JP7692856B2 - New compounds and their manufacturing methods - Google Patents

Description

The present invention relates to a novel compound useful as a raw material for conjugated polymers that contain oligoheteroacenes containing chalcogenochalcogenophenes as structural units, and a method for producing the same.

Conjugated organic compounds are well known as organic semiconductors used in organic thin-film solar cells, organic thin-film transistors, organic electroluminescence (EL), and the like. Conjugated organic compounds have characteristics not found in inorganic compounds, such as energy saving, low cost, solubility in organic solvents, light weight, and flexibility, and can also be used as coating materials applied to printed electronics (Patent Document 1).

Conjugated organic compounds such as oligoacenes, such as pentacene, disclosed in Non-Patent Document 1, and oligoacenes having a thiophene skeleton and a thienothiophene skeleton, etc., disclosed in Non-Patent Document 2 (hereinafter referred to as oligoheteroacenes), are being studied for application to organic thin-film transistors. Among them, oligoheteroacenes having a thienothiophene skeleton tend to show high carrier mobility.

JP 2017-59668 A

Polymer Journal, Vol. 49, pp. 23-30, 2017. Chemical Reviews, Vol. 115, pp. 3036-3140, 2015. Tetrahedron Letters, Vol. 55, pp. 5663-5666, 2014.

However, problems with oligoheteroacenes, such as low solubility, poor film-forming ability, and poor atmospheric stability, have been pointed out (Non-Patent Document 3). Therefore, there is a demand for the development of new conjugated organic compounds and compounds that are useful as raw materials for these compounds.

In order to solve the above problems, the present invention aims to provide a compound that is useful as a raw material for new conjugated polymers that have high carrier mobility, high heat resistance, and high solubility, and a method for producing the compound.

In order to solve the above problems, the inventors conducted extensive research and discovered a specific compound that is useful as a raw material for conjugated polymers that contain a 5,5,10,10-tetraalkyl-5,10-dihydrochalcogeno[2",3":4",5']chalcogeno[2',3':4,5]pentaleno[1,2-b]chalcogeno[2,3-d]chalcogenophene skeleton as a structural unit, leading to the completion of the present invention.

（式中、Ｒ^１及びＲ^２は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^１とＲ^２とが一体となってそれらが結合する炭素原子とともに環を形成しても良い。Ｒ^３及びＲ^４は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^３とＲ^４とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^５及びＲ^６は各々独立に、水素原子、フッ素原子又は炭素数１～５０のアルキル基を表す。Ｊ^１、Ｊ^２、Ｊ^３及びＪ^４は各々独立にカルコゲン原子を表す。Ｍ^１及びＭ^２は各々独立にハロゲン原子、金属含有基、ホウ素含有基及びスズ含有基からなる群から選択される一つの基を表す。）
要旨１に関し、Ｒ^１及びＲ^２は各々独立に炭素数１～３４のアルキル基であり、Ｒ^１とＲ^２とは一体となってそれらが結合する炭素原子とともに環を形成してもよく、Ｒ^３及びＲ^４は各々独立に炭素数１～３４のアルキル基であり、Ｒ^３とＲ^４とは一体となってそれらが結合する炭素原子とともに環を形成してもよく、Ｒ^５及びＲ^６は各々独立に水素原子、フッ素原子又は炭素数１～３４のアルキル基であり、Ｊ^１、Ｊ^２、Ｊ^３及びＪ^４は各々独立に酸素原子、硫黄原子、セレン原子であり、Ｍ^１及びＭ^２は各々独立に臭素原子、ヨウ素原子、ホウ素含有基及びスズ含有基からなる群から選択される一つの基であってもよい。
要旨１に関し、Ｒ^５及びＲ^６は水素原子であり、Ｊ^１、Ｊ^２、Ｊ^３及びＪ^４は硫黄原子であり、Ｍ^１及びＭ^２は各々独立に水素原子、臭素原子、ホウ素含有基及びスズ含有基からなる群から選択される一つの基であってもよい。
［要旨２］
下記一般式（２－ｈａｌ）で表される化合物に、

（式中、Ｒ^１及びＲ^２は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^１とＲ^２とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^３及びＲ^４は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^３とＲ^４とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^５及びＲ^６は各々独立に水素原子、フッ素原子又は炭素数１～５０のアルキル基を表す。Ｊ^１、Ｊ^２、Ｊ^３及びＪ^４は各々独立にカルコゲン原子を表す。Ｍ^{１－ｍｏｎｏ－ｈａｌ}及びＭ^{２－ｍｏｎｏ－ｈａｌ}は各々独立にハロゲン原子を表す。）
酸を作用させることを含む、下記一般式（ｍｏｎｏ－ｈａｌ）で表される化合物の製造方法。

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｊ^１、Ｊ^２、Ｊ^３、Ｊ^４、Ｍ^{１－ｍｏｎｏ－ｈａｌ}、及びＭ^{２－ｍｏｎｏ－ｈａｌ}は、それぞれ前記と同様の意味を表す。）
要旨２に関し、前記酸はルイス酸であってもよい。
要旨２に関し、前記酸は四塩化スズであってもよい。
［要旨３］
下記一般式（ｍｏｎｏ－ｈａｌ）で表される化合物に、

（式中、Ｒ^１及びＲ^２は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^１とＲ^２とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^３及びＲ^４は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^３とＲ^４とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^５及びＲ^６は各々独立に水素原子、フッ素原子又は炭素数１～５０のアルキル基を表す。Ｊ^１、Ｊ^２、Ｊ^３及びＪ^４は各々独立にカルコゲン原子を表す。Ｍ^{１－ｍｏｎｏ－ｈａｌ}及びＭ^{２－ｍｏｎｏ－ｈａｌ}は各々独立にハロゲン原子を表す。）
塩基及び遷移金属触媒の一方又は両方の存在下でホウ素化合物又はスズ化合物を作用させることを含む、下記一般式（ｍｏｎｏ－ｎｕｃ）で表される化合物の製造方法。

