JPWO2008062553A1 - Method for producing cyclic olefin - Google Patents

Abstract

The alicyclic dicarboxylic acid anhydride represented by the following general formula (1) is decarbonylated and decarboxylated using a nickel complex as a catalyst in the presence of a compound that can be a ligand, and represented by the following general formula (2). In the method for producing a cyclic olefin compound, the reaction is carried out while removing the produced cyclic olefin compound from the reaction system.

Description

  The present invention relates to a method for producing a cyclic olefin from an alicyclic dicarboxylic acid anhydride.

  The cyclic olefin is useful as a raw material for COC obtained by copolymerization with a lower olefin such as ethylene or ring-opening metathesis polymerization. There are many known methods for producing cyclic olefins, including (1) decarbonylation and decarboxylation of alicyclic dicarboxylic acid anhydrides, or (2) alicyclic dicarboxylic acid anhydrides. There is an oxidative decarboxylation reaction of a dicarboxylic acid derivative obtained by hydrolysis.

  The alicyclic dicarboxylic acid anhydride used as a raw material for these reactions can be obtained by a Diels-Alder reaction between a conjugated diene compound and maleic anhydrides. In general, maleic anhydrides are highly reactive in the Diels-Alder reaction, so that adducts are often obtained in good yields. Therefore, if the decarbonylation or decarboxylation can be efficiently performed from these alicyclic dicarboxylic acid anhydrides or dicarboxylic acid derivatives obtained by hydrolysis thereof, various structures can be obtained by combining various diene compounds and maleic anhydrides. It can be expected to synthesize cyclic olefins having a high yield.

  However, both of the known methods (1) and (2) have many problems in producing a cyclic olefin industrially advantageously.

  As a method of (1), for example, J.A. Org. Chem. , 41, 887 (1975). However, there is a problem that one equivalent or more of an expensive nickel carbonyl complex is required. There is also an example using a catalytic amount of nickel carbonyl complex (J. Org. Chem., 43, 3074 (1978)), but the catalytic amount is as high as 20 mol% with respect to the raw acid anhydride, and the solvent is strictly purified. However, it is not satisfactory that the catalyst must be newly prepared before use.

  As a method of (2), for example, (a) J. et al. Am. Chem. Soc. , 74, 4370 (1952), (b) Org. React. , 19, 279 (1972), using lead acetate (IV), (c) (Tetrahedron Lett., 4447 (1976) using copper (I) oxide and 2,2′-bipyridyl, ) Electrolytic method described in Tetrahedron Lett., 5117 (1968).

However, these methods also have various problems.
In (a), there is a problem that one or more equivalents of highly toxic lead (IV) oxide is required with respect to the raw material dicarboxylic acid and the yield is very low.

  In (b), although the yield is higher than in (a), it cannot be said to be satisfactory because the rearrangement reaction easily occurs. Similarly, highly toxic lead (IV) is used with respect to the raw dicarboxylic acid. There is a problem that one equivalent or more is required.

  Even in (c), there is a problem that 2 equivalents or more of copper oxide (I) and 1 equivalent or more of 2,2′-bipyridyl are required for the raw material dicarboxylic acid.

  In (d), it is necessary to use expensive platinum for the electrode, and if the raw material concentration in the reaction solution is high, the yield of the product is extremely reduced, so it must be performed under dilute conditions. To do so, it has problems such as poor production efficiency.

As described above, each method requires expensive raw materials or equipment, which is costly and has a problem that the separation and purification of the product is complicated, and further, a large amount of waste is discharged. It is not preferable from the viewpoint of the problem.
J. et al. Org. Chem. , 41, 887 (1975) J. et al. Org. Chem. , 43, 3074 (1978) J. et al. Am. Chem. Soc. , 74, 4370 (1952) Org. React. , 19, 279 (1972) Tetrahedron Lett. , 4447 (1976) Tetrahedron Lett. , 5117 (1968)

  Therefore, in view of the prior art, an object of the present invention is to provide a method for industrially advantageously producing a cyclic olefin useful as a raw material for polyolefin such as COC.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that a compound that can be a ligand in a method for producing a cyclic olefin by decarbonylation and decarboxylation of an alicyclic dicarboxylic acid anhydride. By using a nickel complex as a catalyst in the coexistence and removing the generated cyclic olefin out of the reaction system, it was found that it is possible to produce a high-purity cyclic olefin with high selectivity. It came to be completed.

