JPH06247993A - Production of optically active epoxide and new manganese compound - Google Patents

Abstract

PURPOSE:To obtain an optically active epoxide useful for a synthetic intermediate for medicines, agrochemicals, etc., ferroelectric liquid crystal, etc., by reacting an olefin compound with oxygen in the presence of both an optically active metal compound such as a new Mn (III) complex, etc., and an aldehyde compound. CONSTITUTION:An olefin compound (e.g. 1,2-dihydronaphthalene) is reacted with oxygen in the presence of both an optically active metal compound composed of a new manganese (II) compound of the formula (R<2> and R<2> are H, alkyl or aryl; R<3> to R<5> are H, alkyl, aryl, acyl or alkoxycarbonyl; X<-> is anion) and an aldehyde compound (e.g. pivalic aldehyde) at room temperature in an oxygen atmosphere under stirring to give the objective optically active epoxide [(1R,2S)-epoxy-3,4-dihydronaphthalene, etc.] useful for a synthetic intermediate for physiologically active compounds such as medicines, agr'ichemicals, etc., a functional material such as ferroelectric liquid crystal, etc., and a synthetic intermediate for fine chemicals.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an optically active epoxide and a novel manganese compound, and particularly to a synthetic intermediate for physiologically active compounds such as pharmaceuticals and agricultural chemicals, or functional materials such as liquid crystals, and fine chemicals. The present invention relates to a method for producing an optically active epoxide useful as a raw material, and a novel manganese compound useful as a catalyst used in the method.

[0002]

2. Description of the Related Art Generally, epoxides are synthesized from corresponding olefins, and various synthetic methods are known. Among these methods, as a method for producing an optically active epoxide from an olefin, there are conventionally 1) a method utilizing a microorganism, 2) a method utilizing a chemical reaction and the like. 1) Noca is a method of using microorganisms
It is a method of giving olefins to microorganisms such as rdia corallina to obtain optically active epoxides as their metabolites. Further, 2) a method utilizing a chemical reaction is typically a method utilizing a reaction using a titanium compound having an optically active diethyl tartrate as a ligand and t-butyl hydroperoxide as an oxidizing agent. Is. Using this reaction, the corresponding optically active epoxide can be obtained from allyl alcohol.

However, since the method utilizing microorganisms utilizes the metabolic action of microorganisms, its application is limited only when converting an olefin having a high substrate specificity and having a double bond at the terminal to an epoxide, and the epoxide There is a problem that the production efficiency is extremely low.

Further, even in the method utilizing a chemical reaction, since the reaction substrate is limited to allyl alcohol and there is a danger of explosion, it is necessary to use a peroxide as an oxidant, which requires careful handling. , There are problems in terms of production cost and safety.

Therefore, recently, a new chemical reaction for synthesizing an optically active epoxide has been proposed for the purpose of eliminating the restriction on the reaction substrate. (EN Jacobsen et al.,
J. Org. Chem., 56, 2296 (1991); T. Katsuki et al., Te
trahedron Lett., 32, 1055 (1991)).

[0006]

However, even in the above method, since the peroxide is used as the oxidant, the problems in production cost and safety cannot be solved.

Therefore, the object of the present invention is to provide an optically active epoxide useful as a synthetic raw material for synthetic intermediates for physiologically active compounds such as pharmaceuticals and agricultural chemicals, functional materials such as liquid crystals, fine chemicals, etc. To provide a novel method which can be produced by using various oxygen molecules, and a novel manganese compound suitable as a catalyst in the method.

[0008]

In order to solve the above-mentioned problems, the inventors of the present invention have been keen on a method for synthesizing an optically active epoxide from an olefin by using safe and inexpensive oxygen as an oxidant. I have been studying repeatedly. As a result, they have found that the above-mentioned object can be achieved by a reaction using an optically active metal compound as a catalyst, and further discovered a novel manganese compound as a suitable optically active metal compound, and arrived at the present invention.

That is, the present invention provides a method for producing an optically active epoxide, which comprises a step of reacting an olefin compound with oxygen in the presence of an optically active metal compound and an aldehyde compound in order to solve the above problems. Is.

It is preferable that the optically active metal compound is an optically active manganese (III) complex.

The present invention also provides, as the optically active manganese (III) complex, the following general formula (a):

[0012]

[Chemical 3]

[In the formula, R ¹ and R ² are different groups, and are a hydrogen atom, a linear or branched alkyl group or an aryl group, which may have a substituent, and two R ¹ Or two R ^{2 s} may be bonded to each other to form a ring, and R ³ , R ⁴ and R ⁵ may be the same or different and may be a hydrogen atom, a straight chain or a branched form. Is an alkyl group, an aryl group, an acyl group or an alkoxycarbonyl group, which may have a substituent, and X ⁻ represents an anion].

