Diphenylmethyl 3-acetoxymethyl-7beta-[2-(4-nitrobenzoyloxyimino)-2-phenylacetamido)ceph-3-em-4-carboxylate → 3-Acetoxymethyl-7beta-[2-(4-nitrobenzoyloxyimino)-2-phenyl-acetamido]ceph-3-em-4-carboxylic acid

HRID 1707193Notes

Reaction equation

HRID 1707193 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:29]([NH:30][C:31](=[O:52])[C:32](=[N:39][O:40][C:41](=[O:51])[C:42]3[CH:47]=[CH:46][C:45]([N+:48]([O-:50])=[O:49])=[CH:44][CH:43]=3)[C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C:28](=[O:53])[N:10]2[C:11]=1[C:12]([O:14]C(C1C=CC=CC=1)C1C=CC=CC=1)=[O:13])(=[O:3])[CH3:2]>FC(F)(F)C(O)=O>[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:29]([NH:30][C:31](=[O:52])[C:32](=[N:39][O:40][C:41](=[O:51])[C:42]3[CH:43]=[CH:44][C:45]([N+:48]([O-:50])=[O:49])=[CH:46][CH:47]=3)[C:33]3[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=3)[C:28](=[O:53])[N:10]2[C:11]=1[C:12]([OH:14])=[O:13])(=[O:3])[CH3:2]

Participants

3

Reactant 1

HCID 131710763Diphenylmethyl 3-acetoxymethyl-7beta-[2-(4-nitrobenzoyloxyimino)-2-phenylacetamido)ceph-3-em-4-carboxylate

Product 1

HCID 1317107643-Acetoxymethyl-7beta-[2-(4-nitrobenzoyloxyimino)-2-phenyl-acetamido]ceph-3-em-4-carboxylic acidYield 20%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

A solution of diphenylmethyl 3-acetoxymethyl-7β-[2-(4-nitrobenzoyloxyimino)-2-phenylacetamido]ceph-3-em-4-carboxylate (syn-isomer) (1.0 g) in trifluoroacetic acid (10 ml.) was allowed to stand at room temperature for ten minutes. After evaporation of trifluoroacetic acid under reduced pressure, the residue was dissolved in ethyl acetate and extracted with saturated aqueous sodium bicarbonate. A solid precipitated during the bicarbonate extraction and was collected, washed with water and ethyl acetate, and partitioned between ethyl acetate and 2 -N-hydrochloric acid. The phases were separated and the upper layer was washed with water, dried, concentrated to ca. 10 ml. and added dropwise with stirring to petroleum (b.p. 40°-60°; 200 ml.). The precipitated solid was filtered and dried to give 3-acetoxymethyl-7β-[2-(4-nitrobenzoyloxyimino)-2-phenylacetamido]ceph-3-em-4-carboxylic acid (syn-isomer) (0.150 g; 20%), [α]D +17° (c 0.8, DMSO), λmax. (EtOH) 266.5 nm (ε 33,000), νmax. (Nujol) 3270 (NH), 1780 (β-lactam) 1520 and 1338 (NO2), 1675 and 1520 cm.-1 (CONH), τ (DMSO-d6) values include 1.58 and 1.69 (two doublets J 8 Hz; p-substituted phenyl), 2.1 to 2.5 (multiplet; aromatic protons), 7.79 (singlet; OCOCH3).

Workup

  1. waitto stand at room temperature for ten minutes
  2. customAfter evaporation of trifluoroacetic acid under reduced pressure
  3. dissolutionthe residue was dissolved in ethyl acetate
  4. extractionextracted with saturated aqueous sodium bicarbonate
  5. customA solid precipitated during the bicarbonate extraction
  6. customwas collected
  7. washwashed with water and ethyl acetate
  8. custompartitioned between ethyl acetate and 2 -N-hydrochloric acid
  9. customThe phases were separated
  10. washthe upper layer was washed with water
  11. customdried
  12. concentrationconcentrated to ca. 10 ml
  13. additionand added dropwise
  14. filtrationThe precipitated solid was filtered
  15. customdried

Sources & evidence

ORD record
ord-079c5bea92374bd4aaf36eae4c5a9954
Source dataset
uspto-grants-1980_06
Patent number
US04209616

Reaction notes

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