Yeni Ligandlar Ve Organik Reaksiyonlarda Kullanılmaları
Yeni Ligandlar Ve Organik Reaksiyonlarda Kullanılmaları
Dosyalar
Tarih
2013-09-13
Yazarlar
Sarışan, Şebnem
Süreli Yayın başlığı
Süreli Yayın ISSN
Cilt Başlığı
Yayınevi
Fen Bilimleri Enstitüsü
Institute of Science and Technology
Institute of Science and Technology
Özet
Organik sentezlerde, reaksiyon hızının, veriminin ve seçiciliğin kontrol edilebilmesi büyük önem taşır. Bu kontrollerin sağlanabilmesi için ligand içeren kompleks yada katalizör kullanılır. Fosfor ligandları enantiyoseçici özellik gösteren farklı türlerdeki birçok ligand arasında öne çıkmaktadır. Fosfor ligandları sahip oldukları sterik ve elektronik özellikleriyle seçiciliği sağlar. Optikçe aktif yada kiral özelliği taşıyan fosfor ligandları kullanılarak asimetrik sentez de gerçekleştirilebilir. Son yıllarda yapılan çalışmalarda BINOL tipi fosfor içeren ligandlar kullanılarak yüksek verim, kısa reaksiyon süresi ve enantiyoseçicilik sağlanmıştır. Fosfor ligandlarının kullanıldığı reaksiyonlardaki etkinliği kadar elde edildiği reaksiyonların verimi de önemlidir. Fosfor ligandlarının sentezi için çeşitli reaksiyon mekaizmaları kullanılmaktadır. Helisenler düzlemsel olmayan karakteristik şekilleri ve kiralite özellikleri sebebiyle bilimsel araştırmalarda ilgi çekmektedir. Son yıllarda yapılan araştırmalarda helisenlerin kiral molekül yapısından dolayı asimetrik katalizör olarak kullanılabilirliği gözlenmiştir. Son on yılda helisen sentezi için farklı metotlar geliştirilmiş olsa da bunlardan sadece bir kısmı stereoseçicilik özelliği gösterir. Karakteristik helisen yapısında olan heteroaromatik helisenler enantiyomer seçiciliği sağlayan güçlü optik rotasyona sahiptir. Bu çalışmada fosfor ligandlarının sentezi amaçlanmıştır. Bunun için de naftofuranofuran ve bunun doymamış türevlerinin fosforlanması ile yeni fosfor ligandlarının elde edilmiştir. İlk temel bileşik olarak, 2,13-Dihidroksi-7a,14c-dihidronafto[1’,2’:4,5]furo[3.2-d]furan (1), 2,7-dihidroksinaftalenin glioksalbisülfit ile hafif asidik ortamdaki reaksiyonu ile sentezlenmiştir. İkinci temel bileşik olarak naftofuranofuran olan, 6,9-Dihidroksi-7a,14e-dihidronafto[2,1-b]nafto[1 ,2 :4,5]furo[3,2-d]furan (2), 2,3-dihidroksinaftalenin glioksalbisülfit ile hafif asidik ortamdaki reaksiyonu ile sentezlenmiştir. Daha sonra bileşik (1), ilk hedef olan fosfin içeren naftofuranofuran ligantını sentezlemek için diklorofenilfosfin ile sodyum hidrür ve THF varlığında reaksiyona konulmuştur. Çalışmanın ilerleyen kısımlarında ligand türlerini çeşitlendirebilmek için diklorofenilfosfin oksit kullanılarak çeşitli sentezler yapılmıştır. İlk olarak fosfinin naftalen üzerindeki bir hidroksil grubuna bağlanıp kendi üzerinde de bir metoksi taşıması hedeflenmiştir. Bunun için naftofuranofuran ile diklorofenilfosfin oksit reaksiyona konulmuş, ürün izolasyon aşamasında metanole dökülerek metoksi fosfor bağı oluşturulmuştur. İkinci olarak ligant türlerini çeşitlendirebilmek için yine diklorofenilfosfin oksit ile (1) nolu naftofuranofuran bileşiği aynı koşullarda reaksiyona konmuştur. Fakat ürünün izolasyon aşamasında suya dökülerek, fosfinin naftalen üzerindeki bir hidroksil grubuna bağlanıp kendi üzerinde de bir hidroksil taşıması sağlanmıştır. Ayrıca çalışmanın devamında elde edilen helisen tipi bileşik 2,13-Dihidroksi-nafto[2,1-b]nafto[1’,2’:4,5]furo[3.2-d]furan (7), N-bromsuksinimid (NBS) ile reaksiyona konularak furanofuran halkalarında doymamış yapı oluşturuldu. Yapılan deney sonucunda, gün ışığında NBS ile reaksiyon sonucunda bileşik (7) başarılı bir şekilde elde edildi. Çalışmanın devamında benzer tipte konjuge naftofuranofuran sentezleyebilmek için (2) numaralı bileşik, bileşik (1) ile aynı şartlar altında NBS ile reaksiyona konularak konjuge yapılmaya çalışılmıştır.
