JPH02131451A - Biphenylcarboxylic acid derivative and liquid crystal composition - Google Patents

Abstract

NEW MATERIAL:A biphenylcarboxylic acid derivative shown by formula I (R<1> and R<2> are 1-18C straight-chain or branched chain alkyl and further R<2> is group shown by formula II; R<3> is 1-18C straightchain or branched chain alkyl; X<1> and X<2> are H, Cl or F; n is 1-10 integer). EXAMPLE:(R)-4-Hexyloxymethylphenyl-4-(1-methylnonyl)oxybiphenyl-4'- carboxylate. USE:A ferroelectric liquid crystal substance having stability to light and large spontaneous polarization and a liquid crystal compound having a chiral smectic C phase (SmC*) or smectic C(SmC) phase useful as a component for ferroelectric liquid crystal composition. PREPARATION:A biphenylcarboxylic acid derivative corresponding to a compound shown by formula I is condensed with a phenol derivative to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel liquid crystal compound useful as a component of a ferroelectric liquid crystal composition and having excellent stability, and a liquid crystal composition using this liquid crystal compound.

[Background technology]

A liquid crystal display device that utilizes the optical switching phenomenon of ferroelectric liquid crystals proposed by Clark et al. in 1980 has a response speed several hundred times faster than that of conventional nematic liquid crystal display devices. 2. Description of the Related Art Research on ferroelectric liquid crystal materials and display elements using the same is being actively conducted for applications in a variety of fields that have been difficult to accommodate with display elements.

Ferroelectric liquid crystal refers to a series of smectic liquid crystals in which the long axis of the liquid crystal molecules is at a certain angle with the layer normal direction, but in practical terms it is called chiral smectic C phase (SLIC*
) is used. Liquid crystal materials for producing practical ferroelectric liquid crystal display elements can be prepared as a liquid crystal composition consisting of a large number of ferroelectric liquid crystal compounds, or as a liquid crystal composition consisting of a large number of smectic C (SIIIC) phase compounds and a large number or a small number of ferroelectric liquid crystal compounds. It is used as a liquid crystal composition consisting of a dielectric liquid crystal compound, but as in the case of a practical nematic liquid crystal display element, such a liquid crystal composition consisting of multiple components has the following properties:
It must have various properties required in practical use, such as operating temperature range, response speed, spontaneous polarization, helical pitch, and chemical stability.

However, such compounds or compositions that can be put to practical use have not yet been found, and efforts are being made to develop various compounds with excellent properties that can be useful components of ferroelectric liquid crystal compositions. desired.

Among these characteristics, spontaneous polarization is one of the factors that affects the high-speed response that is a characteristic of ferroelectric liquid crystals. The relationship between response speed and spontaneous polarization is expressed by the formula τ-7/Ps-EC (τ )
is the response time, (1) is the viscosity, Ps is the spontaneous polarization, and E is the electric field. In other words, a substance with a larger spontaneous polarization or a substance with a smaller viscosity enables a faster response.

The present inventors have focused on this spontaneous polarization, and have developed a ferroelectric liquid crystal material that is stable to light and chemically and has a large spontaneous polarization, and as a component of ferroelectric liquid crystal compositions. As a result of intensive research aimed at providing a liquid crystal compound having a useful SmC'' phase or S+mC phase, we succeeded in providing a new compound according to the present invention.

[Disclosure of the Invention] The present invention is based on the general formula, (wherein Rl represents a straight or branched alkyl group having 1 to 18 carbon atoms, and R2 represents a
8 represents a linear or branched alkyl group, or is a branched alkyl group with the formula CHs -CH-Coo-R'; XI and x2 each represent a hydrogen atom, a chlorine atom or a fluorine atom; Representation, n
represents an integer of l −10) and at least one of these compounds.
The present invention provides a liquid crystal composition characterized by containing seeds. The novel liquid crystal compound according to the present invention can be
Not only compounds having the c main phase or the SIIC phase, but also compounds having no phase can be effectively used to adjust the various properties of the ferroelectric liquid crystal composition.

The novel compound according to the present invention can be produced by the synthetic route (Process 11 Process 2, Process 3) exemplified by the formula below. The synthetic route shown here is an example of a process for producing a novel compound according to the present invention, which includes:
The manufacturing process for the compound represented by formula (I) is not limited to this.

and R3 is a straight chain having 1 to 16 carbon atoms or represented by the general formula (I). It can be synthesized by a condensation reaction with the phenol derivative (I[[) obtained by Process 2.

First, the synthesis process of the above biphenylcarboxylic acid derivative (n) will be explained.

(In the case of X'-X''-H) Methyl alkoxybiphenylcarboxylate is produced by an etherification reaction between alkyl tosylate (R'OTs) obtained by tosylation of 2-alkanol and methyl hydroxybienylcarboxylate. The carboxylic acid of formula (n) is then obtained by hydrolyzing this.

(X'- 3- F, X"- H(7) case) 2-
3-7fluoro-4-methoxybiphenyl is obtained by a coupling reaction between 2-fluoro-4-bromoanisole obtained by brominating fluoroanisole and phenylmagnesium bromide. Next, after acetylating this material, the ether bond is cleaved, and the resulting phenolic O
Etherification of H with alkyl tosylate (R'OTs) gives 3-furol-4-alkoxy-4'-acetylbi7enyl. By oxidizing this product, the carboxylic acid of formula (If) is obtained.

(In the case of X'-H. 17-fluoro-4-bromo-4'-hydroxybiphenyl is obtained. Next, the OH group of this product is etherified with an alkyl tosylate (R'OTs), then Br is converted to CN, and a hydrolysis reaction is performed to obtain the carboxylic acid of formula (II).

Next, the phenol derivative (I([
) Describe the synthesis process of -t-ru.

(In the case of n-1. R" single linear chain) By reacting 4-hydroxybenzyl alcohol with a linear alcohol (R"OH) under an acid catalyst, formula
The compound I) is obtained.

(In the case of nl, R” monobranched chain) 4-prompenzyl bromide and branched chain alcohol (R
An ether compound is synthesized from "OH)" and then this compound is reacted with magnesium to prepare a Grignard reagent. This is reacted with boric acid ester and hydrogen peroxide to form the formula (
Compound m) is obtained.

(In the case of n-2) The compound of formula (III) is obtained by brominating 4-hydroxy 7enethyl alcohol and then etherifying it with alcohol (R"OR).

(When n≧3) n-promalkylbenzene is acetylated and then Bayer-Villiger oxidation is performed to form 4-(n-promalkyl).
Phenol is obtained.

By etherifying this product with alcohol (R''OH), a compound of formula (I[) is obtained.

The ester compound obtained by reacting p-cresol with benzoyl chloride is brominated, and then subjected to an etherification reaction with an alkyl lactate to obtain a compound of formula (III).

