KR0142143B1 - Ñò-silyolefins made by allysilation and process for preparing the same - Google Patents

Abstract

Reaction of allylsilanes as in formula (IV) with hydrocarbon compounds having a double or triple bond as in formula (I), (II) or (III) under a Lewis acid catalyst such as aluminum chloride By the (allylsilation) reaction it is possible to prepare new gamma-silylolefins (γ-silylolefins) to which allyl and silyl groups, such as general formula (V), (VI) or (iii), are added at the same time. The allyl silicide is not only a new and advanced process for the production of gamma-silylolefins, but the compounds produced here are capable of producing new types of organosilicon compounds or organosilicon polymer compounds by Useful compound for preparation.

In formula (V), R is an alkyl or alkenyl group up to C ₁ -C ₈ , -CH ₂ SiMe ₃ , benzyl, and the like, and in formula (VI), n is an integer from 3 to 6, and R ¹ represents hydrogen, methyl phenyl and the like, and R ² represents a phenyl group, an alkyl or alkenyl group up to C ₁ -C ₈ . R ³ and R ⁴ independently represent a hydrogen or methyl group and R ⁵ , R ⁶ , R ⁷ independently represent C ₁ -C ₈ alkyl, phenyl, halogenated phenyl (X = F, Cl, Br), benzyl, 2 -Phenylethyl and the like are indicated.

Description

Gamma-silylolefin by Allyl Siliconation and Its Preparation Method

The present invention relates to gamma-silylolefins and their preparation. In more detail, a hydrocarbon compound having a double bond or a triple bond as in formula (I), (II) or (III) is reacted with an allylsilane as in formula (IV) under a Lewis acid catalyst such as aluminum chloride. The present invention relates to a method for synthesizing new gamma-silylolefins to which allyl and silyl groups, such as general formula (V), (VI) or (iii), are added at the same time.

In general formula (I), R is an alkyl or alkenyl group up to C ₁ -C ₈ , -CH ₂ SiMe ₃ , benzyl, etc., in general formula (II), n is an integer of 3 to 6, and in general formula (III) R ¹ is hydrogen, methyl, phenyl and the like, and R ² represents a phenyl group, an alkyl or alkenyl group up to C ₁ -C ₈ .

Wherein R ³ and R ⁴ independently represent a hydrogen or methyl group, and R ⁵ , R ⁶ , R ⁷ independently represent C ₁ -C ₈ alkyl, phenyl, halogenated phenyl (X = F, Cl, Br), benzyl , 2-phenylethyl and the like are shown.

In formula (V), R is an alkyl or alkenyl group up to C ₁ -C ₈ , -CH ₂ SiMe ₃ , benzyl, and the like, and in formula (VI), n is an integer from 3 to 6, and ) R ¹ is hydrogen, methyl, phenyl and the like, R ² is a phenyl group, R represents an alkyl or alkenyl group up to C ₁ -C ₈ . R ³ and R ⁴ independently represent a hydrogen or methyl group and R ⁵ , R ⁶ , R ⁷ independently represent C ₁ -C ₈ alkyl, phenyl, halogenated phenyl (X = F, C1, Br), benzyl, 2 -Phenylethyl and the like are indicated.

Allylsilanes are useful compounds for the allylation of various organic compounds such as alkyl halides, aldehydes, ketones, acetals, acid chlorides, nitriles, etc. (I. Fleming, J. Dunogues and R. Smithers, Organic Reactions, Vo1.37 , Chap. 2, Wiley, New York, 1989, pp 57-575)

Sakurai and co-workers reported that allylsilane and α, β-unsaturated ketones were allylated under a Lewis acid catalyst such as titanium tetrachloride and treated with water to obtain a carbonyl compound with an allyl group. (A. Hosomi and H. Sakurai, J. Am. Chem. Soc., 99, 1673 (1977)).

When various kinds of allylsilanes having a group and α, β-unsaturated ketones are reacted under Lewis acid catalyst such as titanium tetrachloride [3 + 2], a pentagonal cyclic compound having a silyl group added as a main product can be synthesized through a ring addition reaction. Reported. The more bulky the R ¹ , R ² , and R ³ functional groups in this reaction, the more [3 + 2] ring addition reaction occurs (H. -J. Knolker and N. Foitzik, Angew. Chem. Int. Ed. Engl). , 32, 1081 (1993); H.-J. Knolker and R. Graf, Tetrahedron Lett., 34, 4765 (1993)).

In the formula, R ¹ , R ² , and R ³ each independently represent methyl, phenyl, t-butyl, isopropyl.

In the present invention, in the general formula (IV) and the hydrocarbon compound having a double bond or triple bond as in general formula (I), (II) or (III) without using an α, β unsaturated ketone as in Sakurai reaction. By reacting allylsilanes such as allyl silanes such as general formula (V), (VI) or (Ⅶ) new gamma-silylolefins (γ-silylolefins) added at the same time was obtained as the main product.

In general formula (I), R is an alkyl or alkenyl group up to C ₁ -C ₈ , -CH ₂ SiMe ₃ , benzyl, etc., in general formula (II), n is an integer of 3 to 6, and R ¹ is hydrogen, methyl , Phenyl and the like, R ² represents a phenyl group, an alkyl or alkenyl group up to C ₁ -C ₈ .

Wherein R ³ and R ⁴ independently represent a hydrogen or methyl group and R ⁵ , R ⁶ , R ⁷ independently represent C ₁ -C ₈ alkyl, phenyl, halogenated phenyl (X = F, Cl, Br), benzyl, 2-phenylethyl etc. are shown.

In formula (VI), R is an alkyl or alkenyl group up to C ₁ -C ₈ , -CH ₂ SiMe ₃ , benzyl, etc., in formula (VI), n is an integer of 3 to 6, and In i), R ¹ is hydrogen, methyl, phenyl and the like, and R ² represents a phenyl group, an alkyl or alkenyl group up to C ₁ -C ₈ . R ³ and R ⁴ independently represent a hydrogen or methyl group, R ⁵ , R ⁶ , R ⁷ independently represent C ₁ -C ₈ alkyl, phenyl, halogenated phenyl (X = F, Cl, Br), benzyl, 2-phenylethyl and the like are shown.

In the above-mentioned sakurai reaction, an allyl group is added to the unsaturated group of the ketone by reacting α, β-unsaturated ketone with allylsilane, but in the present invention, an allyl group is on one side of the double bond or triple bond, and the other side. Is an allylsilation reaction in which a silyl group is added. In this reaction, unlike hydrogensiliconization, allyl groups are always added only inside the double or triple bond, i.e. with the bulky functional groups, and silyl groups are added only outside the double or triple bond. Has Therefore, this reaction is a new and advanced synthesis method for preparing compounds in which allyl and silyl groups are added at the same time. In addition, the reaction with alkines allows the formation of two isomers, cis and trans, as in hydrogen-siliconization, but this reaction has stereoselective, in which only one isomer is produced. The gamma-silylolefin compounds prepared here contain one or two double bonds in the molecule to synthesize new organosilicon compounds or organosilicon polymer compounds through a hydrosilation reaction or another allyl silicide reaction. Can be.

As a catalyst, Lewis acids such as aluminum chloride may be used, and if necessary, they may be mixed with chlorides such as zinc, boron, titanium, iron repayment, cadmium, and antimony. Allylsilanes of the general formula (III) can cause allyl silication reactions by themselves, so that allylsilanes of the general formula (III) are added to a reaction tank in which an olefin compound of formula (I) or (II), a solvent, and a catalyst are mixed. It is preferable to add dropwise.

As the solvent used in the present invention, benzene, toluene, xylene, n-hexane, methylene chloride, chloroform, carbon tetrachloride, etc. may be used, but benzene or n-hexane is most preferably used. Although the molar ratio of general formula (I), (II) or (III) is most preferably used as 1: 1, in order to suppress the self allyl siliconization reaction of allylsilanes of general formula (IV), general formula (I) Increase the amount of (II) or (III).

In the following examples the temperature is in degrees Celsius, and the abbreviations in the nuclear magnetic resonance (NMR) spectra are as follows. s = single line, d = double line, t = triplet, q = quartet, p = quinine, m = multiline, and the peak position is in parts permillion (ppm) using tetramethylsilane as an internal reference. It is shown.

