DE102018101218A1 - Ruthenium-based catalyst system and ruthenium complex-catalyzed synthesis of primary amines from carbonyl compounds and ammonia - Google Patents

Ruthenium-based catalyst system and ruthenium complex-catalyzed synthesis of primary amines from carbonyl compounds and ammonia Download PDF

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DE102018101218A1
DE102018101218A1 DE102018101218.7A DE102018101218A DE102018101218A1 DE 102018101218 A1 DE102018101218 A1 DE 102018101218A1 DE 102018101218 A DE102018101218 A DE 102018101218A DE 102018101218 A1 DE102018101218 A1 DE 102018101218A1
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catalyst system
ammonia
ruthenium
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Venkata Narayana Kalevaru
Jagadeesh Rajenahally
Thirusangumurugan Senthamarai
Kathiravan Murugesan
Helfried Neumann
Paul C. J. Kamer
Matthias Beller
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Leibniz Institut fur Katalyse E V An Der Univ Rostock
Leibniz-Institut fur Katalyse Ev An Der Universitat Rostock
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Leibniz Institut fur Katalyse E V An Der Univ Rostock
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Abstract

Um ein Katalysatorsystem und ein Verfahren zur Herstellung von primären Aminen aus Carbonylverbindungen und Ammoniak bereitzustellen, das es ermöglicht, einfach und kostengünstig primäre Aminen herzustellen, werden ein Ruthenium-Halogen-Komplex mit Triphenylphosphin-Liganden und ein Verfahren zur Herstellung primärer Amine durch reduktive Aminierung von primären Carbonylverbindungen mittels Ammoniak in Anwesenheit von Wasserstoff und dem Ruthenium-basierten Katalysatorsystem vorgeschlagen.In order to provide a catalyst system and a process for producing primary amines from carbonyl compounds and ammonia, which makes it possible to easily and inexpensively produce primary amines, a ruthenium-halogen complex with triphenylphosphine ligands and a process for the preparation of primary amines by reductive amination of primary carbonyl compounds by means of ammonia in the presence of hydrogen and the ruthenium-based catalyst system proposed.

Description

Die Erfindung betrifft ein Katalysatorsystem zur Herstellung von primären Aminen aus Carbonylverbindungen und Ammoniak In Anwesenheit von Wasserstoff bestehend aus einem Ruthenium-Halogenid-Komplex mit Triphenylphosphin-Liganden sowie ein Verfahren zur Herstellung primärer Amine durch reduktive Aminierung von primären Carbonylverbindungen mittels Ammoniak unter Verwendung des Katalysatorsystems.The invention relates to a catalyst system for the preparation of primary amines from carbonyl compounds and ammonia in the presence of hydrogen consisting of a ruthenium-halide complex with triphenylphosphine ligands and a process for the preparation of primary amines by reductive amination of primary carbonyl compounds by means of ammonia using the catalyst system.

Amine sind wertvolle Chemikalien für den täglichen Einsatz, die in vielen Bereichen der Wissenschaft wie Chemie, Biologie, Medizin und Materialien weit verbreitet sind. So enthalten bemerkenswerterweise die meisten Pharmazeutika, Agrochemikalien, Biomoleküle und Naturstoffe Aminfunktionalitäten, die wichtige strukturelle Motive darstellen. Ca. zwei Drittel der im Jahr 2015 am meisten verschriebenen Medikamente enthalten mindestens eine Aminogruppe, die für die pharmazeutische Wirkung wesentlich istAmines are valuable chemicals for everyday use that are widely used in many areas of science such as chemistry, biology, medicine and materials. Remarkably, most pharmaceuticals, agrochemicals, biomolecules, and natural products contain amine functionalities that are important structural motifs. Approximately Two-thirds of the drugs most prescribed in 2015 contain at least one amino group that is essential for the pharmaceutical effect

Unter den verschiedenen Klassen von Aminen bilden primäre Benzyl- und aliphatische Amine wichtige Fein- und Massenchemikalien, die als zentrale Ausgangsmaterialien und wichtige Zwischenprodukte für Chemikalien, Moleküle und Materialien der Biowissenschaften dienen.Among the various classes of amines, primary benzyl and aliphatic amines constitute important fine and bulk chemicals that serve as key feedstocks and important intermediates for life sciences chemicals, molecules, and materials.

Hinsichtlich der Synthese dieser Klasse von Aminen werden üblicherweise drei Verfahren verwendet:

  • - Hydrierung von Nitrilen,
  • - Aminierung von Alkoholen und
  • - reduktive Aminierung von Carbonylverbindungen.
With regard to the synthesis of this class of amines, three methods are commonly used:
  • - hydrogenation of nitriles,
  • - Amination of alcohols and
  • - Reductive amination of carbonyl compounds.

