The aromatic halogenation of benzo-and dibenzocrown ethers by N-halogenosuccinimides in solid phase, water or organic medium was researched for the first time. Under mechanochemical activation depending on stoichiometry of the process, benzocrown ethers smoothly and selectively transform into corresponding mono or dihalogeno derivatives. Addition of solid N-halogenosuccinimides to benzocrown ethers' water solutions with high yields leads to mono halogenation products. At that, the process proceeds under the action of hypohalogenous acids, i.e. imide hydrolysis products. However, only 4 I ,5 I -dibromo-or -diiodobenzocrown ethers were selectively obtained in 20% solutions of sulphuric acid. In similar conditions, dibenzocrown ethers in solid phase form mixtures of products and do not react with N-halogenosuccinimides in water solutions. In the boiling chloroform medium, the reactivity of investigated macrocycles is vastly varying. If bromination of benzo-and dibenzocrown ethers proceeds easily and with good yields, then under chlorination similar products form with low yields during significantly longer period of time. Only benzocrown ethers out of researched compounds undergo mono iodination at the influence of N-iodosuccinimide. Reaction of Benzocrown Ethers with N-HalogenosuccinoimidesМакрогетероциклы / Macroheterocycles 2008 1(1) 85-89

Key indicatorsSingle-crystal X-ray study T = 164 K Mean (C-C) = 0.008 Å Disorder in solvent or counterion R factor = 0.079 wR factor = 0.213 Data-to-parameter ratio = 14.3For details of how these key indicators were automatically derived from the article, see

Five oxonium tetrahalogenaurate(III) (Hal = Cl, Br) benzo-crown ether (BCE) complexes are prepared and reported. The new compounds are [(H3O)(B18C6)(0.58)(4'-Cl-B18C6)0.42][AuCl4] 1, [(H3O)(B18C6)][AuCl4] 2, [(H3O)(4'-Br-B18C6)][AuCl4] 3, [(H3O)(4'-Br-B18C6)][AuBr4] 4, and [(H3O)(B18C6)][AuBr4] 5. The reaction medium, distinctive from the previously used aqua regia, allowed avoiding the unwanted nitration of initial macrocycles. The compositions and structures for 1, 3, 4, and 5 were proved by single crystal X-ray crystallography. The complete conversion of tetrachloroaurate(III) to the tetrabromoaurate(III) salts resulted in complex 4 isomorphous and isostructural to 3. All compounds form the laminated structures with alternation of cationic and anionic layers. The robustness of the anionic sheets is sustained by the halogen-halogen interactions and makes crucial impact on extraction of stoichiometric products in the case of tetrabromoaurate(III) salts.

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Иодирование бензо-12-краун-4, бензо-15-краун-5 и бензо-18-краун-6 эквимолярными количествами N-иодсукцинимида протекает быстро и селективно в среде этанола в присутствии небольших количеств серной кислоты и приводит к соответствующим 4 I-иодпроизводным с выходами 78-86%. Реакционная способность [3.3]дибензо-18-краун-6 мало отличается от таковой у бензокраун-эфиров, а дииодид (смесь цис-и транс-изомеров) образуется с выходом 76%.