Example l A reaction vessel was charged with 8.4 g of Cs)-2-decanol and 50 mQ of pyridine, and then p-}
10 g of luenesulfonylchloride was added little by little to the mixture under stirring, and the mixture was stirred at the same temperature for 2 hours and then at room temperature for 5 hours. The reaction solution was poured into cold diluted hydrochloric acid and extracted with benzene. The benzene layer was washed with water and dried over sodium sulfate. Then, the benzene was distilled off, and (s)-1-methylenoninole=p-tonoleenesulfonate was obtained as a residue. Obtained.

In a reaction vessel, (s)-1-methylnonyl p-toluenesulfonate 149. obtained in (a) above was added. Methyl = 4
-Hydroxybiphenyl-4'-carpoxylate 10
g, anhydrous potassium carbonate 129 and cyclohexanone 60m
ff was charged and stirred at 120-130°C for 5 hours. The reaction solution was poured into water and extracted with benzene. The benzene layer was washed with water and dehydrated with sodium sulfate. The solvent was distilled off and the residue was recrystallized with methanol to give (R) monomethyl: 4- 14 g of (1-methylnonyl)oxybiphenyl-4'-carpoxylate was obtained. m. p. 55.4-56.3°C Into the reaction vessel, (R)-1 methyl obtained in (b) above = 4-(1
-methylnonyl)oxybiphenyl-4'-monocarpoxylate 149. Methanol 50m12, caustic soda 59
40 mα solution of water and 7 runs of tetrahydride (THF)
40m+2 was charged and stirred under reflux for 2 hours.

After cooling the reaction solution to room temperature and making it acidic by adding hydrochloric acid,
Stirred at 70°C for 30 minutes. The reaction solution was poured into water, the precipitated solid was collected by filtration, and recrystallized with ethanol (R).
5.4 g of -4-(1-methylnonyl)oxybi7enyl-4' monocarboxylic acid was obtained.

The phase transition temperature of this product is shown below.

4-hydroxybenzyl alcohol log in the reaction vessel,
l-hexanol 49mQ and concentrated hydrochloric acid 0.11lα・
and stirred at room temperature for 15 hours. The reaction solution was diluted by adding benzene, the benzene layer was washed with water, dehydrated with sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was distilled under reduced pressure to obtain 8 g of 4-hexynoleoxymethylphenol. Obtained. b. p. 136-137°O/0. 55n+
1.5 mHg of (R)-4-(1-methylnonyl)oxybiphenyl-4'-monocanolebonic acid obtained in (c) in a synthesis reaction vessel.
9. and 1 g of 4-hexynoleoxymethylphenol obtained in (d) above and 0.0 4-pyrrolidinopyridine
Charge 7 g of methylene chloride 20raQ solution, and add 1.1 dicyclohexyllupodiimide (DCC) under stirring at room temperature.
A 10 mQ methylene chloride solution of No. 9 was added dropwise, and after the dropwise addition, the mixture was stirred at room temperature for 4 hours.

The reaction solution was filtered to remove solid matter, and the filtrate was washed with dilute hydrochloric acid and then with water, then dehydrated with sodium sulfate, and the residue obtained by distilling off the solvent was subjected to silica gel column chromatography (eluent: benzene) and further recrystallized from acetone to obtain (R)-4-hexyloxymethyl 7enyl:4-
1.4 g of (l-methylnonyl)oxybi7enyl-4'-carpoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic values of this object are 2800-3000cm-', 1730cm-
' , 1600cm-'1270cm-', and in mass analysis there is a molecular ion peak at 544,
Based on the fact that a reference peak was observed at 337 and the raw materials used, it was confirmed that it was the target substance.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 2 In Example 1 (d), 1-hexanol was replaced with 1-petanol, and the same procedure was repeated except that 4-bentyloxime, thylphenol was obtained.

The characteristic value is 2800~3000cm-'. 173
0c+++-'. 1600cm-'1270c
m-', and mass analysis showed a molecular ion peak at 531 and a reference peak at 337, and it was confirmed to be the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

In Synthesis Example 1 (8) of Example 3, 0.9 g of 4-bentyloxymethylphenol obtained in (a) was used instead of 4-hexyloxymethylphenol 19, and the other procedures were repeated in the same manner. (R)-4-pentyloxymethylphenyl: 4-(
1.1 g of 1-methylnonyl)oxybiphenyl-4'-carpoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. ! According to the R measurement, this object was published in Japanese Patent Publication No. 5
It was synthesized according to the synthesis example of 4-(γ-methoxybuvir)phenol described in Publication No. 8-85825.

In Synthesis Example 1 (e), 4-hexyloxymethylphenol 19 was replaced with 4. (3-
(R)-4-(3-Methoxybutyl)phenyl=4-(1-methylnonyl)oxybi7enyl-4'-monocarpoxylate 0.5g was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800-3000 cm-'. 1730cm-
'． 1600cm Ichitomi 1270cm"". 119
0c+x-', and mass analysis showed a molecular ion peak at 502 and a reference peak at 337, and it was confirmed that it was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 4 Hexyl p-toluenesulfonate was obtained.

Next, in Example 1 (b), instead of 14 g of (s)-1-methylnonyl p-toluenesulfonate,
Using the previously obtained (R)-1-methylhexyl p-toluenesulfone}129, the other procedures were carried out in the same manner as (
S) Monomethyl: 4-(1-methylhexyl)oxybiphenyl-4' monolupoxylate was obtained. This 129 in Example 1 (c) (R) -methyl:4- (
(s)-4-(1-Methylhexyl)oxybiphenyl was used in place of 1-methylnonyl)oxybi7enyl-4'monolypoxylate l49 and in the same manner as in Example 1 (c). 4' monocarboxylic acid was obtained.

The phase transition temperature of this product is shown below.

In Example 1(a), 6.1 g of (R)-2-heptanol was substituted for 8.4 g of (s)-2-decanol.
Synthesis of (R)-1-Methyl Example 1 (e) Using (R)-4-(1-methylnonyl)oxybiphenyl-4'monocarboxylic acid, the above (R)-4-(1-methylnonyl)oxybiphenyl-4' monocarboxylic acid 4-pentyl obtained in Example 2(a) by replacing (s)-4-(1-methylhexyl)oxybiphenyl-4' monocarboxylic acid obtained in a) with 4-hexyloxymethylphenol Using oxymethylphenol and carrying out the same procedure, 0.99 of (s)-4-pentyloxymethylphenyl 4-(1-methylhexyl)oxybiphenyl-4'-monocarpoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800-3000c. 1730cm-'
．． 1600cm-'1270ci+-'.
1 190 cm-' and 4 in Mass analysis.
It was confirmed that this was the target substance based on the fact that 88 molecular ion peaks and a reference peak were observed at 295, and the raw materials used.

This material was sandwiched between hot stages FP-82 (manufactured by Mettler) and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 5 In Example 1 (d), l-hexanol was replaced with l.
4-heptyloxymethylphenol was obtained by using -heptanol and operating in the same manner.

b. p. Synthesis of 138-141'o / 0.35 mmHg In Example 1 (e), (R)-4-(1-methylnonyl)oxybiphenyl-4' monocarboxylic acid was replaced with (s) obtained in Example 4(a). )-4-(1-methylhexyl)oxybiphenyl-4'-monocarboxylic acid;
-Hexyloxymethylphenol (a) instead of lg
4-heptyloxymethylphenol obtained in 1.3
Using No. 9 and carrying out the same procedure, 0.9 g of (s)-4-heptyloxymethylphenyl 4-(1-methylhexyl)oxybi7enyl-4'-carpoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800~3QOOcm-".1730cm-
'． 1600cm-'1270cm-''.
1 190 cm-', and mass analysis showed a molecular ion peak at 516 and a reference peak at 295, and it was confirmed that it was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 6 In Example 1(d), l-hexanol was replaced with l-
4-octyloxymethylphenol was obtained by using octanol and performing the same procedure except for using octanol.

b. p. 149 ~ 152゜O / 0.45mm}
Synthesis of Ig In Example 1(e), 1.59 of (R)-4-(1-methylnonyl)oxybi7enyl-4'monocarboxylic acid was replaced with (s)-4 obtained in Example 4(a). -(1-methylhexyl)oxybiphenyl-4'monocarboxylic acid 1
．． 1 g of 4-hexyloxymethylphenol
(S)-4-octyloxymethylphenyl: 4-(1
-Methylhexyl)oxybiphenyl-4' monolupoxylate 0.5 g was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800-3000 cm-'. 1730C+1
−'． 1600cm-'1270cm-'
．． 1190 cm-', and mass analysis showed a molecular ion peak at 531 and a reference peak at 295, and it was confirmed that it was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 7 In Example 1 (a), 7 g of (R)-2-octanol was used in place of 8.49 g of (s)-2-decanol, and other procedures were repeated in the same manner to produce (R)-1-methyl. Hebutyl p-toluenesulfonate was obtained. Next, Example 1 (b
), replacing 14 g of (s)-1-methylnonyl p-toluenesulfonate with the previously obtained (R)-1
-Methylhebutyl=p-}luenesulfonate 12.5
(S) monomethyl='4-(1-methylhebutyl)oxybi7enyl-
4' monotonic lupoxylate was obtained.

This (S) monomethyl:4-(1-methylheptyl)oxybiphenyl-4'-carpoxylate 139 was added to (R) monomethyl=4-(1-methylnonyl)oxybiphenyl-4 in Example 1 (c). ' monocarboxylic acid was obtained by replacing 149 with mono-rupoxylate 149 and otherwise operating in the same manner as in Example 1(c); . The phase transition temperature is shown below.

162.7 177.9 195.5C
ry s t-〉S m C ”--1÷ch1〉■
Synthesis Example 1 of sO (unit: °C) In (e), (R)-4-(1-methylnonyl)oxybiphenyl-4'-monocarboxylic acid was replaced with (S) to 4- (obtained in (a) above). 1-methylheptyl)
Oxybiphenyl-4' monocarboxylic acid, and 4-pentyloxymethylphenol obtained in Example 2(a) in place of 4-hexyloxymethylphenol,
The rest was operated in the same manner to obtain 0.59 of (s)-4-pentyloxymethylphenyl:4-(1-methylheptyl)oxybiphenyl-4' monolupoxylate.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. ! According to the R measurement, the characteristic value of this object is 2800~3000cm-".1730cm-
'． 1600cm-'1270cm-'. 11
90 cm-', and mass analysis showed a molecular ion peak at 502 and a reference peak at 309, and it was confirmed that it was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table I.

Example 8 In Synthesis Example 1 (e), (R)-4-(1-methylnonyl)oxybiphenyl-4' monocarboxylic acid was replaced with (s)-4-(1- obtained in Example 7(a)). methylheptyl)oxybiphenyl-4'monocarboxylic acid,
-Hexyloxymethylphenol 19 was replaced with 4-octyloxymethylphenol 1.29 obtained in Example 6(a), and the other procedures were repeated in the same manner. (s)-4-Octyloxymethylphenyl: 4 - (1-methylheptyl)oxybiphenyl-4'-carpoxylate lg
I got it.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800~3000c+m-', 1730cm
One plate, 1600c+*-”1270cm-'.1
190 cm-” and 54 cm-” in mass analysis.
From the fact that a molecular ion peak was observed at No. 4 and a reference peak at No. 309, and because of the raw materials used, it was confirmed that this was the target substance.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table 1.

Example 9 Synthesis was carried out in accordance with the synthesis example of p-(5-methoxypentyl)phenol described in JP-A No. 63-93749.

Synthesis Example 1 (e) In (R)-4-(-1-
(s)-4-(1-Methylheptyl)oxybiphenyl-4'-monocarboxylic acid obtained in Example 7(a) in place of 4-hexyl)oxybiphenyl-4'-monocarboxylic acid; (s)-4-(5-
Methoxybentyl)phenyl: 4-(1-methylheptyl)oxybiphenyl-4'-carpoxylate 0.9
I got g.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800" 3000cm-tortoise. 1730cm-
'． 1600c+m-'1270cm-'.
190c+I1-', and mass analysis showed a molecular ion peak at 502 and a reference peak at 309, and it was confirmed that it was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 10 Synthesis was carried out in accordance with the synthesis example of p-(γ-methoxybubutyr)phenol described in JP-A-58-85825.

In Synthesis Example 1 (e), (R)-4-(1-methylnonyl)oxybiphenynoly-4'-monocanoleponic acid was replaced with (s)-4-(1) obtained in Example 7(a). -Methylheptyl)oxybiphenyl-4'-monocarboxylic acid is also replaced with 4-hexyloxymethylphenol (
(s)-4-(3-proboxypyl)7enyl::4-(1-methylheptyl ) Oxybiphenyl-4'-monocarpoxylate 0.
6g was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. II? According to measurements, the characteristic value of this object is 2800-3000 cm-'. 1730cm-
'． 1600cm-'1270c+m-'
, 1190 cm-', and mass analysis showed a molecular ion peak at 503 and a reference peak at 309, and it was confirmed that it was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarized lgi microscope. The results are shown in Table I.

Example 11 7.6 g of (s)-2-nonanol instead of 8.4 g
(s)-1-methyloctyl p-toluenesulfonate was obtained in the same manner as above. Next, Example 1 (
In b), replacing (s)-1-methylnonyl p-toluenesulfonate 149 with the previously obtained (S)-1
- Using 13 g of methyloctyl p-toluenesulfonate and following the same procedure, (1?) monomethyl 4-(1-methyloctyl)oxybi7enyl-4'
I got monocarpoxylate.

13 g of this (R) monomethyl 4-(1-methyloctyl)oxybiphenyl-4'monolupoxylate was carried out.
(R) monomethyl in W1(c): 4-(1-methylnonyl)oxybiphenyl-4'-carpoxylate 1
(R)-4-(1-methyloctyl)oxybiphenyl-4'-monocarboxylic acid was obtained in the same manner as in Example 1 (c), except that 4 g of the compound was used instead of 4 g.

