WO1997030063A2 - Preparation of surface-active compounds based on lactose - Google Patents
Preparation of surface-active compounds based on lactose Download PDFInfo
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- WO1997030063A2 WO1997030063A2 PCT/NL1997/000070 NL9700070W WO9730063A2 WO 1997030063 A2 WO1997030063 A2 WO 1997030063A2 NL 9700070 W NL9700070 W NL 9700070W WO 9730063 A2 WO9730063 A2 WO 9730063A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/04—Disaccharides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/06—Oligosaccharides, i.e. having three to five saccharide radicals attached to each other by glycosidic linkages
Definitions
- the invention relates to a method for preparing surface-active compounds based on aminated galacto-oligosaccharides such as lactose.
- French Patent Application 2661413 discloses the preparation of N-alkyl- lactosylamines and N-alkyllactylamines.
- the N-alkyllactosylamines are prepared by reacting lactose with an N-alkylamine in water/2- propanol.
- the amount of solvent is about 15 times that of the amount of lactose, and the reaction takes about 24 hours.
- the yield is between 48 and 74%.
- the N-alkyllactylamines are prepared, in a second step, from the N-alkyllactosylamines, either by catalysed hydrogenation (yield about 40%, incomplete conversion), or by reduction with sodium borohydride (yield 57- 90%).
- N-acetyl-N-alkyllactosylamines via the reaction of N-alkyilactosylamine with acetic anhydride.
- the reaction is carried out in a large amount (about 13 times the amount of lactosylamine) of aprotic solvent such as dimethylformamide or dimethyl sulphoxide under argon.
- aprotic solvent such as dimethylformamide or dimethyl sulphoxide under argon.
- the yield is in the order of 35-50%.
- a drawback of this method is the low yield and the use of solvents which arc undesirable, certainly for alimentary applications.
- a further drawback of the known methods for the preparation of amines derived from lactose is that they do not lend themselves to continuous operation.
- Lammers et al (Tetrahedron, 27, 8103-8116, 1994) describe the reductive amination of galactose, mannose and glucose with propylamine, ethylenediamine and 1,3-diaminopropane with a platinum catalyst.
- Galactitol mannitol, glucitol
- Galactitol is formed as an important byproduct (about 15%) when an equivalent amount of amine used; the product yield is 80-85 % when 5 equivalents of amine are used. Such results are not attractive for a reaction with long chain alkylamines.
- lactose derivatives known per se which are surface-active, in particular detergent and/or emulsifying, and to provide novel surface-active derivatives of galacto-oligosaccharides.
- galacto-oligosaccharides refers to reducing sugars and sugar derivatives which include at least one galactose unit to which one or more further monosaccharide units are bound.
- lactose ⁇ -galactosyl-glucose: ⁇ Gal-l,4-Glu
- ⁇ Gal-l,6-Gal and melibiose ⁇ Gal-l,6-Glu
- galactoglycosylamine and galactoglycitylamine herein refer to a galacto-oligosaccharide whose reducing hydroxyl group, not necessarily on the galactose unit, has been replaced by an amine group, without reduction or by means of reduction, respectively.
- the invention is hereinafter illustrated with reference to lactose and lact(os)ylamines, but in each case this should be understood as equally implying other galacto-oligo ⁇ saccharides as defined hereinabove or the corresponding amines.
- this group may be saturated or unsaturated, and includes an alkyl, alkenyl, alkynyl, alkadienyl or alkapolyenyl group, each of which may or may not be branched and has 1-19 or 1-20 carbon atoms and in which, at the same time, an aromatic or alicyclic group may be present.
- alkyl groups also comprise mixtures of alkyl groups. These may have an average between e.g. 2 and 20 carbon atoms, in particular between 10 and 18 carbon atoms.
- Such mixtures arc accessible in the form of mixed alkylamines, for example tallow amine (1% C 12 , 4% C 14 , 31% C 16 , 64% C 18 ), cocoamine (5% C 8 , 6% C 10 , 50% C 12 , 19% C 14 , 10% C 16 , 10% C 18 ), and oleylamine (1% C 12 , 4% C 14 , 12% C 16 , 82% C 18 ).
