Methods for manufacturing cyclic olefin compounds

Abstract

A method for producing a cyclic olefin compound includes: a step of decarbonylating and decarboxylating an alicyclic dicarboxylic anhydride by causing a divalent nickel complex represented by the following general formula (1) to function, thereby producing a cyclic olefin compound, wherein the divalent nickel complex comprises at least one specific anionic ligand Y. Ni(Y) m (L) n (1) (Here, Ni is divalent nickel, Y is an anionic monodentate or polydentate ligand with at least one Ni-E covalent bond, E is a heteroatom or π-bonded group, m is 1 or 2, L is a neutral ligand, and n is a real number from 0 to 6.)

Description

Technical Field

[0001] This invention relates to a method for manufacturing cyclic olefin compounds. Background Technology

[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 and ring-opening metathesis polymerization. Various methods for manufacturing cyclic olefin compounds are known, including: (1) decarbonylation and decarboxylation reactions of alicyclic dicarboxylic anhydrides, or (2) oxidative decarboxylation reactions of dicarboxylic acid derivatives obtained by hydrolysis of alicyclic dicarboxylic anhydrides.

[0003] Alicyclic dicarboxylic anhydrides, which serve as starting materials for these reactions, can be obtained via the Diels-Alder reaction of conjugated dienes with maleic anhydrides. Generally, maleic anhydrides exhibit high reactivity in the Diels-Alder reaction, thus yielding addition products in good yields. Therefore, provided that these alicyclic dicarboxylic anhydrides or their dicarboxylic acid derivatives obtained through hydrolysis can be efficiently decarbonylated or decarboxylated, it is expected that various combinations of dienes with maleic anhydrides can be used to synthesize cyclic olefin compounds with diverse structures in high yields.

[0004] As for the technology involved in the method of manufacturing such cyclic olefin compounds, for example, the technology described in Patent Document 1 (International Publication No. 2008 / 062553) can be cited.

[0005] Patent Document 1 discloses a method for manufacturing a cyclic olefin compound, characterized in that a nickel complex is used as a catalyst to decarbonylate and decarboxylate anhydride represented by a specific chemical formula in the presence of compounds that can act as ligands, thereby producing a cyclic olefin compound represented by a specific chemical formula. The above reaction is carried out simultaneously with removing the generated cyclic olefin compound from the reaction system.

[0006] Patent Document 1 describes a manufacturing method described above that can significantly reduce the amount of nickel complex used as a catalyst, thereby solving problems in known methods such as high costs due to the need for large amounts of expensive raw materials, low yield of the product, complicated separation and purification of the product, and large amounts of waste generated.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2008 / 062553 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] According to the inventor's research, the nickel complex catalyst used in Patent Document 1 is essentially a zero-valent compound, which is not only expensive but also unstable as it decomposes in the atmosphere. Therefore, from the viewpoint of operability and stability of the cyclic olefin compound manufacturing method described in Patent Document 1, there is clearly room for improvement.

[0012] The present invention was made in view of the above circumstances, and provides a method for manufacturing cyclic olefin compounds by using a specific divalent nickel complex, wherein the nickel complex can stably produce cyclic olefin compounds even when exposed to the atmosphere.

[0013] Methods for solving problems

[0014] That is, according to the present invention, a method for manufacturing the cyclic olefin compound shown below is provided.

[0015] [1] A method for manufacturing a cyclic olefin compound,

[0016] This includes the process of producing cyclic olefin compounds by decarbonylating and decarboxylating an alicyclic dicarboxylic anhydride by causing the divalent nickel complex represented by the following general formula (1) to function.

[0017] The above-mentioned divalent nickel complex contains at least one anionic ligand Y represented by any one of the following general formulas (2) to (7), (X1) and (Y1).

[0018] Ni(Y) m (L) n (1)

[0019] (Here, Ni is divalent nickel, Y is an anionic monodentate or polydentate ligand with at least one Ni-E covalent bond, E is a heteroatom or π-bonded group, m is 1 or 2, L is a neutral ligand, and n is a real number from 0 to 6.)

[0020] [Chemical Formula 1]

[0021]

[0022] (R1 is a hydrogen atom or a hydrocarbon group that may have substituents.)

[0023] [Chemical Formula 2]

[0024]

[0025] (R2 is a divalent hydrocarbon group that can have substituents.)

[0026] [Chemical Formula 3]

[0027]

[0028] (R3, R4, and R5 are hydrocarbon groups that can have substituents. R3 and R5, or R4 and R5, can also combine to form a ring. In addition, R3, R4, and R5 can also be hydrogen atoms.)

[0029] [Chemical Formula 4]

[0030]

[0031] (R6 is a divalent hydrocarbon group that can have substituents, and R7 is a hydrogen atom, a hydrocarbon group that can have substituents, or an oxo group. When R7 is a hydrocarbon group, it can also combine with R6 to form a ring.)

[0032] [Chemical Formula 5]

[0033]

[0034] (Z' is a halogen or OH.)

[0035] [Chemical Formula 6]

[0036]

[0037] (Ox is selected from NO3) - CO3 2- and PO4 3- (The oxyacids in it.)

[0038] [Chemical Formula 7]

[0039]

[0040] (R1', R2', R3', R4', and R5' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.)

[0041] [Chemical Formula 8]

[0042]

[0043] (R6', R7', and R8' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.)

[0044] [2] In the method for manufacturing the cyclic olefin compound described in [1] above,

[0045] The aforementioned divalent nickel complex contains at least one anionic ligand Y represented by any one of the following general formulas (9), (11) to (13), (Z1), (8), and (10).

[0046] [Chemical Formula 9]

[0047]

[0048] [Chemical Formula 10]

[0049]

[0050] (X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.)

[0051] [Chemical Formula 11]

[0052]

[0053] [Chemical Formula 12]

[0054]

[0055] (R7 and R8 are each independently a hydrogen atom or a hydrocarbon group that can have substituents; R7 and R8 can also combine with each other to form a ring.)

[0056] [Chemical Formula 13]

[0057]

[0058] (R9 and R) 10 Each is independently a hydrogen atom or a hydrocarbon group that can have substituents, R9 and R 10 They can also combine to form a ring.

[0059] [Chemical Formula 14]

[0060]

[0061] (Z'' is Cl or Br.)

[0062] [Chemical Formula 15]

[0063]

[0064] [3] In the method for manufacturing the cyclic olefin compound described in [1] or [2] above,

[0065] In the above-described process for manufacturing cyclic olefin compounds, there are further compounds that can act as ligands for the nickel complexes.

[0066] [4] In the method for manufacturing the cyclic olefin compound described in [3] above,

[0067] In the above-described process for manufacturing cyclic olefin compounds, the compound that can serve as a ligand is present in 10 to 500 moles relative to 1 mole of the nickel complex.

[0068] [5] In the method for manufacturing the cyclic olefin compound described in [3] or [4] above,

[0069] The compounds that can act as ligands include phosphorus-containing compounds.

[0070] [6] In any of the methods for manufacturing the cyclic olefin compounds described in any one of [3] to [5] above,

[0071] The compounds that can serve as ligands include at least one selected from the compounds represented by the following general formula (14) and the compounds represented by the following general formula (15).

[0072] [Chemical Formula 16]

[0073]

[0074] (X) 1 X 2 and X 3 Each can be a hydrocarbon group that independently has substituents.

[0075] [Chemical Formula 17]

[0076]

[0077] (X) 4 X 5 X 6 and X 7 Each can be an independent hydrocarbon group that may have substituents; Z is an alkylene group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a ferrocene group, or a binatyl group.

[0078] [7] In any of the methods for manufacturing the cyclic olefin compound described in any one of [3] to [6] above,

[0079] The compounds that can act as ligands include triphenylphosphine.

[0080] [8] In any of the methods for manufacturing the cyclic olefin compounds described in any one of [1] to [7] above,

[0081] This includes the process of adding alcohol compounds.

[0082] [9] In the method for manufacturing the cyclic olefin compound described in [8] above,

[0083] The boiling point of the above alcohol compounds is lower than that of the above alicyclic dicarboxylic anhydrides.

[0084]

[10] In any of the methods for manufacturing the cyclic olefin compound described in any one of [1] to [9] above,

[0085] The aforementioned alicyclic dicarboxylic anhydride contains at least one of a carboxylic acid compound or a carboxylic anhydride (but not the aforementioned alicyclic dicarboxylic anhydride) as an impurity.

