2-ethylhexyl nitrate

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

実験手順: A reactor is charged with 13.48 parts of mixed acid containing 3.33 parts HNO3, 7.77 parts H2SO4 and 2.38 parts H2O. The mixed acid is agitated and its temperature adjusted to 25°±3° C. Urea (0.40 part) is added to the mixed acid over a period of 1/2 hour and the temperature allowed to rise to 32.5°±2.5° C. 2-Ethylhexyl alcohol (5.85 parts) are added to the reactor at a rate of 0.065 part per minute while maintaining the temperature at 32.5°±2.5° C. After addition of 2-ethylhexyl alcohol, the reaction mixture is held at 32.5°±2.5° C. for 1 hour at which time agitation is stopped and the bottom acid layer which forms is drained from the reactor. An aqueous 10% sodium sulfate solution (2.73 parts) is added to the reactor and the resulting mixture agitated. After 15 minutes, agitation is stopped and the bottom aqueous solution layer, which forms, is separated. An aqueous 10% sodium sulfate solution is added to the ethylhexyl nitrate layer which is agitated for 15 minutes at which point 0.50 part of an aqueous 10% sodium carbonate solution is slowly added. An additional 2.73 parts of a 10% aqueous sodium sulfate solution is added to the reactor and agitated for 15 minutes, after which the lower aqueous layer is drained. Another 2.73 parts of 10% aqueous sodium sulfate solution is added to the reactor and the contents agitated for 15 minutes after which 0.50 part 10% aqueous sodium carbonate is added, the agitation stopped and the lower aqueous layer drained. The 2-ethylhexyl nitrate product is obtained in 97% yield, i.e., 7.64 parts. A reactor is charged with 13.48 parts of mixed acid adjusted to 25°±3° C to rise to 32.5°±2.5° C while maintaining the temperature at 32.5°±2.5° C the resulting mixture agitated After 15 minutes is separated An aqueous 10% sodium sulfate solution is added to the ethylhexyl nitrate layer which is agitated for 15 minutes at which point 0.50 part of an aqueous 10% sodium carbonate solution is slowly added An additional 2.73 parts of a 10% aqueous sodium sulfate solution is added to the reactor agitated for 15 minutes Another 2.73 parts of 10% aqueous sodium sulfate solution is added to the reactor the contents agitated for 15 minutes after which 0.50 part 10% aqueous sodium carbonate is added

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

実験手順: Potasium tert-butoxide (7.6 g, 67.8 mM) and (20S)-20-hydroxymethylpregn-4-en-3-one (6.6 g, 20 mM) are combined in tert-butanol and heated at reflux temperature for 120 minutes. 2-ethylhexylnitrate (3.56 ml, 20 mM) is then added in one continuous portion. After 10 minutes, the reaction vessel is cooled to room temperature. The reaction is then quenched with acetic acid (9 ml) and stirred overnight. After diluting with dichloromethane (200 mL), the solids are removed, washed, and combined with the washing residue and subsequently purified as described in Example 1 to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one. heated at reflux temperature for 120 minutes The reaction is then quenched with acetic acid (9 ml) After diluting with dichloromethane (200 mL) the solids are removed washed subsequently purified to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one

