m-Chloroperbenzoic acid → HCID 20276295, compound

HRID 370595Notes

Reaction equation

HRID 370595 reaction equation
ClC1C=CC=C(C(OO)=[O:9])C=1.[CH:12]([O:25][C:26]([C:28]1[N:29]2[CH:32]([S:33][CH2:34][C:35]=1[CH:36]([Br:39])[CH:37]=[O:38])[CH:31]([NH:40][C:41]([O:43][C:44]([CH3:47])([CH3:46])[CH3:45])=[O:42])[C:30]2=[O:48])=[O:27])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[CH:12]([O:25][C:26]([C:28]1[N:29]2[CH:32]([S:33](=[O:9])[CH2:34][C:35]=1[CH:36]([Br:39])[CH:37]=[O:38])[CH:31]([NH:40][C:41]([O:43][C:44]([CH3:45])([CH3:47])[CH3:46])=[O:42])[C:30]2=[O:48])=[O:27])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

5

Reactant 3

HCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 13175928HCID 13175928, compound

Product 1

HCID 20276295HCID 20276295, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

A solution of 85% pure meta-chloroperbenzoic acid (4.31 g) in methylene chloride (50 cc) is added dropwise, over a period of 30 minutes, to a solution, cooled to between 0° and -5° C., of 2-benzhydryloxycarbonyl-3-(1-bromo-2-oxoethyl)-7-t-butoxycarbonylamino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene (mixture of the diastereoisomers at the substituent in the 3-position) (14.69 g) in methylene chloride (150 cc). After 30 minutes at -5° C., the reaction mixture is poured into a mixture of a semi-saturated solution of sodium bicarbonate (100 cc) and methylene chloride (200 cc). The organic phase is washed with distilled water (150 cc) and a semi-saturated solution of sodium chloride (150 cc) and then dried over sodium sulphate and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 20° C. to give crude 2-benzhydryloxycarbonyl-3-(1-bromo-2-oxoethyl)-7-t-butoxycarbonylamino-8 -oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide (mixture of the diastereoisomers at the substituent in the 3-position) (13.35 g) in the form of a hard, light brown foam. The crude product obtained is divided into 2 batches, which are chromatographed on a column (height: 30 cm, diameter: 5 cm) of silica gel (0.04-0.063 mm), elution being carried out under a pressure of 0.4 bar (40 kPa) with a mixture of cyclohexane and ethyl acetate (40/60 by volume), and 125 cc fractions being collected. Fractions 7 to 10 from both chromatographic separations are combined and concentrated to dryness under reduced pressure (30 mm HG; 4 kPa) at 20° C. to give 2-benzhydryloxycarbonyl-3-(1-bromo-2-oxoethyl)-7-t-butoxycarbonylamino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide (mixture of the diastereoisomers at the substituent in the 3-position) (2.43 g) in the form of a hard yellow foam.

Workup

  1. washThe organic phase is washed with distilled water (150 cc)
  2. dry with materiala semi-saturated solution of sodium chloride (150 cc) and then dried over sodium sulphate
  3. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 20° C.
  4. customto give crude 2-benzhydryloxycarbonyl-3-(1-bromo-2-oxoethyl)-7-t-butoxycarbonylamino-8 -oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide (
  5. additionmixture of the diastereoisomers at the substituent in the 3-position) (13.35 g) in the form of a hard, light brown foam
  6. customThe crude product obtained
  7. customare chromatographed on a column (height: 30 cm, diameter: 5 cm) of silica gel (0.04-0.063 mm), elution
  8. additionbeing carried out under a pressure of 0.4 bar (40 kPa) with a mixture of cyclohexane and ethyl acetate (40/60 by volume), and 125 cc fractions
  9. custombeing collected
  10. concentrationconcentrated to dryness under reduced pressure (30 mm HG; 4 kPa) at 20° C.

Sources & evidence

ORD record
ord-fb406e728be3488ebb98a398c6b05eee
Source dataset
uspto-grants-1985_07
Patent number
US04526962

Reaction notes

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