Novel methods for producing compounds, novel compounds, and metal catalysts

Abstract

One aspect of the present invention is a method for producing a compound represented by general formula (1), the method being characterized by including a step for mixing and reacting ethylene, a compound represented by general formula (2) and a compound represented by general formula (3) to obtain a compound represented by general formula (4). (A1 to A4 each independently denote an aromatic group. Z1 and Z2 independently denote an oxygen atom, a sulfur atom or borane (BH3), Z3 denotes an oxygen atom or a sulfur atom, n1 to n3 each independently denote 0 or 1, and X denotes a halogen atom.)

Description

[Technical Field]

[0001] The present invention relates to a method for producing 1,2-bis(diphenylphosphino)ethane or its derivatives, as well as novel 1,2-bis(diphenylphosphino)ethane derivatives and uses thereof. [Background technology]

[0002] 1,2-Bis(diphenylphosphin)ethane (hereinafter sometimes referred to as "DPPE") is a compound widely used in the field of organic synthesis as a bidentate ligand for transition metals. For this reason, research on methods for synthesizing DPPE is still being actively conducted. DPPE is typically obtained by reacting triphenylphosphine with metallic sodium to synthesize sodium diphenylphospide, as shown in the chemical reaction equation below, and then reacting this with dichloroethane (Non-Patent Literature 1). P(C6H5)3+ 2Na → NaP(C6H5)2+ NaC6H5 2NaP(C6H5)2+ ClCH2CH2Cl →(C6H5)2PCH2CH2P(C6H5)2+2NaCl

[0003] Another similar synthesis method involves using organoalkali metals that have been prepared in advance or generated in the reaction system. N A two-reaction method has been reported (Patent Documents 1 and 2). Another synthesis method has also been reported, which involves the addition of phosphine to a terminal alkene (Non-Patent Document 2).

[0004] Furthermore, compounds having the diphosphinoethane skeleton (-P-(CH2)2-P-) that DPPE possesses in its structure can be synthesized not only by the reactions described above, but also by, for example, the double addition reaction of phosphine oxide to alkynes described in Patent Document 3, or the insertion reaction of ethylene or styrene to diphosphine compounds described in Non-Patent Documents 3 to 7.

[0005] Compounds containing a diphosphinoethane skeleton, including DPPE, can generally be used as metal ligands. In particular, substituents bonded to the phosphorus atom (for example, the phenyl group in the case of DPPE) are thought to significantly influence the three-dimensional structure and electron distribution of the metal complex after it is formed with a transition metal. Since compounds containing a diphosphinoethane skeleton have a total of four substituents, two on each of the two phosphorus atoms, it is expected that if these substituents can be flexibly changed, various physical properties of the metal complex can be adjusted, thereby broadening the range of applications. Non-patent documents 8 and 9 disclose methods for synthesizing compounds in which substituents on the phenyl group of DPPE differ on the left and right phosphorus atoms. Non-patent document 10 also discloses a method for synthesizing compounds having a diphosphinoethane skeleton in which functional groups differ on the left and right phosphorus atoms. In this reaction, the functional group bonded to the phosphorus atom is not limited to a phenyl group; it may also be an aliphatic hydrocarbon group or a heteroatom-containing group, and the reaction is substrate-generalizable. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Specification of Chinese Patent No. 102633836 [Patent Document 2] Chinese Patent Application Publication No. 104177407 Specification [Patent Document 3] Japanese Patent Publication No. 2017-132371 [Non-patent literature]

[0007] [Non-Patent Document 1] H. Hewertson, HR Watson, J. Chem. Soc. 1962, 1490-1494 [Non-Patent Document 2] T.Bunlaksanusorn, P.Knochel, Tetrahedron Lett. 2002, 43, 5817-5819 [Non-Patent Document 3] A.B.Burg, J. Am. Chem. Soc. 1961, 83, 2226-2231 Non-Patent Document 4 K.W.Morse, J.G.Morse, J. Am. Chem. Soc. 1973, 95, 8469-8470 Non-Patent Document 5 J.Chatt, W.Hussain, G.J.Leigh, H.Mohd.Ali, C.J.Pickett, D.A.Rankin, J. Chem. Soc. Dalton Trans. 1985, 1131-1136 Non-Patent Document 6 G.W.Parshall, J. Inorg. Nucl. Chem. 1961, 83, 291-292 Non-Patent Document 7 N.Otomura, Y.Okugawa, K.Hirano, M.Miura, Synthesis 2018, 50, 3402-3407 Non-Patent Document 8 G.-A.Carraz, E.J.Ditzel, A.G.Orpen, D.D.Ellis, P.G.Pringe, G.J.Sunley, Chem. Commun. 2000, 1277-1278 Non-Patent Document 9 C.P.Casey, E.L.Paulsen, E.W.Beuttenmueller, B.R.Proft, B.A.Matter, D.R.Powell, J. Am. Chem. Soc. 1999, 121, 63-70 Non-Patent Document 10 Y.Sato, S.Kawaguchi, A.Nomoto, A.Ogawa, Chem. Eur. J. 2019, 25, 2295-2302 Summary of the Invention Problem to be Solved by the Invention

[0008] As described above, compounds having the diphosphinoethane skeleton have high utility value, and therefore, there is a need for simpler and more substrate-generalizable manufacturing methods. However, the manufacturing methods disclosed in Patent Documents 1-3 and Non-Patent Documents 1, 2, and 8-10 lacked operational simplicity because they used phosphine compounds and organoalkali metal reagents that are unstable in air. In addition, the synthesis of many of the starting compounds was difficult, and the types and number of substituents on the phenyl group of DPPE were limited.

[0009] Furthermore, while the synthesis methods described in Non-Patent Documents 3-6 are considered useful for industrialization because they use ethylene as a raw material, the functional groups bonded to the phosphorus atom of the diphosphine compound, the raw material, were limited to aliphatic hydrocarbon groups or halogen atoms. Moreover, the reaction conditions all required high temperatures of 200°C or higher, indicating a need for improvement.

[0010] According to the synthesis method for DPPE derivatives described in Non-Patent Document 7, which involves the insertion reaction of alkenes, diphenylphosphine compounds and styrene are used as starting compounds, and the reaction proceeds under light irradiation conditions. However, it is explicitly stated that this reaction does not proceed with 1-octene, but selectively proceeds with compounds having aromaticity at the vinyl position, such as styrenes. From this, it can be inferred that this reaction will not proceed even if ethylene is used as a starting compound.

[0011] The present invention has been made in view of the above, and aims to provide a method for producing compounds having a diphosphinoethane skeleton that allows for the flexible introduction of substituents under very mild conditions, regardless of the type and number of substituents, and novel compounds having a diphosphinoethane skeleton that were difficult to synthesize by conventional methods. [Means for solving the problem]

[0012] The inventors of the present invention conducted diligent research to solve the aforementioned problems. As a result, they found that the aforementioned problems could be solved by, for example, the following synthesis method and compound, and thus the present invention was concluded. Configuration examples of the present invention are as follows.

[0013] [1] A method for producing compound (1) represented by the following general formula (1), comprising:

[0014] [Chemical Formula] (A 1 ~A 4 each independently represent an aromatic group. Z 1 and Z 2 each independently represent an oxygen atom, a sulfur atom, or borane (BH3),

[0015] [Chemical Formula] represents a bond between the phosphorus atom and Z 1 or Z 2 .) n 1 and n 2 each independently represent 0 or 1. the method comprising a step of mixing and reacting ethylene, compound (2) represented by the following general formula (2), and compound (3) represented by the following general formula (3) to obtain compound (4) represented by the following general formula (4).

[0016] [Chemical Formula] (A 1 ~A 4 each have the same meaning as A 1 ~A 4 in the aforementioned formula (1). Z 3 represents an oxygen atom or a sulfur atom. n 3 represents 0 or 1. X represents a halogen atom.)

[0017] [2] The manufacturing method according to [1], wherein the step of obtaining compound (4) is to irradiate a mixture of ethylene, compound (2), and compound (3) with light and react to obtain compound (4).

[0018] [3] The manufacturing method according to [2], wherein the light includes light with a wavelength of 380 to 780 nm.

[0019] [4] The manufacturing method according to [2] or [3], wherein the irradiation of the aforementioned light is carried out in the presence of a photoelectron transfer catalyst.

[0020] [5] A manufacturing method according to any one of [1] to [4], comprising the step of subjecting the compound (4) to an oxidation reaction to obtain a compound (5) represented by the following general formula (5).

[0021] [ka] (A 1 ~A 4 These are A in formula (1) above. 1 ~A 4 It is synonymous with [the above]. Z 3 and Z 4 (Each of these independently represents either an oxygen atom or a sulfur atom.)

[0022] [6] The method for producing the compound (5) according to [5], comprising the step of subjecting it to a reduction reaction.

[0023] [7] The aforementioned compound (4) (wherein n 3 The method according to any one of [1] to [4], comprising the step of subjecting ) to a reduction reaction.

[0024] [8] The manufacturing method according to any one of [1] to [4], wherein the compound (1) is the compound (4).

[0025] [9] The manufacturing method according to [5], wherein the compound (1) is the compound (5).

[0026]

[10] The manufacturing method according to [6] or [7], wherein the compound (1) is compound (6) represented by the following general formula (6).

[0027] [ka] (A 1 ~A 4 These are A in formula (1) above. 1 ~A 4 (This is synonymous with...)

