(19) & (11) EP 2 444 386 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 153(4) EPC (43) Date of publication: (51) Int Cl.: 25.04.2012 Bulletin 2012/17 C07C 45/68 (2006.01) C07C 45/80 (2006.01) C07C 49/617 (2006.01) C07C 49/683 (2006.01) (2006.01) (21) Application number: 10789327.3 C07C 49/798 (22) Date of filing: 13.05.2010 (86) International application number: PCT/JP2010/058133 (87) International publication number: WO 2010/146951 (23.12.2010 Gazette 2010/51) (84) Designated Contracting States: • SONE Hisashi AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Yokohama-shi GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Kanagawa 231-0815 (JP) PL PT RO SE SI SK SM TR • KOIKE Takeshi Designated Extension States: Yokohama-shi BA ME RS Kanagawa 231-0815 (JP) • KAWAHAMA Sayako (30) Priority: 19.06.2009 JP 2009146803 Yokohama-shi Kanagawa 231-0815 (JP) (71) Applicant: JX Nippon Oil & Energy Corporation Chiyoda-ku (74) Representative: HOFFMANN EITLE Tokyo 100-8162 (JP) Patent- und Rechtsanwälte Arabellastraße 4 (72) Inventors: 81925 München (DE) • KOMATSU Shinichi Yokohama-shi Kanagawa 231-0815 (JP) (54) PROCESS FOR PREPARATION OF NORBORNENE DERIVATIVES (57) A method for producing a norbornene derivative, comprising: a first step of forming a Mannich base by reacting a carbonyl compound and an amine compound with each other in an acidic solvent, to thereby obtain a reaction liquid comprising the Mannich base in the acidic solvent, the acidic solvent comprising a formaldehyde derivative and 0.01 mol/L or more of an acid represented by the formula: HX (In the formula, X represents F or the like), the carbonyl compound being represented by any of the following general formulae (1) to (3): EP 2 444 386 A1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 2 444 386 A1 [in formulae (1) to (3), R1, R2, R3, R4, R5, and R6 each independently represent a hydrogen atom or the like, and n represents an integer of any of 0 to 4], the amine compound being represented by the following general formula (4): [in the formula (4), R 7S each independently represent a linear chain saturated hydrocarbon group having 1 to 20 carbon atoms or the like, and X- represents F- or the like], the Mannich base being represented by any of the following general formulae (5) to (7): [R1, R2, R3, R4, R5, R6, and n in the formulae (5) to (7) have the same meanings as those of R 1, R2, R3, R4, R5, R6, and n in the formulae (1) to (3), and R7 and X- in the formulae (5) to (7) have the same meanings as those of R7 and X- in the formula (4)] and a second step of reacting the Mannich base and a diene compound with each other by adding an organic solvent, a base in an amount of 1.0 to 20.0 equivalents to the acid, and the diene compound to the reaction liquid, and then heating the reaction liquid, to thereby form a norbornene derivative, the diene compound being represented by the following general formula (8): 2 (Cont. next page) EP 2 444 386 A1 [in the formula (8), R8 represents a hydrogen atom or the like], the norbornene derivative being represented by any of the following general formulae (9) to (11): [R1, R2, R3, R4, R5, R6, and n in the formulae (9) to (11) have the same meanings as those of R1, R2, R3, R4, R5, R6, and n in the formulae (1) to (3), and R 8 in the formulae (9) to (11) has the same meaning as that of R 8 in the formula (8)]. 3 EP 2 444 386 A1 Description [Technical Field] 5 [TECHNICAL FIELD] [0001] The present invention relates to a method for producing a norbornene derivative. [Background Art] 10 [0002] Cyclic olefin-based polymers produced by using cyclic olef ins as monomers have alicyclic structures in their main chain skeletons. Hence, such a cyclic olefin-based polymer is more likely to be amorphous, exhibits an excellent transparency and heat resistance, has a small photo-elastic coefficient, and also has such properties as a low water absorbing property, acid resistance, alkaline resistance, and a high electrical insulation property. For this reason, use 15 of the cyclic olefin-based polymers has been examined in applications such as display applications (retardation films, diffusion films, liquid-crystal substrates, films for touch panels, light guide plates, protection films for polarizing plates, and the like), optical lens applications, optical disk applications (CD, MD, CD-R, DVD, and the like), optical fiber appli- cations, optical film/sheet applications, and sealing applications for optical semiconductors. Of such cyclic olefin- based polymers, hydrogenated products of cyclic olefin-based polymers obtained by ring opening metathesis polymerization 20 of norbornene derivatives are particularly known to exhibit excellent transparency and heat resistance, and to have a characteristic of a small photo-elastic constant. Hence, such a hydrogenated