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

HRID 277587Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 277587
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]

Komponenten

6

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-737c584ad788443184c304eccdec15b1
Quelldatensatz
uspto-grants-2002_03
Patentnummer
US06355633B1

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