CS240333B1 - Method of stereospecific preparation of 1,2-anhydro-2,4-di-O-acetyl-δ-D-glucopyranose - Google Patents
Method of stereospecific preparation of 1,2-anhydro-2,4-di-O-acetyl-δ-D-glucopyranose Download PDFInfo
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Abstract
Spůsob stereošpecifickej přípravy 1,6-anhydro-2,4-di-O-acetyl-/3-D-glukopyranózy. Riešenie sa týká oboru chémie a biochemie sacharidov. Vynález rieši sposob stereospecifickej přípravy l,6-anhydrb-2,4-di-O- -acetyl-/?-D-glukopyranózy působením enzýmov skupiny hydroláz. Uvedeného účelu sa dosiahne tým, že na roztok 1,6-anhydro- -2,3,4-tri-O-acetyl-/S-D-glukopyranózy v citrátovo fosforečnanovom pufri o 0,01 až 0,05 mol . l~'a pH 5,0 až 5,5 sa působí roztokom chymotrypsínu alebo lipázy pšeničného klíčku. Riešenie má využítie v základnej chémii a biochémii sacharidov, predovšetkým pri přípravě derivátov D-glukózy obměněných v polohe C-3, alebo k přípravě disacharidov.Method for stereospecific preparation of 1,6-anhydro-2,4-di-O-acetyl-/3-D-glucopyranose. The solution relates to the field of chemistry and biochemistry of carbohydrates. The invention provides a method for stereospecific preparation of 1,6-anhydro-2,4-di-O- -acetyl-/3-D-glucopyranose by the action of enzymes of the hydrolase group. The stated purpose is achieved by treating a solution of 1,6-anhydro- -2,3,4-tri-O-acetyl-/3-D-glucopyranose in a citrate-phosphate buffer of 0.01 to 0.05 mol . l ~' and pH 5.0 to 5.5 with a solution of chymotrypsin or wheat germ lipase. The solution has applications in basic chemistry and biochemistry of carbohydrates, especially in the preparation of D-glucose derivatives modified at the C-3 position, or for the preparation of disaccharides.
Description
Vynález sa týká stereošpecifickej přípravy l,G-anliydro-2,4-cii-O-acetyl-,'l-Dglukopyranózy. 'The present invention relates to the stereospecific preparation of 1,1 G-anliydro-2,4-cis-O-acetyl-1,1-glucopyranose. '
l.e-AnhydrinS-D-glukopyranóza a jej parciálně acetylované deriváty sú vhodnými prekurzormi pri príprave mnohých derivátov glukózy (dezoxycukry, aminocukry a podobné) ako aj disacharidov glukózového typu. Načhádzajú preto použitie ako čisté chemikálie, vhodné pre teoretické štúdinm chémie a biochémie sacharidov. Doteraz sa připravovali buď acetyláciou l^-anhydro-jS'-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-acetylderivátu 1,6-anhydro-/3-D-glukopyranózy [Š. Kučár, J. Zámocký, J. Zemek, D. Anderle, M. Matulová: Collection Czech. Chem. Commun. 1985). Nevýhodou uvedených spésobov je nízká steréošpécificitá rěákčie, čo má za' nášledok vo vačšine prípadov vznik zmesi monoa di-acetyl-derivátov.1.e-AnhydrinS-D-glucopyranose and its partially acetylated derivatives are suitable precursors in the preparation of many glucose derivatives (deoxy sugars, amino sugars and the like) as well as glucose-type disaccharides. Therefore, they are intended to be 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'-anhydro-1'-D-glucopyranose [D. Shapiro, Y. Rabinsohn, A.J. Acher, A. Diver-Haber, J. Org. Chem. 35, 1464 (1970)] or by chemical hydrolysis of the 2,3,4-tri-O-acetylderivative of 1,6-anhydro- [beta] -D-glucopyranose [S. Kucar, J. Zamocky, J. Zemek, D. Anderle, M. Matulova: Collection Czech. Chem. Commun. 1985). A disadvantage of these methods is the low sterospecificity of the ratchet, which in most cases results in the formation of a mixture of mono-acetyl derivatives.
