6,6′-{OKSİBİS[(p-FENİLEN)İMİNOMETİL]}BİS-(2-tert-BÜTİLFENOL) SCHIFF BAZININ MİKRODALGA IŞINLAMA YOLUYLA SENTEZİ, YAPI KARAKTERİZASYONU, TAUTOMERİK ve SOLVATOKROMİK ÖZELLİKLERİNİN DENEYSEL VE TEORİK OLARAK İNCELENMESİ

Yıl 2016, Cilt: 17 Sayı: 1, 79 - 95, 25.04.2016

Emel Ermiş

https://doi.org/10.18038/btda.70064

Cited By: 1

Öz

3-tert-Bütilsalisilaldehitin (1) 4,4'-diaminodifenil eter (2) ile kondenzasyon reaksiyonundan yararlanılarak 6,6′-{oksibis[(p-fenilen)iminometil]}bis-(2-tert-bütilfenol) (3) sentezi, mikrodalga-ışınlama yöntemi kullanılarak gerçekleştirilmiştir. Bileşik (3)’ün kimyasal yapısı element analizi, FTIR, ¹H NMR, ¹³C NMR ve UV-görünür bölge spektroskopi teknikleri kullanılarak karakterize edilmiştir. Bileşiğin farklı organik çözücülerde fenol-imin (O−H^….N) ve keto-amin (O^….H−N) tautomerik dengeleri ve solvatokromik özelliği UV-görünür bölge spektrofotometrik yöntem kullanılarak incelenmiştir. Ayrıca, bileşiğin geometrisi, farklı çözücülerdeki fenol-imin/fenol-imin ve keto-amin/keto-amin tautomerlerinin enerjisi, molekül içi O−H^….N ve O^….H−N hidrojen bağ uzunlukları, UV-görünür bölge uyarılma enerjisi ve ossilatör kuvveti DFT (B3LYP)/6-311+G(d,p) hesaplama yöntemi kullanılarak hesaplanmıştır ve hesaplamalar deneysel sonuçlar ile karşılaştırılmıştır. Bileşik (3)’ün seçilen organik çözücülerde fenol-imin/fenol-imin tautomer formunu tercih ettiği ve solvatokromik özellik sergilediği deneysel ve teorik olarak belirlenmiştir.

Anahtar Kelimeler

3-ter-Bütilsalisilaldehit, 4, 4'-Diaminodifenil eter; Mikrodalga-ışınlama yöntemi; Tautomerik denge; Solvatokromizm; DFT.

MICROWAVE ASSISTED SYNTHESIS and CHARACTERIZATION of 6,6 '- {OXYBIS [(pPHENYLENE)IMINOMETHYL]}BIS-(2-tert-BUTYL PHENOL), EXPERIMENTAL and THEORETICAL INVESTIGATION of ITS TAUTOMERIC AND SOLVATOCHROMIC PROPERTIES

Öz

The synthesis of 6,6'-{oxybis[(p-phenylene)iminomethyl]}bis-(2-tert-butylphenol) (3) was performed from the condensation reaction of 3-tert-butylsalicylaldehyde (1) with 4,4'-diaminodiphenyl ether (2) using the microwave-irradiation method. The structure of compound (3) was characterized by elemental analysis, FTIR, 1H NMR, 13C NMR and UV-visible spectroscopic techniques. The tautomeric equilibria (for phenol-imine O−H....N and keto-amine O....H−N tautomers) and the behavior of solvatochromic in different organic solvents were studied using UV visible spectrophotometric method. Furthermore, the structure of compound, the energies of phenol-imine/ phenol-imine and keto-amine/keto-amine tautomers in different organic
solvents, intramolecular O−H....N and O....H−N hydrogen bond length, UV-visible excitation energy and oscillator strength were
calculated with the theoretical DFT method (B3LYP)/6-311+G(d,p) and calculations were compared with experimental results.
It was determined theoretically and experimentally that the compound (3) exhibits the phenol-imine/phenol-imine tautomeric structure and solvatochromic feature in selected organic solvents.

Anahtar Kelimeler

4,4'-Diaminodiphenyl ether, Microwave-irradiation method, Tautomeric equilibrium, Solvatochromism, DFT

