CS196996B1 - Method for the release of aldoses from n-phenyl-glycosilamines - Google Patents

Method for the release of aldoses from n-phenyl-glycosilamines Download PDF

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CS196996B1
CS196996B1 CS135778A CS135778A CS196996B1 CS 196996 B1 CS196996 B1 CS 196996B1 CS 135778 A CS135778 A CS 135778A CS 135778 A CS135778 A CS 135778A CS 196996 B1 CS196996 B1 CS 196996B1
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aldoses
chem
release
ion exchanger
phenyl
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CS135778A
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Vojtech Bilik
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Vojtech Bilik
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(54) Spdsob uvďnenia aldóz z N-fenylglykozylamínov(54) Method of listing aldoses from N-phenylglycosylamines

Predmetom vynálezu je nový spdsob uvolněnia aldóz z vodných roztokov N-fenylglykozylamínov silné kyslým ionomeničom - katexom v H+-cy|čle.SUMMARY OF THE INVENTION The present invention provides a novel method for the release of aldoses from aqueous solutions of N-phenylglycosylamines with a strong ion exchange cation-exchange resin in the H + -cyl group.

Všeobecne sú N-arylglykozylamíny dobré kryštalizujúce zlúčeniny (G. P. Ellis, J. Honeyman; Advan. Carbohyd. Chem., 10, 95 (1955)). V niektorých prípadoch sa ich rdzna kryštalizačná schopnost využívá na vzájomné rozdeTovanie aldoz, resp. aldoz od ketoz. Zo všetkých aldopentoz, aldohexoz a aldohepto^ osobitne dobrú kryštalizačnú schopnost vykazujú N-fenylglykozylemíny ribozy, lyxozy, menózy a manoheptózy. Ak sa tieto aldózy nachádzajú v zmesiach aldóz, resp. ketoz v dostatočnej koncentrácii, potom je možné ich izolovat vo forma krystalických N-fenylglykozylamínov (ribózy (R. L. Whistler, J. N. BeMiller; Methods Carbohyd. Chem., Vol. I, p. 79, Academie Press, New York - London 1962, V. Bílik, J. čaplovič; Chem. zvěsti 2J, 547 (1973)), lyxózy (V. Bílik, J. Caplovič; Chem. zvěsti 2J, 547 (1973)), manózy (T. Fujita, T. Sáto; Bull. Chem. Soc. Japan JJ, 353 (1960), V. Bílik,In general, N-arylglycosylamines are good crystallizing compounds (G. P. Ellis, J. Honeyman; Advan. Carbohyd. Chem., 10, 95 (1955)). In some cases, their different crystallization ability is used to distribute aldoses and / or aldoses to each other. aldoz by ketoz. Of all the aldopentoses, aldohexoses and aldohepto, the ribose, lyxose, mennose and manoheptose N-phenylglycosylemines exhibit particularly good crystallinity. If these aldoses are present in mixtures of aldoses, resp. ketos in sufficient concentration, then they can be isolated in the form of crystalline N-phenylglycosylamines (riboses (RL Whistler, JN BeMiller; Methods Carbohyd. Chem., Vol. I, p. 79, Academic Press, New York - London 1962, V.). Bilik, J. Caplovic; Chem. Rumors 2J, 547 (1973)), Lyxoses (V. Bilik, J. Caplovich; Chem. Rumors 2J, 547 (1973)), Mannose (T. Fujita, T. Sato; Bull. Soc. Japan JJ, 353 (1960), V. Bilik,

K. Tihlárik; Chem. zvěsti 2S, 106 (1974)), manoheptózy (V. Bílik, L. Petruš; Chem. zvěsti JO, 359 (1976)). Z hydrolyzátu sacharózy bola D-glukóza izolovaná vo formě N-p-nitrofenylglykozylamínu a podobné z hydrolyzátov mananov D-manóza (F. Weygand, W. Perkow, P. Kuhner; Chem. Ber., 84, 594 (195D).K. Tihlárik; Chem. rumors 2S, 106 (1974)), manoheptosis (V. Bilik, L. Petrus; Chem. rum. JO, 359 (1976)). From sucrose hydrolyzate, D-glucose was isolated as N-p-nitrophenylglycosylamine and the like from mannan hydrolyzates D-mannose (F. Weygand, W. Perkow, P. Kuhner; Chem. Ber., 84, 594 (195D)).

Z N-fenylglykozylamínov sa aldózy uvolňujú kyslou hydrolýzou kyselinou mravčou, resp.The aldoses are released from N-phenylglycosylamines by acid hydrolysis with formic acid, respectively.

kyselinou sírovou (K. Butler, S. Laland, W. G. Overend, M. Stacy; J. Chem. Soc., 1250«Sulfuric acid (K. Butler, S. Laland, W.G. Overend, M. Stacy; J. Chem. Soc., 1250).

