Substituted polyacetylene having ketocoumarin skeleton and method for producing the same

Abstract

To provide a new substituted polyacetylene having a ketocoumarin skeleton, which is expected to be applied to a photo-electroluminescent material, and to provide an industrially advantageous method for producing the same.SOLUTION: The substituted polyacetylene has a ketocoumarin skeleton containing a repeating unit represented by general formula (1). (In the formula, R1 represents a group selected from alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, alkoxy groups, amino groups, carbonyl groups, carboxy groups, hydroxy groups, and nitro groups, and the alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, alkoxy groups, and amino groups may have substituents. X represents a halogen atom. N represents an integer of 0 to 3. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a substituted polyacetylene having a ketocoumarin skeleton and a method for producing the same. [Background technology]

[0002] Coumarin, a lactone, is one of the many naturally occurring fragrance components and is a molecular skeleton that is widely used as a raw material for cosmetics, fragrances, and pharmaceuticals (see, for example, Non-Patent Document 1). Furthermore, molecules with a coumarin skeleton are known to not only exhibit excellent luminescence in the visible light region, but also exhibit antibacterial and antioxidant activities, and have been widely studied for applications in the fields of photoelectroluminescence and medicine (see, for example, Non-Patent Documents 2 and 3).

[0003] On the other hand, polymer compounds are widely used as materials that not only possess diverse functionalities that cannot be realized with small molecules but also have excellent moldability and film-forming properties. Against this background, attempts to develop materials with higher functionality by introducing functional molecular skeletons into polymers have been actively conducted. In particular, polyacetylene, a type of conjugated polymer compound, has been widely studied as a functional material that exhibits excellent optoelectronic functions, such as photoelectroluminescence, and gas permeability, due to its conjugated structure (see, for example, Non-Patent Documents 4 and 5).

[0004] Photon upconversion (also known as "UC") is a technology that converts low-energy light into high-energy light, making it possible to effectively utilize infrared and visible light, which have been considered difficult to utilize until now. This is expected to improve the performance of energy conversion devices such as solar power generation. Known UC material systems include those that combine a donor that functions as a sensitizer and an acceptor that functions as an emitter. UC due to triplet-triplet annihilation, which is caused by energy transfer between a donor that functions as a sensitizer and an acceptor that functions as an emitter, has been widely studied.

[0005] However, many of the conventional UC material donors have used compounds containing heavy atoms such as palladium or platinum, and development of donors that do not contain heavy atoms is underway due to considerations of the environment and reducing the use of precious metals. For example, Patent Document 1 proposes using a ketocoumarin derivative represented by the following general formula (A) as a donor molecule.

[0006] [ka] (In the formula, A1~A 10 represents a hydrogen atom or a substituent. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2023 / 037848 Brochure [Non-patent literature]

[0008] [Non-Patent Document 1] Polymers,2020,13,56. [Non-patent document 2] Molecules,2021,26,501. [Non-patent document 3] Nat. Commun.,2021,12,2873. [Non-patent document 4] Top Curr Chem,2017,375,72. [Non-patent document 5] Molecules, 2023, 28, 2748. Summary of the Invention [Problem to be solved by the invention]

[0009] According to Patent Document 1, a UC material system using a ketocoumarin derivative as a donor molecule and a specific compound as an acceptor exhibits a high UC quantum yield at low excitation light intensity, despite not containing heavy atoms such as palladium or platinum.

[0010] The UC in Patent Document 1 is explained by a mechanism in which triplet-triplet energy transfer from a triplet-excited sensitizer (donor molecule) to an emitter (acceptor molecule) generates an emitter in a triplet excited state, followed by triplet-triplet annihilation between emitters in the triplet excited state. Because this UC proceeds via the Dexter mechanism, molecular diffusion and collision within the system are essential, and studies have mainly been conducted in solution systems. However, to develop a practical UC material, it is necessary to realize UC in a solid system.