Kaynakça

• Layer RW. The chemistry of imines. Chemical Reviews 1963; 63: 489–510.
• Ingold CK. Structure and Mechanism in Organic Chemistry, 2nd ed. Cornell Univ, Ithaca,1969.
• Barton D, Ollis WD. Comprehensive Organic Chemistry. vol 2. Pergamon, Oxford, 1979.
• Lozier RA, Bogomolni W, Stoekenius J. Bacteriorhodopsin: a light-driven proton pump in halobacterium halobium. Biophysical Journal 1975; 15: 955-962.
• Walsh CT, Orme-Johnson WH. Nickel enzymes. Biochemistry 1987; 26(16): 4901–4906.
• Costamagna J, Vargas J, Latorre R, Alvarado A, Mena G. Coordination compounds of copper, nickel and iron with Schiff bases derived from hydroxynaphthaldehydes and salicylaldehydes. Coordination Chemistry Reviews 1992; 119: 67-88.
• Ünver H, Yıldız M, Dülger B, Özgen Ö, Kendi E, Durlu TN. Spectroscopic studies, antimicrobial activities and crystal structures of N-(2-hydroxy-3-methoxybenzalidene)1-aminonaphthalene. Journal of Molecular Structure 2005; 737: 159–164.
• Omar MM, Mohemed GG, Ibrahim AA. Spectroscopic characterization of metal complexes of novel Schiff base. Synthesis, thermal and biological activity studies. Spectrochimica Acta A 2009; 73: 358–369. [9] Abdallah SM, Mohamed GG, Zayed MA, Abou El-Ela MS. Spectroscopic study of molecular structures of novel Schiff base derived from o-phthaldehyde and 2-aminophenol and its coordination compounds together with their biological activity. Spectrochimica Acta A 2009; 73(5): 833–840.
• Taggi AE, Hafez AM, Wack H, Young B, Ferraris D, Lectka T. The development of the first catalyzed reaction of ketenes and imines:  Catalytic, asymmetric synthesis of β-Lactams. Journal of the American Chemical Society 2002; 124: 6626–6635.
• Nejati K, Rezvani Z, Massoumi B. Syntheses and investigation of thermal properties of copper complexes with azo-containing Schiff-base dyes. Dyes Pigments 2007; 75: 653–657.
• Ispir, E. (2009). The synthesis, characterization, electrochemical character, catalytic and antimicrobial activity of novel, azo-containing Schiff bases and their metal complexes. Dyes Pigments 82, 13–19.
• Garnovskii AD, Nivorozhkin AL, Minkin VI. (1993). Ligand environment and the structure of schiff base adducts and tetracoordinated metal-chelates. Coordination Chemistry Reviews 1993; 126(1-2): 1-69. [14] Ogawa K, Harada J. Aggregation controlled proton tautomerization in salicylideneanilines. Journal of Molecular Structure 2003; 647: 211–216.
• Yıldız M, Ünver H, Dülger B, Erdener D, Ocak N, Erdönmez A, Durlu TN. Spectroscopic study, antimicrobial activity and crystal structures of N-(2-hydroxy-5-nitrobenzalidene)4-aminomorpholine and N-(2-hydroxy-1-naphthylidene)4-aminomorpholine. Journal of Molecular Structure 2005; 738: 253–260.
• Temel E, Albayrak Ç, Büyükgüngör O, Odabaşoğlu M. Zwitterionic (E)-2-hydr­oxy-6-[(o- tolyl­iminio)meth­yl]phenolate 0.07-hydrate. Acta Crystallographica Section E 2006; 62: o4484-o4486. [17] Özek A, Albayrak Ç, Odabaşoğlu M, Büyükgüngör O. Three (E)-2-[(bromo­phen­yl)imino­meth­yl]- 4-methoxy­phenols. Acta Crystallographica Section C 2007; C63: o177-o180.
• Basu Baul TS, Das P, Chandra AK, Mitra S, Pyke S. The synthesis, characterization and structures of some 4-[((E)-1-{2-hydroxy-5-[(E)-2-(aryl)-1-diazenyl]phenyl} methylidene)amino]benzoic acid. Dyes and Pigments 2009; 82: 379–386.
• Minkin VI, Tsukanov AV, Dubonosov AD, Bren VA. Tautomeric Schiff bases: Iono-, solvato-, thermo- and photochromism. Journal of Molecular Structure 2011; 998: 179–191.
• Khanmohammadi H, Abdollahi A. New diaminomaleonitrile-based azo-azomethine dyes; synthesis, characterization and spectral properties. Dyes and Pigments 2012; 94: 163–168.
• Moustakali-Mavridis I, Hadjoudis E, Mavridis A. Crystal and molecular structure of some thermochromic Schiff bases. Acta Crystallographica Section B 1978; 34: 3709-3715.
• Hadjoudis E, Vitterakisp M, Mavridis IM. Photochromism and thermochromism of schiff bases in the solid state and in rigid glasses. Tetrahedron 1987; 43: 1345-1360.