- the invention relates to a method for preparing surface- active, detergent, dispersant and/or emulsifying lactose derivatives, lactose being aminated reductively, in a one-step process, using a CI ⁇ C 2Q alkylamine which may or may not be saturated and hydrogen in the presence of a transition metal catalyst.
- This method preferably employs an equivalent amount or a slightly sub- stoichiometric amount or slight excess of alkylamine, in particular 0.8-1.5 equivalents.
- a transition metal used may be selected from the metals known per se for this purpose, such as nickel, palladium, platinum, ruthenium or other metals from group VIII, especially palladium.
- the transition metal may be applied to a support such as carbon.
- the solvent used may, for example, be water, an alcohol or an alcohol-water mixture. It was found, surprisingly, that if a slightly substoichiometric amount (i.e. less than 1.00 equivalent, for example 0.85-0.98 equivalent), based on lactose, of alkylamine is used, the lactose is not reduced to lactitol, the work-up of the product thus being simplified.
- the invention relates to a method for preparing surfactant lactose derivatives, lactose being aminated by means of reactive processing using a C 1 -C 2Q alkylamine, and the N-alkyllactosylamine being reduced in a second step.
- reactive processing refers to a reaction involving little or no solvent, in general less than 4 parts by weight and in particular less than 3 parts by weight of solvent per part by weight of lactose, with mechanical blending. Blending takes place in such a way that a reaction occurs. Optionally, the reaction may be carried out with heating or in the melt, one particular option being that of employing an extrusion process.
- Reactive processing is known per se, for example for the preparation of starch derivatives (sec, for example, Tomasik ct al., Starch/St ⁇ rke 47 (1995), 96-99, and Narkrugsa ct al., Starch/St ⁇ rke 44 (1992), 81-90).
- the present method preferably employs moderate temperatures, for example between 10 and 100°C.
- Suitable solvents are solvents containing carbon, hydrogen and oxygen only, such as water, alcohols especially C j -C 4 alkanols such as methanol, ethanol, isopropanol and methoxyethanol, and relatively polar ethers such as tetrahydrofuran, dioxane, dimethoxyethane, as well as mixtures of water and an alcohol and/or an ether.
- Reactive processing rapidly (in less than 1/2 hour) leads to high yields of alkyllactosylamine.
- Important advantages of reactive processing are that the reaction can be a continuous process, that the processes arc more energy-efficient and less solvent or none at all is consumed, so that fewer work-up steps are required.
- the N-alkyllactosylamine thus obtained is less suitable for use as such, since it is relatively unstable.
- the N-alkyl-lactosylaminc is therefore preferably reduced to an N-acyllactylamine or acylated to an N-alkyl-N-acyllactosylamine.
- the reduction to N-alkyllactylamine can be effected by means of hydrogen in the presence of a transition metal catalyst or alternatively by means of a hydride such as sodium borohydride.
- the catalysed hydrogenation is preferably carried out at elevated temperature, for example between 30 and 80°C.
- the reduction with sodium boro- hydride can be carried out at room temperature. The reduction leads to a yield of 70% or more.
- N-alkyl- galactoglycitylamines having the formula: Sar-NH-R 1 are thus prepared, where Sar represents the radical of a reduced di- or oligosaccharidc which contains at least one galactose unit, and R represents a C j -C 20 alkyl group which may or may not be saturated.
- R represents a C 7 -C 0 group, in particular a C 10 -C 18 group, such as a hexa ⁇ decyl group.
- Another aspect of the invention relates to a method for preparing surface- active lactose derivatives by a lactosylamine, having been obtained from lactose, being acylated using a C 2 -C 2fJ -carboxylic acid anhydride or halide by means of reactive processing.
- Said acylation by reactive processing is preferably effected using a solvent containing carbon, hydrogen and/or oxygen only and/or by means of reactive processing (extrusion), at temperatures which may or may not be elevated, such as 10-100°C.
