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Yeni 4-(2-aminoetil)morfolin substitüe siklotrifosfazenin sentezi ve yapı analizi

Year 2022, Volume: 2 Issue: 1, 40 - 45, 11.11.2022

Elif Yıldız Gül Merve Bal Buse Köse Esra Tanrıverdi Eçik

Abstract

Bu çalışmada, hekzaklorosiklotrifosfazenin primer bir amin olan 4-(2-aminoetil) morfolin ile reaksiyonu THF içerisinde trimetilamin varlığında gerçekleştirilmiştir. Final bileşiğin moleküler yapısı, kütle spektrometresi, FT-IR 31P, 1H ve 13C NMR spektroskopi teknikleri ile doğrulandı. Oluşan ürünün yapı analizi kullanılarak, reaksiyon için olası ilerleme mekanizması önerildi.

Keywords

Siklotrifosfazen aminoetilmorfolin NMR

References

  • [1] Wang, L., Yang. Y.X., Shi. X., Mignani S., Caminde, A.M., Majoral, J.P., “Cyclotriphosphazene core-based dendrimers for biomedical applications: an update on recent advances”, J.Mater.Chem.B, (2018), 6,884-895.
  • [2] Caminade, A.M., Hameauaand, A., Majorala J.P., “The specific functionalization of cyclotriphosphazene for the synthesis of smart dendrimers”, Dalton Trans., (2016), 45,1810-1822.
  • [3] Ainscough, E.W., Brodiei A.M., Derwahl, A., Kirk, S., Otter, C.A. “Conformationally Rigid Chelate Rings in Metal Complexes of Pyridyloxy-Substituted 2,2′-Dioxybiphenyl-Cyclotetra- and Cyclotriphosphazene Platforms”, Inorg. Chem., (2007), 46, 9841-9852.
  • [4] Allen, C.W., “Regio- and stereochemical control in substitution reactions of cyclophosphazenes”, Chem Rev., (1991), 91,119-135.
  • [5] Beşli, S., Coles, S.J., Davies, D.B., Kılıç, A., Shaw, R.A., “Bridged cyclophosphazenes resulting from deprotonation reactions of cyclotriphophazenes bearing a P–NH group”, Dalton Trans., (2011), 40, 5307-5315.
  • [6] Kagit, R., Yildirim, M., Ozay, O., Yesilot, S., Ozay, H. “Phosphazene Based Multicentered Naked-Eye Fluorescent Sensor with High Selectivity for Fe3+ Ions”, Inorg. Chem., (2014), 53, 4, 2144-2151.
  • [7] Tümay S. O., A Novel Selective “Turn-On” Fluorescent Chemosensor Based on Thiophene Appended Cyclotriphosphazene Schiff Base for Detection of Ag+ Ions, Chemistry Select, (2021), 6, 39, 10561-10572.
  • [8] Yıldırım, T., Bilgin, K., Yenilmez Çiftçi, G., Tanrıverdi Eçik, E., Senkuytu, E., Uludag, Y., Tomak, L., Kılıç, A., “Synthesis, cytotoxicity and apoptosis of cyclotriphosphazene compounds as anti-cancer agents”, Eur. J. Med. Chem., (2012), 52, 213-220.
  • [9] Bozkurt B., Elmas G., Yakut M., Okumuş A., Çerçi N. A., Zeyrek C. T., Kılıç Z., Açık L., T. Hökelek, “Phosphorus-nitrogen compounds part 59. The syntheses of tetrachloro and tetraamino-2-pyridylmethylspiro(N/N)ethylenediaminocyclotriphosphazenes: Structural characterization, bioactivity, and molecular docking studies”, J. Chin. Chem. Soc., (2021), 69, 310-331.
  • [10] Elmas G., Okumuş A., Kılıç Z., Özbeden P., Açık L., Tunalı B. Ç., Türk M., Çerçi N. A., Hökelek T., “Phosphorus-nitrogen compounds. Part 48. Syntheses of the phosphazenium salts containing 2-pyridyl pendant arm: Structural characterizations, thermal analysis, antimicrobial and cytotoxic activity studies”, Indian J. Chem. Sec. A, (2020), 59A, 533-550.
  • [11] Mucur S. P., Canımkurbey B., Kavak P., Akbaş H., Karadağ A., “Charge carrier performance of phosphazene-based ionic liquids doped hole transport layer in organic light-emitting diodes”, Appl. Phys. A, (2020), 126, 923.
  • [12] Rao, M. R., Bolligarla, R., Butcher, R.J., Ravikanth, M., “Hexa Boron-Dipyrromethene Cyclotriphosphazenes: Synthesis, Crystal Structure, and Photophysical Properties”, Inorg. Chem., (2010), 40, 10606-10616.
  • [13] Çiftçi, G.Y., Şenkuytu, E, İncir, S.E., Tanrıverdi-Eçik, E., Zorlu, Y, Ölçer, Z., Uludağ, Y., “Characterization of paraben substituted cyclotriphosphazenes, and a DNA interaction study with a real-time electrochemical profiling based biosensor”, Microchim Acta, (2017), 184, 2307–2315.
