Catalyst, method for producing formamides and / or amines, method for producing formamides and / or alcohols, and complex

Abstract

The present invention addresses the problem of providing a new catalyst for selectively generating formamides from urea-based compounds and urethane-based compounds. The present invention pertains to: a complex having a partial structure represented by formula (A); and a catalyst including the complex. The present invention also pertains to: a method that is for producing formamides and / or amines and that includes causing the catalyst to act on a urea-based compound; and a method that is for producing formamides and / or alcohols and that includes causing the catalyst to act on a urethane-based compound.

Description

Catalyst, method for producing formamides and / or amines, method for producing formamides and / or alcohols, and complex

[0001] The present invention relates to a catalyst, a method for producing formamides and / or amines, a method for producing formamides and / or alcohols, and a complex.

[0002] Conventionally, catalysts using organometallic complexes that promote catalytic hydrogenation reactions of carbonyl compounds have been known. For example, Non-Patent Document 1 discloses a ruthenium complex as a catalyst for hydrogenating carbonyl compounds. The ruthenium complex promotes the hydrogenation reaction of carbonyl compounds, ultimately producing alcohols and amines. Patent Document 1 also discloses a method for reducing carbonyl compounds with a reducing agent in the presence of an organometallic complex having a predetermined structure, and describes that alcohols and amines are obtained as products.

[0003] In recent years, formamide and its derivatives have been widely used as basic raw materials in the organic chemical industry, and are widely used in various chemical products, plastics, pharmaceuticals, etc. It is known that when urea compounds or urethane compounds are hydrogenated, formamides are produced as intermediates. However, because formamides are more reactive than urea compounds or urethane compounds, the hydrogenation of the intermediate formamides occurs preferentially, and ultimately the hydrogenation proceeds to alcohols and amines.

[0004] Japanese Patent Application Laid-Open No. 2003-286294

[0005] Journal of the American Chemical Society 2014, 136, 13217-13225

[0006] As described above, when urea compounds or urethane compounds are hydrogenated, formamides are produced as intermediates, but it has been difficult to selectively obtain the intermediate formamides. Therefore, an object of the present invention is to provide a novel catalyst that selectively produces formamides from urea compounds or urethane compounds.

[0007] Specifically, the present invention has the following configuration.

[0008] [1] A catalyst comprising a complex having a partial structure represented by the following formula (A): (In formula (A), M is an element of Group 7, 8 or 9, and is a metal having an Allred-Rochow electronegativity of 1.40 or more and a third ionization potential of 26.5 eV or more, P and M are coordinate bonded, and D １ is an atomic group containing an anionic nitrogen atom as a bond to M, and X １ is a linking group, R １ and R ２ are each independently a substituent containing at least one selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and M is bonded to another moiety by *.) [2] The catalyst according to claim 1, comprising an iridium complex having a partial structure represented by the following formula (1): (In formula (1), P and Ir are coordinate bonded, and D １ is an atomic group containing an anionic nitrogen atom as a bond to Ir, and X １ is a linking group, R １ and R ２ are each independently a substituent containing at least one selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and Ir is linked to another moiety at *.) [3] The catalyst according to [1] or [2], which contains an iridium complex having a partial structure represented by the following formula (2): (In formula (2), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing an anionic nitrogen, and X １ is a linking group, R １ and R ２are each independently a substituent containing at least one selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and Ir is linked to another moiety at *.) [4] The catalyst according to any one of [1] to [3], which contains an iridium complex having a partial structure represented by the following formula (3): (In formula (3), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing anionic nitrogen, ring B represents an aromatic ring, and R １ and R ２ are each independently a substituent containing at least one selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be bonded to each other to form a ring, and Ir is bonded to another moiety at *.) [5] R １ and R ２ are each independently an aromatic hydrocarbon group. [6] A method for producing formamides and / or amines, comprising allowing a urea compound to react with the catalyst according to any one of [1] to [5]. [7] A method for producing formamides and / or amines according to [6], wherein the urea compound is a compound represented by the following formula (11): (In formula (11), L １ and L ２ are each independently a single bond or a linking group, １１ and R １２ are each independently a hydrogen atom or a substituent, １３ and R １４ are each independently a hydrogen atom or a substituent, and R １３ and R １４ At least one of R is a hydrogen atom; １１ and R １２ may be linked together to form a ring, or R １１ and R １３ and R １２ and R １４ may be bonded to each other to form a ring, and n is an integer of 1 or more. [8] In formula (11), R １１ and R １２is a hydrocarbon group, and R １３ and R １４ [9] In the formula (11), R is a hydrogen atom. １１ and R １２ are the same group, and R １３ and R １４ are the same group, and L １ and L ２

[10] In the formula (11), at least R １１ and R １２ , R １３ and R １４ , or L １ and L ２ and (b) are different groups.

[11] A method for producing formamides and / or alcohols, comprising reacting a urethane compound with the catalyst according to any one of [1] to [5].

[12] A complex having a partial structure represented by the following formula (B): (In formula (B), M is an element of Group 7, 8, or 9, and is a metal having an Allred-Rochow electronegativity of 1.40 or more and a third ionization potential of 26.5 eV or more, P and M are coordinate bonded, ring A represents a nitrogen-containing ring containing anionic nitrogen, ring B represents an aromatic ring, and R １ and R ２ are each independently a substituent containing at least one selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and M is bonded to another moiety at *.)

[13] The complex according to

[12] , having a partial structure represented by the following formula (3): (In formula (3), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing anionic nitrogen, ring B represents an aromatic ring, and R １ and R ２are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and Ir is bonded to another moiety at *.

[0009] The present invention also has the following features. [A] A method for partially hydrogenating a urea compound, in the presence of the catalyst described in any one of [1] to [5], to obtain formamides and / or amines by adding hydrogen to a urea compound. [B] A method for partially decomposing a urea compound, in the presence of the catalyst described in any one of [1] to [5], to obtain formamides and / or amines by decomposing a urea compound. [C] A method for partially hydrogenating a urethane compound, in the presence of the catalyst described in any one of [1] to [5], to obtain formamides and / or alcohols by adding hydrogen to a urethane compound. [D] A method for partially decomposing a urethane compound, in the presence of the catalyst described in any one of [1] to [5], to obtain formamides and / or alcohols.

[0010] According to the present invention, a novel catalyst can be provided that selectively produces formamides from urea compounds or urethane compounds.

[0011] The present invention will be described in detail below. The following description of the constituent elements may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] The hydrogen atoms in each formula in this specification include isotopes (such as deuterium atoms), and the atoms constituting each substituent also include their isotopes. Furthermore, the substituents in each formula in this specification may be substituted with other substituents. In this case, the type of other substituents is not particularly limited, and any substitutable group may be used. Examples of other substituents include aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups), aromatic hydrocarbon groups (e.g., phenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, biphenyl groups), heterocyclic groups, acyl groups, alkoxy groups, amino groups, hydroxy groups, mercapto groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, sulfo groups, carboxy groups, nitro groups, hydroxamic acid groups, sulfino groups, hydrazino groups, imino groups, silyl groups, and phosphoryl groups. These substituent groups may be further substituted, and examples of further substituents include groups selected from the substituents described above. In the present specification, unless it is explicitly stated that a group has a substituent, it is preferred that the group does not have a substituent.

[0013] (Catalyst / Complex) The present embodiment relates to a catalyst containing a complex having a partial structure represented by the following formula (A): The present embodiment also relates to a complex having a partial structure represented by the following formula (A):

[0014] In formula (A), M is an element of Group 7, 8, or 9, and is a metal having an Allred-Rochow electronegativity of 1.40 or more and a third ionization potential of 26.5 eV or more, P and M are coordinate bonded, and D １ is an atomic group containing an anionic nitrogen atom as a bond to M, and X １ is a linking group, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and M is bonded to another moiety at *.

[0015] M is an element of Group 7, 8, or 9, and is a metal having an Allred-Rochow electronegativity of 1.40 or more and a third ionization potential of 26.5 eV or more. Examples of such metals include manganese (Mn), iron (Fe), cobalt (Co), ruthenium (Ru), rhodium (Rh), and iridium (Ir). The electronegativity and third ionization potential of each metal are as shown in the table below.

[0016]

[0017] By setting the electronegativity of the metal represented by M within the above range, the metal center has sufficient electronegativity to attract electrons from the ligand, thereby ensuring sufficient acidity of the NH bond of the π-coordinated ligand. Furthermore, by setting the third ionization potential of the metal represented by M within the above range, the generation of highly oxidized intermediates in the catalytic cycle can be suppressed. This allows the hydrogenation reaction rate of the substrate to be more effectively increased.

[0018] Among these, M in formula (A) is preferably at least one selected from the group consisting of manganese (Mn), iron (Fe), ruthenium (Ru), and iridium (Ir), more preferably at least one selected from the group consisting of manganese (Mn), ruthenium (Ru), and iridium (Ir), and particularly preferably iridium (Ir).

[0019] In addition, D in formula (A) １ , X １ and R １ and R ２ is D in formula (1) described later. １ , X １ and R １ and R ２ The same applies to the preferred ranges and examples.

[0020] The present embodiment relates to a catalyst containing an iridium complex having a partial structure represented by the following formula (1): The present embodiment also relates to an iridium complex having a partial structure represented by the following formula (1):

[0021] In formula (1), P and Ir are coordinate bonded, and D １ is an atomic group containing an anionic nitrogen atom as a bond to Ir, and X １ is a linking group, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and Ir is bonded to another moiety at *.

[0022] D １ is an atomic group containing an anionic nitrogen atom as a bond to Ir, and the anionic nitrogen atom and Ir are bonded by a covalent bond. １ is an anionic nitrogen-containing ligand. １ is preferably an atomic group having at least an anionic nitrogen atom as a bond to Ir and a group linked to the anionic nitrogen atom. The group linked to the anionic nitrogen atom may further have another substituent, and examples of the other substituent include the substitutable groups among the above-mentioned substituents.

[0023] For example, D １ may be represented by a structure surrounded by a dotted line and represented by the following formula (1'). In the following formula (1'), R represents a substituent, and examples of the substituent include groups that can be substituted among the above-mentioned substituents. R may be, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an acyl group, a sulfo group, an alkoxy group, or an amino group.

