Isopropanol → 2-Hydrazinyl-6-methylpyridine

HRID 2424759Notes

Reaction equation

HRID 2424759 reaction equation
F[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH3:8])[N:3]=1.C(O)(C)C.[NH2:13][NH2:14]>C(OC)(C)(C)C.[Cl-].[Na+].O>[CH3:8][C:4]1[N:3]=[C:2]([NH:13][NH2:14])[CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 3

HCID 3776IsopropanolHCID 9321HydrazineHCID 960902-Fluoro-6-methylpyridine

Product 1

HCID 135904652-Hydrazinyl-6-methylpyridineYield 76.1%

Reagents, catalysts & solvents 2

HCID 15413tert-Butyl methyl etherSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
10 °C

Procedure

A jacketed reaction flask was equipped with mechanical stirrer, nitrogen inlet, and reflux condenser and the jacket was cooled to 10° C. The reactor was programmed to automatically cool to 0° C. if at any point the internal temperature exceeded 80° C. The reactor was purged with a steady stream of nitrogen gas. To the reactor was charged 25 g (0.225 mol) of 2-fluoro-6-methylpyridine followed by 100 ml of isopropanol and the jacket temperature was adjusted to 73° C. (corresponding to an internal temperature of 70° C.). To the reactor was charged 44 g (0.90 mol) of 65% aqueous hydrazine and the mixture was stirred overnight with the jacket set at 70° C. The reactor contents were diluted with 125 ml of methyl t-butyl ether (MTBE) and 13 ml of saturated brine to give two layers which were separated. The aqueous layer was extracted with 2×60 ml of MTBE. The combined organic layers were combined and dried over sodium sulfate (anhydrous). The drying agent was removed by filtration and the organic filtrate was concentrated by rotary evaporation. The resulting oil solidified upon standing to give the desired product (21.1 g) as a white solid.

Workup

  1. customA jacketed reaction flask was equipped with mechanical stirrer, nitrogen inlet
  2. temperaturereflux condenser
  3. temperatureto automatically cool to 0° C. if at any point the internal temperature
  4. customexceeded 80° C
  5. customThe reactor was purged with a steady stream of nitrogen gas
  6. customwas adjusted to 73° C.
  7. customcorresponding to an internal temperature of 70° C.
  8. customset at 70° C
  9. customto give two layers which
  10. customwere separated
  11. extractionThe aqueous layer was extracted with 2×60 ml of MTBE
  12. dry with materialdried over sodium sulfate (anhydrous)
  13. customThe drying agent was removed by filtration
  14. concentrationthe organic filtrate was concentrated by rotary evaporation

Sources & evidence

ORD record
ord-29c0639755994eb3b12d0fad064b855d
Source dataset
uspto-grants-2011_06
Patent number
US07964612B2

Reaction notes

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