CS240331B1 - Method of stereospecific preparation of 1,6-anhydro-2,3-di-O-α-ethyl-1-D-glucopyranose - Google Patents
Method of stereospecific preparation of 1,6-anhydro-2,3-di-O-α-ethyl-1-D-glucopyranose Download PDFInfo
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Abstract
Sposob stereošpecifickej přípravy 1,6-anhydro-2,3-di-O-acetyl-j3-D-glukopyranózy. Riešenle sa týká sposobu stereošpecifickej přípravy l,6-anhydro-2,3-di-O-acetyl-/f-D- -glukopyranózy. Podstata vynálezu spočívá v tom, že na l,6-anhydro-2,3,4-tri-O-acetyl- -/?-D-glukopyranózu sa katalyticky pósobí esterázou z pečene alebo lipázou z pankreasn vo vodnom roztoku tlmivého roztoku o pH 5,0 až 5,8 pri teplote 20 až 40 °C, pričom vhodným tlmivým roztokom je citranovo fosforečňanový tlmivý roztok. Riešenie má využitie v chemii a biochemii sacharidov.Method of stereospecific preparation of 1,6-anhydro-2,3-di-O-acetyl-j3-D-glucopyranose. The solution relates to a method of stereospecific preparation of 1,6-anhydro-2,3-di-O-acetyl-β-D-glucopyranose. The essence of the invention is that 1,6-anhydro-2,3,4-tri-O-acetyl--/?-D-glucopyranose is catalytically acted upon by esterase from the liver or lipase from the pancreas in an aqueous buffer solution with a pH of 5.0 to 5.8 at a temperature of 20 to 40 °C, a suitable buffer solution being a citrate phosphate buffer solution. The solution is used in the chemistry and biochemistry of carbohydrates.
Description
Vynález sa týká stereošpecifickej přípravy l,6-anhydro-2,3-di-O-acetyl-/?-D-glukopyranózy.The invention relates to the stereospecific preparation of 1,6-anhydro-2,3-di-O-acetyl-β-D-glucopyranose.
Parciálně acetylované deriváty 1,6-anhydro-/3-D-glukopyranózy sú výhodnými prekurzormi pri príprave mnohých látok, napr. aminoderivátov, metylderivátov monosacharidov a k príprave oligosacharidov. Nachádzajú tiež použitie ako čisté chemikálie vhodné pre teoretické štúdium chémie a biochémie sacharidov. Doteraz sa připravovali buď acetyláciou 1,6-anhydro-jíf-D-glukopyranózy [D. Shapiro, Y. Rabinsohn, A. J. Acher, A. Diver-Haber: J. Org. Chem. 35, 1 464 (1970]], alebo chemickou hydrolýzou 2,3,4-tri-O-acetytlderiváu 1,6-anhydro-jS-D-glukopyranózy (Š. Kučár, J. Zámocký, J. Zemek, D. Anderle, M. Matulová: Collection Czech. Chem. Commun.j. Nevýhodou uvedených postupov je nízká stereošpecificita reakcie, čo má za následok vo váčšine prípadov vznik zmesi mono- a di-acetyl-derivátov.Partially acetylated 1,6-anhydro- [beta] -D-glucopyranose derivatives are preferred precursors in the preparation of many substances, e.g. amino derivatives, methyl derivatives of monosaccharides and for the preparation of oligosaccharides. They are also used as pure chemicals suitable for the theoretical study of carbohydrate chemistry and biochemistry. To date, they have been prepared either by acetylation of 1,6-anhydro-N-D-glucopyranose [D. Shapiro, Y. Rabinsohn, A.J. Acher, A. Diver-Haber, J. Org. Chem. 35, 1464 (1970)], or by chemical hydrolysis of 2,3,4-tri-O-acetyl derivative of 1,6-anhydro-β-D-glucopyranose (S. Kučár, J. Zámocký, J. Zemek, D. Anderle) , M. Matulová: Collection Czech Chem Commun A disadvantage of these processes is the low stereospecificity of the reaction, which in most cases results in a mixture of mono- and di-acetyl derivatives.
