metal salt and then alkylated. The metal salt of the hydroxyl group can be obtained by using a reducing reagent such as sodium methoxy, sodium ethoxy, potassium t-butoxy, sodium hydride, lithium hydride, n-butyllithium.

Examples of the alkylating reagent in this case include methyl bromide, ethyl bromide, propyl bromide, octyl bromide, nonane bromide, decane bromide, methoxymethyl bromide, methoxypropyl bromide and octyl iodide. , An alkyl halide such as octyl chloride, a dialkyl sulfuric acid such as diethylsulfate and dibutylsulfate, an alkyl p-toluenesulfonate such as ethyl p-toluenesulfonate and butyl p-toluenesulfonate, and the like can be used. From the viewpoint of sex, alkyl bromide or alkyl iodide is more preferably used.

As the solvent for the alkylation reaction, ether solvents such as tetrahydrofuran, diethyl ether, dioxane, dimethoxyethane and diethylene glycol dimethyl ether, aromatic solvents such as benzene, toluene and xylene, N, N-dimethylformamide (DM) are used.
F), an amide solvent such as dimethylamide, a sulfoxide such as dimethylsulfoxide and sulfolane, or a mixed solvent thereof can be used, and among these, DMF is most preferably used. Further, it is preferable to use the solvent in an anhydrous state.

The elimination of the hydroxyl-protecting group proceeds by adding a base such as sodium hydroxide, potassium hydroxide or calcium hydroxide to the reaction solution after alkylation in the presence of water to make it alkaline.

In the second method of alkoxyalkylation, the alkylation is carried out after converting one hydroxyl group into a metal salt,
It is carried out by reacting an alkylating reagent. The same alkylating reagent, reducing reagent and solvent as those used in the above-mentioned first method are used.

There are two methods for introducing a long-chain alkyl group into 4- (4-hydroxycyclohexylidene) cyclohexanol by alkyl esterification. The first method is a method of reacting with an acid chloride in a basic solvent, and the second method is a method of reacting with a dehydrating reagent such as diisopropylcarbodiimide.

In the first method, the acid chlorides used include acid chlorides obtained by treating a carboxylic acid with thionyl chloride, phosphorus pentoxide, phosphoryl chloride, phosphorus trichloride, etc. Is an ether solvent such as tetrahydrofuran, diethyl ether, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, an aromatic solvent such as benzene, toluene, xylene, N, N-
There are amide solvents such as dimethylformamide (DMF) and dimethylamide, sulfoxides such as dimethyl sulfoxide and sulfolane, and mixed solvents thereof. It is preferable to use the solvent in an anhydrous state. To make a basic solvent, pyridine, dimethylaniline,
Tetramethylurea, magnesium metal, etc. may be added.

In the second method of alkyl esterification, dicyclohexylcarbodiimide, diisopropylcarbodiimide or the like can be used as the dehydrating agent, and 4-dimethylaminopyridine or the like can be used as the catalyst.
Examples of the solvent at this time include halogen solvents such as methylene chloride and chloroform, ether solvents such as tetrahydrofuran, diethyl ether, dioxane, dimethoxyethane and diethylene glycol dimethyl ether, aromatic solvents such as benzene, toluene and xylene, and N, N. An amide solvent such as dimethylformamide (DMF) or dimethylamide, a sulfoxide such as dimethyl sulfoxide or sulfolane, or a mixed solvent thereof can be used. The solvent is preferably dehydrated.

As a method for condensing the compound of formula (III) and the optically active carboxylic acid of formula (IV), an acid chloride is used in a basic solvent in the same manner as in the case of the above alkyl esterification. There is a method of obtaining by reacting or a method of obtaining by reacting with a dehydrating reagent such as diisopropylcarbodiimide. Comparing the two methods, the latter is preferable because the reaction conditions are mild.

Hereinafter, examples of synthesizing the raw material compounds will be shown. <Synthesis Example 1> Synthesis of 4- (4-octoxycyclohexylidene) cyclohexanol

[Chemical 11]

33 mg (1.05 times equivalent) of potassium t-butoxide was weighed into a 10 ml pressure tube, and anhydrous DMF1 was used.
After adding ml, the mixture was stirred at 0 ° C. Transformer-4-
A solution of 50 mg of (4-hydroxycyclohexylidene) cyclohexanol (previously dried at 120 ° C./1 mmHg) in 4 ml of anhydrous DMF was added by a syringe. After 30 minutes, 0.66 ml of octyl bromide (1.5 equivalents) was added and 6
It was left at 105 ° C. for 105 hours. The reaction solution was cooled to 0 ° C., 2 ml of ethanol was added, and the mixture was concentrated under reduced pressure and then subjected to silica gel column chromatography (hexane / ethyl acetate = 3/1;
(Volume ratio). Octanol generated by decomposition of octyl bromide was azeotropically removed with water / chloroform / ethanol to obtain 34 mg of 4- (4-octoxycyclohexylidene) cyclohexanol (yield: 43%). The results of analyzing the physicochemical properties of this product are as follows.