- no solvent is used in reactive extrusion, particularly if the carboxyiic acid anhydride or halide is a liquid.
- a base may also be added to bind any acid formed.
- a solid base is used such as potassium carbonate or sodium bicarbonate, or optionally a liquid base such as triethylamine. Reactive processing can advantageously be carried out continuously.
- the preferred solvent is methanol and no base is necessary.
- the lactosylamine which is the starting material for the above-described acylation can be obtained by reaction of lactose with a C l -C 20 alkylamine in a manner known per se. Said amination can be carried out in water and/or an alcohol, such as isopropanol, as a solvent, for example at a temperature of 30-70°C.
- the lactosylamine can alternatively be obtained in the above-described manner by reactive processing.
- the acylated lactosylamines can be prepared not only by successive amination and acylation, as described above, but also by amidation of lactose. Said amidation is carried out using a C 2 -C 20 -acylamine or using urea or an alkylurea, by means of reactive processing as described hereinabove for the acylation.
- an alkylation can be carried out subsequently, for example using an alkyl halide, alkyl acetate, alkyl benzoate or alkyl sulphonate, so as to introduce the alkyl group which is required for the surface-active properties.
- R 1 and R contains at least 7 and more preferably at least 10 carbon atoms.
- R 1 preferably contains at least 12 carbon atoms or is a mixture of alkyl groups with an average of 10-18 carbon atoms.
- N-alkyl-N-acyl-lactylamines can be prepared either by acylation of an N-alkyllactylamine obtained in the above-described manner, for example by means of reactive processing, or by the reduction of an N-alkyl-N- acyllactosylamine, for example using hydrogen/palladium or sodium borohydride.
- N-acylgalactoglycitylamines having the formula Sar-NR 1 -CO-(NH) m -R 2 are prepared, in which Sar represents the radical of a reduced di- or oligosaccharide which contains at least one galactose unit, m represents the number 0 or 1, R 1 represents hydrogen or an alkyl group which may or may not be saturated and has 1-
- R 2 represents hydrogen or an alkyl group which may or may not be saturated and has 1-19 carbon atoms.
- at least one of the groups R 1 and R 2 preferably contains at least 7 and more preferably at least 10 carbon atoms or is a mixture of alkyl groups with an average of 10-18 carbon atoms.
- a further aspect of the invention relates to surface-active lact(os)ylamines which, on one or more of the oxygen and nitrogen atoms, carry an alkyl or alkanoyl group substituted by one or more acid groups -COOH, -PO(R 4 )(OH), -PO(OR 4 )(OH), -OPO(R )(OH), -OPO(OR 4 )(OH), -SO 3 H or -OSO 3 H and having
- R 4 here represents a hydrogen atom or a C j -Cy-hydrocarbon group such as methyl, ethyl, aUyl, butyl, phenyl, cyclohexyl or benzyl.
- the acid groups may be present in ionised form, and in particular zwitterions may be involved.
- These compounds can be prepared, for example, by the reaction of a lactylamine or lactosylamine as described hereinabove with, for example: a haloacetic acid with the formation of an N- or O-carboxymethyl derivative; acrylonitrile followed by saponification with the formation of an N- or O-carboxy- ethyl derivative; a halomethylphosphonic acid with the formation of an O- or N- phosphonomethyl derivative; formaldehyde and an alkylphosphonic acid with the formation of an N-(ethylphosphonicomcthyl) derivative; hydroxymethylsulphonic acid with the formation of a sulphomethyl derivative; chlorocthylsulphonic acid with the formation of an O- or N-sulpho-ethyl derivative; ethylene oxide and chlorosulphonic acid with the formation of an O-sulphatoethyl derivative; chlorosulphonic acid or chlorophosphonic acid with the formation of an O-sulpha
- Suitable derivatisation methods to introduce the acid groups are described, for example, by Van Havercn ct al., NMR in Biomcdicine, 8, 197-205 (1995), and O'Lenick et al., JAOCS, 73, 935-937 (1996).
