Uluyazi cem İskender

CEYLAN İLHAN Berat
Danışman : Prof.Dr. Bahri ÜLKÜSEVEN

Anabilim Dalı : Kimya

Programı : Anorganik Kimya

Mezuniyet Yılı : 2010

Tez Savunma Jürisi : Prof.Dr. Bahri ÜLKÜSEVEN

: Prof.Dr. Süleyman TANYOLAÇ

: Prof.Dr. Ulvi AVCIATA

: Prof.Dr. Ahmet GÜL

: Prof.Dr. Sabiha MANAV YALÇIN

Bazı Sübstitüe 2-Hidroksi-Benzofenon Tiyosemikarbazonların Oksomolibden(Vı) Kompleksleri

2-hidroksibenzofenon S-metil-4-fenil-tiyosemikarbazon (LI), 5-kloro-2-hidroksibenzofenon S-metil-4-fenil-tiyosemikarbazon (LII) ve 5-kloro-4-metil-2-hidroksibenzofenon S-propil-4-fenil-tiyosemikarbazon (LIII) olmak üzere 3 yeni tiyosemikarbazon sentez edildi.

Tiyosemikarbazon ligandlarının bis-asetilasetonato dioksomolibden(VI) [MoO2(acac)2] kompleksi ile reaksiyonundan, ikinci ligandların metanol, etanol, propanol, butanol, pentanol, etilen glikol monometil eter, etil asetat, alilalkol, DMF, γ-pikolin, piridin ve isoamilalkol olduğu [MoO2(L)D] genel formülü ile gösterilen 24 adet yeni cis-dioksomolibden(VI) çelat yapılı kompleks izole edildi.

Stabil kristal katı formundaki bu kompleksler elementel analiz ve iletkenlik ölçümleri yanısıra elektronik, infrared, 1H-NMR, 13C-NMR ve kütle spektroskopisi ile kararkterize edildi. Uygun tek kristali elde edilebilen kompleksler, [MoO2(LI)Propanol], [MoO2(LII)Pentanol], [MoO2(LII)Alilalkol], [MoO2(LIII)Metanol] ve [MoO2(LIII)Propanol] tek kristal X-ışını kırınımı yöntemi ile ayrıca incelenerek yapıları hakkında detaylı bilgi verildi.

Oxomolybdenum (Vı) Complexes Of Some Substıtuted 2-Hyroxy-Benzophenone Thıosemıcarbazones

The three new ligands have been synthesized namely 2-hydroxybenzophenone S-methyl-N-phenyl-thiosemicarbazone (LI), 5-chloro-2-hydroxybenzophenone S-methyl-N-phenyl-thiosemicarbazone (LII) and 5-chloro-4-methyl-2- hydroxybenzophenone S-propyl-N-phenyl-thiosemicarbazone (LIII).

By the reaction of thiosemicarbazone ligands with bis-acetylasetonato dioxomolybdenum(VI) [MoO2(acac)2] complex, 24 new cis-dioxomolybdenum(VI) chelate complexes in general formula [MoO2(L)D] have been isolated containing methanol, ethanol, propanol, butanol, pentanol, ethylene glycol monomethyl ether, ethyl acetate, allylalcohol, DMF, γ-picoline, pyridine or ısoamylalcohol as a second ligand.

The these stable crystal solid formed complexes have been characterized by elementel analysis, conductivity measurements, electronic, infrared, 1H-NMR, 13C-NMR and mass spectroscopies. Structures of [MoO2(LI)Propanol], [MoO2(LII)Pentanol], [MoO2(LII)Alilalkol], [MoO2(LIII)Metanol] and [MoO2(LIII)Propanol] complexes, whose single crystals can be obtained properly, have been further analysed by X-ray single crystal diffraction method and detailed structure information is given about these complexes.

AYLA ŞAHİNLER Sibel
Danışma : Prof. Dr. Cemil İBİŞ

Anabilim Dalı : Kimya

Programı (Varsa) : 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

Polihalobuten Ve Halobutadienlerin Tiyollerle Reaksiyonundan Yeni Tiyoeterlerin Sentezi

Bu çalışmanın ilk aşamasında Trikloroetilenin dibenzoilperoksit varlığında serbest radikaller üzerinden yürüyen dimerizasyonu sonucu 1,1,3,3,4,4-Heksaklor-1-buten (1) bileşiği elde edildi. Bu bileşikten çıkarak diğer başlangıç maddesi 2H-1,1,3,4-tetraklor-4-brombutadien (2) sentezlendi. Çalışmanın ikinci aşamasında (1) ve (2) bileşikleri başlangıç maddesi olarak kullanıldı ve bilinmeyen yeni –S sübstitüe bileşikleri elde edildi.

