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Collier, S. J.; Xiang, W., Science of Synthesis, (2010) 41, 665.
The direct chlorination of amines can be a useful method of preparing N,N-dichloroamines 47, with early examples employing chlorine gas.[96–98] Hypochlorite is most commonly employed as the chlorinating agent, given the wide availability of hypochlorite salts, and the ease of workup of the reactions. Both inorganic hypochlorites (e.g., calcium hypochlorite,[81,86,89,99–102] potassium hypochlorite,[103] sodium hypochlorite[97,104,105]) and organic hypochlorites such as tert-butyl hypochlorite[106] have been used. Other chlorinating agents such as N-chlorosuccinimide (as a 1:4 heterogeneous mixture with alumina)[83] or 1,3,5-trichloro-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trichloroisocyanuric acid, TCCA)[87] have also been used successfully, giving the products in good yields. Direct chlorination of cycloalkylamines in which the amine function is adjacent to a nitrile or carboxylic acid group is also achieved using elemental chlorine dissolved in an organic solvent (using a base such as sodium hydrogen carbonate to moderate the acidity of the reaction).[107] Representative examples are given in Scheme 12.
Meeeee 88 Meeeee Meeeeeeeeeee ee Meeeee[88,88,88,888,888,888]
M8 | Meeeeeeeeee | Meeee (%) | Mee |
---|---|---|---|
MMe8MM8e-Me | Me(MMe)8, MMe, 8°M | 88 | [88] |
eMe | MMMe, MeMM, 88°M | 88 | [888] |
e-Me | e-MeMMe | 88.8 | [888] |
Me | MMM, eeeeeee (8:8), 88°M, 8.8 Meee; eeeeee eee/eeeee eeeeeeeeeeee | 88 | [88] |
Me | MMM, eeeeeee (8:8), 88°M, 8.8 Meee; eeeeee eee/eeeee eeeeeeeeeeee | 88 | [88] |
Me | MMM, eeeeeee (8:8), 88°M, 8.8 Meee; eeeeee eee/eeeee eeeeeeeeeeee | 88 | [88] |
eMe | MMMM, 8°M ee ee | 888 | [88] |
Me | MMMM, 8°M ee ee | 88 | [88] |
Me8, MeMM8, MM8Me8, 8°M | 88 | [888] |
e MMMM = 8,8,8-eeeeeeeee-8,8,8-eeeeeeee-8,8,8(8M,8M,8M)-eeeeee.
Meeeeeeeeeee Meeeeeeee
M,M-Meeeeeee-8,8,8-eeeeeeeeeeeeeee-8-eeeee (88, M8 = MMe8MM8e-Me); Meeeeee Meeeeeeee:[88]
M eeeeeee ee 8,8,8-eeeeeeeeeeeeeee-8-eeeee (8.8 e, 88 eeee) eee Me(MMe)8 [88% eeee eeee eeeeeeeeeeee, e eeeeeee eeee MeMe8 eee Me(MM)8 eeee 88% eeeeee eeeeeeee; 88 e, 88 eeee] ee MM8Me8 (888 eM) eee eeeeeee eeee 8 M MMe (888 eM) ee 8°M eeee 8 e. Mee eeeeeeee eee eeeeeee eeeeeee ee eee eeee eeeeeeeeeee eee 8 e. Mee eeeeeee eeeee eee eeeeeeeee, eeeeee eeee M8M, eee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeeeeee ee eeeeeee e eeeeee eeeeee; eeeee: 8.8 e (88%).
References
[81] | Meeeeeeeee, M., Mee. Meeee. Meee. Mee., (8888) 8, 888. |
[83] | Meeeeeeee, M. M.; Meeee, M. M., Meeeeeeee, (8888), 8888. |
[86] | Meeeeee, M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 888. |
[87] | Meee, M. M.; Meeeeeeeee, M., Meeeeee, (8888), 8888. |
[89] | Meeeeee, M. M.; Meeeeeee, M. M.; Meeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[96] | Meee, M., Mee. Meee. Meee., (8888) 8[8], 888. |
[97] | Meeeeee, M. M.; Meeee, M. M. M.; Meeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[98] | Meeeeee, M. M.; Meeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[99] | Meeeee, M., Mee. Meeee. Meee. Mee., (8888) 88, 888. |
[100] | Meeeeee, M. M.; Meeeeee, M.; Meeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[101] | Meeee, M. M.; Meeee, M. M.; Meeeeee, M., M. Me. Meee. Mee., (8888) 88, 8888. |
[102] | Meeeeeeee, M. M., M. Meee. Mee., (8888), 888. |
[103] | Meeeeeeeee, M.; Meeee, M., M. Me. Meee. Mee., (8888) 88, 8888. |
[104] | Meee, M., M. M. Meee. Meeeeeee Meee. Mee., (8888) 888, 888. |
[105] | eee Meeeee, M. M.; Meeeee, M. M., Meeeeeeee. Mee., (8888) 88, 888. |
[106] | Meeeee, M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[107] | Meeee, M. M., MM 8 888 888, (8888); Meee. Meeee., (8888) 88, 88888. |