Infrared absorption spectrum (ν cm ^-1 ): 3
452, 2932, 2860, 2356, 1636, 1442, 1366, 1112, 106
4,556,276 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ , δppm):
0.88 (3H, t, J = 6.7Hz), 1.2-1.5
(12H, m), 1.5-1.8 (4H, m), 1.8-2.0
(8H, m) 2.3-2.6 (4H, m) 3.3-3.
5 (1H, m), 3.44 (2H, t, J = 6.6Hz),
3.84 (1H, m)

<Synthesis Example 2> Synthesis of 4- (4-decoxycyclohexylidene) cyclohexanol

[Chemical 12]

T-Butoxy potassium 7 was added to a 10 ml pressure tube.
Weigh 5 mg (1.05 times equivalent) and dry DMF 2 m
1 was added and stirred, and a solution of 110 mg (0.57 mmol) of trans-4- (4-hydroxycyclohexylidene) cyclohexanol dried at 120 ° C./1 mmHg in 9 ml of anhydrous DMF was added by a syringe. After 30 minutes, 0.18 ml (1.5 times equivalent) of octyl bromide was added, and the mixture was left at room temperature for 50 hours. 2 ml of ethanol was added under ice cooling, the reaction solution was concentrated under reduced pressure, and the residue was purified by silica gel column (hexane / ethyl acetate = 3/1, volume ratio) to obtain a crude monoalkyl compound. This was dissolved in chloroform, water was added, and the mixture was homogenized with ethanol. The mixed solution was concentrated under reduced pressure to azeotropically remove the octanol generated by the decomposition of octyl bromide, to give 4- (4-decoxycyclohexylidene) cyclohexanol 100 mg (yield: 53%).
Got The results of analyzing the physicochemical properties of this product are as follows.

Infrared absorption spectrum (ν cm ^-1 ): 3
452, 2932, 2860, 2356, 1636, 1442, 1366, 1112, 1064 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ , δppm):
0.88 (3H, t, J = 6.7Hz), 1.2-1.5
(12H, m), 1.5-1.8 (4H, m), 1.8-
2.0 (8H, m), 2.3-2.6 (4H, m), 3.3
~ 3.5 (1H, m), 3.44 (2H, t, J = 6.6
Hz), 3.84 (1H, m)

<Synthesis Example 3> Synthesis of 4- (4-octanoyloxycyclohexylidene) cyclohexanol

[Chemical 13]

330 mg (1.7 mmol) of trans-4- (4-hydroxycyclohexylidene) cyclohexanol dried at 120 ° C./1 mmHg was dissolved in 67 ml of anhydrous pyridine and -30 ° C. (dry ice / methanol). Then, 0.34 ml (1.2 times equivalent) of octanoyl chloride was added, and the mixture was stirred under ice cooling and left for 6 hours. 2 ml of methanol was added under ice cooling, the reaction solution was concentrated under reduced pressure, and then purified by silica gel column chromatography (hexane / ethyl acetate / ethanol = 10/4/1; volume ratio),
4- (4-Octanoyloxycyclohexylidene) cyclohexanol was obtained. This was recrystallized from hexane to obtain 297 mg of crystals (yield: 54%). The results of its ¹ H-nuclear magnetic resonance spectrum are as follows.

¹ H-nuclear magnetic resonance spectrum (CDCl ₃ ,
δppm): 0.85 to 0.90 (3H, t, J = 6.
6 Hz), 1.2 to 1.4 {10H, m,}, 1.4 to
1.6 (4H, m), 1.8-2.0 (8H, m),
2.25 to 2.31 (2H, t), 2.4 to 2.7 (4
H, m) 3.8-3.9 (1H, m), 4.9-
5.0 (1H, m) ppm

<Synthesis Example 4> Synthesis of 4-[(S) -2-fluoro-2-methylheptanoyloxy] benzoic acid

[Chemical 14]

