Halonitrodien ve halobutadienden yeni tiyoeterlerin sentezi
Synthesis of novel thioethers from halonitrodiene and halobutadienes
Yazar: VAHID HAIERI
Danışman: DOÇ. DR. SİBEL ŞAHİNLER AYLA
İstanbul Üniversitesi-Cerrahpaşa / Lisansüstü Eğitim Enstitüsü / Kimya Ana Bilim Dalı / Kimya Bilim Dalı
Derece: Doktora, 2021
Konu: Kimya = Chemistry
Dizin: Hekzaklorobütadien = Hexachlorobutadiene ; Poliorganilthio-1,3-butadien = Polyorganylthio-1,3-butadiene

Özet:
Bu çalışmada, 1,1,3,3,4,4-heksaklor-1-buten (1a) ve 2-nitro-pentakloro-1,3-butadien (1b) başlangıç maddelerinin S- ve N- nükleofillerle reaksiyonlarından bilinmeyen yeni sübstitüe 2H-klorobutadien ve 2-nitrobutadien bileşiklerinin sentezlendi. Bu amaçla ilk olarak trikloroetilenin benzoil peroksit varlığında radikalik dimerleşmesinden 1,1,3,3,4,4-heksaklor-1-buten (1a) elde edildi. Çalışmanın devamında 1,1,3,3,4,4-heksaklor-1-buten (1a)'in EtOH ve KOH varlığındaki reaksiyonundan 2H-pentakloro-1,3-butadien elde edildi. 2H-pentakloro-1,3-butadienin %58'lik HNO3 ile nitrolanması sonucunda 2-nitro-pentakloro-1,3-butadien (1b) sentezlendi.
İlk başlangıç maddemiz 1,1,3,3,4,4-heksaklor-1-butenin (1a) EtOH ve KOH varlığında oda sıcaklığında 2-dietilaminoetantiyol (2), 3-merkapto-3-metilbutan-1-ol (5), 2,2'-(etilendioksi) dietantiyol (9), bifenil-4,4′-ditiyol (12), 11-merkapto-1-undekanol (14), 3-Merkapto-2-butanon (17), Butil-3-merkapto propiyonat (23), trifenil metil merkaptan (25), 4-metoksibenzil merkaptan (27), 2-amino etantiyol (Sistamin) (29), 2-fenoksietantiyol (38) ile reaksiyonundan sırasıyla yeni N,N-dietil-2-((1,3,4,4-tetraklorobuta-1,3-dien-1-il)tiyo)etan-1-amin (3), 2,2'-((3,4,4-triklorobuta-1,3-dien-1,1-dil)bis(sülfandil))bis(N,N-dietiletan-1-amin) (4), 3,3'-((3,4,4-triklorobuta-1,3-dien-1,1-dil)bis(sülfandil))bis(3-metilbutan-1-ol) (6), 3,3',3'',3'''-((2-klorobuta-1,3-dien-1,1,4,4-tetrail)tetrakis(sülfandil))tetrakis(3-metilbutan-1-ol) (7), metil-3-((3,4,4-triklorobut-3-en-1-in-1-il)tioo)butan-1-ol (8), 8,8'-(1-kloroetan-1,2-diliden)bis(1,4-diokza-7,9-ditiasikloundekan) (10),1,1,2,3,15,17,18,18-octakloro-8,11-diokza-5,14-ditiaoktadeka-1,3,15,17-tetraen (11), 4,4'-bis(-1,3,4,4-tetraklorobuta-1,3-dien-1-yl)tiyo)-1,1'-bifenil (13), 11-((1,3,4,4-tetraklorobuta-1,3-dien-1-il)tiyo)undekan-1-ol (15), 11,11'-((3,4,4-triklorobuta-1,3-dien-1,1-dil)bis(sülfandil))bis(undekan-1-ol) (16), 3-((1,3,4,4-tetraklorobuta-1,3-dien-1-il)tiyo)(butan-2-on) (18), 3,3',3'',3'''-((2-klorobuta-1,3-dien-1,1,4,4-tetrail)tetrakis(sülfandil))tetrakis(butan-2-on) (19), butil-3-((1,3,4,4-tetraklorobuta-1,3-dien-1-il)tio)propanat (24), (3,4,4-(1,3,4,4-tetraklorobuta-1,3-dien-1-il)(tritil)sülfan (26), (3,4-diklorobuta-1,3-dien-1,1,4-tril)tris((4-metoksibenzil)sülfan) (28), 2-((1,3,4,4-tetraklorobuta-1,3-dien-1-il)tiyo)(etan-1-amin) (30),  2,2',2'',2'''-((2-klorobuta-1,3-dien-1,1,4,4-tetrail) tetrakis (sülfandil))tetrakis(etan-1-amin) (31) ve (3,4-diklorobuta-1,3-dien-1,1,4-tril)tris((2-fenoksietil)sülfan) (40) bileşikleri sentezlendi. 1,1,3,3,4,4-heksaklor-1-butenin (1a) DMF ve TEA varlığında oda sıcaklığında 1-naftalentiyol (20) ile reaksiyonunda ise yeni (3,4,4-triklorobuta-1,3-diene-1,1-dil)bis(naftalen-1-ilsülfan) (21), (3,4,4-triklorobuta-1,3-dien-1,1-dil)bis(naftalen-1-ilsülfan) (22) bileşikleri sentezlendi. 
