Cyclohexene → HCID 45094652, compound

HRID 859148Notes

Reaction equation

HRID 859148 reaction equation
[CH2:1]([C:3]1[C:11](/[C:12](/[CH3:15])=[CH:13]\[CH3:14])=[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][N:5]2[N:4]=1)[CH3:2].C(C1C(C(CC)=C)=C2C=CC=CN2N=1)C.C1CCCCC=1>[Pd]>[CH:12]([C:11]1[C:3]([CH2:1][CH3:2])=[N:4][N:5]2[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=12)([CH2:13][CH3:14])[CH3:15]

Participants

5

Reactant 3

HCID 8079CyclohexeneHCID 45094570HCID 45094570, compoundHCID 45094571HCID 45094571, compound

Product 1

HCID 45094652HCID 45094652, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst

Conditions

Temperature
85 °C

Procedure

A 0° C. solution of 1-(2-ethylpyrazolo[1,5-a]pyridin-3-yl)ethanone (1.33 g, 7.1 mmol) in THF (20.0 mL) was treated with 1.0M THF solution of ethyl magnesium bromide (9.0 mL, 9.0 mmol). The reaction was allowed to warm to room temperature and stirred for 2.5 hours. An additional amount of ethyl magnesium bromide (2.0 mL, 2.0 mmol) was added and the reaction stirred for 1.5 hours. The reaction was quenched with 2N HCl then extracted with ethyl acetate, washed with brine, dried over MgSO4 and filtered. The filtrate was concentrated in vacuo to dryness. The residue was subjected to column chromatography (20% ethyl acetate/heptane) to give 0.55 g (39%) of a yellow oil as a 4:1 mixture of the regio-isomers of 2-ethyl-3-[(1Z)-1-methylprop-1-enyl]pyrazolo[1,5-a]pyridine and 2-ethyl-3-(1-ethylvinyl)pyrazolo[1,5-a]pyridine. The mixture (0.22 mg, 1.1 mmol) was placed in a flask with cyclohexene (8.0 mL), 10% palladium on carbon (0.05 g) and AICl3 (0.016 g) and heated to 85° C. for 39 hours. The reaction was cooled to room temperature and filtered through diatomaceous earth. The filtrate was concentrated in vacuo to dryness. The residue was subjected to column chromatography (20% ethyl acetate/heptane) to give 0.19 g (86%) of a clear oil as the title compound: 1H NMR (400 MHz, CDCl3) δ 8.36 (d, J=7.0 Hz, 1H), 7.45 (d, J=9.0 Hz, 1H), 7.00–6.96 (m, 1H), 6.64–6.60 (m, 1H), 2.93–2.82 (m, 3H), 1.83–1.74 (m, 2H), 1.40–1.33 (m, 6H), 0.87 (t, J=7.4 Hz, 3H); MS (EI) m/z 203.1 (M++H).

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. filtrationfiltered through diatomaceous earth
  3. concentrationThe filtrate was concentrated in vacuo to dryness

Sources & evidence

ORD record
ord-c3e09b41ad184275baabbee08d189efd
Source dataset
uspto-grants-2006_12
Patent number
US07151109B2

Reaction notes

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