Tez özetleri Astronomi ve Uzay Bilimleri Anabilim Dalı

Removal Of Some Organic Substances From Water Through Adsorption–Filtration And Adsorptıon-Membrane Hybrid Systems.

Pesticides, surface active agents and other organic compounds cause environmental hazards due to their high degree of toxicity, even at low concentrations. There are many methods to remove these organic compounds from water. Amongst them filtration and membrane systems are widely used techniques to remove organic substances from water. Membrane processes are being in use for few decades and proved efficient in drinking water production.

A membrane serves as a nearly complete barrier to pathogenic microorganism and colloidal particles. However, concentration polarization and fouling by organic contaminants affects the efficiency of these processes. A gradual reduction in flux has been observed in long term applications due to fouling. Pretreatments like coagulation followed by sedimentation, coagulation followed by dissolved air flotation, and activated carbon adsorption to remove foulants (mainly organic matter) have been suggested. The pretreatment with powdered activated carbon (PAC) is considered the most effective method for foul control. It was assumed that the PAC formed porous layer on the membrane surface which did not affect the flux. However, a decline in flux due to cake formation on membrane surface has been observed recently. Cake formation over the membrane surface lengthens the back washing time. It also causes blackening of the flow meter and pipes of the membrane system. Magnetic adsorbents have been used to remove organic and inorganic pollutants from effluents and after their use in treatment; they can be separated from the medium by a simple magnetic process. Iron oxide is efficient against foul control in the membrane processes but it has low surface area as compared to PAC. There is need for such adsorbents having magnetic properties and comparative surface area as that of PAC. Impregnation is the method of choice for developing such adsorbents. Granular activated carbon (GAC) filters are the other alternative to be used for foul control in the membrane processes.

In this study an iron oxide/PAC composite was prepared, characterized and used as foul controlling agent. The adsorptive capacities of PAC and magnetic activated carbon (MAC) for different organic pollutants were determined. These adsorbents were then used as pretreatment for foul control in the ultrafiltration membrane processes. GAC filters were also tested for foul control. PAC and MAC used in this study were characterized by FTIR, surface area analyzer, point of zero charge, Boehm titration and XRD. The adsorption parameters for these adsorbents were determined. In order to determine the kinetic parameters, a specially designed container was used.

Polyethersulfone ultrafiltration (UF) membranes were used in this study and parameters like flux decline with time and percent retention of organic pollutants by membrane was determined. Improved flux and percent retention were observed when ultrafiltration membrane was used in combination with GAC filter and with continuous stirred reactor where organic pollutants solutions were treated with PAC and MAC. The percent rejection in the hybrid UF/MAC process was almost equal to that of UF/PAC for each substance. The same trend was observed for the improvement of permeate flux in both the processes. The little differences were due lower surface area of MAC than the PAC. MAC can be used as pretreatment in UF systems because it has high adsorption capacity and it can be separated easily from medium by application of magnetic field. The problems like cake formation and blackening of the pipes were not observed for MAC.

ÖZKÖK Funda

Danışman : Prof.Dr. Cemil İBİŞ

Anabilim Dalı : Kimya

Programı : Organik Kimya

Mezuniyet Yılı : 2010

Tez Savunma Jürisi : Prof.Dr.Cemil İBİŞ (İstanbul Üniversitesi)

Prof.Dr.Oya ATICI (İstanbul Teknik Üniversitesi)

Prof.Dr.Mustafa BULUT (Marmara Üniversitesi)

Prof.Dr.Süleyman TANYOLAÇ (İstanbul Üniversitesi)

Prof.Dr.F.Serpil GÖKSEL (İstanbul Üniversitesi)

1,3-Butadienil Gruplu Bazı Yeni Tiyoeterlerin Sentezi

1,3-Butadienil Gruplu Bazı Yeni Tiyoeterlerin Sentezi
Çalışmamızda başlangıç maddeleri olarak 2H-1,1,3,4,4-pentaklor-1,3-butadien (1), 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2) ve 4-Brom-2H-1,1,3,4-tetraklor-1,3-butadien (3) bileşikleri kullanıldı.

2H-1,1,3,4,4-pentaklor-1,3-butadien (1)’in 4,4´-Tiyobisbenzentiyol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni Benzen-1,1’-tiyobis[4-(3,4,4-triklor-1-butenil)tiyo] (30) bileşiği elde edildi.

