JP2706628B2 - Silylcyclopentane derivative 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 silylcyclopentane derivative and a method for producing the same. The novel silylcyclopentane derivative of the present invention is extremely useful as a starting material for synthesizing a new physiologically active substance, and has a single double bond. And as an important starting material for preparing new organosilicon polymer compounds.

[0002]

2. Description of the Related Art Allylsilane is a compound useful for the allylation reaction of various organic compounds such as halogen-substituted aliphatic hydrocarbons, aldehydes, ketones, acetals, nitriles and acid chlorides (I. Fleming, J. Dunogues). and R.
Smithers: “Organic Reaction”, Vol.37, Chap.2, Wi
ley, New York, 1989, pp57-575). Sakurai et al. Reacted allylsilane with an α, β-unsaturated ketone in the presence of a Lewis acid catalyst such as titanium tetrachloride and treated with water.
It has been found that a carbonyl compound in which a silyl group is removed and an allyl group is substituted can be obtained by a conjugate addition reaction.

[0003]

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This reaction is called the Sakurai reaction [A. Hosomi and H. Sakurai: J. Am. Chem. Soc., 99,
1673 (1977)], but it has been reported that this reaction also produces as a by-product a compound from which the silyl group is not removed [R. Pardo, JP Zahra and M. Santelli: Terahedron.
Lett., 4557 (1977)].

However, recently, Knolker and co-workers reported that unlike the Sakurai reaction, various allylsilanes having silicon atoms with large side chains and α, β-unsaturated ketones, such as titanium tetrachloride. It has been found that when the reaction is carried out in the presence of a Lewis acid catalyst, a 5-membered ring compound substituted with a silyl group can be synthesized as a main product by a [3 + 2] cycloaddition reaction.

[0006]

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(Wherein R ¹¹ , R ¹² and R ¹³ each represent a methyl group, a phenyl group, a t-butyl group or an isopropyl group)

In this reaction, it is stated that the larger the spatial size of the functional groups of R ¹¹ , R ¹² and R ¹³ , the more easily the [3 + 2] cycloaddition reaction occurs [H. -J. Knolker and N. Foitzi.
k, Anrew. Chem. Int. Ed. Engl., 32, 1081 (1993); H.
-J. Knolker and R. Graf, Tetrahedron Lett, 34, 476
5 (1993)].

[0009]

DISCLOSURE OF THE INVENTION The present invention relates to a novel physiologically active substance, a novel organosilicon compound and a novel silylcyclopentane which can be used as a starting material useful for the synthesis of a novel organosilicon polymer compound. It is intended to provide a derivative.

[0010]

The present invention provides a compound represented by the general formula (I):
Is a silylcyclopentane derivative represented by

[0011]

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[0012] (wherein, R ¹ and R ² each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or R ¹ and R
^{And 2} together form an alkylene group having 1 to 4 carbon atoms. R ^{3 to} R ⁹ each represent a hydrogen atom or a methyl group;
R ¹⁰ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a halophenyl group, a benzyl group or a 2-phenylethyl group)

The silylcyclopentane derivative represented by the general formula (I) of the present invention is produced by reacting a conjugated diene compound represented by the general formula (II) with an allylsilane represented by the general formula (III) in the presence of a Lewis acid catalyst. can do.

[0014]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as described above.) In the general formula (II), R ¹ and R ² are combined together to form an alkylene group having 1 to 4 carbon atoms. The diene compound is represented by the general formula (II ′), and the silylcyclopentane derivative obtained therefrom is represented by the general formula (I ′).

[0016]

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(Wherein R ^{3 to} R ¹⁰ are the same as described above;
Represents an integer of 1 to 4)

The process of the present invention uses a diene compound in which two double bonds are conjugated to obtain a silylcyclopentane derivative which is a compound that was unexpected in an allylsilation reaction. In this reaction, an intermediate in which allylsilane is added to a diene compound is generated as a reaction intermediate, and this intermediate is a [3 + 2] cycloaddition reaction including a 1,2-silyl shift (1,2-silyl shift) reaction. To form a cyclopentadiene derivative. In the Sakurai reaction, in order to produce a five-membered ring compound, an allylsilane compound having a large spatial size had to be used.In contrast, in the present invention, the reaction proceeds favorably even with an allylsilane having a small spatial size. By using a linear or cyclic conjugated diene compound that is not a carbonyl compound, a new and advanced production method capable of easily producing a five-membered ring compound having a hydrocarbon and a silyl group is provided. is there.

