Trimethyl phosphite → HCID 70424507, compound

HRID 2164215Notes

Reaction equation

HRID 2164215 reaction equation
ClC1C=CC=C(C(OO)=[O:9])C=1.[O:12]([CH2:19][C:20]([NH:22][CH:23]1[C:40](=[O:41])[N:25]2[C:26]([C:32]([O:34][CH2:35][C:36]([Cl:39])([Cl:38])[Cl:37])=[O:33])=[C:27]([CH3:31])[CH2:28][S:29](=[O:30])[C@H:24]12)=[O:21])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.COP(OC)OC>CC(C)=O.C(OCC)(=O)C.O.O.O.[Ru](Cl)(Cl)Cl>[O:12]([CH2:19][C:20]([NH:22][CH:23]1[C:40](=[O:41])[N:25]2[C:26]([C:32]([O:34][CH2:35][C:36]([Cl:38])([Cl:39])[Cl:37])=[O:33])=[C:27]([CH3:31])[CH2:28][S:29](=[O:9])(=[O:30])[C@H:24]12)=[O:21])[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

7

Reactant 3

HCID 8472Trimethyl phosphiteHCID 70297m-Chloroperbenzoic acid2×HCID 70425239HCID 70425239, compound

Product 1

HCID 70424507HCID 70424507, compoundYield 57%

Reagents, catalysts & solvents 3

HCID 12090026Ruthenium chloride trihydrateCatalystHCID 180AcetoneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 0.026 g (0.1 mM) of ruthenium trichloride trihydrate in 25 ml of acetone containing 0.5 mM of m-chloroperbenzoic acid was stirred for 10 minutes at 0° to -10° C. under a nitrogen atmosphere. To the stirred reaction mixture were added 4.94 g (10 mM) of 2,2,2-trichloroethyl 7-phenoxyacetamido-1-oxo-3-methyl-3-cephem-4-carboxylate in one portion, followed by the portion-wise addition over ten minutes of a solution of 8.0 g (40 mM) of m-chloroperbenzoic acid in 40 ml of acetone. Following the complete addition, the reaction mixture was warmed to room temperature and stirred for 4 hours. Thin-layer chromatographic analysis indicated that no starting material remained in the reaction mixture. Trimethylphosphite was added to the reaction mixture until a negative starch iodide test was obtained. The solvent was removed from the reaction mixture by evaporation under reduced pressure to provide a solid. The solid was dissolved in 100 ml of ethyl acetate and washed twice with 100 ml portions of dilute sodium carbonate and then with water and finally with brine. The solution was dried and the solvent was removed by evaporation under reduced pressure to provide an oil. Crystallization of the oil from 50 ml of methanol afforded 2.91 g of 2,2,2-trichloroethyl 7-phenoxyacetamido-1,1-dioxo-3-methyl-3-cephem-4-carboxylate. Yield 57%.

Workup

  1. customTo the stirred reaction mixture
  2. additionthe complete addition
  3. customwas obtained
  4. customThe solvent was removed from the reaction mixture by evaporation under reduced pressure
  5. customto provide a solid
  6. washwashed twice with 100 ml portions of dilute sodium carbonate
  7. customThe solution was dried
  8. customthe solvent was removed by evaporation under reduced pressure
  9. customto provide an oil
  10. customCrystallization of the oil from 50 ml of methanol

Sources & evidence

ORD record
ord-95e8747084e24b85b44233ddb7b3c5cc
Source dataset
uspto-grants-1985_03
Patent number
US04502988

Reaction notes

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