2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)’in 2-merkaptofenol ile çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen yeni 3,4,4-Triklor-1-[benzo(1,3-oksatiya)]-2-nitro-1,3-butadien (4) bileşiği elde edildi.

2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)’in Tiyosalisilik asit ile çözücüsüz ortamdaki reaksiyonundan bilinmeyen yeni 1,1-Bis(2-Karboksifeniltiyo)-3,4,4-triklor-2-nitro-1,3-butadien (5) bileşiği elde edildi.

2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)’in o-tiyokresol ile çözücüsüz ortamdaki reaksiyonundan bilinmeyen yeni 2-Nitro-1,3,4,4-tetraklor-1-(2-Metilfeniltiyo)-1,3-butadien (6) ve 1,1-Bis(2-Metilfeniltiyo)-3,4,4-triklor-2-nitro-1,3-butadien (7) bileşiği elde edildi.

2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)’in o-tiyokresol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni 1,1,4-Tris(2-Metilfeniltiyo)-3,4-diklor-2-nitro-1,3-butadien (17) bileşiği elde edildi.

2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)’in 2,4-dimetilbenzentiyol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni 1,1-Bis(2,4-Dimetilfeniltiyo)-3,4,4-triklor-2-nitro-1,3-butadien (18) bileşiği ve 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)’in 2,4-dimetilbenzentiyol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni 1,1,4-Tris(2,4-Dimetilfeniltiyo)-3,4-diklor-2-nitro-1,3-butadien (19) bileşiği elde edildi.

2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)’in 3-Tiyometil-3-propiyonat ile çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen yeni 2-Nitro-1,3,4,4-tetraklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadien (20) bileşiği ve 2-Nitro-1,1,3,4,4-pentaklor-1,3-butadien (2)’in 4,4’-Tiyobisbenzentiyol ile çözücüsüz ortamda gerçekleştirilen reaksiyonundan bilinmeyen yeni Benzen-1,1’-tiyobis[4-(1,3,4,4-tetraklor-2-nitro-1,3-butadienil)tiyo] (29) bileşiği elde edildi.

4-Brom-2H-1,1,3,4-tetraklor-1,3-butadien (3)’in 4,4’-Tiyobisbenzentiyol ile etanollü ortamda NaOH varlığında gerçekleştirilen reaksiyonundan bilinmeyen yeni Benzen-1,1’-tiyobis[4-(3,4-diklor-4-brom-1-butenil)tiyo] (31) bileşiği elde edildi.

Çalışmamızın ikinci aşamasında, elde edilen mono(tiyo)sübstitüe nitrodien bileşiklerinin bazı piperazin türevleri, morfolin türevleri ve piperidin türevleri ile reaksiyonları incelendi.

2-Nitro-1,3,4,4-tetraklor-1-(2-Metilfeniltiyo)-1,3-butadien (6) bileşiği, sırasıyla 1-(2-Florfenil)piperazin, 1-(4-Florfenil)piperazin, N-fenilpiperazin, 1-(2-Metoksifenil)piperazin, 1-(Difenilmetil)piperazin, 1-(4-Nitrofenil)piperazin, 1-(4-Hidroksifenil)piperazin, N-morfolin, 4-(2-Aminoetil)morfolin ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla bilinmeyen yeni 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(2-florfenil)piperazin (8), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(4-florfenil)piperazin (9), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(1-fenil)piperazin (10), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(2-metoksifenil)piperazin (11), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(1-Difenilmetil) piperazin (12), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(4-Nitrofenil)piperazin (13), 1- [2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil] -4-(4-hidroksifenil) piperazin (14), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-morfolin (15), 1-[2-Nitro-3,4,4-triklor-1-(2-Metilfeniltiyo)-1,3-butadienil]-4-(2-aminoetil)morfolin (16) bileşikleri sentezlendi.

