2,6-Dibromotoluene → (2-((3-Bromo-2-methylphenyl)ethynyl)phenyl)methanol

HRID 661885Notes

Reaction equation

[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[CH2:9][OH:10])#[CH:2].[Br:11][C:12]1[CH:17]=[CH:16][CH:15]=[C:14](Br)[C:13]=1[CH3:19]>C1COCC1.[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>[Br:11][C:12]1[C:13]([CH3:19])=[C:14]([C:2]#[C:1][C:3]2[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=2[CH2:9][OH:10])[CH:15]=[CH:16][CH:17]=1

Participants

Conditions

Temperature: 60 °C

Procedure

Step 1 A mixture of (2-ethynylphenyl)methanol (100 mg, 0.757 mmol), 1,3-dibromo-2-methylbenzene (189 mg, 0.757 mmol) and TEA (0.211 mL, 1.513 mmol) in THF (2 mL) was purged with nitrogen and treated with copper (I) iodide (2.88 mg, 0.015 mmol) and bis(triphenylphosphine)palladium(II) chloride (26.6 mg, 0.038 mmol). The mixture was heated in a sealed tube at 60° C. for 1.5 h. The mixture was filtered, the filtrate was washed with NaHCO3 (aq) and water, and dried and concentrated. The residue was purified by column chromatography (eluting with hexane-EtOAc) to provide (2-((3-bromo-2-methylphenyl)ethynyl)phenyl)methanol as a white solid (130 mg, 57%). 1H NMR (400 MHz, chloroform-d) δ 7.44-7.58 (4H, m), 7.39 (1H, td, J=7.54, 1.43 Hz), 7.27-7.34 (1H, m), 7.00-7.09 (1H, m), 4.93 (2H, d, J=6.38 Hz), 2.64 (3H, s). Mass spectrum m/z 323, 325 (M+Na)+.

Workup

customwas purged with nitrogen
filtrationThe mixture was filtered
washthe filtrate was washed with NaHCO3 (aq) and water
customdried
concentrationconcentrated
customThe residue was purified by column chromatography (eluting with hexane-EtOAc)

Sources & evidence

ORD record: ord-9e0ae2c7f0354fd895ed9cba92385191
Source dataset: uspto-grants-2011_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08084620B2

Reaction notes

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