2-amino-3-siyanopiridin türevlerinin sentezi, indirgenme, yükseltgenme ve singlet oksijen ile tepkimelerinin incelenmesi
Synthesis of 2-amino-3-cyanopyridine derivatives, investigation of reduction, oxidation and singlet oxygen reactions
Yazar: BERNA GÜL
Danışman: DOÇ. DR. ALİYE ALTUNDAŞ
Gazi Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı
Derece: Yüksek Lisans, 2011
Konu: Kimya = Chemistry

Özet:
Bu çalışmada biyolojik aktivite gösterebilecek polifonksiyonel grupların bağlı olduğu 2-amino-3-siyanopiridin türevleri sentezlendi.Bu amaçla farklı arilidenmalononitril türevleri kullanılarak 2-amino-5,6,7,8-tetrahidro-4-(5-metilfuran-2-il)kinolin-3-karbonitril, 2-amino-6,7,8,9-tetrahidro -4-(5-metilfuran-2-il)-5H-siklohepta[b]piridin-3-karbonitril, 2-amino-6,8-dihid ro-4-(5-metilfuran-2-il)-5H-pirano[3,4-b]piridin-3-karbonitril, 2-amino-5,6-di hidro-4-(5-metilfuran-2-il)furo[2,3-h]kinolin-3-karbonitril, 2-amino-5,6-dihidro -4-(5-metilfuran-2-il)tiyo[2,3-h]kinolin-3-karbonitril, 2-amino-5,7-dihidro-7- metil-4-(5-metilfuran-2-il)furo[3,4-b]piridin-3-karbonitril, 2-amino-5,6-dihidro-9-metoksi-4-(5-metilfuran-2-il)benzo[h]kinolin-3-karbonitril, 2-amino-5,6,7,8-tetrahidro-4-(4-metiltiyazol-2-il)kinolin-3-karbonitril, 2-amino-6,8-dihidro-4-(4-metiltiyazol-2-il)-5H-pirano[3,4-b]piridin-3-karbonitril, 2-amino-6,8-dihidro-4-(4-metiltiyazol-2-il)-5H-tiyopirano[3,4-b]piridin-3-karbonitril sentezlendi.2-Amino-3-siyanopiridin türevi olan 2-amino-5,6,7,8-tetrahidro-4-(5-metilfuran-2-il)kinolin-3-karbonitril ve 2-amino-6,7,8,9-tetrahidro-4-(5-metilfuran-2-il)-5H-siklohepta[b]piridin-3-karbonitril'deki nitril grubu indirgenerek 3-(amino metil)-4-(5-metilfuran-2-il)-5,6,7,8-tetrahidronaftalin-2-amin ve 3-(aminometil) -4-(5-metilfuran-2-il)-6,7,8,9-tetrahidro-5H-siklohepta[b]piridin-2-amin elde edildi.Elde edilen diamin bileşiklerin asetik asit ile reaksiyonu sonucu N-((2-amino-5,6,7,8-tetrahidro-4-(5-metilfuran-2-il)kinolin-3-il)metil)asetamit ve 3,4,6,7, 8,9,10-heptahidro-2-metil-5-(5-metilfuran-2-il)pirimido[4,5-b]kinolin elde edildi.2-Amino-5,6,7,8-tetrahidro-4-(5-metilfuran-2-il)kinolin-3-karbonitril, 2-amino-6,7,8,9-tetrahidro-4-(5-metilfuran-2-il)-5H-siklohepta[b]piridin-3-karbonitril, 2-amino-6,8-dihidro-4-(5-metilfuran-2-il)-5H-pirano[3,4-b]piridin-3-karbonitril' in singlet oksijen ile reaksiyonu sonucu (E,Z)-2-amino-4-(4-oksipent-2-enoil)-5,6,7,8-tetrahidrokinolin-3-karbonitril, (E)-2-amino-4-(4-oksipent-2-enoil)-6,7, 8,9-tetrahidro-5H-siklohepta[b]piridin-3-karbonitril, (E,Z)-2-amino-4-(4-oksipe nt-2-enoil)-6,8-dihidro-5H-pirano[3,4-b]piridin-3-karbonitril elde edilmiştir.Son aşamada 2-amino-4,5-dihidro-4-(5-metilfuran-2-il)furo[2,3-h]kinolin-3-karbonitril ve 2-amino-5,6-dihidro-4-(5-metilfuran-2-il)tiyo[2,3-h]kinolin-3-karbonitril'in 2,3-dikloro-5,6-disiyano-benzokinon (DDQ) ile yükseltgenmesi sonucu 2-amino-4-(5-metilfuran-2-il)furo[2,3-h]kinolin-3-karbonitril ve 2-amino-4-(5-metilfuran-2-il)tiyo[2,3-h]kinolin-3-karbonitril elde edilmiştir. Sentezlenen bileşiklerin yapıları spektroskopik yöntemler kullanılarak (1H-NMR, 13C-NMR ve FTIR) aydınlatılmıştır.

