JP2763309B2 - Optically active compound and method for producing the same - Google Patents

Description

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] At present, the most widely used liquid crystal display device is a twistmatic (TN) type display device, but the response is slower than a light emitting display device (electroluminescence display, plasma display, etc.). have. Various studies have been made to improve this disadvantage, and a display method using a ferroelectric liquid crystal as a liquid crystal display based on a principle different from that of the TN type display element has been proposed (NA Clark). Et al., Applied Physics Letters
s) 36, 899 (1980) reference).

This display method utilizes a chiral smectic C phase or a chiral smectic I phase of a ferroelectric liquid crystal, and is superior in high flux response and the like as compared with a TN type display element. Further, since there is an advantage that the contrast is improved when a large-capacity display element is manufactured, the value of the spontaneous polarization (hereinafter, referred to as a ferroelectric liquid crystal compound having a chiral smectic phase in such a ferroelectric liquid crystal material). Compounds with large Ps) have been recognized. However, at present, there is no device having a sufficiently satisfactory performance.

On the other hand, it is known that a ferroelectric liquid crystal mixture can also be obtained by adding a chiral compound having optical activity that does not exhibit liquid crystallinity itself to a smectic liquid crystal. Since the performance of this mixture varies greatly depending on the type of liquid crystal monomers used and their composition ratio or compatibility, the range of searching for ferroelectric liquid crystal materials has been further widened.

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

That is, the conventional method for synthesizing an optically active compound by a biochemical means or an organic chemical method has a narrow application range and has the following disadvantages.

For example, biochemical techniques include asymmetric synthesis using baker's yeast and dehydrogenase.In this method, the chemical yield and optical purity tend to decrease significantly due to the solubility of the substrate used in water, On the other hand, the significance of using these methods has not been recognized for compounds that do not dissolve in water.

Another biochemical method is a method of asymmetric transesterification of tributyrin with a secondary alcohol using lipase in an organic solvent. Since the active compound is limited to butyl ester, there is a disadvantage that several steps of synthesis are required to obtain the target compound.

On the other hand, in the case of using an organic chemical technique, the optical purity or chemical yield is low depending on the substrate used, and in many cases, it is limited to the obtained optically active compound or low molecular weight,
It is difficult to synthesize available optically active compounds for smectic liquid crystals.

[Problems to be Solved by the Invention] One of the objects of the present invention is to provide an optically active compound which has good compatibility with existing smectic liquid crystals and can give a liquid crystal mixture having a large Ps value. One of the objects is to provide a method capable of easily producing the useful optically active compound.

[Means for Solving the Problems] The present invention provides a compound represented by the general formula (I): (Wherein, R ¹ is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, X ¹ , X ² and X ³ are each a hydrogen atom, a halogen atom or a cyano group, and X ¹ , X ² and X ³ Need not be the same) (hereinafter, referred to as an optically active compound)
(R) -form alcohol represented by formula (I) is also referred to as (R)-(I) alcohol, and (S) form alcohol is also referred to as (S)-(I) alcohol), formula (II): (Wherein R ¹ , R ² , X ¹ , X ² and X ³ are the same as described above) (hereinafter, an ester of the (R) form represented by the general formula (II) (R)-(II) ester, (S) -form ester is also referred to as (S)-(II) ester) and an organic solvent in the general formula (III): (Wherein, R ¹ , X ¹ , X ² and X ³ are the same as above) and a fatty acid ester of 2,2,2-trichloroethanol (fatty acid having 2 to 16 carbon atoms).
Lipase is acted on the compound to selectively convert only the (R) form of the racemic alcohol into an ester compound, and then is separated from the unreacted (S) form of the alcohol.

[Action and Examples] The optically active compound of the present invention has the general formula (I): And an optically active compound represented by the general formula (II): Is an optically active compound represented by

In the optically active compound represented by the general formula (I),
R ¹ is an alkyl group or alkyloxy group having 1 to 15, preferably 2 to 12 carbon atoms, and X ¹ , X ² and X ³ are all a hydrogen atom, a halogen atom or a cyano group.

When the carbon number of R ¹ exceeds 15, the viscosity increases and the response speed when added to the liquid crystal mixture decreases, and when R ¹ is neither an alkyl group nor an alkyloxy group, the liquid crystal composition has When added, the thermal stability of the smectic phase tends to be rapidly reduced.

Specific examples of the alkyl group having 1 to 15 carbon atoms include, for example, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, pentyl, 1- or 2-methylbutyl, hexyl, 1- or 3-methylpentyl , Heptyl, 1- or 4-methylhexyl, octyl, 1-methylheptyl, nonyl, 1- or 6-methyloctyl, decyl, 1-methylnonyl, undecyl, 1-methyldecyl, dodecyl, 1-methylundecyl and the like. However, the present invention is not limited to these. Asymmetric carbon may be contained in these alkyl groups.

