Oktakis (2-tosilamindetiltia) sübstitüe porfirazinler
Octakis (2-tosylaminoethylthıo) substituted porphyrazines
Yazar: RABİA ZEYNEP USLU
Danışman: PROF. DR. AHMET GÜL
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü / Anorganik Kimya Ana Bilim Dalı
Derece: Yüksek Lisans, 1999
Konu: Kimya = Chemistry
Dizin: Aseton = Acetone ; Kimyasal bileşim = Chemical composition ; Sentezleme = Synthesizing ; Tetrapirol = Tetrapyrrol

Özet:
Tetrapirol türevi olarak tanımlayabileceğimiz tetraazaporfirinler (TAP), 1952' den sonra kimyamn temel araştırma konularından biri olmaya başlamıştır. Birçok organik solventte ftalosiyaninlere kıyasla daha çözünür özellik gösteren porfirazinlerin, periferal sübstitüentlerinde yapılacak değişiklikler, bu niteliklerini iyileştirmeyi mümkün kılmaktadır. Bu çalışmada tosilaminoetiltia sübstitüentleri içeren yeni porfirazinlerin sentezi amaçlanmıştır. Bunun için kullanılan doymamış 1,2-disiyano bileşiğinin eldesinde iki çıkış maddesi kullanılmıştır. Birincisi ditiamaleonitrilin disodyum tuzu, ikincisi di(toluen-p-sülfonil)etanolarnindir. İki temel çıkış maddesinin asetondaki reaksiyonundan porfirazin sentezi için gerekli olan l,2-bis(2-tosilaminoetiltia)maleonitril elde edilmiştir. Bu bileşik magnezyum alkolat etkisiyle siklotetramerizasyon reaksiyonu vermek üzere tepkimeye sokulmuş ve oktakis(2-tosilaminoetiltia)porfîrazinatomagnezyum elde edilmiştir. MgPz'nin metalsiz türevine dönüştürülmesi CF3COOH ile sağlanmıştır. Elde edilen oktakis(2- tosilaminoetiltia)porfirazinin Co (Il)asetat ile reaksiyonundan CoPz, Ni(II)asetat ile reaksiyonundan da NiPz'e geçilebilmiştir. Organik çözücülerde çok iyi çözünen bu yeni porfirazinlerdeki tosilamino grupları, moleküle yeni grupların bağlanmasına uygun bir reaktif grup oldukları gibi, tosil gruplarının uygun şartlarda kopanlmasıyla da aktif primer amin türevlerine de dönüştürülebilirler. Elde edilen yeni maddelerin yapılan, elementel. analiz, İR, UV/Görünür bölge ve 'H NMR spektrumlan yardımıyla aydınlatılmaya çalışılmıştır.

Abstract:
The design of novel substituted tetrapyrrol derivatives closely follows the requirements of their intended applications; e.g. if the aim of the work is to prepare photosensitive materials for photodynamic therapy, the active compounds should have features such as intense absorption on the lower energy side of visible electromagnetic radiation and solubility in water. Execution of minor changes on the nature and position of side groups or using different metal ions in the inner core can be considered as practical methods of tuning the properties of these materials. The aim of the present work has been to synthesize novel soluble porphyrazine derivatives by making use of a simple unsaturated o-dicyano starting material, namely l,2-bis(2-tosylaminoethylthia)maleonitrile. The reactants used to prepare this compound are disodium salt of maleonitrile and di(toluene-p- sulphonyl)ethanolamine. The condensation reaction between these two reactants in acetone leads to the yellow oily product with a high yield. Stretching vibrations due to NH, CH and ON groups appear at 3285, 2927 and 2213 cm"1, respectively. The stretching vibrations of SO2 groups come out at 1370 and 1191 cm'1 as given in the literature. In the *H NMR spectrum, chemical shifts for NH, S-CH2, N-CH2 protons appear at 5.71, 3.25 and 2.51 ppm. The first of these signals disappear by deuterium exchange indicating that it should be the single exchangeable proton in the molecule (Figure 1). SO, "Q5H4 CH, NH-S02 - C6H4- CH3 Figure 1. l,2-Bis(2-tosilaminoetiltia)maleonitril VlllIn order to convert the unsaturated dinitrile derivative into porphyrazine, we have made use of its template reaction in the presence of magnesium propanolate, which is the typical method generally applied in cyclotetramerization to these tetrapyrrol derivatives. The product is dark blue and it is soluble in chloroform, acetone, dichloromethane and pyridine and insoluble in hexane, diethylether or carbontetrachloride. In the IR spectrum of octakis(2-tosylaminoethylthia)porphyrazinatomagnesium (MgPz), the first difference when compared with the o-dicyano derivative, used as the starting material, has been the lack of stretching vibrations due to CN groups around 2200 cm"1. Although there has been no characteristic vibration for the porphyrazine core, the vibrations for SO2, NH and aliphatic CH groups on peripheral substituents come out about the same wave number as given in the literature. The elemenental analytical results closely follow the calculated values for C88Hİ6Ni6016Si6Mg(Figure 2). Figure 2. Octakis(2-tosylaminoethylthio)porphyrazinatomagnesium (MgPz) li In the H NMR spectrum of MgPz obtained in CDCI3, aromatic protons come out around 7.8-6.7 ppm and the deuterium exchangeable NH protons appear as a broad singlet around 6.28 ppm. There are two typical intense absorptions in the UV/Vibisle spectrum of metallo porphyrazines: one of them in the red region (Q band) and the other one near the UV IX(B band). The electronic spectrum of MgPz in chloroform is in accord with the expectations for D4h symmetry and the absorptions are at 670 and 374 nm. This bathochromic shift of Q band absorption in MgPz, when compared with directly alkyl substituted porphyrazines, clearly proves the effect of volumnious thia-donor groups. Almost the single procedure used to prepare metal-free porphyrazines is treatment of Mg-porphyrazine with acids. In the present case, MgPz has been treated with trifluoroacetic acid to obtain octakis(2-tosylaminoethlythia)porphyrazine (H2PZ). The reason for preferring this strong organic acid is because of its function to dissolve this material (Figure 3). Ts Ts \ / Ts NH NH Ts \ \ / / Figure 3. Octakis(2-tosylaminoethylthio)porphyrazine The typical change in the ER. spectrum when going from MgPz to F^Pz is the NH- stretching vibrations of the inner core around 3285 cm"1. This conversion has been verified by the electronic spectrum more elaborately. Since the symmetry of the molecule changes from D^ to Ü2h in this step, the Q band absorptions split into two peaks, one in the lower energy and the other in the higher energy side. The spectrum of H2Pz in chloroform shows these two signals at 705 nm and 638 nm. Preparation of the other metallo-porphyrazines has been usually realized by the reaction of the corresponding metal salt with the metal-free porphyrazine. In thepresent work, CoPz and NiPz have been prepared through the reaction of H2Pz with Co(II) and Ni(II)acetates. (Figure 4). Figure 4. Octakis(2-tosylaminoethylthia)porphyrazinatocobalt (II) and nicel (II) The IR and UV/Vis spectra of these derivatives are very similar to the spectrum of MgPz. As other examples of D^ tetrapyrrols, CoPz and NiPz exhibit single Q bands at 647 and 657 nm and B bands at 344 and 343 nm, respectively. In conclusion, the metal-free and Mg, Co, Ni complexes of octakis(2- tosylaminoethylthia)porphyrazine prepared during this work are extremely soluble in chloroform and number of other common solvents. In addition, tosylamino- substituents are capable of making condensation reactions with various groups to add other functionalities to the system or detosylation will result a completely reactive primary amino groups on the core.