m-Chloroperbenzoic acid → (-)-4,4-Diphenylperhydrothiopyrano[2,3-c]pyrrole 1-oxide

HRID 375476Notes

Reaction equation

HRID 375476 reaction equation
ClC1C=C(C=CC=1)C(OO)=[O:6].[C:12]1([C:18]2([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[CH:26]3[CH:22]([CH2:23][NH:24][CH2:25]3)[S:21][CH2:20][CH2:19]2)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>ClCCl.CO>[C:27]1([C:18]2([C:12]3[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=3)[CH:26]3[CH:22]([CH2:23][NH:24][CH2:25]3)[S:21](=[O:6])[CH2:20][CH2:19]2)[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

5

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 9796194(4aRS, 7aRS)-4,4-diphenylperhydrothiopyrano[2,3-c]pyrrole

Product 1

HCID 18995289(-)-4,4-Diphenylperhydrothiopyrano[2,3-c]pyrrole 1-oxideYield 51.6%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-3 °C

Procedure

A solution of 15.4 g of 3-chloroperoxybenzoic acid (at 85%) in 400 cm3 of dichloromethane is added over 40 minutes to a solution, cooled to -3° C., of 25 g of (4aRS, 7aRS)-4,4-diphenylperhydrothiopyrano[2,3-c]pyrrole in 500 cm3 of dichloromethane and 100 cm3 of methanol. After stirring for one hour at -3° C., the reaction mixture is washed with 200 cm3 of a 10% aqueous solution of potassium hydrogen carbonate and again with 100 cm3 of this same solution, then dried over magnesium sulphate and concentrated to dryness at 40° C. under reduced pressure (2.7 kPa). The residue is crystallized from 50 cm3 of ethyl acetate, the crystals are taken up in 200 cm3 of dichloromethane, the solution obtained is washed with 75 cm3 of a 1N aqueous solution of sodium hydroxide and then dried over magnesium sulphate and concentrated to dryness. The residue is crystallized from 30 cm3 of ethyl acetate, the crystals are washed with ethyl acetate, drained and dried. 13.6 g of (1RS,4aRS,7aRS)-4,4-diphenylperhydrothiopyrano[2,3-c]-pyrrole 1-oxide are obtained in the form of white crystals; melting point 174° C.

Workup

  1. washthe reaction mixture is washed with 200 cm3 of a 10% aqueous solution of potassium hydrogen carbonate and again with 100 cm3 of this same solution
  2. dry with materialdried over magnesium sulphate
  3. concentrationconcentrated to dryness at 40° C. under reduced pressure (2.7 kPa)
  4. customThe residue is crystallized from 50 cm3 of ethyl acetate
  5. customthe solution obtained
  6. washis washed with 75 cm3 of a 1N aqueous solution of sodium hydroxide
  7. dry with materialdried over magnesium sulphate
  8. concentrationconcentrated to dryness
  9. customThe residue is crystallized from 30 cm3 of ethyl acetate
  10. washthe crystals are washed with ethyl acetate
  11. customdried

Sources & evidence

ORD record
ord-481d81b341cb425a949282cdfbf67c67
Source dataset
uspto-grants-1996_01
Patent number
US05484942

Reaction notes

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