[0024] As will be described later, D １ may be an atomic group having a ring containing an anionic nitrogen atom as a bond to Ir, or may be an atomic group having a nitrogen-containing ring containing an anionic nitrogen atom.

[0025] X １is a linking group, and the linking group may have another substituent. Examples of the other substituent include the groups that can be substituted among the above-mentioned substituents, but the other substituent is preferably an aliphatic hydrocarbon group (an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, etc.). Among these, X １ The linking group represented by the formula (I) preferably has an alkyl group or an alkenyl group as another substituent. １ When a plurality of other substituents are introduced into the linking group, these substituents may be linked to each other to form a ring.

[0026] X １ The structure of the linking group represented by X is not particularly limited. １ is preferably a linking group containing at least one selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, more preferably a linking group containing carbon atoms, and even more preferably a hydrocarbon group. In this case, the number of carbon atoms constituting the linking group is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Furthermore, the number of carbon atoms constituting the linking group is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. Note that, when the linking group has other substituents, the number of carbon atoms mentioned above includes the number of carbon atoms contained in the other substituents.

[0027] X １ Examples of the linking group represented by the formula (I) include a divalent hydrocarbon group and a group formed by combining a divalent hydrocarbon group with one or more of -O-, -C(=O)-, -NR- (wherein R represents a hydrogen atom, an alkyl group, or an aryl group), and -S-.

[0028] R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring. １ and R ２ are linked to each other to form a ring" means that R １ and R ２are bonded to each other to form a linking group, which in turn forms a ring structure together with the P atom. In this case, the number of atoms constituting the ring structure is preferably 5 to 7.

[0029] R １ and R ２ are each independently preferably a substituent containing a carbon atom, more preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heteroaliphatic cyclic group, or a heteroaromatic cyclic group, and further preferably an aromatic hydrocarbon group.

[0030] The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aliphatic hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,2-dimethylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1-ethylpropyl group, an n-hexyl group, a 2-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,2-dimethylbutyl group, Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclopentyl group, a cyclooctyl group, a cyclopentyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentyl group, a cyclooctyl group, a cyclopentyl group, a cyclooctyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclooctyl group, a cyclopentyl group, a cyclooctyl group, a cyclooctyl group, a cyclopentyl group, a cyclohexyl group, a cyclooct ...Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, an allyl group, a prop-1-en-1-yl group, a prop-2-en-1-yl group, a prop-1-en-2-yl group, a but-1-en-1-yl group, a but-2-en-1-yl group, a but-3-en-1-yl group, a but-1-en-2-yl group, a but-3-en-2-yl group, a pent-1-en-1-yl group, and a pent-2-en-1-yl group. Examples of the aliphatic hydrocarbon group include a pent-3-en-1-yl group, a pent-4-en-1-yl group, a pent-1-en-2-yl group, a pent-4-en-2-yl group, a 3-methylbut-1-en-1-yl group, a 3-methylbut-2-en-1-yl group, a 3-methylbut-3-en-1-yl group, a hex-1-en-1-yl group, a hex-5-en-1-yl group, and a 4-methylpent-3-en-1-yl group. The aliphatic hydrocarbon group may further have another substituent, and examples of the other substituent include the groups that can be substituted among the above-mentioned substituents.

[0031] Examples of the aromatic hydrocarbon group include aryl groups having 6 to 30 carbon atoms. Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, and biphenyl. The aromatic hydrocarbon group may further have another substituent, and examples of the other substituent include the groups that can be substituted among the substituents described above. In particular, when the aromatic hydrocarbon group further has another substituent, the other substituent is preferably an alkyl group, and in this case, the aromatic hydrocarbon group may be an o-tolyl group, p-tolyl group, m-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, or mesityl group.

[0032] The number of carbon atoms constituting the heteroaliphatic cyclic group is preferably 1 to 30, and more preferably 3 to 30. Examples of the heteroaliphatic cyclic group include a piperidinyl group, a piperazinyl group, a morpholinyl group, a quinuclidinyl group, a pyridinyl group, and an oxetanyl group. The heteroaliphatic cyclic group may further have another substituent, and examples of the other substituent include the groups that can be substituted among the above-mentioned substituents.

[0033] Examples of the heteroaromatic ring group include heteroaryl groups preferably having 1 to 30 carbon atoms, and more preferably having 3 to 30 carbon atoms. Examples of heteroaryl groups having 1 to 30 carbon atoms include furanyl, thiophenyl, pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, indolyl, thianaphthenyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, quinolyl, isoquinolyl, tinolyl, quinoxalyl, dibenzothiophenyl, acridyl, and phenanthryl groups. The heteroaromatic ring group may further have other substituents, and examples of the other substituents include the substitutable groups among the above-mentioned substituents.

[0034] Among them, R １ and R ２ are each preferably independently an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include phenyl groups and polycyclic aryl groups. Examples of polycyclic aryl groups that can be used include bicyclic to tetracyclic aryl groups, more specifically naphthyl groups, anthryl groups, and phenanthryl groups. Among these, R １ and R ２ are each independently preferably a phenyl group. １ and R ２ may each independently further have another substituent, and examples of the other substituent include the groups that can be substituted among the above-mentioned substituents.

[0035] Ir is bonded to other sites at *. The structure of the other sites to which Ir is bonded is not particularly limited, but Ir is usually bonded to D １ and P, and further bonded to one or more atoms or atomic groups (substituents). For example, Ir is D １In addition to P, Ir may be bonded to one substituent, two substituents, three substituents, or four substituents. That is, the iridium complex having the partial structure represented by the above formula (1) is preferably an iridium monovalent complex or an iridium trivalent complex, but may have any other oxidation number. In addition, when Ir is D １ When two or more substituents are bonded to Ir atom and P, these substituents may be bonded to each other to form a ring. "Two or more substituents are bonded to each other to form a ring" means that two or more substituents are bonded to each other to form a linking group that forms a ring structure together with the Ir atom, or two or more substituents are bonded to each other to form a ring structure.

[0036] The formula weight of the other site (atom or atomic group (substituent)) to which Ir is bonded at * is preferably 1 or more, more preferably 10 or more, and even more preferably 20 or more. The formula weight of the other site (atom or atomic group (substituent)) is preferably 500 or less, more preferably 250 or less, and even more preferably 100 or less. The other site to which Ir is bonded at * may be a hydrogen atom.

[0037] The molecular weight of the iridium complex having the partial structure represented by formula (1) is preferably 230 or more, more preferably 250 or more, and even more preferably 300 or more. The molecular weight of the iridium complex having the partial structure represented by formula (1) is preferably 2000 or less, more preferably 1000 or less, even more preferably 900 or less, and particularly preferably 800 or less. The molecular weight of the complex having the partial structure represented by formula (A) is also preferably within the above range.

[0038] Ir may have a linking structure at the * site, and the partial structure represented by formula (1) may be further linked via this linking structure. That is, the iridium complex having the partial structure represented by formula (1) may be a dimer or oligomer compound as shown in the following structure. In this case, the molecular weight of the oligomer compound is preferably 700 or more, more preferably 900 or more. The molecular weight of the oligomer compound is preferably 3000 or less, more preferably 2500 or less. The complex having the partial structure represented by formula (A) may also be a dimer or oligomer compound.

[0039] The catalyst of the present embodiment preferably contains an iridium complex having a partial structure represented by the following formula (1-2): In other words, the iridium complex having the partial structure represented by the above formula (1) is preferably an iridium complex having a partial structure represented by the following formula (1-2):

[0040] In formula (1-2), P and Ir are coordinate bonded, and D １ is an atomic group containing an anionic nitrogen atom as a bond to Ir, and X １ is a linking group, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be bonded to each other to form a ring, and * represents a bonding site to another structure. １ , X １ , R １ and R ２ The preferred range and examples of D in formula (1) are １ , X １ , R １ and R ２ The preferred ranges and examples are the same as those of the above.

[0041] In the above formula (1-2), Ir is D １In addition to P, it is bonded to two substituents. These two substituents may be linked to each other to form a ring. The preferred molecular weights of these two substituents are as described above. These two substituents may be hydrogen atoms.

[0042] The two substituents to which Ir is bonded are not particularly limited, but examples of the substituents include a hydrocarbon group, a halogen atom, or a monovalent group formed by combining a hydrocarbon group with one or more of -O-, -C(=O)-, -NR- (wherein R represents a hydrogen atom, an alkyl group, or an aryl group), and -S-. These groups may form a coordinate bond with Ir as a neutral ligand. Furthermore, these groups may each independently further have another substituent, and examples of the other substituents include the substitutable groups among the substituents described above.

[0043] The catalyst of the present embodiment preferably contains an iridium complex having a partial structure represented by the following formula (1-3): That is, the iridium complex having the partial structure represented by the above formula (1) is preferably an iridium complex having a partial structure represented by the following formula (1-3):

[0044] In formula (1-3), P and Ir are coordinate bonded, and D １ is an atomic group containing an anionic nitrogen atom as a bond to Ir, and X １ is a linking group, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be bonded to each other to form a ring; R ３ and R ４ are each independently a substituent, and these substituents may be linked to each other to form a ring. １ , X １ , R １ and R ２ The preferred range and examples of D in formula (1) are １ , X １ , R １ and R ２The preferred ranges and examples are the same as those of the above.

[0045] R ３ and R ４ are each independently a substituent. The substituent is preferably a hydrocarbon group, a halogen atom, or a monovalent group formed by combining a hydrocarbon group with one or more of -O-, -C(=O)-, -NR- (wherein R represents a hydrogen atom, an alkyl group, or an aryl group), and -S-, and these groups may form a coordinate bond with Ir as a neutral ligand. Furthermore, these groups may each independently have further substituents, and examples of other substituents include the substitutable groups among the above-mentioned substituents. Among these, R ３ and R ４ are each independently preferably a hydrocarbon group, more preferably an unsaturated hydrocarbon group.

