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Phosphorus oxychloride → 7-[2-(2-Formamido-5-bromothiazol-4-yl)-2-methoxyiminoacetamido]-3-(5-methyl-1,3,4-thiadiazol-2-ylthiomethyl)-3-cephem-4-carboxylic acid

HRID 256430
ノート
印刷プレビュー

反応式

HRID 256430 の反応式
P(Cl)(Cl)(Cl)=O.[CH:6]([NH:8][C:9]1[S:10][C:11]([Br:21])=[C:12]([C:14](=[N:18][O:19][CH3:20])[C:15]([OH:17])=O)[N:13]=1)=[O:7].[NH2:22][CH:23]1[C:41](=[O:42])[N:25]2[C:26]([C:38]([OH:40])=[O:39])=[C:27]([CH2:30][S:31][C:32]3[S:33][C:34]([CH3:37])=[N:35][N:36]=3)[CH2:28][S:29][C@H:24]12.C[Si](CC(N)=O)(C)C>C(OCC)(=O)C.O.CN(C)C=O>[CH:6]([NH:8][C:9]1[S:10][C:11]([Br:21])=[C:12]([C:14](=[N:18][O:19][CH3:20])[C:15]([NH:22][CH:23]2[C:41](=[O:42])[N:25]3[C:26]([C:38]([OH:40])=[O:39])=[C:27]([CH2:30][S:31][C:32]4[S:33][C:34]([CH3:37])=[N:35][N:36]=4)[CH2:28][S:29][C@H:24]23)=[O:17])[N:13]=1)=[O:7]
参加物実験手順後処理出典と根拠反応ノート

参加物

8

反応物 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 129420347-Amino-3-(5-methyl-1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acidHCID 538011022-(2-Formamido-5-bromothiazol-4-yl)-2-methoxyiminoacetic acid

生成物 1

HCID 1317153357-[2-(2-Formamido-5-bromothiazol-4-yl)-2-methoxyiminoacetamido]-3-(5-methyl-1,3,4-thiadiazol-2-ylthiomethyl)-3-cephem-4-carboxylic acid
収率 59.2%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒4 回

実験手順

A mixture of dimethylformamide (0.3 ml.), phosphoryl chloride (0.35 ml.) and dry ethyl acetate (1.5 ml.) was stirred for 30 minutes under ice-cooling. Dry ethyl acetate (1.5 ml.) and 2-(2-formamido-5-bromothiazol-4-yl)-2-methoxyiminoacetic acid (syn isomer, 1.0 g.) were added to the solution and stirred for 50 minutes under ice-cooling. The solution was added dropwise to a chilled solution of 7-amino-3-(5-methyl-1,3,4-thiadiazol-2-ylthiomethyl)-3-cephem-4-carboxylic acid (1.1 g.) and trimethylsilylacetamide (2.5 g.) in dry ethyl acetate (30 ml.), and stirred at -20° to -10° C. for an hour. To the reaction mixture were added ethyl acetate (30 ml.) and water 20 ml., and the insoluble substance was filtered off. The ethyl acetate layer was separated from the filtrate, and the aqueous layer was washed with ethyl acetate. The washings and the ethyl acetate layer were combined together, washed with a saturated aqueous sodium chloride, dried over magnesium sulfate and then evaporated in vacuo. The residue was pulverized with diethyl ether, and the precipitates were collected by filtration, washed with diethyl ether and dried to give 7-[2-(2-formamido-5-bromothiazol-4-yl)-2-methoxyiminoacetamido]-3-(5-methyl-1,3,4-thiadiazol-2-ylthiomethyl)-3-cephem-4-carboxylic acid (syn isomer, 1.2 g.).

後処理

  1. temperaturecooling
  2. stirringstirred for 50 minutes under ice-
  3. temperaturecooling
  4. stirringstirred at -20° to -10° C. for an hour
  5. filtration, and the insoluble substance was filtered off
  6. customThe ethyl acetate layer was separated from the filtrate
  7. washthe aqueous layer was washed with ethyl acetate
  8. washwashed with a saturated aqueous sodium chloride
  9. dry with materialdried over magnesium sulfate
  10. customevaporated in vacuo
  11. filtrationthe precipitates were collected by filtration
  12. washwashed with diethyl ether
  13. customdried

出典と根拠

ORDレコード
ord-83bf85e407d849f1a1fd1174db27c2cf
出典データセット
uspto-grants-1987_10
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04703046

反応ノート

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