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｊ^１、Ｊ^２、Ｊ^３、及びＪ^４はそれぞれ前記と同様の意味を表す。Ｍ^{１－ｍｏｎｏ－ｎｕｃ}及びＭ^{２－ｍｏｎｏ－ｎｕｃ}は各々独立にホウ素含有基又はスズ含有基を表す。）
要旨３に関し、前記塩基を前記一般式（ｍｏｎｏ－ｈａｌ）で表される化合物に作用させた後に、前記ホウ素化合物をさらに作用させてもよい。
要旨３に関し、前記塩基を前記一般式（ｍｏｎｏ－ｈａｌ）で表される化合物に作用させた後に、前記スズ化合物をさらに作用させてもよい。
要旨３に関し、前記塩基は有機金属試薬であってもよい。
要旨３に関し、前記塩基はアルキルリチウムであってもよい。
要旨３に関し、前記遷移金属触媒存在下で、前記一般式（ｍｏｎｏ－ｈａｌ）で表される化合物に前記ホウ素化合物を作用させてもよい。
要旨３に関し、前記遷移金属触媒存在下で、前記一般式（ｍｏｎｏ－ｈａｌ）で表される化合物に前記スズ化合物を作用させてもよい。
要旨３に関し、前記遷移金属触媒はパラジウム触媒であってもよい。
［要旨４］
下記一般式（Ｐｕｂ－Ｈ）で表される化合物に、

（式中、Ｒ^１及びＲ^２は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^１とＲ^２とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^３及びＲ^４は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^３とＲ^４とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^５及びＲ^６は各々独立に水素原子、フッ素原子又は炭素数１～５０のアルキル基を表す。Ｊ^１、Ｊ^２、Ｊ^３及びＪ^４は各々独立にカルコゲン原子を表す。）
塩基又は遷移金属触媒存在下でホウ素化合物又はスズ化合物を作用させることを含む、下記一般式（ｍｏｎｏ－ｎｕｃ）で表される化合物の製造方法。

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｊ^１、Ｊ^２、Ｊ^３、及びＪ^４はそれぞれ前記と同様の意味を表す。Ｍ^{１－ｍｏｎｏ－ｎｕｃ}及びＭ^{２－ｍｏｎｏ－ｎｕｃ}は各々独立にホウ素含有基又はスズ含有基を表す。）
要旨４に関し、前記塩基を前記一般式（Ｐｕｂ－Ｈ）で表される化合物に作用させた後に、前記ホウ素化合物をさらに作用させてもよい。
要旨４に関し、前記塩基を前記一般式（Ｐｕｂ－Ｈ）で表される化合物に作用させた後に、前記スズ化合物を作用させてもよい。
要旨４に関し、前記塩基は有機金属試薬であってもよい。
要旨４に関し、前記塩基はアルキルリチウムであってもよい。
要旨４に関し、前記塩基はリチウムアミドであってもよい。
要旨４に関し、前記遷移金属触媒存在下で、前記一般式（Ｐｕｂ－Ｈ）で表される化合物に前記ホウ素化合物を作用させてもよい。
要旨４に関し、前記遷移金属触媒存在下で、前記一般式（Ｐｕｂ－Ｈ）で表される化合物に前記スズ化合物を作用させてもよい。
要旨４に関し、前記遷移金属触媒はイリジウム触媒であってもよい。
［要旨５］
下記一般式（Ｐｕｂ－Ｈ）で表される化合物に、

（式中、Ｒ^１及びＲ^２は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^１とＲ^２とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^３及びＲ^４は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^３とＲ^４とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^５及びＲ^６は各々独立に水素原子、フッ素原子又は炭素数１～５０のアルキル基を表す。Ｊ^１、Ｊ^２、Ｊ^３及びＪ^４は各々独立にカルコゲン原子を表す。）
ハロゲン化剤を作用させることを含む、下記一般式（ｍｏｎｏ－ｈａｌ）で表される化合物の製造方法。

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｊ^１、Ｊ^２、Ｊ^３、及びＪ^４は前記と同様の意味を表す。Ｍ^{１－ｍｏｎｏ－ｈａｌ}及びＭ^{２－ｍｏｎｏ－ｈａｌ}は各々独立にハロゲン原子を表す。）
要旨５に関し、前記ハロゲン化剤は臭素又ヨウ素であってもよい。
要旨５に関し、前記ハロゲン化剤はスクシンイミド化合物であってもよい。 That is, the present invention comprises the following:
[Abstract 1]
A compound represented by the following general formula (mono):

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 50 carbon atoms. R ¹ and R ² may be combined together to form a ring with the carbon atom to which they are bonded. ^{R 3} and R ⁴ each independently represent an alkyl group having 1 to 50 carbon atoms. ^{R 3} and R ⁴ may be combined together to form a ring with the carbon atom to which they are bonded. ^{R 5} and R ⁶ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. J ¹ , J ² , J ³ , and J ⁴ each independently represent a chalcogen atom. ^{M 1} and M ² each independently represent a group selected from the group consisting of a halogen atom, a metal-containing group, a boron-containing group, and a tin-containing group.)
Regarding Summary 1, ^R1 and ^R2 are each independently an alkyl group having 1 to 34 carbon atoms, and ^R1 and ^R2 may be joined together to form a ring with the carbon atom to which they are bonded; ^R3 and ^R4 are each independently an alkyl group having 1 to 34 carbon atoms, and ^R3 and ^R4 may be joined together to form a ring with the carbon atom to which they are bonded; ^R5 and ^R6 are each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 34 carbon atoms; ^J1 , ^J2 , ^J3 , and ^J4 are each independently an oxygen atom, a sulfur atom, or a selenium atom; and ^M1 and ^M2 may each independently be a group selected from the group consisting of a bromine atom, an iodine atom, a boron-containing group, and a tin-containing group.
Regarding Summary 1, ^R5 and ^R6 are hydrogen atoms, ^J1 , ^J2 , ^J3 and ^J4 are sulfur atoms, and ^M1 and ^M2 may each independently be one group selected from the group consisting of a hydrogen atom, a bromine atom, a boron-containing group and a tin-containing group.
[Summary 2]
A compound represented by the following general formula (2-hal),

