Dimethyl Sulfoxide → HCID 13591801, compound

HRID 638155Notes

Reaction equation

HRID 638155 reaction equation
[CH3:1][C:2]1([CH3:12])[CH2:6][C:5]2[CH:7]=[CH:8][CH:9]=[C:10]([OH:11])[C:4]=2[O:3]1.P(Cl)(Cl)(Cl)=O.[CH3:18][S:19](C)=O>Cl(O)(=O)(=O)=O>[CH3:1][C:2]1([CH3:12])[CH2:6][C:5]2[CH:7]=[C:8]([S:19][CH3:18])[CH:9]=[C:10]([OH:11])[C:4]=2[O:3]1

Participants

5

Reactant 3

HCID 679Dimethyl SulfoxideHCID 152782,3-Dihydro-2,2-dimethyl-7-benzofuranolHCID 24813Phosphorus oxychloride

Product 1

HCID 13591801HCID 13591801, compoundYield 46.2%

Reagents, catalysts & solvents 1

HCID 24247Perchloric AcidSolvent

Procedure

To a mixture of 2,3-dihydro-2,2-dimethyl-7-benzofuranol (16.4 g), 20 ml of 70% perchloric acid and 16 ml of phosphorus oxychloride, dimethyl sulfoxide (7.8 g, 0.1 mol) was gradually added at a temperature of not higher than 5° C. The reaction solution was stirred at room temperature for further one hour, then poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, concentrated and then heated and refluxed, together with 200 ml of pyridine, for 4 hours. Pyridine was concentrated under reduced pressure, and the residue was washed with ether. The ether layer was washed with 1N hydrocloric acid and water successibly, then dried over anhydrous sodium sulfate and concentrated. The solid substance thereby obtained was recrystallized from ether-hexane, whereby 9.7 g of 2,3-dihydro-2,2-dimethyl-5-methylthio-7-benzofuranol was obtained. The melting of this product was 57°-59° C. The structure was confirmed by 1H-NMR spectrum and IR spectrum. Then, this phenol derivative was reacted with O-ethyl-ethylthionophosphonic acid chloride in the same manner as in Example 1, whereby the compound (No. 49) identified in Table 1 was obtained.

Workup

  1. additionwas gradually added at a temperature of not higher than 5° C
  2. extractionextracted with ethyl acetate
  3. washThe ethyl acetate layer was washed with water
  4. concentrationconcentrated
  5. temperatureheated
  6. temperaturerefluxed, together with 200 ml of pyridine, for 4 hours
  7. concentrationPyridine was concentrated under reduced pressure
  8. washthe residue was washed with ether
  9. washThe ether layer was washed with 1N hydrocloric acid and water successibly
  10. dry with materialdried over anhydrous sodium sulfate
  11. concentrationconcentrated
  12. customThe solid substance thereby obtained
  13. customwas recrystallized from ether-hexane

Sources & evidence

ORD record
ord-9280ee683c4d4853aee5f69e4e859001
Source dataset
uspto-grants-1985_12
Patent number
US04560682

Reaction notes

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