JPH01113347A - Optically active compound and liquid crystal - Google Patents

Abstract

NEW MATERIAL:An optically active compound of formula I (R<1> is 1-20C alkyl; R<2> is 1-18C alkyl, 3-20C alkyl, cyclohexyl; X is single bond, -O-; Y is single bond, -COO-; Z is single bond, -O-, -COO-; A, B are single bonds, formula II, formula III). EXAMPLE:4-(4'-(1-Methyl-3-propoxybutoxy))biphenyl(1R,3S)-p-n-dodecyloxy- benzoate. USE:Liquid crystal display element material. The compound can be readily modified to give a ferroelectric liquid crystal compound of large spontaneous polarization and high weather resistance. PREPARATION:The reaction of a compound of formula IV with p-toluenesulfonyl chloride gives another compound of formula III, which is hydrogenolyzed to give the compound of formula V.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel optically active substance, optically active 44-2-2
- A novel optically active compound derived from pentanol and a liquid crystal.

Liquid crystals include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals, among which the optically active compound derived from the optically active 4-substituted-2-pentanol of the present invention is a smectic liquid crystal, especially one having ferroelectricity. , is a chiral smectic C liquid crystal useful as a display element material.

Furthermore, such chiral smectic liquid crystals can also be used in optoelectronic devices such as optical printer heads, optical Fourier transform elements, and light valves.

[Conventional technology]

Liquid crystal display elements that are currently widely used are of the twisted nematic (TN) type using nematic liquid crystal compositions. TN type liquid crystal display elements can be manufactured at extremely low cost, but the demand for large screen LCDs has increased in recent years.
In order to realize this, there are serious drawbacks in threshold characteristics, response speed, etc.

For this reason, research and development of liquid crystal display elements to replace the TN system is currently being actively conducted. The high-speed response of ferroelectric LCDs using liquid crystal compositions has been attracting attention.

Chiral smectic C liquid crystal has a helical structure, and its spontaneous polarization is canceled in the bulk state, but it exhibits residual spontaneous polarization in a liquid crystal cell subjected to surface alignment treatment with a cell gap shorter than the pitch length of the helical structure. , responds at an extremely fast rate (1 to 100 microseconds) to an external electric field, and also exhibits memory properties (N, A, C1ar
k et al App 1. Phys, Let t,,36,89
9 (1980)).

By utilizing the high-speed optical switching phenomenon of chiral smectic C liquid crystals, it is possible to produce liquid crystal display elements with significantly faster response times than conventional twisted nematic type liquid crystal display elements, making it possible to manufacture large-screen liquid crystal display devices. can be put into practical use.

As such chiral smectic C liquid crystal, p-
Decyloxybenzylidene-p“-amino-2-methylbutylcinnamate (hereinafter abbreviated as DOBAMBC)
is the first example (R,B.

See Meyer et al. J, de Physique 3 Office, L-69 (1975)).

However, since DOBAMBC has a Schiff base structure, it is unstable to moisture, and the double bond of the cinnamate ester is unstable to light, which is a serious drawback. It goes like this.

In order to overcome the drawbacks of BAMBC, attempts have been made to synthesize chemically stable chiral smectic C liquid crystals, and a number of compounds have already been reported.

[Problem to be Solved by the Invention 3] In order to obtain a chiral smectic liquid crystal exhibiting ferroelectricity, it is essential that the compound contains an optically active group. Conventionally, two chiral sources for ferroelectric liquid crystal synthesis have been used.
-Methylbutanol is widely used. The (S) form of 2-methylbutanol is relatively easily available as a byproduct of ethanol fermentation, but it is difficult to synthesize the (R) form, and since it has only one functional group, it cannot be freely modified by chemical modification. It's also poor. In chiral smectic liquid crystals that use 2-methylbutanol itself or chemically modified 2-methylbutanol as an asymmetric source, the value of spontaneous polarization, which is a measure of ferroelectricity, is small, and high-performance ferroelectric liquid crystals have not been obtained. do not have.

The effects of substituents near the asymmetric center of an optically active group can be divided into steric factors and electronic factors.

Since the response speed of a ferroelectric liquid crystal to an external electric field is proportional to its spontaneous polarization, a material with large spontaneous polarization is desirable for high-speed response. Yoshino et al. investigated steric factors,
It has been found that the use of 1-methylbutyl group instead of 2-methylbutyl group increases the spontaneous polarization (Fer et al.
roelectricsX 58.21 (1984)
). In addition, Ohyori et al. have reported that the use of a 2-octatool is useful for increasing spontaneous polarization (see Japanese Patent Laid-Open Publication No. 149547/1984, etc.). When these optically active groups are used, although spontaneous polarization increases, chiral smectic liquid crystallinity tends to become poor.

As an approach to electronic factors, P. Kelle
reported that it is possible to increase the polarization of the asymmetric carbon by directly bonding a chlorine atom to the asymmetric carbon, thereby increasing the spontaneous polarization of chiral smectic liquid crystals (
C.R.Acad.

Sci, Parr is, 282. C639, (19
76)). In addition, Sakurai et al. reported that by using a similar method and adding steric factors, it was possible to obtain a chiral smectic liquid crystal with extremely large spontaneous polarization (see Japanese Patent Laid-Open No. 60-218358, etc.). . Note et al. have reported that a chiral smectic liquid crystal with large spontaneous polarization can be obtained by bonding a fluorine atom to an asymmetric carbon (see Japanese Patent Laid-Open Publication No. 1986-1986). However, optically active groups containing halogen atoms are chemically unstable, and many problems remain that are difficult to put into practical use, where long-term reliability is a prerequisite.

C1ark et al. used 2-alkoxypropanol as an asymmetric source (see US Pat. No. 4,556,727).
. In the 2-alkoxypropanol molecule, an oxygen atom is bonded to the asymmetric center, so a compound with larger spontaneous polarization than 2-methylbutanol can be obtained.
The degree of increase is not so significant due to the small contribution of steric factors.

[Means and effects for solving the problem] The present inventors have made extensive efforts with the aim of providing a ferroelectric liquid crystal compound that is easy to chemically modify, has a large spontaneous polarization value, and has excellent weather resistance. As a result of investigation, an optically active compound represented by the following general formula (I) derived from optically active 4-substituted-2-pentanol was discovered, and the present invention was achieved.

(In the formula, R1 is a linear alkyl group having 1 to 20 carbon atoms, R
2 is a straight alkyl group having 1 to 18 carbon atoms, 3 to 2 carbon atoms
0 branched alkyl group, cyclohexyl group, carbon number 1-
Cyclohexyl group substituted at the 4-position with 10 linear or branched alkyl groups, phenyl group, or carbon number 1-1
0 represents a phenyl group substituted at the 4-position with a linear or branched alkyl group, where X is a single bond, -〇-1-000-
or 1000-1Y is a single bond, -COO- or 10
OC-12 represents a single bond, -〇- or 1000-,
A and B each independently represent a single bond, sha, -S, (■effectQΣ, Indicates carbon.

