Trifluoroacetic acid → HCID 131710262, compound

HRID 1657389Notes

Reaction equation

HRID 1657389 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[CH2:16][C:15](=[O:17])[N:10]2[C:11]=1[C:12]([O-:14])=[O:13])(=[O:3])[NH2:2].P(Cl)(Cl)(Cl)(Cl)Cl.N1C2C(=CC=CC=2)C=CC=1.C[O-].[Li+].[Li].FC(F)(F)[C:40](O)=[O:41]>O1CCCC1.CO>[CH3:40][O:41][C@H:16]1[C:15](=[O:17])[N:10]2[C:11]([C:12]([OH:14])=[O:13])=[C:6]([CH2:5][O:4][C:1](=[O:3])[NH2:2])[CH2:7][S:8][C@H:9]12

Participants

9

Reactant 6

HCID 6422Trifluoroacetic acidHCID 7047QuinolineHCID 24819Phosphorus pentachlorideHCID 3028194LithiumHCID 4177230Lithium methanolateHCID 131710263HCID 131710263, compound

Product 1

HCID 131710262HCID 131710262, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

Benzhydryl 7-(1',2'-dichloro-2'-α-thienylethylidenimino)-3-carbamoyloxymethyl-3-cephem-4-carboxylate was prepared from benzhydryl 7β-)α-thienylchloroacetamido)-3-carbamoyloxymethyl-3-cephem-4-carboxylate(597 mg), phosphorus pentachloride(220 mg) and quinoline(0.15 ml) according to the same procedure as in Example 23 - (1) and dissolved in tetrahydrofuran(40 ml). To the solution was added a methanol solution of lithium methoxide prepared from lithium(12 mg) and methanol(4 ml) at -70°C. The reaction mixture was stirred at -70°C. for 30 minutes. After the addition of trifluoroacetic acid (5 ml) the solution was stirred at room temperature for 40 minutes. The solution was evaporated under reduced pressure to dryness and the residue was extracted with ethyl acetate, which was re-extracted with a pH 7.5 buffer (disodium hydrogen phosphate-potassium dihydrogen phosphate). The aqueous extracts were acidified to pH 2.0 with diluted hydrochloric acid and extracted with ethyl acetate. The combined extracts were washed with water, dried over magnesium sulfate and evaporated to give 60 mg of 7β-)α-thienylacetamido)-7α-methoxy-3-carbamoyloxymethyl-3-cephem-4-carboxylic acid. IR νmaxNujol cm-1 : 3420, 3330, 3230, 1783, 1715, 1680, 1665. NMR(CD3CN) δ ppm: 3.53(3H, singlet), 3.38(1H, doublet, J=18 Hz), 3.60(1H, doublet, J=18 Hz), 3.90(2H, singlet), 4.88(2H, singlet), 5.07(1H, singlet), 6.95-7.40(3H, multiplet).

Workup

  1. stirringwas stirred at room temperature for 40 minutes
  2. customThe solution was evaporated under reduced pressure to dryness
  3. extractionthe residue was extracted with ethyl acetate, which
  4. extractionwas re-extracted with a pH 7.5 buffer (disodium hydrogen phosphate-potassium dihydrogen phosphate)
  5. extractionextracted with ethyl acetate
  6. washThe combined extracts were washed with water
  7. dry with materialdried over magnesium sulfate
  8. customevaporated

Sources & evidence

ORD record
ord-9a23edc86682474d86ce28ffd0e8c4dc
Source dataset
uspto-grants-1976_06
Patent number
US03960845

Reaction notes

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