[0028]

[11] The manufacturing method according to any one of [1] to

[10] , wherein the compound (2) is a compound represented by the following general formula (7).

[0029] [ka] (A 1 ,A 2 and Z 3 These are A in equation (2) above, respectively. 1 ,A 2 and Z 3 (This is synonymous with...)

[0030]

[12] In the above general formula (1), A 1 ~A 4 The manufacturing method according to any one of [1] to

[11] , wherein at least one of is a substituted aromatic group.

[0031]

[13] In the above general formula (1), A 1 is A 2 It is identical to A 3 is A 4 It is identical to and A 1 is A 3 A manufacturing method described in any of [1] to

[12] , which is different from the above.

[0032]

[14] In the above general formula (1), A 1 is A 2 It is different from, or A 3 is A 4 A manufacturing method described in any of [1] to

[12] , which is different from the above.

[0033]

[15] A compound represented by the following general formula (9).

[0034] [ka] (A 1 ~A 4 Each of these independently represents an aromatic group. One of the following requirements (a) to (c) is met. Requirement (a): A 1 ~A 4 Two types of aromatic groups having substituents are selected, and A 1 is A 2 It is a different aromatic group from A 3 is A 4 The aromatic group is identical to the above, and the substituent is selected from the group consisting of a substituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Requirement (b):A 1 ~A 4 Three or more aromatic groups having substituents are selected. Requirement (c):A 1 is A 2 It is the same aromatic group as A 3 is A 4 It is the same aromatic group as A 1 and A 2 Group I, A 3 and A 4 If we designate this as group II, then group I and group II are distinct aromatic groups, and one of the following conditions (i) to (iv) is satisfied. (i) Aromatic groups that do not have substituents in either group I or group II; (ii) One of group I and group II is an unsubstituted aromatic hydrocarbon group having 10 or more carbon atoms, or an aromatic heterocyclic compound residue, and the other is a substituted aromatic group; (iii) One of the groups I and II is an aromatic group having an unsubstituted hydrocarbon group as a substituent, and the other is an aromatic group having any substituent selected from the group consisting of an unsubstituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group; (iv) An aromatic group having a substituent selected from the group consisting of a hydrocarbon group substituted in either group I or group II, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group.

[0035]

[16] A compound represented by the following general formula (10).

[0036] [ka] (A 1 ~A 4 Each of these independently represents an aromatic group. Z 1 and Z 2 Each of these independently represents an oxygen atom, a sulfur atom, or borane (BH3). n 1 and n 2 Each of these independently represents either 0 or 1, and n 1 =n 2 The value =0 is not true. One of the following requirements (a) to (c) is met. Requirement (a): A 1 ~A 4 Two types of aromatic groups having substituents are selected, and A 1 is A 2 It is a different aromatic group from A 3 is A 4The aromatic group is identical to the one described above, and the substituent is selected from the group consisting of a substituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Requirement (b):A 1 ~A 4 Three or more aromatic groups having substituents are selected. Requirement (c):A 1 is A 2 It is the same aromatic group as A 3 is A 4 It is the same aromatic group as A 1 and A 2 Group I, A 3 and A 4 If we designate this as group II, then group I and group II are distinct aromatic groups, and one of the following conditions (i) to (iv) is satisfied. (i) Aromatic groups that do not have substituents in either group I or group II; (ii) One of group I and group II is an unsubstituted aromatic hydrocarbon group having 10 or more carbon atoms, or an aromatic heterocyclic compound residue, and the other is a substituted aromatic group; (iii) One of the groups I and II is an aromatic group having an unsubstituted hydrocarbon group as a substituent, and the other is an aromatic group having any substituent selected from the group consisting of an unsubstituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group; (iv) An aromatic group having a substituent selected from the group consisting of a hydrocarbon group substituted in either group I or group II, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group.

[0037]

[17] A metal complex comprising a metal atom and a compound described in

[15] coordinated to the metal atom as a ligand.

[0038]

[18] A metal catalyst containing the metal complex described in

[17] . [Effects of the Invention]

[0039] According to the present invention, by using ethylene, which is commonly used industrially, and a compound that can be handled stably even in the atmosphere as raw material compounds, it is possible to produce a compound having a diphosphinoethane skeleton under very mild reaction conditions. Furthermore, the production method of the present invention can flexibly synthesize a desired compound having a diphosphinoethane skeleton, regardless of the type or number of substituents. Furthermore, it is presumed that compounds having a novel diphosphinoethane skeleton can be used as ligands in complex catalysts, and that the selectivity of the catalyst and other properties can be adjusted to desired levels depending on the type or combination of substituents introduced. [Modes for carrying out the invention]

[0040] In this specification, DPPE (1,2-bis(diphenylphosphino)ethane) derivatives refer to a general term for compounds other than DPPE that have a 1,2-diphosphinoethane skeleton (-P-(CH2)2-P-), and the aromatic group bonded to the phosphorus atom is not limited to a phenyl group, nor is the valency of the phosphorus atom relevant. In this specification, for example, among the compounds (1), (4), (5), (6), (8) to (10) described later, compounds other than DPPE are described as DPPE derivatives.

[0041] The first invention of this invention is a method for producing a compound having a 1,2-diphosphinoethane skeleton, and the method for producing it using a specific compound and ethylene as raw materials, as described later. The second aspect of the present invention lies in the novel DPPE derivative. The first invention of this invention, a method for producing a compound having a 1,2-diphosphinoethane skeleton, will be described in detail below.

[0042] Method for producing compounds having a 1,2-diphosphinoethane skeleton The method for producing a compound having a 1,2-diphosphinoethane skeleton according to the present invention (hereinafter also simply referred to as "the production method of the present invention") is a method for producing the compound (1) represented by the following general formula (1), and comprises step (a) described later and optional steps (b) to (d).

[0043]

Chemical Formula

[0044] In the aforementioned general formula (1), A 1 to A 4 each independently represent an aromatic group. Z 1 and Z 2 each independently represent an oxygen atom, a sulfur atom or borane (BH₃), and an oxygen atom or a sulfur atom is preferred. n 1 and n 2 each independently represent 0 or 1.

[0045] Moreover, in the aforementioned general formula (1),

[0046]

Chemical Formula

[0047] The aforementioned aromatic group is an atomic group obtained by removing one hydrogen atom from the hydrogen atoms directly bonded to the aromatic ring of an optionally substituted aromatic compound. The total number of carbon atoms and optional heteroatoms in the aromatic ring is preferably 4 to 60, more preferably 4 to 48, still more preferably 5 to 30, particularly preferably 5 to 25, and most preferably 5 to 20.

[0048] Examples of the aromatic compounds include aromatic carbocyclic compounds and aromatic heterocyclic compounds. For example, aromatic carbocyclic compounds represented by the following formulas (A-1) to (A-15); and aromatic heterocyclic compounds represented by the following formulas (A-16) to (A-32) and (B-1) to (B-10). Preferably, the aromatic compounds are those represented by the following formulas (A-1) to (A-5) and (B-1) to (B-3). Although substituents are not shown in the following formulas (A-1) to (A-32) and (B-1) to (B-10), the aromatic compounds may or may not have substituents as appropriate.

[0049] [ka]

[0050] [ka]

[0051] In the present invention, "substituted aromatic group" refers to a compound in which some or all of the hydrogen atoms in the aromatic group are substituted with substituents. Specifically, it refers to a compound in which some or all of the hydrogen atoms in the aromatic group are substituted with halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, or tin-containing groups, and two or more adjacent groups may be linked to each other to form a ring.

[0052] Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0053] The hydrocarbon group is not particularly limited, but typically includes linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic hydrocarbon groups having 3 to 30 carbon atoms, or aromatic hydrocarbon groups having 6 to 30 carbon atoms. Specifically, this includes linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, and more preferably 1 to 10, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups; Linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as vinyl groups, allyl groups, and isopropenyl groups; Linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20, and more preferably 2 to 10, such as ethynyl groups and propargyl groups; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, norbornyl group, adamantyl group, and other cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, and more preferably 3 to 12 carbon atoms; Cyclopentadienyl, indenyl, and fluorenyl cyclic unsaturated hydrocarbon groups with 5 to 30 carbon atoms; Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, and more preferably 6 to 10, such as phenyl groups, naphthyl groups, biphenyl groups, terphenyl groups, phenanthryl groups, and anthracenyl groups; Alkyl-substituted aryl groups such as tolyl group, iso-propylphenyl group, t-butylphenyl group, dimethylphenyl group, and di-t-butylphenyl group; aryl-substituted alkyl groups such as benzyl and cumyl groups. These are some examples.

[0054] In the hydrocarbon group, the hydrogen atom may be substituted with a halogen atom. Examples of hydrocarbon groups in which hydrogen atoms are substituted with halogen atoms include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20, such as trifluoromethyl groups, pentafluorophenyl groups, and chlorophenyl groups. Furthermore, in the hydrocarbon group, the hydrogen atom may or may not be substituted with a substituent, such as a heterocyclic compound residue described later, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

[0055] Examples of the heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran; and sulfur-containing compounds such as thiophene (atomic groups obtained by removing one hydrogen atom from these compounds); and groups obtained by further substituting these heterocyclic compound residues with substituents such as alkyl groups and alkoxy groups having 1 to 30, preferably 1 to 20 carbon atoms. Examples of the oxygen-containing groups include alkoxy groups, allyloxy groups, alkoxycarbonyl groups, ether groups (groups having a structure derived from ethers), acyl groups, carboxyl groups, carbonate groups (groups having a structure derived from carbonate esters), hydroxyl groups, peroxy groups, and carboxylic acid anhydride groups (groups having a structure derived from carboxylic acid anhydrides).

[0056] Examples of the nitrogen-containing groups include amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and ammonium salts of amino groups. Examples of the boron-containing groups include boranediyl groups, borantriyl groups, and diboranyl groups. Examples of the sulfur-containing groups include mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate groups, isothianeate groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, and sulfenyl groups. Examples of the phosphorus-containing groups include phosphine groups, phosphoryl groups, thiophosphoryl groups, and phosphat groups.

[0057] Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. Specific examples of hydrocarbon-substituted silyl groups include methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, diphenylmethylsilyl groups, triphenylsilyl groups, dimethylphenylsilyl groups, dimethyl-t-butylsilyl groups, and dimethyl(pentafluorophenyl)silyl groups. Among these, methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups, dimethylphenylsilyl groups, and triphenylsilyl groups are preferred, with trimethylsilyl groups, triethylsilyl groups, triphenylsilyl groups, and dimethylphenylsilyl groups being particularly preferred. Specific examples of hydrocarbon-substituted siloxy groups include trimethylsiloxy groups. Examples of the germanium-containing group or the tin-containing group include groups obtained by substituting the silicon in the silicon-containing group with germanium or tin, respectively.

[0058] Examples of the aforementioned alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and t-butoxy groups. Specific examples of the allyloxy group include the phenoxy group, the 2,6-dimethylphenoxy group, and the 2,4,6-trimethylphenoxy group. Specific examples of the aforementioned alkoxycarbonyl group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and the like. Specific examples of the aforementioned acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group, and the like. Specific examples of the aforementioned amino group include a dimethylamino group, an ethylmethylamino group, a diphenylamino group, and the like. Specific examples of the aforementioned imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, a phenylimino group, and the like. Specific examples of the aforementioned amide group include an acetamido group, an N-methylacetamido group, an N-methylbenzamido group, and the like. Specific examples of the aforementioned imide group include an acetimide group, a benzimide group, and the like, Specific examples of the aforementioned thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, a phenylthiocarbonyl group, and the like. Specific examples of the aforementioned alkylthio group include a methylthio group, an ethylthio group, and the like, Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, a naphthylthio group, and the like. Specific examples of the aforementioned sulfonic ester group include a methyl sulfonate group, an ethyl sulfonate group, a phenyl sulfonate group, and the like. Specific examples of the aforementioned sulfonamide group include a phenylsulfonamido group, an N-methylsulfonamido group, an N-methyl-p-toluenesulfonamido group, and the like.

[0059] As a preferred embodiment of the compound (1), for example, a compound in which at least one of A 1 to A 4 is an aromatic group having a substituent; a compound in which A 1 and A 2 are the same aromatic group, A 3 and A 4 are the same aromatic group, and A1 and A 3 Compounds with different aromatic groups; A 1 and A 2 The aromatic groups are different, or A 3 and A 4 Compounds with different aromatic groups; A 1 ~A 4 Examples include compounds in which all aromatic groups are identical; and so on.

[0060] Furthermore, preferred embodiments of the manufacturing method of the present invention include the following: For example, The first embodiment is a method of obtaining compound (4) by reacting ethylene with compounds (2) and (3) in "step (a)" described later. Specifically, this is the case where compound (1) is compound (4); A second aspect is a method for obtaining compound (5) by following "step (a)" described later, followed by "step (b)" described later. Specifically, this is the case where compound (1) is compound (5); A third aspect is a method for obtaining compound (6) by following "step (a)" described later, then "step (b)" described later, and then "step (c)" described later. Specifically, this is the case when compound (1) is compound (6). The following details each step in order.

[0061] <Process (a)> The present invention includes a step (a) for producing the compound (4). Step (a) involves reacting ethylene, the compound (2) represented by the general formula (2), and the compound (3) represented by the general formula (3) to obtain the compound (4). The reaction is preferably a reaction in which light is irradiated onto a mixture of ethylene, compound (2), and compound (3) to obtain compound (4). The reaction can be carried out under very mild conditions because the reaction proceeds more readily with light irradiation. Furthermore, since the reaction exhibits excellent substrate generality and selectivity, the combination of compound (2) and compound (3) can be flexibly selected, and a variety of compounds (4) having various functional groups can be obtained.

[0062] [Raw material compound: Compound (2)] Compound (2), one of the raw material compounds used in the manufacturing method of the present invention, is represented by the following general formula (2).

[0063] [ka]

[0064] In the above general formula (2), A 1 and A 2 These are A in the general formula (1) mentioned above. 1 and A 2 It is synonymous with [the above]. A 1 and A 2 Examples of aromatic groups represented by are those similar to those exemplified in the explanation of general formula (1) above. In the formula, Z 3 This is either an oxygen atom or a sulfur atom. In the formula, n 3 n is an integer of 0 or 1, preferably 1. 3 When n is 1, the phosphorus atom is not oxidized in air, making it easy to handle in air. 3 Compounds in which this value is 1 are represented by the following general formula (7).

[0065] [ka]

[0066] In the above general formula (7), A 1 ,A 2 and Z 3 This is A as explained in the general formula (2) above. 1 ,A 2and Z 3 It is synonymous with [the above]. The aforementioned compound (2) is, for example, Z 3 When is an oxygen atom, see "AJ Bloomfield, JM Qian, SB Herzon, Organometallics 2010, 29, 4193-4196", Z 3 When is a sulfur atom, it can be manufactured based on the known manufacturing method described in "S. Mazieres, I. Kulai, R. Geagea, S. Ladeira, M. Destarac, Chem. Eur. J. 21, 1726-1734". From the viewpoint of the ease of obtaining or manufacturing compound (2), Z 3 As such, oxygen atoms are preferred, and in addition A 1 is A 2 It is more preferable that it be identical to the above.

[0067] From the same viewpoint as above, A 1 and A 2 It is preferably an unsubstituted phenyl group, a substituted phenyl group, or an unsubstituted aromatic group other than a phenyl group, and more preferably an unsubstituted phenyl group, a substituted phenyl group, or an unsubstituted naphthyl group. Furthermore, in the case of a phenyl group having a substituent, the substituent is preferably a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, more preferably a halogen atom, a hydrocarbon group, an oxygen-containing group, or a nitrogen-containing group, and even more preferably a halogen atom such as a chlorine atom or a fluorine atom; a hydrocarbon group such as a methyl group, a t-butyl group, or a trifluoromethyl group; an oxygen-containing group such as a methoxy group; or a nitrogen-containing group such as a dimethylamino group.

[0068] Specific examples of preferred embodiments of the aromatic group in compound (2) include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-furanyl group, 2-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-chlorophenyl group, 4-fluorophenyl group, perfluorophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-dimethylaminophenyl group, and 3,5-t-butyl-4-methoxyphenyl group.

[0069] Preferred specific examples of the compound (2) include compounds represented by the following formulas (II-1) to (II-18).

[0070] [ka]

[0071] [ka]

[0072] [Raw material compound: Compound (3)] Compound (3), one of the raw material compounds used in the manufacturing method of the present invention, is represented by the following general formula (3).

[0073] [ka]

[0074] In the general formula (3) above, X is a halogen atom, and considering the availability of the compound, the stability and reactivity of the compound, a bromine atom or a chlorine atom is preferred, and a chlorine atom is more preferred. A 3 and A 4 These are A in the general formula (1) mentioned above. 1 and A 2 It is synonymous with [the above]. A 3 and A 4Examples of aromatic groups represented by are those similar to those exemplified in the explanation of general formula (1) above.

[0075] The compound (3) can be produced, for example, based on a known production method described in "S. Schweizer, J.-M. Becht, CL Drian, Adv. Synth. Catal. 2007, 349, 1150-1158". From the viewpoint of ease of obtaining or producing compound (3), it is preferable that X is a chlorine atom, and in addition A 3 is A 4 It is more preferable that it be identical to the above.

[0076] From the same viewpoint as above, A 3 and A 4 It is preferably an unsubstituted phenyl group, a substituted phenyl group, or an unsubstituted aromatic group other than a phenyl group, and more preferably a phenyl group, a substituted phenyl group, or an unsubstituted furanyl group. Furthermore, in the case of a phenyl group having a substituent, the substituent is preferably a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, more preferably a halogen atom, a hydrocarbon group, an oxygen-containing group, or a nitrogen-containing group, and even more preferably a halogen atom such as a chlorine atom or a fluorine atom; a hydrocarbon group such as a methyl group, a t-butyl group, or a trifluoromethyl group; an oxygen-containing group such as a methoxy group; or a nitrogen-containing group such as a dimethylamino group.

[0077] Specific examples of preferred embodiments of the aromatic group in compound (3) include a phenyl group, a 2-furanyl group, a 4-trifluoromethylphenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a 4-dimethylaminophenyl group, a 3,5-dimethylphenyl group, a 3,5-t-butyl-4-methoxyphenyl group, and a perfluorophenyl group.

[0078] Preferred specific examples of the compound (3) include compounds represented by the following formulas (III-1) to (III-12).

