JP6459971B2 - Organic semiconductor materials - Google Patents

Description

  The present invention relates to a polymer compound having a structural unit having a specific benzobisthiazole skeleton, an organic semiconductor material, and a method for producing the same.

  The organic semiconductor material is one of the most important materials in the field of organic electronics, and can be classified into an electron donating p-type organic semiconductor material and an electron accepting n-type organic semiconductor material. Various elements can be manufactured by appropriately combining p-type organic semiconductor materials and n-type organic semiconductor materials. Such elements include, for example, excitons formed by recombination of electrons and holes ( It is applied to organic electroluminescence that emits light by the action of excitons), organic thin-film solar cells that convert light into electric power, and organic thin-film transistors that control the amount of current and voltage.

  Among these, organic thin-film solar cells are useful for environmental preservation because they do not release carbon dioxide into the atmosphere, and demand is increasing because they are easy to manufacture with a simple structure. However, the photoelectric conversion efficiency of the organic thin film solar cell is still not sufficient. The photoelectric conversion efficiency η is calculated by the product “η = open circuit voltage (Voc) × short circuit current density (Jsc) × curve factor (FF)” of the short circuit current density (Jsc), the open circuit voltage (Voc), and the fill factor (FF). In order to increase the photoelectric conversion efficiency, it is necessary to improve the short circuit current density (Jsc) and the fill factor (FF) in addition to the improvement of the open circuit voltage (Voc).

  Since the open circuit voltage (Voc) is proportional to the energy difference between the HOMO (highest occupied orbital) level of the p-type organic semiconductor and the LUMO (lowest unoccupied orbital) level of the n-type organic semiconductor, the open circuit voltage (Voc) ) Needs to be deepened (reduced) in the HOMO level of the p-type organic semiconductor.

  Further, the short circuit current density (Jsc) correlates with the amount of energy received by the organic semiconductor material. In order to improve the short circuit current density (Jsc) of the organic semiconductor material, from the visible region to the near infrared region. It is necessary to absorb light in a wide wavelength range. Of the light that can be absorbed by the organic semiconductor material, the wavelength of the light with the lowest energy (the longest wavelength) is the absorption edge wavelength, and the energy corresponding to this wavelength corresponds to the band gap energy. Therefore, in order to absorb light in a wider wavelength range, it is necessary to narrow the band gap (energy difference between the HOMO level and the LUMO level of the p-type organic semiconductor).

On the other hand, research on p-type organic semiconductor materials is also actively conducted. For example, Non-Patent Document 1 includes 4,4′-bis (2-ethylhexyl) dithieno [3,2-b; 2 ′, 3 ′,-d] silole and 2,1,3-benzothiadiazole. Coalescence has been proposed. However, the p-type organic semiconductor material described in Non-Patent Document 1 may not have a sufficiently deep HOMO level. Non-Patent Document 2 proposes a p-type organic semiconductor material having a benzodithiophene skeleton. However, the p-type organic semiconductor material described in Non-Patent Document 2 is limited in the skeleton and substituents that can be introduced due to problems in the synthesis method.
Further, Patent Documents 1 and 2 each propose a compound having a benzobisthiazole skeleton, but the conversion efficiency is not clear.

JP 2007-238530 A JP 2010-053093 A

Jianhui Hou and 4 others, “Synthesis, Characterization, and Photovoltaic Properties of a Low Band Gap Polymer Based on Silole-Containing Polythiophenes and 2,1,3-Benzothiadiazole” Journal of the American Chemical Society, 2008, 130, 16144-16145 . Latian Dou and 8 others, “Systematic Investigation of Benzodithiophene- and Diketopyrrolopyrrole-Based Low-Bandgap Polymers Designed for Single Junction and Tandem Polymer Solar Cells” Journal of the American Chemical Society, 2012, 134, 10071-10079.

  The subject of this invention is providing the organic-semiconductor material excellent in conversion efficiency. Another object of the present invention is to provide a raw material compound in which a chemical structure and a conversion efficiency are closely related to each other and an organic semiconductor material can introduce more various skeletons and substituents. Furthermore, it is providing the manufacturing method of such an organic-semiconductor material and its raw material compound.

  In order to improve the conversion efficiency, that is, to improve the short-circuit current density (Jsc) while improving the open-circuit voltage (Voc), the present inventors have absorbed light in a wide wavelength range into a p-type organic semiconductor. At the same time, it has been found that the HOMO level is appropriately deepened. And earnestly examined paying attention to the correlation of the conversion efficiency and chemical structure in p-type organic-semiconductor material. As a result, by using an organic semiconductor polymer having a specific structure, the HOMO level and the LUMO level can be adjusted to an appropriate range, so that the short circuit current density (Jsc) can be improved while improving the open circuit voltage (Voc). Furthermore, the inventors have found that charge separation can be easily caused between a p-type organic semiconductor and an n-type organic semiconductor, thereby completing the present invention.

  That is, the polymer compound according to the present invention includes a benzobisthiazole structural unit represented by the general formula (1).

[In General Formula (1), A ¹ and A ² are each independently substituted with an thiophene ring, hydrocarbon group or organosilyl group which may be substituted with an alkoxy group, a thioalkoxy group or a hydrocarbon group. It represents a thiazole ring which may be substituted, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. In the general formula (1), A ¹ and A ² are each preferably at least one selected from groups represented by the following general formulas (a1) to (a4).

[In General Formulas (a1) to (a4), R ^{21 to} R ²³ and R ²⁵ each independently represents a hydrocarbon group having 8 to 30 carbon atoms. R ²⁴ represents a hydrogen atom or a hydrocarbon group having 8 to 30 carbon atoms. * Represents a bond bonded to the benzene ring of benzobisthiazole. ]

  The polymer compound of the present invention is preferably a donor-acceptor type semiconductor polymer, and an organic semiconductor material containing the polymer compound of the present invention is also included in the scope of the present invention.

  The present invention also includes a benzobisthiazole compound represented by the general formula (6).

[In general formula (6),
A ¹ and A ² are each independently an alkoxy group, a thioalkoxy group, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or It represents a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
R ^{7 to} R ¹⁰ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ¹ and M ² each independently represent a boron atom or a tin atom. R ⁷ and R ⁸ may form a ring together with M ¹ , and R ⁹ and R ¹⁰ may form a ring together with M ² .
m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ⁷ and R ⁹ may be the same or different. ]

  The present invention also includes a benzobisthiazole compound represented by the general formula (5).

[In General Formula (5), A ¹ and A ² are each independently substituted with an thiophene ring, hydrocarbon group or organosilyl group which may be substituted with an alkoxy group, a thioalkoxy group or a hydrocarbon group. It represents a thiazole ring which may be substituted, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. ]

  The present invention also includes a benzobisthiazole compound represented by the general formula (4).

[In general formula (4),
A ¹ and A ² are each independently an alkoxy group, a thioalkoxy group, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or It represents a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]

  The present invention also includes a benzobisthiazole compound represented by the general formula (3).

[In General Formula (3), X represents a halogen atom. R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]
The present invention also includes a benzobisthiazole compound represented by the general formula (3 ′).

[In general formula (3 ′),
X represents a halogen atom.
R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]
The present invention also includes a benzobisthiazole compound represented by the general formula (2).

[In General Formula (2), R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]
The production method of the present invention comprises a compound represented by the general formula (2) using benzobisthiazole as a starting material,

[In General Formula (2), R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]
A compound represented by the general formula (3),

[In General Formula (3), X represents a halogen atom. R ^{1 to} R ⁶ represent the same groups as described above. ]
A compound represented by the following general formula (4):

[In General Formula (4), A ¹ and A ² are thiazole optionally substituted with an thiophene ring, hydrocarbon group or organosilyl group optionally substituted with an alkoxy group, thioalkoxy group or hydrocarbon group. It represents a ring or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. R ^{1 to} R ⁶ represent the same groups as described above. ]
A compound represented by the following general formula (5), and

[In General Formula (5), A ¹ and A ² represent the same groups as A ¹ and A ² in General Formula (4), respectively. ]
Compound represented by the following general formula (6)

[In General Formula (6), A ¹ and A ² represent the same groups as A ¹ and A ² in General Formula (4), respectively. R ^{7 to} R ¹⁰ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. M ¹ and M ² each independently represent a boron atom or a tin atom. R ⁷ and R ⁸ may form a ring together with M ¹ , and R ⁹ and R ¹⁰ may form a ring together with M ² . m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ⁷ and R ⁹ may be the same or different. ]
It is characterized by going through.

The production method of the present invention preferably includes the following first step and second step.
First step: A step of reacting a benzobisthiazole with a base and a halogenated silane compound to obtain a compound represented by the general formula (2) Second step: A compound represented by the general formula (2) with a base and a halogen A step of obtaining a compound represented by the general formula (3) by reacting with a chemical reagent

The production method of the present invention preferably further includes a third step, a fourth step, and a fifth step.
Third step: reacting the compound represented by the general formula (3) with the compound represented by the general formula (7) and / or (8) in the presence of a metal catalyst,

[In General Formulas (7) and (8), A ¹ and A ² each represent the same group as described above. R ¹¹ and R ¹² each independently represents a hydrogen atom or * -M ³ (R ¹³ ) _k R ¹⁴ . R ¹³ and R ¹⁴ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. M ³ represents a boron atom or a tin atom. R ¹³ and R ¹⁴ may form a ring together with M ³ . k represents an integer of 1 or 2. When k is 2, the plurality of R ¹³ may be the same or different. * Represents a bond with A ¹ or A ² . ]
Step of obtaining compound represented by general formula (4) Fourth step: Process of treating compound represented by general formula (4) with acid or base to obtain compound represented by general formula (5) Fifth step: a step of obtaining a compound represented by the general formula (6) by reacting a compound represented by the general formula (5) with a base and a tin halide compound or a borate ester.

Moreover, it is preferable that the manufacturing method of this invention contains a 6th process and a 7th process further.
Sixth step: General formula (9) and / or general formula (10) in the presence of a metal catalyst in the compound represented by general formula (6)

[In the general formulas (9) and (10),
R ²⁷ and R ²⁸ represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
X ¹ and X ² represent a halogen atom. ]
Is reacted with a compound represented by the general formula (11):

[In general formula (11),
A ¹ , A ² , R ²⁷ and R ²⁸ each represent the same group as described above. ]
Step 7 for obtaining a compound represented by general formula (11): A compound represented by general formula (11) is reacted with a base and a tin halide compound or a borate ester to obtain a compound represented by general formula (12). Obtaining process

[In general formula (12),
A ¹ , A ² , R ²⁷ and R ²⁸ each represent the same group as described above.
R ^{29 to} R ³¹ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ³ and M ⁴ each independently represent a boron atom or a tin atom.
R ²⁹ and R ³⁰ may form a ring together with M ³ , and R ³¹ and R ³² may form a ring together with M ⁴ .
m1 and n1 each represents an integer of 1 or 2. When m1 and n1 are 2, the plurality of R ²⁹ and R ³¹ may be the same or different. ]

  The polymer compound of the present invention has a deep HOMO level and can absorb a wide range of light from the visible region to the near infrared region. Thereby, it becomes possible to obtain both a high open circuit voltage (Voc) and a short circuit current density (Jsc), and it is possible to obtain a high photoelectric conversion efficiency η. Moreover, according to the production method of the present invention, various substituents can be introduced as substituents, and the characteristics (crystallinity, film-forming property, absorption wavelength) of the material can be controlled.

FIG. 1 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 5. FIG. 2 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 8. FIG. 3 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 11. FIG. 4 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 13. FIG. 5 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 16. FIG. 6 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 17. FIG. 7 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 18. FIG. 8 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 19. FIG. 9 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 20. FIG. 10 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 23. FIG. 11 shows the ultraviolet-visible absorption spectrum of the polymer compound of Example 26. FIG. 12 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 29. FIG. 13 shows an ultraviolet-visible absorption spectrum of the polymer compound of Example 30.

1. Polymer Compound The polymer compound of the present invention (hereinafter sometimes referred to as “polymer compound (1)”) has a benzobisthiazole structural unit represented by the general formula (1).

[In General Formula (1), A ¹ and A ² represent a divalent electron-donating group or a divalent electron-withdrawing group. However, when A ¹ is an electron donating group, A ² is an electron donating group, and when A ¹ is an electron withdrawing group, A ² is an electron withdrawing group. ]

  Since the polymer compound (1) of the present invention has a benzobisthiazole structural unit represented by the general formula (1), the band gap can be narrowed while deepening the HOMO level, thereby increasing the photoelectric conversion efficiency. Is advantageous. The polymer compound (1) of the present invention is preferably a donor-acceptor type semiconductor polymer. The donor-acceptor type semiconductor polymer compound means a polymer compound in which donor units and acceptor units are alternately arranged. The donor unit means an electron donating structural unit, and the acceptor unit means an electron accepting structural unit. The donor-acceptor type semiconductor polymer is preferably a polymer compound in which the structural unit represented by the general formula (1) and other structural units are alternately arranged.

In the benzobisthiazole structural unit represented by the general formula (1), A ¹ and A ² may be the same or different from each other, but are preferably the same from the viewpoint of easy production. .

Examples of the electron donating group for A ¹ and A ² include a thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, or a hydrocarbon group. Examples of the electron-withdrawing group include a group represented by the following formula, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom. And a phenyl group which may be substituted with an atom or a trifluoromethyl group.

[In the above formula, R ²⁶ represents a hydrocarbon group having 8 to 30 carbon atoms. * Represents a bond bonded to the benzene ring of benzobisthiazole. ]

Among them, as A ¹ and A ² , an alkoxy group, a thioalkoxy group, a thiophene ring which may be substituted with a hydrocarbon group, a thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group, or carbonization A phenyl group which may be substituted with a hydrogen group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group is preferred. In the benzobisthiazole structural unit represented by the general formula (1), A ¹ and A ² are each selected from groups represented by the following general formulas (a1) to (a5). Are preferable, and groups represented by the following general formulas (a1) to (a4) are more preferable. When A ¹ and A ² are groups represented by the following general formulas (a1) to (a5) (preferably groups represented by the following general formulas (a1) to (a4)), light having a short wavelength is absorbed. Therefore, the photoelectric conversion efficiency can be further increased.

[In General Formulas (a1) to (a5), R ^{21 to} R ²³ and R ^{25 to} R ²⁶ each independently represent a hydrocarbon group having 8 to 30 carbon atoms. R ²⁴ represents a hydrogen atom or a hydrocarbon group having 8 to 30 carbon atoms. * Represents a bond bonded to the benzene ring of benzobisthiazole. ]

R ²⁴ is preferably a hydrocarbon group having 8 to 30 carbon atoms.
The hydrocarbon group having 8 to 30 carbon atoms of R ^{21 to} R ²⁶ is preferably a branched hydrocarbon group, and more preferably a branched saturated hydrocarbon group. Since the hydrocarbon group of R ^{21 to} R ²⁶ has a branch, the solubility in an organic solvent can be increased, and the polymer compound (1) of the present invention can obtain appropriate crystallinity. As the carbon number of the hydrocarbon group of R ^{21 to} R ²⁶ increases, the solubility in an organic solvent can be improved. However, if the carbon number is too large, the reactivity in the coupling reaction described later decreases. It becomes difficult to synthesize. Therefore, the carbon number of the hydrocarbon group of R ^{21 to} R ²⁶ is preferably 8 to 25, more preferably 8 to 20, and still more preferably 8 to 16.

