JPH115033A - Formation of carbon-carbon bond - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for the formation of a carbon-carbon bond capable of controlling a side reaction and capable of steric control under mild conditions and to provide a method for forming a carbon-carbon bond using the catalyst and an addition method using the catalyst. SOLUTION: The catalyst for the formation of a carbon-carbon bond contains an azo compd. represented by formula I (where R1 is lower alkyl). A carbon- carbon bond is formed by reaction in the presence of the catalyst. An α- halogenocarboxylic acid deriv. is added to an unsatd. compd. in the presence of the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel catalyst for forming a carbon-carbon bond and a method for forming a carbon-carbon bond using the catalyst.

[0002]

2. Description of the Related Art In organic synthetic chemistry, formation of carbon-carbon bonds using radical reactions is one of important synthetic strategies. In order to achieve a clean reaction without causing side reactions, it is desirable to carry out the reaction under mild conditions as much as possible, but azobisisobutyronitrile, which is well known as an initiator in radical reactions, is considered to be desirable. (AIB
N) generally requires heat for radical generation and can cause side reactions. The radical addition reaction by light irradiation is possible even at room temperature or lower, but is not suitable for mass synthesis. Recently, a reaction using a Lewis acid as a low-temperature radical initiator has been developed, but it may not be applicable to a substrate having an acid-sensitive functional group.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is intended to provide a catalyst for forming a carbon-carbon bond capable of controlling side reactions and sterically controlling under mild conditions.
And a method for forming a carbon-carbon bond using the catalyst, and an addition method using the catalyst.

[0004]

The present invention comprises the following arrangement. "(1) A catalyst for forming a carbon-carbon bond comprising an azo compound represented by the following general formula [1]:

[0005]

Embedded image

(Wherein, R ₁ represents a lower alkyl group.) (2) A catalyst according to (1),
Carbon-carbon bond forming method.

(3) In the presence of the catalyst described in (1), α-
A method for forming a carbon-carbon bond, comprising reacting a halogenocarboxylic acid derivative with an unsaturated compound.

(4) A method for adding an α-halogenocarboxylic acid derivative to an unsaturated compound, comprising using the catalyst according to (1). "

That is, the present inventors have conducted intensive studies on the control and steric control of side reactions, and furthermore on the reaction capable of simpler and more complete steric control. Focusing on the fact that the azo compound represented by the general formula [1] effectively generates a radical species at a low temperature,
By using this as a catalyst for forming a carbon-carbon bond, the inventors have found that all of the above problems can be solved, and have reached the present invention.

In the general formula [1], examples of the lower alkyl group represented by R ₁ include an alkyl group having 1 to 4 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group and a butyl group. And a methyl group.

The α-halogenocarboxylic acid derivative used in the present invention includes, for example, compounds represented by the following general formula [2].

[0012]

Embedded image

(Wherein X represents a halogen atom, and at least one of R ₃ and R ₄ is an alkyloxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, a cyano group, a carbamoyl group) Or R ₂ represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, an alkoxy group, an aralkyloxy group, an aryloxy group or a hydroxy group. )

In the general formula [2], examples of the halogen atom represented by X include chlorine, bromine and iodine.
Among them, bromine is preferred. The alkyloxycarbonyl group represented by R ₃ and R ₄ may be linear or branched, and includes, for example, an alkyloxycarbonyl group having 2 to 19 carbon atoms, specifically, a methyloxycarbonyl group,
Ethyloxycarbonyl, propyloxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, tert-butyloxycarbonyl And a bonyl group and a 2-ethylhexyloxycarbonyl group. Examples of the aralkyloxycarbonyl group include an aralkyloxycarbonyl group having 8 to 20 carbon atoms, and specific examples include a benzyloxycarbonyl group and a phenethyloxycarbonyl group. The aryloxycarbonyl group includes, for example, an aryloxycarbonyl group having 7 to 20 carbon atoms, specifically, a phenyloxycarbonyl group,
And a naphthyloxycarbonyl group. As the acyloxy group, a carboxylic acid derived, for example, having 2 to 18 carbon atoms
And specific examples include an acetyloxy group, a propionyloxy group, a butyryloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group, an octanoyloxy group, and a benzoyloxy group. The acyl group includes, for example, an acyl group having 1 to 18 carbon atoms derived from a carboxylic acid.Specifically, a formyl group, an acetyl group, a propionyl group, a butyryl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, And a benzoyl group. R
_The alkyl group represented by _{2 to} R ₄ may be linear, branched, or cyclic, and includes, for example, an alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, and an n group.
-Propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 3,
3-dimethylbutyl, 1,1-dimethylbutyl, 1-methylpentyl, n-hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl Group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. As a substituent in the aryl group which may have a substituent, an alkoxy group, a vinyl group,
Examples include a halogen atom, an amino group, a hydroxy group, and a carboxyl group, and specific examples of these aryl groups include
For example, phenyl, tolyl, xylyl, naphthyl, anthryl, 4-ethylphenyl, 4-methoxyphenyl, 4-vinylphenyl, 4-chlorophenyl,
Examples include an aminophenyl group, a hydroxyphenyl group, and a carboxyphenyl group. The alkoxy group may be linear or branched, and includes, for example, an alkoxy group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-propoxy group, tert-butyl
Examples include a toxic group and a 2-ethylhexyloxy group.
Examples of the aralkyloxy group include an aralkyloxy group having 7 to 20 carbon atoms, and specific examples include a benzyloxy group and a phenethyloxy group. Examples of the aryloxy group include an aryloxy group having 6 to 20 carbon atoms, and specific examples include a phenoxy group and a naphthyloxy group.

