EP1769103A1 - Method for the production of primary amines comprising a primary amino group which is bound to an aliphatic or cycloaliphatic c-atom, and a cyclopropyl unit - Google Patents

Method for the production of primary amines comprising a primary amino group which is bound to an aliphatic or cycloaliphatic c-atom, and a cyclopropyl unit

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Publication number
EP1769103A1
EP1769103A1 EP05760066A EP05760066A EP1769103A1 EP 1769103 A1 EP1769103 A1 EP 1769103A1 EP 05760066 A EP05760066 A EP 05760066A EP 05760066 A EP05760066 A EP 05760066A EP 1769103 A1 EP1769103 A1 EP 1769103A1
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EP
European Patent Office
Prior art keywords
alkyl
oxime
substituted
formula
cyclopropyl
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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
EP05760066A
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German (de)
French (fr)
Other versions
EP1769103B1 (en
Inventor
Ulrich Griesbach
Harald Winsel
Hermann Pütter
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BASF SE
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BASF SE
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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
    • C25B3/25—Reduction

Definitions

  • the present invention relates to a process for the preparation of primary amines having a primary amino group bonded to an aliphatic or cycloaliphatic carbon atom and a cyclopropyl moiety.
  • amine A which comprises oximes having a cyclopropyl unit or oxime derivatives in which the Hydrogen atom in the oxime group is replaced by an alkyl or acyl group (oxime O) in a divided Elektrolysezel ⁇ le in an anhydrous electrolyte solution at a temperature of 50 to 100 0 C at the cathode reduced.
  • amines A which are compounds of the general formula H 2 N-CHRiR 2 (formula I), where R 1 is hydrogen, C 3 - to C 8 -cycloalkyl, C 1 - to C 20 alkyl, C 6 -C 20 -aryl or together with R 2 and the methine group between R 1 and R 2 is a C 5 - to Ce-cycloalkyl group, where the abovementioned hydrocarbon radicals are C 1 - to C 6 Alkoxy, or halogen may be substituted, and
  • R 2 C 3 - to C 8 -cycloalkyl, C 1 - to C 20 -alkyl, C 6 - to C 20 -aryl or, together with R 2 and the methine group between R 1 and R 2 , a C 5 - to C 6 cycloalkyl group where the abovementioned hydrocarbon radicals can be substituted by C 1 -C 6 -alkoxy, NH 2 -, C 1 - to C 2 o -alkylamino or halogen, with the proviso that at least one of the radicals R 1 or R 2 is cyclopropyl or substituted by cyciopropyl.
  • R 5 ON GR 3 C 4 (formula Ii), wherein R 3 has the same meaning as R 1 in formula I, R 4 has the same meaning as R 2 in formula I and the radicals R 3 and R 4 optionally substituted by 1-hydroxyimino (Cr to C 2 o) alkyl, 1- (C 1 to C 6 -Akkoxy) imino (Cr bis C 20 ) alkyl radicals or 1- (C 1 to C 6 acyloxy) (Cr to C 20 ) alkyl radicals are substituted and R 5 is hydrogen, C 1 - to C 6 alkyl or C 1 - to C 6 acyl means.
  • phenyl ring is optionally substituted by halogen atoms or C 1 - to C 4 alkoxy groups.
  • the starting compounds for the amines A of the formula Ia are the corresponding oximes O of the general formula (IIa),
  • phenyl ring is optionally substituted by halogen atoms or C 1 - to C 4 alkoxy groups
  • the catholyte contains a solvent in addition to an amine formed in the course of the reaction A and an oxime.
  • these are the inert solvents which are generally customary in organic chemistry, such as dimethyl carbonate, propylene carbonate, tetrahydrofuran, dimethoxyethane, acetonitrile or dimethylformamide.
  • C is preferably used r 4 -alkyl to C as the solvent.
  • C 5 -C 7 -hydrocarbons such as, for example, hexane, are also suitable as solvents.
  • To prepare the conductivity of the catholyte generally includes a Mineralkla ⁇ acid, preferably sulfuric acid or an alkali (C r to C 4) -alkylalkoholat, preferably Natri ⁇ environmentally methoxide.
  • an electrolyte salt is added to the anolyte and optionally also to the catholyte (in addition to one of the above-mentioned conductivity-producing agents).
  • it han ⁇ delt are generally alkali, tetra (C 1 - to C 6 -alkyl) ammonium, tri preferably (Ci to C6 alkyl) -methylammoniumsalze.
  • Suitable counterions are sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate, hexafluorophosphate or perchlorate.
  • MTBS methyltributylammonium methylsulfates
  • methyltriethylammonium methylsulfate methyltri-propylmethylammonium methylsulfates.
  • the water content in the catholyte and anolyte is generally less than 2, preferably less than 1 wt .-%, more preferably less than 0.5 wt .-%. It should be noted that in the reduction of the oxime O to the amine A water is formed in stoichiometric amounts. If, when the process is carried out discontinuously, the starting material is sufficiently dilute and the catholyte and anolyte at the beginning of the reaction have a water content of less than 0.1% by weight, it is generally unnecessary to do so during the reaction tion to remove formed water from the electrolyte. Otherwise, the water content of the electrolyte can be determined by customary methods, e.g. be lowered by distillation.
  • the process according to the invention can be carried out in all customary divided electrolysis cell types in order to be able to conclude within the scope of the process according to the invention that starting materials such as products undergo chemical side reactions as a result of the cathode process.
