Aniline → HCID 9881278, compound

HRID 1595014Notes

Reaction equation

[C:1](ON=O)(C)([CH3:3])[CH3:2].C(Br)C=C.[Br:12][C:13]1[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][C:14]=1N.NC1C=CC=CC=1>CC#N>[CH2:3]([C:14]1[CH:16]=[C:17]([N+:20]([O-:22])=[O:21])[CH:18]=[CH:19][C:13]=1[Br:12])[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), 2-bromo-5-nitroaniline (651 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 23° C. for one hour. The volatile material in the reaction mixture was removed at reduced pressure. Column chromatography (heptane-ethyl acetate 49:1) gave 568 mg (78%) allyl-2-bromo-5-nitrobenzene as a light yellow oil containing 7% of 3,4-dibromo-nitrobenzene, which crystallized upon standing overnight in the refrigerator. This corresponds to 72% yield of allyl-2-bromo-5-nitrobenzene. The allyl-2-bromo-5-nitrobenzene could be purified by crystallization from pentane. 1H NMR (CDCl3, 400 MHz) δ 8.10, (d, 1H, J=2.7 Hz), 7.95, (dd, 1H, J=8.7, 2.7 Hz), 7.74, (d, 1H, J=8.7 Hz), 6.03-5.92, (m, 1H), 5.26-5.13, (m, 2H), 3.60, (m, 2H, J=6.5 Hz); 13C NMR (CDCl3, 100 MHz) δ 147.7, 142.0, 134.1, 134.1, 132.3, 125.3, 122.9, 118.8, 40.5; Anal HRMS Calcd. for C9H8BrNO2 (M): 240.9738. Found: 240.9739.

Workup

additionwas added to the reaction mixture which
customThe volatile material in the reaction mixture was removed at reduced pressure

Sources & evidence

ORD record: ord-7ad1b5af80d042e3affcd12c4f4c60ce
Source dataset: uspto-grants-2001_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06284894B1

Reaction notes

Loading…