JPH02142746A - Optically active compound and production thereof - Google Patents

Abstract

NEW MATERIAL:An optically active compound expressed by formula I (R<1> is 1-15C alkyl or alkyloxy; both X<1> and X<2> are H, halogen or cyano; X<1> and X<2> need not be same). EXAMPLE:(+)-p-(4-Octyloxybenzyloxy)-alpha-methylbenzyl heptanoate. USE:Useful as a component, etc., of ferroelectric liquid crystal mixtures, having high compatibility with the many existing liquid crystal substances and capable of realizing a great Ps value in the resultant smectic phase especially when used as a component of a smectic liquid crystal mixture. The obtained optically active alcohol and optically active ester are useful as a raw material for medicines, agricultural chemicals, perfumes, etc. PREPARATION:A racemic alcohol expressed by formula II and a fatty acid ester of 2,2,2-trichloroethanol are reacted with an enzyme having esterase activity to convert only the (+)-isomer of the racemic alcohol into an ester compound, which is then separated from the (-)-isomer of the alcohol. Thereby, the compound expressed by formula I is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel optically active compound and a method for producing the same. More specifically, the present invention relates to a novel optically active compound useful as a component of a ferroelectric liquid crystal mixture and a method for producing the same.

[Prior Art] Currently, the most widely used liquid crystal display element is a twistmatic (TN) type display element, but its response is slower than that of a light-emitting type display element (electroluminescent display, plasma display, etc.). It has the following drawbacks. Various studies have been attempted to improve this drawback, and a display method using ferroelectric liquid crystal as a liquid crystal display based on a principle different from the TN type display element has been proposed (N.C. Clark (N. A.

C1ark) et al., Applied Physics Letters (
Applied Physics Latters)3
6.899 (1980)).

This display method uses ferroelectric liquid crystal chiral smectic C.
It utilizes a phase or chiral smectic l phase, and is superior in high-speed response compared to a TN type display element. Furthermore, since it has advantages such as improved contrast when manufacturing large-capacity display elements, ferroelectric liquid crystal compounds having a chiral smectic phase are used as ferroelectric liquid crystal materials to increase the value of spontaneous polarization (hereinafter referred to as Ps). )
The current situation is either that there is a demand for a compound with a large value, or that no compound with sufficiently satisfactory performance has been found.

On the other hand, it is known that a ferroelectric liquid crystal mixture can also be converted to a ferroelectric liquid crystal mixture by adding to a smectic liquid crystal an optically active chiral compound that does not itself exhibit liquid crystallinity. The performance of this mixture varies greatly depending on the type of liquid crystal monomers used and their composition ratios and compatibility, so the scope of search for ferroelectric liquid crystal materials is expanding.

However, it is generally difficult to obtain optically active compounds, except for amino acids, organic acids, and sugars, which are relatively easily obtained by fermentation with microorganisms or as natural products. In particular, the technology for obtaining an optically active compound that is used by adding it to the smectic liquid crystal and has high compatibility with the smectic liquid crystal has not been completed.

That is, conventional methods for synthesizing optically active compounds using biochemical means or organic chemical methods have a narrow range of applicability and have the following drawbacks.

For example, as a biochemical method, there is an asymmetric synthesis method using baker's yeast or dehydrogenase, but this method tends to significantly reduce chemical yield and optical purity due to the solubility of the substrate used in water. On the other hand, the significance of using these methods for compounds that do not dissolve in water has not been recognized.

Another biochemical method is to perform an asymmetric transesterification reaction between tributyrin and a secondary alcohol using lipase in an organic solvent, but this method has a very slow reaction rate, and the optical Since the active compound is limited to butyl ester, it has the disadvantage that several additional synthesis steps are required to obtain the target compound.

On the other hand, when using organic chemical methods, the optical purity and chemical yield are low depending on the substrate used, and the optically active compounds obtained are often limited to low molecular weight compounds, which makes it difficult to use them for smectic liquid crystals. The synthesis of possible optically active compounds is difficult.

[Problems to be Solved by the Invention] One of the objects of the present invention is to provide an optically active compound that has good compatibility with existing smectic liquid crystals and can provide a liquid crystal mixture with a large Ps value. One of the objectives is to provide a method by which the above-mentioned useful optically active compounds can be easily produced.

[Means for Solving the Problems] The present invention is based on the general formula (I): H (wherein R1 is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, cyano group, and xl and x2 do not need to be the same) (hereinafter, the (+) alcohol represented by general formula (1)
)-m alcohol, (-) alcohol of (-)-(
1) Also referred to as alcohol), General formula (■): (In the formula, R1 is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, R2 is an alkyl group having 1 to 15 carbon atoms, x
l and x2 are both a hydrogen atom, a halogen atom, or a cyano group, and XI and x2 are not necessarily the same) (hereinafter, general formula (II))
The ester of the (+) form represented by is also referred to as the (+)-(I) ester, and the ester of the (-) form is also referred to as the (-)-(11) ester) and the general formula (I): H ( In the formula, R1 is an alkyl group or an alkyloxy group having 1 to 15 carbon atoms, xl and x2 are each a hydrogen atom, a halogen atom, or a cyano group, and Xi and x2 are not necessarily the same. An enzyme having esterase activity is applied to fatty acid esters of racemic alcohol and 2,2.2-)lichloroethanol (fatty acid has 2 to 1 B carbon atoms) to selectively produce an ester compound of only the racemic alcohol's (+) form. After that, the unreacted (−
) relates to a method for producing an optically active compound characterized by its separation from alcohol in the body;

[Example] The optically active compound of the present invention is an optically active compound represented by the general formula (I): H 2 and an optically active compound represented by the general formula (■).

