FR2713638A1 - New, quaternised, water-soluble, zwitterionic, glycoside tensides - Google Patents
New, quaternised, water-soluble, zwitterionic, glycoside tensides Download PDFInfo
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- FR2713638A1 FR2713638A1 FR9315014A FR9315014A FR2713638A1 FR 2713638 A1 FR2713638 A1 FR 2713638A1 FR 9315014 A FR9315014 A FR 9315014A FR 9315014 A FR9315014 A FR 9315014A FR 2713638 A1 FR2713638 A1 FR 2713638A1
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- zwitterionic
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- glycoside surfactants
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 15
- 229930182470 glycoside Natural products 0.000 title claims description 10
- 150000002338 glycosides Chemical class 0.000 title claims description 10
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 125000002519 galactosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 claims abstract description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 235000000346 sugar Nutrition 0.000 claims description 7
- 238000005956 quaternization reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000006268 reductive amination reaction Methods 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- -1 CO2- Chemical group 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000002596 lactones Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000008053 sultones Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000003586 protic polar solvent Substances 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- KGQCLZJFUIPDGS-UHFFFAOYSA-N dioxaphospholane Chemical compound C1CPOO1 KGQCLZJFUIPDGS-UHFFFAOYSA-N 0.000 claims 1
- 239000003880 polar aprotic solvent Substances 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 12
- 239000002904 solvent Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- YHJIBZIWMKJSHX-WJFTUGDTSA-N (2r,3r,4r,5s)-6-[dodecyl(methyl)amino]hexane-1,2,3,4,5-pentol Chemical compound CCCCCCCCCCCCN(C)C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO YHJIBZIWMKJSHX-WJFTUGDTSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002888 zwitterionic surfactant Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UMCMPZBLKLEWAF-BCTGSCMUSA-N 3-[(3-cholamidopropyl)dimethylammonio]propane-1-sulfonate Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCC[N+](C)(C)CCCS([O-])(=O)=O)C)[C@@]2(C)[C@@H](O)C1 UMCMPZBLKLEWAF-BCTGSCMUSA-N 0.000 description 1
- 108010052285 Membrane Proteins Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UYVXZUTYZGILQG-UHFFFAOYSA-N methoxyboronic acid Chemical class COB(O)O UYVXZUTYZGILQG-UHFFFAOYSA-N 0.000 description 1
- OMEMQVZNTDHENJ-UHFFFAOYSA-N n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCNC OMEMQVZNTDHENJ-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/56—Glucosides; Mucilage; Saponins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/18—Quaternary ammonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Saccharide Compounds (AREA)
Abstract
Description
DESCRIPTION DE L'INVENTION
Au même titre que les tensioactifs ioniques et non ioniques, les amphiphiles zwitterioniques possèdent d'intéressantes propriétés d'autoassociation en solution à l'origine de la formation d'agrégats dans l'eau et dans d'autres milieux polaires. Ils suscitent désormais un intérêt grandissant lié à leurs propriétés particulières. En solution, ils présentent l'avantage, par exemple, d'être très peu sensibles aux variations de force ionique, de pH ou de température [Fernley G.W. J. Am. Oil Chem. Soc., 1978, 55, 98 ; Noble W.R., Linfield W.M. J. Am. Oil Chem. Soc., 1980, 57, 368], contrairement aux solutions de tensioactifs ioniques qui sont sensibles à la force ionique et qui précipitent en solution aqueuse en présence d'ions multivalents.DESCRIPTION OF THE INVENTION
Like ionic and nonionic surfactants, zwitterionic amphiphiles have interesting self-association properties in solution that cause aggregation in water and other polar media. They are now attracting growing interest related to their particular properties. In solution, they have the advantage, for example, of being very insensitive to changes in ionic strength, pH or temperature [Fernley GWJ Am. Oil Chem. Soc., 1978, 55, 98; Noble WR, Linfield WMJ Am. Oil Chem. Soc., 1980, 57, 368], in contrast to solutions of ionic surfactants which are sensitive to ionic strength and which precipitate in aqueous solution in the presence of multivalent ions.
D'autre part, le phénomène de démixion ou point de trouble observé dans le cas de certains tensioactifs non ioniques ne l'a jamais été avec les tensioactifs zwitterioniques [Nilsson P., Lindman B., Laughlin R.G. J. Phys. Chem., 1984, 88, 6357]. On the other hand, the phenomenon of demixing or cloud point observed in the case of some nonionic surfactants has never been with zwitterionic surfactants [Nilsson P., Lindman B., Laughlin R.G. J. Phys. Chem., 1984, 88, 6357].
En outre, la coexistence d'un groupe cationique et d'un groupe anionique leur assure une complète neutralité électrique, ce qui leur confere des propriétés communes à la fois aux amphiphiles ioniques et non ioniques. In addition, the coexistence of a cationic group and an anionic group ensures complete electrical neutrality, which gives them properties common to both ionic and nonionic amphiphiles.
La nature ambivalente de leur tête polaire se traduit par des applications dans la formulation de nombreux produits cosmétiques et produits de soin, shampooings, etc..., dans l'industrie textile où ils interviennent comme adoucissants, dans l'industrie alimentaire, dans des applications biologiques et médicales, etc... The ambivalent nature of their polar head results in applications in the formulation of many cosmetic products and skincare products, shampoos, etc ..., in the textile industry where they act as softeners, in the food industry, in biological and medical applications, etc.
