CN117003663A - Catalytic hydrogenation reaction and application of manganese-based catalyst - Google Patents

Catalytic hydrogenation reaction and application of manganese-based catalyst Download PDF

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CN117003663A
CN117003663A CN202310944715.1A CN202310944715A CN117003663A CN 117003663 A CN117003663 A CN 117003663A CN 202310944715 A CN202310944715 A CN 202310944715A CN 117003663 A CN117003663 A CN 117003663A
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compound
manganese
general formula
catalyst
hydrogen
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李浩然
朱俊
王永涛
王钰
吴雷
王闯
文泽昱
姚加
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Zhejiang University ZJU
Zhejiang NHU Co Ltd
Shandong Xinhecheng Fine Chemical Technology Co Ltd
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Zhejiang University ZJU
Zhejiang NHU Co Ltd
Shandong Xinhecheng Fine Chemical Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
    • 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
    • B01J31/20—Carbonyls
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a catalytic hydrogenation reaction and application of a manganese-based catalyst, in particular to a catalytic hydrogenation reaction of urea or a derivative thereof or a carbamate compound by using a manganese-based multi-tooth ligand compound. And for the first time a new use of manganese-based multidentate ligand compounds for the above reactions has been proposed.

Description

Catalytic hydrogenation reaction and application of manganese-based catalyst
Technical Field
The invention belongs to the field of fine chemical industry, relates to a preparation method for preparing an amide compound by catalytic hydrogenation, in particular to a method for synthesizing the amide compound by catalytic hydrogenation by using a manganese-based catalyst, and also relates to a novel application of the manganese-based catalyst.
Background
Excessive consumption of fossil energy results in excessive carbon dioxide (CO 2 ) Emissions, in turn, cause serious environmental problems, thus CO 2 Is receiving a great deal of attention. To date, only a few CO 2 The process as C1 building block is industrialised and is mainly used for urea (Bosch-Meiser process) and aminomethylAcid ester production.
However, compared to annual emissions of 300 billion tons worldwide, CO 2 The amount of chemical utilization of (c) is still very limited. It has been reported that the further hydrogenation of urea and its derivatives to high value-added chemicals is an indirect expansion of CO 2 Feasible way of resource utilization.
Further carboxamide compounds are a widely used class of chemicals in industry, which are solvents and raw materials for the synthesis of other chemicals.
Traditionally, the synthesis of N-formamide involves the use of stoichiometric amounts of coupling reagents such as chloral, formic acid, formaldehyde or formate, producing large amounts of waste, resulting in poor atomic economy. Industrially, the formamide is prepared from NaOCH in methanol 3 Catalytic amines are produced by reaction with toxic and flammable CO. The process has the defects of harsh reaction conditions, higher energy consumption and the like, and is not in line with the green chemical process.
In addition, the direct catalytic synthesis of N-formamide from amine compounds and carbon dioxide in the presence of a catalyst has become a very interesting field because of high atomic efficiency and environmental friendliness. One of the most challenging aspects for the direct use of carbon dioxide as a source of carbonyl is its thermodynamic and kinetic stability. Therefore, in order to make CO 2 Activation occurs, a certain amount of energy must be supplied or highly active agents must be used. While amine compounds can be combined with CO 2 To form C-N bond to generate urea derivative body, reduce CO 2 Activation energy of reduction. Thus, the hydrogenation of urea derivatives to formamide is an attractive indirect mild utilization of CO 2 Is a method of (2).
Further, klankermayer and Leitner research team (cited document 1) have reported successively a reaction of catalyzing hydrogenation of urea derivatives to formamide using ruthenium-based catalysts.
It is also known that in the field of homogeneous catalytic hydrogenation of ester compounds, many transition metal catalysts have emerged (cited document 3), including noble metal catalysts such as ruthenium, osmium, iridium, and high-yield metal catalysts such as iron, cobalt, and manganese. The ligands in the metal catalyst are greatly expanded, and a series of tridentate pincerlike ligands comprising diethylamine, pyridine and the like as frameworks, tetradentate ligands with bipyridine and pyridine frameworks, and types of bidentate ligands such as diamine, aminophosphine, pyridinamine, amine carbene and the like are presented. Thus, the efficiency of homogeneous catalytic hydrogenation of the ester compounds is also significantly improved.
Citation literature:
citation 1: vom Stein, t.; meuresch, M.; limper, d.; schmitz, m.; holscher, m.; coetzee, j.; cole-Hamilton, d.j.; klankermayer, j.; leitner, W.highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex: molecular control over selectivity and substrate scope. J.am. Chem. Soc.2014,136 (38), 13217-13225.
Citation 2: zhu, j.; zhang, y; wen, z.; ma, q; wang, y; yao, j.; li, H.Highly Efficient Ruthenium-Catalyzed Semihydrogenation of Urea Derivatives to formamides chem. Eur. J.2023, e202300106.
Citation 3: "progress of research on homogeneous catalytic hydrogenation of esters", gu Xuesong et al, chemistry report, 2019, vol.77, pp598-612.
