Hydrochloric Acid → 6,13-Ethanopentacenedione, 6,13-dihydro-

HRID 641126Notes

Reaction equation

HRID 641126 reaction equation
C(Cl)Cl.FC(F)(F)C(O)=O.[OH:11][CH:12]1[CH:25]2[C:26]3[C:35]([CH:14]([C:15]4[CH:16]=[C:17]5[C:22](=[CH:23][C:24]=42)[CH:21]=[CH:20][CH:19]=[CH:18]5)[CH:13]1[OH:36])=[CH:34][C:33]1[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=1)[CH:27]=3.Cl>CS(C)=O.C(N(CC)CC)C>[CH:29]1[C:28]2[C:33](=[CH:34][C:35]3[CH:14]4[C:13](=[O:36])[C:12](=[O:11])[CH:25]([C:26]=3[CH:27]=2)[C:24]2[C:15]4=[CH:16][C:17]3[C:22]([CH:23]=2)=[CH:21][CH:20]=[CH:19][CH:18]=3)[CH:32]=[CH:31][CH:30]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6344DichloromethaneHCID 6422Trifluoroacetic acidHCID 12185917HCID 12185917, compound

Product 1

HCID 121859186,13-Ethanopentacenedione, 6,13-dihydro-Yield 50%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 8471TriethylamineSolvent

Conditions

Temperature
-60 °C

Procedure

A reaction vessel was purged with nitrogen, and then charged with dimethylsulfoxide (8.6 ml, 93.5 mmol) and methylene chloride (48 ml). Once the reaction vessel was cooled to −60° C., the mixture was added with anhydrous trifluoroacetic acid (11.7 ml, 84.3 mmol), and the resultant solution was stirred for 10 minutes. After stirring, a solution of the 6,13-dihydro-15,16-dihydroxy-6,13-ethanopentacene (0.96 g, 2.7 mmol) obtained in Step 2 dissolved in dimethyl sulfoxide (4 ml) was slowly added dropwise into the reaction solution. After the dropwise addition, stirring was performed for 1.5 hours while maintaining the temperature at −60° C., and then the resultant solution was added with triethylamine (27.5 ml). Then, stirring was further performed for 1.5 hours, after which the temperature was returned to room temperature. The reaction solution was poured into 10% hydrochloric acid (150 ml) and was extracted with methylene chloride. The resultant organic layer was washed with water and saturated saline, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The obtained crude product was washed with ethyl acetate to give the intended 6,13-dihydro-6,13-ethanopentacene-15,16-dione (0.45 g, 50%)

Workup

  1. customA reaction vessel was purged with nitrogen
  2. additionwas slowly added dropwise into the reaction solution
  3. additionAfter the dropwise addition
  4. stirringstirring
  5. temperaturewhile maintaining the temperature at −60° C.
  6. stirringThen, stirring
  7. waitwas further performed for 1.5 hours
  8. customwas returned to room temperature
  9. extractionwas extracted with methylene chloride
  10. washThe resultant organic layer was washed with water and saturated saline
  11. dry with materialdried over anhydrous sodium sulfate
  12. concentrationconcentrated under reduced pressure
  13. customThe obtained crude product
  14. washwas washed with ethyl acetate

Sources & evidence

ORD record
ord-9a211a6dd8f04c2ba635c78a51aeb5fd
Source dataset
uspto-grants-2010_04
Patent number
US07695999B2

Reaction notes

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