Brom ve klorlu 2-nitro-dien'den S- ve N,S sübstitüye tiyoeterlerin sentezi
The synthesis of S- and N,S-substituted thioethers from bromo and chloro-2-nitrodiene
Yazar: ELİF AYDIN
Danışman: PROF. DR. F. SERPİL GÖKSEL
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2008
Konu: Kimya = Chemistry

Özet:
Çalışmalarımız, trikloroetilen'in radikalik dimerizasyonundan kolaylıkla elde edilen polihalojenli buten sentezi ve onun 4-bromo-2-nitro-1,1,3,4-tetrakloro-1,3-butadien(6)'e giden daha sonraki reaksiyonları ile başladı.Çalışmanın sonraki aşamasında(6) bileşiğinin tiyollerle olan reaksiyonları incelenmiştir. Önce 4-bromo-2-nitro-1,1,3,4-tetrakloro-1,3-butadien (6)'in 1-siklohekziltiyol ile reaksiyonundan 4-bromo-1-siklohekziltiyo-2-nitro-1,3,4-trikloro-1,3-butadien (8) bileşiği ve 1-dodekantiyol ile reaksiyonundan 4-bromo-1-dodesiltiyo-2-nitro-1,3,4-trikloro-1,3-butadien (10) bileşiği sentezlenmiştir.Çalışmanın son aşamasında ise elde edilen mono(tiyo)sübstitüye nitrodien bileşiklerinin bazı piperazin türevleri ile reaksiyonları incelenmiştir.4-Bromo-1-siklohekziltiyo-2-nitro-1,3,4-trikloro-1,3-butadien (8) bileşiği, sırasıyla N-(difenilmetil)-piperazin (11), N-(2-fluorofenil)-piperazin (13), N-(4-fluorofenil)-piperazin (15) ve N-fenilpiperazin (17) ile reaksiyona sokulmuştur. Reaksiyonlar sonucunda sırasıyla 4-bromo-1-siklohekziltiyo-1-[N-(difenilmetil)-piperazin]-2-nitro-3,4-dikloro-1,3-butadien (12),4-bromo-1-siklohekziltiyo-1-[N-(2-fluorofenil)-piperazin] -2-nitro-3,4-dikloro-1,3-butadien (14), 4-bromo-1-siklohekziltiyo-1-[N-(4-fluorofenil)-piperazin]-2-nitro-3,4-dikloro-1,3-butadien (16) ve 4-bromo-1-siklohekziltiyo-1-(N-fenilpiperazin)-2-nitro-3,4-dikloro-1,3-butadien (18) bileşikleri sentezlenmiştir.4-Bromo-1-dodesiltiyo-2-nitro-1,3,4-trikloro-1,3-butadien (10) bileşiği, sırasıyla N-(difenilmetil)-piperazin (11), N-(2-fluorofenil)-piperazin (13), N-(4-fluorofenil)-piperazin (15), N-fenilpiperazin (17), N-(2-metoksifenil)-piperazin (23) ve N-etoksi-karbonil-piperazin (25) ile reaksiyona sokulmuştur. Reaksiyonlar sonucunda sırasıyla 4-bromo-1-dodesiltiyo-1-[N-(difenilmetil)-piperazin]-2-nitro-3,4-dikloro-1,3-butadien (19), 4-bromo-1-dodesiltiyo-1-[N-(2-fluorofenil)-piperazin]-2-nitro-3,4-dikloro-1,3-butadien (20), 4-bromo-1-dodesiltiyo-1-[N-(4-fluorofenil)-piperazin]-2-nitro-3,4-dikloro-1,3-butadien (21), 4-bromo-1-dodesiltiyo-1-(N-fenilpiperazin)-2-nitro-3,4-dikloro-1,3-butadien (22), 4-bromo-1-dodesiltiyo-1-[N-(2-metoksifenil)-piperazin-2-nitro-3,4-dikloro-1,3-butadien (24) ve 4-bromo-1-dodesiltiyo-1-(N-etoksikarbonil-piperazin)-2-nitro-3,4-dikloro-1,3-butadien (26) bileşikleri sentezlenmiştir.Sentezlenen yeni 1 adet mono(tiyo)nitro-1,3-butadien bileşiği ve 10 adet piperazin türevi orijinaldir. Oluşan bu yeni ürünler, kristallendirme veya kolon kromotografisi yöntemlerinden biriyle saflaştırıldı. Yapıları, mikroanaliz ve spektroskopik yöntemler (IR, 1H-NMR, 13C-NMR, UV ve MS) ile aydınlatıldı.

Abstract:
Our investigations started with the synthesis of polyhalogenated butene which is easily obtained from the radical dimerization of trichloroethylene and its subsequent reactions leading to the compound 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (6).In the following step, reactions of the compound with thiols (6) were investigated. Therefore, 4-bromo-1-cyclohexylthio-2-nitro-1,3,4-trichloro-1,3-butadiene (8) and 4-bromo-1- dodecylthio-2-nitro-1,3,4-trichloro-1,3-butadiene (10) were synthesized from the reactions of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (6) with 1-cyclohexylthiol and 1-dodecanethiol respectively.In the last step, reactions of piperazine derivatives with the mono(thio)substituted nitrodiene compounds were studied.To obtain 4-bromo-1-cyclohexylthio-1-[N-(diphenylmethyl)-piperazine]-2-nitro-3,4-dichloro-1,3-butadiene (12), 4-bromo-1-cyclohexylthio-1-[N-(2-fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-1,3-butadiene (14), 4-bromo-1-cyclohexylthio-1-[N-(4- fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-1,3-butadiene (16) and 4-bromo-1- cyclohexylthio-1-(N-phenylpiperazine)-2-nitro-3,4-dichloro-1,3-butadiene (18), the reactions of 4-bromo-1- cyclohexylthio-2-nitro-1,3,4-trichloro-1,3-butadiene (8) with the N-(diphenylmethyl)-piperazine (11), N-(2-fluorophenyl)-piperazine (13), N-(4-fluorophenyl)-piperazine (15) ve N-phenylpiperazine (17) were performed, respectively.Analogously, 4-bromo-1-dodecylthio-1-[N-(diphenylmethyl)-piperazine]-2-nitro-3,4-dichloro-1,3-butadiene (19), 4-bromo-1-dodecylthio-1-[N-(2-fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-1,3-butadiene (20), 4-bromo-1-dodecylthio-1-[N-(4- fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-1,3-butadiene (21), 4-bromo-1-dodecylthio-1-(N-phenylpiperazine)-2-nitro-3,4-dichloro-1,3-butadiene (22) 4-bromo-1-dodecylthio-1-[N-(2-metoxyphenyl)-piperazine]-2-nitro-3,4-dichloro-1,3-butadiene (24) and 4-bromo-1-dodecylthio-1-[N-etoxycarbonyl-piperazine]-2-nitro-3,4-dichloro-1,3-butadiene (26) were synthesized by the interaction of 4-bromo-1- dodecylthio-2-nitro-1,3,4-trichloro-1,3-butadiene (10) with the N-(diphenylmethyl)-piperazine (11), N-(2-fluorophenyl)-piperazine (13), N-(4-fluorophenyl)-piperazine (15) ve N-phenylpiperazine (17), N-(2-metoxyphenyl)-piperazine (23) and N-etoxycarbonyl-piperazine (25) respectively.Synthesized one of the mono(thio)nitro-1,3-butadiene compound and ten piperazine derivatives are original. The novel products were purified either crystallization or via column chromatography. Structures of these novel products were characterized by microanalysis, spectroscopic methods (IR, 1H-NMR, 13C-NMR, UV and MS).