JPH0269429A - Liquid crystal intermediate and liquid crystal compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X is OH or COOH; n is 1 or 2; p is 0 or 1; q is 0-5; * represents optically active C.; B is formula II (a is 0-4; Z is halogen)]. EXAMPLE:4-Hydroxybenzoic acid 2-chloro-1-methylpropylester. USE:An intermediate for liquid crystal, expressing chiral smectic C phase in temperature range close to ambient temperature, having large spontaneous polarization and useful in synthesis of ferrodielectric liquid crystal compound exhibiting high speed response to electric field. PREPARATION:For example, a compound expressed by formula III is converted to acid chloride, which is then reacted with an optically active alcohol expressed by formula IV and then hydrolyzed to provide the compound expressed by formula I (X is OH and p is 1). Then the compound expressed by formula I is reacted with a compound expressed by formula V (R is alkyl, alkoxy, alkenyl, etc.; m is 1 or 2; A is formula II) to provide the liquid crystal compound expressed by formula VI [r is 0 or 1 provided that (when r is 0, m and n are 1); Y is COO or OCO].

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to liquid crystal intermediates and liquid crystal compounds.

More specifically, the invention of claim 1 of the present invention can be suitably used for producing an intermediate of a liquid crystal compound suitably used in the field of liquid crystal materials such as optoelectronics, particularly the liquid crystal compound of claim 2. Related to liquid crystal intermediates. In addition, the invention of claim 2 of the present invention exhibits excellent properties such as expressing a chiral smectic C phase (SmC" phase) in a temperature range close to room temperature, having large spontaneous polarization, and exhibiting high-speed response to an electric field. The present invention relates to a liquid crystal compound that is a ferroelectric liquid crystal having liquid crystal properties and can be suitably used in various liquid crystal material fields including the field of optoelectronics.

[Conventional technology]

Conventionally, a compound represented by the following formula is known, but a compound in which the benzene ring in this compound is substituted with a hydroxy group, a phenyl group, a benzoyloxy group, etc. is not known.

In addition, as aromatic esters having an optically active chloroalkyl group having a structure in which a methylmethylene type asymmetric carbon and a chloromethylene type asymmetric carbon are directly bonded as described above, Table 1 of JP-A-62-142131 lists The compounds described are known. However, in these aromatic esters, the structure of the terminal portion on the side of the optically active chloroalkyl group is as follows (however, S in formula (ii) is 0 or 1).
The compounds represented by the formula (i) have the positions of C1 and CL swapped, and further have a -CH2- group between the carbonyloxy group and the asymmetric carbon. It belongs to a different classification from the compounds of .

Further, the conventional optically active aromatic esters having the terminal group of formula (ii) are liquid crystal compounds, but in the case of two-ring compounds, SmC''' phase is difficult to develop, and in the case of three-ring compounds, SmC''' phase is difficult to develop. There were problems such as the temperature range in which the ``'' phase was high, making it impractical.

[Problem to be solved by the invention]

An object of the present invention is to provide a novel liquid crystal compound that is a ferroelectric liquid crystal that has an SmC''' phase in a temperature range close to room temperature, has large spontaneous polarization, and has high response speed to an electric field.

Another object of the present invention is to provide a liquid crystal intermediate, which is a novel optically active compound that can be suitably used as an intermediate for liquid crystal compounds having at least the above-mentioned excellent properties. .

[Means to solve the problem]

As a result of extensive research in order to solve the above problems, the present inventors have discovered that the benzene ring has a specific optically active group bonded to the benzene ring via an ester bond or an ether bond, and that a specific optically active group is attached to the p-position of the benzene ring. 2- to 4-ring optically active aromatic esters and ethers with a specific structure in which the group is substituted and the benzene ring may be substituted with a halogen atom are ferroelectric with large spontaneous polarization. It has been discovered that this compound is a novel liquid crystal compound that exhibits high-speed response to external factors such as electric fields, and exhibits an SmC phase in a temperature range close to room temperature.

In addition, as a result of extensive research into the synthesis process of the liquid crystal compound, optically active aromatic hydroxyl or carboxylic acid forms corresponding to the optically active group-containing moiety of the liquid crystal compound have been discovered as intermediates for the liquid crystal compound. The present invention was completed by discovering that the present invention can be suitably used.

