EP1247880A2 - Process for the preparation of glycine derivatives and use thereof - Google Patents

Process for the preparation of glycine derivatives and use thereof Download PDF

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Publication number
EP1247880A2
EP1247880A2 EP02006731A EP02006731A EP1247880A2 EP 1247880 A2 EP1247880 A2 EP 1247880A2 EP 02006731 A EP02006731 A EP 02006731A EP 02006731 A EP02006731 A EP 02006731A EP 1247880 A2 EP1247880 A2 EP 1247880A2
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Prior art keywords
acid
compounds
glycine
hydroxyethylammonium
preparation
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German (de)
French (fr)
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EP1247880A3 (en
EP1247880B1 (en
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Oliver Dr. Thurmüller
Philipp Dr. Thomuschat
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Evonik Operations GmbH
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TH Goldschmidt AG
Goldschmidt GmbH
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • the subject of the invention is a new method of manufacture of glycine derivatives.
  • Glycine derivatives are like betaines known as mild and tolerable substances and are in large quantities for the production of cosmetic preparations Cleaning and care of skin and hair also used.
  • Glycine derivatives are prepared according to the methods known in the art the technology produced by reacting tertiary amines with Part of excess monochloroacetic acid in basic aqueous Solution at elevated temperature.
  • MCA monochloroacetic acid
  • DCA dichloroacetic acid
  • DE-A-39 39 264 relates to a method for lowering the Residual content of free alkylating agent in aqueous solutions amphoteric or zwitterionic surfactants with the mark, that the solutions with ammonia, an amino acid with Treated 2 to 8 carbon atoms or an oligopeptide. Also this post-treatment leaves a residual MCA content and / or DCA in the reaction product. In addition, the Reaction products from ammonia and alkylating agent or Peptide and alkylating agent but produces reaction products which remain as impurities in the process product.
  • the reaction mixtures also contain large amounts of Chloride ions in the form of their alkali or ammonium salts. Therefore they have other disadvantages, such as increasing the viscosity of the end product, impairment of the low temperature stability of formulations and they cannot match a number of others active ingredients.
  • the oxidation of the quaternary amino alcohol to the corresponding one Glycine derivative can in this case by electrochemical oxidation aqueous alkaline solution using coated Nickel electrodes are made.
  • the present invention therefore relates to a method for the production of glycine derivatives by oxidation of ⁇ -hydroxyethylammonium compounds by electrolysis of a aqueous alkaline solution, which is characterized that using oxidation with nickel oxide hydroxide coated anodes is carried out.
  • the process is characterized by exceptional environmental friendliness because there are no environmentally harmful by-products incurred and on the other hand on the use of highly toxic Chloroacetic acid can be dispensed with.
  • the electrolysis is carried out in such a way that the aqueous electrolyte is electrolyzed on electrodes coated with nickel oxide hydroxide.
  • the electrodes can be coated using customary methods, such as the method proposed by HJ Schfer.
  • a Ni (OH) 2 layer is first cathodically deposited on the later anode from a Ni salt solution and then anodically converted to NiO (OH) in alkaline solution (J. Kaulen, HJ Schfer, Tetrahedron, 1982, 38, 3299).
  • Nickel metal other materials are used on which the activated nickel oxide hydroxide layer adheres like Monel, stainless steel, graphite or vitreous carbon.
  • the cathode can be any, usually in the Electrochemical material used for the manufacture of cathodes exist, such as precious metals, stainless steel or nickel.
  • the electrolytic cell can be made of any, against electrolyte and There are reactant-resistant materials such as alkali-resistant Glass, porcelain, polyethylene, rubber or stainless steel.
  • the cell type can be divided or undivided, the latter is preferred because a reduction in the desired electrolysis product need not be feared.
  • the process according to the invention can be carried out continuously or batchwise be carried out, preferably discontinuously is worked.
  • the electrolysis system from an aqueous solution of the ⁇ -Hydroxyethylammonium compound with a pH preferably of over 12.
  • the alkalinity of the solutions is usually caused by alkali metal hydroxides (preferably NaOH and KOH).
  • the lye necessary for the neutralization of the resulting acid is gradually added, slightly less than that theoretically necessary amount is added so that the pH the solution obtained after the electrolysis is complete at about 9 lies.
  • Appropriate levels of ⁇ -hydroxyethylammonium compound alkaline solution are between 1 and 30 wt .-%, preferably between 20 and 30% by weight.
  • the electrolysis temperature is usually 20 to 80 ° C, preferably about 70 ° C.
  • the electrolyzed solution is, for example brought to pH 6 to 7 with phosphoric acid, concentrated and the residue with a suitable solvent extracted.
  • a suitable solvent e.g. Alcohols (ethanol, isopropanol) suitable.
  • the extract obtained is freed from the solvent and delivers the pure betaines.
  • Betaines are to be obtained. They usually interfere with the synthesis of salts, however, so that on a Extraction can be dispensed with.
  • ⁇ -hydroxyethylammonium compounds used in accordance with the invention can by the methods known in this field by reacting amines with ethylene oxide in an acidic solution can be produced (EP-A-0 098 802).
  • the radical R a is preferably derived from natural fatty acids, such as caprylic acid, capric acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, hydroxystearic acid (ricinoleic acid), dihydroxystearic acid, oleic acid, linoleic acid, petroselic acid, araidic acid, elaidic acid, elaidic acid Behenic acid and erucic acid, gadoleic acid and the technical mixtures resulting from the pressure splitting of natural fats and oils, such as oleic acid, linoleic acid, linolenic acid and in particular rapeseed oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, tall oil fatty acid. In principle, all fatty acids with a similar chain distribution are suitable.
  • natural fatty acids such as caprylic acid, capric acid
  • the iodine number is the amount of iodine, which from 100 g Connection for the saturation of the double bonds added becomes.
  • C 8/18 coconut or palm fatty acids Partially hardened C 8/18 coconut or palm fatty acids, rapeseed oil fatty acids, sunflower oil fatty acids, soybean oil fatty acids and tall oil fatty acids with iodine numbers in the range from approx. 80 to 150 and in particular technical C 8/18 coconut fatty acids are used, where appropriate a selection of cis / trans isomers, such as C 16/18 fatty acid cuts rich in elaidic acid, can be advantageous.
  • They are commercially available products and are offered by various companies under their respective trade names.
  • the solution again has a pH of 8 to 9 and 4 ml of saturated NaOH solution are again added.
  • a current of 0.5 A is then set and electrolyzed for a further 7.5 h.
  • the solution obtained has a pH of 8 to 9.
  • the reaction was checked by means of TLC chromatography and ESI mass spectrometry.
  • the electrolysis discharge is carried out with phosphoric acid pH is adjusted from 6 to 7 and concentrated.
  • the residue is extracted with isopropanol and the extract obtained freed from the solvent. As a product you get a yellow-brown solid.
  • Example 2 The experiment was carried out analogously to Example 1.
  • 2-hydroxyethyl (dimethyl) 3-undecylcarboxamidopropylammonium x 0.5 C 2 O 4 H - was used as the starting material.
  • oxalate is first oxidized to CO 2 , which reacts to carbonate under the alkaline conditions and only then oxidizes the ammonium alcohol to the corresponding glycine derivative.
  • the correspondingly larger amount of NaOH required was added to the solution from the start.
  • Example 2 The experiment was carried out analogously to Example 1.
  • 105 ml of a 2.7% solution of an ammonium mixture (based on the coconut fatty acid cut), which contained 2-hydroxyethyl (dimethyl) 3-undecylcarboxamidopropylammonium x 0.5 H 2 PO 4 - as the main component, for 3 h electrolyzed at 2.0 A.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Preparation of glycine derivatives comprises electrochemically oxidizing the hydroxide groups of beta -hydroxyethylammonium compounds to yield the corresponding acid.