When Ai: or B contains an aromatic ring, one or two of its hydrogen atoms may be substituted with a halogen atom. ) R1 in the general formula (I) is a straight alkyl group having 1 to 20 carbon atoms, and a straight alkyl group having 4 to 16 carbon atoms is particularly preferably used. - In formula (I), R2 is a linear alkyl group having 1 to 18 carbon atoms;
1.3-20 branched alkyl group, cyclohexyl group,
Cyclohexyl group, phenyl group or 4-position substituted with a linear or branched alkyl group having 1 to 10 carbon atoms
It is a phenyl group substituted with a linear or branched alkyl group having 1 to 10 carbon atoms. Preferred embodiments of R2 include a methyl group as the linear alkyl group,
Ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-hebutyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group,
n-dodecyl group, n-1-lysocyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-
Examples include heptadecyl group and n-octadecyl group. Examples of branched alkyl groups include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1.
2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1.3-dimethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methyl pentyl group, 1
．． 2-dimethylbentyl group, 1.3-dimethylpentyl group, 1.4-dimethylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4
-Methylhexyl group, 5-methylhexyl group, 1.2-
Dimethylhexyl group, 1,3-dimethylhexyl group, 1
．． 4-dimethylhexyl group, 1-methylhebutyl group, 2
-Methylhebutyl group, 3-methylhebutyl group, 4-methylhebutyl group, 5-methylheptyl group 1,6-methylhebutyl group, 1,2-dimethylheptyl group, 1.3-dimethylhebutyl group , 1.4-dimethylheptyl group, 1.5
-dimethylhebutyl group, 1,6-dimethylhebutyl group,
1-methyloctyl group, 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 7-methyloctyl group, 1.2 dimethyloctyl group, 1 .3-dimethyloctyl group, 1.4-dimethyloctyl group, 1.5-dimethyloctyl group, 1.6-dimethyloctyl group, 1.7-
Examples include dimethyloctyl group. Examples of the cyclohexyl group substituted at the 4-position with a linear alkyl group include 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-n-propylcyclohexyl group, and 4-n-propylcyclohexyl group.
-butylcyclohexyl group, 4-n-pentylcyclohexyl group, 4-n-hexylcyclohexyl group, 4-n
-heptylcyclohexyl group, 4-n-octylcyclohexyl group, 4-n-nonylcyclohexyl group, 4-n
-decylcyclohexyl group, and examples of the cyclohexyl group substituted at the 4-position with a branched alkyl group include 4-(1-methylpropyl)cyclohexyl group, 4-decylcyclohexyl group,
-(1-methylbutyl)cyclohexyl group, 4-(2-
methylbutyl)cyclohexyl group, 4-(1-methylpentyl)cyclohexyl group, 4-(2-methylpentyl)cyclohexyl group, 4-(3-methylpentyl)cyclohexyl group, 4-(1-methylhexyl)cyclohexyl group, 4 -(2-methylhexyl)cyclohexyl group, 4-(3-methylhexyl)cyclohexyl group, 4-
(4-methylhexyl)cyclohexyl group, 4-(1-
Methylhebutyl)cyclohexyl group, 4-(2-methylheptyl)cyclohexyl group, 4-(3-methylhebutyl)cyclohexyl group, 4-(4-methylhebutyl)cyclohexyl group, 4-(5-methylhebutyl) ) cyclohexyl group, 4-(1-methyloctyl)cyclohexyl group, 4-(2-methyloctyl)cyclohexyl group, 4
-(3-methyloctyl)cyclohexyl group, 4-(4
Examples include -methyloctyl)cyclohexyl group, 4-(5-methyloctyl)cyclohexyl group, and 4-(6-methyloctyl)cyclohexyl group. 4
A similar structure can be exemplified in the case of a phenyl group substituted with an alkyl group at the position.

When optical isomers exist in a branched alkyl group,
Optically active forms can also be preferably used in addition to racemic forms.

Optically active 2,4-bentanediol, which is a raw material for the optically active 4-substituted-2-pentanol used in the present invention, is produced by the method of Izumi et al. (Chem, Lett., 1049 (1979).
)), it is possible to synthesize acetylacetone with high optical purity by asymmetric hydrogenation using a Raney nickel catalyst modified with optically active tartaric acid and subsequent recrystallization. Since tartaric acid, which is a catalyst modifier, is available in both the natural (RR) form and the non-natural (SS) form, optically active 2,4-bentanediol also has the (2S,4S) form and the (2R) form. , 4R) bodies can be synthesized,
It can be selected depending on the purpose of use.

Since the optically active 4-substituted-2-pentanol (I) of the present invention has an asymmetric center close to the 2- and 4-positions, the vicinity of the asymmetric center is sterically crowded, resulting in a steric configuration. It is thought that a change in locus is unlikely to occur. In addition, the optically active 4 The optically active compound represented by the general formula (I) derived from -substituted-2-pentanol can become a chiral smectic liquid crystal with very large spontaneous polarization.

In the optically active compound represented by the general formula CI), the following structures can be mentioned as combinations of XXY, Z, A and B forming the liquid crystal skeleton structure.

represents.

R'-A-Coo-B-R"R'-A-Coo-B-OR"R'-A-Coo-B-COOR'"R'-A-B-R"R'-A-B-OR"R1-A-B-COOR"R'-A-00C-B-R"R'-A-00C-B-OR"R'-A-00C-B-COOR'"R'0-A- Coo-B-R1 R'0-A-Coo-B-OR"R'0-A-Coo-B-COOR"R'〇-A-B-R"R'0-A-B-OR" R '0-A-B-COOR'R'0-A-00C-B-R'R'0-A-00C-B-OR'R'0-A-00C-B-COOR'R'C0O-A-Coo-B-R"R'C0O-A-Coo-B-OR"R'C0O-A-Coo-B-COOR"R'C0O-
A-B-R"R'C0O-A-B-OR"R'C0O-A-B-COOR"R'C0O-A-00C-B-R'"R'C0O-A-00C-B-OR"R'C0O-A-00C-B-COOR"R'0OC-
A-Coo-B-R"R'0OC-A-Coo-B-OR"R'0OC-A-Coo-B-COOR"R"0OC-
A-BR"R'0OC-A-B-OR"R'0OC-A-B-C○○R'"R'0OC-A-00C-B-RtR'0OC-A-00C-B-OR"R'0OC-A-00C-B-COOR"A and B are each independently a single bond, Xφ>, -&, -=EH唖>
, +, Yunka H Kankyō, (■←f ト, (H), Habata), Besaka ga weak or threat, but particularly preferred combinations are as follows.

