Trifluoroacetic acid → 7-[2-(5-amino-1,2,4-thiadiazol-3-yl)-2-allyloxyiminoacetamido]-3-[(Z)-2-phenylvinylthiomethyl]-3-cephem-4-carboxylic acid

HRID 1731691Notes

Reaction equation

HRID 1731691 reaction equation
[NH2:1][C:2]1[S:6][N:5]=[C:4]([C:7](=[N:46][O:47][CH2:48][CH:49]=[CH2:50])[C:8]([NH:10][CH:11]2[C:44](=[O:45])[N:13]3[C:14]([C:28]([O:30]C(C4C=CC=CC=4)C4C=CC=CC=4)=[O:29])=[C:15]([CH2:18][S:19]/[CH:20]=[CH:21]\[C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)[CH2:16][S:17][C@H:12]23)=[O:9])[N:3]=1.C1(OC)C=CC=CC=1.C1(SC)C=CC=CC=1.FC(F)(F)C(O)=O.C(OC(C)C)(C)C>C(Cl)Cl>[NH2:1][C:2]1[S:6][N:5]=[C:4]([C:7](=[N:46][O:47][CH2:48][CH:49]=[CH2:50])[C:8]([NH:10][CH:11]2[C:44](=[O:45])[N:13]3[C:14]([C:28]([OH:30])=[O:29])=[C:15]([CH2:18][S:19]/[CH:20]=[CH:21]\[C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)[CH2:16][S:17][C@H:12]23)=[O:9])[N:3]=1

Participants

7

Reactant 5

HCID 6422Trifluoroacetic acidHCID 7519AnisoleHCID 7520ThioanisoleHCID 7914Diisopropyl EtherHCID 131714954benzhydryl 7-[2-(5-amino-1,2,4-thiadiazol-3-yl)-2-allyloxyiminoacetamido]-3-[(Z)-2-phenylvinylthiomethyl]-3-cephem-4-carboxylate

Product 1

HCID 1317149537-[2-(5-amino-1,2,4-thiadiazol-3-yl)-2-allyloxyiminoacetamido]-3-[(Z)-2-phenylvinylthiomethyl]-3-cephem-4-carboxylic acidYield 35.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of benzhydryl 7-[2-(5-amino-1,2,4-thiadiazol-3-yl)-2-allyloxyiminoacetamido]-3-[(Z)-2-phenylvinylthiomethyl]-3-cephem-4-carboxylate (syn isomer) (748 mg) in a mixture of methylene chloride (2.24 ml), anisole (0.37 ml) and thioanisole (0.37 ml) was added trifluoroacetic acid (1.5 ml) under ice-cooling. The mixture was stirred for 30 minutes at the same temperature and poured into diisopropyl ether (50 ml). The resulting precipitate was collected, washed with diisopropyl ether and dissolved in a mixture of ethyl acetate and an aqueous solution of sodium bicarbonate at pH 7. The aqueous layer was separated, adjusted to pH 6.2 with diluted hydrochloric acid and extracted with ethyl acetate three times. The extract was dried over magnesium sulfate and concentrated in vacuo. The residue was triturated in diisopropyl ether to give 7-[2-(5-amino-1,2,4-thiadiazol-3-yl)-2-allyloxyiminoacetamido]-3-[(Z)-2-phenylvinylthiomethyl]-3-cephem-4-carboxylic acid (syn isomer) (207 mg).

Workup

  1. temperaturecooling
  2. customThe resulting precipitate was collected
  3. washwashed with diisopropyl ether
  4. dissolutiondissolved in a mixture of ethyl acetate
  5. customThe aqueous layer was separated
  6. extractionextracted with ethyl acetate three times
  7. dry with materialThe extract was dried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue was triturated in diisopropyl ether

Sources & evidence

ORD record
ord-eda9a47ab20448588b006378fc86d13f
Source dataset
uspto-grants-1986_11
Patent number
US04622318

Reaction notes

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