JP2019042708A - Catalyst composition for producing aromatic carboxylic acid or ester thereof from carbon dioxide and aromatic halogen compound, and a method for producing aromatic carboxylic acid or ester thereof using the catalyst composition - Google Patents

Abstract

To provide a catalyst cycle which carboxylates an aromatic halogen compound without using a metallic reduction agent.SOLUTION: Provided is a catalyst composition for producing an aromatic carboxylic acid or an ester thereof from carbon dioxide and an aromatic halogen compound under a light irradiation condition. The catalyst composition comprises: a light oxidation-reduction catalyst component (A) containing a transition metal M which belongs to Periodic Table Groups 8-10; and a transition metal catalyst component (B) containing a transition metal M' which belongs to Periodic Table Groups 8-11 and is different from the transition metal M.SELECTED DRAWING: None

Description

  The present invention relates to a catalyst composition for producing an aromatic carboxylic acid or an ester thereof from carbon dioxide and an aromatic halogen compound, more specifically to a specific photoredox catalyst component (A) and a specific transition metal catalyst component The present invention relates to a catalyst composition containing (B). In addition, the present invention relates to a method for producing an aromatic carboxylic acid or an ester thereof using the catalyst composition.

  In recent years, a reaction of carboxylating an organic halogen compound with carbon dioxide has attracted attention using transition metal catalyst components such as Pd, Ni and Cu. Specifically, a method is known in which aromatic bromide is directly carboxylated by reaction with carbon dioxide in the presence of a palladium catalyst (Non-patent Document 1). Also known is a method of carboxylating aromatic chloride or vinyl chloride by reaction with carbon dioxide in the presence of a nickel catalyst (Non-patent Document 2).

  On the other hand, as a reaction that does not require a metal reductant, a catalyst cycle is known that emits visible light in the presence of a Rh (I) complex and a photoredox catalyst component and hydrocarboxylates an alkene by reaction with carbon dioxide. (Non-Patent Document 3).

Arkaitz Correa, and Ruben Martin, Palladium-Catalyzed Direct Carboxylation of Aryl Bromides with Carbon Dioxide, J. AM. CHEM. SOC. 2009, 131, 15974-15975, DOI: 10.1021 / ja905264a Tetsuaki Fujihira, Keisuke Nogi, Tinghua Xu, Jun Terao, and Yasushi Tsuji, Nickel-Catalyzed Carboxylation of Aryl and Vinyl Chlorides Employing Carbon Dioxide, J. AM. CHEM. SOC. 2012, 134, 9106-9109, DOI: 10.1021 / ja303514b Kei Murata, Nobutsugu Numsawa, Katsuya Shimomaki, and Jun Takaya, and Nobuharu Iwasawa, Construction of a visible light-driven hydrocarboxylation cycle of alkenylenes by the combined use of Rh (I) and photoredox catalysts, Chem, Comm, DOI

The methods described in Non-Patent Documents 1 and 2 require a large amount of metal reducing agent such as Et ₂ Zn or Mn, which is not preferable from the environmental aspect. In addition, although Non-Patent Document 3 succeeds in hydrocarboxylating an olefin by a photoredox catalytic reaction, it has not reached carboxylation of an aromatic halogen compound.

  Then, this invention aims at solving the said subject. That is, the present invention provides a catalyst composition for carboxylating an aromatic halogen compound without using a metal reducing agent containing a transition metal element such as Zn or Mn (a transition metal element belonging to Group 7 or 12 of the periodic table). Intended to provide.

  By using a catalyst composition containing a specific photoredox catalyst component and a specific transition metal catalyst component, the present inventors can use carbon dioxide and an aromatic without using a metal reducing agent under light irradiation conditions. We have found a catalytic cycle for producing aromatic carboxylic acids or their esters from halogen compounds.

That is, the present invention provides the following specific embodiments.
[1] Photoredox catalyst component (A) containing transition metal M belonging to periodic table groups 8 to 10 and transition metal catalyst containing transition metal M ′ belonging to periodic table groups 8 to 11 and different from said transition metal M Contains component (B),
A catalyst composition for producing an aromatic carboxylic acid or an ester thereof from carbon dioxide and an aromatic halogen compound under light irradiation conditions.

[2] The catalyst composition according to [1], wherein the photoredox catalyst component (A) is a compound represented by the general formula (1).
(N-C) _3-x (N-N) _x M (1)
(In the above general formula (1), N represents a nitrogen atom, C represents a carbon atom, and N—C represents a bidentate ligand coordinated to the transition metal M with a nitrogen atom and a carbon atom. And N-N each represents a bidentate ligand coordinated to the transition metal M with a nitrogen atom and a nitrogen atom, and x represents an integer of 0 to 3.)
[3] The catalyst composition according to [1] or [2], wherein the transition metal M is iridium or ruthenium.
[4] The catalyst composition according to any one of [1] to [3], wherein the transition metal M ′ is at least one selected from the group consisting of palladium, cobalt, nickel and iron.
[5] The catalyst composition according to any one of [1] to [4], wherein the transition metal catalyst component (B) contains a phosphorus atom.

[6] Photoredox catalyst component (A) containing transition metal M belonging to periodic table groups 8 to 10, and transition metal catalyst containing transition metal M ′ belonging to periodic table groups 8 to 11 and different from said transition metal M A method for producing an aromatic carboxylic acid or an ester thereof, comprising the step of irradiating carbon dioxide and an aromatic halogen compound with light in the presence of a catalyst composition containing component (B).
[7] The method for producing an aromatic carboxylic acid or ester thereof according to [6], wherein the aromatic halogen compound is an aromatic chloride, an aromatic bromide or an aromatic iodide.
[8] The method for producing an aromatic carboxylic acid or ester thereof according to [6] or [7], wherein a tertiary amine compound is present together with the catalyst composition.
[9] The method for producing an aromatic carboxylic acid or ester thereof according to any one of [6] to [8], wherein a basic compound is present together with the catalyst composition.

  According to the catalyst composition of the present invention, an aromatic halogen compound can be carboxylated without using a metal reducing agent. Further, according to the production method of the present invention, since the aromatic carboxylic acid or the ester thereof can be produced from carbon dioxide and the aromatic halogen compound by light irradiation in the presence of a specific catalyst composition, the metal reducing agent It is unnecessary and can reduce the environmental load.

  Hereinafter, the embodiments of the present invention will be described in detail, but the following embodiments are exemplifications for explaining the present invention, and the present invention is not limited to these, and does not deviate from the gist thereof It can be arbitrarily changed and implemented within the scope. In addition, in this specification, when expressing using numerical value or physical property value on either side before and behind that using "-", suppose that it uses as a thing containing numerical value or physical property value before and behind that. For example, the notation of the numerical range of "1 to 100" includes both of the lower limit value "1" and the upper limit value "100", and represents "1 or more and 100 or less". The notation of other numerical ranges is also the same.

1. Catalyst Composition The catalyst composition of the present embodiment is used to produce an aromatic carboxylic acid or an ester thereof from carbon dioxide and an aromatic halogen compound under light irradiation conditions, and belongs to periodic table groups 8 to 10 It is characterized by containing a photoredox catalyst component (A) containing a transition metal M and a transition metal catalyst component (B) containing a transition metal M ′ which belongs to Groups 8 to 11 of the periodic table and is different from the transition metal M. I assume.
According to the catalyst composition of the present embodiment, at the stage of elimination of halogen anion and reductive elimination of aromatic carboxylic acid, transition metal catalyst from photoredox catalyst component (A) excited under light irradiation conditions It is presumed that the reaction proceeds by passing electrons to the component (B).

  The components included in the catalyst composition of the present embodiment will be described below in the order of the photoredox catalyst component (A) and the transition metal catalyst component (B).

[Photo-redox catalyst component (A)]
The photoredox catalyst component (A) contains a transition metal M belonging to Group 8 to Group 10 of the periodic table. The transition metal M is not particularly limited as long as it is a transition metal element belonging to periodic table groups 8 to 10, but is preferably iridium or ruthenium, more preferably iridium.

