1070-3632/05/7509-1367 2005 Pleiades Publishing, Inc. Russian Journal of General Chemistry, Vol. 75, No. 9, 2005, pp. 1367 1372. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 9, 2005, pp. 1439 1444. Original Russian Text Copyright 2005 by Trofimov, Gusarova, Malysheva, Kuimov, Sukhov, Shaikhudinova, Tarasova, Smetannikov, Sinyashin, Budnikova, Kazantseva, Smirnov. Reactions of Elemental Phosphorus with Electrophiles in Super Basic Systems: XVII. 1 Phosphorylation of Arylalkenes with Active Modifications of Elemental Phosphorus B. A. Trofimov*, N. K. Gusarova*, S. F. Malysheva*, V. A. Kuimov*, B. G. Sukhov*, S. I. Shaikhudinova*, N. P. Tarasova**, Yu. V. Smetannikov**, O. G. Sinyashin***, Yu. G. Budnikova***, T. I. Kazantseva*, and V. I. Smirnov* * Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia ** Mendeleev Russian University of Chemical Technology, Moscow, Russia *** Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences, Kazan, Tatarstan, Russia Received April 30, 2004 Abstract The example of the phosphorylation of styrene and 2-vinylnaphthalene with elemental phos- phorus in the KOH DMSO system at room or elevated temperature was used to show that the activated red phosphorus prepared from white phosphorus under ionizing radiation has a reactivity com- parable with that of white phosphorus and significantly higher than that of ordinary technical red phosphorus. Direct phosphorylation of organic compounds with elemental phosphorus is being actively developed as one of the most perspective, economical, and ecolo- gically safe synthetic approaches to organophosphorus compounds [1 6]. There has been devised and de- veloped a new method of activation of elemental phosphorus (including its the least active red modifi- cation) in heterogenous super basic systems, that opens up the way to formation of a C P bond and allows preparation of previously unknown or hardly available phosphines and phosphine oxides, including unsaturated, chiral, and polyfunctional [1, 4, 5, 7 9]. To facilitate P P bond cleavage in the P 4 molecule and thus enhance its reactivity, introduction of white phosphorus in the coordination sphere of the transition metal with subsequent (or preceding) electrochemical electron transfer [6], as well as activation and func- tionalization of white phosphorus on Rh [2] have been used to success. Over the past years, conceptually new approaches to controlled modification of chemical properties of red phosphorus (in both inorganic and organic pro- cesses [10, 11]) via controlled defect formation in its structure have been devised. Such approaches involve either synthesis of red phosphorus under specific 1 For communication XVI, see [1]. conditions, for instance, by radiation ( 60 Co) poly- merization of white phosphorus [12 14], or certain outer treatment (X-ray irradiation [15, 16] or me- chanochemical treatment [4, 5]). In the present work, aiming at obtaining further evidence for the perspectiveness and universality of the method of biographical defect formation for acti- vation of red phosphorus in organophosphorus syn- thesis, we have studies the effect of the nature of elemental phosphorus (white, ordinary, and activated red) on the effectiveness and selectivity of the phos- phorylation of arylalkenes in the KOH DMSO system. We used two active modifications of red phos- phorus ( 1* P n and 2* P n ), obtained by the polymeriza- tion of white phosphorus in benzene at room tem- perature under 60 Co irradiation of varied absorbed dose [17, 18]. Previously by IR and X-ray electron spectroscopy Smetannikov and Tarasova [19] detected in these samples P P, P C, and P O C bonds, which points to the presence in the activated red phosphorus of P P R defects (where R is a fragment of the sol- vent). The phosphorus contents of the 1* P n and 2* P n samples are 64 and 50 wt %, respectively. It was found that white and activated red ( 1* P n ) phosphorus react with styrene in the KOH DMSO system under argon already at room temperature to form bis(2-phenylethyl)phosphine oxide (I), tris(2-