JPS62142131A - Liquid crystal intermediate - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R2 is optically active halogenated alkyl and halogenated aralkyl; o is 1-3; Y is OH, -COOH: Z is formula II, -O-CH2-, formula III, -OCO-; Ph' is 1,4-phenylene, which may be substituted with halogen, cyano or nitro on its benzene ring). EXAMPLE:(2S,3S)-4-[4'-(2-chloro-3-methylbenzyloxycarbonyl)phenyl]phenol. USE:Intermediate of liquid crystals. It has optically active groups in its molecule and is especially suitable for use as an intermediate of ferroelectric liquid crystals and cholesteric liquid crystal. Further, it can be mixed with a high- polymeric liquid crystal polymer to give a high polymeric liquid crystal exhibiting electrooptical effects. PREPARATION:For example, the reaction of an optically active halogenated carboxylic chloride with hydroquinone or p,p'-biphenol is carried out in a basic solvent such as pyridine to give the compound of formula I.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a novel liquid crystal intermediate.

Furthermore, in this specification, the term "liquid crystal substance" refers to a substance that is useful as a component of a liquid crystal composition even if it is not detected to exhibit a liquid crystal phase by itself.

BACKGROUND OF THE INVENTION Display systems for liquid crystal display elements that are currently in widespread use are twisted nematic type (TN type) and dynamic scattering type (DS type). These are nematic liquid crystals,
This is a display using a nematic liquid crystal cell as the main component. One of the disadvantages of conventional nematic liquid crystal cells is the fact that the response speed is slow, and a response speed of only a few m5ec can be obtained at most. This is one of the factors that limits the range of applications of nematic liquid crystal cells. However, it has recently been found that a faster response can be obtained by using a smectic liquid crystal cell.

It has become clear that some optically active smectics and liquid crystals exhibit ferroelectricity, and there are great expectations for their use. Problems to be Solved by the Invention None of the currently known ferroelectric liquid crystals exhibits spontaneous polarization sufficient for practical use over a wide temperature range including room temperature. Therefore, efforts are being made to develop compounds that exhibit ferroelectricity over a sufficiently wide temperature range and have strong spontaneous polarization, as well as compounds that can serve as intermediates thereof.

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors searched for various compounds and arrived at the present invention.

That is, the present invention is based on the general formula (1) % formula % () (However, in the above formula, R2 represents an optically active halogenated alkyl group, an optically active, a halogenated aralkyl group,
O is 1.2 or 3, Y represents -0H1-COOH, and Z is -COO-C)12-, -CI-C)12-
1-O-COO-CH2- or -OCO-,
Ph' represents a 1,4-phenylene group or a 1,4-phenylene group in which a benzene ring is substituted with a halogen, a cyano group, or a nitro group. ) Regarding the α-crystal intermediate represented by ).

Compounds of formula (I) can be synthesized by various methods as follows.

After reacting an optically active halogenated carboxylic acid chloride with hydroquinone, p, p'-bipheler, etc. in a basic solvent such as pyridine, the reaction mixture is purified using a silica gel column or the like to obtain various phenol derivatives.

Various phenol derivatives are obtained by azeotropically dehydrating an optically active halogenated alcohol, 4-hydroxybenzoic acid, 4,4'-hydroxyphenylbenzoic acid, etc. with a toluene solvent and esterifying it.

Optically active halogenated carboxylic acid chloride and 4-hydroxybenzoic acid, 4. ．． 4'-Hydroxyphenylbenzoic acid or the like is reacted in a basic solvent such as pyridine to obtain various benzoic acid derivatives.

Detailed synthetic methods for these compounds are described in the Examples below.

