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

HRID 1376840Notes

Reaction equation

HRID 1376840 reaction equation
[C:1]([NH:20][C:21]1[S:22][CH:23]=[C:24]([C:26](=[N:54][O:55][CH3:56])[C:27]([NH:29][CH:30]2[C:37](=[O:38])[N:36]3[CH:31]2[CH2:32][S:33][CH:34]([S:47][CH2:48][C:49]([O:51][CH2:52][CH3:53])=[O:50])[C:35]3(O)[C:39]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])=[O:28])[N:25]=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:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.P(I)(I)P(I)I.C(OCC)(=O)C>N1C=CC=CC=1>[C:1]([NH:20][C:21]1[S:22][CH:23]=[C:24]([C:26](=[N:54][O:55][CH3:56])[C:27]([NH:29][CH:30]2[C:37](=[O:38])[N:36]3[CH:31]2[CH2:32][S:33][C:34]([S:47][CH2:48][C:49]([O:51][CH2:52][CH3:53])=[O:50])=[C:35]3[C:39]([O:41][C:42]([CH3:43])([CH3:45])[CH3:44])=[O:40])=[O:28])[N:25]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 83484Hypodiphosphorous tetraiodide2×HCID 545179441,1-Dimethylethyl 7-[2-(2-tritylaminothiazol-4-yl)-2-methoxyimino-acetamido]-3--(ethoxycarbonylmethylthio)-2-hydroxy-8-oxo-4-thia-1-azabicyclo[4,2,0]octane-2-carboxylate

Product 1

HCID 53798384Racemic 1,1-dimethylethyl 7-[2-(2-tritylaminothiazol-4-yl)-2-methoxyimino-acetamido]-3-(ethoxycarbonylmethylthio)-8-oxo-4-thia-1-azabicyclo[4,2,0]oct-2-ene-2-carboxylateYield 44.5%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

1.55 g of the product of Step A dissolved in 30 ml of pyridine and 1.4 g of diphosphorus tetraiodide were stirred under an inert atmosphere for 30 minutes and after a further 0.76 g of diphosphorus tetraiodide were added, the mixture was stirred for 1 hour. 100 ml of ethyl acetate were added followed by filtering and concentrating to dryness under reduced pressure at a temperature below 30° C. The residue was dissolved in ethyl acetate and the solution was filtered, washed first with 0.1N hydrochloric acid, then with a solution of sodium bicarbonate, and then with a sodium chloride solution, after which it was dried and concentrated to dryness. The residue was chromatographed on silica and eluted with a mixture of methylene chloride and acetone (10-0.75). After crystallization from ether, 675 mg of racemic 1,1-dimethylethyl 7-[2-(2-tritylaminothiazol-4-yl)-2-methoxyimino-acetamido]-3-(ethoxycarbonylmethylthio)-8-oxo-4-thia-1-azabicyclo[4,2,0]oct-2-ene-2-carboxylate melting at 212°-214° C. (decomposes) were obtained.

Workup

  1. filtrationby filtering
  2. concentrationconcentrating to dryness under reduced pressure at a temperature below 30° C
  3. dissolutionThe residue was dissolved in ethyl acetate
  4. filtrationthe solution was filtered
  5. washwashed first with 0.1N hydrochloric acid
  6. dry with materialwith a solution of sodium bicarbonate, and then with a sodium chloride solution, after which it was dried
  7. concentrationconcentrated to dryness
  8. customThe residue was chromatographed on silica
  9. washeluted with a mixture of methylene chloride and acetone (10-0.75)
  10. customAfter crystallization from ether

Sources & evidence

ORD record
ord-38e19bdb3c4b46348852f29d8129825d
Source dataset
uspto-grants-1997_09
Patent number
US05663164

Reaction notes

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