KR20200131174A - Method for manufacturing hetero cyclic compounds for electron acceptor, polymers for electron donor based on the hetero cyclic compounds, and organic semiconductor device comprising the same - Google Patents

Abstract

The present invention relates to a method for manufacturing heterocyclic compounds for an electron acceptor, polymers for an electron donor based on the heterocyclic compounds, and an organic semiconductor element including the same. The method for manufacturing heterocyclic compounds for an electron acceptor reduces the number of synthesis to improve synthesis complexity, and has relatively high yield and excellent economics. The polymers for an electron donor based on the heterocyclic compounds has high oxidation stability, high dipole moment, and balanced crystal and miscibility based on appropriate molecular weight and solubility. The organic semiconductor element includes the polymers based on the heterocyclic compounds having relatively high energy conversion efficiency.

Description

Method for manufacturing hetero cyclic compounds for electron acceptor, polymers for electron donor based on the hetero cyclic compounds, and organic semiconductor device comprising the same}

It relates to a method of preparing an electron accepting heterocyclic compound, an electron donating polymer based on a heterocyclic compound, and an organic semiconductor device including the same.

As the problem of environmental pollution caused by the use of high oil prices and fossil fuels emerges around the world, the demand for sustainable and eco-friendly energy sources is rapidly increasing. Representative eco-friendly energy sources include solar power, wind power, hydropower, wave power, and geothermal heat. Among them, solar cells that can generate power using solar power are attracting attention as an infinite electric energy source with the least number of places. It is estimated that the actual amount of solar energy that can be excavated from 1.7 to 10 ⁵ TW of solar energy reaching the Earth's surface is 600 TW. At this time, if a solar power plant with 10% efficiency is available, about 60 TW of power can be supplied. This is an enormous amount to meet the future demand for sustainable energy sources compared to the Earth's estimated energy demand of 28 TW in 2050.

As for solar cells, first-generation crystalline silicon solar cells using inorganic substances occupy 90% of the solar power generation market. However, this is only used for long-term medium and large-scale power generation, as its power generation cost is 5 to 20 times higher than that of fossil fuels, and its application value is low. As a result, the second-generation thin-film solar cell technology (CdTe, CIGS, etc.) that replaces silicon has emerged rapidly and occupies the remaining 10% of the market. However, the second-generation solar cell technology also requires expensive equipment because some materials are classified as precious metals and semiconductor thin films are formed through vacuum and high-temperature processes when manufacturing devices. An organic solar cell is a low-cost solar cell to solve these problems. Since it uses organic materials, it is possible to process a solution, thereby lowering the unit cost of solar cells, and due to its mechanical flexibility, ease of design, and diversity, its application possibilities are endless, such as clothing, portable electric and electronic products, and are emerging as the next generation solar cells.

For the practical use of organic solar cells, the prerequisites are improvement of efficiency, extension of life, large area, development of printable materials, and securing of transparent electrodes. Of these, by far, the high efficiency of the organic solar cell must be achieved. The development of high-solubility high-efficiency (high-efficiency and high-stability) materials capable of low-temperature solution processing can dramatically lower the production cost and solve technical problems in a chain. In recent years, organic solar cells have achieved rapid development since the large paradigm of electron acceptor materials for photoactive layers changed from fullerene derivatives to non-fullerene derivatives. Currently, the world's highest organic solar cell efficiency is 11.5% (Nature Energy 2016, 1, 15027) based on NREL (National Renewable Energy Laboratory) certification for fullerenes and 15.6% for non-fullerenes (Joule 2019, 3, 1- 16). It took about 15 years or more for fullerene-based organic solar cells to develop to the current level, whereas non-fullerene-based organic solar cells only took less than 5 years. In addition, in terms of the stability of organic solar cells, non-fullerenes are generally reported to be superior to fullerenes (Nature Communication, 2016, 7, 11585, Nature Materials, 2017, 16, 363-369). Representatively, in the case of PCE11, a similar derivative showing the world's highest efficiency in fullerene-based organic solar cells, burn-in decomposition occurs after 5 days of aging in the atmosphere, resulting in a decrease of about 39% in efficiency. Yes (Nature Communications, 2017, 8, 14541). On the other hand, in the case of the non-fullerene system, there is a problem that the efficiency does not decrease by less than 15% even after 5 days aging.

The present invention relates to a method for preparing a heterocyclic compound, a polymer based on a heterocyclic compound, and an organic semiconductor device including the same, and more specifically, a method for preparing a heterocyclic compound that can be used as an electron acceptor by being used as a repeating unit of a polymer An object of the present invention is to provide a heterocyclic compound-based polymer and a method of manufacturing an organic semiconductor device including the same.

The problem to be solved by the present invention is not limited to the above-described problems, and the problems that are not mentioned will be clearly understood by those of ordinary skill in the art from the present specification.

In order to solve the above problems, the present invention can provide a method of preparing an electron accepting heterocyclic compound. The method for preparing the heterocyclic compound includes: a) synthesizing a compound represented by the following formula 1a; And b) reacting a compound represented by Formula 1a synthesized in step a) with a compound represented by Formula 1b to synthesize a compound represented by Formula 1 below:

[Formula 1a]

[Formula 1b]

[Formula 1]

In Formula 1a and Formula 1b,

Q is each independently one selected from O, S, Se and Te,

Z is one independently selected from CR ₃ and N,

X is one independently selected from halogen and haloalkyl substituted sulfonate groups,

Each R ₁ is independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; is selected at least one from the group consisting of,

R ₂ and R ₃ are each independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an arylsulfoxy group; at least one is selected from the group consisting of.

In addition, the present invention can provide a polymer comprising a repeating unit represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

n is an integer from 1 to 10,000,

Q is each independently one selected from O, S, Se and Te,

Z is one independently selected from CR ₃ and N,

Each R ₁ is independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; is selected at least one from the group consisting of,

Each R ₃ is independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; is selected at least one from the group consisting of,

D is the unit of electron donation.

In addition, D may provide a polymer that is an electron donating unit represented by the following Chemical Formula 3.

[Formula 3]

In Chemical Formula 3, Ri is bonded with an adjacent 5-membered heteroaryl derivative to form a fused ring; Single bond; A group derived from a 5 to 6 membered monocyclic carbocyclic compound unsubstituted or substituted with a substituent J; A group derived from a 5 to 6 membered monocyclic heterocyclic compound including at least one selected from N, P, O, S, Se and Te substituted or unsubstituted with a substituent J; And 5 to 6 atoms including at least one selected from 5 to 6 reduced monocyclic carbocyclic compounds substituted or unsubstituted with substituent J and N, P, O, S, Se and Te substituted or unsubstituted with substituent J A group derived from a polycyclic fused ring compound in which at least two or more of the monocyclic heterocyclic compounds are fused; and at least one selected from the group consisting of,

Q is each independently one selected from O, S, Se and Te,

Each R is independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Aryloxy group; Arylsulfoxy group; And an amine group; is selected from the group consisting of,

J is each independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an arylsulfoxy group; at least one is selected from the group consisting of.

Further, the present invention provides an organic semiconductor device comprising the above-described polymer. Specifically, an organic conductor comprising the polymer, for example, a field effect transistor and a charge transport layer of a perovskite solar cell, an organic light emitting diode, a charge injection layer and an ITO planarization layer in a flat screen and a touch screen, an antistatic film, Printed circuits and capacitors, etc. can be provided.

In addition, the present invention can particularly provide an organic solar cell comprising the polymer.

The method for preparing a heterocyclic compound according to the present invention improves synthesis complexity by lowering the number of synthesis compared to the prior art, has a relatively high yield, and is excellent in economy.

In addition, the polymer according to the present invention has high oxidation stability, high dipole moment, balanced crystallinity and miscibility based on an appropriate molecular weight and solubility.

In addition, the organic semiconductor device including the polymer according to the present invention exhibits excellent performance due to relatively high energy conversion efficiency.

The effects of the present invention are not limited to the above-described effects, and effects that are not mentioned will be clearly understood by those of ordinary skill in the art from the present specification.

FIG. 1 is a schematic diagram of the synthesis of carboxylate-chlorine bithiophene (BiT-COOBOCl-in) in Example 1 of the present invention and a diagram of the synthesis mechanism.
2 is a ¹ H NMR picture of Compound 1-1 in Example 1 of the present invention.
3 is a ¹ H NMR picture of Compound 1-2 in Example 1 of the present invention.
4 is a ¹ H NMR picture of Compound 1-3 in Example 1 of the present invention.
5 is a ¹ H NMR picture of compound 1-4 in Example 1 of the present invention.
6 is a ¹ H NMR diagram of P(F-BiT)(COOBO) in Example 2 of the present invention.
7 is a ¹ H NMR diagram of P(Cl-BiT)(COOBO) in Example 3 of the present invention.
8 is a ¹ H NMR diagram of P(F-BiT)(COOBOCl-in) in Example 4 of the present invention.
9 is a schematic diagram of the synthesis of carboxylate-chlorine bithiophene (BiT-COORCl-out) in Example 5 of the present invention and a diagram of the synthesis mechanism.
10 is a ¹ H NMR picture of compound 5-1 in Example 5 of the present invention.
11 is a ¹ H NMR picture of compound 5-2 in Example 5 of the present invention.
12 is a ¹ H NMR picture of Compound 5-3 in Example 5 of the present invention.
13 is a ¹ H NMR picture of compound 5-4 in Example 5 of the present invention.
14 is a ¹ H NMR picture of compound 5-5 in Example 5 of the present invention.
15 is a ¹ H NMR picture of compound 5-6 in Example 5 of the present invention.
16 is a ¹ H NMR picture of Compound 5-7 in Example 5 of the present invention.
17 is a ¹ H NMR picture of compound 5-8 in Example 5 of the present invention.
18 is a ¹ H NMR diagram of P(F-BiT)(COOBOCl-out) in Example 6 of the present invention.
19 is a ¹ H NMR diagram of P(F-BiT)(COOC8Cl-out) in Example 7 of the present invention.
20 is a ¹ H NMR diagram of P(Cl-BiT)(COOC8Cl-out) in Example 8 of the present invention.
21 is a ¹ H NMR diagram of P(Cl-BiT)(COOC10Cl-out) in Example 9 of the present invention.
22 is a ¹ H NMR diagram of P(Cl-BiT)(COOC12Cl-out) in Example 10 of the present invention.
23 is a schematic diagram of the synthesis of carboxylate cyanazole-thiophene (TzT-COOBO) in Example 11 of the present invention and a diagram of the synthesis mechanism.
24 is a ¹ H NMR picture of Compound 11-1 in Example 11 of the present invention.
25 is a ¹ H NMR picture of Compound 11-2 in Example 11 of the present invention.
26 is a ¹ H NMR diagram of P(F-TzT)(COOCBO) in Example 12 of the present invention.
27 shows UV-Vis absorption spectra of the three polymers of Examples 2 to 4 of the present invention: chloroform solution and film state.
28 shows UV-Vis absorption spectra of five polymers of Examples 6 to 10 of the present invention: chloroform solution and film state.
Figure 29 shows the UV-Vis absorption spectrum of Example 12 of the present invention: chloroform solution and film state.
FIG. 30 shows a CV (Cyclic voltammetry) graph of the three polymers of Examples 2 to 4 of the present invention:
FIG. 31 shows a CV (Cyclic voltammetry) graph of five polymers of Examples 6 to 10 of the present invention:
Figure 32 shows a CV (Cyclic voltammetry) graph of Example 12 of the present invention:
33 shows the evaluation results of organic solar cell devices fabricated with inverse structures of two types of polymers showing maximum efficiency as Examples 6 and 12 of the present invention: current density-voltage (JV) graph.
FIG. 34 shows the evaluation results of organic solar cell devices fabricated with inverse structures of two polymers showing maximum efficiency as Examples 6 and 12 of the present invention: IPCE graph.
35 shows a schematic diagram of an inverted structure (or a typical structure) as an organic solar cell device structure of the present invention.

