1,1'-(Diazomethylene)bis(benzene) → 2-Benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-methyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

HRID 1660327노트

반응식

HRID 1660327 반응식
[C:1]1([C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[N+]=[N-])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:16]([O:20][C:21]([NH:23][CH:24]1[C:31](=[O:32])[N:30]2[CH:25]1[S:26][CH2:27][C:28]([CH3:36])=[C:29]2[C:33]([OH:35])=[O:34])=[O:22])([CH3:19])([CH3:18])[CH3:17]>C(#N)C>[CH:7]([O:35][C:33]([C:29]1[N:30]2[CH:25]([S:26][CH2:27][C:28]=1[CH3:36])[CH:24]([NH:23][C:21]([O:20][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:22])[C:31]2=[O:32])=[O:34])([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

참가 물질

4

반응물 2

HCID 612301,1'-(Diazomethylene)bis(benzene)HCID 128967587-tert.-Butoxycarbonylamino-2-carboxy-3-methyl-8-oxo-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene

생성물 1

HCID 128967622-Benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-methyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene수율 66.3%

시약·촉매·용매 1

HCID 6342Acetonitrile용매2회

반응 조건

온도
22 °C

실험 절차

A solution of diphenyldiazomethane (116.5 g) in acetonitrile (800 cc) is added dropwise, in the course of 45 minutes, at a temperature of between 25° and 30° C., to a solution of 7-tert.-butoxycarbonylamino-2-carboxy-3-methyl-8-oxo-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene (188.6 g) in acetonitrile (2,100 cc). The reaction mixture is stirred for 16 hours at 22° C. and then concentrated to dryness under reduced pressure (20 mm Hg) at 40° C. The residue is redissolved in ethyl acetate (2 liters) and the solution is washed with 2 N hydrochloric acid (700 cc) and then with a saturated aqueous sodium bicarbonate solution (700 cc) and a saturated aqueous sodium chloride solution (700 cc). The solution is dried over sodium sulphate, treated with decolorising charcoal, filtered and then concentrated to dryness under reduced pressure (20 mm Hg) at 40° C. The residue is dissolved in boiling ethyl acetate (600 cc). Cyclohexane (1 liter) is added, and the mixture is heated under reflux and then allowed to cool. The crystals which have appeared are filtered off, washed with diethyl ether (3×250 cc) and then dried. 2-Benzhydryloxycarbonyl-7-tert.butoxycarbonylamino-3-methyl-8-oxo-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene (191 g) is obtained in the form of white crystals (m.p.=179° C.). On concentrating the mother liquors to 500 cc, a second fraction of product (32.6 g, m.p.=178° C.) is obtained.

후처리

  1. concentrationconcentrated to dryness under reduced pressure (20 mm Hg) at 40° C
  2. dissolutionThe residue is redissolved in ethyl acetate (2 liters)
  3. washthe solution is washed with 2 N hydrochloric acid (700 cc)
  4. dry with materialThe solution is dried over sodium sulphate
  5. additiontreated with decolorising charcoal
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure (20 mm Hg) at 40° C
  8. dissolutionThe residue is dissolved
  9. additionCyclohexane (1 liter) is added
  10. temperaturethe mixture is heated
  11. temperatureunder reflux
  12. temperatureto cool
  13. filtrationThe crystals which have appeared are filtered off
  14. washwashed with diethyl ether (3×250 cc)
  15. customdried

출처 및 근거

ORD 기록
ord-6bf02738725542178d7d6de317590534
출처 데이터셋
uspto-grants-1981_12
특허 번호
US04307116

반응 노트

불러오는 중…