In the optically active compound represented by general formula (I), R
1 is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, preferably 2 to 12 carbon atoms, and xl and x2 are both a hydrogen atom, a halogen atom, or a cyano group.

When the number of carbon atoms in R1 exceeds 15, the viscosity becomes high and the response speed becomes slow, and if R1 is not an alkyl group or an alkyloxy group, the thermal stability of the smectic phase when added to a liquid crystal composition is drastically reduced. easy to deteriorate.

Specific examples of the alkyl group having 1 to 15 carbon atoms include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, pentyl, l- or 2-methylbutyl, hexyl, - or 3-methylpentyl. , heptyl, ■- or 4-methylhexyl, octyl, 1-methylheptyl, nonyl, ■- or 6-methyloctyl, decyl, ■-methylnonyl, undecyl, ■-methyldecyl, dodecyl, 1-methylundecyl, etc. However, it is not limited to these. These alkyl groups may contain an asymmetric carbon.

Specific examples of alkyloxy groups having 1 to 15 carbon atoms include methoxy, ethoxy, propyloxy,
-propyloxy, butyloxy, i-butyloxy,
pentyloxy, l- or 2-methylbutyloxy,
Hexyloxy, ■- or 3-methylpentyloxy, heptyloxy, ■- or 4-methylhexyloxy, octyloxy, ■-methylhebutyloxy, nonyloxy, 1- or 6-methyloctyloxy, decyloxy, ■-methylnonyl Examples include, but are not limited to, oxy, undecyloxy, l-methyldecyloxy, dodecyloxy, and -methylundecyloxy. These alkyloxy groups may contain asymmetric carbon atoms.

Unless x1 and x2 are each a hydrogen atom, a halogen atom, or a cyano group, it is difficult to recognize its significance as a ferroelectric liquid crystal material.

In the optically active compound represented by the general formula (If), R2 is an alkyl group having 1 to 15 carbon atoms, preferably 2 to 12 carbon atoms, and RI Xl and x2 are both of the compound represented by the general formula (1). The same is true in this case.

When the number of carbon atoms in R2 exceeds 15, the viscosity becomes high and the response speed becomes slow, and if R2 is not an alkyl group, the thermal stability of the smectic phase when added to a liquid crystal composition is sharply reduced. Cheap.

Specific examples of R2 include the same alkyl groups having 1 to 15 carbon atoms as mentioned above as specific examples of R1.

Specific examples of the optically active compound represented by general formula (I) include para=(4-octylbenzyloxy)
-α-Methylbenzyl alcohol, para-(4-butylbenzyloxy)-α-methylbenzyl alcohol, para-(4-amylbenzyloxy)-α-methylbenzyl alcohol, para-(4-ethylbenzyloxy)-α
-Methylbenzyl alcohol, para-(4-substituted-benzyloxy) such as para-(4-octyloxybenzyloxy)-α-methylbenzyl alcohol, para-(4-hexyloxybenzyloxy)-α-methylbenzyl alcohol, etc. -α-methylbenzyl alcohol derivative,
Alcohol groups in which the side 3 or meta position of these benzene rings is substituted with a halogen atom or a cyano group)
body and (-) body. Also, the general formula (I[)
Examples of the optically active compound represented by the formula include esters of the optically active compound represented by the general formula 2 with acetic acid, acetic acid, heptanoic acid, etc. These optically active alcohols and optically active esters have the general formula (11) or the general formula (
This is only one example of the optically active compound represented by It), and the present invention is not limited to the above compound.

The optically active compound may be in the form of (+), (-)
However, the compound represented by the general formula [1] may be a (-) body, and the compound represented by the general formula [1] may be a (+) body.
A body is preferable from the viewpoint of ease of manufacture.

Furthermore, although the optical purity of the optically active compound is 100%, it is necessary to add a small amount (2 to 1 liters) to obtain a ferroelectric liquid crystal mixture.
0%) and the effect on the phase transition temperature of the smectic phase can be ignored, but it is preferable because the optical purity is 85%.
If the amount is above a certain level, there is no particular problem in using it as an additive for obtaining a ferroelectric liquid crystal mixture.

The optically active compounds represented by the general formula +1) and the general formula (It) usually have properties such as white crystals, although they differ depending on the number of carbon atoms in the substituted alkyl group or alkyloxy group.

Furthermore, since the optically active compound represented by the general formula (II) has high compatibility with many existing liquid crystal substances, it can be mixed and used as a component of a liquid crystal material. In particular, when used as a component of a smectic liquid crystal mixture, a large Ps value can be achieved in the resulting smectic phase. Furthermore, both the optically active alcohol and the optically active ester of the present invention can be suitably used as raw materials for medicines, agricultural chemicals, fragrances, and the like.