The method for preparing a heterocyclic compound according to an embodiment of the present invention improves the synthesis complexity by lowering the number of synthesis compared to the prior art through a Steglich esterification (DCC/DMAP) reaction, has a relatively high yield, and is economical. great.

In addition, the heterocyclic compound-based polymer according to the present invention has advantages such as high oxidation stability, high dipole moment, balanced crystallinity and miscibility, appropriate molecular weight and solubility, and is used as a material for a relative electron acceptor and an optimal HOMO (High Ocuupied Molecular Orbital). ) It is designed to have level offset energy.

The heterocyclic compound-based polymer according to an embodiment of the present invention is a high-performance electron donor polymer, and its composition is a horizontal structure of benzodithiophene derivatives with excellent planarity, oxidation stability and mobility (BDT, benzo[1,2- b:4,5-b']dithiophene derivatives) A DAB form capable of electronically push-pull can be designed as a basic main chain by employing a hetero ring substituted with a carboxylate as D and substituted with a carboxylate. In addition, the structure was delicately modified in consideration of the curvature and electrochemical properties of the main chain polymer.

Among the polymers according to an embodiment of the present invention, P(Cl-BiT)(COOBO/Cl-out) is a two-dimensional grazing incidence wide-angle for viewing the orientation of the thin film as an electron donor and a mixed phase with an electron acceptor material. X-ray scattering (2D-GIWAXS) was measured. In addition, an organic solar cell device containing the polymer was fabricated to evaluate its performance. As a result, the maximum efficiency of P(Cl-BiT)(COOBO/Cl-out) was 10.7%.

Hereinafter, the present invention will be described in more detail.

"Including" a certain element throughout the specification means that other elements may be further included rather than excluding other elements unless specifically stated to the contrary.

In the structural formulas of the present specification, the symbol "-" for bonding an atom and/or a group may mean a single bond, and the symbol “=” may mean a double bond. The above symbol may be omitted, and may be indicated if necessary, such as when specifying a bonding atom or a bonding position.

In the present specification, "substituted or unsubstituted" may mean that one or more hydrogen atoms are substituted or not substituted with other atoms or substituents unless otherwise stated. It may be the substituent group J, wherein J is a halogen (chloro (Cl), iodine Chemistry (I), bromo (Br), fluoro (F)), of Seattle furnace, C _{1 ~ 16} alkyl, C _{2 ~ 16} alkenyl group, C _{2 ~ 16} alkynyl, aryl, aralkyl, N, P, O, S, Se, and heterocyclic alkyl containing at least one heteroatom selected from Te, N, P, O, S, Se And heterocyclic alkenyl containing at least one hetero atom selected from Te, heteroaryl containing at least one hetero atom selected from N, P, O, S, Se and Te, hydroxyl, C _1-16 alkoxy , Amino, nitro, thiol, thionyl, thioether, imine, cyano, phosphonato, phosphine, carboxy, carbamoyl, car Bamic acid, acetal, urea, thiocarbonyl, sulfonyl, sulfonamide, sulfonate, silyl, ketone, aldehyde, ester, acetyl, isetoxy, amide, haloalkyl (e.g., Trifluoromethyl), aminoacyl, aminoalkyl, alkylsulfoxy, amine (primary, secondary, or tertiary), aryloxy, and may be one or more selected from the group consisting of arylsulfoxy, but is not limited thereto. In addition, each of the above-exemplified substituents may be again substituted or unsubstituted with a substituent selected from these substituent groups.

In the present specification, "halogen" may be F, Cl, Br or I.

In the present specification, "alkyl", unless otherwise stated, a linear or branched acyclic type; Cyclic; Or it may mean a saturated hydrocarbon to which they are bonded. In addition, "C _1-8 alkyl" may mean an alkyl containing 1 to 8 carbon atoms. Acyclic alkyl is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, sec (sec)-butyl, isobutyl , Tert-butyl, isopentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl, and the like, but are not limited thereto. Cyclic alkyls can include non-fused alkyl and fused alkyl. The non-fused alkyl may include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, but is not limited thereto. In addition, the fused alkyl may include, for example, decahydronaphthalenyl, tetradecahydroanthracenyl or dodecahydro-1H-fluorenyl, but is not limited thereto. Alkyl in which acyclic and cyclic alkyl is bonded is, for example, methylcyclopropyl, cyclopropylmethyl, ethylcyclopropyl, cyclopropylethyl, methylcyclobutyl, cyclobutylmethyl, ethylcyclopentyl, or cyclopentylmethyl. It may include, but is not limited thereto.

In the present specification, “alkenyl” refers to a linear, branched, acyclic type having one or more double bonds unless otherwise stated; Cyclic; Or it may mean an unsaturated hydrocarbon to which they are bonded. In addition, "C _2-8 alkenyl" may mean alkenyl containing 2 to 8 carbon atoms. Non-cyclic alkenyl, as an example, ethenyl, 1-propenyl, prop-2-en-1-yl[-(CH ₂ -CH=CH ₂ )], 2-butenyl, isopropenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, and the like may be included, but are not limited thereto. Cyclic alkenyl may include non-fused alkenyl and fused alkenyl excluding aryl. The non-fused alkenyl may include, for example, cyclopentenyl, cyclohexenyl, cyclohexa-1,3-dienyl, cyclohexa-1,4-dienyl, etc., but is limited thereto. no. The fused alkenyl includes, as an example, 1,2,3,4,5,8-hexahydronaphthalenyl, 2,3,3a, 4,5,7a-hexahydro-1H-indenyl, etc. It can be, but is not limited thereto. Alkenyl to which acyclic and cyclic alkenyl are bonded is, for example, 2-vinyl-1,2,3,4,5,8-hexahydronaphthalenyl, (E)-5-(prop-1 -Enyl)-2,3,3a, 4,5,7a-hexahydro-1H-indenyl, and the like, but are not limited thereto.

In the present specification, “alkynyl” refers to a linear, branched, acyclic type having one or more triple bonds unless otherwise stated; Cyclic; Or it may mean an unsaturated hydrocarbon to which they are bonded. In addition, "C _2-8 alkynyl" may mean an alkynyl containing 2 to 8 carbon atoms. The alkynyl is ethynyl, propynyl, hydroxypropynyl, butyn-1-yl, butyn-2-yl, pentin-1-yl, 3-methylbutyn-1-yl, hexyn-2-yl (hexyn- 2-yl), cyclopentenyl, cyclohexenyl, and the like may be included, but are not limited thereto.

In the present specification, "aryl" may mean an aromatic ring in which one hydrogen has been removed from an aromatic hydrocarbon ring, and may be a single ring or multiple rings. "Aryl of 3 to 16 atoms" may mean an aryl including 3 to 16 atoms forming a ring, as an example, phenyl, naphthyl, tolyl, xylline, anthracenyl phenanthryl, biphenyl, Terphenyl or fluorenyl may be included, but the present invention is not limited thereto.

In the present specification, "aralkyl (aralkyl)" may mean -(alkyl-aryl), where alkyl and aryl are as defined above. In addition, "aralkyl of 3 to 8 atoms" may mean aralkyl containing 3 to 8 carbon atoms.

In the present specification, "a group derived from a carbon ring compound" refers to the cyclic alkyl or alkyl in which acyclic and cyclic alkyl are bonded; Cyclic alkenyl or alkenyl in which acyclic and cyclic alkenyl are bonded; Cyclic alkynyl or alkynyl in which acyclic and cyclic alkynyl are bonded; Aryl; And aralkyl.

In the present specification, "hetero atom" refers to an atom other than hydrogen and carbon in an organic compound, and may include N, P, O, S, Se, and Te.

In the present specification, "heterocyclic alkyl" may mean a cyclic alkyl comprising at least one hetero atom selected from N, P, O, S, Se and Te, wherein cyclic alkyl is defined above. As shown. In addition, "a 3 to 16 membered heterocyclic alkyl" may mean a heterocyclic alkyl including 3 to 16 atoms forming a ring. Heterocyclic alkyl is, for example, pyrrolidinyl, piperidinyl, imidazolidinyl, pyrazolidinyl, butyrolactamyl, valerolactamyl, imidazolidinoneyl, hydantoinyl, dioxolane Yl, 1,4-dioxanyl, morpholinyl, thiomorpholinyl, thiomorpholine-S-oxideyl, piperazinyl, thiomorpholine-S,S-oxideyl, quinuclidinyl, tropanyl, 2 -Azaspiro[3.3]heptanyl may be included, but is not limited thereto.

In the present specification, "heterocyclic alkenyl" may mean a cyclic alkenyl (not including heteroaryl) including one or more heteroatoms selected from N, P, O, S, Se and Te, and , Wherein cyclic alkenyl is as defined above. In addition, "3 to 16-membered heterocyclic alkenyl" may mean a heterocyclic alkenyl including 3 to 16 atoms forming a ring. Heterocyclic alkenyl is, for example, pyrimidine-2,4(1H,3H)-dioneyl, pyranyl, pyridonyl, 3-pyrrolinyl, thiopyranyl, pyronyl, tetrahydrofuranyl, It may include tetrahydrothiophenyl, but is not limited thereto.

In the present specification, "heteroaryl" may mean an aromatic ring containing at least one hetero atom from N, O, S, Se and Te as an atom forming the ring, and may be a single ring or a multi-ring. In addition, "heteroaryl of 3 to 16 atoms" may mean a heteroaryl including 3 to 16 atoms forming a ring, as an example, thienyl group, thiophenyl, furyl, pyrrolyl, pyrazolyl , Imidazolyl, thiazolyl, oxazolyl, isothiazolyl, oxadiazolyl, triazolyl, pyridinyl, bipyridyl, pyrimidyl, triazinyl, triazolyl, acridyl group, pyridazinyl group, pyrazinyl, Quinolinyl, quinazolinyl, quinoxalinyl, phenoxazolinyl, phthalazinyl, pyrimidinyl, pyrido pyrimidinyl, pyrido pyrazinyl, pyrazino pyrazinyl, isoquinolinyl, indole, car Bazolyl, imidazopyridazinyl, phthalimideyl, imidazopyridinyl, imidazopyrimidinyl, pyrazolopyrimidinyl, imidazopyrazinyl, pyrazolopyridinyl, N-arylcarbazole, N- Heteroarylcarbazole, N-alkylcarbazole group, benzooxazolyl, benzoimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenylyl, thienothiophenyl, benzofuranyl, phenanthroli Neil, isoxazolyl, oxadiazolyl, thiadiazolyl, benzothiazolyl, tetrazolyl, phenothiazinyl, dibenzosilol, dibenzofuranyl, and the like may be included, but are not limited thereto.

In the present specification, "a group derived from a heterocyclic compound" refers to the heterocyclic alkyl; Heterocyclic alkenyl; And heteroaryl.

In the present specification, "alkoxy" may mean -(O-alkyl) as an alkyl ether group, where alkyl is as defined above. In addition, "C _1-8 alkoxy" may mean alkoxy containing C _1-8 alkyl, that is, -(OC _1-8 alkyl), and as an example, C _1-8 alkoxy is methoxy ), ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy ( secbutoxy), tert-butoxy, n-pentoxy, and the like, but are not limited thereto.

In the present specification, "alkylamino" may mean -(NR′R″), where R′ and R″ may each independently be selected from the group consisting of hydrogen, and C _1-8 alkyl, and the selected R′ and R″ may each independently be substituted or unsubstituted. In addition, "C _1-8 alkylamino" may mean amino containing C _1-8 alkyl, that is, -NH(C _1-8 alkyl) or -N-(C _1-8 alkyl) ₂ , Dimethylamino, diethylamino, methylethylamino, methylpropylamino, or ethylpropylamino may be included, but is not limited thereto.