  • starting materials such as products undergo chemical side reactions as a result of the cathode process.
  • one works continuously in divided flow cells.
  • Divided cells with plane-parallel electrode arrangement are preferably used.
  • separation media ion exchange membranes, microporous membranes, diaphragms, filter fabrics of non-electron-conducting materials, glass frits and porous ceramics can be used.
  • ion exchange membranes in particular cation exchange membranes, are used.
  • These conductive membranes are commercially available, for example, under the trade name Nafion® (from ET DuPont de Nemours and Company) and Gore Select® (from WL Gore & Associates, Inc.).
  • the cathodes used are preferably those in which the cathode surface is formed from a material with high hydrogen overvoltage, for example from lead, zinc, tin, nickel, mercury, cadmium, copper or alloys of these metals or glassy cabon, graphite or diamond.
  • diamond electrodes e.g. in EP-A-1036863 are beschrie ⁇ ben.
  • anodes preferably those which are also referred to as cathode materials.
  • acidic anolyte preference is given to using platinum, diamond, glassy carbon or graphite anodes or the dimensionally stable anodes (DSA) known to the person skilled in the art. If the anolyte is basic, preferably stainless steel is used.
  • the anodic reaction can be chosen freely, preferably the C 1 -C 4 -alcohol used as solvent is oxidized there.
  • methanol methyl formate, formaldehyde dimethyl acetal or dimethyl carbonate are formed.
  • a sulfuric acid solution diluted with a C 1 -C 4 -alcohol is used for this purpose.
  • the current densities at which the process is carried out are generally 1 to 1000, preferably 10 to 100 mA / cm 2 .
  • the current densities at which the process is carried out are generally 1 to 1000, preferably 10 to 100 mA / cm 2 .
  • Higher pressures are preferably used when working at higher temperatures in order to avoid boiling of the starting compounds or solvents.
  • the electrolyte solution is worked up by general separation methods.
  • the catholyte is generally first distilled and the individual compounds in the form of different fractions separately ge won. Further purification can be carried out, for example, by crystallization, distillation or by chromatography.
  • Apparatus electrolysis system with catholyte and anolyte circulation and two split electrolytic cells connected in series
  • Anode 2 graphite anodes, effective area per 300 cm 2 cathode: 2 lead cathodes, effective area 300 cm 2 each
  • Membrane proton-conducting perfluorinated membrane with sulfonic acid groups, eg National 324 from DuPont Distance of electrode ⁇ Diaphragm: 6 mm
  • composition Anolyte 979.2 g MeOH, 20.8 g H2SO4, 96% pure
  • composition catholyte 5000 g MeOH, 400 g sodium methoxide sol., 30% in MeOH, 600 g cyclopropylphenylmethanone oxime 1
  • Apparatus electrolysis cell with catholyte and anolyte circulation
  • Anode graphite
  • Cathode lead
  • Membrane proton-conducting perfluorinated membrane with sulfonic acid groups, eg Nafion 117 from DuPont
  • composition of anolyte 117.5 g of MeOH, 2.5 g of H2SO4, 96% strength
  • Composition of catholyte 94.0 g of MeOH, 1.0 g of H2SO4, 96% strength, 5 g of cyclopropylphenylmethanone oxime 1
  • Apparatus electrolytic cell with catholyte and anolyte circulation
  • Anode graphite
  • Cathode lead
  • Membrane proton-conducting perfluorinated membrane with sulfonic acid groups, eg National 324 from DuPont
  • composition Anolyte 783 g MeOH, 17 g H 2 SO 4 , 96% pure
  • composition catholyte 2600 g MeOH, 100 g NaOMe, 30% in MeOH,

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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)

Abstract

Process for preparing primary amines having a cyclopropyl unit and a primary amino group bound to an aliphatic or cycloaliphatic carbon atom (amine A) by cathodically reducing oximes having a cyclopropyl unit or oxime derivatives in which the hydrogen atom in the oxime group has been replaced by an alkyl or acyl group (oxime O) at a temperature of from 50 to 100° C. in an essentially anhydrous electrolyte solution in a divided electrolysis cell.

Description

Verfahren zur Herstellung von primären Aminen mit einer an ein aliphatisches oder cycloaliphatisches C-Atom gebunden primären Aminogruppe und einer Cyclopropyl- EinheitA process for preparing primary amines having a primary amino group attached to an aliphatic or cycloaliphatic C atom and a cyclopropyl moiety
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von primären Aminen mit einer an ein aliphatisches oder cycloaliphatisches C-Atom gebunden primären Aminogruppe und einer Cyclopropyl-Einheit.The present invention relates to a process for the preparation of primary amines having a primary amino group bonded to an aliphatic or cycloaliphatic carbon atom and a cyclopropyl moiety.