Disclosure of Invention
Problems to be solved by the invention
In practical production processes, for example for the hydrogenation of urea derivatives, it has been found that urea derivatives are stable due to the additional resonance of the second nitrogen atom, the carboxamide products are more easily hydroconverted than urea derivatives, which makes the semi-hydrogenation of urea derivatives challenging. And there is less research on this problem. Although some progress has been made in this reaction, noble metal ruthenium is used as the catalytically active metal, for example, the above-mentioned cited documents 1 to 2, but there are problems that the noble metal catalyst is costly and has limited usability. Further, although reference 3 has attempted a larger number of metal catalysts having ligands, only homogeneous catalytic hydrogenation of ester compounds has been performed, and there has been no report of attempts to hydrogenate urea derivatives.
Manganese is the third most abundant transition metal in the crust, next to iron and titanium, as there is great interest in developing catalysts based on abundant non-noble metals. Thus, the present invention provides a catalytic hydrogenation reaction from earth-abundant manganese metal complexes. The reaction is carried out in the presence of the manganese-based multi-tooth ligand compound serving as a catalyst, so that compared with the prior noble metal material, the cost of the catalyst is reduced, and the catalyst has excellent catalytic selectivity and efficiency.
Furthermore, the invention also provides a new application of the manganese-based multi-tooth ligand compound for the first time, namely a catalyst for catalytic hydrogenation reaction of the compound of the general formula (1).
Based on the above, the invention also provides a new way for recycling carbon dioxide.
Solution for solving the problem
Through long-term research, the technical problems can be solved through implementation of the following technical scheme:
[1] the invention provides a catalytic hydrogenation method, which comprises the following steps:
a step of contacting a compound of the general formula (1) with hydrogen in the presence of a catalyst and a solvent,
and, in addition, the processing unit,
the compound of the general formula (1) has the following structure:
Wherein R is 1 、R 2 And R is 3 Each occurrence, identical or different, represents a monovalent organic group, and R 1 And R is 2 Can be connected into a ring; x represents a nitrogen atom or an oxygen atom; n represents a number of 1 or 2,
the catalyst is a manganese-based polydentate ligand compound,
the manganese-based polydentate ligand compound is derived from the combination of compounds including at least a manganese-based compound and a ligand structure having the following general formula (2):
(R 4 ) 2 Y-L-Q-L-Y(R 4 ) 2
(2)
wherein Q represents an organic group containing a nitrogen atom or a phosphorus atom, and the sum of the numbers of the nitrogen atom and the phosphorus atom in Q is 1 or 2;
l, which are identical or different at each occurrence, independently of one another represent a single bond or a divalent linking group;
y, which are identical or different for each occurrence, independently of one another represent a phosphorus atom or a nitrogen atom;
R 4 each occurrence, identical or different, represents, independently of the other, a monovalent organic group.
[2] The method according to [1], wherein the manganese-based compound comprises one or more of a manganese compound containing a carbonyl group and/or a halogen; the solvent is selected from one or more organic solvents sufficient to dissolve the catalyst.
[3]According to [1]]Or [2]]The method, wherein R in the general formula (1) 1 、R 2 And R is 3 Each independently selected from hydrogen, a linear, branched or cyclic hydrocarbyl group, optionally having an aromatic structure therein.
[4]According to [1]]～[3]The process according to any one of the above, wherein X in the formula (1) is an oxygen atom and R 3 Is not hydrogen.
[5] The method according to any one of [1] to [4], wherein the manganese-based compound is one or more of polycarbonyl manganese bromide or polycarbonyl manganese chloride.
[6] The method according to any one of [1] to [5], wherein the ligand structure of the general formula (2) comprises one or more of the following general formula (2-1) structure, general formula (2-2) structure or general formula (2-3) structure:
3-t (R 5 -)N(-L-Y(R 4 ) 2 ) t
(2-1)
3-t (R 5 -)P(-L-Y(R 4 ) 2 ) t
(2-3)
wherein t represents 2 or 3; r is R 5 Represents a monovalent organic group;
in the general formula (2-1), N represents a nitrogen atom;
in the general formula (2-2), the cyclic structure a represents a ring having an aromatic structure, N represents a nitrogen atom, and all three covalent bonds of the nitrogen atom are incorporated into the cyclic structure;
in the general formula (2-3), P represents a phosphorus atom.
[7] The method according to [6], wherein the cyclic structure A in the general formula (2-2) has 1 or more rings, and the rings are linked by a single bond or share at least 1 carbon atom.
[8] The method according to any one of [1] to [7], wherein L in the general formula (2) is a hydrocarbon group having 1 to 6 carbon atoms.
[9]According to [1]]～[8]The process according to any one of the above, wherein Y in the general formula (2) is a phosphorus atom, R 4 Is a hydrocarbon group having a straight chain, branched chain or aromatic structure having 1 to 12 carbon atoms.
[10] The process according to any one of [1] to [9], wherein the compound of the general formula (1) is reacted with the hydrogen gas at a temperature of 80 to 160℃and a pressure of 100bar or less.
[11] The method according to any one of [1] to [10], wherein the catalyst is used in an amount of 30 mol% or less based on the number of moles of the compound of the general formula (1) in terms of moles of manganese element.
[12] Use of a catalyst for catalytic hydrogenation to a compound of the general formula (1) in the process according to any one of the above [1] to [11], characterized in that the catalyst is a manganese-based polydentate ligand compound and the manganese-based polydentate ligand compound satisfies the definition of the manganese-based polydentate ligand compound according to the process according to any one of the above [1] to [11].
