JPS6396156A - Biphenylcarboxylic acid derivative and liquid crystal composition - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R* is alkyl having asymmetric carbon atom; R is 1-18C alkyl). EXAMPLE:(S)-Hexyl 4-[(2''-methylbutyl)oxy]biphenyl-4'-carboxylate. USE:A liquid crystal display substance, chemically stable and capable of exhibiting ferroelectricity within a wide temperature range near room temperature. PREPARATION:(S)-2-Methylbutanol expressed by formula II as a starting material is converted into (S)-4[(2''-methylbutyl)oxy]biphenyl-4'-carbonyl chloride expressed by formula III, which is then reacted with hexyl alcohol in the presence of pyridine in benzene solvent while refluxing for 10hr to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel liquid crystal compound and a liquid crystal composition containing at least one of the liquid crystal compounds. recent years,
Liquid crystal compounds are widely used as image display materials, but most of them are nematic liquid crystal compounds.
7-11737) is the mainstream. However, TN type display systems that use nematic liquid crystal compounds have drawbacks such as slow response and the display cannot be seen depending on the viewing angle (poor viewing angle characteristics). It is essential to improve this, and various studies have been conducted for this purpose.

Among them, ferroelectric liquid crystals discovered by R.B. Meyer et al. (J, Physique, 36.
L-69 (1975)) is capable of a much faster response than nematic liquid crystals, so display elements using it (N, A.

C1ark, S, T, Lagerwall; A
ppl, Phys, Lett, 36899
(1980)) is currently being actively researched.

This display method uses chiral smectic C, a ferroelectric liquid crystal.
It utilizes the chiral smectic H phase (hereinafter referred to as "SmC") and the chiral smectic H phase (hereinafter referred to as "SmH"), and currently known compounds include, for example, the following substances.

12℃ 97℃ Crys t-→SmC" ←-→Is,.

415℃ 43℃ 64.2℃CryBt
-1→SmC---→SmA ←−→Is.

A) shows ferroelectricity in a temperature range higher than around room temperature, and b) shows ferroelectricity in a wide temperature range including room temperature, but both of these are chemically unstable. It is a thick base. C) is chemically stable and has a temperature range near room temperature in which it exhibits ferroelectricity, but that temperature range is narrow.

By the way, as a material for practical use, it is desired that it be chemically stable and exhibit ferroelectricity in a wide temperature range around room temperature. As a result of intensive research into its molecular structure,
We have arrived at the present invention. That is, the present invention provides an alkyl group represented by the general formula (wherein R* represents an alkyl group having a non-seasonal carbon atom and has optical activity, and R represents an alkyl group having 1 to 18 carbon atoms) The present invention provides a biphenylcarboxylic acid derivative and a liquid crystal composition containing at least one thereof.

The compound of formula 13 above has a phase transition temperature to the smc* phase near room temperature, especially when R*=6-methyloctyl,
Compounds in which R is butyl or hexyl have an enantiotropic SmC'' phase near room temperature. These compounds can be mixed to widen the temperature range in which they exhibit the SmC'' phase.

Furthermore, when the compound of formula (1) according to the present invention is used by being mixed with other liquid crystal compounds, the temperature range in which the compound exhibits the SmC'' phase can be expanded.

The present invention will be explained in detail below.

The compound according to the present invention can be synthesized by the synthetic route shown in the following scheme.

The compounds according to the present invention, their synthesis examples, and usage examples will be specifically explained below.

In addition, the abbreviations in this specification are used with the following meanings.

Crystal: Crystal SmA: Smectic physiognomy SmH”: Chiral smectic H phase m, p,
: Melting point b, p, : Boiling point Sm: Smectic phase SmC" : Chiral smectic phase C phase I!30
: Isotropic liquid crystal SmB : Smectic B phase Example 1 Synthesis of (S)-hexyl 4-1: (2//-methylbutyl)oxycopiphenyl-4'-carboxylene) (V) (a) (S) -Synthesis of 2-methylbutyl p-)luenesulfonate (1) (S)-2-methylbutanol 250I and pyridine 90
p-Toluenesulfonylchloride F'542F was gradually added to the mixture with OCC at 10° C. or lower while stirring. After reacting at the same temperature for 5 hours, the reaction solution was diluted with water. After extracting the liberated organic layer with benzene, this benzene layer was washed with dilute hydrochloric acid until it became neutral. Furthermore, the benzene layer was washed with water, dried with Glauber's salt, and then the solvent was distilled off to obtain 525I (S)-2-methylbutyl p-toluenesulfur 7one) (+).

