SUMMARYTHE SYNTHESIS OF 4-HYDROXYPHENYLACETIC ACIDDERIVATIVES OF SOME METALLOPHTHALOCYANINESAND CHARACTERIZATION OF THEIR STRUCTURES BYSPECTROSCOPIC METHODSPhthalocyanines are synthetic macrocyclic compounds which are used as dyestuff,photodynamic reagents for cancer therapy and for some other medical applications. Alsophthalocyanines have a great technological potential in areas related to intrinsicsemiconductors and nonlinear optics.Coumarin derivatives are an important class of natural compounds havingpharmaceutical 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-freephthalocyanines 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-freephthalocyanine and metallophthalocyanines were performed by reaction of p-(3,4-dicyanophenoxy)phenylacetic acid and several metal salts in solvents which have highboiling point. Acid chlorides were prepared by reaction of thionylchloride andphthalocyanines containing carboxylic acid groups. Phthalocyanines containing amidmoieties were synthesized by reaction of benzylamine and acid chlorides in THF.Phthalocyanines containing esther moieties were synthesized by reaction of octanol andacid chlorides in pyridine. Phthalocyanin compounds were purified by extraction withseveral solvents.7-Octiloxy-3-[p-(3?,4?-dicyanophenoxy)phenyl]coumarin was synthesized by PerkinReaction. Metal-free phthalocyanine containing coumarin moieties was performed byreaction of 7-octiloxy-3-[p-(3?,4?-dicyanophenoxy)phenyl]coumarin in 2-dimethylaminoethanol. Zinc metallo phthalocyanine containing coumarin moieties wasperformed by reaction of 7-octiloxy-3-[p-(3?,4?-dicyanophenoxy)phenyl]- coumarin andZn(AcO)2.2H2O in 2-dimethylaminoethanol. The purification of phthalocyanines containingcoumarin moieties were made by using silica gel column chromatography.The structures of this new compounds were determined based on the results ofspectroscopic methods such as UV/VIS, FT-IR, 1H-NMR and 13C-NMR .Keywords: 4-Hydroxyphenylacetic acid, Phthalocyanine, Coumarin.May, 2005 Meryem ÇAMUR.

ÖZETBAZI 4-HIDROKSIFENILASETIKASIT TÜREVIFTALOSIYANIN METAL KOMPLEKSLERININ SENTEZI VEYAPILARININ SPEKTROSKOPIK YÖNTEMLERLEAYDINLATILMASISentetik makrohalkali bilesik olan ftalosiyaninler boya sanayiinde, kanser terapisi vediger medikal uygulamalarda, yari iletkenlik ve nonlineer optik özellikleri gösterdigi içinteknolojinin birçok alaninda etkili kullanima sahiptir.Kumarin ve türevleri yararli farmakolojik aktivite gösteren dogal bilesiklerin önemlibir sinifini olustururlar. Antikanserojenik, antifungal, antikoagulan ve etkin fluoresan vermegibi birçok özellikleri vardir.Yapilan bu çalismada, yeni 4-hidroksifenilasetik asit türevi metalsiz ftalosiyaninler veftalosiyanin metal kompleksleri ; kumarin içeren metalsiz ftalosiyanin ve ftalosiyanin metalkompleksleri sentezlenerek yapilari aydinlatildi.Ilk asamada, p-(3,4-disiyanofenoksi)fenilasetik asit sentezlendi. Bu bilesigin yüksekkaynama noktali solventler içinde, çesitli metal tuzlari ile reaksiyonundan metalsizftalosiyanin ve ftalosiyanin metal kompleksleri sentezlendi. Karboksilik asit grubu içeren buftalosiyaninlerin tiyonil klorürle reaksiyonundan olusan ftalosiyanin asit klorürlerin, THFiçinde benzil amin ile tepkimesinden amid türevi ftalosiyaninler sentezlendi. Asit klorürlerinpiridin içinde oktanol ile tepkimesinden ester türevi ftalosiyaninler sentezlendi. Buftalosiyanin türevleri çesitli çözücülerle yikanarak saflastirildi.p-(3,4-Disiyanofenoksi)fenilasetik asit kullanilarak Perkin Reaksiyonu ile 7-oktiloksi-3-[p-(3',4'-disiyanofenoksi)fenil]kumarin sentezlendi. Bu bilesigin 2-dimetilaminoetanol içinde isitilmasiyla kumarin içeren metalsiz ftalosiyanin ve 7-oktiloksi-3-[p-(3',4'-disiyanofenoksi)fenil]kumarin'in 2-dimetilaminoetanol içinde Zn(AcO)2.2H2O ilereaksiyonundan kumarin içeren çinko metalli ftalosiyanin elde edildi. Kumarin içerenftalosiyaninler kolon kromatografisi yöntemiyle saflastirildi.1 13Sentezlenen bilesiklerin yapilari UV/VIS, FT-IR, H-NMR ve C-NMRspektrumlariyla aydinlatildi.Anahtar Kelimeler: 4-Hidroksifenilasetik asit, Ftalosiyanin, Kumarin.Mayis, 2005 Meryem ÇAMUR.