The method for producing the optically active epoxide of the present invention (hereinafter referred to as "the method of the present invention") and the novel manganese compound will be described in detail below.

The olefin compound used as a starting material in the method of the present invention is not particularly limited as long as it is a compound having an olefinic double bond in the molecule, and may be appropriately selected according to the desired epoxide. it can.
As a typical example of this olefin compound, 2-methyl-2
-Aliphatic olefins such as decene, p-nitrostyrene,
Examples thereof include aromatic olefins such as o-nitrostyrene, p-phenylstyrene, α-vinylnaphthalene, β-vinylnaphthalene, and the like.

Among these, in the method of the present invention, the olefin compound as a starting material is a styrene derivative represented by the following formula (b-1) or 1,2 represented by the following formula (b-2). It is effective when a fused olefin represented by dihydronaphthalene is used to produce a corresponding epoxide.

[0017]

[Chemical 4]

[Wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ and R
^10's may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group or an aryl group, which may have a substituent, and n is 0 or 1
And m is an integer of 1 to 4, R ¹¹ is a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, a nitro group, a cyano group, an alkoxy group, an acyl group, An alkoxycarbonyl group, an amino group or a silyl group, and when m is an integer of 2 to 4,
Multiple R ¹¹ may be the same or different]

In the general formula (b-1) or (b-2), a typical example of the linear or branched alkyl group represented by R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ is a methyl group, Examples thereof include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. Typical examples of the cycloalkyl group include cyclohexyl. A group etc. can be mentioned. Further, as the aryl group, a phenyl group, p
-Methoxyphenyl group, p-chlorophenyl group, p-fluorophenyl group and the like can be mentioned.

Further, typical examples of the halogen atom of R ¹¹ include fluorine, chlorine, bromine and the like, and typical examples of the linear or branched aryl group include a methyl group, an ethyl group and an n-propyl group. , Isopropyl group, n-butyl group,
Examples thereof include sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group, and typical examples of cycloalkyl groups include cyclohexyl group. Typical examples of the aryl group include a phenyl group, p-methoxyphenyl group, p-chlorophenyl group, p-fluorophenyl group and naphthyl group, and typical examples of the alkoxy group include a benzyloxy group. You can Representative examples of the acyl group include an acetyl group and a propionyl group, and representative examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, an n-octylcarbonyl group and a benzyloxycarbonyl group. And the like, and typical examples of the amino group include a dimethylamino group, a diethylamino group and the like. Typical examples of the silyl group include a trimethylsilyl group and a tert-butyldimethylsilyl group.

In the method of the present invention, when the styrene derivative represented by the general formula (b-1) is used as the olefin compound, an optically active epoxide represented by the following general formula (c-1) can be obtained. The above-mentioned general formula (b-
When the 1,2-dihydronaphthalene represented by 2) and its derivative are used, the optically active epoxide represented by the following general formula (c-2) can be obtained.

[0022]

[Chemical 5]

An optically active epoxide represented by the formula: [wherein R ^{6 to} R ¹¹ , n and m are as defined in the above general formula (b)] can be obtained.

Examples of the optically active epoxide represented by the general formula (c-1) include p-phenylstyrene oxide, p-nitrostyrene oxide, o-nitrostyrene oxide, 2-naphthylethylene oxide and the like. Examples of the optically active epoxide represented by the formula (c-2) include 1,2-dihydronaphthalene oxide, 3,
3-dimethyl-3,4-dihydronaphthalene oxide,
5,7-Dimethyl-3,4-dihydronaphthalene oxide, 4,4-dimethyl-3,4-dihydronaphthalene oxide, 6-benzyloxy-5-nitro-3,4-dihydronaphthalene oxide, 7-nitro-3 , 4-dihydronaphthalene oxide, 1,2-benzo-3,4-cycloheptadiene oxide and the like.

The method of the present invention is particularly applicable to the above general formula (b-
Among the 1,2-dihydronaphthalenes represented by 2), the following general formula (b-3):

[0026]

[Chemical 6]

[Wherein R ^{8 to} R ¹¹ , n and m are as defined in the above general formula (b)] 1, 2
-The production of a corresponding optically active epoxide using a dihydronaphthalene derivative is effective in that the epoxide can be obtained in a high optical yield.

1,2-represented by the general formula (b-3)
Typical examples of the dihydronaphthalene derivative are 1,2-dihydronaphthalene, 3,3-dimethyl-3,4-dihydronaphthalene, 5,7-dimethyl-3,4-dihydronaphthalene and 4,4-dimethyl-3,4. -Dihydronaphthalene, 6-benzyloxy-5-nitro-3,4-dihydronaphthalene, 7-nitro-3,4-dihydronaphthalene, 1,2-benzo-3,4-cycloheptadiene and the like can be mentioned.

