JPS638959B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds and methods for their production. The present invention aims to provide a novel compound useful as an intermediate in various synthetic reactions and a method for producing the same. The novel compound of the present invention is 1,4-bis(triorganosiloxy)-1,3 represented by the formula ()
-Butadiene. (In the formula, R is an alkyl group or alkenyl group having 1 to 6 carbon atoms, a phenyl group, or a phenyl group substituted with a halogen or an alkyl group having 1 to 6 carbon atoms) When is substituted phenyl, the number of substituents is preferably 1-2. Among the compounds represented by formula (), particularly preferred are those in which R is an alkyl group having 1 to 3 carbon atoms. These compounds are extremely stable, stable against air and moisture, and hardly decompose when stored in the refrigerator. These compounds are useful as intermediates in various synthetic reactions as described below. For example, in addition to being used as an ordinary enolate in carbon-carbon bond formation reactions, it can also be used as an enolate by reacting with alcohol or thiol at low temperatures such as -60 to -70°C, and then treating with sodium hydrogen carbonate. and thioacetals of formula (). Also, by reacting 1,3-diol, bis(1,3-dithiane of formula ()) It can also lead to The compound represented by formula () is synthesized by the following method. That is, acetylene silyl ether represented by formula () is isomerized into a compound of formula () in the presence of a triple bond transfer reaction catalyst (hereinafter abbreviated as an isomerization catalyst), thereby converting it into a compound of formula (). As the isomerization catalyst, a reaction mixture obtained by reacting various complexes of transition metals or complex-forming salts of transition metals with a compound capable of forming a complex can be used as is. Examples of such transition metal complexes are as follows. HRu (C ₂ H ₄ ) [PpH ₂ (C ₆ H ₄ )] (PPh ₃ ) ₂ ,
HRuCl( _PPh3 ) ₃ −Tol, _RuCl2 ( _PPh3 ) ₃ , _H2Ru
(PPh ₃ ) ₄ , HRu (CH ₃ ) (PPh ₃ ) ₃ , HRu (α-naphthyl) (PPh ₃ ) ₄ , HRu (α-naphthyl)
( _{Ph2PCH2CH2PPh2} ) _{2 , H4Ru} ( _{PPh3 ) 3} , _RhCl
(PPh ₃ ) ₃ , [RhCl (cyclooctadiene)] ₂ , CoCl ₂
−AlEt ₃ − Amine, Co (acetylacetone) ₂ −
AlEt ₃ -amine, [Ir (cyclooctadiene)
PMePh ₂ ) ₂ ]PE ₆ (In the formula, Me is metal, Et is ethyl, Ph is phenyl, and Tol is toluene. Examples of amines are pyridine and trialkylamine.) Complex-forming salts of transition metals An example of a reaction mixture of this and a compound capable of forming a complex is as follows. Chlorides of ruthenium, rhodium, cobalt (e.g. RuCl ₃ , RhCl ₃ , CoCl ₂ etc.) can be converted into triphenylphosphine, triethylphosphine, trimethylphosphine, dimethylphenylphosphine,
Mixed with one or more trialkyl or triarylphosphines such as methyldiphenylphosphine, diphenylphosphineethane, dimethylphosphineethane, etc., and further NaBH ₄ ,
A reaction mixture containing unreacted substances obtained by adding a reducing agent such as LiAlH ₄ , AlEt ₃ , H ₂ NEt ₃ . Preferably, HRu(C ₂ H ₄ ) [PPh ₂ (C ₆ H ₄ )] (PPh ₃ ) ₂ ,
HRuCl (PPh ₃ ) ₃ −Tol, HRu (α-naphthyl)
(Ph ₂ PCH ₂ CH ₂ PPh ₂ ) ₂ , RhCl(PPh ₃ ) ₃ , CoCl ₂ −
A transition metal complex selected from the group consisting of AlEt ₃ -pyridine and [Ir (cyclooctadiene) PMePh ₂ ) ₂ ]PF ₆ (in these groups, Me represents methyl, Ph represents phenyl, and Tol represents toluene). , or an isomerization catalyst consisting of a reaction mixture obtained by mixing ruthenium trichloride, triphenylphosphine and triethylaluminum. The number of complexes used as an isomerization catalyst is not limited to one type, and a mixture of two or more types may be used. The amount of catalyst used is not particularly limited, but is usually 1/10 by weight based on the acetylene silyl ether starting material.