- the invention relates to a method for preparing surface- active oxidised lactose derivatives, in which an N-alkyllactosylaminc, N-alkyllactyl ⁇ amine, N-alkyl-N-acyllactylamine or N-alkyl-N-acyllactosylamine is oxidised in such a way that at least some of the primary alcohol groups are converted into a carboxyiic acid.
- the aminated lactose derivatives are oxidised in such a way that out of 100 primary alcohol functions at least two are converted into a car ⁇ boxyiic acid group.
- aminated lactose derivatives contain two primary alcohol functions per molecule, a product is thus obtained which comprises at least approximately 4 mol% of carboxylated compounds. If desired it is also possible for all the primary alcohol functions to be oxidised to carboxyiic acid functions, but to achieve an appropriate surface-active effect it is generally sufficient if a fraction of the functions is oxidised.
- An advantage of partially oxidised lactylamines is that their solubility in water is enhanced or that they result in less precipitation. In particular, from 4 to 100% of the primary alcohol groups are oxidised to a carboxyiic acid.
- the oxidation may be carried out, for example, using molecular halogen (Cl or Br 2 ) or a hypohalite (usually NaOCl or NaOBr).
- This oxidation can be carried out in water or a water/alcohol mixture at a pH of 8-10. This oxidation may give rise not only to a conversion of primary alcohol groups but also to oxidation of C 2 -C 3 -diol groups.
- a more selective oxidation of the aminated lactose derivatives can be achieved if the oxidation is carried out with a hypohalite in the presence of a di- tertiary-alkyl nitroxyl compound as a catalyst.
- the di-t-alkylnitroxyl compound may, for example, be di-t-butylnitroxyl, but in particular is a cyclic compound such as an N-oxylpyrrolidine, -piperidine or -morpholine compound whose carbon atoms next to the nitroxyl group arc methylated and which may additionally contain, for example, methyl or methoxy substituents.
- TEMPO 2,2,6,6-tctramethylpiperidine-l-oxyl
- the di-t-alkyl-nitroxyl may optionally be prepared in the reaction medium, for example by oxidation of the corresponding di-t-alkylamine with hydrogen peroxide and tungstate.
- a catalytic amount of nitroxyl refers to an amount which - after conversion of the nitroxyl radical to the corresponding nitrosonium ion - is less than 10% of the amount required for the oxidation of all the primary hydroxyl groups to carboxyl groups.
- the catalytic amount of nitroxyl, based on the carbohydrate monomer is 0.01 -2 mol%.
- the oxidation of the lactose-amine derivatives may further be carried out using oxygen in the presence of a transition metal catalyst.
- a transition metal catalyst for example, platinum on carbon
- This oxidation can likewise be carried out in water or in a water/alcohol mixture, the pH being maintained, for example, between 7 and 10.
- the oxidation can also be carried out enzymatically, in particular using galactose oxidase (EC 1.1.3.9), the primary alcohol group of the galactose unit being oxidised selectively and a degree of oxidation between 0 and 100% being achievable.
- galactose oxidase EC 1.1.3.9
- the primary alcohol group of the galactose unit being oxidised selectively and a degree of oxidation between 0 and 100% being achievable.
- the invention also relates to the oxidised lactosc-aminc derivatives which can thus be obtained, in particular those of which at least 2%, more in particular at least 4%, of the primary alcohol groups have been converted into a carboxyiic acid group.
- the invention further relates to the use of the above-described derivatives as an emulsifier in foods, as a cleaning agent or an emulsifier in textile washing compositions, detergents, dishwasher detergents, bodycarc products, beauty products, shampoos, as a surfactant in inks and paints and the like, or as a dispersant, inter alia for pesticides and the like. Also a combination of products according to the invention can be used.
- a combination of a nonionic surfactant such as N-octa- decyl-lactylamine or N-hexadccyl-N-acctyllactosylaminc with an anionic surfactant such as N-carboxymethyl-N-hexadccyllactylamine or N-hexadecyl-N-acetyl- lacturonylamine forms an excellent surfactant composition.
