Publication: Etil 7-oksokumarin-3-karboksilat türevi bazı ftalosiyaninlerin sentezi ve karakterizasyonu
Abstract
ETİL 7-OKSOKUMARİN-3-KARBOKSİLAT TÜREVİ BAZI FTALOSİYANİNLERİN SENTEZİ VE KARAKTERİZASYONU Kumarinler (2H-chromen-2-ones) yapısında heteroatom olarak oksijen içeren ve bitkilerde doğal olarak oluşan heterohalkalı bileşiklerdir. Kumarin birimi içeren pek çok bileşik; mantarlara karşı (antifungal), pıhtılaşmayı önleyici (antikoagülant), damar genişletici (vazodilatör), fotoduyarlaştırıcı (fotosensizer), sedatif, antimikrobiyal ve anti-HIV gibi pek çok biyolojik aktiviteye sahiptirler. Biyolojik aktivitelerinin yanısıra, kumarinler besin ve kozmetik maddelerinin üretiminde de katkı maddesi olarak kullanılmaktadır. 7-Hidroksikumarin türevleri floresans özelliklerinden dolayı; lazer ve optik aydınlatma uygulamalarında da kullanılabilmektedir. Diğer yandan, konjuge 18π-elektron sistemine sahip olan ftalosiyanin bileşikleri de, yararlı kullanım alanlarından dolayı, pek çok bilimsel çalışmada incelenmektedir. Ftalosiyaninlerle ilgili yapılan birçok bilimsel çalışmada, ftalosiyanin yapısına periferal olarak bağlı olan fonksiyonel sübstitüentlerin, makrohalkaya olan etkileri incelenmektedir. Bunun yanısıra, ftalosiyaninlerin son zamanlarda fotodinamik terapi, gaz sensör özellikleri ve solar hücre uygulama potansiyelleri de önemli araştırma alanları olmaktadır. Ftalosiyaninlerin yapısal özellikleri, makrohalkaya periferal olarak bağlanan değişik fonksiyonel sübstitüentlerin sayesinde değiştirilebilir olması, onların kumarinler gibi geniş uygulama alanına sahip bileşikler ile sübstitüe olduğu pek çok çalışma için esin kaynağı olmaktadır. Ftalosiyaninlere kumarin birimlerinin sübstitüe olması sonucu elde edilen yeni tip ftalosiyanin bileşiklerinin yapısal özelliklerinde önemli değişmelere neden olduğunu kanıtlayan pek çok çalışma sunulmuştur. Deneysel çalışmalarda, öncelikle 3-nitroftalonitril ve 4-nitroftalonitril bileşikleri sentezlenmiştir. Daha sonra, Knoevenagel reaksiyonuna göre sentezlenen Etil 7-hidroksikumarin-3-karboksilat bileşiği ile 3-nitroftalonitril ve 4-nitroftalonitril bileşiklerinin ayrı ayrı reaksiyonu sonucu, sırası ile Etil 7-(2,3-disiyanofenoksi)kumarin-3-karboksilat ve Etil 7-(3,4-disiyanofenoksi)kumarin-3-karboksilat bileşikleri sentezlenmiştir. Bu bileşiklerden de Zn, Co, Cu, Ni metalleri içeren ftalosiyanin kompleksleri sentezlenmiştir. Ayrıca, Etil 7-(3,4-disiyanofenoksi)kumarin-3-karboksilat bileşiğinden sentezlenen Zn metalli ftalosiyanin bileşiği asidik ortamda hidroliz edilerek, perifal kumarin birimlerinin 3 pozisyonlarında ester grupları karboksilik asit gruplarına dönüştürülmüştür. Daha sonra bu bileşiğin morfolin ile reaksiyonu sonucu, periferal kumarin birimlerinin 3 pozisyonunda amit grupları olan Zn metalli ftalosiyanin bileşiği sentezlenmiştir. Sentezlenen ftalosiyanin bileşikleri organik solventlerde yıkanarak saflaştırılmıştır. Yeni sentezlenen bileşiklerin karakterizasyonu UV-vis, FT-IR, 1H-NMR ve Kütle spektrumlarıyla aydınaltıldı.