In a dried flask, 240 mg (5 equivalents) of (S) -2-fluoro-2-methylhexanoic acid was weighed and 1.2 ml (20 equivalents) of thionyl chloride was added to a Dimroth condenser. And a calcium chloride tube was attached and refluxed for 3 hours. Thionyl chloride was distilled off under reduced pressure (100 mmHg, 50 ° C.) to obtain an acid chloride. 0.45 g (1.2 times equivalent) of this acid chloride was added to 0.45 g of dried 4-hydroxybenzoic acid.
(2.7 mmol) was added to a solution of anhydrous pyridine in 10 ml, and the mixture was allowed to stand at room temperature for 4 hours. After concentration under reduced pressure, 0.1N hydrochloric acid was added to neutralize, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a residue. Purification by silica gel column chromatography (hexane / diethyl ether = 8/1; volume ratio), 21 mg of 4-[(2-fluoro-2-methyl) heptanoyloxy] benzoic acid (yield 54.7)
%) Was obtained. The results of analyzing the physicochemical properties of this product are as follows.

Infrared absorption spectrum (ν cm ^-1 ): 2
932, 1776, 1684, 1606, 1432, 1382, 1322, 1292, 121
2, 1170, 1124, 1062, 948, 906, 864, 828, 760, 366,
312 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ , δppm):
0.95 (3H, t, J = 5.5Hz), 1.4-1.
5 (2H, m), 1.67 (3H, d, J = 11.0H
z), 1.9 to 2.2 (2H, m), 7.24 (2H,
d, J = 8.8 Hz), 8.17 (2H, d, J
= 8.5 Hz)

<Synthesis Example 5> Synthesis of 4-[(S) -4-methylhexoxy] benzoic acid

[Chemical 15]

(S)-(+)-4-
1.7 g (14.6 mmol) of methyl-hexanol was weighed and dissolved in 5 ml of anhydrous pyridine, and 4 g of chloride was added thereto.
-Toluenesulfonyl 4.2 g (1.5 eq.) Was added. After stirring for 15 hours, the reaction solution was poured into a phosphate buffer under ice cooling and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a residue. This was purified by silica gel column chromatography (hexane / ethyl acetate = 8/1; volume ratio), and 1.4 g of (S) -4-methyl-1- (4-toluenesulfonyloxy) hexane (yield 35 %) Was obtained.

Next, 36 mg (1.2 times equivalent) of sodium hydride was weighed into a dry 30 ml two-necked flask,
This was suspended in 2 ml of anhydrous DMF. Ethyl 4-hydroxybenzoate 148 mg (1.2 eq) DM
The F6 ml solution was added dropwise and stirred for 30 minutes. DM of 0.2 g (0.74 mmol) of (S) -4-methyl-1- (4-toluenesulfonyloxy) hexane obtained above was DM.
After adding F4ml solution dropwise and leaving it for 15 hours at room temperature,
The reaction solution was ice-cooled, phosphate buffer was added, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a residue.
This was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1; volume ratio) to give 4-methylhexoxybenzoic acid ethyl ester 1
20 mg (yield 70%) was obtained.

To 120 mg of the obtained 4-methylhexoxybenzoic acid ethyl ester was added 4 ml of a 1N sodium hydroxide aqueous solution, and the mixture was refluxed for 4 hours. The reaction solution was concentrated, 3 g of silica gel was added, and silica gel column chromatography (hexane / ethyl acetate / ethanol =
(10/10/1; volume ratio) as it is and purified to obtain 4-[(S) -4-methylhexoxy] benzoic acid 97 mg (yield 90%). The results of analyzing the physicochemical properties of this product are as follows.

Infrared absorption spectrum (ν cm ^-1 ): 34
52, 1680, 1610, 1516, 1430, 1332,1292, 1258, 1174,
846, 768, 388, 308, 270 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ , δppm):
0.8-1.0 (6H, m), 1.1-1.6 (5H, m),
1.6-2.0 (2H, m), 4.01 (2H, t,
J = 6.6 Hz), 6.93 (2H, d, J = 4.
4), 8.05 (2H, d, J = 4.4)

[0038]

EXAMPLES Example 1 4- (4-octoxycyclohexylidene)
Synthesis of cyclohexyl 4-[(S) -2-fluoro-2-methylhexanoyloxy] benzoate

