User menu

Accès à distance ? S'identifier sur le proxy UCLouvain

Detailed studies of the interaction of 3-chloroaniline with O,O′-diphenylphosphorylisothiocyanate

Primary tabs

Babashkina, M.G. Robeyns, Koen [UCL] Filinchuk, Yaroslav [UCL] Safin, D.A.

The reaction of neat 3-chloroaniline with neat S[double bond, length as m-dash]C[double bond, length as m-dash]N–P(O)(OPh)2 leads to a new N-phosphorylated thiourea, 3-ClC6H4NHC(S)NHP(O)(OPh)2 (1). The same reaction in non-dried CH2Cl2 or C6H6 leads to the salt-like compounds [3-ClC6H4NH3]+[NCS]− (2) and [3-ClC6H4NH3]+[P(O)2(OPh)2]−·0.5C6H6 (3·0.5C6H6), respectively, while using non-dried acetone yields 1-(3-chlorophenyl)-4,4,6-trimethyl-3,4-dihydropyrimidine-2(1H)-thione (4). Dissolution of 1 in non-dried CH2Cl2, C6H6 or Me2C[double bond, length as m-dash]O leads to the direct formation of 2, 3·0.5C6H6 and 4, respectively. It was established that thione 4 is most likely formed through the thiourea 1-assisted aldol condensation of acetone leading to mesityl oxide. In turn the latter ketone interacts with 1 followed by its hydrolysis leading to 4. Compounds 1–4 have been characterized by NMR spectroscopy and elemental analysis and their molecular structures were elucidated by X-ray diffraction. Hirshfeld surface analysis showed that the structures of both 1 and 4 are mainly characterized by H⋯H, H⋯C, H⋯Cl and H⋯S contacts as well as by H⋯O in the structure of 1. The enrichment ratio, derived as the decomposition of the crystal contact surface between pairs of interacting chemical species, for 1 was found, as expected for the polar contacts, which are generally hydrogen bonds, to be significantly larger than unity for the contacts of the type H⋯O and H⋯S. A much larger than unity value was found for the enrichment ratio of the C⋯C contacts in the structure of 1, which is due to extensive π⋯π stacking in the crystal packing. The enrichment ratio for 4 was found to be larger than unity for the contacts of the type H⋯C and, but with a lesser degree, H⋯Cl and H⋯S.

Document type Article de périodique (Journal article)
Access type Accès restreint
Publication date 2016
Language Anglais
Journal information "New Journal of Chemistry" - Vol. 40, no.2, p. 1230-1236 (2016)
Peer reviewed yes
issn 1144-0546
e-issn 1369-9261
Publication status Publié
Affiliation UCL - SST/IMCN/MOST - Molecules, Solids and Reactivity
Links
  1. Sokolov Felix D., Safin Damir A., Zabirov Nail G., Verat Alexander Yu., Brusko Vasiliy V., Krivolapov Dmitry B., Mironova Ekaterina V., Litvinov Igor A., Synthesis, structure and properties of novel N-thiophosphorylated derivatives of 1,3-dihydro-2H-benzimidazol-2-imine and imidazolidine-2-imine, 10.1016/j.poly.2006.07.016
  2. Safin Damir A., Babashkina Maria G., Sokolov Felix D., Zabirov Nail G., Galezowska Joanna, Kozlowski Henryk, Complexes of a novel N-(diisopropxythiophosphoryl)thiourea derivative of 1,4,8,11-tetraazacyclotetradecane with Na+, K+ and cations, 10.1016/j.poly.2006.09.101
