EP1311523A1 - Procede de fabrication d'alkylglucosides, en particulier d'alkylfructosides - Google Patents

Procede de fabrication d'alkylglucosides, en particulier d'alkylfructosides

Info

Publication number
EP1311523A1
EP1311523A1 EP01976144A EP01976144A EP1311523A1 EP 1311523 A1 EP1311523 A1 EP 1311523A1 EP 01976144 A EP01976144 A EP 01976144A EP 01976144 A EP01976144 A EP 01976144A EP 1311523 A1 EP1311523 A1 EP 1311523A1
Authority
EP
European Patent Office
Prior art keywords
montmorillonite
alkyl
alcohol
catalyst
alkyl glycosides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01976144A
Other languages
German (de)
English (en)
Inventor
Martin Walter
Elmar Lampe
Volker Diehl
Klaus Buchholz
Dieter Wullbrandt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nordzucker AG
Original Assignee
Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev
INST TECHNOLOGIE DER KOHLENHYD
Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev, INST TECHNOLOGIE DER KOHLENHYD, Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev filed Critical Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev
Publication of EP1311523A1 publication Critical patent/EP1311523A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical

Definitions

  • the invention relates to a process for the preparation of alkyl glycosides by acid-catalyzed reaction of alcohols with a saccharide or of short-chain alkyl glycosides obtained therefrom to longer-chain alkyl glycosides.
  • Alkyl glycosides especially the higher alkyl glycosides with at least eight carbon atoms in the aglycone, have been known as raw materials for cleaning and detergent formulations for over 60 years. They are also used as wetting agents and emulsifiers in both the food and non-food sectors. They are completely biodegradable and non-toxic substances that can be produced from renewable raw materials. Due to this positive eco-profile and their high synergistic potential in combination with classic commodity surfactants, they have a rapidly growing economic importance.
  • Alkyl glycosides are generally obtained by acidic reaction of saccharides with an alcohol or by so-called transglycosidation of short-chain alkyl glycosides with the corresponding higher alcohol.
  • the reaction conditions generally result in polymerization reactions of the sugar constituents, so that product mixtures of alkyl monoglycosides with the corresponding polymers are obtained as a result.
  • aldoses and ketoses such as e.g. Glucose, mannose, gaiactose, xylose, ribose and fructose as well as disaccharides such as sucrose and maltose are used.
  • WO 96/36640 describes a process for the production of alkyl glycosides using a special catalyst which is a mesoporous molecular sieve based on silicon oxide, wherein fructose and fructose-containing disaccharides are reacted to give the corresponding alkyl fructoside or the corresponding alkylated disaccharide.
  • the disaccharides that are used here consist of a monosaccharide and fructose, the fructose being bound to the further monosaccharide as a reducing monosaccharide, such as, for. B. lactulose and leucrose. The disaccharide is converted into the alkylated product without being cleaved.
  • EP 0 570 056 and EP 0 619 318 relate to processes for the preparation of alkyl polyglycosides, the formation of polysaccharides such as polyglycoses as by-products being prevented by using either a binary catalyst composed of a strong organic acid and a weak organic base or an alkyl or arylsulfonic acid, the sulfone group of which is sterically hindered.
  • Alkyl glycosides in the form of mixtures of alkyl monoglycosides and alkyl oligo- and alkyl polyglycosides from glucose contain colored impurities which are a Make processes for lightening the color of the end products necessary (DE 38 337 80).
  • this object is achieved by a process for the preparation of alkylglycosides from saccharides which contain fructose in non-reducing form, by acid-catalyzed reaction of alcohols with the saccharides, at least one selected from a clay mineral, a Y-zeolite and oxalic acid as catalyst.
  • the corresponding alkyl fructosides can be obtained in addition to the alkyl glycosides which result from the alkylation of the further sugar constituents of the starting saccharide.
  • the saccharides used as starting materials contain fructose in a non-reducing form as a constituent.
  • the fructose is coupled to a further sugar monomer via the anomeric carbon atoms, i.e. via the glycosidic hydroxyl groups.
  • the compound obtained is therefore comparable to an acetal and has no reducing effect.
  • higher alkyl glycosides with, for example, at least eight carbon atoms can be obtained in the aglycone by transglycosidation of lower alkyl glycosides, the lower alkyl glycosides being produced according to the invention.
  • any oligosaccharide or polysaccharide which contains fructose in a non-reducing form is suitable as the saccharide.
  • Disaccharides are particularly preferred, sucrose or difructose anhydride III being mentioned as examples of disaccharides containing fructose in a non-reducing form.
  • the alcohol used as starting material can in principle be selected from a large number of alcohols as are generally known for the production of alkyl glycosides.
  • primary and secondary alcohols can be used.
  • Alcohols with a chain length of C8 to C22 are preferably used for the production of the higher alkyl glycosides, as can also be used for the abovementioned applications, in particular as a surfactant.
  • Primary aliphatic alcohols with a chain length of C1 to C5 are preferably used for the production of lower alkyl glycosides which are suitable for a subsequent transglycosidation with a higher alcohol.
  • a saccharide-alcohol molar ratio of 1: 180 to 1: 5, preferably 1:70 to 1:10, can be selected according to the invention.
  • a catalyst selected from an acid clay mineral, a Y-zeolite, oxalic acid or mixtures thereof is used for the reaction according to the invention.
  • the acidic clay mineral is preferably kaolinite or a montmorillonite such as e.g.
  • Montmorillonite catalyst can also be exchanged interlayer ions.
  • Interlayer metal ions replaced by other metal ions, e.g. Aluminum (III), iron (III), copper (II), sodium or zinc (II).
  • the montmorillonite catalysts in particular montmorillonite K10, K10-Fe and K10-Cu, are particularly preferred according to the invention.
  • the proportion of catalyst mass is usually 5 to 50%, preferably 10 to 20%, based on the saccharide mass used.
  • the alcohol itself or another solvent suitable for this purpose, as is usually used, can be used for the reaction.
