Halobutadienler ve tiyollerden yeni tiyoeterlerin sentezi

Abstract

Çalışmamızın ilk aşamasında başlangıç maddesi olarak kullanılmak üzere 2-nitro-1,1,3,4,4-pentaklor-1,3-butadien (4) bileşiği sentezlendi.Çalışmamızın ikinci aşamasında başlangıç maddesi olarak kullanılan 1,1,2,3,4,4-heksaklor-1,3-butadien (1) ve 2-nitro-1,1,3,4,4-pentaklor-1,3-butadien (4) bileşiklerinin çeşitli tiyol bileşikleri ile olan reaksiyonları incelendi.1,1,2,3,4,4-Heksakloro-1,3-butadien (1) bileşiği ile 2-aminotiyofenol bileşiğinin bazik ortamda (EtOH/NaOH) gerçekleştirilen reaksiyonundan bilinmeyen, yeni 1-(2-aminofeniltiyo)-1,2,3,4,4-pentaklor-1,3-butadien (2) ve 1,4-bis(2-aminofeniltiyo)-1,2,3,4-tetraklor-1,3-butadien (3) bileşikleri elde edildi. 2-nitro-1,1,3,4,4-pentaklor-1,3-butadien (4) bileşiği ile 4-(t-butil)benzilmerkaptan bileşiğinin çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 2-nitro-1-[4-(t-butil)benziltiyo]-1,3,4,4-tetraklor-1,3-butadien (5) bileşiği elde edildi. 2-nitro-1,1,3,4,4-pentaklor-1,3-butadien (4) bileşiği ile 4-(t-butil)benzilmerkaptan bileşiğinin bazik ortamda (EtOH/NaOH) gerçekleştirilen reaksiyonundan bilinmeyen, yeni 4,4-diklor-2-nitro-1,1,3-tris[4-(t-butil)benziltiyo]-1,3-butadien (6) bileşiği elde edildi. 2-nitro-1,1,3,4,4-pentaklor-1,3-butadien (4) bileşiği ile 2,3,5,6-tetraflortiyofenol bileşiğinin çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 2-nitro-1-(2,3,5,6-tetraflorofeniltiyo)-1,3,4,4-tetraklor-1,3-butadien (7) bileşiği elde edildi.Çalışmamızın üçüncü ve son aşamasında, elde ettiğimiz mono(tiyo)sübstitüe-2-nitro-1,3,4,4-tetraklor-1,3-butadien bileşiklerinin N-nükleofil bileşikleri (morfolin, piperazin ve türevleri) ile olan reaksiyonları incelendi ve bilinmeyen, yeni N,S-disübstitüe nitrodien bileşikleri elde edildi.2-nitro-1-[4-(t-butil)benziltiyo]-1,3,4,4-tetraklor-1,3-butadien (5) bileşiği ile morfolin bileşiğinin reaksiyonundan bilinmeyen, yeni 1-morfolino-2-nitro-1-[4-(t-butil)benziltiyo]-3,4,4-triklor-1,3-butadien (8) bileşiği elde edildi. 2-nitro-1-[4-(t-butil)benziltiyo]-1,3,4,4-tetraklor-1,3-butadien (5) bileşiği sırasıyla piperazin, 1-(2-florfenil)piperazin, 1-(4-florfenil)piperazin, 2,5-dimetilpiperazin ve N-metilpiperazin ile reaksiyona sokuldu ve sırasıyla bilinmeyen, yeni N,N-bis[2-nitro-1-[4-(t-butil)benziltiyo]-3,4,4-trikloro-1,3-butadienil]-piperazin (9), 1-[(2-florofenil)piperazinil]-2-nitro-1-[4-(t-butil)benziltiyo]-3,4,4-triklor-1,3-butadien (10), 1-[(4-florofenil)piperazinil]-2-nitro-1-[4-(t-butil)benziltiyo]-3,4,4-triklor-1,3-butadien (11), N,N-bis[2-nitro-1-[4-(t-butil)benziltiyo]-3,4,4-trikloro-1,3-butadienil]-2,5-dimetilpiperazin (12) ve 1-(N-metilpiperazinil)-2-nitro-1-[4-(t-butil)benziltiyo]-3,4,4-triklor-1,3-butadien (13) bileşikleri elde edildi. 2-nitro-1-(2,3,5,6-tetraflorofeniltiyo)-1,3,4,4-tetraklor-1,3-butadien (7) bileşiği ile morfolin bileşiğinin reaksiyonundan bilinmeyen, yeni 1-morfolino-2-nitro-1-(2,3,5,6-tetraflorofeniltiyo)-3,4,4-triklor-1,3-butadien (14) bileşiği elde edildi. 2-nitro-1-(2,3,5,6-tetraflorofeniltiyo)-1,3,4,4-tetraklor-1,3-butadien (7) bileşiği sırasıyla 1-(2-florfenil)piperazin, 1-(4-florfenil)piperazin ve N-metilpiperazin bileşikleri ile reaksiyona sokuldu ve sırasıyla bilinmeyen, yeni 1-[(2-florofenil)piperazinil]-2-nitro-1-(2,3,5,6-tetraflorofeniltiyo)-3,4,4-triklor-1,3-butadien (15), 1-[(4-florofenil)piperazinil]-2-nitro-1-(2,3,5,6-tetraflorofeniltiyo)-3,4,4-triklor-1,3-butadien (16) ve 1-(N-metilpiperazinil)-2-nitro-1-(2,3,5,6-tetraflorofeniltiyo)-3,4,4-triklor-1,3-butadien (17) bileşikleri elde edildi.Sentezlenen bu yeni bileşikler kolon kromatografisi ve kristallendirme yöntemleri ile saflaştırıldı. Yapıları mikroanaliz ve spektroskopik yöntemler (FTIR, 1H-NMR, 13C-NMR ve MS) ile aydınlatıldı.

