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Tetrahydrofuran → HCID 131725149, compound

HRID 496289
Notes
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Reaction equation

HRID 496289 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][C:10]2[CH:15]=[CH:14][C:13](Br)=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.[CH2:17]([Li])[CH2:18][CH2:19][CH3:20].[CH3:22][C:23]1[CH:27]([CH3:28])[CH2:26][C:25](=O)[CH:24]=1.[Cl-].[NH4+].[CH2:32]1[CH2:36]OC[CH2:33]1>C(OCC)C.C(Cl)Cl.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[CH3:20][C:19]1[C:32]([CH3:36])=[CH:33][CH:17]([C:2]2[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][C:10]3[CH:15]=[CH:14][C:13]([CH:25]4[CH:24]=[C:23]([CH3:22])[C:27]([CH3:28])=[CH:26]4)=[CH:12][CH:11]=3)=[CH:4][CH:3]=2)[CH:18]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 5

HCID 8028Tetrahydrofuran2×HCID 25517Ammonium ChlorideHCID 1217103,4-Dimethylcyclopent-2-en-1-oneHCID 125942401,1'-(Ethane-1,2-diyl)bis(4-bromobenzene)HCID 178418339Butyllithium

Product 1

HCID 131725149HCID 131725149, compound
Yield 63%

Reagents, catalysts & solvents 3

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

3.400 g (10 mmol) of 1,2-di(4-bromophenyl) ethane prepared in Synthesis Example 4-1 was dissolved in 50 ml of diethylether, and the solution was cooled down to 0° C. 8.4 ml (2.1 equivalents, 21 mmol) of n-butyllithium was dropped into the solution with a syringe. The solution was stirred for one hour at 0° C., slowly warmed to the room temperature and then stirred for more 2 hours to form a white precipitate. After making the precipitate settle and discarding the supernatant, the precipitate was dissolved in 30 ml of THF at −78° C. In a separate flask, 2.183 g (20.0 mmol) of 3,4-dimethyl-2-cyclopentenone was mixed with 20 ml of THF and the resulting solution was slowly dropped into the precipitate solution with a cannular. The mixed solution was slowly warmed to the room temperature and stirred for more than 6 hours to form a light yellowish solution. After adding an appropriate amount of a saturated ammonium chloride aqueous solution to terminate the reaction, the organic layer was extracted with 50 ml (×3) of diethylether, dried on anhydrous magnesium sulfate and then filtered. The solution was removed of the solvent on a rotary evaporator to obtain a yellowish sticky oil. This oil was dissolved in 50 ml of methylene chloride and mixed Faith a catalytic amount (0.1 g) of p-toluene sulfonate hydrate. The resulting solution was stirred for 2 hours at the room temperature to form a light brown solid. With the solvent vaporized on the rotary evaporator until the solid was wet, the solid was washed with 30 ml of hexane and filtered out. The solid was washed with 30 ml (×3) of anhydrous ethanol and 30 ml (×2) of pentane and dried under vacuum to obtain 2.314 g (63% yield) of an ivory solid.

Workup

  1. temperatureslowly warmed to the room temperature
  2. stirringstirred for more 2 hours
  3. customto form a white precipitate
  4. additionthe resulting solution was slowly dropped into the precipitate solution with a cannular
  5. temperatureThe mixed solution was slowly warmed to the room temperature
  6. stirringstirred for more than 6 hours
  7. customto form a light yellowish solution
  8. customto terminate
  9. customthe reaction
  10. extractionthe organic layer was extracted with 50 ml (×3) of diethylether
  11. dry with materialdried on anhydrous magnesium sulfate
  12. filtrationfiltered
  13. customThe solution was removed of the solvent on a rotary evaporator
  14. customto obtain a yellowish sticky oil
  15. stirringThe resulting solution was stirred for 2 hours at the room temperature
  16. customto form a light brown solid
  17. customWith the solvent vaporized on the rotary evaporator until the solid
  18. washthe solid was washed with 30 ml of hexane
  19. filtrationfiltered out
  20. washThe solid was washed with 30 ml (×3) of anhydrous ethanol and 30 ml (×2) of pentane
  21. customdried under vacuum

Sources & evidence

ORD record
ord-522258696518442fbce56fad090c09ed
Source dataset
uspto-grants-2005_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06943225B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes