EP0984909A1 - Use of a rhodium catalyst for hydroamination and/or oxidative amination of aryl-substituted olefins and method for producing a 2-aryl vinyl amine - Google Patents

Use of a rhodium catalyst for hydroamination and/or oxidative amination of aryl-substituted olefins and method for producing a 2-aryl vinyl amine

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Publication number
EP0984909A1
EP0984909A1 EP98930677A EP98930677A EP0984909A1 EP 0984909 A1 EP0984909 A1 EP 0984909A1 EP 98930677 A EP98930677 A EP 98930677A EP 98930677 A EP98930677 A EP 98930677A EP 0984909 A1 EP0984909 A1 EP 0984909A1
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Prior art keywords
formula
tris
phosphane
rhodium
amine
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EP98930677A
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German (de)
French (fr)
Inventor
Martin Eichberger
Matthias Beller
Harald Trautwein
Jürgen HERWIG
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Evonik Operations GmbH
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Aventis Research and Technologies GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
    • C07D295/073—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings

Definitions

  • the present invention relates to the use of a rhodium catalyst and a new process for the preparation of 2-aryl-substituted ethylene and ethyl amines.
  • Amines and their derivatives are of industrial importance as intermediates for dyes, fine chemicals, pharmaceuticals and agricultural products. Of particular importance are 2-aryl-substituted ethylamines, which find numerous applications as pharmaceuticals, agrochemicals and fine chemicals. As simple and multifunctional derivatives of amines, they are of particular technical interest.
  • the object of the present invention is to provide a simple process for the direct amination or hydroamination of aryl-substituted olefins, in particular a process for the preparation of 2-aryl-substituted ethylene and ethyl amines and their derivatives, with which the disadvantages of the prior art mentioned are avoided.
  • a rhodium catalyst for inter- or intramolecular hydroamination and / or inter- or intramolecular oxidative amination of aryl-substituted olefins using primary or secondary amines, characterized in that the rhodium catalyst contains a cationic rhodium compound of oxidation level I or III.
  • This special catalyst makes it possible for the first time to directly amine aryl-substituted olefins.
  • the anti-Markovnikov products are always formed in the case of asymmetrical olefins. This means that the nitrogen atom of the amine used only attacks the more highly substituted carbon atom of the olefin bond.
  • the rhodium catalyst contains a non-coordinating or only weakly coordinating anion, in particular a perchlorate, hexafluorophosphate, hexafluoroantimonate or tetrafluoroborate, tetraarylborate, trifluoroacetate, alkyl or arylsulfonate anion.
  • a non-coordinating or only weakly coordinating anion in particular a perchlorate, hexafluorophosphate, hexafluoroantimonate or tetrafluoroborate, tetraarylborate, trifluoroacetate, alkyl or arylsulfonate anion.
  • the rhodium catalyst preferably contains a cationic rhodium compound of oxidation state I or III complexed by at least one ligand.
  • a phosphane in particular selected from the group of triphenylphosphine, trifurylphosphine, bis (4-methoxyphenyl) phenylphosphine, bis (3-methoxyphenyl) phenylphosphine, bis (4-fluorophenyl) phenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine, n-butylphosphine, thisopropylphosphine, tris- (4-methoxyphenyl) phosphane, tris- (3-methoxyphenyl) phosphane, Ths- (4-fluorophenyl) phosphine, tris- (3-fluorophenyl) phosphane, Ths- (4-chlorophen
  • the ratio of the phosphorus atoms from the phosphine ligands to the rhodium atoms, based on the catalyst is between 0.5: 1 and 10: 1.
  • a diolefin can also be used as the ligand, which is selected in particular from cyclooctadiene, dicyclopentadiene or norbomadiene.
  • the rhodium catalyst based on the primary and / or secondary amine, is used in amounts from 0.0001 mol% to 20 mol%, in particular from 0.1 mol% to 10 mol%.
  • the rhodium catalyst described above can be used particularly well according to the invention for the preparation of a 2-arylvinylamine of the formula (I)
  • Ar represents an aryl radical, in particular from the group of the condensed or uncondensed C 6 -C 22 aromatics, such as, for example, phenyl, naphthyl, anthryl, phenanthryl and biphenylyl radicals, or the condensed or uncondensed C 5 -C 2 2-heteroaromatics which have at least one nitrogen, oxygen or sulfur atom in the ring, such as, for example, indenyl, pyridyl
  • R 1 and R 2 independently represent a hydrogen atom or a C1-C 4 alkyl radical
  • R 3 and R 4 independently of one another represent a hydrogen atom, a C1-C20-alkyl radical or one of the previously defined aryl radicals Ar, or R 3 and
  • this catalyst can also be used to prepare a 2-arylethylamine of the formula (I)
  • radicals R 1 to R and Ar have the same meaning as previously indicated.
  • the aryl radical Ar originating either from the vinylaryl compound of the formula (II) or from the amine of the formula (III), can have up to 8 substituents which independently of one another represent a fluorine, chlorine, bromine or iodine atom or are selected from the group of HO-, HC (O) -, HCO 2 -, H 2 N-, NC-, HC (O) NH-, H 2 NC (O) -, NO 2 -, HSO 3 -, CF 3 -, R 5 -, R 5 O-, R 5 C (O) -, R 5 CO 2 -, R 5 NH-, R 5 2 N-, R 5 C (O) NH-, R 5 CO 2 CHCH-, R 5 SO 2 -, R 5 S (O) -, R 5 P (O) -, and R 5 3 Si residues, as well as from five and six-membered heteroaromatics which have at least one nitrogen, oxygen or sulfur atom in the ring
  • the vinylaryl compound of the formula (II) is styrene, in particular styrene substituted in the ortho, meta or para position, preferably styrene substituted with a heteroaryl radical.
  • a primary or secondary, aromatic or aliphatic amine can be used as the amine of the formula (III).
  • Morpholine, piperidine, piperazine, dimethylamine, diethylamine, dipropylamine or dibutylamine are particularly preferred.
  • the compounds obtained according to the present process can be isolated or used directly for subsequent reactions such as hydrogenation or reaction with electrophiles (aldehydes, epoxides, alkyl halides).
  • Inert organic solvents are generally used as solvents in the process according to the invention.
