Phosphorus oxychloride → Chloro-N,N-dimethylformiminium chloride

HRID 371241ノート

反応式

HRID 371241 の反応式
P(Cl)(Cl)([Cl:3])=O.[CH:6]1([O:11][N:12]=[C:13]([C:17]2[N:18]=[C:19]([NH:22][CH:23]=[O:24])[S:20][CH:21]=2)[C:14]([OH:16])=O)[CH2:10][CH2:9][CH:8]=[CH:7]1.[CH3:25][N+:26]([CH3:29])=[CH:27][Cl:28].[Cl-].[NH2:31][CH:32]1[C:43](=[O:44])[N:34]2[C:35]([C:40]([OH:42])=[O:41])=[CH:36][CH:37]([CH3:39])[S:38][C@H:33]12.C[Si](CC(N)=O)(C)C>C(OCC)(=O)C.O1CCCC1.O.CN(C)C=O>[CH3:25][N+:26]([CH3:29])=[CH:27][Cl:28].[Cl-:3].[CH:6]1([O:11][N:12]=[C:13]([C:17]2[N:18]=[C:19]([NH:22][CH:23]=[O:24])[S:20][CH:21]=2)[C:14]([NH:31][CH:32]2[C:43](=[O:44])[N:34]3[C:35]([C:40]([OH:42])=[O:41])=[CH:36][CH:37]([CH3:39])[S:38][C@H:33]23)=[O:16])[CH2:10][CH2:9][CH:8]=[CH:7]1

参加物

11

反応物 5

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 128022512-Methyl-7-amino-3-cephem-4-carboxylic acidHCID 538228722-(2-Cyclopenten-1-yl)oxyimino-2-(2-formamidothiazol-4-yl)acetic acid

生成物 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 1317130257-[2-(2-Cyclopenten-1-yl)oxyimino-2-(2-formamidothiazol-4-yl)acetamido]-2-methyl-3-cephem-4-carboxylic acid

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒3 回

実験手順

The solution of Vilsmeier reagent was prepared from dry N,N-dimethylformamide (0.48 g) and phosphoryl chloride (0.98 g) in dry ethyl acetate (3 ml) in a usual manner. A solution of 2-(2-cyclopenten-1-yl)oxyimino-2-(2-formamidothiazol-4-yl)acetic acid (syn isomer)(1.5 g) in dry tetrahydrofuran (12 ml) was added to the stirred suspension of the solution of Vilsmeier reagent under ice-cooling. The resulting mixture was added to a solution of 7-amino-2-methyl-3-cephem-4-carboxylic acid (1.37 g) and trimethylsilylacetamide (5.04 g) in ethyl acetate (14 ml) at -30° to -20° C. and the mixture was stirred at -5°~-10° C. for 2 hours. After the addition of water and ethyl acetate to the reaction mixture, the ethyl acetate layer was separated and adjusted to pH 7 with an aqueous solution of sodium bicarbonate. The aqueous layer was separated and thereto was added ethyl acetate. The mixture was adjusted to pH 2.5 with 10% hydrochloric acid. The ethyl acetate layer was separated, washed with an aqueous solution of sodium chloride, dried over magnesium sulfate and then evaporated. The residue was pulverized in diisopropyl ether to give 7-[2-(2-cyclopenten-1-yl)oxyimino-2-(2-formamidothiazol-4-yl)acetamido]-2-methyl-3-cephem-4-carboxylic acid (syn isomer)(1.98 g).

後処理

  1. temperaturecooling
  2. customthe ethyl acetate layer was separated
  3. customThe aqueous layer was separated
  4. additionwas added ethyl acetate
  5. customThe ethyl acetate layer was separated
  6. washwashed with an aqueous solution of sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. customevaporated

出典と根拠

ORDレコード
ord-376899a47108415bbef72bce76c6465c
出典データセット
uspto-grants-1985_07
特許番号
US04529802

反応ノート

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