It is preferable that such a photo-redox catalyst component (A) is a compound represented by the following general formula (1).
(N-C) _3-x (N-N) _x M (1)
(In the general formula (1), N represents a nitrogen atom, C represents a carbon atom, and N—C represents a bidentate ligand coordinated to the transition metal M with a nitrogen atom and a carbon atom, -N represents a bidentate ligand coordinated to the transition metal M with a nitrogen atom and a nitrogen atom, and x represents an integer of 0 to 3. x is preferably 1 or 2, x Is more preferably 1.)

  The bidentate ligand (N-C) coordinated to the transition metal M by a nitrogen atom and a carbon atom includes one or more nitrogen atoms and one or more carbon atoms in the molecule, and It may be a compound capable of forming a complex by forming a coordinate bond between the nitrogen atom and the carbon atom and the transition metal M to be bidentately coordinated. As such a compound, for example, a compound having a phenylpyridine skeleton, a compound having a phenylquinoline skeleton, a compound having a phenylisoquinoline skeleton, a compound having a phenylimidazole skeleton, a compound having a pyridylpyridine skeleton, a compound having a naphthylpyridine skeleton A compound having a pyridylbenzothiophene skeleton, a compound having a phenylbenzothiazole skeleton, a compound having an isoquinolylbenzothiophene skeleton, a compound having a phenylquinoxaline skeleton, a compound having a phenylbenzoisoquinoline skeleton, a compound having a phenylpyrazole skeleton, phenyl Examples thereof include compounds having a tetrazole skeleton, and compounds having a phenylbenzimidazole skeleton. Among these, a compound having a phenylpyridine skeleton is preferable, and a compound having a 2-phenylpyridine skeleton is more preferable.

As a compound which has 2-phenylpyridine frame | skeleton, 2-phenylpyridine and its derivative (s) are mentioned, for example. Here, derivatives of 2-phenylpyridine include 2-phenylpyridine having a substituent. The substituent which such a derivative has is not particularly limited. For example, the alkyl group having 1 to 10 carbons such as methyl and ethyl (C _{1 to 10} alkyl), and carbons such as methoxy and ethoxy And an alkoxy group having 1 to 10 carbon atoms (C _1-10 alkoxy group), a halogen atom such as a fluorine atom, and an alkyl group containing a fluorine atom such as a trifluoromethyl group.

  When the compound having a 2-phenylpyridine skeleton has a substituent, the number of substituents is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less. For example, a compound having a 2-phenylpyridine skeleton preferably has a substituent at any of positions 5,4 'and 6', and more preferably has a substituent at position 5,4 'and 6' .

Moreover, as a bidentate ligand (N-N) which coordinates to transition metal M by a nitrogen atom and a nitrogen atom, it has 2 or more nitrogen atoms in a molecule, and these nitrogen atoms are transition metal M And a compound capable of forming a complex by forming a coordinate bond between them and forming a bidentate coordinate. As such a compound, a compound having a bipyridine skeleton such as bipyridine and its derivative, a compound having a phenanthroline skeleton such as phenanthroline and its derivative, ethylene diamine and the like can be mentioned. Among these, a compound having a bipyridine skeleton and a compound having a phenanthroline skeleton are preferable, and a compound having a bipyridine skeleton is more preferable. Moreover, among the compounds having a bipyridine skeleton, a compound having a 2,2'-bipyridine skeleton is preferably used. Among the compounds having a phenanthroline skeleton, a compound having a 1,10-phenanthroline skeleton is preferably used.
The derivatives of bipyridine include bipyridine having a substituent. Further, derivatives of phenanthroline include phenanthroline having a substituent. The substituent which these derivatives have is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl and t-butyl (C _1-10 alkyl groups), methoxy groups and the like A C1-C10 alkoxy group ( _C1-10 alkoxy group), a phenyl group, etc., such as an ethoxy group, etc. are mentioned. As these substituents, a C _1-10 alkyl group and a C _1-10 alkoxy group are preferable, a C _1-5 alkyl group and a C _1-5 alkoxy group are more preferable, and a C _1-5 alkyl group is particularly preferable. In addition, these substituents may have another substituent further.

  When the compound having a 2,2′-bipyridine skeleton or the compound having a 1,10-phenanthroline skeleton has a substituent, the number of substituents is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 Below, Preferably it is four or less. For example, a compound having a 2,2'-bipyridine skeleton preferably has a substituent at any of at least the 4, 4 'positions, and more preferably has a substituent at the 4, 4' positions. In addition, the compound having a 1,10-phenanthroline skeleton preferably has a substituent at any of 3,4,7,8 position, and more preferably has a substituent at 3,4,7,8 position preferable.

  The above bidentate ligands can be used alone or in combination of two or more.

Preferred specific examples of the photoredox catalyst component (A) include, for example, tris (2,2'-bipyridine) ruthenium dichloride (Ru (bpy) ₃ Cl ₂ ), tris (2,2'-bipyridine) ruthenium bis ( Hexafluorophosphate) (Ru (bpy) ₃ (PF ₆ ) ₂ ), Tris (2- (2-pyridinyl-κN) phenyl-κC) iridium (fac-Ir (ppy) ₃ ), bis (2- (2- (2-) Pyridinyl-κN) phenyl-κC) (4,4'-ditertiarybutyl-2,2'-bipyridine) iridium (hexafluorophosphate) (Ir (ppy) ₂ (dtbbpy) (PF ₆ )), bis (2- (2)) (5-Trifluoromethylpyridin-2-yl-κN) -4,6-difluorophenyl-κC) (4,4'-ditertiarybutyl-2,2'-bipyridine) iridium (hexafluorophosphate) (Ir ( _{dF (CF 3) ppy) 2} (dtbbpy) (PF 6)), bis (2- (5-trifluoromethyl-pyridin-2-yl -κN) -4, - difluorophenyl-KC) (2,2'-bipyridine) iridium _{(hexafluorophosphate) (Ir (dF (CF 3} ) ppy) 2 (bpy) (PF 6)), bis (2- (pyridinyl -KappaN) phenyl -κC) (4,4'-Dimethoxy-2,2'-dipyridinyl) iridium (hexafluorophosphate) (Ir (ppy) ₂ (dmobpy) (PF ₆ )), bis (2- (pyridinyl-κN) phenyl- κC) (4,4'-diphenyl-2,2'-dipyridinyl) iridium (hexafluorophosphate) (Ir (ppy) ₂ (bpbpy) (PF ₆ )), bis (2- (pyridinyl-κN) phenyl--C ) (1, 10-phenanthroline) iridium (hexafluorophosphate) (Ir (ppy) ₂ (phen) (PF ₆ )), bis (2- (pyridinyl- N N) phenyl- C C) (3, 4, 7, 8) -Tetramethyl-1,10-phenanthroline) iridium (hexafluorophosphate) (Ir (ppy) ₂ (Me ₄ phen) (PF ₆ )) and the like can be mentioned. . You may use these photoredox catalyst components (A) individually or in combination of 2 or more types.

From the viewpoint of excellent yield of the aromatic carboxylic acid, more preferable specific examples of the photo-redox catalyst component (A) are Ir (dF (CF ₃ ) ppy) ₂ (dtbbpy) (PF ₆ ), Ir (ppy) _{2 (dtbbpy) (PF 6),} Ir (ppy) 2 (dmobpy) (PF 6), be _{Ir (ppy) 2 (bpbpy)} (PF 6) , and _{Ir (ppy) 2 (Me 4} phen) (PF 6) Further preferred examples are Ir (ppy) ₂ (dtbbpy) (PF ₆ ) and Ir (ppy) ₂ (dmobpy) (PF ₆ ), and particularly preferred examples are Ir (ppy) ₂ (dtbbpy) (PF) ₆ )

The content ratio of the photoredox catalyst component (A) in the catalyst composition is not particularly limited, but is usually 0.01 mol% or more, preferably to the aromatic halogen compound which is the starting material (substrate) of the carboxylation reaction. It is 0.1 mol% or more, more preferably 0.5 mol% or more, and usually 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less.
If the content of the photoredox catalyst component (A) is low, the catalyst cycle may not proceed sufficiently. On the other hand, when the content ratio of the photoredox catalyst component (A) is high, there is a tendency that no significant improvement in the effect is observed, which is not economical.