  • Aromatic hydrocarbons such as toluene, xylenes, anisole, tetralin and aliphatic ethers such as tetrahydrofuran, dimethoxyethane, dioxane, tetrahydropyran, formaldehyde acetals are preferred.
  • the reaction of the amines with substituted styrenes takes place at temperatures of 20-250 ° C, preferably at 40-200 ° C and particularly preferably at 60-160 ° C.
  • the 2-arylvinylamine or the 2-arylethylamine is preferably formed.
  • the mixture of 2-arylvinylamine or 2-arylethylamine obtained in other cases can be isolated by suitable methods, in particular by column chromatography.
  • the 2-arylvinylamine obtained can then be hydrogenated in the presence of hydrogen and a hydrogenation catalyst according to standard conditions (K Weissermel, HJ Arpe, Industrielle Organische Chemie, VCH, 1988) to the corresponding 2-arylethylamine .
  • the products are generally formed in good yields of up to 99% by the process according to the invention.
  • the hydrogenation products of the vinylaryl compound used are observed as by-products and are easily separable.
  • ethylbenzene is formed as a by-product.
  • Example 2-19 are carried out analogously to Example 1.
  • the starting materials and their amounts and the reaction results are summarized in Table 1 (NBD) 2 RhBF was prepared according to TG Schenk et al., Inorg. Chem. 24 (1985), p. 2334. The subsequent hydrogenation to the amine was not carried out in experiments 14-17.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to the use of a rhodium catalyst for inter- or intra-molecular hydroamination and/or inter- or intra-molecular oxidative amination of aryl-substituted olefins using primary or secondary amines, said rhodium catalyst containing a cationic rhodium compound of oxidation stage I or III. The invention also relates to a novel method for producing 2-aryl-substituted ethylene- and ethylamines.

Description

Verwendung eines Rhodiumkatalysators zur Hydroaminierung und/oder oxidativen Aminierung von arylsubstituierten Olefinen und Verfahren zur Herstellung eines 2- ArylvinylaminsUse of a rhodium catalyst for the hydroamination and / or oxidative amination of aryl-substituted olefins and process for the preparation of a 2-arylvinylamine
Die vorliegende Erfindung betrifft die Verwendung eines Rhodiumkatalysators sowie ein neues Verfahren zur Herstellung von 2-arylsubstituierten Ethylen- und Ethylaminen.The present invention relates to the use of a rhodium catalyst and a new process for the preparation of 2-aryl-substituted ethylene and ethyl amines.
Amine und deren Derivate sind von industrieller Bedeutung als Vorprodukte für Farbstoffe, Feinchemikalien, Pharmazeutika und Agroprodukten. Von besonderer Bedeutung sind 2-arylsubstituierte Ethylamine, die zahlreiche Anwendungen als Pharmaka, Agrochemikalien und Feinchemikalien finden. Als einfache und vielfältig funktionalisierbare Derivate von Aminen sind sie von besonderem technischen Interesse.Amines and their derivatives are of industrial importance as intermediates for dyes, fine chemicals, pharmaceuticals and agricultural products. Of particular importance are 2-aryl-substituted ethylamines, which find numerous applications as pharmaceuticals, agrochemicals and fine chemicals. As simple and multifunctional derivatives of amines, they are of particular technical interest.
Die Herstellung von 2-arylsubstituierten Ethylenaminen sowie der entsprechenden 2-arylsubstituierten Ethylaminen erfolgte bisher üblicherweise durch die in Houben- Weyl, „Methoden der organischen Chemie", Georg Thieme Verlag, Stuttgart, 4. Aufl. (1957), Band XI/1 , S. 341 ff. beschriebene reduktive Aminierung von Arylacetaldehyden gemäß dem Reaktionsschema:Up to now, 2-aryl-substituted ethylene amines and the corresponding 2-aryl-substituted ethyl amines have usually been prepared by Houben-Weyl, "Methods of Organic Chemistry", Georg Thieme Verlag, Stuttgart, 4th edition (1957), volume XI / 1, Pp. 341 ff. Described reductive amination of arylacetaldehydes according to the reaction scheme:
Eine weitere Möglichkeit zur Herstellung von 2-arylsubstituierten Ethylaminen besteht in der nukleophilen Substitution der entsprechenden 2-Aryl-1 -haloethane gemäß dem Reaktionsschema (Houben-Weyl, a.a.O., S. 101 ): Another possibility for the preparation of 2-aryl-substituted ethylamines consists in the nucleophilic substitution of the corresponding 2-aryl-1-haloethanes according to the reaction scheme (Houben-Weyl, loc. Cit., P. 101):
Beide Syntheseverfahren weisen jedoch zahlreiche Probleme auf. Dazu zählen insbesondere: • schlechte Verfügbarkeit und hoher Preis der Edukte;However, both synthetic methods have numerous problems. These include in particular: • poor availability and high price of the educts;
• Mehrstufige Herstellungsverfahren;• multi-stage manufacturing processes;
• Bildung von schwer abtrennbaren Nebenprodukten;• formation of by-products that are difficult to separate;
• Weiterreaktion der gewünschten Produkte zu kondensierten Aldolprodukten im Falle der reduktive Aminierung; • Salzbildung im Falle der nukleophilen Substitution.• Further reaction of the desired products to condensed aldol products in the case of reductive amination; • Salt formation in the case of nucleophilic substitution.
LS. Hegedus beschreibt in Angew. Chem. Int. Ed. Engl. 27 (1988), 1113, die intramolekulare oxidative Aminierung in Gegenwart von Palladiumkatalysatoren. Entsprechend diesem Verfahren entstehen bei Verwendung unsymmetrischer Olefine immer Markovnikov-Produkte, d.h. verzweigte Amine.LS. Hegedus describes in Angew. Chem. Int. Ed. Engl. 27 (1988), 1113, the intramolecular oxidative amination in the presence of palladium catalysts. According to this method, when using asymmetrical olefins, Markovnikov products always arise, i.e. branched amines.
Des weiteren weisen diese zur übergangsmetallkatalysierten Aminierung eingesetzten Palladiumkatalysatoren geringe Aktivitäten auf.Furthermore, these palladium catalysts used for transition metal-catalyzed amination have low activities.
