Head: Prof. Mikhail M. Krayushkin (e-mail: mkrayioc.ac.ru, tel. +7(499)137-6939)
The laboratory had been founded in 1922 by Full Member of the Academy A.E. Chichibabin who headed it until 1931. Before merging with ZIOC, it existed as an independent Laboratory for Research and Synthesis of Vegetable and Animal Products under the Commission for the Study of Natural Productive Forces. In 1931-1945, Laboratory was headed by Professor M. M. Katznelson. Among the research fellows of Laboratory were well-known Chichibabin's associates: Full Members of the Academy I.L. Knunyants and M.I. Kabachnik, Professors N.A. Preobrazhensky and Ya.L. Goldfarb; the latter headed Laboratory in 1945-1985.
Main results (2007-2012)
Laboratory of Heterocyclic Compounds (LHC) is focused on the synthesis of photoactive compounds for optical memory. Chromone-based compounds were designed. These compounds undergo UV-induced rearrangements to form fluorescent products. The reaction is used to prepare light-sensitive media for optical data storage memory.
Methods for the synthesis of reverse photochromic compounds were developed. They are based on thermally irreversible dihetarylethenes containing thiophene and benzothiophene rings linked by cyclopentene, perfluorocyclopentene, maleimide or other heterocyclic bridges. The photochemical properties of a large series of these compounds were studied.
Dihetarylethenes with sulfur-containing functional groups, which enable their efficient binding to noble metal nanoparticles, were synthesized.
An optical device was designed based on chromones and dihetarylethenes for layer-by-layer recording, erasing, storage, and reproduction of rewritable and optical archive-type information in a multilayer (up to ten layers) recording medium.
A large series of various fulgimides, some of which exhibit fluorescence properties, were synthesized by reactions of thiophene-based fulgides with various amines and their photochromic properties were studied. Reactivity of the products and their photochromic properties were shown to be similar to those of dihetarylethenes. These compounds can be used in optical memory devices.
The Fischer reaction of thiophene derivatives has been studied systematically. The research resulted in the synthesis of previously unavailable thienopyrroles and thienopyrrolenines, which were used to design a new type of unique photochromic spiropyrans, spirooxazines, and merocyanine dyes.
Investigations of S-functionalization of organic compounds with elemental sulfur led to the enlargement of the heterocyclic synthesis scope based on simple and easily available starting compounds. Methods were elaborated for the synthesis of a wide range of monothiooxamides, oxamic acid thiohydrazides and their derivatives containing aromatic and heteroaromatic moieties, which served as a basis for the preparation of various antibacterial compounds, in particular biologically active low-toxicity substances that inhibit the type III secretion system of pathogenic bacteria.
An approach to new fused dihydropyridinone-containing heterocyclic systems was developed. It is based on three-component condensation of corresponding aminoheterocycles with aldehydes and Meldrum’s acid. Calculations with the use of the PASS program predicted that the synthesized dihydropyridines should have psychotropic, anti-neurotic, nootropic or antipsychotic activities.
Methods for the synthesis of nitrogen-containing derivatives of aromatic heterocycles such as furazan, furoxan, 1,2,4- and 1,3,4-oxadiazoles, tetrazole, etc. under atmospheric and high pressure (10-14 kbar) were devised. The compounds were used to produce high-density polynitrogen materials. The 1,3-dipolar cycloaddition reactions were studied and original methods for the synthesis of stable aromatic nitrile oxides were developed. These methods provide the basis for a pioneering environmentally friendly technology of low-temperature vulcanization of rubber, which finds applications both in our country and abroad.
Laboratory has great competence in the synthesis of additives for tire manufacturing. A manufacturing technology was worked out for the production of the anticorching agent SANTOGARD PVI. A large series of sulfenimides was synthesized.
LHC successfully collaborates with world's largest companies such as Michelin, Dow Chemical, Intel, DuPont, Samsung, Lanxess, DuPont, Samsung, and so on.
Selected publications (2006-2011)
- V.A.Barachevsky and M. M.Krayushkin; Photochromic organic compounds for optical memory, Russian Chemical Bulletin, International Edition, Vol. 57, No. 4, pp. 867, 2008.
- M.M.Krayushkin, K.S.Levchenko, V.N.Yarovenko, I.V.Zavarzin, V.A.Barachevsky, Y.A. Puankov, T.M.Valova, and O.I. Kobeleva; Synthesis and study of photosensitive chromone derivatives for recording media of archival three-dimensional optical memory, ARKIVOC, 2009 (ix) 269.
