Ethanol → HCID 21436197, compound

HRID 1283979Notes

Reaction equation

HRID 1283979 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][CH2:14][C:13]([C:22]([O:24]CC)=[O:23])([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH:12]1[CH2:27][C:28]1[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[K+].C(O)C>O>[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][CH2:14][C:13]([C:17]([O:19][CH2:20][CH3:21])=[O:18])([C:22]([OH:24])=[O:23])[CH:12]1[CH2:27][C:28]1[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=1)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 702Ethanol2×HCID 14797Potassium Hydroxide2×HCID 21436229HCID 21436229, compound2×

Product 1

HCID 21436197HCID 21436197, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A mixture of 257 g. of diethyl 1-benzyloxycarbonyl-2-(p-methoxybenzyl)-3,3-piperidinedicarboxylate, 35 g. of 86 per cent potassium hydroxide, 530 ml. of ethyl alcohol, and 530 ml. of water was stirred and refluxed for 71/2 hours. The reaction mixture was concentrated under reduced pressure until only water distilled. More water was added to the reaction mixture, which was then extracted twice with diethyl ether. The ether extracts were combined, washed with water, dried, filtered, and the filtrate was concentrated under reduced pressure to recover 108 g. of unhydrolyzed diester starting material. The aqueous layers from the extractions were combined and acidified with concentrated hydrochloric acid, causing separation of an oil. This oil crystallized when shaken from a few ml. of diethyl ether. The mixture was filtered and the solid thus collected was washed with diethyl ether and air-dried. This product was a first crop of 1-benzyloxycarbonyl-2-(p-methoxybenzyl)-3-carbethoxy-3-piperidinecarboxylic acid. By repeating the hydrolysis procedure on the 108 g. of recovered diethyl 1-benzyloxycarbonyl-2-(p-methoxybenzyl)-3,3-piperidinedicarboxylate, using 14.6 g. of 86 per cent potassium hydroxide, 225 ml. of ethyl alcohol, and 225 ml. of water, there was obtained a second crop of 1-benzyloxycarbonyl-2-(p-methoxybenzyl)-3-carbethoxy-3-piperidinecarboxylic acid. The two crops were combined and recrystallized from ethyl alcohol to yield 157 g. of this product as a white solid. When recrystallized from ethyl alcohol, this compound melted at 186°-188°C. (dec.); ir (K.Br) 1740 (ester C=O), 1720 (acid C=O), and 1650 cm-1 (urethane C=O).

Workup

  1. additionA mixture of 257 g
  2. temperaturerefluxed for 71/2 hours
  3. concentrationThe reaction mixture was concentrated under reduced pressure until only water
  4. distillationdistilled
  5. additionMore water was added to the reaction mixture, which
  6. extractionwas then extracted twice with diethyl ether
  7. washwashed with water
  8. customdried
  9. filtrationfiltered
  10. concentrationthe filtrate was concentrated under reduced pressure
  11. customto recover 108 g
  12. extractionThe aqueous layers from the extractions
  13. customseparation of an oil
  14. customThis oil crystallized when
  15. filtrationThe mixture was filtered
  16. customthe solid thus collected
  17. washwas washed with diethyl ether
  18. customair-dried
  19. customthe hydrolysis procedure on the 108 g

Sources & evidence

ORD record
ord-3d7a0397b8c84285959250c73fcd227e
Source dataset
uspto-grants-1976_08
Patent number
US03976653

Reaction notes

Loading…