In the present specification, "hydroxy" may mean -OH.

In the present specification, "carbonyl" may mean -(C=(O))-, and when a cyclic alkyl, aryl, or heterocycloalkyl is substituted with carbonyl, a hydrogen atom is substituted with (=O) It can mean the case.

In the present specification, "alkylcarbonyl" may mean -(C(=O)-alkyl), where alkyl is as defined above. In addition, "C _1-8 alkylcarbonyl" may mean a carbonyl containing C _1-8 alkyl, that is, -(C(=O)-C _1-8 alkyl), as an example, methyl Carbonyl (acetyl, -(C=(O)-CH ₃ )), ethylcarbonyl, n-propylcarbonyl, iso-propylcarbonyl, n-butylcarbonyl, sec-butylcarbonyl, isobutylcarbonyl , tert-butylcarbonyl, n-octylcarbonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, and the like, but are not limited thereto.

In the present specification, "alkenylcarbonyl" may mean -(C(=O)-alkenyl), where alkenyl is as defined above. In addition, "C _2-8 alkenylcarbonyl" may mean a carbonyl containing C _2-8 alkenyl, that is, -(C(=O)- C _2-8 alkenyl).

In the present specification, "cyano" may mean -(CN).

In the present specification, "amine" is a derivative of ammonia, and unless otherwise specified, it may mean a form in which a hydrogen atom is substituted with a substituent such as alkyl, aryl, aralkyl, or heteroaryl. In the ammonia, one When hydrogen is replaced by a substituent, it is called a primary amine, when two hydrogens are replaced by a substituent, it is called a secondary amine, and when three hydrogens are replaced by a substituent, it is called a tertiary amine. As an example, methylamine, dimethylamine, aniline, 3-nitroaniline, and the like may be included, but the present invention is not limited thereto.

The term fuse as used herein refers to forming a polycyclic compound through two or more monocyclic compounds, and a polycyclic compound in which the two or more monocyclic compounds are fused is a fused compound. ) Can be said.

Method for preparing heterocyclic compound

The present invention can provide a method for preparing a heterocyclic compound.

The method for preparing the heterocyclic compound includes: a) synthesizing a compound represented by the following formula 1a; And b) reacting the compound represented by Formula 1a synthesized in step a) with the compound represented by Formula 1b to synthesize a compound represented by Formula 1 below.

[Formula 1a]

[Formula 1b]

[Formula 1]

Each Q may be independently selected from O, S, Se, and Te.

Each Z may be independently selected from CR ₃ and N.

Each of X may independently be one selected from halogen and haloalkyl-substituted sulfonate groups. The haloalkyl-substituted sulfonate groups include, but are not limited to, trifluoroalkanesulfonate, trichloroalkanesulfonate, and the like. The trifluoroalkalsulfonate is, for example, trifluoromethanesulfonate (OTf).

Each R ₁ is independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; may be selected from one or more of the group consisting of.

R ₁ is each independently a halogen group to obtain a polymer having high oxidation stability, high dipole moment, balanced crystallinity and miscibility; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; And a heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; it is preferable that at least one is selected from the group consisting of. In addition, R ₁ is each independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; And C _{2 to 16} alkynyl group; it is more preferable that at least one is selected from the group consisting of. In addition, R ₁ are each independently C is more preferably selected from _{1 to 16} alkyl group and, C _{1 to 16} and most preferably a straight chain or branched C _1-16 acyclic alkaline group of the chain of the alkyl group.

R ₂ and R ₃ are each independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; may be selected from one or more of the group consisting of.

R ₂ is each independently hydrogen, considering the smoothness of the synthesis proceeding according to the method for preparing the heterocyclic compound; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; And a heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; it is preferable that at least one is selected from the group consisting of. In addition, R ₂ is hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; And C _{2 to 16} alkynyl group; more preferably one or more selected from the group consisting of, R ₂ is hydrogen; Or C _{1 ~ 16} alkyl group; most preferably one or more selected from the group consisting of.

R ₃ is each independently hydrogen, considering that the compound represented by Formula 1 is used as an excellent electron acceptor; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; And a heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; it is preferable that at least one is selected from the group consisting of. In addition, R ₃ is hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; And C _{2 to 16} alkynyl group; more preferably one or more selected from the group consisting of, and particularly R ₃ is most preferably selected from a halogen group.

a) synthesizing the compound represented by Formula 1a

The compound represented by Formula 1a is a heterocyclic compound substituted with a carboxylate. For example, a compound represented by the formula 1a, R ₁ and R ₂ as a substituted or unsubstituted 5-bromo-thiophene-3-carboxylate mosayi, R 2- bromo mosayi substituted or unsubstituted by ₁ and R ₂ azole It may be -4-carboxylate or 5-bromo-4-thiophene-3-carboxylate unsubstituted or substituted with R ₁ and R ₂ .

The compound represented by Formula 1a may be one of the compounds represented by Formulas 1a-1 to 1a-6 below.

In Formulas 1a-1 to 1a-6, R ₁ is the same as described above.

In addition, each R is independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; may be selected from one or more of the group consisting of.

In this step of synthesizing a compound represented by Formula 1a, i) a compound represented by Formula 1a-ii is obtained by reacting a compound represented by Formula 1a-i below with at least one of a sulfonate substituted with halogen and haloalkyl in a solvent. And ii) reacting the obtained compound represented by Formula 1a-ii with the compound represented by Formula 1a' in a solvent to obtain a compound represented by Formula 1a.

[Formula 1a-i]

[Formula 1a-ii]

[Formula 1a']

In Formulas 1a-i and 1a-ii,

Each Q may be independently selected from O, S, Se, and Te.

Each Z may be independently selected from CR3 and N.

Each of X may independently be one selected from halogen and haloalkyl-substituted sulfonate groups.

In Formula 1a-i, Formula 1a-ii, and Formula 1a',

R ₁ is the same as described above. In addition, R ₂ and R ₃ are also the same as described above.

I) In the step of reacting the compound represented by Formulas 1a-i with at least one of halogen and haloalkyl-substituted sulfonates in a solvent to obtain a compound represented by Formulas 1a-ii below, polar aprotic One or more selected from a solvent, a nonpolar solvent, and a mixed solvent thereof (eg, a mixed solvent of 1:10 vol% of toluene and dimethylformamide) may be used as the solvent. The polar aprotic solvent is, for example, dimethylsulfoxide (DMSO), dimethylformamide (dimethylformamide, DMF), N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, and the like, and the like, but is not particularly limited thereto. The non-polar solvent is, for example, methylene chloride (DCM), chloroform, toluene, benzene, ethylbenzene, chlorobenzene, dichlorobenzene, Hexane, diethyl ether, or 1,4-dioxane, and the like, but are not particularly limited thereto.

In addition, it is possible to add more acidic substances to improve the solubility and smooth reaction. The acidic substance includes an organic acid and an inorganic acid, and the type is not particularly limited. The organic acid may be a carboxylic acid, a sulfonic acid, an acid containing a phenol group, an acid containing a thiol group, an acid containing an enol group, and the like, and the inorganic acid Silver may be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. However, it is not limited thereto. Considering the solubility of the compound represented by Formula 1a-i, it is preferable to use methylene chloride or acetic acid.

In addition, an oxidizing agent may be further added for smooth reaction. Examples of the oxidizing agent include Al ₂ O ₃ , K ₂ O, CaO, MgO, Ag ₂ O, Cu ₂ O, or lead acetate (vi), and the type is not particularly limited.

In addition, it is possible to obtain a compound represented by Formula 1a-ii by further comprising the step of purifying after terminating the reaction using a reaction terminator.

Ii) In the step of obtaining the compound represented by Formula 1a by reacting the obtained compound represented by Formula 1a-ii with the compound represented by Formula 1a' in a solvent, a solvent and an acidic substance may be used as in step i). have. Considering the solubility with the compounds represented by Formulas 1a-ii, it is preferable to use methylene chloride or acetic acid.

In addition, steps ii) and ii) in this step may be reacted using a catalyst. The catalyst to be used may be used by selecting one or more from the group consisting of a nucleophilic catalyst and a complex compound catalyst. The nucleophilic catalyst includes N,N'-dicyclohexylcarbodiimide (N,N'-dicyclohexylcarbodiimide, DCC) and 4-dimethylaminopyridine (DMAP), but is not particularly limited thereto. The complex compound catalyst is palladium acetate (Pd(OAc) ₂ ), palladium trifluroacetate (Pd(TFA) ₂ ), tetrakis (triphenylphosphine) palladium (Pd(PPh ₃ ) ₄ ), bis(dibenzylidene) Acetone) palladium (Pd(dba) ₂ ), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) and copper acetate (Cu(OAc) ₂ ), and are not particularly limited thereto. In addition, in this step, a cocatalyst may be further added to improve the catalytic activity. The cocatalyst is Al ₂ O ₃ , K ₂ O, CaO, MgO, Ag ₂ O, Cu ₂ O, P(o-tolyl) ₃ (tris( o -tolyl)phosphine), PPh ₃ (triphenylphosphine) and Pcy ₃ One or more of HBF ₄ (tricyclohexylphosphine tetrafluoroborate) may be selected, but is not particularly limited thereto. In order to obtain the compound represented by Formula 1a more quickly, it is preferable to use a nucleophilic catalyst.

In addition, the compound represented by Formula 1a may be obtained by further comprising the step of purifying after terminating the reaction using a reaction terminating agent.

b) synthesizing a compound represented by the following formula 1 by reacting the compound represented by the formula 1a synthesized in step a) with the compound represented by the following formula 1b

The compound represented by Formula 1b is a heterocyclic compound containing a sulfonate group substituted with halogen or haloalkyl. For example, a compound represented by Formula 1b is R ₂ and R ₃ as substituted or unsubstituted 2-bromo-3-chloro-thiophene-between, R ₂ and R ₃ is substituted or unsubstituted 2-bromo -3 to ring Using the method of fluorine in between, R ₂ and R ₃ substituted or unsubstituted 2-bromo-4-chloro-thiophene-between, R ₂ and R ₃ is substituted or unsubstituted 2-bromo-selenide nopen, R ₂ and R ₃ as a ring a substituted or unsubstituted 2-bromo-substituted or unsubstituted between the parent azole, R ₂ and R ₃ as substituted or unsubstituted 2-bromo between adipic azole or R ₂ and R ₃ ring 2-bromo-3-cyano It may be a nothiophene. In addition, in order to synthesize the compound represented by Formula 1b, the precursor containing N-bromosuccinimide and N-chlorosuccinimide in the precursor where X is not substituted in Formula 1b. Halogen radical feeding compounds can be used.

The compound represented by Formula 1b may be one of the compounds represented by Formulas 1b-1 to 1b-18 below.

The step of synthesizing the compound represented by Formula 1 may include reacting the compound represented by Formula 1a with the compound represented by Formula 1b in a solvent to obtain the compound represented by Formula 1.

In this step, in order to dissolve the compound represented by Formula 1a, a polar aprotic solvent, a nonpolar solvent, and a mixed solvent thereof (e.g., toluene and dimethylformamide are 1:10 vol%). A mixed solvent) may be used as a solvent. The polar aprotic solvent is, for example, dimethylsulfoxide (DMSO), dimethylformamide (dimethylformamide, DMF), N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, and the like, and the like, but is not particularly limited thereto. The non-polar solvent is, for example, methylene chloride (DCM), chloroform, toluene, benzene, ethylbenzene, chlorobenzene, dichlorobenzene, Hexane, diethyl ether, or 1,4-dioxane, and the like, but are not particularly limited thereto.

