CS274022B1 - 0-acetyl-(4-0-methyl-alpha-d-glucorono)-beta-d-xylan - Google Patents

0-acetyl-(4-0-methyl-alpha-d-glucorono)-beta-d-xylan Download PDF

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CS274022B1
CS274022B1 CS760888A CS760888A CS274022B1 CS 274022 B1 CS274022 B1 CS 274022B1 CS 760888 A CS760888 A CS 760888A CS 760888 A CS760888 A CS 760888A CS 274022 B1 CS274022 B1 CS 274022B1
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xylan
methyl
acetyl
glucorono
minutes
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CS760888A
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CS760888A1 (en
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Ivan Ing Csc Simkovic
Anna Ing Csc Ebringerova
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Ivan Ing Csc Simkovic
Ebringerova Anna
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Abstract

The invention concerns the preparation of a new compound of 0-acetyl-(4-0-methyl-α-D-glucorono)-β-D-xylan with improved characteristics. The given aim is achieved with 0-acetyl-(4-0-methyl-α-D-glucorono)-β-D-xylan on a base of basic structural units of general formulae, where R represents hydrogen or the acetyl group with a degree of substitution of 0.1 to 1.5, which can be prepared by activating (4-0-methyl-α-D-glucurono)-β-D-xylan in a solvent of trifluoroacetic acid for at least 5 minutes at 10 to 30 degrees C and subsequently acetylating with an anhydride of acetic acid at 10 to 30 degrees C for 5 to 300 minutes, whereas the reciprocal mass ratio of (4-0-methyl-α-D-glucurono)-β-D-xylan, trifluoroacetic acid and anhydride of acetic acid is 1 : 0.8 to 25 : 0.7 to 25. 0-Acetyl-(4-0-methyl-α-D-glucorono)-β-D-xylan can be used in the chemical industry.<IMAGE>

Description

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Účelom riešenia je příprava novej zlúčeniny O-acetyl(4-0-metyl- -D-glukuróno) /3 -D-xylánu s lepšími vlastnosťami. Uvedený účel sa dosiahne O-acetyl-(4-0-metyl- ©4 -D-glukuróno)- /3 -D-xylánom na báze základných štrukturálnych jednotiek všeobecných vzorcov,kde R znamená vodík alebo acetylovú skupinu so stupňom substitúcie 0,1 až 1,5, pripravitel'ný tak, že (4-0-metyl- ob -D-glukuróno)- /5 -D-xylánu sa aktivuje v rozpúšťadle, kyselině trifluoroctovej po dobu alespoň 5 minút pri teplote 10 až 30 c a následné sa acetyluje anhydridom kyseliny octovej pri teplote 10 až 30 C po dobu 5 až 300 minút, pričom vzájomný hmotnostný poměr (4-0-metyl-ov -D-glukuróno)- /3 -D-xylánu, kyseliny trifluoroctovej a anhydridů kyseliny octovej je 1 : 0,8 až 25 ! 0,7 až 25. O-Acetyl-(4-0-metyl- oO -D-glukuróno)- /3 -D-xylán má použitie v chemickom priemysle.The purpose of the solution is to prepare a novel compound O-acetyl (4-O-methyl-D-glucuron) / 3-D-xylan with better properties. This is achieved by O-acetyl- (4-O-methyl-4-D-glucurono) - 3-D-xylan based on basic structural units of the general formulas wherein R is hydrogen or acetyl with a degree of substitution of 0.1 to 1.5, obtainable by (4-O-methyl-ob-D-glucurono) -? - D-xylan being activated in a solvent, trifluoroacetic acid for at least 5 minutes at a temperature of 10 to 30 c and subsequent is acetylated with acetic anhydride at 10 to 30 ° C for 5 to 300 minutes, the ratio by weight of (4-O-methyl-D-glucurono) -? -D-xylan, trifluoroacetic acid and acetic anhydride to each other being 1: 0.8 to 25! 0.7 to 25. O-Acetyl- (4-O-methyl-10-D-glucurono) - 3 -D-xylan has utility in the chemical industry.

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(11) (11) (13) (13) Bl bl (51) (51) Int. Cl.5 C 08 B 37/00Int. Cl. 5 C 08 B 37/00

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Vynález sa týká O-acetyl-(4-0-metyl- -D-glukuróno)- -D-xylánu.The present invention relates to O-acetyl- (4-O-methyl-D-glucurono) -D-xylan.

