CS260394B1 - Method of aldoses preparation - Google Patents
Method of aldoses preparation Download PDFInfo
- Publication number
- CS260394B1 CS260394B1 CS874637A CS463787A CS260394B1 CS 260394 B1 CS260394 B1 CS 260394B1 CS 874637 A CS874637 A CS 874637A CS 463787 A CS463787 A CS 463787A CS 260394 B1 CS260394 B1 CS 260394B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- aldoses
- preparation
- molybdenum
- citric acid
- elution system
- Prior art date
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Saccharide Compounds (AREA)
Abstract
Účelom spósobu přípravy aldóz je zlepšeme spůsobov přípravy aldóz, t. j. zjednodu- šenie a zhospodárnenie týchto spósobov pří pravy. Uvedený účel sa dosiahne tak, že k N-fenylglykozylamínu, formaldehydu, etanolu, vodě a molybdénanovej zlúčenine sa přidá kyselina citrónová v mólovom pomere molybdénu v oxidačnom stupni VI ku kyselině citrónovej 1 : aspoň 2 a nechá reagovat pri teplote do 100 °C. Spósob přípravy aldóz má použitie v organlckej chémii.The purpose of aldose preparation is to improve them methods for preparing aldoses, i.e., enhancing and rationalizing these modalities right. This purpose is achieved by k N-phenylglycosylamine, formaldehyde, ethanol, water and molybdenum compound are added citric acid in molar ratio of molybdenum in the oxidation step VI to the acid lemon 1: at least 2 and react at temperatures up to 100 ° C. A method of preparing aldoses has use in organic chemistry.
Description
Vynález sa týká sposobu přípravy aldóz.The invention relates to a process for the preparation of aldoses.
V niektorých sposoboch izolácií jednej aldózy zo zmesi aldóz sa použila reakcia aldóz s anilínmi, ktorá využívá rozdielnu kryštalizačnú schopnost vzniknutých N-fenylglykozylamínov. Zo zmesi arabinózy a ribózy sa izoluje N-fenylribozylamín, zo zmesi xylózy a lyxózy N-fenyllyxozylamín [V. Bílik, J. Caplovič: Chem. Zvěsti 27, 547 (1973)], zo zmesi fruktózy, glukózy a manózy N-fenylmanozylamín [V. Bílik, K. Tihlárik: Chem. Zvěsti 28, 206 (1984)], zo zmesi D-glycero-L-glukoheptózy a D-glycero-L-manoheptózy N-fenyl-D-glycero-L-manoheptozylamín [ V. Bílik, L. Petruš: Chem. Zvěsti 30, 359 (1976)] a zo zmesi Larabinózy a D-xylózy N-(4-nitrofenyl)-L-arbinozylamín [V. Bílik, A. Kramář: Chem. Zvěsti 33, 641 (1979)]. Z N-fenylglykozylamínov sa můžu aldózy uvolňovat formaldehydom [T. Fujita, T. Sáto: Bull. Chem. Soc. Japn 33, 353 (1960)], benzaldehydom [R. L. Whistler, J. N. BeMiller: Methods Carbohydr. Chem. 1, 81 (1962)], hydrolýzou technikou preháňania vodnou parou [V. Bílik, J. Caplovič: Chem. Zvěsti 27, 547 (1973); V. Bílik, L. Petruš: Chem. Zvěsti 30, 359 (1976)], hydrolýzou silné kyslým iónomeničom (CS AO č. 196 996).In some ways of isolating one aldose from the aldose mixture, the reaction of aldoses with anilines has been utilized, utilizing the different crystallization capacity of the resulting N-phenylglycosylamines. N-phenylribozylamine is isolated from arabinose-ribose mixture, and N-phenyllyxozylamine from V. a mixture of xylose and lyxose [V. Bilik, J. Caplovic: Chem. Rumors 27, 547 (1973)], from a mixture of fructose, glucose and mannose, N-phenylmanozylamine [V. Bílik, K. Tihlárik: Chem. Rumors 28, 206 (1984)], from a mixture of D-glycero-L-glucoheptose and D-glycero-L-manoheptose N-phenyl-D-glycero-L-manoheptozylamine [V. Bilik, L. Petrus: Chem. Rumors 30, 359 (1976)] and from a mixture of Larabinose and D-xylose N- (4-nitrophenyl) -L-arbinozylamine [V. Bilik, A. Kramar: Chem. Rumors 33, 641 (1979)]. Aldoses can be released from formaldehyde from N-phenylglycosylamines [T. Fujita, T. Sato: Bull. Chem. Soc. Japn 33, 353 (1960)], benzaldehyde [R. L. Whistler, J. N. BeMiller: Methods Carbohydr. Chem. 1, 81 (1962)], by hydrolysis by the water vapor bleeding technique [V. Bilik, J. Caplovic: Chem. Rumors 27, 547 (1973); V. Bílek, L. Petruš: Chem. Rumors 30, 359 (1976)], by strong acid ion exchange hydrolysis (CS AO No. 196 996).