In the first step of our study, 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4) was synthesized to use as a starting compound.In the second step of our study, the reactions of 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) and 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4), which are used as starting compounds, with various thiols were investigated.The reaction of 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) with 2-aminothiophenol in the presence of NaOH in EtOH was carried out and new 1-(2-aminophenylthio)-1,2,3,4,4-pentachloro-1,3-butadiene (2) and 1,4-bis(2-aminophenylthio)-1,2,3,4-tetrachloro-1,3-butadiene (3) compounds were obtained. From the direct reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4) with 4-(t-buthyl)benzylmercaptan, new 2-nitro-1-[4-(t-buthyl)benzylthio]-1,3,4,4-tetrachloro-1,3-butadiene (5) compound was obtained. The reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4) with 4-(t-buthyl)benzylmercaptan in the presence of NaOH in EtOH was carried out and new 4,4-dichloro-2-nitro-1,1,3-tris[4-(t-buthyl)benzylthio]-1,3-butadiene (6) compound was obtained. From the direct reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4) with 2,3,5,6-tetrafluorothiophenol new 2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-1,3,4,4-tetrachloro-1,3-butadiene (7) compound was obtained.In the third and last step of our study, the reactions of mono(thio)substituted-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene compounds which we obtained, with N-nucleophile compounds (morpholine, piperazine and their derivatives) were investigated and new N,S-disubstituted nitrodiene compounds were obtained.From the reaction of 2-nitro-1-[4-(t-buthyl)benzylthio]-1,3,4,4-tetrachloro-1,3-butadiene (5) with morpholine, new 1-morpholino-2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadiene (8) compound was obtained. The new compounds N,N-bis[2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadienyl]-piperazine (9), 1-[(2-fluorophenyl)piperazinyl]-2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadiene (10), 1-[(4-fluorophenyl)piperazinyl]-2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadiene (11), N,N-bis[2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadienyl]-2,5-dimethylpiperazine (12) and 1-(N-methylpiperazinyl)-2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadiene (13) were synthesized from the reaction of 2-nitro-1-[4-(t-buthyl)benzylthio]-1,3,4,4-tetrachloro-1,3-butadiene (5) with piperazine, 1-(2-fluorophenyl)piperazine, 1-(4-fluorophenyl)piperazine, 2,5-dimethylpiperazine and N-methylpiperazine in turn. From the reaction of 2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-1,3,4,4-tetrachloro-1,3-butadiene (7) with morpholine, new 1-morpholino-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-butadiene (14) compound was obtained. The new compounds 1-[(2-fluorophenyl)piperazinyl]-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-butadiene (15), 1-[(4-fluorophenyl)piperazinyl]-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-butadiene (16) and 1-(N-methylpiperazinyl)-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-butadiene (17) were synthesized from the reaction of 2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-1,3,4,4-tetrachloro-1,3-butadiene (7) with 1-(2-fluorophenyl)piperazine, 1-(4-fluorophenyl)piperazine and N-methylpiperazine in turn.The novel products were purified either crystallization or via column chromatography. Structures of these novel products were characterized by microanalysis and spectroscopic methods (FTIR, 1H-NMR, 13C-NMR and MS).