The optically active metal compound used as a catalyst in the method of the present invention is not particularly limited and, for example, a complex of at least one transition metal selected from vanadium, manganese, iron, cobalt, nickel and ruthenium is typical. Can be listed as This vanadium,
As the complex of at least one transition metal selected from manganese, iron, cobalt, nickel and ruthenium, for example, optically active iron (III) complex, optically active ruthenium (III) complex, optically active oxovanadium (IV) complex, optical Examples thereof include active manganese (III) complex.
Among them, the optically active manganese (III) complex is preferable.

In the present invention, as the optically active manganese (III) complex, in particular, a novel manganese compound represented by the general formula (a) described later can be easily prepared, and the optically active manganese (III) complex can be produced at a high optical yield. Since an epoxide is obtained, it is suitable as a catalyst in the method of the present invention.

In the method of the present invention, among the novel manganese compounds represented by the general formula (a) described later, the complex of the complex can be easily synthesized, separated and purified, and the optically active epoxide can be obtained in a high optical yield. From the viewpoint of obtaining, the following general formula (a-1) is preferable:

[0032]

[Chemical 7]

A complex represented by the formula [wherein R ¹ , R ² and R ⁴ are the same as those in the above general formula (a)] can be given.

In the method of the present invention, the above general formula (a)
The optically active manganese (III) complex represented by is used either singly or in combination of two or more.

In the method of the present invention, when the novel manganese compound represented by the general formula (a) is used as the optically active manganese (III) complex, epoxide is used as a catalyst with a high optical yield and a high chemical yield. From the viewpoint of being obtained, it is preferably used in a ratio of 1 to 30 mol% with respect to 1 mol of the olefin compound, and more preferably used in a ratio of 5 to 20 mol%.

Further, in the method of the present invention, when the novel manganese compound represented by the general formula (a) is used,
In the case where a manganese compound in which two R ^{1 s} in the general formula (a) have an absolute configuration of (S, S) is used, R ⁶ and R ⁷ in the general formula (c-1) or (c-2) are used.
Can preferentially obtain an optically active epoxide having a positive optical rotation of (1R, 2S) type. For example, 1,2-
Using dihydronaphthalene as the olefin compound, the following formula:

[0037]

[Chemical 8]

When a manganese compound represented by the following is used as a catalyst and reacted, the following formula:

[0039]

[Chemical 9]

(1R, 2S) -epoxy-
Preference is given to 3,4-dihydronaphthalene.

Further, when a manganese compound in which two R ^{1 s} in the general formula (a) have the absolute configurations of (R, R) opposite to the above is used, the above general formula (c-1) or (c) is used. It is possible to preferentially obtain an optically active epoxide in which R ⁶ and R ⁷ in −2) have a negative optical rotation of (1S, 2R) type. For example, using 1,2-dihydronaphthalene as an olefin compound, the following formula:

[0042]

[Chemical 10]

When the reaction is carried out using a manganese compound represented by the formula:

[0044]

[Chemical 11]

(1S, 2R) -epoxy-
Preference is given to 3,4-dihydronaphthalene.

In the method of the present invention, an olefin compound is catalyzed by an optically active metal compound represented by the novel manganese compound represented by the general formula (a) as a catalyst, and further reacted with oxygen in the presence of an aldehyde compound. It is a method to let.

As a typical example of this aldehyde compound, the following formula (d):

[0048]

[Chemical 12]

Examples thereof include compounds represented by the formula: wherein R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms, linear or branched alkyl groups or cycloalkyl groups. Typical examples of the linear or branched alkyl group in the formula (d) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-
Examples thereof include a butyl group and an n-hexyl group, and typical examples of the silloalkyl group include a cyclohexyl group.

Specific examples of the aldehyde compound include acetaldehyde, propionaldehyde, n-butyraldehyde, n-valeraldehyde, isovaleric acid aldehyde, 1-hexanal, isobutyraldehyde, sec.
And aliphatic aldehydes such as butyraldehyde and pivalaldehyde. Of these, aliphatic aldehydes are preferable because epoxides can be obtained with high optical yield and high chemical yield.

In particular, in the method of the present invention, as the aldehyde compound, R ¹² in the general formula (d),
Aldehydes in which R ¹³ and R ¹⁴ are not a hydrogen atom but a linear or branched alkyl group, that is,
The use of a tertiary aldehyde is preferable in that an optically active epoxide can be obtained with a high optical yield and a high chemical yield. In particular, the use of pivalaldehyde is preferable in that an epoxide can be obtained with a high optical yield.

