JPH09249984A - Production of optically active epoxide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optically active epoxide deriv. of high purity at high yield by electrolyzing an olefin compd. in a two-layer liquid of an org. solvent and a halide on the presence of an optically active manganese catalyst. SOLUTION: An olefin compd. expressed by formula I is electrolyzed in a two-layer system of an org. solvent and a halogenated compound aqueous soln. in the presence of an optically active manganese catalyst expressed by formula II so as to obtain an optically active epoxide deriv. expressed by formula III. In formula I, R<1> to R<4> are hydrogen atom or alkyl, alkenyl groups or the like which may have substitutents. In formula II, R<5> and R<8> form a cycloalkane having 5 to 8 carbon atoms, and R<6> and R<7> are hydrogen atoms, etc. In formula III, R<14> to R<17> are the same as R<1> to R<4> in formula I. Thereby, an optically active epoxide deriv. can be produced without using a large amt. of a hazardous oxidizing agent or without producing a large amt. of wastes.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION Optically active epoxide derivatives are described, for example, in Tetrahedron, 50, 8885 (199).
As described in 4), it is a compound that is useful in organic synthesis and is important for the production of physiologically active substances and functional materials.
For example, the introduction of asymmetric carbon is essential in the production of ferroelectric liquid crystals, and optically active epoxide is an important raw material. The present invention relates to an optically active epoxide derivative useful for these organic syntheses, and a method for producing an optically active epoxide derivative which is important for physiologically active substances and functional materials.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an optically active epoxide derivative represented by the general formula (III), J. Am.
Chem. Soc., 102, 5974 (1980), an olefin compound represented by the general formula (IV), that is, an allyl alcohol derivative is reacted with tert-butyl hydroperoxide in the presence of a titanium catalyst and optically active tartaric acid. A so-called Sharpless asymmetric epoxidation reaction, and, for example, International Patent Publication WO93 / 0383.
As described in 8, the general formula (I) (in the formula, R ¹ , R ² , R ³ , R
⁴ is the same as above. ) The olefin compound represented by
General formula (II) (in the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ and Y are as defined above. ), A method of reacting an oxidizing agent (iodosylbenzene, m-chloroperbenzoic acid, etc.) in the presence of an optically active manganese catalyst is reported.

[0003]

Embedded image (In the formula, R ¹ , R ² and R ³ are the same as above.)

Since these methods require the use of large amounts of oxidants, they must deal with large amounts of hazardous oxidant storage and large amounts of waste after reaction, which overcome these drawbacks. Development of a more practical manufacturing method is desired.

[0005]

The object of the present invention is to provide a method capable of producing the desired optically active epoxide derivative with high yield and high purity by overcoming the drawbacks found in the above-mentioned conventional production methods. Especially.

[0006]

The present invention has the general formula (I)
The olefin compound represented by the formula (II) is electrolyzed in the presence of the optically active manganese catalyst represented by the general formula (II) in a two-layer system of an organic solvent and an aqueous solution of a halide to give an optically active epoxide represented by the general formula (III). The present invention relates to a method for producing an optically active epoxide derivative, which comprises obtaining the derivative.

[0007]

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom and may have a substituent, an alkyl group, an alkenyl group, an alkynyl group, an aromatic compound residue, a heteroaromatic compound residue, (Alkoxy group, acyl group, optionally protected hydroxyl group, amino group, carboxyl group, halogen atom, nitro group, cyano group.)