[Transition metal catalyst component (B)]
The transition metal catalyst component (B) belongs to periodic table groups 8 to 11, and contains a transition metal M ′ different from the transition metal M contained in the photoredox catalyst component (A).
The transition metal M ′ is not particularly limited as long as it is a transition metal element belonging to Groups 8 to 11 of the periodic table, but a transition metal element other than rhodium is preferable, and at least one selected from the group consisting of palladium, cobalt, nickel and iron It is more preferably a species, more preferably palladium or nickel, particularly preferably palladium.

  The transition metal catalyst component (B) preferably contains a phosphorus atom. Such transition metal catalyst component (B) is a complex comprising a catalyst precursor containing transition metal M 'and a monodentate ligand containing a phosphorus atom.

Specific examples of the catalyst precursor containing palladium include, for example, Pd (PPh ₃ ) ₄ , Pd (P (o-tol) ₃ ) ₄ , Pd (P (tBu) ₃ ) ₄ , Pd ₂ (dba) ₃ , _{Pd 2 (dba) 3 · CHCl} 3, Pd (dba) 2, Pd (MeCN) 4 (BF 4) 2, PdCl 2, PdBr 2, Pd (acac) 2, Pd (TFA) 2, Pd (allyl) Cl _{2, [(allyl) PdCl]} 2, Pd (PCy 3) 2 Cl 2, Pd (P (o-tol) 3) 2 Cl 2, Pd (OAc) 2, PdCl 2 (dppf), PdCl 2 (dppf) _{CH 2 Cl 2, Pd (MeCN} ) 2 Cl 2, Pd (amPhos) Cl 2, PdCl 2 (dtbpf) or PdCl _{2 (PPh 3) 2,} etc., palladium 0 Ataimata Divalent ones, and the like.
In the present specification, Ph is phenyl, o-tol is o-tolyl, tBu is tert-butyl, dba is dibenzylideneacetone, MeCN is acetonitrile, acac is acetylacetonate, TFA is trifluoroacetate, OAc is acetate, allyl is allyl, Cy is a cyclohexyl group, dppf is 1,1'-bis (diphenylphosphino) ferrocene, dtbpf is 1,1'-di-tert-butylphosphinoferrocene, PPh ₃ is triol Phenyl phosphine, amPhos represents [4- (N, N-dimethylamino) phenyl] di-tert-butyl phosphine.
You may use these catalyst precursors individually or in combination of 2 or more types.
Among these, Pd (OAc) ₂ and [(allyl) PdCl] ₂ are preferable, and Pd (OAc) ₂ is more preferable, from the viewpoint of excellent yield of aromatic carboxylic acid.

As a monodentate ligand containing a phosphorus atom (hereinafter sometimes referred to simply as “ligand”), it has one or more phosphorus atoms in the molecule, and this phosphorus atom is a transition metal M ′. And a compound capable of forming a complex by monodentate coordination by forming a coordinate bond therebetween.
As such a compound, it is preferable to use an organophosphorus compound represented by the general formula P (R _x ) ₃ . R _x represents a substituent bonded to a phosphorus atom (P). R _x is a substituted or unsubstituted C _1-30 alkyl group, a substituted or unsubstituted C _1-30 cycloalkyl group, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms Is preferred. Plural _Rx may be the same as or different from each other. The organic phosphorus compounds of the general formula _{P (R x)} can also be used phosphine salt represented by 3 · (HX _a). R _x is as defined above, H is a hydrogen atom, X _a is an atom or a group of atoms, and HX _a includes, for example, HCl, HBr, HBF _{4 and the} like.

Examples of organic phosphorus compounds include triphenylphosphine (PPh ₃ ), trimesitylphosphine (PMes ₃ ), tricyclohexylphosphine (PCy ₃ ), tri (t-butyl) phosphine (P (tBu) ₃ ), and tri-tert. -Butyl phosphonium tetrafluoroborate (PtBu ₃ -HBF ₄ ), tri-o-tolyl phosphine (P (o-tol) ₃ ), tri-p-tolyl phosphine (P (p-tol) ₃ ), tris (p -Methoxyphenyl) phosphine (P (p-MeOC ₆ H ₄ ) ₃ ), tris (o-methoxyphenyl) phosphine (P (o-MeOC ₆ H ₄ ) ₃ ), trifuranyl phosphine (P (furanyl) ₃ ) , Trithienyl phosphine (P (thienyl) ₃ ), tris (3,5-dimethoxyphenyl) phosphine (P (3,5- (MeO) ₂ C ₆ H ₃ ) ₃ ), dicyclohexylphenyl phosphine (PPh (Cy) ) _2), hexyl diphenylphosphine cyclohexane (PPh ₂ (Cy)), dicyanamide B hexyl phosphine (HPCy _2), di -tert- butylphosphine (HP _{(tBu) 2),} di -tert- butylchlorophosphine _{(P (tBu) 2 Cl)} , trimethyl phosphite (P _{(OMe) 3),} Triphenyl phosphite (P (OPh) ₃ ), diphenyl phosphine oxide (HPOP h ₂ ), tris (dimethylamino) phosphine (HMPT), tris (diethylamino) phosphine (P (NEt ₂ ) ₃ ), 5- (di-t) -Butylphosphino) -1 ', 3', 5'-triphenyl-1'H- [1,4 '] bipyrazole (BippyPhos), 1,2,3,4,5-pentaphenyl-1'- ( Di-t-butylphosphino) ferrocene (QPhos), 1,3,5-triaza-7-phosphaadamantane (PTA), bis [2- (diphenylphosphino) phenyl] ether (DPEPhos), 1,1 ' -Bis (diphenylphosphino) ferrocene (dppf), 1,1'- Scan (diphenylphosphino) methane (dppm), 1,2-bis (diphenylphosphino) ethane (dppe), 1,3-bis (diphenylphosphino) propane (dppp), 1,4-bis (diphenylphosphino) ) Butane (dppb), 1,2-bis (dicyclohexylphosphino) ethane (dcpe), 1,1′-bis (di-tert-butylphosphino) ferrocene (dtbpf), 2,2′-bis (diphenylphos) Fino) -1,1'-binaphthyl (BINAP), 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (SPhos), 2-dicyclohexylphosphino-2', 4 ', 6'-triisopropylbiphenyl XPhos), 2-diphenylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (PhXPhos), 2-di-tert-butylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (tBuXPhos) , 2-diiso Pirphosphino-2 ', 4', 6'-triisopropylbiphenyl (iPrXPhos), 2-bis (p-trifluoromethylphenyl) phosphino-2 ', 4', 6'-triisopropylbiphenyl (Ar ^CF3 XPhos), 2 -(Di-tert-butylphosphino) biphenyl (JohnPhos), 2- (dicyclohexylphosphino) biphenyl (cyclohexyl JohnPhos), 2- (dicyclohexylphosphino) -2'-methylbiphenyl (MePhos), 2- (dicyclophosphino) biphenyl Xylphosphino) -2 ', 6'-diisopropoxy-1,1'-biphenyl (RuPhos), 2- (dicyclohexylphosphino) -3,6-dimethoxy-2', 4 ', 6'-triisopropyl-1 , 1'-biphenyl (BrettPhos), 2 '- (dicyclohexyl Kishiruhosufino) -2,6-dimethoxy - biphenyl-3-sulfonic acid sodium salt ^(s SPhos), 2- ^{(diphenylphosphino)} -2' - (N N'-Dimethylamino) biphenyl (PhDavePhos), 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2 ', 4', 6'-triisopropyl-1,1'-biphenyl (Tetramethyl di-tBuXPhos), 2- (di-tert-butylphosphino) -2'-methylbiphenyl (tBuMePhos), 2-di-tert-butylphosphino-2 '-(N, N-dimethylamino) biphenyl (TBuDavePhos), 2- (bis- [3,5-bis (trifluoromethyl) phenyl] phosphino) -3,6-dimethoxy-2 ', 4', 6'-triisopropyl-1,1'-biphenyl Jackie Phos), (n-butyl) di (1-adamantyl) phosphine (cataCXium A), (n-butyl) di (1-adamantyl) phosphonium hydroiodide (cataCXium AHI), N-phenyl-2- (di) -tert-butylphosphino) pyrrole (cataCXium PtB), 2- (di) -tert-Butylphosphino) -N-phenylindole (cataCXium PlntB), N-phenyl-2- (dicyclohexylphosphino) pyrrole (cataCXium PCy), N- (2-methoxyphenyl) -2- (di-tert-) Butylphosphino) pyrrole (cataCXium POMetB), 2- (di (1-adamantyl) phosphino) -dimethylaminobenzene (Me-DalPhos), di (1-adamantyl) -2-morpholinophenylphosphine (Mor-DalPhos), 2 And-(dicyclohexylphosphino) -2 '-(dimethylamino) biphenyl (DavePhos), and 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (XantPhos).
Among these, XPhos, PhXPhos, iPrXPhos, Ar ^CF3 XPhos and tBuXPhos are preferable.
These organophosphorus compounds may be used alone or in combination of two or more.

