chloro-(2,3-dimethylbutan-2-yl)-dimethylsilane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: After a mixture of 149.9 g (523 mmol) (3β)-3-hydroxy-androsta-5,7-dien-17-one and 56.9 g (836 mmol) imidazole in 500 mL of dichloromethane was cooled to 3° C., 144 mL (732 mmol) dimethylthexylsilyl chloride was added dropwise over 90 min, keeping the temperature below 6° C. After stirring at room temperature overnight, the mixture was washed with 500 mL of water, and the aqueous layer was back-extracted with 200 mL of dichloromethane. The combined organic layers were washed with 500 mL of saturated aqueous NaHCO3, dried over sodium sulfate, and concentrated. The resulting solid was suspended in 700 mL of methanol containing 14 mL of triethylamine, and the suspension was refluxed for 20 minutes. After cooling in a refrigerator overnight, the precipitate was filtered, washed with 600 mL of methanol/H2O (9:1), and dried by suction for 2 hr. Further drying at 40° C. under high vacuum afforded 185.1 g (82.5% yield) of (3β)-3-[[(1,1,2-trimethylpropyl)dimethylsilyl]oxy]androsta-5,7-dien-17-one as a beige solid: mp 119°-125° C.; Anal. Calcd for C27H44O2Si: C, 75.64; H, 10.34; Si, 6.55. Found C, 75.82; H, 10.29; Si, 6.72. the temperature below 6° C the mixture was washed with 500 mL of water the aqueous layer was back-extracted with 200 mL of dichloromethane The combined organic layers were washed with 500 mL of saturated aqueous NaHCO3 dried over sodium sulfate concentrated the suspension was refluxed for 20 minutes After cooling in a refrigerator overnight the precipitate was filtered washed with 600 mL of methanol/H2O (9:1) dried by suction for 2 hr Further drying at 40° C. under high vacuum

反応条件: temp:3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: After a mixture of 149.9 g (523 mmol) (3β)-3-hydroxy-androsta-5,7-dien-17-one and 56.9 g (836 mmol) imidazole in 500 mL of dichloromethane was cooled to 3° C., 144 mL (732 mmol) dimethylthexylsilyl chloride was added dropwise over 90 min, keeping the temperature below 6° C. After stirring at room temperature overnight, the mixture was washed with 500 mL of water, and the aqueous layer was back-extracted with 200 mL of dichloromethane. The combined organic layers were washed with 500 mL of saturated aqueous NaHCO3, dried over sodium sulfate, and concentrated. The resulting solid was suspended in 700 mL of methanol containing 14 mL of triethylamine, and the suspension was refluxed for 20 minutes. After cooling in a refrigerator overnight, the precipitate was filtered, washed with 600 mL of methanol/H2O (9:1), and dried by suction for 2 hr. Further drying at 40° C. under high vacuum afforded 185.1 g (82.5% yield) of (3β)-3-[[(1,1,2-trimethylpropyl)dimethylsilyl]oxy]androsta-5,7-dien-17-one as a beige solid: mp 119°-125° C.; Anal. Calcd for C27H44O2Si: C, 75.64; H, 10.34; Si, 6.55. Found C, 75.82; H, 10.29; Si, 6.72. the temperature below 6° C the mixture was washed with 500 mL of water the aqueous layer was back-extracted with 200 mL of dichloromethane The combined organic layers were washed with 500 mL of saturated aqueous NaHCO3 dried over sodium sulfate concentrated the suspension was refluxed for 20 minutes After cooling in a refrigerator overnight the precipitate was filtered washed with 600 mL of methanol/H2O (9:1) dried by suction for 2 hr Further drying at 40° C. under high vacuum

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

実験手順: To a solution of 75.1 g of 2-formyl-3-hydroxy-5-methoxy-6-methylbenzoic acid allyl ester in 0.6 l of N,N-dimethylformamide were added 81.0 g of dimethyl-(1,1,2-trimethyl-propyl)-chlorosilane and 45.5 g of triethylamine. The mixture was stirred for 4 h at room temperature and then evaporated in vacuo. The residue was taken up in 2 l of ethyl acetate, and the mixture was successively washed with 1N hydrochloric acid and with brine, and dried over sodium sulfate. The solvent was evaporated in vacuo and the residue was crystallized from hexane to give 108.8 g of 2-formyl-5-methoxy-6-methyl-3-[dimethyl-(1,1,2-trimethyl-propyl)silanyloxy]-benzoic acid allyl ester as white crystals of m.p. 81°-82° C. evaporated in vacuo the mixture was successively washed with 1N hydrochloric acid and with brine dried over sodium sulfate The solvent was evaporated in vacuo the residue was crystallized from hexane

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

実験手順: To a solution of 75.1 g of 2-formyl-3-hydroxy-5-methoxy-6-methylbenzoic acid allyl ester in 0.6 l of N,N-dimethylformamide were added 81.0 g of dimethyl-(1,1,2-trimethyl-propyl)-chlorosilane and 45.5 g of triethylamine. The mixture was stirred for 4 h at rootn temperature and then evaporated in vacuo. The residue was taken up in 2 l of ethyl acetate, and the mixture was successively washed with 1N hydrochloric acid and with brine, and dried over sodium sulfate. The solvent was evaporated in vacuo and the residue was crystallized from hexane to give 108.8 g of 2-formyl-5-methoxy-6-methyl-3-[dimethyl-(1,1,2-trimethyl-propyl)silanyloxy]-benzoic acid allyl ester as white crystals of m.p. 81°-82° C. evaporated in vacuo the mixture was successively washed with 1N hydrochloric acid and with brine dried over sodium sulfate The solvent was evaporated in vacuo the residue was crystallized from hexane

