THE SYNTHESIS, STRUCTURE AND PROPERTIES OF 3,4-DIOXO-1,6-HEXANEDIOATE (KETIPIC) ACID ESTERS

Mukovoz Petr Petrovich, Candidate of chemical sciences, leading researcher, Institute of Cellular and Intracellular Symbiosis, Ural Branch of the Russian Academy of Sciences
(Orenburg, 11 Pionerskaya str.) , mpp27@mail.ru
Koz'minykh Vladislav Olegovich, Doctor of chemical sciences, professor, head of sub-department of chemistry, Perm State Pedagogical University, (Perm, 24 Sibirskaya str.) , kvoncstu@yahoo.com

547.341+547.725

Background. 1,3,4,6-tetracarbonyl compounds are widely used in organic synthesis as intermediates to produce various practically relevant azine systems [1]. Such tetracarbonyl structures as 3,4-dioxo-1,6-hexanedioate (ketipic) acid ethers still remain understudied. The purpose of this paper was to enlarge with our own data and generalize the present data on the structure and production methods of ketipi-nates as well as to summarize the data on reactions resulting in new nitrogen acyclic and heterocyclic derivatives.
Materials and methods. Sodium hydride, alkyl acetates and dialkyl oxalates were used as starter compounds while o-xylene was used as inert medium. The modified method based on the ester condensation was used to synthesize ketipinates.
Results. A two-stage ketipinate production process by hydri-dosodium-catalyzed combination of alkyl acetates with dialkyl oxalates was devel-oped. The peculiarities of dialkyl ketipinate structure were studied, previously un-known tautomeric forms were discovered. The reactions between ketipinates with N,N- and О,N-bionucleophiles were studied, new heterofunctional oxa- and aza-ketipinate derivatives were produced. The reaction between ketipinates and acetic anhydride was studied, new O-acyl oxofuran derivatives were produced and the pe-culiarities of their structure were established.
Conclusions. It was discovered that ketipinates in the solid state and in nonpolar solutions are represented by bis-chelate dienol form, while in polar solvents tetraketone form is the dominant one. It was demonstrated that ketipinates and hydrazine derivatives form linear structure prod-ucts, while the combination with urea, 1,2-diaminebenzene, 1,2-aminophenols re-sults in hetercyclic oxa- and aza- derivatives. The study shows that the reaction of ketipinates with acetic anhydride results in either new linear O-acyl systems or (subject to provisions) O-acyl oxofuran derivatives.

dialkyl ketipinates, hydrazones, quinoxalines, О,О-semiacetals, benzo¬xazines, imidazolidins, О-acyloxofurans.

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