In addition, it is possible to add more acidic substances to improve the solubility and smooth reaction. The acidic substance includes an organic acid and an inorganic acid, and the type is not particularly limited. The organic acid may be a carboxylic acid, a sulfonic acid, an acid containing a phenol group, an acid containing a thiol group, an acid containing an enol group, and the like, and the inorganic acid Silver may be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. However, it is not limited thereto. Considering the solubility of the compound represented by Formula 1a-i, it is preferable to use methylene chloride or acetic acid.

In addition, an oxidizing agent may be further added for smooth reaction. Examples of the oxidizing agent include Al ₂ O ₃ , K ₂ O, CaO, MgO, Ag ₂ O, Cu ₂ O, or lead acetate (vi), and the type is not particularly limited.

Considering the solubility with the compound represented by Formula 1a, the solvent is preferably a polar aprotic solvent, and at least one from the group consisting of dimethyl sulfoxide, dimethylformamide and N-methyl-2-pyrrolidone It is more preferable to select and use.

In addition, in this step, it can be reacted using a catalyst. The catalyst may be one or more selected from the group consisting of a nucleophilic catalyst and a complex compound catalyst. The nucleophilic catalyst includes N,N'-dicyclohexylcarbodiimide (N,N'-dicyclohexylcarbodiimide, DCC) and 4-dimethylaminopyridine (DMAP), but is not particularly limited thereto. The complex compound catalyst is palladium acetate (Pd(OAc) ₂ ), palladium trifluroacetate (Pd(TFA) ₂ ), tetrakis (triphenylphosphine) palladium (Pd(PPh ₃ ) ₄ ), bis(dibenzylidene) Acetone) palladium (Pd(dba) ₂ ), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) and copper acetate (Cu(OAc) ₂ ), and are not particularly limited thereto. In addition, in this step, a cocatalyst may be further added to improve the catalytic activity. The cocatalyst is Al ₂ O ₃ , K ₂ O, CaO, MgO, Ag ₂ O, Cu ₂ O, P(o-tolyl) ₃ (tris( o -tolyl)phosphine), PPh ₃ (triphenylphosphine) and Pcy ₃ One or more of HBF ₄ (tricyclohexylphosphine tetrafluoroborate) may be selected, but is not particularly limited thereto. In order to obtain the compound represented by Formula 1 more quickly, it is preferable to use a complex compound catalyst.

In addition, the reaction temperature in this step may be carried out at 0 to 180 °C, and in particular, it may be carried out at room temperature.

In addition, the compound represented by Formula 1 may be obtained by further comprising the step of purifying after terminating the reaction using a reaction terminating agent.

The compound represented by Formula 1 obtainable through this step may be one of the compounds represented by the following Formulas 1-1 to 1-4.

In Formulas 1-1 to 1-4, R ₁ and R are the same as described above.

The step of synthesizing the compound represented by Formula 1 includes reacting the compound represented by Formula 1a with the compound represented by Formula 1b in a solvent to obtain a catalyst reactant, and adding a halogen salt to the catalyst reactant. To obtain the compound represented by Chemical Formula 1.

The step of reacting the compound represented by Formula 1a with the compound represented by Formula 1b in a solvent to obtain a catalytic reactant may be the same as described above. Examples of the halogen salt include lithium chloride, sodium chloride, lithium fluoride, sodium fluoride, and lithium bromide, and are not particularly limited thereto.

In addition, the reaction temperature in this step may be carried out at 0 to 180 °C, and in particular, it may be carried out at room temperature.

In addition, the compound represented by Formula 1 may be obtained by further comprising the step of purifying after terminating the reaction using a reaction terminating agent.

The compound represented by Formula 1 obtainable through this step may be one of the compounds represented by the following Formulas 1-5 to 1-8.

In Formulas 1-5 to 1-8, R and R ₁ are the same as R and R ₁ described in Formulas 1-1 to 1-4.

Heterocyclic compound-based polymer

The present invention can provide a heterocyclic compound-based polymer.

The heterocyclic compound-based polymer may include a repeating unit represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

n may be an integer between 1 and 10,000.

D may be an electron donating unit derived from an electron donating monomer. The electron donating monomer is, for example, benzodithiophene (BDT, benzodithiophene) and its derivatives, benzodithienothiophene (BDTT, benzodithienothiophene) and its derivatives, naphthodithiophene (NDT, naphthodithiophene) and its derivatives, thienothione. Opene (TT, thienothiophene) and derivatives thereof, and bithiophene (BiT, bithiophene) and derivatives thereof, and the like, but are not particularly limited thereto.

Each Q may be independently selected from O, S, Se, and Te.

Z is each independently CR ₃ and It may be one selected from N.

Each R ₁ is independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; may be selected from one or more of the group consisting of.

Each R ₃ is independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; may be selected from one or more of the group consisting of.

The polymer including the repeating unit represented by Chemical Formula 2 may be a heterocyclic compound represented by Chemical Formula 1 and the electron donating unit D combined with each other. In this case, the heterocyclic compound represented by Formula 1 is the same as described above.

In Formula 2, D may be an electron donating unit represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3, Ri is bonded with an adjacent 5-membered heteroaryl derivative to form a fused ring; Single bond; A group derived from a 5 to 6 membered monocyclic carbocyclic compound unsubstituted or substituted with a substituent J; A group derived from a 5 to 6 membered monocyclic heterocyclic compound including at least one selected from N, P, O, S, Se and Te substituted or unsubstituted with a substituent J; And 5 to 6 atoms including at least one selected from 5 to 6 reduced monocyclic carbocyclic compounds substituted or unsubstituted with substituent J and N, P, O, S, Se and Te substituted or unsubstituted with substituent J A group derived from a polycyclic fused ring compound in which at least two or more of the monocyclic heterocyclic compounds are fused; may be at least one selected from the group consisting of.

Each Q may be independently selected from O, S, Se, and Te.

In addition, each R is independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Aryloxy group; Arylsulfoxy group; And an amine group; may be selected from the group consisting of.

In addition, J is a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; may be selected from one or more of the group consisting of.

Specifically, D is benzodithiophene (BDT, benzodithiophene) and its derivatives, benzodithienothiophene (BDTT, benzodithienothiophene) and its derivatives, naphthodithiophene (NDT, naphthodithiophene) and its derivatives, thienothiophene (TT, thienothiophene) and derivatives thereof, and units derived from bithiophene (BiT, bithiophene) and derivatives thereof.

In addition, as the D, it is very important to select a derivative having a regioregular because it minimizes the influence on the coverage of the main chain polymer, and considering this, D is among the compounds represented by the following formulas 3-1 to 3-8. It is preferable to be one.

In Formulas 3-1 to 3-8, Q may each independently be one of O, S, Se, and Te. Each R'is independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Aryloxy group; Arylsulfoxy group; And an amine group; may be selected from the group consisting of.

In addition, each of R'may be unsubstituted or substituted with a substituent selected from these substituent groups.

In addition, R'may be one of the compounds represented by the following Chemical Formulas 4-1 to 4-4.

In Formulas 4-1 to 4-4, each of Q may independently be one of O, S, Se, and Te. R ₄ to R ₈ are each independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; may be selected from one or more of the group consisting of.

More specifically, D may be one of the compounds represented by the following Chemical Formulas 3-i to 3-xxiii.

In Chemical Formulas 3-i to 3-xiiiiii, each Q may independently be one of O, S, Se, and Te. R ₄ to R ₇ are each independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; may be selected from one or more of the group consisting of.

Containing the repeating unit represented by Formula 2 The number average molecular weight of the polymer is not particularly limited. However, preferably, it may be 500 Da to 100 kDa, more preferably, 1 kDa to 90 kDa, and most preferably 5 kDa to 70 kDa. In addition, including the repeating unit represented by Formula 2 The weight average molecular weight of the polymer is not particularly limited. However, preferably, it may be 1 kDa to 250 kDa, more preferably 10 kDa to 200 kDa, and most preferably 50 kDa to 150 kDa. Containing the repeating unit represented by Formula 2 The polydispersity index of the polymer is not particularly limited. However, preferably, it may be 1.0 to 100, more preferably, it may be 1.10 to 30, and most preferably, it may be 1.25 to 5.0. Containing the repeating unit represented by Formula 2 The thermal decomposition temperature of the polymer may be 250 ℃ to 500 ℃. Preferably, it may be 280 °C to 480 °C, more preferably 300 °C to 420 °C.

Method for preparing polymer based on heterocyclic compound

The present invention can provide a method for producing a heterocyclic compound-based polymer. In this case, the heterocyclic compound can be obtained according to the method for preparing the heterocyclic compound described above. The method for preparing the polymer includes a') polymerizing the compound represented by Formula 1 and the electron donating unit D obtained according to the method for preparing the heterocyclic compound in a solvent; And b') obtaining a polymer including the repeating unit represented by Chemical Formula 2 through the polymerization. In addition, c') may further include the step of purifying the polymer obtained in step b'). In this case, the electron donating unit D may be an electron donating unit represented by Chemical Formula 3.

The compound represented by Formula 1 and the electron donating unit D may be dissolved in a solvent. The solvent may be at least one selected from a polar aprotic solvent, a nonpolar solvent, and a mixed solvent thereof (e.g., a mixed solvent of 1:10 vol% of toluene and dimethylformamide). . The polar aprotic solvent is, for example, dimethylsulfoxide (DMSO), dimethylformamide (dimethylformamide, DMF), N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, and the like, and the like, but is not particularly limited thereto. The non-polar solvent is, for example, methylene chloride (DCM), chloroform, toluene, benzene, ethylbenzene, chlorobenzene, dichlorobenzene, Hexane, diethyl ether, or 1,4-dioxane, and the like, but are not particularly limited thereto.

In addition, it is possible to add more acidic substances to improve the solubility and smooth reaction. The acidic substance includes an organic acid and an inorganic acid, and the type is not particularly limited. The organic acid may be a carboxylic acid, a sulfonic acid, an acid containing a phenol group, an acid containing a thiol group, an acid containing an enol group, and the like, and the inorganic acid Silver may be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. However, it is not limited thereto.

In addition, an oxidizing agent may be further added for smooth reaction. Examples of the oxidizing agent include Al ₂ O ₃ , K ₂ O, CaO, MgO, Ag ₂ O, Cu ₂ O, or lead acetate (vi), and the type is not particularly limited.

Considering the solubility of the compound represented by Formula 1 and the electron donating unit D, it is preferable to use a non-polar solvent as a solvent, and toluene, benzene, ethylbenzene, chlorobenzene, It is more preferable that it is at least one selected from dichlorobenzene and a mixed solvent thereof (eg, a mixed solvent obtained by mixing toluene and dimethylformamide at 1:10 vol%).

The compound represented by Formula 1 and D, which is an electron donating unit, may be added to the solvent and dissolved to obtain a mixed solution, and polymerization may be performed by adding a catalyst to the mixed solution.

