Further, the mixture was concentrated under reduced pressure to distill off the solvent, and 1140 g of chloroform was added. Then, insoluble matter was removed by filtration from the obtained brown-green suspension. The obtained solution was washed with 648 g of saturated sodium hydrogencarbonate aqueous solution three times and further with 240 g of purified water three times. Then, 11 g of anhydrous magnesium sulfate was added to the organic phase and stirred, then 5.4 g of activated carbon was added, stirred and filtered. Then, the obtained solution was filtered and concentrated under reduced pressure to obtain 98 g of a yellow liquid. Subsequently, it was purified by distillation under conditions of 178.6 °C/1 mmHg to obtain 80.5 g of trimethyl bicyclo[2. 2. l]heptane-2,3,5-tricarboxylate (NMTE) (purity 95.8% by weight as determined by GC analysis, yield 80.3%) as a pale yellow oil.
INDUSTRIAL APPLICABILITY [0257]
The present invention relates to a method for producing an alicyclic tetracarboxylic dianhydride and an ester compound. In particular, alicyclic tetracarboxylic dianhydrides are compounds useful as monomers for producing polyimide. According to the present invention, there is provided a method for producing an alicyclic tetracarboxylic dianhydride or ester compound suitable for industrial use, which enables the production of an alicyclic tetracarboxylic acid dianhydride or ester compound such as DNDA with high yield under mild conditions by simple method. In addition, it is possible to provide an alicyclic tetracarboxylic acid dianhydride and an ester compound that are suitable as a monomer for producing a polymer such as polyimide. Furthermore, the complete separation of stereoisomers are not necessary in Step 1 of obtaining an olefin compound from norbornadiene and cyclopentadiene and Step 2 of reacting an olefin compound with an alcohol compound and carbon monoxide to obtain an ester compound, and thus, the alicyclic tetracarboxylic acid dianhydride can be obtained by industrially suitable operation and with industrially suitable purity by crystallization.
69

WE CLAIM:
1. A method for producing an alicyclic tetracarboxylic acid dianhydride, the method comprising:
Step V reacting norbornadiene represented by following formula (l) with cyclopentadiene represented by following formula (2) to obtain an olefin compound represented by following formula (3);
Step 2: subsequently, reacting the olefin compound represented by formula (3), an alcohol compound and carbon monoxide in the presence of a palladium compound and a copper compound to obtain an ester compound represented by following formula (4);
Step 3, subsequently reacting the ester compound represented by formula (4) in the presence of an acid in an organic solvent to obtain an alicyclic tetracarboxylic acid dianhydride represented by following formula
(5);
wherein,
in Step 2, at least one of following two operations (A) and (B) is performed;
(A) mixing the palladium compound, the copper compound, and the alcohol compound in a reaction vessel, and then carrying out a substitution operation of (C-2) and a stirring operation of (C-l) sequentially, to mix with the olefin compound represented by formula (3);
(B) mixing the palladium compound, the copper compound, the alcohol compound and an orthoester compound in a reaction vessel, and then carrying out a substitution operation of (C-2), to mix with the olefin compound represented by formula (3);
(C-l) stirring under an atmosphere of carbon monoxide!
(C-2) performing one or more times of an operation of filling with carbon
monoxide gas after reducing pressure in the reaction vessel;

wherein, R represents an alkyl group having 1 to 10 carbon atoms;
2. The method for producing an acid dianhydride according to claim 1, wherein in Step 2, a content of a compound represented by following formula (6) in the olefin compound represented by formula (3) to be used is 50 to 99% by weight;
n
3. The method for producing an acid dianhydride according to claim 1 or 2, wherein when mixing with the olefin compound in the operations (A) and (B) of Step 2, the olefin compound represented by formula (3) is added dropwise to (i) a mixture containing the palladium compound, the copper compound and the alcohol compound, or (ii) a mixture containing the palladium

compound, the copper compound, the alcohol compound, and the orthoester compound.
4. A method for producing an ester compound, the method comprising reacting an olefin compound represented by following general formula (7), an alcohol compound and carbon monoxide in the presence of a palladium compound and a copper compound to obtain an ester compound represented by following general formula (7"l), wherein
at least one of following two operations (A) and (B) is performed;
(A) mixing the palladium compound, the copper compound, and the alcohol compound in a reaction vessel, and then carrying out a substitution operation of (02) and a stirring operation of (Ol) sequentially, to mix with the olefin compound;
(B) mixing the palladium compound, the copper compound, the alcohol compound and an orthoester compound in a reaction vessel, and then carrying out a substitution operation of (C-2), to mix with the olefin compound;

