3-trimethoxysilylpropane-1-thiol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 1,035 grams of 3-mercapto-1-propyltrimethoxysilane, 1,096 grams of a 25 weight percent methanolic solution of sodium methoxide, and 1,764 grams of toluene were charged to a 5-liter flask under an atmosphere of nitrogen. The stirred mixture developed a pinkish color. The flask was placed into a water bath at 64° C. Methanol was removed from the flask by distilling off a methanol-toluene azeotrope under a partial vacuum. The vacuum was kept such that the temperature in the distillation head was maintained at 30° to 35° C. during which time 1,500 ml of distillate, consisting of a toluene-methanol azeotrope, was collected. During this time the contents of the flask turned colorless. An additional 429 grams of toluene were added, and the distillation resumed. The appearance of a strong density current in the distillate, which coincided with an increase in distillation head temperature from 35° to 55° C., and the appearance of a changing liquid surface tension in the condenser signaled the point at which methanol removal from the flask was complete. The contents of the flask had become a viscous fluid. With continued stirring, the contents of the flask were allowed to cool. The flask was placed in an ice-water bath, resulting in what appeared to be a thick paste. 427 grams of propionyl chloride was added to the flask dropwise and/or in small portions with continued stirring in an ice-water bath until the reaction was complete. Aliquots of the stirred mixture were taken periodically. An alkaline reading indicated the completion of the reaction. The final mixture was a white suspension of NaCl in a toluene solution of the product. This mixture was filtered, and the solvent was removed from the filtrate to yield a nearly colorless product. Gas chromatography indicated (by weight) 3 percent of 3-mercapto-1-propyltrimethoxysilane, 1 percent of 3-(methylthio)-1-propyltrimethoxysilane, and 96 percent of 3-(acetylthio)-1-propyltrimethoxysilane (product). Flash distillation from one to two grams of powdered sodium methoxide yielded a colorless product. The sodium methoxide was added to ensure that any remaining acidity was neutralized. Further optional fractional distillation yielded a product in excess of 98 percent purity by GC. The flask was placed into a water bath at 64° C Methanol was removed from the flask by distilling off a methanol-toluene azeotrope under a partial vacuum was maintained at 30° to 35° C. during which time 1,500 ml of distillate was collected An additional 429 grams of toluene were added the distillation an increase in distillation head temperature from 35° to 55° C. at which methanol removal from the flask to cool The flask was placed in an ice-water bath resulting in what in small portions with continued stirring in an ice-water bath until the reaction the completion of the reaction This mixture was filtered the solvent was removed from the filtrate to yield a nearly colorless product Flash distillation from one to two grams of powdered sodium methoxide yielded a colorless product Further optional fractional distillation yielded a product in excess of 98 percent purity by GC

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

Procedure: 816 grams of 3-mercapto-1-propyltrimethoxysilane, 871 grams of 25 weight percent methanolic solution of sodium methoxide, and 1,724 grams of toluene were charged to a 5-liter flask under an atmosphere of nitrogen. The stirred mixture developed a pinkish color. Methanol was removed from the flask by distilling off a methanol-toluene azeotrope, during which time the contents of the flask turned colorless. The appearance of a strong density current in the distillate which coincided with an increased in distillation head temperature from 63° C. to 108° C. signaled the point at which methanol removal from the flask was complete. With continued stirring, the contents of the flask were allowed to cool and were placed in an ice-water bath. 361 grams of propionyl chloride was added to the flask dropwise and/or in small portions with continued stirring in an ice-water bath until the reaction was complete. Aliquots of the stirred mixture were taken periodically and placed onto pH paper. An alkaline reading indicated the completion of the reaction. The final mixture was a white suspension of NaCl in a toluene solution of the product. This mixture was filtered and the solvent was removed from the filtrate to yield a light brown product. Gas chromatography indicated 5 percent 3-mercapto-1-propyltrimethoxysilane, 25 percent of 3-(methylthio)-1-propyltrimethoxysilane, and 70 percent of 3-(acetylthio)-1-propyltrimethoxysilane (product). Flash distillation from one to two grams of powdered sodium methoxide yielded a colorless product. The sodium methoxide was added to ensure that any remaining acidity was neutralized. Further optional fractional distillation yielded a product in excess of 98 percent purity by GC. Methanol was removed from the flask by distilling off a methanol-toluene azeotrope an increased in distillation head temperature from 63° C. to 108° C. at which methanol removal from the flask to cool were placed in an ice-water bath 361 grams of propionyl chloride was added to the flask dropwise in small portions with continued stirring in an ice-water bath until the reaction the completion of the reaction This mixture was filtered the solvent was removed from the filtrate to yield a light brown product Flash distillation from one to two grams of powdered sodium methoxide yielded a colorless product Further optional fractional distillation yielded a product in excess of 98 percent purity by GC

