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WO1992000984A1 - Alkdienylglucosides sulfures - Google Patents

Alkdienylglucosides sulfures Download PDF

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Publication number
WO1992000984A1
WO1992000984A1 PCT/EP1991/001216 EP9101216W WO9200984A1 WO 1992000984 A1 WO1992000984 A1 WO 1992000984A1 EP 9101216 W EP9101216 W EP 9101216W WO 9200984 A1 WO9200984 A1 WO 9200984A1
Authority
WO
WIPO (PCT)
Prior art keywords
glycosides
alkdienyl
sulfated
sulfonation
octadienyl
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.)
Ceased
Application number
PCT/EP1991/001216
Other languages
German (de)
English (en)
Inventor
Bernd Fabry
Bert Gruber
Karlheinz Hill
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.)
Henkel AG and Co KGaA
Zucker AG
Original Assignee
Henkel AG and Co KGaA
Zucker AG
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 Henkel AG and Co KGaA, Zucker AG filed Critical Henkel AG and Co KGaA
Publication of WO1992000984A1 publication Critical patent/WO1992000984A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C07H15/10—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical containing unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H11/00—Compounds containing saccharide radicals esterified by inorganic acids; Metal salts thereof

Definitions

  • the invention relates to sulfated alkdienyl glycosides, obtainable by reacting alkdienyl glycosides with a sulfating agent and subsequent neutralization and hydrolysis of the reaction products with aqueous bases, a process for their preparation and their use as surface-active agents.
  • Sulphated glycosides are also known from European patent application EP-A-0186242, in which the glycoside portion consists of 1 to 10 glycose units and is derived from sugars with 5 to 6 carbon atoms.
  • the aliphatic hydrocarbon radicals which can also be unsaturated, have 6 to 32 carbon atoms.
  • Sulphated compounds of this type are used to liquefy coal slurries.
  • Sulfated alkyl or alkenyl glycosides of the type mentioned have excellent detergent properties, but they do not have sufficient foaming power for applications in the cosmetic field.
  • the object of the invention was therefore to provide sulfonated glycosides which do not have the disadvantages described.
  • the invention relates to sulfated alkdienyl glycosides, obtainable by reacting alkdienyl glycosides with a sulfating agent and then neutralizing and hydrolyzing the reaction products with aqueous bases.
  • the invention includes the knowledge that the sulfated alkdienyl glycosides according to the invention have good detergent properties, are readily soluble in water and have a pronounced foaming power.
  • Sulfated alkdienyl glycosides with particularly advantageous application properties are obtained if one starts from ocadienyl glycosides, especially octadienyl glucosides, and reacts them with sulfur trioxide.
  • Alkdienyl glycosides are accessible by telerization of conjugated danes with glycosides in the presence of palladium salts and phosphine derivatives. This produces mixtures of mono- and polyethers, the degree of etherification being able to be influenced by the amount of catalyst system used.
  • the method is known per se from German patent DE-B-1807491.
  • the alkdienyl glycosides can be derived, in particular, from conjugated dienes which are formed in naphtha pyrolysis and which are therefore also available on an industrial scale. These are therefore primarily isoprene, piperylene and particularly preferably 1,3-butadiene.
  • the glycoside component of the alkdienyl glycosides can be derived from monoglycosides with 5 or 6 carbon atoms, such as, for example, ribose, arabinose, xylose, allose, old rose, glucose, mannose, gulose, idose, galactose, talose, fructose or sorbose.
  • the alkdienyl glycosides can also be derived from diglycosides such as, for example, sucrose, maltose, cellubiose, lactose or isomaltose. Because of their easy accessibility, the preferred alkdienyl glycosides for use in sulfonation are alkdienyl glucosides.
  • the invention further relates to a process for the preparation of sulfated alkdienyl glycosides, characterized in that alkdienyl glycosides are reacted with a sulfating agent and the reaction products are then neutralized and hydrolyzed with aqueous bases.
  • Sulfated alkdienyl glycosides with particularly advantageous application properties are obtained if octadienyl glycosides, in particular octadienyl glucosides, are used in the sulfonation.
  • the sulfonation of the alkdienyl glycosides can be carried out using customary sulfonating agents, for example sulfuric acid, oleum, chlorosulfonic acid or amidosulfonic acid.
  • customary sulfonating agents for example sulfuric acid, oleum, chlorosulfonic acid or amidosulfonic acid.
  • the sulfonation is advantageously carried out with gaseous sulfur trioxide in the known lower alkyl esters [J.Falbe (ed.), "Surfactants in consumer products", Springer Verlag, Berlin-Heidelberg, 1987,
