Water → HCID 57475155, compound

HRID 1095545Notes

Reaction equation

HRID 1095545 reaction equation
[Na+].[O:2]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[C:4]([CH2:11][CH2:12][S:13]S(=O)(=O)[O-])=[CH:3]1.O.P(=O)(O)(O)O.O=O>C(OCC)C>[O:2]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[C:4]([CH2:11][CH2:12][SH:13])=[CH:3]1

Participants

6

Reactant 4

HCID 962WaterHCID 977OxygenHCID 1004Phosphoric AcidHCID 131729506HCID 131729506, compound

Product 1

HCID 57475155HCID 57475155, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

The thiosulfuric acid S-[2-(benzofuran-3-yl)ethyl]ester sodium salt just prepared (3.63 g, contains x mol of water) was suspended in 50 per cent strength phosphoric acid (60 ml) with exclusion of oxygen (argon atmosphere). The reaction mixture obtained was then covered with a layer of diethyl ether (75 ml) and heated under reflux (7 h), with vigorous stirring, until solid was no longer to be observed in the aqueous phase. After cooling, the two phases were separated and the aqueous phase was extracted with diethyl ether (4×15 ml). The combined ethereal phases were washed with water (2×10 ml) and dried over sodium sulfate. The residue (yellowish oil, 1.71 g) obtained after removal of the diethyl ether contained, according to NMR, approx. 80% of the desired thiol Ind-94. Simple purification and dissolving experiments showed that Ind-94 is relatively unstable and by-products already form on standing in an ethereal solution (detection by NMR spectroscopy). The crude product obtained was therefore employed for the thioether synthesis without further working up.

Workup

  1. customThe reaction mixture obtained
  2. temperatureheated
  3. temperatureunder reflux (7 h)
  4. temperatureAfter cooling
  5. customthe two phases were separated
  6. extractionthe aqueous phase was extracted with diethyl ether (4×15 ml)
  7. washThe combined ethereal phases were washed with water (2×10 ml)
  8. dry with materialdried over sodium sulfate
  9. customThe residue (yellowish oil, 1.71 g) obtained
  10. customafter removal of the diethyl ether
  11. customSimple purification
  12. dissolutiondissolving experiments
  13. customby-products already form

Sources & evidence

ORD record
ord-fdb974dea3d0406392d2aad93814bee4
Source dataset
uspto-grants-2012_03
Patent number
US08138187B2

Reaction notes

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