Next, a method for producing the compound represented by general formula (1) or general formula CI[) of the present invention will be explained.

The optically active compound represented by the general formula (1) or [I[) is a bara-(4-alkylbenzyl compound represented by the general formula (■)): oxy)-α-methylbenzyl alcohol, para-(4-alkyloxybenzyloxy)-α-methylbenzyl alcohol, or only one side of the benzene ring of these compounds
is a racemic alcohol substituted with a halogen atom or a cyano group (one of XI and x2, or x
It is produced by optical resolution of a racemic alcohol in which both l and x2 are substituted. That is, the optically active alcohol represented by the general formula (1) is
alkylbenzyloxy)-α-methylbenzyl alcohol, rose-(4-alkyloxybenzyloxy)-
α-Methylbenzyl alcohol or the (+) and (-) alcohols of compounds in which only one side of the benzene ring of these compounds is substituted with a halogen atom or cyano group; The optically active ester represented by [) is a fatty acid ester corresponding to the optically active alcohol represented by the general formula (I).

In the production method of the present invention, a racemic alcohol represented by the general formula (III) and a fatty acid ester of 2,2.2-1-lichloroethanol (fatty acid having 2 to 1 B carbon atoms)
The reaction with is carried out in an organic solvent using an enzyme with esterase activity. Enzymes with esterase activity selectively esterify only the (+) isomer of racemic alcohol, so through this reaction, the (+)-[11) ester and (
-)-(1) Alcohol can be changed. Also (+)-(1
1) Ester is converted into (+)-(1) alcohol by hydrolysis, and (-)-(T) alcohol is converted into (-)-(T) alcohol by esterification.
-)-[11) Can be made into an ester.

There is no particular restriction on the method for obtaining the racemic alcohol represented by the general formula (5), and any method may be used as long as the alcohol can be converted.

For example, when the substituent R1 in general formula (Ill) is an alkyl group, use a methyl rosealkylbenzoate corresponding to the target product, and when the substituent R1 is an alkyloxy group, first use the following reaction formula. As shown in Figure 2, methyl para-alkyloxybenzoate is synthesized by the Williamson synthesis method using methyl para-hydroxybenzoate and an alkyl halide corresponding to the substituent R1 of the target product, and this is used.

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms.) Next, as shown in the reaction formula below, methyl benzoate substituted with L
i A I H4 etc. to reduce, then PBr
For example, the compound is brominated with 3 or the like, reacted with parahydroxyacetophenone, and etherified by the Williamson synthesis method, and then reduced with sodium borohydride or the like.

↓ N a B ) Ia Carbon number of the above 2,2,2-trichloroethanol is 2 to 1
The fatty acid ester of No. 6 is used as a transesterification agent. The number of carbon atoms in this fatty acid corresponds to the number of carbon atoms in R2 of the compound represented by the general formula (I[), and by appropriately selecting and using the number of carbon atoms in the fatty acid, the compound can be changed depending on the purpose.

That is, in the present invention, since fatty acids having different numbers of carbon atoms are used as transesterifying agents, the number of reaction steps can be reduced compared to the conventional method. 2,2.
2-) Specific examples of fatty acid esters of dichloroethanol include 2.2.2-trichloroethyl acetate, 2,2.2-trichloroethyl butyrate, 2,
Examples include 2.2-trichloroethylheptanoate. Other transesterification agents such as 2-chloroethyl acetate, tributyrin, trichloroethyl acetate, and ethyl acetate can be used instead of the fatty acid ester of 2,2.2-trichloroethanol, but the reaction rate is 2.2. It is not practical because it is significantly slower than the fatty acid ester of 2-trichloroethanol.

The enzyme having esterase activity is 2゜2.2-
) It can be used without any restrictions as long as it can asymmetrically esterify only the (+) isomer of the racemic alcohol represented by the general formula [11D] in an organic solvent using a fatty acid ester of dichloroethanol. It can be derived from microorganisms, animals, or commercially available products.

Specific examples of such enzymes include Pseudomonas aeruginosa, which is an enzyme derived from microorganisms.
oIIlonas aeruglnosa), Achromobacterium viscosum (A
chromobacterial Ilviscosm)
Examples of enzymes derived from animals include enzymes produced from microorganisms belonging to the genus Achromobacterium, such as, but are not limited to, enzymes produced from seven viscera of pigs.

Commercial products of these enzymes include, for example, lipase "Amano JP (manufactured by Ohno Pharmaceutical ■, trade name), Lipase Toyo (manufactured by Toyo Jozo ■, trade name), pancreatin lipase (manufactured by Ohno Pharmaceutical Aji, trade name), Examples include creatine lipase (manufactured by Sigma ■, trade name), Lipase B (manufactured by Wako Pure Chemical Industries ■, trade name), and lipase MY (manufactured by Meito Sangyo ■, trade name).

The organic solvent used in the production method of the present invention must dissolve the racemic alcohol represented by the general formula (5) and the fatty acid ester of 2,22-trichloroethanol, and must not inhibit the enzymatic activity of the enzyme having esterase activity. It can be used without any particular limitations as long as it satisfies the requirements. Specific examples of such organic solvents include diethyl ether, methyl ethyl ether, n-hexane, cyclohexane,
Examples include n-hebutane and toluene.