[0046] R ３ and R ４ may be linked to each other to form a ring. ３ and R ４ are linked to each other to form a ring" means that R ３ and R ４ are bonded to each other to form a linking group, which in turn forms a ring structure together with the Ir atom, or ３ and R ４ are bonded to each other to form a ring structure. ３ and R ４ When R are bonded to each other to form a ring, the number of atoms constituting the ring structure is preferably 4 or more, more preferably 5 or more. The number of atoms constituting the ring structure is preferably 12 or less, more preferably 10 or less. For example, R ３ and R ４ may be linked to each other to form a cyclic diene. Examples of the cyclic diene include cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, and cyclooctadiene.

[0047] The catalyst of the present embodiment preferably contains an iridium complex having a partial structure represented by the following formula (2): In other words, the iridium complex having the partial structure represented by the above formula (1) is preferably an iridium complex having a partial structure represented by the following formula (2):

[0048] In formula (2), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing an anionic nitrogen, and X １ is a linking group, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be bonded to each other to form a ring, and Ir is bonded to another moiety at *. １ , R １ and R ２ The preferred range and examples of X in formula (1) are １ , R １ and R ２ The preferred ranges and examples are the same as those of the formula (1). In addition, the structures of other sites where Ir is bonded with * in formula (2) are also the same as those exemplified in formula (1) and the like.

[0049] Ring A represents a nitrogen-containing ring containing anionic nitrogen. The anionic nitrogen atom contained in ring A and Ir are bonded by a covalent bond. The nitrogen-containing ring containing anionic nitrogen may be a nitrogen-containing alicyclic ring or a nitrogen-containing aromatic ring. The nitrogen-containing ring containing anionic nitrogen may be a monocyclic ring or a fused ring. The number of atoms constituting the nitrogen-containing ring containing anionic nitrogen (including the anionic nitrogen atom) is preferably 5 or more. The number of atoms constituting the nitrogen-containing ring containing anionic nitrogen (including the anionic nitrogen atom) is preferably 20 or less. The number of nitrogen atoms contained in ring A, including the anionic nitrogen atom, is preferably 1 to 4, more preferably 1 or 2. Among them, the nitrogen-containing ring containing anionic nitrogen is preferably a nitrogen-containing aromatic ring, and examples of the nitrogen-containing aromatic ring containing anionic nitrogen include pyrrole, imidazole, benzimidazole, indole, pyrazole, triazole, tetrazole, isoindole, indazole, purine, and carbazole. Among them, the nitrogen-containing aromatic ring containing anionic nitrogen is preferably a pyrrole ring, an imidazole ring, or a benzimidazole ring, and particularly preferably a pyrrole ring. The nitrogen-containing ring containing anionic nitrogen represented by ring A may further have another substituent, and examples of the other substituent include the substitutable groups among the above-mentioned substituents.

[0050] The catalyst of the present embodiment preferably contains an iridium complex having a partial structure represented by the following formula (2-2): In other words, the iridium complex having the partial structure represented by the above formula (2) is preferably an iridium complex having a partial structure represented by the following formula (2-2):

[0051] In formula (2-2), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing an anionic nitrogen, and X １ is a linking group, and R １ and R ２are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and * represents a bonding site to another structure. １ , R １ and R ２ The preferred range and examples of X in formula (1) are １ , R １ and R ２ In addition, other structures to which * is bonded in formula (2-2) are also similar to the structures exemplified in formula (1-2) etc., and the preferred range and examples of ring A are similar to the preferred range and examples of ring A in formula (2).

[0052] In the above formula (2-2), Ir is bonded to two substituents in addition to N and P. These two substituents may be bonded to each other to form a ring. The preferred ranges and examples of these two substituents are the same as the preferred ranges and examples of these two substituents in formula (1-2).

[0053] The catalyst of the present embodiment preferably contains an iridium complex having a partial structure represented by the following formula (2-3): In other words, the iridium complex having the partial structure represented by the above formula (2) is preferably an iridium complex having a partial structure represented by the following formula (2-3):

[0054] In formula (2-3), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing an anionic nitrogen, and X １ is a linking group, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be bonded to each other to form a ring; R ３ and R ４ are each independently a substituent, and these substituents may be linked to each other to form a ring. １ , R １ and R ２The preferred range and examples of R in formula (2-3) are the same as those in formula (1). ３ and R ４ The preferred range and examples of are the same as those in formula (1-3), and the preferred range and examples of ring A are the same as those in formula (2).

[0055] The catalyst of the present embodiment preferably contains an iridium complex having a partial structure represented by the following formula (3): In other words, the iridium complex having the partial structure represented by the above formula (1) is preferably an iridium complex having a partial structure represented by the following formula (3):

[0056] In formula (3), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing an anionic nitrogen, ring B represents an aromatic ring, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and Ir is bonded to another moiety at *. １ and R ２ The preferred range and examples of R in formula (1) are １ and R ２ The preferred range and examples of the ring A in formula (2) are the same as those in formula (1).

[0057] Ring B represents an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring. Among these, the aromatic ring is preferably a benzene ring or a naphthalene ring. The aromatic ring represented by ring B may further have another substituent, and examples of the other substituent include the substitutable groups among the above-mentioned substituents.

[0058] The catalyst of the present embodiment preferably contains an iridium complex having a partial structure represented by the following formula (3-2): In other words, the iridium complex having the partial structure represented by the above formula (3) is preferably an iridium complex having a partial structure represented by the following formula (3-2):

[0059] In formula (3-2), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing an anionic nitrogen, ring B represents an aromatic ring, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, and * represents a bonding site to another structure. １ and R ２ The preferred range and examples of R in formula (1) are １ and R ２ In addition, other structures to which * is bonded in formula (3-2) are also similar to the structures exemplified in formula (1-2) etc., the preferred range and examples of ring A are similar to the preferred range and examples of ring A in formula (2), and the preferred range and examples of ring B are similar to the preferred range and examples of ring A in formula (3).

[0060] In the above formula (3-2), Ir is bonded to two substituents in addition to N and P. These two substituents may be bonded to each other to form a ring. The preferred ranges and examples of these two substituents are the same as the preferred ranges and examples of these two substituents in formula (1-2).

[0061] The catalyst of the present embodiment preferably contains an iridium complex having a partial structure represented by the following formula (3-3): In other words, the iridium complex having the partial structure represented by the above formula (3) is preferably an iridium complex having a partial structure represented by the following formula (3-3):

[0062] In formula (3-3), P and Ir are coordinately bonded, ring A represents a nitrogen-containing ring containing an anionic nitrogen, ring B represents an aromatic ring, and R １ and R ２ are each independently a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be bonded to each other to form a ring; R ３ and R ４ are each independently a substituent, and these substituents may be linked to each other to form a ring. １ and R ２ The preferred range and examples of R in formula (1) are １ and R ２ The preferred ranges and examples are the same as those of R in formula (3-3). ３ and R ４ The preferred range and examples of are the same as the preferred range and examples in formula (1-3), the preferred range and examples of ring A are the same as the preferred range and examples of ring A in formula (2), and the preferred range and examples of ring B are the same as the preferred range and examples of ring A in formula (3).

[0063] Specific examples of iridium complexes having the partial structure represented by formula (1) are shown below, but the present invention is not limited to these. In the following, Ph represents a phenyl group.

[0064] For example, when the catalyst of this embodiment is reacted with a urea-based compound as a substrate, hydrogen molecules as a reducing agent are π-coordinated to iridium. The following structure is assumed as the π-coordinated complex.

[0065] In the transition state, the ligand containing the anionic nitrogen atom in the complex changes from σ-coordination to π-coordination. That is, in the complex, covalent bonds are formed between the iridium and the hydrogen atom, and between the anionic nitrogen atom and the hydrogen atom, the bond between the nitrogen atom and the iridium is broken, and a new π-coordination bond is formed between the pyrrole and the iridium. In this way, when the catalyst of this embodiment is allowed to act on a urea-based compound, a reaction occurs accompanied by a change in the coordination mode of the ligand containing the anionic nitrogen atom, so that the hydrogen bonded to the anionic nitrogen atom selectively forms a hydrogen bond with the more basic urea oxygen, and as a result, formamides and amines can be selectively obtained from the urea-based compound. Note that the structure in the transition state when the catalyst of this embodiment is allowed to act on a urea-based compound substrate is assumed to be as follows. Note that the thick dashed line between Ir and pyrrole represents a π-coordination bond.

[0066] In conventional technology, when urea compounds are hydrogenated, formamides are produced as intermediates. However, because formamides are more reactive than urea compounds, the hydrogenation of the intermediate formamides occurs preferentially, and they are ultimately decomposed into alcohols and amines, making it difficult to selectively produce and obtain formamides. However, in the present invention, formamides can be selectively produced by using a catalyst containing a novel complex having a partial structure represented by the above formula (A) or (1). Since formamides are important chemical products in fields such as organic chemical industry, if formamides can be selectively obtained by hydrogenating urea compounds, industrial applications can be expected. In this specification, formamides refer to formamide and its derivatives, and amines refer to amines and their derivatives.

[0067] Furthermore, in this embodiment, by using a catalyst containing a novel complex having the partial structure represented by the above formula, it is also possible to decompose urea-based compounds such as polyurea and urethane-based compounds such as polyurethane. Polyurea and polyurethane are also used as general-purpose plastics, and if such plastic materials can be decomposed, chemical recycling becomes possible, which is very useful from the viewpoint of environmental protection. In this specification, alcohols refer to alcohols and their derivatives.

[0068] (Method of synthesizing complex) An iridium complex having the partial structure represented by the above formula (1) can be produced by combining known methods. For example, an iridium complex can be obtained by coupling an anionic nitrogen atom-containing compound with a phosphorus atom-containing compound and reacting the resulting compound with an iridium-containing compound. Alternatively, an iridium complex can be obtained by introducing a phosphorus atom into a compound containing an anionic nitrogen atom and a linking group.

[0069] For example, an iridium complex, iridium-phosphinepyrrolate complex (Ir / PP complex), can be produced according to the synthesis scheme shown below.

