JPH01254644A - Novel lactic acid derivative and liquid crystal composition containing said derivative - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R1 is 1-16C alkyl; R2 is 2-16C alkyl; Y is group shown by formula VII, group shown by formula VIII or single bond; m and n are O or 1; p is O-2; q is 1-6; groups shown by formula IX, formula X, formula XI and formula XII (1-2 hydrogens may be replaced with fluorine or chlorine) are 1,4-phenylene; C* and C** are asymmetric carbon atom of (S) or (R) configuration)]. EXAMPLE:3-Fluoro-4-[(S)2-methylbutoxycarbonyl] phenyl 4'-[(S)-2- propoxypropanoyloxy]biphenyl-4-carhoxylate. USE:A component for liquid crystal composition, showing ferroelectric chiral smectic phase, useful as a material of liquid crystal device. PREPARATION:A chloride shown by formula II is reacted with a compound shown by formula III in the presence of a base to form a compound shown by formula IV, which is treated with thionyl chloride to give an acid chloride shown by formula V. This acid chloride is reacted with an optically active alcohol ester shown by formula VI to give a compound shown by formula I when Y is group shown by formula VII.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a tF lactic acid spindle useful as an electro-optical display material and a liquid crystal composition containing the same, and particularly to a liquid crystal composition containing the same. The object of the present invention is to provide a liquid crystal material that can be used in liquid crystal devices with particularly excellent responsiveness and memory performance compared to conventional liquid crystal materials.

[Prior art]

Currently, the liquid crystal display elements that are widely used are mainly the TN type, which uses nematic liquid crystal, and although it has many advantages, its responsiveness is inferior to that of the original type such as CRT. The major drawback was that it was much slower than the previous display method. Although many liquid display systems other than the TN type have been studied, improvements in their responsiveness have not yet been made.

However, a liquid crystal device that makes full use of ferroelectric smectic liquid crystals can respond 100 to 1000 times faster than conventional devices, and can maintain display memory even when the multistable crystal is cut off. (memory effect) has recently been revealed. For this reason.

It has great potential for use in optical shutters, printer heads, flat-screen televisions, etc., and research and development is currently underway in various fields to put it into practical use.

Strong bt liquid crystals have a tilted chiral smectic phase as a liquid crystal phase, but among these, the one that is practically desirable is the chiral smectic C (hereinafter abbreviated as SC*) phase, which has the lowest viscosity. It is called.

Liquid crystal compounds exhibiting the SC* phase have been studied so far, and many compounds have already been synthesized. However, these SC compounds alone must meet the following conditions for use as optical switching elements for ferroelectric liquid crystal displays: (a) They must exhibit ferroelectricity over a wide temperature range including room temperature (→ high temperature range) (c) In particular, the chiral nematic (hereinafter abbreviated as N) phase should have an appropriate tilt angle (e) It should have a suitable tilt angle (e) It should have a small viscosity (f) ) Spontaneous polarization must be a large value to a certain extent.Furthermore, as a result of ()) U) and I/), it exhibits good orientation. There is nothing known that satisfies everything.

Therefore, the current situation is that SC liquid crystal compositions are used for research purposes.

As a method for preparing an SC liquid crystal composition, a liquid crystal compound or composition that does not exhibit ferroelectricity and exhibits a non-chiral smectic C (hereinafter abbreviated as SC) phase (hereinafter referred to as a base liquid crystal) is added with a chiral liquid crystal. Generally, a compound (hereinafter referred to as a chiral dopant) is saturated. However, in this method, unless the chiral dopant exhibits a very large spontaneous polarization, the spontaneous polarization of the SC composition will be too small and it will not exhibit a high-speed response.

