Potassium Hydroxide → 3,3''-Dimethyl-1',2',3',4',5',6'-hexahydro-[2,2'; 6',2'']terpyridine

HRID 1784227Notes

Reaction equation

HRID 1784227 reaction equation
[CH3:1][C:2]1[C:3]([CH:8]2[CH2:13][C:12](=O)[CH2:11][CH:10]([C:15]3[C:20]([CH3:21])=[CH:19][CH:18]=[CH:17][N:16]=3)[NH:9]2)=[N:4][CH:5]=[CH:6][CH:7]=1.O.NN.[OH-].[K+]>C(O)COCCO>[CH3:1][C:2]1[C:3]([CH:8]2[CH2:13][CH2:12][CH2:11][CH:10]([C:15]3[C:20]([CH3:21])=[CH:19][CH:18]=[CH:17][N:16]=3)[NH:9]2)=[N:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 14797Potassium HydroxideHCID 24654Hydrazine hydrate (1:1)HCID 68972279HCID 68972279, compound

Product 1

HCID 674211653,3''-Dimethyl-1',2',3',4',5',6'-hexahydro-[2,2'; 6',2'']terpyridineYield 97%

Reagents, catalysts & solvents 1

HCID 8117Diethylene GlycolSolvent

Conditions

Temperature
125 °C

Procedure

To a solution of 3,3″-dimethyl-2′,3′,5′,6′-tetrahydro-1′H-[2,2′;6′,2″]terpyridin-4′-one (9.6 g, 34.1 mmol) in diethylene glycol (170 mL) was added hydrazine monohydrate (90 mL, 2.89 mol) and potassium hydroxide pellets (57.4 g, 1.02 mol) and the reaction stirred at 125° C. for 2 hours. 50 mL of hydrazine distilled off and water (200 mL) was added the remaining mixture. The solution was extracted with CH2Cl2 (4×300 mL). The combined organic extracts were dried (MgSO4) and concentrated under reduced pressure. The residue was dissolved in EtOAc (500 mL) and washed with a saturated solution of NaHCO3 (3×100 mL) to remove the residual diethylene glycol. The organic extract was dried (MgSO4) and concentrated under reduced pressure to afford 8.82 g (97%) of 3,3″-dimethyl-1′,2′,3′,4′,5′,6′-hexahydro-[2,2′;6′,2″]terpyridine as yellow solid. 1H NMR (CDCl3) δ 1.50-1.65 (m, 2H), 1.75-1.95 (m, 3H), 2.13 (m, 1H), 2.37 (s, 6H), 3.09 (br t, 1H), 4.15-4.25 (m, 2H), 7.02 (dd, 2H, J=7.5, 4.8 Hz) 7.38 (d, 2H, J=7.5 Hz), 8.46 (br d, 2H).

Workup

  1. distillation50 mL of hydrazine distilled off
  2. additionwater (200 mL) was added the remaining mixture
  3. extractionThe solution was extracted with CH2Cl2 (4×300 mL)
  4. dry with materialThe combined organic extracts were dried (MgSO4)
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in EtOAc (500 mL)
  7. washwashed with a saturated solution of NaHCO3 (3×100 mL)
  8. customto remove the residual diethylene glycol
  9. extractionThe organic extract
  10. dry with materialwas dried (MgSO4)
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-16d3ff05724c49799b5dd239f1f80e7f
Source dataset
uspto-grants-2009_03
Patent number
US07501518B2

Reaction notes

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