The catalyst may be used as a catalyst by selecting one or more from the group consisting of a nucleophilic catalyst and a complex compound catalyst. The nucleophilic catalyst includes N,N'-dicyclohexylcarbodiimide (N,N'-dicyclohexylcarbodiimide, DCC) and 4-dimethylaminopyridine (DMAP), but is not particularly limited thereto. The complex compound catalyst is palladium acetate (Pd(OAc) ₂ ), palladium trifluroacetate (Pd(TFA) ₂ ), tetrakis (triphenylphosphine) palladium (Pd(PPh ₃ ) ₄ ), bis(dibenzylidene) Acetone) palladium (Pd(dba) ₂ ), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) and copper acetate (Cu(OAc) ₂ ), and are not particularly limited thereto. In addition, in this step, a cocatalyst may be further added to improve the catalytic activity. The cocatalyst is Al ₂ O ₃ , K ₂ O, CaO, MgO, Ag ₂ O, Cu ₂ O, P(o-tolyl) ₃ (tris( o -tolyl)phosphine), PPh ₃ (triphenylphosphine) and Pcy ₃ One or more of HBF ₄ (tricyclohexylphosphine tetrafluoroborate) may be selected, and there is no particular limitation. Considering the polymerization time, it is preferable to use it as a complex compound catalyst or a mixture of a complex compound catalyst and cocatalyst. In addition, among the complex compound catalysts, tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), bis (dibenzylideneacetone) palladium (Pd (dba) ₂ ) and tris (dibenzylideneacetone) dipalladium ( It is preferable to select one or more from the group consisting of Pd ₂ (dba) ₃ ), and among the cocatalysts, P(o-tolyl) ₃ (tris( o -tolyl)phosphine), PPh ₃ (triphenylphosphine) and Pcy ₃ HBF It is preferable to select at least one of ₄ (tricyclohexylphosphine tetrafluoroborate). The polymerization is preferably carried out at a temperature of 80 ℃ to 180 ℃ considering the process efficiency.

In addition, a polymerization terminating agent for terminating the polymerization reaction may be used to obtain a polymer including the repeating unit represented by Chemical Formula 2. The polymerization terminating agent may be an end-capping agent, consisting of 2-bromothiophene, 2-(tributylstannyl)thiophene, 2-bromobenzene, and 20phenylboronic acid. You can select more than one in the county. However, the end-capping agent is not limited thereto.

The step of purifying the polymer may further include removing impurities and oligomers of the polymerized polymer through a Soxhlet extractor, removing the catalyst used in the polymerization reaction through solid phase extraction (SPE), and purifying the polymer. have.

The Soxhlet extraction may be performed in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropane, chloroform and chlorobenzene.

The SPE may not be performed depending on the solubility.

Organic semiconductor device containing heterocyclic compound-based polymer and method for manufacturing the same

The present invention can provide an organic semiconductor device including a heterocyclic compound-based polymer and a method for manufacturing the same. In this case, the heterocyclic compound-based polymer can be obtained according to the method for preparing the heterocyclic compound described above.

The polymer according to the present invention may be included in an organic semiconductor device. Specifically, an organic conductor comprising the polymer, for example, a field effect transistor and a charge transport layer of a perovskite solar cell, an organic light emitting diode, a charge injection layer and an ITO planarization layer in a flat screen and a touch screen, an antistatic film, It may be used as a printed circuit and a capacitor, but is not limited thereto.

As an example, the present invention may particularly provide an organic solar cell including the above-described heterocyclic compound-based polymer as an electron donor material.

Specifically, the method of manufacturing an organic solar cell including a polymer comprises the steps of: a'') preparing a first electrode; b'') preparing a mixed solution by putting the polymer and the non-fullerene derivative prepared according to the method for producing the polymer into a solvent; c'') coating the mixed solution on the first electrode and drying to form a photoactive layer; d'') forming a second electrode on the photoactive layer.

Between each of the above steps, a step of forming a layer by preparing, coating and drying a hole transport layer and an electron transport layer may be included. The organic solar cell device structure may be a conventional structure or an inverted structure.

In step b'') of preparing the mixed solution, the photoactive layer is a heterocyclic compound-based polymer represented by Formula 2 and ITIC (CAS No. 16694293-06-4), ITIC-M (or IT-M or m-ITIC) (CAS No. 2047352-80-5), ITIC-Th (CAS No. 1889344-13-1), IDIC (CAS No. 1883441-92-6), IT-4F (or ITIC-4F) (CAS No. 2097998-59-7) and various non-fullerene derivatives and a bulk hetero junction may form a photoactive layer, but is not limited thereto. In addition, the photoactive layer may be an organic solar cell further comprising a non-fullerene derivative including at least one of indacenodithiophene derivative and indacenodithienothiophene derivative.

Specifically, the bifullerene derivative may include indacenodithiophene derivatives and indacenodithienothiophene derivatives. In addition, the bifullerene derivative may be one or more selected from the group consisting of indacenodithiophene derivatives and indacenodithienothiophene derivatives.

-((2Z,2

Z)-(((4,4,9-tris(4-hexylphenyl)-9-(4-pentylphenyl)-4,9-dihydro-sindaceno[1,2-b:5,6-b dithiophene-2,7-diyl)bis(4-((2-ethylhexyl)oxy)thiophene- 5,2-diyl))bis(methanylylidene))bis(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) 등일 수 있으며 이에 한정되는 것은 아니다.The indacenodithiophene derivative is, for example, IDIC(2,2'-((2Z,2'Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1, 2-b:5,6-b']dithiophene-2,7-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) etc. May be, but is not limited thereto. In addition, the indacenodithienothiophene derivative is, for example, ITIC(3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis (4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene), ITIC(3,9- bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'- d']-s-indaceno[1,2-b:5,6-b']dithiophene), ITIC-Th(3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone) ))-5,5,11,11-tetrakis(5-hexylthienyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6- b']dithiophene), ITIC-M(3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6/7-methyl)-indanone))-5,5,11,11 -tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene), ITIC-4F( 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[ 2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene), IEICO-4F((2,2'-((2Z, 2'Z)-(((4,4,9,9-tetrakis(4-hexylphenyl)-4,9-dihydro-sindaceno[1,2-b:5,6-b']dithiophene-2,7- diyl)bis(4-((2-ethylhexyl)o xy)thiophene-5,2-diyl))bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) and IEICO- 4Cl(2,2

-((2Z,2

Z)-(((4,4,9-tris(4-hexylphenyl)-9-(4-pentylphenyl)-4,9-dihydro-sindaceno[1,2-b:5,6-b dithiophene-2, 7-diyl)bis(4-((2-ethylhexyl)oxy)thiophene- 5,2-diyl))bis(methanylylidene))bis(5,6-dichloro-3-oxo-2,3-dihydro-1H- indene-2,1-diylidene)) dimalononitrile), and the like, but is not limited thereto.

The photoactive layer may include an electron acceptor compound including a non-fullerene derivative and the polymer described above. In the photoactive layer, the mixing ratio of the polymer and the electron acceptor compound is 1:0.5 to 1:2, 1:0.8 to 1:2, 1:0.9 to 1:2, 1:1.0 to 1:2, 1:1.1 to 1 :2, 1:1.2 to 1:2, 1:1.25 to 1:2, 1:1.3 to 1:2, 1:1.4 to 1:2, 1:1.5 to 1:2, 1:0.5 to 1:1.5 , 1:0.8 to 1:1.5, 1:0.9 to 1:1.5, 1:1.0 to 1:1.5, 1:1.1 to 1:1.5, 1:1.2 to 1:1.5, 1:1.25 to 1:1.5, 1 :1.3 to 1:1.5, 1:1.4 to 1:1.5, 1:0.5 to 1:1.3, 1:0.8 to 1:1.3, 1:0.9 to 1:1.3, 1:1.0 to 1:1.3, 1:1.1 To 1:1.3, 1:1.2 to 1:1.3, 1:1.25 to 1:1.3, 1:0.5 to 1:1.2, 1:0.8 to 1:1.2, 1:0.9 to 1:1.2, 1:1.0 to 1 :1.2, 1:1.1 to 1:1.2 or 1:0.5 to 1:0.8.

In addition, the perovskite solar cell according to the present invention may include the above-described polymer as an electron donor material in the hole transport layer. Specifically, the perovskite solar cell may use the polymer as a hole transport layer, and spiro-OMeTAD (2,2',7,7'-tetrakis-(N,Ndi-) typically used in perovskite 4-methoxyphenylamino)-9,9'-spirobifluorene) can be replaced.

Moreover, the field effect transistor according to the present invention may include the above-described polymer in the organic semiconductor layer. Specifically, in the field effect transistor, the polymer may be used as an active semiconductor layer, and silicon or inorganic metal oxide semiconductor may be replaced with an organic material.

In addition, the organic light emitting diode according to the present invention may include the above-described polymer in a hole transport layer or a hole injection layer. Specifically, in the organic light emitting diode, the polymer may be used as a hole transport layer or a hole injection layer, and a single molecule may be substituted.

Hereinafter, specific embodiments of the present invention will be described in detail. However, the spirit of the present invention is not limited to the presented embodiments, and a person skilled in the art who understands the spirit of the present invention can add, change, or delete other elements within the scope of the same idea. However, other embodiments included within the scope of the present invention may be easily proposed, but this will also be said to be within the scope of the present invention.

In the examples of the present invention, the synthesis methods that can generally design a carboxylate-halogen bisaophene unit, which is an example of a heterocyclic compound, and the synthesis method proposed in the present technology are compared with respect to the number of reaction steps and the total yield. The parts that did not proceed with the experiment were shown by replacing or prescribing to the literature.

In addition, in the examples of the present invention, a carboxylate-halogen bisaophene unit, which is an example of a heterocyclic compound, was synthesized in total of 8 types (including similar structures) (see FIGS. 1 to 4). In addition, in the embodiment of the present invention, a total of 8 types of organic semiconductor polymers based on a heterocyclic compound substituted with a carboxylate were synthesized through Still coupling (see FIGS. 5 to 12). All reactions were carried out under a nitrogen atmosphere.

EH-F-2DBDT, a precursor required for polymer synthesis, is EH-Cl-2DBDT (Nano Energy 40 (2017) 214-223, Adv. Mater. 2018, 30, 1800868) from a commercial chemical company (Sunatech Inc.). It was synthesized and used according to. Unless otherwise stated, all chemicals were purchased from Aldrich, TCI, Alfaaesar, etc. and used without purification.

<Example 1> Synthesis of carboxylate-chlorine bithiophene unit (BiT-COOBOCl-in) (see FIG. 1)

FIG. 1 is a schematic diagram of the synthesis of carboxylate-chlorine bithiophene (BiT-COOBOCl-in) in Example 1 of the present invention and a diagram of the synthesis mechanism. In order to synthesize the same final compound (2-butyloctyl 5,5'-dibromo-3'-chloro-2,2'-bithiophene-3-carboxylate), synthetic route 1 ( Synthetic route 1) showed a final yield of 40.5%, but the synthesis process was complicated through five steps, and another synthetic route, synthetic route 2, went through four steps, but the final yield was 12.4%. It was low. The method for preparing a heterocyclic compound according to the present invention simplifies the synthesis process through four steps, and shows a final yield of 60.4%, which is higher than that of the conventional synthetic route.

1-1: Synthesis of 5-bromothiophene-3-carboxylic acid

Prepare a 100 mL 2-neck flask. In the flask, 3.3 g (23.41 mmol) of the compound thiophene-3-carboxylic acid was dissolved in 24 mL of acetic acid, followed by vacuum and nitrogen substitution. 1.34 mL (25.75 mmol) of bromine was slowly added dropwise and reacted at room temperature for 1 hour. The degree of the reaction is checked through thin layer chromatography (TLC), and when the reaction is complete, the reaction is terminated with a saturated aqueous solution of sodium carbonate. Subsequently, a filtering device was installed to filter, and the upper material was recrystallized with hot water to obtain 4.12 g of a white solid (yield 85%). ¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm), 13.02-13.0 (s, 1H) 8.31-8.26 (d, 1H), 7.52-7.48 (d, 1H) (see Fig. 2).

