3,4-Bis(benzyloxy)-6-chloropyridazine → HCID 71270105, compound

HRID 927101Notes

Reaction equation

HRID 927101 reaction equation
[CH2:1]([O:8][C:9]1[N:10]=[N:11][C:12](Cl)=[CH:13][C:14]=1[O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Br-].[CH:25]1([CH2:31][Zn+])[CH2:30][CH2:29][CH2:28][CH2:27][CH2:26]1>CN1CCCC1.C(OCC)(=O)C.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH2:1]([O:8][C:9]1[N:10]=[N:11][C:12]([CH2:31][CH:25]2[CH2:30][CH2:29][CH2:28][CH2:27][CH2:26]2)=[CH:13][C:14]=1[O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 122134743,4-Bis(benzyloxy)-6-chloropyridazine2×HCID 178419774HCID 178419774, compound

Product 1

HCID 71270105HCID 71270105, compoundYield 45.4%

Reagents, catalysts & solvents 3

HCID 178418851HCID 178418851, compoundCatalystHCID 84541-MethylpyrrolidineSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 3,4-bis(benzyloxy)-6-chloropyridazine (Intermediate 1) (1 g, 3.06 mmol) and bis(tri-tert-butylphosphine)palladium (0.063 g, 0.122 mmol) in N-methylpyrrolidine (30.0 ml) under nitrogen was added (cyclohexylmethyl)zinc(II) bromide (0.5 M in tetrahydrofuran) (12.24 ml, 6.12 mmol) and the resulting brown mixture was stirred at room temperature overnight and then heated at 100° C. for 2 hours. The reaction mixture was then allowed to cool, diluted with ethyl acetate and washed with saturated aqueous sodium bicarbonate solution, saturated aqueous ammonium chloride solution and brine. The organics were dried (MgSO4), filtered and solvent removed in vacuo to give a brown oil. The oil was purified by silica chromatography (eluting with 0-30% ethyl acetate in petrol) to yield the title compound (540 mg, 1.39 mmol, 45% yield).

Workup

  1. temperatureheated at 100° C. for 2 hours
  2. temperatureto cool
  3. washwashed with saturated aqueous sodium bicarbonate solution, saturated aqueous ammonium chloride solution and brine
  4. dry with materialThe organics were dried (MgSO4)
  5. filtrationfiltered
  6. customsolvent removed in vacuo
  7. customto give a brown oil
  8. customThe oil was purified by silica chromatography (eluting with 0-30% ethyl acetate in petrol)

Sources & evidence

ORD record
ord-9e8ce9f0d8b5440c85598ec9524507db
Source dataset
uspto-grants-2016_03
Patent number
US09290456B2

Reaction notes

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