Method for producing cyclic olefin compound

Abstract

A method for producing a cyclic olefin compound, which comprises a decarbonylation and decarboxylation step for obtaining a cyclic olefin compound by decarbonylation and decarboxylation of an alicyclic dicarboxylic acid anhydride in the presence of a nickel complex represented by formula (1) and a metal-based cocatalyst, the metal-based co-catalyst contains one or more elements selected from the group consisting of elemental metals and metal compounds. Ni (Y) m (L) n (1) In formula (1), Ni is 0-valent or 2-valent nickel, Y is an anionic monodentate or polydentate ligand and has at least one Ni-E covalent bond, E is a heteroatom or a pi-bondable group, m is a real number of 0-2, L is a neutral ligand, and n is a real number of 0-6.

Description

Technical Field

[0001] The present invention relates to a method for producing a cyclic olefin compound. Background Art

[0002] Cyclic olefin compounds are useful as raw materials for cyclic olefin (co)polymers (COC, COP) obtained by copolymerization with lower olefins such as ethylene or ring-opening metathesis polymerization. Regarding methods for producing cyclic olefin compounds, various methods are known, and among them, there are (1) decarbonylation and decarboxylation reactions of alicyclic dicarboxylic anhydrides, and (2) oxidative decarboxylation reactions of dicarboxylic acid derivatives obtained by hydrolysis of alicyclic dicarboxylic anhydrides.

[0003] The alicyclic dicarboxylic anhydrides used as raw materials for these reactions can be obtained by the Diels-Alder reaction of conjugated diene compounds and maleic anhydride derivatives. Generally, in the Diels-Alder reaction, maleic anhydride derivatives exhibit high reactivity, and thus the adducts can mostly be obtained in good yields. Therefore, if decarbonylation or decarboxylation can be efficiently carried out from these alicyclic dicarboxylic anhydrides or dicarboxylic acid derivatives obtained by their hydrolysis, it is possible to expect the synthesis of cyclic olefin compounds having various structures in high yields by combining various diene compounds and maleic anhydride derivatives.

[0004] As a technique related to such a method for producing a cyclic olefin compound, for example, the technique described in Patent Document 1 can be cited. Patent Document 1 describes a method for producing a cyclic olefin compound, which includes the following steps: a divalent nickel complex having a specific chemical structure is allowed to act to decarbonylate and decarboxylate an alicyclic dicarboxylic anhydride, thereby producing a cyclic olefin compound. Patent Document 1 describes that by the above production method, a cyclic olefin compound can be stably produced even when the nickel complex is exposed to the atmosphere.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2021 / 261264 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] According to the research of the present inventors, it has been clarified that the production method described in Patent Document 1 has room for improvement from the viewpoint of the production efficiency of cyclic olefin compounds.

[0010] The present invention has been completed in view of the above circumstances, and provides a method for producing a cyclic olefin compound that improves the production efficiency of cyclic olefin compounds.

[0011] Means for Solving the Problems

[0012] That is, according to the present invention, there is provided a method for producing a cyclic olefin compound as shown below. [1]

[0014] A method for producing a cyclic olefin compound, which includes a decarbonylation and decarboxylation step of obtaining a cyclic olefin compound by performing decarbonylation and decarboxylation of an alicyclic dicarboxylic anhydride in the presence of a nickel complex represented by the following formula (1) and a metal-based cocatalyst, and the metal-based cocatalyst contains one or more selected from the group consisting of elemental metals and metal compounds.

[0015] Ni(Y) m (L) n (1)

[0016] In formula (1), Ni is nickel of valence 0 or 2, Y is an anionic monodentate or polydentate ligand and has at least one Ni-E covalent bond, E is a heteroatom or a π-bonding group, m is a real number from 0 to 2, L is a neutral ligand, and n is a real number from 0 to 6. [2]

[0018] The method for producing a cyclic olefin compound according to the above [1], wherein the metal-based cocatalyst contains one or more elements selected from the elements of Groups 1 to 14 of the long-form periodic table of the elements. [3]

[0020] The method for producing a cyclic olefin compound according to the above [1] or [2], wherein the elemental metal contains one or more selected from the group consisting of Li, Cs, Rb, K, Ba, Sr, Ca, Na, Mg, Th, Be, Al, Ti, Zr, Mn, Ta, Zn, Cr, Fe, Cd, and Co. [4]

[0022] The method for producing a cyclic olefin compound according to any one of the above [1] to [3], wherein the elemental metal contains one or two selected from the group consisting of Mn and Zn. [5]

[0024] The method for producing a cyclic olefin compound according to any one of the above [1] to [4], wherein the metal compound contains one or more elements selected from the elements of Groups 7 to 12 of the long-form periodic table of the elements. [6]

[0026] The method for producing a cyclic olefin compound according to any one of the above [1] to [5], wherein the metal compound contains one or two selected from the group consisting of Mn and Zn. [7]

[0028] The method for producing a cyclic olefin compound according to any one of [1] to [6] above, wherein the metal compound contains one or more selected from the group consisting of Mn(OAc)2 and ZnO. [8]

[0030] The method for producing a cyclic olefin compound according to any one of [1] to [7] above, wherein in the formula (1), Ni is divalent nickel, and Y contains one or more selected from the group consisting of the ligands represented by the following formula (2), the ligands represented by the following formula (3), the ligands represented by the following formula (4), the ligands represented by the following formula (5), the ligands represented by the following formula (6), the ligands represented by the following formula (7), the ligands represented by the following formula (X1), and the ligands represented by the following formula (Y1).

[0031] [Chemical formula 1]

[0032]

[0033] In the formula (2), R1 is a hydrogen atom or a hydrocarbon group which may have a substituent.

[0034] [Chemical formula 2]

[0035]

[0036] In the formula (3), R2 is a divalent hydrocarbon group which may have a substituent.

[0037] [Chemical formula 3]

[0038]

[0039] In the formula (4), R3, R4, and R5 are hydrocarbon groups which may have a substituent, and R3 and R5 or R4 and R5 may be bonded to each other to form a ring. In addition, R3, R4, and R5 may be hydrogen atoms.

[0040] [Chemical formula 4]

[0041]

[0042] In the formula (5), R6 is a divalent hydrocarbon group which may have a substituent, and R7 is a hydrogen atom, a hydrocarbon group which may have a substituent, or an oxy group. When R7 is a hydrocarbon group, it may be bonded to R6 to form a ring.

[0043] [Chemical formula 5]

[0044]

[0045] In the formula (6), Z’ is a halogen or OH.

[0046] [Chemical Formula 6]

[0047]

[0048] In formula (7), Ox is an oxyacid selected from the group consisting of NO 3- , CO3 2- and PO4 3- and forming a group of oxyacids.

[0049] [Chemical Formula 7]

[0050]

[0051] In formula (X1), R1’, R2’, R3’, R4’ and R5’ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.

[0052] [Chemical Formula 8]

[0053]

[0054] In formula (Y1), R6’, R7’ and R8’ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent. [9]

[0056] According to the method for producing a cyclic olefin compound according to any one of the above [1] to [8], in the above formula (1), the above Y includes one or more selected from the group consisting of the ligand represented by the following formula (8), the ligand represented by the following formula (9), the ligand represented by the following formula (10), the ligand represented by the following formula (11), the ligand represented by the following formula (12), the ligand represented by the following formula (13), and the ligand represented by the following formula (Z1).

