Water → HCID 21517982, compound

HRID 1283392Notes

Reaction equation

HRID 1283392 reaction equation
[Cl:1][C:2]([Cl:7])([Cl:6])[C:3](Cl)=[O:4].[CH3:8][C:9]1[CH2:16][S:15][CH:14]2[N:11]([C:12](=[O:27])[CH:13]2[NH:17]C(=O)CC2C=CC=CC=2)[C:10]=1[C:28]([O:30][CH2:31][C:32]([Cl:35])([Cl:34])[Cl:33])=[O:29].O>N1C=CC=CC=1.C1C=CC=CC=1>[CH3:8][C:9]1[CH2:16][S:15][CH:14]2[N:11]([C:12](=[O:27])[CH:13]2[NH:17][C:3](=[O:4])[C:2]([Cl:7])([Cl:6])[Cl:1])[C:10]=1[C:28]([O:30][CH2:31][C:32]([Cl:35])([Cl:33])[Cl:34])=[O:29]

Participants

6

Reactant 3

HCID 962WaterHCID 6420Trichloroacetyl chlorideHCID 2835862HCID 2835862, compound

Product 1

HCID 21517982HCID 21517982, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 1049PyridineSolvent

Procedure

Trichloroacetyl chloride (1.04 cc.) is added, over the course of 30 minutes and with vigorous stirring, to a solution, cooled to -10°C, of 3-methyl-8-oxo-7-phenylacetamido-2-trichloroethoxycarbonyl-5-thia-1-aza-bicyclo[4,2,0]oct-2-ene (1.38 g) in pyridine (15 cc.). Thereafter, the mixture is stirred for 2 hours 30 minutes at a temperature of between -3° and -1°C. The mixture is then poured into water and crushed ice (100 cc.) and a maroon paste-like product settles out. After removing the liquid phase by decanting, this product is triturated in water (50 cc.) and is then taken up in ethyl acetate (200 cc.). The organic phase is washed with water (3 times 200 cc.), dried over sodium sulphate, filtered and concentrated to dryness under reduced pressure (12 mm Hg) at 30°C. The solid obtained is dissolved in benzene (20 cc.) and the solution obtained is chromatographed on a column of silica gel (20 g) (0.05-0.20 mm, pH neutral; diameter of the column: 1.5 cm, height: 20 cm). Elution is carried out successively with benzene (300 cc.), a mixture of benzene and ethyl acetate (99.5/0.5 by volume) (300 cc.) and a mixture of benzene and ethyl acetate (99/1 by volume) (600 cc.), collecting 25 cc. fractions. Fractions 6 to 36 are combined and concentrated to dryness under reduced pressure (12 mm Hg) at 30°C. 3-methyl-8-oxo-7-trichloroacetamido-2-trichloroethoxycarbonyl-5-thia-1-aza-bicyclo[4,2,0]oct-2-ene (450 mg) is obtained in the form of a light maroon solid, the characteristics of which are as Follows:RF = 0.63 [silica gel; chloroform/ethyl acetate (80/20 by volume)]

Workup

  1. customAfter removing the liquid phase
  2. customby decanting
  3. customthis product is triturated in water (50 cc.)
  4. washThe organic phase is washed with water (3 times 200 cc.)
  5. dry with materialdried over sodium sulphate
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure (12 mm Hg) at 30°C
  8. customThe solid obtained
  9. customthe solution obtained
  10. customis chromatographed on a column of silica gel (20 g) (0.05-0.20 mm
  11. washElution
  12. additiona mixture of benzene and ethyl acetate (99.5/0.5 by volume) (300 cc.)
  13. additiona mixture of benzene and ethyl acetate (99/1 by volume) (600 cc.)
  14. customcollecting 25 cc
  15. concentrationconcentrated to dryness under reduced pressure (12 mm Hg) at 30°C

Sources & evidence

ORD record
ord-7af9722c1f8c4a999368be8d66ed3960
Source dataset
uspto-grants-1976_08
Patent number
US03975385

Reaction notes

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