chloromethyl acetate

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:0.00; pressure:0.00; stir:

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

実験手順: To a solution of dehydroepiandrosterone (2.88 g, 10 mmol) in THF (100 mL) is added sodium hydride (11 mmol, 60% in oil) at room temperature under an argon atmosphere. When all the sodium hydride has reacted, chloromethyl acetate (prepared from acetyl chloride and formaldehyde (or derivative) using ZnCl2 as catalyst) is added and the mixture is heated for a few hours. After cooling, the mixture is poured into water and extracted with ethyl acetate. The organic phase is then washed with water, dried, filtered and evaporated to dryness to give the desired compound. is added the mixture is heated for a few hours After cooling extracted with ethyl acetate The organic phase is then washed with water dried filtered evaporated to dryness

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

実験手順: To a solution of N-methyl-N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]hydroxyamine (700 mg, 1.93 mmol) in THF (10 ml) containing triethylamine (1.2 eq.) is added chloromethylacetate (2 eq.). The mixture is stirred at RT overnight. Excess THF is removed and the product is evaporated to dryness and purified to give N-methyl-N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]acetoxymethoxyamine. Excess THF is removed the product is evaporated to dryness purified

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

実験手順: To a solution of dehydroepiandrosterone (2.88 g, 10 mmol) in THF (100 mL) is added sodium hydride (11 mmol, 60% in oil) at room temperature under an argon atmosphere. When all the sodium hydride has reacted, chloromethyl acetate (prepared from acetyl chloride and formaldehyde (or derivative) using ZnCl2 as catalyst) is added and the mixture is heated for a few hours. After cooling, the mixture is poured into water and extracted with ethyl acetate. The organic phase is then washed with water, dried, filtered and evaporated to dryness to give the desired compound. is added the mixture is heated for a few hours After cooling extracted with ethyl acetate The organic phase is then washed with water dried filtered evaporated to dryness

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

実験手順: To a solution of dehydroepiandrosterone (2.88 g, 10 mmol) in THF (100 mL) is added sodium hydride (11 mmol, 60% in oil) at room temperature under an argon atmosphere. When all the sodium hydride has reacted, chloromethyl acetate (prepared from acetyl chloride and formaldehyde (or derivative) using ZnCl2 as catalyst) is added and the mixture is heated for a few hours. After cooling, the mixture is poured into water and extracted with ethyl acetate. The organic phase is then washed with water, dried, filtered and evaporated to dryness to give the desired compound. is added the mixture is heated for a few hours After cooling extracted with ethyl acetate The organic phase is then washed with water dried filtered evaporated to dryness

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred mixture of 1 ,4-dihydro-2,6-dimethyl-4-(2',3'-dichorophenyl)-5-carboxymethyl-3-pyridinecarboxylic acid (0.3 g, 0.83 mmol) and sodium bicarbonate (0.14 g, 1.69 mmol) in DMF (15 ml) under nitrogen atmosphere was added chloromethyl acetate (0.137 g, 1.26 mmol). The reaction mixture was heated at 80° C. for 18 h. Workup by evaporation of solvent and addition of water. Extraction with dichloromethane, the extract was dried over sodium sulfate and concentrated. The resulting oil was subjected to flash chromatography [silica gel, dichloromethane - dichloromethane/methanol (9/1) gradient] to give colorless crystals (0.17 g, 48%) mp.144.5°-147.6° C. 1H-NMR (CDCl3): 7.30-7.04 (Ar, 3H); 5.97 (s, 1H); 5.73 (d, J=5.5 Hz, 1H); 5.69 (d, J=5.5 Hz, 1H); 5.46 (s, 1H); 3.60 (s, 3H); 2.32 (s, 3H); 2.30 (s, 3H); 2.03 (s, 3H). 13C-NMR (CDCl3): 169.64; 167.63; 165.81; 147.46; 146.77; 143.85; 132.86; 131.15; 129.83; 128.31; 126.98; 103.97; 101.89; 78.73; 50.93; 38.45; 20.80; 19.86; 19.26. Workup by evaporation of solvent and addition of water Extraction with dichloromethane the extract was dried over sodium sulfate concentrated

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: 3α-Hydroxy-11-oxo-5α-androstane-17β-carboxylic acid (1g.) was warmed with tetra-butyl ammonium hydroxide (1.94g. Of 40% solution) and acetone (10 ml.) to effect solution. The solution was refluxed with sodium iodide (100 mg.). potassium bicarbonate (150 mg.) and chloromethyl acetate (0.6 ml.) for 2 hours. The mixture was evaporated to small volume, diluted with ethyl acetate, washed with water, dried (Na2SO4) and evaporated to a residue. Purification by preparative t.l.c. gave title compound (less polar band) (318 mg.) as white foam; [α]D + 52°. The mixture was evaporated to small volume diluted with ethyl acetate washed with water dried (Na2SO4) evaporated to a residue Purification by preparative t.l.c

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

実験手順: 3α-Hydroxy-11-oxo-5α-androstane-17β-carboxylic acid (1g.) was warmed with tetra-butyl ammonium hydroxide (1.94g. Of 40% solution) and acetone (10 ml.) to effect solution. The solution was refluxed with sodium iodide (100 mg.). potassium bicarbonate (150 mg.) and chloromethyl acetate (0.6 ml.) for 2 hours. The mixture was evaporated to small volume, diluted with ethyl acetate, washed with water, dried (Na2SO4) and evaporated to a residue. Purification by preparative t.l.c. gave title compound (less polar band) (318 mg.) as white foam; [α]D + 52°. The mixture was evaporated to small volume diluted with ethyl acetate washed with water dried (Na2SO4) evaporated to a residue Purification by preparative t.l.c

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

実験手順: 0.37 g of 4-ethyl-2-propyl-1-[[2'-(N-triphenylmethyl(tetrazol-5-yl))biphenyl-4-yl]methyl]imidazole-5-carboxylic acid was dissolved in 5 mL THF and 0.5 g chloromethyl acetate and 0.5 mL triethylamine were added. The resulting solution was stirred overnight. The solvent was evaporated and the residue dissolved in methanol with 0.25 mL acetic acid and stirred 8 hours with 10 g silica gel. The mixture was evaporated and the residue on the gel was flash chromatographed with MeOH/CH2Cl2 (1:9) to provide 0.124 g of the title compound. The solvent was evaporated the residue dissolved in methanol with 0.25 mL acetic acid stirred 8 hours with 10 g silica gel The mixture was evaporated chromatographed with MeOH/CH2Cl2 (1:9)