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

HRID 641125Notes

Reaction equation

HRID 641125 reaction equation
FC(F)(F)C(O)=O.[OH:8][CH:9]1[CH:22]2[C:23]3[C:32]([CH:11]([C:12]4[CH:13]=[C:14]5[C:19](=[CH:20][C:21]=42)[CH:18]=[CH:17][CH:16]=[CH:15]5)[CH:10]1[OH:33])=[CH:31][C:30]1[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=1)[CH:24]=3.C(N(CC)CC)C.Cl>CS(C)=O.C(OCC)(=O)C.C(Cl)Cl>[CH:26]1[C:25]2[C:30](=[CH:31][C:32]3[CH:11]4[C:10](=[O:33])[C:9](=[O:8])[CH:22]([C:23]=3[CH:24]=2)[C:21]2[C:12]4=[CH:13][C:14]3[C:19]([CH:20]=2)=[CH:18][CH:17]=[CH:16][CH:15]=3)[CH:29]=[CH:28][CH:27]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 6422Trifluoroacetic acidHCID 8471TriethylamineHCID 12185917HCID 12185917, compound

Product 1

HCID 121859186,13-Ethanopentacenedione, 6,13-dihydro-

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolvent2×HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-60 °C

Procedure

Dry DMSO (dimethyl sulfoxide) (132 mmol, 9.4 ml) and 69 ml of dry CH2Cl2 were charged into a three-necked reaction vessel in an inert gas atmosphere, and cooled to −60° C. with an acetone/liquid nitrogen bath. To the mixture, 119 mmol (16.5 ml) of anhydrous trifluoroacetic acid was slowly added dropwise with the liquid temperature being kept at −60° C. and the resultant solution was stirred for 10 minutes. Then, to the resultant mixture, 6,13-dihydro-15,16-dihydroxy-6,13-ethanopentacene (3.81 mmol, 1.29 g) dissolved in a minimum amount of dry DMSO was slowly added dropwise, and the resultant solution was stirred for 15 hours. Triethylamine (275 mmol, 20.7 ml) was added dropwise into the solution while maintaining the liquid temperature at −60° C., which was then stirred for 1.5 hours. The reaction solution was slowly poured into 2M HCl (200 ml) and was extracted with CH2Cl2. The resultant organic layer was washed with ion-exchanged water and saturated saline, dried over anhydrous sodium sulfate and then concentrated under reduced pressure to give a crude product, which was then added with ethyl acetate. Insoluble matter was collected by filtration to give 6,13-dihydro-6,13-ethanopentacene-15,16-dione.

Workup

  1. custombeing kept at −60° C.
  2. additionwas slowly added dropwise
  3. temperaturewhile maintaining the liquid temperature at −60° C.
  4. extractionwas extracted with CH2Cl2
  5. washThe resultant organic layer was washed with ion-exchanged water and saturated saline
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customto give a crude product, which
  9. filtrationInsoluble matter was collected by filtration

Sources & evidence

ORD record
ord-fd990fd42d2745b68a6386562c4fafef
Source dataset
uspto-grants-2010_04
Patent number
US07695999B2

Reaction notes

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