Aza/tiyol-mıchael katılma reaksiyonları sonucu yeni sübstitüe dion bileşiklerinin sentezi
Synthesis of new substituted dione compounds as a result of aza / thiol-michael addition reactions
Yazar: ZEYNEP ÖZYILDIZ
Danışman: PROF. DR. ZELİHA GÖKMEN
İstanbul Üniversitesi-Cerrahpaşa / Lisansüstü Eğitim Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2020
Konu: Kimya = Chemistry
Dizin: Bismaleimidler = Bismaleimides ; Kinonlar = Quinones ; Konjuge katılma = Conjugate addition ; Sübstitüe = Substitue

Özet:
Bu çalışmada çeşitli kinon ve maleimid bileşiklerinin amin ve tiyollerle belirli koşullar altındaki reaksiyonları incelenmiştir.
Çalışmalarımızın ilk aşamasında başlangıç maddesi olarak kullanılan 2,3-dibromo-1,4-naftakinon (1) bileşiği ile amin ve tiyol türevlerinin reaksiyonlarından N- ve S,S- sübstitüe dion bileşikleri elde edilmiştir. 
2,3-dibromo-1,4-naftakinon (1) ve 1-piperonilpiperazin, 4-benzilpiperidin, 1-(2-furoil) piperazin, 2-piridinilpiperazin, trietilenteraamin, 1-(2-etoksietil)piperazin, 2-etilhekzantiyol, 2-feniletantiyol, 2-klorobenzenmetantiyol, 4-metoksitoluentiyol, 2,2'etilendioksietantiyol ile reaksiyonu sonucu sırasıyla; 2-(4-(benzo[d][1,3]dioksol-5-ilmetil)piperazin-1-il)-3-bromonaftalen-1,4-dion(3), 2-(4-benzilpiperidin-1-il)-3-bromonaftalen-1,4-dion (4), 2-bromo-3-(4-(furan-2-karbonil)piperazin-1-il)naftalen-1,4-dion (5), 2-bromo-3-(4-(pyridin-2-il)piperazin-1-il)naftalen-1,4-dion (6),    3,3'-(((etan-1,2-diilbis(azanediil))bis(etan-2,1-diil))-bis(azanediil))bis(2-bromonaftalen-1,4-dion) (7), 2-bromo-3-(4-(2-etoksietil)piperazin-1-il)naftalen-1,4-dion (8), 2,3-bis((2-etilhekzil)tiyo)naftalen-1,4-dion (9), 2,3-bis(fenetiltiyo)-naftalen-1,4-dion (10)   2,3-bis(2-klorobenziltiyo)naftalen-1,4-dion (11), 2,3-bis((4-metoksi-benzil)tiyo)naftalen-1,4-dion (12), 2,3,5,6,8,9-hekzahidronafto[2,3H][1,4]dioksa[7,10]ditiya-siklododesin-11,16-dion (13) bileşikleri sentezlenmiştir.




Çalışmanın ikinci aşamasında ise 2,3-dikloro-N-fenil maleimid (2) bileşiğinin amin ve tiyol türevlerinin reaksiyonları ile yeni N- ve S,S- sübstitüe dion bileşikleri sentezlenmiştir.
2,3-dikloro-N-fenil-maleimid (2) ile ile 2-piridinilpiperazin, 3-amino-1-propanol, 1-piperonil piperazin, 1-(2-furoil)piperazin, 2,2'-etilendioksietantiyol, 4-hidroksibütantiyol reaksiyonu sonucu sırasıyla; 3-kloro-1-fenil-4-(4-(piridin-2-il)piperazin-1-il)-1H-pirol-2,5-dion (14), 3-kloro-4-((2-hidroksietil)amino)-1-fenil-1H-pirol-2,5-dion (15), 3-(4-(benzo[d][1,3]dioksol-4-ilmetil)piperazin-1-il)-4-kloro-1-fenil-1H-pirol-2,5-dion (16), 3-kloro-4-(4-(furan-2-karbonil)-piperazin-1-il)-1-fenil-1H-pirol-2,5-dion (17), 12-fenil-2,3,5,6,8,9-hekzahidro-11H-[1,4]di-oksa[7,10]ditiyasiklododesino[8,9-c]pirol-11,13(12H)-dion (18), fenil-2,3,4,5,7,8,9,10-okta-hidro-12H-[1]oksa[6,9]ditiyasiklotridesino[7,8-c]pirol-12,14(13H)-dion (19) bileşikleri sentezlenmiştir.
Sentezlenmiş olan on yedi adet bileşik kromatografik metodlar ile saflaştırıldı. Yapıları spektroskopik yöntemlerle (IR, MS, 1H NMR ve 13C NMR… v.b) ortaya çıkarılmıştır.
                           
