反应详情

A solution of trans-2-dimethylaminocyclohexanol (61.1 g., 0.427 mole) prepared as in Procedure I, Part A, using dimethylamine instead of methylamine in 85 ml. of THF is added during 5 min. 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 is heated at 95° for 2 hrs. It is cooled to 10° and treated dropwise with methanesulfonyl chloride (48.91 g., 0.427 mole) during 40 min. keeping the temperature at 15°. N-Methylbenzylamine (103.48 g., 0.854 mole distilled) is then added, THF is evaporated and heating is continued at 95° for 18 hr. The mixture is treated with 500 ml. of 20% NaOH, heated at 95°, cooled and extracted with ether (6 × 100 ml.). The ether solution is extracted with 10% HCl (6 × 100 ml.), backwashed with ether (discard ether), cooled, basified with 20% NaOH and extracted with ether. The ether extract is 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.) is 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 for 22 hrs. The mixture is filtered through Celite, the filtrate evaporated, cooled in ice, and basified with 40% KOH. The resulting thick suspension is extracted with ether (4 × 200 ml.), the ether extract dried (MgSO4) and evaporated. The product boils at 87°-88° (16 min.). Vpc-mass spectrum showed that the first peak (3.4 min.) is N,N-dimethyl-1,2-cyclohexanediamine, and the second peak (4.1 min.) the desired N,N,N'-trimethyl-1,2-cyclohexanediamine.

1. temperatureIt is cooled to 10°
2. customat 15°
3. customTHF is evaporated
4. temperatureheating
5. additionThe mixture is treated with 500 ml
6. temperatureof 20% NaOH, heated at 95°
7. temperaturecooled
8. extractionextracted with ether (6 × 100 ml.)
9. extractionThe ether solution is extracted with 10% HCl (6 × 100 ml.)
10. temperaturecooled
11. extractionextracted with ether
12. extractionThe ether extract
13. washis washed with H2O, saturated salt solution
14. dry with materialdried (MgSO4)
15. customevaporated
16. customto give 48.6 g
17. filtrationThe mixture is filtered through Celite
18. customthe filtrate evaporated
19. temperaturecooled in ice
20. extractionThe resulting thick suspension is extracted with ether (4 × 200 ml.)
21. extractionthe ether extract
22. dry with materialdried (MgSO4)
23. customevaporated
24. customThe product boils at 87°-88° (16 min.)
25. customshowed that the first peak (3.4 min.)
26. customthe second peak (4.1 min.)