Examples of the hydrocarbon group having 8 to 30 carbon atoms represented by R ^{21 to} R ²⁶ include an n-octyl group, 1-n-butylbutyl group, 1-n-propylpentyl group, 1-ethylhexyl group, 2- Ethylhexyl group, 2-n-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 6-methylheptyl group, 2,4,4-trimethylpentyl group, 2, C8 alkyl group such as 5-dimethylhexyl group; n-nonyl group, 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyl 9-carbon atoms such as octyl, 2-methyloctyl, 6-methyloctyl, 2,3,3,4-tetramethylpentyl, 3,5,5-trimethylhexyl Alkyl group; n-decyl group, 1-n-pentylpentyl group, 1-n-butylhexyl group, 2-n-butylhexyl group, 1-n-propylheptyl group, 1-ethyloctyl group, 2-ethyloctyl group Group, 1-methylnonyl group, 2-methylnonyl group, 3,7-dimethyloctyl group and the like alkyl group having 10 carbon atoms; n-undecyl group, 1-n-butylheptyl group, 2-n-butylheptyl group, 1 An alkyl group having 11 carbon atoms such as -n-propyloctyl group, 2-n-propyloctyl group, 1-ethylnonyl group, 2-ethylnonyl group; n-dodecyl group, 1-n-pentylheptyl group, 2-n- 12 alkyl groups such as pentylheptyl, 1-n-butyloctyl, 2-n-butyloctyl, 1-n-propylnonyl, 2-n-propylnonyl; n Carbon number such as tridecyl group, 1-n-pentyloctyl group, 2-n-pentyloctyl group, 1-n-butylnonyl group, 2-n-butylnonyl group, 1-methyltridecyl group, 2-methyltridecyl group 13 alkyl groups; n-tetradecyl group, 1-n-heptylheptyl group, 1-n-hexyloctyl group, 2-n-hexyloctyl group, 1-n-pentylnonyl group, 2-n-pentylnonyl group, etc. An alkyl group having 14 carbon atoms; an alkyl group having 15 carbon atoms such as an n-pentadecyl group, 1-n-heptyloctyl group, 1-n-hexylnonyl group, 2-n-hexylnonyl group; n-hexadecyl group, An alkyl group having 16 carbon atoms such as 2-n-hexyldecyl group, 1-n-octyloctyl group, 1-n-heptylnonyl group, 2-n-heptylnonyl group; n-heptade Alkyl groups having 17 carbon atoms such as 1-n-octylnonyl group; alkyl groups having 18 carbon atoms such as n-octadecyl group and 1-n-nonylnonyl group; 19 alkyl groups such as n-nonadecyl group. An alkyl group having 20 carbon atoms such as an n-eicosyl group; an alkyl group having 21 carbon atoms such as an n-heneicosyl group; an alkyl group having 22 carbon atoms such as an n-docosyl group; a carbon number 23 such as an n-tricosyl group; An alkyl group having 24 carbon atoms such as an n-tetracosyl group and a 2-n-decyltetradecyl group; Preferably it is a C8-20 alkyl group, More preferably, it is a C8-16 alkyl group, More preferably, it is a C8-16 branched alkyl group, Most preferably, it is 2-ethylhexyl. Group, 3,7-dimethyloctyl group, 2-n-hexyldecyl group. When R ^{21 to} R ²⁶ are the above groups, the polymer compound (1) of the present invention has improved solubility in an organic solvent and has appropriate crystallinity.

The benzobisthiazole structural unit represented by the general formula (1) is suitable as a donor unit of a donor-acceptor type semiconductor polymer compound when the divalent groups A ¹ and A ² are electron donating groups. is there. Even if the divalent group of A ¹ or A ² is an electron donating group, it may act as an acceptor unit. The divalent electron donating groups A ¹ and A ² are preferably groups represented by the following general formulas (a1) to (a3), respectively. When the divalent electron donating groups of A ¹ and A ² are groups represented by the following general formulas (a1) to (a3), the benzobisthiazole structural unit of the present invention has high planarity, Since π-π stacking is efficiently formed, the conversion efficiency can be further improved.

[In General Formulas (a1) to (a3), R ^{21 to} R ²⁴ represent the same groups as described above. * Represents a bond bonded to the benzene ring of benzobisthiazole. ]

As the divalent electron-donating group represented by A ¹ or A ² , groups represented by the formulas (a1) and (a3) are preferable from the viewpoint of excellent planarity as the whole structural unit represented by the general formula (1). More preferred are groups represented by formulas (a1-1) to (a1-4) and (a3-1) to (a3-8). In the formula, * represents a bond bonded to the benzene ring of benzobisthiazole.

Further, the benzobisthiazole structural unit represented by the general formula (1) has an acceptor unit of a donor-acceptor type semiconductor polymer compound in which the divalent groups of A ¹ and A ² are electron withdrawing groups. It is suitable as. In addition, even if the divalent group of A ¹ and A ² is an electron donating group, it may act as a donor unit. The divalent electron withdrawing groups of A ¹ and A ² are preferably groups represented by the following general formulas (a4) and (a5), respectively, and are groups represented by the general formula (a4). More preferably. When the divalent electron-withdrawing groups of A ¹ and A ² are groups represented by the following general formulas (a4) and (a5), the benzobisthiazole structural unit of the present invention has high planarity. Since π-π stacking is efficiently formed, the conversion efficiency can be further improved.

[In General Formulas (a4) and (a5), R ²⁵ and R ²⁶ represent the same groups as described above. * Represents a bond bonded to the benzene ring of benzobisthiazole. ]

As the electron withdrawing group of A ^{1 to} A ^2, the group represented by the general formula (a4) is more preferable from the viewpoint of excellent electron acceptability as the entire structural unit represented by the general formula (1).

  Examples of the structural unit represented by the general formula (1) include a group represented by the following formula.

  A conventionally well-known structural unit can be used as a structural unit (a donor unit and an acceptor unit) which forms a donor-acceptor type semiconductor polymer in combination with the structural unit represented by the general formula (1). Specifically, the following structural units can be mentioned.

[In the formulas (b1) to (b28), R ^{30 to} R ⁵⁸ each independently represent the same group as the hydrocarbon group having 8 to 30 carbon atoms of R ^{21 to} R ²⁶ , and A ³⁰ and A ³¹ are And each independently represents the same group as A ¹ and A ² . j represents an integer of 1 to 4. * Represents a bond with the structural unit represented by the general formula (1). ]

The groups represented by the above formulas (b1) to (b15) are groups that act as acceptor units, and the groups represented by formulas (b17) to (b28) are groups that act as donor units. It is. The group represented by the formula (b16) may act as an acceptor unit or may act as a donor unit depending on the types of A ³⁰ and A ³¹ .

  The weight average molecular weight and number average molecular weight of the polymer compound (1) of the present invention are generally 2,000 or more and 500,000 or less, more preferably 3,000 or more and 200,000 or less. The weight average molecular weight and number average molecular weight of the polymer compound (1) of the present invention can be calculated based on a calibration curve prepared using polystyrene as a standard sample using gel permeation chromatography.

  The ionization potential of the polymer compound (1) of the present invention is preferably 4 eV or more, more preferably 4.5 eV or more, still more preferably 5 eV or more, and particularly preferably 5.1 eV or more. Although the upper limit of ionization potential is not specifically limited, For example, it is 7 eV or less, it is preferable that it is 6.5 eV or less, and it is preferable that it is 6 eV or less. When the ionization potential of the polymer compound (1) of the present invention is in the above range, the HOMO level is appropriately deepened (reduced), so that both a high open circuit voltage (Voc) and a short circuit current density (Jsc) are obtained. Thus, higher photoelectric conversion efficiency can be obtained.

2. Compound 2-1. Compound represented by General Formula (6) In the present invention, a compound represented by the following General Formula (6) (hereinafter, a compound represented by General Formula (6) may be referred to as “Compound (6)”. )including.

[In general formula (6),
A ¹ and A ² represent the same groups as described above.
R ^{7 to} R ¹⁰ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ¹ and M ² each independently represent a boron atom or a tin atom. R ⁷ and R ⁸ may form a ring together with M ¹ , and R ⁹ and R ¹⁰ may form a ring together with M ² .
m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ⁷ and R ⁹ may be the same or different. ]

In General Formula (6), the carbon number of the aliphatic hydrocarbon group of R ^{7 to} R ¹⁰ is preferably 1 to 5, and more preferably 1 to 4. As the aliphatic hydrocarbon group for R ^{7 to} R ¹⁰ , a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group and a butyl group are more preferable. Carbon number of the alkoxy group of R < ⁷ > -R < ¹⁰ > becomes like this. Preferably it is 1-3, More preferably, it is 1-2. The alkoxy group of R ⁷ to R ^10, a methoxy group, an ethoxy group, a propoxy group, etc., more preferably methoxy group, an ethoxy group. Carbon number of the aryloxy group of R < ⁷ > -R < ¹⁰ > becomes like this. Preferably it is 6-9, More preferably, it is 6-8. Examples of the aryloxy group for R ^{7 to} R ¹⁰ include a phenyloxy group, a benzyloxy group, and a phenylenebis (methyleneoxy) group.

When M ¹ and M ² are boron atoms, R ^{7 to} R ¹⁰ are preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, and m and n are 1 is preferable. Examples of * -M ¹ (R ⁷ ) _m R ⁸ and * -M ² (R ⁹ ) _n R ¹⁰ when M ¹ and M ² are boron atoms include groups represented by the following formulae. . However, * represents a bond with a thiazole ring.

When M ¹ and M ² are tin atoms, R ^{7 to} R ¹⁰ are preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and m and n are preferably 2. Examples of * -M ¹ (R ⁷ ) _m R ⁸ and * -M ² (R ⁹ ) _n R ¹⁰ when M ¹ and M ² are tin atoms include groups represented by the following formulae. . However, * represents a bond with a thiazole ring.

  The compound (6) is a starting material for the polymer compound (1) of the present invention. Since this compound (6) has the above-mentioned predetermined group, it has high temporal stability and can react efficiently to form the polymer compound (1) of the present invention. Examples of the compound (6) include the following compounds.

2-2. Compound represented by General Formula (5) In the present invention, a compound represented by the following General Formula (5) (hereinafter, a compound represented by General Formula (5) may be referred to as “Compound (5)”. )including.

[In General Formula (5), A ¹ and A ² each represent the same group as described above. ]

  The compound (5) is a raw material for the compound (6). That is, the compound (5) corresponds to an intermediate of the compound (6). Since this compound (5) has the above-mentioned predetermined group, it has high temporal stability and has an efficient reactivity. Examples of compound (5) include the following compounds.

2-3. In the present invention, the compound represented by the following general formula (4) (hereinafter, the compound represented by the general formula (4) may be referred to as “compound (4)”. )including.

[In general formula (4),
A ¹ and A ² represent the same groups as described above.
R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]

R ¹ aliphatic to R ⁶ carbon atoms in the hydrocarbon group is preferably 1 to 18, more preferably 1-8. Examples of the aliphatic hydrocarbon group represented by R ^{1 to} R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, and an octadecyl group. It is done. The carbon number of the aromatic hydrocarbon group of R ^{1 to} R ⁶ is preferably 6 to 8, more preferably 6 to 7, and particularly preferably 6. Examples of the aromatic hydrocarbon group for R ^{1 to} R ⁶ include a phenyl group. Among them, as R ^{1 to} R ⁶ , an aliphatic hydrocarbon group is preferable, an aliphatic hydrocarbon group having a branch is more preferable, and an isopropyl group is particularly preferable.

  The compound (4) is a raw material for the compound (5). That is, the compound (4) corresponds to an intermediate of the compound (6). Since this compound (4) has the above-mentioned predetermined group, it has high aging stability and high solubility in an organic solvent, and thus has an efficient reactivity. Furthermore, by using the compound (4), various skeletons and substituents can be introduced into the polymer compound (1) of the present invention. Examples of the compound (4) include the following compounds.

2-4. In the present invention, a compound represented by the following general formula (3) (hereinafter, a compound represented by the general formula (3) may be referred to as “compound (3)”. )including.

[In General Formula (3), X represents a halogen atom. R ^{1 to} R ⁶ represent the same groups as described above. ]

  Examples of the halogen atom for X include chlorine, bromine, and iodine. Either can be used, but iodine is particularly preferred from the viewpoint of the balance between reactivity and stability.

  The compound (3) is a raw material for the compound (4). That is, the compound (3) corresponds to an intermediate of the compound (6). Since this compound (3) has the above-mentioned predetermined group, it has high aging stability and high solubility in an organic solvent, and thus has an efficient reactivity. Furthermore, by using the compound (3), various skeletons and substituents can be introduced into the polymer compound (1) of the present invention. Examples of the compound (3) include the following compounds.

  The present invention also includes a compound represented by the following general formula (3 ′) (hereinafter, the compound represented by the general formula (3 ′) may be referred to as “compound (3 ′)”).

[In General Formula (3 ′), X and R ^{1 to} R ⁶ represent the same groups as described above. ]

  Examples of the compound represented by the general formula (3 ′) include compounds represented by the following formula.

2-5. Compound represented by General Formula (2) In the present invention, a compound represented by the following General Formula (2) (hereinafter, a compound represented by General Formula (2) may be referred to as “Compound (2)”. )including.

[In General Formula (2), R ^{1 to} R ⁶ each represent the same group as described above. ]

  The compound (2) is a raw material for the compound (3). That is, the compound (2) corresponds to an intermediate of the compound (6). Since this compound (2) has the above-mentioned predetermined group, it has high temporal stability and has an efficient reactivity. Furthermore, by using the compound (2), various skeletons and substituents can be introduced into the polymer compound (1) of the present invention. Examples of the compound (2) include the following compounds.

2-6. In the present invention, the compound represented by the following general formula (11) (hereinafter, the compound represented by the general formula (11) may be referred to as “compound (11)”. )including.

[In general formula (11),
A ¹ and A ² each represent the same group as described above.
R ²⁷ and R ²⁸ represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]

The aliphatic hydrocarbon group having 1 to 20 carbon atoms of R ²⁷ and R ²⁸ is preferably a saturated aliphatic hydrocarbon group, and is preferably a linear or branched saturated aliphatic hydrocarbon group. . Moreover, carbon number of the aliphatic hydrocarbon group of R <^27> , R < ²⁸ > becomes like this. Preferably it is 1-18, More preferably, it is 1-8. Examples of the aliphatic hydrocarbon group for R ²⁷ and R ²⁸ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group. Group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group and the like.

The substitution position of R ²⁷ and R ²⁸ is preferably the 3-position of the thiophene ring to which they are bonded.

The compound (11) is a starting material for the polymer compound (1) of the present invention. It is preferable to use the compound (11) because it is easy to introduce a substituent at a position corresponding to R ²⁷ and R ²⁸ in the formula (11) and the HOMO level and planarity may be adjusted. Examples of the compound (11) include the following compounds. In the formula, R ⁴⁰ is a group similar to the groups exemplified as R ²⁷ and R ²⁸ , and includes a hexyl group, an octyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, and a 2-n-hexyldecyl group. It is particularly preferred.

2-7. The compound represented by the general formula (12) In the present invention, the compound represented by the following general formula (12) (hereinafter, the compound represented by the general formula (12) may be referred to as “compound (12)”. .)including.

[In general formula (12),
A ¹ , A ² , R ²⁷ and R ²⁸ each represent the same group as described above.
R ^{29 to} R ³¹ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ³ and M ⁴ each independently represent a boron atom or a tin atom.
R ²⁹ and R ³⁰ may form a ring together with M ³ , and R ³¹ and R ³² may form a ring together with M ⁴ .
m1 and n1 each represents an integer of 1 or 2. When m1 and n1 are 2, the plurality of R ²⁹ and R ³¹ may be the same or different. ]

In the general formula (12), the number of carbon atoms in the aliphatic hydrocarbon group R ²⁹ to R ³² is preferably 1 to 5, more preferably 1-4. As the aliphatic hydrocarbon group for R ^{29 to} R ³² , a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group and a butyl group are more preferable. The number of carbon atoms of the alkoxy groups R ²⁹ to R ³² is preferably 1 to 3, more preferably 1 to 2. As the alkoxy group of R ^{29 to} R ³² , a methoxy group, an ethoxy group, a propoxy group and the like are preferable, and a methoxy group and an ethoxy group are more preferable. The carbon number of the aryloxy group of R ^{29 to} R ³² is preferably 6 to 9, and more preferably 6 to 8. Examples of the aryloxy group for R ^{29 to} R ³² include a phenyloxy group, a benzyloxy group, and a phenylenebis (methyleneoxy) group.