  • the temperature chosen for the reaction depends on the type of alcohol, but should not exceed 140 ° Celsius.
  • temperatures in a range from 90 ° to 140 ° Celsius, in particular from 110 ° to 125 ° Celsius, are preferably selected.
  • the temperature is set to a value which enables the short-chain alcohol to reflux.
  • the temperature here preferably does not exceed 120 ° Celsius.
  • the selectivity here is not limited to the production of alkyl glycosides by alkylation of fructose, but also relates to transglycosidation. It has thus been found that when transglycodization of mixtures of short-chain alkylfructoside and other short-chain alkylglycosides at 100 ° C. or less is carried out, the short-chain alkylfructosides with the higher-chain alcohol are selectively reacted to the corresponding higher-chain alkylfructosides, while the short-chain alkylglycosides of the other saccharide components are not converted ,
  • the reaction can be carried out under reduced pressure, the pressure value also being able to vary depending on the type of alcohol used.
  • the process according to the invention for the production of alkyl glycosides can be carried out by thermal reaction of the saccharides or transglycosidation of lower alkyl glycosides with higher alcohols in the presence of the acidic catalyst, continuous removal of the water of reaction formed by, for. B. vacuum, filtering off the catalyst and removing the excess alcohol, e.g. B. alternatively by solid phase extraction or distillation.
  • the method can include the following steps:
  • a) be placed on a temperature-controlled column which is filled with a suitable carrier material.
  • a suitable eluent is pumped over the column until no higher alcohol can be detected in the ⁇ eluate.
  • the alkyl glycosides can then be eluted with a suitable eluent, the alcohol removed by evaporation and obtained as a paste or aqueous suspension which can be used for freeze-drying.
  • a suitable eluent for removing the higher alcohol is e.g. B. a C4 to C6 alcohol or mixtures thereof, e.g. B. 1-butanol.
  • a suitable means for eluting the alkyl glycosides obtained is e.g. B. a C1 to C3 alcohol, mixtures thereof or aqueous mixtures thereof.
  • sucrose used as starting material a product of a mixture of alkyl glucosides and alkyl fructosides is obtained.
  • sucrose is preferably used which has crystal diameters in a range from 250 to 800 ⁇ m, in particular from 315 to 500 ⁇ m.
  • a suitable material for the column can be selected from silica gel, celite, montmorillonite K10 or aluminum oxide, preferably basic aluminum oxide, with the column being heated to a temperature of 40 ° to 50 ° Celsius.
  • the mass ratio of alkylylycoside in the solution and the basic aluminum oxide should preferably not be less than 1:10.
  • the volume ratio of higher alcohol / 1-butanol required to remove the higher alcohol is generally between 1: 4 and 1:10, with ratios between 1: 5 and 1: 7 being customary.
  • the 1-butanol used and the excess higher alcohol can be recycled.
  • the elution of the alkyl glycosides from the basic aluminum oxide can be carried out with an aqueous, between 50% and 96%, in particular 70%, ethanol solution. Usually between 50 and 100 ml ethanol solution are required per gram of alkyl glycoside.
  • the solution thus obtained with the alkyl glycosides can either be thickened into a paste or freeze-dried after the ethanol has been distilled off.
  • the catalyst is usually separated from the hot reaction solution using a membrane filter, a 0.45 ⁇ m membrane filter in particular having proven suitable for the catalysts used according to the invention.
  • the saccharide which contains the fructose in a non-reducing form is first split under the reaction conditions.
  • the free fructose in a reducing form does not arise as an intermediate, but the corresponding alkyl fructoside through reaction with the alcohol.
  • the formation of the alkyl fructoside is supported here by the anhydrous conditions, as are usually chosen for the production of alkyl glycosides.
  • sucrose which is also preferred according to the invention
  • alkylfructoside and the free glucose are initially formed, it being also possible to convert glucose into the corresponding alkylglucosides by reaction with excess alcohol. If the reaction is kept at a temperature of 100 ° C or less, the formation of the alkyl glucosides is suppressed and alkyl fructoside is selectively formed.
  • the short-chain alkylfructosides being selectively reacted with the higher-chain alcohol from a mixture of short-chain alkylfructosides and alkylglucosides.
  • alkyl glycosides obtained according to the invention have no strongly colored impurities and can be used directly as such or separated into the individual components without further purification for a wide variety of applications. They are particularly suitable for use in detergent compositions, cosmetic formulations or foods, as wetting agents and emulsifiers.
  • the invention is illustrated below with the aid of individual examples which relate to the preparation of selected alkyl glycosides.
  • reaction mixture was placed on a column filled with 50 g of basic aluminum oxide (90 activity level I) and heated to 40 ° C. After rinsing with 400 mL 1-butanol, 1-dodecanol was no longer eluted. Then the long-chain alkyl glycosides with 300 mL 70 percent. Washed ethanol solution from the carrier material. The ethanol was distilled off and the products suspended in the remaining aqueous solution were freeze-dried. 2.3 g of dodecylglycosides were obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Saccharide Compounds (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'alkylglycosides à partir de saccharides contenant du fructose sous forme non réduite, consistant à transformer un alcool avec les saccharides en présence d'un catalyseur acide. Ledit catalyseur peut être un minéral argileux et/ou un zéolithe Y et/ou de l'acide oxalique, et le mélange de produit contient les alkylfructosides correspondants. Selon ledit procédé, les alkylglycosides obtenus peuvent éventuellement être transglycosidés avec un autre alcool, en particulier un alcool supérieur.
EP01976144A 2000-08-24 2001-08-24 Procede de fabrication d'alkylglucosides, en particulier d'alkylfructosides Withdrawn EP1311523A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10041577 2000-08-24
DE2000141577 DE10041577A1 (de) 2000-08-24 2000-08-24 Verfahren zur Herstellung von Alkylglycosiden, insbesondere Alkylfructosiden
PCT/EP2001/009803 WO2002016379A1 (fr) 2000-08-24 2001-08-24 Procede de fabrication d'alkylglucosides, en particulier d'alkylfructosides

