Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

PP-I-17NEW OSCILLATING REACTION:CARBONYLATION OF PROPARGYL ALCOHOLTO DIMETHYL ESTER OF ITACONIC ACIDKurdiukov A.V., Gorodsky S.N., Temkin O.N.M.V. Lomonosov State Academy of Fine Chemical Technology,Vernadsky av. 86, 119571 Moscow, RussiaPhone: (495)936-89-04; Fax: (495)434-87-11; E-mail: Gorodsky@yandex.ruSome years ago we had found out a number of alkynes oxidative carbonylation processeswhich proceeded in an oscillatory mode [1, 2]. This report deals with one more new processexpanding a range of organometallic catalytic reactions with nonlinear dynamic behavior. Itwas shown that the carbonylation of propargyl alcohol can proceed in system KI - PdI 2 - CO -O 2 - CH 3 OH in an oscillatory regime (reaction 1).+HC C-CH 2 OH + CO + O 2 +MeOH PdI CH 2 OCH 32,KICH 2 =C20C 0 COOCH 3+ CH 3 OCC C-CH 2 COOCH 3 + CH 3 OC(O)C CH-CH 2 COOCH 3(1)OOCH 3The reaction was carried out in the closed system at Т=20 0 С with intensive mixing ofliquid and gas phases. The values of electric potential of a platinum electrode (E Pt ) and glasselectrode (pH) were continuously measured during the reaction. Products of reaction wereidentified using gas chromatography and chrom-mass spectrometry. Dimethyl ester ofpentyne-2-dioic acid, dimethyl ester of 2-methoxypentene-2-dioic acid, dimethyl ester ofitaconic acid have been found out in a reaction solution as main products. The triethyl amine(ТEА) in concentration 0,7-4,0 M was added into the system before the propargyl alcoholaddition. TEA addition created necessary acidity in reaction system (рН = 5-6) for thebeginning of oscillations of intermediates concentrations. These oscillations occur inaccordance with E Pt and рН values oscillations (Fig. 1).E,мВ12080400-40-800.7 M ТEА-1200 40 80 120 160 200 240T,minрН1086420.7 M ТEА00 40 80 120 160 200 240Т,minFig. 1. Change of E Pt and pH during reaction[KI (0,4М), PdI 2 (0,01М), propargyl alcohol (0,068М), ТEА (0,7М)]242