Naftofuranofuran type compounds have the property of many biological activity. Therefore, these compounds are widely used in many fields, these fields could be classified as agriculture and industry in its own. Benzofuranofuran also used in industries such as dyes in laser technology and fluorescent materials for visualization of biomolecules. Structures of naftofuranofuran compounds have resemblance to chiral phosphine ligands, and hence dibenzofuranofuran is possible to use as a catalyst like phosphine ligands in the organic chemistry. Usage of ligand or catalyst obtain the control for selectivity, purity, speed and yield in organic reaction. Due to the fact that the chiral information in the organic products prepared by enantioselective catalysis derives from the optically active ligands bound to the transition metal, the design of these ligands constitutes a meticulous research. Although other ligand types continue to be employed in some enantioselective catalysis, optically active phosphines play a key role as chiral ligands in various transition metal-catalyzed asymmetric synthesis because of their steric and electronic variability. Morever, it has been reported that sterically congested phosphine ligands remarkably increase the catalytic activities of the metal complexes. In last years, the excellent yield and selectivity of many reactions obtain by using 1,1’-binaphtyl-2-2’-diol (BINOL). Furthermore, BINOL also used as a chiral agent in asymmetric synthesis. After the new information of BINOL, numerous publications apperead reporting new or more efficient synthetic routes using this ligand. A broad selection of new substituted chiral auxiliaries which improved the enantioselectivity of certain reaction are developed by using BINOLs. The naphthelene units partially hydrogenate to modification of the classic binaphthyl structure. This hydrogenation provide the corresponding H4-H8-BINOL ligands. Phosphorus containing BINOL ligands increased an unwieldy largeness and diedral angle often give improved results regarding the selectivity of several asymmetric reactions. Modern advanced asymmetric catalysis demands both maximum efficiency in terms of yield and enantioselectivity. Reactions using phosphorus ligand demands the same properties, too. A variety of reaction mechanisms are used for the synthesis of phosphorus ligands. These mechanism could obtain maximum yield, purity and short reaction time. Helicenes have been interesting for academic researcher because helicenes and helicen-like molecules show non-planar characteristics and the feature of helical chirality. In the recent advances shows that helicenes and helicen-like molecules to be potential as liquid crystal molecules, sensors, and dyes. Research give information that helicenes have been applications in areas of asymmetric catalysis and chiral molecular recognation. Oxidative photocyclization of bis(stilbene)s is a traditionally synthesized of helicen method. In past ten years, several new synthetic methods have been developed that contain Diels-Alder cycloaddition, [2+2+2] cycloisomerization, carbenoid coupling, radical tandem cyclization, domino Friedel-Crafts type cyclization, Pd-mediated techniques, intramolecular McMurry reaction, and olefin metathesis. However, some of them obtain high diastreoselectivity or regioselectivity. Aromatic and heteroaromatic helicenes are classes of molecules with a characteristic helical sturucture and a high spesific optical rotation of the seperated enantiomers. Our interest in compounds such as 7,8-dioksa[6]helicene is a simple model of the new horseshoe shaped molecule. There is a low inversion barrier between helical enantiomers. A low-energy barrier between the P and M forms. Interconversion of the two forms which are racemic mixture occurs readily at room temperature in solution due to the geometic features of the five membered furane rings. Structures of naftofuranofuran compounds have resemblance to chiral phosphine ligands, and hence dibenzofuranofuran is possible to use as a catalyst like phosphine ligands in the organic chemistry. In the present study, synthesis of phosphorus have being aimed. For this purpose, new ligand obtain with phosphorylation of naftofuranofuran and unsaturated derivatives of naftofuranofuran. The first compound, 2,13-Dihydroxy-7a,14c-dihydronaphto[1’,2’:4,5]furo[3.2-d]furan, is synthesized by the reaction of 2,7-dihydroxynaphthalene and glyoxal bisulfite in slightly acidic medium. The second compound, 6,9- Dihydroxy -7a,14e-dihidronaptho [2,1-b]naphto[1 ,2 :4,5]furo[3,2-d]furan, is synthesized by the reaction of 2,3-dihydroxynaphthalene and glyoxal bisulfite in slightly acidic environment. After that these compounds are derived with dichloro phenyl phosphine or dicholorophenyl phosphine oxide for the synthesis of phosphorus group