Hydrazine → 3-Bromo-5-fluoro-4-hydrazinylpyridine

HRID 524921Notes

Reaction equation

HRID 524921 reaction equation
[Br:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([F:9])[C:7]=1Cl.[NH2:10][NH2:11].C([O-])([O-])=O.[Na+].[Na+]>C1(O)CCCCC1>[Br:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([F:9])[C:7]=1[NH:10][NH2:11]

Participants

5

Reactant 3

HCID 9321HydrazineHCID 10340Sodium CarbonateHCID 709772193-Bromo-4-chloro-5-fluoropyridine

Product 1

HCID 867209763-Bromo-5-fluoro-4-hydrazinylpyridine

Reagents, catalysts & solvents 1

HCID 7966CyclohexanolSolvent

Procedure

3-bromo-4-chloro-5-fluoro-pyridine (500 mg, 2.376 mmol), hydrazine (761.4 mg, 745.7 μL, 23.76 mmol), Na2CO3 (503.7 mg, 4.752 mmol) in cyclohexanol was heated at 100 C overnight. The reaction mixture was filtered on celite and loaded on a SCX column, washed with DCM/MeOH mixtures and was eluted with a 2M solution of NH3 in MeOH. The filtrate was concentrated in vacuo and the 3/1 mixture of 3-bromo-5-fluoro-4-hydrazinylpyridine and 3-bromo-4-chloro-5-hydrazinylpyridine was used in next step without further purification. MS (ES+) 205.9.

Workup

  1. filtrationThe reaction mixture was filtered on celite and
  2. washwashed with DCM/MeOH mixtures
  3. washwas eluted with a 2M solution of NH3 in MeOH
  4. concentrationThe filtrate was concentrated in vacuo
  5. additionthe 3/1 mixture of 3-bromo-5-fluoro-4-hydrazinylpyridine and 3-bromo-4-chloro-5-hydrazinylpyridine
  6. customwas used in next step without further purification

Sources & evidence

ORD record
ord-7547567c86c9499d93c7b3a0195ea27b
Source dataset
uspto-grants-2016_05
Patent number
US09340546B2

Reaction notes

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