• Nicoud JF, Twieg RJ. Design and Synthesis of Organic Molecular Compounds for Efficient Second-Harmonic Generation. In: Chemla DS, Zyss J, editors. (1987). Nonlinear Optical Properties of Organic Molecules and Crystals. New York, Academic Press, vol. 1, 1987. (Chapter II-3), pp. 227-291. [24] Dürr H, Bouas-Laurent H. Photochromism: Molecules and Systems. 1st Ed. Elsevier, Amsterdam, 1990. [25] Alemi AA, Shaabani, B. Synthesis and characterization of a Schiff base of p-tert-butylcalıx[4]arene and its complex with copper(II). Acta Chimica Slovenica Journal 2000; 47: 363–369.
• Jalali-Heravi M, Khandar AA, Sheikshoaie I. A theoretical investigation of the structure, electronic properties and second-order nonlinearity of some azo Schiff base ligands and their monoanions Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 1999; 55: 2537–2544.
• Karakaş A, Elmalı A, Ünver H, Svoboda I. Nonlinear optical properties of some derivatives of salicylaldimine-based ligands. Journal of Molecular Structure 2004; 702: 103–110.
• Sıdır YG, Sıdır I, Berber H, Türkoğlu G. Solvatochromic behavior and electronic structure of some symmetric 2-aminophenol Schiff base derivatives. Journal of Molecular Liquids 2014; 199: 57–66.
• Sıdır YG, Sıdır I, Berber H, Türkoğlu G. Solvatochromism and electronic structure of some symmetric Schiff base derivatives. Journal of Molecular Liquids 2015; 204: 33–38.
• Sıdır İ, Sıdır YG, Berber H, Demiray F. Emerging ground and excited state dipolemoments and external electric field effect on electronic structure. A solvatochromism and theoretical study on 2- ((phenylimino)methyl)phenol derivatives. Journal of Molecular Liquids 2015; 206: 56–67.
• Sprung MM. A summary of the reaction of aldehydes with amines. Chemical Reviews 1940; 26: 297–334.
• Gedye R, Smith F, Westaway K, Ali H, Baldisera L, Laberge L, Roussel J. The use of microwave ovens for rapid organic synthesis. Tetrahedron Letters 1986; 27(3): 279-282.
• Giguere RJ, Bray, TL, Duncan SM, Majetich G. (1986). Application of commercial microwave ovens to organic synthesis. Tetrahedron Letters 1986; 27(41): 4945-4598.
• Wade LG. Organic Chemistry. New York, Wiley, 1999.
• Aghayan MM, Ghassemzadeh M, Hoseini M, Bolourtchian M. Microwave assisted synthesis of the tetradentate Schiff bases under solvent free-and catalyst free condition. Synthetic Communications 2003; 33: 521-525.
• Lamiri M, Bougrin K, Daou B, Souflaoui M, Nicolas E, Giralt E. Microwaves assited solvent free regiospecific synthesis of 5-alkylidene and 5-arylidene hydantoins. Synthetic Communications 2006; 36: 1575–1584.
• Aghera VK, Ghumara RY, Parsania PH. Microwave assisted and classical synthesis of symmetric double Schiff bases of 1,1-bis(4-mino3-methylphenyl)cyclohexane and their antimcrobial asay. Journal of Scientific Industrial Research 2015; 74: 43-47.
• Loupy A, Petit A, Hamelin I, Texier-Boullet F, Jacquault P, Mathe D. New solvent free organic synthesis using focused microwaves. Synthesis 1998; 1213–1234.
• Varma RS. Solvent free organic syntheses using supported reagent and microwave irradiation. Green Chemistry 1999; 1: 43–55.
• Lidström P, Tiemey J, Wathey B, Westman J. Microwave assisted organic synthesis-a review. Tetrahedron 2001; 57: 9225-9283.
• Ayoubi SA-E, Texier-Boullet F, Hamelin J. Minute synthesis of electrophilic alkenes under microwave irridation. Synthesis 1994; 258-260.
• Bose DS, Jayalakshmi BJ. Reagents for organic synthesis: Use of organostannyl oxides as catalytic neutral agents in the preparation of nitriles from primary amides under microwave irradiation. Journal of Organic Chemistry 1999; 64 (5): 1713-1714.
• Schwartz JB. Optimization techniques in pharmaceutical formulation and processing. In: Banker, editors. Modern Pharmaceutics. 4th ed. Marcel Dekker, New York, 2000. pp. 803-828.
• Somani R, Pawar S, Nikam S, Shirodkar P, Kadam V. Microwave assisted synthesis and antimicrobial activity of some Schiff’s bases. International Journal of ChemTech Research 2010; 2(2): 860-864.
• Yang H, Sun W, Li Z, Wang L. Solvent-free syntheses of salicylaldimines assisted by microwave irradiation. Synthetic Communications 2002; 32(15): 2395–2402.