Publications (1)

Publication Number Publication Date
EP1311523A1 true EP1311523A1 (fr) 2003-05-21

Family

ID=7653638

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01976144A Withdrawn EP1311523A1 (fr) 2000-08-24 2001-08-24 Procede de fabrication d'alkylglucosides, en particulier d'alkylfructosides

Country Status (4)

Country Link
EP (1) EP1311523A1 (fr)
AU (1) AU2001295508A1 (fr)
DE (1) DE10041577A1 (fr)
WO (1) WO2002016379A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2627247C (fr) 2005-10-28 2013-04-02 Boehringer Ingelheim International Gmbh Analyse de l'activite de ns2/3 du virus de l'hepatite c

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994009019A1 (fr) * 1992-10-14 1994-04-28 Unichema Chemie B.V. Procede de preparation d'alkylglycosides
IT1272109B (it) * 1993-03-19 1997-06-11 Eniricerche Spa Processo per la preparazione di apg
US5717081A (en) * 1993-09-17 1998-02-10 Unichema Chemie B.V. Process for producing an alkylglycoside using a pervaporation membrane to remove reaction water
WO1996036640A2 (fr) * 1995-05-19 1996-11-21 Technische Universiteit Delft Procede pour la preparation d'alkylglycosides
JP3751099B2 (ja) * 1996-12-27 2006-03-01 ローム株式会社 電源回路
JP3388382B2 (ja) * 1997-01-24 2003-03-17 独立行政法人産業技術総合研究所 アルキルグルコピラノシドの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0216379A1 *

Also Published As

Publication number Publication date
AU2001295508A1 (en) 2002-03-04
WO2002016379A1 (fr) 2002-02-28
DE10041577A1 (de) 2002-03-14

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