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EP-4174047-B1 - METHOD FOR PRODUCING CYCLIC OLEFIN COMPOUND

EP4174047B1EP 4174047 B1EP4174047 B1EP 4174047B1EP-4174047-B1

Inventors

  • MAKIO, HARUYUKI
  • YANO, TAKAAKI
  • MATSUURA, AKIRA

Dates

Publication Date
20260513
Application Date
20210610

Claims (15)

  1. A method for producing a cyclic olefin compound, comprising: a step of producing a cyclic olefin compound by applying a divalent nickel complex represented by General Formula (1) to decarbonylate and decarboxylate an alicyclic dicarboxylic acid anhydride, wherein the divalent nickel complex includes at least one anionic ligand Y represented by any of General Formulae (2) to (7), (X1), and (Y1), Ni(Y) m (L) n (1) (here, Ni is divalent nickel, Y is an anionic monodentate or polydentate ligand and has at least one Ni-E covalent bond, E is a heteroatom or a π-bonding group, m is 1 or 2, L is a neutral ligand, and n is a real number of 0 to 6) (R 1 is a hydrogen atom or a hydrocarbon group which may have a substituent) (R 2 is a divalent hydrocarbon group which may have a substituent) (R 3 , R 4 , and R 5 are hydrocarbon groups which may have a substituent, R 3 and R 5 or R 4 and R 5 may be bonded to each other to form a ring, and R 3 , R 4 , and R 5 may be hydrogen atoms) (R 6 is a divalent hydrocarbon group which may have a substituent, R 7 is a hydrogen atom, a hydrocarbon group which may have a substituent, or an oxo group, and in a case where R 7 is a hydrocarbon group, R 7 may be bonded to R 6 to form a ring) (Z' is halogen or OH) (Ox is an oxoacid selected from NO 3- , CO 3 2- , and PO 4 3- ) (R 1 ', R 2 ', R 3 ', R 4 ', and R 5 ' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent) (R 6 ', R 7 ', and R 8 ' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent).
  2. The method for producing a cyclic olefin compound according to Claim 1, wherein the divalent nickel complex includes at least one anionic ligand Y represented by any of General Formulae (9), (11) to (13), and (Z1), and Formulae (8) and (10), (X is a group of non-metal atoms required to form a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent) (R 7 and R 8 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and R 7 and R 8 may be bonded to each other to form a ring) (R 9 and R 10 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and R 9 and R 10 may be bonded to each other to form a ring) (Z" is Cl or Br)
  3. The method for producing a cyclic olefin compound according to Claim 1 or 2, wherein, in the step of producing a cyclic olefin compound, a compound which can be a ligand for the nickel complex is further present.
  4. The method for producing a cyclic olefin compound according to Claim 3, wherein, in the step of producing a cyclic olefin compound, the compound which can be a ligand is present in an amount of 10 to 500 mol with respect to 1 mol of the nickel complex.
  5. The method for producing a cyclic olefin compound according to Claim 3 or 4, wherein the compound which can be a ligand includes a phosphorus-containing compound.
  6. The method for producing a cyclic olefin compound according to any one of Claims 3 to 5, wherein the compound which can be a ligand includes at least one selected from a compound represented by General Formula (14) and a compound represented by General Formula (15), (X 1 , X 2 , and X 3 are each independently a hydrocarbon group which may have a substituent) (X 4 , X 5 , X 6 , and X 7 are each independently a hydrocarbon group which may have a substituent, and Z is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a ferrocenylene group, or a binaphthylene group).
  7. The method for producing a cyclic olefin compound according to any one of Claims 3 to 6, wherein the compound which can be a ligand includes triphenylphosphine.
  8. The method for producing a cyclic olefin compound according to any one of Claims 1 to 7, further comprising: a step of adding an alcohol compound.
  9. The method for producing a cyclic olefin compound according to any one of Claims 1 to 8, wherein the alicyclic dicarboxylic acid anhydride includes at least one of a carboxylic acid compound or a carboxylic acid anhydride (excluding the alicyclic dicarboxylic acid anhydride) as an impurity.
  10. The method for producing a cyclic olefin compound according to Claim 9, further comprising: a step of adding an alcohol compound; and a step of contacting the alcohol compound with the impurity in a liquid phase to react the alcohol compound with the carboxylic acid compound or the carboxylic acid anhydride in the impurity, and removing an unreacted alcohol compound.
  11. The method for producing a cyclic olefin compound according to any one of Claims 1 to 10, wherein the alicyclic dicarboxylic acid anhydride includes a compound represented by General Formula (16), and the cyclic olefin compound includes a compound represented by General Formula (17), (X is a group of non-metal atoms required to form a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent) (X is a group of non-metal atoms required to form a ring, and R and R' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent).
  12. The method for producing a cyclic olefin compound according to any one of Claims 1 to 11, wherein the alicyclic dicarboxylic acid anhydride includes 5,6-benzo-2,3-dicarboxylic acid anhydrides represented by General Formula (18), (R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are each independently a hydrogen atom or a substituent which may have a heteroatom).
  13. The method for producing a cyclic olefin compound according to Claim 12, wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 in General Formula (18) are all hydrogens.
  14. The method for producing a cyclic olefin compound according to any one of Claims 1 to 11, wherein the alicyclic dicarboxylic acid anhydride includes a dicarboxylic acid anhydride represented by General Formula (19), (n is 0 or 1, and X' is O or CH 2 ).
  15. The method for producing a cyclic olefin compound according to any one of Claims 1 to 14, wherein the step of producing a cyclic olefin compound is performed while removing the generated cyclic olefin compound to an outside of a reaction system.

