Hydrochloric Acid → HCID 59293914, compound

HRID 2280368Notes

Reaction equation

HRID 2280368 reaction equation
[CH3:1][S:2][C:3]1[CH:4]=[C:5]([C:9]2[CH2:10][CH2:11][N:12]([CH2:15][CH2:16][CH3:17])[CH2:13][CH:14]=2)[CH:6]=[CH:7][CH:8]=1.Cl>[Pd].C(O)C>[CH3:1][S:2][C:3]1[CH:4]=[C:5]([CH:9]2[CH2:14][CH2:13][N:12]([CH2:15][CH2:16][CH3:17])[CH2:11][CH2:10]2)[CH:6]=[CH:7][CH:8]=1

Participants

5

Reactant 2

HCID 313Hydrochloric AcidHCID 166553434-[3-(Methylsulfanyl)phenyl]-1-propyl-1,2,3,6-tetrahydropyridine

Product 1

HCID 59293914HCID 59293914, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

4-(3-Methylsulfanyl-phenyl)-1-propyl-1,2,3,6-tetrahydropyridine (2) (290 mg, 1.17 mmol) was brought in a Parr-flask with 10 mL of ethanol (100%) in a nitrogen atmosphere. 100 mg of Pd/C and 0.5 mL of HCl (37%) were added. The flask was attached to a Parr reduction apparatus and H2 gas was added to a pressure of 3 Bar. It was left shaking for 1 h. Then, the mixture was filtered over celite, put back in the flask and another 100 mg of Pd/C and 1 ml of HCl (37%) was added before attaching the flask to the Parr apparatus again and starting another session of 75 min this time. This procedure was repeated another 3 times, with session durations of 105 min, 1 night and 2 h. Eventually, the mixture was filtered, the solvent evaporated in vacuo on a rotavapor. 10 mL of NaHCO3 10% was added (pH 8). Then 30 mL of water and 40 mL of diethyl ether were added and shaken. The aqueous layer was extracted three times with diethyl ether. The combined organic layers were washed with brine, dried on MgSO4, filtered and the solvent was evaporated on a rotavapor. The slightly yellow oil was taken up in CH2Cl2 and purified by gradient column chromatography (Al2O3, CH2Cl2, CH2Cl2:MeOH 10:1). Fractions 9-20 contained the desired product. The fractions were collected and the solvent was evaporated in under reduced pressure. Yield: 335 mg (115%). The reaction was followed on thin layer chromatography (SiO2 flushed with NH3, CH2Cl2:MeOH 20:1 and Al2O3, CH2CL2:MeOH 40:1). 1H-NMR (CDCl3, 300 MHz): δ 7.2 (m), 3.1 (t), 2.5 (s), 2.4 (m), 2.0 (m), 1.8 (m), 1.6 (m), 1.2 (m), 0.9 (m) ppm; 13C-NMR (CDCl3, 300 MHz): δ 145.673, 136.767, 127.345, 126.882, 126.722, 125.372, 124.576, 123.650, 123.430, 122.793, 122.216, 120.479, 59.631, 52.841, 41.333, 31.888, 26.630, 18.680, 14.287, 10.577 ppm; GCMS (EI): m/z 249 (M+), 220 (M−29); GC (100-320° C., 10° C./min): 4.7, 9.9 min.

Workup

  1. additionwas added to a pressure of 3 Bar
  2. waitIt was left
  3. filtrationThen, the mixture was filtered over celite
  4. additionanother 100 mg of Pd/C and 1 ml of HCl (37%) was added
  5. customanother session of 75 min
  6. customwith session durations of 105 min, 1 night and 2 h
  7. filtrationEventually, the mixture was filtered
  8. customthe solvent evaporated in vacuo on a rotavapor
  9. addition10 mL of NaHCO3 10% was added (pH 8)
  10. additionThen 30 mL of water and 40 mL of diethyl ether were added
  11. stirringshaken
  12. extractionThe aqueous layer was extracted three times with diethyl ether
  13. washThe combined organic layers were washed with brine
  14. customdried on MgSO4
  15. filtrationfiltered
  16. customthe solvent was evaporated on a rotavapor
  17. custompurified by gradient column chromatography (Al2O3, CH2Cl2, CH2Cl2:MeOH 10:1)
  18. customThe fractions were collected
  19. customthe solvent was evaporated in under reduced pressure
  20. customThe reaction was followed on thin layer chromatography (SiO2 flushed with NH3, CH2Cl2:MeOH 20:1 and Al2O3, CH2CL2:MeOH 40:1)
  21. customGC (100-320° C., 10° C./min)
  22. custom4.7, 9.9 min.

Sources & evidence

ORD record
ord-bec214b574a54a99b603a957b34d2f31
Source dataset
uspto-grants-2015_09
Patent number
US09139525B2

Reaction notes

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