Synthesis of (s)-2-decanol in Example 1 (a) In Example 1 (e), (R)-4-(1-methylnonyl)oxybiphenyl-4'-monocarboxylic acid was replaced with the above (a). The obtained (R)-4-(1-methyloctyl)oxybiphenyl-4'-monocarboxylic acid was also replaced with 4-hexyloxymethylphenol to obtain 4-bentyloxymethyl obtained in Example 2(a). Using phenol and following the same procedure, (R)4-bentyloxymethylphenyl=4-(l-methyloctyl)oxybiphenyl-
0.5 g of 4'-carpoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800~3000c+x-low, 1730cm-
'． 1600ci-'1270CI1-'. 11
90C+++-' and 516 in Mass analysis
A molecular ion beak was observed at , a reference peak was observed at 323, and it was confirmed that this was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 12 In Example 1 (a), 9 g of (s)-2-undecanol was used in place of 8.4 g of (S)-2-decanol, and the other procedures were repeated in the same manner to prepare (s)-1-methyldecyl=
p-4 luenesulfonate was obtained. Next, Example 1 (
In b), replace 14 g of (s)-1-methylnonyl p-toluenesulfo filtrate with the previously obtained (s)
- 1-methyldecyl p-toluenesulfonate 14
．． By using 5g and performing the same procedure, (R)monomethyl=4-(1-methyldecyl)oxybiphenyl-
4'-carpoxylate was obtained.

This (+?)monomethyl==4-(1-methyldecyl)oxybiphenyl-4' monolupoxyle} 14.59
was used in place of 14 g of (R) monomethyl:4-(1-methylnonyl)oxybiphenyl-4' monolupoxylate in Example 1(C), and the other operations were carried out in the same manner as in Example 1(C), to obtain (R) -4-(1-methyldecyl)oxybiphenyl-4'-monocarboxylic acid was obtained. The phase transition temperature of this product is shown below.

In Example 1 (d), 4-butoxymethylphenol was obtained by using 1-butanol instead of 1-hexanol and performing the same procedure except for the same procedure.

Synthesis Example 1 In (e), (R)-4-(1-methylnonyl)oxybiphenyl-4' monocarboxylic acid was replaced with (R)-4-(1-methyldecyl)oxybiphenyl- obtained in (a) above. 4'-monocarboxylic acid or 4-hexyloxymethylphenol 19 obtained in (b)
Using 0.8 g of butoxymethylphenol and performing the same procedure as above, (R)-4-1-butyloxymethyl-7enyl:
: 0.49 of 4-(1-methyldecyl)oxybiphenyl-4'-carpoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLc.
It was spot on. rR[According to the definition, the characteristic value of this object is 2800". 3000C+I1-'. 173
0cm-'. 1600cm- '1270cm-
', 1190 cm-', and in lJass analysis, a molecular ion peak was observed at 530 and a reference peak at 35l, and it was confirmed that it was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table I.

Example 13 In Example 1 (e), (R)-4-(1-methylnonyl)oxybi7enyl-4'-monocarboxylic acid was replaced with (R)-4-( obtained in Example 12(a)). 1-methyldecyl)oxybi7enyl-4'-monocarboxylic acid, and 4
-Hexyloxymethylphenol 1g was replaced with 0.9g of 4-pentyloxymethylphenol obtained in Example 2(a), and the other procedures were repeated in the same manner to produce (R)-4-
Pentyloxymethyl 7-enyl::4-(1-methyldecyl)oxybi-7enyl-4'-carpoxylate 1.
I got 19.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to JR measurements, the characteristic value of this object is 2800-3000cm-', 17300! l
-breath, 1600cm- '1270cm-'.
1 190 cm-' and 5 in Mass analysis.
From the fact that a molecular ion peak was observed at 44 and a reference peak at 35L, and from the raw materials used, it was confirmed that this was the target substance.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 14 (R)-4-(1-methyldecyl) obtained in Example 12(a) in place of (R)-4-(1-methylnonyl)oxybiphenyl-41 monocarboxylic acid in Example 1(e) Oxybiphenyl-4'-monocarboxylic acid, also 4
-Hexyloxymethylphenol in Example 6 (
Using 4-octyloxymethylphenol obtained in step a) and following the same procedure, (R)-4-octyloxymethyl 7enyl 4-(1-methyldecyl)oxybi722-4' Poxylate 1.09 was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800~3000c+n-'. 1730cm
−'． 1600C++1- '1270c++-
', 1 190cm-', and Mass
In the analysis, a molecular ion beak was observed at 587, a reference peak was observed at 35L, and it was confirmed that this was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Synthesis of Example 15 In Example 1 (e), (R)-4-(1-methylnonyl)oxybi7enyl-4'-carpon al. 59 was replaced with 4-year-old ctyloxybiphenyl-4'-carboxylic acid (commercial product) 1.49, and 4-hexyloxymethylphenol was replaced with real N fl 2 (a). 4-pentyloxymethylphenyl = 4 using tinoleoxymethylphenol and otherwise operating in the same manner
0.8 g of -octyloxybiphenyl-4' monolupoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. ! According to the R measurement, the characteristic value of this object is 2800"3000cm-'. 1730cm
−'． 1600cm-"1200c+l-', and mass analysis showed a molecular ion peak at 503 and a reference peak at 309, and it was confirmed that it was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table I.

Example 16 In Example 1(e), 4-octyloxybiphenyl-4'-monocarboxylic acid (commercial product) was substituted for (R)-4-(1-methylnonyl)oxybiphenyl-4'-monocarboxylic acid 1.59. 4-( obtained in Example 10(a) by replacing 1.49 with 4-hexyloxymethylphenol
4-(3-propoxypropyl)phenyl=
1.2 g of 4-year-old cutyloxybi-7enyno-4'-monoleboxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to the IR standard, the characteristic value of this object is 2800~3000cm-', 1730C+1
- ". 1600cm- ', and Mass
In the analysis, a molecular ion peak was observed at 502, a reference peak was observed at 309, and it was confirmed that this was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 17 In Example 1 (e), 4-decyloxybiphenyl-4'carboxylic acid (4-decyloxybiphenyl-4'carboxylic acid
commercially available product) 1.59, and 4-hexyloxymethyl 7
4-(5- obtained in Example 9(a)) in place of enol
4-(5-methoxypentyl)7enyl = 4-decyloxybi7enyl-4'-carpoxylate 0.99
I got it.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to the IRm constant, the characteristic values of this object are 2800~3000cm-', 1730cm-
'． 1600cm-'1270cm-', and mass analysis shows a molecular ion peak at 531,
Based on the fact that a reference peak was observed at 337 and the raw materials used, it was confirmed that it was the target substance.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table I.

Example 18 A reaction vessel was charged with 15 g of (R)-2-heptanol and 50+ mQ of dimethylformamide (DMF), and 6.29 g of sodium hydride (content: 60%) was added little by little at 20° C. or lower, followed by thorough stirring. Next, 40 mff of a DMF solution of 30 g of 4-promobenzyl bromide was added to the solution at 30 mff.
It was added dropwise at ~35°C and stirred at the same temperature for 3 hours.