[0057] [Chemical Formula 9]

[0058]

[0059] [Chemical Formula 10]

[0060]

[0061] In formula (9), X is a group of non-metal atoms required to form a ring, and R and R’ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.

[0062] [Chemical Formula 11]

[0063]

[0064] [Chemical Formula 12]

[0065]

[0066] In formula (11), R7 and R8 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and R7 and R8 may be bonded to each other to form a ring.

[0067] [Chemical Formula 13]

[0068]

[0069] In formula (12), R9 and R 10 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and R9 and R 10 may be bonded to each other to form a ring.

[0070] [Chemical Formula 14]

[0071]

[0072] In formula (13), Z” is Cl or Br.

[0073] [Chemical Formula 15]

[0074]

[10]

[0076] According to the method for producing a cyclic olefin compound according to any one of the above [1] to [9], in the decarbonylation and decarboxylation steps, a compound capable of being a ligand with respect to the nickel complex further exists.

[11]

[0078] According to the method for producing a cyclic olefin compound according to the above

[10] , in the decarbonylation and decarboxylation steps, the charged amount of the compound capable of being a ligand is 1 mol or more and 500 mol or less with respect to 1 mol of the nickel complex.

[12]

[0080] According to the method for producing a cyclic olefin compound according to the above

[10] or

[11] , the compound capable of being a ligand contains a phosphorus-containing compound.

[13]

[0082] According to the method for producing a cyclic olefin compound according to any one of the above

[10] to

[12] , the compound capable of being a ligand contains one or more selected from the group consisting of the compound represented by the following formula (14) and the compound represented by the following formula (15).

[0083] [Chemical Formula 16]

[0084]

[0085] In formula (14), X 1 、X2 and X 3 are each independently a hydrocarbon group which may have a substituent.

[0086] [Chemical Formula 17]

[0087]

[0088] In formula (15), X 4 , X 5 , X 6 and X 7 are each independently a hydrocarbon group which may have a substituent, and Z is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a ferrocenylene group, or a binaphthylene group.

[14]

[0090] The method for producing a cyclic olefin compound according to any one of the above

[10] to

[13] , wherein the compound capable of being a ligand contains triphenylphosphine.

[15]

[0092] The method for producing a cyclic olefin compound according to any one of the above [1] to

[14] , wherein the alicyclic dicarboxylic anhydride contains one or more selected from the group consisting of the compounds represented by the following formula (16) and the compounds represented by the following formula (17).

[0093] [Chemical Formula 18]

[0094]

[0095] In formula (16), X is a group of non-metal atoms required for forming a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.

[0096] [Chemical Formula 19]

[0097]

[0098] In formula (17), X is a group of non-metal atoms required for forming a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.

[16]

[0100] The method for producing a cyclic olefin compound according to any one of the above [1] to

[15] , wherein the alicyclic dicarboxylic anhydride contains the compound represented by the following formula (18).

[0101] [Chemical Formula 20]

[0102]

[0103] In formula (18), R 11 , R12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom or a substituent that may have a heteroatom.

[17]

[0105] The method for producing a cyclic olefin compound according to the above

[16] , wherein in the above formula (18), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are all hydrogen.

[18]

[0107] The method for producing a cyclic olefin compound according to any one of the above [1] to

[17] , wherein the alicyclic dicarboxylic anhydride contains a compound represented by the following formula (19).

[0108] [Chemical formula 21]

[0109]

[0110] In formula (19), n is 0 or 1, and X' is O or CH2.

[19]

[0112] The method for producing a cyclic olefin compound according to any one of the above [1] to

[18] , wherein in the above decarbonylation and decarboxylation steps, decarbonylation and decarboxylation are carried out while removing the produced cyclic olefin compound out of the reaction system.

[0113] Advantages of the Invention

[0114] The present invention provides a method for producing a cyclic olefin compound with improved production efficiency of the cyclic olefin compound. Detailed Embodiments

[0115] Hereinafter, the embodiments of the present invention will be described in detail. It should be noted that in the present embodiment, unless otherwise specified, "A to B" representing a numerical range means A or more and B or less.

[0116] The method for producing a cyclic olefin compound of the present embodiment includes a decarbonylation and decarboxylation step of obtaining a cyclic olefin compound by decarbonylating and decarboxylating an alicyclic dicarboxylic anhydride in the presence of a nickel complex represented by the following formula (1) and a metal-based cocatalyst, and the metal-based cocatalyst contains one or more selected from the group consisting of elemental metals and metal compounds.

[0117] Ni(Y) m (L) n (1)

[0118] In formula (1), Ni is nickel with a valence of 0 or 2, Y is an anionic monodentate or polydentate ligand and has at least one Ni-E covalent bond, E is a heteroatom or a π-bonding group, m is a real number from 0 to 2, L is a neutral ligand, and n is a real number from 0 to 6.

[0119] According to the production method of the present invention, the production efficiency of the cyclic olefin compound can be improved.

[0120] The mechanism by which the production efficiency of the cyclic olefin compound can be improved by the production method of the present invention is not yet clear, but the following mechanism can be speculated: the metal-based cocatalyst functions as a reducing agent to inhibit the oxidation of the nickel complex, or the nickel complex that has been oxidized and lost its activity is reduced and reactivated, thereby suppressing the amount of catalyst used while improving the efficiency of the decarbonylation and decarboxylation processes, and thus improving the production efficiency of the cyclic olefin compound.

[0121] In this embodiment, the yield of the cyclic olefin compound can be an index of the production efficiency, or, in the case of using a compound such as TPP that can be a ligand in the production of the cyclic olefin compound, the yield of the cyclic olefin compound per unit of the compound that can be a ligand can be an index of the production efficiency.

[0122] [Metal-based cocatalyst]

[0123] Hereinafter, the aforementioned metal-based cocatalyst will be described.

[0124] The aforementioned metal-based cocatalyst includes one or more selected from the group consisting of elemental metals and metal compounds. There is no particular limitation on whether to use elemental metals and metal compounds or a combination thereof, and it can be arbitrarily selected according to the embodiment. In the case of obtaining a cyclic olefin compound by a semi-batch method in which the metal-based cocatalyst (and, if necessary, a compound that can be a ligand) is pre-added to the reaction system and the alicyclic dicarboxylic anhydride and the nickel complex are separately added dropwise thereto, from the viewpoint of further improving the production efficiency, it is preferable to use elemental metals.

[0125] From the viewpoint of improving the production efficiency, the aforementioned metal-based cocatalyst preferably includes one or more elements selected from the elements of Groups 1 to 14 of the long form periodic table of the elements.

[0126] In this embodiment, the aforementioned elemental metal refers to a substance composed of one metal element.

[0127] From the viewpoint of improving production efficiency, the aforementioned elemental metal preferably contains one or more elements selected from the group consisting of Li, Cs, Rb, K, Ba, Sr, Ca, Na, Mg, Th, Be, Al, Ti, Zr, Mn, Ta, Zn, Cr, Fe, Cd, and Co, and more preferably contains one or more elements selected from the group consisting of Mn and Zn.

