CS271973B1 - 4-Matylumbelliferyl-3,4-di-O-acetyl-4-D-xylopyranoside and its Preparation - Google Patents

4-Matylumbelliferyl-3,4-di-O-acetyl-4-D-xylopyranoside and its Preparation Download PDF

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CS271973B1
CS271973B1 CS887597A CS759788A CS271973B1 CS 271973 B1 CS271973 B1 CS 271973B1 CS 887597 A CS887597 A CS 887597A CS 759788 A CS759788 A CS 759788A CS 271973 B1 CS271973 B1 CS 271973B1
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xylopyranoside
acetyl
methylumbelliferyl
preparation
acatyl
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CS887597A
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Czech (cs)
Slovak (sk)
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CS759788A1 (en
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Stefan Rndr Csc Kucar
Jan Rndr Kozak
Peter Rndr Csc Biely
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Kucar Stefan
Kozak Jan
Biely Peter
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Priority to CS887597A priority Critical patent/CS271973B1/en
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Publication of CS271973B1 publication Critical patent/CS271973B1/en

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Abstract

RieSenie ea týká novej zlúčeniny a sposobu pripravy 4-metylumbelliferyl-3,4- -di-O-acetyl-4-D-xylopyranozidu. Uvedeného účelu ea dosiahne tým, že na 4-metylumbelliferyl-2,3,4-trl-O-acetyl-Á-D-xylopyranozid v prostředí pyridinu ea posobl hydrazinhydrátom po dobu 2 hodin a teplote 20 oc až 25 oc a z reakčnej zmesi sa pomocou chromatografickej separácle ziska 4-matylumbelliferyl-3,4-di-0-acatyl- -4-D-xylopyranozid. Rieéenla mé použitia Jednak v základnom chemickom a blochemickm výskume sacharidov, jednak pri priprave komerčně zaujímá vých 4-metylumbelliferyl-/3-glykozidov oligosacharidov potenciálnych fluorogenných substrátov pra /f-xylozidázy.The present invention relates to a new compound and a method for preparing 4-methylumbelliferyl-3,4- -di-O-acetyl-4-D-xylopyranoside. The above purpose is achieved by treating 4-methylumbelliferyl-2,3,4-tri-O-acetyl-4-D-xylopyranoside in a pyridine environment with hydrazine hydrate for 2 hours at a temperature of 20°C to 25°C and chromatographic separation is used to obtain 4-methylumbelliferyl-3,4-di-O-acetyl-4-D-xylopyranoside from the reaction mixture. The solution has many uses, both in basic chemical and molecular research on carbohydrates and in the preparation of commercially interesting 4-methylumbelliferyl-3-glycosides of oligosaccharides, potential fluorogenic substrates for /f-xylosidase.