1-2: Synthesis of 2-butyloctyl2-bromothiophene-3-carboxylate

Prepare a 100 mL 2-neck flask. In the flask, 3.5 g (16.90 mmol) of compound 1-1 was dissolved in 50 mL of methylenechloride, and degassed and nitrogen substituted. Then, 724 mg (5.92 mmol) of DMAP and 4.8 g (25.40 mmol) of 2-butyloctan-1-ol were added thereto, followed by stirring at room temperature for 15 minutes, and then 3.86 g (18.60 mmol). ) Of DCC and reacted for 48 hours. The degree of reaction is checked by TLC (thin layer chromatography), and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent from hexane vs. methylene chloride. After column purification in a volume ratio of 1:1, 6.03 g of colorless oil (95% yield) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.97 (s, 1H), 7.45 (s, 1H), 4.17-4.16 (d, 2H), 1.74-1.73 (m, 1H), 1.35-1.28 (m, 16H), 0.92-0.87 (m, 6H) (see Fig. 3).

1-3: 2-butyloctyl 5,5'-dibromo-2,2'-bithiophene-3-carboxylate (2-butyloctyl 5,5'-dibromo-2,2'-bithiophene-3 -carboxylate) synthesis

Prepare a 10-20 mL vial. In the vial, 0.6 g (1.60 mmol) of compound 1-2 is dissolved in 10 mL of dimethylsulfoxide. Thereafter, 22 mg (0.098 mmol) of Pd(OAc)2, 990 mg (4.27 mmol) of Ag ₂ O, and 0.326 g of 2-bromothiophene were added to the vial, and the vial lid was and- After capping, vacuum and nitrogen are replaced. Thereafter, the mixture was stirred at room temperature for 15 minutes and then reacted with reflux for 10 hours. The degree of reaction is checked by TLC (thin layer chromatography), and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent from hexane vs. methylene chloride. After column purification in a volume ratio of 1:1, 0.76 g of yellow oil (88% yield) was obtained. ¹ H NMR (400-20 -MHz, CDCl ₃ ) δ (ppm), 7.40 (s, 1H), 7.10 (s, 1H), 7.00 (s, 1H), 4.14-4.12 (d,2H), 1.66 ( m, 1H), 1.27 (m, 16H), 0.90-0.87 (m, 6H) (see Fig. 4).

1-4: 2-butyloctyl 5,5'-dibromo-3'-chloro-2,2'-bithiophene-3-carboxylate (2-butyloctyl-5,5'-dibromo-3' -chloro-2,2'-bithiophene-3-carboxylate)

Prepare a 10-20 mL vial. In the vial, 0.536 g (1.0 mmol) of compound 1-3 is dissolved in 15 mL of chloroform. Thereafter, 1.33 g (3.0 mmol) of lead tetraacetate was added to the vial, followed by degassing and strong nitrogen substitution. Then, 63.6 mg (1.5 mmol) of lithium chloride was added and stirred at room temperature for 15 minutes, followed by a reflux reaction for 10 hours. The degree of reaction is checked by TLC (thin layer chromatography) (if the reaction has not been completed, lithium chloride is added every 30 minutes depending on the situation). When the reaction is complete, a filtration device is installed to remove celite. After crushing and filtering with methylene chloride, the lower material was purified by column with a volume ratio of hexane to methylene chloride 1:1 by removing the solvent under reduced pressure, and then 0.49 g of yellow oil (yield 85%) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.50 (s,1H), 7.01-6.97 (s, 1H), 4.09-4.07 (d, 2H), 1.60 (m, 1H), 1.25-1.20 (m,16H), 0.90-0.87 (m, 6H) (see Fig. 5).

<Example 2> Synthesis of P(F-BiT) (COOBO)

2.1: Polymerization of EH-F-2DBDT and 1-3

Prepare a 2-5 mL vial. 53.64 mg (0.10 mmol) of compound 1-3 and 94.5 mg (0.10 mmol) of compound EH-F-2DBDT were added to the vial. Subsequently, 8.0 mg (0.00693 mmol, 6.925 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 3 mL of anhydrous toluene and 0.3 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour and 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material was dried in a vacuum oven at 50° C. for 24 hours, and then red-pink colored particles were obtained in a yield of 85.0%. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 6.

<Example 3> Synthesis of P(Cl-BiT) (COOBO)

3.1: Polymerization of EH-Cl-2DBDT and 1-3

Prepare a 2-5 mL vial. 53.64 mg (0.10 mmol) of compound 1-3 and 97.3 mg (0.10 mmol) of compound EH-Cl-2DBDT were added to the vial. Subsequently, 8.0 mg (0.00693 mmol, 6.925 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 3 mL of anhydrous toluene and 0.3 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour and 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material was dried in a vacuum oven at 50° C. for 24 hours, and then red-pink colored particles were obtained in a yield of 87.0%. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 7.

<Example 4> Synthesis of P(F-BiT) (COOBOCl-in)

4.1: Polymerization of EH-F-2DBDT and 1-4

Prepare a 2-5 mL vial. 57.1 mg (0.10 mmol) of compound 1-4 and 94.5 mg (0.10 mmol) of compound EH-F-2DBDT are added to the vial. Subsequently, 8.0 mg (0.00693 mmol, 6.925 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 3 mL of anhydrous toluene and 0.3 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour and 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material is dried in a vacuum oven at 50° C. for 24 hours, and then a bright red color is obtained in a yield of 74.0%. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 8.

<Example 5> Synthesis of carboxylate-chlorine bithiophene unit (BiT-COORCl-out) (R: BO, C8, C10, C12) (see FIG. 9)

9 is a schematic diagram of the synthesis of carboxylate-chlorine bithiophene (BiT-COORCl-out) in Example 5 of the present invention and a diagram of the synthesis mechanism. In order to synthesize the same final compound (2-butyloctyl-5,5'-dibromo-4'-chloro-2,2'-bithiophene-3-carboxylate), the synthetic route previously possible is The synthesis process was very complicated through seven steps, and the final yield was somewhat low at 35.7%. The method for preparing the heterocyclic compound according to the present invention dramatically simplifies the synthesis process through four steps, and the final yield is 65.4%, which is higher than the conventional synthetic route. In addition, not only the 2-butyloctyl-5,5'-dibromo-4'-chloro-2,2'-bithiophene-3-carboxylate, but also octyl-5,5'-dibromo- 4'-chloro-2,2'-bithiophene-3-carboxylate (yield: 64.6%), decyl-5,5'-dibromo-4'-chloro-2,2'-bithiophene -3-carboxylate (yield: 61.9%), dodecyl-5,5'-dibromo-4'-chloro-2,2'-bithiophene-3-carboxylate (yield: 59.8%) In the manufacture of, it was confirmed that the number of synthesis was reduced to improve the synthesis complexity and relatively high yield.

5-1: Synthesis of 2-octyl-5-bromothiophene-3-carboxylate

Prepare a 100 mL 2-neck flask. In the flask, 3.5 g (16.90 mmol) of compound 1-1 was dissolved in 50 mL of methylenechloride, and degassed and nitrogen substituted. Then, 724 mg (5.92 mmol) of DMAP and 3.3 g (25.40 mmol) of octan-1-ol (octan-1-ol) were added and stirred at room temperature for 15 minutes, followed by 3.86 g (18.60 mmol) of DCC. React for 48 hours. After checking the degree of reaction by TLC, and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent in a volume of hexane vs. methylene chloride 1:1. After column purification by ratio, 5.23 g of colorless oil (yield 97%) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.98 (s, 1H), 7.47 (s, 1H), 4.27-4.23 (d, 2H), 1.72-1.70 (m, 2H), 1.33-1.28 (m, 10H), 0.90-0.87 (m, 3H) (see Fig. 10).

5-2: Synthesis of 2-decyl-5-bromothiophene-3-carboxylate

Prepare a 100 mL 2-neck flask. In the flask, 3.5 g (16.90 mmol) of compound 1-1 was dissolved in 50 mL of methylenechloride, and degassed and nitrogen substituted. Subsequently, 724 mg (5.92 mmol) of DMAP and 4.0 g (25.40 mmol) of decan-1-ol were added, followed by stirring at room temperature for 15 minutes, followed by 3.86 g (18.60 mmol) of DCC. React for 48 hours. After checking the degree of reaction by TLC, and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent in a volume of hexane vs. methylene chloride 1:1. After column purification by ratio, 5.40 g of a colorless oil (92% yield) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.98 (s, 1H), 7.47 (s, 1H), 4.27-4.23 (d, 2H), 1.72-1.70 (m, 2H), 1.33-1.28 (m, 10H), 0.90-0.87 (m, 3H) (see Fig. 11).

5-3: Synthesis of 2-dodecyl-5-bromothiophene-3-carboxylate

Prepare a 100 mL 2-neck flask. In the flask, 3.5 g (16.90 mmol) of compound 1-1 was dissolved in 50 mL of methylenechloride, and degassed and nitrogen substituted. Then, 724 mg (5.92 mmol) of DMAP and 4.7 g (25.40 mmol) of dodecan-1-ol were added and stirred at room temperature for 15 minutes, followed by 3.86 g (18.60 mmol) of DCC. And react for 48 hours. After checking the degree of reaction by TLC, and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent in a volume of hexane vs. methylene chloride 1:1. After column purification by ratio, 5.90 g of colorless oil (yield 93%) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.98 (s, 1H), 7.47 (s, 1H), 4.27-4.23 (d, 2H), 1.72-1.70 (m, 2H), 1.33-1.28 (m, 10H), 0.90-0.87 (m, 3H) (see Fig. 12).

5-4: Synthesis of 2-bromo-3-chlorothiophene

Prepare a 10-20 mL vial. In the vial, 6.52 g (55.0 mmol) of 3-chlorothiophene is dissolved in 30 mL of chloroform and 30 mL of acetic acid. Thereafter, 9.80 g (55.0 mmol) of N-Bromosuccinimide was divided by 1/10 and reacted with reflux for 1 hour at room temperature. Check the degree of the reaction by TLC (if the reaction has not been completed, add a small amount of N-bromosuccinimide depending on the situation). When the reaction is complete, the reaction is terminated with a saturated aqueous solution of sodium carbonate. , Extraction with chloroform, removal of the solvent under reduced pressure, and column purification with hexane to give 9.78 g of colorless oil (yield 90%). ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.27-7.26 (d, 1H), 6.89-6.87 (d, 1H) (see FIG. 13).

5-5: 2-butyloctyl-5,5'-dibromo-4'-chloro-2,2'-bithiophene-3-carboxylate (2-butyloctyl-5,5'-dibromo-4 Synthesis of'-chloro-2,2'-bithiophene-3-carboxylate)

Prepare a 10-20 mL vial. In the vial, 0.3 g (0.8 mmol) of Compound 1-2 is dissolved in 5 mL of dimethylsulfoxide. Then, 11 mg (0.049 mmol) of Pd(OAc) ₂ , 495 mg (2.14 mmol) of Ag ₂ O, and 0.20 g of compound 5-4 were added thereto, followed by end-capping, followed by vacuum and nitrogen substitution. Then, the mixture was stirred at room temperature for 15 minutes and subjected to reflux for 10 hours. After checking the degree of reaction by TLC, and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent in a volume of hexane vs. methylene chloride 1:1. After column purification in a ratio, 0.41 g of yellow oil (90% yield) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.42 (s, 1H), 7.14 (s, 1H), 4.15-4.13 (d, 2H), 1.67 (m, 1H), 1.27-1.20 (m) , 16H), 0.90-0.83 (m, 6H) (see Fig. 14).