As the Lewis acid catalyst, halides of elements of Groups II to V and VIII of the periodic table are used, and among them, aluminum chloride, titanium chloride, tin chloride, boron chloride and mixtures thereof are preferred. Zinc, boron, titanium, iron, lead,
A mixture of chlorides such as cadmium and antimony can be used.

The conjugated diene compound of the general formula (II) or (II ') can be easily polymerized with a Lewis acid catalyst, and allylsilane (III) can cause an allylsilation reaction by itself. From, a mixture of a conjugated diene compound and allylsilane (III) at a predetermined molar ratio,
It is preferable that the reaction is performed by dropping into a reaction tank containing a solvent in which a catalyst has been previously mixed.

Specific examples of the solvent used in the present invention include:
Benzene, toluene, xylene, n-hexane, methylene chloride, chloroform, carbon tetrachloride and the like can be mentioned, preferably benzene, hexane, methylene chloride, chloroform and carbon tetrachloride, particularly preferably methylene chloride. . Allylsilane (III)
Is used in an amount of 0.1 to the amount of the conjugated diene compound (II).
The molar amount is preferably 5 to 20 times, more preferably 1 to 10 times, and most preferably 1 time. Reaction temperature is -4
The temperature is preferably from 0 to 40 ° C., but when the polymerization reaction of the conjugated diene compound is fast, it is preferable to increase the amount used or to lower the reaction temperature.

[0022]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
In the examples, the following symbols were used for nuclear magnetic resonance (NMR) spectrum analysis. S: single line, d: 2
Doublet, t: triplet, q: quadruple, p: quintuple, m: multiplet. The peak positions are shown in ppm using tetramethylsilane as the internal reference substance.

Example 1 3- (1-methylvinyl) -1
-Preparation of trimethylsilylcyclopentane Dry nitrogen gas was passed through a 50 ml 3-neck round bottom flask reaction vessel equipped with a magnetic stirrer, reflux condenser and dropping funnel, and flash dried. 0.25 g (1.9 mmol) of aluminum chloride and 10.0 ml of methylene chloride were added thereto, and 2.16 g (18.9 mmol) of allyltrimethylsilane and 1.29 g of isoprene were added to the dropping funnel.
(18.9 mmol) was added and mixed well. 20 reactors
Then, the mixture was kept in a water bath at a temperature of 0 ° C. and kept for several minutes so that the temperature of the reaction product became the same as the temperature of the water bath. After completion of the dropwise addition, the mixture was further stirred for 10 minutes and confirmed by gas chromatography. As a result, it was shown that the starting material had almost reacted. Then, 5 ml of water was put into the reaction vessel and stirred for 5 minutes to completely remove the activity of the catalyst, transferred to a separation funnel to separate a lower organic layer, and dried over anhydrous magnesium sulfate. The dried organic layer is subjected to vacuum distillation (22 to 24).
° C, 0.6 Torr), 0.87 g of 3- (1-methylvinyl) -1-trimethylsilylcyclopentane (yield 26
%). The NMR analysis data of this is shown below. _{^{1 H NMR (CDCl 3, δ}} ): 0.03 (s, 9H, Si-Me 3); 1.00-1.14
(m, 1H, ring-CH-SiMe ₃ ); 1.24-1.50 (m, 2H, ring-CH ₂ );
1.62 (t, 2H, ring-CH ₂ ); 1.75 (s, 3H, -CH ₃ ); 1.76-1.
87 (m, 2H, ring-CH ₂ ); 2.36-2.47 (p, 1H, ring-CH); 4.
69 (d, 2H, = CH ₂ )