Uvedené nedostatky y podstatnej miere odstraňuje postup podlá vynálezu, ktorého podstata spočívá v tom, že na 1,6-anhydro-2,3,4-tri-O-acetyl-(3-D-glukopyranózu sa katalyticky posobí esterázou z pečene alebo lipázou z pankreasu vo vodnom roztoku tlmivého roztoku o pH 5,0 až 5,8 pri teplotě 20 až 40 °C, pričom vhodným tlmivým roztokom je citranovofosforečňanový tlmivý roztok.The above-mentioned drawbacks are substantially eliminated by the process according to the invention, characterized in that the 1,6-anhydro-2,3,4-tri-O-acetyl- (3-D-glucopyranose) is catalytically impregnated with liver esterase or lipase from a pancreas in an aqueous buffer solution of pH 5.0-5.8 at 20-40 ° C, wherein a suitable buffer is citrate-phosphate buffer.
Výhodou předmětného sposobu je jeho jednoduchost, stereošpecifický priebeh a vysoké výťažky l,6-anhydro-2,3-di-O-acetyl-jŠ-D-glukopyranózy v jedinom reakčnom stupni.The advantage of the present process is its simplicity, stereospecific course and high yields of 1,6-anhydro-2,3-di-O-acetyl-β-D-glucopyranose in a single reaction step.
Příklad 1 l,6-anliydro-2,3,4-tri-O-acetyl-/?-D-glukopyranóža (1 gj sa rozpustí v 10 ml metanolu a takto připravený roztok sa přidá do 50 ml citranovo fosforečňanového pufru, 0,05 mol . I1 o pH 5 a k tomuto roztoku sa přidá ali-esteráza z bravčovej pečene [EC 3.1.1.1,] 1 ml o celkovej aktivitě 2,6 ncat a špecifickej aktivitě 2 ncat . mg-1. Enzýmová hydrolýza prebieha pri teplote 40 °C po dobu 48 h. Získaný reakčný produkt obsahoval 70 % hmotnostných l,6-anhydro-2,3-di-O-acetyl-/S-D-glukopyranózy, t. j. 0,7 g. Reakčná zmes mimo tohto hlavného produktu obsahovala 0,6 % hmotnostných 1,6-anhydro-^-D-glukopyranózy, 6,6'% hmotnostných l,6-anhydro-4-0-acetyl-/3-D-glukopyranózy, 4 % hmotnostně l,6-anhydro-2-O-acetyl-/S-D-glukopyranózy, 8,4 % hmotnostně l,6-anhydro-3-O-acetyl-jíi-D-glukopyranózy, 8,5 % hmotnostných l,6-anhydro-2,4-di-O-acetyl-/l-D-glukopyranózy a 7 % hmotnostných l,6-anhydro-3,4-di-0-acetyl-/3-D-glukopyranózy. Separácia l,6-anhydro-2,3-di-O-acetyl-jS-D-glukopyranózy sa prevedie na kolóne s náplňou hydroxidu křemičitého v chromatografickej sústave octan etýlnatý — benzen -- 2-propanol (8:4:1, objemových podielov).EXAMPLE 1 1,6-Anliydro-2,3,4-tri-O-acetyl-R-D-glucopyranose (1 g is dissolved in 10 ml of methanol and the solution thus prepared is added to 50 ml of citrate phosphate buffer, 0, 05 mole l of pH 5 and to this solution is added pork liver allyterase [EC 3.1.1.1,] 1 ml with a total activity of 2,6 ncat and a specific activity of 2 ncat mg mg -1 . The reaction product obtained contained 70% by weight of 1,6-anhydro-2,3-di-O-acetyl- / SD-glucopyranose, i.e. 0.7 g. The reaction mixture outside this main product contained 0%. 6,6% by weight 1,6-anhydro-4-D-glucopyranose, 6,6% by weight 1,6-anhydro-4-O-acetyl- [beta] -D-glucopyranose, 4% by weight 1,6-anhydro- 2-O-acetyl- / SD-glucopyranose, 8.4% by weight of 1,6-anhydro-3-O-acetyl-β-D-glucopyranose, 8.5% by weight of 1,6-anhydro-2,4-di -O-acetyl- (1'-D-glucopyranose) and 7% by weight of 1,6-anhydro-3,4-di-O-acetyl- (3-D-glucopyranose) Separation of 1,6-anhydro-2,3- The di-O-acetyl-β-D-glucopyranose was applied to a silica column packed with ethyl acetate-benzene-2-propanol (8: 4: 1 by volume).