[0008]

[Chemical 6] (Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ together form a C ₅ -C ₈ cycloalkane with R ⁵ and R ⁸ and R ⁶ and R ⁷ are hydrogen atoms, or R ⁶ and R ⁷ To form a C ₅ -C ₈ cycloalkane and R ⁵ and R ⁸ are hydrogen atoms, or R ⁵ and R ⁸ are aryl groups and R ⁶ and R ⁷ are hydrogen atoms, or R ⁶ and R ^{7 are} .R ^9, R ^10, R but representing a and R ⁵ and R ⁸ are hydrogen atoms with an aryl group
¹¹ , R ¹² and R ¹³ are each a hydrogen atom, an optionally substituted alkyl group, an aromatic compound residue, an alkoxy group, an acyl group, a hydroxyl group optionally having a protective group,
Amino group, carboxyl group, halogen atom, nitro group,
A cyano group is shown. Y represents an anion. )

[0009]

Embedded image (In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic compound residue, a heteroaromatic compound residue, which may have a substituent, (Alkoxy group, acyl group, optionally protected hydroxyl group, amino group, carboxyl group, halogen atom, nitro group, cyano group.)

The inventors of the present invention focused on an indirect electrolytic oxidation reaction using a halide as a mediator in providing a general-purpose production method capable of producing an optically active epoxide derivative. That is, as an oxidant for recycling the optically active oxomanganese complex, which is considered to be an oxidatively active species for the asymmetric epoxidation reaction, the oxidative activity produced by electrolytically oxidizing an aqueous halide solution that is readily available and does not pose a risk A halogen species was used. At this time, if the halogen active species reacts directly with the olefin compound, the yield and the enantiomeric excess rate will decrease. Enantiomeric excess is the difference in the ratio of both enantiomers,
Usually, the ratio is expressed as a percentage of the total amount of both antipodes, and the difference is expressed as%. Therefore, a low enantiomeric excess ratio results in the production of an undesired stereoisomer (optical isomer), resulting in a low yield of the desired compound. Therefore, as a result of extensive studies on various electrolytic oxidation reactions, we have found that the target optically active manganese catalyst is selected by selecting the counter anion of the optically active manganese catalyst in a two-layer system of an organic solvent and an aqueous halide solution. The present invention has been completed by discovering a new fact that an epoxide derivative can be obtained with high selectivity.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION More specifically, each group shown in the present specification is as follows. In the following description, unless otherwise specified, the halogen atom means an atom such as fluorine, chlorine, bromine or iodine. The lower alkyl group means, for example, a linear or branched C ₁ -C ₄ alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. To do. Further, the aryl group means, for example, phenyl, naphthyl and the like. Examples of the alkyl group represented by R ¹ , R ² , R ³ , and R ⁴ of the general formula (I) and R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ of the general formula (III) include a lower alkyl group. , A linear or branched C _{1 to} C ₂₀ alkyl group, and a cyclic alkyl chain in which R ¹ and R ³ or R ¹⁴ and R ¹⁶ are connected by a C _{3 to} C ₆ methylene chain are exemplified. it can. R ¹ , R ² of the general formula (I),
R ³ , R ⁴ , and R ¹⁴ , R ¹⁵ of the general formula (III),
Examples of the alkenyl group represented by R ¹⁶ and R ¹⁷ include linear or branched C _{1 to} C ₂₀ alkenyl groups.

As the alkynyl group represented by R ¹ , R ² , R ³ , and R ⁴ of the general formula (I) and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ of the general formula (III), a straight-chain is shown. Or branched C _{1 to} C
₂₀ alkynyl groups can be illustrated. R ¹ and R in the general formula (I)
² , R ³ , R ⁴ , and R ¹⁴ , R ¹⁵ , and R of the general formula (III)
Examples of the heteroaromatic compound residue represented by ¹⁶ and R ¹⁷ include an aromatic compound residue containing an oxygen atom, a nitrogen atom or a sulfur atom, such as furyl, pyrrolyl, thienyl, oxazolyl, thiazolyl, thiadiazolyl, tetrazolyl or pyridyl. A group can be illustrated.

