Diisopropylamine → 2-{[3-(7-amino-6-chloro-1,3-benzodioxol-4-yl)prop-2-yn-1-yl]oxy}-N,N-dimethylacetamide

HRID 1785172Notes

Reaction equation

HRID 1785172 reaction equation
C(NC(C)C)(C)C.[Cl:8][C:9]1[CH:17]=[C:16](I)[C:12]2[O:13][CH2:14][O:15][C:11]=2[C:10]=1[NH2:19].[CH3:20][N:21]([CH3:29])[C:22](=[O:28])[CH2:23][O:24][CH2:25][C:26]#[CH:27]>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>[NH2:19][C:10]1[C:11]2[O:15][CH2:14][O:13][C:12]=2[C:16]([C:27]#[C:26][CH2:25][O:24][CH2:23][C:22]([N:21]([CH3:29])[CH3:20])=[O:28])=[CH:17][C:9]=1[Cl:8]

Participants

6

Reactant 3

HCID 7912DiisopropylamineHCID 17980527HCID 17980527, compoundHCID 45087887HCID 45087887, compound

Product 1

HCID 688813182-{[3-(7-amino-6-chloro-1,3-benzodioxol-4-yl)prop-2-yn-1-yl]oxy}-N,N-dimethylacetamideYield 81.9%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-20 °C

Procedure

Bis(triphenylphosphine)palladium(II) chloride (0.236 g), cuprous iodide (0.96 g) and diisopropylamine (0.47 ml) were added to a stirred solution of 5-chloro-7-iodo-1,3-benzodioxol-4-amine (0.500 g) and N,N-dimethyl-2-(prop-2-yn-1-yloxy)acetamide (0.474 g) in ethyl acetate (8 ml) cooled to −20° C. under a nitrogen atmosphere; the resultant mixture was stirred for 4 hr at ambient temperature. The reaction mixture was filtered through Celite, ethyl acetate (12 ml) was then added and the resultant solution washed with saturated aqueous sodium bicarbonate (20 ml). The aqueous layer was re-extracted with ethyl acetate (20 ml). The combined organic extracts were washed with brine (20 ml), dried over sodium sulphate and then evaporated. The residue was purified by column chromatography on silica using ethyl acetate as eluent. There was thus obtained the title compound as a solid (0.428 g). NMR Spectrum: (CDCl3) 2.96 (s, 3H), 3.02 (s, 3H), 4.06 (s, 2H), 4.31 (s, 2H), 4.52 (s, 2H), 6.02 (s, 2H), 6.89 (s, 1H); Mass Spectrum: M+H+ 311 and 313.

Workup

  1. filtrationThe reaction mixture was filtered through Celite, ethyl acetate (12 ml)
  2. additionwas then added
  3. washthe resultant solution washed with saturated aqueous sodium bicarbonate (20 ml)
  4. extractionThe aqueous layer was re-extracted with ethyl acetate (20 ml)
  5. washThe combined organic extracts were washed with brine (20 ml)
  6. dry with materialdried over sodium sulphate
  7. customevaporated
  8. customThe residue was purified by column chromatography on silica

Sources & evidence

ORD record
ord-9a1a3174c3a84c88a3ce45c1227eb5c7
Source dataset
uspto-grants-2009_03
Patent number
US07504408B2

Reaction notes

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