Specific examples of the alkyloxy group having 1 to 15 carbon atoms include, for example, methoxy, ethoxy, proloxy, i-
Propyloxy, butyloxy, i-butyloxy, pentyloxy, 1- or 2-methylbutyloxy, hexylyloxy, 1- or 3-methylpentyloxy, heptyloxy, 1- or 4-methylhexyloxy, octyloxy, -Methylheptyloxy, nonyloxy, 1- or 6-methyloctyloxy, decyloxy, 1-methylnonyloxy, undecyloxy, 1-methyldecyloxy, dodecyloxy, 1-methylundecyloxy, and the like. However, the present invention is not limited to this. Asymmetric carbon may be contained in these alkyloxy groups.

When X ¹ , X ² and X ³ are not each a hydrogen atom, a halogen atom or a cyano group, the compound is unlikely to be significant as a ferroelectric liquid crystal material.

In the optically active compound represented by the general formula (II), R ² is an alkyl group having 1 to 15, preferably 2 to 12 carbon atoms, and R ¹ , X ¹ , X ² and X ³ are all represented by the general formula The same applies to the compound represented by (I).

When the carbon number of R ² exceeds 15, the viscosity increases and the response speed when added to the liquid crystal mixture becomes slow, and when R ² is not an alkyl group, the smectic phase when added to the liquid crystal composition. , It is easy to rapidly reduce the thermal stability.

Specific examples of the above R ² may for example same may be mentioned the alkyl group of said R ¹ embodiment and with carbon was raised to 15.

Specific examples of the optically active compound represented by the general formula (I) include, for example, ((S)) or ((R))-4'-
(N-octyloxy) -4- {4- (1-hydroxyethyl) phenoxymethyl} biphenyl, ((S)) or ((R))-4 '-(n-heptyloxy) -4-
{4- (1-hydroxyethyl) phenoxymethyl} biphenyl and 4 ′-(1-methylheptyloxy) -4- {4- (1-hydroxyethyl) phenoxymethyl} biphenyl having two asymmetric carbons '-(1-Methyloctyloxy) -4- {4- (1-hydroxyethyl) phenoxymethyl} biphenyl, 4'-(1-methylhexyloxy) -4- {4- (1-hydroxyethyl) phenoxymethyl ｝ Biphenyl and the like,
Furthermore, 4'- which can be arbitrarily synthesized depending on the type of 2-alkanol and alkyl halide selected as a synthesis raw material.
(Alkyloxy) -4- {4- (1-hydroxyethyl) phenyloxymethyl} biphenyl derivatives, in which the hydrogen atom bonded to the 3- or meta-position of the benzene ring has been replaced by a halogen atom or a cyano group (R) -form and (S) -form of alcohol. In addition, the compound having two asymmetric carbons is represented by ((S,
(S)), ((S, R)), ((R, S)) and ((R, R)) forms. Specific examples of the optically active compound represented by the general formula (II) include esters of the optically active compound represented by the general formula (I) with acetic acid, butyric acid, heptanoic acid, and the like. In addition, these optically active alcohols and optically active esters are represented by the general formula (I) or (II)
Is only an example of the optically active compound represented by the formula, and the present invention is not limited to the compound.

The optically active compound may be an (R) form,
The compound represented by the general formula (I) may be an (S) form, and the compound represented by the general formula (II) may be an (R) form. It is preferable from the point of view.

The optical purity of the optically active compound is 100%, so that a small amount (2 to 10) is required to obtain a ferroelectric liquid crystal mixture.
%), And the effect of the smectic phase on the phase transition temperature can be neglected. However, if the optical purity is about 85% or more, it is used as an additive for obtaining a ferroelectric liquid crystal mixture. There is no particular problem to do.

The optically active compound represented by the general formula (I) and the optically active compound represented by the general formula (II) usually have properties such as white crystals, though they vary depending on the carbon number of the substituted alkyl group or the alkyloxy group.

In particular, the optically active compound represented by the general formula (II) has high compatibility with many existing liquid crystal substances, and thus is useful for mixing and using 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 realized in the obtained smectic phase. Furthermore, the optically active alcohols and optically active esters of the present invention can both be suitably used as raw materials for pharmaceuticals, agricultural chemicals, fragrances and the like.

Next, a method for producing the optically active compound represented by formula (I) or (II) of the present invention will be described.

The optically active compound represented by the general formula (I) or (II) has the general formula (III): (Wherein, R ¹ , X ¹ , X ² and X ³ are the same as those described above) or only one of the hydrogen atoms bonded to the benzene ring of these compounds is a halogen atom or a cyano group in any one of the substituted racemic alcohol (X ^1, X ² and X ^3, 2 or one of X ^1, X ² and X ^3, or all of X ^1, X ² and X ³ are substituted (Racemic alcohol) by optical resolution. That is, the optically active alcohol represented by the general formula (I) is 4 '-(alkyl) -4- {4- (1-hydroxyethyl) phenoxymethyl} biphenyl, 4'-
(Alkyloxy) -4- {4- (1-hydroxyethyl) phenoxymethyl} biphenyl or a compound in which only one hydrogen atom bonded to the benzene ring of these compounds is substituted with a halogen atom or a cyano group R)
The optically active ester represented by the general formula (II) 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, the reaction between the racemic alcohol represented by the general formula (III) and a fatty acid ester of 2,2,2-trichloroethanol (fatty acid having 2 to 16 carbon atoms) is carried out in an organic solvent using lipase. This is performed using Since lipase selectively esterifies only the (R) form of racemic alcohol, the reaction yields (R)-(II) ester and (S)-(I) alcohol. Also, (R)-
(II) Ester can be converted to (R)-(I) alcohol by hydrolysis, and (S)-(I) alcohol can be converted to (S)-(II) ester by esterification.

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

For example, when the substituent R ¹ in the general formula (III) is an alkyl group, use is made of ethyl 4'-alkylbiphenyl-4-carboxylate corresponding to the target compound. When the substituent R ¹ is an alkyloxy group, Ainiwa, Williamson because firstly with an alkyl halide or alkyl p- toluenesulfonate corresponding to substituents R ¹ of 4'-hydroxybiphenyl-4-carboxylic acid ethyl and target product as shown in the following reaction scheme (RTs) Ethyl 4'-alkyloxybiphenyl-4-carboxylate is synthesized by a synthesis method and used.

(Wherein R represents an alkyl group having 1 to 15 carbon atoms) Next, as shown in the following reaction formula, ethyl 4′-substituted biphenyl-4-carboxylate is reduced with lithium aluminum hydride (LiAlH ₄ ) or the like, Then phosphorus tribromide (PB
r ₃₎ After brominated due, a compound etherified by Williamson synthesis is reacted with para-hydroxyacetophenone, a method of reducing the like LiAlH ₄ and the like.

The fatty acid ester of 2,2,2-trichloroethanol having 2 to 16 carbon atoms is used as a transesterification agent. The number of carbon atoms in the fatty acid corresponds to the number of carbon atoms in R ² of the compound represented by the general formula (II) to be example, compounds according to the purpose by appropriately selected and used number of carbon atoms in the fatty acid will be obtained. That is, in the present invention, as an ester exchange agent,
Since a fatty acid having a different carbon number is used for each, the number of reaction steps can be reduced as compared with the conventional method.
Specific examples of the fatty acid ester of 2,2,2-trichloroethanol include, for example, 2,2,2-trichloroethyl acetate, 2,2,2-trichloroethyl butyrate, 2,2,2-trichloroethyl heptanoate And so on. 2,2,
In place of the fatty acid ester of 2-trichloroethanol, other transesterification agents such as 2-chloroethyl acetate, tributyrin, trichloroethyl acetate, ethyl acetate and the like can be used, but the reaction rate is low.
It is not practical because it is significantly slower than the fatty acid ester of 2,2,2-trichloroethanol.

The lipase is a fatty acid ester of 2,2,2-trichloroethanol in an organic solvent represented by the general formula (III):
Any of the racemic alcohols represented by can be used without limitation as long as it is capable of asymmetrically esterifying only the (R) form, and it can be of microbial origin, animal origin, or commercially available May be. Specific examples of such enzymes include, for example, microorganisms belonging to the genus Pseudomonas, such as Pseudomonas aeruginosa, which are enzymes derived from microorganisms, and microorganisms belonging to the genus Achromobacterium, such as Achromobacterium viscosm. Such as the enzymes produced,
In addition, examples of animal-derived enzymes include enzymes produced from swine gut, but are not limited thereto.

Commercial products of these enzymes include, for example, lipase "Amano" P (trade name, manufactured by Amano Pharmaceutical Co., Ltd.), Lipase Toyo (trade name, manufactured by Toyo Brewery Co., Ltd.), pancreatin lipase (Amano Pharmaceutical Co., Ltd.) Pancreatin lipase (product name, manufactured by Sigma), lipase B (product name, manufactured by Wako Pure Chemical Industries, Ltd.), Lipase MY (product name, manufactured by Meito Sangyo Co., Ltd.) And so on.