Die Herstellung von primären Aminen durch elektrochemische Reduktion von Oximen ohne weitere funktionelle Gruppen ist aus J. Indian Chem. Soc. 1991 , 68, 95-97 be¬ kannt. Dabei wurde eine Quecksilbersee-Kathode verwendet und der Elektrolyt auf ca. 5°C gekühlt. Bei der Herstellung von primären Aminen, die Cyolopropyleinheiten ent- ' halten, ausgehend von entsprechenden Oximen zeigte es sich jedoch, dass bei An¬ wendung relativ niedrigen Reaktionstemperaturen unter diese Bedingungen neben dem gewünschten Wertprodukt unerwünschte Nebenprodukte entstehen. Der Fach¬ mann würde erwarten, dass die Bildung von unerwünschten Nebenprodukten bei höhe¬ ren Reaktionstemperaturen eher noch zunimmt, da es eine allgemein anerkannte Grundregel ist, dass die Selektivität einer Reaktion mit steigender Temperatur abnimmt und so die Bildung von Nebenprodukten begünstigt ist.The preparation of primary amines by electrochemical reduction of oximes without further functional groups is known from J. Indian Chem. Soc. 1991, 68, 95-97 be¬ known. In this case, a mercury-cathode was used and the electrolyte was cooled to about 5 ° C. However keep in the production of primary amines, corresponds the Cyolopropyleinheiten ', starting from corresponding oximes, it was found that at relatively low reaction temperatures An¬ application under these conditions not only the desired product undesirable by-products. It would be expected by one skilled in the art that the formation of undesirable byproducts tends to increase at higher reaction temperatures, since it is a generally accepted rule that the selectivity of a reaction decreases with increasing temperature, thus favoring the formation of by-products.
Aufgabe der vorliegenden Erfindung war es deshalb, ein Verfahren bereitzustellen, mit dem sich die definitionsgemäßen Amine elektrochemisch in hohen Ausbeuten herstel- len lassen.It was therefore an object of the present invention to provide a process with which the amines according to the definition can be prepared electrochemically in high yields.
Demgemäß wurde ein Verfahren zur Herstellung von primären Aminen mit einer an ein aliphatisches oder cycloaliphatisches C-Atom gebunden primären Aminogruppe und einer Cyclopropyl-Einheit (Amin A) gefunden, bei dem man Oxime mit einer Cyclopro- pyl-Einheit oder Oximderivate, bei denen das Wasserstoffatom in der Oximgruppe durch eine Alkyl- oder Acylgruppe ersetzt ist (Oxim O) in einer geteilten Elektrolysezel¬ le in einer wasserfreien Elektrolytlösung bei einer Temperatur von 50 bis 1000C an der Kathode reduziert.We have found that this object is achieved by a process for the preparation of primary amines having a primary amino group attached to an aliphatic or cycloaliphatic C atom and a cyclopropyl unit (amine A) which comprises oximes having a cyclopropyl unit or oxime derivatives in which the Hydrogen atom in the oxime group is replaced by an alkyl or acyl group (oxime O) in a divided Elektrolysezel¬ le in an anhydrous electrolyte solution at a temperature of 50 to 100 0 C at the cathode reduced.
Besonders eignet sich das Verfahren zur Herstellung von Aminen A, bei denen es sich um Verbindungen der allgemeinen Formel H2N-CHRiR2 (Formel I) handelt, wobei R1 Wasserstoff, C3- bis C8-Cycloalkyl, C1- bis C20-Alkyl, C6- bis C20-Aryl oder zusammen mit R2 und der zwischen R1 und R2 liegenden Methin-Gruppe eine C5- bis Ce-Cycloalkylgruppe bedeutet, wobei die vorgenannten Kohlenwasserstoffreste mit C1- bis C6-Alkoxy, oder Halogen substituiert sein können, undThe process is particularly suitable for the preparation of amines A, which are compounds of the general formula H 2 N-CHRiR 2 (formula I), where R 1 is hydrogen, C 3 - to C 8 -cycloalkyl, C 1 - to C 20 alkyl, C 6 -C 20 -aryl or together with R 2 and the methine group between R 1 and R 2 is a C 5 - to Ce-cycloalkyl group, where the abovementioned hydrocarbon radicals are C 1 - to C 6 Alkoxy, or halogen may be substituted, and
R2 C3- bis C8-Cycloalkyl, C1- bis C20-Alkyl, C6- bis C20-Aryl oder zusammen mir R2 und der zwischen R1 und R2 liegenden Methin-Gruppe eine C5- bis C6-Cycloalkylgruppe bedeutet, wobei die vorgenannten Kohlenwasserstoff reste mit C1 -bis C6-Alkoxy, NH2-, C1- bis C2o-Aikylamino oder Halogen substituiert sein können, bedeutet, mit der Maßgabe, dass mindestes einer der Reste R1 oder R2 Cyclopropyl bedeutet oder durch Cyciopropyl substituiert ist.R 2 C 3 - to C 8 -cycloalkyl, C 1 - to C 20 -alkyl, C 6 - to C 20 -aryl or, together with R 2 and the methine group between R 1 and R 2 , a C 5 - to C 6 cycloalkyl group where the abovementioned hydrocarbon radicals can be substituted by C 1 -C 6 -alkoxy, NH 2 -, C 1 - to C 2 o -alkylamino or halogen, with the proviso that at least one of the radicals R 1 or R 2 is cyclopropyl or substituted by cyciopropyl.