That is, the invention of Claim 1 of the present application is based on the following general formula CHi ct [However, in formula (1), (7) X is -OB or -coon''
il' ant, n is 1 or 2, p is 0 or 1, q represents an integer of 0 to 5, each represents an optically active carbon atom, each B is independently, Z is a halogen atom and may be the same or different from each other. ] It consists of a liquid crystal intermediate represented by the following.

In addition, the invention of claim 2 of the present application is based on the following general formula [wherein R in formula (n) represents an alkyl group, an alkoxy group, an alkenyl group, or an alkenyloxy group having 1 to 30 carbon atoms, and - is l or 2, n is 1 or 2, r is O or 1 (however, if r = 0, m-n = 1), p is 0 or 1, and q represents an integer from O to 5,
Y represents -C00- or 10CO-, A and B each independently, Z represents a halogen atom, Z may be the same or different, A and B are the same It is made of a liquid crystal compound represented by the following, which may or may not be the same.

In the formula (I) and formula (Tl''), 2 is a halogen atom, and the halogen atom includes a fluorine atom,
Examples include chlorine atom, bromine atom and iodine atom, among which fluorine atom and chlorine atom are preferred, with fluorine atom being particularly preferred.

In formula H) and formula (I[), a is an integer of O to 4, with O or 1 being preferred.

In the formulas (1) and (II), preferred examples of A and B include the following, and among these, the following are particularly preferred.

In the formula (n), the combination of m, r and n is (m, r, n)=(1,0,1).

(1,1,1), (2,1,1), (1,1°2) and (2,1,2), among which (1,
0,1), (1,1,1), (2°1.1) and (1,
1, 2) are preferred.

The carbon number of R in the formula (U) is 1 to 30, preferably about 4 to 18, particularly preferably about 6 to 14.

Some specific examples of groups having preferable carbon numbers as R are as follows.

When R is an alkyl group, examples of the alkyl group include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group. etc. can be mentioned.

When R is an alkoxy group, examples of the alkoxy group include a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, Examples include a tetradecyloxy group, a hexadecyloxy group, and an octadecyloxy group.

When R is an alkenyl group, examples of the alkenyl group include butenyl group, pentenyl group, hexenyl group, octenyl group, nonenyloxy group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, etc. Can be done.

When R is an alkenyloxy group, examples of the alkenyloxy group include a butenyloxy group, a pentenyloxy group, a hexenyloxy group, a heptenyloxy group, an octenyloxy group, a nonenyloxy group, a decenyloxy group, an undecenyloxy group, dodecenyloxy group, tetradecenyloxy group, hexadecenyloxy group,
Examples include octadecenyloxy group.

Note that the various alkyl groups, alkenyl groups in the alkoxy groups, and alkenyl groups in the alkenyloxy groups may be linear or branched, but are usually linear. Chain-shaped ones and branched ones with a low degree of branching having a lower alkyl group such as a methyl group in the side chain are preferred, and linear ones are particularly preferred.

In addition, there is no particular restriction on the position of the carbon-carbon double bond in the alkenyl groups in the various alkenyl groups and alkenyloxy groups, but those having a vinyl group at the end are usually preferred, and specific For example, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, 7-octenyl group, 9-decenyl group, 10-undecenyl group, 1
Examples include 1-dodecenyl group, 13-tetradecenyl group, 15-hexadecenyl group, and 17-octadecenyl group.

In the formula (1) and formula (II), q is an integer of 0 to 5, preferably an integer of 0 to 4, particularly q-
O is preferable because it takes the SmC0 phase in a lower temperature range.

The optically active group CHz C in the above formulas (1) and (II)
I 1+4l-CI(-(CHz) Q-Cl:l (
Specific examples of m) (q and * represent the same meanings as above) include 2-chloro-1-methylpropyl group, 2-
Chloro-1-methylbutyl group, 2-chloro-1-methylpentyl group, 2-chloro-1-methylhexyl group, 2-
Mention may be made of the chloro-1-methylheptyl group and the 2-chloro-1-methyloctyl group.

The structures of these optically active groups, when expressed as alcohol CH3CI (q and * represent the same meanings as above), are (+)-erythro form, (-)-erythro form, (
+)-threo form and (-)-threo form can be mentioned.

Specific examples of the compound represented by the formula (1) are
compound C1,) where X is =OR and p=o, χ is -coon
and the compound (IC) is p-1 and X is -coo
Compounds (I4) which are i and p-0 are classified as follows.