In the case of Y = single bond, A = Yutaka, B = -4 Defense A = ((gi, B = () =-OH>, B=-@- A=(Q bar 5k, B=〈〉 A=(), B=-C edge) If Y=-CO2- or -00C-, A=sha, B=
(NaA=sha, B=(cba) A=(sawagi, B=goA=sha, B=l鑵A=sha, B=% A=(ku4, B=-@- A=( *When A and B in general formula (I) contain an aromatic ring, one or two hydrogen atoms of the aromatic ring may be substituted with a halogen atom.The halogen atom is , fluorine atom, chlorine atom, and bromine atom are preferably used, and fluorine atom is particularly preferably used. In a compound containing an appropriate halogen-substituted aromatic ring, it is possible to increase the spontaneous polarization of chiral smectic liquid crystal or expand the temperature range. A desirable effect can be obtained.

The synthesis of optically active compounds containing these structural units can be carried out by methods well known to those skilled in the art, but in particular, optically active compounds derived from optically active 4-substituted-2-pentanol newly discovered by the present inventors can be synthesized by methods well known to those skilled in the art. The method for synthesizing the main optically active moieties will be explained below.

B) HO+○R8 Optically active 4-substituted-2-pentanol R''OH is reacted with p-toluenesulfonyl chloride in the presence of an organic base to form I)-toluenesulfonic acid ester, and then hydroquinone monobenzyl ether By reacting with an alkali metal salt of B n O+ OR” is obtained. This compound is hydrogenolyzed in the presence of a hydrogenation catalyst such as palladium/carbon to obtain optically active hydroquinone monoether HO+OR8.

HO-o-o-ORx Optically active 4-substituted-2-pentanol R''OH is reacted with p-toluenesulfonyl chloride in the presence of an organic base to form p-toluenesulfonic acid ester, and then 4 .4“
- Reaction with an alkali metal salt of dihydroxybiphenyl. The reaction product is purified by recrystallization and column chromatography to obtain the desired HoRg)-(GooOR'').

C) No. and deacetylation to obtain p-hydroxybenzoic acid optically active ester HO-@-COOR''.

2) HOBeans') -R8 Optically active 4-substituted-2-pentanol is converted to the corresponding bromide R''Br, and Grignard reagent BnO (macro)MgB
5no(φ'')-R' is synthesized by reacting with r, and hydrogenolysis is carried out in the same manner as in a) to obtain HObeakari R''.

The optically active compound (i) of the present invention does not have functional groups that are unstable to moisture or light, such as an azomethine group, an azo group, an azoxy group, or an ethynyl group as a structural component, and only has a stable ester structure and ether structure. Since it consists of
In addition to having extremely excellent weather resistance, by optimizing the substituent R2 of the optically active moiety and the chemical modification of the liquid crystal skeleton structure, it is possible to have an extremely large spontaneous polarization value of 100 nC/am' or more. It is possible to reverse the electric field at high speed. By chemically modifying the substituent R2 of the optically active moiety, it is also possible to provide a compound that becomes a chiral smectic liquid crystal at low temperatures and over a wide temperature range. Also,
Since such a compound has good mutual solubility with other liquid crystal compounds, when used as a component of a liquid crystal composition, it is effective in expanding the liquid crystal temperature range and improving the properties of the chiral smectic C phase of the liquid crystal composition. Compounds that do not form a smectic CM product by themselves can also be preferably used as one component of a chiral smectic CFi product composition.

The optically active compound (I) of the present invention can also be used as an additive component for providing a necessary twisted structure in a TN mode or super TN mode liquid crystal display element.

〔Example〕

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

In the identification of liquid crystal phases in the examples, Ct is crystal, ■ is liquid, Ch is cholesteric liquid crystal, SmAu smectic 8 liquid crystal, SmC'' smectic C liquid crystal, S
mX represents an unidentified smectic liquid crystal.

Example 1 (IR,3S)-p-n-dodecyloxybenzoic acid 4-
(4'-(1-methyl-3-propoxybutoxy))piphenyl ester (-R'''C in formula (1)
1□H2s, R' = Cx Hs, X=-O-1Y=
(2S,4S)-4-propoxy-2-pentanol 1
4 g (95.7 mmol) and 31 ml (3
83 mmol) into a dry 200 ml flask,
18.2 g of 4-toluenesulfonyl chloride (
95.7 mmol) was added in several portions. After the addition was completed, the reaction product was stirred overnight at room temperature and dissolved in 150 ml of 3N hydrochloric acid.
In addition, the mixture was extracted with 250 ml of diethyl ether. The ether layer was washed successively with IN hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine, and dried over anhydrous magnesium sulfate.

After filtering off the magnesium sulfate, the filtrate was concentrated to give 23°5 g of crude (IS, 3S)-p-toluenesulfonic acid 1-methyl-3-propoxybutyl, ester!
Obtained.

Next, 9.46 g of 4.4°-dihydroxypiphenyl (
50,8 mmol) and 100 ml of ethanol and 30
% potassium hydroxide aqueous solution'e was put into a 300 ml flask, heated to 80°C, and then the crude (is, 3S
) -p-1-luenesulfonic acid 1-methyl-3-propoxybutyl ester 23°5g in ethanol 40ml
A solution dissolved in was added dropwise, and the mixture was heated and stirred at 80° C. for 5 hours. After the reaction mixture was allowed to cool to room temperature, the precipitated crystals were filtered off and the filtrate was concentrated. Add 100ml of benzene to the concentrated filtrate.
1 and 100 ml of ethyl acetate were added, stirred well, and then filtered. The filtrate was washed with 3N hydrochloric acid and then with saturated brine.
It was dried with anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the filtrate was concentrated to obtain crude (IR, 3S)-4-hydroxy-4'-(1-methyl-3-propoxybutoxy)piphenyl.

This was purified by silica gel column chromatography and 4.5 g (14
, 3 mmol) was obtained.

p-n-dodecyloxybenzoic acid 708 mg (2,31
After adding 6.2 ml (85 mmol) of thionyl chloride to the mixture and heating under reflux for 2 hours, excess thionyl chloride was distilled off to obtain the corresponding acid chloride.

Next, (IR,3S)-4-hydroxy-4゛-(1-
Methyl-3-propoxybutoxy)piphenyl 800m
g (2,54 mmol) and dry triethylamine 4.8
A solution of p-n-dodecyloxybenzoic acid chloride dissolved in 7 ml of benzene was added dropwise to a mixture of 4 ml (34.7 mmol) under water cooling, and the mixture was stirred at 70° C. for 2 hours. The mixture was allowed to cool to room temperature, 20 ml of 3N hydrochloric acid was added, and extracted with 50 ml of ethyl acetate. The organic layer was washed with IN hydrochloric acid and saturated brine, and then dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the solvent was distilled off and the crude product was purified by silica gel column chromatography and recrystallization from ethanol to give (IR,3S)-p-
n-dodecyloxybenzoic acid 4-(4°-(1-methyl-3-propoxybutoxy))biphenyl ester 93
0 mg (1.54 mmol) was obtained.

(2S,4S)-4-propoxy-2-pentanol used as a starting material was synthesized by the following method.

