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İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Anabilim Dalı / Organik Kimya Bilim Dalı

Yeni doymamış gruplu tiyoeterlerin sentezi

The synthesis of the new thioethers with unsaturated group

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Özet:

Çalışmamızda başlangıç maddesi olarak 1,1,2,3,4,4-hekzaklor-1,3-butadien (1), 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2), 2H-1,1,3,4,4-pentaklor-1,3-butadien (31) bileşikleri kullanıldı.1,1,2,3,4,4-hekzaklor-1,3-butadien (1)'in Bis-2-merkaptoetilsülfit ile etanollü ortamda, NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni 1, 1, 2, 3, 4, 12, 13, 14, 15, 23, 24, 25, 26, 26-tetradekaklor-5, 8, 11, 16, 19, 22-hekzatiyo-1, 3, 12, 14, 23, 25-hekzaen-hekzakosan (3) bileşiği elde edildi.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)' in 6-merkapto-1-hekzanol ile direkt reaksiyonundan mono(tiyo)sübstitüe dien bileşiği olan, bilinmeyen yeni 2-Nitro-1,3,4,4-tetraklor-1-(6-hidroksihekziltiyo)-1,3-butadien (4) bileşiği elde edildi.2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)' in 4-merkaptofenol ile etanol varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni 2-Nitro-1,3,4,4-tetraklor-1-(4-hidroksifeniltiyo)-1,3-butadien (5) ve 2-Nitro-3,4,4-triklor-1,1-bis(4-hidroksifeniltiyo)-1,3-butadien (6) bileşikleri elde edildi.Çalışmamızın sonraki aşamasında, elde edilen mono(tiyo)sübstitüe nitrodien bileşiklerinin bazı piperazin türevleri, morfolin ve tiyomorfolin ile reaksiyonları incelendi.2-Nitro-1,3,4,4-tetraklor-1-(6-hidroksihekziltiyo)-1,3-butadien (4) bileşiği, sırasıyla 1-(2-florfenil piperazin), N-fenil piperazin, 2,5-Dimetil piperazin, 1-(2-Metoksifenil) piperazin, 1-(4-Hidroksifenil) piperazin, Piperazin, 1-(Difenil metil piperazin), 1-Etoksikarbonil piperazin, 1-(4-Florfenil) piperazin, 1-(4-Nitrofenil) piperazin, Morfolin, Tiyomorfolin ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla bilinmeyen yeni 1-[2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil]-4-(2-flor fenil) piperazin (7), 1-[2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil]-4-fenil piperazin (8), N,N'-Bis(2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil)-2,5-dimetil piperazin (9), 1-[2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil]-4-(2-metoksifenil) piperazin (10), 1-[2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil]-4-(4-hidroksifenil) piperazin (11), N,N'-Bis(2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil)-piperazin (12), 1-[2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil]-4-(difenilmetil piperazin) (13), 1-[2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil]-4-(etoksikarbonil piperazin) (14), 1-[2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil]-4-(4-florfenil) piperazin (15), 1-[2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadienil]-4-(4-nitrofenil) piperazin (16), 2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1-(morfolinil)-1,3-butadien (17), 2-Nitro-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1-(tiyomorfolinil)-1,3-butadien (18) bileşikleri sentezlendi.2-Nitro-1,3,4,4-tetraklor-1-(4-hidroksifeniltiyo)-1,3-butadien (5) bileşiği, sırasıyla 1-(2-florfenil piperazin), N-fenil piperazin, 2,5-Dimetil piperazin, 1-(2-Metoksifenil) piperazin, 1-(4-Hidroksifenil) piperazin, piperazin, 1-(Difenil metil piperazin), 1-Etoksikarbonil piperazin, 1-(4-Florfenil) piperazin, 1-(4-Nitrofenil) piperazin, Morfolin, Tiyomorfolin ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla bilinmeyen yeni 1-[2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-4-(2-florfenil piperazin) (19), 1-[2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-4-fenil piperazin (20), N,N'-Bis(2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-2,5-Dimetil piperazin (21), 1-[2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-4-(2-metoksifenil) piperazin (22), 1-[2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-4-(4-hidroksifenil) piperazin (23), N,N'-Bis(2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-piperazin (24), 1-[2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-4-(difenil metil piperazin) (25), 1-[2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-4-(1-etoksikarbonil) piperazin (26), 1-[2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-4-(4-florfenil) piperazin (27), 1-[2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1,3-butadienil]-4-(4-nitrofenil) piperazin (28), 2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1-(morfolinil)-1,3-butadien (29), 2-Nitro-3,4,4-triklor-1-(4-hidroksifeniltiyo)-1-(tiyomorfolinil)-1,3-butadien (30) bileşikleri sentezlendi.Çalışmamızın son aşamasında 2H-1,1,3,4,4-pentaklor-1,3-butadien (31)'in 6-merkapto-1-hekzanol ile etanollü ortamda NaOH varlığında reaksiyonu gerçekleştirildi. Reaksiyon sonucunda bilinmeyen yeni 1,1,2-Triklor-4-(6-hidroksihekziltiyo)-1-buten-3-in (32) bileşiği, 1,1,2-Triklor-4-(6-hidroksihekziltiyo)-1-buten-3-in (32) bileşiğinin CCl4 varlığında Br2 ile reaksiyonundan bilinmeyen yeni 1,2-Dibrom-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadien (33) bileşiği, 1,2-Dibrom-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadien (33) bileşiğinin piridin içerisinde SOCl2 ile reaksiyonundan bilinmeyen yeni 1,2-Dibrom-3,4,4-triklor-1-(6-klorhekziltiyo)-1,3-butadien (34) bileşiği, 1,2-Dibrom-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadien (33) bileşiğinin 3-klorperbenzoikasit (metaklorperbenzoikasit) (m-CPBA) ile 1:1 reaksiyonundan bilinmeyen yeni 1,2-Dibrom-3,4,4-triklor-1-(6-hidroksihekzilsülfinil)-1,3-butadien (35), 1,2-Dibrom-3,4,4-triklor-1-(6-hidroksihekziltiyo)-1,3-butadien (33) bileşiğinin 3-klorperbenzoikasit (metaklorperbenzoikasit) (m-CPBA) ile 1:2 reaksiyonundan bilinmeyen yeni 1,2-Dibrom-3,4,4-triklor-1-(6-hidroksihekzilsülfinil)-1,3-butadien (36) ve 1,2-Dibrom-3,4,4-triklor-1-(6-hidroksihekzilsülfonil)-1,3-butadien (37) bileşikleri, 2H-1,1,3,4,4-pentaklor-1,3-butadien (31)'in 4-merkapto fenol ile etanollü ortamda NaOH varlığında reaksiyonundan bilinmeyen yeni 2H-1,3,4,4-tetraklor-1-(4-hidroksifeniltiyo)-1,3-butadien (38) bileşiği sentezlendi.Sentezlenen tiyoeter yapılı bileşikler kristallendirme veya kolon kromatografisi yöntemleri ile saflaştırıldı. Yapıları mikroanaliz ve spektroskopik yöntemler (IR, 1H-NMR, 13C-NMR, UV ve MS) ile aydınlatıldı.