In addition, although it is not necessarily necessary for the chiral dopant to exhibit a liquid crystal phase, in order not to narrow the liquid crystal temperature range of the composition, it is necessary to exhibit a liquid crystal phase, especially chiral smectic (chiral smectic).
Hereinafter, it will be abbreviated as SX. ) phase, if possible, it is desirable to exhibit the SC phase up to a high temperature range. Furthermore, in liquid crystal compounds that exhibit strong spontaneous polarization, there are many that have strong torsion for the liquid crystal phase, such as SC* phase where spirals appear, ♂
In the phase, the helical pitch becomes short, giving the orientation a form W. Next, in order to use a liquid crystal compound with strong spontaneous polarization as a chiral dopant, how much should be added? It was necessary to adjust the helical pitch km of the SC liquid crystal composition by restricting or adding a chiral compound with the opposite twist direction. In this case, if the direction of the spontaneous polarization of the chiral compound opposite to the twist direction is also opposite, the spontaneous polarization of the composition will cancel out and become smaller.
There were many troublesome problems in adjusting the spiral pitch.

[Problem to be solved by the invention]

For the above reasons, while having as large a spontaneous polarization as possible, the helical pitch is large and the SC
*A chiral liquid crystal compound that exhibits a phase was desired.

The problem to be solved by the present invention is that the chiral dopant exhibits extremely large spontaneous polarization, particularly in the ♂ phase, and exhibits an extremely large helical pitch even at room temperature. The object of the present invention is to provide a novel chiral compound that exhibits an SC* phase over a wide temperature range, has good orientation, and exhibits high-speed response.

[Means to solve the problem]

The present invention solves the above problems.Next, the present invention solves the above problems.
) is provided. In the above formula, R1 represents an alkyl group having 1 to 18 carbon atoms, but in order to obtain a compound with large spontaneous polarization and low viscosity, an alkyl group having 2 to 8 carbon atoms is preferable. Two hydrogen atoms are preferably fluorine atoms or chlorine atoms. Y is an intermediate linking group, -C-0-.

10-C- or a single bond. m and n each represent independent KO or 1, m = H = Q
In the case of m = n = 1, the compound of formula (1) is a two-ring type and its liquid crystallinity is poor, and in the case of m = n = l, it is a four-salt type and the viscosity increases. +n =
This is the case of the 33J1 type. p represents an integer from 0 to 2, and q represents an integer from 1 to 6. C* and C# each independently represent an asymmetric carbon atom with (S) or (8) configuration.

The compound of general formula (1) according to the present invention can be produced, for example, as follows.

(1) When Y is -C-O- CH.

1°...(1-!L) [R1 * R2+ in the above formula (ID ~ formula (■))
Each has the same meaning as in m s n * P + ] That is, an acid chloride which is a lactic acid derivative represented by formula (I[) is mixed with a hydroxycarboxylic acid of formula (III) in the presence of a base such as pyridine. A carboxylic acid of formula (IV) is obtained. Next, this is made into an acid chloride (V) using thionyl chloride, etc., and reacted with this in the same manner as the optically active alcohol nystyl of the hydroxycarboxylic acid represented by the formula (M). When Y is 10-0-, A compound of the general formula (I-&) can be prepared. It can also be produced by esterifying the compound of formula (IV) and the compound of formula (Vl) in the presence of a dehydration condensation agent such as metal liquid dicyclohexylcarbodiimide.

Here, the lactic acid derivative (ID is % of the Ministry of the Invention et al.
As shown in No. 140157, it can be produced by using ethyl lactate as a raw material, alkylating it with silver oxide and alkyl iodide, hydrolyzing it, and then treating it with thiol chloride.

Optically active alcohol ester of hydroxycarzanoic acid (
't4) is directly dehydrated and esterified with a hydroxycarboxylic acid represented by the formula and an optically active alcohol represented by the formula H6 1 HO-+CH2-)-CH-R2... in the presence of an acid catalyst. or hydroxycarzanic acid (■)
It can be produced by protecting the OH fund, converting it into an acid chloride, reacting it with an optically active alcohol to form an ester, and finally removing the protection fund.

Most of the hydroxycarboxylic acids (~n) are known compounds (especially when p=Q), and some are commercially available. It can be easily prepared from substituted phenol or substituted phenylphenol.

That is, after total methylation of the hydroxyl group, gold bromination at the 4- or 4'-position to form a Grignard reagent, (1) reaction with carbon dioxide (when p = 0), (reaction with 2J ethylene oxide, and then oxidation). (if p=1), (
3) A method of obtaining a carboxylic acid by reacting it with an acrylic ester in the presence of a copper compound, followed by hydrolysis (in the case of p=2), and finally removing the methyl group.

