Nitrodienlerin alifatik ve aromatik tiyolatlarla reaksiyonundan yeni mono- ve politiyoeterlerin sentezi
Synthesis of mono- and polythioethers from the reaction of nitrodienes with aliphatic and aromatic thiolates
Yazar: AMAÇ FATİH TUYUN
Danışman: PROF. DR. CEMİL İBİŞ
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Organik Kimya Ana Bilim Dalı
Derece: Doktora, 2012
Konu: Kimya = Chemistry
Dizin: Aminler = Amines ; Nitro bileşikleri = Nitro compounds ; Poliorganilthio-1,3-butadien = Polyorganylthio-1,3-butadiene ; Tiyoller = Thiols

Özet:
Bu çalışmaya trikloroetilen'in radikalik dimerleşmesi ile hazırlanan polihalojenli organik bileşiğin sentezlenmesi ve bu bileşiğin çeşitli reaksiyonları ile elde edilen 1,1,3,4,4-pentaklor-2-nitro-buta-1,3-dien bileşiğinin (8) ve 1,1,3,4-tetraklor-2,4-dinitro-buta-1,3-dien bileşiğinin (9) sentezlenmeleri ile başlandı.Çalışmanın sonraki aşamasında 1,1,3,4,4-pentaklor-2-nitro-buta-1,3-dien bileşiğinin (8) ve 1,1,3,4-tetraklor-2,4-dinitro-buta-1,3-dien (9) bileşiğinin tiyollerle olan reaksiyonları incelendi. Çalışmada 1,1,3,4,4-pentaklor-2-nitro-buta-1,3-dien bileşiğinin (8) bileşiğinin 2-merkaptobenzotiyazol (17) ile reaksiyonundan 3,4,4-triklor-2-nitro-1,1-di(benzo-1,3-tiyazolil-(2)-tiyo)-buta-1,3-dien (18) ve 4,4-diklor-2-nitro-1,1,3-tri(benzo-1,3-tiyazolil-(2)-tiyo)-buta-1,3-dien (19) bileşikleri elde edildi. Aynı şekilde, çalışmada 1,1,3,4-tetraklor-2,4-dinitro-buta-1,3-dien bileşiğinin (9) 1-oktantiyol (20), p-metilbenzentiyol (23), p-klorbenzentiyol (28), p-brombenzentiyol (32), 1-heptantiyol (35), benzil merkaptan (37), 1-etantiyol (40) ve 2,3,5,6-tetraflorbenzentiyol (43) ile reaksiyonundan 1,3,4-triklor-2,4-dinitro-1-oktiltiyo-buta-1,3-dien (21), 3,4-diklor-2,4-dinitro-1,1-dioktiltiyo-1,3-butadien (22), 1,3,4-triklor-2,4-dinitro-1-(4-metilfeniltiyo)-buta-1,3-dien (24), 3,4-diklor-2,4-dinitro-1,1-di(4-metilfeniltiyo)-buta-1,3-dien (25), 4-klor-2,4-dinitro-1,1,3-tri(4-metilfeniltiyo)-buta-1,3-dien (26), 2,4-dinitro-1,1,3,4-tetra(4-metilfeniltiyo)-buta-1,3-dien (27), 3,4-diklor-2,4-dinitro-1,1-di(4-klorfeniltiyo)-buta-1,3-dien (29), 4-klor-2,4-dinitro-1,1,3-tri(4-klorfeniltiyo)-buta-1,3-dien (30), 2,4-dinitro-1,1,3,4-tetra(4-klorfeniltiyo)-buta-1,3-dien (31), 4-klor-2,4-dinitro-1,1,3-tri(4-bromfeniltiyo)-buta-1,3-dien (33), 2,4-dinitro-1,1,3,4-tetra(4-bromfeniltiyo)-buta-1,3-dien (34), 2,4-dinitro-1,1,3,4-tetra(heptiltiyo)-buta-1,3-dien (36), 1,3,4-diklor-2,4-dinitro-1-(benziltiyo)-buta-1,3-dien (38), 3,4-diklor-2,4-dinitro-1,1-di(benziltiyo)-buta-1,3-dien (39), 1,3,4-triklor-2,4-dinitro-1-etiltiyo-buta-1,3-dien (41), 4-klor-2,4-dinitro-1,1,3-trietiltiyo-buta-1,3-dien (42), 1,3,4-triklor-2,4-dinitro-1-(2,3,5,6-tetraflor)benzentiyo-buta-1,3-dien (44) ve 3,4-diklor-2,4-dinitro-1,1-di(2,3,5,6-tetraflor)benzentiyo-buta-1,3-dien (45) bileşikleri sentezlendi.Çalışmanın ikinci aşamasında ise elde edilen mono(tiyo)sübstitüe dinitrodien bileşiklerinin pirolidin, morfolin ve piperidin ile reaksiyonları incelendi. Sırasıyla pirolidin (57), morfolin (59), piperidin (61) ve N-fenil-piperazin (64) ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 3,4-diklor-2,4-dinitro-1-pirolidin-1-oktiltiyo-buta-1,3-dien (58), 3,4-diklor-1-morfolin-2,4-dinitro-1-oktiltiyo-buta-1,3-dien (60), 3,4-diklor-2,4-dinitro-1-piperidin-1-oktiltiyo-buta-1,3-dien (62) ve 4-klor-2,4-dinitro-1,3-di(N-fenilpiperazin)-1-oktiltiyo-buta-1,3-dien (65) bileşikleri sentezlendi.