[0079] [ka]

[0080] [ka]

[0081] In the manufacturing method of the present invention, the amount of compound (3) used is not particularly limited, but from an economic standpoint, it is usually 0.8 to 5 equivalents (hereinafter also referred to as "equiv (eq)") relative to compound (2), preferably 0.9 to 2.0 eq, and more preferably 0.9 to 1.5 eq. Here, equivalent (eq) means chemical equivalent, and in this specification, it refers to the "molar equivalent" relative to the raw material compound.

[0082] [Raw material compound: ethylene] In the manufacturing method of the present invention, ethylene is used as a raw material. Ethylene is usually used in a gaseous state. The ethylene content in the atmosphere of the reaction system is not particularly limited, but is usually 50 to 100% by volume, and preferably 70 to 100% by volume. The method of introducing ethylene will be described in detail later in the [Reaction Conditions] section. The atmosphere of the reaction system may contain gases other than ethylene, as long as they do not hinder the effects of the present invention. Examples of gases other than ethylene in the atmosphere of the reaction system include inert gases (helium gas, nitrogen gas, argon gas, etc.).

[0083] Furthermore, industrially produced ethylene can be used, and even if separated and purified pure ethylene is used, a mixed gas containing hydrocarbons other than ethylene may be used, as long as it does not hinder the effects of the present invention.

[0084] The above step (a) may include the following steps (a-1) and (a-2). Step (a-1) is a step in which compound (2) and compound (3) are reacted to obtain a diphosphine compound represented by the following general formula (Y) (hereinafter also referred to as "compound (Y)").

[0085] [ka]

[0086] In the above general formula (Y), A 1 ~A 4 , Z 3 and n 3 This is equivalent to the same symbol as in compounds (2) and (3) above.

[0087] Step (a-2) is a step of reacting compound (Y) with ethylene to obtain compound (4). The inventors presume that compound (4) is obtained when the reactant species obtained by the cleavage of compound (Y) reacts with ethylene.

[0088] Steps (a-1) and (a-2) may, for example, involve isolating the compound (Y) obtained in step (a-1) and then adding ethylene in step (a-2) to carry out the reaction. However, since the compound (Y) may be unstable, it is preferable to carry out the steps continuously without isolation or other procedures. The compound (Y) obtained in step (a-1) is presumed to rapidly generate compound (4) in step (a-2), preferably by light irradiation, when ethylene is present in the reaction system. In other words, the reactions in steps (a-1) and (a-2) may proceed simultaneously within the reaction system.

[0089] Although the detailed reaction mechanism in step (a) is unknown, the inventors estimate the reaction mechanism in step (a) as follows: After compound (Y) is formed from compound (2) and compound (3), a small amount of Ar derived from compound (2) is released due to the uniform cleavage of compound (Y). 1 Ar 2 P(=Z 3 ) n3The phospholyl radical represented by · (e.g., Ph2P(=O)·) and the Ar from compound (3) 3 Ar 4 A phosphenyl radical represented by P· (for example, Ph2P·) is generated. The phospholyl radical selectively adds to ethylene, forming a primary alkyl radical (Ar 1 Ar 2 P(=Z 3 ) n3 CH2CH· (for example, Ph2P(=O)CH2CH·) is generated. Subsequently, the primary alkyl radical adds to another compound (Y) generated in the system, producing compound (4) and a new phosphoryl radical, and these reactions proceed in succession (radical chain mechanism). Furthermore, a reaction mechanism is also hypothesized in which the compound (Y) generated in the system is cleaved and ethylene is inserted without generating radicals, and it is also hypothesized that the insertion reaction proceeds in parallel with the radical chain mechanism.

[0090] [light] In the manufacturing method of the present invention, step (a) is preferably carried out by irradiating the mixture of raw material compounds with light. In addition to the radical chain mechanism in step (a), the inventors have estimated the reaction mechanism in step (a) when light irradiation is performed as follows: Compound (Y) is produced from compound (2) and compound (3). When light irradiation is performed, the phospholyl radical and the phosphenyl radical are produced by energy transfer from the photocatalyst or excitation by light. Subsequently, the phospholyl radical is selectively added to ethylene to produce the primary alkyl radical, and finally, compound (4) is produced by radical-radical coupling between the alkyl radical and the phosphenyl radical.

[0091] In the manufacturing method of the present invention, the target compound can be produced by including step (a). More specifically, it is presumed that the reaction proceeds via an extremely advantageous reaction pathway by using ethylene, compounds (2) and (3) as reactant compounds. Preferably, in step (a), the reaction is accelerated by light irradiation. In particular, when steps (a-1) and (a-2) are followed, it is presumed that the compound (Y) obtained in step (a-1) readily reacts with the phospholyl radical and the phosphenyl radical upon light irradiation, allowing for a more efficient reaction pathway and accelerating the reaction with ethylene.

[0092] The dominant wavelength of the light source used is not particularly limited as long as it includes light in the wavelength range in which the effects of the present invention can be obtained, and can be appropriately used as sunlight and light in natural environments based on it, or as artificial light sources such as lighting. The aforementioned wavelength range is not particularly limited, but is usually 250 to 800 nm. It is preferable that it includes 380 to 780 nm, which is the wavelength range of visible light in which the effects of the present invention are highly effective. When the catalyst described later is not added, it is more preferable that the dominant wavelength of the light source includes 380 to 630 nm, and when the catalyst described later is added, it is more preferable that the dominant wavelength of the light source includes 400 to 600 nm. From the estimated reaction mechanism, the dominant wavelength of the light source can be appropriately selected considering the main excitation wavelength of the raw material compound or catalyst used.

[0093] As for the light source, there are no particular restrictions as long as it is commonly used for lighting, such as LED lamps, fluorescent lamps, and incandescent bulbs. Among these, LED lamps whose main wavelength falls within the aforementioned range are preferred. When adding a catalyst, as described later, if the excitation wavelength of the catalyst is known, the reaction efficiency can be expected to improve by selecting the wavelength of light from the LED lamp used. For example, for compounds that have absorption around 450 nm, a blue LED (wavelength approximately 440 nm) can be used as the light source.

[0094] The intensity and amount of light to be irradiated are not particularly limited as long as they can promote the reaction in step (a) above, and are not limited to the amount of light typically used for light sources for photochemical reactions. For example, while there are no particular limitations on LED lamps, it is generally sufficient to use an LED lamp equivalent to 10W or more, and a stronger light intensity is preferable as it is advantageous for the progress of the reaction, and the upper limit of the light intensity is not limited as long as it does not hinder the effects of the present invention. Furthermore, the intensity of the light, for example, when expressed in terms of irradiance, is not particularly limited as long as it is within a range that can excite the reaction in step (a). Typically 50 mW / cm² 2 Anything above this level is acceptable, and a stronger level is preferable as it is advantageous in the progress of the reaction. The upper limit is not limited as long as it does not hinder the manufacturing method of the present invention.

[0095] Furthermore, the irradiation time is not particularly limited and can be set appropriately depending on the reactant material used and the light intensity of the light source. Typically, it is 10 minutes or more, and the irradiation time can be extended as needed to allow the reaction to proceed. Alternatively, the light can be irradiated as needed while monitoring the progress of the reaction.

[0096] [Photoelectron transfer catalyst] In the manufacturing method of the present invention, a photoelectron transfer catalyst can be further present in the reaction system for the purpose of improving reaction efficiency. The photoelectron transfer catalyst is added to the reaction system, for example, to the reaction solution, to promote the reaction in step (a). Specifically, when steps (a-1) and (a-2) are included, although not particularly limited, the reaction in step (a-2) is usually promoted, and it is presumed that the reaction to produce compound (Y) proceeds efficiently, preferably when light irradiation is performed. While there are no particular limitations on the photoelectron transfer catalyst, based on the estimated reaction mechanism described above, it is preferable that the photoelectron transfer catalyst improves the reaction efficiency of step (a-2) by light irradiation in step (a).

[0097] The photoelectron transfer catalyst is not particularly limited, but it should have photosensitizing properties that enable the production method of the present invention, and both metal complex catalysts and organic catalysts can be used. As metal complex catalysts, transition metal complexes are preferred, such as iridium complexes and ruthenium complexes. Compounds (α) to (ε) listed in Table 1 are examples of such transition metal complexes. As organic catalysts, for example, compounds (ζ) to (ι) listed in Table 1 can be used. The compounds listed in Table 1 are examples of photoelectron transfer catalysts, and known compounds generally considered to have similar properties can be used.

[0098] [Table 1]

[0099] In Table 1, ppy is an abbreviation for 2-phenylpyridine, bpy for 2,2'-bipyridine, dtbbpy for 4,4'-di-tert-butyl-2,2'-bipyridine, and TPP for triphenylpipyrium.

[0100] These photoelectron transfer catalysts can be used individually or in combination of two or more types. Among these, iridium complexes are preferred when considering reactivity, and more preferably compound (α) Ir(ppy)3 or compound (δ) [Ir(ppy)2(dtbbpy)]PF6 in Table 1. For example, when compound (δ) is used, since there is light absorption around 440 nm, a blue LED with a maximum wavelength of 440 nm may be used as the light source.

[0101] The photoelectron transfer catalyst may be a commercially available product or may be manufactured and used according to a known method.

[0102] In the manufacturing method of the present invention, when the photoelectron transfer catalyst is used, the amount of the photoelectron transfer catalyst used is not particularly limited, but considering the reactivity, it is usually preferable to use 0.00010 to 1.0 moles (0.010 to 100 mol%), more preferably 0.00050 to 0.5 moles (0.050 to 50 mol%), and even more preferably 0.0010 to 0.2 moles (0.10 to 20 mol%) per mole of compound (2). When multiple types of photoelectron transfer catalysts are used, the amount of the photoelectron transfer catalyst used is based on the total number of moles.

[0103] [base] In the manufacturing method of the present invention, it is preferable that step (a) be carried out in the presence of a base. The reaction in step (a) is accelerated by adding a base to the reaction system, for example, to the reaction solution. Specifically, when steps (a-1) and (a-2) are included, although not particularly limited, it is generally assumed that the reaction in step (a-1) is accelerated and the reaction to produce compound (Y) proceeds efficiently. The base is not particularly limited, but based on the estimated reaction mechanism described above, it is preferable to use a base that improves the reaction efficiency of step (a-1) in step (a).

[0104] The base used in the manufacturing method of the present invention can be an inorganic base or an organic base, etc., without any limitations. Specifically, alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, magnesium carbonate, calcium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydride, sodium hydride, potassium hydride, sodium t-butoxide, potassium t-butoxide, etc. Examples of organic bases include pyridine, N,N-dimethylaminopyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, quinoline, tetrabutylammonium hydroxide, benzyldimethylammonium hydroxide, diazabicyclononene, diazabicycloundecene, and quinuclidine.

[0105] These bases can be used individually or in combination. Among these, organic bases are preferred considering their reactivity, availability, and ease of processing in subsequent steps. Of these, triethylamine and diazabicycloundecene are preferred in order to obtain the target compound (4) in high yield.

[0106] The amount of base used is not particularly limited, but considering reactivity and ease of processing in subsequent steps, it is usually 0.5 eq or more, preferably 0.7 eq or more, more preferably 1.0 eq or more, and usually 10 eq or less, preferably 5.0 eq or less, and more preferably 3.0 eq or less, per mole of compound (2). If the amount of base is too small relative to compound (2), the reaction may not proceed sufficiently, and if the amount of base is extremely excessive, the excess base may cause side reactions. Therefore, it is preferable to use 0.5 to 10 eq, more preferably 0.5 to 5.0 eq, even more preferably 0.7 to 3.0 eq, even more preferably 0.9 to 1.2 eq, as this has a high probability of preventing the effects of excess base, and most preferably 1.0 to 1.2 eq, which allows for sufficient reaction and is economically advantageous. When two or more types of base are used, the total number of moles of the bases should not exceed the above range.

[0107] [Reaction solvent] The reaction solvent used in the manufacturing method of the present invention is not particularly limited as long as it is a solvent capable of dissolving or dispersing the three types of raw material compounds and any reactant (base, photoelectron transfer catalyst, etc.) and carrying out the reaction. The reaction may be carried out in either a homogeneous or heterogeneous system in the solvent, but considering the reactivity, it is preferable to carry out the reaction in a homogeneous system.

[0108] The reaction solvent is, Halogenated hydrocarbons such as dichloroethane, dichloromethane, and benzotrifluoride; Alcohols such as methanol, ethanol, isopropyl alcohol, 1-octanol, 1-nonanol, and benzyl alcohol; Ethers such as diethyl ether, tetrahydrofuran, dioxane, cyclopentyl methyl ether, benzyl ethyl ether, and dihexyl ether; Glycols such as ethylene glycol and propylene glycol; Alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; Alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Hydrocarbons such as cyclohexane, toluene, and xylene; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; Esters such as ethyl acetate, butyl acetate, ethoxyethyl acetate, hydroxyethyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and ethyl lactate; Examples include N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonylacetone, isophorone, caproic acid, caprylic acid, benzyl acetate, ethyl benzoate, diethyl oxalate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and acetonitrile.

[0109] These reaction solvents can be used individually or in combination of two or more. Among these, halogenated hydrocarbons are preferred considering solubility and reactivity, and dichloroethane is more preferred considering reactivity, ease of processing in subsequent steps, and cost.

[0110] In the present invention, the amount of reaction solvent used is not particularly limited, and it is sufficient to use an amount that allows the starting compound to come into sufficient contact with the reaction system. Specifically, it is preferable to use an amount of reaction solvent such that the amount of reaction solvent is 0.5 to 100 ml per 1 g of compound (2), and more preferably 1 to 20 ml. The above amounts are the amounts of reaction solvent at 23°C. If multiple types of reaction solvents are used, it is sufficient that the mixed solvent satisfies the above range.

[0111] [Other reaction conditions] To carry out the manufacturing method of the present invention, it is preferable to bring ethylene, compound (2), and compound (3) into contact with light in the reaction solvent. To promote efficient contact of each component, it is preferable to stir-mix compound (2) and compound (3) in the reaction solvent under an ethylene-containing atmosphere while irradiating with light.

[0112] In the manufacturing method of the present invention, the procedure for introducing each component into the reaction system is not particularly limited. For example, the components may be dissolved or suspended in a reaction solvent as needed before being added. Specifically, for example, a method can be employed in which compound (2), compound (3), and a base and photoelectron transfer catalyst used as needed are simultaneously introduced into the reaction system while ethylene gas is introduced and stirred; or a method can be employed in which one of the starting compounds, compound (2) or compound (3), is introduced into the reaction system first and stirred, and then the other starting compound is added to the reaction system. When adding the other starting compound to the reaction system, the base and catalyst used as needed can be introduced into the reaction system beforehand together with the first starting compound, added to the reaction system at the same time as the other starting compound is added, or added to the reaction system separately after the other starting compound has been added.

[0113] In the manufacturing method of the present invention, conventional methods known to introduce a gaseous substance into the reaction vessel can be used as a method for introducing ethylene into the reaction system. For example, methods such as creating a desired gas atmosphere in the reaction system, separately adding a solution in which the gaseous substance has been dissolved in the reaction solvent, or adding other components to the said solution can be selected. In the present invention, considering the reactivity, an introduction method that creates an ethylene-containing atmosphere is preferred.

[0114] In the manufacturing method of the present invention, when a method of introducing a gas containing ethylene is used, the pressure inside the reaction system is not particularly limited, but is usually 1 atm or higher, preferably 1 to 20 atm, and more preferably 5 to 15 atm. When the pressure is within the above range, the reactivity of the reaction is improved.

[0115] In the manufacturing method of the present invention, the reaction temperature is not particularly limited, but is usually between -30°C and 150°C. For higher yields, a temperature of 0°C or higher is preferred, 5°C or higher is more preferred, and 10°C or higher is even more preferred. Similarly, for higher selectivity, a temperature of 100°C or lower is preferred, 70°C or lower is more preferred, and 60°C or lower is even more preferred. The reaction time is not particularly limited and can be determined as appropriate while checking the consumption of the starting compounds or the amount of intermediate produced. Specifically, it is usually around 0.5 to 72 hours, or 1 to 48 hours.

[0116] [Extraction and purification of the target substance] The method for removing compound (4) from the reaction system in the production method of the present invention is not particularly limited, and known methods can be used. For example, methods such as slurry purification, recrystallization, and column purification can be used. One or more purification methods can be used, and the purification operation may be performed multiple times to achieve the desired purity.

[0117] Examples of the compound (1) produced by the manufacturing method of the present invention include compound (4), as well as compounds (5), (6), and (8) described later. When producing compound (5), compound (6), or compound (8) described later, the process may proceed to steps (b) to (d) described later without purifying compound (4). Whether or not purification is necessary can be appropriately selected by considering all steps leading to the target compound.

[0118] [Product; Compound (4)] By carrying out step (a) in accordance with the above conditions, the following compound (4) can be produced.

[0119] [ka]

[0120] In the above general formula (4), A 1 ~A 4 A in the general formula (1) is 1 ~A 4 It is synonymous with Z 3 Z in the general formula (2) above 3 It is synonymous with n 3 This represents 0 or 1. As a preferred embodiment of compound (4), examples include compounds having the same substituents as A mentioned in the preferred embodiment of the aforementioned compound (1) 1 to A 4 mentioned above.

[0121] As described above, the production method of the present invention optionally includes steps (b) to (d) subsequent to the aforementioned step (a).

[0122] <Step (b)> The production method of the present invention can optionally include step (b) of producing compound (5) represented by the following general formula (5). This step (b) is a step of subjecting the aforementioned compound (4) to an oxidation reaction to obtain the aforementioned compound (5).

[0123] [Chemical Formula]

[0124] In the aforementioned general formula (5), A 1 to A 4 have the same definitions as A in the aforementioned general formula (1) 1 to A 4 , and Z 3 and Z 4 each independently represent an oxygen atom or a sulfur atom. As a preferred embodiment of compound (5), examples include compounds having, as A 1 to A 4 , the same substituents as A mentioned in the preferred embodiment of the aforementioned compound (1) 1 to A 4 mentioned above. That is, when the aforementioned compound (1) produced by the production method of the present invention is the aforementioned compound (5), the aforementioned compound (5) can be produced by a method including the aforementioned step (a) and step (b).

[0125] The oxidation reaction can be any known oxidation reaction, and is not particularly limited as long as it can oxidize trivalent phosphorus atoms to pentavalent phosphorus atoms. In the production method of the present invention, for example, an oxidation reaction using hydrogen peroxide (H2O2) as the oxidizing agent (example reference: JA Buonomo, CG Eiden, CC Aldrich, Chem. Eur.J. 2017, 23, 14434-14438) or an oxidation reaction using sulfur (S8) as the oxidizing agent (example reference: A. Sato, H. Yorimitsu, K. Oshima, Angew. Chem. Int. Ed. 2005, 44, 1694-1696) can be used. The reaction conditions for the above reaction can be appropriately selected according to the respective references.