That is, specific examples of the compound (1,) include: 4-hydroxybenzoic acid 2-chloro-1-methylpropyl ester 4-hydroxybenzoic acid 2-chloro-1-methylbutyl ester 4-hydroxybenzoic acid 2 -Chloro-1-methylpentyl ester 4-hydroxybenzoic acid 2-chloro-1-methylhexyl ester 4-hydroxybenzoic acid 2-chloro-1-methylheptyl ester 4-hydroxybenzoic acid 2-chloro-1-methyloctyl ester 2-fluoro-4-hydroxybenzoic acid 2-chloro-
1-Methylpropyl ester 3-fluoro-4-hydroxybenzoic acid 2-chloro-
1-Methylpropyl ester 4-hydroxy-2-chlorobenzoic acid 2-chloro-1
-Methylpropyl ester 4-hydroxy-3-chlorobenzoic acid 2-chloro-1
-Methylpropyl ester 4-(4-hydroxyphenyl)benzoic acid 2-chloro-
Examples include 1-methylpropyl ester.

Specific examples of the compound Nb) include 4-(2-chloro-1-methylpropyloxy)phenol 2-fluoro-4-(2-chloro-1-methylpropyloxy)phenol 3-fluoro-4- (2-chloro-1-methylpropyloxy)phenol 2-chloro-4-(2-chloro-1-methylpropyloxy)phenol 3-chloro-4-(2-chloro-1-methylpropyloxy)phenol 4- (4-(2-chloro-1-methylpropyloxy)phenyl)phenol and the like can be mentioned.

Specific examples of the compound (IC) include 4-(2-chloro-1-methylpropyloxycarbonyl)benzoic acid 2-fluoro-4-(2-chloro-1-methylpropyloxycarbonyl)benzoic acid 3 -Fluoro-4-(2-chloro-1-methylpropyloxycarbonyl)benzoic acid 2-chloro-4-(2-chloro-1-methylpropyloxycarbonyl)benzoic acid 3-chloro-4-(2-chloro- Examples include 1-methylpropyloxycarbonyl)benzoic acid and 4-(4-(2-chloro-1-methylpropyloxycarbonyl)phenyl)benzoic acid.

Specific examples of the compound (I4) include 2-fluoro-4-(2-chloro-1-methylpropyloxy)benzoic acid 3-fluoro-4-(2-chloro-1-methylpropyloxy)benzoate. -4-(2-chloro-1-methylpropyloxy)benzoic acid 2-chloro-4-(2-chloro-1-methylpropyloxy)benzoic acid 3-chloro-4-(2-chloro-1-methylpropyl) Examples include 4-(4-(2-chloro-1-methylpropyloxy)phenyl)benzoic acid and the like.

Specific examples of the compound represented by the formula (II) are a compound (■,) in which r is 1 and Y is -COO-, a compound (Ilb) in which r is 1 and Y is -COO-, and r is O
and m=n=1 (■.

) are classified as follows.

That is, specific examples of the compound (■,) include 4-(4-hexyloxybenzoyloxy)benzoic M
2-chloro-1-methylpropyl ester 4-(4-decyloxybenzoyloxy)benzoic acid
2-chloro-1-methylpropyl ester 4-(4-decyloxybenzoyloxy)-2-fluorobenzoic acid 2-chloro-1-methylpropyl ester 4-(4-decyloxy-3-fluorobenzoyloxy)benzoic acid 2 -Chloro-1-methylpropyl ester 4-(4-decyloxybenzoyloxy)benzoic acid
2-chloro-1-methylhebutyl ester 4-(4-tetradecyloxybenzoyloxy)benzoic acid 2-chloro-1-methylpropyl ester 4-(4-decylbenzoyloxy)benzoic acid 2-chloro-1-methyl Propyl ester 4- [4-(9-decenyloxy)benzoyloxy)benzoic acid 2-chloro-1-methylpropyl ester 4- (4-(9-decenyl)benzoyloxy)benzoic acid 2-chloro-1-methylpropyl ester 4- (4-(4-decyloxybenzoyloxy)phenyl)benzoic acid 2-chloro-1-methylpropyl ester 4- (4-(4-decyloxyphenyl)benzoyloxy)benzoic acid 2-chloro-1-methyl Propyl ester 4- (4-(4-decyloxyphenyl)benzoyloxy)-2-fluorobenzoic acid 2-chloro-1-methylpropyl ester 4-decyloxybenzoic acid 4'-(2-chloro-1
-methylpropyloxy)phenyl ester 4-(4-decyloxyphenyl)benzoic acid 4' -(
2-Chloro-3-methylpropyloxy)phenyl ester 4-(4-octyloxybenzoyloxy)benzoic acid 2-chloro-1-methylpentyl ester 4-[4-(4-(9-decenyloxy)phenyl)
benzoyloxy]benzoic H2-rio.