When M ³ and M ⁴ are boron atoms, R ^{29 to} R ³² are preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, and m1 and n1 are 1 is preferable. Examples of * -M ³ (R ²⁹ ) _m1 R ³⁰ and * -M ⁴ (R ³¹ ) _n1 R ³² when M ³ and M ⁴ are boron atoms include groups represented by the following formulae. . However, * represents a bond with a thiophene ring.

When M ³ and M ⁴ are tin atoms, R ^{29 to} R ³² are preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and m1 and n1 are preferably 2. Examples of * -M ³ (R ²⁹ ) _m1 R ³⁰ and * -M ⁴ (R ³¹ ) _n1 R ³² when M ³ and M ⁴ are tin atoms include groups represented by the following formulae. . However, * represents a bond with a thiophene ring.

The substitution position of * -M ³ (R ²⁹ ) _m1 R ³⁰ and * -M ⁴ (R ³¹ ) _n1 R ³² is preferably the 5-position of the thiophene ring to which they are bonded.

The compound (12) is a starting material for the polymer compound (1) of the present invention. It is preferable to use the compound (12) because it is easy to introduce a substituent at a position corresponding to R ²⁷ and R ²⁸ in the formula (12) and the HOMO level and planarity may be adjusted. As a compound (12), the following compound can be illustrated, for example.

3. Production method The compound represented by the general formula (1) of the present invention is a compound represented by the general formula (2) using benzobisthiazole as a starting material,

[In General Formula (2), R ^{1 to} R ⁶ each represent the same group as described above. ]
A compound represented by the general formula (3),

[In General Formula (3), X and R ^{1 to} R ⁶ represent the same groups as described above. ]
A compound represented by the general formula (4),

[In General Formula (4), A ¹ , A ² and R ^{1 to} R ⁶ each represent the same group as described above. ]
A compound represented by the general formula (5), and

[In General Formula (5), A ¹ and A ² each represent the same group as described above. ]
Compound represented by general formula (6)

[In General Formula (6), A ¹ , A ² , R ^{7 to} R ¹⁰ , M ¹ and M ² each represent the same group as described above. ]
It is manufactured by the manufacturing method characterized by passing through.

  According to the production method of the present invention, various substituents can be introduced into the benzobisthiazole skeleton, and a material design with a high degree of freedom becomes possible. As a result, the characteristics of the material (energy level, solubility, crystallinity, film forming property, absorption wavelength) can be easily controlled.

3-1. 1st process and 2nd process It is preferable that the manufacturing method of this invention includes the following 1st process and 2nd process.
First step: A step of reacting a benzobisthiazole with a base and a halogenated silane compound to obtain a compound represented by the general formula (2) Second step: A compound represented by the general formula (2) with a base and a halogen A step of obtaining a compound represented by the general formula (3) by reacting with a chemical reagent

3-1-1. First Step In the first step, examples of the base to be reacted with benzobisthiazole include alkyl lithium, alkyl metal amide, alkyl magnesium and magnesium complex, and alkali metal hydride.

  Examples of the alkyl lithium include n-butyl lithium, sec-butyl lithium, and tert-butyl lithium. Examples of the alkyl metal amide include lithium diisopropylamide, lithium diethylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium-2,2,6,6-tetramethylpiperidide , Lithium amide, sodium amide, potassium amide. Examples of the alkylmagnesium and magnesium complexes include tert-butylmagnesium chloride, ethylmagnesium chloride, 2,2,6,6-tetramethylpiperidinylmagnesium chloride, and lithium chloride complex. Examples of the alkali metal hydride include lithium hydride, sodium hydride, and potassium hydride. Of these, n-butyllithium and alkyl metal amide are preferable from the viewpoint of regioselectivity, and n-butyllithium and lithium diisopropylamide are particularly preferable.

  In the first step, the molar ratio of benzobisthiazole and base (benzobisthiazole: base) is generally about 1: 1.8 to 1: 3.0 and is not particularly limited, but the viewpoint of yield and reaction efficiency To 1: 1.9 to 1: 2.6, preferably 1: 2.0 to 1: 2.4, and more preferably 1: 2.0 to 1: 2.2.

  In the first step, examples of the halogenated silane compound to be reacted with benzobisthiazole together with a base include alkyl halogenated silanes and arylalkyl halogenated silanes. Examples of the alkyl halogenated silane include chloro (trimethyl) silane, chloro (ethyl) dimethylsilane, chloro (isopropyl) dimethylsilane, chloro (triisopropyl) silane, tert-butyl (chloro) dimethylsilane, chloro (triethyl) silane, Examples include alkylchlorosilanes such as chloro (triisobutyl) silane; arylchlorosilanes such as chloro (tripropyl) silane, tributyl (chloro) silane, chloro (dimethyl) phenylsilane, and chloro (methyl) diphenylsilane. Examples of the arylalkyl halogenated silane include arylchlorosilanes such as chlorotriphenylsilane and tert-butyl (chloro) diphenylsilane. Of these, alkylchlorosilane is preferable, and chloro (triisopropyl) silane is particularly preferable.

In the first step, the molar ratio of benzobisthiazole and halogenated silane compound (benzobisthiazole: halogenated silane compound) is generally about 1: 1.8 to 1: 3.0 and is not particularly limited. From the viewpoint of rate and reaction efficiency, 1: 1.9 to 1: 2.6 is preferable, 1: 2.0 to 1: 2.4 is more preferable, and 1: 2.0 to 1: 2.2 is more preferable. .
The molar ratio of the base and the halogenated silane compound (base: halogenated silane compound) is, for example, about 1: 0.5 to 1: 2.0, preferably 1: 0.6 to 1: 1.7. 1: 0.7 to 1: 1.5 is more preferable, and 1: 0.8 to 1: 1.2 is more preferable.

  In the first step, the base and the halogenated silane compound may be reacted simultaneously, but from the viewpoint of reaction efficiency and regioselectivity, it is preferable to first react the base and then react the halogenated silane compound.

  In the first step, the solvent for reacting the base and the halogenated silane compound with benzobisthiazole is not particularly limited, but ether solvents and hydrocarbon solvents can be used. Examples of ether solvents include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane. Examples of the hydrocarbon solvent include pentane, hexane, heptane, benzene, toluene, and xylene. Of these, ether solvents are preferable, and tetrahydrofuran is particularly preferable. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.

  The amount of the solvent used in the first step is generally 5 mL or more and about 150 mL with respect to 1 g of benzobisthiazole, and is not particularly limited, but is preferably 10 mL or more and 120 mL or less from the viewpoint of yield and reaction efficiency, 20 mL As mentioned above, 100 mL or less is more preferable, and 30 mL or more and 80 mL or less are still more preferable.

  In the first step, the temperature at which the base and the halogenated silane compound are reacted with benzobisthiazole is preferably room temperature or less and more preferably −20 ° C. or less from the viewpoint of suppressing the formation of by-products. Preferably, it is -30 degrees C or less.

3-1-2. Second Step In the second step, examples of the base to be reacted with the compound represented by the general formula (2) include the same compounds as the base used in the first step. Among these, an alkyl metal amide is preferable, and lithium diisopropylamide is particularly preferable.

  In the second step, the molar ratio of the compound represented by the general formula (2) and the base (compound (2): base) is generally about 1: 1.8 to 1: 3.0 and is not particularly limited. From the viewpoint of yield and reaction efficiency, 1: 1.9 to 1: 2.6 is preferable, 1: 2.0 to 1: 2.4 is more preferable, and 1: 2.0 to 1: 2.2 is preferable. Further preferred.

  In the second step, examples of the halogenating reagent to be reacted with the compound represented by the general formula (2) together with a base include a halogen molecule and N-halogenated succinimide. Halogen molecules include chlorine, bromine and iodine. Examples of the N-halogenated succinimide include N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide. From the viewpoint of availability and reactivity, halogen molecules are preferable, and iodine is particularly preferable.

In the second step, the molar ratio of the compound represented by the general formula (2) and the halogenating reagent (compound (2): halogenating reagent) is generally about 1: 1.5 to 1: 20.0. Although not particularly limited, from the viewpoint of yield and reaction efficiency, it is preferably 1: 1.7 to 1: 17.0, more preferably 1: 1.9 to 1: 15.0, and 1: 2.0 to 1: 1. 10.0 is more preferable.
The molar ratio of the base and the halogenating reagent (base: halogenating reagent) is, for example, about 1: 0.5 to 1: 2.0, preferably 1: 0.6 to 1: 1.7, and 1: 0. 7 to 1: 1.5 is more preferable, and 1: 0.8 to 1: 1.2 is more preferable.

  In the second step, the base and the halogenating reagent may be reacted at the same time, but from the viewpoint of reaction efficiency, it is preferable to first react the basic compound and then react with the halogenating reagent.

  In the second step, examples of the solvent for reacting the compound represented by the general formula (2) with the base and the halogenating reagent include the same solvents as those used in the first step. In that case, it is preferable to use the same solvent as the solvent used in the first step from the viewpoint that can be achieved. Of these, tetrahydrofuran is particularly preferred.

  The amount of the solvent used in the second step is generally 1 mL or more and 50 mL or less with respect to 1 g of the compound represented by the general formula (2), and is not particularly limited, but is 5 mL from the viewpoint of yield and reaction efficiency. As mentioned above, 40 mL or less is preferable, 8 mL or more and 35 mL or less are more preferable, and 10 mL or more and 30 mL or less are more preferable.

  In the second step, the temperature at which the compound represented by the general formula (2) is reacted with the base and the halogenating reagent is preferably room temperature or lower from the viewpoint of suppressing the formation of by-products, and is −40 ° C. It is more preferable that the temperature is -60 ° C. or lower.

3-2. 3rd process, 4th process, and 5th process It is preferable that the manufacturing method of this invention contains the following 3rd process, 4th process, and 5th process further.
Third step: In the presence of a metal catalyst, a compound represented by the general formula (3) is added to the general formula (7) and / or (8).

[In General Formulas (7) and (8), A ¹ and A ² each represent the same group as described above. R ¹¹ and R ¹² each independently represents a hydrogen atom or * -M ³ (R ¹³ ) _k R ¹⁴ . R ¹³ and R ¹⁴ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. M ³ represents a boron atom or a tin atom. R ¹³ and R ¹⁴ may form a ring together with M ³ . k represents an integer of 1 or 2. When k is 2, the plurality of R ¹³ may be the same or different. * Represents a bond with A ¹ or A ² . ]
A step of obtaining a compound represented by the general formula (4) by reacting the compound represented by general formula (4) Fourth step: The compound represented by the general formula (4) is treated with an acid or a base, and the general formula ( Step 5 for obtaining the compound represented by 5) Step 5: The compound represented by the general formula (5) is reacted with a base and a tin halide compound or a borate ester, and represented by the general formula (6). Step of obtaining a compound

3-2-1. Third Step In the third step, A ¹ and A ² are the same as described above as the compound represented by the general formula (7) and / or (8) to be reacted with the compound represented by the general formula (3). A compound in which R ¹¹ and R ¹² are a hydrogen atom or * -M ³ (R ¹³ ) _k R ¹⁴ is preferred.

The carbon number of the aliphatic hydrocarbon group of R ¹³ and R ¹⁴ when R ¹¹ and R ¹² are * -M ³ (R ¹³ ) _k R ¹⁴ is preferably 1 to 5, more preferably 1-4. Examples of the aliphatic hydrocarbon group for R ¹³ and R ¹⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group. Carbon number of the alkoxy group of R <^13> , R < ¹⁴ > becomes like this. Preferably it is 1-3, More preferably, it is 1-2. The alkoxy group for R ¹³ and R ¹⁴ is preferably a methoxy group, an ethoxy group, a propoxy group, or the like, more preferably a methoxy group or an ethoxy group. Carbon number of the aryloxy group of R <^13> , R < ¹⁴ > becomes like this. Preferably it is 6-9, More preferably, it is 6-8. Examples of the aryloxy group for R ¹³ and R ¹⁴ include a phenyloxy group, a benzyloxy group, and a phenylenebis (methyleneoxy) group.

When R ¹¹ and R ¹² are * -M ³ (R ¹³ ) _k R ¹⁴ and M ³ is a boron atom, R ¹³ and R ¹⁴ are a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a carbon number. A 6-10 aryloxy group is preferred, and k is preferably 1. Examples of * -M ³ (R ¹³ ) _k R ¹⁴ in the case where M ³ is a boron atom include groups represented by the following formulae. However, * represents a bond with A ¹ or A ² .

When R ¹¹ and R ¹² are * -M ³ (R ¹³ ) _k R ¹⁴ and M ³ is a tin atom, R ¹³ and R ¹⁴ are each an aliphatic hydrocarbon group having 1 to 6 carbon atoms. And k is preferably 2. Examples of * -M ³ (R ¹³ ) _k R ¹⁴ in the case where M ³ is a tin atom include groups represented by the following formulae. However, * represents a bond with A ¹ or A ² .

R ¹¹ and R ¹² can be appropriately selected according to the types of A ¹ and A ² . For example, when A ¹ and A ² are groups represented by general formulas (a1) and (a2), R ¹¹ and R ¹² are preferably hydrogen atoms. When A ¹ and A ² are groups represented by the general formulas (a3) to (a5), R ¹¹ and R ¹² are groups represented by * -M ³ (R ¹³ ) _k R ^14. Preferably, * -Sn (R ¹³ ) ₂ R ¹⁴
It is more preferable that it is group represented by these.

  Examples of the compounds (7) and (8) include compounds represented by the following formulas.

  The compounds (7) and (8) may be the same or different depending on the target compound, but are preferably the same from the viewpoint of suppressing the formation of by-products.

  In the third step, the molar ratio of compound (3) to the sum of compounds (7) and (8) (compound (3): total of compounds (7) and (8)) is generally 1: 1 to 1: Although it is about 10 and is not particularly limited, it is preferably 1: 1.5 to 1: 8, more preferably 1: 2 to 1: 6, and still more preferably 1: 2 to 1: 5 from the viewpoint of yield and reaction efficiency. .

  In the third step, the metal catalyst used when the compound represented by the general formula (3) and the compound represented by the general formula (7) and / or (8) are reacted includes a palladium catalyst and a nickel catalyst. And transition metal catalysts such as iron-based catalysts, copper-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Among these, a copper catalyst and a palladium catalyst are preferable. Note that the valence of palladium is not particularly limited, and may be zero or divalent.

  Examples of the palladium-based catalyst include palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, palladium (II) oxide, palladium (II) sulfide, palladium (II) telluride, palladium hydroxide ( II), palladium selenide (II), palladium cyanide (II), palladium acetate (II), palladium trifluoroacetate (II), palladium acetylacetonate (II), diacetate bis (triphenylphosphine) palladium (II) ), Tetrakis (triphenylphosphine) palladium (0), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium (II), dichloro [1,2- Sus (diphenylphosphino) ethane] palladium (II), dichloro [1,3-dis (diphenylphosphino) propane] palladium (II), dichloro [1,4-bis (diphenylphosphino) butane] palladium (II) Dichloro [1,1-bis (diphenylphosphinoferrocene)] palladium (II), dichloro [1,1-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane adduct, bis (dibenzylideneacetone) palladium ( 0), tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, dichloro [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene ] (3-Chloropyridyl) paradiu (II), bis (tri-tert-butylphosphine) palladium (0), dichloro [2,5-norbornadiene] palladium (II), dichlorobis (ethylenediamine) palladium (II), dichloro (1,5-cyclooctadiene) Palladium (II) and dichlorobis (methyldiphenylphosphine) palladium (II) are mentioned. These catalysts may be used individually by 1 type, and may mix and use 2 or more types.

