Substitüe yeni tip ftalosiyoninlerin sentez ve özellikleri
Başlık çevirisi mevcut değil.
- Tez No: 56027
- Danışmanlar: PROF.DR. ÖZER BEKAROĞLU
- Tez Türü: Doktora
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1996
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 104
Özet
ÖZET Organik pigment ve boyar maddelerin yapılarında uzun yıllar kullanılan ftalosiyaninler, gösterdikleri çeşitli özelliklerden dolayı özellikle son 20-30 yılda geniş uygulama alanları bulmuştur. Substitüe olmayan ftalosiyaninler suda ve bir çok organik çözücüde çözünmediklerinden, son yıllarda yapılan çalışmaların önemi çözünür ürünler elde etme doğrultusunda olmuştur. Yapılan çok sayıda araştırmalar(gerek gurubumuz ve gerekse diğer grublar tarafından) göstermiştir ki bu bileşiklerin çözünürlükleri periferal olarak hacimli iyonik substiüentler (örneğin; -S03Na, -NR3+), ya da makrohalkalarda (tetraaza, diazadioxa, diazaditiya, crown eter, diazatrioxa,vb) artmaktadır. Bu yapılarının incelenebilmeleri için çok önemlidir. Bu çalışmada öncelikle 4,5 dikloro- 1,2 benzendikarboksilik asitten çıkılarak sırasıyla 5,6-dikloro-1,3-isobenzofurandion, 5,6-dikloro-1 H-isoindol- 1,3(2H)-dion, 4,5-dikloro~1,2-benzendikarboxsamid ve 4,5-dikloro-1,2-disiya no benzen elde edilmiştir. 2-Aminofenol ve 2-aminotiofenol'ün 4,5-dikloro- 1,2-disiyanobenzen ile olan reaksiyonundan yola çıkılarak 4,5-bis(2'- aminofenol)-1,2-disiyanobenzenin ve 4,5-bis(2'-aminotiofenol)-1,2-disiyano benzen elde edildi, öncelikle bu substitüe aminlerden ilkinin Ni, ikincisinin Ni.Zn.Co ftalosiyaninleri yapıldı. Ardından 4,5-bis(2'-aminotiofenol)-1,2 disiyano benzen 'in p-toluen sulfonil klorür ile tosillendirilmesiyle elde edilen tosil aminin 4,5-bis(chloromethyl)[benzo-15crown-5]-ile reksiyonundan iki- kat (diazaditio substitüe) makrosiklik halka elde edildi. Elde edilen bu madde üzerinden Nikel ftalosiyanin'e geçilmiştir. Sentezlenen bu maddelerin yapıları; Elementel analiz, İR, UV-VIS, NMR, MS ile aydınlatılmıştır. vu
Özet (Çeviri)
SUMMARY THE SYNTHESIS AND PROPERTIES OF NEW SUBSTITUTED PHTHALOCYANINES Phthalocyanines (Pc) are macrocyclic molecules containing four isoindole units, which are synthetic analogs of naturally occurring porphyrines derived from the porphin ring system. The rich coordination chemistry of phthalocyanine complexes has promoted the researches to 'tailor“ specific product with certain properties which are required by high technology applications. Two variables are the central metal ion and the peripheral substituents. When the possibility of inserting great number of different metal ion into phthalocyanine core is combined with the opportunity of unlimited number type of substituents the possibility of obtaining novel products is infinite. Since their synthesis early this century, phthalocyanines established themselves as blue and green dyestuffs par excel lenge. They are an important industrial commodity (output 45.000 tons in 1987) used primarily in inks (especially ball point pens), coloring for plastics and metal surfaces and dyestuffs for jeans and other clothing. More recently their use as the photocunducting agent in photocopying machines heralds a resurgence of interest in these species. In coming decade, their commercial utility is expected to have significant ramifications. Thus future potential uses of metal phthalocyanines, currently under study, include sensing elements in chemical sensors, electrochromic display devices, photodynamic reagent for cancer therapy and other medical applications, application to optical computers read-write discs, and related information storage system, catalysts for control of sulfur effluents, electrocatalysis for fuel cell applications, photovoltaic cell elements for energy generation, laser dyes, new-red-sensitive photocopying applications, liquid crystal color display applications and molecular metals and conducting polymers. In recent years, interest has been focused, inter alia, on the synthesis of a new type of soluble and unsymmetrical phthalocyanines, on the development of new approach to the synthesis of polynuclear, bridged, and polymeric species, on their electronic structure and redoxs properties, and their electro- and photovoltaic reactivity. VUlMost of the applications rely critically upon the redox properties of the Mpc species. The Pc unit is an 18 k- electron aromatic system that in its common oxidation state carries two negative charges. This will be designated Pc(-2). This unit is capable oxidation or reduction. The central metal ion may be incapable of a redox process in the usual electrochemical regime or may be a transition element that undergoes oxidation or reduction at potentials comparable to the ring processes. A common prerequisite for the materials for each field is the solubility in practical solvents. Additional factors such as wavelength of the Q-band absorption, thermal stability, electrical conductivity and redoxs potentials are accomlished by purpose designed substitution patterns. Most unsubstituted Mpc species have only very limited solubility in virtually all solvents, thereby limiting solution phase redoxs measurements. Ring substitution has proved to