# Reaction between phenylamine and halogens

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?

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

## 1 Answer

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

• Why is this the case then? – H.Linkhorn Mar 12 at 21:16
• In general researchers don't want trichloroaniline, with NCS it is easier to isolate the desired mono or di-chloro aniline products. – Waylander Mar 12 at 21:20
• No, why does the reaction of chlorine result in a different product and no chloro aniline? – H.Linkhorn Mar 12 at 21:23
• 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. – Waylander Mar 12 at 21:27
• It could be that, though iodine is a fairly weak deactivator. Sterics are against it too – Waylander Mar 12 at 21:39