Als Ausgangsprodukte zur Herstellung der Amine A der allgemeinen Formel I setzt man als Oxime O Verbindungen der allgemeinen Formel R5O-N=GR3C4 (Formel Ii) ein, wobei R3 die gleiche Bedeutung wie R1 in Formel I hat, R4 die gleiche Bedeutung wie R2 in Formel I hat und die Reste R3 und R4 gegebenenfalls durch 1-Hydroxyimino(Cr bis C2o)-alkylreste, 1-(C1- bis C6-AIkOXi)- imino(Cr bis C20)-alkyl reste oder 1-(C1- bis C6-Acyloxi)-imino(Cr bis C20)-alkylreste substituiert sind und R5 Wasserstoff, C1- bis C6-Alkyl oder C1- bis C6-Acyl bedeutet.As starting materials for the preparation of the amines A of the general formula I are used as oximes O compounds of the general formula R 5 ON = GR 3 C 4 (formula Ii), wherein R 3 has the same meaning as R 1 in formula I, R 4 has the same meaning as R 2 in formula I and the radicals R 3 and R 4 optionally substituted by 1-hydroxyimino (Cr to C 2 o) alkyl, 1- (C 1 to C 6 -Akkoxy) imino (Cr bis C 20 ) alkyl radicals or 1- (C 1 to C 6 acyloxy) (Cr to C 20 ) alkyl radicals are substituted and R 5 is hydrogen, C 1 - to C 6 alkyl or C 1 - to C 6 acyl means.
Ganz besonders eignet sich das erfindungsgemäße Verfahren zur Herstellungen von Aminen A der allgemeinen Formel IaThe process according to the invention is very particularly suitable for the preparation of amines A of the general formula Ia
bei der der Phenylring gegebenenfalls durch Halogenatome oder C1- bis C4-Alkoxi- gruppen substituiert ist. in which the phenyl ring is optionally substituted by halogen atoms or C 1 - to C 4 alkoxy groups.
Als Ausgangsverbindung für die Amine A der Formel Ia dienen die entsprechenden Oxime O der allgemeinen (Formel IIa),The starting compounds for the amines A of the formula Ia are the corresponding oximes O of the general formula (IIa),
wobei der Phenylring gegebenenfalls durch Halogenatome oder C1- bis C4-Alkoxi- gruppen substituiert ist wherein the phenyl ring is optionally substituted by halogen atoms or C 1 - to C 4 alkoxy groups
Gegebenenfalls enthält der Katholyt neben einem im Laufe der Reaktion gebildeten Amin A und einem Oxim O ein Lösungsmittel. Dabei handelt es sich um die in der or¬ ganischen Chemie allgemein üblichen inerten Lösungsmittel wie Dimethylcarbonat, Propylencarbonat, Tetrahydrofuran, Dimethoxyethan, Acetonitril oder Dimethylforma- mid. Bevorzugt wird als Lösungsmittel ein Crbis C4-Alkylalkohol eingesetzt. In Kombi¬ nation mit den genannten Lösungsmittel eignen sich auch C5- bis C7-Kohlenwasser- stoffe wie z.B. Hexan als Lösungsmittel. Zur Herstellung der Leitfähigkeit enthält der Katholyt im Allgemeinen eine Mineralsäu¬ re, bevorzugt Schwefelsäure oder ein Alkali(Crbis C4)-alkylalkoholat, bevorzugt Natri¬ um- Methanolat.Optionally, the catholyte contains a solvent in addition to an amine formed in the course of the reaction A and an oxime. These are the inert solvents which are generally customary in organic chemistry, such as dimethyl carbonate, propylene carbonate, tetrahydrofuran, dimethoxyethane, acetonitrile or dimethylformamide. C is preferably used r 4 -alkyl to C as the solvent. In combination with the abovementioned solvents, C 5 -C 7 -hydrocarbons, such as, for example, hexane, are also suitable as solvents. To prepare the conductivity of the catholyte generally includes a Mineralsäu¬ acid, preferably sulfuric acid or an alkali (C r to C 4) -alkylalkoholat, preferably Natri¬ environmentally methoxide.
Im Allgemeinen setzt man dem Anolyt und ggf. auch dem Katholyt (zusätzlich zu einem der oben genannten die Leitfähigkeit herstellenden Mittel) ein Leitsalz zu. Dabei han¬ delt es sich im Allgemeinen um Alkali, Tetra(C1- bis C6-alkyl)ammonium-, bevorzugt Tri(Ci- bis C6-alkyl)-methylammoniumsalze. Als Gegenion kommen Sulfat, Hydrogen¬ sulfat, Alkylsulfate, Arylsulfate, Halogenide, Phosphate, Carbonate, Alkylphosphate, Alkylcarbonate, Nitrat, Alkoholate, Tetrafluoroborat, Hexafluorophosphat oder Perchlo¬ rat in Betracht.In general, an electrolyte salt is added to the anolyte and optionally also to the catholyte (in addition to one of the above-mentioned conductivity-producing agents). In this case, it han¬ delt are generally alkali, tetra (C 1 - to C 6 -alkyl) ammonium, tri preferably (Ci to C6 alkyl) -methylammoniumsalze. Suitable counterions are sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate, hexafluorophosphate or perchlorate.
Bevorzugt sind Methyltributylammoniummethylsulfate (MTBS), Methyltriethylammoni- ummethylsulfat oder Methyl-tri-propylmethylammoniummethylsulfate.Preference is given to methyltributylammonium methylsulfates (MTBS), methyltriethylammonium methylsulfate or methyltri-propylmethylammonium methylsulfates.
