I understand that phenylamine is considerably more reactive than benzene, meaning that it is able to react with bromine water to give 2,3,6-tribromophenylamine. But I was then wondering why I haven't seen anywhere mention reactions with other halogens. So will phenylamine react with other halogens to produce a similar compound, I see no reason why it wouldn't happen? Do text books just use bromine water as it is convenient?

Will $\ce{C_6H_5NH_2 + 3Cl_2 -> C_6H_2NH_2 Cl_3 + 3HCl}$ happen?

  • $\begingroup$ Why would you get N,N-Dichloroaniline instead? and would iodine do the same? Why isn't bromine behaving in this way? $\endgroup$ – H.Linkhorn Mar 12 '19 at 20:12
  • $\begingroup$ @user55119 Yeah, redox would happen, but this product is unlikely. $\endgroup$ – Mithoron Mar 12 '19 at 20:14
  • $\begingroup$ It's aniline's ring that is easily oxidated, not nitrogen. $\endgroup$ – Mithoron Mar 12 '19 at 20:16

Chlorination of aniline with chlorine is rapid and gives 2,4,6-trichloroaniline according to the references cited in this paper here. The earliest reference cited is 1845 by AW Hofmann so it has been around a long time. More modern approaches use N-Chlorosuccinimide as the reaction is more controllable

  • $\begingroup$ Why is this the case then? $\endgroup$ – H.Linkhorn Mar 12 '19 at 21:16
  • $\begingroup$ In general researchers don't want trichloroaniline, with NCS it is easier to isolate the desired mono or di-chloro aniline products. $\endgroup$ – Waylander Mar 12 '19 at 21:20
  • $\begingroup$ No, why does the reaction of chlorine result in a different product and no chloro aniline? $\endgroup$ – H.Linkhorn Mar 12 '19 at 21:23
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    $\begingroup$ I'm not sure I understand you. The reaction of chlorine directly with aniline gives chlorination of the benzene ring with the same substitution pattern as Bromine does. $\endgroup$ – Waylander Mar 12 '19 at 21:27
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    $\begingroup$ It could be that, though iodine is a fairly weak deactivator. Sterics are against it too $\endgroup$ – Waylander Mar 12 '19 at 21:39

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