EP3551640A1 - Verfahren zur herstellung von tensidzusammensetzungen mit alkyl l-iduronamiden, d-glucuronamiden und l-rhamnosiden aus ulvanen - Google Patents

Verfahren zur herstellung von tensidzusammensetzungen mit alkyl l-iduronamiden, d-glucuronamiden und l-rhamnosiden aus ulvanen

Info

Publication number
EP3551640A1
EP3551640A1 EP17821978.8A EP17821978A EP3551640A1 EP 3551640 A1 EP3551640 A1 EP 3551640A1 EP 17821978 A EP17821978 A EP 17821978A EP 3551640 A1 EP3551640 A1 EP 3551640A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
acid
formula
composition
surfactant
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Withdrawn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
EP17821978.8A
Other languages
English (en)
French (fr)
Inventor
Thierry Benvegnu
Nouha SARI-CHMAYSSEM
Samir TAHA
Hiba MAWLAWI
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.)
Ecole Nationale Superieure De Chimie
Original Assignee
Ecole Nationale Superieure De Chimie
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 Ecole Nationale Superieure De Chimie filed Critical Ecole Nationale Superieure De Chimie
Publication of EP3551640A1 publication Critical patent/EP3551640A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9706—Algae
    • A61K8/9722—Chlorophycota or Chlorophyta [green algae], e.g. Chlorella
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10—Antimycotics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H7/00—Compounds containing non-saccharide radicals linked to saccharide radicals by a carbon-to-carbon bond
    • C07H7/02—Acyclic radicals
    • C07H7/033—Uronic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/49—Solubiliser, Solubilising system

Definitions

  • the present invention relates to a new process for preparing compositions comprising alkyl L-iduronamides, alkyl L-rhamnosides and alkyl D-glucuronamides, directly from biosourced raw materials (ulvans, green algae). ) or biocompatible / biodegradable, the compositions obtained by said process and their uses.
  • the present invention finds, for example, applications in the field of surfactants, in particular for cosmetics, phytosanitary, agri-food, detergency (industrial).
  • references in brackets ([]) refer to the list of references at the end of the text.
  • carbohydrate surfactants represent a large class of amphiphilic compounds whose increasing interest can be explained by functional, economic and environmental factors (Hill and Lehen-Ferrenbach, 2009) [1].
  • the amide derivatives of sugars characterized by the presence of an amide function connecting the hydrophilic sugar head to the lipophilic chain have the advantage of being resistant to hydrolysis in neutral and alkaline media, especially compared to the derivatives esters (Laurent et al., 201 1) [2].
  • amide surfactant is derived from the transformation of oligomers of D-mannuronic acid from the depolymerization of alginates.
  • Ulvans are a family of polysaccharides that have recently been described in green algae of the Ulva or Enteromorpha type, species very present on the Mediterranean and Brittany coasts. These are polysaccharides whose composition is unique. They consist mainly of rhamnose and uronic acids (L-iduronic and D-glucuronic), elementary units to which are added glucose and xylose in the minority. The sulfation rate is generally high (5-30%). However, the use of ulvans as sources of L-iduronic and D-glucuronic acids and L-rhamnose for the potential preparation of monosaccharide surfactants has not been developed or even considered to date.
  • esters sorbitan esters, sucroesters
  • acetals alkylpolyglucosides
  • amides alkyl glucamides
  • the alkyl sucroamides are produced in two steps: reductive amination of a carbohydrate with an alkylamine, followed by the acylation of the resulting ⁇ -glycoside (International Application WO 92/06984, International Application WO 93/03004, EP Patent 0 536,939; US Patent 5,872,1 1 1) [3-6].
  • gluconamides are obtained in two stages: the oxidation of a carbohydrate leading to a lactone or an aldonic acid followed by a reaction with alkylamines to form gluconamides (US Pat. No. 2,670,345) [7].
  • Derivatives having an amide bond between the hydrophilic and lipophilic parts via a / V-glycoside linkage have been more recently developed (US Pat. No. 7,655,61 1) [8].
  • Mannuronamide surfactants have been produced from oligomers of D-mannuronic acid (Benvegnu and Sassi, 2010, International Application WO 03/104248) [9, 10]. The process is based on the production of saturated oligomannuronates (acid depolymerization) which are then converted into a monosaccharide intermediate having two butyl chains. This synthon is then subjected to an aminolysis reaction using a fatty amine in a solvent such as methanol or isopropanol in the presence or absence of an organic base. The surfactant / V-acylated thus obtained has emulsifying properties.
  • compositions comprising alkyl L-guluronamides or a mixture of alkyl L-guluronamides and alkyl D-mannuronamides have been produced from poly (oligo) guluronates, oligoalginates, alginates and the like. or brown algae, following a butanolysis and Fischer glycosylation step and an aminolysis step (Sari-Chmayssem et al., 2016) [13].
  • the inventors have therefore developed a novel process, without solvent, using biocompatible / biodegradable reagents, to simply access surfactant compositions based on alkyl L-iduronamide, alkyl L-rhamnoside and Alkyl D-glucuronamide, directly from ulvans or green algae. Ulvans are for example extracted from the green alga Ulva lactuca or
  • the subject of the present invention is therefore a process for the preparation of a composition
  • a composition comprising a mixture of alkyl D-glucuronamides of formula (I) in the pyranoside form of formula (Ia) and of furanoside of formula (Ib), of L - Alkyl iduronamide of formula (II), and of alkyl L-rhamnoside of formula (III):
  • Ri is an alkyl linear chain of 2 to 22 carbon atoms linear or branched, saturated or unsaturated;
  • R2 is a hydrogen, Ri, a linear or branched, saturated or unsaturated alkyl chain of 2 to 22 carbon atoms containing an amino terminal function;
  • step b) an aminolysis reaction step on the reaction medium resulting from step a), in the presence of an amine of formula R'Nh where R 'is composed of 2 to 22, preferably of 8 to 18, preferentially from 12 to 18 carbon atoms, linear or branched, saturated or unsaturated.
  • the term "ulvans” is understood to mean sulfated anionic polysaccharides dissolved in water, extracted from green algae of the ulva or enteromorphic type.
