Diethyl (cyanomethyl)phosphonate → 3-(3,4-Dimethoxyphenyl)-3-(3,5-dimethoxyphenyl)prop-2-enenitrile

HRID 366606Notes

Reaction equation

HRID 366606 reaction equation
COC1C=C(C(C2C=CC(OC)=C(OC)C=2)=CC(OC)=O)C=CC=1OC.[CH3:27][O:28][C:29]1[CH:30]=[C:31]([CH:44]=[CH:45][C:46]=1[O:47][CH3:48])[C:32]([C:34]1[CH:39]=[C:38]([O:40][CH3:41])[CH:37]=[C:36]([O:42][CH3:43])[CH:35]=1)=O.C(OP([CH2:57][C:58]#[N:59])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>>[CH3:27][O:28][C:29]1[CH:30]=[C:31]([C:32]([C:34]2[CH:39]=[C:38]([O:40][CH3:41])[CH:37]=[C:36]([O:42][CH3:43])[CH:35]=2)=[CH:57][C:58]#[N:59])[CH:44]=[CH:45][C:46]=1[O:47][CH3:48]

Participants

5

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 9820154Methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylateHCID 21584591(3,4-Dimethoxyphenyl)(3,5-dimethoxyphenyl)methanone

Product 1

HCID 542380573-(3,4-Dimethoxyphenyl)-3-(3,5-dimethoxyphenyl)prop-2-enenitrile

Procedure

3-(3,4-Dimethoxyphenyl)-3-(3',5'-dimethoxyphenyl)acrylonitrile was prepared analogously to methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylate using 3,4,3',5'-tetramethoxybenzophenone (0.7 g, 2.3 mmol), diethylcyanomethylphosphonate (0.42 mL, 2.5 mmol) and lithium hexamethyldisilazide (1.9 mL, 2.5 mmol, 1.3M) with a reaction time of 60 hours at room temperature. The crude product was purified by flash chromatography (silica gel, 1% ethyl acetate/methylene chloride) to afford 0.66 g (81%) of a mixture of the E and Z isomers as a white solid: mp 88-90° C.; 1H NMR (CDCl3) δ 7.10-6.80 (m, 6 H), 6.61-6.40 (m, 6 H), 5.66 (s, 1 H), 5.61 (s, 1 H), 3.94 (s, 3 H), 3.91 (s, 3 H), 3.87 (s, 3 H), 3.84 (s, 3 H), 3.80 (s, 3 H), 3.77 (s, 6 H); 13C NMR (CDCl3) δ 162.7, 162.5, 160.7, 160.6, 151.1, 150.6, 148.8, 148.5, 141.3, 138.9, 131.1, 129.2, 123.2, 122.1, 118.2, 118.0, 112.6, 110.9, 110.7, 110.7, 107.6, 107.0, 102.1, 102.0, 93.4, 93.1, 56.0, 55.9, 55.5, 55.4; Anal. Calcd for C19H19NO4. Theoretical: C, 70.14; H, 5.89; N, 4.30. Found: C, 70.33; H, 5.89; N, 4.03.

Workup

  1. customwith a reaction time of 60 hours
  2. customat room temperature
  3. customThe crude product was purified by flash chromatography (silica gel, 1% ethyl acetate/methylene chloride)

Sources & evidence

ORD record
ord-cfa80a2044bf47a4abb83ca91694ccd0
Source dataset
uspto-grants-2000_10
Patent number
US06130226

Reaction notes

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