SYNTHESIS AND CHARACTERIZATION OF PHTHALOCYANINES WITH FOUR ETHYL 7-OXOCOUMARIN-3-CARBOXYLATE SUBSTITUENTS Coumarins (2H-chromen-2-ones), belong to a very large class of oxygen heterocycles found in nature. Compounds containing a coumarin moiety display a broad spectrum of biological activities such as antifungal, anticoagulant, vasodilator, dermal, photosensitizing, sedative, antimicrobial, anti-inflammatory, anti-HIV activities. Moreover, coumarins are widely used as additives in food and cosmetics, dispersed fluorescent, laser dyes, optically brightening agents. Phthalocyanines (Pcs), nitrogen containing planar 18π–electron heterocyclic conjugated compounds, have been the subject of intense research. Emphasis in this area has recently switched to the exploration of practical usefulness of functionalized Pc molecules. Research is now focused on the investigation of their conductive, catalytic, photocatalytic and electrochromic properties when a simple functional unit (e.g., redox-active, photo-active, catalytic) is attached to the periphery of a phthalocyanine core. Pcs have found application as dyes and pigments. Also many other applications have appeared recently including photodynamic therapy, gas sensors and solar cell technology. Coumarins can also be used as intermediates for the synthesis of other useful molecules such as Pcs. Within the class of 7-hydroxycoumarins that typically display favorable fluorescence and lasing properties, the derivatives that bear an additional carboxylate substituents at the 3-position have several differentiating properties. The coumarins contain a lactone ring, which is involved in pharmaceutical activity. 7-Hydroxycoumarins allow the binding of this structure to a Pc via a phenoxy bond. This covalent binding should not affect significantly the biological activity of the coumarin moiety. The combined structure of the coumarin and Pc may be a potential candidate molecule in the application of photodynamic therapy. In view of the biological importance of both coumarins and Pcs, it is worthwhile to combine these two functional molecules into a single compound via synthetic methodology and to prepare and characterize their Co and ZnPc derivatives, which may also exhibit biological activities. In this study, we have been concerned with the synthesis and characterization of novel, soluble metallo phthalocyanines [MPc, M: Zn, Co, Cu and Ni] carrying ethyl 7-oxocoumarin-3-carboxylate substituents on the peryphery and examined their spectral data as well. In addition, the ethyl carboxylate functional group was reacted with morpholine after having reacted with thionyl chloride. The novel phthalocyanines were purified by washing with some organic solvents. Novel compounds were characterized by UV-Vis, FT-IR, 1H-NMR and Mass spectroscopy.
SYNTHESIS AND CHARACTERIZATION OF PHTHALOCYANINES WITH FOUR ETHYL 7-OXOCOUMARIN-3-CARBOXYLATE SUBSTITUENTS Coumarins (2H-chromen-2-ones), belong to a very large class of oxygen heterocycles found in nature. Compounds containing a coumarin moiety display a broad spectrum of biological activities such as antifungal, anticoagulant, vasodilator, dermal, photosensitizing, sedative, antimicrobial, anti-inflammatory, anti-HIV activities. Moreover, coumarins are widely used as additives in food and cosmetics, dispersed fluorescent, laser dyes, optically brightening agents. Phthalocyanines (Pcs), nitrogen containing planar 18π–electron heterocyclic conjugated compounds, have been the subject of intense research. Emphasis in this area has recently switched to the exploration of practical usefulness of functionalized Pc molecules. Research is now focused on the investigation of their conductive, catalytic, photocatalytic and electrochromic properties when a simple functional unit (e.g., redox-active, photo-active, catalytic) is attached to the periphery of a phthalocyanine core. Pcs have found application as dyes and pigments. Also many other applications have appeared recently including photodynamic therapy, gas sensors and solar cell technology. Coumarins can also be used as intermediates for the synthesis of other useful molecules such as Pcs. Within the class of 7-hydroxycoumarins that typically display favorable fluorescence and lasing properties, the derivatives that bear an additional carboxylate substituents at the 3-position have several differentiating properties. The coumarins contain a lactone ring, which is involved in pharmaceutical activity. 7-Hydroxycoumarins allow the binding of this structure to a Pc via a phenoxy bond. This covalent binding should not affect significantly the biological activity of the coumarin moiety. The combined structure of the coumarin and Pc may be a potential candidate molecule in the application of photodynamic therapy. In view of the biological importance of both coumarins and Pcs, it is worthwhile to combine these two functional molecules into a single compound via synthetic methodology and to prepare and characterize their Co and ZnPc derivatives, which may also exhibit biological activities. In this study, we have been concerned with the synthesis and characterization of novel, soluble metallo phthalocyanines [MPc, M: Zn, Co, Cu and Ni] carrying ethyl 7-oxocoumarin-3-carboxylate substituents on the peryphery and examined their spectral data as well. In addition, the ethyl carboxylate functional group was reacted with morpholine after having reacted with thionyl chloride. The novel phthalocyanines were purified by washing with some organic solvents. Novel compounds were characterized by UV-Vis, FT-IR, 1H-NMR and Mass spectroscopy.