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İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Anabilim Dalı / Organik Kimya Bilim Dalı

Alifatik ve aromatik gruplu yeni tiyoeterlerin sentezi

Synthesis of new thioethers with aliphatic and aromatic groups

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Özet:

Çalışmanın ilk aşamasında, trikloretilenin radikalik dimerizasyonundan polihalojenli butadien ve sonra bu bileşiğin çeşitli reaksiyonlarından başlangıç maddeleri 4-bromo-2-nitro-1,1,3,4-tetrakloro-1,3-butadien (1) ve 2-nitro-1,1,3,4,4-pentakloro-1,3-butadien (2) sentezlendi.Çalışmanın ikinci aşamasında, 4-bromo-2-nitro-1,1,3,4-tetrakloro-1,3-butadien (1) ve 2-nitro-1,1,3,4,4-pentakloro-1,3-butadien (2) bileşiğinin tiyollerle olan reaksiyonları incelendi. Bu reaksiyonlardan yeni mono-, di-, tri-sübstitüe nitrodien bileşikleri sentezlendi.4-Bromo-2-nitro-1,1,3,4-tetrakloro-1,3-butadien (1) ile 1-heptantiyol'ün çözücüsüz ortamda reaksiyonundan 4-bromo-1,3,4-trikloro-2-nitro-1-heptiltiyo-1,3-butadien (3) ve 3,4-dikloro-2-nitro-1,1,4-tris-(1-heptiltiyo)-1,3-butadien (4), bazik ortamdaki reaksiyonundan ise 4-bromo-3,4-dikloro-2-nitro-1,1-bis-(1-heptiltiyo)-1,3-butadien (5) bileşikleri elde edildi. 4-Bromo-2-nitro-1,1,3,4-tetrakloro-1,3-butadien (1) ile 2-izopropil benzentiyol'ün çözücüsüz ortamda reaksiyonundan 4-bromo-1,3,4-trikloro-2-nitro-1-[2-izopropilbenzentiyo]-1,3-butadien (12) ve bazik ortamda reaksiyonundan, 4-bromo-3,4-dikloro-2-nitro-1,1-bis-[2-izopropilbenzentiyo]-1,3-butadien (13) bileşikleri sentezlendi. 4-Bromo-2-nitro-1,1,3,4-tetrakloro-1,3-butadien (1) ile 4-metoksitiyofenol'ün çözücüsüz ortamda reaksiyonundan 4-bromo-1,3,4-trikloro-2-nitro-1-[4-metoksifeniltiyo]-1,3-butadien (16) ve 4-bromo-3,4-dikloro-2-nitro-1,1-bis-[4-metoksifeniltiyo]-1,3-butadien (17) bileşikleri elde edildi. 2-Nitro-1,1,3,4,4-pentakloro-1,3-butadien (2) ile 2-izopropil benzentiyol'ün çözücüsüz ortamda reaksiyonundan 2-nitro-1,3,4,4-tetrakloro-1-[2-izopropilbenzentiyo]-1,3-butadien (22) bileşiği sentezlendi. 2-Nitro-1,1,3,4,4-pentakloro-1,3-butadien (2) ile 4-metoksitiyofenol'ün çözücüsüz ortamda reaksiyonundan 2-nitro-1,3,4,4-tetrakloro-1-[4-metoksifeniltiyo]-1,3-butadien (26) ve 2-nitro-3,4,4-trikloro-1,1-bis-[4-metoksifeniltiyo]-1,3-butadien (27) bileşikleri elde edildi.Çalışmanın son aşamasında ise elde edilen mono(tiyo)sübstitüe nitrodien bileşiklerinin morfolin, piperazin türevleri ve amin bileşikleri ile reaksiyonları incelendi. Bu reaksiyonlardan yeni N,S-disübstitüe nitrodien bileşikleri sentezlendi.4-Bromo-1,3,4-trikloro-2-nitro-1-heptiltiyo-1,3-butadien (3)`nin sırasıyla N-fenil piperazin, N-(difenilmetil)-piperazin, N-(4-fluorofenil)-piperazin, N-(2-fluorofenil)-piperazin, morfolin ve piperazin ile reaksiyonundan, 4-bromo-3,4-dikloro-2-nitro-1-heptiltiyo-1-[N-fenilpiperazin]-1,3-butadien (6), 