[0128] In the present embodiment, the aforementioned metal compound refers to a compound containing a metal element. Examples of the metal compound include metal oxides, metal hydroxides, metal salts, and metal complexes. It should be noted that examples of the metal salt include salts derived from inorganic acids such as chlorides, sulfates, and nitrates, and salts derived from organic acids such as formates, acetates, and oxalates. In addition, in the present embodiment, the metal compound is a concept including the acid anhydride of the metal compound and the hydrate of the metal compound.

[0129] From the viewpoint of improving production efficiency, the aforementioned metal compound preferably contains one or more selected from oxides and acetates.

[0130] From the viewpoint of improving production efficiency, the aforementioned metal compound preferably contains one or more elements selected from the elements of Groups 7 to 12 of the long-form periodic table of elements, more preferably contains one or more elements selected from the group consisting of Cu, Ni, Fe, Co, Zn, Ag, Cd, Sb, Ga, In, Sn, Ge, Pb, Bi, Ru, Ti, Al, Cr, Mn, Ir, V, rare earth elements, Zr, Hf, Ta, Nb, Tl, Re, W, As, Si, Mo, and Pd, and further preferably contains one or more elements selected from the group consisting of Cu, Ni, Fe, Co, Zn, Ag, Cd, Sb, Ga, In, Sn, Ge, Pb, Bi, Ru, Al, Cr, Mn, Ir, Tl, Re, W, As, Si, Mo, and Pd, and further preferably contains one or two elements selected from the group consisting of Mn and Zn.

[0131] From the viewpoint of improving production efficiency, the aforementioned metal compound preferably contains one or more selected from the group consisting of Cu(OAc)2, (HCOO)2Cu, Cu(C2O4), Cu(acac)2; Co(OAc)2, (HCOO)2Co, Co(C2O4), Co(acac)2; Ni(OAc)2, (HCOO)2Ni, Ni(C2O4), Ni(acac)2; MnO, (HCOO)2Mn, Mn(C2O4), Mn(acac)2, ZnO, Zn(OAc)2, Zn(OAc)2·4H2O, (HCOO)2Zn, Zn(C2O4), Zn(acac)2; Pd(OAc)2, (HCOO)2Pd, Pd(C2O4) and Pd(acac)2, and more preferably contains one or more selected from the group consisting of Mn(OAc)2 and ZnO. It should be noted that in this embodiment, "Ac" refers to an acetyl group, and "acac" refers to acetyl acetonate.

[0132] As described above, the aforementioned metal compound can be an anhydride or a hydrate, and from the viewpoint of further improving production efficiency, it is preferably an anhydride.

[0133] Relative to 1 mol of the aforementioned nickel complex, the amount of the aforementioned metal-based cocatalyst is preferably 0.1 mol or more, more preferably 0.5 mol or more, further preferably 1 mol or more, further preferably 2 mol or more, and preferably 100 mol or less, more preferably 90 mol or less, further preferably 80 mol or less, further preferably 70 mol or less, further preferably 60 mol or less, further preferably 50 mol or less, and further preferably 45 mol or less.

[0134] It should be noted that in the case of a semi-batch process in which a metal-based cocatalyst and a compound capable of becoming a ligand are previously charged into the reaction system and a nickel complex and a raw material are continuously supplied thereto respectively, with respect to 1 mol of the aforementioned nickel complex, the amount of the aforementioned metal-based cocatalyst is preferably 0.10 mol or more, more preferably 0.50 mol or more, still more preferably 1.00 mol or more, still more preferably 2.00 mol or more, and is preferably 100.00 mol or less, more preferably 90.00 mol or less, still more preferably 80.00 mol or less, still more preferably 70.00 mol or less, still more preferably 60.00 mol or less, still more preferably 50.00 mol or less, still more preferably 45.00 mol or less, still more preferably 41.00 mol or less, still more preferably 30.00 mol or less, still more preferably 20.00 mol or less, still more preferably 10.00 mol or less, still more preferably 5.00 mol or less, still more preferably 4.00 mol or less.

[0135] [Nickel complex]

[0136] Hereinafter, the aforementioned nickel complex will be described.

[0137] The aforementioned nickel complex is represented by the following formula (1).

[0138] Ni(Y) m (L) n (1)

[0139] In formula (1), Ni is nickel of valence 0 or 2, Y is an anionic monodentate or polydentate ligand and has at least one Ni-E covalent bond, E is a heteroatom or a π-bonding group, m is a real number from 0 to 2, L is a neutral ligand, and n is a real number from 0 to 6.

[0140] [Zero-valent nickel complex]

[0141] Hereinafter, the nickel complex in which Ni is nickel of valence 0 (zero-valent nickel complex) will be described.

[0142] When Ni is nickel of valence 0, in the aforementioned formula (1), the neutral ligand L preferably contains one or more selected from the group consisting of the ligands represented by the following formulas (14) and (15).

[0143] [Chemical formula 22]

[0144]

[0145] In formula (14), X 1 、X 2 and X 3 are each independently a hydrocarbyl group which may have a substituent.

[0146] The ligand represented by the aforementioned formula (14) includes, for example, one or more selected from the group consisting of trialkylphosphines such as tricyclohexylphosphine, tricyclopentylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, trioctylphosphine, and tribenzylphosphine; triarylphosphines such as triphenylphosphine, mesitylphosphine (including various substituted isomers of ortho, meta, and para), tris(methoxyphenyl)phosphine (including various substituted isomers of ortho, meta, and para), tris(fluorophenyl)phosphine (including various substituted isomers of ortho, meta, and para), and tris(α-naphthyl)phosphine; diarylalkylphosphines such as diphenylcyclohexylphosphine; and dialkylarylphosphines such as dicyclohexylphenylphosphine. Preferably, it includes one or more selected from the group consisting of triarylphosphines, and more preferably, it includes triphenylphosphine.

[0147] In addition, in the aforementioned formula (14), X 1 , X 2 and X 3 can also be crosslinked between two groups to form a ring containing a phosphorus atom. As such a phosphine, phenylbiphenylphosphine can be exemplified.

[0148] [Chemical formula 23]

[0149]

[0150] In formula (15), X 4 , X 5 , X 6 and X 7 are each independently a hydrocarbon group which may have a substituent, and Z is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a ferrocenylene group, or a binaphthylene group.

[0151] The ligand represented by the aforementioned formula (15) includes, for example, one or more selected from the group consisting of 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, 1,2-bis(diphenylphosphinomethyl)cyclohexane, 1,3-bis(diphenylphosphino)benzene, and 1,1'-bis(diphenylphosphino)ferrocene.

[0152] The nickel(0) complex of the present embodiment can be obtained by reacting a nickel complex such as nickel tetracarbonyl, bis(1,5-cyclooctadiene)nickel, or nickel tris(triphenylphosphite) with the aforementioned neutral ligand L.

[0153] Specific examples of the nickel(0) complex include tetrakis(triphenylphosphine)nickel ([(C6H5)3P]4Ni) and bis(triphenylphosphine)dicarbonylnickel ([(C6H5)3P]2Ni(CO)2).