The organic solvent used in the production method of the present invention has the general formula (II)
The racemic alcohol represented by I) and the fatty acid ester of 2,2,2-trichloroethanol can be dissolved and used without particular limitation as long as they satisfy factors such as not inhibiting the enzyme activity of lipase. Specific examples of such an organic solvent include, for example, diethyl ether, methyl ethyl ether, n-hexane, cyclohexane, n-heptane, triene and the like.

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 a lipase is prepared, but this preparation method is not particularly limited, For example, a racemic alcohol represented by the general formula (III), a fatty acid ester of 2,2,2-trichloroethanol and a lipase may be added to an organic solvent to prepare them, and a solution obtained by separately dissolving or dispersing them is mixed. Alternatively, it may be prepared by first dissolving only those which are difficult to dissolve but can be dissolved by heating, and then adding other components.

Racemic alcohol represented by general formula (III) and 2,2,2
The proportion of trichloroethanol to the fatty acid ester is preferably 0.5 to 2.0 mol of 2,2,2-trichloroethanol fatty acid ester per mol of racemic alcohol represented by the general formula (III). It is more preferred to use up to 1.5 moles. When the use ratio is less than 0.5 mol, the molar ratio is smaller than that of the (R) form in the racemic alcohol represented by the general formula (III).
(R) It becomes impossible to esterify all of the isomers, and when the amount exceeds 2 moles, the proportion of the 2,2,2-trichloroethanol fatty acid esters used that does not participate in the reaction increases. , The economy tends to decrease.

The amount of the lipase to be used is preferably 10 to 600 g per 1 mol of the compound represented by the general formula (III),
100-500 g is preferred. If the amount used is less than 10 g, the reaction rate is low, which is economically disadvantageous. If it exceeds 600 g, the enzyme becomes excessive in comparison with the reaction rate, which is economically disadvantageous.

Furthermore, the ratio of the total amount of the racemic alcohol represented by the general formula (III) and the fatty acid ester of 2,2,2-trichloroethanol used is 0.1 to 50% (weight %, The same applies hereinafter), and more preferably 10 to 30%. When the use ratio is less than 0.1%, the yield tends to be low relative to the amount of the reaction solution, which is economically disadvantageous. When the use ratio exceeds 50%, the concentration is too high and the reaction rate is too high. And the yield tends to decrease.

Since lipase is used in the production method of the present invention, a reaction temperature of usually 10 to 40C, preferably 25 to 30C is employed. The reaction time depends on the type of the racemic alcohol or lipase represented by the general formula (III), the racemic alcohol represented by the general formula (III), the proportion of the fatty acid ester of 2,2,2-trichloroethanol and the lipase, the stirring state, and the like. Unlikely, it cannot be stipulated in general, but usually 1 to 150
Time, preferably about 24 to 96 hours.

The completion of the reaction is determined by liquid chromatography using the general formula (II
The conversion is determined by measuring the conversion of the racemic alcohol to the ester represented by I) and keeping the conversion constant.

The lipase is first removed from the reaction mixture thus obtained by excess or the like. After removing the organic solvent and the like, if necessary, the (R)-(II) ester and (S)-
(I) Separated from alcohol. Further, when the alcohol separated by the transesterification reaction or the unreacted fatty acid ester of 2,2,2-trichloroethanol is mixed in the thus separated product, it is purified by a method such as distillation. I just need. As a developing solvent for column chromatography, for example, ethyl acetate
/ n-hexane mixture (ethyl acetate / n-hexane in a volume ratio of 1/4 to 1/20), chloroform / methanol mixture (chloroform / methanol in a volume ratio of 1/10 to 1/40) ) Is preferably used.

The separated and used lipase can be reused.

The obtained compound is identified by measuring its ¹ H-NMR spectrum, IR spectrum, specific rotation, and the like.

Further, the obtained (R)-(II) ester is easily hydrolyzed by an enzymatic or chemical method or the like to easily form (S)
(R)-(I) alcohol which is a mirror image of (I) alcohol. Further, (S)-(I) alcohol can be converted into (S)-(II) ester which is a mirror image of (R)-(II) ester by esterification.

Thus, the optically active compound represented by the general formula (I) or (II) can be obtained in a yield of 80 to 90%.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

In each of the examples, the absolute configuration of the compound having two asymmetric carbon atoms was not determined, but for convenience, the absolute configuration ((S,
(S)), ((S, R)), ((R, S)), ((R, R)), etc. That is, when (R) -2-octanol is used as a starting material to give (R) -2-octyl p-toluenesulfonate and then reacted with ethyl 4'-hydroxybiphenyl-4-carboxylate, the reaction is naturally an inversion reaction. The product, 4 '-(1-methylheptyloxy)
Ethyl biphenyl-4-carboxylate was in the form of ((S)). On the other hand, the enantiomer that undergoes transesterification with the fatty acid ester of the transesterifying agent 2,2,2-trichloroethanol in the enzymatic optical resolution is referred to as “Journal of American” by AM Klobanov.
Chemical Society (J.Am.Chem.Soc.) 107,7072
(1985) ".

