Hydrochloric Acid → HCID 86702314, compound

HRID 923821Notes

Reaction equation

HRID 923821 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[C:10](Br)[CH:11]=1)[O:8][C:7](=[O:13])[C:6]([C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=1)=[CH:5]2.[CH:22](NC(C)C)([CH3:24])[CH3:23].[C:29]([OH:33])#[C:30][CH2:31][CH3:32].Cl.CN([CH:38]=[O:39])C>[Cu]I.CC#N.CC#N.Cl[Pd]Cl.O>[OH:33][CH2:29][CH2:30][C:31]#[C:32][C:2]1[CH:3]=[C:4]2[C:9](=[C:10]([C:23]#[C:22][CH2:24][CH2:38][OH:39])[CH:11]=1)[O:8][C:7](=[O:13])[C:6]([C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=1)=[CH:5]2

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 6228Dimethylformamide2×HCID 7912DiisopropylamineHCID 15129470HCID 15129470, compoundHCID 86702313HCID 86702313, compound

Product 1

HCID 86702314HCID 86702314, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6093782Bis(acetonitrile)dichloropalladiumCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

6,8-Dibromo-3-(4-methoxy-phenyl)-chromen-2-one (30.8 g, 75.1 mmol), copper(1)iodide (1.50 g, 7.88 mmol) and bis(acetonitril)palladium(II) chloride (5.00 g, 7.12 mmol) are dissolved in 300 ml DMF and 50 ml diisopropylamin at 70° C., and a solution of butyne-1-ol (20.0 g, 285 mmol) in 50 ml DMF is added dropwise within 30 min. The reaction mixture is stirred overnight at 80° C., then poured onto 300 ml water and acidified with 2 N hydrochloric acid. The precipitated product is filtered by vacuum, then filtered through silica gel with THF/toluene (4:1) and addition of a small amount of ethanol, and the crude product is recrystallized from toluene. 6,8-Bis-(4-hydroxy-but-1-ynyl)-3-(4-methoxy-phenyl)-chromen-2-one is obtained as light brown solid, which is pure enough to be used as starting material for the next step.

Workup

  1. filtrationThe precipitated product is filtered by vacuum
  2. filtrationfiltered through silica gel with THF/toluene (4:1) and addition of a small amount of ethanol
  3. customthe crude product is recrystallized from toluene

Sources & evidence

ORD record
ord-1b24b17df7ce45bbb43be29c557c773d
Source dataset
uspto-grants-2016_03
Patent number
US09279082B2

Reaction notes

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