(■...n p=2 (i+) When Y is -o-6-, the lactic acid conductor of [[)...(1-b) 2〇) can be expressed as hydroquinone or 4.47 expressed by the formula (DO). - can be reacted with biphenols or substituted products thereof to produce phenol derivatives (XI).On the other hand, monoesters of dicarboxylic acids (X[)
A compound of general formula (1-b) when Y is OCO can be produced by using an acid chloride (Kari) and reacting it with a phenolic conductor OO.

Alternatively, the compound of formula (3) and the compound of formula (XI) may be condensed and esterified directly with a dehydrating agent.

Some of the compounds of formula (EK) are commercially available, and can be produced by treating the corresponding acetyl compound with performic acid and then carrying out a demethylation reaction.

The dicarboxylic acid monoester (XI) or its acid chloride can be produced, for example, by the following method.

(1) Direct monoesterification from dicarboxylic acid (
only if p=0).

(jl) After esterifying formilka/I/ynic acid,
Oxidize formyl group to form carboxylic acid and sulfate.

GiD Introduces a carboxyl group into an optically active ester.

The transition temperature, direction of induced helix, and direction of spontaneous polarization of a typical compound of formula (1) produced in this way are determined as follows.
Listed in the table.

The liquid crystal phase and phase transition temperature were measured using a polarizing microscope with a temperature control stage and a differential scanning calorimeter (DSC).
The transition temperature may vary slightly depending on the purity of the sample or the measurement conditions.

Nohe/' In Table 1, C is a crystalline phase, SX is a chiral smectic phase, SC is a chiral smectic C@i, SA is a smectic human phase, and N is a chiral nematic phase t-r.
represent isotropic liquid phases, respectively.

- indicates that a lotus phase exists, - indicates that the phase does not exist (or cannot be confirmed), the number to the right of . indicates the transition temperature from that phase to a phase in a much higher temperature range, ( ) indicates that the phase is monotropic. 1fc
The term "direction of spiral" refers to the direction of spiral induced when the compound is added to a liquid crystal exhibiting a nematic phase. *The melting point is unknown because it does not crystallize even if left at low temperatures for a long time.

The purity of the product was confirmed by thin layer chromatography, gas chromatography, and high performance liquid chromatography.

The most significant structural feature of the compound of formula (I) of the present invention is that it has two small carbon atoms in the molecule, which are separated on both sides of the core.

On the other hand, the O2-flukoxypropanoyloxy group is derived from lactic acid and its ester, and its configuration is (6) or (S). The compound having this photoactive group' has a concentration of 100 n
C/? It has been falsely reported that it shows a large spontaneous polarization of - or more. (For example, if the phase transition temperature gold is shown below, the spontaneous polarization at the lO'' low temperature part (121,8℃) of the ♂-8C* transition point is 78 nC/an'', the 49° low temperature part (82, 8℃)
There are 144 ncAyn''-t' in .

101.4℃ *131.8℃ 133.2℃CSC
NI) However, in this compound, the helical pitch in the N phase is extremely small, and there is no SA phase between the N phase and the SC phase, so the orientation is extremely poor.

Even with the radicals used as chiral dopants, it is impossible to obtain a large pitch unless the content of i is significantly reduced.
Furthermore, with such a low force, the spontaneous polarization becomes small, making it impossible to obtain a high-speed response.

However, in the present compound (I), the opposite side chain also has an optically active group containing an ester group.In addition, the pitch of the N phase is extremely thick, and spontaneous polarization is also caused. This is an extremely desirable effect of increasing the amount of energy.

For example, the compound in Example 2 of the present invention has 11
It becomes an N phase at 1.5°C, then an SA phase at 110.5°C, an SC phase at 66°C, and the SC phase is maintained until room temperature or below. If left at low temperature for a long time, it will crystallize and its melting point will be 38℃.
It is. The pitch in this N phase is extremely large (20 μm or more), especially near the transition point to the SA phase, and
Since it has SAa, orientation is also extremely easy.

Its spontaneous polarization is 9 at the 10° low temperature part of the 5A-8C transition point.
7nΦ, 146 nC/cn1” at 30° low temperature part
It was extremely large. The response speed at 28°C was as fast as 104 μsec, and the tilt angle at that time was as large as 33.8°.

