Ammonium Acetate → Acridine, 9-butyl-1,2,3,4,5,6,7,8-octahydro-

HRID 1086616Notes

Reaction equation

HRID 1086616 reaction equation
C([O-])(=O)C.[NH4+:5].[CH2:6]([CH:10]1[CH:21]2[C:22](=O)[CH:17]([CH2:18][CH2:19][CH2:20]2)[C:16]2(O)[CH:11]1[CH2:12][CH2:13][CH2:14][CH2:15]2)[CH2:7][CH2:8][CH3:9]>C(O)(=O)C>[CH2:6]([C:10]1[C:21]2[CH2:20][CH2:19][CH2:18][CH2:17][C:22]=2[N:5]=[C:16]2[C:11]=1[CH2:12][CH2:13][CH2:14][CH2:15]2)[CH2:7][CH2:8][CH3:9]

Participants

4

Reactant 2

HCID 517165Ammonium AcetateHCID 13567523HCID 13567523, compound

Product 1

HCID 10890121Acridine, 9-butyl-1,2,3,4,5,6,7,8-octahydro-

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A 500 mL, one-necked flask equipped with a magnetic stirring bar, a Claisen adapter, and a reflux condenser equipped with a nitrogen inlet attached to a bubble (Note 6) is charged with 17.0 g (0.22 mol) of ammonium acetate, 82 g (0.41 mol) of cupric acetate monohydrate and 200 mL of glacial acetic acid, then flushed with nitrogen. The mixture is stirred and heated at reflux under a static atmosphere of nitrogen for 15 min., then the resulting solution is cooled slightly as 53 g (0.20 mol) of 8-n-butyl-2-hydroxytricyclo[7.3.1.02,7 ]tridecan-13-one is added in several portions. The blue-green reaction mixture is stirred and heated at reflux under nitrogen for 3 hrs., then the reaction flask is cooled in an ice bath for 2-3 hours. Precipitated cuprous acetate is removed by vacuum filtration using a fitted glass funnel (medium or coarse porosity) and washed with 100 mL of acetic acid. The combined filtrates are diluted with 500 mL of water, cooled in ice and carefully neutralized by slow addition of aqueous sodium hydroxide (Note 7). The resulting cloudy mixture is transferred to a separatory funnel and extracted with ether (400 mL, then 2× 200 mL). The combined ether extracts are washed with 140 mL of 3% aqueous sodium hydroxide and 70 mL of saturated aqueous sodium chloride, then dried using anhydrous magnesium sulfate with 1 g of decolorizing charcoal (Norit). The solids are removed by filtration and washed with at least 200 ml of ether. The combined filtrates are concentrated to minimum volume using a rotary evaporator and residual solvent is removed under vacuum (1mm). The product is obtained as a beige crystalline solid, mp 35-37° C., 47 g (97%) (Note 8).

Workup

  1. customA 500 mL, one-necked flask equipped with a magnetic stirring bar
  2. customa Claisen adapter, and a reflux condenser equipped with a nitrogen inlet
  3. customa bubble (Note 6)
  4. customflushed with nitrogen
  5. temperatureheated
  6. temperatureat reflux under a static atmosphere of nitrogen for 15 min.
  7. additionis added in several portions
  8. stirringThe blue-green reaction mixture is stirred
  9. temperatureheated
  10. temperatureat reflux under nitrogen for 3 hrs
  11. temperature, then the reaction flask is cooled in an ice bath for 2-3 hours
  12. customPrecipitated cuprous acetate is removed by vacuum filtration
  13. washcoarse porosity) and washed with 100 mL of acetic acid
  14. additionThe combined filtrates are diluted with 500 mL of water
  15. temperaturecooled in ice
  16. additioncarefully neutralized by slow addition of aqueous sodium hydroxide (Note 7)
  17. customThe resulting cloudy mixture is transferred to a separatory funnel
  18. extractionextracted with ether (400 mL
  19. washThe combined ether extracts are washed with 140 mL of 3% aqueous sodium hydroxide and 70 mL of saturated aqueous sodium chloride
  20. customdried
  21. customThe solids are removed by filtration
  22. washwashed with at least 200 ml of ether
  23. concentrationThe combined filtrates are concentrated to minimum volume
  24. customa rotary evaporator and residual solvent
  25. customis removed under vacuum (1mm)
  26. customThe product is obtained as a beige crystalline solid, mp 35-37° C., 47 g (97%) (Note 8)

Sources & evidence

ORD record
ord-87dcc574a1254345a38bb2cf921b9ebf
Source dataset
uspto-grants-1991_07
Patent number
US05030728

Reaction notes

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