Methylamine → N,2,6-trimethylaniline

HRID 1448924Notes

Reaction equation

HRID 1448924 reaction equation
[CH:1]([CH:3]=[CH2:4])=O.[CH3:5][CH:6](N1CCOCC1)[CH:7]=[CH:8][CH3:9].[CH3:16][NH2:17]>[Pd]>[CH3:16][NH:17][C:4]1[C:8]([CH3:9])=[CH:7][CH:6]=[CH:5][C:3]=1[CH3:1]

Participants

5

Reactant 3

HCID 6329MethylamineHCID 7847AcroleinHCID 3828336N-(3-penten-2-yl)-morpholine

Product 1

HCID 136604N,2,6-trimethylaniline

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst

Conditions

Temperature
25 °C

Procedure

14.0 g (0.25 mol) of acrolein is added dropwise at 25° to 30° C. to 23.3 g (0.15 mol) of N-(3-penten-2-yl)-morpholine. The mixture obtained is stirred for 15 hours at 25° C. and subsequently, for further 15 hours at 50° C. Then the mixture is transferred into an autoclave and after addition of 400 ml of a 40% by weight aqueous solution of methylamine and 10.0 g of palladium coal (5%), the whole is heated under a nitrogen pressure of 50 bar for 5 hours at 280° to 290° C. Subsequently the catalyst is separated off by filtration and washed with ether. The filtrate is several times extracted with ether, the combined extracts are dried over magnesium sulphate and the ether is distilled off. Then water is added to the residue and the whole is acidified by addition of hydrochloric acid. The acid solution obtained is extracted with ether and the extract is discarded. Now sodium bicarbonate is added to the acid solution until the mixture shows alkaline reaction and the whole is again extracted with ether. The extract is dried over sodium sulphate and the ether is distilled off. N-methyl-2,6-dimethylaniline is obtained by distillation of the residue at 0.1 Torr.

Workup

  1. customThe mixture obtained
  2. waitsubsequently, for further 15 hours at 50° C
  3. temperaturethe whole is heated under a nitrogen pressure of 50 bar for 5 hours at 280° to 290° C
  4. customSubsequently the catalyst is separated off by filtration
  5. washwashed with ether
  6. extractionextracted with ether
  7. dry with materialthe combined extracts are dried over magnesium sulphate
  8. distillationthe ether is distilled off
  9. additionThen water is added to the residue
  10. additionthe whole is acidified by addition of hydrochloric acid
  11. customThe acid solution obtained
  12. extractionis extracted with ether
  13. additionNow sodium bicarbonate is added to the acid solution until the mixture
  14. customreaction
  15. extractionthe whole is again extracted with ether
  16. dry with materialThe extract is dried over sodium sulphate
  17. distillationthe ether is distilled off

Sources & evidence

ORD record
ord-348401d06bef4724be1c64985eba19a4
Source dataset
uspto-grants-1980_02
Patent number
US04188341

Reaction notes

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