skip to main content

Palladium Complexes Catalysed Telomerisation of Arylamines with Butadiene and Their Cyclisation into Quinoline Derivatives

1Department of Technologies of Meat, Dairy Products and Chemicals, Federal State Budgetary Educational Establishment of Higher Education, Bashkir State Agrarian University, Ufa, Russian Federation

2Laboratory of Pharmacophore Cyclic Systems, Ufa Institute of Chemistry, Ufa Federal Research Center of the Russian Academy of Sciences, Ufa, Russian Federation

Received: 25 Jan 2022; Revised: 1 Mar 2022; Accepted: 7 Mar 2022; Available online: 15 Mar 2022; Published: 30 Jun 2022.
Editor(s): Dmitry Murzin
Open Access Copyright (c) 2022 by Authors, Published by BCREC Group
Creative Commons License This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.

Citation Format:
Cover Image

Since alkynyl-arylamines are widely used in the chemical industry as pre products, a method of catalytic synthesis of problematic substituted quinolines from aromatic amines containing octadienal substituents has been developed. For this purpose, the processes of N-2,7-octa-dienyl anilines cyclisation under the action of transition metal complexes and telomerisation of arylamines with butadiene in the presence of palladium complexes were studied. Suppose N-2,7-octa-dienyl anilines are synthesised by telomerisation of arylamines with butadiene in the presence of palladium complexes. In that case, the cyclisation process is carried out in the presence of catalytic amounts of Pd(II) complex with dimethyl sulfoxide or nitrobenzene. The conducted research made it possible to study the opportunity of obtaining in one stage aromatic amines substituted in the nucleus by the reaction of butadiene with arylamines in the presence of palladium complexes. The research proved the principal possibility of obtaining ortho-substituted naphthylamines from butadiene and corresponding naphthylamines in one stage. A catalytic method for the synthesis of problematic substituted quinolines in the presence of palladium complexes has been developed. It has been established that the cyclisation of N-octadienyl-arylamines into quinolines proceeds through the stage of Kleisen amino rearrangement. N-2,7-octa-dienyl anilines and their derivatives can be widely used in the paint, pharmaceutical and chemical industries. Quinoline alkenylene derivatives can be used to produce unique polymer materials, hardeners, stabilisers, extractants, sorbing agents, catalysts for the synthesis of polyurethanes, biologically active substances and their analogues. They are pre-products in synthesising alkaloids, medicines and products used in agriculture. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (


Fulltext View|Download
Keywords: telomerization; cyclazation; N-2.7-okta-dienyl aniline; 2-(1,7-octadien-3-yl) aniline; quiniline

Article Metrics:

  1. Zaripov, R.R. (2015). 2-(Cyclopent-1-enyl)aniline in the synthesis of new 3,1-benzoxazine-4,1'-cyclopentane derivatives. Dissertation of the Candidate of Chemical Sciences. Ufa: Federal State Budgetary Educational Establishment of Higher Education «Bashkir State Agrarian University»
  2. Krawczyk, M., Pastuch-Gawołek, G., Pluta, A., Erfurt, K., Domiński, A., Kurcok, P. (2019). 8-Hydroxyquinoline glycoconjugates: Modifications in the linker structure and their effect on the cytotoxicity of the obtained compounds. Molecules, 24(22), 4181. DOI: 10.3390/molecules24224181
  3. Nagargoje, A.A., Akolkar, S.V., Siddiqui, M.M., Subhedar, D.D., Sangshetti, J.N., Khedkar, V.M., Shingate, B.B. (2020). Quinoline based monocarbonyl curcumin analogs as potential antifungal and antioxidant agents: synthesis, bioevaluation and molecular docking study. Chemistry & Biodiversity, 17(2), e1900624. DOI: 10.1002/cbdv.201900624
  4. Roberts, L., Egan, T.J., Joiner, K.A., Hoppe, H.C. (2008). Differential effects of quinoline antimalarials on endocytosis in Plasmodium falciparum. Antimicrobial Agents and Chemotherapy, 52(5), 1840–1842. DOI: 10.1128/AAC.01478-07
  5. Kadela-Tomanek, M., Bębenek, E., Chrobak, E., Boryczka, S. (2019). 5, 8-Quinolinedione scaffold as a promising moiety of bioactive agents. Molecules, 24(22), 4115. DOI: 10.3390/molecules24224115
  6. Katritzky, A.R., Rachwal, S., Rachwal, B. (1996). Recent progress in the synthesis of 1,2,3,4,-tetrahydroquinolines. Tetrahedron, 52(48), 15031–15070. DOI: 10.1016/S0040-4020(96)00911-8
  7. Shigireva, Zh.V. (2000). 2,2,4-trimethyl-hydro quinolines. Voronezh: Publishing House of the Voronezh University
  8. Weyesa, A., Mulugeta, E. (2020). Recent advances in the synthesis of biologically and pharmaceutically active quinoline and its analogues: a review. Rsc Advances, 10(35), 20784–20793. DOI: 10.1039/D0RA03763J
  9. Farooq, S., Mazhar, A., Ghouri, A., Ullah, N. (2020). One-Pot Multicomponent Synthesis and Bioevaluation of Tetrahydroquinoline Derivatives as Potential Antioxidants, α-Amylase Enzyme Inhibitors, Anti-Cancerous and Anti-Inflammatory Agents. Molecules, 25(11), 2710. DOI: 10.3390/molecules25112710
  10. Krawczyk, M., Pastuch-Gawołek, G., Hadasik, A., Erfurt, K. (2020). 8-Hydroxyquinoline Glycoconjugates Containing Sulfur at the Sugar Anomeric Position—Synthesis and Preliminary Evaluation of Their Cytotoxicity. Molecules, 25(18), 4174. DOI: 10.3390/molecules25184174
  11. Khoshimov, Sh.M., Absarova, D.K., Sobirov, A.O., Mamazhnova, R.T. (2020). Preparation of quinoline bases based on aromatic amines by reaction with carbonyl compounds to produce heterocycles in the vapour phase. Universum: Technical Sciences, 11(68), 67–74
  12. Czaplińska, B., Malarz, K., Mrozek-Wilczkiewicz, A., Slodek, A., Korzec, M., Musiol, R. (2020). Theoretical and experimental investigations of large stokes shift fluorophores based on a quinoline scaffold. Molecules, 25(11), 2488. DOI: 10.3390/molecules25112488
  13. Hackler, L., Gyuris, M., Huzián, O., Alföldi, R., Szebeni, G.J., Madácsi, R., Knapp, L., Kanizsai, I., Puskás, L.G. (2019). Enantioselective synthesis of 8-hydroxyquinoline derivative, Q134 as a hypoxic adaptation inducing agent. Molecules, 24(23), 4269. DOI: 10.3390/molecules24234269
  14. Selimov, F.A., Dzhemilev, U.M., Ptashko, V.A. (2003). Metal complex catalysis. Synthesis of pyridine bases. Moscow: Chemistry
  15. Hegedus, L.S., Winton, P.M., Varaprath, S. (1981). Palladium-assisted N-alkylation of indoles: Attempted application to polycyclization. The Journal of Organic Chemistry, 46(11), 2215–2221. DOI: 10.1021/jo00324a004
  16. Insuasty, B., Fernéandez, F., Quiroga, J., Moreno, R., Martinez, R., Angeles, E., Gaviñto, R., De Almeida, R.H. (1998). Synthesis of 2‐(p‐R‐benzoylmethylene)‐3‐(p‐R‐phenyl)‐1H‐quinoxalines. Journal of Heterocyclic Chemistry, 35(4), 977–981. DOI: 10.1002/jhet.5570350432
  17. Salikhov, S.M., Zaripov, R.R., Latypova, L.R., Abdrakhmanov, I.B. (2019). Intramolecular heterocyclization of o-(1-cycloalkenyl) anilines 2*. Synthesis of new 4 Н-3, 1-benzoxazine and 4 Н-3, 1-benzothiazine 2-amino derivatives. Chemistry of Heterocyclic Compounds, 55(7), 660–664. DOI: 10.1007/s10593-019-02513-6
  18. Danishefsky, S., Taniyama, E. (1983). Cyclizations of mercury and palladium substituted acyrylanilides. Tetrahedron Letters, 24(1), 15–18. DOI: 10.1016/S0040-4039(00)81314-3
  19. Tolstikov, G.A., Dzhemilev, U.M. (1980). Synthesis of heterocyclic compounds in the presence of transition metal complexes. Chemistry of Heterocyclic Compounds, 16(2), 99–113. DOI: 10.1007/BF00554196
  20. Abdrakhamanov, I., Mustafin, A.G., Tolstikov, G.A., Fakhretdinov, R.N., Dzhemilev, U.M. (1986). Synthesis of Indole and Quinoline Derivatives by Intramolecular Catalytic Cyclization of Allylanilines. Chemischer Informationsdienst, 17(32), 325–327. DOI: 10.1002/chin.198632102
  21. Feng, E., Zhou, Y., Zhang, D., Zhang, L., Sun, H., Jiang, H., Liu, H. (2010). Gold (I)-catalyzed tandem transformation: A simple approach for the synthesis of pyrrolo/pyrido [2,1-a][1,3] benzoxazinones and pyrrolo/pyrido [2, 1-a] quinazolinones. The Journal of Organic Chemistry, 75(10), 3274–3282. DOI: 10.1021/jo100228u
  22. Venkataramu, S.D., Macdonell, G.D., Purdum, W.R., Dilbeck, G.A., Berlin, K.D. (1977). Polyphosphoric acid catalyzed cyclization of aralkenyl-substituted quaternary ammonium salts. The Journal of Organic Chemistry, 42(13), 2195–2200. DOI: 10.1021/jo00433a001
  23. Koch‐Pomeranz, U., Hansen, H.J., Schmid, H. (1975). Photochemical Cyclization of Allylated Anisole and N‐Alkyl Aniline Derivatives. Preliminary communication. Helvetica Chimica Acta, 58(1), 178–182. DOI: 10.1002/hlca.19750580122
  24. Egoshin, V.L., Ivanov, S.V., Savvina, N.V., Kapanova, G.Z., Grjibovski, A.M. (2018). Basic Principles of Biomedical Data Analysis in R. Ekologiya cheloveka (Human Ecology), 7, 55–64. DOI: 10.33396/1728-0869-2018-7-55-64
  25. Nadirov, R.K., Nadirov, K.S., Esimova, A.M., Nadirova, Z.K. (2013). Electrochemical synthesis of biflavonoids. Chemistry of Natural Compounds, 49(1), 108–109. DOI: 10.1007/s10600-013-0521-4
  26. Nadirov, R.K., Nadirov, K.S., Bimbetova, G.Z., Nadirova, Z.K. (2016). Synthesis and Cytotoxic Activity of New Flavopiridol Analogs. Chemistry of Natural Compounds, 52(3), 499–500. DOI: 10.1007/s10600-016-1686-4

Last update:

No citation recorded.

Last update:

No citation recorded.