WO2005066112A1 - Method for the catalytic reduction of amides - Google Patents
Method for the catalytic reduction of amides Download PDFInfo
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- WO2005066112A1 WO2005066112A1 PCT/NL2004/000018 NL2004000018W WO2005066112A1 WO 2005066112 A1 WO2005066112 A1 WO 2005066112A1 NL 2004000018 W NL2004000018 W NL 2004000018W WO 2005066112 A1 WO2005066112 A1 WO 2005066112A1
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/50—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acid amides
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- 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
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Definitions
- the invention relates to a novel method for the catalytic reduction of amides at mild reaction conditions, using novel bimetallic and trimetallic catalysts, active in the reduction of amines and to a method for the selection of such catalysts.
- Amines constitute an important class of compounds with extensive use as medicines or basic raw materials for the preparation of pharmaceuticals. Therefore, economically viable and green methods of synthesising amines are important.
- a simple and direct approach would be catalytic reduction of amides, and, indeed, there are numerous reports claiming the reduction of amides either by using hydrogen gas or by means of hydride containing reagents.
- Hiroshawa et al (Hirosawa, C; Wakasa, N.; Takamasa, F. Tetrahedron Lett . 1996, 37, 6749-6752) describe such catalytic reduction using the bimetallic catalysts RhRe, Rh , RhMo, RuRe and RuMo.
- Primary, secondary and tertiary amides were reduced to the corresponding amines, although the reaction conditions where still moderately harsh (100 bar at 160°C) .
- the present inventors have now found a novel method for the catalytic reduction of amides for the preparation of amines at mild reaction conditions to obviate the above drawbacks, i.e.
- a catalyst chosen from bimetallic and trimetallic catalysts of the group, consisting of ABC, AB, AC and BC, wherein: A is a metal, chosen from the group, consisting of Co, Fe, Ir, Pt, Rh and Ru, B is a metal, chosen from the group, consisting of Cr, Mo, Re and V, and, C is a metal, chosen from the group, consisting of Cu, In and Zn, were surprisingly suitable for the reduction of amides at mild reaction conditions.
- the reduction process is preferably performed with a heterogeneous catalyst. However, it is not necessary for the metals of the catalyst to be bound on the same support.
- one of the metals can be present on a carbon support, whereas another metal of the said catalyst can be present on e.g. a silica, titania or carbon support.
- a metal of the catalyst can be present on different supports. It is however preferred to provide the bimetallic and/or trimetallic catalyst on similar support material, although the different metals do not necessary have to be present on the very same support particles .
- the support is chosen from carbon, titania, amorphous silica-alumina and silica or a combination thereof.
- the catalytic reduction can even be performed at pressures of 30 bar or less, even at 15 bar or less.
- the method according to the invention can also successfully be performed at a pressure of 10 bar, preferably between 5-10 bar, more preferably between 6-10 bar.
- the reduction is performed in a continuous flow mode.
- such a continuous flow mode can be performed in a liquid phase, it is preferably performed in gaseous phase, i.e. wherein one or more, preferably all of the reactants are passed in gaseous phase over the catalyst at the above-mentioned reaction conditions .
- the above method according to the invention can successfully be performed at a temperature of 160°C or less, even at a temperature of 130°C or less. Also, it has been found that the method can be suitably performed at a temperature between 70-100°C, preferably around 80°C. "About" means that a deviation of 5°C is allowed.
- the method of the invention is performed at batch mode reactions, e.g. wherein at least one but preferably all of the reactants are in a liquid phase, e.g. in solution, and contacted with the catalyst.
- the amide substrate is dissolved in an appropriate solvent, such as an acid, an ether, an ester or an alcohol, preferably an acid, preferably a Bronsted acid, more preferably an organic acid.
- an appropriate solvent such as an acid, an ether, an ester or an alcohol, preferably an acid, preferably a Bronsted acid, more preferably an organic acid.
- Carboxylic acid is a preferred organic acid; most preferably, the organic acid comprises acetic acid.
- the solvent preferably has a pKa value of 5 or less, more preferably between 3 and 5.
- the preferred concentration of the acid, preferably organic acid, more preferably carboxylic acid and most preferably acetic " acid is up to 1.0 M, preferably between 0.2 and 0.8 M, more preferably between 0.4 and 0.5 M.
