JPH06166651A - Production of epoxy group-containing compound or alpha-hydroxycarbonyl compound and their derivative - Google Patents

Abstract

PURPOSE:To obtain the subject compound under mild condition in high yield by reacting a compound having double bond with an oxygencontaining gas in the presence of a transition metal compound and an metal compound. CONSTITUTION:An epoxy-containing compound of formula IV or alphahydroxycarbonyl compound of formula V or formula VI can be produced by reacting a compound having double bond, e.g. an olefin of formula II (R<5> and R<6> are H, alkyl or aryl; R<7> and R<8> are H, alkyl, alkenyl, aryl, etc.) or an enolate of formula III (R<9> and R<10> are H, alkyl or aryl; R<11> is H, alkyl, alkoxy, etc.; R<12> to R<14> are alkyl or aryl) with an oxygen-containing gas at 10-180 deg.C (preferably 30-150 deg.C) in the presence of a compound containing transition metal (preferably a compound containing Co, Mn or Fe) and a compound of formula I (R<1> and R<2> are H, OH, alkoxy, siloxy, alkyl, etc.; R<3> and R<4> are H, alkyl, aryl, silyl, etc.).

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 epoxy group-containing compound or an .alpha.-hydroxycarbonyl compound and its derivative, and particularly to a double reaction by a novel reaction carried out in the presence of a cobalt, manganese or iron compound and an acetal compound. The present invention relates to a method capable of obtaining an epoxy group-containing compound or a carbonyl group-containing compound and its derivative from a compound having a bond.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an epoxy group-containing compound, a compound having a double bond is treated with an inert solvent such as benzene, chloroform or carbon tetrachloride.
A method of oxidizing with an organic peroxide such as perbenzoic acid, formic acid, perphthalic acid, perpropionic acid, perbutyric acid or trifluoroperacetic acid is known. Particularly, industrially, a strong acid catalyst is added to a substance that produces a peroxide, for example, a mixture of glacial acetic acid and an unsaturated compound, and hydrogen peroxide is added while heating at 60 to 70 ° C. to remove peracetic acid. A method for producing an epoxy group-containing compound using this peracetic acid is used. On the other hand, as a method for producing a carbonyl compound, a method is known in which an enol compound is reacted with hydrogen peroxide or the like in the presence of an oxidizing agent composed of a peracid such as peracetic acid or a transition metal catalyst.

[0003]

However, since the reaction in the above method is a hypersensitive reaction, it is difficult to selectively carry out the epoxidation reaction, and moreover, it is generated with the formation of the epoxy group-containing compound. A part of the epoxy group-containing compound may polymerize. Moreover, since this reaction is carried out under severe reaction conditions, side reactions are likely to occur, and the epoxy group-containing compound cannot be obtained in high yield. Further, since the peracids used as the oxidizing agent are expensive and dangerous to handle, there is a problem that the cost becomes industrially high. Further, the above-mentioned conventional method for producing a carbonyl compound has the same problem.

Further, as a method for producing an epoxy group-containing compound without using an organic peroxide, halohydrin is produced by using hypohalous acid as an unsaturated compound, and then this halohydrin is treated with an alkali to produce an epoxy group. However, this method cannot be applied to olefins having a complicated structure.

Further, in the method in which the reaction system is acidic due to the catalyst used, the solvent, the by-products produced by the progress of the reaction, etc., some compounds having a double bond as a starting material may decompose or may be decomposed. Further, there is a problem in that the produced epoxy group-containing compound may be decomposed or converted, and the range of application is limited.

Therefore, the object of the present invention is that the reaction can be carried out under milder reaction conditions than the conventional reactions used for the production of epoxy group-containing compounds, and no expensive oxidizing agents such as peracids are used. It can be performed industrially at low cost. Further, since it can be carried out under neutral conditions, it can be applied to the production using a double bond compound which is easily decomposed in an acidic state as a starting material, and further, an epoxy group which may be decomposed or converted in an acidic state. It is an object of the present invention to provide a novel method that can be applied to the production of a compound containing a compound and can obtain an epoxy group-containing compound or an α-hydroxycarbonyl compound with good catalytic efficiency.

[0007]

In order to solve the above problems, the present invention provides a compound having a double bond with a compound of formula (I):

[0008]

[Chemical 4]

[In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, a hydroxyl group, an alkoxy group, a siloxy group, a linear or branched alkyl group, an alicyclic hydrocarbon group or an aryl group. And R ³ and R ⁴ may be the same or different, and may have a hydrogen atom, a linear or branched alkyl group. It is a group, an alicyclic hydrocarbon group, an aryl group, an arylalkyl group or a silyl group, which may have a substituent and may be bonded to each other to form a ring. ] The compound which has the acetal structure represented by these, and the process of reacting with an oxygen containing gas in the presence of a transition metal containing compound are provided, The manufacturing method of an epoxy group containing compound or an alpha-hydroxy carbonyl group containing compound is provided. is there.