  3. Safin Damir A., Sokolov Felix D., Szyrwiel Łukasz, Babashkina Maria G., Gimadiev Timur R., Hahn F. Ekkehardt, Kozlowski Henryk, Krivolapov Dmitriy B., Litvinov Igor A., Nickel(II) complexes with N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2: Versatile coordination of phosphoryl (X=O) and thiophosphoryl (X=S) derivatives, 10.1016/j.poly.2008.04.014
  4. Sokolov Felix D., Safin Damir A., Bolte Michael, Shakirova Elmira R., Babashkina Maria G., New bifunctional N-thiophosphorylated thiourea and 2,5-dithiobiurea derivatives. Crystal structures of R[C(S)NHP(S)(OiPr)2]2 (R=–N(Ph)CH2CH2N(Ph)– and –NHNH–), 10.1016/j.poly.2008.06.034
  5. Safin Damir A., Sokolov Felix D., Gimadiev Timur R., Brusko Vasiliy V., Babashkina Maria G., Chubukaeva Dinara R., Krivolapov Dmitriy B., Litvinov Igor A., Complexes ofN-ThiophosphorylthioureatBuNHC(S)NHP(S)(OiPr)2 with Zinc(II), Cadmium(II), Nickel(II), and Cobalt(II) Cations, 10.1002/zaac.200700549
  6. Safin Damir A., Babashkina Maria G., Bolte Michael, Klein Axel, The influence of the spacer Z on N-phosphorylated bis-thioureas and 2,5-dithiobiurea Z[C(S)NHP(O)(OiPr)2]2 (Z=NHCH2CH2NH, NHC6H4-2-NH, NHNH) crystal design, 10.1016/j.poly.2009.02.044
  7. Luckay Robert C., Sheng Xia, Strasser Christoph E., Raubenheimer Helgard G., Safin Damir A., Babashkina Maria G., Klein Axel, Competitive bulk liquid membrane transport and solvent extraction of some metal ions using RC(S)NHP(X)(OiPr)2 (X = O, S) as ionophores. Formation of the polynuclear complex of [Ag(NC–NP(S)(OiPr)2)]n, 10.1039/b910650b
  8. Safin, Croat. Chem. Acta, 83, 353 (2010)
  9. Safin Damir A., Babashkina Maria G., Bolte Michael, Klein Axel, Tetraphenylphosphonium salts of N-thiophosphorylated thiobenzamide, mono-thioureas or bis-thioureas, 10.1002/hc.20607
  10. Babashkina Maria G., Safin Damir A., Complexes of [(iPrO)2P(O)NHC(S)NHCH2]2CH2with Co(II), Ni(II), Zn(II), and Pd(II): Reaction of [(iPrO)2P(O)NHC(S)NHCH2]2with KOH Leading to the Imidazolidine-2-Imine Derivative, 10.1080/10426500903061566
  11. Babashkina Maria G., Shakirova Elmira R., Safin Damir A., Sokolov Felix D., Klein Axel, Szyrwiel Łukasz, Kubiak Maria, Kozlowski Henryk, Krivolapov Dmitriy B., Dinuclear Complexes of Copper(I) with Crown Ether-containing N-Thiophosphorylated Bis-thioureas and 2,2′-Bipyridine or 1,10-Phenanthroline: Synthesis, Characterization, and Picrate Extraction Properties, 10.1002/zaac.201000263
  12. Babashkina Maria G., Safin Damir A., Klein Axel, Bolte Michael, Synthesis, Characterisation and Luminescent Properties of Mixed-Ligand Copper(I) Complexes Incorporating N-Thiophosphorylated Thioureas and Phosphane Ligands, 10.1002/ejic.201000165
  13. Safin Damir A., Babashkina Maria G., Bolte Michael, Köckerling Martin, Heteroligand copper(I) complexes of N-thiophosphorylated thioureas and phosphanes: Versatile structures and luminescence, 10.1016/j.ica.2011.01.035
  14. Babashkina Maria G., Safin Damir A., Srebro Monika, Kubisiak Piotr, Mitoraj Mariusz P., Bolte Michael, Garcia Yann, Solvent-induced 1,3-N,S- vs. 1,5-S,S′-coordination in the NiII complex [Ni{p-Me2NC6H4NHC(S)NP(S)(OiPr)2}2], 10.1039/c1ce05387f