Among the organic phosphorus compounds, at least one of the substituents (R _x ) bonded to the phosphorus atom (P) is preferably a bulky substituent. Specifically, it is preferable to at least one of R _x having at least two aromatic rings, more preferably having at least one xantphos skeleton or biphenyl skeleton of R _x, at least one of R _x have the biphenyl skeleton More preferably, it is particularly preferred that one of R _x has a biphenyl skeleton.
By selecting such an organophosphorus compound, the yield of aromatic carboxylic acid is further improved.

Moreover, it is preferable that a biphenyl skeleton has a substituent. Such substituents, _{C 1 to 10} alkyl group such as a methyl group, an ethyl group or an isopropyl group, _{C 1 to 10} alkyl group such as a methoxy group or an ethoxy group, a dimethylamino group, _{C 1 to 10} of diethylamino The dialkylamino group etc. which have the alkyl group of these are mentioned, Preferably it is a _C1-5 alkyl group. The number of substituents is not particularly limited, but is usually 1 or more, preferably 3 or more, and usually 6 or less, preferably 5 or less.

The transition metal catalyst component (B) may be prepared by reacting a catalyst precursor containing transition metal M 'in advance with an organophosphorus compound, or a catalyst precursor containing transition metal M' in the reaction system An organophosphorus compound may be added to prepare a reaction system.
When preparing in a reaction system, the order of adding the catalyst precursor containing transition metal M ′ and the organophosphorus compound is not particularly limited, and the catalyst precursor containing transition metal M ′ is added before the organophosphorus compound. Or may be added later. When preparing the transition metal catalyst component (B) in the reaction system, the presence of a transition metal catalyst component (B), and ^{1 H-NMR} spectrum of the previously prepared transition metal catalyst component (B), ¹ of the catalyst composition It can confirm by contrasting with the 1 H-NMR spectrum.

The content ratio of the transition metal catalyst component (B) in the catalyst composition is not particularly limited, but generally 0.01 mol% or more, preferably 0 based on the aromatic halogen compound which is the starting material (substrate) for the carboxylation reaction. .1 mol% or more, more preferably 0.5 mol% or more, usually 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less.
When the content ratio of the transition metal catalyst component (B) is low, the catalyst cycle may not proceed sufficiently. On the other hand, when the content ratio of the transition metal catalyst component (B) is high, there is a tendency that significant improvement in the effect is not observed, which is not economical.

In addition, when preparing a transition metal catalyst component (B) in a reaction system, each content ratio of the catalyst precursor containing transition metal M 'and an organic phosphorus compound is as follows.
The content ratio of the catalyst precursor containing the transition metal M ′ is usually 0.1 mol% or more, preferably 0.5 mol% or more, more preferably 1.0 mol% or more, and further preferably 2 with respect to the aromatic halogen compound. It is not less than 0.3 mol%, usually not more than 30 mol%, preferably not more than 25 mol%, more preferably not more than 20 mol%, still more preferably not more than 15 mol%.
In addition, the content ratio of the organic phosphorus compound is usually 0.5 mol% or more, preferably 1.0 mol% or more, more preferably 2.0 mol% or more, still more preferably 3.0 mol% or more based on the aromatic halogen compound. And is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, and still more preferably 25 mol% or less.
When the content ratio of the catalyst precursor containing the transition metal M ′ and the content ratio of the organic phosphorus compound are small, the amount of the transition metal catalyst component (B) produced may be small, and the catalyst cycle may not proceed sufficiently.
On the other hand, when the content ratio of the catalyst precursor containing the transition metal M 'and the content ratio of the organic phosphorus compound are high, the improvement of the effect tends not to be recognized, which is not economical. In addition, the residue after the transition metal catalyst component (B) is formed (excess catalyst precursor or organophosphorus compound) may not allow the catalyst cycle to proceed sufficiently.

In addition, the molar ratio (organic phosphorus compound / catalyst precursor) of the organophosphorus compound to the catalyst precursor containing transition metal M ′ is usually 0.1 or more, preferably 0.5 or more, more preferably 1 or more, Usually 20 or less, preferably 10 or less, more preferably 5 or less.
When the molar ratio of the organophosphorus compound to the catalyst precursor containing the transition metal M ′ is small, the amount of the transition metal catalyst component (B) produced may be small, and the catalyst cycle may not proceed sufficiently. On the other hand, when the molar ratio of the organophosphorus compound to the catalyst precursor containing the transition metal M ′ is large, it is not economical because a significant improvement in the effect tends not to be observed. In addition, when the molar ratio of the organophosphorus compound to the catalyst precursor containing the transition metal M ′ is too small or too large, the residue after the transition metal catalyst component (B) is formed (excess catalyst precursor Or, due to organophosphorus compounds, the catalytic cycle may not proceed sufficiently.

The molar ratio (B / A) of the transition metal catalyst component (B) to the photooxidation reduction catalyst component (A) is usually 1/20 or more, preferably 1/10 or more, more preferably 1/5 or more, It is 20/1 or less, preferably 15/1 or less, more preferably 10/1 or less.
If the molar ratio of the transition metal catalyst component (B) to the photoredox catalyst component (A) is too small or too large, the catalyst cycle may not proceed sufficiently. In addition, an excessive amount of the component may remain in the reaction system, which may affect the catalyst cycle.

2. Method for Producing Aromatic Carboxylic Acid or Ester Thereof A method for producing an aromatic carboxylic acid or an ester thereof according to the present embodiment comprises: photoredox catalyst component (A) containing transition metal M belonging to periodic table groups 8 to 10; A step of irradiating carbon dioxide and an aromatic halogen compound in the presence of a catalyst composition which belongs to Groups 8 to 11 and contains the transition metal M and a transition metal catalyst component (B) containing a different transition metal M ′. including.

  The wavelength of light to be irradiated may be determined according to the photoredox catalyst component (A) to be used, but when the transition metal M contained in the photoredox catalyst component (A) is ruthenium or iridium, visible light is It is preferable to irradiate (for example, light having a wavelength of 400 to 700 nm), and more preferable to emit blue light (for example, light having a wavelength of 400 to 500 nm). The light to be emitted may be natural light such as sunlight or artificial light using an LED or the like as a light source.

  The temperature (reaction temperature) at the time of light irradiation is not particularly limited, but is usually 0 ° C. or more, preferably 15 ° C. or more, and is usually 70 ° C. or less, preferably 50 ° C. or less. In addition, reaction temperature means the temperature in the reaction container for manufacturing aromatic carboxylic acid or its ester. If the reaction temperature is too low, the catalyst cycle may not proceed sufficiently. In addition, when the reaction temperature is too high, the yield of hydrogenation products tends to increase.

  The light irradiation time (reaction time) is not particularly limited, but is usually 1 hour or more, preferably 2 hours or more, and usually 24 hours or less, preferably 10 hours or less. If the reaction time is short, the catalyst cycle may not proceed sufficiently. On the other hand, even if the reaction time is long, no significant improvement in the yield of the aromatic carboxylic acid is observed, and the yield of the hydrogenated product tends to increase.

  Further, the intensity of the light to be irradiated is not particularly limited. For example, in the case of using a light emitting device such as an LED lamp, the light intensity can be controlled by increasing or decreasing the number of sockets. When the intensity of the light to be irradiated is increased, the conversion of the starting aromatic halogen compound may be improved.