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

実験手順: A reactor is charged with 13.48 parts of mixed acid containing 3.33 parts HNO3, 7.77 parts H2SO4 and 2.38 parts H2O. The mixed acid is agitated and its temperature adjusted to 25°±3° C. Urea (0.40 part) is added to the mixed acid over a period of 1/2 hour and the temperature allowed to rise to 32.5°±2.5° C. 2-Ethylhexyl alcohol (5.85 parts) are added to the reactor at a rate of 0.065 part per minute while maintaining the temperature at 32.5°±2.5° C. After addition of 2-ethylhexyl alcohol, the reaction mixture is held at 32.5°±2.5° C. for 1 hour at which time agitation is stopped and the bottom acid layer which forms is drained from the reactor. An aqueous 10% sodium sulfate solution (2.73 parts) is added to the reactor and the resulting mixture agitated. After 15 minutes, agitation is stopped and the bottom aqueous solution layer, which forms, is separated. An aqueous 10% sodium sulfate solution is added to the ethylhexyl nitrate layer which is agitated for 15 minutes at which point 0.50 part of an aqueous 10% sodium carbonate solution is slowly added. An additional 2.73 parts of a 10% aqueous sodium sulfate solution is added to the reactor and agitated for 15 minutes, after which the lower aqueous layer is drained. Another 2.73 parts of 10% aqueous sodium sulfate solution is added to the reactor and the contents agitated for 15 minutes after which 0.50 part 10% aqueous sodium carbonate is added, the agitation stopped and the lower aqueous layer drained. The 2-ethylhexyl nitrate product is obtained in 97% yield, i.e., 7.64 parts. A reactor is charged with 13.48 parts of mixed acid adjusted to 25°±3° C to rise to 32.5°±2.5° C while maintaining the temperature at 32.5°±2.5° C the resulting mixture agitated After 15 minutes is separated An aqueous 10% sodium sulfate solution is added to the ethylhexyl nitrate layer which is agitated for 15 minutes at which point 0.50 part of an aqueous 10% sodium carbonate solution is slowly added An additional 2.73 parts of a 10% aqueous sodium sulfate solution is added to the reactor agitated for 15 minutes Another 2.73 parts of 10% aqueous sodium sulfate solution is added to the reactor the contents agitated for 15 minutes after which 0.50 part 10% aqueous sodium carbonate is added

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

実験手順: Potasium tert-butoxide (7.6 g, 67.8 mM) and (20S)-20-hydroxymethylpregn-4-en-3-one (6.6 g, 20 mM) are combined in tert-butanol and heated at reflux temperature for 120 minutes. 2-ethylhexylnitrate (3.56 ml, 20 mM) is then added in one continuous portion. After 10 minutes, the reaction vessel is cooled to room temperature. The reaction is then quenched with acetic acid (9 ml) and stirred overnight. After diluting with dichloromethane (200 mL), the solids are removed, washed, and combined with the washing residue and subsequently purified as described in Example 1 to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one. heated at reflux temperature for 120 minutes The reaction is then quenched with acetic acid (9 ml) After diluting with dichloromethane (200 mL) the solids are removed washed subsequently purified to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one

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

実験手順: Potasium tert-butoxide (7.6 g, 67.8 mM) and (20S)-20-hydroxymethylpregn-4-en-3-one (6.6 g, 20 mM) are combined in tert-butanol and heated at reflux temperature for 120 minutes. 2-ethylhexylnitrate (3.56 ml, 20 mM) is then added in one continuous portion. After 10 minutes, the reaction vessel is cooled to room temperature. The reaction is then quenched with acetic acid (9 ml) and stirred overnight. After diluting with dichloromethane (200 mL), the solids are removed, washed, and combined with the washing residue and subsequently purified as described in Example 1 to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one. heated at reflux temperature for 120 minutes The reaction is then quenched with acetic acid (9 ml) After diluting with dichloromethane (200 mL) the solids are removed washed subsequently purified to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one

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

実験手順: Potasium tert-butoxide (7.6 g, 67.8 mM) and (20S)-20-hydroxymethylpregn-4-en-3-one (6.6 g, 20 mM) are combined in tert-butanol and heated at reflux temperature for 120 minutes. 2-ethylhexylnitrate (3.56 ml, 20 mM) is then added in one continuous portion. After 10 minutes, the reaction vessel is cooled to room temperature. The reaction is then quenched with acetic acid (9 ml) and stirred overnight. After diluting with dichloromethane (200 mL), the solids are removed, washed, and combined with the washing residue and subsequently purified as described in Example 1 to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one. heated at reflux temperature for 120 minutes The reaction is then quenched with acetic acid (9 ml) After diluting with dichloromethane (200 mL) the solids are removed washed subsequently purified to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one