-1-methylpentyl ester 4- (4-(4-octyloxybenzoyloxy)
phenyl)benzoic acid 2-chloro-1-methylpentyl ester 2-fluoro-4-(4-octyloxybenzoyloxy)benzoic acid 2-chloro-1-methylpropyl ester 4- (4-(4-decyloxyphenyl) Examples include benzoyloxy)benzoic acid 2-chloro-1-methylbutyl ester.

Specific examples of the compound (■,) include 4-(4-decyloxyphenoxycarbonyl)benzoic acid 2-chloro-1-methylpropyl ester 4-(4-decyloxyphenoxycarbonyl)-2-
Fluorobenzoic acid 2-'7oo-1-methylpropyl ester 4-(4-decyloxy-3-fluorophenoxycarbonyl)benzoic acid 2-chloro-1-methylpropyl ester 4- (4-(4-decyloxyphenoxycarbonyl) Phenyl)benzoic acid 2-chloro-1-methylpropyl ester 4- (4-(4-decyloxyphenyl)phenoxycarbonyl)benzoic acid 2-chloro-1-methylpropyl ester 4- (4-(4-decyloxyphenyl) ) phenoxycarbonyl)-2-fluorobenzoic acid 2-chlorol
-Methylpropyl ester 4-(2-chloro-1-methylpropyloxy) Benzoic acid 4'-decyloxyphenyl ester 3-fluoro-4-(2-chloro-1-methylpropyloxy) Benzoic acid 4'-decyloxy Phenyl ester 4-(2-chloro-1-methylpropyloxy')benzoylt 4'-(4-decyloxyphenyl)
Examples include phenyl ester 4-(4-(2-chloro-1-methylpropyloxy)phenyl)benzoic acid 4'-decyloxyphenyl ester.

Specific examples of the compound (nc) include 4-(4-decyloxyphenyl)benzo[2-chloro-1-methylpropyl ester 4-decyloxy-4'
-(2-chloro-1-methylpropyloxy)biphenyl and the like can be mentioned.

Next, an example of a suitable method for synthesizing the compound represented by formula (1) will be briefly illustrated by a chemical formula according to the above classification.

In addition, in the example of the following synthetic steps, (■') means an optically active alcohol represented by the following formula (% formula %) (q and * represent the same meanings as above). This optically active alcohol (
As (2'), (+)-erythro form, (-)-erythro form, (+)-threo form, or (-)-threo form can be used.

The optical purity of these optically active alcohols used is preferably pure, but can be appropriately selected depending on the purpose.

Moreover, the symbols in the following compounds represent the same meanings as above.

(Ib ”) Hi ■, Input method (Ic1) (1-z) (IC) (1゜I6 A method NC-(B)--OR+ (Ib+) (II[' 5O CH-CH -(CHt), -CH5 (■1 lul+ Cflz C1 Hydrolysis 11 (I□) HOCO-(B) r-0-CH-
C1(-(CHt) a-CHz(1,) Next, an example of a suitable method for synthesizing the liquid crystal compound represented by formula (II) will be briefly illustrated by a chemical formula according to the above classification.

The symbols used in the following synthesis steps have the same meanings as above.

R-(A), -COOH+ (1,') or (I,)
R-(A), -OH 1 IC) or (a CH, CI R-A-B-COOII + (III'
) CHa Cl Esterification 11 -→R-A-B-COO-CH-CH-(C1h)-
CHs(IIc) P-^-B-OH+ (Ib+) C1,CI Etherification II-1→R-A-BJ-C1l-CI-(CHz)-CH
The compound represented by formula (I), that is, the liquid crystal intermediate of the present invention, and the compound represented by formula (■), that is, the liquid crystal compound of the present invention can be synthesized as described above. The compound can be recovered as a product or intermediate product of desired purity using conventional separation and purification methods.

Note that, if necessary, a method for synthesizing the liquid crystal compound may be employed without isolating the liquid crystal intermediate.