  • [14] Sarıkaya, S.Y., Yeşilot, S., Kılıç, A., Okutan, E., “Novel BODIPY-Cyclotriphosphazene- Fullerene triads: Synthesis, characterization and singlet oxygen generation efficiency”, Dyes and Pigments, (2018), 153, 26–34.
  • [15] Şenkuytu E., Okutan E., Tanrıverdi-Eçik E., “Cyclotriphosphazene-BODIPY Dyads: Synthesis, halogen atom effect on the photophysical and singlet oxygen generation properties” Inorg. Chem Acta., (2020), 502, 119342.
  • [16] Ainscough, E.W., Brodie, A.M., Derwahl, A., Kirk, S., Otter, C.A. “Conformationally Rigid Chelate Rings in Metal Complexes of Pyridyloxy-Substituted 2,2′-Dioxybiphenyl-Cyclotetra- and Cyclotriphosphazene Platforms”, Inorg. Chem., (2007), 46, 9841-9852.
  • [17] Chaplin, A.B., Harrison, J.A., Dyson, P.J. “Revisiting the Electronic Structure of Phosphazenes”, Inorg. Chem., (2005), 44, 8407−8417.
  • [18] Chandrasekhar, V., Thilagar, P., Pandian, B. M., “Cyclophosphazene-based multi-site coordination ligands”, Coord. Chem. Rev., (2007), 251, 1045-1074.
  • [19] Eçik, E.T., Beşli, S., Çiftçi, G.Y., Davies, D.B., Kılıç, A., Yuksel, F. “Stereo-selectivity in a cyclotriphosphazene derivative bearing an exocyclic P–O moiety”. Dalton Trans., (2012), 41, 6715-6725.
  • [20] Ganapathiappan, S., Krishnamurthy, S. S., "Studies of phosphazenes. Part 30. Reactions of hexachlorocyclotriphosphazene with aromatic primary amines: interplay of geminal and non-geminal modes of chlorine replacement", J. Chem. Soc., Dalton Trans., (1987), 579-584.
  • [21] Lee, S. B., Song, S.-C., Jin, J.-I., Sohn, Y. S. " Thermosensitive Cyclotriphosphazenes", J. Am. Chem. Soc., (2000), 122, 8315-8316.
  • [22] Uslu, A., Yeşilot, S., “Chiral configurations in cyclophosphazene chemistry”, Coord. Chem. Rev., (2015), 291, 28-67.
  • [23] Uslu, A., Özcan, E., Dural, S., Yuksel, F., “Synthesis and characterization of cyclotriphosphazene derivatives bearing azole groups”, Polyhedron, (2016), 117, 394-403.
  • [24] Ibisoglu, H., Besli, S., Yuksel, F., Un, I., Kılıç, A., “Investigation of nucleophilic substitution pathway for the reactions of 1,4-benzodioxan-6-amine with chlorocyclophosphazenes”, Inorganica Chimica Acta (2014), 409, 216-226.
  • [25] Bartlett, S.W., Coles, S.J, Davies, D.B., Hursthouse, M.B., Ibisoglu H., et al. “Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6-n)(NHBut)n derivatives” Acta Crystallographica Section B (2006), B62, 321-329.
  • [26] Besli, S., Balcı, C. M., Doğan S., Allen, C.W.,” Regiochemical Control in the Substitution Reactions of Cyclotriphosphazene Derivatives with Secondary Amines” Inorg. Chem., (2018), 57, 19, 12066-12077.
  • [27] Kourounakis A.P., Xanthopoulos D., Tzara A. “Morpholine as a Privileged Structure: A Review on the Medicinal Chemistry and Pharmacological Activity of Morpholine Containing Bioactive Molecules” Med. Res. Rev., (2019), 1-44.
  • [28] Tzara A., Kourounakis A.P., Xanthopoulos D. “Morpholine As a Scaffold in Medicinal Chemistry: An Update on Synthetic Strategies” ChemMedChem, (2020), 15, 392-403.
  • [29] Kumari A., Singh R.K. “Morpholine as ubiquitous pharmacophore in medicinal chemistry: Deep insight into the structure-activity relationship (SAR)” Bioorganic Chem., (2020), 96, 103578
  • [30] Uslu, A., Güvenaltın, S., “The investigation of structural and thermosensitive properties of new phosphazene derivatives bearing glycol and amino acid” Dalton Trans, (2010), 39, 10685–10691.
  • [31] Tanrıvedi-Eçik, E., İbisoğlu, H., Yenilmez-Çiftçi, G., Demir, G., Erdemir, E., Yuksel, F., “Nucleophilic subtitution reactions of mono-functional nucleophilic reagents with cyclotriphosphazenes containing 2, 2- dioxybiphenyl units”, Turkish Journal of Chemistry, (2020), 44, 87-98.