In particular, the present invention provides that the double bond compound has the following general formula (II):

[0011]

[Chemical 5]

[In the formula (II), R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group or aryl group, and may have a substituent. , R ⁷ and R ⁸ may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or an alkoxy group, which may have a substituent, and R ⁵ and R 8 ⁶ may combine with each other to form a ring, and further, R ⁵ , R ⁶ , and R ⁷
At least two or more groups selected from R ⁸ and R ⁸ may be bonded to each other to form a ring.
In I) ′, R ⁹ and R ^{10, which} may be the same or different, each is a hydrogen atom, a linear or branched alkyl group or aryl group, which may have a substituent, and R ¹¹ is hydrogen. An atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group or an alkoxy group, which may have a substituent, and R ⁹ and R ¹¹ are bonded to each other to form a ring. R ¹² , R ¹³ and R ¹⁴ may be the same or different and each is a lower alkyl group or an aryl group. ] It is useful as a method for producing the corresponding epoxy group-containing compound or α-hydroxycarbonyl compound or its derivative.

The transition metal-containing compound has the following general formula (III) or (III) ':

[Chemical 6]

[In the formula, R ^{15 to} R ¹⁷ , R ^{18 to} R ²⁰ , R ²³ to
R ²⁵ , R ^{26 to} R ²⁸ and R ^{29 to} R ³¹ may be the same or different and each is a lower alkyl group, an aryl group, a lower alkoxy group, a halogenated alkyl group, or the following formula (a):
(B) or (c): —CO ₂ R ³² (a) (wherein R ³² is an alkyl group or an aryl group) or the following formula (b): —N (R ³³ ) (R ³⁴ ) ( b) (wherein R ³³ and R ³⁴ may be the same or different,
It is an alkyl group or an aryl group, R ³³ and R ³⁴ may be bonded to each other to form a ring, and the ring may contain an oxygen atom or a nitrogen atom. ) —OCOR ³⁵ (c) (R ³⁵ represents an alkyl group or an aryl group), and R ^{15 to} R ¹⁷ , R ^{18 to} R ²⁰ , and R ^23.
To R ²⁵ , R ^{26 to} R ²⁸ , and R ^{29 to} R ^{31 which} are adjacent to each other may bond to each other to form a ring, and may contain a nitrogen atom in the ring; To form an aromatic ring, and the aromatic ring may have a substituent.
Further, X ¹ and X ² are oxygen atoms or nitrogen atoms, R ²¹ and R ²² are absent when X ¹ and X ² are oxygen atoms, and X ¹ and X ² are nitrogen atoms, R ²¹ and R ²² may be the same or different and each is a lower alkyl group, an aryl group, a lower alkoxy group or a halogenated alkyl group, and R ²¹ and R ²² may be bonded to each other to form a ring. Of course, a nitrogen atom may be contained in the ring, and the ring may be further bonded to form an aromatic ring, and the aromatic ring may have a substituent. ] It is preferable that it is at least 1 sort (s) chosen from the cobalt, manganese, or iron compound represented by this.

Further, it is preferable that the above step is carried out in the presence of zeolite.

Hereinafter, a method for producing the epoxy group-containing compound or the α-hydroxycarbonyl compound of the present invention (hereinafter, referred to as
The "method of the present invention" will be described in detail.

The method of the present invention is a method in which a double bond compound is used as a starting material, and an epoxy group-containing compound or an α-hydroxycarbonyl compound and its derivative can be obtained corresponding to the starting material. In the method of the present invention, the double bond compound means, for example, various olefins represented by the compound represented by the general formula (II) as a representative example, or the enolate represented by the general formula (II) ′. A compound such as a compound including a double bond in the molecule and having various groups having atoms other than carbon atoms and hydrogen atoms as constituent atoms.

In particular, in the method of the present invention, when the compound represented by the general formula (II) is used as the starting double bond compound, the epoxy group-containing compound represented by the following general formula (IV) is contained. The compound can be obtained. When the enolate represented by the general formula (II) ′ is used as a starting material, the following general formula (IV) ′ or (I
It is possible to obtain the α-hydroxycarbonyl compound represented by V) ″ and its derivatives.