Pri všetkých týchto reakciáeh třeba, aby inolybdénanové ióny v postupoch uvotňovania neboli přítomné. Preto sa museli roztoky aldóz před příslušnou derivatizáciou na odpovedajúce N-fenylglykozylamíny deionizovať, čo zvyšuje pracnost a zdražuje připravené aldózy. Aldózy sa v slabo kyslých vodných roztokoch za přítomnosti molybdénanových iónov epimerizujú a vytvárajú rovnovážnu zmes C—2-epimérnych aldóz [V. Bílik: Chem. listy 77, 496 (1983)].In all of these reactions, the inolybdenate ions need not be present in the release procedures. Therefore, aldose solutions had to be deionized prior to appropriate derivatization to the corresponding N-phenylglycosylamines, which increases laboriousness and makes the prepared aldoses more expensive. The aldoses are epimerized in weakly acidic aqueous solutions in the presence of molybdenum ions to form an equilibrium mixture of C-2-epimeric aldoses [V. Bilik: Chem. 77, 496 (1983)].
Uvedené nevýhody v podstatnej miere odstraňuje spósob přípravy aldóz podlá vynáleze, ktorého podstata spočívá v tom, že k N-fenylglykozylamínu, formaldehydu, etanolu, vodě a molybdénanovej zlúčenine sa přidá kyselina citrónová v mólovom pomere molybdénu v oxidačnom stupni VI ku kyselině citrónovej 1 : aspoň 2 a nechá reagovat pri teplote do· 100 °C.The above-mentioned disadvantages are substantially eliminated by the process for the preparation of the aldoses according to the invention, which comprises adding to the N-phenylglycosylamine, formaldehyde, ethanol, water and molybdenum compound citric acid in a molar ratio of molybdenum in oxidation stage VI to citric acid 1: 2 and allowed to react at a temperature of up to · 100 ° C.
Výhodou navrhovaného sposobu přípravy aldóz je, že netřeba molybdénanové ióny odstraňovat, najčastejšie anexami, s následným zahušťováním roztokov, čím sa ušetří na mzdách, materiáloch, energii a v podstatnej miere ušetří použitie niektorých zariadení (odpariek, kolon).The advantage of the proposed process for the preparation of aldoses is that there is no need to remove molybdenum ions, most often with anion exchangers, followed by concentration of the solutions, thus saving on wages, materials, energy and substantially saving the use of some devices (evaporators, columns).
Příklad 1Example 1
Zmes 25,5 g (0,1 mólu) N-fenyl-D-manozylamínu, 0,25 g (2.10-4 mólov) tetrahydrátu heptamolybdénanu hexaamonného, 0,59 gramu (2,8 . 10~3 mólov) monohydrátu kyseliny citrónovej (mólový poměr kyseliny citrónovej k molybdénu v oxidačnom stupni VI je 2 : 1), 15,8 ml (0,2 mólu) 35 % hmot. vodného roztoku formaldehydu, 35 ml 96 % hmot. etanolu a 190 ml vody sa zahrieva počas 3 h pri teplote 90 °C. Inhibícia epimerizácie D-manózy sa zisťuje papierovou chromatografiou (Whatman No 1) s použitím elučného systému A: acetonu, 1-butanolu a vody v objemovom pomere 5 : 1 : 4, s dobou prietoku elučných systémov 18 až 20 h a následuj úcou detekciou s anilíniumhydrogénftalátom. Chromatograficky záznam dokazuje přítomnost D-manózy a v stopovém množstve přítomnost D-glukózy. Pohyblivost vzťahujúca sa na glukózu 1,00 je pre manózu v elučnom systéme A: 1,31 a v elučnom systéme B: 1,30.A mixture of 25.5 g (0.1 mole) of N-phenyl-D-mannoslamine, 0.25 g (2.10 -4 mole) of hexaammonium heptamolybdate tetrahydrate, 0.59 g (2.8, 10 -3 mole) of citric acid monohydrate (mole ratio of citric acid to molybdenum in oxidation stage VI is 2: 1), 15.8 ml (0.2 mol) 35 wt. % aqueous formaldehyde solution, 35 ml 96 wt. of ethanol and 190 ml of water are heated at 90 ° C for 3 h. Inhibition of D-mannose epimerization was determined by paper chromatography (Whatman No 1) using an A: acetone, 1-butanol and water elution system in a 5: 1: 4 by volume ratio, elution system flow time 18-20 h followed by detection with aniline hydrogen phthalate . Chromatography shows the presence of D-mannose and trace amounts of D-glucose. Glucose-related mobility of 1.00 is for mannose in the elution system A: 1.31 and in the elution system B: 1.30.
