Bazı halodienler ve halokinonların mono- ve difonksiyonel gruplu tiyollerle reaksiyonlarından yeni tiyoeterlerin sentezi
The synthesis of the new thioethers from the reactions of some halodienes and haloquinones with thiols with mono- and difunctional groups
Yazar: NAHİDE GÜLŞAH DENİZ
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: Kristal yapı = Crystal structure ; Kükürt = Sulfur ; Organik moleküller = Organic molekules ; Spektroskopik veri = Spectroscopic data ; X ışını kırınımı yöntemi = X ray diffraction method

Özet:
Bu çalışmada, S-, N, S-, S, S-, S, O-nükleofilleri ile halokinon ve halobutadienlerin çeşitli reaksiyonları sonucu bilinmeyen yeni sübstitüekinon ve butadien bileşikleri sentezlendi. Yeni kinon bileşiklerinin sentezlenmesinde; başlangıç maddesi olarak 2,3-diklor-1,4-naftakinon (1a) ve p-kloranil (1b) bileşikleri kullanıldı. Yeni butadien bileşikleri sentezlemek için; trikloretilenin serbest radikal dimerleşmesi ile hazırlanan hekzaklorbuten bileşiği üzerinden, 1,1,3,4,4-Pentaklor-2-nitro-1,3-butadien (1c) bileşiği sentezlendi. 1,1,3,4,4-Pentaklor-2-nitro-1,3-butadien'in (1c) propantiyol ve oktadekantiyol ile reaksiyonundan, sırasıyla bilinmeyen yeni 2-Nitro-1,3,4,4-tetraklor-1-(propilsülfanil)-1,3-butadien (21) ve bilinen 2-Nitro-1,3,4,4-tetraklor-1-(oktadesilsülfanil)-1,3-butadien (1d) bileşikleri sentezlendi. Yeni nitrobutadien bileşiklerinin sentezlenmesinde; (1c), (1d) ve 21 bileşikleri başlangıç maddesi olarak kullanıldı.2,3-Dikloro-1,4-naftakinon (1a) bileşiğinin siklohekzilmerkaptan ile reaksiyonundan bilinmeyen yeni 2,3-bis(siklohekzilsülfanil)-1,4-naftakinon (2) ve 2-(1-siklohekzilsülfanil)-3-(1-etoksi)-1,4-naftakinon (3) bileşikleri sentezlendi. 2,3-Diklor-1,4-naftakinon (1a) ile 6-merkapto-1-hekzanol'ün reaksiyonundan bilinmeyen yeni 2-(6-sülfanil-1-hekzanol)-3-klor-1,4-naftakinon (4) ve 2,3-bis(6-sülfanil-1-hekzanol)-1,4-naftakinon (5) bileşikleri sentezlendi. Bilinmeyen yeni 2,3,4,5,6,7-hekzahidronafta[2,3-e][1,8]ditiyonin-9,14-dion (6), 7,8,9,10,11,12?hekzahidrodinafta[2,2':e]-dikloro[3,3'][1,8]ditiyonin-5,14,19,20-tetron (7), 7,8,9,10,11,12,21,22,23,24,25,26-dodekahidrodinafta[2,3-e:2',3'-n][1,8,11,18]tetratiyasiklotetrakosin-5,14,19,28-tetron (8) ve 7,8,9,10,11,12?hekzahidrodinafta[2,2'-e]?dietoksi[3,3'][1,8]ditiyonin-5,14,19,20-tetron (9) bileşikleri 2,3-Dikloro-1,4-naftakinon (1a) ile 1,6-hekzanditiyol'ün reaksiyonundan elde edildi. 2,3-Dikloro-1,4-naftakinon (1a) bileşiğinin 7-merkapto-4-metil-kumarin ile reaksiyonundan bilinmeyen yeni 2-(7-sülfanil-4-metil-kumarinil)-3-(1-etoksi)-1,4-naftakinon (10) ve 2,3-bis(7-sülfanil-4-metil-kumarinil)-1,4-naftakinon (11) bileşikleri sentezlendi. Bilinmeyen yeni [2,3-siklo-(2-butilamino)etansülfanil]-1,4-naftakinon (12), 2-[2-(butilamino)etansülfanil]-3-klor-1,4-naftakinon (13) ve [2-(butilamino)etansülfanil][2,2']-diklor[3,3']-bis[1,4-naftakinon] (14) bileşikleri 2,3-diklor-1,4-naftakinon'un (1a) 2-(butilamino)etantiyol ile reaksiyonundan elde edildi. 2,3-Diklor-1,4-naftakinon (1a) ile 11-merkapto-1-undekanol'ün reaksiyonundan bilinmeyen yeni 2-(11-sülfanil-1-undekanol)-3-etoksi-1,4-naftakinon (15) ve 2,3-bis(11-sülfanil-1-undekanol)-1,4-naftakinon (16) bileşikleri sentezlendi. p-Kloranil (1b) ile 11-merkapto-1-undekanol'un reaksiyonundan bilinmeyen yeni 2,3,6-tris(11-sülfanil-1-undekanol)-5-etoksi-1,4-benzokinon (17) ve 2,3,5,6-tetrakis(11-sülfanil-1-undekanol)-1,4-benzokinon (18) bileşikleri elde edildi. 