- the additive preferably comprises an acid, more preferably a Lewis acid, most preferably a boron-containing compound.
- the term "Lewis acid” is well known in the art.
- the substrate: additive ratio in the reaction mixture is preferably 4 or less, more preferably 2 or less, and most preferably between 0.9-1.1.
- the reaction mixture is preferably subjected to hydrogen pressures between 1 and 17 bar, more preferably between 5 and 10 bar.
- the reaction temperature is preferably between 90 and 140 °C, more preferably between 100 and 130°C.
- the catalyst is chosen from the group, consisting of:
- the catalyst is chosen from the group consisting of PtRe, IrMo, IrRe, PtRe, PtV, RhRe, RhV, FeReln, PtReCu, PtReln, PtReZn, RhMoCu, RuReZn, PtMo, RhMo, RuRe, IrReZn and PtMoCu, most preferably more preferably from the group consisting of PtRe, PtReCu, PtReln, FeReln, PtMo, PtV, RhMo, PtMoCu, RhMoCu, and RuRe, even more preferably from the group, consisting of PtReCu, PtReln, FeReln, PtMo, PtV, RhMo, PtMoCu, RhMoCu, PtRe and RuRe, and most preferably from the group consisting of PtReCu, PtReln, FeReln, PtMo, PtV, RhMo, PtMo
- the above-identified catalysts can effectively be used at the mild reaction conditions according to the invention.
- the invention relates to novel bi- or trimetallic catalysts for the reduction of amides to amines, chosen from the group, consisting of:
- the catalyst is preferably supported on a carrier, as outlined above .
- the invention relates to a method for the selection of at least one bi- or trimetallic catalyst, active in the reduction of amides into amines from a collection of bi- and/or trimetallic catalysts, comprising the steps of A) preparing the catalysts on separate carriers, B) loading the catalysts prepared in step A) in separate reactor vessels, the vessels having a parallel arrangement, C) feeding and incubating the reactor vessels with an amide and hydrogen at identical conditions regarding at least one of the quantities, chosen from reaction time, temperature and pressure, D) measuring the conversion of amides into amines in each reactor vessel, E) selecting one or more of the catalysts, based on the measured conversion in step D) .
- step A the catalysts are prepared in parallel.
- the carriers can be the same for the catalysts to be tested, but may also be different in order to test and select an optimal catalyst-carrier combination.
- the prepared catalysts on a carrier are loaded in reactor vessels arranged in parallel , so that the reactions to be performed with the catalysts can be done simultaneously.
- the reaction conditions such as reaction time, temperature and pressure are identical for the catalysts to be tested.
- the reactions are performed at identical conditions, so that relevant selections of active catalysts can be made.
- the said catalyst can be further tested at reaction conditions that differ from the first selection process to identify one or more catalysts that are optimally suitable for the envisaged reaction conditions.
- the selection method that is preferably performed in a gaseous phase in flow mode, can be extrapolated to batch mode reaction for industrial processes for the preparation of amines at suitably mild reaction conditions.
- Figures 1 to 5 refer to the results of amide reduction in flow mode.
- Figure 1 shows a gas chromatogram of a reduction reaction of 1-acetylpyrrolidine with the catalyst RhReCu on a carbon carrier at a temperature of 160°C and a pressure of 10 bar.
- the metal molar ratio of the catalyst was 1:1:1.
- Figure 2 and Figure 3 show the performance of silica and carbon supported catalysts, respectively, in the reduction of 1-acetylpyrrolidine at several different temperatures. In these examples, the metal molar ratio of the catalysts is 1:1 or 1:1:1 for bimetallic or trimetallic catalysts, respectively.
- Figure 4 shows the amine (in this case, 1-ethylpyrrolidine) formation profile at 100°C and 130°C as a function of the catalyst composition (bi- and trimetallic catalysts from groups A and B-C) .
- FIG. 6-10 refer to results of amide reduction in batch mode, wherein figures 6-7 show the performance of trimetallic catalysts without and with the presence of BF 3 as additive, respectively, and wherein figures 8-9 show the performance of bimetallic catalysts without and with the presence of BF 3 as additive, respectively.
- Figure 10 shows the performance of physical-mixture and pre-made catalysts, as well as the importance of having more than one metal element in the catalyst composition.
- the Nanoflow Equipment The catalyst screening in flow mode was carried out in reactors, arranged in parallel, the Avantium' s Nanoflow 2b (Avantium Technologies B.V., Netherlands), designed to allow gas and liquid feeds in trickle flow mode performed for this application.
- the equipment consists of 64 parallel reactors divided into four blocks of 16 reactors. Each reactor can be loaded with up to 200 mg of catalyst. Temperature can be varied independently on each block. The maximum temperature of the unit is 450-500°C, and the maximum pressure is 40 bar. An evaporator is placed up-stream of each reactor, so that controlled evaporation of liquid can take place.
- the QS Equipment The catalyst screening in batch mode was carried out in 96 pressure reactors, arranged in parallel: the Avantium QS Equipment (Avantium Technologies B.V., Netherlands). This equipment is divided into eight blocks of 12 reactors that operate in the so-called gas- on-demand system. This means that gas is added as soon as it is consumed by reaction, but no gas leaves the reactor at the exit.
- the maximum volume of each reactor is 7 ml; the maximum operating pressure for the blocks is 17 bar, and the maximum temperature is 140°C. Stirring is provided via magnetic stirring.
- Amine quantification was performed via on-line and off-line GC for flow and batch reactions, respectively. In both cases, a suitable internal standard was added to the reaction mixture to allow quantification of amide consumption and product formation.
- the gas- chromatograph was mounted with a COT fused silica 10 m x 0.32 mm column (coating: CP-Volamine) .
- Catalyst Preparation and Handling The two or three metals forming the catalysts were deposited onto the carrier using the techniques known by the skilled person, and preferably by incipient wetness impregnation directly from aqueous solutions containing a mixture of all desired metal salts. The total metal loading was kept between 2 and 5 wt% for the catalysts.
- Catalyst reduction can be attained by several reductants, like, and not limited to, NaBH, hydrazine, and hydrogen gas. Reduction by hydrogen gas was the preferred method, mainly in case of the reactions in flow mode. Catalyst reduction can be carried out in situ (immediately before addition of the reaction mixture) or beforehand.
- the support particle size between 50 and 1000 ⁇ m, preferably between 100 and 700 ⁇ m, and most preferably between 200 and 400 ⁇ m.
- Table 2 shows those catalysts that formed the amine in yields higher than 35% and at temperatures lower than 160 °C.
- Figure 4 shows that many of the active species result from combinations of Pt, Rh or Ir (Group A metals) with Re (followed by Mo and V from Group B) .
- Figure 5 shows the amine yield obtained with catalysts containing only metals from groups B and C. As can be seen, only combinations of Re and Mo with In formed 1-ethylpyrrolidine in yields higher than 35%, and at temperature of 130°C. This result bears the important message that the presence of a metal from Group A is important in the formation of active catalytic species.
- Figure 4 and Figure 5 also show that the support may also affect the catalyst activity.
- Table 2 List of silica- and carbon-supported catalysts that formed amine in yields equal or higher than 35%. Values lower than 35% were left blank. The table is divided into bi- and trimetallic catalysts, and within each division the content is sorted by catalyst alphabetical order.
- Figures 6 to 9 show the performance of several bi- and trimetallic catalysts in the reduction of 1-acetylpiperidine at 10 bar and 130°C having acetic acid as solvent.
- the amount of catalyst on each reaction was kept constant at 5 mol% (calculated considering the total number of moles of metals on each catalyst) .
- the ratio in front of each catalyst name refers to the molar fraction of each metal in the catalyst composition.
- the code for the first metal element is related to the type of salt used during the catalyst preparation:
- FeN03 Fe (N0 3 ) 3 .9H 2 0
- IrCl4 IrCl 4 .H 2 0
- IrNH4 NH 4 IrCl 6
- PtN03 Pt (N0 3 ) 2 (H 2 0) 2
- RhNH4 (NH 4 ) 3 RhCl 6
- RhN03 Rh(N0 3 ) 3 RuCl3: RuCl 3 .H 2 0
- RuNO Ru(NO) (N0 3 ) x . (H 2 0) y
- Rh/C + Re/C constitutes one of the most active catalytic systems, capable to form 1-ethylpiperidine from 1-acetylpiperidine in 98% yield in a reaction carried out in 1,2-DME at 100 bar, 170°C, for 16 h and using 1 mol% of catalyst (Hirosawa, C; akasa, N.; Takamasa, F. Tetrahedron Lett. 1996, 37, 6749-6752) .