  That is, the present invention is as described in the following (1) to (9).

  (1) General formula (1)

(Wherein X represents a nonmetallic atom group necessary for forming a ring, and R and R ′ each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent). An alicyclic dicarboxylic acid anhydride is decarbonylated and decarboxylated using a nickel complex as a catalyst in the presence of a compound capable of acting as a ligand.

(Wherein X represents a nonmetallic atom group necessary for forming a ring, and R and R ′ each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent). A method for producing a cyclic olefin compound comprising:
The said reaction is performed, removing the produced | generated said cyclic olefin compound out of the reaction system, The manufacturing method of the cyclic olefin compound characterized by the above-mentioned.

  (2) The manufacturing method of the cyclic olefin compound as described in (1) using 10-500 mol of said compounds which can become a ligand with respect to 1 mol of said nickel complexes.

  (3) The production method according to (1) or (2), wherein the compound that can be a ligand is a phosphorus-containing compound.

  (4) The method for producing a cyclic olefin compound according to any one of (1) to (3), wherein the compound that can be a ligand is represented by the general formula (5) or (6);

(Wherein X ¹ , X ² and X ³ each independently represents a hydrocarbon group which may have a substituent)

(In the formula, X ⁴ , X ⁵ , X ⁶ and X ⁷ each independently represent a hydrocarbon group which may have a substituent. Z represents an alkylene group having 1 to 8 carbon atoms or an arylene group. And represents a ferrocenylene group).

  (5) The production method according to (4), wherein the compound that can be a ligand is triphenylphosphine.

  (6) The manufacturing method according to any one of (1) to (5), wherein the nickel complex is a zero-valent nickel complex.

  (7) The alicyclic dicarboxylic acid anhydride is represented by the general formula (3)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or a substituent that may have a hetero atom). The production method according to any one of (1) to (6), which is 5,6-benzo-2,3-dicarboxylic anhydride.

(8) The production method according to (7), wherein in formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are all hydrogen.

  (9) The alicyclic dicarboxylic acid anhydride is represented by the general formula (4)

(Wherein n represents an integer of 0 to 1 and X ′ represents O or CH ₂ ). The production method according to any one of (1) to (8), which is a dicarboxylic acid anhydride represented by:

  According to the present invention, a cyclic olefin compound useful as a raw material for a polyolefin such as COC obtained by copolymerization with a lower olefin such as ethylene or ring-opening metathesis polymerization by decarbonylation or decarboxylation of an alicyclic dicarboxylic acid anhydride. Can be provided.

  According to the method of the present invention, it is possible to significantly reduce the amount of nickel complex used as a catalyst, and a large amount of expensive raw material is required, which is costly and produces a low yield of product. It is possible to solve problems in known methods such as complicated separation and purification of wastes and discharge of a large amount of waste.

  For the above reasons, the present invention is extremely advantageous as an industrial production method for cyclic olefins, and is particularly useful when cyclic olefins that are difficult to obtain from easily available alicyclic dicarboxylic acid anhydrides can be produced.

¹ is a ¹ H-NMR chart of benzonorbornene-2,3-dicarboxylic acid anhydride obtained in Examples. It is a ¹³ C-NMR chart of benzonorbornene-2,3-dicarboxylic anhydride obtained in the examples. ^{1 is} a ¹ H-NMR chart of benzonorbornadiene obtained in Examples. It is a ¹³ C-NMR chart of benzonorbornadiene obtained in Examples.

Hereinafter, the present invention will be described in detail.
The alicyclic dicarboxylic acid anhydride used as a raw material in the present invention is represented by the general formula (1).

