chloro-(3-chloropropyl)-dimethylsilane

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An initial charge of 508 g (6.94 mol) of 1-butylamine is admixed dropwise over the course of 2.5 h with 171 g (1.00 mol) of chloropropyldimethylchlorosilane and the mixture is heated at reflux for 12 h. Following distillative removal of the excess 1-butylamine, the residue is diluted with 350 ml of toluene and cooled to 10° C. The precipitate it forms is filtered off and the filtrate is distilled in vacuo. This gives 134.5 g of N-butyl-1,1-dimethyl-1-sila-2-azacyclopentane. the mixture is heated at reflux for 12 h removal of the excess 1-butylamine the residue is diluted with 350 ml of toluene The precipitate it forms is filtered off the filtrate is distilled in vacuo

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An initial charge of 508 g (6.94 mol) of 1-butylamine is admixed dropwise over the course of 2.5 h with 171 g (1.00 mol) of chloropropyldimethylchlorosilane and the mixture is heated at reflux for 12 h. Following distillative removal of the excess 1-butylamine, the residue is diluted with 350 ml of toluene and cooled to 10° C. The precipitate it forms is filtered off and the filtrate is distilled in vacuo. This gives 134.5 g of N-butyl-1,1-dimethyl-1-sila-2-azacyclopentane. the mixture is heated at reflux for 12 h removal of the excess 1-butylamine the residue is diluted with 350 ml of toluene The precipitate it forms is filtered off the filtrate is distilled in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The above-synthesized 3-chloropropylchlorodimethylsilane (1) (15.6 g, 91.2 mmol) was dissolved in 50 mL of THF, to which 1.6 M vinylmagnesium chloride (85.6 mL, 137 mmol) was slowly added at 0°, and the mixture was stirred for 2 hours. After the reaction, the organic layer was extracted with aqueous NH4Cl solution and ether, and the organic layer was washed with aqueous saturated NaCl solution. The washed organic solution was dried with anhydrous MgSO4, and then filtered through celite to remove MgSO4. After evaporating the solvent, the resulting residue was purified by column chromatography (n-Hex:EA=10:1, Rf=0.78) to give 14.2 g (96% yield) of pure 3-chloropropyldimethylvinylsilane (2). was slowly added at 0° After the reaction the organic layer was extracted with aqueous NH4Cl solution and ether the organic layer was washed with aqueous saturated NaCl solution The washed organic solution was dried with anhydrous MgSO4 filtered through celite to remove MgSO4 After evaporating the solvent the resulting residue was purified by column chromatography (n-Hex:EA=10:1, Rf=0.78)

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml apparatus, there were combined 8.6 g (0.075 mol) of MeSiHCl2, 7.1 g (0.075 mol) of Me2SiHCl, and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution (0.01 ml) was added at 37° C., followed by heating up to 45° C. over 1 hr. Vacuum distillation yielded 31.3% of MeSiCl2CH2CH2CH2Cl and 22.6% of Me2SiClCH2CH2CH2Cl. This example shows that neither Me2SiHCl nor MeSiHCl2 is a very effective promoter at the equimolar level for reactions of the other with allyl chloride. Vacuum distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml apparatus, there were combined 7.1 g (0.075 mol) of Me2SiHCl, 10.2 g (0.075 mol) of Cl3SiH, and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution (0.01 ml) was added at 33° C., causing an exothermic reaction to 47° C. in 7 min. VPC analysis 14 min. later showed a complete reaction. Vacuum distillation yielded 60.4% Cl3SiCH2CH2CH2Cl and 8.6% Me2SiClCH2CH2CH2Cl. This example shows that Me2SiHCl is an effective promoter for the reaction of Cl3SiH with allyl chloride at the equimolar level. an exothermic reaction to 47° C. in 7 min VPC analysis 14 min. a complete reaction Vacuum distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml apparatus, there were combined 7.1 g (0.075 mol) of Me2SiHCl, 8.7 g (0.075 mol) of Et3SiH and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution was added (0.05 ml) at 34° C. Gentle heating caused a smooth exothermic reaction to 92° over 36 min. Vacuum distillation yielded 42.5% of Me2SiClCH2CH2CH2Cl and 4.8% of Et3SiCH2CH2CH2Cl. This example shows that Et3SiH at the equimolar level is an effective promoter for the reaction between Me2SiHCl and allyl chloride. Pt catalyst solution was added (0.05 ml) at 34° C Gentle heating a smooth exothermic reaction to 92° over 36 min Vacuum distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The above-synthesized 3-chloropropylchlorodimethylsilane (1) (15.6 g, 91.2 mmol) was dissolved in 50 mL of THF, to which 1.6 M vinylmagnesium chloride (85.6 mL, 137 mmol) was slowly added at 0°, and the mixture was stirred for 2 hours. After the reaction, the organic layer was extracted with aqueous NH4Cl solution and ether, and the organic layer was washed with aqueous saturated NaCl solution. The washed organic solution was dried with anhydrous MgSO4, and then filtered through celite to remove MgSO4. After evaporating the solvent, the resulting residue was purified by column chromatography (n-Hex:EA=10:1, Rf=0.78) to give 14.2 g (96% yield) of pure 3-chloropropyldimethylvinylsilane (2). was slowly added at 0° After the reaction the organic layer was extracted with aqueous NH4Cl solution and ether the organic layer was washed with aqueous saturated NaCl solution The washed organic solution was dried with anhydrous MgSO4 filtered through celite to remove MgSO4 After evaporating the solvent the resulting residue was purified by column chromatography (n-Hex:EA=10:1, Rf=0.78)