Diğer başlangıç bileşiğimiz 2-Nitropentaklor-1,3-butadienin (1b) CH2Cl2 varlığında oda sıcaklığında 5-metoksi-1H-indol (35) ile reaksiyonundan ve 5-metoksi-3-(1,3,4,4-tetrakloro-2-nitrobuta-1,3-dien-1-il)-1H-indol (36) bileşiği sentezlendi. 2-Nitropentaklor-1,3-butadienin (1b) çözücüsüz ortamda 3-indol asetonitril (32), 2,2'-(etilendioksi) dietantiyol (9), 2-fenoksietantiyol (38) ile reaksiyonundan ise yeni 2-(2-(1,3,4,4-tetrakloro-2-nitrobuta-1,3-dien-1-il)-1H-indol-3-il) asetonitril (33),  2,2'-((3,4,4-trikloro-2-nitrobuta-1,3-dien-1,1-dil)bis(1H-indol-2,3-dil))diasetonitril (34), 8-(2,3,3-trikloro-1-nitroalliliden)-1,4-diokza-7,9-ditiasikloundekan (37), (2-kloro-3-nitrobuta-1,3-dien-1,1,4,4-tetrail)tetrakis((2-fenoksietil)sülfan) (39)  bileşikleri sentezlendi. 
Sentezlenen yeni bileşikler kromatografik yöntemler ile saflaştırıldı, yapıları IR, 1H-NMR, 13C-NMR, MS, UV gibi spektroskopik yöntemler kullanılarak aydınlatıldı.

Abstract:
In this study, novel substituted 2H-chlorobutadiene and 2-nitrobutadiene compounds were synthesized by reactions of 1,1,3,3,4,4-hexachlor-1-butene (1a) and 2-nitro-pentachloro-1,3-butadiene (1b) as starting materials with S- and N- nucleophiles. Therefore, firstly 1,1,3,3,4,4-hexachlor-1-butene (1a) was obtained from the radical dimerization of trichlorethylene in the presence of benzoyl peroxide. In the continuation of the study, 2H-pentachloro-1,3-butadiene was obtained by reaction of 1,1,3,3,4,4-hexachlor-1-butene (1a) in the presence of EtOH and KOH. 2-Nitro-pentachloro-1,3-butadiene (1b) was synthesized by nitration of 2H-pentachloro-1,3-butadiene with 58% HNO3.
