Fitalimid işlevsel gruplar taşıyan yeni bir simetrik benzimidazol tuzunun sentezi, yapısal ve spektroskopik özelliklerinin araştırılması

Abstract

Yeni bir N‒Heterosiklik karben tuzu olan 1,3‒bis (N‒ (3‒etil) fitalimid)‒benzimidazol‒3‒yum bromür (BEFIBR) yüksek (%83) verimle sentezlenmiştir. Sentezlenen tuzun FT‒IR ve 1H ve 13C NMR deneysel olarak ölçülmüştür. Bu ölçümlerde, karben C’u 169.35 ppm’de ve asidik karben H’i ise 9.65ppm’de gözlenmiştir. SPARTAN‒14 kuantum kimya paket yazılımı kullanılarak kuantum mekaniksel hesaplamalar gerçekleştirilmiştir. Temel enerji ve spektroskopik değerlerin hesaplanmasında “Yoğunluk Fonksiyonel Kuramı” (DFT/EDF2) yöntemi ve 6‒31G* temel seti kullanılmıştır. Bu hesaplamalar sonucunda bağ uzunlukları, bağ açıları FT‒IR ve 1H ve 13C spektrumları hesaplanmıştır. Hesaplanan değerler, deneysel değerlere son derece yakındır. Ckarben 169.3ppm ve asidik H ise 9.62ppm olarak bulunmuştur. Böylece molekülün uzaysal duruşu da tahmin edilmiştir. Hesaplanan değerler ile deneysel yöntemle bulunan sonuçlar şekil ve tablolar üzerinde karşılaştırılmıştır. HOMO ve LUMO şekil ve enerji değerleri hesaplanarak tablo halinde aktarılmıştır.

Keywords

• Benzimidazol
• Yoğunluk Fonksiyonel Teorisi (DFT)
• N-heterosiklik karben tuzları
• SPARTAN paket yazılımı

Synthesis, Investigation of Structural and Spectroscopic Properties of a Novel Symmetrical Benzimidazole Salt with Phthalimid Functional Groups

Abstract

1,3‒bis (N‒ (3‒ethyl) phthalimide)‒benzimidazole‒3‒yum bromide (BEFIBR), a new N‒Heterocyclic carbene salt, was synthesized with high (83%) yield. FT‒IR and 1H and 13C NMR of the synthesized salt were measured experimentally. In these measurements, the peak for Ccarbene was observed at 169.35ppm and acidic H was observed at 9.65ppm. Quantum mechanical calculations were performed using SPARTAN‒14 quantum chemistry software. “Density Functional Theory” (DFT / EDF2) method and 6‒31G* Basis set were used for calculating basic energy and spectroscopic values. The calculated values were found to be very close to experimental results. 169.3 for Ccarbene and 9.65ppm for H. As a result of these calculations, bond lengths, bond angles FT‒IR and 1H and 13C spectra were calculated. In addition, the spatial stance of the molecule was predicted. The calculated values and the results found by the experimental method were compared on the figures and tables. The shape and energy values of HOMO and LUMO were calculated and tabulated.

Keywords

• Benzimidazole
• Density Functional Theory (DFT)
• N‒heterocyclic carbene salts
• SPARTAN suite

References

1. W.A. Herrmann, ve C. Köcher, ”N‒Heterocyclic Carbenes”. Angew. Chem. Int. Ed. Engl., 36: pp. 2162‒2187. 1997
2. J. C. Garrison, ve W. J. Youngs, “Ag(I) N‒Heterocyclic Carbene Complexes: Synthesis, Structure, and Application” Chem. Rev. Cilt: 105, pp. 3978‒4008, 2005
3. W. Wan-Qiang, C. Hua, Y. Ye, H. Yu-Qing, W. Hua-Jing, W. Zhi-Qin, S. Wei, C. Cheng, and F. Verpoort, “Highly Efficient N-Heterocyclic Carbene/Ruthenium Catalytic Systems for the Acceptorless Dehydrogenation of Alcohols to Carboxylic Acids: Effects of Ancillary and Additional Ligands”, Catalysts, Cilt: 10, pp.1‒12, ISSN: 0009‒2665, 2020, doi:10.3390/catal10010010
4. Y. Zhoua, W. Liub, Y. Liua, J. Guana, J. Yana, J.J. Yuana,, D.-J. Taoa,, Z. Songa, “Oxidative NHC catalysis for base-free synthesis of benzoxazinones and benzoazoles by thermal activated NHCs precursor ionic liquid catalyst using air as oxidant”, Mol. Catal., Cilt: 492 (51), pp.1–8, 2020
5. A. Kascatan‒Nebioglu, M.J. Panzner, C.A. Tessier, C.L. Cannon, ve W.J. Youngs, “N‒Heterocyclic carbene‒silver complexes: A new class of antibiotics”, Coordination Chemistry Reviews , Cilt: 251, pp. 884‒895, 2007
6. C. O'Beirne, N.F. Alhamad, Q. Mab, H. Müller-Bunza, K. Kavanagh, G. Butler, X. Zhua ve M. Tack, “Synthesis, structures and antimicrobial activity of novel NHC∗- and Ph3P-Ag(I)-Benzoate derivatives”, Inorganica Chim. Acta, Cilt: 486, pp. 294‒303, 2019
7. F. Guarra, N. Busto, A. Guerri, L. Marchetti, T. Marzo, B. García, T. Biver ve C. Gabbiani, “Cytotoxic Ag(I) and Au(I) NHC-carbenes bind DNA and show TrxRinhibition” J. Inorg. Biochem. Cilt: 205, pp. 1−11, 2020
8. K.B. Choo, S.M. Lee, W. L. Lee ve Y.L. Cheow, “Synthesis, characterization, in vitro antimicrobial and anticancer studies of new platinum N-heterocyclic carbene (NHC) complexes and unexpected nickel complexes” J. Organomet. Chem, Cilt: 898, pp. 1‒14, 2019

