Ethyl Acetate → HCID 21192629, compound

HRID 1169117Notes

Reaction equation

HRID 1169117 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>[Cl:22][C:19]1[N:18]=[N:17][C:16]([N:15]=[C:3]([N:2]([CH3:9])[CH3:1])[C:4]([CH3:7])([CH3:6])[CH3:5])=[CH:21][CH:20]=1

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, dried over sodium a sulfate and 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 N2-(6-chloropyridazin-3-yl)-N1,N1-dimethylpivalamidine. The filtrate was purified by silica gel column chromatography to yield 6.07 g of the amidine. 12.5 g of the amidine derivative obtained was dissolved in 60 ml of methanol; a solution of 4.31 g of hydroxylamine hydrochloride in 40 ml of 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 over sodium a sulfate
  5. concentrationconcentrated under reduced pressure
  6. washeluted with hexane:ethyl acetate:triethylamine (50:50:2)
  7. customThe desired fraction was collected

Sources & evidence

ORD record
ord-0b6a45aa8ca144f7a011bf2de4a56675
Source dataset
uspto-grants-2003_09
Patent number
US06627630B1

Reaction notes

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