Ethanol → HCID 70562820, compound

HRID 127652Notes

Reaction equation

HRID 127652 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.C(O)C>[Pd].O1CCCC1.C(O)C>[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 702EthanolHCID 8028TetrahydrofuranHCID 13178111HCID 13178111, compound

Product 1

HCID 70562820HCID 70562820, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21873804Tetrahydrofuran ethanolSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2.6 g (5 mmols) of 3-methylthio-7β-phenoxyacetylamino-3-cephem-4-carboxylic acid p-nitrobenzyl ester in 75 ml of a warm 5:1 mixture of tetrahydrofurane and ethanol is added to a mixture, which has been pre-hydrogenated for 30 minutes in a hydrogenation apparatus, of 2.5 g of 5% strength palladium-on-charcoal catalyst in 10 ml of tetrahydrofurane/ethanol, 1:1, and the mixture is hydrogenated for 4 hours whilst stirring. The solution is filtered, the catalyst is washed with ethyl acetate and the filtrate and washing liquor are combined, washed successively with an aqueous citric acid solution and water and then extracted several times with 5% strength aqueous sodium bicarbonate solution. The bicarbonate extracts are combined, washed with methylene chloride, cooled to 0° C., slowly acidified with 2 N hydrochloric acid and extracted with ethyl acetate. The organic phase is washed with water and saturated aqueous sodium chloride solution, dried over sodium sulphate, filtered and evaporated. The residue is recrystallised from methylene chloride/diethyl ether and gives 3-methylthio-7β-phenoxyacetylamino-3-cephem-4-carboxylic acid of melting point 164°-166° C. (decomposition); [α]D20 =+109°±1° (c=1; dioxane); thin layer chromatogram: silica gel (toluene/ethyl acetate/water, 5:5:1) Rf=0.16; UV spectrum (ethanol); λmax =269 nm (ε=4800), 276 nm (ε=5200) and 308 nm (ε=7700); IR spectrum (KBr): characteristic bands at 3.00; 3.40; 5.63; 5.91; 6.25; 6.53; 6.68; 8.20; 8.55; 8.90; 9.25; 9.43; 13.20 and 14.45μ.

Workup

  1. additionis added to a mixture, which
  2. filtrationThe solution is filtered
  3. washthe catalyst is washed with ethyl acetate
  4. washthe filtrate and washing liquor
  5. washwashed successively with an aqueous citric acid solution and water
  6. extractionextracted several times with 5% strength aqueous sodium bicarbonate solution
  7. washwashed with methylene chloride
  8. extractionextracted with ethyl acetate
  9. washThe organic phase is washed with water and saturated aqueous sodium chloride solution
  10. dry with materialdried over sodium sulphate
  11. filtrationfiltered
  12. customevaporated
  13. customThe residue is recrystallised from methylene chloride/diethyl ether

Sources & evidence

ORD record
ord-658a0b74799d45c68ff053e923e625f1
Source dataset
uspto-grants-1981_03
Patent number
US04256739

Reaction notes

Loading…