2-Aminoresorcinol ditosylate → 2-(3,5-Dimethyl-1H-pyrazol-1-yl)-3-hydroxyphenyl 4-methylbenzenesulfonate

HRID 337343Notes

Reaction equation

HRID 337343 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([O:18]S(C3C=CC(C)=CC=3)(=O)=O)[C:13]=2[NH2:29])(=[O:10])=[O:9])=[CH:4][CH:3]=1>N([O-])=O.[Na+].O.Cl>[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([S:8]([O:11][C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([OH:18])[C:13]=2[N:29]2[C:17]([CH3:16])=[CH:12][C:13]([CH3:14])=[N:29]2)(=[O:10])=[O:9])=[CH:6][CH:7]=1

Participants

5

Reactant 1

HCID 867032532-Aminoresorcinol ditosylate

Product 1

HCID 867032542-(3,5-Dimethyl-1H-pyrazol-1-yl)-3-hydroxyphenyl 4-methylbenzenesulfonateYield 54.7%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolventHCID 23668193Sodium NitriteSolvent

Procedure

To 278 mg of 2-amino-1,3-phenylene bis(4-methylbenzene sulfonate) was added 0.64 ml of 5N-hydrochloric acid, and to the mixture a solution in which 58 mg of sodium nitrite was dissolved in 0.4 ml of water was added dropwise at 0° C., and stirred for 30 minutes. Then, a solution in which 289 mg of stannous chloride was dissolved in 0.32 ml of 5N-hydrochloric acid was added dropwise at 0° C. and stirred for 1 hour. The solvent was distilled off under reduced pressure, and 1.3 ml of ethanol and 66 μl of acetyl acetone were added and heated at reflux for 2 hours. To the reaction mixture was added 50 ml of water, and neutralized with a saturated sodium bicarbonate solution and extracted with 50 ml of ethyl acetate. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and purified using silica gel column chromatography (hexane:ethyl acetate=4:1 to 1:1) to yield 62.9 mg of the title compound.

Workup

  1. additionwas added dropwise at 0° C.
  2. additionwas added dropwise at 0° C.
  3. stirringstirred for 1 hour
  4. distillationThe solvent was distilled off under reduced pressure, and 1.3 ml of ethanol and 66 μl of acetyl acetone
  5. additionwere added
  6. temperatureheated
  7. temperatureat reflux for 2 hours
  8. additionTo the reaction mixture was added 50 ml of water
  9. extractionextracted with 50 ml of ethyl acetate
  10. dry with materialAfter the organic layer was dried over anhydrous magnesium sulfate
  11. distillationthe solvent was distilled off under reduced pressure
  12. custompurified

Sources & evidence

ORD record
ord-c76a3cc9afb64337ba027a8af58cd767
Source dataset
uspto-grants-2014_11
Patent number
US08889727B2

Reaction notes

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