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

HRID 329241ノート

反応式

HRID 329241 の反応式
[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]

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

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%).

後処理

  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

出典と根拠

ORDレコード
ord-08c4294e32394290af1f523b1423b593
出典データセット
uspto-grants-1977_04
特許番号
US04020077

反応ノート

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