Tez özetleri Astronomi ve Uzay Bilimleri Anabilim Dalı

YILDIRIM Hatice

Danışman : Prof.Dr. Cemil İBİŞ

Anabilim Dalı : Kimya

Programı : Organik Kimya

Mezuniyet Yılı : 2010

Tez Savunma Jürisi : Prof.Dr. Cemil İBİŞ

Prof.Dr. Süleyman TANYOLAÇ

Prof.Dr. Ahmet AKAR

Prof.Dr. F.Serpil GÖKSEL

Prof.Dr. Belkıs BİLGİN ERAN

Bazı Yeni S-, N,S- Sübstitüe Dienler Ve S-Sübstitüe Buteninlerin Sentezi

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.

  

 

 

Synthesis Of Some New S- And N,S-Substituted Dienes And S-Substituted Butenins

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).

DÖĞER M. Mutluhan
Danışman : Prof. Dr. Refiye YANARDAĞ

Anabilim Dalı : Kimya

Programı : Biyokimya

Mezuniyet Yılı : 2010

Tez Savunma Jürisi : Prof. Dr. Refiye YANARDAĞ

Prof. Dr. Nuriye AKEV

Prof. Dr. Ayşen YARAT

Prof. Dr. İnci ARISAN ATAÇ

Prof. Dr. Ayşe YUSUFOĞLU

Ispıt’ın (Trachystemon Orientalis (L.) G. Don) Antioksidan Aktivitesi

Ispıt (Trachystemon orientalis (L.) G. Don), Türkiye’de Marmara ve Karadeniz bölgesinde yetişir ve bu bölgelerde sebze olarak yaygın bir şekilde kullanılır. Literatürde, ıspıtın balgam söktürücü, terletici, idrar söktürücü ve ateş düşürücü etkiye sahip olduğu belirtilmektedir. Ispıtın bu etkilerinin antioksidan aktiviteden ileri gelebileceği düşünülebilir.

Bu çalışmada, ıspıttan hazırlanan sulu, etil alkollü ve etil asetatlı ekstrelerin antioksidan aktiviteleri; DPPH radikal giderme aktivitesi, hidroksi radikal giderme aktivitesi, ABTS radikal giderme aktivitesi, DMPD radikal giderme aktivitesi, metal kelatlama aktivitesi, hidrojen peroksid radikal giderme aktivitesi ve lipozom peroksidasyonu üzerine antioksidan aktivitesi ve ferri iyonu üzerine redükleyici antioksidan potansiyeli gibi çeşitli antioksidan testler kullanılarak incelendi. Sonuçlar butillenmiş hidroksianisol, butillenmiş hidroksitoluen, Troloks, vitamin E gibi sentetik antioksidanlarda karşılaştırıldı. Ekstrelerin total fenolik bileşikleri, flavonoid miktarları, prolin miktarları ve E vitamini miktarları da tayin edildi. Ekstrelerin bütün testlerde antioksidan aktivite gösterdiği ve bu ekstrelerin doğal bir antioksidan kaynağı olabileceği sonucuna varıldı.

Antioxidant activity of Trachystemon orientalis (L.) G.Don

Trachystemon orientalis (L.) G. Don is grown in Marmara and Black Sea regions of Turkey and is commonly used as a vegetable in these regions. In literature, it is pointed out that orientalis has expectorant, diaphoretic, diuretic and antipyretic effects. It can be thought that these effects of Trachystemon orientalis (L.) G. Don arise from its antioxidant acitivity.

In this study, some tests are evaluated of water, ethanol and ethyl acetate extracts of Trachystemon orientalis to find out antioxidant activity depends at different maturing stages of plant or not. These tests are; DPPH radical scavenging, hydroxyl radical scavenging, ABTS radical scavenging, DMPD radical scavenging, metal chelating activity, hydrogen peroxide radical scavenging, antioxidant activity on liposome peroxidation, ferric ion reducing antioxidant power assay were employed in order to evaluate the antioxidant activities of water, ethanol and ethyl acetate extracts of Trachystemon orientalis (L.) G. Don. The results were compared with synthetic antioxidants, e. g. butylated hydroxyanisole, butylated hydroxytoluene, Trolox, and vitamin E. The levels of total phenolic compounds, total flavonoids, proline and vitamin E of the extracts were also determined. It was determined that extracts have shown antioxidant activity in all tests and that they could be considered as a source of natural antioxidants.

DENİZ Nahide Gülşah
Danışman : Prof. Dr. Cemil İBİŞ

Anabilim Dalı : Kimya

Programı : Organik Kimya

Mezuniyet Yılı : 2010

Tez Savunma Jürisi : Prof. Dr. Cemil İBİŞ

Prof. Dr. Mustafa BULUT

Prof. Dr. F. Serpil GÖKSEL

Prof. Dr. Süleyman TANYOLAÇ

Prof. Dr. Ahmet AKAR


Bazı Halodienler Ve Halokinonların Mono- Ve Difonksiyonel Gruplu Tiyollerle Reaksiyonlarından Yeni Tiyoeterlerin Sentezi

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.

The Synthesis Of The New Thioethers From The Reactions Of Some Halodienes And Haloquinones With Thiols With Mono- And Difunctional Groups

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.