Cyclohexene → 3-(3,5-Dimethoxy-phenyl)-3-(3-hydroxy-phenyl)-acrylonitrile

HRID 971007Notes

Reaction equation

HRID 971007 reaction equation
C([O:8][C:9]1[CH:10]=[C:11]([C:15]([C:19]2[CH:24]=[C:23]([O:25][CH3:26])[CH:22]=[C:21]([O:27][CH3:28])[CH:20]=2)=[CH:16][C:17]#[N:18])[CH:12]=[CH:13][CH:14]=1)C1C=CC=CC=1.C1CCCCC=1>[OH-].[OH-].[Pd+2].C(O)C>[CH3:28][O:27][C:21]1[CH:20]=[C:19]([C:15]([C:11]2[CH:12]=[CH:13][CH:14]=[C:9]([OH:8])[CH:10]=2)=[CH:16][C:17]#[N:18])[CH:24]=[C:23]([O:25][CH3:26])[CH:22]=1

Participants

5

Reactant 2

HCID 8079CyclohexeneHCID 692025963-(3-Benzyloxyphenyl)-3-(3,5-dimethoxyphenyl)acrylonitrile

Product 1

HCID 692024963-(3,5-Dimethoxy-phenyl)-3-(3-hydroxy-phenyl)-acrylonitrileYield 64%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 702EthanolSolvent

Procedure

3-(3-Benzyloxyphenyl)-3-(3,5-dimethoxyphenyl)acrylonitrile (3.45 g), 20% palladium hydroxide on charcoal (0.103 g, 3% w.t.), cyclohexene (12 ml), and ethanol (24 ml) were heated to reflux overnight. The black suspension was cooled, filtered through a Celite pad, and concentrated to an oil, which was purified via flash column chromatography (5% EtOAc in hexane gradient to 30% EtOAc in hexane in about 30 min.) to give 3-(3,5-dimethoxy-phenyl)-3-(3-hydroxy-phenyl)-acrylonitrile as an off-white solid (1.66 g, 64%): mp, 127-129° C.; 1HNMR (DMSO-d6) δ 9.73 (s, 0.67H, OH of one isomer), 9.65 (s, 0.26H, OH of the other isomer), 7.33-7.23 (m, 1H, Ar), 6.92-6.62 (m, 4H, Ar), 6.46 (d, J=2 Hz, 2H, Ar), 6.32 (s, 0.73H, double bond proton of one isomer), 6.27 (s, 0.27H, double bond proton of the other isomer), 3.77 (s, 1.85H, 2OCH3 of one isomer), 3.73 (s, 4.29H, 2OCH3 of the other isomer), isomer ratio 27.6%:72.4%; 13C NMR (DMSO-d6) δ 161.5, 160.4, 157.4, 157.2, 139.9, 138.7, 138.1, 129.7, 119.7, 118.7, 118.0, 117.5, 116.7, 115.7, 115.0, 107.1, 106.6, 101.8, 101.0, 96.3, 96.0, 55.4; Anal. Calcd. For C17H15NO3: C, 72.58; H, 5.37; N, 4.98. Found: C, 72.40; H, 5.26; N, 4.85.

Workup

  1. temperatureto reflux overnight
  2. temperatureThe black suspension was cooled
  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 30% EtOAc in hexane in about 30 min.)

Sources & evidence

ORD record
ord-e87f451f27024130892b554ce18ca0f7
Source dataset
uspto-grants-2007_12
Patent number
US07312241B2

Reaction notes

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