Description

TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin compound. BACKGROUND ART A cyclic olefin compound is useful as a raw material for a cyclic olefin (co)polymer (COC, COP) which is obtained by copolymerization of a cyclic olefin with lower olefins such as ethylene or ring-opening metathesis polymerization of a cyclic olefin. Various methods have been known for producing the cyclic olefin compound, and among these, there is (1) decarbonylation and decarboxylation reaction of an alicyclic dicarboxylic acid anhydride or (2) oxidative decarboxylation reaction of a dicarboxylic acid derivative obtained by hydrolysis of an alicyclic dicarboxylic acid anhydride. 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 anhydride and its derivatives. In general, as the maleic anhydrides exhibit high reactivity in the Diels-Alder reaction, an adduct is often obtained in a good yield. Therefore, in a case where the decarboxylation and/or decarboxylation can be efficiently carried out from these alicyclic dicarboxylic acid anhydrides or dicarboxylic acid derivatives obtained by hydrolysis thereof, it can be expected that cyclic olefin compounds having various structures can be synthesized in high yields by combining various diene compounds and maleic anhydrides. Examples of the technique relating to the method for producing such a cyclic olefin compound include those disclosed in Patent Document 1 (International Publication No. WO 2008/062553). Patent Document 1 discloses a method for producing a cyclic olefin compound represented by a specific chemical formula via decarbonylation and decarboxylation of an alicyclic dicarboxylic acid anhydride represented by a specific chemical formula, using a nickel complex as a catalyst in the coexistence of a compound which can be a ligand, and removing the generated cyclic olefin compound to an outside of the reaction system. Patent Document 1 discloses that the above-described production method enables significant reduction of an amount of the nickel complex used as a catalyst, and helps to solve problems in known methods, such as high cost due to a large amount of expensive raw materials, low product yields, complicated product separation and purification, and discharge of a large amount of wastes. RELATED DOCUMENT PATENT DOCUMENT [Patent Document 1] International Publication No. WO 2008/062553 SUMMARY OF THE INVENTION TECHNICAL PROBLEM According to studies by the present inventors, it has been found that since the nickel complex catalyst used in Patent Document 1 is in effect a zero-valent compound, it becomes expensive and so unstable that it decomposes in the atmosphere, and that the method for producing a cyclic olefin compound disclosed in Patent Document 1 has room for improvement from the viewpoint of operation and stability in producing the cyclic olefin compound. The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a method for producing a cyclic olefin compound, in which, by using a specific divalent nickel complex, a cyclic olefin compound can be stably produced even in a case where the nickel complex is exposed to the atmosphere. SOLUTION TO PROBLEM That is, according to the present invention, the following methods for producing a cyclic olefin compound are provided. [1] A method for producing a cyclic olefin compound, including: a step of producing a cyclic olefin compound by applying a divalent nickel complex represented by General Formula (1) to decarbonylate and decarboxylate an alicyclic dicarboxylic acid anhydride,in which the divalent nickel complex includes at least one anionic ligand Y represented by any of General Formulae (2) to (7), (X1), and (Y1),         Ni(Y)m(L)n     (1) (here, Ni is divalent nickel, Y is an anionic monodentate or polydentate ligand and has at least one Ni-E covalent bond, E is a heteroatom or a π-bonding group, m is 1 or 2, L is a neutral ligand, and n is a real number of 0 to 6) (R1 is a hydrogen atom or a hydrocarbon group which may have a substituent) (R2 is a divalent hydrocarbon group which may have a substituent) (R3, R4, and R5 are hydrocarbon groups which may have a substituent, R3 and R5 or R4 and R5 may be bonded to each other to form a ring, and R3, R4, and R5 may be hydrogen atoms) (R6 is a divalent hydrocarbon group which may have a substituent, R7 is a hydrogen atom, a hydrocarbon group which may have a substituent, or an oxo group, and in a case where R7 is a hydrocarbon group, R7 may be bonded to R6 to form a ring) (Z' is halogen or OH) (Ox is an oxoacid selected from NO3-, CO32-, and PO43-) (R1', R2' , R3', R4', and R5' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent) (R6', R7', and R8' are each independently a hydrogen atom or a hydrocarb