JP2019084524A - Catalyst for hydrogenation reaction used in hydrogenation of amide compound, and manufacturing method of amine compound using the same - Google Patents

Abstract

To provide a catalyst capable of conducting a reduction reaction for converting an amide compound to an amine compound, capable of being used even under moderate conditions, and having durability capable of being used repeatedly while maintaining high activity.SOLUTION: There is provided a catalyst for hydrogenation reaction of an amide compound in which platinum and vanadium are carried on a carrier, and a manufacturing method of an amine compound using the same.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a catalyst supported on a carrier containing platinum and vanadium used in a hydrogenation reaction to convert an amide compound to an amine compound, and a method for producing an amine compound using the same.

  The reduction reaction for converting an amide compound to an amine compound is one of the most difficult reactions among the reductions of carboxylic acid derivatives because the amide is non-reducing.

The reduction reaction is lithium aluminum hydride in small amounts test studies like for the amide compound to amine compound (LiAlH _4), a method using stoichiometrically a strong reducing agent such as sodium borohydride (NaBH ₄₎ is but generally When used for industrial scale synthesis, the generation and reaction of a large amount of metal waste cause high hydrogen and other hazards when used in large amounts, and the post-treatment operations are complicated. It had become.

  On the other hand, the reduction reaction from amide to amine, which uses molecular hydrogen as a reducing agent, is a method of synthesizing environmentally friendly amines because only harmless water is by-produced. The catalytic hydrogen reduction reaction of this amide has been studied for a long time and has been carried out using a copper-chromium, rhenium or nickel catalyst, but high temperature and high pressure reaction conditions such as hydrogen pressure 200 atm and reaction temperature 200 ° C or more Need.

  In recent years, in Non-Patent Documents 1 and 2, hydrogenation of an amide under low temperature and low pressure conditions of 120 ° C., 10 atm or 160 ° C., 5 atm has been reported by adding molecular sieves into the reaction system. However, there is a problem in that the substrate applicability is poor and alcohol by-products generated by CN cleavage is by-produced. Also, these catalysts can not be reused.

  In addition, although there is also a reaction using a homogeneous catalyst reported in Non-Patent Document 3, there is a problem that an alcohol by-product by CN cleavage is generated. In addition, it is difficult to repeatedly use an expensive catalyst in a reaction using a homogeneous catalyst.

  Therefore, for industrial use, there is a demand for a highly durable catalyst that can be used under mild conditions and can be repeatedly used while maintaining high activity.

R. Burch, C. Paun, X.-M. Cao, P. Crawford, P. Goodrich, C. Hardacre, P. Hu, L. McLaughlin, J. Sa, JM Thompson, Catalytic hydrolysis of tertiary amides at low temperatures and pressures using bimetallic Pt / Re-based catalysts. J. Catal. 283, 89-97 (2011) Angew. Chem. Int. Ed. 125, 2287-2290 (2013) M. Stein, B. Breit, Catalytic hydrolysis of amides to amines under amines conditions. E. Balaraman, B. G. nanaprakasam, L. J. W. Shimon, D. Milstein, Direct hydrogenation of amides to alcohols and amines under mild conditions. J. Am. Chem. Soc. 132, 16756-16758 (2010)

  Therefore, an object of the present invention is a catalyst capable of reducing an amide compound to an amine compound, which catalyst can be used even under mild conditions, and has a durability that can be repeatedly used while maintaining high activity. To provide.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a catalyst supported on a carrier containing platinum and vanadium has high hydrogenation activity, selectivity, durability, and reactivity to an amide compound. The present invention has been completed.

  That is, the present invention is a catalyst for hydrogenation reaction of an amide compound characterized in that platinum and vanadium are supported on a carrier.

  Further, the present invention is a method for producing a catalyst for a hydrogenation reaction of the above-mentioned amide compound, characterized in that platinum and vanadium are supported on a carrier in a solvent and then dried.

  Furthermore, the present invention is a catalyst for the hydrogenation reaction of an amide compound characterized in that platinum, vanadium and ruthenium are supported on a support.

  Still further, the present invention is a method for producing a catalyst for hydrogenation reaction of the above-mentioned amide compound, characterized in that platinum, vanadium and ruthenium are supported on a carrier in a solvent and then dried.

  Furthermore, the present invention is a method for producing an amine compound, which comprises contacting an amide compound with the catalyst for a hydrogenation reaction of the above-mentioned amide compound and hydrogenating the catalyst to obtain an amine compound.

  Further, the present invention is an amine compound produced by the above method for producing an amine compound.

  Since the catalyst of the present invention can be used under mild conditions, the synthesis of an amide compound to an amine compound is safe and easy.

  In addition, since the catalyst of the present invention does not require any special operation in the production, it can be produced inexpensively and safely.

  Therefore, the catalyst of the present invention can be used for industrial synthesis of amide compounds to amine compounds.

  In addition, since the catalyst of the present invention is supported on a carrier, expensive platinum can be easily recovered by filtration after use, and the recovered catalyst can maintain its initial activity and selectivity.

  Therefore, the catalyst of the present invention is easy to reuse.

It is a TEM image of catalyst Pt-V / HAP of this invention. 5 is an ADF-STEM image of Pt-V / HAP obtained in Production Example 1; It is an elemental mapping image of Ca of Pt-V / HAP obtained by manufacture example 1. FIG. It is an elemental mapping image of V of Pt-V / HAP obtained by manufacture example 1. FIG. It is an elemental mapping image of Pt of Pt-V / HAP obtained by manufacture example 1. FIG. The elemental mapping image of Ca * V * Pt of Pt-V / HAP obtained by manufacture example 1 is accumulated. It is a figure which shows the result of EDS line analysis of Pt-V / HAP obtained by manufacture example 1. FIG.

  The catalyst for the hydrogenation reaction of the amide compound of the present invention (hereinafter referred to as "the catalyst of the present invention") is one in which platinum and vanadium are supported on a carrier. In the present specification, the catalyst of the present invention may be described as "XY / Z" (where X and Y are metal names such as platinum and vanadium, and Z is a carrier name).

(platinum)
The platinum constituting the catalyst of the present invention is not particularly limited, but for example, platinum particles are preferable. Here, the platinum particles are particles of platinum selected from at least one of metal platinum and platinum oxide, and preferably particles of metal platinum.

  Here, the platinum particles are not particularly limited as long as they contain platinum, and may contain a small amount of a noble metal such as ruthenium (Ru), rhodium (Rh) or palladium (Pd), but preferably It is metal platinum. The platinum particles may be primary particles or secondary particles. 1-30 nm is preferable and, as for the average particle diameter of a platinum particle, 1-10 nm is more preferable. In the present specification, the "average particle size" refers to an average value of the diameters of particles of any number observed by an electron microscope.

(vanadium)
The vanadium constituting the catalyst of the present invention is not particularly limited. For example, vanadium oxide is preferable. The vanadium oxide is, for example, one selected from at least one of vanadate ions (VO ₄ ^3- and VO ₃ ^3- ), vanadium pentoxide, vanadium oxide (II) and vanadium oxide (IV). , Preferably V ₂ O ₅ .

(Molar ratio of platinum-vanadium [Pt-V])
In the catalyst of the present invention, the composition ratio of platinum to vanadium is platinum (Pt) as metal: molar ratio [Pt: V] = 1: 0 of the number of moles of vanadium (V) as metal. It is 1-10, preferably 1: 0.5-5, more preferably 1: 0.8-1.2.

(ruthenium)
The catalyst of the present invention can further contain ruthenium. The ruthenium is not particularly limited, and examples thereof include ruthenium oxide, metallic ruthenium and the like. The metal ruthenium may be alloyed with platinum, and the ruthenium oxide may form a complex oxide with vanadium oxide. The alloying and the formation of the composite oxide can be carried out according to a conventional method.

  When the catalyst of the present invention contains ruthenium, part of platinum or vanadium described above may be replaced with ruthenium.

(Molar ratio of platinum-ruthenium-vanadium [Pt-Ru-V])
In the catalyst of the present invention, the composition ratio of platinum to ruthenium to vanadium is as described above with respect to the composition ratio of platinum to vanadium, and platinum (Pt) as a metal: mole of moles of ruthenium (Ru) as a metal The molar ratio [Pt: Ru] = 1: 0.1 to 10, preferably 1: 0.5 to 5, more preferably 1: 0.8 to 1.2 in number conversion.

(Carrier)
The support (base material) of the catalyst of the present invention is not particularly limited. Various physical properties such as the adsorption ability of the carrier are not particularly limited, but for example, the adsorption ability may be 0.1 to 300 m ² / g as a so-called BET value, and 0 as an average particle diameter. It may be from .02 to 100 .mu.m. In the present invention, the adsorption capacity of the carrier is preferably 0.5 to 180 m ² / g.

  The form of the carrier is not particularly limited, and examples thereof include powder, spherical particles, irregular granules, cylindrical pellets, extruded shapes, and ring shapes.

  As the above-mentioned carrier, for example, inorganic oxides such as hydroxyapatite (HAP), titania, alumina, silica and carbon powder can be used, and preferred is hydroxyapatite.

The hydroxyapatite is not particularly limited, and it is possible to use not only calcium hydroxide phosphate having the stoichiometric composition of general Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ but also water having a composition similar to this composition. Including calcium oxide phosphate compounds and tricalcium phosphate.

  In the catalyst of the present invention, the mode in which platinum and vanadium are supported on the carrier is not particularly limited, and various modes can be adopted depending on the form of the carrier, and the position at which the catalyst is supported is also simply controlled. There is no need, or it may be inside the pore or layer, or only on the surface, but platinum of small particle size is dispersed and supported, and vanadium is present in the vicinity of platinum or on platinum. Is preferred. Although the amount of platinum and vanadium oxide supported on the carrier in the catalyst of the present invention is not particularly limited, it is preferably, for example, 0.1 to 10 wt% in terms of platinum in terms of metal.

  It goes without saying that since the catalyst of the present invention uses the above-mentioned support, it can be easily separated after being used for the reaction, and it is also advantageous in reuse of the catalyst.

(Components that can be added to the catalyst)
The catalyst of the present invention may be supported on the support as long as platinum and vanadium (optionally ruthenium) are supported on the support, and a transition metal, an alkali metal, an alkaline earth metal, etc., as a catalyst component or a support component It may be contained according to a conventional method.

(Method of producing the catalyst of the present invention)
Among the catalysts of the present invention, a catalyst for the hydrogenation reaction of an amide compound characterized in that platinum and vanadium are supported on a support is prepared by supporting platinum and vanadium on a support in a solvent and then drying the support. (Hereinafter referred to as “the present invention method A”).