[0019]

[Chemical 7]

In the above general formula (II) representing a compound which is a representative example of the double bond compound which is a starting material in the method of the present invention, R ⁵ and R ⁶ may be the same or different, and a hydrogen atom, It is a linear or branched alkyl group or aryl group, which may have a substituent.
Examples of the linear or branched alkyl group include, for example,
Methyl group, ethyl group, n-propyl group, n-butyl group,
sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group,
Examples include n-dodecyl group. As an aryl group,
Examples thereof include a phenyl group, a p-methoxyphenyl group, a p-chlorophenyl group, a p-fluorophenyl group, a naphthyl group and the like. When it has a substituent, examples of the substituent include a methyl group, an ethyl group, an isopropyl group,
Examples thereof include a tert-butyl group, a sulfonyl group, a nitro group, an N-dimethylamino group and a cyano group.

R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, a linear or branched alkyl group,
It is an alkenyl group, an aryl group, an arylalkyl group or an alkoxy group, which may have a substituent. As the linear or branched alkyl group and aryl group,
For example, the same as those exemplified above for R ⁵ and R ⁶ can be mentioned. Examples of the alkenyl group include 1-pentenyl group, 3-methyl-1-pentenyl group, 3-methyl-3-hydroxy-1-pentenyl group and the like. Examples of the arylalkyl group include:
Examples thereof include a benzyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a te group.
Examples thereof include rt-butoxy group. When having a substituent, as the substituent, for example, an alkyl group such as a methyl group and an ethyl group, a methoxy group, an alkoxy group such as an ethoxy group, a halogen, a nitro group, a cyano group, a sulfonyl group,
Hydroxyl group, acetoxy group, siloxy group, trimethylsilyloxy group, tert-butyldimethylsilyloxy group,
Examples thereof include a phenyldimethylsilyloxy group.

R ⁵ and R ⁶ may combine with each other to form a ring, and R ⁵ , R ⁶ , R ⁷ and R
^At least two or more groups selected from ⁸ may be bonded to each other to form a ring. For example, R ⁶ and R ⁷ may be bonded to each other to form a ring such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. Further, R ⁵ and R ⁸ are linked to each other, for example,
A group such as a norbornyl group may be formed.

Typical examples of the compound represented by the general formula (II) include the compounds represented by the following formulas (II-1) to (II-17).

[0024]

[Chemical 8]

As examples of the epoxy group-containing compound obtained from such a compound, the following formulas (IV-1) to (IV-1
Examples include those represented by 7).

[0026]

[Chemical 9]

Further, in the general formula (II) 'which represents an enolate which is a typical example of a double bond compound as a starting material in the method of the present invention, R ⁹ and R ¹⁰ may be the same or different, and It is an atom, a linear or branched alkyl group or aryl group, which may have a substituent. Examples of the linear or branched alkyl group or aryl group include R ⁷ and R in the general formula (II).
^The same thing as the example of ⁸ is mentioned. Also,
When R ⁹ or R ¹⁰ has a substituent, examples of the substituent include a nitro group, a cyano group and an N-dimethylamino group.

R ¹¹ is a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group or an alkoxy group. Examples of the alkyl group and the aryl group are the same as those exemplified for R ⁵ and R ⁶ in the general formula (II). Examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. Examples of the alkoxy group include, for example, the above general formula (I
The same ones as exemplified for R ⁷ and R ⁸ in I) can be mentioned.

R ⁹ and R ¹¹ may be bonded to each other to form a ring. For example, R ⁹ and R ¹¹ may be bonded to each other to form a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group or the like. The group may be formed.

R ¹² , R ¹³ and R ^{14, which} may be the same or different, are lower alkyl groups or aryl groups. The lower alkyl group is, for example, a C _{1 to} C ₆ alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group. Examples of the aryl group include a phenyl group and the like.

As typical examples of the enolates represented by the general formula (II) ', the following formulas (II-18) to (II-
26) are mentioned.

[0032]

[Chemical 10]

As an example of the α-hydroxycarbonyl compound obtained from such a compound, the following formula (IV-18)
To (IV-26) can be mentioned.

[0034]

[Chemical 11]

Particularly, as the starting material, the above-mentioned general formula (I
When an enolate in which R ¹¹ is an alkoxy group is used in I) ′, the product represented by the formula (IV) ″ is a hydroxy ester. For example,
From the compounds represented by the formulas (II-21) to (II-23), the compounds represented by the formulas (IV-21) to (IV-23) can be obtained.

