Bazı oksim eter bileşiklerinin sentezi, yapısal, spektroskopik ve fizikokimyasal özelliklerinin deneysel ve kuramsal incelenmesi
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Dosyalar
Tarih
2019
Yazarlar
Dergi Başlığı
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Yayıncı
Bursa Teknik Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Bu çalışmada, asetofenon, bromoasetofenon ve 2-asetonaftalin moleküllerinin hidroksilamin hidroklorür ve kloropropan ile reaksiyonları sonucunda üç oksim eter bileşiği, 1-fenil-etanon-O-propil-oksim, 1-(4-bromo-fenil)-etanon-O-propil-oksim ve 1-naftalin-2-il-etanon O-propil-oksim sentezlenmiştir. Sentezlenen moleküllerin yapıları IR ve NMR spektroskopi teknikleri ile aydınlatılmıştır. Moleküllerin sentezinin gerçekleştiğinin en önemli kanıtı, keton moleküllerinde 1700 cm-1 civarında gözlenen karbonil gerilme titreşiminin oksim eter bileşiklerinde kaybolması ve yerine 1660-1600 cm-1 aralığında imin (C=N) bandının oluşmasıdır. Ayrıca, NMR spektrumlarında gözlenen oksim hidrojenlerinin oksim eter bileşiklerinin NMR spektrumlarında gözlenmemesi de moleküllerin oluştuğunu doğrulamaktadır. Sentezlenen ve yapıları önerilen moleküller, Gaussian 09 paket programı ve Yoğunluk Fonksiyonel Kuramı (YFK)/B3LYP kullanılarak modellenmiştir. Literatürde sentezlediğimiz üç molekülün yapısına uygun ve deneysel bağ uzunlukları bilinen 4-[2-5(-etilpridin-2-propil)etoksi]benzaldehit oksim molekülü seçilerek taban küme taraması yapılmıştır. En küçük taban küme, STO 3G ile başlayıp sırayla 3-21G, 6-31G, 6-31G(d,p), 6-31G++(d,p), 6-311G, 6-311G(d,p), 6-311G++(d,p) ve 6-311G++(2d,p) taban kümelerinde optimizasyonları yapılmıştır. Her bir taban küme için seçilmiş bağ uzunlukları tabloya geçirilerek deneysel bağ uzunluklarına en yakın sonucu veren taban küme, 6-311G++(d,p) olarak belirlenmiştir. Sonraki tüm kuramsal çalışmalarda bu taban küme kullanılmıştır. Her üç molekülün konformasyon analizi yapılıp enerji diyagramları çizilerek en kararlı molekül yapıları belirlenmiştir. Moleküllerin bağ uzunluğu, bağ açısı ve dihedral açıları gibi moleküler özellikleri belirlenmiş, spektroskopik (IR, NMR ve UV-Gör. Bölge) özellikleri kuramsal olarak incelenerek deneysel değerler ile karşılaştırılmıştır. Moleküllerin bazı fizikokimyasal özellikleri, atomik yükleri, HOMO-LUMO molekül orbitalleri ve enerjileri, kimyasal potansiyel, yumuşaklık, kimyasal sertlik ve elektrofilik indeks gibi kimyasal parametreleri, potansiyel enerji grafikleri ve termodinamik özellikleri, entalpi, ısı sığası ve entropi değerleri kuramsal olarak incelenmiştir. Deneysel olarak gözlenen ve kuramsal olarak hesaplanan tüm sonuçlar literatür ile uyumlu olup, literatüre kazandırılmıştır. Çıkan sonuçların, bu tür molekülleri çalışan araştırmacılara yol gösterici olacağı düşünülmektedir.
