Phosphorus oxychloride → Benzhydryl 7-(2-benzyloxycarbonylmethoxyimino-4-bromo-3-oxobutyramido)-3-vinyl-3-cephem-4-carboxylate

HRID 569366

反応式

HRID 569366 の反応式
C[N+](C)=CCl.[Cl-].P(Cl)(Cl)(Cl)=O.[CH2:12]([O:19][C:20]([CH2:22][O:23][N:24]=[C:25]([C:29](=[O:32])[CH2:30][Br:31])[C:26]([OH:28])=O)=[O:21])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.Cl.[NH2:34][CH:35]1[C:60](=[O:61])[N:37]2[C:38]([C:44]([O:46][CH:47]([C:54]3[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=3)[C:48]3[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=3)=[O:45])=[C:39]([CH:42]=[CH2:43])[CH2:40][S:41][C@H:36]12.C[Si](CC(N)=O)(C)C>O1CCCC1.C(Cl)Cl.C(OCC)(=O)C.CN(C)C=O>[CH2:12]([O:19][C:20]([CH2:22][O:23][N:24]=[C:25]([C:29](=[O:32])[CH2:30][Br:31])[C:26]([NH:34][CH:35]1[C:60](=[O:61])[N:37]2[C:38]([C:44]([O:46][CH:47]([C:48]3[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=3)[C:54]3[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=3)=[O:45])=[C:39]([CH:42]=[CH2:43])[CH2:40][S:41][C@H:36]12)=[O:28])=[O:21])[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

参加物

10

反応物 5

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 12818005Benzhydryl 7-amino-3vinyl-3cephem-4-carboxylate hydrochlorideHCID 540321592-Benzyloxycarbonylmethoxyimino-4-bromo-3-oxobutyric acid

生成物 1

HCID 131713331Benzhydryl 7-(2-benzyloxycarbonylmethoxyimino-4-bromo-3-oxobutyramido)-3-vinyl-3-cephem-4-carboxylate収率 74.5%

試薬・触媒・溶媒 4

HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

Vilsmeier reagent prepared from N,N-dimethylformamide (0.67 ml) and phosphorus oxychloride (0.79 ml) was suspended in dry tetrahydrofuran (25 ml). Thereto was added 2-benzyloxycarbonylmethoxyimino-4-bromo-3-oxobutyric acid (2.8 g) at 0° C. with stirring, and the stirring was continued at 0° to 5° C. for an hour to prepare the activated acid solution. This activated acid solution was added at a time to a solution of benzhydryl 7-amino-3-vinyl-3-cephem-4-carboxylate hydrochloride (2.2 g) and trimethylsilylacetamide (7.0 g) in methylene chloride (30 ml) at -35° C., and the mixture was stirred at -10° to -5° C. for 30 minutes. The reaction mixture was poured into ethyl acetate (200 ml), and the separated organic solution was washed with a saturated aqueous sodium bicarbonate and a saturated aqueous sodium chloride, followed by drying over magnesium sulfate. Removal of the solvent gave benzhydryl 7-(2-benzyloxycarbonylmethoxyimino-4-bromo-3-oxobutyramido)-3-vinyl-3-cephem-4-carboxylate (2.8 g).

後処理

  1. waitthe stirring was continued at 0° to 5° C. for an hour
  2. customto prepare the activated acid solution
  3. stirringthe mixture was stirred at -10° to -5° C. for 30 minutes
  4. washthe separated organic solution was washed with a saturated aqueous sodium bicarbonate
  5. dry with materialby drying over magnesium sulfate
  6. customRemoval of the solvent

出典と根拠

ORDレコード
ord-fe439d98f61542b2aa8425050489ac81
出典データセット
uspto-grants-1988_03
特許番号
US04731443

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