X represents a nonmetallic atom group necessary for forming a ring, and the ring composed of these may be a saturated ring or an unsaturated ring. For example, cyclohexane, norbornane, bicyclo [2.2.2] octane, tetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] saturated ring such as dodecane, norbornene, tetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -8-dodecene, unsaturated rings such as benzonorbornene, aprotic heterocycles such as 7-oxabicyclo [2.2.1] heptane, 7-thiabicyclo [2.2.1] heptane Can be mentioned.

  R and R ′ each independently represent a hydrogen atom or a hydrocarbon group that 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 propynyl; phenyl, Aryl groups such as tolyl; aralkyl groups such as benzyl and phenethyl.

  R and R ′ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, a methyl group or an ethyl group.

  R and R ′ may be bridged with each other or with a ring composed of X to form an alkylene group having 2 to 8 carbon atoms. Further, the ring constituted by X, R and R ′ may have a substituent inert to the reaction. Examples of the substituent include halogen, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyloxy group, acyl group, alkylamino group, carbamoyl group, nitro group, nitroso group. , Cyano group, alkylthio group, sulfinyl group, sulfonyl group, silyl group and the like. In addition, among these substituents, adjacent substituents may be bridged to form a ring containing the bonded carbon atoms.

  Specific examples of the alicyclic dicarboxylic acid anhydride represented by the general formula (1) include 5,6-benzo-2,3-dicarboxylic acid anhydrides represented by the general formula (3), The dicarboxylic acid anhydride represented by 4) can be used.

In the general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or a substituent that may have a hetero atom. As the substituent, the above-described substituents can be used. In the present invention, a compound in which any substituent of R ^{1 to} R ⁷ is a hydrogen atom can be used.

  In the present invention, a nickel complex is used as a catalyst. Specific examples thereof include a nickel carbonyl complex obtained by reaction of nickel tetracarbonyl and a tertiary phosphine, such as bis (triphenylphosphine) nickel dicarbonyl, Alternatively, a nickel complex such as tetrakis (triphenylphosphine) nickel that can be converted to a nickel carbonyl complex in the presence of carbon monoxide.

  As the nickel complex, a commercially available one can be used as it is, for example, U.S. Pat. Am. Chem. Soc. 81, 4200 (1959); Am. Chem. Soc. 94, 2669 (1972); 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); Chem. Soc. , 2099 (1962), and the like.

  In addition, the above nickel complex includes nickel tetracarbonyl, or a compound that can act as a ligand for nickel complexes such as bis (1,5-cyclooctadiene) nickel, bis (π-allyl) nickel, nickelocene, and the like. It may be formed in situ by adding to the reaction solution. Generally the usage-amount of a nickel complex catalyst is 0.0001-0.2 mol per mol of alicyclic dicarboxylic acid anhydride which is a raw material, Preferably it is 0.001-0.05 mol.

  The “compound that can be a ligand” used in the present invention (hereinafter also simply referred to as a compound) is a monodentate or polyvalent compound having a group V element of the periodic table as a coordinating atom, that is, nitrogen, phosphorus, arsenic, and antimony. It is an electron donating compound of the locus. In addition, the compound that can be a ligand used in the present invention may be the same as or different from the ligand in the nickel complex.

Compounds that can be ligands include tributylamine, trioctylamine, triphenylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,2 -Tertiary amines such as phenylenediamine, nitrogen-containing aromatics such as 2,2'-bipyridyl and 1,10-phenanthroline, N, N'-diphenyl-1,4-diazabutadiene, 1,6- Nitrogen-containing compounds represented by imines such as diphenyl-2,5-diaza-1,5-hexadiene; arsenic-containing compounds such as tributylarsenic and triphenylarsenic;
Examples thereof include antimony-containing compounds such as tributylantimony and triphenylantimony; and phosphorus-containing compounds represented by the general formula (5) or (6).

(Wherein X ¹ , X ² and X ³ each independently represents a hydrocarbon group which may have a substituent)

(In the formula, X ⁴ , X ⁵ , X ⁶ and X ⁷ each independently represent a hydrocarbon group which may have a substituent. Z represents an alkylene group having 1 to 8 carbon atoms or an arylene group. Represents a ferrocenylene group.)

