JP2801692B2 - Method for producing silyl peroxide - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel method for producing silyl peroxide using a cobalt complex.

Technical Background of the Invention and Problems Thereof Conventionally, silyl peroxide has been used as a polymerization initiator, an oxidizing agent, a coupling agent, or the like.

Such silyl peroxide can be obtained by first converting an olefin such as 4-phenyl-1-butene into a 30%
After mixing with the above hydrogen peroxide solution and carefully adding a strong acid such as concentrated sulfuric acid and the like to react with each other, a hydroperoxide is synthesized, and once the hydroxyperoxide is isolated and purified, a silyl chloride or the like is obtained. It has been synthesized by a method of reacting with such a silylating agent.

However, this method is extremely dangerous because it has a low acid stability and synthesizes a potentially explosive peroxide in the presence of a strong acid such as concentrated sulfuric acid.

Further, since the silylating agent used in the above reaction has high reactivity with water, it is necessary to once separate peroxide produced under water-containing conditions to remove water, and then react with the silylating agent. That is, this reaction had to be carried out in two stages, and there was a problem that the operation became very complicated.

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a method capable of efficiently producing silyl peroxide from an olefin compound using a cobalt complex. It is an object.

The production method of the present invention is a method for producing a silyl peroxide represented by the following formula [V] and / or a silyl peroxide represented by the following formula [VI].

However, in the formulas [V] and [VI], R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, an aryl group, a lower alkoxy group and an arylalkyl group. And at least one of R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom,
R ¹⁰ and R ¹¹ , R ¹² and R ¹³ are a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an arylalkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a carbamoyl group And an atom or group selected from the group consisting of a cyano group, and R ¹⁰ and R ¹² or R ¹¹ and R ¹³ may form a ring together. Where R ¹⁰
Of to R ^13, any one is a group other than a hydrogen atom.

The method according to the present invention for producing the silyl peroxide as described above includes a cobalt complex of a β-dicarbonyl compound represented by the following formula [I]; [In the above formula [I], R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, an arylalkyl group, Fluoromethyl group, alkoxycarbonyl group,
An alkylcarbonyl group, an atom or a group selected from the group consisting of a cyano group and a carbamoyl group, wherein R ³ and R ⁶ each independently represent a lower alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group and a cycloalkyl group; Represents a group selected from the group consisting of alkyl groups. And a hydroperoxide of the formula [II] (In the above formula [II], X, Y and Z each independently represent a hydrogen atom, an atom selected from the group consisting of a lower alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group and an arylalkyl group, or X and Y
And at least one of Z is a group other than a hydrogen atom. A) a derivative represented by the following formula [III]; (In the above formula [III], R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms,
It represents a group or an atom selected from the group consisting of an aryl group, a lower alkoxy group and an arylalkyl group, and at least one of R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom. ) And a chain olefin represented by the following formula [IV]; (In the above formula [IV], R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are
Each independently selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an arylalkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a carbamoyl group and a cyano group. Represents an atom or a group, and R ¹⁰ and R ¹² or R ¹¹ and R ¹³ may form a ring together. However, R ^{10 to} R ¹³ are not all hydrogen atoms. And an oxygen-containing gas.

According to the method for producing a silyl peroxide according to the present invention, since a cobalt complex is used as a catalyst, silyl peroxide can be synthesized from an olefin in one step. Further, this reaction is highly safe because it is not necessary to react a highly dangerous intermediate such as peroxide under unstable conditions as in the conventional reaction.

Further, by using the above-mentioned catalyst, silyl peroxide can be produced in high yield using an olefin having a functional group as a raw material.

Next, the present invention will be specifically described.

First, a cobalt complex used as a catalyst in the production method of the present invention will be described.

The cobalt complex used in the present invention is a cobalt complex of a β-dicarbonyl compound, and this cobalt complex can be represented by the following formula [I].

In the above formula [I], R ¹ , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, an arylalkyl group, a trifluoro group. Methyl group, alkoxycarbonyl group,
An alkylcarbonyl group, an atom or a group selected from the group consisting of a cyano group and a carbamoyl group, wherein R ³ and R ⁶ are each independently a lower alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group and a siluloalkyl group; Represents a group selected from the group consisting of groups;

The lower alkyl group is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and this alkyl group may be linear or branched. Specific examples of such an alkyl group include a methyl group, an ethyl group, and n-
Propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl and n-nonyl Groups. Among these lower alkyl groups, preferred alkyl groups as R ¹ , R ² , R ⁴ and R ⁵ are alkyl groups having 1 to 6 carbon atoms, particularly ethyl group, n-butyl group, t-butyl group,
Isobutyl group, n-hexyl group, an alkyl group preferred as R ³ and R ⁶ is an alkyl group having 1 to 6 carbon atoms,
Particularly, an ethyl group, an n-butyl group, a t-butyl group, an isobutyl group and an n-hexyl group.