The method of the present invention comprises a transition metal containing a double bond compound represented by the compound represented by the general formula (II) or the enolate represented by the general formula (II) '. It is a method of reacting with an oxygen-containing gas in the presence of the compound and the acetal compound represented by the general formula (I).

General formula (I) representing the acetal compound
In, R ¹ and R ² may be the same or different,
A hydrogen atom, a hydroxyl group, an alkoxy group, a siloxy group, a linear or branched alkyl group, an alicyclic hydrocarbon group or an aryl group, which may be bonded to each other to form a ring. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-ptoxy group, and examples of the linear or branched alkyl group or aryl group include those described above. Examples of R ⁵ and R ⁶ in the formula (II) are the same as those exemplified, or those having a substituent such as a cyanomethyl group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and examples of the aryl group include a phenyl group, a cumenyl group, a mesityl group, and a tolyl group. , Xylyl group, naphthyl group, anthryl group, phenanthryl group and the like.

In addition, R³And R^FourAre the same or different
May be a hydrogen atom, straight-chain or branched alkyl
Group, alicyclic hydrocarbon group, aryl group, arylalkyl
Group or silyl group. This straight or branched
As a rualkyl group, an aryl group or an arylalkyl group
Is, for example, R in the general formula (II).⁷And R
⁸The same thing as what was illustrated is mentioned about. Also,
Examples of the alicyclic hydrocarbon group include the above R¹And R
²The same thing as what was illustrated is mentioned about.

R ³ and R ⁴ may combine with each other to form a ring, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group or the like. .

Typical examples of the acetal compound represented by the general formula (I) include compounds represented by the following formulas (I-1) to (I-26), which are acetals of aldehydes, and ketone compounds. The following formula (I-2
7) to (I-28), compounds represented by the following formula (I-29) which is a hemiacetal, and compounds represented by the following formula (I-30) which is an orthoester. Can be mentioned.

[0041]

[Chemical 12]

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

The amount of the acetal compound represented by the general formula (I) used is 1 mol of the double bond compound represented by the general formula (II) or the general formula (II) 'which is a starting material. On the other hand, it is usually about 1 mol or more, preferably 1 to 100 mol, and may be used as a solvent.

In the method of the present invention, a transition metal-containing compound is used together with the acetal compound represented by the general formula (I). This transition metal-containing compound includes Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Examples thereof include various salts, oxides, complexes and the like of transition metals such as Zn.

Examples of the transition metal salt include halides such as cobalt chloride and cobalt bromide; cobalt acetate,
Examples thereof include salts of organic acids or inorganic acids such as cobalt carbonate, cobalt nitrate, and cobalt sulfate; hydroxides such as cobalt hydroxide.

Examples of transition metal oxides include cobalt oxide, iron oxide, manganese oxide, nickel oxide, copper oxide, zinc oxide and the like.

As a typical example of the transition metal complex,
Examples include diketones such as cobalt, manganese, and iron complexes.

Among these transition metal-containing compounds, the complex represented by the general formula (III) or (III) ″ is particularly representative. Further, in the general formula (III) or (III) ″, M is Co, Mn and F.
e is ^{desirable, R 15 ~R 17, R 18} ~R 20, R 23 ~R 25,
R ^{26 to} R ²⁸ and R ^{29 to} R ³¹ may be the same or different, and a lower alkyl group, an aryl group, a lower alkoxy group,
A halogenated alkyl group, an ester group represented by the above formula (a), an amino group represented by the above formula (b), or an acetoxy group represented by the above formula (c). The lower alkyl group is, for example, a C _{1 to} C ₆ alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group. Examples thereof include a phenyl group, a p-methoxyphenyl group and a p-chlorophenyl group. The lower alkoxy group is, for example, a C _{1 to} C ₆ alkoxy group, specifically, a methoxy group, an ethoxy group,
Examples thereof include propyloxy group and phenoxy group. Examples of the halogenated alkyl group include a trifluoromethyl group and the like.

In the formula (a), R ³² is an alkyl group or an aryl group. Examples of the alkyl group include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. To be

Further, in the above formula (b), R ³³ and R ³⁴ may be the same or different and each is an alkyl group or an aryl group. Examples of the alkyl group include a methyl group, an ethyl group and the like. , As the aryl group,
Examples thereof include a phenyl group, R ³⁰ and R
³¹ may be bonded to each other to form a pyrrolidine ring, a piperidine ring or the like, or may contain an oxygen atom or a nitrogen atom in the ring to form a morpholine ring or the like.

In the formula (c), R ³⁵ represents an alkyl group or an aryl group, and the alkyl group or the aryl group is, for example, R in the formula (a).
^The same thing as the example of ³² is mentioned.

Further, R ^{15 to} R ¹⁷ , R ^{18 to} R ²⁰ , R ^{23 to} R
Adjacent ones of ²⁵ , R ^{26 to} R ²⁸ , and R ^{29 to} R ³¹ may be bonded to each other to form a ring, may contain a nitrogen atom in the ring, and may be further bonded to an aromatic group. A ring may be formed, and this aromatic ring has a lower alkyl group such as a methyl group or an ethyl group, a lower alkoxy group such as a methoxy group or an ethoxy group, a halogen atom such as fluorine, chlorine or bromine as a substituent. You may have.

X¹And X²Is selected from oxygen or nitrogen
X is an atom¹And X²When is an oxygen atom, R
^{twenty one}, R^{twenty two}Shall not exist. X¹And X²Is
When it is a elementary atom, R^{twenty one}, R^{twenty two}Can be the same or different
, Lower alkyl groups such as methyl and ethyl, phenyl
And aryl groups such as naphthyl groups. Also, R^{twenty one}, R
^{twenty two}May be bonded to each other to form a ring,
For example, -CH₂CH ₂-Group, -CH₂CH₂CH₂−
An alicyclic ring such as a group may be formed. Furthermore, this ring is good
It may form an incense ring, and may be in the 1- or 2-position of the phenyl group or
This aromatic ring may be in the 2- or 3-position of the futyl group.
Include lower alkyl groups such as methyl groups and lower alkyl groups such as methoxy groups.
It may have a lucoxy group, and also has an alicyclic ring or aromatic group.
The incense ring may contain atoms such as oxygen and nitrogen
Which is, for example, -CH₂CH ₂CH₂N (C
H₃) CH₂CH₂CH₂-And the 2- and 3-positions of pyridine
It may be.

This general formula (III) or (III) '
As typical examples of the cobalt, manganese, or iron compound represented by, there can be mentioned compounds represented by the following formulas (III-1) to (III-22).

[0055]

[Chemical 13]

These cobalt, manganese or iron compounds
For example, the desired cobalt, manganese, iron compound
A compound forming a corresponding ligand, CoCl₂, Mn
Cl ₃, FeCl₃To be produced by the desalination method using
You can The product thus obtained is the reaction solvent
After removing etc., it may be dried and used as it is,
It may be extracted and purified with an organic solvent, or purified by sublimation under reduced pressure.
You may use it.

In the method of the present invention, the transition metal-containing compound may be used alone or in combination of two or more. Further, these transition metal-containing compounds may be obtained by any method and are not particularly limited.
Moreover, you may use a commercial item.

In the present invention, the amount of the transition metal-containing compound used is usually 0. 1 with respect to 1 mol of the double bond compound represented by the formula (II) or the formula (II) 'which is a starting material. The proportion is 005 to 30 mol%, and in particular, the proportion is 0.1 to 10 mol% in view of the high yield of the epoxy group-containing compound or the α-hydroxycarbonyl compound.

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

The partial pressure of oxygen in the oxygen-containing gas is preferably about 0.1-10 atm, more preferably 0.2-.
It is about 2.0 atm.

The reaction temperature is usually 10 to 180 ° C.,
Furthermore, 30-150 degreeC is preferable.

The reaction pressure may be normal pressure as long as the solvent is not vaporized.

In the method of the present invention, when the reaction is carried out in the presence of zeolite, the reaction rate can be increased and the epoxy group-containing compound or carbonyl group-containing compound can be obtained in high yield. It is preferable in that respect. Specific examples of this zeolite include those commercially available under the trade name Molecular Sieve, which is a synthetic zeolite.

In the method of the present invention, the reaction can also be carried out using an inert solvent. When using an inert solvent, for example, hydrocarbon solvents such as hexane and benzene, ester solvents such as ethyl acetate and butyl acetate, tetrahydrofuran, 2,5-dimethyltetrahydrofuran,
Alternatively, a halogenated hydrocarbon solvent such as dichloroethane is preferable.

From the reaction mixture obtained by the above reaction, the desired epoxy group-containing compound or α-hydroxycarbonyl compound can be recovered and purified by known methods such as distillation, adsorption, extraction and recrystallization. Can be performed in combination.