[0126] The oxidation reaction using hydrogen peroxide described above is not limited in purpose, but is preferably used to selectively oxidize trivalent phosphorus atoms and convert them to phosphine oxide. Specifically, for example, the trivalent phosphorus atoms of compound (4) are oxidized, Z 4 It is used to introduce an oxygen atom and convert it into the aforementioned compound (5). The aforementioned oxidation reaction using sulfur is used for no particular purpose, but preferably for the purpose of selectively oxidizing trivalent phosphorus atoms and converting them to phosphine sulfide. Specifically, for example, the trivalent phosphorus atoms of compound (4) are oxidized, Z 2 It is used to introduce a sulfur atom and convert it to the aforementioned compound (5). Since the oxidation reaction with sulfur proceeds relatively easily, it is also used to protect the trivalent phosphorus atom, which is considered to be relatively reactive.

[0127] Furthermore, the sulfur atoms present in the molecule of compound (5) can be converted to oxygen atoms using another oxidizing agent. Specifically, the Z in compound (5) 3 or Z 4 If it is a sulfur atom, it can be oxidized with an oxidizing agent and converted into oxygen atoms. When the reduction reaction is carried out in step (c) when producing compound (6) described later, Z in compound (5)3 and Z 4 It is preferable for both to be oxygen atoms in terms of reaction control. The oxidizing agent used to oxidize the sulfur atom is not particularly limited as long as it can achieve its purpose, but for example, m-chloroperbenzoic acid (mCPBA) can be used.

[0128] <Process (c)> The manufacturing method of the present invention may optionally include a step (c) for producing a compound (6) represented by the following general formula (6). Step (c) is the compound (4) (wherein n 3 The step is to obtain compound (6) by subjecting compound (5) to a reduction reaction.

[0129] [ka]

[0130] In the above general formula (6), A 1 ~A 4 A in the general formula (1) is 1 ~A 4 It is synonymous with [the above]. As a preferred embodiment of compound (6), A is listed in the preferred embodiment of compound (1). 1 ~A 4 Examples include compounds having the same substituents as [the given compound]. In other words, if the compound (1) produced by the manufacturing method of the present invention is the compound (6), then the compound (6) can be produced by a method including the steps (a) and (c) described above.

[0131] The reduction reaction can be any known reduction reaction, and is not particularly limited as long as it can reduce pentavalent phosphorus atoms to trivalent phosphorus atoms. In the production method of the present invention, for example, a reduction reaction using 1,3-diphenyldisiloxane as a reducing agent can be used (example reference: JA Buonomo, CG Eiden, CC Aldrich, Chem. Eur. J. 2017, 23, 14434-14438). Other reducing agents that can be used include PhSiH3, Ph2SiH2, (EtO)2SiHMe, (EtO)3SiH, Cl3SiH, etc. The reaction conditions for the above reaction should be appropriately selected according to the respective references.

[0132] <Process (d)> The manufacturing method of the present invention may optionally include a step (d) for producing a compound (8) represented by the following general formula (8). Step (d) is the compound (4) (wherein n 3 The step is to use compound (6) as phosphine borane. Although phosphine borane has a trivalent phosphorus atom, it is generally known to be stable in the atmosphere by forming a coordinate bond with boron, and is therefore used in various reactions as a precursor of phosphine, which is unstable in the atmosphere.

[0133] [ka]

[0134] In the above general formula (8), A 1 ~A 4 A in the general formula (1) is 1 ~A 4 It is synonymous with [the above]. As a preferred embodiment of compound (8), A is listed in the preferred embodiment of compound (1). 1 ~A 4 Examples include compounds having the same substituents as [the given compound]. In other words, if the compound (1) produced by the manufacturing method of the present invention is the compound (8), then the compound (8) can be produced by a method including steps (a) and (d) described above.

[0135] For the synthesis reaction of the aforementioned phosphine borane, a known reaction can be adopted. Usually, the synthesis can be achieved by reacting phosphine with a reagent serving as a borane source, for example, BH3·THF, NaBH4, etc. (Reference example: O. M. Demchuk, R. Jasinski, D. Strzelecka, K. Dziuba, K. Kula, J. Chrzanowski, D. Krasowska, Pure Appl. Chem. 2018, 90, 49-62). As for the reaction conditions of the aforementioned reaction, appropriate conditions may be selected as appropriate according to each document.

[0136] Any of the above optional steps (b) to (d) can be appropriately selected in consideration of the intended use of the converted compound, storage environment, equipment status, and the like. The conversion step can include one or two or more of the aforementioned optional steps (b) to (d) depending on its purpose. The purification treatment can be carried out by the method described in [isolation and purification of the target product] in step (a) in any of steps (b) to (d). When a plurality of reactions are combined, the presence or absence of a purification treatment between each reaction can be appropriately selected. The determination may be made in consideration of the stability of the product after each reaction, the yield, the influence of residues on the next reaction, and the like. In the Examples (Examples 1 to 8, Comparative Examples 1 and 2) described later, in consideration of the stability of the product, isolation and purification were performed at the stage after step (b) following step (a), and the results were compared.

[0137] According to the production method of the present invention, it is also possible to produce a novel DPPE derivative by selecting a combination of the aforementioned compound (2) and the aforementioned compound (3). Hereinafter, the novel DPPE derivatives which are the second and third inventions of the present invention (hereinafter sometimes collectively referred to as "the DPPE derivatives of the present invention") will be described.

[0138] «DPPE Derivatives» The DPPE derivative of the present invention is represented by the following general formula (9) or the following general formula (10). Hereinafter, the compound represented by the following general formula (9) is also referred to as "DPPE derivative (IX)", and the compound represented by the following general formula (10) is also referred to as "DPPE derivative (X)". The molecular structure of the DPPE derivative can be determined by nuclear magnetic resonance spectroscopy (NMR) ( 1 H and 31 P).

[0139]

Chemical Formula

[0140] In the general formula (9), A 1 to A 4 each independently represent an aromatic group. Examples of the aromatic group include the same groups as those exemplified in the description of A 1 to A 4 in the aforementioned general formula (1). In the general formula (10), Z 1 and Z 2 each independently represent an oxygen atom, a sulfur atom, or borane (BH3). In the general formula (10), n 1 and n 2 each independently represent 0 or 1, and n 1 =n 2 =0 is not satisfied.

[0141] <DPPE Derivative (IX)> In the general formula (9) representing the DPPE derivative (IX), any one of the following requirements (a) to (d) is satisfied. Requirement (a): Two types of aromatic groups having a substituent are selected as A 1 to A 4 , and A 1 is an aromatic group different from A 2 , and A 3 is A 4The aromatic group is identical to the above, and the substituent is selected from the group consisting of a substituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Requirement (b):A 1 ~A 4 Three or more aromatic groups having substituents are selected. Requirement (c):A 1 is A 2 It is the same aromatic group as A 3 is A 4 It is the same aromatic group as A 1 and A 2 Group I, A 3 and A 4 If we designate this as group II, then group I and group II are distinct aromatic groups, and one of the following conditions (i) to (iv) is satisfied. (i) Aromatic groups that do not have substituents in either group I or group II; (ii) One of group I and group II is an unsubstituted aromatic hydrocarbon group having 10 or more carbon atoms, or an aromatic heterocyclic compound residue, and the other is a substituted aromatic group; (iii) One of the groups I and II is an aromatic group having an unsubstituted hydrocarbon group as a substituent, and the other is an aromatic group having any substituent selected from the group consisting of an unsubstituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group; (iv) An aromatic group having a substituent selected from the group consisting of a hydrocarbon group that is substituted in either group I or group II, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Requirement (d):A 1 ~A 4 This is a 3,5-di-t-butyl-4-methoxyphenyl group.

[0142] In the above requirements (a) to (c), "substituted hydrocarbon group" means a hydrocarbon group in which some or all of the hydrogen atoms are substituted by substituents. Examples of the substituents include halogen atoms, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, or tin-containing groups. For example, a trifluoromethyl group is an example of a hydrocarbon group in which a hydrogen atom is substituted with a halogen atom.

[0143] In compounds that satisfy the above requirements (a) to (c), A 1 ~A 4 Preferably, one of these is an unsubstituted phenyl group, a phenyl group having substituents at the ortho, meta, or para position, or an unsubstituted aromatic group other than a phenyl group, and preferably a phenyl group having substituents at the ortho, meta, or para position. Furthermore, it is preferable that the substituent is a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, more preferably a hydrocarbon group, oxygen-containing group, or nitrogen-containing group in which some or all of the hydrogen atoms are substituted with halogen atoms, and even more preferably a halogen atom such as a chlorine atom or a fluorine atom; a hydrocarbon group such as a trifluoromethyl group in which some or all of the hydrogen atoms are substituted with halogen atoms; an alkoxy group such as a methoxy group; or an amino group such as a dimethylamino group.

[0144] Among the compounds that satisfy requirement (b) above, compounds having three types of aromatic groups are preferred, and among them, A 1 is A 2 It is identical to, or A 3 is A 4 A compound identical to the one described above is preferred.

[0145] A preferred embodiment of the compound represented by the general formula (9) that satisfies any of the above requirements (a) to (c) is, for example, the compounds represented by the following formulas (IX-1) to (IX-23). ​​In the following formulas, Me represents a methyl group, tBu represents a t-butyl group, and Mes represents a mesityl group (2,4,6-trimethylphenyl group).

