JPH03258793A - 1-siloxy-1-silylethylele derivative and production thereof - Google Patents

Abstract

PURPOSE:To obtain under mild condition the title derivative useful as an intermediate for synthesizing medicines and pesticides etc., using inexpensive raw materials available in large quantities by reaction between a hydrosilane and a ketene in the presence of a catalyst. CONSTITUTION:The objective compound of formula II can be obtained by reaction between (A) a hydrosilane of formula I (Y is divalent organic group, O, N or S; R<1>-R<4> are each monovalent organic group, halogen or H) and (B) a ketene of formula R<5>R<6>C=C=O (R<5> and R<6> are each monovalent organic group or H) in the presence of (C) a transition metal complex catalyst (said metal being selected from platinum, palladium and nickel). It is preferable that the objective compound be a compound of formula III (R7R<14> are each 1-15C organic group, H or halogen; R<15> and R<16> are each 1-15C organic group or H).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 1-siloxy-1-silylethylene derivatives by reacting hydrosilanes and ketenes.

1-Siloxy-1-silylethylene derivatives are useful as synthetic intermediates for fine chemicals such as medicines and agricultural chemicals.

[Prior art] General formula RlR"5i-Y-5iR3R'-0-C=C
R'R' (in the formula, RL, RZ, R3, R4, R
5, RI and Y are respectively as described above).
There is no known industrially advantageous method for producing -siloxy-1-silylethylene derivatives.

[Problems to be Solved by the Invention] The present invention provides a method for industrially advantageously producing 1-siloxy-1-silylethylene derivatives under mild conditions using raw materials that are inexpensive and available in large quantities. The task is to do so.

Another object of the present invention is to provide a novel disiloxy-1-silylethylene derivative obtained thereby.

[Means for Solving the Problems] As a result of intensive research by the present inventors to solve the above problems, (a) - Narrowing down f(R1R2Si-Y-SiR'R'H
(wherein, R1, R2, R', R' and Y are each as described above) and (b) -
Ketenes represented by R5R''C=C=O (wherein R5 and R' are as described above) are (c) in the presence of a transition metal complex selected from platinum, palladium, and nickel. reacts rapidly under mild conditions to 1
-Siloxy-1-silylethylene derivatives were discovered, and the present invention was completed based on this discovery.

That is, according to the present invention, the general formula RlR"5i-Y-5iR'R'-0-C=C
R5R' (in the formula, R1, R2, R3, R', Rs
, R@ and HiY are respectively expressed as above).
- A method for producing a siloxy-1-silylethylene derivative is provided.

The method of the present invention proceeds by a reaction represented by the following formula.

HR1R2Si-Y-SiR3R'H+ RsR”C=
C=O-+ (wherein, R1, R2, R", R',
(R', R' and Y are as described above) The hydrosilane (a) used in the present invention is
R1R2Si-Y-SiR3R'H (wherein, R1,
p, 2. R3, R4 and Y are as described above)
R1, R2, R3 and R4 represented by are an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Examples include an acyloxy group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, etc., and they may be the same or different from each other. -During narrowing down, Y is a divalent organic group, an oxygen atom, These are nitrogen atoms and sulfur atoms, and specific examples of divalent organic groups include (A) a divalent organic group having an aromatic ring structure, (B) an alkylene group, and (c) a divalent group containing typical elements as a heteroatom. Examples of the organic group (D) heteroatom include a divalent organic group containing a transition metal.

Examples of (A) include the following, examples of (B) include the following, and examples of (c) include -0-CH,-, -CH2-0-CH2-, - CH2-
N(cH3)-CH2-.

etc. are listed.

As (D), for example, etc. can be mentioned.

Moreover, various substituents can be included as substituents on the carbon atoms of the divalent organic group. Specific examples of such substituents include alkoxy groups, aryloxy groups, acyloxy groups, alkoxycarbonyl groups, acyl groups, bis(hydrocarbyl)amino groups, halogen atoms, and hydrogen atoms.

More specific examples of hydrosilanes used in the present invention include O-bis(dimethylsilyl)benzene, O-bis(
diphenylsilyl)benzene, 0-bis(dimethoxysilyl)benzene, O-bis(diphenoxysilyl)benzene, 0-(bis(dimethylamino)silyl)(dimethylsilyl)benzene, 0-bis(dichlorosilyl)benzene, 3 .4-bis(dimethylsilyl)pyridine, 2゜3-bis(dimethylsilyl)thiophene, 2,3-bis(dimethylsilyl)furan, 1,2-bis(dimethylsilyl)naphthalene, 1,2-bis(dimethyl) silyl)anthracene, 1,2-bis(dimethylsilyl)-4-methoxybenzene, 3゜4-bis(dimethylsilyl)phenylethyl ether, 1,2-bis(dimethylsilyl)
-4-Globenzene, 1,2-bis(dimethylsilyl)ethane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetramethyldisilazane.

Examples include bis-η5-((dimethylsilyl)cyclopentadienyl)iron, bis-η5-((dimethylsilyl)cyclopentagenyl)ruthenium, and the like.

The ketene (b) used in the present invention is represented by the general formula R'R' C=C=0 (in the formula, R5 and R@ are each as described above). Examples of RG and R1 include an alkyl group, an aryl group, an alkoxymethyl group, an aryloxymethyl group, an alkoxycarbonyl group, and a hydrogen atom.

More specific examples of ketenes used in the present invention include unsubstituted ketene, methyl ketene, dibutyl ketene, ethyl phenyl ketene, and diphenyl ketene.

Phenylmethoxycarbonylketene, o-, m- or P-tolylmethoxycarbonylketene, 0-5m-1
Or p-chlorophenylketene, 0-1m-1 or p-acetoxyphenylketene.

The molar ratio of hydrosilanes and ketenes is usually in the range of 1/100 to 100, preferably in the range of 1,710 to 10.

According to the present invention, a novel 1-siloxy-1-silylethylene derivative represented by the following general formula is provided.

In the above formula, R7, R2, R' and R'' are alkyl groups,
a R11, R2, R" and "Jin9 are alkyl groups,
R11 and R'' represent an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, etc. Indicates a group, hydrogen atom, etc.

Examples of the alkyl group, alkoxy group and acyl group include lower alkyl groups, alkoxy groups and acyl groups having 1 to 10 carbon atoms, and aryl groups.

The aryloxy group includes a phenyl group, tolyl group, phenoxy group, etc. having 6 to 15 carbon atoms, and the acyloxy group, alkoxycarbonyl group, and bis(hydrocarbyl)amino group includes an acyloxy group having 1 to 10 carbon atoms;
Examples include an alkoxycarbonyl group and a bis(hydrocarbyl)amino group. Examples of halogen atoms include fluorine, chlorine, and bromine.

An example is an iodine atom.

In the transition metal complex catalyst (c) used in the present invention, examples of the transition metal component include platinum, palladium, and nickel, and the use of platinum is particularly suitable for Wku-11. As the transition metal complex, various conventionally known ones can be used, but from the viewpoint of reaction rate, it is preferable to use a compound that is at least partially soluble in one reaction system. As these compounds, complexes containing organic ligands or carbon monoxide are particularly preferably used. Specific examples of these include (η-ethylene)bis(triphenylphosphine)platinum, tetrakis(diphenylmethylphosphine)platinum, dichlorobis(phenyldimethylphosphine)platinum, chlorohydridobis(tributylphosphine)platinum, dichloro(tetra methylethylenediamine)
Platinum, dibromobis(triethylphosphite) platinum,
Dichlorobis(benzonitrile)platinum, bis(η-1,
5-cyclooctadiene) platinum, dichloro(η-1,5
-cyclooctadiene) platinum, dicarbonylbis(tributylphosphine)platinum, carbonatobis(tricyclohexylphosphine)platinum, diphenylacetylenebis(triphenylphosphine)platinum, bis(dibenzylideneacetone)bis(triphenylphosphine) (shi: η Platinum, (η-ethylene)bis(triphenylphosphine)palladium, tetrakis(diphenylmethylphosphine)palladium, dichlorobis(phenyldimethylphosphine)palladium, tris(dibenzylideneacetone)nipalladium, dichloro(η-1,5-cyclo octadiene)palladium, bis(η-allyl)palladium, (η-ethylene)bis(triphenylphosphine)nickel, tricarbonyl(diphenylmethylphosphine)nickel, dibromobis(triethylphosphine)nickel, tetrakis(phenyldimethylphosphine)nickel , Bromotris (tributylphosphine)
Examples include nickel, bis(η5-cyclopentagenyl)nickel, bis(acetylacetonato)nickel, but are not limited thereto. In addition, these transition metal compounds may be used not only alone, but also in combination of two or more, and in addition, an organic ligand that is the same as or different from that contained in the transition metal compound is added together with the transition metal compound. Examples of such organic ligands of the present invention include phosphine, phosphonite, phosphinite, phosphite, olefin, acetylene, β
-diketones, amines, nitriles, etc. Examples include trimethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(P-tolyl)phosphine, tri(p-anisyl) phosphine,
Chain phosphine such as diphenylmethylphosphine, phenyldimethylphosphine, p-methylphosphine, p-
Cyclic phosphines such as methylbospol, 9-methyl-9-phosphabicyclo[4,2,11 nonane, 1,2-bis(dimethylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, 1 .4-bis(dimethylphosphino)butane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1.1 '-bis(dime1/'':: C: i-difuphosphino)ferrocene, 1,1'-bis(diphenylphosphino)ferrocene, α, α'-bis(dimethylphosphino)-〇-xylene, 1゜2 - Bisphosphine such as bis(dimethylphosphino)benzene, phosphonite such as dimethylmethylphosphonite, dimethylphenylphosphonite, phosphinite such as methyldimethylphosphinite, diphenylphosphinite, triethylphosphite, triphenylphosphite, triethylphosphite, etc. Phosphites such as methylolpropane phosphite, ethylene, propene, cyclooctene, 1,5-hexadiene, 1,5-cyclooctadiene, 1°3-cyclopentadiene, norbornadiene, 1°3.5.7-cyclo Olefins such as octatetraene, acetylenes such as phenylacetylene and diphenylacetylene, β-diketones such as acetylacetone, ethylenediamine, 2,2'-
Examples include amines such as bipyridyl and nitriles such as benzonitrile.