Thus, the compound of Example 2, when compared alone, is more effective than any of the previously known SC compounds.
It can be said that it has excellent performance in all aspects. Also,
25% of the compound of Example 3 was added to a pyrimidine-phenylbenzoate-based SC composition (base liquid crystal prisoner), and S
C composition was prepared and its response speed was measured.
It showed an extremely fast response of 51 μsec at 0°C and 63 μsec at 25°C. This composition has an SC phase of 6
It shows an SA phase at 6.5°C or lower and an N phase at 74°C or lower. Since the upper limit (Tc) of the SC phase of the base liquid crystal A is 56°C,
The compound of Example 3 also has the effect of expanding the temperature range of the SC* phase. The N phase of this *SC composition at 70° C. was about 4 μm, and good orientation was obtained.

Further, when 25% of the compound of Example 3 was added to another pyrimidine-phenylbenzier)-based SC composition (i-form FF crystal (B)) and the SC composition was prepared in the same manner, 2
An even faster response of 35 μsec at 5° C. was obtained.

This composition exhibits an SC phase at 70° C. or below, an SA phase at 84° C. or below, and a ♂* phase at 104° C. or below, indicating that the temperature range of the SC phase has been greatly expanded.

The spontaneous polarization of this compound is Tc - T = 10° (Tc is SC
*Maximum phase temperature) is 105 nC/c! n2. Tc-
It was as thick as 180n C7cm" at T=30°.

The parent liquid crystal matrix used was 10% by weight n-C. H,,0-G-Coo-CI)O-n-C8
H1710 penalty 0 n-C7H1,0-o-CooX subΣ0- n-C6
H13 consists of 10% by weight, 24% by weight, 27% by weight, 6% by weight, and 3% by weight.The phase transition temperature of the parent liquid crystal matrix is shown below.

The parent liquid crystal (BJ) consists of 65 kji (%) and 35 N!%, and the phase transition temperature of the parent liquid crystal (B) is shown below.

Examples of compounds used in the parent liquid crystal mixed with the compound of formula (I) of the present invention include, for example, the aforementioned phenylbenzoate compounds and pyrimidine compounds (B) in the second type. I can give it to you.

A2 (R3, R4 are each independently linear or branched (7
) represents any one of a furkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkoxylzenyl crystal, and an alkoxycarbonyloxy group. ) B: (R,, R4 are the same as above.) Further, any compound represented by the general formula C including A and B'i can be used for this purpose.

C: (R3+ R4 is the same as above, Z is -coo-
.

-0CO-, -CH20-, -0CH2-, -CH2C
Represents H2-, -CEI:C-, or a halogen-substituted product thereof. ) Further, in order to expand the temperature range of the SC phase of these compositions to a high temperature range, a tricyclic compound can be used. This tricyclic compound can generally be represented by the formula p.

D: (R3 and R4 are the same as above. ■, ■ and and 22
are -coo- and -oco-, respectively.

-CH20-, -0CH2-, -CH2-CH2-, -
C-represents C- or a single bond. ) These can be used alone, but it is more convenient to use them as a composition of two or more components because a wider temperature range can be obtained. In addition, compounds other than (6) can be used in the same manner as long as the side chain alkyl group is straight and exhibits an SC phase. Compounds shown in 4 to q, or (
4) Compounds other than ~q, even if they are not completely sold in the SC phase, as long as they are liquid crystal compounds with low viscosity, they can be added to reduce the viscosity of the composition, or they can be added to improve the response. This is an effective method for speeding up the process.

For this purpose, compounds in which both side chains are n-alkyl groups are particularly effective.

Now, the obtained liquid crystal compound or composition has a uniform thickness (approximately 1 μm to 20 μm) between two transparent glass electrodes.
By encapsulating it with g, it can be used as a crystal device. In order to obtain good contrast, uniformly oriented monodomains are required, and many methods have been tried for this purpose. Especially recently, isotropic liquid phase (1) → chiral nematic phase (N*) → smeknak phase (Sk) → chiral smectic C phase (SC
), which is a cell treated with crystalline gold orientated gold that exhibits a phase series of
Generally, a method of increasing the total helical pitch of the N-phase for orientation is generally used, and it can be said that the compound (1) of the present invention is suitable for this purpose.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but of course the gist and scope of the present invention are not limited to these Examples.

