JP2500382B2 - Bis (1,2-bissilylethylene) s and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel bis (1,2-bissilylethylene) derivative useful as a synthetic intermediate for fine chemicals such as pharmaceuticals and agricultural chemicals, and a method for producing the same.

[0002]

2. Description of the Related Art Hitherto, bis (1,2-bissilylethylene) s having an aromatic condensed ring and a method for producing the same have not been known.

[0003]

DISCLOSURE OF THE INVENTION The present invention industrially advantageously produces bis (1,2-bissilylethylene) s having an aromatic condensed ring under mild conditions using readily available raw materials. A method, especially for the purpose of providing a novel compound.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that 1,2,4,5-tetrakis (dimethylsilyl) benzene and a specific acetylene compound are platinum compounds. It was found that the bis (1,2-bissilylethylene) derivative can be rapidly reacted in the presence of ## STR3 ## under mild conditions, and the present invention has been completed based on these findings.

That is, according to the present invention, 1,2,4,5-tetrakis (dimethylsilyl) benzene and general formula (I) R ¹ -C≡C-R ² (R ¹ and R ² are alkyl groups, cycloalkyl Group, an aryl group or an aralkyl group) is reacted with an acetylene group represented by the general formula (II) in the presence of a platinum compound.

Embedded image (In the formula, Me is a methyl group, R ¹ and R ² have the same meanings as described above), or the general formula (III)

[Chemical 6] (Wherein Me, R ¹ and R ² have the same meanings as described above), and a method for producing bis (1,2-bissilylethylene) s represented by the above formula The present invention provides new compounds represented by II) and (III).

In the acetylenes represented by the general formula (I) used in the method of the present invention, R ¹ and R ² in the formula are:
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, dodecanyl group, cycloalkyl groups such as cyclohexyl group, phenyl group, tolyl group, 1-naphthyl group, 2-naphthyl group, etc. An aralkyl group such as an aryl group, a benzyl group and a phenethyl group. Examples of such acetylenes include 3-hexyne, 1-phenyl-1-propyne, diphenylacetylene, phenyl (cyclohexyl) acetylene and the like.

In the method of the present invention, the reaction is considered to proceed according to the following equation.

[Chemical 7] (In the formula, Me, R ¹ and R ² each have the same meaning as described above).

In the method of the present invention, 1,2,
The molar ratio of 4,5-tetrakis (dimethylsilyl) benzene and acetylenes is usually 1: 100 to 20.
It is used in the range of 0: 1, preferably 1: 5 to 10: 1.

In the method of the present invention, the platinum compound acts as a catalyst, and various conventionally known compounds can be used. However, it is preferable in terms of reaction rate to use a compound which is at least partially soluble in the reaction system. . A complex containing an organic ligand is particularly preferably used as these compounds. Examples of the ligand used in the present invention include phosphine, phosphonite, phosphinite, phosphite, olefin, acetylene, β-diketonato ligand, conjugated ketone,
Examples include amines and carbon monoxide. Specific examples thereof include trimethylphosphine, tributylphosphine, triethylphosphine, tricyclohexylphosphine, triphenylphosphine and tri (p-tolyl).
Chain phosphines such as phosphine, tri (p-anisyl) phosphine, diphenylmethylphosphine and phenyldimethylphosphine, p-methylphosphorene, p-methylphosphole, 9-methyl-9-phosphabicyclo [4.
2.1] Cyclic phosphines such as 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) benzene and other bisphosphines, dimethyl methylphosphonite, dimethyl phenylphosphonite and other phosphonites, methyl dimethylphosphinite , Phenyldiphenylphosphinite and other phosphinites, and triethylphosphite, triphenylphosphite, 1-phospha-
2,6,7-trioxa-4-ethylbicyclo [2,
2,2] octane and other phosphites, ethylene, propene, cyclooctene, maleic anhydride, 1,5-hexadiene, 1,5-cyclooctadiene, 1,3-cyclopentadiene, 2,5-norbornadiene, 1, 3,
Olefins such as 5,7-cyclooctatetraene and dienes, β-diketonato ligands such as acetylacetonato, conjugated ketones such as dibenzylideneacetone, amines such as ethylenediamine and 2,2′-bipyridyl, and carbon monoxide Is mentioned. Therefore, specific examples of the platinum compound used in this reaction include (η-ethylene) bis (triphenylphosphine) platinum, tetrakis (diphenylmethylphosphine) platinum, dichlorobis (phenyldimethylphosphine) platinum and chlorohydridobis (tributylphosphine). ) Platinum, dichloro (tetramethylethylenediamine) platinum, dibromobis (triethylphosphite)
Platinum, bis (η-1,5-cyclooctadiene) platinum,
Dichloro (η-1,5-cyclooctadiene) platinum, dicarbonylbis (tributylphosphine) platinum, carbonatobis (tricyclohexylphosphine) platinum, bis (dibenzylideneacetone) bis (triphenylphosphine) platinum, bis (dibenzylideneacetone) ) Platinum and the like can be mentioned, but the invention is not limited thereto.