[0086]

[11] In the method for manufacturing the cyclic olefin compound described in

[10] above,

[0087] This includes the process of adding alcohol compounds.

[0088] The process includes: contacting the alcohol compound with the impurity in a liquid phase, reacting the alcohol compound with the carboxylic acid compound or the carboxylic anhydride in the impurity, and then removing the unreacted alcohol compound.

[0089]

[12] In the method for manufacturing the cyclic olefin compound described in

[11] above,

[0090] The boiling point of the above alcohol compounds is lower than that of the above alicyclic dicarboxylic anhydrides.

[0091]

[13] In any of the methods for manufacturing the cyclic olefin compounds described in [1] to

[12] above,

[0092] The above-mentioned alicyclic dicarboxylic anhydrides include compounds represented by the following general formula (16).

[0093] The above-mentioned cyclic olefin compounds include compounds represented by the following general formula (17).

[0094] [Chemical Formula 18]

[0095]

[0096] (X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.)

[0097] [Chemical Formula 19]

[0098]

[0099] (X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.)

[0100]

[14] In any of the methods for manufacturing the cyclic olefin compounds described in [1] to

[13] above,

[0101] The above-mentioned alicyclic dicarboxylic anhydrides include 5,6-benzonorbornene-2,3-dicarboxylic anhydrides represented by the following general formula (18).

[0102] [Chemical Formula 20]

[0103]

[0104] (R) 11 R 12 R 13 R 14 R 15 R 16 and R 17 Each atom is independently a hydrogen atom or may have substituents that contain heteroatoms.

[0105]

[15] In the method for manufacturing the cyclic olefin compound described in

[14] above,

[0106] In the above general formula (18), R 11 R 12 R 13 R 14 R 15 R 16 and R 17 Both are hydrogen.

[0107]

[16] In any of the methods for manufacturing the cyclic olefin compounds described in [1] to

[13] above,

[0108] The above-mentioned alicyclic dicarboxylic anhydrides include the dicarboxylic anhydrides represented by the following general formula (19).

[0109] [Chemical Formula 21]

[0110]

[0111] (n is 0 or 1, X' is O or CH2.)

[0112]

[17] In any of the methods for manufacturing the cyclic olefin compounds described in [1] to

[16] above,

[0113] In the process of manufacturing the above-mentioned cyclic olefin compound, the process is carried out simultaneously with removing the generated cyclic olefin compound from the reaction system.

[0114] The effects of the invention

[0115] According to the present invention, a method for manufacturing cyclic olefin compounds is provided, which can stably produce cyclic olefin compounds even when the nickel complex is exposed to the atmosphere. Detailed Implementation

[0116] The embodiments of the present invention will be described in detail below. It should be noted that, in this embodiment, unless otherwise specified, "A to B" representing a numerical range means A or less than B.

[0117] The method for manufacturing cyclic olefin compounds according to this embodiment includes a step of manufacturing cyclic olefin compounds by decarbonylating and decarboxylating an alicyclic dicarboxylic anhydride by making a divalent nickel complex represented by the following general formula (1) function.

[0118] The divalent nickel complex contains at least one anionic ligand Y represented by any one of the following general formulas (2) to (7), (X1) and (Y1).

[0119] Ni(Y) m (L) n (1)

[0120] Here, Ni is divalent nickel, Y is an anionic monodentate or polydentate ligand with at least one Ni-E covalent bond, E is a heteroatom or π-bonded group, m is 1 or 2, L is a neutral ligand, and n is a real number from 0 to 6.

[0121] Since the divalent nickel complex represented by the above general formula (1) is stable even when exposed to an atmosphere containing oxygen and moisture, the method for manufacturing cyclic olefin compounds according to this embodiment can stably manufacture cyclic olefin compounds.

[0122] Furthermore, since the divalent nickel complex represented by the above general formula (1) is easy to process and synthesize and is inexpensive, the method for manufacturing cyclic olefin compounds according to this embodiment is suitable for the mass production of cyclic olefin compounds.

[0123] In the above general formula (1), E is preferably a carboxylic acid ester group or a cyclopentadienyl group.

[0124] π-bonded groups, for example, include cyclopentadienyl and its derivatives, π-allyl and its derivatives, etc. When E is a π-bonded group, the above-mentioned divalent nickel complexes, for example, include nickel dicerocene and its derivatives, di(π-allyl)nickel and its derivatives, etc.

[0125] From the perspective of improving the stability of water and oxygen, E in the above general formula (1) is more preferably a heteroatom.

[0126] L is a neutral compound containing phosphorus, nitrogen, sulfur, oxygen, etc., such as phosphine, amine, ether, thioether, alcohol, thiol, water, carbon monoxide, etc., preferably water, phosphine, or carbon monoxide.

[0127] [Chemical Formula 22]

[0128]

[0129] R1 is a hydrogen atom or a hydrocarbon group that may have substituents. Examples of hydrocarbon groups include groups having 1 to 30 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; and long-chain alkyl groups like lauryl and stearyl. Of these, R1 is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, methyl, or ethyl.

[0130] Examples of substituents include halogens, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, acyl groups, alkylamino groups, carbamoyl groups, nitro groups, nitroso groups, cyano groups, alkylthio groups, sulfinyl groups, sulfonyl groups, and silyl groups. Furthermore, adjacent substituents can be cross-linked to form a ring containing the bonded carbon atom.

[0131] [Chemical Formula 23]

[0132]

[0133] R2 is a divalent hydrocarbon group that may have substituents. Examples of divalent hydrocarbon groups include methylene, ethylene, trimethylene, vinylene, 1,2-phenylene, 2,3-naphthylene, 1,2-cyclohexylene, 1,2-bicyclo[2,2,1]heptene, and 1,4-dihydro-1,4-methylene-2,3-naphthylene. Among these, R2 is preferably 1,4-dihydro-1,4-methylene-2,3-naphthylene.

[0134] [Chemical Formula 24]

[0135]

[0136] R3, R4, and R5 are hydrocarbon groups that can have substituents, and R3 and R5 or R4 and R5 can also combine with each other to form a ring. Additionally, R3, R4, and R5 can also be hydrogen atoms. Examples of hydrocarbon groups that have 1 to 8 carbon atoms include 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; and aralkyl groups such as benzyl and phenethyl. Among these, hydrogen atoms and alkyl groups are preferred as R3, R4, and R5, and hydrogen atoms, methyl, and ethyl groups are more preferred.

[0137] Examples of substituents include halogens, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, acyl groups, alkylamino groups, carbamoyl groups, nitro groups, nitroso groups, cyano groups, alkylthio groups, sulfinyl groups, sulfonyl groups, and silyl groups. Furthermore, adjacent substituents can be cross-linked to form a ring containing the bonded carbon atom.

[0138] [Chemical Formula 25]

[0139]

[0140] R6 is a divalent hydrocarbon group that can have substituents, and R7 is a hydrogen atom, a hydrocarbon group that can have substituents, or an oxo group. When R7 is a hydrocarbon group, it can also combine with R6 to form a ring.

[0141] Examples of divalent hydrocarbon groups for R6 include methylene, ethylene, and trimethylene. Additionally, R7-C-R6 together can form double bonds or cyclic structures such as vinylene, 1,2-phenylene, 2,3-naphthylene, 1,2-cyclohexylene, 1,2-bicyclo[2,2,1]heptene, and 1,4-dihydro-1,4-methylene-2,3-naphthylene. Ethylene, 1,2-bicyclo[2,2,1]heptene, and 1,4-dihydro-1,4-methylene-2,3-naphthylene are preferred.

[0142] As the hydrocarbon group of R7, examples 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 propynyl; aryl groups like phenyl and tolyl; and aralkyl groups like benzyl and phenethyl. Among these, as R7, a hydrogen atom or an alkyl group is preferred, and a hydrogen atom, methyl, or ethyl group is more preferred.

[0143] Examples of substituents include halogens, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, acyl groups, alkylamino groups, carbamoyl groups, nitro groups, nitroso groups, cyano groups, alkylthio groups, sulfinyl groups, sulfonyl groups, and silyl groups. Furthermore, adjacent substituents can be cross-linked to form a ring containing the bonded carbon atom.

[0144] [Chemical Formula 26]

[0145]

[0146] Z' is a halogen or OH, preferably Cl or Br.

[0147] [Chemical Formula 27]

[0148]

[0149] Ox is selected from NO3. - CO3 2- and PO4 3- The oxyacid in it is preferably CO3. 2- .