The amount of transition metal complex catalyst used is the so-called catalyst amount of 0.00
It is used in the range of 001 to 0.5.

The reaction of the present invention can be easily carried out without using any particular solvent by using a mixture of hydrosilanes and ketenes to be subjected to the reaction. However, the use of a solvent is not an obstacle to the occurrence of this reaction, and the reaction can be carried out in a solvent if necessary.

These solvents are preferably selected from commonly used solvents, such as hydrocarbon-based or ether-based solvents, taking into consideration the reactivity and boiling point of the hydrosilanes to be reacted, the boiling point of the ketenes, etc.

Although the reaction of the present invention will proceed below 0°C, it can be heated to temperatures up to 250°C to achieve preferred rates. Although it depends on the structure of the raw material, the preferred temperature range for boat fishing is 0 to 150°C.

Separation of the product after the reaction is easily carried out by separating unreacted raw materials by distillation or the like, and then subjecting the product to rectification, recrystallization, chromatography, or the like.

According to the present invention, 1-siloxy-1-silylethylene derivatives can be easily obtained from hydrosilanes and ketenes, and the industrial significance thereof is great.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

Example I Pt (cH,=CH2) (ppha)2 to 0.0
2 m of a benzene solution containing 0.5 mmol and 0.25 mmol of 〇-bis(dimethylsilyl)benzene at 30°C.
Then, 2 mA of a benzene solution containing 0.25 mmol of diphenylketene was added, and the mixture was reacted at 30°C. After reacting for one day, it was concentrated and distilled to reveal a new compound based on 1,1,4,4-tetramethyl-3-(diphenyl)methylidene-2,1,4-benzoxadisilane, and its physical properties and spectrum The data were as follows.

H-NMR (cDCI, ): 67.46-7.0
2 (m, 14H).

0.38 (s, 6H), 0.01 (s, 6H)
) GC-MS (E engineering, 70eV); 386 (M
', 96).

371 (10), 193 (100) IR (Figure 1)

[Brief explanation of drawings]

FIG. 1 shows 1°1.4.
4-tetramethyl-3-(diphenyl)methyltin-2
, 1,4-benzoxadisilane measured by a liquid film method, the vertical axis is transmittance (%), and the horizontal axis is wave number (rho 1). Procedural amendment (meiyu) 3 Kagiken No. 606 1, Case description 2, Title of invention 1990 Patent Application No. 57277 1-Siloxy-1-silylethylene derivative and its manufacturing method 3, Person making the amendment Address of patent applicant related to the case: 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo Name (1
14) Ken Sugiura, Director of the Agency of Industrial Science and Technology (6) Number of claims increased by amendment (8), Contents of amendment The following amendments will be made to the specification of this application. (1) In the line next to "rIR (Fig. 1)" on page 17, line 8, "Elemental analysis value: Actual value C74, 33%, H6,69
Insert "% theoretical value C74,56%, H6,78%".

Claims (2)

[Claims] (1) (a) General formula HR^1R^2Si-Y-SiR^
3R^4H (wherein, Y is a divalent organic group, an oxygen atom,
Hydrosilanes represented by a nitrogen atom, a sulfur atom, and R^1, R^2, R^3, and R^4 represent a monovalent organic group, a halogen atom, or a hydrogen atom; and (b) Ketenes represented by the general formula R^5R^6C=C=O (wherein R^5 and R^6 represent a monovalent organic group or a hydrogen atom), , the reaction is carried out in the presence of a transition metal complex selected from nickel, with the general formula R^1R^2Si-Y-SiR^3R^4-O-
C=CR^5R^6 (however, in the formula, R^1, R^2, R^
3, R^4, R^5, R^6 and Y are each as described above). (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^7, R^8, R^9, R^1^0, R
^1^1, R^1^2, R^1^3 and R^1^4 are organic groups with 1 to 15 carbon atoms, hydrogen atoms, and halogen atoms, R^1^5 and R^1 ^6 is an organic group having 1 to 15 carbon atoms,
A 1-siloxy-1-silylethylene derivative represented by (can be selected from hydrogen atoms).