Water → 6-Oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrile

HRID 600248Notes

Reaction equation

HRID 600248 reaction equation
[Cu][C:2]#[N:3].CN1[CH2:9][CH2:8][CH2:7][C:6]1=[O:10].O.C(O[CH2:16][CH3:17])(=O)C>>[O:10]=[C:6]1[CH2:17][CH2:16][C:9]2[CH:9]=[C:8]([C:2]#[N:3])[CH:7]=[CH:6][C:8]=2[CH2:7]1

Participants

5

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 13387N-methyl-2-pyrrolidoneHCID 178418546HCID 178418546, compound

Product 1

HCID 162445046-Oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrileYield 78%

Conditions

Temperature
190 °C

Procedure

See also generally Org. Prep. Proced. Int. Vol. 32, No. 1, 2000, p. 88. Charged 50 mL round bottom flask with copper(I) cyanide (1.34 g., 0.0150 moles, 1.12 eq.), 6-bromo-2-tetraline (3.0 g., 1.33 mmoles, 1.0 eq.) and 13 mL N-methylpyrrolidinone. Heated for 5 hours at 180-200° C. Allowed reaction mixture to stir at room temperature over the weekend. Transferred reaction mixture to 250 mL 3-necked, round bottomed flask fitted with a mechanical stirrer, a condenser, and an addition funnel. Added 6.0 g. Celite® and heated with stirring to 80° C. Added 70 mL water and 90 mL ethyl acetate to hot stirring reaction mixture. Turned off heat and allowed to cool overnight with stirring. The next day, filtered the reaction mixture through a Celite® pad. Partitioned off water layer from filtered reaction mixture. Washed ethyl acetate layer with water once, then washed with a 50:50 mixture of brine and water twice. Dripped organic layer through sodium sulfate to dry and removed solvents under reduced pressure to obtain 2.67 g. of light brown solid. Purified crude material via Biotage FLASH 40 L® cartridge (175 g. of silica gel) using an ethylacetate:hexane stepwise gradient. Obtained 1.77 g. (yield=78%). Product was not completely pure, but used it as is in the next reaction. H-NMR (CDCL3): 7.55 (1H, s), 7.53 (1H, d), 3.64 (2H, s), 3.12 (1H, t, J=7 Hz), 2.58 (1H, t, J=7 Hz.

Workup

  1. customTransferred reaction mixture to 250 mL 3-necked, round bottomed flask fitted with a mechanical stirrer, a condenser, and an addition funnel
  2. additionAdded 6.0 g
  3. temperatureCelite® and heated
  4. stirringwith stirring to 80° C
  5. stirringto hot stirring
  6. customreaction mixture
  7. temperatureTurned off heat
  8. temperatureto cool overnight
  9. stirringwith stirring
  10. filtrationThe next day, filtered the reaction mixture through a Celite® pad
  11. customPartitioned off water layer
  12. filtrationfrom filtered
  13. customreaction mixture
  14. washWashed ethyl acetate layer with water once, then washed with a 50:50 mixture of brine and water twice
  15. dry with materialDripped organic layer through sodium sulfate to dry
  16. customremoved solvents under reduced pressure
  17. customto obtain 2.67 g
  18. customPurified crude material via Biotage FLASH 40 L® cartridge (175 g. of silica gel)
  19. customObtained 1.77 g
  20. customas is in the next reaction

Sources & evidence

ORD record
ord-52e75c62bac34287832bedf269634314
Source dataset
uspto-grants-2011_03
Patent number
US07902191B2

Reaction notes

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