Halojenli monoen ve nitrodien bileşiklerinden S-, ve N,S-substitüe organik bileşiklerin sentezi

Abstract

Bu tez çalışmamızda güçlü elektrofil olan polihalo-1,3-butadien bileşikleri ile güçlü nükleofil olan tiyollerin reaksiyonları incelenmiştir. Bu reaksiyonlar sonucunda mono(tiyo)substitüe 2-nitro-1,3-butadien yapısına sahip uzun zincirli tiyoeter bileşikleri elde edilmiştir.Yeni bileşiklerin sentezlenmesinde başlangıç maddesi olarak 2-nitro-pentaklor-1,3-butadien (1) bileşiği kullanılmıştır. 2-nitro-pentaklor-1,3-butadien bileşiğinin sentezi için sırasıyla; 1,1,3,3,4,4-heksaklor-1-buten (1a) ve 2H-pentaklor-1,3-butadien (1b) bileşikleri öncelikli olarak sentezlenmiştir. Çalışmanın ikinci aşamasında 2-nitro-pentaklor-1,3-butadien bileşiğinin 4-(tert-butil)benzilmerkaptan, etilmerkaptan, siklo-pentilmerkaptan, 4-klorofenil merkaptan ile reaksiyonundan S-substitüe nitrodien bileşikleri (2a, 2b, 2c ve 2d) sentezlenmiştir. Elde edilen S-substitüe nitrodien bileşikleri de başlangıç maddeleri olarak kullanılmıştır. Bazı piperazin türevleri ile uygun şartlardaki reaksiyonlarından yeni N,S-disubstitüe 2-nitro-polihalo-1,3-butadien bileşikleri sentezlenmiştir.Başlangıç maddelerinden 2-nitro-1-[4-(tert-butil)benziltiyo]-1,3,4,4-tetraklor-1,3-butadien (2a) bileşiğinin 1-(2-furoil)piperazin, 1-(tetrahidro-2-furoilmetil)piperazin, 1-(tetrahidro-2-furoil)piperazin, 1-piperonilpiperazin ile reaksiyonu sonucu sırasıyla, yeni; [1-(1-(2-furoil)piperazinil]-1-[4-(tert-butil)benziltiyo]-3,4,4-trikloro-2-nitro-1,3-butadien (3), [1-(1-(tetrahidro-2-furilmetil)piperazinil)]-1-[4-(tert-butil)benziltiyo]- 3,4,4-trikloro-2-nitro-1,3-butadien (4), [1-(1-(tetrahidro-2-furoil)piperazinil)]-1-[4-(tert-butil)benziltiyo]-3,4,4-trikloro-2-nitro-1,3-butadien (5), [1-(1-(piperonil)-piperazinil)]-1-[4-(tert-butil)benziltiyo]-3,4,4-trikloro-2-nitro-1,3-butadien (14) bileşikleri sentezlendi.Başlangıç maddelerinden 2-nitro-1-(etiltiyo)-1,3,4,4-tetraklor-1,3-butadien (2b) bileşiğinin 1-(2-furoil)piperazin, 1-(tetrahidro-2-furoil)piperazin, 1-(tetrahidro-2-furilmetil)piperazin, 1-bis(4-florfenil)metilpiperazin, piperonil piperazin ile reaksiyonu sonucu sırasıyla, yeni; [1-(1-(2-furoil)piperazinil)]-furoil)piperazin)-1-(etiltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (6), [1-(1-(tetrahydro-2-furoil)piperazinil)]-1-(etiltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (7), [1-(1-(tetrahidro-2-furilmetil)piperazinil)]-1-(etiltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (8), [1-(1-bis(4-florofenil)metilpiperazinil]-1-(etiltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (10) bileşikleri sentezlendi.Başlangıç maddelerinden 2-nitro-1-(siklopentiltiyo)-1,3,4,4-tetraklor-1,3-butadien (2c) bileşiği sırasıyla 1-(2-furoil)piperazin, 1-(tetrahidro-2-furoil)piperazin, 1-(tetrahidro-2-furilmetil)piperazin, piperonil piperazin, 1-bis(4-florfenil)metilpiperazin ile reaksiyonu sonucu sırasıyla, yeni; [1-(1-(2-furoil)piperazinil)]-1-(siklopentiltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (11), [1-(1-(tetrahidro-2-furoil)piperazinil)]-1-(siklopentiltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (12), [1-(1-(tetrahidro-2-furilmetil)piperazinil)]-1-(siklopentiltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (13), [1-(1-bis(4-florofenil) metilpiperazinil]-1-(siklopentiltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (15) bileşikleri sentezlendi.Başlangıç maddelerinden 2-nitro-1-(p-klorofeniltiyo)-1,3,4,4-tetraklor-1,3-butadien (2d) bileşiği ile 1-(2-furoil)piperazin'in reaksiyonundan yeni [1-(1-(2-furoil)piperazinil)]-1-(p-klorofeniltiyo)-3,4,4-trikloro-2-nitro-1,3-butadien (9) bileşiği elde edildi.Elde edilen 13 adet yeni bileşik kromatografik metodlar ile saflaştırıldı. Yapıları spektroskopik yöntemlerle (IR, 1H-NMR, 13C-NMR, MS…v.b) aydınlatıldı.