  Specifically, in the method A of the present invention, the method for supporting platinum and vanadium on a carrier in a solvent is not particularly limited. For example, platinum is obtained by mixing the carrier and a solvent mixture containing a platinum compound and a vanadium compound. And vanadium, supported on a carrier in a solvent, or the carrier, a solvent liquid containing a platinum compound, and a solvent liquid containing a vanadium compound are mixed in any order, and platinum and vanadium are contained in the solvent. A method of supporting on a carrier can be mentioned.

The platinum compound used in the method A of the present invention is not particularly limited, but preferably becomes platinum particles on a carrier when dried. As such a platinum compound, for example, platinum acetylacetonato (Pt (acac) ₂ ), tetraammine platinum (II) acetate, dinitrodiammine platinum (II), hexaammine platinum (IV) carbonate, bis (diben) (Zaruacetone) Platinum complex salts such as platinum (0), salts such as platinum chloride, platinum nitrate, potassium tetrachloroplatinate and the like, and Pt (acac) ₂ are particularly preferable.

In addition, the vanadium compound used in the method A of the present invention is not particularly limited, but preferably it produces vanadium oxide on a carrier when dried. As such a vanadium compound, for example, vanadium complex salts such as vanadyl acetylacetonato (VO (acac) ₂ ), bis (taltrato) bis [oxovanadium (IV)] tetramethylammonium, vanadate (V) ammonium And salts thereof such as vanadium naphthenate, and in particular, VO (acac) ₂ is preferable.

  The solvent mixture liquid containing a platinum compound and a vanadium compound used in the method A of the present invention is obtained by suspending the platinum compound and the vanadium compound in a solvent. The platinum compound and the vanadium compound in this solvent mixture liquid have a molar ratio of 1: 0.1 to 10, preferably 1: 0.5 to 5, and more preferably 1: 1. Examples of the solvent include water, and organic solvents such as alcohol and acetone. Water is preferable because it is excellent in both cost and safety. These solvents may be used alone or in combination of two or more. The temperature of the solvent is not particularly limited, and is, for example, 0 to 100 ° C, preferably 10 to 50 ° C.

  The solvent mixture prepared as described above may then be mixed with the carrier. The method of mixing the solvent mixture and the carrier is not particularly limited, as long as there is a sufficient amount of each component to be dispersed, 0.1 to 100 g of the carrier, preferably 1 to 0.1 mmol of platinum in metal conversion. With stirring in an amount of ̃10 g. After mixing, stirring is continued for 0.5 to 12 hours, preferably 1 to 6 hours.

  The solvent liquid containing a platinum compound and the solvent liquid containing a vanadium compound used in the method A of the present invention are obtained by suspending the platinum compound and the vanadium compound in a solvent, respectively. The content of each compound in these solvent liquids may be the same as that in the solvent liquid mixture containing the platinum compound and the vanadium compound when the solvent liquids are mixed. Further, the temperature of the solvent used for these and the solvent may be the same as that of the above-mentioned solvent mixture.

  Next, the solvent liquid containing the platinum compound prepared as described above and the solvent liquid containing the vanadium compound are prepared by adding a carrier, a solvent liquid containing the platinum compound, and a solvent liquid containing the vanadium compound. It may be mixed in any order. If the carrier liquid and the solvent liquid containing the platinum compound are mixed and then mixed in the order of the solvent liquid containing the vanadium compound, the transition metal tends to be supported on the platinum compound, and it is expensive when the platinum compound is mixed later It is good because the loss of platinum may be reduced. Further, the method of mixing the solvent liquid and the carrier may be the same as in the case of using the mixed solution.

  As described above, the solvent mixture and the carrier may be mixed, or each solvent liquid and the carrier may be mixed, and platinum and vanadium may be supported on the carrier in the solvent and then dried. Before drying, it is preferable to remove the solvent by pretreatment such as washing, filtration, concentration and the like. Although the conditions for drying are not particularly limited, for example, drying is performed at 80 to 200 ° C. for 1 to 56 hours. After drying, for example, it is preferable to perform firing or the like at 250 to 700 ° C. for 1 to 12 hours using a muffle furnace or the like, and further pulverization or the like may be performed.

When water is used as a solvent in the method A of the present invention, examples of platinum compounds include hexachloroplatinum (IV) acid salt (H ₂ PtCl ₆ ), tetrachloroplatinum (II) acid salt (K ₂ PtCl _4, etc.) And platinum salts. Among these, potassium tetrachloroplatinate (II) (K ₂ PtCl ₄ ) is preferable. Also, as the vanadium compound, for example, vanadium salts such as vanadium chloride (VCl ₃ ), sodium metavanadate (NaVO ₃ ), sodium orthovanadate (V) (Na ₃ VO ₄ ), potassium metavanadate (KVO ₃ ) And vanadate salts such as ammonium metavanadate (NH ₄ VO ₃ ). Among these, vanadium chloride is preferred.

  When water is used as a solvent in the method A of the present invention, if the compound is difficult to dissolve in the solvent, a pH adjuster, a binder, etc. may be used, or ultrasonic waves may be applied, as long as there is no problem in catalyst performance. The temperature may be adjusted. Examples of pH adjusters include sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, ammonia, acetic acid, citric acid, carbonic acid, lactic acid and the like. Further, examples of the binder include organic compounds such as polyethylene glycol and polyvinyl alcohol, and inorganic compounds such as silica.

  Among the catalysts of the present invention, platinum, vanadium and ruthenium are supported on a support, and the catalyst for hydrogenation reaction of an amide compound is supported on platinum, vanadium and ruthenium on the support in a solvent, It can manufacture by drying this (henceforth "the present invention method B").