Description

Gegenstand der Erfindung ist ein neues Verfahren zur Herstellung von Glycinderivaten. Glycinderivate wie Betaine sind als milde und verträgliche Substanzen bekannt und werden in großen Mengen zur Herstellung von kosmetischen Präparaten zur Reinigung und Pflege von Haut und Haaren mitverwendet.The subject of the invention is a new method of manufacture of glycine derivatives. Glycine derivatives are like betaines known as mild and tolerable substances and are in large quantities for the production of cosmetic preparations Cleaning and care of skin and hair also used.

Glycinderivate werden nach den Verfahren gemäß bekanntem Stand der Technik hergestellt durch Umsetzung tertiärer Amine mit zum Teil überschüssiger Monochloressigsäure in basischer wässriger Lösung bei erhöhter Temperatur.Glycine derivatives are prepared according to the methods known in the art the technology produced by reacting tertiary amines with Part of excess monochloroacetic acid in basic aqueous Solution at elevated temperature.

Es wurden in der Vergangenheit große Anstrengungen unternommen, Glycinderivate herzustellen, die frei sind von Verunreinigungen, welche Hautreizungen verursachen können oder in sonstiger Weise aus toxikologischen und physiologischen Gründen unerwünscht sind.Great efforts have been made in the past To produce glycine derivatives that are free of impurities, which can cause skin irritation or otherwise Way undesirable for toxicological and physiological reasons are.

Hierzu zählen insbesondere die verfahrensbedingten Restmengen an Verbindungen mit organisch gebundenem Chlor, wie Monochloressigsäure (MCA) und insbesondere Dichloressigsäure (DCA) oder deren Salze, welche mit der eingesetzten Chloressigsäure in das Endprodukt eingebracht werden.This includes in particular the procedural residual quantities on compounds with organically bound chlorine, such as monochloroacetic acid (MCA) and especially dichloroacetic acid (DCA) or their salts, which with the chloroacetic acid used in the End product are introduced.

Versuche, den Gehalt an diesen Verbindungen durch verlängerte Reaktionszeiten oder Erhöhung der pH-Werte zu reduzieren, führten zu keiner wesentlichen Verringerung. Die Anwendung von pH-Werten oberhalb ca. 10 bringt insbesondere bei erhöhten Temperaturen um oder oberhalb 100 °C das Risiko einer zunehmenden Zersetzung mit sich (DE-B-29 26 479, EP-B-0 557 835).Attempts to prolong the content of these compounds Reduce response times or increase in pH values to no significant reduction. The application of pH values above approx. 10 bring especially with increased Temperatures around or above 100 ° C the risk of increasing decomposition with it (DE-B-29 26 479, EP-B-0 557 835).