2-Nitro-1,3,4,4-tetraklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadien (20) bileşiği, sırasıyla 1-(4-Florfenil)piperazin, 1-(2-Metoksifenil)piperazin, 1-(4-nitrofenil)piperazin, N-fenilpiperazin, 1-(2-Florfenil)piperazin, N-morfolin, N-piperidin, 1-(4-Metil)piperidin ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla bilinmeyen yeni 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(4-florfenil)piperazin (21), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(2-Metoksifenil)piperazin (22), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(4-nitrofenil)piperazin (23), 1-

[ 2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(1-Fenil)piperazin (24), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(2-Florfenil)piperazin (25), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-morfolin (26), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-piperidin (27), 1-[2-Nitro-3,4,4-triklor-1-(3-butil-3-propiyoniltiyo)-1,3-butadienil]-4-(4-Metil)piperidin (28) bileşikleri kazanıldı.

Sentezlenen bu yeni bileşikler kristallendirme veya kolon kromatografisi yöntemleri ile saflaştırıldı. Bileşiklerin yapısı mikro analiz ve spektroskopik yöntemlerle (-IR, -¹H-NMR, -¹³C-NMR veya -APT-NMR, -UV ve –MS) ile aydınlatıldı. Bazı yeni bileşiklerin X-ışınları kristalografisi ile konformasyonal yapısı aydınlatıldı.

The Synthesıs Of Some New Thıoethers Havıng 1,3-Butadıenyl Groups
In our study, 2H-1,1,3,4,4-pentachloro-1,3-butadiene (1), 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) and 4-Bromo-2H-1,1,3,4-tetrachloro-1,3-butadiene (3) compounds were used as starting compounds.

The unknown, new compound Benzene-1,1’-thiobis[4-(3,4,4-trichloro-1-butenyl)thio] (30) was obtained from the reaction of 2H-1,1,3,4,4-pentachloro-1,3-butadiene (1) with 4,4’-thiobisbenzenethiol in the presence of NaOH in ethanol.

The unknown, new compound 3,4,4-Trichloro-1-[benzo(1,3-oxathia)]-2-nitro-1,3-butadiene (4) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 4,4’-thiobisbenzenethiol.

The unknown, new compound 1,1-Bis(2-Carboxyphenylthio)-3,4,4-trichloro-2-nitro-1,3-butadiene (5) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with thiosalicylic acid.

The unknown, new compounds 2-Nitro-1,3,4,4-tetrachloro-1-(2-Methylphenylthio)-1,3-butadiene (6) and 1,1-Bis(2-Methylphenylthio)-3,4,4-trichloro-2-nitro-1,3-butadiene (7) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with o-thiocresol.

The unknown, new compound 1,1,4-Tris(2-Methylphenylthio)-3,4-dichloro-2-nitro-1,3-butadiene (17) was obtained from the reaction of with 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with o-thiocresol in the presence of NaOH in ethanol.

The unknown, new compound 1,1-Bis(2,4-Dimethylphenylthio)-3,4,4-trichloro-2-nitro-1,3-butadiene (18) was obtained from the reaction of with 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 2,4-dimethylbenzenethiol in the presence of NaOH in ethanol.

The unknown, new compound 1,1,4-Tris(2,4-Dimethylphenylthio)-3,4-dichloro-2-nitro-1,3-butadiene (19) was obtained from the reaction of with 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 2,4-dimethylbenzenethiol in the presence of NaOH in ethanol.

The unknown, new compound 2-Nitro-1,3,4,4-tetrachloro-1-(3-butyl-3-propionyl)-1,3-butadiene (20) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 3-Thiomethyl-3-propionate.

The unknown, new compound Benzene-1,1’-thiobis[4-(1,3,4,4-tetrachloro-2-nitro-1,3-butadienyl)thio] (29) was obtained from the reaction of 2-Nitro-1,1,3,4,4-pentachloro-1,3-butadiene (2) with 4,4’-Thiobisbenzenethiol.

The unknown, new compound Benzene-1,1’-thiobis[4-(3,4-dichloro-4-bromo-1-butenyl)thio] (31) was obtained from the reaction of 4-Bromo-2H-1,1,3,4-tetrachloro-1,3-butadiene (3) with 4,4’-Thiobisbenzenethiol in the presence of NaOH in ethanol.

In the second step, reactions of derivatives of some piperazine, morpholine and piperidine with the mono(thio)substituted nitrodiene compounds were investigated.

