Monoen ve dien yapılı polihalojenli organik bileşiklerden S- ve N- substitue organik bileşiklerin sentezi
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Abstract
ÖZET `MONOEN VE DİEN YAPILI POLİHALOJENLİ ORGANİK BİLEŞİKLERDEN S- VE N-SÜBSTİTÜE ORGANİK BİLEŞİKLERİN SENTEZİ` Bu çalışmada ilk aşama olarak trikloretilenin dimerleşmesi ile hazırlanan polihalojenli organik bileşikler sentezlendi. Oluşan 2-H-4-brom-tetraklor-l,3-butadien ve 2-H-pentaklor-l,3-butadien bileşiklerinden 4-Brom-l,l,3,4-tetraklor-2-nitro-l,3- butadien (1) ve 1,1, 3,4,4-pentaklor-2-rıitro- 1,3-butadien (18) bileşikleri elde edildi. Çalışmanın ikinci aşamasında (1) ve (18) bileşikleri başlangıç maddesi olarak kullanıldı. Bu aşamada S-sübstitüe nitrodien bileşikleri elde edildi. Bunun için 4-Brom-l,l,3,4-tetraklor-2-nitro-l,3-butadien (1) p-klortiyofenol ile reaksiyona sokuldu ve 4-Brom-1354-trMor-l-rnono(p-klorfeniltiyo)-2-nitro-l,3-butadien (8) elde edildi. Ayrıca 1,1, 3, 4,4-PentaMor-2-nitro- 1,3-butadien (18) allilmerkaptan ile reaksiyona sokularak, l-(Amhiyo)-l,3,4,4-tetraklor-2-nitro-l,3-butadien (19), l,l-Bis(Alliltiyo)- 3,4,4-triklor-2-nitro-l,3-butadien (20) ve l,l,4-Tris(Alültiyo)-3,4-diklor-2-nitro-l,3- butadien (21) bileşikleri elde edildi. Üçüncü aşamada elde edilen S-sübstitüe nitrodien bileşikleri ve 4-Brom-l,3,4- triklor-l-mono(p-metilfemltiyo)-2-nitro-l,3-butadien (2) bileşiği bazı N-nükleofillerle reaksiyona sokuldu. 4-Brom- 1,3,4-triklor- 1 -mono(p-klorfeniltiyo)-2-nitro- 1,3 -butadien (8) sırasıyla piperazin, 2,5-dimetilpiperazin, l-(4-fluorfenil)piperazin, 4-fenilpiperazin, 4-metilpiperazin, 4-morfolin, piperidin, 4-metilpiperidin ve anilin ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırayla N,N'-Bis(4-brom-3,4-diklor-l-(p-klorfenilti- yo)-2-nitro-l,3-butadienil)-piperazin (9), N,N'-Bis(4-brom-3,4-diklor-l-(p-klorfenilti- yo)-2-nitro- 1,3-butadienil)-2,5-dimetilpiperazin (10), 4-Brom-3,4-diklor- 1 -( 1 -(4-fluor- fenil)piperazin)-l-(p-klorfeniltiyo)-2-nitro- 1,3 -butadien (11), 4-Brom-3,4-diklor-l-(4- fenilpiperazin)- 1 -(p-klorfeniltiyo)-2-nitro- 1,3-butadien (12), 4-Brom-3,4-diklor- 1 -(p- klorfeniltiyo)- 1 -(4-metilpiperazin)-2-nitro- 1,3-butadien (13), 4-Brom-3,4-diklor- 1 -(4- morfolino)- 1 -(p-klorfeniltiyo)-2-nitro- 1,3-butadien (14), 4-Brom-3,4-diklor- 1 -(p-klorfe- niltiyo)-2-nitro- 1 -piperidino- 1,3-butadien (15), 4-Brom-3,4-diklor- 1 -(p-klorfeniltiyo)-2- nitro-l-(4-metilpiperidino)- 1,3-butadien (16) ve 4-Brom-3,4-dMor-l-(fenilamino)-l-(p- klorfeniltiyo)-2-nitro-l,3-butadien (17) sentezlendi. Aym şekilde 4-Brom-l,3,4-triklor-l-mono(p-metilfeniltiyo)-2-nitro-l,3-butadien (2) bileşiği sırasıyla 2,5-dimetil piperazin, l-(4-fluorfenil)piperazin, 4-fenilpiperazin, benzidin ve 4-piperidinol ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla N,N'-Bis(4-brom-3,4-dildor-l-(p-ıreti]fe^ perazin (3), 4-Brom-3,4-diklor- 1 -( 1 -(4-fluorfenil)piperazin)- 1 -(p-metilfeniltiyo)-2-nit- ro-1,3-butadien (4), 4-Brom-3,4-diklor-l-(4-ferıilpiperazin)-l-(p-metilfeniltiyo)-2-nitro- 1,3-butadien (5), N,N'-Bis(4-brom-3,4-diklor- 1 -(p-metilfeniftiyo)-2-nitro- 1,3-butadien- il)-benzidin (6) ve 4-Brom-3,4-dMor-l-(p-metilfemltiyo)-2-nitro-l-(4-piperidinol)-l,3- butadien (7) bileşikleri elde edildi. l-(Amltiyo)-l,3,4,4-tetraklor-2-nitro-l,3-butadien (19) bileşiğinin