  • green algae in the sense of the present invention is meant a set of algae whose main photosynthetic pigments are chorophylls a and b. They include various organisms whose sizes can range from a few millimeters to more than one meter and whose aspects can be very diverse. Green algae are represented by the following groups: Euglenophyceae, Chlorarachniophyta, Chlorophytes, Chlorokybophyceae, Klebsormidiophyceae, Zygnematophyceae, Chaetosphaeridiophyta, Charophyceae, and Coleochaetales. Examples of green algae species include Caulerpa taxifolia, Chara globularis, Ulva lactuca, Ulva linza and Boergesenia forbesii.
  • said method comprises, before step a), a step of preparing ulvans.
  • the supernatant containing the ulvans is purified (elimination of polyphenol contaminants) by precipitation with ethanol (2.5 to 3 times the volume of the aqueous solution containing ulvans) and the precipitated ulvans are neutralized with an aqueous solution of 0.1 M NaOH and the solution is lyophilized to yield ulvans in the form of sodium salts (white solid).
  • the chemical composition of ulvan is characterized for example by a molar mass of 565100 g.
  • the butanolysis and glycosylation step of Fisher a) is carried out in the presence of (i) water and / or an ionic solvent and / or a eutectic solvent, (ii) a linear or branched, saturated or unsaturated ROH alcohol having 1 to 4 carbon atoms, preferably n-butanol, and (iii) an acidic catalyst such as, for example, hydrochloric acid sulfuric acid, an alkyl sulfuric acid such as decyl or lauryl sulfuric acid, a sulphonic acid such as benzenesulphonic acid, paratoluene sulphonic acid, camphorsulphonic acid, an alkylsulphonic acid such as methylsulphonic acid, (AMS), decylsulfonic acid, laurylsulfonic acid, sulfosuccinic acid or an alkyl sulfosuccinate such as decyl sulfo
  • an acidic catalyst such as, for
  • ionic solvent is understood to mean, for example, 1-butyl-3-methylimidazolium chloride [BMIM] CI, 1-butyl-3-methylimidazolium bromide [BMIM] Br, tris methylsulfate and the like. - (2-hydroxyethyl) methylammonium (HEMA) and 1-ethyl-3-methylimidazolium acetate [EMIM] AcO; said ionic solvent typically comprising up to 10% water.
  • BMIM 1-butyl-3-methylimidazolium chloride
  • BMIM 1-butyl-3-methylimidazolium bromide
  • HEMA 2-hydroxyethyl) methylammonium
  • EMIM 1-ethyl-3-methylimidazolium acetate
  • eutectic solvent within the meaning of the present invention is meant systems formed of a eutectic mixture of bases or Lewis or Bronsted acids which may contain a variety of anionic species and / or cationic species.
  • the first generation eutectic solvents were based on mixtures of quaternary ammonium salts with hydrogen bonding donors such as amines and carboxylic acids (eg quaternary ammonium salt and (hydrate of) metal chloride.
  • This step a) is carried out, for example, by bringing into contact an equivalent of ulvan with a molar mass of between 150,000 and 3,600,000 g. mol "1 , preferably about 560000 g, mol- 1 , from Ulva linza or Ulva lactuca; 10 to 1000 molar equivalents of water, and preferably 500 molar equivalents; From 2 to 300 molar equivalents of an alcohol as defined above, for example n-butanol, and preferably 150 molar equivalents; 10 "3 to 10 molar equivalents of an acid catalyst, such as hydrochloric acid, sulfuric acid, an alkyl sulfuric acid such as decyl or lauryl sulfuric acid, a sulfonic acid such as benzenesulphonic acid, para-toluenesulfonic acid, camphorsulfonic acid, an alkylsulfonic acid such as methylsulfonic acid, decylsulfonic acid, lauryls
  • composition thus formed consists mainly of (n-alkyl) -n-alkyl L-iduronate, (n-alkyl) -n-alkyl D-glucuronate and n-alkyl L-rhamnoside (with, for example, the alkyl group which corresponds to butyl in the case of the use of butanol).
  • said method may further comprise a step a ') of neutralization of the reaction medium resulting from step a), and carried out before step b), leading to a final composition including a variable amount of residual fatty amine salt.
  • the neutralization step is carried out in the presence of 1 M sodium hydroxide, up to a pH of 7.
  • the reaction is carried out at a temperature of preferably 65-70 ° C and under reduced pressure for the recycling of the above-mentioned alcohol.
  • the aminolysis reaction is carried out according to the two protocols below:
  • R'Nh linear or branched, saturated or unsaturated where R 'is composed of 2 to 22 carbon atoms, and preferably 3 molar equivalents.
  • the fatty amine is selected from the group consisting of dodecylamine and oleic amine.
  • the reaction is conducted at a temperature of preferably 65-70 ° C and under reduced pressure for the recycle of the above-mentioned alcohol.
  • the composition thus formed constitutes a product of use derived from L-iduronic acid and D-glucuronic acid in the form of amides and rhamnose in the form of glycoside as emulsifiers.
  • the unreacted salts and sugars can be removed from this composition by taking up in an organic solvent, preferably diethyl ether, and then filtered and rinsed several times with the organic solvent.
  • the filtrate containing the L-iduronamides, L-rhamnosides and alkyl D-glucuronamides is concentrated to give a composition enriched in products of interest which also constitutes a product of use such as an emulsifying agent having antibacterial and antifungal properties at the concentrations used for emulsion formation.
  • the fatty amine is selected from the group consisting of dodecylamine and oleic amine.
  • the reaction is conducted at a temperature of preferably 65-70 ° C and under reduced pressure for the recycling of the aforementioned alcohol.
  • from 100 to 1000 molar equivalents of water, preferably 500 equivalents are added to the medium.
  • the mixture is stirred for about 15 minutes at 65-70 ° C.
  • the medium is left for about 10 minutes at this same temperature so that the organic products flocculate.
  • the organic phase solidifies and it is then easy to remove the salt-laden water according to techniques well known to those skilled in the art.
  • the preparation of a composition comprising L-iduronamide derivatives, L-rhamnosides and alkyl D-glucuronamides, where the alkyl chain is longer, is continued by a step c) trans-glycosylation carried out on this composition resulting from step b) or on one or more isolated / purified derivatives of this composition by means well known to those skilled in the art (eg silica gel column chromatography) , for example on L-rhamnoside derivatives, in the presence of an alcohol of formula R'OH, linear or branched, saturated or unsaturated, where R 'is composed of 2 to 22, preferably 8 to 18, preferably 12 at 18, carbon atoms.
  • the alcohol R'OH is selected from the group consisting of linear, saturated or unsaturated fatty alcohols such as dodecanol and oleic alcohol.
  • This trans-glycosylation step c) is carried out, for example, by introducing into the reaction medium resulting from step b) from 2 to 50 molar equivalents of an alcohol of formula R'OH as defined above, and preferably 15 molar equivalents; 10 "3-10 molar equivalents of an acid catalyst as defined above, and preferably from 0.1 to 10 molar equivalents of alkyl sulfonic acid, and preferably 1 molar equivalent of methanesulfonic acid.
  • reaction trans-glycosylation is then continued to recycle the short-chain alcohol ROH previously used for the formation of the composition rich in (n-alkyl) -n-alkyl L-iduronate, (n-alkyl) -n-alkyl-D
  • the reaction is carried out for 1 hour to 24 hours at a temperature preferably of 70 ° C. and under reduced pressure for the recycling of the above-mentioned alcohol.
  • product derived from L-acid iduronic acid and D-glucuronic acid in the form of amides and rhamnose in the form of glycoside such as a hydrophone agent, a non-ionic detergent or an emulsifying agent.
  • a neutralization step d) of the reaction medium resulting from stage c), once brought back to ambient temperature and at atmospheric pressure, can be carried out in the presence of (i) water and (ii) an M (OH) x base in which M is an alkali or alkaline earth metal, and x is valence.
  • This step d) is carried out, for example, by introducing into the reaction medium resulting from stage c), once brought back to room temperature and at atmospheric pressure, from 0 to 19 molar equivalents of an aqueous solution containing a base of M (OH) x formula as defined above, and preferably 2.2 equivalents of a solution of sodium hydroxide (NaOH) 1 N; from 100 to 1000 molar equivalents of water and preferably 780 molar equivalents. Then, the whole is heated to 80 ° C with vigorous stirring for 15 min. Once the mixture has returned to room temperature, the aqueous phase is separated from the organic phase. The latter is finally dried by azeotropic distillation of the water using butanol.
  • the excess alcohol of formula R'OH present in the organic crude may be partially or completely removed by molecular distillation. After a possible purification by chromatography on silica gel (ChbC / MeOH 97: 3 then 96: 4 then 90:10), a product mixture is obtained.
  • the mass composition is about 10% alkyl L-iduronamides, 50% alkyl L-rhamnosides, and 40% alkyl D-glucuronamides.
  • compositions thus formed by the process of the invention constitute useful products derived from L-iduronic acid and D-glucuronic acid in the form of amides and rhamnose in the form of glycosides, such as emulsifiers having anti-bacterial and / or antifungal properties at the concentrations used for emulsion formation.
  • the present invention also relates to a composition obtained by a method according to the invention.
  • the compositions of the invention consist of L-iduronic acid derivatives and D-glucuronic acid in the form of amides and rhamnose in glycoside form.
  • the amide derivatives of the acid D-glucuronic acid are in the form of both pyranosides (6-membered ring) and furanosides (5-membered rings), whereas amide derivatives of L-iduronic acid and L-rhamnose glycosides are exclusively in the form of pyranoside.
  • compositions of the invention are considered as emulsifiers for water-in-oil (W / O) or oil-in-water (O / W) emulsions. .
  • they may have antibacterial and antifungal properties.
  • the present invention also relates to the use of a composition according to the invention as a surfactant.
  • said surfactant is selected from the group consisting of solubilizing, hydrotropic, wetting, foaming, emulsifying, emulsifying and / or detergent agents.