In the present invention, the aldehyde compound represented by the general formula (d) may be used alone or in combination of two or more.

In the method of the present invention, the aldehyde compound is used in an amount of 1 to 10 mol based on 1 mol of the olefin compound in terms of obtaining an epoxide with a high optical yield and a high chemical yield. Is preferred, and
A ratio of 2.5 to 5 mol is preferable.

The oxygen used in the method of the present invention may be oxygen gas (pure oxygen) or oxygen-containing nitrogen gas (for example,
An oxygen-containing inert gas such as air) may be used.

Further, in the method of the present invention, preferably the reaction is carried out in the liquid phase. If necessary, a solvent can be used, and as the solvent used, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ester solvent is effective. Is. In particular, aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene and fluorobenzene are preferable.

The amount of this solvent used is usually about 1 to 10 ml per 1 mmol of the olefin compound. At this time, if the amount of the solvent is reduced, the epoxide can be obtained with a high optical yield.

The reaction temperature is usually preferably 0 to 60 ° C, more preferably 20 to 40 ° C. The reaction pressure may be normal pressure as long as the solvent does not vaporize.

The reaction time is usually about 5 minutes to 1 hour. Further, the progress of the reaction can be confirmed by sequentially collecting samples of the reaction mixture and analyzing them by thin layer chromatography (TLC), gas chromatography (GC) and the like.

Recovery and purification of the desired epoxide from the reaction mixture obtained by the above reaction can be carried out by combining known methods such as distillation, adsorption, extraction and recrystallization.

The present invention also provides a novel manganese compound represented by the above general formula (a), which is useful as an optically active manganese (III) complex.

In the above general formula (a) representing the novel manganese compound, R ¹ and R ² are different groups, a hydrogen atom, a linear or branched alkyl group or an aryl group, and have a substituent. You may have. Examples of the linear or branched alkyl group include a methyl group, an ethyl group,
Typical examples are a propyl group, an isopropyl group and a tert-butyl group. As the aryl group, a phenyl group, p-
Typical examples are a methoxyphenyl group, a p-chlorophenyl group, a p-nitrophenyl group and the like.

Further, two R ^{1 s} or two R ^{2 s} may be bonded to each other to form a ring.
They may be bonded to each other via a group such as — (CH ₂ ) ₄ — to form a ring such as a 6-membered ring.

Further, R ³ , R ⁴ and R ⁵ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, an aryl group, an acyl group or an alkoxycarbonyl group and has a substituent. You may have. Typical examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group and a tert-butyl group. As the aryl group, a phenyl group,
p-methoxyphenyl group, p-chlorophenyl group, p-
A nitrophenyl group and a naphthyl group are typical. As the acyl group, an acetyl group, a perfluoroacetyl group,
A propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group and the like are typical, and an alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group,
Typical examples are a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cyclooctyloxycarbonyl group, an adamantyloxycarbonyl group and a trifluorooxycarbonyl group.

X ^- represents an anion. Typical examples of this anion include F ⁻ , Cl ⁻ , Br ⁻ , PF ₆ ⁻ ,
Examples include ClO ₄ ⁻ , BF ₄ ⁻ , SO ₄ ^{2− and the} like.

As typical examples of the novel manganese compound represented by the general formula (a), the following formulas (III-a) to (I
Examples thereof include those represented by II-o).

[0066]

[Chemical 13]

[0067]

[Chemical 14]

[0068]

[Chemical 15]

[0069]

[Chemical 16]

[0070]

[Chemical 17]

The novel manganese (III) compound represented by the general formula (a) can be prepared by a known method. For example, LJ Boucher et al., Inor
g. Chem., 16,1360 (1977), T. Matsusita et al., Bul
l. Chem. Soc. Jpn., 54,3743 (1981), or T. Katsu
It can be prepared according to the method reported in ki et al., Tetrahedron Lett., 32, 1055 (1991). For example,
Ligands corresponding to the complex and manganese (III) acetate
Can be prepared by heating lithium chloride in dichloromethane and then adding lithium chloride. Alternatively, the 1,3-diketone derivative and the optically active 1,2-diaminoethane derivative may be directly reacted with manganese (III) acetate and then added with lithium chloride.

The novel manganese compound of the present invention is not limited to the use as a catalyst in the method of the present invention, and is also useful as a catalyst for other asymmetric oxidation reactions such as synthetic reactions of various optically active organic compounds. is there.

[0073]

The present invention will be described in more detail below with reference to examples of the present invention, but the present invention is not limited to these examples.

