1-Amino-3,3-dimethylbutan-2-one hydrochloride

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

実験手順: 35.2 g. 1-Amino-3,3-dimethylbutan-2-one hydrochloride and 30 g. potassium thiocyanate in 50 ml. water was warmed on the steam bath for 2 hours. After cooling, the solid formed was collected, washed with water, dried and recrystallised from industrial methylated spirit to give 4-tert.butylimidazole-2-thiol, melting point 232° - 234° C. A solution/suspension of this in industrial methylated spirit was added to a solution of 4.5 g. sodium hydroxide in 100 ml. water. 17.6 g. Ethyl iodide was added forming a lower layer and the mixture was shaken for two minutes whilst the ethyl iodide reacted and dispersed. After 20 minutes the alkali was neutralised by passing in carbon dioxide and the methylated spirit removed by evaporation. The solid was collected, washed with water, dried and on recrystallisation from toluene gave 2-ethylthio-4-tert.butylimidazole, melting point 116.5° - 120° C. After cooling the solid formed was collected washed with water dried recrystallised from industrial methylated spirit

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

実験手順: To a 2 L three-necked round-bottom flask fitted with a mechanical stirrer were added azidopinacolone (28.6 g, 203 mmol, 1.0 equiv), methanol (1145 mL), concentrated HCl (18 mL), and 10% Pd/C (3.5 g, 50% water wet). The reaction mixture was stirred under hydrogen at 20 psi for 2 h, the mixture was filtered through a pad of Celite, and the residue rinsed with methanol (2×50 mL). The filtrate was concentrated under reduced pressure at a temperature below 40° C. The resulting wet solid was azeotroped with 2-propanol (2×100 mL), anhydrous ether (100 mL) was added, and the slurry which formed was stirred for 5 min. The solid product was collected by filtration, and the cake was washed with diethyl ether (2×30 mL) and then dried in vacuo to give aminopinacolone hydrochloride A-2. To a 2 L three-necked round-bottom flask fitted with a mechanical stirrer the mixture was filtered through a pad of Celite the residue rinsed with methanol (2×50 mL) The filtrate was concentrated under reduced pressure at a temperature below 40° C The resulting wet solid was azeotroped with 2-propanol (2×100 mL), anhydrous ether (100 mL) was added the slurry which formed was stirred for 5 min The solid product was collected by filtration the cake was washed with diethyl ether (2×30 mL) dried in vacuo

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

実験手順: To a mixture of 1-amino-3,3-dimethylbutan-2-one hydrochloride salt (35 g, 231 mmol) in CH2Cl2 (500 mL) at 0° C. are added N,N-diisopropylethylamine (74 g, 577 mmol) and ethyl chloro(oxo)acetate (31.5 g, 231 mmol) slowly over a period of 15 min. The reaction mixture is stirred at room temperature for 2 h and is filtered through Celite. The filtrate is concentrated to afford the title compound (40 g, 81%). is filtered through Celite The filtrate is concentrated

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

実験手順: 35.2 g. 1-Amino-3,3-dimethylbutan-2-one hydrochloride and 30 g. potassium thiocyanate in 50 ml. water was warmed on the steam bath for two hours. After cooling, the solid formed was collected, washed with water, dried and recrystallised from industrial methylated spirit to give 4-tert.butylimidazole-2-thiol, melting point 232°-234° C. A solution/suspension of this in industrial methylated spirit was added to a solution of 4.5 g. sodium hydroxide in 100 ml. water. 17.6 g. Ethyl iodide was added forming a lower layer and the mixture was shaken for two minutes whilst the ethyl iodide reacted and dispersed. After 20 minutes the alkali was neutralised by passing in carbon dioxide and the methylated spirit removed by evaporation. The solid was collected, washed with water, dried and on recrystallisation from toluene gave 2-ethylthio-4-tert.butylimidazole, melting point 116.5°-120° C. After cooling the solid formed was collected washed with water dried recrystallised from industrial methylated spirit

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

実験手順: 35.2 g. 1-Amino-3,3-dimethylbutan-2-one hydrochloride and 30 g. potassium thiocyanate in 50 ml. water was warmed on the steam bath for two hours. After cooling, the solid formed was collected, washed with water, dried and recrystallised from industrial methylated spirit to give 4-tert.butylimidazole-2-thiol, melting point 232°-234°C. A solution/suspension of this in industrial methylated spirit was added to a solution of 4.5 g. sodium hydroxide in 100 ml. water. 17.6 g. Ethyl iodide was added forming a lower layer and the mixture was shaken for two minutes whilst the ethyl iodide reacted and dispersed. After 20 minutes the alkali was neutralised by passing in carbon dioxide and the methylated spirit removed by evaporation. The solid was collected, washed with water, dried and on recrystallisation from toluene gave 2-ethylthio-4-tert.butylimidazole, melting point 116.5°-120°C. After cooling the solid formed was collected washed with water dried recrystallised from industrial methylated spirit