  • composition according to the invention is also the use of a composition according to the invention as an antibacterial and / or antifungal agent.
  • the present invention also relates to a surfactant comprising a composition according to the invention.
  • Said surfactant may have the following properties:
  • the present invention also relates to antifungal and / or antibacterial comprising a composition according to the invention.
  • the process of the invention leads to novel surfactant compositions using exclusively biobased raw materials (ulvan, green algae) or biocompatible / biodegradable raw materials:
  • the process of the invention thus makes it possible to produce compositions derived from L-iduronic acid and D-glucuronic acid in the form of amides and rhamnose in the form of glycoside which have the advantage of forming water emulsions. in oil (W / O) and oil in water (W / O) very stable in comparison with commercial emulsifiers, and possess antibacterial and antifungal properties at the concentrations used for the formation of emulsions.
  • the process of the invention makes it possible at the same time to reduce the production costs of the surfactant compositions and to propose new compositions with a view to improving performance (emulsifying properties in particular).
  • the presence of uronic sugars and rhamnose contributes to interesting biological activities in addition to surfactant properties.
  • the presence of rhamnoside in the surfactant composition can therefore provide valuable biological activities in several fields and in particular in cosmetics.
  • Other advantages may still appear to those skilled in the art on reading the examples below, illustrated by the appended figures, given for illustrative purposes.
  • Figure 1 shows the measurement of the emulsifying power of the surfactant composition UlvC 4 Ni2 (A) W / O emulsion and (B) O / W emulsion, in comparison with commercial references Montanov ® and Xyliance ® .
  • EXAMPLE 1 METHOD FOR OBTAINING COMPOSITIONS BASED ON ALKYL IDURONAMIDES, ALKYL D-GLUCURONAMIDES AND ALKYL L-RHAMNOSIDES FROM ULVANES
  • pH 0.5 M hydrochloric acid
  • the temperature of the medium was lowered to 60 ° C before adding 3 molar equivalents of C12H25NH2 dodecylamine (34.21 mmol, 7.86 grams) necessary to increase the pH to 8.5.
  • the butanol was evaporated while reducing the pressure of 150 mbar at 6 mbar under a period of 1 hour.
  • the medium was left under reduced pressure of 6 mbar and at 65 ° C. for 1.5 hours to ensure the evaporation of the traces of butanol which have formed.
  • the residue obtained was taken up in diethyl ether and then filtered on sintered and rinsed several times with diethyl ether to remove the salts and the unreacted starting sugar.
  • the filtrate (containing butyl rhamnoside, dodecyl glucuronamides and iduronamides) is concentrated in vacuo to give a dark brown oil.
  • the surfactant composition UlvC 4 Ni 2 is then formed of n- (12-dodecyl) -n-butyl ⁇ -D-glucurofuranosiduronamide (47%), n- (12-dodecyl) -n-butyl ⁇ -D-glucuropyranosiduronamide (26%), n- (12-dodecyl) -n-butyl ⁇ -D-glucuropyranosiduronamide (7%), n- (12-dodecyl) -n-butyl aL-iduronopyranosiduronamide (20%).
  • the proportions of the form furanose (a) and pyranose forms (a and ⁇ ) in the mixtures UlvC 4 Ni2 made it possible to evaluate a ratio pyranose / furanose.
  • the value of the pyranose / furanose ratio is of the order of 1 .12 for the mixture UlvC 4 Ni2 indicating that the pyranose forms (a and ⁇ ) of n-dodecyl n-butyl D-glucuronamide and n-dodecyl n-butyl L-iduronamide are predominant with respect to the form furanose of n dodecyl n-butyl D-glucuronamide.
  • N-Butyl ⁇ -Lhamnopyranoside (0.5 g, 2.27 mmol, 1 equiv.) Separated from the surfactant composition UlvC 4 Ni 2 by silica gel column chromatography was taken up in dodecanol (15 equiv.) In the presence of an equivalent of AMS (2.27 mmol, 148 ⁇ ). The transglycosylation was then carried out for 3 hours at 65 ° C. under reduced pressure (6 mbar) in a sufficiently diluted medium in order to avoid degradation of the butyl rhamnoside. At the end of the reaction, the reaction medium was allowed to cool and then neutralized with a solution of NaOH (0.1 M).
  • the interfacial properties of the surfactant composition UlvC 4 Ni 2 were evaluated via the measurement of oil-water interfacial tensions.
  • the surfactants were solubilized in sunflower oil at concentrations ranging from 0.12 to 0.46 g / L. In order to promote the solubility of the surfactants in the oil, the solutions were left in an ultrasonic bath for 10 minutes at 50 ° C. The interfacial tension measurements were made between Milli-Q water and the sample solutions in the oil.
  • Measurements of the voltages at the interface between the oil and the water were carried out at 25 ° C. with a ring tensiometer (Kruss, model K 100C).
  • the ring used was platinum iridium calibrated suspended horizontally. Before each measurement, the ring was thoroughly cleaned and flame dried.
  • the bucket for sample is a cylindrical glass container placed in a thermoregulated chamber.
