DE2845216C2 - Process for the preparation of N-acyl-α-amino carboxylic acids by asymmetric hydrogenation - Google Patents

Process for the preparation of N-acyl-α-amino carboxylic acids by asymmetric hydrogenation

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DE2845216C2
DE2845216C2 DE2845216A DE2845216A DE2845216C2 DE 2845216 C2 DE2845216 C2 DE 2845216C2 DE 2845216 A DE2845216 A DE 2845216A DE 2845216 A DE2845216 A DE 2845216A DE 2845216 C2 DE2845216 C2 DE 2845216C2
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asymmetric hydrogenation
hydrogenation
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DE2845216A1 (en
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Walter San Donato Milanese Milano Marconi
Marcello Roma Mazzei
Mario Monterotondo Roma Riocci
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/1855—Triamide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • B01J31/187—Amide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B01J31/188—Amide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

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

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von N-Acyl-alpha-amlnocarbonsäuren durch asymmetrische Hydrierung der entsprechenden alpha-AcylaminoacrvlsSuren unter Anwendung eines Katalysatorsystems, bei dem es sich um einen kationischen Rhodium-Komplex handelt, der auf einem tonartigen Mineral immobilisiert Ist, wie Hectorit, Bentonlt und Halloyslt, entsprechend dem Patentanspruch.The invention relates to a method of manufacture of N-acyl-alpha-aminocarboxylic acids by asymmetric Hydrogenation of the corresponding alpha-acylamino acrylic acids using a catalyst system which is a cationic rhodium complex which is immobilized on a clay-like mineral, such as hectorite, bentonite and halloysite, accordingly the claim.

Bei dem erfindungsgemäßen Verfahren werden katlonlsche Komplexe von Rhodium mit Aminderivaten von Phosphor, die immobilisiert wurden an Silikaten, Insbesondere der Art der Smectite und des Serpentins und Kaolins, eingesetzt.In the method according to the invention, catalytic Complexes of rhodium with amine derivatives of phosphorus, which have been immobilized on silicates, in particular the type of smectite and serpentine and kaolin.

Beim Studium der technischen Literatur der letzten Jahre findet man ein beträchtliches Interesse an der Anwendung der asymmetrischen katalytlschen Systeme zur Herstellung von Optisch aktiven Verbindungen durch Hydrierungs-, Hydrosllyllerungs- und Hydroformyllerungsreaktionen. In studying the technical literature of recent years one finds considerable interest in the Application of asymmetric catalytic systems for the production of optically active compounds Hydrogenation, hydrosilylation and hydroformylation reactions.

Bei Hydrierungsreaktionen von ar-Acylamlnoacrylsäuren beispielsweise, die durch chlraJe Komplexe von Rhodlum-o-Anlsylcyclohexylmethylphosphln katalysiert werden, werden hohe optische Ausbeuten von 95 bis 96% beschrieben, die tatsächlich den bei enzymatlschen Verfahren festgestellten nahekommen (vgl. J. Amer. Chem. Soc. 97, 1975, 2567-8).In hydrogenation reactions of ar-acylaminoacrylic acids for example, which is catalyzed by chlraJe complexes of Rhodlum-o-Anlsylcyclohexylmethylphosphln high optical yields of 95 to 96% described, which actually apply to enzymatic processes found close (see. J. Amer. Chem. Soc. 97, 1975, 2567-8).

Jedoch bringt die Anwendung homogener Katalysatoren eine große Anzahl von Problemen mit sich, einschließlich der Schwierigkeit, die Reaktionsprodukte abzutrennen und den Katalysator wiederzugewinnen. Dies wird besonders schwierig, wenn Spuren des Katalysators In dem Reaktionsprodukt zurückgehalten werden. Um diese Schwierigkelten auszuschalten, wurden die homogenen Katalysatoren unlöslich gemacht durch kovalente Bindungen mit Substraten, die vorwiegend organischer Natur sind.However, the use of homogeneous catalysts poses a large number of problems, including the difficulty of separating the reaction products and recovering the catalyst. This becomes particularly difficult when traces of the catalyst are retained in the reaction product. In order to eliminate these difficulties, the homogeneous catalysts were made insoluble by covalent bonds with substrates that are predominantly organic in nature.