- a textile washing composition may contain one or more surfactants according to the invention at a level of 1-10 wt.%, together with other conventional constituents such as soaps, optical brighteners, zeolites, enzymes, perborate, builders, anionic polymers, foam regulators etc.
- surfactants for delicate textile it may contain 1-15 wt.% of a surfactant of the invention, 5-25 wt.% of soap, and further fatty acid ethoxylates, alcohols, polyglycols, perfumes and enzymes.
- a dish-washing composition may contain 1-15 wt.% of a surfactant of the invention and further 5-40 wt.% of other ionic surfactants, 0-10 wt.% of other zwitterionic or amphoteric surfactants, and proteins, polymers, hydrotropics. fragrances and preservatives.
- a hair cleansing composition or a shower bath composition may contain 1-10 wt.% of a surfactant of the invention, in addition to 1-20 wt.% of optional other surfactants, and further thickeners, perfumes, preservatives, colorants, vitamines etc.
- a skin cream cream may contain 1-10 wt.% of a surfactant of the invention, and 1-30% of other surfactants, together with optional mineral or ester oils, 1-10 wt.% of consistency improvers, perfumes, colourants, preservatives and the like.
- An emulsifier composition can contain 15-30 wt.% of non-ionic surfactant in addition to 20-35 wt.% of other non-ionic surfactants, mineral oil (20-45%) and water.
- An ink composition may contain 1-5 wt.% of a surfactant of the invention, together with optional polymers, humectants, colorants, foam breakers, and biocides.
- a paint composition may contain 0.5-5 wt.% of a surfactant of the invention, 10-80% of a resin, and further components such as pigments, reactive diluents, solvents, driers, fillers, extenders and additives.
- table 1 lists the critical micelle concentrations (CMC) of some alkyllactylamines prepared accord ⁇ ing to the invention.
- Table 2 lists the surface tension (ST) as a function of the concentration of hexadecyllactylaminc.
- the product was obtained with a yield of 90%.
- Example 1 One-step procedure for the synthesis of N-octyllactylamine Lactose (10.26 g, 30 mmol) was dissolved in 10 ml of warm water. To this, 4.65 g of octylamine (36 mmol, 1.2 eq) in 70 ml of 2-propanol and 750 mg of 10% Pd C were added. The reaction mixture was hydrogenated in a Parr apparatus (3.5 bar, 50°C) overnight. A sample was taken by a few ml of reaction mixture being filtered through celite and the solvent being evaporated.
- Lactose (53 g, 147 mmol) was introduced, together with hcxadecylamine (57 g, 183 mmol), 46 g of water and 64 g of 2-propanol, into a Haacke Rhcocord 50 kneader. The mixture was heated to 68°C and then kneaded for 15 minutes at a speed of 33 ⁇ m. Analysis ( 1 C solid-phase NMR) showed that 60-70% of the lactose had been converted to hexadecyllactosylaminc.
- Hexadecyllactosylamine was processed, with a throughput of 2 kg h, on a Werner and Pfleiderer ZKS 25 co-rotating twin-screw extruder. Water was injected into the extruder with a throughput of 1.3 kg/h. The total length of the extruder was 28D, with a diameter D of 25 mm. At a distance of 12D, acetic anhydride was added with a throughput of 0.55 kg/h, as was sodium bicarbonate with a throughput of 0.45 kg/h. A speed of 50 ⁇ m was used. With the aid of a dye, the average residence time of the product in the extruder was found to be about 3 minutes.
- the temperature profile set over the extruder was 40-60-60-70-70°C. At the extruder head the temperature measured of the material was 72°C. Analysis by L C-NMR showed that complete conversion to N-acyl-N-hexadecyl lactosylamine had occurred. Example 4. Oxidation of dodecyllactylamine with bleach
- Dodecyllactylamine (0.5 g, 0.98 mmol) was dissolved in 50 ml of water.