(1) stirring under an atmosphere of carbon monoxide;
(2) performing one or more times of an operation of filling with carbon monoxide gas after reducing pressure in the reaction vessel;
wherein, R1 is an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 1 to 15 carbon atoms; three RA's may be the same or different each other, and two or more of R^s may be bonded to each other to form one or more rings together with carbon atoms to which they are bonded; hydrogen atom on the alkyl group may be substituted with alkenyl group having 1 to 5 carbon atoms, ester group represented by -COORa, aryl group having 6 to 15 carbon atoms, alkoxy group represented by -ORb, a cyano group, or -OSCbR0, and carbon atom in the alkyl group may form a carbonyl group; hydrogen atom on the aryl group may be substituted with phenyl group, alkyl group

having 1 to 10 carbon atoms, or alkenyl group having 1 to 10 carbon atoms; and Ra, Rb and Rc each is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms;
wherein R1 has the same meaning as defined above, and R represents an alkyl group having 1 to 10 carbon atoms.
5. The method for producing an ester compound according to claim 4, wherein when mixing with the olefin compound in the operations (A) and (B), the olefin compound is added dropwise to (i) a mixture containing the palladium compound, the copper compound and the alcohol compound, or (ii) a mixture containing the palladium compound, the copper compound, the alcohol compound, and the orthoester compound.
6. The method for producing an ester compound according to claim 4 or 5, wherein the olefin compound and the ester compound are respectively represented by following formulae (8) and (8-1), following formulae (9) and (9-l), following formulae (10) and (l0-l), following formulae (ll) and (ll-l), following formulae (11-2) and (ll"3), following formulae (12) and (l2-l), following formulae (13) and (l3-l), following formulae (14) and (l4-l), following formulae (15) and (l5-l), following formulae (16) and (l6-l), or following formulae (ll) and (l7-l);
wherein R2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an ester group represented by -COORd, or a cyano group; hydrogen atom on the alkyl group may be substituted with an ester group represented by -COORa or an aryl group having 6 to 10 carbon atoms; two R2's may be the

same or different each other, and may be bonded to each other to form one or more rings together with carbon atoms to which they are bonded; Rd and Ra in the ester group are an alkyl group having 1 to 10 carbon atoms or an aryl groups having 6 to 10 carbon atoms; and R represents an alkyl group having 1 to 10 carbon atoms;
wherein R3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group or an ester group represented by -COORd; hydrogen atom on the alkyl group may be substituted with an ester group represented by -COORa or an aryl group having 6 to 10 carbon atoms; two R3's may be the same or different each other, and may be bonded to each other to form one or more rings together with carbon atoms to which they are bonded; Rd and Ra in the ester groups are an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; and R represents an alkyl group having 1 to 10 carbon atoms;
wherein R4 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; two R4's may be the same or different each other, and may be bonded to each other to form one or more rings together with carbon atoms to which they are bonded; R represents an alkyl group having 1 to 10 carbon atoms;

wherein R5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group represented by -ORb, or a group represented by -OS02Rc; Rb represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, Rc represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; two R5's may be the same or different each other, and may be bonded to each other to form one or more rings together with carbon atoms to which they are bonded; R represents an alkyl group having 1 to 10 carbon atoms;
wherein, R represents an alkyl group having 1 to 10 carbon atoms;
wherein R6 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms; six R6's may be the same as or different each other, and two or more of R6's may be bonded to each other to form one or more rings together with carbon atoms to which they are bonded; R represents an alkyl group having 1 to 10 carbon atoms;
wherein R7 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms; three R7's may be the same or different each

other, and two or more of R7's may be bonded to each other to form one or more rings together with carbon atoms to which they are bonded? R represents an alkyl group having 1 to 10 carbon atoms;
wherein R8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms?' four R8's may be the same or different each other, and two or more of R8's may be bonded to each other to form one or more rings together with carbon atoms to which they are bonded; R represents an alkyl group having 1 to 10 carbon atoms?'
wherein R9 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms?' three R9's may be the same or different each other, and two or more of R9's may be bonded to each other to form one or more rings together with the carbon atoms to which they are bonded?' R represents an alkyl group having 1 to 10 carbon atoms?'
wherein, R represents an alkyl group having 1 to 10 carbon atoms?'
wherein, R represents an alkyl group having 1 to 10 carbon atoms.

7. An ester compound represented by following formula (18);
wherein R10 may be the same or different and represents a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.
8. An olefin compound represented by following formula (19);
wherein, Ms represents a mesyl group represented by -SO2CH3. 9. An ester compound represented by following formula (20);
wherein, Ms represents a mesyl group represented by -SO2CH3; and R11 may be the same or different, and represents a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.
77