Halodienlerden yeni tiyoeterlerin sentezi
The synthesis of new thioethers from halodienes
Yazar: AMAÇ FATİH TUYUN
Danışman: PROF.DR. CEMİL İBİŞ ; YRD. DOÇ. DR. GÖKŞİN AYDINLI
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2007
Konu: Kimya = Chemistry
Dizin: Piperazin = Piperazine ; Tiyoeterler = Thioethers ; Tiyoller = Thiols

Özet:
Bu çalımaya trikloroetilen'in radikalik dimerlemesi ile hazırlanan polihalojenliorganik bileiin sentezlenmesi ve çeitli reaksiyonları ile elde edilen 4-bromo-2-nitro-1,1,3,4-tetrakloro-buta-1,3-dien bileiinin (6) sentezlenmesi ile balandı.Çalımanın sonraki aamasında (6) bileiinin tiyollerle olan reaksiyonları incelendi.Çalımaya 4-bromo-2-nitro-1,1,3,4-tetrakloro-buta-1,3-dien (6) 1-dekantiyol ilereaksiyonundan 4-bromo-1-desiltiyo-2-nitro-1,3,4-trikloro-buta-1,3-dien (15) bileii vep-bromotiyofenol ile reaksiyonundan 4-bromo-1-(4-bromofeniltiyo)-2-nitro-1,3,4-trikloro-buta-1,3-dien (17) bileii sentezlenerek devam edildi.Çalımanın son aamasında ise elde edilen mono(tiyo)sübstitüe nitrodien bileiklerininmorfolin ve bazı piperazin türevleri ile reaksiyonları incelendi.4-bromo-1-desiltiyo-2-nitro-1,3,4-trikloro-buta-1,3-dien (15) bileii, sırasıyla N-(difenilmetil)-piperazin (18), N-(2-florofenil)-piperazin (20), morfolin (22), N-(2-metoksifenil)-piperazin (24), N-etoksikarbonil-piperazin (26), N-(4-florofenil)-piperazin(28) ve N-fenilpiperazin (30) ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla4-bromo-1-desiltiyo-1-[N-(difenilmetil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien(19), 4-bromo-1-desiltiyo-1-[N-(2-florofenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (21), 4-bromo-1-desiltiyo-1-morfolin-2-nitro-3,4-dikloro-buta-1,3-dien (23), 4-bromo-1-desiltiyo-1-[N-(2-metoksifenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien(25), 4-bromo-1-desiltiyo-1-[N-etoksikarbonil-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (27), 4-bromo-1-desiltiyo-1-[N-(4-florofenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (29) ve 4-bromo-1-desiltiyo-1-(N-fenilpiperazin)-2-nitro-3,4-dikloro-buta-1,3-dien (31) bileikleri sentezlendi.4-bromo-1-(4-bromofeniltiyo)-2-nitro-1,3,4-trikloro-buta-1,3-dien (17) bileii,sırasıyla N-(difenilmetil)-piperazin (18), N-(2-florofenil)-piperazin (20), morfolin (22),N-(2-metoksifenil)-piperazin (24), N-etoksikarbonil-piperazin (26), N-(4-florofenil)-piperazin (28) ve N-fenilpiperazin (30) ile reaksiyona sokuldu. Reaksiyonlar sonucundasırasıyla 4-bromo-1-(4-bromofeniltiyo)-1-[N-(difenilmetil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (32), 4-bromo-1-(4-bromofeniltiyo)-1-[N-(2-florofenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (33), 4-bromo-1-(4-bromofeniltiyo)-1-morfolino-2-nitro-3,4-dikloro-buta-1,3-dien (34), 4-bromo-1-(4-bromofeniltiyo)-1-[N-(2-metoksifenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (35), 4-bromo-1-(4-bromofeniltiyo)-1-[N-etoksikarbonilpiperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (36), 4-bromo-1-(4-bromofeniltiyo)-1-[N-(4-florofenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (37) ve 4-bromo-1-(4-bromofeniltiyo)-1-(N-fenilpiperazin)-2-nitro-3,4-diklorobuta-1,3-dien (38) bileikleri sentezlendi.Sentezlenen yeni 2 adet mono(tiyo)nitrobuta-1,3-dien bileikleri ve bu bileiklerin 14adet piperazin türevi ürünleri orjinaldir. Oluan bu yeni ürünler kristallendirme veyakolon kromotografisi yöntemlerinden biriyle saflatırıldı. Yapıları mikroanaliz vespektroskopik yöntemler (IR, 1H-NMR, 13C-NMR, UV ve MS) ile aydınlatıldı.