The reaction solution was poured into cold diluted hydrochloric acid and extracted with benzene. The benzene layer was washed with water and dehydrated with sodium sulfate. The solvent was distilled off and the residue was distilled under reduced pressure to obtain (R)-1-bromo-4-( l-Methylhexyloxymethyl)benzene 24s was obtained.

b. p. toa℃/Q. 3 mmHg A small amount of magnesium 2.39 and iodine pieces was charged in a reaction vessel, and the (R) obtained in the above (a) was prepared under a nitrogen stream.
- Tetrahydrofuran (THF) of 1-bromo-4-(l-methylhexyloxymethyl)benzene 249 7
After a small amount of the 0 mff solution was added dropwise to initiate the reaction, the remaining THF solution was added dropwise to the extent that reflux was maintained while stirring, and after the dropwise addition, the mixture was stirred and refluxed for 3 hours to prepare a Grignard reagent.

In a separate reactor, add 14 g of borosilicate triptyl ester and T.
HF30! lα was charged, and the previously prepared Grignard reagent was added dropwise under a nitrogen stream while stirring at 40°C, and the mixture was further stirred at the same temperature for 1 hour. Next, 10% sulfuric acid 60+
IIQ was added dropwise at 20°C or lower, stirred for a while at the same temperature, and then added to the separated THF layer at 20°C or lower with stirring.
0% hydrogen peroxide solution 80r
Stir for hours.

The reaction solution was extracted with benzene, the benzene layer was washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain (R)-
4-(1-methylhexyloxymethyl)phenol 4
．． 7g was obtained.

b. p. 108 - 115°C/0.2 mmHg Synthesis Example 1 (e) In place of (R)-4-(1-methylnonyl)oxybiphenyl-4'-monocarboxylic acid 1.59, 4-octyloxybiphenyl-4'- Carpon ra (commercial product) Obtained in the above (b) by replacing 1-4y with 4-hexyloxymethylphenol 19 (R
)-4-(1-methylhexyloxymethyl)phenol 1.19 and the other procedures were the same to prepare (R)-4-(
1-Methylhexyloxymethyl)phenyl = 4-octyloxybiphenyl-4' monolupoxylate 0.6
I got g.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800-3000 cm-'. 1730cm-
'． 1600c+*-'1270cm'''l, and in mass analysis, a reference peak was observed at 530 bimolecular ion beak and 309, and based on the raw materials used, it was confirmed that it was the target substance.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarized S microscope. The results are shown in Table 1.

Example 19 25 g of 4-hydroxyphenethyl alcohol in a reaction vessel
In addition, 200 lα of 48% hydrobromic acid was charged, and the mixture was reacted for 4 hours under stirring and reflux. After cooling, extract with benzene, wash the benzene layer with water, dehydrate with sodium sulfate, and distill off the solvent.
The residue was distilled under reduced pressure to obtain 14 g of 4-(2-promoethyl)phenol.

b. p. 123℃/l. 2mmHg, m. p. 8
(s)-2-octanol 19 in the reaction vessel at 6-88°C.
．． 79 and DMF 70ml2, and stirred
Sodium hydride (content 60%) 69 was added little by little at a temperature below .degree. C., and the mixture was thoroughly stirred at the same temperature. Add to this the above (a)
4-(2-promethyl)phenol obtained in 13.99
A solution of 2 in 50 ml of DMF was added dropwise at 10° C. or lower with stirring, and the mixture was reacted with stirring at the same temperature for 1 hour and at room temperature for 1 hour. The reaction solution was poured into dilute hydrochloric acid, extracted with benzene, the benzene layer was washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain (s)-4-(2-(1-methyl) 5 g of heptyloxy)ethylphenol was obtained.

b-p. 128℃/0.25a+a+Hg Synthesis Example 1 In (e), (R)-4-(1-methylnonyl)oxybi7enyl-4'monocarboxylic acid 1.59 was replaced with 41nonyloxybiphenyl=4'carpon. acid(
(commercial product) obtained in the above (b) by replacing 1.4 g with 4-hexyloxymethylphenol 19 (s) -
Using 1.2 g of 4-(2-(1-methylheptyloxy)ethyl)phenol, the rest was carried out in the same manner (s
) -4-(2-(1-methylheptyloxy)ethyl]phenyl=4-nonyloxybi7enyl-
4'-carpoxylate l. Obtained Og.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800-3000 cm-'. 1730c+a
−'． 1600c+m-'1270cm-'
In addition, mass analysis revealed a molecular ion peak at 573 and a reference peak at 323, and it was confirmed that this was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 20 A reaction vessel was charged with 400 mQ of methylene chloride and 61 g of anhydrous aluminum chloride, and while cooling in an ice bath, acetyl chloride 399 was added little by little with stirring, and after stirring and reacting at the same temperature for a while, 3-brombrobylbenzene 75
g was added dropwise at 0° C. or below, and the mixture was stirred and reacted at the same temperature for 3 hours.

The reaction solution was poured into cold dilute hydrochloric acid, and the methylene chloride layer was thoroughly washed with water, then dehydrated with sodium sulfate, and the solvent was distilled off. The residue was distilled under reduced pressure to obtain 4-(3-bromoprobyl)acetophenone 8.
8g was obtained.

b. p. 120℃/0.25mmHg 76g of 4-(3-bromoprobyl)aceto7enone obtained in (a) and 350ml of methylene chloride were placed in a reaction vessel, and while cooling in an ice-water bath, 88% formic acid 570+12 and anhydrous were added under stirring. Acetic acid 290+x12 and concentrated sulfuric acid 3
．． Add 7mQ of water in sequence, then add 110% of 35% hydrogen peroxide solution.
I was added dropwise to the mixture while stirring at room temperature, and after the addition, the mixture was stirred and reacted at 45 to 50°C for 16 hours. The reaction solution was poured into water, the methylene chloride layer was separated, and the methylene chloride was distilled off. To the residue obtained, an aqueous solution of caustic soda and benzene were added and stirred.
The aqueous layer was separated and made acidic by adding hydrochloric acid.

The oily substance was extracted with benzene, the benzene layer was washed with water, and after dehydration with sodium sulfate, the solvent was distilled off and distilled under reduced pressure to obtain 4-
Obtained 15 g of (3-bromoprovir)phenol.

b. p. 120°C/0.3mmHg in the reaction vessel (s
)-2-octanol 8.59 and DMF 30ml2
2.7 g of sodium hydrogen monoxide (content 60%) was added little by little at below 10'C with stirring, and the mixture was thoroughly stirred at the same temperature. To this, obtained in (b) above: t: 4-<3-
A solution of 7 g of (bromoprovir) phenol in 20 mQ of DMF was added dropwise under stirring at 10° or lower, and the mixture was reacted with stirring at the same temperature for 1 hour and at room temperature for 1 hour.

