Bazı yeni S-, N,S- sübstitüe dienler ve S-sübstitüe buteninlerin sentezi
Synthesis of some new S- and N,S-substituted dienes and S-substituted butenins
Yazar: HATİCE YILDIRIM
Danışman: PROF. DR. CEMİL İBİŞ
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Doktora, 2010
Konu: Kimya = Chemistry

Özet:
Çalışmamızda başlangıç maddesi olarak kullanılan 2H-pentaklor-1,3-butadien (1a), 2-nitropentaklor-1,3-butadien (2a), 1-brom-1,2,4,4-tetraklor-1,3-butadien (1b) ve 4-brom-2-nitro-1,1,3,4-tetraklor-1,3-butadien (2b) bileşiklerinin çeşitli tiyoller ve N-nükleofil bileşikleri ile reaksiyonları incelenmiştir.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2a) ile 2-metil-2-propantiyolün bazik ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 1,1-bis(2-metil-2-propiltiyo)-2-nitro-3,4,4-triklor-1,3-butadien (3) bileşiği elde edildi. 4-Brom-2-nitro-1,1,3,4-tetraklor-1,3-butadien (2b) ile 2-metil-2-propantiyolün bazik ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 1,1-bis(2-metil-2-propiltiyo)-4-brom-3,4-diklor-2-nitro-1,3-butadien (4) bileşiği elde edildi. 4-Brom-2-nitro-1,1,3,4-tetraklor-1,3-butadien (2b) ile 2-naftilmerkaptanın etanollü ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 4-brom-1-(2-naftiltiyo)-2-nitro-1,3,4-triklor-1,3-butadien (5) bileşiği elde edildi. 4-Brom-2-nitro-1,1,3,4-tetraklor-1,3-butadien (2b) ile benzilmerkaptanın çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 1-benziltiyo-4-brom-2-nitro-1,3,4-triklor-1,3-butadien (7) bileşiği elde edildi. 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2a) ile 4-metiltiyofenil merkaptanın etanollü ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 1-[(4-metiltiyofenil)tiyo]-2-nitro-1,3,4,4-tetraklor-1,3-butadien (13) ve 1,1-bis[(4-metiltiyofenil)tiyo]-2-nitro-3,4,4-triklor-1,3-butadien (14) bileşikleri elde edildi. 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2a) ile 4-metoksibenzil merkaptanın çözücüsüz ortamda 1:1 ve 1:3 oranında gerçekleştirilen reaksiyonlarından bilinmeyen, yeni 1-(4-metoksibenziltiyo)-2-nitro-1,3,4,4-tetraklor-1,3-butadien (20), 1,1-bis(4-metoksibenziltiyo)-2-nitro-3,4,4-triklor-1,3-butadien (21) ve 4,4-diklor-2-nitro-1,1,3-tris(4-metoksibenziltiyo)-1,3-butadien (22) bileşikleri elde edildi. 4-Brom-2-nitro-1,1,3,4-tetraklor-1,3-butadien (2b) ile 4-metoksibenzil merkaptanın etanollü ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 4-brom-1-(4-metoksibenziltiyo)-2-nitro-1,3,4-triklor-1,3-butadien (24) bileşiği elde edildi. 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2a) ile 2-propil merkaptanın çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 2-nitro-1,3,4,4-tetraklor-1-(2-propiltiyo)-1,3-butadien (28) bileşiği elde edildi. 4-Brom-2-nitro-1,1,3,4-tetraklor-1,3-butadien (2b) ile 2-propil merkaptanın çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 4-brom-2-nitro-1,3,4-triklor-1-(2-propiltiyo)-1,3-butadien (29) bileşiği elde edildi.Çalışmamızın diğer aşamasında, elde ettiğimiz bu monotiyosübstitüe-2-nitro-1,3-butadien bileşiklerinin morfolin, tiyomorfolin ve piperazin türevleri ile reaksiyonu incelendi. 4-Brom-1-(2-naftiltiyo)-2-nitro-1,3,4-triklor-1,3-butadien (5)'in 1-(4-florofenil) piperazin ile reaksiyonundan bilinmeyen, yeni 4-brom-3,4-driklor-1-[(4-florofenil)piperazinil]-1-(2-naftiltiyo)-2-nitro-1,3-butadien (6) bileşiği elde edildi. 