  • the sulfur trioxide is diluted with an inert gas, preferably air or nitrogen, and used in the form of a gas mixture which contains the sulfonating agent in a concentration of 1 to 8, in particular 2 to 5,% by volume.
  • the sulfonation with sulfur trioxide is carried out in an inert solvent, for example orthoformate, diethylformamide, pyridine, tetrahydrofuran or 1,2-dichloroethane.
  • an inert solvent for example orthoformate, diethylformamide, pyridine, tetrahydrofuran or 1,2-dichloroethane.
  • the molar ratio of the alkdienyl glycosides to the sulfonating agent can be 1: 0.5 to 1: 1.5.
  • chlorosulfonic acid or gaseous sulfur trioxide it is advisable to set a molar ratio of 1: 0.5 to 1: 0.95, while sulfonation with SO3 in the solvent advantageously with a ratio of 1: 0.75 to 1: 1,2 is carried out.
  • the sulfonation can be carried out at temperatures from 5 to 80. If the sulfonation takes place in the absence of an organic solvent, the theological behavior of the alkynyl glycosides requires reaction temperatures of at least 30 ° C. When the alkdienylglycosides are reacted with the sulfonating agents, there is also a secondary reaction of oxidative damage to the starting material, which is noticeable through discoloration and / or caramelization. bar and gains in importance with increasing reaction temperature. With regard to light-colored or easily bleachable products, it has therefore proven optimal to limit the sulfonation temperature to 50 ° C.
  • this advantageous embodiment of the invention provides particularly light-colored products.
  • the acidic sulfonation products obtained during the sulfonation are stirred into aqueous bases, neutralized and adjusted to a pH of 6.5 to 8.5.
  • bases for the neutralization come alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C2-4-alkanolamines, for example mono- , Di- and triethanolamine and primary, secondary or tertiary C ⁇ _4 ⁇ Alkyla ine into consideration.
  • the neutralization bases are preferably used in the form of 5 to 55% by weight aqueous solutions, 5 to 25% by weight aqueous sodium hydroxide solutions being preferred.
  • the free hydroxyl function is primarily sulfated; the attack of the S03 on the free hydroxyl groups of the glycoside body takes place statistically instead.
  • As a side reaction there is also an electrophilic addition of sulfur trioxide molecules to the double bonds of the hydrocarbon radicals.
  • the primarily formed sultones are not thermodynamically stable and disintegrate over time to form sulfonic acids, which greatly reduce the pH of the aqueous solutions of the sulfonated alkdienyl glycosides and can contribute to their decomposition.
  • the sulfated alkdienyl glycosides must be hydrolyzed after neutralization in the presence of excess aqueous base over a period of 0.1 to 6, preferably 2 to 4 hours and at temperatures of 50 to 95 ° C.
  • sultonants formed are converted quantitatively into stable sulfonates.
  • the sulfated alkdienyl glycosides are therefore anionic surfactants with a sulfate and sulfonate structure.
  • the sulfonation products can be bleached in a manner known per se by adding hydrogen peroxide or sodium hypochlorite solution. Based on the solids content in the solution of the sulfonation products, 0.2 to 2% by weight of hydrogen peroxide, calculated as a 100% substance, or corresponding amounts of sodium hypochlorite are used.
  • the pH of the solutions can be adjusted using suitable buffering agents, e.g. B. be kept constant with sodium phosphate or citric acid. To stabilize against bacterial attack, conservation is also recommended, e.g. B. with formaldehyde solution, p-hydroxybenzoate, sorbic acid or other known preservatives.
  • the invention also relates to the use of the sulfonated alkdienyl glycosides as surface-active agents and for the production of cosmetic products.
  • the following examples are intended to explain the subject matter of the invention in more detail without restricting it.
  • Octadienyl glucoside, degree of etherification 1.5 (A). 1.7 g (0.0057 mol) of palladium (II) acetylacetonate, 3 g (0.011 mol) of triphenylphosphine, 865 g (14.4 mol) of propa- nol-2, 110 g (6.1 mol) of water and 1284 g (7.1 mol) of anhydrous glucose.
  • the reactor was alternately flushed with nitrogen three times and evacuated.
  • a lifter 768 g (14.2 mol) were charged 1,3-butadiene then using and Re ⁇ action mix '3 h at 75 ° C heated. After cooling, the reactor was carefully let down, with small amounts of undissolved butadiene escaping.
  • Trioctadienylglucoside 5% by weight
  • the anionic surfactant content (WAS) and the unsulfonated contents (US) were determined according to the DGF standard methods, Stuttgart, 1950-1984, H-111-10 and G-II-6b.
  • the sulfate content was calculated as sodium sulfate, the water content was determined by the Fischer method.
  • Tab. 1 sulfated octadiene ll cosides