In the method of the present invention, when the compound represented by the general formula (II) is used as the double bond compound as the starting material, the epoxy group-containing compound represented by the general formula (IV) is obtained. be able to. When the enolate represented by the general formula (II) ′ is used as the starting double bond compound, the compound represented by the general formula (I) is usually used.
An α-hydroxycarbonyl compound represented by V) ′ is obtained. The α-hydroxycarbonyl compound represented by the general formula (IV) ′ has the following general formula (I):
A carbonyl group-containing compound represented by V) ″ can be obtained. The carbonyl group-containing compound represented by the general formula (IV) ″ can also be obtained by 2) treatment with a fluoride ion, for example, by adding a catalytic amount of tetrabutylammonium fluoride.

[0067]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention.

Examples 1 to 12 In each example, the formula (I
-1) represented by 3.2 mmol, (II-
Cobalt compound represented by 4) 0.06 mmol (2.
0 mol%), and the acetal compounds shown in Table 1.
With 0 ml under pure oxygen atmosphere at 45-75 ° C for 3
The mixture was heated and stirred for 10 hours to react to obtain an epoxy group-containing compound (IV-1). Moreover, the production amount of the obtained epoxy group-containing compound (IV-1) was determined by gas chromatography. The results are shown in Table 1.

[0069]

[Table 1]

(Examples 13 to 16) In each example, 3.2 mmol of the olefin represented by the formula (I-1), (I
I-4) cobalt compound represented by 0.06 mmol
(2.0 mol%) and 5.0 ml of the acetal compound shown in Table 2 under pure oxygen atmosphere at 75 ° C.
The mixture was heated and stirred for ~ 6 hours to be reacted to obtain an epoxy group-containing compound (IV-1). Moreover, the production amount of the obtained epoxy group-containing compound (IV-1) was determined by gas chromatography. The results are shown in Table 2.

[0071]

[Table 2]

(Examples 17 to 23) In each example, 3.2 mmol of the olefin represented by the formula (I-1), (I
I-4) cobalt compound represented by 0.06 mmol
(2.0 mol%) and 5.0 ml of the acetal compound shown in Table 3 are reacted by heating and stirring at 75 ° C. for 6 hours in a pure oxygen atmosphere to react with the epoxy group-containing compound (IV-
1) was obtained. The obtained epoxy group-containing compound (IV-
The amount of 1) produced was determined by gas chromatography. The results are shown in Table 3.

[0073]

[Table 3]

Examples 24 to 27 Epoxy group-containing compounds (IV-1) were obtained in the same manner as in Example 1 except that the acetal compound shown in Table 4 was used instead of the acetal compound. Further, the obtained epoxy group-containing compound (IV-1)
The production amount of was determined by gas chromatography. The results are shown in Table 4.

[0075]

[Table 4]

(Examples 28 to 36) In each example, 3.2 mmol of the olefin represented by the formula (I-1), Table 5
The cobalt compound represented by 0.06 mmol (2.0 m
ol%) and 5.0 ml of the acetal compound represented by the formula (III-18) under a pure oxygen atmosphere at 75%.
The epoxy group-containing compound (IV-
1) was obtained. The obtained epoxy group-containing compound (IV-
The amount of 1) produced was determined by gas chromatography. The results are shown in Table 5.

[0077]

[Table 5]

(Examples 37 to 42) In each example, 3.2 mmol of the olefin represented by the formula (I-1), Table 6
Cobalt compound shown in 0.06 mmol (2.0 mol
%) And 5.0 ml of the acetal compound represented by the formula (III-18), and reacted by heating and stirring at 75 ° C. for 6 hours in a pure oxygen atmosphere to react the epoxy group-containing compound (I
V-1) was obtained. The obtained epoxy group-containing compound (IV
The amount of -1) produced was determined by gas chromatography. The results are shown in Table 6.

[0079]

[Table 6]

(Examples 43 to 49) In each example, 3.2 mmol of the olefin represented by the formula (I-1), Table 7
Cobalt, manganese or iron compound shown in 0.06mm
ol (2.0 mol%) and 5.0 ml of the acetal compound represented by the formula (III-18), and reacted by heating and stirring at 45 to 75 ° C. for 3 to 12 hours in a pure oxygen atmosphere for reaction. (IV-1) was obtained. The amount of the obtained epoxy group-containing compound (IV-1) produced was determined by gas chromatography. The results are shown in Table 7.

[0081]

[Table 7]

(Examples 50 and 51) In each example, Table 8
An epoxy group-containing compound (IV-1) was obtained in the same manner as in Example 28 except that the cobalt compound shown in was used.
The amount of the obtained epoxy group-containing compound (IV-1) produced was determined by gas chromatography. The results are shown in Table 8.

