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EP0019226A1 - 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
EP0019226A1
EP0019226A1 EP80102539A EP80102539A EP0019226A1 EP 0019226 A1 EP0019226 A1 EP 0019226A1 EP 80102539 A EP80102539 A EP 80102539A EP 80102539 A EP80102539 A EP 80102539A EP 0019226 A1 EP0019226 A1 EP 0019226A1
Authority
EP
European Patent Office
Prior art keywords
electrolysis
alkyl
alkoxyethyl
carboxylic acid
anode
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.)
Granted
Application number
EP80102539A
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German (de)
English (en)
Other versions
EP0019226B1 (fr
Inventor
Michael Dr. Mitzlaff
Jürgen Dr. Cramer
Rudolf Dr. Pistorius
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.)
Hoechst AG
Original Assignee
Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT80102539T priority Critical patent/ATE1454T1/de
Publication of EP0019226A1 publication Critical patent/EP0019226A1/fr
Application granted granted Critical
Publication of EP0019226B1 publication Critical patent/EP0019226B1/fr
Expired legal-status Critical Current

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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- ⁇ -alkoxyethyl-carboxamides are valuable intermediates, in particular for the production of N-vinyl-carboxylic acid amide (DE-OS 23 36 977), which can be converted into water-soluble polymers with interesting and diverse application properties (Ullmann's 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, Cl, Br or J as the central atom or F in complex bound form with P, B, Ti, Sb, As, Sn or Si as the central atom.
  • electrolyte salts especially ammonium or alkali metal nitrate, ammonium or Alkalihexafluorop h osp h at, hexa- fluorotitanate, -hexafluorosilikat, hexafluoroantimonate, -hexafluoroarsenat, tetrafluoroborate, perchlorate or -trifluorostannat, Tetraalkylammoniumtetrafluoroborat or tetraalkylammonium chloride with (C 1 -C 6 ) alkyl groups 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
  • the anodic alkoxylation of N- (mono-) methylformamide under the same conditions succeed only on a Pt anode and with tetrafluoroborates as conductive salts
  • the subject of the invention is thus a process for the preparation of N - «- alkoxyethyl-carboxamides by anodic alkoxylation of N-ethyl-carboxamides with a Alcohol in an electrolytic cell provided with anode (s) and cathode (s) in the presence of a conductive salt; the V out is characterized in that there is used as the material for the anode and glassy carbon as a conducting salt at least one alkali and / or Tetraalkylammoniumalkosulfat.
  • 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-PS 837 906: wherein R 1 H, (C 1 -C 6 ) alkyl or (C 6 -C 10 ) aryl - especially H or CH3.
  • N-ethylcarboxamides of the formula III are, for example: N-ethylformamide, N-ethyl acetamide, N-ethylpropionamide, N-ethylbutyramide, * etc .; the preferred compounds are N-ethylformamide and N-ethyl acetamide.
  • N-Ethylbenzamide Alcohols R'OH suitable for the process are - as in the process of BE-PS 837 906 - mainly (C1-C6) alkanols (methanol, ethanol, n-propano. 1, 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.
  • the electrolysis starting solution contains the starting amide III 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 electrolyte salt is suitably between about 0.1 and about 4 wt .-% 0, preferably between about 5 and about 20 wt .-%.
  • 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 current of at least about 2.5 Faraday / mol carboxamide is used.
  • the use of smaller amounts of electricity is possible; however, it reduces the conversion of starting amide III.
  • the current density is expediently set between approximately 10 and 1000 mA / cm 2 , preferably between approximately 20 and 600 mA / cm 2 . 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.
  • the 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 reactive 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 tightly closing cover (2), through which the current leads for the electrodes (3) and (4) are guided, and in which there are openings (5) for the supply of the electrolysis solution, (6) for the discharge of the gas and (11) for a thermometer (9).
  • the opening for the discharge of the gas can be provided with a reflux cooler in which evaporating portions of the electrolysis mixture can be recondensed.
  • the electrolysis 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.
  • T non-noble 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.
  • the electrodes are 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 mixed vigorously by means of a stirrer, for example a magnetic stirrer (10), or by pumping around, especially in the case of the block-like combinations.
  • 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 removal of material which is also known for electrodes made of glass-containing carbon (see NL Weinberg "Technique of Electroorganic Synthesis” Vol. 5, Part 1, S. 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 less soluble tetrafluoroborates, hexafluorophosphates and nitrates in alcohols; this enables higher sales in a shorter time.
  • the invention thus represents a significant advance.
  • the process according to the invention - that is, using glassy carbon as the anode material and alkali metal and / or tetraalkylammonium alkosulfates as conductive salts - can also be used in the processes of BE-PSs 845 901 and 849 625 alkoxylate cyclic N compounds, in which case the be written end products arise.
  • 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.
  • a stack of nickel mesh (2 layers of mesh size 0.19 mm and 0.1 mm wire gauge and in between two layers of mesh size 0.5 mm and 0.3 mm wire gauge) and of polyethylene mesh (1 layer of mesh size 0) is placed between these plates , 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.
  • All electrode plates are surrounded by a polyethylene frame which 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)
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)

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

Family

ID=6070873

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80102539A Expired EP0019226B1 (fr) 1979-05-16 1980-05-08 Procédé de préparation de N-(alpha-alcoxyéthyl)-carboxamides

Country Status (7)

Country Link
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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0330205A3 (en) * 1988-02-24 1990-10-24 Air Products And Chemicals, Inc. Process for the synthesis of carboxamides

Families Citing this family (4)

* 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
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

Citations (3)

* 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
DE2539767A1 (de) * 1975-09-06 1977-03-17 Hoechst Ag Verfahren zur herstellung von n-(alpha-alkoxyaethyl)-carbonsaeureamiden

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* 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
DE2539767A1 (de) * 1975-09-06 1977-03-17 Hoechst Ag Verfahren zur herstellung von n-(alpha-alkoxyaethyl)-carbonsaeureamiden

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0330205A3 (en) * 1988-02-24 1990-10-24 Air Products And Chemicals, Inc. Process for the synthesis of carboxamides

Also Published As

Publication number Publication date
JPS55154589A (en) 1980-12-02
CA1135656A (fr) 1982-11-16
AU5843680A (en) 1980-11-20
EP0019226B1 (fr) 1982-08-11
DE2919756A1 (de) 1980-11-27
US4288300A (en) 1981-09-08
DE3060750D1 (en) 1982-10-07
ATE1454T1 (de) 1982-08-15

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