[0146]

Chemical Formula

[0147]

Chemical Formula

[0148]

Chemical Formula

[0149]

Chemical Formula

[0150]

Chemical Formula

[0151] <DPPE Derivative (X)> In the aforementioned general formula (10), n 1 =n 2 =1, and Z 1 and Z 2 are not the same, it is preferred that Z 1 is an oxygen atom and Z 2 is a sulfur atom, or Z 1 is a sulfur atom and Z 2 is an oxygen atom, and it is more preferred that Z 1 is an oxygen atom and Z 2 is a sulfur atom. n 1 =n 2 =1, and Z 1 and Z 2 are the same, Z 1 and Z 2 are preferably an oxygen atom or a sulfur atom, and it is more preferred that Z 1 and Z 2 are oxygen atoms. In the aforementioned general formula (10), n 1 or n2 If either of the two is 1, then Z has a bond with the phosphorus atom. 1 or Z 2 However, it is preferable that it be an oxygen atom or a sulfur atom.

[0152] In the general formula (10) above, which represents the DPPE derivative (X), Z 1 and Z 2 If they are the same, then either requirement (a) to (c) above or requirement (e) below is satisfied. Requirement (e):A 1 ~A 4 One type of aromatic group is selected. However, Z 1 and Z 2 When is an oxygen atom, the aromatic group does not include unsubstituted phenyl group, unsubstituted naphthyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, 2-alkoxyphenyl group (where the number of carbon atoms in the alkoxy group is 4 or less), 4-methylphenyl group, 3-sulfophenyl group, 4-bromophenyl group, 4-ethynylphenyl group, 4-trimethylsilylethynylphenyl group, 4-(p-methoxycarbonylbenzoxy)phenyl group, perfluorophenyl group, and 5-t-butyl-3-methyl-2-methoxyphenyl group. Z 1 and Z 2 When the atom is a sulfur atom, the aromatic group does not include an unsubstituted phenyl group, a 4-ethynylphenyl group, or a 4-trimethylsilylethynylphenyl group.

[0153] Among the compounds that satisfy requirement (e), A 1 ~A 4 It is preferably a phenyl group having substituents at the ortho, meta, or para position, or an unsubstituted aromatic group other than a phenyl group, and is preferably a phenyl group having substituents at the para or meta position. Furthermore, preferred embodiments of the substituents are the same as those described in the explanations of requirements (a) to (c) above.

[0154] Preferred embodiments of the compound represented by the general formula (10) that satisfy any of the above requirements (a) to (c) or (e) include, for example, the compounds represented by the following formulas (X-1) to (X-27) and (X-29) to (X-32). In the following formulas, Me represents a methyl group, tBu represents a t-butyl group, and Ph represents an unsubstituted phenyl group.

[0155] [ka]

[0156] [ka]

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [Applications of DPPE derivatives] The DPPE derivative of the present invention is expected to be applicable to the same uses as DPPE and known DPPE derivatives. Compounds having a diphosphinoethane skeleton generally function as catalysts by forming complexes with metal atoms. As described in the above-mentioned document (S.-J. Poingdestre, JD Goodacre, ASWeller, MC Willis, Chem. Commun. 2012, 48, 6354-6356), differences in the electronic state and stereostructure around the phosphorus atom result in differences in selectivity in chemical reactions. Therefore, it is considered that the DPPE derivative of the present invention can be applied to the reactions described in the above-mentioned document and other known catalytic reactions after forming a metal complex.

[0162] [ka] [Examples]

[0163] An embodiment of the present invention will be described in detail below with reference to examples, but these are specific examples and the present invention is not limited thereto. [Measurement method] DPPE derivatives are 1 H-NMR spectrum and 31 The P-NMR spectrum was measured and identified.

[0164] <Nuclear Magnetic Resonance Spectrum (NMR)> ( 1 (H-NMR spectrum) Using chloroform-d as the measurement solvent, under the following measurement conditions: measurement temperature 25°C, spectral width 15 ppm, pulse repetition time 4 seconds, and pulse width 3.05 μs (45° pulse), a JNM-ECZ400S (manufactured by JEOL Ltd.) was used. 1 1H-NMR spectra (400 MHz) were measured, and various signals were assigned using conventional methods. ( 31 (P-NMR spectrum) Using chloroform-d as the measurement solvent, under the following measurement conditions: measurement temperature 25°C, spectral width 700 ppm, pulse repetition time 2 seconds, and pulse width 4.73 μs (30° pulse), a JNM-ECZ400S (manufactured by JEOL Ltd.) was used. 31 P-NMR spectra (162 MHz) were measured, and various signals were assigned using conventional methods.

[0165] [Example 1] A pressure-resistant glass cylinder (HPG-10 model, manufactured by Pressure Glass Industry Co., Ltd.) was used as the reaction vessel. Compound (δ) [Ir(ppy)2(dtbbpy)]PF6 (0.9 mg, 0.0010 mmol, 0.20 mol%) from Table 1 was added to this reaction vessel as a photoelectron transfer catalyst, and bis(4-dimethylaminophenyl)phosphine oxide (144 mg, 0.50 mmol; synthesized by the method described in our product (S. Molitor, J. Becker, VH Gessner, J. Am. Chem. Soc. 2014, 136, 15517-15520), etc.) was added as compound (2). After that, the reaction vessel was purged with nitrogen gas. Next, 1,2-dichloroethane (DCE) (1.5 mL; Aldrich) was added to the reaction vessel as the reaction solvent, bis(4-trifluoromethylphenyl)phosphine chloride (126 μL, 0.50 mmol, 1.0 eq; Alfa Aesar) as compound (3), and diazabicycloundecene (DBU) (75 μL, 0.50 mmol, 1.0 eq; Fujifilm Wako Pure Chemical Industries) as the base, and these were dissolved to form the reaction solution. Then, ethylene gas was introduced into the reaction vessel until the pressure reached 10 atm, and while maintaining the pressure at 10 atm, an LED lamp (Blue LED) (Kessil, PR160L-440nm, equivalent to 40W, illuminance 352 mW / cm²) was used. 2The reaction solution was irradiated with blue light using a ) and stirred at room temperature for 4 hours. After returning the pressure in the reaction vessel to atmospheric pressure, sulfur powder (19 mg, 0.60 mmol, 1.2 eq) was added to the reaction solution and stirred at room temperature for 30 minutes. After removing the solvent from the reaction solution by distillation, the product was separated and purified by silica gel column chromatography (solvent composition: dichloromethane / acetone = 9 / 1 → 4 / 1) to obtain product 1 (210 mg, 0.31 mmol, yield 63%) as a white solid.

[0166] [Table 2]

[0167] [ka]

[0168] [Example 2] A reaction solution was prepared using the same reaction materials, quantities, and procedures as in Example 1, except that a photoelectron transfer catalyst was not used. Next, ethylene gas was introduced into the reaction vessel as in Example 1, and the pressure inside the reaction vessel was set to 10 atmospheres. Subsequently, an LED lamp (White LED) (Kessil, A160WE Tuna Sun, equivalent to 40W, illuminance 352 mW / cm²) was added to the reaction solution. 2 The mixture was irradiated with white light using a fluorine filter and stirred at room temperature for 24 hours. After returning the pressure in the reaction vessel to atmospheric pressure, the process was carried out in the same manner as in Example 1 to obtain Product 1 (192 mg, 0.29 mmol, yield 57%).

[0169] [ka]

[0170] [Examples 3-10, and Comparative Example 1] As shown in Table 3, the synthesis of various compounds was carried out using the same procedure as in Example 1, except that the reaction conditions were changed. The results for each example and comparative example are shown in Table 3. In Table 3, "Scale" indicates the amount (mmol) of compound (2) used, and the numbers listed in the "Catalyst" column correspond to compounds (α) to (ι) in Table 1. The formation of products 1-4 to 10 and B1 synthesized in each example and comparative example was confirmed by NMR, similar to product 1.

[0171] [Example 24] A metal pressure-resistant vessel (TVS-1 type, manufactured by Pressure-Resistant Glass Industry Co., Ltd.) and a corresponding glass inner cylinder were used as the reaction vessel. As shown in Table 3, the reaction solution was prepared using the same reaction materials, ratios, and procedures as in Example 2, except that light irradiation was not performed and compound (2) was used on a 0.1 mmol scale. Here, "light irradiation was not performed" means that the reaction vessel was completely shielded from light and placed in a dark place during the procedure. Next, ethylene gas was introduced into the reaction vessel as in Example 1, the pressure inside the reaction vessel was set to 10 atmospheres, and the vessel was stirred at room temperature for 4 hours. After returning the pressure inside the reaction vessel to atmospheric pressure, product 1 was obtained by the same method as in Example 1. 1 The yield determined by 1H-NMR (internal standard: 1,1,2,2-tetrachloroethane) was 22%.

[0172] [Table 3]

[0173] [Example 11] Product 1 (334 mg, 0.50 mmol, 1.0 eq) was added to a reaction glass flask, and while cooling at 0°C, dichloromethane (DCM) (10.5 mL) was added. Subsequently, m-chloroperbenzoic acid (mCPBA) (225 mg, 0.90 mmol, 1.8 eq) was slowly added and dissolved, and the mixture was stirred at room temperature for 2 hours. The reaction was stopped by adding saturated sodium bicarbonate aqueous solution to the reaction solution, and the product was extracted using dichloromethane. Subsequently, the product was dried using anhydrous sodium sulfate, and the solvent was removed by distillation. The obtained crude product was separated and purified using silica gel column chromatography (solvent composition: dichloromethane / methanol = 20 / 1 → 9 / 1) to obtain product 2 (295 mg, 0.45 mmol, yield 90%) as a white solid.