Example 1 [4 '-(1-methylheptyloxy) -4- {4-
Synthesis of (1-butanoyloxyethyl) phenoxymethyl} biphenyl ((S, R)) form and 4 ′-(1-methylheptyloxy) -4- {4- (1-hydroxyethyl) phenoxymethyl} biphenyl ( Synthesis of (S, S)) form] (i) Synthesis of (R) -2-octyl p-toluenesulfonate 130.0 g (1 mol) of (R) -2-octanol was dissolved in pyridine 1 dehydrated with KOH, Cooled to 5 ° C. With gentle stirring, 350 ml of a toluene solution of 190.5 g (1 mol) of p-toluenesulfonyl chloride was heated to an internal temperature of 10 ° C.
Over 2 hours, being careful not to exceed
The reaction was performed at 5 ° C. for 48 hours. After the reaction, toluene 2 was added, the precipitated crystals were separated, washed with 1% hydrochloric acid, water, and then with a saturated saline solution, and the organic layer was dried over magnesium sulfate and distilled under reduced pressure to remove (R)-. 2-octyl p
239.7 g of toluenesulfonate were obtained.

(Ii) Synthesis of 4 '-(1-methylheptyloxy) -4-hydroxymethylbiphenyl ethyl 4'-hydroxybiphenyl-4-carboxylate
242.3 g (1.0 mol) and 67.3 g (1.2 mol) of KOH were dissolved in 1.5 ethanol, and (R) -2-octyl p was added thereto.
-Add 341.3 g (1.2 mol) of toluenesulfonate and add 8
Refluxed for hours. After completion of the reaction, ethanol was distilled off under reduced pressure.
The precipitated crystals were separated, toluene 3 was added to separate insolubles again, and the mixture was washed with 1N KOH, water, and saturated saline. The organic layer was dried over magnesium sulfate and evaporated under reduced pressure to give 4'-
Ethyl (1-methylheptyloxy) biphenyl-4-carboxylate was obtained. Next, 265.9 g (0.75 mol) of 4-
Ethyl (1-methylheptyloxy) biphenyl-4-carboxylate was dissolved in anhydrous ether, and 17.1 g of LiAlH ₄ (0.1 g) was added.
(45 mol) was added dropwise to the suspended ether and reacted for 4 hours, followed by washing with 1% hydrochloric acid, water and saturated saline. The organic layer was dried over magnesium sulfate and evaporated under reduced pressure to give 4'-
187.2 g (0.6 mol) of (1-methylheptyloxy) -4-hydroxymethylbiphenyl was obtained (80% yield).

(Iii) 4 '-(1-methylheptyloxy) -4-
Synthesis of {4- (1-hydroxyethyl) phenoxymethyl} biphenyl 50 g (0.16 mol) of 4 '-(1-methylheptyloxy) -4-hydroxymethylbiphenyl was dissolved in 200 ml of carbon tetrachloride, and ice-cooled. 48.7 g of PBr ₃ below (0.18 mol)
Was added dropwise. After reacting for 5 hours, 0.5N NaOH, water,
The extract was washed with saturated saline, the organic layer was dried over magnesium sulfate, and the solvent was distilled off to obtain 55 g (yield 95%) of 4'-.
(1-Methylheptyloxy) -4-bromomethylbiphenyl was obtained. Then, 50 g (0.13 mol) of 4 '-(1-
(Methylheptyloxy) -4-bromomethylbiphenyl and 21.8 g (0.16 mol) of parahydroxyacetophenone were dissolved in 500 ml of acetone, 30.4 g (0.22 mol) of anhydrous potassium carbonate was added, and the mixture was reacted under reflux for 30 hours. . After the completion of the reaction, the inorganic salt was separated and then acetone was distilled off under reduced pressure, and the residue was recrystallized with acetone. The crystals were separated and dried to obtain 51 g (yield 90%) of 4 '-(1-methylheptyloxy) -4-{(4-acetyl) -phenoxymethyl}.
I got biphenyl.

