Quinone → HCID 21292347, compound

HRID 623169Notes

Reaction equation

HRID 623169 reaction equation
[C:1]1([C:7]#[CH:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:9]([Li])[CH2:10][CH2:11][CH3:12].C1(C(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:33]1(=[O:40])[CH:38]=[CH:37][C:36](=[O:39])[CH:35]=[CH:34]1>C1COCC1.CN1C(=O)N(C)CCC1>[OH:39][C:36]1([C:8]#[C:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH:37]([CH2:12][CH2:11][CH:10]=[CH2:9])[CH2:38][C:33](=[O:40])[CH:34]=[CH:35]1

Participants

7

Reactant 4

HCID 4650QuinoneHCID 10614TriphenylmethaneHCID 10821PhenylacetyleneHCID 178418339Butyllithium

Product 1

HCID 21292347HCID 21292347, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Procedure

Phenylacetylene (0.61 g, 0.006 mole) was added to a dry 25 mL flask containing dry THF (5 mL), n-butyllithium (4 mL of 1.48 M) and a few crystals of triphenylmethane. After stirring for several min at RT, the reaction was cooled to about 0 C., added to a flask containing benzoquinone (0.63 g, 0.006 mole) dissolved in dry THF (10 mL) and cooled to -78° C. The reaction was maintained at -35° C. to -25° during the addition. After stirring for about 15 min at -30° C., 4.6 mL of DMPU was added. The dialkylmagnesium product of Example 6a was filtered under nitrogen into the reaction mixture and the filter cake washed with ether. After stirring at -35° C. for 5 min, the reaction was allowed to warm to RT and stirred overnight. The reaction was quenched into saturated ammonium chloride solution and extracted with ether. The ether extracts were washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to yield 1.1 g of a mixture which was purified by flash chromatography on silica gel using 4:1 hexane/EtOAc to yield two major fractions. The first compound-bearing fraction, 0.63 g (39%) represented the desired 1,2-1,4 product. A second compound-bearing fraction, 0.51 g (32%) was the 1,2-1,2 adduct.

Workup

  1. temperaturethe reaction was cooled to about 0 C
  2. addition, added to a flask
  3. temperaturecooled to -78° C
  4. temperatureThe reaction was maintained at -35° C. to -25° during the addition
  5. stirringAfter stirring for about 15 min at -30° C.
  6. filtrationThe dialkylmagnesium product of Example 6a was filtered under nitrogen into the reaction mixture
  7. washthe filter cake washed with ether
  8. stirringAfter stirring at -35° C. for 5 min
  9. temperatureto warm to RT
  10. stirringstirred overnight
  11. customThe reaction was quenched into saturated ammonium chloride solution
  12. extractionextracted with ether
  13. washThe ether extracts were washed with saturated sodium chloride solution
  14. dry with materialdried over anhydrous sodium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8a515a5c63a9417f8125f6fe9cf7eecb
Source dataset
uspto-grants-1988_09
Patent number
US04772755

Reaction notes

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