JP2911192B2 - Method for producing epoxy group-containing compound - Google Patents

Description

The present invention relates to a method for producing an epoxy group-containing compound, and more particularly to a method for producing an epoxy group-containing compound by a novel reaction carried out in the presence of a nickel compound and an aldehyde compound. On how you can do it.

<Conventional technology> Conventionally, as a method for producing an epoxy group-containing compound,
Compound having a double bond in an inert solvent such as benzene, chloroform or carbon tetrachloride, perbenzoic acid,
A method of oxidizing with an organic peroxide such as formic acid, perphthalic acid, perpropionic acid, perbutyric acid or trifluoroperacetic acid is known. In particular, industrially, peroxide-generating substances, such as mixtures of glacial acetic acid and unsaturated compounds,
A method is known in which a strong acid catalyst is added, hydrogen peroxide is added while heating to 60 to 70 ° C. to generate peracetic acid, and an epoxy group-containing compound is produced using the peracetic acid.

<Problems to be Solved by the Invention> However, the reaction in the above method is a hypersensitive reaction, so that it is difficult to selectively perform an epoxidation reaction, and with the production of an epoxy group-containing compound,
Some of the generated epoxy group-containing compounds may be polymerized. In addition, since this reaction is performed under severe reaction conditions at a reaction temperature of 50 ° C. or higher, side reactions easily occur, and an epoxy group-containing compound cannot be obtained in high yield. In addition, peracids used as oxidizing agents are expensive and dangerous to handle, and thus have the disadvantage of high industrial cost.

Furthermore, as a method for producing an epoxy group-containing compound without using an organic peroxide, there is also known a method of generating a halohydrin by using hypohalous acid as an unsaturated compound and then treating the halohydrin with an alkali to generate an epoxy group. However, this method is not applicable to olefins having a complicated structure.

Accordingly, an object of the present invention is to carry out the reaction under milder reaction conditions than the reaction conventionally used in the production of this type of epoxy group-containing compound, and to use an industrial method because expensive oxidizing agents such as peracids are not used. It is an object of the present invention to provide a novel method which can be carried out at low cost and can obtain an epoxy group-containing compound with good catalytic efficiency.

<Means for Solving the Problems> The present invention provides a compound represented by the general formula (I): Wherein R ¹ is a linear or branched alkyl group;
May have a substituent, R ² and R ³ may be the same or different, a hydrogen atom, a substituted or unsubstituted alkyl group, may be mutually bonded to form a ring, R ¹ and R ³ may be bonded to each other to form a ring,
Further, R ¹ , R ² and R ³ may be simultaneously bonded to form a condensed ring.] A nickel compound and / or a compound represented by the following formula (IVA): And a catalyst comprising a nickel complex represented by the following general formula (II): R ⁷ CHO (II) wherein R ⁷ is a linear or branched alkyl group or an aryl group, and has a substituent. A step of reacting with an oxygen-containing gas in the presence of an aldehyde compound represented by the following general formula (III): [Wherein R ¹ , R ² and R ³ are as defined in the above general formula (I)].

Hereinafter, the method for producing the epoxy group-containing compound of the present invention will be described in detail.

In the general formula (I) representing the double bond-containing compound as a starting material of the present invention, R ¹ is a linear or branched alkyl group, which may have a substituent. Examples of the linear or branched alkyl group for R ¹ include an ethyl group, n
-Propyl group, n-butyl group, sec-butyl group, tert-
Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and the like.

R ² and R ³ may be the same or different and are a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, and a phenylmethyl group. Further, R ² and R ³ may be bonded to each other to form a ring.For example, R ² and R ³ may be bonded to each other to form a ring such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Is also good.

R ¹ and R ³ may be bonded to each other to form a ring, for example, R ¹ and R ³ may be bonded to each other to form a group such as a norbornyl group.

Further, R ¹ , R ² and R ³ may be simultaneously bonded to form a condensed ring, for example, the following formula: May form a condensed ring represented by

Representative examples of the double bond-containing compound represented by the general formula (I) include 2-methyl-2-decene, cis-2-octene, trans-2-octene, 2-methyl-1-decene, and 1-decene Olefins such as 2-norbornene; aromatic unsaturated hydrocarbons such as styrene; and those represented by the following formulas (IA) to (II). .

In the method of the present invention, the double bond-containing compound represented by the general formula (I) may be selected so as to obtain an epoxy group-containing compound having a desired structure.

The catalyst used in the method of the present invention comprises nickel acetate and / or a nickel complex. Representative examples of nickel complexes used as catalysts include, for example,
The following general formulas (IVA), (IVB) and (IVC): And a nickel compound represented by the following formula:

In the method of the present invention, nickel acetate or a nickel complex may be used alone or in combination of two or more.

The nickel complex may be obtained by any method, and is not particularly limited. Moreover, you may use a commercial item.

This nickel complex can be prepared, for example, by mixing a diketone compound corresponding to a desired nickel complex with NiSO ₄ , NiCl ₂ or Ni (OA
c) It can be produced by a desalting method using ₂ . The product thus obtained may be dried and used as it is after removing the reaction solvent and the like. Further, it may be used as a purified product extracted with an organic solvent, or under reduced pressure,
It may be used after sublimation purification, or a combination of these purification methods may be used after purification.

In the method of the present invention, the amount of the catalyst comprising nickel acetate and / or the nickel complex is usually 0.005 to 10 mol per mol of the double bond-containing compound represented by the general formula (I) as a starting material. Mole%, especially
The ratio of 0.0096 to 4 mol% is generally used in that the yield of the epoxy group-containing compound is high.