The unknown, new compounds 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(2-florophenyl)piperazine (8), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(4-florophenyl)piperazine (9), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(1-phenyl)piperazine (10), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl] -4-(2-metoxyphenyl)piperazine (11), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(1-Diphenylmethyl) piperazine (12), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(4-Nitrophenyl) piperazine

(13), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(4-Hidroxyphenyl)piperazine (14), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-morfoline (15), 1-[2-Nitro-3,4,4-trichloro-1-(2-Methylphenylthio)-1,3-butadienyl]-4-(2-aminoethyl)morfoline (16) were synthesized from the reactions of 2-Nitro-1,3,4,4-tetrachloro-1-(2-Methylphenylthio)-1,3-butadiene (6) with the 1-(2-Florophenyl)piperazine, 1-(4-Florophenyl)piperazine, N-phenylpiperazine, 1-(2-Metoxyphenyl)piperazine, 1-(Diphenylmethyl)piperazine, 1-(4-Nitrophenyl)piperazine, 1-(4-Hidroxyphenyl)piperazine, N-morfoline, 4-(2-Aminoethyl)morfoline, respectively.

The unknown, new compounds 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-(4-florophenyl)piperazine (21), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-(2-Metoxyphenyl)piperazine (22), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl] -4-(4-nitrophenyl)piperazine (23), 1-[ 2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-(1-Phenyl)piperazine (24), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-(2-Florophenyl)piperazine (25), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-morfoline (26), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl]-4-piperidine (27), 1-[2-Nitro-3,4,4-trichloro-1-(3-butyl-3-propionylthio)-1,3-butadienyl] -4-(4-Methyl)piperidine (28) were synthesized from the reactions of 2-Nitro-1,3,4,4-tetrachloro-1-(3-butyl-3-propionylthio)-1,3-butadiene (20) with the 1-(4-Florophenyl)piperazine, 1-(2-Metoxyphenyl)piperazine, 1-(4-nitrophenyl)piperazine, N-phenylpiperazine, 1-(2-Florophenyl)piperazine, N-morfoline, N-piperidine, 1-(4-Methyl)piperidine, respectively.

Synthesized the new compounds were purified either crystallization or via column chromatography. Structure of these new compounds were characterized by microanalysis and spectroscopic methods (-IR, - ¹H-NMR, - ¹³C-NMR or APT-NMR, -UV and –MS). Some new compounds of conformational structure were characterized by X-Ray crystallography.

GÜNEŞ ÖZSOY Zeliha

Danışman :Prof. Dr. Cemil İBİŞ

Anabilim Dalı :Kimya

Programı :Organik Kimya

Mezuniyet Yılı :2010

Tez Savunma Jürisi : Prof. Dr. Cemil İBİŞ (Danışman)

Prof. Dr. Süleyman TANYOLAÇ

Prof. Dr. F.Serpil GÖKSEL

Prof. Dr. Mustafa BULUT

Prof. Dr. Belkıs BİLGİN ERAN

Halokinonların S-, O- Ve N- Nükleofilleri İle Reaksiyonlarından Bazı Yeni Kinon Boyalarının Sentezi

