Metal katalizli sübstitüye amin sentezi
Yükleniyor...
Dosyalar
Tarih
2014
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
İnönü Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/embargoedAccess
Özet
Aminler kimya ve biyolojide, çok önemli bir bileşik sınıfını oluşturur. Bunlar ilaç, kimyasal, tarım ilaçları, polimerler, boyar maddeler, pigmentler, emülgatörler ve plastikleştiricilerin üretiminde yaygın olarak kullanılır. Son on yılda aminlerin sentezinde pratik yöntemler geliştirilmiştir. Bununla beraber bu yöntemler çevreye zararlı halojenür türevlerinin kullanılması, başlangıç maddesi olarak pahalı aminlerin kullanılması, fazla miktarda atık tuz oluşması ve seçiciliğin düşük olması gibi dezavantajlara sahiptir. Bu yüzden daha etkili ve çevre dostu katalitik proseslerin geliştirilmesi önem taşımaktadır. Son yıllarda amin sentezinde kullanılan hidrojen ototransfer yöntemi ilave hidrojen gerektirmediğinden, atmosfer basıncında ve özel düzenekler kullanılmadan gerçekleştirilmektedir. N-heterosiklik karbenler, fosfinlere benzer özelliklere sahip ilginç bir ligand sınıfıdır. Çok kuvvetli -verici sübstitüyentler tarafından kararlı hale getirilmiş olduklarından, karbenler iyi -donörlerdir. Metal-NHC kompleksleri genelde katalitik uygulamalarda çok kullanılmaktadır. Karben komplekslerinin bu alandaki kullanımı sınırlı olduğundan yeni katalizörlerin geliştirilmesi önemlidir. Bu yüzden tez kapsamında yeni karben öncülleri ve kompleksleri sentezlenerek sübstitüye amin sentezindeki katalitik aktiviteleri incelenmiştir. Bulunan sonuçlar üç başlıkta özetlenebilir; 1) Tezde 1,3-dialkilimidazolidinyum (1a-f) ve 1,3-dialkil-benzimidazolyum (2a-i ve 3a-e) karben öncülleri sentezlenmiş, yapıları uygun spektroskopik yöntemlerle aydınlatılmıştır. 2) Sentezi gerçekleştirilen monodentat yapılı imidazolidinyum ve beznimidazoltum karben öncüllerinin uygun baz ile etkileştirilmesinden elde edilen NHC'ler, [RuCl2(p-simen)]2 kompleksi ile etkileştirilerek karşılık gelen NHC-Ru kompleksleri (4a-e, 5a-i ve 6a-d) sentezlenmiş ve yapıları uygun spektroskopik yöntemler ile aydınlatılmıştır. 3) Sentezlenen Ru-NHC komplekslerinin (4, 5) anilinin alkolerle alkilasyonu reaksiyonundaki katalitik aktiviteleri incelenmiştir.
Amines are a very important family of compounds in chemistry and biology. They are widely used in the production of pharmaceuticals, fine chemicals, ahrochemicals, polymers, dyestuffs, pigments, emulsifiers, and plasticizing agents. Clearly, a number of practical methods have been developed for the synthesis of amines in the past decades. However these conventional procedures have disadvantages like the use of enviromentally unfriendly halides, use of expensive amines as starting materials, production of large amounts of wasteful salts and low selectivies. Therefore, the development of more efficient and enviromentally friendly catalytic synthetic procedure is important. In recent years, hydrogen autotransfer process used in the synthesis of amine does not require additional hydrogen, carried out at atmospheric pressure and the use of special mechanisms. N-Heterocyclic carbenes (NHCs) are an interesting class of ligands with donor properties similar to phosphines. As they are strongly stabilized by -donating substituents, NHCs are good -donors. Metal–NHC complexes are mostly used in catalytic applications. Up to date, the use carbene complexes in this field is limited, improving the use of these catalyst will be very helpful. For this reason new carbene precursors and their metal complexes have been prepared and tested for synthesis of substituted amin in this work. This work could be summarized in three chapters. 1) In the first chapter, 1,3-dialkylimidazolidinium (1a-f) and 1,3-dialkilbenzimidazolium (2a-i ve 3a-e) NHC precursors were prepared and their structure were elucidated by spectroscopic techniques. 2) NHC complexes, obtained by the interaction of a monodentate carbene precursors and a base, reacted with [RuCl2(p-cimene)]2 complexes and the corresponding complexes (4a-e, 5a-i and 6a-d) were prepared and their structure was investigated with proper techniques. 3) Ru-NHC complexes (4 and 5) have been tested alkylation of aniline with alcohols and catalytic activities were investigated.
Amines are a very important family of compounds in chemistry and biology. They are widely used in the production of pharmaceuticals, fine chemicals, ahrochemicals, polymers, dyestuffs, pigments, emulsifiers, and plasticizing agents. Clearly, a number of practical methods have been developed for the synthesis of amines in the past decades. However these conventional procedures have disadvantages like the use of enviromentally unfriendly halides, use of expensive amines as starting materials, production of large amounts of wasteful salts and low selectivies. Therefore, the development of more efficient and enviromentally friendly catalytic synthetic procedure is important. In recent years, hydrogen autotransfer process used in the synthesis of amine does not require additional hydrogen, carried out at atmospheric pressure and the use of special mechanisms. N-Heterocyclic carbenes (NHCs) are an interesting class of ligands with donor properties similar to phosphines. As they are strongly stabilized by -donating substituents, NHCs are good -donors. Metal–NHC complexes are mostly used in catalytic applications. Up to date, the use carbene complexes in this field is limited, improving the use of these catalyst will be very helpful. For this reason new carbene precursors and their metal complexes have been prepared and tested for synthesis of substituted amin in this work. This work could be summarized in three chapters. 1) In the first chapter, 1,3-dialkylimidazolidinium (1a-f) and 1,3-dialkilbenzimidazolium (2a-i ve 3a-e) NHC precursors were prepared and their structure were elucidated by spectroscopic techniques. 2) NHC complexes, obtained by the interaction of a monodentate carbene precursors and a base, reacted with [RuCl2(p-cimene)]2 complexes and the corresponding complexes (4a-e, 5a-i and 6a-d) were prepared and their structure was investigated with proper techniques. 3) Ru-NHC complexes (4 and 5) have been tested alkylation of aniline with alcohols and catalytic activities were investigated.
Açıklama
22.09.2017 tarihine kadar kullanımı yazar tarafından kısıtlanmıştır.
Anahtar Kelimeler
Kaynak
WoS Q Değeri
Scopus Q Değeri
Cilt
Sayı
Künye
Şahin, Z. (2014). Metal katalizli sübstitüye amin sentezi. İnönü Üniversitesi Fen Bilimleri Enstitüsü. 1-198 ss.