[0011] Furthermore, according to Non-Patent Document 3, photopolymerization reactions using ketocoumarin derivatives as sensitizers can be utilized in high-resolution 3D printers. Thus, ketocoumarin derivatives are useful molecular skeletons for photo-electroluminescent materials, and incorporating these derivative moieties into polymers is expected to enhance the functionality of the polymers.

[0012] The object of the present invention is to provide a novel substituted polyacetylene having a ketocoumarin skeleton, which is expected to be applied to photo-electroluminescent materials, and an industrially advantageous method for producing the same. [Means for solving the problem]

[0013] While investigating polymer compounds that exhibit optical functionality, the inventors discovered a novel conjugated polymer that is expected to be used as a photo-electroluminescent material, leading to the completion of the present invention.

[0014] A first aspect that the present invention provides is a substituted polyacetylene having a ketocoumarin skeleton containing a repeating unit represented by the following general formula (1).

[0015] [ka] (In the formula, R 1 represents a group selected from an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an amino group, a carbonyl group, a carboxy group, a hydroxy group, and a nitro group, and the alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, and amino group may have a substituent. X represents a halogen atom. n represents an integer of 0 to 3.

[0016] A second aspect of the present invention is a method for producing a substituted polyacetylene having a ketocoumarin skeleton containing a repeating unit represented by the following general formula (1), which comprises carrying out a polymerization reaction of a substituted acetylene compound having a ketocoumarin skeleton represented by the following general formula (2) in the presence of a polymerization initiator comprising a transition metal catalyst.

[0017] [ka] (In the formula, R 1 represents a group selected from an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an amino group, a carbonyl group, a carboxy group, a hydroxy group, and a nitro group, and the alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, and amino group may have a substituent. X represents a halogen atom. n represents an integer of 0 to 3.

[0018] [ka] (R in the formula 1 , X and n have the same meanings as in general formula (1).

[0019] A third aspect of the present invention is a substituted acetylene compound having a ketocoumarin skeleton represented by the following general formula (2a).

[0020] [ka] (In the formula, R 1a represents a tertiary amino group. a indicates a halogen atom. a represents an integer from 0 to 3.) [Effects of the Invention]

[0021] The present invention provides a novel substituted polyacetylene having a ketocoumarin skeleton that is expected to be applicable to photoelectroluminescent materials. Furthermore, the production method of the present invention enables the industrially advantageous production of a substituted polyacetylene having a ketocoumarin skeleton. [Brief explanation of the drawings]

[0022] [Figure 1] 1 shows the UV-vis spectrum and emission spectrum of the substituted polyacetylene obtained in Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0023] The present invention will be described below based on preferred embodiments thereof. The substituted polyacetylene having a ketocoumarin skeleton of the present invention (hereinafter, may be simply referred to as "substituted polyacetylene") contains a repeating unit represented by the following general formula (1).

[0024] [ka] (In the formula, R 1 represents a group selected from an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an amino group, a carbonyl group, a carboxy group, a hydroxy group, and a nitro group, and the alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, and amino group may have a substituent. X represents a halogen atom. n represents an integer of 0 to 3.

[0025] R in general formula (1) 1represents a group selected from an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an amino group, a carbonyl group, a carboxy group, a hydroxy group, and a nitro group, and the alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, and amino group may have a substituent.

[0026] In the present invention, unsubstituted and substituted alkyl groups, unsubstituted and substituted cycloalkyl groups, unsubstituted and substituted aryl groups, unsubstituted and substituted heteroaryl groups, unsubstituted and substituted aralkyl groups, unsubstituted and substituted alkoxy groups, and unsubstituted and substituted amino groups will hereinafter be collectively referred to as alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, alkoxy groups, and amino groups, respectively.

[0027] Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms. Specific examples include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, tert-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and 5-methylpentyl groups.

[0028] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 16 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cycloheptyl, 2-methylcyclohexyl, 3-methylcyclohexyl, and 4-methylcyclohexyl groups. The cycloalkyl group also includes polycyclic cycloalkyl groups. Examples thereof include menthyl, bornyl, and norbornyl groups.

