EP1247880B1 - Procédé de préparation de dérivés de glycine - Google Patents

Procédé de préparation de dérivés de glycine Download PDF

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Publication number
EP1247880B1
EP1247880B1 EP02006731A EP02006731A EP1247880B1 EP 1247880 B1 EP1247880 B1 EP 1247880B1 EP 02006731 A EP02006731 A EP 02006731A EP 02006731 A EP02006731 A EP 02006731A EP 1247880 B1 EP1247880 B1 EP 1247880B1
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EP
European Patent Office
Prior art keywords
acid
glycine derivatives
compounds
oxidation
solution
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.)
Expired - Lifetime
Application number
EP02006731A
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German (de)
English (en)
Other versions
EP1247880A2 (fr
EP1247880A3 (fr
Inventor
Oliver Dr. Thurmüller
Philipp Dr. Thomuschat
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.)
Evonik Goldschmidt GmbH
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Evonik Goldschmidt GmbH
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Publication of EP1247880A3 publication Critical patent/EP1247880A3/fr
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Classifications

    • 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
    • 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
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/01—Products
    • C25B3/09—Nitrogen containing compounds

Definitions

  • the invention relates to a novel process for the preparation of glycine derivatives.
  • Glycine derivatives such as betaines are known as mild and compatible substances and are used in large quantities for the production of cosmetic preparations for the cleansing and care of skin and hair.
  • Glycine derivatives are prepared by the processes known in the art by reacting tertiary amines with excess monochloroacetic acid in excess in basic aqueous solution at elevated temperature.
  • MCA monochloroacetic acid
  • DCA dichloroacetic acid
  • the DE-A-39 39 264 relates to a process for lowering the residual content of free alkylating agent in aqueous solutions of amphoteric or zwitterionic surfactants, characterized in that the solutions are aftertreated with ammonia, an amino acid having 2 to 8 C atoms or an oligopeptide.
  • This residual treatment also leaves a residual content of MCA and / or DCA in the reaction product.
  • the reaction products of ammonia and alkylating agent or peptide and alkylating agent produce reaction products which remain as impurities in the process product.
  • reaction mixtures contain large amounts of chloride ions in the form of their alkali or ammonium salts.
  • they have other disadvantages such as increasing the viscosity of the final product, adversely affecting the low temperature stability of formulations, and they can not be formulated with a number of other active ingredients.
  • the oxidation of the quaternary amino alcohol to the corresponding glycine derivative can be carried out by electrochemical oxidation in aqueous alkaline solution using coated nickel electrodes.
  • the present invention therefore relates to a process for the preparation of glycine derivatives by oxidation of ⁇ -hydroxyethylammonium compounds by electrolysis of an aqueous alkaline solution, which is characterized in that the oxidation is carried out using nickel oxide hydroxide-coated anodes.
  • the method is characterized by extraordinary environmental friendliness, since on the one hand no polluting by-products are incurred and on the other hand can be dispensed with the use of highly toxic chloroacetic acid.
  • a product is obtained directly free of inorganic chlorine, so that can be dispensed with a technically complex separation of the chloride ions.
  • the electrolysis is in principle carried out so that the aqueous electrolyte is electrolyzed on nickel oxide hydroxide coated electrodes.
  • the coating of the electrodes can be carried out according to customary methods such as, for example, the method proposed by HJ Schfer.
  • a Ni (OH) 2 layer is first cathodically deposited from a Ni salt solution on the later anode and then converted anodically in alkaline solution to NiO (OH) ( J. Kaulen, HJ Schaefer, Tetrahedron, 1982, 38, 3299 ).
  • NiO OH
  • other materials to which the activated nickel oxide hydroxide layer is adhered such as Monel, stainless steel, graphite or glassy carbon, may be used.
  • the cathode may be made of any material commonly used in electrochemistry for the manufacture of cathodes, such as precious metals, stainless steel or nickel.
  • the electrolysis cell may consist of any material resistant to electrolyte and reactants, such as alkali-resistant glass, porcelain, polyethylene, rubber or stainless steel.
  • the cell type may be divided or undivided, with the latter being preferred, since no reduction of the desired electrolysis product must be feared.
  • the electrolysis system consists of an aqueous solution of the ⁇ -hydroxyethylammonium compound having a pH preferably above 12.
  • the alkalinity of the solutions is generally effected by alkali metal hydroxides (preferably NaOH and KOH).
  • the necessary for the neutralization of the resulting acid liquor is added gradually, with slightly less than the theoretically necessary amount is added, so that the pH of the solution obtained after completion of the electrolysis is about 9.
  • Advantageous levels of ⁇ -hydroxyethylammonium compound of the alkaline solution are between 1 and 30 wt .-%, preferably between 20 and 30 wt .-%.
  • the electrolysis temperature is usually 20 to 80 ° C, preferably about 70 ° C.
  • the electrolyzed solution is brought to pH 6 to 7, for example with phosphoric acid, concentrated and the residue extracted with a suitable solvent.
  • a suitable solvent e.g. Alcohols (ethanol, isopropanol) suitable.
  • the resulting extract is freed from the solvent and gives the pure betaines.
  • ⁇ -hydroxyethylammonium compounds used in accordance with the invention can be prepared by reaction of amines with ethylene oxide in acidic solution by the processes known in the art (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, petroselinic acid, elaidic acid, arachidic acid, Behenic acid and erucic acid, gadoleic acid and the technical mixtures obtained in 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, 2-ethylhe
  • the content of these fatty acids or fatty acid esters in unsaturated proportions is - as far as necessary - adjusted by the known catalytic hydrogenation to a desired iodine value or achieved by mixing fully hydrogenated with non-hydrogenated fat components.
  • the iodine number is the amount of iodine absorbed by 100 g of the compound to saturate the double bonds.
  • C 8/18 coconut or palm oil fatty acids Preferably, partially cured C 8/18 coconut or palm oil 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 of about 80 to 150 and in particular technical C 8/18 coconut fatty acids are used, it being possible where appropriate for a selection of cis / trans isomers, such as elaidic acid C 16/18 fatty acid cuts, to be advantageous. They are commercial 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 added again. Subsequently, a current of 0.5 A is set and electrolyzed for a further 7.5 h. The resulting solution has a pH of 8 to 9.
  • the reaction was monitored by TLC chromatography and ESI mass spectrometry.
  • the Elektrolyseaustrag is adjusted with phosphoric acid to a pH of 6 to 7 and concentrated.
  • the residue is extracted with isopropanol and the extract obtained freed from the solvent.
  • the product gives 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 starting material.
  • oxalate is first oxidized to CO 2 , which reacts under the alkaline conditions to carbonate 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 beginning.
  • Example 2 The experiment was carried out analogously to Example 1.

Landscapes

  • 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)

Claims (3)

  1. Procédé pour la préparation de dérivés de glycine, caractérisé en ce que les groupes hydroxyle de composés de β-hydroxyéthylammonium sont oxydés par voie électrochimique en acides correspondants.
  2. Procédé selon la revendication 1, caractérisé en ce que les solutions aqueuses de composés de β-hydroxyéthylammonium sont oxydées par voie électrochimique avec utilisation d'électrodes revêtues par de l'hydroxyde d'oxyde de nickel en acides correspondants.
  3. Procédé selon les revendications 1 à 2, caractérisé en ce que les composés de β-hydroxyéthylammonium sont oxydés à des pH dans la plage de 8 à 14.
EP02006731A 2001-04-06 2002-03-23 Procédé de préparation de dérivés de glycine Expired - Lifetime EP1247880B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10117222A DE10117222B4 (de) 2001-04-06 2001-04-06 Verfahren zur Herstellung von Glycinderivaten
DE10117222 2001-04-06

Publications (3)

Publication Number Publication Date
EP1247880A2 EP1247880A2 (fr) 2002-10-09
EP1247880A3 EP1247880A3 (fr) 2004-04-14
EP1247880B1 true EP1247880B1 (fr) 2008-12-24

Family

ID=7680661

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02006731A Expired - Lifetime EP1247880B1 (fr) 2001-04-06 2002-03-23 Procédé de préparation de dérivés de glycine

Country Status (5)

Country Link
US (1) US6663764B2 (fr)
EP (1) EP1247880B1 (fr)
JP (1) JP2003013270A (fr)
AT (1) ATE418629T1 (fr)
DE (2) DE10117222B4 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004024991A1 (fr) 2002-09-10 2004-03-25 Solvay Sa Sels organiques et leur utilisation en tant que reactifs dans des reactions electrochimiques

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE348380C (de) * 1922-02-07 Anilin Fabrikation Ag Verfahren zur Reingewinnung von Betain
GB614984A (en) * 1945-09-05 1948-12-30 Roche Products Ltd A process for the manufacture of ª‰-alanine
FR1437540A (fr) * 1965-03-22 1966-05-06 Kuhlmann Ets Procédé de préparation d'hydrate de bétaïne
DE3374305D1 (en) 1982-07-05 1987-12-10 Basf Ag Process for the preparation of quaternary ammonium salts
JPS5975998A (ja) * 1982-10-22 1984-04-28 味の素株式会社 両性界面活性剤の精製法
US4488944A (en) * 1983-10-19 1984-12-18 The Dow Chemical Company Electrocatalytic oxidation of (poly)alkylene glycols
DE3443303A1 (de) 1984-11-28 1986-06-05 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von 3-hydroxy-3-methylglutarsaeure
GB8509746D0 (en) 1985-04-16 1985-05-22 Shell Int Research Preparing azetidine derivatives
JPS63130129A (ja) 1986-11-18 1988-06-02 Kao Corp 界面活性剤の製造法
DE3929063A1 (de) 1989-09-01 1991-03-07 Henkel Kgaa Verfahren zur herstellung von alkalisalzen von ethercarbonsaeuren
DE3939264A1 (de) 1989-11-28 1991-05-29 Henkel Kgaa Verfahren zur nachbehandlung amphoterer oder zwitterionischer tenside
ES2066534T3 (es) * 1991-09-19 1995-03-01 Hoechst Ag Procedimiento para la oxidacion de derivados de hidroximetilpiridina en derivados de acido piridincarboxilico.
US5179218A (en) 1991-09-30 1993-01-12 Shell Oil Company Process for the oxidation of alcohols to acids
DE4205880A1 (de) 1992-02-26 1993-09-02 Goldschmidt Ag Th Verfahren zur herstellung von betainen
EP0701999B1 (fr) * 1994-09-16 1998-08-19 Th. Goldschmidt AG Procédé de préparation de bétaines
US5792737A (en) * 1994-11-07 1998-08-11 Th. Goldschmidt Ag Mild, aqueous, surfactant preparation for cosmetic purposes and as detergent
DE19510313A1 (de) 1995-03-22 1996-09-26 Henkel Kgaa Verbessertes Oxidationsverfahren zur Herstellung von Polycarboxylaten aus Polysacchariden

Also Published As

Publication number Publication date
DE10117222B4 (de) 2004-12-30
ATE418629T1 (de) 2009-01-15
EP1247880A2 (fr) 2002-10-09
US20020157943A1 (en) 2002-10-31
US6663764B2 (en) 2003-12-16
DE10117222A1 (de) 2002-10-24
JP2003013270A (ja) 2003-01-15
EP1247880A3 (fr) 2004-04-14
DE50213141D1 (de) 2009-02-05

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