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

実験手順: Potasium tert-butoxide (7.6 g, 67.8 mM) and (20S)-20-hydroxymethylpregn-4-en-3-one (6.6 g, 20 mM) are combined in tert-butanol and heated at reflux temperature for 120 minutes. 2-ethylhexylnitrate (3.56 ml, 20 mM) is then added in one continuous portion. After 10 minutes, the reaction vessel is cooled to room temperature. The reaction is then quenched with acetic acid (9 ml) and stirred overnight. After diluting with dichloromethane (200 mL), the solids are removed, washed, and combined with the washing residue and subsequently purified as described in Example 1 to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one. heated at reflux temperature for 120 minutes The reaction is then quenched with acetic acid (9 ml) After diluting with dichloromethane (200 mL) the solids are removed washed subsequently purified to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one

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

実験手順: A reactor is charged with 13.48 parts of mixed acid containing 3.33 parts HNO3, 7.77 parts H2SO4 and 2.38 parts H2O. The mixed acid is agitated and its temperature adjusted to 25°±3° C. Urea (0.40 part) is added to the mixed acid over a period of 1/2 hour and the temperature allowed to rise to 32.5°±2.5° C. 2-Ethylhexyl alcohol (5.85 parts) are added to the reactor at a rate of 0.065 part per minute while maintaining the temperature at 32.5°±2.5° C. After addition of 2-ethylhexyl alcohol, the reaction mixture is held at 32.5°±2.5° C. for 1 hour at which time agitation is stopped and the bottom acid layer which forms is drained from the reactor. An aqueous 10% sodium sulfate solution (2.73 parts) is added to the reactor and the resulting mixture agitated. After 15 minutes, agitation is stopped and the bottom aqueous solution layer, which forms, is separated. An aqueous 10% sodium sulfate solution is added to the ethylhexyl nitrate layer which is agitated for 15 minutes at which point 0.50 part of an aqueous 10% sodium carbonate solution is slowly added. An additional 2.73 parts of a 10% aqueous sodium sulfate solution is added to the reactor and agitated for 15 minutes, after which the lower aqueous layer is drained. Another 2.73 parts of 10% aqueous sodium sulfate solution is added to the reactor and the contents agitated for 15 minutes after which 0.50 part 10% aqueous sodium carbonate is added, the agitation stopped and the lower aqueous layer drained. The 2-ethylhexyl nitrate product is obtained in 97% yield, i.e., 7.64 parts. A reactor is charged with 13.48 parts of mixed acid adjusted to 25°±3° C to rise to 32.5°±2.5° C while maintaining the temperature at 32.5°±2.5° C the resulting mixture agitated After 15 minutes is separated An aqueous 10% sodium sulfate solution is added to the ethylhexyl nitrate layer which is agitated for 15 minutes at which point 0.50 part of an aqueous 10% sodium carbonate solution is slowly added An additional 2.73 parts of a 10% aqueous sodium sulfate solution is added to the reactor agitated for 15 minutes Another 2.73 parts of 10% aqueous sodium sulfate solution is added to the reactor the contents agitated for 15 minutes after which 0.50 part 10% aqueous sodium carbonate is added

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

実験手順: Potasium tert-butoxide (7.6 g, 67.8 mM) and (20S)-20-hydroxymethylpregn-4-en-3-one (6.6 g, 20 mM) are combined in tert-butanol and heated at reflux temperature for 120 minutes. 2-ethylhexylnitrate (3.56 ml, 20 mM) is then added in one continuous portion. After 10 minutes, the reaction vessel is cooled to room temperature. The reaction is then quenched with acetic acid (9 ml) and stirred overnight. After diluting with dichloromethane (200 mL), the solids are removed, washed, and combined with the washing residue and subsequently purified as described in Example 1 to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one. heated at reflux temperature for 120 minutes The reaction is then quenched with acetic acid (9 ml) After diluting with dichloromethane (200 mL) the solids are removed washed subsequently purified to give crystallized (20S)-20-hydroxymethyl-4-nitropregn-4-en-3-one