The light irradiation step is preferably carried out by placing the catalyst composition, carbon dioxide and an aromatic halogen compound in a reaction vessel. The light irradiation step may be performed under atmospheric pressure or under pressure higher than atmospheric pressure.
Here, carbon dioxide may be added by bubbling into the reaction system under atmospheric pressure or under pressure, or it may be added under atmospheric pressure or under pressure, preferably while stirring up and down. It may be dissolved in the phase.

  The reaction system is not particularly limited, and may be, for example, either a continuous system or a batch system.

  In the light irradiation step under the above conditions, at the stage of elimination of the halogen anion and reductive elimination of the aromatic carboxylic acid, electrons are transferred from the excited photoredox catalyst component (A) to the transition metal catalyst component (B) It is assumed that the reaction will proceed.

  After completion of the reaction, the method for separating the aromatic carboxylic acid is not particularly limited. For example, distillation and concentration are preferable. As a means for this distillation and concentration, a conventional distillation and concentration apparatus, such as a vacuum continuous distillation apparatus and a vacuum batch type distillation apparatus can be used.

  The aromatic carboxylic acid thus obtained is a compound in which a halogen atom (-X) in an aromatic halogen compound described later is substituted with a carboxy group (-COOH). In addition to aromatic carboxylic acids, hydrogenated products can also be obtained as by-products. The hydrogenation product is a compound in which the halogen atom (-X) in the aromatic halogen compound is replaced by a hydrogen atom (-H).

[Aromatic halogen compounds]
The aromatic halogen compound used in the production method of the present embodiment is not particularly limited as long as it is a compound having a structure in which a halogen atom is directly chemically bonded to an atom constituting the ring of the aromatic compound. Here, the "atom which constitutes the ring of the aromatic compound" includes, for example, a carbon atom which constitutes a benzene ring. The number of benzene rings may be one or two or more, and the benzene ring may be a fused cyclic structure like a naphthalene ring. Moreover, as long as it has aromaticity, a ring structure is not limited to a benzene ring, A heterocyclic type may be sufficient, 5 membered rings other than a 6-membered ring, 7 membered ring, etc. may be sufficient. Furthermore, only one aromatic halogen compound may be used, or two or more different aromatic halogen compounds may be used in combination.

（式中、Ｘはハロゲン原子を表し、ｎ_１は１〜３の整数を表す。ｎ_１が２以上の場合には、Ｘは互いに同一でも異なっていてもよい。Ｒは水素原子、フッ素原子、塩素原子、アルキル基、フッ素原子を含有するアルキル基、アルコキシ基、シクロアルキル基、アリール基、カルボニル基、エステル基、ニトリル基又はシリル基を表し、ｎ_２は１〜３の整数を表す。ｎ_２が２以上の場合にはＲは互いに同一でも異なっていてもよい。またＲは隣接炭素原子に結合し、それらの炭素原子とともに炭化水素環又は複素環を形成してもよい。） For example, it is preferable that the aromatic halogen compound in the case of one benzene ring is represented by following Structural formula (I).

(Wherein, X represents a halogen atom, and n ₁ represents an integer of ₁ to 3. When n ₁ is 2 or more, X may be the same or different from each other. R is a hydrogen atom or a fluorine atom , a chlorine atom, an alkyl group, an alkyl group containing a fluorine atom, an alkoxy group, a cycloalkyl group, an aryl group, a carbonyl group, an ester group, a nitrile group or a silyl group, n ₂ represents an integer of 1 to 3. When n ₂ is 2 or more, Rs may be the same as or different from each other, and R may be bonded to adjacent carbon atoms, and together with their carbon atoms may form a hydrocarbon ring or a heterocyclic ring.

From the viewpoint of excellent progress of the catalyst cycle, the halogen atom X is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a bromine atom or a chlorine atom. That is, the aromatic halogen compound is preferably an aromatic chloride, an aromatic bromide or an aromatic iodide, more preferably an aromatic chloride or an aromatic bromide.
In addition, in the structural formula (I), n ₁ is preferably 1 or 2, more preferably 1, and n ₂ is preferably 1 or 2 from the viewpoint of excellent progress of the catalyst cycle.

  When the halogen atom X is a bromine atom, specific examples of the compound represented by Structural Formula (I) are shown below. These are merely examples of the case where the halogen atom X is a bromine atom, and the same aromatic halogen compounds can be exemplified also when the halogen atom X is a chlorine atom or an iodine atom. The compounds exemplified below include the o-position, the m-position and the p-position.

  As an example of R being a hydrogen atom, bromobenzene etc. are mentioned.

  As an example of R being a fluorine atom and / or a chlorine atom, fluorobromobenzene, difluorobromobenzene, chlorobromobenzene, dichlorobromobenzene, fluorochlorobromobenzene and the like can be mentioned.

As an example of R being an alkyl group, bromotoluene, bromoxylene, trimethylbromobenzene, ethylbromobenzene, methylethyl bromobenzene, tert-butyl bromobenzene, 2-ethylhexyl bromobenzene, 2,4,6-triisopropyl bromobenzene Etc. Among the alkyl groups, a C _1-10 alkyl group is preferable, and a C _1-5 alkyl group is more preferable.

  Examples of the alkyl group in which R contains a fluorine atom include trifluoromethylbromobenzene and the like.

Examples of R are alkoxy groups such as bromoanisole, dimethoxybromobenzene, trimethoxybromobenzene, ethoxybromobenzene, methoxyethoxybromobenzene, propoxybromobenzene, ethoxypentoxybromobenzene, phenoxybromobenzene, benzoxbromobenzene and the like It can be mentioned. Among the alkoxy groups, a C _1-10 alkoxy group is preferable, and a C _1-5 alkoxy group is more preferable.

  Examples of cycloalkyl group represented by R include cyclopentylbromobenzene, cyclohexylbromobenzene, cyclooctylbromobenzene and the like.

  As an example of R being an aryl group, bromobiphenyl etc. are mentioned.

  As an example of R being a carbonyl group, acetylbromobenzene, t-butoxycarbonylaminobromobenzene and the like can be mentioned.

  Examples of the ester group where R is an ester group include methyl bromobenzoate, ethyl bromobenzoate, butyl bromobenzoate, dimethyl bromophthalate and the like.

  Examples of the nitrile group represented by R include cyanobromobenzene and the like.

  Examples of silyl groups for R include trimethylsilylbromobenzene, triethylsilylbromobenzene, triisopropylsilylbromobenzene, di-t-butylmethylsilylbromobenzene, triisopropylsilylethynylbromobenzene and the like.

  Examples of isopropenyl group, allyl group and vinyl group for R include isopropenylbromobenzene, allylbromobenzene, vinylbromobenzene and the like.

  Examples of hydrocarbon rings or heterocycles in which R is a hydrocarbon ring or a heterocycle include methylenedioxybromobenzene, bromothiophene, N-tert-butoxycarbonylbromoindole, bromoindole and the like.

〔solvent〕
The carboxylation reaction of this embodiment is carried out in a reaction solvent. The reaction solvent is preferably an organic solvent, and is not particularly limited. For example, dimethylsulfoxide, toluene, benzene, 1,4-dioxane, ethanol, butanol, xylene, N, N-dimethylformamide (DMF), N Methyl pyrrolidone (NMP), acetonitrile (MeCN), acetone, tetrahydrofuran (THF), N, N-dimethylacetamide (DMA) and the like. Among these, from the viewpoint of excellent aromatic carboxylic acid yield, DMF, NMP, acetone or DMA is preferable, DMF, NMP or DMA is more preferable, and DMA is particularly preferable.

[Esterification reaction]
An aromatic carboxylic acid ester is obtained by esterifying an aromatic carboxylic acid obtained from the above aromatic halogen compound and carbon dioxide.
The esterification reaction can be carried out using a known esterification method, such as alkyl esterification method (alkanol + acid catalyst), aralkyl esterification method (aralkyl alcohol + acid catalyst), or methylation using diazomethane or trimethylsilyldiazomethane Law etc. are mentioned.

Tertiary amine compounds
In the method for producing an aromatic carboxylic acid or an ester thereof in the present embodiment, it is preferable to allow a tertiary amine compound to be present together with the catalyst composition. Tertiary amine compounds can hydrate halogen ions as electron donors to improve the yield of aromatic carboxylic acids.

