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

HRID 1017953Notes

Reaction equation

HRID 1017953 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, 1.3 M) 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-c781951896ed47409155d0b75db79736
Source dataset
uspto-grants-2002_11
Patent number
US06479554B2

Reaction notes

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