- the authors also claim that the performance of the physical mixture is equivalent to the pre-made Rh-Re/C catalyst. We decided to test these aspects under our reaction conditions (i.e.
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PCT/NL2004/000018 WO2005066112A1 (en) | 2004-01-09 | 2004-01-09 | Method for the catalytic reduction of amides |
EP04701131A EP1708986A1 (en) | 2004-01-09 | 2004-01-09 | Method for the catalytic reduction of amides |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013030316A2 (en) | 2011-09-01 | 2013-03-07 | Johannes Gutenberg-Universität Mainz | Process for cathodic deoxygenation of amides and esters |
WO2015124595A1 (en) * | 2014-02-18 | 2015-08-27 | Qid S.R.L. | Method for the catalyzed reduction of halogen oxyanions in aqueous solutions |
DE102015201496A1 (en) | 2015-01-29 | 2016-08-04 | Thyssenkrupp Ag | Use of bimetallic catalysts in a process for the hydrogenation of amides of carboxylic acids from renewable resources |
WO2018181563A1 (en) * | 2017-03-31 | 2018-10-04 | 国立大学法人大阪大学 | Hydrogenation reaction catalyst used to hydrogenate amide compound and method for producing amine compound using same |
JP2019084524A (en) * | 2017-03-31 | 2019-06-06 | 国立大学法人大阪大学 | Catalyst for hydrogenation reaction used in hydrogenation of amide compound, and manufacturing method of amine compound using the same |
WO2020050160A1 (en) * | 2018-09-05 | 2020-03-12 | 国立大学法人大阪大学 | Hydrogenation catalyst for use in hydrogenating amide compound and method for producing amine compound using same |
WO2020175309A1 (en) * | 2019-02-26 | 2020-09-03 | 国立大学法人大阪大学 | Hydrogenation catalyst used in amide compound hydrogenation and method for producing amine compound using same |
WO2021109114A1 (en) * | 2019-12-06 | 2021-06-10 | Rhodia Operations | Supported heterogeneous catalyst, preparation and use thereof |
WO2021109109A1 (en) * | 2019-12-06 | 2021-06-10 | Rhodia Operations | Process for converting amide to amine |
JPWO2020080165A1 (en) * | 2018-10-17 | 2021-09-16 | 国立大学法人大阪大学 | Compounds and methods for producing them |
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US4035353A (en) * | 1973-12-18 | 1977-07-12 | Mitsubishi Petrochemical Company Limited | Process for producing hexamethyleneimine |
US4772750A (en) * | 1985-06-14 | 1988-09-20 | The Dow Chemical Company | Method of producing amines |
EP0286280A1 (en) * | 1987-03-26 | 1988-10-12 | BP Chemicals Limited | Process for the production of amines |
-
2004
- 2004-01-09 EP EP04701131A patent/EP1708986A1/en not_active Withdrawn
- 2004-01-09 WO PCT/NL2004/000018 patent/WO2005066112A1/en active Application Filing
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US4035353A (en) * | 1973-12-18 | 1977-07-12 | Mitsubishi Petrochemical Company Limited | Process for producing hexamethyleneimine |
US4772750A (en) * | 1985-06-14 | 1988-09-20 | The Dow Chemical Company | Method of producing amines |
EP0286280A1 (en) * | 1987-03-26 | 1988-10-12 | BP Chemicals Limited | Process for the production of amines |
Non-Patent Citations (1)
Title |
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HIROSAWA C ET AL: "Hydrogenation of Amides by the Use of Bimetallic Catalysts Consisting of Group 8 to 10, and Group 6 or 7 Metals", TETRAHEDRON LETTERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 37, no. 37, 9 September 1996 (1996-09-09), pages 6749 - 6752, XP004088084, ISSN: 0040-4039 * |
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