Bu doktora tez çalışmasının amacı, geniş bir uygulama alanına sahip olan kinon bileşiklerinin S-, S,S-, S,O- nükleofilleri ile reaksiyonlarının incelenmesi ve bilinmeyen yeni tiyosübstitüe kinon bileşiklerinin sentezlenmesidir.Bu çalışmada, S-, S,S-, S,O- nükleofilleri ile halokinon bileşiklerinin çeşitli reaksiyonları sonucu bilinmeyen yeni sübstitüe kinon bileşikleri sentezlendi. Yeni kinon bileşiklerinin sentezlenmesinde; başlangıç maddesi olarak 2,3,5,6-tetrakloro-1,4-benzokinon (p-kloranil) (1a) ve 2,3-diklor-1,4-naftakinon (1b) bileşikleri kullanıldı.p-Kloranil (1a) bileşiğinin 4-florobenzil merkaptan ile sentez yöntemi 1’e göre reaksiyonundan yeni 2-kloro-3,5,6-tris(4-florobenziltiyo)siklohekza-2,5-dien-1,4-dion (2), 2,3,5,6-tetrakis(4-florobenziltiyo)siklohekza-2,5-dien-1,4-dion (3) ve 2-etoksi-3,5,6-tris(4-florobenziltiyo)siklohekza-2,5-dien-1,4-dion (4) bileşikleri sentezlendi. p-Kloranil (1a) ile 4-florobenzil merkaptan’ın sentez yöntemi 2’ye göre olan reaksiyonundan yeni 2,5-dikloro-3,6-bis(4-florobenziltiyo)siklohekza-2,5-dien-1,4-dion (5), 2,6-dikloro-3,5-bis(4-florobenzil tiyo)siklohekza-2,5-dien-1,4-dion (6), 2-kloro-3,5,6-tris(4-florobenziltiyo)siklohekza-2,5-dien-1,4-dion (2) ve 2,3,5,6-tetrakis(4-florobenziltiyo)siklohekza-2,5-dien-1,4-dion (3) bileşikleri sentezlendi. Bilinmeyen yeni 6H,6H-dibenzo[1,2-b:4,5-e]bis[1,4]oksatiefin-6,14(8H,16H)-dion (7), 6H,6H-dibenzo[1,2-b:5,4-e]bis[1,4]oksatiefin-6,14(12H,16H)-dion (8) ve 2-etoksi-3,5,6-tris(2-(hidroksimetil)feniltiyo)siklohekza-2,5-dien-1,4-dion (9) bileşikleri p-kloranil (1a) ile 2-merkaptobenzil alkol bileşiklerinin reaksiyonundan sentez yöntemi 1’e göre elde edildi. p-Kloranil (1a) bileşiğinin 3-merkapto-1-propanol ile sentez yöntemi 1’e göre reaksiyonundan yeni 3,4,9,10-tetrahidro-2H,8H-benzo[1,2-b:4,5-b']bis[1,4]oksatiefin-6,12-dion (10), 3,4,9,10-tetrahidro-2H,8H-benzo[1,2-b:5,4-b']bis[1,4] oksatiefin-6,12-dion (11) ve 2-kloro-3,5,6-tris(3-hidroksipropiltiyo)siklohekza-2,5-dien-1,4-dion (12) bileşikleri sentezlendi. p-Kloranil (1a) ile, 1,6-hekzanditiyol’ün sentez yöntemi 1’ye göre olan reaksiyonundan yeni 10,11-dikloro-2,3,4,5,6,7-hekzahidro benzo[b][1,4]ditiesin-9,12-dion (13) bileşiği