Příklad 2Example 2
Postupuje sa ako v příklade 1 s tým rozdielom, že sa zmes zahrieva počas 2 h pri teplote 100 °C. Chromatograficky záznam dokazuje přítomnost D-manózy a v stopovom množstve přítomnost D-glukózy.The procedure is as in Example 1 except that the mixture is heated at 100 ° C for 2 h. Chromatography shows the presence of D-mannose and traces of D-glucose.
Příklad 3Example 3
Postupuje sa ako v příklade 1 s tým rozdielom, že sa použije zmes 22,5 g (0,1 mólu) N-fenyl-D-ribozylamínu, 25 mg (2.10-5 mólov) tetrahydrátu heptamolybdénanu hexaamonného, 59 mg (2,8.10-4 mólov) monohydrátu kyseliny citrónovej (mólový poměr kyseliny citrónovej k molybdénu v oxidačnom stupni VI je 2 : 1), 15,8 ml (0,2 mólu) 35 .% hmot. vodného roztoku formaldehydu, 35 ml 96 % hmot. etanolu a 190 ml vody. Chromatograficky záznam dokazuje přítomnost D-ribózy a v stopovom množstve přítomnost D-arabinózy. Pohyblivost vzťahujúca sa na D-glukózu 1,00 je pre D-ribózu v elučnom systéme A: 2,13 a v elučnom systéme B: 1,90 a pre D-arabinózu v elučnom systéme A: 1,41 a v elučnom systéme B: 1,30. PříkladůThe procedure is as in Example 1 except that a mixture of 22.5 g (0.1 mol) of N-phenyl-D-ribozylamine, 25 mg (2.10 -5 mol) of hexaammonium heptamolybdate tetrahydrate, 59 mg (2.8.10 mol) is used. -4 mol) of citric acid monohydrate (molar ratio of citric acid to molybdenum of oxidation state VI 2: 1), 15.8 ml (0.2 mol) 35th% by weight. % aqueous formaldehyde solution, 35 ml 96 wt. ethanol and 190 ml of water. Chromatography shows the presence of D-ribose and traces of D-arabinose. Mobility related to D-glucose 1.00 is for D-ribose in elution system A: 2.13 and in elution system B: 1.90 and for D-arabinose in elution system A: 1.41 and in elution system B: 1 , 30th examples
Postupuje sa ako v příklade 3 s tým rozdielom, že sa použije N-fenyl-L-lyxozylamín. Chromatograficky záznam dokazuje přítomnost' L-lyxózy a v stopovom množstve přítomnost L-xylózy. Pohyblivost vzťahujúca sa na D-glukózu je pre L-lyxózu v elučnom systéme A: 1,82 a v elučnom systéme B: 1,66 a pre L-xylózu v elučnom systéme A: 1,72 a v elučnom systéme B: 1,54.The procedure is as in Example 3 except that N-phenyl-L-lyxozylamine is used. Chromatography shows the presence of L-lyxose and trace amounts of L-xylose. The mobility related to D-glucose is for L-lyxose in elution system A: 1.82 and in elution system B: 1.66 and for L-xylose in elution system A: 1.72 and in elution system B: 1.54.