The obtained compound was analyzed by ¹ H-NMR spectrum analysis and the results of the measurement are as shown below. ¹ H-NMR (300 MHz, CDCl ₃ , δ value ppm): 0.87 (t, 3H), 1.22-1.81 (m, 14H), 2.53 (s, 3
H), 4.39 (m, 1H), 5.12 (s, 2H), 6.93 (d, 2H), 7.0
1 (d, 2H), 7.46 (d, 2H), 7.49 (d, 2H), 7.58 (d, 2
H), 7.93 (d, 2H) This compound was reduced in the same manner as in the above (ii) to give the ((S), (R, S)) form of 4 '-(1-methylheptyloxy) -4- 50 g of {4- (1-hydroxyethyl) phenoxymethyl} biphenyl was obtained (98% yield).

The results of analyzing the obtained compound by ¹ H-NMR spectrum analysis and IR spectrum analysis are shown below. ¹ H-NMR (300 MHz, CDCl ₃ , δ value ppm): 0.87 (t, 3H), 1.23-1.81 (m, 16H), 4.38 (m, 1
H), 4.83 (q, 1H), 5.07 (s, 2H), 6.92 (d, 2H), 6.9
7 (d, 2H), 6.99 (d, 2H), 7.44 (d, 2H), 7.49 (d, 2
H), 7.56 (d, 2H) IR (KHr, cm ^-1 ): 3344, 3032, 2958, 2924, 2854, 1909, 1608, 1581,
1512, 1500, 1465, 1377, 1288, 1246, 1192, 1177, 11
19, 1080, 1022, 945, 933, 906, 875, 837, 814, 77
5, 756, 725, 551, 520 (iv) Optical resolution into ((S, S)) form and ((S, R)) form ((S), (R, S)) form in anhydrous diethyl ether 2 4 '-(1-methylheptyloxy) -4- {4-
3.89 g (9 mmol) of (1-hydroxyethyl) phenoxymethyl dibiphenyl and 2.69 g (10.2 mmol) of 2,2,2-trichloroethyl butyrate were dissolved, and then lipase P “Amano” (manufactured by Amano Pharmaceutical Co., Ltd.) , Product name) 5g
Was added thereto, and the mixture was reacted at 25 ° C. for 96 hours with stirring so as to be well dispersed. The reaction was carried out every 8 hours by monitoring the conversion to the ester by liquid chromatography. After confirming that the conversion to ester was constant and the reaction was completed, the lipase was removed by suction filtration.

The filtrate was concentrated, and then subjected to silica gel chromatography (ethyl acetate / n-hexane = 1/4 (volume ratio, the same applies hereinafter)) to give the ((S, S)) form of 4 '-(1-methylheptyloxy) -4. -{4- (1-hydroxyethyl) phenoxymethyl) biphenyl, 2,2,2-trichloroethanol and ((S, R)) form 4 '-(1-methylheptyloxy)
-4- {4- (1-butanoyloxyethyl) phenoxymethyl} biphenyl and 2,2,2-trichloroethyl butyrate, and unreacted 2,2
Since 2,2-trichloroethyl butyrate was contaminated, it was removed under reduced pressure. Of these fractions,
((S, S)) form of 4 '-(1-methylheptyloxy)
The fraction of 4- {4- (1-hydroxyethyl) phenoxymethyl} biphenyl was concentrated to give 1.65 g (yield 6
9%). Similarly, fractionation of the ((S, R)) form of 4 '-(1-methylheptyloxy) -4- {4- (1-butanoyloxyethyl) phenoxymethyl} biphenyl was similarly concentrated under reduced pressure to 2.32 g (94% yield).

The obtained compound was analyzed by ¹ H-NMR spectrum analysis and IR spectrum analysis to confirm that it was the target compound. The measurement results of the specific rotation and the clearing point were as shown below.