[13] A method of carbon dioxide utilization, wherein the method comprises:
carbon dioxide is used to synthesize a compound of the following general formula (1-1):
wherein R is 1 、R 2 And R is 3 Each occurrence, identical or different, represents, independently of the other, a monovalent organic group;
And further reacting the compound having the structure of the general formula (1-1) with hydrogen using the method involving the X being a nitrogen atom in the method according to any one of [1] to [11 ].
[14] The method according to [13], wherein the carbon dioxide is recycled carbon dioxide.
ADVANTAGEOUS EFFECTS OF INVENTION
By implementing the technical scheme, the invention can obtain the following technical effects:
1) The present invention provides a novel catalytic hydrogenation process for compounds of the general formula (1) wherein a novel (homogeneous) catalyst is used which is a multidentate ligand compound of a manganese-based compound with improved production costs compared to the noble metal catalysts previously used in the catalytic hydrogenation of the above-mentioned compounds.
2) The catalytic hydrogenation method has the advantages of high selectivity, mild reaction conditions, high atom economy, low-cost and easily-obtained catalytic active manganese metal, environmental friendliness and the like.
3) The invention provides a new catalytic application of the manganese-based polydentate ligand compound for the first time, and expands the industrial application range of the catalyst.
4) The present invention also provides a cheaper and viable method of recycling carbon dioxide.
Drawings
Fig. 1: example 1 MS-ESI spectrum of the catalytically active component detected in the reaction solution.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In the present specification, the use of "optional" or "optional" means that some substances, components, steps of execution, conditions of application, and the like may or may not be used, and the manner of use is not limited.
In the present specification, the use of "unsaturated structure" refers to a structure formed by carbon-carbon double bonds, unless otherwise specifically indicated.
In the present invention, "hydrogen atom" is included in the use of "monovalent organic group".
In the present specification, "hydrocarbon group" is used to denote an organic structure formed of two elements of carbon and hydrogen, and may be an aromatic or non-aromatic group.
In the present specification, the use of "halogen" means fluorine, chlorine, bromine or iodine. Preferred are fluorine, chlorine or bromine, and more preferred are bromine and chlorine.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
The invention mainly provides a catalytic hydrogenation method of a compound with the structure shown in the following formula (1), for example, the compound with the structure shown in the formula (1) can be urea (or derivatives thereof) or carbamate compounds. Further, the compound is subjected to hydrogenation reaction with hydrogen under the catalysis of a manganese-based multi-tooth ligand compound, so that products such as amide compounds and the like can be obtained in an economic and efficient mode.
The invention is mainly based on the following findings:
although, for example, as described in reference 3, metal compounds having a multidentate ligand have been used for the homogeneous catalytic hydrogenation of ester compounds to synthesize alcohol compounds. Although it is possible to use a greater variety of metal complexes as catalysts, it involves selective catalytic cleavage of the C-O bond in-C-CO-O-. Therefore, it has not been reported that the catalyst thereof can be used for the hydrogenation of urea (or its derivative) or urethane compounds, especially considering that the catalyst commonly used in the latter is a limited noble metal-based catalyst and the resonance stabilization phenomenon of the nitrogen atom adjacent to the carbonyl group existing.
It has been unexpectedly found that when a manganese-based multidentate ligand compound is used as a catalyst to catalyze a compound of the structure of the general formula (1), it is possible to have good catalytic selectivity, thus enabling to increase the yield of the product, and also to have good catalytic activity even under milder conditions, significantly reducing the cost of the catalytic process.
(reaction raw materials)
The reaction raw material or the catalytic hydrogenation object of the present invention is urea or a derivative thereof or a carbamate compound used in the art.
In some embodiments of the present invention, the compound of the reaction raw material may be one or more of compounds having the structure of the following formula (1).
Wherein R is 1 、R 2 And R is 3 Each occurrence, identical or different, represents a monovalent organic group, and R 1 And R is 2 May be connected in a ring.
The monovalent organic group is not particularly limited in principle, and may be selected and used according to the kind of compounds existing in the art. In some specific embodiments, the monovalent organic group may be selected from a hydrogen atom, a straight or branched chain or a hydrocarbon group having a cyclic structure, a hydrocarbon group having an unsaturated structure (or an aromatic structure), and these hydrocarbon groups may have optional substituents, preferably, these substituents may be halogen or a halogen-containing group; alternatively, the carbon atoms in the above hydrocarbon groups may be substituted with other N, O or S atoms.
In some preferred embodiments, the monovalent organic group may be selected from hydrogen atoms, linear, branched, cyclic, saturated or unsaturated hydrocarbon groups of 1 to 25 carbon atoms (preferably 1 to 15), optionally with halogen-containing substituents or optionally with carbon aromatic or heteroaromatic structures in the structure.
In some more preferred embodiments, the monovalent organic group may be selected from one or more of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl), cycloalkyl (4 to 6 membered ring), phenyl, pyridyl, imidazolyl, and these groups optionally have an alkyl group, a substituent containing a halogen group, such as one or more of a chlorine atom, a fluorine atom, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, and the like.
