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Synthesis of 3,4,5-trimethylpyrazole. Single Crystal X-ray Molecular Structure at 100 K and Thermal Behaviour

Year 2010, Volume: 5 Issue: 2, 200 - 210, 11.11.2010

Abstract

The X-ray molecular structure of 3,4,5-trimethylpyrazole (tmp) at 100 K has been determineted. The compound cyristallizes as a catemer with the N-H protons located. The thermal behaviour of the compound was investigated by diferantial thermal analysis and thermogravimetry. Additionally, compound also characterized by elementel analysis, IR, UV-vis spectroscopy, 1 H-NMR and 13C-NMR.

References

  • Eicher T., Hauptmann, S., 2003. The Chemistry of Heterocycles: Structure, Reactions, Synthesis, and Applications, Wiley-VCH, Weinheim, p.179.
  • Sener A., Kasımogulları R., Sener M., Bildirici K., Akçamur Y., 2002. Studies on the reactions of cyclic oxalyl compounds with hydrazines or hydrazones : Synthesis and reactions of 4-benzoyl- 1-(3-nitrophenyl)-5-phenyl-1H-pyrazole-3-carboxylic acid, Journal of Heterocyclic Chemistry, 39 (5): 869-875.
  • Halcrow M.A., 2005. The synthesis and coordination chemistry of 2,6-bis(pyrazolyl)pyridines and related ligands-Versatile terpyridine analogues, Coordination Chemistry Reviews, 249 (24): 2880–2908.
  • Dias L.R.S., Alvim M.J., Freitas A.C.C., Barreiro E.J., Miranda A.L.P., 1994. Synthesis and analgesic properties of 5-acyl-arylhydrazone 1-H pyrazolo [3,4-b] pyridine derivatives, Pharmaceutica Acta Helvetiae, 69 (3): 163-169.
  • Anandarajagopal K., Sunilson J.A.J., Illavarasu A., Thangavelpandian N., Kalirajan R., 2010. Antiepileptic and Antimicrobial Activities of Novel 1-(unsubstituted/substituted)-3,5-dimethyl- 1H-pyrazole Derivatives, International Journal of ChemTech Research, 2 (1): 45-49.
  • Bailey D.M., Hansen P.E., Hlavac A.G., Baizman E.R., Pearl J., Defelice A.F., Feigenson M.E., 1985. 3,4-Diphenyl-1H-pyrazole-1-propanamine antidepressants, Journal of Medicinal Chemistry, 28 (2): 256-260.
  • Sugiura S., Ohno S., Ohtani O., Izumi K., Kitamikado T., Asai H., Kato K., 1977. Syntheses and antiinflammatory and hypnotic activity of 5-alkoxy-3-(N-substituted carbamoyl)-1- phenylpyrazoles. 4, Journal of Medicinal Chemistry, 20 (1): 80-85.
  • Behr L.C., Fusco R., Jarboe C.H., 1967. The Chemistry of Heterocyclic Compounds, Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and Condensed Rings, Vol.22, John Wiley & Sons, New York, p.81.
  • Palwinder S., Kamaldeep P., Wolfgang H., 2006. Synthesis of pyrazole-based hybrid molecules: search for potent multidrug resistance modulators, Bioorganic & Medicinal Chemistry, 14 (14): 5061-5071.
  • Padmaja A., Payani T., Reddy G.D., Padmavathi V., 2009. Synthesis, antimicrobial and antioxidant activities of substituted pyrazoles, European Journal of Medicinal Chemistry, 44 (11): 4557– 4566.
  • Farghaly A.M., Soliman R., Khalil M.A., Bekhit A.A., el-Din A., Bekhit A., 2002. Thioglycolic acid and pyrazole derivatives of 4(3H)-quinazolinone: synthesis and antimicrobial evaluation, Bollettino chimico farmaceutico, 141 (5): 372-378.
  • Moedritzer K., Allgood S.G., Charumilind P., Clark R.D., Gaede B.J., Kurtzweil M.L., Mischke D.A., Parlow J.J., Rogers M.D., Singh R.K., Stikes G.L., Webber R.K., 1992. Novel Pyrazole Phenyl Ether Herbicides, American Chemical Society, 504 (15): 147-160.
  • White G.A., Phillips J.N., Huppatz J.L., Witrzens B., Grant S.J., 1986. Pyrazole carboxanilide fungicides : I. Correlation of mitochondrial electron transport inhibition and anti-fungal activity, Pesticide Biochemistry and Physiology, 25 (2): 163-168.