(b) (s)-Methyl 4-((2'-methylbutyl)oxycopiphenyl-4'-carboxyle) (11
), methyl 4-hyProxypiphenyl-4'-
Carboxylate 90.9. (8)-2-Methylbutyl p-toluenesulfonate (1) N11, anhydrous potassium carbonate 114! 1 and cyclohexanone 11 were added, and the mixture was stirred at 130 to 140°C for 5 hours. After cooling, the reaction solution was poured into water, and the liberated organic layer was extracted with benzene. After thoroughly washing the benzene layer with water, it was dried with Glauber's salt. When the solvent is distilled off and the residue is recrystallized from acetone, Kyoshi9
4F (S)-methyl 4-C(2"-methylbutyl)oxycopiphenyl-4'-carboxylene (8m) (II) was obtained. m, p, 118 122°C (c)
(S)-4-((2'-Methylbutyl)oxy]biphenyl-4'-carboxylic acid (IIL) synthesis reaction vessel, (S)-methyl4-CC2''-methylbutyl)oxyfubiphenyl-4'-carboxylic acid (IIL) Rate (11) 9
4Ii (dissolved in Nato2 Hydrofura/200CH), 20 occ of methanol, and 30Ii of 95'16 caustic soda (dissolved in 150CC of water) were charged and stirred under reflux for 4 hours. Next, hydrochloric acid was added to the reaction solution to make it acidic, and the precipitate was filtered under reduced pressure. The roasted crystals were heated and dried to give 851 (S)-4-(:(2'-methylbutyl)oxyfubiphenyl-4'-carbon a (lit
) t gain.

(d) (s) -4-(: (2'-methylbutyl)oxyfubiphenyl-4'-carbonylchloride)'
(IV)+Z) In the synthesis reaction vessel, (s)-4-[:(2″-methylbutyl)
Oxycopyphenyl-4'-carboxylic acid (lit) 8
59, 700 CC of benzene and a small amount of pyridine were charged, and thionyl chloride 54I was added dropwise while stirring under reflux. After reacting at the same temperature for 10 hours, the solvent and excess thionyl chloride were distilled off to give (S)-4-C(2'-
90 g of methylbutyl)oxyfubiphenyl-4'-carbonylchloride)' (IV) was obtained.

(e) (8)-Hexyl 4- ((2'-methylbutyl)oxyfubiphenyl-4'-carboxylate (
V) Synthesis 1.11. of hexyl alcohol was added to the reaction vessel. benzene 2
0CC, pyridine r3.8611 were charged, and (S)-4-((2'-methylbutyl)oxyfubiphenyl-4'-carbonyl chloride (IV) was added at room temperature while stirring.
3.071i (dissolved in 30 CC of benzene) was added dropwise.

Furthermore, after reacting for 10 hours under reflux, the reaction solution was diluted with water, and the liberated benzene layer was washed with water and dried with Glauber's salt. Benzene was distilled off, and the residue was recrystallized four times from acetone to give (S)-hexyl 4-[(2'-methylbutyl)oxy]pi7-di-4'-carboxylate (■)0.
76Ii was obtained.

The content of this product was 99% or more by liquid chromatography and 1 spot by thin layer chromatography. Also, according to infrared absorption spectrum measurement, the characteristic value is 2.
800~3000cm-', 1700cm-',
A molecular ion peak was observed at 368 in the → simass vector analysis of 1190, which indicates that this is the target (S)-hexyl 4-[(2'-methylbutyl)oxyfubiphenyl-4'-carboxylate. I confirmed that there is.

This was placed on a Mettler hot stage FP-82, and the phase change was observed under a polarizing microscope, and the following was observed.

Examples 2 to 3 A biphenylcarboxylic acid derivative was synthesized in the same manner as in Example 1 except that decyl alcohol and P-decyl alcohol were used in place of the hexyl alcohol used in Example 1(e), and the phase thereof was The transition temperature was measured.

The results are shown in Table 1.

