Ammonia → 4-Ethinyl-2-(p-methoxybenzyl)-1,3,3-trimethyl-4-piperidinol

HRID 596876Notes

Reaction equation

HRID 596876 reaction equation
[CH3:1][O:2][C:3]1[CH:19]=[CH:18][C:6]([CH2:7][CH:8]2[C:13]([CH3:15])([CH3:14])[C:12](=[O:16])[CH2:11][CH2:10][N:9]2[CH3:17])=[CH:5][CH:4]=1.[CH:20]#[CH:21].N>CCOCC>[C:20]([C:12]1([OH:16])[CH2:11][CH2:10][N:9]([CH3:17])[CH:8]([CH2:7][C:6]2[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:19][CH:18]=2)[C:13]1([CH3:15])[CH3:14])#[CH:21]

Participants

5

Reactant 3

HCID 222AmmoniaHCID 6326AcetyleneHCID 167261392-[(4-Methoxyphenyl)methyl]-1,3,3-trimethylpiperidin-4-one

Product 1

HCID 214486184-Ethinyl-2-(p-methoxybenzyl)-1,3,3-trimethyl-4-piperidinol

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A stream of acetylene, after successively having been washed with water, cooled to -80° C and dried with CaCl2, is led into a mechanically stirred solution of 7 g of lithium in 750 ml of dry liquid ammonia which is cooled at about -50° C. After about 5 hours the blue colour disappears. To the solution of acetylene lithium so obtained there is added dropwise 60 g of 2-(p-methoxybenzyl)-1,3,3-trimethyl-4-piperidone dissolved in 250 ml of absolute ether. During the addition a slow stream of acetylene is maintained, but afterwards this is stopped and the reaction mixture is stirred for 16 hours, the ammonia being allowed to evaporate gradually. The resulting suspension is diluted by addition of 250 ml of absolute ether and stirred for another 2 hours at 30° C. After cooling 54 g of ammonium chloride and water are added. The reaction product is secured from the organic layer in the usual manner. It is recrystallized from a mixture of benzene and petroleum ether. Yield 88%. Melting point 103°-110° C.

Workup

  1. temperatureis maintained
  2. customto evaporate gradually
  3. additionThe resulting suspension is diluted by addition of 250 ml of absolute ether
  4. stirringstirred for another 2 hours at 30° C
  5. temperatureAfter cooling 54 g of ammonium chloride and water
  6. additionare added
  7. customIt is recrystallized from a mixture of benzene and petroleum ether

Sources & evidence

ORD record
ord-9d5899bc7047425399e7fbb91a543d16
Source dataset
uspto-grants-1977_03
Patent number
US04012392

Reaction notes

Loading…