sentezlendi. Bilinmeyen yeni 2,3,4,5,6,7,8,9, 13,14,15,16,17,18,19,20-hekzadekahidrobenzo[1,2-b:4,5-b']bis[1,4]ditiasiklododesin-11,22 -dion (14) bileşiği p-kloranil (1a) ile 1,8-oktanditiyol bileşiklerinin reaksiyonundan sentez yöntemi 1’e göre elde edildi. p-Kloranil (1a) bileşiğinin siklopentil merkaptan ile sentez yöntemi 1’e göre reaksiyonundan yeni 2-kloro-3,5,6-tris(siklopentiltiyo)siklohekza-2,5-dien-1,4-dion (15), 2-kloro-3,6-bis(siklopentiltiyo)-5-etoksisiklohekza-2,5-dien-1,4-dion (16), 2,3,5,6-tetrakis(siklopentiltiyo)siklohekza-2,5-dien-1,4-dion (17), 2,5-bis(siklopentil tiyo)-3,6-dietoksisiklohekza-2,5-dien-1,4-dion (18) ve 2,6-bis(siklopentiltiyo)-3,5-dietoksi siklohekza-2,5-dien-1,4-dion (19) bileşikleri sentezlendi. p-Kloranil (1a) ile siklopentil merkaptan’ın sentez yöntemi 2’ye göre olan reaksiyonundan yeni 2,3,5-trikloro-6-(siklopentiltiyo)siklohekza-2,5-dien-1,4-dion (20), 2,5-dikloro-3,6-bis (siklopentiltiyo)siklo hekza-2,5-dien-1,4-dion (21), 2-kloro-3,5,6-tris(siklopentiltiyo)siklohekza-2,5-dien-1,4-dion (15) ve 2,3,5,6-tetrakis(siklopentiltiyo)siklohekza-2,5-dien-1,4-dion (17) bileşikleri sentezlendi. Bilinmeyen yeni 2,3,5,6-tetrakis(2,3,5,6-tetraflorofeniltiyo)siklohekza-2,5-dien-1,4-dion (22) ve 2,6-dietoksi-3,5-bis(2,3,5,6-tetraflorofeniltiyo)siklohekza-2,5-dien-1,4-dion (23) bileşikleri p-kloranil (1a) ile 2,3,5,6-tetrafloro benzentiyol bileşiklerinin reaksiyonundan sentez yöntemi 1’e göre elde edildi. 2,3-Dikloro-1,4-naftakinon (1b) bileşiğinin 2,3,5,6-tetrafloro benzentiyol ile reaksiyonundan bilinmeyen yeni 2,3-bis(2,3,5,6-tetraflorofeniltiyo)naftalen-1,4-dion (24) ve 2-etoksi-3-(2,3,5,6-tetraflorofeniltiyo)naftalen-1,4-dion (25) bileşikleri sentezlendi. 2,3-Dikloro-1,4-naftakinon (1b) ile siklopentil merkaptan’ın reaksiyonundan bilinmeyen yeni 2,3-bis(siklopentiltiyo)naftalen-1,4-dion (26) ve 2-etoksi-3-(siklopentiltiyo)naftalen-1,4-dion (27) bileşikleri sentezlendi. Bilinmeyen yeni 2,3-bis(4-florobenziltiyo)naftalen-1,4-dion (28), 2-kloro-3-(4-florobenziltiyo)naftalen-1,4-dion (29) ve 2-etoksi-3-(4-florobenzil tiyo)naftalen-1,4-dion (30) bileşikleri 2,3-dikloro-1,4-naftakinon (1b) ile 4-florobenzil merkaptan’ın reaksiyonundan elde edildi.