[Practice 1] Synthesis of 4-((S)-2-methylbutoxycarbonyl)phenyl 4'-((Si 2-7'lopoxyglopanoyloxy)biphenyl-4-calgexylate 1-a 4'-( (S)-2-7'ohoxif'
ot'? Synthesis of (S)-ethyl lactate 20.0,9, propyl iodide 45
．． OI, and 30.0.9'a-100 of silver oxide were stirred in dimethylformamide for 40 hours. Insoluble materials were separated from each other, water was added to solution F, and the mixture was extracted three times with hexane.

After dehydrating hexane NI, it was distilled under reduced pressure in a bathing bath N' (S
)-2-pro-ethyl xyglobionate 20.0 Jl-
Obtained. (boiling point 78°C 750-Hg) this 18.0.9
After stirring for 6 hours in a total of 5N sodium hydroxide water %ilOOmt, the mixture was made into a solution of 3-4 with water-cooled royal sulfuric acid. Extract with ether several times, dehydrate after fC, and distill off the ether.Te10.2
, VI7) (S)-2-f Roboxyglopion Eikin Tokutomo. To this mixture, 20-thionyl chloride and 0.5-thion pyridine were added and heated for 2 hours. After distilling off excess thionyl chloride from the reaction mixture under reduced pressure, benzene was added to the reaction mixture and the mixture was bath-dissolved to remove insoluble matter' (f-Dobesashi Tomogo, P
Benzene is extracted from the liquid.

Oily (S)-2-f lopoxypropionic acid chloride 1
0.5. I got li+.

5.27/ml of this chloride was added dropwise to 7.06 i of 4'-hydroxybiphenyl-4-carboxylic acid dissolved in 35 rnl of pyridine and 20 m of methylene chloride, and after completion of the dropwise addition, the reaction was carried out at reflux temperature for 6 hours. . After the reaction was over, a small amount of ethanol was added to safely esterify the unreacted acid salt 1, and then dilute gold hydrochloride was added to make it weakly acidic, followed by extraction with ether. A mixed solvent of n-hexane and ether was added to the crude crystals obtained by distilling off all the crude edges, and the mixture was heated to reflux temperature to completely remove the insoluble 47-hydroxybiphenyl-4-carboxylic acid. The mixture was cooled to 10° C., and the crystals tF were collected. Most of the no-esterified products were present in KN in the p-liquid. This operation was further repeated to obtain 4.487 white crystals of 4'-((S)-2-globoxyglopanoyloxy)biphenyl-4-carboxylic acid.

This compound showed a liquid crystal phase. Its melting point was 155°C, and its clearing point was 220°C.

ib Synthesis of the listed compound Carboxylic acid obtained in 1-a 4.48. V is thionyl chloride 1
5tnt' and, with stirring, added pyridine 2-. After dissolving, it was heated to 40 to 50°C and reacted for 3 hours. Excess thionyl chloride was distilled off, toluene was added directly to the residue, and the mixture was thoroughly stirred. After all insoluble matter was removed by filtration, the solvent was distilled off again to obtain oily 4'-(<5)-2-f loboxyprononoyloxy)biphenyl-4-carboxylic acid with a yield of 4.50 liters. .

This acid chloride 220~ is dissolved in methylene chloride 5-
4-((S)-2-methylbutoxycaryl)phenol synthesized from S)-2-methylbutanol and 4-hydroxybenzoic acid 140~ was processed, and further pyridine 0.
5- was added, and the mixture was reacted for 3 hours under reflux of the solvent.

After cooling, 100% ether was added, and the mixture was washed successively with 10% hydrochloric acid, saturated carbonic acid (1) rum water bath solution, water, and saturated brine. After dehydration with IJ (anhydrous sulfuric acid), the solvent was distilled off.
+'J'J. Further recrystallization from ethanol yielded 237m9 of white crystals of the title compound.

The phase transition temperatures of this compound are summarized in Table 1.