Uvedené nedostatky v podstatné] miere odstraňuje postup podlá vynálezu, ktorého podstata spočívá v posobení chymotrypsínu EC 3.4.4.5 alebo lipázy z pšeničných klíčkov EC 3.1.1.3 v 0,01 až 0,05 mol . I-1 citranovo fosforečnanovom tlmivom roztoku o pH -5- až 5,8 . pri teplote-29--až-áO^C- na 1,6-anhydro-2,3,4-tri-O-acetyl-/3-D-glukopyranózu.The above-mentioned drawbacks are substantially eliminated by the process according to the invention, which consists in impregnating chymotrypsin EC 3.4.4.5 or wheat germ lipase EC 3.1.1.3 in 0.01 to 0.05 moles. I -1 citrate phosphate buffer pH -5- to 5.8. at a temperature of 29- to 0 ° C to 1,6-anhydro-2,3,4-tri-O-acetyl- β-D-glucopyranose.
Výťažok l,6-anhydro-2,4-di-O-acetyl-/3-D-glukopyranózy v tejto reakcii je okolo 90 pere. V reakcii s chymotrypsínom podiel všetkých ostatných deacetylačných produktov v reakčnej zmesi je okolo 10 %. Reakcia s lipázou z pšeničných klíčkov prebieha podstatné rýchlejšie, už za 1 hodinu je pri rovnakých aktivitách enzýmov ako v případe chymotrypsínu východzí 1,6-anhydro-2,3,4-tri-O-acetyl-l3-D-glukopyranóza čiastočne deacetylovaná, výťažok 1,6-anhydro-2,4-di-O-acetyl-jž-D-glukopyranózy v reakčnej zmesi je však nižší, okolo 52 %. Výhodou tohto postupu je jeho jednoduchost, vysoké výtažky l,6-anhydro-2,4-dl-O-acetyl-j3-D-glukopyranózy v jednom reakčnom stupni.The yield of 1,6-anhydro-2,4-di-O-acetyl- [beta] -D-glucopyranose in this reaction is about 90 washes. In reaction with chymotrypsin, the proportion of all other deacetylation products in the reaction mixture is about 10%. The reaction of a lipase from wheat germ proceeds considerably faster, as little as 1 hour at the same enzyme activity as in the case of chymotrypsin the starting 1,6-anhydro-2,3,4-tri-O-acetyl-L 3-D-glucopyranose partially deacetylated however, the yield of 1,6-anhydro-2,4-di-O-acetyl-β-D-glucopyranose in the reaction mixture is lower, about 52%. The advantage of this process is its simplicity, high yields of 1,6-anhydro-2,4-dl-O-acetyl-β-D-glucopyranose in one reaction step.
Příklad 1 l,6-Anhydro-2,3,4-tri-O-acetyl-/3-D-glukopyranoza (1 g) sa rozpustí v 10 ml metanolu a takto připravený roztok sa přidá do 50 ml citranovo fosforečnanového pufru, 0,05 mol . I1 o pH 5,8 a přidá sa chymotrypsín z bravčového pankreasu, 1 ml o celkovej aktivitě 1,5 ncat a špecifickej aktivitě 2,8 ncat . mg1. Enzýmová hydrolýza prebieha pri teplote 20 °C po dobu 90 hodin. Získaný reakčný produkt obsahoval 91,2% normalizovaných to je 0,912 mg 1,6-anhydro-2,4-di-O-acetyl-/?-D-glukopyranózy. Reakčná zmes mimo tohoto hlavného produktu obsahovala 1,6 % l,6-anhydro-4-O-acetyl-(S-D-glukopyranózy, 0,8 % l,6-anhydro-3-O-acetyl-/3-D-glukopyranózy, 6,4 % 1,6-anhydro-2,3-di-O-acetyl-/3-D-glukopyranózy. Separácia l,6-anhydro-2,4-di-O-acetyl-(S-D-glukopyranózy sa prevedie chromatograficky na kolene s náplňou silikagélu v chromatografickej sústave octan etylnatý : benzen : 2-propanol (8:4:1 objemových podielov).EXAMPLE 1 1,6-Anhydro-2,3,4-tri-O-acetyl- [beta] -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. , 05 mol. 1 I, pH 5.8 and treated with chymotrypsin from porcine pancreas, 1 mL of the total activity of 1.5 ncat a specific activity of 2.8 ncat. mg 1 . The enzyme hydrolysis is carried out at 20 ° C for 90 hours. The reaction product obtained contained 91.2% normalized i.e. 0.912 mg of 1,6-anhydro-2,4-di-O-acetyl-β-D-glucopyranose. The reaction mixture outside this main product contained 1.6% 1,6-anhydro-4-O-acetyl- (SD-glucopyranose, 0.8% 1,6-anhydro-3-O-acetyl- / 3-D-glucopyranose) 6,4% 1,6-anhydro-2,3-di-O-acetyl- [3-D-glucopyranose] The separation of 1,6-anhydro-2,4-di-O-acetyl- (SD-glucopyranose) Chromatography on silica gel eluting 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 ako je uvedené v příklade 1, s tým rozdielom, že sa použije chymotrypsín z hovadzieho pankreasu. Výsledky boli rovnaké, ako v případe použitia chymotrypsínu z pankreasu ošípaných.The procedure is as described in Example 1 except that chymotrypsin from bovine pancreas is used. The results were the same as in the case of pig pancreas chymotrypsin.
