Bazı Hidrazo-oksim Türevlerinin Sentezi ve Karakterizasyonu

Yıl 2021, Cilt: 47 Sayı: 1, 69 - 79, 30.04.2021

Yasemin İpek İbrahim Karataş Önder Alıcı

https://doi.org/10.35238/sufefd.854364

Öz

Bu çalışmada, önce bifenil ile asetilklorürün reaksiyonundan 4-asetilbifenil (I), sonra, bunun izobütilnitrit ve (CH3)3SiCl varlığında 4-izonitrozoasetildifenil (keto oksim) (II) sentezlenmiştir. Daha sonra bu 4-izonitrozoasetildifenil’in hidrazinhidrat ile reaksiyonundan 2-(bifenil)-2-hidrazonoasetaldehit oksim (III) sentezlenmiştir. Elde edilen bu hidrazo oksimin asetaldehit, benzaldehit ve o-hidroksibenzaldehit ile olan kondenzasyon reaksiyonları incelenmiştir (IV, V, VI). Reaksiyon sonucu, bileşiklerin oksim grubu ile hidrazon grupları arasında halka kapanması (1,2,4-triazin yapısı) olup olmadığı araştırılmıştır. Bu bileşiklerin, Elementel Analiz, FT-IR ve 1H-NMR spektroskopi teknikleri verilerinden, halka kapanması reaksiyonu vermediği anlaşılmıştır. Ayrıca III, V ve VI nolu bileşiklerin Cu(II) ve Co(II) ile verdiği kompleksleri incelenmiştir. Bu bileşiklerin metal iyonu ile etkileşerek kompleks oluşturması da halkalaşma reaksiyonu (1,2,4-triazin yapısı) vermesine yol açmamıştır.

Anahtar Kelimeler

İzonitrozo oksim (keto oksim), Hidrazo oksim, Metal Kompleks

The Synthesis of Some Hydrazo Oximes Derivatives and Their Characterization

Öz

In this study, 4-acetylbiphenyl (I) was synthesized from the reaction of biphenyl and acetyl chloride, then 4-isonitrozoacetyldiphenyl (keto oxime) (II) in the presence of its isobutyl nitrite derivative and (CH3)3SiCl. Later, 2-(biphenyl)-2-hydrazonoacetaldehyde oxime (III) was synthesized from the reaction of 4-isonitrozoacetyldiphenyl with hydrazine hydrate. Compounds (IV, V, VI) were synthesized by the condensation reaction of the prepared hydrazo oxime with acetaldehyde, benzaldehyde and o-hydroxybenzaldehyde. As a result of the reaction, it has been investigated whether the compounds undergo a cyclization reaction (1,2,4-triazine structure) between the oxime group and the hydrazone groups. It is understood that these compounds could not give a ring closure reaction from data of elemental analysis, FT-IR and 1H-NMR spectroscopy techniques. In addition, the complexes of compounds III, V and VI with Cu (II) or Co (II) were investigated. The complex formation of these compounds by interacting with the metal ion could not cause a cyclization reaction.