  • the interfacial tension between sunflower oil (Carrefour brand) and water at 25 ° C varied between 24.71 and 25.04 mN / m.
  • the apparatus For each concentration of the surfactant composition, the apparatus initially measured the surface tension of the sunflower oil containing the surfactant (low density liquid) and then the surface tension of the water (high density liquid). Finally, the oil was gently added to the water, while avoiding the formation of bubbles, the device began to measure the interfacial tension between sunflower oil and water (average of 10 measurements).
  • the surfactant composition UlvC 4 Ni2 is capable of reducing the interfacial tension to a value of 10.32 mN / m at a concentration of 0.46 g / L to give the composition emulsifying powers.
  • EXAMPLE 3 MEASURING THE EMULSIFYING POWER OF SURFACE-FREE COMPOSITIONS BASED ON L-IDURONAMIDES OF ALKYL AND D-GLUCURONAMIDES OF ALKYL FROM ULVANES
  • the stability of the two types of O / W emulsions and W / O were evaluated by considering the two water / oil ratios 75/25 and 25/75 respectively in round bottom graduated tubes, 0.5% of the surfactant product is introduced ( 20 mg). Sunflower oil was introduced (1 or 3 mL), then the surfactants were solubilized in an ultrasonic bath for 10 minutes at 50 ° C. After solubilization of the emulsifier, the ultrapure water was added (1 or 3 ml).
  • the two phases were then emulsified using an Ultraturraxika T18 basic ® homogenizer for 10 minutes at 1000 rpm.
  • the emulsion was placed in a bath thermostated at 20 ° C.
  • Figure 1 shows the results of analysis of the emulsifying power of the compositions of the invention.
  • the surfactant composition UlvC 4 Ni 2 derived from dodecylamine has led to an O / W emulsion characterized by a high stability ranging from several weeks to several months.
  • the W / O emulsion formed by the product UlvC 4 Ni 2 is very stable.
  • EXAMPLE 4 ANTIBACTERIAL ACTIVITY OF SURFACTANT COMPOSITIONS BASED ON L-IDURONAMIDES OF ALKYL, OF D- ALKYL GLUCURONAMIDES AND ALKYL L-RHAMNOSIDES FROM ULVANES
  • Protocol A Diffusion Method on Agar in Petri dishes
  • the culture medium used was a mixture of 21 g / L Muller Hinton Broth and 10 g / L agar in water. This mixture was stirred and allowed to boil. Then, a step of autoclaving this mixture, for 30 minutes, was necessary in order to sterilize it before any manipulation. This culture medium was poured, hot, into petri dishes and then allowed to cool.
  • the bacterial strains used were Pseudomonas aeruginoa,
  • Escherichia coli, Enterococcus faecium and Staphylococcus aureus in addition to the fungal strain Candida albicans. June 10 bacteria were collected and transferred in a 0.9% NaCl solution. Each petri dish, containing Muller Hinton medium, was flooded with a different bacterial suspension.
  • the positive controls used were ampicillin-soaked disks for
  • Escherichia coli and Enterococcus faecium ceftazidime disks for Pseudomonas aeruginosa and vancomycin disks for Staphylococcus aureus.
  • the Petri dishes were finally incubated at 37 ° C. in the oven for 24 hours.
  • the antibacterial activity was evaluated by measuring the clarification zone in mm around the place of deposition of the different concentrations of the RhamOC 4 solution to be tested.
  • Rhamnoside RhamOC 4 exhibited a very good ability to inhibit the growth of gram-positive bacteria Staphylococcus aureus and yeast Candida albicans. Its potency against Enterococcus faecium (6 mm at 5 mg.mL "1 ) was average, and rhamnoside RhamOC 4 showed an inhibitory activity of the gram negative bacterium Escherichia coli at concentrations 2.5 and 5 mg.mL " 1 with a weak inhibitory capacity of the growth of Pseudomonas aeruginosa.
  • Protocol B Method for Evaluating Number of Living Bacteria The antibacterial and antifungal activities of the surfactant composition UlvC 4 Ni 2 were evaluated. In this context, the ability of this monosaccharide surfactant composition to kill bacteria has been studied by counting the number of living bacteria on Muller-Hinton agar.
  • the inoculum was prepared at a turbidity equivalent to 0.5 MacFarland (Biomérieux France), then diluted to 1/100 (10 6 CFU / ml)
  • each tube of the surfactant dilutions 1 ml of the bacterial inoculum was added. After incubation for 24 h at 36 ° C., 100 ⁇ l of each clear tube was spread on the surface of a Muller-Hinton agar followed by incubation for 24 hours at 37 ° C.
  • the percentage of living bacteria was calculated: ⁇ 0 / ⁇ ⁇ 100.
  • the minimum concentration of 100% inhibition of Enterococcus faecium and Candida albicans was of the order of 1.58 mg.mL -1 for the monosaccharide surfactant composition based on D-glucuronic and L-iduronic acids.
  • very high concentrations of UlvC 4 Ni2 were required to 100% inhibit both these bacteria showing that UlvC 4 Ni2 (25.375 mg.mL "1 ) has a low antibacterial power against both types of bacteria.
  • the hydrophobic carbon chain could interact with the lipid membrane of the gram-positive bacterium thus promoting its deformation and subsequently bacterial cell death (Reis et al., J. Brazilian Chem. Soc., 19 (6), 1065-1072, 2008) [12].

