CS209557B1 - Method of preparation of the 14c-masked d-galactose - Google Patents

Method of preparation of the 14c-masked d-galactose Download PDF

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CS209557B1
CS209557B1 CS40080A CS40080A CS209557B1 CS 209557 B1 CS209557 B1 CS 209557B1 CS 40080 A CS40080 A CS 40080A CS 40080 A CS40080 A CS 40080A CS 209557 B1 CS209557 B1 CS 209557B1
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Czechoslovakia
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labeled
galactose
xylose
converted
preparation
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CS40080A
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Czech (cs)
Slovak (sk)
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Vojtech Bilik
Peter Biely
Josef Kolina
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Vojtech Bilik
Peter Biely
Josef Kolina
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Priority to CS40080A priority Critical patent/CS209557B1/en
Publication of CS209557B1 publication Critical patent/CS209557B1/en

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Abstract

Vynález sa týká spSsobu prípravy ^^Cznačkovanej D-galaktózy katalyzovanou epimerizáciou ^^C-značkovanej D-xylózy. Podstata vynálezu spočívá v tom, že D-xylóza sa vo vodnom roztoku za přítomnosti kyseliny molýbdénovej epimerizuje a epimérne aldepentózy sa prevedú nitrometánovou syntézou na 1-deoxy-l-nitrohexitoly, ktoré sa oxidačným rozkladom' konvertujú na odpovedajúce aldozy. Vynález má význam v tom, že 3^C-značkovaná D-galaktóza má široké uplatnenie v biochemickom výskume, a to v oblasti štúdia transportu a metabolizmu sacharidov.The invention relates to a method for preparing 3^C-labeled D-galactose by catalyzed epimerization of 3^C-labeled D-xylose. The essence of the invention lies in the fact that D-xylose is epimerized in aqueous solution in the presence of molybdenic acid and the epimeric aldepentoses are converted by nitromethane synthesis to 1-deoxy-1-nitrohexitols, which are converted to the corresponding aldoses by oxidative decomposition. The invention is of importance in that 3^C-labeled D-galactose has wide application in biochemical research, namely in the field of studying the transport and metabolism of carbohydrates.

Description

Predmetom vynálezu je spĎsob přípravy 14C-značkovanej D-galakto'zy katalyzovanou'epi-merizáciou 14C-značkovanej D-xylozy a následným uplatněním nitrometánovej syntézy a oxidač-ného rozkladu reakciou vzniknutých nitrohexitolov.The present invention provides a process for the preparation of 14C-labeled D-galactose catalyzed by 14C-labeled D-xylose followed by nitromethane synthesis and oxidative decomposition by the resulting nitrohexitols.

Efektivně postupy syntézy galakto'zy stí založené hlavně na predlžovaní uhlíkatého re-ťazca lyxozy. Kyanhydrínovou syntézou, hydrolýzou a následnou reakciou galakto'novej kyseli-ny sa získá z D-(1-14C Jlyxo'zy Dt-(2-14C)galakto'za (H. S. Isbell, H. L. Frush, R. Scheffer; J. Res1. Nat. Buř. Stand. 51. 201 (1953)), resp. z D-lyxózy a 14C~značkovaného kyanovodíkaD-d-^C) galaktoza (H. S. Isbell, H. L..Frush, N. B. Holt; J. Res. Nat. Buř. Stand 51, 307(1953)), připadne uplatněním.nitrometánove.j syntézy a oxidačného rozkladu 1-deoxy-l-nitro-galaktitolu na galaktozu (V. Bílik; Coll. Czechoslov. Chem. Commun. 39, 1621 (1974)). Vovšetkých týchto prípadoch je potřebná relativné menej dostupná lyxoza. Navrhovaný spĎsobpřípravy využívá ako východisková zllčeninu relativné dostupnejšiu D-xylózu.Effectively synthesize galactosite synthesis techniques based mainly on extending the lyxose carbon chain. Cyanhydrin synthesis, hydrolysis and subsequent reaction of galactonic acid is obtained from D- (1-14C Jlyxyl-Dt- (2-14C) galactose (HS Isbell, HL Frush, R. Scheffer; J. Res1. Nat., Bu. Stand 51, 201 (1953), respectively, of D-lyxose and 14 C-labeled cyanogen D-d-C galactose (HS Isbell, HL.Frush, NB Holt; J. Res. Nat. Stand 51, 307 (1953), possibly by the use of nitromethane synthase and oxidative decomposition of 1-deoxy-1-nitro-galactitol on galactose (V. Bilik; Coll. Czechoslov. Chem. Commun. 39, 1621 (1974)) ). In all these cases, relatively less available lyxosis is needed. The proposed method of preparation utilizes a relatively more affordable D-xylose as the starting material.

