Selenyum içeren heterosiklik yeni bileşiklerin sentezi
Synthesis of containing-selenium heterocyclic new compounds
Yazar: KADİR DOĞANAY
Danışman: PROF. DR. ALİYE ALTUNDAŞ
Gazi Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı
Derece: Yüksek Lisans, 2012
Konu: Kimya = Chemistry

Özet:
Bu çalışmada biyolojik etkinlik gösterebilecek polifonksiyonel grupların bağlı olduğu sikloheptaselenofen-2-il benzamit türevleri ve sikloheptaselenopirimidin türevleri sentezlendi.Bu amaçla Gewald metodunu kullanarak, sikloheptanon, malonitril ve metalik selenyumun reaksiyonu sonucunda 2-amino-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-3-karbonitril sentezlenmiştir. 2-amino-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-3-karbonitril' in benzoil klorür türevleri ile reaksiyonu sonucunda N-(3-siyano-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-2-il)-benzamit, N-(3-siyano-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-2-il)-4-florobenzamit, N-(3-siyano-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-2-il)-4-klorobenzamit, N-(3-siyano-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-2-il)-4-bromo-benzamit, N-(3-siyano-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-2-il)-4-metoksibenzamit ve N-(3- siyano-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-2-il)-4-nitrobenzamit bileşikleri elde edildi.Elde edilen 2-amino-5,6,7,8-tetrahidro-4H-siklohepta[b]selenofen-3-karbonitril' in formamit ile reaksiyonu sonucunda 6,7,8,9-tetrahidro-5H-siklohepta[4,5]seleno [2,3-d]pirimidin-4-amin, formik asit ile reaksiyonu sonucunda 1,5,6,7,8,9-hekzahidro-4H-siklohepta[4,5]seleno[2,3-d]pirimidin-4-on sentezlendi. 1,5,6,7,8,9-hekzahidro-4H-siklohepta[4,5]seleno[2,3-d]pirimidin-4-on' un POCl3 ile etkileşiminden 4-kloro-6,7,8,9-tetrahidro-5H-siklohepta[4,5]seleno[2,3-d]pirimidin elde edildi. 4-kloro-6,7,8,9-tetrahidro-5H-siklohepta[4,5]seleno[2,3-d]pirimidin' in pirolidin ile etkileşiminden 6,7,8,9-tetrahidro-4-(1-pirolidinil)-5H-siklohepta[4,5] seleno[2,3-d]pirimidin, morfolin ile etkileşiminden 6,7,8,9-tetrahidro-4-(4-morfolinil)-5H-siklohepta[4,5]seleno[2,3-d]pirimidin sentezlendi. Daha sonra 4-kloro-6,7,8,9-tetrahidro-5H-siklohepta[4,5]seleno[2,3-d]pirimidin' in hidrazin hidrat ile reaksiyonu sonucunda 1-hidrazino siklohepta(b)seleno[2,3-d]pirimidin elde edildi.Son aşamada 1-hidrazino siklohepta(b)seleno[2,3-d]pirimidin' in trimetil ortoformat ile etkileşiminden 9,10,11,12-tetrahidro-8H-siklohepta[4,5]seleno[3,2-e]-1,2,4-triazolo[4,3-c]pirimidin, NaNO2 ile etkileşiminden 9,10,11,12-tetrahidro-8H-siklohepta[4,5]seleno[3,2-e]tetrazolo[1,5-c]pirimidin bileşikleri sentezlenmiştir. Sentezlenen bileşiklerin yapıları spektroskopik yöntemler (1H-NMR, 13C-NMR, FTIR ve HR-MS ) ve element analizi ile aydınlatılmıştır.Anahtar Kelimeler : Selenofen, Selenofenilbenzamit, Selenopirimidin, Gewald Metodu