Die DE-A-39 39 264 betrifft ein Verfahren zur Erniedrigung des Restgehaltes an freiem Alkylierungsmittel in wässrigen Lösungen amphoterer oder zwitterionischer Tenside mit dem Kennzeichen, dass man die Lösungen mit Ammoniak, einer Aminosäure mit 2 bis 8 C-Atomen oder einem Oligopeptid nachbehandelt. Auch durch diese Nachbehandlung verbleibt ein Restgehalt an MCA und/oder DCA im Reaktionsprodukt. Zusätzlich werden durch die Umsetzungsprodukte aus Ammoniak und Alkylierungsmittel oder Peptid und Alkylierungsmittel aber Reaktionsprodukte erzeugt, welche als Verunreinigungen im Verfahrensprodukt verbleiben.DE-A-39 39 264 relates to a method for lowering the Residual content of free alkylating agent in aqueous solutions amphoteric or zwitterionic surfactants with the mark, that the solutions with ammonia, an amino acid with Treated 2 to 8 carbon atoms or an oligopeptide. Also this post-treatment leaves a residual MCA content and / or DCA in the reaction product. In addition, the Reaction products from ammonia and alkylating agent or Peptide and alkylating agent but produces reaction products which remain as impurities in the process product.

Weiterhin enthalten die Reaktionsmischungen große Mengen an Chloridionen in Form ihrer Alkali- oder Ammoniumsalze. Daher weisen sie weitere Nachteile auf, wie Erhöhung der Viskosität des Endproduktes, Beeinträchtigung der Tieftemperaturstabilität von Formulierungen und sie können nicht mit einer Anzahl weiterer aktiver Ingredienzien formuliert werden.The reaction mixtures also contain large amounts of Chloride ions in the form of their alkali or ammonium salts. Therefore they have other disadvantages, such as increasing the viscosity of the end product, impairment of the low temperature stability of formulations and they cannot match a number of others active ingredients.

Weiterhin sind sie aufgrund des Chloridionen-Gehaltes zu aggressiv für die Reinigung korrosionsempfindlicher metallischer Untergründe wie sie insbesondere in der elektronischen Industrie eingesetzt werden.Furthermore, they are due to the chloride ion content aggressive for cleaning corrosion-sensitive metallic Substrates like those in particular in the electronic Industry.

Es gab daher eine Reihe von Versuchen, diese Salze zu entfernen wie beispielsweise durch Lösungsmittelextraktion wie in der JP-A-759981984 beschrieben oder durch Elektrodialyse gemäß EP-A-0 269 940. Abgesehen davon, dass keine vollständige Entfernung der Chloridionen erreicht werden kann, sind diese Verfahren durch die erforderlichen zusätzlichen Stufen aufwendig und ökonomisch unvorteilhaft. There have been a number of attempts to remove these salts such as by solvent extraction as in the JP-A-759981984 or by electrodialysis EP-A-0 269 940. Apart from that no complete removal these methods are the chloride ions can be reached complex due to the required additional stages and economically disadvantageous.

Es gibt zahlreiche Verfahren, die die Oxidation von Alkoholen zu Carbonsäuren gestatten. Neben den klassischen Verfahren der Oxidation im Labormaßstab mittels Schwermetalloxiden (z.B. KMnO4) existieren auch Verfahren, die im technischen Maßstab durchgeführt werden können, wie die Oxidation durch NO2 (US-A-5 856 470), durch Nitriloxide (US-A-5 179 218), durch O2 unter Edelmetallkatalyse (DE-39 29 063) oder auch elektrochemisch (EP-A-0 199 413, DE-A-34 43 303).There are numerous processes that allow the oxidation of alcohols to carboxylic acids. In addition to the classic methods of oxidation on a laboratory scale using heavy metal oxides (eg KMnO 4 ), there are also methods that can be carried out on an industrial scale, such as oxidation by NO 2 (US Pat. No. 5,856,470) by nitrile oxides (US Pat. 5 179 218), by O 2 with noble metal catalysis (DE-39 29 063) or also electrochemically (EP-A-0 199 413, DE-A-34 43 303).

Aus Arbeiten von H.-J. Schäfer ist es bekannt (Übersicht: Topics in Current Chemistry, 1987, 142, 102 bis 129), dass primäre Alkohole durch Elektrolyse in alkalischer Lösung unter Verwendung von mit Nickeloxidhydroxid NiO(OH) beschichteten Anoden und von Stahl-Kathoden mit Ausbeuten zwischen 46 und 99 % der Theorie (d. Th.) zu den entsprechenden Carbonsäuren oxidiert werden können. Die Oxidation erfolgt dabei hauptsächlich nach einem indirekten Anodenprozess, bei dem der Alkohol durch das Nickeloxidhydroxid mit 3wertigem Nickel zur Carbonsäure oxidiert wird, wobei das NiO(OH) zu Nickeloxid oder Nickelhydroxid mit 2wertigem Nickel reduziert wird. Durch Elektronenentzug an der Anode geht das 2wertige Nickel anschließend wieder in das 3wertige Nickel über.From works by H.-J. Schäfer knows it (overview: Topics in Current Chemistry, 1987, 142, 102 to 129) that primary Alcohols by electrolysis in alkaline solution Use of nickel oxide hydroxide NiO (OH) coated Anodes and steel cathodes with yields between 46 and 99% of theory (ie.) To the corresponding Carboxylic acids can be oxidized. The oxidation takes place mainly after an indirect anode process, at which the alcohol through the nickel oxide hydroxide with trivalent Nickel is oxidized to the carboxylic acid, the NiO (OH) too Nickel oxide or nickel hydroxide reduced with divalent nickel becomes. By removing electrons from the anode, the 2-valued one can do it Nickel then again into the trivalent nickel.

