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

反応式

HRID 235764 の反応式
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]

参加物

8

反応物 4

HCID 67749Trifluoromethanesulfonic anhydrideHCID 81531Diisopropylethylamine2 回HCID 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、化合物

生成物 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-carboxylate収率 85.1%

試薬・触媒・溶媒 3

HCID 142844-(Dimethylamino)pyridine触媒HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-30 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-ae36646df03d4b37ada7f25852a629fa
出典データセット
uspto-grants-1987_02
特許番号
US04640915

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