be a very effective procedure for rendering these substituted Mpc species soluble in a range of solvents, to an extend that, of course, depends upon the substituents used. On could pursue the comparative electrochemistry of the phthalocyanines with their cousins the porphyrins. Higher oxidation states of central transition metal ions are more readily accessible in the porphyrins series than in the phthalocyanine series, or, where formed, higher oxidation state metallo phthalocyanines are stronger oxidizing agents than their porphyrins analogues. Important step in combining macro-heterocycles with phthalocyanines has been the synthesis of phthalocyanines with four 14- or 15-membered tetraazamacrocycles which give the opportunity to prepare pentanuclear complexes with transition metal ions. Monoazatetraoxa-, diazatrioxa-.diazadioxa-, diazadithia-, tetraaza, tetrathia, tetraaza-crownether double layer and have been also substituted on the ohthalocyanine nucleus. Pure substituted phthalocyanines are preparred by cyclotetramerization of substituted 1,2-dicyanobenzenes or 1,3-diimino-1 H-isoindoles. If monosubstituted 1,2-dicyanobenzenes are employed, tetrasubstituted phthalocyanines with the disadvantage of a mixture of place isomers are obtained. 4,5-Disubstituted derivatives as starting materials lead to 2,3,9, 10,1 6, 17,23,24-identically substituted phthalocyanines. The two substituents of the 1,2-dicyanobezenes had to be introduced at a precursor, and a longer preparative route is necessary for 2,3,9,10,16,17,23,24- octasubstituted phthalocyanines. Phthalocyanines substituted with thia donors are rather few. Also a small proceeding describe the use of these types of compounds as IR absorbans. The shift at the high intensity Q-bands to the longer wavelength is a common feature of these compounds. IXIn the present work, we report for the first time preparation and characterization of new 4,5-disubstituted-phthalonitrile derivatives through base-catalyzed nucleofilic aromatic displacement reaction. That is, the reaction route was applied to prepare 4,5-bis(2'-aminothiophenoxy)- and 4,5- bis(2'-aminophenoxv)-1,2-dicyanobenzene(1 a and lb) from the corre sponding 2-aminothiophenol, 2-aminophenol and 4,5-dicholoro-1,2- dicyanobenzene (scheme 1). The reactions were carried out in tetrahydrofuran at room temperature with a pretty high yield( %75). CI CI CN CN A. M=Ni R=S 4a M=Ni R=0 5_ M=Zh R=S 6 M=Co R=S (Scheme 1 ). Cyclotetramerization of the 4,5-disubstituted-1,2-dicyanobenzene derivative (la and lb ) in to metal phthalocyanines(4, 4a, 5, 6 ) were obtained by usingthe anhydrous metal salts (NiCI2, (ZnOAc)2 and CoCI2 ). Dissolving in H2S04 and precipitating by addition of the ice-water and then column chromatography with silicagel was the method to obtain the pure product from the reaction mixture. The intense green colored products are soluble in a number of solvents such as DMF, pridin.DMSO, DMA and quinoline. In addition to above work, we report the preparation and characterization of a 14- membered symmetrical tetrabenzodiazadithia-substituted macrocycle and metal phthalocyanine derived from it.(7)(M=Ni) (Scheme 2). (Scheme 2). Diazadithia two-fold substituted macrocycle(3) was converted into Ni(ll)phthalocyanine derivative 7 directly by the reaction with anhydrous NiCI2 in quinoline. The yields of the la, lb and 3 in high boiling aprotic solvent, such as quinoline with appropriate metal salts gave the monomeric phthalocyanines 4a, 4-7(M=Ni”, Co“,Zn”) XIDetosylation of two-fold macrocycle-substituted phthalocyanin(7) in concentrated sulfuric acid at 125 C for 3h resulted in decomposition of phthalocyanine (7) Elemental analysis, İR, 1H-NMR, MASS and UV/VIS spectra confirm the proposed structures of the compounds. Comparison of IR spectral data 4,5-Dicholoro-1,2-dicyanobenzen and la, lb clearly indicates appearence of the -NH2 bands at 3350-3450 cm“1 in la and 1b and appearence of a old -CN band at 2220 cm”1 in la and lb. Tosylation of 1a and lb is verified by the appearance of the tosyl group stretches around 1370 and 1150 cm“1 of the 2a and 2b. IR spectrum of 3 clearly indicates the absence of -NH group by the intense characteristic stretching bands of -NH around 3250 cm'1. In the IR spectra of la and 1b, the intense absorption bands at 2220 and 2200 cm”1 respectively, corresponding to the -CN groups, and then disappear after the convention to the phthalocyanines(4, 4a, 5,6,7 ). In the 1H-NMR spectrum (D6) DMSO of la, 2a and 4 are also consistent with the proposed structures. Octakis (2' - aminothiophenoxy), octakis (2' - aminophenoxy) - substituted phthalocyanines (4, 4a, 5, 6 ) and 14-membered diazâdithia-substituted phthalocyanine (7) show intense Q absorption bands over 600-700 nm. There is a shoulder at slightly higher energy side for these product. The longer wavelength encountered for Zn(ll) phthalocyanine (4, 4a, 7 ) is especially noteworthy to donate the shift of this intense band near IR region as a results of S-substitution. Mass spectra of the substituted phthalonitriles and phthalocyanines have confirmed the proposed structures. Xll
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