For X in the structure of the general formula (1), it may represent a nitrogen atom or an oxygen atom. When X represents a nitrogen atom, the compound of the structure of the general formula (1) may be urea or a derivative thereof having the structure of the following general formula (1-1); when X represents an oxygen atom, the compound of the structure of the general formula (1) may be a carbamate compound having the structure of the following general formula (1-2):
for n, it can be selected according to the case of X, and thus n can be 1 or 2.
In addition, in the case of the general formula (1-2), it is preferable that the R 3 Not a hydrogen atom.
Further, as preferable reaction raw materials of the present invention, there may be mentioned compounds comprising the following structures:
(catalyst)
The catalyst for catalytic hydrogenation of the compound with the general formula (1) can be one or more of manganese-based multi-tooth ligand compounds. The manganese-based polydentate ligand compound may be derived from the combination of components comprising at least a manganese-based compound and a polydentate ligand compound.
In some specific embodiments of the present invention, the manganese-based compound comprises one or more of a manganese compound containing carbonyl and/or halogen, and in some preferred embodiments, the manganese-based compound may be selected from manganese pentacarbonyl bromide (Mn (CO) 5 Br), cyclopentadienyl manganese tricarbonyl, 2-methylcyclopentadienyl manganese tricarbonyl, mnCl 2 Mn (CO) is preferred 5 Br。
Further, the multidentate ligand compound includes one or more of compounds having a ligand structure of the following general formula (2):
(R 4 ) 3 Y-L-Q-L-Y(R 4 ) 3
(2)
wherein the compound with the structure of the general formula (2) is a ligand with more than three teeth, preferably a tridentate ligand or a tetradentate ligand. The Q is an organic group containing a nitrogen atom or a phosphorus atom, and the total number of the nitrogen atom and the phosphorus atom is 1 or 2.Y, which are identical or different at each occurrence, independently of one another represent a phosphorus atom or a nitrogen atom, and preferably are each a phosphorus atom.
As regards L mentioned above, it represents a single bond or a divalent linking group, and there is in principle no particular limitation on the divalent linking groups that can be used for L, and linking groups that are usual in the art can be used, and in some preferred embodiments the divalent groups can be hydrocarbon groups having from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms.
For R 4 Which are identical or different at each occurrence and which independently represent a monovalent organic group, in some embodiments each R 4 Independently of each other, a hydrocarbon group having a linear, branched or aromatic structure having 1 to 20 carbon atoms, preferably 2 to 15 or 3 to 10 carbon atoms.
In a further specific embodiment of the present invention, the ligand of the structure of formula (2) comprises one or more of the following structures of formula (2-1), formula (2-2) or formula (2-3):
3-t (R 5 -)N(-L-Y(R 4 ) 2 ) t
(2-1)
3-t (R 5 -)P(-L-Y(R 4 ) 2 ) t
(2-3)
wherein, for the structure of the general formula (2-1), R 5 Represents a monovalent organic group, preferably R 5 And is identical or different on each occurrence and represents a hydrogen atom or a hydrocarbon radical of linear, branched or aromatic structure having a number of carbon atoms ranging from 1 to 20, preferably from 2 to 15 or from 3 to 10; t represents 2 or 3; n represents a nitrogen atom.
With respect to the structure of the general formula (2-2), wherein, with respect to the above-mentioned cyclic structure a, it represents a ring having an aromatic structure, and all three bonds of the nitrogen atom represented by N are incorporated into the cyclic structure of the ring, preferably, the N-incorporated ring (ring of the smallest unit) is an aromatic structure nitrogen heterocycle.
In other specific embodiments, the cyclic structure a has 4 to 20, preferably 6 to 18, ring carbon atoms, and for such cyclic structures may be composed of one or more rings which may be linked by single bonds or share at least one carbon atom, for example, forming the cyclic structure a in a parallel ring fashion. In a further preferred embodiment, the cyclic structure a may be a structure derived from (poly) benzopyridine, (poly) benzopyrrole with pyridine, pyrrole, and these structures may optionally further have substituents such as alkyl group.
For the structure of the general formula (2-3), R 5 Represents a monovalent organic group having the same definition as the general formula (2-1), preferably R 5 A hydrocarbon group having a linear, branched or aromatic structure, which represents a hydrogen atom or a carbon number of 1 to 20, preferably 2 to 15 or 3 to 10; t represents 2 or 3; p represents a phosphorus atom.
From the viewpoint of improving the conversion rate of the catalyst hydrogenation reaction described below, the compound of the structure of the general formula (2-2) is preferable as the ligand compound forming the catalyst of the present invention.
(formation of catalyst)
The catalyst of the present invention can be obtained by reacting a manganese-based compound with a multidentate ligand compound having the structure of the general formula (2) under alkaline conditions. The base that can be used is not particularly limited, and may be generally an organic base or an inorganic base. In some preferred embodiments, the base may be selected from KO t Bu、NaHBEt 3 、KOH、NaOH、Cs 2 CO 3 、Na 2 CO 3 、NaHCO 3 Any one or more of them, more preferably KO t Bu。
It is mainly explained that, with respect to the above catalyst, the catalyst may be added to a subsequent hydrogenation reaction system after the formation of the complete catalyst, or the above manganese-based compound, the multidentate ligand compound having the structure of the above general formula (2), and the above base may be directly added to a reaction vessel, and then the reactants of the hydrogenation reaction may be added in situ in the vessel after the formation of the catalyst.
