Diethyl (cyanomethyl)phosphonate → 3-(4-Biphenylyl)-3-(3,4-dimethoxyphenyl)acrylonitrile
Reaction equation
COC1C=C(C(C2C=CC(OC)=C(OC)C=2)=CC(OC)=O)C=CC=1OC.[CH3:27][O:28][C:29]1[CH:30]=[C:31]([CH:46]=[CH:47][C:48]=1[O:49][CH3:50])[C:32]([C:34]1[CH:39]=[CH:38][C:37]([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)=[CH:36][CH:35]=1)=O.C(OP([CH2:59][C:60]#[N:61])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>>[C:37]1([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[CH:38]=[CH:39][C:34]([C:32]([C:31]2[CH:46]=[CH:47][C:48]([O:49][CH3:50])=[C:29]([O:28][CH3:27])[CH:30]=2)=[CH:59][C:60]#[N:61])=[CH:35][CH:36]=1Participants
Procedure
3-(4-Biphenylyl)-3-(3,4-dimethoxyphenyl)acrylonitrile was prepared analogously to methyl 3,3-bis-(3′,4′-dimethoxyphenyl)acrylate using 3,4-dimethoxy-4′-phenylbenzophenone (2.33 g, 7.32 mmol), diethylcyanomethylphosphonate (1.5 mL, 8.1 mmol) and lithium hexamethyldisilazide (8.1 mL, 8.1 mmol, 1M) with a reaction time of 22 hours. The crude product was purified by chromatography (silica gel, 1% ethyl acetate/methylene chloride) to afford 1.76 g (70%) of a mixture of the E and Z isomers as a white solid: mp 132.0-134° C.; 1H NMR (CDCl3) δ7.70-7.39 (m, 18 H), 7.10-6.80 (m, 6 H), 5.69 (s, 1 H), 5.68 (s, 1 H), 3.95 (s, 6 H), 3.93 (s, 3 H), 3.89 (s, 3 H), 3.85 (s, 3 H); 13C NMR (CDCl3) δ162.2, 151.1, 148.8, 148.6, 143.0, 142.6, 140.0, 137.9, 135.9, 131.4, 130.1, 129.3, 129.1, 128.8, 128.8, 127.9, 127.1, 127.0, 126.0, 126.9, 123.1, 122.2, 118.3, 118.2, 112.6, 111.1, 110.7, 93.2, 92.9, 56.0, 55.9, 55.8; Anal. Calcd for C23H19NO2. Theoretical: C, 80.92; H, 5.61; N, 4.10. Found: C, 80.55; H, 5.80; N, 3.95.
Workup
- customwith a reaction time of 22 hours
- customThe crude product was purified by chromatography (silica gel, 1% ethyl acetate/methylene chloride)
Sources & evidence
- ORD record
- ord-e374b5400e3843d392b2bd15ebac139d
- Source dataset
- uspto-grants-2001_07
- Patent number
- US06262101B1
Reaction notes
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