Example 4 (S)-octyl 4-(”(4/I-methylhexyl)
Oxycopiphenyl-4'-carboxylate (IX)
Synthesis (a) (s)-Methyl 4-CC4"-methylhexyl)oxycopyphenyl-4'-carboxylate (■
Synthesis reaction vessel of 1) Cemethyl 4-hyP roxypiphenyl-4'-carboxylate 67.5#, (S)-4-methy/Lzhexyl! Lomide (Mol, Cryst, Liq,
Cryst.

Synthesized according to reaction examples 267-2471984 above. b, p
.

71-b 82.8+ and 750 CC of cyclohexanone were charged, and the mixture was stirred at 130-140°C for 5 hours. After cooling, the reaction solution was poured into water, and the liberated organic layer was extracted with benzene.

After thoroughly washing the benzene layer with water, it was dried with Glauber's salt. By distilling off the solvent and recrystallizing the residue from acetone,
(S)-Methyl 4-[(4'-methylhexyl)oxyfubiphenyl-4'-carboxylate (
Vi) was obtained. When the phase change of this product was observed under a polarizing microscope, it was as follows.

104℃ 119.5 125 CrySt--SmB←-→S臥←-→ENG60(b)
(3) Synthesis of -4-[(4'-methylhexyl)oxyfubiphenyl-4'-carboxylic acid (vli) In a reaction vessel, (s)-methyl 4-C(4#-methylhexyl)oxyfubiphenyl- 4'-carboxylate (■1) 7
5g (dissolved in 200cc of Tetrahyroa), 200cc of methanol, 30g of caustic soda 95%. S+ (water 1
(dissolved in 50 seeds) and stirred under reflux for 4 hours. Next, hydrochloric acid was added to the reaction solution to make it acidic, and the precipitate was filtered under reduced pressure.

The P-collected fCM crystal was heated and dried to obtain (S)-4(
(4'-methylhexyl)oxycopyphenyl-4'-
Carboxylic acid (Vi+) was obtained.

(C) (S) -4-((4'-methylhexyl)
oxyfubiphenyl-4'-carbonylchloride)'(
%(S)-4-((4'-methylhexyl)
Oxycopiphenyl-4'-carboxylic acid (Vio 67
1. 600cc of benzene and a small amount of pyridine were charged, and thionyl chloride 5119' was added dropwise while stirring under reflux. After reacting for 1 g at the same temperature, the solvent and excess thionyl chloride were distilled off to give (S) -4-C(4''-methylhexyl)oxycopyphenyl-4'-carbonylchloride l' ( 70 g of viiD was obtained.

(a) (s)-octyl 4-[:(4"-methylhexyl)oxy]biphenyl-4'-carboxylate)
Octyl alcohol 13 in the synthesis reaction vessel of (IX)! M', benzene 2
0CC and bilicin α79! (S)-4-((4#-methylhexyl)oxycopiphenyl-4'-carbonylchloride)' (
viiD 3. o 7 Cef 30 CC solution was added dropwise to 1 g of the mixture. After reacting under reflux for 9 hours, the reaction solution was poured into water, and the liberated benzene layer was washed with water and dried over Glauber's salt.

Benzene was distilled off, and the residue was recrystallized four times from acetone to give (S)-octyl 4 + I"(4//-methylhexyl)oxyfubiphenyl-4'-carboxylate (IX) 1.18 I got g.

The content of this product was 99 or more by liquid chromatography, and 1 spot by thin layer chromatography. Also, according to infrared absorption spectrum measurements, the characteristic values are 275o~3000an-', 1700G, 1190
cm, and mass spectrometry reveals that 424 has a molecular ion, so the obtained substance is (
It was confirmed that it was S)-octyl 4-((4//-methylhexyl)oxycopiphenyl-4'-carboxylate.

This product was placed on a Mettler hot stage FP-82, and the phase change was observed under a polarizing microscope, as shown below.

Examples 5, 6, 7.8 In Example 4(d), octyl alcohol used was replaced with nipentyl alcohol, hexyl alcohol, tecyl alcohol, and undecyl alcohol, respectively, and the other conditions were the same as in Example 4. We synthesized various biphenylcarboxylic acid derivatives and measured their transition temperatures.

The results are shown in Table 2.

Example 9 Synthesis of (S)-butyl 4-C(6''-methyloctyl)oxy]bifu22-4'-carboxylate (xlv) (a) (S)-,S-methyloctyl bromide (X
) powdered magnesium 13.811 and tetrahypfuran (purified by distillation after treatment with lithium aluminum hydride) 1600C were charged into a reaction vessel for the synthesis of (s
) -2-Methylbutylpuromy (Mox, Cr
yst, Liq, Cryst, , l, s 7~
52, 1978, p=12
3-124°C) 781 was added dropwise to prepare a Grignard reagent.