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Biotechnology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Molecular Biology (AREA)
  • Genetics & Genomics (AREA)
  • Biochemistry (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Dispersion Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Communicable Diseases (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Oncology (AREA)
  • Dermatology (AREA)
  • Toxicology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Botany (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
EP17821978.8A 2016-12-12 2017-12-11 Verfahren zur herstellung von tensidzusammensetzungen mit alkyl l-iduronamiden, d-glucuronamiden und l-rhamnosiden aus ulvanen Withdrawn EP3551640A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1662342A FR3060005A1 (fr) 2016-12-12 2016-12-12 Procede de preparation de compositions tensioactives comprenant des l-iduronamides, d-glucuronamides et l-rhamnosides d'alkyle a partir d'ulvanes
PCT/FR2017/053501 WO2018109348A1 (fr) 2016-12-12 2017-12-11 Procédé de préparation de compositions tensioactives comprenant des l-iduronamides, d-glucuronamides et l-rhamnosides d'alkyle à partir d'ulvanes

Publications (1)

Publication Number Publication Date
EP3551640A1 true EP3551640A1 (de) 2019-10-16

Family

ID=58455176

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17821978.8A Withdrawn EP3551640A1 (de) 2016-12-12 2017-12-11 Verfahren zur herstellung von tensidzusammensetzungen mit alkyl l-iduronamiden, d-glucuronamiden und l-rhamnosiden aus ulvanen

Country Status (4)

Country Link
US (1) US20200045962A1 (de)
EP (1) EP3551640A1 (de)
FR (1) FR3060005A1 (de)
WO (1) WO2018109348A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2021007992A (es) * 2019-01-08 2021-11-04 Isdin Sa Composiciones para uñas con propiedades antifúngicas.

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2670345A (en) 1949-04-05 1954-02-23 Charles L Mehltretter Substituted gluconamides
PL168355B1 (pl) 1990-10-12 1996-02-29 Procter & Gamble Sposób wytwarzania N-polihydroksyalkiloamin PL PL PL PL PL PL
CA2114106C (en) 1991-07-26 2002-05-28 Junan Kao Process for preparing n-alkyl polyhydroxyalkyl amines in aqueous/hydroxy solvents
GB9121279D0 (en) 1991-10-08 1991-11-20 Cerestar Holding Bv Process for the production of aminopolyols
US5872111A (en) 1997-05-19 1999-02-16 Lever Brothers Company, Division Of Conopco, Inc. Compositions comprising glycosylamide surfactants
FR2840306B1 (fr) 2002-05-29 2005-07-01 Ct D Etude Et De Valorisation Derives d'acide(alkyl d-mannopyranoside) uronique, des procedes pour leur preparation, ainsi que leurs applications
US7655611B2 (en) 2004-12-14 2010-02-02 The University Of Houston System Structural family on non-ionic carbohydrate based surfactants (NICBS) and a novel process for their synthesis

Also Published As

Publication number Publication date
WO2018109348A1 (fr) 2018-06-21
FR3060005A1 (fr) 2018-06-15
US20200045962A1 (en) 2020-02-13

Similar Documents

Publication Publication Date Title
Rikalović et al. Rhamnolipid biosurfactant from Pseudomonas aeruginosa: from discovery to application in contemporary technology
WO2015074750A1 (de) Teilkristalline glucamid-zusammensetzungen und verfahren zu deren herstellung
Dengle Pulate et al. Microbial oxidation of medium chain fatty alcohol in the synthesis of sophorolipids by Candida bombicola and its physicochemical characterization
DE19749413A1 (de) Neuartige Sophoroselipide, Verfahren zu deren Herstellung und Verwendung
WO1986002076A1 (fr) Derives d'hydrates de carbone tensioactif et procede pour leur preparation
Sari-Chmayssem et al. Direct and one-pot conversion of polyguluronates and alginates into alkyl-L-guluronamide-based surfactant compositions
Bhangale et al. Optimization and monitoring of water soluble substrate for synthesis of mannosylerythritol lipids by Pseudozyma antarctica (ATCC 32657)
EP1682158B9 (de) Kosmetische Zusammensetzung enthaltend mindestens ein Rhamnosemonomer zur kosmetische Behandlung der Haut
EP3551640A1 (de) Verfahren zur herstellung von tensidzusammensetzungen mit alkyl l-iduronamiden, d-glucuronamiden und l-rhamnosiden aus ulvanen
Benvegnu et al. Oligomannuronates from seaweeds as renewable sources for the development of green surfactants
EP1211258B1 (de) Verfahren zur Herstellung von Solubilisierzusatzstoffen aus Fuselölen und Osen
EP3560916A1 (de) Syntheseverfahren von 5-dialkylazetal-2-furoaten von alkyl, und ihre verwendung für die zubereitung von biobasierten tensiden
FR3044876B1 (fr) Procede d'obtention de compositions tensioactives a base de l-guluronamides d'alkyle
EP3386999B1 (de) Verfahren zur herstellung von zusammensetzungen (alkylgulosid)alkyl uronsäurederivate enthaltend, diese zusammensetzungen und ihre verwendung als tensid
FR2892119A1 (fr) Produit resultant du greffage de chaines grasses sur des ulvanes et son utilisation comme tensioactif
EP2350108B1 (de) C-glycosidverbindungen und verfahren zur herstellung von c-glycosidverbindungen
EP3271369B1 (de) Verfahren zur herstellung von derivaten und zusammensetzungen auf galacturonsäure-basis direkt aus pektinen
US11192913B2 (en) C-glycoside amine derivatives and methods of making
CN118974068A (zh) 生物基表面活性剂
EP1589022B1 (de) Verfahren zur Herstellung eines Gemischs enthaltend Fettalkohole und APG- ethercarboxylat
Zhu Aldolisation of unprotected ketoses to surfactants
FR2727110A1 (fr) Composes amphiphiles mixtes
Hibert Glycolipids: from synthesis and self-assembly studies to the design of original bio-based polymers
Benvegnu et al. Springer-Verlag Berlin Heidelberg 2010 Published online: 23 March 2010
Pratap et al. Current Research in Green and Sustainable Chemistry

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190529

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20201016

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20210227