Amination of octafluoronaphthalene in liquid ammonia: 2,6- and 2,7-Diaminohexafluoronaphthalenes selective preparation

Monoamination of octafluoronaphthalene by liquid ammonia affords 2-aminoheptafluoronaphthalene mainly (isolated yield 85–90%). Diamination of octafluoronaphthalene or amination of 2-aminoheptafluoronaphthalene affords a mixture of isomeric 1,6-, 1,7-, 2,6-, and 2,7-diaminohexafluoronaphthalenes with considerable prevalence of the 2,7-isomer (∼70%), thus being the first example of the predominant substitution at position 7 in 2-substituted polyfluoronaphthalenes. The 2,7/2,6 ratio of 2-X-heptafluoronaphthalene (X = −NH, NH2 and NHAc) amination diminishes with the decrease of electron-donating effect of the substituent; 2,7-diaminohexafluoronaphthalene forms in the reactions of 2-aminoheptafluoronaphthalene or octafluoronaphthalene with excess of NaNH2 in liquid ammonia and 2,6-diaminohexafluoronaphthalene—in the reaction of 2-acetylamidoheptafluoronaphthalene with liquid ammonia followed by acetylamido group hydrolysis. The method of the selective preparation of these diamines based on the reversible transformation of amino group and a convenient technique of their high purity isolation by complexation with crown ether have been elaborated.