(2S,4S)-bentanediol 2 to 11 flasks
8.3 g (0.27 mol), propionaldehyde 83.6 ml (1.44 mol) and dry benzene 3
00ml of p-toluenesulfonic acid under stirring.
8 mg (2.88 mmol) were added.

After stirring for 20 minutes, add 20 g of molecular sieve 4A.
was added and stirred for an additional 5 minutes. By filtering off the solid, distilling off the solvent from the filtrate, and distilling it under reduced pressure, (4S
, 6S)-2-ethyl-4,6-dimethyl-1,3-dioxane (bp 50-51°C/14mmHg) 20.7
g (144 mmol) was obtained.

52.4 g (393 mmol) of aluminum chloride in 11
After cooling to 0° C., 110 ml of dry diethyl ether was added and stirred for 30 minutes. Adding a suspension of 3.62 g (955 mmol) of lithium aluminum hydride and 110 ml of dry diethyl ether
After stirring for 0 minutes, add 40 m of dry diethyl ether.
20.5 g (142 mmol) of (4S,6S)-2-ethyl-4,6-dimethyl=1,3-dioxane dissolved in 1 was added dropwise. After the dropwise addition was completed, the temperature was raised and refluxed for 20 minutes.
Don't let the reaction complete. After cooling to room temperature, 2.7 ml of water,
230 ml of 10% dilute sulfuric acid and 80 ml of water were added sequentially. After separating the ether layer, the aqueous layer was extracted twice with ether, the ether layers were collected, washed with a saturated aqueous sodium bicarbonate solution and then with saturated brine, and dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered off and the ether was distilled off to obtain a crude product, which was distilled under reduced pressure to obtain (2S, 4S)-4.
-Propoxy-2-pentanol (bp61.5-62
．． 5℃/3mmHg) 19.3g (132 mmol)
I got it.

The infrared absorption spectrum of the obtained (IR,3S)-p-n-dodecyloxybenzoic acid 4-(4°-(1-methyl-3-propoxybutoxy))biphenyl ester was
As shown in the figure. In addition, 'HNMR of this compound (CDC13
, TMS internal standard) is as follows.

0.7-2.4 (36H, -CHl- and -G Hz
) 3.2-3.8 (m, 3H, -OCH and -OC
H2-) 4.0 (t12H, Ph0CHz-) 4.3-4.9 (ril 1H, Ph0CH-) 6.8
~7.7.8.05~8.2 (12H, benzene ring) The results of elemental analysis of this compound are as follows, and were in good agreement with the theoretical values. Theoretical value (as Cz*Hs40) C77,70% 8 9.03% Analysis value C7
7,8% H9,1% Based on the above analytical data, this compound was (IR13S)-
It was identified as pn-dodecyloxybenzoic acid 4-(4°-(1-methyl-3-propoxybutoxy))biphenyl ester.

The liquid crystal phase transition temperature of this compound is shown in Table 1, and it had an SmC'' phase over a wide temperature range.

This compound was coated with polyimide and rubbed.
The sample was sealed in a 10 micron thick liquid crystal cell made of O glass, and the value of spontaneous polarization Ps was measured using the triangular wave method (peak height ±20 mm, 5 Hz). The value of Ps at 53°C is 34
nC/am”.

Example 2 (IR, 3S) -p-n-octyloxybenzoic acid 4
-(4°-(1-methyl-3-propoxybutoxy))
Biphenyl ester (-formula (I) te R' =
Ca HI 7, R2= C2Hs, X=-O-1Y=
- p-n- instead of p-n-dodecyloxybenzoic acid
(IR,3S)-p-n-octyloxybenzoic acid 4-(4'-D-methyl-3-propoxybutoxy))biphenyl ester in exactly the same manner as in Example 1 except that octyloxybenzoic acid was used. was synthesized.

Table 1 shows the liquid crystal phase transition temperature of this compound.

Examples 3 to 6 p-n-dodecyloxybenzoic acid in Example 1 was
The following compound was synthesized in exactly the same manner as in Example 1 except that -n-alkoxy-3-pyridinecarboxylic acid was used.

Example 3 (IR,3S)-6-n-A, xyloxy-3-pyridinecarboxylic acid 4-(4°-(1-methyl-
3-propoxybutoxy)) biphenyl ester (-in formula (I), R''' CG Ht i, R''-=
Cx Hs, X=-O-1Y=-COO-12=-0-
1A = association, B = n) Example 4 (IR13S)-6-n-octyloxy-3
-Pyridinecarboxylic acid 4-(4°-(1-methyl-3-
propoxybutoxy)) biphenyl ester (-formula (
In I), R””CeH+□, R′L=C2Hs, X
=-O-1Y=-COO-12=-〇-1A=sha, B=
(b)) Example 5 (IR,3S,)-6-n-decyloxy-
3-pyridinecarboxylic acid 4-(4'-(1-methyl-3
-propoxybutoxy)) biphenyl ester (-in formula (I), R'=Cl0H21, R2=CyuH6,
X=-O-1Y=-COO-12=-0-1A=Example 6 (IR,3S)-6-n-dodecyloxy-3-pyridinecarboxylic acid 4-(4°-(1-methyl-3 -propoxybutoxy)) biphenyl ester (-formula CI)
In R1=C+zHzs, R'=C=Hs, X=-
O-1Y=-COO-12=-0-1A=<t, B=zuH)) Identification of these compounds was performed by elemental analysis, infrared absorption spectrum, and 'HNMR spectrum. Table 1 shows the liquid crystal phase transition temperatures of these compounds.

Example 7 (IR,3S)-p-n-dodecyloxybenzoic acid 4-
(4°-(1-methyl-3-pentyloxybutoxy)
) biphenyl ester (-in formula (I), R'=C
tthHts, R'L=C4H,
- (IR13S)-p-n-dodecyloxybenzoic acid 4-(4'-(1-methyl-3-pentyloxybutoxy))biphenyl ester was prepared in the same manner as in Example 1, except for changing to pentanol. Synthesized. Also, (2S
, 4S)-4-pentyloxy-2-pentanol is
(2S.

It was synthesized in exactly the same manner as in Example 1 using 4S)-bentanediol and valeraldehyde as raw materials.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

Further, the liquid crystal phase transition temperature of this compound was as follows, and it had an SmC'' phase in a relatively low temperature range.

Example 8 (IR,3S)-6-n-hexyloxy-3-pyridinecarboxylic acid 4-(4°-(1-methyl-3-pentyloxybutoxy))biphenyl ester (-formula (I)
In R' = CG HI 3, R' = CaHs
, X=-O-1Y=-COO-12=-0-1A=amount,
B=-@-@-> (2S,4S)-4-propoxy-2 in Example 3
- (IR,3S)-6-n-hexyloxy-
3-pyridinecarboxylic acid 4-(4°-(1-methyl-3
-pentyloxybutoxy)) biphenyl ester was synthesized.

