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

Year 2019, , 659 - 668, 21.05.2019

Nilgün Yenil

https://doi.org/10.21205/deufmd.2019216228

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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