Ethyl Acetate → Racemic 1,1-dimethylethyl 7-[2-(2-tritylaminothiazol-4-yl)-2-methoxyimino-acetamido]-3-(3-nitrophenylthio)-8-oxo-4-thia-1-azabicyclo[4,2,0]oct-2-ene-2-carboxylate

HRID 1376835Notes

Reaction equation

HRID 1376835 reaction equation
P(I)(I)P(I)I.[C:7]([NH:26][C:27]1[S:28][CH:29]=[C:30]([C:32](=[N:63][O:64][CH3:65])[C:33]([NH:35][CH:36]2[C:43](=[O:44])[N:42]3[CH:37]2[CH2:38][S:39][CH:40]([S:53][C:54]2[CH:59]=[CH:58][CH:57]=[C:56]([N+:60]([O-:62])=[O:61])[CH:55]=2)[C:41]3(O)[C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])=[O:34])[N:31]=1)([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.C(OCC)(=O)C>N1C=CC=CC=1>[C:7]([NH:26][C:27]1[S:28][CH:29]=[C:30]([C:32](=[N:63][O:64][CH3:65])[C:33]([NH:35][CH:36]2[C:43](=[O:44])[N:42]3[CH:37]2[CH2:38][S:39][C:40]([S:53][C:54]2[CH:59]=[CH:58][CH:57]=[C:56]([N+:60]([O-:62])=[O:61])[CH:55]=2)=[C:41]3[C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])=[O:34])[N:31]=1)([C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 83484Hypodiphosphorous tetraiodide2×HCID 537770691,1-Dimethylethyl 7-[2-(2-tritylaminothiazol-4-yl)-2-methoxyimino-acetamido]-2-hydroxy-3-(3-nitrophenylthio)-8-oxo-4-thia-1-azabicyclo[4,2,0]octane-2-carboxylate

Product 1

HCID 53941303Racemic 1,1-dimethylethyl 7-[2-(2-tritylaminothiazol-4-yl)-2-methoxyimino-acetamido]-3-(3-nitrophenylthio)-8-oxo-4-thia-1-azabicyclo[4,2,0]oct-2-ene-2-carboxylateYield 45.6%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A suspension of 677 mg of diphosphorus tetraiodide in 7 ml of pyridine was stirred under an inert atmosphere for 5 minutes and then 780 mg of the product of Step A were added. The mixture was stirred for 2 hours and then a further 363 mg of diphosphorus tetraiodide were added. The stirring was maintained for 1 hour and the reaction mixture was poured into 50 ml of ethyl acetate and filtered. The filtrate was evaporated to dryness under reduced pressure and the residue was dissolved in methylene chloride. The organic phase was washed with 0.1N hydrochloric acid, then with water, dried and concentrated to dryness. The residue was chromatographed on silica and eluted with a mixture of chloroform and acetone (10-0.5) to obtain 348 mg of racemic 1,1-dimethylethyl 7-[2-(2-tritylaminothiazol-4-yl)-2-methoxyimino-acetamido]-3-(3-nitrophenylthio)-8-oxo-4-thia-1-azabicyclo[4,2,0]oct-2-ene-2-carboxylate which crystallized from ether.

Workup

  1. stirringThe mixture was stirred for 2 hours
  2. temperatureThe stirring was maintained for 1 hour
  3. filtrationfiltered
  4. customThe filtrate was evaporated to dryness under reduced pressure
  5. dissolutionthe residue was dissolved in methylene chloride
  6. washThe organic phase was washed with 0.1N hydrochloric acid
  7. dry with materialwith water, dried
  8. concentrationconcentrated to dryness
  9. customThe residue was chromatographed on silica
  10. washeluted with a mixture of chloroform and acetone (10-0.5)

Sources & evidence

ORD record
ord-1fd019655fe64d5780bc8451a36df9b7
Source dataset
uspto-grants-1997_09
Patent number
US05663164

Reaction notes

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