3-oksopropannitrillerin mangan(ııı) asetat aracılığında α,β-doymamış amitlerle radikalik halkalaşma reaksiyonları
Free radical cyclization of 3-oxopropanenitriles mediated manganese(III) acetate with α,β-unsaturated amides
Yazar: EMİNE VİLDAN BURGAZ
Danışman: PROF. DR. TARIK PEKEL
Ankara Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı
Derece: Yüksek Lisans, 2006
Konu: Kimya = Chemistry

Özet:
Bu tez, elektrokimyasal yöntemle sentezlenen mangan(III) asetat aracılığıyla 3-oksopropannitrillerin Î±,Î²-doymamış amitlerle radikalik halkalaşma reaksiyonlarıtemeline dayanmaktadır. Bu reaksiyonlar sonucunda 4-siyano-2,3-dihidrofuran-3-karboksiamit bileşikleri elde edildi.Çalışmada 3-oksopropannitril olarak; 3-fenil-3-oksopropannitril (1a), 3-(4-metilfenil)-3-oksopropannitril (1b), 3-(4-metoksifenil)-3-oksopropannitril (1c), 3-(4-klorfenil)-3-oksopropannitril (1d), 3-(2-tiyenil)-oksopropannitril (1e), 3-(2-furil)-oksopropannitril(1f) ve 3-(2-benzofuroil)-3-oksopropannitril (1g) ve 4,4-dimetil-3-oksopentannitril (1h)ve Î±,Î²-doymamış amit olarak; (2E)-3-tiyen-2-il-akrilamit (2a), (2E)-3-(2-furil)akrilamit(2b), (2E)-3-(5-metil-2-furil)akrilamit (2c), (2E) ve (2Z)-3-fenilakrilamit (2d) ve (2E,4E)-5-fenilpenta-2,4-dienamit (2e) kullanıldı.3-Oksopropannitrillerin 2a ve 2c alkenleri ile radikalik halkalaşma reaksiyonlarısonucunda 4-siyano-2,3-dihidrofuran-3-karboksiamit bileşikleri elde edildi. Fakat bu 3-oksopropannitrillerin 2b ve 2d ile reaksiyonlarında hiçbir ürün oluşmadı. Ayrıca, (2E,4E)-5-fenilpenta-2,4-dienamitin (2e) 1a-h ile reaksiyonlarında alkenil sübstitüe 4-siyano-2,3-dihidrofuran bileşikleri elde edildi. Bu bileşiklerin yapıları; IR, 1H-NMR,13C-NMR, LC-MS spektrumları ile aydınlatıldı.2006, 145 sayfaAnahtar Kelimeler: Mangan(III) asetat, Î±,Î²-doymamış amit, radikalik katılma, 4-siyano-2,3-dihidrofuran-3-karboksiamit, 3-oksopropannitril.

Abstract:
This study is based on the radical cyclization reactions of 3-oxopropanenitriles with Î±,Î²-unsaturated amides mediated manganese(III) acetate which is synthesized byelectrochemical method. By the end of these reactions 4-cyano-2,3-dihydrofuran-3-carboxyamide compounds were formed.3-phenyl-3-oxopropanenitrile (1a), 3-(4-metylphenyl)-3-oxopropanenitrile (1b), 3-(4-metoxyphenyl)-3-oxopropanenitrile (1c), 3-(4-chlorophenyl)-3-oxopropanenitrile (1d),3-(2-tienyl)-oxopropanenitrile (1e), 3-(2-furyl)-oxopropanenitrile (1f) 3-(2-benzofuroyl)-3-oxopropanenitrile (1g) and 4,4-dimetyl-3-oxopentanenitrile (1h)compounds were used as 3-oxopropanenitriles and (2E)-3-tien-2-yl-acrylamide (2a),(2E)-3-(2-furyl)acrylamide (2b), (2E)-3-(5-metyl-2-furyl)acrylamide (2c), (2E) and(2Z)-3-phenylacrylamide (2d) and (2E, 4E)-5-phenylpenta-2,4-dienamide (2e)compounds were used as Î±,Î²-unsaturated amides.4-cyano-2,3-dihydrofuran-3-carboxyamide compounds were synthesized by the radicalcyclization reactions with 3-oxopropanenitriles and 2a and 2c alkenes. However noproducts were observed with the reactions between 3-oxopropanenitriles and 2b and 2d.Also, alkenyl substituted 4-cyano-2,3-dihydrofuran compounds were formed with thereactions between (2E, 4E)-5-phenylpenta-2,4-dienamide (2e) and 1a-h. The structureof these compounds were identified with spectroscopic methods.2006, 145 pagesKey Words: Manganese(III) acetate, Î±,Î²-unsaturated amide, radical addition, 4-cyano-2,3-dihydrofuran-3-carboxyamide, 3-oxopropanenitrile.