1-Benziltiyo-4-brom-2-nitro-1,3,4-triklor-1,3-butadien (7) bileşiği sırasıyla 1-(4-florofenil) piperazin, morfolin, 1-(2-florofenil) piperazin, 1-(4-hidroksifenil) piperazin ve tiyomorfolin ile reaksiyona sokuldu. Reaksiyonlar sonucu sırasıyla bilinmeyen, yeni 1-benziltiyo-4-brom-3,4-diklor-1-[(4-florofenil) piperazinil]-2-nitro-1,3-butadien (8), 1-benziltiyo-4-brom-3,4-diklor-1-morfolino-2-nitro-1,3-butadien (9), 1-benziltiyo-4-brom-3,4-diklor-1-[(2-florofenil) piperazinil]-2-nitro-1,3-butadien (10), 1-benziltiyo-4-brom-3,4-diklor-1-[(4-hidroksifenil) piperazinil]-2-nitro-1,3-butadien (11), 1-benziltiyo-4-brom-3,4-diklor-1-tiyomorfolino-2-nitro-1,3-butadien (12) bileşikleri elde edildi. 1-[(4-metiltiyofenil)tiyo]-2-nitro-1,3,4,4-tetraklor-1,3-butadien (13) bileşiği sırasıyla 1-(4-florofenil) piperazin, morfolin, 1-(2-florofenil) piperazin, 1-(4-hidroksifenil) piperazin, 4-floroanilin ile reaksiyona sokuldu ve sırasıyla bilinmeyen, yeni 1-[(4-florofenil) piperazinil)-1-[(4-metiltiyofenil)tiyo]-2-nitro-3,4,4-triklor-1,3-butadien (15), 1-[(4-metiltiyofenil)tiyo]-1-morfolino-2-nitro-3,4,4-triklor-1,3-butadien (16), 1-[(2-florofenil) piperazinil]-1-[(4-metiltiyofenil)tiyo]-2-nitro-3,4,4-triklor-1,3-butadien (17), 1-[(4-hidroksifenil)piperazinil]-1-[(4-metiltiyofenil)tiyo]-2-nitro-3,4,4-triklor-1,3-butadien (18), 1-(4-floroanilino)-1-[(4-metiltiyofenil)tiyo]-2-nitro-3,4,4-triklor-1,3-butadien (19) bileşikleri elde edildi. 1-(4-Metoksibenziltiyo)-2-nitro-1,3,4,4-tetraklor-1,3-butadien (20) bileşiği ile 1-(4-florofenil) piperazinin reaksiyonundan bilinmeyen, yeni 1-[(4-florofenil) piperazinil]-1-(4-metoksibenziltiyo)-2-nitro-3,4,4-triklor-1,3-butadien (23) bileşiği elde edildi. 4-Brom-1-(4-metoksibenziltiyo)-2-nitro-1,3,4-triklor-1,3-butadien (24) bileşiği ile 1-(4-florofenil) piperazinin reaksiyonundan bilinmeyen yeni 4-brom-3,4-diklor-1-[(4-florofenil)piperazinil]-1-(4-metoksibenziltiyo)-2-nitro-1,3-butadien (25) bileşiği elde edildi. Bilinen 1-(4-bromfeniltiyo)-2-nitro-1,3,4,4-tetraklor-1,3-butadien (26) bileşiği ile homopiperazinin reaksiyonundan ise bilinmeyen, yeni 1,4-bis[1-(4-bromofeniltiyo)-3,4,4-triklor-2-nitrobuta-1,3-dienil]-1,4-diazepan (27) bileşiği elde edildi.Çalışmamızın son aşamasında ise 2H-polihalobutadien bileşiği ile çeşitli tiyollerin bazik ortamdaki reaksiyonları incelenmiştir. 1,1,2,4,4-Pentaklor-1,3-butadien (1a) ile 4-metiltiyofenil merkaptanın bazik ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 4-[(4-metiltiyofenil)tiyo]-1,1,2-triklor-1-buten-3-in (30) ve 1-[(4-metiltiyofenil)tiyo]-1,3,4,4-tetraklor-1,3-butadien (31) bileşikleri karışım halinde elde edildi. 1-Brom-1,2,4,4-tetraklor-1,3-butadien (1b) ile 4-metiltiyofenil merkaptanın bazik ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 1-brom-1,2-diklor-4-[(4-metiltiyofenil)tiyo]-1-buten-3-in (32) bileşiği elde edildi. 1,1,2,4,4-Pentaklor-1,3-butadien (1a) ile 4-metoksifenil merkaptanın bazik ortamda gerçekleştirilen reaksiyonundan bilinmeyen, yeni 4-(4-metoksifeniltiyo)-1,1,2-triklor-1-buten-3-in (33) ve 1,1-bis(4-metoksifeniltiyo)-3,4,4-triklor-1,3-butadien (34) bileşikleri elde edildi.Sentezlenen bu yeni bileşikler kolon kromatografisi ve kristallendirme yöntemleri ile saflaştırıldı. Yapıları mikroanaliz ve spektroskopik yöntemler (FTIR, NMR, UV-vis ve MS) ile aydınlatıldı.

