Aniline → HCID 10219815, compound

HRID 1595013Notes

Reaction equation

HRID 1595013 reaction equation
[C:1](ON=O)(C)([CH3:3])[CH3:2].C(Br)C=C.[Cl:12][C:13]1[CH:19]=[C:18]([N+:20]([O-:22])=[O:21])[CH:17]=[CH:16][C:14]=1N.NC1C=CC=CC=1>CC#N>[CH2:3]([C:14]1[CH:16]=[CH:17][C:18]([N+:20]([O-:22])=[O:21])=[CH:19][C:13]=1[Cl:12])[CH:1]=[CH2:2]

Participants

6

Reactant 4

HCID 6115AnilineHCID 7841Allyl bromideHCID 84922-Chloro-4-nitroanilineHCID 10906Tert-Butyl nitrite2×

Product 1

HCID 10219815HCID 10219815, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
12 °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-chloro-4-nitroaniline (518 mg, 3.0 mmol) was added during 20 minutes, while maintaining the temperature of the reaction mixture at 11-13° 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 then removed at reduced pressure. Column chromatography (heptane-ethyl acetate 97:3) gave 497 mg (84%) allyl-2-chloro-4-nitrobenzene as a light yellow oil containing 5% of 2-chloro-4-nitrobromobenzene. This corresponds to 79% yield of allyl-2-chloro-4-nitrobenzene. 1H NMR (CDCl3, 400 MHz) δ 8.25, (d, 1H, J=2.4 Hz), 8.08, (dd, 1H, J=8.5, 2.3 Hz), 7.42, (d, 1H, J=8.5 Hz), 6.01-5.89, (m, 1H), 5.23-5.10, (m, 2H), 3.59, (d, 2H, J=6.5 Hz); 13C NMR (CDCl3, 100 MHz) δ 147.3, 145.9, 135.3, 134.0, 131.2, 125.0, 122.2, 118.5, 38.0; Anal HRMS Calcd. for C9H8ClNO2 (M): 197.0244. Found: 197.0247.

Workup

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

Sources & evidence

ORD record
ord-803f821409d34a8e930519b8edbe1e68
Source dataset
uspto-grants-2001_09
Patent number
US06284894B1

Reaction notes

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