硫代丙酰胺乙酯

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl 3-amino-3-thioxopropionate (73.5 g) in diethyl ether (100 ml) was added to a solution of bromopiruvic acid (88.5 g) in diethyl ether (300 ml) and stirred for 15 hours at ambient temperature. The precipitates were collected by filtration and added to a mixture of water (500 ml) and diethyl ether (300 ml) and then adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous solution was adjusted to pH 1.0 with conc. hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was dried over magnesium sulfate and evaporated. The residue was washed with diisopropyl ether to give ethyl 2-(4-carboxythiazol-2-yl)acetate (57.1 g). The precipitates were collected by filtration added to a mixture of water (500 ml) and diethyl ether (300 ml) extracted with diethyl ether The diethyl ether layer was dried over magnesium sulfate evaporated The residue was washed with diisopropyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl 3-amino-3-thioxopropionate (73.5 g) in diethyl ether (100 ml) was added to a solution of bromopiruvic acid (88.5 g) in diethyl ether (300 ml) and stirred for 15 hours at ambient temperature. The precipitates were collected by filtration and added to a mixture of water (500 ml) and diethyl ether (300 ml) and then adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous solution was adjusted to pH 1.0 with conc. hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was dried over magnesium sulfate and evaporated. The residue was washed with diisopropyl ether to give ethyl 2-(4-carboxythiazol-2-yl)acetate (57.1 g). The precipitates were collected by filtration added to a mixture of water (500 ml) and diethyl ether (300 ml) extracted with diethyl ether The diethyl ether layer was dried over magnesium sulfate evaporated The residue was washed with diisopropyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl 3-amino-3-thioxopropionate (73.5 g) in diethyl ether (100 ml) was added to a solution of bromopiruvic acid (88.5 g) in diethyl ether (300 ml) and stirred for 15 hours at ambient temperature. The precipitates were collected by filtration and added to a mixture of water (500 ml) and diethyl ether (300 ml) and then adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous solution was adjusted to pH 1.0 with conc. hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was dried over magnesium sulfate and evaporated. The residue was washed with diisopropyl ether to give ethyl 2-(4-carboxythiazol-2-yl)acetate (57.1 g). The precipitates were collected by filtration added to a mixture of water (500 ml) and diethyl ether (300 ml) extracted with diethyl ether The diethyl ether layer was dried over magnesium sulfate evaporated The residue was washed with diisopropyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl 3-amino-3-thioxopropionate (73.5 g) in diethyl ether (100 ml) was added to a solution of bromopiruvic acid (88.5 g) in diethyl ether (300 ml) and stirred for 15 hours at ambient temperature. The precipitates were collected by filtration and added to a mixture of water (500 ml) and diethyl ether (300 ml) and then adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous solution was adjusted to pH 1.0 with conc. hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was dried over magnesium sulfate and evaporated. The residue was washed with diisopropyl ether to give ethyl 2-(4-carboxythiazol-2-yl)acetate (57.1 g). The precipitates were collected by filtration added to a mixture of water (500 ml) and diethyl ether (300 ml) extracted with diethyl ether The diethyl ether layer was dried over magnesium sulfate evaporated The residue was washed with diisopropyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl 3-amino-3-thioxopropionate (73.5 g) in diethyl ether (100 ml) was added to a solution of bromopiruvic acid (88.5 g) in diethyl ether (300 ml) and stirred for 15 hours at ambient temperature. The precipitates were collected by filtration and added to a mixture of water (500 ml) and diethyl ether (300 ml) and then adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous solution was adjusted to pH 1.0 with conc. hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was dried over magnesium sulfate and evaporated. The residue was washed with diisopropyl ether to give ethyl 2-(4-carboxythiazol-2-yl)acetate (57.1 g). The precipitates were collected by filtration added to a mixture of water (500 ml) and diethyl ether (300 ml) extracted with diethyl ether The diethyl ether layer was dried over magnesium sulfate evaporated The residue was washed with diisopropyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl 3-amino-3-thioxopropionate (73.5 g) in diethyl ether (100 ml) was added to a solution of bromopiruvic acid (88.5 g) in diethyl ether (300 ml) and stirred for 15 hours at ambient temperature. The precipitates were collected by filtration and added to a mixture of water (500 ml) and diethyl ether (300 ml) and then adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous solution was adjusted to pH 1.0 with conc. hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was dried over magnesium sulfate and evaporated. The residue was washed with diisopropyl ether to give ethyl 2-(4-carboxythiazol-2-yl)acetate (57.1 g). The precipitates were collected by filtration added to a mixture of water (500 ml) and diethyl ether (300 ml) extracted with diethyl ether The diethyl ether layer was dried over magnesium sulfate evaporated The residue was washed with diisopropyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl 3-amino-3-thioxopropionate (73.5 g) in diethyl ether (100 ml) was added to a solution of bromopiruvic acid (88.5 g) in diethyl ether (300 ml) and stirred for 15 hours at ambient temperature. The precipitates were collected by filtration and added to a mixture of water (500 ml) and diethyl ether (300 ml) and then adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous solution was adjusted to pH 1.0 with conc. hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was dried over magnesium sulfate and evaporated. The residue was washed with diisopropyl ether to give ethyl 2-(4-carboxythiazol-2-yl)acetate (57.1 g). The precipitates were collected by filtration added to a mixture of water (500 ml) and diethyl ether (300 ml) extracted with diethyl ether The diethyl ether layer was dried over magnesium sulfate evaporated The residue was washed with diisopropyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl 3-amino-3-thioxopropionate (73.5 g) in diethyl ether (100 ml) was added to a solution of bromopiruvic acid (88.5 g) in diethyl ether (300 ml) and stirred for 15 hours at ambient temperature. The precipitates were collected by filtration and added to a mixture of water (500 ml) and diethyl ether (300 ml) and then adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous solution was adjusted to pH 1.0 with conc. hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was dried over magnesium sulfate and evaporated. The residue was washed with diisopropyl ether to give ethyl 2-(4-carboxythiazol-2-yl)acetate (57.1 g). The precipitates were collected by filtration added to a mixture of water (500 ml) and diethyl ether (300 ml) extracted with diethyl ether The diethyl ether layer was dried over magnesium sulfate evaporated The residue was washed with diisopropyl ether