In the production method of the present invention, an organic solvent containing a racemic alcohol represented by the general formula (III), a fatty acid ester of 2,2,2-trichloroethanol, and an enzyme having esterase activity is prepared. Without limitation, for example, a racemic alcohol represented by the general formula (ll), a fatty acid ester of 2,2,2-trichloroethanol, and an enzyme having esterase activity may be added to an organic solvent, and they may be prepared separately. It may be prepared by mixing liquids that have been dissolved or dispersed, or it may be prepared by first dissolving only those materials that are difficult to dissolve but can be dissolved by heating, and then adding other materials.

Racemyl alcohol represented by the general formula (In) and 2゜2.
The ratio of the fatty acid ester of 2-1-lichloroethanol used is 0.5 to 2.0 mol of the fatty acid ester of 2,2.2-trichloroethanol per 1 mol of the racemic alcohol represented by the general formula (II). is preferably used, and more preferably 1 to 1.5 mol. 2
．． 2. If the proportion of fatty acid ester in 2-trichloroethanol used is less than 0.5 mol, the molar amount is smaller than that of the (+) compound in the racemic alcohol represented by the general formula (I[D). ) It becomes impossible to esterify all of the 2,2,2-trichloroethanol, and if the amount exceeds 2 moles, the proportion of the fatty acid ester of the 2,2,2-trichloroethanol used that does not participate in the reaction increases, making it less economical. decreases.

The amount of the enzyme having esterase activity used is 10 to 600 per mole of the compound represented by the general formula (5).
g is preferable, and 100 to 500 g is more preferable.

If the amount used is less than 10 g, the reaction rate will be slow and it will be economically disadvantageous, and if it exceeds 600 g, the enzyme will be in excess compared to the reaction rate and will be economically disadvantageous.

Furthermore, the ratio of the total amount of fatty acid ester of general formula (I[D represented by racemic alcohol and 2.2.2-)lichloroethanol used is 0.1 to the weight of the solution in which these are dissolved in an organic solvent. It is preferably 50% (by weight, hereinafter the same), more preferably 10 to 30%.

If the usage ratio is less than 0.1%, the yield tends to be low relative to the amount of reaction liquid, resulting in high cost.
If it exceeds 50%, the concentration is too high and the reaction rate tends to decrease, resulting in a low yield.

In the production method of the present invention, since an enzyme having esterase activity is used, it is usually 10 to 40°C, preferably 25 to 40°C.
A reaction temperature of 30°C is employed. The reaction time is determined by the general formula (I
II) The type of racemic alcohol represented by the general formula (IID) and the enzyme having esterase activity, the proportion of the racemic alcohol represented by the general formula (IID), the fatty acid ester of 2,2,2-trichloroethanol, and the enzyme having esterase activity, and the stirring conditions. - Although it cannot be generally specified, it is usually 1 to 150 hours, preferably 24 to 96 hours.
It takes about an hour.

The reaction is completed using the general formula (8) using gas chromatography.
This is confirmed by measuring the conversion rate of racemic alcohol to ester represented by , and checking that the conversion rate becomes constant.

The reaction mixture thus obtained is first filtered to remove the enzyme having esterase activity. after that,
After removing the organic solvent, if necessary, it is separated into (+)-(I[) ester and (-)-(I) alcohol, for example, by silica gel chromatography. Furthermore, alcohol produced by transesterification or unreacted 2.2.2 is added to the thus separated product.
- If fatty acid ester of trichloroethanol is mixed, it may be purified by a method such as distillation.

In addition, as a developing solvent for column chromatography,
For example, a mixed solution of ethyl acetate/n-hexane (ethyl acetate/n-hexane in a volume ratio of 1/4 to 1120),
It is preferable to use a chloroform/methanol mixture (chloroform/methanol in a volume ratio of 1/10 to 1/40).

Moreover, the separated used enzyme having esterase activity can be reused.

The obtained compound was identified by 11f-NMR spectrum,
This is done by measuring the IR spectrum, specific rotation, etc.

Furthermore, the obtained (+)-(I[) ester can be easily converted to (-) by hydrolysis using an enzymatic or chemical method.
-(1) It is an enantiomer of alcohol (+)-(11).Also, when (-)-(1) alcohol is esterified, it becomes an enantiomer of (+)-[11) ester. -') -[1[) Can be made into an ester.

In this way, the optically active compound represented by the general formula (1) or the general formula (It) can be obtained with a yield of 80 to 90%.

EXAMPLES Below, the present invention will be explained in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 (±)-para(
3.57 g (0.01 mol) of 4-octyloxybenzyloxy)-α-methylbenzyl alcohol and 2
,2.2-)lichloroethylhebutanoate 2.69g
(0,0102 mol) and then lipase P
Add 5g of “Amano” (manufactured by Ohno Pharmaceutical ■, product name),
The reaction was carried out at 25° C. for 96 hours while stirring to ensure good dispersion. The reaction was carried out by monitoring the conversion rate to ester by gas chromatography every 8 hours. After confirming that the conversion rate to ester was constant and the reaction was complete, the lipase was removed by suction filtration.