Der Wassergehalt im Katholyten und Anolyten beträgt im Allgemeinen weniger als 2, bevorzugt weniger als 1 Gew.-%, besonders bevorzugt weniger als 0,5 Gew.-%. Dabei ist zu berücksichtigen, dass bei der Reduktion des Oxims O zum Amin A Wasser in stöchiometrischen Mengen gebildet wird. Wenn bei diskontinuierlicher Durchführung des Verfahrens mit ausreichend großer Verdünnung des Ausgangsprodukts gearbeitet wird und der Katholyt und Anolyt zu Beginn der Reaktion einen Wassergehalt von we¬ niger als 0,1 Gew.-% aufweist, erübrigt es sich im Allgemeinen, das während der Reak¬ tion gebildete Wasser aus dem Elektrolyt zu entfernen. Ansonsten kann der Wasser¬ gehalt des Elektrolyten nach üblichen Methoden, z.B. durch Destillation, abgesenkt werden.The water content in the catholyte and anolyte is generally less than 2, preferably less than 1 wt .-%, more preferably less than 0.5 wt .-%. It should be noted that in the reduction of the oxime O to the amine A water is formed in stoichiometric amounts. If, when the process is carried out discontinuously, the starting material is sufficiently dilute and the catholyte and anolyte at the beginning of the reaction have a water content of less than 0.1% by weight, it is generally unnecessary to do so during the reaction tion to remove formed water from the electrolyte. Otherwise, the water content of the electrolyte can be determined by customary methods, e.g. be lowered by distillation.
Das erfindungsgemäße Verfahren kann in allen üblichen geteilten Elektrolysezellenty¬ pen durchgeführt werden, um im Rahmen des erfindungsgemäßen Verfahrens aus¬ schließen zu können, dass Edukte wie Produkte durch den Kathodenprozess chemi- sehe Nebenreaktionen unterlaufen. Vorzugsweise arbeitet man kontinuierlich in geteil¬ ten Durchflusszellen.The process according to the invention can be carried out in all customary divided electrolysis cell types in order to be able to conclude within the scope of the process according to the invention that starting materials such as products undergo chemical side reactions as a result of the cathode process. Preferably, one works continuously in divided flow cells.
Geteilte Zellen mit planparalleler Elektrodenanordnung kommen bevorzugt zum Ein¬ satz. Als Trennmedien können lonenaustauschermembranen, mikroporöse Membra- nen, Diaphragmen, Filtergewebe aus nichtelektronenleitenden Materialien, Glasfritten, sowie poröse Keramiken eingesetzt werden. Vorzugsweise werden lonenaustau¬ schermembranen, insbesondere Kationaustauschermembranen verwendet. Diese leit¬ fähigen Membranen sind handelsüblich z.B. unter dem Handelsnamen Nafion® (Fa. ET. DuPont de Nemours and Company) und Gore Select® (Fa. W. L. Gore & Associa- tes, Inc.) erhältlich. Als Kathoden verwendet man bevorzugt solche, bei denen die Kathodenoberfläche gebildet ist aus einem Material mit hoher Wasserstoffüberspannung, z.B. aus Blei, Zink, Zinn, Nickel, Quecksilber, Cadmium, Kupfer oder Legierungen dieser Metalle oder Glassy Cabon, Grafit oder Diamant.Divided cells with plane-parallel electrode arrangement are preferably used. As separation media, ion exchange membranes, microporous membranes, diaphragms, filter fabrics of non-electron-conducting materials, glass frits and porous ceramics can be used. Preferably, ion exchange membranes, in particular cation exchange membranes, are used. These conductive membranes are commercially available, for example, under the trade name Nafion® (from ET DuPont de Nemours and Company) and Gore Select® (from WL Gore & Associates, Inc.). The cathodes used are preferably those in which the cathode surface is formed from a material with high hydrogen overvoltage, for example from lead, zinc, tin, nickel, mercury, cadmium, copper or alloys of these metals or glassy cabon, graphite or diamond.
Besonders bevorzugt sind Diamantelektroden, wie z.B. in der EP-A-1036863 beschrie¬ ben sind.Particularly preferred are diamond electrodes, e.g. in EP-A-1036863 are beschrie¬ ben.
Als Anoden kommen grundsätzlich alle üblichen Materialien in Betracht, bevorzugt die, die auch als Kathodenmaterialien genannt. Im sauren Anolyten werden bevorzugt Pla¬ tin-, Diamant-, Glassy Carbon- oder Grafitanoden oder die dem Fachmann bekannte dimensionsstabile Anoden (DSA) eingesetzt. Ist der Anolyt basisch, wird bevorzugt Edelstahl verwendet.In principle, all conventional materials are suitable as anodes, preferably those which are also referred to as cathode materials. In the acidic anolyte, preference is given to using platinum, diamond, glassy carbon or graphite anodes or the dimensionally stable anodes (DSA) known to the person skilled in the art. If the anolyte is basic, preferably stainless steel is used.
Die Anodenreaktion kann frei gewählt werden, bevorzugt wird dort der als Lösungsmit¬ tel verwendete C1- bis C4-Alkohol oxidiert. Bei der Verwendung von Methanol wird Me- thylformiat, Formaldehyd-Dimethylacetal bzw. Dimethylcarbonat gebildet. Hierzu dient z.B. eine mit einem C1- bis C4-Alkohol verdünnte Schwefelsäurelösung.The anodic reaction can be chosen freely, preferably the C 1 -C 4 -alcohol used as solvent is oxidized there. When methanol is used, methyl formate, formaldehyde dimethyl acetal or dimethyl carbonate are formed. For example, a sulfuric acid solution diluted with a C 1 -C 4 -alcohol is used for this purpose.
