EP0019226B1 - Procédé de préparation de N-(alpha-alcoxyéthyl)-carboxamides - Google Patents

Procédé de préparation de N-(alpha-alcoxyéthyl)-carboxamides Download PDF

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Publication number
EP0019226B1
EP0019226B1 EP80102539A EP80102539A EP0019226B1 EP 0019226 B1 EP0019226 B1 EP 0019226B1 EP 80102539 A EP80102539 A EP 80102539A EP 80102539 A EP80102539 A EP 80102539A EP 0019226 B1 EP0019226 B1 EP 0019226B1
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EP
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Prior art keywords
alkyl
acid amides
electrolysis
alpha
ammonium
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EP80102539A
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German (de)
English (en)
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EP0019226A1 (fr
Inventor
Michael Dr. Mitzlaff
Jürgen Dr. Cramer
Rudolf Dr. Pistorius
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Hoechst AG
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Hoechst AG
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Priority to AT80102539T priority Critical patent/ATE1454T1/de
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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

  • N-alpha-alkoxyethyl-carboxamides are valuable intermediates, in particular for the production of N-vinyl-carboxamides (DE-A 23 36 977), which can be converted into water-soluble polymers with interesting and diverse application properties (Ullmanns Encyclopedia of Industrial Chemistry, 3 Edition, vol. 14, pages 261-264).
  • Electrodes Nets or sheets made of Pd or Pt as well as noble metal or mixed oxide coated metal electrodes, preferably titanium electrodes, are mentioned as electrode materials for this process.
  • the main salts used are salts whose cation is the ammonium, an alkali or tetraalkylammonium ion with (C 1 -C 6 ) -alkyl groups, the nitryl or nitrosyl ion, and whose anion is the nitrate or chloride ion, or oxygen in complex contain bound form with P, CI, Br or J as central atom or F in complex bound form with P, B, Ti, Sb, As, Sn or Si as central atom.
  • electrolyte salts especially ammonium or alkali metal nitrate, ammonium or Alkalihexafluorophosphat, -hexafluorotitanat, -hexafluorosilikat, hexafluoroantimonate, -hexafluoroarsenat, tetrafluoroborate, perchlorate or -trifluorostannat, Tetraalkylammoniumtetrafluoroborat or tetraalkylammonium chloride with (C 1 -C 8) alkyl mentioned.
  • conductive salts are alkali and tetraalkylammonium tetrafluoroborates, hexafluorophosphates and nitrates.
  • the ratios in the anodic alkoxylation of ring-shaped N compounds cannot be transferred to the anodic alkoxylation of open-chain N-alkylcarboxamides, especially since it is known that even within the class of open-chain carboxamides under one and the same electrolysis conditions - in particular using the same electrode material - completely different results can occur.
  • the anodic alkoxylation of dimethylformamide to N-alkoxymethyl-methylformamide succeeds easily both on Pt and on graphite anodes with tetrafluoroborates or nitrates as conductive salts, whereas the anodic alkoxylation of N- (mono-) methylformamide under the same conditions (to N -Alkoxymethylformamide) only on a Pt anode and with tetrafluoroborates as conductive salts
  • N-alpha-alkoxyethyl carboxamides would result, for example, in the anodic oxidation of N-ethylcarboxamides with an alcohol according to BE-A837906 using graphite anodes instead of the noble metal electrodes described there.
  • the glassy carbon instead of normal graphite, which is also known as the electrode material, since glassy carbon does not differ chemically from normal graphite and since the other properties important for electrolysis, such as e.g. the porosity of the material is essentially the same in both cases (N.L. Weinberg, Technique of Electroorganic Synthesis, Vol. V, Part 1, p. 19, John Wiley and Sons 1976).
  • the subject of the invention is thus a process for the preparation of N-alpha-alkoxy-ethyl-carboxamides by anodic alkoxylation of N-ethyl-carboxamides with an alcohol in an electrolysis cell provided with anode (s) and cathode (s) in the presence of a conductive salt; the process is characterized in that at least 1 alkali and / or tetraalkylammonium alkosulfate is used as the material for the anode vitreous carbon and as the conducting salt.
  • N-ethylcarboxamides - the amide nitrogen of which is only substituted by the ethyl group - can be used as starting materials for the process.