Example 2: Preparation of 3-vinyl-1-trimethylsilylcyclopentane i) In a 50 ml glass sealed tube, 18.0 ml of h-hexane and 0.44 g of aluminum chloride (3. 33 mmol), and the sealed tube was placed in a dry ice / acetone trap at −78.
℃, further 3.79 g of allyltrimethylsilane
(33.3 mmol) was added. ii) Separately, 1.80 g (33.3 mmol) of 1,3-butadiene was sealed in a metal sealed tube under vacuum. iii) After connecting i) and ii) and transferring the 1,3-butadiene of ii) to the sealed tube of i) under vacuum, close the connecting cock and stir the temperature of the sealed tube while stirring with a magnetic stirrer. The dry ice / acetone trap was removed from -78 ° C to room temperature. After confirming the reaction was completed by gas chromatography after about 3.5 hours, 5 ml of water was added.
Was placed in a sealed tube, and stirred for 5 minutes to completely remove the activity of the catalyst. The mixture was transferred to a separation funnel to separate the upper organic layer, and then dried over anhydrous magnesium sulfate. The dried organic layer was subjected to vacuum distillation to obtain 2.23 g (yield: 40%) of 3-vinyl-1-trimethylsilylcyclopentane. The NMR analysis data of this is shown below. _{^{1 H NMR (CDCl 3, δ}} ): -0.03 (s, 9H, Si-Me 3); 1.00-1.14
(p, 1H, CH-SiMe ₃ ); 1.24-1.43 (m, 2H, ring-CH ₂ ); 1.
50-1.66 (m, 2H, ring-CH ₂ ); 1.75-1.87 (m, 2H, ring-CH ₂ )
₂ ); 2.40-2.52 (m, 1H, ring-CH); 4.70-5.00 (m, 2H, = C
H ₂ ); 5.75-5.88 (m, 1H, -CH =)

Example 3 3- (1-methylvinyl) -3
Preparation of -methyl-1-trimethylsilylcyclopentane Except that n-hexane was used instead of methylene chloride and 1.55 g (18.9 mmol) of 2,3-dimethyl-1,3-butadiene were used instead of isoprene. 1.19 g of 3- (1-methylvinyl) -3-methyl-1-trimethylsilylcyclopentane in the same manner as in Example 1.
(Yield 32%) was obtained. _{^{1 H NMR (CDCl 3, δ}} ): -0.03 (s, 9H, Si-Me 3); 1.00-1.18
(m, 1H, ring-CH-SiMe ₃ ); 1.09 (s, 3H, -CH ₃ ); 1.30-1.
60 (m, 4H, ring-CH ₂ ); 1.76 (s, 3H, -CH ₃ ); 1.76-1.90
(m, 2H, ring-CH ₂ ); 4.70-4.77 (m, 2H, = CH ₂ )

Example 4: 3- (2-methylvinyl) -1
Preparation of trimethylsilylcyclopentane 1.29 g of 1,3-pentadiene instead of isoprene
Except that (18.9 mmol) was used, the procedure was carried out in the same manner as in Example 1 to obtain 1.20 g (yield 35%) of 3- (2-methylvinyl) -1-trimethylsilylcyclopentane. _{^{1 H NMR (CDCl 3, δ}} ): -0.01 (s, 9H, Si-Me 3); 1.02-1.16
(p, 1H, CH-SiMe ₃ ); 1.23-1.42 (m, 2H, ring-CH ₂ ); 1.5
1-1.68 (m, 2H, ring-CH ₂ ); 1.73-1.85 (m, 2H, ring-C
H ₂ ); 1.95 (d, 2H, -CH ₃ ); 2.35-2.47 (m, 1H, ring-CH);
5.55-5.62 (m, 1H, = CH-); 5.75-5.83 (m, 1H, -CH =)