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

Abstract

On obtient des substances ayant des propriétés tensio-actives en faisant réagir des alkdiénylglucosides avec des agents sulfurants, puis en neutralisant et en hydrolysant les produits de la réaction avec des bases aqueuses.
PCT/EP1991/001216 1990-07-07 1991-06-28 Alkdienylglucosides sulfures Ceased WO1992000984A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904021760 DE4021760A1 (de) 1990-07-07 1990-07-07 Sulfierte alkdienylglykoside
DEP4021760.4 1990-07-07

Publications (1)

Publication Number Publication Date
WO1992000984A1 true WO1992000984A1 (fr) 1992-01-23

Family

ID=6409913

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/001216 Ceased WO1992000984A1 (fr) 1990-07-07 1991-06-28 Alkdienylglucosides sulfures

Country Status (2)

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DE (1) DE4021760A1 (fr)
WO (1) WO1992000984A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2769223B1 (fr) 1997-10-03 2003-08-22 Oreal Composition oxydante et utilisations pour la teinture, pour la deformation permanente ou pour la decoloration des fibres keratiniques
FR2773476B1 (fr) 1998-01-13 2001-02-23 Oreal Composition tinctoriale et procedes de teinture des fibres keratiniques la mettant en oeuvre
FR2782450B1 (fr) 1998-08-19 2004-08-27 Oreal Composition de teinture pour fibres keratiniques avec un colorant direct cationique et un agent tensio-actif anionique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1604269A (fr) * 1967-11-10 1971-10-11
EP0186242A1 (fr) * 1984-12-24 1986-07-02 The Procter & Gamble Company Composition en suspension charbon-eau
US4609478A (en) * 1984-02-21 1986-09-02 Olin Corporation Sulfonated alkyl glucosides and use thereof in oil recovery
WO1988001640A1 (fr) * 1986-09-05 1988-03-10 A.E. Staley Manufacturing Company Derives ioniques de mono et polyglycosides d'alkyle
EP0363601A2 (fr) * 1988-10-13 1990-04-18 Hüls Aktiengesellschaft Procédé de sulfatation d'alkylglycosides
DE3918135A1 (de) * 1989-06-03 1990-12-13 Henkel Kgaa Sulfierte alkenylglykoside als tenside

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1604269A (fr) * 1967-11-10 1971-10-11
US4609478A (en) * 1984-02-21 1986-09-02 Olin Corporation Sulfonated alkyl glucosides and use thereof in oil recovery
EP0186242A1 (fr) * 1984-12-24 1986-07-02 The Procter & Gamble Company Composition en suspension charbon-eau
WO1988001640A1 (fr) * 1986-09-05 1988-03-10 A.E. Staley Manufacturing Company Derives ioniques de mono et polyglycosides d'alkyle
EP0363601A2 (fr) * 1988-10-13 1990-04-18 Hüls Aktiengesellschaft Procédé de sulfatation d'alkylglycosides
DE3918135A1 (de) * 1989-06-03 1990-12-13 Henkel Kgaa Sulfierte alkenylglykoside als tenside

Also Published As

Publication number Publication date
DE4021760A1 (de) 1992-01-09

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