Fosforlu Dibenzoksanten Türevlerinin Sentezi
Fosforlu Dibenzoksanten Türevlerinin Sentezi
Dosyalar
Tarih
2013-07-05
Yazarlar
Güler, Biyanka
Süreli Yayın başlığı
Süreli Yayın ISSN
Cilt Başlığı
Yayınevi
Fen Bilimleri Enstitüsü
Institute of Science and Technology
Institute of Science and Technology
Özet
Bu çalışmada optikçe aktif merkeze sahip fosfor ve azot bağlı dibenzoksanten türevlerinin sentezlenip bu bileşiklerin katalitik aktivitelerinin incelenmesi amaçlanmıştır. Çalışmanın ilk bölümünde benzaldehit ve β-naftol türevleri kullanılarak dibenzoksanten türevleri iki farklı metotla sentezlenmiştir. Birinci metotta benzaldehit ve β-naftol türevlerinin amberlyst-15 katalizörlüğünde petrol eteri (100–120 oC) içerisinde kaynama sıcaklığında gerçekleşen Friedel-Crafts reaksiyonu ile dibenzoksanten türevleri elde edilmiştir. İkinci metotta ise benzaldehit ve β-naftol türevlerinin P2O5 katalizörlüğünde çözücüsüz ortamda 120 oC’de gerçekleşen Friedel-Crafts reaksiyonu ile dibenzoksanten türevleri meydana gelmiştir. Çalışmanın ikinci aşamasında ise sentezlenen dibenzoksanten türevleri fosfin bileşikleri ile piridin varlığında THF içerisinde inert atmosferde 60 oC’de diklorofenilfosfin ile tepkimeye sokularak fosforlu dibenzoksanten türevleri elde edilmiştir. Çalışmanın üçüncü bölümünde ise azotlu dibenzoksanten türevlerinin eldesi amaçlanmıştır. Bunun için ilk önce hidroksibenzaldehit türevinin 1,2-dibromoetan ile K2CO3 varlığında aseton çözücüsünde 85 oC’de nükleofilik sübstitüsyon reaksiyonu ile mono ve bis benzaldehit türevleri sentezlenip kolon kromatografisi ile mono türevi ayrılır ve β-naftol türevi ile ikinci metoda göre reaksiyona sokularak kolay ayrılan gruba sahip dibenzoksanten türevi oluşturulmuştur . Daha sonra bu dibenzoksanten türevinin kinin ile toluen çözücüsünde reflaks sıcaklığındaki reaksiyonu sonucunda azotlu dibenzoksanten türevi sentezlenmiştir. Çalışmanın son bölümünde ise fosforlu ve azotlu dibenzoksanten türevlerinin katalitik özellikleri incelenmiştir. Bu amaçla; fosforlu ve azotlu dibenzoksaten türevleri, benzillik alkollerin 1,3-dikarbonil bileşikleriyle kenetlenme/halka kapama reaksiyonları ile inden türevlerinin sentez reaksiyonunda katalizör olarak kullanılmıştır.
The aim of this study is to synthesise phosphorous and nitrogenous dibenzoxanthene derivatives that are optically active and analyse their catalytic activities. In the first part of our study some dibenzoxanthene derivatives are synthesised by two different methods. In the first one, some benzaldehyde and β-naphthol compounds are reacted in petrolium ether (100-120oC) at 130oC by amberlyst-15 catalyst. In the other method benzaldehyde and β-naphthol compounds are reacted at 130oC under solvent free conditions by using P2O5 as catalyst. In the second part of this study, the dibenzoxanthene derivatives are reacted with dichlorophenylphosphine in the presence of pyridine in THF under inert atmosphere at 60oC and phosphorous dibenzoxanthene derivatives are achieved. In the following part of our study the nitrogenous dibenzoxanthene derivatives are synthesised. For this porpuse first of all a hydroxybenzaldehyde derivative is reacted with 1,2-dibromoethane in the presence of K2CO3 in aceton at 85oC. Mono and bis benzaldehyde derivatives that are obtained at the end of this reactin are seperated by colon chromatography. Then the mono derivative is reacted with β-naphthol derivative according to the second method to give dibenzoxanthene derivative which includes leaving group. Then this dibenzoxanthene derivative is reacted with quinine in toluen at reflax temperature in order to give nitrogenous dibenzoxanthene derivative. At the last part of this study the catalytic activities of both phosphorous and nitrogenous dibenzoxanthene derivatives are searched. For this aim the all derivatives are used as catalyst in the coupling/cyclization reactions of benzylic alcohols and 1,3-dicarbonyls to obtain indene derivatives.
The aim of this study is to synthesise phosphorous and nitrogenous dibenzoxanthene derivatives that are optically active and analyse their catalytic activities. In the first part of our study some dibenzoxanthene derivatives are synthesised by two different methods. In the first one, some benzaldehyde and β-naphthol compounds are reacted in petrolium ether (100-120oC) at 130oC by amberlyst-15 catalyst. In the other method benzaldehyde and β-naphthol compounds are reacted at 130oC under solvent free conditions by using P2O5 as catalyst. In the second part of this study, the dibenzoxanthene derivatives are reacted with dichlorophenylphosphine in the presence of pyridine in THF under inert atmosphere at 60oC and phosphorous dibenzoxanthene derivatives are achieved. In the following part of our study the nitrogenous dibenzoxanthene derivatives are synthesised. For this porpuse first of all a hydroxybenzaldehyde derivative is reacted with 1,2-dibromoethane in the presence of K2CO3 in aceton at 85oC. Mono and bis benzaldehyde derivatives that are obtained at the end of this reactin are seperated by colon chromatography. Then the mono derivative is reacted with β-naphthol derivative according to the second method to give dibenzoxanthene derivative which includes leaving group. Then this dibenzoxanthene derivative is reacted with quinine in toluen at reflax temperature in order to give nitrogenous dibenzoxanthene derivative. At the last part of this study the catalytic activities of both phosphorous and nitrogenous dibenzoxanthene derivatives are searched. For this aim the all derivatives are used as catalyst in the coupling/cyclization reactions of benzylic alcohols and 1,3-dicarbonyls to obtain indene derivatives.
Açıklama
Tez (Yüksek Lisans) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 2013
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2013
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2013
Anahtar kelimeler
faz geçiş katalizör,
4-hidroksibenzaldehit,
2-naftol,
amberlist-15,
ksanten,
phase transfer catalyst,
4-hydroxybenzaldehyde,
2-naphthol,
amberlyst-15,
xanthene