[0150] [Chemical Formula 28]

[0151]

[0152] R1', R2', R3', R4' and R5' are each independently a hydrogen atom or a hydrocarbon group that may have substituents, preferably a hydrogen atom.

[0153] [Chemical Formula 29]

[0154]

[0155] R6', R7', and R8' are each independently a hydrogen atom or a hydrocarbon group that may have substituents, preferably a hydrogen atom.

[0156] In the method for manufacturing the cyclic olefin compound according to this embodiment, the divalent nickel complex preferably contains at least one anionic ligand Y represented by any one of the following general formulas (9), (11) to (13), (Z1), (8) and (10), and preferably contains a carboxylic acid ester group.

[0157] [Chemical Formula 30]

[0158]

[0159] [Chemical Formula 31]

[0160]

[0161] X is the set of non-metallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents. Examples of hydrocarbon groups 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 propynyl; aryl groups like phenyl and tolyl; and aralkyl groups like benzyl and phenethyl. Among these, R and R' are preferably hydrogen atoms or alkyl groups, and more preferably hydrogen atoms, methyl, or ethyl.

[0162] In addition, X is for the purpose of forming R in general formula (3). 2 A portion of the ring requires a set of non-metallic atoms.

[0163] Examples of substituents include halogens, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, acyl groups, alkylamino groups, carbamoyl groups, nitro groups, nitroso groups, cyano groups, alkylthio groups, sulfinyl groups, sulfonyl groups, and silyl groups. Furthermore, adjacent substituents can be cross-linked to form a ring containing the bonded carbon atom.

[0164] [Chemical Formula 32]

[0165]

[0166] [Chemical Formula 33]

[0167]

[0168] R7 and R8 are each independently a hydrogen atom or a hydrocarbon group that may have substituents, and R7 and R8 may also combine with each other to form a ring. Examples of hydrocarbon groups 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 propynyl; aryl groups like phenyl and tolyl; and aralkyl groups like benzyl and phenethyl. Among these, hydrogen atoms and alkyl groups are preferred as R7 and R8, and hydrogen atoms, methyl, and ethyl groups are more preferred. Furthermore, examples of cyclic structures formed by the combination of R7 and R8 include 1,2-phenylene, 2,3-naphthylene, 1,2-cyclohexylene, 1,2-bicyclo[2,2,1]heptylene, and 1,4-dihydro-1,4-methylene-2,3-naphthylene. Preferably, 1,2-bicyclo[2,2,1]heptenyl or 1,4-dihydro-1,4-methylene-2,3-naphthylene are used.

[0169] Examples of substituents include halogens, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, acyl groups, alkylamino groups, carbamoyl groups, nitro groups, nitroso groups, cyano groups, alkylthio groups, sulfinyl groups, sulfonyl groups, and silyl groups. Furthermore, adjacent substituents can be cross-linked to form a ring containing the bonded carbon atom.

[0170] [Chemical Formula 34]

[0171]

[0172] R9 and R 10 Each is independently a hydrogen atom or a hydrocarbon group that can have substituents, R9 and R 10 They can also combine to form rings. As hydrocarbon groups, examples 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 propynyl; aryl groups like phenyl and tolyl; and aralkyl groups like benzyl and phenethyl. Among these, R9 and R... 10 Preferably, it is a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

[0173] Examples of substituents include halogens, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, acyl groups, alkylamino groups, carbamoyl groups, nitro groups, nitroso groups, cyano groups, alkylthio groups, sulfinyl groups, sulfonyl groups, and silyl groups. Furthermore, adjacent substituents can be cross-linked to form a ring containing the bonded carbon atom.

[0174] [Chemical Formula 35]

[0175]

[0176] Z'' is either Cl or Br.

[0177] [Chemical Formula 36]

[0178]

[0179] In this embodiment, the alicyclic dicarboxylic anhydride used as a raw material can be, for example, a compound represented by the following general formula (16), and the cyclic olefin compound obtained can be, for example, a compound represented by the following general formula (17).

[0180] [Chemical Formula 37]

[0181]

[0182] X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.

[0183] [Chemical Formula 38]

[0184]

[0185] X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.

[0186] X represents the set of nonmetallic atoms required to form the ring. The ring formed by these atoms can be either saturated or unsaturated. Examples include cyclohexane, norbornane, bicyclo[2.2.2]octane, and tetracyclo[4.4.0.1]. 2.5 .1 7.10 [Saturated rings such as dodecane; norbornene, tetracyclic [4.4.0.1] 2.5 .1 7.10 Unsaturated rings such as 8-dodecene and benzonorbornene; aprotic heterocycles such as 7-oxabicyclo[2.2.1]heptane and 7-thiabicyclo[2.2.1]heptane.

[0187] R and R' each independently represent a hydrogen atom or a hydrocarbon group that may have substituents. Examples of hydrocarbon groups 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 propynyl; aryl groups like phenyl and tolyl; and aralkyl groups like benzyl and phenethyl.

[0188] R and R' are preferably hydrogen atoms or alkyl groups, and more preferably hydrogen atoms, methyl groups, or ethyl groups.

[0189] R and R' can also crosslink with each other or with the ring formed by X to form an alkylene group with 2 to 8 carbon atoms. Furthermore, the ring formed by X, R, and R' can have substituents that are inactive in the reaction. Examples of substituents include halogens, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, acyl groups, alkylamino groups, carbamoyl groups, nitro groups, nitroso groups, cyano groups, alkylthio groups, sulfinyl groups, sulfonyl groups, and silyl groups. Additionally, adjacent substituents can crosslink to form a ring containing the carbon atom to which they are bonded.

[0190] As the alicyclic dicarboxylic anhydride represented by general formula (16), specifically, 5,6-benzonorbornene-2,3-dicarboxylic anhydrides represented by general formula (18) and dicarboxylic anhydrides represented by general formula (19) can be used.

[0191] [Chemical Formula 39]

[0192]

[0193] R 11 R 12 R 13 R 14 R 15 R 16 and R 17 Each is an independent hydrogen atom or may have substituents that are heteroatoms.

[0194] In general formula (18), R 11 R 12 R 13 R 14 R 15 R 16 and R 17 Each can independently represent a hydrogen atom or a substituent that may have heteroatoms, preferably R. 11 R 12 R 13 R 14 R 15 R 16 and R 17 All are hydrogen. The aforementioned substituents can be used as substituents. In this embodiment, R is preferred. 11 ~R 17 A compound in which all substituents are hydrogen atoms.

[0195] [Chemical Formula 40]

[0196]

[0197] n is 0 or 1, and X' is O or CH2.

[0198] Divalent nickel complexes can be used directly as commercially available products, but they can also be synthesized and used, for example, by known methods.

[0199] Regarding the amount of divalent nickel complex used, generally speaking, it is 0.0001 to 0.2 moles relative to 1 mole of alicyclic dicarboxylic anhydride used as a raw material, preferably 0.001 to 0.05 moles.

[0200] In the method for manufacturing cyclic olefin compounds according to this embodiment, in the above-mentioned process of manufacturing cyclic olefin compounds, in order to activate the nickel complex and to improve the stability of the generated catalyst species, a compound that can act as a ligand for the nickel complex (hereinafter also referred to as the compound) may be further present.

[0201] In the method for manufacturing cyclic olefin compounds according to this embodiment, in order to activate the nickel complex and to improve the stability of the generated catalyst species, a compound that can act as a ligand for the nickel complex (hereinafter also simply referred to as the compound) may be further present in the reaction system during the manufacturing of the cyclic olefin compound.

[0202] The compounds used in this embodiment that can act as ligands are monodentate or polydentate electron-donating compounds containing Group V elements of the periodic table, namely nitrogen, phosphorus, arsenic, and antimony, as coordinating atoms. It should be noted that the compounds used in this embodiment that can act as ligands may be the same as or different from the ligands in the nickel complex.

[0203] Examples of compounds that can act as ligands include tertiary amines such as tributylamine, trioctylamine, triphenylamine, N,N,N',N'-tetramethylethylenediamine, and N,N,N',N'-tetramethyl-1,2-phenylenediamine; nitrogen-containing aromatic compounds such as 2,2'-bipyridine and 1,10-phenanthroline; and imines such as N,N'-diphenyl-1,4-diazabutadiene and 1,6-diphenyl-2,5-diaza-1,5-hexadiene; arsenic compounds such as tributylarsenic and triphenylarsenic; antimony compounds such as tributylantimony and triphenylantimony; and phosphorus-containing compounds represented by the following general formula (14) or the following general formula (15).