Bien qu'il existe un nombre important de groupes fonctionnels organiques susceptibles de conférer un caractère zwitterionique à des amphiphiles, les dérivés de l'imidazoline, les bétaïnes et les sulfobétaines, ainsi que les lécithines et phosphatides constituent les principaux matériaux tensioactifs de nature zwitterionique actuellement rencontrés [Myers D. Sulfatant Science and Technology, VCH Publishers, Inc. (1988) pp74]. Although there are a large number of organic functional groups capable of imparting a zwitterionic character to amphiphiles, imidazoline derivatives, betaines and sulfobetaines, and lecithins and phosphatides are the main surfactants of zwitterionic nature at present. encountered [Myers D. Sulfating Science and Technology, VCH Publishers, Inc. (1988) pp74].
Dans l'étude des biomembranes, parmi les détergents zwitterioniques disponibles commercialement ne figurent que le CHAPS et la série des N-alkylsulfobétaïnes ou
Zwittergents [Gonenne A., Ernst R. Anal. Biochem., 1978, 87, 28]. Au niveau de l'extraction de certains complexes membranaires, il a été montré que la capacité d'extraction des
Zwittergents augmentait avec la longueur de la chaîne allyle [Byers S., Hopkins T.J., Kuettner
K.E., Kimura J.H. J. Biol. Chem., 1987, 262, 9166], capacité rapidement limitée cependant par un facteur limitant: la solubilité dans l'eau.In the study of biomembranes, commercially available zwitterionic detergents include only CHAPS and the series of N-alkylsulfobetaines or
Zwittergents [Gonenne A., Ernst R. Anal. Biochem., 1978, 87, 28]. At the level of the extraction of certain membrane complexes, it has been shown that the extraction capacity of
Zwittergents increased with the length of the allyl chain [Byers S., Hopkins TJ, Kuettner
KE, Kimura JHJ Biol. Chem., 1987, 262, 9166], capacity quickly limited however by a limiting factor: the solubility in water.
De plus, l'utilisation de ces Zwittergents en membranologie se limite à la solubilisation et à l'extraction des protéines membranaires, les tentatives de purification et de caractérisation physique de ces dernières en présence de N-alkylsulfobétaïnes laissant apparaître un caractère dénaturant important [Hjelmeland L.M., Nebert D.W., Chrambach A. Anal. In addition, the use of these zwittergents in membranology is limited to the solubilization and extraction of membrane proteins, the attempts of purification and physical characterization of the latter in the presence of N-alkylsulfobetaines revealing a significant denaturant character [Hjelmeland LM, Nebert DW, Chrambach A. Anal.
Biochem., 1979, 95, 201; Hjelmeland L.M., Nebert D.W., Osborne Jr J.C. Anal. Biochem., 1983, 130, 72]. Biochem., 1979, 95, 201; Hjelmeland L.M., Nebert D.W., Osborne Jr.C. Anal. Biochem., 1983, 130, 72].
I1 apparaît donc que la recherche de nouveaux tensioactifs zwitterioniques très hydrosolubles et peu dénaturants vis-à-vis des matériaux biologiques est d'un intérêt fondamental. A la différence de l'art antérieur, la présente invention vise de nouveaux tensioactifs zwitterioniques comportant une entité biocompatible de nature glucidique au niveau de la tête polaire. Cette invention décrit donc la synthèse de nouveaux amphiphiles zwitterioniques et glycosidiques en deux étapes à partir de sucres naturels, ainsi que leurs propriétés tensioactives. It thus appears that the search for new zwitterionic surfactants that are highly water-soluble and not very denaturing with regard to biological materials is of fundamental interest. Unlike the prior art, the present invention relates to novel zwitterionic surfactants comprising a biocompatible entity of carbohydrate nature at the polar head. This invention therefore describes the synthesis of novel zwitterionic and glycosidic amphiphiles in two stages from natural sugars, as well as their surfactant properties.
L'invention vise des tensioactifs glycosidiques et zwitterioniques de formule générale:
R1 étant une chaîne aliphatique saturée ou insaturée, linéaire ou ramifiée comportant de 1
à 18 atomes de carbone
n représentant le nombre d'atomes de carbone sur le bras intercharge ; celui-ci peut
varierde 1 à 10
Y représentant un groupe anionique tel que CO2-, S03-, OSO3-, OPROIL-, PRO2-, etc
R2 représentant un atome d'hydrogène ou un groupe glucosyle ou galactosyle.R1 being a saturated or unsaturated aliphatic chain, linear or branched having 1
at 18 carbon atoms
n represents the number of carbon atoms on the intercharge arm; this one can
vary from 1 to 10
Y representing an anionic group such as CO2-, S03-, OSO3-, OPROIL-, PRO2-, etc.
R2 represents a hydrogen atom or a glucosyl or galactosyl group.
