S-5,5-二苯基-4-甲基-2-噁唑烷酮

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of (S)-4-methyl-5,5-diphenyl-2-oxazolidinone (11) (3.52 g, 13.90 mmol) in MeOH/AcOH and a 10% Pd (148 mg, 1.39 mmol) on activated carbon was shaken for 45 h under 4–5 atm pressure of hydrogen at room temperature. The catalyst was filtered off over Hyflo Super Cell and organic solvents were evaporated under reduced pressure. The resulting residue was treated with HCl (2M, 100 ml), stirred overnight at room temperature, made basic with NaOH pellets, and saturated with K2CO3. The organics were then extracted into diethyl ether (3×100 ml), dried over MgSO4/K2CO3 and concentrated under reduced pressure to obtain a crude product. Impurities were washed with AcOEt over silica gel by means of dry-flash column chromatography, and then further elution with a mixture of MeOH and AcOEt, ranging from 5% up to 30%, gave the title compound (12) (1.90 g, 65%) as a white solid. m.p. 76–77° C. [α]D25=−19.32 (c, 0.10765 in CHCl3). δH 1.04 (3H, d, 3J=6.30 Hz, CH3), 1.31 (2H, broad s, NH2), 3.55 (1H, d, J=9.90 Hz, CH—Ph2), 3.73 (1H, dq, 3J=6.30 and 10.20 Hz, CH—NH2), 7.10–7.40 (10H, m, Ar—H). δC 22.4 (CH3), 50.3 (CH—NH2), 62.4 (CH—Ph2), 126.5, 126.8, 128.2, 128.5, 128.7 and 129.0 (o-, m- and p-Ar), 143.3 and 143.7 (α-Ar). Anal. Calcld for C15H17NO: C 85.26; H 8.11; N 6.63. Found: C 85.10; H 8.08; N 6.36. ir 3343 (NH2). m/e (CI—NH3) 212 (MH+, 100%). The catalyst was filtered off over Hyflo Super Cell and organic solvents were evaporated under reduced pressure The resulting residue was treated with HCl (2M, 100 ml) The organics were then extracted into diethyl ether (3×100 ml) dried over MgSO4/K2CO3 concentrated under reduced pressure to obtain a crude product Impurities were washed with AcOEt over silica gel by means of dry-flash column chromatography further elution with a mixture of MeOH and AcOEt

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Trichloromethyl chloroformate (6.37 g, 32.19 mmol) was added to a mixture of (S)-2-amino-1,1-diphenyl-1-propanol (10) (6.65 g, 29.26 mmol) and triethylamine (6.31 g, 62.3 mmol) in CH2Cl2 at 0° C. The reaction mixture was stirred for 5 h at the same temperature, poured into a brine solution (150 ml), and diluted with more dichloromethane. After collecting insoluble impurities through the Buchner funnel, the organic layer was separated and the aqueous layer was washed once with a mixture of dichloromethane and AcOEt. The combined organic extracts were dried over MgSO4/K2CO3 and concentrated under reduced pressure. The resulting crude product was washed with diethyl ether, water, AcOEt and diethyl ether again, to obtain the title compound (11) (5.67 g, 76%) as a white solid. m.p. 264–266° C. [α]D25=−279.71° (c, 0.0414 in DMSO). δH 0.82 (3H, d, 3J=6.30 Hz, CH3), 4.65 (1H, q, 3J=6.0 Hz, CH—NH2), 7.10–7.70 (10H, m, Ar—H), 7.93 (1H, broad s, NH). δC 19.6 (CH3), 55.9 (CH—NH2), 85.6 (C—O), 126.3, 126.4, 128.1, 128.6, 128.8 and 129.1 (o-, m- and p-Ar), 140.6 and 144.2 (α-Ar), 157.6 (C═O). ir 3254 (NH), 1745 and 1725 (C═O). m/e (CI—NH3) 254 (MH+, 9%), 271 (MNH4+, 55%), 52 (100%). After collecting insoluble impurities through the Buchner funnel the organic layer was separated the aqueous layer was washed once with a mixture of dichloromethane and AcOEt The combined organic extracts were dried over MgSO4/K2CO3 concentrated under reduced pressure The resulting crude product was washed with diethyl ether, water, AcOEt and diethyl ether again