(6-amino-2,3-dichlorophenyl)methanol

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 solution of 6-amino-2,3-dichlorobenzyl alcohol (10.0 g., 0.0521 mol) in 250 ml. of boiling benzene was treated with a slow-stream of dry hydrogen chloride for 0.5 hour. The finely divided suspension was cooled slightly, thionyl chloride (12.4 g, 0.104 mol) was added in one portion, and reflux was continued for 2.5 hours. The solution was evaporated in vacuo to remove excess thionyl chloride and hydrogen chloride, and the residue was redissolved in 250 ml. benzene. This solution was added over 1 hour to a reluxing mixture of glycine ethyl ester hydrochloride (29.1 g, 0.208 mol) and triethylamine (31.6 g, 0.313 mol) in 600 ml. CH2Cl2. Reflux was continued for 1 hour, the mixture was allowed to stand overnight and was then extracted with 1N HCl. The extract was washed with CH2Cl2 and ether, made slightly alkaline with concentrated NH4OH and extracted with ether. After drying (K2CO3) and evaporation there remained 8.3 g (58%) of the title product as a light yellow oil which crystallized. The analytical sample was obtained from Skellysolve B as white needles, mp. 60°-61° C. The finely divided suspension was cooled slightly reflux The solution was evaporated in vacuo to remove excess thionyl chloride and hydrogen chloride the residue was redissolved in 250 ml Reflux was continued for 1 hour to stand overnight was then extracted with 1N HCl The extract was washed with CH2Cl2 and ether extracted with ether After drying (K2CO3) and evaporation there remained 8.3 g (58%) of the title product as a light yellow oil which crystallized The analytical sample was obtained from Skellysolve B as white needles, mp. 60°-61° C.

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

実験手順: A solution of 6-amino-2,3-dichlorobenzyl alcohol (10.0 g., 0.0521 mol) in 250 ml. of boiling benzene was treated with a slow-stream of dry hydrogen chloride for 0.5 hour. The finely divided suspension was cooled slightly, thionyl chloride (12.4 g, 0.104 mol) was added in one portion, and reflux was continued for 2.5 hours. The solution was evaporated in vacuo to remove excess thionyl chloride and hydrogen chloride, and the residue was redissolved in 250 ml. benzene. This solution was added over 1 hour to a reluxing mixture of glycine ethyl ester hydrochloride (29.1 g, 0.208 mol) and triethylamine (31.6 g, 0.313 mol) in 600 ml. CH2Cl2. Reflux was continued for 1 hour, the mixture was allowed to stand overnight and was then extracted with 1N HCl. The extract was washed with CH2Cl2 and ether, made slightly alkaline with concentrated NH4OH and extracted with ether. After drying (K2CO3) and evaporation there remained 8.3 g (58%) of the title product as a light yellow oil which crystallized. The analytical sample was obtained from Skellysolve B as white needles, mp. 60°-61° C. The finely divided suspension was cooled slightly reflux The solution was evaporated in vacuo to remove excess thionyl chloride and hydrogen chloride the residue was redissolved in 250 ml Reflux was continued for 1 hour to stand overnight was then extracted with 1N HCl The extract was washed with CH2Cl2 and ether extracted with ether After drying (K2CO3) and evaporation there remained 8.3 g (58%) of the title product as a light yellow oil which crystallized The analytical sample was obtained from Skellysolve B as white needles, mp. 60°-61° C.

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

実験手順: A solution of borane (0.55 mol) in 550 ml of tetrahydrofuran was slowly added, over a period of 1 hour, to a solution of 5,6-dichloroanthranilic acid (44.5 g, 0.216 mol) in tetrahydrofuran (1200 ml). The solution was heated at reflux for 18 hours, cooled and treated slowly with 550 ml of 1N HCl. The tetrahydrofuran was removed in vacuo at 30° and the aqueous mixture was washed with ether and then made basic with concentrated NH4OH. The resulting solid was extracted with ether, dried (K2CO3) and the solvent was evaporated to leave 31.5 g. (76%) of the title compound as light pinkish needles, m.p. 133.5°-135°. An analytical sample was prepared by recrystallization from benzene; white needles, m.p. 134°-135.5°. The solution was heated at reflux for 18 hours cooled The tetrahydrofuran was removed in vacuo at 30° the aqueous mixture was washed with ether The resulting solid was extracted with ether dried (K2CO3) the solvent was evaporated to leave 31.5 g

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 solution of 6-amino-2,3-dichlorobenzyl alcohol (10.0 g., 0.0521 mol) in 250 ml. of boiling benzene was treated with a slow-stream of dry hydrogen chloride for 0.5 hour. The finely divided suspension was cooled slightly, thionyl chloride (12.4 g, 0.104 mol) was added in one portion, and reflux was continued for 2.5 hours. The solution was evaporated in vacuo to remove excess thionyl chloride and hydrogen chloride, and the residue was redissolved in 250 ml. benzene. This solution was added over 1 hour to a reluxing mixture of glycine ethyl ester hydrochloride (29.1 g, 0.208 mol) and triethylamine (31.6 g, 0.313 mol) in 600 ml. CH2Cl2. Reflux was continued for 1 hour, the mixture was allowed to stand overnight and was then extracted with 1N HCl. The extract was washed with CH2Cl2 and ether, made slightly alkaline with concentrated NH4OH and extracted with ether. After drying (K2CO3) and evaporation there remained 8.3 g (58%) of the title product as a light yellow oil which crystallized. The analytical sample was obtained from Skellysolve B as white needles, mp. 60°-61° C. The finely divided suspension was cooled slightly reflux The solution was evaporated in vacuo to remove excess thionyl chloride and hydrogen chloride the residue was redissolved in 250 ml Reflux was continued for 1 hour to stand overnight was then extracted with 1N HCl The extract was washed with CH2Cl2 and ether extracted with ether After drying (K2CO3) and evaporation there remained 8.3 g (58%) of the title product as a light yellow oil which crystallized The analytical sample was obtained from Skellysolve B as white needles, mp. 60°-61° C.

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

実験手順: A solution of borane (0.55 mol) in 550 ml of tetrahydrofuran was slowly added, over a period of 1 hour, to a solution of 5,6-dichloroanthranilic acid (44.5 g, 0.216 mol) in tetrahydrofuran (1200 ml). The solution was heated at reflux for 18 hours, cooled and treated slowly with 550 ml of 1N HCl. The tetrahydrofuran was removed in vacuo at 30° and the aqueous mixture was washed with ether and then made basic with concentrated NH4OH. The resulting solid was extracted with ether, dried (K2CO3) and the solvent was evaporated to leave 31.5 g. (76%) of the title compound as light pinkish needles, m.p. 133.5°-135°. An analytical sample was prepared by recrystallization from benzene; white needles, m.p. 134°-135.5°. The solution was heated at reflux for 18 hours cooled The tetrahydrofuran was removed in vacuo at 30° the aqueous mixture was washed with ether The resulting solid was extracted with ether dried (K2CO3) the solvent was evaporated to leave 31.5 g