Hydrazine hydrate (1:1) → 6-Chloro-5-(morpholin-4-yl)pyridazin-3-ylhydrazine

HRID 47231Notes

Reaction equation

HRID 47231 reaction equation
[Cl:1][C:2]1[N:3]=[N:4][C:5](Cl)=[CH:6][C:7]=1[N:8]1[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1.O.[NH2:16][NH2:17]>O1CCOCC1>[Cl:1][C:2]1[N:3]=[N:4][C:5]([NH:16][NH2:17])=[CH:6][C:7]=1[N:8]1[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 31249534-(3,6-Dichloropyridazin-4-yl)morpholine

Product 1

HCID 2161086-Chloro-5-(morpholin-4-yl)pyridazin-3-ylhydrazineYield 74%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

A mixture of 4-(3,6-dichloropyridazin-4-yl)morpholine (5 g, 21.3 mmol) and hydrazine hydrate (7.0 ml, 141 mmol) in 1,4-dioxane (100 ml) was stirred and heated at reflux for 20 hours. Upon cooling the 1,4-dioxane was removed in vacuo. The residue was then partitioned between dichloromethane and saturated aqueous sodium hydrogen carbonate. The aqueous layer was further extracted with dichloromethane (×2). The combined organic extracts were dried (Na2SO4), filtered and evaporated. The residue was purified by chromatography on silica gel, eluting with dichloromethane/methanol/aqueous ammonia (91:8:1) to give 6-chloro-5-(morpholin-4-yl)pyridazin-3-ylhydrazine (3.6 g, 74%): 1H NMR (250 MHz, d6-DMSO) δ3.17-3.37 (4H, m), 3.72-3.77 (4H, m), 4.31 (2H, br s), 6.58 (1H, s), 7.97 (1H, br s); MS (ES+) m/e 230, 232 [MH+].

Workup

  1. temperatureheated
  2. temperatureat reflux for 20 hours
  3. customwas removed in vacuo
  4. customThe residue was then partitioned between dichloromethane and saturated aqueous sodium hydrogen carbonate
  5. extractionThe aqueous layer was further extracted with dichloromethane (×2)
  6. dry with materialThe combined organic extracts were dried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue was purified by chromatography on silica gel
  10. washeluting with dichloromethane/methanol/aqueous ammonia (91:8:1)

Sources & evidence

ORD record
ord-bd60b97190a341a2b4820fa21b88814e
Source dataset
uspto-grants-2004_03
Patent number
US06699859B1

Reaction notes

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