[0204] In this embodiment, the compound that can serve as a ligand preferably includes at least one of the compounds represented by the following general formula (14) and the compounds represented by the following general formula (15).

[0205] [Chemical Formula 41]

[0206]

[0207] In the formula, X 1 X 2and X 3 Each can be independently represented as a hydrocarbon group that may have substituents.

[0208] [Chemical Formula 42]

[0209]

[0210] In the formula, X 4 X 5 X 6 and X 7 Each can independently represent a hydrocarbon group that may have substituents. In addition, Z represents an alkylene group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a ferrocene group, or a naphthylene group.

[0211] As X 1 ~X 7 The hydrocarbon group in the compound can be, for example, an alkyl group having 1 to 6 carbon atoms, an aromatic group, or a fused ring formed by the condensation of a carbocyclic ring and / or a heterocyclic ring. Substituents can be, for example, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or halogen atoms.

[0212] Examples of compounds that can serve as ligands, as represented by the above general formula (14), include trialkylphosphines such as tricyclohexylphosphine, tricyclopentylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, trioctylphosphine, and tribenzylphosphine; triphenylphosphine; trimethylbenzylphosphine (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); triarylphosphines such as tri(α-naphthyl)phosphine; diarylalkylphosphines such as diphenylcyclohexylphosphine; and dialkylarylphosphines such as dicyclohexylphenylphosphine, with triarylphosphines being preferred, and triphenylphosphine being even more preferred. Additionally, X 1 X 2 and X 3 Phosphorus-containing rings can also be formed by cross-linking between two groups. Examples of such phosphines include phenylphosphine phosphine.

[0213] Examples of compounds that can serve as ligands, as represented by the above general formula (15), include 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, and 1,4-bis(diphenylphosphine)butane.

[0214] In this embodiment, from the viewpoint of obtaining a target substance with high selectivity, it is preferable to use a compound that can serve as a ligand, represented by general formula (14) or (15).

[0215] In this embodiment, to improve the stability of the nickel complex, it is preferable to allow an excess of compounds that can act as ligands to coexist. If the amount of compounds that can act as ligands is too small, the stability of the catalyst may sometimes decrease. On the other hand, when the amount of ligands is large, the stability of the catalyst does not increase proportionally to the amount used, which is uneconomical, or sometimes the reaction rate may decrease.

[0216] Therefore, in the process of manufacturing cyclic olefin compounds according to this embodiment, the amount of the compound that can be used as a ligand is not necessarily fixed depending on its type. For example, it is 10 to 500 moles relative to 1 mole of nickel complex, preferably 20 to 200 moles.

[0217] By using compounds that can act as ligands in the amounts described above, high-purity cyclic olefins can be produced with high selectivity. Furthermore, within this range, the compound itself can be used as a solvent. The compounds used in this case are preferably substances that are stable to the target compound and relatively inexpensive. Triphenylphosphine is one such useful compound.

[0218] These ligand-forming compounds can be used alone or as a mixture of two or more. When using mixtures of these ligand-forming compounds, they can be mixed in any proportion, but preferably the total amount of these compounds used is within the range described above relative to 1 mole of the nickel complex.

[0219] Higher reaction temperatures are generally more advantageous in terms of reaction rate, but excessively high temperatures can lead to undesirable side reactions such as catalyst decomposition, rearrangement of cyclic olefins as products, and polymerization, resulting in reduced selectivity. Therefore, it is generally preferred to carry out the reaction at 100–300°C, and particularly preferred at 150–250°C.

[0220] In the method for manufacturing cyclic olefin compounds according to this embodiment, in order to suppress the decrease in activity of the nickel complex and, further, to improve the selectivity by reducing the thermal history of the generated cyclic olefin compounds, it is preferable to perform this step simultaneously with removing the generated cyclic olefin compounds from the reaction system. Therefore, reactive distillation is preferred.

[0221] The reaction pressure depends largely on the boiling point of the olefin produced, but there are no particular limitations as long as rapid removal of the product from the reaction system is achievable. When the product has a low boiling point, the reaction can be carried out at atmospheric pressure. On the other hand, when the product has a high boiling point, the reaction is preferably carried out under reduced pressure.

[0222] The cyclic olefin compound represented by general formula (17) obtained from the alicyclic dicarboxylic anhydride of general formula (16) is separated from the gas containing CO and CO2 by condensation after being removed in gaseous form. The crude cyclic olefin compound thus obtained can be further purified as needed by distillation or the like.

[0223] During the reaction, if the compound that can act as a ligand can itself act as a solvent, it is not necessary to use an external solvent. However, it is also fine to use a new solvent as needed.

[0224] As a solvent, any solvent can be used as long as it is inactive to the raw materials, catalysts, and compounds that can act as ligands. Examples include ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diphenyl ether, anisole, and veratrine ether; aromatic hydrocarbons such as tetrahydronaphthalene and naphthalene; and nonprotic polar solvents such as nitrobenzene, benzyl nitrile, N-methylpyrrolidone, and dimethylimidazolinone.

[0225] The solvent (or the compound that can act as a ligand) is preferably a substance that is easily separated from the cyclic olefin that is the product. Generally, a solvent with a boiling point higher than that of the cyclic olefin that is produced is used. If such a solvent is used, when separating the product containing the cyclic olefin that is the target substance from the reaction mixture by reactive distillation, the distillation of the solvent (or the compound that can act as a ligand) from the reaction liquid containing the catalyst and the compound that can act as a ligand can be suppressed. Therefore, it is not necessary to replenish these solvents (or the compounds that can act as ligands). In addition, it is advantageous to avoid complicated separation and purification of the product.

[0226] The reaction is preferably carried out under conditions in which oxygen and moisture have been removed, typically in an inert atmosphere such as nitrogen or argon.

[0227] The reaction can be carried out in any manner, either batchwise or continuously, by supplying the reactor with nickel complexes, compounds that can act as ligands, dicarboxylic anhydrides as raw materials, and solvents.

[0228] Furthermore, the reaction can be carried out in any manner, either batch, continuously by supplying the reactor with the nickel complex, the ligand-forming compound, the dicarboxylic anhydride as a raw material, and the solvent, or in a semi-batch manner combining them, with a semi-batch manner being preferred. This shortens the time required before the reaction begins (reaction induction period), and because the residence time of the raw materials and products can be shortened, the generation of byproducts can be suppressed by reducing the thermal history.

[0229] Furthermore, as described later, in the process of manufacturing cyclic olefin compounds, if there are compounds that can act as ligands for nickel complexes, by pre-introducing a certain amount of compounds that can act as ligands into the reaction system and carrying out the reaction in a semi-batch manner with continuous supply of raw materials and nickel complexes, the yield of cyclic olefin compounds relative to each unit of compounds that can act as ligands can be increased.

[0230] The method for manufacturing cyclic olefin compounds according to this embodiment can include a step of adding an alcohol compound. This eliminates impurities generated during the manufacturing of alicyclic dicarboxylic anhydrides. If impurities present in alicyclic dicarboxylic anhydrides are present, they hinder the activation of divalent nickel complexes, increasing the time required before the reaction begins (reaction induction period). Therefore, by adding an alcohol compound to eliminate impurities in alicyclic dicarboxylic anhydrides, the reaction induction period can be shortened, and the production rate of cyclic olefin compounds can be accelerated.

[0231] Here, the step of adding the alcohol compound can be performed separately from the step of producing the cyclic olefin compound, or it can be performed simultaneously with the step of producing the cyclic olefin compound. That is, the alicyclic dicarboxylic anhydride containing impurities can be treated with the alcohol compound first, and then a divalent nickel complex and a compound that can act as a ligand are mixed into the alicyclic dicarboxylic anhydride before proceeding with the step of producing the cyclic olefin compound. Alternatively, the alcohol compound can be added further when the alicyclic dicarboxylic anhydride containing impurities, the divalent nickel complex, and the compound that can act as a ligand are mixed. In this case, the order in which the alicyclic dicarboxylic anhydride containing impurities, the divalent nickel complex, the compound that can act as a ligand, and the alcohol compound are added is not particularly limited. However, it is preferable to add the alcohol compound before the decarbonylation and decarboxylation reactions of the alicyclic dicarboxylic anhydride begin, and to remove the alcohol compound before the decarbonylation and decarboxylation reactions of the alicyclic dicarboxylic anhydride begin.

