Synthesis of N-(4′-Benzo[15-crown-5])thiophenoxyphenylaminoglyoxime and its complexes with some transition metals

Original Article


4-(Chloroacetyl)diphenyl thioether (1) was synthesized from chloroacetyl chloride and diphenyl thioether in the presence of AlCl3 as catalyst in a Friedel-Crafts reaction. Subsequently, its keto oxime (2) and glyoxime (3) derivatives were prepared. N-(4′-Benzo[15-crown-5]thiophenoxyphenylaminoglyoxime (H2L) and its sodium chloride complex (H2L · NaCl) were prepared from 4-(thiophenoxy)chlorophenylglyoxime (3), 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Ni(II), Co(II) and Cu(II) complexes of H2L and H2L · NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF2-capped Ni(II) mononuclear complex of the vic-dioxime was prepared. The macrocyclic ligands and their transition metal complexes were characterized on the basis of FT-IR, 1H NMR, 13C NMR spectroscopy and elemental analyses data.


BF2+-capped complex Crown compounds Glyoximes Transition metal complexes 



The authors are please to acknowledge the Scientific Research Projects (BAP) of Selçuk University for grant with grant number No 2005/05401005.


  1. 1.
    Guerriero, P., Tamburini, S., Vigato, P.A.: From mononuclear to polynuclear macrocyclic or macroacyclic complexes. Coord. Chem. Rev. 139, 17–243 (1995)CrossRefGoogle Scholar
  2. 2.
    Melson, G.A.: Coordination Chemistry of Macrocyclic Compounds, Plenum, New York (1979)Google Scholar
  3. 3.
    Alexander, V.: Design and synthesis of macrocyclic ligands and their complexes of lanthanides and actinides. Chem. Rev. 95, 273–342 (1995)CrossRefGoogle Scholar
  4. 4.
    Gund, A., Kepler, B.K.: Synthesis and characterization of new anti-tumor platinum bipyridyl crown ether complexes. J. Inorg. Biochem. 51, 437 (1993)CrossRefGoogle Scholar
  5. 5.
    Pedersen, C.J.: Cyclic polyethers and their complexes with metal salts. J. Am. Chem. Soc. 89, 7017–7036 (1967)CrossRefGoogle Scholar
  6. 6.
    Shinkai, S., Ishihara, M., Ueda, K., Manabe, O.: Photoresponsive crown ethers. Part 14. Photo regulated crown–metal complexation by competitive intramolecular tail(ammonium)-biting. J. Chem. Soc. Perkin. Trans. 2, 511–518 (1985)Google Scholar
  7. 7.
    Rasokha, S.V., Lampeka, Y.D., Moloshtar, L.M.: Synthesis and properties of a new series of bis(macrocyclic) dicopper(II,II), dinickel(II,II) and dinickel(III,III) complexes based on the 14-membered pentaaza unit. J. Chem. Soc., Dalton Trans. 4, 631–636 (1993)CrossRefGoogle Scholar
  8. 8.
    Shakir, M., Varkeyand, S.P., Nasmon, O.S.M.: Transition metal complexes of 20–22-membered octaazamacrocycles: synthesis and characterization. Polyhedron 14, 1283–1288 (1995)CrossRefGoogle Scholar
  9. 9.
    Mehrotra, R.C.: Comprehensive Coordination Chemistry, Pergamon Pres, New York (1988)Google Scholar
  10. 10.
    Chakravorty, A.: Structural chemistry of transition metal complexes of oximes. Coord. Chem. Rev. 13, 1–46 (1974)CrossRefGoogle Scholar
  11. 11.
    Gök, Y.: The synthesis and characterization of novel tetraoxime and its mono- and poly-nuclear complexes containing 12-membered diaza-dithia macrocycles. Polyhedron. 15, 1355–1361 (1996)CrossRefGoogle Scholar
  12. 12.
    Gök , Y.: The synthesis and characterization of new substituted diaminoglyoxime and its cobalt(III) complexes containing 15-membered dioxa-trithia macrocyclic moieties. Polyhedron 15, 3933–3940 (1996)CrossRefGoogle Scholar
  13. 13.
    Gök, Y., Karaböcek, S., Kantein, H.: Axial-ligation and macrocyclization of novel (E,E)-dioximes of nickel(II), palladium(II), platinum(II) and cobalt(III). Trans. Met. Chem. 20, 234–238 (1995)CrossRefGoogle Scholar
  14. 14.
    Mendil, D., Bilgin, A., Gök, Y., Sentürk, H.B.: Synthesis and characterization of a new (E,E)-dioxime and its homo and heteronuclear complexes containing macrobicylic moieties. J. Incl. Phenom. 43, 265–270 (2002)CrossRefGoogle Scholar
  15. 15.
    Pandya, B.R., Agrawal, Y.K.: Dyes and pigments. Synthesis and characterisation of crown ether based azo dyes. Dyes Pigments 52, 161–168 (2002)CrossRefGoogle Scholar
  16. 16.
    Ewa, W.W., Marzena, J., Marina, S.F., Biernat, J.F.: Azomacrocyclic derivatives of imidazole: synthesis, structure, and metal ion complexation properties. Tetrahedron 63, 4414–4421 (2007)CrossRefGoogle Scholar
  17. 17.
