Aniline → HCID 9837020, compound

HRID 1595015Notes

Reaction equation

[C:1](ON=O)(C)([CH3:3])[CH3:2].C(Br)C=C.[CH3:12][O:13][C:14]1[CH:20]=[CH:19][C:17](N)=[CH:16][C:15]=1[N+:21]([O-:23])=[O:22].NC1C=CC=CC=1>CC#N>[CH2:3]([C:17]1[CH:19]=[CH:20][C:14]([O:13][CH3:12])=[C:15]([N+:21]([O-:23])=[O:22])[CH:16]=1)[CH:1]=[CH2:2]

Participants

Conditions

Temperature: 37.5 °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-methoxy-3-nitroaniline (504 mg, 3.0 mmol) was added during 20 minutes, while maintaining the temperature of the reaction mixture at 35-40° 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 40° C. for one hour. The volatile material in the reaction mixture was removed at reduced pressure. The crude product was dissolved in ethyl acetate-heptane (1:2, 20 ml) and filtered through a pad of silica. The solvent was removed at reduced pressure. Column chromatography (heptane-ethyl acetate 97:3) gave 230 mg (40%) allyl-4-methoxy-3-nitrobenzene as a yellow oil. 1H NMR (CDCl3, 400 MHz) δ 7.45, (d, 1H, J=2.7 Hz), 7.27, (d, 1H, J=8.6 Hz), 7.10, (dd, 1H, J=8.6, 2.7 Hz), 6.02-5.90, (m, 1H), 5.12-5.02, (m, 2H), 3.86, (s, 3H), 3.62, (m, 2H, J=6.4 Hz); 13C NMR (CDCl3, 100 MHz) δ 158.8, 150.0, 135.9, 133.2, 127.2, 120.2, 117.1, 109.6, 56.2, 36.8; Anal HRMS Calcd. for C10H11NO3 (M): 193.0739. Found: 193.0743

Workup

additionwas added to the reaction mixture which
customThe volatile material in the reaction mixture was removed at reduced pressure
dissolutionThe crude product was dissolved in ethyl acetate-heptane (1:2, 20 ml)
filtrationfiltered through a pad of silica
customThe solvent was removed at reduced pressure

Sources & evidence

ORD record: ord-bf638b2cc02c4911a17293da4f754b07
Source dataset: uspto-grants-2001_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06284894B1

Reaction notes

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