196 996196 996

198 999198 999

1433), alebo kyselinou octovou (F, Weygand et al.; Chem. Ber., 8£, 594 (1951)), připadne vytěsňováním anilínu formaldehydem (T. Fujita, T. Sáto; Bull, Chem. Soc. Japan 22» 353 (1960)), ale najčaetejšie benzaldehydom (R. L. Whistler, J. N. BeMiller; Methods Carbohyd. Chem, Vol. I, p. 79, 1962). V případe N-fenylglykozylamínov je vhodná autokatalyzovaná hydrolýza - technikou preháňania vodnou parou (V. Bílik et al.; Chem. zvěsti 27. 547 (1973), ibid. 28. 106 (1974), ibid. JO, 359 (1976)). Oproti doteraz používaným spósobom má navrhovaný spósob uvolňovánia aldóz predovšetkým tú výhodu, Sa roztok po hydrolýze N-fenylglykozylaminu neobsahuje žiadne ňalšie zlúčeniny, len žiadanú aldózu.1433), or acetic acid (F, Weygand et al .; Chem. Ber., 8, 594 (1951)), respectively, by displacement of aniline with formaldehyde (T. Fujita, T. Sato; Bull, Chem. Soc. Japan 22 » 353 (1960)), but most commonly benzaldehyde (RL Whistler, JN BeMiller; Methods Carbohyd. Chem. Vol. I, p. 79, 1962). In the case of N-phenylglycosylamines, autocatalyst hydrolysis by steam-jetting technique is suitable (V. Bilik et al .; Chem. Rum. 27, 547 (1973), ibid. 28, 106 (1974), ibid. JO, 359 (1976)). . In contrast to the methods used hitherto, the proposed method of releasing aldoses has the particular advantage that the solution after hydrolysis of N-phenylglycosylamine contains no other compounds, only the desired aldose.

Predmet vynálezu spočívá v tom, že N-fenylglykozylamíny sa vo vodnom roztoku za teploty miestnosti v přítomnosti silné kysláho ionomeniča - katexu v H+-cykle hydrolyzujú a súčasne uvolněné arylamíny sa na iónomenič viažu. Zahuštěním vodného roztoku sa získajú aldožy vyeokej čistoty.It is an object of the present invention that N-phenylglycosylamines hydrolyze in an aqueous solution at room temperature in the presence of a strong acidic ion exchanger-cation exchanger in an H + -cycle and simultaneously released arylamines bind to the ion exchanger. Concentration of the aqueous solution gives aldozes of high purity.

Výhodou navrhovaného spósobu uvolňovania aldóz z N-fenylglykozylamínov je, žeAn advantage of the proposed method of releasing aldoses from N-phenylglycosylamines is that

- hydrolyzačný roztok obsahuje len žiadanú aldózu,- the hydrolysis solution contains only the desired aldose,

- zahuštěním hydrolyzačného roztoku ea získajú aldózy vysokej čistoty,- by concentrating the hydrolysis solution ea to obtain aldoses of high purity,

- umožňuje čietenie roztokov od zvyškov N-fenylglykozylamínov, resp. bázických zložiek vznikajúcich pri hydrolýze technikou preháňania vodnou parou,- allows solutions to be read from N-phenylglycosylamine residues, resp. the basic constituents formed by hydrolysis by the water vapor bleeding technique,

- použitý iónomenič je po recyklizácii vhodný na Salšie uvolňovanie aldóz z N-fenylglykozylamínov,- the ion exchanger used, after recycling, is suitable for the saler release of aldoses from N-phenylglycosylamines,

- je nenáročný na technologické zariadenie.- it is undemanding for technological equipment.

Příklady prevedeniaExamples of design

Příklad 1Example 1

L-ribóza. Zmes 100 g N-fenyl-L-ribozylamínu, 500 ml ionomeniča Wofatit KPS v H+-cykle (50/100 mesh) a 300 ml vody ea mieša 3 h. pri teplote miestnosti. iónomenič sa odfiltruje, premyje aa 3 x 200 ml vody a filtrát aa zahustí za zníženého tlaku (teplota do 60 °C) na sirup, ktorý představuje 63 až 65 g tj. 92 až 97 % čiatej L-ribózy. Kryštalizáciou sirupu (A g) v 99 % etanole (3 A ml) Ba získá krystalická L-ribóza.L-ribose. A mixture of 100 g of N-phenyl-L-ribozylamine, 500 ml of Wofatit KPS ion exchanger in H + -cycle (50/100 mesh) and 300 ml of water and stirred for 3 h. at room temperature. the ion exchanger is filtered off, washed with aa 3 x 200 ml of water and the filtrate aa is concentrated under reduced pressure (temperature up to 60 ° C) to a syrup of 63 to 65 g, i. 92-97% of pure L-ribose. Crystallization of the syrup (A g) in 99% ethanol (3 A mL) of Ba yields crystalline L-ribose.

Příklad 2Example 2

L-lyxóza. Zmes 100 g N-fenyl-L-lyxozylamínu, 500 ml ionomeniča Amberlit IRA 120 v H+-cykle (50/100 meah) a 300 ml vody sa mieša 3 h. pri teplote miestnosti. Po Salšom spracování (ako je uvedená v příklade 1) aa získá sirupovitá, ako aj krystalická L-lyxóza vysokej čistoty (ca 95 % výťažok).L-lyxose. A mixture of 100 g of N-phenyl-L-lyxozylamine, 500 ml of Amberlit IRA 120 ion exchanger in H + -cycle (50/100 meah) and 300 ml of water is stirred for 3 h. at room temperature. After the salting-up treatment (as in Example 1) aa, the syrupy as well as the crystalline L-lyxose are obtained in high purity (ca 95% yield).