Example 5: 3- (2-ethylvinyl) -1
Preparation of trimethylsilylcyclopentane 1.55 g of 1,3-hexadiene instead of isoprene
Except that (18.9 mmol) was used, the procedure was carried out in the same manner as in Example 1 to obtain 1.40 g (yield 38%) of 3- (2-ethylvinyl) -1-trimethylsilylcyclopentane. ¹ H NMR (CDCl ₃ , δ): -0.01 (s, 9H, Si-Me ₃ ); 0.93 (t, 3
H, -CH ₂ CH ₃ ); 1.02-1.16 (p, 1H, CH-SiMe ₃ ); 1.23-1.42
(m, 2H, ring-CH ₂ ); 1.51-1.68 (m, 2H, ring-CH ₂ ); 1.7
3-1.85 (m, 2H, ring-CH ₂ ); 1.80-1.89 (m, 2H, -CH ₂ C
H ₃ ); 2.35-2.47 (m, 1H, ring-CH); 5.50-5.57 (m, 1H, =
CH-); 5.72-5.80 (m, 1H, -CH =)

Example 6 Preparation of 4-methyl-3- (2-methylvinyl) -1-trimethylsilylcyclopentane Instead of isoprene, 1.55 g of 2,4-hexadiene
(18.9 mmol), except that 4-methyl-3- (2-methylvinyl) -1- was used.
1.56 g of trimethylsilylcyclopentane (yield 42
%). ¹ H NMR (CDCl ₃ , δ): -0.01 (s, 9H, Si-Me ₃ ); 0.83 (d, 3
H, -CH ₃ ); 1.02-1.16 (p, 1H, CH-SiMe ₃ ); 1.51-1.68
(m, 2H, ring-CH ₂ ); 1.95 (d, 3H, -CH ₃ ); 1.63-1.76 (m,
2H, ring-CH ₂ ); 1.80-1.93 (m, 1H, ring-CH-); 2.35-
2.47 (m, 1H, ring-CH); 5.55-5.62 (m, 1H, = CH-); 5.75
-5.83 (m, 1H, -CH =)

Example 7: 4,4-dimethyl-3- (2,
Production of 2-dimethylvinyl) -1-trimethylsilylcyclopentane The same operation as in Example 1 was carried out except that 2.08 g (18.9 mmol) of 2,5-dimethyl-2,4-hexadiene was used instead of isoprene. 4,4-dimethyl-3-
1.40 g (yield 33%) of (2,2-dimethylvinyl) -1-trimethylsilylcyclopentane was obtained. ¹ H NMR (CDCl ₃ , δ): -0.01 (s, 9H, Si-Me ₃ ); 0.85 (s, 6
H, -CH ₃ ); 1.02-1.16 (p, 1H, CH-SiMe ₃ ); 1.51-1.68 (m,
2H, ring-CH ₃ ); 1.63-1.76 (m, 2H, ring-CH ₂ ); 1.93 (s,
6H, -CH ₃ ); 2.35-2.47 (t, 1H, ring-CH); 5.75-5.83 (m,
1H, -CH =)

Example 8: Preparation of 3-methyl-3- (2,2-dimethylvinyl) -1-trimethylsilylcyclopentane In place of isoprene, 1.81 g of 2,3-dimethyl-2,4-hexadiene (18 3.9 mmol) was used, except that 3-methyl-3- (2,2) was used.
1.11 g (yield 28%) of 2-dimethylvinyl) -1-trimethylsilylcyclopentane was obtained. ¹ H NMR (CDCl ₃ , δ): -0.01 (s, 9H, Si-Me ₃ ); 0.93 (s, 3
H, -CH ₃ ); 1.02-1.16 (p, 1H, CH-SiMe ₃ ); 1.32-1.49 (m,
2H, ring-CH ₂ ); 1.51-1.68 (m, 2H, ring-CH ₂ ); 1.63-1.7
6 (m, 2H, ring-CH ₂ ); 1.93 (s, 6H, -CH ₃ ); 5.75-5.83
(m, 1H, -CH =)

