Potassium Phosphate, Tribasic → HCID 86675934, compound

HRID 572686Notes

Reaction equation

HRID 572686 reaction equation
Br[C:2]1[C:3](=[O:10])[N:4]([CH3:9])[N:5]=[C:6]([Cl:8])[CH:7]=1.[CH:11](B(O)O)=[CH:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:8][C:6]1[CH:7]=[C:2]([CH:11]=[CH:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:3](=[O:10])[N:4]([CH3:9])[N:5]=1

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 27343812-Phenylvinylboronic acidHCID 592164744-Bromo-6-chloro-2-methyl-2,3-dihydropyridazin-3-one

Product 1

HCID 86675934HCID 86675934, compoundYield 67.9%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of 4-bromo-6-chloro-2-methylpyridazin-3(2H)-one (8 g, 35.8 mmol, Preparation #28), styrylboronic acid (6.62 g, 44.8 mmol, Combiblocks), bis(triphenylphosphine)palladium(II) chloride (2.51 g, 3.58 mmol, Hindustan Platiniums) and potassium phosphate (11.40 g, 53.7 mmol, Aldrich) in aqueous dioxane (75%: 100 mL) was heated to about 85° C. for 6 h. The reaction mixture was cooled to RT and then concentrated on the rotovapor to 25 mL. The oily residue obtained was partitioned between EtOAc (100 mL) and water (50 mL). The layers were separated and then the aqueous layer was extracted with EtOAc (2×100 mL). The combined organic layers were dried over sodium sulphate and evaporated under reduced pressure. The residue obtained was purified by silica gel column chromatography by eluting with 10-20% ETOAc in hexane. The relevant fractions containing the product were combined and evaporated under reduced pressure to afford 6-chloro-2-methyl-4-styrylpyridazin-3(2H)-one 6 g (67.9%) as yellow solid. 1H NMR (400 MHz, CDCl3) δ 7.878-7.838 (d, J=17 Hz, 1H), 7.620-7.560 (m, 2H) 7.412-7.344 (m, 3H) 7.279 (s, 1H) 7.177-7.136 (d, J=16 Hz, 1H) 3.809 (s, 3H); MS m/z: 247.1 (M+H)+

Workup

  1. temperatureThe reaction mixture was cooled to RT
  2. concentrationconcentrated on the rotovapor to 25 mL
  3. customThe oily residue obtained
  4. customwas partitioned between EtOAc (100 mL) and water (50 mL)
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with EtOAc (2×100 mL)
  7. dry with materialThe combined organic layers were dried over sodium sulphate
  8. customevaporated under reduced pressure
  9. customThe residue obtained
  10. customwas purified by silica gel column chromatography
  11. washby eluting with 10-20% ETOAc in hexane
  12. additionThe relevant fractions containing the product
  13. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-3ea1e00df270444b98a5eaacc417be7f
Source dataset
uspto-grants-2015_05
Patent number
US09029409B2

Reaction notes

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