Separately, in a reaction vessel, add 1,4-dibromobutane 12319
．． Tetrahythm O7 Run'' (THF) 350 CC.

and 0.1 molA dilithium tetrachlorocuprate-THF solution (Li□CuCt4/4rHF
) 18 CC was charged, and the above Grignard reagent was added dropwise at a temperature below 0°C.

1 hour at 0℃ or below, 1 hour at 10℃, and 1 hour at room temperature.
After stirring for an hour, the reaction solution was poured into dilute hydrochloric acid. The liberated organic layer was extracted with benzene, and the benzene layer was thoroughly washed with water. This benzene layer was dried with Glauber's salt and steamed, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain (8)-6-methyloctyl bromide (X) 60 Ii. b, p,
102~b(b) (S)-Methyl 4-[:(6”
-Methyl 4-hydroxypiphenyl-4'-
Carboxylate 3819. (S)-6-methyloctyl bromide (x) 38J', anhydrous potassium carbonate 53g
, 50cc of cyclohexanone was added, 130~14
The mixture was stirred at 0°C for 5 hours. After cooling, the reaction solution was poured into water.
The liberated organic layer was extracted with benzene. After thoroughly washing the benzene layer with water, it was dried with Glauber's salt. The solvent was distilled off and the residue was recrystallized from acetone to obtain psoy (S).
-Methyl 4-((6'-methyloctyl)oxycopiphenyl-4'-carboxylate (XI) was obtained*.

8mm m, p, 113-125 (c) (8) -4-C (6'-methyloctyl)
Synthesis of oxybiphenyl-4'-carboxylic acid (xii) (S)-Methyl 4-((6''-methyloctyl)oxycopyphenyl-4'-carboxylate (
Xi) 50 N (tetrahydro 7; yy200cc
), 200 CC of methanol and 151 cc of 95% caustic soda (dissolved in 150 CH of water) were added, and under reflux
Stir for hours.

Next, hydrochloric acid was added to the reaction solution to make it acidic, and the precipitate was filtered under reduced pressure. The dried crystals were dried by heating to obtain 45.9 (S)-4-C(6-methyloctyl)oxycopyphenyl-4'-carboxylic acid (xii).

(d) (S) -4-((6”-methyloctyl)
oxycopyphenyl-4'-carbonylchloride)'(
(S)-4-[” (6'-methyloctyl)oxycopiphenyl-4'-carboxylic acid (xiD
45I, 500 cc of benzene, and a small amount of pyridine were charged, and 329 thionyl chloride was added dropwise while stirring under reflux. After reacting at the same temperature for 10 hours, the solvent and excess thionyl chloride were distilled off to give 47.9 (S) -4
-C(6'-methyloctyl)oxyfubiphenyl-4
'-Carbonyl chloride r(xlil) was obtained.

(e) (S)-Butyl 4-((6”-methyloctyl)oxyfubiphenyl-4′-carboxylate (x
lv) in a synthesis reaction vessel, butyl alcohol α70I, benzene 20
CC and 0.75 g of pyridine were charged, and with constant stirring, (S)-4-((6'-methyloctyl)oxycopiphenyl-4'-carbonylchloride)' (x
lii) 31 (dissolved in acK)' was added dropwise. After further reacting under reflux for 15 hours, the reaction solution was poured into water, and the liberated benzene layer was washed with water and dried with sodium sulfate. Benzene was distilled off, and the residue was recrystallized twice from an ether-hexane mixed solvent to obtain (S)-butyl 4-
C(6'-methyloctyl)oxycopyphenyl-4
'-carboxylate (AV) tOi was obtained.

The content of this product was 99 or more by liquid chromatography, and 1 spot by thin layer chromatography. According to infrared absorption spectrum measurement, the characteristic values are 2800-6000i1.1710crIV1.
1200crIN-1, and mass spectrometry analysis showed that 396 contained a molecular ion, indicating that the obtained substance was (S)-butyl 4-((6"-methyloctyl)oxycopyphenyl-4' - It was confirmed that it was a carboxylate.This product was placed on a Mettler hot stage FP-82, and the phase change was observed under a polarizing microscope, and the following was observed.