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may combine with the carbon atom to which they are bonded to form a ring. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may combine with the carbon atom to which they are bonded to form a ring. ^R5 and ^R6 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-mono-hal and M2 ^-mono-hal each independently represent a halogen atom.)
A method for producing a compound represented by the following general formula (mono-hal), which comprises reacting with an acid:

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , M ^1-mono-hal , and M ^2-mono-hal are each as defined above.)
Regarding aspect 2, the acid may be a Lewis acid.
Regarding aspect 2, the acid may be tin tetrachloride.
[Summary 3]
A compound represented by the following general formula (mono-hal):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may combine with the carbon atom to which they are bonded to form a ring. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may combine with the carbon atom to which they are bonded to form a ring. ^R5 and ^R6 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-mono-hal and M2 ^-mono-hal each independently represent a halogen atom.)
A method for producing a compound represented by the following general formula (mono-nuc):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , and J ⁴ are as defined above. M ^1-mono-nuc and M ^2-mono-nuc each independently represent a boron-containing group or a tin-containing group.)
Regarding the aspect 3, after the base is reacted with the compound represented by the general formula (mono-hal), the compound may be further reacted with the boron compound.
Regarding the aspect 3, after the base is reacted with the compound represented by the general formula (mono-hal), the compound may be further reacted with the tin compound.
Regarding aspect 3, the base may be an organometallic reagent.
Regarding Aspect 3, the base may be an alkyl lithium.
Regarding the aspect 3, the compound represented by the general formula (mono-hal) may be reacted with the boron compound in the presence of the transition metal catalyst.
Regarding the aspect 3, the compound represented by the general formula (mono-hal) may be reacted with the tin compound in the presence of the transition metal catalyst.
Regarding Aspect 3, the transition metal catalyst may be a palladium catalyst.
[Abstract 4]
A compound represented by the following general formula (Pub-H):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may combine with the carbon atom to which they are bonded to form a ring. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may combine with the carbon atom to which they are bonded to form a ring. ^R5 and ^R6 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom.)
A method for producing a compound represented by the following general formula (mono-nuc):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , and J ⁴ are as defined above. M ^1-mono-nuc and M ^2-mono-nuc each independently represent a boron-containing group or a tin-containing group.)
Regarding the aspect 4, after reacting the compound represented by the general formula (Pub-H) with the base, the compound may be further reacted with the boron compound.
Regarding the aspect 4, the compound represented by the general formula (Pub-H) may be reacted with the base and then with the tin compound.
Regarding aspect 4, the base may be an organometallic reagent.
Regarding the aspect 4, the base may be an alkyl lithium.
Regarding aspect 4, the base may be lithium amide.
Regarding the aspect 4, the compound represented by the general formula (Pub-H) may be reacted with the boron compound in the presence of the transition metal catalyst.
Regarding the aspect 4, the compound represented by the general formula (Pub-H) may be reacted with the tin compound in the presence of the transition metal catalyst.
Regarding the fourth aspect, the transition metal catalyst may be an iridium catalyst.
[Abstract 5]
A compound represented by the following general formula (Pub-H):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may combine with the carbon atom to which they are bonded to form a ring. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may combine with the carbon atom to which they are bonded to form a ring. ^R5 and ^R6 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom.)
A method for producing a compound represented by the following general formula (mono-hal), comprising reacting with a halogenating agent:

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , and J ⁴ are as defined above. M ^1-mono-hal and M ^2-mono-hal each independently represent a halogen atom.)
Regarding Aspect 5, the halogenating agent may be bromine or iodine.
Regarding Aspect 5, the halogenating agent may be a succinimide compound.

The conjugated polymer produced using the compound of the present invention has high carrier mobility, high heat resistance, and high solubility, and can efficiently drive an organic thin-film transistor element that uses this as the active layer.

FIG. 2 is a diagram showing a cross-sectional structure of an organic thin film transistor element.

The following describes in detail the embodiments of the present invention. However, the present invention is not limited to these, and various modifications are possible within the scope described. The technical scope of the present invention also includes embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. In this specification, unless otherwise specified, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B."

[Compound]
A compound according to one embodiment of the present invention (sometimes referred to as "the compound of the present embodiment" in this specification) is a compound represented by the general formula (mono).

（式中、Ｒ^１及びＲ^２は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^１とＲ^２とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^３及びＲ^４は各々独立に炭素数１～５０のアルキル基を表す。Ｒ^３とＲ^４とが一体となってそれらが結合する炭素原子とともに環を形成してもよい。Ｒ^５及びＲ^６は各々独立に、水素原子、フッ素原子又は炭素数１～５０のアルキル基を表す。Ｊ^１、Ｊ^２、Ｊ^３及びＪ^４は各々独立にカルコゲン原子を表す。Ｍ^１及びＭ^２は各々独立にハロゲン原子、金属含有基、ホウ素含有基及びスズ含有基からなる群から選択される一つの基を表す。）

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 50 carbon atoms. R ¹ and R ² may be combined together to form a ring with the carbon atom to which they are bonded. ^{R 3} and R ⁴ each independently represent an alkyl group having 1 to 50 carbon atoms. ^{R 3} and R ⁴ may be combined together to form a ring with the carbon atom to which they are bonded. ^{R 5} and R ⁶ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. J ¹ , J ² , J ³ , and J ⁴ each independently represent a chalcogen atom. ^{M 1} and M ² each independently represent a group selected from the group consisting of a halogen atom, a metal-containing group, a boron-containing group, and a tin-containing group.)