R. Taube beschreibt in "Reactions with Nitrogen Compounds: Hydroamination", Applied Homogeneous Catalysis with Organometallic Compounds, B. Cornils, W. A. Herrmann, VCH Verlagsgesellschaft, Weinheim 1996, S. 507 - 520, die direkte Aminierung von Ethylen. Hinsichtlich der Aminierung höherer Olefine als Ethylen wird in dieser Veröffentlichung festgestellt, daß die direkte Aminierung nicht möglich ist, da die höheren Olefine im wesentlichen nicht reagieren. Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines einfachen Verfahrens zur direkten Amininierung oder Hydroaminierung von arylsubstituierten Olefinen, insbesondere ein Verfahren zur Herstellung von 2-arylsubstituierten Ethylen- und Ethylaminen und deren Derivaten, mit dem die genannten Nachteile des Standes der Technik vermieden werden.R. Taube describes in "Reactions with Nitrogen Compounds: Hydroamination", Applied Homogeneous Catalysis with Organometallic Compounds, B. Cornils, WA Herrmann, VCH Verlagsgesellschaft, Weinheim 1996, pp. 507 - 520, the direct amination of ethylene. With regard to the amination of olefins higher than ethylene, it is stated in this publication that direct amination is not possible since the higher olefins essentially do not react. The object of the present invention is to provide a simple process for the direct amination or hydroamination of aryl-substituted olefins, in particular a process for the preparation of 2-aryl-substituted ethylene and ethyl amines and their derivatives, with which the disadvantages of the prior art mentioned are avoided.
Diese Aufgabe wird erfindungsgemäß gelöst durch die Verwendung eines Rhodiumkatalysators zur inter- oder intramolekularen Hydroaminierung und/oder inter- oder intramolekularen oxidativen Aminierung von arylsubstituierten Olefinen mittels primären oder sekundären Aminen, dadurch gekennzeichnet, daß der Rhodiumkatalysator eine kationische Rhodiumverbindung der Oxidationsstufe I oder III enthält.This object is achieved according to the invention by the use of a rhodium catalyst for inter- or intramolecular hydroamination and / or inter- or intramolecular oxidative amination of aryl-substituted olefins using primary or secondary amines, characterized in that the rhodium catalyst contains a cationic rhodium compound of oxidation level I or III.
Durch diesen speziellen Katalysator ist es erstmals möglich, arylsubstituierte Olefine auf direktem Wege zu aminieren.This special catalyst makes it possible for the first time to directly amine aryl-substituted olefins.
Wesentlich bei der Verwendung des erfindungsgemäßen Katalysators ist, daß bei unsymmetrischen Olefinen immer die anti-Markovnikov-Produkte entstehen. Das bedeutet, daß das Stickstoffatom des eingesetzten Amins ausschließlich an dem höher substituierten Kohlenstoffatom der Olefinbindung angreift.It is essential when using the catalyst according to the invention that the anti-Markovnikov products are always formed in the case of asymmetrical olefins. This means that the nitrogen atom of the amine used only attacks the more highly substituted carbon atom of the olefin bond.
Gemäß einer bevorzugten Ausführungsform enthält der Rhodiumkatalysator ein nicht oder nur schwach koordinierendes Anion, insbesondere ein Perchlorat-, Hexafluorophosphat-, Hexafluoroantimonat- oder Tetrafluoroborat-, Tetraarylborat-, Trifluoracetat-, Alkyl- oder Arylsulfonatanion.According to a preferred embodiment, the rhodium catalyst contains a non-coordinating or only weakly coordinating anion, in particular a perchlorate, hexafluorophosphate, hexafluoroantimonate or tetrafluoroborate, tetraarylborate, trifluoroacetate, alkyl or arylsulfonate anion.
Vorzugsweise enthält der Rhodiumkatalysator eine durch mindestens einen Liganden komplexierte kationische Rhodiumverbindung der Oxidationsstufe I oder III. Als Ligand kann ein Phosphan, insbesondere ausgewählt aus der Gruppe von Triphenylphosphan, Trifurylphosphan, Bis-(4-methoxyphenyl)phenylphosphan, Bis- (3-methoxyphenyl)-phenylphosphan, Bis-(4-fluorphenyl)phenylphosphan, Diphenylmethylphosphan, Tricyclohexylphosphan, Tri-n-butylphosphan, Thisopropylphosphan, Tris-(4-methoxyphenyl)phosphan, Tris-(3- methoxyphenyl)phosphan, Ths-(4-fluorophenyl)phosphan, Tris-(3- fluorophenyl)phosphan, Ths-(4-chlorophenyl)phosphan, Tris-(3- chlorophenyl)phosphan, Diphenylphosphinopyridin, Bispyridinophenylphosphan, verwendet werden.The rhodium catalyst preferably contains a cationic rhodium compound of oxidation state I or III complexed by at least one ligand. A phosphane, in particular selected from the group of triphenylphosphine, trifurylphosphine, bis (4-methoxyphenyl) phenylphosphine, bis (3-methoxyphenyl) phenylphosphine, bis (4-fluorophenyl) phenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine, n-butylphosphine, thisopropylphosphine, tris- (4-methoxyphenyl) phosphane, tris- (3-methoxyphenyl) phosphane, Ths- (4-fluorophenyl) phosphine, tris- (3-fluorophenyl) phosphane, Ths- (4-chlorophenyl) phosphane , Tris (3-chlorophenyl) phosphane, diphenylphosphinopyridine, bispyridinophenylphosphine can be used.
Besonders vorteilhaft ist es, wenn das Verhältnis der aus den Phosphanliganden stammenden Phosphoratome zu den Rhodiumatomen - bezogen auf den Katalysator - zwischen 0,5 : 1 und 10 : 1 liegt.It is particularly advantageous if the ratio of the phosphorus atoms from the phosphine ligands to the rhodium atoms, based on the catalyst, is between 0.5: 1 and 10: 1.
Als Ligand kann aber auch ein Diolefin eingesetzt werden, das insbesondere ausgewählt ist aus Cyclooctadien, Dicyclopentadien oder Norbomadien.However, a diolefin can also be used as the ligand, which is selected in particular from cyclooctadiene, dicyclopentadiene or norbomadiene.
In einer weiteren, vorteilhaften Ausführungsform wird der Rhodiumkatalysator, bezogen auf das primäre und/oder sekundäres Amin, in Mengen von 0,0001 mol% bis 20 mol%, insbesondere von 0,1 mol% bis 10 mol%, eingesetzt.In a further advantageous embodiment, the rhodium catalyst, based on the primary and / or secondary amine, is used in amounts from 0.0001 mol% to 20 mol%, in particular from 0.1 mol% to 10 mol%.
