Permanently increasing manufacture needs in broad spectrum of halogen containing organic compounds resulted in active development of research in this field. Use of HHal-H2O2 system represented convenient source of halogen generation immediately in reaction medium permits to create universal and safe method of organic compounds halogenation. This system permits to carry out chlorination and bromination reactions in simpler technological design than using other halogenatic agents such as chlorine or bromine. As a practical matter HHal-H2O2 system presents special interest inasmuch as one permits to generate the halogenatic particles having various natures (Figure 1, by the example of hydrochloric acid). Variation of reaction conditions (solvent, ratio substrate:HHal:H2O2, temperature, sequence and duration of components adding) enable selective synthesis of broad spectrum of halogen containing organic compounds.

Figure 1 – Generation of halogenatic particles in HHal-H2O2 system On initial research stage we used HHal – H2O2 system for receiving dichloro- and dibromoacetophenone (Figure 2). These compounds are of high interests as intermediates for synthesis of plant protection agents and biologically active substances. Over 30 compounds possessed electron-seeking as well as electron-donor substitutes was obtained with yields about 90%. Technological developmental work was carried out and optimal conditions for manufacturing of these substances were determined.

Figure 2 – Reactions scheme of receiving dihalogenacetophenone (R- electron-seeking or electron-donor substitute) Recently main efforts of our research groups concentrated to development ecologically safe and effective industrial method of production chloronitroso- and chloronitrocompounds. The first synthesis stage is based on chlorination by means of HCl–H2O2 system. The second stage (synthesis of chloronitrocompounds) is carried out by one-pot oxidation of chloronitrosocompounds by interaction with peracetic acid (Figure 3).

Figure 3 – Reactions scheme of receiving chloronitroso- and chloronitrocompounds Two-phase system is the important condition for carrying out synthesis; chlorine generates in aquatic layer and then converts to organic one who chlorinates oxime (Figure 4).

Figure 4 – Two-phase system scheme Using this method over 40 compounds with cyclic and linear fragments has been obtained. These substances may be of interest as explosives and intermediate products in organic synthesis. At present we develop ecologically safe methods for manufacturing other important industrial products.

Acknowledgment This work is supported by the Russian Science Support Foundation. References 1. A.O. Terent'ev, S.V. Khodykin, N.A. Troitskii, Yu.N. Ogibin, G.I. Nikishin. A convenient and efficient synthesis of 1-aryl-2,2-dichloroethanones. Synthesis, 2004, 2845-2848.

2. A. O. Terent'ev, S. V. Khodykin, I. B. Krylov, Y. N. Ogibin, G. I. Nikishin. A Convenient synthesis of 2,2-dibromo-1-arylethanones by bromination of 1-arylethanones with H2O2-HBr system. Synthesis, 2006, 1087-1092.

3. A. O. Terent'ev, I. B. Krylov, Y. N. Ogibin, G. I. Nikishin. Chlorination of oximes with an H2O2-HCl system: facile synthesis of gem-chloronitroso- and gem-chloronitroalkanes, gem-chloronitroso- and gem-chloronitrocycloalkanes. Synthesis, 2006, in press.