The unsaturated compound used in the present invention may be a chain compound or a cyclic compound, and may have an aromatic ring group. Further, it may be symmetric or asymmetric. Examples of the unsaturated compound include alkenes having a carbon-carbon double bond in the molecule.

Examples of such an alkene include a compound represented by the following general formula [3].

[0017]

Embedded image

(Wherein R ₅ is a hydrogen atom, an alkyl group, a haloalkyl group, an aryl group which may have a substituent,
Optionally substituted aralkyl groups, aliphatic heterocyclic groups, aromatic heterocyclic groups, alkyloxycarbonyl groups, hydroxyalkyloxycarbonyl groups, aralkyloxycarbonyl groups, aryloxycarbonyl groups,
Acyloxy group, an acyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, a cyano group, an amino group, a carbamoyl group, a hydroxyl group, a sulfonic acid group, aldehyde group or carboxyl group, R ₆ is a hydrogen atom, a halogen atom, Represents an alkyl group, an aralkyl group which may have a substituent, an alkyloxycarbonyl group, a hydroxyalkyloxycarbonyl group, a hydroxyl group or a carboxyl group, R ₉ represents an alkylene group or a bond, and R ₇ represents a hydrogen atom , An alkyl group, a carboxyl group, an alkyloxycarbonyl group, a hydroxyalkyloxycarbonyl group or a hydroxyl group, and R ₈ represents a hydrogen atom, a halogen atom or an alkyl group. Further, R ₇ and R ₈ may form an aliphatic ring. )

In the general formula [3], aralkyl groups which may have a substituent represented by R ₅ and R ₆ include:
Examples thereof include an aralkyl group having 7 to 20 carbon atoms and a nuclear substituent thereof, and specific examples thereof include a benzyl group, a phenethyl group, a 3-phenylpropyl group, and a 3- (4-methyloxycarbonylphenyl) propyl group. . The alkyloxycarbonyl group represented by R ₅ , R ₆ and R ₇ may be linear or branched, and includes, for example, an alkyloxycarbonyl group having 2 to 19 carbon atoms. Group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, tert-butyl Oxycarbonyl group, 2-ethylhexyloxycarbonyl group and the like can be mentioned. R ₅
Examples of the hydroxyalkyloxycarbonyl group represented by include a hydroxyalkyloxycarbonyl group having 2 to 19 carbon atoms in which a hydrogen atom of the alkyl group of the alkyloxycarbonyl group is substituted with a hydroxyl group as described above. Hydroxymethyloxycarbonyl, hydroxyethyloxycarbonyl, hydroxypropyloxycarbonyl, hydroxybutyloxycarbonyl, hydroxypentyloxycarbonyl, hydroxyhexyloxycarbonyl, hydroxyheptyloxycarbonyl, hydroxyoctyloxycarbonyl, hydroxydodecyl Oxycarbonyl group, hydroxyoctadecyloxycarbonyl group and the like can be mentioned. The alkyl group represented by R ₅ may be linear, branched or cyclic, and has, for example, 1 carbon atom.
To 20 alkyl groups, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl , Neopentyl, tert-pentyl, 3,3-dimethylbutyl, 1,1-dimethylbutyl, 1-methylpentyl, n-hexyl, isohexyl, heptyl, octyl, nonyl, decyl ,
Undecyl, dodecyl, hexadecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. As the haloalkyl group,
For example, when the alkyl group is halogenated (for example, fluorinated,
Chlorination, bromination, iodination, etc. A) haloalkyl group having 1 to 20 carbon atoms, specifically, chloromethyl group,
Bromomethyl group, trifluoromethyl group, 2-chloroethyl group, 3-chloropropyl group, 3-bromopropyl group, 3,3,
3-trifluoropropyl group, 2-perfluorooctylethyl group, perfluorooctyl group, 1-chlorodecyl group,
Examples thereof include a 1-chlorooctadecyl group and an 8-iodooctyl group. Examples of the substituent of the aryl group which may have a substituent include an alkoxyl group, a halogen atom, an amino group,
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a 4-ethylphenyl group, and a 4-methoxyphenyl group. Group,
Examples thereof include a 4-vinylphenyl group, a 4-chlorophenyl group, an aminophenyl group, a hydroxyphenyl group, a sulfophenyl group, and a carboxyphenyl group. As the aliphatic heterocyclic group, for example, a 5- or 6-membered aliphatic heterocyclic group is preferable, and those containing 1 to 3 hetero atoms such as a nitrogen atom, an oxygen atom, and a sulfur atom as isomer atoms are preferable. Specific examples thereof include a pyrrolidyl-2-one group, a piperidinyl group, a piperazinyl group, and a morpholinyl group. As the aromatic heterocyclic group, for example, a 5- or 6-membered aromatic heterocyclic group is preferable, and those containing 1 to 3 hetero atoms such as nitrogen, oxygen, and sulfur as isomer atoms are preferable. Specific examples thereof include a pyridyl group, an imidazolyl group, a thiazolyl group, a furanyl group, and a pyranyl group. Examples of the aralkyloxycarbonyl group include those having 8 carbon atoms.
To 15 aralkyloxycarbonyl groups, specifically, benzyloxycarbonyl group, phenethyloxycarbonyl group and the like. As the aryloxycarbonyl group, for example, an aryloxycarbonyl group having 7 to 20 carbon atoms is preferable, and specific examples include a phenyloxycarbonyl group and a naphthyloxycarbonyl group. Examples of the acyloxy group include, for example, an acyloxy group having 2 to 18 carbon atoms derived from a carboxylic acid.Specific examples include an acetyloxy group, a propionyloxy group, a butyryloxy group, a pentanoyloxy group, a hexanoyloxy group, and a heptanoyloxy group. Group, octanoyloxy group, benzoyloxy group and the like. As the acyl group,
For example, an acyl group having 1 to 18 carbon atoms derived from a carboxylic acid, such as a formyl group, an acetyl group, a propionyl group, a butyryl group, a pentanoyl group, a hexanoyl group,
Examples include a heptanoyl group, an octanoyl group, and a benzoyl group. The alkoxy group may be linear or branched, for example, having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms.
Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-propoxy group, a tert-butoxy group, and 2 -Ethylhexyloxy group and the like. Examples of the aralkyloxy group include an aralkyloxy group having 7 to 20 carbon atoms, and specific examples include a benzyloxy group and a phenethyloxy group. As the aryloxy group, for example, an aryloxy group having 7 to 15 carbon atoms is preferable, and specific examples include a phenoxy group and a naphthyloxy group. As the alkyl group represented by R ₆ , R ₇ and R ₈ ,
It may be linear or branched, and a lower alkyl group, for example, an alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, te
Examples thereof include an rt-pentyl group, a 3,3-dimethylbutyl group, a 1,1-dimethylbutyl group, a 1-methylpentyl group, an n-hexyl group, and an isohexyl group. Examples of the halogen atom represented by R ₆ and R ₈ include chlorine, bromine, fluorine, iodine and the like. Examples of the aliphatic ring formed by R ₇ and R ₈ include those in which an alkylene chain having 3 to 10 carbon atoms forms a ring, and the ring may be a single ring or a polycyclic ring. Specific examples of these rings include a norbornene ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, and a cyclodecene ring. The alkylene group represented by R ₉ may be linear or branched and has, for example, 1 to 10 carbon atoms.
Examples of the alkylene group, specifically methylene group, ethylene group, propylene group, butylene group, 2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group, 2-
Examples include an ethylpropylene group, a hexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, and a decylene group.

The alkene represented by the general formula [3] according to the present invention may be symmetric or asymmetric. Specific examples of the alkene include C2-C20 ethylenically unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, and isobutylene, and C3 carbon atoms such as norbornene, cyclopentene, cyclohexene, cyclooctene, and cyclodecene. To 20 unsaturated alicyclic hydrocarbons, for example, α-ethylenically unsaturated aromatic hydrocarbons having 8 to 20 carbon atoms such as styrene, 4-methylstyrene, 4-ethylstyrene, and 4-methoxystyrene, for example, formic acid 3 to 20 carbon atoms such as vinyl, vinyl acetate, vinyl propionate, and isopropenyl acetate
Alkenyl esters such as vinyl chloride, vinylidene chloride and vinylidene fluoride; halogenoethylenically unsaturated compounds having 2 to 20 carbon atoms such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, Ethylenically unsaturated carboxylic acids having 3 to 20 carbon atoms such as citraconic acid, mesaconic acid, vinyl acetic acid, allyl acetic acid, and vinyl benzoic acid (these acids include salts of salts such as alkali metal salts such as sodium and potassium and ammonium salts). May be in the form of). For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, vinyl methacrylate, allyl methacrylate, Phenyl methacrylate, methacrylic acid Benzyl, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, vinyl acrylate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl maleate, fumaric acid Dimethyl, diethyl fumarate, methyl crotonate, ethyl crotonate, vinyl crotonate, dimethyl citrate, diethyl citrate, dimethyl mesate, diethyl mesate, methyl 3-butenoate, 2-hydroxyethyl methacrylate, methacrylate 3 4-hydroxypropyl, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, etc.
To 20 ethylenically unsaturated carboxylic acid esters such as acrylonitrile, methacrylonitrile, allyl cyanide and the like having 3 to 20 cyanoethylenically unsaturated compounds such as acrylamide and methacrylamide; 20 ethylenically unsaturated amide compounds such as acrolein and crotonaldehyde having 3 to 20 carbon atoms; and ethylenically unsaturated aldehydes having 2 to 20 carbon atoms such as vinyl sulfonic acid and 4-vinylbenzene sulfonic acid. Unsaturated sulfonic acids (these acids may be in the form of a salt such as an alkali metal salt such as sodium and potassium), and ethylenically unsaturated sulfonic acids having 2 to 20 carbon atoms such as vinylamine and allylamine. Aliphatic amines, for example, ethylenically unsaturated aromatic amines having 8 to 20 carbon atoms such as vinylaniline; , For example, C5-C20 ethylenically unsaturated aliphatic heterocyclic amines such as N-vinylpyrrolidone and vinylpiperidine; C5-C20 ethylenically unsaturated aromatics such as vinylpyridine and 1-vinylimidazole Group 3 heterocyclic amines, for example, C3-20 ethylenically unsaturated alcohols such as allyl alcohol and crotyl alcohol, and C8-20 ethylenically unsaturated phenols such as 4-vinylphenol, etc. Can be

Among the alkenes as described above, an alkene represented by the following general formula [3 '] is particularly preferred.

[0022]

Embedded image

(Wherein R _{5 ′} , R _{6 ′} , R _{7 ′} and R _{8 ′} each independently represent a hydrogen atom, a lower alkyl group, a carboxyl group,
It represents an aryl group which may have a substituent, a lower alkyloxycarbonyl group, a lower hydroxyalkyloxycarbonyl group or a lower acyloxy group. Further, R _{7 ′} and R _{8 ′} may form an aliphatic ring. )

In the general formula [3 '], the lower alkyl group may be linear or branched and includes an alkyl group having 1 to 6 carbon atoms. The lower alkyloxycarbonyl group may be linear or branched and has 2 to 2 carbon atoms.
And 7 alkyloxycarbonyl groups. Also,
As the lower hydroxyalkyloxycarbonyl group,
A hydroxyalkyloxycarbonyl group having 2 to 7 carbon atoms is exemplified, and the lower acyloxy group is an acyloxy group having 2 to 7 carbon atoms derived from carboxylic acid.
The specific examples of the other groups and the groups represented by R _{5 ′} , R _{6 ′} , R _{7 ′} and R _{8 ′} are the same as those of the above-mentioned general formula [3].

When the catalyst of the present invention represented by the general formula [1] is used, a carbon-carbon bond can be formed. For example, the unsaturated compound as described above can be regioselectively treated with the α-halogenocarboxylic acid derivative as described above. Can be added to

The method of forming a carbon-carbon bond and the method of addition according to the present invention will be described below, taking an example in which an alkene is used as an unsaturated compound.

That is, the α-halogenocarboxylic acid derivative as described above and an alkene represented by the general formula [3] or [3 ′] as described above are reacted in a suitable reaction solvent in the presence of the catalyst of the present invention. If necessary, the compound (adduct) represented by the general formula [4] or [4 ′] can be obtained by reacting in an inert gas atmosphere according to a conventional method.

[0028]

Embedded image

(Where X, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ , R ₈ and R ₉ are the same as above. ).

[0030]

Embedded image

(Where X, R ₂ , R ₃ , R ₄ , R _{5 ′} ,
R _{6 ′} , R _{7 ′} and R _{8 ′} are the same as described above. ).

The post-treatment after the reaction may be carried out according to a usual post-treatment method, and the produced compound may be purified by a method known per se, that is, various chromatography, recrystallization and the like.

In the present invention, the amount of the α-halogenocarboxylic acid derivative and the unsaturated compound used is such that the amount of the unsaturated compound is
-It is desirable to use an equivalent amount or more based on the halogenocarboxylic acid derivative.

The amount of the catalyst for forming a carbon-carbon bond may be appropriately determined in consideration of the progress of the reaction and the cost, but is usually determined with respect to the α-halogenocarboxylic acid derivative.
0.01 equivalent or more, preferably 0.1 to 5 equivalent is used.

Examples of the reaction solvent include hydrocarbons such as toluene, xylene, benzene, cyclohexane, n-hexane and n-octane; halogenated hydrocarbons such as methylene chloride, dichloroethane and trichloroethane;
For example, methyl acetate, ethyl acetate, n-butyl acetate, esters such as methyl propionate, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, tert-butyl methyl ketone, ketones such as cyclohexanone, for example, dimethyl ether, diethyl ether, diisopropyl ether, Dimethoxyethane, tetrahydrofuran,
Ethers such as dioxane; These may be used alone or in combination of two or more.

Examples of the inert gas include nitrogen gas, argon gas and the like.

If the reaction temperature is too low, the progress of the reaction is slowed down due to little decomposition of the azo group, and if the reaction temperature is too high, by-products are liable to be formed, and selective addition reaction is difficult to occur. The temperature may be lower than ℃, but -30 to 60 ° C is preferable, and -10 to 30 ° C is more preferable.

The reaction time varies depending on the reaction conditions such as the reaction temperature, the type and amount of the α-halogenocarboxylic acid derivative and unsaturated compound to be reacted, the catalyst for forming a carbon-carbon bond, and the amount used. It is determined by monitoring the progress by high performance liquid chromatography (HPLC) or the like, and is usually 10 minutes to 170 hours.

As the α-halogenocarboxylic acid derivative and the unsaturated compound, commercially available products or those appropriately produced by a conventional method may be used. Also, the azo compound represented by the general formula [1] may be a commercially available product or may be a US Patent No.
Those manufactured according to the manufacturing methods described in Japanese Patent No. 2586995 and Japanese Patent Application Laid-Open No. 50-13328 may also be used.

As described above, the carbon to which the halogen atom of the α-halogenocarboxylic acid derivative represented by the general formula [2] is bonded and the R of the alkene represented by the general formula [3] or [3 ′] _The compound (adduct) represented by the above general formula [4] or [4 ′] is obtained by forming a new carbon-carbon bond by bonding with the carbon to which ₉ or R ₅ is bonded. The resulting compound (adduct) has a high reactivity because it contains a halogen atom in the molecule. If the compound (adduct) is reacted with, for example, a lower alcohol or the like, the alcohol using the halogen atom can be used. An alkoxy derivative substituted with a derived alkoxy group can be obtained.

The present invention is characterized in that the azo compound represented by the above general formula [1] used as a radical initiator is used as a catalyst for forming a carbon-carbon bond. Since the azo compound generates a radical species at around room temperature, it does not require heating or the like to generate a radical species such as azobisisobutyronitrile, which is usually used as a radical initiator, so that a side reaction may occur. Control and stereo control are possible. That is, by using the catalyst for forming a carbon-carbon bond comprising the azo compound represented by the general formula [1] of the present invention, for example, the α-formula represented by the general formula [2] can be obtained.
For example, a regioselective addition reaction of a halogenocarboxylic acid derivative to an unsaturated compound such as an alkene represented by the above general formula [3] or [3 '], that is, a reaction of the α-halogenocarboxylic acid derivative with the alkene or the like. Selective addition to a saturated compound becomes possible, and the desired compound (adduct) represented, for example, by the above general formula [4] or [4 ′] can be obtained in high yield.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0043]

The formal names of the abbreviations used in the following Examples, Comparative Examples and Tables are as follows. V-70: 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) [Wako Pure Chemical Industries, Ltd. Product name. AIBN: azobisisobutyronitrile BPO: benzoyl peroxide Et ₃ B: triethylborane IPE: diisopropyl ether TBME: tert-butyl methyl ether

Embodiment 1 A mixture of 10 mmol of styrene, 10 mmol of bromomalononitrile and 10 ml of methylene chloride was added with 5 mol% of V-70, and the mixture was added at room temperature (25 ° C.).
The reaction was stirred for a period of time. After completion of the reaction, the solvent was distilled off, and 10 ml of 2-propanol was added to the residue to precipitate the desired product.
This is collected by filtration, washed and dried to obtain the desired adduct (yield
79%).

[0045]

(Equation 1)

Comparative Examples 1 to 3. The reaction was carried out in the same manner as in Example 1 except that the kind of the radical polymerization initiator to be used and the reaction time were as shown in Table 1. The results are shown in Table 1 together with the results of Example 1.

Comparative Example 4 In Comparative Example 1, the reaction temperature was
The temperature was raised to 40 ° C., and the reaction was carried out in the same manner as in Comparative Example 1. As a result, (1,2-dibromoethyl) benzene was obtained.

[0048]

[Table 1]

From the above results, when AIBN (Comparative Example 1) which is a typical azo radical initiator and BPO (Comparative Example 2) which is a typical peroxide radical initiator were used, At room temperature (25 ° C.), the reaction did not proceed.
When t ₃ B was used (Comparative Example 3), the desired adduct was obtained, but the yield was low because Et ₃ B was thought to have accelerated the decomposition of bromomalononitrile. on the other hand,
When V-70 was used as a radical initiator (Example 1), the target adduct could be obtained in a yield of 79% under the same conditions. Furthermore, in Comparative Example 1, AIB
Since no N radical species was generated, the same synthesis was performed by heating (40 ° C.) to generate a radical species (Comparative Example 4), but even in that case, (1,2-dibromo) represented by the following formula was used. Ethyl) benzene (dibromo form) was produced preferentially, and the desired adduct could not be obtained.

[0050]

Embedded image

From the above, it can be seen that the method of the present invention is clearly superior to the conventional method using AIBN or the like.

Embodiments 2 to 5 A target adduct was obtained in the same manner as in Example 1 except that the reaction temperature and the reaction time were changed as shown in Table 2. The results are shown in Table 2 together with the results of Example 1.

[0053]

[Table 2]

From the above results, V-70 was measured at 10 ° C. and 0 ° C.
It can be seen that, even under the condition of ° C., by extending the reaction time, the desired adduct can be obtained in high yield.

Embodiments 6-9. In Example 1, V-7
A target adduct was obtained in the same manner as in Example 1 except that the amount of 0 and the reaction time were as shown in Table 3. The results are shown in Table 3 together with the results of Example 1.

Comparative Example 5 The reaction was carried out in the same manner as in Example 1 except that V-70 was not used and the reaction time was changed to 48 hours. The results are shown in Table 3.

[0057]

[Table 3]

From the above results, it can be seen that V-70 works effectively even at a concentration of 0.1 mol% and gives an adduct in high yield.

Example 10 10 mmol of 2-methyl-2-butene, 10 mmol of bromomalononitrile and 10 ml of methylene chloride were mixed, and 5 mol% of V-70 was added thereto.
The reaction was stirred for a period of time. After completion of the reaction, the solvent was distilled off, and the residue was subjected to silica gel column chromatography [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.), eluent: n
-Hexane / ethyl acetate] to give the desired adduct (81% yield). Table 4 shows the results.

Embodiments 11 to 19 The desired adduct was obtained in the same manner as in Example 10 except that 2-methyl-2-butene and the reaction time were changed as shown in Table 4.
The results are shown in Table 4.

The reaction formulas of Examples 10 to 19 are shown below.

[0062]

(Equation 2)

[0063]

[Table 4]

From the above results, it can be seen that the addition reaction of bromomalononitrile to the alkene gives the corresponding desired adduct in high yield under mild conditions at room temperature. When AIBN is used under heating conditions, bromomalononitrile is bonded via an oxygen-containing substituent such as ethyl 1-propenyl ether (that is, via an oxygen atom such as an alkoxy group or an alkyloxycarbonyl group). Although it has been reported that the compound does not react with an alkene having a functional group represented by (J. Am. Chem. Soc., 114 , 4436 (199)
2).), It was found that when V-70 was used, the reaction proceeded almost quantitatively with alkenes having oxygen-containing substituents such as enol derivatives (Examples 14 and 15). This also shows that the method of the present invention is clearly superior.

Example 20 1 g of 1-methoxy-5-methoxycarbonylphenyl-1-pentene, bromomalononitrile
0.62 g and methylene chloride (15 ml) were mixed.
After adding 25 mol% of 0, the mixture was stirred and reacted at 25 ° C. for 2 hours. After completion of the reaction, the solvent was distilled off, methanol was added to the residue, and the mixture was further reacted at the same temperature for 15 minutes with stirring. After the completion of the reaction, 10 ml of a saturated aqueous solution of sodium hydrogen carbonate was added, and the mixture was extracted with methylene chloride.
I got This was purified by column chromatography to obtain 1.3 g of the desired product. Table 5 shows the results.

Comparative Example 6. 10 mmol of 1-methoxy-5-methoxycarbonylphenyl-1-pentene, 10 mmol of bromomalononitrile and 10 ml of methylene chloride were mixed, and AI was added thereto.
After adding 10 mol% of BN, the mixture was stirred and reacted at 25 ° C. for 24 hours. After the completion of the reaction, the solvent was distilled off, methanol was added to the residue, and the mixture was further reacted with stirring at the same temperature for 15 minutes. After completion of the reaction, 10 ml of a saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with methylene chloride. The solvent was distilled off to obtain 1.7 g of a crude product. The results are shown in Table 5.

The reaction formulas of Example 20 and Comparative Example 6 are shown below.

[0068]

(Equation 3)

[0069]

[Table 5] 1) Isolation yield after column chromatography. 2) Object ³⁾ Ratio of by-product 3) Object

[0070]

Embedded image

From the above results, it was found that bromomalononitrile was
Compared with the case where the addition reaction to 1-methoxy-5-methoxycarbonylphenyl-1-pentene was performed using AIBN,
It can be seen that when the reaction was carried out using -70, the desired product was obtained in high yield. This also indicates that the method using V-70 of the present invention is clearly superior to the method using conventional AIBN.

Embodiment 21 FIG. Styrene (10 mmol), methylbromomalononitrile (10 mmol) and methylene chloride (10 ml) were mixed, and V-70 (10 mol%) was added thereto, followed by stirring and reaction at 25 ° C. for 24 hours. After the completion of the reaction, the solvent is distilled off to give a residue.
10 ml of 2-propanol was added to precipitate the desired product. This was collected by filtration, washed and dried to obtain the desired adduct.
Table 6 shows the results.

Comparative Example 7 Styrene (10 mmol), methylbromomalononitrile (10 mmol) and methylene chloride (10 ml) were mixed, AIBN (10 mol%) was added thereto, and the mixture was stirred and reacted at 80 ° C. for 1 hour. After the completion of the reaction, the solvent is distilled off to give a residue.
10 ml of 2-propanol was added to precipitate the desired product. This was collected by filtration, washed and dried to obtain the desired adduct.
The results are shown in Table 6.

The reaction formulas of Example 21 and Comparative Example 7 are shown below.

[0075]

(Equation 4)

[0076]

[Table 6]

As is evident from the above results, the addition reaction of methyl bromomalononitrile to styrene is carried out by AIB
Under heating conditions when N is used, the diastereomer formation ratio of the product is 50:50, but the reaction is carried out at room temperature using V-70 to produce the desired adduct (86:14). (syn form) can be obtained. That is, it can be seen that the intended adduct (syn form) can be selectively obtained by using V-70.

[0078]

As described above, the present invention provides a novel catalyst for forming a carbon-carbon bond, a method for forming a carbon-carbon bond using the catalyst, and a regioselective addition reaction using the catalyst. By using such a catalyst, a method for regioselectively adding to an unsaturated bond, which has been difficult in the past, becomes possible, and the desired adduct can be obtained in high yield.

Embedded image

Embedded image

Embedded image

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 255/31 C07C 255/31 255/35 255/35 255/41 255/41 255/65 255/65 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Masahisa Oka 1633 Oji-machiba, Kawagoe-shi, Saitama Wako Pure Chemical Industries, Ltd.Tokyo Research Laboratory (72) Inventor Masato Matsugi 3-5-38 Onohara Higashi, Minoh-shi, Osaka ( 72) Inventor Takenori Gotanda 2-18-19-210 Ishimaru, Minoh-shi, Osaka

Claims (14)

[Claims] 1. A catalyst for forming a carbon-carbon bond comprising an azo compound represented by the following general formula [1]. Embedded image (In the formula, R ₁ represents a lower alkyl group.) 2. The catalyst according to claim 1, wherein the carbon-carbon bond formation is a carbon-carbon bond formation by an addition reaction. 3. The catalyst according to claim 2, wherein the addition reaction is an addition of an α-halogenocarboxylic acid derivative to the unsaturated compound. 4. The method according to claim 3, wherein the unsaturated compound is an alkene.
The catalyst according to the above. 5. The catalyst according to claim 3, wherein the α-halogenocarboxylic acid derivative is a compound represented by the following general formula [2]. Embedded image (Wherein X represents a halogen atom, and at least one of R ₃ and R ₄ is an alkyloxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, a cyano group, a carbamoyl group or a carboxyl group. And R ₂ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group which may have a substituent, an alkoxy group, an aralkyloxy group, an aryloxy group or a hydroxy group.) 6. The catalyst according to claim 4, wherein the alkene is a compound represented by the following general formula [3]. Embedded image (Wherein, R ₅ is a hydrogen atom, an alkyl group, a haloalkyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an aliphatic heterocyclic group, an aromatic heterocyclic group. Group, alkyloxycarbonyl group, hydroxyalkyloxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, acyloxy group, acyl group, alkoxy group, aralkyloxy group, aryloxy group, cyano group, amino group, carbamoyl group, hydroxyl R ₆ represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group which may have a substituent, an alkyloxycarbonyl group, a hydroxyalkyloxycarbonyl group, a hydroxyl group, a sulfonic acid group, an aldehyde group or a carboxyl group; It represents a group or a carboxyl group, R ₉ is alkylene Represents a group or a bond, R ₇ is a hydrogen atom, an alkyl group, a carboxyl group, an alkyloxycarbonyl group, hydroxyalkyl alkyloxycarbonyl group or a hydroxyl group, R ₈ represents a hydrogen atom, a halogen atom or an alkyl group. The , R ₇ and R ₈ may form an aliphatic ring.) 7. A method for forming a carbon-carbon bond, comprising using the catalyst according to claim 1. 8. A method for forming a carbon-carbon bond, comprising reacting an α-halogenocarboxylic acid derivative with an unsaturated compound in the presence of the catalyst according to claim 1. 9. The unsaturated compound is an alkene.
5. The method for forming a carbon-carbon bond according to item 1. 10. The α-halogenocarboxylic acid derivative is a compound represented by the following general formula [2].
5. The method for forming a carbon-carbon bond according to item 1. Embedded image (In the formula, X represents a halogen atom, and at least one of R ₃ and R ₄ is an alkyloxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, a cyano group, a carbamoyl group or a carboxyl group. And R ₂ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group which may have a substituent, an alkoxy group, an aralkyloxy group, an aryloxy group or a hydroxy group.) 11. The method for forming a carbon-carbon bond according to claim 10, wherein the alkene is a compound represented by the following general formula [3]. Embedded image (Wherein R ₅ is a hydrogen atom, an alkyl group, a haloalkyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an aliphatic heterocyclic group, an aromatic heterocyclic group. Group, alkyloxycarbonyl group, hydroxyalkyloxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, acyloxy group, acyl group, alkoxy group, aralkyloxy group, aryloxy group, cyano group, amino group, carbamoyl group, hydroxyl R ₆ represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group which may have a substituent, an alkyloxycarbonyl group, a hydroxyalkyloxycarbonyl group, a hydroxyl group, a sulfonic group, an aldehyde group or a carboxyl group; It represents a group or a carboxyl group, R ₉ is alkylene Represents a group or a bond, R ₇ is a hydrogen atom, an alkyl group, a carboxyl group, an alkyloxycarbonyl group, hydroxyalkyl alkyloxycarbonyl group or a hydroxyl group, R ₈ represents a hydrogen atom, a halogen atom or an alkyl group. The , R ₇ and R ₈ may form an aliphatic ring.) 12. A method for adding an α-halogenocarboxylic acid derivative to an unsaturated compound, comprising using the catalyst according to claim 1. 13. The method according to claim 13, wherein the unsaturated compound is an alkene. 14. The addition method according to claim 13, wherein the addition method is a position-selective addition method.