In the method of the present invention, an aldehyde compound represented by the general formula (II) is used together with the catalyst. In the general formula (II), R ⁷ is a linear or branched alkyl group, or a cycloalkyl group or an aryl group. Representative examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, iso-butyl, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group,
Examples thereof include an n-decyl group, an n-undecyl group, and an n-dodecyl group. Representative examples of the cycloalkyl group include a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and a cyclooctyl group. Representative examples of the aryl group include a phenyl group and a P-methoxyphenyl group. Further, these linear or branched alkyl groups, or cycloalkyl groups or aryl groups may have a substituent, for example, a halogen atom such as chlorine or fluorine, or a substituent such as a methoxy group. It may be.

Representative examples of the aldehyde compound represented by the general formula (II) include acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde,
Nonylaldehyde, decylaldehyde, undecylaldehyde, dodecylaldehyde, isobutyraldehyde,
Examples include 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, isovaleraldehyde, pivalaldehyde, 2-phenylpropionaldehyde, 3-phenylpropanal, and cyclohexanecarbaldehyde.

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

The amount of the aldehyde compound represented by the general formula (II) is usually 1 mol or more per 1 mol of the double bond-containing compound represented by the general formula (I) as a starting material.
Preferably, 1 to 10 mol is generally used. This reaction can also be carried out using a solvent. In this case, usually, 1 to 10 mol of the aldehyde compound is used after diluting with a solvent with respect to 1 mol of the above catalyst. Can also. As the solvent used, a solvent inert to the reaction can be used. Specific examples of such a solvent include benzene, toluene, o-, m- or p-.
Aromatic hydrocarbon solvents such as xylene and mesitylene; halogenated hydrocarbon solvents such as chloroform, dichloromethane and dichloroethane; ethyl acetate, propyl acetate;
Ester solvents such as butyl acetate; acetonitrile, acetone, diethyl ketone, THF and the like. These solvents can be used alone or in combination. In particular, dichloroethane is preferable in that the yield of the epoxy group-containing compound is high.

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

The partial pressure of oxygen in the oxygen-containing gas is preferably 0.1 atm or more.
It is about 10 kg / cm ² , more preferably about 0.2 to 1.0 atm. When the partial pressure of oxygen is within this range, the reaction rate is high and the reaction yield is good.

In the method of the present invention, when the reaction is carried out in the presence of a synthetic zeolite, a higher yield of the compound represented by the general formula (II)
It is preferable because the epoxy group-containing compound represented by I) can be obtained.

The reaction temperature is usually about 0 to 100 ° C.,
-50 ° C is preferred in that the yield of the epoxy group-containing compound is increased.

 The reaction pressure is not particularly limited, and normal pressure is sufficient.

The reaction in the method of the present invention may be performed continuously in the liquid phase or may be performed batchwise.

Since the reaction mixture obtained by the above reaction usually contains by-products, unreacted starting materials, catalysts, and the like, the epoxy group-containing compound, which is the object of the present invention, is separated and purified from the reaction mixture. You can get it. The separation method used is not particularly limited, and may be, for example, a known separation method such as a method by distillation and adsorption, extraction, and recrystallization.

Representative examples of the epoxy group-containing compound represented by the general formula (III) obtained by the method of the present invention include those represented by the following formula.

The epoxy group-containing compound obtained by the method of the present invention is useful for applications such as synthetic intermediates and polymer raw materials.

<Examples> Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

(Examples 1 to 4) In each example, 2-methyl-2-decene was added to the reaction vessel.
3.0 mmol, 6.0 mmol of isobutyraldehyde and 2 ml of dichloroethane, and 0.06 mmol of a nickel compound shown in Table 1 as a catalyst were charged. Next, 1 atm of oxygen gas was charged into the reaction vessel and reacted at room temperature for 13 hours.

After completion of the reaction, the obtained reaction mixture was analyzed by gas chromatography, and the starting material 2-methyl-2
The conversion of decene and the product epoxide (2,
The yield of 2-dimethyl-3-heptyloxirane) was determined. Table 1 shows the results.

<Effect of the Invention> According to the method of the present invention, an epoxy group-containing compound can be obtained by a novel reaction using a nickel compound having a specific structure as a catalyst. This reaction can be carried out under mild reaction conditions such as a reaction temperature and a reaction pressure as compared with a reaction conventionally applied to the production of this type of epoxy group-containing compound. A small amount is sufficient, which is industrially advantageous.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C07D 301/06

Claims (1)

(57) [Claims] 1. A compound of the general formula (I): [Wherein, R ¹ is a linear or branched alkyl group, which may have a substituent, R ² and R ³ may be the same or different, and include a hydrogen atom, a substituted or unsubstituted alkyl And may be mutually bonded to form a ring;
R ¹ and R ³ may be bonded to each other to form a ring, and R ¹ , R ² and R ³ may be simultaneously bonded to form a condensed ring. The compound containing a double bond is converted to nickel acetate and / or the following formula (IVA): And a catalyst comprising a nickel complex represented by the following general formula (II): R ⁷ CHO (II) wherein R ⁷ is a linear or branched alkyl group or an aryl group, and has a substituent. A step of reacting with an oxygen-containing gas in the presence of an aldehyde compound represented by the following general formula (III): [Wherein R ¹ , R ² and R ³ are as defined in the above general formula (I)].