(General formula (mono))
R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R The alkyl group having 1 to 50 carbon atoms, represented by ^6, may be any of linear, branched, and cyclic, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentriacontyl, dodoriacontyl, tritriacontyl, tetratriacontyl, pentatriacontyl, hexatriacontyl, tetracontyl, hexatria ... Examples of such alkyl groups include linear alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl, 2-tetradecylhexadecyl, 3-decylpentadecyl, 3-dodecylheptadecyl, 3-tetradecylnonacosyl, 4-decylhexadecyl, 4-dodecyloctadecyl, and 4-tetradecylicocosyl groups.

As the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ , an alkyl group having 1 to 34 carbon atoms is preferred in terms of increasing the solubility of the compound of this embodiment, and an alkyl group having 6 to 34 carbon atoms is more preferred, and examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dodoriacontyl group, a tritriacontyl group, a tetratriacontyl group, and a pentatriacontyl group. More preferred are a hexatriacontyl group, a tetracontyl group, a hentetracontyl group, a dotetracontyl group, a tritetracontyl group, a tetratetracontyl group, a pentacontyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyloctyl group, a 2-hexyldecyl group, a 2-octyldodecyl group, a 2-decyltetradecyl group, a 2-dodecyltetradecyl group, a 2-dodecylhexadecyl group, a 2-tetradecylhexadecyl group, a 3-decylpentadecyl group, a 3-dodecylheptadecyl group, a 3-tetradecylnonacosyl group, a 4-decylhexadecyl group, a 4-dodecyloctadecyl group, or a 4-tetradecylicocosyl group, and a hexyl group or a decyl group is particularly preferred.

R ¹ and R ² may be united to form a ring together with the carbon atom to which they are bonded. Examples of the ring include a cyclopropane-1,1-diyl group, a cyclobutane-1,1-diyl group, a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, a cycloheptane-1,1-diyl group, a cyclooctane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group. In terms of increasing the solubility of the compound of this embodiment, the ring is preferably a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group, and more preferably a cyclohexane-1,1-diyl group or a fluorene-9,9-diyl group. R ³ and R ⁴ may be united to form a ring together with the carbon atom to which they are bonded. Examples of the ring include a cyclopropane-1,1-diyl group, a cyclobutane-1,1-diyl group, a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, a cycloheptane-1,1-diyl group, a cyclooctane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group. In terms of increasing the solubility of the compound of this embodiment, a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group is preferred, and a cyclohexane-1,1-diyl group or a fluorene-9,9-diyl group is more preferred.

R ⁵ is preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 34 carbon atoms, more preferably a hydrogen atom, a fluorine atom, or an alkyl group having 6 to 34 carbon atoms, in that the solubility of the compound of this embodiment is high, and a hydrogen atom, a fluorine atom, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dodoriacontyl group, a tritriacontyl group, More preferred are tetratriacontyl, pentatriacontyl, hexatriacontyl, tetracontyl, hentetracontyl, dotetracontyl, tritetracontyl, tetratetracontyl, pentacontyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl, 2-tetradecylhexadecyl, 3-decylpentadecyl, 3-dodecylheptadecyl, 3-tetradecylnonacosyl, 4-decylhexadecyl, 4-dodecyloctadecyl, or 4-tetradecylicosyl. Among these, R ⁵ is particularly preferably a hydrogen atom or a fluorine atom in terms of increasing carrier mobility.

R ⁶ is preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 34 carbon atoms, more preferably a hydrogen atom, a fluorine atom, or an alkyl group having 6 to 34 carbon atoms, from the viewpoint of increasing the carrier mobility or solubility of the conjugated polymer described later, and more preferably a hydrogen atom, a fluorine atom, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dodoriacontyl group, a tritriacontyl group, More preferred are pentyl, tetratriacontyl, pentatriacontyl, hexatriacontyl, tetracontyl, hentetracontyl, dotetracontyl, tritetracontyl, tetratetracontyl, pentacontyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl, 2-tetradecylhexadecyl, 3-decylpentadecyl, 3-dodecylheptadecyl, 3-tetradecylnonacosyl, 4-decylhexadecyl, 4-dodecyloctadecyl, or 4-tetradecylicosyl. Among these, it is particularly preferred that R ⁶ is a hydrogen atom or a fluorine atom in terms of increasing carrier mobility.

As the chalcogen atom represented by J ¹ , J ² , J ³ or J ⁴ , an oxygen atom, a sulfur atom or a selenium atom is preferable, an oxygen atom or a sulfur atom is more preferable, and a sulfur atom is even more preferable, in terms of increasing the solubility of the compound of this embodiment.

As the halogen atom represented by ^M1 and ^M2 , a chlorine atom, a bromine atom or an iodine atom is preferable, a bromine atom or an iodine atom is more preferable, and a bromine atom is even more preferable, in terms of increasing the solubility of the compound of this embodiment.

As the metal-containing group represented by ^M1 and ^M2 , a lithium atom, a chloromagnesio group, or a bromomagnesio group is preferable, and a chloromagnesio group is more preferable, in that the solubility of the compound of this embodiment is increased.