[0154] The zero-valent nickel complex of the present embodiment can be synthesized, for example, by the methods described in U.S. Patent No. 4,012,399, J. Am. Chem. Soc., 81, 4800 (1959), J. Am. Chem. Soc., 94, 2669 (1972), J. Am. Chem. Soc., 96, 53 (1974), Inorg. Chim. Acta, 12, 167 (1975), Inorg. Chim. Acta, 37, L455 (1979), Chem. Lett., 831 (1974), Chem. Lett., 1119 (1972), J. Chem. Soc., 2099 (1962), etc.

[0155] <Divalent nickel complex>

[0156] Hereinafter, a nickel complex in which Ni is divalent nickel (divalent nickel complex) will be described.

[0157] In the aforementioned formula (1), Ni is divalent nickel, and the anionic ligand Y preferably contains one or more selected from the group consisting of the ligands represented by the following formula (2), the ligands represented by the following formula (3), the ligands represented by the following formula (4), the ligands represented by the following formula (5), the ligands represented by the following formula (6), the ligands represented by the following formula (7), the ligands represented by the following formula (X1), and the ligands represented by the following formula (Y1).

[0158] [Chemical formula 24]

[0159]

[0160] In formula (2), R1 is a hydrogen atom or a hydrocarbon group which may have a substituent.

[0161] Examples of the hydrocarbon group include groups having 1 to 30 carbon atoms, such as alkyl groups such as methyl, ethyl, and propyl; alkenyl groups such as vinyl and allyl; alkynyl groups such as ethynyl and propynyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenethyl; and long-chain alkyl groups such as lauryl and stearyl. Among them, as R1, a hydrogen atom or an alkyl group is preferred, and a hydrogen atom, methyl, or ethyl is more preferred.

[0162] Examples of the substituent include halogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, acyl, alkylamino, carbamoyl, nitro, nitroso, cyano, alkylthio, sulfinyl, sulfonyl, silyl, etc. In addition, among these substituents, adjacent substituents may be crosslinked to form a ring containing the bonded carbon atoms.

[0163] [Chemical formula 25]

[0164]

[0165] In formula (3), R2 is a divalent hydrocarbon group which may have substituents.

[0166] Examples of the divalent hydrocarbon group include methylene, ethylene, trimethylene, vinylidene, 1,2-phenylene, 2,3-naphthylene, 1,2-cyclohexylene, 1,2-bicyclo[2,2,1]heptylene, 1,4-dihydro-1,4-methano-2,3-naphthylene, etc. Among them, R2 is preferably 1,4-dihydro-1,4-methano-2,3-naphthylene.

[0167] [Chemical formula 26]

[0168]

[0169] In formula (4), R3, R4 and R5 are hydrocarbon groups which may have substituents, and R3 and R5 or R4 and R5 may be bonded to each other to form a ring. In addition, R3, R4 and R5 may also be hydrogen atoms.

[0170] Examples of the hydrocarbon group include groups having 1 to 8 carbon atoms, such as alkyl groups such as methyl, ethyl, propyl; alkenyl groups such as vinyl, allyl; alkynyl groups such as ethynyl, propynyl; aryl groups such as phenyl, tolyl; aralkyl groups such as benzyl, phenethyl. Among these, as R3, R4 and R5, hydrogen atoms and alkyl groups are preferred, and hydrogen atoms, methyl and ethyl are more preferred.

[0171] Examples of the substituent include, for example, halogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, acyl, alkylamino, carbamoyl, nitro, nitroso, cyano, alkylthio, sulfinyl, sulfonyl, silyl, etc. In addition, among these substituents, adjacent substituents may be crosslinked to form a ring containing the bonded carbon atoms.

[0172] [Chemical formula 27]

[0173]

[0174] In formula (5), R6 is a divalent hydrocarbon group which may have substituents, and R7 is a hydrogen atom or a hydrocarbon group which may have substituents, or an oxy group. When R7 is a hydrocarbon group, it may be bonded to R6 to form a ring.

[0175] Examples of the divalent hydrocarbon group as R6 include, for example, methylene, ethylene, and trimethylene. Additionally, R7-C-R6 may be combined to form a double bond or a cyclic structure such as vinylidene, 1,2-phenylene, 2,3-naphthylene, 1,2-cyclohexylene, 1,2-bicyclo[2,2,1]heptylene, 1,4-dihydro-1,4-methano-2,3-naphthylene, etc. Among them, ethylene, 1,2-bicyclo[2,2,1]heptylene, and 1,4-dihydro-1,4-methano-2,3-naphthylene are preferred.

[0176] Examples of the hydrocarbon group as R7 include, for example, a group having 1 to 8 carbon atoms, such as alkyl groups like methyl, ethyl, and propyl; alkenyl groups like vinyl and allyl; alkynyl groups like ethynyl and propynyl; aryl groups like phenyl and tolyl; aralkyl groups like benzyl and phenethyl. Among them, as R7, a hydrogen atom and an alkyl group are preferred, and a hydrogen atom, methyl, and ethyl are more preferred.

[0177] Examples of the substituent include, for example, halogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, acyl, alkylamino, carbamoyl, nitro, nitroso, cyano, alkylthio, sulfinyl, sulfonyl, silyl, etc. Additionally, among these substituents, adjacent substituents may crosslink to form a ring containing the bonded carbon atoms.

[0178] [Chemical formula 28]

[0179]

[0180] In formula (6), Z' is halogen or OH, preferably Cl or Br.

[0181] [Chemical formula 29]

[0182]

[0183] In formula (7), Ox is an oxyacid selected from the group consisting of NO 3- , CO3 2- and PO4 3- , preferably CO3 2- .

[0184] [Chemical formula 30]

[0185]

[0186] In formula (X1), R1', R2', R3', R4', and R5' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, preferably a hydrogen atom.

[0187] [Chemical formula 31]

[0188]

[0189] In formula (Y1), R6’, R7’ and R8’ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, preferably a hydrogen atom.

[0190] In the aforementioned formula (1), Y preferably contains one or more selected from the group consisting of the ligand represented by the following formula (8), the ligand represented by the following formula (9), the ligand represented by the following formula (10), the ligand represented by the following formula (11), the ligand represented by the following formula (12), the ligand represented by the following formula (13), and the ligand represented by the following formula (Z1).

[0191] [Chemical formula 32]

[0192]

[0193] [Chemical formula 33]

[0194]

[0195] In formula (9), X is a group of non-metal atoms required to form a ring, and R and R’ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include groups having 1 to 8 carbon atoms, such as alkyl groups such as methyl, ethyl, and propyl; alkenyl groups such as vinyl and allyl; alkynyl groups such as ethynyl and propargyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl. Among them, as R and R’, a hydrogen atom and an alkyl group are preferred, and a hydrogen atom, a methyl group, and an ethyl group are more preferred.

[0196] In addition, X is a group of non-metal atoms required to form a ring which is a part of R 2 in formula (3).

[0197] Examples of the substituent include halogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, acyl, alkylamino, carbamoyl, nitro, nitroso, cyano, alkylthio, sulfinyl, sulfonyl, silyl, etc. In addition, among these substituents, adjacent substituents may crosslink to form a ring containing the carbon atom to which they are bonded.

