butan-2-yl carbonochloridate

反応条件: temp:7.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a well-stirred reaction vessel equipped with a thermometer and a pH electrode were added 100 ml of diethyl ether, 40 ml of a 25 wt % aqueous NaCl solution, and 0.4 g of Arquad CB50. After cooling the reaction mixture to 5-10° C., 0.066 mole of phenoxy acetic acid was added. The pH was adjusted to a value between 6 and 7 using a 25 wt % aqueous NaOH solution. Then, 0.066 mole of sec-butyl chloroformate was dosed within 5 min at 5-10° C. During this time and a post-reaction time of 40 min at 5-10° C. the pH was kept at 6-7. The reaction mixture was allowed to separate. After removal of the diethyl ether, 15 g of phenoxyacetyl 1-methyl-1-propyl carbonate having a content of 90% were obtained in a yield of 81%. To a well-stirred reaction vessel equipped with a thermometer a post-reaction time of 40 min at 5-10° C. to separate After removal of the diethyl ether, 15 g of phenoxyacetyl 1-methyl-1-propyl carbonate having a content of 90% were obtained in a yield of 81%

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

実験手順: To a well-stirred reaction vessel equipped with a thermometer and a pH electrode were added 39 g of water and 0.20 g of Arquad CB50 at 5° C. After the addition of 0.05 mole of 3-chlorobenzoic acid the pH was adjusted to 6 using a 10 wt % aqueous NaOH solution. Then, 0.05 mole of sec-butyl chloroformate was dosed within 5 min at 5° C. During this time and a post-reaction time of 165 min at 5° C. the pH was kept at a value between 6 and 9. The reaction mixture was allowed to separate, giving 12.5 g of 3-chlorobenzoyl 1-methyl-1-propyl carbonate having a content of 98% in a yield of 95%. To a well-stirred reaction vessel equipped with a thermometer a post-reaction time of 165 min at 5° C. to separate

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a well-stirred reaction vessel equipped with a thermometer and a pH-electrode were added 39 g of water and 0.20 g of Arquad CB50 at 5° C. After the addition of 0.05 mole of 3-chlorobenzoic acid the pH was adjusted to 6 using a 10 wt % aqueous NaOH solution. Then, 0.05 mole of sec-butyl chloroformate was dosed within 5 min at 5° C. During this time and a post-reaction time of 165 min at 5° C. the pH was kept at a value between 6 and 9. After the post-reaction, 8.1 g of TBHP were added (0.063 mole), and using a 33 wt % aqueous NaOH solution the pH was adjusted to 13 within 5 min while keeping the temperature at 5° C. During a post-reaction time of 75 min at 5° C. the pH was maintained at 13. Then, 25 g of diethyl ether were added, and the reaction mixture was allowed to separate. After separation of the water layer, the organic layer was washed, twice with 40 g of a 15 wt % aqueous NaCl solution. The ether layer was dried over MgSO4, and the diethyl ether was removed under vacuum. As a result, 9.4 g of tert-butylperoxy 3-chlorobenzoate having a content of 95.4% were obtained in a yield of 80% based on 3-chlorobenzoic acid. The molar ratio of tert-butylperoxy 3-chlorobenzoate to tert-butylperoxy 1-methyl-1-propylcarbonate was calculated to be 97.6:2.4. To a well-stirred reaction vessel equipped with a thermometer a post-reaction time of 165 min at 5° C. were added (0.063 mole) at 5° C to separate After separation of the water layer the organic layer was washed, twice with 40 g of a 15 wt % aqueous NaCl solution The ether layer was dried over MgSO4 the diethyl ether was removed under vacuum

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

実験手順: To 3.0 g of 3-phenoxyphenyl hydrazine, 100 ml of ethyl acetate and 2.5 ml of pyridine were added and the resultant solution was then stirred at room temperature for 30 minutes. Then, 2.5 ml of sec-butyl chloro-formate was added dropwise to the solution and stirred for 1 hour at room temperature. The solution was then washed twice, each time with 100 ml of water. After each wash, the aqueous fraction was removed from the organic (ethyl acetate) fraction. The resulting ethyl acetate fraction was then dried over anhydrous sodium sulfate, evaporated under reduced pressure, and then purified by column chromatography on silica gel, to produce 1.5 g of 1-methylpropyl 2-(3-phenoxyphenyl)hydrazine carboxylate as an oil. The solution was then washed twice After each wash, the aqueous fraction was removed from the organic (ethyl acetate) fraction The resulting ethyl acetate fraction was then dried over anhydrous sodium sulfate evaporated under reduced pressure purified by column chromatography on silica gel