Besonders gut kann der zuvor beschriebene Rhodiumkatalysator erfindungsgemäß verwendet werden für die Herstellung eines 2-Arylvinylamins der Formel (I)The rhodium catalyst described above can be used particularly well according to the invention for the preparation of a 2-arylvinylamine of the formula (I)
durch Umsetzung einer Vinylarylverbindung der Formel (II) by reacting a vinylaryl compound of the formula (II)
mit einem Amin der Formel (III)with an amine of formula (III)
FT N (III )FT N (III)
H rTH rT
bei einer Temperatur zwischen 20 und 250 °C in Gegenwart dieses Rhodiumkatalysators, wobeiat a temperature between 20 and 250 ° C in the presence of this rhodium catalyst, wherein
• Ar einen Arylrest darstellt, insbesondere aus der Gruppe der kondensierten oder nicht kondensierten C6-C22-Aromaten, wie z.B. Phenyl-, Naphthyl-, Anthryl-, Phenanthryl- und Biphenylylreste, oder der kondensierten oder nicht kondensierten C5-C22-Heteroaromaten, die im Ring mindestens ein Stickstoff-, Sauerstoff- oder Schwefelatom aufweisen, wie z.B. Indenyl-, Pyridyl-• Ar represents an aryl radical, in particular from the group of the condensed or uncondensed C 6 -C 22 aromatics, such as, for example, phenyl, naphthyl, anthryl, phenanthryl and biphenylyl radicals, or the condensed or uncondensed C 5 -C 2 2-heteroaromatics which have at least one nitrogen, oxygen or sulfur atom in the ring, such as, for example, indenyl, pyridyl
Pyrazyireste;Pyrazate residues;
• R1 und R2 unabhängig voneinander ein Wasserstoffatom oder einen C1-C4- Alkylrest darstellen; und• R 1 and R 2 independently represent a hydrogen atom or a C1-C 4 alkyl radical; and
• R3 und R4 unabhängig voneinander ein Wasserstoffatom, einen C1-C20- Alkylrest oder einen der zuvor definierten Arylreste Ar darstellen, oder R3 und• R 3 and R 4 independently of one another represent a hydrogen atom, a C1-C20-alkyl radical or one of the previously defined aryl radicals Ar, or R 3 and
R4 zusammen mit dem Stickstoffatom des Amins der Formel (III) zu einem C-ι-Cιo-Heterocyclus verbunden sind, wobei dieser Heterocyclus noch weitere Heteroatome, wie z.B. Sauerstoff, Stickstoff oder Schwefel, enthalten kann. Ebenso kann dieser Katalysator erfindungsgemäß zur Herstellung eines 2- Arylethylamins der Formel (I)R 4 together with the nitrogen atom of the amine of the formula (III) are joined to form a C 1 -C 10 heterocycle, which heterocycle may also contain further heteroatoms, such as oxygen, nitrogen or sulfur. According to the invention, this catalyst can also be used to prepare a 2-arylethylamine of the formula (I)
durch Umsetzung einer Vinylarylverbindung der Formel (II)by reacting a vinylaryl compound of the formula (II)
mit einem Amin der Formel (III)with an amine of formula (III)
R3 R 3
H RMR
bei einer Temperatur zwischen 20 und 250 °C verwendet werden, wobei die Reste R1 bis R und Ar die gleiche Bedeutung haben, wie zuvor angegeben.be used at a temperature between 20 and 250 ° C, wherein the radicals R 1 to R and Ar have the same meaning as previously indicated.
Der entweder aus der Vinylarylverbindung der Formel (II) oder dem Amin der Formel (III) stammende Arylrest Ar kann bis zu 8 Substituenten aufweisen, die unabhängig voneinander ein Fluor-, Chlor-, Brom- oder lodatom darstellen oder ausgewählt sind aus der Gruppe der HO-, HC(O)-, HCO2-, H2N-, NC-, HC(O)NH-, H2NC(O)-, NO2-, HSO3-, CF3-, R5-, R5O-, R5C(O)-, R5CO2-, R5NH-, R5 2N-, R5C(O)NH-, R5CO2CHCH-, R5SO2-, R5S(O)-, R5P(O)-, und R5 3Si-Reste, sowie aus fünf- und sechsgliedrigen Heteroaromaten, die im Ring mindestens ein Stickstoff-, Sauerstoff- oder Schwefelatom aufweisen; wobei R einen linearen oder verzweigten C1-C20- Alkylrest oder den zuvor beschriebenen Aryirest Ar darstellt.The aryl radical Ar, originating either from the vinylaryl compound of the formula (II) or from the amine of the formula (III), can have up to 8 substituents which independently of one another represent a fluorine, chlorine, bromine or iodine atom or are selected from the group of HO-, HC (O) -, HCO 2 -, H 2 N-, NC-, HC (O) NH-, H 2 NC (O) -, NO 2 -, HSO 3 -, CF 3 -, R 5 -, R 5 O-, R 5 C (O) -, R 5 CO 2 -, R 5 NH-, R 5 2 N-, R 5 C (O) NH-, R 5 CO 2 CHCH-, R 5 SO 2 -, R 5 S (O) -, R 5 P (O) -, and R 5 3 Si residues, as well as from five and six-membered heteroaromatics which have at least one nitrogen, oxygen or sulfur atom in the ring; where R represents a linear or branched C 1 -C 20 alkyl radical or the aryl radical Ar described above.
In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung ist die Vinylarylverbindung der Formel (II) Styrol, insbesondere ein in ortho-, meta- oder para-Position substituiertes Styrol, vorzugsweise ein mit einem Heteroarylrest substituiertes Styrol.In a particularly preferred embodiment of the present invention, the vinylaryl compound of the formula (II) is styrene, in particular styrene substituted in the ortho, meta or para position, preferably styrene substituted with a heteroaryl radical.
Als Amin der Formel (III) kann ein primäres oder sekundäres, aromatisches oder aliphatisches Amin eingsetzt werden.A primary or secondary, aromatic or aliphatic amine can be used as the amine of the formula (III).