Über die elektrochemische Oxidation von Alkoholen, die über eine Ethylengruppe an einen quartären positiv geladenen Stickstoff gebunden sind, wird in der genannten Arbeit nicht berichtet.About the electrochemical oxidation of alcohols an ethylene group to a quaternary positively charged Nitrogen bound is not in the work mentioned reported.

In dem Bestreben, die Nachteile des Standes der Technik zu überwinden und ein Verfahren bereitzustellen, welches die Herstellung von Glycinderivaten ermöglicht, wurde nun gefunden, dass dieses Ziel durch die Oxidation quartärer Aminoalkohole erreicht wird. Überraschenderweise stört der quartäre, positiv geladene Stickstoff den Oxidationsprozess nicht, und es können weder Oxidationsprodukte des Stickstoffs, wie N-Oxide, noch Abbauprodukte nach Hoffmann nachgewiesen werden. Glycinderivate, die auf diese Weise hergestellt werden, sind frei von anorganischem Chlor und organisch gebundenem Chlor, wie insbesondere Monochloressigsäure, Dichloressigsäure und deren Salzen.In an effort to address the disadvantages of the prior art overcome and to provide a method that the manufacture of glycine derivatives has now been found that this goal through the oxidation of quaternary amino alcohols is achieved. Surprisingly, the quaternary, positive charged nitrogen does not oxidize and it can neither oxidation products of nitrogen, such as N-oxides, nor decomposition products according to Hoffmann. glycine, produced in this way are free of inorganic Chlorine and organically bound chlorine, such as in particular Monochloroacetic acid, dichloroacetic acid and their salts.

Die Oxidation des quartären Aminoalkohols zum entsprechenden Glycinderivat kann dabei durch elektrochemische Oxidation in wässriger alkalischer Lösung unter Verwendung beschichteter Nickelelektroden erfolgen.The oxidation of the quaternary amino alcohol to the corresponding one Glycine derivative can in this case by electrochemical oxidation aqueous alkaline solution using coated Nickel electrodes are made.

Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung von Glycinderivaten durch Oxidation von β-Hydroxyethylammonium-Verbindungen durch Elektrolyse einer wässrigen alkalischen Lösung, das dadurch gekennzeichnet ist, dass die Oxidation unter Verwendung von mit Nickeloxidhydroxid beschichteten Anoden durchgeführt wird.The present invention therefore relates to a method for the production of glycine derivatives by oxidation of β-hydroxyethylammonium compounds by electrolysis of a aqueous alkaline solution, which is characterized that using oxidation with nickel oxide hydroxide coated anodes is carried out.

Das Verfahren zeichnet sich durch außerordentliche Umweltfreundlichkeit aus, da zum einen keine umweltbelastenden Nebenprodukte anfallen und zum anderen auf den Einsatz der hochtoxischen Chloressigsäure verzichtet werden kann. Daneben wird direkt ein Produkt frei von anorganischem Chlor erhalten, so dass auf eine technisch aufwendige Abtrennung der Chloridionen verzichtet werden kann.The process is characterized by exceptional environmental friendliness because there are no environmentally harmful by-products incurred and on the other hand on the use of highly toxic Chloroacetic acid can be dispensed with. Next to it received a product free of inorganic chlorine, so that on a technically complex separation of the chloride ions can be dispensed with.

Nach dem elektrochemischen Verfahren werden Ausbeuten durchweg größer 80 % d. Th. erhalten. Die Elektrolyse wird im Prinzip so durchgeführt, dass der wässrige Elektrolyt an mit Nickeloxidhydroxid beschichteten Elektroden elektrolysiert wird. Die Beschichtung der Elektroden kann dabei nach üblichen wie z.B. nach dem von H.J. Schäfer vorgeschlagenen Verfahren erfolgen. Im Prinzip wird dabei aus einer Ni-Salzlösung zunächst kathodisch eine Ni(OH)2-Schicht auf der späteren Anode abgeschieden und dann anodisch in alkalischer Lösung in NiO(OH) überführt (J. Kaulen, H.J. Schäfer, Tetrahedron, 1982, 38, 3299).After the electrochemical process, yields are consistently greater than 80% of theory. Th. Received. In principle, the electrolysis is carried out in such a way that the aqueous electrolyte is electrolyzed on electrodes coated with nickel oxide hydroxide. The electrodes can be coated using customary methods, such as the method proposed by HJ Schäfer. In principle, a Ni (OH) 2 layer is first cathodically deposited on the later anode from a Ni salt solution and then anodically converted to NiO (OH) in alkaline solution (J. Kaulen, HJ Schäfer, Tetrahedron, 1982, 38, 3299).

Als mit NiO(OH) zu beschichtende Anodenmaterialien können außer Nickelmetall auch andere Materialien verwendet werden, auf welchen die aktivierte Nickeloxidhydroxidschicht haftet, wie Monel, rostfreier Stahl, Graphit oder glasartiger Kohlenstoff.As anode materials to be coated with NiO (OH), Nickel metal other materials are used on which the activated nickel oxide hydroxide layer adheres like Monel, stainless steel, graphite or vitreous carbon.

Die Kathode kann aus einem beliebigen, üblicherweise in der Elektrochemie für die Herstellung von Kathoden verwendeten Material bestehen, wie etwa Edelmetallen, Edelstahl oder Nickel.The cathode can be any, usually in the Electrochemical material used for the manufacture of cathodes exist, such as precious metals, stainless steel or nickel.