反応条件: temp:7.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a well-stirred reaction vessel equipped with a thermometer and a pH electrode were added 100 ml of diethyl ether, 40 ml of a 25 wt % aqueous NaCl solution, and 0.4 g of Arquad CB50. After cooling the reaction mixture to 5-10° C., 0.066 mole of phenoxy acetic acid was added. The pH was adjusted to a value between 6 and 7 using a 25 wt % aqueous NaOH solution. Then, 0.066 mole of sec-butyl chloroformate was dosed within 5 min at 5-10° C. During this time and a post-reaction time of 40 min at 5-10° C. the pH was kept at 6-7. The reaction mixture was allowed to separate. After removal of the diethyl ether, 15 g of phenoxyacetyl 1-methyl-1-propyl carbonate having a content of 90% were obtained in a yield of 81%. To a well-stirred reaction vessel equipped with a thermometer a post-reaction time of 40 min at 5-10° C. to separate After removal of the diethyl ether, 15 g of phenoxyacetyl 1-methyl-1-propyl carbonate having a content of 90% were obtained in a yield of 81%

反応条件: temp:7.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a well-stirred reaction vessel equipped with a thermometer and a pH electrode were added 100 ml of diethyl ether, 40 ml of a 25 wt % aqueous NaCl solution, and 0.4 g of Arquad CB50. After cooling the reaction mixture to 5-10° C., 0.066 mole of phenoxy acetic acid was added. The pH was adjusted to a value between 6 and 7 using a 25 wt % aqueous NaOH solution. Then, 0.066 mole of sec-butyl chloroformate was dosed within 5 min at 5-10° C. During this time and a post-reaction time of 40 min at 5-10° C. the pH was kept at 6-7. The reaction mixture was allowed to separate. After removal of the diethyl ether, 15 g of phenoxyacetyl 1-methyl-1-propyl carbonate having a content of 90% were obtained in a yield of 81%. To a well-stirred reaction vessel equipped with a thermometer a post-reaction time of 40 min at 5-10° C. to separate After removal of the diethyl ether, 15 g of phenoxyacetyl 1-methyl-1-propyl carbonate having a content of 90% were obtained in a yield of 81%

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

実験手順: To a well-stirred reaction vessel equipped with a thermometer and a pH electrode were added 39 g of water and 0.20 g of Arquad CB50 at 5° C. After the addition of 0.05 mole of 3-chlorobenzoic acid the pH was adjusted to 6 using a 10 wt % aqueous NaOH solution. Then, 0.05 mole of sec-butyl chloroformate was dosed within 5 min at 5° C. During this time and a post-reaction time of 165 min at 5° C. the pH was kept at a value between 6 and 9. The reaction mixture was allowed to separate, giving 12.5 g of 3-chlorobenzoyl 1-methyl-1-propyl carbonate having a content of 98% in a yield of 95%. To a well-stirred reaction vessel equipped with a thermometer a post-reaction time of 165 min at 5° C. to separate

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a well-stirred reaction vessel equipped with a thermometer and a pH-electrode were added 39 g of water and 0.20 g of Arquad CB50 at 5° C. After the addition of 0.05 mole of 3-chlorobenzoic acid the pH was adjusted to 6 using a 10 wt % aqueous NaOH solution. Then, 0.05 mole of sec-butyl chloroformate was dosed within 5 min at 5° C. During this time and a post-reaction time of 165 min at 5° C. the pH was kept at a value between 6 and 9. After the post-reaction, 8.1 g of TBHP were added (0.063 mole), and using a 33 wt % aqueous NaOH solution the pH was adjusted to 13 within 5 min while keeping the temperature at 5° C. During a post-reaction time of 75 min at 5° C. the pH was maintained at 13. Then, 25 g of diethyl ether were added, and the reaction mixture was allowed to separate. After separation of the water layer, the organic layer was washed, twice with 40 g of a 15 wt % aqueous NaCl solution. The ether layer was dried over MgSO4, and the diethyl ether was removed under vacuum. As a result, 9.4 g of tert-butylperoxy 3-chlorobenzoate having a content of 95.4% were obtained in a yield of 80% based on 3-chlorobenzoic acid. The molar ratio of tert-butylperoxy 3-chlorobenzoate to tert-butylperoxy 1-methyl-1-propylcarbonate was calculated to be 97.6:2.4. To a well-stirred reaction vessel equipped with a thermometer a post-reaction time of 165 min at 5° C. were added (0.063 mole) at 5° C to separate After separation of the water layer the organic layer was washed, twice with 40 g of a 15 wt % aqueous NaCl solution The ether layer was dried over MgSO4 the diethyl ether was removed under vacuum