Die Polymeren, die man am häufigsten verwendet, sind Polystyrol, das mit Dlvlnylbenzol quervernetzt wurde und mit Phosphln-Blndungen, an die Übergangsmetalle koordiniert sind, funktionell gemacht wurde. The most commonly used polymers are polystyrene, which cross-links with vinylbenzene and made functional with phosphine compounds to which transition metals are coordinated.

Auch Copolymere des In gleicher Weise funktionell gemachten Polystyrols werfen verwendet.Copolymers of polystyrene made functional in the same way are also used.

Die Erfindung betrifft das Im Patentanspruch vorstehend gekennzeichnete Verfahren. Für homogene Katalysatoren für asymmetrische Hydrierungsreaktionen werden tonartige Mineralien, insbesondere aus der Klasse der Smectite und Kaolin eingesetzt.The invention relates to the claim above marked procedures. Be for homogeneous catalysts for asymmetric hydrogenation reactions Clay-like minerals, especially from the class of smectites and kaolin, are used.

Smectite sind Phylloslllkate, deren Struktureinheit zusammengesetzt 1st aus einer tetraedrischen Schicht, ίο einer oktaedrischen Schicht und einer weiteren tetraedrischen Schicht, mit einer Schichtbeladung von 0,25 bis 0,60 pro Formeleinheit durch isomorphe Substitutionen, die in den tetraedrischen und den oktaedjischen Schichten verteilt sind; eine derartige Ladung wirf Ins Glelchgewicht gebracht durch leicht austauschbare Zwischenschicht-Kationen. Die Austauschkapazität 1st vergleichsweise hoch und variiert von 80 bis 150 Mllllkqulvalenten pro 100 Gramm.Smectites are phyllosllcates, the structural unit of which is composed of a tetrahedral layer, ίο an octahedral layer and another tetrahedral Layer, with a layer loading of 0.25 to 0.60 per formula unit due to isomorphic substitutions, those in the tetrahedral and octahedral layers are distributed; such a charge throws into balance brought about by easily exchangeable interlayer cations. The exchange capacity is comparative high and varies from 80 to 150 waste quantities per 100 grams.

Zusätzlich sind von besonderem Interesse einige Mine-In addition, some mines are of particular interest J° rauen des Tontyps aus der Gruppe, von Serpentin Kaolin,J ° roughening of the clay type from the group, from serpentine kaolin,

wie Halloyslt, der die wäßrigste Form darstellt und einelike Halloyslt, which represents the wateriest form and one

Austauschfähigkeit von etwa 40 Mlllläqulvalent pro 100Interchangeability of about 40 waste equivalent per 100 Gramm besitzt.Gram owns.

Die erfindungsgemäßen Katalysatoren erhält man durch einfache Austauschreaktion zwischen dem kationischen Rhodium-Komplex und den tonartigen Materialien. The catalysts of the invention are obtained by a simple exchange reaction between the cationic Rhodium complex and the clay-like materials.

Derartige katalytlsche Systeme weisen den beträchtlichen Vorteil auf, daß sie einfach nerzustellen und *> kostensparend sind, Insbesondere Im Vergleich mit den üblichen Heterogenlslerungssystemen, die modifizierte organische Polymermatrlces verwenden.Such catalytic systems have the considerable The advantage is that they are easy to create and *> are cost-saving, especially when compared to the usual heterogeneity systems, the modified use organic polymer matrices.

Die genannten Katalysatoren können In der Form eines feinen Pulvers oder von Granulaten verwendet werden oder können jegliche Formen aufweisen, die für die anzuwendende Kontaktverfahrenswelse geeignet sind.The catalysts mentioned can be in the form of fine powder or granules can be used, or can be of any shape suitable for the applicable contact process catfish are suitable.

Das asymmetrische Reduktionsverfahren wird bei einer Temperatur von -70 bis +200° C, vorzugsweise von 0 bis 500C bei einem Wasserstoffdruck bis zu etwa 200 bar, vorzugsweise von etwa 1 bis 50 bar sowie bei einem Molverhältnis von Substrat zu dem Katalysator, das von 10 bis 10 000 variiert, durchgeführt.The asymmetric reduction process is conducted at a temperature of -70 to + 200 ° C, preferably from 0 to 50 0 C at a hydrogen pressure up to about 200 bar, preferably from about 1 to 50 bar and at a molar ratio of substrate to the catalyst, varies from 10 to 10,000.