  Examples of the copper catalyst include copper, copper fluoride (I), copper chloride (I), copper bromide (I), copper iodide (I), copper fluoride (II), copper chloride (II), odor Copper halide compounds such as copper (II) iodide, copper (II) iodide; copper (I) oxide, copper (I) sulfide, copper oxide (II), copper sulfide (II), copper acetate (I), acetic acid Examples include copper (II) and copper (II) sulfate.

The metal catalyst can be appropriately selected according to the types of A ¹ and A ^{2. In} the general formulas (7) and (8), A ¹ and A ² are groups represented by the general formulas (a1) and (a2). In this case, the metal catalyst is preferably a copper-based catalyst, more preferably a copper halide compound, and most preferably copper (I) iodide. In the general formulas (7) and (8), when A ¹ and A ² are groups represented by the general formulas (a3) to (a5), the metal catalyst is preferably a palladium catalyst, and tris ( Dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferred.

  In the third step, the molar ratio of the compound (3) to the metal catalyst (compound (3): metal catalyst) is generally about 1: 0.0001 to 1: 0.5 and is not particularly limited. From the viewpoint of reaction efficiency, 1: 0.001 to 1: 0.4 is preferable, 1: 0.005 to 1: 0.3 is more preferable, and 1: 0.01 to 1: 0.2 is more preferable.

  In the third step, a specific ligand may be coordinated to a metal catalyst such as a copper catalyst or a palladium catalyst. Examples of the ligand include trimethylphosphine, triethylphosphine, tri (n-butyl) phosphine, tri (isopropyl) phosphine, tri (tert-butyl) phosphine, tri-tert-butylphosphonium tetrafluoroborate, bis (tert-butyl). ) Methylphosphine, tricyclohexylphosphine, diphenyl (methyl) phosphine, triphenisphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, tris (2-methoxyphenyl) phosphine , Tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2-furyl) phosphine, 2-dicyclohexylphosphinobiphenyl, 2-dicyclohexylphosphine No-2'-methylbiphenyl, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropyl-1,1'-biphenyl, 2-dicyclohexylphosphino-2 ', 6'-dimethoxy-1,1 '-Biphenyl, 2-dicyclohexylphosphino-2'-(N, N'-dimethylamino) biphenyl, 2-diphenylphosphino-2 '-(N, N'-dimethylamino) biphenyl, 2- (di-tert -Butyl) phosphino-2 '-(N, N'-dimethylamino) biphenyl, 2- (di-tert-butyl) phosphinobiphenyl, 2- (di-tert-butyl) phosphino-2'-methylbiphenyl, 1 , 2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphos) Dino) butane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3-bis (dicyclohexylphosphino) propane, 1,4-bis (dicyclohexylphosphino) butane, 1,2-bisdiphenylphosphinoethylene 1,1-bis (diphenylphosphino) ferrocene, 1,2-ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 2,2′-bipyridyl, 1,3-diphenyldihydroimidazolylidene, 1,3-dimethyldihydroimidazolidene, diethyldihydroimidazolylidene, 1,3-bis (2,4,6-trimethylphenyl) dihydroimidazolidene, 1,3-bis (2,6-diisopropylphenyl) dihydro Imidazolylidene, 1,10-phenanthroline, 5,6-dimethyl-1 , 10-phenanthroline, butophenanthroline. Only 1 type may be used for a ligand and 2 or more types may be used for it.

  In the third step, when the ligand is coordinated to the metal catalyst, the molar ratio of the metal catalyst to the ligand (metal catalyst: ligand) is generally about 1: 0.5 to 1:10. Although not particularly limited, 1: 1 to 1: 8 are preferable from the viewpoint of yield and reaction efficiency, 1: 1 to 1: 7 are more preferable, and 1: 1 to 1: 5 are even more preferable.

In the third step, when the compound represented by the general formula (7) and / or (8) is reacted with the compound represented by the general formula (3) in the presence of a metal catalyst, a base coexists. You may let them. In particular, in the general formulas (7) and (8), when A ¹ and A ² are groups represented by the general formulas (a1) and (a2), it is preferable that a base coexists. In the general formulas (7) and (8), when A ¹ and A ² are groups represented by the general formulas (a3) to (a5), the base may be changed depending on the types of substituents R ¹¹ and R ¹² . The presence or absence of coexistence can be determined. For example, when R ¹¹ and R ¹² are groups represented by * -M ³ (R ¹³ ) _k R ¹⁴ and M ³ is a boron atom, it is preferable that a base coexists, and M ³ is tin. When it is an atom, a base does not have to coexist.

  Bases include alkali metal salt compounds such as lithium hydride, sodium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, carbonate Alkaline earth metal salt compounds such as calcium and barium carbonate; lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide, potassium isopropoxy Lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide, potassium tert Alkoxy alkali metal compounds such as amyl alkoxide; lithium hydride, sodium hydride, metal hydride compounds such as potassium hydride. Among these, as the base, an alkoxyalkali metal compound is preferable, and lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and cesium carbonate are more preferable.

  In the third step, the molar ratio of the compound represented by the general formula (3) and the base (compound represented by the general formula (3): base) is generally about 1: 1 to 1:10 and is particularly limited. However, from the viewpoint of yield and reaction efficiency, 1: 1.5 to 1: 8 is preferable, 1: 1.8 to 1: 6 is more preferable, and 1: 2 to 1: 5 is more preferable.

In the third step, as a solvent for reacting the compound represented by the general formula (3) with the compound represented by the general formula (7) and / or (8) in the presence of a metal catalyst, the reaction is affected. The solvent is not particularly limited as long as it does not reach, and ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents, and the like can be used. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of the hydrocarbon solvent include pentane, hexane, and heptane. Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl3,4,5,6-tetrahydro- (1H ) -Pyrimidine. A nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane can be used.
Among these, tetrahydrofuran, dioxane, and N, N-dimethylformamide are particularly preferable.

  The amount of the solvent used in the third step is generally 1 mL or more and 50 mL or less with respect to 1 g of the compound represented by the general formula (3), and is not particularly limited, but is 5 mL from the viewpoint of yield and reaction efficiency. As mentioned above, 40 mL or less is preferable, 8 mL or more and 35 mL or less are more preferable, and 10 mL or more and 30 mL or less are more preferable.

  In the third step, the reaction temperature is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 30 ° C. or higher and 180 ° C. or lower, and 40 ° C. or higher from the viewpoint of increasing the reaction yield. More preferably, it is 150 ° C. or lower.

3-2-2. Fourth Step In the fourth step, the compound for treating the compound represented by the general formula (4) may be an acid or a base. From the viewpoint of reactivity, a base is preferable. As the base, tetraalkylammonium fluoride and the like can be used. Examples of the tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrapentylammonium fluoride, and tetrahexylammonium fluoride. Among these, tetrabutylammonium fluoride is preferable, and tetra-n-butylammonium fluoride is particularly preferable.

  Although it does not specifically limit as a solvent which processes the compound represented by General formula (4) with an acid or a base in a 4th process, The thing similar to the solvent used at a 3rd process is mentioned. From the viewpoint of preventing impurity contamination, it is preferable to add an acid or base as it is to the reaction solution obtained in the third step. The amount of solvent used in the fourth step is generally 1 mL or more and 50 mL or less with respect to 1 g of the compound represented by the general formula (4), and is not particularly limited, but is 5 mL from the viewpoint of yield and reaction efficiency. As mentioned above, 40 mL or less is preferable, 8 mL or more and 35 mL or less are more preferable, and 10 mL or more and 30 mL or less are more preferable. Although reaction temperature is not specifically limited, Generally it is 0 degreeC or more and 100 degrees C or less.

3-2-3. Fifth Step In the fifth step, as the base to be reacted with the compound represented by the general formula (5), any of the bases exemplified in the first step can be used, and among these, alkyl metal amide is preferable, and lithium diisopropyl Amides are particularly preferred.

  In the fifth step, the molar ratio of the compound represented by the general formula (5) to the base (compound (5): base) is generally about 1: 1 to 1: 5 and is not particularly limited. From the viewpoint of reaction efficiency, 1: 1.1 to 1: 4 is preferable, 1: 1.5 to 1: 3 is more preferable, and 1: 1.8 to 1: 2.5 is more preferable.

  In the fifth step, examples of the tin halide compound to be reacted with the compound represented by the general formula (5) together with a base include a halogenated alkyltin compound, a halogenated cycloalkyltin compound, and a halogenated aryltin compound. Examples of the halogenated alkyltin compound include trimethyltin chloride, triethyltin chloride, tripropyltin chloride, tributyltin chloride, trimethyltin bromide, triethyltin bromide, tripropyltin bromide, and tributyltin bromide. Examples of the halogenated cycloalkyl tin compound include tricyclohexyl tin chloride and tricyclohexyl tin bromide. Examples of the halogenated aryl tin compound include triphenyl tin chloride, tribenzyl tin chloride, triphenyl tin bromide, and tribenzyl tin bromide. Among these, a halogenated alkyltin compound is preferable, and trimethyltin chloride and tributyltin chloride are more preferable.

  In the fifth step, boric acid ester to be reacted with the compound represented by the general formula (5) together with a base is trimethyl borate, triethyl borate, triilopropyl borate, 2-methoxy-4, 4, 5, 5 -Tetramethyl-1,3,2-dioxaborolane, 2-ethoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-isopropoxy-4,4,5,5-tetramethyl -1,3,2-dioxaborolane, 2-methoxy-5,5-dimethyl-1,3,2-dioxaborinane, 2-ethoxy-5,5-dimethyl-1,3,2-dioxaborinane, 2-isopropoxy- 5,5-dimethyl-1,3,2-dioxaborinane, B-methoxycatecholborane, B-ethoxycatecholborane, B-isopropoxycatechol Borane, and the like. Among these, trimethyl borate, triethyl borate, triilopropyl borate, 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-ethoxy-4,4,5,5- Tetramethyl-1,3,2-dioxaborolane, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-methoxy-5,5-dimethyl-1,3,2 -Dioxaborinane, 2-ethoxy-5,5-dimethyl-1,3,2-dioxaborinane, 2-isopropoxy-5,5-dimethyl-1,3,2-dioxaborinane are preferred, trimethyl borate, triethyl borate, triborate Iropropyl, 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-ethoxy-4,4,5, - tetramethyl-1,3,2-dioxaborolane, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane is preferred.

In the fifth step, the molar ratio of the compound represented by the general formula (5) to the tin halide compound or borate ester (compound (5): tin halide compound or borate ester) is generally 1: 1 to Although it is about 1: 5 and is not particularly limited, it is preferably 1: 1.1 to 1: 4, more preferably 1: 1.5 to 1: 3, and more preferably 1: 1.8 to 1: 4 from the viewpoint of yield and reaction efficiency. 1: 2.5 is more preferable.
The molar ratio of the base to the tin halide compound or borate (base: tin halide compound) is, for example, about 1: 0.5 to 1: 2.0, and 1: 0.6 to 1: 1. 7 is preferable, 1: 0.7 to 1: 1.5 is more preferable, and 1: 0.8 to 1: 1.2 is more preferable.

  The base and the tin halide compound or borate may be simultaneously reacted with the compound represented by the general formula (5). From the viewpoint of the reaction yield, the compound represented by the general formula (5) is first used. It is preferable to react a base with a tin halide compound or a borate ester. In the fifth step, the temperature at which the compound (5) is reacted with the base and then the tin halide compound or borate ester is added is preferably room temperature or less, and 0 ° C. or less from the viewpoint of suppressing the formation of by-products. It is more preferable that

  In the fifth step, the solvent for reacting the compound represented by the general formula (5) with a base and a tin halide compound or a borate ester is not particularly limited, but an ether solvent, a hydrocarbon solvent, or the like is used. be able to. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane. Examples of the hydrocarbon solvent include pentane, hexane, heptane, benzene, toluene, and xylene. Of these, tetrahydrofuran is preferred. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.

  The amount of solvent used in the fifth step is generally 1 mL or more and 70 mL or less with respect to 1 g of the compound represented by the general formula (5), and is not particularly limited, but is 5 mL from the viewpoint of yield and reaction efficiency. As mentioned above, 60 mL or less is preferable, 10 mL or more and 50 mL or less are more preferable, and 20 mL or more and 45 mL or less are more preferable.

3-3. Sixth Step and Seventh Step In the manufacturing method of the present invention, the following sixth step and seventh step may be performed after the fifth step. The compound represented by the general formula (12) obtained in the seventh step can also be subjected to the next coupling reaction.
Sixth step: General formula (9) and / or general formula (10) in the presence of a metal catalyst in the compound represented by general formula (6)

[In the general formulas (9) and (10),
R ²⁷ and R ²⁸ represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
X ¹ and X ² represent a halogen atom. ]
A step of obtaining a compound represented by the general formula (11) by reacting the compound represented by general formula (11) Seventh step: a base and a tin halide compound or a borate ester to the compound represented by the general formula (11) A step of reacting to obtain a compound represented by the general formula (12)

3-3-1. Sixth Step In the sixth step, as the compound represented by the general formula (9) and / or (10) to be reacted with the compound represented by the general formula (6), R ²⁷ and R ²⁸ are as defined above. And compounds in which X ¹ and X ² are halogen atoms such as chlorine atom, bromine atom and iodine atom are preferred. Among them, X ¹ and X ² are preferably bromine atoms or iodine atoms, and particularly preferably bromine atoms. A compound represented by the following formula is preferred.

  In the sixth step, the molar ratio of the compound represented by the general formula (6) and the sum of the compounds represented by the general formulas (9) and (10) is in the range of 1:99 to 99: 1. It is preferable that it is in the range of 20:80 to 80:20, and it is more preferable that it is in the range of 40:60 to 60:40.

  The metal catalyst used in the sixth step is preferably a transition metal catalyst, and examples of the transition metal catalyst include a palladium catalyst, a nickel catalyst, an iron catalyst, a copper catalyst, a rhodium catalyst, and a ruthenium catalyst. . Among these, a palladium-based catalyst is preferable. The palladium of the palladium-based catalyst may be zero-valent or divalent.

  As the palladium-based catalyst, any of the palladium-based catalysts exemplified in the third step can be used, and these catalysts may be used singly or in combination of two or more. Among these, tris (dibenzylideneacetone) dipalladium (0) and tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferable.

  In the sixth step, the molar ratio of the compound represented by the general formula (6) to the metal catalyst (compound (6): metal catalyst) is generally about 1: 0.0001 to 1: 0.5, Although not limited, from the viewpoint of yield and reaction efficiency, 1: 0.001 to 1: 0.3 is preferable, 1: 0.005 to 1: 0.2 is more preferable, and 1: 0.01 to 1: 0. .1 is more preferable.

  In the sixth step, a specific ligand may be coordinated with the metal catalyst. As the ligand, any of the ligands exemplified in the third step can be used, and a catalyst coordinated with any of these ligands may be used in the reaction. A ligand may be used individually by 1 type and may be used in mixture of 2 or more types. Of these, tris (o-tolyl) phosphine is preferable.

  In the sixth step, when the ligand is coordinated to the metal catalyst, the molar ratio of the metal catalyst to the ligand (metal catalyst: ligand) is generally about 1: 0.5 to 1:10. Although not particularly limited, 1: 1 to 1: 8 are preferable from the viewpoint of yield and reaction efficiency, 1: 1 to 1: 7 are more preferable, and 1: 1 to 1: 5 are even more preferable.

  In the sixth step, the solvent for reacting the compound represented by the general formula (6) and the compound represented by the general formulas (9) and (10) is not particularly limited as long as the reaction is not affected. Conventionally known solvents can be used. For example, ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents and the like can be used. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of the hydrocarbon solvent include pentane, hexane, and heptane. Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro- (1H ) -Pyrimidinone. In addition, nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane can be used. Among these, tetrahydrofuran, chlorobenzene, and N, N-dimethylformamide are preferable, and chlorobenzene is particularly preferable. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.

