2,4,6-Trimethylpyridine → HCID 24902916, compound

HRID 582005Notes

Reaction equation

HRID 582005 reaction equation
[F:1][C:2]([F:17])([F:16])[C:3]1[CH:15]=[CH:14][C:6]([C:7]([CH:9]([C:12]#[N:13])[C:10]#[N:11])=O)=[CH:5][CH:4]=1.N1C(C)=CC(C)=CC=1C.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.Cl.[C:43]([NH:47][NH2:48])([CH3:46])([CH3:45])[CH3:44].C(=O)([O-])[O-].[Na+].[Na+]>C(Cl)Cl.C1COCC1>[NH2:11][C:10]1[N:47]([C:43]([CH3:46])([CH3:45])[CH3:44])[N:48]=[C:7]([C:6]2[CH:14]=[CH:15][C:3]([C:2]([F:17])([F:16])[F:1])=[CH:4][CH:5]=2)[C:9]=1[C:12]#[N:13]

Participants

8

Reactant 5

HCID 79532,4,6-TrimethylpyridineHCID 10340Sodium CarbonateHCID 67749Trifluoromethanesulfonic anhydrideHCID 81889tert-Butylhydrazine monohydrochlorideHCID 53851481HCID 53851481, compound

Product 1

HCID 24902916HCID 24902916, compoundYield 31.8%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-(4-trifluoromethylbenzoyl)propanedinitrile (1.70 g, 7.15 mmol) in CH2Cl2 (60 ml), was added collidine (1.89 ml, 14.3 mmol) followed by trifluoromethanesulphonic anhydride (1.45 ml, 8.58 mmol) and the mixture stirred at room temperature for 2 h. The reaction was concentrated under reduced pressure and the residue dissolved in THF (100 ml). This was added to a suspension of tert-butyl hydrazine hydrochloride (0.98 g, 7.86 mmol) and sodium carbonate (1.14 g, 10.73 mmol) in THF and heated at reflux for 2.5h. The reaction was again concentrated under reduced pressure, the residue dissolved in ethyl acetate (100ml), washed with 2M hydrochloric acid (1×100 ml), water (1×100 ml) and brine (1×100 ml), dried (MgSO4) and solvent then removed under reduced pressure. The resulting solid was subjected to column chromatography to give the title compound (700 mg) as a pale pink solid after recrystallisation from ether, m.p. 155-156°. δH (CDCl3) 1.68 (9H, s), 4.46 (2H, br s), 7.66 (2H, d, J 8.0 Hz), and 8.03 (2H, d, J 8.0 Hz).

Workup

  1. concentrationThe reaction was concentrated under reduced pressure
  2. dissolutionthe residue dissolved in THF (100 ml)
  3. temperatureheated
  4. temperatureat reflux for 2.5h
  5. concentrationThe reaction was again concentrated under reduced pressure
  6. dissolutionthe residue dissolved in ethyl acetate (100ml)
  7. washwashed with 2M hydrochloric acid (1×100 ml), water (1×100 ml) and brine (1×100 ml)
  8. dry with materialdried (MgSO4) and solvent
  9. customthen removed under reduced pressure

Sources & evidence

ORD record
ord-cec34ee81b3a43ccba1b351f934cad2a
Source dataset
uspto-grants-1999_07
Patent number
US05922741

Reaction notes

Loading…