m-Chloroperbenzoic acid → HCID 131709948, compound

HRID 1580507Notes

Reaction equation

HRID 1580507 reaction equation
[C:1]1([CH:7]([O:14][C:15]([CH:17]2[N:22]3[C:23](=[O:34])[C@@H:24]([C:25](=[O:33])[CH2:26][C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[C@H:21]3[S:20][C:19]([NH2:35])=[C:18]2[CH2:36][C:37]2[CH:42]=[CH:41][C:40]([OH:43])=[CH:39][CH:38]=2)=[O:16])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.ClC1C=CC=C(C(OO)=[O:52])C=1>C(Cl)Cl>[C:1]1([CH:7]([O:14][C:15]([C:17]2[N:22]3[C:23](=[O:34])[C@@H:24]([C:25](=[O:33])[CH2:26][C:27]4[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=4)[C@H:21]3[S:20](=[O:52])[CH:19]([NH2:35])[C:18]=2[CH2:36][C:37]2[CH:42]=[CH:41][C:40]([OH:43])=[CH:39][CH:38]=2)=[O:16])[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 131709949HCID 131709949, compound

Product 1

HCID 131709948HCID 131709948, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 1.51 g of 3-(4-hydroxy-benzyl)-7βphenylacetyl-amino-ceph-2-em-4ξ-carboxylic acid diphenylmethylester in 40 ml of methylene chloride is cooled in an ice bath and treated with 0.52 g of purified 3-chloro-perbenzoic acid. The mixture is allowed to react for 1 hour at room temperature and the reaction solution is extracted successively with a 5% aqueous sodium hydrogen sulphite solution, a 0.5 molar aqueous dipotassium phosphate solution and water. The aqueous phases are re-extracted twice with small amounts of methylene chloride. The organic extracts are combined, dried over anhydrous magnesium sulphate and evaporated to dryness under reduced pressure. The residue is crystallised from a mixture of methyl acetate and cyclohexane and yields the 3-(4-hydroxybenzyl)-7β-phenylacetyl-amino-ceph-3-em-4-carboxylic acid diphenylmethyl ester-1-oxide, which after further crystallisation from a mixture of methyl acetate and cyclohexane and drying under a high vacuum for 20 hours at 35° melts at 192°-193°; [α]D20 = +36° ± 1° (c = 1.025 in dioxane); thin-layer chromatogram (silica gel: development with iodine): Rf = 0.18 (system: toluene/ethyl acetate 2:1), Rf = 0.36 (system: toluene/ethyl acetate 1:1), Rf = 0.24 (system: toluene/acetone 4:1), Rf = 0.07 (system: toluene/acetone 9:1) and Rf = 0.52 (system: methylene chloride/acetone 6:1); ultraviolet absorption spectrum (95% ethanol): λmax = 268 mμ (ε = 11300) and λmin = 241 mμ: infrared absorption spectrum (in mineral oil): characteristic bands at 2,94μ, 3,00μ, 5,60μ, 5,78μ, 5,85μ, 6,58μ, 6,65μ, 7,30μ, 7,99μ, 8,48μ, 8,70μ, 9,02μ, 9,78μ, 12,03μ, 13,45μ and 14,26μ.

Workup

  1. customto react for 1 hour at room temperature
  2. extractionthe reaction solution is extracted successively with a 5% aqueous sodium hydrogen sulphite solution
  3. extractionThe aqueous phases are re-extracted twice with small amounts of methylene chloride
  4. dry with materialdried over anhydrous magnesium sulphate
  5. customevaporated to dryness under reduced pressure
  6. customThe residue is crystallised from a mixture of methyl acetate and cyclohexane

Sources & evidence

ORD record
ord-6eb07c633c1f450fbc0160ee3d1f1c0d
Source dataset
uspto-grants-1976_01
Patent number
US03932465

Reaction notes

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