  • Londershausen M., 1996. Review: Approaches to New Parasiticides, Pesticide. Science, 48 (4): 269- 292.
  • Lubs H.A., 1970. The Chemistry of Synthetic Dyes and Pigments, American Chemical Society, Vol.127, Washington, p. 730.
  • Garcia H., Iborra S., Miranda M.A., Morera I.M., Primo J., 1991. Pyrazoles and isoxazoles derived from 2-hydroxyaryl phenylethynyl ketones: Synthesis and spectrophotometric evaluation of their potential applicability as sunscreens, Heterocycles, 32 (9): 1745-1755.
  • Elhaik J., Kilner C.A., Halcrow M.A., 2006. Structural diversity in iron(II) complexes of 2,6- di(pyrazol-1-yl)pyridine and 2,6-di(3-methylpyrazol-1-yl)pyridine, Dalton Transactions, (6): 823-830.
  • Ehrlich H.W.W., 1960. The crystal and molecular structure of pyrazole, Acta Crystallographica, 13 (11): 946-952.
  • Fusco R., 1967. Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and Condensed Rings, (Eds.: R.H. Wiley, John Wiley), Wiley Interscience, New York, p.684.
  • Berthou J., Elguero J., Rerat C., 1970. Affinement de la structure cristalline du pyrazole, Acta Crystallographica, Section B, 26 (11): 1880-1881.
  • Schofield K., Grimmett M.R., Keene B.R.T., 1976. The Azoles, Cambridge University Press, Cambridge, p.257.
  • Goddard R., Claramunt R.M., Escolastico C., Elguero J., 1999. Structures of NH-pyrazoles bearing only C-methyl substituents: 4-methylpyrazole is a hydrogen-bonded trimer in the solid (100 K), New Journal of Chemistry, 23 (2): 237-234.
  • Baldy A., Elguero J., Faure R., Pierrot M., Vincent E.J., 1985. Dynamic intermolecular tautomerism of 3,5-dimethylpyrazole in the solid state by carbon-13 CP/MAS NMR spectroscopy and x-ray crystallography, American Chemical Society, 107 (18): 5290-5291.
  • Infantes L., Foces-Foces C., Elguero J., 1999. 3(5),4-Dimethyl- and 3,4,5-trimethylpyrazole at 200 K. X-ray crystallography and quantum-chemical analysis, Acta Crystallographica Section B, 55 (3): 441-447.
  • Erdik E., Obalı M., Yüksekışık N., Öktemer A., Pekel T., İhsanoğlu E., 1997. Denel Organik Kimya, 2.baskı, Ankara Üniversitesi Fen Fakültesi Döner Sermaye İşletmesi Yayınları, Ankara, s.1226.
  • Kurtaran R., Namlı H., Kazak C., Turhan O., Atakol O., 2007. Synthesis, characterization, crystal structure and thermal analysis of a copper(II) mononuclear compound with 2,6-bis(3,5-dimethyl- N-pyrazolyl)pyridine (bdmpp) and selenocyanate as ligands, Journal of Coordination Chemistry, 60 (20): 2133-2138.
  • Schofield K., Grimmett M.R., Keene B.R.T, 1976. Heteroaromatic nitrogen compounds: the azoles, First edition, Cambridge University Press, p.16.
  • Sokolov S.D., 1979. Advances in the Chemistry of 1,2-Azoles, Russian Chemical Reviews, 48 (3): 289-297.
  • Çiğdem Hopa e-posta: cigdem@balikesir.edu.tr
  • Mahir Alkan e-posta: malkan@balikesir.edu.tr
  • Hülya Kara e-posta: hkara@balikesir.edu.tr

3,4,5-trimetilpirazolün Sentezi. 100K’de Tek Kristal X-Işınları Yapısı ve Termal Özellikleri

Year 2010, Volume: 5 Issue: 2, 200 - 210, 11.11.2010

Abstract

3,4,5-tirmetilpirazol (tmp) bileşiğinin X-ışınları moleküler yapısı 100 K’de tayin edildi. Bileşik NH protonları ile katemer yapı oluşturacak şekilde kristallenir. Termal davranışları diferansiyel termal
analiz ve termogravimetrik analiz ile incelendi. Ayrıca karakterizasyonda elementel analiz, IR, UV-vis spektroskopisi, 1 H-NMR ve 13C-NMR yöntemlerinden faydalanıldı.

