Aniline → 2-(3,5-Dinitrobenzyl)acrylic acid

HRID 1595023

Reaction equation

HRID 1595023 reaction equation
C(ON=O)(C)(C)C.Br[CH2:9][C:10](=[CH2:14])[C:11]([OH:13])=[O:12].[N+:15]([C:18]1[CH:19]=[C:20]([CH:22]=[C:23]([N+:25]([O-:27])=[O:26])[CH:24]=1)N)([O-:17])=[O:16].NC1C=CC=CC=1>CC#N>[N+:15]([C:18]1[CH:19]=[C:20]([CH:22]=[C:23]([N+:25]([O-:27])=[O:26])[CH:24]=1)[CH2:9][C:10](=[CH2:14])[C:11]([OH:13])=[O:12])([O-:17])=[O:16]

Participants

6

Reactant 4

HCID 6115AnilineHCID 10906Tert-Butyl nitriteHCID 120683,5-DinitroanilineHCID 5588842-(Bromomethyl)propenoic acid

Product 1

HCID 109995222-(3,5-Dinitrobenzyl)acrylic acidYield 60%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
17.5 °C

Procedure

To a solution of t-butylnitrite (535 μl, 4.5 mmol) and 2-(bromomethyl)acrylic acid (7.42 g, 45.0 mmol) in CH3CN (10 ml), 3,5-dinitroaniline (549 mg, 3.0 mmol) was added during 20 minutes, while maintaining the temperature of the reaction mixture at 15-20° C. At the end of the addition of the aniline extra t-butylnitrite (180 μl, 1.5 mmol) was added to the reaction mixture. After heating to 35° C. for 5 minutes, the mixture was stirred at room temperature for one hour. The volatile material in the reaction mixture was then removed at reduced pressure. The remaining crystalline residue was washed with heptane (5×50 ml) to remove unreacted 2-(bromomethyl)acrylic acid. Column chromatography (heptane-ethyl acetate-methanol-acetic acid 5:4:1:0.04) of the remaining crude product followed by crystallization from toluene gave 450 mg (60%) of 2-(3,5-dinitrobenzyl)acrylic acid as yellow needles. 1H NMR (CDCl3, 300 MHz) δ 8.93, (t, 1H, J=2.1 Hz), 8.43, (d, 2H, J=2.1 Hz), 6.56, (s, 1H), 5.93, (m, 1H), 3.85, (s, 2H).

Workup

  1. additionwas added to the reaction mixture
  2. temperatureAfter heating to 35° C. for 5 minutes
  3. customThe volatile material in the reaction mixture was then removed at reduced pressure
  4. washThe remaining crystalline residue was washed with heptane (5×50 ml)
  5. customto remove unreacted 2-(bromomethyl)acrylic acid
  6. customColumn chromatography (heptane-ethyl acetate-methanol-acetic acid 5:4:1:0.04) of the remaining crude product followed by crystallization from toluene

Sources & evidence

ORD record
ord-170ab3fd81694b2c9913cb870e3c5486
Source dataset
uspto-grants-2001_09
Patent number
US06284894B1

Linked notes

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