Example 9: Preparation of 7-trimethylsilyl-bicyclo [3.3.0] oct-2-ene 1.25 g of cyclopentadiene instead of isoprene
(18.9 mmol), except that 7-trimethylsilyl-bicyclo [3.3.
0] oct-2-ene (0.87 g, yield 26%). _{^{1 H NMR (CDCl 3, δ}} ): -0.04 (s, 9H, Si-Me 3); 0.82-0.95
(m, 1H, -CH-SiMe ₃ ); 1.31-1.52 (m, 4H, ring-CH ₂ ); 1.
92-2.01 (m, 1H, ring-CH); 2.60-2.83 (m, 2H, ring-C
H ₂ ); 2.20-2.28 (br m, 1H, ring-CH); 5.41-5.46 (m, 1
H, ring-CH =); 5.62-5.67 (m, 1H, ring-CH =)

Example 10: Preparation of 8-trimethylsilyl-bicyclo [4.3.0] non-2-ene Instead of isoprene, 1,3-cyclohexadiene 1.
Except that 51 g (18.9 mmol) was used, the same procedure as in Example 1 was carried out to give 8-trimethylsilyl-bicyclo [4.
3.0] Nona-2-ene (1.07 g, yield 29%) was obtained. ¹ H NMR (CDCl ₃ , δ): -0.01 (s, 9H, Si-Me ₃ ); 1.18 (p, 1
H, -CH-SiMe ₃ ); 1.41-1.70 (m, 6H, ring-CH ₂ ); 1.88-2.
08 (m, 2H, ring-CH ₂ ); 2.10-2.21 (m, 1H, ring-CH); 2.
45 (br m, 1H, ring-CH); 5.60-5.75 (m, 2H, ring-CH =)

Example 11: Preparation of 9-trimethylsilyl-bicyclo [5.3.0] dec-2-ene Instead of isoprene, 1,3-cycloheptadiene 1.
Except that 78 g (18.9 mmol) was used, the same procedure as in Example 1 was carried out to give 9-trimethylsilyl-bicyclo [5.
3.0] 1.73 g of deca-2-ene (44% yield). _{^{1 H NMR (CDCl 3, δ}} ): 0.00 (s, 9H, Si-Me 3); 1.20-1.33
(m, 1H, ring-CH-SiMe ₃ ); 1.50-1.84 (m, 8H, ring-CH ₃ );
1.85-2.05 (m, 2H, ring-CH ₂ ); 2.03-2.14 (m, 1H, ring
-CH); 2.35 (br m, 1H, ring-CH); 5.55-5.70 (m, 2H, ri
ng-CH =)

Example 12: Preparation of 10-trimethylsilyl-bicyclo [6.3.0] undec-2-ene Instead of isoprene, 1,3-cyclooctadiene 2.
1.93 g of 10-trimethylsilyl-bicyclo [5.3.0] undec-2-ene (yield 4) was carried out in the same manner as in Example 1 except that 04 g (18.9 mmol) was used.
8%). _{^{1 H NMR (CDCl 3, δ}} ): 0.00 (s, 9H, Si-Me 3); 1.25-1.36
(m, 1H, ring-CH-SiMe ₃ ); 1.43-1.80 (m, 10H, ring-C
H ₂ ); 1.85-2.05 (m, 2H, ring-CH ₂ ); 2.00-2.17 (m, 1H,
ring-CH); 2.27 (br m, 1H, ring-CH); 5.52-5.73 (m, 2
H, ring-CH =)

Example 13: 1-methyl-3-vinyl-1
Preparation of trimethylsilylcyclopentane 0.25 g (1.9 mmol) of aluminum chloride and 10.0 ml of methylene chloride as solvent, and 2.4 g (18.9 mmol) of 2-methylallyltrimethylsilane instead of allyltrimethylsilane and Except that 1.0 g (18.9 mmol) of 1,3-butadiene was used, 1.62 g of 1-methyl-3-vinyl-1-trimethylsilylcyclopentane was carried out in the same manner as in Example 2 (yield 47).
%). _{^{1 H NMR (CDCl 3, δ}} ): 0.01 (s, 9H, Si-Me 3); 0.62 (s, 3
H, CCH ₃ -SiMe ₃ ); 1.22-1.42 (m, 2H, ring-CH ₂ ); 1.51-
1.68 (m, 2H, ring-CH ₂ ); 1.76-1.85 (m, 2H, ring-CH ₂ );
2.43-2.55 (m, 1H, ring-CH); 4.69-4.99 (m, 2H, = C
H ₂ ); 5.67-5.89 (m, 1H, -CH =)

Example 14: 2-methyl-3-vinyl-1
-Production of trimethylsilylcyclopentane The procedure of Example 13 was repeated except that 2.4 g (18.9 mmol) of crotyltrimethylsilane was used instead of 2-methylallyltrimethylsilane.
Vinyl-1-trimethylsilylcyclopentane 1.62
g (yield 47%) was obtained. _{^{1 H NMR (CDCl 3, δ}} ): 0.02 (s, 9H, Si-Me 3); 1.33 (d, 3
H, -CH ₃ ); 1.24-1.44 (m, 2H, ring-CH ₂ ); 1.78-1.87 (m,
2H, ring-CH ₂ ); 1.95 (t, 1H, ring-CH); 2.45-2.58 (p,
1H, ring-CH); 4.70-5.02 (m, 2H, = CH ₂ ); 5.65-5.86 (m,
1H, -CH =)

Example 15: Preparation of 3-vinyl-1- (dimethylphenylsilyl) cyclopentane Except that 3.6 g (18.9 mmol) of allyldimethylphenylsilane was used instead of 2-methylallyltrimethylsilane. The same procedure as in Example 13 was followed to give 3-vinyl-
1- (dimethylphenylsilyl) cyclopentane 1.7
0 g (37% yield) was obtained. _{^{1 H NMR (CDCl 3, δ}} ): 0.32 (s, 6H, Si-Me 3); 1.32-1.46
(p, 1H, CH-SiMe ₃ ); 1.34-1.53 (m, 2H, ring-CH ₂ ); 1.5
5-1.72 (m, 2H, ring-CH ₂ ); 1.80-1.975 (m, 2H, ring-C
H ₂ ); 2.55-2.63 (m, 1H, ring-CH); 4.75-5.06 (m, 2H, =
CH ₂ ); 5.80-5.93 (m, 1H, -CH =); 7.30-7.55 (m, 5H, Ph)

Example 16: Preparation of 3-vinyl-1- (benzyldimethylsilyl) cyclopentane Except that 3.9 g (18.9 mmol) of allylbenzyldimethylsilane was used instead of 2-methylallyltrimethylsilane. The same procedure as in Example 13 was followed to give 3-vinyl-
1- (benzyldimethylsilyl) cyclopentane 1.9
1 g (yield 39%) was obtained. _{^{1 H NMR (CDCl 3, δ}} ): 0.00 (s, 6H, Si-Me 3); 1.05-1.19
(p, 1H, CH-SiMe ₃ ); 1.25-1.44 (m, 2H, ring-CH ₂ ); 1.5
2-1.68 (m, 2H, ring-CH ₂ ); 1.78-1.90 (m, 2H, ring-C
H ₂ ); 2.12 (s, 2H, -CH ₂ -Ph); 2.41-2.53 (m, 1H, ring-C
H); 4.71-5.02 (m, 2H, = CH ₂ ); 5.65-5.78 (m, 1H, -CH
=); 7.02-7.29 (m, 5H, Ph)

Example 17: Preparation of 3-vinyl-1-[(2-phenylethyl) dimethylsilyl] cyclopentane In place of 2-methylallyltrimethylsilane, 4.1 g of allyldimethyl (2-phenylethyl) silane was obtained. 18.
Except that 9 mmol) was used, 1.32 g (yield 26%) of 3-vinyl-1-[(2-phenylethyl) dimethylsilyl] cyclopentane was obtained in the same manner as in Example 13. ¹ H NMR (CDCl, δ): -0.02 (s, 6H, Si-Me ₃ ); 0.63 (t, 2
H, Si-CH _2- ); 1.03-1.16 (p, 1H, CH-SiMe ₃ ); 1.25-1.44
(m, 2H, ring-CH ₂ ); 1.52-1.68 (m, 2H, ring-CH ₂ ); 1.7
8-1.90 (m, 2H, ring-CH ₂ ); 2.30 (t, 2H, -CH ₂ -Ph); 2.4
1-2.53 (m, 1H, ring-CH); 4.71-5.02 (m, 2H, = CH ₂ ); 5.
65-5.78 (m, 1H, -CH =); 7.12-7.40 (m, 5H, Ph)

Example 18: Preparation of 3-vinyl-1-[(4-fluorophenyl) dimethylsilyl] cyclopentane Instead of 2-methylallyltrimethylsilane, 3.9 g of allyl (4-fluorophenyl) dimethylsilane ( 1
Except that 8.9 mmol) was used, 1.52 g of 3-vinyl-1-[(4-fluorophenyl) dimethylsilyl] cyclopentane was obtained in the same manner as in Example 13 (yield 31).
%). _{^{1 H NMR (CDCl 3, δ}} ): 0.16 (s, 6H, Si-Me 3); 1.16-1.30
(p, 1H, CH-SiMe ₃ ); 1.31-1.50 (m, 2H, ring-CH ₂ ); 1.5
1-1.68 (m, 2H, ring-CH ₂ ); 1.77-1.94 (m, 2H, ring-C
H ₂ ); 2.53-2.61 (m, 1H, ring-CH); 4.70-5.01 (m, 2H, =
CH ₂ ); 5.82-5.95 (m, 1H, -CH =); 7.12-7.37 (m, 4H, Ph)

[0041]

Since the novel silylcyclopentane derivative of the present invention has a double bond in the molecule, it can be used to produce a novel physiologically active substance, a novel organosilicon compound and a novel organosilicon compound. Useful for the synthesis of molecular compounds.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Han-Soo, Korea 453-1, Gwangsang-dong, Seong-gu, Seoul, Korea Republic of Korea 501-56 (56) Reference European Patent Application Publication 480528 (EP, A) TETRAHEDRON LETT . , 34-30! (1993), 4765. TETRAHEDRON, 49-44! (1993), 9555-9972.

Claims (6)

(57) [Claims] 1. A silylcyclopentane derivative represented by the general formula (I). Embedded image (Wherein, R ¹ and R ² each represent a hydrogen atom or a carbon number of 1 to 8)
Or R ¹ and R ² together form an alkylene group having 1 to 4 carbon atoms. R ³ ~
R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a halophenyl group, a benzyl group or a 2-phenylethyl group. 2. A method for producing a silylcyclopentane derivative of the general formula (I), wherein a conjugated diene compound of the general formula (II) is reacted with an allylsilane of the general formula (III) in the presence of a Lewis acid catalyst. Embedded image (In the above formula, R ¹ and R ² each represent a hydrogen atom or a carbon atom 1
Represents an alkyl group of ８8, or R ¹ and R ² together form an alkylene group having 1 to 4 carbon atoms. R ³
To R ⁹ each represent a hydrogen atom or a methyl group, and R ¹⁰ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a halophenyl group,
Represents a benzyl group or a 2-phenylethyl group) 3. The method for producing a silylcyclopentane derivative according to claim 2, wherein the reaction is carried out in a solvent selected from the group consisting of benzene, hexane, methylene chloride, chloroform and carbon tetrachloride. 4. The Lewis acid catalyst is aluminum chloride,
The method for producing a silylcyclopentane derivative according to claim 2, which is a Lewis acid selected from the group consisting of titanium chloride, tin chloride, boron chloride and a mixture thereof. 5. The use amount of the allylsilane of the general formula (III) is 1 to 1 with respect to the use amount of the conjugated diene compound of the general formula (II).
3. The method for producing a silylcyclopentane derivative according to claim 2, wherein the molar amount is 0-fold. 6. The method for producing a cyclopentane derivative according to claim 2, wherein the reaction temperature is -40 to 40 ° C.