In den folgenden Beispielen werfen einige Arbeltscharakteristlka beschrieben.The following examples throw out some work characteristics described.

Beispiel 1example 1

1 g Hectorit, aufgeschlämmt in wasserfreiem Methanol, wurde mit Rhodium ausgetauscht, wobei man ihn zur Gleichgewichtseinstellung zusammen mit 0,475 g [Rh COD L]* ClO? in 50 ml Methanol einbrachte.1 g of hectorite, slurried in anhydrous methanol, was exchanged for rhodium, whereby it was replaced to establish equilibrium together with 0.475 g [Rh COD L] * ClO? introduced in 50 ml of methanol.

COD = Cydooctadlen; L = N,N'-Bls[R(+)-«-methylbenzyl)-N,N'-bls-<dlphenylphosphlno)-älhylendlamln. COD = cydooctadlene; L = N, N'-Bls [R (+) - «- methylbenzyl) -N, N'-bls- <dlphenylphosphhlno) -alhylenedlamine.

Der Hectorit nimmt eine Intensiv gelbe Farbe an und wird sorgfältig mit wasserfreiem Methanol gewaschen und anschließend getrocknet. Der Rhodiumgehalt betragt 1,6 Gew.-».The hectorite takes on an intense yellow color and is carefully washed with anhydrous methanol and then dried. The rhodium content is 1.6 wt. ».

Diese Verbindung wurde in wasserfreiem Äthanol aufgeschlämmt und In einem Autoklaven bei einem Wasserstoffdruck von etwa 20 bar (20 atm) hydriert. Man erhielt ein dunkelrot gefärbtes Produkt, was charakteristisch 1st für die Hydridarten des Rhodiumkomplexes, der für die Hydrierung der or-Acetamlnozlmtsäure verwendet wurde.This compound was slurried in anhydrous ethanol and Hydrogenated in an autoclave at a hydrogen pressure of about 20 bar (20 atm). Man received a dark red colored product, which is characteristic Is for the hydride types of the rhodium complex, which is used for the hydrogenation of the or-acetaminophenic acid became.

Ein Glaskolben wurde mit 0,942 g Substrat In 25 ml wasserfreiem Äthanol und 0,450 g vorausgehend hydriertem Katalysator beschickt. Der Kolben wurde an eine Hydriervorrichtung angeschlossen, die unter Atmosphärendruck arbeitete. Das Fortschreiten der ReaktionA glass flask was previously hydrogenated with 0.942 g of substrate in 25 ml of anhydrous ethanol and 0.450 g Catalyst loaded. The flask was connected to a hydrogenation device operating under atmospheric pressure worked. The progression of the reaction

wurde mittels üblicher Druckmeßvorrichtungen überwacht. Nach 8 Stunden wurde die Reaktion unterbrochen, der Katalysator wurde abfUtriert und die LOscung wurde zur Trockne verdampft. Das Produkt wurde durch NMR-Analyse charakterisiert; es handelte sich um R(+)N-Acetylphenylalanln;was monitored by means of conventional pressure measuring devices. After 8 hours the reaction was interrupted, the catalyst was filtered off and the solution was evaporated to dryness. The product was through Characterized by NMR analysis; it was R (+) N-acetylphenylalanine;

[arg, 21,5 (c= 1, wasserfreies Äthanol).[arg, 21.5 (c = 1, anhydrous ethanol).

Die Ausbeute In g entsprach 100% der Theorie. OptischeThe yield in g corresponded to 100% of theory. Optical

Ausbeute 46%.Yield 46%.

Beispiele 2 bis 6Examples 2 to 6

Mit dem gleichen Katalysator wie Im vorstehenden Beispiel wurden Hydrierungscyclen der a-Acctaminozlmtsäure durchgeführt: Die erhaltenen Daten sind In der Tabelle 1 aufgeführt.With the same catalyst as Im above Examples are hydrogenation cycles of α-acctaminozlmtsäure performed: The data obtained are in the Table 1 listed.