[0232] In the method for manufacturing cyclic olefin compounds according to this embodiment, the boiling point of the alcohol compound is preferably lower than that of the alicyclic dicarboxylic acid anhydride. Therefore, after the impurities have been rendered harmless, the alcohol compound can be selectively removed from the system before the synthesis of the cyclic olefin compound.

[0233] As an alcohol compound, when the cyclic olefin compound produced is benzonorbornene, it preferably includes, for example, one or more selected from 1-butanol, 3-pentanol, 2-methoxyethanol, isoamyl alcohol, 1-pentanol, 1-hexanol, cyclohexanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol.

[0234] In the method for manufacturing cyclic olefin compounds according to this embodiment, the alicyclic dicarboxylic anhydride may contain at least one of a carboxylic acid compound or a carboxylic anhydride (but not the alicyclic dicarboxylic anhydride) as an impurity.

[0235] Depending on the type of divalent nickel complex, these impurities can sometimes hinder its activation. In the method for manufacturing cyclic olefin compounds according to this embodiment, when a step of adding an alcohol compound is further included, the carboxylic acid compounds or acid anhydrides in the impurities react with the alcohol compound and are rendered harmless.

[0236] In the method for manufacturing cyclic olefin compounds according to this embodiment, the step of adding the alcohol compound preferably includes the following steps: contacting the alcohol compound with the impurities in a liquid phase, reacting the alcohol compound with the carboxylic acid compound or the carboxylic anhydride in the impurities, and then removing the unreacted alcohol compound.

[0237] Therefore, the inhibition of the synthesis reaction of cyclic olefin compounds caused by alcohols is suppressed, thus accelerating the production rate of cyclic olefin compounds.

[0238] Example

[0239] The usefulness of the present invention will be described in more detail below through examples, but the present invention is not limited thereto. It should be noted that the analysis was performed by gas chromatography, and the conversion rate and selectivity were determined by the internal standard method (mol%), while the purity was determined by the area percentage (%). Furthermore, the concentrations of the generated carbon monoxide and carbon dioxide were measured using a Shimadzu CGT-7000 infrared gas concentration measuring device.

[0240] [Synthesis example 1]

[0241] Synthesis of Benzonorbornene-2,3-dicarboxylic anhydride (BNDCA)

[0242] In a 1.5L autoclave prepared by SUS316, 380.1 g (3.14 mol) of indene (prepared by JFE Chemical, 96% purity), 282.9 g (2.88 mol) of maleic anhydride, 5.69 g (28.6 mmol) of phenothiazine, and 501.5 g of methyl isobutyl ketone were added and stirred at 220 °C for 4 hours. After cooling the reaction solution to room temperature, the precipitated solid was separated by suction filtration, washed with methyl isobutyl ketone, and dried (424.0 g). Mass spectrometry and NMR analysis of the solid revealed that benzonorbornene-2,3-dicarboxylic anhydride (EI m / z 214 (M + The results of gas chromatography analysis showed a purity of over 99% (69% separation yield based on maleic anhydride).

[0243] It should be noted that the obtained compound was used in the following synthesis example 4.

[0244] [Synthesis example 2]

[0245] Synthesis of [(tmeda)Ni(C2H4COO)] (N,N'-Tetramethylethylenediamine Nickelacyclopropionate, N,N'-Tetramethylethylenediamine Nickelacyclopropionate)

[0246] (Reference: Z.a.Norg.allg.Chem.,1989,577,111-114)

[0247] Weigh 0.207 g of finely ground succinic anhydride into a dry 50 mL flask. In a glove box under nitrogen atmosphere, add 0.854 g of bis(1,5-cyclooctadiene)nickel, followed by 2.077 g of dried tetramethylethylenediamine (TMEDA). Stir the resulting yellow slurry overnight at room temperature to obtain a pale green slurry. Filter the slurry under nitrogen atmosphere, dissolving the residual solid in dry methanol. Then, filter the solution under nitrogen atmosphere and wash with dry methanol. Concentrate the filtrate and recover the precipitated solid (0.4 g, 78% yield). 1 H NMR (CD3OD, 25℃): δ0.46 (br,2H,Ni-CH2), 1.83 (br,2H,CH2COO), 2.26-2.52 (m,4H+6H+6H,NCH2CH2N+N(CH3)2+N(CH3)2)ppm.

[0248] It should be noted that (tmeda)Ni(C2H4COO) is represented by the following formula (A).

[0249] [Chemical Formula 43]

[0250]

[0251] [Synthesis example 3]

[0252] Synthesis of [(dppe)Ni(C2H4COO)] (dppe: Ph2P(CH2)2PPh2) (Ph is phenyl)

[0253] 0.835 g of the crude product [(tmeda)Ni(C2H4COO)] synthesized in the same manner as in Synthesis Example 2 was added to 1.03 g of dppe, followed by the addition of 30 mL of dry THF, yielding a dark green slurry. The slurry was then stirred at room temperature for 4 hours, filtered under nitrogen, and dried to obtain a yellow solid (1.23 g, 69% yield).1 H NMR (CD2Cl2, 25℃): δ0.82 (m, 2H, Ni-CH2), 2.03-2.36 (m, 2H+2H+4H, P-CH2+P-CH2+CH2COO), 7.47-7.87 (m, 20H, 4Ph) ppm.

[0254] It should be noted that (dppe)Ni(C2H4COO) is represented by the following formula (B).

[0255] [Chemical Formula 44]

[0256]

[0257] [Synthesis example 4]

[0258] Synthesis of benzonorbornene-2,3-dicarboxylate nickel (BNDCA-Ni)

[0259] In a 200 ml three-necked flask, 3.20 g (80 mmol) of sodium hydroxide and 80 ml of water were added and dissolved. Then, 8.57 g (40 mmol) of benzonorbornene-2,3-dicarboxylic anhydride (BNDCA) was added in a single batch and stirred at 80 °C. After confirming the dissolution of BNDCA, 9.51 g (40 mmol) of nickel chloride hexahydrate dissolved in 20 ml of water was added using a dropping funnel, and the mixture was stirred at 80 °C for 1.5 hours. After cooling the reaction solution to room temperature, the precipitated solid was separated by suction filtration, washed with water and acetone, and dried to obtain a green solid (9.91 g, yield 86%). It should be noted that benzonorbornene-2,3-dicarboxylic acid nickel (BNDCA-Ni) is represented by the following formula (C).

[0260] [Chemical Formula 45]

[0261]

[0262] [Example 1]

[0263] In a 50mL glass flask equipped with a distillation apparatus, add 9.97g of benzonorbornene-2,3-dicarboxylic anhydride (BNDCA), 5.10g of triphenylphosphine, and nickel acetate-4-hydrate (Ni(OAc)). 2· Mix 0.097g of 4H2O and heat to 223℃ under reduced pressure of 30 torr.

[0264] The time to reach 223°C was defined as the reaction initiation time. Liquid distillation began 50 minutes after the start of the reaction, and almost ceased after 5.5 hours. 1¹H NMR analysis of the distillate yielded benzonorbornene. The yield of benzonorbornene was 85.1%, the selectivity was 99.7%, and the purity was 99.3%. Furthermore, the molar ratio of benzonorbornene to triphenylphosphine was 1.94.

[0265] It should be noted that the molar ratio of benzonorbornene to triphenylphosphine indicates the molar amount of benzonorbornene obtained relative to 1 mole of triphenylphosphine. The larger the value, the greater the yield of benzonorbornene relative to each unit of triphenylphosphine.

[0266] [Example 2]

[0267] Using the same apparatus as in Example 1, 10.20 g of BNDCA, 5.20 g of triphenylphosphine, and 0.114 g of BNDCA-Ni (nickel benzonorbornene-2,3-dicarboxylate) were added, and the reaction temperature was changed to 228°C. The same operation as in Example 1 was performed. The yield of benzonorbornene was 67.6%, the selectivity was 99.4%, and the purity was 98.4%. Furthermore, the aforementioned BNDCA-Ni (nickel benzonorbornene-2,3-dicarboxylate) is the substance represented by the following formula (C) obtained in Synthesis Example 4.

[0268] [Chemical Formula 46]

[0269]

[0270] [Example 3]

[0271] Using the same apparatus as in Example 1, 10.28 g of BNDCA, 5.33 g of triphenylphosphine, and 0.0984 g of the nickel complex obtained in Synthesis Example 2 were added, and the procedure was carried out in the same manner as in Example 1. The yield of benzonorbornene was 21.5%.

