JP2690038B2 - Benzo-1,4-disilacyclohexene derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention provides a novel 5,6-useful intermediate for fine chemicals such as pharmaceuticals and agricultural chemicals.
The present invention relates to a benzo-1,4-disilacyclohexene derivative and a method for producing the same.

[0002]

2. Description of the Prior Art 5,6-Benzo-1,4- according to the present invention
The disilacyclohexene derivative is a compound that has not been published in the literature, and its production method is not known.

[0003]

DISCLOSURE OF THE INVENTION The present invention uses novel raw materials which are inexpensive and can be obtained in large quantities under mild conditions and has a novel composition of 5,6.
-The problem is to produce a benzo-1,4-disilacyclohexene derivative.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that o-bis (dialkylsilyl) benzene compounds and 1,3-dienes are present in the presence of a specific catalyst. By reacting below, the above 5, 6
It was found that a -benzo-1,4-disilacyclohexene derivative was obtained, and based on this, the present invention was completed. That is, the present invention relates to (1) a compound represented by the general formula (I):

[0005]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different lower alkyl groups or hydrogen atoms, R ⁵ , R 3
⁶ and R ⁷ are a hydrogen atom or a lower alkyl group. ) 5,6-benzo-1,4-disilacyclohexene derivative represented by the formula (2), and (2) general formula (II)

[0007]

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(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups or hydrogen atoms.)
And a compound represented by the general formula (III)

[0009]

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(In the formula, R ⁵ , R ⁶ and R ⁷ are selected from a hydrogen atom, an alkyl group , a phenyl group or a naphthyl group.
Is an aryl group. And a 1,3-diene represented by the formula (1) are separately added to the platinum complex catalyst having a phosphine ligand (provided that the phosphine ligand is initially coordinated on the platinum complex). It may be in the form of.)
Of the general formula (IV), characterized by reacting in the presence of

[0011]

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(However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formula have the same meanings as defined in the above general formulas (II) and (III) .) 5,6-benzo-1,4-represented by
The present invention provides a method for producing a disilacyclohexene derivative.

In the manufacturing method (2) of the present invention,
R ¹ , R ² , R ³ and R ⁴ in the compound represented by the general formula (II) used as a starting material are each an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hydrogen atom. Thus, these may be the same as or different from each other. In addition, this general formula (II)
The benzene ring in may be substituted by a substituent inert to the reaction. Therefore, examples of the compound of the general formula (II) include o-bis (dimethylsilyl) benzene, o-bis (diethylsilyl) benzene, o-bis (dipropylsilyl) benzene, o-bis (dibutylsilyl) benzene. , O- (dimethylsilyl) (diethylsilyl) benzene, o-bis (methylethylsilyl) benzene, 1-dimethylsilyl-2-diethylsilylbenzene, 1,2-bis (dimethylsilyl) -3-methylbenzene, 1 , 2-bis (dimethylsilyl) -3-ethylbenzene, 1,2-bis (dimethylsilyl) -3-chlorobenzene, o-bis (methylsilyl) benzene and the like.

In the present invention, the 1,3-dienes to be reacted with the compound of the general formula (II) include R ⁵ and R ^{6 in the} general formula (III).
And R ⁷ is a hydrogen atom or a group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a benzyl group, a phenyl group and a naphthyl group. Examples of such 1,3-butadienes include 1,3-
Butadiene, 1,3-pentadiene, isoprene, 2-
Chloro-1,3-butadiene, cyclopentadiene,
1,3-decadiene, 1-phenyl-1.3-butadiene, etc. are mentioned.

In the method of the present invention, the compound represented by the general formula (II)
The quantity relationship between the compound represented by the formula (1) and the 1,3-dienes represented by the general formula (III) is usually 1/100 in molar ratio.
To 100, preferably 1/10 to 10
However, when a gaseous raw material is used, it may be used beyond this range, and a method of bubbling the gaseous raw material into the reaction system should be considered as an advantageous embodiment of the present invention. is there.

In the method of the present invention, the general formula (II)
The platinum complex catalyst having a phosphine ligand (however, the phosphine ligand is initially coordinated on the platinum complex) in the reaction between the compound represented by the formula (1) and the 1,3-dienes represented by the general formula (III) It may be contained in the form or may be added separately). Examples of such phosphine ligands include triphenylphosphine, trimethylphosphine, triethylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, tributylphosphine, tricyclohexylphosphine, and the like.

Therefore, as an example of the platinum complex catalyst containing a phosphine ligand used in the present invention, (η-ethylene) bis (triphenylphosphine) platinum, tetrakis (diphenylmethylphosphine) platinum, dichlorobis (phenyldimethylphosphine) platinum, Chlorohydridobis (tributylphosphine) platinum, dibromobis (triethylphosphine) platinum, dicarbonylbis (tributylphosphine) platinum, carbonatobis (tricyclohexylphosphine) platinum, diphenylacetylenebis (triphenylphosphine) platinum, bis (dibenzylideneacetone) Examples thereof include, but are not limited to, bis (triphenylphosphine) platinum.

Further, a method of adding a phosphine ligand to a platinum complex catalyst containing no phosphine ligand instead of using the platinum complex catalyst containing these phosphine ligands is also included in an advantageous embodiment of the present invention. Be done. Examples of such platinum complex catalysts include dichloro (tetramethylethylenediamine) platinum, dichlorobis (benzonitrile) platinum, tris (dibenzylideneacetone) diplatinum, bis (cyclooctadiene) platinum, and the like. It is not limited.