2,3-Diklor-1,4-naftakinon (1a) ile 1,8-oktanditiyol'ün reaksiyonundan bilinmeyen yeni 2,3,4,5,6,7,8,9-oktahidronafta[2,3-e][1,10]ditiyonin-11,16-dion (19) ve 7, 8, 9, 10, 11, 12, 13, 14, 23, 24, 25 ,26, 27, 28, 29,30-hekzadekahidrodinafta-[2,3-e:2',3'-n][1,10,13,22]-tetratiyasiklotetrakosin-5,16,21,32-tetron (20) bileşikleri sentezlendi. Bilinmeyen yeni 2-nitro-3,4,4-triklor-1-(propilsülfanil)-1-(tiyomorfolinil)-1,3-butadien (22) bileşiği; 2-nitro-1,3,4,4-tetraklor-1-(propiltiyo)-1,3-butadien (21) ile tiyomofolin'in reaksiyonundan elde edildi. Yeni 2-nitro-3,4,4-triklor-1-(oktadesilsülfanil)-1-(tiyomorfolinil)-1,3-butadien (23) bileşiği; bilinen 2-nitro-1,3,4,4-tetraklor-1-(oktadesilsülfanil)-1,3-butadien (1d) ile tiyomorfolin'in reaksiyonundan elde edildi. 2-Nitro-1,3,4,4-tetraklor-1-(propilsülfanil)-1,3-butadien (21) ile N-(difenilmetil)piperazin'in reaksiyondan bilinmeyen yeni 2-nitro-3,4,4-triklor-1-(propilsülfanil)-1-[4-(difenilmetil)piperazin-1-il]-1,3-butadien (24) bileşiği sentezlendi. Yeni 2-nitro-3,4,4-triklor-1-(oktadesilsülfanil)-1-[4-(difenilmetil) piperazin-1-il]-1,3-butadien (25) bileşiği; bilinen 2-nitro-1,3,4,4-tetraklor-1-(oktadesilsülfanil)-1,3-butadien (1d) ile N-(difenilmetil)piperazin'in reaksiyonundan elde edildi. 2-Nitro-1,3,4,4-tetraklor-1-(propilsülfanil)-1,3-butadien (21) ile 4-(florofenil)piperazin'in reaksiyonundan bilinmeyen yeni 2-nitro-3,4,4-triklor-1-(propilsülfanil)-1-[4-(florfenil) piperazin-1-il]-1,3-butadien (26) bileşiği sentezlendi. Yeni 2-Nitro-3,4,4-triklor-1-(oktadesilsülfanil)-1-[4-(florfenil) piperazin-1-il]-1,3-butadien (27) bileşiği; bilinen 2-nitro-1,3,4,4-tetraklor-1-(oktadesilsülfanil)-1,3-butadien (1d) ile 4-(florfenil)piperazin'in reaksiyonundan elde edildi. 2-Nitro-1,3,4,4-tetraklor-1-(propilsülfanil)-1,3-butadien (21) ile 2-(florfenil)piperazin'in reaksiyonundan bilinmeyen yeni 2-nitro-3,4,4-triklor-1-(propilsülfanil)-1-[2-(florfenil)piperazin-1-yil]-1,3-butadien (28) bileşiği sentezlendi. Yeni 2-nitro-3,4,4-triklor-1-(oktadesilsülfanil)-1-[2-(florfenil)piperazin-1-il]-1,3-butadien (29) bileşiği; 2-nitro-1,3,4,4-tetraklor-1-(oktadesilsülfanil)-1,3-butadien (1d) ile 2-(florfenil)piperazin'in reaksiyonundan elde edildi. Bilinen 1,1,3,4,4-pentaklor-2-nitro-1,3-butadien (1c) ile 2-(butilamino)etantiyol'ün reaksiyonundan yeni 3,4,4-triklor-2-nitro-1-[siklo-(2-butilaminoetilsülfanil)]-1,3-butadien (30) bileşiği sentezlendi. 2-Nitro-1,3,4,4-tetraklor-1-(oktadesilsülfanil)-1,3-butadien (1d) ile 1-(piperonil)piperazin'in reaksiyonundan, bilinmeyen yeni 3,4,4-triklor-2-nitro-1-(oktadesilsülfanil)-1-[1-piperonilpiperazin-1-il)]-1,3-butadien (31) bileşiği sentezlendi.Sentezlenen yeni kinon ve 2-nitro-butadien bileşiklerinin yapıları; mikro analiz, 1H-NMR, 13C-NMR, FT-IR ve MS teknikleri kullanılarak aydınlatıldı. Sentezlenen yeni kinon bileşikleri için UV-vis ve Floresans Spektroskopisi yöntemleri uygulandı. (10), (22), (24) ve (26) bileşiklerinin tek kristal yapısı, birim hücre parametreleri ve kritalografik değerleri X-Işını Tek Kristal Kırınımı yöntemi kullanılarak bulundu.

