Ethanol → HCID 70615714, compound

HRID 1763813Notes

Reaction equation

HRID 1763813 reaction equation
C(N(CC)CC)C.[CH3:8][SH:9].[Cl:10][C:11]([Cl:38])([Cl:37])[CH2:12][O:13][C:14]([C:16]1[N:21]2[C:22](=[O:34])[C@@H:23]([NH:24][C:25](=[O:33])[CH2:26][C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[C@H:20]2[S:19][CH2:18][C:17]=1[CH2:35]Br)=[O:15].C(O)C>CN(C)C=O>[CH3:8][S:9][CH2:35][C:17]1[CH2:18][S:19][C@@H:20]2[C@H:23]([NH:24][C:25](=[O:33])[CH2:26][C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[C:22](=[O:34])[N:21]2[C:16]=1[C:14]([O:13][CH2:12][C:11]([Cl:38])([Cl:37])[Cl:10])=[O:15]

Participants

6

Reactant 4

HCID 702EthanolHCID 878MethanethiolHCID 8471TriethylamineHCID 70615562HCID 70615562, compound

Product 1

HCID 70615714HCID 70615714, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

Triethylamine (0.70 ml, 5 mmole) and a solution of methanethiol (2.8 ml, ca. 10 equiv.) in dimethylformamide (10 ml,), previously cooled to -30°, were added to a solution of 2,2,2-trichloroethyl-3-bromomethyl-7β-phenylacetamidoceph-3-em-4-carboxylate, 1β-oxide (2.79 g, 5 mmole) in dimethylformamide (40 ml) cooled to -30°. The reaction solution was allowed to warm to 20° and then stirred at this temperature for 30 minutes then dilution of an aliquot with ethanol gave a solution with λmax. 274 nm. Nitrogen was passed through the dimethylformamide solution for 45 minutes to remove the excess of thiol and potassium iodide (5 g.) and acetyl chloride (5 ml.) were added. After 4 hours at 20°, t.l.c. (acetone-methylene chloride, 1:15) showed that reduction was complete. The solution was cooled in an ice-bath, and 0.1 N-sodium thiosulphate solution was added until the solution became pale-yellow. Methylene chloride and water (80 ml of each) were added and the aqueous layer was separated and reextracted with methylene chloride (100 ml.). The combined methylene chloride layers were washed with water (3 × 100 ml.), dried and evaporated to give the title ester as a solvated yellow gelatinous solid (2.76 g), λmax. 268 nm (E1cm1% 133).

Workup

  1. temperaturecooled to -30°
  2. temperatureto warm to 20°
  3. customto remove the excess of thiol and potassium iodide (5 g.) and acetyl chloride (5 ml.)
  4. additionwere added
  5. waitAfter 4 hours at 20°
  6. temperatureThe solution was cooled in an ice-bath
  7. addition0.1 N-sodium thiosulphate solution was added until the solution
  8. additionMethylene chloride and water (80 ml of each) were added
  9. customthe aqueous layer was separated
  10. washThe combined methylene chloride layers were washed with water (3 × 100 ml.)
  11. customdried
  12. customevaporated

Sources & evidence

ORD record
ord-d2c6a185de7a45cfac44b7668c3614a4
Source dataset
uspto-grants-1978_09
Patent number
US04113591

Reaction notes

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