Determination of the Structures of m- and p-nitro Bromoacetophenone Compounds by Experimental (FT‒IR, NMR) and theoretical approaches

Abstract

2-Bromo-3-nitroacetophenone (I) and 2-Bromo-4-nitroacetophenone (II), which are structural isomers of each other, were characterized using proton/carbon NMR, FT-IR, and density functional methods. The effects of the substituents on the molecular geometry parameters were investigated by comparing the optimized molecular structures obtained by computational methods with root mean square error calculations. The potential energy surface scan of the torsion angle between the bromoacetone group and the ring revealed that the lowest energy conformation is at 110°. The molecules' chemical reactivity and kinetic stability in different solvents were studied using frontier molecular orbital analyses. NMR core assignments and IR vibration assignments revealed similarities between the isomers. At the computational level that we determined to be sufficient in accuracy and precision for molecular geometry and spectrum calculations, it was found that the average polarizability of the compounds are approximately five times, and the total high-level polarizability are approximately four times greater than the reference compound when their nonlinear optical properties are theoretically calculated.

Keywords

• Spectroscopy
• DFT
• Non-linear optic
• Molecular modelling

m- ve p-nitro Bromoasetofenon Bileşiklerinin Deneysel (FT‒IR, NMR) ve Teorik Yaklaşımlarla Yapılarının Belirlenmesi

Abstract

Birbirlerinin yapısal izomerleri olan 2-Bromo-3-nitroasetofenon (I) ve 2-Bromo-4-nitroasetofenon (II) bileşikleri proton/karbon NMR, FT-IR ve yoğunluk fonksiyoneli yöntemleri kullanılarak karakterize edildi. Hesaplamalı yöntemlerle elde edilen en iyileştirilmiş moleküler yapıları ortalama hata kare kökü hesapları ile karşılaştırılarak sübstitüentlerin konumlarının moleküler geometri parametreleri üzerindeki etkileri araştırıldı. Bromoaseton grubu ile halka arasıdaki burulma açısının potansiyel enerji yüzey taraması yapılarak en düşük enerjili şekillenimin 110°’de olduğu belirlendi. Farklı çözücüler içinde sınır moleküler orbital analizleri ile moleküllerin kimyasal reaktiviteleri ve kinetik kararlılıkları araştırıldı. NMR’da yapılan çekirdek atamaları ve IR’de yapılan titreşim atamaları izomerler arasındaki benzerlikleri ortaya çıkardı. Moleküler geometri ve spektrum hesaplamalarında yeterli doğruluk ve hassasiyette olduğunu belirlediğimiz hesaplama seviyesinde, bileşiklerin doğrusal olmayan optik özellikleri teorik olarak hesaplandığında referans bileşiğe göre ortalama kutuplanabilirliklerinin yaklaşık dört kat, toplam yüksek mertebe kutuplanabilirliklerinin yaklaşık beş kat fazla olduğu belirlendi.

