Diethyl (cyanomethyl)phosphonate → HCID 54463059, compound

HRID 1745353Notes

Reaction equation

HRID 1745353 reaction equation
COC1C=C(C(C2C=CC(OC)=C(OC)C=2)=CC([O-])=O)C=CC=1OC.[CH2:26]([O:28][C:29]1[CH:30]=[C:31]([CH:40]=[CH:41][C:42]=1[O:43][CH3:44])[C:32]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)=O)[CH3:27].C(OP([CH2:53][C:54]#[N:55])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>>[CH2:26]([O:28][C:29]1[CH:30]=[C:31]([C:32]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)=[CH:53][C:54]#[N:55])[CH:40]=[CH:41][C:42]=1[O:43][CH3:44])[CH3:27]

Participants

5

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 14297383HCID 14297383, compoundHCID 21584610HCID 21584610, compound

Product 1

HCID 54463059HCID 54463059, compound

Procedure

3-(3-Ethoxy-4-methoxyphenyl)-3-phenylacrylonitrile was prepared analogously to 3,3-bis-(3,4-dimethoxyphenyl)acrylate using 3-ethoxy-4-methoxybenzophenone (1.3 g, 5 mmol), diethylcyanomethylphosphonate (0.9 mL, 5.5 mmol) and lithium hexamethyldisilazide (4.2 mL, 5.5 mmol, 1.3M) with a reaction time of 24 hours at room temperature. The crude mixture was purified by flash column chromatography (silica gel, methylene chloride) to afford 1.35 g (96%) of a mixture of the E and Z isomers as a white solid: mp 74–77° C.; 1H NMR (CDCl3) δ 7.50–7.24(m, 10H), 7.07–6.75 (m, 6H), 5.60 (s, 1H), 4.15–3.95 (m, 4H), 3.92 (s, 3H), 3.89 (s, 3H), 1.50–1.36 (m, 6H); 13C NMR (CDCl3) δ 162.8, 162.7, 151.4, 150.9, 148.1, 147.1, 147.9, 139.3, 137.1, 131.3, 130.2, 129.9, 129.5, 129.3, 128.6, 128.5, 128.4, 123.1, 122.0, 118.3, 118.2, 113.9, 112.5, 110.9, 93.3, 92.9, 64.4, 55.9, 55.9, 14.6; Anal. Calcd for C18H17NO2. Theoretical: C, 77.40; H, 6.13; N, 5.01. Found: C, 77.14; H, 6.06; N, 4.75.

Workup

  1. customwith a reaction time of 24 hours
  2. customat room temperature
  3. customThe crude mixture was purified by flash column chromatography (silica gel, methylene chloride)

Sources & evidence

ORD record
ord-73ddbc999c9845349db1cb046ad648cc
Source dataset
uspto-grants-2006_03
Patent number
US07019030B2

Reaction notes

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