Die Hydrierung von Nitrilen wird jedoch nur zur Herstellung von linearen, unverzweigten primären Aminen angewendet. Darüber hinaus beruht die Herstellung von Nitrilen hauptsächlich auf einem toxischen Cyanierungsverfahren.The hydrogenation of nitriles, however, is only used for the preparation of linear, unbranched primary amines. Moreover, the production of nitriles is mainly due to a toxic cyanation process.

Obwohl die Herstellung von Aminen aus Alkoholen und Ammoniak im Gegensatz zum erstgenannten Verfahren verbreiteter ist, begrenzen drastische Reaktionsbedingungen, die für die Aktivierung von Alkoholen mit Ammoniak erforderlich sind, und eine geringere Verfügbarkeit von verzweigten Alkoholen die Anwendung für die Synthese von verschiedenen Aminen.Although the production of amines from alcohols and ammonia is more common, unlike the former, drastic reaction conditions required for the activation of alcohols with ammonia and reduced availability of branched alcohols limit their application to the synthesis of various amines.

Zudem erfolgt eine reduktive Aminierung von Carbonylverbindungen unter Verwendung von Ammoniak zur Herstellung von primären Aminen in der Regel unter Verwendung von heterogenen Katalysatoren, da eine homogene Katalyse Probleme mit Übergangsmetallkomplexen aufweist und sich allenfalls unter Schwierigkeiten realisieren lässt.In addition, a reductive amination of carbonyl compounds using ammonia for the production of primary amines is usually carried out using heterogeneous catalysts, since a homogeneous catalysis has problems with transition metal complexes and can be implemented at best with difficulty.

Die Anwendung von homogenen Katalysatoren für diese Reaktion weist Schwierigkeiten auf, da Übergangsmetallkomplexe, die üblicherweise Reaktionen mit Ammoniak katalysieren, unter anderem durch die Bildung stabiler Werner-Aminkomplexe deaktiviert werden. Darüber hinaus treten häufig Probleme auf, wie Nichtselektivität, Überalkylierungen und Reduktion zu entsprechenden Alkoholen.The use of homogeneous catalysts for this reaction presents difficulties, since transition metal complexes, which usually catalyze reactions with ammonia, are deactivated inter alia by the formation of stable Werner-amine complexes. In addition, problems such as non-selectivity, overalkylations and reduction to corresponding alcohols often occur.

Bekannt sind daher wenige Katalysatoren für die homogene Katalyse auf der Basis von Rh-, Ir- und Ru-Metallkomplexen. So wurde [Rh(COD)Cl]2-TPPTS (TPPTS = 3,3',3"-Phosphinidynetris(benzolsulfonsäure)trinatriumsalz) als Katalysator für die Herstellung von einfachen primären Aminen aus Aldehyden beschrieben, wobei zudem wässriger Ammoniak und NH4OAC als Additiv eingesetzt wird ( Gross, T.; Seayad, A. M.; Ahmad, M.; Beller, M. Org. Lett. 2002, 4, 2055-2058 ). Rh[(dppb)(COD)]BF4 und [Rh(COD) Cl]2-BINAS Katalysatoren werden ebenfalls verwendet (COD= 1,5-Cyclooctadien; BINAS= 2,2'-bis[[bis(3-sulfophenyl)phosphino]methyl]-4,4',7,7'-tetrasulfo-1,1'-binaphthyl octanatriumsalz), (Riermeier, T.; Haack, K.-J. Uwe Dingerdissen, Boerner, Tararov, A. V.; Kadyrov, R.; Weniger; US 6,884,887 B1, 2005). Ir-basierte Komplexe wie [Ir(COD)Cl]2-BINAS können die Reaktion von einzelnen einfachen Ketonen mit Ammoniak katalysieren (Riermeier, T.; Haack, K.-J. Uwe Dingerdissen, Boerner, Tararov, A. V.; Kadyrov, R.; Weniger. US 6,884,887 B1, 2005). Katalysatorsysteme wie Ru(CO)CIH(PPh3)-Xantphos-dppe (Gallardo-Donaire, J.; Ernst, M.; Trapp, O.; Schaub, T.; Adv. Synth. Catal. 2016, 358, 358-363) und Ru(CO)CIH(PPh3)- (S,S)-f-binaphane ((S,S)-f-binaphane=1,1'-Bis[(S)-4,5-dihydro-3H-binaphthol[2,1-c:1',2'-e]phosphepino]ferrocen) werden zur reduktiven Aminierung von einfachen Ketonen zur Herstellung von racemischen und chiralen primären Aminen genutzt ( Gallardo-Donaire, J.; Hermsen, M.; Wysocki, J.; Ernst, M.; Rominger, F.; Trapp, O.; Stephen, A.; Hashmi, L.; Schaefer, A.; Comba, P.; Schaub, T. J. Am. Chm. Soc. 2017, DOI: 10.1021/jacs.7b10496 ). Vorgenannte Katalysatoren sind nachteilhafterweise auf die Herstellung von nur einfachen und wenigen Verbindungen beschränkt. Darüber hinaus sind die verwendeten Katalysatorpräkursoren und Liganden sehr kostenintensiv.Therefore, few catalysts are known for homogeneous catalysis based on Rh, Ir and Ru metal complexes. For example, [Rh (COD) Cl] 2 -TPPTS (TPPTS = 3,3 ', 3 "-phosphinidynetris (benzenesulfonic acid) trisodium salt) has been described as a catalyst for the preparation of simple primary amines from aldehydes, with aqueous ammonia and NH 4 OAC used as an additive ( Gross, T .; Seayad, AM; Ahmad, M .; Beller, M. Org. Lett. 2002, 4, 2055-2058 ). Rh [(dppb) (COD)] BF 4 and [Rh (COD) Cl] 2 -BINAS catalysts are also used (COD = 1,5-cyclooctadiene; BINAS = 2,2'-bis [bis (3-sulfophenyl ) phosphino] methyl] -4,4 ', 7,7'-tetrasulfo-1,1'-binaphthyl octasodium salt), (Riermeier, T., Haack, K.-J. Uwe Dingerdissen, Boerner, Tararov, AV; Kadyrov , R .; Less, US 6,884,887 B1, 2005). Ir-based complexes such as [Ir (COD) Cl] 2 -BINAS can catalyze the reaction of single simple ketones with ammonia (Riermeier, T., Haack, K.-J. Uwe Dingerdissen, Boerner, Tararov, AV, Kadyrov, R , Less, US 6,884,887 B1, 2005). Catalyst systems such as Ru (CO) ClH (PPh 3 ) -Xantphos-dppe (Gallardo-Donaire, J .; Ernst, M. Trapp, O .; Schaub, T .; Adv. Synth. Catal. 2016, 358, 358- 363) and Ru (CO) ClH (PPh 3 ) - (S, S) -f-binaphane ((S, S) -f-binaphane = 1,1'-bis [(S) -4,5-dihydro- 3H-binaphthol [2,1-c: 1 ', 2'-e] phosphepino] ferrocene) are used for the reductive amination of simple ketones for the preparation of racemic and chiral primary amines ( Gallardo-Donaire, J .; Hermsen, M .; Wysocki, J .; Ernst, M .; Rominger, F .; Trapp, O .; Stephen, A .; Hashmi, L .; Schaefer, A .; Comba, P .; Schaub, TJ Am. Chm. Soc. 2017, DOI: 10.1021 / jacs.7b10496 ). The aforementioned catalysts are disadvantageously limited to the preparation of only simple and few compounds. In addition, the catalyst precursors and ligands used are very expensive.

