Hacimli gruplar içeren dendritik ftalosiyaninlerin sentezi ve karakterizasyonu
Yükleniyor...
Dosyalar
Tarih
2019
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
İnönü Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Ftalosiyaninler, optik, kimyasal ve fiziksel özelliklerinden dolayı katalitik reaksiyonlar, gaz sensörleri, güneş pilleri, sıvı kristaller ve fotodinamik kanser tedavisi gibi çok farklı alanlarda kullanılmaktadır. Sterik etkisi büyük gruplar içeren ftalosiyanin ve dendritik ftalosiyanin türevlerinin homojen katalitik tepkimelerde, özellikle seçimli katalitik oksidasyon tepkimelerinde kullanıldığı görülmektedir. Bu nedenlerden dolayı elektron sağlayıcı ve sterik etkisi büyük gruplar içeren dendritik ftalosiyaninlerin sentezi ve karakterizasyonu önemli olacaktır. Bu çalışmada, elektron verici ve sterik etki özelliklerine sahip p-tersiyer bütilfenoksi gruplarının tris türevine bağlandığı dendritik ftalosiyaninler hazırlanmıştır. Tris(hidroksimetil)nitrometanın piridinde tiyonil klorür ile tepkimesi sonucu tris(klorometil)nitrometan, bu bileşiğin Pd/C ile indirgenmesi ile tris(klorometil)aminometan elde edildi. Dendritik grup 3, THF'de fenoksi tuzu (NaH ve p-tert-bütilfenol reaksiyonu ile elde edilen) ve tris(klorometil)aminometan tepkimesiyle hazırlandı. Oda sıcaklığında, DMF de K2CO3 varlığında 3 ve 4,5-dikloroftalonitrilin tepkimesi sonucu 4 bileşiği hazırlandı. 4 bileşiğinin Li metali ile tetramerizasyonu sonucu lityum ftalosiyanin türevi hazırlandı ve bu bileşiğin derişik H2SO4 ile hidrolizi ile metalsiz dendritik ftalosiyanin 5 sentezlendi. DMF de, DBU varlığında 4 bileşiğinin Zn(OAc)2 ve Co(OAc)2 ile tepkimesi sonucunda ise dendritik çinko ftalosiyanin türevi 6 ve dendritik kobalt ftalosiyanin türevi 7 hazırlandı. Tüm ftalosiyanin türevleri eter, CHCl3, aseton gibi organik çözgenlerde çözünmektedir. Hazırlanan bileşikler 1H-NMR,13C-NMR UV-vis ve IR spektroskopi yöntemleriyle karakterize edildi.
Phthalocyanines are used in catalytic reactions, gas sensors, solar cells, liquid crystals and photodynamic cancer treatment because of their optical, chemical and physical properties. Phthalocyanine and dendritic phthalocyanine derivatives containing large groups of steric effect appear to be used in homogeneous catalytic reactions, particularly in selective catalytic oxidation reactions. For these reasons, the synthesis and characterization of dendritic phthalocyanin containing electron donor groups and large groups of steric effect will be important. In this study, dendritic phthalocyanines were prepared in which p-tertiary butylphenoxy groups having large the steric effect and electron donor properties were bound to tris derivated. The reaction of tris(hydroxymethyl)nitromethane with thionyl chloride in pyridine gave the tris(chloromethyl)nitromethane, which was reduced by Pd / C to give tris(chloromethyl)aminomethane. The dendritic group 3 was prepared by the reaction of phenoxy salt (which obtained by reaction of NaH and p-tert-butylphenol) and tris(chloromethyl)aminomethane in THF. At room temperature, the reaction of 3 and 4,5-dichlorophthalonitrile in the presence of K2CO3 in DMF was used to prepare compound 4. The tetramerisation of the compound 4 and Li metal in pentanol was prepared and the lithium phthalocyanine derivative, and the metal-free dendritic phthalocyanine 5 was synthesized by hydrolysis of this compound with concentrated H2SO4. In DMF the presence of DBU, the reaction of 4 compounds with Zn(OAc)2 and Co(OAc)2 resulted in the preparation of dendritic zinc phthalocyanine derivative 6 and dendritic cobalt phthalocyanine derivative 7 respectively. All phthalocyanine derivatives are soluble in organic solvents such as ether, CHCl3, acetone. The prepared compounds were characterized by 1H-NMR, 13C-NMR,UV-vis and IR spectroscopic methods.
Phthalocyanines are used in catalytic reactions, gas sensors, solar cells, liquid crystals and photodynamic cancer treatment because of their optical, chemical and physical properties. Phthalocyanine and dendritic phthalocyanine derivatives containing large groups of steric effect appear to be used in homogeneous catalytic reactions, particularly in selective catalytic oxidation reactions. For these reasons, the synthesis and characterization of dendritic phthalocyanin containing electron donor groups and large groups of steric effect will be important. In this study, dendritic phthalocyanines were prepared in which p-tertiary butylphenoxy groups having large the steric effect and electron donor properties were bound to tris derivated. The reaction of tris(hydroxymethyl)nitromethane with thionyl chloride in pyridine gave the tris(chloromethyl)nitromethane, which was reduced by Pd / C to give tris(chloromethyl)aminomethane. The dendritic group 3 was prepared by the reaction of phenoxy salt (which obtained by reaction of NaH and p-tert-butylphenol) and tris(chloromethyl)aminomethane in THF. At room temperature, the reaction of 3 and 4,5-dichlorophthalonitrile in the presence of K2CO3 in DMF was used to prepare compound 4. The tetramerisation of the compound 4 and Li metal in pentanol was prepared and the lithium phthalocyanine derivative, and the metal-free dendritic phthalocyanine 5 was synthesized by hydrolysis of this compound with concentrated H2SO4. In DMF the presence of DBU, the reaction of 4 compounds with Zn(OAc)2 and Co(OAc)2 resulted in the preparation of dendritic zinc phthalocyanine derivative 6 and dendritic cobalt phthalocyanine derivative 7 respectively. All phthalocyanine derivatives are soluble in organic solvents such as ether, CHCl3, acetone. The prepared compounds were characterized by 1H-NMR, 13C-NMR,UV-vis and IR spectroscopic methods.
Açıklama
Anahtar Kelimeler
Chemistry, Kimya
Kaynak
WoS Q Değeri
Scopus Q Değeri
Cilt
Sayı
Künye
Perktaş, D. (2019). Synthesis and characterization of dendritic phthalocyanines containing large steric effect groups. Yüksek Lisans Tezi, İnönü Üniversitesi.