N,N-diethyl-2-((1,3,4,4-tetrachlorobuta-1,3-dien-1-yl) thio) ethan-1-amine (3), 2,2'-((3,4,4-trichlorobuta-1,3-diene-1,1-diyl) bis(sulfanediyl)) bis(N,N-diethylethan-1-amine) (4), 3,3'- ((3,4,4-trichlorobuta-1,3-diene-1,1-diyl) bis(sulfanediyl) bis(3-methylbutan-1-ol) (6), 3,3',3'', 3'''-((2-chlorobuta-1,3-diene-1,1,4,4-tetrayl) tetrakis (sulfanediyl) tetrakis (3-methylbutan-1-ol) (7), methyl-3-((3,4,4-trichlorobut-3-en-1-yn-1-yl)thio)butan-1-ol (8), 8,8'-(1-chloroethane-1,2-diylidene)bis(1,4-dioxa-7,9-dithiacycloundecane) (10), 1,1,2,4,15,17,18,18-octachloro-8,11-dioxa-5,14-dithiaoctadeca-1,3,15,17-tetraene (11), 4,4'-bis-(1,3,4,4-tetrachlorobuta-1,3-dien-1-yl) thio) -1,1'-biphenyl (13), 11-((3,4,4-trichlorobut-3-en-1-yn-1-yl)thio)undecan-1-ol (15), 11,11'-((3,4,4-trichlorobuta-1,3-diene) -1,1-dil) bis (sulfanedyl) bis (undecan-1-ol) (16), 3-((1,3,4,4-tetrachlorobuta-1,3-dien-1-yl)thio)butan-2-one (18), 3,3', 3'', 3'''-((2-chlorobuta-1,3-diene-1,1,4,4-tetrail) tetrakis (sulfandyl)) tetrakis (butan-2-one) (19), butyl-3-((1,3,4,4-tetrachlorobuta-1,3-dien-1-yl)thio)propanate (24), (1,3,4,4-tetrachlorobuta-1,3-dien-1-yl)(trityl)sulfane (26), (3,4-dichlorobuta-1,3-diene-1,1,4-triyl)tris((4-methoxybenzyl)sulfane) (28), 2-((1,3,4,4-tetrachlorobuta-1,3-dien-1-yl) thio) ethane-1-amine (30), 2,2',2'',2'''-((2-chlorobuta-1,3-diene-1,1,4,4-tetrale) tetrakis (sulfandyl) tetrakis (ethane-1-amine) (31) and (3,4-dichlorobuta-1,3-diene-1,1,4-tryl) tris ((2-phenoxyethyl) sulfan) (40) compounds were synthesized from reactions of 1,1,3,3,4,4-hexachlor-1-butene (1a) as starting compound with 2-diethylaminoethanthiol (2), 3-mercapto-3-methylbutan-1-ol (5), 2,2'-(ethylenedioxy) diethanthiol (9), biphenyl-4,4′-dithiol (12), 11-mercapto -1-undecanol (14), 3-Mercapto-2-butanone (17), butyl-3-mercapto propionate (23), triphenyl methyl mercaptan (25), 4-methoxybenzyl mercaptan (27), 2-amino ethanethiol (Cystamine) (29), 2-phenoxyethanethiol (38) in the presence of EtOH and KOH at room temperature respectively. Other novel compounds 3,4,4-trichlorobuta-1,3-diene-1,1-diyl-bis(naphthalene-1-ylsulfane) (21) and (3,4,4-trichlorobuta-1,3-diene-1,1-dil) bis (naphthalen-1-ylsulfane) (22) were synthesized by reaction of 1,1,3,3,4,4-hexachlor-1-butene (1a) with 1-naphthalenethiol (20) in the presence of DMF and TEA at room temperature.
New compound 5-methoxy-3-(1,3,4,4-tetrachloro-2-nitrobuta-1,3-dien-1-yl)-1H-indole (36) was synthesized from reaction of 2-Nitropentachlor-1,3-butadiene (1b) as another starting compound with 5-methoxy-1H-indole (35) in the presence of CH2Cl2 at room temperature. Novel 2-(2-(1,3,4,4-tetrachloro-2-nitrobuta-1,3-dien-1-yl)-1H-indol-3-yl) acetonitrile (33), 2,2'-(3,4,4-trichloro-2-nitrobuta-1,3-diene-1,1-diyl)-bis-1H-indole-2,3-diyl))diacetonitrile(34), 8-(2,3,3-trichloro-1-nitroalllylidene)-1,4-dioxa-7,9-dithiacycloundecane (37) and (2-chloro-3-nitrobuta-1,3-diene-1,1,4,4-tetrale)tetrakis((2-phenoxyethyl) sulfane) (39) were synthesized from reaction of 2-Nitropentachlor-1,3-butadiene (1b) with 3-indole acetonitrile (32),  2,2'-(ethylenedioxy) dietethiol (9) and 2-phenoxyethanethiol (38) in solvent-free medium.
The structures of novel synthesized compounds were purified by chromatographic methods and their structures were characterized by using spectroscopic methods such as MS, FTIR, 1H-NMR, 13C-NMR and UV.