492℃ 58.5℃ 697℃Crys -
-→SmC” -1→SmA Is.

Examples 10-15 Examples? In (e), various other biphenylcarboxylic acid derivatives were synthesized in the same manner as in Example 9 except that various other alcohols were used instead of the butyl alcohol used, and the phase transition temperatures were measured.

The results are shown in Table 5.

Example 16 (S)-Butyl 4-[(6'-methyloctyl)oxirabiphenyl-4'-carboxylate (Example?) and (S)-hexyl 4-((6''-methyloctyl)oxira Biphenyl-4'-carboxylate (Example 12)
) has the following phase transition temperature:
This shows that the compound has properties more suitable for use in display devices than any single compound.

46.8℃ 61.2℃ 68.2℃Cryschiichi→SmC*−SmA←−→I s.

Example 17 (S)-Butyl 4-((6'-methyloctyl)oxy]biphenyl-4'-carboxylate) (Example M 9) and the known compound (S)-4-[(2-methylbutyl)oxyphenyl) In an equal weight mixture of phenyl 4-decyloxype/soate, SmC'' appears at 40°C when the temperature is lowered, and SmC'' appears even at -10°C.
The mC'' phase did not disappear.

As described above, the compound according to the present invention can obtain properties suitable for display devices even when mixed with a known ferroelectric liquid crystal.

Example 18 On the surface? A liquid crystal cell was assembled by spreading two transparent electrodes coated with a limide-based polymer film and rubbing them, and sandwiching a Mylar film 9 μm apart so that the rubbing directions were parallel to each other. The compounds obtained in each of the above Examples were sealed in this liquid crystal cell, and slowly cooled from an isotropic liquid to an Sm phase. When this liquid crystal cell was sandwiched between two polarizing plates and a voltage was applied to cause a polarity reaction, the display state changed. From this, the SmC'' phase of the compound obtained in the example has ferroelectricity,
It can be seen that it can be used as a display element.

Table 1 Phase transition temperature (°C) Example number RCryschi SmC” SmA
Is.

1 C6H13* 53.0-(-40,4)-
2C,. H21・65.2--3 Cl2H,oI 70.0--Table
2 Phase transition temperature (°C) Example number RCryst SmC”
SmA Is.

5 C5H,, 65.8- (Φ 61
．． 1)・6 C'6H1, -65,2-(@57.
2)・4 C8H,,・52.1 (Fist 40.
6)・54,2・7 C4゜H21弗 47
．． 8- unit 51.9 ・8 CHH23・
50.3- ・53.0 ・Table 3 Phase transition temperature (℃) Example number RCr'f51t SmC"
SmA Is.

10 C3) I, -58,0--80,5-9
C4H7・492・58.5・697
・11C5H11・6&8(・64.4)・7
1.5 ・12 C6H,, 56.8 ・
62.5 ・67.4 ・13 C8H4
,・ 66.6 (・ 59.6) (・ 62.7)・
14C1oH21・56.2 (・52.4)・
598 ・15C11H23・ 460(・ 46.
6)・ 57.9 ・In each table, the numbers in parentheses indicate the monotropic phase transition temperature.

Claims (4)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^* represents an alkyl group having an asymmetric carbon atom, and R represents an alkyl group having 1 to 18 carbon atoms.)
A biphenylcarboxylic acid derivative represented by (2) In the above formula [I], R^* is a general formula, ▲a mathematical formula, a chemical formula, a table, etc.▼ (In the formula, m is an integer from 0 to 11, and n is an integer from 1 to 11. , m+n≦14, and R has 1 to 1 carbon atoms.
The biphenylcarboxylic acid derivative according to claim 1, which is an alkyl group represented by the following formula (18). (3) General formulas, ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^* represents an alkyl group having an asymmetric carbon atom, and R represents an alkyl group having 1 to 18 carbon atoms. ) A liquid crystal composition comprising at least one biphenylcarboxylic acid derivative represented by: (4) In the formula [I] above, R^* is a general formula, ▲a mathematical formula, a chemical formula, a table, etc.▼ (In the formula, m is an integer from 0 to 11, n is an integer from 1 to 11, and , m+n≦14, and R has 1 carbon atom.
The liquid crystal composition according to claim 3, wherein the liquid crystal composition is represented by: -18 alkyl groups.