2-[4-(p-Toluenesulphonylthio)-3-phenoxyacetamido-2-oxoazetidin-1-yl]-3-methylenebutyric acid p-nitrobenzyl ester → (4-Nitrophenyl)methyl (2R-(1(E),2alpha,3alpha))-alpha-(1-hydroxyethylidene)-4-oxo-3-((phenoxyacetyl)amino)-2-(((p-tolyl)sulphonyl)thio)azetidine-1-acetate

HRID 847702Notes

Reaction equation

HRID 847702 reaction equation
[N+:1]([C:4]1[CH:44]=[CH:43][C:7]([CH2:8][O:9][C:10](=[O:42])[CH:11]([N:15]2[CH:18]([S:19][S:20]([C:23]3[CH:28]=[CH:27][C:26]([CH3:29])=[CH:25][CH:24]=3)(=[O:22])=[O:21])[CH:17]([NH:30][C:31](=[O:40])[CH2:32][O:33][C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C:16]2=[O:41])[C:12](=[CH2:14])C)=[CH:6][CH:5]=1)([O-:3])=[O:2].S(=O)(O)[O-:46].[Na+]>C(OC)(=O)C.O.C(OCC)(=O)C>[N+:1]([C:4]1[CH:44]=[CH:43][C:7]([CH2:8][O:9][C:10](=[O:42])/[C:11](/[N:15]2[CH:18]([S:19][S:20]([C:23]3[CH:24]=[CH:25][C:26]([CH3:29])=[CH:27][CH:28]=3)(=[O:21])=[O:22])[CH:17]([NH:30][C:31](=[O:40])[CH2:32][O:33][C:34]3[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=3)[C:16]2=[O:41])=[C:12](\[OH:46])/[CH3:14])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

6

Reactant 2

HCID 128048172-[4-(p-Toluenesulphonylthio)-3-phenoxyacetamido-2-oxoazetidin-1-yl]-3-methylenebutyric acid p-nitrobenzyl esterHCID 23665763Sodium Bisulfite

Product 1

HCID 54709824(4-Nitrophenyl)methyl (2R-(1(E),2alpha,3alpha))-alpha-(1-hydroxyethylidene)-4-oxo-3-((phenoxyacetyl)amino)-2-(((p-tolyl)sulphonyl)thio)azetidine-1-acetate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6584Methyl AcetateSolventHCID 8857Ethyl AcetateSolvent

Procedure

(di) The crude 2-[4-(p-toluenesulphonylthio)-3-phenoxyacetamido-2-oxoazetidin-1-yl]-3-methylenebutyric acid p-nitrobenzyl ester, obtained according to Example 1 (cyii), is dissolved in 20 ml of methyl acetate and ozonised at -70° C. until no further starting material is present, according to a thin layer chromatogram. A stream of nitrogen is then passed through the solution and the latter is warmed to 0°-5° C. A solution of 300 mg of sodium bisulphite in 5 ml of water is added and the mixture is stirred for about 5 minutes until no further ozonide can be detected with potassium iodide/starch paper. The mixture is diluted with ethyl acetate, the aqueous phase is separated off, and the organic phase is washed with water, dried over magnesium sulphate and freed from solvent in vacuo. The crude product is dissolved in 3 ml of methylene chloride and 15 ml of toluene are added. The precipitate is filtered off and the filtrate is evaporated in vacuo. The residue is recrystallised from methanol and gives 2-[4-(p-toluenesulphonylthio)-3-phenoxyacetamido-2-oxoazetidin-1-yl]-3-hydroxycrotonic acid p-nitrobenzyl ester of melting point 159°-160° C.

Workup

  1. customozonised at -70° C.
  2. temperaturethe latter is warmed to 0°-5° C
  3. customthe aqueous phase is separated off
  4. washthe organic phase is washed with water
  5. dry with materialdried over magnesium sulphate
  6. dissolutionThe crude product is dissolved in 3 ml of methylene chloride
  7. addition15 ml of toluene are added
  8. filtrationThe precipitate is filtered off
  9. customthe filtrate is evaporated in vacuo
  10. customThe residue is recrystallised from methanol

Sources & evidence

ORD record
ord-8d9764c574994a8aaea2c40f9f3c0bed
Source dataset
uspto-grants-1981_10
Patent number
US04293462

Reaction notes

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