[0070] The iridium complex having the partial structure represented by the above formula (1) is produced, for example, using (2-bromophenyl)diphenylphosphine as a raw material. Specifically, methanol is added to (2-bromophenyl)diphenylphosphine, and then hydrogen peroxide is added to obtain an oxidized form of (2-bromophenyl)diphenylphosphine. Next, the oxidized form of (2-bromophenyl)diphenylphosphine is treated with 1-Boc-2-pyrroleboronic acid, Pd(dba), ２ , PPh ３ , Na ２ CO ３ and dehydrated DMF are added, and the reaction is allowed to proceed to obtain a coupling product of (2-bromophenyl)diphenylphosphine and 1-Boc-2-pyrroleboronic acid. ３ , dehydrated and degassed Et ３N and dehydrated and degassed toluene were added to carry out the reaction, and the reaction was followed by vacuum drying to obtain the reduced product. Then, THF was added to the reduced product, and the mixture was stirred. NaH was then added to carry out the reaction, and the filtrate after the reaction was treated with [IrCl(cod)]. ２ The reaction is carried out by adding the compound (Ir) and extracting it with a solvent, whereby an iridium-phosphine pyrrolate complex (Ir / PP complex) having phosphine pyrrolate as a supporting ligand can be obtained.

[0071] The complex having the partial structure represented by formula (A) can be produced by combining known methods. For example, a ruthenium complex or a manganese complex can be obtained by coupling an anionic nitrogen atom-containing compound with a phosphorus atom-containing compound and reacting the resulting compound with a ruthenium-containing compound or a manganese-containing compound.

[0072] (Method for producing formamides and / or amines) <Urea-based compound> The present embodiment relates to a method for producing formamides and / or amines, which includes allowing a catalyst containing a complex having the partial structure described above to act on a urea-based compound. The present embodiment may relate to a method for producing formamides, which includes allowing a catalyst containing a complex having the partial structure described above to act on a urea-based compound, or may relate to a method for producing amines, which includes allowing a catalyst containing a complex having the partial structure described above to act on a urea-based compound, or may relate to a method for producing formamides and amines, which includes allowing a catalyst containing a complex having the partial structure described above to act on a urea-based compound.

[0073] The urea compound used in the method for producing formamides and / or amines of the present embodiment is preferably a compound represented by the following formula (11).

[0074] In formula (11), L １ and L ２ are each independently a single bond or a linking group, and R １１ and R １２ are each independently a hydrogen atom or a substituent, and R １３ and R １４are each independently a hydrogen atom or a substituent, and R １３ and R １４ At least one of R is a hydrogen atom; １１ and R １２ may be linked together to form a ring, or R １１ and R １３ and R １２ and R １４ may be linked to each other to form a ring, and n is an integer of 1 or more.

[0075] L １ and L ２ are each independently a single bond or a linking group. When n is 1, L １ and L ２ is preferably a single bond. When n is an integer of 2 or more, L １ and L ２ are each independently preferably a single bond or a linking group, more preferably a linking group. In this case, the linking group is preferably a linking group containing at least one atom selected from the group consisting of carbon atoms, oxygen atoms, and nitrogen atoms, more preferably a linking group containing carbon atoms. For example, the linking group is preferably a divalent hydrocarbon group, or a group formed by combining a divalent hydrocarbon group with one or more of -O-, -NR-, and -C(=O)-. In addition, in formula (11), L １ and L ２ The atom directly bonded to the nitrogen atom to which each of the is linked is a carbon atom. The divalent hydrocarbon group may be an unsaturated hydrocarbon group, a saturated hydrocarbon group, or an arylene group. When the divalent hydrocarbon group is a divalent unsaturated hydrocarbon group or a saturated hydrocarbon group, the number of carbon atoms therein is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Furthermore, when the divalent hydrocarbon group is an arylene group, the arylene group is preferably a phenylene group. L １ and L ２ When is a linking group, the linking group may further have another substituent, and examples of the other substituent include the substitutable groups among the above-mentioned substituents.

[0076] R１１ and R １２ are each independently a hydrogen atom or a substituent. The substituent is preferably a substituent containing at least one selected from the group consisting of carbon atoms, oxygen atoms, and nitrogen atoms. Examples of such a substituent include a hydrocarbon group, an amino group, an isocyanate group, or a monovalent group formed by combining a hydrocarbon group with one or more of -O-, -C(=O)-, or -NR- (wherein R represents a hydrogen atom, an alkyl group, or an aryl group). Among these, the substituent is preferably a hydrocarbon group, an amino group, an isocyanate group, or a carbamoyl group. These substituents may further have other substituents, and examples of such other substituents include the groups that can be substituted among the above-mentioned substituents.

[0077] When n is 1, R １１ and R １２ are each independently preferably a substituent containing at least one selected from the group consisting of carbon atoms, oxygen atoms, and nitrogen atoms, more preferably a substituent containing carbon atoms, and even more preferably a hydrocarbon group. These substituents may further have other substituents, and examples of the other substituents include the groups that can be substituted among the above-mentioned substituents. Among them, R １１ and R １２ are each independently preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. For example, R １１ and R １２ Examples of groups that R can take include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. １１ and R １２ At least one of R is preferably an aromatic hydrocarbon group, and the aromatic hydrocarbon group is more preferably a phenyl group. １１ and R １２ In a preferred embodiment, both of the above are aromatic hydrocarbon groups, and in this case too, the aromatic hydrocarbon group is more preferably a phenyl group.

[0078] R １３ and R １４are each independently a hydrogen atom or a substituent, and R １３ and R １４ At least one of the groups is a hydrogen atom. The substituent is preferably a substituent containing at least one selected from the group consisting of carbon atoms, oxygen atoms, and nitrogen atoms, more preferably a substituent containing carbon atoms, even more preferably a hydrocarbon group, and particularly preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. Note that R １３ and R １４ At least one of R １３ and R １４ It is also preferred that both of are hydrogen atoms.

[0079] Among them, a preferred embodiment of the urea-based compound used in the method for producing formamides and / or amines is a compound represented by the formula (11) where R １１ and R １２ is a hydrocarbon group, and R １３ and R １４ is a hydrogen atom.

[0080] R １１ and R １２ may be linked to each other to form a ring. １１ and R １２ When R are linked to each other to form a ring, n is preferably 5 or less, more preferably 3 or less, and particularly preferably 1. １１ and R １２ When they are linked to each other to form a ring, R １１ 、 R １２ , L １ , L ２ The C atom and two N atoms form a ring structure. The number of atoms constituting the ring structure (the number of atoms including the C atom and two N atoms) is not particularly limited, but is preferably 5 to 30, and more preferably 5 to 20.

[0081] Also, R １１ and R １３ and R １２ and R １４ may be linked to each other to form a ring. １１ and R １３ When they are linked to each other to form a ring, R １１ , R １３ , L １ and N atoms form a ring structure. １２ and R １４ When they are linked to each other to form a ring, R １２ , R １４ , L ２ and N atoms form a ring structure. １１ and R １３ and R １２ and R １４ are bonded to each other to form a ring, and when n is 2 or more, the R at the most terminal １３ is R １１ and R １４ is R １２ A ring is formed with R １１ and R １３ and R １２ and R １４ When each of them is linked to each other to form a ring, n is preferably 1.

[0082] n may be an integer of 1 or more. There is no particular limitation on the upper limit of n, but for example, it is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. In this specification, when n is 2 or more, the urea-based compound may be referred to as polyurea. In other words, the urea-based compound also includes polyurea. In this embodiment, it is also preferable to use a urea-based compound in which n is 1 and does not have a repeating unit.

[0083] In this specification, R in formula (11) １１ and R １２ are the same group, and R １３ and R １４ are the same groups, and L １ and L２ A urea compound in which R is the same group is also called a symmetrical urea compound. A symmetrical urea compound has a bilaterally symmetrical structure with the carbonyl bond site as the center line. In addition, in formula (11), at least R １１ and R １２ , R １３ and R １４ , or L １ and L ２ A urea compound in which the groups are different is also referred to as an asymmetric urea compound. In the method for producing formamides and / or amines of this embodiment, not only symmetric urea compounds but also asymmetric urea compounds can be used as substrates. Therefore, in this embodiment, an appropriate urea compound can be selected from symmetric urea compounds and asymmetric urea compounds to produce the target formamides and amines.

[0084] When n is 1, the urea compound is preferably a urea compound represented by formula (11-2) or formula (11-3).

[0085] In formula (11-2), L １ and L ２ are each independently a single bond or a linking group, and R １１ and R １２ are each independently a hydrogen atom or a substituent, and R １３ and R １４ are each independently a hydrogen atom or a substituent, and R １３ and R １４ At least one of L is a hydrogen atom. １ and L ２ , R １１ and R １２ , R １３ and R １４ When these are the same, the urea compound is a symmetric urea compound, and when any of these are different, the urea compound is an asymmetric urea compound.

[0086] In formula (11-3), L １ and L ２are each independently a single bond or a linking group, and R １３ and R １４ are each independently a hydrogen atom or a substituent, and R １３ and R １４ At least one of R is a hydrogen atom; ２１ and R ２２ are each independently a substituent, and m1 and m2 are each independently an integer of 0 to 5. In formula (11-3), L １ and L ２ , R １３ and R １４ , R ２１ and R ２２ When m1 and m2 are the same, the urea compound is a symmetric urea compound, and when any of the above is different, the urea compound is an asymmetric urea compound.

[0087] In formula (11-2) and formula (11-3), L １ and L ２ are each independently preferably a single bond or an alkylene group, more preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and particularly preferably a single bond. １３ and R １４ At least one of the groups is a hydrogen atom and the other is an alkyl group having 1 to 3 carbon atoms, or R １３ and R １４ are preferably both hydrogen atoms.

[0088] In formula (11-2), R １１ and R １２ are each independently a hydrogen atom or a substituent. The substituent is preferably a substituent containing at least one selected from the group consisting of carbon atoms, oxygen atoms, and nitrogen atoms. Examples of such a substituent include a hydrocarbon group, an amino group, an isocyanate group, or a monovalent group formed by combining a hydrocarbon group with one or more of -O-, -C(=O)-, or -NR- (wherein R represents a hydrogen atom, an alkyl group, or an aryl group). Among these, the substituent is preferably a hydrocarbon group, and more preferably an aromatic hydrocarbon group.

[0089] In formula (11-3), R ２１ and R ２２ are each independently a substituent. Examples of the substituent include an aliphatic hydrocarbon group (an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, etc.), an aliphatic oxy group (an alkoxy group, an alkyleneoxy group, an ethyleneoxy group, a propyleneoxy group, etc.), an amino group, a hydroxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group, a carboxy group, a nitro group, etc. Note that m1 and m2 are each independently an integer of 0 to 5, and are preferably 0 or 1.

[0090] Usually, R ２１ or R ２２ When easily reducible functional groups such as halogen atoms, ester groups, or nitro groups are present in the urea-based compound, hydrogenation of these easily reducible functional groups is predicted, and there is a concern that the decomposition (hydrogenation) properties of the urea-based compound will be impaired. However, in the present invention, by using a catalyst containing a complex having the above-mentioned partial structure as the catalyst, formamides and amines can be produced without impairing the decomposition (hydrogenation) properties of the urea-based compound even in the coexistence of easily reducible functional groups such as those described above. As such, the catalyst in the present invention acts on the urea-based compound even in the presence of easily reducible functional groups, and can efficiently produce formamides and amines.

[0091] Specific examples of the symmetric urea compound represented by formula (11) are shown below, but the urea compound used in the present invention is not limited to these. In the following, Bu represents a butyl group, and Me represents a methyl group.

[0092] Specific examples of the asymmetric urea compound represented by formula (11) are shown below, but the urea compound used in the present invention is not limited to these.

[0093] Specific examples of polyurea represented by formula (11) are shown below, but the urea compounds used in the present invention are not limited to these.

[0094] When n is 1 in formula (11), the molecular weight of the urea-based compound is preferably 70 or more, more preferably 100 or more. Furthermore, the molecular weight of the urea-based compound is preferably 1,000 or less, more preferably 500 or less. On the other hand, when n is 2 or more in formula (11) and the compound is polyurea, the molecular weight of the polyurea is preferably 200 or more, more preferably 1,000 or more. Furthermore, the molecular weight of the polyurea is preferably 1,000,000 or less, more preferably 10,000 or less.

[0095] <Formamides / Amines> The formamides produced by the method for producing formamides and / or amines of this embodiment are preferably compounds represented by the following formula (12-1) or formula (12-2), and the amines produced by the method for producing formamides and / or amines of this embodiment are preferably compounds represented by the following formula (13-1) or formula (13-2). Note that when the substrate is a urea compound and the urea compound is a symmetric urea compound, the compound represented by formula (12-1) and the compound represented by formula (12-2) are the same compound, and the compound represented by formula (13-1) and the compound represented by formula (13-2) are also the same compound.

[0096] In the formulas (12-1), (12-2), (13-1) and (13-2), L １ and L ２ are each independently a single bond or a linking group, and R １１ and R １２ are each independently a hydrogen atom or a substituent, and R １３ and R １４ are each independently a hydrogen atom or a substituent, and R １３ and R １４ At least one of R is a hydrogen atom; １１ and R １３ and R １２ and R １４ may be bonded to each other to form a ring.１ and L ２ , R １１ and R １２ , R １３ and R １４ The preferred range and examples of are L in formula (11). １ and L ２ , R １１ and R １２ , R １３ and R １４ The preferred ranges and examples are the same as those of the above.

[0097] The molecular weight of the formamides represented by formula (12-1) or formula (12-2) is preferably 60 or more, more preferably 70 or more. The molecular weight of the formamides is preferably 500 or less, more preferably 250 or less. The molecular weight of the amines represented by formula (13-1) or formula (13-2) is preferably 30 or more, more preferably 40 or more. The molecular weight of the amines is preferably 470 or less, more preferably 230 or less.

[0098] In the method for producing formamides and / or amines of this embodiment, the amount of the complex reacted with 1 mol of the urea compound is not particularly limited to a lower limit, but is preferably 0.001 mol or more, more preferably 0.01 mol or more, and even more preferably 0.03 mol or more. Also, the amount of the complex reacted with 1 mol of the urea compound is not particularly limited to an upper limit, but is, for example, preferably 1 mol or less, more preferably 0.1 mol or less, and even more preferably 0.05 mol or less.

[0099] In the method for producing formamides and / or amines of this embodiment, a urea compound as a substrate, hydrogen as a reducing agent, and a complex as a catalyst are mixed and reacted. The reaction temperature is preferably 50 to 200°C, and more preferably 120 to 170°C. The hydrogen pressure is preferably 0.1 to 10 MPa, and more preferably 1 to 3 MPa. The reaction time is preferably 10 to 200 hours, and more preferably 40 to 150 hours.

[0100] To promote the reaction, a base may be added to the mixture, if necessary. In this case, examples of the base that can be used include potassium t-butoxide, sodium t-butoxide, lithium t-butoxide, potassium methoxy, and potassium ethoxy. Among these, potassium t-butoxide is preferably used. The amount of the base added is preferably, for example, 0.1 to 1 mol per 1 mol of the urea compound.

[0101] In the method for producing formamides and / or amines of this embodiment, both formamides and amines are produced. The ratio of the amount (mol) of formamides produced to the amount (mol) of amines produced is preferably 5:1 to 1:5, more preferably 4:1 to 1:4, even more preferably 3:1 to 1:3, and particularly preferably 2:1 to 1:2. In the method for producing formamides and / or amines of this embodiment, the amounts of formamides and amines produced can be approximately equal, which means that the hydrogenation of the urea compound is selectively carried out.

[0102] (Method for producing formamides and / or alcohols) <Urethane-based compound> The present embodiment relates to a method for producing formamides and / or alcohols, which includes allowing a urethane-based compound to react with a catalyst containing a complex having the partial structure described above. The present embodiment may relate to a method for producing formamides, which includes allowing a urethane-based compound to react with a catalyst containing a complex having the partial structure described above, or may relate to a method for producing alcohols, which includes allowing a urethane-based compound to react with a catalyst containing a complex having the partial structure described above, or may relate to a method for producing formamides and alcohols, which includes allowing a catalyst containing a complex having the partial structure described above to react.

[0103] The urethane compound used in the method for producing formamides and / or alcohols of the present embodiment is preferably a compound represented by the following formula (21).

[0104] In formula (21), L １ and L ２ are each independently a single bond or a linking group, and R １１ and R １２ are each independently a hydrogen atom or a substituent, and R １１ and R １２ may be linked to each other to form a ring, and n is an integer of 1 or more.

[0105] L １ and L ２ are each independently a single bond or a linking group. When n is 1, L １ and L ２ is preferably a single bond. When n is an integer of 2 or more, L １ and L ２ are each independently preferably a single bond or a linking group, more preferably a linking group. In this case, the linking group is １ and L ２ Examples of linking groups include the same as those shown in the above.

[0106] R １１ and R １２ are each independently a hydrogen atom or a substituent. １１ and R １２ Examples of linking groups include the same as those shown in the above.

[0107] n may be an integer of 1 or more. There is no particular upper limit to n, but for example, it is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. In this specification, when n is 2 or more, the urethane-based compound may be referred to as polyurethane. In other words, the urethane-based compound also includes polyurethane. In this embodiment, it is also preferable to use a urethane-based compound in which n is 1 and does not have a repeating unit.

[0108] When n is 1, the urethane compound is preferably a urethane compound represented by formula (21-2).

[0109] In formula (21-2), L １ and L ２ are each independently a single bond or a linking group, and R １１ is a hydrogen atom or a substituent, and R １１ and R １２ may be linked to each other to form a ring, and R ２２ is a substituent, and m2 is an integer of 0 to 5.

[0110] In formula (21-2), L １ and L ２ are each independently preferably a single bond or an alkylene group, more preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and particularly preferably a single bond. １１ is preferably a substituent, and examples of the substituent include R １２ Examples of linking groups include the same as those shown in the above. Examples include a hydrocarbon group, an amino group, an isocyanate group, or a monovalent group formed by combining a hydrocarbon group with one or more of -O-, -C(=O)-, or -NR- (wherein R represents a hydrogen atom, an alkyl group, or an aryl group), and a monovalent group formed by combining a hydrocarbon group with one or more of -O- is preferred. Note that m2 is each independently an integer of 0 to 5, and is preferably 0 or 1.

[0111] <Formamides / Alcohols> Formamides produced by the method for producing formamides and / or alcohols of the present embodiment are preferably compounds represented by the following formula (22), and alcohols produced by the method for producing formamides and / or alcohols of the present embodiment are preferably compounds represented by the following formula (23).

[0112] In formula (22) and formula (23), L １ and L ２ are each independently a single bond or a linking group, and R １１ and R １２ are each independently a hydrogen atom or a substituent. １ and L２ , R １１ and R １２ The preferred range and examples of are L in formula (21). １ and L ２ , R １１ and R １２ The preferred ranges and examples are the same as those of the above.

[0113] The molecular weight of the formamides represented by formula (22) is preferably 60 or more, more preferably 70 or more. The molecular weight of the formamides is preferably 500 or less, more preferably 250 or less. The molecular weight of the alcohols represented by formula (23) is preferably 20 or more, more preferably 30 or more. The molecular weight of the alcohols is preferably 470 or less, more preferably 300 or less.

[0114] In the method for producing formamides and / or alcohols of this embodiment, the amount of the complex reacted with 1 mol of the urethane compound is not particularly limited to a lower limit, but is preferably 0.001 mol or more, more preferably 0.01 mol or more, and even more preferably 0.03 mol or more. Also, the amount of the complex reacted with 1 mol of the urethane compound is not particularly limited to an upper limit, but is preferably 1 mol or less, more preferably 0.1 mol or less, and even more preferably 0.05 mol or less.

[0115] In the method for producing formamides and / or alcohols of this embodiment, a urethane compound as a substrate, hydrogen as a reducing agent, and a complex as a catalyst are mixed and reacted. The reaction temperature is preferably 50 to 200°C, and more preferably 120 to 170°C. The hydrogen pressure is preferably 0.1 to 10 MPa, and more preferably 1 to 3 MPa. The reaction time is preferably 10 to 200 hours, and more preferably 40 to 150 hours.

[0116] To promote the reaction, a base may be added to the mixture, if necessary. In this case, examples of the base that can be used include potassium t-butoxide, sodium t-butoxide, lithium t-butoxide, potassium methoxy, and potassium ethoxy. Among these, potassium t-butoxide is preferred. The amount of the base added is preferably 0.1 to 1 mol, for example, per 1 mol of the urethane compound.