1-c Preparation of SC compositions and manufactured devices using the listed compound vjJk (the above-mentioned pyrimidine-phenylbenzier)! 25% of the solution was added to the parent liquid crystal cell to prepare an SCm parabolic tube.

This composition exhibited an SCC of 2073 at temperatures below 5435°C, an SA phase of 181 at temperatures below 5°C and 78°C. This composition is heated to 85°C to form an isotropic liquid phase, which has a thickness of 1.
A liquid crystal device was created by filling the space between two glass transparent electrodes (one of which was coated with polyimide and subjected to rubbing alignment treatment) with a 9 μm spacer in between.

This liquid crystal device was slowly cooled at a rate of 5° for a total of 1 minute, so that N phase, SA@'i orientation was achieved, and SC phase monodomains could be obtained at 54° C. or lower.

A rectangular ik of 19V and 50Hz was applied to this liquid crystal device, and the transmitted light intensity M' was measured to be 96μ at 25℃.
A fast response time of seconds was confirmed. The tilt angle at this time was 19.9°, and the spontaneous polarization was 8.57 nC/cm''.The pitch of the fcN phase was also sufficiently large, and a good contrast was obtained.

Note that the spontaneous polarization of this compound alone is T−Tc=10°
120 nC1cm" and 7'c.

[Example 2] 2-fluoro-4-hydroxybenzoic acid and (S)-2
-3-Fluoro-4-((S)-2-methylbutoxycarbonyl)phenol was completely synthesized from methylbutanol using sulfuric acid as a catalyst. 4-((S)- in Example 1
(2-methylbutoxycarbonyl)phenol instead of
3-
Fluoro-4-((S)-2-methylbutoxycarbonyl)phenyl 4'-((S)-2-f lopoxyglopanoyloxy)biphenyl-4-carboxyle)W
Profit a.

When a liquid crystal device was prepared using this compound in the same manner as in Example 1, it showed good alignment and a short time of 104 μsec at 28° C. even when the above-mentioned method was used alone. The spontaneous polarization at this time was 162 nc/crn2.

[Example 3] 4'-hydroxybiphenyl-4-7 in Example 1
4-((SJ-2-f
Roboxyglopanoyloxy)benzoic acid was synthesized, and this compound was reacted with 4'-[(s)-2-methylbutoxycarbonyl)biphenyl-4-ol.
S) -2-methylbutoxycarbonyl)biphenyl-
4-yl 4-((87-2-globoxyglopanoyloxy)benzoate was obtained. This compound was added to the parent liquid crystal (C) having the following composition) and the parent liquid crystal (C) having the following composition. was added to prepare the SCm composition.

Table 2 shows the phase transition temperature, response time, and spontaneous polarization values of each SC composition.

In Table 2, the parent liquid crystal <C) is composed of 33.53% of 33.5% and 33.5%, and the phase transition temperature of the parent liquid crystal C) is shown below.

[Example 4] 4- (2-(S)-propoxydiglopanoyloxy)
Benzoic [1071n9.4-((S)-2-methylbutoxycarbonyl)phenol 95Irv/and dicyclohexylcarbodiimide 1401V' with methylene chloride 1
A catalytic amount of 4-dimethylaminopyridine dissolved in 2-?
The mixture was added and stirred at the same temperature. After 5 hours, ether was added, insoluble matter was separated, and the p solution was washed with 10% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate, water, and saturated brine, and then dried over sodium sulfate.

The oil obtained by evaporating all the solvent was purified by silica dull column chromatography to obtain 4-((t)2-methyl7'')oxycarbonyl)phenyl 4-((S)-2
-7'ropoxyglopanoyloxy)/shade 139 cm of a transparent oil was obtained. This compound did not crystallize even when left at room temperature or below for a long time. The structure is NMR, IR
Confirmed by.

[Example 5] Synthesized from 4-hydroxyphenylacetic acid and (S)-2-methylbutanol in place of 4-((SJ-2-methylbutoxycarbonyl)phenol in Example 1)
8) -2-Methylbutyl 4-hydroxyphenylacetate-)k was prepared in the same manner as in Example 1, except that 4-(
White crystalline gold of (S)-2-methylbutoxycarbonylmethyl)phenyl 4'-((s)-2-yropoxyglopanoyloxy)biphenyl-4-carboxylate was obtained.〇This compound was completely converted into a liquid crystal matrix. When an SC* composition was prepared by adding 10%, SC phase t at 57°C or lower and ♂ at 70°C or lower
It showed the phase. The helical pitch of the SC* phase of this composition was extremely large, the N-helical pitch was right-handed and 3.8 μm, and there was almost no change due to temperature, and the polarity of the 9-spontaneous polarization was ■.