[0083]

[Table 8]

Examples 52 to 58 In each example, 3.2 mmol of the olefin represented by the formula (I-1) and 0.06 mmo of the cobalt compound represented by the formula (II-4).
1 (2.0 mol%) and 5.0 ml of the acetal compound shown in Table 9 under pure oxygen atmosphere at 45 ° C.
The epoxy group-containing compound (I
V-1) was obtained. The obtained epoxy group-containing compound (IV
The amount of -1) produced was determined by gas chromatography. The results are shown in Table 9.

[0085]

[Table 9]

(Examples 59 to 65) In each example, 3.2 mmol of the olefin represented by the formula (I-1) and 0.06 mmo of the cobalt compound represented by the formula (II-4).
1 (2.0 mol%), 500 mg of synthetic zeolite (manufactured by Nikka Seiko Co., Ltd., Molecular Sieves 4A), and 5.0 ml of the acetal compound shown in Table 10 were heated and stirred at 45 ° C. for 10 hours in a pure oxygen atmosphere. And reacted to obtain an epoxy group-containing compound (IV-1). The amount of the obtained epoxy group-containing compound (IV-1) produced was determined by gas chromatography. The results are shown in Table 10.

[0087]

[Table 10]

(Examples 66 to 69) In each example, 3.2 mmol of the olefin represented by the formula (I-6) and 0.06 mmo of the cobalt compound represented by the formula (II-4).
1 (2.0 mol%), synthetic zeolite (manufactured by Nikka Seiko Co., Ltd., Molecular Sieves 4A) 500 mg, and the amount of the acetal compound represented by the formula (III-3) shown in Table 11 in a pure oxygen atmosphere. 20 at 45 ° C
The epoxy group-containing compound (IV
-6) was obtained. The obtained epoxy group-containing compound (IV-
The amount of 6) produced was determined by gas chromatography. The results are shown in Table 11.

[0089]

[Table 11]

(Examples 70 to 79) In each example, Table 1
3.2 mmol of the olefin shown in 2 and 0.06 mmol (2.0 mo of the cobalt compound represented by the formula (II-1).
1%), synthetic zeolite (Nika Seiko Co., Ltd., Molecular Sieves 4A) 500 mg, and formula (III-
Acetal compound represented by 3) 5.0 ml to 20.0
The reaction is carried out by stirring the mixture with ml in a pure oxygen atmosphere at 45 ° C. for 10 to 20 hours to cause reaction, and epoxy group-containing compounds (IV-1) to (IV-1 corresponding to each starting material olefin.
0) was obtained. The obtained epoxy group-containing compound (IV-
The production amounts of 1) to (IV-10) were determined by gas chromatography. The results are shown in Table 12.

[0091]

[Table 12]

(Examples 80 to 86) In each example, Table 1
3.2 mmol of the olefin shown in 3 and 0.06 mmol (2.0 mo of the cobalt compound represented by the formula (II-1).
1%), synthetic zeolite (Nika Seiko Co., Ltd., Molecular Sieves 4A) 500 mg, and formula (III-
With 20.0 ml of the acetal compound represented by 3), the mixture was heated and stirred at 45 ° C. for 4 to 20 hours in a pure oxygen atmosphere, and the epoxy group-containing compounds (IV-11) to (IV- 17) was obtained. The obtained epoxy group-containing compounds (IV-11) to (IV-17)
The production amount of was determined by gas chromatography. The results are shown in Table 13.

[0093]

[Table 13]

(Examples 87 to 95) In each example, Table 1
3.2 mmol of the enolate shown in FIG. 4 and 0.06 mmol of the cobalt compound represented by the formula (II-1) (2.0 mo
1%), synthetic zeolite (Nika Seiko Co., Ltd., Molecular Sieves 4A) 500 mg, and formula (III-
Acetal compound represented by 3) 5.0 ml to 20.0
After stirring and reacting with ml in a pure oxygen atmosphere at 45 ° C. for 4 to 14 hours, a small amount of tetrabutylammonium fluoride was added to the α-hydroxycarbonyl compound (IV-18 corresponding to each starting material enolate. )
~ (IV-26) were obtained. The amount of the obtained α-hydroxycarbonyl compounds (IV-18) to (IV-26) was determined by gas chromatography. The results are shown in Table 14.

[0095]

[Table 14]

[0096]

According to the method of the present invention, an epoxy group-containing compound or an α-hydroxycarbonyl compound can be efficiently produced by a simple reaction with a mild reaction using an oxygen-containing gas. Further, it has an advantage that the consumption of acetal to be coexisted in the reaction can be as small as about 1 to 2 equivalents with respect to the epoxy compound produced. Further, since an expensive oxidizing agent such as peracids is not used, it can be industrially carried out at low cost. Further, since it can be carried out under neutral conditions, it can be applied to the production using a double bond compound which is easily decomposed in an acidic state as a starting material, and an epoxy group which may be decomposed or converted in an acidic state. There is an advantage that it can be applied to the production of contained compounds.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 69/732 9279-4H C07D 301/06 303/04 303/14 C07F 7/18 A 8018-4H // C07B 61/00 300 (72) Inventor Toru Yamada 580-32 Mitsui Petrochemical Industry Co., Ltd.

Claims (4)

[Claims] 1. A double bond-forming compound is represented by the formula (I): [Wherein R ¹ and R ^{2, which} may be the same or different, each represents a hydrogen atom, a hydroxyl group, an alkoxy group, a siloxy group, a linear or branched alkyl group, an alicyclic hydrocarbon group or an aryl group, And R ³ and R ⁴ may be the same or different, and may be a hydrogen atom, a linear or branched alkyl group, or an aliphatic group. It is a cyclic hydrocarbon group, an aryl group, an arylalkyl group or a silyl group, which may have a substituent and may be bonded to each other to form a ring. ]
A method for producing an epoxy group-containing compound or an α-hydroxycarbonyl compound and a derivative thereof, which comprises a step of reacting with an oxygen-containing gas in the presence of a compound having an acetal structure represented by and a transition metal-containing compound. 2. The double bond compound is represented by the following general formula (I
I) or (II) ': [In the formula (II), R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom, a linear or branched alkyl group or aryl group, which may have a substituent, R 5
⁷ and R ⁸ may be the same or different and each is a hydrogen atom,
It is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or an alkoxy group, which may have a substituent, and R ⁵ and R ⁶ may be bonded to each other to form a ring. , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring, and in formula (II) ′, R ⁹ and R ¹⁰ May be the same or different and each is a hydrogen atom, a linear or branched alkyl group or an aryl group, which may have a substituent, and R ¹¹ is a hydrogen atom, an alkyl group,
An alicyclic hydrocarbon group, an aryl group or an alkoxy group, which may have a substituent, and R ⁹ and R
¹¹ may combine with each other to form a ring, R ¹²
R ¹³ and R ¹⁴ may be the same or different and each is a lower alkyl group or an aryl group. ] The epoxy group-containing compound or α- according to claim 1, which is a compound represented by
A method for producing a hydroxycarbonyl group-containing compound. 3. The transition metal-containing compound is represented by the following general formula (III) or (III) ′: ^{Wherein, R 15 ~R 17, R 18} ~R 20, R 23 ~R 25, R 26 ~
R ²⁸ and R ^{29 to} R ³¹ may be the same or different and each is a lower alkyl group, an aryl group, a lower alkoxy group, a halogenated alkyl group, or the following formula (a), (b) or (c): —CO ₂ R ³² (a) (wherein R ³² is an alkyl group or an aryl group) or the following formula (b): —N (R ³³ ) (R ³⁴ ) (b) (wherein R ³³ and R ³⁴ May be the same or different,
It is an alkyl group or an aryl group, R ³³ and R ³⁴ may be bonded to each other to form a ring, and the ring may contain an oxygen atom or a nitrogen atom. ) —OCOR ³⁵ (c) (R ³⁵ represents an alkyl group or an aryl group), and R ^{15 to} R ¹⁷ , R ^{18 to} R ²⁰ , and R ^23.
To R ²⁵ , R ^{26 to} R ²⁸ , and R ^{29 to} R ^{31 which} are adjacent to each other may bond to each other to form a ring, and may contain a nitrogen atom in the ring; To form an aromatic ring, and the aromatic ring may have a substituent.
Further, X ¹ and X ² are oxygen atoms or nitrogen atoms, R ²¹ and R ²² are absent when X ¹ and X ² are oxygen atoms, and X ¹ and X ² are nitrogen atoms, R ²¹ and R ²² may be the same or different and each is a lower alkyl group, an aryl group, a lower alkoxy group or a halogenated alkyl group, and R ²¹ and R ²² may be bonded to each other to form a ring. Of course, a nitrogen atom may be contained in the ring, and the ring may be further bonded to form an aromatic ring, and the aromatic ring may have a substituent. ] The manufacturing method of the epoxy group containing compound or carbonyl group containing compound of Claim 1 which is at least 1 sort (s) selected from the cobalt, manganese, or iron compound represented by these. 4. The method for producing an epoxy group-containing compound or a carbonyl group-containing compound according to claim 1, wherein the step is carried out in the presence of zeolite.