4-Nitrobenzaldehyde → Ethyl 3-(4-nitrophenyl)-2-propenoate

HRID 222568Notes

Reaction equation

HRID 222568 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH:8]=O)=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:12]([CH:17]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:14][CH2:15][CH3:16])=[O:13].C1(P(=O)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[CH2:15]([O:14][C:12](=[O:13])[CH:17]=[CH:8][C:7]1[CH:10]=[CH:11][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)[CH3:16]

Participants

5

Reactant 3

HCID 5414-NitrobenzaldehydeHCID 13097Triphenylphosphine OxideHCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester

Product 1

HCID 95370Ethyl 3-(4-nitrophenyl)-2-propenoate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 4-nitrobenzaldehyde (53, 10.00 g, 66.23 mmol) and (carbethoxymethylene)triphenylphosphorane (27.92 g, 72.85 mmol, 1.1 equiv) was refluxed in CH2Cl2 (74 mL) for 24 h. The solvent was removed at reduced pressure. The oily residue was chromatographed (silica, hexanes/diethyl ether, 1:1) to give a pale yellow solid, which was shown by 1H NMR and TLC analysis to contain triphenylphosphine oxide. This sample was further purified by short-path Kugelrohr distillation (0.05 mmHg, up to 180° C.) to yield a pale yellow solid (3.74 g, 26%, mixture of E and Z isomers): 1H NMR δ 1.33 (t, J=7.5 Hz, 3H), 4.27 (q, J=7.5 Hz, 2H), 6.54 (d, J=15.6 Hz, 1H), 7.62-7.71 (m, 3H), 8.17-8.24 (m, 2H); 13C NMR δ 14.48, 61.22, 122.81, 123.54, 124.38, 130.43, 132.24, 140.76, 141.82, 166.24.

Workup

  1. customThe solvent was removed at reduced pressure
  2. customThe oily residue was chromatographed (silica, hexanes/diethyl ether, 1:1)
  3. customto give a pale yellow solid, which
  4. distillationThis sample was further purified by short-path Kugelrohr distillation (0.05 mmHg
  5. customup to 180° C.) to yield
  6. additiona pale yellow solid (3.74 g, 26%, mixture of E and Z isomers)

Sources & evidence

ORD record
ord-9144c21a79664c039b5a2faa444a0679
Source dataset
uspto-grants-2012_06
Patent number
US08207329B2

Reaction notes

Loading…