[Chemical 16] 3 equipped with a Jimroth condenser and argon balloon
4- (4-octoxycyclohexylidene) cyclohexanol (Synthesis example 1) 11.0 was placed in a 0 ml two-necked flask.
mg (0.037 mmol), 4-[(S) -2-fluoro-2-methylheptanoyloxy] benzoic acid (Synthesis Example 4) 10.0 mg (1 equivalent), 4-dimethylaminopyridine 0.9 mg (0.2 times equivalent) was added and dissolved in 1 ml of methylene chloride. After adding 7 μl (1.2 times equivalent) of 1,3-diisopropylcarbodiimide and refluxing for 6 hours, the reaction solution was concentrated under reduced pressure to obtain a residue. This was purified by silica gel column chromatography (hexane / ethyl acetate = 6/1; volume ratio), and 4-
6.2 mg (yield 30%) of (4-octoxycyclohexylidene) cyclohexyl 4-[(S) -2-fluoro-2-methyl] hexanoyloxybenzoate was obtained.
The results of analyzing the physicochemical properties of this product are as follows.

Infrared absorption spectrum (ν cm ^-1 ): 293
2, 2860, 1788, 1722, 1606, 1506,1458, 1276, 1204,
1162, 1110, 1016, 760, 416 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ , δppm): 0.0
7-1.0 (6H, m), 1.0-1.5 (24H,
m), 1.5 to 1.6 (4H, m), 1.8 to 2.1 (8)
H, m) 2.4-2.6 (4H, m) 3.3-3.5
(3H, m), 5.1-5.3 (1H, m), 7.1-7.2
(2H, m), 8.1-8.2 (2H, m)

Example 2 Synthesis of 4- (4-decoxycyclohexylidene) cyclohexyl 4-[(S) -2-fluoro-2-methylhexanoyloxy] benzoate

[Chemical 17] 3 equipped with a Jimroth condenser and an argon balloon
4- (4-decoxycyclohexylidene) cyclohexanol (Synthesis example 2) 10.0 m in a 0 ml two-necked flask.
g (0.030 mmol), 4-[(S) -2-fluoro-2-methylheptanoyloxy] benzoic acid (Synthesis example 4) 8 mg (1 equivalent) and 4-dimethylaminopyridine 0.9 mg (0 .2 equivalents) was taken and dissolved in 1 ml of methylene chloride. Add 1,3-diisopropylcarbodiimide (4.7 μl, 1.2 times equivalent) to give 6
After refluxing for an hour, the reaction solution was concentrated under reduced pressure to obtain a residue. This is subjected to silica gel column chromatography (hexane /
Ethyl acetate = 6/1; volume ratio), and purified by 4- (4-decoxycyclohexylidene) cyclohexyl 4-
7.2 mg (41% yield) of [(S) -2-fluoro-2-methylhexanoyloxy] benzoate were obtained. The results of analyzing the physicochemical properties of this product are as follows.

Infrared absorption spectrum (ν cm ^-1 ): 293
2, 2860, 1788, 1722, 1606, 1506, 1458, 1276, 1204,
1162, 1110, 1016, 760, 416 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ , δppm): 0.0
7-1.0 (6H, m), 1.0-1.5 (28H, m),
1.5-1.6 (4H, m), 1.8-2.1 (8H,
m) 2.4 to 2.6 (4H, m) 3.3 to 3.5 (3
H, m), 5.1-5.3 (1H, m), 7.1-7.2
(2H, m), 8.1-8.2 (2H, m)

Example 3 4- (4-Octanoyloxycyclohexylidene) cyclohexyl 4-[(S) -2-
Synthesis of fluoro-2-methylhexanoyloxy] benzoate

[Chemical 18] 3 equipped with a Jimroth condenser and an argon balloon
4- (4-octanoyloxycyclohexylidene) cyclohexanol (Synthesis example 3) 1 was added to a 0 ml two-necked flask.
0.0 mg (0.031 mmol), 4-[(S) -2
-Fluoro-2-methylheptanoyloxy] benzoic acid (Synthesis Example 4) 8.3 mg (1 equivalent) and 4
-Dimethylaminopyridine 0.9 mg (0.2 times equivalent)
It was taken and dissolved in 1 ml of methylene chloride. 5.8 μl of 1,3-diisopropylcarbodiimide (1.2 times equivalent)
Was added and refluxed for 6 hours, and then the reaction solution was concentrated under reduced pressure to obtain a residue. This was purified by silica gel column chromatography (hexane / ethyl acetate = 6/1; volume ratio), and 4-
(4-Octanoyloxycyclohexylidene) cyclohexyl 4-[(S) -2-fluoro-2-methylhexanoyloxy] benzoate 9.3 mg (yield 52%)
Got The results of analyzing the physicochemical properties of this product are as follows.

