Dimethylformamide → [(2,6-Difluoro-3,5-dimethoxyphenyl)ethynyl](trimethyl)silane

HRID 1052308Notes

Reaction equation

HRID 1052308 reaction equation
[F:1][C:2]1[C:7](I)=[C:6]([F:9])[C:5]([O:10][CH3:11])=[CH:4][C:3]=1[O:12][CH3:13].[CH3:14][Si:15]([C:18]#[CH:19])([CH3:17])[CH3:16].C(N(CC)CC)C.CN(C)C=O>[Cu]I.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>[F:1][C:2]1[C:3]([O:12][CH3:13])=[CH:4][C:5]([O:10][CH3:11])=[C:6]([F:9])[C:7]=1[C:19]#[C:18][Si:15]([CH3:17])([CH3:16])[CH3:14]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 867228052,4-Difluoro-3-iodo-1,5-dimethoxybenzene

Product 1

HCID 89963360[(2,6-Difluoro-3,5-dimethoxyphenyl)ethynyl](trimethyl)silaneYield 94.3%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Procedure

To a stirred mixture of 2,4-difluoro-3-iodo-1,5-dimethoxybenzene (740 mg, 2.47 mmol), (trimethylsilyl)acetylene (0.697 mL, 4.93 mmol), copper(I) iodide (38 mg, 0.20 mmol), and triethylamine (0.52 mL, 3.7 mmol) in N,N-dimethylformamide (DMF) (4 mL, 50 mmol), bis(triphenylphosphine)palladium(II) chloride (86 mg, 0.12 mmol) was added. The reaction mixture was stirred at room temperature for 70 hours. The reaction was quenched with saturated aq. NH4Cl, then extracted with methylene chloride. The combined organic layers were dried over MgSO4, then concentrated. The residue was purified on silica gel (eluting with 0 to 30% EtOAc in hexanes) to give the desired product (630 mg, 94%).

Workup

  1. additionwas added
  2. customThe reaction was quenched with saturated aq. NH4Cl
  3. extractionextracted with methylene chloride
  4. dry with materialThe combined organic layers were dried over MgSO4
  5. concentrationconcentrated
  6. customThe residue was purified on silica gel (eluting with 0 to 30% EtOAc in hexanes)

Sources & evidence

ORD record
ord-d2912e01a0ff4cc98eca9c1a70fdb86b
Source dataset
uspto-grants-2016_07
Patent number
US09388185B2

Reaction notes

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