Besonders bevorzugt sind hierbei Morpholin, Piperidin, Piperazin, Dimethylamin, Diethylamin, Dipropylamin oder Dibutylamin.Morpholine, piperidine, piperazine, dimethylamine, diethylamine, dipropylamine or dibutylamine are particularly preferred.
Die gemäß dem vorliegenden Verfahren erhaltenen Verbindungen, insbesondere die 2-Arylvinylamine können isoliert oder für Folgereaktionen wie Hydrierung oder Umsetzung mit Elektrophilen (Aldehyden, Epoxiden, Alkylhalogeniden) direkt weiter eingesetzt werden. Als Lösungsmittel dienen im erfindungsgemäßen Verfahren generell inerte organische Lösungsmittel. Bevorzugt sind aromatische Kohlenwasserstoffe wie Toluol, Xylole, Anisol, Tetralin und aliphatische Ether wie Tetrahydrofuran, Dimethoxyethan, Dioxan, Tetrahydropyran, Formaldehydacetale. Die Umsetzung der Amine mit substituierten Styrolen findet bei Temperaturen von 20 - 250 °C, bevorzugt bei 40 - 200 °C und besonders bevorzugt bei 60 - 160 °C statt.The compounds obtained according to the present process, in particular the 2-arylvinylamines, can be isolated or used directly for subsequent reactions such as hydrogenation or reaction with electrophiles (aldehydes, epoxides, alkyl halides). Inert organic solvents are generally used as solvents in the process according to the invention. Aromatic hydrocarbons such as toluene, xylenes, anisole, tetralin and aliphatic ethers such as tetrahydrofuran, dimethoxyethane, dioxane, tetrahydropyran, formaldehyde acetals are preferred. The reaction of the amines with substituted styrenes takes place at temperatures of 20-250 ° C, preferably at 40-200 ° C and particularly preferably at 60-160 ° C.
Je nach Wahl der Ausgangsprodukte wird bevorzugt das 2-Arylvinylamin oder das 2-Arylethylamin gebildet.Depending on the choice of the starting products, the 2-arylvinylamine or the 2-arylethylamine is preferably formed.
So entsteht einerseits beispielsweise unter Verwendung von 2-Vinylnaphtalin und Piperidin entsprechend dem erfindungsgemäßen Verfahren ausschließlich das 2- Arylvinylamin. Auf der anderen Seite entsteht z.B. aus der Reaktion von 2-Vinylpyridin und Morpholin ausschließlich das 2-Arylethylamin.On the one hand, for example, using 2-vinylnaphthalene and piperidine, only 2-arylvinylamine is formed in accordance with the process of the invention. On the other hand, the reaction of 2-vinylpyridine and morpholine, for example, produces only 2-arylethylamine.
Das in anderen Fällen erhaltene Gemisch aus 2-Arylvinylamin oder 2-Arylethylamin kann man durch geeignete Verfahren, insbesondere säulenchromatographisch isolieren.The mixture of 2-arylvinylamine or 2-arylethylamine obtained in other cases can be isolated by suitable methods, in particular by column chromatography.
Um die Ausbeute des entstandenen 2-Arylethylamins zu erhöhen, kann man das erhaltene 2-Arylvinylamin anschließend in Gegenwart von Wasserstoff und einem Hydrierkatalysator nach Standardbedingungen (K Weissermel, H. J. Arpe, Industrielle Organische Chemie, VCH, 1988) zu dem korrespondierenden 2- Arylethylamin hydrieren.To increase the yield of the resulting 2-arylethylamine, the 2-arylvinylamine obtained can then be hydrogenated in the presence of hydrogen and a hydrogenation catalyst according to standard conditions (K Weissermel, HJ Arpe, Industrielle Organische Chemie, VCH, 1988) to the corresponding 2-arylethylamine .
Die Produkte bilden sich nach dem erfindungsgemäßen Verfahren generell in guten Ausbeuten bis zu 99 %.The products are generally formed in good yields of up to 99% by the process according to the invention.
Als Nebenprodukte werden die Hydrierprodukte der eingesetzten Vinylarylverbindung beobachtet, die leicht abtrennbar sind. Im Fall von Styrol entsteht als Nebenprodukt Ethylbenzol.The hydrogenation products of the vinylaryl compound used are observed as by-products and are easily separable. In the case of styrene, ethylbenzene is formed as a by-product.
Beispiele: Alle Versuche wurden unter Ausschluß von Luft und Feuchtigkeit durchgeführt. Die verwendeten Chemikalien wurden nach allgemein üblichen Vorschriften absolutiert und unter N2 bzw. Argon aufbewahrt. (COD)2RhBF4 (Bis-1-2:5-6-η- cyclooctadien(1 ,5)rhodium(l)tetrafluoroborat) wurde gemäß R.R. Schrock, J. Osborn in J. Am. Chem. Soc. 93 (1971 ), S. 3089, hergestellt.Examples: All experiments were carried out in the absence of air and moisture. The chemicals used were absolute according to generally accepted regulations and stored under N 2 or argon. (COD) 2 RhBF 4 (bis-1-2: 5-6-η-cyclooctadiene (1, 5) rhodium (l) tetrafluoroborate) was determined according to RR Schrock, J. Osborn in J. Am. Chem. Soc. 93 (1971), p. 3089.
Beispiel 1:Example 1:
17,6 mmol Styrol werden mit 4,4 mmol Piperidin in Gegenwart von 2,5 mol% (45 mg) Rhodiumkatalysator (Bis-1-2:5-6-η-cyclooctadien(1 ,5)rhodium(l)tetrafluoroborat) und 2 eq. Triphenylphosphan (58 mg) in 10,0 ml Tetrahydrofuran gemischt. Diese Mischung wird 20 h lang unter Schutzgas refluxiert. Anschließend wird 48 h lang unter einem Wasserstoffdruck von 1 bar und 0,5 g Pd/C (5%-ig) hydriert. Nach Abfiltrieren von Pd/C wird das Lösemittel mittels eines Rotationsverdampfers entfernt und der Rückstand mit 20,0 ml Methylenchlorid aufgenommen, danach 3 mal gegen je 20 ml 5 %-ige Salzsäure ausgeschüttelt und die wäßrigen Phasen vereinigt. Anschließend wird die wäßrige Phase mit NaOH-Plätzchen vorsichtig auf einen pH-Wert von 9 gebracht und 3 mal gegen 20 ml Methylenchlorid ausgeschüttelt. Die vereinigte organische Phase wird über Magnesiumsulfat getrocknet, mittels eines Rotationsverdampfers eingeengt und im Vakuum (10"3 bar) getrocknet. Das Produkt wird säulenchromatographisch gereinigt. Man erhält das gewünschte Produkt (Λ/-2-Phenylethylpiperidin) in 55 % Ausbeute. Das Produkt wird mittels 1H-NMR, 13C-NMR, DEPT-13C-NMR und MS charakterisiert. Beispiele 2 - 19 Die Beispiele 2 - 19 werden analog Beispiel 1 ausgeführt. Die Edukte und deren Mengen sowie die Reaktionsergebnisse sind in Tabelle 1 zusammengefaßt. (NBD)2RhBF wurde gemäß T.G. Schenk et al. in Inorg. Chem. 24 (1985), S. 2334, hergestellt. Die anschließende Hydrierung zum Amin wurde in den Versuchen 14 - 17 nicht durchgeführt. 17.6 mmol styrene are mixed with 4.4 mmol piperidine in the presence of 2.5 mol% (45 mg) rhodium catalyst (bis-1-2: 5-6-η-cyclooctadiene (1, 5) rhodium (l) tetrafluoroborate) and 2 eq. Triphenylphosphine (58 mg) mixed in 10.0 ml tetrahydrofuran. This Mixture is refluxed under protective gas for 20 h. The mixture is then hydrogenated for 48 hours under a hydrogen pressure of 1 bar and 0.5 g of Pd / C (5%). After Pd / C has been filtered off, the solvent is removed by means of a rotary evaporator and the residue is taken up in 20.0 ml of methylene chloride, then shaken 3 times against 20 ml of 5% hydrochloric acid and the aqueous phases are combined. The aqueous phase is then carefully brought to pH 9 with NaOH cookies and shaken out 3 times against 20 ml of methylene chloride. The combined organic phase is dried over magnesium sulfate, concentrated using a rotary evaporator and dried in vacuo (10 -3 bar). The product is purified by column chromatography. The desired product (Λ / -2-phenylethylpiperidine) is obtained in 55% yield. The product is characterized by 1 H-NMR, 13 C-NMR, DEPT- 13 C-NMR and MS Examples 2-19 Examples 2-19 are carried out analogously to Example 1. The starting materials and their amounts and the reaction results are summarized in Table 1 (NBD) 2 RhBF was prepared according to TG Schenk et al., Inorg. Chem. 24 (1985), p. 2334. The subsequent hydrogenation to the amine was not carried out in experiments 14-17.
Tabelle 1Table 1
Abkürzungen:Abbreviations:
COD = Cyclooctadien NBD = Norbornadien COD = cyclooctadiene NBD = norbornadiene

Claims

Patentansprüche: Claims:
1. Verwendung eines Rhodiumkatalysators zur inter- oder intramolekularen1. Use of a rhodium catalyst for inter- or intramolecular
Hydroaminierung und/oder inter- oder intramolekularen oxidativen Aminierung von arylsubstituierten Olefinen mittels primären oder sekundären Aminen, dadurch gekennzeichnet, daß der Rhodiumkatalysator eine kationische Rhodiumverbindung der Oxidationsstufe I oder III enthält.Hydroamination and / or inter- or intramolecular oxidative amination of aryl-substituted olefins by means of primary or secondary amines, characterized in that the rhodium catalyst contains a cationic rhodium compound of oxidation level I or III.
2. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, daß der Rhodiumkatalysator ein nicht oder schwach koordinierendes Anion, insbesondere ein Perchlorat-, Hexafluorophosphat-, Hexafluoroantimonat- oder Tetrafluoroborat-, Tetraarylborat-, Trifluoracetat-, Alkyl- oder Arylsulfonatanion enthält.2. Use according to claim 1, characterized in that the rhodium catalyst contains a non-coordinating or weakly coordinating anion, in particular a perchlorate, hexafluorophosphate, hexafluoroantimonate or tetrafluoroborate, tetraarylborate, trifluoroacetate, alkyl or arylsulfonate anion.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Rhodiumkatalysator eine durch mindestens einen Liganden komplexierte kationische Rhodiumverbindung der Oxidationsstufe I oder IM enthält.3. Use according to claim 1 or 2, characterized in that the rhodium catalyst contains a cationic rhodium compound of oxidation state I or IM complexed by at least one ligand.
4. Verwendung nach Anspruch 3, dadurch gekennzeichnet, daß mindestens ein Ligand ein Phosphan ist, insbesondere ausgewählt aus der Gruppe von Triphenylphosphan, Trifurylphosphan, Bis-(4-methoxyphenyl)phenylphosphan, Bis-(3-methoxyphenyl)-phenylphosphan, Bis-(4-fluorphenyl)phenylphosphan, Diphenylmethylphosphan, Tricyclohexylphosphan, Tri-n-butylphosphan,4. Use according to claim 3, characterized in that at least one ligand is a phosphine, in particular selected from the group of triphenylphosphine, trifurylphosphine, bis (4-methoxyphenyl) phenylphosphine, bis (3-methoxyphenyl) phenylphosphine, bis ( 4-fluorophenyl) phenylphosphine, diphenylmethylphosphane, tricyclohexylphosphine, tri-n-butylphosphine,
T isopropylphosphan, Tris-(4-methoxyphenyl)phosphan, Tris-(3- methoxyphenyl)phosphan, Tris-(4-fluorophenyl)phosphan, Tris-(3- fluorophenyl)phosphan, Tris-(4-chlorophenyl)phosphan, Tris-(3- chlorophenyl)phosphan, Diphenylphosphinopyridin und Bispyridinophenylphosphan T isopropylphosphine, tris- (4-methoxyphenyl) phosphane, tris- (3-methoxyphenyl) phosphane, tris- (4-fluorophenyl) phosphane, tris- (3-fluorophenyl) phosphane, tris- (4-chlorophenyl) phosphane, tris- (3-chlorophenyl) phosphane, diphenylphosphinopyridine and bispyridinophenylphosphine
5. Verwendung nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß bezogen auf den Katalysator das Verhältnis der aus den Phosphanliganden stammenden Phosphoratome zu den Rhodiumatomen zwischen 0,5 : 1 und 10 : 1 liegt.5. Use according to claim 3 or 4, characterized in that, based on the catalyst, the ratio of the phosphorus atoms originating from the phosphine ligands to the rhodium atoms is between 0.5: 1 and 10: 1.
