Nucleophilic substitution of hydrogen in nitroarenes. An alogous and complementary process to electrophilic substitution

Nucleophiles add to electron-deficient arenes, also those containing halogens, initially in positions occupied by hydrogen to form óH adducts. This addition is faster than addition in similarly activated positions occupied by halogens. Formation of the óH adducts is a reversible process, thus they dissociate and slower addition in positions occupied by halogens results in formation of óH adducts followed by fast departure of X– to form products of nucleophilic substitution of halogen, SNAr. In the review it is shown that there are a few ways for fast further conversion of initially formed óH adducts into products of nucleopilic substitution of hydrogen such as oxidative substitution, vicarious substitution, etc. Since formation of óH adducts is faster than óH adducts and the former undergo fast transformations into products of nucleophilic substitution of hydrogen we should accept than this is the major, primary reaction whereas conventional nucleophilic substitution of halogens, SNAr reaction “ipso” substitution is just a secondary process. In modern textbooks only SNAr reactions are discussed whereas nucleophilic substitution of hydrogen is not mentioned, thus it is necessary to introduce proper corrections in textbooks and teaching of this chapter of chemistry of arenes