1-Iodo-4-nitrobenzene → N-(2,4-dimethoxybenzyl)-3-(4-nitrophenyl)prop-2-yn-1-amine

HRID 2096278Notes

Reaction equation

HRID 2096278 reaction equation
[CH3:1][O:2][C:3]1[CH:13]=[C:12]([O:14][CH3:15])[CH:11]=[CH:10][C:4]=1[CH2:5][NH:6][CH2:7][C:8]#[CH:9].I[C:17]1[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][CH:18]=1>CN(C)C=O.C(N(CC)CC)C.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][O:2][C:3]1[CH:13]=[C:12]([O:14][CH3:15])[CH:11]=[CH:10][C:4]=1[CH2:5][NH:6][CH2:7][C:8]#[C:9][C:17]1[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][CH:18]=1

Participants

7

Reactant 2

HCID 124951-Iodo-4-nitrobenzeneHCID 28419238N-(2,4-dimethoxybenzyl)prop-2-yn-1-amine

Product 1

HCID 67443629N-(2,4-dimethoxybenzyl)-3-(4-nitrophenyl)prop-2-yn-1-amine

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Procedure

To a solution of EXAMPLE 23A (12.47 g, 60.83 mmol) in a mixture of N,N-dimethylformamide (150 mL) and triethylamine (150 mL) was added 1-iodo-4-nitrobenzene (18.18 g, 73 mmol), CuI (2.33 g, 12.2 mmol) and tetrakis(triphenylphosphine)palladium(0) (3.51 g, 3.04 mmol). The reaction mixture was stirred at room temperature overnight, and partitioned between ethyl acetate and brine. The organic phase was washed with brine, and concentrated. The crude material was purified by flash chromatography (20% ethyl acetate in hexane) to afford the title compound 1H NMR (400 MHz, dimethylsulfoxide-d6): δ 2.36 (br s, 1H), 3.59 (s, 2H), 3.72 (s, 2H), 3.74 (s, 3H), 3.77 (s, 3H), 6.48 (dd, J=6.0, 2.4 Hz, 1H), 6.53 (d, J=2.0 Hz, 1H), 7.20 (d, J=8.4 Hz, 1H), 7.67 (d, J=8.8 Hz, 2H), 8.22 (d, J=8.8 Hz, 2H).

Workup

  1. custompartitioned between ethyl acetate and brine
  2. washThe organic phase was washed with brine
  3. concentrationconcentrated
  4. customThe crude material was purified by flash chromatography (20% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-1e12a24e45ac4167bdcd6a9daec620d5
Source dataset
uspto-grants-2013_05
Patent number
US08450320B2

Reaction notes

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