chloromethyl-methoxy-dimethylsilane

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 230.4 kg (1.662 kmol) of (chloromethyl)-methoxydimethylsilane and 11.8 kg (34.8 mol) of tetrabutylphosphonium bromide was heated up to 90° C. and admixed during 3 h with 150 kg (1.828 kmol) of sodium acetate (anhydrous) in 6 portions of 25 kg each such that the temperature did not exceed 114° C. The mixture was subsequently stirred without additional heating for 1 h and then at 115-122° C. for a further 2 h. Thereafter, the product was distilled out through a column at 18-30 mbar (head), 50-53° C. (head) and 84-120° C. (pot), while 150 kg of Hydroseal G 400 H were metered into the residue during the distillation to ensure stirrability. The product (acetoxymethyl)methoxydimethylsilane (249.2 kg, 1.536 kmol, 92% of theory; purity 99.6% (GC area %)) was obtained as a colorless liquid. The solvent, sodium chloride, excess sodium acetate and the phase transfer catalyst in the form of the chloride, bromide and acetate salt of tetrabutylphosphonium remained in the residue. did not exceed 114° C without additional heating for 1 h Thereafter, the product was distilled out through a column at 18-30 mbar (head), 50-53° C. (head) and 84-120° C. (pot), while 150 kg of Hydroseal G 400 H were metered into the residue during the distillation

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 61.1 kg of Hydroseal G 400 H and 50 kg (609.4 mol) of sodium acetate was dried by heating at 150° C./2 mbar for 1 h. After cooling down to 112° C., the vacuum was broken with nitrogen, 3.76 kg (11.1 mol) of tetrabutylphosphonium bromide were added and the temperature was adjusted to 120° C. Then, under agitation, 76.8 kg (554 mol) of (chloromethyl)methoxydimethylsilane were metered in over 1 h. The mixture was subsequently stirred at the same temperature for a further 6 h. The product was then distilled out through a column at 20 mbar (head), 50-56° C. (head) and 70-145° C. (pot), while a further 36.7 kg of Hydroseal G 400 H were metered in during the distillation to ensure stirrability. The product (acetoxymethyl)methoxydimethylsilane (89.0 kg, 548.5 mol, 99% of theory; purity 99.5% (GC area %)) was obtained as a colorless liquid. The solvent, sodium chloride, excess sodium acetate and the phase transfer catalyst in the form of the chloride, bromide and acetate salt of tetrabutylphosphonium remained in the residue. was dried After cooling down to 112° C. were added was adjusted to 120° C were metered in over 1 h The product was then distilled out through a column at 20 mbar (head), 50-56° C. (head) and 70-145° C. (pot), while a further 36.7 kg of Hydroseal G 400 H were metered in during the distillation

