Ethyl Acetate → HCID 21192629, compound

HRID 1067583Notes

Reaction equation

HRID 1067583 reaction equation
[CH3:1][N:2]([CH3:9])[C:3](=O)[C:4]([CH3:7])([CH3:6])[CH3:5].P(Cl)(Cl)(Cl)=O.[NH2:15][C:16]1[N:17]=[N:18][C:19]([Cl:22])=[CH:20][CH:21]=1.C(OCC)(=O)C>C1(C)C=CC=CC=1>[CH3:1][N:2]([CH3:9])[C:3](=[N:15][C:16]1[N:17]=[N:18][C:19]([Cl:22])=[CH:20][CH:21]=1)[C:4]([CH3:7])([CH3:6])[CH3:5]

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 216436-Amino-3-chloropyridazineHCID 24813Phosphorus oxychlorideHCID 141102N,N-Dimethyl-tert-butylcarboxamide

Product 1

HCID 21192629HCID 21192629, compoundYield 28.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

36 g of N,N-dimethylpivalamide was dissolved in 85 ml of toluene; under ice cooling conditions, 11.3 ml of phosphorus oxychloride was added drop by drop, followed by stirring at room temperature for 24 hours. To this solution, 12.0 g of 3-amino-6-chloropyridazine was added, followed by stirring at 60-70° C. for 24 hours. After cooling, ethyl acetate was added; the mixture was washed with a 2 N aqueous solution of sodium hydroxide and saline and dried with sodium sulfate. After the dry product was concentrated under reduced pressure, the residue was subjected to silica gel column chromatography and eluted with hexane:ethyl acetate:triethylamine (50:50:2). The desired fraction was collected to yield 6.38 g of N,N-dimethyl-N′-(6-chloropyridazin-3-yl)pivalamidine. The mother liquor was purified by silica gel column chromatography to yield 6.07 g of the amidine. 12.45 g of the amidine derivative obtained was dissolved in 100 ml of methanol; a solution of 4.31 g of hydroxylamine hydrochloride in methanol was added, followed by stirring at room temperature for 2 hours. The methanol was concentrated to half volume under reduced pressure; the crystal precipitated was collected by filtration, washed with water and ethyl ether and dried to yield 10.44 g of the title compound.

Workup

  1. stirringby stirring at 60-70° C. for 24 hours
  2. temperatureAfter cooling
  3. washthe mixture was washed with a 2 N aqueous solution of sodium hydroxide and saline
  4. dry with materialdried with sodium sulfate
  5. concentrationAfter the dry product was concentrated under reduced pressure
  6. washeluted with hexane:ethyl acetate:triethylamine (50:50:2)
  7. customThe desired fraction was collected

Sources & evidence

ORD record
ord-a2e97f73bc134b5eaa2ab50ecc9b268f
Source dataset
uspto-grants-2001_06
Patent number
US06248740B1

Reaction notes

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