Malononitrile → 2-[(3,5-Dimethoxy-phenyl)-(3-methoxy-phenyl)-methylene]-malononitrile

HRID 971006Notes

Reaction equation

HRID 971006 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:11]([C:13]2[CH:18]=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[CH:14]=2)=O)[CH:6]=[C:7]([O:9][CH3:10])[CH:8]=1.[C:21](#[N:25])[CH2:22][C:23]#[N:24].[O-2].[Al+3].[O-2].[O-2].[Al+3]>>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:11]([C:13]2[CH:18]=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[CH:14]=2)=[C:22]([C:21]#[N:25])[C:23]#[N:24])[CH:6]=[C:7]([O:9][CH3:10])[CH:8]=1

Participants

4

Reactant 3

HCID 8010MalononitrileHCID 9989226AluminaHCID 69203980(3,5-Dimethoxyphenyl)-(3-methoxyphenyl)methanone

Product 1

HCID 104037152-[(3,5-Dimethoxy-phenyl)-(3-methoxy-phenyl)-methylene]-malononitrileYield 34%

Conditions

Temperature
160 °C

Procedure

(3,5-dimethoxyphenyl)-(3-methoxyphenyl)methanone (0.31 g, 1.12 mmol), malononitrile (0.08 ml, 1.23 mmol), and aluminum oxide (0.57 g, 5.6 mmol) were mixed and heated in an oil bath at 160° C. overnight. After cooling down to r.t., the brown mixture was extracted with CH2Cl2 (˜50 ml), filtered through a Celite pad and concentrated to an oil, which was purified via flash column chromatography (5% EtOAc in hexane gradient to 20% EtOAc in hexane in about 40 min.) and lyophilized to give 2-[(3,5-dimethoxy-phenyl)-(3-methoxy-phenyl)-methylene]-malononitrile as a greenish solid (0.12 g, 34%): mp, 100-102° C.; 1HNMR (DMSO-d6) δ 7.47 (t, J=8 Hz, 1H, Ar), 7.22 (dd, J=2.36, 8 Hz, 1H, Ar), 7.16 (t, J=1 Hz, 1H, Ar), 6.96 (d, J=7 Hz, 1H, Ar), 6.78 (t, J=2 Hz, 1H, Ar), 6.62 (d, J=2 Hz, 2H, Ar), 3.79 (s, 3H, OCH3), 3.76 (s, 6H, 2OCH3); 13C NMR (DMSO-d6) δ 173.4, 160.3, 158.9, 137.5, 136.8, 130.1, 122.4, 118.0, 115.3, 114.1, 114.0, 108.1, 103.6, 82.9, 55.6, 55.5; Anal. Calcd. For C19H16N2O3: C, 71.24; H, 5.03; N, 8.74. Found: C, 71.10; H, 4.87; N, 8.59.

Workup

  1. temperatureAfter cooling down to r.t.
  2. extractionthe brown mixture was extracted with CH2Cl2 (˜50 ml)
  3. filtrationfiltered through a Celite pad
  4. concentrationconcentrated to an oil, which
  5. customwas purified via flash column chromatography (5% EtOAc in hexane gradient to 20% EtOAc in hexane in about 40 min.)

Sources & evidence

ORD record
ord-2ceb6f956dbe4bbc9b58dcf537294cf3
Source dataset
uspto-grants-2007_12
Patent number
US07312241B2

Reaction notes

Loading…