4-Nitrobenzyl bromide → p-nitrobenzyl (3S,5R,6R)-6-formamido-2,2-dimethylpenam-3-carboxylate

HRID 329241Notes

Reaction equation

HRID 329241 reaction equation
[CH:1]([NH:3][C@@H:4]1[C:15](=[O:16])[N:6]2[C@@H:7]([C:12]([O-:14])=[O:13])[C:8]([CH3:11])([CH3:10])[S:9][C@H:5]12)=[O:2].[Na+].[N+:18]([C:21]1[CH:28]=[CH:27][C:24]([CH2:25]Br)=[CH:23][CH:22]=1)([O-:20])=[O:19]>CN(C)C=O>[CH:1]([NH:3][C@@H:4]1[C:15](=[O:16])[N:6]2[C@@H:7]([C:12]([O:14][CH2:25][C:24]3[CH:27]=[CH:28][C:21]([N+:18]([O-:20])=[O:19])=[CH:22][CH:23]=3)=[O:13])[C:8]([CH3:11])([CH3:10])[S:9][C@H:5]12)=[O:2]

Participants

4

Reactant 2

HCID 660114-Nitrobenzyl bromideHCID 86733807sodium (3S,5R,6R)-6-formamido-2,2-dimethylpenam-3-carboxylate

Product 1

HCID 22791970p-nitrobenzyl (3S,5R,6R)-6-formamido-2,2-dimethylpenam-3-carboxylate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of sodium (3S,5R,6R)-6-formamido-2,2-dimethylpenam-3-carboxylate (15.0109 g., 56.4 mmole) and p-nitrobenzyl bromide (12.16805 g., 56.3 mmole) in N,N-dimethylformamide (250 ml.) was stirred for 4 hours at +20 to +25°, after which time all the solid had dissolved. The solvent was removed by evaporation and the residual paste was suspended in ethyl acetate (100 ml.) and washed with brine. The aqueous layer was washed with ethyl acetate (150 ml.) and the combined organic layers washed with water (5 × 250 ml.), passed through phase-separating paper and evaporated to a pale-yellow foam. Chromatography on kieselgel G (600 g.) in benzene-ethyl acetate (1:1) gave p-nitrobenzyl (3S,5R,6R)-6-formamido-2,2-dimethylpenam-3-carboxylate which crystallised from ether-ethyl acetate (3:1) as a white solid (8.73 g., 23 mmole, 41%); m.p. 129° to 132°; [α]D + 190°; λmax. 262 (ε 10,170); νmax. 3420 (NH), 2880 (HCO), 1788 (azetidin-2-one), 1750 (CO2R), 1695 and 1505 (CONH), 1528 and 1346 (Ar-NO2), 841 cm.-1 (para-disubstituted aromatic ring); τ 1.73, 2.43 (2H, AB-q, J 8.5 Hz, p-nitrophenyl), 1.75 (1H, s, HCO), 3.37 (1H, d, J 9 Hz, NH), 4.21 (1H, dd, J 9 and 4.5 Hz, C6 -H), 4.42 (1H, d, J 4.5 Hz, C5 -H), 4.68 (2H, s, NO2C6H4CH2), 5.46 (1H, s, C3 -H), 8.36 (3H, s) and 8.54 (3H, s) (C[CH3 ]2). (Found : C, 50.5; H, 4.6; N, 11.1; S, 8.5. C16H17N3O6S (379.4) requires C, 50.7; H, 4.6; N, 11.1; S, 8.4%).

Workup

  1. dissolutionafter which time all the solid had dissolved
  2. customThe solvent was removed by evaporation
  3. washwashed with brine
  4. washThe aqueous layer was washed with ethyl acetate (150 ml.)
  5. washthe combined organic layers washed with water (5 × 250 ml.)
  6. customthrough phase-separating paper
  7. customevaporated to a pale-yellow foam

Sources & evidence

ORD record
ord-08c4294e32394290af1f523b1423b593
Source dataset
uspto-grants-1977_04
Patent number
US04020077

Reaction notes

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