V príkladoch prevedenia sa uvádzajú teploty inhibície epimerizácie 90 a 100 °C, ale epimerizácia je inhibovaná aj pri podstatné nižších teplotách, například pri zahušťovaní roztokov aldóz. Kyselina citrónová vytvára s molybdénanovýml iónmi stabilný komplex, ktorým sa inhibuje epimerizácia aldóz aj podstatné dlhší čas, ako sa uvádza v príkladoch prevedenia. Nie je ale efektívne skladovat roztoky aldóz dlhší čas pri nižších teplotách, nakolko rozlgky aldóz sú dobré živné pódy pre niektoré mikroorganizmy, ktoré ich móžu znehodnotit’.In the examples, epimerization inhibition temperatures of 90 ° C and 100 ° C are reported, but epimerization is also inhibited at substantially lower temperatures, such as the concentration of aldose solutions. Citric acid forms a stable complex with molybdate ions, which inhibits the epimerization of aldoses even for a substantial period of time, as exemplified in the examples. However, it is not efficient to store aldose solutions for extended periods of time at lower temperatures, since aldose rags are good nutrients for some microorganisms that may degrade them.
Spósob přípravy aldóz móže nájsť široké použitie v organickej chemii pri přípravo aldóz D- i L-radu.The process for the preparation of aldoses can be widely used in organic chemistry in the preparation of aldoses of the D- and L-series.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS874637A CS260394B1 (en) | 1987-06-23 | 1987-06-23 | Method of aldoses preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS874637A CS260394B1 (en) | 1987-06-23 | 1987-06-23 | Method of aldoses preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS463787A1 CS463787A1 (en) | 1988-05-16 |
| CS260394B1 true CS260394B1 (en) | 1988-12-15 |
Family
ID=5389597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS874637A CS260394B1 (en) | 1987-06-23 | 1987-06-23 | Method of aldoses preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS260394B1 (en) |
-
1987
- 1987-06-23 CS CS874637A patent/CS260394B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS463787A1 (en) | 1988-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Conchie et al. | Methyl and phenyl glycosides of the common sugars | |
| Isbell | Synthesis of D-glucose-1-C14 and D-mannose-1-C14 | |
| Pierce et al. | Anomerization of furanose sugars and sugar phosphates | |
| Farmer et al. | The alkylation of 2′-deoxyguanosine and of thymidine with diazoalkanes. Some observations on o-alkylation | |
| Harris et al. | Mechanism of the interconversion of D-glucose, D-mannose, and D-fructose in acid solution | |
| Carson | The Reaction of Fructose with Isopropylamine and Cyclohexylamine2 | |
| Anet | Chemistry of Non-enzymic Browning. VII. Crystalline Di-D-fructose-glycine and some related compounds | |
| Rittenberg et al. | A Comparison of the Rate of Mutarotation and O18 Exchange of Glucose1 | |
| Ozinskas et al. | Formation of N‐Hydroxy‐amines of Spin Labeled Nucleosides for 1H‐NMR. Analysis | |
| Bilik | Reactions of Saccharides Catalyzed by Molybdate Ions. IV.* Epimerization of Aldopentoses | |
| Ferrier et al. | Studies with radioactive sugars: Part I. Aspects of the alcoholysis of D-xylose and D-glucose; the role of the acyclic acetals | |
| CS260394B1 (en) | Method of aldoses preparation | |
| Perchemlides et al. | Synthesis of α-L-idopyranosyl,(α-L-idopyranosyluronic acid), α-D-mannopyranosyl, and (α-D-mannopyranosyluronic acid) phosphates | |
| Simonov et al. | Possible prebiotic synthesis of monosaccharides from formaldehyde in presence of phosphates | |
| Azéma et al. | Chemical and enzymatic synthesis of fructose analogues as probes for import studies by the hexose transporter in parasites | |
| Rosen et al. | Reactions of Carbohydrates with Nitrogenous Substances. VI. The Amadori Rearrangement in Methanol1, 2 | |
| Barker et al. | Linkage analysis of carbohydrates by using saccharinic acid formation | |
| Sattler et al. | Unfermentable Reducing Substances in Molasses. Volatile Decomposition Products of Sugars and their Role in Melanoidin Formation. | |
| Lee et al. | Synthesis of 2-(6-aminohexanamido) ethyl 1-thio-β-d-galactopyranoside and 1-thio-β-d-glucopyranoside, and related compounds | |
| JP3081016B2 (en) | Crystalline thionicotinamide-adenine dinucleotide potassium phosphate and process for producing the same | |
| KATO et al. | Fluorometric Analysis of Biological Materials. I. A Fluorophotometric Determination of Carbohydrates Using Taurine and Borate | |
| US4894363A (en) | Derivatives of serotonin | |
| CS260393B1 (en) | Method of aldoses preparation | |
| CS260398B1 (en) | Method of aldoses preparation | |
| Neish | PREPARATION OF 1-C14 PENTONIC ACIDS BY THE CYANHYDRIN SYNTHESIS |