Polihalobuten ve halobutadienlerin tiyollerle reaksiyonundan yeni tiyoeterlerin sentezi
Synthesis of new thioethers from the reaction of polyhalobutene and halobuthadienes with thiols
Yazar: SİBEL ŞAHİNLER AYLA
Danışman: PROF. DR. CEMİL İBİŞ
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Doktora, 2009
Konu: Kimya = Chemistry
Dizin: Butadien = Butadiene ; Tiyoeterler = Thioethers ; Tiyoller = Thiols

Özet:
Bu çalışmanın ilk aşamasında Trikloroetilenin dibenzoilperoksit varlığında serbest radikaller üzerinden yürüyen dimerizasyonu sonucu 1,1,3,3,4,4-Heksaklor-1-buten (1) bileşiği elde edildi. Bu bileşikten çıkarak diğer başlangıç maddesi 2H-1,1,3,4-tetraklor-4-brombutadien (2) sentezlendi. Çalışmanın ikinci aşamasında (1) ve (2) bileşikleri başlangıç maddesi olarak kullanıldı ve bilinmeyen yeni ?S sübstitüe bileşikleri elde edildi.1,1,3,3,4,4-Heksaklor-1-buten (1) başlangıç maddesiyle dipolar aprotik çözücü varlığında 7-merkapto-4-metil kumarin, 2-merkaptofenol, 2-metiltiyofenol, 4-flortiyofenol, 4-metoksitiyofenol, 2,4-dimetiltiyofenol, 3,4-dimetokstiyofenol, pentaflortiyofenol ve p-nitrotiyofenol reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 2-Klor-1,1,4,4-(7-merkapto-4-metil-kumarinil)-1,3-butadien (3), 2-Klor-1,1,4,4-(2-hidroksifeniltiyo)-1,3-butadien (4), 2-Klor-1,1,4,4-(2-metilfeniltiyo)-1,3-butadien (5), 2-Kloro-1,4,4-(4-florofeniltiyo)-1,3-butadien (6), 2-Klor-1,4,4,4-(4-metoksifeniltiyo)-1,3-butadien (7), 2-Klor-1,1,4,4-(2,4-dimetilfeniltiyo)-1,3-butadien (8), 1,1,2,4-Tetraklor-4-(3,4-dimetoksifeniltiyo)-1,3-butadien (9), 2-Klor-1,1,4,4-(pentaflorfeniltiyo)-1,3-butadien (10) ve 1,1,3-Triklor-4,4-(4-nitrofeniltiyo)-1,3-butadien (28) bileşikleri sentezlendi.1,1,3,3,4,4-Heksaklor-1-buten (1) başlangıç maddesiyle protik çözücü varlığında 7-merkapto-4-metil kumarin, 2-metiltiyofenol, 2,4-dimetiltiyofenol, 3,4-dimetoksitiyofenol, 2-merkaptobenzotiazol, 2-merkaptobenzimidazol, 2,2,2-trifloretantiyol, 3-merkapto-1-propanol ve siklopentil merkaptan reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 1,1,2,4-Tetraklor-4-(7-merkapto-4-metil-kumarinil)-1,3-butadien (11), 1,2-Diklor-1,4,4-(7-merkapto-4-metil-kumarinil)-1,3-butadien (12) ve 1,1,2-Triklor-4-(7-merkapto-4-metil-kumarinil)-1-buten-3-in (13), 1,1,2-Triklor-4-(2-metilfeniltiyo)-1-buten-3-in (14), 1,1,2-Triklor-4-(2,4-dimetilfeniltiyo)-1-buten-3-in (15), 1,2-Diklor-1,4-(3,4-dimetoksifeniltiyo)-1-buten-3-in (16) ve 2-Klor-1,1,4-(3,4-dimetoksifeniltiyo)-1-buten-3-in (17), 1,1,2,4-Tetraklor-4-(benzo-1,3-tiyazolil-(2)-tiyo)-1,3-butadien (18), 1,1,2,4-Tetraklor-4-(benzo-1,3-imidazolil-(2)-tiyo)-1,3-butadien (19), 2-Klor-1,1,4,4-(2,2,2-triflor-etil-sülfanil)-1,3-butadien (20), 2-Klor-1,1,3,4,4-(2,2,2-triflor-etil-sülfanil)-1,3-butadien (21), 2-Klor-1,1,4,4-(1-propanol-3-sülfanil)-1-buten-3-in (22), 1,1,2-Triklor-4,4-(siklopentil-sülfanil)-1,3-butadien (26), 1,1,2,4-(siklopentil-sülfanil)-1-buten-3-in (27) bileşikleri elde edildi.2H-1,1,3,4-tetraklor-4-brombutadien (2) başlangıç maddesiyle protik çözücü varlığında 7-merkapto-4-metil kumarin, 2,4-dimetiltiyofenol ve 2-merkaptobenzotiazol bileşikleri reaksiyona sokuldu. Reaksiyonlar sonucunda 1-Brom-1,2-Diklor-4-(7-merkapto-4-metil-kumarinil)-1-buten-3-in (23), 1-Brom-1,2-Diklor-4-(2,4-dimetilfeniltiyo)-1-buten-3-in (24) ve 1-Brom-1,2-Diklor-4-(benzo-1,3-tiyazolil-(2)-tiyo)-1,3-butadien (25) bileşikleri elde edildi.Sentezlenen bu yeni bileşiklerin yapıları mikroanaliz, FTIR, 1H NMR, 13C NMR, 19F NMR, MS, UV-Vis ve floresans spektroskopi teknikleri kullanılarak aydınlatıldı.