- V.A.Barachevsky, O.I.Kobeleva, T.M.Valova, A.O.Ait, A.A.Dunaev, A.M.Gorelik, M.M. Krayushkin, K.S.Levchenko, V.N.Yarovenko,V.V.Kiyko, E.P.Grebennikov; Photochromic and irreversible photofluorescent organic materials for 3D bitwise optical memory, Optical Memory&Neural Networks (InformationOptics), v.19, N2, 187, 2010.
- M.M.Krayushkin, K.S.Levchenko, V.N.Yarovenko, L.V.Christoforova, V.A.Barachevsky, Y.A.Puankov, T.M.Valova, O.I.Kobeleva and K.A.Lyssenko, Synthesis and reactivity of 1-aryl-9Н-thieno[3,4-b]chromen-9-ones, New J. Chem., 2009, 33, 2267.
- M.M.Krayushkin and M.A.Kalik, Syntheses of Photochromic Dihetarylethenes, In: Katritzky, editors: Advances in Heterocyclic Chemistry, Vol 103, Oxford: Academic Press; 2011, p. 1.
- V.A.Migulin, M.M.Krayushkin, V.A.Barachevsky, O.I.Kobeleva, T.M.Valova, and
- K.A.Lyssenko, Synthesis and Characterization of Nonsymmetric Cyclopentene-Based Dithienylethenes, J. Org. Chem., 2012, 77 (1), pp 332.
- V.A.Barachevsky, O.I.Kobeleva, T.M.Valova, A.O.Ait, A.A.Dunaev, A.M.Gorelik, M.M. Krayushkin, K.S.Levchenko, V.N.Yarovenko, V.V.Kiyko, E.P.Grebennikov. Photochromic and irreversible photofluorescent organic materials for 3D bitwise optical memory, Optical Memory&Neural Networks (Information Optics), v.19, N2, 187, 2010.
- V.Z.Shirinian, S.O.Besugliy, A.V.Metelitsa. M.M.Krayushkin, D.M.Nikalin, and V.I. Minkin, Novel photochromic spirocyclic compounds of thienopyrroline series: 1. Spiropyrans, J. Photochem. Photobiol. A: Chem., 189, 161 (2007).
- V.Z.Shirinian, A.A.Shimkin, "Merocyanines: Synthesis and Application", in "Topics in Heterocyclic Chemistry", Springer, Berlin / Heidelberg, 2008, p. 75.
- V.Z.Shirinian, A.A.Shimkin, S.N.Tipikin., M.M.Krayushkin, Efficient methods for the synthesis of thieno[3,2-b]thiophene and thieno[3,2-b]furan derivatives,/ Synthesis, 2009, No. 22, 3803.
- V.N.Yarovenko; A.V.Polushina; I.V.Zavarzin; M.M.Krayushkin; S.K.Kotovskaya; V.N. Charushin, Synthesis of dihydrothiazoles and thiazoles based on monothiooxamides, Journal of Sulfur Chemistry, 2009, V. 30, Issue 3 & 4, 327.
- V.N.Yarovenko, A.S.Nikitina, I.S.Zavarzin, M.M.Krayushkin, L.V.Kovalenko, "A convenient synthesis of N-substituted 2-thioxo-1,3-thiazolidin-4-ones", Synthesis, 2006, No. 8, 1246.
- V.N.Yarovenko, E.S.Zayakin, M.M.Krayushkin, V.V.Zorina, L.N.Kapotina, and N.A. Zigangirova, Derivatives of Thiohydrazides as Effective Antibacterial Remedies for Chlamydial Infection Treatment at Chronic Stages of Infections, Journal of Chemistry and Chemical Engineering, 2010, 4(4), 55.
- B.V.Lichitsky, A.N.Komogortsev, А.А.Dudinov, M.M.Krayushkin, "Synthesis of 5-oxo-4,5,6,7-tetrahydro-1H-pyrrolo-[3,2-b]pyridine-3-carboxylic acids by three-component condensation of 3-aminopyrrole derivatives", Mendeleev Communications, 2010, 20, N5, 255.
- А.А.Dudinov, A.N.Komogortsev, B.V.Lichitsky, M.M.Krayushkin, "Three-component condensation of 2,4-diaminoselenazole with aldehydes and Meldrum’s acid. Synthesis of 7-aryl(alkyl)-substituted 2-amino-6,7-dihydro-4H-selenazolo[4,5-b]pyridine-5-ones", Phosphorus, Sulfur, and Silicon and the Related Elements, 2010, 185, 1230.
- L.I.Belen’kii, Nitrile Oxides in Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis: Novel Strategies in Synthesis, Second Edition, By Henry Feuer; 2008, John Wiley & Sons, Inc., p.1.