JPH02275864A - Optically active alcohols and its production - Google Patents

Abstract

NEW MATERIAL:Optically active alcohols expressed by formula I (R1 is 1 to 20C alkyl; Y is O, COO or OCO; Ar is formula II, formula III, formula IV or formula V; (n) is 0 to 5; (m) is 0 or 1; * is asymmetric carbon). EXAMPLE:(-)-2-[4-(3-Hydroxybutyl)phenyl]-5-decyloxypyrimidine. USE:An intermediate for agricultural chemical, medicine and organic electron material, especially ferroelectric liquid material capable of providing ferroelectric liquid product in low temperature area. PREPARATION:Esters expressed by formula VII obtained by hydrogenating unsaturated esters expressed by VI (R' is lower alkyl) using H2 and hydrogenating catalyst is subjected to asymmetric hydrolysis using an esterase of Pseudomonas lipase capable of hydrolyzing either one among the esters in a buffer (pH5 to 8) such as phosphoric acid buffer and inert organic solvent such as chloroform to industrially and provide the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to optically active alcohols useful as intermediates for agricultural chemicals, medicines, organic electronic (especially ferroelectric liquid crystal) materials, and the like.

<Prior art> Although mild compounds have been developed as liquid crystal materials, there are very few compounds that have excellent characteristics such as high-speed response and can become ferroelectric liquid crystal materials at low temperatures. Since the development of intermediates is still insufficient, there has been a desire for intermediates and industrially advantageous production methods thereof.

<Problems to be Solved by the Invention> The present invention particularly relates to novel optically active alcohols that become ferroelectric liquid crystals in a low temperature range and are useful as intermediates for ferroelectric liquid crystal materials having excellent properties as described above; A manufacturing method is provided.

Here, the above-mentioned ferroelectric liquid crystal material can be synthesized by the following steps.

(In the formula, R1 represents an alkyl group having 1 to 20 carbon atoms, and Y
is -o--coo- or -0CO-n is an integer of 0 to 6, and m is 0 or 1. R1 is 1 to 20 alkyl group or alkoxyalkyl group, 8 is 0 or l
shows. * indicates an asymmetric carbon atom) Means for Solving the Problems> The present invention is based on the general formula (1) % formula % () (wherein R1 represents an alkyl group having 1 to 20 carbon atoms, Y
represents -o--coo- or -0CO-.

n is an integer from 0 to 5, and m is O or 1. *marks are asymmetric carbon atoms. ) Optically active alcohols shown in the following and methods for producing the same.

The present invention will be explained in detail below.

The optically active alcohol (I) represented by has the general formula (Tf
') Hs (In the formula, R represents a lower alkyl group. R1, Y.

Ar%m and n represent the same meanings as above. ) can be produced by asymmetric hydrolysis using an esterase capable of hydrolyzing either one of the optically active forms of esters.

In addition, esterase in the present invention means esterase in a broad sense including lipase.

The microorganism that produces esterase used in this reaction may be any microorganism that produces esterase that has the ability to asymmetrically hydrolyze esters (but is not particularly limited).

Specific examples of such microorganisms include Enterobacter, Arthrobacter, Brevibacterium, Pseudomonas, alkaline earth metals, Micrococcus, Chromobacterium, Crobacterium, Corynebacterium, etc. Genus, Bacillus, Lactobacillus metall, Trichoderma, Candida, Satucharomyces, Rhodotorula, Cryptococcus, Torulopsis, Pichia, Penicillium, Aspergillus, Rhizopus, Mucor, Aureopacidium, Examples include microorganisms belonging to the genus Actinomycosis, genus Nocardia, genus Streptomyces, genus Hansenula, and genus Achromobacter.

The above-mentioned microorganisms are usually cultured according to conventional methods, and a culture solution can be obtained by performing liquid culture.

For example, sterilized liquid medium [malt extract/yeast extract medium for frequent use of mold and yeast (dissolve 8 g of hepton 61, glucose top, malt extract 8y1 and yeast extract in 1j of water and adjust the pH to 6.5), and for bacteria. For sweetened bouillon medium (glucose 10F, peptone 62, meat extract x sys NaCjBy dissolved in water 11, pH 7.2
shall be. )] and inoculated with microorganisms, usually at 20-40℃.
This is carried out by performing reciprocating shaking culture for up to 8 days, and solid culture may be performed if necessary.

