Diethyl (cyanomethyl)phosphonate → 3-(3,4-Diethylphenyl)-3-(3,4-dimethoxyphenyl)acrylonitrile

HRID 1745382Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1745382
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]([C:37](=O)[C:38]2[CH:43]=[CH:42][C:41]([O:44][CH3:45])=[C:40]([O:46][CH3:47])[CH:39]=2)[CH:32]=[CH:33][C:34]=1[CH2:35][CH3:36])[CH3:28].C(OP([CH2:57][C:58]#[N:59])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>CCCCCC>[CH2:27]([C:29]1[CH:30]=[C:31]([C:37]([C:38]2[CH:43]=[CH:42][C:41]([O:44][CH3:45])=[C:40]([O:46][CH3:47])[CH:39]=2)=[CH:57][C:58]#[N:59])[CH:32]=[CH:33][C:34]=1[CH2:35][CH3:36])[CH3:28]

Komponenten

6

Edukt 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 9820154Methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylateHCID 215846043',4'-Diethyl-3,4-dimethoxybenzophenone

Produkt 1

HCID 540401063-(3,4-Diethylphenyl)-3-(3,4-dimethoxyphenyl)acrylonitrile

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8058HexaneLösungsmittel

Versuchsvorschrift

3-(3,4-Diethylphenyl)-3-(3,4-dimethoxyphenyl)acrylonitrile was prepared analogously to methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylate using 3′,4′-diethyl-3,4-dimethoxybenzophenone (0.51 g, 1.7 mmol), diethylcyanomethylphosphonate (0.31 mL, 1.9 mmol) and lithium hexamethyldisilazide (1.4 mL, 1.9 mmol, 1.3M) with a reaction time of 60 hours at room temperature. The crude product was purified by chromatography (silica gel, 1% 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 dried in vacuo to afford 0.31 g (57%) of a mixture of the E and Z isomers as an off white solid: mp 78–82° C.; 1H NMR (CDCl3) δ 7.30–6.75 (m, 12H), 5.61 (s, 1H), 5.60 (s, 1H), 3.94 (s, 3H), 3.92 (s, 3H), 3.87 (s, 3H), 3.83 (s, 3H), 2.80–2.59 (m, 8H), 1.35–1.14 (m, 12H); 13C NMR (CDCl3) δ 163.0, 163.0, 151.0, 150.5, 148.8, 148.6, 144.6, 143.9, 142.1, 141.8, 136.8, 134.5, 131.9, 129.7, 128.6, 128.5, 128.2, 127.3, 126.3, 123.2, 122.2, 118.7, 118.6, 112.8, 111.3, 110.7, 92.5, 92.2, 56.1, 56.0, 25.5, 25.4, 25.4, 25.3, 15.3, 15.2, 15.0, 14.9; Anal. Calcd for C21H23NO2. Theoretical: C, 78.47; H, 7.21; N, 4.36. Found: C, 77.80; H, 7.25; N, 4.68.

Aufarbeitung

  1. customwith a reaction time of 60 hours
  2. customat room temperature
  3. customThe crude product was purified by chromatography (silica gel, 1% 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

Quellen und Nachweise

ORD-Eintrag
ord-573bd092d7674ff2a10bd170bcbe200f
Quelldatensatz
uspto-grants-2006_03
Patentnummer
US07019030B2

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