1,3-butadienil gruplu bazı yeni tiyoeterlerin sentezi
The synthesis of some new thioethers having 1,3-butadienyl groups
Yazar: FUNDA ÖZKÖK
Danışman: PROF. DR. CEMİL İBİŞ
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Doktora, 2010
Konu: Kimya = Chemistry
Dizin: Kimya = Chemistry ; Kristal yapı = Crystal structure ; Kristalografi = Crystallography ; Organik = Organic ; Organik kimya = Organic chemistry ; Organik madde bileşikleri = Organic matter compounds ; Organik moleküller = Organic molekules ; Sentez = Synthesis ; Tiyoeterler = Thioethers ; Tiyoller = Thiols

Özet:
Çalışmamızda başlangıç maddeleri olarak 2H-1,1,3,4,4-pentaklor-1,3-butadien (1), 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2) ve 4-Brom-2H-1,1,3,4-tetraklor-1,3-butadien (3) bileşikleri kullanıldı.2H-1,1,3,4,4-pentaklor-1,3-butadien (1)'in 4,4´-Tiyobisbenzentiyol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni Benzen-1,1'-tiyobis[4-(3,4,4-triklor-1-butenil)tiyo] (30) bileşiği elde edildi.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)'in 2-merkaptofenol ile çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen yeni 3,4,4-Triklor-1-[benzo(1,3-oksatiya)]-2-nitro-1,3-butadien (4) bileşiği elde edildi.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)'in Tiyosalisilik asit ile çözücüsüz ortamdaki reaksiyonundan bilinmeyen yeni 1,1-Bis(2-Karboksifeniltiyo)-3,4,4-triklor-2-nitro-1,3-butadien (5) bileşiği elde edildi.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)'in o-tiyokresol ile çözücüsüz ortamdaki reaksiyonundan bilinmeyen yeni 2-Nitro-1,3,4,4-tetraklor-1-(2-Metilfeniltiyo)-1,3-butadien (6) ve 1,1-Bis(2-Metilfeniltiyo)-3,4,4-triklor-2-nitro-1,3-butadien (7) bileşiği elde edildi.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)'in o-tiyokresol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni 1,1,4-Tris(2-Metilfeniltiyo)-3,4-diklor-2-nitro-1,3-butadien (17) bileşiği elde edildi.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)'in 2,4-dimetilbenzentiyol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni 1,1-Bis(2,4-Dimetilfeniltiyo)-3,4,4-triklor-2-nitro-1,3-butadien (18) bileşiği ve 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)'in 2,4-dimetilbenzentiyol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni 1,1,4-Tris(2,4-Dimetilfeniltiyo)-3,4-diklor-2-nitro-1,3-butadien (19) bileşiği elde edildi.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)'in 3-Tiyometil-3-propiyonat ile çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen yeni 2-Nitro-1,3,4,4-tetraklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadien (20) bileşiği ve 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)'in 4,4'-Tiyobisbenzentiyol ile çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen yeni Benzen-1,1'-tiyobis[4-(1,3,4,4-tetraklor-2-nitro-1,3-butadienil)tiyo] (29) bileşiği elde edildi.4-Brom-2H-1,1,3,4-tetraklor-1,3-butadien (3)'in 4,4'-Tiyobisbenzentiyol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni Benzen-1,1'-tiyobis[4-(3,4-diklor-4-brom-1-butenil)tiyo] (31) bileşiği elde edildi.Çalışmamızın ikinci aşamasında, elde edilen mono(tiyo)sübstitüe nitrodien bileşiklerinin bazı piperazin türevleri, morfolin türevleri ve piperidin türevleri ile reaksiyonları incelendi.2-Nitro-1,3,4,4-tetraklor-1-(2-Metilfeniltiyo)-1,3-butadien (6) bileşiği, sırasıyla 1-(2-Florfenil)piperazin, 1-(4-Florfenil)piperazin, N-fenilpiperazin, 1-(2-Metoksifenil)piperazin, 1-(Difenilmetil)piperazin, 1-(4-Nitrofenil)piperazin, 1-(4-Hidroksifenil)piperazin, N-morfolin, 4-(2-Aminoetil)morfolin ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla bilinmeyen yeni 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(2-florfenil)piperazin (8), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(4-florfenil)piperazin (9), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(1-fenil)piperazin (10), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(2-metoksifenil)piperazin (11), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(1-Difenilmetil) piperazin (12), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(4-Nitrofenil)piperazin (13), 1- [2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil] -4-(4-hidroksifenil) piperazin (14), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-morfolin (15), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(2-aminoetil)morfolin (16) bileşikleri sentezlendi.2-Nitro-1,3,4,4-tetraklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadien (20) bileşiği, sırasıyla 1-(4-Florfenil)piperazin, 1-(2-Metoksifenil)piperazin, 1-(4-nitrofenil)piperazin, N-fenilpiperazin, 1-(2-Florfenil)piperazin, N-morfolin, N-piperidin, 1-(4-Metil)piperidin ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla bilinmeyen yeni 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(4-florfenil)piperazin (21), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(2-Metoksifenil)piperazin (22), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(4-nitrofenil)piperazin (23), 1-[ 2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(1-Fenil)piperazin (24), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(2-Florfenil)piperazin (25), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-morfolin (26), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-piperidin (27), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(4-Metil)piperidin (28) bileşikleri kazanıldı.Sentezlenen bu yeni bileşikler kristallendirme veya kolon kromatografisi yöntemleri ile saflaştırıldı. Bileşiklerin yapısı mikro analiz ve spektroskopik yöntemlerle (-IR, -1H-NMR, -13C-NMR veya -APT-NMR, -UV ve ?MS) ile aydınlatıldı. Bazı yeni bileşiklerin X-ışınları kristalografisi ile konformasyonal yapısı aydınlatıldı.