In some specific embodiments, the molar ratio of manganese-based compound, ligand of the structure of formula (2) above, to the base may be 1.0: (0.01-10): (0.01 to 10), preferably 1.0: (1-3): (1-3).
In addition, any desired formation of the catalyst may be performed in the presence of a solvent, and the solvent may be the same as the solvent used in the catalytic hydrogenation reaction described below.
(catalytic hydrogenation reaction)
The catalytic hydrogenation reaction of the present invention is a catalytic hydrogenation of a compound of the general formula (1) by contacting with hydrogen in the presence of a solvent to give the desired product.
For the catalytic hydrogenation reaction of the present invention, according to the difference of X in the compound of the general formula (1), it can be carried out as follows:
In the case of the mode (a), a carboxamide compound and an amine compound can be obtained, and in the case of the mode (b), a corresponding alcohol can be obtained in addition to the carboxamide compound. In some preferred embodiments, the carboxamide compound comprises p-halophenyl formamide.
In addition, with the embodiment (a), since the reaction raw materials have symmetrical and asymmetrical structures, one or two different carboxamide compounds can be obtained.
There is no particular limitation on the solvent that can be used, as long as it is sufficient to dissolve the catalyst. In some specific embodiments, the solvent may include one or more of an azacyclic solvent, an oxacyclic solvent, a benzene solvent, or a sulfone solvent, and more specifically, the solvent may be one or more of 1, 4-dioxane, toluene, tetrahydrofuran, and dimethyl sulfoxide, and particularly preferably 1, 4-dioxane is used as the solvent.
For the reaction conditions, it is possible to carry out the reaction under high pressure, in some specific embodiments at a pressure of 100bar or less, preferably 20 to 90bar, more preferably 40 to 80bar, most preferably 55 to 70bar. Thus, the hydrogenation reaction may be carried out in an autoclave.
In the hydrogenation step, the reaction temperature is not particularly limited in principle, and may be dependent on the kind of the reaction raw material, and may be generally 160℃or less, preferably 80 to 140℃and more preferably 105 to 120 ℃.
Further, in the catalytic hydrogenation reaction, the catalyst is used in an amount of 30 mol% or less, preferably 0.1 to 25 mol%, more preferably 0.5 to 15 mol%, and still more preferably 1 to 5 mol% based on the mole number of manganese element in the catalyst.
The reaction time is not particularly limited, and may be usually 8 to 60 hours, preferably 10 to 50 hours, and more preferably 10 to 20 hours.
For the catalytic hydrogenation reaction of the present invention, in some preferred embodiments, it may have a yield of 28 mass% or more, preferably 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, etc., and for its conversion, it may be preferably 90 mass% or more, more preferably 95 mass% or more.
(recovery and utilization of carbon dioxide)
Further, the present invention also provides a method for utilizing carbon dioxide, and in particular, the carbon dioxide may be carbon dioxide recovered from the environment by adsorption or the like.
The method comprises the following steps:
the above carbon dioxide is used to synthesize a compound having the structure of the following formula (1-1):
wherein R is 1 、R 2 And R is 3 Each occurrence, identical or different, represents, independently of the other, a monovalent organic group, which is as defined for formula (1) above.
Further, the compound of the structure of the general formula (1-1) is further reacted with hydrogen using the catalytic hydrogenation method as described above.
Examples
Embodiments of the present invention will be described in detail below with reference to examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
At N 2 In an atmospheric glove box, 0.01mmol of Mn (CO) 5 Br, 0.015mmol KO t Bu and 0.015mmol of the different ligands 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine, 2, 6-bis ((di-t-butylphosphino) methyl) pyridine, bis (2- (di-t-butylphosphinoalkyl) ethyl) amine hydrochloride, ((phenylphosphinodi) bis (ethane-2, 1-diyl)) bis (diphenylphosphine) and tris (2- (diphenylphosphino) ethyl) phosphine were each charged into a 50mL autoclave charged with 2mL of tetrahydrofuran solvent. Stirring was carried out for about 5min, and 1mmol of 1, 3-bis (4-chlorophenyl) urea was added.
Taking out the sealed autoclave from the glove box, flushing the autoclave with hydrogen for 4-6 times (the hydrogen pressure is firstly filled to 50bar and then released to about 2bar, the autoclave is circularly operated for 4-6 times), and finally pressurizing the autoclave to 50bar respectively, and stirring and heating the autoclave at 140 ℃ respectively to carry out hydrogenation reaction. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, conversion and yield are shown in table 1.
The qualitative and quantitative method of the product in the invention is based on gas chromatography-temperature programming detection (chem. Eur. J.2023, e 202300106), and the instrument used is GC-2010 (Shimadzu, japan) HP-1 chromatographic column.
TABLE 1 conversion of 1, 3-bis (4-chlorophenyl) urea and yield of formamide with different ligands
As can be seen from the comparison of the results in Table 1, the use of various ligands can show industrial usefulness even without excessive optimization of the reaction conditions.
