819190

Hindawi Publishing Corporation Organic Chemistry International V olume 2012, Article ID 819190, 6 pages doi:10.1155/2012/819190 Research Article Oxi dat iv e Carbon ylat ion of 2-P rop yn- 1-o l and 2-M eth yl-3 -bu tyn-2- ol in an Osci ll at ory Mode Serge y Nik olaevic h Gorods ky Department of Basic Organic Synthesis, Lomonosov Moscow State University of Fine Chemical T echnologies (MITHT), Vernadsky Avenue 86, 119571 Moscow, Russia Correspondence should be addressed to Sergey Nikolaevich Gorodsky, [email protected] Received 31 October 2011; Accepted 18 January 2012 Academic Editor: Dipakranjan Mal Copyr ight © 2012 Sergey Nik olaevic h Goro dsky . This is an open acce ss articl e distri buted unde r the Crea tiv e Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The oscillatory modes of oxidative carbonylation reaction of two new substrates—2-methyl-3-butyn-2-ol and 2-propyn-1-ol in homogeneous system PdI 2 -KI-CO-O 2 -CH 3 OH are found. Borders of oscillatory areas are drawn, the basic products of reaction are identified, and probable processes routes are o ff ered. 1. Intr oductio n The phen omeno n of intermediates conc entrati on oscil la- tions is found already in several tens of homogeneous [ 1] and heterogeneous [2] chemical systems. The most interesting thing, in our opinion, is the oscillations occurring in homogeneous catalysis conditions. They are evolving out of intermediates complex interactions, which are formed dur- ing process. So this type of oscillations has a chemical nature only. Influence of diff usion, processes of mass and heat ex- change, certainly, can be observed in these systems, but these processes, to all appea rance, are not resp onsible for an occur- rence of concentration oscillations in the homogeneous systems. We were lucky to find out oscillatory modes of oxidative carbon ylati on reacti ons of two new alkyn es: 2-met hyl- 3- butyn-2-ol (MB) and 2-propyn-1-ol (P). As fa r as we k now it is the first mention of oscillatory process with participation of oxygen containing alkynes in metal complexes catalysis conditions. In early works we investigated the oscillations in palladium halogenide solutions in reactions of alkynes oxidative carbonylation [3–11]. These are examples of reactions in whi ch comple x pro duc ts—carb ox yli c aci ds and the ir derivatives—are synthesized from simple substances-H 2 O, CH 3 OH, CO, and so on. The carbonylation reactions are interesting with relation to important products of organic synthesis obtaining 2-methyl-3-butyn-2-ol is that used as semiproduct in synthesis of fragrance compounds, medical products, and vitamins, applied as anticorrosive means to pro tec tion of the pet rol eum equ ipment, the mod ifier of motor fuels , emul gators . MB is an int ere sti ng resear ch obj ect. On the one hand, it has triple bond in the molecule, and so it can participate in reactions of hydrogenation, halogenations and other addition processes on the triple bond. It is active also in reactions of oligomerization and polymerization, and owing to presence of hydroxyl groups MB is the participant of reactions that are characteristic for alcohols generally, and for tertiary alcohols particularly. Finally, MB participates in reactions of carbonylation as any unsaturated reactant. MB reacts in butanol with nickel carbonyl in the presence of HCl even at room temperature and gives as main product butylic ether of 4-hydroxy-4-methyl-2-pentenoic acid with a good yield [12]. After the further hydrogenation and hydrolysis, isohexane acid and corresponding lactone (1).

819190

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