Polysacharidy nachádzajú čoraz vačšie uplatnenie v praxi (P. A. Stanford, J. Baird: The Polysaccharides, Academie Press, New York, 1983, vol. 2, str. 411). Okrem celulózy nachádzajú uplatnenie aj necelulózové polysacharidy. V mnohých prípadoch je nutné modifikovat' hydroxylové skupiny týchto zlúčenín, aby sa stali rozpustné vo vodě aj nevodných rozpúšťadlách. Toto umožní ich použitie ako přísady do farbív, lakov, filmotvorných zlúčenín, plniv, pomocných chemikálií a ako medziproduktov pre 9alŠie modifikácie a aplikácie. Doteráz známe postupy acylácie hemicelulóz modifikujú substrát v heterogénnej fáze alebo používajú rozpúštadlá degradujúce substrát /CS AO 210 220; N. I. Nikitin: Chimija dřeva, SNTL, Praha, 1956, str. 195; P. E. Gardner, Μ. Y. Chány: Tappi 57 (8), 71 (1974); J. Kocourek, C. E. Ballou: J. Bacteriol. 100, 1175 (1989)/. Nevýhodou týchto postupov je vysoký stupeň substitúcie a nízké výťažky produktu. Starým postupom acetylácie hemicelulóz sa získal produkt s vysokým stupňom substitúcie (DS^2). Doteráz sa nepřipravil O-acetyl-(4-O-acetyl- oo -D-glukuróno)- /3 -D-xylán so stupňom substitúcie nižším ako 1-5.Polysaccharides find increasing use in practice (P.A. Stanford, J. Baird: The Polysaccharides, Academic Press, New York, 1983, vol. 2, p. 411). In addition to cellulose, non-cellulosic polysaccharides also find application. In many cases, it is necessary to modify the hydroxyl groups of these compounds to become soluble in both water and non-aqueous solvents. This will allow them to be used as additives to dyes, lacquers, film-forming compounds, fillers, auxiliary chemicals and as intermediates for further modifications and applications. The hitherto known acylation procedures of hemicelluloses modify the substrate in a heterogeneous phase or use substrate degrading solvents / CS AO 210 220; NI Nikitin: Chimija dreva, SNTL, Prague, 1956, p. 195; P. E. Gardner, Μ. Y. Khan: Tappi 57 (8), 71 (1974); J. Kocourek, C.E. Ballou: J. Bacteriol. 100, 1175 (1989)]. A disadvantage of these processes is the high degree of substitution and low product yields. The old hemicellulose acetylation procedure yielded a product with a high degree of substitution (DS ^ 2). To date, O-acetyl- (4-O-acetyl-β-D-glucurono) - β-D-xylan with a degree of substitution of less than 1-5 has not been prepared.

Tieto nevýhody odstraňuje tento vynález. Podstatou vynálezu je O-acetyl-(4-O-metyl- íX/ -D-glukuróno)-./3 -D-xylán na báze základných štrukturálnych jednotiek všeobecných vzorcovThese disadvantages are overcome by the present invention. The present invention provides O-acetyl- (4-O-methyl-1 H -D-glucurono) -. Beta.-D-xylan based on the basic structural units of the general formulas

kde R znamená sodík alebo acetylovú skupinu so stupňom substitúcie 0,1 až 1,5, pripravitel'ný tak, že (4-O-metyl- ob -D-glukuróno)- /3 -D-xylán sa aktivuje v rozpúšťadle, kyselině trifluoroctovej po dobu aspoň 5 minút pri teplote 10 až 30 c a následné acetyluje anhydridom kyseliny octovej pri teplote 10 až 30 ’c po dobu 5 až 300 minút, pričom vzájomný hmotnostný poměr (4-O-metyl- e</ -D-glukuróno,-.£> -D-xylánu, kyseliny trifluoroctovej a anhydridů kyseliny octovej je 1 : 0,8 až 25 : 0,7 až 25.wherein R is sodium or acetyl having a degree of substitution of 0.1 to 1.5, obtainable by (4-O-methyl-ob-D-glucuronium) -? - D-xylan being activated in a solvent, acid trifluoroacetic acid for at least 5 minutes at a temperature of 10 to 30 c and subsequently acetylated with acetic anhydride at a temperature of 10 to 30 ° C for a period of 5 to 300 minutes, the relative weight ratio of (4-O-methyl-ε-D-glucuron, The? -D-xylan, trifluoroacetic acid and acetic anhydrides are 1: 0.8 to 25: 0.7 to 25.