4-bromo-3,4-dikloro-2-nitro-1-heptiltiyo-1-[N-(difenilmetil)-piperazin]-1,3-butadien (7), 4-bromo-3,4-dikloro-2-nitro-1-heptiltiyo-1-[N-(4-fluorofenil)-piperazin]-1,3-butadien (8), 4-bromo-3,4-dikloro-2-nitro-1-heptiltiyo-1-[N-(2-fluorofenil)-piperazin]-1,3-butadien (9), 4-bromo-3,4-dikloro-2-nitro-1-heptiltiyo-1-morfolino-1,3-butadien (10), N,N-bis[4-bromo-2-nitro-1-heptiltiyo-3,4-dikloro-1,3-butadienil]-piperazin (11) bileşikleri elde edildi. 4-Bromo-1,3,4-trikloro-2-nitro-1-[2-izopropilbenzentiyo]-1,3-butadien (12)'nin N-fenil piperazin ve N-(difenilmetil) piperazin ile reaksiyonundan, 4-bromo-3,4-dikloro-2-nitro-1-[2-izopropilbenzentiyo]-1-[N-fenilpiperazin]-1,3-butadien (14) ve 4-bromo-3,4-dikloro-2-nitro-1-[2-izopropilbenzentiyo]-1-[N-(difenilmetil)-piperazin]-1,3-butadien (15) bileşikleri sentezlendi. 4-Bromo-1,3,4-trikloro-2-nitro-1-[4-metoksi feniltiyo]-1,3-butadien (16)'nın sırasıyla N-fenil piperazin, N-(difenilmetil) piperazin, diheksilamin ve N-metilsikloheksilamin ile reaksiyonundan, 4-bromo-3,4-dikloro-2-nitro-1-[4-metoksifeniltiyo]-1-[N-fenilpiperazin]-1,3-butadien (18), 4-Brom-3,4-diklor-2-nitro-1-[4-metoksifeniltiyo]-1-[N-(difenilmetil)-piperazin]-1,3-butadien (19), 4-bromo-3,4-dikloro-2-nitro-1-[4-metoksifeniltiyo]-1-dihekzilamin-1,3-butadien (20), 4-bromo-3,4-dikloro-2-nitro-1-[4-metoksifeniltiyo]-1-[N-metilsiklohekzilamin]-1,3-butadien (21) bileşikleri elde edildi. 2-Nitro-1,3,4,4-tetrakloro-1-[2-izopropilbenzentiyo]-1,3-butadien (22)'nin N-fenil piperazin, N-(difenilmetil) piperazin ve N-(4-fluorofenil)-piperazin ile reaksiyonundan, 2-nitro-3,4,4-trikloro-1-[2-izopropilbenzentiyo]-1-[N-fenilpiperazin]-1,3-butadien (23), 2-nitro-3,4,4-trikloro-1-[2-izopropilbenzentiyo]-1-[N-(difenilmetil)-piperazin]-1,3-butadien (24), 2-nitro-3,4,4-trikloro-1-[2-izopropilbenzentiyo]-1-[N-(4-fluorofenil)-piperazin]-1,3-butadien (25) bileşikleri sentezlendi. 2-Nitro-1,3,4,4-tetrakloro-1-[4-metoksifeniltiyo]-1,3-butadien (26)'nın sırasıyla N-fenil piperazin, N-(difenilmetil) piperazin, N-(4-fluorofenil)-piperazin, morfolin, diheksilamin ve N-metilsikloheksilamin ile reaksiyonundan, 2-nitro-3,4,4-trikloro-1-[4-metoksifeniltiyo]-1-[N-fenilpiperazin]-1,3-butadien (28), 2-nitro-3,4,4-trikloro-1-[4-metoksifeniltiyo]-1-[N-(difenilmetil)-piperazin]-1,3-butadien (29), 2-nitro-3,4,4-trikloro-1-[4-metoksifeniltiyo]-1-[N-(4-fluorofenil)-piperazin]-1,3-butadien (30), 2-nitro-3,4,4-trikloro-1-[4-metoksifeniltiyo]-1-morfolino-1,3-butadien (31), 2-nitro-3,4,4-trikloro-1-[4-metoksifeniltiyo]-1-dihekzilamin-1,3-butadien (32), 2-nitro-3,4,4-trikloro-1-[4-metoksifeniltiyo]-1-N-metilsiklohekzilamin-1,3-butadien (33) bileşikleri sentezlendi.Sentezlenen bu bileşikler kristallendirme veya kolon kromotografisi ile saflaştırıldı. Yapıları mikroanaliz ve spektroskopik yöntemler (FTIR, 1H-NMR, 13C-NMR, UV-Vis ve MS) ile aydınlatıldı.