Abstract:
In our study, the reactions of 2H-pentachloro-1,3-butadiene (1a), 2-nitropentachloro-1,3-butadiene (2a), 1-bromo-1,2,4,4-tetrachloro-1,3-butadiene (1b) and 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (2b) as starting materials with various thiols and N-nucleophil compounds were investigated.The reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2a) with 2-methyl-2-propanethiol in the presence of NaOH in ethanol was performed to give new 1,1-bis(2-methyl-2-propanethio)-2-nitro-3,4,4-trichloro-1,3-butadiene (3). The new compound 1,1-bis(2-metil-2-propiltiyo)-4-bromo-3,4-dichloro-2-nitro-1,3-butadiene (4) was obtained from the reaction of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (2b) with 2-methyl-2-propanethiol in the presence of NaOH in ethanol. The new compound 4-bromo-1-(2-naphthylthio)-2-nitro-1,3,4-trichloro-1,3-butadiene (5) was obtained from the reaction of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (2b) with 2-naphthyl mercaptan in ethanol. The new compound 1-benzylthio-4-bromo-2-nitro-1,3,4-trichloro-1,3-butadiene (7) was obtained from the direct reaction of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (2b) with benzyl mercaptan. The new compound 1-[(4-methylthiophenyl)thio]-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene (13) and 1,1-bis[(4-methylthiophenyl)thio]-2-nitro-3,4,4-trichloro-1,3-butadiene (14) were obtained from the reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2a) with 4-methylthiophenyl mercaptan in ethanol. The new compounds 1-(4-methoxybenzylthio)-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene (20), 1,1-bis(4-methoxybenzylthio)-2-nitro-3,4,4-trichloro-1,3-butadiene (21) and 4,4-dichloro-2-nitro-1,1,3-tris(4-methoxybenziltiyo)-1,3-butadiene (22) were obtained from the reactions of 1:1 and 1:3 molar ratios of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2a) with 4-methoxybenzyl mercaptan in ethanol. The new compound 4-bromo-1-(4-methoxybenzylthio)-2-nitro-1,3,4-trichloro-1,3-butadiene (24) was obtained from the reaction of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (2b) with 4-methoxybenzyl mercaptan in ethanol. The new compound 2-nitro-1-(2-propylthio)-1,3,4,4-tetrachloro-1,3-butadiene (28) was obtained from the direct reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2a) with 2-propyl mercaptan. The new compound 4-bromo-2-nitro-1-(2-propylthio)-1,3,4-trichloro-1,3-butadiene (29) was obtained from the direct reaction of 4-bromo-2-nitro-1,1,3,4-tetrachloro-1,3-butadiene (2b) with 2-propyl mercaptan.In the next step, the reactions of monothiosubstituted-2-nitro-1,3-butadienes with morpholine, thiomopholine and the derivatives of piperazine. The new compound 4-bromo-3,4-dichloro-1-[1-(4-fluorophenyl)piperazinyl]-1-(2-naphthylthio)-2-nitro-1,3-butadiene (6) was obtained from the reaction of 4-bromo-1-(2-naphthylthio)-2-nitro-1,3,4-trichloro-1,3-butadiene (5) with 1-(4-fluorophenyl) piperazine. The new compounds 1-benzylthio-4-bromo-3,4-dichloro-1-[(4-fluorophenyl) piperazinyl]-2-nitro-1,3-butadiene (8), 1-benzylthio-4-bromo-3,4-dichloro-1-morpholino-2-nitro-1,3-butadiene (9), 