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31.32.1.1.2 Variation 2: By Reaction with Inorganic or Organic Hypochlorites

DOI: 10.1055/sos-SD-031-01909

Chiara, J. L.Science of Synthesis, (2007311729.

Hypochlorous acid[‌10‌,‌11‌,‌13‌,‌41‌] and metal hypochlorites, in particular sodium,[‌14‌,‌42‌] potassium,[‌43‌] and calcium hypochlorite,[‌8‌,‌12‌‌14‌,‌43‌‌45‌] are widely used for the preparation of N-chloroarylamines 15 (Scheme 5) and N,N-dichloroarylamines 16 (Scheme 6). The reaction is generally performed at low temperature (30 to 0°C) in an inert organic solvent (e.g., diethyl ether, chloroform, or carbon tetrachloride). In the case of hypochlorous acid, which is soluble in organic solvents, the reaction occurs under homogeneous conditions. In the case of the hypochlorite salts the reaction occurs under heterogeneous conditions, using either a suspension of the powdered reagent or an aqueous biphasic solvent system. Hypochlorous acid and metal hypochlorites are weaker N-chlorinating reagents than chlorine (see Section 31.32.1.1.1) for poorly reactive substrates, such as 2-nitroanilines.

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M8 M8 Meee (°M) Meee Meeee (%) Mee
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e-Me Me 88 8e 88 [‌88‌]
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M M Meee (°M) Meee (e) Meeee (%) Mee
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MMM8 MM 88 8 88 [‌88‌]
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M MMe 88 88 88 [‌88‌]
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References