Phosphorus oxychloride → HCID 178460200、化合物

HRID 615762ノート

反応式

HRID 615762 の反応式
[O:1]1[C:6]([C:7](=[N:11][O:12][CH2:13][CH2:14][CH3:15])[C:8]([OH:10])=O)=[CH:5][S:4][CH2:3][CH2:2]1.P(Cl)(Cl)(Cl)=O.[NH2:21][CH:22]1[C:39](=[O:40])[N:24]2[C:25]([C:36]([OH:38])=[O:37])=[C:26]([CH2:29][S:30][C:31]3[NH:35][N:34]=[N:33][CH:32]=3)[CH2:27][S:28][C@H:23]12.C[Si](CC(N)=O)(C)C>O.C(OCC)(=O)C.CN(C)C=O>[O:1]1[C:6]([C:7](=[N:11][O:12][CH2:13][CH2:14][CH3:15])[C:8]([NH:21][CH:22]2[C:39](=[O:40])[N:24]3[C:25]([C:36]([OH:38])=[O:37])=[C:26]([CH2:29][S:30][C:31]4[NH:35][N:34]=[N:33][CH:32]=4)[CH2:27][S:28][C@H:23]23)=[O:10])=[CH:5][S:4][CH2:3][CH2:2]1

参加物

8

反応物 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 537836602-(2,3-Dihydro-1,4-oxathiin-6-yl)-2-n-propoxyiminoacetic acidHCID 178508102HCID 178508102、化合物

生成物 1

HCID 178460200HCID 178460200、化合物収率 69.3%

試薬・触媒・溶媒 3

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

反応条件

温度
40 °C

実験手順

2-(2,3-Dihydro-1,4-oxathiin-6-yl)-2-n-propoxyiminoacetic acid (syn isomer, 1.6 g.), dry N,N-dimethylformamide (0.56 ml.), dry ethyl acetate (22.3 ml.) and phosphoryl chloride (0.69 ml.) were treated in a similar manner to that of Example 14 to give an activated acid solution. On the other hand, 7-amino-3-(1H-1,2,3-triazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (2.0 g.) and trimethylsilylacetamide (5.9 g.) were added to dry ethyl acetate (40 ml.), and stirred at 40° C. for an hour. To the solution was added the activated acid solution at -15° C. and stirred at -10° to -20° C. for 50 minutes. Water (30 ml.) was added to the resultant solution, and the ethyl acetate layer was separated. Water (30 ml.) was added to the ethyl acetate solution and adjusted to pH 7.0 with sodium bicarbonate. The aqueous solution was separated, washed with ethyl acetate and adjusted to pH 2.7 with 10% hydrochloric acid. The precipitates were collected by filtration, washed with water and dried over phosphorus pentoxide under reduced pressure. The product was added to diethyl ether (100 ml.) and stirred. The precipitates were collected by filtration and washed with diethyl ether to give 7-[2-(2,3-dihydro-1,4-oxathiin-6-yl)-2-n-propoxyiminoacetamido]-3-(1H-1,2,3-triazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer, 2.33 g.).

後処理

  1. customto give an activated acid solution
  2. additionTo the solution was added the activated acid solution at -15° C.
  3. stirringstirred at -10° to -20° C. for 50 minutes
  4. customthe ethyl acetate layer was separated
  5. additionWater (30 ml.) was added to the ethyl acetate solution
  6. customThe aqueous solution was separated
  7. washwashed with ethyl acetate
  8. filtrationThe precipitates were collected by filtration
  9. washwashed with water
  10. dry with materialdried over phosphorus pentoxide under reduced pressure
  11. additionThe product was added to diethyl ether (100 ml.)
  12. stirringstirred
  13. filtrationThe precipitates were collected by filtration
  14. washwashed with diethyl ether

出典と根拠

ORDレコード
ord-3e6805307d064356b835e99263e858df
出典データセット
uspto-grants-1985_02
特許番号
US04500709

反応ノート

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