  • preference is given to using the N-ethylcarboxamides of the formula III which are also used for the process of BE-A 837 906 wherein R 1 H, (C 1 -C 6 ) alkyl or (C 6 -C 10 ) aryl - preferably H or CH 3 .
  • N-ethylcarboxamides of the formula 111 are, for example: N-ethylformamide, N-ethyl acetamide, N-ethylpropionamide, N-ethylbutyramide and N-ethylbenzamide; the preferred compounds are N-ethylformamide and N-ethyl acetamide.
  • Alcohols R'OH suitable for the process are - just like in the process of BE-PS 837 906 - mainly (C 1 -C 6 ) alkanols (methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol Etc.) ; methanol and ethanol, in particular methanol, are preferred.
  • Anode material for the process is commercially available glassy carbon.
  • the common base metals such as steel, nickel etc. can be used as cathode materials.
  • Conductive salts for the electrolysis process according to the invention are alkali and / or tetraalkylammonium alkosulfates.
  • alkali ions of Li, Na, K, Rb, Cs
  • alkali ions of these salts with the ions of Na and K being preferred.
  • Alkyl groups in the tetraalkylammonium salts are mainly those with 1-6 C atoms, preferably methyl and ethyl groups.
  • the tetramethylammonium salts are particularly preferred.
  • Alkosulfates are salts of sulfuric acid alkyl half-esters; preferred are the (C 1 -C 6 ) alkyl and especially the methyl and ethyl half esters.
  • Tetramethylammoniummethosulfat Methyltriethylammoniummethosulfat, Methyltripropylammoniumthosulfat, methyltri-n-butylammoniummethosulfat, Methyltriamylammoniummethosulfat, Methyltrihexylammoniummethosulfat, Tetraethylammoniumethosulfat, Ethyltrimethylammoniumethosulfat, Ethyltripropylammoniumethosulfat, ethyltri-n-butylammoniumethosulfat, Methyltriamylammoniumethosulfat, etc.
  • Ethyltrihexylammoniumethosulfat; the preferred conductive salts are tetramethylammonium methosulfate and tetraethylammonium ethosulfate, especially tetramethylammonium methosulfate.
  • the conductive salts can be used both individually and as a mixture.
  • the starting electrolysis solution contains the starting amide 111 and the conducting salt in alcoholic solution. It is advantageous if the molar ratio of N-ethylcarboxamide to alcohol is between about 1: 1 and about 1: 100, preferably between 1: 2 to about 1:60 and in particular between 1: 5 and about 1:50.
  • the concentration of the (total) electrolysis solution of conductive salt is advantageously between about 0.1 and about 40% by weight, preferably between about 5 and about 20% by weight.
  • the conductive salt is usually added after the alcoholic solution has been prepared, but the order can also be changed.
  • the electrolysis process according to the invention is advantageously carried out in such a way that an amount of electricity of at least about 2.5 Faraday / mol carboxamide is used.
  • the use of smaller amounts of electricity is possible; however, it reduces the sales of starting amide III.
  • the current density is expediently set between approximately 10 and 1000 mA / cm z , preferably between approximately 20 and 600 mA / cm z . Lower current densities are possible, but without advantage; rather, they slow down product formation.
  • a temperature which is below the boiling temperature of the respective alcohol and above the melting temperature of the electrolysis solution is advantageously chosen as the working temperature for the electrolysis.
  • temperatures from about -10 to + 100 ° C, preferably from about 0 to 60 ° C, are used.
  • Electrolysis is normally carried out at atmospheric pressure, but it can also be carried out under reduced or increased pressure, although without advantages.
  • the process can be optimized in terms of energy or material yield in that the conversion of the N-ethylcarboxamide is very high, e.g. over 99%, which also has a very advantageous effect on the processing of the electrolysis solution. It is therefore generally electrolyzed until practically all of the starting product has been converted, so that there is no need to separate it later from the reaction product. After the desired amount of electricity has been passed through, the electrolysis current is switched off, the electrolysis discharge is freed of the conducting salt and worked up in a known manner, preferably by distillation.
  • the reaction product of the electrolysis can e.g. be examined for purity by nuclear magnetic resonance spectroscopy.
