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Process for Producing Fused-Ring Aromatic Compound, and Conjugated Polymer

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Process for Producing Fused-Ring Aromatic Compound, and Conjugated Polymer (19) TZZ ¥__T (11) EP 2 774 931 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 153(4) EPC (43) Date of publication: (51) Int Cl.: 10.09.2014 Bulletin 2014/37 C07F 19/00 (2006.01) C07F 7/08 (2006.01) C07F 7/22 (2006.01) C07F 7/30 (2006.01) (2006.01) (2014.01) (21) Application number: 12844675.4 C08G 61/12 H01L 31/04 (22) Date of filing: 02.11.2012 (86) International application number: PCT/JP2012/078517 (87) International publication number: WO 2013/065836 (10.05.2013 Gazette 2013/19) (84) Designated Contracting States: • KAWAI, Jyunya 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 227-8502 (JP) PL PT RO RS SE SI SK SM TR •SATO,Wataru Yokohama-shi (30) Priority: 02.11.2011 JP 2011241498 Kanagawa 227-8502 (JP) 29.11.2011 JP 2011260973 • SATAKE, Kenichi Yokohama-shi (71) Applicant: Mitsubishi Chemical Corporation Kanagawa 227-8502 (JP) Chiyoda-ku • FURUYA, Mitsunori Tokyo 100-8251 (JP) Yokohama-shi Kanagawa 227-8502 (JP) (72) Inventors: • FUJITA, Rieko (74) Representative: HOFFMANN EITLE Yokohama-shi Patent- und Rechtsanwälte Kanagawa 227-8502 (JP) Arabellastrasse 4 81925 München (DE) (54) PROCESS FOR PRODUCING FUSED-RING AROMATIC COMPOUND, AND CONJUGATED POLYMER (57) The invention addresses a problem of purifying having n active groups (wherein n is an integer of 1 or a monomer to be a precursor according to a simpler and more and 4 or less), which comprises bringing a compo- milder method so as to obtain a polymer having a higher sition containing the condensed polycyclic aromatic com- molecular weight. The invention relates to a method for pound and a solvent into contact with zeolite. producing a condensed polycyclic aromatic compound EP 2 774 931 A1 Printed by Jouve, 75001 PARIS (FR) EP 2 774 931 A1 Description Technical Field 5 [0001] The present invention relates to a method for producing a condensed polycyclic aromatic compound and to a conjugated polymer. Background Art 10 [0002] As semiconductor materials for devices such as organic EL devices, organic thin film transistors, organic light- emitting sensors and the like, π-conjugated polymers are used, and above all, attention is focused on application thereof to polymer organic solar cells. In particular, in organic solar cells, there have been reported a lot of cases of using a copolymer of a donor-like monomer and an acceptor-like monomer (hereinafter this may be referred to as a copolymer) in a photoelectric conversion element. 15 [0003] Examples of the donor-like monomer skeleton include, for example, those described in NPL 1 and NPL 2. In these publications, there are disclosed copolymers produced through coupling polymerization of a condensed polycyclic structure-having monomer in which at least three 5-membered rings are condensed, such as dithieno[3,2-b:2’,3’-d]silole, and any other monomer. It is reported that an organic solar cell using the copolymer exhibits a high photoelectric conversion efficiency of more than 5%. 20 Citation List Non-Patent Literature 25 [0004] NPL 1: J. Am. Chem. Soc., 2008, 130, 16144-16415. NPL 2: J. Am. Chem. Soc., 2011,133,4250-4253. NPL 3: Chem. Commun., 2010,46,6335-6337. 30 NPL 4: Chem. Commun., 2004,1968-1969. Summary of Invention Technical Problem 35 [0005] For developing a higher-performance device, it is desired to obtain a polymer having a higher molecular weight. For obtaining a copolymer having a higher molecular weight, it is important to use monomers having a higher purity. However, the purification method through GPC (gel permeation chromatography) that has heretofore been employed in the art is unsuitable to industrial mass-production of monomers. 40 [0006] Investigations made by the present inventors have revealed that relatively unstable monomers often undergo substituent removal under ordinary purification conditions in a method of leading the monomer to pass through a silica gel column (NPL 3), a method of leading the monomer to pass through a silica gel/potassium fluoride column (NPL 4) or the like. [0007] An object of the present invention is to purify and produce a monomer to be a precursor in a simpler and milder 45 method so as to give a polymer having a higher molecular weight. Solution to Problem [0008] For solving the above-mentioned problems, the present inventors have assiduously studied and, as a result, 50 have found that purification of monomers by the use of zeolite provides a material capable of giving a polymer having a higher molecular weight. [0009] Specifically, the gist of the invention is as follows. 