Es ist daher Aufgabe der Erfindung ein Katalysatorsystem und ein einfaches und kostengünstiges Verfahren zur Herstellung von primären Aminen bereitzustellen, das zumindest teilweise die Nachteile des Standes der Technik überwindet. It is therefore an object of the invention to provide a catalyst system and a simple and inexpensive process for the preparation of primary amines, which at least partially overcomes the disadvantages of the prior art.

Diese Aufgabe wird durch ein Katalysatorsystem (Katalysator) und ein Verfahren zur Herstellung von primären Aminen aus Carbonylverbindungen und Ammoniak in Anwesenheit von Wasserstoff mit den Merkmalen der unabhängigen Ansprüche gelöst. Vorteilhafte Ausgestaltungen der Erfindung sind in den Unteransprüchen gekennzeichnet.This object is achieved by a catalyst system (catalyst) and a process for the preparation of primary amines from carbonyl compounds and ammonia in the presence of hydrogen having the features of the independent claims. Advantageous embodiments of the invention are characterized in the subclaims.

Erfindungsgemäß wird ein Katalysatorsystem zur Herstellung von primären Aminen aus Carbonylverbindungen und Ammoniak bestehend aus einem Ruthenium-Halogen-Komplex mit Triphenylphosphin- Liganden bereitgestellt, wobei die Phenylringe unsubstituiert oder substituiert sein können.According to the invention, a catalyst system is provided for the preparation of primary amines from carbonyl compounds and ammonia consisting of a ruthenium-halogen complex with triphenylphosphine ligands, wherein the phenyl rings may be unsubstituted or substituted.

Vorzugsweise basiert der Präkursor zur Ausbildung des Ruthenium-Komplexes auf einem Rutheniumhalogenid, vorzugsweise ist das Halogen ein Chlor, Brom oder Iod. Bevorzugt als Präkursor ist insbesondere [RuCl2(p-Cymol)]2.Preferably, the precursor for forming the ruthenium complex is based on a ruthenium halide, preferably the halogen is a chlorine, bromine or iodine. Preference is given in particular to [RuCl 2 (p-cymene)] 2 as precursor.