  In the sixth step, the amount of the solvent used relative to 1 g in total of the compound represented by the general formula (6) and the compounds represented by the general formulas (9) and (10) is generally about 1 mL or more and 100 mL or less. Although not specifically limited, 10 mL or more and 80 mL or less are preferable from a viewpoint of a yield or reaction efficiency, 15 mL or more and 70 mL or less are more preferable, and 20 mL or more and 60 mL or less are more preferable.

3-3-2. Seventh Step In the seventh step, any of the bases exemplified in the first step can be used as the base to be reacted with the compound represented by the general formula (11). Among these, alkyl metal amide is preferable, and lithium diisopropyl is used. Amides are particularly preferred.

  In the seventh step, the molar ratio of the compound represented by the general formula (11) and the base (compound (11): base) is generally about 1: 1 to 1: 5 and is not particularly limited. From the viewpoint of reaction efficiency, 1: 1.1 to 1: 4 is preferable, 1: 1.5 to 1: 3 is more preferable, and 1: 1.8 to 1: 2.5 is more preferable.

  In the seventh step, the tin halide compound to be reacted with the compound represented by the general formula (11) together with the base includes the same compounds as the tin halide compounds exemplified in the fifth step. Tin compounds are preferred, and trimethyltin chloride and tributyltin chloride are more preferred.

  In addition, in the seventh step, the boric acid ester to be reacted with the compound represented by the general formula (5) together with the base includes the same compounds as the boric acid ester exemplified in the fifth step. Among them, trimethyl borate, Triethyl borate, triisopropyl borate, 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-ethoxy-4,4,5,5-tetramethyl-1,3,2 -Dioxaborolane, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-methoxy-5,5-dimethyl-1,3,2-dioxaborinane, 2-ethoxy-5 , 5-dimethyl-1,3,2-dioxaborinane, 2-isopropoxy-5,5-dimethyl-1,3,2-dioxaborinane are preferred, Trimethyl, triethyl borate, triisopropyl borate, 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-ethoxy-4,4,5,5-tetramethyl-1,3 , 2-dioxaborolane and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane are more preferred.

In the seventh step, the molar ratio of the compound represented by the general formula (11) and the tin halide compound or borate ester (compound (11): tin halide compound or borate ester) is generally 1: 1 to Although it is about 1: 5 and is not particularly limited, it is preferably 1: 1.1 to 1: 4, more preferably 1: 1.5 to 1: 3, and more preferably 1: 1.8 to 1: 4 from the viewpoint of yield and reaction efficiency. 1: 2.5 is more preferable.
The molar ratio of the base to the tin halide compound or borate ester (base: tin halide compound or borate ester) is, for example, about 1: 0.5 to 1: 2.0, and 1: 0.6 to The ratio is preferably 1: 1.7, more preferably 1: 0.7 to 1: 1.5, and still more preferably 1: 0.8 to 1: 1.2.

  The base and the tin halide compound or boric acid ester may be simultaneously reacted with the compound represented by the general formula (11). From the viewpoint of the reaction yield, the compound represented by the general formula (11) is first used. It is preferable to react a base with a tin halide compound or a borate ester. In the seventh step, the temperature at which the compound (11) is reacted with the base and then the tin halide compound or borate ester is added is preferably room temperature or less, and 0 ° C. or less from the viewpoint of suppressing the formation of by-products. It is more preferable that

  In the seventh step, a solvent for reacting the compound represented by the general formula (11) with a base and a tin halide compound or a borate ester is not particularly limited, but ether solvents and hydrocarbon solvents are used. be able to. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane. Examples of the hydrocarbon solvent include pentane, hexane, heptane, benzene, toluene, and xylene. Of these, tetrahydrofuran is preferred. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.

  The amount of the solvent used in the seventh step is generally 1 mL or more and 70 mL or less with respect to 1 g of the compound represented by the general formula (11), and is not particularly limited, but is 5 mL from the viewpoint of yield and reaction efficiency. As mentioned above, 60 mL or less is preferable, 10 mL or more and 50 mL or less are more preferable, and 20 mL or more and 45 mL or less are more preferable.

3-4. Coupling reaction Further, by the coupling reaction, the structural unit of the present invention and the structural unit forming the donor-acceptor polymer compound in combination with the structural unit of the present invention are alternately arranged, thereby A polymer compound (1) can be produced.

  In the presence of a metal catalyst, the coupling reaction may be any of the compound represented by the general formula (6) or the compound represented by the general formula (12) and the compounds represented by the following formulas (B1) to (B21). This is done by reacting the heel.

[In the formulas (B1) to (B28), R ^{50 to} R ⁷⁸ each independently represents the same group as the hydrocarbon group having 8 to 30 carbon atoms of R ^{21 to} R ²⁶ , A ⁵⁰ , A ⁵¹ independently represents the same group as A ¹ and A ^2, and Y represents a halogen atom. j represents an integer of 1 to 4. ]

The compounds represented by the above formulas (B1) to (B15) are compounds that form acceptor units, and the compounds represented by formulas (B17) to (B28) are compounds that form donor units. It is. The group represented by the formula (B16) may form an acceptor unit or a donor unit depending on the types of A ⁵⁰ and A ⁵¹ .

  The molar ratio of the compound represented by the general formula (6) or the compound represented by the general formula (12) to any one of the compounds represented by the formulas (B1) to (B28) is 1:99 to 99: 1 is preferable, 20:80 to 80:20 is more preferable, and 40:60 to 60:40 is more preferable.

  As the metal catalyst for coupling, a transition metal catalyst is preferable. Examples of the transition metal catalyst include a palladium catalyst, a nickel catalyst, an iron catalyst, a copper catalyst, a rhodium catalyst, and a ruthenium catalyst. Among these, a palladium-based catalyst is preferable. The palladium of the palladium-based catalyst may be zero-valent or divalent.

  As the palladium-based catalyst, any of the palladium-based catalysts exemplified in the third step can be used, and these catalysts may be used singly or in combination of two or more. Among these, tris (dibenzylideneacetone) dipalladium (0) and tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferable.

  In the coupling step, the molar ratio of the compound represented by the general formula (6) or the compound represented by the general formula (12) and the metal catalyst (compound (6): metal catalyst) is generally 1: 0.0001. ˜1: 0.5 and is not particularly limited, but is preferably 1: 0.001 to 1: 0.3, more preferably 1: 0.005 to 1: 0.2 from the viewpoint of yield and reaction efficiency. 1: 0.01 to 1: 0.1 is more preferable.

  In the coupling reaction, a specific ligand may be coordinated with the metal catalyst. As the ligand, any of the ligands exemplified in the third step can be used, and a catalyst coordinated with any of these ligands may be used in the reaction. A ligand may be used individually by 1 type and may be used in mixture of 2 or more types. Of these, tris (o-tolyl) phosphine is preferable.

  In the coupling step, when the ligand is coordinated to the metal catalyst, the molar ratio of the metal catalyst to the ligand (metal catalyst: ligand) is generally about 1: 0.5 to 1:10. Although not particularly limited, 1: 1 to 1: 8 are preferable from the viewpoint of yield and reaction efficiency, 1: 1 to 1: 7 are more preferable, and 1: 1 to 1: 5 are even more preferable.

  In the coupling reaction, as a solvent for reacting the compound represented by the general formula (6) or the compound represented by the general formula (12) with any of the compounds represented by the formulas (B1) to (B28) The solvent is not particularly limited as long as it does not affect the reaction, and conventionally known solvents can be used, for example, ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents. An amide solvent or the like can be used. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of the hydrocarbon solvent include pentane, hexane, and heptane. Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro- (1H ) -Pyrimidinone. In addition, nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane can be used. Among these, tetrahydrofuran, chlorobenzene, and N, N-dimethylformamide are preferable, and chlorobenzene is particularly preferable. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.

  In the coupling step, the amount of the solvent used relative to 1 g in total of the compound represented by the general formula (6) or the compound represented by the general formula (12) and the compounds represented by the formulas (B1) to (B28) is: Generally, it is about 1 mL or more and about 100 mL or less, and is not particularly limited. However, from the viewpoint of yield and reaction efficiency, 10 mL or more and 80 mL or less are preferable, 15 mL or more and 70 mL or less are more preferable, and 20 mL or more and 60 mL or less are more preferable.

  This application claims the benefit of priority based on Japanese Patent Application No. 2013-222658 filed on October 25, 2013. The entire contents of the specification of Japanese Patent Application No. 2013-222658 filed on October 25, 2013 are incorporated herein by reference.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

  The measurement methods used in the examples are as follows.

NMR spectrum measurement About the benzobis thiazole compound, NMR spectrum measurement was performed using the NMR spectrum measuring device (Agilent (formerly Varian), "400MR", and Bruker, "AVANCE 500").

High-resolution mass spectrum measurement The benzobisthiazole compound was subjected to high-resolution mass spectrum measurement (APCI: atmospheric pressure chemical ionization method) using a mass spectrometer (manufactured by Bruker Dartnics, “MicrOTOF”).

Gel permeation chromatography (GPC)
The molecular weight of the benzobisthiazole compound was measured using gel permeation chromatography (GPC). In the measurement, the benzobisthiazole compound was dissolved in a mobile phase solvent (chloroform) so as to have a concentration of 0.5 g / L, measured under the following conditions, and based on a calibration curve prepared using polystyrene as a standard sample. By converting, the weight average molecular weight of the benzobisthiazole compound was calculated. The GPC conditions in the measurement are as follows.
Mobile phase: Chloroform flow rate: 0.6 ml / min
Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: TSKgel (registered trademark) SuperHM-H'2 + TSKgel (registered trademark) SuperH2000 (manufactured by Tosoh Corporation)

IR spectrum About the benzobis thiazole compound, IR spectrum measurement was performed using the infrared spectroscopy apparatus (the JASCO company make, "FT / IR-6100").

Ultraviolet-visible absorption spectrum The obtained benzobisthiazole compound was dissolved in chloroform so as to have a concentration of 0.03 g / L, and an ultraviolet / visible spectrometer (“UV-2450”, “UV-3150” manufactured by Shimadzu Corporation) was dissolved. )) And UV-visible absorption spectrum measurement was performed using a cell having an optical path length of 1 cm.

Melting | fusing point measurement About the benzobis thiazole compound, melting | fusing point measurement was performed using the melting | fusing point measuring apparatus (the product made by Buchi, "M-560").

Measurement of ionization potential A benzobisthiazole compound was formed on a glass substrate so as to have a thickness of 50 nm to 100 nm. The ionization potential of this membrane was measured with an ultraviolet photoelectron analyzer (“AC-3” manufactured by Riken Keiki Co., Ltd.) under normal temperature and normal pressure.

Example 1
Synthesis of DBTH-DT (2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole)

Under a nitrogen atmosphere, DBTH (benzo [1,2-d; 4,5-d ′] bisthiazole, 4 g, 20.8 mmol) and tetrahydrofuran (160 mL) were added to a 200 mL flask, cooled to −40 ° C., and lithium diisopropylamide was added. The solution (1.5M solution, 29.1 mL, 43.7 mmol) was added dropwise. Then, after stirring at −40 ° C. for 1 hour, triisopropyl chloride (8.8 mL, 41.6 mmol) was added dropwise, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, the aqueous layer obtained by adding 10% brine and separating the layers was extracted once with ethyl acetate, and then the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, chloroform), and then DBTH-DT (2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d '] Bisthiazole) was obtained as a white solid in 7.14 g (68% yield). ¹ H-NMR measurement, ¹³ C-NMR measurement, melting point measurement, and high-resolution mass spectrum analysis confirmed that the target compound was produced.

¹ H NMR (500MHz, CDCl ₃ ): δ8.73 (s, 2H), 1.54 (sep, J = 7.3 Hz, 6H), 1.19 (d, J = 7.3 Hz, 36H).
¹³ C NMR (125 MHz, CDCl ₃ ): δ175.30, 154.18, 134.76, 115.14, 18.52, 11.76.
IR (ATR): 2943, 2865, 1466, 1388, 1308, 1056, 1016, 997, 957, 864, 650 cm ^-1 .
Melting point: 245 ° C (decomposition)
Calculated value of high resolution mass spectrum analysis: C ₂₆ H ₄₄ N ₂ S ₂ Si ₂ + H: 505.2557
Measurement: 505.2553

Example 2
Synthesis of DI-DBTH-DT (4,8-diiodo-2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole)

In a 200 mL flask under nitrogen atmosphere, DBTH-DT (2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole, 3 g, 5.88 mmol), N, N, Add N ′, N′-tetramethylethylenediamine (1.84 mL, 12.4 mmol) and tetrahydrofuran (60 mL) and cool to −40 ° C. to obtain a lithium diisopropylamide solution (1.5 M solution, 8.24 mL, 12.4 mmol). Was dripped. Thereafter, the mixture was stirred at 0 ° C. for 30 minutes, cooled to −80 ° C., iodine (7.47 g, 29.4 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, a 10% aqueous sodium hydrogen sulfite solution was added to separate the aqueous layer, and the aqueous layer was extracted once with ethyl acetate. The organic layers were combined and washed with 5% aqueous sodium bicarbonate and then with saturated brine. Dry using magnesium sulfate. The crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain DI-DBTH-DT (4,8-diiodo-2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole) was obtained as a white solid in 1.95 g (44% yield). ¹ H-NMR measurement, ¹³ C-NMR measurement, melting point measurement, and high-resolution mass spectrum analysis confirmed that the target compound was produced.

¹ H NMR (500MHz, CDCl ₃ ): δ1.52 (sep, J = 7.3 Hz, 6H), 1.19 (d, J = 7.3 Hz, 36H). ¹³ C NMR (125MHz, CDCl ₃ ): δ174.06, 151.85, 141.40, 80.24, 18.55, 11.74.
IR (ATR): 2944, 2866, 1459, 1316, 1146, 1000, 957, 878, 679, 661, 606 cm ^-1 .

Melting point: 251 ° C-252 ° C
Calculated value of high-resolution mass spectrum analysis: C ₂₆ H ₄₂ I ₂ N ₂ S ₂ Si ₂ + H: 757.0490
Measurements: 757.0521

Example 3
Synthesis of DBTH-C8THO (4,8-bis (5-octylthiophen-2-yl) benzo [1,2-d; 4,5-d ′] bisthiazole)

In a 50 mL flask under a nitrogen atmosphere, DI-DBTH-DT (4,8-diiodo-2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole, 500 mg, 0 .66 mmol), tributyl (5-octylthiophen-2-yl) stannane (962 mg, 1.98 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (62 mg, 0.06 mmol), tris (2 -Furyl) phosphine (28 mg, 0.12 mmol) and N, N-dimethylformamide (10 mL) were added and the mixture was heated to 60 ° C. and reacted for 18 hours. Then, it cooled to room temperature, the tetrabutylammonium fluoride solution (1M tetrahydrofuran solution, 2.0 mL, 1.98 mmol) was added, and it reacted for 3 hours. After completion of the reaction, water was added and the organic layer obtained by extraction twice with chloroform was washed with water and dried over anhydrous magnesium sulfate. The crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to give DBTH-C8THO (4,8-bis (5-octylthiophen-2-yl) benzo [1, 2-d; 4,5-d ′] bisthiazole) was obtained as a yellow solid in 323 mg (84% yield). ¹ H-NMR measurement, IR spectrum measurement, and high-resolution mass spectrum analysis confirmed that the target compound was produced.

