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Phosphorus oxychloride → 7-[2-(2-formamidothiazol-4-yl)-2-(2-formyloxyethoxyimino)acetamido]-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid

HRID 255775
ノート
印刷プレビュー

反応式

HRID 255775 の反応式
[CH:1]([NH:3][C:4]1[S:5][CH:6]=[C:7]([C:9](=[N:13][O:14][CH2:15][CH2:16][O:17][CH:18]=[O:19])[C:10]([OH:12])=O)[N:8]=1)=[O:2].C[N+](C)=CCl.[Cl-].P(Cl)(Cl)(Cl)=O.[NH2:31][CH:32]1[C:52](=[O:53])[N:34]2[C:35]([C:49]([OH:51])=[O:50])=[C:36]([CH2:39][S:40][C:41]3[N:45]([CH2:46][CH:47]=[CH2:48])[N:44]=[N:43][N:42]=3)[CH2:37][S:38][C@H:33]12.C[Si](CC(N)=O)(C)C.C(=O)(O)[O-].[Na+]>C(OCC)(=O)C.O.CN(C)C=O>[CH:1]([NH:3][C:4]1[S:5][CH:6]=[C:7]([C:9](=[N:13][O:14][CH2:15][CH2:16][O:17][CH:18]=[O:19])[C:10]([NH:31][CH:32]2[C:52](=[O:53])[N:34]3[C:35]([C:49]([OH:51])=[O:50])=[C:36]([CH2:39][S:40][C:41]4[N:45]([CH2:46][CH:47]=[CH2:48])[N:44]=[N:43][N:42]=4)[CH2:37][S:38][C@H:33]23)=[O:12])[N:8]=1)=[O:2]
参加物実験手順後処理出典と根拠反応ノート

参加物

10

反応物 6

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 516892Sodium BicarbonateHCID 541333172-(2-Formamidothiazol-4-yl)-2-(2-formyloxyethoxyimino)acetic acidHCID 704326537-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid

生成物

1
HCID 1317153037-[2-(2-formamidothiazol-4-yl)-2-(2-formyloxyethoxyimino)acetamido]-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid収率 67.4%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒2 回

実験手順

2-(2-Formamidothiazol-4-yl)-2-(2-formyloxyethoxyimino)acetic acid (syn isomer, 3.6 g.) was added to Vilsmeier reagent prepared from N,N-dimethylformamide (1.1 g.) and phosphoryl chloride (2.3 g.) in dry ethyl acetate (48.4 ml.) at 0° to 5° C. and stirred for 30 minutes to give an activated acid solution. The solution was added to a solution of 7-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (4.4 g.) and trimethylsilylacetamide (11.4 g.) in ethyl acetate (88 ml.) at -10° C. and stirred at -10° to -5° C. for 1.5 hours. After adding water (100 ml.) to the resultant solution, the solution was adjusted to pH 7.0 with a saturated aqueous solution of sodium bicarbonate. The aqueous layer was separated washed with ethyl acetate and diethyl ether in turn and acidified to pH 2.5 with conc. hydrochloric acid. The precipitates were collected by filtration, washed with water and dried over phosphorus pentoxide to give 7-[2-(2-formamidothiazol-4-yl)-2-(2-formyloxyethoxyimino)acetamido]-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer, 5.22 g.)

後処理

  1. customto give an activated acid solution
  2. stirringstirred at -10° to -5° C. for 1.5 hours
  3. customThe aqueous layer was separated
  4. washwashed with ethyl acetate and diethyl ether in turn
  5. filtrationThe precipitates were collected by filtration
  6. washwashed with water
  7. dry with materialdried over phosphorus pentoxide

出典と根拠

ORDレコード
ord-a10c28f971164f79a6f1988d5fb605f3
出典データセット
uspto-grants-1987_10
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04698337

反応ノート

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