Methylene blue cation → Benzofuran

HRID 1799359Notes

Reaction equation

HRID 1799359 reaction equation
O[C:2]1[CH:7]=[C:6](OC)[CH:5]=[C:4]([O:10]C)[C:3]=1[CH:12](SCCC(O)=O)[CH2:13]C(C)C.CC1C=C[C@@H](C(C)C)CC=1.[N+](CC)([O-])=O.[C].[S].CN(C1C=CC2N=C3C(=CC(C=C3)=[N+](C)C)SC=2C=1)C>C1CCCCC1.[N+](C)([O-])=O>[CH:7]1[CH:2]=[C:3]2[CH:12]=[CH:13][O:10][C:4]2=[CH:5][CH:6]=1

Participants

8

Reactant 5

HCID 4139Methylene blue cation3×HCID 6587NitroethaneHCID 442482(R)-alpha-PhellandreneHCID 58835499HCID 58835499, compoundHCID 178503045HCID 178503045, compound

Product 1

HCID 9223BenzofuranYield 53%

Reagents, catalysts & solvents 2

HCID 6375NitromethaneSolventHCID 8078CyclohexaneSolvent2×

Conditions

Temperature
55 °C

Procedure

Under the condition of 25° C. and 1 atmospheric pressure, 5.2 mg of 3-[1-(2-hydroxy-4,6-dimethoxyphenyl)-3-methylbutylthio] propanoic acid and 7.2 mg of α-phellandrene were added to the solvent system consisting of of 5 mL of cyclohexane, 4 mL of nitroethane and 1 mL of nitromethane contained in a pyrex glass container and dissolved. Further, 264 mg of lithium perchloride (acceleration of carbon-sulfur cleavage reaction along with the photo electron transportation of a sulfur atom progressed by light irradiation to methylene blue and acceleration of inner molecular ring forming reaction) and 2.3 mg of methylene blue were added and dissolved completely. Lithium perchloride and methylene blue were completely dissolved in the lower layer (nitroalkane layer). By heating this solution to 55° C., homogenized completely and under the argon gas flow halogen lamp (visible ray lamp, wave length from 400 nm to 700 nm) was irradiated for 4 hours. After irradiation, by cooling the reaction solution to 25° C., phase separation occurred again (separated solution system). In the lower layer, methylene blue, lithium perchloride, disulfide generated along with the progress of the reaction and un-reacted starting materials were refined. And, in the cyclohexane layer, the reacted product is refined. Yield is 53%.

Workup

  1. dissolutiondissolved
  2. customforming
  3. additionwere added
  4. dissolutiondissolved completely
  5. customwas irradiated for 4 hours
  6. customAfter irradiation
  7. temperatureby cooling the reaction solution to 25° C.
  8. customphase separation
  9. custom(separated solution system)
  10. customIn the lower layer, methylene blue, lithium perchloride, disulfide generated along with the progress of the reaction
  11. customun-reacted

Sources & evidence

ORD record
ord-8484c4737b8f488eb12bbb7e0d0e1c9d
Source dataset
uspto-grants-2013_01
Patent number
US08344103B2

Reaction notes

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