pentyl nitrate

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: A mixture containing 100 g. of amyl nitrate and 600 ml. of bromoform is warmed to 70° C and then a total of 100 g. of 2-amino-5-methoxycarbonylthiazole is added portionwise with rapid stirring while maintaining the temperature at about 95°-100° C. The mixture is then stirred for an additional ten minutes at this temperature and then the bromoform is distilled off under vacuum. The residue is chromatographed on silica gel yielding 2-bromo-5-methoxycarbonylthiazole. A mixture containing 100 g while maintaining the temperature at about 95°-100° C The mixture is then stirred for an additional ten minutes at this temperature the bromoform is distilled off under vacuum The residue is chromatographed on silica gel

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

実験手順: Amyl nitrate (40 ml.) is added in 10 ml. increments at two hour intervals to 2-methyl-2-phenyl-5-methoxy-6,7-dichloro-1-indanone (9.36 g., 0.03 mole) in polyphosphoric acid (150 g.) at 50°-60° C. with stirring. The total heating period is 8 hours. The reaction mixture is treated with crushed ice-water to precipitate 4.82 g. of 2-methyl-2-(4-nitrophenyl)-5-methoxy-6,7-dichloro-1-indanone which melts at 179°-180° C. after crystallization from butyl chloride. The total heating period to precipitate 4.82 g of 2-methyl-2-(4-nitrophenyl)-5-methoxy-6,7-dichloro-1-indanone which melts at 179°-180° C. after crystallization from butyl chloride

反応条件: temp:38.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of methyl 3-amino-4-cyano-5-(methylthio)thiophene-2-carboxylate (4.0 g, 17.5 mmol) in acetonitrile (20 mL) was added diiodomethane (4.94 mL, 61.3 mmol). The reaction mixture was heated at 38° C. Isoamyl nitrate (5.13 g, 43.8 mmol) was added dropwise over five minutes. After the addition of amyl nitrate, the reaction mixture was allowed to cool to room temperature and stirred for two hours. The reaction mixture was cooled in an ice bath and hexanes (20 mL) were added. The resultant precipitate was filtered and washed with a solution of 90% hexanes in acetonitrile (10 mL), 75% hexanes in diethyl ether (10 mL) and 100% hexanes (20 mL) to give methyl 4-cyano-3-iodo-5-(methylsulfanyl)thiophene-2-carboxylate (3.4 g, 57%) as a light orange solid. 1H NMR (400 MHz, CDCl3) δ: 3.91 (s, 3H), 2.70 (s, 3H) to cool to room temperature The reaction mixture was cooled in an ice bath The resultant precipitate was filtered washed with a solution of 90% hexanes in acetonitrile (10 mL), 75% hexanes in diethyl ether (10 mL)

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

実験手順: Amyl nitrate (1 ml.) was added to a stirred suspension of ethyl 6-amino-4-hydroxycinnolin-3-yl carboxylate (1 g.) in thiophen (100 ml.). The suspension was stirred and heated under reflux for 2 hours. The suspension was filtered whilst hot and the filtrate was evaporated, giving a brown crystalline residue. The solid was applied to a silica column (100 g. of Kieselgel 60) and eluted with a 10% v/v mixture of dry ethanol and chloroform. The appropriate fractions were evaporated, and the residue was crystallised from 1:1 v/v aqueous ethanol to give ethyl 4-hydroxy-6-thienylcinnolin-3-yl carboxylate, m.p. 258°-260° C. heated under reflux for 2 hours The suspension was filtered whilst hot and the filtrate was evaporated giving a brown crystalline residue eluted with a 10% v/v mixture of dry ethanol and chloroform The appropriate fractions were evaporated the residue was crystallised from 1:1 v/v aqueous ethanol

