Benzyl Alcohol → 3,4-Bis(benzyloxy)-6-chloropyridazine

HRID 927057Notes

Reaction equation

HRID 927057 reaction equation
[C:1]1([CH2:7][OH:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].[Na+].[Cl:11][C:12]1[N:13]=[N:14][C:15](Cl)=[CH:16][C:17]=1Cl.[OH2:20]>O1CCCC1>[CH2:7]([O:8][C:15]1[N:14]=[N:13][C:12]([Cl:11])=[CH:17][C:16]=1[O:20][CH2:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 962WaterHCID 24758Sodium hydrideHCID 951233,4,6-Trichloropyridazine

Product 1

HCID 122134743,4-Bis(benzyloxy)-6-chloropyridazineYield 39.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Phenylmethanol (6.72 g, 62.2 mmol) was added dropwise to a suspension of sodium hydride (60% suspension in mineral oil; 2.486 g, 62.2 mmol) in tetrahydrofuran (total volume: 100 ml) at room temperature. The resulting mixture was stirred for 1 hour and then cooled to 0° C. before 3,4,6-trichloropyridazine (5.7 g, 31.1 mmol) was added portionwise over 10 minutes. The reaction was then allowed to warm to room temperature and stirred for 16 hours before being poured into water and extracted with ethyl acetate (twice). The organic layer was washed with brine, dried (magnesium sulphate) and evaporated. The residue was purified by silica chromatography (eluting with 5-20% ethyl acetate in petrol containing 5% tetrahydrofuran) to yield 3,4-bis(benzyloxy)-6-chloropyridazine (4.0 g, 12.24 mmol, 39.4% yield) as the major product.

Workup

  1. additionwas added portionwise over 10 minutes
  2. stirringstirred for 16 hours
  3. extractionextracted with ethyl acetate (twice)
  4. washThe organic layer was washed with brine
  5. dry with materialdried (magnesium sulphate)
  6. customevaporated
  7. customThe residue was purified by silica chromatography (eluting with 5-20% ethyl acetate in petrol containing 5% tetrahydrofuran)

Sources & evidence

ORD record
ord-079142a0a8054badb7da45e65e58e6ff
Source dataset
uspto-grants-2016_03
Patent number
US09290456B2

Reaction notes

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