Water → Benzhydryl 3-formyl-7-(2-thienylacetamido)-3-cephem-4-carboxylate-1-oxide

HRID 1605405Notes

Reaction equation

HRID 1605405 reaction equation
[OH:1][CH2:2][C:3]1[CH2:4][S:5](=[O:37])[C@@H:6]2[CH:26]([NH:27][C:28](=[O:35])[CH2:29][C:30]3[S:31][CH:32]=[CH:33][CH:34]=3)[C:25](=[O:36])[N:7]2[C:8]=1[C:9]([O:11][CH:12]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:10].C(OCC)(=O)C.O>CC(C)=O.OS(O)(=O)=O>[CH:2]([C:3]1[CH2:4][S:5](=[O:37])[C@@H:6]2[CH:26]([NH:27][C:28](=[O:35])[CH2:29][C:30]3[S:31][CH:32]=[CH:33][CH:34]=3)[C:25](=[O:36])[N:7]2[C:8]=1[C:9]([O:11][CH:12]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)=[O:10])=[O:1]

Participants

6

Reactant 3

HCID 962WaterHCID 8857Ethyl AcetateHCID 70535309Benzhydryl 3-hydroxymethyl-7-(2-thienylacetamido)-3-cephem-4-carboxylate-1-oxide

Product 1

HCID 88803489Benzhydryl 3-formyl-7-(2-thienylacetamido)-3-cephem-4-carboxylate-1-oxideYield 39.4%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 1118Sulfuric AcidSolvent

Procedure

As described in Belgian Patent 770,531, to a solution of 1.80 g (3.4 mmole) of benzhydryl 3-hydroxymethyl-7-(2-thienylacetamido)-3-cephem-4-carboxylate-1-oxide in 100 ml of acetone at 0° was added over the period of 2 min. 0.90 ml of 8N CrO3 in H2SO4 and the mixture was stirred at 0° for 5 min., then poured into a mixture of 300 ml ethyl acetate and 300 ml of water and the ethyl acetate layer was washed with water, dried (MgSO4) and evaporated in vacuo. The residue was chromatographed on silica with CHCl3 to yield 0.716 g of benzhydryl 3-formyl-7-(2-thienylacetamido)-3-cephem-4-carboxylate-1-oxide after crystallization from methanol; uv max (C2H5OH): 269 nm (4600), 292 nm (4300), and 355 nm (1760); nmr (dmso-d6): 3.75 and 4.32 (AB, 2 (JAB = 19 Hz), C2 -CH2), 3.88 (s, 2, α-thienyl CH2), 5.08 (d, 1 (J = 5 Hz), C6 -H), 6.18 (dd, 1 (J = 5 Hz, J' = 8.5 Hz), C -H), 7.17 (1, s, -CO2CH Ph2), 7.02 (d, 2 (J = 3.0 Hz), thiophene 3- and 5-H), 7.44 (10, s, phenyl-H), 8.72 (d, 1 (J = 8.5 Hz), amide N-H), and 9.85 (s, 1, aldehyde-H).

Workup

  1. additionwas added over the period of 2 min
  2. washthe ethyl acetate layer was washed with water
  3. dry with materialdried (MgSO4)
  4. customevaporated in vacuo
  5. customThe residue was chromatographed on silica with CHCl3

Sources & evidence

ORD record
ord-6705da2507c84a3aa47a5ea45f939969
Source dataset
uspto-grants-1976_04
Patent number
US03950329

Reaction notes

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