Infrared absorption spectrum (ν cm ^-1 ): 342
8, 2932, 2860, 1795, 1775, 1724, 1466, 1380, 1276, 1202, 1162, 1110, 1016, 368, 34
4, 310, 292, 258 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ , δppm): 0.0
_{7~1.0 (6H, m, CH 3} ), 1.1~1.5 (12
H, m), 1.5-1.8 (9H, m), 1.8-2.3
(8H, m), 2.27 to 2.33 (2H, t, J = 7.
5 Hz), 2.4 to 2.6 (4H, m), 4.9 to 5.0
(1H, m), 5.1-5.3 (1H, m), 7.1-7.
2 (2H, d, J = 9Hz), 8.1-8.2 (2H,
m, J = 8.8)

Example 4 Synthesis of 4- (4-octoxycyclohexylidene) cyclohexyl 4-[(S) -4-methylhexanoyloxy] benzoate

[Chemical 19] 3 equipped with a Jimroth condenser and an argon balloon
4- (4-octanoyloxycyclohexylidene) cyclohexanol (Synthesis example 3) 1 was added to a 0 ml two-necked flask.
2.0 mg (0.038 mmol), 4-[(S) -4
-Methylhexoxy] benzoic acid (Synthesis example 5) 9.0 mg (1 equivalent) and 4-dimethylaminopyridine 0.9 mg (0.2 equivalent) were taken and dissolved in 1 ml of methylene chloride. After adding 6.7 μl (1.2 times equivalent) of 1,3-diisopropylcarbodiimide and refluxing for 6 hours, the reaction solution was concentrated under reduced pressure to obtain a residue. This was purified by silica gel column chromatography (hexane / ethyl acetate = 6/1; volume ratio), and 4- (4-octoxycyclohexylidene) cyclohexyl 4-[(S)
-4-Methylhexanoyloxy] benzoate 16 mg
(Yield 55%) was obtained. The results of analyzing the physicochemical properties of this product are as follows.

Infrared absorption spectrum (ν cm ^-1 ): 293
2, 2860, 2364, 1708, 1610, 1512, 1470, 1282, 1256, 1168, 1104, 412, 386, 314, 262 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ , δppm): 0.
_{7~1.0 (9H, m, CH 3} ), 1.1~1.5 (15
H, m), 1.5-1.9 (12H, m), 1.9-2.3
(4H, m), 2.5-2.7 (4H, t), 3.4-3.
5 (3H, m), 3.96-4.02 (2H, t), 5.
1 to 5.3 (1H, m), 6.88 to 6.91 (2H,
d), 7.97 to 8.00 (2H, d)

Example 5 The compounds obtained in Examples 1 to 4 were filled in a liquid crystal cell [polyimide alignment film: LQ-1800 (manufactured by Hitachi Chemical Co., Ltd.), cell gap: 2 μm, rubbing direction: parallel] to change the liquid crystal phase. Was measured. The results are shown in Table 1.

[Table 1]

[0046]

The 4- (4-substituted cyclohexylidene) cyclohexanol derivative of claim 1 is a novel liquid crystal compound. According to the manufacturing method of claim 2, the 4- (4
-Substituted cyclohexylidene) cyclohexanol derivatives can be prepared.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C07D 237/14 237/24 239/28 239/34 241/14 241/18 C09K 19/30 9279- 4H 19/34 9279-4H G02F 1/13 500

Claims (2)

[Claims] 1. A compound represented by the general formula (I): [In the general formula (I), R represents an alkyl group which may have a branch, Ar represents an aromatic group which may have a substituent,
X and Y each independently represent O or COO, m and n each independently represent 0 or 1, and Q * represents an optically active alkyl group having an asymmetric carbon atom. ] Represented by 4
-(4-Substituted cyclohexylidene) cyclohexanol derivative. 2. Formula (II): 4- (4-hydroxycyclohexylidene) represented by
A long-chain alkyl group is introduced into cyclohexanol by alkoxyalkylation or alkylesterification to give a compound represented by the formula (III): [In the formula (III), R represents an alkyl group which may have a branch, and X represents O or COO. ] HOOC- (Ar) m- (Y) n-Q * (IV) [wherein Ar is a fragrance which may have a substituent] Represents a group group, Y represents O or COO, m and n each independently represent 0 or 1, and Q * represents an optically active alkyl group having an asymmetric carbon atom. ] The method for producing a 4- (4-substituted cyclohexylidene) cyclohexanol derivative according to claim 1, which comprises condensing an optically active carboxylic acid.