  15. Babashkina Maria G., Safin Damir A., Robeyns Koen, Brzuszkiewicz Anna, Kozlowski Henryk, Garcia Yann, Thiophosphorylated bis-thioureas for competitive bulk liquid membrane transport of some metal ions, 10.1039/c1ce06244a
  16. Babashkina Maria G., Safin Damir A., Garcia Yann, Heteroleptic Cu(I) and Ag(I) complexes of N-thiophosphorylated tris–thioureas and triphenylphosphane, 10.1016/j.poly.2011.11.028
  17. Babashkina Maria G., Safin Damir A., Robeyns Koen, Garcia Yann, Complexation properties of the crown ether-containing N-thiophosphorylated thiourea towards NiII, 10.1039/c1dt11958c
  18. Safin Damir A., Babashkina Maria G., Railliet Antoine P., Tumanov Nikolay A., Robeyns Koen, Devlin Eamonn, Sanakis Yiannis, Filinchuk Yaroslav, Garcia Yann, First structurally characterized self-assembly of bipodal N-thiophosphorylated bis-thiourea with CoII: magnetic properties and thermal decomposition, 10.1039/c3dt50254f
  19. Safin Damir A., Babashkina Maria G., Robeyns Koen, Mitoraj Mariusz P., Kubisiak Piotr, Brela Mateusz, Garcia Yann, Experimental and theoretical investigations of the NiII complex with N-phosphorylated thiourea iPrNHC(S)NHP(O)(OPh)2, 10.1039/c3ce41195h
  20. Safin Damir A., Babashkina Maria G., Bolte Michael, Garcia Yann, Novel facile single source precursor N-phosphorylated bis-thiourea [NHC(S)NHP(O)(OPh)2]2 for the “criss-cross” formation of s-triazolidino[1,2-a]-s-triazolidine-3,7-dithiones: First structurally characterized representative, 10.1016/j.poly.2013.06.034
  21. Safin Damir A., Babashkina Maria G., Robeyns Koen, Bolte Michael, Garcia Yann, N-Salicylidene aniline derivatives based on the N′-thiophosphorylated thiourea scaffold, 10.1039/c4ce00598h
  22. Safin Damir A., Babashkina Maria G., Kubisiak Piotr, Mitoraj Mariusz P., Le Duff Cécile S., Robeyns Koen, Garcia Yann, Supramolecular Coordination Complexes of theN-Thiophosphorylated 2,5-Dithiobiurea [NHC(S)NHP(S)(OiPr)2]2with ZnIIand CdIIIons - Cation-Induced Dinuclear Mesocate Structure versus Tetranuclear Nanoscaled Aggregate : Supramolecular ZnIIand CdIIIon Complexes, 10.1002/ejic.201402544
  23. Babashkina Maria G., Safin Damir A., Robeyns Koen, Garcia Yann, A Neutral 1D Coordination Polymer Constructed from the NiIIComplex of theN-Phosphorylated Thiourea PhNHC(S)NHP(O)(OPh)2and Pyrazine: A Single-Source Precursor for Nickel Nanoparticles : A Single-Source Precursor for Nickel Nanoparticles, 10.1002/ejic.201402278
  24. Ugi Ivar, Dömling Alexander, Hörl Werner, Multicomponent reactions in organic chemistry, 10.1016/s0160-9327(05)80086-9
  25. Armstrong Robert W., Combs Andrew P., Tempest Paul A., Brown S. David, Keating Thomas A., Multiple-Component Condensation Strategies for Combinatorial Library Synthesis, 10.1021/ar9502083
  26. Tietze Lutz F, Lieb Monika E, Domino reactions for library synthesis of small molecules in combinatorial chemistry, 10.1016/s1367-5931(98)80010-0
  27. Dömling, Comb. Chem. High Throughput Screening, 1, 1 (1998)
  28. Dax, Curr. Med. Chem., 6, 255 (1999)
  29. Plunkett Matthew J., Ellman Jonathan A., Combinatorial Chemistry and New Drugs, 10.1038/scientificamerican0497-68