[0272] [Example 4]

[0273] Using the same apparatus as in Example 1, 10.15 g of BNDCA, 5.18 g of triphenylphosphine, and 0.2103 g of the nickel complex obtained in Synthesis Example 3 were added. The reaction temperature was changed to 218 °C, and the operation was carried out in the same manner as in Example 1. The yield of benzonorbornene was 49.3%, the selectivity was 99.7%, and the purity was 98.1%.

[0274] [Example 5]

[0275] In Example 4, the reaction temperature was changed to 228°C; otherwise, the operation was the same as in Example 4. The yield of benzonorbornene was 59.6%, the selectivity was 99.6%, and the purity was 98.0%.

[0276] [Example 6]

[0277] Using the same apparatus as in Example 1, 10.36 g of BNDCA, 5.28 g of triphenylphosphine, and 0.106 g of nickel(II) acetylacetonate (Ni(acac)2) were added, and the reaction temperature was changed to 228 °C. The operation was carried out in the same manner as in Example 1. The yield of benzonorbornene was 79.0%, the selectivity was 99.6%, and the purity was 99.3%.

[0278] [Example 7]

[0279] In Example 1, 0.097 g of nickel acetate-4 hydrate was replaced with 0.0956 g of nickel chloride-6 hydrate (NiCl2·6H2O), and the reaction temperature was changed to 220°C. Otherwise, the operation was the same as in Example 1.

[0280] The yield of benzonorbornene was 40.3%, the selectivity was 96.4%, and the purity was 95.1%.

[0281] [Example 8]

[0282] In Example 1, 0.097 g of nickel acetate-4 hydrate was replaced with 0.088 g of nickel bromide (NiBr2), and the components were mixed in the same manner as in Example 1. The mixture was heated to 220°C under reduced pressure of 30 torr, and then progressively increased to 235°C while reacting for 150 minutes. The yield of benzonorbornene was 28.2%, the selectivity was 98.3%, and the purity was 96.5%.

[0283] [Example 9]

[0284] In Example 1, 0.0628 g of nickel dicerocene (Cp₂Ni) was used instead of 0.097 g of nickel acetate-4 hydrate, and the reaction temperature was changed to 220 °C. Otherwise, the procedure was the same as in Example 1. The yield of benzonorbornene was 74.9%, the selectivity was 99.5%, and the purity was 98.4%.

[0285] [Example 10]

[0286] In Example 1, 0.097 g of nickel acetate-4 hydrate was replaced with 0.0819 g of nickel carbonate (NiCO3), and the components were mixed in the same manner as in Example 1. The reaction was carried out under reduced pressure of 30 torr at 220°C for 160 minutes, and then the temperature was gradually increased to 235°C for 8 hours. The yield of benzonorbornene was 26.5%, the selectivity was 99.8%, and the purity was 96.1%.

[0287] [Example 11]

[0288] In Example 1, 0.097 g of nickel acetate-4 hydrate was replaced with 0.074 g of nickel formate-2 hydrate (Ni(OCOH)2·2H2O), and the reaction temperature was changed to 228 °C. Otherwise, the operation was the same as in Example 1.

[0289] After reacting at 228°C for 70 minutes, the temperature was increased to 237°C, and the reaction was continued for another 100 minutes. The yield of benzonorbornene was 62.8%, the selectivity was 99.8%, and the purity was 98.5%.

[0290] [Example 12]

[0291] In Example 1, in addition to benzonorbornene-2,3-dicarboxylic anhydride, triphenylphosphine, and nickel acetate-4-hydrate, 0.142 g of 1-hexanol was added, and the operation was otherwise the same as in Example 1. CO and CO2 gases were produced when the reaction temperature was about to reach 220°C. Liquid distillation began immediately after reaching 220°C, and almost ceased after 280 minutes. The yield of benzonorbornadiene was 68.4%, the selectivity was 99.5%, and the purity was 99.2%. Table 2 shows the induction period (minutes) from the time of reaching the reaction temperature (220°C) until the production of CO and CO2 gases, with or without the addition of 1-hexanol. The molar ratio of benzonorbornadiene to triphenylphosphine was 1.64.

[0292] [Example 13]

[0293] In a 50 mL glass flask equipped with a distillation apparatus, 9.97 g of benzonorbornene-2,3-dicarboxylic anhydride, 5.06 g of triphenylphosphine, and 0.135 g of 1-hexanol were added. The mixture was heated at 220 °C for 5 minutes under reduced pressure (30 torr). After cooling to approximately 60 °C, the pressure was restored to atmospheric pressure with nitrogen, and 0.096 g of nickel acetate-4 hydrate was added. The mixture was then heated again to 220 °C under reduced pressure (30 torr). CO and CO2 gases were produced just before reaching 220 °C. Liquid distillation began 10 minutes later, and almost completely ceased after 3.5 hours. The yield of benzonorbornene was 87.9%, the selectivity was 99.7%, and the purity was 98.3%. Table 2 shows the induction period (minutes) from the time of reaching the reaction temperature (220 °C) until the production of CO and CO2 gases, with or without the addition of 1-hexanol. In addition, the molar ratio of benzonorbornene to triphenylphosphine is 2.12.

[0294] [Example 14]

[0295] In a 50 mL glass flask equipped with a distillation apparatus and a dropping funnel, 10.01 g of benzonorbornene-2,3-dicarboxylic anhydride, 5.13 g of triphenylphosphine, and 0.072 g of 1-hexanol were added. In another flask, 0.157 g of nickel acetate-4 hydrate was added, and a slurry was prepared with 2.27 g of tetraethylene glycol dimethyl ether, while stirring and exposing the mixture to air. The reactor was heated to 220 °C under reduced pressure (30 torr), and the air-exposed nickel slurry was added dropwise through the dropping funnel over 280 minutes. Distillation of the liquid began 20 minutes after the initial slurry addition and almost disappeared after 280 minutes. The distillate contained 5.84 g of benzonorbornene and 1.09 g of tetraethylene glycol dimethyl ether. The yield of benzonorbornene in this reaction was 96.9%, the selectivity was 99.8%, and the purity after removing tetraethylene glycol dimethyl ether was 94.0%. Furthermore, the molar ratio of benzonorbornene to triphenylphosphine was 2.32.

[0296] [Example 15]

[0297] In a 50 mL glass flask equipped with a distillation apparatus, add 18.33 g of benzonorbornene-2,3-dicarboxylic anhydride (BNDCA), 3.97 g of triphenylphosphine, and 0.353 g of nickel acetate-4 hydrate (Ni(OAc)2·4H2O). Mix the components and then heat to 220 °C under reduced pressure of 30 torr.

[0298] The time to reach 220°C was defined as the reaction initiation point. Liquid distillation began 90 minutes after the start of the reaction, and almost ceased after 3 hours. Analysis of the distillate by 1H NMR revealed benzonorbornene to be present. The yield of benzonorbornene was 77.0%, the selectivity was 99.9%, and the purity was 92.2%. Furthermore, the molar ratio of benzonorbornene to triphenylphosphine was 4.3. The results are shown in Table 3.

[0299] [Example 16]

[0300] In a 50 mL glass flask (1) equipped with a distillation apparatus and a dropping funnel with a valve-operated equalizing tube, 4.34 g of triphenylphosphine was added. In another two-necked flask (2), under nitrogen atmosphere, 22.24 g of benzonorbornene-2,3-dicarboxylic anhydride (BNDCA), 0.323 g of nickel acetate-4-hydrate (Ni(OAc)2·4H2O), and 29.43 g of tetraethylene glycol dimethyl ether were added and slurried. Flask (1) was heated to 220 °C in an oil bath under reduced pressure of 30 torr.

[0301] Next, (a) a certain amount (about 2g) of the slurry in flask (2) was drawn with a pipette while stirring and placed into a dropping funnel. The weight of the slurry was accurately measured by the weight of the pipette before and after the addition. Then, (b) the equalizing valve of the dropping funnel was slowly opened to make it the same pressure as the reactor, and then the slurry was loaded into the reactor (the reaction began). The operations (a) and (b) were repeated 22 times at 20-minute intervals. Gas production and liquid distillation were observed immediately after the reaction began.

[0302] After 460 minutes, 41 mL of liquid was distilled off. This liquid was a tetraethylene glycol dimethyl ether solution of benzonorbornene, with a yield of 97.9%, a selectivity of 99.9%, and a purity of 96.4% after removing the tetraethylene glycol dimethyl ether. Furthermore, the molar ratio of benzonorbornene to triphenylphosphine was 5.9. The results are shown in Table 3.

