Potassium Hydroxide → Benzenesulfonic acid, 4-hydroxy-, phenyl ester

HRID 1577077Notes

Reaction equation

HRID 1577077 reaction equation
[O-:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Na+].C(OC([O:14][C:15]1[CH:20]=[CH:19][C:18]([S:21](Cl)(=[O:23])=[O:22])=[CH:17][CH:16]=1)=O)C.C1(S([O-])(=O)=O)C=CC=CC=1.C(OC(OC1C=CC(S([O-])(=O)=O)=CC=1)=O)C.[OH-].[K+]>C(O)C.C1C=CC=CC=1>[O:1]([S:21]([C:18]1[CH:19]=[CH:20][C:15]([OH:14])=[CH:16][CH:17]=1)(=[O:23])=[O:22])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 5

HCID 14797Potassium HydroxideHCID 91526BenzenesulfonateHCID 4445035Phenolate Sodium2×HCID 128842674-(Chlorosulfonyl)phenyl ethyl carbonateHCID 205717844-Ethoxycarbonyloxybenzene sulfonate

Product 1

HCID 593816Benzenesulfonic acid, 4-hydroxy-, phenyl ester

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 702EthanolSolvent2×

Conditions

Temperature
80 °C

Procedure

Sodium phenoxide, 9.0 g. (0.078 mole) is added in portions to a solution of 20 g. (0.076 mole) of 4-ethoxycarbonyloxybenzenesulfonyl chloride in 250 ml. of dry benzene. The slurry is brought to reflux (80° C.) for 1.5 hours and then allowed to stir at room temperature overnight. The reaction is followed by thin layer chromatography, additional sodium phenoxide is added as needed, and the reaction is refluxed until complete. The slurry is then cooled to room temperature and filtered to remove sodium chloride. The filtrate is concentrated to give 22.3 g. (88%) of the desired benzene sulfonate as an oil of suitable purity for the next reaction. The 4-ethoxycarbonyloxybenzene sulfonate (22.3 g., 0.069 mole) is taken up in 120 ml. of ethanol and stirred at 20° C. while a solution of 5.3 g. (0.08 mole) of potassium hydroxide in 50 ml. of ethanol is added dropwise. After two hours at room temperature, the solution is brought to 40° C. for 30 minutes and then concentrated in vacuo. The residue is taken up in 250 ml. of water (pH=10), extracted once with ether, acidified to pH 1 with 10 ml. of concentrated hydrochloric acid and then extracted three times with 200 ml. portions of chloroform. The chloroform extracts are combined, dried over sodium sulfate and concentrated in vacuo to give 15.9 g. (91%) of the phenol as an oil which crystallizes on standing; m.p.=114°-116.5° after recrystallization from xylene.

Workup

  1. addition(0.078 mole) is added in portions to a solution of 20 g
  2. additionis added
  3. temperaturethe reaction is refluxed until complete
  4. temperatureThe slurry is then cooled to room temperature
  5. filtrationfiltered
  6. customto remove sodium chloride
  7. concentrationThe filtrate is concentrated
  8. customto give 22.3 g
  9. waitAfter two hours at room temperature
  10. waitthe solution is brought to 40° C. for 30 minutes
  11. concentrationconcentrated in vacuo
  12. extractionof water (pH=10), extracted once with ether
  13. extractionof concentrated hydrochloric acid and then extracted three times with 200 ml
  14. dry with materialdried over sodium sulfate
  15. concentrationconcentrated in vacuo
  16. customto give 15.9 g
  17. custom(91%) of the phenol as an oil which crystallizes on standing
  18. customm.p.=114°-116.5° after recrystallization from xylene

Sources & evidence

ORD record
ord-c314ab97bbd140478559cb7a702da61a
Source dataset
uspto-grants-1981_09
Patent number
US04287189

Reaction notes

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