2-chloro-4-fluoro-3-methylaniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: 2-chloro-4-fluoro-3-methylaniline (73 g) was added dropwise, with vigorous stirring to 50% hydrochloric acid (256 ml). The resulting white suspension was cooled to 5° C. and with stirring, sodium nitrite (34.5 g) in water (50 ml), added dropwise. The resultant yellow solution after filtration was cooled to 0° C. and with stirring sodium tetrafluoroborate (71 g) in water (140 ml), added dropwise. The yellow solid formed was filtered off and washed with petroleum ether (6.p 60°-80°) and combined with further similarly washed solid obtained by treating the filtrate, maintained at 0° C., with sodium tetrafluroborate (71 g) in water (140 ml). The solid was dried overnight over phosphorus pentoxide in vacuo, giving a yield of 98.8 g 2-chloro-4-fluoro-3-methylbenzenediazonium tetrafluoroborate. This was divided into three protions each being placed in a round-bottomed flask (250 ml). The flasks were in turn heated with a naked bunsen flame until decomposition set in and an orange vapor was emitted, which was condensed and collected in a cooled receiver. The orange oil obtained from the three batches was dissolved in diethyl ether (200 ml) and washed with aqueous sodium hydroxide solution (10%, 300 ml) then saturated brine (200 ml). After drying the ethereal solution over anhydrous magnesium sulphate, filtering and evaporating at atmospheric pressure, the residual oil was distilled to give 2-chloro-3,6-difluorotoluene (45 g) The resultant yellow solution after filtration was cooled to 0° C. and with stirring sodium tetrafluoroborate (71 g) in water (140 ml) added dropwise The yellow solid formed was filtered off washed with petroleum ether (6.p 60°-80°) obtained by treating the filtrate The solid was dried overnight over phosphorus pentoxide in vacuo

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

実験手順: 2-chloro-4-fluoro-3-methylaniline (73 g) was added dropwise, with vigorous stirring to 50% hydrochloric acid (256 ml). The resulting white suspension was cooled to 5° C. and with stirring, sodium nitrite (34.5 g) in water (50 ml), added dropwise. The resultant yellow solution after filtration was cooled to 0° C. and with stirring sodium tetrafluoroborate (71 g) in water (140 ml), added dropwise. The yellow solid formed was filtered off and washed with petroleum ether (6.p 60°-80°) and combined with further similarly washed solid obtained by treating the filtrate, maintained at 0° C., with sodium tetrafluroborate (71 g) in water (140 ml). The solid was dried overnight over phosphorus pentoxide in vacuo, giving a yield of 98.8 g 2-chloro-4-fluoro-3-methylbenzenediazonium tetrafluoroborate. This was divided into three protions each being placed in a round-bottomed flask (250 ml). The flasks were in turn heated with a naked bunsen flame until decomposition set in and an orange vapor was emitted, which was condensed and collected in a cooled receiver. The orange oil obtained from the three batches was dissolved in diethyl ether (200 ml) and washed with aqueous sodium hydroxide solution (10%, 300 ml) then saturated brine (200 ml). After drying the ethereal solution over anhydrous magnesium sulphate, filtering and evaporating at atmospheric pressure, the residual oil was distilled to give 2-chloro-3,6-difluorotoluene (45 g) The resultant yellow solution after filtration was cooled to 0° C. and with stirring sodium tetrafluoroborate (71 g) in water (140 ml) added dropwise The yellow solid formed was filtered off washed with petroleum ether (6.p 60°-80°) obtained by treating the filtrate The solid was dried overnight over phosphorus pentoxide in vacuo

反応条件: temp:82.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 2-chloro-6-fluoro-3-nitrotoluene (140 g), isopropanol (560 ml) and water (147 ml), hydrogen reduced iron (172.2 g) was added hydrochloric acid (43 drops) and with vigorous stirring the whole heated to reflux temperature (82° C.) for 4 hours. The cooled mixture was then filtered and the filtrate evaporated under reduced pressure giving an oil which on distillation gave 2-chloro-4-fluoro-3-methylaniline (72 g). whole heated The cooled mixture was then filtered the filtrate evaporated under reduced pressure giving an oil which on distillation

