Methyl iodide → 2-(p-Methoxybenzyl)-1,3,3,4-tetramethyl-4-piperidinol

HRID 596873Notes

Reaction equation

HRID 596873 reaction equation
[CH3:1][Li].CI.[Li].Cl.[CH3:7][O:8][C:9]1[CH:25]=[CH:24][C:12]([CH2:13][CH:14]2[C:19]([CH3:21])([CH3:20])[C:18](=[O:22])[CH2:17][CH2:16][N:15]2[CH3:23])=[CH:11][CH:10]=1>O>[CH3:7][O:8][C:9]1[CH:10]=[CH:11][C:12]([CH2:13][CH:14]2[C:19]([CH3:21])([CH3:20])[C:18]([CH3:1])([OH:22])[CH2:17][CH2:16][N:15]2[CH3:23])=[CH:24][CH:25]=1

Participants

6

Reactant 4

HCID 6328Methyl iodideHCID 3028194Lithium2×HCID 204746822-(p-Methoxybenzyl)-1,3,3-trimethyl-4-piperidone hydrochlorideHCID 178418348HCID 178418348, compound

Product 1

HCID 214486362-(p-Methoxybenzyl)-1,3,3,4-tetramethyl-4-piperidinolYield 84%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

To a mechanically stirred and nitrogen flushed ethereal solution (200 ml) of methyl lithium (prepared in the usual manner from 43 g of methyl iodide and 4.8 g of lithium) there is added in small quantities 9 g of 2-(p-methoxybenzyl)-1,3,3-trimethyl-4-piperidone hydrochloride. During the addition, which takes some 1.5 hour, the mixture is cooled with water. It is stirred at room temperature for 16 hours and finally refluxed for 1 hour. Then the lithium compounds are hydrolysed by careful addition of water (cooling with ice) and the basic material is extracted from the mixture with the aid of 4 N hydrochloric acid. Basification of the aqueous solution followed by extraction with ether and processing of the ethereal solution as usual, gives crystals which after recrystallization from petroleum ether melt at 55°-65° C. Yield 84%. Evidently a mixture of epimeric piperidinols has been formed.

Workup

  1. additionDuring the addition, which
  2. stirringIt is stirred at room temperature for 16 hours
  3. temperaturefinally refluxed for 1 hour
  4. extractionthe basic material is extracted from the mixture with the aid of 4 N hydrochloric acid
  5. extractionBasification of the aqueous solution followed by extraction with ether and processing of the ethereal solution as usual,
  6. customgives crystals which
  7. customafter recrystallization from petroleum ether
  8. custommelt at 55°-65° C
  9. additionEvidently a mixture of epimeric piperidinols
  10. customhas been formed

Sources & evidence

ORD record
ord-0619fd34022642baa46b81623bf9aa01
Source dataset
uspto-grants-1977_03
Patent number
US04012392

Reaction notes

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