TECHNICAL FIELD
[0001]
The present invention relates to a method for producing a
cyclic olefin compound.
10 BACKGROUND ART
[0002]
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
15 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
20 reaction of a dicarboxylic acid derivative obtained by
hydrolysis of an alicyclic dicarboxylic acid anhydride.
[0003]
The alicyclic dicarboxylic acid anhydride used as a raw
material for these reactions can be obtained by a Diels-Alder
25 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,
2
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
5 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.
[0004]
10 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).
[0005]
15 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
20 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
25 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
3
of a large amount of wastes.
RELATED DOCUMENT
PATENT DOCUMENT
5 [0006]
[Patent Document 1] International Publication No. WO
2008/062553
SUMMARY OF THE INVENTION
10 TECHNICAL PROBLEM
[0007]
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
15 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.

CLAIMS
1. A method for producing a cyclic olefin compound, comprising:
a step of producing a cyclic olefin compound by acting a
5 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
10 (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
15 neutral ligand, and n is a real number of 0 to 6)
[Chem. 1]
(R1 is a hydrogen atom or a hydrocarbon group which may have
a substituent)
20 [Chem. 2]
(R2 is a divalent hydrocarbon group which may have a
69
substituent)
[Chem. 3]
(R3, R4, and R5 are hydrocarbon groups which may have a
5 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)
[Chem. 4]
(R6 is a divalent hydrocarbon group which may have a
10 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)
[Chem. 5]
15 (Z’ is halogen or OH)
[Chem. 6]
(Ox is an oxoacid selected from NO3-, CO3
2-, and PO4
3-)
70
[Chem. 7]
(R1’, R2’, R3’, R4’, and R5’ are each independently a
hydrogen atom or a hydrocarbon group which may have a
5 substituent)
[Chem. 8]
(R6’, R7’, and R8’ are each independently a hydrogen atom or
a hydrocarbon group which may have a substituent).
10
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),
15 (11) to (13), and (Z1), and Formulae (8) and (10),
[Chem. 9]
71
[Chem. 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
5 hydrocarbon group which may have a substituent)
[Chem. 11]
[Chem. 12]
10 (R7 and R8 are each independently a hydrogen atom or a
hydrocarbon group which may have a substituent, and R7 and R8 may
be bonded to each other to form a ring)
[Chem. 13]
72
(R9 and R10 are each independently a hydrogen atom or a
hydrocarbon group which may have a substituent, and R9 and R10
may be bonded to each other to form a ring)
5 [Chem. 14]
(Z’’ is Cl or Br)
[Chem. 15]
.
10
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
15 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,
73
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
5 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
10 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),
[Chem. 16]
15
(X1, X2, and X3 are each independently a hydrocarbon group
which may have a substituent)
[Chem. 17]
20 (X4, X5, X6, and X7 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).
74
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
5 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.
10
9. The method for producing a cyclic olefin compound according
to Claim 8,
wherein a boiling point of the alcohol compound is lower
than a boiling point of the alicyclic dicarboxylic acid
15 anhydride.
10. The method for producing a cyclic olefin compound according
to any one of Claims 1 to 9,
wherein the alicyclic dicarboxylic acid anhydride includes
20 at least one of a carboxylic acid compound or a carboxylic acid
anhydride (excluding the alicyclic dicarboxylic acid anhydride)
as an impurity.
11. The method for producing a cyclic olefin compound according
25 to Claim 10, further comprising:
a step of adding an alcohol compound; and
a step of contacting the alcohol compound with the impurity
75
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.
5 12. The method for producing a cyclic olefin compound according
to Claim 11,
wherein a boiling point of the alcohol compound is lower
than a boiling point of the alicyclic dicarboxylic acid
anhydride.
10
13. The method for producing a cyclic olefin compound according
to any one of Claims 1 to 12,
wherein the alicyclic dicarboxylic acid anhydride includes
a compound represented by General Formula (16), and
15 the cyclic olefin compound includes a compound represented
by General Formula (17),
[Chem. 18]
(X is a group of non-metal atoms required to form a ring,
20 and R and R’ are each independently a hydrogen atom or a
hydrocarbon group which may have a substituent)
[Chem. 19]
76
(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).
5
14. The method for producing a cyclic olefin compound according
to any one of Claims 1 to 13,
wherein the alicyclic dicarboxylic acid anhydride includes
5,6-benzo-2,3-dicarboxylic acid anhydrides represented by
10 General Formula (18),
[Chem. 20]
(R11, R12, R13, R14, R15, R16, and R17 are each independently a
hydrogen atom or a substituent which may have a heteroatom).
15
15. The method for producing a cyclic olefin compound according
to Claim 14,
wherein R11, R12, R13, R14, R15, R16, and R17 in General Formula
(18) are all hydrogens.
20
16. The method for producing a cyclic olefin compound according
77
to any one of Claims 1 to 13,
wherein the alicyclic dicarboxylic acid anhydride includes
a dicarboxylic acid anhydride represented by General Formula
(19),
5 [Chem. 21]
(n is 0 or 1, and X’ is O or CH2).
17. The method for producing a cyclic olefin compound according
10 to any one of Claims 1 to 16,
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.