Nach einer bevorzugten Ausführungsform der Erfindung weist das Triphenylphosphin eine der allgemeinen Strukturen L1 bis L3 auf

Figure DE102018101218A1_0001
According to a preferred embodiment of the invention, the triphenylphosphine has one of the general structures L1 to L3
Figure DE102018101218A1_0001

Bevorzugterweise ist das Katalysatorsystem RuCl2(PPh3)3 oder RuCl2(PPh3)4, besonders bevorzugt RuCl2(PPh3)3.The catalyst system is preferably RuCl 2 (PPh 3 ) 3 or RuCl 2 (PPh 3 ) 4 , particularly preferably RuCl 2 (PPh 3 ) 3 .

Zudem wird die Aufgabe durch ein erfindungsgemäßes Verfahren zur Herstellung primärer Amine durch reduktive Aminierung von primären Carbonylverbindungen mittels Ammoniak in Anwesenheit von Wasserstoff gelöst, bei dem das vorbeschriebene Katalysatorsystem eingesetzt wird.In addition, the object is achieved by a novel process for the preparation of primary amines by reductive amination of primary carbonyl compounds by means of ammonia in the presence of hydrogen, in which the above-described catalyst system is used.

Dieses Verfahren ermöglicht vorteilhafterweise unter Verwendung von preiswerten und leicht erhältlichen Ausgangsmaterialien und dem Katalysatorsystem (Katalysator) die Herstellung von einer Vielzahl verschiedener linearer und verzweigter Amine unter industriell variablen und skalierbaren Bedingungen.This process advantageously allows the production of a variety of different linear and branched amines under industrially variable and scalable conditions using inexpensive and readily available starting materials and the catalyst system (catalyst).

Insbesondere die Synthese von primären Benzyl- und aliphatischen Aminen, die zentrale Ausgangsmaterialien und Schlüsselintermediate für wertvolle Chemikalien, Moleküle und Materialien der Biowissenschaften darstellen, ist dabei von besonderer Bedeutung.In particular, the synthesis of primary benzylic and aliphatic amines, which are central starting materials and key intermediates for valuable chemicals, molecules and materials in the life sciences, is of particular importance.

Auch funktionalisierte und strukturell verschiedene Moleküle, Steroidderivate und Arzneimittel können verfahrensgemäß mit Ausbeuten bis zu 95 % aminiert werden.Also functionalized and structurally different molecules, steroid derivatives and drugs can be aminated according to the method in yields up to 95%.

Besonders bevorzugt erfolgt die Aminierung als homogene katalytische Umsetzung in Gegenwart eines Lösungsmittels. Vorzugsweise ist das Lösungsmittel tert-Amylalkohol, tert-Butanol, Methanol und besonders bevorzugt tert-Amylalkohol.Particularly preferably, the amination is carried out as a homogeneous catalytic reaction in the presence of a solvent. The solvent is preferably tert-amyl alcohol, tert-butanol, methanol and particularly preferably tert-amyl alcohol.

Das Katalysatorsystem wird vorzugsweise in einem Bereich von 0,001 mol% bis 50 mol%, mehr bevorzugt im Bereich von 0,01 mol% bis 10 mol% und am meisten bevorzugt 1 mol% bis 5 mol% in Relation zu der eingesetzten Carbonylverbindung eingesetzt.The catalyst system is preferably used in a range of 0.001 mol% to 50 mol%, more preferably in the range of 0.01 mol% to 10 mol%, and most preferably 1 mol% to 5 mol% in relation to the carbonyl compound used.

Der vorzugsweise zugeführte Wasserstoff steht vorzugsweise unter einem Partialdruck p(H2) im Bereich von 0.01 bar bis 100 bar, besonders bevorzugt von 2 bar bis 50 bar und am bevorzugtesten von 10 bis 40 bar.The preferably supplied hydrogen is preferably under a partial pressure p (H 2 ) in the range of 0.01 bar to 100 bar, more preferably from 2 bar to 50 bar and most preferably from 10 to 40 bar.

Der Partialdruck des zugeführten Ammoniaks p(NH3) liegt vorzugsweise im Bereich von 0.01 bar bis 100 bar, mehr bevorzugt im Bereich von 1 bar bis 50 bar am bevorzugtesten im Bereich 5 bis 7 bar liegt. The partial pressure of the supplied ammonia p (NH 3 ) is preferably in the range of 0.01 bar to 100 bar, more preferably in the range of 1 bar to 50 bar, most preferably in the range 5 to 7 bar.

Die verfahrensgemäße Reaktionstemperatur liegt vorzugsweise im Bereich von 0°C bis 180°C, besonders bevorzugt zwischen 25°C bis 140°C und ist am meisten bevorzugt 130°C.The reaction temperature according to the invention is preferably in the range from 0 ° C to 180 ° C, more preferably between 25 ° C to 140 ° C and most preferably 130 ° C.

Die Reaktionsdauer des Verfahrens beträgt vorzugsweise 20 h bis 40 h, mehr bevorzugt bei 24 h bis 30 h.The reaction time of the process is preferably 20 hours to 40 hours, more preferably 24 hours to 30 hours.