containing naphthofuranofuran ligand. Firstly, 2,13-Dihydroxy-7a,14c-dihydronaphto[1’,2’:4,5]furo[3.2-d]furan and dichlorophenylphosphine react with sodyum hidrür in tetrahidrofuran for the synthesize of naphthofuranofuran ligand including phoshine. Secondly, 2,13-Dihydroxy-7a,14c-dihydronaphto[1’,2’:4,5]furo[3.2-d]furan and diphenilphophine react with piridin and tetrahidrofuran for the derivation. Later part of study various synthesis is made for increase ligand types with dichlorophenylphosphine oxide. Firstly, phosphine connect to hydroxyl group on naphthalene and purpose is phosphine is intended to carry methoxy group.For this purpose naphthofuranofuran and dichlorophenylphosphine oxide react with sodyum hidrür in tetrahidrofuran, product of reaction pour into methanol to make methoxy- phosphorus bond. In the following stages of study, 2,13-Dihydroxy-7a,14c-dihydronaphto[1’,2’:4,5]furo[3.2-d]furan reacted with N-Bromosuccinimide in carbon tetrachloride under daylight to obtain 2,13- Dihydroxy-naphto[2,1-b]naphto[1’,2’:4,5]furo[3.2-d]furan which is helicen type unsaturated molecule.The aim here is to achieve a helicen type characteristic structure. We want to observe to variation of catalytic activity due formed a helix structure. The experiment succesfully performed in this manner helicene type 2,13- Dihydroxy-naphto[2,1-b]naphto[1’,2’:4,5]furo[3.2-d]furan is obtained. Following the part of the study, the purpose is synthesize of similar type conjugate naphtofuranofuran. For this purpose, 6,9- Dihydroxy -7a,14e-dihidronaptho [2,1-b]naphto[1 ,2 :4,5]furo[3,2-d]furan and excess N-Bromosuccinimide reacted under daylight to obtain 6,9-Dihidroksi-naphto[2,1-b]naphto[1 ,2 :4,5]furo[3,2-d]furan. The experiment is ineffectice so that the reaction conditions should change. In conclusion, phosphorous containing naftofuranofuran type ligands were succesfully synthesized. However these compounds have properties of high volatility, unair-stable, toxicity, stench and spantaneous inflammability. Because of these properties, phosphorous compound are very difficult to work. Otherwise, naphtofuranofuran compound react with N-Bromosuccinimide in daylight over radical mechanism. Naphtofuranofuran compound is transform to conjugate planar form with have unsaturated form.
Naftofuranofuran type compounds have the property of many biological activity. Therefore, these compounds are widely used in many fields, these fields could be classified as agriculture and industry in its own. Benzofuranofuran also used in industries such as dyes in laser technology and fluorescent materials for visualization of biomolecules. Structures of naftofuranofuran compounds have resemblance to chiral phosphine ligands, and hence dibenzofuranofuran is possible to use as a catalyst like phosphine ligands in the organic chemistry. Usage of ligand or catalyst obtain the control for selectivity, purity, speed and yield in organic reaction. Due to the fact that the chiral information in the organic products prepared by enantioselective catalysis derives from the optically active ligands bound to the transition metal, the design of these ligands constitutes a meticulous research. Although other ligand types continue to be employed in some enantioselective catalysis, optically active phosphines play a key role as chiral ligands in various transition metal-catalyzed asymmetric synthesis because of their steric and electronic variability. Morever, it has been reported that sterically congested phosphine ligands remarkably increase the catalytic activities of the metal complexes. In last years, the excellent yield and selectivity of many reactions obtain by using 1,1’-binaphtyl-2-2’-diol (BINOL). Furthermore, BINOL also used as a chiral agent in asymmetric synthesis. After the new information of BINOL, numerous publications apperead reporting new or more efficient synthetic routes using this ligand. A broad selection of new substituted chiral auxiliaries which improved the enantioselectivity of certain reaction are developed by using BINOLs. The naphthelene units partially hydrogenate to modification of the classic binaphthyl structure. This hydrogenation provide the corresponding H4-H8-BINOL ligands. Phosphorus containing BINOL ligands increased an unwieldy largeness and diedral angle often give improved results regarding the selectivity of several asymmetric reactions. Modern advanced asymmetric catalysis demands both maximum efficiency in terms of yield and enantioselectivity. Reactions using phosphorus ligand demands the same properties, too. A variety of reaction mechanisms are used for the synthesis of phosphorus ligands. These mechanism could obtain maximum yield, purity and short reaction time. Helicenes have been interesting for academic researcher because helicenes and helicen-like molecules show non-planar