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

Procedure: Into a reaction vessel equipped with a stirrer were charged 3.0 parts of tolylene diisocyanate, 50.5 parts of a ring-opening copolymer from ethylene oxide and butene oxide, having a number average molecular weight of 4,000, and 0.01 part of 2,6-di-t-butyl-p-cresol, as a polymerization inhibitor. The mixture was cooled with ice to a temperature of below 10° C., while stirring. When the temperature was lower than 10° C., 0.04 part of dibutyltindilaurate was added and the mixture was stirred for 2 hours while controlling the temperature at 20-30° C. Then, after the addition of 0.3 part of γ-mercaptopropyltrimethoxy silane, the mixture was stirred for a further one hour at 30-40° C., whereupon 1.2 parts of hydroxyethyl acrylate was added. The mixture was stirred for 4 hours at 50-60° C., until the amount of remaining isocyanate is 0.1% by weight or less. The liquid urethane acrylate obtained in this manner is hereinafter referred to as UA-1. Into a reaction vessel equipped with a stirrer The mixture was cooled with ice to a temperature of below 10° C. was lower than 10° C. 0.04 part of dibutyltindilaurate was added the mixture was stirred for 2 hours at 20-30° C was added

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 267.6 g of a methanol solution of 22% sodium hydrogensulfide anhydride (1.05 mol) was put into an autoclave with an internal volume of 1 liter and the air was replaced by nitrogen. 0.3 mol of hydrogen sulfide was then blown in and the system was pressurized to 0.9 kgf/cm2 to oversaturate hydrogen sulfide. After heating the system up to 90° C., 198.7 g (1.0 mole) of 3-chloropropyltrimethoxy silane was dripped for 3 hours, and during the dripping, 0.1 mol of hydrogen sulfide was blown into the system so that the pressure in the system was kept at 3.5 kgf/cm2. After the dripping, the system was aged for 2 hour at 90° C., followed by cooling. By-product salts produced in the reaction were filtered away. The composition was analyzed by means of gas chromatography. 3-mercaptopropyltrimethoxy silane was obtained with a yield of 93.5%. by cooling By-product salts produced in the reaction were filtered away

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 267.6 g of a methanol solution of 22% sodium hydrogensulfide anhydride (1.05 mol) was put into an autoclave with an internal volume of 1 liter, and the air was replaced by nitrogen. 0.3 mol of hydrogen sulfide was then blown in and the system was pressurized to 0.9 kgf/cm2 to oversaturate hydrogen sulfide. After heating the system up to 70° C., 198.7 g (1.0 mole) of 3-chloropropyltrimethoxy silane was dripped for 3 hours, and, during the dripping, 0.05 mol of hydrogen sulfide was blown into the system so that the pressure in the system was kept at 2.5 kgf/cm2. After the dripping, the temperature was raised to 100° C. and the system was aged for 1 hour, followed by cooling. By-product salts produced in the reaction were filtered away. The composition was analyzed by means of gas chromatography. 3-mercaptopropyltrimethoxy silane was obtained with a yield of 94.1%. After the dripping, the temperature was raised to 100° C. by cooling By-product salts produced in the reaction were filtered away

Conditions: temp:7.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (3-Mercaptopropyl)trimethoxysilane (1.97 g, 0.01 mol) was added within 10 minutes to a stirred suspension of sodium hydride (60% w/w, 0.42 g, 0.0175 mol) in dry diethyl ether (20 mL) whilst maintaining the reaction temperature between 5-10° C. The reaction mixture was then cooled to ˜0° C. when carbon disulfide (1.34 g, 0.012 mol) was added and the resulting mixture was kept at this temperature for one hour. Then α-Chloroacetonitrile (1.30 g, 0.017 mol) was added and the mixture was stirred at ambient temperature for a one hour. The reaction mixture was the filtered and the filtrate concentrated on rotary evaporator. Purification by chromatography on a short silica gel column (ethyl acetate: n-hexane 1:4) gave the title compound as a yellow liquid (2.25 g, 72%). 1H-nmr (CDCl3) δ 0.75 (m, 2H), 1.86 (m, 2H), 3.46 (t, 2H), 3.58 (s, 9H), 4.15 (s, 2H). was added filtered the filtrate concentrated on rotary evaporator Purification by chromatography on a short silica gel column (ethyl acetate: n-hexane 1:4)

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 566 g (10.1 mols) of sodium hydrogen sulfide together with 2,400 g of dimethylformamide were introduced into the apparatus described in Example 1. While stirring, 2,000 g (10.1 mols) of 3-chloropropyltrimethoxysilane were added to the contents of the flask over a period of 60 minutes, whereby the temperature of the contents of the flask rose to about 100° C. By application of additional heat the temperature was increased to 110° C. and maintained at this level. Samples of the reaction mixture were taken at intervals of 15 minutes and gas-chromatographically analyzed. After the elapse of 75 minutes of reaction time only traces of the provided silane compound could be detected in the reaction mixture. The distillative work-up of the raw reaction mixture gave a yield of 84% of 3-mercaptopropyltrimethoxysilane. rose to about 100° C By application of additional heat the temperature maintained at this level were taken at intervals of 15 minutes and gas-chromatographically After the elapse of 75 minutes of reaction time The distillative work-up of the raw reaction mixture

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

Procedure: ##STR16## HSCH2CH2CH2Si(OCH3)3 ; HO(C2H4O)3C2H4N(CH3)(CH2)3Si(OC4H9)3 ;