Identification of this compound was carried out by elemental analysis, infrared absorption spectrum and HNMR spectrum.

Moreover, the melting point of this compound was 23° C., and it exhibited a monotropic ch phase and an SmA phase.

Example 9 Example using (IR,3S)-4-n-dodecyloxy-4°-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxy) phenyl ester (-formula % formula % - as a starting material) (Is,3S)-p-toluenesulfonic acid 1-methyl-3-propoxybutyl ester was synthesized in the same manner as in Example 1.

Next, 4.5 g of hydroquinone monobenzyl ether (
A mixture of 22.3 mmol), 30 m of ethanol, and 2.4 g of 30% aqueous sodium hydroxide solution was heated to 70°C to dissolve the previously synthesized (Is, 3S)-p-
6.7 g (22.3 mmol) of toluenesulfonic acid 1-methyl-3-butyl ester was added to 5 ml of ethanol.
ml of the solution was added dropwise, and the mixture was heated under reflux for 5 hours. After cooling to room temperature, the solvent was distilled off, 20 ml of 3N hydrochloric acid was added, and the mixture was extracted with 100 ml of ethyl acetate. The separated organic layer was washed successively with IN hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine, and then dried over anhydrous magnesium sulfate. The crude product obtained by filtering off magnesium sulfate and distilling off the solvent was purified by silica gel column chromatography to obtain (IR,3S)-4-benzyloxyphenyl-(1-methyl-3-propoxy). Butyl ether 3
．． 29 g (10.0 mmol) was used.

1i) Synthesis of (IR13S)-p-(1-methyl-3-propoxybutoxy)phenol (IR,3S)-4-benzyloxyphenyl-(1-methyl-3-propoxy)butyl ether 3 obtained in i) .21 g (9.77 mmol) in ethanol 3
0 ml of the solution, 640 mg of 5% palladium on carbon catalyst was added, and a hydrogenation reaction was carried out at room temperature.

After filtering off the catalyst and distilling off the solvent, it was purified by silica gel column chromatography to obtain (IR,3S)-p-(1-
Methyl-3-broboxybutoxynophenol 1.92
g (8.1 mmol) was obtained.

1ii) (IR,3S)-4-n-dodecyloxy-4
Synthesis of ``-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxy)phenyl ester'' Thionyl chloride 5.
After adding 4 ml (74 mmol) and heating under reflux for 2 hours, excess thionyl chloride was distilled off to obtain the corresponding acid chloride.

Next, 500 mg (2°1 mmol) of (IR,3S)-p-(1-methyl-3-propoxybutoxy)phenol and 4.2 ml (30 mmol) of dry triethylamine were added.
Into the mixture, the above 4-n-totoxyloxy-4-biphenylcarboxylic acid chloride was dissolved in 7 ml of benzene (8 liquids were added dropwise under water cooling, and stirred at 70°C for 2 hours. Allowed to cool to room temperature. Add 20 ml of 3N hydrochloric acid,
After extraction with 50 ml of ethyl acetate, the organic layer was washed with IN hydrochloric acid and saturated brine, and then dried over anhydrous magnesium sulfate.

After filtering off the magnesium sulfate, the solvent was distilled off and the crude product was purified by silica gel column chromatography f- and recrystallization from ethanol, (IR, 3S)
450 mg (0.75 mmol) of p-n-dodecyloxy-4'-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxy)phenyl ester were obtained.

The infrared absorption spectrum of this compound is shown in FIG. In addition, 'HNMR spectrum of this compound (CD Cl ]
, δ (ppm) of TMS internal standard 4) was as follows.

0.7-2.2 (36H, -CL- and -C) (3)
3,:2-3.7(m,3H,-〇CH- and 10C
H2-) 4.0 (t, 2H, Ph0CH2-) 4.3-4.8 (m, LH, PhOCH-) 6.8-7
．． 7.8.1 to 8.3 (12H, benzene ring) The results of elemental analysis of this compound were in accordance with Ikko's own, and agreed well with the theoretical values. Theoretical value (as C]9Hs405) C77,70% 8 9.03% Analysis value C
77.6% 8 Based on the analytical data of 9.2% or more, this compound was identified as (IR13S)-4-n-dodecyloxy-4
It was identified as °-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxy)phenyl ester.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an SmC''' phase over a wide temperature range.

70'97'106'C-1→SmC"-1→SmA-1→ ■Example 10 (IR, 3S)-4-n-octyloxy-4'-biphenylcarboxylic acid p-(1-methyl-3 -Propoxybutoxy) phenyl ester (-Formula %Formula %) As carried out except that 4-n-dodecyloxy-4°-biphenylcarboxylic acid in Example 9 was changed to 4-n-octyloxy-4°-biphenylcarboxylic acid. (IR,3S)-4-n-octyloxy-4'-biphenylcarboxylic acid p-(1-methyl-3-
Propoxybutoxy) phenyl ester was synthesized.

The liquid crystal phase transition temperature of this compound was as follows.

65@89'121' (:, -)SmC'''-)SmA-〉■Example 11 (IR13S)-4-n-octyloxy-4゛-biphenylcarboxylic acid p-(1-methyl-3- xyloxybutoxy) phenyl ester (-in formula (I) R''' Ca Hl 7, R'' = Cs H1+,
X=-〇-1Y=-COO-1z=-o-1A=-@-
@-1B=-@-) (2S,4S)-4-propoxy- in Example 1o
(IR,3S)-4-n-ctyloxy-4'- biphenylcarboxylic acid p-(1-methyl-3
-hexyloxybutoxy) phenyl ester was synthesized. Also, (2S.

4S)-4-hexyloxy-2-pentanol is (
It was synthesized in exactly the same manner as in Example 1 using 2S,4S)-bentanediol and hexanal as raw materials.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an SmC'' phase in a relatively low temperature range.

12° 48° 72° 107°C→SmX-+SmC"→SmA→Working Example 12 (IR, 3S)-p-n-dodecyloxybenzoic acid p'
-(1-methyl-3-propoxybutoxy)phenyl ester (-in formula (I) R' = CI!H2s
, R2=Cx Hs, X=-O-1Y=-COO-1
z=-o-1A=kai, B=((kun) (IR,3S)-p-(1-methyl-3-propoxybutoxy) synthesized from (2S,4S)-4-propoxy-2-pentanol By reacting phenol with p-n-dodecyloxybenzoic acid chloride (IR
13S)-p-n-dodecyloxybenzoyl ap'-(1
-Methyl-3-propoxybutoxy) phenyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

Further, the melting point of this compound was 14°C, and it exhibited a monotropic SmC'' phase.

Example 13 (Is, 3S)-4-n-dodecyloxy-4°-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl) phenyl ester (-in formula (1), R1=C+!Hzs, R”=C:R5, X=-O
-1Y=-COO-1z=-coo-1A=(Binka, B
=-@-) i) Synthesis of (Is, 3S)-4-acetoxybenzoic acid 1-methyl-3-propoxybutyl ester. ) and heated under reflux for 2 hours, and then excess thionyl chloride was distilled off to obtain the corresponding acid chloride.