Keywords

• Spektroskopi
• YFT
• Doğrusal olmayan optik
• Moleküler Modelleme

References

1. AIST (2022a). Advanced Industrial Science and Technology. 2-bromo-3’-nitroacetophenone. Erişim adresi: https://sdbs.db.aist.go.jp/sdbs/cgi-bin/landingpage?sdbsno=32094 (Erişim tarihi: 10 Ekim 2022)
2. AIST (2022b). Advanced Industrial Science and Technology. 2-bromo-4’-nitroacetophenone. Erişim adresi: https://sdbs.db.aist.go.jp/sdbs/cgi-bin/landingpage?sdbsno=23286 (Erişim tarihi: 10 Ekim 2022)
3. Alaşalvar, C., Öztürk, N., Gökçe, H., Güder, A., Menteşe, E. ve Bektaş, H. (2021). Synthesis, structural, spectral, antioxidant, bioactivity and molecular docking investigations of a novel triazole derivative. Journal Of Biomolecular Structure And Dynamics, 40(14), 6642-6655. https://doi.org/10.1080/07391102.2021.1887764
4. Aoki, Y., Oshima, K., & Utimoto, K. (1995). Preparation of Enolates from α -Haloketones with n -BuLi, PhMgBr, or Et 2 Zn via Halogen-Metal Exchange Reaction. Chemistry Letters, 24(6), 463–464. https://doi.org/10.1246/cl.1995.463
5. Austin, A., Petersson, G. A., Frisch, M. J., Dobek, F. J., Scalmani, G., & Throssell, K. (2012). A Density Functional with Spherical Atom Dispersion Terms. Journal of Chemical Theory and Computation, 8(12), 4989–5007. https://doi.org/10.1021/ct300778e
6. Becke, A. D. (1993). Density-functional thermochemistry. III. The role of exact exchange, The Journal of Chemical Physics. 98 (1993) 5648-5652. https://doi.org/10.1063/1.464913
7. Cancès, E., Mennucci, B. & Tomasi, J. (1997). A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics. The Journal of Chemical Physics, 107(8), 3032. https://doi.org/10.1063/1.474659
8. Céspedes, C. L., Uchoa, A., Salazar, J. R., Perich, F. & Pardo, F. (2002). Plant Growth Inhibitory Activity of p -Hydroxyacetophenones and Tremetones from Chilean Endemic Baccharis Species and Some Analogous: A Comparative Study. Journal of Agricultural and Food Chemistry, 50(8), 2283–2292. https://doi.org/10.1021/jf011108g

