Konjuge siklik dionlar ve polihalobutadienlerin heteroatom substitüe nükleofiller ile reaksiyonları

Abstract

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.

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.).