  • the electrolysis can e.g. in the electrolytic cell (1) shown in the figure. It is provided with a tight-fitting lid (2) through which the current leads for the electrodes (3) and (4) are guided and in which there are openings (5) for the inlet of the electrolysis solution, (6) for the discharge of the Gases and for a thermometer (9).
  • the opening for the discharge of the gas can be provided with a reflux condenser in which evaporating portions of the electrolysis mixture can be re-condensed.
  • the electrolytic cell is encased and can be connected to a heating or cooling liquid circuit through the inlet (7) and outlet connection (8).
  • the temperature of the electrolysis solution is monitored by a thermometer (9) or a thermal sensor.
  • the two electrodes (3) (anode) and (4) (cathode) are arranged at a distance of 0.5 to 50 mm, preferably between 1 and 15 mm, from one another.
  • Anode material is glassy carbon.
  • a base metal such as nickel or a metal alloy such as VA steel is used as the cathode material.
  • the vertical arrangement of the electrodes can also be replaced by a horizontal one.
  • Electrodes it is also possible to arrange several pairs of electrodes, as has proven particularly useful in the block-like combination of angled or non-angled capillary gap electrodes with and without vibration of the electrodes. It is also possible to use the electrodes in a bipolar circuit.
  • the solution is passed through a stirrer, for example a magnetic stirrer (10), or by pumping around. especially with the block-like combinations, vigorously mixed.
  • a further opening is provided in the cover (2) of the electrolysis vessel (1) for continuously pumping around the electrolysis solution.
  • a part of each product preparation is separated from the circulated electrolysis solution.
  • the solution is worked up in a known manner.
  • the starting materials recovered in the distillation, after having been adjusted to the molar ratio used, are metered in again together with the required amount of the conductive salt of the continuously pumped-over electrolysis solution.
  • the method according to the invention has the particular advantage that, contrary to the material removal known also for electrodes made of glass-containing carbon (see NL Weinberg “Technique of Electroorganic Synthesis Vol. 5, Part 1, p. 19, Par. 2, John Wiley 1972) - practically no removal occurs in the electrolyte system used here. In addition, no troublesome, hardly soluble precipitate forms on the cathode. Because of the higher solubility of the conductive salts used according to the invention in alcohols, considerably higher current densities can be used than in the known processes which mainly work with the tetrafluoroborates, hexafluorophosphates and nitrates which are less soluble in alcohols; as a result, higher sales are possible in a shorter time.
  • the invention thus represents a significant advance.
  • a mixture of the respective carboxamide and the corresponding alcohol is poured into an electrolysis cell according to the figure of about 500 ml with a lid and reflux condenser, in which the conductive salt is dissolved.
  • the cell contents are stirred during the electrolysis using a magnetic stirrer at 50 to 60 revolutions per minute and kept at the value T given in Table 1 below. After the amount of current Q (also shown in Table 1) has been passed through, the current is switched off.
  • the electrolysis solution is worked up in a known manner.
  • An undivided electrolytic cell with a block-like electrode combination is installed in a flow-through apparatus with a circulation pump, heat exchanger and degassing vessel.
  • This consists of a glass-like carbon anode, a steel cathode and four bipolar electrode plates made of glass-like carbon. Between these plates is a stack of nickel mesh (2 layers of 0.19 mm and 0.1 mm wire gauge and two layers of 0.5 mm and 0.3 mm wire gauge) and polyethylene mesh (1 layer of 0 mesh) , 9 mm and 0.3 mm thread thickness) so that the nickel fabric came to rest on the cathode sides of the carbon plates or the steel plate. These combinations are built in to minimize the electrode gap.
  • All electrode plates are surrounded by a polyethylene frame that was 22 mm wide perpendicular to the flow direction of the electrolyte - parallel to the flow direction 12 mm wide - and, like each of the plates, was approximately 2.5 mm thick.
  • the effective electrode area of each anode was 255 cm 2 .