Der Katalysator wurde nach jedem Cyclus durch Filtrieren des Reaktlonsgemlschs wiedergewonnen, mit wasserfreiem Äthanol gewaschen und erneut unter den gleichen Bedienungen verwendet.The catalyst was recovered after each cycle by filtering the reaction mixture with washed with anhydrous ethanol and used again under the same conditions.

Tabelle 1Table 1 Cyclen [c] SubstratCyclen [c] substrate

Reaktionszeit StundenResponse time hours

[α] 1% Lösung[α] 1% solution

wasserfreiesanhydrous

ÄthanolEthanol

e. e.e. e.

4,4
4,4
4,3
4,3
4,54.4
4.4
4.3
4.3
4.5

20
2020th
20th

4
204th
20th

+0,170 +0,218 +0,230 +0,144 +0,184+0.170 +0.218 +0.230 +0.144 +0.184

37 47 50 31 4037 47 50 31 40

Katalysator: Hectorit (RhCODL) 0,510 g Substrat: a-AcetanunozimisäureCatalyst: hectorite (RhCODL) 0.510 g Substrate: a-acetanunozimic acid

Druck: etwa 20 bar H2 Pressure: approx. 20 bar H 2

Temperatur: Raumtemperatur. 23° C
Lösungsmittel: wasserfreies ÄthanolTemperature: room temperature. 23 ° C
Solvent: anhydrous ethanol

Beispiele 7 bis 12Examples 7 to 12

Hectorit wurde vor dem Ausgleich mit dem katlonlschen Rhodiumkomplex mit verdünnter Essigsaure behandelt, um die Karbonate zu entfernen, die vorhanden waren, worauf er sorgfältig gewaschen wurde, bis zur Neutralltat der Waschwasser. Der Katalysator wurde nach der gleichen Verfahrensweise wie im vorstehenden Beispiel beschrieben, hergestellt.Hectorite was before equalizing with the katlonlschen Rhodium complex treated with dilute acetic acid to remove the carbonates that are present were, after which it was carefully washed until the washing water was neutral. The catalyst was following the same procedure as above Example described, produced.

Die Tabelle 2 gibt die Daten an, die man bei aufeinanderfolgenden Reduktlonscyclen der ar-Acetamlnoacrylsäure erhalt.Table 2 shows the data that can be obtained from successive Reductlonscyclen of ar-Acetamlnoacryläure receive.

Tabelle 2Table 2 Cyclen |c] SubstratCyclen | c] substrate

Reaktionszeit StundenResponse time hours

[α] c= 1, % H2O e. e.[α] c = 1,% H 2 O ee

1,9
2,0
2,0
2,0
2,1
2,01.9
2.0
2.0
2.0
2.1
2.0

1,1/21.1 / 2

1,1/41.1 / 4

1,01.0

1,3/41.3 / 4

1,1/41.1 / 4

2,1/22.1 / 2

-0,355 -0,425 -0,430 -0,440 -0,437 -0,412-0.355 -0.425 -0.430 -0.440 -0.437 -0.412

53 64 65 66 66 6253 64 65 66 66 62

Hydrierung von a-Acetaminoacrylsäure
Katalysator: Hectorit (RhCODL) 0,550 gHydrogenation of a-acetaminoacrylic acid
Catalyst: hectorite (RhCODL) 0.550 g

Raumtemperatur: 23° C
Druck: etwa I bar HjRoom temperature: 23 ° C
Pressure: about I bar Hj

Lösungsmittel: wasserfreies ÄthanolSolvent: anhydrous ethanol

Beispiel 13Example 13

Mit dem wie In Beispiel 7 hergestellten Katalysator wurden 0,725 g 3-Acc*oxy-4-methoxy-cr-acetamInozimtsäure, in 25 ml wasserfreiem Äthanol gelöst, reduziert. Die Reaktion wird In einem Glasautoklaven durchgeführt mit einem Wasserstoffdruck von etwa 2 bar (2 atm), wobei man bei Raumtemperatur arbeitete. Man erhielt S-Acetoxy^-methoxy-N-acetylphenylalanln mit einer optischen Ausbeute von 58%;With the catalyst prepared as in Example 7 0.725 g of 3-Acc * oxy-4-methoxy-cr-acetaminocinnamic acid, dissolved in 25 ml of anhydrous ethanol, reduced. The reaction is carried out in a glass autoclave with a hydrogen pressure of about 2 bar (2 atm), operating at room temperature. Man received S-acetoxy ^ -methoxy-N-acetylphenylalanine with an optical yield of 58%;

[ag2 +12,8° (C=-1, Aceton). [ag 2 + 12.8 ° (C = -1, acetone).