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

In the reaction of the present invention, a mixture of the compound represented by the general formula (II) and the 1,3-dienes represented by the general formula (III) to be subjected to the reaction is used without using a solvent. Easier to implement. However, the use of a solvent does not hinder the occurrence of this reaction, and the reaction is carried out in a solvent if necessary. These solvents are selected in consideration of the reactivity and boiling point of the compound represented by the general formula (II) to be reacted, the boiling point of the 1,3-diene represented by the general formula (III), etc. For example, it is preferable to select from hydrocarbon-based or ether-based solvents. The reaction of the present invention 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.

The product after the reaction can be easily separated by separating unreacted raw materials by distillation or the like and then subjecting it to rectification, recrystallization, chromatography and the like.

[0022]

According to the present invention, the compound represented by the general formula (II) and 1,3 represented by the general formula (III)
5,6, which is easily represented by the general formula (I) from diene
A benzo-1,4-disilacyclohexene derivative is obtained, and its industrial significance is great.

[0023]

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

Example 1 Isoprene was added to 2 ml of a 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 25 ° C. 0.25m
2 ml of a benzene solution containing a mole was added, and the mixture was stirred and reacted at 25 ° C. After reacting for 7 days, 1,1,4,4
-Tetramethyl-2-isopropenyl-1,3H-1,
4-benzodicillin

[0025]

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And 1,1,3,3-tetramethyl-2-
(2-Methyl-1-propenyl) -1,4-benzodisilolane

[0027]

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And 1,1,6,6-tetramethyl-3-
Methyl-1,5H-1,6-benzodisirocin

[0029]

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The mixtures of 75%, 10% and 9 respectively.
% Yield. The production ratio was determined by gas chromatography. Each compound was isolated and identified by preparative gas chromatography.

All of the present compounds are new compounds not listed in the literature, and their spectral data are as follows. 1,1,4,4-tetramethyl-2-isopropenyl-
1,3H-1,4-benzodicillin ¹ H-NMR (CDCl ₃ ): δ 7.55-7.19 (m, 4H), 4.76 (s, 1H), 4.6
3 (s, 1H), 1.98 (dd, J = 14,3Hz, 1H), 1.81 (s, 3H), 1.22 (t, J = 1
4Hz, 1H), 1.04 (dd, J = 14,3Hz, 1H), 0.34 (s, 3H), 0.28 (s, 3
H), 0.22 (s, 3H), 0.12 (s, 3H) GC-MS; 260 (M ⁺ , 19), 245 (19), 218 (60), 177 (100) IR; Figure 1

1,1,3,3-tetramethyl-2- (2
-Methyl- ¹ -propenyl) -1,4-benzodisilolane ¹ H-NMR: δ 7.52-7.27 (m, 4H), 5.09 (ddd, J = 111,1,1Hz, 1
H), 1.68 (d, J = 1Hz, 3H), 1.56 (d, J = 1Hz, 3H), 1.49 (d, J = 11H
z, 1H), 0.26 (s, 6H), 0.15 (s, 6H) ¹³ C-NMR; 149.56,131.97,129.67,127.06,120.33,25.
88,17.71,17.16, -0.53, -1.91 GC-MS; 260 (M ⁺ , 100), 245 (49), 217 (14), 203 (21), 191 (43)

1,1,6,6-Tetramethyl-3-methyl-1,5H-1,6-benzodisirocin ¹ H-NMR: δ 7.62-7.29 (m, 4H), 5.17 (dt, J = 8, 1Hz, 1H), 1.
76 (s, 1H), 1.69 (d, J = 8Hz, 2H), 1.59 (d, J = 1Hz, 3H), 1.55 (s,
1H), 0.40 (s, 6H), 0.34 (s, 6H) GC-MS; 260 (M ⁺ , 25), 245 (190), 218 (49), 177 (100) IR; Fig. 2

[Brief description of the drawings]

FIG. 1 is a schematic diagram of 1, synthesized according to an embodiment of the present invention.
1,4,4-tetramethyl-2-isopropenyl-1,
The infrared absorption spectrum of 3H-1,4-benzodicillin was measured by a liquid film method, the vertical axis represents the transmittance (%), and the horizontal axis represents the wave number (cm ^-1 ).

FIG. 2 is a schematic diagram of 1, synthesized according to an embodiment of the present invention.
1,6,6-Tetramethyl-3-methyl-1,5H-
The infrared absorption spectrum of 1,6-benzodisirocin was measured by the liquid film method, and the vertical axis represents the transmittance (%).
The horizontal axis is (cm ^-1 ).

Claims (2)

(57) [Claims] 1. A compound of the general formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different lower alkyl groups or hydrogen atoms, and R ⁵ , R ⁶ and R ⁷ are hydrogen atoms or lower alkyl groups). 5,
6-benzo-1,4-disilacyclohexene derivative. 2. A compound of the general formula (II) (Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups or hydrogen atoms), and a compound represented by the general formula (III): (Wherein R ⁵ , R ⁶ and R ⁷ are hydrogen atoms, alkyl groups , or aryl groups selected from a phenyl group or a naphthyl group .) The reaction is carried out in the presence of a platinum complex catalyst having a ligand (however, the phosphine ligand may be initially contained in the platinum complex in the form of coordination or may be added separately). Is represented by the general formula (IV): (However, in the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the above general formulas.
It has the same meaning as defined in (II) and (III) . ] The manufacturing method of the 5,6-benzo-1,4-disilacyclohexene derivative represented by these.