References

  • Eicher T., Hauptmann, S., 2003. The Chemistry of Heterocycles: Structure, Reactions, Synthesis, and Applications, Wiley-VCH, Weinheim, p.179.
  • Sener A., Kasımogulları R., Sener M., Bildirici K., Akçamur Y., 2002. Studies on the reactions of cyclic oxalyl compounds with hydrazines or hydrazones : Synthesis and reactions of 4-benzoyl- 1-(3-nitrophenyl)-5-phenyl-1H-pyrazole-3-carboxylic acid, Journal of Heterocyclic Chemistry, 39 (5): 869-875.
  • Halcrow M.A., 2005. The synthesis and coordination chemistry of 2,6-bis(pyrazolyl)pyridines and related ligands-Versatile terpyridine analogues, Coordination Chemistry Reviews, 249 (24): 2880–2908.
  • Dias L.R.S., Alvim M.J., Freitas A.C.C., Barreiro E.J., Miranda A.L.P., 1994. Synthesis and analgesic properties of 5-acyl-arylhydrazone 1-H pyrazolo [3,4-b] pyridine derivatives, Pharmaceutica Acta Helvetiae, 69 (3): 163-169.
  • Anandarajagopal K., Sunilson J.A.J., Illavarasu A., Thangavelpandian N., Kalirajan R., 2010. Antiepileptic and Antimicrobial Activities of Novel 1-(unsubstituted/substituted)-3,5-dimethyl- 1H-pyrazole Derivatives, International Journal of ChemTech Research, 2 (1): 45-49.
  • Bailey D.M., Hansen P.E., Hlavac A.G., Baizman E.R., Pearl J., Defelice A.F., Feigenson M.E., 1985. 3,4-Diphenyl-1H-pyrazole-1-propanamine antidepressants, Journal of Medicinal Chemistry, 28 (2): 256-260.
  • Sugiura S., Ohno S., Ohtani O., Izumi K., Kitamikado T., Asai H., Kato K., 1977. Syntheses and antiinflammatory and hypnotic activity of 5-alkoxy-3-(N-substituted carbamoyl)-1- phenylpyrazoles. 4, Journal of Medicinal Chemistry, 20 (1): 80-85.
  • Behr L.C., Fusco R., Jarboe C.H., 1967. The Chemistry of Heterocyclic Compounds, Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and Condensed Rings, Vol.22, John Wiley & Sons, New York, p.81.
  • Palwinder S., Kamaldeep P., Wolfgang H., 2006. Synthesis of pyrazole-based hybrid molecules: search for potent multidrug resistance modulators, Bioorganic & Medicinal Chemistry, 14 (14): 5061-5071.
  • Padmaja A., Payani T., Reddy G.D., Padmavathi V., 2009. Synthesis, antimicrobial and antioxidant activities of substituted pyrazoles, European Journal of Medicinal Chemistry, 44 (11): 4557– 4566.
  • Farghaly A.M., Soliman R., Khalil M.A., Bekhit A.A., el-Din A., Bekhit A., 2002. Thioglycolic acid and pyrazole derivatives of 4(3H)-quinazolinone: synthesis and antimicrobial evaluation, Bollettino chimico farmaceutico, 141 (5): 372-378.
  • Moedritzer K., Allgood S.G., Charumilind P., Clark R.D., Gaede B.J., Kurtzweil M.L., Mischke D.A., Parlow J.J., Rogers M.D., Singh R.K., Stikes G.L., Webber R.K., 1992. Novel Pyrazole Phenyl Ether Herbicides, American Chemical Society, 504 (15): 147-160.
  • White G.A., Phillips J.N., Huppatz J.L., Witrzens B., Grant S.J., 1986. Pyrazole carboxanilide fungicides : I. Correlation of mitochondrial electron transport inhibition and anti-fungal activity, Pesticide Biochemistry and Physiology, 25 (2): 163-168.
  • Londershausen M., 1996. Review: Approaches to New Parasiticides, Pesticide. Science, 48 (4): 269- 292.
  • Lubs H.A., 1970. The Chemistry of Synthetic Dyes and Pigments, American Chemical Society, Vol.127, Washington, p. 730.