(Example 1) (1) Preparation of β-diketone type optically active manganese (III) complex catalyst (S, S) -1,2-diphenyl-1,2-ethylenediamine 640 g (3.0 mmol) Dissolved in a mixed solution of methanol-dichloromethane (15 ml each), and with stirring, 680 mg of manganese (III) acetate dihydrate.
(2.5 mmol) was added. Further, 5 ml of a dichloromethane solution containing 1.12 g (6.0 mmol) of ethyl ethoxymethyleneacetoacetate was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, 320 mg of lithium chloride (7.6 mmo
1) was added, the mixture was again heated to 40 ° C. and stirred for 1 hour.
After allowing to cool, the reaction mixture was concentrated and extracted with dichloromethane-water to separate a dichloromethane solution as an organic layer, which was dried over anhydrous sodium sulfate. Next, the dichloromethane solution was concentrated, chloroform was added, and ether was slowly added to precipitate a reaction product. The precipitated reaction product was filtered, washed with ether, and dried under reduced pressure to give the following formula (a-2):

[0075]

[Chemical 18]

780 mg (yield: 54%) of a brown solid of an optically active manganese (III) complex represented by the following formula was obtained.

This β-diketone type optically active manganese (I
II) The complex catalyst was prepared according to the following reaction formula.

[0078]

[Chemical 19]

(2) Asymmetric epoxidation reaction 60 m of the optically active manganese (III) complex obtained above
g (0.104 mmol) of benzene solution (1.0 m
l-, separately prepared under argon atmosphere in 1,2-
1.0 ml of a benzene solution containing 104 mg (0.8 mmol) of dihydronaphthalene and 241 mg (2.8 mmol) of pivalaldehyde was added at room temperature in an oxygen atmosphere and reacted with stirring. This reaction was followed sequentially by TLC. The reaction is completed in about 30 minutes, and the reaction mixture is purified by silica gel column chromatography to give 1,2-epoxy-3,4-dihydronaphthalene 4 as an oil.
4 mg was obtained. (Yield: 38%)

The optical yield of the obtained 1,2-epoxy-3,4-dihydronaphthalene was measured by GC using an optically active GC column to determine the optical yield. As a result, the optical yield of the obtained 1,2-epoxy-3,4-dihydronaphthalene was 36% ee. Moreover, when the optical rotation of this epoxide was measured, [α] _D + 46.0 °
(CHCl ₃ , c = 1.00). From the measured values of this optical rotation, the literature: DRBoyd, DM Jerina, and JWD
According to aly, J. Org. Chem., 35, 3170 (1970), it was found that (1R, 2S) -epoxy-3,4-dihydronaphthalene represented by the following formula was preferentially obtained.

[0081]

[Chemical 20]

Here, the optical yield is a value obtained based on the following formula. ｜ ([1R, 2S]-[1S, 2R]) / ([1R, 2S] + [1S, 2
R]) | × 100 (%) where [1R, 2S] :( 1R, 2S) -epoxy-
Yield or yield of 3,4-dihydronaphthalene [1S, 2R] :( 1S, 2R) -epoxy-3,4-
Dihydronaphthalene yield or yield

(Examples 2 to 4) In each example, the amount of the optically active manganese (III) complex represented by the above formula (a-2) was 28 mg (0.048 mmo).
l), 46 mg (0.080 mmol), 138 mg
(0.24 mmol) except that the reaction was performed,
1,2-Epoxy-3,4-dihydronaphthalene was obtained in the same manner as in Example 1, and the yield and optical yield of 1,2-epoxy-3,4-dihydronaphthalene were determined. The results are shown in Table 1.

[0084] Note a): optically active manganese for olefins (II
I) Molar ratio of complex catalyst

(Examples 5 and 6) In each example, the amount of pivalaldehyde used was 138 mg (1.6 mg).
mmol) and 413 mg (4.8 mmol) were changed, and 1,2-epoxy-3,4-dihydronaphthalene was obtained in the same manner as in Example 1 to obtain 1,2-epoxy-3,4. -Dihydronaphthalene yield and optical yield were determined. The results are shown in Table 2.

[0086]

[Table 1]

(Example 7) 20 minutes after the initiation of the reaction, the same procedure as in Example 5 was repeated except that 69 mg (0.8 mmol) of pivalaldehyde was added and the reaction was continued by stirring at room temperature for 30 minutes. 1,2-epoxy-3,4
-Dihydronaphthalene is obtained, 1,2-epoxy-3,4
-Dihydronaphthalene yield and optical yield were determined.
As a result, the yield of 1,2-epoxy-3,4-dihydronaphthalene was 40% and the optical yield of 1,2-epoxy-3,4-dihydronaphthalene was 49% ee.