After concentrating the filtrate, (-)-para-(4-octyloxybenzyloxy)-α-methylbenzyl alcohol and 2,2.2-
It is separated into trichloroethanol and (+) para-(4-octyloxybenzyloxy)-α-methylbenzylheptanoate, and the unreacted 2.
2.24 Lichloroethyl hebutanoate was mixed in, so column chromatography (ethyl acetate/n-
The two ester components were separated and purified using hexane (1/6 to 1/12). Of these fractions, (−)−
When the fraction of para-(4-octyloxybenzyloxy)-α-methylbenzyl alcohol was concentrated under reduced pressure,
1.59 g (yield 89.1%) was obtained.

Furthermore, the fraction of (+)-para-(4-octyloxybenzyloxy)-α-methylbenzylheptanoate was similarly concentrated under reduced pressure to yield 2.01 g (yield 85.8
%) was obtained.

The obtained compound was analyzed by 1) 1-NMR spectrum analysis and IR spectrum analysis, and was confirmed to be the desired compound. Further, the measurement results of specific optical rotation and melting point were as shown below.

(-)-para-(4-octyloxybenzyloxy)
-α-Methylbenzyl alcohol Specific optical rotation: [α] 25=-19,72° (cm1.0
0°CHCl3) Melting point: 86.5°C IH-NMR (300MHz, CDCls
Medium, δ value (ppm): 0.89 (m, 3H)
, 1.30 (m, IOH), 1.47 (d.

3H), 1.70(s, IH), 1.77(m,
2H), 3.94(t, 211), 4.83(
q, IH), 4.97(s, 2)1), 8.91
(m, 4H) , 7.30 (m, 4H) IR (KB
r, cm-1) 3302.3063.3040.2955.2932.
2855.1890.1609.1586.1516.
1466.1370.1300.1246.1177.
1069.1015.895.829.787.725
．． 613 (+)-para-(4-octyloxybenzyloxy)
-α-Methylbenzylhebutanoate 1・Specific rotation: [α
] , j5- +52.98° (c-1,01°CHC
l3) Melting point: 53.0°C 'H-NMR (300MIIz, in CDCIa, δ value (
ppm) ): 0.89 (m, 6H), 1.3
0(+a, 14H), 1.43(m.

2H), 1.50(d, 3H), 1.57(Il
l, 21+), 1.77(1,2H), 2.28
(t, 2H), 3.94 (t, 2H), 4.95
(s, 2H) , 5.84 (q, IH) , 6.9
2 (m.

4H), 7.30(Ill, 4H)IR(KBr,
ts-') :3445.3067.3032
．． 2955.2932.2874.2855.1886
．． 1732.1613.1582.1516.1467
．． 1420.1292.1250.1173.1111
．． 1065.1007.907.841, 814.7
25, Example 2 2.2.2-) Lichloroethylbutyrate 2.24 g instead of 2.2.2-) Lichloroethylheptanoate
The same operation as in Example 1 was carried out except that (0,0102 mol) was used, and (-)-para-(4-octyloxybenzyloxy)-α-methylbenzyl alcohol 1.6
3 g (yield 91.3%) and 1.77 g (yield 83.0%) of (+)-para-(4-octyloxybenzyloxy)-α-methylbenzylbutyrate were obtained.

(-)-para-(4-octyloxybenzyloxy)
-α-Methylbenzyl alcohol specific optical rotation = [α] 25 = -21,17° (c-1,0
0°CHCl3) Melting point: 87.5°C IH-NMR (300MHz, in CDCl5, δ value (
ppm) ): 0, H(t, 3H), 1.29
(IIl, IOH), 1.47 (d.

3H), 1.70(s, 1)l), 1.77(I
Il, 2H), 3.94(t, 2H), 4.8
3 (q, LH), 4.96 (s, 2H), 6.9
1(Ul, 4H), 7.30(m, 4H)IR(
KBr, am-”) :3302.3063.
3040.2955.2932.2855.1890,
18 (19,158B, 151B, 148B, 137
0゜1300.1246, ll77.1069.101
5.895.829, 787, 725, 613
(+)-hala-(4-octyloxybenzyloxy)
-α-Methylbenzylbutyrate specific optical rotation: ra ] ”5- +83.15° (c-1
, 03°ClICl5) Melting point: 47.5°C IH-NMR (300MHz, CDC1a, δ value (p
pm) ) :0, H(s, 13H), 1
．． 29 (a+, 8H), 1.43 (m.

2H), 1.50(d, 3B), 1.62(+a
, 2H) , 1.77(m, 2H) , 2.28(
t, 2H), 3.94(t, 2H), 4.95(
s, 2H), 5.84 (q, LH), 6.91
(n.

4H), 7.30 (m, 4H) IR (KBr, ca-1): 3445.3067.3 [132,2959,2932
, 2874, 2855, 1886, 1732, 1613
, 1582, 1516, 1470, 1420, 1385
,1300,1246,1177,1110,1065
, 1003, 841, 814, 813 Example 3 Anhydrous diethyl ether 70 ml, (±)-para-(4
-Octyloxybenzyloxy)-α-methylbenzyl alcohol was replaced with (±)-para-(4-hexyloxybenzyloxy)-α-methylbenzyl alcohol (3.28 g (0.01 mol)). Perform the same operation as in Example 1, and obtain 1.47 g of (-)-para-(4-hexyloxy)-α-methylbenzyl alcohol.
(yield: 89.6%) and 1.74 g (yield: 79.0%) of (+)-para-(4-hexyloxybenzyloxy)-α-methylbenzylheptanoate.