Abstract:
Our investigations started with the synthesis of polyhalogenated butenes 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-buta-1,3-dien (6).In the following step, reactions of thiols with the compound (6) were investigated.Therefore, 4-bromo-1-decylthio-2-nitro-1,3,4-trichloro-buta-1,3-dien (15) and 4-bromo-1-(4-bromophenylthio)-2-nitro-1,3,4-trichloro-buta-1,3-dien (17) were synthesized fromthe reactions of 4-bromo-2-nitro-1,1,3,4-tetrachloro-buta-1,3-dien (6) with 1-decanethiol and p-bromothiophenol, respectively.In the last step, reactions of morpholine and derivatives of piperazine with themono(thio)substituted nitrodien compounds were explored.To obtain 4-bromo-1-decylthio-1-[N-(diphenylmethyl)-piperazine]-2-nitro-3,4-dichlorobuta-1,3-dien (19), 4-bromo-1-decylthio-1-[N-(2-fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (21), 4-bromo-1-decylthio-1-morpholine-2-nitro-3,4-dichlorobuta-1,3-dien (23), 4-bromo-1-decylthio-1-[N-(2-metoxyphenyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (25), 4-bromo-1-decylthio-1-[N-etoxycarbonyl-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (27), 4-bromo-1-decylthio-1-[N-(4- fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (29) and 4-bromo-1-decylthio-1-(Nphenylpiperazine)-2-nitro-3,4-dichloro-buta-1,3-dien (31), the reactions of 4-bromo-1-decylthio-2-nitro-1,3,4-trichloro-buta-1,3-dien (15) with the N-(diphenylmethyl)-piperazine (18), N-(2-fluorophenyl)-piperazine (20), morpholine (22), N-(2-metoxyphenyl)-piperazine (24), N-etoxycarbonyl-piperazine (26), N-(4-fluorophenyl)-piperazine (28) ve N-phenylpiperazine (30) were performed, respectively.Analogously, 4-bromo-1-(4-bromophenylthio)-1-[N-(diphenylmethyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (32), 4-bromo-1-(4-bromophenylthio)-1-[N-(2-fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (33), 4-bromo-1-(4-bromophenylthio)-1-morpholine-2-nitro-3,4-dichloro-buta-1,3-dien (34), 4-bromo-1-(4-bromophenylthio)-1-[N-(2-metoxyphenyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (35), 4-bromo-1-(4-bromophenylthio)-1-[N-etoxycarbonyl-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (36), 4-bromo-1-(4-bromophenylthio)-1-[N-(4- fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (37) and 4-bromo-1-(4-bromophenylthio)-1-(N-phenylpiperazine)-2-nitro-3,4-dichloro-buta-1,3-dien (38) were synthesized bythe interaction of 4-bromo-1-(4-bromophenylthio)-2-nitro-1,3,4-trichloro-buta-1,3-dien(17) with the N-(diphenylmethyl)-piperazine (18), N-(2-fluorophenyl)-piperazine (20),morpholine (22), N-(2-metoxyphenyl)-piperazine (24), N-etoxycarbonyl-piperazine(26), N-(4-fluorophenyl)-piperazine (28) ve N-phenylpiperazine (30), respectively.Synthesized two mono(thio)nitrobuta-1,3-dien compounds and their fourteen piperazinederivatives are original. The novel products were purified either crystallization or viacolumn chromatography. Structure of these novel products were characterized bymicroanalysis, spectroscopic methods (IR, 1H-NMR, 13C-NMR, UV and MS).