  Specifically, in the method B of the present invention, the method for supporting platinum, vanadium and ruthenium on a carrier in a solvent is not particularly limited. For example, a carrier and a solvent mixture containing a platinum compound, a vanadium compound and a ruthenium compound A method of mixing platinum, vanadium and ruthenium on a carrier by mixing, a carrier mixed solution containing a platinum compound and a solvent mixed solution containing a vanadium compound, and a solvent mixed containing a ruthenium compound There is a method of mixing platinum, vanadium and ruthenium in a solvent by mixing the liquids in any order and supporting them on a carrier.

The platinum compound and vanadium compound used in the method B of the present invention are the same as those used in the method A of the present invention. Further, the ruthenium compound used in the method B of the present invention is not particularly limited, and for example, salts such as ruthenium chloride and ruthenium acetate, ruthenium acetylacetonate, dodecacarbonyltriruthenium (0), formatodicarbonylruthenium (I), Complex salts such as ruthenium (II) nitrosyl nitrate and hexaammineruthenium acetate are listed. Among these, ruthenium chloride and Ru (acac) ₃ are preferable.

  The solvent mixture liquid containing a platinum compound, a vanadium compound and a ruthenium compound used in the method B of the present invention is obtained by suspending the platinum compound, the vanadium compound and the ruthenium compound in a solvent. The platinum compound and the vanadium compound in this solvent mixture liquid have a molar ratio of 1: 0.1 to 10, preferably 1: 0.5 to 5, and more preferably 1: 1. And a ruthenium compound should just substitute a part of platinum compound or vanadium compound mentioned above to ruthenium. Further, the temperature of the solvent used for these and the solvent may be the same as in the method A of the present invention.

  The solvent mixture prepared as described above may then be mixed with the carrier. The method of mixing the solvent mixture and the carrier may be the same as in the method A of the present invention except that the solvent mixture is used.

  The solvent liquid containing a platinum compound, the solvent liquid containing a vanadium compound, and the solvent liquid containing a ruthenium compound used in the method B of the present invention respectively contain the platinum compound, the vanadium compound and the ruthenium compound as solvents. It is suspended. The content of each compound in the solvent mixture may be the same as that in the solvent mixture containing the platinum compound, the vanadium compound and the ruthenium compound when the solvent solution is mixed. Further, the temperature of the solvent used for these and the solvent may be the same as in the method A of the present invention.

  The solvent liquid containing a platinum compound prepared as described above, the solvent liquid containing a vanadium compound, and the solvent liquid containing a ruthenium compound are then treated with a carrier and a solvent liquid containing a platinum compound, A solvent liquid containing a vanadium compound and a solvent liquid containing a ruthenium compound may be mixed in any order. Further, the method of mixing the solvent liquid and the carrier may be the same as in the method A of the present invention except that the solvent liquid is used.

  As described above, after the solvent mixture and the carrier are mixed or each solvent liquid and the carrier are mixed and platinum, vanadium and ruthenium are supported on the carrier in the solvent, drying is carried out in the same manner as the method A of the present invention. You should do it. After drying, calcination, pulverization and the like may be performed as in the method A of the present invention.

When water is used as a solvent in the method B of the present invention, as ruthenium compounds, ruthenium (III) chloride (RuCl ₃ ), sodium ruthenate (K ₂ RuO ₄ ), ruthenium nitrosyl nitrate (Ru (NO) (NO) ₃ ) Ruthenium salts such as ₃ ) can be mentioned. Among these, ruthenium chloride is preferred. The conditions other than this may be the same as in the method A of the present invention.

  In the catalyst of the present invention, platinum and vanadium (optionally ruthenium) (hereinafter simply referred to as "platinum etc.") may be uniformly supported in the carrier particles, and are supported unevenly on the surface side of the carrier. It is also good. With regard to the position of supporting such platinum or the like, it is desirable to carry out uneven distribution on the surface side of the carrier, particularly when it is intended to effectively use an expensive component such as platinum. By unevenly supporting the surface of the support, the reaction substrate and the platinum and the like are more likely to be in contact with each other, and the activity of the catalyst can be expected to be improved.

  A method for causing platinum or the like to be unevenly supported on the surface of such a carrier is not particularly limited, and can be appropriately selected from known methods according to the catalyst material to be used. Specific examples include a solvent mixture containing the platinum compound or vanadium compound (optionally a ruthenium compound), a solvent liquid containing a platinum compound, or a solvent solution containing a vanadium compound (optionally containing a ruthenium compound) Method for adjusting the pH of the solvent solution), and before or after mixing the carrier with the solvent mixture or the solvent solution in order to cause the platinum and the like to become non-water soluble (precipitated) on the carrier, A method of fixing platinum and the like by treatment with an aqueous solution used for immobilization, a method of mixing the carrier with the solvent mixture or the solvent solution, managing the temperature and the standing time, and aging After catalyst manufacture, the method etc. which add a calcination process further are mentioned. In the above method, washing, drying and the like may be appropriately performed.

  In the method of adjusting the pH of the solvent mixture or the solvent liquid, the above-mentioned pH adjusters can be used, and using these, the pH of the solvent mixture or the solvent liquid can be adjusted so that the carrier can be easily supported. It may be acid, it may be alkaline, or it may be neutral.

  Before or after mixing the carrier and the solvent mixture solution or the solvent solution, an alkaline aqueous solution in which an alkaline compound is dissolved in water or the like is used in the method of treating with an aqueous solution used for water nonsolubilization such as an alkaline aqueous solution. Examples of the alkaline compound include hydroxides of alkali metals and alkaline earth metals, bicarbonates of alkali metals and alkaline earth metals, carbonates of alkali metals and alkaline earth metals, and alkali metals and alkaline earth metals. Silicate, ammonia and the like can be mentioned. Moreover, pH in this case is although it does not specifically limit, 7-14, Preferably it is 8-13.