Alkyl groups, alkenyl groups and alkynyl groups represented by R ¹ , R ² , R ³ and R ⁴ of the general formula (I) and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ of the general formula (III). The group, the aromatic compound residue, the heteroaromatic compound residue, the alkoxy group, the substituent which the acyl group may have, for example, an aryl group such as phenyl, naphthyl, for example, furyl, pyrrolyl, thienyl, Oxygen atom, such as oxazolyl, thiazolyl, thiadiazolyl, tetrazolyl, pyridyl,
Aromatic compound residue containing nitrogen atom, sulfur atom, for example,
Halogen substituents such as fluorine, chlorine, bromine and iodine, for example, linear or branched C ₁ -C such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy. ₄ lower alkoxy groups, for example, straight-chain or branched C ₁ -C ₅ acyloxy groups such as formyloxy, acetoxy, propionyloxy, butyryloxy, isobutyryloxy, pivaloyloxy, for example, benzoyloxy, toluoyloxy. Examples thereof include an aroyloxy group and a hydroxyl group, an amino group, a carboxyl group, a keto group, a nitro group, a cyano group, which may have a protective group. R ¹ , R ² ,
The substituted alkyl group, substituted alkenyl group and substituted alkynyl group represented by R ³ , R ⁴ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are
One or more substituents on the same or different carbons may be substituted with the same or different kinds of substituents selected from the above substituents.

The alkyl group, alkenyl group and alkynyl group represented by R ¹ , R ² , R ³ and R ⁴ of the general formula (I) and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ of the general formula (III) are A protecting group for a hydroxyl group which may be present, R ¹ , R ² , R ³ , R ⁴ of the general formula (I) and R ^{14 of} the general formula (III),
Examples of the protecting group for the hydroxyl group represented by R ¹⁵ , R ¹⁶ and R ¹⁷ include Protective Group in Organic Synthesis (Protective Group Inorganic Synthesis).
sis, Theodora W. The groups described in Chapter 2 (pp. 10 to 72) of Geene, 1981, hereinafter simply referred to as "references" can be exemplified.

The alkyl group, alkenyl group and alkynyl group represented by R ¹ , R ² , R ³ and R ⁴ of the general formula (I) and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ of the general formula (III) are An optionally protecting group for an amino group, R ¹ in the general formula (I),
R ² , R ³ , R ⁴ and R ¹⁴ , R ¹⁵ of the general formula (III),
Examples of the protecting group for the amino group represented by R ¹⁶ and R ¹⁷ include various groups described in Chapter 7 (pages 218 to 287) of the literature, phenoxyacetamide, p-methylphenoxyacetamide, p-methoxy. Phenoxyacetamide, p-chlorophenoxyacetamide, p-bromophenoxyacetamide, phenylacetamide, p-methylphenylacetamide, p-methoxyphenylacetamide, p-chlorophenylacetamide, p-bromophenylacetamide, phenylmonochloroacetamide, phenyldichloroacetamide, phenyl Hydroxyacetamide, thienylacetamide, phenylacetoxyacetamide, α-oxophenylacetamide, benzamide, p-methylbenzamide, p-methoxybenzamide p-chlorobenzamide, p-bromobenzamide, phenylglycylamide and phenylglycylamide with protected amino group, p-hydroxyphenylglycylamide and p-hydroxyphenyl with protected amino group and / or hydroxyl group Examples thereof include amides such as glycylamide and imides such as phthalimide and nitrophthalimide. Phenylglycylamide and p-
Examples of the protective group for the amino group of hydroxyphenylglycylamide include various groups described in Chapter 7 (pages 218 to 287) of the above literature. Examples of the hydroxyl-protecting group of p-hydroxyphenylglycylamido include various groups described in Chapter 2 (pages 10 to 72) of the above document.

