Acetic Acid → HCID 131712007, compound

HRID 1733740Notes

Reaction equation

HRID 1733740 reaction equation
[S:1]1[CH:6]=[C:5]([C:7](=[N:33][O:34][CH3:35])[C:8]([NH:10][CH:11]2[C:31](=[O:32])[N:13]3[C:14]([C:18]([O:20]CC4C=CC([N+]([O-])=O)=CC=4)=[O:19])=[CH:15][CH2:16][S:17][C@H:12]23)=[O:9])[S:4][CH2:3][CH2:2]1.CO.O1CCCC1.C(O)(=O)C>[C].[Pd].O>[S:1]1[CH:6]=[C:5]([C:7](=[N:33][O:34][CH3:35])[C:8]([NH:10][CH:11]2[C:31](=[O:32])[N:13]3[C:14]([C:18]([OH:20])=[O:19])=[CH:15][CH2:16][S:17][C@H:12]23)=[O:9])[S:4][CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 887MethanolHCID 8028TetrahydrofuranHCID 131712008HCID 131712008, compound

Product 1

HCID 131712007HCID 131712007, compoundYield 60.1%

Reagents, catalysts & solvents 2

HCID 178418390HCID 178418390, compoundCatalystHCID 962WaterSolvent

Procedure

Palladium carbon (0.8 g.) was added to a mixture of 4-nitrobenzyl 7-[2-(2,3-dihydro-1,4-dithiin-5-yl)-2-methoxyiminoacetamido]-3-cephem-4-carboxylate (syn isomer, 2.0 g.), methanol (20 ml.), tetrahydrofuran (40 ml.), acetic acid (0.3 ml.) and water (3 ml.), and subjected to catalytic reduction under ordinary pressure at room temperature for 4 hours. After removing the catalyst from the resultant mixture by filtration, the filtrate was concentrated at 40° C. in vacuo. Ethyl acetate (20 ml.) was added to the residue, and the solution was adjusted to pH 6.5 to 7.0 with a saturated aqueous solution of sodium bicarbonate, stirred for 30 minutes and then filtered. The insoluble product was washed with water (10 ml.). The filtrate and washings were combined together, and the aqueous layer was separated washed with ethyl acetate and adjusted to pH 5.0 with 10% hydrochloric acid. The solution was treated with activated charcoal (0.1 g.) for 5 minutes and then filtered in vacuo. The filtrate was washed with diethyl ether and the organic solvent was removed by introducing nitrogen gas. The aqueous layer was adjusted to pH 2.0 with 10% hydrochloric acid under ice cooling and extracted with ethyl acetate (50 ml.) twice. The extract was washed with ice-water, dried over magnesium sulfate and filtered. The filtrate was concentrated at 40° C. in vacuo and the residue was crystallized with diethyl ether (30 ml.). The crystals were collected by filtration, washed with diethyl ether and dried to give 7-[2-(2,3-dihydro-1,4-dithiin-5-yl)-2-methoxyiminoacetamido]-3-cephem-4-carboxylic acid (syn isomer, 0.9 g.), pale yellow powder.

Workup

  1. customAfter removing the catalyst from the resultant mixture
  2. filtrationby filtration
  3. concentrationthe filtrate was concentrated at 40° C. in vacuo
  4. additionEthyl acetate (20 ml.) was added to the residue
  5. filtrationfiltered
  6. washThe insoluble product was washed with water (10 ml.)
  7. customthe aqueous layer was separated
  8. washwashed with ethyl acetate
  9. additionThe solution was treated with activated charcoal (0.1 g.) for 5 minutes
  10. filtrationfiltered in vacuo
  11. washThe filtrate was washed with diethyl ether
  12. customthe organic solvent was removed
  13. additionby introducing nitrogen gas
  14. extractionextracted with ethyl acetate (50 ml.) twice
  15. washThe extract was washed with ice-water
  16. dry with materialdried over magnesium sulfate
  17. filtrationfiltered
  18. concentrationThe filtrate was concentrated at 40° C. in vacuo
  19. customthe residue was crystallized with diethyl ether (30 ml.)
  20. filtrationThe crystals were collected by filtration
  21. washwashed with diethyl ether
  22. customdried

Sources & evidence

ORD record
ord-0077c83121104595a6947f4649954326
Source dataset
uspto-grants-1980_12
Patent number
US04242510

Reaction notes

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