Nach dem erfindungsgemäßen Verfahren können einfache und auch anspruchsvolle Amine hergestellt werden, die in den nachfolgenden Beispielen gezeigt sind.Simple and also demanding amines which are shown in the examples below can be prepared by the process according to the invention.

Aber auch sonstige primäre Amine können vorteilhafterweise unkompliziert mit dem erfindungsgemäßen Verfahren hergestellt werden.But also other primary amines can advantageously be produced easily by the method according to the invention.

Bemerkenswerterweise kann der synthetische Nutzen dieser homogenen Ru-katalysierten Aminierungsreaktion durch Durchführung von Reaktionen im Gramm-Maßstab demonstriert werden.Remarkably, the synthetic utility of this homogeneous Ru-catalyzed amination reaction can be demonstrated by performing gram-scale reactions.

Die im Rahmen der vorstehenden Beschreibung gemachten Ausführungen betreffen, das Katalysatorsystem und das Verfahren gleichermaßen.The statements made in the above description relate equally to the catalyst system and the process.

Nachstehend wird die Erfindung anhand von Beispielen näher erläutert.The invention will be explained in more detail by way of examples.

Beispiel 1example 1

Die Eignung von Ru-Präkursoren im Vergleich zu anderen Metall-Präkursoren bei der Ausbildung eines Katalysatorsystems wird anhand der Ausbeute einer reduktiven Aminierung von Benzaldehyd mit Ammoniak in Gegenwart von Wasserstoff festgestellt.The suitability of Ru precursors in comparison with other metal precursors in the formation of a catalyst system is determined by the yield of a reductive amination of benzaldehyde with ammonia in the presence of hydrogen.

Reaktionsbedingungen:Reaction conditions:

  • 0.5 mmol Benzaldehyd, 2 mol% Metall-Präkursor, 6 mol% PPh3,0.5 mmol benzaldehyde, 2 mol% metal precursor, 6 mol% PPh 3 ,
  • p(NH3) 5-7 bar, p(H2) 40 bar, 1.5 ml tert-Amylalkohol, 130 °C, 24 h.p (NH 3 ) 5-7 bar, p (H 2 ) 40 bar, 1.5 ml of tert-amyl alcohol, 130 ° C, 24 h.

Die Ausbeute wird mittels Gaschromatographie (n-Hexan Standard) bestimmt. Metall-Präkursor Ligand Ausbeute Benzylamin [%] 1.1 FeCI2 PPh3 0 1.2 CoCl2 6 H2O PPh3 0 1.3 NiCl2 .6 H2O PPh3 0 1.4 CuCl2(II) PPh3 0 1.5 RuCl3(III).H2O PPh3 0 1.6 [RuCl2(p-Cymol)]2 PPh3 40 1.7 [RuCl2(p-Cymol)]2 - 0 The yield is determined by gas chromatography (n-hexane standard). Metal precursor ligand Yield benzylamine [%] 1.1 FeCl 2 PPh 3 0 1.2 CoCl 2 6 H 2 O PPh 3 0 1.3 NiCl 2 .6H 2 O PPh 3 0 1.4 CuCl 2 (II) PPh 3 0 1.5 RuCl 3 (III) .H 2 O PPh 3 0 1.6 [RuCl 2 (p-cymene)] 2 PPh 3 40 1.7 [RuCl 2 (p-cymene)] 2 - 0

Es zeigt sich, dass das auf Ruthenium basierende [RuCl2(p-Cymol)]2 zu EINEM Katalysatorsystemen führt, das eine hohe Ausbeute liefert, während alle anderen getesteten Varianten zu keiner Ausbeute führen.It turns out that the ruthenium-based [RuCl 2 (p-cymene)] 2 leads to ONE catalyst system that provides a high yield while all other variants tested do not yield any.

Beispiel 2Example 2

Die Eignung von Triphenylphospin (PPh3) im Vergleich zu anderen Liganden bei der Ausbildung eines Katalysatorsystems wird anhand der Ausbeute einer reduktiven Aminierung von Benzaldehyd mit Ammoniak in Gegenwart von Wasserstoff festgestellt.The suitability of triphenylphosphine (PPh 3 ) in comparison to other ligands in the formation of a catalyst system is determined by the yield of a reductive amination of benzaldehyde with ammonia in the presence of hydrogen.

Reaktionsbedingungen: Reaction conditions:

0.5 mmol Benzaldehyde, 2 mol% (RuCl2(p-Cymol)]2 (korrespondierend zum Monomer), 6 mol% Ligand, p(NH3) 5-7 bar, p(H2) 40 bar, 1.5 ml tert-Amylalkohol, 130 °C, 24 h.0.5 mmol benzaldehydes, 2 mol% (RuCl 2 (p-cymene)] 2 (corresponding to the monomer), 6 mol% ligand, p (NH 3 ) 5-7 bar, p (H 2 ) 40 bar, 1.5 ml tert. Amyl alcohol, 130 ° C, 24 h.