Abstract:
In this study, the unknown new substituted-quinone and halobutadiene compounds were synthesized by reactions of S-, N, S-, S, S-, S, O- nucleophiles with haloquinones and halobutadienes. 2,3-Dichloro-1,4-naphthoquinone (1a) and p-chloranil (1b) were used as starting materials to synthesis of new quinone compounds. 1,1,3,4,4-pentachloro-2-nitro-1,3-butadiene (1c) was synthesized starting from free radical dimerization of trichloroethylene through hexachlorobutene compound as to synthesis of new butadiene compounds. Respectively, unknown new 2-nitro-1,3,4,4-tetrachloro-1-(propylsulfanyl)-1,3-butadiene (21) and known 2-nitro-1,3,4,4-tetrachloro-1-(octadecylsulfanyl)-1,3-butadiene (1d) compounds were synthesized from reactions of 1,1,3,4,4-pentachloro-2-nitro-1,3-butadiene (1c) with propanethiol and octadecanthiol. (1c), (1d) and 21 compounds were used as starting materials of sythesis of new nitrobutadiene compounds.Unknown new 2,3-bis(cyclohexylsulfanyl)-1,4-naphthoquinone (2) and 2-(1- cyclohexylsulfanyl)-3-(1-etoxy)-1,4-naphthoquinone (3) compounds were synthesized by reaction of 2,3-dichloro-1,4-naphthoquinone (1a) with cyclohexylmercaptane. Unknown new 2-(6-sulfanyl-1-hexanol)-3-chloro-1,4-naphthoquinone (4) and 2,3-bis(6-sulfanyl-1-hexanol)-1,4-naphthoquinone (5) were synthesized by reaction of 2,3-dichloro-1,4-naphthoquinone (1a) with 6-mercapto-1-hexanol. Unknown new 2,3,4,5,6,7-hexahydronaphtha[2,3-e][1,8]dithionine-9,14-dione (6), 7,8,9,10,11,12?hexahydrodinaphtha[2,2':e]-dichloro[3,3'][1,8]dithionine-5,14,19,20-tetrone (7), 7,8,9,10,11,12,21,22,23,24,25,26-dodecahydrodinaphtha [2,3-e:2',3'-n] [1,8,11,18] tetrathiacyclotetracosine-5,14,19,28-tetrone (8) and 7,8,9,10,11,12?hexahydrodinaphtha [2,2'-e]?diethoxy[3,3'][1,8]dithionine-5,14,19,20-tetrone (9) were obtained from reaction of 2,3-dichloro-1,4-naphthoquinone (1a) with 1,6-hexanedithiol. Unknown new 2-(7-sulfanyl-4-methyl-coumarinyl)-3-(1-ethoxy)-1,4-naphthoquinone (10) and 2,3-bis(7-sulfanyl-4-methyl-coumarinyl)-1,4-naphthoquinone (11) compounds were synthesized by reaction of 2,3-dichloro-1,4-naphthoquinone (1a) with 7-mercapto-4-methyl-coumarine. Unknown new [2,3-cyclo-(2-butylamino)ethanesulfanyl]-1,4-naphthoquinone (12), 2-[2-(butylamino)ethanesulfanyl]-3-chloro-1,4-naphthoquinone (13) and [2-(butylamino)ethanesulfanyl][2,2']-dichloro[3,3']-bis[1,4-naphthoquinone] (14) compounds were obtained from reaction of 2,3-dichloro-1,4-naphthoquinone (1a) with 2-(butylamino)ethanethiol. Unknown new 2-(11-sulfanyl-1-undecanol)-3-ethoxy-1,4-naphthoquinone (15) and 2,3-bis(11-sulfanyl-1-undecanol)-1,4-naphthoquinone (16) compounds were synthesized by reaction of 2,3-dichloro-1,4-naphthoquinone (1a) with 11-mercapto-1-undecanol. Unknown new 2,3,6-tris(11-sulfanyl-1-undecanol)-5-ethoxy-1,4-benzoquinone (17) and 2,3,5,6-tetrakis(11-sulfanyl-1-undecanol)-1,4- benzoquinone (18) were obtained from reaction of p-chloranil (1b) with 11-mercapto-1-undecanol. Unknown new 2,3,4,5,6,7,8,9-octahydronaphtha[2,3-e][1,10]dithionine-11,16-dione (19) and 