Phosphorus oxychloride → Chloro-N,N-dimethylformiminium chloride

HRID 615412노트

반응식

HRID 615412 반응식
P(Cl)(Cl)([Cl:3])=O.[C:6]([O:10][C:11]([CH2:13][O:14][N:15]=[C:16]([C:20]1[N:21]=[CH:22][S:23][CH:24]=1)[C:17]([OH:19])=O)=[O:12])([CH3:9])([CH3:8])[CH3:7].[CH3:25][N+:26]([CH3:29])=[CH:27][Cl:28].[Cl-].C[Si](CC(N)=O)(C)C.[NH2:39][CH:40]1[C:65](=[O:66])[N:42]2[C:43]([C:49]([O:51][CH:52]([C:59]3[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=3)[C:53]3[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=3)=[O:50])=[C:44]([CH2:47][Cl:48])[CH2:45][S:46][C@H:41]12>C(OCC)(=O)C.O.CN(C)C=O>[CH3:25][N+:26]([CH3:29])=[CH:27][Cl:28].[Cl-:3].[C:6]([O:10][C:11]([CH2:13][O:14][N:15]=[C:16]([C:20]1[N:21]=[CH:22][S:23][CH:24]=1)[C:17]([NH:39][CH:40]1[C:65](=[O:66])[N:42]2[C:43]([C:49]([O:51][CH:52]([C:53]3[CH:54]=[CH:55][CH:56]=[CH:57][CH:58]=3)[C:59]3[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=3)=[O:50])=[C:44]([CH2:47][Cl:48])[CH2:45][S:46][C@H:41]12)=[O:19])=[O:12])([CH3:7])([CH3:8])[CH3:9]

참가 물질

10

반응물 5

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 13239626Benzhydryl 7-Amino-3-chloromethyl-3-cephem-4-carboxylateHCID 544727372-t-Butoxycarbonylmethoxyimino-2-(4-thiazolyl)acetic acid

생성물 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 131714103Benzhydryl 7-[2-t-butoxycarbonylmethoxyimino-2-(4-thiazolyl)acetamido]-3-chloromethyl-3-cephem-4-carboxylate

시약·촉매·용매 3

HCID 962Water용매HCID 6228Dimethylformamide용매HCID 8857Ethyl Acetate용매3회

실험 절차

Vilsmeier reagent was prepared from phosphorus oxychloride (14.4 g) and N,N-dimethylformamide (6.9 g) in ethyl acetate (27.6 ml) in a usual manner. 2-t-Butoxycarbonylmethoxyimino-2-(4-thiazolyl)acetic acid (syn isomer) (22.8 g) was added to the stirred suspension of Vilsmeier reagent in ethyl acetate (200 ml) under ice-cooling and the mixture was stirred for 20 minutes at the same temperature to produce an activated acid solution. Trimethylsilylacetamide (56.9 g) was added to a stirred suspension of benzhydryl 7-amino-3-chloromethyl-3-cephem-4-carboxylate (30 g) in ethyl acetate (300 ml) and the resultant mixture was stirred for 30 minutes at ambient temperature. To the solution was added the activated acid solution obtained above at -10° C. and the mixture was stirred for 30 minutes at the same temperature. Water was added to the reaction mixture, and the separated organic layer was washed with a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride, successively. The ethyl acetate layer was dried over magnesium sulfate and evaporated to give benzhydryl 7-[2-t-butoxycarbonylmethoxyimino-2-(4-thiazolyl)acetamido]-3-chloromethyl-3-cephem-4-carboxylate (syn isomer) (37.3 g).

후처리

  1. temperaturecooling
  2. customto produce an activated acid solution
  3. additionTo the solution was added the activated acid solution
  4. customobtained above at -10° C.
  5. stirringthe mixture was stirred for 30 minutes at the same temperature
  6. washthe separated organic layer was washed with a saturated aqueous solution of sodium bicarbonate
  7. dry with materialThe ethyl acetate layer was dried over magnesium sulfate
  8. customevaporated

출처 및 근거

ORD 기록
ord-6a87edf9da864810a31c086466d28ccf
출처 데이터셋
uspto-grants-1985_02
특허 번호
US04499088

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