Die Ausbeute wird mittels Gaschromatographie (n-Hexan Standard) bestimmt.The yield is determined by gas chromatography (n-hexane standard).

Folgende Liganden werden getestet:

Figure DE102018101218A1_0002
Figure DE102018101218A1_0003
 Metall-Präkursor Ligand Ausbeute Benzylamin [%] 2.1 [RuCl2(p-Cymol)]2 L1 40 2.2 [RuCl2(p-Cymol)]2 L2 50 2.3 [RuCl2(p-Cymol)]2 L3 53 2.4 [RuCl2(p-Cymol)]2 L4 5 2.5 [RuCl2(p-Cymol)]2 L5 2 2.6 [RuCl2(p-Cymol)]2 L6 10 2.7 [RuCl2(p-Cymol)]2 L7 0 2.8 [RuCl2(p-Cymol)]2 L8 0 2.9 [RuCl2(p-Cymol)]2 L9 0 2.10 [RuCl2(p-Cymol)]2 L10 0 The following ligands are tested:
Figure DE102018101218A1_0002
Figure DE102018101218A1_0003
 Metal precursor ligand Yield benzylamine [%] 2.1 [RuCl 2 (p-cymene)] 2 L1 40 2.2 [RuCl 2 (p-cymene)] 2 L2 50 2.3 [RuCl 2 (p-cymene)] 2 L3 53 2.4 [RuCl 2 (p-cymene)] 2 L4 5 2.5 [RuCl 2 (p-cymene)] 2 L5 2 2.6 [RuCl 2 (p-cymene)] 2 L6 10 2.7 [RuCl 2 (p-cymene)] 2 L7 0 2.8 [RuCl 2 (p-cymene)] 2 L8 0 2.9 [RuCl 2 (p-cymene)] 2 L9 0 2.10 [RuCl 2 (p-cymene)] 2 L10 0

Es zeigt sich, dass Triphenylphospin-Liganden unabhängig davon, ob diese zusätzlich substituiert sind oder nicht zu einer höheren Ausbeute führen als die anderen getesteten Liganden.It can be shown that triphenylphosphine ligands, whether they are additionally substituted or not, lead to a higher yield than the other ligands tested.

Beispiel 3Example 3

Der Einfluss der Anzahl der Liganden wird anhand der Ausbeute einer reduktiven Aminierung von Benzaldehyd mit Ammoniak in Gegenwart von Wasserstoff festgestellt, wobei RuCl2(PPh3)3 mit RuCl2(PPh3)4 verglichen wird.The influence of the number of ligands is determined by the yield of a reductive amination of benzaldehyde with ammonia in the presence of hydrogen, comparing RuCl 2 (PPh 3 ) 3 with RuCl 2 (PPh 3 ) 4 .

Reaktionsbedingungen:Reaction conditions:

  • 0.5 mmol Benzaldehyd, 2 mol% Katalysator,0.5 mmol benzaldehyde, 2 mol% catalyst,
  • p(NH3) 5-7 bar, p(H2) 40 bar, 1.5 ml tert-Amylalkohol, 130 °C, 24 h,p (NH 3 ) 5-7 bar, p (H 2 ) 40 bar, 1.5 ml of tert-amyl alcohol, 130 ° C., 24 h,

Die Ausbeute wird mittels Gaschromatographie (n-Hexan Standard) bestimmt. Katalysatorsystem Ausbeute Benzylamin [%] 3.1 RuCl2(PPh3)3 95 3.2 RuCl2(PPh3)4 90 The yield is determined by gas chromatography (n-hexane standard). catalyst system Yield benzylamine [%] 3.1 RuCl 2 (PPh 3 ) 3 95 3.2 RuCl 2 (PPh 3 ) 4 90

Es zeigt sich, dass beide Katalysatoren hohe Ausbeuten bringen, wobei das Dichlorotris(triphenylphosphine)ruthenium(II) (3.1) eine nochmals bessere Ausbeute als die Tetra(triphenylphospin)-Variante (3.2) aufweist.It can be seen that both catalysts yield high yields, with the dichlorotris (triphenylphosphine) ruthenium (II) (3.1) showing an even better yield than the tetra (triphenylphosphine) variant (3.2).

Beispiel 4Example 4

Es werden nachstehend eine Reihe von verschiedenen primären Aminen mit den jeweils erhaltenen Ausbeuten aufgelistet.A number of different primary amines with the respective yields obtained are listed below.

Reaktionsbedingungen:Reaction conditions:

  • 0.5 mmol Aldehyd, 2 mol% RuCl2(PPh3)3,0.5 mmol aldehyde, 2 mol% RuCl 2 (PPh 3 ) 3 ,
  • p(NH3) 5-7 bar, p(H2) 40 bar, 1.5 ml tert-Amylalkohol, 130 °C, 24 h oder 30 h, wenn angegeben,p (NH 3 ) 5-7 bar, p (H 2 ) 40 bar, 1.5 ml tert-amyl alcohol, 130 ° C, 24 h or 30 h, if indicated,

Die Ausbeute wurde nach der Synthese isoliert und bestimmt. Wurden die Ausbeuten mittels GC (n-Hexadecan Standard) bestimmt, so ist dies extra angegeben..The yield was isolated and determined after the synthesis. If the yields were determined by means of GC (n-hexadecane standard), this is indicated separately.