product, as well as polycarbonate, has been used for retardation films for liquid crystal displays (LCD) and the like. For this reason, development of cyclic olefin- based polymers obtained by using norbornene derivatives has been actively conducted. Under such circumstances, cyclic olefin-based polymers having various structures have been developed. In particular, cyclic olefin- based polymers 25 having a spiro structure, which is one of the cardo structures, and the like have attracted attention, because desired birefringence and wavelength dependence, which are required for retardation films for LCDs, can be controlled freely. [0003] As a method for producing a norbornene derivative having a specific structure such as the spiro- type structure, for example, Japanese Unexamined Patent Application Publication No. 2006-189474 (PTL 1) discloses a method for producing a norbornene derivative having a spiro- type structure, comprising carrying out a Diels- Alder reaction of a vinyl 30 ketone synthesized by a Mannich reaction or the like with cyclopentadiene (Total yield: 53%). Meanwhile, Japanese Unexamined Patent Application Publication No. 2008-7733 (PTL 2) discloses a method for producing a norbornene derivative having a spiro-type structure by utilizing a Diels-Alder addition reaction of cyclopentadiene with an olefin compound (the yield of the vinyl ketone is not shown). In addition, Bulletin de la Societe Chimique de France (5) published in 1966, pages 1693 to 1698 (NPL 1) discloses a method for producing a norbornene having a spiro-type structure, 35 comprising: synthesizing a Mannich base (N,N-dimethylamino methyl-a-tetralone) (yield: 65%) by reacting α-tetralone, which is a cyclic ketone, and dimethylamine hydrochloride in a 35% aqueous formalin solution; and then reacting the Mannich base with cyclopentadiene. Furthermore, Chem. Ber. vol. 117 published in 1984, pages 682 to 693 (NPL 2) discloses a method for producing a norbornene derivative having a spiro-type structure, comprising: synthesizing a Mannich base from a cyclic ketone such as cyclopentanone, cyclohexanone, 1- indanone, or 1-benzosuberone in a usual 40 manner; and then reacting the Mannich base and cyclopentadiene. However, none of the conventional methods for producing a norbornene derivative described in PTLs 1 and 2 and NPLs 1 and 2 is necessarily sufficient from the viewpoint of producing the norbornene derivative in a sufficient yield. [Citation List] 45 [Patent Literature] [0004] 50 [PTL 1] Japanese Unexamined Patent Application Publication No. 2006-189474 [PTL 2] Japanese Unexamined Patent Application Publication No. 2008-7733 [Non Patent Literature] 55 [0005] [NPL 1] Bulletin de la Societe Chimique de France(5), published in 1966, pages 1693 to 1698 4 EP 2 444 386 A1 [NPL 2] Chem. Ber., published in 1984, vol. 117, pages 682 to 693 [Summary of Invention] 5 [Technical Problem] [0006] The present invention has been made in view of the above described problem of the conventional technologies, and an object of the present invention is to provide a method for producing a norbornene derivative, which makes it possible to produce a norbornene derivative having a predetermined structure such as a spiro- type norbornene derivative 10 in a sufficiently high yield. [Solution to Problem] [0007] The present inventors have conducted earnest study to achieve the above-described object, and obtained the 15 following results. Specifically, the present inventors first examined the reasons why the above-described conventional technologies are not capable of producing a norbornene derivative in a sufficient yield, and have found that one of the reasons is as follows. Specifically, a vinyl ketone used as a raw material for producing a spiro norbornene undergoes spontaneous dimerization by a hetero Diels- Alder reaction under a temperature condition of 5 °C or above as described in the following reaction formula: 20 25 30 35 40 45 50 [in the reaction formula, Ra and Rb represent hydrocarbon groups or the like]. Hence, the dimerization of the vinyl ketone proceeds in parallel under an ordinary condition, and thus a vinyl ketone dimer is easily formed. As a result, the yield is lowered due to the dimer formation in the stage of synthesizing the vinyl ketone. Moreover, the present inventors have found that another of the reasons is as follows. Specifically, in the conventional method in which a spiro 55 norbornene is synthesized by preparing a Mannich base as a precursor of a vinyl ketone, isolating the Mannich base, and then subjecting the isolated Mannich base to the Hofmann degradation in the presence of a diene, to thereby generate the vinyl ketone in situ and simultaneously carry out a Diels-Alder reaction, the Mannich base is difficult to utilize sufficiently because of the following reason.