5-6: octyl-5,5'-dibromo-4'-chloro-2,2'-bithiophene-3-carboxylate (octyl-5,5'-dibromo-4'-chloro-2 ,2'-bithiophene-3-carboxylate)

Prepare a 10-20 mL vial. In the vial, 0.26 g (0.8 mmol) of compound 5-1 is dissolved in 5 mL of dimethylsulfoxide. Then, 11 mg (0.049 mmol) of Pd(OAc) ₂ , 495 mg (2.14 mmol) of Ag ₂ O, and 0.20 g of compound 5-4 were added thereto, followed by end-capping, followed by vacuum and nitrogen substitution. Then, the mixture was stirred at room temperature for 15 minutes and subjected to reflux for 10 hours. After checking the degree of reaction by TLC, and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent in a volume of hexane vs. methylene chloride 1:1. After column purification by ratio, 0.36 g of yellow oil (yield 87%) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ(ppm),7.44 (s, 1H), 7.15 (s, 1H), 4.25-4.21 (d, 2H), 1.69 (m, 2H), 1.31-1.25 (m , 10H), 0.90-0.87 (m, 3H) (see Fig. 15).

5-7: decyl-5,5'-dibromo-4'-chloro-2,2'-bithiophene-3-carboxylate (decyl-5,5'-dibromo-4'-chloro-2 ,2'-bithiophene-3-carboxylate)

Prepare a 10-20 mL vial. In the vial, 0.28 g (0.8 mmol) of compound 5-2 is dissolved in 5 mL of dimethylsulfoxide. Then, 11 mg (0.049 mmol) of Pd(OAc) ₂ , 495 mg (2.14 mmol) of Ag ₂ O, and 0.20 g of compound 5-4 were added thereto, followed by end-capping, followed by vacuum and nitrogen substitution. Then, the mixture was stirred at room temperature for 15 minutes and subjected to reflux for 10 hours. After checking the degree of reaction by TLC, and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent in a volume of hexane vs. methylene chloride 1:1. After column purification by ratio, 0.38 g of yellow oil (88% yield) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.43 (s, 1H), 7.15 (s, 1H), 4.24-4.21 (d, 2H), 1.68-1.66 (m, 2H),1.31-1.27 (m, 12H), 0.90-0.86 (m, 3H) (see Fig. 16).

5-8: dodecyl-5,5'-dibromo-4'-chloro-2,2'-bithiophene-3-carboxylate (dodecyl-5,5'-dibromo-4'-chloro- 2,2'-bithiophene-3-carboxylate) synthesis

Prepare a 10-20 mL vial. In the vial, 0.3 g (0.8 mmol) of compound 5-3 is dissolved in 5 mL of dimethylsulfoxide. Then, 11 mg (0.049 mmol) of Pd(OAc) ₂ , 495 mg (2.14 mmol) of Ag ₂ O, and 0.20 g of compound 5-4 were added thereto, followed by end-capping, followed by vacuum and nitrogen substitution. Then, the mixture was stirred at room temperature for 15 minutes and subjected to reflux for 10 hours. After checking the degree of reaction by TLC, and when the reaction is complete, a filtration device is installed to spread celite, filter with methylene chloride, and remove the solvent under reduced pressure to remove the solvent in a volume of hexane vs. methylene chloride 1:1. After column purification by ratio, 0.38 g of yellow oil (84% yield) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.68 (s, 1H), 7.21 (s, 1H), 4.28-4.04 (d, 2H), 1.70-1.66 (m, 2H), 1.31-1.27 (m, 14H), 0.77-0.70 (m, 3H) (see Fig. 17).

<Example 6> Synthesis of P(F-BiT) (COOBOCl-out)

6.1: Polymerization of EH-F-2DBDT and 5-5

Prepare a 2-5 mL vial. 57.1 mg (0.10 mmol) of compound 5-5 and 94.5 mg (0.10 mmol) of compound EH-F-2DBDT are added to the vial. Subsequently, 8.0 mg (0.00693 mmol, 6.925 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 3 mL of anhydrous toluene and 0.3 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour and 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material is dried in a vacuum oven at 50° C. for 24 hours, and then red-pink powder is obtained in a yield of 89.0%. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 18.

<Example 7> Synthesis of P(F-BiT)(COOC8Cl-out)

7.1: Polymerization of EH-F-2DBDT and 5-6

Prepare a 2-5 mL vial. 51.5 mg (0.10 mmol) of compound 5-6 and 94.5 mg (0.10 mmol) of compound EH-F-2DBDT are added to the vial. Subsequently, 8.0 mg (0.00693 mmol, 6.925 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 3 mL of anhydrous toluene and 0.3 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour and 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material is dried in a vacuum oven at 50° C. for 24 hours, and then red-pink powder is obtained in a yield of 89.0%. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 19.

<Example 8> Synthesis of P(Cl-BiT)(COOC8Cl-out)

8.1: Polymerization of EH-Cl-2DBDT and 5-6

Prepare a 2-5 mL vial. 51.5 mg (0.10 mmol) of compound 5-6 and 97.3 mg (0.10 mmol) of compound EH-Cl-2DBDT are added to the vial. Subsequently, 8.0 mg (0.00693 mmol, 6.925 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 3 mL of anhydrous toluene and 0.3 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material is dried in a vacuum oven at 50° C. for 24 hours, and then red-pink powder is obtained in a yield of 88.0%. ¹ H NMR (400 MHz, CDCl ₃ ) appeared as shown in FIG. 20.

<Example 9> Synthesis of P(Cl-BiT)(COOC10Cl-out)

9.1: Polymerization of EH-Cl-2DBDT and 5-7

Prepare a 2-5 mL vial. 54.3 mg (0.10 mmol) of compound 5-7 and 97.3 mg (0.10 mmol) of compound EH-Cl-2DBDT are added to the vial. Subsequently, 8.0 mg (0.00693 mmol, 6.925 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 3 mL of anhydrous toluene and 0.3 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour and 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material is dried in a vacuum oven at 50° C. for 24 hours, and then red-pink powder is obtained in a yield of 82.0%. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 21.

<Example 10> Synthesis of P(Cl-BiT)(COOC16Cl-out)

10.1: Polymerization of EH-Cl-2DBDT and 5-8

Prepare a 2-5 mL vial. 57.1 mg (0.10 mmol) of compound 5-8 and 97.3 mg (0.10 mmol) of compound EH-Cl-2DBDT are added to the vial. Subsequently, 8.0 mg (0.00693 mmol, 6.925 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 3 mL of anhydrous toluene and 0.3 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour and 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material is dried in a vacuum oven at 50° C. for 24 hours, and then red-pink powder is obtained in a yield of 82.0%. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 22.

<Example 11> Synthesis of carboxylate cyazole-thiophene (TzT) unit (TzT-COOBO) (see FIG. 23)

23 is a schematic diagram of the synthesis of carboxylate cyanazole-thiophene (TzT-COOBO) in Example 11 of the present invention and a diagram of the synthesis mechanism. The synthesis route that was previously possible went through four steps and the final yield was 65.9%, but the method for preparing the heterocyclic compound according to the present invention simplified the synthesis process through two steps, and the final yield was 76.4%. The yield was higher than that of the root.

11-1: Synthesis of 2-butyloctyl-2-bromothiazole-4-carboxylate

Prepare a 100 mL 2-neck flask. In the flask, 1.76 g (8.45 mmol) of 2-bromothiazole-4-carboxylic acid was dissolved in 25 mL of methylenechloride, followed by degassing and nitrogen substitution. Then, 362 mg (2.96 mmol) of DMAP and 2.4 g (16.70 mmol) of 2-butyloctan-1-ol were added and stirred at room temperature for 15 minutes, followed by 1.93 g (9.30 mmol). ) Of DCC and reacted for 48 hours. The degree of reaction was checked by TLC, and when the reaction was completed, a filtration device was installed to spread celite, filtered with methylene chloride, and the lower material was removed under reduced pressure to remove the solvent, and the volume of hexane vs. methylene chloride 1:2. After column purification by ratio, 3.12 g of colorless oil (yield 98%) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 8.06 (s, 1H), 4.26-4.25 (d, 2H), 1.79 (m, 2H), 1.37-1.29 (m, 16H), 0.91-0.86 (m, 6H) (see Fig. 24).

11-2: 2-butyloctyl-2-bromo-5-(5-bromothiophen-2-yl)cyazole-4-carboxylate (2-butyloctyl-2-bromo-5-(5- Synthesis of bromothiophen-2-yl)thiazole-4-carboxylate)

Prepare a 10-20 mL vial. In the vial, 0.3 g (0.80 mmol) of compound 5-3 is dissolved in 5 mL of dimethylsulfoxide. Then, 11 mg (0.049 mmol) of Pd(OAc) ₂ , 495 mg (2.14 mmol) of Ag ₂ O, and 0.20 g of compound 5-4 were added thereto, followed by end-capping, followed by vacuum and nitrogen substitution. Then, the mixture was stirred at room temperature for 15 minutes and subjected to reflux for 10 hours. The degree of reaction was checked by TLC, and when the reaction was completed, a filtration device was installed to spread celite, filtered with methylene chloride, and the lower material was removed under reduced pressure to remove the solvent, and the volume of hexane vs. methylene chloride 1:2. After column purification by ratio, 0.38 g of yellow oil (yield 78%) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm), 7.13-7.12 (d,1H), 7.04-7.03 (d, 1H), 4.23-4.22 (d, 2H), 1.74 (m, 1H), 1.27 (m, 16H), 0.89-0.88 (m, 6H) (see Fig. 25).

<Example 12> Synthesis of P(F-TzT) (COOBO)

12.1: Polymerization of EH-F-2DBDT and 11-2

Prepare a 2-5 mL vial. 50.0 mg (0.093 mmol) of compound 11-2 and 87.5 mg (0.093 mmol) of compound EH-F-2DBDT are added to the vial. Subsequently, 7.4 mg (0.00644 mmol, 6.435 mol%) of Pd(PPh ₃ ) ₄ was added and the cap of the vial was capped. Then, the mixture is stirred for 30 minutes in a vacuum state. After nitrogen replacement, add 2.8 mL of anhydrous toluene and 0.28 mL of anhydrous dimethylamide, and hold a vacuum for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture in the vial is reacted for 3 hours at 100 °C (if bubbling and precipitated portions are found when shaking, 0.1 mL of 2-bromothiophene is immediately added and end-capped for 1 hour 30 minutes. ). Thereafter, 0.2 mL of 2-(tributylstannyl)thiophene was added and end-capped for 1 hour and 30 minutes. Thereafter, the temperature was lowered and 6 mL of methanol was added, followed by stirring for 30 minutes. Thereafter, the cap of the vial was removed and the reacted polymer in the vial was transferred to a thimble, followed by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene, and chloroform. More refined. The dissolved material in the chloroform fraction is concentrated under reduced pressure, purified by SPE, dissolved in chlorobenzene to a high concentration, and then reprecipitated with cold methanol. Thereafter, the material is collected after filtration using a Buchner panel. The collected material is dried in a vacuum oven at 50° C. for 24 hours, and then red-pink powder is obtained in a yield of 88.0%. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 26.