Selon la présente invention, le procédé de synthèse des tensioactifs glycosidiques zwitterioniques visés consiste à effectuer, dans un premier temps, l'amination réductrice d'un sucre réducteur par une amine primaire ou secondaire en présence d'un réducteur tel que le borohydrure de sodium, l'hydrure d'aluminium ou de lithium, le cyanoborohydrure de sodium ou par hydrogénation catalytique. According to the present invention, the process for the synthesis of the targeted zwitterionic glycoside surfactants consists in initially performing the reductive amination of a reducing sugar by a primary or secondary amine in the presence of a reducing agent such as sodium borohydride. , aluminum or lithium hydride, sodium cyanoborohydride or by catalytic hydrogenation.
Les résultats les plus intéressants sont obtenus en utilisant le D-glucose comme sucre réducteur et le borohydrure de sodium comme agent réducteur. The most interesting results are obtained using D-glucose as reducing sugar and sodium borohydride as reducing agent.
Toujours selon la présente invention, la deuxième étape du procédé de synthèse consiste à effectuer une réaction de quaternisation de l'azote des N-alkylglycamines précédemment citées en procédant à l'ouverture d'hétérocycles (lactones, sultones, sulfates cycliques, dioxaphospholanes, etc...) [Gresham T.L., Jansen J.E., Shaver F.W., Bankert
R.A., Fiedoreck F.T. J. Am. Chem. Soc., 1951, 73, 3168 ; Parris N., Weil J.K., Linfield
W.M. J. Am. Oil Chem. Soc., 1973, 50, 509 ; Phuong N.H., Thuong N.T., Chabrier P.Still according to the present invention, the second step of the synthesis process consists in carrying out a quaternization reaction of the nitrogen of the N-alkylglycamines mentioned above by opening heterocycles (lactones, sultones, cyclic sulphates, dioxaphospholanes, etc. ...) [Gresham TL, Jansen JE, Shaver FW, Bankert
RA, Fiedoreck FTJ Am. Chem. Soc., 1951, 73, 3168; Parris N., Weil JK, Linfield
WMJ Am. Oil Chem. Soc., 1973, 50, 509; Phuong NH, Thuong NT, Chabrier P.
Bull. Soc. Chim. Fr., 1975, 2326] ou en utilisant des halogénures d'alkyle fonctionnalisés [Beckett A.H., Woodward R.J. J. Phare. Pharmacol., 1963, 15, 422; Barnhurst J.D. J. Org.Bull. Soc. Chim. Fr., 1975, 2326] or using functionalized alkyl halides [Beckett A.H., Woodward R.J. J. Lighthouse. Pharmacol., 1963, 15, 422; Barnhurst J.D. J. Org.
Chem., 1961, 26, 4520 ; Parris N., Weil J.K., Linfield W.M. J. Am. Oil Chem. Soc., 1976, 53, 97 ; Germanaud L., Brunel S., Chevalier Y., Le Perchec P. Bull. Soc. Chim. Fr., 1988, 699]. Chem., 1961, 26, 4520; Parris N., Weil J.K., Linfield, W. M. J. Am., Oil Chem. Soc., 1976, 53, 97; Germanaud L., Brunel S., Knight Y., Perchec P. Bull. Soc. Chim. Fr., 1988, 699].
Les résultats les plus intéressants sont obtenus en procédant à l'ouverture d'alkanesultones [Helberger J.H., Nierdel J.B. Ger. Patent, 1957, 1, 018, 421] ou en utilisant des bromoalkanoates d'alkyle [Laughlin R.G. U.S. Patent, 1981, 4, 287, 174]. The most interesting results are obtained by proceeding with the opening of alkanesultones [Helberger J.H., Nierdel J.B. Ger. Patent, 1957, 1, 018, 421] or using alkyl bromoalkanoates [Laughlin, R.G. U.S. Patent, 1981, 4, 287, 174].
En pratique, le procédé de la première étape consiste à mettre en réaction: - 1 équivalent de sucre réducteur - 1 à 1,5 équivalent d'amine primaire ou secondaire dans 10 à 20 équivalents en poids par rapport au sucre d'un solvant pouvant être le méthanol, l'éthanol ou tout autre solvant hydroxylé ou non. On peut également utiliser un mélange de 2 ou plusieurs de ces solvants ou réaliser l'amination réductrice en l'absence de solvant lorsque l'amine est liquide à température ambiante et utilisée en plus large excès (10 à 50 équivalents molaires par rapport au sucre). In practice, the method of the first step consists in reacting: 1 equivalent of reducing sugar -1 to 1.5 equivalents of primary or secondary amine in 10 to 20 equivalents by weight relative to the sugar of a solvent which may be be methanol, ethanol or any other hydroxylated solvent or not. It is also possible to use a mixture of two or more of these solvents or to carry out the reductive amination in the absence of a solvent when the amine is liquid at room temperature and used in greater excess (10 to 50 molar equivalents relative to the sugar). ).
La réaction est réalisée à une température allant de la température ambiante à 1200C mais les meilleurs résultats sont obtenus à 60-65 OC pendant 15 à 30 minutes. Après refroidissement du milieu réactionnel à température ambiante puis à 0 OC, on ajoute 1 à 2 équivalents de réducteur. A la fin de l'addition, la réaction est maintenue de quelques minutes à plusieurs heures en fonction de la température. A température ambiante, la réaction dure généralement de 1 à 5 heures. Après traitement et recristallisation, on isole les Nalkylglycamines sous forme de poudres blanches. The reaction is carried out at a temperature ranging from room temperature to 1200C but the best results are obtained at 60-65 OC for 15 to 30 minutes. After cooling the reaction medium to ambient temperature and then to 0 ° C., 1 to 2 equivalents of reducing agent are added. At the end of the addition, the reaction is maintained for a few minutes to several hours depending on the temperature. At room temperature, the reaction generally lasts from 1 to 5 hours. After treatment and recrystallization, the Nalkylglycamines are isolated in the form of white powders.