[0029] Examples of the aryl group include aryl groups having a carbon number of 6 to 16. Specific examples include a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a naphthyl group, and an anthryl group.

[0030] Examples of the heteroaryl group include 5- or 6-membered monocyclic and polycyclic aromatic heterocyclic groups containing 1 to 3 heteroatoms such as nitrogen atoms, oxygen atoms, and / or sulfur atoms. Specific examples include pyridyl, imidazolyl, thiazolyl, furfuryl, pyranyl, furyl, benzofuryl, and thienyl groups.

[0031] Examples of the aralkyl group include aralkyl groups having 7 to 12 carbon atoms. Specific examples include benzyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, 1-phenylpentyl, 2-phenylpentyl, 3-phenylpentyl, 4-phenylpentyl, 5-phenylpentyl, 1-phenylhexyl, 2-phenylhexyl, 3-phenylhexyl, 4-phenylhexyl, 5-phenylhexyl, and 6-phenylhexyl groups.

[0032] Examples of the alkoxy group include groups in which the alkyl group, cycloalkyl group, aryl group, heteroaryl group, and aralkyl group are bonded to oxygen, such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, phenyloxy group, benzyloxy group, and p-methoxybenzyloxy group.

[0033] Examples of the amino group include linear or branched amino groups such as amino, dimethylamino, diethylamino, di-n-propyl, di-isopropylamino, di-n-butylamino, di-2-butylamino, di-isobutylamino, di-tert-butylamino, di-n-pentylamino, di-2-pentylamino, di-tert-pentylamino, di-2-methylbutylamino, di-3-methylbutylamino, di-2,2-dimethylpropylamino, di-n-hexylamino, di-3-hexylamino, di-tert-hexylamino, di-2-methylpentylamino, di-3-methylpentylamino, di-4-methylpentylamino, and di-5-methylpentylamino.

[0034] Examples of the carbonyl group include an aldehyde group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group.

[0035] Examples of the halogen atom represented by X in general formula (1) include bromine, chlorine, and iodine. In the present invention, X is preferably a bromine atom. Furthermore, n in the formula represents an integer of 0 to 3, and preferably 0 to 2.

[0036] In the present invention, R in the general formula (1) 1 is preferably a tertiary amino group, particularly preferably a dimethylamino group, a diethylamino group, or a di-tert-butylamino group, and more preferably a diethylamino group. That is, a particularly preferred repeating unit of the substituted polyacetylene having a ketocoumarin skeleton represented by the general formula (1) is a repeating unit represented by the following general formula (1a):

[0037] [ka]

[0038] The substituted polyacetylene of the present invention preferably has a number average molecular weight of 1,000 to 1,000,000, more preferably 5,000 to 500,000, and particularly preferably 5,000 to 100,000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 20 or less, more preferably 6 or less, and particularly preferably 1.1 to 2.

[0039] The method for producing the substituted polyacetylene having a ketocoumarin skeleton of the present invention will be described below. The method for producing the substituted polyacetylene represented by the general formula (1) involves polymerizing a substituted acetylene compound having a ketocoumarin skeleton represented by the following general formula (2) (hereinafter, sometimes simply referred to as a "substituted acetylene compound") in a solvent in the presence of a polymerization initiator consisting of a transition metal catalyst.

[0040] [ka] (R in the formula 1 , X and n have the same meanings as in general formula (1).

[0041] In the present invention, R in the general formula (2) 1 is preferably a tertiary amino group, particularly preferably a dimethylamino group, a diethylamino group, or a di-tert-butylamino group, and even more preferably a diethylamino group. That is, a preferred compound as the substituted acetylene compound represented by the general formula (2) is a compound represented by the following general formula (2a), which is a novel compound.

[0042] [ka] (In the formula, R 1a represents a tertiary amino group. a indicates a halogen atom. a represents an integer from 0 to 3.)