Here, the optically active group is easily derived from, for example, the following optically active alcohols and optically active carboxylic acids. 2-halo 2-phenylethanoic acid, 2-halopropanoic acid, 3-
halo 2-methylbutanoic acid, 2.3-dihalopropanoic acid, 2-phenyl-3-halopropanoic acid, 3.3.3-)
Rimulo 2-halopropanoic acid, 2-herobutanoic acid, 3-
Halobutanoic acid, 2,3-dihalobutanoic acid, 2,4-dihalobutanoic acid, 3,4-dihalobutanoic acid, 4,4゜4-trihalo-3-herobutanoic acid, 2,3.4-trioctabutanoic acid, 2- halo 3-methylbutanoic acid, 2-halo 3,
3-dimethylbutanoic acid, 2-halopentanoic acid, 3-halopentanoic acid, 4-halopentanoic acid, 2,4-dihalopentanoic acid, 2,5-dihalopentanoic acid, 2-halo 3-methylpentanoic acid, 2-halo 4- Me, tilpencunic acid,
2-Hero 3-monohexanoic acid, 4-methylpentanoic acid, 2-halohexanoic acid, 3-halohexanoic acid, 4-halohexanoic acid, 5-halohexanoic acid, 2゜5-dihalohexanoic acid, 2,6-dihalohexanoic acid, 2 , 5.6)
Dihalohexanoic acid, 2-halooctanoic acid, 2-halooctanoic acid, 2-trihalomethylbentanoic acid, 2-trihalomethylhexanoic acid, 2-trihalomethylhebutanoic acid, 2
-halo 2-phenylethanol, 2-phenyl-3-
halo 1-propertool, 3-phenyl-2-halo 1
-propertool, 1-phenyl-2-halo 1-propertool, 3-halo 2-methyl-1-propertool, 1
．． 1.1-) Rim low 2-Proper tool, 2-Harrow 1
-butanol, 3-hello-1-butanol, 2,3-dihalo-1-phtanol, 2,4-dihalo-1-butanol, 3,4-dihalo-1-butanol, 1,1.1-)
rimlow 2-butanol, 4,4.4-) rimlow 3-
halo 1-butanol, 2,3.4-) rimlow 1-butanol, 3,3. ．． 4,4.4-Penta-8-2-butanol, 2-Hero-3-methyl-1-butanol, 2
-halo 3,3-dimethyl-1-butanol, 2-hero 1-pentanol, 3-hero 1-pentanol, 4
-Halo-1-pentanol, 2,4-dihalo-1-pentanol, 2.5-dihalo-1-pentanol, 1.1
．． 1-trihalo2-pentanol, 1,1.1.2.
2-pentahalo/3-pentanol, 2-halo 3-
Methyl-1-pentanol, 2-halo 4-methyl-1
-pentanol, 2-halo 3-monohalomethyl-4-
Methyl-1-pentanol, 2-halo-1-hexanol, 3-halo-1-no\xanol, 4-halo-1-hexanol, 5-halo-1-hexanol, 2,5-dihalo-1-hexanol, 2 , 6-cyhalo-1-hexanol, 1.1.1-1lyhalo-2-hexanol, 2
゜5.6-Dorihalo 1-hexanol, 2-halo 1
- Heptatool, 1,1. l-trihalo 2-heptatool, 2-halo 1-octanol, 1.1.1-trihalo2. -Octatool et al.

(However, halo in the above chemical formula represents chlorine or bromine.) Also, some of the above optically active carboxylic acids and optically active alcohols can be obtained by optical resolution, asymmetric synthesis, or oxidation of the corresponding alcohol. reactor. Others can be derived from optically active amino acids and optically active oxyacids, such as those naturally occurring or obtained by resolution.

Alanine, valine, leucine, isoleucine, phenylalanine, serine, threonine, allothreonine, homoserine, alloisoleucine, tert-leucine, γ-
Methylleucine, 2-aminobutyric acid, norvaline, norleucine, ornithine, lysine, hydroxylysine, phenylchrysine, trifluoroalanine, aspartic acid, curtamic acid, lactic acid, mandelic acid, tropic acid, 3-hydroxybutyric acid, malic acid, tartaric acid , isopropyl malate, etc.

action of invention The compounds of the present invention are useful as monomers.