En pratique, le procédé de synthèse de la seconde étape consiste à mettre en réaction: - 1 équivalent de N-alkylglycamine - 1 à 1,5 équivalent d'un hétérocycle (lactones, sultones, sulfates cycliques, dioxaphospholanes, etc...) ou d'un halogénure d'alkyle fonctionnalisé dans 20 à 50 équivalents en poids par rapport au substrat d'un solvant organique protique (alcools) ou d'un solvant polaire aprotique (l'acétonitrile). In practice, the synthesis process of the second step consists in reacting: 1 equivalent of N-alkylglycamine-1 to 1.5 equivalents of a heterocycle (lactones, sultones, cyclic sulphates, dioxaphospholanes, etc.) or an alkyl halide functionalized in 20 to 50 equivalents by weight relative to the substrate of a protic organic solvent (alcohols) or an aprotic polar solvent (acetonitrile).
Les réactions sont réalisées à reflux du solvant pendant une durée de 7 heures à plusieurs jours. Après traitement et une purification par flash chromatographie sur colonne de gel de silice, on isole les amphiphiles glycosidiques et zwitterioniques sous forme de critaux blancs. The reactions are carried out at reflux of the solvent for a period of 7 hours to several days. After treatment and purification by flash column chromatography on silica gel, the glycoside and zwitterionic amphiphiles are isolated in the form of white crystals.
La présente invention est illustrée par les exemples suivants, donnés à titre indicatif et non limitatif. The present invention is illustrated by the following examples, given by way of indication and not limitation.
Exemple 1
Préparation de la N-dodécyl-N-méthylglucamine
A une suspension de 12,1 mmoles de D-glucose (2,18 g) dans 25 ml de méthanol anhydre, on ajoute 13,3 mmoles (1,1 équivalent) de N-dodécyl-N-méthylamine. La solution homogène est ensuite portée à reflux 20 à 25 minutes après la totale dissolution du Dglucose. A la solution refroidie à température ambiante puis à 0 OC, on additionne par petites fractions 12,1 mmoles de borohydrure de sodium. Après 2 heures 30 minutes à température ambiante, le mélange réactionnel est neutralisé par quelques gouttes d'acide chlorhydrique.Example 1
Preparation of N-dodecyl-N-methylglucamine
To a suspension of 12.1 mmol of D-glucose (2.18 g) in 25 ml of anhydrous methanol, 13.3 mmol (1.1 equivalents) of N-dodecyl-N-methylamine are added. The homogeneous solution is then brought to reflux 20 to 25 minutes after the total dissolution of Dglucose. To the cooled solution at room temperature and then at 0 ° C., 12.1 mmol of sodium borohydride are added in small portions. After 2 hours 30 minutes at room temperature, the reaction mixture is neutralized with a few drops of hydrochloric acid.
Après évaporation du solvant sous pression réduite, le résidu est repris par une solution méthanolique d'acide chlorhydrique concentré et le solvant est de nouveau chassé sous pression réduite. Cette opération est répétée une nouvelle fois, puis 6 fois avec du méthanol afin d'éliminer les borates de méthyle résiduels. Le résidu blanc est ensuite dissous dans du tampon phosphate pH 7, puis le composé attendu est extrait 3 fois avec un mélange acétate d'éthyle/n butanol (1:1,5 ; v/v). Les phases organiques rassemblées sont lavées 3 fois avec une solution aqueuse de bicarbonate de sodium à 5 % et finalement par de l'eau. Les solvants organiques sont évaporés à 35-40 OC sous pression réduite. On recueille alors 4 g (90 % de rendement) de
N-dodécyl-N-méthylglucamine recristallisé par la suite dans l'éthanol absolu.After evaporation of the solvent under reduced pressure, the residue is taken up in a methanolic solution of concentrated hydrochloric acid and the solvent is again removed under reduced pressure. This operation is repeated once more, then 6 times with methanol in order to remove the residual methyl borates. The white residue is then dissolved in phosphate buffer pH 7, and the expected compound is then extracted 3 times with ethyl acetate / n-butanol (1: 1.5 v / v). The combined organic phases are washed 3 times with a 5% aqueous solution of sodium bicarbonate and finally with water. The organic solvents are evaporated at 35-40 ° C. under reduced pressure. We then collect 4 g (90% yield) of
N-dodecyl-N-methylglucamine subsequently recrystallized from absolute ethanol.
F = 91-920C (EtOH) ; rendement 90 %
CCM [MeOH] : Rf = 0.32 [a]D20 = -80 (c = 1, MeOH).Mp 91-920 ° C (EtOH); 90% yield
TLC [MeOH]: Rf = 0.32 [a] D20 = -80 (c = 1, MeOH).