Summary:

In our study, 1,1,2,3,4,4-hexachloro-1,3-butadiene (1), 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2), 2H-1,1,3,4,4-pentachloro-1,3-butadiene (31) compounds were used as starting compounds.1, 1, 2, 3, 4, 12, 13, 14, 15, 23, 24, 25, 26, 26-tetradecachloro-5, 8, 11, 16, 19, 22-hexaathia-1, 3, 12, 14, 23, 25-hexaen-hexacosan (3) was obtained from the reaction of 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) with Bis-2-mercaptoethylsulfide in the presence of NaOH in ethanol.The new thiosubstituted diene compound 2-Nitro-1,3,4,4-tetrachloro-1-(6-hydroxyhexylthio)-1,3-butadiene (4) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 6-mercapto-1-hexanol.The new compounds 2-Nitro-1,3,4,4-tetrachloro-1-(4-hydroxyphenylthio)-1,3-butadiene (5) and 2-Nitro-3,4,4-trichloro-1,1-bis(4-hydroxyphenylthio)-1,3-butadiene (6) were obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 4-mercaptophenol in ethanol.In the following step, reactions of derivatives of piperazine, morpholine, thiomorpholine with the mono(thio)substituted nitrodiene compounds were explored.The new compounds 1-[2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl]-4-(2-fluoro phenyl) piperazine (7), 1-[2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl]-4-phenyl piperazine (8), N,N?-Bis(2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl)-2,5-dimethyl piperazine (9), 1-[2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl]-4-(2-methoxyphenyl) piperazine (10), 1-[2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl]-4-(4-hydroxyphenyl) piperazine (11), N,N?-Bis(2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl)-piperazine (12), 1-[2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl]-4-(diphenylmethyl piperazine) (13), 1-[2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl]-4-(ethoxycarbonyl piperazine) (14), 1-[2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl]-4-(4-fluorophenyl) piperazine (15), 1-[2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadienyl]-4-(4-nitrophenyl) piperazine (16), 2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1-(morpholinyl)-1,3-butadiene (17), 2-Nitro-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1-(tiyomorpholinyl)-1,3-butadiene (18) were synthesized from the reaction of 2-Nitro-1,3,4,4-tetrachloro-1-(6-hydroxyhexylthio)-1,3-butadiene (4) with the 1-(2-Fluorophenyl piperazine), N-phenyl piperazine, 2,5-Dimethyl piperazine, 1-(2-Methoxyphenyl) piperazine, 1-(4-Hydroxyphenyl) piperazine, Piperazine, 1-(Diphenyl methyl piperazine), 1-Ethoxycarbonyl piperazine, 1-(4-Fluorophenyl) piperazine, 1-(4-Nitrophenyl) piperazine, Morpholine, Thiomorpholine, respectively.The new compounds 1-[2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-4-(2-fluorophenyl piperazine) (19), 1-[2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-4-phenyl piperazine (20), N,N?-Bis(2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-2,5-dimethyl piperazine (21), 1-[2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-4-(2-methoxyphenyl) piperazine (22), 1-[2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-4-(4-hydroxyphenyl) piperazine (23), N,N?-Bis(2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-piperazine (24), 1-[2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-4-(diphenyl methyl piperazine) (25), 1-[2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-4-(1-ethoxycarbonyl) piperazine (26), 1-[2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-4-(4-fluorophenyl) piperazine (27), 1-[2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1,3-butadienyl]-4-(4-nitrophenyl) piperazine (28), 2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1-(morpholinyl)-1,3-butadiene (29), 2-Nitro-3,4,4-trichloro-1-(4-hydroxyphenylthio)-1-(thiomorpholinyl)-1,3-butadiene (30) were synthesized from the reaction of 2-Nitro-1,3,4,4-tetrachloro-1-(4-hydroxyphenylthio)-1,3-butadiene (5) with the 1-(2-Fluorophenyl piperazine), N-phenyl piperazine, 2,5-Dimethyl piperazine, 1-(2-Methoxyphenyl) piperazine, 1-(4-Hydroxyphenyl) piperazine, Piperazine, 1-(Diphenyl methyl piperazine), 1-Ethoxycarbonyl piperazine, 1-(4-Fluorophenyl) piperazine, 1-(4-Nitrophenyl) piperazine, Morpholine, Thiomorpholine, respectively.In the last step, the new compound 1,1,2-Trichloro-4-(6-hydroxyhexylthio)-1-buten-3-in (32) was synthesized from the reaction of 2H-1,1,3,4,4-pentachloro-1,3-butadiene (31) with 6-mercapto-1-hexanol in the presence of NaOH in ethanol. The new compound 1,2-Dibromo-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadiene (33) was synthesized from the reaction of 1,1,2-Trichloro-4-(6-hydroxyhexylthio)-1-buten-3-in (32) with Br2 in CCl4. The new compound 1,2-Dibromo-3,4,4-trichloro-1-(6-chlorohexylthio)-1,3-butadiene (34) was synthesized from the reaction of 1,2-Dibromo-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadiene (33) with SOCl2 in pyridine. The new compound 1,2-Dibromo-3,4,4-trichloro-1-(6-hydroxyhexylsulfinyl)-1,3-butadiene (35) was synthesized from the reaction of 1,2-Dibromo-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadiene (33) with 3-chloroperbenzoicacid (m-CPBA) (1:1), the new compounds 1,2-Dibromo-3,4,4-trichloro-1-(6-hydroxyhexylsulfinyl)-1,3-butadiene (36) and 1,2-Dibromo-3,4,4-trichloro-1-(6-hydroxyhexylsulfonyl)-1,3-butadiene (37) were synthesized from the reaction of 1,2-Dibromo-3,4,4-trichloro-1-(6-hydroxyhexylthio)-1,3-butadiene (33) with 3-chloroperbenzoicacid (m-CPBA) (1:2). The new compound 2H-1,3,4,4-tetrachloro-1-(4-hydroxyphenylthio)-1,3-butadiene (38) was synthesized from the reaction of 2H-1,1,3,4,4-pentachloro-1,3-butadiene (31) with 4-mercatophenol in the presence of NaOH in ethanol.Synthesized thioether compounds were purified either crystallization or via column chromatography. Structure of these novel products were characterized by microanalysis and spectroscopic methods (IR, 1H-NMR, 13C-NMR, UV and MS)