  The amount of the alkaline aqueous solution used for the treatment of non-solubilization is intended to immobilize a platinum compound or a vanadium compound (a ruthenium compound, if necessary), so the amount of alkali slightly excess to the object to be reduced, For example, it is preferable to use it by adjusting the concentration to 1.05 to 1.2 times.

  In the above method of ripening, the temperature and the standing time after mixing the carrier, the solvent mixture and the solvent may be appropriately set, and are not particularly limited, but for example, 1 to 72 hours at 10 to 100 ° C. Preferably, it may be aged at 30 to 70 ° C. for 2 to 24 hours.

  In the method of further adding a calcining step after the production of the catalyst of the present invention, the produced catalyst of the present invention may be fired while being subjected to a thermal reduction treatment in a hydrogen-containing gas atmosphere. Such baking is also called gas phase reduction or hydrogen reduction. In the case of gas phase reduction, there is no solvent involved during reduction, and migration of the component to be reduced is difficult, and particles such as platinum are difficult to aggregate, and platinum and the like can be supported in the form of small particles.

  When this firing step is performed, platinum and the like may be oxidized after the firing. In such a case, it is preferable to carry out a reduction treatment. Gas phase reduction and liquid phase reduction can be employed for such reduction treatment. In the gas phase reduction, a reducing gas is supplied to a catalyst heated to 100 to 500 ° C. to perform reduction treatment. As such a reducing gas, carbon monoxide and low molecular weight hydrocarbons may be used in addition to hydrogen as described above. As low molecular weight hydrocarbons, methane, ethane, propane, butane, ethylene and the like can also be used. In the case of gas phase reduction, the composition of the gas may be a gas consisting of only a reducing component, but may be used as a mixture with an inert gas such as nitrogen at the time of reduction.

  Moreover, liquid phase reduction mixes a reducing liquid and a catalyst, and reduces the oxidized catalyst component by heating at 80-150 degreeC. The reducing component to be used is not particularly limited and may be appropriately selected depending on the reducing conditions, and examples thereof include formic acid, sodium formate and hydrazine.

  The catalyst of the present invention thus obtained has platinum and vanadium (optionally ruthenium) supported on a carrier.

  The fact that the catalyst of the present invention can be produced includes, for example, TEM (Transmission Electron Microscope; transmission electron microscope), FE-SEM (Field Emission-Scanning Electron Microscope; field emission scanning electron microscope), EDX (Energy Dispersive) It can confirm by X-ray spectroscopy (energy dispersive X ray spectroscopy) etc.

(Hydrogenation of amide compounds)
The catalyst of the present invention is for the hydrogenation reaction of an amide compound. Therefore, when the catalyst of the present invention is contacted with an amide compound, it can be hydrogenated (reduced) to produce an amine compound.

  The amide compound is not particularly limited as long as it is a compound having an amide bond, and examples thereof include a secondary or higher amide compound or an amide compound containing an aromatic substituent, a lactam or a carbonyl bonded to an N atom in a tertiary amide. The amide compound etc. which two of the substituents which do not contain mutually couple | bond with each other, and take a cyclic structure are preferable, and the amide compound which contains a secondary or more class amide compound or an aromatic substituent is more preferable.

  The method of contacting the amide compound with the catalyst of the present invention and hydrogenating the catalyst is not particularly limited, and may be appropriately selected. Specifically, the amide compound may be hydrogenated by bringing the catalyst of the present invention, the amide compound, and hydrogen gas into contact in a liquid phase in a pressure resistant container such as an autoclave. In addition, in the case of hydrogenation, a molecular sieve or the like may be placed in a container in order to remove water and allow the reaction to proceed. Furthermore, the catalyst of the present invention may be subjected to reduction treatment prior to hydrogenation.

  The liquid phase is preferably an organic solvent alone or a mixture of several organic solvents, and more preferably only an organic solvent. Although the organic solvent used above is not particularly limited, for example, aliphatic hydrocarbons having 5 to 20 carbon atoms such as dodecane and cyclohexane, aromatic hydrocarbons having 7 to 9 carbon atoms such as toluene and xylene, and dimethyl ether From ethers having a linear or cyclic structure such as dimethoxyethane (DME), oxetane, tetrahydrofuran (THF), tetrahydropyran (THP), furan, dibenzofuran, furan, etc., polyethers such as polyethylene glycol, polypropylene glycol, etc. One or more selected may be mentioned, and among these, DME is particularly preferable.

  The use amount of the organic solvent is, for example, preferably in a range in which the concentration of the amide compound is about 0.5 to 2.0% by mass. The amount of the catalyst of the present invention is, for example, about 0.0001 to 50 mol%, preferably about 0.01 to 20 mol%, based on the amount of platinum in the catalyst, with respect to the amide compound. About 1 to 5 mol% is more preferable.

  The catalyst of the present invention can smoothly proceed the hydrogenation reaction even under mild conditions. The reaction temperature can be appropriately adjusted according to the type of substrate, type of target product, etc., and is, for example, 100 ° C. or less, preferably 10 to 100 ° C., more preferably 20 to 80 ° C., particularly preferably It is about 30 to 70 ° C. The pressure at the time of reaction is 5 MPa or less, preferably normal pressure to 4 MPa, more preferably 2 to 3.5 MPa. The reaction time can be appropriately adjusted according to the reaction temperature and pressure, and is, for example, about 10 minutes to 56 hours, preferably about 20 minutes to 48 hours, and particularly preferably about 40 minutes to 30 hours.