Die Elektrolysezelle kann aus beliebigem, gegen Elektrolyt und Reaktanden beständigem Material bestehen, wie alkalibeständiges Glas, Porzellan, Polyethylen, Kautschuk oder Edelstahl.The electrolytic cell can be made of any, against electrolyte and There are reactant-resistant materials such as alkali-resistant Glass, porcelain, polyethylene, rubber or stainless steel.

Der Zelltyp kann geteilt oder ungeteilt sein, wobei letzteres bevorzugt wird, da eine Reduktion des gewünschten Elektrolyseproduktes nicht befürchtet werden muß.The cell type can be divided or undivided, the latter is preferred because a reduction in the desired electrolysis product need not be feared.

Das erfindungsgemäße Verfahren kann kontinuierlich oder diskontinuierlich durchgeführt werden, wobei bevorzugterweise diskontinuierlich gearbeitet wird. Bei dieser Arbeitsweise besteht das Elektrolysesystem aus einer wässrigen Lösung der β-Hydroxyethylammonium-Verbindung mit einem pH-Wert vorzugsweise von über 12. Die Alkalität der Lösungen wird in der Regel durch Alkalihydroxide (vorzugsweise NaOH und KOH) bewirkt. Die für die Neutralisation der entstehenden Säure notwendige Lauge wird nach und nach zugegeben, wobei etwas weniger als die theoretisch notwendige Menge zugesetzt wird, so dass der pH-Wert der nach Abschluss der Elektrolyse erhaltenen Lösung bei etwa 9 liegt. The process according to the invention can be carried out continuously or batchwise be carried out, preferably discontinuously is worked. In this way of working there is the electrolysis system from an aqueous solution of the β-Hydroxyethylammonium compound with a pH preferably of over 12. The alkalinity of the solutions is usually caused by alkali metal hydroxides (preferably NaOH and KOH). The lye necessary for the neutralization of the resulting acid is gradually added, slightly less than that theoretically necessary amount is added so that the pH the solution obtained after the electrolysis is complete at about 9 lies.

Zweckmäßige Gehalte an β-Hydroxyethylammonium-Verbindung der alkalischen Lösung liegen zwischen 1 und 30 Gew.-%, vorzugsweise zwischen 20 und 30 Gew.-%.Appropriate levels of β-hydroxyethylammonium compound alkaline solution are between 1 and 30 wt .-%, preferably between 20 and 30% by weight.

Die Elektrolysetemperatur beträgt normalerweise 20 bis 80 °C, vorzugsweise etwa 70 °C.The electrolysis temperature is usually 20 to 80 ° C, preferably about 70 ° C.

Es ist weiterhin zweckmäßig, die Elektrolyse mit einer höheren als der theoretisch erforderlichen Strommenge durchzuführen, vorzugsweise der 1,5- bis 3fachen Strommenge.It is also expedient to use a higher electrolysis than the amount of electricity theoretically required, preferably 1.5 to 3 times the amount of electricity.

Nach beendeter Elektrolyse wird die elektrolysierte Lösung beispielsweise mit Phosphorsäure auf pH 6 bis 7 gebracht, eingeengt und der Rückstand mit einem geeigneten Lösungsmittel extrahiert. Hierfür sind z.B. Alkohole (Ethanol, Isopropanol) geeignet. Der erhaltene Extrakt wird vom Lösungsmittel befreit und liefert die reinen Betaine.After the electrolysis has ended, the electrolyzed solution is, for example brought to pH 6 to 7 with phosphoric acid, concentrated and the residue with a suitable solvent extracted. For this, e.g. Alcohols (ethanol, isopropanol) suitable. The extract obtained is freed from the solvent and delivers the pure betaines.

Die Extraktion ist nur dann erforderlich, wenn die salzfreien Betaine erhalten werden sollen. Üblicherweise stören die bei der Synthese anfallenden Salze jedoch nicht, so dass auf eine Extraktion verzichtet werden kann.The extraction is only necessary if the salt-free Betaines are to be obtained. They usually interfere with the synthesis of salts, however, so that on a Extraction can be dispensed with.

Die erfindungsgemäß mitverwendeten β-Hydroxyethylammonium-Verbindungen können nach den auf diesem Gebiet bekannten Verfahren durch Umsetzung von Aminen mit Ethylenoxid in saurer Lösung hergestellt werden (EP-A-0 098 802).The β-hydroxyethylammonium compounds used in accordance with the invention can by the methods known in this field by reacting amines with ethylene oxide in an acidic solution can be produced (EP-A-0 098 802).

Als β-Hydroxyethylammonium-Verbindungen sind alle Verbindungen verwendbar, welche mindestens eine quartäre Aminogruppe und mindestens eine OH-Gruppe, vorzugsweise der Formeln (I) und/oder (II) und/oder (III) enthalten

Figure 00070001
Figure 00070002
in welcher die Reste

R
unabhängig voneinander Alkylreste mit 1 bis 3 C-Atomen und/oder -CH2-CH2-OH sein kann und
n,m,o
Werte zwischen 1 bis 5, vorzugsweise 1 bis 3, insbesondere 1 sein können, und
R1
ein gegebenenfalls Heteroatome, inbesondere Sauerstoff- und/oder Stickstoffatome enthaltender Alkylrest oder der Rest Ra-[C(O)-NH-(CH2) q]r- mit q = 1 bis 6, vorzugsweise 2 oder 3, und r = 0 oder 1, ist.
All compounds which contain at least one quaternary amino group and at least one OH group, preferably of the formulas (I) and / or (II) and / or (III), can be used as β-hydroxyethylammonium compounds
Figure 00070001
Figure 00070002
in which the remains
R
can independently be alkyl radicals having 1 to 3 carbon atoms and / or -CH 2 -CH 2 -OH and
n, m, o
Values can be between 1 to 5, preferably 1 to 3, in particular 1, and
R 1
an alkyl radical optionally containing heteroatoms, in particular oxygen and / or nitrogen atoms, or the radical R a - [C (O) -NH- (CH 2 ) q ] r - with q = 1 to 6, preferably 2 or 3, and r = 0 or 1.