¹ H NMR (500MHz, CDCl ₃ ): δ9.13 (s, 2H), 7.70 (d, J = 3.8 Hz, 2H), 6.93 (d, J = 3.8 Hz, 2H), 2.91 (t, J = 7.8 Hz, 4H), 1.78 (m, 4H), 1.53-1.28 (m, 20H), 0.88 (t, J = 6.8 Hz, 6H).
IR (ATR): 3048, 2957, 2924, 2852, 1478, 1342, 869, 842, 780 cm ^-1 .
High-resolution mass spectrum analysis calculated value: C ₃₂ H ₄₀ N ₂ S ₄ + H: 581.2147
Measurement: 581.2102

Example 4
Synthesis of DBTH-C8THO-DSM (4,8-bis (5-octylthiophen-2-yl) -2,6-bistrimethylstannylbenzo [1,2-d; 4,5-d ′] bisthiazole)

DBTH-C8THO (4,8-bis (5-octylthiophen-2-yl) benzo [1,2-d; 4,5-d ′] bisthiazole, 180 mg, 0.31 mmol) in a 30 mL flask under nitrogen atmosphere And tetrahydrofuran (6 mL) were added, and the mixture was cooled to 0 ° C. and a lithium diisopropylamide solution (2 M solution, 0.33 mL, 0.65 mmol) was added dropwise. Then, after stirring at 0 ° C. for 30 minutes, the mixture was cooled to −80 ° C., trimethyltin chloride (0.65 mL, 0.65 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and the organic layer obtained by extraction once with toluene was washed with saturated brine and dried over anhydrous magnesium sulfate. When the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), DBTH-C8THO-DSM (4,8-bis (5-octylthiophen-2-yl) -2,6 -Bistrimethylstannylbenzo [1,2-d; 4,5-d ′] bisthiazole) was obtained in 93 mg (33% yield) as an orange solid. It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400MHz, CDCl ₃ ): δ7.90 (d, J = 3.8 Hz, 2H), 6.90 (d, J = 3.8 Hz, 2H), 2.91 (t, J = 7.6 Hz, 4H), 1.76 ( m, 4H), 1.53-1.28 (m, 20H), 0.88 (t, J = 6.8 Hz, 6H), 0.57 (s, 18H).

Example 5
Synthesis of P-DBTH-C8TH-O-DPP

  In a 30 mL flask under nitrogen atmosphere, DBTH-C8THO-DSM (4,8-bis (5-octylthiophen-2-yl) -2,6-bistrimethylstannylbenzo [1,2-d; 4,5- d ′] bisthiazole, 92 mg, 0.10 mmol), O-DPP-DB (3,6-bis (5-bromothiophen-2-yl) -2,5-dioctyl-2,5-dihydropyrrolo [3, 4-c] pyrrole-1,4-dione, 69 mg, 0.10 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4.2 mg, 4.1 μmol), tris (o-tolyl) Phosphine (4.9 mg, 16 μmol) and chlorobenzene (6 mL) were added and reacted at 110 ° C. for 46 hours. After completion of the reaction, the reaction solution was added to methanol (35 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, Soxhlet extraction (chloroform) yielded 42 mg (37%) of P-DBTH-C8TH-O-DPP as a black solid. The measurement result of the ultraviolet-visible absorption spectrum is shown in FIG.

GPC measurement result Mw (weight average molecular weight): 12000
Mn (number average molecular weight): 9300
Ionization potential: 5.28 eV (HOMO-5.28 eV)

Preparation and Evaluation of Photoelectric Conversion Element Using P-DBTH-C8TH-O-DPP obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, a donor material: acceptor Material = 1: 1 (mass), dissolved in chlorobenzene at a total concentration of 1.6 wt%, and passed through a 0.45 μm filter to obtain a mixed solution.

  After cleaning the glass substrate on which ITO has been formed and performing surface treatment (ozone treatment), PEDOT-PSS (poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) is applied with a spin coater. After coating, it was annealed at 200 ° C. Next, the mixed solution of the above donor material and acceptor material was formed into a film with a spin coater and dried under reduced pressure at room temperature. On top of that, an ethanol solution of tetraisopropyl orthotitanate (about 0.3 v%) was spin-coated, and a film converted into titanium oxide by moisture in the atmosphere was prepared. Then, aluminum which is an electrode was vapor-deposited to make a device.

The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). As a result, Jsc (short-circuit current density) = 0.91 mA / cm ² , Voc (open-circuit voltage) = 0.65 V, FF (curve factor) = 0.46, and conversion efficiency is 0.27%. confirmed.

Example 6
Synthesis of DBTH-DMOT (4,8-bis [5- (3,7-dimethyloctyl) thiophen-2-yl) benzo [1,2-d; 4,5-d ′] bisthiazole)

In a 50 mL flask under a nitrogen atmosphere, DI-DBTH-DT (4,8-diiodo-2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole, 1.40 g , 1.85 mmol), tributyl [5- (3,7-dimethyloctyl) thiophen-2-yl] stannane (3.32 g, 6.48 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (115 mg, 0.11 mmol), tris (2-furyl) phosphine (52 mg, 0.22 mmol), and N, N-dimethylformamide (28 mL) were added, and the mixture was heated to 80 ° C. and reacted for 18 hours. Then, it cooled to room temperature, the tetrabutylammonium fluoride solution (1M tetrahydrofuran solution, 5.6 mL, 5.55 mmol) was added, and it reacted for 3 hours. After completion of the reaction, water was added and the organic layer obtained by extraction twice with chloroform was washed with water and dried over anhydrous magnesium sulfate. The crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain DBTH-DMOT (4,8-bis [5- (3,7-dimethyloctyl) thiophene-2. -Yl] benzo [1,2-d; 4,5-d ′] bisthiazole) was obtained in 977 mg (83% yield) as a yellow solid. ¹ H-NMR measurement, ¹³ C-NMR measurement, IR spectrum measurement, and high-resolution mass spectrum analysis confirmed that the target compound was produced.

¹ H NMR (500MHz, CDCl ₃ ): δ9.14 (s, 2H), 7.71 (d, J = 3.8 Hz, 2H), 6.94 (d, J = 3.8 Hz, 2H), 2.91 (m, 4H), 1.81 (m, 2H), 1.64-1.51 (m, 6H), 1.38-1.26 (m, 6H), 1.21-1.14 (m, 6H), 0.94 (d, J = 6.8 Hz, 6H), 0.88 (d, J = 6.8 Hz, 12H).
¹³ C NMR (125 MHz, CDCl ₃ ): δ154.91, 149.09, 148.43, 135.83, 133.15, 128.70, 124.12, 123.02, 39.34, 38.82, 37.10, 32.52, 27.98, 27.88, 24.70, 22.97, 22.61, 19.54.

IR (ATR): 3051, 2953, 2926, 1477, 1343, 842, 783, 640 cm ^-1 .
High-resolution mass spectrum analysis calculated value: C ₃₆ H ₄₈ N ₂ S ₄ + H: 637.2773
Measurement: 637.2773

Example 7
DBTH-DMOT-DSM (4,8-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -2,6-bistrimethylstannylbenzo [1,2-d; 4,5-d '] Bisthiazole)

DBTH-DMOT (4,8-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole in a 30 mL flask under nitrogen atmosphere 1 g, 1.57 mmol) and tetrahydrofuran (20 mL) were added, the mixture was cooled to 0 ° C., and a lithium diisopropylamide solution (2 M solution, 1.65 mL, 3.30 mmol) was added dropwise. Then, after stirring at 0 ° C. for 30 minutes, the mixture was cooled to −80 ° C., trimethyltin chloride (3.30 mL, 3.30 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and the organic layer obtained by extraction once with toluene was washed with saturated brine and dried over anhydrous magnesium sulfate. When the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), DBTH-DMOT-DSM (4,8-bis [5- (3,7-dimethyloctyl) thiophene-2 was obtained. -Yl] -2,6-bistrimethylstannylbenzo [1,2-d; 4,5-d ′] bisthiazole) was obtained in 518 mg (34% yield) as an orange solid. It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400MHz, CDCl ₃ ): δ7.90 (d, J = 3.8 Hz, 2H), 6.90 (d, J = 3.8 Hz, 2H), 2.93 (m, 4H), 1.81 (m, 2H), 1.64-1.51 (m, 6H), 1.38-1.26 (m, 6H), 1.21-1.14 (m, 6H), 0.94 (d, J = 6.8 Hz, 6H), 0.88 (d, J = 6.8 Hz, 12H) , 0.58 (s, 18H).

Example 8
Synthesis of P-DBTH-DMOT-TDZ

  In a 30 mL flask under nitrogen atmosphere, DBTH-DMOT-DSM (4,8-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -2,6-bistrimethylstannylbenzo [1,2 -D; 4,5-d '] bisthiazole, 180 mg, 0.19 mmol), TDZ-DB (4,7-dibromobenzo [1,2,5] thiadiazole, 55 mg, 0.19 mmol), tris (dibenzylidene) Acetone) dipalladium (0) -chloroform adduct (7.8 mg, 7.5 μmol), tris (o-tolyl) phosphine (9.1 mg, 30 μmol) and chlorobenzene (12.6 mL) were added and the reaction was carried out at 110 ° C. for 41 hours. did. After completion of the reaction, the reaction solution was added to methanol (80 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) yielded 112 mg (78%) of P-DBTH-DMOT-TDZ as a black solid. The measurement result of the ultraviolet-visible absorption spectrum is shown in FIG.

GPC measurement result Mw (weight average molecular weight): 4400
Mn (number average molecular weight): 3700
Ionization potential: 5.55 eV (HOMO -5.55 eV)

Example 9
Synthesis of DBTH-EHT (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole)

In a 30 mL flask under a nitrogen atmosphere, DI-DBTH-DT (4,8-diiodo-2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole, 800 mg, 1 .06 mmol), tributyl [5- (2-ethylhexyl) thiophen-2-yl] stannane (1.80 g, 3.70 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (115 mg, .0. 08 mmol), tris (2-furyl) phosphine (39 mg, 0.37 mmol), and N, N-dimethylformamide (16 mL) were added, and the mixture was heated to 60 ° C. and reacted for 19 hours. Then, it cooled to room temperature, the tetrabutylammonium fluoride solution (1M tetrahydrofuran solution, 5.2 mL, 3.18 mmol) was added, and it reacted for 3 hours. After completion of the reaction, water was added and the organic layer obtained by extraction twice with chloroform was washed with water and dried over anhydrous magnesium sulfate. The crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain DBTH-EHT (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl]. Benzo [1,2-d; 4,5-d ′] bisthiazole) was obtained as a yellow solid in 442 mg (yield 83%). ¹ H-NMR measurement, ¹³ C-NMR measurement, IR spectrum measurement, and high-resolution mass spectrum analysis confirmed that the target compound was produced.

¹ H NMR (500MHz, CDCl ₃ ): δ9.15 (s, 2H), 7.73 (d, J = 3.4 Hz, 2H), 6.92 (d, J = 3.4 Hz, 2H), 2.87 (dd, J = 6.4 , 3.2 Hz, 4H), 1.70 (m, 2H), 1.52-1.31 (m, 16H), 0.94 (d, J = 6.8 Hz, 6H), 0.92 (d, J = 6.8 Hz, 6H).
¹³ C NMR (125 MHz, CDCl ₃ ): δ154.87, 148.40, 147.44, 136.13, 133.04, 128.74, 125.31, 122.97, 41.44, 34.30, 32.54, 28.93, 25.69, 23.02, 14.11, 10.85.
IR (ATR): 2959, 2925, 1475, 1344, 842, 782, 638 cm ^-1 .
High-resolution mass spectrum analysis calculated value: C ₃₂ H ₄₀ N ₂ S ₄ + H: 581.2147
Measurement: 581.2146

Example 10
DBTH-EHT-DSM (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl] -2,6-bistrimethylstannylbenzo [1,2-d; 4,5-d ′] bis Synthesis of thiazole)

In a 30 mL flask under nitrogen atmosphere, DBTH-EHT (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole, 400 mg, 0.69 mmol) and tetrahydrofuran (12 mL) were added and cooled to 0 ° C., and a lithium diisopropylamide solution (2 M solution, 0.76 mL, 1.51 mmol) was added dropwise. Then, after stirring at 0 ° C. for 30 minutes, it was cooled to −80 ° C., trimethyltin chloride (1.72 mL, 1.72 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and the organic layer obtained by extraction once with toluene was washed with saturated brine and dried over anhydrous magnesium sulfate. When the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), DBTH-EHT-DSM (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl]] -2,6-bistrimethylstannylbenzo [1,2-d; 4,5-d '] bisthiazole) was obtained in 434 mg (70% yield) as an orange solid. It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400MHz, CDCl ₃ ): δ7.93 (d, J = 3.8 Hz, 2H), 6.91 (d, J = 3.8 Hz, 2H), 2.87 (dd, J = 6.4, 3.2 Hz, 4H), 1.70 (m, 2H), 1.47-1.33 (m, 16H), 1.38-1.26 (m, 6H), 0.94 (d, J = 6.8 Hz, 6H), 0.91 (d, J = 6.8 Hz, 6H), 0.58 (s, 18H).

Example 11 Synthesis of P-DBTH-EHT-EH-DPP

  In a 20 mL flask under nitrogen atmosphere, DBTH-EHT-DSM (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl] -2,6-bistrimethylstannylbenzo [1,2-d; 4,5-d ′] bisthiazole, 120 mg, 0.13 mmol), EH-DPP-DB (3,6-bis (5-bromothiophen-2-yl) -2,5- (2-ethylhexyl) -2 , 5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione, 90 mg, 0.13 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (5.5 mg, 5.3 μmol) ), Tris (o-tolyl) phosphine (6.5 mg, 21 μmol) and chlorobenzene (8.5 mL) were added and reacted at 110 ° C. for 42 hours. After completion of the reaction, the reaction mixture was added to methanol (45 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, by Soxhlet extraction (chloroform), 65 mg (43%) of P-DBTH-EHT-EH-DPP was obtained as a black solid. The measurement results of the ultraviolet-visible absorption spectrum are shown in FIG.

GPC measurement result Mw (weight average molecular weight): 14900
Mn (number average molecular weight): 7300
Ionization potential: 5.30 eV (HOMO-5.30 eV)

Example 12
DBTH-EHT-DSB (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl] -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] bis Synthesis of thiazole)

In a 30 mL flask under nitrogen atmosphere, DBTH-EHT (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole, 450 mg, 0.78 mmol) and tetrahydrofuran (30 mL) were added and cooled to 0 ° C., and a lithium diisopropylamide solution (2 M solution, 0.81 mL, 1.64 mmol) was added dropwise. Then, after stirring at 0 ° C. for 30 minutes, the mixture was cooled to −40 ° C., tributyltin chloride (0.44 mL, 1.67 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and the organic layer obtained by extraction once with toluene was washed with saturated brine and dried over anhydrous magnesium sulfate. When the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), DBTH-EHT-DSB (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl]] -2,6-bistributylstannylbenzo [1,2-d; 4,5-d '] bisthiazole) was obtained as a brown oil in 353 mg (yield 39%). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 8.29 (d, J = 3.8 Hz, 2H), 6.95 (d, J = 3.8 Hz, 2H), 2.86 (d, J = 6.8 Hz, 4H), 1.84-1.76 (m, 14H), 1.51-1.30 (m, 40H), 0.99-0.91 (m, 30H).

Example 13
Synthesis of P-DBTH-EHT-O-IMTH

  In a 20 mL flask under nitrogen atmosphere, DBTH-EHT-DSB (4,8-bis [5- (2-ethylhexyl) thiophen-2-yl] -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] bisthiazole, 150 mg, 0.13 mmol), O-IMTH-DB (1,3-dibromo-5-octylthieno [3,4-c] pyrrole-4,6-dione, 57 mg, 0 .13 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (5.4 mg, 5.2 μmol), tris (o-tolyl) phosphine (6.3 mg, 21 μmol) and chlorobenzene (12 mL) were added. The reaction was carried out at 120 ° C. for 23 hours. After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, hexane). Subsequently, Soxhlet extraction (chloroform) yielded 89 mg (82%) of P-DBTH-EHT-O-IMTH as a black solid.