Example 2
At N 2 In an atmospheric glove box, 0.01mmol of Mn (CO) 5 Br, 0.015mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand and 0.015mmol KO t Bu was added to a 50mL autoclave charged with 2mL of tetrahydrofuran, toluene and 1, 4-dioxane solvent, respectively. Stirring was carried out for about 5min, and 1mmol of 1, 3-bis (4-chlorophenyl) urea was added. Taking out the sealed autoclave from the glove box, flushing the autoclave with hydrogen for 4-6 times (the hydrogen pressure is firstly filled to 50bar and then released to about 2bar, the autoclave is circularly operated for 4-6 times), and finally pressurizing the autoclave to 50bar respectively, and stirring and heating the autoclave at 140 ℃ respectively to carry out hydrogenation reaction. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, conversion and yield are shown in table 2.
TABLE 2 conversion of 1, 3-bis (4-chlorophenyl) urea and yield of formamide in various solvents
As can be seen from a comparison of the results in Table 2, the hydrogenation of 1, 3-bis (4-chlorophenyl) urea in different solvents was generally satisfactory, although the yield of formamide had some fluctuation.
Example 3
At N 2 In a glove box with atmosphere, 0.01mmol of Mn (CO) 5 Br, 0.015mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, 0.015mmol KO t Bu and 2mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring was carried out for about 5min, and 1mmol of 1, 3-bis (4-chlorophenyl) urea was added. Taking out the sealed high-pressure reaction kettle from the glove box, flushing the high-pressure reaction kettle with hydrogen for 4-6 times (firstly filling the hydrogen pressure to 50bar, then releasing the hydrogen pressure to about 2bar, circularly operating for 4-6 times), finally respectively pressurizing the high-pressure reaction kettle to 60bar, and respectively stirring and heating the high-pressure reaction kettle at 140, 120, 110 and 100 ℃ to carry out hydrogenation reaction. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, conversion and yield are shown in table 3.
TABLE 3 conversion of 1, 3-bis (4-chlorophenyl) urea and yield of formamide at various reaction temperatures
Example 4
At N 2 In an atmospheric glove box, 0.01mmol of Mn (CO) 5 Br, 0.015mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, 0.015mmol KO t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring was carried out for about 5min, and 2mmol of 1, 3-bis (4-chlorophenyl) urea was added. Taking out the sealed autoclave from the glove box, flushing the autoclave with hydrogen for 4-6 times (the hydrogen pressure is firstly filled to 50bar and then released to about 2bar, the autoclave is circularly operated for 4-6 times), and finally pressurizing to 30, 40 and 50bar respectively, and stirring and heating the autoclave at 110 ℃ to carry out hydrogenation reaction. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, conversion and yield are shown in table 4.
TABLE 4 different H 2 Conversion of 1, 3-bis (4-chlorophenyl) urea under pressure and yield of formamide
As can be seen from comparison of the results in Table 4, H 2 The pressure has the same effect on the conversion efficiency of 1, 3-bis (4-chlorophenyl) urea as in the prior art when other catalysts are used.
Example 5
At N 2 In an atmospheric glove box, 0.01mmol of Mn (CO) 5 Br, 0.015mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand and 0.015mmol of different additives KOtBu, cs 2 CO 3 Or NaHCO 3 Into a 50mL autoclave equipped with 4mL of 1, 4-dioxane, respectively. Stirring was carried out for about 5min, and 2mmol of 1, 3-bis (4-chlorophenyl) urea was added. Taking out the sealed autoclave from the glove box, flushing the autoclave with hydrogen for 4-6 times (the hydrogen pressure is firstly filled to 60bar and then released to about 2bar, the autoclave is circularly operated for 4-6 times), and finally pressurizing the autoclave to 50bar respectively, and stirring and heating the autoclave at 110 ℃ respectively to carry out hydrogenation reaction. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, conversion and yield are shown in table 5.