[0117] In the method for producing formamides and / or alcohols of this embodiment, both formamides and alcohols are produced. The ratio of the amount (mol) of formamides produced to the amount (mol) of alcohols produced is preferably 5:1 to 1:5, more preferably 4:1 to 1:4, even more preferably 3:1 to 1:3, and particularly preferably 2:1 to 1:2. In the method for producing formamides and / or alcohols of this embodiment, the amounts of formamides and alcohols produced can be approximately equal, which means that the hydrogenation of the urethane compound is selectively carried out.

[0118] (Partial Hydrogenation Method / Partial Decomposition Method) <Urea Compound> This embodiment may relate to a method for hydrogenating a urea compound, in which hydrogen is added to a urea compound in the presence of a catalyst containing a complex having the partial structure described above to obtain formamides and / or amines. The hydrogenation method of this embodiment is not a complete hydrogenation method for producing alcohols and amines from a urea compound, but is a method for producing formamides and amines from a urea compound, and therefore can also be called a partial hydrogenation method. In other words, this embodiment relates to a method for partially hydrogenating a urea compound in the presence of a catalyst containing a complex having the partial structure described above.

[0119] Furthermore, this embodiment may also relate to a method for decomposing a urea compound in the presence of a catalyst containing a complex having the partial structure described above, thereby obtaining formamides and / or amines. The decomposition method of this embodiment is not a complete decomposition method in which a urea compound is decomposed to produce alcohols and amines, but rather a method in which a urea compound is decomposed to produce formamides and amines, and therefore can also be called a partial decomposition method. In other words, this embodiment relates to a method for partially decomposing a urea compound in the presence of a catalyst containing a complex having the partial structure described above.

[0120] The above-described partial hydrogenation method and partial decomposition method also make it possible to decompose urea-based compounds such as polyurea. This embodiment may relate to a partial hydrogenation method or partial decomposition method for polyurea. If plastic materials such as polyurea can be decomposed, chemical recycling becomes possible. In this way, the above-described partial hydrogenation method and partial decomposition method are very useful methods from the viewpoint of environmental protection.

[0121] <Urethane Compound> This embodiment may relate to a method for hydrogenating a urethane compound, in which hydrogen is added to a urethane compound in the presence of a catalyst containing a complex having the partial structure described above to obtain formamides and / or alcohols. The hydrogenation method of this embodiment is not a complete hydrogenation method for producing amines and alcohols from a urethane compound, but rather a method for producing formamides and alcohols from a urethane compound, and therefore can also be called a partial hydrogenation method. In other words, this embodiment relates to a method for partially hydrogenating a urethane compound in the presence of a catalyst containing a complex having the partial structure described above.

[0122] This embodiment may also relate to a method for decomposing a urethane compound in the presence of a catalyst containing a complex having the partial structure described above, thereby obtaining formamides and / or alcohols. The decomposition method of this embodiment is not a complete decomposition method in which a urethane compound is decomposed to produce amines and alcohols, but rather a method in which a urethane compound is decomposed to produce formamides and alcohols, and therefore can also be called a partial decomposition method. In other words, this embodiment relates to a method for partially decomposing a urethane compound in the presence of a catalyst containing a complex having the partial structure described above.

[0123] The partial hydrogenation method and partial decomposition method described above also make it possible to decompose urethane-based compounds such as polyurethane. This embodiment may relate to a partial hydrogenation method or partial decomposition method for polyurethane. If plastic materials such as polyurethane can be decomposed, chemical recycling becomes possible. In this way, the partial hydrogenation method and partial decomposition method described above are very useful methods from the viewpoint of environmental protection.

[0124] The features of the present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[0125] (Test Example 1) (Synthesis of Iridium-Phosphine Pyrrolate Complex (Ir / PP Complex)) 5.29 g (0.0155 mol) of (2-bromophenyl)diphenylphosphine and 200 ml of MeOH were added to a 300 ml recovery flask, cooled to 0°C, and 8 equivalents of aqueous hydrogen peroxide (34.5% by mass) were added. The solution temperature was then raised to room temperature and reacted for 1 hour. After the reaction, completion of the reaction was confirmed by TLC, and the mixture was extracted with dichloromethane (DCM) and diluted with MgSO ４ The oxidized product was obtained by filtration and vacuum drying.

[0126] In a 20 ml Schlenk flask, 847 mg (2.37 mmol) of the obtained oxidized product, 2.0 equivalents of 1-Boc-2-pyrroleboronic acid, and Pd(dba) were added. ２0.03 equivalent, PPh ３ 0.12 equivalent, Na ２ CO ３ 3.0 equivalents of dehydrated DMF (8.5 ml) was added, and N ２ The reaction was carried out under an atmosphere at 130°C for 4 days. After the reaction, the solution temperature was returned to room temperature, diluted with water, extracted with DCM, and ４ After drying with hexane and filtering, the mixture was subjected to silica gel column chromatography (Hex / EtOAc=4:1) and dried in vacuo to obtain a coupling product.

[0127] In a 20 ml Schlenk tube, 755 mg (2.2 mmol) of the resulting coupling product and HSiCl ３ 5.0 equivalents, dehydrated and degassed Et ３ Add 5.5 equivalents of N and dehydrated and degassed toluene (20 ml), ２ The mixture was refluxed under atmospheric pressure at 120°C for 5 hours. After the reaction, saturated NaHCO ３ 2 ml of an aqueous solution was added, and the mixture was stirred for 5 minutes, then filtered through alumina. The filtrate was concentrated and subjected to silica gel column chromatography (Hex / EtOAc=9:1), and dried in vacuo to obtain the reduced product.

[0128] In a glove box, 33 mg (0.1 mmol) of the resulting reduced product and 2 ml of THF were added to a vial and stirred. 1.5 equivalents of NaH were added and the mixture was allowed to react at room temperature for 14 hours. After the reaction, the solution was filtered using a membrane filter, and the filtrate was diluted with [IrCl(cod)]. ２ 0.5 equivalents of the compound was added and reacted at room temperature for 24 hours. After the reaction, the solution was concentrated, washed with hexane, extracted with toluene, and the extracted solution was concentrated to obtain an iridium-phosphinepyrrolate complex (Ir / PP complex).

[0129]

[0130] The spectral data of the obtained iridium-phosphine pyrrolate complex (Ir / PP complex) was as follows: PP ligand １ H NMR (400MHz, CDCl ３): δ8.78 (brs, 1H), 7.54-7.28 (m, 12H), 7.16 (dd, J = 7.6, 7.6Hz, 1H), 6.97 (dd, J = 6.8, 4.8Hz, 1H), 6.77 (m, 1H), 6.25 (m, 1H), 6.19 (m, 1H) ３１ P NMR (162 MHz, CDCl ３ ): δ-11.2 PP / Ir complex １ H NMR (400MHz, C ６ D ６ ): δ7.87 (dd, J=8.0, 4.8Hz, 1H), 7.50 (m, 4H), 7.19-6.91 (m, 10H), 6.74 (m, 1H), 6.61 (m, 1H), 5. 46 (dd, J=5.6, 2.4Hz, 2H), 2.82 (dd, J=5.2, 2.8Hz, 2H), 2.19 (m, 2H), 2.01 (m, 2H), 1.70 (m, 4H); ３１ P NMR (162MHz, C ６ D ６ ): δ 16.9

[0131] (Reaction with Urea Compounds (Symmetric Urea Compounds)) <Hydrogenation Reaction> In a glove box, 0.5 mmol of substrate (urea compounds 1a to 1q exemplified below), 3 mol % of catalyst (Ir complex obtained above), and optionally a base (potassium t-butoxide) and 3 ml of solvent (THF or toluene) were placed in a glass tube, which was then sealed in an autoclave. The tube was then removed from the glove box, hydrogen pressure was applied, and the reaction was initiated in a chemistration set to each reaction temperature.

[0132] <Quenching and quantification> The autoclave was removed from the chemistry station, cooled to room temperature, and then the hydrogen pressure was released. If the urea compound substrate remained dissolved in the solution after the reaction, it was dissolved in DMSO-d ６ (2 ml) was added to make the solution homogenous, and then NMR analysis was performed. ６ Dibromomethane was used as the internal standard, but if peak overlapping was observed, heptane was used instead as the internal standard, or DMSO-d ６A mixed solvent of toluene and THF was added so that the ratio of the solvent was 4:1:1, and NMR analysis was carried out.

[0133] <Isolation> -Isolation as hydrochloride- After diluting the solution after the hydrogenation reaction with ethyl acetate, anilines were extracted as aniline hydrochlorides with 1M aqueous hydrochloric acid. The extracted aqueous layer was neutralized with sodium bicarbonate, and subsequently extracted as anilines with DCM. Thereafter, the DCM layer was washed with brine, and Na ２ SO ４ After drying with HCl and filtering, the solution was reacted with MeOH.HCl solution to form aniline hydrochlorides, and the solution was concentrated and dried under vacuum to isolate the aniline hydrochlorides. The ethyl acetate layer was washed with brine and ２ SO ４ After drying and filtration, the formamides were isolated by silica gel column chromatography (DCM / EtOAc).

[0134] When the urea compounds 1c, 1i, and 1l were used, the anilines were isolated instead of the aniline hydrochlorides. Specifically, the reaction solution was concentrated, and the anilines were isolated by silica gel column chromatography (DCM / EtOAc).

[0135] The structures of the urea compounds used as substrates and the formamides and anilines obtained after the hydrogenation reaction are as follows. The values ​​written below each compound are the yields of formamides and anilines obtained after the hydrogenation reaction. The yields of each compound (molar yield of each compound relative to 1 mol of the urea compound) were calculated using dibromomethane / heptane as an internal standard. １ The yield was measured by H NMR. The numbers in parentheses are the yields after isolation.

[0136]

[0137]

[0138]

[0139]

[0140] (Reaction with Urea Compound (Asymmetric Urea Compound)) A hydrogenation reaction was carried out in the same manner as above, except that the urea compound shown below was used as the substrate.

[0141] The structures of the urea compounds used as substrates and the formamides and anilines obtained after the hydrogenation reaction are as follows. The values ​​written below each compound are the yields of formamides and anilines obtained after the hydrogenation reaction. The yields of each compound (molar yield of each compound relative to 1 mol of the urea compound) were calculated using dibromomethane / heptane as an internal standard. １ The yield was measured by H NMR. The numbers in parentheses are the yields after isolation.

[0142]

[0143]

[0144]

[0145]

[0146] (Study on additives) Potassium t-butoxide (KO) was used as an additive (base) during the hydrogenation reaction. ｔ Instead of sodium t-butoxide (NaO ｔ Bu) or t-butoxylithium (LiO ｔ As an additive (base) during the hydrogenation reaction, potassium t-butoxide (KO ｔ Bu) gave favorable results.

[0147]

[0148]

[0149] (Reaction with Polyurea) <Synthesis of Polyurea> 1.60 g (10 mmol) of 1,4-phenylenediisocyanate and dehydrated DMF were added to a 50 ml two-necked recovery flask, and 1.0 equivalent of N,N'-dimethyl-1,6-hexanediamine was added dropwise thereto. The solution temperature was then raised to 80°C, and the reaction was carried out for 17 hours. After the reaction, 1.0 equivalent of water was added, and the mixture was washed twice with 200 ml of THF, followed by vacuum drying at 100°C for 8 hours to obtain polyurea.

[0150]

[0151] A hydrogenation reaction was carried out in the same manner as above, except that the above polyurea was used as the substrate. The structures of the formamides and anilines obtained after the hydrogenation reaction were as follows. The yield of the soluble components after the reaction was calculated by NMR in the same manner as above. Phenylenediamine (product, upper left) was added to the soluble portion, and the solid component after the reaction was isolated in a yield of 39% by washing with a solvent.

[0152]

[0153] (Hydrogenolysis of Polyurea) Using the above polyurea as a substrate, a hydrogenation reaction was carried out under the following conditions.

[0154]

[0155]

[0156] Regarding the hydrogenolysis of polyurea, the results of entry 4 were as follows:

[0157]

[0158] (Hydrogenolysis of Urethane Compounds) The following urethane compounds were used as substrates, and hydrogenation reactions were carried out under the following conditions.

[0159]

[0160] The Ir complex partially hydrogenated the urethane compounds to produce formamides and alcohols.

[0161] (Results) As described above, the Ir complex partially hydrogenated urea compounds to produce formamides and amines. The Ir complex partially hydrogenated both symmetric and asymmetric urea compounds. In the partial hydrogenation of asymmetric urea compounds, the combination of substituents on the nitrogen atom allowed selective hydrogenation of one of the carbon-nitrogen bonds. Furthermore, the urea compounds were selectively hydrogenated even when they contained easily reducible functional groups such as halogen atoms, ester groups, and cyano groups. The Ir complex also partially hydrogenated urethane compounds to produce formamides and alcohols.

[0162] (Test Example 2) (Synthesis of Iridium-Phosphine Benzimidazolate Complex (Ir / PB Complex)) A 300 ml recovery flask was charged with 13 mL of a mixed solvent of ethanol / water (5 / 1), 27 mg (2.0 mmol) of 2-nitroaniline, 697 mg (2.4 mmol) of (2-diphenylphosphino)benzaldehyde, and Na ２ S ２ O ４　 1.4 g (8.0 mmol) of the ethanol was added and reacted for 6 hours at 75° C. After the reaction, ethanol was distilled off under reduced pressure, water and ethyl acetate were added, the mixture was extracted with ethyl acetate, concentrated, subjected to silica gel column chromatography (hexane / ethyl acetate), and dried in vacuo to obtain an oxidized product in a 39% yield.

[0163] To toluene (6.4 mL), 253 mg (0.64 mmol) of the oxidant, 567 mg (4.2 mmol) of trichlorosilane, and 480 mg (4.7 mmol) of triethylamine were added at 0° C. The solution was refluxed for 17 hours. After the reaction, the solvent and excess reagent were distilled off under reduced pressure, and the residue was purified by degassing saturated NaHCO 3 ３ 10 mL of the aqueous solution was added, and the mixture was extracted with dichloromethane under a nitrogen atmosphere, and the solvent was evaporated under reduced pressure. The resulting solid was washed with hexane and dried in vacuo to obtain the reduced product in 97% yield.

[0164] In a glove box, 128 mg (0.34 mmol) of the reduced product was added to 9 mL of THF and stirred, and 13.5 mg (0.51 mmol) of 90% pure NaH was added thereto and reacted at room temperature for 24 hours. After the reaction, the solution was filtered using a membrane filter, and the filtrate was diluted with [IrCl(cod)]. ２ After the reaction, the solution was evaporated under reduced pressure, extracted with hexane, filtered through alumina (washed with 2 CV of diethyl ether and then eluted with 4 CV of THF), and dried in vacuo to obtain an iridium-phosphine benzimidazolate complex (Ir / PB complex) in a 23% yield.

[0165]

[0166] The spectral data of the obtained iridium-phosphine benzimidazolate complex (Ir / PB complex) was as follows: PB ligand １ H NMR (500MHz, DMSO-d ６ ): δ12.7 (s, 1H), 7.88 (dd, J=7.5, 3.5Hz, 1H), 7.56 (t, J=5.0Hz, 1H), 7.49-7.43 (m, 3H), 7. 35-7.30 (m, 6H), 7.23-7.17 (m, 5H), 7.14-7.11 (m, 1H), 7.04-7.02 (dd, J = 7.5, 3.5Hz, 1H); ３１ P NMR (202MHz, DMSO-d ６ ): δ?10.7; １３ C NMR (126MHz, DMSO-d ６ ): δ151.2, 143.2, 138.4 (d, J = 11.8 Hz), 137.6 (d, J = 23.7 Hz), 135.5 (d, J = 23.7 Hz), 134.4 (d, J = 18.3Hz), 133.3 (d, J = 20.0Hz), 129.3, 128.8, 128.4 (d, J = 7.3Hz), 122.5, 121.3, 119.0, 111.3. Ir / PB complex １ H NMR (500MHz, C ６ D ６):δ9.32-9.29(m,1H),8.11(d,J=7.5Hz,1H),7.97(d,J=8.0Hz,1H),7.44-7.41(m,4H),7.32-7.27(m,1H),7.24-7.20(m,2H),6.89-6.80(m,7H),5.36(br,2H),3.11(d,J=2.0Hz,2H),2.09-2.06(m,2H),1.91-1.83(m,2H),1.60-1.51(m,4H),the one remaining proton peak is overlapped with the solvent peak; ３１ P NMR(202MHz,C ６ D ６ ):δ22.3; １３ C NMR(126MHz,C ６ D ６ ):δ156.0(d,J=6.4Hz),150.3,145.7,142.5(d,J=13.9Hz),134.6(d,J=11.1Hz),132.1(d,J=9.2Hz),131.4(d,J=1.9Hz),130.8(d,J=1.9Hz),130.7(d,J=2.8Hz),129.5(d,J=52.5Hz),128.4(overlapped with solvent peaks and confirmed by DEPT analysis,d,J=10.5Hz),127.6(d,J=7.3Hz),123.0(d,J=49.6Hz),121.3,120.3(d,J=8.3Hz),116.1,92.0(d,J=12.0Hz),58.5,33.0,30.2;m.p.:no clear melting point was observed upon heating until 227oC;HRMS(ESI)m / z calcd. for C ３３ H ３０ IrN ２ P([M] ＋ )678.1776,found 678.1747.

[0167] (Reaction with Urea Compound (Symmetric Urea Compound)) <Hydrogenation Reaction> In a glove box, 0.5 mmol of a substrate (a urea compound exemplified below), 3 mol % of a catalyst (the Ir / PB complex obtained above), and 3 ml of a solvent (toluene) were placed in a glass tube, which was then sealed in an autoclave. The tube was then removed from the glove box, hydrogen pressure was applied, and the reaction was initiated in a chemistry station set to the reaction temperature described below. Quantitation was performed in the same manner as described above.

[0168]

[0169] As mentioned above, the Ir / PB complex also partially hydrogenated urea-based compounds to produce formamides and amines.

[0170] (Test Example 3) (Synthesis of PSP Ligand) Sodium hydride (oil-free, 90% purity, 43.2 mg, 1.62 mmol) was added to a THF (1.1 mL) solution of ethyl 2-(diphenylphosphoneyl)benzoate (451.2 mg, 1.35 mmol) at room temperature. The mixture was cooled to 0°C, and 1-vinylpyrrolidine-2-one (162.0 mg, 1.46 mmol) was added. After stirring at 80°C for 2.5 hours, 6M aqueous HCl solution (2.2 mL) was added dropwise. After the reaction solution changed from brown to yellow, THF was distilled off under reduced pressure. 6M aqueous HCl solution (3 mL) was added to the residue, and the mixture was stirred at 100°C for 14 hours. After cooling, 6M aqueous NaOH (6 mL) was added to basify the mixture, resulting in a deep red solution. Extraction with EtOAc (6 mL, seven times) under nitrogen was performed, and the EtOAc was evaporated to give a white solid. This solid was purified using a silica gel column (dichloromethane / methanol = 100 / 0 to 85 / 15) to give the imine (100.6 mg). This imine was dissolved in methanol (2.5 mL) and acetic acid (1.0 mL), and sodium borohydride (27.1 mg, 0.72 mmol, separated into three times) was added at -65°C, followed by stirring at room temperature for 17 hours. The solvent was evaporated, and the residue was added with water (3 mL) and 6 M HCl aqueous solution (2 mL) and washed with Et2O (5 mL, four times). 10 M NaOH aqueous solution (1.5 mL) was added to the aqueous phase, and the mixture was made basic. Extraction with dichloromethane (7 mL, five times) was performed, and the solvent was evaporated to obtain a white solid. This was purified using a silica gel column (dichloromethane / methanol = 100 / 0 to 80 / 20) to obtain PSP as a white solid (17.5 mg, 0.053 mmol, 3.9%).