characteristics and the feature of helical chirality. In the recent advances shows that helicenes and helicen-like molecules to be potential as liquid crystal molecules, sensors, and dyes. Research give information that helicenes have been applications in areas of asymmetric catalysis and chiral molecular recognation. Oxidative photocyclization of bis(stilbene)s is a traditionally synthesized of helicen method. In past ten years, several new synthetic methods have been developed that contain Diels-Alder cycloaddition, [2+2+2] cycloisomerization, carbenoid coupling, radical tandem cyclization, domino Friedel-Crafts type cyclization, Pd-mediated techniques, intramolecular McMurry reaction, and olefin metathesis. However, some of them obtain high diastreoselectivity or regioselectivity. Aromatic and heteroaromatic helicenes are classes of molecules with a characteristic helical sturucture and a high spesific optical rotation of the seperated enantiomers. Our interest in compounds such as 7,8-dioksa[6]helicene is a simple model of the new horseshoe shaped molecule. There is a low inversion barrier between helical enantiomers. A low-energy barrier between the P and M forms. Interconversion of the two forms which are racemic mixture occurs readily at room temperature in solution due to the geometic features of the five membered furane rings. Structures of naftofuranofuran compounds have resemblance to chiral phosphine ligands, and hence dibenzofuranofuran is possible to use as a catalyst like phosphine ligands in the organic chemistry. In the present study, synthesis of phosphorus have being aimed. For this purpose, new ligand obtain with phosphorylation of naftofuranofuran and unsaturated derivatives of naftofuranofuran. The first compound, 2,13-Dihydroxy-7a,14c-dihydronaphto[1’,2’:4,5]furo[3.2-d]furan, is synthesized by the reaction of 2,7-dihydroxynaphthalene and glyoxal bisulfite in slightly acidic medium. The second compound, 6,9- Dihydroxy -7a,14e-dihidronaptho [2,1-b]naphto[1 ,2 :4,5]furo[3,2-d]furan, is synthesized by the reaction of 2,3-dihydroxynaphthalene and glyoxal bisulfite in slightly acidic environment. After that these compounds are derived with dichloro phenyl phosphine or dicholorophenyl phosphine oxide for the synthesis of phosphorus group containing naphthofuranofuran ligand. Firstly, 2,13-Dihydroxy-7a,14c-dihydronaphto[1’,2’:4,5]furo[3.2-d]furan and dichlorophenylphosphine react with sodyum hidrür in tetrahidrofuran for the synthesize of naphthofuranofuran ligand including phoshine. Secondly, 2,13-Dihydroxy-7a,14c-dihydronaphto[1’,2’:4,5]furo[3.2-d]furan and diphenilphophine react with piridin and tetrahidrofuran for the derivation. Later part of study various synthesis is made for increase ligand types with dichlorophenylphosphine oxide. Firstly, phosphine connect to hydroxyl group on naphthalene and purpose is phosphine is intended to carry methoxy group.For this purpose naphthofuranofuran and dichlorophenylphosphine oxide react with sodyum hidrür in tetrahidrofuran, product of reaction pour into methanol to make methoxy- phosphorus bond. In the following stages of study, 2,13-Dihydroxy-7a,14c-dihydronaphto[1’,2’:4,5]furo[3.2-d]furan reacted with N-Bromosuccinimide in carbon tetrachloride under daylight to obtain 2,13- Dihydroxy-naphto[2,1-b]naphto[1’,2’:4,5]furo[3.2-d]furan which is helicen type unsaturated molecule.The aim here is to achieve a helicen type characteristic structure. We want to observe to variation of catalytic activity due formed a helix structure. The experiment succesfully performed in this manner helicene type 2,13- Dihydroxy-naphto[2,1-b]naphto[1’,2’:4,5]furo[3.2-d]furan is obtained. Following the part of the study, the purpose is synthesize of similar type conjugate naphtofuranofuran. For this purpose, 6,9- Dihydroxy -7a,14e-dihidronaptho [2,1-b]naphto[1 ,2 :4,5]furo[3,2-d]furan and excess N-Bromosuccinimide reacted under daylight to obtain 6,9-Dihidroksi-naphto[2,1-b]naphto[1 ,2 :4,5]furo[3,2-d]furan. The experiment is ineffectice so that the reaction conditions should change. In conclusion, phosphorous containing naftofuranofuran type ligands were succesfully synthesized. However these compounds have properties of high volatility, unair-stable, toxicity, stench and spantaneous inflammability. Because of these properties, phosphorous compound are very difficult to work. Otherwise, naphtofuranofuran compound react with N-Bromosuccinimide in daylight over radical mechanism. Naphtofuranofuran compound is transform to conjugate planar form with have unsaturated form.
Açıklama
Tez (Yüksek Lisans) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 2013
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2013
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2013
Anahtar kelimeler
Ligand,
Organik Reaksiyonlar,
Ligands,
Organic Reactions