Erfindungsgemäß bevorzugt sind Verbindungen, in denen die freien Valenzen der allgemeinen Formel (I) gebunden sind an den Rest Ra-C(O)-NH, wobei Ra ein gegebenenfalls substituierter Alkyl- oder Alkenylrest mit 7 bis 21 C-Atomen oder ein gegebenenfalls substituierter Alkyl- oder Alkenylrest mit 1 bis 22 C-Atomen, vorzugsweise mit 7 bis 17 C-Atomen, sein kann und die Reste R unabhängig voneinander Alkylreste mit 1 bis 3 C-Atomen sein können; oder, wenn r = 0 ist, Ra ein Alkyl- oder Alkenylrest mit 8 bis 22 C-Atomen sein kann; Valenzen der allgemeinen Formeln (I) bis (III) gebunden sind an einen gegebenenfalls substituierten Alkyl- oder Alkenylrest mit 1 bis 22 C-Atomen, vorzugsweise mit 8 bis 18 C-Atomen oder an den Rest Ra-C(O)-[NH-(CH2)z]y- in dem Ra die oben angegebene Bedeutung hat, und z,y unabhängig voneinander Zahlen von 1 bis 3 sein können; in denen die freien Valenzen der allgemeinen Formel (IV) gebunden sind an den Rest Ra, mit der oben angegebenen Bedeutung.According to the invention, preference is given to compounds in which the free valences of the general formula (I) are bonded to the radical R a -C (O) -NH, where R a is an optionally substituted alkyl or alkenyl radical having 7 to 21 C atoms or a optionally substituted alkyl or alkenyl radical having 1 to 22 carbon atoms, preferably having 7 to 17 carbon atoms, and the radicals R can independently be alkyl radicals having 1 to 3 carbon atoms; or, if r = 0, R a can be an alkyl or alkenyl radical having 8 to 22 carbon atoms; Valences of the general formulas (I) to (III) are bonded to an optionally substituted alkyl or alkenyl radical having 1 to 22 C atoms, preferably having 8 to 18 C atoms, or to the radical R a -C (O) - [ NH- (CH 2 ) z ] y - in which R a has the meaning given above, and z, y can independently be numbers from 1 to 3; in which the free valences of the general formula (IV) are bound to the radical R a , with the meaning given above.

Der Rest Ra leitet sich bevorzugt von natürlichen Fettsäuren ab, wie Caprylsäure, Caprinsäure, 2-Ethylhexansäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Isostearinsäure, Stearinsäure, Hydroxystearinsäure (Ricinolsäure), Dihydroxystearinsäure, Ölsäure, Linolsäure, Petroselinsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure, Gadoleinsäure sowie die bei der Druckspaltung natürlicher Fette und Öle anfallenden technischen Mischungen, wie Ölsäure, Linolsäure, Linolensäure und insbesondere Rapsölfettsäure, Sojaölfettsäure, Sonnenblumenölfettsäure, Tallölfettsäure. Geeignet sind prinzipiell alle Fettsäuren mit ähnlicher Kettenverteilung.The radical R a is preferably derived from natural fatty acids, such as caprylic acid, capric acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, hydroxystearic acid (ricinoleic acid), dihydroxystearic acid, oleic acid, linoleic acid, petroselic acid, araidic acid, elaidic acid, elaidic acid Behenic acid and erucic acid, gadoleic acid and the technical mixtures resulting from the pressure splitting of natural fats and oils, such as oleic acid, linoleic acid, linolenic acid and in particular rapeseed oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, tall oil fatty acid. In principle, all fatty acids with a similar chain distribution are suitable.

Der Gehalt dieser Fettsäuren bzw. Fettsäureester an ungesättigten Anteilen wird - soweit dies erforderlich ist - durch die bekannten katalytischen Hydrierverfahren auf eine gewünschte Jodzahl eingestellt oder durch Abmischung von vollhydrierten mit nichthydrierten Fettkomponenten erzielt.The content of these fatty acids or fatty acid esters in unsaturated Shares will - if this is necessary - through the known catalytic hydrogenation processes on a desired iodine number or by mixing fully hydrated with unhydrogenated fat components.

Die Jodzahl, als Maßzahl für den durchschnittlichen Sättigungsgrad einer Fettsäure, ist die Jodmenge, welche von 100 g der Verbindung zur Absättigung der Doppelbindungen aufgenommen wird.The iodine number, as a measure of the average degree of saturation a fatty acid, is the amount of iodine, which from 100 g Connection for the saturation of the double bonds added becomes.

