Diisopropylamine → Phenyl-t-butylacetylene

HRID 1804468

Reaction equation

HRID 1804468 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(NC(C)C)(C)C.[CH3:15][C:16]([CH3:20])([CH3:19])[C:17]#[CH:18]>CN(C)C=O.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>[CH3:15][C:16]([CH3:20])([CH3:19])[C:17]#[C:18][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 3

HCID 7912DiisopropylamineHCID 11575IodobenzeneHCID 135123,3-Dimethyl-1-butyne

Product 1

HCID 138165Phenyl-t-butylacetyleneYield 95.4%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
75 °C

Procedure

A degassed solution of iodobenzene (0.549 mL, 4.90 mmol), dichlorobis(triphenylphosphine)-palladium(II) (0.206 g, 0.294 mmol), copper(I) iodide (0.047 g, 0.245 mmol), and diisopropylamine (3.49 mL, 24.5 mmol) in N,N-dimethylformamide (20 mL) was added 3,3-dimethylbut-1-yne (0.896 mL, 7.35 mmol). The reaction mixture was and heated to 75° C. for 45 minutes. The reaction mixture was then diluted with ethyl acetate (150 mL), washed with 10% aqueous solution of lithium chloride (2×100 mL), washed with a 2M aqueous solution of ammonium hydroxide, washed with brine (100 mL), and dried over anhydrous sodium sulfate. Concentration followed by purification on silica gel chromatography with hexanes/dichloromethane (10/1) afforded (3,3-Dimethylbut-1-ynyl)benzene (740 mg). The compound had an HPLC ret. time=3.78 min.−Column: YMC S5 COMBISCREEN® 4.6×50 mm; Gradient time: 4 min; Flow rate=4 ml/min; Solvent A=10% MeOH−90% Water−0.2% H3PO4; Solvent B=90% MeOH−10% water−0.2% H3PO4; Start % B=0; Final % B=100.

Workup

  1. washwashed with 10% aqueous solution of lithium chloride (2×100 mL)
  2. washwashed with a 2M aqueous solution of ammonium hydroxide
  3. washwashed with brine (100 mL)
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationConcentration
  6. customfollowed by purification on silica gel chromatography with hexanes/dichloromethane (10/1)

Sources & evidence

ORD record
ord-23ca2e0987d44b8cac48d7fb6a8a6c7f
Source dataset
uspto-grants-2013_01
Patent number
US08354398B2

Linked notes

Loading…