Summary:

In the first step of the study, polyhalogenated butadiene was synthesized from the radical dimerization of trichloroethylene and then starting compounds 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (1) and 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) were synthesized from the various reactions of this compound.In the second step of the study, reactions of thiols with 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (1) and 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) were studied. New mono-, di-, tri-substituted nitrodiene compounds were synthesized from these reactions.4-Bromo-1,3,4-trichloro-2-nitro-1-heptylthio-1,3-butadiene (3) and 3,4-dichloro-2-nitro-1,1,4-tris-(1-heptylthio)-1,3-butadiene (4) were synthesized from the reactions of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (1) with 1-heptanethiol without solvent, and from the similarly reaction in the basic medium, 4-bromo-3,4-dichloro-2-nitro-1,1-bis-(1-heptylthio)-1,3-butadiene (5) was obtained. From the reaction of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (1) with 2-isopropyl benzenethiol without solvent, 4-bromo-1,3,4-trichloro-2-nitro-1-[2-isopropylbenzenethio]-1,3-butadiene (12) and in the presence of NaOH in EtOH, 4-bromo-3,4-dichloro-2-nitro-1,1-bis-[2-isopropylbenzenethio]-1,3-butadiene (13) were synthesized. 4-Bromo-1,3,4-trichloro-2-nitro-1-[4-methoxyphenylthio]-1,3-butadiene (16) ve 4-bromo-3,4-dichloro-2-nitro-1,1-bis-[4-methoxyphenylthio]-1,3-butadiene (17) were obtained from the reaction of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (1) with 4-methoxythiophenol without solvent. From the direct reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 2-isopropyl benzenethiol, 2-nitro-1,3,4,4-tetrachloro-1-[2-isopropylbenzenethio]-1,3-butadiene (22) was synthesized. 2-Nitro-1,3,4,4-tetrachloro-1-[4-methoxyphenylthio]-1,3-butadiene (26) and 2-nitro-3,4,4-trichloro-1,1-bis-[4-methoxyphenylthio]-1,3-butadiene (27) were syntesized by the direct reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 4-methoxythiophenol.In the last step of the study, the reactions of mono(thio)substituted compounds which we were obtained, with morpholine, piperazine derivatives and amines were investigated. N,S-disubstituted nitrodiene compounds were synthesized.From the reactions of 4-bromo-1,3,4-trichloro-2-nitro-1-heptylthio-1,3-butadiene (3) with N-phenylpiperazine, N-(diphenylmethyl)piperazine, N-(4-fluorophenyl)piperazine, N-(2-fluorophenyl)piperazine, morpholine and piperazine, 4-bromo-3,4-dichloro-2-nitro-1-heptylthio-1-[N-phenylpiperazine]-1,3-butadiene (6), 4-bromo-3,4-dichloro-2-nitro-1-heptylthio-1-[N-(diphenylmethyl)-piperazine]-1,3-butadiene (7), 4-bromo-3,4-dichloro-2-nitro-1-heptylthio-1-[N-(4-fluorophenyl)piperazine]-1,3-butadiene (8), 4-bromo-3,4-dichloro-2-nitro-1-heptylthio-1-[N-(2-fluorophenyl)piperazine]-1,3-butadiene (9), 4-bromo-3,4-dichloro-2-nitro-1-heptylthio-1-morpholino-1,3-butadiene (10), N,N-bis[4-bromo-2-nitro-1-heptylthio-3,4-dichloro-1,3-butadienil]-piperazine (11) compounds were obtained. 