Examples of tertiary amine compounds include N, N, N-tri (C _1-4 alkyl) amines such as trimethylamine, dimethylethylamine, triethylamine, tri (n-butyl) amine, diisopropylethylamine, diisobutylmethylamine, etc .; N- (C _1-4 alkyl) azacycloalkanes such as tetramethylsilyl) amine, N-methylpyrrolidine, N-methylpiperidine, N-ethyl-2,2,6,6-tetramethylpiperidine; N-methyl N- (C _1-4 alkyl) azaoxycycloalkanes such as morpholine and N-ethylmorpholine; N-benzyl-N, such as N-benzyl-N, N-dimethylamine and N-benzyl-N, N-diethylamine N- di _{(C 1 to 4} alkyl) amine; N, N- dimethylaniline or the like of N, N- di _{(C 1 to 4} alkyl) aniline; Can be mentioned N, such as triethanolamine, N, the N- tri (C _{1 to 4} alcohols) amine; aza bicyclo Crowe down decene, bicyclic amines such as diazabicyclononene. These tertiary amine compounds can be used alone or in combination of two or more.
Among these, from the viewpoint of improving the yield of aromatic carboxylic acid, N, N, N-tri (C _1-4 alkyl) amine is preferable, and diisopropylethylamine is more preferable.

  The compounding amount of the tertiary amine compound is not particularly limited, but is usually 1 equivalent or more, preferably 2 equivalents or more, more preferably 3 equivalents or more, and usually 20 equivalents or less, with respect to the halogen atom in the aromatic halogen compound. Preferably, it is 15 equivalents or less, more preferably 10 equivalents or less. By making the compounding quantity of a tertiary amine compound into the said range, the yield of aromatic carboxylic acid can be improved.

[Basic compound]
Moreover, in the method for producing an aromatic carboxylic acid or ester thereof according to the present embodiment, it is preferable to allow a basic compound to be present as an additive together with the catalyst composition. The basic compound can capture the liberated acid component to improve the yield of aromatic carboxylic acid. Further, the formation of a by-product can be suppressed by blending a basic compound.

Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; Alkali metal hydrogen carbonates such as sodium hydrogen, potassium hydrogen carbonate and cesium hydrogen carbonate; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide; alkalis such as magnesium carbonate, calcium carbonate and barium carbonate Earth metal carbonate, alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal organic acid salts such as sodium acetate; amines such as triethylamine, piperidine and N-methylpiperidine, pyridine, picoline Nitrogen containing such as It can be exemplified heterocyclic compounds. These basic compounds can be used alone or in combination of two or more.
Among these, from the viewpoint of improving the yield of aromatic carboxylic acid, alkali metal carbonates are preferable, sodium carbonate, potassium carbonate or cesium carbonate is more preferable, and cesium carbonate is more preferable.

  The compounding amount of the basic compound is not particularly limited, but is usually 1 equivalent or more, preferably 2 equivalents or more, more preferably 3 equivalents or more, usually 20 equivalents or less, preferably to the halogen atom in the aromatic halogen compound. Is 15 equivalents or less, more preferably 10 equivalents or less. By making the compounding quantity of a basic compound into the said range, the yield of aromatic carboxylic acid can be improved.

  When a tertiary amine compound and a basic compound are used in combination, the compounding ratio of the basic compound to the tertiary amine compound (calculated as the equivalent ratio to the halogen atom, basic compound / tertiary amine compound) is usually 0.1 or more Preferably it is 0.5 or more, normally 5 or less, preferably 3 or less.

  After completion of the light irradiation step, the aromatic carboxylic acid or its ester is separated from the reaction substance by a conventionally known method. After separation of the aromatic carboxylic acid or ester thereof, the catalyst composition in the bottoms can be recycled for reuse in a new operation. The yield of the aromatic carboxylic acid or ester thereof is usually 2% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, further preferably, with respect to the total amount of the starting aromatic halogen compound. It is 50% by mass or more, particularly preferably 60% by mass or more. The upper limit of the yield is not particularly limited, but is usually 100% by mass or less.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples as long as the gist thereof is not exceeded. The present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the scope of the present invention. The values of various manufacturing conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit described above The range defined by the values of the following examples or the combination of the values of the examples may be used.

In the following, all operations were performed under an atmosphere of argon, nitrogen or carbon dioxide unless otherwise stated.
¹ H-NMR spectra were measured on a JEOL ECZ-500 and ECX-500 (500 MHz) spectrometer in CDCl ₃ using residual CHCl ₃ (for 1 H, δ = 7.26) as internal standard.
Merck Kiesel gel 60 F254 plates (0.25 mm thick, coated with 20 × 20 cm ² glass) are used for analytical thin layer chromatography (TLC), and 0 nm thick on glass for preparative TLC A 9 mm coated Wakogel B-5F was used.
Visible light irradiation was performed using Relyon Twin LED Light (3 W × 2, λ _irr. = 425 ± 15 nm) for photocatalytic reaction.

The Et ₂ O was dried by passing through a column of activated alumina (A-2, Purity) followed by a column of Q-5 scavenger (Engelhard).
Dehydrated acetone, acetonitrile (MeCN), dimethylacetamide (DMA), dimethylformamide (DMF) and methanol (MeOH) are purchased from Kanto Chemical Co., and N-methylpyrrolidone (NMP) is purchased from Sigma Aldrich, prior to use Degassed by bubbling with argon.
The tertiary amine compound was distilled and degassed by freeze degassing (3 times) and stored under nitrogen atmosphere.
CO ₂ gas was purchased from Taiyo Nippon Acid Co., Ltd.

Pd (OAc) ₂ , XPhos, tBuXPhos, bromobenzene (compound 1 b), acetylbromobenzene (compound 1 r) and methyl 3-chlorobenzoate (compound 6 u) were purchased from Sigma Aldrich.

  3,4-Methylenedioxybromobenzene (compound 1a), 4-bromotoluene (compound 1c), 4-bromoanisole (compound 1d), 4-trifluoromethylbromobenzene (compound 1e), 4-fluorobromobenzene (compound 1e) Compound 1f), 4-chlorobromobenzene (compound 1g), methyl 4-bromobenzoate (compound 1i), 4-cyanobromobenzene (compound 1j), 2-bromotoluene (compound 1m), 2,4,6- Triisopropylbromobenzene (compound 1n), 3-bromothiophene (compound 1o), chlorobenzene (compound 6b), 4-chlorotoluene (compound 6c), 4-trifluoromethylchlorobenzene (compound 6e), 4-cyanochlorobenzene (compound 6j), 4-acetylchlorobenzene (compound 6s), 3-chloroanisole (compound Compound 6t) and 2-chloronaphthalene (compound 6v) were purchased from Tokyo Chemical Industry Co., Ltd.

  Cesium carbonate and N-tert-butoxycarbonylbromoindole (compound 1p) were purchased from Wako Pure Chemical Industries, Ltd.

_{PhXPhos, Ru (bpy) 3 (} PF 6) 2, Ir (dF (CF 3) ppy) 2 (dtbbpy) (PF 6), Ir (ppy) 2 (dtbbpy) (PF 6), Ir (ppy) 2 ( dmobpy) (PF ₆ ), Ir (ppy) ₂ (Me ₄ phen) (PF ₆ ), TMSCHN ₂ , t-butoxycarbonylaminobromobenzene (Compound 1h), 4-triisopropylsilylethynylbromobenzene (Compound 1k), 4-Isopropenylbromobenzene (compound 1l), 5-bromoindole (compound 1q), 4-chloroanisole (compound 6d) were prepared by a conventionally known method.

  The liquid materials, compounds 1a to 1f, 1m, 1o, 1r and 6b to 6e, 6s to 6u, were stored in argon atmosphere after distillation.

