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41.11.2.1.1 Method 1: Direct Chlorination of Amines

DOI: 10.1055/sos-SD-041-00614

Collier, S. J.; Xiang, W.Science of Synthesis, (201041665.

The direct chlorination of amines can be a useful method of preparing N,N-dichloroamines 47, with early examples employing chlorine gas.[‌96‌‌98‌] 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,[‌81‌,‌86‌,‌89‌,‌99‌‌102‌] 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.

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