1H RMN (300 MHz, CD30D) 6 (ppm) : 0.90 (t, 3H, CH3); 1.29 [m, 18H, CH3(CH2)g]; 1.54 (m, 2H, NCH2C) ; 2.33 (s, 3H, NCH3); 2.46 (m, 2H, 2JH-H = 13, N-CH2-CH2); 2.59 (dd, 2H, 2JH-H = 13, 3JH-H = 5.5, H1); 3.64 (dd, 1H, 3JH-H = 5.4, H4) ; 3.69 (m, 1H, 3JH-H = 5.0, H5); 3.75 (dd, 1H, 3JH-H = 4.7, H3); 3.58-3.79 (dd, 2H, 2JH-H = 11, 3JH-H = 5.3, H6); 3.89 (m, 1H, 3JH-H = 4.7, H2).1H NMR (300 MHz, CD30D) δ (ppm): 0.90 (t, 3H, CH3); 1.29 [m, 18H, CH3 (CH2) g]; 1.54 (m, 2H, NCH 2 C); 2.33 (s, 3H, NCH 3); 2.46 (m, 2H, 2H-H = 13, N-CH 2 -CH 2); 2.59 (dd, 2H, 2H-H = 13.3HH = 5.5, H1); 3.64 (dd, 1H, 3H-H = 5.4, H4); 3.69 (m, 1H, 3H-H = 5.0, H5); 3.75 (dd, 1H, 3H-H = 4.7, H3); 3.58-3.79 (dd, 2H, 2H-H = 11, 3H-H = 5.3, H6); 3.89 (m, 1H, 3H-H = 4.7, H2).
13C RMN (75 MHz, CD30D) (ppm) : 14.44 (CH3); 23.71, 27.88, 28.55, 30.45, 30.69, 30.73, 33.05 [CH3(CH2)10]; 42.99 (NCH3); 59.58 (NCH2CH2); 61.52 (C1); 64.91(C6); 71.69 (C2) ; 72.96 (C3); 72.99 (C5); 73.38 (C4).13C NMR (75 MHz, CD30D) (ppm): 14.44 (CH3); 23.71, 27.88, 28.55, 30.45, 30.69, 30.73, 33.05 [CH3 (CH2) 10]; 42.99 (NCH3); 59.58 (NCH2CH2); 61.52 (C1); 64.91 (C6); 71.69 (C2); 72.96 (C3); 72.99 (C5); 73.38 (C4).
SM (CI: NH3) m/z(rel. intens.) : 363 [M]+ (non observé) ; 364(100) [M+H]+.MS (CI: NH 3) m / z (Int.Re): 363 [M] + (not observed); 364 (100) [M + H] +.
Anal. élem. calc. pour C19H41N05 : C, 62.77 ; H, 11.36 ; N, 3.85; 0,22.00 Trouvé: C, 62.91; H, 11.39 ; N, 3.80 ;0, 22.41. Anal. ELEM. calc. for C19H41NO5: C, 62.77; H, 11.36; N, 3.85; 0.22.00 Found: C, 62.91; H, 11.39; N, 3.80, 0, 22.41.
Exemple 2
Préparation du N-dodécyl-N-méthyl glucammonium- 1 -propanesulfonate
6,61 mmoles de N-dodécyl-N-méthylglucamine (2,4 g), 6,61 mmoles de 1,3propanesultone (807 mg) et 50 ml d'acétonitrile distillé sont portés à reflux 3 jours à l'abri de l'humidité atmosphérique. 0,2 à 0,3 équivalent de propanesultone sont ajoutés après 24 heures afin de consommer entièrement le substrat. La sulfobétaine attendue, insoluble dans l'acétonitrile, précipite et est recueillie par filtration. Après sa mise en solution dans du tampon phosphate à pH 7, la phase aqueuse est extraite 2 fois par du dichlorométhane afin d'éliminer toute trace de matériaux organiques résiduels, puis 4 extractions avec un mélange acétate d'éthyle/n-butanol (1:1; v/v) suffisent à réextraire le zwitterion attendu. Après évaporation des solvants organique s sous pression réduite, le résidu est purifié par flash chromatographie sur colonne de gel de silice [éluant MeOH/28-30% NH3/H2O (95:5 ; v/v) puis MeOH]. On recueille alors 2,06 g (64 % de rendement) de N-dodécyl-N-méthylglucammonium-1-propanesulfonate sous la forme de cristaux blancs. rendement 64 %
CCM [MeOH/28-30% NH3/H2O (95:5, v/v)] : Rf = 0.48 [a]D20 = -12 (c = 0.90, H2O)
IR (HCB) v (cm-l): 1175 and 1040 (SO3-). Example 2
Preparation of N-dodecyl-N-methyl glucammonium-1-propanesulfonate
6.61 mmol of N-dodecyl-N-methylglucamine (2.4 g), 6.61 mmol of 1,3-propanesultone (807 mg) and 50 ml of distilled acetonitrile are refluxed for 3 days in a vacuum. atmospheric humidity. 0.2 to 0.3 equivalents of propanesultone are added after 24 hours in order to consume the entire substrate. The expected sulfobetaine, insoluble in acetonitrile, precipitates and is collected by filtration. After being dissolved in phosphate buffer at pH 7, the aqueous phase is extracted twice with dichloromethane in order to remove all traces of residual organic materials, then 4 extractions with ethyl acetate / n-butanol (1 : 1; v / v) are sufficient to re-extract the expected zwitterion. After evaporation of the organic solvents under reduced pressure, the residue is purified by flash chromatography on a column of silica gel (eluent MeOH / 28-30% NH 3 / H 2 O (95: 5 v / v) then MeOH]. 2.06 g (64% yield) of N-dodecyl-N-methylglucammonium-1-propanesulfonate are then collected in the form of white crystals. yield 64%
TLC [MeOH / 28-30% NH3 / H2O (95: 5, v / v)]: Rf = 0.48 [a] D2 0 = -12 (c = 0.90, H2O)
IR (HCB) v (cm-1): 1175 and 1040 (SO3-).