4-Bromo-3,4-dichloro-2-nitro-1-[2- isopropylbenzenethio]]-1-[N-phenylpiperazine]-1,3-butadiene (14) and 4-bromo-3,4-dichloro-2-nitro-1-[2- isopropylbenzenethio]-1-[N-(diphenylmethyl)-piperazine]-1,3-butadiene (15) were synthesized by the reactions of 4-bromo-1,3,4-trichloro-2-nitro-1-[2-isopropylbenzenethio]-1,3-butadiene (12) with N-phenylpiperazine, N-(diphenylmethyl) piperazine. From the reactions of 4-bromo-1,3,4-trichloro-2-nitro-1-[4-methoxyphenylthio]-1,3-butadiene (16) with N-phenylpiperazine, N-(diphenylmethyl)-piperazine, dihexylamine and N-methylcyclohexylamine, 4-bromo-3,4-dichloro-2-nitro-1-[4-methoxyphenylthio]-1-[N-phenylpiperazine]-1,3-butadiene (18), 4-bromo-3,4-dichloro-2-nitro-1-[4-methoxyphenylthio]-1-[N-(diphenylmethyl)-piperazine]-1,3-butadiene(19), 4-bromo-3,4-dichloro-2-nitro-1-[4-methoxyphenylthio]-1-dihexylamine-1,3-butadiene (20), 4-bromo-3,4-dichloro-2-nitro-1-[4-methoxyphenylthio]-1-[N-methylcyclohexylamine]-1,3-butadiene (21) compounds were obtained. 2-Nitro-3,4,4-trichloro-1-[2-isopropylbenzenethio]-1-[N-phenylpiperazine]-1,3-butadiene (23), 2-nitro-3,4,4-trichloro-1-[2-isopropylbenzenethio]-1-[N-(diphenylmethyl)-piperazine]-1,3-butadiene (24), 2-nitro-3,4,4-trichloro-1-[2-isopropylbenzenethio]-1-[N-(4- fluorophenyl)piperazine]-1,3-butadiene (25) were synthesized from the reactions of 2-nitro-1,3,4,4-tetrachloro-1-[2-isopropylbenzenethio]-1,3-butadiene (22) with N-phenylpiperazine, N-(diphenylmethyl)piperazine, N-(4-fluorophenyl)piperazine. From the reactions of 2-nitro-1,3,4,4-tetrachloro-1-[4-methoxyphenylthio]-1,3-butadiene (26) with N-phenylpiperazine, N-(diphenylmethyl)piperazine, N-(4-fluorophenyl)piperazine, morpholine, dihexylamine and N-methylcyclohexylamine, 2-nitro-3,4,4-trichloro-1-[4-methoxyphenylthio]-1-[N-phenylpiperazine]-1,3-butadiene (28), 2-nitro-3,4,4-trichloro-1-[4-methoxyphenylthio]-1-[N-(diphenylmethyl) piperazine]-1,3-butadiene (29), 2-nitro-3,4,4-trichloro-1-[4-methoxyphenylthio]-1-[N-(4-fluorophenyl)piperazine]-1,3-butadiene (30), 2-nitro-3,4,4-trichloro-1-[4-methoxyphenylthio]-1-morpholino-1,3-butadiene (31) 2-nitro-3,4,4-trichloro-1-[4-methoxyphenylthio]-1-dihexylamine-1,3-butadiene (32), 2-nitro-3,4,4-trichloro-1-[4-methoxyphenylthio]-1-[N-methylcyclohexylamine]-1,3-butadiene (33) compounds were synthesized.These novel products were purified either via crystallization or column chromatography. The structures of these newly products were characterized by microanalysis, spectroscopic methods (FTIR, 1H-NMR, 13C-NMR, UV-Vis, and MS).