Publication: Bazı 4-Hidroksifenilasetikasit türevi ftalosiyanin metal komplekslerinin sentesi ve yapılarının spektroskopik yöntemlerle aydınlatılması
Abstract
BAZI 4-HİDROKSİFENİLASETİKASİT TÜREVİ FTALOSİYANİN METAL KOMPLEKSLERİNİN SENTEZİ VE YAPILARININ SPEKTROSKOPİK YÖNTEMLERLE AYDINLATILMASI Sentetik makrohalkalı bileşik olan ftalosiyaninler boya sanayiinde, kanser terapisi ve diğer medikal uygulamalarda, yarı iletkenlik ve nonlineer optik özellikleri gösterdiği için teknolojinin birçok alanında etkili kullanıma sahiptir. Kumarin ve türevleri yararlı farmakolojik aktivite gösteren doğal bileşiklerin önemli bir sınıfını oluştururlar. Antikanserojenik, antifungal, antikoagulan ve etkin fluoresan verme gibi birçok özellikleri vardır. Yapılan bu çalışmada, yeni 4-hidroksifenilasetik asit türevi metalsiz ftalosiyaninler ve ftalosiyanin metal kompleksleri ; kumarin içeren metalsiz ftalosiyanin ve ftalosiyanin metal kompleksleri sentezlenerek yapıları aydınlatıldı. İlk aşamada, p-(3,4-disiyanofenoksi)fenilasetik asit sentezlendi. Bu bileşiğin yüksek kaynama noktalı solventler içinde, çeşitli metal tuzları ile reaksiyonundan metalsiz ftalosiyanin ve ftalosiyanin metal kompleksleri sentezlendi. Karboksilik asit grubu içeren bu ftalosiyaninlerin tiyonil klorürle reaksiyonundan oluşan ftalosiyanin asit klorürlerin, THF içinde benzil amin ile tepkimesinden amid türevi ftalosiyaninler sentezlendi. Asit klorürlerin piridin içinde oktanol ile tepkimesinden ester türevi ftalosiyaninler sentezlendi. Bu ftalosiyanin türevleri çeşitli çözücülerle yıkanarak saflaştırıldı. p-(3,4-Disiyanofenoksi)fenilasetik asit kullanılarak Perkin Reaksiyonu ile 7-oktiloksi-3-[p-(3',4'-disiyanofenoksi)fenil]kumarin sentezlendi. Bu bileşiğin 2-dimetilaminoetanol içinde ısıtılmasıyla kumarin içeren metalsiz ftalosiyanin ve 7-oktiloksi-3-[p-(3',4'-disiyanofenoksi)fenil]kumarin'in 2-dimetilaminoetanol içinde Zn(AcO)2.2H2O ile reaksiyonundan kumarin içeren çinko metalli ftalosiyanin elde edildi. Kumarin içeren ftalosiyaninler kolon kromatografisi yöntemiyle saflaştırıldı. Sentezlenen bileşiklerin yapıları UV/ VIS, FT-IR, 1H-NMR ve 13C-NMR spektrumlarıyla aydınlatıldı. droksifenilasetik asit, Ftalosiyanin, Kumarin. Kimya Organik Kimya Mayıs, 2005 Meryem ÇAMUR
THE SYNTHESIS OF 4-HYDROXYPHENYLACETIC ACID DERIVATIVES OF SOME METALLOPHTHALOCYANINES AND CHARACTERIZATION OF THEIR STRUCTURES BY SPECTROSCOPIC METHODS Phthalocyanines are synthetic macrocyclic compounds which are used as dyestuff, photodynamic reagents for cancer therapy and for some other medical applications. Also phthalocyanines have a great technological potential in areas related to intrinsic semiconductors and nonlinear optics. Coumarin derivatives are an important class of natural compounds having pharmaceutical activities. These compounds have many effects such as anticarcinogenecity, antifungal, anticoagulant and dispersed fluorescent. In this study, the synthesis of novel 4-hydroxyphenylacetic acid derivatives of metal-free phthalocyanines and metallophthalocyanines were performed. Also metal-free phthalocyanines and metallophthalocyanines containing coumarin moieties were performed. The structures of these new compounds were determined. First, p-(3,4-dicyanophenoxy)phenylacetic acid was synthesized. Metal-free phthalocyanine and metallophthalocyanines were performed by reaction of p-(3,4-dicyanophenoxy)phenylacetic acid and several metal salts in solvents which have high boiling point. Acid chlorides were prepared by reaction of thionylchloride and phthalocyanines containing carboxylic acid groups. Phthalocyanines containing amid moieties were synthesized by reaction of benzylamine and acid chlorides in THF. Phthalocyanines containing esther moieties were synthesized by reaction of octanol and acid chlorides in pyridine. Phthalocyanin compounds were purified by extraction with several solvents. 