Potassium Hydroxide → HCID 10569169, compound

HRID 1729219Notes

Reaction equation

HRID 1729219 reaction equation
[OH-].[K+].C([O:6][CH2:7][C:8]1[CH:9]=[C:10]([CH2:14][N:15]2[CH2:20][CH2:19][N:18]([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=3[O:27][CH:28]([CH3:30])[CH3:29])[CH2:17][CH2:16]2)[CH:11]=[CH:12][CH:13]=1)(=O)C>CO.C(O)(C)C>[OH:6][CH2:7][C:8]1[CH:9]=[C:10]([CH2:14][N:15]2[CH2:20][CH2:19][N:18]([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=3[O:27][CH:28]([CH3:30])[CH3:29])[CH2:17][CH2:16]2)[CH:11]=[CH:12][CH:13]=1

Participants

5

Reactant 2

HCID 14797Potassium Hydroxide2×HCID 10714935HCID 10714935, compound

Product 1

HCID 10569169HCID 10569169, compoundYield 84.6%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3776IsopropanolSolvent

Procedure

To a solution of 85% KOH (0.5 g, 7.57 mmol) in 50 mL of methanol was added compound 3 (2.50 g, 5.97 mmol). After overnight stirring, thin layer chromatography indicated very little reaction progress so the reaction mixture was refluxed under argon for several minutes. Chromatographic analysis still indicated little reaction progress so the reaction mixture was cooled. Additional KOH (0.53 g) was added and reflux was continued another 15 minutes. After this period of time, the starting material was completely consumed. The reaction mixture was concentrated, and the residue was partitioned between methylene chloride and water. The layers were separated, and the aqueous layer was further extracted with methylene chloride. The organic extracts were combined, washed with brine, and dried (MgSO4). The organic extract was concentrated to provide an oil which was dissolved in isopropanol and filtered through MgSO4. To the filtrate was added maleic acid (0.725 g), and the resulting mixture was concentrated in vacuo to provide an oil which was partitioned between 3N NaOH and methylene chloride. The layers were separated and the aqueous layer was extracted with dichloromethane. The organic extracts were combined, washed with brine, and dried (MgSO4). The organic extract was concentrated, and the resulting oil was purified on TLC mesh silica (97:3 methylene chloride:methanol). The purified material was dissolved in ethyl ether and added to ethereal HCl. The resulting precipitate was collected by suction filtration and washed with ether. The sample was dried to provide 1.72 g (70%) of benzyl alcohol dihydrochloride 4, mp 201° C. (dec). The 1H NMR supported the desired structure.

Workup

  1. temperaturewas refluxed under argon for several minutes
  2. temperatureChromatographic analysis still indicated little reaction progress so the reaction mixture was cooled
  3. temperaturereflux
  4. waitwas continued another 15 minutes
  5. waitAfter this period of time
  6. customthe starting material was completely consumed
  7. concentrationThe reaction mixture was concentrated
  8. customthe residue was partitioned between methylene chloride and water
  9. customThe layers were separated
  10. extractionthe aqueous layer was further extracted with methylene chloride
  11. washwashed with brine
  12. dry with materialdried (MgSO4)
  13. extractionThe organic extract
  14. concentrationwas concentrated
  15. customto provide an oil which
  16. filtrationfiltered through MgSO4
  17. additionTo the filtrate was added maleic acid (0.725 g)
  18. concentrationthe resulting mixture was concentrated in vacuo
  19. customto provide an oil which
  20. customwas partitioned between 3N NaOH and methylene chloride
  21. customThe layers were separated
  22. extractionthe aqueous layer was extracted with dichloromethane
  23. washwashed with brine
  24. dry with materialdried (MgSO4)
  25. extractionThe organic extract
  26. concentrationwas concentrated
  27. customthe resulting oil was purified on TLC mesh silica (97:3 methylene chloride:methanol)
  28. dissolutionThe purified material was dissolved in ethyl ether
  29. additionadded to ethereal HCl
  30. filtrationThe resulting precipitate was collected by suction filtration
  31. washwashed with ether
  32. customThe sample was dried

Sources & evidence

ORD record
ord-6d6510713c0146a98f00e07adf8e9308
Source dataset
uspto-grants-1994_07
Patent number
US05332743

Reaction notes

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