m-Chloroperbenzoic acid → 3-Phenylsulfinyl-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic Acid, Diphenylmethyl Ester

HRID 2164583Notes

Reaction equation

HRID 2164583 reaction equation
[C:1]1([S:7][C:8]2[CH2:14][CH:13]3[CH:10]([C:11](=[O:15])[CH2:12]3)[C:9]=2[C:16]([O:18][CH:19]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[O:17])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.ClC1C=CC=C(C(OO)=[O:40])C=1>C(Cl)Cl>[C:1]1([S:7]([C:8]2[CH2:14][CH:13]3[CH:10]([C:11](=[O:15])[CH2:12]3)[C:9]=2[C:16]([O:18][CH:19]([C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)=[O:17])=[O:40])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 134769553-Phenylthio-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic Acid, Diphenylmethyl Ester

Product 1

HCID 134769563-Phenylsulfinyl-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic Acid, Diphenylmethyl Ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To a stirred solution of 150 mg of 3-phenylthio-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid, diphenylmethyl ester in 7 mL of methylene chloride at -50° under argon was added 75 mg of 85% m-chloroperbenzoic acid in methylene chloride solution. The resulting solution was stirred between -40° and -35° for 30 min and then allowed to warm to room temperature over approximately 30 min. The solution was diluted with methylene chloride, washed successively with aqueous sodium sulfite and aqueous sodium bicarbonate, and then dried over sodium sulfate. Evaporation of the solvent afforded a crude product mixture which was purified by preparative thin layer chromatography on a 20×20×0.2 cm silica gel plate eluted with ether. The most prominent band, which was in the center of the plate, contained 115 mg (73.9%) of 3-phenylsulfinyl-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid, diphenylmethyl ester, as a colorless solid [an approximately 3:1 mixture of diastereoisomers at sulfur (by NMR)]. IR (neat): 1785, 1710, 1720, 1605 cm-1 : NMR (220 MHz; CDCl3): δ 2.32 (1H, m), 2.55 (1H, dd, J=18, 4), 2.7-3.0 (1H, m), 3.0-3.3 (1H, m), 3.36 (1H, m), 4.57 (1/4H, m, from minor isomer), 4.70 (3/4H, m, from major isomer), 6.86 (1H, broad s), and 7.1-7.6 (15H, m).

Workup

  1. washwashed successively with aqueous sodium sulfite and aqueous sodium bicarbonate
  2. dry with materialdried over sodium sulfate
  3. customEvaporation of the solvent

Sources & evidence

ORD record
ord-674d5188338e4860b37a0ed3d0a6a069
Source dataset
uspto-grants-1985_03
Patent number
US04505905

Reaction notes

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