Furthermore, some of these microbial-derived esterases are commercially available and can be easily obtained. Specific examples of commercially available esterases include the following.

Lipase of the genus Pseudomonas [Lipase P (manufactured by Ohno Pharmaceutical)], lipase of the genus Aspergillus [Lipase AP (manufactured by Ohno Pharmaceutical)], lipase of the genus Mucor (Lipase M-A)
P (manufactured by Ohno Pharmaceutical Co., Ltd.)], Candida cylindrasse lipase [Lipase MY (Meito Sangyo *)], alkaline earth metal lipase [Lipase PL (Meito Sangyo Co., Ltd.)], Achromobacter lipase [Lipase AL] (Meito Sangyo Co., Ltd.)], ] Arthrobacter lipase [Lipase Godo BSL (Godo Sake Refining Co., Ltd.)], Chromobacterium lipase (Toyo Jojo Co., Ltd.), Rhizopus delemer lipase [Talipase (Tanabe Seiyaku Co., Ltd.)] , Rhizopus lipase [Lipase Saiken (Osaka Bacteria Research Institute)].

Further, animal/plant esterases can also be used, and specific examples of these esterases include the following.

Steapsin, pancreatin, porcine liver esterase, Wheat Germ esterase.

As the esterase used in this reaction, enzymes obtained from animals, plants, and microorganisms are used, and their usage forms include purified enzymes, crude enzymes, enzyme-containing substances, microbial culture fluids, cultures, bacterial cells, and culture microorganisms. They can be used as needed in various forms such as and processed products, and enzymes and microorganisms can also be used in combination. Or again,
It can also be used as an immobilized enzyme immobilized on a resin or the like, or as an immobilized bacterial cell.

The asymmetric hydrolysis reaction is usually carried out by vigorously stirring a mixture of the raw material ester (TI) and the enzyme or microorganism in a buffer solution.

Buffers include commonly used buffers of inorganic acid salts such as sodium phosphate and potassium phosphate, sodium acetate,
A buffer solution of organic acid salts such as sodium citrate is used, and its pH is 8 to 11 for culture solutions of alkalophilic bacteria and alkaline esterases, and pH 8 to 11 for culture solutions of microorganisms that are not alkalophilic and esterases that do not have alkali tolerance. pH 6-8 is preferred. The concentration is usually 0.05-2M,
Preferably it is in the range of 0.06-0.5M.

The reaction temperature is generally 10 to 60°C, and the reaction time is generally 10 to 70 hours, but is not limited thereto.

Note that when a lipase belonging to the genus Pseudomonas or Arthrobacter is used as the lipase in this asymmetric hydrolysis reaction, optically active alcohol (1) with relatively high optical purity can be obtained.

Furthermore, during this asymmetric hydrolysis reaction, in addition to a buffer solution, it is also possible to use an organic solvent inert to the reaction, such as toluene, chloroform, methyl isobutyl ketone, or dichloromethane. Hydrolysis can advantageously be carried out.

Through this asymmetric hydrolysis reaction, only one of the raw material esters (optically active odors) is hydrolyzed to produce optically active alcohols represented by the general formula (1), while the raw material The esters (optically active esters, which are the other optically active forms of the esters) remain as they are as hydrolyzed residues.

After completion of such hydrolysis reaction, the hydrolysis reaction solution is extracted with a solvent such as methyl isobutyl ketone, ethyl acetate, ethyl ether, etc., the solvent is distilled off from the organic layer, and the concentrated residue is treated with column chromatography. Optically active alcohols (I), which are hydrolysis products, and optically active esters, which are hydrolysis residues [raw material esters (those that were not hydrolyzed among the optically active substances in Xunzhong)] can be separated.

The optically active esters obtained in ξ are further hydrolyzed as necessary to obtain optically active alcohols that are enantiomers of the previously obtained optically active alcohols.