Abstract:
In this work, firstly 1,1,3,3,4,4-hexachloro-1-butene (1) compound was synthesized from the trichloroetylene?s free radical dimerization with dibenzoylperoxide. 2H-1,1,3,4-tetrachloro-4-bromobutadien (2) was synthesized from compound (1). In the second part of this study (1) and (2) were used as starting materials and new unknown -S substitue compounds were synthesized.2-Chloro-1,1,4,4-(7-mercapto-4-methyl-coumarinyl)-1,3,butadiene (3), 2-Chloro-1,1,4,4,-(2-hydroxyphenylthio)-1,3-butadiene (4), 2-Chloro-1,1,4,4-(2-methylphenylthio)-1,3-butadiene (5), 2-Chloro-1,4,4-(4-phlorophenilthio)-1,3-butadiene (6), 2-Chloro-1,4,4,4-(4-methoxyphenilthio)1,3-butadiene (7), 2-Chloro-1,1,4,4-(2,4-dimethylphenilthio)-1,3-butadiene (8), 1,1,2,4-Tetrachloro-4-(3,4-dimethoxyphenilthio)-1,3-butadiene (9), 2-Chloro-1,1,4,4-(pentfluorophenilthio)-1,3-butadiene (10) and 1,1,3-Trichloro-4,4-(4-nitrophenilthio)-1,3-butadiene (28) compounds were synthesized from the reaction of 1,1,3,3,4,4-hexachloro-1-butene (1) with 7-mercapto-4-methyl coumarin, 2-mercaptophenol, 2-methylthiophenol, 4-fluorothiophenol, 4-methoxythiophenol, 2,4-dimethylthiophenol, 3,4-dimethoxythiophenol, pentafluorothiophenol and p-nitrothiophenol in the presence of dipolar aprotic solvent.In the same way, 1,1,2,4-Tetrachloro-4-(7-mercapto-4-methyl-coumarinyl)-1,3-butadiene (11), 1,2-Dichloro-1,4,4-(7-mercapto-4-methyl-coumarinyl)-1,3-butadiene (12), 1,1,2-Trichloro-4-(7-mercapto-4-methil-coumarinyl)-1-butene-3-yne (13), 1,1,2-Trichloro-4-(2-methylphenilthio)-1-butene-3-yne (14), 1,1,2-Trichloro-4-(2,4-dimethylphenilthio)-1-butene-3-yne (15), 1,2-Dichloro-1,4-(3,4-dimethoxyphenilthio)-1-butene-3-yne (16), 2-Chloro-1,1,4-(3,4-dimethoxyphenilthio)-1-butene-3-yne (17), 1,1,2,4-Tetracloro-4-benzo-1,3-thiazolyl-(2)-thio)-1,3-butadiene (18), 1,1,2,4-Tetracloro-4-benzo-1,3-imidazolyl-(2)-thio)-1,3-butadiene (19), 2-Chloro-1,1,4,4-(2,2,2-trifluoro-ethyl-sulphanyl)-1,3-butadiene (20), 2-Chloro-1,1,3,4,4-(2,2,2-tripholoro-ethil-sulphanyl)-1,3-butadiene (21), 2-Chloro-1,1,4,4-(1-propanol-3-sulphanyl-1-butene-3-yne (22), 1,1,2-Trichloro-4,4-(cyclopenthyl-sulphanyl)-1,3-butadiene (26) and 1,1,2,4-(cyclopentyl-sulphanyl)-1-butene-3-yne (27) compounds were synthesized from the reaction of starting material 1,1,3,3,4,4-hexachloro-1-butene (1) with 7-mercapto-4-methyl coumarin, 2-methylthiophenol, 2,4-dimethylthiophenol, 3,4-dimethoxythiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2,2,2-trifluoroethanthiol, 3-mercapto-1-propanol and cyclopentyl mercaptan in the presence of protic solvent.1-Bromo-1,2-Dichloro-4-(7-mercapto-4-methyl-coumarinyl)-1-butene-3-yne (23), 1-Bromo-1,2-Dichloro-4-(2,4-dimethylphenylthio)-1-butene-3-yne (24) and 1-Bromo-1,2-Dichloro-4-(benzo-1,3-thiazolyl-(2)-thio)-1,3-butadiene (25) compounds were synthesized from the reaction of starting material 2H-1,1,3,4-tetrachloro-4-bromobutadien (2) with 7-mercapto-4-methyl coumarin, 2,4-dimethylthiophenol and 2-mercaptobenzothiazol compounds in the presence of protic solvent.The structures of these newly synthesized compounds were charecterized by using microanalyses, FTIR, 1H NMR, 13C NMR, 19F NMR, MS, U V-Vis and fluorescence spectroscopy.