- 0.4 ml (0.21 mmol) of a sodium hypochlorite solution containing 4% of active chlorine was set to a pH of 9 and added to the dodecyllactylamine solution, after which the pH was maintained at 9 by means of 1 M NaOH. After the oxidation reaction was complete,
- Example 6 Oxidation of dodecyllactylamine using Pt/C and oxygen 0.1 g of 5% Pt/C was added to 25 ml of H 2 0. Dodecyllactylamine (0.5 g, 0.98 mmol) was dissolved in 30 ml of H 2 O and added to the Pt/C. The reaction mixture was brought to a pH of 9, and oxygen was passed through the mixture. After the reaction was complete, the catalyst was filtered off and the reaction mixture was concentrated to dryness. 13 C-NMR showed that an oxidised dodecyllactylamine had been obtained, the oxidation primarily having taken place at the primary alcohol groups of the dodecyllactylamine.
- Example 8 N -Acetyl -N-hexadecyl lactosylamine
- N-Hexadecyllactosylamine (20.1 g, 35.4 mmol) was dissolved in 1000 ml methanol at 60°C, and 10.83 g (106 mmol, 3.0 eq.) of acetic anhydride was added dropwise within 3 minutes. The reaction was complete after 2 hours and the reaction mixture was worked up by removing the solvent, acetic acid formed and the excess of acetic anhydride using a rotavapor. The product was purified by stirring overnight in 500 ml of acetone and separating it by filtration. The product was decolorised with activated carbon in methanol. The isolated yield was 50%; purity > 95%.
- Example 9 Preparation of hexadecyllactylamine 5.00 g (13.88 mmol) of lactose monohydrate were dissolved in 120 ml of water. To this solution, a solution of 3.05 g (12.63 mmol, 0.91 equivalent) of hexadecylamine in 200 ml of 2-propanol was added. This solution, together with 502 mg of Pd/C, was introduced into a Parr apparatus at 50°C under a hydrogen pressure of 2.8 bar. After 40 hours the reaction was stopped.
- Example 10 N -Carboxymethyl ' -hexadecyllactylamine 17.17 g (30.24 mmol) of N-hexadecyllactylaminc were suspended in 350 ml of water.
- the pH of the suspension was 8.1.
- 1 M NaOH solution and a pH-stat the pH of the suspension was raised to 10.
- 10.5 g (75.6 mmol, 2.5 eq) of bromoacetic acid were added by the spoonful, the pH being maintained at 10.
- the reaction mixture was stirred at 60°C for 4 hours, a clear solution being formed.
- the reaction temperature was raised to 70°C.
- 34.1 ml of 1 M NaOH solution 1.1 cq based on N-hexadccyllactylamine
- the reaction was stopped by neutralisation with 4 M hydrochloric acid.
- Example 11 Preparation of 6,6' -dicarboxy-N -acetyl -N-hexadecyllactosylamine N-Acetylhexadecyllactosylamine (0.502 g, 0.826 mol) was dissolved in 40 ml of water, and the solution was cooled to 1°C. NaBr (69.6 mg, 0.676 mmol, 0.82 eq.) and TEMPO (1.93 mg, 0.012 mmol, 0.015 eq.) were added.
- N-alkyl-lactylaminc N-alkyl derived from tallow amine, mixture of C 12 -C 18 alkyls, average chain length 17.2 carbon atoms
- 9 ml paraffin oil was added to 10 ml of a 2 wt.% solution of N-alkyl-lactylaminc (N-alkyl derived from tallow amine, mixture of C 12 -C 18 alkyls, average chain length 17.2 carbon atoms) in water.
- 9 ml paraffin oil was added.
- the mixture was thoroughly mixed for 30 seconds using an Ultra Turrax T 25 at 800 ⁇ m.
- the resulting product was a stable white emulsion, which remained stable for extended periods of time.