As the boron-containing group represented by ^M1 and ^M2 , from the viewpoint of increasing the solubility of the compound of the present embodiment, boronic acid, boronic acid ester, borate salt, or the like is preferable, groups represented by formulas (12-1) to (12-6) are more preferable, groups represented by formula (12-1), formula (12-3), formula (12-5) or formula (12-6) are even more preferable, formula (12-1) or formula (12-3) is even more preferable, and formula (12-3) is particularly preferable.

Examples of the tin-containing group represented by ^M1 and ^M2 include a trialkylstannyl group, a dialkylarylstannyl group, an alkyldiarylstannyl group, and a triarylstannyl group. In terms of increasing the solubility of the compound of this embodiment, a trialkylstannyl group or a triarylstannyl group is preferred, with the groups represented by formulae (13-1) to (13-5) being more preferred, and the group represented by formula (13-1) being even more preferred. In this specification, Me, Et, ⁱ Pr, ^t Bu, and Ph represent a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a phenyl group, respectively.

Examples of compounds of this embodiment include those represented by the following general formulae (mono-hal-1) to (mono-hal-60), (mono-B-1) to (mono-B-60), and (mono-Sn-1) to (mono-Sn-60).

As the compound of this embodiment, the formulas (mono-hal-1) to (mono-hal-48), (mono-B-1) to (mono-B-48), and (mono-Sn-1) to (mono-Sn-48) are preferred in that the film-forming properties and carrier mobility of the conjugated polymer obtained using the compound as a monomer are improved, and the formulas (mono-hal-1) to (mono-hal-48) are preferred. More preferred are the formulas (mono-hal-1), (mono-hal-2), (mono-hal-4), (mono-hal-5), (mono-hal-7), (mono-hal-8), (mono-hal-10), (mono-hal-11), (mono-hal-12), (mono-hal-13), (mono-hal-14), (mono-hal-15), (mono-hal-16), (mono-hal-17), (mono-hal-18), (mono-hal-19), (mono-hal-20), (mono-hal-21), (mono-hal-22), (mono-hal-23), (mono-hal-24), (mono-hal-25), (mono-hal-26), (mono-hal-27), (mono-hal-28), (mono-hal-2 ...9), (mono-hal-20), (mono-hal-21), (mono-hal-22), (mono-hal-23), (mono-hal-24), (mono-hal-25), (mono-hal-25), (mono-hal-2 ), formula (mono-hal-11), formula (mono-hal-13), formula (mono-hal-14), formula (mono-hal-16), formula (mono-hal-17), formula (mono -hal-19), formula (mono-hal-20), formula (mono-hal-22), formula (mono-hal-23), formula (mono-hal-25), formula (mono-hal-26) , formula (mono-hal-28), formula (mono-hal-29), formula (mono-hal-31), formula (mono-hal-32), formula (mono-hal-34), formula (mono- hal-35), formula (mono-B-1), formula (mono-B-2), formula (mono-B-4), formula (mono-B-5), formula (mono-B-7), formula (mono-B-8), formula (m formula (mono-B-10), formula (mono-B-11), formula (mono-B-13), formula (mono-B-14), formula (mono-B-16), formula (mono-B-17), formula (mono-B-19), formula (mono-B-20), formula (mono-B-22), formula (mono-B-23), formula (mono-B-25), formula (mono-B-26), formula (mono-B-28), Formula (mono-B-29), Formula (mono-B-31), Formula (mono-B-32), Formula (mono-B-34), Formula (mono-B-35), Formula (mono-Sn-1), Formula (mon o-Sn-2), Formula (mono-Sn-4), Formula (mono-Sn-5), Formula (mono-Sn-7), Formula (mono-Sn-8), Formula (mono-Sn-10), Formula (mono-Sn -11), formula (mono-Sn-13), formula (mono-Sn-14), formula (mono-Sn-16), formula (mono-Sn-17), formula (mono-Sn-19), formula (mono-Sn-20), formula (mono-Sn-22), formula (mono-Sn-23), formula (mono-Sn-25), formula (mono-Sn-26), formula (mono-Sn-28), formula (mono- More preferred are (mono-Sn-29), (mono-Sn-31), (mono-Sn-32), (mono-Sn-34) or (mono-Sn-35), and especially preferred are (mono-hal-28), (mono-hal-29), (mono-B-28), (mono-B-29), (mono-Sn-28) or (mono-Sn-29).

[Method for producing compounds]
Next, a method for producing the compound of this embodiment (hereinafter referred to as the "production method of this embodiment") will be described. The production method of this embodiment is as shown in the following production methods (A) to (E).

<Manufacturing method (A)>
The production method (A) is a method for producing the compound of the present embodiment represented by the general formula (mono-hal) by reacting a compound represented by the general formula (2-hal) with an acid.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ are as defined above. M ^1-hal represents a halogen atom. M ^2-hal represents a halogen atom.)

As the halogen atom represented by M ^1-hal and M ^2-hal , a chlorine atom, a bromine atom or an iodine atom is preferable, a bromine atom or an iodine atom is more preferable, and a bromine atom is even more preferable, in terms of good production efficiency of the compound of this embodiment.

It is essential that the manufacturing method (A) is carried out in the presence of an acid, and examples of such acids include Brønsted acids and Lewis acids. Examples of Brønsted acids include inorganic acids such as hydroiodic acid, hydrogen chloride, hydrogen bromide, hydroxylamine-O-sulfonic acid, phosphonic acid, chlorosulfonic acid, and nitric acid; acetic acid, glycolic acid, palmitic acid, sorbic acid, phthalic acid, chlorodifluoroacetic acid, palmitic acid, formic acid, difluoroacetic acid, aminomethanesulfonic acid, 2-hydroxybenzoic acid, maleic acid, croconic acid, tribromoacetic acid, thioacetic acid, anthranilic acid, bis(trifluoromethanesulfonyl)imide, benzenesulfonic acid, trifluoromethanesulfonic acid, thioctic acid, pyridinium p-toluenesulfonate, 5-sulfosalicylic acid, fumaric acid, propionic acid, thiogly Examples of organic acids include cholic acid, sulfanilic acid, bromoacetic acid, tartaric acid, benzenesulfonic acid, gallic acid, ethylenediaminetetraacetic acid, hydroxypropionic acid, dichloroacetic acid, benzoic acid, succinic acid, malic acid, 2-hydroxypropionic acid, trichloroacetic acid, malonic acid, chloroacetic acid, methanesulfonic acid, 1,2-benzenedisulfonic acid imide, p-toluenesulfonic acid, camphorsulfonic acid, triglycolaminic acid, trifluoroacetic acid, citric acid, and ascorbic acid. Examples of Lewis acids include aluminum isopropoxide, aluminum chloride (III), and bis(2,6-di-tert-butyl-4-methylphenoxy)methyl. aluminum-based Lewis acids such as ethylaluminum, aluminum bromide, triethylaluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum, ethylaluminum dichloride, and diethylaluminum chloride; tin-based Lewis acids such as tin(IV) tetrachloride; titanium-based Lewis acids such as titanium(IV) chloride and tetraisopropyl orthotitanate; boron-based Lewis acids such as boron trifluoride, boron trichloride, and dicyclohexyl(trifluoromethanesulfonyloxy)borane; cerium(III) trifluoromethanesulfonate, lanthanum(III) trifluoromethanesulfonate, trifluoromethanesulfonate, Examples of Lewis acids include triflate-based Lewis acids such as barium trifluoromethanesulfonate (II), silver trifluoromethanesulfonate, zinc trifluoromethanesulfonate (II), neodymium trifluoromethanesulfonate (III), ytterbium trifluoromethanesulfonate (III), scandium trifluoromethanesulfonate (III), hafnium trifluoromethanesulfonate (IV), copper trifluoromethanesulfonate (II), thulium trifluoromethanesulfonate (III), and yttrium trifluoromethanesulfonate (III); indium-based Lewis acids such as indium chloride (III); and the like, which may be mixed in any ratio. Lewis acids are preferred in terms of good reaction yield, with tin-based Lewis acids or aluminum-based Lewis acids being more preferred, and tin tetrachloride (IV) or aluminum chloride being even more preferred.

There are no particular limitations on the amount of acid used, but in terms of good yield, a range of 0.5 to 2.0 molar equivalents per molar equivalent of compound (2-hal) is preferred, and a range of 1.0 to 1.2 molar equivalents is even more preferred.

The manufacturing method (A) can be carried out in a solvent. There are no particular limitations on the solvent that can be used as long as it does not inhibit the reaction, and examples of the solvent include aliphatic hydrocarbon solvents such as hexane, heptane, decane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; dimethyl sulfoxide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and the like. ) and other amide solvents; urea solvents such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU); sulfoxide solvents such as dimethylsulfoxide (DMSO); alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol; halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene; fluorine solvents such as bis(2,2,2-trifluoroethyl)=N,N-diisopropylphosphoramidate (PF-37) and phosphoric acid=tris(2,2,2-trifluoroethyl) (TFEP); nitromethane; water, and the like; and these may be mixed and used in any ratio.

In terms of good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, and fluorine solvents are preferred, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, and ether solvents are more preferred, tetralin, toluene, chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, orthodichlorobenzene, and THF are even more preferred, and dichloromethane is especially preferred.

There are no particular limitations on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL/mg, more preferably in the range of 0.005 to 10 mL/mg, and even more preferably in the range of 0.01 to 0.1 mL/mg, relative to the weight of compound (2-hal).

Production method (A) can be carried out at a temperature appropriately selected from -80°C to 100°C, and is preferably carried out at a temperature appropriately selected from -50°C to 50°C in terms of good yield, and more preferably at a temperature appropriately selected from -20°C to 0°C.

Production method (A) can also be carried out using a microwave reaction device.

It is preferable to carry out the manufacturing method (A) under an inert gas atmosphere such as argon gas or nitrogen gas, or under vacuum, in terms of good yield.

In the manufacturing method (A), the reaction time with the acid varies depending on the compound (2-hal) used, the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, and more preferably 0.5 to 10 hours.

The compound (mono-hal) of this embodiment can be obtained by carrying out a normal treatment after completion of the production method (A). If necessary, it may be purified using a general means used by those skilled in the art for purifying organic compounds, such as washing, precipitation, filtration, dialysis, recrystallization, column chromatography, preparative HPLC, or Soxhlet extraction.

The compound represented by the general formula (2-hal) used in the production method (A) may be obtained by any method, but may be produced by referring to, for example, methods described in the literature (Angewante Chemie international edition, Vol. 56, pp. 2898-2902, 2017, etc.). Commercially available products may also be used.

<Manufacturing method (B)>
The production method (B) of this embodiment is a method for producing a compound of this embodiment represented by the general formula (mono-nuc) by reacting a compound represented by the general formula (mono-hal) with a boron compound or a tin compound.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , M ^1-hal and M ^2-hal are the same as defined above. ^{M 1-mono-nuc} represents a group selected from the group consisting of boron-containing groups or tin-containing groups. ^{M 2-mono-nuc} represents a group selected from the group consisting of boron-containing groups or tin-containing groups.)

As the boron-containing group represented by M ^1-mono-nuc and M ^2-mono-nuc , in terms of the efficient production of the compound of this embodiment, boronic acid, boronic acid ester, borate salt, etc. are preferred, groups represented by formulas (12-1) to (12-6) are more preferred, groups represented by formulas (12-1), (12-3), (12-5) or (12-6) are even more preferred, groups represented by formulas (12-1) or (12-3) are even more preferred, and groups represented by formula (12-3) are particularly preferred.