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a well-stirred reaction vessel equipped with a thermometer and a pH-electrode were added 39 g of water and 0.20 g of Arquad CB50 at 5° C. After the addition of 0.05 mole of 3-chlorobenzoic acid the pH was adjusted to 6 using a 10 wt % aqueous NaOH solution. Then, 0.05 mole of sec-butyl chloroformate was dosed within 5 min at 5° C. During this time and a post-reaction time of 165 min at 5° C. the pH was kept at a value between 6 and 9. After the post-reaction, 8.1 g of TBHP were added (0.063 mole), and using a 33 wt % aqueous NaOH solution the pH was adjusted to 13 within 5 min while keeping the temperature at 5° C. During a post-reaction time of 75 min at 5° C. the pH was maintained at 13. Then, 25 g of diethyl ether were added, and the reaction mixture was allowed to separate. After separation of the water layer, the organic layer was washed, twice with 40 g of a 15 wt % aqueous NaCl solution. The ether layer was dried over MgSO4, and the diethyl ether was removed under vacuum. As a result, 9.4 g of tert-butylperoxy 3-chlorobenzoate having a content of 95.4% were obtained in a yield of 80% based on 3-chlorobenzoic acid. The molar ratio of tert-butylperoxy 3-chlorobenzoate to tert-butylperoxy 1-methyl-1-propylcarbonate was calculated to be 97.6:2.4. To a well-stirred reaction vessel equipped with a thermometer a post-reaction time of 165 min at 5° C. were added (0.063 mole) at 5° C to separate After separation of the water layer the organic layer was washed, twice with 40 g of a 15 wt % aqueous NaCl solution The ether layer was dried over MgSO4 the diethyl ether was removed under vacuum

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

実験手順: To 3.0 g of 3-phenoxyphenyl hydrazine, 100 ml of ethyl acetate and 2.5 ml of pyridine were added and the resultant solution was then stirred at room temperature for 30 minutes. Then, 2.5 ml of sec-butyl chloro-formate was added dropwise to the solution and stirred for 1 hour at room temperature. The solution was then washed twice, each time with 100 ml of water. After each wash, the aqueous fraction was removed from the organic (ethyl acetate) fraction. The resulting ethyl acetate fraction was then dried over anhydrous sodium sulfate, evaporated under reduced pressure, and then purified by column chromatography on silica gel, to produce 1.5 g of 1-methylpropyl 2-(3-phenoxyphenyl)hydrazine carboxylate as an oil. The solution was then washed twice After each wash, the aqueous fraction was removed from the organic (ethyl acetate) fraction The resulting ethyl acetate fraction was then dried over anhydrous sodium sulfate evaporated under reduced pressure purified by column chromatography on silica gel

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

実験手順: To 3.0 g of 3-phenoxyphenyl hydrazine, 100 ml of ethyl acetate and 2.5 ml of pyridine were added and the resultant solution was then stirred at room temperature for 30 minutes. Then, 2.5 ml of sec-butyl chloro-formate was added dropwise to the solution and stirred for 1 hour at room temperature. The solution was then washed twice, each time with 100 ml of water. After each wash, the aqueous fraction was removed from the organic (ethyl acetate) fraction. The resulting ethyl acetate fraction was then dried over anhydrous sodium sulfate, evaporated under reduced pressure, and then purified by column chromatography on silica gel, to produce 1.5 g of 1-methylpropyl 2-(3-phenoxyphenyl)hydrazine carboxylate as an oil. The solution was then washed twice After each wash, the aqueous fraction was removed from the organic (ethyl acetate) fraction The resulting ethyl acetate fraction was then dried over anhydrous sodium sulfate evaporated under reduced pressure purified by column chromatography on silica gel

反応条件: temp:-50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: trans-1-Benzyloxycarbonyl-4-hydroxy-L-proline (3.55 g) was dissolved in dry tetrahydrofuran (60 ml), and triethylamine (2.80 ml) was added thereto, followed by addition of sec-butyl chloroformate (2.75 g) at 0° to 5° C. under nitrogen stream. The resultant mixture was stirred at the same temperature for 30 minutes and cooled to -50° C. 28 Aqueous ammonia (3.62 ml) was added thereto, and the resulting mixture was stirred at the same temperature for 30 minutes, followed by removal of the solvent. The residue was diluted with ethyl acetate and dried over magnesium sulfate. After removal of the solvent, the residue was purified by silica gel column chromatography to give (2S,4R)-1-benzyloxycarbonyl-2-aminocarbonyl-4-hydroxypyrrolidine. followed by removal of the solvent The residue was diluted with ethyl acetate dried over magnesium sulfate After removal of the solvent the residue was purified by silica gel column chromatography