Diethyl (cyanomethyl)phosphonate → HCID 69205046, compound

HRID 970982Notes

Reaction equation

HRID 970982 reaction equation
COC1C=C(C(C2C=CC=CC=2)=O)C=C(OC)C=1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].C(OP(CC#N)(=O)OCC)C.O1[C:45]2[CH:46]=[CH:47][C:48]([C:50]([C:54]3[CH:59]=[C:58]([O:60][CH3:61])[CH:57]=[C:56]([O:62][CH3:63])[CH:55]=3)=[CH:51][C:52]#[N:53])=[CH:49][C:44]=2OCC1>C1COCC1>[CH3:63][O:62][C:56]1[CH:55]=[C:54]([C:50]([C:48]2[CH:49]=[CH:44][CH:45]=[CH:46][CH:47]=2)=[CH:51][C:52]#[N:53])[CH:59]=[C:58]([O:60][CH3:61])[CH:57]=1

Participants

6

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 24261623HCID 24261623, compoundHCID 692032153-(2,3-Dihydrobenzo[1,4]dioxin-6-yl)-3-(3,5-dimethoxyphenyl)acrylonitrile

Product 1

HCID 69205046HCID 69205046, compoundYield 89%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

(3,5-Dimethoxyphenyl)phenylmethanone (0.34 g, 1.40 mmol), lithium bis (trimethylsilyl)amide (1.0 M solution in THF, 2.81 ml, 2.81 mmol), and cyanomethylphosphonic acid diethyl ester (0.44 ml, 2.81 mmol) in anhydrous THF (5 ml) were treated in the same manner as described above for the synthesis of 3-(2,3-dihydrobenzo[1,4]dioxin-6-yl)-3-(3,5-dimethoxyphenyl)acrylonitrile. The crude material was purified via flash column chromatography (10% EtOAc in hexane) to give 3-(3,5-dimethoxy-phenyl)-3-phenyl-acrylonitrile as an oil (0.33 g, 89%): 1HNMR (DMSO-d6) δ 7.55-7.35 (m, 5H, Ar), 6.67-6.62 (2ts, 1H, Ar), 6.48-6.45 (2ds, 2H, Ar), 6.39 (s, 0.57H, double bond proton of one isomer), 6.34 (s, 0.43H, double bond proton of the other isomer), 3.76 (s, 3H, OCH3), 3.73 (s, 3H, OCH3); 13C NMR (CDCl3) δ 163.2, 163.1, 160.9, 160.9, 141.2, 138.9, 138.7, 137.0, 130.6, 130.2, 129.7, 128.8, 128.6, 128.5, 117.9, 117.8, 107.8, 107.0, 102.3, 102.2, 95.3, 95.1, 55.7, 55.6; Anal. Calcd. For C17H15NO2 (+0.03 H2O): C, 76.80; H, 5.71; N, 5.27. Found: C, 76.41; H, 5.40; N, 5.18.

Workup

  1. customThe crude material was purified via flash column chromatography (10% EtOAc in hexane)

Sources & evidence

ORD record
ord-306d027f867248a28df734d422815223
Source dataset
uspto-grants-2007_12
Patent number
US07312241B2

Reaction notes

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