The reaction solution was poured into dilute hydrochloric acid and extracted with benzene. The benzene layer was washed with water and dehydrated with sodium sulfate. The solvent was distilled off and the residue was distilled under reduced pressure to obtain (s)-4-(3-(1) -Methylhebutyloxy)propyl]phenol 2.39% was obtained.

b. p. In Synthesis Example 1(e) of 135 to 140°O/0.3mmHg, (R)-4-(1-methylnonyl)oxybi7enyl-4'-carbonyl 1.5 was replaced with 4-octyloxybiphenyl- (s) obtained in the above (c) by replacing 1.49 of 4' monocarboxylic acid (commercially available) with lg of 4-hexyloxymethylphenol
-4-(3-(1-methylheptyloxy)
Provil]phenol 1.39 was used, and the other procedures were carried out in the same manner to produce (s)-4-(3-(1-methylheptyloxy)furobyl]phenyl = 4-octyloxybiphenyl-4'monolupoxyle-} t.Og was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800-3000 cm-'. 1730cm-
".1600cm-'1270c++-", and mass analysis shows a molecular ion peak at 573.
A reference peak was observed in 309, and it was confirmed that it was the target substance based on the raw materials used.

This product was sandwiched between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under polarized light llI@mirror. The results are shown in Table-1.

Example 2l A reaction vessel was charged with 50 g of p-cresol, 419 pyridine, and 200 mff of benzene, and penzoyl chloride 729 was added dropwise with stirring at room temperature, followed by stirring under reflux for 3 hours after the dropwise addition. The reaction solution was poured into water, the benzene layer was washed with water, dehydrated with sodium sulfate, and the residue was distilled under reduced pressure to obtain 4-methyl-7enyl.
Benzoe}969 was obtained.

b. p. 124-127℃/0.55mmHg, m
．． p. 67-69°C A reaction vessel was charged with 4-methylphenyl:bezoate 96SF obtained in (a), 80 g of N-promusuccinimide, 0.6 g of benzoyl peroxide, and 300 TRα of carbon tetrachloride, and the mixture was stirred and refluxed for 4 hours. The reaction solution was filtered, the carbon tetrachloride layer was washed with water, and dehydrated with sodium sulfate. The solvent was distilled off, and the residue was recrystallized once with ethanol and once with a mixed solvent of benzene/hexane to give 4-7' 42 g of rommethylphenyl benzoate were obtained.

9 g of (R) ethyl monolactate and 60 DMF in a reaction vessel.
mQ was charged, and sodium hydride (content 60%) 3.69 was added little by little at 20°C or less while stirring, and after thorough stirring, 10 g of 4-prommethylphenyl bezoate obtained in (b) above was added. A solution of 40 ml of DMF was added dropwise at a temperature below 10° C., and the reaction was further stirred at the same temperature for 1 hour and at room temperature for 1 hour. The reaction solution was poured into cold dilute hydrochloric acid and extracted with benzene. The benzene layer was washed with water and dehydrated with sodium sulfate. The solvent was distilled off and the residue was distilled under reduced pressure to obtain (R)-4-(1-ethoxy (Polyponylethyloxy)methylphenol 19 was obtained.

b. p. 155-160℃/0.7mmHg Synthesis Example 1 In (e), 4-decyloxybiphenyl-4 was used in place of (R)-4-(1-methylnonyl)oxybi7enyl-4'-monocarboxylic acid 1.59. ′Carboxylic acid (
Commercially available product) (R)-4 obtained in the above (C) by replacing 1.59 with 4-hexyloxymethylphenol 19
-(1-ethoxylponylethyloxy)methylphenol 19 was used, and the other procedures were carried out in the same manner as (R)-4-(
0.19 of 1-ethoxyluponylethyloxy)methylphenyl 4-decyloxybi-7enyl-4'-lupoxylate was obtained.

The purity of this product is 98% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800-3000cm-'. 1720-17
40cm-"1600cm-" and Mass
In the analysis, a molecular ion peak was observed at 560, a reference peak was observed at 337, and it was confirmed that this was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table I.

Example 22 A reaction vessel was charged with 2-7 fluoroanisole 1289 and chloroform 250+12, and 177 g of I-bromine was added dropwise over 3 hours while stirring at room temperature. Dilute the reaction solution with N
The chloroform layer was separated, washed with brine, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to give 2-furol 4-bromoanisole 192.
I got a 9.

b. p. 107~118°C/25~31mmH
g Magnesium (Mg) 229 in the reaction vessel under a nitrogen stream
．． A small amount of iodine and 50+lα of THF were charged, and a suitable amount of a solution of 144 g of bromobenzene in 150 ml of THF was added thereto and heated. After the start of the reaction, the remaining THF solution was added dropwise while stirring under reflux, and the mixture was refluxed for 2 hours to prepare a Grignard reagent.

In a separate container, 3.6 g of dichlorbistri7enylposphinpalladium (CfftPd(PPhs)z) and TH
Prepare FIOO■ and diisobutylaluminum')mu/N hydride ((iso-C4H*)*A under nitrogen flow.
26+ mα of a 1 molar solution of QH)/hexane was added, and a solution of 120 g of the 2-fluoro-4-bromoanisole obtained in (a) above in 50 mm of IF1 was added. This was heated to 50 to 60°C, and the previously prepared Grignard reagent was added dropwise thereto, followed by aging at the same temperature for 2 hours. After the reaction was completed, the reaction solution was poured into diluted hydrochloric acid, extracted with benzene, washed with water, dehydrated with sodium sulfate, and the solvent was distilled off. The residue was recrystallized from a mixed solvent of t-chloroform/hexane and purified by silica gel column chromatography using hexane as an eluent to obtain 3-7fluoro-4-methoxybi-7enyl 9
I got 69.

959 3-fluoro-4-methoxybiphenyl obtained in the above (b) and 400 m of methylene chloride (
Add 94 g of anhydrous aluminum chloride little by little at below 0°C while stirring, and add 5 ml of acetyl chloride.
6 g was added dropwise. After the dropwise addition, the mixture was stirred for 6 hours while gradually raising the temperature to room temperature.

The reaction solution was poured into diluted hydrochloric acid, the organic layer was washed with water, dehydrated with sodium sulfate, and then the solvent was distilled off. The residue was recrystallized with C00 form to obtain 114 g of 3-fluoro4-methoxy4'-acetylbiphenyl.

F1 A reaction vessel was charged with 84 g of 3-fluoro-4-methoxy-4'-acetylbiphenyl obtained in (C) above, 700 mQ of 48% hydrobromic acid, and 900 mQ of acetic acid.
The mixture was heated and stirred at ~110°C for 12 hours. The reaction solution was poured into water, the precipitated crystals were collected by filtration, washed with water, and purified by silica gel column chromatography using methylene chloride as the eluent to obtain 3-fluoro-4-hydroxy-4'-acetylbiphenyl. 58g was obtained.

12.69, (s
)-6-methyloctyl bromide 12.7 g. Potassium carbonate 15.19 and cyclohexanone 200 m (2
The mixture was heated and stirred at 90 to 100°C for 12 hours.

The solid material obtained by filtering the reaction solution was washed with benzene,
The washing solution and filtrate were combined, washed with water, and dehydrated with Glauber's salt. The solvent was distilled off, and the residue was recrystallized from a7ton/methanol to give (S)-3-7fluoro-4-(6 -Methyloctyl)oxy-4'-acetylbi7enyl 13.1g was obtained.

21.2 g of NaOH and 100 mff of water in a synthesis reaction vessel.
i, add bromine 299 dropwise under stirring at 5°C or below,
After the dropwise addition, the mixture was stirred at 10° C. or lower for 1.5 hours to prepare an aqueous sodium hypobromite solution. In another container, (s)-3-fluoro-4-(6-methyloctyl)oxy-4'-acetylbiphenyl obtained in (e) above 11.09
Also, 100 mffi of dioxane was charged, and the previously prepared aqueous sodium hypobromite solution was added dropwise while stirring at room temperature.
After the dropwise addition, the mixture was heated and stirred at 50 to 60°C for 3 hours.

The reaction solution was poured into an aqueous sodium sulfite solution and acidified with hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and dried (s
) - 9.8 g of 3-fluoro-4-(6-methyloctyl)oxybi-7enyl-4'-monocarboxylic acid was obtained.

Synthesis Example 1 In (e), 1.5 t of (R)-4-(1-methylnonyl)oxybiphenyl-4'-monocarboxylic acid was replaced with (s)-3-7fluoro- obtained in (f) above. 4
-(6-Methyloctyl)oxybiphenyl-4'monocarboxylic acid 1.59 was used and other procedures were carried out in the same manner as (s)-
4-hexyloxymethylphenyl = 3-ful 4
1.29 of -(6-methyloctyl)oxybiphenyl-4' monolupoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800-3000 cm-'. 1730cm-
' , 1600c+x- '1280cm-', and in mass analysis there is a molecular ion peak at 548,
Based on the fact that a reference peak was observed at 341 and the raw materials used, it was confirmed that it was the target substance.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table 1.

Example 23 In Example 22(e), 18 g of (R)-1-methylheptyl tosylate obtained in Example 7(a) was used in place of 12.79 of (s)-6-methyl bromide, and was operated in the same manner to prepare (s)-3-yfluoro-4-(1
9.1 g of '-methylheptyl)oxy-4'-acetylbi7enyl was obtained.

A reaction vessel was charged with 8.89 ml of NaOH and 30 mff of water, and 14 g of bromine was added dropwise at 5° C. or lower with stirring. After the dropwise addition, the mixture was stirred at 10° C. or lower for 1.5 hours to prepare an aqueous sodium hypobromite solution. (s) obtained in (a) above in a separate container
- 3 - 4.06 g of 7-fluoro-4-(1'-methylheptyl)oxy-4'-acetylbiphenyl and 75 mg of dioxane were charged, and the previously prepared aqueous sodium hypobromite solution was added dropwise under stirring at room temperature. After, 5
The mixture was heated and stirred at 0 to 60°C for 5 hours.

The reaction solution was poured into an aqueous sodium sulfite solution and made acidic with hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and dried.
s) -3-7luoro'4-(1'-monomethylheptyl)oxy-4'-biphenylcarboxylic acid 4.07
I got a 9.

Synthesis Example 1 In (e), (R)-4-(1-methylnonyl)oxybiphenyl-4'-monocarboxylic acid 1.59 was replaced with (s)-3-7fluoro4 obtained in (b) above. -(1'-methylheptyl)oxybifu-4'
1.5 g of monocarboxylic acid, and 4-hexyloxymethylphenol 19 was replaced with 4 obtained in Example 2(a).
-Using 1 g of pentyloxymethylphenol, and performing the same procedure as above, (S)-4-pentyloxymethylphenyl = 3-fluorol-4-(1-methylheptyl)oxybi7enyl-4' 0.69 was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. According to IR measurement, the characteristic value of this object is 2800~3000c+m-'. 1730cm
−'． 1600c+a-'1280cm-'
Furthermore, in mass analysis, a molecular ion peak was observed at 521, a reference peak at 215, and a fragment peak at 327, and it was confirmed that this was the target substance based on the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 24 F Anhydrous aluminum chloride 1139 and methylene chloride 60 () mQ were charged in a reaction vessel, and acetyl chloride 1139 was added dropwise at 0°C or below while stirring, and then 4-bromo-2-fluorobin7enyl 100 g of methylene chloride 400
After dropping the mQ solution, the mixture was stirred and reacted for 7 hours while gradually returning to room temperature. The reaction solution was poured into ice and diluted hydrochloric acid, the methylene chloride layer was washed with water, an aqueous sodium bicarbonate solution, water, and then dehydrated with sodium sulfate. The solvent was distilled off, and the residue was recrystallized with acetone. 4-acetyl-2'-7-fluoro-
I got 96g of 4'-from biphenyl.

A reaction vessel was charged with 65 g of 4-acetyl-2'-7-fluoro-4'-brombiphenyl obtained in (a) above and 300 IIQ of methylene chloride, and heated at 10°C or below with stirring.
% formic acid 500a4, then acetic anhydride 480tnQ was added dropwise, and after further adding concentrated sulfuric acid 1.5mα, 35% hydrogen peroxide solution 150mQ was added dropwise over 3 hours. After the dropwise addition, the temperature was gradually raised to 45~ The reaction was carried out at 50°C for 30 hours.

The reaction solution was poured into ice water and extracted with benzene. The benzene layer was washed with an aqueous sodium bicarbonate solution, washed with water, and dehydrated with sodium sulfate. The solvent was distilled off to obtain a residue. Place this residue and ethyl alcohol 2a in another container, and add 2a to this.
A 5% KOH aqueous solution was added, and the mixture was stirred under reflux for 8 hours. The reaction solution was poured into ice and diluted hydrochloric acid, extracted with benzene, the benzene layer was washed with brine, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (eluent base). 4-hydroxy-2'-7-fluoro-
28.19 of 4'-prombin-7enyl was obtained.

4-Hydroxy-2'-fluoro-4'-brombiphenyl 1 (h, obtained in (b) above, Example 4 (
15 g of (R)-1-methylhexyl tosylate obtained in a), 8 g of potassium carbonate and 10 g of 2-butanone
0++12 was charged, and the mixture was reacted for 8 hours under reflux and stirring. The reaction solution was poured into dilute hydrochloric acid, extracted with benzene, the benzene layer was washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (eluent: hexane). (s)-4-(1-methylhexyl)
Oxy-2'-fluoro-4'-brombiphenyl 12
I got g.

In a reaction vessel, (s)-4-(1-methylhexyl)oxy-2'-fluoro-4'-bromubi7 obtained in (c) above was added.
enyl 10.59. Cuprous cyanide 3.6g and DI
JF50+IQ was charged, and the mixture was heated and stirred at 150 to 155°C for 24 hours. After cooling, the reaction solution was poured into dilute hydrochloric acid in which 13 g of ferric chloride was dissolved, and stirred at 50-55°C for 1 hour. The oil was extracted with benzene, the benzene layer was washed with water, and after dehydration with sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent: benzene/hexane - 1/1). S)-4-(1-methylhexyl)oxy-2'-7fluoro-4'-cyanobin7enyl 4.69'r was obtained.