1,1,3,3,4,4-Heksaklor-1-buten (1) başlangıç maddesiyle dipolar aprotik çözücü varlığında 7-merkapto-4-metil kumarin, 2-merkaptofenol, 2-metiltiyofenol, 4-flortiyofenol, 4-metoksitiyofenol, 2,4-dimetiltiyofenol, 3,4-dimetokstiyofenol, pentaflortiyofenol ve p-nitrotiyofenol reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 2-Klor-1,1,4,4-(7-merkapto-4-metil-kumarinil)-1,3-butadien (3), 2-Klor-1,1,4,4-(2-hidroksifeniltiyo)-1,3-butadien (4), 2-Klor-1,1,4,4-(2-metilfeniltiyo)-1,3-butadien (5), 2-Kloro-1,4,4-(4-florofeniltiyo)-1,3-butadien (6), 2-Klor-1,4,4,4-(4-metoksifeniltiyo)-1,3-butadien (7), 2-Klor-1,1,4,4-(2,4-dimetilfeniltiyo)-1,3-butadien (8), 1,1,2,4-Tetraklor-4-(3,4-dimetoksifeniltiyo)-1,3-butadien (9), 2-Klor-1,1,4,4-(pentaflorfeniltiyo)-1,3-butadien (10) ve 1,1,3-Triklor-4,4-(4-nitrofeniltiyo)-1,3-butadien (28) bileşikleri sentezlendi.

1,1,3,3,4,4-Heksaklor-1-buten (1) başlangıç maddesiyle protik çözücü varlığında 7-merkapto-4-metil kumarin, 2-metiltiyofenol, 2,4-dimetiltiyofenol, 3,4-dimetoksitiyofenol, 2-merkaptobenzotiazol, 2-merkaptobenzimidazol, 2,2,2-trifloretantiyol, 3-merkapto-1-propanol ve siklopentil merkaptan reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 1,1,2,4-Tetraklor-4-(7-merkapto-4-metil-kumarinil)-1,3-butadien (11), 1,2-Diklor-1,4,4-(7-merkapto-4-metil-kumarinil)-1,3-butadien (12) ve 1,1,2-Triklor-4-(7-merkapto-4-metil-kumarinil)-1-buten-3-in (13), 1,1,2-Triklor-4-(2-metilfeniltiyo)-1-buten-3-in (14), 1,1,2-Triklor-4-(2,4-dimetilfeniltiyo)-1-buten-3-in (15), 1,2-Diklor-1,4-(3,4-dimetoksifeniltiyo)-1-buten-3-in (16) ve 2-Klor-1,1,4-(3,4-dimetoksifeniltiyo)-1-buten-3-in (17), 1,1,2,4-Tetraklor-4-(benzo-1,3-tiyazolil-(2)-tiyo)-1,3-butadien (18), 1,1,2,4-Tetraklor-4-(benzo-1,3-imidazolil-(2)-tiyo)-1,3-butadien (19), 2-Klor-1,1,4,4-(2,2,2-triflor-etil-sülfanil)-1,3-butadien (20), 2-Klor-1,1,3,4,4-(2,2,2-triflor-etil-sülfanil)-1,3-butadien (21), 2-Klor-1,1,4,4-(1-propanol-3-sülfanil)-1-buten-3-in (22), 1,1,2-Triklor-4,4-(siklopentil-sülfanil)-1,3-butadien (26), 1,1,2,4-(siklopentil-sülfanil)-1-buten-3-in (27) bileşikleri elde edildi.

H-1,1,3,4-tetraklor-4-brombutadien (2) başlangıç maddesiyle protik çözücü varlığında 7-merkapto-4-metil kumarin, 2,4-dimetiltiyofenol ve 2-merkaptobenzotiazol bileşikleri reaksiyona sokuldu. Reaksiyonlar sonucunda 1-Brom-1,2-Diklor-4-(7-merkapto-4-metil-kumarinil)-1-buten-3-in (23), 1-Brom-1,2-Diklor-4-(2,4-dimetilfeniltiyo)-1-buten-3-in (24) ve 1-Brom-1,2-Diklor-4-(benzo-1,3-tiyazolil-(2)-tiyo)-1,3-butadien (25) bileşikleri elde edildi.

Sentezlenen bu yeni bileşiklerin yapıları mikroanaliz, FTIR, 1H NMR, 13C NMR, 19F NMR, MS, UV-Vis ve floresans spektroskopi teknikleri kullanılarak aydınlatıldı.