• Yang Z, Sun P. Compare of three ways of synthesis of simple Schiff base. Molbank 2006; M514: 1-3. [49] Zhang Y, Guo ZJ, You XZ. Hydrolysis Theory for Cisplatin and Its Analogues Based on Density Functional Studies. Journal of American Chemical Society 2001; 123: 9378–9387.
• Tanak H, Ağar A, Yavuz M. Experimental and quantum chemical calculational studies on 2-[(4- Fluorophenylimino)methyl]-3,5-dimethoxyphenol. Journal of Molecular Modeling 2010; 16: 577-587. [51] Albayrak Ç, Kosar B, Odabaşoğlu M, Büyükgüngör O. Molecular and Computational Structure Characterizations of (E)-2-Ethoxy-6-[(4-fluorophenylimino)methyl]phenol. Journal of the Iranian Chemical Society 2011; 8(3): 674-686.
• Khalaji AD, Mighani H, Gotoh K, Ishida H. Synthesis, Characterization, Structure, Ab Initio and DFT Calculations of 2-Amino-N-(3-phenylprop-2-enylidene)aniline. Journal of Chemical Crystallography 2011; 41: 1154–1157.
• Annaraj B, Pan S, Neelakantan MA, Chattaraj PK. DFT study on the ground state and excited state intramolecular proton transfer of propargyl arm containing Schiff bases in solution and gas phases. Computational and Theoretical Chemistry 2014; 1028: 19-26.
• Demircioğlu Z, Albayrak Ç, Büyükgüngör O. Theoretical and experimental investigation of (E)-2- ([3,4-dimethylphenyl)imino]methyl)-3-methoxyphenol:
• properties, NLO, NBO and NPA analysis. Journal of Molecular Structure 2014; 1065-1066: 210–222. Enol–keto tautomerism,
• spectroscopic [55] Demircioğlu Z, Albayrak Ç, Büyükgüngör O. Experimental (X-ray, FT-IR and UV–vis spectra) and
• Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014; 128: 748–758. (DFT study) of
• (E)-3-methoxy-2-[(p-tolylimino)methyl]phenol. [56] Eshtiagh-Hosseini H, Beyramabadi SA, Morsali A, Mirzaei M, Chegini H, Elahi M, Naseri MA. Synthesis, characterization and intramolecular proton transfer of 3,30-dihydroxy-4,40-[5-methyl-1,3- phenylenebis(nitrilomethylidyne)]-bis-phenol. Journal of Molecular Structure 2014; 1072: 187–194.
• Percino MJ, Cerón M, Castro ME, Ramírez R, Soriano G, Chapela VM. (E)-2-[(2- hydroxybenzylidene)amino]phenylarsonic acid Schiff base: Synthesis, characterization and theoretical studies. Journal of Molecular Structure 2015; 1081: 193–200.
• Yıldız M, Karpuz Ö, Zeyrek CT, Boyacıoğlu B, Dal H, Demir N, Yıldırım N, Ünver H. Synthesis, biological activity, DNA binding and anion sensors, molecular structure and quantum chemical studies of a novel bidentate Schiff base derived from 3,5-bis(triflouromethyl)aniline and salicylaldehyde. Journal of Molecular Structure 2015; 1094: 148-160.
• Oleinik II, Oleinik IV, Ivanchev SS, Tolstikov GA. Design of Postmetallocene Schiff Base-Like Catalytic Systems for Polymerization of Olefins: XII. Synthesis of Tetradentate Bis-salicylaldehyde Imine Ligands. Russian Journal of Organic Chemistry 2009; 45(4): 528–535.
• Hayvalı Z, Hayvalı M, Kılıç Z, Hökelek T, Weber E. New Benzo-15-Crown-5 Ethers Featuring Salicylic Schiff Base Substitutions–Synthesis, Complexes and Structural Study. Journal of Inclusion Phenomena and Macrocyclic Chemistry 2003; 45: 285–294.
• CS ChemOffice Pro for Microsoft Windows.
• Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA ve ark. Gaussian 09, Revision B.01. 2009.
• Corsaro A, Chiacchio U, Pistara V, Romeo G. Microwave-assisted chemistry of carbohydrates. Current Organic Chemistry 2004; 8(6): 511-538.
• Bilge S, Kılıç Z, Hayvalı Z, Hökelek T, Safran S. Intramolecular hydrogen bonding and tautomerism in Schiff bases: Part VI. Syntheses and structural investigation of salicylaldimine and naphthaldimine derivatives. Journal of Chemical Sciences 2009; 121 (6): 989–1001.
• https://www.organicdivision.org/orig/organic_solvents.html.
• Alizadeh K, Amraie A. Electronic absorption spectroscopic behavior and acidity constants of some new dinitrophenylhydrazone derivatives. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2015; 147: 67–72.
• Zakerhamidi MS, Nejati K, Alidousti S, Saati M. The interactional behaviors and photo-physical properties of azo-salicylaldehyde ligands in solvents media. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2015; 150: 696–703.