Sülfonamit grubu bağlı 1,2,3-triazol halkası içeren bazı monosakkaritlerin sentezi
Synthesis of some monosaccharides containing 1,2,3-triazole ring linkaged sulfonamide group
Yazar: BEYZA ISPARTALOĞLU
Danışman: DOÇ. DR. KADİR AY
Celal Bayar Üniversitesi / Fen Bilimleri Enstitüsü / Organik Kimya Ana Bilim Dalı
Derece: Yüksek Lisans, 2015
Konu: Kimya = Chemistry

Özet:
Bu çalışmada, potansiyel biyolojik aktiviteye sahip 1,2,3-triazol köprülü sülfonamit monosakkaritleri elde ettik. Bunun için önce, N-asetilbenzensülfonil klorürden başlanarak  4-asetamido-N-(prop-2-inil)benzensülfonamit (A2) ve 4-amino-N-(prop-2-inil)benzensülfonamit (A3) bileşikleri ve monoazit, monosakkaritler  (B1, C1, D2, E2), uygun başlangıç maddelerinden literatüre göre sentezlendi. 2,3,4,6-Tetra-O-asetil-β-D-glukopiranozil azit (B1), 2,3,4,6-tetra-O-asetil-β-D-galaktopiranozil azit (C1), 6-azido-6-deoksi-1,2;3,4-di-O-izopropiliden-α-D-galaktopiranoz (D2), 2,3;5,6-di-O-izopropiliden-β-D-mannofuranozil azit (E2), THF:t-BuOH:H2O (3:1:1) çözücü karışımında CuSO4.5H2O-sodyum askorbat katalizörlüğünde 55 C'de 4 saat ısıtılarak A2 ve A3 bileşikleri ile bakır katalizli alkin azit siklokatılma (CuAAC) tepkimesine (Klik tepkimesi) sokuldu. Klik tepkimesi ürünleri olan  1,4-disübstitüe 1,2,3-triazol bileşikleri, silika jel kolon kromatografisi ile saflaştırılarak 4-({[4′-asetamidobenzensülfonil]amino}metil)-1-(2″,3″,4″,6″-tetra-O-asetil-β-D-glukopiranozil)-1H-1,2,3-triazol (B1A2, %78), 4-({[4′-asetamido benzensülfonil]amino}metil)-1-(2″,3″,4″,6″-tetra-O-asetil-β-D-galaktopiranozil)-1H-1,2,3-triazol (C1A2, %83), 4-({[4′-asetamidobenzensülfonil]amino}metil)-1-(6″-deoksi-1″,2″;3″,4″-di-O-izopropiliden-α-D-galaktopiranoz-6″-il)-1H-1,2,3-triazol (D2A2, %86), 4-({[4′-asetamidobenzen sülfonil]amino}metil)-1-(2″,3″;5″,6″-di-O-izopropiliden-β-D-mannofuranozil)-1H-1,2,3-triazol (E2A2, %77), 4-({[4′-aminobenzensülfonil]amino}metil)-1-(2″,3″,4″,6″-tetra-O-asetil-β-D-glukopiranozil)-1H-1,2,3-triazol (B1A3, %76), 4-({[4′-aminobenzen sülfonil]amino}metil)-1-(2″,3″,4″,6″-tetra-O-asetil-β-D-galaktopiranozil)-1H-1,2,3-triazol (C1A3, %78), 4-({[4′-aminobenzensülfonil]amino}metil)-1-(6″-deoksi-1″,2″;3″,4″-di-O-izopropiliden-α-D-galaktopiranoz-6″-il)-1H-1,2,3-triazol (D2A3, %81), 4-({[4′-aminobenzensülfonil] amino}metil)-1-(2″,3″;5″,6″-di-O-izopropiliden-β-D-mannofuranozil)-1H-1,2,3-triazol (E2A3, %75) elde edildi. Literatürde bulunmayan yeni 8 bileşiğin yapı aydınlatmaları için FTIR, 1H-, 13C-, NOESY-, HSQC-, HMQC-, HMBC- NMR, LC-ESI-MS gibi modern spektroskopik yöntemler kullanıldı.

Abstract:
In this study, we are synthesized the 1,2,3-triazole-bridged sulfonamide monosaccharides, which have potential biological activity. For this purpose, 4-acetamido-N-(prop-2-ynyl)benzenesulfonamide (A2) and 4-amino-N-(prop-2-ynyl) benzenesulfonamide (A3) compounds were synthesized from N-acetylbenzenesulfonyl chloride and monoazido monosaccharides (B1, C1, D2, E2) from appropriate starting materials according to literature. The copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) reaction (click reaction) of 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl azide (B1), 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl azide (C1), 6-azido-6-deoxy-1,2;3,4-di-O-isopropylidene-α-D-galactopyranose (D2), 2,3;5,6-di-O-isopropylidene-β-D-mannofuranosyl azide (E2) with the compounds of A2 and A3 were seperately performed in THF:t-BuOH:H2O (3:1:1) in the catalyst of CuSO4.5H2O-sodium ascorbate in 55C for 4h. The obtained products 1,4-disubstituted 1,2,3-triazole compounds, 4-({[4′-acetamidobenzenesulfonyl]amino}methyl)-1-(2″,3″,4″,6″-tetra-O-acetyl-β-D-glucopyranosyl)-1H-1,2,3-triazole (B1A2, %78), 4-({[4′-acetamido benzenesulfonyl]amino}methyl)-1-(2″,3″,4″,6″-tetra-O-acetyl-β-D-galacto pyranosyl)-1H-1,2,3-triazole (C1A2, %83), 4-({[4′-acetamidobenzenesulfonyl] amino}methyl)-1-(6″-deoxy-1″,2″;3″,4″-di-O-isopropylidene-α-D-galactopyranose-6″-yl)-1H-1,2,3-triazole (D2A2, %86), 4-({[4′-acetamidobenzenesulfonyl]amino}methyl)-1-(2″,3″;5″,6″-di-O-isopropylidene-β-D-mannofuranosyl)-1H-1,2,3-triazole (E2A2, %77), 4-({[4′-aminobenzenesulfonyl]amino}methyl)-1-(2″,3″,4″,6″-tetra-O-acetyl-β-D-glucopyranosyl) -1H-1,2,3-triazole (B1A3, %76), 4-({[4′-aminobenzene sulfonyl]amino}methyl)-1-(2″,3″,4″,6″-tetra-O-acetyl-β-D-galactopyranosyl)-1H-1,2,3-triazole (C1A3, %78), 4-({[4′-amino benzenesulfonyl]amino}methyl)-1-(6″-deoxy-1″,2″;3″,4″-di-O-isopropylidene-α-D-galacto pyranose-6″-yl)-1H-1,2,3-triazole (D2A3, %81), 4-({[4′-aminobenzenesulfonyl]amino}methyl)-1-(2″,3″;5″,6″-di-O-isopropylidene-β-D-mannofuranosyl)-1H-1,2,3-triazole (E2A3, %75), were purified by  column chromatography  over silica gel. The structures of these new 8 compounds not found in literature were elucidated on the basis of FTIR, 1H-, 13C-, NOESY-, HSQC-, HMQC-, HMBC- NMR, LC-ESI-MS spectroscopic methods.