The liquid crystal compound of the present invention thus obtained has large spontaneous polarization, exhibits high-speed response to an electric field, and
It is a ferroelectric liquid crystal that exhibits excellent properties such as taking an SmC1 phase in a temperature range close to room temperature, and can be suitably used in a wide range of fields in which liquid crystal materials are used, including the field of optoelectronics.

Furthermore, the liquid crystal intermediate of the present invention can be particularly suitably used as a raw material (intermediate raw material) for synthesizing the liquid crystal compound of the present invention, as exemplified above. Furthermore, it is expected that this liquid crystal intermediate can be suitably used as a raw material (intermediate raw material) for synthesizing other liquid crystal compounds.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

The structure of each compound obtained can be identified by NMR, IR
This was done by single element analysis etc.

Table 1 shows the phase transition behavior, spontaneous polarization value, and electric field response time of the liquid crystal compounds obtained in Examples 6 to 11, and Table 2 shows the liquid crystal intermediates obtained in Examples 1 to 5. and Example 6
The elemental analysis values of the liquid crystal compounds obtained in ~11 are shown.

In addition, FIGS. 1 and 2 show the NMR chart and IR chart of the compound obtained in Example 1, respectively,
FIGS. 3 to 7 show Example 2.3.6.7, respectively.
, and NMR of the liquid crystal intermediate or liquid crystal compound obtained in 8
Show chart.

Measurement of the phase transition temperature and confirmation of the phase were performed using DSC and a polarizing microscope, respectively. (Cry: crystalline state, SmC
": chiral smectic C phase, SmA: smectic A phase, Iso: isoyoshi phase, the number of phase transition behavior is the phase change temperature expressed in °C.) Nobisono 6 (Example 1) ■4- Synthesis of acetoxybenzoic acid 2-chloro-1-methylpropyl ester 30 mmol (5,4 g) of 4-acetoxybenzoic acid and 90 mmol (10,8 g) of thionyl chloride in toluene 1
After stirring the 00IR1 solution at 80°C for 2 hours, the reaction solution was concentrated under reduced pressure to obtain an acid chloride. (−) −
(erythro) 3-chloro-2-butanol 1
0 mmol (1,1 g) and T of triethylamine 5d
HF30al! Add THF 1 of the above acid chloride to the solution.
After dropping the 0d solution, the mixture was stirred for 10 hours. After concentrating the reaction solution, water was added and extracted with ether. The extract concentrate was purified by column chromatography to obtain 2.3 g of ester (yield: 85%).

(2) Synthesis of 4-hydroxybenzoic acid 2-chloro-1-methylpropyl ester To a solution of 8 mmol (2.2 g) of the ester obtained in (1) in 200 d of ether, benzylamine 20- was added and stirred for 5 hours. After washing the reaction solution with water, it was purified by column chromatography to obtain 1.7 g of the desired hydroxyl compound (
A yield of 93% was obtained.

(Liquid: Boiling point is unknown because vacuum distillation is not possible) (Example 2
) ■Synthesis of 4-(4-acetoxyphenyl)benzoic acid 2-chloro-1-methylpropyl ester 4-( obtained by acetylating 4-(4-hydroxyphenyl)benzoic acid)
4-acetoxyphenyl)benzoic acid 20 mmol (5,
After stirring a solution of 1 g) and 90 mmol (10.8 g) of thionyl chloride in 100 rIdl of toluene at 80"C for 2 hours, the reaction solution was concentrated under reduced pressure to obtain an acid chloride. (
-)-(erythro) 10 mmol (1,1 g) of 3-chloro-2-butanol and 5 triethylamine
T) of the above acid chloride compound in a THF 30d solution of In1
(After dropping the FlOrn1 solution, it was stirred for 10 hours.

After concentrating the reaction solution, water was added and extracted with ether.

The extract concentrate was purified by column chromatography to obtain 2.6 g of ester (yield: 75%).

■4-(4-hydroxyphenyl)benzoic acid 2chloro-
To a solution of 7 mmol (2.4 g) of the ester obtained in the synthesis of 1-methylpropyl ester in ether 200 d, benzylamine 20 d was added and stirred for 5 hours. After washing the reaction solution with water, it was purified by column chromatography to obtain 1.8 g (yield: 84%) of the desired hydroxyl compound.