Esters (n), which are raw material compounds, have the general formula (IO(
In the formula, R1%Y%Ar%m and n represent the same meanings as above. ) can be produced by reacting an alcohol represented by formula (5)% with a carboxylic acid represented by formula (5) (wherein R represents the same meaning as above) or a derivative thereof. can.

In such an acylation reaction, lower alkyl carboxylic acids (i.e., the above carboxylic acid (2)) are used as acylating agents.
The acid anhydride or acid halide of a lower alkylcarboxylic acid (or its derivative) is usually used, such as acetic anhydride, propionic anhydride, acetic acid chloride or bromide, propionic acid chloride or bromide,
Examples include butyryl chloride or bromide, valeroyl chloride or bromide, and the like.

The reaction between the alcohol (Ill) and the lower alkyl carboxylic acid is carried out under normal esterification conditions using a catalyst in the presence or absence of a solvent.

In this reaction, when a solvent is used, the solvent may be a t-aliphatic group such as tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, hexane, etc. Alternatively, solvents inert to the reaction such as aromatic hydrocarbons, ethers, ketones, halogenated hydrocarbons, and aprotic polar solvents may be used alone or in mixtures. The amount used can be used without any particular restriction.

The lower alkylcarboxylic acids used in the above reaction are required in an amount of 1 equivalent or more based on the raw material alcohol (4),
The upper limit is not particularly limited, but is preferably 4 equivalents.

Examples of the catalyst used in the above reaction include organic or inorganic basic substances such as dimethylaminoviridine, triethylamine, tri-n-butylaminol, pyridine, picoline, imidazole, sodium carbonate, sodium methylate, and potassium bicarbonate. The amount used is not particularly limited, but it is usually 1 to 5
It is equivalent.

In addition, when an organic amine is used as a solvent, the main amine acts as a catalyst.

Furthermore, acids such as toluenesulfonic acid, methanesulfonic acid, and sulfuric acid can also be used as catalysts.

The amount of catalyst used varies depending on the type of lower alkyl carboxylic acid and the combination of catalyst used, and cannot necessarily be specified, but for example, when using an acid halide as the lower alkyl carboxylic acid, 1 More than equivalent amount is used.

The reaction temperature is usually -80 to 100°C, preferably -20 to 90°C.

The reaction time is not particularly limited, and the raw material alcohol (6)
The end point of the reaction can be defined as the point at which .

After the reaction is completed, esters (Ir) can be obtained in good yield by conventional separation methods such as extraction, separation, concentration, and recrystallization, which can be purified by column chromatography or the like if necessary. However, the reaction mixture can also be used as is for the next step.

The above alcohol (4) has the general formula CV) (wherein, RI
Y%Ar, m and n have the same meanings as above.

) can be easily obtained by reducing the ketones represented by the following using a reducing agent.

Suitable reducing agents in this reaction include sodium borohydride, zinc borohydride, aluminum isopropoxide, lithium-tri-t-butoxyaluminum hydride, lithium-tri-S-butylborohydride, borane, lithium aluminum hydride. Compound-silica gel, alkali metal-ammonia, Raney nickel-hydrogen, etc. are used, and the amount used is at least 1 equivalent or more relative to the raw material ketones (V), and is usually in the range of 1 to 10 equivalents.

This reaction is usually carried out in a solvent, such as
For example, solvents inert to the reaction such as tetrahydrofuran, dioxane, ethyl ether, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, toluene, benzene, chloroform, ethers such as dichloromethane, halogenated hydrocarbons, and alcohols may be used alone or in mixtures. used.

The reaction temperature of the above reaction is usually in the range of -80 to 100°C, preferably in the range of -20 to 90°C.

From the reaction mixture thus obtained, liquid separation, concentration,
By operations such as distillation and crystallization, the alcohols (ff
1) can be obtained in good yield, but in order to obtain esters (II) in the next step, alcohols (II
It is not necessary to isolate I), and the reaction mixture may proceed to the next step as it is.

In the case of ketones (■ is n ” O or 1), which are raw materials, the method described in the literature (Orga Reaction
s Vol.