7, 8, 9, 10, 11, 12, 13, 14, 23, 24, 25, 26, 27, 28, 29, 30-hexadecahydrodinaphtha-[2,3-e:2',3'-n][1,10,13,22]-tetrathiacyclotetracosine- 5, 16, 21, 32-tetrone (20) compounds were synthesized by reaction of 2,3-dichloro-1,4-naphthoquinone (1a) with 1,8-octanedithiol. Uknown new 2-Nitro-3,4,4-trichloro-1-(propylsulfanyl)-1-(thiomorpholinyl)-1,3-butadiene (22) was obtained from reaction of 2-Nitro-1,3,4,4-tetrachloro-1-(propylthio)-1,3-butadiene (21) with thiomorpholine. Novel 2-nitro-3,4,4-trichloro-1-(octadecylsulfanyl)-1-(thiomorpholinyl)-1,3-butadiene (23) compound was obtained from reaction of known 2-nitro-1,3,4,4-tetrachloro-1-(octadecylsulfanyl)-1,3-butadiene (1d) with thiomorpholine. Unknown new 2-nitro-3,4,4-trichloro-1-(propylsulfanyl)-1-[4-(diphenylmethyl)piperazine-1-yl]-1,3-butadiene (24) was synthesized by reaction of 2-nitro-1,3,4,4-tetrachloro-1-(propylsulfanyl)-1,3-butadiene (21) with N-(diphenylmethyl)piperazine. Novel 2-nitro-3,4,4-trichloro-1-(octadecylsulfanyl)-1-[4-(diphenylmethyl)piperazine-1-yl]-1,3-butadiene (25) compound was obtained from reaction of known 2-nitro-1,3,4,4-tetrachloro-1-(octadecylsulfanyl)-1,3-butadiene (1d) with N-(diphenylmethyl)piperazine. Unknown novel 2-nitro-3,4,4-trichloro-1-(propylsulfanyl)-1-[4-(fluorophenyl) piperazine-1-yl]-1,3-butadiene (26) compound was synthesized by reaction of 2-Nitro-1,3,4,4-tetrahloro-1-(propylsulfanyl)-1,3-butadiene (21) with 4-(fluorophenyl)piperazine. Novel 2-nitro-3,4,4-trichloro-1-(octadecylsulfanyl)-1-[4-(fluorophenyl) piperazine-1-yl]-1,3-butadiene (27) compound was obtained from reaction of known 2-nitro-1,3,4,4-tetrachloro-1-(octadecylsulfanyl)-1,3-butadiene (1d) with 4-(fluorophenyl)piperazine. Unknown new 2-Nitro-3,4,4-trichloro-1-(propylsulfanyl)-1-[2-(fluorophenyl) piperazine-1-yl]-1,3-butadiene (28) was synthesized by reaction of 2-nitro-1,3,4,4-tetrachloro-1-(propylsulfanyl)-1,3-butadiene (21) with 2-(fluorophenyl)piperazine. New 2-nitro-3,4,4-trichloro-1-(octadecylsulfanyl)-1-[2-(fluorophenyl)piperazine-1-yl]-1,3-butadiene (29) compound was obtained from reaction of 2-nitro-1,3,4,4-tetrachloro-1-(octadecylsulfanyl)-1,3-butadiene (1d) with 2-(fluorophenyi)piperazine. New 3,4,4-trichloro-2-nitro-1-[cyclo-(2-butylaminoethylsulfanyl)]-1,3-butadiene (30) was synthesized by reaction of known 2-nitropentachloro-1,3-butadiene (1c) with 2-(butylamino)ethanethiol. Unknown new 3,4,4-trichloro-2-nitro-1-(octadecylsulfanyl)-1-[1-piperonylpiperazine-1-yl)]-1,3-butadiene (31) compound was synthesized by reaction of 2-nitro-1,3,4,4-tetrachloro-1-(octadecylsulfanyl)-1,3-butadiene (1d) with 1-(piperonyl)piperazine.The structure of novel synthesized quinone and 2-nitro-butadiene compounds was determined by using micro analysis, 1H-NMR, 13C-NMR, FT-IR and MS techniques. UV-vis and fluorescence spectroscopy method were used for new synthesized quinone compounds. The crystal structure of compounds (10), (22), (24) and (26), unit cell parameters and crystallographic data were determined by using X-Ray Single Crystal Diffraction method.