[0303] [Example 17]

[0304] In Example 16, the following ingredients were used instead: 4.33 g of triphenylphosphine, 21.57 g of benzonorbornene-2,3-dicarboxylic anhydride (BNDCA), 0.209 g of nickel acetate-4 hydrate (Ni(OAc)2·4H2O), and 27.24 g of tetraethylene glycol dimethyl ether. Otherwise, the procedure was the same as in Example 16.

[0305] After 480 minutes, 40 mL of liquid was distilled off. This liquid was a tetraethylene glycol dimethyl ether solution of benzonorbornene, with a yield of 96.0%, a selectivity of 99.8%, and a purity of 96.7% after removing the tetraethylene glycol dimethyl ether. Furthermore, the molar ratio of benzonorbornene to triphenylphosphine was 5.6. The results are shown in Table 3.

[0306] [Example 18]

[0307] In a 50 mL glass flask (1) equipped with a distillation apparatus and two dropping funnels with valves for equalizing pressure, 3.54 g of triphenylphosphine was added. One dropping funnel was covered with a rubber heating element and kept at 180 °C. In another two-necked flask (2), under nitrogen atmosphere, 27.00 g of benzonorbornene-2,3-dicarboxylic anhydride (BNDCA) and 44.07 g of tetraethylene glycol dimethyl ether were added and slurried. Then, in another Schulenck tube, 0.424 g of nickel acetate-4 hydrate (Ni(OAc)2·4H2O) and 10.20 g of tetraethylene glycol dimethyl ether were added and slurried. Flask (1) was heated to 220 °C in an oil bath under reduced pressure of 30 torr.

[0308] (a) Take a certain amount (about 2.5g) of the slurry from the flask (2) with a pipette and put it into a dropping funnel kept at 180℃. The weight is accurately measured by the weight of the pipette before and after the slurry is added.

[0309] (ii) Take a certain amount (about 2.5g) of the slurry from the Schlenk tube with a pipette while stirring, put it into another dropping funnel, and accurately weigh it by the weight of the pipette before and after the addition.

[0310] (iii) Using the same operation as in Example 16, the solution of (i) and the slurry of (ii) were loaded into the reactor at 20-minute intervals over a period of 500 minutes.

[0311] As a result, gas production and liquid distillation were observed immediately after the reaction began, with a final volume of 54 mL distilled. This liquid was a tetraethylene glycol dimethyl ether solution of benzonorbornene, with a yield of 86.8%, a selectivity of 99.9%, a purity of 95.2% after removing the tetraethylene glycol dimethyl ether, and a molar ratio of benzonorbornene to triphenylphosphine of 7.3. The results are shown in Table 3.

[0312] In Examples 16-18, there was no induction period, and the yield of benzonorbornene relative to each unit of triphenylphosphine was increased while maintaining a high yield.

[0313] [Comparative Example 1]

[0314] In Example 1, 0.097 g of nickel acetate-4 hydrate was replaced with 0.100 g of nickel sulfate-6 hydrate (NiSO4·6H2O), and the reaction temperature was changed to 228 °C. Otherwise, the operation was the same as in Example 1. The temperature was raised to 240 °C in stages, but no liquid distillate was obtained.

[0315] [Comparative Example 2]

[0316] In Example 1, 0.097 g of nickel acetate-4 hydrate was replaced with 0.03 g of nickel oxide (NiO), and the reaction temperature was changed to 222°C. Otherwise, the operation was the same as in Example 1. The temperature was increased to 237°C in stages, but no liquid distillate was obtained.

[0317] [Table 1]

[0318]

[0319] [Table 2]

[0320]

[0321] [Table 3]

[0322]

[0323] The following are examples of implementation methods.

[0324] [1] A method for manufacturing a cyclic olefin compound, comprising: a step of decarbonylating and decarboxylating an alicyclic dicarboxylic anhydride by causing a divalent nickel complex represented by the following general formula (1) to function, thereby manufacturing a cyclic olefin compound.

[0325] The divalent nickel complex contains at least one anionic ligand Y represented by any one of the following general formulas (2) to (7), (X) and (Y).

[0326] Ni(Y) m (L) n (1)

[0327] (Here, Ni is divalent nickel, Y is an anionic monodentate or polydentate ligand with at least one Ni-E covalent bond, E is a heteroatom or π-bonded group, m is 1 or 2, L is a neutral ligand, and n is a real number from 0 to 6.)

[0328] [Chemical Formula 47]

[0329]

[0330] (R1 is a hydrogen atom or a hydrocarbon group that may have substituents)

[0331] [Chemical Formula 48]

[0332]

[0333] (R2 is a divalent hydrocarbon group that can have substituents)

[0334] [Chemical Formula 49]

[0335]

[0336] (R3, R4, and R5 are hydrocarbon groups that can have substituents. R3 and R5 or R4 and R5 can also combine with each other to form a ring.)

[0337] [Chemical Formula 50]

[0338]

[0339] (R6 is a divalent hydrocarbon group that can have substituents, and R7 is a hydrogen atom, a hydrocarbon group that can have substituents, or an oxo group. When R7 is a hydrocarbon group, it can also combine with R6 to form a ring.)

[0340] [Chemical Formula 51]

[0341]

[0342] (Z' is a halogen or OH)

[0343] [Chemical Formula 52]

[0344]

[0345] (Ox is selected from NO3) - CO3 2- and PO4 3- (oxyacids in)

[0346] [Chemical Formula 53]

[0347]

[0348] (R1', R2', R3', R4', and R5' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.)

[0349] [Chemical Formula 54]

[0350]

[0351] (R6', R7', and R8' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.)

[0352] In the method for manufacturing the cyclic olefin compound described in [2] [1],

[0353] The divalent nickel complex contains at least one anionic ligand Y represented by any one of the following general formulas (8) to (13) and (Z).

[0354] [Chemical Formula 55]

[0355]

[0356] [Chemical Formula 56]

[0357]

[0358] (X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that can have substituents.)

[0359] [Chemical Formula 57]

[0360]

[0361] [Chemical Formula 58]

[0362]

[0363] (R7 and R8 are each independently a hydrogen atom or a hydrocarbon group that can have substituents; R7 and R8 can also combine with each other to form a ring.)

[0364] [Chemical Formula 59]

[0365]

[0366] (R9 and R) 10 Each is independently a hydrogen atom or a hydrocarbon group that can have substituents, R9 and R 10 They can also combine to form a ring.

[0367] [Chemical Formula 60]

[0368]

[0369] (Z'' is Cl or Br)

[0370] [Chemical Formula 61]

[0371]

[0372] In the method for manufacturing the cyclic olefin compound described in [3], [1] or [2],

[0373] In the process of manufacturing the cyclic olefin compound, there is further a compound that can act as a ligand for the nickel complex.

[0374] In the method for manufacturing the cyclic olefin compound described in [4] [3],

[0375] In the process of manufacturing the cyclic olefin compound, the compound that can act as a ligand is present in 10 to 500 moles relative to 1 mole of the nickel complex.

[0376] In the method for manufacturing the cyclic olefin compound described in [5], [3] or [4],

[0377] The compounds that can act as ligands include phosphorus-containing compounds.

[0378] In any of the methods for producing the cyclic olefin compound described in [6] [3] to [5],

[0379] The compounds that can serve as ligands include at least one selected from the compounds represented by the following general formula (14) and the compounds represented by the following general formula (15).

[0380] [Chemical Formula 62]

[0381]

[0382] (X) 1 X 2and X 3 Each can be an independent hydrocarbon group that has substituents.

[0383] [Chemical Formula 63]

[0384]

[0385] (X) 4 X 5 X 6 and X 7 Each can be an independent hydrocarbon group that may have substituents, where Z is an alkylene group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, a ferrocene group, or a binatyl group.

[0386] In any of the methods for producing the cyclic olefin compound described in [7] [3] to [6],

[0387] The compounds that can act as ligands include triphenylphosphine.

[0388] In any of the methods for producing the cyclic olefin compound described in [8] [1] to [7],

[0389] This includes the process of adding alcohol compounds.

[0390] In the method for manufacturing the cyclic olefin compound described in [9] [8],

[0391] The boiling point of the alcohol compound is lower than that of the alicyclic dicarboxylic anhydride.

