Perchloric Acid → 1-Ethylphenoxathiin 10,10-dioxide

HRID 37247Notes

Reaction equation

HRID 37247 reaction equation
O[CH:2]([C:4]1[C:17]2[S:16](=[O:19])(=[O:18])[C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[O:9][C:8]=2[CH:7]=[CH:6][CH:5]=1)[CH3:3].Cl(O)(=O)(=O)=O>C(O)(=O)C.[OH-].[OH-].[Pd+2]>[CH2:2]([C:4]1[C:17]2[S:16](=[O:19])(=[O:18])[C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[O:9][C:8]=2[CH:7]=[CH:6][CH:5]=1)[CH3:3]

Participants

5

Reactant 2

HCID 24247Perchloric AcidHCID 99935861-(1-Hydroxyethyl)phenoxathiin 10,10-dioxide

Product 1

HCID 1261111-Ethylphenoxathiin 10,10-dioxide

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 176Acetic AcidSolvent

Procedure

A solution of 1-(1-hydroxyethyl)phenoxathiin 10,10-dioxide (590.2) g) in acetic acid (5.4 L) containing 70% aqueous perchloric acid (250 mL) was blanketed with nitrogen and 65 g of Pearlman's catalyst (20% palladium hydroxide on carbon, Aldrich Chemical Co., Milwaukee, Wis.) was added. The atmosphere above the reaction mixture was replaced by successive evacuation and flushing with nitrogen, and then the nitrogen was displaced by successive evacuations and flushing with hydrogen. The reaction mixture was then stirred vigorously and hydrogen was added until no more was taken up. The catalyst was filtered off and rinsed with acetic acid. The combined acetic acid solutions were diluted to approximately 23.5 L with water and stirred overnight at room temperature. The resulting off-white solid was collected by filtration, washed with water (2 L) and dried at 50° C. in a vacuum oven, giving 1-ethylphenoxathiin 10,10-dioxide. After recrystallization from ethyl acetate/hexanes it had a melting point of 114°-115° C. Recrystallization from ethyl acetate/pentane appeared to give a different crystalline form, mp 101°-103° C.

Workup

  1. additionwas added
  2. customflushing with nitrogen
  3. customflushing with hydrogen
  4. additionhydrogen was added until
  5. filtrationThe catalyst was filtered off
  6. washrinsed with acetic acid
  7. additionThe combined acetic acid solutions were diluted to approximately 23.5 L with water
  8. stirringstirred overnight at room temperature
  9. filtrationThe resulting off-white solid was collected by filtration
  10. washwashed with water (2 L)
  11. customdried at 50° C. in a vacuum oven

Sources & evidence

ORD record
ord-42f6728e4af5444ab9547d526e41ad07
Source dataset
uspto-grants-1995_05
Patent number
US05420156

Reaction notes

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