Phenylhydrazine hydrochloride → HCID 356862, compound

HRID 2176098Notes

Reaction equation

HRID 2176098 reaction equation
Cl.[C:2]1([NH:8]N)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:10][N:11]1[CH:15]2[CH2:16][C:17]([CH2:19][CH:12]1[CH2:13][CH2:14]2)=O>C(O)C>[CH3:10][N:11]1[CH:12]2[C:19]3[C:7]4[C:2](=[CH:3][CH:4]=[CH:5][CH:6]=4)[NH:8][C:17]=3[CH2:16][CH:15]1[CH2:14][CH2:13]2

Participants

4

Reactant 2

HCID 60962Phenylhydrazine hydrochlorideHCID 79038Npc164516

Product 1

HCID 356862HCID 356862, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of phenylhydrazine hydrochloride (2.89 g, 19.99 mmol; Aldrich) and tropinone (2.78 g, 19.99 mmol; Aldrich) in ethanol (15 mL) was heated at reflux for 3 hours. The resulting solution was cooled to room temperature and the volatiles were removed under vacuum. The residue was taken up in 7% (w/w) H2SO4/dioxane (42 g) and heated at 60° C. under nitrogen for 14 hours. The mixture was cooled to room temperature and concentrated under vacuum. The residue was dissolved in water (25 mL) and the solution was made basic (pH >9) by addition of 25% NaOH (20 mL). The resulting mixture was extracted with CH2Cl2 (2×25 mL) and the extract was concentrated to residue which was purified by flash chromatography (120 g silica eluted with CH2Cl2—CH3OH-14.8 M aqueous, 90:10:1) followed by crystallization from ethyl acetate to provide the title compound: 1H NMR (300 MHz, methanol-d4) δ ppm 1.56-1.72 (m, 1H), 1.89 (t, J=9.3 Hz, 1H), 2.20-2.34 (m, 2H), 2.36 (s, 3H), 2.46 (d, J=16.7 Hz, 1H), 3.25 (dd, J=16.7, 4.8 Hz, 1H), 3.55 (t, J=5.4 Hz, 1H), 4.20 (d, J=5.2 Hz, 1H), 6.90-7.05 (m, 2H), 7.25 (d, J=7.1 Hz, 1H), 7.38 (d, J=7.1 Hz, 1H); MS (DCI) m/z 213 (M+H)+.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 3 hours
  3. customthe volatiles were removed under vacuum
  4. temperatureheated at 60° C. under nitrogen for 14 hours
  5. temperatureThe mixture was cooled to room temperature
  6. concentrationconcentrated under vacuum
  7. dissolutionThe residue was dissolved in water (25 mL)
  8. additionby addition of 25% NaOH (20 mL)
  9. extractionThe resulting mixture was extracted with CH2Cl2 (2×25 mL)
  10. concentrationthe extract was concentrated to residue which
  11. customwas purified by flash chromatography (120 g silica eluted with CH2Cl2—CH3OH-14.8 M aqueous, 90:10:1)
  12. customfollowed by crystallization from ethyl acetate

Sources & evidence

ORD record
ord-72828ca956234c12a393fb13762b3e70
Source dataset
uspto-grants-2015_06
Patent number
US09063126B2

Reaction notes

Loading…