(Melting point = 131-133°C) (Example 3) ■Synthesis of 4-acetoxy 2-fluorobenzoic acid 2-chloro-1-methylpropyl ester 2-fluoro-4
-20 mmol (4.0 g) of 4-acetoxy-2-fluorobenzoic acid obtained by acetylating hydroxybenzoic acid
A solution of 60 mmol (7.2 g) of thionyl chloride in 100 d of toluene was stirred at 80°C for 2 hours, and the reaction solution was concentrated under reduced pressure to obtain an acid chloride. (-) -(er
ythro)-3-chloro-2-butanol 10 mmol (1°Ig) and triethylamine 5d) (F3
A THF 10 mffi solution of the above acid chloride compound was added dropwise to the 0d solution, and the mixture was stirred for 10 hours. After concentrating the reaction solution, water was added and extracted with ether. The extract concentrate was purified by column chromatography to obtain ester form 2.
2 g (yield 76%) was obtained.

(2) Synthesis of 2-fluoro-4-hydroxybenzoic acid 2-chloro-1-methylpropyl ester To a solution of 7 mmol (2.0 g) of the ester obtained in (1) in 200 d of ether, benzylamine 20- was added and stirred for 5 hours. After washing the reaction solution with water, it was purified by column chromatography.
1.5 g (yield: 87%) of the desired hydroxyl compound was obtained.

(Melting point: 56-58°C) (Example 4) ■Synthesis of 4-acetoxybenzoic acid 2-chloro-1-methylhebutyl ester 30 mmol (5.4 g) of 4-acetoxybenzoic acid and 90 mmol of thionyl chloride ( 10,8g) of toluene 1
After stirring the 00d solution at 80° C. for 2 hours, the reaction solution was concentrated under reduced pressure to obtain an acid chloride. (-) -(er
ythro) 10 mmol (1,6 g) of 3-chloro-2-octatool and 5! of triethylamine! TH of d
The THFIO-solution of the acid chloride compound was added dropwise to the F30d melt, and then stirred for 10 hours. After concentrating the reaction solution, water was added and extracted with ether. The extract concentrate was purified by column chromatography to obtain ester 2.5
g (yield 76%) was obtained.

■Synthesis of 4-hydroxybenzoic acid 2-chloro-1-methylhebutyl ester 20 m of benzylamine was added to a solution of 7 mmol (2.3 g) of the ester obtained in step (2) in 200 d of ether, and the mixture was stirred for 5 hours. After washing with water, it was purified by column chromatography and 1.8g of the desired hydroxyl compound (
A yield of 90% was obtained.

(Liquid: boiling point is unknown as vacuum distillation is not possible) (Example 5)
) ■Synthesis of 4-(2-chloro-1-methyl-lupropyloxy)phenol () p~tosylnsulfonic acid 2- obtained by tosylating (erythro)-3-chloro-2-butanol
Chloro-1-methylpropyl ester 10 mmol (2
, 6 g) and 30 mmol (3,3 g) of hydroquinone
A solution of 30 mmol (1.3 g) of sodium hydroxide in 2 ttrfl of water + 6 d of n-butanol was added dropwise to the n-butanol concentrate, followed by stirring at 120°C for 5 hours. After adding water to the reaction solution and extracting it with ether, the extract was dried and concentrated, and the concentrate was purified by column chromatography to obtain 1.0 g of the desired hydroxyl compound (yield: 50
%) was obtained.

(Melting point = 42 to 44°C) Eyes and people ■4-(4-octyloxybenzoyloxy)benzoic acid M Synthesis of 2-chloro-1-methylpropyl ester 4-octyloxybenzoic acid 2.1 mmol (0° 53
A toluene 10d solution of g) and 6.3 mmol (0.76 g) of thionyl chloride was stirred at 80°C for 2 hours and then concentrated under reduced pressure to obtain an acid chloride. A THF51111 solution of the acid chloride was added dropwise to a THFIO solution of 0.77 mmol (160 µ) of the hydroxyl obtained in Example 1 and triethylamine 1-, and the mixture was stirred for 10 hours. After concentrating the reaction solution, water was added and extracted with ether. After concentrating the extract, it was purified by column chromatography to obtain the desired ester 220cm (yield: 68%).
) was obtained.

(Example 7) ■ Synthesis of 4-(4-(9-decenyloxy)phenyl)benzonitrile 20 mmol (5.4 g) of IO-iodo-1-decene,
MEK 100ad of 20 mmol (3,9 g) of 4-(4-hydroxyphenyl)benzonitrile and 80 mmol (11 g) of anhydrous potassium carbonate! The suspension was stirred at reflux for 20 hours. After filtering and concentrating the reaction solution, it was purified by column chromatography to obtain 4.0 g (yield: 60%) of the ether.

(4) Synthesis of 4-(4-(4-(9-decenyloxy)phenyl)benzoyloxy)benzoic acid 2-chloro-1-methylpropyl ester 5 mmol (1,76 g) of the carboxylic acid compound obtained in (1) and Example 1 4 mmol (0.91 g) of the hydroxyl compound obtained in
It was synthesized in the same manner as in Example 6 (2) using. (Yield 65%) (Example 8) ■Synthesis of 4-(4-(9-decenyloxy)phenyl)benzoic acid 10 mmol (3.3 g) of the nitrile compound obtained in (■), 40 mmol (1,3 g) of potassium hydroxide, 3g), ethanol 10I
After stirring the mixture of Ii and water 2 for 5 hours under reflux, dilute hydrochloric acid was added to make an acidic solution. After adding water and extracting with methylene chloride, the mixture was dried and concentrated to obtain 3.2 g (yield: 91%) of a carboxylic acid.

■Synthesis of 4-(4-(4-octyloxybenzoyl)oxyphenyl)benzoic acid 2-chloro-1-methylpropyl ester 4-octyloxybenzoic acid 10 mmol (2°5g)
and 7 mmol (2,1
Synthesis was carried out in the same manner as in Example 6 (2) using g). (Yield 9
0%) (Example 9) Synthesis was carried out in the same manner as in Example 6 (2) using 0 mmol (3.5 g) and 5 mmol (1.4 g) of the hydroxyl compound obtained in Example 4. (Yield 48%)■2-fluoro4-(
4-Octyloxybenzoyloxy)benzoic acid 2-
Synthesis of chloro-1-methylpropyl ester 10 mmol (2°5 g) of 4-octyloxybenzoic acid
and 5 mmol (1,2
Synthesis was carried out in the same manner as in Example 6 (2) using g). (yield 7
7%) (Example 10) (Example 11) ■4-(4-decyloxyphenyl)benzoic acid 4'-(
Synthesis of 2-chloro-3-methylpropyloxyphenyl ester) Using 8 mmol (2.8 g) of 4-(4-decyloxyphenyl)benzoic acid and 4 mmol (0.8 g) of the hydroxyl compound obtained in Example 5. It was synthesized in the same manner as in Example 6 (2). (Yield 54%) ■Synthesis of 4-(4-(4-decyloxyphenyl)benzoyloxy)benzoic acid 2-chloro-1-methylheptyl ester 4-(4-decyloxyphenyl)benzoic acid 1 strength bH
Table 2 [Effects of the Invention] According to the present invention, the present invention has excellent properties such as large spontaneous polarization, fast response to an electric field, and SmC''' phase in a temperature region close to room temperature. A novel liquid crystal compound exhibiting liquid crystal properties and a liquid crystal intermediate that can be advantageously used in the production thereof can be provided.

[Brief explanation of the drawing]

Figures 1, 3 and 4 show Example 1.2, respectively.
and 3 shows an NMR chart of the liquid crystal intermediate of the present invention obtained in 3. FIG. 2 shows the I of the liquid crystal intermediate of the present invention obtained in Example 1.
An R chart is shown. Moreover, FIGS. 5 to 7 show NMR charts of the liquid crystal compounds of the present invention obtained in Examples 6 to 8, respectively.

Claims (1)

[Claims] 1. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [However, in formula (I), X is -OH or -COOH, and n is 1 or 2. Yes, p is 0 or 1, and q is 0
Represents an integer of ~5, * represents an optically active carbon atom, and B each independently has a ▲mathematical formula, chemical formula, table, etc.▼
Here, a is an integer of 0 to 4, Z is a halogen atom, and they may be the same or different. ] A liquid crystal intermediate represented by . 2. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [However, R in formula (II) is an alkyl group, alkoxy group, alkenyl group, or alkenyloxy group having 1 to 30 carbon atoms. , m is 1 or 2, n is 1 or 2, r is 0 or 1 (however, if r=0, m=n=1), and p is 0 or 1, q represents an integer from 0 to 5, Y represents -COO- or -OCO-, A and B each independently represent ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where a is an integer of 0 to 4, Z represents a halogen atom, Z may be the same or different from each other, and A and B may be the same or different from each other. ] A liquid crystal compound represented by