Description

Vynález sa týká 4-matylumbelllfaryl-3,4-O-acatyl-X-D-xylopyranozldu a sposobu jeho prlpravy. 4-Matylumballifaryl-/í-D-xylopyranozid(UMB-/í-D-xylopyranozid) prip. Jaho deriváty možu nájsť uplatnenie ako fluoroganné substráty pra yý-xylozidázy (EC 3.2.1.37). 4-Matylumballifaryl-3,4-di-O-acatyl-4-D-xylopyranozid ja vhodným prakurzorom pri priprava 4-matylumballlfaryl-ií-glykozldov oligoaacharidov, potanciálnych aubstrátov pra yý-D-xylozidázy xylobiázového alabo axo-xylanázového typu. Analogické deriváty glukózy, calobiózy a laktózy ea využívajú na detekciu β dlfaranciáciu calulolytlckých enzýmov /Van Tilbaurgh H., Claaysaana M., Oa Bruyna C.K. FEBS Lattara 149, 152 (19S2)t Van Tllbaurgh H., Claayaaane M. FEBS Lattara 178, 283 (1985)j Bialy P., Markovič O. Blotachnol. Appl. Blechám. 10, 99 (1988)/. 4-Matylumballifaryl-3,4-dl-O-acatyl-/J-D-xylopyranozid, ktorý nabol doteraz v literatúre popísaný Je predmetom tohto vynálezu. Podstata vynálezu spočiva tiež v posobani hydrazínhydrátu pri teplota 20 °C až 25 °C na 4-metylumballiferyl-2,3,4-tri-0-acatyl-/?-D-xylopyranozid po dobu 2 hodin. Výtažok 4-matylumballifaryl-3,4-di-0-acatyl-X-D-xylopyranozldu v tejto raakcii ja cca 27 %. Z vedlejších produktov, okrem Salšich di-O-acatyl darivátov 4-matylumbellifaryl-^-D-xylopyranozidu, převláda východzí 2,3,4-tri-0-acatyl derivát v cca 40 % zastúpeni, ktorý po eaparácil Ja možné použit na dalšiu hydrozlnolýzu. Výhodou tohto postupu Ja jednoduchost prevedenia a možnost prlpravy 4-metylumballifaryl-3,4-di-Ó-acatyl-/í-D-xylopyranozidu v jednom raakčnom stupni. Přiklad 1 2,17 g 4-matylumbelllfaryl-2,3,4-tri-O-acetyl-4-D-xylopyranozidu sa rozpustí v 50 ml pyridinu a do reakčného roztoku sa přidá 1 ml hydrazínhydrátu. Výsledný reakčný roztok sa drži pri teplota 20 - 25 °C po dobu 2 hodin. Potom sa k němu přidá 50 ml acetonu a po 2-hodinovom miešaní sa zahusti do sirupu. Separácia 4-metylumballifary1-3,4-di-O-acatyl-yř-O-xylopyranozidu z reakčnej zmesi sa uskutoční chromatografiou na kolona a náplňou sillkagal v chromatografickej aúatava octan etylový : banzón t hexán (6:2:2 objemových podielov). Zíaka aa 0,52 g (27 %) chromatografický čistý 4-matylumbellifaryl-3,4-di-O-acatyl-y?-D-xylopyranozid o t.t. 197 °C až 198 °C, /«/g° - -62,3° (CH4Cl3).The present invention relates to 4-methylumbellyl-3,4-O-acatyl-X-D-xylopyranoside and to its preparation. 4-Matylumbalipharyl- [beta] -D-xylopyranoside (UMB- [beta] -D-xylopyranoside); Its derivatives can be found to be useful as fluorogenic substrates for xylosidase (EC 3.2.1.37). 4-Matylumballiphyl-3,4-di-O-acatyl-4-D-xylopyranoside is a suitable precursor for the preparation of 4-methylbutylphenyl-1-glycosides of oligoaaccharides, of the d-xylosidase xylobiase and axo-xylanase-type substrates. Analogous derivatives of glucose, calobiosis and lactose e are used for detection of β long-linguistic enzymes (Van Tilbaurgh H., Claaysaana M., Oa Bruyna C.K.). FEBS Lattara 149, 152 (19S2) t Van Tllbaurgh H, Claayaaane M. FEBS Lattara 178, 283 (1985) Bialy P., Markovic O. Blotachnol. Appl. Fleas. 10, 99 (1988)]. 4-Matylumballifaryl-3,4-d1-O-acyl- [beta] -D-xylopyranoside, which has been disclosed in the literature so far, is an object of the present invention. The invention also relates to providing hydrazine hydrate at 4 ° C to 25 ° C to 4-methylumballiferyl-2,3,4-tri-O-acatyl-2-D-xylopyranoside for 2 hours. The yield of 4-methylumbalipharyl-3,4-di-O-acatyl-X-D-xylopyranoside in this reaction was about 27%. Of the by-products, in addition to the di-O-acatyl 4-matylumbellifaryl-β-D-xylopyranoside di-O-acyl derivative, the starting 2,3,4-tri-O-acatyl derivative predominates in about 40% of the moiety which can be used for further hydrozololysis. The advantage of this process is the ease of design and the possibility of preparing 4-methylumbalipharyl-3,4-di-ac-acatyl-β-D-xylopyranoside in one reaction step. EXAMPLE 1 2.17 g of 4-methylumbellyl-2,3,4-tri-O-acetyl-4-D-xylopyranoside are dissolved in 50 ml of pyridine and 1 ml of hydrazine hydrate is added to the reaction solution. The resulting reaction solution was held at 20-25 ° C for 2 hours. Then 50 ml of acetone are added and after stirring for 2 hours it is concentrated to syrup. Separation of 4-methylumbalipharyl-3,4-di-O-acyl-.alpha.-O-xylopyranoside from the reaction mixture is carried out by column chromatography and sillkagal chromatography in ethyl acetate: banzone t hexane (6: 2: 2 by volume). And 0.52 g (27%) of chromatographic pure 4-methylumbellifaryl-3,4-di-O-acyl-γ-D-xylopyranoside of m.p. 197 ° C to 198 ° C; [α] D -62.3 ° (CH 4 Cl 3).

Vynález moža nájel uplatnenie pri syntéza komerčně zaujimavých 4-metylumbellíferyl-/f-glykozldov oligoaacharidov ako potanciálnych fluorogenných subatrátov pra ^-xylozidázy.The invention has been found to be useful in the synthesis of commercially interesting 4-methylumbelliferyl- [omega] -glycosides of oligoaaccharides as potent fluorogenic prat-oxylozidase subatrates.

Claims (2)

PREDMET VYNÁLEZU 1. 4-Matylumballifaryl-3,4-di-O-acetyl-/f"D_xylopyranozid.OBJECT OF THE INVENTION 1. 4-Matylumbalipharyl-3,4-di-O-acetyl- (f) D-xylopyranoside. 2. Sposob prlpravy 4-matyluraballifaryl-3,4-di-O-acatyl-4-D-xylopyranozidu podlá bodu 1 vyznačený tým, ža sa poeobi na 4-matyiumballifaryl-2,3,4-tri-O-acatyl-/J-O-xylopyranozid hydrazinhydrátom v pyridine po dobu 2 hod., pri teplota 20 až 25 °C a po chromatograf ickaj saparácii aa ziska čistý produkt·2. A process for the preparation of 4-matylurabalipharyl-3,4-di-O-acatyl-4-D-xylopyranoside according to claim 1, characterized in that it is treated with 4-methyl-1-propyl-2,3,4-tri-O-acatyl- JO-xylopyranoside by hydrazine hydrate in pyridine for 2 hours, at 20 to 25 ° C and after chromatographic treatment and obtain pure product ·
CS887597A 1988-11-21 1988-11-21 4-Matylumbelliferyl-3,4-di-O-acetyl-4-D-xylopyranoside and its Preparation CS271973B1 (en)

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