1H RMN (300 MHz, D2O) (ppm) : 0.89 (t, 3H, CH3); 1.30-1.80 [m, 20H, CH3(CH2)10]; 2.22 (m, 2H, N+CH2CH2CH2SO3-); 2.95 (t, 2H, J = 6.8, CH2SO3-) ; 3.17 (d, 2H, H1); 3.57 (d, 3H, 4JH-H = 1, N+CH3); 3.74 (t, 2H, N+CH2); 3.43-4.39 (m, H2-H6).1 H NMR (300 MHz, D 2 O) (ppm): 0.89 (t, 3H, CH 3); 1.30-1.80 [m, 20H, CH3 (CH2) 10]; 2.22 (m, 2H, N + CH 2 CH 2 CH 2 SO 3 -); 2.95 (t, 2H, J = 6.8, CH 2 SO 3 -); 3.17 (d, 2H, H1); 3.57 (d, 3H, 4H-H = 1, N + CH 3); 3.74 (t, 2H, N + CH 2); 3.43-4.39 (m, H2-H6).
13C RMN (75 MHz, CD30D) (ppm) 15.24 (CH3); 20.43, 24.05, 24.48, 28.28, 31.06, 31.21, 31.44, 31.51, 33.81 [CH3H2)10 and CH2SO3-] ; 50.65, 50.79 (2N+CH3); 62.69, 63.06 (2N+CH2CH2CH2SO3-); 65.05 (N+CH2) ; 65.44 (C6) ; 65.77, 66.02 (2C1) ; 69.32, 72.42, 72.91, 73.77 (C2, C3, C4, C5). 13C NMR (75 MHz, CD30D) (ppm) 15.24 (CH3); 20.43, 24.05, 24.48, 28.28, 31.06, 31.21, 31.44, 31.51, 33.81 [CH3H2) 10 and CH2SO3-]; 50.65, 50.79 (2N + CH3); 62.69, 63.06 (2N + CH2CH2CH2SO3-); 65.05 (N + CH2); 65.44 (C6); 65.77, 66.02 (2C1); 69.32, 72.42, 72.91, 73.77 (C2, C3, C4, C5).
SM (LRP + ESPRAY) : 486 [M+H]+; 972 [M+H]2+. MS (LRP + ESPRAY): 486 [M + H] +; 972 [M + H] 2+.
Anal. élem calc. pour (C22H47NOgS, H2O) : C, 52.45; H, 9.80; N, 2.78 ; O, 28.58 ; S, 6.36
Trouvé : C, 51.78 ; H, 9;83 ; N, 2.85 ; 0, 27.91; S, 6.30.Anal. calc. for (C22H47NO8S, H2O): C, 52.45; H, 9.80; N, 2.78; O, 28.58; S, 6.36
Found: C, 51.78; H, 9, 83; N, 2.85; 0, 27.91; S, 6.30.
Exemple 3
Préparation du N-dodécyl-N-méthyl glucammonium-1-butanesulfonate
La réaction est effectuée selon le protocole décrit dans l'exemple 2 avec 2,83 mmoles de N-dodécyl-N-méthylglucamine (1,03 g), 2,83 mmoles de 1,4-butanesultone, 20 ml d'acétonitrile distillé et une durée de 5 jours. On recueille ainsi 900 mg (64 % de rendement) de
N-dodécyl-N-méthylglucammonium-1-butanesulfonate sous la forme de critaux blancs. rendement 64 %
CCM [MeOH/28-30% NH3/H2O (95:5, v/v)] : Rf = 0.45 IR (HCB) v (cm-1):1175 and 1040 (SO3-). Example 3
Preparation of N-dodecyl-N-methyl glucammonium-1-butanesulfonate
The reaction is carried out according to the protocol described in Example 2 with 2.83 mmol of N-dodecyl-N-methylglucamine (1.03 g), 2.83 mmol of 1,4-butanesultone and 20 ml of distilled acetonitrile. and a duration of 5 days. Thus, 900 mg (64% yield) of
N-dodecyl-N-methylglucammonium-1-butanesulfonate in the form of white crystals. yield 64%
TLC [MeOH / 28-30% NH3 / H2O (95: 5, v / v)]: Rf = 0.45 IR (HCB) v (cm-1): 1175 and 1040 (SO3-).
