Method of producing heteroannular 1,1'-bis-(dimethylalkoxysilyl)ferrocenes

FIELD: chemistry.

SUBSTANCE: disclosed is a method of producing heteroannular 1,1'-bis-(dimethylalkoxysilyl)-ferrocenes by reacting anhydrous iron chloride and dimethylalkoxysilyl cyclopentadienes in the medium of an organic solvent, wherein the deprotonation agent of the condensation reaction of iron chloride with silyl derivatives of cyclopentadiene used is sodium derivatives of lower alcohols, such as sodium methylate, ethylate or isopropylate.

EFFECT: high cost-effectiveness and high output of non-defective products.

4 ex

 

The present invention relates to methods for symmetric disubstituted 1,1'-bis-(triorganotin)ferrocene, in particular to a method for heteroaromatic bis-(dimethylethoxysilane)ferrocene, the formula

where R=a hydrocarbon radical of the type CnH2n+1. Such ferrocene are used as additives in various compositions, inhibitors of oxidative polymer degradation, as well as raw materials in the silicone synthesis.

There are two General ways to obtain symmetrical disubstituted 1,1'-bis-(dimethylethoxysilane)ferrocenes: digitalnirvana unsubstituted ferrocene with subsequent processing metalloproteinase alkylalkoxysilane or monomethylamine relevant cyclopentadienylsodium with subsequent interaction of the intermediate formed silicon cyclopentadienide metals with anhydrous chloride of iron.

The first of these methods difficult to realize in practice due to the need digitalnirvana ferrocene using superocean and can not provide high yields of the target products.

A method of obtaining a symmetrical 1,1'-bis-(dimethylethoxysilane)ferrocene by metallation of silicacontaining butyllithium with subsequent processing between the exact liepoisson of silicacontaining anhydrous iron chloride (U.S. Pat. U.S. No. 3060215, IPC C07F 17/00, 1962).

The disadvantages of this method are the use of extremely flammable, utility, low yield of the target product because of side desirelove kremnezemnogo cyclopentadiene.

A method of obtaining a symmetrical disubstituted siliverstovs containing alkoxy - or auxigro the silicon atoms, consisting in the use of cyclopentadienylsodium derivatives, in which the metallation of the corresponding silicacontaining carry out the alkaline metal in the environment of an organic solvent and treated metalloprotein chloride iron (Boars B.K. and other Synthesis of some functional heteroaromatic disubstituted organosilazane. Journal Of General Chemistry. 1972, V.42, VIP, S-1752).

The disadvantage of this method is the low yield of the target product, for example, with respect to 1,1'-bis-(octoxynol)ferrocene not exceeding 16%.

Closest to the proposed method and adopted us as a prototype is a method for heteroaromatic disubstituted bis-(triorganotin)-ferrocene, including 1,1'-bis-(octoxynol) ferrocene, the interaction of organosilicate with metallic sodium, followed by processing the received intermediate ORGANOMETALLIC compound chloride VC is contained in the environment of an organic solvent and isolation of the target product, in order to reduce the formation of by-products and increase the purity of the target product of the process is conducted in the presence of a catalyst, which apply an organic amine (A.S. USSR №280478, IPC CO7F 15/03, IPC CO7F 07/02, 1973).

Significant disadvantages of the known method include:

low yield of the desired 1,1'-bis-(dimethylethoxysilane)ferrocene;

- the formation of by-products, such as mono - and trailersmashine solifenacin;

- a large number of difficult recyclable wastes;

- fire process;

- high energy and labor.

The task of the invention to develop a method of obtaining 1,1'-bis-(dimethylethoxysilane)ferrocene with a high yield of the target products and the elimination of these disadvantages.

The problem is solved by the fact that developed a way to get heteroaromatic 1,1'-bis-(dimethylethoxysilane)ferrocene interaction relevant dimethylaminobenzylidene with chloride of iron, which as deproteinised reactant in the condensation reaction used nitropropane lower alcohols, such as methylate, ethylate or isopropylate sodium.

Detailed description of the method of obtaining heteroaromatic 1,1'-bis-(dimethylethoxysilane)ferrocene illustrated in the following examples.