Example 1
Ir (ppy) ₂ (dtbbpy) (PF ₆ ) (0.002 mmol, 1.0 mol%) was used as the photoredox catalyst component (A). In addition, palladium acetate (1.1 mg, 0.005 mmol, 2.5 mol%) is used as a catalyst precursor for obtaining the transition metal catalyst component (B), and the organophosphorus compounds (0.01 mmol, 5.0 mol%) was used. In addition, N, N-diisopropylethylamine (iPr ₂ NEt, 0.10 mL, 0.60 mmol, 3.0 equivalents) was used as a tertiary amine compound. Furthermore, cesium carbonate (Cs ₂ CO ₃ , 195 mg, 0.60 mmol, 3.0 equivalents) was used as a basic compound.
N of 3,4-methylenedioxybromobenzene (compound 1a, 24 μL, 0.20 mmol) containing the above-mentioned photoredox catalyst component (A), transition metal catalyst component (B), tertiary amine compound and basic compound , N-Dimethylacetamide (DMA) solution (1.0 mL) was prepared in a test tube under a nitrogen atmosphere. Note that contain a ^{1 H-NMR} spectrum of the previously prepared transition metal catalyst component (B), was compared with the ^{1 H-NMR} spectrum of the sample in the test tube, the transition metal catalyst component into a test tube (B) is It could be confirmed that

The gas phase was then replaced with atmospheric CO ₂ and the reaction vessel was placed in a water bath placed at a distance of 10 mm from the light source. Then, using a blue LED lamp having two sockets, visible light (λ _irr. = 425 nm) was irradiated at room temperature (specifically 25 ° C.) in a closed system for 6 hours. After irradiation with visible light, the reaction was quenched with H ₂ O, and the mixture in the reaction vessel was extracted three times with Et ₂ O (diethyl ether).

The organic layer was washed with H ₂ O and then dried by adding Na ₂ SO ₄ . After filtration, the filtrate was concentrated to obtain a composition. The composition was subjected to spectroscopic analysis using ¹ H-NMR to determine the recovery of the starting material 3,4-methylenedioxybromobenzene (compound 1a) and the yield of the hydrogenated product (compound 3a) (the compound 3a) Internal standard: dibromomethane).
The aqueous layer was also acidified with 1 N aqueous HCl, and then extracted three times with Et ₂ O (diethyl ether). The organic layer was dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure to obtain an aromatic carboxylic acid (compound 2a). The yield of aromatic carboxylic acid (compound 2a) was determined by ¹ H-NMR (internal standard: 1,4-dioxane).
The conversion of Compound 1a was calculated from the amount of Compound 1a initially blended and the recovery of Compound 1a. The results are shown in Table 1.

(Examples 2 to 6)
The same operations as in Example 1 were carried out except that in Example 1, the ligands were changed to those described in Table 1. Example 6 performed the same operation as Example 4 except having used (A) component 2.5 mol%. The obtained results are shown in Table 1.

  Table 1 showed that various organophosphorus compounds can be used as a ligand for producing the transition metal catalyst component (B). In addition, from Example 6, when the content ratio of the photoredox catalyst component (A) is increased, the yield of the aromatic carboxylic acid (compound 2a) is increased, and the yield of the hydrogenated product (compound 3a) is reduced. I understand that.

(Example 7)
The same operation as in Example 1 was carried out except that the basic compound was not used in Example 1. The results are shown in Table 2.
(Comparative Examples 1 to 5)
The same operations as in Example 7 were performed except that the combination components, the presence or absence of light irradiation, and the gas phase were changed as described in Table 2 below (Comparative Examples 1 to 5). The results are shown in Table 2.

  From Table 2, in order to obtain the aromatic carboxylic acid (compound 2a) from the aromatic halogen compound, it is essential that the photoredox catalyst component (A), the transition metal catalyst component (B), carbon dioxide and light irradiation I understand. It was shown that the absence of one of these did not yield an aromatic carboxylic acid (Compound 2a).

(Examples 8 to 25)
Compounds 1a to 1r were used as aromatic bromides in Examples 8 to 25, respectively. Compounds 1a to 1r are compounds in which a carboxylic acid ester part (-CO ₂ Me) of an aromatic carboxylic acid methyl ester (compounds 5a to 5r in Table 3 below) is substituted with bromine (-Br).
Ir (ppy) ₂ (dtbbpy) (PF ₆ ) (4.6 mg, 0.005 mmol, 2.5 mol%) was used as the photoredox catalyst component (A). In addition, palladium acetate (1.1 mg, 0.005 mmol, 2.5 mol%) was used as a catalyst precursor for obtaining the transition metal catalyst component (B), and PhXPhos (0.01 mmol, 5.0 mol%) was used as a ligand. . In addition, iPr ₂ NEt (0.10 mL, 0.60 mmol, 3.0 equivalents) was used as a tertiary amine compound. Furthermore, Cs ₂ CO ₃ (195 mg, 0.60 mmol, 3.0 equivalents) was used as a basic compound.
DMA solution (1.00 mmol, compound 1a to 1r in Table 3) of the aromatic bromide (0.20 mmol, compound 1a to 1r) containing the photoredox catalyst component (A), transition metal catalyst component (B), tertiary amine compound and basic compound mL) was prepared in a test tube under a nitrogen atmosphere. Note that contain a ^{1 H-NMR} spectrum of the previously prepared transition metal catalyst component (B), was compared with the ^{1 H-NMR} spectrum of the sample in the test tube, the transition metal catalyst component into a test tube (B) is It could be confirmed that

The gas phase was then replaced with atmospheric CO ₂ and the reaction vessel was placed in a water bath placed at a distance of 10 mm from the light source. Then, using a blue LED lamp having two sockets, visible light (λ _irr. = 425 nm) was irradiated at room temperature (specifically 25 ° C.) in a closed system for 6 hours. After irradiation with visible light, the reaction was quenched with H ₂ O, and the mixture in the reaction vessel was extracted three times with Et ₂ O (diethyl ether).

The organic layer was washed with H ₂ O. The aqueous layer was acidified with 1 N aqueous HCl and then extracted three times with Et ₂ O (diethyl ether). The organic layer was dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure to obtain an aromatic carboxylic acid. The aromatic carboxylic acid was dissolved in Et ₂ O (2.0 mL) and MeOH (methanol, 0.5 mL), and a solution of trimethylsilyldiazomethane (TMSCHN ₂ , 2.0 eq.) In Et ₂ O was added at 0 ° C. The mixture was stirred at 0 ° C. for 30 minutes and the solvent was removed under reduced pressure to obtain a composition. The resulting composition was purified by preparative thin layer chromatography, and methyl esters corresponding to aromatic carboxylic acids (aromatic carboxylic acid methyl esters, in Examples 8 to 25 respectively, compounds 5a to 5 in Table 3 I got 5r). The yield of aromatic carboxylic acid methyl ester is shown in Table 3. The yield was measured by ¹ H-NMR spectrum in the same manner as in Example 1.
In Example 14, the visible light irradiation time was 4 hours, and in Example 21, the visible light irradiation time was 8 hours. In Examples 15 to 17 and 25, tBuXPhos was used instead of PhXPhos.

  The "reaction time" in Table 3 means the visible light irradiation time. The results are shown in Table 3.

Table 3 shows that as starting material, aromatic bromides having various functional groups R can be used. Specifically, when an aromatic bromide (compound 1c to 1g, 1k, 1l) having an alkyl group, an alkoxy group, a halogen atom, and an internal alkyne or alkene as the functional group R at the 4-position is used, trimethylsilyldiazomethane (TMSCHN ₂ The yield of the aromatic carboxylic acid methyl ester obtained by the methyl esterification with (1) exceeded 80%, and good results were obtained.
In particular, when 4-chlorobromobenzene (Compound 1g) was used as a substrate (starting material), 4-chlorobenzoate (Compound 5g) was selectively obtained despite the short reaction time.

  Cobalt and nickel catalyzed carboxylation reactions of sterically hindered aryl triflates are known, but this carboxylation reaction did not yield carboxylic acids from 2,6-diisopropylphenyl triflate. On the other hand, the carboxylation reaction of 2,4,6-triisopropylbromobenzene (Compound 1n) having the same steric hindrance is obtained by the combined use of a photoredox catalyst component (A) and a transition metal catalyst component (B). Proceeding in% yield. This indicates that it can also be used for bulky substrates.

  Methyl esters (compounds 5o-5q) were also obtained from electron-rich heteroarene bromides such as thiophene (compound 1o) and indole (compounds 1p, 1q).

(Examples 26 to 34)
The same operations as in Examples 8 to 25 were carried out except that aromatic chloride was used instead of aromatic bromide and tBuXPhos was used as a ligand for obtaining the transition metal catalyst component (B).