6. Verwendung nach einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, daß mindestens ein Ligand ein Diolefin ist, insbesondere ausgewählt aus Cyclooctadien, Dicyclopentadien oder Norbornadien.6. Use according to any one of claims 3 to 5, characterized in that at least one ligand is a diolefin, especially selected from cyclooctadiene, dicyclopentadiene or norbornadiene.
7. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Rhodiumkatalysator, bezogen auf die Komponenten Ammoniak, primäres Amin und sekundäres Amin, in Mengen von 0,0001 mol% bis 20 mol%, insbesondere von 0,1 mol% bis 10 mol%, eingesetzt wird.7. Use according to one of the preceding claims, characterized in that the rhodium catalyst, based on the components ammonia, primary amine and secondary amine, in amounts of 0.0001 mol% to 20 mol%, in particular from 0.1 mol% to 10 mol% is used.
8. Verfahren zur Herstellung eines 2-Arylvinylamins der Formel (I)8. Process for the preparation of a 2-arylvinylamine of the formula (I)
durch Umsetzung einer Vinylarylverbindung der Formel (II)by reacting a vinylaryl compound of the formula (II)
mit einem Amin der Formel (III) with an amine of formula (III)
RR
(III)(III)
H -N -R<H - N -R <
in Gegenwart eines Rhodiumkatalysators, der eine kationischein the presence of a rhodium catalyst, which is a cationic
Rhodiumverbindung der Oxidationsstufe I oder IM enthält, bei einer Temperatur zwischen 20 und 250 °C, wobeiRhodium compound of oxidation level I or IM contains, at a temperature between 20 and 250 ° C, wherein
• Ar einen Aryirest darstellt, insbesondere aus der Gruppe der kondensierten oder nicht kondensierten C6-C22-Aromaten, wie z.B. Phenyl-, Naphthyl-, Anthryl-, Phenanthryl- und Biphenylylreste, oder der kondensierten oder nicht kondensierten C5-C22-Heteroaromaten, die im Ring mindestens ein Stickstoff-, Sauerstoff- oder Schwefelatom aufweisen, wie z.B. Indenyl-, Pyridyl- oder Pyrazylreste;• Ar represents an aryl radical, in particular from the group of the condensed or uncondensed C 6 -C 22 aromatics, such as, for example, phenyl, naphthyl, anthryl, phenanthryl and biphenylyl radicals, or the condensed or uncondensed C 5 -C 22 Heteroaromatics which have at least one nitrogen, oxygen or sulfur atom in the ring, such as, for example, indenyl, pyridyl or pyrazyl radicals;
• R und R unabhängig voneinander ein Wasserstoffatom oder einen C1-C4- Alkylrest darstellen; und• R and R independently of one another represent a hydrogen atom or a C 1 -C 4 alkyl radical; and
• R3 und R4 unabhängig voneinander ein Wasserstoffatom, einen C-1-C20- Alkylrest oder einen der zuvor definierten Arylreste Ar darstellen, oder R3 und R4 zusammen mit dem Stickstoff atom des Amins der Formel (IM) zu einem C4-Cιo-Heterocyclus verbunden sind, wobei dieser Heterocyclus noch weitere Heteroatome, wie z.B. Sauerstoff, Stickstoff oder Schwefel, enthalten kann.R 3 and R 4 independently of one another represent a hydrogen atom, a C-1-C20-alkyl radical or one of the previously defined aryl radicals Ar, or R 3 and R 4 together with the nitrogen atom of the amine of the formula (IM) to give a C4- Cιo-heterocycle are connected, which heterocycle may contain further heteroatoms, such as oxygen, nitrogen or sulfur.
9. Verfahren zur Herstellung eines 2-Arylethylamins der Formel (I) 9. Process for the preparation of a 2-arylethylamine of the formula (I)
durch Umsetzung einer Vinylarylverbindung der Formel (II)by reacting a vinylaryl compound of the formula (II)
mit einem Amin der Formel (IM)with an amine of the formula (IM)
R°R °
. N „ 4 (III ) H R. N "4 (III) H R
in Gegenwart eines Rhodiumkatalysators, der eine kationische Rhodiumverbindung der Oxidationsstufe I oder IM enthält, bei einer Temperatur zwischen 20 und 250 °C, wobei die Reste R1 bis R4 und Ar die gleiche Bedeutung haben, wie in Anspruch 8.in the presence of a rhodium catalyst which contains a cationic rhodium compound of oxidation state I or IM, at a temperature between 20 and 250 ° C, the radicals R 1 to R 4 and Ar having the same meaning as in claim 8.
10. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß der Aryirest Ar bis zu 8 Substituenten aufweist, die unabhängig voneinander ein Fluor-, Chlor-, Brom- oder lodatom darstellen oder ausgewählt sind aus der Gruppe der HO-, HC(O)-, HCO2-, H2N-, NC-, HC(O)NH-, H2NC(O)-, NO2-, HS03-, CF3- , R5-, R5O-, R5C(O)-, R5CO2-, R5NH-, R5 2N-, R5C(O)NH-, R5CO2CHCH-,10. The method according to claim 8 or 9, characterized in that the Aryirest Ar has up to 8 substituents which independently represent a fluorine, chlorine, bromine or iodine atom or are selected from the group of HO, HC (O ) -, HCO 2 -, H 2 N-, NC-, HC (O) NH-, H 2 NC (O) -, NO 2 -, HS0 3 -, CF 3 -, R 5 -, R 5 O- , R 5 C (O) -, R 5 CO 2 -, R 5 NH-, R 5 2 N-, R 5 C (O) NH-, R 5 CO 2 CHCH-,
R5SO2-, R5S(O)-, R5P(O)-, und R5 3Si-Reste, sowie aus fünf- und sechsgliedrigen Heteroaromaten, die im Ring mindestens ein Stickstoff-, Sauerstoff- oder Schwefelatom aufweisen; wobei R5 einen linearen oder verzweigten C-|-C2o-Alkylrest oder Ar darstellt, wobei Ar die gleiche Bedeutung hat wie in Anspruch 8.R 5 SO 2 -, R 5 S (O) -, R 5 P (O) -, and R 5 3 Si residues, as well as from five- and six-membered heteroaromatics which contain at least one nitrogen, Have oxygen or sulfur atom; wherein R 5 represents a linear or branched C- | -C 2 o-alkyl radical or Ar, where Ar has the same meaning as in claim 8.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß die Vinylarylverbindung der Formel (II) Styrol ist.11. The method according to claim 10, characterized in that the vinylaryl compound of the formula (II) is styrene.