The alkyl group, alkenyl group and alkynyl group represented by R ¹ , R ² , R ³ and R ⁴ of the general formula (I) and R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ of the general formula (III) are A protecting group for a carboxyl group which may be present, R ¹ , R ² , R ³ and R ⁴ of the general formula (I) and R ^{14 of} the general formula (III),
Examples of the protecting group for the carboxyl group represented by R ¹⁵ , R ¹⁶ and R ¹⁷ include allyl groups, benzyl groups and p-methoxy groups, in addition to various groups described in Chapter 5 (pages 152 to 192) of the literature. Examples thereof include a benzyl group, a p-nitrobenzyl group, a diphenylmethyl group, a trichloromethyl group and a tert-butyl group. R ⁵ , R ⁶ in the optically active manganese catalyst of the general formula (II), which is subjected to this electrolytic asymmetric epoxidation reaction,
R ⁷ and R ⁸ are R ⁵ and R ⁸ to form a C _{5 to} C ₈ cycloalkane, and R ⁶ and R ⁷ are hydrogen atoms, or R ⁶ and R ⁷ are C ₅
To C ₈ cycloalkane and R ⁵ and R ⁸ are hydrogen atoms, or R ⁵ and R ⁸ are aryl groups and R ⁶ and R ⁷ are hydrogen atoms, or R ⁶ and R ⁷ are aryl groups. And R ⁵ and R ⁸ represent a hydrogen atom. Here, the C _{5 to} C ₈ cycloalkane formed by R ⁵ and R ⁸ or R ⁶ and R ⁷ is
Cyclohexane is particularly preferable, and examples of the aryl group represented by R ⁵ and R ⁸ or R ⁶ and R ⁷ include a phenyl group and a naphthyl group. R ⁹ and R in the general formula (II)
Examples of the alkyl group represented by ¹⁰ , R ¹¹ , R ¹² , and R ¹³ include
Examples thereof include linear or branched C _{1 to} C ₄ lower alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Examples of the aromatic compound residue represented by R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ include phenyl and naphthyl. Examples of the alkoxy group represented by R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ include linear groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy. Alternatively, a branched C ₁ -C ₄ lower alkoxy group and the like can be exemplified. Examples of the acyl group represented by R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ include linear or branched C _{1 to} C ₅ such as formyl, acetyl, propionyl, butyryl, isobutyryl and pivaloyl. Examples thereof include an acyl group, benzoyl, and an aroyl group such as toluoyl. R ⁹ , R ¹⁰ ,
Examples of the protecting group represented by R ¹¹ , R ¹² and R ¹³ that the hydroxyl group, amino group and carboxyl group may have include the same protecting groups as those described for the compound (I).

Examples of the anion represented by Y in the compound of the general formula (II) include halide ions such as chloride, bromide and iodide, halogenate ions such as perchloric acid, formic acid, acetic acid and butyric acid. , Lower carboxylic acid ion such as valeric acid, methanesulfonic acid, hexanesulfonic acid, benzenesulfonic acid, sulfonic acid ion such as toluenesulfonic acid, phosphate ion such as hexafluorophosphate, chloride ion, Acetate ion and hexafluorophosphate ion are preferred.

The optically active manganese catalyst represented by the general formula (II) is described in, for example, J. Org. Chem., 56, 2296
(1991), Tetrahedron, Asymmetry, 2,481.
(1991) and the like, the corresponding optically active diamine derivative, the corresponding aromatic aldehyde or ketone,
And can be readily synthesized using the appropriate manganese salt. Specific examples of the compound of the general formula (II) include, for example,
(1R, 2R) -N, N'-bis (4,6-di-tert-butylsalicylidene) -1,2-cyclohexanediaminomanganese (III) chloride (IIa), (1S, 2S) -N,
N'-bis (4,6-di-tert-butylsalicylidene)-
1,2-Cyclohexanediaminomanganese (III) chloride (IIb), (1R, 2R) -N, N'-bis (4,6-di-tert-butylsalicylidene) -1,2-diphenylethylenediaminomanganese (III) chloride (IIc),
Examples include (1S, 2S) -N, N'-bis (4,6-di-tert-butylsalicylidene) -1,2-diphenylethylenediaminomanganese (III) chloride (IId). The structural formulas of the compounds (IIa) and (IId) are shown below.