Synthesis and structure analysis of the novel 4-(2-aminoethyl)morpholine substituted cyclotriphosphazene

Year 2022, Volume: 2 Issue: 1, 40 - 45, 11.11.2022

Elif Yıldız Gül Merve Bal Buse Köse Esra Tanrıverdi Eçik

Abstract

In this study, the reaction of hexachlorocyclotriphosphazene with 4-(2-aminoethyl) morpholine which is a primary amine was carried out in the presence of Trimethylamine in THF. The molecular structure of the final compound was confirmed by mass spectrometry, FT-IR, 31P, 1H and 13C NMR spectroscopies. The possible progress mechanism of the reaction was proposed using the structure analysis of the product formed.

Keywords

Cyclotriphosphazene aminoethylmorpholine NMR Cyclotriphosphazene aminoethylmorpholine NMR Siklotrifosfazen aminoetilmorfolin NMR

References

  • [1] Wang, L., Yang. Y.X., Shi. X., Mignani S., Caminde, A.M., Majoral, J.P., “Cyclotriphosphazene core-based dendrimers for biomedical applications: an update on recent advances”, J.Mater.Chem.B, (2018), 6,884-895.
  • [2] Caminade, A.M., Hameauaand, A., Majorala J.P., “The specific functionalization of cyclotriphosphazene for the synthesis of smart dendrimers”, Dalton Trans., (2016), 45,1810-1822.
  • [3] Ainscough, E.W., Brodiei A.M., Derwahl, A., Kirk, S., Otter, C.A. “Conformationally Rigid Chelate Rings in Metal Complexes of Pyridyloxy-Substituted 2,2′-Dioxybiphenyl-Cyclotetra- and Cyclotriphosphazene Platforms”, Inorg. Chem., (2007), 46, 9841-9852.
  • [4] Allen, C.W., “Regio- and stereochemical control in substitution reactions of cyclophosphazenes”, Chem Rev., (1991), 91,119-135.
  • [5] Beşli, S., Coles, S.J., Davies, D.B., Kılıç, A., Shaw, R.A., “Bridged cyclophosphazenes resulting from deprotonation reactions of cyclotriphophazenes bearing a P–NH group”, Dalton Trans., (2011), 40, 5307-5315.
  • [6] Kagit, R., Yildirim, M., Ozay, O., Yesilot, S., Ozay, H. “Phosphazene Based Multicentered Naked-Eye Fluorescent Sensor with High Selectivity for Fe3+ Ions”, Inorg. Chem., (2014), 53, 4, 2144-2151.
  • [7] Tümay S. O., A Novel Selective “Turn-On” Fluorescent Chemosensor Based on Thiophene Appended Cyclotriphosphazene Schiff Base for Detection of Ag+ Ions, Chemistry Select, (2021), 6, 39, 10561-10572.
  • [8] Yıldırım, T., Bilgin, K., Yenilmez Çiftçi, G., Tanrıverdi Eçik, E., Senkuytu, E., Uludag, Y., Tomak, L., Kılıç, A., “Synthesis, cytotoxicity and apoptosis of cyclotriphosphazene compounds as anti-cancer agents”, Eur. J. Med. Chem., (2012), 52, 213-220.
  • [9] Bozkurt B., Elmas G., Yakut M., Okumuş A., Çerçi N. A., Zeyrek C. T., Kılıç Z., Açık L., T. Hökelek, “Phosphorus-nitrogen compounds part 59. The syntheses of tetrachloro and tetraamino-2-pyridylmethylspiro(N/N)ethylenediaminocyclotriphosphazenes: Structural characterization, bioactivity, and molecular docking studies”, J. Chin. Chem. Soc., (2021), 69, 310-331.
  • [10] Elmas G., Okumuş A., Kılıç Z., Özbeden P., Açık L., Tunalı B. Ç., Türk M., Çerçi N. A., Hökelek T., “Phosphorus-nitrogen compounds. Part 48. Syntheses of the phosphazenium salts containing 2-pyridyl pendant arm: Structural characterizations, thermal analysis, antimicrobial and cytotoxic activity studies”, Indian J. Chem. Sec. A, (2020), 59A, 533-550.
  • [11] Mucur S. P., Canımkurbey B., Kavak P., Akbaş H., Karadağ A., “Charge carrier performance of phosphazene-based ionic liquids doped hole transport layer in organic light-emitting diodes”, Appl. Phys. A, (2020), 126, 923.
  • [12] Rao, M. R., Bolligarla, R., Butcher, R.J., Ravikanth, M., “Hexa Boron-Dipyrromethene Cyclotriphosphazenes: Synthesis, Crystal Structure, and Photophysical Properties”, Inorg. Chem., (2010), 40, 10606-10616.
  • [13] Çiftçi, G.Y., Şenkuytu, E, İncir, S.E., Tanrıverdi-Eçik, E., Zorlu, Y, Ölçer, Z., Uludağ, Y., “Characterization of paraben substituted cyclotriphosphazenes, and a DNA interaction study with a real-time electrochemical profiling based biosensor”, Microchim Acta, (2017), 184, 2307–2315.