27.845-890), n -2-
In the case of 5, Heck (Heck) as shown in the reaction below
) can be synthesized by the following method.

Ha R1-(Y)m-Ar-X + CH2-CH(CH
2) ,,'-,CHOH (In the formula, R1, Y%Ar and m represent the same meanings as above, X represents a bromine atom or an iodine atom, and n represents an integer of 2 to 5.) Further optical Active alcohols (n-2~
Compound No. 5 can also be produced by the method shown below. In other words, the general formula (b)? H8 Rt-(Y)m, -Ar-CH-CH-(CH2)n"
2CHOHCVD (wherein, R1, Y, Ar%m, n
and *marks have the same meanings as above. ) Compounds with nm 2 to 5 in the general formula (R) can also be produced by hydrogenating optically active unsaturated alcohols represented by the following using hydrogen and a hydrogenation catalyst.

In the above reaction, a Raney nickel palladium metal catalyst is preferably used as the hydrogenation catalyst, and specific examples thereof include palladium-carbon, palladium oxide, palladium black, and palladium chloride. .

Such a hydrogenation catalyst is usually used in an amount of 0.001 to 0.6 times by weight, preferably 0.005 to 0.8 times by weight, based on the optically active unsaturated alcohol (b). The reaction is carried out in a solvent, such as water, a hydrocarbon such as dioxane, tetrahydrofuran, methanol, ethanol, n-propyl alcohol, acetone, dimethylformamide, toluene, dichloromethane or ethyl acetate,
Solvents inert to the reaction, such as alcohols, ethers, ketones, esters, halogenated hydrocarbons or amides, may be used alone or in mixtures.

The above reaction is carried out under normal or increased hydrogen pressure, and the amount of hydrogen absorbed is determined by the optically active unsaturated alcohol used as the raw material (
It is preferable to set the reaction end point at the time when the amount becomes 1 to 1.2 times the amount of

The reaction is carried out at -10 to 100°C, preferably at 10 to 60°C.

After the reaction is completed, the catalyst is removed from the reaction mixture by filtration, etc., and then concentrated, etc., to obtain the target optically active alcohol (I) with n-2 to n-5 compounds, which are necessary. Purification can also be carried out by recrystallization, column chromatography, etc., depending on the situation.

The optically active unsaturated alcohol (b) which is a raw material compound in the above reaction has the general formula (■) Hs (where R1, Y, Ar, m% n' and R' have the same meanings as above). ) can be produced by asymmetric hydrolysis using an esterase capable of hydrolyzing either one of the optically active forms of unsaturated esters shown in
This reaction can be carried out in the same manner as the method for producing the optically active alcohol (1) from the esters described above.

In addition, unsaturated esters (
(2) is hydrogenated according to the hydrogenation reaction and reaction conditions used for optically active unsaturated alcohols (10) to obtain
Compounds of ~5 can also be obtained. Optically active esters (II) thus obtained [n-2 to 6]
is led to optically active alcohol (I) (n-2-5) by an asymmetric hydrolysis reaction.

Finally, the unsaturated esters (■) are combined with a halide represented by the general formula % (wherein, R1, Y%Ar%X' and m have the same meanings as above) and the general formula (IX ) Hs (wherein R and n have the same meanings as above) are reacted with a metal catalyst in the presence of a basic substance.

Note that the raw material compounds represented by the general formulas (■) and (IX,) can be easily produced using commercially available products or from commercially available products.

In the above reaction, the amount of olefin 1) used is usually 0.9 to 10 times the equivalent of the halide (Ml), but preferably 1 to 2 times the equivalent.

Metal catalysts include palladium chloride, palladium chloride,
Palladium acetate, triphenylphosphine palladium complex, palladium/carbon, etc. are used, and the same catalysts as the above-mentioned palladium-based catalysts are also used for nickel-based and rhodium-based catalysts.

The amount of these metal catalysts used is based on the raw material halide (■)
It is in the range of 10 to 10 times the equivalent amount. In addition to the above-mentioned metal catalyst, this reaction requires an octavalent phosphorus compound or an octavalent arsenic compound as a cocatalyst. , Y represents a phosphorus atom or an arsenic atom, R2, R
8 and R4 are the same or different and represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom. ) Specific examples include tri-n-butylphosphine, triphenylphosphine, trirotolylphosphine, trio-tolylphosphite, phosphorus trichloride, triphenylarsenic, and the like.

The amount of these phosphorus compounds or arsenic compounds used is 0.5 to 50 times the amount of the above metal catalyst! 1, preferably 10 to 80 times equivalent.

Examples of basic substances include alkali metal carbonates, carboxylates, alkoxides, hydroxides, etc., and organic bases, but 8th-class amines or secondary amines (organic bases) are preferably used, and these include triethylamine. ,
Examples include di-isopropylethylamine, tri-n-butylamine, tetramethylethylenediamine, and dimethylaniline.

The amount of base used is usually 1% per halide (■).
~6 times equivalent.

If necessary, a suitable solvent such as acetonitrile, tetrahydrofuran, dimethylformamide, hexamethylphosphorylamide, N-methylpyrrolidone, methanol, etc. can also be used as a reaction solvent.

The amount of these reaction solvents used is not particularly limited.

Incidentally, the above reaction is usually carried out in an inert gas such as nitrogen or argon.

In this reaction, the yield of the target unsaturated ester can be improved by increasing the reaction temperature, but if the temperature is too high, by-products will increase, so the reaction temperature is usually 15 to 190 ° C. Preferably 100-150
It is ℃.

After the reaction is completed, unsaturated esters (■) can be obtained by conventional means such as extraction, distillation, recrystallization, etc.

Examples of compounds represented by the general formula (RI) obtained through the above steps are shown below.

6-alkyl-2-(1-hydroxyethyl)phenylpyrimidine, 6-alkyloxy-2-(1-hydroxyethyl)phenylpyrimidine, 5-alkylcarbonyloxy-2-(1-hydroxyethyl)phenylpyridine, 5-alkyloxycarbonyl-2-(1-hydroxyethyl)phenylpyrimidine, 2-alkylphenyl-5-(1-hydroxyethyl)pyrimidine, 2-alkyloxyphenyl-5-(1-hydroxyethyl)pyrimidine, 2- Alkylcarbonyloxyphenyl-5-(1-hydroxyethyl)pyrimidine, 2-alkyloxycarbonylphenyl-6-(1-hydroxyethyl)pyrimidine, 2-alkyl-5-(1- and droxyethyl)phenylpyrimidine, 2-alkyl Oxy-5-(1-hydroxyethyl)phenylpyrimidine, 2-alkylcarbonyloxy-5-(1-hydroxyethyl)phenylpyrimidine, 2-alkyloxycarbonyl-6-(1- and droxyethyl)phenylpyrimidine and substituents (1-hydroxyethyl) group is 2-hydroxypropyl, 8-hydroxybutyl, 4-hydroxypentyl, 5-hydroxyhexyl, 6-hydroxyhebutyl, 8-hydroxy-1-butenyl, 4-hydroxy-1-pentenyl, A compound that replaces either 5-hydroxy-1-hexenyl or 6-hydroxy-1-heptenyl.

Here, the alkyl in the compound name indicates an alkyl group having 1 to 20 carbon atoms.

<Effects of the Invention> The compound of the present invention is not only useful as an intermediate for liquid crystal materials, but also can be used as an intermediate for agricultural chemicals, medicines, and the like.

Further, according to the method of the present invention, optically active alcohols represented by general formula (I) can be produced industrially advantageously.

<Example> The present invention will be explained below with reference to Examples.

Example 1 2-(
4-acetylphenyl)-5-decyloxypyrimidine 85.5y (0.1 mol), ethanol 800- and chloroform 800- were charged, and at 80 to 40°C, sodium borohydride 2.87 (0,075 mol) was added. was added and stirred at the same temperature for 4 hours. After the reaction is complete, the reaction mixture is diluted with 5 liters of water.
After pouring into 0.0-ml, extraction, and liquid separation, the obtained chloroform layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 2-(4-(1- and droxyethyl)phenyl). -6-decyloxypyrimidine 85.8y
(1-1) (yield 100%) was obtained.