Výhodou O-acetyl-(4-O-metyl- οϋ -D-glukuróno,- -D-xylánu so stupňom substitúcie 0,1 až 1,5 acetylových skupin oproti doteráz známým O-acetyl derivátom hemicelulóz je, že sa dajú použiť ako substráty pre dalšiu modifikáciu, ako aj rozpustností vo vodě a vačšom množstve rozpúštíadiel a ich zmesi.An advantage of O-acetyl- (4-O-methyl- οϋ -D-glucuronium, -D-xylan with a degree of substitution of 0.1 to 1.5 acetyl groups over the prior art O-acetyl derivatives of hemicelluloses is that they can be used as substrates for further modification, as well as water solubility and more solvents and mixtures thereof.

Uvedené příklady demonstrujú, ale neobmedzujú predmet vynálezu.The examples given illustrate, but do not limit the scope of the invention.

Příklad 1 g (4-O-Metyl- -D-glukuróno)- /3 -D-xylánu z bukového dřeva sa rozpúšťa 2 hodiny pri teplote 20 *C v 27 g kyseliny trifluoroctovej za intenzívneho miešania. Potom sa přidá 7,7 g anhydridů kyseliny octovej a mieša sa počas 2 hodin. Reakcia sa zastaví přenesením reakčnej zmesi do dialyzačného čreva za súčasného zriedenia s vodou. Po oddialyCS 274022 Bl zování nízkomolekulárnych reakčných zložiek sa lyofilizáoiou získá 2,6 g vzduchosuchého produktu so stupňom substitúcie 1,3.EXAMPLE 1 1 g of (4-O-Methyl-D-glucurono) - [beta] -D-xylan from beechwood were dissolved in 27 g of trifluoroacetic acid under vigorous stirring at 20 DEG C. for 2 hours. Then 7.7 g of acetic anhydride are added and stirred for 2 hours. The reaction is stopped by transferring the reaction mixture to the dialysis gut while diluting with water. After separating the low molecular weight reactants, 2.6 g of an air-dry product with a degree of substitution of 1.3 are obtained by lyophilization.

Příklad 2Example 2

Postupuje sa ako v příklade 1 s tým rozdielom, že sa použije 0,7 g (4-O-metyl- oO. -D-glukuróno)- fa -D-xylánu z brezy a aktivuje sa s 17 g kyseliny trifluoroctovej po dobu 5 minút pri teplote 20 ‘c. Potom sa přidá 2,6 g anhydridu kyseliny octovej a acetyluje sa 15 minút pri teplote 20 *C. Získá sa 1,2 g O-acetyl-(4-O-metyl- cKz-D-glukuróno) - /3 -D-xylánu so stupňom substitúcie 0,5.The procedure is as in Example 1 except that 0.7 g of (4-O-methyl-o, -D-glucuron) -f-D-xylan from birch is used and activated with 17 g of trifluoroacetic acid for 5 hours. minutes at 20 ° C. 2.6 g of acetic anhydride are then added and acetylated for 15 minutes at 20 ° C. 1.2 g of O-acetyl- (4-O-methyl-cis-D-glucuron) -? - D-xylan with a degree of substitution of 0.5 are obtained.

Příklad 3Example 3

Postupuje sa ako v příklade 1 s tým rozdielom, že sa 1,4 g (4-O-metyl- «O-D-glukuróno)-/3 -D-xylánu z habru aktivuje v 28 g kyseliny trifluoroctovej pri teplote 10 *C, acetyluje 1,6 g anhydridu kyseliny octovej pri teplote 10 ’c počas 4 hodin. Získá sa 1,1 g O-acetyl- (4-O-metyl- -D-glukoróno) - /3 -D-xylánu so stupňom substitúcie 0,9.The procedure is as in Example 1 except that 1.4 g of (4-O-methyl-4-O-glucurono) - 3-D-xylan from hornbeam is activated in 28 g of trifluoroacetic acid at 10 ° C, acetylated 1.6 g of acetic anhydride at 10 DEG C. for 4 hours. 1.1 g of O-acetyl- (4-O-methyl-D-glucorono) -? - D-xylan with a degree of substitution of 0.9 are obtained.