When is EP 1

To a solution of 35.1 g (of 0.65 mol) of sodium methylate in 90 ml of methanol in the temperature range of 20-35°C was added dropwise a solution of 99,45 g (of 0.65 mol) of dimethylethoxysilane in 100 ml of toluene, the reaction mixture is stirred and cooled to 5-10°C. at this temperature the reaction mass is injected 41,27 g (0,323 mol) of chloride of iron. After stirring for 6 h at 25-30°C the mixture is filtered from the precipitate and distillation of the filtrate in vacuo get a 94.2 g of the target product is 1,1'-bis-(dimethylethoxysilane)ferrocene, so Kip. 122-124°C/ 0.2 mm Hg, density at 20°C was 1.12 g/cm3. Yield 80% of theoretical.

Found %: C 53,2; H 7,11. C16H26Fe1O2Si2.

Calculated, %: C 53,38; H 7,18.

Example 2

To a suspension 44,3 g (of 0.65 mol) of powder ethylate of sodium in 150 ml of toluene was added dropwise a solution of 150 g (of 0.65 mol) of dimethyl(2-ethylhex-1 yloxy)silicacontaining in 150 ml of toluene in the temperature range of 20-35°C, stirred for 0.5 hour and cooled the mixture to 5-10°C. at this temperature the reaction mass is injected 41,27 g (0,323 mol) of chloride of iron. After stirring for 6 h at 25-30°C the mixture is filtered from the precipitate and distillation of the filtrate in vacuo obtain 140 g of the target product is 1,1'-bis[dimethyl(2-ethylhex-1 yloxy)silyl]ferrocene.

Output 77.4% of theoretical, so Kip-200°C/ 0.3 to 0.5 mm Hg, density at 20°C was 1,036 g/cm3, show the eh of refraction n 20D=1,4955.

Found %: C 64,58; H 9,6; Fe To 9.93. C30H54Fe1O2Si2.

Calculated, %: C 64,51; H 9,68; Fe There Is A 10.03.

Example 3

To a freshly prepared solution 44,3 g (of 0.65 mol) of ateleta sodium in a mixture of 20 ml ethanol and 150 ml of toluene was added dropwise a solution of 108,55 g (of 0.65 mol) of dimethylethoxysilane in 100 ml of toluene in the temperature range of 20-35°C, stirred for 0.5 hour and cooled the mixture to 5-10°C. at this temperature the reaction mass is injected 41,27 g (0,323 mol) of chloride of iron. After stirring for 6 h at 25-30°C the mixture is filtered from the precipitate and distillation of the filtrate in vacuo get 166,8 g of the target product is 1,1'-bis-(dimethylethoxysilane)ferrocene.

Exit 86% of theoretical, so Kip-112°C/0.1 mm Hg, density at 20°C was 1.13 g/cm3the refractive index n20D=1,5262.

Found, %: C 55,35; H To 7.67. C18H30Fe1O2Si2.

Calculated, %: C 55,38; H 7,69.

Example 4

To a solution of 53.3 per g (of 0.65 mol) of isopropylate of sodium in 400 ml of isopropanol in the temperature range 20-25°C was added dropwise to 150 g (of 0.65 mol) of dimethyl(2-ethylhex-1 yloxy)silicacontaining, stirred for 30 min and cooled the mixture to 5-10°C. at this temperature the reaction mass is injected 41,27 g (0,323 mol) of chloride of iron. After stirring for 5 h at 40°C evaporated in vacuum to 250 ml of ethanol, the mixture is filtered from the precipitate and justify the filter is in the vacuum obtain 154 g of the target product - 1,1'-bis[dimethyl(2-ethylhex-1 yloxy)silyl]ferrocene.

Exit 85% of theoretical. Mass spectrum (m/z): 558 (M+.). C30H54Fe1O2Si2. The calculated molecular mass 558,7596.

The method of obtaining heteroaromatic 1,1'-bis-(dimethylethoxysilane)ferrocene interaction anhydrous chloride of iron and dimethylaminobenzylidene in the environment of an organic solvent, characterized in that as deproteinised agent is the condensation reaction of chloride of iron with cylindrosporium cyclopentadiene use nitropropane lower alcohols, such as methylate, ethylate or isopropylate sodium.



 

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2 cl, 8 dwg, 2 tbl, 8 ex

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Catalyst system // 2326123

FIELD: chemistry.

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45 cl, 32 ex, 9 tbl

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EFFECT: stable method of producing palladium propionate and extraction with high output in monophase state.

2 cl, 41 ex, 2 tbl

FIELD: semi-conductors.

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12 cl, 1 dwg, 1 ex

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