Here, a large amount of Cm-1)82y (0.09 mol) is mixed with toluene soomt and pyridine 100. 12.29 (0.12 mol) of acetic anhydride at 4°C.
Time stirring.

After the reaction was completed, the reaction mixture was poured into 500ml of water, and after separation, the toluene layer was diluted with 2-(4
-(1-acetoxyethyl)phenyl)-5-decyloxypyrimidine (n-1) 85.8y (yield 99.6%)
) was obtained.

The (n-i) 81.9y (0.08 mol) obtained here was added to 0.8M phosphate buffer (pH 7.0) at 500%.
The mixture was added to a mixture of 20-z, chloroform and 8.2y of Pseudomonas lipase (Lipase "P", Amano) and stirred vigorously at 86-88°C for 20 hours.

The resulting mixture was extracted with 400 J of methyl isobutyl ketone, and the organic layer was washed with water and then concentrated under reduced pressure.

The resulting residue was subjected to silica gel column chromatography (
Elute! 14.0
2 (yield 49%l (dl D-"+26.0'(c-
1, rioo form), mp, 65-66°C) and (
-)-2-(4-(1-acetoxyethyl)phenyl)
-6-decyloxypyrimidine 16.1y (yield 5ON
, (α)''--71,5 (C-1°chloroform), m
p, 42-48°C).

In addition, (c)-(4-(1-acetoxyethyl)phenyl)-5-decyloxypyrimidine 4 obtained above was dissolved in methanol (50 mm) and 20X sodium hydroxide solution (10 mm) and heated to 80°C for 2 hours. Stir for hours to perform hydrolysis, and add 200% water to the reaction solution. The mixture was extracted and separated by adding 200ml of toluene and 200ml of toluene.

The obtained organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 8.52 of H-(4-(1-hydroxyethyl)phenyl-1-5-decyloxypyrimidine) as a white solid. Ta.

Example 2 2-(4-acetylphenyl)-5-decylcarbonyloxypyrimidine 88.8y instead of 2-(4-acetylphenyl)-5-decyloxypyrimidine 85.5P
Reaction was carried out in the same manner as in Example 1 except that (0.1 mol) was used.
After post-treatment as an enzymatic asymmetric hydrolyzate, <+)−
2-(4-(1-and droxyethyl)phenyl)-5-
Decylcarbonyloxypyrimidine (I-2) 18y(
(α)20-+24.5° (c=1.chloroform))
I got it.

Example 8 2-(4-acetylphenyl)-5-octyloxypyrimidine 82.6F (0,1
The reaction and post-treatment were carried out in the same manner as in Example 1 except that (+)-2-(4
-(1-hydroxyethyl)phenyl-5-octyloxypyrimidine (I 8 ) 12.59 (('
) Suga = + 26.9 (c -1.

(Chloroform) 1 was obtained.

Example 4 2-(
4-Bromophenyl)-5-decyloxypyrimidine 7
．． 8y (0.02 mol), 8.4y (0.08 mol) of 2-7cetoxy-8-butene, 5y of sodium bicarbonate and 10- of N-methylpyrrolidone, and 0.16f of triphenylphosphine in a nitrogen atmosphere. 0.06 P of palladium acetate was added, and the mixture was heated and stirred at 110 to 120°C for 20 hours.

After the reaction was completed, the reaction mixture was poured into 200ml of water and extracted with 200ml of toluene. The obtained toluene layer was washed with water and then concentrated under reduced pressure to obtain a blackish brown residue.

This was purified by silica gel column chromatography (
Eluent: toluene-ethyl acetate) and 2-(4-(8
-acetoxy-1-butenyl)phenyl)-5-decyloxypyrimidine (■-4) 8.6F (yield: 42) was obtained.

Obtained here (■-4)2. IP (5 mmol) 0,8
86-8 in addition to a mixture of 50 mt of M phosphate buffer y-(pH 7,0), 5-chloroform, and 0.5 y of Pseudomonas lipase (Lipase rPJ Amano).
The mixture was stirred vigorously at 8° C. for 80 hours.