Since the compound of the present invention has an optically active group in its molecule, it is particularly useful as a ferroelectric liquid crystal intermediate or a cholesteric liquid crystal intermediate.

Moreover, by introducing the compound of the present invention into a polymer liquid crystal polymer, it is also possible to obtain a polymer liquid crystal exhibiting an electro-optical effect.

Effects of the Invention A compound synthesized using the compound of the present invention as an intermediate becomes an excellent ferroelectric liquid crystal. A ferroelectric liquid crystal synthesized using the compound of the present invention exhibits ferroelectricity enantiotropically over a wide temperature range and has large spontaneous polarization. Also, for example.

Unlike BAMBC, it does not have a carbon-nitrogen double bond, so it is chemically stable.

Generally, liquid crystal compounds have a rod-like structure consisting of a core made of a benzene ring, etc., and an alkyl chain. Among them, it is well known that those whose alkyl chain has more than a certain number of carbon atoms tend to form a smectic phase. That is,
The compound represented by the above general formula (1) can be used as an alkyl alcohol, an alkyl carboxylic acid, an alkoxy carboxylic acid,
4-alkylphenol, 4-alkoxyphenol, 4-alkylcarbonyloxyphenol, 4-alkoxyluponylphenol, 4-alkoxycarbonyloxyphenol, 4-(4'-'; rukylphenyl)phenol, 4-(4 4-(4'-alkoxycarbonyloxyphenyl)phenol;4-(4'-alkoxycarbonyloxyphenyl)phenol;4-(4'-alkoxycarbonyloxyphenyl)phenol; Alkoxybenzoic acid/4-alkylcarbonyloxybenzoic acid, 4-alkoxycarbonylbenzoic acid, 4-alkoxycarbonyloxybenzoic acid, 4- (4'-alkylphenyl)benzoic acid, 4- (4'-alkoxyphenyl) Benzoic acid, 4-(4'-furkylcarbonyloxyphenyl)benzoic acid, 4-(4'-alkoxycarbonylphenyl)benzoic acid, 4-(4'-alkoxycarbonyloxyphenyl)benzoic acid, or compounds thereof A useful ferroelectric liquid crystal can be obtained by reacting the benzene ring with a derivative in which a halogen, cyano group, or nitro group is substituted.

For example, as shown in Example 7, (2S,3S)-4-(4'-(2-chloro-3-
・,(2S,3S)-4' synthesized using methylpentyloxycarbonyl)phenyl)phenol as an intermediate
-(4”-(2-chloro-3-methylpentyloxycarbonyl)phenyl)phenyl-4-octylcarbonyloxybenzoic acid ester* *C8H17-Coo-Ph-C0O-Ph-Ph-CO
O-CH2-CH-CH-C2H5CI CH3 exhibits ferroelectricity at 70 to 130°C. Moreover, its spontaneous polarization is extremely large at 109 nC/cm''.

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

Hereinafter, the C, SC tree, SA, Sl tree, N tree, and N2 phase represent crystal, chiral smectic C, smectic A, chiral smectic, chiral nematic, nematic, and isotropic phases, respectively.

Example 1 Synthesis of (2S,3S)-4-(4'-(2-chloro-3-methylpentyloxycarbonyl)phenyl)phenol t*HO-Ph-Ph-COO-CH2-C)l-CH- C
2) 15CI C) 13 (2S,3S)-2-chloro-3-methylpentanol 5.0 g, 4-(4'-hydroxyphenyl)benzoin'
t17.5g and p-) toluenesulfonic acid 7.0g,) toluene 10. Pour Oml into a reaction vessel equipped with a dehydrator 1
Reflux for 5 hours. Water was added and the toluene layer was separated and concentrated to obtain 10 g of 2S,3S)-4-(4'-(2-chloro-3-methylpentyloxycarbonyl)phenyl)phenol.

The IR spectrum of the compound measured by the Nujol method is shown in FIG.

