β-L-Arabinokloraloz’un Mono- ve Di-Sülfonat Esterleri; 3-O-Korunmuş-5-Azido ve 5-O-Alkil Türevleri

Abstract

Bu araştırmada, basit monosakkarit iskeleti üzerinde di-mesilat (metan sülfonat) ve di-tosilat ester grupları ile primer pozisyonda azido gruplarının bulunduğu mono-mesilat ve mono-tosilat yapılı organik türevlerin sentezi hedeflenmiştir. Bu hedef doğrultusunda, β-L-Arabinofuranoz başlangıç şekeri olarak seçilmiştir. Bu monosakkarit biriminin kloral ile derişik H₂SO₄ varlığındaki tepkimesi sonrası 1,2-O-(S)-Trikloroetiliden-β-L-arabinofuranoz elde edilmiştir. Daha sonra, trikloroetiliden asetal halkası ile korunmuş olan bu şekerin iskelet yapısı üzerinde öncelikle 3,5-Di-O-mesil (di-mesilat) ve 3,5-di-O-tosil (di-tosilat) gruplarının var olduğu ester türevleri sentezlenmiştir. Devamında, uygun reaksiyon koşullarında bu di-mesilat ve di-tosilat ester türevlerinden 5-Azido-3-O-mesil ve 5-azido-3-O-tosil türevleri elde edilmiştir. Ayrıca, 1,2-O-(S)-Trikloroetiliden-β-L-arabinofuranoz’un mono-tosilat ester türevi, ilgili 5-O-tosil-3-O-metil türevini elde etmek için gümüş oksit varlığında metil iyodür ile reaksiyona sokulmuştur. Elde edilen bu türev uygun reaksiyon koşullarında 5-Azido-3-O-metil türevine dönüştürülmüştür. İlaveten, 1,2-O-(S)-Trikloroetiliden-β-L-arabinofuranoz ilgili 5-O-tritil türevi elde etmek için tritil klorür ile reaksiyona sokulmuştur. 5-O-Tritil türevinin metilleme reaksiyonuyla 5-O-tiritil-3-O-metil arabinokloraloz sentezlenmiştir. Böylelikle, 5-O-Tosil ve 5-O-tiritil türevlerinde, karbohidrat iskelet biriminin sekonder hidroksil grubu metil grubu ile korunmuştur. Sentezlenen tüm yeni moleküller spektroskopik teknikler (IR, NMR ve Kütle) kullanılarak yapısal olarak karakterize edilmiştir.

Keywords

• Arabinoz,Azit,Furanoz,Kloraloz,Monosakkarit

Mono- and Di-Sulfonate Esters of -L-Arabinochloralose; 3-O-Protected-5-Azido and 5-O-Alkyl Derivatives

Abstract

In this research, it was aimed to synthesize the organic compounds containing di-mesylate (methane sulfonate) and di-tosylate ester groups on the simple monosaccharide skeleton and mono-mesylate and mono-tosylate organic derivatives including azido groups in the primer position. In this target, β-L-arabinofuranose was chosen as the starting sugar. After the reaction of this monosaccharide unit with chloral in the presence of concentrated H₂SO₄, 1,2-O-(S)-trichloroethylidene-β-L-arabinofuranose was firstly obtained. The ester derivatives, 3,5-di-O-mesyl (di-mesylate) and 3,5-di-O-tosyl (di-tosylate), were then synthesized on this sugar skeleton protected with trichloroethylidene acetal ring. 5-Azido-3-O-mesyl and 5-azido-3-O-tosyl derivatives of these di-mesylate and di-tosylate ester derivatives were subsequently obtained under appropriate reaction conditions. Furthermore, the mono-tosylate ester derivative of 1,2-O-(S)-Trichloroethylidene-β-L-arabinofuranose was reacted with methyl iodide in the presence of silver oxide to obtain the corresponding 5-O-tosil-3-O-methyl derivative. This obtained derivative was converted to the 5-Azido-3-O-methyl derivative under suitable reaction conditions. In addition, the 1,2-O-(S)-Trichloroethylidene-β-L-arabinofuranose was reacted with trityl chloride to produce the corresponding 5-O-trityl derivative. The 5-O-Trityl-3-O-methyl arabinochloralose was synthesized by the methylation reaction of 5-O-trityl derivative. Thus, the secondary hydroxyl group of the carbohydrate skeleton unit is protected by methyl group in the 5-O-tosyl and 5-O-trityl derivatives. All newly synthesized molecules were structurally characterized by using spectroscopic techniques (IR, NMR and Mass).

Keywords

• Arabinoz,Azit,Furanoz,Kloraloz,Monosakkarit,Sülfonat ester

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