Diethyl (cyanomethyl)phosphonate → 3-(3,4-Dimethoxyphenyl)-3-(2-furyl)acrylonitrile

HRID 366628Notes

Reaction equation

HRID 366628 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:11]([C:17]2C=C[C:20]([O:23]C)=[C:19](OC)[CH:18]=2)=[CH:12][C:13](OC)=O)[CH:6]=[CH:7][C:8]=1[O:9][CH3:10].COC1C=C(C=CC=1OC)C(C1OC=CC=1)=O.C(OP(CC#[N:54])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:11]([C:17]2[O:23][CH:20]=[CH:19][CH:18]=2)=[CH:12][C:13]#[N:54])[CH:6]=[CH:7][C:8]=1[O:9][CH3:10]

Participants

5

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 8383262-(3,4-Dimethoxybenzoyl)furanHCID 2733832Lithium HexamethyldisilazideHCID 9820154Methyl 3,3-bis-(3,4-dimethoxyphenyl)acrylate

Product 1

HCID 536710503-(3,4-Dimethoxyphenyl)-3-(2-furyl)acrylonitrile

Procedure

3-(3,4-Dimethoxyphenyl)-3-(2-furyl)acrylonitrile was prepared analogously to methyl 3,3-bis-(3',4'-dimethoxyphenyl)acrylate using 2-(3,4-dimethoxybenzoyl)furane (0.87 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 3 hours at room temperature. The crude product was purified by chromatography (silica gel, 2% ethyl acetate/methylene chloride) to afford 0.78 g (76%) of a mixture of the E and Z isomers as an off white solid: mp 78-82° C.; 1H NMR (CDCl3) δ 7.68-7.73 (m, 2 H), 7.16-6.75 (m, 7 H), 6.54-6.39 (m, 3 H), 5.87 (s, 1 H), 5.30 (s, 1 H), 3.93 (s, 3 H), 3.93 (s, 3 H), 3.91 (s, 3 H), 3.88 (s, 3 H); 13C NMR (CDCl3) δ 152.0, 150.7, 150.5, 150.4, 149.3, 148.8, 148.7, 148.7, 145.2, 145.0, 129.6, 126.7, 122.1, 121.6, 118.1, 118.0, 116.5, 115.6, 112.5, 112.1, 112.0, 111.5, 110.9, 110.8, 90.5, 90.2, 55.9, 55.9, 55.9, 55.8; Anal. Calcd for C15H13NO3. Theoretical: C, 70.58; H, 5.13; N, 5.49. Found: C, 70.61; H, 5.09; N, 5.18.

Workup

  1. customwith a reaction time of 3 hours
  2. customat room temperature
  3. customThe crude product was purified by chromatography (silica gel, 2% ethyl acetate/methylene chloride)

Sources & evidence

ORD record
ord-b68ca4649348449595c6ed4982b51aad
Source dataset
uspto-grants-2000_10
Patent number
US06130226

Reaction notes

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