Examples of the hydrocarbon group for X ^{1 to} X ⁷ include condensed rings formed by condensation of alkyl groups having 1 to 6 carbon atoms, aromatic groups, carbocycles and / or heterocycles. Moreover, as the substituent, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, etc. can be mentioned.

Examples of the compound that can be a ligand represented by the general formula (5) include tricyclohexylphosphine, tricyclopentylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, trioctylphosphine, and tribenzylphosphine. Trialkylphosphines such as triphenylphosphine, tolylphosphine (including ortho, meta, and para substituted isomers), tris (methoxyphenyl) phosphine (ortho, meta, and para substituted isomers) ), Tris (fluorophenyl) phosphine (including various ortho, meta, and para substituted isomers), triarylphosphine such as tri (α-naphthyl) phosphine, and diarylalkylphosphine such as diphenylcyclohexylphosphine. Although such dialkyl aryl phosphines such as dicyclohexyl phenyl phosphine, preferably triarylphosphines, even more preferably triphenylphosphine. X ¹ , X ² and X ³ may be bridged between two groups to form a ring containing a phosphorus atom, and examples of such phosphine include phenylbiphenylenephosphine.

  Examples of the compound that can be a ligand represented by the general formula (6) include 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, and 1,4-bis. And (diphenylphosphino) butane.

  In the present invention, it is preferable to use a compound that can be a ligand represented by the general formula (5) or (6) from the viewpoint of obtaining a target substance with high selectivity and high purity.

  In the present invention, in order to improve the stability of the nickel complex catalyst, it is important that a compound capable of being a ligand coexists excessively. If the amount of the compound that can be a ligand is too small, the stability of the catalyst is lowered. On the other hand, when the amount of the ligand is large, the stability of the catalyst is not improved in proportion to the amount used, but it is uneconomical or the reaction rate tends to decrease.

  Therefore, the amount of the compound that can be a ligand is not necessarily constant depending on the type, but is usually 10 to 500 mol, preferably 20 to 200 mol, per mol of the nickel complex catalyst.

  By using the compound that can be a ligand in the above amount, a high-purity cyclic olefin can be produced with high selectivity. Further, within this range, the compound itself may be used as a solvent. The compound used in that case is preferably stable with respect to the target compound and relatively inexpensive. Among them, triphenylphosphine is one of useful compounds.

  These compounds that can be ligands may be used alone or as a mixture of any two or more thereof. When using a mixture of compounds that can become these ligands, they may be mixed in an arbitrary ratio, but the total amount of these compounds used is within the above range with respect to 1 mol of the nickel complex catalyst. Is preferred.

  A higher reaction temperature is advantageous in terms of reaction rate. However, if the reaction temperature is too high, it may cause undesirable side reactions such as decomposition of the catalyst, rearrangement of the cyclic olefin product, polymerization, and the like, leading to a decrease in selectivity. . Therefore, it is usually preferable to carry out the reaction at 100 to 300 ° C., particularly 150 to 250 ° C.

  In the present invention, the product is removed from the reaction system as quickly as possible in order to suppress the decrease in the activity of the nickel complex catalyst, and further to increase the selectivity by reducing the thermal history of the cyclic olefin compound to be produced. is important. Therefore, it is desirable to employ a reactive distillation method.

  The reaction pressure largely depends on the boiling point of the olefin to be produced, but is not particularly limited as long as rapid removal of the product from the outside of the reaction system is achieved. When the boiling point of the product is low, the reaction can be performed at normal pressure. On the other hand, when the boiling point of the product is high, the reaction is preferably performed under reduced pressure.

The cyclic olefin compound represented by the general formula (2) obtained from the alicyclic dicarboxylic acid anhydride of the general formula (1) is taken out in the form of a gas and then separated from the gas containing CO and CO ₂ by condensation. Is done. The crude cyclic olefin compound thus obtained may be further purified by distillation or the like, if necessary.

  In the reaction, if the compound that can be a ligand itself can play the role of a solvent, the reaction may be performed without using any other solvent, but a new solvent may be used if necessary. Absent.

