Benzaldehyde → Diphenylmethyl 7-Benzylideneamino-3-(3-chloro-1-propen-1-yl)-3-cephem-4-carboxylate

HRID 580213Notes

Reaction equation

HRID 580213 reaction equation
[NH2:1][CH:2]1[C:29](=[O:30])[N:4]2[C:5]([C:13]([O:15][CH:16]([C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)[C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)=[O:14])=[C:6]([CH:9]=[CH:10][CH2:11][Cl:12])[CH2:7][S:8][C@H:3]12.[CH:31](=O)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.[OH-].[Na+]>C(OCC)(=O)C>[CH:31](=[N:1][CH:2]1[C:29](=[O:30])[N:4]2[C:5]([C:13]([O:15][CH:16]([C:23]3[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=3)[C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=3)=[O:14])=[C:6]([CH:9]=[CH:10][CH2:11][Cl:12])[CH2:7][S:8][C@H:3]12)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1

Participants

5

Reactant 3

HCID 240BenzaldehydeHCID 14798Sodium HydroxideHCID 131715606Diphenylmethyl 7-Amino-3-(3-chloro-1-propen-1-yl)-3-cephem-4-carboxylate

Product 1

HCID 131715607Diphenylmethyl 7-Benzylideneamino-3-(3-chloro-1-propen-1-yl)-3-cephem-4-carboxylateYield 111%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To an ice-cooled mixture of the crystalline 7-aminocephem intermediate XVIII (Z isomer) (13.4 g, 28 mmole) and benzaldehye (3.3 g, 31 mmole) in ethyl acetate (150 ml) was added dropwise 0.5N sodium hydroxide (56 ml, 28 mmole) over a period of 20 minutes, to maintain the temperature of the reaction mixture below 10° C. The mixture was stirred with cooling for another 15 minutes, and the organic layer was separated, washed with saturated aqueous sodium bicarbonate (100 ml×2) and dried over magnesium sulfate. To the dried solution was added a small amount of charcoal and the mixture was filtered. The filtrate was concentrated to dryness. The residual oil was dissolved in carbon tetrachloride (50 ml), and concentrated again. This procedure was repeated 3 times, and the mixture was monitored by reverse phase tlc to confirm that all of the starting 7-aminocephalosporin was converted to the Schiff's base. Removing the solvent in vacuo gave 16.45 g of the title compound XVII (Z isomer) as a pale yellow powder (estimated purity 85%; M.p. 74° C. (dec.), which was used for the next step without purification.

Workup

  1. temperatureto maintain the temperature of the reaction mixture below 10° C
  2. temperaturewith cooling for another 15 minutes
  3. customthe organic layer was separated
  4. washwashed with saturated aqueous sodium bicarbonate (100 ml×2)
  5. dry with materialdried over magnesium sulfate
  6. additionTo the dried solution was added a small amount of charcoal
  7. filtrationthe mixture was filtered
  8. concentrationThe filtrate was concentrated to dryness
  9. dissolutionThe residual oil was dissolved in carbon tetrachloride (50 ml)
  10. concentrationconcentrated again
  11. customRemoving the solvent in vacuo

Sources & evidence

ORD record
ord-dfe17b7902b845bb94837b2ee87b4c4f
Source dataset
uspto-grants-1988_06
Patent number
US04751295

Reaction notes

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