Examples of the tin-containing group represented by M ^1-mono-nuc and M ^2-mono-nuc include a trialkylstannyl group, a dialkylarylstannyl group, an alkyldiarylstannyl group, a triarylstannyl group, etc. In terms of good production efficiency of the compound of this embodiment, a trialkylstannyl group or a triarylstannyl group is preferred, groups represented by formulae (13-1) to (13-5) are more preferred, and a group represented by formula (13-1) is even more preferred.

M ^1-mono-nuc and M ^2-mono-nuc are preferably a boron-containing group or a tin-containing group in terms of high production efficiency of the compound of this embodiment, more preferably formula (12-1), formula (12-3), formula (13-1) or formula (13-4), and even more preferably formula (13-1).

The boron compounds that can be used in manufacturing method (B) are not particularly limited, but examples include compounds (Brea-1) to (Brea-9).

In terms of good reaction yield, it is preferable to use (Brea-1), (Brea-2), (Brea-3), (Brea-4), (Brea-5) or (Brea-6), with (Brea-5) being more preferable.

There is no particular limit to the amount of boron compound used, but in terms of good reaction yield, it is preferable that the amount is in the range of 1 to 10 molar equivalents per molar equivalent of the compound (mono-hal), and more preferably in the range of 2 to 8 molar equivalents.

The tin compounds that can be used are not particularly limited, but examples include (Snrea-1) to (Snrea-3). It is preferable to use (Snrea-1) because it has a good reaction yield.

There is no particular limit to the amount of tin compound used, but in terms of good reaction yield, it is preferably in the range of 1 to 10 molar equivalents per molar equivalent of compound (mono-hal), more preferably in the range of 2 to 8 molar equivalents, and even more preferably in the range of 2 to 5 molar equivalents.

The manufacturing method (B) can be carried out in the presence of a base. Examples of bases that can be used include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium hexamethyldisilazide, lithium tetramethylpiperidide, lithium diisopropylamide, and 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex. In terms of good reaction yield, alkyllithium is preferred, with methyllithium, n-butyllithium, sec-butyllithium, or tert-butyllithium being more preferred, and n-butyllithium being even more preferred.

There is no limit to the amount of base used, but in terms of good yield, 1 to 10 molar equivalents per molar equivalent of compound (mono-hal) is preferred, 2 to 5 molar equivalents is more preferred, and 2 to 3 molar equivalents is even more preferred.

The manufacturing method (B) can be carried out in a solvent. Examples of solvents that can be used include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, Examples of solvents include ester solvents such as γ-lactone, amide solvents such as DMF, DMAc, and NMP; urea solvents such as TMU and DMPU, sulfoxide solvents such as DMSO; alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol; halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene; nitromethane; and water. These may be mixed in any ratio. In terms of good reaction yield, aliphatic hydrocarbon solvents, ether solvents, aromatic hydrocarbon solvents, mixed solvents of aliphatic hydrocarbon solvents and ether solvents, or mixed solvents of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred, ether solvents are more preferred, and THF is even more preferred.

There are no particular limitations on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL/mg, more preferably in the range of 0.001 to 10 mL/mg, even more preferably in the range of 0.005 to 1.0 mL/mg, and most preferably in the range of 0.01 to 1.0 mL/mg, relative to the weight of the compound (mono-hal) used.

It is preferable to carry out production method (B) under an inert gas atmosphere such as argon gas or nitrogen gas in terms of good yield.

There is no limit to the reaction temperature at which production method (B) is carried out, but in terms of good yield, it is preferable to carry out the reaction at a temperature in the range of -78°C to 100°C, and more preferably -78°C to 30°C.

The reaction time varies depending on the type of compound (mono-hal), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 78 hours, even more preferably 1 to 48 hours, and most preferably 1 to 24 hours.

The compound (mono-nuc) of this embodiment can be obtained by carrying out the usual treatment after the completion of the production method (B). If necessary, it may be purified by recrystallization, precipitation, filtration, dialysis, column chromatography, preparative HPLC, Soxhlet extraction, etc.

<Manufacturing method (C)>
The production method (C) is a method for producing the compound of the present embodiment represented by the general formula (mono-nuc) by allowing a boron compound or a tin compound to act on the compound of the present embodiment represented by the general formula (mono-hal) in the presence of a transition metal catalyst.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , M ^1-hal , M ^2-hal , M ^1-mono-nuc and M ^2-mono-nuc are as defined above.)

The boron compound is not particularly limited, but examples include (BBrea-1) to (BBrea-9), etc.

Because of the good reaction yield, it is preferable to use (BBrea-2), (BBrea-7) or (BBrea-8), with (BBrea-2) being more preferable.

There is no particular limit to the amount of boron compound used, but in terms of good reaction yield, it is preferable that the amount is in the range of 1 to 10 molar equivalents per molar equivalent of the compound (mono-hal), and more preferably in the range of 2 to 8 molar equivalents.

The tin compounds that can be used are not particularly limited, but examples include the formulas (SnSnrea-1) to (SnSnrea-2). It is preferable to use (SnSnrea-2) because of its good yield.

There is no particular limit to the amount of tin compound used, but in terms of good yield, it is preferable that the amount is in the range of 1 to 10 molar equivalents per molar equivalent of the compound (mono-hal), and more preferably in the range of 2 to 8 molar equivalents.