    April, L., Ellis, J. Christian, M., Lee, H.W., et al.: Design, synthesis, and characterization of a calcium-sensitive near infrared dye. Talanta 56, 1099–1107 (2002)CrossRefGoogle Scholar
  18. 18.
    Zolotov, Yu.A., Formanovskii, A.A., Pletnev, I.V., et al.: Makrotsiklicheskie soedineniya analiticheskoi khimii (Macrocyclic Compounds in Analytical Chemistry), Nauka, Moscow (1993)Google Scholar
  19. 19.
    Steed, J.W., Atwood, J.L.: Supramolecular Chemistry, Wiley, Chichester (2000)Google Scholar
  20. 20.
    Lehn, J.M.: Supramolecular Chemistry. Concepts and Perspectives. VCH, Weinheim (1998)Google Scholar
  21. 21.
    Ungaro, R., El Haj B., Smid, J.: Substituent effects on the stability of cation complexes 4’-substitued monobenzo crown ethers. J. Am. Chem. Soc. 98, 5198–5202 (1976)CrossRefGoogle Scholar
  22. 22.
    Shchori, E., Jagur-Grodzinski, J., Shporer M.: Kinetics of complexation of macrocyclic polyethers with sodium ions by nuclear magnetic resonance spectroscopy. II. Solvent effects. J. Am. Chem. Soc. 95, 3842–3846 (1973)CrossRefGoogle Scholar
  23. 23.
    Harry Szmant, H., Palopoli, F.P.: Mono- and di-acetodiphenyl sulfide and related compounds. J. Am. Chem. Soc. 72, 1757–1758 (1950)CrossRefGoogle Scholar
  24. 24.
    Gül, A., Bekaroglu, Ö.: Syntheses of NN’-bis(4’-benzo[15-crown-5])diaminoglyoxime and its complexes with copper(II), nickel(II), cobalt(II), cobalt(III), palladium(II), platinum(II), and uranyl(VI). J. Chem. Soc. Dalton. Trans. 12, 2537–2541 (1983)CrossRefGoogle Scholar
  25. 25.
    Ahsen, V., Gökceli, F., Bekaroglu, Ö.: Synthesis of SS’-bis(4’-benzo[15-crown-5])dithiogly-oxime and its complexes with copper(II) nickel(II), cobalt(II), cobalt(III), palladium(II), platinum(II), and platinum(IV). J. Chem. Soc. Dalton. Trans. 8, 1827–1831 (1987)CrossRefGoogle Scholar
  26. 26.
    Kantekin, H., Ocak, Ü., Gök, Y.: Synthesis and characterization of a novel macrocyclic vic-dioxime and some of its mono and trinuclear complexes. Z. Anorg. Allg. Chem. 1, 1095–1102 (2001)CrossRefGoogle Scholar
  27. 27.
    Karapinar, E.: Synthesis and characterization of a new (E,E)-dioxime and its homonuclear complexes. J. Incl. Phenom. Macro. 53, 171–175 (2005)CrossRefGoogle Scholar
  28. 28.
    Özcan, E., Karapınar, E., Demirtas, B.: Synthesis of four new vic-dioximes and their nickel (II), cobalt(II), copper(II) and cadmium(II) complexes. Trans. Met. Chem. 27, 557–561 (2002)CrossRefGoogle Scholar
  29. 29.
    Özcan, E., Mirzaoglu, R.: Synthesis of 4 new substituted arylaminoglyoximes and their complexes with copper(II), nickel(II), cobalt(II), and palladium(II). Synth. React. Inorg. Met. -Org. Chem. 18, 559–574 (1998)Google Scholar
  30. 30.
    Pedersen S.B., Larsen, E.: Anti-amphi and cis-trans isomerisms in some bis(dioximato) nickel(II) complexes. Acta Chemica Scandinavica 27, 3291–3301 (1973)CrossRefGoogle Scholar
  31. 31.
    Karaböcek, S., Bilgin, A., Gök, Y.: A new vicinal-dioxime and its mono and trinuclear complexes containing the monoazatetraoxa macrocyclic moiety. Transition Met.Chem. 22, 420–424 (1997)CrossRefGoogle Scholar
  32. 32.
    Gök, Y., Kantekin, H.: The synthesis and characterization of new (E,E)-dioxime and its mono and heteronuclear complexes containing 14-membered tetraaza macrocyclic moiety. Polyhedron 16, 2413–2420 (1997)CrossRefGoogle Scholar
  33. 33.
    Burakevich, J.V., Lore, A.M., Volpp, G.P.: Phenylglyoxime. seperation, characterization, and structure of three isomers. J. Org. Chem. 36, 1–4 (1971)CrossRefGoogle Scholar
  34. 34.
    Ahsen, V., Musluoglu, E., Gürek, A., Gül, A., Bekaroglu, Ö., Zehnder, M.: Synthesis and complexation of 1,2-bis[(Monoaza[15]Crown-5)-N-Yl]glyoxime-crystal-structure of (1,2-bis[(Monoaza[15]Crown-5)-N-Yl]glyoximato)palladium(II). Helv. Chim. Acta. 73, 174–179 (1990)CrossRefGoogle Scholar
  35. 35.
    Hussain, M.S., Almohdhar, H.M., Alarfaj, A.: Template reactions-axial-ligation and macrocyclization of alpha-furilglyoximates and alpha-aminedioximates of cobalt(III) and rhodium(III). J. Coord. Chem. 18, 339–349 (1988)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2007

Authors and Affiliations

  1. 1.Department of ChemistrySelçuk UniversityKonyaTurkey
  2. 2.Department of Chemistry, Faculty of Arts and SciencesPamukkale UniversityDenizliTurkey

Personalised recommendations