[0198] [Chemical formula 34]

[0199]

[0200] [Chemical formula 35]

[0201]

[0202] In formula (11), R7 and R8 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and R7 and R8 may bond to each other to form a ring.

[0203] [Chemical formula 36]

[0204]

[0205] In formula (12), R9 and R 10 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and R9 and R 10 may be bonded to each other to form a ring.

[0206] [Chemical formula 37]

[0207]

[0208] In formula (13), Z” is Cl or Br.

[0209] [Chemical formula 38]

[0210]

[0211] The nickel complex of the present embodiment may be a hydrate of the nickel complex exemplified above.

[0212] As the divalent nickel complex, specifically, nickel acetate (Ni(OAc)2), nickel chloride (NiCl2), nickel bromide (NiBr2), etc. can be cited.

[0213] Relative to 1 mol of the alicyclic dicarboxylic anhydride as a raw material, the amount of the nickel complex in the present embodiment is preferably 0.0001 mol or more, more preferably 0.0005 mol or more, further preferably 0.0008 mol or more, and preferably 0.2 mol or less, more preferably 0.1 mol or less, further preferably 0.05 mol or less, further preferably 0.02 mol or less, further preferably 0.01 mol or less, further preferably 0.008 mol or less.

[0214] [Compound capable of being a ligand]

[0215] In the above-mentioned decarbonylation and decarboxylation steps, it is preferable that there is further a ligand capable of coordinating with the above-mentioned nickel complex.

[0216] Hereinafter, compounds capable of being ligands with respect to the nickel complex will be described.

[0217] In the aforementioned decarbonylation and decarboxylation steps, relative to 1 mol of the aforementioned nickel complex, the loading amount of the aforementioned compound that can become a ligand is preferably 1 mol or more, more preferably 2 mol or more, and further preferably 4 mol or more, and preferably 500 mol or less, more preferably 400 mol or less, further preferably 300 mol or less, further preferably 280 mol or less, and further preferably 270 mol or less. In the present embodiment, the loading amount of the compound that can become a ligand refers to the total loading amount of the compound that can become a ligand at the end of the aforementioned decarbonylation and decarboxylation steps.

[0218] The aforementioned compound capable of serving as a ligand preferably includes a phosphorus-containing compound.

[0219] The compound that can serve as a ligand preferably includes one or two or more selected from the group consisting of a compound represented by the following formula (14) and a compound represented by the following formula (15).

[0220] [Chemistry 39]

[0221]

[0222] In formula (14), X 1 , X 2 and X 3 Each independently represents a hydrocarbon group which may have a substituent.

[0223] The compound represented by the above formula (14) includes, for example, one or more selected from the group consisting of trialkyl phosphines such as tricyclohexylphosphine, tricyclopentylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, trioctylphosphine, and tribenzylphosphine; triaryl phosphines such as triphenylphosphine, tritolylphosphine (including various substituted isomers at the ortho, meta and para positions), tri(methoxyphenyl)phosphine (including various substituted isomers at the ortho, meta and para positions), tri(fluorophenyl)phosphine (including various substituted isomers at the ortho, meta and para positions), and tri(α-naphthyl)phosphine; diaryl alkyl phosphines such as diphenylcyclohexylphosphine; and dialkyl aryl phosphines such as dicyclohexylphenylphosphine. It preferably includes one or more selected from the group consisting of triaryl phosphines, and more preferably includes triphenylphosphine.

[0224] In addition, in the above formula (14), X 1 , X 2 and X 3 Two groups may be cross-linked to form a ring containing a phosphorus atom, and examples of such phosphines include phenylbiphenylphosphine.

[0225] [Chemistry 40]

[0226]

[0227] In formula (15), X4 , X 5 , X 6 and X 7 are each independently a hydrocarbon group which may have a substituent, and Z is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a ferrocenylene group or a binaphthylene group.

[0228] The compound represented by the aforementioned formula (15) includes, for example, one or more selected from the group consisting of 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, 1,2-bis(diphenylphosphinomethyl)cyclohexane, 1,3-bis(diphenylphosphino)benzene, and 1,1'-bis(diphenylphosphino)ferrocene.

[0229] The compound capable of being a ligand preferably includes triphenylphosphine.

[0230] [alicyclic dicarboxylic anhydride]

[0231] Hereinafter, the alicyclic dicarboxylic anhydride, which is a raw material for the method for producing the cyclic olefin compound of the present embodiment, will be described.

[0232] The aforementioned alicyclic dicarboxylic anhydride preferably includes one or more selected from the group consisting of the compound represented by the following formula (16) and the compound represented by the following formula (17).

[0233] [Chemical formula 41]

[0234]

[0235] In formula (16), X is a group of non-metal atoms required to form a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.

[0236] [Chemical formula 42]

[0237]

[0238] In formula (17), X represents a group of non-metal atoms required to form a ring, and the ring formed by them may be a saturated ring or an unsaturated ring. Examples thereof include saturated rings such as cyclohexane, norbornane, bicyclo[2.2.2]octane, and tetracyclo[4.4.0.1 2,5 .1 7,10 dodecane; unsaturated rings such as norbornene, tetracyclo[4.4.0.1 2,5 .1 7,10 -8-dodecene, and benzonorbornene; and aprotic heterocycles such as 7-oxabicyclo[2.2.1]heptane and 7-thiabicyclo[2.2.1]heptane.

[0239] R and R' each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include groups having 1 to 8 carbon atoms, such as alkyl groups like methyl, ethyl, and propyl; alkenyl groups like vinyl and allyl; alkynyl groups like ethynyl and propargyl; aryl groups like phenyl and tolyl; and aralkyl groups like benzyl and phenethyl.

[0240] R and R' are preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group, and more preferably one or more selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group.

[0241] R and R' may crosslink with each other or with the ring formed by X to form an alkylene group having 2 to 8 carbon atoms. In addition, the ring formed by X, R, and R' may also have substituents that are inert in the reaction. Examples of the substituent include, for example, halogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, acyl, alkylamino, carbamoyl, nitro, nitroso, cyano, alkylthio, sulfinyl, sulfonyl, silyl, etc. In addition, among these substituents, adjacent substituents may crosslink to form a ring containing the carbon atom to which they are bonded.

[0242] The aforementioned alicyclic dicarboxylic anhydride preferably contains the compound represented by formula (18).

[0243] [Chemical formula 43]

[0244]

[0245] In formula (18), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom or a substituent which may have a heteroatom.

[0246] In formula (18), preferably R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are all hydrogen. When R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are all hydrogen in formula (18), formula (18) becomes benzonorbornene-2,3-dicarboxylic anhydride (BNDCA).

[0247] The aforementioned alicyclic dicarboxylic anhydride preferably contains the compound represented by the formula (19).

[0248] [Chemical formula 44]

[0249]

[0250] In the formula (19), n is 0 or 1, and X' is O or CH2.

[0251] [Manufacturing conditions, etc.]

[0252] Hereinafter, the manufacturing conditions, etc. of the cyclic olefin compound of the present embodiment will be described.