  30. Schreiber S. L., Target-Oriented and Diversity-Oriented Organic Synthesis in Drug Discovery, 10.1126/science.287.5460.1964
  31. Biginelli, Gazz. Chim. Ital., 23, 360 (1893)
  32. Kappe C. Oliver, Recent Advances in the Biginelli Dihydropyrimidine Synthesis. New Tricks from an Old Dog, 10.1021/ar000048h
  33. Alam, Indian J. Heterocycl. Chem., 14, 293 (2005)
  34. Swamy S. Nanjunda, Basappa, Priya B.S., Prabhuswamy B., Doreswamy B.H., Prasad J. Shashidhara, Rangappa Kanchugarakoppal S., Synthesis of pharmaceutically important condensed heterocyclic 4,6-disubstituted-1,2,4-triazolo-1,3,4-thiadiazole derivatives as antimicrobials, 10.1016/j.ejmech.2005.12.009
  35. Sriram Dharmarajan, Yogeeswari Perumal, Devakaram Ruth Vandana, Synthesis, in vitro and in vivo antimycobacterial activities of diclofenac acid hydrazones and amides, 10.1016/j.bmc.2005.12.042
  36. Leite Ana Cristina Lima, de Lima Renata Souza, Moreira Diogo Rodrigo de M., Cardoso Marcos Veríssimo de O., Gouveia de Brito Ana Carolina, Farias dos Santos Luciene Maria, Hernandes Marcelo Zaldini, Kiperstok Alice Costa, de Lima Ricardo Santana, Soares Milena B.P., Synthesis, docking, and in vitro activity of thiosemicarbazones, aminoacyl-thiosemicarbazides and acyl-thiazolidones against Trypanosoma cruzi, 10.1016/j.bmc.2006.01.034
  37. Rovnyak George C., Kimball S. David, Beyer Barbara, Cucinotta Gabriella, DiMarco John D., Gougoutas Jack, Hedberg Anders, Malley Mary, McCarthy James P., Calcium Entry Blockers and Activators: Conformational and Structural Determinants of Dihydropyrimidine Calcium Channel Modulators, 10.1021/jm00001a017
  38. Sokolov F., Brusko V., Zabirov N., Cherkasov R., N-Acylamidophosphinates: Structure, Properties and Complexation Towards Main Group Metal Cations, 10.2174/138527206775193031
  39. Spackman Mark A., Jayatilaka Dylan, Hirshfeld surface analysis, 10.1039/b818330a
  40. Spackman Mark A., McKinnon Joshua J., Fingerprinting intermolecular interactions in molecular crystals, 10.1039/b203191b
  41. Safin Damir A., Mitoraj Mariusz P., Robeyns Koen, Filinchuk Yaroslav, Vande Velde Christophe M. L., Luminescent mononuclear mixed ligand complexes of copper(i) with 5-phenyl-2,2′-bipyridine and triphenylphosphine, 10.1039/c5dt02755a
  42. Jelsch Christian, Ejsmont Krzysztof, Huder Loïc, The enrichment ratio of atomic contacts in crystals, an indicator derived from the Hirshfeld surface analysis, 10.1107/s2052252514003327
  43. Sheldrick George M., A short history ofSHELX, 10.1107/s0108767307043930
  44. Bruno Ian J., Cole Jason C., Edgington Paul R., Kessler Magnus, Macrae Clare F., McCabe Patrick, Pearson Jonathan, Taylor Robin, New software for searching the Cambridge Structural Database and visualizing crystal structures, 10.1107/s0108768102003324
Bibliographic reference Babashkina, M.G. ; Robeyns, Koen ; Filinchuk, Yaroslav ; Safin, D.A.. Detailed studies of the interaction of 3-chloroaniline with O,O′-diphenylphosphorylisothiocyanate. In: New Journal of Chemistry, Vol. 40, no.2, p. 1230-1236 (2016)
Permanent URL http://hdl.handle.net/2078.1/174801