7-Octiloxy-3-[p-(3',4'-dicyanophenoxy)phenyl]coumarin was synthesized by Perkin Reaction. Metal-free phthalocyanine containing coumarin moieties was performed by reaction of 7-octiloxy-3-[p-(3',4'-dicyanophenoxy)phenyl]coumarin in 2-dimethylaminoethanol. Zinc metallo phthalocyanine containing coumarin moieties was performed by reaction of 7-octiloxy-3-[p-(3',4'-dicyanophenoxy)- phenyl]coumarin and Zn(AcO)2.2H2O in 2-dimethylaminoethanol. The purification of phthalocyanines containing coumarin moieties were made by using silica gel column chromatography. The structures of this new compounds were determined based on the results of spectroscopic methods such as UV/ VIS, FT-IR, 1H-NMR and 13C-NMR . Hydroxyphenylacetic acid, Phthalocyanine, Coumarin. May, 2005 Meryem ÇAMUR
THE SYNTHESIS OF 4-HYDROXYPHENYLACETIC ACID DERIVATIVES OF SOME METALLOPHTHALOCYANINES AND CHARACTERIZATION OF THEIR STRUCTURES BY SPECTROSCOPIC METHODS Phthalocyanines are synthetic macrocyclic compounds which are used as dyestuff, photodynamic reagents for cancer therapy and for some other medical applications. Also phthalocyanines have a great technological potential in areas related to intrinsic semiconductors and nonlinear optics. Coumarin derivatives are an important class of natural compounds having pharmaceutical activities. These compounds have many effects such as anticarcinogenecity, antifungal, anticoagulant and dispersed fluorescent. In this study, the synthesis of novel 4-hydroxyphenylacetic acid derivatives of metal-free phthalocyanines and metallophthalocyanines were performed. Also metal-free phthalocyanines and metallophthalocyanines containing coumarin moieties were performed. The structures of these new compounds were determined. First, p-(3,4-dicyanophenoxy)phenylacetic acid was synthesized. Metal-free phthalocyanine and metallophthalocyanines were performed by reaction of p-(3,4-dicyanophenoxy)phenylacetic acid and several metal salts in solvents which have high boiling point. Acid chlorides were prepared by reaction of thionylchloride and phthalocyanines containing carboxylic acid groups. Phthalocyanines containing amid moieties were synthesized by reaction of benzylamine and acid chlorides in THF. Phthalocyanines containing esther moieties were synthesized by reaction of octanol and acid chlorides in pyridine. Phthalocyanin compounds were purified by extraction with several solvents. 7-Octiloxy-3-[p-(3',4'-dicyanophenoxy)phenyl]coumarin was synthesized by Perkin Reaction. Metal-free phthalocyanine containing coumarin moieties was performed by reaction of 7-octiloxy-3-[p-(3',4'-dicyanophenoxy)phenyl]coumarin in 2-dimethylaminoethanol. Zinc metallo phthalocyanine containing coumarin moieties was performed by reaction of 7-octiloxy-3-[p-(3',4'-dicyanophenoxy)- phenyl]coumarin and Zn(AcO)2.2H2O in 2-dimethylaminoethanol. The purification of phthalocyanines containing coumarin moieties were made by using silica gel column chromatography. The structures of this new compounds were determined based on the results of spectroscopic methods such as UV/ VIS, FT-IR, 1H-NMR and 13C-NMR . Hydroxyphenylacetic acid, Phthalocyanine, Coumarin. May, 2005 Meryem ÇAMUR