[0253] The manufacturing of the cyclic olefin compound of the present embodiment can be carried out without a solvent or can be carried out using a solvent.

[0254] As the solvent, any solvent can be used as long as it is inert to the raw materials, the catalyst, and the compound that can become a ligand. For example, the following can be cited: ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diphenyl ether, anisole, veratrole; aromatic hydrocarbons such as tetralin, naphthalene; aprotic polar solvents such as nitrobenzene, benzonitrile, N-methylpyrrolidone, dimethylimidazolinone, etc.

[0255] The manufacturing of the cyclic olefin compound of the present embodiment is preferably carried out in a state where oxygen and moisture are removed, for example, in an inert atmosphere such as nitrogen or argon.

[0256] In the decarbonylation and decarboxylation steps, in order to suppress the decrease in the activity of the nickel complex, and further from the viewpoint of improving the selectivity by reducing the thermal history of the generated cyclic olefin compound, it is preferred to carry out decarbonylation and decarboxylation while removing the generated cyclic olefin compound out of the reaction system.

[0257] As a method of carrying out decarbonylation and decarboxylation while removing the aforementioned generated cyclic olefin compound out of the reaction system, a reactive distillation method can be cited.

[0258] The higher the temperature in the decarbonylation and decarboxylation steps, the more favorable it is in terms of reaction rate. However, when it is too high, there may be undesirable side reactions such as decomposition of the nickel complex, rearrangement, and polymerization of the cyclic olefin as a product, resulting in a decrease in selectivity. Therefore, the temperature in the decarbonylation and decarboxylation steps is preferably 100 °C or higher, more preferably 120 °C or higher, further preferably 150 °C or higher, and preferably 300 °C or lower, more preferably 280 °C or lower, further preferably 250 °C or lower.

[0259] As a method for the decarbonylation and decarboxylation steps, the following methods can be exemplified: a batch method in which a metal-based cocatalyst, a compound capable of becoming a ligand, a nickel complex, and a raw material are charged into the reaction system all at once; a semi-batch method in which a metal-based cocatalyst, a compound capable of becoming a ligand, and a nickel complex are previously charged into the reaction system and a raw material is continuously supplied thereto by dropping the raw material, etc.; a semi-batch method in which a metal-based cocatalyst and a compound capable of becoming a ligand are previously charged into the reaction system and a nickel complex and a raw material are continuously supplied thereto by separately dropping the nickel complex and the raw material, etc.; or a continuous method in which a metal-based cocatalyst, a compound capable of becoming a ligand, a nickel complex, and a raw material are continuously supplied to the reaction system, etc.

[0260] The method for the decarbonylation and decarboxylation steps is preferably a semi-batch method, and more preferably a semi-batch method in which a metal-based cocatalyst and a compound capable of becoming a ligand are previously charged into the reaction system and a nickel complex and a raw material are continuously supplied thereto separately. Thereby, the time required until the start of the reaction (reaction induction period) can be shortened. In addition, since the residence times of the raw material and the product can be shortened, by-products can be suppressed by shortening the heat history. Further, when there is a compound capable of becoming a ligand with respect to the nickel complex in the decarbonylation and decarboxylation steps, the production efficiency can be improved by carrying out the reaction in a semi-batch manner.

[0261] In the method for producing a cyclic olefin compound of the present embodiment, a step of adding an alcohol compound may be included. Thereby, impurities generated when producing an alicyclic dicarboxylic anhydride can be rendered harmless. If there are impurities contained in the alicyclic dicarboxylic anhydride, the activation of the divalent nickel complex is hindered, and the time required until the start of the reaction (reaction induction period) becomes long. Therefore, by adding an alcohol compound to render harmless the impurities contained in the alicyclic dicarboxylic anhydride, the reaction induction period can be shortened, and the production rate of the cyclic olefin compound can be increased.

[0262] Here, the step of adding an alcohol compound may be carried out separately from the aforementioned decarbonylation and decarboxylation steps, or may be carried out simultaneously with the aforementioned decarbonylation and decarboxylation steps. That is, the alicyclic dicarboxylic anhydride containing impurities may be treated with an alcohol compound, and then a divalent nickel complex and a compound capable of becoming a ligand may be mixed in the alicyclic dicarboxylic anhydride, and then the aforementioned decarbonylation and decarboxylation steps may be carried out. Alternatively, an alcohol compound may be further added when the alicyclic dicarboxylic anhydride containing impurities, the divalent nickel complex, and the compound capable of becoming a ligand are mixed. In this case, the addition order of the alicyclic dicarboxylic anhydride containing impurities, the divalent nickel complex, the compound capable of becoming a ligand, and the alcohol compound is not particularly limited. However, it is preferable to add the alcohol compound before the start of the decarbonylation and decarboxylation reactions of the alicyclic dicarboxylic anhydride and to remove the alcohol compound before the start of the decarbonylation and decarboxylation reactions of the alicyclic dicarboxylic anhydride.

[0263] In the method for producing a cyclic olefin compound according to this embodiment, the boiling point of the above alcohol compound is preferably lower than that of the alicyclic dicarboxylic anhydride. Thereby, the alcohol compound can be selectively removed from the system after the detoxification of impurities and before the synthesis of the cyclic olefin compound.

[0264] As the alcohol compound, when the cyclic olefin compound to be produced is benzonorbornadiene, for example, it preferably contains one or more selected from the group consisting of 1-butanol, 3-pentanol, 2-methoxyethanol, isopentanol, 1-pentanol, 1-hexanol, cyclohexanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol.

[0265] In the method for producing a cyclic olefin compound according to this embodiment, the alicyclic dicarboxylic anhydride may sometimes contain at least any one of a carboxylic acid compound or a carboxylic anhydride (wherein, the aforementioned alicyclic dicarboxylic anhydride is not included) as an impurity.

[0266] Depending on the type of divalent nickel complex, these impurities may sometimes hinder its activation. In the case where the method for producing a cyclic olefin compound according to this embodiment further includes a step of adding an alcohol compound, the carboxylic acid compound or acid anhydride in the impurities reacts with the alcohol compound and is detoxified.

[0267] In the method for producing a cyclic olefin compound according to this embodiment, in the step of adding the above alcohol compound, it preferably includes the following steps: bringing the alcohol compound into contact with the above impurities in the liquid phase, and after the carboxylic acid compound or the carboxylic anhydride in the above impurities reacts with the alcohol compound, removing the unreacted alcohol compound.

[0268] Thereby, the inhibition of the hindrance of the alcohol to the synthesis reaction of the cyclic olefin compound can be achieved, and thus the production rate of the cyclic olefin compound can be increased.

[0269] The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can also be adopted.

[0270] Examples

[0271] Hereinafter, the usefulness of the present invention will be described in more detail by way of examples, but the present invention is not limited to these.

[0272] In Comparative Example 1 and Examples 1 to 3, BNBD was obtained by a batch method in which the raw materials (alicyclic dicarboxylic anhydride), nickel complex, metal-based cocatalyst, and a compound capable of becoming a ligand were charged into the reaction system at once for reaction. The detailed method is as described below.