  As the solvent, any solvent can be used as long as it is inert to the raw material, the catalyst, and the compound that can be a ligand. For example, ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diphenyl ether, anisole and veratrol, aromatic hydrocarbons such as tetralin and naphthalene, aprotic such as nitrobenzene, benzonitrile, N-methylpyrrolidone and dimethylimidazolidinone Examples include polar solvents.

  The solvent (or a compound that can be a ligand) is preferably one that can be easily separated from the product cyclic olefin, and generally has a higher boiling point than the cyclic olefin to be produced. When a solvent such as the above is used, when the product containing the target cyclic olefin is separated from the reaction mixture by reactive distillation, the solvent from the reaction solution in which the catalyst and the compound capable of being a ligand are dissolved. Since distillation of (or a compound that can be a ligand) can be suppressed, there is no need to newly supply these solvents (or compounds that can become a ligand), and complicated separation and purification of the product. This is also advantageous in that it can be avoided.

  The reaction is preferably carried out without oxygen or moisture, and is usually carried out in an inert atmosphere such as nitrogen or argon.

  The reaction can be carried out either in a batch system or in a continuous system in which a nickel complex catalyst, a compound capable of becoming a ligand, a raw material dicarboxylic acid anhydride, and a solvent are continuously supplied to a reactor. .

  Hereinafter, the usefulness of the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The analysis was performed by gas chromatography, the conversion rate and selectivity were determined by the internal standard method (mol%), and the purity was determined by area percentage (%).

[Synthesis Example 1]
Synthesis of benzonorbornene-2,3-dicarboxylic acid anhydride Into a 1.5 L autoclave made of SUS316, 380.1 g (3.14 mol) of indene (manufactured by JFE Chemical, purity 96%), 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, and the mixture was 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). The solid was analyzed by mass spectrum and NMR. As a result, it was benzonorbornene-2,3-dicarboxylic anhydride (EI m / z 214 (M ⁺ )). NMR charts are shown in FIGS. As a result of analysis by gas chromatography, the purity was 99% or more (isolation yield 69% based on maleic anhydride).

[Example 1]
In a 100 mL glass flask equipped with a distillation apparatus, 21.42 g (0.100 mol) of benzonorbornene-2,3-dicarboxylic acid anhydride, 26.23 g (0.100 mol) of triphenylphosphine, bis (triphenylphosphine) nickel 1.28 g (2.0 mmol) of dicarbonyl was charged and heated to 200 to 210 ° C. under a reduced pressure of 25 mmHg. The reaction liquid boiled, and gas generation and liquid distillation were observed. After 2 hours, the liquid distillate has subsided (13.55 g). As a result of analysis of the reaction residue, the conversion of benzonorbornene-2,3-dicarboxylic anhydride was 99.0%. Further, the liquid distilled was benzonorbornadiene (EI m / z 142 (M ⁺ )) as a result of analysis by mass spectrum and NMR. The NMR chart is shown in FIGS. The selectivity was 96.0% and the purity was 99.7%.

[Example 2]
21.42 g (0.100 mol) of benzonorbornene-2,3-dicarboxylic acid anhydride, 39.34 g (0.150 mol) of triphenylphosphine, 0.64 g (1.0 mmol) of bis (triphenylphosphine) nickel dicarbonyl The same reaction as in Example 1 was performed. After 9 hours, the conversion of benzonorbornene-2,3-dicarboxylic anhydride was 94.9%. The selectivity of benzonorbornadiene (13.19 g) was 97.2%, and the purity was 99.4%.

[Example 3]
In Example 1, the same operation was performed except that the nickel complex used was changed to bis (1,5-cyclooctadiene) nickel (0.55 g, 2.0 mmol).
The conversion of benzonorbornene-2,3-dicarboxylic acid anhydride was 95.1%. The selectivity of benzonorbornadiene (13.27 g) was 97.4%, and the purity was 99.2%.

[Example 4]
In Example 1, the same operation was performed except that the nickel complex used was changed to tetrakis (triphenylphosphine) nickel (2.22 g, 2.0 mmol).
The conversion of benzonorbornene-2,3-dicarboxylic acid anhydride was 99.1%. The selectivity for benzonorbornadiene (13.27 g) was 93.0%, and the purity was 99.0%.