The resulting mixture was extracted with 200 g of toluene, and the organic layer was washed with water and then concentrated under reduced pressure.

The resulting residue was subjected to silica gel column chromatography (
Eluent: toluene-ethyl acetate) to separate θ-2-(4
-(8-hydroxy-1-butenyl)phenyl)-5-
Decyloxypyrimidine (Vl-4) 0.949 (
Yield 49 .06F (yield 60X), (a) D--x
O,1° (C-1, chloroform) was obtained.

0.88P (it remole) of (W-4) obtained here was dissolved in 20-tetrahydrofuran and 10% P b/Co,
o5y was added, and a hydrogenation reaction was carried out under a hydrogen atmosphere at normal pressure. The reaction was stopped when about 25-hydrogen was consumed, and after separating with 10% Prl/C1eP, the furnace liquid was concentrated to give (c)-2-(4-(8-hydroxybutyl)phenyl)-5- Decyloxypyrimidine (1-4) 0.8
8 F (Yield t 00X, ((1), -5.6°
(C-1, chloroform)) was obtained.

Example 5 2-(
4-bromophenyl)-5-octyloxypyrimidine 7.85' (0.02 mol), 2-acetoxy-8-butene 8.4y (0.08 mol), tri-n-butylamine 52 and N-methylpyrrolidone 10 - was charged, 0.169 y of triphenylphosphine and 0.06 y of palladium acetate were added in a nitrogen atmosphere, and the mixture was heated and stirred at 120°C for 26 hours.

After the reaction was completed, the reaction mixture was poured into 200 mj of water, and 200 mj of toluene was added. , lj. The obtained toluene layer was washed with water and then concentrated under reduced pressure to obtain a blackish brown residue.

This was purified using silica gel column chromatography! !
! (Eluate: toluene-ethyl acetate) and 2-(4-
(8-acetoxy-!-butenyl)phenyl 1-5-octyloxypyrimidine (■-5)4. (1 (yield 51
%) was obtained.

The (■-5) 8.969 (10 mmol) obtained here was dissolved in tetrahydrofuran 80- and 5% Pd/G
O05y was added and a hydrogenation reaction was carried out under a hydrogen atmosphere. The reaction was stopped when approximately 280 rnl of hydrogen was consumed, and after removing 10% Pd/C from P, the furnace liquid was concentrated to produce 2-(4-(8-acetoxybutyl)phenyl)-5
-Octyloxypyrimidine ('-5) 8.97F (yield 100) was obtained.

Obtained here (II 5) 2. OF (5°C remol) in 0.8 M phosphate buffer (pH 7.0) 50J
, 6rnl of chloroform and 0.57ml of Arthrobacter lipase and stirred vigorously at 88-1118°C for 80 hours.

The resulting mixture was extracted with 200 g of toluene, and the organic layer was washed with water and then concentrated under reduced pressure.

The resulting residue was subjected to silica gel column chromatography (
Eluent: Separated with toluene-ethyl acetate), ←)-2-
(4-(8-hydroxybutyl)phenyl)-6-octyloxypyrimidine (I-5>0.86 PC yield 4
s OIy (yield 50%, [α]o−5.2°(c
ml, chloroform)) was obtained.

Example 6 2-(4-(8-ketobutyl)phenyl)-5-dodecyloxypyrimidine 41.05'(0
, 1 mol) was used, and the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain the enzymatic asymmetric hydrolyzate, ←)-2-(
4-(8-hydroxy-1-butyl)phenyl)-5-
Dodecyloxypyrimidine (1-6) ((m), -5,
1°C-1°chloroform)) was obtained.

Examples 7 to 22 Reactions and post-treatments were carried out in the same manner as in Example 4 except that the starting materials shown in Table 1 were used, and the optically active unsaturated alcohols (b) shown in Table 1 and the optical Active alcohols (I) were obtained.

