Formic Acid → HCID 12764266, compound

HRID 597152Notes

Reaction equation

HRID 597152 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:16]([NH2:17])[C:15](=[O:18])[N:10]2[C:11]=1[C:12]([OH:14])=[O:13])(=[O:3])[CH3:2].[CH:19](O)=[O:20].C(OCC)(=O)C>C(OC(=O)C)(=O)C>[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:16]([NH:17][CH:19]=[O:20])[C:15](=[O:18])[N:10]2[C:11]=1[C:12]([OH:14])=[O:13])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 284Formic AcidHCID 8857Ethyl AcetateHCID 4413287-Aminocephalosporanic acid

Product 1

HCID 12764266HCID 12764266, compound

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent

Procedure

3-Acetoxymethyl-7β-aminoceph-3-em-4-carboxylic acid (50.0 g) was dissolved in acetic anhydride (75 ml.) and formic acid (400 ml.) with stirring at 20° C. When complete solution was obtained (~ 5 min.) the solvents were evaporated (rotary evaporator, oil-pump), leaving a gum which was shaken with ethyl acetate (250 ml.). The insoluble material was removed by filtration and the filtrate was evaporated to dryness leaving a gum which was triturated under ether and petroleum-ether (b.p. 40°-60°), giving 3-acetoxymethyl-7β-formamidoceph-3-em-4-carboxylic acid as a pale yellow powder (43.6 g.), TLC RF 0.19, [α]D20 + 113.5° (c 1.00, dioxan), λ max (pH6 buffer) 259 nm. (ε 8,400), νmax (Nujol) 1772 (β-lactam) 1748 (acetate), 1708 (carboxylic acid), 1654, 1548 cm.-1 (amide), τ (D2O with NaHCO3)1.67 (0.9-proton singlet: CHO), 1.75 (0.1-proton singlet: CHO), 4.20 (1-proton doublet, J 4.5 Hz.: C-7 H), 4.80 (1-proton doublet, J4.5 Hz.: C-6 H), 5.00, 5.26 [two 1-proton doublets (branches of a quartet), J 13 Hz: C-3 CH2 ], 6.24 6.64 [two 1-proton doublets (branches of a quartet), J 18 Hz.: C-2 H2 ] 7.86 (3-proton singlet: CH3CO) (there is evidence for "cis" and "trans" forms in the secondary amide part).

Workup

  1. customWhen complete solution was obtained (~ 5 min.) the solvents
  2. customwere evaporated
  3. custom(rotary evaporator, oil-pump)
  4. customleaving a gum which
  5. customThe insoluble material was removed by filtration
  6. customthe filtrate was evaporated to dryness
  7. customleaving a gum which
  8. customwas triturated under ether

Sources & evidence

ORD record
ord-fd3d53dba29d47bcaac6065b834610da
Source dataset
uspto-grants-1977_03
Patent number
US04013645

Reaction notes

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