[Example 5]
In a 50 mL glass flask equipped with a distillation apparatus, 9.96 g (0.060 mol) of endo-norbornane-2,3-dicarboxylic acid anhydride, 23.60 g (0.090 mol) of triphenylphosphine, bis (triphenylphosphine) 0.64 g (1.0 mmol) of nickel dicarbonyl was charged and heated to 270 ° C. under normal pressure. The reaction liquid boiled, and gas generation and liquid distillation were observed. After 2 hours, the liquid distillate has subsided (4.78 g). As a result of analysis of the reaction residue, the conversion of endo-norbornane-2,3-dicarboxylic anhydride was 99.5%. As a result of analyzing the distilled liquid by mass spectrum, it was norbornene (EI m / z 94 (M ⁺ )), the selectivity was 86.4%, and the purity was 98.7%.

[Comparative Example 1]
In a 100 mL glass flask equipped with a reflux condenser, 21.42 g (0.100 mol) of benzonorbornene-2,3-dicarboxylic acid anhydride, 0.64 g (1.0 mmol) of bis (triphenylphosphine) nickel dicarbonyl, Tetraethylene glycol dimethyl ether (39.5 g) was charged and heated to 210 ° C. under a nitrogen atmosphere at normal pressure. As a result of analysis of the reaction solution, the yield of benzonorbornadiene was 1% or less after 2 hours, and no further improvement was observed.

[Comparative Example 2]
In a 100 mL glass flask equipped with a reflux condenser, 21.42 g (0.100 mol) of benzonorbornene-2,3-dicarboxylic acid anhydride, 39.34 g (0.150 mol) of triphenylphosphine, bis (triphenylphosphine) 0.64 g (1.0 mmol) of nickel dicarbonyl was charged and heated to 210 ° C. under a nitrogen atmosphere at normal pressure. As a result of analysis of the reaction solution, the yield of benzonorbornadiene was 3% after 2 hours, and no further improvement was observed.

Claims (9)

General formula (1)

(Wherein X represents a nonmetallic atom group necessary for forming a ring, and R and R ′ each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent). An alicyclic dicarboxylic acid anhydride is decarbonylated and decarboxylated using a nickel complex as a catalyst in the presence of a compound capable of acting as a ligand.

(Wherein X represents a nonmetallic atom group necessary for forming a ring, and R and R ′ each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent). A method for producing a cyclic olefin compound comprising:
The said reaction is performed, removing the produced | generated said cyclic olefin compound out of the reaction system, The manufacturing method of the cyclic olefin compound characterized by the above-mentioned.   The manufacturing method of the cyclic olefin compound of Claim 1 using 10-500 mol of said compounds which can become a ligand with respect to 1 mol of said nickel complexes.   The method according to claim 1 or 2, wherein the compound that can be a ligand is a phosphorus-containing compound. The said compound which can become a ligand is represented by General formula (5) or (6), The manufacturing method of the cyclic olefin compound of Claim 3 characterized by the above-mentioned;

(Wherein X ¹ , X ² and X ³ each independently represents a hydrocarbon group which may have a substituent)

(In the formula, X ⁴ , X ⁵ , X ⁶ and X ⁷ each independently represent a hydrocarbon group which may have a substituent. Z represents an alkylene group having 1 to 8 carbon atoms or an arylene group. And represents a ferrocenylene group).   The method according to claim 4, wherein the compound that can be a ligand is triphenylphosphine.   The manufacturing method according to claim 1, wherein the nickel complex is a zerovalent nickel complex. The alicyclic dicarboxylic acid anhydride has the general formula (3)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or a substituent that may have a hetero atom). The production method according to any one of claims 1 to 6, which is 5,6-benzo-2,3-dicarboxylic acid anhydrides. The production method according to claim 7, wherein in the general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are all hydrogen. The alicyclic dicarboxylic acid anhydride has the general formula (4)

(Wherein, n an integer of 0 to 1, X 'is. Representing O or CH ₂₎ The process according to any one of claims 1 to 8 is a dicarboxylic acid anhydride represented by.

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