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (5)

1. Procédé de préparation de N-(a-alcoxy-éthyl-)-carboxamides par alcoxylation anodique de N-éthyl- carboxamides avec un alcool dans une cellule d'électrolyse équipée d'anode(s) et de cathode(s), en présence d'un sel conducteur, procédé caractérisé en ce qu'on utilise, comme matière pour l'anode, du carbone vitreux et, comme sel conducteur, au moins un alcosulfate de métal alcalin et/ou de tétraalkyl- ammonium.
2. Procédé de préparation selon la revendication 1 caractérisé en ce qu'on utilise, comme N-éthyl- carboxamides, des composés répondant à la formule III
Figure imgb0014
dans laquelle R1 représente l'hydrogène, un alkyle en C1-C6 ou un aryle en C6-C10, de préférence H ou CH3.
3. Procédé selon l'une des revendications 1 et 2, caractérisé en ce qu'on utilise, comme alcool, un alcanol en C1-C6, de préférence le méthanol ou l'éthanol, plus spécialement le méthanol.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on utilise, comme alcosulfates de métaux alcalins, le métho-sulfate et/ou l'éthosulfate de sodium et/ou de potassium.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on utilise, comme alco-sulfates de tétraalkyl-ammoniums, des méthosulfates et/ou des étho-sulfates d'alkyl-ammoniums contenant de 1 à 6 atomes de carbone dans chacun des alkyles, de préférence le métho-sulfate de tétraméthyl-ammonium.
EP80102539A 1979-05-16 1980-05-08 Procédé de préparation de N-(alpha-alcoxyéthyl)-carboxamides Expired EP0019226B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80102539T ATE1454T1 (de) 1979-05-16 1980-05-08 Verfahren zur herstellung von n-alpha-alkoxyethyl-carbons[ureamiden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792919756 DE2919756A1 (de) 1979-05-16 1979-05-16 Verfahren zur herstellung von n- alpha -alkoxyethyl-carbonsaeureamiden
DE2919756 1979-05-16

Publications (2)

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EP0019226A1 EP0019226A1 (fr) 1980-11-26
EP0019226B1 true EP0019226B1 (fr) 1982-08-11

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US (1) US4288300A (fr)
EP (1) EP0019226B1 (fr)
JP (1) JPS55154589A (fr)
AT (1) ATE1454T1 (fr)
AU (1) AU5843680A (fr)
CA (1) CA1135656A (fr)
DE (2) DE2919756A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3529531A1 (de) * 1985-08-17 1987-02-26 Basf Ag Verfahren zur herstellung von carbamidsaeureestern
US4927508A (en) * 1988-02-11 1990-05-22 The Dow Chemical Company Alkyl 2-fluoro-1-methoxyethylcarbamates
US5144074A (en) * 1988-02-24 1992-09-01 Air Products And Chemicals, Inc. Process for the synthesis of carboxamides
US4997984A (en) * 1989-12-19 1991-03-05 Shawa Denko K.K. Process for preparation of N-(α-alkoxyethyl)-carboxylic acid amide
DE102012008612A1 (de) * 2012-04-27 2013-10-31 Ika-Werke Gmbh & Co. Kg Temperaturmessvorrichtung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193483A (en) * 1964-01-14 1965-07-06 Monsanto Co Electrolysis of acrylamides
DE2336976A1 (de) * 1973-07-20 1975-02-13 Hoechst Ag Verfahren zur herstellung von n-(alphaalkoxyaethyl)-carbonsaeureamiden
DE2539767C2 (de) * 1975-09-06 1982-06-16 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von N-(α-Alkoxyäthyl)-carbonsäureamiden
NL7600544A (nl) * 1975-01-25 1976-07-27 Hoechst Ag Werkwijze voor de bereiding van n-(gamma-alkoxy- ethyl)-carbonzuuramiden.
US4149941A (en) * 1975-09-06 1979-04-17 Hoechst Aktiengesellschaft Process for preparing fungicidal monoalkoxy and dialkoxy N-substituted cyclic amines
US4138408A (en) * 1975-12-20 1979-02-06 Hoechst Aktiengesellschaft ω-Alkoxy derivatives of lactams and process for their manufacture

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Publication number Publication date
DE3060750D1 (en) 1982-10-07
ATE1454T1 (de) 1982-08-15
AU5843680A (en) 1980-11-20
DE2919756A1 (de) 1980-11-27
US4288300A (en) 1981-09-08
CA1135656A (fr) 1982-11-16
EP0019226A1 (fr) 1980-11-26
JPS55154589A (en) 1980-12-02

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