The following examples will further illustrate the present invention but are not limited thereto.

Example 1. Preparation of 4- (trimethylsilyl) methyl-1-octene]

A 50 ml three-necked round bottom flask was equipped with a magnetic lid, a reflux condenser and a dropping funnel, and the flame was dried while passing the dried N ₂ gas. After adding 0.58 g (4.3 mmole) of aluminum chloride and 10.0 ml of n-hexane, dropwise funnel was mixed with 5.0 g (40 mmole) of 1-hexene and 11.1 g (132 mmole) of allyltrimethylsilane. The reactants were added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactants with magnetic milk. After completion of the addition, the reaction was performed at room temperature for 2 hours, and then confirmed by gas chromatography. After the reaction was completed, 5 ml of water was added to the reactor and stirred for 5 minutes to completely remove the activity of the catalyst, and then transferred to a separatory funnel, and the organic layer was separated from the upper layer, and dried over anhydrous magnesium sulfate. The dried organic layer was distilled under vacuum to obtain 5.7 g (yield 65%, 28-30 ° C./0.6 torr) of 4- (trimethylsilyl) methyl-1-octene.

¹ HNMR (CDCl ₃ , δ): 0.01 (s, 9H, Si-Me ₃ ); 0.51-0.60 (m, 2H, CH ₂ -Si); 0.90 (t, 3H, -CH ₃ ); 1.18-1.40 (m, 6H, -CH _2- ); 1.50-1.60 (m, 1H, -CH-); 1.98-2.10 (m, 2H, -CH _2- ); 4.97-5.01 (m, 2H, = CH ₂ ); 5.70-5.85 (m, 1H, -CH)

Example 2. Preparation of 2, 2-dimethyl-4- (trimethylsilyl) methyl-2-silahept-1-ene

Using the same reactor as in Example 1, 0.58 g (4.3 mmole) of aluminum chloride and 10.0 ml of n-hexane were added, and only 5.0 g (40 mmole) of allyltrimethylsilane was added to the dropping funnel, followed by vigorous stirring with magnetic milk. The reaction was added dropwise from the dropping funnel over about 20 minutes at room temperature. After completion of the dropwise reaction, the mixture was reacted at room temperature for 12 hours, and then treated in the same manner as in Example 1 and distilled to give 2.4 g of 2,2-dimethyl-4- (trimethylsilyl) methyl-6-heptene (yield 48%, 30- 32 ° C./0.6 torr).

¹ HNMR (CDCl ₃ , δ): 0.01 (s, 9H, Si-Me ₃ ); 0.50-0.71 (m, 2H, CH ₂ -Si); 1.72-1.83 (hep, 1H, -CH-); 2.03 (t, 2H, -CH _2- ); 4.96-5.02 (m, 2H, = CH ₂ ); 5.70-5.81 (m, 1H, -CH)

Example 3. Preparation of 2, 2-dimethyl-4- (trimethylsilyl) methyl-1-dekene

Using the same reactor as in Example 1, 0.58 g (4.3 mmole) of aluminum chloride and 10.0 ml of n-hexane were added, and then 5.0 g (40 mmole) of 1-octene and 14.8 g (132 mmole) of allyltrimethylsilane were added to the dropping funnel. After the reaction was stirred vigorously with magnet milk, the reaction was added dropwise from the dropping funnel over about 20 minutes at room temperature. After the addition, the reaction was carried out at room temperature for 3 hours, and then treated and distilled in the same manner as in Example 1 to obtain 2,2-dimethyl-4- (trimethylsilyl) methyl-1-dekene x, xg (yield 60%, 46 -48 ° C / 0.6torr).