(Examples 8 to 10) In each example, the total amount of benzene used as a solvent was 16 m.
1,2-epoxy-3,4-dihydronaphthalene was obtained in the same manner as in Example 1 except that the amounts of 1,2-epoxy-3,4-dihydronaphthalene were changed to 1, 8 ml and 4 ml. I asked for the rate. The results are shown in Table 3.

[0089]

(Examples 11 to 14) In each example, 1,2-epoxy-3, was prepared in the same manner as in Example 1 except that the reaction temperature was changed to -30 ° C, 0 ° C, 25 ° C and 40 ° C. 4-
Obtained dihydronaphthalene, 1,2-epoxy-3,4-
The yield and optical yield of dihydronaphthalene were determined. The results are shown in Table 4.

[0091]

(Examples 15 to 17) In the same manner as in Example 1, except that isobutyraldehyde, isovaleric acid aldehyde, and n-butyraldehyde were used instead of pivalaldehyde in each of Examples 1 and 2, -Epoxy-
3,4-dihydronaphthalene is obtained, 1,2-epoxy-
The yield and optical yield of 3,4-dihydronaphthalene were determined. The results are shown in Table 5.

[0093]

[Table 2]

(Examples 18 to 24) Examples 18 to 24 were carried out except that acetonitrile, 1,2-dichloroethane, diethyl ketone, ethyl acetate, toluene, fluorobenzene and nitrobenzene were used as the solvent instead of benzene, respectively. 1,2-Epoxy-3,4-dihydronaphthalene was obtained in the same manner as in Example 1, and the yield and optical yield of 1,2-epoxy-3,4-dihydronaphthalene were determined. The results are shown in Table 6.

[0095]

[Table 3]

Examples 25 to 28 In each example, the following general formula (a-3):

[0097]

[Chemical 21]

[Wherein R ¹⁵ is as shown in Table 7]
Of various β-diketone type optically active manganese (I
The II) complex was prepared by the method described in the section (1) of Example 1. Next, this β-diketone type optically active manganese (I
II) 1.0 m of benzene solution of 0.104 mmol of complex
1, 1 and 2, which had been prepared in advance in an argon atmosphere,
-Dihydronaphthalene 104 mg (0.8 mmol)
And 1.0 ml of a benzene solution of 241 mg (2.8 mmol) of pivalaldehyde were added at room temperature in an oxygen atmosphere and reacted with stirring. After completion of the reaction, the reaction product is purified by silica gel column chromatography,
1,2-Epoxy-3,4-dihydronaphthalene was obtained as an oil. Obtained 1,2-epoxy-3,4-
The yield and optical yield of dihydronaphthalene were determined. The results are shown in Table 7.

[0099]

[Table 4]

Examples 29 to 32 In each of Examples 30 to 32, instead of ethyl ethoxyethylene acetoacetate, the following general formula (d-1):

[0101]

[Chemical formula 22]

[Wherein R ¹⁶ is as shown in Table 8]
The aldehyde represented by
Instead of dichloromethane, a mixed solvent of ethanol-1,2-dichloroethane was used, and the reaction was carried out by heating at 80 ° C. to carry out the reaction, and in the same manner as in the method described in the item (1) of Example 1, the following general formula (A-4):

[0103]

[Chemical formula 23]

[In the formula, R ¹⁶ is as shown in Table 8]
Of various β-diketone type optically active manganese (I
II) a complex was obtained.

Next, in Examples 29 to 32, various β-diketone type optically active manganese (II) prepared above were prepared.
An epoxide was obtained in the same manner as in Example 1 except that the complex I) was used, and the yield and the optical yield of the obtained optically active epoxide were determined. The results are shown in Table 8.

[0106]

[Table 5]

(Examples 33 to 41) In each example, the following formula (a-5) is obtained in the same manner as in Examples 30 to 32:

[0108]

[Chemical formula 24]

[In the formula, R ¹⁷ is as shown in Table 9]
Represented by various β-diketone type optically active manganese (I
II) The complex was prepared.

Then, an epoxide was obtained in the same manner as in Example 1 except that these β-diketone type optically active manganese (III) complexes were used. The yield and the optical yield of the obtained optically active epoxide were obtained. I asked. The results are shown in Table 9.

[0111]

[Table 6]

(Examples 42 to 47, Comparative Example 1) In each Example, the β-diketone type optically active manganese (III) complex used in Example 33 was used as a catalyst, and 1,2-dihydronaphthalene was used instead of the catalyst. 1,2-dihydronaphthalene, 3,3-dimethyl-3,4-dihydronaphthalene, 4,4-dimethyl-3,4-dihydronaphthalene, 6-benzyloxy-5-nitro-3,4-dihydro, respectively. An epoxide was obtained in the same manner as in Example 1 except that naphthalene, 6-methoxycarbonyl-3,4-dihydronaphthalene and 1,2-benzo-3,4-cycloheptadiene were used and the reaction temperature was 30 ° C. It was The optical purity of the obtained epoxide was measured by the method shown in Table 10 to obtain the epoxide yield and the optical yield. The results are shown in Table 10.

