Water → HCID 22940234, compound

HRID 2424316Notes

Reaction equation

HRID 2424316 reaction equation
[CH2:1]([S:3][CH:4]([C:6]1[C:11]([CH3:12])=[CH:10][C:9]([CH3:13])=[C:8]([CH3:14])[C:7]=1[OH:15])[CH3:5])[CH3:2].CC(C)([O-])C.[K+].Cl[C:23]1[N:24]=[N:25][C:26]([Cl:31])=[CH:27][C:28]=1[O:29][CH3:30].O>O1CCOCC1.CS(C)=O>[Cl:31][C:26]1[N:25]=[N:24][C:23]([O:15][C:7]2[C:8]([CH3:14])=[C:9]([CH3:13])[CH:10]=[C:11]([CH3:12])[C:6]=2[CH:4]([S:3][CH2:1][CH3:2])[CH3:5])=[C:28]([O:29][CH3:30])[CH:27]=1

Participants

7

Reactant 4

HCID 962WaterHCID 64013433,6-dichloro-4-methoxypyridazineHCID 22940123HCID 22940123, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 22940234HCID 22940234, compoundYield 10.9%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 312751,4-DioxaneSolvent

Procedure

In a mixed solvent of 1,4-dioxane (2 mL) and dimethylsulfoxide (2 mL) was dissolved 150 mg (0.670 mmol) of 2-[1-(ethylsulfanyl)ethyl]-3,5,6-trimethylphenol obtained in Example 633(5), 93 mg (0.83 mmol) of potassium tert-butoxide was added to the solution in an ice bath, and the resulting mixture was stirred at room temperature for 20 minutes. The mixture was again cooled in an ice bath, 120 mg (0.670 mmol) of 3,6-dichloro-4-methoxypyridazine was added to the mixture, and the resulting mixture was stirred at room temperature overnight. The reaction mixture was poured into water, and extracted with ethyl acetate. The organic layers were combined, washed successively with water and brine, and dried over anhydrous magnesium sulfate. The solvent was removed, and the obtained residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) and by preparative thin-layer chromatography (available from MERCK CO., 1.05744, 2 plates were used, developed by hexane:ethyl acetate=2:1) to obtain 26.7 mg (0.0728 mmol, Yield: 10.9%) of 6-chloro-3-{2-[1-(ethylsulfanyl)ethyl]-3,5,6-trimethylphenoxy}-4-methoxypyridazine. Also, 60.0 mg (0.163 mmol, Yield: 24.3%) of 3-chloro-6-{2-[1-(ethylsulfanyl)ethyl]-3,5,6-trimethylphenoxy}-4-methoxypyridazine was obtained.

Workup

  1. additionwas added to the solution in an ice bath
  2. temperatureThe mixture was again cooled in an ice bath
  3. stirringthe resulting mixture was stirred at room temperature overnight
  4. extractionextracted with ethyl acetate
  5. washwashed successively with water and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customThe solvent was removed
  8. customthe obtained residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) and by preparative thin-layer chromatography (available from MERCK CO., 1.05744, 2 plates were used, developed by hexane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-c72eacfbadcc4f4aabd01a3954ef5702
Source dataset
uspto-grants-2011_06
Patent number
US07964531B2

Reaction notes

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