[0273] In a 50 mL glass flask equipped with a distillation apparatus, the raw materials, nickel complex, metal-based cocatalyst, and ligand-forming compound of the types and amounts described in Table 1 were charged and mixed, and then heated to 220 °C under a reduced pressure of 30 torr. Sixty minutes after reaching 220 °C, the liquid began to distillate.

[0274] By 1 1H-NMR analysis of the distillated liquid showed that the main component of the distillated liquid was benzonorbornadiene (BNBD).

[0275] The distillated liquid and the reaction residue in the flask were analyzed by GC (gas chromatography) according to the following <Analysis Conditions> respectively, and the yield of BNBD and the recovery rate of BNDCA as a raw material were calculated.

[0276] <Analysis Conditions>

[0277] Apparatus: manufactured by Shimadzu Corporation, model: GC-2014s

[0278] Column: manufactured by Phenomenex, ZB-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)

[0279] Carrier gas: He, 0.33 mL / min

[0280] Injection conditions: 250 °C, split ratio 10 / 1

[0281] Injection volume: 1 μL

[0282] Detection conditions: FID mode, 300 °C

[0283] Column temperature conditions: First, hold at 60 °C for 1 minute, then increase the temperature to 300 °C at a rate of 8 °C / minute, and then hold at 300 °C for 20 minutes.

[0284] Internal standard: When analyzing the distillated liquid, toluene was used as the internal standard. In addition, when analyzing the reaction residue in the 50 mL glass flask, 1,2-dichlorobenzene was used as the internal standard.

[0285] The yield of BNBD calculated by the above method is shown in Table 1.

[0286] The selectivity of BNBD was calculated by the following formula. The results are shown in Table 1.

[0287] [Selectivity of BNBD] = [Yield of BNBD] / (100 - [Recovery rate of BNDCA]) × 100

[0288] [Table 1]

[0289]

[0290] When the examples and comparative examples described in Table 1 are compared, the yield of BNBD in the examples is improved. From this, it can be seen that the production efficiency of the cyclic olefin compound is improved according to the production method of the present embodiment.

[0291] In Comparative Example 2, Example 4, Comparative Example 3, and Examples 5 to 7, BNBD was obtained by a semi-batch method in which a nickel complex, a metal-based cocatalyst, and a compound capable of becoming a ligand were previously charged into the reaction system and a raw material (alicyclic dicarboxylic anhydride) was added dropwise thereto. The detailed method is as follows.

[0292] First, in a 50 mL glass flask (1) equipped with a distillation apparatus and a dropping funnel with a pressure equalizing tube that can be opened and closed with a valve, the nickel complex, the metal-based cocatalyst, and the compound capable of becoming a ligand described in Table 2 in terms of type and amount were charged, and one dropping funnel was covered with a rubber heater and kept at 200 °C.

[0293] Next, in another two-necked flask (2), the raw materials described in Table 2 in terms of type and amount and about 1.5 times the weight of tetraethylene glycol dimethyl ether of the raw materials were charged, and stirring and slurrying were carried out.

[0294] Next, the flask (1) was heated to 220 °C under reduced pressure of 30 torr using an oil bath.

[0295] Next, the operations of (I) and (II) below were repeated every 20 minutes, the slurry in the flask (2) was charged into the flask (1), and the slurry was reacted with the contents of the flask (1).

[0296] (I) A certain amount (about 1.8 g) of the slurry was withdrawn from the flask (2) using a syringe, and the withdrawn slurry was charged into the dropping funnel provided in the flask (1).

[0297] (II) The pressure equalizing tube valve of the dropping funnel was slowly opened to make the pressure inside the dropping funnel and the flask (1) equal, and then the slurry was charged from the dropping funnel into the flask (1) to start the reaction.

[0298] From just after the start of the reaction, distillation of the liquid was observed. By 1 1H-NMR analysis of the distilled liquid, the distilled liquid was a solution of benzonorbornadiene (BNBD) in tetraethylene glycol dimethyl ether.

[0299] Based on the GC analysis results of the distilled liquid, as an index of production efficiency, the yield of BNBD, the selectivity of BNBD, and the production amount of BNBD per 1 mol of TPP were determined. The results are shown in Table 2.

[0300] [Table 2]

[0301]

[0302] When the examples and comparative examples described in Table 2 are compared, the yield of BNBD in the examples is improved. Moreover, the production amount of BNBD per 1 mol of the compound that can be a ligand, i.e., TPP, in the examples is improved.

[0303] From this, it can be understood that the production efficiency of the cyclic olefin compound is improved according to the production method of the present embodiment.

[0304] In Comparative Example 4 and Examples 8 to 9, BNBD was obtained by a semi-batch method in which a metal-based cocatalyst and a compound that can be a ligand were pre-charged into the reaction system and the raw materials (alicyclic dicarboxylic anhydride) and nickel complex were respectively added dropwise thereto. The detailed method is described below.

[0305] First, into a 50 mL glass flask (1) equipped with a distillation apparatus and two dropping funnels each having a pressure equalizing tube that can be opened and closed with a valve, the metal-based cocatalyst and the compound that can be a ligand in the types and amounts described in Table 3 were charged, and one of the dropping funnels was covered with a rubber heater and kept at 200 °C.

[0306] Next, in another two-necked flask (2), the raw materials in the types and amounts described in Table 3 and tetraethylene glycol dimethyl ether having a weight about 1.5 times that of the raw materials were charged, and stirring and slurrying were carried out.

[0307] Next, in another Schlenk tube, the nickel complex in the types and amounts described in Table 3 and tetraethylene glycol dimethyl ether having a weight about 20 times that of the nickel complex were added, and stirring and slurrying were carried out.

[0308] Next, the flask (1) was heated to 220 °C using an oil bath under a reduced pressure of 30 torr.

[0309] Next, the operations of (I) to (III) described below were repeated every 20 minutes, and the slurries in the flask (2) and the Schlenk tube were charged into the flask (1) so that the slurries reacted with the contents of the flask (1).

[0310] (I) A certain amount (about 4.8 g) of the slurry was extracted from the flask (2) using a syringe, and the extracted slurry was charged into one of the dropping funnels of the flask (1) covered with a rubber heater.

[0311] (II) A certain amount (about 0.50 g) of the slurry was extracted from the Schlenk tube using a syringe, and the extracted slurry was charged into the other dropping funnel of the flask (1).

[0312] (III) Slowly open the equalizing tube valves of the two dropping funnels separately. After making the pressures inside the two dropping funnels and the flask (1) equal, charge the slurry into the flask (1) from the two dropping funnels to start the reaction.

[0313] Immediately after the start of the reaction, distillation of the liquid was observed. By 1 1H-NMR analysis of the distilled liquid, the distilled liquid was found to be a solution of benzobicyclonorbadiene (BNBD) in diethylene glycol dimethyl ether.

[0314] Based on the GC analysis results of the distilled liquid, the selectivity of BNBD and the yield of BNBD per 1 mol of TPP were determined. The results are shown in Table 3.

[0315] [Table 3]

[0316]

[0317] When the examples described in Table 3 were compared with the comparative examples, the yield of BNBD per 1 mol of the compound that can be a ligand, i.e., TPP, in the examples was increased.