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-hydroxy-4-[2-(5-methyl-2-phenyl-oxazol-4-yl)-ethoxy]-benzaldehyde (540 mg, 1.67 mmol) in 8 ml N,N-dimethylformamide cooled to 0° C., were added 398 mg (5.85 mol) imidazole and 1.1 ml (5.85 mmol) thexyl-dimethylchlorosilane. The reaction mixture was stirred 50 minutes at 0° C., diluted with AcOEt, washed with water/ice, HCl (1M)/ice and brine and the aqueous layer was extracted with AcOEt. The combined organic layers were dried over Na2SO4 and evaporated. Chromatography (SiO2; AcOEt/heptane) delivered 346 mg (45%) of the title compound as an oil. washed with water/ice, HCl (1M)/ice and brine the aqueous layer was extracted with AcOEt The combined organic layers were dried over Na2SO4 evaporated

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-hydroxy-4-[2-(5-methyl-2-phenyl-oxazol-4-yl)-ethoxy]-benzaldehyde (540 mg, 1.67 mmol) in 8 ml N,N-dimethylformamide cooled to 0° C., were added 398 mg (5.85 mol) imidazole and 1.1 ml (5.85 mmol) thexyl-dimethylchlorosilane. The reaction mixture was stirred 50 minutes at 0° C., diluted with AcOEt, washed with water/ice, HCl (1M)/ice and brine and the aqueous layer was extracted with AcOEt. The combined organic layers were dried over Na2SO4 and evaporated. Chromatography (SiO2; AcOEt/heptane) delivered 346 mg (45%) of the title compound as an oil. washed with water/ice, HCl (1M)/ice and brine the aqueous layer was extracted with AcOEt The combined organic layers were dried over Na2SO4 evaporated

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

実験手順: This intermediate (hereinafter "intermediate A") was prepared in two steps. 4-Bromophenylacetic acid underwent diborane (B2H6) reduction. A solution of the resulting alcohol then underwent silylation with sodium hydride (NaH) and thexyl dimethyl silyl chloride.

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

実験手順: This intermediate (hereinafter "intermediate A") was prepared in two steps. 4-Bromophenylacetic acid underwent diborane (B2H6) reduction. A solution of the resulting alcohol then underwent silylation with sodium hydride (NaH) and thexyl dimethyl silyl chloride.

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

実験手順: A solution of thexyldimethylchlorosilane (100.0 g, 559.3 mmol) and imidazole (38.08 g, 559.3 mmol) in DMF (350 mL) was reacted with 2-indanone (67.40 g, 510.0 mmol) and then stirred for two days at room temperature. The reaction mixture was treated with water (300 mL). and extracted with Et2O (3×200 mL). The combined organic phases were washed with water (2×200 mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil. Distillation under reduced pressure gave 116.89 g (83.5%) of the title compound as a yellow oil (bp. 128-130° C./0.4 mbar). 1H NMR (CDCl3, δ): 7.24-7.10 (m, 3H); 7.00 (td, 3J=7.3 Hz, 4J=1.3 Hz, 1H); 5.74 (d, 4J=0.6 Hz, 1H); 3.28 (s, 2H); 1.70 (sept, 3J=6.8 Hz, 1H); 0.93 (s, 6H); 0.92 (d, 3J=6.8 Hz, 6H); 0.29 (s, 6H). 13C NMR (CDCl3, δ): 162.82; 145.71; 137.03; 126.86; 123.45; 122.73; 119.29; 106.92; 40.00; 34.49; 25.51; 20.51; 18.89; −2.26. and extracted with Et2O (3×200 mL) The combined organic phases were washed with water (2×200 mL) dried over sodium sulfate Evaporation of the solvents left a red oil Distillation under reduced pressure

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

実験手順: A solution of thexyldimethylchlorosilane (100.0 g, 559.3 mmol) and imidazole (38.08 g, 559.3 mmol) in DMF (350 mL) was reacted with 2-indanone (67.40 g, 510.0 mmol) and then stirred for two days at room temperature. The reaction mixture was treated with water (300 mL). and extracted with Et2O (3×200 mL). The combined organic phases were washed with water (2×200 mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil. Distillation under reduced pressure gave 116.89 g (83.5%) of the title compound as a yellow oil (bp. 128-130° C./0.4 mbar). 1H NMR (CDCl3, δ): 7.24-7.10 (m, 3H); 7.00 (td, 3J=7.3 Hz, 4J=1.3 Hz, 1H); 5.74 (d, 4J=0.6 Hz, 1H); 3.28 (s, 2H); 1.70 (sept, 3J=6.8 Hz, 1H); 0.93 (s, 6H); 0.92 (d, 3J=6.8 Hz, 6H); 0.29 (s, 6H). 13C NMR (CDCl3, δ): 162.82; 145.71; 137.03; 126.86; 123.45; 122.73; 119.29; 106.92; 40.00; 34.49; 25.51; 20.51; 18.89; −2.26. and extracted with Et2O (3×200 mL) The combined organic phases were washed with water (2×200 mL) dried over sodium sulfate Evaporation of the solvents left a red oil Distillation under reduced pressure