P r í k 1 a d 2Example 1 a d 2
Postupuje sa tak ako v příklade 1, s tým rozdielom, že sa použije lipáza bravčového pankreasu [EC. 3.1.1.3] 2 ncat, o špecifickej aktivitě 1 rozpuštěná v 50 ml cltran-fosforečňanového pufru, 0,01 mol . 1_1 o pH 5,8. l,6-anhydro-2,3,4-tri-O-acetyl-(S-D-glukopyranóza (1 g) sa rozpustila v 10 ml metanolu a přidala k pufrovanému roztoku enzýmu. Enzýmová hydrolýza prebiehala po dobu 24 h pri teplote 40 °C. Výťažok 1,6-anhydro-2,3-di-O-acetyl-jS-D-glukopyranózy bol 0,75 g. Sprievodné ďalšie mono- a di-O-acetylderiváty boli v reakčnej zmesi obsiahnuté následovně: l,6-anhydro-4-O-acetyl-^-D-glukopyranóza 0,09 g, 1,6-anhydro-3-O-acetyl-/3-D-glukopyranóza 0,011 g, 1,6-anhydro-2-0 -acetyl-jíř-D-glukopyranóza 0,04 gramu a l,6-anhydro-2,4-di-O-acetyl-;3-D-glukopyranóza 0,09 g a l,6-anhydro-3,4-di-0-acetyl-/S-D-glukopyranóza 0,02 g. 1,6-anhydro-2,3-di-O-acetyl-^-D-glukopyranóza sa odseparovala z reakčnej zmesi stlpcovou chromatografiou; tak ako je uvedené v příklade 1.The procedure is as in Example 1, except that pancreatic lipase [EC. 3.1.1.3] 2 ncat, with specific activity 1 dissolved in 50 ml cltran-phosphate buffer, 0.01 mol. 1 _1 pH 5.8. 1,6-anhydro-2,3,4-tri-O-acetyl- (SD-glucopyranose (1 g) was dissolved in 10 ml of methanol and added to the buffered enzyme solution. The enzyme hydrolysis was carried out for 24 h at 40 ° C. The yield of 1,6-anhydro-2,3-di-O-acetyl-β-D-glucopyranose was 0.75 g. The accompanying additional mono- and di-O-acetylderivatives were contained in the reaction mixture as follows: 1.6 -anhydro-4-O-acetyl-4-D-glucopyranose 0.09 g, 1,6-anhydro-3-O-acetyl- [beta] -D-glucopyranose 0.011 g, 1,6-anhydro-2-O- acetyl-β-D-glucopyranose 0.04 grams α1,6-anhydro-2,4-di-O-acetyl-; 3-D-glucopyranose 0.09 gal, 6-anhydro-3,4-di-O- acetyl / SD-glucopyranose 0.02 g 1,6-anhydro-2,3-di-O-acetyl-4-D-glucopyranose was separated from the reaction mixture by column chromatography as in Example 1.
Vynález móže nájsť široké uplatnenie v základnej organickej syntéze v oblasti sa* charidov, predovšetkým glukózových derivátov modifikovaných substitučně na hydrdxylovej skupině v polohe C-4 a oligosacharidov zložených z D-glukózy viazaných a alebo β -1,4 alebo -1,6 vazbami.The invention can find wide application in basic organic synthesis in the field of sacharides, in particular glucose derivatives modified at the C-4 position on the hydroxyl group and oligosaccharides composed of D-glucose bound by or or β -1,4 or -1,6 bonds.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS847046A CS240331B1 (en) | 1984-09-20 | 1984-09-20 | Method of stereospecific preparation of 1,6-anhydro-2,3-di-O-α-ethyl-1-D-glucopyranose |
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| Application Number | Priority Date | Filing Date | Title |
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| CS847046A CS240331B1 (en) | 1984-09-20 | 1984-09-20 | Method of stereospecific preparation of 1,6-anhydro-2,3-di-O-α-ethyl-1-D-glucopyranose |
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| CS704684A1 CS704684A1 (en) | 1985-06-13 |
| CS240331B1 true CS240331B1 (en) | 1986-02-13 |
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| CS847046A CS240331B1 (en) | 1984-09-20 | 1984-09-20 | Method of stereospecific preparation of 1,6-anhydro-2,3-di-O-α-ethyl-1-D-glucopyranose |
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