13C RMN (22.50 MHz, CD30D) (ppm):15.26 (CH3); 22.90, 23.87, 24.09, 24.47, 28.29, 31.05, 31.21, 31.37, 31.51, 33.81 [CH3(CH2)1o and CH2SO3-] ; 51.23 (N+CH3) ; 64.26 [N+CH2(CH2)3SO3-]; 65.13 (N+CH2) ; 65.48 (C6); 65.86 (C1); 69.43, 72.47, 73.01, 73.88 (C2, C3, C4, C5). 13C NMR (22.50 MHz, CD30D) (ppm): 15.26 (CH3); 22.90, 23.87, 24.09, 24.47, 28.29, 31.05, 31.21, 31.37, 31.51, 33.81 [CH3 (CH2) 10 and CH2SO3-]; 51.23 (N + CH3); 64.26 [N + CH 2 (CH 2) 3 SO 3 -]; 65.13 (N + CH2); 65.48 (C6); 65.86 (C1); 69.43, 72.47, 73.01, 73.88 (C2, C3, C4, C5).
SM (LRP + ESPRAY) : 500 [M+H]+; 1000 [M+H]2+.MS (LRP + ESPRAY): 500 [M + H] +; 1000 [M + H] 2+.
Exemple 4
Préparation du N-dodécyl-N-méthylglucammonium-méthanecarboxylate
6,33 mmoles de N-dodécyl-N-méthylglucamine (2,3 g), 12,67 mmoles de bromoacétate d'éthyle (1,4 ml) et 20 ml méthanol absolu sont portés à reflux 8 heures à l'abri de l'humidité atmosphérique. Le solvant est ensuite chassé sous pression réduite. Le résidu est alors partagé entre de l'eau et de l'éther diéthylique. Une autre extraction à l'éther diéthylique suffit à éliminer l'excès de bromoacétate d'éthyle et, à la carboxybétaine attendue en solution aqueuse, on ajoute une résine échangeuse d'ions (Dowex 1X2-200, OH-). Le mélange réactionnel est agité quelques heures à température ambiante puis 1 heure à 50-60 OC sous forte agitation. La résine échangeuse d'ions est ensuite éliminée par filtration. Après évaporation de l'eau sous pression réduite, le résidu est purifié par flash chromatographie [éluant: MeOH]. On recueille alors 2,1 g (80 % de rendement) de N-dodécyl-N-méthylglucammoniumméthanecarboxylate. rendement 80%
CCM [MeOH] : Rf = 0.55 [a]D20 = -120 (c = 1, H2O).Example 4
Preparation of N-dodecyl-N-methylglucammonium-methanecarboxylate
6.33 mmol of N-dodecyl-N-methylglucamine (2.3 g), 12.67 mmol of ethyl bromoacetate (1.4 ml) and 20 ml of absolute methanol are refluxed for 8 hours under atmospheric humidity. The solvent is then removed under reduced pressure. The residue is then partitioned between water and diethyl ether. Further extraction with diethyl ether is sufficient to remove excess ethyl bromoacetate and, with the expected carboxybetaine in aqueous solution, an ion exchange resin (Dowex 1X2-200, OH-) is added. The reaction mixture is stirred for a few hours at room temperature and then for 1 hour at 50-60 ° C. with vigorous stirring. The ion exchange resin is then removed by filtration. After evaporation of the water under reduced pressure, the residue is purified by flash chromatography [eluent: MeOH]. 2.1 g (80% yield) of N-dodecyl-N-methylglucammoniummethanecarboxylate are collected. 80% yield
TLC [MeOH]: Rf = 0.55 [a] D20 = -120 (c = 1, H2O).
IR (Nujol) v (cm-l) 1627 (C=O).IR (Nujol) v (cm-1) 1627 (C = O).
13C RMN (75 MHz, CD30D) (ppm) 15.22 (CH3); 24.22, 24.50, 28.34, 31.03, 31.24, 31.35, 31.43, 31.52, 33.84 [CH3tCH2)l0]; 51.08, 51.48 (2N+CH3) ; 64.24, 64.71 (N+CH2CO2-); 65.38, 65.62 (2N+CH2CH2) ; 65.51 (cl) ; 66.39, 66.52 (2CI); 69.79, 73.03, 73.10, 73.84 (C2, C3, C4, C5) ; 170.06, 170.09 (2C=O).13C NMR (75 MHz, CD30D) (ppm) 15.22 (CH3); 24.22, 24.50, 28.34, 31.03, 31.24, 31.35, 31.43, 31.52, 33.84 [CH3tCH2) 10]; 51.08, 51.48 (2N + CH3); 64.24, 64.71 (N + CH2CO2-); 65.38, 65.62 (2N + CH2CH2); 65.51 (cl); 66.39, 66.52 (2CI); 69.79, 73.03, 73.10, 73.84 (C2, C3, C4, C5); 170.06, 170.09 (2C = O).
Anal. élem. calc. pour [C21H43N07. (H2O)1/2] : C, 58.57 ; H, 10.30; N, 3.25; O, 27.87
C, 58.53 ; H, 10.62 ; N, 3.18 ; 0, 27.88. Anal. ELEM. calc. for [C21H43NO7. (H2O) 1/2]: C, 58.57; H, 10.30; N, 3.25; O, 27.87
C, 58.53; H, 10.62; N, 3.18; 0, 27.88.