¹ HNMR (CDCl ₃ , δ): 0.02 (s, 9H, Si-Me ₃ ); 0.52-0.59 (m, 2H, CH ₂ -Si); 0.89 (t, 3H, -CH ₃ ); 1.24-1.35 (m, 10H, -CH _2- ); 1.51-1.62 (m, 1H, -CH-); 2.01-2.06 (m, 2H, -CH _2- ); 4.96-5.02 (m, 2H, = CH ₂ ); 5.70-5.85 (m, 1H, -CH)

Example 4. Preparation of 1-allyl-2-trimethylsilylcyclohexane

Using the same reactor as in Example 1, 0.58 g (4.3 mmole) of aluminum chloride and 10.0 ml of benzene were added, and then 5.0 g (40 mmole) of allyltrimethylsilane and 10.8 g (132 mmole) of cyclohexene were added to the dropping funnel. The reactants were added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactants with milk. After completion of the dropwise reaction, the mixture was reacted at room temperature for 1.5 hours, and then treated and distilled in the same manner as in Example 1 to obtain 1.72 g (yield 22%, 38-41 ° C./0.6 torr) of 1-allyl-2-trimethylsilylcyclohexane. .

¹ HNMR (CDCl ₃ , δ): 0.02 (s, 9H, Si-Me ₃ ); 0.45-0.54 (m, 1H, CH-Si); 0.85-0.98, 1.78-1.84 (m, 2H, -CH ₂ ); 1.08-1.19, 1.67-1.69 (m, 2H, -CH _2- ); 1.31-1.42 (m, 1H, -CH-); 1.70-1.77 (m, 2H, -CH _2- ); 1.85-1.92, 2.23-2.35 (m, 2H, CH ₂ -C═C); 4.96-5.01 (m, 2H, = CH ₂ ); 5.74-5.83 (m, 1H, -CH)

Example 5. Preparation of 1-allyl-2-trimethylsilylcyclopentane]

Using the same reactor as in Example 1, 0.58 g (4.3 mmole) of aluminum chloride and 10.0 ml of benzene were added, and then 5.0 g (40 mmole) of allyltrimethylsilane and 9.0 g (132 mmole) of cyclopentane were added to the dropping funnel. The reactants were added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactants with milk. After completion of the dropwise reaction, the mixture was reacted at room temperature for 6 hours, and then treated and distilled in the same manner as in Example 1 to obtain 2.84 g (yield 39%, 23-25 ° C./0.6 torr) of 1-allyl-2-trimethylsilylcyclopentane. .

¹ HNMR (CDCl ₃ , δ): -0.02 (s, 9H, Si-Me ₃ ); 0.64 (q, 1 H, CH-Si); 1.24-1.41, 1.1.46-1.57, 1.60-1.70, 1.75-1.86 (m, 6H, ring-CH _2- ); 1.85-1.95, 2.17-2.30 (m, 2H, -CH _2- ); 4.93-5.03 (m, 2H, = CH ₂ ); 5.73-5.86 (m, 1H, -CH-)

Example 6. Preparation of 4-methyl-4- (trimethylsilyl) methylhex-1-ene

After adding 0.58 g (4.3 mmole) of aluminum chloride and 10.0 ml of benzene using the same reactor as in Example 1, 5.0 g (40 mmole) of allyltrimethylsilane and 9.0 g (132 mmole) of 2-methyl-2-butene were added to the dropping funnel. After stirring, the reactants were stirred vigorously with a magnetic milk drop, and the reactants were added dropwise at room temperature for about 20 minutes. After completion of the dropwise addition, the reaction was carried out at 40 ° C. for 14 hours, followed by the same method as in Example 1, and distillation to yield 0.81 g of 4-methyl-4- (trimethylsilyl) methylhex-1-ene (yield 11%, 21- 23 ° C./0.6torr).

¹ HNMR (CDCl ₃ , δ): 0.05 (s, 9H, Si-Me ₃ ); 0.66 (s, 1 H, CH-Si); 0.81 (t, 3H, -CH ₃ ); 0.90 (t, 3H, -CH ₃ ); 1.25-1.35 (q, 2H, -CH _2- ); 1.99 (d, 2H, -CH _2- ); 4.97-5.03 (m, 2H, = CH ₂ ); 5.76-5.80 (m, 1H, -CH)

Example 7. Preparation of 4- (2-phenyl) ethyl-2, 2-dimethyl-2-silahept-6-ene

Using the same reactor as in Example 1, 0.58g (4.3mmole) of aluminum chloride and 10.0ml of n-hexane were added, and then 5.0g (40mmole) of allyltrimethylsilane and 15.6g (132 mmole) of allylbenzene were added to the dropping funnel. The reactants were added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactants with a magnetic milk. After completion of the dropwise addition, the mixture was reacted at room temperature for 6 hours, and then treated in the same manner as in Example 1 and distilled to give 2.04 g of 4- (2-phenyl) ethyl-2,2-dimethyl-2-silahept-6-ene ( Yield 20%, 50-52 ° C./0.6torr).

