Diisopropylamine → 3-Cyano-6,7-dimethoxy-4-[6chloro-4-(3-methoxyprop-1-ynyl)-2,3-methylene dioxyanilino]quinoline

HRID 347424Notes

Reaction equation

HRID 347424 reaction equation
[Cl:1][C:2]1[C:7]([NH:8][C:9]2[C:18]3[C:13](=[CH:14][C:15]([O:21][CH3:22])=[C:16]([O:19][CH3:20])[CH:17]=3)[N:12]=[CH:11][C:10]=2[C:23]#[N:24])=[C:6]2[O:25][CH2:26][O:27][C:5]2=[C:4](I)[CH:3]=1.[CH2:29]([O:32][CH3:33])[C:30]#[CH:31].C(NC(C)C)(C)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.C(OCC)(=O)C>[C:23]([C:10]1[CH:11]=[N:12][C:13]2[C:18]([C:9]=1[NH:8][C:7]1[C:2]([Cl:1])=[CH:3][C:4]([C:31]#[C:30][CH2:29][O:32][CH3:33])=[C:5]3[O:27][CH2:26][O:25][C:6]=13)=[CH:17][C:16]([O:19][CH3:20])=[C:15]([O:21][CH3:22])[CH:14]=2)#[N:24]

Participants

6

Reactant 3

HCID 7912DiisopropylamineHCID 693933-MethoxypropyneHCID 179805104-(6-Chloro-4-iodo-2,3-methylenedioxyan ilino)-3-cyano-6,7-dimethoxyquinoline

Product 1

HCID 104339863-Cyano-6,7-dimethoxy-4-[6chloro-4-(3-methoxyprop-1-ynyl)-2,3-methylene dioxyanilino]quinoline

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 4-(6-chloro-4-iodo-2,3-methylenedioxyanilino)-3-cyano-6,7-dimethoxyquinoline (0.25 g), methyl 2-propynyl ether (0.09 ml), N,N-diisopropylamine (0.154 ml), bis(triphenylphosphine)palladium(II) dichloride (0.069 g), cuprous iodide (0.028 g) and ethyl acetate (10 ml) was stirred and heated to reflux for 12 hours. The reaction mixture was cooled to ambient temperature and partitioned between ethyl acetate and water. The organic layer was dried over magnesium sulphate and evaporated and the residue was purified by column chromatography on silica using increasingly polar mixtures of hexane and ethyl acetate as eluent. There was thus obtained the title compound as an oil (0.138 g); NMR Spectrum: (DMSOd6) 3.42 (s, 3H), 3.97 (s, 3H), 3.99 (s, 3H), 4.38 (s, 2H), 6.17 (s, 2H), 7.13 (s, 1H), 7.36 (s, 1H), 7.92 (s, 1H), 8.39 (s, 1H), 9.42 (br s, 1H); Mass Spectrum: M+H+ 452.

Workup

  1. temperatureheated
  2. temperatureto reflux for 12 hours
  3. custompartitioned between ethyl acetate and water
  4. dry with materialThe organic layer was dried over magnesium sulphate
  5. customevaporated
  6. customthe residue was purified by column chromatography on silica using
  7. temperatureincreasingly polar mixtures of hexane and ethyl acetate as eluent

Sources & evidence

ORD record
ord-ef3b890825fd4f318b4f1a3c911c3a11
Source dataset
uspto-grants-2007_02
Patent number
US07173135B2

Reaction notes

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