Nitrogen → 3-Chloro-2-(p-tolyl)pyridine

HRID 1434713Notes

Reaction equation

HRID 1434713 reaction equation
Cl[C:2]1[C:7]([Cl:8])=[CH:6][CH:5]=[CH:4][N:3]=1.B(O)(O)[C:10]1[CH:11]=[CH:12][C:13]([CH3:16])=[CH:14][CH:15]=1.N#N>C([O-])([O-])=O.[Na+].[Na+].C(#N)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:8][C:7]1[C:2]([C:10]2[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=2)=[N:3][CH:4]=[CH:5][CH:6]=1

Participants

7

Reactant 3

HCID 947NitrogenHCID 169882,3-DichloropyridineHCID 79799Tolylboronic acid

Product 1

HCID 207099363-Chloro-2-(p-tolyl)pyridine

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 6342AcetonitrileSolventHCID 10340Sodium CarbonateSolvent

Conditions

Temperature
85 °C

Procedure

A solution of 2,3-dichloropyridine (0.9663 g, 6.5 mmol), p-tolylboronic acid (0.8569 g, 6.3 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.3618 g, 0.31 mmol) in 0.5 M Na2CO3 (25 mL) and acetonitrile (25 mL) was flushed with N2, sealed and heated at 85° C. for 16 hours. The reaction mixture was cooled to room temperature and the volume reduced by half under vacuum. The concentrate was extracted with dichloromethane (3×20 mL), dried (MgSO4) and condensed to yellow-green oil. The residue was purified by column chromatography, eluted with hexanes:ethyl acetate:dichloromethane (7:2:1)) to provide the title compound as a yellow-orange oil. MS (ESI+) m/z 203 (M+H)+; 1H NMR (DMSO-d6) δ 2.38 (s, 3H), 7.30 (d, J 8.2, 2H), 7.42 (d, J 8.2, 1H), 7.59 (d, J 8.2, 2H), 8.03 (d, J 8.1, 1H), 8.62 (d, J 6.1, 1H); Anal. Calc'd for C12H10ClN.0.1H2O: C, 70.15; H, 5.00; N, 6.82. Found: C, 70.06; H, 4.67; N, 6.67.

Workup

  1. customsealed
  2. temperatureThe reaction mixture was cooled to room temperature
  3. extractionThe concentrate was extracted with dichloromethane (3×20 mL)
  4. customdried
  5. custom(MgSO4) and condensed to yellow-green oil
  6. customThe residue was purified by column chromatography
  7. washeluted with hexanes:ethyl acetate:dichloromethane (7:2:1))

Sources & evidence

ORD record
ord-6ab9ec91de294126bcb40422f59fecd7
Source dataset
uspto-grants-2009_11
Patent number
US07615570B2

Reaction notes

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