Diisopropylamine → 4-(4-Methoxybut-1-yn-1-yl)-2,3-methylendioxyaniline

HRID 347445Notes

Reaction equation

HRID 347445 reaction equation
I[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]2[O:9][CH2:10][O:11][C:3]=12.[CH3:12][O:13][CH2:14][CH2:15][C:16]#[CH:17].C(NC(C)C)(C)C>C(OCC)(=O)C.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I>[CH3:12][O:13][CH2:14][CH2:15][C:16]#[C:17][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]2[O:9][CH2:10][O:11][C:3]=12

Participants

7

Reactant 3

HCID 7912DiisopropylamineHCID 5421524-Methoxybut-1-yneHCID 226627507-Iodo-1,3-benzodioxol-4-amine

Product 1

HCID 210827084-(4-Methoxybut-1-yn-1-yl)-2,3-methylendioxyanilineYield 82%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 4-iodo-2,3-methylenedioxyaniline (1.32 g, 5.00 mmol) and 4-methoxybut-1-yne (0.84 g, 10.00 mmol) in ethyl acetate (25 ml) was cooled in ice-methanol, under an atmosphere of nitrogen, then treated with bis(triphenylphosphine) palladium(II) dichloride (350 mg, 10 mol %) followed by copper(I) iodide (95 mg, 10 mol %) and diisopropylamine (1.40 ml, 10.0 mmol). The reaction was stirred for 2 hours in the cooling bath and then allowed to warm to room temperature over 4 hours: The mixture was filtered through Celite and the filtrate was then purified by column chromatography on silica using a gradient of methanol in dichloromethane (0–2%) as eluent to give 4-(4-methoxybut-1-yn-1-yl)-2,3-methylendioxyaniline (524 mg, 82%) as a dark oil; LCMS: M+H+ 220 (82%).

Workup

  1. filtrationThe mixture was filtered through Celite
  2. customthe filtrate was then purified by column chromatography on silica using a gradient of methanol in dichloromethane (0–2%) as eluent

Sources & evidence

ORD record
ord-d9b71c28ada04a5b82e8ed3d6b9b6242
Source dataset
uspto-grants-2007_02
Patent number
US07173135B2

Reaction notes

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