2,3-dimetoksifenilboronik asit molekülünün konformasyon ve FTIR analizi

2,3-dimetoksifenil boronik asit molekülünün (2,3-dmpba; C6H3(OCH3)2B(OH)2) konformasyonel yapısı ve hidroksil (OH) gerilmeleri titreşimi üzerindeki çözücü etkisi Fourier dönüşümlü kızılötesi spektroskopisi (FTIR) ve yoğunluk fonksiyonel teorisi (YFT) ile birlikte hem deneysel hem de teorik olarak araştırılmıştır. Hesaplamalar polarize süreklilik modeli (PCM) kullanılarak on sekiz farklı organik çözücüde ve bileşiğin dört konformasyonel izomeri üzerinde odaklanmıştır. Titreşim analizleri için skalanmış kuantum mekanik model (SQM) kullanılmıştır. Ele alınan molekülün en kararlı konformasyonel izomeri çözücü etkisinden bağımsızdır. SQM metodu titreşim frekansları üzerindeki çözücü etkisini belirlemede oldukça başarılıdır. Bu çalışmadan elde edilen deneysel ve teorik tüm bulgular fenil boronik asit türevlerinin yapısal karakteristiklerini anlamada faydalı olacaktır.

Anahtar Kelimeler:

Fenilboronik asit türevleri, FTIR, DFT, SQM, Çözücü etkisi

Conformational and FTIR analyses of 2,3-dimethoxyphenylboronic acid

The experimental and theoretical investigations of solvent effect on conformational structure and the hydroxyl stretching vibration of 2,3-dimethoxyphenylboronic acid (2,3-dmpba; C6H3(OCH3)2B(OH)2) molecule were studied by Fourier transform infrared (FTIR) spectroscopy and density functional theory (DFT). Calculations were performed by four conformational isomers of the title compound in eighteen different organic solvents by the polarizable continuum model (PCM). Scaled quantum mechanical (SQM) method was performed for the vibrational analysis. Most stable conformational isomer of the compound is independent of the solvent effect. Results of SQM method are very successful in determining the solvent effect on vibrational frequency. Experimental and theoretical findings from the present search will be useful to understand structural characteristics of phenylboronic acid derivatives.

Keywords:

Phenylboronic acid derivatives, FTIR, DFT, SQM, Solvent effect,

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Hall DG. Boronic Acids: Preparation and Applications in Organic Synthesis and Medicine. Alberta, Canada, Wiley, 2005.
Yang W, Gao X, Wang B. Biological and medicinal applications of boronic acids. Editor: Hall DG. Preparation and Applications in Organic Synthesis and Medicine, 481-512, Alberta, Canada, Wiley, 2005.
Cambre JN, Sumerlin BS. “Biomedical applications of boronic acid polymers”. Polymer, 52(21), 4631-4643, 2011.
Wang B, Yoshida K, Sato K, Anzai J. “Phenylboronic acid-functionalized layer-by-layer assemblies for biomedical applications”. Polymers, 9(6), 202, 2017.
Rettig SJ, Trotter J. “Crystal and molecular structure of phenylboronic acid, C6H5B(OH)2”. Canadian Journal of Chemistry, 55(17), 3071-3075, 1977.
Cyran´ski MK, Jezierska A, Klimentowska P, Panek JJ, Sporzyns´ki AA. “Impact of intermolecular hydrogen bond on structural properties of phenylboronic acid: quantum chemical and X‐ray study”. Journal of Physical Organic Chemistry, 21(6), 472-482, 2008.
Faniran JN, Shurvell HF. “Infrared spectra of phenylboronic acid (normal and deuterated) and diphenyl phenylboronate”. Canadian Journal of Chemistry, 46(12), 2089-2095, 1968.
Wu YM, Dong CC, Liu S, Zhu HJ, Wu YZ. “3-Fluorophenylboronic acid”. Acta Crystallographica Section E, 62(10), 4236-4237, 2006.
Shimpi MR, SeethaLekshmi N, Pedireddi VR. “Supramolecular architecture in some 4-halophenylboronic acids”. Crystal Growth& Design, 7(10), 1958-1963, 2007.
Rodriguez-Cuamatzi P, Tlahuext H, Höpfl H. “2,4-Difluorophenylboronic acid”. Acta Crystallographica Section E, 65(1), 44-45, 2009.
Zarychta B, Zaleski J, Sporzynski A, Dabrowski M, Serwatowski J. “3-Formylphenylboronic acid”. Acta Crystallographica Section C, 60(5), 344-345, 2004.
Vega A, Zarate N, Tlahuext H, Höpfl H. “3-aminophenylboronic acid monohydrate”. Acta Crystallographica Section E, 66(6), 1260-1267, 2010.
Kurt M, Sertbakan TR, Özduran M. “An experimental and theoretical study of molecular structure and vibrational spectra of 3-and 4-pyridineboronic acid molecules by density functional theory calculations”. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 70(3), 664-673, 2008.
Rani U, Karabacak M, Tanrıverdi O, Kurt M, Sundaraganesan N. “The spectroscopic (FTIR, FT-Raman, NMR and UV), first-order hyperpolarizability and HOMO-LUMO analysis of methylboronic acid”. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 92(15), 67-77, 2012.
Karabacak M, Sinha L, Prasad O, Asiri AM, Cinar M. “An experimental and theoretical investigation of Acenaphthene-5-boronic acid: conformational study, NBO and NLO analysis, molecular structure and FT-IR, FT-Raman, NMR and UV spectra”. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 115, 753-766, 2013.
Sachan AK, Pathak SK, Sinha L, Prasad O, Karabacak M, Asiri AM. “A combined experimental and theoretical investigation of 2-Thienylboronic acid: Conformational search, molecular structure, NBO, NLO and FT-IR, FT-Raman, NMR and UV spectral analysis”. Journal of Molecular Structure, 1076, 639-650, 2014.
Kurt M. “DFT simulations and vibrational spectra of 4-chloro and 4-bromophenylboronic acid molecules”. Journal of Raman Spectroscopy, 40(1), 67-75, 2009.
Kurt M, Sertbakan TR, Özduran M, Karabacak M. “Infrared and Raman spectrum, molecular structure and theoretical calculation of 3,4-dichlorophenylboronic acid”. Journal of Molecular Structure, 92(1), 178-187, 2009.
Alver Ö. “DFT, FT-Raman, FT-IR, solution and solid state NMR studies of 2,4-dimethoxyphenylboronic acid”. Comptes Rendus Chimie, 14(5), 446-455, 2011.
Alver Ö, Parlak C. “DFT, FT-Raman, FT-IR, liquid and solid state NMR studies of 2,6-dimethoxyphenylboronic acid”. Vibrational Spectroscopy, 54(1), 1-9, 2010.
Karabacak M, Kose E, Atac A, Cipiloglu MA, Kurt M. “Molecular structure investigation and spectroscopic studies on 2,3-difluorophenylboronic acid: A combined experimental and theoretical analysis”. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 97, 892-908, 2012.
Karabacak M, Kose E, Atac A, Sas EB, Asiri AM, Kurt M. “Experimental (FT-IR, FT-Raman, UV-Vis, 1H and 13C NMR) and computational (density functional theory) studies on 3-bromophenylboronic acid”. Journal of Molecular Structure, 1076, 358-372, 2014.
Karabacak M, Kose E, Atac A, Asiri AM, Kurt. “Monomeric and dimeric structures analysis and spectroscopic characterization of 3,5-difluorophenylboronic acid with experimental (FT-IR, FT-Raman, 1H and 13C NMR, UV) techniques and quantum chemical calculations”. Journal of Molecular Structure, 1058, 79-96, 2014.
Karabacak M, Kose E, Sas EB, Kurt M, Asiri AM, Atac A. “DFT calculations and experimental FT-IR, FT-Raman, NMR, UV-Vis spectral studies of 3-fluorophenylboronic acid”. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 136, 306-320, 2015.
Parlak C, Ramasami P, Tursun M, Rhyman L, Kaya MF, Atar N, Alver Ö, Şenyel M. “4-Mercaptophenylboronic acid: Conformation, FT-IR, Raman, OH stretching and theoretical studies”. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 144, 131-138, 2015.
Dikmen G, Alver Ö, Parlak C. “NMR determination of solvent dependent behavior and XRD structural properties of 4-carboxy phenylboronic acid: A DFT supported study”. Chemical Physics Letters, 698, 114-119, 2018.
Alver Ö, Kaya MF, Dikmen G. “Structural characterization, solvent effects on nuclear magnetic shielding tensors, experimental and theoretical DFT studies on the vibrational and NMR spectra of 3-(acrylamido)phenylboronic acid”. Journal of Molecular Structure, 1102, 285-294, 2015.
Sas EB, Kose E, Kurt M, Karabacak M. “FT-IR, FT-Raman, NMR and UV-Vis spectra and DFT calculations of 5-bromo-2-ethoxyphenylboronic acid (monomer and dimer structures)”. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 137, 1315-1333, 2015.
Kurt M, “An experimental and theoretical study of molecular structure and vibrational spectra of pentafluorophenylboronic acid molecule by density functional theory and ab initio Hartree Fock calculations”. Journal of Molecular Structure, 874(1), 159-169, 2008.
Frisch MJ, Trucks, GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenb DJ. Gaussian 09, Revision A.1, Gaussian, Inc., Wallingford, USA, 2008.
Dennington RD, Keith TA, Millam JM. GaussViev 5.0.8, Gaussian, Inc., Wallingford, USA, 2008.
Miertus S, Scrocco E, Tomasi T. “Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects”. Chemical Physics, 55(1), 117-129, 1981.
Balcı K, Akyüz S. “A vibrational spectroscopic investigation on benzocaine molecule”. Vibrational Spectroscopy, 48(2), 215-218, 2008.
Baker J, Jarzecki AA, Pulay P. “Direct scaling of primitive valence force constants: an alternative approach to scaled quantum mechanical force fields”. The Journal of Physical Chemistry A, 102(8), 1412-1424, 1998.
Rauhut G, Pulay P. “Transferable scaling factors for density functional derived vibrational force fields”. The Journal of Physical Chemistry, 99(10), 3093-3100, 1995.
Parlak C. “Theoretical and experimental vibrational spectroscopic study of 4-(1-Pyrrolidinyl) piperidine”. Journal of Molecular Structure, 966(1), 1-7, 2010.
Tursun M, Parlak C. “Conformation stability, halogen and solvent effects on CO stretching of 4-chloro-3-halogenobenzaldehydes”. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 141, 58-63, 2015.
Sharma RK. Stereochemistry. New Delhi, India, Discovery Publishing House, 2007.