Hydrazine hydrate (1:1) → 6-Hydrazinonicotinic acid

HRID 526399Notes

Reaction equation

HRID 526399 reaction equation
Cl[C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][N:3]=1.O.[NH2:12][NH2:13]>O1CCOCC1>[NH:12]([C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][N:3]=1)[NH2:13]

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 792226-Chloronicotinic acid

Product 1

HCID 37826176-Hydrazinonicotinic acidYield 57.7%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

A suspension of 6-chloronicotinic acid (30.0 g, 189 mmol) in 1,4-dioxane (29.0 mL) was treated with hydrazine hydrate (134 mL, 1.51 mol) and heated to 90° C. overnight. The mixture was cooled to ambient temperature and then in ice for 30 min. Precipitate formation was induced by etching the side of the flask and the precipitate was filtered and re-suspended in EtOH (500 mL) with vigorous stirring. The resulting suspension was filtered. The precipitate was dissolved in water (300 mL) and HCl (6N) was added until pH=1. The pH was then adjusted to 5 with NaOH (50%, aq.) and the resulting suspension was stirred for 1 h. The solids were collected by filtration and dried in vacuum to give the title compound (16.65 g, 57.7% yield) as an off-white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 6.70 (d, 1H) 7.86 (dd, J=8.97, 2.15 Hz, 1H) 8.32 (br. s., 1H) 8.52 (d, J=1.77 Hz, 1H). MS m/z [M+H]+ 154.

Workup

  1. temperatureThe mixture was cooled to ambient temperature
  2. filtrationthe precipitate was filtered
  3. filtrationThe resulting suspension was filtered
  4. dissolutionThe precipitate was dissolved in water (300 mL)
  5. additionHCl (6N) was added until pH=1
  6. filtrationThe solids were collected by filtration
  7. customdried in vacuum

Sources & evidence

ORD record
ord-329b9db2eecb4417a66ed8646ba89fa9
Source dataset
uspto-grants-2016_05
Patent number
US09345713B2

Reaction notes

Loading…