Yeni kiral ß-hidroksi amin ve kaliks[4]aren türevlerinin sentezi, enantiyomerlerin tanınmasında kullanılması
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Dosyalar
Tarih
2011-10-20
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Selçuk Üniversitesi Fen Bilimleri Enstitüsü
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Bu çalışmada, çeşitli kiral ve akiral amin türevleri ile (R)-(?)-N-(2,3- epoksipropil)ftalimid (3) bileşiğinin reaksiyonu sonucunda % 56?93 verimle yedi farklı optikçe aktif amino alkol türevi sentezlendi. Bu optikçe aktif amino alkol türevlerinin (8?11) rasemik yapıdaki karboksilik asitlere karşı enantiyomerik tanıma özellikleri 1H NMR spektroskopisi kullanılarak araştırıldı. Bu çalışmada kullanılan kiral reseptörler arasında, en iyi kiral kaydırma reaktifinin amino alkol türevi 9 olduğu belirlendi. Ayrıca, kiral ftalimid türevleri hidrazin mono hidrat ile indirgenerek kiral primer amin bileşikleri (12?15 ve 22?24) hazırlandı. Bu primer amin türevleri ile 25,27-dietoksikarbonilmetoksi-26,28-dihidroksi-5,11,17,23-(tetra-ter)bütil-kaliks[4]aren (2) bileşiğinin reaksiyonu sonucunda yedi farklı yeni kiral amit kaliks[4]aren bileşiği (25?31) başarıyla sentezlendi. Bazı amino asit metil ester tuzları ve mandelik asitin taşınması kiral kaliks[4]arenler (25?30) kullanılarak sıvı-sıvı membran sistemi ile çalışıldı. Özellikle kaliks[4]aren türevi 25 'in triptofan metilesterin taşınmasında, D enantiyomerini L enantiyomerine göre 3.29 kat daha fazla taşıma gösterdiği tespit edildi. Elde edilen sonuçlara göre enantiyoseçiciliğin ilk iki saat içinde artmasına rağmen bundan sonraki zamanda azaldığı gözlendi.
In this study, seven optically active amino alcohol derivatives were synthesized via the ring opening of (R)-N-(2,3-epoxypropyl)phthalimide (3) with chiral and achiral amines in 56?93% yields. The enantioselective recognition properties of these receptors (8?11) towards the enantiomers of racemic carboxylic acids was examined by 1H NMR spectroscopy. Among the chiral receptors used in this study, amino alcohol 9 was determined to be the best chiral shift reagent. In addition, chiral primary amine derivatives (12?15 and 22?24) were readily prepared by cleavage of chiral phthalimides with hydrazine hydrate by refluxing in ethanol. The synthesis of seven diamide derivatives of the p-tert-butylcalix[4]arenes (25?31) from the reaction of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-dihydroxy calix[4]arene (2) with this primary amines was performed succesfully. The transport of amino acid derivatives (phenylglycine, phenylalanine and tryptophan methyl ester hydrochlorides) and mandelic acid were studied through a bulk liquid membrane in the presence of chiral calix[4]arene derivatives (25?30). It was found that compound 25 showed the best enantioselectivity for tryptophane metylester, affording a KD/KL value of 3.29. According to the results, the enantioselectivity increased linearly during the ? rst two hours, after which time a decrease in enantioselectivity was observed.
In this study, seven optically active amino alcohol derivatives were synthesized via the ring opening of (R)-N-(2,3-epoxypropyl)phthalimide (3) with chiral and achiral amines in 56?93% yields. The enantioselective recognition properties of these receptors (8?11) towards the enantiomers of racemic carboxylic acids was examined by 1H NMR spectroscopy. Among the chiral receptors used in this study, amino alcohol 9 was determined to be the best chiral shift reagent. In addition, chiral primary amine derivatives (12?15 and 22?24) were readily prepared by cleavage of chiral phthalimides with hydrazine hydrate by refluxing in ethanol. The synthesis of seven diamide derivatives of the p-tert-butylcalix[4]arenes (25?31) from the reaction of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-dihydroxy calix[4]arene (2) with this primary amines was performed succesfully. The transport of amino acid derivatives (phenylglycine, phenylalanine and tryptophan methyl ester hydrochlorides) and mandelic acid were studied through a bulk liquid membrane in the presence of chiral calix[4]arene derivatives (25?30). It was found that compound 25 showed the best enantioselectivity for tryptophane metylester, affording a KD/KL value of 3.29. According to the results, the enantioselectivity increased linearly during the ? rst two hours, after which time a decrease in enantioselectivity was observed.
Açıklama
Anahtar Kelimeler
β-hidroksi amin, Kiral kaliks[4]aren, Kiral tanınma, Kiral taşıma, NMR titrasyonu, Membran, β-hydroxyamine, Chiral calix[4]arene, Chiral recognition, Chiral transport, NMR titration, Membrane
Kaynak
WoS Q Değeri
Scopus Q Değeri
Cilt
Sayı
Künye
Bozkurt, S. (2011). Yeni kiral ß-hidroksi amin ve kaliks[4]aren türevlerinin sentezi, enantiyomerlerin tanınmasında kullanılması. Selçuk Üniversitesi, Yayımlanmış doktora tezi, Konya.