Der Wert des enantlonmerrelnen S-Acetoxy^-methoxy-The value of the enantlon merrelnen S-acetoxy ^ -methoxy-

N-acetyl-N-acetyl-

phenylalanlns istis phenylalanlns

[ag,-22° (C=I, Aceton).[ag, -22 ° (C = I, acetone).

Beispiele 14 bis 18Examples 14-18

In den folgenden Beispielen sind die Daten (Tabelle 3) aufgeführt, die bei Untersuchung der asymmetrischen Hydrierung mit einem Katalysator erhalten wurden, der durch Immobilisieren des katlonlschen Komplexes von Rhodium an Betonlt hergestellt wurde. Die Herstellung des Katalysators wurde wie In Beispiel 1 beschrieben durchgeführt. Die Reduktlonscyclen warden wie In Beispiel 2 durchgeführt.In the following examples the data (Table 3) listed when examining the asymmetrical Hydrogenation with a catalyst obtained by immobilizing the catalytic complex of Rhodium was produced on concrete. The preparation of the catalyst was described as in Example 1 carried out. The reducton cycles are as in example 2 carried out.

Tabelle 3Table 3

Cyclen [c] Substrat Reaktionszeit [ο] c
*> Stunden H2OCyclen [c] substrate reaction time [ο] c
*> Hours H 2 O

1,951.95

1,951.95

1,951.95

2,02.0

2,02.0

3
6
83
6th
8th

10
2410
24

-0,272
-0,348
-0,375
-0,352
-0,416-0.272
-0.348
-0.375
-0.352
-0.416

Hydrierung von a-Acetaminoacrylsäure
Katalysator: Bentonit (RhCODL) 0,450 gHydrogenation of a-acetaminoacrylic acid
Catalyst: Bentonite (RhCODL) 0.450 g

Raumtemperatur: 23° C
Druck: etwa 1 bar H? Room temperature: 23 ° C
Pressure: about 1 bar H ?

Lösungsmittel: wasserfreies ÄthanolSolvent: anhydrous ethanol

Beispiele 19 bis 21Examples 19 to 21

Es sind die Datea aufgeführt, die man bei Reduktionsuntersuchungen mit einem Katalysator erhielt, der durch Immobilisieren des kationischen Komplexes von Rhodium an Halloyslt erhalten wurde. Die Herstellung des Katalysators wurde wie in Beispiel 1 beschrieben durchgeführt. Die Reduktlonscyclen wurden durchgeführt wie In Beispiel 2 beschrieben.The data are listed that were obtained from reduction studies with a catalyst that was produced by Immobilizing the cationic complex of rhodium on halloysl was obtained. The manufacture of the The catalyst was carried out as described in Example 1. The reduktlonscyclen were carried out as Described in example 2.

Tabelle 4Table 4

Cyclen [c] Substrat Reaktionszeit [<x]c=l, %
% Stunden HjO e. e.Cyclen [c] substrate reaction time [<x] c = l,%
% Hours HjO ee

1,8
2,0
2,01.8
2.0
2.0

-0,495 74
-0,515 77
-0,500 75-0.495 74
-0.515 77
-0.500 75

Hydrierung von a-Acetaminoacrylsäure
Katalysator: Halloysil (RhCODL) 0.500 gHydrogenation of a-acetaminoacrylic acid
Catalyst: Halloysil (RhCODL) 0.500 g

Raumtemperatur: 23° C
Wasserstoffdruck: etwa 1 bar
Lösungsmittel: wasserfreies ÄthanolRoom temperature: 23 ° C
Hydrogen pressure: about 1 bar
Solvent: anhydrous ethanol