12. Verfahren nach Anspruch 11 , dadurch gekennzeichnet, daß die Vinylarylverbindung ein in ortho-, meta- oder para-Position substituiertes Styrol ist.12. The method according to claim 11, characterized in that the vinylaryl compound is a styrene substituted in the ortho, meta or para position.
13. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, daß das Styrol der Formel (II) ein mit einem Heteroarylrest substituiertes Styrol ist.13. The method according to claim 11 or 12, characterized in that the styrene of formula (II) is a substituted with a heteroaryl styrene.
14. Verfahren nach einem der Ansprüche 8 bis 13, dadurch gekennzeichnet, daß das Amin der Formel (III) ein primäres oder sekundäres, aromatisches oder aliphatisches Amin ist.14. The method according to any one of claims 8 to 13, characterized in that the amine of formula (III) is a primary or secondary, aromatic or aliphatic amine.
15. Verfahren nach einem der Ansprüche 8 bis 13, dadurch gekennzeichnet, daß das Amin der Formel (IM) Morpholin, Piperidin, Piperazin, Dimethylamin,15. The method according to any one of claims 8 to 13, characterized in that the amine of the formula (IM) morpholine, piperidine, piperazine, dimethylamine,
Diethyiamin, Dipropylamin oder Dibutylamin ist.Diethyiamine, Dipropylamin or Dibutylamin is.
16. Verfahren nach einem der Ansprüche 8 bis 15, dadurch gekennzeichnet, daß der Rhodiumkatalysator ein nicht oder schwach koordinierendes Anion, insbesondere ein Perchlorat-, Hexafluorophosphat-, Hexafluoroantimonat- oder Tetrafluoroborat-, Tetraarylborat-, Trifluoracetat-, Alkyl- oder Arylsulfonatanion enthält.16. The method according to any one of claims 8 to 15, characterized in that the rhodium catalyst contains a non or weakly coordinating anion, in particular a perchlorate, hexafluorophosphate, hexafluoroantimonate or tetrafluoroborate, tetraaryl borate, trifluoroacetate, alkyl or arylsulfonate anion.
17. Verfahren nach einem der Ansprüche 8 bis 16, dadurch gekennzeichnet, daß der Rhodiumkatalysator eine durch mindestens einen Liganden komplexierte kationische Rhodiumverbindung der Oxidationsstufe I oder IM enthält. 17. The method according to any one of claims 8 to 16, characterized in that the rhodium catalyst contains a cationic rhodium compound of oxidation state I or IM complexed by at least one ligand.
18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, daß mindestens ein Ligand ein Phosphan ist, insbesondere ausgewählt aus der Gruppe von Triphenylphosphan, Trifurylphosphan, Bis-(4-methoxyphenyl)phenylphosphan, Bis-(3-methoxyphenyl)-phenylphosphan, Bis-(4-fluorphenyl)phenylphosphan,18. The method according to claim 17, characterized in that at least one ligand is a phosphine, in particular selected from the group of triphenylphosphine, trifurylphosphine, bis (4-methoxyphenyl) phenylphosphine, bis (3-methoxyphenyl) phenylphosphine, bis ( 4-fluorophenyl) phenylphosphine,
Diphenylmethylphosphan, Tricyclohexylphosphan, Tri-n-butylphosphan, Triisopropylphosphan, Tris-(4-methoxyphenyl)phosphan, Tris-(3- methoxyphenyl)phosphan, Tris-(4-fluorophenyl)phosphan, Tris-(3- fluorophenyl)phosphan, Tris-(4-chlorophenyl)phosphan, Tris-(3- chlorophenyl)phosphan, Diphenylphosphinopyridin undDiphenylmethylphosphine, tricyclohexylphosphine, tri-n-butylphosphine, triisopropylphosphine, tris- (4-methoxyphenyl) phosphine, tris- (3-methoxyphenyl) phosphane, tris- (4-fluorophenyl) phosphane, tris- (3-fluorophenyl) phosphane, tris- (4-chlorophenyl) phosphane, tris (3-chlorophenyl) phosphane, diphenylphosphinopyridine and
Bispyridinophenylphosphan.Bispyridinophenylphosphine.
19. Verfahren nach Anspruch 17 oder 18, dadurch gekennzeichnet, daß bezogen auf den Katalysator das Verhältnis der aus den Phosphanliganden stammenden Phosphoratome zu den Rhodiumatomen zwischen 0,5 : 1 und19. The method according to claim 17 or 18, characterized in that based on the catalyst, the ratio of the phosphorus atoms originating from the phosphine ligands to the rhodium atoms between 0.5: 1 and
10 : 1 liegt.10: 1 lies.
20. Verfahren nach einem der Ansprüche 17 bis 19, dadurch gekennzeichnet, daß mindestens ein Ligand ein Diolefin ist, insbesondere ausgewählt aus Cyclooctadien, Dicyclopentadien oder Norbornadien.20. The method according to any one of claims 17 to 19, characterized in that at least one ligand is a diolefin, in particular selected from cyclooctadiene, dicyclopentadiene or norbornadiene.
21. Verfahren nach einem der Ansprüche 8 bis 20, dadurch gekennzeichnet, daß der Rhodiumkatalysator, bezogen auf das Amin der Formel (IM), in Mengen von 0,0001 mol% bis 20 mol%, insbesondere von 0,1 mol% bis 10 mol%, eingesetzt wird. 21. The method according to any one of claims 8 to 20, characterized in that the rhodium catalyst, based on the amine of the formula (IM), in amounts of 0.0001 mol% to 20 mol%, in particular from 0.1 mol% to 10 mol% is used.
EP98930677A 1997-05-28 1998-05-08 Use of a rhodium catalyst for hydroamination and/or oxidative amination of aryl-substituted olefins and method for producing a 2-aryl vinyl amine Withdrawn EP0984909A1 (en)

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DE19722373A1 (en) 1998-12-03
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WO1998054115A1 (en) 1998-12-03
JP2002500653A (en) 2002-01-08

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