  Although an amine compound can be obtained by hydrogenating an amide compound by the above-mentioned method, an amine compound which is difficult to manufacture by a usual cross coupling reaction etc. can also be manufactured by the method of the present invention. Specifically, in the Buchwald-Hartwig reaction, which is a typical example of C—N coupling, an aryl halide is reacted with a 1 · secondary amine in the presence of a Pd catalyst to directly bond an aryl group to the N atom of the amine. However, one or more carbon atoms or methylene chains can not be interposed between the N atom and the aromatic ring. However, in the method described above, the amide compound obtained by acylating the N atom of the amine is hydrogenated, resulting in the C having one or more carbon atoms or methylene chains intervened in the N atom of the original amine. -N bond can be generated. As such an example, morpholine → 4-cyclohexyl carbonyl morpholine → 4-cyclohexyl methyl morpholine, piperidine → 1-phenyl acetyl piperidine → 1-phenethyl piperidine, benzyl methyl amine → benzyl methyl phenyl acetyl amide → benzyl methyl phenethyl amine etc. are mentioned. Be

(Reuse of catalyst)
In the catalyst of the present invention, since platinum, which is an active component, is supported on a carrier, the supported platinum is unlikely to be large particles even during the reaction. Also, the catalyst of the present invention can be easily recovered from the reaction solution after hydrogenation, for example, by physical separation methods such as filtration and centrifugation. The recovered catalyst of the present invention can be reused as it is or, if necessary, after being subjected to washing, drying, calcination and the like. Washing, drying, calcination and the like may be carried out in the same manner as in the production of the catalyst of the present invention.

  The recovered catalyst of the present invention can exhibit almost the same catalytic ability as that of the unused catalyst of the present invention, and significantly suppresses the decrease in catalytic ability even after repeated use-regeneration. Can. Therefore, according to the present invention, since the catalyst which usually accounts for a large proportion of the cost of hydrogenation can be recovered and repeatedly used, the cost of hydrogenation of the amide compound can be significantly reduced.

  Hereinafter, the catalyst of the present invention and examples of the present invention will be specifically described, but the present invention is not limited to the following examples, and can be widely applied within the scope of the present invention. is there.

Production example 1
Preparation of Pt-V / HAP:
0.4 mmol of NE Chemcat Co., Ltd. Pt (acac) 2 and 0.4 mmol of Sigma Aldrich Co. of VO (acac) 2 were added to 90 mL of acetone and stirred at room temperature for 30 minutes. Furthermore, 1.0 g of HAP (trade name "tricalcium phosphate") manufactured by Wako Pure Chemical Industries, Ltd. was added, and the mixture was stirred at room temperature for 4 hours. The solvent was removed from the resulting mixture on a rotary evaporator to obtain a pale green powder. The resulting powder was dried at 110 ° C. overnight. Furthermore, the dried powder was ground in an agate pot, and fired in air at 300 ° C. for 2 hours to obtain a dark gray powder (Pt-V / HAP).

Various analyzes were performed about Pt-V / HAP obtained above. The TEM image of Pt-V / HAP is shown in Figure 1, the ADF-STEM image in Figure 2, the elemental mapping image of Ca in Figure 3, the elemental mapping image of V in Figure 4 and the elemental mapping image of Pt in Figure 5 In addition, Fig. 6 shows an element mapping image of Ca, V, and Pt. From these results, in the catalyst of the present invention, platinum particles are supported on a support, vanadium oxide (V ₂ O ₅ ) is present in the vicinity of or on platinum particles, and platinum (Pt) as a metal: vanadium as a metal It was found that the molar ratio [Pt: V] = 6: 7, and the amount of platinum as a metal was 5.8 wt%, in terms of the number of moles of (V). Moreover, the average particle diameter of platinum particle | grains was 2.2 nm from the result (FIG. 7) of the EDS line analysis of Pt-V / HAP.

Production example 2
Preparation of Pt-V / C:
Pt-V / C was similarly obtained except having replaced HAP of manufacture example 1 with porous carbon (brand name: carbon, mesoporous) of Sigma Aldrich company. The molar ratio [Pt: V] = 6: 7, and the amount of platinum as metal is 5.8 wt% in terms of the number of moles of platinum (Pt) as metal: vanadium (V) as metal I understand.

Production example 3
Preparation of Pt-V / TiO ₂ :
Except that the HAP of Preparation 1 was changed to titania (JRC TIO-4) is a reference catalyst of Catalyst Society Pt-V / TiO ₂ was obtained in the same manner. The molar ratio [Pt: V] = 6: 7, and the amount of platinum as metal is 5.8 wt% in terms of the number of moles of platinum (Pt) as metal: vanadium (V) as metal I understand.

Production example 4
Preparation of Pt-V / Al ₂ O ₃ :
Pt-V / Al ₂ O ₃ was similarly obtained except that HAP of Production Example 1 was changed to alumina (AKP-G015) of Sumitomo Chemical Co., Ltd. The molar ratio [Pt: V] = 6: 7, and the amount of platinum as metal is 5.8 wt% in terms of the number of moles of platinum (Pt) as metal: vanadium (V) as metal I understand.