In this study, three oxime ether compounds, 1-phenyl-ethanone-O-propyl-oxime, 1- (4-bromo-phenyl)-ethanone-O -propyl-oxime and 1-naphthalen-2-yl-ethanone O-propyl-oxime have been synthesized from reacting of acetophenone, bromoacetophenone and 2-acetonaphthalene molecules with hydroxylamine hydrochloride and chloropropane. Structures of synthesized molecules have been revealable by IR and NMR spectroscopy techniques. The most important evidence the synthesis of molecules is the loss of carbonyl stretching vibration observed in ketone molecules around 1700 cm-1 in the oxime ether compounds and the formation of imine (C=N) band in the 1660-1600 cm-1 range. Furthermore, the oxime hydrogens observed in the NMR spectra confirm the formation of molecules observed in the NMR spectra of oxime ether compounds. Molecules synthesized and proposed molecular structures have been modeled by using Gaussian 09 package program and Density Functional Theory (DFT)/B3LYP method. The basis set screening has been performed by selecting 4- [2-5 (-ethyl-pyridine-2-propyl) ethoxy] benzaldehyde oxime molecule from literature which is suitable for the structure of the three molecules we synthesized and are available experimental bond lengths. The optimizations have been performed starting the smallest basis set 3-21G and then respectively 6-31G, 6-31G(d,p), 6-31G++(d,p), 6-311G, 6-311G(d,p), 6-311G++(d,p) and 6-311G++(2d,p) basis sets. The selected bond lengths are tabled, the basis set giving the closest results to the experimental values has been determined as 6-311++G(d,p). This basis set has been used in all subsequent theoretical studies. The most stable molecular structures were determined from conformation analysis of three molecules and drawn energy diagrams. The molecular properties such as bond length, bond angle and dihedral angles have been determined the spectroscopic properties such as IR, NMR and UV-Vis. have been examined as theoretically and compared with the experimental values. Some physicochemical properties of molecules, atomic charges, HOMO-LUMO molecule orbitals and their energies, chemical parameters such as chemical potential, softness, chemical hardness and electrophilic index, potential energy graphs and thermodynamic properties, enthalpy, heat capacity and entropy values were investigated as theoretically. All results observed experimentally and calculated theoretically are compatible with the literature and have been presented to the literature. The results are thought to be useful for researchers working on such molecules.
In this study, three oxime ether compounds, 1-phenyl-ethanone-O-propyl-oxime, 1- (4-bromo-phenyl)-ethanone-O -propyl-oxime and 1-naphthalen-2-yl-ethanone O-propyl-oxime have been synthesized from reacting of acetophenone, bromoacetophenone and 2-acetonaphthalene molecules with hydroxylamine hydrochloride and chloropropane. Structures of synthesized molecules have been revealable by IR and NMR spectroscopy techniques. The most important evidence the synthesis of molecules is the loss of carbonyl stretching vibration observed in ketone molecules around 1700 cm-1 in the oxime ether compounds and the formation of imine (C=N) band in the 1660-1600 cm-1 range. Furthermore, the oxime hydrogens observed in the NMR spectra confirm the formation of molecules observed in the NMR spectra of oxime ether compounds. Molecules synthesized and proposed molecular structures have been modeled by using Gaussian 09 package program and Density Functional Theory (DFT)/B3LYP method. The basis set screening has been performed by selecting 4- [2-5 (-ethyl-pyridine-2-propyl) ethoxy] benzaldehyde oxime molecule from literature which is suitable for the structure of the three molecules we synthesized and are available experimental bond lengths. The optimizations have been performed starting the smallest basis set 3-21G and then respectively 6-31G, 6-31G(d,p), 6-31G++(d,p), 6-311G, 6-311G(d,p), 6-311G++(d,p) and 6-311G++(2d,p) basis sets. The selected bond lengths are tabled, the basis set giving the closest results to the experimental values has been determined as 6-311++G(d,p). This basis set has been used in all subsequent theoretical studies. The most stable molecular structures were determined from conformation analysis of three molecules and drawn energy diagrams. The molecular properties such as bond length, bond angle and dihedral angles have been determined the spectroscopic properties such as IR, NMR and UV-Vis. have been examined as theoretically and compared with the experimental values. Some physicochemical properties of molecules, atomic charges, HOMO-LUMO molecule orbitals and their energies, chemical parameters such as chemical potential, softness, chemical hardness and electrophilic index, potential energy graphs and thermodynamic properties, enthalpy, heat capacity and entropy values were investigated as theoretically. All results observed experimentally and calculated theoretically are compatible with the literature and have been presented to the literature. The results are thought to be useful for researchers working on such molecules.
Açıklama
Anahtar Kelimeler
Kimya, Chemistry
