Diisopropylamine → 5-Chloro-7-(4-methoxypent-1-yn-1-yl)-1,3-benzodioxol-4-amine

HRID 1785147Notes

Reaction equation

HRID 1785147 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][CH:15]([CH3:19])[CH2:16][C:17]#[CH:18].C(NC(C)C)(C)C>C(OCC)(=O)C.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.[Cu]I>[Cl:1][C:2]1[CH:10]=[C:9]([C:18]#[C:17][CH2:16][CH:15]([O:14][CH3:13])[CH3:19])[C:5]2[O:6][CH2:7][O:8][C:4]=2[C:3]=1[NH2:12]

Participants

7

Reactant 3

HCID 7912DiisopropylamineHCID 179805275-Chloro-7-iodo-1,3-benzodioxol-4-amineHCID 866015644-Methoxypent-1-yne

Product 1

HCID 688812175-Chloro-7-(4-methoxypent-1-yn-1-yl)-1,3-benzodioxol-4-amineYield 92%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

5-chloro-7-iodo-1,3-benzodioxol-4-amine (600 mg, 2.02 mmol) and 4-methoxypent-1-yne (500 mg, 5.10 mmol) in ethyl acetate (8 ml) were cooled in ice-methanol, under an atmosphere of nitrogen, then treated with bis(triphenylphosphine)palladium(II) dichloride (141 mg, 10 mol %) followed by copper(I) iodide (38 mg, 10 mol %) and diisopropylamine (407 mg, 5.69 mmol). The reaction was allowed to warn to room temperature and stirred 90 min 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-(4-methoxypent-1-yn-1-yl)-1,3-benzodioxol-4-amine (495 mg, 92%) as a dark brown oil;

Workup

  1. customto warn to room temperature
  2. filtrationthen filtered through Celite
  3. customThe filtrate was purified by column chromatography on silica using
  4. additiona 1:1 mixture of methyl tert-butyl ether and iso-hexane as eluent

Sources & evidence

ORD record
ord-64136a8cd324442f9a988bcc15cbb60e
Source dataset
uspto-grants-2009_03
Patent number
US07504408B2

Reaction notes

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