[0020]

Embedded image

In this electrolytic asymmetric epoxidation reaction, an olefin compound represented by the general formula (I) and an optically active manganese catalyst represented by the general formula (II) are mixed with an organic solvent and an aqueous halide solution in a suitable electrolytic cell. It can be carried out by dissolving in a two-layer system and using an appropriate electrode and applying current. The amount of compound (II) used is 0.1 with respect to compound (I).
˜200 mol%, preferably 1 to 50 mol%. The organic solvent used in this reaction may be any one that dissolves the compounds (I) and (II) and forms a double layer with the aqueous halide solution used, and specific examples include methyl formate, ethyl formate and propyl formate. Lower alkyl esters of lower carboxylic acids such as butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone,
Methyl isobutyl ketone, ketones such as diethyl ketone, diethyl ether, ethyl propyl ether, ethyl butyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl cellosylbu, ethers such as dimethoxyethane, tetrahydrofuran,
Cyclic ethers such as dioxane and dioxolane, nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile and valeronitrile, and substituted or unsubstituted aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and anisole. , Halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, trichloroethane, dibromoethane, propylene dichloride, carbon tetrachloride and freons, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, cyclo Examples thereof include cycloalkanes such as heptane and cyclooctane. These may be used alone or as a mixture of two or more. These solvents are compounds of general formula (I) 1k
Usually about 1 to 200 L, preferably 5 to 10 per g
It is better to use about 0L.

Various chlorides and bromides can be used as the halide serving as a mediator of the present electrolytic asymmetric epoxidation reaction. For example, inorganic materials such as lithium chloride, sodium chloride, potassium chloride, calcium chloride and ammonium chloride can be used. Quaternary ammonium chloride such as chloride, tetraethylammonium chloride, tetrabutylammonium chloride, ethyltributylammonium chloride, benzyltributylammonium chloride, lithium bromide, sodium bromide, potassium bromide, calcium bromide, ammonium bromide, etc. Examples thereof include quaternary ammonium bromide such as inorganic bromide, tetraethylammonium bromide, tetrabutylammonium bromide, ethyltributylammonium bromide, and benzyltributylammonium bromide. These halides are usually 0.001 per 1 L of water.
~ 5 mol, preferably about 0.01 to 2 mol of an aqueous solution is dissolved per 1 kg of the compound of the general formula (I), usually 1
It is good to use about -200 L, preferably about 5-100 L.

Various types of electrolytic cells can be used. For example, a beaker type anode cell, a non-separation type electrolytic cell that does not separate the cathode cell, for example, porous glass, ion exchange resin such as Nafion, etc. The reaction can be carried out in a separate type electrolytic cell in which a cell and a cathode cell are separated. The electrode material can be widely used as long as it is not easily corroded by the electrolytic oxidation system. Usually, platinum, beta-type lead dioxide, various stainless steels, etc. can be used as the anode, and platinum, various stainless steels, lead, etc. can be used as the cathode, but the present invention is not limited to these specific examples.
If necessary, these plated electrodes and alloys can also be used.
The above electrolysis reaction is usually performed under conditions such as constant current, constant voltage, and constant potential until the compound (I) is almost consumed.
The reaction temperature of the above reaction is usually about 30 to 100 ° C, preferably about 10 to 50 ° C. The resulting general formula (II
The optically active epoxide represented by I) can also be isolated by a conventional purification operation such as concentration and chromatography.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples. Me is methyl and Ph is phenyl. Example 1 In a beaker-type electrolytic cell, compound (Ia) (R ¹ = Ph, R
³ = Me, R ² = R ⁴ = H) 118 mg, compound (IIa)
^{[(R 6, R 7)} = (CH 2) 4, R 11 = R 13 = t-Bu, R 5
= R ⁸ = R ⁹ = R ¹⁰ = R ¹² = H, Y = Cl) 36 mg (5 mol
%), 5 ml of methylene chloride, and 15 ml of 1N sodium chloride aqueous solution are weighed out, and two platinum plates (1.0 × 1.5c)
m ² ) was used as an anode and a cathode, respectively, and electrolysis was carried out at a constant current of 10 mA for 24 hours while stirring at 5 to 0 ° C. After the electrolytic reaction,
The methylene chloride layer was washed with a 5% aqueous sodium thiosulfate solution, the methylene chloride solution was concentrated, and the residue was separated and purified with a silica gel column to give compound (IIIa) (R ¹⁴ = P
h, R ¹⁶ = Me, R ¹⁵ = R ¹⁷ = H) (101 mg, yield 75)
%)was gotten. The obtained compound (IIIa) was used as an optically active column (DAICEL CHIRALCEL OB-
As a result of analysis by high performance liquid chromatography equipped with (H), the enantiomeric excess rate was 81%. IR (neat) 3064, 2996, 2968, 293
0, 1605, 1496, 1451, 1358 cm ^{-1 1} H NMR (200 MHz, CDCl ₃ ) δ 1.07 (d, J = 5 Hz, 3 H), 2.93 (dq,
J = 4.5Hz, 1H), 3.46 (d, J = 4Hz, 1
H), 7.18 to 7.41 (m, 5H) ¹³ C NMR (50 MHz, CDCl ₃ ) δ 13.0, 55.6, 58.0, 127.1, 128.
0,128.5,136.1

