Methyl vinyl ketone → 4-(3-Chloropyridin-2-yl)-4-methylcyclohex-2-enone

HRID 661376Notes

Reaction equation

HRID 661376 reaction equation
[Cl:1][C:2]1[C:3]([CH:8]([CH3:11])[CH:9]=O)=[N:4][CH:5]=[CH:6][CH:7]=1.[OH-].[K+].[CH:14]([C:16]([CH3:18])=[O:17])=[CH2:15]>C(OCC)C>[Cl:1][C:2]1[C:3]([C:8]2([CH3:11])[CH2:15][CH2:14][C:16](=[O:17])[CH:18]=[CH:9]2)=[N:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 6570Methyl vinyl ketoneHCID 14797Potassium HydroxideHCID 866302832-(3-Chloropyridin-2-yl)propanal

Product 1

HCID 674999494-(3-Chloropyridin-2-yl)-4-methylcyclohex-2-enoneYield 22%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To a 0° C. solution of the product of Example 38D (0.71 g, 4.19 mmol) in diethyl ether (10 mL) was added a solution of potassium hydroxide (3M in methanol, 0.56 mL, 1.68 mmol), followed by methyl vinyl ketone (0.47 g, 0.55 mL, 6.70 mmol). The reaction was allowed to warm to ambient temperature and stirred overnight. The reaction mixture was diluted with diethyl ether, and washed with water and brine. The organic layer was concentrated, and the residue was chromatographed on silica gel eluting with 25% ethyl acetate-hexane to give the title compound (0.20 g, 22%). 1H NMR (300 MHz, DMSO-d6) δ ppm 8.53 (dd, J=1.5, 4.6, 1H), 7.92 (dd, J=1.5, 8.0, 1H), 7.45-7.26 (m, 2H), 5.92 (d, J=10.2, 1H), 2.82-2.67 (m, 1H), 2.64-2.52 (m, 1H), 2.31 (ddd, J=4.8, 7.2, 17.3, 1H), 2.12-2.00 (m, 1H). MS (DCI) m/z 222 (M+H)+.

Workup

  1. washwashed with water and brine
  2. concentrationThe organic layer was concentrated
  3. customthe residue was chromatographed on silica gel eluting with 25% ethyl acetate-hexane

Sources & evidence

ORD record
ord-671b2026bdc7401dba48c375eba86d9e
Source dataset
uspto-grants-2011_12
Patent number
US08084616B2

Reaction notes

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