In addition, these platinum compounds are not used alone, but 2
It may be carried out in the coexistence of two or more species, and it is also included in an advantageous embodiment of the present invention that the same or different organic ligands from those contained in the platinum compound are added together with the platinum compound. .

The platinum compound may be used in a so-called catalytic amount, and is used in the range of 0.00001 to 0.5 mol per mol of 1,2,4,5-tetrakis (dimethylsilyl) benzene. The ligand is used in an amount of 1 to 20 mol, preferably 1 to 4 mol, per 1 mol of platinum atom.

The reaction of the present invention is easily carried out without using a solvent by using a mixture of 1,2,4,5-tetrakis (dimethylsilyl) benzene and acetylene to be subjected to the reaction. 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 selected in consideration of the reactivity and boiling point of 1,2,4,5-tetrakis (dimethylsilyl) benzene to be reacted, the boiling point of acetylenes and the like, and commonly used solvents such as hydrocarbon solvents. , Or an ether solvent is preferably selected.

In the method of the present invention, the reaction proceeds even 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 a commonly used means of organic chemistry such as ordinary distillation, recrystallization, chromatography, extraction with a solvent, or reprecipitation.

[0015]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 0.005 mmol of Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ (where Ph is a phenyl group), 1,2,4,5-
0.125 m of tetrakis (dimethylsilyl) benzene
When 4 ml of a benzene solution containing 0.25 mmol of diphenylacetylene and 1 mol of diphenylacetylene was reacted at 30 ° C. for 8 hours, it was confirmed by gas chromatography analysis that the starting compound had completely disappeared. 91% white sparingly soluble 1,4,5,8-tetrahydro-1,4
5,8-Tetrasila-1,1,4,4,5,5,8,8
-Octamethyl-2,3,6,7-tetraphenylanthracene was obtained. This compound could be crystallized from a large amount of benzene. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.

[0017]

Embedded image Melting point: 310 ° C. (DSC) ¹ H-NMR (C ₆ D ₆ ): δ 8.1 (s, 2H),
7.1-6.8 (m, 20H), 0.5 (s, 12
H), 0.4 (s, 12H) IR (KBr): 1259 cm ^-1 Elemental analysis C ₄₂ H ₄₆ Si ₄ (theoretical value) C 76.07%; H 6.99%: (actual value) C 76. 24%; H 7.04%

[0018]

According to the present invention, easily obtainable 1, 2,
Novel bis (1,2-bissilylethylene) s can be obtained from 4,5-tetrakis (dimethylsilyl) benzene and acetylenes in a single step, and their separation and purification are easy. It is useful as a synthetic intermediate for fine chemicals such as agricultural chemicals.

Claims (2)

(57) [Claims] 1. A compound of the general formula (In the formula, Me is a methyl group, R ¹ and R ² are alkyl groups, cycloalkyl groups, aryl groups or aralkyl groups), or a general formula: (In the formula, Me, R ¹ and R ² have the same meanings as described above) and bis (1,2-bissilylethylene) s. 2. 1,2,4,5-Tetrakis (dimethylsilyl) benzene and the general formula R ¹ -C≡C—R ² (R ¹ and R ² are an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. And a acetylene compound represented by the formula: in the presence of a platinum compound. (Wherein Me is a methyl group, R ¹ and R ² have the same meanings as described above), or the general formula: (In the formula, Me, R ¹ and R ² have the same meanings as described above.) A method for producing bis (1,2-bissilylethylene) s.