[Example 6] In Example 1, 4-((,S)-2-methylbutoxycaryl) was replaced with phenol, and 3-(4-hydroxyphenyl)f-ropion relative and (S)-2- Synthesized from methylbutanol*(SJ-2-methylbutyl 3-
4-(2-((st-2-
Methylbutoxycarbonyl)ethyl)phenyl 4'-
White crystals of ((S)-2-f lopoxyglopanoyloxy)biphenyl-4-carboxylate were obtained.

When a 10% SC composition was prepared by adding 10% to this compound 'm'i matrix crystallization factor, the SC key metal showed an SA phase at 58°C or below, the SC key metal showed 64°C or below, the SA phase showed 72.5°C or below, the ♂ phase showed m, The helical pitch of the N* phase is 3.4 μm (70°) for right-handed winding.
The polarity of spontaneous polarization was ■.

[Example 7] 4'-acetoxybiphenyl-4-caldic acid 5.80
．． It was made into an acid chloride with 9-gold thionyl chloride and reacted with (S)-2-methyloctatool. Complete ether extraction,
Ether pigeon ↓〈I added benzylamine little by little to this at room temperature. After adding hydrochloric acid and further washing with water, the solvent was distilled off, and the resulting crude product was decolorized through a silica dull column (dissolved &: n-hexane-ethyl acetate mixture) and then re-purified from n-hexane. Crystallize (S
) -2-Methyloctyl 4'-hydroxybiphenyl-4-:/1F White crystals of lupoxylate 6.2!
I got ik. 4′-((S) −2 in melting point Example 3
-Methylbutoxycarzanyl)biphenyl-4-ol dimethylether, actual MIv/l13 except when this compound is used.
Similarly, 4'-((S)-2-methyloctoxycarbonyl)biphenyl-4-yl 4-((S)-2
-Proboxyglopanoyloxy)benzoate white crystals were obtained.

[Example 8] Commercially available terephthalaldehydic acid (4-formylbenzoic acid) was added to dichloropyridine of thionyl chloride in total methylene chloride and heated to form an acid chloride. To this, 2-methylbutanol was added, followed by (S)-2-methylbutyl 4-formylbenzoate.

Dissolve this in acetic acid, chromic anhydride water bath, total 30 to 4 g.
Methanol was added, and after the thread turned green, it was poured into ice water and extracted with ether.

After rinsing with water, perform 'p+i crystals from hexane with a width of 4-
((S)-2-methylbutoxycarbonyl)ammonium, 1% acid was obtained as follows.

This carboxylic acid was then treated with thionyl chloride to give 4-
((t))-2-methylbutoxycarbonyl)benzate chloride. To this, 4/-hydroxybiphenyl-4-yl obtained from (t)-2-f lopoxypropionic acid chloride and 414'-biphenol, (S)-2
-Proboxyglopionate The reaction was carried out in the same manner as in Example 1 to give 4-((S)-2
-,,l methylbutoxycarbonyl)benzonite hairyo14t=.

This compound could be similarly synthesized by the following steps.

Terephthalic acid chloride in methylene chloride, about A in pyridine
Our friend's 47-hydroxybiphenyl-4-yl (S)
-2-Propoxypropionate was reacted completely, and then an excess amount of (S)-2-methylbutanol was added and reacted. After post-treatment in the same manner, p, di(S)-2-methylbutyl terephthalic acid, etc. were removed by silica gel column chromatography, and recrystallized from ethanol to obtain the target compound. However, the method on the back right produced a product with a considerably lower @ degree than the former method.

[Example 9] (S) -3-Methylpentyl 4-hydroxybenzoate was prepared in the same manner as in U7 from the veterinary test using -3-methylpentanol and 4-acetoxybenzoate.

