JPH07113035B2 - 1-siloxy-1-silylmethane derivative and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a 1-siloxy-1-silylmethane derivative by reacting hydrosilanes with aldehydes.

The 1-siloxy-1-silylmethane derivative is useful as a synthetic intermediate for fine chemicals such as medical and agricultural chemicals.

[Prior Art] No industrially advantageous method is known as a method for producing a 1-siloxy-1-silylmethane derivative according to the present invention.

[Problems to be Solved by the Invention] The present invention provides a method capable of industrially advantageously producing a 1-siloxy-1-silylmethane derivative under mild conditions using raw materials that are inexpensive and available in large quantities. That is the subject.

Moreover, it aims at providing the novel 1-siloxy-1-silylmethane derivative obtained by it.

[Means for Solving Problems] As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, the specific hydrosilanes and aldehydes are at least selected from unsaturated hydrocarbons and phosphines. The present invention was completed based on this finding based on the finding that it rapidly reacts under mild conditions in the presence of a platinum complex containing one kind of ligand to give a novel 1-siloxy-1-silylmethane derivative. Came to let.

That is, the present invention provides (1) the general formula (III) (In the formula, R ¹ , R ² , R ³ and R ^{4, which} may be the same or different, each represents a lower alkyl group or a hydrogen atom, and R ⁵
Represents a phenyl group. ) 1-siloxy-1-silylmethane derivative represented by
And (2) (a) general formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ represent the same or different alkyl groups or hydrogen atoms) and (b) the general formula (II) R ⁵ CHO (wherein , R ⁵ represents an alkyl group or an aryl group.) In the presence of (c) a platinum complex containing at least one ligand selected from unsaturated hydrocarbons and phosphines. General formula (III) characterized by (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above), and a method for producing a 1-siloxy-1-silylmethane derivative.

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

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.) The hydrosilanes of (a) used in the production method of the present invention have the general formula (I) In the formula, R ¹ , R ² , R ³ and R ⁴ are alkyl groups or hydrogen atoms and may be the same or different.

Further, it may have a substituent inert to the reaction on the benzene ring. More specific examples of the hydrosilanes used in the present invention include o-bis (dimethylsilyl) benzene, 1,2-bis (dimethylsilyl) -4-methoxybenzene, and 1,2-bis (dimethylsilyl) -4. -Chlorobenzene and the like can be mentioned.

The aldehydes of (b) used in the production method of the present invention are represented by the general formula (II) R ⁵ CHO, where R ⁵ is an alkyl group, an alkenyl group,
Represents an aryl group.

More specifically, examples of aldehydes used in the present invention include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, isovaleraldehyde, 2-methylbutanal, 2-methylpropanal, 2- Ethylhexanal, 1-hexanal, 1-undecanal, citronellal, 2-ethylcrotonaldehyde, cyclohexanecarbaldehyde, benzaldehyde, o-, m-, or p-tolualdehyde, o-, m-, or p-chlorobenzaldehyde Can be given.

The molar relationship between the hydrosilanes and the aldehydes is usually in the range of 1/100 to 100, preferably 1/10 to 10 in terms of the molar ratio of the hydrosilanes and the aldehydes.

In the compound of the present invention, the alkyl group may be an alkyl group having 1 to 10 carbon atoms, and the aryl group may be, for example, a phenyl group or tolyl group having 6 to 15 carbon atoms.

The platinum complex catalyst (c) used in the present invention is a platinum complex containing at least one ligand selected from unsaturated hydrocarbons and phosphines, and various conventionally known ones may be used. However, it is preferable in terms of reaction rate to use a compound that is at least partially soluble in the reaction system. Specific examples of these are (η-ethylene) bis (triphenylphosphine) platinum, tetrakis (diphenylmethylphosphine) platinum, dichlorobis (phenyldimethylphosphine) platinum, chlorohydridobis (tributylphosphine) platinum, dichloro (tetramethyl). Ethylenediamine) 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) platinum, etc. However, it is not limited to this.

