Aniline → 4-allyl-benzonitrile
Reaction equation
[C:1](ON=O)(C)([CH3:3])[CH3:2].C(Br)C=C.N[C:13]1[CH:20]=[CH:19][C:16]([C:17]#[N:18])=[CH:15][CH:14]=1.NC1C=CC=CC=1>CC#N>[CH2:3]([C:13]1[CH:20]=[CH:19][C:16]([C:17]#[N:18])=[CH:15][CH:14]=1)[CH:1]=[CH2:2]Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 43 °C
Procedure
To a solution of t-butylnitrite (535 μl, 4.5 mmol) and allyl bromide (3.9 ml, 45.0 mmol) in CH3CN (3 ml), 4-aminobenzonitrile (354 mg, 3.0 mmol) was added during 20 minutes, while maintaining the temperature of the reaction mixture at 42-44° C. At the end of the addition of the aniline, extra t-butylnitrite (180 μl, 1.5 mmol) was added to the reaction mixture which then was stirred at 50° C. for three hours during which extra t-butylnitrite (180 μl, 1.5 mmol) was added. The volatile material in the reaction mixture was removed at reduced pressure. Heptane-ethyl acetate (10 ml, 1:1) was then added to the crude product and the mixture was filtered. Column chromatography (heptane-ethyl acetate 49:1) of the concentrated filtrate gave 160 mg (37%) 4-allyl-benzonitrile as a clear oil containing 16% of 4-bromo-benzonitrile. This corresponds to 30% yield of 4-allylbenzonitrile. 1H NMR (CDCl3, 400 MHz) δ 7.60, (m, 2H, J=8.3 Hz), 7.31, (m, 2H, J=8.3 Hz), 5.99-5.88, (m, 1H), 5.18-5.08, (m, 2H), 3.46, (d, 2H, J=6.7 Hz); Anal HRMS Calcd. for C10H9N (M): 143.0735. Found: 143.0734.
Workup
- additionwas added to the reaction mixture which
- additionwas added
- customThe volatile material in the reaction mixture was removed at reduced pressure
- additionHeptane-ethyl acetate (10 ml, 1:1) was then added to the crude product
- filtrationthe mixture was filtered
Sources & evidence
- ORD record
- ord-c57721df3b854368a869372d70875581
- Source dataset
- uspto-grants-2001_09
- Patent number
- US06284894B1
Reaction notes
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