Water → 7-(1-Hydroxy-1-benzyloxycarbonylmethyl)-8-oxo-7-azabicyclo[4,2,0]oct-3-ene

HRID 67931Notes

Reaction equation

HRID 67931 reaction equation
[C:1]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)(=[O:4])[CH:2]=[O:3].O.[O:14]=[C:15]1[CH:22]2[CH:17]([CH2:18][CH:19]=[CH:20][CH2:21]2)[NH:16]1>C1C=CC=CC=1>[OH:3][CH:2]([N:16]1[C:15](=[O:14])[CH:22]2[CH:17]1[CH2:18][CH:19]=[CH:20][CH2:21]2)[C:1]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:4]

Participants

5

Reactant 3

HCID 962WaterHCID 3002787-Azabicyclo[4.2.0]oct-3-en-8-oneHCID 11008258Benzyl glyoxylate

Product 1

HCID 127969367-(1-Hydroxy-1-benzyloxycarbonylmethyl)-8-oxo-7-azabicyclo[4,2,0]oct-3-ene

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Benzyl glyoxylate (2.73 g) was refluxed in benzene (25 ml) with provision for the removal of water. After 45 minutes 8-oxo-7-azabicyclo[4,2,0]oct-3-ene (28) (ref: I. A. Paquette and T. Kakihana, J. Amer. Chem. Soc., 1968, 90, 2897) (1.23 g) was added and refluxing continued for 3 hours. Removal of solvent under reduced pressure followed by chromatography gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1. δ ppm (CDCl3) 1.76-2.73 (4H, m, 2-CH2), 3.12-3.33 (1H, m, β-lactam proton), 3.76-3.93 (1H, m, β-lactam proton), 4.40 (1H, d, J 6 Hz, exch. D2O), 5.16 (2H, s, CH2), 5.47 (1H, d, J 6 Hz collapsing to s on D2O exch. CH-OH), 5.67-5.83 (2H, m, CH=CH), 7.34 (5H, Ar). M+ at m/e 287 (Found; C, 66.2; H, 5.9; N, 4.9.C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). Isomer II, m.p. 100°-101°, νmax (CHCl3) 3450, 1750 (b), δ ppm (CDCl3) 1.80-2.63 (4H, m, 2-CH2), 3.13-3.36 (1H, m, β-lactam proton), 3.93-4.13 (1H, m, β-lactam proton), 4.20 (1H, bs, exch, D2O), 5.16 (2H, s, CH2), 5.50 (1H, b, sharpening to s on D6O exchange), 5.50-6.00 (2H, m, CH=CH), 7.34 (5H, Ar). (Found; C, 67.2; H, 6.0; N, 4.8. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%).

Workup

  1. addition, 1968, 90, 2897) (1.23 g) was added
  2. temperaturerefluxing
  3. customRemoval of solvent under reduced pressure
  4. customgave two
  5. customseparate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1

Sources & evidence

ORD record
ord-2368a94ca1874857ac8b078795d06480
Source dataset
uspto-grants-1982_08
Patent number
US04347181

Reaction notes

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