GPC measurement result Mw (weight average molecular weight): 29000
Mn (number average molecular weight): 6800
Ionization potential: 5.70 eV (HOMO-5.70 eV)

Example 14
Synthesis of DHD-DBTH (4,8-bis (2-hexyldecyloxy) benzo [1,2-d; 4,5-d ′] bisthiazole)

In a 50 mL flask under a nitrogen atmosphere, DI-DBTH-DT (4,8-diiodo-2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole, 3 g, 4.0 mmol), 2-hexyldecanol (5.8 g, 23.8 mmol), copper (I) iodide (151 mg, 0.79 mmol), 1,10-PHT (1,10-phenanthroline, 286 mg, 1.59 mmol) , T-butoxy sodium (1.14 g, 11.9 mmol) and 1,4-dioxane (30 mL) were added and reacted under reflux for 23 hours. After cooling to room temperature, tetrabutylammonium fluoride (1M-tetrahydrofuran solution, 12.0 mL, 11.9 mmol) was added, and the mixture was further reacted at room temperature for 3 hours. After completion of the reaction, water was added and the organic layer obtained by extraction with chloroform twice was washed with water and dried over anhydrous magnesium sulfate. The crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain DHD-DBTH (4,8-bis (2-hexyldecyloxy) benzo [1,2-d ; 4,5-d '] bisthiazole) was obtained as a brown oil in 1.30 g (49% yield). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.94 (s, 2H), 4.61 (d, J = 5.6 Hz, 4H), 1.83 (m, 2H), 1.56 (m, 4H), 1.48-1.25 (m , 44H), 0.91-0.85 (m, 12H).

Example 15
Synthesis of DHD-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] bisthiazole)

Under a nitrogen atmosphere, a 30 mL flask was charged with DHD-DBTH (4,8-bis (2-hexyldecyloxy) benzo [1,2-d; 4,5-d ′] bisthiazole, 1 g, 1.49 mmol) and tetrahydrofuran ( 20 mL) was added and the mixture was cooled to −80 ° C. and n-butyllithium (1.6 M hexane solution, 1.95 mL, 3.12 mmol) was added dropwise. After stirring for 30 minutes, tributyltin chloride (0.87 mL, 3.19 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and the organic layer obtained by extraction once with toluene was washed with saturated brine and dried over anhydrous magnesium sulfate. When the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), DHD-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributyl was obtained. Stannylbenzo [1,2-d; 4,5-d ′] bisthiazole) was obtained as a brown oil in 1.12 g (yield 63%). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 4.64 (d, J = 5.6 Hz, 4H), 1.82 (m, 2H), 1.69-1.55 (m, 16H), 1.44-1.20 (m, 68H), 0.94 -0.88 (m, 30H).

Example 16
Synthesis of P-DHD-DBTH-O-IMTH

  In a 20 mL flask under nitrogen atmosphere, DHD-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] Bisthiazole, 159 mg, 0.13 mmol), O-IMTH-DB (1,3-dibromo-5-octylthieno [3,4-c] pyrrole-4,6-dione, 54 mg, 0.13 mmol), tris (di Benzylideneacetone) dipalladium (0) -chloroform adduct (5.3 mg, 5.2 μmol), tris (o-tolyl) phosphine (6.2 mg, 21 μmol) and chlorobenzene (12 mL) were added and reacted at 120 ° C. for 24 hours. . After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone). Subsequent Soxhlet extraction (chloroform) yielded 87 mg (74%) of P-DHD-DBTH-O-IMTH as a reddish brown solid.

GPC measurement result Mw (weight average molecular weight): 17200
Mn (number average molecular weight): 6300
Ionization potential: 5.96 eV (HOMO -5.96 eV)

Example 17
Synthesis of P-DHD-DBTH-O-IMTHT

  In a 20 mL flask under nitrogen atmosphere, DHD-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] Bisthiazole, 150 mg, 0.12 mmol), O-IMTHT-DB (1,3-dibromo-5-octylthieno [3,4-c] pyrrole-4,6-dione, 71 mg, 0.12 mmol), tris (di Benzylideneacetone) dipalladium (0) -chloroform adduct (5.0 mg, 4.8 μmol), tris (o-tolyl) phosphine (5.8 mg, 19 μmol) and chlorobenzene (12 mL) were added and reacted at 120 ° C. for 24 hours. . After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) yielded 98 mg (75%) of P-DHD-DBTH-O-IMHT as a black solid.

GPC measurement result Mw (weight average molecular weight): 12100
Mn (number average molecular weight): 4400
Ionization potential: 5.61 eV (HOMO -5.61 eV)

Production / Evaluation of Photoelectric Conversion Element Using P-DHD-DBTH-O-IMTHT obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, a donor material: acceptor Material = 1: 2 (weight), dissolved in orthodichlorobenzene containing 6% (v / v) 1,8-diiodooctane at a total concentration of 3.0 wt% and passed through a 0.45 μm filter to obtain a mixed solution It was.

A device was produced in the same manner as in Example 5.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). as a result,
It was confirmed that the conversion efficiency was 0.53% when Jsc (short-circuit current density) = 1.49 mA / cm ² , Voc (open-circuit voltage) = 0.75 V, FF (curve factor) = 0.47. .

Example 18
Synthesis of P-DHD-DBTH-TDZT

  In a 20 mL flask under nitrogen atmosphere, DHD-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] Bisthiazole, 154 mg, 0.12 mmol), TDZT-DB (4,7-bis (5-bromothiophen-2-yl) benzo [1,2,5] thiadiazole, 56 mg, 0.12 mmol), tris (dibenzylidene) Acetone) dipalladium (0) -chloroform adduct (5.1 mg, 4.9 μmol), tris (o-tolyl) phosphine (6.0 mg, 20 μmol) and chlorobenzene (12 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, hexane). Subsequently, Soxhlet extraction (chloroform) yielded 44 mg (37%) of P-DHD-DBTH-TDZT as a black solid.

GPC measurement result Mw (weight average molecular weight): 10100
Mn (number average molecular weight): 3500
Ionization potential: 5.49 eV (HOMO-5.49 eV)

Production / Evaluation of Photoelectric Conversion Element Using P-DHD-DBTH-TDZT obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, donor material: acceptor material = 1: 1.5 (weight), dissolved in chlorobenzene at a total concentration of 2.0 wt%, and passed through a 0.45 μm filter to obtain a mixed solution.

A device was produced in the same manner as in Example 5.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). As a result, Jsc (short-circuit current density) = 2.80 mA / cm ² , Voc (open-circuit voltage) = 0.77 V, FF (curve factor) = 0.42, and a conversion efficiency of 0.89%. confirmed.

Example 19
Synthesis of P-DHD-DBTH-DTH

  In a 20 mL flask under nitrogen atmosphere, DHD-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] Bisthiazole, 155 mg, 0.12 mmol), DTH-DB (5,5′-dibromo-2,2′-bithiophene, 40 mg, 0.12 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (5.1 mg, 4.9 μmol), tris (o-tolyl) phosphine (6.0 mg, 20 μmol) and chlorobenzene (12 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone). Subsequently, by Soxhlet extraction (chloroform), 72 mg (69%) of P-DHD-DBTH-DTH was obtained as a dark red-brown solid.

GPC measurement result Mw (weight average molecular weight): 11600
Mn (number average molecular weight): 5800
Ionization potential: 5.42 eV (HOMO -5.42 eV)

Production / Evaluation of Photoelectric Conversion Element Using P-DHD-DBTH-DTH obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, donor material: acceptor material = 1: 2 (weight), dissolved in chlorobenzene at a total concentration of 3.0 wt%, and passed through a 0.45 μm filter to obtain a mixed solution.

A device was produced in the same manner as in Example 5.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). As a result, Jsc (short-circuit current density) = 0.68 mA / cm ² , Voc (open-circuit voltage) = 0.62 V, FF (curve factor) = 0.34, and a conversion efficiency of 0.14%. confirmed.

Example 20
Synthesis of P-DHD-DBTH-DMO-DPP

  In a 20 mL flask under nitrogen atmosphere, DHD-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] Bisthiazole, 170 mg, 0.14 mmol), DMO-DPP-DB (3,6-bis (5-bromothiophen-2-yl) -2,5- (3,7-dimethyloctyl) -2,5-dihydro Pyrrolo [3,4-c] pyrrole-1,4-dione, 100 mg, 0.14 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (5.6 mg, 5.4 μmol), tris ( o-Tolyl) phosphine (6.2 mg, 22 μmol) and chlorobenzene (12 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone). Subsequently, P-DHD-DBTH-DMO-DPP was obtained as a black solid at 153 mg (99%) by Soxhlet extraction (chloroform).

GPC measurement result Mw (weight average molecular weight): 29500
Mn (number average molecular weight): 6500
Ionization potential: 5.48 eV (HOMO-5.48 eV)

Production and Evaluation of Photoelectric Conversion Element Using P-DHD-DBTH-DMO-DPP obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, a donor material: acceptor Material = 1: 1.5 (weight), dissolved in chlorobenzene at a total concentration of 2.5 wt%, and passed through a 0.45 μm filter to obtain a mixed solution.

A device was produced in the same manner as in Example 5.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). As a result, Jsc (short-circuit current density) = 0.93 mA / cm ² , Voc (open-circuit voltage) = 0.42 V, FF (curve factor) = 0.36, and a conversion efficiency of 0.14%. confirmed.

Example 21
DHD-DBTH-3HT (4,8-bis (2-hexyldecyloxy) -2,6-bis (3-hexylthiophen-2-yl) benzo [1,2-d; 4,5-d ′] bis Synthesis of thiazole)

In a 30 mL flask under nitrogen atmosphere, DHD-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] bis Thiazole, 350 mg, 0.28 mmol), 3HTB (2-bromo-3-hexylthiophene, 207 mg, 0.84 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (11.6 mg, 11.2 μmol) ), Tris (2-methoxyphenyl) phosphine (16 mg, 44.8 μmol), and tetrahydrofuran (7 mL) were added, and the mixture was heated to 70 ° C. and reacted for 17 hours. Thereafter, the crude product obtained by concentration was purified by column chromatography (silica gel, ethyl acetate / hexane = 5/95) to obtain DHD-DBTH-3HT (4,8-bis (2-hexyldecyloxy) -2,6 -Bis (3-hexylthiophen-2-yl) benzo [1,2-d; 4,5-d ′] bisthiazole) was obtained as a brown oil in 236 mg (yield 84%). It was confirmed by ¹ H-NMR measurement analysis that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ6.83 (d, J = 3.8 Hz, 2H), 6.65 (d, J = 3.8 Hz, 2H), 4.98 (d, J = 5.6 Hz, 4H), 3.07 (t, J = 5.6 Hz, 4H), 2.00 (m, 2H), 1.69-1.55 (m, 16H), 1.81-1.20 (m, 64H), 0.92-0.83 (m, 18H).

Example 22
DHD-DBTH-3HT-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bis (3-hexyl-5-tributylstannylthiophen-2-yl) benzo [1,2-d; 4,5-d '] bisthiazole)

In a 10 mL flask under nitrogen atmosphere, DHD-DBTH-3HT (4,8-bis (2-hexyldecyloxy) -2,6-bis (3-hexylthiophen-2-yl) benzo [1,2-d; , 5-d ′] bisthiazole, 159 mg, 0.16 mmol), N, N, N ′, N ′,-tetramethylethylenediamine (59 μL, 0.39 mmol) and tetrahydrofuran (3 mL) were added and cooled to −80 ° C. N-butyllithium (1.6M hexane solution, 0.25 mL, 0.39 mmol) was added dropwise. Thereafter, after stirring for 30 minutes, tributyltin chloride (107 μL, 0.39 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and the organic layer obtained by extraction once with toluene was washed with saturated brine and dried over anhydrous magnesium sulfate. When the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), DHD-DBTH-3HT-DSB (4,8-bis (2-hexyldecyloxy) -2,6- Bis (3-hexyl-5-tributylstannylthiophen-2-yl) benzo [1,2-d; 4,5-d ′] bisthiazole) was obtained as a brown oil in 76 mg (yield 30%). . It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, C ₆ D ₆ ): δ7.22 (s, 2H), 4.99 (d, J = 5.2 Hz, 4H), 3.28 (t, J = 8.0 Hz, 4H), 2.01 (m, 2H), 1.85-1.41 (m, 28H), 1.39-1.30 (m, 60H), 1.76 (m, 12H), 0.95-0.82 (m, 36H).

Example 23
Synthesis of P-DHD-DBTH-3HTDZT

  In a 30 mL flask under nitrogen atmosphere, DHD-DBTH-3HT-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bis (3-hexyl-5-tributylstannylthiophen-2-yl) Benzo [1,2-d; 4,5-d ′] bisthiazole, 115 mg, 72.6 μmol), TDZ-DB (4,7-dibromobenzo [1,2,5] thiadiazole, 21 mg, 72.6 μmol) , Tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3.0 mg, 2.9 μmol), tris (o-tolyl) phosphine (3.5 mg, 11.6 μmol) and chlorobenzene (10 mL) were added. The reaction was carried out at 22 ° C. for 22 hours. After completion of the reaction, the reaction solution was added to methanol (80 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone). Subsequently, P-DHD-DBTH-3HTDZT was obtained as a black solid at 33 mg (40%) by Soxhlet extraction (chloroform).

GPC measurement result Mw (weight average molecular weight): 18900
Mn (number average molecular weight): 9700
Ionization potential: 5.52 eV (HOMO -5.52 eV)

Production / Evaluation of Photoelectric Conversion Element Using P-DHD-DBTH-3HTDZT obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, donor material: acceptor material = 1: 2 (weight), dissolved in orthodichlorobenzene at a total concentration of 3.0 wt%, and passed through a 0.45 μm filter to obtain a mixed solution.

A device was produced in the same manner as in Example 5.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). As a result, Jsc (short-circuit current density) = 1.57 mA / cm ² , Voc (open-circuit voltage) = 0.84 V, FF (curve factor) = 0.39, and a conversion efficiency of 0.51%. confirmed.

Example 24
Synthesis of DEH-DBTH (4,8-bis (2-ethylhexyloxy) benzo [1,2-d; 4,5-d ′] bisthiazole)

In a 50 mL flask under a nitrogen atmosphere, DI-DBTH-DT (4,8-diiodo-2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole, 3 g, 4.0 mmol), 2-ethylhexanol (3.1 g, 23.8 mmol), copper (I) iodide (151 mg, 0.79 mmol), 1,10-PHT (1,10-phenanthroline, 286 mg, 1.59 mmol) ), T-butoxy sodium (1.14 g, 11.9 mmol) and 1,4-dioxane (30 mL) were added, and the mixture was reacted under reflux for 40 hours. After cooling to room temperature, tetrabutylammonium fluoride (1M-tetrahydrofuran solution, 12.0 mL, 11.9 mmol) was added, and the mixture was further reacted at room temperature for 3 hours. After completion of the reaction, water was added and the organic layer obtained by extraction with chloroform twice was washed with water and dried over anhydrous magnesium sulfate. The crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain DEH-DBTH (4,8-bis (2-ethylhexyloxy) benzo [1,2-d. ; 4,5-d ′] bisthiazole) was obtained as a brown oil in 1.07 g (yield 60%). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.92 (s, 2H), 4.60 (dd, J = 5.8, 2.6 Hz, 4H), 1.76 (m, 2H), 1.62-1.42 (m, 8H), 1.35 -1.31 (m, 8H), 0.95 (t, J = 7.4 Hz, 6H), 0.89 (dd, J = 3.4 Hz, 6H).