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml apparatus, there were combined 8.6 g (0.075 mol) of MeSiHCl2, 7.1 g (0.075 mol) of Me2SiHCl, and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution (0.01 ml) was added at 37° C., followed by heating up to 45° C. over 1 hr. Vacuum distillation yielded 31.3% of MeSiCl2CH2CH2CH2Cl and 22.6% of Me2SiClCH2CH2CH2Cl. This example shows that neither Me2SiHCl nor MeSiHCl2 is a very effective promoter at the equimolar level for reactions of the other with allyl chloride. Vacuum distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml apparatus, there were combined 7.1 g (0.075 mol) of Me2SiHCl, 10.2 g (0.075 mol) of Cl3SiH, and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution (0.01 ml) was added at 33° C., causing an exothermic reaction to 47° C. in 7 min. VPC analysis 14 min. later showed a complete reaction. Vacuum distillation yielded 60.4% Cl3SiCH2CH2CH2Cl and 8.6% Me2SiClCH2CH2CH2Cl. This example shows that Me2SiHCl is an effective promoter for the reaction of Cl3SiH with allyl chloride at the equimolar level. an exothermic reaction to 47° C. in 7 min VPC analysis 14 min. a complete reaction Vacuum distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml apparatus, there were combined 7.1 g (0.075 mol) of Me2SiHCl, 8.7 g (0.075 mol) of Et3SiH and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution was added (0.05 ml) at 34° C. Gentle heating caused a smooth exothermic reaction to 92° over 36 min. Vacuum distillation yielded 42.5% of Me2SiClCH2CH2CH2Cl and 4.8% of Et3SiCH2CH2CH2Cl. This example shows that Et3SiH at the equimolar level is an effective promoter for the reaction between Me2SiHCl and allyl chloride. Pt catalyst solution was added (0.05 ml) at 34° C Gentle heating a smooth exothermic reaction to 92° over 36 min Vacuum distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 500 mL (0.73 mol) a tetrahydrofuran solution of 1.46M vinylmagnesium chloride, to which 119.8 g (0.7 mol) of chloropropyldimethylchlorosilane was added dropwise over 2 hours at an internal temperature of 25-50° C. The reaction solution was stirred for 2 hours. A salt formed was removed by filtration. By subsequent distillation, the target compound, chloropropyldimethylvinylsilane was collected as a fraction having a boiling point of 82° C./5 kPa in an amount of 104.4 g (yield 92%). A flask equipped with a stirrer reflux condenser A salt formed was removed by filtration By subsequent distillation the target compound, chloropropyldimethylvinylsilane was collected as a fraction

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a glass reactor fitted with a motor-driven stirrer, a thermometer, water-cooled reflux condenser and dropping funnel was charged 0.5 moles of 4-t-butylphenylmagnesium bromide in THF (prepared in the usual manner from 4-t-butylbromobenzene, magnesium chips and tetrahydrofuran). While maintaining an atmosphere of nitrogen in the reactor, 64.0 g of 3-chloro-n-propyldimethylchlorosilane (prepared in Step A above) was added dropwise to the reactor over a period of 25 minutes, keeping the temperature between 35°-40° C. After the addition was complete, the mixture was stirred for 1 hour while allowing the reation temperature to drop to ~30°. To this mixture was added 400 ml of a 5 percent aqueous ammonium chloride solution. The organic layer was separated and dried over magnesium sulfate. After evaporation of solvent, the residue, weighing 113.6 g, was distilled under vacuum. The fraction boiling at 110°-120° C. at 0.5 mm was collected. It weighed 93.2 g and was a colorless, oily liquid of refractive index 1.5088 at 23° C. Analysis showed the compound to contain 67.4 percent carbon, 9.2 percent hydrogen and 13.0 percent chlorine. Theory for the compound is 67.0 percent carbon, 9.4 percent hydrogen and 13.2 percent chlorine. Gas chromatography showed the compound to be ~90 percent pure. To a glass reactor fitted with a motor-driven stirrer reflux condenser was added dropwise to the reactor over a period of 25 minutes between 35°-40° C After the addition to drop to ~30° The organic layer was separated dried over magnesium sulfate After evaporation of solvent was distilled under vacuum The fraction boiling at 110°-120° C. at 0.5 mm was collected at 23° C