Příklad 4Example 4

Postupuje sa ako v příklade 1 s tým rozdielom, že sa 1,1 g (4-O-metyl-<x> -D-glukuróno)- fa) -D-xylánu z topol'a, aktivuje 14,3 g kyseliny trifluoroctovej pri teplote 30 c po dobu 5 minút a acetyluje s 4,6 g anhydridu kyseliny octovej po dobu 15 minút pri teplo te 30 ’c. Po izolácii sa získá 1,5 g O-acetyl-(4-O-metyl-cK/ -D-glukuróno)- /3 -D-xylánu so stupňom substitúcie 1,4.The procedure is as in Example 1 except that 1.1 g of (4-O-methyl- [x] -D-glucuronol) -α-D-xylan from poplar is activated with 14.3 g of trifluoroacetic acid. at 30 ° C for 5 minutes and acetylated with 4.6 g acetic anhydride for 15 minutes at 30 ° C. After isolation, 1.5 g of O-acetyl- (4-O-methyl-cis-D-glucurono) - 3-D-xylan with a degree of substitution of 1.4 are obtained.

Přiklad 5Example 5

Postupuje sa ako v příklade 1 s tým rozdielom, že sa použije 1 g (4-0-metyl-oCz -D-glukuróno)- fa) -D-xylánu z dubu a aktivuje sa s 18 g kyseliny trifluoroctovej v priebehu 5 minút za miešania. K vzorke sa přidá 0,2 g anhydridu kyseliny octovej a acetyluje sa po dobu 15 minút. Po izolácii produktu ako v příklade 1 sa získá 0,9 g O-acetyl-(4-0-metyl- oR, -D-glukuróno)- -D-xylánu so stupňom substitúcie 0,5.The procedure is as in Example 1 except that 1 g (4-O-methyl-oC of -D-glucuron) -α) -D-xylan from oak is used and activated with 18 g of trifluoroacetic acid over 5 minutes with stirring. 0.2 g of acetic anhydride is added to the sample and acetylated for 15 minutes. After isolation of the product as in Example 1, 0.9 g of O-acetyl- (4-O-methyl-oR, -D-glucurono) -D-xylan with a degree of substitution of 0.5 is obtained.

O-Acetyl-(4-O-metyl- ofJ -D-glukuróno)- /3 ”D~xylán m3že nájsť široké použitie v chemickom priemysle ako filmotvorný materiál, medziprodukt v organickéj chémii, přísada do lakov, pomocných prostriedkov v textilnom priemysle a pracích prostriedkoch.O-Acetyl- (4-O-methyl-η-D-glucuron) - / 3'D-xylan can be used widely in the chemical industry as a film-forming material, an intermediate in organic chemistry, lacquer additive, textile aids and detergents.

PREDMET VYNÁLEZUOBJECT OF THE INVENTION

O-Acetyl-(4-O-metyl- 00 -D-glukuróno,- /3 -D-xylán na báze štrukturálnych jednotiek všeobecných vzorcov ^0O-Acetyl- (4-O-methyl- 00- D-glucuronium) - β-D-xylan based on structural units of formulas

Claims (5)

0*10 * 1 CS 274022 Bl kde R znamená vodík alebo acetylovú skupinu so stupňom substitúcie 0,1 až 1,5, pripravitel'ný tak, že (4-O-metyl- e>c/ -D-glukuróno)-./3 ,-D-xylán sa aktivuje v rozpúšťadle, kyselině trifluoroctovej po dobu aspoň 5 minút pri teplote 10 až 30 ‘c a následovně sa acetyluje anhydridom kyseliny octovej pri teplote 10 až 30 *C po dobu 15 až 300 minút, pričom vzájomný hmotnostný poměr (4-0-metyl- dO -D-glukuróno)^-D-xylánu, kyseliny trifluoroctovej a anhydridu kyseliny octovej je 1 : 0,8 až 25 : 0,7 až 25.CS 274022 B1 wherein R represents hydrogen or an acetyl group with a degree of substitution of 0.1 to 1.5, obtainable by (4-O-methyl-cis-D-glucuron) - (3, -D). -xylan is activated in solvent, trifluoroacetic acid for at least 5 minutes at 10 to 30 ° C and subsequently acetylated with acetic anhydride at 10 to 30 ° C for 15 to 300 minutes, whereby the weight ratio (4-0- methyl-D-D-glucuron-4-D-xylan, trifluoroacetic acid and acetic anhydride is 1: 0.8 to 25: 0.7 to 25.
CS760888A 1988-11-21 1988-11-21 0-acetyl-(4-0-methyl-alpha-d-glucorono)-beta-d-xylan CS274022B1 (en)

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