[0318] From this, it can be seen that the production efficiency of the cyclic olefin compound is improved according to the production method of the present embodiment.

[0319] This application claims priority based on Japanese Patent Application No. 2022-199586 filed on December 14, 2022, and the entire disclosure thereof is incorporated herein.

Claims

1. A method for producing a cyclic olefin compound, which includes a decarbonylation and decarboxylation step of obtaining a cyclic olefin compound by performing decarbonylation and decarboxylation on an alicyclic dicarboxylic anhydride in the presence of a nickel complex represented by the following formula (1) and a metal-based cocatalyst, The metal-based cocatalyst contains one or more selected from the group consisting of elemental metals and metal compounds, Ni(Y) m (L) n (1) In formula (1), Ni is nickel of valence 0 or 2, Y is an anionic monodentate or polydentate ligand and has at least one Ni-E covalent bond, where E is a heteroatom or a π-bonding group, m is a real number from 0 to 2, L is a neutral ligand, n is a real number from 0 to 6.

2. The method for producing a cyclic olefin compound according to claim 1, wherein, The metal-based cocatalyst contains one or more elements selected from the elements of Groups 1 to 14 of the long-form periodic table of elements.

3. The method for producing a cyclic olefin compound according to claim 1 or 2, wherein, The elemental metal contains one or more selected from the group consisting of Li, Cs, Rb, K, Ba, Sr, Ca, Na, Mg, Th, Be, Al, Ti, Zr, Mn, Ta, Zn, Cr, Fe, Cd, and Co.

4. The method for producing a cyclic olefin compound according to any one of claims 1 to 3, wherein, The elemental metal contains one or two selected from the group consisting of Mn and Zn.

5. The method for producing a cyclic olefin compound according to any one of claims 1 to 4, wherein, The metal compound contains one or more elements selected from the elements of Groups 7 to 12 of the long-form periodic table of elements.

6. The method for producing a cyclic olefin compound according to any one of claims 1 to 5, wherein, The metal compound contains one or two selected from the group consisting of Mn and Zn.

7. The method for producing a cyclic olefin compound according to any one of claims 1 to 6, wherein, The metal compound contains one or more selected from the group consisting of Mn(OAc)2 and ZnO.

8. The method for producing a cyclic olefin compound according to any one of claims 1 to 7, wherein, In the formula (1), Ni is nickel of valence 2, The Y contains one or more selected from the group consisting of the ligands represented by the following formula (2), the ligand represented by the following formula (3), the ligand represented by the following formula (4), the ligand represented by the following formula (5), the ligand represented by the following formula (6), the ligand represented by the following formula (7), the ligand represented by the following formula (X1), and the ligand represented by the following formula (Y1), [Chemical formula 1] In formula (2), R1 is a hydrogen atom or a hydrocarbon group which may have a substituent, [Chemical formula 2] In formula (3), R2 is a divalent hydrocarbon group which may have a substituent, [Chemical formula 3] In formula (4), R3, R4, and R5 are hydrocarbon groups which may have a substituent, and R3 and R5 or R4 and R5 may be bonded to each other to form a ring. In addition, R3, R4, and R5 may also be hydrogen atoms, [Chemical formula 4] In formula (5), R6 is a divalent hydrocarbon group which may have a substituent, R7 is a hydrogen atom, a hydrocarbon group which may have a substituent, or an oxy group. When R7 is a hydrocarbon group, it may be bonded to R6 to form a ring, [Chemical formula 5] In formula (6), Z’ is a halogen or OH, [Chemical formula 6] In formula (7), Ox is an oxyacid selected from the group consisting of NO 3- , CO3 2- , and PO4 3- ; [Chemical formula 7] In formula (X1), R1’, R2’, R3’, R4’, and R5’ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, [Chemical formula 8] In formula (Y1), R6’, R7’, and R8’ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.

9. The method for producing a cyclic olefin compound according to any one of claims 1 to 8, wherein, In the formula (1), Y includes one or more selected from the group consisting of the ligand represented by the following formula (8), the ligand represented by the following formula (9), the ligand represented by the following formula (10), the ligand represented by the following formula (11), the ligand represented by the following formula (12), the ligand represented by the following formula (13), and the ligand represented by the following formula (Z1). [Chemical formula 9] [Chemical formula 10] In formula (9), X is a group of non-metallic atoms required to form a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent. [Chemical formula 11] [Chemical formula 12] In formula (11), R7 and R8 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and R7 and R8 may be bonded to each other to form a ring. [Chemical formula 13] In formula (12), R9 and R 10 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and R9 and R 10 may be bonded to each other to form a ring, [Chemical formula 14] In formula (13), Z” is Cl or Br. [Chemical formula 15] 10. The method for producing a cyclic olefin compound according to any one of claims 1 to 9, wherein, In the decarbonylation and decarboxylation steps, there further exists a compound that can be a ligand with respect to the nickel complex.

11. The method for producing a cyclic olefin compound according to claim 10, wherein, In the decarbonylation and decarboxylation steps, with respect to 1 mol of the nickel complex, the charged amount of the compound that can be a ligand is 1 mol or more and 500 mol or less.

12. The method for producing a cyclic olefin compound according to claim 10 or 11, wherein, The compound that can be a ligand includes a phosphorus-containing compound.

13. The method for producing a cyclic olefin compound according to any one of claims 10 to 12, wherein, The compound that can be a ligand includes one or more selected from the group consisting of the compound represented by the following formula (14) and the compound represented by the following formula (15). [Chemical formula 16] In formula (14), X 1 , X 2 and X 3 are each independently a hydrocarbyl group which may have substituents. [Chemical formula 17] In formula (15), X 4 , X 5 , X 6 and X 7 are each independently a hydrocarbyl group which may have substituents, and Z is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a ferrocenylene group or a binaphthylene group.

14. The method for producing a cyclic olefin compound according to any one of claims 10 to 13, wherein, The compound that can be a ligand includes triphenylphosphine.

15. The method for producing a cyclic olefin compound according to any one of claims 1 to 14, wherein, The alicyclic dicarboxylic anhydride includes one or more selected from the group consisting of the compound represented by the following formula (16) and the compound represented by the following formula (17). [Chemical formula 18] In formula (16), X is a group of non-metallic atoms required to form a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent. [Chemical formula 19] In formula (17), X is a group of non-metallic atoms required to form a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.

16. The method for producing a cyclic olefin compound according to any one of claims 1 to 15, wherein, The alicyclic dicarboxylic anhydride includes the compound represented by the following formula (18). [Chemical formula 20] In formula (18), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom or a substituent that may have a heteroatom.

17. The method for producing a cyclic olefin compound according to claim 16, wherein, In the formula (18), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are all hydrogen.

18. The method for producing a cyclic olefin compound according to any one of claims 1 to 17, wherein, The alicyclic dicarboxylic anhydride includes the compound represented by the following formula (19). [Chemical formula 21] In formula (19), n is 0 or 1, and X’ is O or CH2.

19. The method for producing a cyclic olefin compound according to any one of claims 1 to 18, wherein, In the decarbonylation and decarboxylation steps, the generated cyclic olefin compound is removed from the reaction system while performing decarbonylation and decarboxylation.

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