Diethyl (cyanomethyl)phosphonate → 3-(3,4-Diethylphenyl)-3-(3,4-dimethoxyphenyl)acrylonitrile

HRID 1017955

Reaction equation

HRID 1017955 reaction equation
COC1C=C(C(C2C=CC(OC)=C(OC)C=2)=CC(OC)=O)C=CC=1OC.[CH2:27]([C:29]1[CH:30]=[C:31]([C:37](=O)[C:38]2[CH:43]=[CH:42][C:41]([O:44][CH3:45])=[C:40]([O:46][CH3:47])[CH:39]=2)[CH:32]=[CH:33][C:34]=1[CH2:35][CH3:36])[CH3:28].C(OP([CH2:57][C:58]#[N:59])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>CCCCCC>[CH2:27]([C:29]1[CH:30]=[C:31]([C:37]([C:38]2[CH:43]=[CH:42][C:41]([O:44][CH3:45])=[C:40]([O:46][CH3:47])[CH:39]=2)=[CH:57][C:58]#[N:59])[CH:32]=[CH:33][C:34]=1[CH2:35][CH3:36])[CH3:28]

Participants

6

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 9820154Methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylateHCID 215846043',4'-Diethyl-3,4-dimethoxybenzophenone

Product 1

HCID 540401063-(3,4-Diethylphenyl)-3-(3,4-dimethoxyphenyl)acrylonitrile

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

3-(3,4-Diethylphenyl)-3-(3,4-dimethoxyphenyl)acrylonitrile was prepared analogously to methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylate using 3′,4′-diethyl-3,4-dimethoxybenzophenone (0.51 g, 1.7 mmol), diethylcyanomethylphosphonate (0.31 mL, 1.9 mmol) and lithium hexamethyldisilazide (1.4 mL, 1.9 mmol, 1.3 M) with a reaction time of 60 hours at room temperature. The crude product was purified by chromatography (silica gel, 1% ethyl acetate/methylene chloride) to afford an oil which was stirred in hexane until it solidified. The resulting slurry was filtered, the solid washed with hexane, air dried, and dried in vacuo to afford 0.31 g (57%) of a mixture of the E and Z isomers as an off white solid: mp 78-82° C.; 1H NMR (CDCl3) δ 7.30-6.75 (m, 12 H), 5.61 (s, 1 H), 5.60 (s, 1 H), 3.94 (s, 3 H), 3.92 (s, 3 H), 3.87 (s, 3 H), 3.83 (s, 3 H), 2.80-2.59 (m, 8 H), 1.35-1.14 (m, 12 H); 13C NMR (CDCl3) δ 163.0, 163.0, 151.0, 150.5, 148.8, 148.6, 144.6, 143.9, 142.1, 141.8, 136.8, 134.5, 131.9, 129.7, 128.6, 128.5, 128.2, 127.3, 126.3, 123.2, 122.2, 118.7, 118.6, 112.8, 111.3, 110.7, 92.5, 92.2, 56.1, 56.0, 25.5, 25.4, 25 4, 25.3, 15.3, 15.2, 15.0, 14.9; Anal. Calcd for C21H23NO2. Theoretical: C, 78.47; H, 7.21; N, 4.36. Found: C, 77.80; H, 7.25; N, 4.68.

Workup

  1. customwith a reaction time of 60 hours
  2. customat room temperature
  3. customThe crude product was purified by chromatography (silica gel, 1% ethyl acetate/methylene chloride)
  4. customto afford an oil which
  5. filtrationThe resulting slurry was filtered
  6. washthe solid washed with hexane, air
  7. customdried
  8. customdried in vacuo

Sources & evidence

ORD record
ord-51274f1f392e49ec92e8efcc58659466
Source dataset
uspto-grants-2002_11
Patent number
US06479554B2

Linked notes

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