¹ HNMR (CDCl ₃ , δ): 0.03 (s, 9H, Si-Me ₃ ); 0.50-68 (m, 2H, CH ₂ -Si); 0.81 (t, 3H, -CH ₃ ); 0.90 (t, 3H, -CH ₃ ); 1.25-1.35 (q, 2H, -CH _2- ); 1.85-1.96 (m, 1H, -CH-); 1.97-2.11 (m, 2H, -CH ₂ -Ph); 2.59 (d, 2H, -CH _2- ); 4.97-5.08 (m, 2H, = CH ₂ ); 5.74-5.90 (m, 1H, -CH); 7.13-7.32 (m, 5H, Ph)

Example 8. Preparation of 4- (dimethylphenylsilyl) methyl-1-octene]

After adding 0.58g (4.3mmole) of aluminum chloride and 10.0ml of benzene using the same reactor as in Example 1, 7.0g (40mmole) and 1-hensen 11.1g (132mmole) of allyldimethylphenylsilane were added to the dropping funnel. Mix well. The reactant was added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactant with magnet milk. After completion of the dropwise reaction, the mixture was reacted at room temperature for 30 minutes, and then treated and distilled in the same manner as in Example 1 to 4.88 g of 4- (dimethylphenylsilyl) methyl-1-octene (yield 47%, 72-74 ° C / 0.6torr). )

¹ HNMR (CDCl ₃ , δ): 0.30 (s, 6H, Si-Me ₂ ); 0.80-0.88 (m, 2H, CH ₂ -Si); 0.80 (t, 3H, -CH ₃ ); 1.13-1.28 (m, 6H, -CH _2- ); 1.52-1.64 (m, 1H, -CH-); 1.93-2.08 (m, 2H, -CH _2- ); 4.90-5.00 (m, 2H, = CH ₂ ); 5.65-5.80 (m, 1H, -CH =); 7.30-7.55 (m, 5H, Ph)

Example 9 Preparation of 4- (benzyldimethylsilyl) methyl-1-octene

0.58g (4.3mmole) of aluminum chloride and 10.0ml of n-hexane were added using the same reactor as in Example 1, and 7.6g (40mmole) and 1-hexene 11.1g (132mmole) of allylbenzyldimethylsilane were added to the dropping funnel. After mixing, mix well. The reactants were added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactants with a magnetic milk. After completion of the addition, the reaction was carried out at room temperature for 2 hours, followed by the same method as in Example 1, distillation, and 4.60 g of 4- (benzyldimethylsilyl) methyl-1-octene (yield 42%, 78-80 ° C / 0.6torr). )

¹ HNMR (CDCl ₃ , δ): 0.00 (s, 6H, Si-Me ₂ ); 0.50-0.65 (m, 2H, CH ₂ -Si); 0.90 (t, 3H, -CH ₃ ); 1.21-1.33 (m, 6H, -CH _2- ); 1.53-1.62 (m, 1H, -CH-); 1.97-2.09 (m, 2H, -CH _2- ); 2.10 (s, 2H, -CH ₂ -Ph); 4.95-5.04 (m, 2H, = CH ₂ ); 5.69-5.83 (m, 1H, -CH =); 6.98-7.27 (m, 5H, Ph)

Example 10 Preparation of 4- (2-phenylethyl) dimethylsilyl) methyl-1-octene

0.58g (4.3mmole) of aluminum chloride and 10.0ml of n-hexane were added using the same reactor as in Example 1, and then 8.1g (40mmole) of 1-hexene and 11.1 of allyl (2-phenylethyl) dimethylsilane were added to the dropping funnel. g (132mmole) was added and mixed well. The reactants were added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactants with a magnetic milk. After completion of the dropwise reaction, the mixture was reacted at room temperature for 2 hours, and then treated and distilled in the same manner as in Example 1 to 5.49 g of 4-((2-phenylethyl) dimethylsilyl) methyl-1-octene (yield 48%, 82- 84 ° C./0.6torr).