Podstata vynálezu spočívá v tom, že D-xyloza sa vo vodnom roztoku za přítomnosti kata-lytických množstiev kyseliny molybdénovej při teplote 80 až 100 °C po dobu 0,5 až 3 hodi-ny epimerizuje a epímérne aldopentozy sa bez osobitného delenia převedu nitrometánovou syn-tézou na odpovedajúce 1-deoxy-l-nitrohexitoly, ktoré sa oxidačným rozkladom konvertuji naodpovedajlce aldozy. Zo zmesi aldoz sa galaktoza osobitne jednoducho izoluje chromatogra-fiou na papieri. Z D--(U-^C) xylozy a ^^C-značkovaného nitrometáhu sa uvedeným postupom získá D-(U-^4CJgalaktoza. Obměnou D-xylózy, resp. Specificky 14C-žnačkovanej D-xylózy a nitrometán i, resp.l^C-značkovaného nitr.ometánu je daná možnost přípravy celej palety specificky značkova-ných D-galaktoz. Výhodou navrhovaného spĎsobu přípravy ^^G-značkovanej D-galaktózy je, že - využívá relativné dostupnejšiu aldopentozu, - značná.časť aldopentóz (60 - 70 %) sa spát regeneruje a mfiže sa použit do 3alšiehocyklu přípravy D-galaktozy (nitrohexitoly odvodené od xylozy sa za podmienok oxidačně-ho rozkladu retrogresnou reakciou konvertuji na východiskoví xylozu), - celý postup přípravy je v technickorn převedení velmi jednoduchý, - všetky potřebné chemikálie - vynímajíc 14C-značkovanl D-xylózu sl bežne dostupné. Příklad prevedenia V eklmavke opatrenej zábrusom a spfitným chladičom sa' zmes D-xylózy (25 mg), D-(U-14C)xylózy (10 yCi o špecifickej aktivitě 90 mCi/mmol), 0,1 % vodný roztok kyselinymolybdénovej zahrieva 2 hodiny pri 90 °C. Roztok sa potom zahustí (vákuová rotačná odpar-ka) a k suchému destilačnému zvyšku sa přidá metanolický roztok metanolátu sodného (0,25 mlpřipravený rozpuštěním 0,3 g sodíka v 10 ml metanolu) a nitrometán (0,1 ml). Reakčná zmessa nechá stát pri teplote miestnosti 20 hodin a po přidaní 15 % vodného roztoku peroxiduvodika (1 ml) sa nechá stát 5alších 24 hodin. Roztok sá deionizuje na štipci (20 x 1 cm)zmesného ionomeniča "Bio-Deminrolit" (Permutit) a eluát (60 - 80 ml) sa-po zahuštění a porozpuštění destilačného zvyšku v zmesi metanol - voda chromatografuje na papieri Whatman i r v <x .mi ainMm xvstémom 1-butanol-etanol-voda (5 : 1 : 4, v/v) zo3tupnou chro-SUMMARY OF THE INVENTION The present invention provides that the D-xylose is epimerized in an aqueous solution in the presence of catalyzed amounts of molybdic acid at 80-100 ° C for 0.5-3 hours and the nitromethane son is converted without epithelial separation. to the corresponding 1-deoxy-1-nitrohexitols, which are converted to the corresponding aldose by oxidative decomposition. From the aldoz mixture, galactose is particularly easily isolated by paper chromatography. D- (U-4-Cgalactose, D-xylose, 14C-labeled D-xylose and nitromethane and nitromethane and nitromethane, respectively, respectively) are obtained by the above procedure from D - (C 1 -C 4) xylo and N-C-labeled nitromethane. C-labeled nitrate is given the opportunity to prepare a full range of specifically labeled D-galactose, and the advantage of the proposed method for the preparation of N-labeled D-galactose is that it utilizes a relatively more affordable aldopentose, a significant portion of aldopentoses (60). - 70%) sleep regenerates and can be used in the 3-cycle D-galactose preparation (xylo-derived nitrohexitols are converted to xylocase under the oxidative decomposition reaction by retrogressive reaction), - the whole process is very simple in the technical conversion, - all the required chemicals - removing 14 C-labeled D-xylose s1 commercially available Example of Example In a ground-glass flask and flare cooler, a mixture of D-xylose (25 mg), D- (U-14C) xylose (10 µCi of specific with an activity of 90 mCi / mmol), a 0.1% aqueous solution of molybdic acid is heated at 90 ° C for 2 hours. The solution was then concentrated (vacuum rotary evaporator) and methanolic sodium methanolate solution (0.25 ml prepared by dissolving 0.3 g of sodium in 10 ml of methanol) and nitromethane (0.1 ml) was added to the dry distillation residue. The reaction mixture was allowed to stand at room temperature for 20 hours and after addition of a 15% aqueous peroxide solution (1 ml) was allowed to stand for another 24 hours. The solution is deionized on a 20 x 1 cm blend of Bio-Deminrolite (Permutite) and the eluate (60-80 ml) is chromatographed on Whatman irv paper after concentration and dissolution of the distillation residue in methanol-water. me ainMm xvstém 1-butanol-ethanol-water (5: 1: 4, v / v)

Claims (1)

Spdsob přípravy ^^C-značkovanej D-galaktózy, vyznačujúci sa tým, že ^^C-značkovaná L-xylóza sa vo vodnom roztoku.za přítomnosti katalytických množstiev kyseliny molybdénovej při teplotě 80 až 100 °G po dobu 0,5 až 3 hodiny epimerizuje a epimérne aldopentózy sa bez osobitného delenia prevedú nitrometánovou syntézou na odpovedajúce nitrohexitoly, ktoré sa oxidačným rozkladem konvertujú na odpovedajúce aldozy.A process for the preparation of C-labeled D-galactose, characterized in that the C-labeled L-xylose is present in an aqueous solution in the presence of catalytic amounts of molybdic acid at a temperature of 80 to 100 ° C for 0.5 to 3 hours. epimerized, and epimeric aldopentoses are converted, without separate separation, by nitromethane synthesis to the corresponding nitrohexitols, which are converted to the corresponding aldoses by oxidative decomposition.
CS40080A 1980-01-21 1980-01-21 Method of preparation of the 14c-masked d-galactose CS209557B1 (en)

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