Exclusive β‐Substitution in the Reaction of Octafluoronaphthalene with Secondary Amines

Abstract

The reaction between octafluoronaphthalene and dimethylamine, pyrrolidine or piperidine in DMF, dimethyl(ethylene)urea (DMEU) or without solvent leads to the exclusive substitution of β‐fluorine atoms giving naphthalene derivatives with four NR2 groups. This was proved by 19F NMR of the products and a crystal structure determination for 1,4,5,8‐tetrafluoro‐2,3,6,7‐tetrakis(piperidin‐1‐yl)naphthalene. The main feature of the reaction in DMF was a transamidation process. The remaining four fluorine atoms in the synthesised tetraamines could be smoothly replaced by reduction with LiAlH4. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

A New Route to Polykis(dialkylamino)benzenes and -naphthalenes Based on Protodefluorination of Electron-Rich Fluoroaromatics: Anion Radicals of Arenes as a Simple and Effective Alternative to ‘Classical’ LAH-Based Systems

“…Elemental analyses were obtained from the elemental analysis laboratory of Institute of Physical and Organic Chemistry (Rostov-on-Don). Compounds 1-11 were synthesized in conformity with the literature, 4,5 their properties are identical with those described. The…”

“…2 As an alternative for C-F bond cleavage, Ni(0)/N-heterocyclic carbene complexes, recently suggested by Fort et al, should also be mentioned. 3 Earlier, we developed an effective approach to a wide variety of 1,4-bis(dialkylamino)tetrafluoro-(1-4) and 1,2,4,5-tetrakis(dialkylamino)difluorobenzenes (5-8) ( Figure 1) 4 as well as 2,3,6,7-tetrakis(dialkylamino)tetrafluoronaphthalenes (9-11) ( Figure 2), 5 via nucleophilic substitution of fluorines in hexafluorobenzene and octafluoronaphthalene. Continuing our investigations in the field of amino-substituted perfluoroaromatics, we noticed that their defluorinated analogues, due to their easily oxidizable nature, find application, for example, in the preparation of different magnetic and conductive materials, 6 or as mediators of glucose oxidase in glucose amperometric detection.…”