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

実験手順: Amyl nitrate (1 ml.) was added to a stirred suspension of ethyl 6-amino-4-hydroxycinnolin-3-yl carboxylate (1 g.) in thiophen (100 ml.). The suspension was stirred and heated under reflux for 2 hours. The suspension was filtered whilst hot and the filtrate was evaporated, giving a brown crystalline residue. The solid was applied to a silica column (100 g. of Kieselgel 60) and eluted with a 10% v/v mixture of dry ethanol and chloroform. The appropriate fractions were evaporated, and the residue was crystallised from 1:1 v/v aqueous ethanol to give ethyl 4-hydroxy-6-thienylcinnolin-3-yl carboxylate, m.p. 258°-260° C. heated under reflux for 2 hours The suspension was filtered whilst hot and the filtrate was evaporated giving a brown crystalline residue eluted with a 10% v/v mixture of dry ethanol and chloroform The appropriate fractions were evaporated the residue was crystallised from 1:1 v/v aqueous ethanol

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

実験手順: A mixture containing 100 g. of amyl nitrate and 600 ml. of bromoform is warmed to 70° C and then a total of 100 g. of 2-amino-5-methoxycarbonylthiazole is added portionwise with rapid stirring while maintaining the temperature at about 95°-100° C. The mixture is then stirred for an additional ten minutes at this temperature and then the bromoform is distilled off under vacuum. The residue is chromatographed on silica gel yielding 2-bromo-5-methoxycarbonylthiazole. A mixture containing 100 g while maintaining the temperature at about 95°-100° C The mixture is then stirred for an additional ten minutes at this temperature the bromoform is distilled off under vacuum The residue is chromatographed on silica gel

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

実験手順: A mixture containing 100 g. of amyl nitrate and 600 ml. of bromoform is warmed to 70° C and then a total of 100 g. of 2-amino-5-methoxycarbonylthiazole is added portionwise with rapid stirring while maintaining the temperature at about 95°-100° C. The mixture is then stirred for an additional ten minutes at this temperature and then the bromoform is distilled off under vacuum. The residue is chromatographed on silica gel yielding 2-bromo-5-methoxycarbonylthiazole. A mixture containing 100 g while maintaining the temperature at about 95°-100° C The mixture is then stirred for an additional ten minutes at this temperature the bromoform is distilled off under vacuum The residue is chromatographed on silica gel

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: Amyl nitrate (40 ml.) is added in 10 ml. increments at two hour intervals to 2-methyl-2-phenyl-5-methoxy-6,7-dichloro-1-indanone (9.36 g., 0.03 mole) in polyphosphoric acid (150 g.) at 50°-60° C. with stirring. The total heating period is 8 hours. The reaction mixture is treated with crushed ice-water to precipitate 4.82 g. of 2-methyl-2-(4-nitrophenyl)-5-methoxy-6,7-dichloro-1-indanone which melts at 179°-180° C. after crystallization from butyl chloride The total heating period to precipitate 4.82 g of 2-methyl-2-(4-nitrophenyl)-5-methoxy-6,7-dichloro-1-indanone which melts at 179°-180° C. after crystallization from butyl chloride

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

実験手順: Amyl nitrate (40 ml.) is added in 10 ml. increments at two hour intervals to 2-methyl-2-phenyl-5-methoxy-6,7-dichloro-1-indanone (9.36 g., 0.03 mole) in polyphosphoric acid (150 g.) at 50°-60° C. with stirring. The total heating period is 8 hours. The reaction mixture is treated with crushed ice-water to precipitate 4.82 g. of 2-methyl-2-(4-nitrophenyl)-5-methoxy-6,7-dichloro-1-indanone which melts at 179°-180° C. after crystallization from butyl chloride The total heating period to precipitate 4.82 g of 2-methyl-2-(4-nitrophenyl)-5-methoxy-6,7-dichloro-1-indanone which melts at 179°-180° C. after crystallization from butyl chloride

反応条件: temp:97.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture containing 100 g. of amyl nitrate and 600 ml. of bromoform is warmed to 70° C and then a total of 100 g. of 2- amino-5-methoxycarbonylthiazole is added portionwise with rapid stirring while maintaining the temperature at about 95-100° C. The mixture is then stirred for an additional 10 minutes at this temperature and then the bromoform is distilled off under vacuum. The residue is chromatographed on silica gel yielding 2-bromo-5-methoxycarbonylthiazole. A mixture containing 100 g The mixture is then stirred for an additional 10 minutes at this temperature the bromoform is distilled off under vacuum The residue is chromatographed on silica gel