Příklad 3Example 3

L-arabinóza. Zmes 50 g N-p-nitrofenyl-L-arabinozylamínu, 200 ml ionomeniča Dowex 50 W v H+-cykle (100/200! meah) a 300 ml vody sa mieša 4 h. Po odatránení ionomeniča sa roztok zahustí a destilačný zvyšok ea prekryštalizuje zametanolu, čím ea získá 24,5 až 25,5 g tj. 90 až 94 % kryštalickej L-arabinózy.L-arabinose. A mixture of 50 g of Np-nitrophenyl-L-arabinozylamine, 200 ml of Dowex 50 W ion exchanger in H + -cycle (100/200 µmeah) and 300 ml of water is stirred for 4 h. After removal of the ion exchanger, the solution is concentrated and the distillation residue ea is recrystallized from methanol to obtain 24.5 to 25.5 g. 90 to 94% of crystalline L-arabinose.

19β 99819β 998

Příklad 4Example 4

Cistenie D-manózy z hydrolyzátov N-fenyl-D-manozylamínu.Purification of D-mannose from N-phenyl-D-manozylamine hydrolyzates.

Hydrolýzou 300 g N-fenyl-D-manozylamínu - technikou preháňaním vodnou (Jarou (ukončené po získaní 3 1 distilátu) sa hydrolyzát přefiltruje, přidá 50 ml iónomeniča Wofatit KPS v H+-cykle a mieša sa 4 h. při teplote miestnosti. iónomenič sa odfiltruje, premyje sa vodou a filtrát zahustí za zníženého tlaku. Destičlaný zvyšok sa prekryštalizuje z metanolu, čím sa získá 134 až 146 g t.j 68 až 74 % kryštalickej D-manózy vysokej čistoty.Hydrolysis of 300 g of N-phenyl-D-mannoslamine - by aqueous sweeping technique (Spring (terminated after obtaining 3 L of distillate)) was filtered, 50 ml of Wofatit KPS ion exchanger in H + -cycle were added and stirred for 4 h at room temperature. The filtrate is concentrated under reduced pressure, and the residue is recrystallized from methanol to give 134-146 g (68-74%) of high purity crystalline D-mannose.

Regenerácia iónomeničov.Regeneration of ion exchangers.

Použitý katex (Wofatit KPS, Amberlit IRA 120, Dowex 50 W) 500 ml sa maceruje v 500 ml zmesi kyseliny octovej a 37 % kyseliny chlorovodíkovej (9 : 1) a za občasného premiešania sa nechá stáť 2 h. pri teplote miestnosti. iónomenič sa odfiltruje, opSť maceruje v 500 ml zmesi kysělín, po odfiltrovaní sa premyje 3 x 300 ml kyseliny octovej a nakoniec vodou do neutrálnej reakcie. Regenerovaný katex sa použije pre Salšie cykly uvoTnovania aldóz z ich N-fenylglykozylamínov.The used cation exchanger (Wofatit KPS, Amberlite IRA 120, Dowex 50 W) 500 ml is macerated in 500 ml of a 9: 1 mixture of acetic acid and 37% hydrochloric acid and allowed to stand for 2 hours with occasional stirring. at room temperature. The ion exchanger is filtered off, macerated in 500 ml of acidic mixture, after filtration it is washed with 3 x 300 ml of acetic acid and finally with water until neutral. The regenerated cation exchanger is used for saler release cycles of aldoses from their N-phenylglycosylamines.

Vynález má praktické uplatnenie pri výrobě L-ribózy, L-lyxózy, D-manózy, resp. ich antipódov a pri príprave Salších aldoz.The invention has practical application in the production of L-ribose, L-lyxose, D-mannose, resp. their antipodes and in the preparation of Other aldoses.

Claims (1)

PREDMET VYNÁLEZUOBJECT OF THE INVENTION Spfisob uvoTnenia aldóz z N-fenylglykozylamínov, vyznačujúci aa tým, že N-fenylglykozyl aminy sa vo vodnom roztoku v přítomnosti silné kyslého iónomeniča - katexu v H+ - cykle pri teplote miestnosti hydrolyzujú a súčasne uvolněné arylamíny sa na iónomenič viažu ja zahuštěním vodného roztoku sa získajú aldózy vysokej čistoty.A method for the release of aldoses from N-phenylglycosyl amines, characterized in that the N-phenylglycosyl amines are hydrolyzed at room temperature in the presence of a strong acidic ion exchanger-cation exchanger in the H + cycle and the liberated arylamines bind to the ion exchanger by concentration of the aqueous solution. they obtain aldoses of high purity.
CS135778A 1978-03-03 1978-03-03 Method for the release of aldoses from n-phenyl-glycosilamines CS196996B1 (en)

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