Reaktion #54535

Reaktionsgleichung

NaH

trans-2-dimethylaminocyclohexanol

N,N,N'-trimethyl-N'-benzyl-1,2-cyclohexanediamine

methanesulfonyl chloride

N-Methylbenzylamine

→

trans-N,N,N'-Trimethyl-1,2-cyclohexanediamine

Lösungsmittel

THF

THF

EtOH

Reaktionsbedingungen

Aufarbeitung

1. 1
   TemperaturIt was cooled to 10°
2. 2
   Sonstigeat 15°
3. 3
   SonstigeTHF was evaporated
4. 4
   Temperaturheating
5. 5
   workup.ADDITIONThe mixture was treated with 500 ml
6. 6
   Temperaturof 20% NaOH, heated at 95°
7. 7
   Temperaturcooled
8. 8
   Extraktionextracted with ether (6×100 ml.)
9. 9
   ExtraktionThe ether solution was extracted with 10% HCl (6×100 ml.)
10. 10
    Temperaturcooled
11. 11
    Extraktionextracted with ether
12. 12
    ExtraktionThe ether extract
13. 13
    Waschenwas washed with H2O, saturated salt solution
14. 14
    Trocknendried (MgSO4)
15. 15
    Sonstigeevaporated
16. 16
    Sonstigeto give 48.6 g
17. 17
    workup.WAITfor 22 hours
18. 18
    FiltrationThe mixture was filtered through Celite
19. 19
    Sonstigethe filtrate was evaporated
20. 20
    Temperaturcooled in ice and basified with 40% KOH
21. 21
    ExtraktionThe resulting thick suspension was extracted with ether (4×200 ml.)
22. 22
    Extraktionthe ether extract
23. 23
    Trocknenwas dried (MgSO4)
24. 24
    Sonstigeevaporated
25. 25
    workup.WAITwas 3.4 minutes

Vorschrift

A solution of trans-2-dimethylaminocyclohexanol (61.1 g.; 0.427 mole) in 85 ml. of THF was added during 5 minutes to a suspension of NaH (17.97 g.; 0.427 mole of 57% dispersion in mineral oil) in 250 ml. of THF, and the mixture was heated at 95° for 2 hours. It was cooled to 10°, and treated dropwise with methanesulfonyl chloride (48.91 g.; 0.427 mole) during 40 minutes keeping the temperature at 15°.N-Methylbenzylamine (103.48 g.; 0.854 mole distilled) was then added, THF was evaporated and heating continued at 95° for 18 hours. The mixture was treated with 500 ml. of 20% NaOH, heated at 95°, cooled and extracted with ether (6×100 ml.). The ether solution was extracted with 10% HCl (6×100 ml.), backwashed with ether (discard ether), cooled, basified with 20% NaOH and extracted with ether. The ether extract was washed with H2O, saturated salt solution, dried (MgSO4) and evaporated to give 48.6 g. of crude N,N,N'-trimethyl-N'-benzyl-1,2-cyclohexanediamine as an oil. A solution of this oil (46.6 g.) was hydrogenated in two portions each in 130 ml. of EtOH, with 2.6 g. of 10% Pd-C and 28.6 g. of 70% HClO4 at initial pressure of 51 p.s.i. for 22 hours. The mixture was filtered through Celite, the filtrate was evaporated, cooled in ice and basified with 40% KOH. The resulting thick suspension was extracted with ether (4×200 ml.), the ether extract was dried (MgSO4) and evaporated. The product boiled at 87°-88° (15 mm.Hg). Vpc-mass spectrum showed that the first peak was 3.4 minutes, was N,N-dimethyl-1,2-cyclohexanediamine and the second peak the desired N,N,N'-trimethyl-1,2-cyclohexanediamine.

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