Çalışmanın üçüncü aşamasında ise elde edilen di(tiyo)sübstitüe dinitrodien bileşiklerinin pirolidin, morfolin ve piperidin ile reaksiyonları incelendi. Sırasıyla pirolidin (57), piperidin (61) ve morfolin (59) ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 4-klor-2,4-dinitro-3-pirolidin-1,1-dioktiltiyo-buta-1,3-dien (63), 4-klor-2,4-dinitro-3-piperidin-1,1-di(4-klorfeniltiyo)-buta-1,3-dien (66), 4-klor-3-morfolin-2,4-dinitro-1,1-di(4-metilfeniltiyo)-buta-1,3-dien (67) ve 4-klor-2,4-dinitro-3-piperidin-1,1-di(4-metilfeniltiyo)-buta-1,3-dien (68) bileşikleri sentezlendi.Çalışmanın son aşamasında ise 1,1,3,4-tetraklor-2,4-dinitro-buta-1,3-dien (9) bileşiğinin siklizasyon reaksiyonları incelendi. Sırasıyla 1,2-etanditiyol (46), 1,3-propanditiol (48), 2-aminotiyofenol (51), 2-amino-4-klor-tiyofenol (53) ve pentaeritritol tetrakis(3-merkaptopropiyonat) (55) ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 2-(2,3-diklor-1,3-dinitroalliliden)-1,3-ditiyolan (47), 2-(2,3-diklor-1,3-dinitroalliliden)-1,3-ditiyan (49), 1,3-di((1,3,4-triklor-2,4-dinitrobuta-1,3-dien-1-il)tiyo)propan (50), 2-(2,3-diklor-1,3-dinitroalliliden)-2,3-dihidrobenzo[d]tiyazol (52), 5-klor-2-(2,3-diklor-1,3-dinitroalliliden)-2,3-dihidrobenzo[d]tiyazol (54) ve 7-(2,3-diklor-1,3-dinitroalliliden)-21-(2,3-diklor-1,3-dinitroalliliden)-2,12,16,26-tetraoksa-6,8,20,22-tetratiyaspiro[13.13]heptakosan-3,11,17,25-tetraon (56) bileşikleri sentezlendi.Sentezlenen mono-, poli- ve persübstitüe 2,4-dinitro-buta-1,3-dien bileşikleri yenidir. Oluşan bu yeni ürünler kristallendirme veya kolon kromotografisi yöntemlerinden biriyle saflaştırıldı. Yapıları mikroanaliz ve spektroskopik yöntemler (FTIR, 1H-NMR, 13C-NMR, UV-Vis ve MS) ile aydınlatıldı.

Abstract:
Our investigations started with the synthesis of polyhalogenated butenes which is easily obtained from the radical dimerization of trichloroethylene and its subsequent reactions leading to the compounds 1,1,3,4,4-pentachloro-2-nitro-buta-1,3-dien (8) and 1,1,3,4-tetrachloro-2,4-dinitro-buta-1,3-dien (9).In the following step, reactions of thiols with 1,1,3,4,4-pentachloro-2-nitro-buta-1,3-dien (8) and 1,1,3,4-tetrachloro-2,4-dinitro-buta-1,3-dien (9) were investigated. Therefore, 3,4,4-trichloro-2-nitro-1,1-di(benzo-1,3-thiazoyl-(2)-thio)-buta-1,3-dien (18) and 4,4-trichloro-2-nitro-1,1,3-tri(benzo-1,3-thiazoyl-(2)-thio)-buta-1,3-dien (19) were synthesized from the reactions of 1,1,3,4,4-pentachloro-2-nitro-buta-1,3-dien (8) with 2-mercaptobenzothiazole (17). Similarly, 1,3,4-trichloro-2,4-dinitro-1-octylthio-buta-1,3-dien (21), 3,4-dichloro-2,4-dinitro-1,1-dioctylthio-1,3-butadien (22), 1,3,4-trichloro-2,4-dinitro-1-(4-methylphenylthio)-buta-1,3-dien (24), 3,4-dichloro-2,4-dinitro-1,1-di(4-methylphenylthio)-buta-1,3-dien (25), 4-chloro-2,4-dinitro-1,1,3-tri(4-methylphenylthio)-buta-1,3-dien (26), 2,4-dinitro-1,1,3,4-tetra(4-methylphenylthio)-buta-1,3-dien (27), 3,4-dichloro-2,4-dinitro-1,1-di(4-chlorophenylthio)-buta-1,3-dien (29), 4-chloro-2,4-dinitro-1,1,3-tri(4-chlorophenylthio)-buta-1,3-dien (30), 2,4-dinitro-1,1,3,4-tetra(4-chlorophenylthio)-buta-1,3-dien (31), 4-chloro-2,4-dinitro-1,1,3-tri(4-bromphenylthio)-buta-1,3-dien (33), 2,4-dinitro-1,1,3,4-tetra(4-bromphenylthio)-buta-1,3-dien (34), 