Example 2 Synthesis of (S)-4-(4'-(1-chloro-2-methylpropylcarbonyloxy)phenyl)phenol HO-Ph-Ph-OCO-C)I(CI)-C)I
(CH3)2* 4.47 g of 4'-biphenol is dissolved in 200 ml of pyridine, and 25 ml of (S)-2-chloro-3-methylbutanoic acid chloride is added while stirring. After further stirring for 2 hours and neutralizing with hydrochloric acid, the mixture was extracted with chloroform to obtain crude 4-(4'-(1-chloro-2-methylpropylcarbonyloxy)phenyl)phenol. This was purified using a silica gel column, and (S)-4
20 g of -(4'-(1-chloro-2-methylbrobylcarboni, 5oxy)phenyl)phenol is obtained.

The IR spectrum of the compound measured by the Nujol method is shown in FIG.

Example 3 (S)-4-(4'-(1-chloro-2-methylpropylcarbonyloxy)phenyl)benzoic acid synthesis HOOC-Ph-Ph-OCO-CH(CI)-CH
(CH3)2-4-(4'-hydroxyphenyl)benzoic acid 3°5g
was dispersed in a mixture of 30 ml of carbon tetrachloride and 5 ml of pyridine and heated. While stirring under dandelion (S)-2-
2.5 ml of chloro-3-methylbutanoic acid chloride is added dropwise. After heating for 3 hours, the solvent was distilled off, a small amount of water was added to decompose the unreacted nonanoyl chloride, and the residue was washed with methanol.5)-4-(4'-(
1-chloro-2-methylpropylcarbonyloxy)phenyl)benzoic acid is obtained.

The IR spectrum of the compound measured by the Nujol method is shown in FIG.

Example 4 Synthesis of (S)-4-(1-chloro-2-methylpropylcarbonyloxy)phenol HO-Ph-OCO-CH(CI)-CH(CH3)2
* 25 g of hydroquinone is dissolved in 200 ml of lysine, and while stirring, 2.5 ml of (S)'-2-chloro-3-methylbutanoic acid chloride is added. After roughly stirring for 2 hours and neutralizing with hydrochloric acid, the mixture was extracted with chloroform.
A crude product of -(1-chloro0-2-methylpropylcarbonyloxy)phenol is obtained. This was purified using a silica gel column to obtain 15 g of (S)-4-(1-chloro-2-methylpropylcarbonyloxy)phenol.

The IR spectrum of the compound measured by the Nujol method is shown in FIG.

Example 5 Synthesis of (S)-4-(1-chloro-2-methylpropylcarbonyloxy)benzoic acid HOOC-Ph-OCO-C)I(CI)-C)l(
CH3)2* 2.5g of 4-hydroxybenzoic acid in 30ml of carbon tetrachloride
and 5 ml of pyridine and heat. While stirring under reflux, 2.5 ml of (S)-2-chloro-3-methylbutanoic acid chloride was added dropwise. After heating for 3 hours, the solvent was distilled off, a small amount of water was added to decompose unreacted acid chloride, and the residue was washed with methanol.
4 g of )-4-(1-chloro-2-methylpropylcarbonyloxy)benzoic acid are obtained.

The IR spectrum of the compound measured by the Nujol method is shown in FIG.

Example 6 Synthesis of (2S,3S)-4-(2-chloro-3-methylpentyloxycarbonyl)phenol* Ne110-Ph-Coo-CH2-CH-CH-C2H5
CI CH3 (2S, 3S) - 5.0 g of -2-chloro-3-methylpentanol, 3.5 g of 4-hydroxybenzoic acid, 3.0 g of p-)luenesulfonic acid, and 100 ml of toluene in a dehydrator. The mixture was charged into a reaction vessel equipped with a gasket and refluxed for 15 hours. Add water, separate the toluene layer, and concentrate.25,3S)-4-
(2-chloro-3-methylpentyloxycarbonyl)
6 g of phenol) is obtained.