[0043] R in general formula (2a) 1a Examples of the tertiary amino group represented by R include a dimethylamino group, a diethylamino group, and a di-tert-butylamino group. 1a is particularly preferably a diethylamino group.

[0044] X in general formula (2a) a Examples of the halogen atom represented by the formula (I) include bromine, chlorine, and iodine. a is preferably a bromine atom. a represents an integer of 0 to 3, preferably 0 to 2.

[0045] The substituted acetylene compound represented by the general formula (2) can be produced, for example, according to the following reaction scheme (1).

[0046] [ka] (R in the formula 1 , X and n have the same meanings as in general formula (1).

[0047] The polymerization reaction of the substituted acetylene compound represented by the general formula (2) is preferably carried out in a solvent, and the solvent can be used without any particular limitation as long as it can dissolve the raw materials and is inert to the product. Examples of the solvent include tetrahydrofuran, N,N-dimethylformamide, toluene, dichloromethane, chloroform, acetonitrile, etc., and these can be used in combination of two or more kinds.

[0048] The polymerization reaction of the substituted acetylene compound represented by the general formula (2) is preferably carried out in the presence of a polymerization initiator consisting of a transition metal catalyst. Any catalyst can be used without particular limitation as long as it is inert to the substituted acetylene compound of the present invention and promotes the polymerization reaction. Examples of such catalysts include molybdenum chloride (V), tungsten chloride (VI), niobium chloride (V), tantalum chloride (V), chloronorbornadiene rhodium (I) (dimer), 1,5-norbornadiene rhodium (I) tetraphenylborate, and 1,5-norbornadiene (phenylethynyl) bistriphenylphosphine rhodium (I). Further examples include phosphine-rhodium complexes and phosphine-palladium complexes described in JP-A Nos. 2017-203053, 2014-162745, 2013-47198, 2012-72124, and 2012-46706.

[0049] The molar ratio of the substituted acetylene compound represented by the general formula (2) to the polymerization initiator is preferably 10 to 1,000, and more preferably 50 to 500.

[0050] In many cases, the reaction temperature for the polymerization reaction is preferably 0 to 100° C., more preferably 20 to 90° C. Furthermore, the reaction time is often 1 hour or longer, preferably 3 to 36 hours.

[0051] After the polymerization reaction is completed, the reaction solvent is removed by a conventional method, and if necessary, purification such as reprecipitation is carried out to obtain the desired substituted polyacetylene represented by the general formula (1).

[0052] The number average molecular weight of the resulting substituted polyacetylene represented by the general formula (1) is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, and particularly preferably 5,000 to 100,000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 20 or less, more preferably 6 or less, and particularly preferably 1.1 to 2.

[0053] The substituted polyacetylene having a ketocoumarin skeleton represented by the general formula (1) of the present invention is particularly useful as a photo-electroluminescent material, and from the viewpoint of exhibiting further functionality, it can also be copolymerized with other acetylene compounds to obtain a copolymer. [Example]

[0054] The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

[0055] [Example 1] <Synthesis of compound (A3)> A 100 mL flask equipped with a thermometer and Dimroth trap was charged with compound (A1) (4-dimethylamino-2-hydroxybenzaldehyde: 5.80 g, 30.0 mmol), degassed, and purged with argon. Ultra-dehydrated methanol (30.0 mL) and compound (A2) (1,3-dimethyl acetonedicarboxtlate; 6.07 g, 30.0 mmol) were added via syringe. Then, piperazine (0.06 mL, 0.60 mmol) was added. The reaction vessel was transferred to an oil bath and stirred at 65 °C for 2 hours. After the reaction was complete, the solution was cooled to room temperature and concentrated to obtain an orange solid. Recrystallization from ethanol (400 mL) yielded 7.34 g (77% yield) of orange solid (A3). (Identification data of compound (A3)) 1 H-NMR (500MHz, CDCl3): δ(ppm)1.25(t,J=7.2Hz,6H),3.44-3.49(m,4H),3.75(s,3H) ,4.11(s,2H),6.46-6.47(m,1H),6.61-6.64(m,1H),7.39-7.43(m,1H),8.50(s,1H).

[0056] [ka]

[0057] <Synthesis of compound (A6)> A 100 mL flask was charged with compound (A4) (4-bromo-2-hydroxybenzaldehyde; 4.02 g, 20.0 mmol), Pd(PPh3)2Cl2 (dichlorobis(triphenylphosphine)palladium(II); 140.4 mg, 0.20 mmol), XPhos (Bachwald ligand, Nippon Chemical Industry Co., Ltd.; 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl; 190.6 mg, 0.40 mmol), and CuI (38.1 mg, 0.20 mmol). The flask was degassed and purged with argon. Ultra-dehydrated toluene (30.0 mL) and dehydrated triethylamine (10.0 mL) were added via syringe and stirred at room temperature for 10 min. Then, trimethylsilylacetylene (A5) (3.4 mL, 24.0 mmol) was added via syringe. The reaction vessel was transferred to an oil bath and stirred at 60°C for 2.5 hours and then at 80°C overnight. After the reaction was completed, the solution was cooled to room temperature and concentrated to obtain a solid. The obtained solid was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 20 / 1 (v / v)) to obtain 4.03 g (yield 92%) of a yellow solid, 4-(2-(trimethylsilyl)ethynyl)-2-hydroxybenzaldehyde (A6). (Identification data of compound (A6)) 1 H-NMR (500MHz, CDCl3): δ(ppm) 0.26(s,9H),7.05-7.09(m,2H),7.49(d,J=7.7Hz,1H),9.87(br,1H),10.99(br,1H).

[0058] [ka]

[0059] <Synthesis of compound (A7)> Compound (A6) (4.03 g, 18.5 mmol) was placed in a 100 mL flask, degassed, and purged with argon. A 1.0 M tetrahydrofuran solution (22.1 mL) of tetra-n-butylammonium fluoride was added via syringe and stirred at room temperature for 1 hour. After the reaction was complete, the solvent was distilled off. Dichloromethane (100 mL) and saturated aqueous ammonium chloride (100 mL) were added, followed by separation and extraction of the organic layer. The aqueous layer was further extracted with dichloromethane (50 mL x 2). The resulting organic layer was dried over anhydrous MgSO4 and concentrated to give a brown solid. The residue was purified by silica gel column chromatography (eluent: dichloromethane) to give 2.44 g (yield: 90%) of a yellow solid, 4-ethynyl-2-hydroxybenzaldehyde (A7). (Identification data of compound (A7)) 1 H-NMR (500MHz, CDCl3): δ(ppm)3.24-3.36(s,1H),7.07-7.14(m,2H),7.51-7.53(m,1H),9.89(s,1H),11.01(s,1H).

[0060] [ka]

[0061] <Synthesis of substituted acetylene compound (2A) having a ketocoumarin skeleton> Compound (A3) (635 mg, 2.00 mmol) and compound (A7) (292 mg, 2.00 mmol) were placed in a reaction vessel, which was then degassed and replaced with argon. Ultra-dehydrated methanol (5.0 mL) and piperidine (17.2 mg, 0.20 mmol) were added via syringe, and the mixture was stirred overnight at 70 °C. After completion of the reaction, the resulting precipitate was filtered and dried to obtain 789 mg (yield: 95%) of an orange solid, substituted acetylene compound (2A). (Identification data of compound (2A)) 1H-NMR (500MHz, CDCl3): δ(ppm)1.24(t,J=7.1Hz,6H),3.31(s,1H),3.47(q,J=7.1Hz,4H),6.48 (d,J=2.7Hz,1H),6.63(dd,J=9.1,2.3Hz,1H),7.46-7.38(m,3H),7.53(d,J=7.7Hz,1H),8.02(s,1H),8.36(s,1H).