<Test Example 1> Analysis of physical, optical and electrochemical properties of polymers based on heterocyclic compounds

1. Physical properties of polymers based on heterocyclic compounds

Physical properties were analyzed according to structural changes of the synthesized heterocyclic compound-based polymers. Molecular weight analysis such as number average molecular weight (M _n ), weight average molecular weight (M _w ) and polydispersity index (PDI) is performed by GPC (Gel permeation chromatography) measurement using chloroform. (NS-4000, FUTECS). Thermal decomposition temperature (T _d ) was performed by TGA (Thermogravimetric analysis) measurement (NETZSCH 209 F3) (see Table 1).

division M _n (Da) M _w (Da) PDI T _d (℃) Example 2 33,900 78,180 2.30 398 Example 3 32,050 89,200 2.78 392 Example 4 14,500 24,200 1.67 334 Example 6 52,200 92,990 1.78 385 Example 7 45,900 76,500 1.67 395 Example 8 42,050 88,810 2.11 391 Example 9 47,000 83,600 1.78 405 Example 10 38,500 91,000 2.36 408 Example 12 41,999 72,105 1.72 349

2. Optical and electrochemical properties of polymers based on heterocyclic compounds

Optical and electrochemical properties were analyzed according to structural changes of the synthesized heterocyclic compound-based polymers. Analysis such as Highest occupied molecular orbital (HOMO), Lowest occupied molecular orbital (LUMO), and bandgap (E _g ^opt ) were performed with UV (HP Agilent 8453 UV-Vis spectrophotometer) and CV (Znahner IM6eX electrochemical workstation) measurements. The optical band gap of the synthesized heterocyclic compound-based polymers was calculated through 1239/λonset. The ferrocene half-wave level (E _1/2 , _ferrocene ) was measured to be 0.49 eV. This is introduced together with the measured oxidation onset energy (E _onset ) value in the following electrochemical formula [E _HOMO = -4.8-(E _onset -E _1/2 , _ferrocene )] to determine the HOMO energy levels of the heterocyclic compound-based polymers. Each was obtained. The LUMO energy levels were calculated as the difference between the chemical HOMO energy levels using each optical bandgap (see Table 2 and FIGS. 27 to 32).

division HOMO (eV) LUMO (eV) E _g ^opt (eV) Example 2 -5.54 -3.55 1.97 Example 3 -5.57 -3.58 1.99 Example 4 -5.71 -3.56 2.15 Example 6 -5.66 -3.60 1.99 Example 7 -5.62 -3.71 2.00 Example 8 -5.71 -3.69 2.02 Example 9 -5.68 -3.74 1.95 Example 10 -5.73 -3.75 1.98 Example 12 -5.77 -3.76 2.01

<Example 13> Fabrication of organic solar cell device containing heterocyclic compound-based polymer

The performance was evaluated by fabricating an inverted structure organic solar cell device containing the heterocyclic compound-based polymer. The reverse structure organic solar cell was manufactured as ITO/ZnO/polymer:IT-4F=1:1/MoO ₃ /Ag (see FIG. 35). The production method is as follows in detail. First, the patterned ITO glass substrate was washed with a cleaning agent (Alconox), acetone, isopropanol (Isopropanol, IPA), and ultrapure water in that order. After drying, the surface was modified to hydrophilic properties by UV-ozone treatment. Then, a ZnO precursor solution was prepared by a sol-gel method to form a ZnO thin film having a thickness of about 30-40 nm. The thin film was heated at 200 °C for 1 hour in the air. Subsequent processes were performed in a nitrogen atmosphere in the glove box. The photoactive layer was spin coated to a thickness of 90-100 nm according to the conditions of each solution. Finally, the MoO _3/100 nm Ag film of 5 nm and an upper electrode were thermally deposited in a vacuum (less than 10 ^-6 Torr). The photoactive area of the manufactured device was 0.04 to 0.12 cm ² . The solar simulator (Newport Oriel, 1000 W) was characterized with an air mass (AM) 1.5G filter. The intensity of the solar simulator was set to 100 mW·cm ^-2 using an AIST-certified silicon reference element.

<Test Example 2> Evaluation of an organic solar cell device containing a heterocyclic compound-based polymer

Current-voltage behavior was measured using a Keithley 2400 SMU. EQE (External quantum efficiency) behavior was measured using a Polaronix K3100 IPCE measurement system (McScience Inc.).

The reverse structure organic solar cell device was fabricated and evaluated based on the analysis of the properties of the polymers based on the heterocyclic compound synthesized according to the structural change. For efficiency optimization, a small amount of Diiodooctane (DIO) was added to Chlorobeznene (CB) in a small amount of 0.5%, and a concentration of 1.2-1.5 wt% was used (see Table 3, FIGS. 33 and 34). Adv.Funct. Mater. It is superior to the polymer P (BDT-S-TC) of similar structure of 2018, 28, 1706517 (Comparative Example 1).

division V _oc (V) J _se (mA/cm ² ) FF(%) PCE (%) Example 6: IT-4F = 1:1 0.879 18.2 66.7 10.7 Comparative Example 1: ITIC
=1:1 0.960 16.4 64.3 10.12

In addition, when the organic solar cell device fabricated in Example 12: IT-4F=1:1 was evaluated in the same manner as above, V _oc was 0.798V, J _sc was 13.9 mA/cm ² , FF was 41.1% and PCE was 4.6%. Cyazole-thiophene (TzT)-containing polymer had a high degree of change in the frontier energy level and the direction of the bonding dipole moment, so that the electric charge could not flow well. Solar cells appeared to be at a usable level.

In the present invention, a method of manufacturing high-performance polymers has been described through the above examples as described above, but the method of manufacturing the polymers is not particularly limited, and any manufacturing method that satisfies the above reaction equations may be used.

In addition, the organic solar cell device of the present invention may be manufactured in the order of anode/hole transport layer/photoelectric conversion layer/electron transport layer/cathode as described above, and the reverse order, that is, cathode/electron transport layer/photoelectric conversion layer/ It may be manufactured in the order of hole transport layer/anode.

In the above, the configuration and features of the present invention have been described based on the embodiments according to the present invention, but the present invention is not limited thereto, and various changes or modifications can be made within the spirit and scope of the present invention. It will be apparent to those skilled in the art, and therefore, such changes or modifications are found to belong to the appended claims.

101: cathode/anode; Indium Tin Oxide (ITO) glass substrate
102: cathode/anode buffer layer; ZnO
103: photoactive layer
104: anode/cathode buffer layer; MoO ₃
105: anode/cathode; Ag

Claims (19)

a) synthesizing a compound represented by the following formula 1a; And
b) A method for preparing a heterocyclic compound comprising the step of synthesizing a compound represented by the following Formula 1 by reacting the compound represented by Formula 1a synthesized in step a) with a compound represented by Formula 1b
[Formula 1a]

[Formula 1b]

[Formula 1]

In Formula 1a and Formula 1b,
Q is each independently one selected from O, S, Se and Te,
Z is each independently selected from CR ₃ and N,
X is one independently selected from halogen and haloalkyl substituted sulfonate groups,
Each R ₁ is independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; is selected at least one from the group consisting of,
R ₂ and R ₃ are each independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an arylsulfoxy group; at least one is selected from the group consisting of.
The method of claim 1,
The step a) comprises: i) reacting a compound represented by the following formulas 1a-i with at least one of a sulfonate substituted with halogen and haloalkyl in a solvent to obtain a compound represented by the following formulas 1a-ii, and ii) A method for producing a heterocyclic compound further comprising the step of reacting the obtained compound represented by Formula 1a-ii with a compound represented by Formula 1a' in a solvent to obtain a compound represented by Formula 1a:
[Formula 1a-i]

[Formula 1a-ii]

[Formula 1a']

The method of claim 2,
The solvent is a method for producing a heterocyclic compound comprising at least one selected from a polar aprotic solvent, a nonpolar solvent, and a mixed solvent thereof.
The method of claim 2,
A catalyst is used for the reaction, and the catalyst is a method for producing a heterocyclic compound comprising at least one selected from the group consisting of a nucleophilic catalyst and a complex compound catalyst.
The method of claim 4,
The nucleophilic catalyst is a hetero containing at least one selected from the group consisting of N,N'-dicyclohexylcarbodiimide (N,N'-dicyclohexylcarbodiimide, DCC) and 4-dimethylaminopyridine (DMAP) Method for producing a cyclic compound.
The method of claim 1,
The step b) is a method for producing a heterocyclic compound performed in a solvent.
The method of claim 6,
The solvent is a polar aprotic solvent, a method for producing a heterocyclic compound.
The method of claim 6,
A catalyst is used in the reaction, and the catalyst is palladium acetate (Pd(OAc) ₂ ), palladium trifluroacetate (Pd(TFA) ₂ ), tetrakis (triphenylphosphine) palladium (Pd(PPh ₃ ) ₄ ), bis (dibenzylideneacetone) palladium (Pd(dba) ₂ ), tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ) and copper acetate (Cu(OAc) ₂ ) selected from the group consisting of Method for producing a heterocyclic compound containing one or more.
The method of claim 1,
In the step b), the compound represented by Formula 1a is reacted with the compound represented by Formula 1b in a solvent to obtain a reactant, and a halogen salt is added to the reactant to obtain a compound represented by Formula 1 Method for producing a heterocyclic compound comprising the step.
Polymer containing a repeating unit represented by the following formula (2):
[Formula 2]

In Chemical Formula 2,
n is an integer between 1 and 10,000,
Q is each independently one selected from O, S, Se and Te,
Z is each independently selected from CR ₃ and N,
Each R ₁ is independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; is selected at least one from the group consisting of,
Each R ₃ is independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an aryl sulfoxy group; is selected at least one from the group consisting of,
D is the unit of electron donation.
The method of claim 10,
D is a polymer which is an electron donating unit represented by the following formula (3):
[Formula 3]

In Chemical Formula 3, Ri is bonded with an adjacent 5-membered heteroaryl derivative to form a fused ring; Single bond; A group derived from a 5 to 6 membered monocyclic carbocyclic compound unsubstituted or substituted with a substituent J; A group derived from a 5 to 6 membered monocyclic heterocyclic compound including at least one selected from N, P, O, S, Se and Te substituted or unsubstituted with a substituent J; And 5 to 6 atoms including at least one selected from 5 to 6 reduced monocyclic carbocyclic compounds substituted or unsubstituted with substituent J and N, P, O, S, Se and Te substituted or unsubstituted with substituent J A group derived from a polycyclic fused ring compound in which at least two or more of the monocyclic heterocyclic compounds are fused; and at least one selected from the group consisting of,
Q is each independently one selected from O, S, Se and Te,
Each R is independently hydrogen; Halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Aryloxy group; Arylsulfoxy group; And an amine group; is selected from the group consisting of,
J is each independently a halogen group; Cyanogi; C _1-16 alkyl group; _{2 ~} C ₁₆ alkenyl group; C _{2 ~ 16} alkynyl group; Aryl group; Aralkyl group; A heterocyclic alkyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heterocyclic alkenyl group containing at least one hetero atom selected from N, P, O, S, Se and Te; A heteroaryl group containing at least one hetero atom selected from N, P, O, S, Se and Te; Hydroxyl group; C _1-16 alkoxy group; Amino group; Nitro group; Thiol group; Thionyl group; Thioether group; Lee Min-ki; Cyano group; Phosphonato group; Phosphine group; Carboxyl group; Carbam oil group; Carbamic acid group; Acetal group; Urea; Thiocarbonyl group; Sulfonyl group; Sulfonamide group; Sulfonate group; Silyl group; Ketone group; Aldehyde group; Ester group; Acetyl group; Isetoxy group; Amide group; Haloalkyl group; Aminoacyl group; Aminoalkyl group; Alkyl sulfoxy group; Amine group; Aryloxy group; And an arylsulfoxy group; at least one is selected from the group consisting of.
The method of claim 10,
The polymer has a number average molecular weight of 500 Da to 100 kDa.
The method of claim 10,
The polymer has a polydispersity index (PDI) of 1.0 to 100.
An organic solar cell comprising the polymer according to any one of claims 10 to 13 as a photoactive layer.
The method of claim 14,
The photoactive layer is an organic solar cell further comprising a non-fullerene derivative including at least one of an indacenodithiophene derivative and an indacenodithienothiophene derivative.
A perovskite solar cell comprising the polymer according to any one of claims 10 to 13 as a charge transport layer.
A field effect transistor comprising the polymer according to any one of claims 10 to 13.
An organic light-emitting diode comprising the polymer according to any one of claims 10 to 13.
A flat or touch screen comprising the polymer according to any one of claims 10 to 13 as a charge injection layer.

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