4-Bromophenacyl bromide → 7-(1-Hydroxy-1-p-bromophenacyloxycarbonylmethyl)-8-oxo-7-azabicyclo[4,2,0]oct-3-ene

HRID 1388290Notes

Reaction equation

HRID 1388290 reaction equation
[O:1]=[C:2]1[CH:9]2[CH:4]([CH2:5][CH:6]=[CH:7][CH2:8]2)[NH:3]1.O.[C:11]([OH:15])(=[O:14])[CH:12]=[O:13].C(=O)([O-])[O-].[K+].[K+].[Br:22][C:23]1[CH:32]=[CH:31][C:26]([C:27](=[O:30])[CH2:28]Br)=[CH:25][CH:24]=1>CN(C)C=O.CN(C)P(=O)(N(C)C)N(C)C.C(OCC)(=O)C>[OH:13][CH:12]([N:3]1[C:2](=[O:1])[CH:9]2[CH:4]1[CH2:5][CH:6]=[CH:7][CH2:8]2)[C:11]([O:15][CH2:28][C:27]([C:26]1[CH:31]=[CH:32][C:23]([Br:22])=[CH:24][CH:25]=1)=[O:30])=[O:14]

Participants

8

Reactant 4

HCID 74544-Bromophenacyl bromideHCID 11430Potassium CarbonateHCID 3002787-Azabicyclo[4.2.0]oct-3-en-8-oneHCID 15620607Glyoxylic acid, monohydrate

Product 1

HCID 127969407-(1-Hydroxy-1-p-bromophenacyloxycarbonylmethyl)-8-oxo-7-azabicyclo[4,2,0]oct-3-eneYield 148.4%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolventHCID 12679HexamethylphosphoramideSolvent2×

Procedure

The azetidinone (1) (0.4 g) in ahydrous dimethylformamide (2 ml) was stirred with glyoxylic acid hydrate (0.32 g) in the presence of hexamethylphosphorictriamide (0.1 ml) and molecular sieves (3A; 4 pieces) for 5 h. Potassium carbonate (0.226 g) was added, and the solution stirred until effervescence had ceased (5 min.). p-Bromophenacylbromide (1.00 g; 1.05 equiv.) in dimethylformamide (1.0 ml) and hexamethylphosphorictriamide (0.25 ml) was added, and the solution stirred overnight. The solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution (x 3), dried (Na2SO4) and evaporated to give a gum (1.9 g) which was chromatographed on Kieselgel. Elution of the column with ethyl acetate-petroleum ether (1:1) gave the glyoxylate ester (58). Isomer I as a foam, which slowly crystallised (ethyl acetate-petroleum ether) as needles (0.60 g.) (47%) m.p. 135°-136°, νmax (CHCl3) 3250br, 1760sh, 1750, 1710, 1590, 970 cm-1 ; δ (d6DMSO) 1.9-2.8 (4H, m), 3.35 (1H, m), 4.17 (1H, m) 5.51 (1H, d, J 6.5 Hz; sharpens to a singlet on D2O exchange) 5.55 (2H, s, phenacyl CH2), 5.72br (2H, s), 6.81 (1H, d, J 6.5H, D2O exchangeable), 7.75 (2H, d, J 9 Hz) and 7.90 (2H, d, J 9 Hz) (Found: C, 51.9; H, 4.2; N, 3.6; Br, 20.00. C17H16BrNO5 requires C, 51.8; H, 4.1; N, 3.6; Br, 20.3%).

Workup

  1. custom(5 min.)
  2. stirringthe solution stirred overnight
  3. washwashed with saturated aqueous sodium chloride solution (x 3)
  4. dry with materialdried (Na2SO4)
  5. customevaporated

Sources & evidence

ORD record
ord-99fac0e1f1a344a4ac5da0acb8bf22a7
Source dataset
uspto-grants-1984_02
Patent number
US04431587

Reaction notes

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