Lineare substituierte und funktionalisierte primäre BenzylamineLinear substituted and functionalized primary benzylamines

Figure DE102018101218A1_0004
Figure DE102018101218A1_0004
Figure DE102018101218A1_0005
Figure DE102018101218A1_0005
Figure DE102018101218A1_0006
Figure DE102018101218A1_0006
Figure DE102018101218A1_0007
Figure DE102018101218A1_0007
Figure DE102018101218A1_0008
Figure DE102018101218A1_0008
Figure DE102018101218A1_0009
Figure DE102018101218A1_0009
Figure DE102018101218A1_0010
Figure DE102018101218A1_0010
Figure DE102018101218A1_0011
Figure DE102018101218A1_0011
Figure DE102018101218A1_0012
Figure DE102018101218A1_0012

Heterocyclische lineare primäre AmineHeterocyclic linear primary amines

Figure DE102018101218A1_0013
Figure DE102018101218A1_0013
Figure DE102018101218A1_0014
Figure DE102018101218A1_0014
Figure DE102018101218A1_0015
Figure DE102018101218A1_0015

Anspruchsvolle aliphatische lineare primäre AmineSophisticated aliphatic linear primary amines

Figure DE102018101218A1_0016
Figure DE102018101218A1_0016
Figure DE102018101218A1_0017
Figure DE102018101218A1_0017
Figure DE102018101218A1_0018
Figure DE102018101218A1_0018

Verzweigte primäre Amine von aromatischen Ketonen Branched primary amines of aromatic ketones

Bei dieser Gruppe von Aminen wurde der Katalysator in einer Menge von 3 mol% eingesetzt. Die sonstigen Reaktionsbedingungen sind wie bei den anderen Aminen.

Figure DE102018101218A1_0019
Figure DE102018101218A1_0020
Figure DE102018101218A1_0021
Figure DE102018101218A1_0022
 In this group of amines, the catalyst was used in an amount of 3 mol%. The other reaction conditions are the same as for the other amines.
Figure DE102018101218A1_0019
Figure DE102018101218A1_0020
Figure DE102018101218A1_0021
Figure DE102018101218A1_0022

Verzweigte aliphatische Amine und Steroid-Derivate mit AminfunktionBranched aliphatic amines and steroid derivatives with amine function

Figure DE102018101218A1_0023
Figure DE102018101218A1_0023
Figure DE102018101218A1_0024
Figure DE102018101218A1_0024
Figure DE102018101218A1_0025
Figure DE102018101218A1_0025
Figure DE102018101218A1_0026
Figure DE102018101218A1_0026
Figure DE102018101218A1_0027
Figure DE102018101218A1_0027
Figure DE102018101218A1_0028
Figure DE102018101218A1_0028
Figure DE102018101218A1_0029
Figure DE102018101218A1_0029

Aminsynthesen im Gramm-MaßstabAmine syntheses in grams scale

Bei diesen Synthesen wurde die Menge der eingesetzten Carbonylverbindung stark erhöht, während die sonstigen Reaktionsbedingungen gleich geblieben sind, um die gute Skalierbarkeit des erfindungsgemäßen Verfahrens zu demonstrieren. So werden auch hierbei sehr gute Ausbeuten von mindestens 90% erhalten.

Figure DE102018101218A1_0030
Figure DE102018101218A1_0031
 In these syntheses, the amount of the carbonyl compound used was greatly increased, while the other reaction conditions remained the same to demonstrate the good scalability of the method according to the invention. Thus, also very good yields of at least 90% are obtained.
Figure DE102018101218A1_0030
Figure DE102018101218A1_0031

ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION

Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Zitierte Nicht-PatentliteraturCited non-patent literature

  • Gross, T.; Seayad, A. M.; Ahmad, M.; Beller, M. Org. Lett. 2002, 4, 2055-2058 [0009]Gross, T .; Seayad, A.M .; Ahmad, M .; Beller, M. Org. Lett. 2002, 4, 2055-2058 [0009]
  • Gallardo-Donaire, J.; Hermsen, M.; Wysocki, J.; Ernst, M.; Rominger, F.; Trapp, O.; Stephen, A.; Hashmi, L.; Schaefer, A.; Comba, P.; Schaub, T. J. Am. Chm. Soc. 2017, DOI: 10.1021/jacs.7b10496 [0009]Gallardo-Donaire, J .; Hermsen, M .; Wysocki, J .; Ernst, M .; Rominger, F .; Trapp, O .; Stephen, A .; Hashmi, L .; Schaefer, A .; Comba, P .; Schaub, T.J. Am. Chm. Soc. 2017, DOI: 10.1021 / jacs.7b10496 [0009]