Exemple 5
Concentrations micellaires critiques et propriétés tensioactives
Le N-dodécyl-N-méthylglucammonium- l-propanesulfonate et le N-dodécyl-N méthylglucammonium- l-butanesulfonate ont été préparés respectivement selon les exemples 2 et 3, le N-dodécyl-N-méthylglucammonium-méthanecarboxylate a été préparé selon l'exemple 4.Example 5
Critical micellar concentrations and surfactant properties
N-dodecyl-N-methylglucammonium-1-propanesulfonate and N-dodecyl-N-methylglucammonium-1-butanesulphonate were prepared according to Examples 2 and 3 respectively. N-dodecyl-N-methylglucammonium-methanecarboxylate was prepared according to US Pat. Example 4
Pour les mesures de tensions de surface, les tensioactifs sont dissous dans de l'eau déminéralisée et bidistillée. Les tensions de surface sont déterminées à 20 OC et à diverses concentrations à l'aide d'un tensiomètre Krüss K10 muni d'un anneau Du Noüy.
Tableau : Détermination des concentrations micellaires critiques (CMC), des aires
moléculaires à l'interface eau-air (ag) et des tensions de surface à la CMC (ycMc)
Table: Determination of critical micellar concentrations (CMC), areas
molecules at the water-air interface (ag) and surface tensions at the CMC (ycMc)
<tb> <SEP> tensioactif <SEP> CMC <SEP> aO <SEP> YCMC
<tb> <SEP> (mM) <SEP> ( 2/ <SEP> (mN.m-1)
<tb> <SEP> molécule)
<tb> <SEP> OH <SEP> O <SEP> H
<tb> - <SEP> 4.5 <SEP> 53 <SEP> 35
<tb> <SEP> OH <SEP> OH <SEP> Q
<tb> <SEP> So3
<tb> <SEP> OH <SEP> OH
<tb> 3.8 <SEP> 3.8 <SEP> 57 <SEP> 35
<tb> <SEP> OH <SEP> OH <SEP> t <SEP> so
<tb> <SEP> SO3
<tb> <SEP> OH <SEP> OH
<tb> 2.6 <SEP> 2.6 <SEP> 47 <SEP> X <SEP> 33
<tb> <SEP> OH <SEP> OH
<tb>
Les résultats montrent que les sulfobétaines ou carboxybétaines glycosylées abaissent la tension superficielle de l'eau (72 mN.m-l) jusqu'à des valeurs proches de 35 mN.m-l tout en présentant des valeurs de concentrations micellaires critiques relativement faibles. <tb><SEP> surfactant <SEP> CMC <SEP> aO <SEP> YCMC
<tb><SEP> (mM) <SEP> (2 / <SEP> (mN.m-1)
<tb><SEP> molecule)
<tb><SEP> OH <SE> O <SEP> H
<tb> - <SEP> 4.5 <SEP> 53 <SEP> 35
<tb><SEP> OH <SEP> OH <SEP> Q
<tb><SEP> So3
<tb><SEP> OH <SEP> OH
<tb> 3.8 <SEP> 3.8 <SEP> 57 <SEP> 35
<tb><SEP> OH <SEP> OH <SEP> t <SEP> N / A
<tb><SEP> SO3
<tb><SEP> OH <SEP> OH
<tb> 2.6 <SEP> 2.6 <SEP> 47 <SEP> X <SEP> 33
<tb><SEP> OH <SEP> OH
<Tb>
The results show that glycosylated sulfobetaines or carboxybetaines lower the surface tension of water (72 mN.ml) to values close to 35 mN.ml while presenting relatively low critical micellar concentration values.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9315014A FR2713638A1 (en) | 1993-12-14 | 1993-12-14 | New, quaternised, water-soluble, zwitterionic, glycoside tensides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9315014A FR2713638A1 (en) | 1993-12-14 | 1993-12-14 | New, quaternised, water-soluble, zwitterionic, glycoside tensides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| FR2713638A1 true FR2713638A1 (en) | 1995-06-16 |
Family
ID=9453916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR9315014A Withdrawn FR2713638A1 (en) | 1993-12-14 | 1993-12-14 | New, quaternised, water-soluble, zwitterionic, glycoside tensides |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2713638A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725254A (en) * | 2015-02-13 | 2015-06-24 | 陕西科技大学 | Preparation method of glycosylated surfactant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05148288A (en) * | 1991-11-29 | 1993-06-15 | Kao Corp | New betaine saccharide compound |
| EP0569904A2 (en) * | 1992-05-11 | 1993-11-18 | ALBRIGHT & WILSON UK LIMITED | Process for the preparation of carbohydrate derived surfactants and their precursors |
-
1993
- 1993-12-14 FR FR9315014A patent/FR2713638A1/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05148288A (en) * | 1991-11-29 | 1993-06-15 | Kao Corp | New betaine saccharide compound |
| EP0569904A2 (en) * | 1992-05-11 | 1993-11-18 | ALBRIGHT & WILSON UK LIMITED | Process for the preparation of carbohydrate derived surfactants and their precursors |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 17, no. 533 (C - 1114) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725254A (en) * | 2015-02-13 | 2015-06-24 | 陕西科技大学 | Preparation method of glycosylated surfactant |
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