1-benzylthio-4-bromo-3,4-dichloro-1-[(2-fluorophenyl) piperazinyl]-2-nitro-1,3-butadiene (10), 1-benzylthio-4-bromo-3,4-dichloro-1-[(4-hydroxyphenyl) piperazinyl]-2-nitro-1,3-butadiene (11) and 1-benzylthio-4-bromo-3,4-dichloro-2-nitro-1-thiomorpholinyl-1,3-butadiene (12) were synthesized from the reaction of 1-benzylthio-4-bromo-2-nitro-1,3,4-trichloro-1,3-butadiene (7) with 1-(4-fluorophenyl) piperazine, morpholine, 1-(2-fluorophenyl) piperazine, 1-(4-hydroxyphenyl) piperazine and thiomorpholine in turn. The new compounds 1-[(4-fluorophenyl) piperazinyl]-1-[(4-methylthiophenyl)thio]-2-nitro-3,4,4-trichloro-1,3-butadiene (15), 1-[(4-methylthiophenyl)thio]-1-morpholinyl-2-nitro-3,4,4-trichloro-1,3-butadiene (16), 1-[(2-fluorophenyl) piperazinyl]-1-[(4-methylthiophenyl) thio]-2-nitro-3,4,4-trichloro-1,3-butadiene (17), 1-[(4-hydroxyphenyl) piperazinyl]- 1-[(4-methylthiophenyl) thio]-2-nitro-3,4,4-trichloro-1,3-butadiene (18) and 1-(4-fluoroanilino)-1-[(4-methylthiophenyl) thio]-2-nitro-3,4,4-trichloro-1,3-butadiene (19) were synthesized from the reaction of 1-[(4-methylthiophenyl)thio]-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene (13) with 1-(4-fluorophenyl) piperazin, morpholine, 1-(2-fluorophenyl) piperazine, 1-(4-hydroxyphenyl) piperazine and 4-fluoroaniline in turn. The new compound 1-(4-fluorophenyl piperazinyl)-1-(4-methoxybenziltiyo)-2-nitro-3,4,4-trichloro-1,3-butadiene (23) was synthesized from the reaction of 1-(4-methoxybenzylthio)-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene (20) with 1-(4-fluorophenyl) piperazine. The new compound 4-bromo-3,4-dichloro-1-[(4-fluorophenyl) piperazinyl]-1-(4-methoxybenzylthio)-2-nitro-1,3-butadiene (25) was synthesized from the reaction of 4-bromo-1-(4-methoxybenzylthio)-2-nitro-1,3,4-trichloro-1,3-butadiene (24) with 1-(4-fluorophenyl) piperazine. The new compound 1,4-bis[1-(4-bromophenylthio)-3,4,4-trichloro-2-nitrobuta-1,3-dienyl]-1,4-diazepan (27) was synthesized from the reaction of known 1-(4-bromophenylthio)-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene (26) with homopiperazine.In the last step, the reactions of 2H-polyhalogenated-1,3-butadiene compounds with some various thiols in the presence of NaOH in ethanol were investigated. The new compounds 4-[(4-methylthiophenyl)thio]-1,1,2-trichloro-1-buten-3-yne (30) and 1-[(4-methylthiophenyl)thio]-1,3,4,4-tetrachloro-1,3-butadiene (31) were synthesized from the reaction of 2H-pentachloro-1,3-butadiene (1a) with 4-methylthiophenyl mercaptan. The new compound 1-bromo-1,2-dichloro-4-[(4-methylthiophenyl)thio]-1-buten-3-yne (32) was synthesized from the reaction of 1-bromo-1,2,4,4-tetrachloro-1,3-butadiene (1b) with 4-methylthiophenyl mercaptan. The new compounds 4-(4-methoxyphenylthio)-1,1,2-trichloro-1-buten-3-yne (33) and 1,1-bis(4-methoxyphenylthio)-3,4,4-trichloro-1,3-butadiene (34) were synthesized from the reaction of 2H-pentachloro-1,3-butadiene (1a) with 4-methoxyphenyl mercaptan.These novel products were purified either crystallization or via column chromatography. Structures of these novel products were characterized by microanalysis and spectroscopic methods (FTIR, NMR,UV-vis and MS).