  • [14] Sarıkaya, S.Y., Yeşilot, S., Kılıç, A., Okutan, E., “Novel BODIPY-Cyclotriphosphazene- Fullerene triads: Synthesis, characterization and singlet oxygen generation efficiency”, Dyes and Pigments, (2018), 153, 26–34.
  • [15] Şenkuytu E., Okutan E., Tanrıverdi-Eçik E., “Cyclotriphosphazene-BODIPY Dyads: Synthesis, halogen atom effect on the photophysical and singlet oxygen generation properties” Inorg. Chem Acta., (2020), 502, 119342.
  • [16] Ainscough, E.W., Brodie, A.M., Derwahl, A., Kirk, S., Otter, C.A. “Conformationally Rigid Chelate Rings in Metal Complexes of Pyridyloxy-Substituted 2,2′-Dioxybiphenyl-Cyclotetra- and Cyclotriphosphazene Platforms”, Inorg. Chem., (2007), 46, 9841-9852.
  • [17] Chaplin, A.B., Harrison, J.A., Dyson, P.J. “Revisiting the Electronic Structure of Phosphazenes”, Inorg. Chem., (2005), 44, 8407−8417.
  • [18] Chandrasekhar, V., Thilagar, P., Pandian, B. M., “Cyclophosphazene-based multi-site coordination ligands”, Coord. Chem. Rev., (2007), 251, 1045-1074.
  • [19] Eçik, E.T., Beşli, S., Çiftçi, G.Y., Davies, D.B., Kılıç, A., Yuksel, F. “Stereo-selectivity in a cyclotriphosphazene derivative bearing an exocyclic P–O moiety”. Dalton Trans., (2012), 41, 6715-6725.
  • [20] Ganapathiappan, S., Krishnamurthy, S. S., "Studies of phosphazenes. Part 30. Reactions of hexachlorocyclotriphosphazene with aromatic primary amines: interplay of geminal and non-geminal modes of chlorine replacement", J. Chem. Soc., Dalton Trans., (1987), 579-584.
  • [21] Lee, S. B., Song, S.-C., Jin, J.-I., Sohn, Y. S. " Thermosensitive Cyclotriphosphazenes", J. Am. Chem. Soc., (2000), 122, 8315-8316.
  • [22] Uslu, A., Yeşilot, S., “Chiral configurations in cyclophosphazene chemistry”, Coord. Chem. Rev., (2015), 291, 28-67.
  • [23] Uslu, A., Özcan, E., Dural, S., Yuksel, F., “Synthesis and characterization of cyclotriphosphazene derivatives bearing azole groups”, Polyhedron, (2016), 117, 394-403.
  • [24] Ibisoglu, H., Besli, S., Yuksel, F., Un, I., Kılıç, A., “Investigation of nucleophilic substitution pathway for the reactions of 1,4-benzodioxan-6-amine with chlorocyclophosphazenes”, Inorganica Chimica Acta (2014), 409, 216-226.
  • [25] Bartlett, S.W., Coles, S.J, Davies, D.B., Hursthouse, M.B., Ibisoglu H., et al. “Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6-n)(NHBut)n derivatives” Acta Crystallographica Section B (2006), B62, 321-329.
  • [26] Besli, S., Balcı, C. M., Doğan S., Allen, C.W.,” Regiochemical Control in the Substitution Reactions of Cyclotriphosphazene Derivatives with Secondary Amines” Inorg. Chem., (2018), 57, 19, 12066-12077.
  • [27] Kourounakis A.P., Xanthopoulos D., Tzara A. “Morpholine as a Privileged Structure: A Review on the Medicinal Chemistry and Pharmacological Activity of Morpholine Containing Bioactive Molecules” Med. Res. Rev., (2019), 1-44.
  • [28] Tzara A., Kourounakis A.P., Xanthopoulos D. “Morpholine As a Scaffold in Medicinal Chemistry: An Update on Synthetic Strategies” ChemMedChem, (2020), 15, 392-403.
  • [29] Kumari A., Singh R.K. “Morpholine as ubiquitous pharmacophore in medicinal chemistry: Deep insight into the structure-activity relationship (SAR)” Bioorganic Chem., (2020), 96, 103578
  • [30] Uslu, A., Güvenaltın, S., “The investigation of structural and thermosensitive properties of new phosphazene derivatives bearing glycol and amino acid” Dalton Trans, (2010), 39, 10685–10691.
  • [31] Tanrıvedi-Eçik, E., İbisoğlu, H., Yenilmez-Çiftçi, G., Demir, G., Erdemir, E., Yuksel, F., “Nucleophilic subtitution reactions of mono-functional nucleophilic reagents with cyclotriphosphazenes containing 2, 2- dioxybiphenyl units”, Turkish Journal of Chemistry, (2020), 44, 87-98.
There are 31 citations in total.