Further, as Comparative Example 1, a literature of epoxidation reaction of 1,2-benzo-3,4-cycloheptadiene (Chemistry Letters) using a Salen-type manganese (III) complex represented by the following formula as a catalyst was used. , 2231 (1992)
The results shown in Table 10 are also shown in Table 10.

[0114]

[Chemical 25]

[0115]

[Table 7]

(Examples 48 to 52) In each example, the β-diketone type optically active manganese (II) used in Example 33 was used.
I) using the complex as a catalyst, p-nitrostyrene, o-nitrostyrene, p-phenylstyrene, α-vinylnaphthalene and β-vinylnaphthalene are used instead of 1,2-dihydronaphthalene, respectively, and the reaction temperature is An epoxide was obtained in the same manner as in Example 1 except that the temperature was 30 ° C.
The optical purity of the obtained epoxide was measured by the method shown in Table 11, and the epoxide yield and the optical yield were determined. The results are shown in Table 11.

[0117]

[Table 8]

(Example 53) Preparation of β-diketone type optically active manganese (III) complex catalyst [Synthesis of ligand] (S, S) -1,2-biphenyl-
0.64 g of 1,2-ethylenediamine (3.0 mmo
1) was dissolved in 20 ml of dichloromethane, and 1.12 g of ethyl ethoxymethylene acetoacetate (6.0 mm) was stirred.
was added to a dichloromethane solution (5 ml), and the mixture was stirred at room temperature for 1 hour for reaction. Next, the solvent was distilled off under reduced pressure to obtain a white solid reaction product. The reaction product was washed with ether to give the following formula (a-2a):

[0119]

[Chemical formula 26]

The optically active N, N'-1,2-diphenylethylenebis (α-ethoxycarbonyl-β-
Ketoimine) was obtained. (Yield: 82%) ¹ H-NMR (CDCl ₃ ): δ 7.87 (d, J = 12.9 Hz, 2H), 7.3
5-7.25 (m, 6H), 7.10-7.00 (m,
4H), 4.60 (d, J = 8.9Hz, 2H), 4.
14 (q, J = 7.2 Hz, 4H), 2.49 (s, 6
H), 1.26 (t, J = 7.2 Hz, 6H) IR (KBr method): 2984, 1078, 1636, 1
573, 1411, 1383, 1365, 1304, 1
233, 1197, 1059 cm ^-1 (see Fig. 1)

[Synthesis of Manganese (III) Complex] The optically active N, N′-1,2-diphenylethylenebis (α-ethoxycarbonyl-β-ketoimine) obtained above.
0.98 g (2.0 mmol) of methanol-dichloromethane mixed solvent (methanol / dichloromethane = 1
(0 ml / 10 ml), and then manganese (III) acetate dihydrate 0.46 g (1.7 mmol) was added with stirring, and the mixture was reacted by stirring at 40 ° C. for 1 hour. After allowing to cool, 0.23 g (5.5 mmol) of lithium chloride was added, the mixture was heated again to 40 ° C., and stirred for 1 hour to cause a reaction. After allowing to cool, the reaction mixture was concentrated, extracted with dichloromethane-water, and the organic layer consisting of a dichloromethane solution was dried over anhydrous sodium sulfate. Next, the dichloromethane solution was concentrated, reprecipitated in chloroform-ether, the precipitate was suction filtered, and then the solvent was distilled off under reduced pressure to obtain the compound of the formula (a-
2):

[0122]

[Chemical 27]

560 mg (yield: 57%) of an optically active manganese (III) complex represented by the above formula was obtained as a brown solid. This solid was recrystallized from a hexane-dichloromethane mixed solution to obtain dark brown needle crystals.
The results of the analysis are: melting point: 210 ° C. (by differential scanning calorimetry (DSC)) IR (KBr method): 2980, 1705, 1596, 1
452, 1388, 1255, 1196, 1084cm
^-1 (see FIG. 2) Elemental analysis: measured value (%): C 56.76; H 4.9
7; N 4.39 Predicted calculation value (C ₂₈ H ₃₀ ClMnN ₂ O ₆ ,%): C 5
It was 7.89; H 5.20; N 4.82, which was confirmed to be the same compound as that prepared in Example 1.