(-)-para-(4-hexyloxybenzyloxy)
-a-Methylbenzyl alcohol specific optical rotation = [α co25--24.42° (c-1,04
°ClICl5) Melting point: 84.0°C IH-NMR (300MHz, in CDCl5, δ value (
ppm) )0.90(t, 3H), 1.32(+
n, 6H), 1.47 (d.

3H), 1. B3(s, IH), 1.77(n+
, 2H) , 3.95(t, 2H) , 4.84(
q, LH), 4°97(s, 2H), 6.91(
m, 4H), 7.30(n, 4H)IR(KBr
, cm-1): 3302.3063.3040,2955.2932.
2862.1890.1609, l586, 1516
．． 1466, 1385.1300, ■24B, 1177
．． 1069.1015, 895.829, 787,
613 (+)-para-(4-hexyloxybenzyloxy)
-α-Methylbenzylheptanoate specific optical rotation: [α]
, g5- +55.0[lo(c-1,05゜CHC
l3) Melting point: 4B, 5°C IH-NMR (300MHz, in CDCIB, δ value (
ppOl) :0, H(m, 6B), 1.2
9 (m, IOH), 1.43 (n+.

2H), 1.50(d, 3H), 1.58(m,
2H), 1.77(m, 2H), 2.28(t
, 2H), 3.94(t, 2)1), 4.95(
s, 2H) , 5.84(q, 1)1) , 13.
91 (m.

4H), 7.30 (m, 4H) IR (KBr, Cl11-'): 3445.3
067.3032.2951.293B, 2866, ■
88B, 1732.1613.158B, 1516.1
48B, 141B, 1385.1292.1250.1
173, till, 1067.1003.934.87
5.841.818, 725, 810 Example 4 2.24 g of 2.2.2-)lichloroethylbutyrate instead of 2.2.2-trichloroethylheptanoate
(-)-P-(4-hexyloxybenzyloxy)-α-methylbenzyl alcohol 144
g (yield 87.8%), (+)-para-(4-hexyloxybenzyloxy)-α-methylbenzylbutyre) 1.68 g (yield 84.3%) were obtained.

(-)-para-(4-hexyloxybenzyloxy)
-α-Methylbenzyl alcohol specific optical rotation: [α] 25=-24,26°CC-1,0
2゜ClICl5) Melting point: 84.5℃ IH-NMR (300M) iz, in CDCl5, δ value (
ppm) ) : 0.89 (t, 3) 1) , 1.
32 (m, 8H), 1.47 (d.

:Hl), 1. [12(s, 1)1) , 1.77
(m, 2H) , 3.94 (t, 2) 1) , 4.
83(q, 1)I), 4.98(s, 2)1),
6.91 (m, 4) 1), 7.30 (m, 4H)
IR (KBr, crn-1): 3302, 3063, 3040, 2955, 2932,
2862.1890, 1609, 1586, 1516,
1466, 1385.1300, 1246, 1177,
1069, 1015, 895.829, 787,
613 (+)-para=(4-hexyloxybenzyloxy)
-α-Methylbenzylbutyrate specific optical rotation = [α] 25-+64.67° (c-1,0
0°CHCl3) Melting point: 4B, 0°C IN-NMR (300 liver z, CDC1a, δ value (p
pm) ) : 0.90 (o+, OH) , 1.3
2(II, 4H), 1.43(m.

2H), 1.50(d, 3H), 1. Ei3(m
, 211) , 1.77(a, 2H) , 2.28
(t, 2H), 3.94 (t, 2H), 4.96
(s, 2H) , 5.85 (q, IH) , 8.9
1 (m.

4H), 7.30 (m, 4H) IR (KBr, cm-1): 3445.3067.3032.2959.2936.
2874.1886.1732.1613.1586,
l516.1466.141B, 1385.1300.
1246.1177, IIIL1065, l003,
87G, 841, 814, 748, Example 5 Anhydrous diethyl ether 70ml (±)-para-(4
-Octyloxybenzyloxy)-α-methylbenzyl alcohol was replaced with (±)-para-(4-butyloxybenzyloxy)-α-methylbenzyl alcohol (3.0 Hg (0.01 mol)). Example 1
By carrying out the same operation as above, 1.32 g (yield 88.0%) of (-)-para-(4-butyloxybenzyloxy)-α-methylbenzyl alcohol, (+)-para-(4-
1.66 g (yield: 80.5%) of (butyloxybenzyloxy)-α-methylbenzylheptanoate was obtained.

(-)-para-(4-butyloxybenzyloxy)-
α-Methylbenzyl alcohol specific rotation = [α] ””-25,92° (c-1,0
2°CHCl3) Melting point: 88.5°C HNMR (300MHz, CDC1a, δ value (pp
m) ) :0.97(t, 3)1) ,1.
47(d, 3N), 1.49(i+.