(s)-4-(1-Methylhexyl)oxy-2'-fluoro-4'-cyanobi7 obtained in (d) above was placed in a reaction vessel.
Enil 4.5g, NaOHl3ip water 40mQ solution,
50 mg of THF and 100 ml of methanol were charged, and the mixture was stirred under reflux for 22 hours. After cooling, the reaction solution was poured into water and made acidic with hydrochloric acid. The precipitated crystals were collected by filtration, washed with warm water, and dried to give (s)-4-(1-methylhexyl). 4.6 g of oxy-2'-fluorobiphenyl-4' monocarboxylic acid was obtained.

Synthesis Example 1 In (e), 1.59 of (R)-4-(1-methylnonyl)oxybiphenyl-4'monocarboxylic acid was replaced with (s)-4-(1-methyl obtained in (e) above). 4-pentyloxymethylphenol obtained in Example 2(a) by replacing 1.49 g of 4-hexyloxymethyloxy-2'-7-fluorobiphenyl-4'-carboxylic acid with lg of 4-hexyloxymethylphenol. Using (s)-4-pentyloxymethylphenyl::
0.59 of 4-(1-methylhexyl)oxy-2'-fluorobiphenyl-4'-carpoxylate was obtained.

The purity of this product is 99% or more by HPLC analysis and 1 by TLC.
It was spot on. ! According to the R measurement, the characteristic value of this object is 2800 to 3000 cm-'. 1730cm-
凰. 1600c+i-'1280cix-'', and Mass analysis Teha 506 bimolecular ion beak, 2l5
It was confirmed that this was the target substance based on the fact that a reference peak was observed in , and a 7-lagment peak was observed in 313, as well as the raw materials used.

This product was placed between hot stages FP-82 (manufactured by Mettler), and phase changes were observed under a polarizing microscope. The results are shown in Table-1.

Example 25 Polyvinyl alcohol is applied to two ITO glass substrates with transparent electrodes to form a thin film, and this is rubbed in a certain direction, and one substrate and the other substrate are rubbed in parallel directions. The evaluation elements were assembled so that the spacing was 3μ.

In addition, Example 4, Example 7, and Example 9. Example 10, Example 18. Example 19, Example 20. Each compound obtained in Example 2l was encapsulated in an isotropic liquid state to produce a liquid crystal element. This liquid crystal element was installed in a polarizing microscope equipped with a Mettler hot stage, and the temperature was lowered from the isotropic liquid state to the SmC main phase at a rate of 0.1 degrees per minute. After confirming the formation of monodomains, Sawyer Tower circuit using 50
Apply a triangular AC voltage of 60 V (±30 V) at Hz, and determine the spontaneous polarization (Ps) of each compound from the size of the steresis curve displayed on the oscilloscope screen.
was measured. The results are shown in Table-2.

Also, using the liquid crystal element manufactured by the above procedure, S
After forming mC main phase monodomain, 200Hz, 50V
Changes in transmitted light intensity when a square wave AC voltage of (±25V) is applied to the photodiode, photosensor amplifier,
Response time was measured using a digital storage scope. The results are shown in Table-2.

The response time is the time required for the light intensity to reach 90% of the maximum light intensity starting from the time when the polarity of the applied voltage is reversed (
I).

Example 26 4-pentyloxymethylphenyl 4-octyloxybiaenyl-4'-carpoxylate obtained in Example 15 and (s)-4-hentyloxymethyl obtained in Example 23 Phenyl 3-fluoro-4(l-methylheptyl)oxybiphenyl-4' monolupoxylate was mixed at a weight ratio of 90:10 to prepare a liquid crystal composition.

The spontaneous polarization (Ps) and response time (τ
) was measured according to the procedure shown in Example 25.

Incidentally, this composition exhibits an SmC main phase in the range of 79.4 to 125.8°C when the temperature is increased.

Example 27 The (s)-4-pentyloxymethyl7enyl 4-(1-methylhexyl)oxybiphenyl-4'-carpoxylate obtained in Example 4 was mixed with the pyrimidine liquid crystal composition shown in the table below in a weight ratio of 10. :90 to prepare a new liquid crystal composition.

The response time (τ) of this liquid crystal composition was measured according to the procedure shown in Example 25. Note that this liquid crystal composition exhibited a Srac'' phase when the temperature was raised in the range of 20 to 50°C.

(Measurement temperature 20℃)

Claims (12)

[Claims] (1) General formula, ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R^1 represents a linear or branched alkyl group having 1 to 18 carbon atoms, and R^ 2 is the number of carbon atoms from 1 to
18 straight-chain or branched alkyl group, or the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^3 is a straight-chain or branched alkyl group having 1 to 16 carbon atoms. is an alkyl group, X^1 and X^2 each represent a hydrogen atom, a chlorine atom or a fluorine atom,
n represents an integer of 1 to 10) A biphenylcarboxylic acid derivative compound represented by: (2) The compound according to claim 1, wherein R^1 in the general formula (I) is an alkyl group having 4 to 18 carbon atoms and having an asymmetric carbon atom. (3) The compound according to claim 1, wherein R^2 in the general formula (I) is an alkyl group having 4 to 18 carbon atoms and having an asymmetric carbon atom. (4) R^1 and R^2 in the above general formula (I)
The compound according to claim 1, wherein both are straight-chain alkyl groups. (5) X^1 and X^2 in the above general formula (I)
5. The compound according to claim 1, wherein both are hydrogen atoms. (6) X^1 and X^2 in the above general formula (I)
Claims 1 to 3, wherein either one of them is a fluorine atom.
4. The compound described in 4. (7) General formulas, ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 represents a linear or branched alkyl group having 1 to 18 carbon atoms, and R^ 2 is the number of carbon atoms from 1 to
18 straight-chain or branched alkyl group, or the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1 is a straight-chain or branched alkyl group having 1 to 16 carbon atoms. is an alkyl group, X^1 and X^2 each represent a hydrogen atom, a chlorine atom or a fluorine atom,
(n represents an integer of 1 to 10) A liquid crystal composition comprising at least one biphenylcarboxylic acid derivative compound represented by the following. (8) The liquid crystal composition according to claim 7, containing a compound in which R^1 in the general formula (I) is an alkyl group having 4 to 18 carbon atoms and having an asymmetric carbon atom. (9) The liquid crystal composition according to claim 7, containing a compound in which R^2 in the general formula (I) is an alkyl group having 4 to 18 carbon atoms and having an asymmetric carbon atom. (10) R^1 and R^ in the above general formula (I)
8. The liquid crystal composition according to claim 7, comprising a compound in which both of 2 are linear alkyl groups. (11) X^1 and X^ in the above general formula (I)
Claims 7 to 7 containing a compound in which 2 are both hydrogen atoms.
11. The liquid crystal composition according to 10. (12) X^1 and X^ in the above general formula (I)
11. The liquid crystal composition according to claim 7, further comprising a compound in which one of the two atoms is a fluorine atom.