9. De Kimpe, N. & Verhe, R., (1988). α-Haloketones,α-Haloaldehydes and α-Haloimines. Chichester, UK: John Wiley & Sons, Inc.
10. Erian, A., Sherif, S. & Gaber, H. (2003). The Chemistry of α-Haloketones and Their Utility in Heterocyclic Synthesis. Molecules, 8(11), 793–865. https://doi.org/10.3390/81100793
11. Filarowski, A., Kochel, A., Kluba, M. & Kamounah, F. S. (2008). Structural and aromatic aspects of tautomeric equilibrium in hydroxy aryl Schiff bases. Journal of Physical Organic Chemistry, 21(11), 939–944. https://doi.org/10.1002/poc.1403
12. Foster, J. P. & Weinhold, F. (1980). Natural Hybrid Orbitals. Journal of the American Chemical Society, 102(22), 7211–7218. https://doi.org/10.1021/ja00544a007
13. Fouad, M., Richard D. & Gandour, F. R. F. (2013). 2-bromo-1-(3-nitrophenyl)ethanone. CSD Communication. https://doi.org/10.5517/cc11jd76
14. Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A., Jr., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N.,…(2009). Gaussian 09, Revision D.01. Wallingford CT: Gaussian Inc.
15. Garcia-Salas, P., Morales-Soto, A., Segura-Carretero, A., & Fernández-Gutiérrez, A. (2010). Phenolic-Compound-Extraction Systems for Fruit and Vegetable Samples. Molecules, 15(12), 8813–8826. https://doi.org/10.3390/molecules15128813
16. GaussView, Dennington, R., Keith, T., Millam, J. (2009). Version 5, Semichem Inc., Shawnee Mission, KS.
17. Jamróz, M. H. (2010). Vibrational Energy Distribution Analysis (VEDA) 4. Vibrational Energy Distribution Analysis VEDA 4, Warsaw.
18. Jasinski, J. P., Butcher, R. J., Praveen, A. S., Yathirajan, H. S., & Narayana, B. (2011). 2-Bromo-1-(3-Nitrophenyl)Ethanone. Acta Crystallographica Section E: Structure Reports Online, 67(1), 1562–1565. https://doi.org/10.1107/S1600536810049585
19. Karunasingha, D. S. K. (2022). Root mean square error or mean absolute error? Use their ratio as well, Information Sciences. 585, 609–629. https://doi.org/10.1016/j.ins.2021.11.036
20. Kemp, W. (1991). Organic Spectroscopy (C. 4). London: Macmillan Education UK. https://doi.org/10.1007/978-1-349-15203-2
21. Kim, H. K., Tak, J. H. & Ahn, Y. J. (2004). Acaricidal Activity of Paeonia suffruticosa Root Bark-Derived Compounds against Dermatophagoides farinae and Dermatophagoides pteronyssinus (Acari: Pyroglyphidae). Journal of Agricultural and Food Chemistry, 52(26), 7857–7861. https://doi.org/10.1021/jf048708a
22. Köse, E. (2016). the Spectroscopic Analysis of 2,4’-Dibromoacetophenone Moleculeby Using Quantum Chemical Calculations. Anadolu University Journal of Science and Technology A - Applied Sciences and Engineering, 17(AFG5 SPECIAL ISSUE), 677–677. https://doi.org/10.18038/aubtda.267115
23. Kruszewski, J. & Krygowski, T. M. (1972). Definition of aromaticity basing on the harmonic oscillator model. Tetrahedron Letters, 13(36), 3839–3842. https://doi.org/10.1016/S0040-4039(01)94175-9
24. Krygowski, T. M. (1993). Crystallographic studies of inter- and intramolecular interactions reflected in aromatic character of Pi-electron systems. Journal of Chemical Information and Modeling, 33(1), 70–78. https://doi.org/10.1021/ci00011a011
25. Lalama, S. J., & Garito, A. F. (1979). Origin of the nonlinear second-order optical susceptibilities of organic systems. Physical Review A, 20(3), 1179–1194. https://doi.org/10.1103/PhysRevA.20.1179
26. Ma, Y.-T., Fan, H.-F., Gao, Y.-Q., Li, H., Zhang, A.-L., & Gao, J.-M. (2013). Natural Products as Sources of New Fungicides (I): Synthesis and Antifungal Activity of Acetophenone Derivatives Against Phytopathogenic Fungi. Chemical Biology & Drug Design, 81(4), 545–552. https://doi.org/10.1111/cbdd.12064
27. Oh, M. S., Yang, J.-Y., & Lee, H. S. (2012). Acaricidal Toxicity of 2′-Hydroxy-4′-methylacetophenone Isolated from Angelicae koreana Roots and Structure–Activity Relationships of Its Derivatives. Journal of Agricultural and Food Chemistry, 60(14), 3606–3611. https://doi.org/10.1021/jf205379u
28. Pattison, G. (2017). Conformational preferences of α-fluoroketones may influence their reactivity. Beilstein Journal of Organic Chemistry, 13, 2915–2921. https://doi.org/10.3762/bjoc.13.284 Socrates, G. (2004). Infrared and Raman Characteristic Group Frequencies: Tables and Charts, 3rd Edition (3rd baskı). John Wiley & Sons.
29. Stuart, B. H. (2004). Infrared Spectroscopy: Fundamentals and Applications. Chichester, UK: John Wiley & Sons, Ltd. https://doi.org/10.1002/0470011149
30. Sundaraganesan, N., Ilakiamani, S., Saleem, H., Wojciechowski, P. M., & Michalska, D. (2005). FT-Raman and FT-IR spectra, vibrational assignments and density functional studies of 5-bromo-2-nitropyridine. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 61(13–14), 2995–3001. https://doi.org/10.1016/j.saa.2004.11.016
31. Vijayalakshmi, S., & Kalyanaraman, S. (2014). DFT and TD-DFT approach for the analysis of NLO and OLED applications of 9-anthraldehyde. Optik, 125(10), 2429–2432. https://doi.org/10.1016/j.ijleo.2013.10.104
32. Wolinski, K., Hinton, J. F. & Pulay, P. (1990). Efficient Implementation of the Gauge-Independent Atomic Orbital Method for NMR Chemical Shift Calculations. Journal of the American Chemical Society, 112(23), 8251–8260. https://doi.org/10.1021/ja00179a005
33. Yi, C., Chen, J., Wei, C., Wu, S., Wang, S., Hu, D. & Song, B. (2020). α-Haloacetophenone and analogues as potential antibacterial agents and nematicides. Bioorganic & Medicinal Chemistry Letters, 30(2), 126814. https://doi.org/10.1016/j.bmcl.2019.126814
34. Yıldırım, A. Ö., Yıldırım, M. H. & Kaştaş, Ç. A. (2016). Studies on the synthesis, spectroscopic analysis and DFT calculations on (E)-4,6-dichloro-2-[(2-chlorophenylimino)methyl]-3methoxyphenol as a novel Schiff’s base. Journal of Molecular Structure, 1113, 1–8. https://doi.org/10.1016/j.molstruc.2016.02.041