Example 2 In the same manner as in Example 1 except that the 1N sodium bromide aqueous solution was used instead of the 1N sodium chloride aqueous solution, the compound (I
When a) was electrolytically oxidized, compound (IIIa) (94 m
g, yield 70%, enantiomeric excess 80%) were obtained. Example 3 Compound (Ib) (R ¹ = Ph, R ² = Me, R ³ = R ⁴ = H)
118 mg, compound (IIb) [(R ⁵ , R ⁸ ) =-(CH ₂ ) ₄
^{-, R 11 = R 13 =} t-Bu, R 6 = R 7 = R 9 = R 10 = R 12
= H, Y = Cl) 36 mg (5 mol%), electrolytic reaction and post-treatment were carried out in the same manner as in Example 1. As a result, the compound (III
b) (R ¹⁴ = Me, R ¹⁵ = Ph, R ¹⁶ = R ¹⁷ = H) (74
mg, yield 55%) was obtained. Obtained compound (III
b) is an optically active column (DAICEL CHIRALC
As a result of high performance liquid chromatography equipped with ELOB-H), the enantiomeric excess rate was 51%. IR (neat) 3032, 2983, 2933, 281
6,2717,1604,1496,1447,132
8,1343 cm ^{-1 1} H NMR (200 MHz, CDCl ₃ ) δ 1.72 (s, 3 H), 2.88 (ABq, J = 6 Hz,
2H), 7.23 to 7.39 (m, 5H) ¹³ C NMR (50 MHz, CDCl ₃ ) δ 21.8, 57.0, 125.2, 127.4, 128.
3, 129.0, 141.1 Examples 4 to 9 The compound (Ia) was electrolytically oxidized under the conditions shown in Table 1 in the same manner as in Example 1. Table 1 shows the results.

[0026]

[Table 1]

Example 10 Instead of the beaker type electrolytic cell, a separation type electrolytic cell partitioned by a porous glass filter was used, and 118 mg of compound (Ia) and 36 mg (5 mol of compound (IIa) were used as an anode cell solution.
%) Methylene chloride solution (5 ml), 1N sodium chloride aqueous solution (15 ml), and 1N sodium chloride aqueous solution (20 ml) as a cathode bath solution, and the two platinum plates (1.0 x
1.5 cm ² ) was used as an anode and a cathode, and electrolysis was carried out at a constant current of 10 mA for 24 hours while stirring at -5 to 0 ° C. After the electrolytic reaction, the same post-treatment as in Example 1 was performed. As a result, the compound (IIIa) (97 mg, yield 72%, enantiomeric excess 79
%)was gotten. The spectral data of the obtained compound (IIIa) completely coincided with that of Example 1.