2H), 1.70(s, IH), 1.77
(m, 2H), 3.95(t, 2H)
, 4.84 (q, IH) , 4.97 (s,
2H), 11i, 92(m, 4)1), 7
．． 30(+n, 4H)IR(KBr, cab-
1) :3306, 3067, 3040, 2955,
2932, 2870.1863.1609.1586.
1516.1470.1385.1300, 1246,
1177, 1069, 1007, 895.829,
783, 613 (+)-para-(4-butyloxybenzyloxy)α
-Methylbenzylheptanoate specific optical rotation: [(Z] 2" -+B1.25° (c-
1,13, CHCl3) Melting point Nioleic IH-NMR (300MHz, CDCl3)
Medium, δ value (ppm): 0.87 (1,3H), 0
．． 97 (t, 3H), 1.28 (m, 8H), 1.
47 (i+, 2H), 1.50 (d, 3) 1), 1
, 58 (m, 2H), 1, 7 B (m,
2H), 2,28(t, 2H), 3.95(
t, 2M), 4.95 (s, 2H), 5.84 (Q, I
H), 6.91 (m, 4H), 7.30 (m, 4)
1) IR (KBr, cm'): 3445,
3036, 2959, 2932, 2870, l883
．． 1732, 1613, 1586, 1512, 1466
, 1377.1300, 1242, 1173, 1111
, 1065, 1011.872, 829, 729,
637, 610 Example 6 2.2.2-)lichloroethylbutyrate 2.24 instead of 2.2.2-trichloroethylheptanoate
The same operation as in Example 5 was carried out except that g (0,0102 mol) was used, and (-)-para-(4-butyloxybenzyloxy)-α-methylbenzyl alcohol 1.8
7 g (yield 91.3%) and 1.81 g (yield 8B, 9%) of (+)-para-(4-butyloxybenzyloxy)-α-methylbenzylbutyrate were obtained.

(-)-para-(4-butyloxybenzyloxy)-
α-Methylbenzyl alcohol specific optical rotation: [ff] ]25--28.15°c-1
, 09, CHCl3) Melting point: 89.5°C lH-NMR (300MHz, CDCl3)
Medium, δ value (ppm): 0.97 (t, 3H),
1.47 (d, 3H), 1.48 (m, 2
H), 1.88(s, LH), 1.76(
n, 2) 1) , 3.95 (t, 2H) , 4.
83 (q, to), 4.96 (s, 2H)
, 6.92(Ill, 4)1) , 7.30(
m, 4H) IR (KBr, am-1): 3306.3067.3040.2955.2932.
2870.1863.1609.158B, 151B,
1470.1385.1300.124B, 1177.
1069.1007, 895.829, 783, 6
13 (+)-para-(4-butyloxybenzyloxy)-
α-Methylbenzylbutyrate specific optical rotation = [α] 25-+71.19° (c-1,1
2, ClCl5) Melting point: 37.5°C 'H-NMR (300 MHz, in CDCl5, δ value (p
pm)): 0.91 (t, 3H), 0.97 (t, 3H)
H), l, 47 (s, 2H), 1.50 (d, 3
)1), 1. B3 (m, 2H), 1.76 (m, 2H)
, 2.28(t, 2H), 3.95(t, 2H
), 4°913 (s, 2H), 5.85 (q, I
H), 6.91 (■, 4H), 7.30 (m, 4H) I
R (KBr, cm'): 3445, 306
7, 3035, 2959, 2932.2874.189
0, 1736, 1813, 1582, 1516, 146
6.1377, 1300. 1242, 1177, 11
11, 1069.1007, 972, 876, 8
26, 610 Example 7 (±)-para-(4-octyloxybenzyloxy)
The same procedure as in Example 1 was carried out, except that 3.41 g (0.01 mol) of (±)-para-(4-octylbenzyloxy)-α-methylbenzyl alcohol was used instead of α-methylbenzyl alcohol. conduct, (-)-para-(4
-octylbenzyloxy)-α-methylbenzyl alcohol 1.48 g (yield 85.6%), (+)-para-(4-octylbenzyloxy)-α-methylbenzylheptanoate 1.92 g (yield 84.8%).

(-)-para-(4-octylbenzyloxy)-α-
Methylbenzyl alcohol specific optical rotation: [α co”5--21.50° (c-1,03
, CHCl3) Melting point: 87.5°C H-NMR (300 MHz, CDC1a, δ value (p
pm)) :0.97(t,3)1), 1.3
8 (m, 10H), 1.55 (d, 3H),
1.87(a, 2H), 1.8[i(s, IH)
, 2.8ft(t, 2H), 4.93(q,
IH), 4.96(s, 2H), 7
, 23 (+a, 4H), 7.40 (m, 4
H) IR (KBr, cm-1); 3302, 3063, 3040, 2955, 2932,
2850.1889, 1609, 1585, 151B,
1465, 1370.1300, 1246, 1178
, 1070, 1015, 895.830, 787,
813 (+)-para-(4-octylbenzyloxy)-α-
Methylbenzylheptanoate specific optical rotation: [α] 25-+51.88° (c-1,0
1, CHCl3) Melting point: 53.1'C'H-NMR (800MHz, in CDC1a, δ value (
ppm)): 0.95(s, BH), t, 3
B (m, 14H), 1.43 (s, 2M), 1.5
0 (d, 3) 1), 1.57 (m, 2H), 1.78 (
layer, 2H), 2.28(t, 214),
2.66 (t, 2) 1), 4.96 (s, 2H)
, 5.84(Q, 1)l) , 7.23(i,
4H), 7.40(m, 4H)IR(KBr,
Cm-t) ;3445.3067.3032
．． 2955.2932.2874.2855.1886
．． 1732.1613.151B, 1470.1419
．． 1250.1173, 1065.1007, 876
．． 841, 814 Example 8 The same operation as in Example 1 was carried out, except that 5 g of Lipase Type II (manufactured by Sigma, derived from porcine pancreas) was used instead of Lipase P "Amano" (manufactured by Ohno Pharmaceutical ■, trade name). (-)-para-(4-octyloxybenzyloxy)-α-methylbenzyl alcohol 1.70 g (yield 9
5.2%), (+)-para-(4-octyloxybenzyloxy)-α-methylbenzylheptanoate 1
．． 78 g (yield 75.1%) was obtained.