实验步骤: 投料: 向50L反应釜中依次加入20L(10V)乙醇1.18kg（0.7eq）MgCl2(放热明显），2.38kg(2.4eq)NaHS，搅拌均匀溶解（有气体产生），滴加2.0kg(1.0eq)氰基乙酸乙酯，滴毕升温至45~50℃,保温反应，8hGCMS高温方法监测原料反应完全(TLC监测PE:EA=2:1)(反应直至原料反应完全） \n后处理: 体系加入(5V)H2O，6V饱和氯化铵溶液，5V(DCM)搅拌30min，静置分相，水相加入5V（DCM）萃取二次，有机相浓缩溶剂，浓缩干加入8V(H2O),5V(DCM)搅拌静置分相，水相加入5V(DCM)萃取四次，有机相干燥浓缩干\n纯化: 向三口瓶中依次加入粗品，(PE:EA=2:1)体系2.5V,降温至-30℃~-40℃，保温搅拌1h，体系过滤，滤饼用(PE:EA=10:1)提前预冷-30℃，淋洗得产品，减压干燥送样检测

实验步骤: 投料: 三口瓶中依次加入50ml(10V)乙醇2.52g（0.6eq）MgCl2(放热明显），5.95g(2.4eq)NaHS，搅拌均匀溶解（有气体产生），滴加50.0g(1.0eq)氰基乙酸乙酯，滴毕升温至45~50℃,保温反应，7hGCMS监测原料反应完全(TLC监测PE:EA=3:1)

实验步骤: 投料: 向三口瓶中依次加入50ml(10V)乙醇2.52g（0.6eq）MgCl2(放热明显），5.08g(2.05eq)NaHS，搅拌均匀溶解（有气体产生），滴加50.0g(1.0eq)氰基乙酸乙酯，滴毕升温至60~65℃,保温反应，7hGCMS监测原料反应完全(TLC监测PE:EA=3:1)

实验步骤: 纯化: 领取300gCIM100113-58-159-P（高温GC纯度95%）粗品，柱层析（PE:EA=30:1~25:1）出杂点，保持此极性继续冲，直到杂点冲完，会有损失，加大极性EA冲产品，得210g纯度98%，50g纯度97%。