Perhalonitrobutadienlerden s- ve n-, s-sübstitüe tiyoeterlerin sentezi
The synthesis of s- and n-, s-substituted thioethers from perhalonitrobutadienes
Yazar: YASEMİN ÖZDAMAR
Danışman: YRD. DOÇ. DR. SERDAR GÖKŞİN AYDINLI
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2017
Konu: Kimya = Chemistry

Özet:
Perhalonitro-1,3-butadienler, güncel araştırmalarda kullanım alanı geniş, organik sentez ve farmasötik alanda önemli özelliklere sahip, oldukça fonksiyonel heterosiklik bileşiklerin sentezi için önemli başlangıç maddeleridir. Bu çalışmada Trikloretilen'den çıkılarak birkaç aşamada sentezlenen 2-Nitropentakloro-1,3-butadien (1) bileşiği başlangıç maddesi olarak kullanılmıştır.

Çalışmanın ilk aşamasında 2-Nitropentakloro-1,3-butadien (1) bileşiği, 1-Oktiltiyol ve 4-Metoksitiyofenol bileşikleri ile doğrudan reaksiyona sokuldu. Reaksiyon sonucunda sırasıyla bilinen 2-Nitro-1,3,4,4-tetrakloro-1-oktiltiyo-1,3-butadien (2) ve 2-Nitro-1,3,4,4-tetrakloro-1-(4-metoksifeniltiyo)-1,3-butadien (3) monotiyosübstitüe perhalonitro-1,3-butadien bileşikleri elde edildi. Son olarak sentezlenen (2) ve (3) bileşikleri bazı aromatik ve heterosiklik amin bileşikleri ile reaksiyona sokuldu. Reaksiyon sonucunda bilinmeyen yeni N,S-sübstitüe perhalonitro-1,3-butadien bileşikleri elde edildi. (2) bileşiği sırasıyla 1-(2-Furoil)piperazin, 1-(3,4-Diklorofenil)piperazin, 1-Bis(4-florofenil)metilpiperazin, 1-(4-Florobenzil)piperazin, 1-(2-Piridil)piperazin, 4-Morfolinoanilin ve β-Naftilamin ve ile reaksiyona sokuldu. Reaksiyon sonucunda sırası ile (4-(3,4,4-Trikloro-2-nitro-1-(oktiltiyo)buta-1,3-dien-1-il)piperazin-1-il)(furan-2-il)metanon (4), 1-(3,4-Diklorofenil)-4-(3,4,4-trikloro-2-nitro-1-(oktiltiyo)buta-1,3-dien-1-il)piperazin (6), 1-(Bis(4-florofenil)metil)-4-(3,4,4-trikloro-2-nitro-1-(oktiltiyo)buta-1,3-dien-1-il)piperazin (8), 1-(4-Florobenzil)-4-(3,4,4-trikloro-2-nitro-1-(oktiltiyo)buta-1,3-dien-1-il)piperazin (10), 1-(Piridin-2-il)-4-(3,4,4-trikloro-2-nitro-1-(oktiltiyo)buta-1,3-dien-1-il)piperazin (12), 4-Morfolino-N-(3,4,4-trikloro-2-nitro-1-(oktiltiyo)buta-1,3-dien-1-il)anilin (14) ve N-(3,4,4-Trikloro-2-nitro-1-(oktiltiyo)buta-1,3-dien-1-il)naftalin-2-amin (16) bileşikleri sentezlendi. (3) bileşiği aynı aminlerle reaksiyona sokulduğunda sırası ile (4-(3,4,4-Trikloro-1-(4-metoksifeniltiyo)-2-nitrobuta-1,3-dien-1-il)piperazin-1-il)(furan-2-il)metanon (5), 1-(3,4-Diklorofenil)-4-(3,4,4-trikloro-1-(4-metoksifeniltiyo)-2-nitrobuta-1,3-dien-1-il)piperazin (7), 1-(Bis(4-florofenil)metil)-4-(3,4,4-trikloro-1-(4-metoksifeniltiyo)-2-nitrobuta-1,3-dien-1-il)piperazin (9), 1-(4-Florobenzil)-4-(3,4,4-trikloro-1-(4-metoksifeniltiyo)-2-nitrobuta-1,3-dien-1-il)piperazin (11), 1-(Piridin-2-il)-4-(3,4,4-trikloro-1-(4-metoksifeniltiyo)-2-nitrobuta-1,3-dien-1-il)piperazin (13), 4-Morfolino-N-(3,4,4-trikloro-1-(4-metoksifeniltiyo)-2-nitrobuta-1,3-dien-1-il)anilin (15) ve N-(3,4,4-Trikloro-1-(4-metoksifeniltiyo)-2-nitrobuta-1,3-dien-1-il)naftalin-2-amin (17) bileşikleri sentezlendi.
Bu çalışmada ondört adet yeni bileşik sentezlenmiştir. Elde edilen bileşikler kolon kromatografisi veya kristallendirme yöntemi ile saflaştırıldı. Bileşiklerin yapıları spektroskopik yöntemler (IR, MS, 1H- ve 13C-NMR) ile aydınlatıldı.