4 '-(1-methylheptyloxy) -4- {4-
(1-hydroxyethyl) phenoxymethyl フ ェ biphenyl ((S, S)) form Specific rotation: ▲ [α] ²⁰ _D ▼ = -20.6 ゜ (c = 1.00, CHCl
₃₎ clearing ^{point: 95.3 ℃ 1 H-NMR (} 300MHz, in CDCl _3, [delta] value (ppm)): 0.88 (t , 3H), 1.26 (m, 8H), 1.31 (d, 3H), 1.48
(D, 3H), 1.56 (m, 2H), 1.73 (m, 2H), 4.38 (m, 1
H), 4.84 (q, 1H), 5.08 (s, 2H), 6.92 (d, 2H), 7.2
9 (d, 2H), 7.43 (d, 2H), 7.49 (d, 2H), 7.54 (d, 2
H) IR (KHr, cm ^-1 ): 3344, 2458, 2924, 2854, 1909, 1608, 1581, 1512,
1500, 1465, 1377, 1300, 1288, 1246, 1192, 1172, 11
18, 1068, 1022, 968, 902, 875, 856, 837, 810 4 '-(1-methylheptyloxy) -4- {4-
(1-butanoyloxyethyl) phenoxymethyl｝ biphenyl ((S, R)) form Specific rotation: ▲ [α] ²⁵ _D ▼ = + 52.7 ゜ (c = 1.01, CHCl
₃ ) Clearing point: 60 ° C. (had a liquid crystal phase in the range of 40 to 60 ° C.) ¹ H-NMR (300 MHz, in CDCl ₃ , δ value (ppm)): 0.89 (t, 6H), 1.21 −1.80 (m, 20H), 2.28 (t, 2
H), 4.38 (m, 1H), 5.08 (s, 2H), 5.86 (q, 1H), 6.9
1 (d, 2H), 6.96 (d, 2H), 7.28 (d, 2H), 7.45 (d, 2
H), 7.49 (d, 2H), 7.58 (d, 2H) IR (KBr, cm ^-1 ): 2958, 2931, 2873, 2854, 1901, 1735, 1608, 1581,
1512, 1496, 1458, 1377, 1296, 1249, 1176, 1130, 10
37, 1014, 956, 933, 868, 829, 748, 725 Example 2 [4 '-(1-methylheptyloxy) -4- {4-
(1-heptanoyloxyethyl) phenoxymethyl}
Synthesis of Biphenyl ((S, S)) Form] 4 ′-(1-Methylheptyloxy) -4- {4- (1-hydroxyethyl) of the ((S, S)) form obtained in Example 1 3.0 g (6.9 mmol) of phenoxymethyl dibiphenyl was dissolved in 1.1 g (14 mmol) of pyridine dehydrated with KOH, and 1.2 g (8.3 mmol) of heptanoyl chloride was added under ice cooling. After reacting for 5 hours at room temperature, 100m
1% hydrochloric acid, water, 0.5N KO
H, and washed with saturated saline. The organic layer was dried over magnesium sulfate and evaporated under reduced pressure to give 3.5 g (93% yield) of 4'-.
(1-Methylheptyloxy) -4- {4- (1-heptanoyloxyethyl) phenoxymethyl} biphenyl ((S, S)) was obtained.

The obtained compound was analyzed by ¹ H-NMR spectrum analysis and IR spectrum analysis to confirm that it was the desired compound. The measurement results of the specific rotation and the clearing point were as shown below.

Specific rotation: ▲ [α] ²⁰ _D ▼ = -46.4 ゜ (c = 1.0, CHC
l ₃ ) Clearing point: 40.6 ° C. (had a liquid crystal phase in the range of 30 to 40.6 ° C.) ¹ H-NMR (300 MHz, δ value ppm in CDCl ₃ ): 0.84 (t, 3H), 0.88 (t , 3H), 1.20-1.82 (m, 24
H), 2.28 (t, 2H), 4.38 (m, 1H), 5.55 (s, 2H), 5.8
5 (q, 1H), 6.91-6.98 (m, 4H), 7.28 (d, 2H), 7.43
−7.58 (m, 6H) IR (KBr, cm ⁻¹ ): 2954, 2931, 2870, 2854, 1901, 1735, 1608, 1581,
1512, 1406, 1458, 1415, 1318, 1296, 1249, 1172, 11
14, 1068, 1033, 976, 941, 871, 824, 810, 725, 69
0, 644, 632 Example 3 [4 '-(1-methylheptyloxy) -4- {4-
(1-heptanoyloxyethyl) phenoxymethyl}
Synthesis of Biphenyl ((S, R)) Form] Instead of 2,2,2-trichloroethylbutyrate, 2,2,2
2.6 g (10 mmol) of trichloroethylheptanoate
The same operation as in Example 1 was performed except that
2.4 g (95% yield) of (1-methylheptyloxy) -4- {4- (1-heptanoyloxyethyl) phenoxymethyl} biphenyl ((S, R)) was obtained.

The results of ¹ H-NMR and IR of the obtained compound were the same as those in Example 2. The measurement results of the specific rotation and the clearing point were as shown below.

Specific rotation: ▲ [α] ²⁰ _D ▼ = + 47.4 ゜ (c = 1.03, CHCl
₃ ) Clearing point: 62 ° C (had a liquid crystal phase in the range of 40 to 62 ° C) In addition, 4 ′-(1-methylheptyloxy) -4- {4- (1- Hydroxyethyl)
Phenoxymethyl-biphenyl has specific rotation ▲ [α] ²⁰ _D
▼ = -20.2 DEG (c = 1.06, CHCl ₃₎ had a, ¹ H-
NMR and IR results and clearing point were similar to those obtained in Example 1.

