Sodium Hydroxide → 3-Chloro-6-propylpyridazine

HRID 1982124Notes

Reaction equation

HRID 1982124 reaction equation
P(Cl)(Cl)([Cl:3])=O.[CH2:6]([C:9]1[CH:10]=[CH:11][C:12](=O)[NH:13][N:14]=1)[CH2:7][CH3:8].[OH-].[Na+].C(=O)([O-])O.[Na+]>O>[Cl:3][C:12]1[N:13]=[N:14][C:9]([CH2:6][CH2:7][CH3:8])=[CH:10][CH:11]=1

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 544302216-Propylpyridazin-3(2H)-one

Product 1

HCID 197973033-Chloro-6-propylpyridazineYield 73.2%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

46.0 g of phosphorus oxychloride were heated to 60° C. in a sulphonation flask under nitrogen and treated within 1 hour with 27.6 g of 6-propyl-3(2H)-pyridazinone (prepared according to Example 3) in small portions. The mixture was subsequently heated slowly to 100° C. and stirred at this temperature until the reaction was complete according to thin-layer chromatography (about 2 hours). After cooling to room temperature, the dark brown solution was poured into 1 l of water and neutralized with solid sodium hydroxide and sodium hydrogen carbonate. The aqueous phase was subsequently extracted once with 500 ml of tert.butyl methyl ether and then twice with 250 ml of tert.butyl methyl ether each time. The organic phases were washed with 500 ml of water and the aqueous phase was back-extracted twice with 100 ml of tert.butyl methyl ether each time. The combined organic phases were dried over sodium sulphate and freed from solvent on a rotary evaporator. Distillation of the resulting dark brown oil in a high vacuum gave in the main run 22.9 g (73.1%) of 3-chloro-6-propylpyridazine as a colourless liquid; b.p. 72°-74° C./0.4 Torr.

Workup

  1. customwas complete according to thin-layer chromatography (about 2 hours)
  2. temperatureAfter cooling to room temperature
  3. extractionThe aqueous phase was subsequently extracted once with 500 ml of tert.butyl methyl ether
  4. washThe organic phases were washed with 500 ml of water
  5. extractionthe aqueous phase was back-extracted twice with 100 ml of tert.butyl methyl ether each time
  6. dry with materialThe combined organic phases were dried over sodium sulphate
  7. customfreed from solvent on a rotary evaporator
  8. distillationDistillation of the resulting dark brown oil in a high vacuum

Sources & evidence

ORD record
ord-6be48780269843fc9ec744a01292feb6
Source dataset
uspto-grants-1986_06
Patent number
US04595521

Reaction notes

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