Diethyl (cyanomethyl)phosphonate → 3-(3,4-Diethylphenyl)-3-phenylacrylonitrile

HRID 366630

Reaction equation

HRID 366630 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]([CH:40]=[CH:41][C:42]=1[CH2:43][CH3:44])[C:32]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)=O)[CH3:28].C(OP([CH2:53][C:54]#[N:55])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>CCCCCC>[CH2:27]([C:29]1[CH:30]=[C:31]([C:32]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)=[CH:53][C:54]#[N:55])[CH:40]=[CH:41][C:42]=1[CH2:43][CH3:44])[CH3:28]

Participants

6

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 9820154Methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylateHCID 215845983,4-Diethylbenzophenone

Product 1

HCID 543068803-(3,4-Diethylphenyl)-3-phenylacrylonitrile

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

3-(3,4-Diethylphenyl)-3-phenylacrylonitrile was prepared analogously to methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylate using 3,4-diethylbenzophenone (0.95 g, 4 mmol), diethylcyanomethylphosphonate (0.73 mL, 4.4 mmol) and lithium hexamethyldisilazide (3.4 mL, 4.4 mmol, 1.3M) with a reaction time of 2 hours at room temperature. The crude product was purified by flash chromatography (silica gel, 8% 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 then dried in vacuo to afford 0.6 g (57%) of a mixture of the E and Z isomers as a white solid: mp 63-64° C.; 1H NMR (CDCl3) δ 7.51-6.99 (m, 16 H), 5.72 (s, 2 H), 2.76-2.55 (m, 8 H), 1.32-1.14 (m, 12 H); 13C NMR (CDCl3) δ 163.3, 144.7, 142.2, 137.3, 136.5, 130.2, 129.8, 129.6, 128.6, 128.5, 128.4, 128.3, 127.2, 126.2, 118.2, 93.9, 93.7, 25.5, 25.3, 15.2, 15.0.

Workup

  1. customwith a reaction time of 2 hours
  2. customat room temperature
  3. customThe crude product was purified by flash chromatography (silica gel, 8% 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-2f971f3528ee4d93a5e1f2583d38984f
Source dataset
uspto-grants-2000_10
Patent number
US06130226

Linked notes

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