4-Vinylpyridine → 6-chloro-5-[(E)-2-pyridin-4-ylvinyl]pyridin-3-amine

HRID 2307761Notes

Reaction equation

HRID 2307761 reaction equation
[NH2:1][C:2]1[CH:3]=[N:4][C:5]([Cl:9])=[C:6](Br)[CH:7]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[CH:32]([C:34]1[CH:39]=[CH:38][N:37]=[CH:36][CH:35]=1)=[CH2:33].C(N(CC)CC)C>CN(C=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C>[Cl:9][C:5]1[N:4]=[CH:3][C:2]([NH2:1])=[CH:7][C:6]=1/[CH:33]=[CH:32]/[C:34]1[CH:39]=[CH:38][N:37]=[CH:36][CH:35]=1

Participants

8

Reactant 4

HCID 75024-VinylpyridineHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 145952215-Bromo-6-chloropyridin-3-amine

Product 1

HCID 226076916-chloro-5-[(E)-2-pyridin-4-ylvinyl]pyridin-3-amineYield 84%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3-amino-5-bromo-6-chloropyridine (2.0 g, 9.64 mmol), Pd2(dba)3 (440 mg, 0.48 mmol), tri-o-tolylphosphine (438 mg, 1.44 mmol), 4-vinylpyridine (2.08 mL, 19.28 mmol), and triethylamine (4.03 mL, 29 mmol) in DMF (30 mL) was stirred at 100° C. for 15 hours, cooled to room temperature, treated with ethyl acetate (200 mL), washed twice with brine, dried (MgSO4), filtered and concentrated. The residual solid recrystallized from hexanes/dichloromethane to provide desired product (1.86 g, 84%). MS (APCI) m/e 232 (M+H)+.

Workup

  1. washwashed twice with brine
  2. dry with materialdried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residual solid recrystallized from hexanes/dichloromethane

Sources & evidence

ORD record
ord-59f5f35fd7d04022a1cd64366ea73e84
Source dataset
uspto-grants-2004_12
Patent number
US06831175B2

Reaction notes

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