4-Nitrobenzaldehyde → 5-Nitro-2-[2-(4-nitro-phenyl)-vinyl]-benzenesulfonic Acid 2,2-Dimethylpropyl Ester

HRID 277587ノート

反応式

HRID 277587 の反応式
C(OP([CH2:9][C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][C:11]=1[S:19]([O:22][CH2:23][C:24]([CH3:27])([CH3:26])[CH3:25])(=[O:21])=[O:20])(OCC)=O)C.[H-].[Na+].[N+:30]([C:33]1[CH:40]=[CH:39][C:36]([CH:37]=O)=[CH:35][CH:34]=1)([O-:32])=[O:31]>O1CCCC1.C(OCC)(=O)C>[CH3:27][C:24]([CH3:25])([CH3:26])[CH2:23][O:22][S:19]([C:11]1[CH:12]=[C:13]([N+:16]([O-:18])=[O:17])[CH:14]=[CH:15][C:10]=1[CH:9]=[CH:37][C:36]1[CH:39]=[CH:40][C:33]([N+:30]([O-:32])=[O:31])=[CH:34][CH:35]=1)(=[O:20])=[O:21]

参加物

6

反応物 3

HCID 5414-NitrobenzaldehydeHCID 24758Sodium hydrideHCID 571066172-(Diethoxyphosphorylmethyl)-5-nitro-benzenesulfonic Acid, 2,2-Dimethylpropyl Ester

生成物 1

HCID 867578655-Nitro-2-[2-(4-nitro-phenyl)-vinyl]-benzenesulfonic Acid 2,2-Dimethylpropyl Ester収率 91%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

2-(Diethoxyphosphorylmethyl)-5-nitro-benzenesulfonic acid, 2,2-dimethylpropyl ester Example 55, 1.15 g, 2.72 mmol) was dissolved in 55 mL of anhydrous tetrahydrofuran. Sodium hydride (0.12 g, 2.99 mmol) was added in one portion and the reaction mixture was stirred for twenty minutes. The solution turned a deep red color. After attaching a reflux condenser, 4-nitrobenzaldehyde (0.821 g, 5.43 mmol) was added and the mixture was heated to reflux in an oil bath. After six hours the solution was cooled to room temperature, diluted with ethyl acetate (300 mL), washed with brine (2×), washed with conc. sodium bisulfite (2×), and the organic layer was dried (MgSO4). After concentration on a rotovap the crude material was purified by a gradient flash column using 30 to 60% ethyl acetate in hexanes as the eluant to afford 1.13 g of the title compound as a yellow solid (91%): 1HNMR (CDCl3) δ8.91 (d, J=2 Hz, 1H), 8.51 (dd, J=9 Hz, 2 Hz, 1H), 8.29 (d, J=9 Hz, 2H), 8.09 (d, J=16 Hz, 1H), 8.06 (d, J=9Hz, 1H), 7.74 (d, J=9Hz, 2H), 7.31 (d, J=16 Hz, 1H), 3.75 (s, 2H), 0.88 (s, 9H); MS (ES-NEG): [M−H]− 419; Anal. Calc. for C19H20N2O7S: C, 54.28; H, 4.79; N, 6.66. Found: C, 54.13; H, 4.68; N, 6.54.

後処理

  1. temperaturethe mixture was heated
  2. temperatureto reflux in an oil bath
  3. washwashed with brine (2×)
  4. washwashed with conc. sodium bisulfite (2×)
  5. dry with materialthe organic layer was dried (MgSO4)
  6. concentrationAfter concentration on a rotovap the crude material
  7. customwas purified by a gradient flash column

出典と根拠

ORDレコード
ord-737c584ad788443184c304eccdec15b1
出典データセット
uspto-grants-2002_03
特許番号
US06355633B1

反応ノート

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