In this thesis, reactions between strong electrophilic polyhalo-1,3-butadiene compounds and strong nucleophilic thiols are investigated. According to results of this reactions, long chain thioether compounds were obtained which has mono(thio)substitue-2-nitro-1,3-butadienes structure.2-nitro-pentachloro-1,3-butadiene (1) was used as the starting material in new compounds syhthesis. At first 1,1,3,3,4,4-hexachloro-1-butene (1a) and 2H-pentachloro-1,3-butadiene (1b) compounds were synthesized for 2-nitro-pentachloro-1,3-butadiene (1) compound syhthesis. Second step of investigation, S-substitue nitrodiene compounds (2a, 2b, 2c and 2d) were synthesized with reactions of 4-(tert-butyl) benzyl mercaptan, etylmercaptan, cyclopentyl mercaptan and 4-chlorophenyl mercaptan by 2-nitro-pentachloro-1,3-butadiene (1). S-substitue nitrodiene compounds used as the starting materials in new compounds syhthesis. N, S-disubstitue 2-nitro-polyhalo-1,3-butadiene compounds were synthesized with reactions of some piperazine derivatives with appropriate circumstance.[1-(1-(2-furoyl)piperazin-1-yl]-1-(4-tert-butylbenzyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (3), [1-(1-(tetrahydro-2-furylmethyl)piperazin-1-yl)]-1-(4-tert-butylbenzyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (4), [1-(1-(tetrahydro-2-furoyl)piperazin-1-yl)]-1-(4-tert-butylbenzyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (5), [1-(1-(piperonyl)piperazin-1-yl)]-1-(4-tert-butylbenzyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (14) new compounds were synthesized. In accordance with the reaction of starting material 2-nitro-1-(4-tert-butylbenzyl-sulfanyl)-1,3,4,4-tetrachloro-1,3-butadiene (2a) with 1-(2-furoyl)piperazine, 1-(tetrahydro-2-furoylmethyl)piperazine, 1-(tetrahydro-2-furoyl)piperazine, 1-piperonylpiperazine, respectively.[1-(1-(2-furoyl)piperazin-1-yl)]-furoyl)piperazine)-1-(ethyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (6), [1-(1-(tetrahydro-2-furoyl)piperazin-1-yl)]-1-(ethyl-sulfanyl)- 3,4,4-trichloro-2-nitro-1,3-butadiene (7), [1-(1-(tetrahydro-2-furylmethyl)piperazin-1-yl)]-1-(ethyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (8), [1-(1-bis(4-fluoro-phenyl)methylpiperazin-1-yl]-1-(ethylsulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (10) new compounds were synthesized. In accordance with the reaction of starting material 2-nitro-1-(ethylsulfanyl)-1,3,4,4-tetrachloro-1,3-butadiene (2b) with 1-(2-furoyl)piperazine, 1-(tetrahydro-2-furoyl)piperazine, 1-(tetrahydro-2-furylmethyl) piperazine, 1-bis(4-fluoropheynl)methylpiperazine, 1-piperonylpiperazine, respectively.[1-(1-(2-furoyl)piperazin-1-yl)]-1-(cyclopentyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (11), [1-(1-(tetrahydro-2-furoyl)piperazin-1-yl)]-1-(cyclopentyl-sulfanyl)- 3,4,4-trichloro-2-nitro-1,3-butadiene (12), [1-(1-(tetrahydro-2-furylmethyl)piperazin-1-yl)]-1-(cyclopentyl-sulfanyl)- 3,4,4-trichloro-2-nitro-1,3-butadiene (13), [1-(1-bis(4-fluorophenyl)methylpiperazin-1-yl]-1-(cyclopentyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (15) new compounds were synthesized. In accordance with the reaction of starting material 2-nitro-1-(cyclopentyl-sulfanyl)-1,3,4,4-tetrachloro-1,3-butadiene (2c) with 1-(2-furoyl)piperazine, 1-(tetrahydro-2-furoyl)piperazine, 1-(tetrahydro-2-furylmethyl)piperazine, 1-piperonylpiperazine, 1-bis(4-fluoropheynl)methyl piperazine, respectively.[1-(1-(2-furoyl)piperazin-1-yl)]-1-(p-chlorophenyl-sulfanyl)-3,4,4-trichloro-2-nitro-1,3-butadiene (9) compound was obtained. In accordance with the reaction of starting material 2-nitro-1-(p-chloro-phenylsulfanyl)-1,3,4,4-tetrachloro-1,3-butadiene (2d) with 1-(2-furoyl)piperazine.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.).