Claims (11)

Katalysatorsystem zur Herstellung von primären Aminen aus Carbonylverbindungen und Ammoniak bestehend aus einem Ruthenium-Halogen-Komplex mit Triphenylphosphin-Liganden.Catalyst system for the preparation of primary amines from carbonyl compounds and ammonia consisting of a ruthenium-halogen complex with triphenylphosphine ligands. Katalysatorsystem nach Anspruch 1, dadurch gekennzeichnet, dass ein Präkursor zur Ausbildung des Ruthenium-Komplexes auf einem Rutheniumhalogenid basiert, vorzugsweise ist das Halogen ein Chlor, Brom oder lod.Catalyst system after Claim 1 , characterized in that a precursor for forming the ruthenium complex is based on a ruthenium halide, preferably the halogen is a chlorine, bromine or iodine. Katalysatorsystem nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Triphenylphosphin eine der allgemeinen Strukturen L1 bis L3 aufweist
Figure DE102018101218A1_0032
 Catalyst system after Claim 1 or 2 , characterized in that the triphenylphosphine has one of the general structures L1 to L3
Figure DE102018101218A1_0032
 Katalysatorsystem nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Katalysator RuCl2(PPh3)3 oder RuCl2(PPh3)4, vorzugsweise RuCl2(PPh3)3 ist.Catalyst system according to one of Claims 1 to 3 , characterized in that the catalyst is RuCl 2 (PPh 3 ) 3 or RuCl 2 (PPh 3 ) 4 , preferably RuCl 2 (PPh 3 ) 3 . Verfahren zur Herstellung primärer Amine durch reduktive Aminierung von primären Carbonylverbindungen mittels Ammoniak in Anwesenheit von Wasserstoff unter Verwendung eines Katalysatorsystems nach einem der Ansprüche 1-4.Process for the preparation of primary amines by reductive amination of primary carbonyl compounds by means of ammonia in the presence of hydrogen using a catalyst system according to any one of Claims 1 - 4 , Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Aminierung als homogene katalytische Umsetzung in Gegenwart eines Lösungsmittels erfolgt, vorzugsweise ist das Lösungsmittel tert-Amylalkohol, tert-Butanol, Methanol, besonders bevorzugt tert-Amyalkohol.Method according to Claim 5 , characterized in that the amination is carried out as a homogeneous catalytic reaction in the presence of a solvent, preferably the solvent is tert-amyl alcohol, tert-butanol, methanol, more preferably tert-amyl alcohol. Verfahren nach einem der Ansprüche 5 bis 6, dadurch gekennzeichnet, dass das Katalysatorsystem in einem Bereich von 0,001 mol% bis 50 mol%, bevorzugt 0,01 mol% bis 10 mol% und besonders bevorzugt 1 mol% bis 5 mol% in Relation zu der Carbonylverbindung eingesetzt wird.Method according to one of Claims 5 to 6 , characterized in that the catalyst system is used in a range of 0.001 mol% to 50 mol%, preferably 0.01 mol% to 10 mol% and particularly preferably 1 mol% to 5 mol% in relation to the carbonyl compound. Verfahren nach einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, dass der Partialdruck des Wasserstoffs p(H2) im Bereich von 0.01 bar bis 100 bar, bevorzugt im Bereich 2 bar bis 50 bar und besonders bevorzugt im Bereich von 10 bar 40 bar liegt.Method according to one of Claims 5 to 7 , characterized in that the partial pressure of the hydrogen p (H 2 ) in the range of 0.01 bar to 100 bar, preferably in the range 2 bar to 50 bar and particularly preferably in the range of 10 bar 40 bar. Verfahren nach einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, dass der Partialdruck des Ammoniaks p(NH3) im Bereich von 0.01 bar bis 100 bar, bevorzugt im Bereich von 1 bar bis 50 bar und besonders bevorzugt im Bereich von 5 bis 7 bar liegt.Method according to one of Claims 5 to 8th , characterized in that the partial pressure of the ammonia p (NH 3 ) in the range of 0.01 bar to 100 bar, preferably in the range of 1 bar to 50 bar and more preferably in the range of 5 to 7 bar. Verfahren nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, dass die Reaktionstemperatur im Bereich von 0°C bis 180°C, bevorzugt zwischen 25°C bis 140°C liegt und besonders bevorzugt 130°C ist.Method according to one of Claims 5 to 9 , characterized in that the reaction temperature in the range of 0 ° C to 180 ° C, preferably between 25 ° C to 140 ° C and more preferably 130 ° C. Verfahren nach einem der Ansprüche 5 bis 10, dadurch gekennzeichnet, dass die Reaktionsdauer 20 h bis 40 h, vorzugsweise 24 h bis 30 h beträgt.Method according to one of Claims 5 to 10 , characterized in that the reaction time is 20 h to 40 h, preferably 24 h to 30 h.
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