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung von N-Acyl-alpha-amlnocarbonsäuren durch asymmetrische Hydrierung der entsprechenden cr-Acylaminoacrylsäuren In Gegenwart eines Katalysatorsystems aus einer Rhodium-Koordinationsverbindung und einem der asymmetrischen Aminophosphine
N,N'-Bls[S(-)cr-methylbenzyl]-N,N'-bis-Process for the preparation of N-acyl-alpha-aminocarboxylic acids by asymmetric hydrogenation of the corresponding-acylaminoacrylic acids in the presence of a catalyst system composed of a rhodium coordination compound and one of the asymmetric aminophosphines
N, N'-Bls [S (-) cr-methylbenzyl] -N, N'-bis- (diphenylphosphin)-äthylendiamin,
N,N'-Bis[R(+)-«-methylbenzyI]-N,N'-bIs-(diphenylphosphine) ethylenediamine,
N, N'-Bis [R (+) - «- methylbenzyI] -N, N'-bIs- (diphenylphosphln)-äthylendiamin,
2(S),5(S)-Dtmethyl-N,N'-bisdiphenylphosphln-(+)-(diphenylphosphine) ethylenediamine,
2 (S), 5 (S) -Dtmethyl-N, N'-bisdiphenylphosphhln - (+) - piperazln oder
l-Phenyl-2,5-bls-S(-)-a-methyIbenzyl-l-phospha-piperazln or
l-phenyl-2,5-bls-S (-) - a-methyIbenzyl-l-phospha- 2,5-azacyclopentan,2,5-azacyclopentane, bei einer Temperatur von -70° C bis +200° C und einem Wasserstoifdruck von bis zu etwa 200 bar, wobei man mit einem Molverhältnis von alpha-Acylaminoacrylsäure zu Katalysator Im Bereich von 10 bis 10 000 arbeitet, dadurch gekennzeichnet, daß man das Verfahren mit Katalysatoren durchführt, die durch Immobilisieren dieser Rhodium-Komplexe an einem tonartigen Material erhalten worden sind.at a temperature of -70 ° C to + 200 ° C and a hydrogen pressure of up to about 200 bar, being with a molar ratio of alpha-acylaminoacrylic acid to catalyst in the range from 10 to 10,000 works, characterized in that the process is carried out with catalysts that by immobilizing these rhodium complexes a clay-like material.
DE2845216A 1977-10-17 1978-10-17 Process for the preparation of N-acyl-α-amino carboxylic acids by asymmetric hydrogenation Expired DE2845216C2 (en)

Applications Claiming Priority (1)

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IT28666/77A IT1087963B (en) 1977-10-17 1977-10-17 ASYMMETRICAL HYDROGENATION OF PROCHIRAL OLEFINS BY COMPLEX OF TRANSITION METALS IMMOBILIZED IN CLAY MINERALS.

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DE2845216A1 DE2845216A1 (en) 1979-04-19
DE2845216C2 true DE2845216C2 (en) 1984-05-10

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HU190864B (en) * 1983-12-08 1986-11-28 Alkaloida Vegyeszeti Gyar Process for production of phenil-alanin derivatives
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US4008281A (en) * 1973-12-03 1977-02-15 Monsanto Company Asymmetric catalysis
CA1109074A (en) * 1976-04-26 1981-09-15 Mario Fiorini Asymmetrical hydrogenation and related means for this purpose

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SE435923B (en) 1984-10-29
DE2845216A1 (en) 1979-04-19
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HU181953B (en) 1983-11-28
GB2006770A (en) 1979-05-10
DD139251A5 (en) 1979-12-19
AU4025178A (en) 1980-04-03
IT1087963B (en) 1985-06-04
FR2405911A1 (en) 1979-05-11
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NO148778C (en) 1983-12-14
YU237578A (en) 1983-01-21
IL55733A0 (en) 1978-12-17
BE871320A (en) 1979-04-17
CA1148564A (en) 1983-06-21
LU80370A1 (en) 1979-03-19
JPS5466615A (en) 1979-05-29
FR2405911B1 (en) 1981-03-20
CH636589A5 (en) 1983-06-15
NO783492L (en) 1979-04-18
CS208483B2 (en) 1981-09-15
ZA785486B (en) 1979-09-26
DK461478A (en) 1979-04-18
AU520574B2 (en) 1982-02-11
GB2006770B (en) 1982-03-17

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