Production example 5
Preparation of Pt-V / SiO ₂ :
Except for changing the HAP of Preparation 1 Fuji Silysia Chemical Ltd. of silica (Q-3) is Pt-V / SiO ₂ was obtained in the same manner. The molar ratio [Pt: V] = 6: 7, and the amount of platinum as metal is 5.8 wt% in terms of the number of moles of platinum (Pt) as metal: vanadium (V) as metal I understand.

Production example 6
Preparation of Pt-Ru-V / TiO ₂ :
To 90 mL of water, add 5.0 mL (Ru: 0.2 mmol) of 40 mM RuCl ₃ aqueous solution manufactured by NY Chemcat Co., and 0.55 g TiO ₂ , 0.085 g (Pt: 0.2 mmol) K ₂ (PtCl ₄ ), and further The solution was added with 5.0 mL (V: 0.2 mmol) of 40 mM VCl ₃ aqueous solution and stirred at room temperature for 6 hours. To the resulting mixture was added 1.0 mL of 28 wt% aqueous ammonia, and the mixture was heated and stirred at 90 ° C. for 6 hours. The solution was filter washed with deionized water and the resulting powder was dried at 110 ° C. overnight. The dried powder was ground in an agate pot to obtain a gray powder (Pt-Ru-V / HAP). The metal ratio in the obtained powder is platinum (Pt) as metal: ruthenium (Ru) as metal: molar ratio [Pt: Ru: V] in terms of the number of moles of vanadium (V) as metal It was 1: 1: 1, and the amount of platinum as a metal was 7.8 wt%.

Production example 7
Preparation of Pt-Re / HAP:
Except for changing the VO _{(acac) 2} in Production Example 1 to _Re 2 _{(CO) 10} in Strem Chemicals Inc. Pt-Re / HAP was obtained in the same manner. The molar ratio [Pt: Re] = 6: 7, and the amount of platinum as metal is 5.8 wt% in terms of the number of moles of platinum (Pt) as metal: rhenium (Re) as metal I understand.

Production example 8
Preparation of Pt-Mo / HAP:
Except for changing the VO _{(acac) 2} in Production Example 1 Nacalai Tesque Inc. _{(NH 4)} to _{6 Mo 7 O 24 · 4H 2} O is Pt-Mo / HAP was obtained in the same manner. The molar ratio [Pt: Mo] = 6: 7, and the amount of platinum as metal is 5.8 wt% in terms of the number of moles of platinum (Pt) as metal: molybdenum (Mo) as metal I understand.

Production example 9
Preparation of Pt-W / HAP:
Except for changing the VO _{(acac) 2} Preparation Example 1 Sigma-Aldrich Co. _{(NH 4)} to _{10 H 2 (W 2 O 7} ) 6 · xH 2 O is Pt-W / HAP was obtained in the same manner. The molar ratio [Pt: W] = 6: 7, and the amount of platinum as metal is 5.8 wt% in terms of the number of moles of platinum (Pt) as metal: tungsten (W) as metal I understand.

Production example 10
Preparation of Pd-V / HAP:
Pd-V / HAP was similarly obtained except having replaced Pt (acac) ₂ by NE CHEMCAT Co., Ltd. of Production Example 1 with Pd (acac) ₂ of Sigma Aldrich. Palladium (Pd) as a metal: the molar ratio [Pd: V] = 6: 7, and the amount of palladium as a metal is 3.2 wt% in terms of the number of moles of vanadium (V) as a metal I understand.

Production example 11
Preparation of Ru-V / HAP:
Ru-V / HAP was obtained in the same manner as in Production Example 1 except that Pt (acac) ₂ manufactured by NE Chemcat Co., Ltd. was replaced with Ru (acac) ₃ manufactured by NE Chemcat Co., Ltd. Ruthenium (Ru) as a metal: the molar ratio [Ru: V] = 6: 7, and the amount of ruthenium as a metal is 3.0 wt% in terms of the number of moles of vanadium (V) as a metal I understand.

Production example 12
Preparation of Rh-V / HAP:
Rh-V / HAP was obtained in the same manner as in Production Example 1 except that Pt (acac) ₂ manufactured by N.E. Chemcat Co., Ltd. was changed to Rh (acac) ₃ manufactured by Mitsutsu Kagaku Co., Ltd. Rhodium (Rh) as metal: molar ratio [Rh: V] = 6: 7 in terms of the number of moles of vanadium (V) as metal, and the amount of rhodium as metal is 3.1 wt% I understand.

Production example 13
Preparation of Pt / HAP:
Pt / HAP was similarly obtained except that VO (acac) ₂ in Production Example 1 was removed. The amount of platinum as metal was found to be 5.8 wt%.

Production example 14
Preparation of V / HAP:
V / HAP was obtained in the same manner as in Production Example 1 except that Pt (acac) ₂ manufactured by N.E. Chemcat Inc. was removed. The amount of vanadium as metal was found to be 1.8 wt%.

Example 1
Catalysts obtained in Preparation Examples 1 to 14 were each made of stainless steel in a catalytic amount of Table 1, 5 mL of solvent 1,2-dimethoxyethane (DME), and 50 mL of N-acetylmorpholine as substrate 50 mL of 50 mL. The hydrogenation reaction was carried out under the conditions of Table 1 after being added to the autoclave. After the reaction, the yield of 2 was measured using a gas chromatograph. The results are shown in Table 1.

It has been found that the catalyst supporting at least both platinum and vanadium can carry out the hydrogenation reaction of the amide compound under mild conditions. Moreover, it turned out that Pt-V / HAP can perform the hydrogenation reaction of an amide compound with sufficient yield on mild conditions. Further, it was found that Pt-Ru-V / TiO ₂ also without problems reaction proceeds.

