Diethyl Ether → 3-(3,5-Dimethoxy-phenyl)-3-(3-hydroxy-4-methoxy-phenyl)-acrylonitrile

HRID 970960Notes

Reaction equation

HRID 970960 reaction equation
[F-].C([N+](CCCC)(CCCC)CCCC)CCC.[Si]([O:26][C:27]1[CH:28]=[C:29]([C:35]([C:39]2[CH:44]=[C:43]([O:45][CH3:46])[CH:42]=[C:41]([O:47][CH3:48])[CH:40]=2)=[CH:36][C:37]#[N:38])[CH:30]=[CH:31][C:32]=1[O:33][CH3:34])(C(C)(C)C)(C)C.CCOCC>C1COCC1>[CH3:48][O:47][C:41]1[CH:40]=[C:39]([C:35]([C:29]2[CH:30]=[CH:31][C:32]([O:33][CH3:34])=[C:27]([OH:26])[CH:28]=2)=[CH:36][C:37]#[N:38])[CH:44]=[C:43]([O:45][CH3:46])[CH:42]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 2724141Tetrabutylammonium FluorideHCID 692025173-[3-(Tert-butyldimethylsilanyloxy)-4-methoxyphenyl]-3-(3,5-dimethoxyphenyl)acrylonitrile

Product 1

HCID 692025153-(3,5-Dimethoxy-phenyl)-3-(3-hydroxy-4-methoxy-phenyl)-acrylonitrileYield 90%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Tetrabutylammonium fluoride (1.0 M solution in THF, 1.49 ml, 1.49 mmol) was added at rt to a stirred solution of 3-[3-(tert-butyldimethylsilanyloxy)-4-methoxyphenyl]-3-(3,5-dimethoxyphenyl)acrylonitrile (0.53 g, 1.25 mmol) in THF (15 ml). The colorless clear solution immediately turned into brown/red wine color. The reaction should be done within one hour. Ice water (10 ml) was poured into the reddish solution, followed by addition of ether (50 ml). The mixture was washed with water (2×80 ml), dried over MgSO4, filtered and concentrated to a yellow oil, which was lyophilized to give 3-(3,5-dimethoxy-phenyl)-3-(3-hydroxy-4-methoxy-phenyl)-acrylonitrile as a foamy solid (0.35 g, 90%): mp, 43-45° C.; 1HNMR (DMSO-d6) δ 9.36 (s, 1H, OH group of one isomer), 9.28 (s, 1H, OH group of the other isomer), 7.07 (d, J=8 Hz, 1H, Ar), 7.00 (d, J=8 Hz, 1H, Ar), 6.91-6.82 (m, 4H, Ar), 6.69-6.65 (m, 2H, Ar), 6.49 (t, J=2 Hz, 4H, Ar), 6.19 (s, 1H, double bond proton of one isomer), 6.17 (s, 1H, double bond proton of the other isomer), 3.87 (s, 3H, OCH3), 3.84 (s, 3H, OCH3), 3.81 (s, 6H, 2OCH3), 3.78 (s, 6H, 2OCH3), isomer ratio based on 1HNMR was 45%:55%; 13C NMR (CDCl3) δ 162.8, 162.6, 160.8, 160.8, 148.7, 148.2, 145.7, 145.5, 141.4, 139.1, 131.9, 130.2, 122.3, 121.3, 118.2, 118.1, 116.0, 114.4, 110.4, 110.4, 107.8, 107.1, 102.2, 94.2, 93.5, 56.2, 56.1, 55.6; Anal. Calcd. For C18H17NO4: C, 69.12; H, 5.53; N, 4.48. Found: C, 68.76; H, 5.69; N, 4.22.

Workup

  1. customThe reaction
  2. washThe mixture was washed with water (2×80 ml)
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated to a yellow oil, which

Sources & evidence

ORD record
ord-770db1a651384eb18f89d96212470427
Source dataset
uspto-grants-2007_12
Patent number
US07312241B2

Reaction notes

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