[0062] [ka]

[0063] <Synthesis of substituted polyacetylene (1a) having a ketocoumarin skeleton> A reaction vessel was charged with 1,5-norbornadienorhodium(I) tetraphenylborate (5.14 mg, 0.01 mmol), degassed, and purged with argon. N,N-dimethylformamide (0.5 mL) was added via syringe, followed by a solution of compound (2A) (207 mg, 0.50 mmol) in N,N-dimethylformamide (2 mL). After stirring at 30°C for 3 hours, the resulting solution was added to purified water. The resulting precipitate was collected using a membrane filter, yielding a quantitative yellow solid.

[0064] [ka]

[0065] [Example 2] <Synthesis of substituted polyacetylene (1a) having a ketocoumarin skeleton> A reaction vessel was charged with 1,5-norbornadienorhodium(I) tetraphenylborate (2.57 mg, 0.005 mmol), degassed, and purged with argon. Chloroform (1 mL) was added via syringe, followed by a chloroform (4 mL) solution of compound (2A) (413 mg, 0.250 mmol). After stirring at 30°C for 3 hours, the resulting solution was added to diethyl ether. The resulting precipitate was collected using a membrane filter, yielding 96.5 mg of an orange solid (yield: 93%).

[0066] <Evaluation of number average molecular weight (Mn) and weight average molecular weight (Mw)> The number average molecular weight (Mn), weight average molecular weight (Mw), and ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) were determined for the substituted polyacetylenes obtained in Examples 1 and 2. The results are shown in Table 1. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were evaluated by SEC (Shodex LF-804, JASCO RI-930, JASCO UV-4570, JASCO PU-4580, JASCO DG-2080-53, JASCO CO-965, JASCO LC-NetII / ADC, 10 mM LiBr in N,N-dimethylformamide, polystyrene equivalent).

[0067] [Table 1]

[0068] The substituted polyacetylene (1a) obtained in Example 2 was dissolved in N,N-dimethylformamide, and the UV-vis spectrum and emission spectrum were measured. The concentration of the monomer unit of the substituted polyacetylene was 0.1 mM. The excitation wavelength for the emission spectrum measurement was 450 nm. The UV-vis spectrum and emission spectrum of the substituted polyacetylene (1a) obtained in Example 2 are shown in FIG. 1, it can be seen that the substituted polyacetylene (1a) obtained in Example 2 has an absorption region at 450 nm, which is the visible light region. Furthermore, it can be seen that when excited at 450 nm, light emission is observed in the vicinity of 470-540 nm.

Claims

1. A substituted polyacetylene having a ketocoumarin skeleton containing a repeating unit represented by the following general formula (1): 【Chemistry 1】 (In the formula, R １ represents a group selected from an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an amino group, a carbonyl group, a carboxy group, a hydroxy group, and a nitro group, and the alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, and amino group may have a substituent. X represents a halogen atom. n represents an integer of 0 to 3.

2. R in general formula (1) １ The substituted polyacetylene having a ketocoumarin skeleton according to claim 1 , wherein is a tertiary amino group.

3. A method for producing a substituted polyacetylene having a ketocoumarin skeleton containing a repeating unit represented by the following general formula (1), comprising carrying out a polymerization reaction of a substituted acetylene compound having a ketocoumarin skeleton represented by the following general formula (2) in the presence of a polymerization initiator comprising a transition metal catalyst: 【Chemistry 2】 (In the formula, R １ represents a group selected from an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an amino group, a carbonyl group, a carboxy group, a hydroxy group, and a nitro group, and the alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, and amino group may have a substituent. X represents a halogen atom. n represents an integer of 0 to 3. 【Transformation 3】 (R in the formula １ , X and n have the same meanings as in general formula (1).

4. A substituted acetylene compound having a ketocoumarin skeleton represented by the following general formula (2a): 【Chemistry 4】 (In the formula, R １ａ represents a tertiary amino group. ａ represents a halogen atom. ａ represents an integer of 0 to 3.)

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