[0392] In any of the methods for producing the cyclic olefin compound described in

[10] [1] to [9],

[0393] The alicyclic dicarboxylic anhydride contains at least one of a carboxylic acid compound or a carboxylic anhydride (but not the alicyclic dicarboxylic anhydride) as an impurity.

[0394] In the method for manufacturing the cyclic olefin compound described in

[11]

[10] ,

[0395] The process includes: contacting the alcohol compound with the impurity in a liquid phase, reacting the alcohol compound with the carboxylic acid compound or the carboxylic anhydride in the impurity, and then removing the unreacted alcohol compound.

[0396] In any of the methods for producing the cyclic olefin compound described in

[12] to

[11] ,

[0397] The alicyclic dicarboxylic anhydride comprises compounds represented by the following general formula (16).

[0398] The cyclic olefin compounds include those represented by the following general formula (17).

[0399] [Chemical Formula 64]

[0400]

[0401] (X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that can have substituents.)

[0402] [Chemical Formula 65]

[0403]

[0404] (X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that can have substituents.)

[0405] In any of the methods for producing the cyclic olefin compound described in

[13] [1] to

[12] ,

[0406] The alicyclic dicarboxylic anhydride includes 5,6-benzonorbornene-2,3-dicarboxylic anhydrides represented by the following general formula (18).

[0407] [Chemical Formula 66]

[0408]

[0409] (R) 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is an independent hydrogen atom or may have substituents with heteroatoms.

[0410] In the method for manufacturing the cyclic olefin compound described in

[14]

[13] ,

[0411] In the general formula (18), R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Both are hydrogen.

[0412] In any of the methods for producing the cyclic olefin compound described in

[15] [1] to

[14] ,

[0413] The alicyclic dicarboxylic anhydride comprises the dicarboxylic anhydride represented by the following general formula (19).

[0414] [Chemical Formula 67]

[0415]

[0416] (n is 0 or 1, X' is O or CH2)

[0417] In any of the methods for producing the cyclic olefin compound described in

[16] [1] to

[15] ,

[0418] In the process of producing the cyclic olefin compound, the process is carried out simultaneously with removing the generated cyclic olefin compound from the reaction system.

[0419] This application claims priority based on Japanese Patent Application No. 2020-110761, filed on June 26, 2020, the entire contents of which are incorporated herein by reference.

Claims

1. A method for producing a cyclic olefin compound, comprising: The process of producing cyclic olefin compounds by decarbonylating and decarboxylating alicyclic dicarboxylic anhydrides through the action of a divalent nickel complex represented by the following general formula (1). The divalent nickel complex comprises at least one anionic ligand Y represented by any one of the following general formulas (2) to (7) and (X1), Ni(Y) m (L) n (1) Here, Ni is divalent nickel, Y is an anionic monodentate or polydentate ligand having at least one Ni-E covalent bond, E is a heteroatom or π-bonded group, m is 1 or 2, L is a neutral ligand, and n is a real number from 0 to 6, wherein L is a phosphine, amine, ether, alcohol, water, or carbon monoxide. R1 is a hydrogen atom or a hydrocarbon group that may have substituents. R2 is a divalent hydrocarbon group that can have substituents. R3, R4, and R5 are hydrocarbon groups that can have substituents. R3 and R5, or R4 and R5, can also combine to form a ring. In addition, R3, R4, and R5 can also be hydrogen atoms. R6 is a divalent hydrocarbon group that can have substituents, and R7 is a hydrogen atom, a hydrocarbon group that can have substituents, or an oxo group. When R7 is a hydrocarbon group, it can also combine with R6 to form a ring. Z' is a halogen or OH. Ox is CO3 2- , R1', R2', R3', R4', and R5' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.

2. The method for manufacturing the cyclic olefin compound according to claim 1, The divalent nickel complex comprises at least one anionic ligand Y represented by any one of the following general formulas (9), (11) to (13), (Z1), (8), and (10). X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents. R7 and R8 are each independently a hydrogen atom or a hydrocarbon group that can have substituents. R7 and R8 can also combine with each other to form a ring. R9 and R 10 Each is independently a hydrogen atom or a hydrocarbon group that can have substituents, R9 and R 10 They can also combine to form a ring. Z'' is Cl or Br. 。 3. The method for producing the cyclic olefin compound according to claim 1 or 2, In the process of manufacturing the cyclic olefin compound, a compound that can act as a ligand for the nickel complex is further present, wherein... The compounds that can act as ligands for the nickel complex are monodentate or polydentate electron-donating compounds with nitrogen, phosphorus, arsenic, or antimony as coordinating atoms.

4. The method for manufacturing the cyclic olefin compound according to claim 3, In the process of manufacturing the cyclic olefin compound, the compound that can act as a ligand is present in 10 to 500 moles relative to 1 mole of the nickel complex.

5. The method for producing the cyclic olefin compound according to claim 3, The compounds that can act as ligands include phosphorus-containing compounds.

6. The method for producing the cyclic olefin compound according to claim 3, The compounds that can act as ligands include at least one selected from compounds represented by the following general formula (14) and compounds represented by the following general formula (15). X 1 X 2 and X 3 Each can be an independent hydrocarbon group that has substituents. X 4 X 5 X 6 and X 7 Each can be a hydrocarbon group that has substituents, and Z is an alkylene group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, a ferrocene group, or a naphthylene group.

7. The method for producing the cyclic olefin compound according to claim 3, The compounds that can act as ligands include triphenylphosphine.

8. The method for producing the cyclic olefin compound according to claim 1 or 2, This includes the process of adding alcohol compounds.

9. The method for producing the cyclic olefin compound according to claim 8, The boiling point of the alcohol compound is lower than that of the alicyclic dicarboxylic anhydride.

10. The method for producing the cyclic olefin compound according to claim 1 or 2, The alicyclic dicarboxylic anhydride contains at least one of a carboxylic acid compound or a carboxylic anhydride as an impurity, wherein... The impurities do not include the alicyclic dicarboxylic anhydride.

11. The method for producing the cyclic olefin compound according to claim 10, This includes the process of adding alcohol compounds. include: The process involves contacting the alcohol compound with the impurity in a liquid phase, reacting the alcohol compound with the carboxylic acid compound or the carboxylic anhydride in the impurity, and then removing the unreacted alcohol compound.

12. The method for producing the cyclic olefin compound according to claim 11, The boiling point of the alcohol compound is lower than that of the aforementioned alicyclic dicarboxylic anhydride.

13. The method for producing the cyclic olefin compound according to claim 1 or 2, The alicyclic dicarboxylic anhydride comprises compounds represented by the following general formula (16). The cyclic olefin compounds include those represented by the following general formula (17). X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents. X is the set of nonmetallic atoms required to form the ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group that may have substituents.

14. The method for producing the cyclic olefin compound according to claim 1 or 2, The alicyclic dicarboxylic anhydrides include 5,6-benzonorbornene-2,3-dicarboxylic anhydrides represented by the following general formula (18). R 11 R 12 R 13 R 14 R 15 R 16 and R 17 Each is an independent hydrogen atom or may have substituents that are heteroatoms.

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

16. The method for producing the cyclic olefin compound according to claim 1 or 2, The alicyclic dicarboxylic anhydride comprises the dicarboxylic anhydride represented by the following general formula (19). n is 0 or 1, and X' is O or CH2.

17. The method for producing the cyclic olefin compound according to claim 1 or 2, In the process of producing the cyclic olefin compound, the process is carried out simultaneously with removing the generated cyclic olefin compound from the reaction system.

18. The method for producing the cyclic olefin compound according to claim 1 or 2, wherein, The substituent is selected from any one of the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, acyl, alkylamino, carbamoyl, nitro, nitrosyl, cyano, alkylthio, sulfinyl, sulfonyl, and silyl. The substituents may also be adjacent substituents cross-linked to form a ring containing the carbon atom they bind.

19. The method for producing the cyclic olefin compound according to claim 1, wherein, R1 is selected from any one of the groups consisting of hydrogen atoms, methyl groups, and ethyl groups. R2 is 1,4-dihydro-1,4-methylene-2,3-naphthylene. R3, R4, and R5 are each independently selected from any one of the groups consisting of hydrogen atoms, methyl groups, and ethyl groups. R6 is selected from any one of the groups consisting of methylene, ethylene, and trimethylene. R7 is selected from any one of the groups consisting of hydrogen atoms, methyl groups, and ethyl groups. Z' is halogen. Ox is CO3 2- , R1', R2', R3', R4', and R5' are each an independent hydrogen atom.

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