Reference Example 1 H-2-(4-(8-hydroxybutyl)phenyl)-5-decyloxypyrimidine (1-4) obtained in Example 4
0.11 was dissolved in 5-butyl iodide, 8 parts of silver oxide was added thereto, and the mixture was stirred at 25-80°C for 4 days. After the reaction is complete, i
After removing silver oxide through p-filtration, the resulting residue was purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to give (he)-2-(4-(8-butoxybutyl) ) Phenyl)-5-decyloxypyrimidine 0.989 was obtained.

This compound was found to be a ferroelectric liquid crystal compound from observation results using a polarizing microscope and DSC.

Claims (10)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms,
Y represents -O-, -COO- or -OCO-, Ar
indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n is 0 to is an integer of 5, and m is 0 or 1. * indicates an asymmetric carbon atom. ) optically active alcohols. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms,
R' represents a lower alkyl group, Y is -O-, -COO-
or -OCO-, Ar is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas, chemical formulas, tables, etc. indicates ▼, n is an integer from 0 to 5, and m is 0 or 1. ) The production of optically active alcohols according to claim 1, characterized in that the asymmetric hydrolysis is carried out using an esterase having the ability to hydrolyze any one of the optically active forms of esters represented by Method. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms,
Y represents -O-, -COO- or -OCO-, Ar
indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n is 0. It is an integer of ~5, and m is 0 or 1. ) The optically active compound according to claim 2, wherein esters are obtained by reacting an alcohol represented by the formula R'COOH with a carboxylic acid represented by the general formula R'COOH (in the formula, R' represents a lower alkyl group) or a derivative thereof. A method for producing alcoholic beverages. (4) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms,
Y represents -O-, -COO- or -OCO-, Ar
is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. n is an integer from 0 to 5, and m is 0 or 1. 4. The method for producing optically active alcohols according to claim 3, wherein the alcohols are obtained by reducing the ketones represented by: (5) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms,
Y represents -O-, -COO- or -OCO-, Ar
indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n' is It is an integer from 2 to 5, and m is 0 or 1. * indicates an asymmetric carbon atom. ) is characterized by hydrogenating the optically active unsaturated alcohols shown in the following using hydrogen and a hydrogenation catalyst. A method for producing optically active alcohols represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, Y, Ar, m, n' and * have the same meanings as above.) (6) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms,
R' represents a lower alkyl group, Y is -O-, -COO-
or -OCO-, Ar is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, n' is an integer from 2 to 5, and m is 0 or 1. ) The optically active unsaturated alcohol is obtained by asymmetric hydrolysis using an esterase having the ability to hydrolyze any one of the optically active forms of the unsaturated esters shown in A method for producing optically active alcohols. (7) General formula R_1-(Y)_m-Ar-X (wherein R_1 represents an alkyl group having 1 to 20 carbon atoms,
Y represents -O-, -COO- or -OCO-, Ar
indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X is bromine Indicates an atom or an iodine atom. ) and olefins represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 7. The method for producing optically active alcohols according to claim 6, wherein unsaturated esters are obtained by conducting a Heck reaction in the presence of a palladium catalyst and a basic substance. (8) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms,
R represents a lower alkyl group, Y represents -O-, -COO-, or -OCO-, and Ar represents ▲Mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, Chemical formulas, tables, etc. are available ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ where n' is an integer from 2 to 5, and m is 0 or 1. ) Unsaturated esters represented by are hydrogenated using hydrogen and a hydrogenation catalyst to obtain esters represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the optically active form of the esters is obtained. General formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, Y, Ar, m and n represents the same meaning as above, * mark represents an asymmetric carbon atom.) A method for producing an optically active alcohol. (9) General formula R_1-(Y)_m-Ar-X (wherein, R_1 represents an alkyl group having 1 to 20 carbon atoms,
Y represents -O-, -COO- or -OCO-, Ar
indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X is bromine Indicates an atom or an iodine atom. ) and olefins represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 9. The method for producing optically active alcohols according to claim 8, wherein unsaturated esters are obtained by reacting with a metal catalyst in the presence of a basic substance. (10) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms,
Y represents -O-, -COO- or -OCO-, Ar
There are ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where n is an integer from 2 to 5, and m is 0 or 1. * indicates an asymmetric carbon atom. ) Optically active unsaturated alcohols.