9. F. Zhang, Y. Bai, X. Yang, J. Li ve J. Peng, “N‒heterocyclic carbene platinum complexes functionalized with a polyether chain and silyl group: Synthesis and application as a catalyst for hydrosilylation”, Phosphorus Sulfur Silicon Relat Elem, 192:12, pp. 1271‒1278, 2017
10. Z. Taşcı, A. Kunduracıoğlu, İ. Kani. ve B. Çetinkaya, “A New Application Area for Ag‒NHCs: CO2 Fixation Catalyst”, ChemCatChem, Cilt: 4, pp. 1–6, 2012
11. Q.Y. Meng, N. Döben, ve A. Studer, “Cooperative NHC and Photoredox Catalysis for the Synthesis of β-Trifluoromethylated Alkyl Aryl Ketones”, Angew. Chem. Int. Ed. Cilt: 59, pp. 19956–19960, 2020
12. R.A. Haque, N. Hasanudin, M.A. Hussein, S.A. Ahamed ve M.A. Iqbal, “Bis‒N‒heterocyclic carbene silver(I) and palladium(II) complexes: Efficient antiproliferative agents against breast cancer cells”, Inorganic and Nano‒Metal Chemistry, 47:1, pp. 131‒137, 2017
13. A. Kunduracioğlu, “Fitalimid Fonksiyonel Grup İçeren Yeni Bir Benzimidazol Tuzunun Sentezlenmesi, Yapısal Özelliklerinin Spektroskopik ve Hesapsal Yöntemlerle İncelenmesi” El‒Cezeri Journal of Science and Engineering, Cilt:3, Sayı: 3, pp. 391‒400, 2016.
14. A. Kunduracıoğlu, Ö. Tamer, D. Avcı, İ. Kani, Y. Atalay, ve B. Çetinkaya “1‒Pentamethylbenzyl‒3‒nbuthylbenzimidazolesilver(I)bromide complex: Synthesis, characterization and DFT calculations”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Cilt: 121, pp. 35–45, 2014
15. Spartan 14, Wavefunction Inc. Irvine CA, USA, 2014
16. Dhandapani, A., Manivarman, S., Subashchandrabose, S. ve H. Saleem “Molecular structure and vibrational analysis on (E)‒1‒(3‒methyl‒2,6‒diphenyl piperidin‒4‒ylidene) semicarbazide” Journal of Molecular Structure, Cilt: 1058, pp. 41‒50, 2014
17. E. Karakaş‒Sarıkaya, ve Ö. Dereli, “Study on Molecular Structure and Vibrational Spectra of 5,7‒Dimethoxycoumarin Using DFT: A Combined Experimental and Quantum Chemical Approach” Optics And Spectroscopy, Cilt: 117, 2, pp. 240‒249, 2014
18. Ö. Dereli, Y. Erdoğdu ve M.T.Güllüoğlu, “Study on molecular structure and vibrational spectra of (triphenylphosphoranylidene) acetaldehyde using DFT: A combined experimental and quantum chemical approach” Journal of Molecular Structure, Cilt: 1012, pp. 105‒112, 2012
19. E.K. Sarıkaya, Ö. Dereli, Y. Erdoğdu, ve M.T. Güllüoğlu, “Molecular structure and vibrational spectra of 7‒Ethoxycoumarin by density functional method.” Journal of Molecular Structure, 1049, pp. 220‒226, 2013
20. T. Onishi, “Quantum Computational Chemistry: Modelling and Calculation for Functional Materials”, Springer-Singapore, pp. 49‒53, 2018
21. N. Islam ve S. Kaya, “Conceptual Density Functional Theory And Its Applıcation In The Chemical Domain”, pp: 15-41, Apple Academic Press, Inc.Canada&USA 2018
22. A. Greenberg, C.M.Breneman ve J.F.Liebman, “The amide linkage: Structural significance in chemistry, biochemistry and materials science”, pp. 218‒220 JohnWiley&Sons Inc., NewJersey, USA, 2003
23. X.S. Fu, X.P.Yu, W.M. Wang ve F. Lin, “N‒(3,4‒Difluorophenyl)phthalimide”, Acta Cryst. E66, pp. o1809 2010.
24. N. Vila, M.C. Costas‒Lago, P. Besada ve C. Teran “2‒Benzyl‒5‒methoxyisoindoline‒1,3‒dione”, Acta Cryst. E69, pp. o1594–o1595 2013.
25. M. Flores‒Alamo, M. del C. Romero‒Quiroz, ve J. Morgado, “N‒Crotylphthalimide”, Acta Cryst. E66, pp. o3209, 2010.