Sentezlenen yeni kinon bileşikleri kromatografik yöntemlerle saflaştırıldı. Bu bileşiklerin yapıları mikroanaliz ve spektroskopik yöntemler (IR, UV, ¹H-NMR, ¹³C-NMR, MS) kullanılarak aydınlatıldı.

 

The Synthesıs Of The Some New Quınone Dyes From The Reactıons Of Haloquınones Wıth S-, O- And N- Nucleophıles

The purpose of this doctoral thesis was to investigate the reactions of quinone compounds which has a wide application area with some S-, S,S-, S,O- nucleophiles and to synthesize unknown new thiosubstituted quinone compounds.In this study, the unknown new substituted-quinone compounds were synthesized by reactions of S-, S,S-, S,O- nucleophiles with haloquinones. 2,3,5,6-Tetrachloro-1,4-benzoquinone (p-chloranil) (1a) and 2,3-dichloro-1,4-naphthoquinone (1b) were used as starting materials to synthesis of new quinone compounds.Unknown new 2-chloro-3,5,6-tris(4-fluorobenzylthio)cyclohexa-2,5-diene-1,4-dione (2), 2,3,5,6-tetrakis(4-fluorobenzylthio)cyclohexa-2,5-diene-1,4-dione (3) and 2-ethoxy-3,5,6-tris(4-fluorobenzylthio)cyclohexa-2,5-diene-1,4-dione (4) compounds were synthesized by reaction of p-chloranil (1a) with 4-fluorobenzyl mercaptan according to synthesis method 1. Unknown new 2,5-dichloro-3,6-bis(4-fluorobenzylthio)cyclohexa-2,5-diene-1,4-dione (5), 2,6-dichloro-3,5-bis(4-fluorobenzylthio)cyclohexa-2,5-diene-1,4-dione (6), 2-chloro-3,5,6-tris(4-fluorobenzylthio)cyclohexa-2,5-diene-1,4-dione (2) and 2,3,5,6-tetrakis(4-fluorobenzylthio)cyclohexa-2,5-diene-1,4-dione (3) compounds were synthesized by reaction of p-chloranil (1a) with 4-fluorobenzyl mercaptan according to synthesis method 2. Unknown new 6H,6H-dibenzo[1,2-b:4,5-e]bis[1,4]oxathiepin-6,14(8H,16H)-dione (7), 6H,6H-dibenzo[1,2-b:5,4-e]bis[1,4]oxathiepin-6,14(12H,16H)-dione (8) and 2-ethoxy-3,5,6-tris(2-(hydroxymethyl)phenylthio)cyclohexa-2,5-diene-1,4-dione (9) compounds were synthesized by reaction of p-chloranil (1a) with 2-mercaptobenzyl alcohol according to synthesis method 1. Unknown new 3,4,9,10-tetrahydro-2H,8H-benzo[1,2-b:4,5-b']bis [1,4]oxathiepin-6,12-dione (10), 3,4,9,10-tetrahydro-2H,8H-benzo[1,2-b:5,4-b']bis[1,4]oxa thiepin-6,12-dione (11) and 2-chloro-3,5,6-tris(3-hydroxpropylthio)cyclohexa-2,5-diene-1,4-dione (12) compounds were synthesized by reaction of p-chloranil (1a) with 3-mercapto-1-propanol according to synthesis method 1. Unknown new 10,11-dichloro-2,3,4, 5,6,7-hexahydrobenzo[b][1,4]dithiecine-9,12-dione (13) compounds were synthesized by reaction of p-chloranil (1a) with 1,6-hexanedithiol according to synthesis method 1. Unknown new 2,3,4,5,6,7,8,9,13,14,15,16,17,18,19,20-hexadecahydrobenzo[1,2-b:4,5-b'] bis[1,4]dithiacyclododecine-11,22-dione (14) compounds were synthesized by reaction of p-chloranil (1a) with 1,8-octanedithiol according to synthesis method 1. Unknown new 2-chloro-3,5,6-tris(cyclopentylthio)cyclohexa-2,5-diene-1,4-dione (15), 2-chloro-3,6-bis (cyclopentylthio)-5-ethoxycyclohexa-2,5-diene-1,4-dione (16), 2,3,5,6-tetrakis (cyclopentyl thio)cyclohexa-2,5-diene-1,4-dione (17), 2,5-bis(cyclopentylthio)-3,6-dietoksicyclohexa-2, 5-diene-1,4-dione (18) and 2,6-bis(cyclopentylthio)-3,5-diethoxycyclohexa-2,5-diene-1,4-dione (19) compounds were synthesized by reaction of p-chloranil (1a) with cyclopentyl mercaptan according to synthesis method 1. Unknown new 2,3,5-trichloro-6-(cyclopentyl thio)cyclohexa-2,5-diene-1,4-dione (20), 2,5-dichloro-3,6-bis(cyclopentylthio)cyclohexa-2, 5-diene-1,4-dione (21), 2-chloro-3,5,6-tris(cyclopentylthio)cyclohexa-2,5-diene-1,4-dione (15) and 2,3,5,6-tetrakis(cyclopentylthio)cyclohexa-2,5-diene-1,4-dione (17) compounds were synthesized by reaction of p-chloranil (1a) with cyclopentyl mercaptan according to synthesis method 2. Unknown new 2,3,5,6-tetrakis(2,3,5,6-tetrafluorophenylthio)cyclohexa -2,5-diene-1,4-dione (22) and 2,6-diethoxy-3,5-bis(2,3,5,6-tetrafluorophenylthio)cyclohexa -2, 5-diene-1,4-dione (23) compounds were synthesized by reaction of p-chloranil (1a) with 2,3,5,6-tetrafluoro benzenthiol according to synthesis method 1.

Unknown new 2,3-bis(2,3,5,6-tetrafluorophenylthio)naphthalene-1,4-dione (24) and 2-ethoxy-3-(2,3,5,6-tetrafluorophenylthio)naphthalene-1,4-dione (25) compounds were synthesized by reaction of 2,3-dichloro-1,4-naphthoquinone (1b) with 2,3,5,6-tetrafluoro benzenthiol according to synthesis method 1. Unknown new 2,3-bis(cyclopentylthio) naphthalene-1,4-dione (26) and 2-ethoxy-3-(cyclopentylthio)naphthalene-1,4-dione (27) compounds were synthesized by reaction of 2,3-dichloro-1,4-naphthoquinone (1b) with cyclopentyl mercaptan according to synthesis method 1. Unknown new 2,3-bis(4-fluoro benzylthio)naphthalene-1,4-dione (28), 2-chloro-3-(4-fluorobenzylthio)naphthalene-1,4-dione (29) and 2-ethoxy-3-(4-fluorobenzylthio)naphthalene-1,4-dione (30) compounds were synthesized by reaction of 2,3-dichloro-1,4-naphthoquinone (1b) with 4-fluorobenzyl mercaptan according to synthesis method 1.

The novel synthesized quinone compounds were purified by chromatographic methods. The structures of compounds were determined by using micro analysis and spectroscopic methods (IR, UV, ¹H-NMR, ¹³C-NMR, MS).