Further, specific examples of the cycloalkyl group include a cyclohexyl group, a cyclopentyl group, a cyclohebutyl group,
A cyclooctyl group can be mentioned. As described above, the cycloalkyl group may have a substituent on the cycloalkyl ring. Among these cycloalkyl groups, preferred cycloalkyl groups as R ¹ , R ² , R ⁴ and R ⁵ are a 1-methylcyclopentyl group, a 1-methylcyclohexyl group, a 4-t-butylcyclohexyl group,
Preferred cycloalkyl groups as R ³ and R ⁶ are a 1-methylcyclopentyl group and a 1-methylcyclohexyl group.

In the aryl group, a hydrogen atom on the aromatic ring may be substituted with another atom such as a halogen atom, or a substituent, and specific examples of such an aryl group include p-bromo. A halogenated phenyl group such as a phenyl group,
In addition to a naphthyl group and a phenyl group, the following formula (1)
To (19).

The aryl group may be bonded to a carbon atom via a lower alkylene group such as a methylene group, and specific examples of these groups are those represented by the following formulas (21) to (39).
And the group represented by

Among these aryl groups, preferred arylalkyl groups as R ¹ , R ² , R ⁴ and R ⁵ are those represented by formulas (29) and (3)
0), Equation (31), Equation (32), Equation (33), Equation (34), Equation (3
5), groups represented by the formulas (36), (37), (38) and (39).

Further, examples of the alkoxycarbonyl group include a group represented by the following formula.

Here, in the above formula, p represents an integer of 1 to 6. Specific examples of such an alkoxycarbonyl group include a methoxy group, an ethoxy group, and an n-
Examples include a propoxy group and an alkoxycarbonyl group which is an n-butoxy group or an n-pentoxy group. Of these alkoxycarbonyl groups, R ¹ ,
Preferred groups for R ² , R ⁴ and R ⁵ are alkoxycarbonyl groups wherein the alkoxy groups are methoxy, ethoxy, propoxy and butoxy groups.

Examples of the alkylcarbonyl group include a group in which an alkyl group constituting the above-mentioned alkoxycarbonyl group is bonded to a carbonyl group.

 The carbamoyl group is represented by the following formula.

However, in the above formula, R ¹⁴ and R ¹⁵ each independently represent an atom or a group selected from a hydrogen atom, a lower alkyl group and a cycloalkyl group. Further, R ¹⁴ and R ¹⁵ may form a ring together.
In this case, -O-, -S-, -NR ^16- (where R ¹⁶ is a lower alkyl group or a hydrogen atom), or-
R ¹⁴ and R ¹⁵ may be linked via N = to form a ring.

Here, examples of the lower alkyl group and the cycloalkyl group include the groups exemplified above.

Specific examples of such a carbamoyl group include a dimethylaminocarbamoyl group, a methylaminocarbamoyl group, a diethylaminocarbamoyl group, a dipropylaminocarbamoyl group, a methylethylaminocarbamoyl group, a piperidinocarbamoyl group, and a piperazinocarbamoyl group. Morpholinocarbamoyl group, ethylaminocarbamoyl group, cyclohexylaminocarbamoyl group, cyclohexylethylaminocarbamoyl group, and the like.

Of these carbamoyl groups, in the formula [I]
Preferred groups for R ¹ , R ² , R ⁴ and R ⁵ are a diethylaminocarbamoyl group, a piperidinocarbamoyl group, a piperazinocarbamoyl group and a morpholinocarbamoyl group.

R ¹ , R ² , R ⁴ and R ⁵ in the formula [I] may be the same or different.

Further, R ³ and R ⁶ may be the same or different.

In the present invention, among the cobalt complexes represented by the above formula [I], compounds having particularly excellent catalytic activity include:
The following formulas [I-1], [I-2], [I-3], [I-4]
And [I-5].

However, in the above formula [I-1], R ¹⁶ , R ¹⁷ , R ¹⁸
And R ¹⁹ are each independently a lower alkyl group such as a methyl group, an n-propyl group, a sec-butyl group, a t-butyl group, an n-pentyl group; a trifluoromethyl group; a phenyl group, a pentafluorophenyl group, a substituted or unsubstituted aryl group such as a p-bromophenyl group or a methoxyphenyl group; a cycloalkyl group such as a cyclohexyl group; a hydrogen atom;

However, in the above formula [I-2], R ²⁰ , R ²¹ , R ²²
And R ²³ are preferably each independently a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, a t-butyl group and an n-butyl group.

However, in the above formula [I-3], R ²⁴ , R ²⁶ , R ²⁷
And R ²⁶ ′ are preferably each independently a lower alkyl group such as a methyl group, an ethyl group, a sec-butyl group and a t-butyl group,
R ²⁵ and R ²⁵ ′ are each independently preferably a lower alkoxy group such as a methoxy group, an ethoxy group, a sec-butyl group and a t-butyl group; and a lower alkyl group such as a methyl group and an ethyl group.

However, in the above formula [I-4], R ²⁸ , R ²⁹ , R ³¹
And R ³² are each independently a lower alkyl group such as a methyl group or an ethyl group, or R ^32
28 , R ²⁹ , and R ³¹ and R ³² preferably incorporate a nitrogen atom to form a group consisting of a heterocyclic ring such as a piperidine group, a piperazino group, or a morpholino group, and R ³⁰ and R It is preferable that ³³ are each independently a lower branched alkyl group such as a t-butyl group.

However, in the above formula [I-5], at least one of R ³⁴ and R ³⁶ is a fluorine-containing group such as a trifluoromethyl group or a p-trifluoromethylphenyl group. Is preferred, and R ³⁵
And R ³⁷ is an aromatic group such as a p-methylphenyl group, an m-methoxyphenyl group, a 2,4,6-trimethylphenyl group, a 2,4-dimethoxyphenyl group, a 1-naphthyl group, and a 2-naphthyl group. Preferably, there is.

Among the compounds represented by the formula [I] as described above, compounds particularly preferred as the catalyst used in the present invention are compounds represented by the following formulas (50) to (94).

Preferred examples of the compound represented by the formula [I-1]: (50) bis (3,7-dimethyl-4,6-nonanedionate)
Cobalt (II) (51) bis (1,3-dicyclohexyl-1,3-propanedionato) cobalt (II) (52) Bis (2,2,6,6-tetramethyl-3,5-heptanedionato) cobalt (II) (53) bis (2,4-hexanedionato) cobalt (I
I) (54) bis [1,3-bis (4-methoxyphenyl)-
1,3-Propanedionato] cobalt (II) (55) bis (1-pentafluorophenyl-2,4-butanedionato) cobalt (II) (56) bis (4,4-dimethyl-1-pentafluorophenyl-1,3-pentanedionato) cobalt (57) bis (4,4-dimethyl-1-phenyl-1,3-pentanedionato) cobalt (II) (58) bis [1- (4-bromophenyl) -4,4-dimethyl-1,3-pentanedionato) cobalt (II) (59) Bis (2,4-nonangionato) cobalt (II) (60) bis (2,2-dimethyl-3,5-hexanedionato) cobalt (II) (61) Bis [4,6-nonangionato) cobalt (II) (62) bis (1,1,1-trifluoro-2,4-pentanedionato) cobalt (II) (63) bis (1-phenyl-1,3-butanedionato)
Cobalt (II) (64) Cobalt (II) bis (acetylacetonate) (65) bis (1-ethoxycarbonyl-1,3-butanedionato) cobalt (II) (66) bis (1-n-butoxycarbonyl-4,4-dimethyl-1,3-pentanedionato) cobalt (II) (67) bis (1-n-methoxycarbonyl-3-methyl-1,3-butanedionato) cobalt (II) (68) bis (1-methoxycarbonyl-4,4-dimethyl-1,3-pentanedionato) cobalt (II) (69) bis (1-ethoxycarbonyl-4,4-dimethyl-1,3-pentanedionato) cobalt (II) (70) bis (1-n-propoxycarbonyl-4-4
-Dimethyl-1,3-pentanedionato) cobalt (II) (71) bis (2-ethoxycarbonyl-1-phenyl-1,3-butanedionato) cobalt (II) (72) bis (3-ethoxycarbonyl-2,4-pentanedionato) cobalt (II) (73) bis (2-acetyl-1-phenyl-2,4-pentanedionato) cobalt (II) (74) bis (2-methoxycarbonyl-1,3-butanedionato) cobalt (II) (75) bis (2-ethoxycarbonyl-1,3-butanedionato) cobalt (II) (76) bis (2-sec-butoxycarbonyl-1,3-butanedionato) cobalt (II) (77) bis (2-t-butoxycarbonyl-1,3-butanedionato) cobalt (II) (78) Bis (1-piperidinocarbamoyl-4,4-dimethyl-1,3-pentanedionato) cobalt (II) Examples of suitable compounds among the compounds represented by the formula [I-4]: (79) bis (1-dimethylaminocarbamoyl-4,4
-Dimethyl-1,3-pentanedionato) cobalt (II) (80) bis (1-diethylaminocarbamoyl-4,4
-Dimethyl-1,3-pentanedionato) cobalt (II) (81) bis (1-piperazinocarbamoyl-4,4-dimethyl-1,3-pentanedionato) cobalt (II) (82) bis (1-morpholinocarbamoyl-4,4-
Dimethyl-1,3-pentanedionato) cobalt (II) (83) (1-Dimethylaminocarbamoyl-4,4-dimethyl-1,3-pentanedionato) (1-piperazinocarbamoyl-4,4-dimethyl-1,3-pentanedionato)
Cobalt (II) (84) Bis [1,1,1-trifluoro-5- (4-methylphenyl) -2,4-pentanedionato] Examples of suitable compounds among the compounds represented by the formula [I-5] Cobalt (I
I) (85) bis [1,1,1-trifluoro-5- (4-methoxyphenyl) -2,4-pentanedionato] cobalt (I
I) (86) Bis [1,1,1-trifluoro-5- (3-trifluoromethylphenyl) -2,4-pentanedionato]
Cobalt (II) (87) bis [1,1,1-trifluoro-4- (4-methylphenyl) -2,4-butanedionato] cobalt (II) (88) bis [1,1,1-trifluoro-4- (2,4,6-trimethylphenyl) -2,4-butanedionato] cobalt (II) (89) bis [1,1,1-trifluoro-4- (2,4-dimethoxyphenyl) -2,4-butanedionato] cobalt (I
I) (90) bis [1,1,1-trifluoro-4- (1-naphthyl) -2,4-butanedionato] cobalt (II) (91) bis [1,1,1-trifluoro-4- (2-naphthyl) -2,4-butanedionato] cobalt (II) (92) bis [1- (4-methylphenyl) -3- (4
-Trifluoromethylphenyl) -1,3-propanedionato] cobalt (II) (93) bis [1- (4-trifluoromethylphenyl) -3- (2,4,6-trimethylphenyl) -1,3-propanedionato] cobalt (II) (94) bis [1- (2,4-dimethoxyphenyl) -3
-(4-trifluoromethylphenyl) -1,3-propanedionato] cobalt (II) The cobalt complex of such a β-dicarbonyl compound may be a hydrate or a salt. The expression “cobalt complex of β-dicarbonyl compound” in the present invention includes hydrates and salts of cobalt complex of β-dicarbonyl compound.

The cobalt complex of the β-dicarbonyl compound as described above is, for example, an alcoat solution or an aqueous solution in which a dicarbonyl compound or a salt thereof corresponding to a ligand of the complex to be obtained is dispersed or dissolved, as shown below. Then, an aqueous solution of sodium hydroxide is added dropwise with stirring, and then a cobalt compound such as cobalt chloride is added to the solution.

The reaction of the β-dicarbonyl compound with the cobalt compound is usually performed by adjusting the pH value of the reaction solution to an alkaline value within the range of 8 to 12. This reaction is completed at a reaction temperature of usually 0 to 50 ° C for 0.1 to 2 hours.

In the cobalt complex produced as described above, R ¹ and R ⁴ , R ² and R ⁵ , and R ³ and R ⁶ generally represent a cobalt atom as a symmetry point in the above formula [I]. Compounds having the same group.

The cobalt complex of the present invention may be a compound having symmetry as described above, but may not have symmetry, and a compound having no such symmetry may be a target compound as described above. It can be produced by preparing two or more types of cobalt complexes having properties, mixing the two or more types of cobalt complexes, and refluxing the mixture in the presence of a reaction solvent such as toluene. The following is an example of such a reaction.

As the β-dicarbonyl compound used for producing the cobalt complex as described above, any compound capable of forming the above-described cobalt complex can be used without particular limitation. Specific examples of such a β-dicarbonyl compound include 3,7-dimethyl-4,6-nonanedione, 1,3-dicyclohexyl-1,3-propanedione, 2,2,8,8-tetramethyl -4,6-nonanedione, 1,3-butanedione, 1,3-bis (4-methoxyphenyl) -1,3-propanedione, 1-pentafluorophenyl-1,3-butanedione, 4,4-dimethyl- 1-pentafluorophenyl-1,3-
Pentanedione, 4,4-dimethyl-1-phenyl-1,4-pentanedione, 1- (4-bromophenyl) -4,4-dimethyl-1,3-
Pentanedione, 2,4-nonanedione, 2,2-dimethyl-3,5-hexanedione, 4,6-nonanedione, 1-ethoxycarbonyl-1,3-butanedione, 1-n-butoxycarbonyl-4,4- Dimethyl-1,3-
Pentanedione, 1-n-methoxycarbonyl-4--4-dimethyl-1,
3-butanedione, 1-methoxycarbonyl-1,3-butanedione, 1-methoxycarbonyl-4,4-dimethyl-1,3-pentanedione, 1-ethoxycarbonyl-4,4-dimethyl-1,3-pentanedione 1-n-propoxycarbonyl-4,4-dimethyl-1,3
-Pentanedione, 2-ethoxycarbonyl-1-phenyl-1,3-butanedione, 3-ethoxycarbonyl-2,3-pentanedione, 2-acetyl-1-phenyl-1,3-butanedione, 2-methoxymethyleneacetate Acetic acid methyl ester, 2-ethoxymethyleneacetoacetic acid methyl ester, 2-methoxymethyleneacetoacetic acid sec-butoxy ester 2-t-hydroxymethyleneacetoacetic acid-t-butyl ester, 1,1,1-trifluoro-5- (4 -Methylphenyl)
-2,4-pentanedione, 1,1,1-trifluoro-5- (4-methoxyphenyl-2,4-pentanedione, 1-piperidinocarbamoyl-4,4-dimethyl-1,3-
Pentanedione, 1-dimethylaminocarbamoyl-4,4-dimethyl-
1,3-pentanedione, 1-diethylaminocarbamoyl-4--4-dimethyl-1,3-pentanedione, 1-piperazinocarbamoyl-4,4-dimethyl-1,3-
Pentanedione, 1-morpholinocarbamoyl-4,4-dimethyl-1,3
-Pentanedione, 1,1,1-trifluoro-5- (4-methylphenyl)
-2,4-pentanedione, 1,1,1-trifluoro-5- (4-nitrophenyl)
-2,4-pentanedione, 1,1,1-trifluoro-5- (3-trifluoromethylphenyl) -2,4-pentanedione, 1,1,1-trifluoro-4- (4-methyl Phenyl)
-2,4-bitandione, 1,1,1-trifluoro-4- (2,4,6-trimethylphenyl) -2,4-butanedione, 1,1,1-trifluoro-4- (2,4 -Dimethoxyphenyl) -2,4-butanedione, 1,1,1-trifluoro-4- (1-naphthyl) -2,4-
Butanedione, 1,1,1-trifluoro-5- (2-naphthyl) -2,4-
Butanedione, 1- (4-methylphenyl) -3- (4-trifluoromethylphenyl) -1,3-propanedione, 1- (4-trifluoromethylphenyl) -3- (2,
4,6-trimethylphenyl) -1,3-propanedione, 1- (2,4-dimethoxyphenyl) -3- (4-trifluoromethylphenyl) -1,3-propanedione, and 1-phenyl-1 , 3-propanedione. These β-dicarbonyl compounds can be used alone or in combination.

The cobalt compound used for producing the cobalt complex of the present invention together with the β-dicarboxy compound as described above is not particularly limited. Examples of the cobalt compound that can be used in the present invention include CoCl _{2 and the} like. Examples thereof include an inorganic cobalt compound and an organic cobalt compound such as Co (CH ₃ COO) ₂ , and these cobalt compounds can be used alone or in combination.

The reaction between the β-dicarboxylic acid and the cobalt compound is as follows:
Although the reaction can be carried out in water, the reaction is preferably carried out in a mixed solvent of water and alcohol. The weight ratio of water to alcohol in the reaction solvent used in the present invention is usually in the range of 10:90 to 100: 0.

The hydroperoxide used in the present invention can be represented by the following formula [III].

However, in the formula [III], X, Y and Z are each independently a group selected from the group consisting of a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group and an arylalkoxy group. . However, at least one group among X, Y, and Z is a group other than a hydrogen atom.

Specific examples of the lower alkyl group, cycloalkyl group, aryl group, and arylalkyl group having 1 to 10 carbon atoms include the groups exemplified in the description of the cobalt complex represented by the formula [I]. be able to.

Specific examples of such a hydroperoxide include t-butyl hydroperoxide, cumene hydroperoxide, cyclohexane hydroperoxide, cyclopentane hydroperoxide, cyclooctane hydroperoxide, 1-phenylethane-1- Hydroperoxide, 4-phenylbutane-1-hydroperoxide, decane-2-hydroperoxide and the like can be mentioned.

These hydroperoxides can be used alone or in combination.

Among these hydroperoxides, in particular, t-
The use of butyl hydroperoxide, cumene hydroperoxide and cyclohexane hydroperoxide is preferred.

The method for producing a silyl peroxide according to the present invention uses a cobalt complex of a β-carbonyl compound as described above, and in the presence of a hydroperoxide as described above, a silane derivative, an olefinic hydrocarbon compound, and an oxygen-containing compound. The gas is brought into contact with the gas.

The silane derivative used in the present invention has the following formula [II
I].

However, in the formula [III], R ⁷ , R ⁸ and R ⁹ are each independently selected from the group consisting of a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, an aryl group, a lower alkoxy group and an arylalkyl group. Represents a group or atom.

However, in the above formula [III], at least one of R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom. Therefore, in the present invention, SiH ₄ is not used.

These lower alkyl groups having 1 to 10 carbon atoms, aryl groups,
Specific examples of the lower alkoxy group and the arylalkyl group include the groups exemplified in the description of the cobalt complex represented by the formula [I].

As specific examples of the silane derivative represented by the above formula [III], methylsilane, ethylsilane, phenylsilane, diethylsilane, dimethylsilane, pentylsilane, diphenylsilane, methylethylsilane,
Methylphenylsilane, trimethylsilane, triethylsilane, tri-n-propylsilane, dimethylphenylsilane, diethylphenylsilane, dimethylethylsilane, t-butyldimethylsilane, t-butyldiethylsilane, methoxysilane, ethoxysilane, methylmethoxysilane , Diethylmethoxysilane, phenylmethoxysilane, phenylethoxysilane, methyldimethoxysilane and dimethylethoxysilane. These silane derivatives can be used alone or in combination.

Among these silane derivatives, dimethylsilane, diethylsilane, trimethylsilane, triethylsilane,
Dimethylphenylsilane, diethylmethoxysilane, dimethylethoxysilane, t-butyldimethylsilane, phenylsilane and the like are particularly preferred.

The olefinic hydrocarbon compound used in the present invention is usually an olefinic hydrocarbon compound having 2 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and can be represented by, for example, the following formula [IV].

However, in the above formula [IV], R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a lower alkyl group,
A lower alkenyl group, a lower alkynyl group, an arylalkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an atom or a group selected from the group consisting of a carbamoyl group and a cyano group, R ¹⁰ and R ¹² or R ¹¹ and R ¹³ may form a ring together. However, any one of R ^{10 to} R ¹³ is a group other than a hydrogen atom.

Such olefinic hydrocarbon compounds represented by the formula [IV] include aliphatic olefinic compounds, alicyclic olefinic compounds, and aromatic olefinic compounds. These compounds may have a substituent. In the method of the present invention, the double bond contributing to the reaction may be located at the terminal of the main chain, or may be located at a portion other than the terminal, for example, near the center of the main chain. (Ex
o-terminal), a portion other than the end of the side chain,
For example, it may be located near the center of the side chain.

The olefinic hydrocarbon compound used in the present invention is generally a compound having at least one double bond having activity in the reaction of the present invention, as shown by the above formula [IV]. Compounds having two or more such double bonds can also be used. If it has two or more double bonds, these double bonds need not show the same activity in the reaction of the present invention.

Specific examples of the olefinic hydrocarbon compound used in the present invention include isoprene, butadiene, propylene, 1-butene, 2-butene, isobutene, 1-
Pentene, 2-pentene, 2-methyl-1-butene, 3
-Methyl-1-butene, 2-methyl-2-butene, 1-
Aliphatic olefin compounds such as hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, 5-decene and 1-methyl-2-decene; cyclopentene, cyclo Octene, cyclohexene,
Cyclodecene, cycloheptene, 1,4-cyclohexadiene, 1,3-cyclohexadiene, 1,4-cyclooctadiene, 1-methylcyclohexene, 2-methylcyclohexene, 4-carbethoxycyclohexene, 4,5-dicarbomethoxycyclohexene Alicyclic olefins such as, 4-vinylcyclohexene, pinene, camphene, norbornene, cyclopentadiene, 1,2,3,4,5-pentamethylcyclopentadiene, indene, 1-methylindene and 1,2-dihydronaphthalene Compounds; Aromatic olefins such as 4-phenyl-1-butene, 4-phenyl-2-butene 2-methyl-4-phenyl-1-butene, stilbene, styrene and 5-phenyl-3-methyl-2-pentene Compounds can be mentioned.

Further, in the method of the present invention, an olefin compound having a functional group can be used in addition to the olefin compound as described above. The olefinic hydrocarbon compound that can be used in the present invention is represented by the above formula [II
It is a compound having a functional group that does not directly react with the silane derivative represented by I]. Specific examples of such olefinic hydrocarbon compounds include methyl acrylate, ethyl acrylate, propyl acrylate, methyl crotonate, ethyl crotonate, hexenoic acid methyl ester, nonanoic acid methyl ester, Canoic acid methyl ester, aryl benzoate, aryl acetate, aryl alcohol methyl ester, arylamine benzoic acid amide, arylamine acetic acid amide, ethyl cinnamate, methyl cinnamate, 5-hexen-1-ol benzoate, 6-methyl-5-hepten-2-ol benzoate, benzalacetophenone, benzalacetone,
Punyl alcohol p-methoxybenzoate can be mentioned.

Even if an olefinic hydrocarbon compound having such a functional group is used, silyl peroxide can be produced according to the production method of the present invention without affecting the functional group.

As the oxygen-containing gas used in the present invention, not only oxygen itself can be used, but also a gas containing components other than oxygen, such as air, can be used. When a gas containing a component other than oxygen is used, a gas having an oxygen concentration of 5% by volume or more is preferably used in consideration of the economics of the reaction.

In the method for producing silyl peroxide of the present invention, it is not particularly necessary to use a reaction solvent, but a reaction solvent can be used.

When a reaction solvent is used in the present invention, the reaction solvent that can be used is not particularly limited as long as it is a solvent having no activity for the reaction raw materials. Examples of solvents that can be used as a reaction solvent in the present invention include: hydrocarbon solvents such as hexane, benzene, and toluene; halogenated hydrocarbon solvents such as dichloromethane, ethylene dichloride, and chloroform: methyl formate, ethyl formate, Methyl acetate, ethyl acetate,
Ester solvents such as butyl acetate; and ether solvents such as dimethoxyethane, dioxane, diethyl ether and the like. These solvents can be used alone or in combination.

Among these solvents, benzene, toluene, dichloromethane, and ethylene dichloride are preferably used.

In the method for producing a silyl peroxide according to the present invention, the cobalt complex of the β-carbonyl compound and the hydroperoxide are usually 0.001 to 1 mol, preferably 0.01 to 1 mol, per 1 mol of the olefinic hydrocarbon compound used. It is used in an amount in the range of 0.2 mole. In the present invention, the cobalt complex may be used alone, or may be supported on a simple substance. in this case,
A commonly used carrier can be used.

The silane derivative is usually used in an amount of 0.3 to 50 mol, preferably 0.5 to 1 mol per mol of the olefinic hydrocarbon compound.
It is used in an amount in the range of ~ 3.0 mol.

The amount of oxygen-containing gas introduced into the reaction system is:
1 to 1 mole of olefinic hydrocarbon compound used
It is sufficient if it is at least mol, and usually it is excessively introduced into the reaction system. The supply form of the oxygen-containing gas to the reaction system is not particularly limited as long as the reaction raw materials such as the silane derivative and the olefinic hydrocarbon compound and the cobalt complex acting as a catalyst can be brought into contact with the oxygen-containing gas. A method of stirring below, a method of bubbling an oxygen-containing gas in the reaction solution, and the like can be adopted.

This reaction can be carried out under any of reduced pressure or increased pressure, and it is preferable that the reaction is usually performed at a pressure in the range of 0.1 to 50 atm and 0.2 to 2 atm.

The reaction temperature of the above reaction varies depending on other conditions, but is usually set in a range of −70 to 100 ° C., preferably −10 to 50 ° C.

By reacting at such a temperature, usually 0.5
The reaction is completed within 5050 hours, preferably 1-20 hours.

The above reaction can be performed in various forms such as a fixed bed, a fluidized bed, and a moving bed.

By reacting in this manner, a silyl peroxide represented by the following formula [V] and / or a silyl peroxide represented by the formula [VI] can be obtained.

However, in the formulas [V] and [VI], R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, an aryl group, a lower alkoxy group and an arylalkyl group. In addition, at least one of R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom.
And R ¹⁰ and R ¹¹ , R ¹² and R ¹³ are a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group,
Arylalkyl group, cycloalkyl group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, represents an atom or group selected from the group consisting of a carbamoyl group and a cyano group, R ¹⁰ and R ¹² or
R ¹¹ and R ¹³ may form a ring together. However, at least one of R ^{10 to} R ¹³ is a group other than a hydrogen atom.

Specific examples of the lower alkyl group, aryl group, arylalkyl group, cycloalkyl group, lower alkenyl group, lower alkynyl group, alkoxycarbonyl group, alkylcarbonyl group and arylcarbonyl group in the above formulas [V] and [VI] Typical examples are the same as the groups exemplified in the formula [IV].

The silyl peroxide obtained by the production method according to the present invention can be used as a coupling agent, a reaction initiator, an oxidizing agent and the like. Alternatively, it is highly useful as a reaction intermediate, a solvent, a fragrance, a polymer raw material, or the like.

Note that the expressions [V] and [V
After dissolving or dispersing a silyl peroxide represented by I] in a polar solvent such as methanol,
By adding an acid such as hydrochloric acid and hydrolyzing, the following formula [VI
I] can be obtained. The peroxide thus obtained is useful, for example, as a reaction initiator.

However, in the above formula [VII], R ¹⁰ and R ¹¹ and R ¹² and R ¹³ have the same meanings as in the above formulas [V] and [VI].

Effect of the Invention According to the method for producing silyl peroxide according to the present invention, since a cobalt complex is used as a catalyst, silyl peroxide can be synthesized from an olefin in one step. Further, this reaction is highly safe because it is not necessary to react a highly dangerous intermediate such as peroxide under unstable conditions as in the conventional reaction.

Further, by using the above-mentioned catalyst, silyl peroxide can be produced in high yield using an olefin having a functional group as a raw material.

Further, according to the method of the present invention, since the reaction is not an equilibrium reaction, silyl peroxide can be produced at a high conversion without performing a complicated operation for removing a reaction product from the reaction system. .

Moreover, even when the olefinic hydrocarbon compound has a functional group, the functional group is not decomposed, and therefore, the olefinic hydrocarbon compound having a functional group
Silyl peroxide having such a functional group can be produced.

Next, the present invention will be described with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1 Preparation of ethyl 2-triethylsiliperoxyacrylate 100 mg (1 mmol) of ethyl acrylate, 230 mg (2 mmol) of triethylsilane, and 13 mg (0.05 mmol) of bis (acetylacetonato) cobalt (II) complex were obtained.
It was dissolved in 5 ml of 1,2-dichloroethane.

To this solution was added a solution of t-BuOOH (tert-butyl hydroperoxide) in 2,4,4-trimethylpentane (3.
12 mg (0.05 mmol) was added dropwise and stirred at 25 ° C. for 5 hours under an oxygen atmosphere.

After 5 hours, the reaction solution was concentrated under reduced pressure, and the residue was purified using thin-layer chromatography (silica gel).

By purifying as described above, 135 mg of ethyl 2-triethylsilylperoxyacrylate as the title compound was obtained. Yield 55%, colorless oil Nuclear magnetic resonance spectrum (in deuterated chloroform) δ = 0.71 (3H, q, J = 8 Hz), 0.99 (3H, t, J = 8 Hz), 1,
30 (3H, t, J = 7Hz), 1.34 (3H, q, J = 7Hz), 4,23 (2H,
q, J = 7 Hz), 4.48 (1H, q, 7 Hz); infrared absorption spectrum (Neat) λ (cm ⁻¹ ) = 1758, 1745, 1199 cm ⁻¹ Comparative Example 1 In Example 1, t-BuOOH was not added. Then, the same operation was carried out except that the reaction was carried out for 24 hours. As a result, the yield of the target ethyl 2-triethylsilylperoxyacrylate was 25%.

Examples 2 to 5 In Example 1, bis (acetylacetonato) cobalt (I
I) The reaction was carried out in the same manner as above except that the complex was replaced with various cobalt complexes (0.05 mmol) and reacted for a predetermined time.

The production conditions for ethyl 2-triethylsilylperoxyacrylate are as follows.

Production of ethyl 2-triethylsilylperoxyacrylate The results are shown in Table 1.

Comparative Examples 2 to 5 The same procedure was performed as in Example 2 except that the reaction was performed without adding t-BuOOH.

 The results are shown in Table 2.

Examples 6 to 10 Synthesis of ethyl 2-triethylsilylperoxyacrylate The reaction was carried out in the same manner as in Example 1 except that the hydroperoxide shown in Table 3 was used in place of t-BuOOH (0.05 mmol was used). went.

 The results are shown in Table 3.

Examples 11 to 15 The same reaction as in Example 1 was carried out except that the α, β-unsaturated ester described in Table 4 was used in place of ethyl acrylate and the reaction time was changed as shown in Table 4. Was done.

Table 4 shows the structure and yield of the obtained silyl peroxide.

Example 16 Production of 2-triethylsilylperoxy-2-phenylethane In Example 1, 104 mg of styrene was used instead of ethyl acrylate
(1 mmol), the reaction was carried out in the same manner, and the relationship between the reaction time and the product was examined.

The total yield of the reaction product was 213 mg, and the total yield was 85%.

FIG. 1-A shows the change over time of the product and the raw material. No. 1-
In FIG. A, the change over time of the raw material is indicated by 1 (（), and the change over time Indicated by

Comparative Example 6 The same procedure was performed as in Example 16 except that the reaction was performed for 24 hours without using t-BuOOH.

 The overall yield of the reaction product was 30%.

FIG. 1-B shows the change over time of the product and the raw material. No. 1-
In FIG. B, the change over time of the raw material is indicated by 1 (（), and the change over time of the product is 2 Indicated by

Examples 17 to 19 Preparation of 2-triethylsilylperoxy-2-phenylethane In Example 16, the cobalt complex shown in Table 5 was used in place of the bis (acetylacetonato) cobalt complex (0.05 mmol). The reaction was carried out in the same manner except that the reaction was carried out for an hour.

 The results are shown in Table 5.

[Brief description of the drawings]

FIG. 1-A is a graph showing an example of reaction time and yield of a reaction product when synthesizing 2-triethylsilylperoxy-2-phenylenyl from styrene. FIG. 1-B is a graph showing an example of the yield of 2-triethylsilylperoxy-2-phenylethyl with respect to the reaction time when t-BuOOH is not used.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/18 B01J 31/22 CA (STN) REGISTRY (STN) WPIDS (STN) BEILSTEIN (STN)

Claims (1)

(57) [Claims] 1. A cobalt complex of a β-dicarbonyl compound represented by the following formula [I]: [In the above formula [I], R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms,
Cycloalkyl group, aryl group, arylalkyl group,
A trifluoromethyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an atom or group selected from the group consisting of a cyano group and a carbamoyl group; R ³ and R
⁶ independently represents a group selected from the group consisting of a lower alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group and a cycloalkyl group. And a hydroperoxide of the formula [II] (In the above formula [II], X, Y and Z each independently represent a hydrogen atom, an atom selected from the group consisting of a lower alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group and an arylalkyl group, or X and Y
And at least one of Z is a group other than a hydrogen atom. A) a silane derivative represented by the following formula [III]; (In the above formula [III], R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms,
It represents a group or an atom selected from the group consisting of an aryl group, a lower alkoxy group and an arylalkyl group, and at least one of R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom. ) And a chain olefin represented by the following formula [IV]; (In the above formula [IV], R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are
Each independently an atom selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an arylalkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a carbamoyl group and a cyano group Or a group, and R ¹⁰ and R ¹² or R ¹¹ and R ¹³ may form a ring together. However, at least one of R ^{10 to} R ¹³ is a group other than a hydrogen atom. ) And an oxygen-containing gas.
And / or a silyl peroxide represented by the formula [V
A method for producing a silyl peroxide represented by I]; (In the above formulas [V] and [VI], R ⁷ , R ⁸ and R ⁹
Independently represent a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, an aryl group, a lower alkoxy group and an arylalkyl group, and among R ⁷ , R ⁸ and R ⁹ ,
At least one group is a group other than a hydrogen atom, and R ¹⁰
And R ¹¹ , R ¹² and R ¹³ are a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an arylalkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a carbamoyl group, and Represents an atom or group selected from the group consisting of a cyano group, and R ¹⁰ and R ¹² or R ¹¹ and R ¹³ may form a ring together. Where R
At least one of ¹⁰ to R ¹³ is a group other than a hydrogen atom. ).