Anahtar Kelimeler

Isonitrozo oxime (keto oxime), Hydrazo oxime, Metal Complex

Kaynakça

• Akiba K and Freisher H (1982). The Role of the Solvent in Equilibrum and Kinetic Aspect of Metal Chelate Extractions. Analytica Chimica Acta 136: 329-337.
• Alici Ö and Karatas İ (2012). Synthesis of New Substituted 1, 2, 4‐Triazines from Isonitrosoketones and Terephthalaldehydedihydrazone. Journal of Heterocyclic Chemistry 49(3): 576-579.
• Burakevich JV, Lore AM and Volpp GP (1971). Phenylglyoxime. Separation, characterization, and structure of three isomers. The Journal of Organic Chemistry 36(1): 1-4.
• Chakravorty A (1974). Structural chemistry of transition metal complexes of oximes. Coordination Chemistry Reviews 13(1): 1-46.
• Clayden J, Greeves N and Warren S (2001). P. Wothers in Organic Chemistry. Oxford University Press.
• Constantinos JM, Stamatatos TC and Perlepes SP (2005). The coordination chemistry of pyridyl oximes. Polyhedron 25: 134–194.
• Coogan NT, Chimes MA, Raftery J, Mocilac P and Denecke MA (2015). Regioselective Synthesis of V-Shaped Bistriazinyl-phenanthrolines. The Journal of Organic Chemistry 80(17): 8684-8693.
• El-Sherif AA (2009). Synthesis, Spectroscopic Characterization and Biological Activity on Newly Synthesized Copper(II) and Nickel(II) Complexes İncorporating Bidentate Oxygen–Nitrogen Hydrazone Ligands. Inorganica Chimica Acta 362(14):.4991-5000.
• Gök Y and Bekaroğlu Ö (1981). The Synthesis and Complex Formatirn of Stererisomers of some new α-Dioximes. Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry 11(7): 621-631.
• Hüseyinzade A ve İrez G (1990). Bazı Aminoglioksimlerin Ka Sabitlerinin Tayini. S.Ü. Fen Edebiyat Fakültesi Fen Dergisi 10: 16.
• Kara A (1995). Çeşitli oksimlerin sentezi ve özelliklerinin incelenmesi. Yüksek Lisans Tezi, U.Ü. Fen Bilimleri Enstitüsü, Bursa.
• Karaböcek S, Bilgin A, Gök Y (1997). A New Vicinal-Dioxime and its Mono and Trinüclear Complexes Containing the Monoaza Tetraoxa Macrocyclic Moity. Transition Met. Chem. 22: 420-424.
• Karataş I and Uçan HI (1998). The synthesis of biphenylglyoxime and bis (phenylglyoxime) and their complexes with Cu (II), Ni (II) and Co (II). Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry 28(3): 383-391.
• Keeney ME and Asare KO (1984). Transition Metal Hydroxyoxime Complexes, Coordination Chemistry Reviews 59: 141-201.
• Koçak N, Sahin M and Ucan HI (2012). The synthesis of two new isonitrosoacetophenone derivatives and investigation of their Ni (II), Co (II), Cu (II), and Zr (IV) complexes. Russian Journal of Inorganic Chemistry 57 (9): 1227-1231.
• Kurtoğlu M, Purtas F and Toroğlu S (2008). A new vic-dioxime Ligand Containing Two Azo Substituents and its Mononuclear Nickel(II), Cobalt(II), and Copper(II) Complexes; Synthesis, Characterization, Spectroscopic and Biological Studies. Transition Met. Chem. 33: 705–710.
• Li H, Rao PNP, Habeeb AG and Knaus EE (2002). Design, Syntheses, and Evaluation of 2,3-Diphenylcycloprop-2-en-1-ones and Oxime Derivatives as Potential Cyclooxygenase-2 (COX-2) Inhibitors with Analgesic-Antiinflammatory Activity. Drug Development Research 57: 6-17.
• Milios CJ, Stamatatos TC and Perlepes SP (2006). The coordination chemistry of pyridyl oximes. Polyhedron 25: 134–194.
• Mohammed AH and Nagendrappa G (2003). A remarkably simple α-oximation of ketones to 1, 2-dione monooximes using the chlorotrimethylsilane–isoamyl nitrite combination. Tetrahedron Letters 44 (13): 2753-2755.
• Ohshima T, Komyoji T, Mitani S, Matsuo N. and Nakajima T (2004). Development of a Novel Fungicide: Cyazofamid. Journal of Pesticide Science 29: 147-152.
• Patai S (1970). Chemistry of the Carbon-Nitrogen Double Bond. Interscience Publisher, London.
• Purtaş F (2006). Suda çözünebilir yeni vic-dioksim ligandı ve bazı metal Komplekslerinin Sentezi. Yüksek Lisans Tezi, K.S.Ü. Fen Bilimleri Enstitüsü, Kahramanmaraş, s.3-4.
• Sharghi,H., Jokar, M., Doroodmand, M.M. and Khalifeh, R., 2010, Catalytic Friedel–Crafts Acylation and Benzoylation of Aromatic Compounds Using Activated Hematite as a Novel Heterogeneous Catalyst. Synth. Catal. 352: 3031-3044.
• Silverstein RM, Bassler GC and Morrill TC (1974). Spectrometric identification of organic compounds. 159-229, John Wiley.
• Smith PAS (1966). The Chemistry of Open-chain Organic Nitrogen Compounds: Derivatives of oxidized nitrogen: hydrazines to nitrates. 2: 28-68, New York.
• Yu H, Cheng J, Cui Y, Shang H, Ding Z and Jin H (2004). Application of Toxicity Identification Evaluation Procedures on Wastewatersand Sludge from a Municipal Sewage Treatment Works with Industrial Inputs. Ecotoxicology and Environmental Safety 57(3): 426-430