N,N-Dimethylaniline → 1H,5H-Benzo[ij]quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-

HRID 2371847Notes

Reaction equation

HRID 2371847 reaction equation
[CH2:1]1[CH2:13][N:12]2[C:4]3[C:5]([CH2:9][CH2:10][CH2:11]2)=[CH:6][CH:7]=[CH:8][C:3]=3[CH2:2]1.P(Cl)(Cl)(Cl)=O.CN(C)C1C=CC=CC=1.CN(C)[CH:30]=[O:31]>>[CH2:10]1[CH2:11][N:12]2[CH2:13][CH2:1][CH2:2][C:3]3=[C:4]2[C:5](=[CH:6][C:7]([CH:30]=[O:31])=[CH:8]3)[CH2:9]1

Participants

5

Reactant 4

HCID 949N,N-DimethylanilineHCID 6228Dimethylformamide2×HCID 24813Phosphorus oxychlorideHCID 680691H,5H-Benzo[ij]quinolizine, 2,3,6,7-tetrahydro-

Product 1

HCID 987001H,5H-Benzo[ij]quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-

Procedure

9-JA is synthesized by the formulation julolidine with phosphorus oxychloride in N,N-dimethyl formamide by a procedure similar to that described for the formulation of N,N-dimethylaniline (Organic Synthesis, Coll. Vol. 4, Wiley, New York, 1963, pp 331-333). N,N-Dimethyl formamide (45 mL) is added to a round bottom flask fitted with a magnetic stirrer, pressure equalizing dropping funnel, and a Claisen head whose sidearm was fitted with a drying tube. The flask is flushed with dry nitrogen and then cooled in a dry ice/isopropyl alcohol bath. Phosphorus oxychloride (16 mL, about 26.3 g) is added. After 10 min, 19 g of julolidine is added dropwise with stirring. The reaction mixture is stirred for 15 min after addition of the julolidine is complete, heated on a steam bath for 2 hr, and poured into a slurry of about 400 mL of crushed ice and water. The resulting solution is carefully neutralized by the addition of 150 g of sodium acetate in 250 mL of water. The precipitated aldehyde is collected by filtration, and the filtrate is kept at 0° C. overnight. The additional precipitate thus formed is collected and combined with the first crop. The combined precipitates are treated with activated charcoal (Darco® G-60) and recrystallized from ethanol/water to give 21.2 g (96%) of 9-JA as light yellow needles, mp 81° C.-82° C. [lit. 83° C., J. Org. Chem., 17, 1281 (1952)].

Workup

  1. customfitted with a magnetic stirrer
  2. customa Claisen head whose sidearm was fitted with a drying tube
  3. customThe flask is flushed with dry nitrogen
  4. temperaturecooled in a dry ice/isopropyl alcohol bath
  5. additionPhosphorus oxychloride (16 mL, about 26.3 g) is added
  6. addition19 g of julolidine is added dropwise
  7. stirringThe reaction mixture is stirred for 15 min
  8. additionafter addition of the julolidine
  9. temperatureheated on a steam bath for 2 hr
  10. additionpoured into a slurry of about 400 mL of crushed ice and water
  11. additionThe resulting solution is carefully neutralized by the addition of 150 g of sodium acetate in 250 mL of water
  12. filtrationThe precipitated aldehyde is collected by filtration
  13. waitthe filtrate is kept at 0° C. overnight
  14. customThe additional precipitate thus formed
  15. customis collected
  16. customThe combined precipitates
  17. additionare treated with activated charcoal (Darco® G-60)
  18. customrecrystallized from ethanol/water
  19. customto give 21.2 g (96%) of 9-JA as light yellow needles, mp 81° C.-82° C. [lit. 83° C., J. Org. Chem., 17, 1281 (1952)]

Sources & evidence

ORD record
ord-860ed431b81a4ab6b9c7145faa41abd3
Source dataset
uspto-grants-1992_03
Patent number
US05096790

Reaction notes

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