From the synthesis of the above ligands, manganese (II
The reaction leading to the synthesis of I) complex was carried out according to the following reaction formula.

[0125]

[Chemical 28]

(Example 54) In the same manner as in Example 53,
From the corresponding compounds, the following formulas (a-6) to (a-17)
An optically active manganese (III) complex represented by
The properties, melting points, IR spectra were measured, and elemental analysis was performed.

[0127]

[Chemical 29]

[0128]

[Chemical 30]

[0129]

[Chemical 31]

[0130]

[Chemical 32]

[0131]

[Chemical 33]

[0132]

[Chemical 34]

[0133]

According to the method of the present invention, an optically active epoxide can be produced from an olefin by using a safe and inexpensive oxygen molecule as an oxidizing agent. The obtained optically active epoxide is useful as a synthetic intermediate for physiologically active compounds such as pharmaceuticals and agricultural chemicals, functional materials such as liquid crystals, and other synthetic raw materials for fine chemicals. Further, the novel manganese compound of the present invention is a novel compound not described in the literature, is useful as a catalyst in the method of the present invention, and further asymmetric oxidation reaction such as synthetic reaction of various optically active organic compounds. It is also useful as a catalyst.

[Brief description of drawings]

FIG. 1 Optically active N, N′-prepared in Example 53
IR spectrum of 1,2-diphenylethylenebis (α-ethoxycarbonyl-β-ketoimine).

FIG. 2 shows the optically active manganese (II) obtained in Example 54.
I) Measurement chart of the differential scanning calorimetry analysis of the complex (a-6).

FIG. 3 Optically active manganese (III) complex (a-6)
IR spectrum of.

FIG. 4 Optically active manganese (III) complex (a-7)
IR spectrum of.

FIG. 5: Optically active manganese (III) complex (a-8)
IR spectrum of.

FIG. 6 Optically active manganese (III) complex (a-9)
IR spectrum of.

FIG. 7 shows an optically active manganese (III) complex (a-1
IR spectrum of 0).

FIG. 8 shows optically active manganese (III) complex (a-1
IR spectrum of 1).

FIG. 9 shows an optically active manganese (III) complex (a-1
IR spectrum of 2).

FIG. 10 shows an optically active manganese (III) complex (a-1
IR spectrum of 3).

FIG. 11 shows an optically active manganese (III) complex (a-1
4) Measurement chart of differential scanning calorimetry.

FIG. 12 shows an optically active manganese (III) complex (a-1
IR spectrum of 4).

FIG. 13 shows an optically active manganese (III) complex (a-1
IR spectrum of 5).

FIG. 14 shows an optically active manganese (III) complex (a-1
IR spectrum of 6).

FIG. 15 shows an optically active manganese (III) complex (a-1
IR spectrum of 7).

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 21, 1993

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Correction target item name] All drawings

[Correction method] Change

[Correction content]

[Fig. 2]

[Figure 1]

[Figure 3]

[Figure 5]

[Figure 6]

[Figure 4]

[Figure 7]

[Figure 8]

[Figure 9]

[Figure 10]

FIG. 11

[Fig. 12]

[Fig. 13]

FIG. 14

FIG. 15

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C07D 303/08 303/40 // C07B 53/00 B 7419-4H (72) Inventor Shimizu Imakawa Chiba Prefecture 580-32, Takuji Nagaura, Sodegaura-shi 32 Mitsui Petrochemical Industry Co., Ltd.

Claims (4)

[Claims] 1. A process for producing an optically active epoxide, which comprises a step of reacting an olefin compound with oxygen in the presence of an optically active metal compound and an aldehyde compound. 2. The method for producing an optically active epoxide according to claim 1, wherein the optically active metal compound is an optically active manganese (III) complex. 3. The optically active manganese (III) complex comprises:
General formula (a): [Wherein, R ¹ and R ² are different groups, and are a hydrogen atom, a linear or branched alkyl group or an aryl group,
It may have a substituent, two R ^{1 s} or two R ^{2 s} may be bonded to each other to form a ring,
R ³ , R ⁴ and R ⁵ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, an aryl group, an acyl group or an alkoxycarbonyl group and has a substituent. The method for producing an optically active epoxide according to claim 2, which is a novel manganese compound represented by the formula: X ⁻ represents an anion. 4. The following general formula (a): [Wherein, R ¹ and R ² are different groups, and are a hydrogen atom, a linear or branched alkyl group or an aryl group,
It may have a substituent, two R ^{1 s} or two R ^{2 s} may be bonded to each other to form a ring,
R ³ , R ⁴ and R ⁵ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group, an aryl group, an acyl group or an alkoxycarbonyl group and has a substituent. , X ⁻ represents an anion].