Diethyl (cyanomethyl)phosphonate → 3-(3,4-Dimethoxyphenyl)-3-pyridin-4-ylacrylonitrile

HRID 1745375Notes

Reaction equation

HRID 1745375 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:40]=[CH:41][C:42]=1[O:43][CH3:44])[C:32]([C:34]1[CH:39]=[CH:38][N:37]=[CH:36][CH:35]=1)=O.C(OP([CH2:53][C:54]#[N:55])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>CCCCCC>[CH3:27][O:28][C:29]1[CH:30]=[C:31]([C:32]([C:34]2[CH:39]=[CH:38][N:37]=[CH:36][CH:35]=2)=[CH:53][C:54]#[N:55])[CH:40]=[CH:41][C:42]=1[O:43][CH3:44]

Participants

6

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 9820154Methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylateHCID 215846084-(3,4-Dimethoxybenzoyl)pyridine

Product 1

HCID 542468793-(3,4-Dimethoxyphenyl)-3-pyridin-4-ylacrylonitrile

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

3-(3,4-Dimethoxyphenyl)-3-pyridin-4-ylacrylonitrile was prepared analogously to methyl 3,3-bis-(3′,4′-dimethoxyphenyl)acrylate using 4-(3,4-dimethoxybenzoyl)pyridine (1 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 24 hours at room temperature. The crude product was slurried in 10 mL of hexane. The mixture was filtered, the solid was washed with hexane, air dried and then dried in vacuo to afford 0.91 g (85%) of a mixture of the E and Z isomers as an off white solid: mp 116–125° C.; 1H NMR (CDCl3) δ 8.80–8.63 (m, 4H), 7.40–7.20 (n, 4H), 7.04–6.74 (m, 6H 5.81 (s, 1H), 5.70 (s, 1H), 3.94 (s, 3H), 3.92 (s, 3H), 3.87 (s, 3H), 3.84 (s, 3H); 13C NMR (CDCl3) δ 160.1, 157.0, 151.6, 151.1, 150.3, 149.2, 148.9, 146.7, 144.9, 129.6, 127.8, 123.7, 123.1, 122.7, 122.1, 117.4, 117.1, 112.3, 111.0, 110.5, 96.1, 94.8, 56.0, 56.0; Anal. Calcd for C16H14N2O2. Theoretical: C, 72.17; H, 5.30; N, 16.52. Found: C, 72.35; H, 5.43; N, 10.47.

Workup

  1. customwith a reaction time of 24 hours
  2. customat room temperature
  3. filtrationThe mixture was filtered
  4. washthe solid was washed with hexane, air
  5. customdried
  6. customdried in vacuo

Sources & evidence

ORD record
ord-ee10b0af7f8d4728b58441936ab549cf
Source dataset
uspto-grants-2006_03
Patent number
US07019030B2

Reaction notes

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