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 61.1 kg of Hydroseal G 400 H and 50 kg (609.4 mol) of sodium acetate was dried by heating at 150° C./2 mbar for 1.5 h. After cooling down to below 120° C., the vacuum was broken with nitrogen, 3.76 kg (11.1 mol) of tetrabutylphosphonium bromide were added and the temperature was adjusted to 120° C. Then, under agitation, 73.2 kg (528 mol) of (chloromethyl)methoxydimethylsilane were metered in over 2.5 h. The mixture was subsequently stirred at the same temperature for a further 4 h. The product was then distilled out through a column at 20 mbar (head), 46-55° C. (head) and 73-145° C. (pot), while a further 36.7 kg of Hydroseal G 400 H were metered in during the distillation to ensure stirrability. The product (acetoxymethyl)methoxydimethylsilane (80.4 kg, 495.5 mol, 94% of theory; purity 99.4% (GC area %)) was obtained as a colorless liquid. The solvent, sodium chloride, excess sodium acetate and the phase transfer catalyst in the form of the chloride, bromide and acetate salt of tetrabutylphosphonium remained in the residue. The residue was worked up by filtration using an inverting filter centrifuge to give 93 kg of filtrate (Hydroseal) and 41 kg of solid material (NaCl, NaOAc, Bu4PBr; anions and cations exchanged in part). The filter cake was washed with xylene (isomer mixture, 2×20 L) and filtered once more by the same method. The filtrate contained the xylene-soluble phase transfer catalyst in the form of the chloride, bromide and acetate salt of tetrabutylphosphonium, the filter cake contained above all the sodium salts of the chloride, in part also of the acetate and of the bromide. The solvent thus recovered and the recovered catalyst can be reused, in which case the xylene can optionally be distilled off or co-used. was dried After cooling down to below 120° C. were added was adjusted to 120° C were metered in over 2.5 h The product was then distilled out through a column at 20 mbar (head), 46-55° C. (head) and 73-145° C. (pot), while a further 36.7 kg of Hydroseal G 400 H were metered in during the distillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 20 mL of high boiler solvent as per Table 1, 13.5 g (165 mmol) of sodium acetate (anhydrous) and the Table 1 amount of phase transfer catalyst (amount specified in mol % based on employed amount of silane) was heated to the temperature reported in Table 1 and dried at this temperature under a vacuum of 10 mbar for minutes. The vacuum was subsequently broken with argon, and (chloromethyl)methoxydimethylsilane (20.8 g, 150 mmol) was metered in at this temperature over 30 minutes under agitation. The mixture was further stirred at this temperature until a gas chromatogram (FID detector) or a 1H NMR spectrum indicated more than 99% conversion of the silane; the reaction times required for this are reported in Table 1. The product was subsequently distilled off at 10-90 mbar (head), 50-90° C. (head) and 70-120° C. (pot) through a Widmer column (20 cm) to obtain the Table 1 yields of (acetoxymethyl)methoxydimethylsilane as a colorless liquid having a purity of >99% (GC area %). The solvent, sodium chloride, excess sodium acetate and the phase transfer catalyst in the form of its chloride and acetate salts (and also of the bromide salt when a bromide was used) remained in the residue. dried at this temperature under a vacuum of 10 mbar for minutes the reaction times The product was subsequently distilled off at 10-90 mbar (head), 50-90° C. (head) and 70-120° C. (pot) through a Widmer column (20 cm) to obtain the Table 1

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 20 mL of high boiler solvent as per Table 1, 13.5 g (165 mmol) of sodium acetate (anhydrous) and the Table 1 amount of phase transfer catalyst (amount specified in mol % based on employed amount of silane) was heated to the temperature reported in Table 1 and dried at this temperature under a vacuum of 10 mbar for minutes. The vacuum was subsequently broken with argon, and (chloromethyl)methoxydimethylsilane (20.8 g, 150 mmol) was metered in at this temperature over 30 minutes under agitation. The mixture was further stirred at this temperature until a gas chromatogram (FID detector) or a 1H NMR spectrum indicated more than 99% conversion of the silane; the reaction times required for this are reported in Table 1. The product was subsequently distilled off at 10-90 mbar (head), 50-90° C. (head) and 70-120° C. (pot) through a Widmer column (20 cm) to obtain the Table 1 yields of (acetoxymethyl)methoxydimethylsilane as a colorless liquid having a purity of >99% (GC area %). The solvent, sodium chloride, excess sodium acetate and the phase transfer catalyst in the form of its chloride and acetate salts (and also of the bromide salt when a bromide was used) remained in the residue. dried at this temperature under a vacuum of 10 mbar for minutes the reaction times The product was subsequently distilled off at 10-90 mbar (head), 50-90° C. (head) and 70-120° C. (pot) through a Widmer column (20 cm) to obtain the Table 1

反応条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 69.3 g of (chloromethyl)methoxydimethyl-silane, 40.6 g of potassium cyanate and 42.6 g of 2-pyrrolidinone in 150 ml of anhydrous DMF was heated at 130° C. with stirring for 5 h. The solvent was then removed under reduced pressure. This gave N-[(methoxydimethylsilyl)methyl]-2-oxo-1-pyrrolidinecarboxamide in quantitative yield with a purity of >90% (analysis by 1H NMR, see Example 2a). The solvent was then removed under reduced pressure

反応条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 69.3 g of (chloromethyl)methoxydimethyl-silane, 40.6 g of potassium cyanate and 42.6 g of 2-pyrrolidinone in 150 ml of anhydrous DMF was heated at 130° C. with stirring for 5 h. The solvent was then removed under reduced pressure. This gave N-[(methoxydimethylsilyl)methyl]-2-oxo-1-pyrrolidinecarboxamide in quantitative yield with a purity of >90% (analysis by 1H NMR, see Example 2a). The solvent was then removed under reduced pressure