Hydrochloric Acid → 4-(1-Adamantylmethyl)piperidine hydrochloride

HRID 1861792Notes

Reaction equation

HRID 1861792 reaction equation
[C:1]12([CH2:11][C:12]3[CH:17]=[CH:16][N:15]=[CH:14][CH:13]=3)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.Cl.C(Cl)[Cl:20]>CO.O=[Pt]=O>[ClH:20].[C:1]12([CH2:11][CH:12]3[CH2:17][CH2:16][NH:15][CH2:14][CH2:13]3)[CH2:10][CH:5]3[CH2:4][CH:3]([CH2:9][CH:7]([CH2:6]3)[CH2:8]1)[CH2:2]2

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 6344DichloromethaneHCID 186215114-(1-Adamantylmethyl)pyridine

Product 1

HCID 186214804-(1-Adamantylmethyl)piperidine hydrochlorideYield 62%

Reagents, catalysts & solvents 2

HCID 345198Adams' catalystCatalystHCID 887MethanolSolvent2×

Procedure

A mixture of 4-(1-adamantylmethyl)pyridine (500 mg, 2.20 mmol) and PtO2 (15 mg) in MeOH (20 mL) containing concd HCl (1 mL) was allowed to shake under H2 (25-30 psi) for 24 h. NMR analysis showed only about 45% reaction. An additional portion of catalyst was added and the reaction was allowed to proceed as above for an additional 24 h. The analysis now showed about 70% reaction. The reaction was allowed to proceed at 50 psi for a final 24 h (72 h total). A crystalline solid was observed in the reaction mixture. The addition of CH2Cl2 and warming dissolved this material. The analysis now showed ˜95% reaction. The catalyst was removed by filtration (Celite) and the solvent was removed to give a yellow solid. The solid was dissolved in boiling MeOH (12 mL) and the solution was hot filtered. The filtrate was concd to 8 mL and was cooled in an ice bath to give a suspension. The solid was collected, was washed with ice cold MeOH (3×1 mL) and was dried in vacuo (100° C., 0.005 Torr) to give the title compound as a pale yellow crystalline solid (365 mg, 62%): mp >300° C.; 1H NMR (DMSO-d6) 0.95 (d, J =4.5, 2H), 1.22-1.78 (m, 17H), 1.90 (s, 3H), 2.81 (dd, J=22 and 11, 2H), 3.13 (d, J=12, 2H), 8.68 (bs, 1H), 8.89 (bs, 1H).

Workup

  1. customabout 45% reaction
  2. additionAn additional portion of catalyst was added
  3. customabove for an additional 24 h
  4. customThe analysis now showed about 70% reaction
  5. custom24 h (72 h total)
  6. temperaturewarming
  7. dissolutiondissolved this material
  8. customThe analysis now showed ˜95% reaction
  9. customThe catalyst was removed by filtration (Celite)
  10. customthe solvent was removed
  11. customto give a yellow solid
  12. dissolutionThe solid was dissolved
  13. temperaturewas cooled in an ice bath
  14. customto give a suspension
  15. customThe solid was collected
  16. washwas washed with ice cold MeOH (3×1 mL)
  17. customwas dried in vacuo (100° C., 0.005 Torr)

Sources & evidence

ORD record
ord-cb98dafb9a5642cdb5c453106648360d
Source dataset
uspto-grants-2003_03
Patent number
US06534522B2

Reaction notes

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