Phosphoric Acid → 2,2,2-Trichloroethyl 2-methyl-2,3-methylene-6-(2-phenylacetamido)penam-3-carboxylate

HRID 1287320Notes

Reaction equation

HRID 1287320 reaction equation
[CH3:1][C:2]1([CH2:28]Br)[CH:6]([C:7]([O:9][CH2:10][C:11]([Cl:14])([Cl:13])[Cl:12])=[O:8])[N:5]2[C:15](=[O:27])[CH:16]([NH:17][C:18](=[O:26])[CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C@H:4]2[S:3]1.C(OCC)(=O)C.P(=O)(O)(O)O>CN(C)C=O>[CH3:1][C:2]12[CH2:28][C:6]1([C:7]([O:9][CH2:10][C:11]([Cl:14])([Cl:13])[Cl:12])=[O:8])[N:5]1[C:15](=[O:27])[CH:16]([NH:17][C:18](=[O:26])[CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C@H:4]1[S:3]2

Participants

5

Reactant 3

HCID 1004Phosphoric AcidHCID 8857Ethyl AcetateHCID 128952622,2,2-Trichloroethyl 2-bromomethyl-2-methyl-6-(2-phenylacetamido)penam-3-carboxylate

Product 1

HCID 128339582,2,2-Trichloroethyl 2-methyl-2,3-methylene-6-(2-phenylacetamido)penam-3-carboxylateYield 39.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
-10 °C

Procedure

To a solution of 2,2,2-trichloroethyl 2-methyl-2-bromomethyl-6-(2-phenylacetamido)penam-3-carboxylate(1.08 g.) in dimethylformamide (10 ml.) was added 1,8-diazabicyclo[5,4,0]undecene-7(360 mg.) under cooling at -50° to -60°C and stirred at the same temperature for an hour The inner temperature of the reaction mixture was raised to -10°C. The mixture was poured into a solution of ethyl acetate and dilute phosphoric acid and then extracted. The extract was washed with dilute phosphoric acid, water, a saturated aqueous solution of sodium bicarbonate and water in turn, treated with activated charcoal and dried over magnesium sulfate. After removing the solvent, the residue was purified by column chromatography on silica gel using chloroform as developing solvent to give 2,2,2-trichloroethyl 2-methyl-2,3-methylene-6-(2-phenylacetamido)penam-3-carboxylate(360 mg.), mp. 140° to 143°C.

Workup

  1. temperatureunder cooling at -50° to -60°C
  2. extractionextracted
  3. washThe extract was washed with dilute phosphoric acid, water
  4. additiona saturated aqueous solution of sodium bicarbonate and water in turn, treated with activated charcoal
  5. dry with materialdried over magnesium sulfate
  6. customAfter removing the solvent
  7. customthe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-87a7fa84456e487e9287195ea431add6
Source dataset
uspto-grants-1976_10
Patent number
US03984397

Reaction notes

Loading…