JP3434526B2 - Method for producing epoxy-containing compound, α-hydroxycarbonyl compound or alkylsilyl or arylsilyl derivative of α-hydroxycarbonyl compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an epoxy group-containing compound, an α-hydroxycarbonyl compound or an alkylsilyl or arylsilyl derivative of an α-hydroxycarbonyl compound, and particularly cobalt, manganese or iron as a transition metal (element). A compound having a double bond, an epoxy group-containing compound, an α-hydroxycarbonyl compound, or a compound having an acetal structure (also referred to as “acetal compound” in the present invention) in the presence of It relates to a method by which an alkylsilyl or arylsilyl derivative of an α-hydroxycarbonyl compound can be obtained.

[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 perbenzoic acid, performic acid or perphthalic acid in an inert solvent such as benzene, chloroform or carbon tetrachloride. There is known a method of oxidizing with an organic peroxide such as perpropionic acid, perbutyric acid or trifluoroperacetic acid. 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, an 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 expensive oxidants such as peracids are not 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. A novel method which can be applied to the production of a containing compound, and can obtain an epoxy group-containing compound, an α-hydroxycarbonyl compound or an alkylsilyl or arylsilyl derivative of an α-hydroxycarbonyl compound with good catalytic efficiency To provide.

[0007]

In order to solve the above problems, the present invention provides the following general formula (II) or (II) ':

[0008]

[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 an 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 an 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. ] The double bond compound represented by general formula (I):

[0010]

[Chemical 6]

[Wherein 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 having an acetal structure represented by the formula, and a step of reacting with an oxygen-containing gas in the presence of a transition metal-containing compound , represented by the following general formula (IV)
Table in that the epoxy group-containing compound represented by the following general formula (IV) ''
Α- hydroxy carbonyl compound or the following general be
The present invention provides a method for producing an alkylsilyl or arylsilyl derivative of an α-hydroxycarbonyl compound represented by formula (IV) ′ .

[Chemical 7] [In the formula (IV), R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above.
R ⁵ in the formula ^{(II), R 6, R} 7 and R ⁸ as defined der
R ⁹ in formula (IV) ′ and formula (IV) ″
R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each represented by the above formula (I
I) ′ in R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ ;
Are synonymous. ]

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

[Chemical 8]

[Wherein 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) —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 M in the above general formula is at least one selected from cobalt, manganese, and iron.

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

Hereinafter, the epoxy group-containing compound of the present invention, α
-Method for producing alkylsilyl or arylsilyl derivative of hydroxycarbonyl compound or α-hydroxycarbonyl compound (hereinafter referred to as "method of the present invention")
Will be described in detail.

In the method of the present invention, a double bond compound is used as a starting material, and an epoxy group-containing compound, an α-hydroxycarbonyl compound or an alkylsilyl or arylsilyl derivative of an α-hydroxycarbonyl compound corresponding to the starting material is used. It is a method that can be obtained. 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 above general formula (II) is used as the starting double bond compound, it contains an epoxy group represented by the following general formula (IV). The compound can be obtained. When the enolate represented by the general formula (II) ′ is used as the starting material, α represented by the following general formula (IV) ′ is used.
It is possible to obtain an alkylsilyl or arylsilyl derivative of a hydroxycarbonyl compound or an α-hydroxycarbonyl compound represented by the general formula (IV) ″.

[0018]

[Chemical 9]

In the general formula (II), which represents a compound that is a typical example of a double bond compound that 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,
tert-butyl group, sulfonyl group, nitro group, N, N
-A dimethylamino group, a cyano group, etc. are mentioned.

R ⁷ and R ⁸ may be the same or different and each is a hydrogen atom, a linear or branched alkyl group or alkenyl group, an aryl group, an arylalkyl group or an alkoxy group and has a substituent. You may have. As the linear or branched alkyl group and aryl group, for example, the same groups as those exemplified 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 a benzyl group and the like, and examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group and the like. When having a substituent, as the substituent, for example, a methyl group, an alkyl group such as 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, a hydroxyl group, an acetoxy group, Examples thereof include a siloxy group, a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group and 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 ring such as a norbornene ring may be formed.

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

[0023]

[Chemical 10]

As examples of the epoxy group-containing compound obtained from such a compound, the following general formulas (IV-1) to (I
And those represented by V-17).

[0025]

[Chemical 11]

Further, in the general formula (II) 'which represents an enolate which is a typical example of the 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 hydrogen 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 and aryl group include R ⁷ and R ⁸ in the general formula (II).
The same thing as what was illustrated is mentioned about. Also, R
^{When 9} or R ¹⁰ has a substituent, examples of the substituent include a nitro group, a cyano group and an N, 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 are bonded to each other to form a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a norbornyl group. Groups such as

R ¹² , R ¹³ and R ^{14, which} may be the same or different, are a lower alkyl group or an aryl group. 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 general formula (II-18)' to
Examples include those represented by (II-26) ′.

[0031]

[Chemical 12]

Examples of α-hydroxycarbonyl compounds and alkylsilyl or arylsilyl derivatives of α-hydroxycarbonyl compounds obtained from such compounds are represented by the following general formulas (IV-18) '' to (IV-
20) '', (IV-22) '' and (IV-2
4) ″ to (IV-26) ″, and those represented by the following general formulas (IV-21) ′ and (IV-23) ′.

[0033]

[Chemical 13]

Particularly, as a starting material, the above-mentioned general formula (I
In the case of using an enolate in which R ¹¹ is an alkoxy group in I) ′, the product of the general formula (I
V) ″ or a compound represented by the general formula (IV) ′ is
It becomes an α-hydroxy ester or its alkylsilyl or arylsilyl derivative. For example, the general formula (I
I-21) 'to (II-23)' and an α-hydroxy ester represented by the general formula (IV-22) '' and general formulas (IV-21) 'and (IV-2
An alkylsilyl derivative of α-hydroxy ester represented by 3) ′ is 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:
Examples of R ⁵ and R ⁶ in the general 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. , A xylyl group,
Examples thereof include a naphthyl group, an anthryl group and a phenanthryl group.

R ³ and R ^{4, which} may be the same or different, are a hydrogen atom, a linear or branched alkyl group, an alicyclic hydrocarbon group, an aryl group, an arylalkyl group or a silyl group. Examples of the linear or branched alkyl group, aryl group or arylalkyl group include R ⁷ and R in the general formula (II).
^The same thing as the example of ⁸ is mentioned. Also,
Examples of the alicyclic hydrocarbon group include R ¹ and R described above.
^The same thing as the example of ² is mentioned.

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 ketones. 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.

[0040]

[Chemical 14]

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.

Further, 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 and the like.

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

Typical examples of the transition metal complex include:
Examples include diketones such as cobalt, manganese, and iron complexes.

Of these transition metal-containing compounds, the complex (compound) represented by the general formula (III) or (III) 'is particularly representative. Furthermore, the general formula (I
In II) or (III) ', M is Co, Mn and Fe is ^{preferably, 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 each is a lower alkyl group, an aryl group, a lower alkoxy group, a halogenated alkyl group or an ester group represented by the above formula (a), An amino group represented by the above formula (b),
Alternatively, it is an acetoxy group (acyloxy group) represented by the above formula (c). The lower alkyl group is, for example, a C ₁ -C ₆ alkyl group, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert group.
Examples of the aryl group include a phenyl group, a p-methoxyphenyl group and a p-chlorophenyl group. As the lower alkoxy group, for example,
An alkoxy group C ₁ -C _6, specifically, methoxy group, an ethoxy group, a propyloxy group (propoxy group), 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, and R ³³ and R ³⁴
May combine with 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 examples of the alkyl group or the aryl group include 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.

X ¹ and X ² represent an atom selected from oxygen and nitrogen, and when X ¹ and X ² are oxygen atoms, R
²¹ and R ²² do not exist. When 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 such as a methyl group or an ethyl group, or an aryl group such as a phenyl group or a naphthyl group. Also, R ²¹ , R
²² may form a bond each other respectively, for example, -CH ₂ CH ₂ - group, -CH ₂ CH ₂ CH ₂ - may form a group. Further, R ²¹ and R ²² are the 1- and 2-positions of the phenyl group (benzene ring) and the naphthyl group (naphthalene ring).
In the 2, 3 position, and the aromatic ring may have a lower alkyl group such as a methyl group or a lower alkoxy group such as a methoxy group. Furthermore, an atom such as oxygen or nitrogen may be contained in the above-mentioned bond, which is, for example, —CH ₂ CH ₂ CH ₂ N (CH ₃ ) CH ₂ CH ₂ C.
H ₂ - may become a 2,3-position of or pyridine ring.

This general formula (III) or (III) '
As typical examples of the cobalt, manganese, or iron compound represented by the following, compounds represented by the following formulas (III-1) to (III-19) and (III-20) 'to (III-22)' are listed. You can

[0054]

[Chemical 15]

These cobalt, manganese or iron compounds include, for example, a compound which forms a ligand corresponding to a desired cobalt, manganese or iron compound, CoCl ₂ , Mn.
It can be produced by a desalting method using Cl ₃ and FeCl ₃ . The product thus obtained may be dried and used as it is, after removing the reaction solvent and the like,
It may be extracted and purified with an organic solvent, or may be purified by sublimation under reduced pressure before use.

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 above formula (II) or the above formula (II) 'which is a starting material. It is a proportion of 005 to 30 mol%, and in particular, in terms of high yield of the epoxy group-containing compound, the α-hydroxycarbonyl compound or the alkylsilyl or arylsilyl derivative of the α-hydroxycarbonyl compound,
A proportion of 1 to 10 mol% is common.

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 (eg 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 does not vaporize.

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, α-hydroxycarbonyl compound or α-hydroxycarbonyl compound alkyl group can be used. It is preferable in that a silyl or arylsilyl derivative can be obtained in high yield. 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 an inert solvent is used, for example, a hydrocarbon solvent such as hexane and benzene, an ester solvent such as ethyl acetate and butyl acetate, an ether solvent such as tetrahydrofuran and 2,5-dimethyltetrahydrofuran, or a halogenation such as dichloroethane. Hydrocarbon solvents are preferred.

Recovery of the desired epoxy group-containing compound, α-hydroxycarbonyl compound and alkylsilyl or arylsilyl derivative of α-hydroxycarbonyl compound from the reaction mixture obtained by the above reaction,
Purification is a known method, for example, a method by distillation, adsorption,
It can be performed by combining methods such as extraction and recrystallization.

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 alkylsilyl or arylsilyl derivative of the α-hydroxycarbonyl compound represented by V) ′ is obtained. The derivative of the alkylsilyl or arylsilyl derivative of the α-hydroxycarbonyl compound represented by the general formula (IV) 'is treated under 1) hydrolysis conditions, or 2) treated with fluoride ion (for example, tetrabutylammonium). By adding a catalytic amount of fluoride), the α-hydroxycarbonyl compound represented by the general formula (IV) ″ can be obtained.

[0066]

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, 3.2 mmol of the olefin represented by the general formula (II-1) and 0.06 mmol (2.0 mol%) of the cobalt compound represented by (III-4). , And 5.0 ml of the acetal compound shown in Table 1 under a pure oxygen atmosphere at 45 to 75 ° C. for 3 to 10 hours with stirring and reaction 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.

[0068]

[Table 1]

Examples 13 to 16 In each example, 3.2 mmol of the olefin represented by the general formula (II-1) and 0.06 mmol (2.0 mol%) of the cobalt compound represented by (III-4). , And 5.0 ml of the acetal compound shown in Table 2 under a pure oxygen atmosphere at 75 ° C. under heating with stirring for 3 to 6 hours to cause reaction 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.

[0070]

[Table 2]

Examples 17 to 23 In each example, 3.2 mmol of the olefin represented by the general formula (II-1) and 0.06 mmol (2.0 mol%) of the cobalt compound represented by (III-4). , And 5.0 ml of the acetal compound shown in Table 3 were reacted by heating and stirring at 75 ° C. for 6 hours in a pure oxygen atmosphere 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 3.

[0072]

[Table 3]

Examples 24 to 27 In each example, an epoxy group-containing compound (IV-1) was obtained in the same manner as in Example 1 except that the acetal compound shown in Table 4 was replaced. Moreover, the production amount of the obtained epoxy group-containing compound (IV-1) was determined by gas chromatography. The results are shown in Table 4.

[0074]

[Table 4]

(Examples 28 to 36) In each example, 3.2 mmol of the olefin represented by the general formula (II-1) and the cobalt compound 0.
06 mmol (2.0 mol%), and the general formula (I-
The compound (IV-1) containing an epoxy group was obtained by reacting with 5.0 ml of the acetal compound represented by 18) by heating and stirring at 75 ° C. for 6 hours in a pure oxygen atmosphere. The amount of the obtained epoxy group-containing compound (IV-1) produced was determined by gas chromatography. The results are shown in Table 5.

[0076]

[Table 5]

Examples 37 to 42 In each example, 3.2 mmol of the olefin represented by the general formula (II-1) and 0.06 of the cobalt compound shown in Table 6 were used.
mmol (2.0 mol%), and the general formula (I-1
Together with 5.0 ml of the acetal compound represented by 8),
In a pure oxygen atmosphere, the mixture was heated and stirred at 75 ° C. for 6 hours to cause a reaction 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 6.

[0078]

[Table 6]

Examples 43 to 49 In each example, 3.2 mmol of the olefin represented by the general formula (II-1), 0.06 mmol (2.0 mol%) of the cobalt, manganese or iron compound shown in Table 7, And an acetal compound represented by the general formula (I-18).
0 ml with pure oxygen atmosphere at 45-75 ℃ 3 ~
The mixture was heated and stirred for 12 hours for reaction 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 7.

[0080]

[Table 7]

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

[0082]

[Table 8]

Examples 52 to 58 In each example, 3.2 mmol of the olefin represented by the general formula (II-1) and 0.06 mmol (2.0 mol of the cobalt compound represented by the general formula (III-4). %), And 5.0 ml of the acetal compound shown in Table 9,
In a pure oxygen atmosphere, the mixture was heated and stirred at 45 ° C. for 10 hours to be 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 9.

[0084]

[Table 9]

Examples 59 to 65 In each example, 3.2 mmol of the olefin represented by the general formula (II-1) and 0.06 mmol (2.0 mol of the cobalt compound represented by the general formula (III-4). %), Synthetic zeolite (manufactured by Nikka Seiko Co., Ltd., Molecular Sieves 4A) 500 mg, and 5.0 ml of the acetal compound shown in Table 10 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 10.

[0086]

[Table 10]

Examples 66 to 69 In each example, 3.2 mmol of the olefin represented by the general formula (II-6) and 0.06 mmol (2.0 mol of the cobalt compound represented by the general formula (III-4). %), Synthetic zeolite (manufactured by Nikka Seiko Co., Ltd., Molecular Sieves 4A) 500 mg, and the acetal compound represented by the general formula (I-3) together with the amounts shown in Table 11 under pure oxygen atmosphere at 45 ° C. The mixture was heated and stirred for 20 hours for reaction to obtain an epoxy group-containing compound (IV-6). The amount of the obtained epoxy group-containing compound (IV-6) produced was determined by gas chromatography. The results are shown in Table 11.

[0088]

[Table 11]

Examples 70 to 79 In each example, the olefins of 3.2 mmo shown in Table 12 were used.
1, 0.06 mmol (2.0 mol%) of a cobalt compound represented by the general formula (III-1), synthetic zeolite (manufactured by Nikka Seiko Co., Ltd., Molecular Sieves 4A) 50
0 mg, and 5.0 ml to 20.0 ml of the acetal compound represented by the general formula (I-3) are reacted by heating and stirring at 45 ° C. for 10 to 20 hours in a pure oxygen atmosphere,
Epoxy group-containing compounds (IV-1) to (IV-10) corresponding to each starting material olefin were obtained. The production amount of the obtained epoxy group-containing compounds (IV-1) to (IV-10) was determined by gas chromatography. The results are shown in Table 12.

[0090]

[Table 12]

(Examples 80 to 86) In each example, the olefins of 3.2 mmo shown in Table 13 were used.
1, 0.06 mmol (2.0 mol%) of a cobalt compound represented by the general formula (III-1), synthetic zeolite (manufactured by Nikka Seiko Co., Ltd., Molecular Sieves 4A) 50
0 mg and 20.0 ml of the acetal compound represented by the general formula (I-3) in a pure oxygen atmosphere at 45 ° C.
And stirring for 4 to 20 hours, and the epoxy group-containing compounds (IV-11) to (IV
-17) was obtained. The obtained epoxy group-containing compound (IV
The amounts of -11) to (IV-17) produced were determined by gas chromatography. The results are shown in Table 13.

[0092]

[Table 13]

Examples 87 to 95 In each example, the enolate of 3.2 mmo shown in Table 14 was used.
1, 0.06 mmol (2.0 mol%) of a cobalt compound represented by the general formula (III-1), synthetic zeolite (manufactured by Nikka Seiko Co., Ltd., Molecular Sieves 4A) 50
0 mg and 5.0 ml to 20.0 ml of the acetal compound represented by the general formula (I-3) are reacted by heating and stirring at 45 ° C. for 4 to 14 hours in a pure oxygen atmosphere, and then reacted with tetrabutylammonium fluoride. A small amount of a ride was added to the α-hydroxycarbonyl compound (IV-18) '' to (IV-2 corresponding to each starting material enolate.
0) '', (IV-22) '', (IV-24) '' ~
(IV-26) '' and an alkylsilyl derivative of an α-hydroxycarbonyl compound (IV-21) ', (IV
-23) 'was obtained. The production amounts of the obtained α-hydroxycarbonyl compound and the alkylsilyl derivative of the α-hydroxycarbonyl compound were determined by gas chromatography. The results are shown in Table 14.

[0094]

[Table 14]

[0095]

According to the method of the present invention, an epoxy group-containing compound, an α-hydroxycarbonyl compound or an α-hydroxycarbonyl compound or an α-hydroxycarbonyl compound or an α-hydroxycarbonyl compound or
-Alkylsilyl or arylsilyl derivatives of hydroxycarbonyl compounds can be prepared. 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 front page (51) Int.Cl. ⁷ Identification code FI C07C 49/82 C07C 49/82 67/00 67/00 69/732 69/732 Z C07D 301/06 C07D 301/06 303/04 303/04 303/14 303/14 303/16 303/16 303/32 303/32 C07F 7/18 C07F 7/18 A // C07B 61/00 300 C07B 61/00 300 (72) Inventor Toru Yamada Sodegaura, Chiba Prefecture Mayor Ura Takuji No. 580-32 Mitsui Petrochemical Industry Co., Ltd. (56) Reference JP-A-4-169547 (JP, A) JP-A-4-334342 (JP, A) JP-A-54-122218 ( JP, A) US Patent 2785185 (US, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 45/37 C07C 49/17 C07C 49/713 C07C 49/82 C07C 67/00 C07C 69 / 732 C07D 301/06 C07D 303/04 C07D 303/14 C07D 303/16 C07D 303/32 B01J 31/28 B01J 31/32 B01J 29/00 C07F 7/18 C07B 61/00 300 CA (STN) CAOLD (STN ) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. The following general formula (II) 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 an 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 the 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 double bond compound represented by the following general 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. ]
Compounds having an acetal structure represented in, and the presence of a transition metal-containing compound, comprising the step of reacting with an oxygen-containing gas, an epoxy group-containing compound represented by the following general formula (IV), the following general formula (IV) And an α-hydroxycarbonyl compound represented by the following general formula (IV) ′
A method for producing an alkylsilyl or arylsilyl derivative of an represented α-hydroxycarbonyl compound. [Chemical 3] [In the formula (IV), R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above.
R ⁵ in the formula ^{(II), R 6, R} 7 and R ⁸ as defined der
R ⁹ in formula (IV) ′ and formula (IV) ″
R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each represented by the above formula (I
I) ′ in R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ ;
Are synonymous. ] 2. 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) —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 epoxy group-containing compound, α-hydroxycarbonyl compound or α-hydroxycarbonyl according to claim 1, wherein M in the above general formula is at least one selected from cobalt, manganese and iron. A method for producing an alkylsilyl or arylsilyl derivative of a compound. 3. The method for producing an epoxy group-containing compound, an α-hydroxycarbonyl compound or an alkylsilyl or arylsilyl derivative of an α-hydroxycarbonyl compound according to claim 1, wherein the step is carried out in the presence of zeolite.