Abstract:
In this study, 2-amino-3-cyanopyridine derivatives having polifunctional groups was synthesized. The synthesized compounds is thought to show biological activity.For this reason, the syntheses of 2-amino-5,6,7,8-tetrahydro-4-(5-methylfuran-2-yl)quinolin-3-carbonitrile, 2-amino-6,7,8,9-tetrahydro-4-(5-methylfuran-2-yl)-5H-cyclohepta[b]pyridine-3-carbonitrile, 2-amino-6,8-dihydro-4-(5-methyl furan-2-yl)-5H-pyrano[3,4-b]pyridine-3-carbonitrile, 2-amino-5,6-di hydro-4-(5-methylfuran-2-yl)furo[2,3-h]quinolin-3-carbonitrile, 2-amino-5,6-dihydro-4-(5-methylfuran-2-yl)thio[2,3-h]quinolin-3-carbonitrile, 2-amino-5,7-dihydro-7-methyl-4-(5-methyl furan-2-il)furo[3,4-b]pyridine-3-carbonitrile, 2-amino-5,6-dihydro-9-methoxy-4-(5-methylfuran-2-il)benzo[h]quinolin-3-carbo nitrile, 2-amino-5,6,7,8-tetrahydro-4-(4-methylthiazol-2-yl)quinolin-3-carbo nitrile, 2-amino-6,8-dihydro-4-(4-methylthiazol-2-yl)-5H-pyrano[3,4-b]pyridine-3-carbo nitrile, 2-amino-6,8-dihydro-4-(4-methylthiazol-2-yl)-5H-thiopyrano[3,4-b] pyridine-3-carbonitrile were carried out by using different arylidene malononitrile derivatives.3-(Aminomethyl)-4-(5-metihyfuran-2-yl)-5,6,7,8-tetrahydronapthalene-2-amine and 3-(aminomethyl)-4-(5-methylfuran-2-yl)-6,7,8,9-tetrahydro-5H-cyclohepta [b]pyridine-2-amine were obtained by reducing nitrile groups of 2-amino-5,6,7,8-tetrahydro-4-(5-methylfuran-2-yl)quinolin-3-carbonitrile and 2-amino-6,7,8,9-tetrahydro-4-(5-methylfuran-2-yl)-5H-cycohepta[b]pyridine-3-carbo nitrile which are the derivatives of 2-amino-3-cyanopyridine.Then these diamine compounds were reacted with acetic acid to obtain N-((2-amino-5,6,7,8-tetrahydro-4-(5-methylfuran-2-yl)quinolin-3-yl)methyl)acetamide and 3,4,6,7,8,9,10-heptahydro-2-methyl-5-(5-methylfuran-2-yl)pyrimido[4,5-b] quinolin. Some of 2-amino-3-cyanopyridine derivatives, such as 2-amino-5,6,7,8-tetrahydro-4-(5-metihyfuran-2-yl)quinolin-3-carbonitrile, 2-amino-6,7,8,9-tetra hydro-4-(5-methylfuran-2-yl)-5H-cyclohepta[b]pyridine-3-carbonitrile, 2-amino -6,8-dihydro-4-(5-methylfuran-2-yl)-5H-pyrano[3,4-b]pyridine-3-carbonitrile was reacted with singlet oxygen in order to get (E,Z)-2-amino-4-(4-oxypent-2-enoyl)-5,6,7,8-tetrahydoquinolin-3-carbonitrile, (E)-2-amino-4-(4-oxypent-2-enoyl)-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridine-3-carbonitrile and (E,Z)-2-amino-4-(4-oxypent-2-enoyl)-6,8-dihydro-5H-pyrano[3,4-b]pyridine-3-carbonit rile.At the last stage of this study, 2-amino-4-(5-methylfuran-2-yl)furo[2,3-h]quinolin-3-carbonitrile and 2-amino-4-(5-methylfuran-2-yl)thieno[2,3-h] quinolin-3-carbonitrile was synthesized by the oxidation of 2-amino-4,5-dihydro-4-(5-methylfuran-2-yl)furo[2,3-h]quinolin-3-carbonitrile and 2-amino-5,6-dihydro-4-(5-methylfuran-2-yl)thieno[2,3-h]quinolin-3-carbonitrile with DDQ. The structure of the obtained compounds were determined by the spectroscopic methods (1H-NMR, 13C-NMR and FTIR).