[0171] The spectral data of the obtained PSP ligand was as follows: PSP ligand ３１ P(CDCl ３ , 162MHz): δ-15.5 １ H(CDCl３ , 400MHz): δ7.74-7.66 (m, 1H), 7.58-7.41 (m, 1H), 7.38-7.30 (m, 7H), 7.14-7.10 (m, 1H), 6.86-6.83 (m, 1H), 4.88 (dd, J=15.4) Hz, 7.2Hz, 1H), 3.19-3.14 (m, 1H), 2.97-2.91 (m, 1H), 2.38 (s, 1H), 1.93-1.80 (m, 2H), 1.79-1.60 (m, 1H), 1.52-1.43 (m, 1H). the three remaining aromatic proton peaks are overlapped with the solvent peak.

[0172] (Hydrogenolysis of Urea Using Ir / PSP Complex) In a glove box, 0.5 mmol of a substrate (a urea-based compound exemplified below), 3 mol% of the PSP ligand obtained above, [IrCl(cod)] ２ 3 mol% Ir and 3 ml of a solvent (toluene) were placed in a glass tube, which was then sealed in an autoclave. The tube was then removed from the glove box, hydrogen pressure was applied, and the reaction was initiated in a chemistry station set to the reaction temperature described below. Quantitative analysis was performed in the same manner as described above.

[0173]

[0174] In the reaction system, an Ir / PSP complex was formed, and the Ir / PSP complex also partially hydrogenated the urea-based compound to produce formamides and amines.

[0175] Test Example 4 Synthesis of Ruthenium-Phosphine Pyrrolate Complex (Ru / PP Complex) In a glove box, 15 mg (0.045 mmol) of 2-(2-diphenylphosphinophenyl)pyrrole was added to 0.8 mL of THF and stirred, and 2.5 equivalents of 90% pure NaH was added thereto and reacted at room temperature for 23 hours. After the reaction, the solution was filtered using a membrane filter, and the filtrate was diluted with [RuCl ２ (cod)] ｎOne equivalent of was added, 1.0 mL of THF was added, and the reaction was carried out for 18 hours at 50° C. After the reaction, 0.2 mL of the 1.8 mL of THF solution was taken to obtain a ruthenium-phosphine pyrrolate complex (Ru / PP complex).

[0176] (Reaction with Urea Compound (Symmetric Urea Compound)) <Hydrogenation Reaction> In a glove box, 0.17 mmol of substrate (a urea compound exemplified below), 0.2 mL of catalyst / THF solution (the Ru / PP complex obtained above), and 1.8 mL of solvent (toluene) were placed in a medium-sized glass tube, which was then sealed in an autoclave. The tube was removed from the glove box, and a hydrogen pressure of 2 MPa was applied. The reaction was initiated for 18 hours in a chemistration set to 130° C. Quantitation was performed in the same manner as described above.

[0177]

[0178] As mentioned above, the Ru / PP complex also partially hydrogenated urea-based compounds to produce formamides and amines.

[0179] (Test Example 5) (Synthesis of manganese-phosphine pyrrolate complex (Mn / PP complex)) Following the synthesis of the Ir / PP complex in Test Example 1, MnBr(CO) ５ By using this, a manganese-phosphine pyrrolate complex (Mn / PP complex) was obtained in 87% yield.

[0180]

[0181] (Reaction with Urea Compound (Symmetric Urea Compound)) <Hydrogenation Reaction> In a glove box, 0.167 mmol of substrate (urea compound exemplified below), 3 mol % of catalyst (Mn / PP complex obtained above), 10 mol % of base (potassium t-butoxide), and 3 ml of solvent (toluene) were placed in a glass tube, which was then sealed in an autoclave. The tube was then removed from the glove box, hydrogen pressure was applied, and the reaction was initiated in a chemistry station set to the reaction temperature described below. Quantitation was performed in the same manner as described above.

[0182]

[0183] As mentioned above, the Ru / PP complex also partially hydrogenated urea-based compounds to produce formamides and amines.

[0184] (Test Example 6) (Synthesis of Cationic Complex) 49 mg (0.15 mmol) of 2-(2-diphenylphosphinophenyl)pyrrole and [Ir(cod)] were dissolved in THF (3 mL). ２ ]BAr Ｆ ４ After the reaction, the solution was evaporated under reduced pressure, and the resulting solid was washed with hexane and dried in vacuo to obtain 220 mg of an Ir complex (cationic complex).

[0185] The spectral data of the obtained Ir complex (cationic complex) was as follows: １ H NMR (500MHz, THF-d ８ ): δ11.8 (br, 0.8H), 8.11-7.46 (m, 33H), 7.39 (s, 0.8H), 7.24 (d, J = 5.5Hz, 0.2H), 7.04 (d, J = 2.0Hz, 0.8H), 6.25 (s, 0.8H), 5.38 (br, 0 .4H), 5.21 (br, 1.6H), 4.96 (s, 0.4H), 3.45 (br, 0.4H), 3.41 (br, 1.6H), 2.33-2.08 (m, 8H), 1.63-1.31 (m, 8H); 31PNMR (202MHz, THF-d ８ ): δ26.1, 18.0; 13CNMR (126MHz, THF-d ８): δ162.9 (q, J = 49.7 Hz), 156.2, 141.7 (d, J = 7.3 Hz), 141.1 (d, J = 19.0 Hz), 137.0 (d, J = 14.5 Hz), 136.6, 135.7, 135.3 (d, J = 11. 0Hz), 134.5 (d, J = 8.2Hz), 133.9, 133.8 (d, J = 1.8Hz), 133.7 (d, J = 5.5Hz), 133.6 (d, J = 20.0Hz), 133.0 (d, J = 2.6Hz), 132.9 (d, J = 2.8Hz), 131.4 (d, J = 6.3Hz), 131.0, 130.5-129.7 (m), 129.4, 128.8, 127.4 (d, J = 55.6Hz), 126.7, 126.2 (d, J = 47.3Hz), 125.7, 124.5, 122.3, 118.3-118.2 (m), 95.9 (d, J = 12.7 Hz), 85.8, 72.6, 71.4, 66.0, 33.2 (d, J = 2.6 Hz), 31.2, 30.6 (d, J = 1.9 Hz), 27.7.

[0186] The π-coordination of pyrrole was confirmed in the cationic complex. Furthermore, the π-coordination and σ-coordination of pyrrole were in equilibrium. This result supports the reaction mechanism described in paragraphs 0064 and 0065 above.

[0187]

Claims

1. A catalyst comprising a complex having a partial structure represented by the following formula (A): 【Chemistry 1】 (In formula (A), M is a metal that is an element of Group 7, 8, or 9 and has an Allred-Rochow electronegativity of 1.40 or more and a third ionization potential of 26.5 eV or more; P and M are coordinate bonded, D １ represents an atomic group containing an anionic nitrogen atom as a bond to M, X １ is a linking group, R １ and R ２ each independently represents a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, M is connected to other sites with *.)

2. The catalyst according to claim 1, comprising an iridium complex having a partial structure represented by the following formula (1): 【Chemistry 2】 (In formula (1), P and Ir are coordinate bonded, D １ represents an atomic group containing an anionic nitrogen atom as a bond to Ir, X １ is a linking group, R １ and R ２ each independently represents a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, Ir is bonded to other sites with *.)

3. The catalyst according to claim 1, comprising an iridium complex having a partial structure represented by the following formula (2): 【Transformation 3】 (In formula (2), P and Ir are coordinate bonded, Ring A represents a nitrogen-containing ring containing an anionic nitrogen; X １ is a linking group, R １ and R ２ each independently represents a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, Ir is bonded to other sites with *.)

4. The catalyst according to claim 1, comprising an iridium complex having a partial structure represented by the following formula (3): 【Chemistry 4】 (In formula (3), P and Ir are coordinate bonded, Ring A represents a nitrogen-containing ring containing an anionic nitrogen; Ring B represents an aromatic ring; R １ and R ２ each independently represents a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, Ir is bonded to other sites with *.)

5. R １ and R ２ The catalyst of claim 1 , wherein each of the groups is independently an aromatic hydrocarbon group.

6. A method for producing formamides and / or amines, comprising reacting a urea compound with the catalyst according to any one of claims 1 to 5.

7. The method for producing formamides and / or amines according to claim 6 , wherein the urea compound is a compound represented by the following formula (11): 【Transformation 5】 (In formula (11), L １ and L ２ are each independently a single bond or a linking group, R １１ and R １２ are each independently a hydrogen atom or a substituent, R １３ and R １４ are each independently a hydrogen atom or a substituent, and R １３ and R １４ at least one of is a hydrogen atom, R １１ and R １２ may be linked together to form a ring, or R １１ and R １３ and R １２ and R １４ may be linked to each other to form a ring, n is an integer of 1 or more.

8. In the formula (11), R １１ and R １２ is a hydrocarbon group, and R １３ and R １４ The method for producing formamides and / or amines according to claim 7, wherein is a hydrogen atom.

9. In the formula (11), R １１ and R １２ are the same group, and R １３ and R １４ are the same group, and L １ and L ２ The method for producing formamides and / or amines according to claim 7, wherein are the same group.

10. In the formula (11), at least R １１ and R １２ , R １３ and R １４ , or L １ and L ２ The method for producing formamides and / or amines according to claim 7 , wherein

11. A method for producing formamides and / or alcohols, comprising reacting a urethane compound with the catalyst according to any one of claims 1 to 5.

12. A complex having a partial structure represented by the following formula (B): 【Transformation 6】 (In formula (B), M is a metal that is an element of Group 7, 8, or 9 and has an Allred-Rochow electronegativity of 1.40 or more and a third ionization potential of 26.5 eV or more; P and M are coordinate bonded, Ring A represents a nitrogen-containing ring containing an anionic nitrogen; Ring B represents an aromatic ring; R １ and R ２ each independently represents a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, M is connected to other sites with *.)

13. The complex according to claim 12, having a partial structure represented by the following formula (3): 【Transformation 7】 (In formula (3), P and Ir are coordinate bonded, Ring A represents a nitrogen-containing ring containing an anionic nitrogen; Ring B represents an aromatic ring; R １ and R ２ each independently represents a substituent containing at least one atom selected from the group consisting of a carbon atom, an oxygen atom, and a nitrogen atom, and these substituents may be linked to each other to form a ring, Ir is bonded to other sites with *.)

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