Die Stromdichten, bei denen man das Verfahren durchführt, betragen im allgemeinen 1 bis 1000, bevorzugt 10 bis 100 mA/cm2. Im allgemeinen wird bei Normaldruck gearbei¬ tet. Höhere Drücke werden bevorzugt dann angewandt, wenn bei höheren Temperatu¬ ren gearbeitet werden soll, um eine Sieden der Ausgangsverbindungen bzw. Lösungs¬ mittel zu vermeiden.The current densities at which the process is carried out are generally 1 to 1000, preferably 10 to 100 mA / cm 2 . In general, at normal pressure gearbei¬ tet. Higher pressures are preferably used when working at higher temperatures in order to avoid boiling of the starting compounds or solvents.
Nach Beendigung der Reaktion wird die Elektrolytlösung nach allgemeinen Trennme¬ thoden aufgearbeitet. Hierzu wird der Katholyt im allgemeinen zunächst destilliert und die einzelnen Verbindungen in Form von unterschiedlichen Fraktionen getrennt ge¬ wonnen. Eine weitere Reinigung kann beispielsweise durch Kristallisation, Destillation oder chromatographisch erfolgen.After completion of the reaction, the electrolyte solution is worked up by general separation methods. For this purpose, the catholyte is generally first distilled and the individual compounds in the form of different fractions separately ge won. Further purification can be carried out, for example, by crystallization, distillation or by chromatography.
Experimenteller TeilExperimental part
Beispiel 1example 1
Apparatur: Elektrolyseanlage mit Katholyt- und Anolytkreislauf und zwei hintereinandergeschalteten geteilten Elekt¬ rolysezellenApparatus: electrolysis system with catholyte and anolyte circulation and two split electrolytic cells connected in series
Anode: 2 Grafitanoden, effektive Fläche je 300 cm2 Kathode: 2 Bleikathoden, effektive Fläche je 300 cm2 Anode: 2 graphite anodes, effective area per 300 cm 2 cathode: 2 lead cathodes, effective area 300 cm 2 each
Membran: protonenleitenede perfluorierte Membran mit SuI- fonsäuregruppen, z.B. Nation 324 der Firma DuPont Abstand Elektrode <→ Membran: 6 mmMembrane: proton-conducting perfluorinated membrane with sulfonic acid groups, eg Nation 324 from DuPont Distance of electrode <→ Diaphragm: 6 mm
Stromdichte: 3,4 A/dm2Current density: 3.4 A / dm2
Spannung: 20 - 40 VVoltage: 20 - 40 V
Temperatur: 55°CTemperature: 55 ° C
Zusammensetzung Anolyt: 979,2 g MeOH, 20,8 g H2SO4, 96%igComposition Anolyte: 979.2 g MeOH, 20.8 g H2SO4, 96% pure
Zusammensetzung Katholyt: 5000 g MeOH, 400 g Natriummethanolat-Lsg., 30% in MeOH, 600 g Cyclopropylphenylmethanonoxim 1Composition catholyte: 5000 g MeOH, 400 g sodium methoxide sol., 30% in MeOH, 600 g cyclopropylphenylmethanone oxime 1
Durchflussgeschwindigkeit: 150 - 200 L/hFlow rate: 150 - 200 L / h
Bei der Elektrolyse unter den angegebenen Bedingungen wurden Anolyt und Katholyt 24 h (entspricht einer Ladungsmenge von 5 F/mol 1) durch die jeweiligen Halbzellen gepumpt. Die gaschromatographische Untersuchung des Reaktionsaustrages ergab 95,1 FI.-% des gewünschten Wertproduktes 2, 0,10% der ringgeöffneten Verbindung 3, 0,82% Edukt 1 sowie 3,18% Hochsieder.During the electrolysis under the conditions indicated, the anolyte and catholyte were pumped through the respective half-cells for 24 h (corresponding to an amount of charge of 5 F / mol 1). The gas chromatographic analysis of the reaction yield showed 95.1 FI .-% of the desired value product 2, 0.10% of the ring-opened compound 3, 0.82% starting material 1 and 3.18% high boilers.
