tert-Butoxy bis(dimethylamino)methane → (E)-2-(2-(dimethylamino)vinyl)-4-nitrobenzonitrile

HRID 1438099Notes

Reaction equation

[CH3:1][C:2]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].CC(C)(O[CH:17](N(C)C)[N:18]([CH3:20])[CH3:19])C>CN(C=O)C>[CH3:17][N:18]([CH3:20])/[CH:19]=[CH:1]/[C:2]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5]

Participants

Conditions

Temperature: 70 °C

Procedure

A mixture of 2-methyl-4-nitrobenzonitrile (Aldrich, 5.0 g, 31 mmol) and 1-(1,1-dimethylethoxy)-N,N,N′,N′-tetramethyl-methanediamine (Aldrich, 12.2 mL, 59 mmol) in dry DMF (8 mL) was stirred at 70° C. for 2 h under N2. After cooling to rt, DMF was removed in vacuo and the crude product was triturated with hexanes/ethyl acetate (5:1). The solid was collected by filtration and washed with hexane to give (E)-2-(2-(dimethylamino)vinyl)-4-nitrobenzonitrile (6.5 g, 97% yield) as a black solid. 1H NMR (400 MHz, CDCl3) δ ppm 2.97 (s, 6H) 5.36 (d, J=513.18 Hz, 1H) 7.16 (d, J=13.62 Hz, 1H) 7.52 (d, J=8.79 Hz, 1H) 7.60 (m, 1H) 8.11 (d, J=1.76 Hz, 1H).

Workup

temperatureAfter cooling to rt
customDMF was removed in vacuo
customthe crude product was triturated with hexanes/ethyl acetate (5:1)
filtrationThe solid was collected by filtration
washwashed with hexane

Sources & evidence

ORD record: ord-5e5e126cf55a481aa24aa41e6315e662
Source dataset: uspto-grants-2009_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07622585B2

Reaction notes

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