Diisopropylamine → 5-Chloro-7-(3-methoxyprop-1-ynyl)-1,3-benzodioxol-4-amine

HRID 347446Notes

Reaction equation

HRID 347446 reaction equation
C(NC(C)C)(C)C.[Cl:8][C:9]1[C:14]([NH2:15])=[C:13]2[O:16][CH2:17][O:18][C:12]2=[C:11](I)[CH:10]=1.[CH2:20]([O:23][CH3:24])[C:21]#[CH:22]>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)I>[Cl:8][C:9]1[C:14]([NH2:15])=[C:13]2[O:16][CH2:17][O:18][C:12]2=[C:11]([C:22]#[C:21][CH2:20][O:23][CH3:24])[CH:10]=1

Participants

7

Reactant 3

HCID 7912DiisopropylamineHCID 693933-MethoxypropyneHCID 17980527HCID 17980527, compound

Product 1

HCID 210827165-Chloro-7-(3-methoxyprop-1-ynyl)-1,3-benzodioxol-4-amine

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Bis(Triphenyl-phosphine)palladium(II) chloride (472 mg), copper iodide (192 mg) and diisopropylamine (680 mg) were added to a stirred solution of 6-chloro-4-iodo-2,3-methylenedioxyaniline (1000 mg) and methyl propargyl ether (471 mg) in ethyl acetate (10 mls) at −20° C. The reaction was allowed to warm to ambient temperature over 16 hours. The reaction mixture was partitioned between ethyl acetate and saturated NaHCO3. The organics were washed with water and saturated brine and dried over magnesium sulfate. The product was purified by column chromatography on silica using a gradient of 80–100% Dichloromethane/isohexane as eluent. 6-chloro-4-(3-methoxyprop-1-ynyl)-2,3-methylendioxyaniline was thus obtained as a tan crystalline solid (200 mg); NMR Spectrum: (DMSOd6) 3.28 (s, 3H), 4.26 (s, 2H), 5.52 (s, 2H), 6.05 (s, 2H), 6.93 (s, 1H).

Workup

  1. customThe reaction mixture was partitioned between ethyl acetate and saturated NaHCO3
  2. washThe organics were washed with water and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. customThe product was purified by column chromatography on silica using a gradient of 80–100% Dichloromethane/isohexane as eluent

Sources & evidence

ORD record
ord-1010025365684dbd9ac3598d385949e6
Source dataset
uspto-grants-2007_02
Patent number
US07173135B2

Reaction notes

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