  • Garcia H., Iborra S., Miranda M.A., Morera I.M., Primo J., 1991. Pyrazoles and isoxazoles derived from 2-hydroxyaryl phenylethynyl ketones: Synthesis and spectrophotometric evaluation of their potential applicability as sunscreens, Heterocycles, 32 (9): 1745-1755.
  • Elhaik J., Kilner C.A., Halcrow M.A., 2006. Structural diversity in iron(II) complexes of 2,6- di(pyrazol-1-yl)pyridine and 2,6-di(3-methylpyrazol-1-yl)pyridine, Dalton Transactions, (6): 823-830.
  • Ehrlich H.W.W., 1960. The crystal and molecular structure of pyrazole, Acta Crystallographica, 13 (11): 946-952.
  • Fusco R., 1967. Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and Condensed Rings, (Eds.: R.H. Wiley, John Wiley), Wiley Interscience, New York, p.684.
  • Berthou J., Elguero J., Rerat C., 1970. Affinement de la structure cristalline du pyrazole, Acta Crystallographica, Section B, 26 (11): 1880-1881.
  • Schofield K., Grimmett M.R., Keene B.R.T., 1976. The Azoles, Cambridge University Press, Cambridge, p.257.
  • Goddard R., Claramunt R.M., Escolastico C., Elguero J., 1999. Structures of NH-pyrazoles bearing only C-methyl substituents: 4-methylpyrazole is a hydrogen-bonded trimer in the solid (100 K), New Journal of Chemistry, 23 (2): 237-234.
  • Baldy A., Elguero J., Faure R., Pierrot M., Vincent E.J., 1985. Dynamic intermolecular tautomerism of 3,5-dimethylpyrazole in the solid state by carbon-13 CP/MAS NMR spectroscopy and x-ray crystallography, American Chemical Society, 107 (18): 5290-5291.
  • Infantes L., Foces-Foces C., Elguero J., 1999. 3(5),4-Dimethyl- and 3,4,5-trimethylpyrazole at 200 K. X-ray crystallography and quantum-chemical analysis, Acta Crystallographica Section B, 55 (3): 441-447.
  • Erdik E., Obalı M., Yüksekışık N., Öktemer A., Pekel T., İhsanoğlu E., 1997. Denel Organik Kimya, 2.baskı, Ankara Üniversitesi Fen Fakültesi Döner Sermaye İşletmesi Yayınları, Ankara, s.1226.
  • Kurtaran R., Namlı H., Kazak C., Turhan O., Atakol O., 2007. Synthesis, characterization, crystal structure and thermal analysis of a copper(II) mononuclear compound with 2,6-bis(3,5-dimethyl- N-pyrazolyl)pyridine (bdmpp) and selenocyanate as ligands, Journal of Coordination Chemistry, 60 (20): 2133-2138.
  • Schofield K., Grimmett M.R., Keene B.R.T, 1976. Heteroaromatic nitrogen compounds: the azoles, First edition, Cambridge University Press, p.16.
  • Sokolov S.D., 1979. Advances in the Chemistry of 1,2-Azoles, Russian Chemical Reviews, 48 (3): 289-297.
  • Çiğdem Hopa e-posta: cigdem@balikesir.edu.tr
  • Mahir Alkan e-posta: malkan@balikesir.edu.tr
  • Hülya Kara e-posta: hkara@balikesir.edu.tr
There are 31 citations in total.

Details

Primary Language Turkish
Subjects Chemical Engineering
Journal Section Makaleler
Authors

Raif Kurtaran This is me

Çiğdem Hopa

Mahir Alkan

Hülya Kara

Publication Date November 11, 2010
Published in Issue Year 2010 Volume: 5 Issue: 2

Cite

IEEE R. Kurtaran, Ç. Hopa, M. Alkan, and H. Kara, “3,4,5-trimetilpirazolün Sentezi. 100K’de Tek Kristal X-Işınları Yapısı ve Termal Özellikleri”, Süleyman Demirel University Faculty of Arts and Science Journal of Science, vol. 5, no. 2, pp. 200–210, 2010.