2-phenylmethoxybenzenesulfonyl chloride

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:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 148 ml of concentrated hydrochloric acid and 45 ml of acetic acid, maintained at <10°, was added 39.2 g of 2-(benzyloxy)aniline [See Berichte, 58, 79 (1925)]. White solid formed. Sufficient additional acetic acid was added to render the mixture stirrable. While temperature was 0° to 3°, a solution of 28 g of sodium nitrite in 75 ml of water was dripped into it. The mixture was kept at 5° to 10° for 15 minutes, then added to a mixture of 5.2 g of cuprous chloride, 37 ml of sulfur dioxide and 211 ml of acetic acid at 3°. Next, 290 ml of butyl chloride was added and the mixture allowed to warm to ambient temperature. After 16 hours, the mixture was diluted with water and the organic layer washed with water and dilute sodium bicarbonate solution until the washings were basic. The mixture was then dried (MgSO4) and evaporated to an oil (A). The effervescing aqueous portion (from which the butyl chloride solution had been removed) was depositing an oil; it was then treated portionwise with sodium bisulfite over several hours. After about 16 hours the oil was extracted into butyl chloride and the butyl chloride solution washed, dried and evaporated, providing an oil (B). Oils A and B are 2-(benzyloxy)benzenesulfonyl chloride. To oils A and B was added an excess of concentrated aqueous ammonia, the mixture was swirled and a white solid was observed. The solid was filtered off and extracted with hot butyl chloride; upon cooling, the extract precipitated 2-(benzyloxy)benzenesulfonamide as a white solid, m.p. 127°-129°. The solid was filtered off extracted with hot butyl chloride upon cooling the extract precipitated 2-(benzyloxy)benzenesulfonamide as a white solid, m.p. 127°-129°

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

実験手順: To 148 ml of concentrated hydrochloric acid and 45 ml of acetic acid, maintained at <10°, was added 39.2 g of 2-(benzyloxy)aniline [See Berichte, 58, 79 (1925)]. White solid formed. Sufficient additional acetic acid was added to render the mixture stirrable. While temperature was 0° to 3°, a solution of 28 g of sodium nitrite in 75 ml of water was dripped into it. The mixture was kept at 5° to 10° for 15 minutes, then added to a mixture of 5.2 g of cuprous chloride, 37 ml of sulfur dioxide and 211 ml of acetic acid at 3°. Next, 290 ml of butyl chloride was added and the mixture allowed to warm to ambient temperature. After 16 hours, the mixture was diluted with water and the organic layer washed with water and dilute sodium bicarbonate solution until the washings were basic. The mixture was then dried (MgSO4) and evaporated to an oil (A). The effervescing aqueous portion (from which the butyl chloride solution had been removed) was depositing an oil; it was then treated portionwise with sodium bisulfite over several hours. After about 16 hours the oil was extracted into butyl chloride and the butyl chloride solution washed, dried and evaporated, providing an oil (B). Oils A and B are 2-(benzyloxy)benzenesulfonyl chloride. To oils A and B was added an excess of concentrated aqueous ammonia, the mixture was swirled and a white solid was observed. The solid was filtered off and extracted with hot butyl chloride; upon cooling, the extract precipitated 2-(benzyloxy)benzenesulfonamide as a white solid, m.p. 127°-129°. The solid was filtered off extracted with hot butyl chloride upon cooling the extract precipitated 2-(benzyloxy)benzenesulfonamide as a white solid, m.p. 127°-129°

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

実験手順: 2-Benzyloxy-benzenesulfonyl chloride (see Example 23, step 1) (1.7 g, 6 mmol) and (S)-3-amino-4,4-diethoxy-butyric acid tert-butyl ester (see Example 93) (1.5 g, 6 mmol) and pyridine (1.9 g, 30 mmol) were dissolved in chloroform (150 mL) and stirred at room temperature for 3 days. The reaction was diluted with ethyl acetate (500 mL) and washed with 5% citric acid, sat. sodium bicarbonate, and sat. sodium chloride. The organic layer was then dried over anhydrous sodium sulfate, filtered, and concentrated. Purification by flash chromatography (SiO2, hexane:ethyl acetate, 8:1, then 4:1) gave the desired product (2.7 g, 91%) as a colorless oil. 1H NMR (400 MHz) CDCl3 δ 7.92 (m, 1H), 7.52 (d, 2H), 7.47 (t, 1H), 7.40 (t, 2H), 7.34 (d, 1H), 7.04 (t, 2H), 5.61 (d, 1H), 5.23 (q, 2H), 4.30 (d, 1H), 3.77 (m, 1H), 3.47 (m, 2H), 3.36 (m, 1H), 3.15 (m, 1H), 2.45 (t, 2H), 1.37 (s, 9H), 1.02 (t, 3H), 0.92 (t, 3H). washed with 5% citric acid, sat. sodium bicarbonate, and sat. sodium chloride The organic layer was then dried over anhydrous sodium sulfate filtered concentrated Purification by flash chromatography (SiO2, hexane

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

実験手順: To 2-benzyloxy-benzenesulfonyl chloride (3.11 g, 11 mmol) in dichloromethane (50 mL) and pyridine (2.6 mL, 3 equiv) was added 3-amino-N-methoxy-N-methyl-succinamic acid tert-butyl ester (1 equiv). The reaction stirred for 16 h and was washed with 10% sulfuric acid, water, and then brine. To give (S)-3-(2-benzyloxy-benzenesulfonylamino)-N-methoxy-N-methyl-succinamic acid tert-butyl ester as a yellow oil (4.82 g, 92%) that was sufficiently pure for further use. 1H NMR (CDCl3) 7.88(d,1H), 7.57(d,2H), 7.40(m,3H), 7.17(d,1H), 7.03(m,2H), 5.92(d,1H), 5.25(s,2H), 4.73(bs,1H), 3.57(s,3H), 2.86(s,3H), 2.63-2.39(AB quartet, 2H), 1.40(s,9H). was washed with 10% sulfuric acid, water

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

実験手順: To 2-benzyloxy-1-bromo benzene (4.0 g, 15.2 mmol) in diethyl ether/THF (1:1, 100 mL) at −78° C. was added n-butyllithium (2 equiv.). After 30 min sulfur dioxide/THF (1:1, 40 mL) was added. The reaction warmed to room temperature over 1.5 h and the solvent was removed under reduced pressure. Hexanes (75 mL) was added and the reaction was cooled to 0° C. prior to adding sulfuryl chloride (2 equiv.). After 15 min the reaction was poured into water, washed with brine and dried over magnesium sulfate to give a colorless oil. Chromatography silica gel, eluting with 1:1 hexanes/diethyl ether gave 2-benzyloxy-benzenesulfonyl chloride (3.11 g, 72%) as a colorless solid. 1H NMR (CDCl3) 8.00(d,1H), 7.65(t,1H), 7.54(d,2H), 7.38(m,3H), 7.12(m,2H), 5.37 (s,2H). the solvent was removed under reduced pressure Hexanes (75 mL) was added the reaction was cooled to 0° C. washed with brine dried over magnesium sulfate to give a colorless oil Chromatography silica gel, eluting with 1:1 hexanes/diethyl ether