Beispiel 2Example 2
Apparatur: Elektrolysezelle mit Katholyt- und Anolytkreislauf Anode: Grafit, effektive Fläche 35 cm2 Kathode: Blei, effektive Fläche 35 cm2 Membran: protonenleitende perfluorierte Membran mit Sulfon- säuregruppen, z.B. Nafion 117 der Firma DuPontApparatus: electrolysis cell with catholyte and anolyte circulation Anode: graphite, effective area 35 cm 2 Cathode: lead, effective area 35 cm 2 Membrane: proton-conducting perfluorinated membrane with sulfonic acid groups, eg Nafion 117 from DuPont
Stromdichte: 3,4 A/dm2 Spannung: 15 - 20 V Temperatur: 400CCurrent density: 3.4 A / dm2 Voltage: 15 - 20 V Temperature: 40 0 C
Zusammensetzung Anolyt: 117,5 g MeOH, 2,5 g H2SO4, 96%ig Zusammensetzung Katholyt: 94,0 g MeOH, 1 ,0 g H2SO4, 96%ig, 5 g Cyclopro¬ pylphenylmethanonoxim 1Composition of anolyte: 117.5 g of MeOH, 2.5 g of H2SO4, 96% strength Composition of catholyte: 94.0 g of MeOH, 1.0 g of H2SO4, 96% strength, 5 g of cyclopropylphenylmethanone oxime 1
Bei der Elektrolyse unter den angegebenen Bedingungen wurden Anolyt und Katholyt 4,11 h (entspricht einer Ladungsmenge von 6 F/mol 1) durch die jeweiligen Halbzellen gepumpt. Die gaschromatographische Untersuchung des Reaktionsaustrages ergab 83,3 FI.-% des gewünschten Wertproduktes 2, 1,3% der ringgeöffneten Verbindung 3 sowie 15,6% Hoch- und Mittelsieder. Beispiel 3 (zum Vergleich)During the electrolysis under the conditions indicated, the anolyte and catholyte were pumped through the respective half-cells for 4.11 h (corresponding to an amount of charge of 6 F / mol 1). The gas chromatographic analysis of the reaction yield showed 83.3 FI .-% of the desired product of value 2, 1.3% of the ring-opened compound 3 and 15.6% high and medium boilers. Example 3 (for comparison)
Apparatur: Eiektrolysezelle mit Katholyt- und Anolytkreislauf Anode: Grafit, effektive Fläche 300 cm2 Kathode: Blei, effektive Fläche 300 cm2 Membran: protonenleitenede perfluorierte Membran mit Sulfon- säuregruppen, z.B. Nation 324 der Firma DuPontApparatus: electrolytic cell with catholyte and anolyte circulation Anode: graphite, effective area 300 cm 2 Cathode: lead, effective area 300 cm 2 Membrane: proton-conducting perfluorinated membrane with sulfonic acid groups, eg Nation 324 from DuPont
Stromdichte: 3,4 A/dm2 Current density: 3.4 A / dm 2
Spannung: 14 - 33 VVoltage: 14 - 33 V
Temperatur: 400CTemperature: 40 ° C
Zusammensetzung Anolyt: 783 g MeOH, 17 g H2SO4, 96%igComposition Anolyte: 783 g MeOH, 17 g H 2 SO 4 , 96% pure
Zusammensetzung Katholyt: 2600 g MeOH, 100 g NaOMe, 30%ig in MeOH,Composition catholyte: 2600 g MeOH, 100 g NaOMe, 30% in MeOH,
300 g Cyclopropylphenylmethanonoxim 1300 g of cyclopropylphenylmethanone oxime 1
Bei der Elektrolyse unter den angegebenen Bedingungen wurden Anolyt und Katholyt 27,6 h (entspricht einer Ladungsmenge von 6,5 F/mol 1) durch die jeweiligen Halbzel¬ len gepumpt. Die gaschromatographische Untersuchung des Reaktionsaustrages er¬ gab 77,3 FI.-% des gewünschten Wertproduktes 2, 2.0% nicht umgesetztes Oxim 1 sowie 20,7% Hoch- und Mittelsieder. During the electrolysis under the conditions indicated, anolyte and catholyte were pumped through the respective half cells for 27.6 hours (corresponding to a charge of 6.5 F / mol 1). Gas chromatographic analysis of the reaction output gave 77.3% by weight of the desired desired product 2, 2.0% of unreacted oxime 1 and 20.7% of high and medium boilers.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von primären Aminen mit einer an ein aliphatisches oder cycloaliphatisches C-Atom gebunden primären Aminogruppe und einer Cyclopropyl-Einheit (Amin A)1 indem man Oxime mit einer Cyclopropyl-Einheit oder Oximderivate, bei denen das Wasserstoffatom in der Oximgruppe durch eine Alkyl- oder Acylgruppe ersetzt ist (Oxim O) in einer geteilten Elektrolysezelle in einer im wesentlichen wasserfreien Elektrolytlösung bei einer Temperatur von 50 bis 1000C an der Kathode reduziert.A process for the preparation of primary amines having a primary amino group bonded to an aliphatic or cycloaliphatic C atom and a cyclopropyl unit (amine A) 1 by reacting oximes with a cyclopropyl moiety or oxime derivatives in which the hydrogen atom in the oxime group an alkyl or acyl group is replaced (oxime O) in a divided electrolytic cell in a substantially anhydrous electrolyte solution at a temperature of 50 to 100 0 C at the cathode reduced.
2. Verfahren nach Anspruch 1 , wobei es sich bei den Aminen A um Verbindungen der allgemeinen Formel H2N-CHR1R2 (Formel I) handelt,2. The method of claim 1, wherein the amines A are compounds of the general formula H 2 N-CHR 1 R 2 (formula I),
wobei R1 Wasserstoff, C3- bis C8-Cycloalkyl, C1- bis C20-Alkyl, C6- bis C20-Aryl oder zusammen mit R2 und der zwischen R1 und R2 liegenden Methin-Gruppe eine C5- bis C6-Cycloalkylgruppe bedeutet, wobei die vorgenanntenwhere R 1 is hydrogen, C 3 - to C 8 -cycloalkyl, C 1 - to C 20 -alkyl, C 6 - to C 20 -aryl or together with R 2 and the methine group between R 1 and R 2 is a C 5 - to C 6 cycloalkyl group, the abovementioned
Kohlenwasserstoffreste mit C1-Ws C6-Alkoxy, oder Halogen substituiert sein können, undHydrocarbon radicals may be substituted by C 1 -Ws C 6 alkoxy, or halogen, and
R2 C3- bis Qj-Cycloalkyl, C1-bis C20-Alkyl, C6 bis C20-Aryl oder zusammen mir R2 und der zwischen R1 und R2 liegenden Methin-Gruppe eine C5- bis C6-R 2 C 3 - to Qj-cycloalkyl, C 1 - to C 20 -alkyl, C 6 - to C 20 -aryl or, together with R 2 and the methine group between R 1 and R 2 , a C 5 - to C 6 -
Cycloalkylgruppe bedeutet, wobei die vorgenannten Kohlenwasserstoffreste mitCycloalkyl group means, wherein the aforementioned hydrocarbon radicals with
Crbis C6-Alkoxy, NH2-, C1- bis C20-Alkylamino oder Halogen substituiert sein können, bedeutet, mit der Maßgabe, dass mindestes einer der Reste R1 oder R2 Cyclopropyl bedeutet oder durch Cyclopropyl substituiert ist, und es sich bei den Oximen O um Verbindungen der allgemeinen Formel R5O-Crbis C 6 alkoxy, NH 2 -, C 1 - to C 20 alkylamino or halogen may be substituted, with the proviso that at least one of R 1 or R 2 is cyclopropyl or substituted by cyclopropyl, and it in the oximes O are compounds of the general formula R 5 O-
N=CR3R4 (Formel II) handelt, wobei R3 die gleiche Bedeutung wie R1 in Formel I hat,N = CR 3 R 4 (formula II), where R 3 has the same meaning as R 1 in formula I,
R4 die gleiche Bedeutung wie R2 in Formel I hat und die Reste R3 und R4 gegebenenfalls durch 1-Hydroxyimino(Cr bis C20)-alkylreste, 1-(C1- bis C6-R 4 has the same meaning as R 2 in formula I and the radicals R 3 and R 4 are optionally substituted by 1-hydroxyimino (C r to C 20 ) -alkyl radicals, 1- (C 1 - to C 6 -
Alkoxi)-imino(Cr bis C20)-alkylreste oder 1-(C1- bis C6-Acyloxi)-imino(Cr bisAlkoxy) -imino (Cr to C 20 ) alkyl radicals or 1- (C 1 to C 6 acyloxy) -imino (Cr to
C20)-alkylreste substituiert sind undC 20 ) -alkyl radicals are substituted and
R5 Wasserstoff, C1- bis C6-Alkyl oder C1- bis C6- Acyl bedeutetR 5 is hydrogen, C 1 - to C 6 -alkyl or C 1 - to C 6 - acyl
3. Verfahren nach Anspruch 1 oder 2, wobei es sich bei den Aminen A um Verbindungen der allgemeinen Formel Ia handelt,3. Process according to Claim 1 or 2, where the amines A are compounds of the general formula Ia,
(Ia) bei der der Phenylring gegebenenfalls durch Halogenatome oder C1- bis C4-(Ia) in which the phenyl ring is optionally substituted by halogen atoms or C 1 - to C 4 -
Alkoxigruppen substituiert ist und es sich bei den Oximen O um Verbindungen der allgemeinen (Formel IIa) handelt,Alkoxig is substituted and it is in the oximes O compounds of general (formula IIa),
bei der der Phenylring gegebenenfalls durch Halogenatome oder C1- bis C4- Alkoxigruppen substituiert ist. in which the phenyl ring is optionally substituted by halogen atoms or C 1 - to C 4 -alkoxy groups.
4. Verfahren nach einem der vorstehenden Ansprüche, wobei der Katholyt neben einem Amin A und einem Oxim O als Lösungsmittel einen Crbis C4-Alkylalkohol enthält.4. The method according to any one of the preceding claims, wherein the catholyte in addition to an amine A and an oxime O as a solvent contains a C r to C 4 alkyl alcohol.
5. Verfahren nach einem der vorstehenden Ansprüche, wobei der Katholyt eine Mineralsäure oder ein Alkali(Crbis C4)-alkylalkoholat enthält.5. The method according to any one of the preceding claims, wherein the catholyte contains a mineral acid or an alkali (C r to C 4 ) alkylalkoholat.
6. Verfahren nach einem der vorstehenden Ansprüche, wobei die Kathoden¬ oberfläche gebildet ist aus einem Material mit hoher Wasserstoffüberspannung.6. The method according to any one of the preceding claims, wherein the cathode surface is formed of a material with high hydrogen overvoltage.
7. Verfahren nach einem der vorstehenden Ansprüche, wobei die Kathoden- Oberfläche aus Blei, Zink, Zinn, Nickel, Quecksilber, Cadmium, Kupfer oder7. The method according to any one of the preceding claims, wherein the cathode surface of lead, zinc, tin, nickel, mercury, cadmium, copper or
Legierungen dieser Metalle oder Glassy Carbon, Grafit oder Diamant gebildet ist.Alloys of these metals or glassy carbon, graphite or diamond is formed.
8. Verfahren nach einem der vorstehenden Ansprüche, wobei der Wassergehalt im Katholyt weniger als 2 Gew.-% beträgt. 8. The method according to any one of the preceding claims, wherein the water content in the catholyte is less than 2 wt .-%.
EP05760066A 2004-07-13 2005-07-08 Electrochemical process for preparing cyclopropylbenzylamines Not-in-force EP1769103B1 (en)

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DE102004033718A DE102004033718A1 (en) 2004-07-13 2004-07-13 A process for preparing primary amines having a primary amino group attached to an aliphatic or cycloaliphatic C atom and a cyclopropyl moiety
PCT/EP2005/007400 WO2006005531A1 (en) 2004-07-13 2005-07-08 Method for the production of primary amines comprising a primary amino group which is bound to an aliphatic or cycloaliphatic c-atom, and a cyclopropyl unit

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