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: 2-chloro-4-fluoro-3-methylaniline (73 g) was added dropwise, with vigorous stirring to 50% hydrochloric acid (256 ml). The resulting white suspension was cooled to 5° C. and with stirring, sodium nitrite (34.5 g) in water (50 ml), added dropwise. The resultant yellow solution after filtration was cooled to 0° C. and with stirring sodium tetrafluoroborate (71 g) in water (140 ml), added dropwise. The yellow solid formed was filtered off and washed with petroleum ether (6.p 60°-80°) and combined with further similarly washed solid obtained by treating the filtrate, maintained at 0° C., with sodium tetrafluoroborate (71 g) in water (140 ml). The solid was dried overnight over phosphorus pentoxide in vacuo, giving a yield of 98.8 g 2-chloro-4-fluoro-3-methylbenzenediazonium tetrafluoroborate. This was divided into three portions each being placed in a round-bottomed flask (250 ml). The flasks were in turn heated with a naked bunsen flame until decompositio set in and an orange vapor was emitted, which was condensed and collected in a cooled receiver. The orange oil obtained from the three batches was dissolved in diethyl ether (200 ml) and washed with aqueous sodium hydroxide solution (10%, 300 ml) then saturated brine (200 ml). After drying the ethereal solution over anhydrous magnesium sulphate, filtering and evaporating at atmospheric pressure, the residual oil was distilled to give 2-chloro-3,6-difluorotoluene (45 g) The resultant yellow solution after filtration was cooled to 0° C. and with stirring sodium tetrafluoroborate (71 g) in water (140 ml) added dropwise The yellow solid formed was filtered off washed with petroleum ether (6.p 60°-80°) obtained by treating the filtrate The solid was dried overnight over phosphorus pentoxide in vacuo

反応条件: temp:82.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 2-chloro-6-fluoro-3-nitrotoluene (140 g), isopropanol (560 ml) and water (147 ml), hydrogen reduced iron (172.2 g) was added hydrochloric acid (43 drops) and with vigorous stirring the whole heated to reflux temperature (82° C.) for 4 hours. The cooled mixture was then filtered and the filtrate evaporated under reduced pressure giving an oil which on distillation gave 2-chloro-4-fluoro-3-methylaniline (72 g). whole heated The cooled mixture was then filtered the filtrate evaporated under reduced pressure giving an oil which on distillation

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

実験手順: 2-chloro-4-fluoro-3-methylaniline (73 g) was added dropwise, with vigorous stirring to 50% hydrochloric acid (256 ml). The resulting white suspension was cooled to 5° C. and with stirring, sodium nitrite (34.5 g) in water (50 ml), added dropwise. The resultant yellow solution after filtration was cooled to 0° C. and with stirring sodium tetrafluoroborate (71 g) in water (140 ml), added dropwise. The yellow solid formed was filtered off and washed with petroleum ether (6.p 60°-80°) and combined with further similarly washed solid obtained by treating the filtrate, maintained at 0° C., with sodium tetrafluroborate (71 g) in water (140 ml). The solid was dried overnight over phosphorus pentoxide in vacuo, giving a yield of 98.8 g 2-chloro-4-fluoro-3-methylbenzenediazonium tetrafluoroborate. This was divided into three protions each being placed in a round-bottomed flask (250 ml). The flasks were in turn heated with a naked bunsen flame until decomposition set in and an orange vapor was emitted, which was condensed and collected in a cooled receiver. The orange oil obtained from the three batches was dissolved in diethyl ether (200 ml) and washed with aqueous sodium hydroxide solution (10%, 300 ml) then saturated brine (200 ml). After drying the ethereal solution over anhydrous magnesium sulphate, filtering and evaporating at atmospheric pressure, the residual oil was distilled to give 2-chloro-3,6-difluorotoluene (45 g) The resultant yellow solution after filtration was cooled to 0° C. and with stirring sodium tetrafluoroborate (71 g) in water (140 ml) added dropwise The yellow solid formed was filtered off washed with petroleum ether (6.p 60°-80°) obtained by treating the filtrate The solid was dried overnight over phosphorus pentoxide in vacuo

反応条件: temp:82.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 2-chloro-6-fluoro-3-nitrotoluene (140 g), isopropanol (560 ml) and water (147 ml), hydrogen reduced iron (172.2 g) was added hydrochloric acid (43 drops) and with vigorous stirring the whole heated to reflux temperature (82° C.) for 4 hours. The cooled mixture was then filtered and the filtrate evaporated under reduced pressure giving an oil which on distillation gave 2-chloro-4-fluoro-3-methylaniline (72 g). whole heated The cooled mixture was then filtered the filtrate evaporated under reduced pressure giving an oil which on distillation

反応条件: temp:0.00; pressure:0.00; stir: