Methylhydroquinone → HCID 19816406, compound

HRID 2248058Notes

Reaction equation

HRID 2248058 reaction equation
[C:1]([O:4][C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][CH:6]=1)(=[O:3])[CH3:2].S(Cl)(Cl)=O.[CH3:18][C:19]1[CH:25]=[C:24]([OH:26])[CH:23]=[CH:22][C:20]=1O.[OH-:27].[Na+].S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+]>O.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(Cl)Cl>[C:1]([O:4][C:5]1[CH:13]=[CH:12][C:8]([C:9]([O:11][C:20]2[CH:22]=[CH:23][C:24]([O:26][C:9](=[O:10])[C:8]3[CH:12]=[CH:13][C:5]([O:27][C:1](=[O:3])[CH3:2])=[CH:6][CH:7]=3)=[CH:25][C:19]=2[CH3:18])=[O:10])=[CH:7][CH:6]=1)(=[O:3])[CH3:2]

Participants

9

Reactant 5

HCID 7253MethylhydroquinoneHCID 14798Sodium HydroxideHCID 16865Benzoic acid, 4-(acetyloxy)-HCID 24386Thionyl ChlorideHCID 656671Sodium Pyrosulfite

Product 1

HCID 19816406HCID 19816406, compound

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
5 °C

Procedure

An amount of 4-acetoxybenzoic acid (9.0 g, 0.05 mole) and 45 ml of thionyl chloride (74.5 g, 0.63 mole) were refluxed on a steam bath for 4 hours in a 100-ml, single neck, round bottom flask equipped with a reflux condenser, magnetic stir bar and drying tube. The reflux condenser was replaced with a distillation head, condenser and receiver and the excess thionyl chloride was distilled. When the rate of distillation slowed, a vacuum was applied to remove the last traces of unreacted thionyl chloride. The remaining colorless oil was taken up in 180 ml of methylene chloride and the solution was cooled to 5° C. In a one-pint bottle, methylhydroquinone (2.79 g, 22.5 millimoles (mmol)) was quickly dissolved in a solution of sodium hydroxide (2.4 g, 60 mmol) and sodium pyrosulfite (0.19 g, 1 mmol) in 50 ml of water which had been purged with nitrogen. Tetrabutylammonium bromide (0.16 g, 0.5 mmol) was added and the solution was cooled to 5° C. The acid chloride solution in methylene chloride was added and the capped bottle was shaken for 16 hours. The two layers were separated and the lower organic layer was washed with aqueous 1 N hydrochloric acid, a 5 percent solution of sodium bicarbonate and water. The solution was dried over magnesium sulfate and reduced to dryness leaving a white crystalline solid which was recrystallized from 550 ml of methanol. There remained 8.0 g of white crystalline solid with a m.p. of 127.5° C. to 129.5° C.

Workup

  1. customequipped with a reflux condenser, magnetic stir bar
  2. customdrying tube
  3. distillationthe excess thionyl chloride was distilled
  4. distillationWhen the rate of distillation
  5. customto remove the last traces of unreacted thionyl chloride
  6. customhad been purged with nitrogen
  7. temperaturethe solution was cooled to 5° C
  8. customThe two layers were separated
  9. washthe lower organic layer was washed with aqueous 1 N hydrochloric acid
  10. dry with materialThe solution was dried over magnesium sulfate
  11. customleaving a white crystalline solid which
  12. customwas recrystallized from 550 ml of methanol

Sources & evidence

ORD record
ord-f2045d7c8ddd4aa98c43d42939b8e28d
Source dataset
uspto-grants-1991_08
Patent number
US05037938

Reaction notes

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