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

Bazı tiyol ve tiyoeterlerin sentezi ve oksidasyon reaksiyonlarının incelenmesi

The Investigation of synthesis and oxidation reactions of some thiols and thioethers

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Özet:

s ÖZET J I i BAZI TİYOL VE TTYOETERLERİN SENTEZİ VE OKSİDASYON REAKSİYONLARININ İNCELENMESİ Bu çalışmada ilk aşamada trikloretilenin dimerleşmesi sonucu 2-H-pentaklor- 1,3-butadien bileşiği sentezlendL Elde edilen bu bileşiğin nitrolanması sonucu 2- Nitro-1,1,3,4,4-pentaklor-l,3-butadien (1) bileşiği kazanıldı. Bu bileşik başlangıç maddesi olarak kullanıldı. 2-Nitro-l,l,3,4,4-pentaklor-l,3- butadien (1)' in p-metilfenütiyoLÜe-reaksiyonundan 2-Nitro-l,3,4,4-tetraklorrl-(p- metilfeniltiyo)-l,3-butadien (2)> p-klorfeniltiyol ile reaksiyonundan 2-Nitro- l,3A4-tetraMor-l^-Morfeniltiyo)-l,3-butadien (7), 2-Naftiltiyol ile reaksiyo nundan 2-Ni1xo-l3,4,4-teöaklor-l-(2--naftiltiyo)-l,3-bul2dien (11), etantiyol ile reaksiyonundan 2-Nirro-13:44=tetraMor-l-(etiltryo)-13-butadien _ (22) ve.. feniltiyol ile reaksiyonundan 2rNilTO-3,4-dMor-tris(feniltiyo)-l,3-butadien (31) gibi bilinen S-sübstitüe nitrodien bileşikleri elde edildi. Çalışmanın ikinci aşamasında elde edilen mono(tiyo)sübstitüe nitrodien bileşikleri N-nükleofiller ile reaksiyona sokuldu. 2-Nitro-l,3,4,4-tetraklor-l-(p- metilfeniltiyo)-l,3-butadien (2)'in 4-metilpiperidin, l-(4-fluorfenil)piperazin, 4- benzilpiperidin, N-fenilpiperazin ile reaksiyonundan sırasıyla yeni 3,4,4-triklor-l- (4-metüpiperidino)-l-(p-metilfeniltiyo)-2-nitro-l,3-butadien (3), 3,4,4-triklor-l- ^-metilfenütryo)-l-(4-fluorfenüpiperazm)-2-nitro-l,3-b^ (4), 3,4,4-tri-klor- l-(4-benzilpiperidmo)-l-(p-metin%m^iyo>2-nitro-l,3-butadien (5), 3,4,4-tri-klor- l^-fenüpipera2İn)-l-(p-metilfeniftiyo)-2-nitro-l,3-butadien (6) bileşikleri elde edildi. i *?%.' 2-Nitro-13,4,4-tetraklor-l-(p-klorfemltiyo)-l,3-butadien (7)*in 4-metilpipe ridin, l-(4-ıîûorfenil)piperazin, 4ibenzüpiperidin ile reaksiyonundan sırasıyla yeni 3,4,4-triklor- 1 -(4-metilpiperidino )- 1 -(p-klorfeniltiyo)-2-nitro- 1,3-butadien (8), 3,4,4-triklor-İ-(p-klorfenkiyo)-lK^ (9), 3,4,4-triktor-l-(4-benzilpiperidmo)-l-(p-klorfeniltiyo)-2-nitro-l,3-butadien (10) bileşikleri elde edildi. [ \ Aym şekilde 2-Nitro-l,3,4,4-lletraklor-l-(2-Naftiltiyo)-l,3-butadien (l'l)'in 1- (4-fluorfenil)piperazin, 4-metilpiperidin, l-(2-bidroksietil)-piperazin, piperidin, 4- benzilpiperidin, piperazdn, benzidin, N-fenilpiperazin,; 1-metilpiperazin ve o- fenilendiamin ile reaksiyonundan sırasıyla yeni 3,4,4-triklor-l-(2-naftiltiyo)-l-(4- fluorfenilpiperazin)-2-nitro- 1,3-butadien (12), 3,4,4-triklor- 1 -(4-metilpiperidino)- H2-naftütiyo)-2-nitro-l,3-butadıen (13), 3,4,4-triklor-l-(2-naftiltiyo)-l-(2- bidroksietilpiperazin)-2-nitro-l,3l-butadien(14), 3,4,4-rriklor-l-(piperidino)-l-(2- naftiltiyo)-2-nitro- 1,3-butadien (15), 3,4,4-triklor- 1 -(4-benzilpiperidino)- 1 -(2- JOL& ~,; i" I EST:" V;,, r g;V, naftiltiyo)-2-nitro-l,3-butadien (16),. N^f-Bis(3,4,4-triklor-l-(2-naftil-tiyo)-2- nltro-l,3-butadienil)-piperazin (17), 3^4,4-triklor-(2-naftiltiyo)-l-(benzidirio)-2- nitro4,3-butadien(18)?i3,4,4-triklor-l-(N^^ 1,3-butadien (19), 3i4,4-trildor-l-(l-metüpiperazin)-l-(2-nafliltiyo)f2-nitro-l,3- bıktadien (20), N^Bis(3,4,4-triklor-l-(2-nafti]tiyo)-2-nitro-l,3-buta-dieiiil)-o- fejnilendiamin (21) bileşikleri elde edildi ^g'*-. :-" ! 2-NitiX)-13,4,4-tetraklor-l-(etiltiyo)-l,3-butadien (22)'in 4-morfolin, pipe- razin ve piperidin ile reaksiyonundan sırası ile yeni 3,4,4-triklor-l-(4--morfolino)- l-j(etütiyo)-2-nhro-13-butadien (23), 3,4,4-triklor-l-(etiltiyo)-l-(piperazin)-2- nitro-l,3-butadien (24) ve 3,4,4-triMor-l-(jpçeridino)-l-(etiltiyo>2-nitro-l,3- butadien (25) bileşikleri elde edildi Üçüncü aşamada heksaklorbutadien'in 2-merkaptoetanol ve 2-nafültiyol ile etanoflü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan yeni mono(tiyo)sübstitüe ve di(tiyo)sübstitüe l,2,3,4,4-pentaklor-l-(2-nidrpksietiltiyo)- 1,3-butadien (26), U,3,454-pentaklor-l-(2-naftiltiyo)-l,3-butadien (27) ve 1,4- B^2-Mdroksietikiyo>lİ^,4-tetra]dor-l,3-butadien (28) bileşikleri elde edildi. Elde edilen l^,3,4,4-pentaklor-l-(2-hidroksietiltiyo)-l,3-butadien (26), l^,3,4,4-pentaklor-l-(2rnaftiltiyo)-l,3-butadien (27) ve 2-Nitro-3,4-diklor- tris(feniltiyo)-l,3-butadien (31) bileşiklerinin 3-klorperoksibenzoikasit ile klorofonnlu ortamda soğukta gerçekleştirilen reaksiyonundan yeni 1^,3,4,4- penta-Mor-l-(2-Mdroksietü^ülfM)-l,3-butadien (29), l,2,3,4,4-pentaklor-l-(2- naftilsülfinil)-l,3-butadien (30) ve 2-Nîtxo-bis(feniltiyo)-3,4-diklor-4-(fenil- sülfonil)- 1,3-butadien (32) bileşikleri elde edilmiştir. Aynca^pHaıetiltryofenol, o-aminotiyofenol, p-klortiyofenorün 2-kloretanol ile NaOH varlığında gerçekleştirilen reaksiyonundan sırasıyla bilinen 2-(p- metüfeniltiyo)-etanol (33), 2-(o-aminofeniltiyo)-etanol (34) ve 2-(p-klorfeniltiyo)- etanol (35) bileşikleri sentezlendl Elde edilen (33), (34) ve (35) bileşiklerinin tryoüre ile asitli ortamda gerçekleştirilen reaksiyonundan bilinen 2-(p- metüTenütiyo)-etantiyol (36), 2-(o-aminofeniltiyo)-etantiyol (37) ve 2-(p- klorfeniltiyo)-etantiyol (38) bileşikleri elde edildi i : Elde edilen bu 28 adet yeni bileşik kristalizasyon ve kromatografîk yöntemler ile saflaştınkh. Yapılan mikroanaliz ve spektroskopik yöntemler ile (İR, NMR, MS vb.) aydınlatılmıştır. XIII

Summary:

?**,?'».'.? % *.flnEgSZBlllI^B??i-ViL^*'?EJnl»''-ıi'ı.-jjij--ırjı...T -- n... SUMMARY THE INVESTIGATION OF SYNTHESIS AND OXIDATION REACTIONS OF SOME THIOLS AND TÖIOETHERS In this work, firstly 2-H-pen1achloro-l,3-butadiene compound was synthesized from dimerization oftrichlorethylene. 2-Nitro-l,l,3,4,4-pentachloro-l,3-butadiene (1) compound was obtained from nitration of that synthesized compound. This compound was used as starting compound. 2-Nitro-l,3,4,4-te1iachloro-l- (p-methylpheniythio)-l,3-butadiene (2), 2~Nitro-l,3,4,4-tetrachloro-l-(p- chorophenyltMo)-l,3~butadiejje (7), 2-Nitro-13,4Atetracloro-l-(2-naphthylthio)- 1,3-butadiene (11), 2-Nitro43A4-tetı^Woro-l<ethylthıo>U-butadiene (22) and 2-Nitro-3,4-dicMoro-tris(phenylthio)-l,3-butadiene (31) as known S- substituted nitrodiene compounds were obtained from the reactions of 2-Nitro- 1^3?454-pentacUoro-l-3-butkiiene-(l) with p-methylphenylthiol, -p-chloro- phenylthiol, 2-Naphthylthiol, lethanethiol and phenylthioL *H r In the second step of this work, the reaction of N-nucleophiles with mono(thio)substituted nitrodiene compounds was carried out 3,4,4-trichloro-l-(4- memylpiperidmo)-l-(p-memylphenyltMo)-2-nitro-l,3-butadiene (3), 3,4,4- tricUoro-l-(p-me1iiylphenyitMo)-l-(4-fiuorophenylpiperazme)-2-rdtro-l,3-buta- diene (4), 3,4,4-trichloro- 1 -(4-benzylpiperidino)- 1 -(p-methylphenylthio)-2-nitro- 1,3-butadiene (5), 3,4,4-tricUoro-l-^-phenylpiperazme)-l-^-methylphenylthio)- 2-nitro-l,3-butadiene (6) unknown compounds were obtained from the reactions of 2-Nitro-l,3,4,44etracMoro7İ-(r)-me%lphenylthia)-l,3-butadiene (2) with 4- methyl-piperidine, l-(4-fluorophenyl)piperazine, 4-benzylpiperidine, N- phenylpiperazine, respectively. 3,4,4-trichloro- 1 -(4-methylpiperidino)- 1 -(p-chlorophenykhio)-2-nitro-l,3-buta- diene (8), 3,4,4-tricMoro-l-(p^Uorophenylthio)-l-(4-fluoiophenylpiperazine)-2- nitro-l,3-butadiene (9), 3,4,4ftrichloro-l-(4-benzylpiperidino>l-(p-chlorophenyl- thio)-2-nitro-l,3-butadiene (1İ0) unknown compounds were obtained from the reactions of 2-Nhro-l,3,4,4-tetracrüoro-l-(p-chlorophenylthio>l,3-butadiene (7) with 4-methylpiperidine, l-(4-fluorophenyl)piperazine, 4-benzylpiperidine res pectively. ?, ^ j I Similarly, l-(3,4,4-1xicUoro-l-(2-naphmyfthio)-l-(4-fluorophenylpiperazine)- 2-nitro-l;3-butadiene (12), 3,4,4-trichloro-l-(4-methylpiperidino)-l-(2- naphthylthio)-2-nitro-l,3-butâdiene (13), 3,4,4-trichloro-l-(2-naphthylthio)-l-(2- hidroxye|tylpiperazine)-2-mtro-l,3-butadiene. (İ4), 3,4,4-trichloro- 1 -(2- naphthylthio)-l-(piperidino)-2-nitro-l,3-butadiene \ (15), 3,4,4-trichloro- 1 -(4- benzylpiperidino)-l-(2-naphthylthio)-2-nitro-l,3-butadiene (16), N^f-Bis(3,4,4- trichJoro-l-(2-naphthylthio)-2-nitro-l,3-butadienyl)-piperazine (17), 3,4,4- tricrdpro-(2-naph%Mo)-Hr«nzidino)-2-nitro-l,3-butadiene(18), 3,4,4-trichloro- XIVl-(N-phenylpiperazine)-l-(2-mph1iıyltMo)-2-rdtro-l,3-butadieıi.e (19), 3,4,4-tri- clıloro-l-(l-methylpiperaz3n)4-(2-mphthyft^ (20), N,N- Bis(3,4,4-McWoro~l-(2-mphthyftMo)-2-riitro-l,3-^ (21) unknown compounds were obtained from the reactions; of 2-Nitro-l,3,4,4- tetrachloro-l-(2-Naphthylthio)-l,3-butadiene (11) with! l-(4-fluoro- phenyl)piperazine, 4-methylpiperidine, 1^2-Mdroxyetibyhhio)-piperazine, piperidine, 4-benzyl-piperidin, piperazine, benzidine, N-pnenylpiperazine, 1- methyl-piperazine and o-phenylendiamine, respectively. | 3,4,4-tricWoro-l-(4-morpholko)-l-(ethyltMo)-2-nitro-l,3-butadiene (23), 3,4,4-1ricUoro-l^ethyhMo)-l-(piperazme)-2-nitro-l,3-butadiene (24) and 3,4,4- tricUoro-l-(piperidino)-l-(ethylthio)-2-mtro-l,3-butadiene (25) new compounds were obtained from the reactions of 2-Nitro-l,3,4,4-tetrachloto-l-(ethylthio)-l,3- butadiene (22) with 4-morpholine, piperazine and piperidine, respectively. 1 In the third step, mono(thio)substituted and di(tinq)substituted new compounds l^3,4,4^pentacWoro-l-(2-Mdroxye1±iyltMo)-l,3-butadiene (26), l^,3,4,4-pentacWoro-l-(2-naphthylthio)-l,3-butadiene (27)i and 1,4-Bis(2- hidroxyethylthio)~l,2,3,4-tetrachloro- 1,3-butadiene (28) were obtained from the reactions of hexachlorobutadiene with 2imercaptoetiwnol and 2-naphthylthiol in the presence of NaOH in Ethanol. U,3,4,4-pentacMoro-l-(2-rndroxye%lsülfmyl)4,3-butadiene (29), l,2,3,4,4-pentacHoro-l<2-naphmylsû1fmyl)-l,3-butadiene (30) and 2-Nitro- bis(phenylthio)-3,4^cMoro-4^(phenylsülfonyl)-l,3-butadiene (32) new compounds were obtained from the reactions of obtained 1,2,3,4,4-pentachloro-l- (2-hidroxyethylthio)-l,3-butadien (26), ll^,3,4,4-pentachloro-l-(2-naphthylthio)- 1,3-butadiene (27) and 2-Nitro-3,4^cMoro-tris(phenyhhio)-l,3-butadiene (31) compounds with 3-chloroperoxibenzoicacid in cold chloroform. Also 2-(p-methylphenylthio)-ethanol (33), 2-(o-aminophenylthio)-ethanol (34) and 2-(p-clorophenykhio)-ethanol (35) known compounds were synthesized from the reactions of p-methylthiophenol, o-aminothiophenol, p-clorothiophenol with 2-chloroethanol in the presence of NaOH, respectively. 2-(p-methylphenylthio)- ethanetiyol (36), 2-(o-arnmophenyltiiio)-ethanethiol (37) and 2-(p-cloro- phenylthio)-ethanethiol (38) known compounds were obtained from the reactions of obtained (33), (34) ve (35) compounds with thiourea in the presence of acid. These 28 novel compounds were obtained that either crystallized or purified by column cromatography. Structure of the products were characterized by microanalysis and spectroscopic methods ( IR, NMR, MS..etc). XV--