Abstract:
In our study, 2H-1,1,3,4,4-pentachloro-1,3-butadiene (1), 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) and 4-Bromo-2H-1,1,3,4-tetrachloro-1,3-butadiene (3) compounds were used as starting compounds.The unknown, new compound Benzene-1,1?-thiobis[4-(3,4,4-trichloro-1-butenyl)thio] (30) was obtained from the reaction of 2H-1,1,3,4,4-pentachloro-1,3-butadiene (1) with 4,4?-thiobisbenzenethiol in the presence of NaOH in ethanol.The unknown, new compound 3,4,4-Trichloro-1-[benzo(1,3-oxathia)]-2-nitro-1,3-butadiene (4) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 4,4?-thiobisbenzenethiol.The unknown, new compound 1,1-Bis(2-Carboxyphenylthio)-3,4,4-trichloro-2-nitro-1,3-butadiene (5) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with thiosalicylic acid.The unknown, new compounds 2-Nitro-1,3,4,4-tetrachloro-1-(2-Methylphenylthio)-1,3-butadiene (6) and 1,1-Bis(2-Methylphenylthio)-3,4,4-trichloro-2-nitro-1,3-butadiene (7) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with o-thiocresol.The unknown, new compound 1,1,4-Tris(2-Methylphenylthio)-3,4-dichloro-2-nitro-1,3-butadiene (17) was obtained from the reaction of with 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with o-thiocresol in the presence of NaOH in ethanol.The unknown, new compound 1,1-Bis(2,4-Dimethylphenylthio)-3,4,4-trichloro-2-nitro-1,3-butadiene (18) was obtained from the reaction of with 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 2,4-dimethylbenzenethiol in the presence of NaOH in ethanol.The unknown, new compound 1,1,4-Tris(2,4-Dimethylphenylthio)-3,4-dichloro-2-nitro-1,3-butadiene (19) was obtained from the reaction of with 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 2,4-dimethylbenzenethiol in the presence of NaOH in ethanol.The unknown, new compound 2-Nitro-1,3,4,4-tetrachloro-1-(3-butyl-3-propionyl)-1,3-butadiene (20) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 3-Thiomethyl-3-propionate.The unknown, new compound Benzene-1,1?-thiobis[4-(1,3,4,4-tetrachloro-2-nitro-1,3-butadienyl)thio] (29) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 4,4?-Thiobisbenzenethiol.The unknown, new compound Benzene-1,1?-thiobis[4-(3,4-dichloro-4-bromo-1-butenyl)thio] (31) was obtained from the reaction of 4-Bromo-2H-1,1,3,4-tetrachloro-1,3-butadiene (3) with 4,4?-Thiobisbenzenethiol in the presence of NaOH in ethanol.In the second step, reactions of derivatives of some piperazine, morpholine and piperidine with the mono(thio)substituted nitrodiene compounds were investigated.The unknown, new compounds 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(2-florophenyl)piperazine (8), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(4-florophenyl)piperazine (9), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(1-phenyl)piperazine (10), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl] -4-(2-metoxyphenyl)piperazine (11), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(1-Diphenylmethyl) piperazine (12), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(4-Nitrophenyl) piperazine(13), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(4-Hidroxyphenyl)piperazine (14), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-morfoline (15), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(2-aminoethyl)morfoline (16) were synthesized from the reactions of 2-Nitro-1,3,4,4-tetrachloro-1-(2-Methylphenylthio)-1,3-butadiene (6) with the 1-(2-Florophenyl)piperazine, 1-(4-Florophenyl)piperazine, N-phenylpiperazine, 1-(2-Metoxyphenyl)piperazine, 1-(Diphenylmethyl)piperazine, 1-(4-Nitrophenyl)piperazine, 1-(4-Hidroxyphenyl)piperazine, N-morfoline, 4-(2-Aminoethyl)morfoline, respectively.The unknown, new compounds 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-(4-florophenyl)piperazine (21), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-(2-Metoxyphenyl)piperazine (22), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl] -4-(4-nitrophenyl)piperazine (23), 1-[ 2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-(1-Phenyl)piperazine (24), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-(2-Florophenyl)piperazine (25), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-morfoline (26), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-piperidine (27), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl] -4-(4-Methyl)piperidine (28) were synthesized from the reactions of 2-Nitro-1,3,4,4-tetrachloro-1-(3-butyl-3-propionylthio)-1,3-butadiene (20) with the 1-(4-Florophenyl)piperazine, 1-(2-Metoxyphenyl)piperazine, 1-(4-nitrophenyl)piperazine, N-phenylpiperazine, 1-(2-Florophenyl)piperazine, N-morfoline, N-piperidine, 1-(4-Methyl)piperidine, respectively.Synthesized the new compounds were purified either crystallization or via column chromatography. Structure of these new compounds were characterized by microanalysis and spectroscopic methods (-IR, - 1H-NMR, - 13C-NMR or APT-NMR, -UV and ?MS). Some new compounds of conformational structure were characterized by X-Ray crystallography.