Diisopropylamine → 5-Chloro-7-[3-(2-methoxyethoxy)prop-1-yn-1-yl]-1,3-benzodioxol-4-amine

HRID 1785105Notes

Reaction equation

HRID 1785105 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][O:14][CH2:15][CH2:16][O:17][CH2:18][C:19]#[CH:20].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>[Cl:1][C:2]1[CH:10]=[C:9]([C:20]#[C:19][CH2:18][O:17][CH2:16][CH2:15][O:14][CH3:13])[C:5]2[O:6][CH2:7][O:8][C:4]=2[C:3]=1[NH2:12]

Participants

7

Reactant 3

HCID 7912DiisopropylamineHCID 155665773-(2-Methoxyethoxy)prop-1-yneHCID 179805275-Chloro-7-iodo-1,3-benzodioxol-4-amine

Product 1

HCID 688813295-Chloro-7-[3-(2-methoxyethoxy)prop-1-yn-1-yl]-1,3-benzodioxol-4-amineYield 86%

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 (1.0 g, 3.36 mmol) and 3-(2-methoxyethoxy)prop-1-yne (766 mg, 6.72 mmol) in ethyl acetate (12 ml) were cooled in ice-methanol, under an atmosphere of nitrogen, and then treated with bis(triphenylphosphine) palladium(II) dichloride (236 mg, 10 mol %) followed by copper(I) iodide (64 mg, 10 mol %) and diisopropylamine (681 mg, 6.74 mmol). The reaction mixture was allowed to warm to room temperature and stirred for 2.5 hours and then filtered through Celite. The filtrate was purified by column chromatography on silica using a 1:1 mixture of methyl tert-butyl ether and iso-hexane as eluent to give 5-chloro-7-[3-(2-methoxyethoxy)prop-1-yn-1-yl]-1,3-benzodioxol-4-amine (816 mg, 86%) as a dark orange oil; solidified on standing; NMR Spectrum: (CDCl3) 3.40 (s, 3H), 3.58 (m, 2H), 3.74 (m, 2H), 4.06 (s, 2H), 4.42 (s, 2H), 6.01 (s, 2H), 6.88 (s, 1H).

Workup

  1. filtrationfiltered through Celite
  2. customThe filtrate was purified by column chromatography on silica using
  3. additiona 1:1 mixture of methyl tert-butyl ether and iso-hexane as eluent

Sources & evidence

ORD record
ord-da4f073e48274596bac6afd0de47976e
Source dataset
uspto-grants-2009_03
Patent number
US07504408B2

Reaction notes

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