Details

Primary Language Turkish
Journal Section Research Articles
Authors

Elif Yıldız Gül This is me 0000-0001-7422-5665

Merve Bal This is me 0000-0003-0069-0286

Buse Köse This is me 0000-0001-8121-0875

Esra Tanrıverdi Eçik This is me 0000-0003-2953-6872

Publication Date November 11, 2022
Published in Issue Year 2022 Volume: 2 Issue: 1

Cite

APA Yıldız Gül, E., Bal, M., Köse, B., Tanrıverdi Eçik, E. (2022). Yeni 4-(2-aminoetil)morfolin substitüe siklotrifosfazenin sentezi ve yapı analizi. Ata-Kimya Dergisi, 2(1), 40-45.
AMA Yıldız Gül E, Bal M, Köse B, Tanrıverdi Eçik E. Yeni 4-(2-aminoetil)morfolin substitüe siklotrifosfazenin sentezi ve yapı analizi. J Ata-Chem. November 2022;2(1):40-45.
Chicago Yıldız Gül, Elif, Merve Bal, Buse Köse, and Esra Tanrıverdi Eçik. “Yeni 4-(2-aminoetil)morfolin substitüe Siklotrifosfazenin Sentezi Ve Yapı Analizi”. Ata-Kimya Dergisi 2, no. 1 (November 2022): 40-45.
EndNote Yıldız Gül E, Bal M, Köse B, Tanrıverdi Eçik E (November 1, 2022) Yeni 4-(2-aminoetil)morfolin substitüe siklotrifosfazenin sentezi ve yapı analizi. Ata-Kimya Dergisi 2 1 40–45.
IEEE E. Yıldız Gül, M. Bal, B. Köse, and E. Tanrıverdi Eçik, “Yeni 4-(2-aminoetil)morfolin substitüe siklotrifosfazenin sentezi ve yapı analizi”, J Ata-Chem, vol. 2, no. 1, pp. 40–45, 2022.
ISNAD Yıldız Gül, Elif et al. “Yeni 4-(2-aminoetil)morfolin substitüe Siklotrifosfazenin Sentezi Ve Yapı Analizi”. Ata-Kimya Dergisi 2/1 (November 2022), 40-45.
JAMA Yıldız Gül E, Bal M, Köse B, Tanrıverdi Eçik E. Yeni 4-(2-aminoetil)morfolin substitüe siklotrifosfazenin sentezi ve yapı analizi. J Ata-Chem. 2022;2:40–45.
MLA Yıldız Gül, Elif et al. “Yeni 4-(2-aminoetil)morfolin substitüe Siklotrifosfazenin Sentezi Ve Yapı Analizi”. Ata-Kimya Dergisi, vol. 2, no. 1, 2022, pp. 40-45.
Vancouver Yıldız Gül E, Bal M, Köse B, Tanrıverdi Eçik E. Yeni 4-(2-aminoetil)morfolin substitüe siklotrifosfazenin sentezi ve yapı analizi. J Ata-Chem. 2022;2(1):40-5.
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