Pyridine → HCID 53885382, compound

HRID 329236Notes

Reaction equation

HRID 329236 reaction equation
N1C=CC=CC=1.C(Cl)(Cl)=O.[C:11]([O:14][CH2:15][C:16]1[CH2:17][S:18][C@@H:19]2[C@H:39]([NH:40][CH:41]=O)[C:38](=[O:43])[N:20]2[C:21]=1[C:22]([O:24][CH:25]([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:23])(=[O:13])[CH3:12]>C(Cl)Cl>[C:11]([O:14][CH2:15][C:16]1[CH2:17][S:18][C@@H:19]2[C@H:39]([N+:40]#[C-:41])[C:38](=[O:43])[N:20]2[C:21]=1[C:22]([O:24][CH:25]([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:23])(=[O:13])[CH3:12]

Participants

5

Reactant 3

HCID 1049PyridineHCID 6371PhosgeneHCID 12764268HCID 12764268, compound

Product 1

HCID 53885382HCID 53885382, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Pyridine (8.1ml, 100mmole) and a solution of phosgene (2.94g, 29.7mmole) in dry methylene chloride (3.5ml) at -60° were added successively to a cold (-70°) solution of diphenylmethyl (6R,7R)-3-acetoxymethyl-7-formamidoceph-3-em-4-carboxylate (9.301g, 19.96mmole) in dry methylene chloride (150ml), under a dry nitrogen atmosphere. The reaction was allowed to warm to 0° and then partitioned between ethyl acetate (300ml) and water (100ml). The organic layer was washed with water (100ml) and combined with the ethyl acetate backwash (50ml) of the combined aqueous layers, dried, and then evaporated. The residual foam was dissolved in ethyl acetate (ca 50ml) and the solution slowly added to rapidly stirred petroleum ether (b.p. 60° to 80°). The petroleum ether was decanted from the precipitated solid which was dissolved in ethyl acetate (100ml). The solution was evaporated leaving the title compound as a pale-brown foam containing 1 /5 mole-equivalent of ethyl acetate (n.m.r., microanalysis) (7.176g, 15.4mmole, 77%), λmax 250.5nm (ε7,160); νmax 2153 (C≡N-), 1805 (azetidin-2-one), 1740 (OCOCH3) and 1730 cm-1 (CO2R); τ 2.66 (10H,s, [C6H5 ]2CH), 3.02 (1H,s, [C6H5 ]2CH), 4.81 and 5.12 (2H, 2D,J5Hz, C6 -H and C7 -H), 4.85 and 5.19 (2H, ABq, J14Hz, CH2OCOCH3), 6.49 (2H, broad s, C2 -H2), 7.98 (3H,s, C3 -CH3). (Found: C, 63.2, 62.8; H,4.5; N,5.8; S,6.8. C24H20N2O5S. 1 /5CH3CO2C2H5 (466.1) requires: C, 63.7; H, 4.65; N,6.0; S,6.9%).

Workup

  1. temperatureto warm to 0°
  2. custompartitioned between ethyl acetate (300ml) and water (100ml)
  3. washThe organic layer was washed with water (100ml)
  4. customdried
  5. customevaporated
  6. dissolutionThe residual foam was dissolved in ethyl acetate (ca 50ml)
  7. additionthe solution slowly added to rapidly stirred petroleum ether (b.p. 60° to 80°)
  8. customThe petroleum ether was decanted from the precipitated solid which
  9. dissolutionwas dissolved in ethyl acetate (100ml)
  10. customThe solution was evaporated

Sources & evidence

ORD record
ord-2bff636b8cc54c7b97db8f7cddf74c4a
Source dataset
uspto-grants-1977_04
Patent number
US04020077

Reaction notes

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