p-Toluenesulfonic acid → (2S)-2-(4,5-diphenyloxazol-2-yl)oxirane

HRID 1741388노트

반응식

HRID 1741388 반응식
[OH:1][C@H:2]([C:5]1[O:6][C:7]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[C:8]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[N:9]=1)[CH2:3]O.COC(OC)(OC)C.C1(C)C=CC(S(O)(=O)=O)=CC=1>C(Cl)Cl>[C:10]1([C:8]2[N:9]=[C:5]([C@@H:2]3[CH2:3][O:1]3)[O:6][C:7]=2[C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

참가 물질

5

반응물 3

HCID 6101p-Toluenesulfonic acidHCID 15050Trimethyl orthoacetateHCID 569827262-((1S)-1,2-dihydroxyethyl)-4,5-diphenyloxazole

생성물 1

HCID 57131304(2S)-2-(4,5-diphenyloxazol-2-yl)oxirane수율 75.9%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

To a solution of 2-((1S)-1,2-dihydroxyethyl)-4,5-diphenyloxazole (20 g) in CH2Cl2 (400 ml) were added orthoacetic acid trimethyl ester (12.8 ml) and p-toluenesulfonic acid (130 mg) at room temperature under N2, After being stirred for 30 minutes, the solvent was evaporated in vacuo. The residue was diluted with CH2Cl2 (200 ml) and acetyl bromide (7.6 ml) was added to the solution at 0° C. under N2. After being stirred for 2 hours at room temperature, the solvent was evaporated in vacuo, the residue was diluted with methanol (200 ml), and K2CO3 (16 g) was added to the solution at 0° C. The mixture was stirred for 30 minutes at the same temperature and partitioned between ethyl acetate and water. The organic layer was washed with 1N-HCl, water, sat. NaHCO3 and brine. The dried solvent was evaporated in vacuo and the residue was purified by trituration with ether-hexane to give (2S)-2-(4,5-diphenyloxazol-2-yl)oxirane (14.2 g). MS (m/z): 264 (M+ +1) IR (Neat): 1460 cm-1NMR (CDCl3, δ): 3.23 (1H, dd, J=4.0, 5.6 Hz), 3.43 (1H, dd, J=2.6, 5.6 Hz), 4.08 (1H, dd, J=2.6, 4.0 Hz), 7.2-7.6 (10H, m) HPLC; chiralcel OD, 10% isopropanol/hexane, 11.3 ml/min

후처리

  1. customthe solvent was evaporated in vacuo
  2. additionThe residue was diluted with CH2Cl2 (200 ml) and acetyl bromide (7.6 ml)
  3. additionwas added to the solution at 0° C. under N2
  4. stirringAfter being stirred for 2 hours at room temperature
  5. customthe solvent was evaporated in vacuo
  6. additionthe residue was diluted with methanol (200 ml), and K2CO3 (16 g)
  7. additionwas added to the solution at 0° C
  8. stirringThe mixture was stirred for 30 minutes at the same temperature
  9. custompartitioned between ethyl acetate and water
  10. washThe organic layer was washed with 1N-HCl, water, sat. NaHCO3 and brine
  11. customThe dried solvent was evaporated in vacuo
  12. customthe residue was purified by trituration with ether-hexane

출처 및 근거

ORD 기록
ord-71dce0c5160b460380b5d9dab5aee08e
출처 데이터셋
uspto-grants-1999_10
특허 번호
US05972965

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