Next, a solution of the previously synthesized acid chloride in a mixture of 4 g (27.4 mmol) of (2S,4S)-4-bucoboxy-2-pentanol and 45 ml (324 mmol) of dry triethylamine in 40 ml of benzene was added. After the mixture was added dropwise under water cooling, the mixture was heated and stirred at 70° C. for 2 hours. Cool to room temperature, add 130ml of 3N hydrochloric acid, and add 200ml of ethyl acetate.
Extracted with m1.

The separated organic layer was washed sequentially with IN hydrochloric acid and saturated saline,
It was dried with anhydrous magnesium sulfate. The crude product obtained by filtering off magnesium sulfate and distilling off the solvent was purified by silica gel column chromatography to obtain (Is, 3S
4.46 g (22.5 mmol) of 1-methyl-3-propoxybutyl )-4-acetoxybenzoate were obtained.

1i) (Is, 3S) -4-hydroxybenzoic acid 1-
Synthesis of methyl-3-propoxybutyl ester (Is, 3S)-4-acetoxybenzoic acid 1-methyl-3-propoxybutyl ester obtained in i) 4.46
g (22.5 mmol), benzylamine 3.2 ml
(28,9 mmol) and diethyl ether 56 ml
After stirring the mixture at room temperature for 6 hours, 20 ml of 3N hydrochloric acid was added.
was added and extracted with 150ml of diethyl ether. The separated organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate.

After filtering off magnesium sulfate and distilling off the solvent, it was purified by silica gel column chromatography (Is, 3S).
3.59 g (13.5 mmol) of -4-hydroxybenzoic acid 1-methyl-3-propoxybutyl ester were obtained.

1ii) (IS, 3S)-4-n-dodecyloxy-4
Synthesis of p-(1-methyl-3-propoxybutoxycarbonyl)phenyl ester of ゛-biphenylcarboxylic acid 574 mg (1.5 mmol) of 4-n-dodecyloxy-4°-biphenylcarboxylic acid was added with 5.0 m of thionyl chloride.
1 (68.5 mmol) was added, and after heating under reflux for 2 hours, excess thionyl chloride was distilled off to obtain the corresponding acid chloride.

Next, in a mixture of 450 mg (1,69 mmol) of (IR,3S)-4-hydroxybenzoic acid 1-methyl-3-propoxybutyl ester obtained in ii) and 7 ml (51 mmol) of dry triethylamine, the above 4-n
A solution of -dodecyloxy-4''-biphenylcarboxylic acid chloride dissolved in 6 ml of benzene was added dropwise under water cooling, and then stirred at 70°C for 2 hours. After cooling to room temperature, 3N hydrochloric acid 2
After extracting with 50 ml of ethyl acetate, the organic layer was washed with IN hydrochloric acid and saturated brine, and then dried over anhydrous magnesium sulfate. After filtering out magnesium sulfate,
The solvent was evaporated and the crude product was purified by silica gel column chromatography and recrystallization from ethanol to give (Is,3S)-4-n-totoxyloxy-4°
-Biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl)phenyl ester 710mg
(1.13 mmol) was obtained.

The infrared absorption spectrum of this compound is shown in FIG. In addition, 'HNMR spectrum of this compound (CD C13,
TMS internal standard) were as follows.

0.7-2.0 (36H1-CHz- and -CR2)
3.2-3.7 (m, 3H, -OCH and -0CH2
-) 3.95 (t, 2H, Ph0CHi) 5.1 to 5.6 (m, LH, -COOCH-) 6.85
~7.7.8.0~8.25 (12H, benzene ring) The results of elemental analysis of this compound are as follows, and were in good agreement with the theoretical values. Theoretical value (as C4oH9406) C76, 16% H8, 63% Analysis value C76
,1% H8,8% Based on the above analytical data, this compound is (Is,3S)-4
-n-dodecyloxy-4'-biphenylcarboxylic acid p
-(1-methyl-3-propoxybutoxycarbonyl)
It was identified as phenyl ester.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an SmC'' phase over a wide temperature range.

66' 102° 113°C-+
The spontaneous polarization PsO value measured by the I triangular wave method was 134 nC/a at 57°C.
It was m2.

Example 14 (Is, 3S)-4-n-octyloxy-4'-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl) phenyl ester (in general formula (I), R' = Ca Hl 7 , R” = CtH9
, X=-O-1Y=-COO-1z=-coo-1A=
((B = -4 prevention)) The procedure was exactly the same as in Example 13 except that 4-n-octyloxy-4-biphenylcarboxylic acid was used instead of 4-n-totysyloxy-4-biphenylcarboxylic acid. (IS, 3S)-4-n-octyloxy-
4"-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl)phenyl ester was synthesized.

The liquid crystal phase transition temperature of this compound was as follows, and it had an SmC'' phase over a wide temperature range.

Example 15 (IS, 3S)-4-n-decyl-4"- and phenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl) phenyl ester (-formula % formula % single bond, Y=-COO -1z=-coo-1A=((Labe interaction, B=association) Self-contained except that 4-n-decyl-4°-biphenylcarboxylic acid was used instead of 4-n-totysyloxy-4°-biphenylcarboxylic acid. Completely similar to Example 13,
(IS, 3S) -4-n-decyl-4'-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl)phenyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an SmC'' phase at low temperatures and in a wide temperature range.

Example 16 (Is, 3S) 4-n-dodecyl-4'- and phenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl) phenyl ester (-formula % formula % 4-n instead of rubonic acid (IS, 3S)-4-n-dodecyl-4'-biphenylcarboxylic acid p-(1-methyl-3- Propoxybutoxycarbonyl) phenyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and IHNMR spectrum.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an SmC''' phase at low temperatures and in a wide temperature range.

The spontaneous polarization Ps of this compound was measured by the triangular wave method and was found to be 114 nC/cm' at 26°C. Also,
The response speed to an external electric field was measured using a 2 micron thick cell. When a ±20V, IHz square wave was applied at 26°C, clear switching was observed.
Response time was 55 microseconds.

Example 17 (IS, 3S) p-n-dodecyloxybenzoic acid p
'-(L-methyl-3-propoxybutoxycarbonyl) phenyl ester (R''' in general formula (I)
Cl□H25, R2=C, i(S, X=-〇-1Y--
coo-1z=-coo-1A=combination, B=C)4-n
(Is, 3S) p
-n-dodecyloxybenzoic acid p-(1-methyl-3-
Propoxybutoxycarbonyl) phenyl ester was synthesized.

The melting point of this compound is 22°C, and the monotropic S
It had mX phase.

Example 18 (IS, 3S) -4-n-dodecyloxy-4"-biphenylcarboxylic acid 1-methyl-3-propoxybutyl ester (-in formula (I), R1=C1□Hz,
R"=C2Hs, X=-O-1Y=single bond, z=-
coo-1A = -@-, B = -@-) After converting 4-n-dodecyloxy-4゛-biphenylcarboxylic acid to acid chloride, (2S,4S)-4-propoxy-2-
By esterification with pentanol, (IS,
3S)-4-n-dodecyloxy-4'-biphenylcarboxylic acid 1-methyl-3-propoxybutyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The melting point of this compound was 30°C, and it did not exhibit liquid crystallinity.

Example 19 (IR,3S)-4-n-octyloxy-3-fluorobenzoic acid 4-(4'-(1-methyl-3-propoxybutoxy))piphenyl ester (-R' in formula (1) = Ca Hs 7, R' = C2Hs, B
=(European)' In the same manner as in Example 1 except that p-n-dodecyloxybenzoic acid in Example 1 was changed to 4-n-year-old ctyloxy-3-fluorobenzoic acid, (IR, 3
S)-4-n-octyloxy-3-fluorobenzoic acid 4-(4'-(1-methyl-3-propoxybutoxy)
) Biphenyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The melting point of this compound was 71°C, and it exhibited a monotropic cholesteric phase.

Example 20 (IR13S)-4-n-cutyloxy-3=fluoro-4'-biphenylcarboxylic acid p-(1-methyl-3
-propoxybutoxy) phenyl ester (-formula (1
), R'"Ce H engineering 7, R2 = 4-n-dodecyloxy-4'-biphenylcarboxylic acid in Example 9 was replaced with 4-n-dodecyloxy-3-fluoro-4'-biphenylcarboxylic acid. (IR,3S)-4-n-octyloxy-3-fluoro-4'-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxy)phenyl ester was prepared in exactly the same manner as in Example 9 except that it was used. was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an SmC'' phase over a very wide temperature range.

150″t67″ 83’C-1 → SmC
“--→SmA -1→I”-50℃”! This is the lower limit temperature of a constant device, and the SmC'' state was exhibited even at this temperature. Therefore, the exact melting point is unknown.

When the spontaneous polarization Ps of this compound was measured using the triangular wave method, it was found to be 2
It was 79 nC/cm' at 5°C.

In addition, the response time measured in the same manner as in Example 16 was
It was 260 microseconds at 25°C.

Example 21 (IR,3S)-4-n-octyloxy-3-fluoro-4'-biphenylcarbon ap-(1-methyl-3
-hexyloxybutoxy) phenyl ester (-R''' Ce H1° in formula (I), (2S,4S)-4 in place of (2S,4S)-4-propoxy-2-pentanol in Example 20 -hexyloxy-
(IR13S)-4-n-octyloxy-
3-Fluoro-4°-biphenylcarboxylic acid p-(1-
Methyl-3-hexyloxybutoxy) phenyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an S m C'' phase at low temperatures and in a very wide temperature range.

-50"48' 73°C-→S
mC''-→SmA-→■''-50°C is the lower limit temperature of the measuring device, and the SmC'' state was also exhibited at this temperature. Therefore, the exact melting point is unknown.

When the spontaneous polarization Ps of this compound was measured using the triangular wave method, it was found to be 2
It was 49 nC/cm2 at 5°C.

In addition, the response time measured in the same manner as in Example 16 was
It was 220 microseconds at 25°C.

Example 22 (IR,3S)-4-n-octyloxy-3-fluoro-4'-biphenylcarboxylic acid p-(1-methyl-3
-ethoxybutoxy) phenyl ester (general formula (I)
R'=CeH+7, R'=C except that (2S,4S)-4-nitoxy-2-pentanol was used instead of (2S,4S)-4-propoxy-2-pentanol in Example 2o. was carried out in exactly the same manner as in Example 20,
(IR,3S)-4-n-octyloxy-3-fluoro-4°-biphenylcarboxylic acid p-(1-methyl-3
-ethoxybutoxy) phenyl ester was synthesized.

Further, (2S,4S)-4-ethoxy-2-pentanol was synthesized in exactly the same manner as in Example 1 using (2S,4S)-bentanediol and acetaldehyde as raw materials.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an SmC''' phase at low temperatures and in a very wide temperature range.

-50"65'84"C-1→
SmCll−→SmA−1→■−50° C. is the lower limit temperature of the measuring device, and the SmC” state was exhibited even at this temperature. Therefore, the exact melting point is unknown.

Example 23 (IS, 3S) -4-n-octyloxy-3-fluoro-4°-biphenylcarboxylic acid p-(1-methyl-
3-propoxybutoxycarbonyl) phenyl ester (in general formula (I), R'' = Cs 4-n-octyloxy-3-fluoro-4 instead of 4-n-decyloxy-4°-biphenylcarboxylic acid in Example 13)
Example 13 except that °-biphenylcarboxylic acid was used.
In exactly the same manner as (Is,3S)-4-n-cutyloxy-3-fluoro-4°-biphenylcarboxylic acid p
-(1-methyl-3-propoxybutoxycarbonyl)
Phenyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The liquid crystal phase transition temperature of this compound was as shown below, and it had an SmC'' phase over a very wide temperature range.

44° 84' 107@C-1→
SmC"--→SmA--→■Example 24 (Is, 3S)-4-(5-hebutyl-2-pyrimidyl)benzoic acid 1-methyl-3-propoxybutyl ester (R in general formula (I) '=C7H□5, R'=C
tHs, X=single bond, Y=single bond, Z=-C4-(5-
(Is,3S)-4 by converting hebutyl-2-pyrimidyl)benzoic acid to the acid chloride and then esterifying it with (2S,4S)-4-propoxy-2-pentanol.
-(5-hebutyl-2-pyrimidyl)benzoic acid 1-methyl-3-propoxybutyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The melting point of this compound was 46°C, and it did not exhibit liquid crystallinity.

Example 25 (IR,3S)-5-n-year-old cutyl-2-(4-(1-
Methyl-3-propoxybutoxy)phenyl)pyrimidine (R” ” in general formula (I) Ce H17, R
''' Cz H1, X=single bond, Y=single bond, Z=5
- 1.08 g (3.81 mmol) of octyl-2-(p-hydroxyphenyl)pyrimidine in 10 ml of ethanol.
1, and after adding 1.3 g of 30% aqueous sodium hydroxide solution, (Is,3S)-p-toluenesulfonic acid 1
-Methyl-3-propoxybutyl ester 1.26g (
A solution of 1 g of 4.19 mmol) in 3 ml of ethanol was added dropwise. After heating for 4 hours, the mixture was allowed to cool to room temperature and the solvent was distilled off. After adding 10 ml of 3N hydrochloric acid, extraction was performed with 50 ml of ethyl acetate, and the organic layer was washed with IN hydrochloric acid and then with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off and the resulting crude product was purified by silica gel column chromatography to obtain the target product (IR13S)-5-octyl-2-(4-(1
120 mg (0.29 mmol) of -methyl-3-propoxybutoxy)phenyl)pyrimidine was obtained.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

This compound was in a liquid state at room temperature and did not crystallize even when cooled to -80'C, but no liquid crystallinity was observed.