Bu çalışma İstanbul Üniversitesi Bilimsel Araştırma Projeleri Koordinasyon Birimi
tarafından desteklenmiştir. Proje numarası : FYL-2016-20351

Abstract:
Perhalonitro-1,3-butadienes, are valuable starting materials for the synthesis of highly functionalized heterocycles which became topic of recent investigations due to wide variety of synthetically and pharmacologically important properties. In this work, 2-Nitropentachloro-1,3-butadiene (1) compound obtained in several steps from Trichloroethylene was used as a starting material.

Firstly, 2-Nitropentachloro-1,3-butadiene (1) compound was directly reacted with 1-Octylthiol and 4-Methoxythiophenol compounds. As a result of the reaction, previously  known monothio substituted perhalonitro-1,3-butadiene compounds 2-Nitro-1,3,4,4-tetrachloro-1-(octylthio)-1,3-butadiene (2) and 2-Nitro-1,3,4,4-tetrachloro-1-(4-methoxy phenylthio)-1,3-butadiene (3) were obtained respectively. After that, compounds (2) and	(3) were reacted with some aromatic and heterocyclic amine compounds. As a result of the reaction, new and previously unknown N,S-substituted perhalonitro-1,3-butadiene compounds were obtained. Compound (2) was reacted with 1-2(Furoyl)piperazine, 1-(3,4-Dichlorophenyl)piperazine, 1-Bis(4-fluorophenyl)methyl piperazine, 1-(4-Fluorobenzyl)piperazine, 1-(2-Pyridyl)piperazine, 4-Morpholinoaniline and β-Naphthylamine, respectively. As a result of the reaction, (4-(3,4,4-trichloro-2-nitro-1-(octylthio)buta-1,3-dien-1-yl)piperazin-1-yl)(furan-2-yl)methanone (4), 1-(3,4-Dichlorophenyl)-4-(3,4,4-trichloro-2-nitro-1-(octylthio)buta-1,3-dien-1-yl)piperazine (6), 1-(Bis(4-fluorophenyl)methyl)-4-(3,4,4-trichloro-2-nitro-1-(octylthio)buta-1,3-dien-1-yl)piperazine (8), 1-(4-Fluorobenzyl)-4-(3,4,4-trichloro-2-nitro-1-(octylthio)buta-1,3-dien-1-yl)piperazine (10), N-(3,4,4-Trichloro-2-nitro-1-(octylthio)buta-1,3-dien-1-yl)naphthalen-2-amine (12), 4-Morpholino-N-(3,4,4-trichloro-2-nitro-1-(octylthio)buta-1,3-dien-1-yl)aniline (14) 1-(Pyridin-2-yl)-4-(3,4,4-trichloro-2-nitro-1-(octylthio)buta-1,3-dien-1-yl)piperazine (16) compounds were synthesized, respectively. In the same way, compound (3) was reacted with the same amines. As a result of the reaction, (4-(3,4,4-trichloro-1-(4-methoxyphenylthio)-2-nitrobuta-1,3-dien-1-yl)piperazin-1-yl)(furan-2-yl)methanone (5), 1-(3,4-Dichlorophenyl)-4-(3,4,4-trichloro-1-(4-methoxyphenylthio)-2-nitrobuta-1,3-dien-1-yl)piperazine (7), 1-(Bis(4-fluorophenyl)methyl)-4-(3,4,4-trichloro-1-(4-methoxyphenylthio)-2-nitrobuta-1,3-dien-1-yl)piperazine (9), 1-(4-Fluorobenzyl)-4-(3,4,4-trichloro-1-(4-methoxyphenylthio)-2-nitrobuta-1,3-dien-1-yl)piperazine (11), 1-(Pyridin-2-yl)-4-(3,4,4-trichloro-1-(4-methoxyphenylthio)-2-nitrobuta-1,3-dien-1-yl)piperazine (13), 4-Morpholino-N-(3,4,4-trichloro-2-nitro-1-(4-methoxyphenylthio)buta-1,3-dien-1-yl)aniline (15), N-(3,4,4-Trichloro-1-(4-methoxyphenylthio)-2-nitrobuta-1,3-dien-1-yl)naphthalen-2-amine (17), compounds were synthesized, respectively.
The new fourteen compounds were synthesized. The obtained compounds were purified by column chromatography or crystallization. The structures of the compounds were elucidated by spectroscopic methods (IR, MS, 1H- ve 13C-NMR).

This work was supported by Scientific Research Projects Coordination Unit of Istanbul
University. Project number : FYL-2016-20351