JPH03258791A - 1-siloxy-3-silyl-1-propene 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 vinylketone in the presence of a catalyst. CONSTITUTION:The objective compound of formula III 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 atom or H) and (B) a vinylketone of formula II (R<5> is monovalent organic group) 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 IV (R<7>-R<11> are each 1-15C organic group, H or halogen; R<15> is 1-15C organic group).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing 1-siloxy-3-silyl-1-propene derivatives by reacting hydrosilanes and vinyl ketones.

1-Siloxy-3-silyl-1-propene derivatives are useful as synthetic intermediates for fine chemicals such as medicines and agricultural chemicals.

[Prior art] General formula 81R''5i-CH, -CH=CR' -0-
5iR'R'-Y (in the formula, R', R", R"
, R', R' and Y are as described above), and there is no known industrially advantageous method for producing the 1-siloxy-3-silyl-1-propene derivative.

[Problems to be Solved by the Invention] The present invention makes it possible to industrially advantageously produce 1-siloxy-3-silyl-1-propene derivatives under mild conditions using raw materials that are inexpensive and available in large quantities. The IIM is to provide a method.

Another object of the present invention is to provide a novel 1-siloxy-3-silyl-1-propene derivative obtained thereby.

[Means for Solving the Problems] W(1) As a result of intensive research by the present inventors to solve the above problems, (a) General formula HRlR"5i-Y-5iR3R'H(
However, in the formula, R'', R2, R3, R' and Y are each as described above) and (b) hydrosilanes represented by the general formula CH2=CH-R5C=0 (however, in the formula, R5 is as described above) ) is rapidly reacted under mild conditions in the presence of (C) a transition metal complex selected from platinum, palladium, and nickel.
-Siloxy-3-silyl-1-propene 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-CH, -CH=CR' -0
-SiR'R' -Y (wherein, R1, R2, R3
, R4, R5 and Y are each as described above).

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

HRlR"5L-Y-5iR3R'H+ CH2=CH
-R'C=O-)RlR''5i-CH2-C)I=CR
'-0-5iR3R'-Y + 82 (However, in the formula, R'
, R2, R", R', Rs and U'Y are as described above) The hydrosilanes (a) used in the present invention have the formula -H
R"R"5i-Y-5iR3R'H (wherein, R1,
R2, R3, R4 and Y are each as described above) R1, R2, R3 and R4 include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a bis(hydrocarbyl)amino group, a halogen Examples include atoms, hydrogen atoms, etc., and they may be the same or different.

In the general formula, Y is a divalent organic group, an oxygen atom, a nitrogen atom, or a sulfur atom, and the divalent organic group specifically includes (A) a divalent organic group having an aromatic ring structure (B) alkylene Group (C) A divalent group containing a typical element as a heteroatom (D)
Examples of heteroatoms include divalent organic groups containing transition metals.

etc. are listed.

Examples of (B) include the following, and examples of (C) include 10-CH2-, -CH, -0-CH, -, -CH, -
N(CH3)-CH2-.

etc. are mentioned, As (D), for example.

o-Ω mouth 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 0-bis(dimethylsilyl)benzene, 0-bis(
diphenylsilyl)benzene, 0-bis(dimethoxysilyl)benzene, 0-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-chlorobenzene, 1,2-bis(dimethylsilyl)ethane, 1. l, 3.3-tetramethyldisiloxane, 1,1,3.3-tetramethyldisilazane, bis-η
5-((dimethylsilyl)cyclopentadienyl)iron,
Examples include bis-η5-((dimethylsilyl)cyclopentadienyl)ruthenium.

The vinyl ketones (b) used in the present invention are:

General formula CH2=CH-R' C=0 (wherein, Rs is as described above).

Examples of Rs include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkoxymethyl group, and an aryloxymethyl group.

More specific examples of vinyl ketones used in the present invention include 3-buten-2-one, 4-penten-3-one,
1-phenyl-2-propen-1-one, 1-(4-chloro)phenyl-2-pronyl-2-propen-1-one, 1-(4-(N.

N-dimethylamino)) phenyl-2-propene-1-
on, 1-(4-methoxycarbonyl)phenyl-2-
Examples include propene-1-one.

The amount relationship between hydrosilanes and vinyl ketones is usually 1/100 to 10 in molar ratio of hydrosilanes and vinyl ketones.
It is carried out in the range of 0, preferably in the range of 1/10 to 10.

According to the present invention, a novel 1-siloxy-3-silyl-1-propene derivative represented by the following general formula is provided.

In the above formula, R7, R'', R' and R'' are alkyl groups,
Indicates an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, etc. R11, R'', R13 and R'' are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a bis(hydrocarbyl)amino group, a halogen atom,
Indicates hydrogen atoms, etc.

R15 can be selected from an alkyl group and an aryl group. Examples of the alkyl group, alkoxy group and acyl group include lower alkyl groups, alkoxy groups and acyl groups having 1 to 1 carbon atoms, and examples of the aryl group and aryloxy group include phenyl groups having 6 to 15 carbon atoms, Indicates tolyl group, phenoxy group, etc. Examples of the acyloxy group, alkoxycarbonyl group, and dos(hydrocarbyl)amino group include an acyloxy group having 1 to 1 o carbon atoms, an alkoxycarbonyl group, and a bis(hydrocarbyl)amino group. Fluorine is a halogen atom.