Example 4 [4 '-(1-methylheptyloxy) -4- {4-
(Synthesis of (1-butanoyloxyethyl) phenoxymethyl} biphenyl ((S, S)) Form] 4 ′-(1-methylheptyloxy) -form of the ((S, S)) form obtained in Example 1 3.2 g (7.5 mmol) of 4- {4- (1-hydroxyethyl) phenoxymethyl} biphenyl was dissolved in 1.2 g (15 mmol) of pyridine, and 1.0 g (9.4 mmol) of a butyryl chloride solution was added under ice-cooling. .
After reacting for 4 hours, 100 ml of diethyl ether was added, and the mixture was washed with 1% hydrochloric acid, water, 0.5N KOH, and saturated saline.
The organic layer was dried over magnesium sulfate and evaporated under reduced pressure to give 3.
4g (90% yield) of 4 '-(1-methylheptyloxy)
-4- {4- (1-butanoyloxyethyl) phenoxymethyl} biphenyl was obtained.

The obtained compound had a specific rotation of [[α] ²⁰ _D ▼ = -51.8 ゜ (c = 1.01, CHCl ₃ ) and a clearing point of 40.5 ° C., and the results of ¹ H-NMR and IR are shown in Examples. It was the same as the ((S, R)) form obtained in 1.

Example 5 [4 '-(1-methylheptyloxy) -4- {4-
(Synthesis of (1-decanoyloxyethyl) phenoxymethyl} biphenyl ((S, S)) form] ((S, S)) form of 4 ′-(1-methylheptyloxy) -4- {4- (1 -Hydroxyethyl) phenoxymethyl dibiphenyl 4.0 g (9.3 mmol), n-decanoyl chloride 2.1 g (11.2 mmol), pyridine 1.8 g (22
The procedure of Example 2 was repeated, except that the compound used was 5.1 mmol (yield: 93 mmol) of 4 '-(1-methylheptyloxy) -4- {4- (1-decanoyloxyethyl). ) Phenoxymethyl dibiphenyl was obtained.

The obtained compound was analyzed by ¹ H-NMR spectrum analysis and I
Analysis by R spectrum analysis confirmed that it was the target compound. The measurement results of the specific rotation and the clearing point were as shown below.

Specific rotation: ▲ [α] ²⁰ _D ▼ = -36.5 ゜ (c = 1.04, CHCl
₃₎ clearing point: 49.2 ° C. (had a liquid crystal phase within a range of ^{35~40 ℃) 1 H-NMR (} 300MHz, in CDCl _3, [delta] value ppm): 0.86 (m, 6H ), 1.15-1.82 ( m, 27H), 2.29 (t, 2
H), 4.38 (m, 1H), 5.07 (s, 2H), 5.84 (q, 1H), 6.9
4 (d, 2H), 6.96 (d, 2H), 7.29 (d, 2H), 7.46 (d, 2
H), 7.48 (d, 2H), 7.55 (d, 2H) IR (KBr, cm ^-1 ): 3032, 2954, 2920, 2850, 1898, 1728, 1608, 1581,
1516, 1500, 1465, 1419, 1342, 1292, 1249, 1215, 11
76, 1118, 1041, 1026, 937, 875, 829, 775, 721 [Effect 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 the production method of the present invention. According to the method, the optically active compound can be easily produced.

Continued on the front page (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 43/23 C07C 69/025 C12P 41/00 REGISTRY (STN) CA (STN)

Claims (4)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, R ¹ is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, X ¹ , X ² and X ³ are each a hydrogen atom, a halogen atom or a cyano group, and X ¹ , X ² and X ³ Need not be the same). 2. The general formula (II): (Wherein, R ¹ is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, R ² is an alkyl group having 1 to 15 carbon atoms, X ¹ , X ² and X ³ are each a hydrogen atom, a halogen atom or a cyano group. And X ¹ , X ² and X ³ need not be the same). 3. An organic solvent comprising a compound represented by the general formula (III): (Wherein, R ¹ is an alkyl group or alkyloxy group having 1 to 15 carbon atoms, X ¹ , X ² and X ³ are each a hydrogen atom, a halogen atom or a cyano group, and X ¹ , X ² and X ³ Need not be the same).
A lipase is allowed to act on a fatty acid ester of 2,2,2-trichloroethanol (fatty acid having 2 to 16 carbon atoms), and only the (R) form of racemic alcohol is selectively converted into an ester compound. A method for producing an optically active compound, which is separated from body alcohol. 4. The method of claim 1, wherein said lipase is Pseudomonas (Pseudomonas).
nas) or Achromobacterium
4. The method according to claim 3, wherein the enzyme is an enzyme produced from a microorganism belonging to the genus ium) or an enzyme produced from an animal gut.