[0174] [Table 4]

[0175] [ka]

[0176] [Example 12] Product 2 (326 mg, 0.50 mmol, 1.0 eq), 1,3-diphenyldisiloxane (340 mg, 1.5 mmol, 3.0 eq), and toluene (1.0 mL) were sequentially added to a sealed tube container and stirred at 110°C for 16 hours under a nitrogen atmosphere. Hexane was added to the crude product obtained by distillation to precipitate a white solid, and Product 3 (263 mg, 0.42 mmol, yield 85%) was filtered off.

[0177] [Table 5]

[0178] [ka]

[0179] [Example 13] The reaction was carried out using the same reaction materials, quantities, and procedures as in Example 1, up to the step of irradiating the reaction solution with blue light and stirring. After removing the solvent from the reaction solution, the product was separated and purified by silica gel column chromatography (solvent composition: dichloromethane / acetone = 19 / 1 → 3 / 2) to obtain product 4 (194 mg, 0.30 mmol, yield 61%) as a white solid.

[0180] [Table 6]

[0181] [ka]

[0182] [Example 14] Product 4 (64 mg, 0.10 mmol, 1.0 eq), 1,3-diphenyldisiloxane (35 mg, 0.15 mmol, 1.5 eq), and toluene (0.2 mL) were sequentially added to a sealed tube container and stirred at 110°C for 16 hours under a nitrogen atmosphere. Hexane was added to the crude product obtained by distilling off the solvent from the reaction solution, and the precipitated crystals were filtered off to obtain product 3 (49 mg, 0.080 mmol, 80%), a white solid.

[0183] [ka]

[0184] [Examples 15-19] Using products 1-5 to 7, 9, and 10 obtained in Examples 5 to 7, 9, and 10 as starting compounds, various compounds were synthesized following the same procedure as in Example 11, except that the reaction conditions were changed as shown in Table 7. The results of each example are shown in Tables 7 and 8. In Table 7, "Scale" indicates the amount (mmol) of the starting compound used.

[0185] [Table 7]

[0186] [Table 8]

[0187] [Examples 20-23] Using products 2-5, 6, 9, and 10 obtained in Examples 15-18 as starting materials, various compounds were synthesized following the same procedure as in Example 12, except that the reaction conditions were changed as shown in Table 9. The results of each example are shown in Tables 9 and 10. In Table 9, "Scale" indicates the amount (mmol) of the starting material used.

[0188] [Table 9]

[0189] [Table 10]

Claims

1. A method for producing compound (1) represented by the following general formula (1), 【Chemistry 1】 (In general formula (1), A １ ~A ４ Each of these independently represents an aromatic group. Z １ and Z ２ These are, independently, an oxygen atom, a sulfur atom, or a borane (BH ３ ) represents, 【Chemistry 2】 The phosphorus atom and Z １ or Z ２ This represents a combination with. n １ and n ２ each independently represent 0 or 1.) A manufacturing method characterized by comprising the step of mixing ethylene, compound (2) represented by the following general formula (2), and compound (3) represented by the following general formula (3) and reacting them to obtain compound (4) represented by the following general formula (4). 【Transformation 3】 (In general formulas (2) to (4), A １ ~A ４ These are A in the general formula (1) mentioned above. １ ~A ４ It is synonymous with [the above]. Z ３ This represents an oxygen atom or a sulfur atom. n ３ It represents 0 or 1. X represents a halogen atom.

2. The manufacturing method according to claim 1, wherein the step of obtaining compound (4) is a step of irradiating a mixture of ethylene, compound (2), and compound (3) with light to cause a reaction and obtain compound (4).

3. The manufacturing method according to claim 2, wherein the light includes light with a wavelength of 380 to 780 nm.

4. The manufacturing method according to claim 2, wherein the irradiation of the aforementioned light is carried out in the presence of a photoelectron transfer catalyst.

5. The manufacturing method according to claim 1 or 2, comprising the step of subjecting the compound (4) to an oxidation reaction to obtain a compound (5) represented by the following general formula (5). 【Chemistry 4】 (In general formula (5), A １ ~A ４ These are A in the general formula (1) mentioned above. １ ~A ４ It is synonymous with [the above]. Z ３ and Z ４ Each of these independently represents either an oxygen atom or a sulfur atom.

6. The manufacturing method according to claim 5, comprising the step of subjecting the compound (5) to a reduction reaction.

7. The aforementioned compound (4) (wherein n ３ The manufacturing method according to claim 1 or 2, comprising the step of subjecting (1) to a reduction reaction.

8. The manufacturing method according to claim 1 or 2, wherein the compound (1) is the compound (4).

9. The manufacturing method according to claim 5, wherein the compound (1) is the compound (5).

10. The manufacturing method according to claim 6, wherein the compound (1) is a compound represented by the following general formula (6). 【Transformation 5】 (In general formula (6), A １ ~A ４ These are A in the general formula (1) mentioned above. １ ~A ４ (This is synonymous with...)

11. The manufacturing method according to claim 7, wherein the compound (1) is a compound represented by the following general formula (6). 【Transformation 6】 (In general formula (6), A １ ~A ４ These are A in the general formula (1) mentioned above. １ ~A ４ (This is synonymous with...)

12. The manufacturing method according to claim 1 or 2, wherein the compound (2) is a compound represented by the following general formula (7). 【Transformation 7】 (In general formula (7), A １ A ２ and Z ３ These are A in the general formula (2) mentioned above. １ A ２ and Z ３ (This is synonymous with...)

13. In the above general formula (1), A １ ~A ４ The manufacturing method according to claim 1 or 2, wherein at least one of the groups is an aromatic group having a substituent.

14. In the above general formula (1), A １ is A ２ It is identical to A ３ is A ４ It is identical to and A １ is A ３ A manufacturing method according to claim 1 or 2, which differs from the other method.

15. In the above general formula (1), A １ is A ２ It is different from, or A ３ is A ４ A manufacturing method according to claim 1 or 2, which differs from the other method.

16. A compound represented by the following general formula (9). 【Transformation 8】 (In general formula (9), A １ ~A ４ Each of these independently represents an aromatic group. One of the following requirements (a) to (c) must be met. Requirement (a): A １ ~A ４ Two types of aromatic groups having substituents are selected, and A １ is A ２ It is a different aromatic group from A ３ is A ４ The aromatic group is identical to the above, and the substituent is selected from the group consisting of a substituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Requirement (b): A １ ~A ４ Three or more aromatic groups having substituents are selected. Requirement (c): A １ is A ２ It is the same aromatic group as A ３ is A ４ It is the same aromatic group as A １ and A ２ Group I, A ３ and A ４ If we designate this as group II, then group I and group II are distinct aromatic groups, and one of the following conditions (i) to (iv) is satisfied. (i) Aromatic groups that do not have substituents in either group I or group II; (ii) One of group I and group II is an unsubstituted aromatic hydrocarbon group having 10 or more carbon atoms, or an aromatic heterocyclic compound residue, and the other is a substituted aromatic group; (iii) One of the groups I and II is an aromatic group having an unsubstituted hydrocarbon group as a substituent, and the other is an aromatic group having any substituent selected from the group consisting of an unsubstituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group; (iv) An aromatic group having a substituent selected from the group consisting of a hydrocarbon group substituted in either group I or group II, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group.

17. A compound represented by the following general formula (10). 【Chemistry 9】 (In general formula (10), A １ ~A ４ Each of these independently represents an aromatic group. Z １ and Z ２ Each of these independently consists of an oxygen atom, a sulfur atom, or a borane (BH ３ ) represents. n １ and n ２ Each of these independently represents either 0 or 1, and n １ = n ２ The value = 0 is not true. One of the following requirements (a) to (c) must be met. Requirement (a): A １ ~A ４ Two types of aromatic groups having substituents are selected, and A １ is A ２ It is a different aromatic group from A ３ is A ４ The aromatic group is identical to the above, and the substituent is selected from the group consisting of a substituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Requirement (b): A １ ~A ４ Three or more aromatic groups having substituents are selected. Requirement (c): A １ is A ２ the same aromatic group, and A ３ is A ４ the same aromatic group, wherein A １ and A ２ are defined as Group I, and A ３ and A ４ are defined as Group II, Group I and Group II are different aromatic groups respectively, and any one of the following (i) to (iv) is satisfied. (i) Aromatic groups that do not have substituents in either group I or group II; (ii) One of group I and group II is an unsubstituted aromatic hydrocarbon group having 10 or more carbon atoms, or an aromatic heterocyclic compound residue, and the other is a substituted aromatic group; (iii) One of the groups I and II is an aromatic group having an unsubstituted hydrocarbon group as a substituent, and the other is an aromatic group having any substituent selected from the group consisting of an unsubstituted hydrocarbon group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group; (iv) An aromatic group having a substituent selected from the group consisting of a hydrocarbon group substituted in either group I or group II, a halogen atom, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group.

18. A metal complex comprising a metal atom and the compound according to claim 16, which is coordinated to the metal atom, as a ligand.

19. A metal catalyst comprising the metal complex described in claim 18.

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