Examples include chlorine, bromine, and iodine atoms.

In the transition metal complex catalyst (C) used in the present invention, examples of the transition metal component include platinum, palladium, and nickel, and use of platinum is particularly preferred.

However, it is preferable from the viewpoint of reaction rate to use a compound that is at least partially soluble in the 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(tetramethylethylenediamine)platinum, dibromobis(triethylphosphite)platinum, dichlorobis(benzonitrile)platinum, bis(η-1,5-cyclooctadiene)platinum, dichloro(η- 1,5-cyclooctazine) platinum.

Dicarbonylbis(tributylphosphine)platinum, carbonatobis(tricyclohexylphosphine)platinum, diphenylacetylenebis(triphenylphosphine)platinum, bis(dibenzylideneacetone)bis(triphenylphosphine)platinum, (η-ethylene)bis(triphenyl) phosphine)palladium, tetrakis(diphenylmethylphosphine)palladium, dichlorobis(phenyldimethylphosphine)palladium, tris(dibenzylideneacetone)nipalladium, dichloro(η-1,5
-cyclooctadiene)palladium, bis(η-allyl)palladium, (η-ethylene)bis(triphenylphosphine)nickel, tricarbonyl(diphenylmethylphosphine)nickel, dibromobis(triethylphosphine)nickel, tetrakis(phenyldimethylphosphine) ) Nickel, bromotris (tributylphosphine) nickel 5bis (η5-cyclopentagenyl)
Examples include, but are not limited to, nickel, bis(acetylacetonato)nickel, and the like. 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. It is also included in an advantageous aspect of the invention.

Examples of such organic ligands include phosphine, phosphonite, phosphinite, phosphite, olefin, acetylene, β-diketone, amine, and nitrile. Examples of these include chains such as trimethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(p-tolyl)phosphine, tri(p-anilyl)phosphine, diphenylmethylphosphine, and phenyldimethylphosphine. cyclic phosphine, p-methylphosphole, p-methylphosphole, cyclic phosphine such as 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(dimethylphosphino)ferrocene, 1,1'-bis(diphenylphosphino)ferrocene, α,α'-bis(dimethylphosphino)
-o-xylene, 1,2-bis(dimethylphosphino)
Bisphosphines such as benzene, phosphonites such as dimethylmethylphosphonite and dimethylphenylphosphonite, phosphinites such as methyldimethylphosphinite and diphenyldisphinite, and phosphites such as triethyldisulfite, triphenylphosphite, and trimethylolpropane phosphite. .

Olefins such as ethylene, propene, cyclooctene, 1,5-hexadiene, 1,5-cyclooctadiene, 1゜3-cyclopentadiene, norbornadiene, 1゜3.5.7-cyclooctatetraene, phenylacetylene , acetylene such as diphenylacetylene, β-diketone 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 may be a so-called catalytic amount, and the molar ratio to hydrosilane is o, O○001 to 0.5.
used within the range.

The reaction of the present invention can be easily carried out without using a solvent or a mixture of hydrosilanes and vinyl ketones 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 vinyl ketones, 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.

[Effects of the Invention] According to the present invention, 1-siloxy-3-silyl-1-propene derivatives can be easily obtained from hydrosilanes and vinyl ketones, 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 (C)12=CH2)(PPh, )2 to 0.0
05mmol and.

-3-Ptene-2-
Add 2mβ of a benzene solution containing 0.25mmol of On,
The mixture was stirred and reacted at 40°C. After reacting for 2 days, it was concentrated and distilled to give 1゜1.6,6-tetramethyl-3-
Methyl-5H-2,1,6-benzoxadisilocin was obtained in a yield of 88%.

CH3''CH3 This compound is a new compound that has not been described in any literature, and its physical property values and spectral data are as follows.

Boiling point 65℃ 10.5mmHg (Kugerrohr)”
H-NMR (CDCl2); δ 7.67-7
．． 31 (m, 4H).

4.70 (d d , J = 6.IHz, LH
).

1.72 (d, J = IHz, 3H).

1.51 (d d , J = 6. IHz , Z
H).

0.46 (s, 6H), 0.31 (s, 6H)
) 13C-NMR (CDC5); 146.81.
146.04.143.44゜134.90.133.
85.12L67゜127.94.103.89.22
．． 13゜14.75.1.30 (2C), 0.35
(2C)GC-MS (EI, 70eV);
262 (M”, 45).

247 (8), 194 (100) IR (Figure 1)

[Brief explanation of drawings]

Figure 1 shows the 1°1.6,
The infrared absorption spectrum of 6-tetramethyl-3-methyl-5H-2,1,6-benzoxadisilosin was measured using the liquid m method, and the vertical axis is transmittance (%) and the horizontal axis is is the wave number (rho 1).

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) Vinyl ketones represented by the general formula CH_2=CH-R^5C=O (in the formula, R^5 represents a monovalent organic group or a hydrogen atom), (c) Among platinum, palladium, and nickel. The reaction is carried out in the presence of a transition metal complex selected from the general formula R^1R^2Si-CH_2-CH=CR^5-
O-SiR^3R^4-Y (However, in the formula, R^1, R^2
, R^3, R^4, R^5 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, and R^1^5 is an organic group with 1 carbon number. 1-siloxy-3-silyl-1-, which can be selected from among ~15 organic groups)
Propene derivative.