Example 2
The Pt-V / HAP obtained in Preparation Example 1 was added to a 50 mL stainless steel autoclave by adding the catalytic amount of Table 2, 0.5 mmol of the substrate, and 0.5 mg of molecular sieves of Wako Pure Chemical Industries, Ltd. After adding 5 mL of 1,2-dimethoxyethane (DME), the hydrogenation reaction was carried out at a reaction temperature of 70 ° C. under a hydrogen pressure of 3 MPa. After the reaction, the yield of 4 was measured using a gas chromatograph. The results are shown in Table 2.

  It was found that Pt-V / HAP can carry out the hydrogenation reaction of an amide compound with good yield under mild conditions even if the substrate changes.

Example 3
Catalyst reuse:
After the reaction of Example 1, the used Pt-V / HAP was separated by centrifugation, washed with a solvent 1,2-dimethoxyethane (DME) and recovered from the reaction system. The recovered Pt-V / HAP was again used for the same reaction. The results are shown in Table 3.

  It was found that Pt-V / HAP can be reused without degradation of performance.

Example 4
The Pt-V / HAP obtained in Preparation Example 1 was added to a 50 mL stainless steel autoclave by adding 0.1 g of a catalyst and 0.5 mmol of a substrate, and molecular sieves 4 Å of Wako Pure Chemical Industries, Ltd .: 0.1 g, respectively. Then, 5 mL of 2-dimethoxyethane (DME) was added to carry out a hydrogenation reaction under the reaction temperature and hydrogen pressure described in Table 4. After the reaction, the yield of 4 was measured using a gas chromatograph. The results are shown in Table 4.

  It was found that Pt-V / HAP was able to perform the hydrogenation reaction of an amide compound with good yield under mild conditions even if the substrate, hydrogen pressure or reaction temperature changed.

The catalyst of the present invention is useful for safely producing, under mild conditions, amino compounds useful in various medicines, agricultural chemicals, and various other industrial fields. In addition, the catalyst of the present invention can be manufactured inexpensively and safely.
that's all

Claims (20)

  A catalyst for the hydrogenation reaction of an amide compound, wherein platinum and vanadium are supported on a carrier.   The catalyst for hydrogenation reaction of an amide compound according to claim 1, wherein the support comprises at least one of hydroxyapatite, titania, alumina, silica and carbon.   The catalyst for hydrogenation reaction of an amide compound according to claim 1, wherein the support is hydroxyapatite.   The catalyst for hydrogenation reaction of an amide compound according to any one of claims 1 to 3, wherein the amide compound is a secondary or higher amide compound or an amide compound containing an aromatic substituent.   Furthermore, ruthenium is supported, The catalyst for hydrogenation reaction of the amide compound in any one of Claims 1-4.   A method for producing an amine compound comprising contacting an amide compound with the catalyst for hydrogenation reaction of an amide compound according to any one of claims 1 to 5 and hydrogenating the catalyst to obtain an amine compound.   The method for producing an amine compound according to claim 6, wherein the hydrogenation is performed at 100 ° C or less.   8. The method for producing an amine compound according to claim 6, wherein the hydrogenation is performed at 5 MPa or less.   The method for producing an amine compound according to any one of claims 6 to 8, wherein the amide compound is a secondary or higher amide compound or an amide compound containing an aromatic substituent.   The amine compound manufactured by the manufacturing method of the amine compound in any one of Claims 6-9.   The method for producing a catalyst for a hydrogenation reaction of an amide compound according to any one of claims 1 to 4, wherein platinum and vanadium are supported on a carrier in a solvent and then dried.   A method for producing a catalyst for a hydrogenation reaction of an amide compound according to claim 11, wherein platinum and vanadium are supported on the carrier by mixing the carrier and a solvent mixture liquid containing a platinum compound and a vanadium compound in a solvent. .   12. The amide according to claim 11, wherein platinum and vanadium are supported on the carrier by mixing the carrier, the solvent liquid containing the platinum compound, and the solvent liquid containing the vanadium compound in any order. Process for producing a catalyst for hydrogenation reaction of a compound.   The method for producing a catalyst for hydrogenation reaction of an amide compound according to any one of claims 11 to 13, wherein the solvent is water.   The method for producing a catalyst for a hydrogenation reaction of an amide compound according to any one of claims 11 to 14, wherein the support comprises at least one of hydroxyapatite, titania, alumina, silica and carbon.   6. The method for producing a catalyst for a hydrogenation reaction of an amide compound according to claim 5, wherein platinum, vanadium and ruthenium are supported on a carrier in a solvent and then dried.   17. The hydrogenation reaction of an amide compound according to claim 16, wherein the support is mixed with a solvent mixture containing a platinum compound, a vanadium compound and a ruthenium compound to support platinum, vanadium and ruthenium on the support in a solvent. For producing a catalyst   A carrier, a solvent liquid containing a platinum compound, a solvent liquid containing a vanadium compound, and a solvent liquid containing a ruthenium compound are mixed in any order, and platinum, vanadium and ruthenium are used as a carrier in a solvent. The method for producing a catalyst for hydrogenation reaction of an amide compound according to claim 16, which is supported.   The method for producing a catalyst for hydrogenation reaction of an amide compound according to any one of claims 16 to 18, wherein the solvent is water.   The method for producing a catalyst for hydrogenation reaction of an amide compound according to any one of claims 16 to 19, wherein the support comprises at least one of hydroxyapatite, titania, alumina, silica and carbon.