Benzenamine, 2-bromo-4-nitro- → 4-Nitroaniline

HRID 1964310Notes

Reaction equation

HRID 1964310 reaction equation
Br[C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].C(C1(C)CC1)#C>C(N(CC)CC)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[N+:9]([C:7]1[CH:8]=[CH:2][C:3]([NH2:4])=[CH:5][CH:6]=1)([O-:11])=[O:10]

Participants

6

Reactant 2

HCID 25840Benzenamine, 2-bromo-4-nitro-HCID 215905601-Ethynyl-1-methylcyclopropane

Product 1

HCID 74754-NitroanilineYield 123.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
70 °C

Procedure

To a deoxygenated solution of 2-bromo-4-nitroaniline (430 mg, 2.0 mmol) and 1-ethynyl-1-methyl-cyclopropane (630 mg, 8.0 mmol) in triethylamine (20 mL) was added CuI (76 mg, 0.40 mmol) and Pd(PPh3)2Cl2 (140 mg, 0.20 mmol) under N2. The mixture was heated at 70° C. and stirred for 24 h. The solid was filtered off and washed with EtOAc (50 mL×3). The filtrate was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate=10/1) to give 24(1-methylcyclopropyl)ethynyl)-4-nitroaniline (340 mg, 79%). 1H NMR (300 MHz, CDCl3) δ 8.15-8.14 (m, 1 H), 7.98-7.95 (m, 1 H), 6.63 (d, J=6.9 Hz, 1 H), 4.80 (brs, 2 H), 1.38 (s, 3 H), 1.04-1.01 (m, 2 H), 0.76-0.73 (m, 2 H).

Workup

  1. filtrationThe solid was filtered off
  2. washwashed with EtOAc (50 mL×3)
  3. customThe filtrate was evaporated under reduced pressure
  4. customthe residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-4234b5e9ae7840d3af8191b3ec31cb76
Source dataset
uspto-grants-2013_04
Patent number
US08415387B2

Reaction notes

Loading…