Example 26 6-(p-n-dodecyloxyphenyl)-3-pyridinecarboxylic acid p'-(1-methyl-3-hexyloxybutoxycarbonyl)phenyl ester (-formula (I)
In R””C+zH2s, R”=Cs H1r,X
=-O-1Y=-COO-12=-0-1A=(8),
B, =-o-) Example 11 except that 4-n-dodecyloxy-4'-biphenylcarboxylic acid in Example 11 was changed to 6-(p-n-dodecyloxyphenyl)-3-pyridinecarboxylic acid. 6-(p-n-dodecyloxyphenyl)-3-pyridinecarboxylic acid p'-(1-
Methyl-3-hexyloxybutoxycarbonyl)phenyl ester was synthesized.

Identification of this compound was performed by elemental analysis, infrared absorption spectrum and 'HNMR spectrum.

The liquid crystal phase transition temperature of this compound is as follows, and Sm
It had a C” phase.

Example 27 (Liquid crystal composition) 10% by weight of (IR,3S)-5-n-octyl-2-(4-(1-methyl-3-propoxybutoxy)phenyl)pyrimidine, which is the compound of Example 25, 2 -(4-octyloxyphenyl)-5-octylpyrimidine 49
Weight% and 2-(4-octyloxyphenyl)-5
A liquid crystal composition consisting of 41% by weight of -decylpyrimidine was prepared. This liquid crystal composition exhibited the following liquid crystal phase transition temperature and had an SmC'' phase at room temperature.

10' 39° 61°C--→S
mC" -1 → SmA -1 → I (IR, 3S) -
5-n-octyl-2-(4-(1-methyl-3-propoxybutoxy)phenyl)pyrimidine alone produces SmC
``Although it does not form a liquid crystal, by mixing it with 2-(4-octyloxyphenyl)-5-octylpyrimidine and 2-(4-octyloxyphenyl)-5-decylpyrimidine, which have an SmC phase, it can be formed over a wide temperature range. S
A mixture forming mC8 phase could be obtained.

Example 28 (Liquid crystal composition) 40 weight of (IS, 3S)-4-n-decyl-4°-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl) phenyl ester, which is the compound of Example 15 %, the compound of Example 17 (IS, 3S
) p-n-dodecyloxybenzoic acid p-(1-methyl-3-propoxybutoxycarbonyl) phenyl ester 40% by weight and the compound of Example 23 (IR
,3S)-4-n-cutyloxy-3-fluoro-4
A liquid crystal composition comprising 20% by weight of '-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl)phenyl ester was prepared. This liquid crystal composition exhibited the following liquid crystal phase transition temperature, and had an S m C''' phase over an extremely wide temperature range including room temperature.

t) 50°C is the lower limit temperature of the measuring device, and the SmC'' state was exhibited even at this temperature. Therefore, the exact melting point is unknown.

〔Effect of the invention〕

According to the present invention, a novel optically active compound derived from optically active 4-substituted-2-pentanol can be provided. Such optically active compounds have excellent performance as liquid crystals, especially ferroelectric liquid crystals.

[Brief explanation of the drawing]

FIG. 1 shows the compound (IR13S)-p of Example 1.
FIG. 2 is an infrared absorption spectrum of n-dodecyloxybenzoic acid 4-(4°-(1-methyl-3-propoxybutoxy))biphenyl ester, and FIG. 2 is the compound of Example 9 (IR13S)- 4-n-dodecyloxy-4
3 is an infrared absorption spectrum of '-biphenylcarbon mp-(1-methyl-3-propoxybutoxy) phenyl ester, which is the compound of Example 13 (Is
, 3S)=infrared absorption spectrum of 4-n-dodecyloxy-4°-biphenylcarboxylic acid p-(1-methyl-3-propoxybutoxycarbonyl)phenyl ester. Special 7 [Applyed by Daito Shimeikan Co., Ltd.

Claims (3)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is a linear alkyl group having 1 to 20 carbon atoms,
R^2 is a linear alkyl group having 1 to 18 carbon atoms, 3 carbon atoms
~20 branched alkyl groups, cyclohexyl groups, cyclohexyl groups substituted at the 4-position with linear or branched alkyl groups having 1 to 10 carbon atoms, phenyl groups, or cyclohexyl groups having 1 to 10 carbon atoms
~10 represents a phenyl group substituted at the 4-position with a linear or branched alkyl group, X is a single bond, -O-, -CO
O- or -OOC-, Y is a single bond, -COO- or -OOC-, Z is a single bond, -O- or -COO-, A and B are each independently a single bond, ▲ mathematical formula, chemical formula, There are tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ^x indicates an asymmetric carbon. When A or B contains an aromatic ring, one of its hydrogen atoms
One or two atoms may be substituted with a halogen atom. ) An optically active compound represented by (2) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is a linear alkyl group having 1 to 20 carbon atoms,
R^2 is a linear alkyl group having 1 to 18 carbon atoms, 3 carbon atoms
~20 branched alkyl groups, cyclohexyl groups, cyclohexyl groups substituted at the 4-position with linear or branched alkyl groups having 1 to 10 carbon atoms, phenyl groups, or cyclohexyl groups having 1 to 10 carbon atoms
~10 represents a phenyl group substituted at the 4-position with a linear or branched alkyl group, X is a single bond, -O-, -CO
O- or -OOC-, Y is a single bond, -COO- or -OOC-, Z is a single bond, -O- or -COO-, A and B are each independently a single bond, ▲ mathematical formula, chemical formula, There are tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ^x indicates an asymmetric carbon. When A or B contains an aromatic ring, one of its hydrogen atoms
One or two atoms may be substituted with a halogen atom. ) A liquid crystal consisting of an optically active compound represented by (3) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is a linear alkyl group having 1 to 20 carbon atoms,
R^2 is a linear alkyl group having 1 to 18 carbon atoms, 3 carbon atoms
~20 branched alkyl groups, cyclohexyl groups, cyclohexyl groups substituted at the 4-position with linear or branched alkyl groups having 1 to 10 carbon atoms, phenyl groups, or cyclohexyl groups having 1 to 10 carbon atoms
~10 represents a phenyl group substituted at the 4-position with a linear or branched alkyl group, X is a single bond, -O-, -CO
O- or -OOC-, Y is a single bond, -COO- or -OOC-, Z is a single bond, -O- or -COO-, A and B are each independently a single bond, ▲ mathematical formula, chemical formula, There are tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ^* indicates an asymmetric carbon. When A or B contains an aromatic ring, one of its hydrogen atoms
One or two atoms may be substituted with a halogen atom. ) A liquid crystal composition containing at least one optically active compound represented by: