JPH0314591A - Production of 1-silyl-1,3-diene - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the subject compound useful as a silane compound agent, modifier for resins, etc., by reacting a vinyl halide with a vinylsilane in the presence of a palladium catalyst having a phosphine ligand. CONSTITUTION:A vinyl halide expressed by formula I (R<1>, R<2> and R<3> are monofunctional substituent group; X is halogen atom) is reacted with a vinylsilane expressed by formula II (R<4> is monofunctional hydrocarbon group; R<5> is alkyl or siloxanyl; (n) is an integer of 0-2) at 0.8-1.2 charging ratio in the presence of a palladium catalyst having a phosphine ligand (preferably in an amount of 0.001-20mol% based on the vinyl halide) and amines are added as a dehydrohalogenating agent to carry out reaction, as necessary, in a solvent, such as toluene, at 30-250 deg.C to afford the objective compound expressed by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel method for producing organosilicon compounds. More specifically, the present invention relates to a method for producing a 1,3-diene in which silicon having an alkoxy group or a siloxanyloxy group is substituted at the 11-position.

[Technical background of the invention and its problems]

1,3-Butadiene derivatives substituted with a silyl group having a hydrolyzable group are known and are known to be useful as silane coupling agents, resin modifiers, and raw materials for combinations of various compounds.

However, the synthesis method uses 1,4-dichloro-2-butyne as a starting material and synthesizes it through steps such as hydrosilylation and dechlorination (Japanese Patent Application Laid-open No. 197694/1983), 1.3- Butadienyl halogen H′-di=[one H=
L: HS+(OR'')s-n...(3) By a special reaction such as the method of reacting magnesium chloride with a silane compound (Japanese Patent Application Laid-open No. 151196/1986, 205286/1986) However, its scope of application was narrow, and the substituents bonded to butadiene were extremely limited to halogen atoms or lower alkyl groups.

On the other hand, the reaction of vinyl iodide derivatives with vinylsilanes having only alkyl groups (e.g. trimethylvinylsilane) in the presence of a palladium catalyst is known, but in the literature, it is reported that the desilylation product or the target substance 1-silyl -1.3
-Desilylation is reported to be suppressed only in the presence of silver nitrate or in larger amounts than diene derivatives (J, Or
g. Chem. , 53. 4909 (1988)).

This report also reveals that under the same conditions, simple vinyl bromide hardly reacts. moreover,
This production method has the disadvantage that it is not suitable for industrial production because it uses an equivalent amount of silver nitrate to vinyl iodide.

[Purpose of the invention]

An object of the present invention is to provide a method for industrially obtaining 1-silyl-1,3-diene in high yield from vinyl halide and vinyl silane.

[Structure of the invention]

As a result of intensive studies on such a method, the present inventors discovered that a vinyl silane having a silyl group having an alkoxy group or a siloxanyloxy group with a vinyl halide in the presence of a palladium catalyst having a phosphine ligand. It has been discovered that the above object can be achieved by reacting, and the present invention has been hereby accomplished.

That is, the present invention provides a combination of a vinyl halide represented by the general formula (1) (where RI, R2.R3 represents a monovalent substituent, and x represents a halogen atom) and a vinyl halide represented by the general formula (2) OR')s-. , ・・
・(2) (However, R4 is a substituted or unsubstituted monovalent hydrocarbon group, R5 is an alkyl group or a siloysanyl group, n
represents an integer from 0 to 2) in the presence of a palladium catalyst having a phosphine ligand. , 3-diene.

R', R', and R' in the vinyl halide represented by the general formula (1) used in the present invention represent a monovalent substituent, and include a hydrogen atom, a halogen atom, an alkyl group, an aryl group, and a double bond. Aldehyde groups, ketone groups, ester groups, etc. that have a carboxyl group conjugated with are common. Further, as the halogen atom represented by X in general formula (1), iodine and bromine are preferable from the viewpoint of reactivity and easy availability.

Such vinyl halides include β-bremostyrene, α-promostyrene, β-iodostyrene, vinyl bromide, 1-bromo-1-proben, 1-iodocyclohexene, methyl 2-promobropenoate,
3-bromo-2-cyclohexenone, l-iodo-1-
Examples include hexene and (1-bromovinyl)trimethylsilane.

On the other hand, R4 in the vinyl silane represented by the general formula (2) of the present invention represents a substituted or unsubstituted l-valent hydrocarbon group, such as an alkyl group such as a methyl group, an ethyl group, a probyl group, a butyl group, or a hexyl group. Groups: cycloalkyl groups such as cyclopentyl group, cyclohexyl group; aralkyl groups such as 2-phenylethyl group, aryl groups such as phenyl group, tolyl group; and chloromethyl group, chlorophenyl group, 3,3,3-trifluoro group. Examples include substituted hydrocarbon groups such as a lobrovir group.

Further, as R5, methyl group, ethyl group, brobyl group,
Examples include alkyl groups such as isoprobyl group and butyl group, and siloxanyl groups such as trimethylsilyl group, pentamethyldisiloxanyl group, and heptamethyltrisiloxanyl group.

Such vinylsilanes include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinylmethyldiethoxysilane, vinylmethyldiproboxysilane,
Examples include vinyldimethylethoxysilane, vinyldimethylpropoxysilane, vinylphenyldiethoxysilane, vinylphenyldimethoxysilane, vinyltris(trimethylsiloxy)silane, and vinylmethylbis(trimethylsiloxy)silane.

The present invention is characterized in that a palladium catalyst having a phosphine ligand is used as a reaction catalyst when the vinyl halide and vinylsilane are reacted. It can be anything as long as it has
A complex having a phosphine ligand may be used, or the complex may be generated in the system. For example, tetrakis(triphenylphosphine)palladium(0), (η-ethylene)bis(triphenylphosphine)haladium(0),
Carbonyltris(triphenylphosphine>palladium(0), dichlorobis(triphenylphosphine)haladium(II), dichlorobis(phenyldiethylphosphine)palladium(II), dichloro[bis(diphenylphosphino)ethane]palladium(n), dichloro [Bis(diphenylphosphino)broban]palladium(II) and dichlorobis(benzonitrile)palladium(II), dichlorobis(acetonitrile)palladium(IF), diμ-chlorodichloropis(η-ethylene)nipalladium(■) , tris(dibenzylideneacetone)nipalladium(0>, diμ-chlorobis(η-allyl)nipalladium(II), cyclo(
Palladium complexes having ligands exchangeable with phosphine ligands such as l,5-cyclooctadiene) palladium (■) and palladium diacetate (n), triphenylphosphine, tri(0-}lyl)phosphine, Examples include combinations of phosphine ligands such as triethylphosphine.

The amount of catalyst used is 0, relative to the vinyl halide.
．． 001 to 20 mo 1% is preferable, and more preferably 0.1 to 5 mo 1%.

The charging ratio of the vinyl halide and vinyl silane used in the reaction may be any ratio, but is preferably in the range of 0.8 to 1.2 in order to use the reactants efficiently. However, it is also possible to use one of the reactants in large excess and use it as a reaction solvent.

In addition, during the reaction, it is preferable to add amines as a dehydrohalogenating agent to improve the reaction yield.
As such, tertiary amines such as triethylamine, tribubylamine, tributylamine, and benzyldimethylamine, and aromatic amines such as pyridine are commonly used. The amount of amines is preferably at least equivalent to the amount of hydrogen halide produced in the reaction.

The reaction temperature may range from 30 to 250°C, but preferably from 70 to 180°C. This reaction is generally carried out at normal pressure, but may be under increased or reduced pressure if necessary.

Further, the solvent used in the reaction is not particularly required, but may be used to improve the solubility of the catalyst or to control the temperature. Examples of such solvents include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, n-hebutane, naphtha, mineral spirits, and petroleum benzene; chloroform: carbon tetrachloride, trichloroethylene, perchloroethylene, 1.1.1 - } U Halogenated hydrocarbon solvents such as chloroethylene; ethyl ether, tetrahydrofuran, nitrite? Ether solvents such as glycol diethyl ether; ethyl acetate, butyl acetate,
Examples include ester solvents such as alcohol acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and aprotic polar solvents such as dimethyl formamide and dimethyl acetamide.

Alternatively, a large excess of the reactant used in the reaction, such as the vinylsilane described above, may be used as a solvent.

The reaction time is not particularly limited because it varies depending on the raw materials, catalyst or solvent used, reaction temperature, etc.

However, conditions are usually set so that the reaction is completed in 0.5 to 12 hours. The reaction is carried out by mixing the vinyl halide, vinyl silane, amines, palladium catalyst, and solvent, and heating and stirring the mixture.

Since the obtained compound was obtained through a highly selective reaction, it can be purified by known techniques such as distillation, gas chromatography, liquid chromatography, and column chromatography.

In order to increase the stability of raw materials and raw materials during reaction and purification, there is no problem in adding known appropriate polymerization inhibitors and antioxidants in advance as a conventional method.

〔Effect of the invention〕

According to the present invention, 1-silyl- 1,3
It has become possible to industrially produce -gen with good yield.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 β-promostyrene 1. 83g (10m
mol) vinyltriethoxysilane 2.85g (15
mmol), triethylamine 1.11g (llm
0.115 g (0.10 mmol) of trakistriphenylphosphine palladium (0) was added thereto, and the mixture was stirred at 150° C. for 5 hours under a nitrogen atmosphere. 20ml of benzene! In addition, the raw salt was filtered off, and a pale yellow transparent liquid was obtained by Kugel distillation (180-200°C (bath temperature)/2 mmHg). Furthermore, gas chromatography (S)
B30. 10%) yielded 1.78 g of liquid. From the results of NMR, IR, mass, and elemental analysis, it was found that the obtained compound was 1-triethoxysilyl-4-phenyl-1,3-butadiene. The yield was 61%. The analysis results are shown in Table I, N
The MR chart and IR chart are shown in FIG. 1 and FIG. 2, respectively.

Example 2 A reaction was carried out in the same manner as in Example 1 except that vinyltriethoxysilane was replaced with 4.85 g (15 mmol) of vinyltris(trimethylsiloxy)silane.Results 1-
2.45 g of tris(trimethylsiloxy)silyl-4-phenyl-1,3-butadiene was obtained. Yield is 58
%Met. The analysis results are summarized in Table 1.

Example 3 β-promostyrene was converted into 1-bromo-1-bropene 1.2
1g (10mmol) of vinyltriethoxysilane and 2.40g of vinylmethyljethoxysilane (
15 mmol) and 100 ml. The reaction was carried out in the same manner as in Example 1 in a pressure-resistant container. As a result, 1-methyldiethoxysilyl-1,3-pentadiene was 0.74
g was obtained. The yield was 37%. The analysis results are summarized in Table 1.

Comparative Example 1 The catalyst was tetrakistriphenylphosphine (0),
Dichlorobis(benzonitrile)palladium (II
) 0. 038g (0.10rnmol), and the reaction was carried out in the same manner as in Example (2). However, 150
”c. Even after 5 hours of reaction, no or almost no salt was observed, so a gas chromatograph (SE30, 10%)
The reaction mixture was analyzed. As a result, the β-
More than 90% of bromostyrene remained, and the target compound, 1-triethoxysilyl-4-phenyl-1,
It was confirmed that about 2% of 3-butadiene was produced.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an NMR chart of the compound obtained in Example 1, and FIG. 2 is a diagram showing the same <IR chart.

Claims (1)

[Claims] General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, R^1, R^2, R^3 are monovalent substituents,
represents a halogen atom) and the general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (However, R^4 is a substituted or unsubstituted monovalent carbonized Hydrogen group, R^5 is an alkyl group or siloxanyl group, n is 0
General formula (3) characterized by reacting vinylsilane (representing an integer between ~2) in the presence of a palladium catalyst having a phosphine ligand ▲There are mathematical formulas, chemical formulas, tables, etc.▼...・(3) (However, R^1, R^2, R^3, R^4, R^5,
(n is the same as above) A method for producing 1-silyl-1,3-diene.