Vorzugsweise werden teilgehärtete C8/18-Kokos- bzw. Palmfettsäuren, Rapsölfettsäuren, Sonnenblumenölfettsäuren, Sojaölfettsäuren und Tallölfettsäuren, mit Jodzahlen im Bereich von ca. 80 bis 150 und insbesondere technische C8/18-Kokosfettsäuren eingesetzt, wobei gegebenenfalls eine Auswahl von cis/trans-Isomeren, wie elaidinsäurereiche C16/18-Fettsäureschnitte von Vorteil sein können. Sie sind handelsübliche Produkte und werden von verschiedenen Firmen unter deren jeweiligen Handelsnamen angeboten.Partially hardened C 8/18 coconut or palm fatty acids, rapeseed oil fatty acids, sunflower oil fatty acids, soybean oil fatty acids and tall oil fatty acids with iodine numbers in the range from approx. 80 to 150 and in particular technical C 8/18 coconut fatty acids are used, where appropriate a selection of cis / trans isomers, such as C 16/18 fatty acid cuts rich in elaidic acid, can be advantageous. They are commercially available products and are offered by various companies under their respective trade names.

Die Verbindungen der allgemeinen Formeln (I) bis (III) werden wie nachfolgend beschrieben elektrochemisch zu den entsprechenden Säuren oxidiert.The compounds of general formulas (I) to (III) are as described below electrochemically to the corresponding Acids oxidized.

Beispiel 1:Example 1:

An einer Netzelektrode (60,5 cm2, Nickelnetz mit NiO(OH) beschichtet) und einer Kathode (Zylinder, Ø 1,7 cm, 7 cm hoch, rostfreier Edelstahl) wurden in einer 150-ml-Becherglaszelle mit Rückflusskühler 105 ml einer 27 %igen Lösung von 2-Hydroxyethyl(dimethyl)3-undecylcarboxamidopropylammonium x 0,5 H2PO4 -, die 4,2 g NaOH enthielt, für 7 h bei einer Stromstärke von 2,0 A elektrolysiert. Dabei stieg der pH-Wert binnen 5 h auf 8 bis 9 an, und es wurden 4 ml gesättigte NaOH-Lösung zugesetzt. Anschließend wurde die Stromstärke auf 1,0 A eingestellt und für weitere 7 h elektrolysiert. Nach dieser Zeit weist die Lösung wiederum einen pH-Wert von 8 bis 9 auf, und es werden erneut 4 ml gesättigte NaOH-Lösung zugesetzt. Anschließend wird eine Stromstärke von 0,5 A eingestellt und für weitere 7,5 h elektrolysiert. Die erhaltene Lösung weist einen pH-Wert von 8 bis 9 auf. Die Reaktionskontrolle erfolgte mittels DC-Chromatographie und ESI-Massenspektrometrie.On a mesh electrode (60.5 cm 2 , nickel mesh coated with NiO (OH)) and a cathode (cylinder, Ø 1.7 cm, 7 cm high, stainless steel) in a 150 ml beaker cell with reflux condenser 105 ml 27% solution of 2-hydroxyethyl (dimethyl) 3-undecylcarboxamidopropylammonium x 0.5 H 2 PO 4 - , which contained 4.2 g NaOH, was electrolyzed for 7 h at a current of 2.0 A. The pH rose to 8 to 9 within 5 h and 4 ml of saturated NaOH solution were added. The current was then set to 1.0 A and electrolyzed for a further 7 h. After this time, the solution again has a pH of 8 to 9 and 4 ml of saturated NaOH solution are again added. A current of 0.5 A is then set and electrolyzed for a further 7.5 h. The solution obtained has a pH of 8 to 9. The reaction was checked by means of TLC chromatography and ESI mass spectrometry.

Der Elektrolyseaustrag wird mit Phosphorsäure auf einen pH-Wert von 6 bis 7 eingestellt und eingeengt. Der Rückstand wird mit Isopropanol extrahiert und der erhaltene Extrakt vom Lösungsmittel befreit. Als Produkt erhält man einen gelb-braunen Feststoff.The electrolysis discharge is carried out with phosphoric acid pH is adjusted from 6 to 7 and concentrated. The residue is extracted with isopropanol and the extract obtained freed from the solvent. As a product you get a yellow-brown solid.

Analytikanalytics

Ausbeute: 23,3 g (91 % d. Th.)
13C-NMR (100 MHz, CDCl3): δ = 13,67 (CH3), 22,24 bis 31,48 (CH2), 35,86 und 35,87 (CH2CONH und CONHCH2), 50,32 (N+(CH3)2), 62,12 (CH2N+), 63,98 (N+ CH2COO-), 167,09 (COO-), 174,06 (CONH) ppm.Yield: 23.3 g (91% of theory)
13 C NMR (100 MHz, CDCl 3 ): δ = 13.67 (CH 3 ), 22.24 to 31.48 (CH 2 ), 35.86 and 35.87 ( C H 2 CONH and CONH C H 2 ), 50.32 (N + (CH 3 ) 2 ), 62.12 (CH 2 N + ), 63.98 (N + C H 2 COO - ), 167.09 (COO - ), 174.06 (CONH) ppm.

Beispiel 2:Example 2:

Der Versuch wurde analog zu Beispiel 1 durchgeführt. Im Unterschied zu Beispiel 1 wurde 2-Hydroxyethyl(dimethyl)3-undecylcarboxamidopropylammonium x 0,5 C2O4H- als Edukt verwendet. Während der Oxidation wird zunächst Oxalat zu CO2 oxidiert, das unter den alkalischen Bedingungen zu Carbonat reagiert und erst anschließend der Ammoniumalkohol zum entsprechenden Glycinderivat oxidiert. Die entsprechend größere notwendige Menge an NaOH wurde der Lösung von Anfang an zugesetzt.The experiment was carried out analogously to Example 1. In contrast to Example 1, 2-hydroxyethyl (dimethyl) 3-undecylcarboxamidopropylammonium x 0.5 C 2 O 4 H - was used as the starting material. During the oxidation, oxalate is first oxidized to CO 2 , which reacts to carbonate under the alkaline conditions and only then oxidizes the ammonium alcohol to the corresponding glycine derivative. The correspondingly larger amount of NaOH required was added to the solution from the start.

