Hexane → HCID 9877656, compound

HRID 1835829Notes

Reaction equation

HRID 1835829 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH3:8])[N:3]=1.C(N(CC)CC)C.[CH:16]1([C:22]#[CH:23])[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1.CCCCCC>COCCOC.C(OCC)(=O)C.[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>[CH:16]1([C:22]#[C:23][C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([CH3:8])[N:3]=2)[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1

Participants

9

Reactant 4

HCID 8058HexaneHCID 8471TriethylamineHCID 70263EthynylcyclohexaneHCID 792052-Bromo-6-methylpyridine2×

Product 1

HCID 9877656HCID 9877656, compoundYield 77%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

2-Bromo-6-methyl pyridine (2.0 g, 11.6 mmol) and CuI (440 mg, 2.3 mmol) were combined in DME (30 mL), and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (8.0 mL, 58 mmol) and PdCl2(PPh3)2 (814 mg, 1.16 mmol) were added, followed by the dropwise addition of cyclohexylethyne (1.25 g, 11.6 mmol). The reaction was stirred at ambient temperature overnight. GC/MS showed no starting 2-bromo-6-methylpyridine remaining. The mixture was diluted with ethyl acetate (100 mL), and filtered through Celite™. The pad was then thoroughly washed with ethyl acetate and the combined filtrates were washed with water (200 mL), brine (200 mL), dried over Na2SO4, and filtered. The filtrate was concentrated in vacuo, and the residue was purified by column chromatography eluting with hexane then 98:2, 96:4 hexane:ethyl acetate to afford 2-(cyclohexylethynyl)-6-methylpyridine (1.78 g, 77% yield) as a pale brown liquid that partially solidified on standing in the freezer. 1H NMR (CDCl3, 300 MHz) δ 7.52-7.46 (m, 1H), 7.20 (d, J=9 Hz, 1H), 7.03 (d, J=9 Hz, 1H), 2.6 (m, 1H), 2.54 (s, 3H), 2.93-2.89 (m, 2H), 1.78-1.73 (m, 2H), 1.57-1.54 (m, 3H), 1.36-1.32 (m, 3H). MS (ESI) 200.1 (M++H).

Workup

  1. customargon gas was bubbled through the suspension for several minutes
  2. customto deoxygenate the mixture
  3. filtrationfiltered through Celite™
  4. washThe pad was then thoroughly washed with ethyl acetate
  5. washthe combined filtrates were washed with water (200 mL), brine (200 mL)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated in vacuo
  9. customthe residue was purified by column chromatography
  10. washeluting with hexane

Sources & evidence

ORD record
ord-baaa8cb67c6e4d4a977cbec746b55614
Source dataset
uspto-grants-2004_08
Patent number
US06774138B2

Reaction notes

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