Trifluoroacetic acid → 7-[2-(6-Aminopyridin-2-yl)-2-carboxymethoxyiminoacetamido]-3-vinyl-3-cephem-4-carboxylic acid

HRID 1195562Notes

Reaction equation

HRID 1195562 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([C:8](=[N:39][O:40][CH2:41][C:42]([O:44]C(C)(C)C)=[O:43])[C:9]([NH:11][CH:12]2[C:37](=[O:38])[N:14]3[C:15]([C:21]([O:23]C(C4C=CC=CC=4)C4C=CC=CC=4)=[O:22])=[C:16]([CH:19]=[CH2:20])[CH2:17][S:18][C@H:13]23)=[O:10])[CH:5]=[CH:4][CH:3]=1.C1(OC)C=CC=CC=1.FC(F)(F)C(O)=O>C(OC(C)C)(C)C>[NH2:1][C:2]1[N:7]=[C:6]([C:8](=[N:39][O:40][CH2:41][C:42]([OH:44])=[O:43])[C:9]([NH:11][CH:12]2[C:37](=[O:38])[N:14]3[C:15]([C:21]([OH:23])=[O:22])=[C:16]([CH:19]=[CH2:20])[CH2:17][S:18][C@H:13]23)=[O:10])[CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 7519AnisoleHCID 131713202Benzhydryl 7-[2-(6-aminopyridin-2-yl)-2-tert-butoxycarbonylmethoxyiminoacetamido]-3-vinyl-3-cephem-4-carboxylate

Product 1

HCID 1317132017-[2-(6-Aminopyridin-2-yl)-2-carboxymethoxyiminoacetamido]-3-vinyl-3-cephem-4-carboxylic acidYield 59.9%

Reagents, catalysts & solvents 1

HCID 7914Diisopropyl EtherSolvent

Procedure

A mixture of benzhydryl 7-[2-(6-aminopyridin-2-yl)-2-tert-butoxycarbonylmethoxyiminoacetamido]-3-vinyl-3-cephem-4-carboxylate (syn isomer) (6.0 g), anisole (10 ml) and trifluoroacetic acid (60 ml) was stirred at ambient temperature for an hour. The reaction mixture was poured into diisopropyl ether (600 ml) with stirring, and the precipitated substance was collected by filtration, washed with diisopropyl ether and the dissolved in water (100 ml), followed by adjusting to pH 7.5 with 5% aqueous sodium bicarbonate and washing with ethyl acetate (50 ml). The resultant aqueous solution was adjusted to pH 2.5 with conc. hydrochloric acid, and extracted with ethyl acetate (200 ml) and tetrahydrofuran (200 ml). The remaining aqueous solution was further adjusted to pH 1.5 with conc. hydrochloric acid and extracted with tetrahydrofuran (100 ml). The combined extracts were washed with a saturated aqueous sodium chloride and then dried over magnesium sulfate. Removal of the solvent gave a residue, which was washed with acetone and diisopropyl ether to obtain 7-[2-(6-aminopyridin-2-yl)-2-carboxymethoxyiminoacetamido]-3-vinyl-3-cephem-4-carboxylic acid (syn isomer) (2.4 g), mp 173°-178° C. (dec.).

Workup

  1. stirringwith stirring
  2. filtrationthe precipitated substance was collected by filtration
  3. washwashed with diisopropyl ether
  4. dissolutionthe dissolved in water (100 ml)
  5. washwashing with ethyl acetate (50 ml)
  6. extractionextracted with ethyl acetate (200 ml) and tetrahydrofuran (200 ml)
  7. extractionextracted with tetrahydrofuran (100 ml)
  8. washThe combined extracts were washed with a saturated aqueous sodium chloride
  9. dry with materialdried over magnesium sulfate
  10. customRemoval of the solvent
  11. customgave a residue, which
  12. washwas washed with acetone and diisopropyl ether

Sources & evidence

ORD record
ord-82f0d0bbc2844825a2277430038d0435
Source dataset
uspto-grants-1992_05
Patent number
US05110921

Reaction notes

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