Diethyl (cyanomethyl)phosphonate → 3-(3,4-Dimethoxyphenyl)-3-(3,4-methylenedioxyphenyl)acrylonitrile
Reaction equation
C[O:2][C:3]1[CH:4]=[C:5]([C:11]([C:17]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[C:19]([O:25][CH3:26])[CH:18]=2)=[CH:12][C:13](OC)=O)[CH:6]=[CH:7][C:8]=1[O:9][CH3:10].COC1C=C(C=CC=1OC)C(C1C=CC2OCOC=2C=1)=O.C(OP(CC#[N:58])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>>[CH3:26][O:25][C:19]1[CH:18]=[C:17]([C:11]([C:5]2[CH:6]=[CH:7][C:8]3[O:9][CH2:10][O:2][C:3]=3[CH:4]=2)=[CH:12][C:13]#[N:58])[CH:22]=[CH:21][C:20]=1[O:23][CH3:24]Participants
Procedure
3-(3,4-Dimethoxyphenyl)-3-(3,4-methylenedioxyphenyl)acrylonitrile was prepared analogously to methyl 3,3-bis-(3′,4′-dimethoxyphenyl)acrylate using 1-(3,4-dimethoxy-benzoyl)-3,4-methylenedioxybenzene (1.43 g, 5 mmol), diethylcyanomethylphosphonate (0.91 mL, 5.5 mmol) and lithium hexamethyldisilazide (4.2 mL, 5.5 mmol, 1.3M) with a reaction time of 1 hour at reflux and 24 hours at room temperature. The crude product was purified by chromatography (silica gel, 2% ethyl acetate/methylene chloride) to afford 0.79 g (51%) of a mixture of the E and Z isomers as an off white solid: mp 121–123° C.; 1H NMR (CDCl3) δ 7.10–6.73 (m, 12H), 6.13–5.94 (m, 4H), 5.57 (s, 1H), 5.53 (s, 1H), 3.94 (s, 3H), 3.92 (s, 3H), 3.87 (s, 3H), 3.84 (s, 3H); 13C NMR (CDCl3) δ 162.3, 151.0, 150.5, 149.6, 149.1, 148.8, 148.5, 147.9, 133.2, 131.6, 130.8, 129.4, 124.3, 123.5, 123.1, 122.1, 118.5, 118.3, 112.6, 111.1, 110.7, 109.9, 108.5, 108.2, 101.6, 101.5, 92.2, 92.2, 56.0, 55.9, 55.9; Anal. Calcd for C18H15NO4. Theoretical C, 69.89; H, 4.89; N, 4.53. Found: C, 69.61; H, 5.01; N, 4.37.
Workup
- customwith a reaction time of 1 hour
- customThe crude product was purified by chromatography (silica gel, 2% ethyl acetate/methylene chloride)
Sources & evidence
- ORD record
- ord-f9eb2493c61549279de69ba6e1871e12
- Source dataset
- uspto-grants-2006_03
- Patent number
- US07019030B2
Reaction notes
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