piperazin, 1-etoksikarbonilpiperazin, 2,5-dimetilpiperazin, 4-fenilpiperazin, 4-(p-fluorfenil)pipera- XIzin, 4-morfolin ve piperidin ile reaksiyonundan sırasıyla N,N'-Bis(l-Alliltiyo-3,4,4- triklor-2-nitro-l,3-butadienil)-piperazin (22),l-(Alliltiyo-3,4,4-triklor-2-nitro-l,3-buta- dienil)-4-(etoksikarbonil)-piperazin (23), N,N'-Bis(l-Allütiyo-3,4,4-triklor-2-nitro-l,3- butadienil)-2,5-dimetilpiperazin (24), l-(AMtiyo-3,4,4-triklor-2-nitro-l,3-butadienil)- 4-fenilpiperazin (25), l-(AMtiyo-3,4,4-tı^or-2-nitro-l,3-butadienil)-4-(4-fluorfenilpi- perazin (26), l-Alliltiyo-3,4,4-triklor-l-(4-morfolino)-2-nitro-l,3-butadien (27) ve 1- AllütiyoO,4,4-triklor-2-nitro-l-piperidino-l,3-butadien (28) bileşikleri elde edildi Heksaklorbutadien butanditiyol ile etanollü ortamda sodyum hidroksit varlığında reaksiyona sokuldu. Reaksiyon sonucunda 4,4'-Butanditiyo-bis(l, 1,2,3,4- pentaklor- 1,3-butadien) (29), 1,6,7, 1 2-Tetratiyo-bis( 1,2,3,4,4-pentaklor- 1,3-butadienil)- ikosan (30) ve 2,3,4,5-Tetraklor-l,6-ditiya-siklodeka-2,4-dien (31) bileşikleri elde edildi. Ayrıca heksaklorbutadien' in allilmerkaptan ile reaksiyonundan mono(tiyo)- ve di(tiyo)sübstitüe bileşikler elde edildi. Heksaklorbutadien allilmerkaptan ile sodyum hidroksit varlığında reaksiyona sokuldu ve l-Mono(alliltiyo)-l,2,3,4,4-pentaklor-l,3- butadien (32) ve l,4-Bis(alliltiyo)-l,2,3,4-tetraklor-l,3-butadien (33) elde edildi. Elde edilen bu yeni bileşikler kristalizasyon ve kromatografîk yöntemlerle saflaştırılmıştır. Mikro analiz ve spektroskopik yöntemlerle (İR, NMR, MS v.b.) yapıları aydınlatılmıştır. xn SUMMARY `THE SYNTHESIS OF S- AND N-SUBSTITUTED ORGANIC COMPOUNDS FROM MONOEN AND DİEN STRUCTURE HAVING POLYHALOGENATED ORGANIC COMPOUNDS` In this work, firstly polihalogenated organic compounds were synthesized from dimerization of trichloroethylene. 4-Bromo-l,l,3,4-tetracMoro-2-nitro-l,3-butadiene (1) and l,l,3»4,4-Pentachloro-2-nitro-l,3-butadiene (18) compounds were obtained from the synthesized 2-H-4-Bromo-tetracMoro-l,3-butadiene and 2-H-Pentachloro-l,3- butadiene compounds. In the second step of this work, (1) and (18) compounds were used as starting compounds. In this step, S-substituted nitrodiene compounds were obtained. Therefore 4-Bromo- 1,3,4-trichloro- 1 -mono(p-chlorophenylthio)-2-nitro- 1,3-butadiene (8) were obtained from the reactions of 4-Bromo-l,l,3,4-tetrachloro-2-nitro-l,3-butadiene (1) with p-chlorothiophenol. Also l-(Allylthio)-l,3,4,4-tetrachloro-2-nitro-l,3-butadiene (19), l,l-Bis(allyltWo)0,4,4-tricmoro-2-nitro-l,3-butadiene (20) and l,l,4-Tris(allyl- thio)-3,4-dichloro-2-nitro-l,3-butadiene (21) compounds were obtained from the reactions of l,l,3,4,4-Pentachloro-2-nitro-l,3-butadiene (18) with allylmercaptan. In the third step, the reactions of some N-nucleophiles with S-substituted nitrodiene compounds that obtained and 4-Bromo- 1,3, 4-trichloro-l -mono(p-methyl- phenylthio)-2-nitro-l,3-butadiene (2) compound were done. N,N'-Bis(4-bromo-3,4-dichloro- 1 -(p-chlorophenylthio)-2-nitro- 1,3-butadienyl)- piperazine (9), N,N'-Bis(4-bromo-3,4-dichloro- 1 -(p-chlorophenylthio)-2-nitro- 1,3-buta- dienyl)-2,5-dimethy lpiperazine (10), 4-Bromo-3,4-dichloro- 1 -( 1 -(4-fluorophenyl)pipe- razme)-l-(p-cUorophenylthio)-2-nitro-l,3-butadiene (11), 