¹ HNMR (CDCl ₃ , δ): -0.03 (s, 6H, Si-Me ₂ ); 0.50-0.58 (m, 2H, CH ₂ -Si); 0.89 (t, 3H, -CH ₃ ); 0.93-1.02 (m, 2H, -CH _2- ); 1.18-1.39 (m, 6H, -CH _2- ); 1.50-1.62 (m, 1H, -CH-); 1.99-2. 12 (m, 2H, CH _2- ); 2.30-2.42 (m, 2H, -CH _2- ); 4.99-5.04 (m, 2H, = CH ₂ ); 5.72-5.87 (m, 1 H, -CH); 7.00-7.30 (m, 5H, Ph)

Example 11. Preparation of 4- (fluorophenyldimethylsilyl) methyl-1-octene]

Using the same reactor as in Example 1, 0.58g (4.3mmole) of aluminum chloride and 10.0ml of n-hexane were added thereto, and then 7.7g (40mmole) of allylic (fluorophenyl) dimethylsilane and 11.1g of 1-hexene were added to the dropping funnel. 132mmole) and mixed well. The reactant was added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactant with magnet milk. After completion of the dropwise reaction, the mixture was reacted at room temperature for 2 hours, and then treated and distilled in the same manner as in Example 1 to 6.03 g of 4- (fluorophenyldimethylsilyl) dimethylsilyl) methyl-1-octene (yield 55%, 73-75). ℃ / 0.6torr).

¹ HNMR (CDCl ₃ , δ): 0.13 (s, 6H, Si-Me ₂ ); 0.65-0.73 (m, 2H, CH ₂ -Si); 0.72 (t, 3H, -CH ₃ ); 1.09-1.23 (m, 6H, -CH _2- ); 1.48-1.57 (m, 1H, -CH-); 1.86-2.00 (m, 2H, -CH _2- ); 4.91-5.03 (m, 2H, = CH ₂ ); 5.63-5.78 (m, 1H, -CH =); 7.14-7.40 (m, 5H, Ph)

Example 12 Reaction of 2-methyl-2-propenyltrimethylsilane with Alkenes

Nuclear magnetic resonance of the reaction product and reaction product obtained by using the same reactor as in Example 1 and reacting 2-methyl-2-propenyltrimethylsilane with various alkene compounds in the same manner as in Examples 1, 2, 3, and 4 The analysis results are listed in Table 1.

Example 13. Preparation of 3-methyl-4- (trimethylsilyl) methyl-1-octene]

0.58g (4.3mmole) of aluminum chloride and 10.0ml of n-hexane were added using the same reactor as in Example 1, and then 5.1g (40mmole) and 1-hexene of (Z) -crotyltrimethylsilane were added to the dropping funnel. (132mmole) was added and mixed well. The reactants were added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactants with a magnetic milk. After completion of the dropwise addition, the mixture was reacted at room temperature for 2 hours, and then treated and distilled in the same manner as in Example 1 to 2.12 g of 3-methyl-4- (trimethylsilyl) methyl-1-octene (yield 25%, 73-75 ° C). /0.6torr)

¹ HNMR (CDCl ₃ , δ): 0.01 (s, 9H, Si-Me ₃ ); 0.30-0.65 (m, 2H, CH ₂ -Si); 0.90 (t, 3H, -CH ₃ ); 0.93 (s, 3H, -CH ₃ ); 1.18-1.35 (m, 6H, -CH _2- ); 1.48-1.52 (m, 1H, -CH-); 2.20-2.31 (m, 1H, -CH-); 4.90-5.00 (m, 2H, = CH ₂ ); 5.68-5.82 (m, 1H, -CH)

Example 14. Preparation of 2-phenyl-1-trimethylsilyl-1, 4-pentadiene

A 50 ml three-necked round bottom flask was equipped with a magnetic lid, a reflux condenser and a dropping funnel, and the flame was dried while passing the dried N ₂ gas. After adding 0.25 g (1.9 mmole) of aluminum chloride and 10.0 ml of benzene to the reactor, 2.16 g (18.9 mmoles) of allylicmethylsilane and 1.93 g (18.9 mmoles) of phenylacetylene were added to the dropping funnel and mixed well. At this time, the reaction tank was equipped with a water bath at 25 ° C. to cool the reaction heat. The reactants were added dropwise from the dropping funnel over about 20 minutes at room temperature while vigorously stirring the reactants with a magnetic milk. After completion of the addition, the reaction was carried out in a water bath for 25 minutes, and then confirmed by gas chromatography. After the reaction was completed, 5 ml of water was added to the reactor and stirred for 5 minutes to completely remove the activity of the catalyst, and then transferred to a separatory funnel, and the organic layer was separated from the upper layer, and dried over anhydrous magnesium sulfate. The dried organic layer was distilled under vacuum to obtain 1.39 g of 2-phenyl-1-trimethylsilyl-1 and 4-pentadiene (yield 34%, bp 55-7 ° C./0.6 torr).

¹ H-NMR (CDCl ₃ , δ): 0.17 (s, 9H, Si-CH ₃ ), 3.16 (d, 2H, —CH ₂ —); 5.01-5.07 (m, 2H, CH ₂ =), 5.62 (t, -1H, Si -CH =), 5.79-5.86 (m, 1H, -CH =); 7.15-7.35 (m, 5H, C ₆ H _5- )

Example 15 Preparation of 1-methyl-2-phenyl-1-trimethylsilyl-1,4-pentadiene]

After adding 0.25 g (1.9 mmole) of aluminum chloride and 10.0 ml of benzene using the same reactor as in Example 14, 4.3 g (37.8 mmole) of allyltrimethylsilane and 2.2 g (18.9 mmole) of 1-phenylpropene were added to the dropping funnel. After mixing the mix well. At this time, the reaction tank was equipped with a water bath at 25 ° C. to cool the reaction heat. After completion of the dropwise reaction, the mixture was reacted in a water bath for 25 minutes, and then treated and distilled in the same manner as in Example 14 to obtain 2.96 g of 1-methyl-2-methyl-2-phenyl-1-trimethylsilyl-1,4-pentadiene ( Yield 68%, 58-60 ° C. 0.6torr).

¹ H-NMR (CDCl ₃ , δ): -0.02 (s, 9H, Si-CH ₃ ), 1.84 (s, 3H, C-CH ₃ ), 3.18 (d, 2H, -CH _2- ); 4.94-5.03 (m, 2H, CH ₂ =), 5.67-5.80 (m, 1H, -CH =), 7.07-7.31 (m, 5H, C ₆ H _5- )

Example 16 Preparation of 1,2-diphenyl-1-trimethylsilyl-1,4-pentadiene

0.25 g (1.9 mmol e) of aluminum chloride and 5.0 ml of n-hexane were added using the same reactor as in Example 14. The dropping funnel was dissolved in 2.16 g of allyltrimethylsilane (18.9 mmol) in 10.0 ml of n-hexane. 3.36g (18.9mmole) of diphenylacetylene was added and mixed well. At this time, the reaction tank was equipped with a water bath at 25 ° C. to cool the reaction heat. After completion of the dropwise addition, the reaction was carried out in a water bath for 18 hours, followed by treatment in the same manner as in Example 14, and distillation to yield 1.38 g of 1,2-diphenyl-1-trimethylsilyl-1,4-pentadiene (yield 25%, 102). -5 ° C / 0.6 toor).