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU17359/97A AU1735997A (en) | 1996-02-19 | 1997-02-19 | Preparation of surface-active compounds based on lactose |
EP97904647A EP0882056A2 (en) | 1996-02-19 | 1997-02-19 | Preparation of surface-active compounds based on lactose |
JP9529225A JP2000504719A (en) | 1996-02-19 | 1997-02-19 | Production of lactose-based surface-active compounds |
BR9707558-2A BR9707558A (en) | 1996-02-19 | 1997-02-19 | Preparation of superficially active compounds based on lactose. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1002389A NL1002389C2 (en) | 1996-02-19 | 1996-02-19 | Preparation of surfactant derivatives of galacto-oligosaccharide compounds |
NL1002389 | 1996-02-19 | ||
NL1004372 | 1996-10-28 | ||
NL1004372 | 1996-10-28 |
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WO1997030063A2 true WO1997030063A2 (en) | 1997-08-21 |
WO1997030063A3 WO1997030063A3 (en) | 1997-10-09 |
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PCT/NL1997/000070 WO1997030063A2 (en) | 1996-02-19 | 1997-02-19 | Preparation of surface-active compounds based on lactose |
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EP (1) | EP0882056A2 (en) |
JP (1) | JP2000504719A (en) |
AU (1) | AU1735997A (en) |
BR (1) | BR9707558A (en) |
CA (1) | CA2245222A1 (en) |
WO (1) | WO1997030063A2 (en) |
Cited By (1)
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EP1529832A1 (en) * | 2003-11-04 | 2005-05-11 | Metall-Chemie Handelsgesellschaft mbH & Co. KG | Metal Working Fluids |
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EP0326673A2 (en) * | 1988-02-05 | 1989-08-09 | Hüls Aktiengesellschaft | Method for the preparation of oxidised substituted saccharides |
US4985553A (en) * | 1986-01-30 | 1991-01-15 | Roquette Freres | Process for the oxidation of di-, tri-, Oligo- and polysaccharides into polyhydroxycarboxylic acids, catalyst used and products thus obtained |
EP0454321A2 (en) * | 1990-04-27 | 1991-10-30 | Kao Corporation | Glycoside ester of sulfosuccinic acid and process for producing the same |
FR2661413A1 (en) * | 1990-04-26 | 1991-10-31 | Stepan Europe | N-Alkyllactylamines and process for preparing them |
US5434061A (en) * | 1992-11-27 | 1995-07-18 | Takeda Chemical Industries, Ltd. | Production of saccharide carboxylic acids |
EP0723972A1 (en) * | 1995-01-30 | 1996-07-31 | Stepan Europe | Lactylamines and their pharmaceutical application |
-
1997
- 1997-02-19 AU AU17359/97A patent/AU1735997A/en not_active Abandoned
- 1997-02-19 EP EP97904647A patent/EP0882056A2/en not_active Withdrawn
- 1997-02-19 WO PCT/NL1997/000070 patent/WO1997030063A2/en not_active Application Discontinuation
- 1997-02-19 JP JP9529225A patent/JP2000504719A/en active Pending
- 1997-02-19 CA CA 2245222 patent/CA2245222A1/en not_active Abandoned
- 1997-02-19 BR BR9707558-2A patent/BR9707558A/en not_active Application Discontinuation
Patent Citations (7)
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US2181929A (en) * | 1937-09-21 | 1939-12-05 | Du Pont | Maltosamine and process for preparing it |
US4985553A (en) * | 1986-01-30 | 1991-01-15 | Roquette Freres | Process for the oxidation of di-, tri-, Oligo- and polysaccharides into polyhydroxycarboxylic acids, catalyst used and products thus obtained |
EP0326673A2 (en) * | 1988-02-05 | 1989-08-09 | Hüls Aktiengesellschaft | Method for the preparation of oxidised substituted saccharides |
FR2661413A1 (en) * | 1990-04-26 | 1991-10-31 | Stepan Europe | N-Alkyllactylamines and process for preparing them |
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EP1529832A1 (en) * | 2003-11-04 | 2005-05-11 | Metall-Chemie Handelsgesellschaft mbH & Co. KG | Metal Working Fluids |
Also Published As
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WO1997030063A3 (en) | 1997-10-09 |
JP2000504719A (en) | 2000-04-18 |
BR9707558A (en) | 2000-01-04 |
AU1735997A (en) | 1997-09-02 |
CA2245222A1 (en) | 1997-08-21 |
EP0882056A2 (en) | 1998-12-09 |
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