P r í k 1 a d 3EXAMPLE 1 a d 3
Postupuje sa tak ako v příklade 1 s tým rozdielom, že sa použije ako enzým lipáza z pšeničného klíčku o celkovej aktivitě 1,9 ncat a špecifickej aktivitě 1,8 ncat . mg-1, rozpuštěná v 50 ml citranovo fosforečnanového pufru, 0,01 mol . I1 o pH 5,0. 1,6-Anhydro-2,3,4-tri-O-acetyl-/3-D-glukopyranóza sa rozpustí v 10 ml metanolu a přidá k pufrovanému roztoku enzýmu. Enzýmová hydrolýza prebieha po dobu 1 hodiny pri teplote 40 °C. Výťažok l,6-anhydro-2,4-di-O-acetyl-^-D-glukopyranózy bol 0,52 g, to je 52 %. Obsah dalších sprievodných mono- a di-O-acetylderivátov v reakčnej zmesi bol nasledovný: l,6-anhydro-4-O-acetyl-/í-D-glukopyranózy bol 0,23 g, l,6-anhydro-2-O-acetyl-/3-D-glukopyranózy 0,04 g, 1,6-anhydro-3-O-acetyl-/3-D-glukopyranózy 0,06 g, 1,6-anhydro-3,4-di-O-acetyl-/?-D-glukopyranózy 0,08 g a l,6-anhydro-2,3-di-O-acetyl-/3'-D-glukopyranózy 0,07 g.The procedure is as in Example 1 except that wheat germ lipase with a total activity of 1.9 ncat and a specific activity of 1.8 ncat is used as the enzyme. mg -1 , dissolved in 50 ml of citrate phosphate buffer, 0.01 mol. 1 I, pH 5.0. 1,6-Anhydro-2,3,4-tri-O-acetyl- [beta] -D-glucopyranose is dissolved in 10 ml of methanol and added to the buffered enzyme solution. The enzyme hydrolysis is carried out for 1 hour at 40 ° C. The yield of 1,6-anhydro-2,4-di-O-acetyl-4-D-glucopyranose was 0.52 g, i.e. 52%. The content of other concomitant mono- and di-O-acetylderivatives in the reaction mixture was as follows: 1,6-anhydro-4-O-acetyl-1-D-glucopyranose was 0.23 g, 1,6-anhydro-2-O -acetyl- (3-D-glucopyranose) 0.04 g, 1,6-anhydro-3-O-acetyl- (3-D-glucopyranose) 0.06 g, 1,6-anhydro-3,4-di-O -acetyl-β-D-glucopyranose 0.08 gal, 6-anhydro-2,3-di-O-acetyl- β'-D-glucopyranose 0.07 g.
Vynález móže nájsť široké uplatnenie v základnej organickej syntéze v oblasti sacharidov, predovšetkým glukózových derivátov modifikovaných substitučně na hydroxylovej skupině v polohe C-3 a oligosacharidov zložených z D-glukopyranozylových jednotiek viazaných a- alebo /3-1,3-vazbami.The invention can find wide application in basic organic synthesis in the field of carbohydrates, in particular glucose derivatives modified at the C-3 position on the hydroxyl group and oligosaccharides composed of D-glucopyranosyl units bound by α- or β-1,3-bonds.
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| CS847048A CS240333B1 (en) | 1984-09-20 | 1984-09-20 | Method of stereospecific preparation of 1,2-anhydro-2,4-di-O-acetyl-δ-D-glucopyranose |
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| CS847048A CS240333B1 (en) | 1984-09-20 | 1984-09-20 | Method of stereospecific preparation of 1,2-anhydro-2,4-di-O-acetyl-δ-D-glucopyranose |
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| CS240333B1 true CS240333B1 (en) | 1986-02-13 |
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