Konjuge siklik dionlar ve polihalobutadienlerin heteroatom substitüe nükleofiller ile reaksiyonları
The reactions of conjugated cyclic diones and polyhalobutadienes with heteroatom-substituted nucleophiles
Yazar: MEHMET ERDİ ONAN
Danışman: DOÇ. DR. ZELİHA GÖKMEN
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2017
Konu: Kimya = Chemistry

Özet:
Bu çalışmada bazı nitrodien ve kinon bileşiklerinin piperazin ve tiyoeterlerle çeşitli reaksiyon şartlarında reaksiyonları incelenmiştir.
Çalışmalarımızın ilk kısmında başlangıç maddesi olarak daha önce sentezlenen üç adet nitrobutadien bileşiğinin 1-[hekzadesiltiyo]-1,3,4,4-tetrakloro-2-nitro-1,3-bütadien (1) , 1-siklopentiltiyo-1,3,4,4-tetrakloro-2-nitro-1,3-bütadien (2) , 1-oktadesiltiyo-1,3,4,4-tetrakloro-2-nitro-1,3-bütadien (3) bileşiklerinin piperazin türevleriyle reaksiyonuyla N-substitüe bileşikler kazanılmıştır.
1-[hekzadesiltiyo]-1,3,4,4-tetrakloro-2-nitro-1,3-bütadien (1) ile 1-(2-furoil)piperazin, 1-(4-florobenzil)piperazin ve 1-(3-fluorofenil)piperazin reaksiyonu sonucu sırasıyla; 1-[1-(2-furoil)piperazil]-1-hekzadesiltiyo-3,4,4-triklor-2-nitro-1,3-bütadien (5) , 1-[1-(4-florobenzil)piperazil]-1-hekzadesiltiyo-3,4,4-triklor-2-nitro-1,3-bütadien (6) , 1-[1-(3-florofenil)piperazil]-1-hekzadesiltiyo-3,4,4-trikloro-2-nitro-1,3-bütadien (7) yeni bileşikler sentezlendi. 
1-siklopentiltiyo-1,3,4,4-tetrakloro-2-nitro-1,3-bütadien (2) ile 1-(4-florobenzil) piperazin ve 1-(3-florofenil)piperazin reaksiyonu sonucu sırasıyla; 1-[1-(4-florobenzil)piperazinil]-1-siklopentiltiyo-3,4,4-trikloro-2-nitro-1,3-bütadien (8) ve 1-[1-(3-florofenil)piperazil]-1-siklopentiltiyo-3,4,4-triklor-2-nitro-1,3-bütadien (9) yeni bileşikler sentezlendi.
1-oktadesiltiyo-1,3,4,4-tetrakloro-2-nitro-1,3-bütadien (3) ile 1-(1-tetrahidro-2-furil)piperazin, 1-(4-florobenzil)piperazin reaksiyonu sonucu sırasıyla; 1-[1-(1-tetrahidro-2-furil)piperazinil]-1-oktadesiltiyo-3,4,4-triklor-2-nitro-1,3-bütadien (10) ve 1-[1-(4-florobenzil]-1-oktadesiltiyo-3,4,4-triklor-2-nitro-1,3-bütadien (11) yeni bileşikler sentezlendi.
İkinci aşamada ise başlangıç maddesi olan 2,3-dikloro-1,4-naftakinon (4) birleşiğinin çeşitli N-,O- ve S-substitue bileşikler ile çeşitli reaksiyon şartlarında reaksiyonları incelenmiştir.
Başlangıç maddesi olan 2,3-dikloro-1,4-naftakinon (4)  ile 1-(2-furoil) piperazin, siklopentiltiyol, 1,4- bütanditiyol, 1-(2-piridinil)piperazin, 1-(3-florofenil)piperazin ,1-Bis(4-florofenil)metilpiperazin,6-amino-hekzan-1-ol, 1-(3,4-diklorofenil)piperazin reaksiyonu sonucu sırasıyla; 2-(1-(2-furoil)piperazinil)-3-kloro-1,4-naftakinon (12), 2-[1-(2-Piridinil)piperazinil]-3-klor-1,4-naftakinon (13), 2-(1-(3-florofenil)piperazin)-3-klor-1,4-naftakinon (14), 2-(1-Bis(4-florofenil)metilpiperazinil)-3-kloro-1,4-naftakinon (15), 2-(1-(3,4-diklorofenil) piperazinil)-3-klor-1,4-naftakinon (16), 2-(6-amino-hekzil-1-ol)-3-kloro-1,4-naftakinon (17), 2,3-Bis(siklopentiltiyo)-1,4-naftakinon (18), 2,3-bis(siklobütiltiyol)-1,4-naftakinon (19) yeni bileşikler sentezlendi.