Anahtar kelimeler: 1,4-Naftakinon; Maleimid; Amin; Tiyol.

Abstract:
In this work the reactions of some quinone and maleimide compounds with thiols and amines under various reaction conditions were investigated.
In the first stage of our study, N- and S,S- sübstitued dione compounds synthesized by the reaction of amine and thiol derivates with 2,3-dibromo-1,4-naphtoquinone, which was used as starting material.
2-(4-(benzo[d][1,3]dioxol-5-ylmethyl) piperazin-1-yl)-3-bromonaphthalene-1,4-dione (3), 2-(4-benzylpiperidin-1-yl)-3-bromo-naphthalene-1,4-dione (4), 2-bromo-3-(4-(furan-2-carbonyl)piperazin-1-yl) naphthalene-1,4-dione (5), 2 -bromo-3-(4-(pyridin-2-yl)piperazin-1-yl)naphthalene-1,4-dione (6), 3,3'- (((ethane-1,2-diylbis(azanediyl)))bis(ethane-2,1-diyl))bis(azanediyl)bis(2-bromonaphthalene-1,4-dione) (7), 2-bromo-3-(4-(2-ethoxyethyl)piperazine-1-yl)naphthalene-1,4-dione (8), 2,3-bis((2-ethylhexyl)thio)naphthalene-1,4-dione (9), 2,3-bis(phenethylthio)naphthalene-1,4-dione (10),  2,3-bis(2-chlorobenzylthio)naphthalene-1,4-dione (11), 2,3-bis((4-methoxy-benzyl)thio)naphthalene-1,4-dione (12), 2,3,5,6,8,9-hexahydronaphtho[2,3H][1,4]-dioxa-[7,10]dithiasyclo-dodecine-11,16-dione (13) were synthesized by the reaction of compounds 2,3-dibromo-1,4-naphthoquinone (1) and 1-piperonylpiperazine, 4-benzylpiperidine, 1-(2-furoyl)piperazine, 2-pyridinylpiperazine, triethyleneteraamine, 1-(2-ethoxyethyl)piperazine, 2-ethylhexanthiol, 2-phenylethanethiol, 2-chlorobenzenethiol, 4-methoxytoluenthiol, 2,2'ethylenedioxyethanethiol respectively.
In the second stage of our study, new N- and S, S-substituted dione compounds were synthesized by the reaction of 2,3-dichloro-N-phenyl-maleimide (2) with amines and thiol derivates.
3-chloro-1-phenyl-4-(4-(pyridin-2-yl)piperazin-1-yl)-1H-pyrrole-2,5-dione (14), 3-chloro-4-((2-hydroxyethyl)amino)-1-phenyl-1H-pyrrole-2,5-dione (15), 3- (4-(benzo[d][1,3]dioxol-4-ylmethyl)piperazin-1-yl)-4-chloro-1-phenyl-1H-pyrrole-2,5-dione (16), 3-chloro-4-(4-(furan-2-carbonyl)piperazin-1-yl)-1-phenyl-1H-pyrrole-2,5-dione (17), 12-phenyl-2,3,5,6,8,9-hexahydro-11H-[1,4]dioxa[7,10]dithiasyclododecino[8,9-c]pyrrole-11,13(12H)-dione (18), phenyl-2,3,4,5,7,8,9,10-octahydro-12H-[1]oxa[6,9]dithia-syclo-tridecino[7,8-c]pyrrole-12,14(13H)-dione (19) were synthesized by the reaction of compounds 2-pyridinylpiperazine, 3-amino-1-propanol, 1-piperonylpiperazine, 1-(2-furoyl)piperazine, 2,2'-ethylenedioxyethanethiol, 4-hydroxybutanthiol with 2,3-dichloro-N-phenyl-maleimide respectively.
Seventeen compounds synthesized were purified by chromatographic methods. Its structures were revealed by spectroscopic methods (IR, MS, 1H NMR and 13C NMR… etc).

Keywords: 1,4-Naphthoquinone; Maleimide; Amine; Thiol.