~1/2000 is used. The reaction temperature is preferably in the range of 100 to 250°C, particularly preferably 120 to 200°C. Preferably, the reaction is carried out in a closed system under autogenous pressure. Further, it is preferable to create an inert atmosphere in the reaction system before heating it to the reaction temperature. The reaction time can vary widely depending on conditions such as the type of acetylene silyl ether as a starting material, the type and amount of the catalyst, and the reaction temperature, but is usually 2 to 5 hours. Reactions are carried out in various solvents. Examples of solvents used are as follows. Aromatic hydrocarbons such as benzene, toluene and xylene, saturated hydrocarbons such as pentane, hexane, heptane and octane, ethers such as diethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane. Note that halogenated solvents are unsuitable. Although the amount of the solvent is not particularly limited, the preferred amount of the solvent is 0 to 10 parts by volume per 1 part by weight of the starting acetylene silyl ether. Acetylene silyl ether represented by formula () is butyne diol represented by formula () can be produced by reacting with triorganochlorosilane in the presence of a dehydrochlorinating agent such as pyridine or triethylamine. Examples are shown below. These examples are presented only for carrying out the invention and should not be construed as limiting the invention. Example 1 Synthesis of 1,4-bis(trimethylsiloxy)-2-butyne 10 g (0.117 mol) of 2-butyne-1,4-diol and 22.7 ml (0.28 mol) of pyridine were added to 400 ml of dry ether. , 35.7 ml (0.28 mL) of trimethylsilyl chloride with stirring in a nitrogen atmosphere
mol) was added dropwise over about 1 hour. A white precipitate of pyridine hydrochloride was generated simultaneously with the dropping. After the dropwise addition of trimethylsilyl chloride was completed, the mixture was further stirred at room temperature for 1 hour to complete the reaction. Then, add the reaction solution
It was washed with 400 ml of water and the organic phase was separated. The aqueous phase was further extracted twice with 400 ml of ether, the resulting organic phase was dried over calcium chloride, and the ether was distilled off using a rotary evaporator.
Bis(trimethylsiloxy)-2-butyne 25.2g
I got it. Yield 94%. NMR-spectrum (in _CCl4 ) δ0.06 (s, 18H, -Si( _CH3 ) ₃ ) 4.18 (s, 4H, _-CH2- ) Example 2 1,4-bis(trimethylsiloxy)-1 ,3
- Synthesis of butadiene HRuCl (PPh ₃ ) ₄ -Tol51.9 mg (0.051 mmol)
was placed in a Pyrex reaction tube with a diameter of 15 mm, and after purging with nitrogen, dry benzene was added in a nitrogen atmosphere.
When the catalyst was thoroughly shaken to dissolve as much of the catalyst as possible, the solution turned reddish brown. This solution contains 1,4-
Bis(trimethylsiloxy)-2-butyne 991mg
(4.30 mmol), sealed the tube, and heated to 150°C.
The mixture was heated in an oil bath for 3 hours. After concentrating the resulting reddish-brown homogeneous solution under reduced pressure, a small amount of pentane was added, the precipitated catalyst ruthenium complex was filtered off, and the filtrate was concentrated to give 1,4-bis(trimethylsiloxy) as a pale yellow oily liquid.
871 mg (3.78 mmol) of -1,3-butadiene was obtained. Yield 88%. Example 3 500 mg (2.17 mmol) of 1,4-bis(trimethylsiloxy)-2-butyne and a ruthenium catalyst (ruthenium trichloride, triphenylphosphine, and triethylaluminum) were mixed in a 15 mm diameter Pyrex reaction tube purged with nitrogen. 5.3 mg of the reaction mixture (obtained by the reaction mixture) was added, and then 2 ml of dry benzene was added. After the reaction tube was cooled in a dry ice-acetone bath and replaced with nitrogen twice, the reaction tube was sealed and heated in an oil bath at 150° C. for 3 hours.
After the reaction is complete, the benzene is distilled off using a rotary evaporator to obtain 1,4-bis(trimethylsiloxy).
500 mg of -1,3-butadiene was obtained. Yield 100%. IR-spectrum (in _CCl4 , cm ^-1 ) 1253, 1138, 1093, 1068, 868 NMR-spectrum (in _CCl4 ) δ0.12 (s, 18H, -Si( _CH3 ) ₃ ) 4.63-6.38 (m, 4H, olefinic) ppm 1,4-bis(trimethylsiloxy)-1,3-butadiene obtained by dissolving the olefinic spectral pattern has (Z, Z) and (Z , E) was found to be a monolithic 1:1 mixture. Example 4-8 A reaction was carried out in the same manner as in Example 2 or 3 by changing the starting material and catalyst. Starting materials, reaction conditions and results are shown in Table 1. 【table】

Claims (1)

[Claims] 1. 1,4-bis(triorganosiloxy)-1,3-butadiene represented by formula (). (In the formula, R is an alkyl group or alkenyl group having 1 to 6 carbon atoms, a phenyl group, or a phenyl group substituted with a halogen or an alkyl group having 1 to 6 carbon atoms) 2 Acetylene silyl ether represented by formula () (wherein, R is an alkyl group or alkenyl group having 1 to 6 carbon atoms, a phenyl group, or a phenyl group substituted with a halogen or an alkyl group having 1 to 6 carbon atoms), HRu(C ₂ H ₄ ) [ PPh ₂ (C ₆ H ₄ )] (PPh ₃ ) ₂ ,
HRuCl (PPh ₃ ) ₃ −Tol, HRu (α-naphthyl)
(Ph ₂ PCH ₂ CH ₂ PPh ₂ ) ₂ , RhCl(PPh ₃ ) ₃ , CoCl ₂ −
A transition metal complex selected from the group consisting of AlEt ₃ -pyridine and [Ir (cyclooctadiene) PMePh ₂ ) ₂ ]PF ₆ (in these groups, Me represents methyl, Ph represents phenyl, and Tol represents toluene). , or isomerized in the presence of an isomerization catalyst consisting of a reaction mixture obtained by mixing with ruthenium trichloride, triphenylphosphine and triethylaluminum () 1,4-bis(triorganosiloxy)- (wherein R is the same as in the above formula ())
A method for producing 1,3-butadiene.