3,6-Dichloropyridazin-4-amine → HCID 21515359, compound

HRID 1475419Notes

Reaction equation

HRID 1475419 reaction equation
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[K+].[Cl:7][C:8]1[N:9]=[N:10][C:11]([Cl:15])=[CH:12][C:13]=1[NH2:14].BrCC(C)=C>C1COCC1>[Cl:7][C:8]1[N:9]=[N:10][C:11]([Cl:15])=[CH:12][C:13]=1[NH:14][CH2:1][C:2]([CH3:5])=[CH2:3]

Participants

5

Reactant 3

HCID 2984983,6-Dichloropyridazin-4-amineHCID 3577853-Bromo-2-methyl-1-propeneHCID 23665647Potassium tert-butoxide

Product 1

HCID 21515359HCID 21515359, compoundYield 75.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Potassium tert-butoxide (157.5 g) was charged portionwise to a stirred solution of 3,6-dichloro-pyridazin-4-ylamine (210 g) in THF (3.36 L). After 15 minutes, 3-bromo-2-methylpropene (141.8 mL) was added dropwise over a period of 30 minutes, maintaining the temperature <25° C. The solution was allowed to stir at room temperature for 16 h, after which time the reaction was concentrated and the residue partitioned between DCM (6 L) and water (6 L). The aqueous phase was extracted with DCM (2×5 L). The combined organic phases were washed (brine, 5 L), dried with magnesium sulfate, filtered and concentrated. Chromatography (Silica gel, eluting with 70:30 Heptane:-EtOAc) gave the title compound (211.7 g). 1H NMR (270 MHz, CDCl3): 6.49 (1H, s), 5.48 (1H, br s), 5.00 (1H, s), 4.91 (1H, s), 3.81 (2H, d, J ═6 Hz), 1.80 (3H, s).

Workup

  1. temperaturemaintaining the temperature <25° C
  2. concentrationafter which time the reaction was concentrated
  3. customthe residue partitioned between DCM (6 L) and water (6 L)
  4. extractionThe aqueous phase was extracted with DCM (2×5 L)
  5. washThe combined organic phases were washed (brine, 5 L)
  6. dry with materialdried with magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. washChromatography (Silica gel, eluting with 70:30 Heptane:-EtOAc)

Sources & evidence

ORD record
ord-14d467e0105b4d04a9a930678965aecb
Source dataset
uspto-grants-2015_04
Patent number
US09018214B2

Reaction notes

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