Abstract:
In this study, derivatives of cycloheptaselenophen-2-yl benzamide and cycloheptaselenopyrimidine having polyfunctional groups were synthesized. The synthesized compounds are thought to show biological activity.For this reason, 2-amino-5,6,7,8-tetrahydro-4H-cyclohepta[b]selenophen-3-carbonitrile was synthesized from the reaction of malonitrile with cycloheptanone and metallic selenium by Gewald method. Treatment of 2-amino-5,6,7,8-tetrahydro-4H-cyclohepta[b]selenophen-3-carbonitrile with derivatives of benzoyl chloride generated N-(3-cyano-5,6,7,8-tetrahydro-4H-cyclohepta[b]selenophen-2-yl)-benzamide, N-(3-cyano-5,6,7,8-tetrahydro-4H-cyclohepta[b]selenophen-2-yl)-4-fluorobenzamide, N-(3-cyano-5,6,7,8-tetrahydro-4H-cyclohepta[b]selenophen-2-yl)-4-chlorobenzamide, N-(3-cyano-5,6,7,8-tetrahydro-4H-cyclohepta[b]selenophen-2-yl)-4-bromobenzamide, N-(3-cyano-5,6,7,8-tetrahydro-4H-cyclohepta[b]selenophen -2-yl)-4-methoxybenzamide and N-(3-cyano-5,6,7,8-tetrahydro-4H-cyclohepta[b] selenophen-2-yl)-4-nitrobenzamide.The reaction of synthesized 2-amino-5,6,7,8-tetrahydro-4H-cyclohepta[b] selenophen-3-carbonitrile with formamide gave 6,7,8,9-tetrahydro-5H-cyclohepta[4,5]seleno[2,3-d]pyrimidin-4-amine and the reaction of synthesized 2-amino-5,6,7,8-tetrahydro-4H-cyclohepta[b]selenophen-3-carbonitrile with formic acid gave 1,5,6,7,8,9-hexahydro-4H-cyclohepta[4,5]seleno[2,3-d]pyrimidin-4-one. 1,5,6,7,8,9-hexahydro-4H-cyclohepta[4,5]seleno[2,3-d]pyrimidin-4-one was then reacted with POCl3 to obtain 4-chloro-6,7,8,9-tetrahydro-5H-cyclohepta[4,5]seleno[2,3-d]pyrimidine. Treatment of 4-chloro-6,7,8,9-tetrahydro-5H-cyclohepta[4,5]seleno[2,3-d]pyrimidine with pyrrolidine generated 6,7,8,9-tetrahydro-4-(1-pyrrolidinyl)-5H-cylohepta[4,5]seleno[2,3-d]pyrimidine and treatment of 4-chloro-6,7,8,9-tetrahydro-5H-cyclohepta[4,5]seleno[2,3-d]pyrimidine with morpholine generated 6,7,8,9-tetrahydro-4-(4-morpholinyl)-5H-cyclohepta[4,5]seleno[2,3-d] pirimidine. Reaction of 4-chloro-6,7,8,9-tetrahydro-5H-cyclohepta[4,5]seleno[2,3-d]pyrimidine with hydrazine gave 1-hydrazino cyclohepta(b)seleno[2,3-d]pyrimidine.At the last stage of this study, 1-hydrazino cyclohepta(b)seleno[2,3-d]pyrimidine was reacted with trimethylorthoformate in order to obtain 9,10,11,12-tetrahydro-8H-cyclohepta[4,5]seleno[3,2-e]-1,2,4-triazolo[4,3-c]pyrimidine and 1-hydrazino cyclohepta(b)seleno[2,3-d]pyrimidine was reacted with NaNO2 to obtain 9,10,11,12-tetrahydro-8H-cyclohepta[4,5]seleno[3,2-e]tetrazolo[1,5-c]pyrimidine. The structures of the synthesized compounds were confirmed by spectroscopic techniques (1H-NMR, 13C-NMR, FTIR ve HR-MS) and elemental analyses.Key Words : Selenophen, Selenophenylbenzamide, Selenopyrimidine, Gewald Method