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

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)

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• 2001
  • 2001-04-06 DE DE10117222A patent/DE10117222B4/de not_active Expired - Fee Related
• 2002
  • 2002-03-23 EP EP02006731A patent/EP1247880B1/fr not_active Expired - Lifetime
  • 2002-03-23 DE DE50213141T patent/DE50213141D1/de not_active Expired - Lifetime
  • 2002-03-23 AT AT02006731T patent/ATE418629T1/de not_active IP Right Cessation
  • 2002-04-04 US US10/116,599 patent/US6663764B2/en not_active Expired - Fee Related
  • 2002-04-05 JP JP2002104069A patent/JP2003013270A/ja active Pending

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