¹ H-NMR (CDCl ₃ , δ): -0.33 (s, 9H, Si-CH ₃ ), 2.90 (d, 2H, -CH _2- ), 4.66-4.84 (m, 2H, CH ₂ =), 5.47 -5.62 (m, 1H, -CH =), 7.00-7.36 (m, 10H, C ₆ H _5- )

Example 17 Preparation of 4-methyl-1,2-diphenyl-1-trimethylsilyl-1,4-pentadiene

0.25g (1.9mmole) of aluminum chloride and 5.0ml of n-hexane were added using the same reactor as in Example 16, and then, in a dropping funnel, 2.42g (18.9mmole) of allyltrimethylsilane and 10.0ml of n-hexane were dissolved. 3.36g (18.9mmole) of diphenylacetylene was added and mixed well. At this time, the reaction tank was equipped with a water bath at 25 ° C. to heat the reaction. After completion of the dropwise addition, the reaction was carried out in a water bath for 9 hours, and then treated in the same manner as in Example 16, and distilled to give 2.78 g of 4-methyl-1,2-diphenyl-1-trimethylsilyl-1,4-pentadiene (yield). 48%, 107-10 ° C / 0.6torr).

¹ H-NMR (CDCl ₃ , δ), -0.20 (s, 9H, Si-CH ₃ ), 1.59 (s, 3H, CH ₃ ), 3.05 (s, 2H, -CH ₂ ), 4.61 (d, 2H , = CH ₂ ), 7.14-7.41 (m, 10H, Ph)

[Example 18. Preparation of 3-methyl-1,2-diphenyl-1-trimethylsilyl-1,4-pentadiene]

0.25g (1.9mmole) of aluminum chloride and 5.0ml of n-hexane were added using the same reactor as in Example 16, and then, in a dropping funnel, 2.42g (18.9mmole) of allyltrimethylsilane and 10.0ml of n-hexane were dissolved. 3.36g (18.9mmole) of diphenylacetylene was added and mixed well. At this time, the reaction tank was equipped with a water bath at 25 ° C. to cool the reaction heat. After completion of the dropwise addition, the reaction was carried out in a water bath for 25 minutes, followed by the same method as in Example 16, and distillation to yield 1.50 g of 3-methyl-1,2-diphenyl-1-trimethylsilyl-1,4-pentadiene (yield). 26%, 106-9 ° C./0.6 torr).

¹ H-NMR (CDCl ₃ , δ), -0.28 (s, 9H, Si-CH ₃ ), 0.96 (d, 3H, -CH ₃ ), 3.39 (p, 2H, -CH ₂ ), 4.81-4.98 ( m, 2H, = CH ₂ ), 5.70-5.81 (m, 1H, -CH =), 7.12-7.65 (m, 10H, Ph)

Claims (8)

Gamma-silylolefins of the general formula (V): Wherein R is an alkyl or alkenyl group up to C ₁ -C ₈ , —CH ₂ SiMe ₃ , or benzyl, R ³ and R ⁴ are independently hydrogen or methyl, and R ⁵ , R ⁶ , R ⁷ are independent a represents an alkyl, phenyl, halogenated phenyl (X = F, Cl, Br), benzyl 2-phenylethyl of C ₁ -C _8. Unsaturated hydrocarbon compound of formula (I) A method for producing a gamma silylolefin compound of formula (V) by reacting with a compound of formula (IV). Wherein R represents an alkyl or alkenyl group up to C ₁ -C ₈ , —CH ₂ SiMe ₃ , or benzyl. Wherein R ³ and R ⁴ are independently hydrogen or methyl, and R ⁵ , R ⁶ , R ⁷ are independently C ₁ -C ₈ alkyl, phenyl, halogenated phenyl (X = F, Cl, Br), benzyl 2-phenylethyl is indicated. The process according to claim 2, wherein benzene, hexane, methylene chloride, chloroform and carbon tetrachloride are used as a solvent. The process according to claim 2, wherein one of aluminum chloride, titanium chloride, tin chloride and boron chloride is used as a single catalyst as the Lewis acid. The process according to claim 2, wherein at least two of aluminum chloride, titanium chloride, tin chloride and boron chloride are used as Lewis acids as catalysts. The process according to claim 2, wherein the solvent and the catalyst are first added to the reaction tank, and the mixture is added dropwise by mixing the unsaturated hydrocarbon compound of general formula (I) with allylsilane of general formula (IV). The production method according to claim 2, wherein the allylsilanes of the general formula (IV) are used 1 to 10 times in molar ratio with respect to the unsaturated hydrocarbon compound of the general formula (I). The production method according to claim 2, wherein the reaction temperature is -40 ° C.