Specifically, compounds 6b to 6e, 6j, 6s to 6v were used as aromatic chlorides in Examples 26 to 34, respectively. Compound 6b~6e, 6j, 6s~6v is an aromatic carboxylic acid methyl ester (compound in Table 4 5b~5e, 5j, 5s~5v) carboxylic acid ester moiety of the _(-CO 2 Me) chlorine (- It is a compound substituted by Cl).
Ir (ppy) ₂ (dtbbpy) (PF ₆ ) (4.6 mg, 0.005 mmol, 2.5 mol%) was used as the photoredox catalyst component (A). In addition, palladium acetate (1.1 mg, 0.005 mmol, 2.5 mol%) was used as a catalyst precursor for obtaining the transition metal catalyst component (B), and tBuXPhos (0.01 mmol, 5.0 mol%) was used as a ligand. . In addition, iPr ₂ NEt (0.10 mL, 0.60 mmol, 3.0 equivalents) was used as a tertiary amine compound. Furthermore, Cs ₂ CO ₃ (195 mg, 0.60 mmol, 3.0 equivalents) was used as a basic compound.
Aromatic chloride (0.20 mmol, compounds 6b to 6e, 6j, 6s in Table 4) containing the photoredox catalyst component (A), the transition metal catalyst component (B), the tertiary amine compound and the basic compound 6v) DMA solution (1.0 mL) was prepared in a test tube under nitrogen atmosphere. Note that contain a ^{1 H-NMR} spectrum of the previously prepared transition metal catalyst component (B), was compared with the ^{1 H-NMR} spectrum of the sample in the test tube, the transition metal catalyst component into a test tube (B) is It could be confirmed that

The gas phase was then replaced with atmospheric CO ₂ and the reaction vessel was placed in a water bath placed at a distance of 10 mm from the light source. Then, using a blue LED lamp having two sockets, visible light (λ _irr. = 425 nm) was irradiated at room temperature (specifically 25 ° C.) in a closed system for 6 hours. After irradiation with visible light, the reaction was quenched with H ₂ O, and the mixture in the reaction vessel was extracted three times with Et ₂ O (diethyl ether).

The organic layer was washed with H ₂ O. The aqueous layer was acidified with 1 N aqueous HCl and then extracted three times with Et ₂ O (diethyl ether). The organic layer was dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure to obtain an aromatic carboxylic acid. The aromatic carboxylic acid was dissolved in Et ₂ O (2.0 mL) and MeOH (methanol, 0.5 mL), and a solution of trimethylsilyldiazomethane (TMSCHN ₂ , 2.0 eq.) In Et ₂ O was added at 0 ° C. The mixture was stirred at 0 ° C. for 30 minutes and the solvent was removed under reduced pressure to obtain a composition. The resulting composition is purified by preparative thin layer chromatography, and methyl ester corresponding to aromatic carboxylic acid (aromatic carboxylic acid methyl ester, in Examples 26 to 34, compounds 5b to 5 in Table 4 respectively) 5e, 5j, 5s to 5v) were obtained. The yield of aromatic carboxylic acid methyl ester is shown in Table 4. The yield was measured by ¹ H-NMR spectrum in the same manner as in Example 1.

From Table 4, it was shown that methyl esterification using TMSCHN ₂ gives various aromatic carboxylic acid methyl esters in various yields from various aromatic chlorides.

In the Pd-catalyzed carboxylation reaction using ZnEt ₂ , an aromatic carboxylic acid could not be obtained from an aromatic chloride which is cheaper than the brominated product. On the other hand, in a carboxylation reaction using a catalyst composition containing a photoredox catalyst component (A) and a transition metal catalyst component (B), a wide variety of substrates can be used, and aromatics having various functional groups The aromatic carboxylic acid or its ester was obtained in good yield from the chloride and proved to be very useful.

(Examples 35 to 36)
A basic compound is used, wherein the content of the tertiary amine compound is 6.0 equivalents to the halogen atom in the aromatic halogen compound, using the photo-redox catalyst component (A) described in Table 5 below. The same operation as in Example 1 was performed except that it was not present. The results are shown in Table 5.

From Table 5, when Ir (ppy) ₂ (dmobpy) (PF ₆ ), which is more excellent in reducing power than Ir (ppy) ₂ (Me ₄ phen) (PF ₆ ), is used as the photoredox catalyst component (A), the substrate It can be seen that the conversion rate of (compound 1a) and the yield of aromatic carboxylic acid (compound 2a) are excellent.

(Examples 37 to 38)
In Example 37, the content ratio of the tertiary amine compound was 6.0 equivalents, and the same operation as in Example 1 was performed except that the basic compound was not used.
In addition, in Example 38, the same operation as in Example 37 was performed except that the content ratio of the photooxidation reduction catalyst component (A) was changed to 2.5 mol%. The results are shown in Table 6.

  From Table 6, it can be seen that the target compound can be obtained with good yield without using a basic compound. Furthermore, it can also be seen that the generation of the hydrogenation product (compound 3a) is suppressed and the yield of the aromatic carboxylic acid (compound 2a) is improved by increasing the content ratio of the photoredox catalyst component (A).

(Examples 39 to 40)
The photoredox catalyst component (A) described in Table 7 below is used, the content of the tertiary amine compound is 6.0 equivalents, and the basic compound is not used. I did the operation. The results are shown in Table 7.

It was shown from Table 7 that even when Ru (bpy) ₃ (PF ₆ ) ₂ was used as the photoredox catalyst component (A), an aromatic carboxylic acid could be produced from the aromatic halogen compound. In addition, since the reducing power of Ir (dF (CF ₃ ) ppy) ₂ (dtbbpy) (PF ₆ ) is superior to that of Ru (bpy) ₃ (PF ₆ ) ₂ , photooxidation of an appropriate transition metal is included. It is understood that the yield of the aromatic carboxylic acid is improved by selecting the reduction catalyst component (A).

  The catalyst composition according to the present invention does not use a metal reducing agent containing a transition metal element such as Zn or Mn (a transition metal element belonging to Group 7 or 12 of the periodic table) under light irradiation conditions. Since the aromatic carboxylic acid or ester thereof can be produced from the compound and the aromatic halogen compound, the environmental load can be reduced.

Claims (9)

Photoredox catalyst component (A) containing transition metal M belonging to periodic table groups 8 to 10, and transition metal catalyst component (B) containing transition metal M ′ belonging to periodic table groups 8 to 11 and different from said transition metal M And contains
A catalyst composition for producing an aromatic carboxylic acid or an ester thereof from carbon dioxide and an aromatic halogen compound under light irradiation conditions. The catalyst composition according to claim 1, wherein the photoredox catalyst component (A) is a compound represented by the general formula (1).
(N-C) _3-x (N-N) _x M (1)
(In the above general formula (1), N represents a nitrogen atom, C represents a carbon atom, and N—C represents a bidentate ligand coordinated to the transition metal M with a nitrogen atom and a carbon atom. And N-N each represents a bidentate ligand coordinated to the transition metal M with a nitrogen atom and a nitrogen atom, and x represents an integer of 0 to 3.)   The catalyst composition according to claim 1 or 2, wherein the transition metal M is iridium or ruthenium.   The catalyst composition according to any one of claims 1 to 3, wherein the transition metal M 'is at least one selected from the group consisting of palladium, cobalt, nickel and iron.   The catalyst composition according to any one of claims 1 to 4, wherein the transition metal catalyst component (B) contains a phosphorus atom.   Photoredox catalyst component (A) containing transition metal M belonging to periodic table groups 8 to 10, and transition metal catalyst component (B) containing transition metal M ′ belonging to periodic table groups 8 to 11 and different from said transition metal M And irradiating the carbon dioxide and the aromatic halogen compound with light in the presence of the catalyst composition.   The method for producing an aromatic carboxylic acid or an ester thereof according to claim 6, wherein the aromatic halogen compound is an aromatic chloride, an aromatic bromide or an aromatic iodide.   The manufacturing method of the aromatic carboxylic acid or its ester of Claim 6 or 7 which makes a tertiary amine compound exist with the said catalyst composition. The manufacturing method of the aromatic carboxylic acid or its ester as described in any one of Claims 6-8 which makes a basic compound exist with the said catalyst composition.