Acetic Acid → 2,4'-Bipyridine

HRID 2241093Notes

Reaction equation

HRID 2241093 reaction equation
[Cl-].C[N+:3]1C(=O)N(C)[CH:6]=[CH:7][CH:8]=1.[C:11]([C:14]1[CH:19]=[CH:18][N:17]=[CH:16][CH:15]=1)(=O)[CH3:12].C(O)(=O)C.C([O-])(=O)C.[NH4+].[OH-].[Na+]>C(#N)C.C(N(CC)CC)C>[N:3]1[CH:8]=[CH:7][CH:6]=[CH:12][C:11]=1[C:14]1[CH:19]=[CH:18][N:17]=[CH:16][CH:15]=1

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 142824-AcetylpyridineHCID 14798Sodium HydroxideHCID 517165Ammonium AcetateHCID 230833421,3-dimethyl-2,3-dihydro-2-oxopyrimidinium Chloride

Product 1

HCID 684882,4'-BipyridineYield 80%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolvent2×HCID 8471TriethylamineSolvent2×

Procedure

14.0 g (87 mmol) of 1,3-dimethyl-2,3-dihydro-2-oxopyrimidinium chloride obtained in Example 1 was dissolved in 25 ml of acetonitrile and mixed with 10 g (83 mmol) of 4-acetylpyridine, and 12.6 g (125 mmol) of triethylamine was added dropwise thereto at 45° C. or less. After 30 minutes of the reaction at 45° C., acetonitrile and triethylamine were evaporated under a reduced pressure, and 25 ml (416 mmol) of acetic acid and 39 g (454 mmol) of ammonium acetate were added to the residual liquid to carry out the reaction at 120° C. for 8 hours. After completion of the reaction, this was cooled to room temperature, neutralized with 217 g of 25% sodium hydroxide aqueous solution and then extracted three times with 200 ml of toluene. The organic layer was concentrated and then purified by distillation under a reduced pressure to obtain 10.3 g (yield 80%) of the title compound (purity 99.9%, melting point 56-57° C.).

Workup

  1. additionwas added dropwise
  2. customat 45° C. or less
  3. customAfter 30 minutes of the reaction at 45° C.
  4. additionwere added to the residual liquid
  5. customthe reaction at 120° C. for 8 hours
  6. customAfter completion of the reaction
  7. extractionextracted three times with 200 ml of toluene
  8. concentrationThe organic layer was concentrated
  9. distillationpurified by distillation under a reduced pressure

Sources & evidence

ORD record
ord-efaf63fc123240fc83bf711e3f51a450
Source dataset
uspto-grants-2010_05
Patent number
US07723522B2

Reaction notes

Loading…