Formaldehyde → HCID 70621161, compound

HRID 2420567Notes

Reaction equation

HRID 2420567 reaction equation
C=O.[C:3](=O)([O-])O.[Na+].[Br-].[O:9]([CH2:16][C:17]([NH:19][C@@H:20]1[C:55](=[O:56])[N:22]2[C:23]([C:47]([O:49][CH2:50][C:51]([Cl:54])([Cl:53])[Cl:52])=[O:48])=[C:24]([CH2:27][P+](C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)[CH2:25][S:26][C@H:21]12)=[O:18])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>C(Cl)Cl>[O:9]([CH2:16][C:17]([NH:19][C@@H:20]1[C:55](=[O:56])[N:22]2[C:23]([C:47]([O:49][CH2:50][C:51]([Cl:53])([Cl:52])[Cl:54])=[O:48])=[C:24]([CH:27]=[CH2:3])[CH2:25][S:26][C@H:21]12)=[O:18])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 516892Sodium BicarbonateHCID 88802296HCID 88802296, compound

Product 1

HCID 70621161HCID 70621161, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

40%-Aqueous formaldehyde (24 ml.) and 3%-sodium hydrogen carbonate solution (80 ml.) were added to a solution of [7β-phenoxyacetamido-4-(2,2,2-trichloroethoxycarbonyl) ceph-3-em-3-ylmethyl]-triphenylphosphonium bromide (4.93 g, 6 mmole) in methylene chloride (40 ml.). The two-phase mixture was stirred vigorously for 2 hours and the organic phase was washed with water (100 ml.), dried (MgSO4), and evaporated to an orange foam. This foam was chromatographed on Kieselgel G (Merck; 150 g) with methylene chloride and 0.5%-acetone in methylene chloride as eluants. The appropriate fractions were combined and evaporated to a colourless oil which crystallised on addition of ether. The solvent was removed to give the title ester as a white solid (0.50 g, 17%), m.p. 136° to 140° (decomp), [α]D23 - 33° (c 1.01; Me2SO), λmax. (EtOH), 296 nm (ε 12,100), νmax. (Nujol) 3300 (NH), 1764 (azetidin-2-one), 1716 (CO2R), 1668 and 1509 (CONH) and 920 cm-1 (=CH2), τ (Me2SO-d6) 0.81 (1H, d, J 8 Hz; NH), 2.67 and 2.99 (2H and 3H, 2m; C6H5O), 3.01 (1H, dd, J 11 and 18 Hz; CH=CH2), 4.19 (1H, dd, J 8 and 5 Hz; C7 -H), 4.24 (1H, d, J 18 Hz) and 4.55 (1H, d, 11 Hz) (CH=CH2), 4.71 (1H, d, J 5 Hz; C6 -H), 4.79 and 5.01 (2H, AB-q, J 12 Hz; CH2CCl3), 5.36 (2H, s; C6H5OCH2), 5.98 and 6.34 (2H, AB-q, J 18 Hz; C2 -H2).

Workup

  1. washthe organic phase was washed with water (100 ml.)
  2. dry with materialdried (MgSO4)
  3. customevaporated to an orange foam
  4. customThis foam was chromatographed on Kieselgel G (Merck; 150 g) with methylene chloride and 0.5%-acetone in methylene chloride as eluants
  5. customevaporated to a colourless oil which
  6. customcrystallised on addition of ether
  7. customThe solvent was removed

Sources & evidence

ORD record
ord-778c88c97aeb41b58e60f3e53415d9d0
Source dataset
uspto-grants-1978_08
Patent number
US04110534

Reaction notes

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