4-Bromo-3,4-dichloro-l-(4- phenylpiperazine)-l-(p-chlorophenylthio)-2-nitro-l,3-butadiene (12), 4-Bromo-3,4-di chloro- 1 -(p-chlorophenylthio)- 1 -(4-methylpiperazine)-2-nitro- 1,3-butadiene (13), 4-Bromo-3,4-dichloro- 1 -(4-morpholino)- 1 -(p-chlorophenylthio)-2-nitro- 1,3-butadiene (14), 4-Bromo-3,4-dichloro- l-(p-chlorophenylthio)-2-nitro- 1 -piperidino- 1,3-butadiene (15), 4-Bromo-3,4-dichloro- 1 -(p-chloropheny lthio)-2-nitro- 1 -(4-methylpiperidino)- 1,3- butadiene (16) and 4-Bromo-3,4-dichloro- l-(phenylamino)-l -(p-chloropheny lthio)-2- nitro-l,3-butadine (17) were synthesized from the reactions of 4-Bromo- 1,3,4-trichloro- l-mono(p-chlorophenylthio)-2-nitro-l,3-butadiene (8) with piperazine, 4-morpholine, piperidine, 4-methylpiperidine and aniline, respectively. In the same way, N,N'-Bis(4-bromo-3,4-dichloro- l-(p-methylphenylthio)-2- nhro- 1,3-butadienyl)-2,5-dimethylpiperazine (3), 4-Bromo-3,4-dichloro- 1 -(4-fluorop- henylpiperazine)- 1 -(p-methylphenylthio)-2-nitro- 1,3-butadiene (4), 4-Bromo-3,4-dich loro- l-(4-phenylpiperazme)-l-(p-methylphenylthio)-2-nitro-l,3-butadiene (5), N,N'- Bis(4-hromo-3,4-dichloro- 1 -(p-methylphenylthio)-2-nitro- 1,3-butadienyl)-benzidine (6) and 4-Bromo-3,4-dichloro- 1 -(p-methylphenylthio)-2-nitro- l-(4-piperidinol)- 1,3-butadi- ne (7) compounds were obtained from the reactions 4-Bromo-l,3,4-trichloro-l-mono(p- metiiylphenylthio)-2-nitro-l,3-butadiene (2) with 2,5-dimethylpiperazine, l-(4-fluoro- phenyl)piperazine, 4-phenylpiperzaine, benzidine and 4-piperidinol, respectively. N,N'- xmBis(l-aUylthio-3,4,4-trichloro-2-nitro-l,3-butadienyl)-piperazine (22), l-(l-Allyltio)- 3,4,4-trichloro-2-nitro- 1,3-butadienyl)-4-(ethoxycarbonyl)-piperazine (23), N,N'-Bis(l - allyltbio-3,4,4-trichloro-2-nitro- 1,3-butadienyl)-2,5-dimethylpiperazine (24), 1 -( 1 - Allylthio)-3,4,4-trichloro-2-nitro- 1,3 -butadienyl)-4-phenylpiperazine (25), 1 -( 1 - Allyl- thio)-3,4,4-trichloro-2-nitro- 1,3-butadienyl)-4-(4-fluorphenyl)piperazine (26), l-(Ally- hhio)-3,4,4-trichloro-l-(4-morpholino)-2-nitro-l,3-butadiene (27) and l-(Allylthio)- 3,4,4-trichloro-2-nitro-l-piperidino-l,3-butadiene (28) compounds were obtained from the reactions of l-(AUylthio)-l,3,4,44etrachloro-2-nitro-l,3-butadiene (19) compound with piperazine, 1-ethoxycarbonylpiperazine, 2,5-dimethylpiperazine, 4-phenylpiperazi- ne, 4-morpholine and piperidine, respectively. 4,4'-Butandithio-bis(l, 1,2,3,4-pentachloro- 1,3-butadiene) (29), 1,6,7, 1 2-Tetra- thio-bis(l,2,3,4,4-pentachloro-l,3-butadienyl)-ikosane (30) and 2,3,4,5-Tetrachloro-l,6- dithia-cyclodeca-2,4-diene (31) compounds were obtained from the reactions of hexachlorobutadiene with butanditbiol in the presence of NaOH in ethanol. Also monothio- and dithio substituted compounds were obtained from the reactions of hexachlorobutadiene with allylmercaptan. Hexachlorobutadiene was reacted with allylmercaptan in the precence of NaOH. 1 -Mono(allylthio)- 1,2,3, 4,4- pentachloro- 1,3 -butadiene (32) and l,4-Bis(allylthio)-l,2,3,4-tetrachloro-l,3-butadiene (33) were obtained from this reactioa These novel compounds were obtained that either crystallized or purified by column chromatography. Structure of the products were characterized by microanalysis and spectroscopic methods (namely, ^-NMR, IR, MS). XTV
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