Halodienlerden yeni tiyoeterlerin sentezi

Abstract

Bu çalımaya trikloroetilen'in radikalik dimerlemesi ile hazırlanan polihalojenliorganik 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 ilereaksiyonundan 4-bromo-1-desiltiyo-2-nitro-1,3,4-trikloro-buta-1,3-dien (15) bileii vep-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 bileiklerininmorfolin 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 sırasıyla4-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 sonucundasırasıyla 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 14adet piperazin türevi ürünleri orjinaldir. Oluan bu yeni ürünler kristallendirme veyakolon kromotografisi yöntemlerinden biriyle saflatırıldı. Yapıları mikroanaliz vespektroskopik yöntemler (IR, 1H-NMR, 13C-NMR, UV ve MS) ile aydınlatıldı.

Our investigations started with the synthesis of polyhalogenated butenes which is easilyobtained from the radical dimerization of trichloroethylene and its subsequent reactionsleading 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 fromthe 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 themono(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 bythe 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 piperazinederivatives are original. The novel products were purified either crystallization or viacolumn chromatography. Structure of these novel products were characterized bymicroanalysis, spectroscopic methods (IR, 1H-NMR, 13C-NMR, UV and MS).