Methanol → HCID 70562820, compound

HRID 127651Notes

Reaction equation

HRID 127651 reaction equation
[N+](C1C=CC(C[O:9][C:10]([C:12]2[N:17]3[C:18](=[O:31])[C@@H:19]([NH:20][C:21](=[O:30])[CH2:22][O:23][C:24]4[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=4)[C@H:16]3[S:15][CH2:14][C:13]=2[S:32][CH3:33])=[O:11])=CC=1)([O-])=O.O1CCCC1.CO>[Pd].O1CCCC1.CO>[CH3:33][S:32][C:13]1[CH2:14][S:15][C@@H:16]2[C@H:19]([NH:20][C:21](=[O:30])[CH2:22][O:23][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C:18](=[O:31])[N:17]2[C:12]=1[C:10]([OH:11])=[O:9]

Participants

6

Reactant 3

HCID 887MethanolHCID 8028TetrahydrofuranHCID 13178111HCID 13178111, compound

Product 1

HCID 70562820HCID 70562820, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

A solution of 53 mg of 3-methylthio-7β-phenoxyacetylamino-3-cephem-4-carboxylic acid p-nitrobenzyl ester in 5 ml of a warm 2:1 mixture of tetrahydrofurane and methanol is added to a mixture, which has been prehydrogenated for 30 minutes in a hydrogenation apparatus, of 51 mg of 5% strength palladium-on-charcoal catalyst in 1 ml of tetrahydrofurane/methanol, 1:1, and the mixture is hydrogenated for 4 hours whilst stirring. The solution is filtered, the catalyst is washed with 4 times 6 ml of ethyl acetate and the filtrate and the washing liquid are evaporated in vacuo. The residue is dissolved in methylene chloride and extracted with dilute aqueous sodium bicarbonate solution. The aqueous phase is extracted by shaking three times with methylene chloride and the yellow oil of the intermediate layer is discarded. The aqueous bicarbonate solution is cooled in an ice bath, covered with ethyl acetate and acidified to about pH 2 with 2 N hydrochloric acid. The organic phase is separated off, the yellow oil of the intermediate layer is again discarded and the aqueous phase is extracted with methylene chloride. The combined ethyl acetate and methylene chloride phases are washed with water, dried over sodium sulphate and evaporated in vacuo. The residue is recrystallised from methylene chloride/diethyl ether and gives 3-methylthio-7β-phenoxyacetylamino-3-cephem-4-carboxylic acid of melting point 122°-125° C.; IR spectrum (KBr): characteristic bands at 5.64; 5.95; 6.25; 6.55; 6.70; 8.20; 8.58; 8.94 and 13.25μ.

Workup

  1. additionis added to a mixture, which
  2. filtrationThe solution is filtered
  3. washthe catalyst is washed with 4 times 6 ml of ethyl acetate
  4. customthe filtrate and the washing liquid are evaporated in vacuo
  5. dissolutionThe residue is dissolved in methylene chloride
  6. extractionextracted with dilute aqueous sodium bicarbonate solution
  7. extractionThe aqueous phase is extracted
  8. stirringby shaking three times with methylene chloride
  9. temperatureThe aqueous bicarbonate solution is cooled in an ice bath
  10. customThe organic phase is separated off
  11. extractionthe aqueous phase is extracted with methylene chloride
  12. washThe combined ethyl acetate and methylene chloride phases are washed with water
  13. dry with materialdried over sodium sulphate
  14. customevaporated in vacuo
  15. customThe residue is recrystallised from methylene chloride/diethyl ether

Sources & evidence

ORD record
ord-3a280a093788416b94c4845b952dd208
Source dataset
uspto-grants-1981_03
Patent number
US04256739

Reaction notes

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