EP2171128B1 - Procédé de production d'isocyanates par oxydation anodique de formamides - Google Patents

Procédé de production d'isocyanates par oxydation anodique de formamides Download PDF

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Publication number
EP2171128B1
EP2171128B1 EP08774881A EP08774881A EP2171128B1 EP 2171128 B1 EP2171128 B1 EP 2171128B1 EP 08774881 A EP08774881 A EP 08774881A EP 08774881 A EP08774881 A EP 08774881A EP 2171128 B1 EP2171128 B1 EP 2171128B1
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EP
European Patent Office
Prior art keywords
formamides
isocyanates
formamide
anodic oxidation
area
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.)
Not-in-force
Application number
EP08774881A
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German (de)
English (en)
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EP2171128A1 (fr
Inventor
Ulrich Griesbach
Lars Wittenbecher
Hermann Pütter
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BASF SE
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BASF SE
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Publication of EP2171128A1 publication Critical patent/EP2171128A1/fr
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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00Electrolytic production of organic compounds
    • C25B3/20Processes
    • C25B3/23Oxidation

Definitions

  • the invention relates to a process for the preparation of isocyanates by oxidation of formamides.
  • Isocyanates are important raw materials e.g. for the production of polyurethanes. They are industrially produced by reacting amines with phosgene with elimination of HCl. The disadvantage here is the use of very toxic phosgene, which makes high investments in security technology necessary, as well as the formation of two equivalents of HCl, which must be removed and disposed of or recycled.
  • isocyanates are the carbonylation of aromatic nitro compounds or amines, as in Weissermel-Arpe, Industrial Organic Chemistry, 4th Edition, pp. 408-413 as well as the catalytic oxidation of formamides to isocyanates in the presence of a copper or silver catalyst, as in EP-A 0 000 602 .
  • a major disadvantage of the catalytic oxidation of formamides with oxygen is that water forms as dehydrogenation, which can react with the moisture-sensitive isocyanates.
  • This disadvantage can be circumvented by the fact that as in US 3,960,914 described working in inert solvents in the absence of moisture.
  • Still existing disadvantages of the catalytic dehydrogenation of formamides to isocyanates are the relatively high reaction temperatures of up to 300 ° C and a high substrate-catalyst ratio of 2: 1 (m / m).
  • oxidation of formamides can also be carried out with halogens, eg bromine, as in T. Lesiak, K. Seyda, J. Prakt. Chem. 1979, 321, 161-163 described. This procedure produces the corresponding hydrohalic acids which must be removed from the reaction mixture.
  • halogens eg bromine
  • isocyanates can be made accessible by oxidation of alkyl and aryloxamic acids RNH-C (OO) -C (OO) -OH and their derivatives.
  • a corresponding method is in EP-A 0 067 463 described.
  • Corresponding methods are in EP-A 243 607 and DE-A 35 29 531 described.
  • hydroxamic acids by reacting acid amides with carboxylic acid metal salts such as e.g. Potassium acetate.
  • carboxylic acid metal salts such as e.g. Potassium acetate.
  • the hydroxamic acids can be thermally decomposed to the isocyanates.
  • the object of the invention is to provide an easy to carry out process for the preparation of isocyanates.
  • the object is achieved by a process for the preparation of isocyanates R-NCO by anodic oxidation of formamides of the general formula (I) where R is hydrogen or any organic radical, wherein the Elektroylsemakers in addition to the formamide (I) contains at least one conductive salt.
  • R is hydrogen or any organic radical.
  • Preferred radicals R are hydrogen, straight-chain or branched C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl or C 2 -C 10 -alkynyl, C 6 -C 10 -aryl or C 4 -C 11 heteroaryl, which may optionally be mono- or polysubstituted by alkyl, benzyl, alkoxy, phenyl or alkoxyphenyl.
  • radicals mentioned can also be substituted twice, 3 times or more with -NH-CHO.
  • radicals R are methyl, ethyl, propyl, isopropyl, tert-butyl, phenylethyl and 6- N- formylhexyl.
  • N- substituted formamides do not cyclotrimerize.
  • the electrolysis solution contains in addition to the formamide (I) at least one conductive salt.
  • the conductive salts which are contained in the electrolysis solution are generally alkali metal salts such as salts of Li, Na, K or quaternary ammonium salts such as tetra (C 1 - to C 6 -alkyl) ammonium or tri (C 1 - bis C 6 alkyl) methylammonium salts.
  • Suitable counterions are sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate, hexafluorophosphate, perchlorate or bis-triflimide.
  • ionic liquids ionic liquids
  • electrochemically stable ionic liquids are described in “ Ionic Liquids in Synthesis ", ed. Peter Wasserscheid, Tom Welton, Verlag Wiley-VCH 2003, Chapters 1 to 3 ,
  • Preferred conductive salts are tetrabutylammonium fluoroborate, methyltributylammonium methylsulfate, methyltriethylammonium methylsulfate or lithium bis-triflimide.
  • the electrolysis solution may further contain an inert solvent.
  • Suitable solvents are polar-aprotic solvents having high electrochemical stability, such as acetonitrile, propionitrile, adiponitrile, suberonitrile, propylene carbonate, ethylene carbonate, dichloromethane, nitromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, trichlorethylene, Tetrachlorethylene, hexafluoroacetone, N- methylpyrrolidinone, hexamethylphosphoric triamide, dimethylsulfoxide and dimethylpropyleneurea (DMPU).
  • polar-aprotic solvents having high electrochemical stability, such as acetonitrile, propionitrile, adiponitrile, suberonitrile, propylene carbonate, ethylene carbonate, dichloromethane, nitromethane, chloroform, carbon t
  • the formamides if liquid, are preferably electrolyzed in the absence of an additional solvent.
  • Solid formamides are generally dissolved in a solvent and electrolyzed in the solvent in the presence of the conducting salt. However, solid formamides can be converted to the liquid state by working at temperatures above their melting point.
  • the process according to the invention can be carried out in all customary divided or undivided types of electrolytic cell. Preferably, one works continuously with undivided flow cells. It is expedient to work in the absence of moisture.
  • bipolar switched capillary gap cells or plate stacked cells in which the electrodes are designed as plates and are arranged plane-parallel ( Ullmann's Encyclopedia of Industrial Chemistry, 1999 electronic release, Sixth Edition, VCH-Verlag Weinheim, Volume Electrochemistry, Chapter 3.5 special cell designs, as well Chapter 5, Organic Electrochemistry, Subchapter 5.4.3.2 Cell Design ).
  • the electrode material graphite is preferable.
  • the current densities at which the process is carried out are generally 0.1 to 100, preferably 0.3 to 10 A / dm 2 .
  • working at atmospheric pressure higher pressures are preferably used when operating at higher temperatures in order to avoid boiling of the starting compounds or the solvent.
  • Suitable anode materials are, for example, noble metals such as platinum or metal oxides such as ruthenium or chromium oxide or mixed oxides of the type RuO x , TiO x and diamond electrodes. Preference is given to graphite or carbon electrodes.
  • cathode materials for example, iron, steel, stainless steel, nickel or precious metals such as platinum and graphite or carbon materials and diamond electrodes into consideration.
  • the system is graphite or platinum as the anode and cathode and graphite or platinum as the anode and nickel, stainless steel or steel as the cathode.
  • the electrolyte solution is worked up by general separation methods.
  • the electrolysis solution is generally first distilled and the individual compounds are recovered separately in the form of different fractions. Further purification can be carried out, for example, by crystallization, extraction, distillation or by chromatography.
  • the isocyanate formed may also be continuously removed from the electrolysis solution by distillation during anodic oxidation.
  • reaction mixture was examined by qualitative GC analysis. There were 0.42 area% (1-isocyanatoethyl) benzene formed, at the same time were still 97.9 area% N - (1-phenylethyl) formamide present (99.3 area% at the beginning). As a further product, 4-methyl-4H-benzo [e] [1,3] oxazine (0.58 area%) was formed as the product of an intramolecular cyclization of (1-isocyanatoethyl) benzene.
  • the reaction mixture was examined by qualitative GC analysis. There were 0.31 area% N - emerged formamide (6-isocyanatohexyl), while still 7.5 area% N, N '-Diformylhexamethylendiamin and 87.1 area-% were dichloromethane present.

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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 (4)

  1. Procédé pour la préparation d'isocyanates R-NCO par oxydation anodique de formamides de formule générale (I)
    Figure imgb0008
    où R signifie hydrogène ou un radical organique quelconque,
    où la solution d'électrolyse contient, outre le formamide (I), au moins un sel conducteur, caractérisé en ce que la solution électrolytique ne contient pas de solvant organique supplémentaire.
  2. Procédé selon la revendication 1, caractérisé en ce que le sel conducteur est un sel d'ammonium quaternaire.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'oxydation anodique a lieu sur une anode en graphite.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'isocyanate formé est éliminé en continu par distillation de la solution d'électrolyse.
EP08774881A 2007-07-13 2008-07-08 Procédé de production d'isocyanates par oxydation anodique de formamides Not-in-force EP2171128B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08774881A EP2171128B1 (fr) 2007-07-13 2008-07-08 Procédé de production d'isocyanates par oxydation anodique de formamides

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07112435 2007-07-13
EP08774881A EP2171128B1 (fr) 2007-07-13 2008-07-08 Procédé de production d'isocyanates par oxydation anodique de formamides
PCT/EP2008/058836 WO2009010420A1 (fr) 2007-07-13 2008-07-08 Procédé de production d'isocyanates par oxydation anodique de formamides

Publications (2)

Publication Number Publication Date
EP2171128A1 EP2171128A1 (fr) 2010-04-07
EP2171128B1 true EP2171128B1 (fr) 2011-09-21

Family

ID=39776863

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08774881A Not-in-force EP2171128B1 (fr) 2007-07-13 2008-07-08 Procédé de production d'isocyanates par oxydation anodique de formamides

Country Status (3)

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EP (1) EP2171128B1 (fr)
AT (1) ATE525497T1 (fr)
WO (1) WO2009010420A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4430262A (en) * 1981-06-05 1984-02-07 Shell Oil Company Preparation of isocyanates and/or derivatives thereof
JPH03104892A (ja) * 1989-08-15 1991-05-01 Osaka City 有機イソシアネート類の製造法

Also Published As

Publication number Publication date
ATE525497T1 (de) 2011-10-15
EP2171128A1 (fr) 2010-04-07
WO2009010420A1 (fr) 2009-01-22
WO2009010420A9 (fr) 2009-03-19

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