The IH-NMR spectrum and IR spectrum of the obtained compound were the same as those shown in Example 1, and the measurement results of the specific optical rotation and melting point were as shown below.

(=)-para-(4-octyloxybenzyloxy)
-α-Methylbenzyl alcohol specific optical rotation: [α] 25--17.9B° (c-1,0
5, C) IcI3) Melting point: 85.0°C (+)-para-(4-octyloxybenzyloxy)
-α-Methylbenzylheptanoate specific optical rotation: [(!] D 5- “53.01” (
c=1. Melting point: 53.0°C Example 9 Example except that Lipase MY (manufactured by Meito Sangyo ■, trade name >5 g) was used instead of Lipase P "Amano" (manufactured by Ohno Pharmaceutical ■, trade name) The same operation as in 1 was performed to obtain 1.96 g of (-)-para-(4-octyloxybenzyloxy)-α-methylbenzyl alcohol (yield: 109.
8%), (10)-para-(4-octyloxybenzyloxy)-α-methylbenzylheptanoate 1.5
3 g (yield 65.3%) was obtained.

The IH-NMR spectrum and IR spectrum of the obtained compound were the same as those shown in Example 1, and the measurement results of the specific optical rotation and melting point were as shown below.

(-)-para-(4-octyloxybenzyloxy)
α-Methylbenzyl alcohol specific optical rotation = [α] 25 = -13,01° (c = 1.0
8, CHCl3) Melting point: 83.5°C (+)-para-(4-octyloxybenzyloxy)
-α-Methylbenzylheptanoate specific optical rotation = [α] 25-+52.34° (c-1,1
2, CHCl3) Melting point: 53.0°C Example 10 A liquid crystal having the composition shown below was prepared by using the compound +)-para-(4-octylbenzyloxy)-α-methylbenzylheptanoate obtained in Example 7. A composition was prepared.

-0CO-C6H13 2% This liquid crystal composition exhibited a smectic C phase at room temperature, and its phase transition was as follows.

46℃ 69℃ 71'Cs
-1→sA-1→N ->I (Here, S SSA, N, and I represent smectic C phase, smectic A phase, nematic phase, and isotropic liquid, respectively.) ITO film on two glass substrates and further 5to
Two films were formed, and a nylon film was applied and rubbed. Next, these two glass substrates are pasted together so that the cell thickness is 2 times, and after injecting a liquid crystal composition, the cell is heated to 75°C, where the liquid crystal composition changes to an isotropic liquid, and then 1°C. By cooling to room temperature using C/win, a ferroelectric liquid crystal display element with good alignment was obtained.

This liquid crystal display element was placed between two orthogonal polarizers, and a rectangular wave of V-20V was applied -P, and a change in the transmitted light intensity was observed. The response speed determined from the change in transmitted light intensity was 190 μ5 ecs at 25° C. and the tilt angle was 12 @.

[Effects of the Invention] The optically active compound of the present invention is a compound useful as a component of a ferroelectric liquid crystal mixture, and according to the production method of the present invention, the optically active compound can be easily produced.

Claims (1)

[Claims] 1. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, X^1 and X^2 are all hydrogen atoms, halogen atoms, or cyano groups, and X^1 and X^
2). 2 General formula (II): ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, and R^2 is an alkyl group having 1 to 15 carbon atoms. The alkyl group, X^1 and X^2 are all hydrogen atoms, halogen atoms or cyano groups, and X^1 and X^2 are not necessarily the same). 3 General formula (III) in an organic solvent: ▲Mathematical formula, chemical formula, table, etc.▼(III) (In the formula, R^1 is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, X^1 and Both ^2 are hydrogen atoms, halogen atoms, or cyano groups, and X^1 and X^
2) and a fatty acid ester of 2,2,2-trichloroethanol (fatty acid having 2 to 16 carbon atoms) are treated with an enzyme having esterase activity to produce racemic alcohol. A method for producing an optically active compound, which comprises selectively converting only the (+) form into an ester compound, and then separating it from the unreacted (-) form of the alcohol. 4. The production method according to claim 3, wherein the enzyme having esterase activity is an enzyme produced from a microorganism belonging to the genus Pseudomonas or Achromobacterium, or an enzyme produced from animal viscera.