Example 11 Instead of the compound (IIa), the compound (IIc) (R ⁶ = R ⁷ =
Ph, R ¹¹ = R ¹³ = tBu, R ⁵ = R ⁸ = R ⁹ = R ¹⁰ = R ¹² =
H, Y = Cl) 41 mg (5 mol%) was used, and the same reaction as in Example 1 was carried out. As a result, the compound (IIIa) (98 m
g, yield 73%, enantiomeric excess 74%). The spectral data of the obtained compound (IIIa) is shown in Example 1.
It was an exact match with that.

Reference Example 1 (Production of Functional Material from Compound III) Compound (IIIa) (R ¹⁴ = Ph, R ¹⁶ = Me, R ¹⁵ = R ¹⁷
= H) 100 mg of ethylmagnesium bromide was allowed to act, and the produced alcohol derivative was allowed to act with methanesulfonyl chloride to give methanesulfonate, and then reduced with lithium aluminum hydride. When a phenol derivative is formed with hydrogen peroxide and aluminum chloride and reacted with p′-octylbiphenyl-p-carboxylic acid chloride,
41 mg (total yield 12%) of compound (IVa), which is one kind of liquid crystal molecule, was obtained. ^{IR (KBr) 3060,1716,1604cm -1 1 H} NMR (200MHz, DMF-d 7) δ 0.94~2.47 (m, 28H), 6.81~8.2
5 (m, 12H) Incidentally, the compound (IVa) is, for example, “Molecular Functional Materials and Device Development” Takeo Shimizu, Katsumi Yoshino, published by NTS Co., Ltd., Chapter 2, Section 11, p.641.

[0030]

Embedded image

[0031]

The olefin compound represented by the general formula (I) of the present invention is electrolyzed in the presence of the optically active manganese catalyst represented by the general formula (II) in a two-phase system of an organic solvent and an aqueous halide solution. As a result, the optically active epoxide derivative represented by the general formula (III) can be obtained in high yield and high purity without using a large amount of dangerous oxidizing agent.
In addition, it can be manufactured without producing a large amount of waste.

Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C07M 7:00 (72) Inventor Yutaka Kameyama 463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. (72) Inventor Ryo Kikuchi 463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd.

Claims (1)

[Claims] 1. An olefin compound represented by the general formula (I) is electrolyzed in a two-layer system of an organic solvent and a halide aqueous solution in the presence of an optically active manganese catalyst represented by the general formula (II), A method for producing an optically active epoxide derivative, which comprises obtaining the optically active epoxide derivative represented by the formula (III). Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom and may have a substituent, an alkyl group, an alkenyl group, an alkynyl group, an aromatic compound residue, a heteroaromatic compound residue, An alkoxy group, an acyl group, an optionally protected hydroxyl group, an amino group, a carboxyl group, a halogen atom, a nitro group, and a cyano group are shown. (Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ together form a C ₅ -C ₈ cycloalkane with R ⁵ and R ⁸ and R ⁶ and R ⁷ are hydrogen atoms, or R ⁶ and R ⁷ To form a C ₅ -C ₈ cycloalkane and R ⁵ and R ⁸ are hydrogen atoms, or R ⁵ and R ⁸ are aryl groups and R ⁶ and R ⁷ are hydrogen atoms, or R ⁶ and R ^{7 are} .R ^9, R ^10, R but representing a and R ⁵ and R ⁸ are hydrogen atoms with an aryl group
¹¹ , R ¹² and R ¹³ are each a hydrogen atom, an optionally substituted alkyl group, an aromatic compound residue, an alkoxy group, an acyl group, a hydroxyl group optionally having a protective group,
Amino group, carboxyl group, halogen atom, nitro group,
A cyano group is shown. Y represents an anion. ) (In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic compound residue, a heteroaromatic compound residue, which may have a substituent, (Alkoxy group, acyl group, optionally protected hydroxyl group, amino group, carboxyl group, halogen atom, nitro group, cyano group.)