Further, these platinum complexes may be carried out not only individually but also in a combination of two or more kinds, and may be carried out by adding together with the platinum complex an organic ligand which is the same as or different from that contained in the platinum complex. Included in an advantageous aspect of the invention.
Examples of such an organic ligand include phosphine, phosphonite, phosphinite, phosphite, olefin, β-diketone, amine and nitrile.
Examples of these are trimethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (p
-Chain phosphines such as -tolyl) phosphine, tri (p-anisyl) phosphine, diphenylmethylphosphine and phenyldimethylphosphine, p-methylphosphorene,
Cyclic phosphines such as p-methylphosphole, 9-methyl-9-phosphabicyclo [4.2.1] 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
-(Diphenylphosphino) butane, 1,1'-bis (dimethylphosphino) ferrocene, 1,1 '-(diphenylphosphino) ferrocene, α, α'-bis (dimethylphosphino) -o-xylene, 1 Bisphosphines such as 2,2-bis (dimethylphosphino) benzene, phosphonites such as dimethylmethylphosphonite and dimethylphenylphosphonite, phosphinites such as methyldimethylphosphinite and diphenylphosphanite, and triethylphosphite and triphenylphosphite Phosphites such as trimethylolpropane phosphite, ethylene, propene, cyclooctene, 1,5-hexadiene, 1,5-cyclooctadiene, 1,3-cyclopentadiene, norbornadiene, 1,3,5,7-cyclo Olefin such as octatetraene, β such as acetylacetone -Diketone, 2,2 '
Examples include amines such as bipyridyl and ethylenediamine, and nitrites such as benzonitrile.

The platinum complex catalyst may be used in a so-called catalytic amount, and the platinum complex catalyst is used in a molar ratio of 0.00001 to 0.5 with respect to hydrosilane.

The reaction of the present invention can be easily carried out by using a mixture of hydrosilanes and aldehydes to be subjected to the reaction without using a solvent. However, the use of a solvent does not hinder the occurrence of this reaction, and is carried out in a solvent if necessary. These solvents are preferably selected from commonly used solvents, for example, hydrocarbon-based or ether-based solvents in consideration of the reactivity and boiling point of hydrosilanes to be reacted and the boiling point of aldehydes.

The reaction of the present invention proceeds at 0 ° C. or lower, but heating to a temperature of up to 250 ° C. is also possible in order to reach a preferable rate. Although it depends on the structure of the raw material, a generally preferable temperature range is 0 to 150 ° C.

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

EFFECT OF THE INVENTION According to the present invention, a 1-siloxy-1-silylmethane derivative can be easily obtained from hydrosilanes and aldehydes,
Its industrial significance is enormous.

EXAMPLES Next, the present invention will be described in more detail with reference to examples.

Example 1 Benzene solution containing 0.25 mmol of benzaldehyde in 2 ml of benzene solution containing 0.005 mmol of Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ and 0.25 mmol of o-bis (dimethylsilyl) benzene at 80 ° C. 2 ml of the solution was added and reacted at 80 ° C. After reacting for 40 hours, the mixture was concentrated and distilled to obtain 1,1,4,4-tetramethyl-3-phenyl-2,1,4-benzoxadisilane at a yield of 40%.

This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows. ¹ H-NMR (CDCl ₃ ): δ 7.6-7.1 (m, 9H), 5.0 (s, 1
H), 0.43 (s, 3H), 0.37 (s, 3H), 0.29 (s, 3H), 0.00
(S, 3H), ¹³ C-NMR (CDCl ₃ ): δ 144.6,143.7,142.6,133.4,13
2.5,128.64,128.60,128.1 (2C), 125.5,124.5 (2C), 6
9.8,0.21, -0.62, -4.98, -5.03 GC-MS (EI, 70eV); 298 (M ⁺ , 39), 283 (16), 193 (10
0) IR (Fig. 1) Elemental analysis value: Measured value C 68.09%, H 7.48% Theoretical value C 68.40%, H 7.43%

[Brief description of drawings]

FIG. 1 shows the infrared absorption spectrum of 1,1,4,4-tetramethyl-3-phenyl-2,1,4-benzoxadisilane synthesized according to the example of the present invention, which was measured by the Nujol method. Yes, the vertical axis is the transmittance (%) and the horizontal axis is the wave number (cm
^-1 ).

Claims (2)

[Claims] 1. A general formula (III) (In the formula, R ¹ , R ² , R ³ and R ^{4, which} may be the same or different, each represents a lower alkyl group or a hydrogen atom, and R ⁵
Represents a phenyl group. ) 1-siloxy-1-silylmethane derivative represented by: 2. (a) General formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents an alkyl group or a hydrogen atom) and (b) the general formula (II) R ⁵ An aldehyde represented by CHO (wherein R ⁵ represents an alkyl group or an aryl group), and (c) platinum containing at least one ligand selected from unsaturated hydrocarbons and phosphines. General formula (III) characterized by reacting in the presence of a complex (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.) A method for producing a 1-siloxy-1-silylmethane derivative.