1-chloro-2,2-bis(chloromethyl)butane

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

Procedure: To 300 parts of ethanol were successively added 6.9 parts of metallic sodium, 23.4 parts of 2-mercaptoethanol and 18.9 parts of 1,1,1-tris(chloromethyl)propane in this order, and the resulting mixture was heated under reflux. Thereafter, the deposited sodium chloride was removed, and the solution was concentrated to obtain 1,1,1-tris(2-hydroxyethyl-thiomethyl) propane. This compound was added to 50 parts of chloroform, and 45 parts of thionyl chloride was dropped into the resulting mixture. Subsequently, the mixture was heated under reflux, and then the solvent chloroform and unreacted thionyl chloride were removed by distillation under reduced pressure. The residual oily substance was poured into ice water and extracted with ether, and the ether extract was dehydrated over anhydrous sodium sulfate and then freed from the solvent by distillation to obtain 1,1,1-tris(2-chloroethylthiomethyl)propane. To this compound were successively added 0.3 part of phosphoric acid and 60 parts of 30% aqueous hydrogen peroxide, and the resulting medium mixture was heated under reflux and then cooled to deposit 1,1,1-tris(2-chloroethylsulfonylmethyl)propane. The deposited compound was recovered by filtration and dissolved in 200 parts of acetone, and the resulting acetone solution was incorporated with 30 parts of triethylamine and then stirred at room temperature to deposit triethylamine hydrochloride. This hydrochloride was removed, and the acetone solution was concentrated to deposit white solids. The solids were recrystallized from ethanol-acetone to obtain 1,1,1-tris(vinylsulfonylmethyl)propane. the resulting mixture was heated under reflux Thereafter, the deposited sodium chloride was removed the solution was concentrated

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 8.50 g of dry magnesium shavings was added 100 ml of tetrahydrofuran and a small crystal of iodine. After 20 minutes, 0.5 ml of 1,2-dibromoethene was added using a syringe followed by the dropwise addition of 5 ml of a 70% solution of 1,1,1-tris(chloromethyl)propane in tetrahydrofuran with evolution of heat and gas. While stirring, additional 1,1,1-tris(chloromethyl)propane solution was added, to total 44.7 g at a rate to maintain reflux. The refluxing was continued for an additional 0.5 hour. Then, the reaction mixture was cooled to -62° to -43° C. and 15.0 g of 4H-pyran-4-one (Aldrich) in 20 ml of tetrahydrofuran was added dropwise. After 1 hour at -60° C., the reaction mixture was allowed to warm to -20° C. and then poured into a mixture of ice-cold diethyl ether (500 ml) and saturated ammonium chloride (350 ml). The aqueous fraction was extracted twice with 300 ml diethyl ether. The combined ether solutions were washed with saturated sodium chloride solution, dried and stripped to yield 16.52 g of the desired product as a pale yellow liquid. of heat to maintain reflux The refluxing was continued for an additional 0.5 hour Then, the reaction mixture was cooled to -62° to -43° C. After 1 hour at -60° C. The aqueous fraction was extracted twice with 300 ml diethyl ether The combined ether solutions were washed with saturated sodium chloride solution dried

Conditions: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 0.99 g of dry magnesium shavings was added 14 ml of dry tetrahydrofuran and a small crystal of iodine. After 20 minutes, 0.25 ml of 1,2-dibromoethane was added by syringe and then 0.5 ml of a 70% tetrahydrofuran solution of 1,1,1-tris(chloromethyl)propane. The reaction mixture was warmed to reflux and more 70% 1,1,1-tris(chloromethyl)propane solution was added to total 5.29 g at a rate to maintain reflux. After the addition was complete, the reaction was refluxed for an additional half hour. After the addition of 10 ml of tetrahydrofuran, the reaction mixture was cooled to -60° C. and 2.06 g of 1,4-dioxepin-6-one in 10 ml of tetrahydrofuran was added dropwise. After 2.5 hours at -60° C., the reaction mixture was warmed to -20° C. and poured into a mixture of 200 ml of saturated ammonium chloride and diethyl ether. The resulting layers were separated and the aqueous layer was extracted twice with diethyl ether. The combined organic layers were washed with water, dried and stripped to yield 3.05 g of the desired product as a dark yellow liquid. The reaction mixture was warmed to reflux to maintain reflux After the addition the reaction was refluxed for an additional half hour After 2.5 hours at -60° C. the reaction mixture was warmed to -20° C. The resulting layers were separated the aqueous layer was extracted twice with diethyl ether The combined organic layers were washed with water dried

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

Procedure: To 300 parts of ethanol were successively added 6.9 parts of metallic sodium, 23.4 parts of 2-mercaptoethanol and 18.9 parts of 1,1,1-tris(chloromethyl)propane in this order, and the resulting mixture was heated under reflux. Thereafter, the deposited sodium chloride was removed, and the solution was concentrated to obtain 1,1,1-tris(2-hydroxyethyl-thiomethyl) propane. This compound was added to 50 parts of chloroform, and 45 parts of thionyl chloride was dropped into the resulting mixture. Subsequently, the mixture was heated under reflux, and then the solvent chloroform and unreacted thionyl chloride were removed by distillation under reduced pressure. The residual oily substance was poured into ice water and extracted with ether, and the ether extract was dehydrated over anhydrous sodium sulfate and then freed from the solvent by distillation to obtain 1,1,1-tris(2-chloroethylthiomethyl)propane. To this compound were successively added 0.3 part of phosphoric acid and 60 parts of 30% aqueous hydrogen peroxide, and the resulting medium mixture was heated under reflux and then cooled to deposit 1,1,1-tris(2-chloroethylsulfonylmethyl)propane. The deposited compound was recovered by filtration and dissolved in 200 parts of acetone, and the resulting acetone solution was incorporated with 30 parts of triethylamine and then stirred at room temperature to deposit triethylamine hydrochloride. This hydrochloride was removed, and the acetone solution was concentrated to deposit white solids. The solids were recrystallized from ethanol-acetone to obtain 1,1,1-tris(vinylsulfonylmethyl)propane. the resulting mixture was heated under reflux Thereafter, the deposited sodium chloride was removed the solution was concentrated

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 8.50 g of dry magnesium shavings was added 100 ml of tetrahydrofuran and a small crystal of iodine. After 20 minutes, 0.5 ml of 1,2-dibromoethene was added using a syringe followed by the dropwise addition of 5 ml of a 70% solution of 1,1,1-tris(chloromethyl)propane in tetrahydrofuran with evolution of heat and gas. While stirring, additional 1,1,1-tris(chloromethyl)propane solution was added, to total 44.7 g at a rate to maintain reflux. The refluxing was continued for an additional 0.5 hour. Then, the reaction mixture was cooled to -62° to -43° C. and 15.0 g of 4H-pyran-4-one (Aldrich) in 20 ml of tetrahydrofuran was added dropwise. After 1 hour at -60° C., the reaction mixture was allowed to warm to -20° C. and then poured into a mixture of ice-cold diethyl ether (500 ml) and saturated ammonium chloride (350 ml). The aqueous fraction was extracted twice with 300 ml diethyl ether. The combined ether solutions were washed with saturated sodium chloride solution, dried and stripped to yield 16.52 g of the desired product as a pale yellow liquid. of heat to maintain reflux The refluxing was continued for an additional 0.5 hour Then, the reaction mixture was cooled to -62° to -43° C. After 1 hour at -60° C. The aqueous fraction was extracted twice with 300 ml diethyl ether The combined ether solutions were washed with saturated sodium chloride solution dried

Conditions: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 0.99 g of dry magnesium shavings was added 14 ml of dry tetrahydrofuran and a small crystal of iodine. After 20 minutes, 0.25 ml of 1,2-dibromoethane was added by syringe and then 0.5 ml of a 70% tetrahydrofuran solution of 1,1,1-tris(chloromethyl)propane. The reaction mixture was warmed to reflux and more 70% 1,1,1-tris(chloromethyl)propane solution was added to total 5.29 g at a rate to maintain reflux. After the addition was complete, the reaction was refluxed for an additional half hour. After the addition of 10 ml of tetrahydrofuran, the reaction mixture was cooled to -60° C. and 2.06 g of 1,4-dioxepin-6-one in 10 ml of tetrahydrofuran was added dropwise. After 2.5 hours at -60° C., the reaction mixture was warmed to -20° C. and poured into a mixture of 200 ml of saturated ammonium chloride and diethyl ether. The resulting layers were separated and the aqueous layer was extracted twice with diethyl ether. The combined organic layers were washed with water, dried and stripped to yield 3.05 g of the desired product as a dark yellow liquid. The reaction mixture was warmed to reflux to maintain reflux After the addition the reaction was refluxed for an additional half hour After 2.5 hours at -60° C. the reaction mixture was warmed to -20° C. The resulting layers were separated the aqueous layer was extracted twice with diethyl ether The combined organic layers were washed with water dried

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

Procedure: To 300 parts of ethanol were successively added 6.9 parts of metallic sodium, 23.4 parts of 2-mercaptoethanol and 18.9 parts of 1,1,1-tris(chloromethyl)propane in this order, and the resulting mixture was heated under reflux. Thereafter, the deposited sodium chloride was removed, and the solution was concentrated to obtain 1,1,1-tris(2-hydroxyethyl-thiomethyl) propane. This compound was added to 50 parts of chloroform, and 45 parts of thionyl chloride was dropped into the resulting mixture. Subsequently, the mixture was heated under reflux, and then the solvent chloroform and unreacted thionyl chloride were removed by distillation under reduced pressure. The residual oily substance was poured into ice water and extracted with ether, and the ether extract was dehydrated over anhydrous sodium sulfate and then freed from the solvent by distillation to obtain 1,1,1-tris(2-chloroethylthiomethyl)propane. To this compound were successively added 0.3 part of phosphoric acid and 60 parts of 30% aqueous hydrogen peroxide, and the resulting medium mixture was heated under reflux and then cooled to deposit 1,1,1-tris(2-chloroethylsulfonylmethyl)propane. The deposited compound was recovered by filtration and dissolved in 200 parts of acetone, and the resulting acetone solution was incorporated with 30 parts of triethylamine and then stirred at room temperature to deposit triethylamine hydrochloride. This hydrochloride was removed, and the acetone solution was concentrated to deposit white solids. The solids were recrystallized from ethanol-acetone to obtain 1,1,1-tris(vinylsulfonylmethyl)propane. the resulting mixture was heated under reflux Thereafter, the deposited sodium chloride was removed the solution was concentrated