4-((S)-3-methylbentoxy carbonyl) phenyl 4'-((S)
-2-propoxygulono9noyloxy)biphenyl-
4-carboxylene)'eobtain7'2:,.

A 5CBi base material was prepared by adding 18% of this compound to the base liquid crystal (5).

This composition has an SC phase at 57.5°C or lower, an SA phase at 72.5°C or lower, and [? ! It showed a male phase below -74.5°C.

The helical pitch in the N'* phase was 3.8 μm in right-handed rotation, and it hardly changed with temperature.

[Example 10] 4'-((S)-2-f roboxyglopanoyloxy)biphenyl-4-carboxylic acid chloride and (S)-3-methylpentanol, which are the intermediates of Example 1, were 4'-((S)-3-methylpentoxy)biphenyl-4-yl (SJ-2-proboxyglopionate) was obtained by reaction in methylene pyridine chloride. It did not crystallize even after being left at temperatures below room temperature for a long time.

〔Effect of the invention〕

The compound of the present invention has an extremely large spontaneous polarization when used alone or as a mixture to form an SC* liquid crystal composition, and the helical pitch is also extremely large, especially at N*, making it an SC liquid crystal compound or composition. When added and used as an sc g crystal composition, helical pinch adjustment is extremely easy.

In addition, as shown in the examples, the compound of the present invention can be easily produced industrially, is colorless, and is sensitive to light.
It has excellent chemical stability against moisture, heat, etc.
Very practical.

Furthermore, the strong V5 electromagnetic crystal compound of the present invention or the composition containing the compound of the present invention has good alignment, has an extremely high response speed of more than 100 times that of conventional nematic liquid crystal, and is suitable for use in liquid crystal devices. It is livable and useful as a material.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 16 carbon atoms, and R_2 represents an alkyl group having 2 to 16 carbon atoms. Represents.Y has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ or represents a single bond. m and n each independently represent 0 or 1, p represents an integer of 0 to 2, and q represents an integer of 1 to 6. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are each independently 1~ 2
represents a 1,4-phenylene group in which hydrogen atoms may be replaced with fluorine atoms or chlorine atoms. C^*
and C^*^* each independently represent an asymmetric carbon atom having the (S) or (R) configuration. ). 2. Claim 1 in which ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are 1,4-phenylene groups Compounds described in. 3. A liquid crystal composition containing the compound according to claim 1. 4. The liquid crystal composition according to claim 3, which exhibits a ferroelectric chiral smectic phase. 5. (1) The compound described in claim 1, and (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_3 and R_4 each independently represent a linear or branched represents an alkyl group, alkoxyl group, alkylcarbonyloxy group, alkoxycarbonyl group, or alkoxycarbonyloxy group) and (3) general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R_5 and R_6 each independently represent a linear or branched alkyl group, alkoxyl group, alkylcarbonyloxy group, alkoxycarbonyl group, or alkoxycarbonyloxy group. 6. The liquid crystal composition according to claim 5, wherein the mixing ratio of the compound according to claim 1 is 90% by weight or more. 7, (1) the compound according to claim 1, and (
2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_3 and R_4 each independently represent a linear or branched alkyl group, alkoxyl group, alkylcarbonyloxy group, alkoxycarbonyl group, or alkoxycarbonyl (represents an oxy group) and (3) general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_7 and R_8 each independently represent a linear or branched alkyl group or alkoxyl group) represents, Z
At least one of _1 and Z_2 represents a single bond, and the other is ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula,
Chemical formulas, tables, etc. are available▼, -CH_2O-, -OCH
_2- or represents a single bond. At least one of ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and each of the others independently represents ▲Mathematical formulas, chemical formulas, etc. , there are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
Represents ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. ) A liquid crystal composition consisting of a compound represented by: 8. The liquid crystal composition according to claim 7, wherein the mixing ratio of the compound according to claim 1 is 80% by weight or more. 9. A liquid crystal device comprising the compound according to claim 1 as a constituent element. 10. A liquid crystal device comprising the liquid crystal composition according to claim 3 as a constituent element. 11. A liquid crystal device comprising the liquid crystal composition according to claim 5 as a constituent element. 12. A liquid crystal device comprising the liquid crystal composition according to claim 7 as a constituent element.