1. A method for producing a condensed polycyclic aromatic compound having n active groups (wherein n is an 55 integer of 1 or more and 4 or less), which comprises bringing a composition containing the condensed polycyclic aromatic compound and a solvent into contact with zeolite. 2. The method for producing a condensed polycyclic aromatic compound according to the item 1 above, wherein the condensed polycyclic aromatic compound satisfies the following requirement: 2 EP 2 774 931 A1 Requirement: When 5 ml of a hexane solution containing 1.0 g of the condensed polycyclic aromatic compound (Ar(n)) having n active groups is charged in a column (having an inner diameter 15 mm, and charged with 50 mL of a hexane solution containing 20 g of silica gel (spherical, neutral (pH 7.06 0.5), and having a particle size of from 63 to 210 mm) and 2 g of anhydrous potassium carbonate) and developed with a developing solvent of hexane 5 (at a flow rate of 50 ml/min), the total proportion of the condensed polycyclic aromatic compound in which the number of the active groups is smaller than n in the solution having passed through the column in 3 minutes at room temperature is 5 mol% or more relative to the aromatic compound (Ar(n)) before charged in the column. 3. The method for producing a condensed polycyclic aromatic compound according to the item 1 or 2 above, wherein the condensed polycyclic aromatic compound is a condensed polycyclic aromatic compound represented by the 10 following formula (I): 15 20 25 30 (In the formula (I), the Ring A and the Ring B each independently represent a 5-membered aromatic hetero ring, 35 and the Ring C represents a ring optionally having a substituent, X 1 and X2 each independently represent an active group, R1 and R 2 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group optionally having a hetero atom.) 4. The method for producing a condensed polycyclic aromatic compound according to the item 3 above, wherein the compound represented by the formula (I) is a condensed polycyclic aromatic compound represented by the 40 following formula (II) or formula (III): 45 50 55 (In the formula (II) and the formula (III), X1, X2, R1, R2 and the Ring C have the same meanings as in the formula (I), and X 11 and X 21 each independently represent an atom selected from Group 16 elements of the Periodic Table.) 3 EP 2 774 931 A1 5. The method for producing a condensed polycyclic aromatic compound according to the item 4 above, wherein the compound represented by the formula (II) or the formula (III) is a condensed polycyclic aromatic compound represented by the following formula (IV), formula (V), formula (VI) or formula (VII): 5 10 15 in the formula (IV), formula (V), formula (VI) or formula (VI), X1, X2, R1 and R2 have the same meanings as in the formula (I), in the formula (IV), Z1 represents Z11(R3)(R4), Z12(R5), or Z13, Z11 represents an atom selected from Group 14 20 elements of the Periodic Table, R3 and R4 are the same as the above-mentioned R1 and R2, Z12 represents an atom selected from Group 15 elements of the Periodic Table, R 5 has the same meaning as R 3 and R 4. Z13 represents an atom selected from Group 16 elements of the Periodic Table, in the formula (V), R6 and R7 each represent a hydrogen atom, a halogen atom, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, an 25 aromatic group optionally having a substituent, an alkoxy group optionally having a substituent, or an aryloxy group optionally having a substituent, in the formula (VI), R8 to R11 have the same meanings as R3 and R4; and R12 and R13 have the same meanings as R 1and R 2.Z 2and Z 3 eachindependently representan atom selectedfrom Group14 elements of the Periodic Table, in the formula (VII), R 14 and R 15 have the same meanings as R 3 and R 4. Z4 represents an atom selected from Group 30 16 elements of the Periodic Table. 6. The method for producing a condensed polycyclic aromatic compound according to any one of the items 3 to 5 above, wherein at least one of X 1 and X2 is a tin-containing group. 7. The method for producing a condensed polycyclic aromatic compound according to any one of the items 3 to 6 above, which, in the condensed compound represented by the formula (II), comprises producing the condensed 35 polycyclic aromatic compound represented by the formula (I) through reaction of a condensed polycyclic aromatic compound represented by the following formula (VIII) with a non-nucleophilic base followed by reaction thereof with an electrophilic reagent: 40 45 50 55 (In the formula (VIII), the Ring A, the Ring B, the Ring C, R 1 and R2 have the same meanings as in the formula (I).) 4 EP 2 774 931 A1 8.
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