Kimyasal ve biyoteknolojik yöntemlerle kiral yapıların sentezleri
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Dosyalar
Tarih
2006-06-13
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Yayıncı
Selçuk Üniversitesi Fen Bilimleri Enstitüsü
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Bu çalışma iki bölümden oluşmaktadır. Birinci bölümde kimyasal ve biyoteknolojik yöntemler kullanılarak çok fonksiyonlu kiral karboksilli asit türevleri sentezlenmiştir. İkinci bölümde ise supramoleküler kimya ve host-guest kimyasında pek çok kullanım alanına sahip olan kaliks[4]arenin kiral olan ve olmayan türevleri sentezlenmiş ve bazı özellikleri incelenmiştir. 1,3-siklohekzandiondan çıkılarak önce karbonil gruplarından biri seçimli olarak korunmuş (1) daha sonra Mn(OAc)3 ile α'-asetoksilleme (2) yapılmıştır. Oluşan rasemik bileşik enzimatik kinetik ayırma metodu ile lipaz enzimi (Amano PS) kullanılarak enantiyomerlerine (3) ayrılmıştır. Rasemik haldeki asetoksi enon bileşiği hidroliz edilerek dikarbonil türevine dönüştürülmüş (4) ve oxone varlığında bağ kırılmasıyla yükseltgenme reaksiyonu sonucu rasemik karboksilik asit metil esteri (5) elde edilmiştir. Bu reaksiyon referans olarak kullanılmış ve aynı reaksiyonlar enzimatik hidroliz sonucu elde edilen asetoksi ve hidroksi enon bileşikleri ile de gerçekleştirilmiştir. Sonuç olarak kiral yapıda karboksilik asit diester türevleri (7, 9) elde edilmiştir. Bu çalışma bu türde maddelerin sentezi için model bir yöntemdir. Çalışmanın ikinci bölümünde ise literatürde verilen metotlara göre önce p-t- bütilkaliks[4]aren (10) sentezlenmiş, sonra bu bileşiğin dealkilasyonu ile kaliks[4]aren (11) elde edilmiştir. Fenolik -OH gruplarının seçimli alkilasyonu sonucu dipropoksi türevi (12) elde edilmiş ve boşta kalan hidroksil gruplarının para konumlarına yine seçimli olarak aldehit grupları (13) bağlanmıştır. Sonraki basamakta ise sırasıyla 3-aminometil pridin ve 1,8-diaminooktan ile tepkimeye sokularak kaliks[4]arenin Schiff bazı türevleri (14 ve 15) elde edilmiştir. Bu bileşikler ticari olarak satılan Merrifield reçinesine bağlanarak polimerik türevleri (16 ve 17) elde edilmiştir. Kaliks[4]aren Schiff bazları ve polimerik türevleri alkali, toprak alkali ve geçiş metali katyonları ile dikromat anyonunun sulu fazdan organik faza taşınması çalışmalarında kullanılmıştır. Kaliks[4]arenin kiral tartarik ester türevi (19) yine literatürdeki metodun geliştirilmesiyle sentezlenmiş ve para köşelerinden seçimli nitrolama ile kromojenik kiral kaliks[4]aren türevi (20) elde edilmiştir. Kiral kaliks[4]aren türevleri bazı amino asitlerin faz transfer ekstraksiyonunda kullanılmıştır. Ayrıca bu bileşiklerin feniletil amin, 1,2-propandiol ve serin metil ester (SerOMe) guestlerine karşı kiral tanınma özellikleri 1H NMR spektroskopisi kullanılarak incelenmiştir. Gerçekleştirilen tüm reaksiyonlar İTK ile izlenmiş ve elde edilen ürünler kolon kromatografisi ile saflaştırılarak yapıları IR ve 1H NMR, 13 C NMR ve FAB MS teknikleriyle aydınlatıldıktan sonra kiral bileşiklerin optik çevirme açıları ölçülmüştür.