2,4-dinitro-1,1,3,4-tetra(heptylthio)-buta-1,3-dien (36), 1,3,4-dichloro-2,4-dinitro-1-(benzilthio)-buta-1,3-dien (38), 3,4-dichloro-2,4-dinitro-1,1-di(benzylthio)-buta-1,3-dien (39), 1,3,4-trichloro-2,4-dinitro-1-ethylthio-buta-1,3-dien (41), 4-chloro-2,4-dinitro-1,1,3-triethylthio-buta-1,3-dien (42), 1,3,4-trichloro-2,4-dinitro-1-(2,3,5,6-tetrafloro)benzenethio-buta-1,3-dien (44), and 3,4-dichloro-2,4-dinitro-1,1-di(2,3,5,6-tetrafloro)benzenethio-buta-1,3-dien (45) were synthesized from the reactions of 1,1,3,4-tetrachloro-2,4-dinitro-buta-1,3-dien (9) with 1-octanethiol (20), p-methylbenzenethiol (23), p-chlorobenzenethiol (28), p-bromobenzenethiol (32), 1-heptanethiol (35), benzyl mercaptan (37), 1-ethanethiol (40), and 2,3,5,6-tetraflorobenzenethiol (43), respectively.In the second step of the study, reactions of pyrrolidine (57), morpholine (59), piperidine (61), and N-phenyl-piperazine (64) with mono(thio)substituted dinitrodien compounds were explored. Therefore, 3,4-dichloro-2,4-dinitro-1-pyrrolidine-1-octylthio-buta-1,3-dien (58), 3,4-dichloro-1-morpholine-2,4-dinitro-1-octylthio-buta-1,3-dien (60), 3,4-dichloro-2,4-dinitro-1-piperidine-1-octylthio-buta-1,3-dien (62), and 4-chloro-2,4-dinitro-1,3-di(N-phenylpiperazine)-1-octylthio-buta-1,3-dien (65) were synthesized from the reactions of mono(thio)substituted dinitrodien compounds with pyrrolidine (57), morpholine (59), piperidine (61), and N-phenyl-piperazine (64), respectively.In the third step of the study, reactions of pyrrolidine (57), morpholine (59), and piperidine (61) with di(thio)substituted dinitrodien compounds were explored. Therefore, 4-chloro-2,4-dinitro-3-pyrrolidine-1,1-dioctylthio-buta-1,3-dien (63), 4-chloro-2,4-dinitro-3-piperidine-1,1-di(4-chlorophenylthio)-buta-1,3-dien (66), 4-chloro-3-morpholine-2,4-dinitro-1,1-di(4-methylphenylthio)-buta-1,3-dien (67), and 4-chloro-2,4-dinitro-3-piperidine-1,1-di(4-methylphenylthio)-buta-1,3-dien (68) were synthesized from the reactions of di(thio)substituted dinitrodien compounds with pyrrolidine (57), morpholine (59), and piperidine (61), respectively.Analogously, in the last step of the study, cyclization reactions of 1,1,3,4-tetrachloro-2,4-dinitro-buta-1,3-dien (9) were explored. Therefore, 2-(2,3-dichloro-1,3-dinitroallylidene)-1,3-dithiolane (47), 2-(2,3-dichloro-1,3-dinitroallylidene)-1,3-dithiane (49), 1,3-di((1,3,4-trichloro-2,4-dinitrobuta-1,3-dien-1-yl)thio)propane (50), 2-(2,3-dichloro-1,3-dinitroallylidene)-2,3-dihydrobenzo[d]thiazole (52), 5-chloro-2-(2,3-dichloro-1,3-dinitroallylidene)-2,3-dihydrobenzo[d]thiazole (54), and 7-(2,3-dichloro-1,3-dinitroallylidene)-21-(2,3-dichloro-1,3-dinitroallylidene)-2,12,16,26-tetraoxa-6,8,20,22-tetrathiaspiro[13.13]heptacosane-3,11,17,25-tetraone (56) were synthesized from the reactions of 1,1,3,4-tetrachloro-2,4-dinitro-buta-1,3-dien (9) with 1,2-ethanedithiol (46), 1,3-propanedithiol (48), 2-aminothiophenol (51), 4-chloro-2-amino-thiophenol (53), and pentaerythritol tetrakis(3-mercaptopropionate) (55), respectively.Synthesized mono-, poly-, and persubstituted 2,4-dinitro-buta-1,3-dien compounds are new. The novel products were purified either via crystallization or column chromatography. Structure of these novel products were characterized by microanalysis, spectroscopic methods (FTIR, 1H-NMR, 13C-NMR, UV-Vis, and MS).