Bromhydrol → HCID 12834047, compound

HRID 1763999Notes

Reaction equation

HRID 1763999 reaction equation
[CH3:1][C:2]12[CH2:15][C:6]1([C:7]([O:9][CH2:10][C:11]([Cl:14])([Cl:13])[Cl:12])=[O:8])[N:5]1[C:16](=[O:29])[CH:17]([NH:18][C:19](=[O:28])[CH2:20][O:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C@H:4]1[S:3]2.[Br-].[Al+3].[Br-].[Br-]>ClCCl>[CH3:1][CH:2]1[CH:15]=[C:6]([C:7]([O:9][CH2:10][C:11]([Cl:13])([Cl:12])[Cl:14])=[O:8])[N:5]2[C:16](=[O:29])[CH:17]([NH:18][C:19](=[O:28])[CH2:20][O:21][C:22]3[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=3)[C@H:4]2[S:3]1

Participants

4

Reactant 2

HCID 166749BromhydrolHCID 70528477HCID 70528477, compound

Product 1

HCID 12834047HCID 12834047, compoundYield 64.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 2,2,2-trichloroethyl 2-methyl-2,3-methylene-6-(2-phenoxyacetamido)penam-3-carboxylate (1.39 g.) in dried dichloromethane (7 ml.) was dropwise added over 10 minutes at -10° C. to a solution of aluminum bromide (1.16 g.) in dried dichloromethane (12 ml.), and the reaction temperature was gradually elevated to room temperature, after which the mixture was stirred for 4 hours at room temperature. After the reaction, the reaction mixture was poured into ice-water (70 ml.) and the dichloromethane layer was separated, after which the aqueous layer was once extracted with chloroform. The combined dichloromethane and chloroform layer was washed in turn with water, 2% hydrochloric acid, water, a dilute sodium bicarbonate aqueous solution and water, and then dried over magnesium sulfate. After the solvent was distilled off, the obtained pale brown oil (1.2 g.) was crystallized by adding ether and a small amount of isopropyl ether. The crystals were collected by filtration, followed by washing with isopropyl ether and recrystallized from a mixture of benzene: isopropyl ether (1:3) to give colorless granules of 2,2,2-trichloroethyl 2-methyl-7-(2-phenoxyacetamido)-3-cephem-4-carboxylate (0.9 g.), mp 118° to 120° C.

Workup

  1. customwas gradually elevated to room temperature
  2. customAfter the reaction
  3. customthe dichloromethane layer was separated
  4. extractionafter which the aqueous layer was once extracted with chloroform
  5. washThe combined dichloromethane and chloroform layer was washed in turn with water, 2% hydrochloric acid, water
  6. dry with materiala dilute sodium bicarbonate aqueous solution and water, and then dried over magnesium sulfate
  7. distillationAfter the solvent was distilled off
  8. customthe obtained pale brown oil (1.2 g.) was crystallized
  9. additionby adding ether
  10. filtrationThe crystals were collected by filtration
  11. washby washing with isopropyl ether
  12. customrecrystallized from a mixture of benzene: isopropyl ether (1:3)

Sources & evidence

ORD record
ord-810eeb38215e4583aa22b35f5faa6596
Source dataset
uspto-grants-1978_09
Patent number
US04113940

Reaction notes

Loading…