Phenylacetylene → HCID 11514215, compound

HRID 1847403Notes

Reaction equation

HRID 1847403 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:12]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)#[CH:13]>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:6]=[CH:5][C:3]([NH2:4])=[C:2]([C:13]#[C:12][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:8]=1)([O-:11])=[O:10]

Participants

6

Reactant 2

HCID 10821PhenylacetyleneHCID 25840Benzenamine, 2-bromo-4-nitro-

Product 1

HCID 11514215HCID 11514215, compoundYield 14,271.2%

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 (2.17 g, 0.01 mmol), ethynylbenzene (1.53 g, 0.015 mol) and CuI (10 mg, 0.05 mmol) in triethylamine (20 mL) was added Pd(PPh3)2Cl2 (210 mg, 0.2 mmol) under N2. The mixture was heated at 70° C. and stirred for 24 hours. 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 4-nitro-2-(phenylethynyl)aniline (340 mg, 14%). 1H NMR (300 MHz, CDCl3) δ 8.37-8.29 (m, 1H), 8.08-8.00 (m, 1H), 7.56-7.51 (m, 2H), 7.41-7.37 (m, 3H), 6.72 (m, 4.95 (brs, 2H).

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-af05f1c983574b8291a0b0512454bebd
Source dataset
uspto-grants-2015_02
Patent number
US08952050B2

Reaction notes

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