 
Synthesıs Of New Thıoethers From The Reactıon Of Polyhalobutene And Halobuthadıenes Wıth Thıols

In this work, firstly 1,1,3,3,4,4-hexachloro-1-butene (1) compound was synthesized from the trichloroetylene’s free radical dimerization with dibenzoylperoxide. 2H-1,1,3,4-tetrachloro-4-bromobutadien (2) was synthesized from compound (1). In the second part of this study (1) and (2) were used as starting materials and new unknown -S substitue compounds were synthesized.

2-Chloro-1,1,4,4-(7-mercapto-4-methyl-coumarinyl)-1,3,butadiene (3), 2-Chloro-1,1,4,4,-(2-hydroxyphenylthio)-1,3-butadiene (4), 2-Chloro-1,1,4,4-(2-methylphenylthio)-1,3-butadiene (5), 2-Chloro-1,4,4-(4-phlorophenilthio)-1,3-butadiene (6), 2-Chloro-1,4,4,4-(4-methoxyphenilthio)1,3-butadiene (7), 2-Chloro-1,1,4,4-(2,4-dimethylphenilthio)-1,3-butadiene (8), 1,1,2,4-Tetrachloro-4-(3,4-dimethoxyphenilthio)-1,3-butadiene (9), 2-Chloro-1,1,4,4-(pentfluorophenilthio)-1,3-butadiene (10) and 1,1,3-Trichloro-4,4-(4-nitrophenilthio)-1,3-butadiene (28) compounds were synthesized from the reaction of 1,1,3,3,4,4-hexachloro-1-butene (1) with 7-mercapto-4-methyl coumarin, 2-mercaptophenol, 2-methylthiophenol, 4-fluorothiophenol, 4-methoxythiophenol, 2,4-dimethylthiophenol, 3,4-dimethoxythiophenol, pentafluorothiophenol and p-nitrothiophenol in the presence of dipolar aprotic solvent.
In the same way, 1,1,2,4-Tetrachloro-4-(7-mercapto-4-methyl-coumarinyl)-1,3-butadiene (11), 1,2-Dichloro-1,4,4-(7-mercapto-4-methyl-coumarinyl)-1,3-butadiene (12), 1,1,2-Trichloro-4-(7-mercapto-4-methil-coumarinyl)-1-butene-3-yne (13), 1,1,2-Trichloro-4-(2-methylphenilthio)-1-butene-3-yne (14), 1,1,2-Trichloro-4-(2,4-dimethylphenilthio)-1-butene-3-yne (15), 1,2-Dichloro-1,4-(3,4-dimethoxyphenilthio)-1-butene-3-yne (16), 2-Chloro-1,1,4-(3,4-dimethoxyphenilthio)-1-butene-3-yne (17), 1,1,2,4-Tetracloro-4-benzo-1,3-thiazolyl-(2)-thio)-1,3-butadiene (18), 1,1,2,4-Tetracloro-4-benzo-1,3-imidazolyl-(2)-thio)-1,3-butadiene (19), 2-Chloro-1,1,4,4-(2,2,2-trifluoro-ethyl-sulphanyl)-1,3-butadiene (20), 2-Chloro-1,1,3,4,4-(2,2,2-tripholoro-ethil-sulphanyl)-1,3-butadiene (21), 2-Chloro-1,1,4,4-(1-propanol-3-sulphanyl-1-butene-3-yne (22), 1,1,2-Trichloro-4,4-(cyclopenthyl-sulphanyl)-1,3-butadiene (26) and 1,1,2,4-(cyclopentyl-sulphanyl)-1-butene-3-yne (27) compounds were synthesized from the reaction of starting material 1,1,3,3,4,4-hexachloro-1-butene (1) with 7-mercapto-4-methyl coumarin, 2-methylthiophenol, 2,4-dimethylthiophenol, 3,4-dimethoxythiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2,2,2-trifluoroethanthiol, 3-mercapto-1-propanol and cyclopentyl mercaptan in the presence of protic solvent.

1-Bromo-1,2-Dichloro-4-(7-mercapto-4-methyl-coumarinyl)-1-butene-3-yne (23), 1-Bromo-1,2-Dichloro-4-(2,4-dimethylphenylthio)-1-butene-3-yne (24) and 1-Bromo-1,2-Dichloro-4-(benzo-1,3-thiazolyl-(2)-thio)-1,3-butadiene (25) compounds were synthesized from the reaction of starting material 2H-1,1,3,4-tetrachloro-4-bromobutadien (2) with 7-mercapto-4-methyl coumarin, 2,4-dimethylthiophenol and 2-mercaptobenzothiazol compounds in the presence of protic solvent.

The structures of these newly synthesized compounds were charecterized by using microanalyses, FTIR, 1H NMR, 13C NMR, 19F NMR, MS, U V-Vis and fluorescence spectroscopy.

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

Anabilim Dalı : Kimya

Programı (Varsa) : 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 (Varsa) : 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.