TABLE 5 conversion of 1, 3-bis (4-chlorophenyl) urea and yield of formamide with the addition of various bases
Example 6
At N 2 In an atmospheric glove box, 0.01mmol of Mn (CO) 5 Br, 0.015mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, 0.015mmol KO t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring was carried out for about 5min, and 2mmol of 1, 3-bis (4-fluorophenyl) urea was added. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 24h. After the reaction was completed, the mixture was placed in an ice bath Cooled for about 30 minutes and then slowly vented to atmospheric pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Example 7
In a glove box with N2 atmosphere, 0.01mmol of Mn (CO) 5 Br, 0.015mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, 0.015mmol KO t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring was carried out for about 5min, and 2mmol of 1, 3-bis (3, 4-dichlorophenyl) urea was added. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 12h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Example 8
At N 2 In an atmospheric glove box, 0.01mmol of Mn (CO) 5 Br, 0.015mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, 0.015mmol KO t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring for about 5min, adding 2mmol of 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] ]Urea. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 12h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Example 9
At N 2 In an atmospheric glove box, 0.02mmol of Mn (CO) 5 Br, 0.03mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, 0.03mmol NaHBEt 3 4mL of 1, 4-dioxane solvent was added to a 50mL autoclave. Stirring for about 5min, 2mmol of 1, 3-diphenylurea was added. From glove boxThe sealed autoclave was taken out, flushed with hydrogen 4-6 times (hydrogen pressure was first charged to 50bar, then released to about 2bar, and the operation was cycled 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 48h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Example 10
At N 2 In an atmospheric glove box, 0.02mmol of Mn (CO) 5 Br, 0.03mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, KO of 0.03mmol t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring is carried out for about 5min, and 2mmol of 1, 3-bipyridin-2-yl urea are added. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 48h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Example 11
At N 2 In an atmospheric glove box, 0.03mmol of Mn (CO) 5 Br, 0.045mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, KO of 0.045mmol t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring was carried out for about 5min, and 2mmol of 1, 3-bis (4-methylphenyl) urea was added. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 48h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Example 12
At N 2 In an atmospheric glove box, 0.03mmol of Mn (CO) 5 Br, 0.045mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, KO of 0.045mmol t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring for about 5min, and adding 2mmol of 1, 3-dicyclohexylurea. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 48h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Example 13
At N 2 In an atmospheric glove box, 0.04mmol of Mn (CO) 5 Br, 0.06mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, 0.06mmol KO t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring is carried out for about 5min, and 2mmol of 1, 3-dibutylurea are added. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 48h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Example 14
At N 2 In an atmospheric glove box, 0.02mmol of Mn (CO) 5 Br, 0.03mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, KO of 0.03mmol t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring was carried out for about 5min, and 2mmol of 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea was added. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110℃for 24h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. Adding an internal standardBiphenyl was sampled for GC detection and yields are shown in table 6.
Example 15
At N 2 In an atmospheric glove box, 0.02mmol of Mn (CO) 5 Br, 0.03mmol of 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine ligand, KO of 0.03mmol t Bu and 4mL of 1, 4-dioxane solvent were added to a 50mL autoclave. Stirring was carried out for about 5min, and 2mmol of methyl N-phenylcarbamate was added. The sealed autoclave was taken out of the glove box, flushed with hydrogen 4-6 times (hydrogen pressure was first brought to 50bar, then released to around 2bar, and operated cyclically 4-6 times), finally pressurized to 60bar, and heated with stirring at 110 ℃ for 16h. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, the yields are shown in table 6.
Table 6: reaction conditions and yields of examples 6 to 15
As can be seen from the experimental results in Table 6, the in-situ manganese-based catalyst system has a wide application range for the hydrogenation of urea derivatives and carbamates.
Example 16
At N 2 In an atmospheric glove box, 0.01mmol of Mn (CO) 5 Br, 0.015mmol KO t Bu and 0.015mmol of the different ligands from Table 1 were each charged into a 50mL autoclave containing 2mL of tetrahydrofuran solvent. Stirring was carried out for about 5min, and 1mmol of 1, 3-bis (4-chlorophenyl) urea was added.
Taking out the sealed autoclave from the glove box, flushing the autoclave with hydrogen for 4-6 times (the hydrogen pressure is firstly filled to 50bar and then released to about 2bar, the autoclave is circularly operated for 4-6 times), and finally pressurizing the autoclave to 60bar respectively, and stirring and heating the autoclave at 110 ℃ respectively to carry out hydrogenation reaction. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, conversion and yield are shown in table 7.
The qualitative and quantitative method of the product in the invention is based on gas chromatography-temperature programming detection (chem. Eur. J.2023, e 202300106), and the instrument used is GC-2010 (Shimadzu, japan) HP-1 chromatographic column.
TABLE 7 conversion of 1, 3-bis (4-chlorophenyl) urea and yield of formamide for different ligands
Example 17
At N 2 In an atmospheric glove box, 0.01mmol of the Mn-based compound of Table 8 and 0.015mmol of KO were added t Bu and 0.015mmol of ligand 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine was added to a 50mL autoclave containing 2mL of tetrahydrofuran solvent, respectively. Stirring was carried out for about 5min, and 1mmol of 1, 3-bis (4-chlorophenyl) urea was added.
Taking out the sealed autoclave from the glove box, flushing the autoclave with hydrogen for 4-6 times (the hydrogen pressure is firstly filled to 50bar and then released to about 2bar, the autoclave is circularly operated for 4-6 times), and finally pressurizing the autoclave to 60bar respectively, and stirring and heating the autoclave at 110 ℃ respectively to carry out hydrogenation reaction. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, conversion and yield are shown in table 8.
The qualitative and quantitative method of the product in the invention is based on gas chromatography-temperature programming detection (chem. Eur. J.2023, e 202300106), and the instrument used is GC-2010 (Shimadzu, japan) HP-1 chromatographic column.
TABLE 8 conversion of 1, 3-bis (4-chlorophenyl) urea and yield of formamide for different ligands
Reference comparative example
At N 2 Atmosphere glove box, 0.01mmol of the metal precursor in Table 9, 0.015mmol of KO t Bu and 0.015mmol of ligand 2, 6-bis [ (diphenylphosphino) methyl)]Pyridine was added to a 50mL autoclave containing 2mL of tetrahydrofuran solvent, respectively. Stirring was carried out for about 5min, and 1mmol of 1, 3-bis (4-chlorophenyl) urea was added.
