2,2,2-Trichloroethyl chloroformate → HCID 70611649, compound

HRID 1679574Notes

Reaction equation

HRID 1679574 reaction equation
[O:1]([CH2:8][C:9]([NH:11][CH:12]1[C:33](=[O:34])[N:14]2[CH:15]([C:20]([O:22][CH2:23][C:24]3[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=3)=[O:21])[C:16]([CH3:19])([CH3:18])[S:17][C@H:13]12)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl[C:36]([O:38][CH2:39][C:40]([Cl:43])([Cl:42])[Cl:41])=[O:37]>C(Cl)Cl>[O:1]([CH2:8][C:9]([N:11]([CH:12]1[C:33](=[O:34])[N:14]2[CH:15]([C:20]([O:22][CH2:23][C:24]3[CH:25]=[CH:26][C:27]([N+:30]([O-:32])=[O:31])=[CH:28][CH:29]=3)=[O:21])[C:16]([CH3:18])([CH3:19])[S:17][C@H:13]12)[C:36]([O:38][CH2:39][C:40]([Cl:43])([Cl:42])[Cl:41])=[O:37])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 870632,2,2-Trichloroethyl chloroformateHCID 70545852HCID 70545852, compound

Product 1

HCID 70611649HCID 70611649, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of 4.855 gms. (10 mmol.) of p-nitrobenzyl 6-phenoxyacetamido-2,2-dimethylpenam-3-carboxylate, 16.94 gms. (80 mmol.) of 2,2,2-trichloroethyl chloroformate, 18 ml. of N,O-(bis-trimethylsilyl)trifluoromethylacetamide, and 20ml. of methylene chloride was prepared. The mixture was permitted to stand at room temperature overnight. The mixture then was heated at reflux for 7 hours after which it was again permitted to stand at room temperature overnight. Heating then was continued for an additional 6 hours. The mixture then was evaporated to a residue, and the residue was dissolved in benzene which then was added to a large excess of heptane. The resulting insoluble material was filtered off, dissolved in benzene, and chromatographed over silica gel using a benzene-ethyl acetate elution gradient. p-Nitrobenzyl 6-[N-(phenoxyacetyl)-N-(2,2,2-trichloroethoxycarbonyl)amino]-2,2-dimethylpenam-3-carboxylate (4.76 gms.; 72 percent) was obtained as product.

Workup

  1. additionA mixture of 4.855 gms
  2. temperatureThe mixture then was heated
  3. temperatureat reflux for 7 hours after which it
  4. waitto stand at room temperature overnight
  5. temperatureHeating
  6. waitthen was continued for an additional 6 hours
  7. customThe mixture then was evaporated to a residue
  8. dissolutionthe residue was dissolved in benzene which
  9. additionthen was added to a large excess of heptane
  10. filtrationThe resulting insoluble material was filtered off
  11. dissolutiondissolved in benzene
  12. customchromatographed over silica gel using
  13. washa benzene-ethyl acetate elution gradient

Sources & evidence

ORD record
ord-66ff4b6c7fb44136abf7f91980239fbb
Source dataset
uspto-grants-1978_03
Patent number
US04081440

Reaction notes

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