Diisopropylamine → N-[3-(7-amino-6-chloro-1,3-benzodioxol-4-yl)prop-2-yn-1-yl]-N'-methylurea

HRID 1785118Notes

Reaction equation

HRID 1785118 reaction equation
[Cl:1][C:2]1[CH:10]=[C:9](I)[C:5]2[O:6][CH2:7][O:8][C:4]=2[C:3]=1[NH2:12].[CH3:13][NH:14][C:15]([NH:17][CH2:18][C:19]#[CH:20])=[O:16].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>[NH2:12][C:3]1[C:4]2[O:8][CH2:7][O:6][C:5]=2[C:9]([C:20]#[C:19][CH2:18][NH:17][C:15]([NH:14][CH3:13])=[O:16])=[CH:10][C:2]=1[Cl:1]

Participants

7

Reactant 3

HCID 7912DiisopropylamineHCID 14344952N-Methyl-N'-2-propyn-1-ylureaHCID 179805275-Chloro-7-iodo-1,3-benzodioxol-4-amine

Product 1

HCID 68884460N-[3-(7-amino-6-chloro-1,3-benzodioxol-4-yl)prop-2-yn-1-yl]-N'-methylureaYield 37.4%

Reagents, catalysts & solvents 3

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

Procedure

5-Chloro-7-iodo-1,3-benzodioxol-4-amine (500 mg, 1.68 mmol) and N-methyl-N′-prop-2-yn-1-ylurea (226 mg, 2.02 mmol) in ethyl acetate (10 ml) were cooled in ice-methanol, under an atmosphere of nitrogen, then treated with bis(triphenylphosphine) palladium(II) dichloride (118 mg, 10 mol %) followed by copper(I) iodide (32 mg, 10 mol %) and diisopropylamine (339 mg, 4.03 mmol). The reaction was allowed to warm to room temperature and stirred 3 hr. then filtered through Celite. The filtrate was purified by column chromatography on silica using ethyl acetate as eluent to give N-[3-(7-amino-6-chloro-1,3-benzodioxol-4-yl)prop-2-yn-1-yl]-N′-methylurea (177 mg, 37%) as an colourless solid; NMR Spectrum:(DMSOd6) 2.55 (d, 3), 4.00 (d, 2H), 5.52 (s, 2H), 5.84 (q, 1H), 6.05 (s, 2H), 6.27 (t, 1H), 6.78 (s, 1H).

Workup

  1. filtrationthen filtered through Celite
  2. customThe filtrate was purified by column chromatography on silica

Sources & evidence

ORD record
ord-406e541964b44e17bdd87d62440fc6cf
Source dataset
uspto-grants-2009_03
Patent number
US07504408B2

Reaction notes

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