This study contains two chapters. In the first chapter polyfunctionalized chiral carboxylic acid derivatives have been synthesized by chemical and biotechnological methods. In the second chapter chiral and achiral derivatives of calix[4]arene which have important application fields in supramolecular and host-guest chemistry, have been synthesized and some properties of these new compounds investigated. In the first step, 1,3-cyclohexandione is protected under acid catalyzation and 3-methoxy-2-cyclohex-1-one (1) is obtained and converted to α-acetoxy enone (2) by Mn(OAc)3 mediated oxidation. Enzymatic kinetic resolution is applied to the racemic form of this product using lipase (Amano PS) and enantiomerically pure α-acetoxy enone and α-hydroxy enone (3) are obtained. Then, dicarbonyl derivative (4) is obtained by hydrolyzing racemic α-acetoxy enone and oxidative cleavage of 4 in the presence of oxone is furnished racemic carboxylic acid methyl ester (5). Using this reaction as a reference, similar reactions were carried out for enantiomerically pure α-acetoxy enone and α-hydroxy enone. At last, chiral carboxylic acid diester derivatives (7, 9) are obtained. This work is model for synthesis of these type of compounds. In the second section of study, p-tert-buthylcalix[4]arene (10) is synthesized and converted to calix[4]arene (11) by dealkylation reaction according to literature methods. Dipropoxy derivative of calix[4]arene (12) is obtained by selective alkylation of phenolic -OH groups and converted to dialdehyde derivative (13) by formylation reaction. Then, this compound was treated by respectively 3- aminomethyl pyridine and 1,8-diaminooctane and Schiff base derivatives of calix[4]arene (14, 15) were obtained. These compound are supported to Merrifield?s resin which commercial avaliable and their polimeric derivatives (16, 17) are obtained. The extraction properties of calix[4]arene Schiff bases and polimeric derivatives alkali, transition, post transition metal cations and for dichromate anions are investigated. Chiral tartaric ester derivative of calix[4]arene (19) is synthesized by the modification of method in the literature and then converted to chromogenic chiral calix[4]arene derivative (20) by the selective nitration at the para position. Chiral derivatives of calix[4]arene were used in phase transfer extraction of some selected α-amino acids. Moreover chiral recognition capability of these compounds towards the guests; phenylethyl amine, 1,2-propanediol and serine methyl ester (SerOMe) by 1H NMR spectroscopy was investigated. The reactions were monitored by TLC and pure compounds were obtained after crystallysation, column chromatography or both. The structures of synthesized compounds were identified by IR, 1H NMR 13 C NMR ve FAB MS and optical rotation measurements were also included.
This study contains two chapters. In the first chapter polyfunctionalized chiral carboxylic acid derivatives have been synthesized by chemical and biotechnological methods. In the second chapter chiral and achiral derivatives of calix[4]arene which have important application fields in supramolecular and host-guest chemistry, have been synthesized and some properties of these new compounds investigated. In the first step, 1,3-cyclohexandione is protected under acid catalyzation and 3-methoxy-2-cyclohex-1-one (1) is obtained and converted to α-acetoxy enone (2) by Mn(OAc)3 mediated oxidation. Enzymatic kinetic resolution is applied to the racemic form of this product using lipase (Amano PS) and enantiomerically pure α-acetoxy enone and α-hydroxy enone (3) are obtained. Then, dicarbonyl derivative (4) is obtained by hydrolyzing racemic α-acetoxy enone and oxidative cleavage of 4 in the presence of oxone is furnished racemic carboxylic acid methyl ester (5). Using this reaction as a reference, similar reactions were carried out for enantiomerically pure α-acetoxy enone and α-hydroxy enone. At last, chiral carboxylic acid diester derivatives (7, 9) are obtained. This work is model for synthesis of these type of compounds. In the second section of study, p-tert-buthylcalix[4]arene (10) is synthesized and converted to calix[4]arene (11) by dealkylation reaction according to literature methods. Dipropoxy derivative of calix[4]arene (12) is obtained by selective alkylation of phenolic -OH groups and converted to dialdehyde derivative (13) by formylation reaction. Then, this compound was treated by respectively 3- aminomethyl pyridine and 1,8-diaminooctane and Schiff base derivatives of calix[4]arene (14, 15) were obtained. These compound are supported to Merrifield?s resin which commercial avaliable and their polimeric derivatives (16, 17) are obtained. The extraction properties of calix[4]arene Schiff bases and polimeric derivatives alkali, transition, post transition metal cations and for dichromate anions are investigated. Chiral tartaric ester derivative of calix[4]arene (19) is synthesized by the modification of method in the literature and then converted to chromogenic chiral calix[4]arene derivative (20) by the selective nitration at the para position. Chiral derivatives of calix[4]arene were used in phase transfer extraction of some selected α-amino acids. Moreover chiral recognition capability of these compounds towards the guests; phenylethyl amine, 1,2-propanediol and serine methyl ester (SerOMe) by 1H NMR spectroscopy was investigated. The reactions were monitored by TLC and pure compounds were obtained after crystallysation, column chromatography or both. The structures of synthesized compounds were identified by IR, 1H NMR 13 C NMR ve FAB MS and optical rotation measurements were also included.
Açıklama
Anahtar Kelimeler
Enzimatik hidroliz, Enzymatic hydrolysis, Polifonksiyonel karboksilik asitler, Polyfunctionalized carboxylic acids, Kaliks[4]aren, Calix[4]arene, Schiff bazı, Schiff base, Faz transfer ekstraksiyonu, Phase transfer extraction, Enantiyomerik tanınma, Enantiomeric recognition
Kaynak
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Künye
Karaküçük, A. (2006). Kimyasal ve biyoteknolojik yöntemlerle kiral yapıların sentezleri. Selçuk Üniversitesi, Yayımlanmış doktora tezi, Konya.