Analytikanalytics

Ausbeute: 20,28 g (82 % d. Th.)
13C-NMR (100 MHz, CDCl3) : δ = 13,39 (CH3), 21,95 bis 31,18 (CH2), 35,55 (br, CH2CONH und CONHCH2), 50,15 (N+(CH3)2), 61,77 (CH2N+), 63,73 (N+ CH2COO-), 165,81 (COO-), 173,65 (CONH) ppm. Yield: 20.28 g (82% of theory)
13 C-NMR (100 MHz, CDCl 3 ): δ = 13.39 (CH 3 ), 21.95 to 31.18 (CH 2 ), 35.55 (br, C H 2 CONH and CONH C H 2 ) , 50.15 (N + (CH 3 ) 2 ), 61.77 (CH 2 N + ), 63.73 (N + C H 2 COO - ), 165.81 (COO - ), 173.65 (CONH ) ppm.

Beispiel 3:Example 3:

Der Versuch wurde analog zu Beispiel 1 durchgeführt. Im Unterschied zu Beispiel 1 wurden 105 ml einer 2,7 %igen Lösung eines Ammoniumgemisches (zugrunde liegt der Kokosfettsäureschnitt), das als Hauptkomponente das 2-Hydroxyethyl(dimethyl)3-undecylcarboxamidopropylammonium x 0,5 H2PO4 - enthielt, für 3 h bei 2,0 A elektrolysiert.The experiment was carried out analogously to Example 1. In contrast to Example 1, 105 ml of a 2.7% solution of an ammonium mixture (based on the coconut fatty acid cut), which contained 2-hydroxyethyl (dimethyl) 3-undecylcarboxamidopropylammonium x 0.5 H 2 PO 4 - as the main component, for 3 h electrolyzed at 2.0 A.

Analytikanalytics

Ausbeute: 2,35 g (96 % d. Th.)
13C-NMR (100 MHz, CDCl3) : δ = 13,69 (CH3), 22,24 bis 31,48 (CH2), 35,84 und 35,87 (CH2CONH und CONHCH2), 50,41 (N+(CH3)2), 62,23 (CH2N+), 64,31 (N+ CH2COO-), 166,14 (COO-), 173,93 (CONH) ppm.
MS (ESI) : m/z = 365 (M+ +Na, 100 %).Yield: 2.35 g (96% of theory)
13 C-NMR (100 MHz, CDCl 3 ): δ = 13.69 (CH 3 ), 22.24 to 31.48 (CH 2 ), 35.84 and 35.87 ( C H 2 CONH and CONH C H 2 ), 50.41 (N + (CH 3 ) 2 ), 62.23 (CH 2 N + ), 64.31 (N + C H 2 COO - ), 166.14 (COO - ), 173.93 (CONH) ppm.
MS (ESI): m / z = 365 (M + + Na, 100%).

Claims (6)

Verfahren zur Herstellung von Glycinderivaten, dadurch gekennzeichnet, dass die Hydroxylgruppen von β-Hydroxyethylammonium-Verbindungen elektrochemisch zu den entsprechenden Säuren oxidiert werden.Process for the preparation of glycine derivatives, characterized in that the hydroxyl groups of β-hydroxyethylammonium compounds are oxidized electrochemically to the corresponding acids. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die wässrigen Lösungen von β-Hydroxyethylammonium-Verbindungen elektrochemisch unter Verwendung von mit Nickeloxidhydroxid beschichteten Elektroden zu den entsprechenden Säuren oxidiert werden.A method according to claim 1, characterized in that the aqueous solutions of β-hydroxyethylammonium compounds are oxidized electrochemically to the corresponding acids using electrodes coated with nickel oxide hydroxide. Verfahren nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, dass die β-Hydroxyethylammoniumverbindungen bei pH-Werten im Bereich von 8 bis 14 oxidiert werden.Process according to claims 1 to 2, characterized in that the β-hydroxyethylammonium compounds are oxidized at pH values in the range from 8 to 14. Glycinverbindungen, frei von organisch gebundenem Halogen und/oder Halogenidionen, dadurch hergestellt, dass die Hydroxylgruppen von β-Hydroxyethylammonium-Verbindungen elektrochemisch zu den entsprechenden Säuren oxidiert werden.Glycine compounds, free of organically bound halogen and / or halide ions, produced in that the hydroxyl groups of β-hydroxyethylammonium compounds electrochemically to the corresponding acids be oxidized. Glycinverbindungen, frei von organisch gebundenem Halogen und/oder Halogenidionen, hergestellt gemäß den Ansprüchen 2 bis 3.Glycine compounds, free of organically bound halogen and / or halide ions, produced according to the claims 2 to 3. Verwendung der gemäß Ansprüche 1 bis 3 hergestellten Glycinverbindungen zur Herstellung von tensidischen Zubereitungen.Use of those produced according to claims 1 to 3 Glycine compounds for the preparation of surfactant preparations.
EP02006731A 2001-04-06 2002-03-23 Process for the preparation of glycine derivatives Expired - Lifetime EP1247880B1 (en)

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