Example 25
Synthesis of DEH-DBTH-DSB (4,8-bis (2-ethylhexyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d '] bisthiazole)

In a 10 mL flask under nitrogen atmosphere, DEH-DBTH (4,8-bis (2-ethylhexyloxy) benzo [1,2-d; 4,5-d ′] bisthiazole, 100 mg, 0.22 mmol) and tetrahydrofuran ( 2 mL) was added and the mixture was cooled to −80 ° C. and n-butyllithium (1.6 M hexane solution, 0.29 mL, 0.47 mmol) was added dropwise. Thereafter, after stirring for 30 minutes, tributyltin chloride (127 μL, 0.47 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and the organic layer obtained by extraction once with toluene was washed with saturated brine and dried over anhydrous magnesium sulfate. When the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), DEH-DBTH-DSB (4,8-bis (2-ethylhexyloxy) -2,6-bistributyl was obtained. Stannylbenzo [1,2-d; 4,5-d ′] bisthiazole) was obtained as a brown oil in 1.12 g (yield 63%). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ4.65 (dd, J = 5.8 Hz, 4H), 1.76 (m, 2H), 1.68-1.22 (m, 50H), 1.00-0.80 (m, 30H).

Example 26
Synthesis of P-DEH-DBTH-EH-DPP

  In a 20 mL flask under nitrogen atmosphere, DEH-DBTH-DSB (4,8-bis (2-hexyldecyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] Bisthiazole, 163 mg, 0.16 mmol), EH-DPP-DB (3,6-bis (5-bromothiophen-2-yl) -2,5- (2-ethylhexyl) -2,5-dihydropyrrolo [3 , 4-c] pyrrole-1,4-dione, 108 mg, 0.16 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4.9 mg, 6.4 μmol), tris (o-tolyl) ) Phosphine (5.8 mg, 25.4 μmol) and chlorobenzene (10 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) gave 118 mg (77%) of P-DEH-DBTH-EH-DPP as a black solid.

GPC measurement result Mw (weight average molecular weight): 21100
Mn (number average molecular weight): 13300
Ionization potential: 5.49 eV (HOMO-5.49 eV)

Production / Evaluation of Photoelectric Conversion Element Using P-DEH-DBTH-EH-DPP obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, a donor material: acceptor Material = 1: 1.5 (weight), dissolved in chlorobenzene at a total concentration of 2.0 wt%, and passed through a 0.45 μm filter to obtain a mixed solution.

A device was produced in the same manner as in Example 5.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). As a result, Jsc (short circuit current density) = 1.32 mA / cm ² , Voc (open-circuit voltage) = 0.75 V, FF (curve factor) = 0.38, and conversion efficiency is 0.38%. confirmed.

Example 27
Synthesis of DDMO-DBTH (4,8-bis (3,7-dimethyloctyloxy) benzo [1,2-d; 4,5-d ′] bisthiazole)

In a 50 mL flask under a nitrogen atmosphere, DI-DBTH-DT (4,8-diiodo-2,6-bis-triisopropylsilanylbenzo [1,2-d; 4,5-d ′] bisthiazole, 3 g, 4.0 mmol), 3,7-dimethyloctanol (5.7 g, 35.7 mmol), copper (I) iodide (151 mg, 0.79 mmol), 1,10-PHT (1,10-phenanthroline, 286 mg, 1 .59 mmol), sodium t-butoxy (1.14 g, 11.9 mmol) and 1,4-dioxane (30 mL) were added and reacted under reflux for 24 hours. After cooling to room temperature, tetrabutylammonium fluoride (1M-tetrahydrofuran solution, 12.0 mL, 11.9 mmol) was added, and the mixture was further reacted at room temperature for 3 hours. After completion of the reaction, water was added and the organic layer obtained by extraction with chloroform twice was washed with water and dried over anhydrous magnesium sulfate. The crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain DDMO-DBTH (4,8-bis (3,7-dimethyloctyloxy) benzo [1,2 -D; 4,5-d ′] bisthiazole) was obtained as a brown oil in 0.89 g (yield 44%). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.99 (s, 2H), 4.72 (m, 4H), 1.88 (m, 2H), 1.75 (m, 2H), 1.62 (m, 2H), 1.52 (m , 2H), 1.36-1.10 (m, 14H), 0.97 (d, J = 6.4 Hz, 6H), 0.83 (d, J = 6.4 Hz, 12H).

Example 28
Synthesis of DDMO-DBTH-DSB (4,8-bis (3,7-dimethyloctyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d ′] bisthiazole)

In a 30 mL flask under nitrogen atmosphere, DDMO-DBTH (4,8-bis (3,7-dimethyloctyloxy) benzo [1,2-d; 4,5-d ′] bisthiazole, 0.85 mg, 1.69 mmol ) And tetrahydrofuran (17 mL) were added, and the mixture was cooled to −80 ° C. and n-butyllithium (1.6 M hexane solution, 0.2.32 mL, 3.71 mmol) was added dropwise. Then, after stirring for 30 minutes, tributyltin chloride (1.01 mL, 3.71 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and the organic layer obtained by extraction once with toluene was washed with saturated brine and dried over anhydrous magnesium sulfate. When the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), DDMO-DBTH-DSB (4,8-bis (3,7-dimethyloctyloxy) -2,6- Bistributylstannylbenzo [1,2-d; 4,5-d ′] bisthiazole) was obtained as a brown oil in 0.66 g (yield 36%). It was confirmed by ¹ H-NMR measurement that the target compound was produced.

¹ H NMR (400 MHz, CDCl ₃ ): δ 4.80 (m, 4H), 1.89 (m, 2H), 1.77 (m, 2H), 1.69-1.55 (m, 12H), 1.51 (m, 2H), 1.41-1.11 (m, 38H), 0.97-0.84 (m, 36H).

Example 29
Synthesis of P-DDMO-DBTH-HTT

  In a 20 mL flask under nitrogen atmosphere, DDMO-DBTH-DSB (4,8-bis (3,7-dimethyloctyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d '] Bisthiazole, 160 mg, 0.15 mmol), HTT-DB (5,5'-dibromo-3-hexyl-2,2'-bithiophene, 60 mg, 0.15 mmol), tris (dibenzylideneacetone) dipalladium ( 0) -Chloroform adduct (6.1 mg, 5.9 μmol), tris (2-methoxyphenyl) phosphine (8.3 mg, 23.6 μmol) and chlorobenzene (13 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (70 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone). Subsequently, P-DDMO-DBTH-HTT was obtained in 69 mg (62%) as a dark brown solid by Soxhlet extraction (chloroform).

Ionization potential: 5.27 eV (HOMO-5.27 eV)

Example 30
Synthesis of P-DDMO-EH-BDT

  In a 20 mL flask under nitrogen atmosphere, DDMO-DBTH-DSB (4,8-bis (3,7-dimethyloctyloxy) -2,6-bistributylstannylbenzo [1,2-d; 4,5-d '] Bisthiazole, 160 mg, 0.15 mmol), EH-BDT-DB (2,6-dibromo-4,8-bis (2-ethylhexyloxy) -1,5-dithia-S-indene, 89 mg, 0 .15 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (6.1 mg, 5.9 μmol), tris (2-methoxyphenyl) phosphine (8.3 mg, 23.6 μmol) and chlorobenzene (13 mL) ) Was added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (70 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone). Subsequent Soxhlet extraction (chloroform) gave 99 mg (71%) of P-DDMO-DBTH-EH-BDT as a dark red-brown solid.

GPC measurement result Mw (weight average molecular weight): 26800
Mn (number average molecular weight): 13400
Ionization potential: 5.50 eV (HOMO-5.50 eV)

Production / Evaluation of Photoelectric Conversion Element Using P-DDMO-DBTHEH-BDT obtained as described above as a donor material and PCBM (C61) (phenyl C61-butyric acid methyl ester) as an acceptor material, donor material: acceptor material = It was dissolved in orthodichlorobenzene at a total concentration of 3.0 wt% at 1: 2.0 (weight) and passed through a 0.45 μm filter to obtain a mixed solution.

A device was produced in the same manner as in Example 5.
The obtained device was subjected to characteristic evaluation using a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). As a result, Jsc (short circuit current density) = 2.17 mA / cm ² , Voc (open circuit voltage) = 0.75 V, FF (curve factor) = 0.38, and conversion efficiency is 0.63%. confirmed.

  As described above, each of the polymer compounds of the present invention has an improved open circuit voltage (Voc) and an improved short circuit current density (Jsc), and has a moderately deep HOMO level. It was confirmed to be excellent. Furthermore, it was confirmed that various skeletons and substituents can be introduced by the production method of the present invention.

  Since the polymer compound of the present invention has high photoelectric conversion efficiency, it is useful for organic electro devices such as organic electroluminescence elements and organic thin film transistor elements.

Claims (13)

A polymer compound comprising a benzobisthiazole structural unit represented by the general formula (1), wherein a donor unit and an acceptor unit are alternately arranged.
[In general formula (1),
A ¹ and A ² are each independently an alkoxy group, a thioalkoxy group, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or hydrocarbon group, an alkoxy group, a thioalkoxy group, organosilyl group, and display the phenyl group which may be substituted with a halogen atom or trifluoromethyl group,
A ¹ and A ² are each independently a thiophene ring optionally substituted with an alkoxy group, a thioalkoxy group, or a hydrocarbon group, and the benzobisthiazole structural unit represented by the general formula (1) is a donor When it is a sex unit, the acceptor unit includes groups represented by formulas (b1) to (b16),
A ¹ and A ² are each independently a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or a hydrocarbon group, alkoxy group, thioalkoxy group, organosilyl group, halogen atom or trifluoro When it is a phenyl group which may be substituted with a methyl group and the benzobisthiazole structural unit represented by the general formula (1) is an acceptor unit, formulas (b16) to (b28) are used as donor units. The group represented by this is included.
[In the formulas (b1) to (b28),
R ^{30 to} R ⁵⁸ each independently represents a hydrocarbon group having 8 to 30 carbon atoms.
A ³⁰ and A ³¹ are each a thiophene ring in which A ¹ and A ^{2 in} the general formula (1) may be each independently substituted with an alkoxy group, a thioalkoxy group, or a hydrocarbon group. When the benzobisthiazole structural unit represented by 1) is a donor unit, each independently represents a thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group, or a hydrocarbon group or an alkoxy group. , A thioalkoxy group, an organosilyl group, a phenyl group which may be substituted with a halogen atom or a trifluoromethyl group, and A ¹ and A ^{2 in} the general formula (1) are each independently a hydrocarbon group or an organo Thiazole ring optionally substituted with silyl group, or hydrocarbon group, alkoxy group, thioalkoxy group, organosilyl group, halogen atom Or a phenyl group optionally substituted with a trifluoromethyl group, and when the benzobisthiazole structural unit represented by the general formula (1) is an acceptor unit, each independently represents an alkoxy group, a thiol group, It represents a thiophene ring optionally substituted with an alkoxy group or a hydrocarbon group.
j represents an integer of 1 to 4.
* Represents a bond with the structural unit represented by the general formula (1). ] ] The polymer compound according to claim ¹ , wherein A ¹ and A ² are each independently at least one selected from groups represented by the following general formulas (a1) to (a4).
[In the general formulas (a1) to (a4),
R ^{21 to} R ²³ and R ²⁵ each independently represents a hydrocarbon group having 8 to 30 carbon atoms. R ²⁴ represents a hydrogen atom or a hydrocarbon group having 8 to 30 carbon atoms. * Represents a bond bonded to the benzene ring of benzobisthiazole. ] Donor - The polymer compound according to claim 1 or 2 is an acceptor-type semiconductor polymers. The organic-semiconductor material containing the high molecular compound in any one of Claims 1-3 . A benzobisthiazole compound represented by the general formula (5).
[In general formula (5),
A ¹ and A ² are each independently an alkoxy group, a thioalkoxy group, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or It represents a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. ] A benzobisthiazole compound represented by the general formula (4).
[In general formula (4),
A ¹ and A ² are each independently an alkoxy group, a thioalkoxy group, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or It represents a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ] A benzobisthiazole compound represented by the general formula (3).
[In general formula (3),
X represents a halogen atom.
R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ] A benzobisthiazole compound represented by the general formula (3 ′).
[In general formula (3 ′),
X represents a halogen atom.
R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ] A benzobisthiazole compound represented by the general formula (2).
[In general formula (2),
R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ] A compound represented by the general formula (2) using benzobisthiazole as a starting material,
[In general formula (2),
R ^{1 to} R ⁶ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]
A compound represented by the general formula (3),
[In general formula (3),
X represents a halogen atom.
R ^{1 to} R ⁶ represent the same groups as described above. ]
A compound represented by the general formula (4),
[In general formula (4),
A ¹ and A ² are each independently an alkoxy group, a thioalkoxy group, a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, or It represents a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group.
R ^{1 to} R ⁶ represent the same groups as described above. ]
A compound represented by the general formula (5), and
[In general formula (5),
A ^1, A ² each represent the same group as A ^1, A ² in the general formula (4). ]
Compound represented by general formula (6)
[In General Formula (6), A ¹ and A ² represent the same groups as A ¹ and A ^{2 in} General Formula (4), respectively.
R ^{7 to} R ¹⁰ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ¹ and M ² each independently represent a boron atom or a tin atom.
R ⁷ and R ⁸ may form a ring together with M ¹ , and R ⁹ and R ¹⁰ may form a ring together with M ² .
m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ⁷ and R ⁹ may be the same or different. ]
Method for producing a polymer according to any one of claims 1 to 3, characterized in that through the. The manufacturing method of Claim 10 including the following 1st process and 2nd process.
1st process: The process which makes a base and a halogenated silane compound react with benzobis thiazole, and obtains the compound represented by General formula (2) 2nd process: A base and the compound represented by General formula (2) A step of obtaining a compound represented by the general formula (3) by reacting with a halogenating reagent. Furthermore, the manufacturing method of Claim 10 or 11 containing a 3rd process, a 4th process, and a 5th process.
Third step: In the presence of a metal catalyst, a compound represented by general formula (3) is added to general formula (7) and / or general formula (8).
[In the general formulas (7) and (8),
A ¹ and A ² each represent the same group as described above.
R ¹¹ and R ¹² each independently represents a hydrogen atom or * -M ³ (R ¹³ ) _k R ¹⁴ .
R ¹³ and R ¹⁴ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ³ represents a boron atom or a tin atom. * Represents a bond with A ¹ or A ² .
R ¹³ and R ¹⁴ may form a ring together with M ³ .
k represents an integer of 1 or 2. When k is 2, the plurality of R ¹³ may be the same or different. ]
A step of obtaining a compound represented by the general formula (4) by reacting the compound represented by general formula (4) Fourth step: The compound represented by the general formula (4) is treated with an acid or a base, and the general formula ( Step 5 for obtaining the compound represented by 5) Step 5: The compound represented by the general formula (5) is reacted with a base and a tin halide compound or a borate ester, and represented by the general formula (6). Step of obtaining a compound Furthermore, the manufacturing method in any one of Claims 10-12 including a 6th process and a 7th process.
Sixth step: General formula (9) and / or general formula (10) in the presence of a metal catalyst in the compound represented by general formula (6)
[In the general formulas (9) and (10),
R ²⁷ and R ²⁸ represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
X ¹ and X ² represent a halogen atom. ]
Is reacted with a compound represented by the general formula (11):
[In general formula (11),
A ¹ , A ² , R ²⁷ and R ²⁸ each represent the same group as described above. ]
Step 7 for obtaining a compound represented by general formula (11): A compound represented by general formula (11) is reacted with a base and a tin halide compound or a borate ester to obtain a compound represented by general formula (12). Obtaining process
[In general formula (12),
A ¹ , A ² , R ²⁷ and R ²⁸ each represent the same group as described above.
R ^{29 to} R ³² each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
M ³ and M ⁴ each independently represent a boron atom or a tin atom.
R ²⁹ and R ³⁰ may form a ring together with M ³ , and R ³¹ and R ³² may form a ring together with M ⁴ .
m1 and n1 each represents an integer of 1 or 2. When m1 and n1 are 2, the plurality of R ²⁹ and R ³¹ may be the same or different. ]