Example 7 (2S,3S)-4'-(4''-(2-chloro-3
-methylpentyloxycarbonyl)phenyl)phenyl-4-octylcarbonyloxybenzoic acid ester (
Synthesis and evaluation of A) *C3H17-C00-Ph-COO-Ph-Ph-CO
O-COO-CH-C)I-C2)15CI CI
(3 4-octylcarbonyloxybenzoic acid chloride 1.
5 g was dissolved in a mixture of 80 ml of carbon tetrachloride and 10 ml of pyridine and cooled. Under ice cooling, (2S,3S)-4-
Add 1.7 g of (4'-, (2-chloro-3-methylpentyloxycarbonyl)phenyl)phenol and stir for a while. - overnight, the precipitated crystals are filtered off, the solvent is distilled off, the mixture is purified using a silica gel column, and the desired product is obtained by recrystallization from ethyl acetate.

The IR spectrum of the compound measured by the Nujol method is shown in FIG.

This compound is a smectic liquid crystal compound exhibiting an SC* phase, and its phase transition temperature is shown in Table 1.

In addition, a 25 μm thick polyethylene terephthalate film was used as a spacer, and a cell made of Nesa glass (
Enclose A), apply 300H2 alternating current, and use Sawyer
- Spontaneous polarization was measured by the Tower method. As a result, (A
) is 109 n C/ c tn
', and was found to have strong spontaneous polarization.

Example 8 Table 1 summarizes the phase transition temperatures of various liquid crystals synthesized using the compounds of the present invention.

As is clear from Table 1, the compounds of the present invention were proven to be very useful as intermediates for ferroelectric liquid crystals and chiral nematic liquid crystals.

[Brief explanation of drawings]

Figure 1 shows the (2S, 3S) -4-(4') obtained in Example 1.
The infrared absorption spectrum of -(2-chloro-3-methylpentyloxycarbonyl)phenyl)phenol is shown. FIG. 2 shows an infrared absorption spectrum of (S)-4-(4'-(1-chloro-2-methylpropylcarbonyloxy)phenyl)phenol obtained in Example 2. FIG. 3 shows an infrared absorption spectrum of (S)-4-(4'-(1-chloro-2-methylpro-benzoyloxy)phenyl)benzoic acid obtained in Example 3. Figure 4 shows the (S)-4-(1-chloro-2
-Methylpropylcarbonyloxy)phenol shows an infrared absorption spectrum. FIG. 5 shows the (S)-4-(1-chloro0-2-
Methylpropylcarbonyloxy)an,! . This shows the infrared absorption spectrum of aromatic acid. Figure 6 shows the (2S, 3S)-4'-(4''
The infrared absorption spectrum of -(2-chloro-3-methylpentyloxycarbonyl)phenyl)phenyl-4-octylcarbonyloxybenzoate ester is shown.

Claims (6)

[Claims] (1) General formula (I) Y-(Ph')o-Z-R2 (I) (However, in the above formula, R2 represents an optically active halogenated alkyl group, an optically active halogenated aralkyl group, o
is 1, 2 or 3, Y represents -OH, -COOH, and Z represents -COO-CH2-, -O-CH2-, -O-
It represents COO-CH2- or -OCO-, and Ph' represents a 1,4-phenylene group or a 1,4-phenylene group in which a benzene ring is substituted with a halogen, a cyano group, or a nitro group. ). (2) In the general formula (I), R2 is the following general formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (R3 is an alkyl group, an aralkyl group, X is Cl or Br, * represents an optically active carbon atom) according to claim (1). (3) In general formula (II), R3 is the following general formula (III)-C
The compound according to claim (2), which is represented by nH2n+1 (III) (n is a natural number from 1 to 5). (4) In general formula (II), R3 is the following general formula (IV) -CH
A compound according to claim (2), which is represented by 2-CH(CH3)2 (IV). (5) In general formula (II), R3 is the following general formula (V) -CH
A compound according to claim (2), which is represented by (CH3)-C2H5 (V). (6) In general formula (II), R3 is the following general formula (VI)-Ph
(VI) The compound according to claim (2), represented by (Ph represents a phenyl group).