OP-II-3

PP-I-23SELF-OSCILLATIONS DURING OXIDATIVE CARBONYLATION OFUNSATURATED COMPOUNDSGorodsky S.N., Temkin O.N., Bruk L.G.Lomonosov State Academy of Fine Chemical Technology (MITHT), Moscow,Gorodsky@yandex.ruThe report is devoted to review of the reactions by metal complexes proceedingin a self-oscillatory mode, which was discovered on the faculty of Basic OrganicSynthesis of MITHT last years. For last 50 years many oscillating reactions indifferent areas of chemistry and biochemistry [1] were revealed.We managed to find oscillatory modes in a number of carbonylation reactions ofunsaturated compounds. The first oscillatory process we discovered was a reactionof acetylene carbonylation in the system PdBr 2 – PPh 3 – HBr – butan-1-ol –dimethylsulfide.There were periodic changes of gas mixture absorption rate, color of catalyticsolution, values of electric potential and pH found [2]. At research of alkynesoxidative carbonylation reaction on ≡С-Н bond it was shown, that reaction process incatalytic system PdI 2 –KI–MeOH proceeds in an oscillatory mode [3-5] (Fig.1).Ept. мВ200150100500-500 50 100 150 200 250 300 350Т (min)Fig. 1. Oxidative carbonylation of methylacetylene: [PdI 2 ] 0 = 0,01 M, [KI] 0 = 0,4 M,[CH 3 C≡CH] 0 = 0,5 atm, СО/О 2 = 1,5The critical behavior of acetylene oxidative carbonylation reaction to maleicanhydride in the system PdBr 2 -LiBr-CH 3 CN was also discovered. At ratioP CO :P C2H2 > 3 and P O2 up to 0,2 atm the main product is succinic anhydride, at ratioP CO :P C2H2 < 3 – maleic anhydride [6].Recently the oscillations of E Pt and pH of reaction solution in the systemLiBr-PdBr 2 -H 2 O-aceton-phenylacetilene (or methylacetylene) were found (1); the262