Trifluoromethanesulfonic anhydride → 4-nitrobenzyl (5R,6R)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-3-(5-methyl-1,3,4-thiadiazol-2-ylthio)-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate

HRID 235764

반응식

HRID 235764 반응식
C(N(C(C)C)CC)(C)C.O=[C:11]1[CH2:17][C@H:16]2[N:13]([C:14](=[O:35])[C@H:15]2[C:18]([CH3:34])([O:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=2)=[O:22])[CH3:19])[C@H:12]1[C:36]([O:38][CH2:39][C:40]1[CH:45]=[CH:44][C:43]([N+:46]([O-:48])=[O:47])=[CH:42][CH:41]=1)=[O:37].FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[CH3:64][C:65]1[S:69][C:68]([SH:70])=[N:67][N:66]=1>CN(C1C=CN=CC=1)C.C(Cl)Cl.CN(C)C=O>[CH3:34][C:18]([C@@H:15]1[C:14](=[O:35])[N:13]2[C@@H:16]1[CH2:17][C:11]([S:70][C:68]1[S:69][C:65]([CH3:64])=[N:66][N:67]=1)=[C:12]2[C:36]([O:38][CH2:39][C:40]1[CH:41]=[CH:42][C:43]([N+:46]([O-:48])=[O:47])=[CH:44][CH:45]=1)=[O:37])([O:20][C:21]([O:23][CH2:24][C:25]1[CH:26]=[CH:27][C:28]([N+:31]([O-:33])=[O:32])=[CH:29][CH:30]=1)=[O:22])[CH3:19]

참가 물질

8

반응물 4

HCID 67749Trifluoromethanesulfonic anhydrideHCID 81531Diisopropylethylamine2회HCID 185992114-nitrobenzyl (2R,5R,6R)-3,7-dioxo-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-1-azabicyclo[3.2.0]heptane-2-carboxylateHCID 178434161HCID 178434161, 화합물

생성물 1

HCID 545641394-nitrobenzyl (5R,6R)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-3-(5-methyl-1,3,4-thiadiazol-2-ylthio)-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate수율 85.1%

시약·촉매·용매 3

HCID 142844-(Dimethylamino)pyridine촉매HCID 6228Dimethylformamide용매HCID 6344Dichloromethane용매2회

반응 조건

온도
-30 °C

실험 절차

N,N-Diisopropyl-N-ethylamine (0.309 ml) was added to a solution of 4-nitrobenzyl (2R,5R,6R)-3,7-dioxo-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-1-azabicyclo[3.2.0]heptane-2-carboxylate (800 mg) and 4-(N,N-dimethylamino)pyridine (18 mg) in methylene chloride (40 ml) at -30° C. To this mixture was added a solution of trifluoromethanesulfonic anhydride (0.261 ml) in methylene chloride (2.35 ml). After the mixture was stirred at -30° C. for 30 minutes, to the reaction mixture was added N,N-diisopropyl-N-ethylamine (0.772 ml) at -30° C., and further a solution of 5-methyl-1,3,4-thiadiazole-2-thiol (205 mg) in N,N-dimethylformamide (10 ml) was added. The mixture was allowed to warm to ambient temperature over a period of 30 minutes and stirred at the same temperature for 2.5 hours. The resultant mixture was evaporated in vacuo and the residue was dissolved in ethyl acetate (100 ml). The solution was washed with water and a saturated aqueous sodium chloride, dried over magnesium sulfate and evaporated in vacuo. The residue was chromatographed on deactivated silica gel with 10% water (10 g), eluting with a mixture of benzene and acetone (50:1 to 20:1) to give 4-nitrobenzyl (5R,6R)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-3-(5-methyl-1,3,4-thiadiazol-2-ylthio)-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (824 mg) as an oil.

후처리

  1. temperatureto warm to ambient temperature over a period of 30 minutes
  2. stirringstirred at the same temperature for 2.5 hours
  3. customThe resultant mixture was evaporated in vacuo
  4. dissolutionthe residue was dissolved in ethyl acetate (100 ml)
  5. washThe solution was washed with water
  6. dry with materiala saturated aqueous sodium chloride, dried over magnesium sulfate
  7. customevaporated in vacuo
  8. customThe residue was chromatographed on deactivated silica gel with 10% water (10 g)
  9. washeluting with a mixture of benzene and acetone (50:1 to 20:1)

출처 및 근거

ORD 기록
ord-ae36646df03d4b37ada7f25852a629fa
출처 데이터셋
uspto-grants-1987_02
특허 번호
US04640915

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