Elde edilen 15 adet yeni bileşik kromatografik metodlar ile saflaştırıldı. Yapıları spektroskopik yöntemlerle (IR, 1H-NMR, 13C-NMR, MS… v.b) aydınlatıldı.

Abstract:
In this work, the reactions of some nitrodiene and quinone compounds with piperazine and thioethers under various reaction conditions were investigated.
In the first part of our work as a startup item previously synthesized the compound again of three nitrobutadiene, 
1-[hexadecylthio]-1,3,4,4-tetrachloro-2-nitro-1,3-butadiene (1), 1-cyclopentylthio-1,3,4,4-tetrachloro-2-nitro-1,3 -butadien  (2), 1-octadecylthio-1,3,4,4-tetrachloro-2-nitro-1,3-butadiene (3), variation of reaction of piperazine compounds with N-substitüe compounds.
1-[1-(4-fluorobenzyl)piperazyl]-1-hexadecanethiol-3,4,4-trichloro-2-nitro-1,3-butadiene (5), 1-[1-(4-fluorobenzyl)piperazyl]-1-hexadecylthio-3,4,4-trichloro-2-nitro-1,3-butadiene (6), 1- [1-(3-fluorophenyl)piperazyl]-1-trichloro-2-nitro-1,3-butadiene (7)  new compounds were synthesized. In accordance with the reaction of starting material 1-[hexadecylthio]-1,3,4,4-tetrachloro-2-nitro-1,3-butadiene (1) with 1-(3-fluorophenyl) piperazine, 1-(2-furoyl)piperazine, 1-(4-fluorobenzyl) piperazine and 1-(2-fluorobenzyl) piperazine respectively. 
1-[1-(3-fluorobenzyl)piperazinyl]-1-cyclopentylthio-3,4,4-trichloro-2-nitro-1,3-butadiene(8), 1-[1-(3-fluorophenyl)piperazyl]-1-cyclopentylthio-3,4,4-trichloro-2-nitro-1,3-butadiene(9)  new compounds were synthesized. In accordance with the reaction of starting material 1-Cyclopentylthio-1,3,4,4-tetrachloro-2-nitro-1,3-butadiene (2) with 
1-(4-fluorobenzyl)piperazine and 1-(3-fluorophenyl)piperazine respectively.
1-[1-(2-furoyl)piperazine]-1-octadecylthio-3,4,4-trichloro-2-nitro-1,3-butadiene (10) and 1-[1-(4-fluorobenzyl)piperazinyl]-1-octadecylthio-3,4,4-trichloro-2-nitro-1,3-butadiene (11) new compunds were synthesized. In accordance with the reaction of starting material 1-octadecylthio-1,3,4,4-tetrachloro-2-nitro-1,3-butadiene (3) with 
1-(2-furoyl)piperazine, 1-(4-fluorobenzyl)piperazine respectively.
In the second step of the thesis, 2,3-dichloro, 1,4-naphthaquinone (4) was used as the starting material.
2-(1-(2-furoyl)piperazinyl)-3-chloro-1,4-naphthaquinone(12), 2-[1-(2-pyridyl)piperazinyl]-3-chloro-1,4-naphthaquinone(13), 2-(1-(3-fluorophenyl) piperazinyl)-3-chloro-1,4-naphthaquinone(14), 2-(1-Bis(4-fluorophenyl)methyl piperazinyl)-3-chloro-1,4-naphthaquinone (15), 2-(1-(3,4-dichlorophenyl)piperazinyl)-3-chloro-1,4-naphthaquinone(16), 2-(6-amino-hexyl-1-ol)-3-chloro-1,4-naphthaquinone(17), 2,3-Bis-(Cyclopentanethiol)-1,4-naphthaquinone(18), 2,3-bis-cyclobutanethiol-1,4-naphthaquinone(19) new compunds were synthesized. In accordance with the reaction of starting material 2,3-dichloro-1,4-naphthaquinone (4) with 1-(2-furoyl)piperazine, Cyclopentanethiol,1,4-butanedithiol,1-(2-Pyridyl)piperazine,1-(3-fluoropheny)piperazine, 1-Bis(4-fluorophenyl)methylpiperazine, 6-amino-hexan-1-ol, 1-(3,4-dichloro phenyl)piperazine respectively.
These 13 new compounds were refined with chromatographic methods. Structure of the products were characterized by spectroschopic methods (IR, 1H-NMR, 13C-NMR, MS… etc.).