Taking out the sealed autoclave from the glove box, flushing the autoclave with hydrogen for 4-6 times (the hydrogen pressure is firstly filled to 50bar and then released to about 2bar, the autoclave is circularly operated for 4-6 times), and finally pressurizing the autoclave to 60bar respectively, and stirring and heating the autoclave at 110 ℃ respectively to carry out hydrogenation reaction. After the reaction was completed, the mixture was cooled in an ice bath for about 30 minutes, and then slowly vented to normal pressure. The internal standard biphenyl was added and sampled for GC detection, conversion and yield are shown in table 9.
The qualitative and quantitative method of the product in the invention is based on gas chromatography-temperature programming detection (chem. Eur. J.2023, e 202300106), and the instrument used is GC-2010 (Shimadzu, japan) HP-1 chromatographic column.
TABLE 9 conversion of 1, 3-bis (4-chlorophenyl) urea and yield of formamide with other metal precursors
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims (14)

1. A method of catalytic hydrogenation, the method comprising:
a step of contacting a compound of the general formula (1) with hydrogen in the presence of a catalyst and a solvent,
and, in addition, the processing unit,
the compound of the general formula (1) has the following structure:
wherein R is 1 、R 2 And R is 3 Each occurrence, identical or different, represents, independently of the other, a monovalent organic group; and R is 1 And R is 2 Can be connected into a ring; x represents a nitrogen atom or an oxygen atom; n represents a number of 1 or 2,
the catalyst is a manganese-based polydentate ligand compound,
the manganese-based polydentate ligand compound is derived from the combination of compounds including at least a manganese-based compound and a ligand structure having the following general formula (2):
(R 4 ) 2 Y—L-Q-L-Y(R 4 ) 2
(2)
wherein Q represents an organic group containing a nitrogen atom or a phosphorus atom, the sum of the numbers of nitrogen atoms and phosphorus atoms in Q is 1 or 2,
l, which are identical or different at each occurrence, independently of one another represent a single bond or a divalent linking group;
y, which are identical or different for each occurrence, independently of one another represent a phosphorus atom or a nitrogen atom;
R 4 each occurrence, identical or different, represents, independently of the other, a monovalent organic group.
2. The method of claim 1, wherein the manganese-based compound comprises one or more of a manganese compound comprising a carbonyl group and/or a halogen; the solvent is selected from one or more organic solvents sufficient to dissolve the catalyst.
3. The method according to claim 1 or 2, wherein R in the general formula (1) 1 、R 2 And R is 3 Each independently selected from hydrogen, a linear, branched or cyclic hydrocarbyl group, optionally having an aromatic structure therein.
4. A process according to any one of claims 1 to 3, wherein X in formula (1) is an oxygen atom and R 3 Is not hydrogen.
5. The method of any one of claims 1-4, wherein the manganese-based compound is one or more of a multicarbonyl manganese bromide or a multicarbonyl manganese chloride.
6. The method of any one of claims 1 to 5, wherein the ligand structure of formula (2) comprises one or more of the following formula (2-1), formula (2-2) or formula (2-3):
wherein t represents 2 or 3; r is R 5 Represents a monovalent organic group;
in the general formula (2-1), N represents a nitrogen atom;
in the general formula (2-2), the cyclic structure a represents a ring having an aromatic structure, N represents a nitrogen atom, and all three covalent bonds of the nitrogen atom are incorporated into the cyclic structure;
in the general formula (2-3), P represents a phosphorus atom.
7. The method according to claim 6, wherein the cyclic structure A in the general formula (2-2) has 1 or more rings, and the rings are linked by single bonds or share at least 1 carbon atom.
8. The method according to any one of claims 1 to 7, wherein L in the general formula (2) is a hydrocarbon group having 1 to 6 carbon atoms.
9. The method according to any one of claims 1 to 8, wherein Y in the general formula (2) is a phosphorus atom, R 4 Is a hydrocarbon group having a linear, branched or aromatic structure and having 1 to 20 carbon atoms.
10. The process according to any one of claims 1 to 9, wherein the compound of formula (1) is reacted with the hydrogen gas at a temperature of 80 to 160 ℃ and a pressure of 100bar or less.
11. The method according to any one of claims 1 to 10, wherein the catalyst is used in an amount of 30 mol% or less based on the number of moles of the compound of the general formula (1) in terms of moles of manganese element.
12. Use of a catalyst for catalytic hydrogenation of a compound of the general formula (1) according to any one of claims 1 to 11, characterized in that the catalyst is a manganese-based polydentate ligand compound and that the manganese-based polydentate ligand compound fulfils the definition of the manganese-based polydentate ligand compound according to the method according to any one of claims 1 to 11.
13. A method for utilizing carbon dioxide, the method comprising:
carbon dioxide is used to synthesize a compound of the following general formula (1-1):
wherein R is 1 、R 2 And R is 3 Each occurrence, identical or different, represents, independently of the other, a monovalent organic group;
and further reacting the compound having the structure of the general formula (1-1) with hydrogen using the method involving the X being a nitrogen atom in the method according to any one of claims 1 to 11.
14. The method of claim 13, wherein the carbon dioxide is recycled carbon dioxide.
CN202310944715.1A 2023-07-28 2023-07-28 Catalytic hydrogenation reaction and application of manganese-based catalyst Pending CN117003663A (en)

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