Examples of transition metal catalysts that can be used include palladium catalysts, nickel catalysts, platinum catalysts, and the like. These transition metal catalysts can be "metals," "supported metals," "metal salts such as metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides," or "complex compounds such as olefin complexes, phosphine complexes, amide complexes, amine complexes, carbene complexes, or acetylacetonate complexes." Furthermore, these metals, supported metals, metal salts, and complex compounds can be used in combination with tertiary phosphorus compounds or carbene compounds. In terms of good yield, it is preferable to use palladium catalysts or nickel catalysts as the transition metal catalyst, and palladium catalysts are more preferable.

Examples of palladium catalysts include, but are not limited to, palladium metal such as palladium black and palladium sponge. Other examples of palladium catalysts include supported palladium metal such as palladium/alumina, palladium/carbon, palladium/silica, and palladium/Y-type zeolite. In addition, metal salts such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, and palladium nitrate, π-allylpalladium chloride dimer, palladium acetylacetonate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, dichlorodiamminepalladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)propane]palladium, Examples of palladium catalysts include palladium, dichloro[1,1'-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-IPent), [1,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-IPr), and [1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-SIPr).

In terms of good yield, it is preferable to use, as the palladium catalyst, palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ), bis(tri-tert-butylphosphine)palladium, or dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium.

The nickel catalyst is not particularly limited, but specific examples include nickel chloride (II), bis(triphenylphosphine)nickel (II) dichloride, bis(2,4-pentanedionato)nickel (II) hydrate, bis(1,5-cyclooctadiene)nickel (0), dichloro(1,1'-bis(diphenylphosphino)ethane)nickel, dichloro(1,1'-bis(diphenylphosphino)propane)nickel, and [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]triphenylphosphinenickel (II) dichloride.

There are no particular limitations on the amount of transition metal catalyst used, but in terms of good yield, it is preferably in the range of 0.00005 to 0.5 molar equivalents per molar equivalent of compound (mono-hal), and more preferably in the range of 0.0005 to 0.2 molar equivalents.

The production method (C) can also be carried out in the presence of a transition metal catalyst and a base. Examples of bases that can be used include organic salts such as sodium butoxide, potassium butoxide, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium hexamethyldisilazide, lithium diisopropylamide, 2,2,6,6-tetramethylpiperidinyl lithium complex, and 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex; inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate; and organic bases such as triethylamine, diisopropylethylamine, pyridine, lutidine, DBU, TBD, MTBD, and DABCO; and the like, which may be mixed in any ratio. Inorganic bases are preferred in terms of good reaction yield, and sodium carbonate or potassium carbonate is more preferred.

The manufacturing method (C) can be carried out in a solvent. Examples of solvents that can be used include the solvents exemplified in the explanation of the manufacturing method (B). In terms of good reaction yield, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, an ether solvent, or an amide solvent is preferred, a sulfoxide solvent, an ether solvent, or an amide solvent is more preferred, a sulfoxide solvent is even more preferred, and DMSO is particularly preferred.

There are no particular limitations on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL/mg, and more preferably in the range of 0.01 to 10 mL/mg, relative to the weight of the compound (mono-hal) used.

It is preferable to carry out production method (C) under an inert gas atmosphere such as argon gas or nitrogen gas in terms of good yield.

There is no limit to the reaction temperature at which production method (C) is carried out, but it is preferably carried out in the range of -78°C to 200°C, and more preferably in the range of 60°C to 180°C.

Production method (C) can also be carried out using a microwave reaction apparatus. The reaction time varies depending on the type of compound (mono-hal), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 78 hours.

The compound (mono-nuc) of this embodiment can be obtained by carrying out the usual treatment after the completion of the production method (C). If necessary, it may be purified by recrystallization, precipitation, filtration, dialysis, column chromatography, preparative HPLC, Soxhlet extraction, etc.

<Manufacturing method (D)>
The production method (D) is a method for producing the compound of the present embodiment represented by the general formula (mono-nuc) by reacting a compound represented by the general formula (Pub-H) with a boron compound or a tin compound in the presence of a transition metal catalyst.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , M ^1-mono-nuc and M ^2-mono-nuc have the same meanings as defined above.)

Although there is no particular limitation on the boron compound, examples include (BBrea-1) to (BBrea-9), etc.

Because of the good reaction yield, it is preferable to use (BBrea-2), (BBrea-7) or (BBrea-8), with (BBrea-2) being more preferable.

There is no particular limit to the amount of boron compound used, but in terms of good reaction yield, it is preferable that the amount is in the range of 1 to 10 molar equivalents per molar equivalent of the compound (mono-hal), and more preferably in the range of 2 to 8 molar equivalents.

The tin compounds that can be used are not particularly limited, but examples include the formulas (SnSnrea-1) to (SnSnrea-2). It is preferable to use (SnSnrea-2) because of its good yield.

There is no particular limit to the amount of tin compound used, but in terms of good yield, it is preferable that the amount is in the range of 1 to 10 molar equivalents per molar equivalent of the compound (mono-hal), and more preferably in the range of 2 to 8 molar equivalents.

The transition metal catalyst is not particularly limited, but specific examples include iridium complexes such as (1,5-cyclooctadiene)(methoxy)iridium(I)(dimer); salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate; complex compounds such as π-allylpalladium chloride dimer, palladium acetylacetonate, and tris(dibenzylideneacetone)dipalladium; and palladium complexes having a tertiary phosphorus compound as a ligand such as dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, and bis(tricyclohexylphosphine)palladium chloride. Palladium complexes can also be prepared in the reaction system by adding a tertiary phosphorus compound to a palladium salt or complex compound. Examples of the tertiary phosphorus compound that can be used in this case include triphenylphosphine, trimethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, bis(diphenylphosphine), Examples include 1,2-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, tri(2-furyl)phosphine, tri(o-tolyl)phosphine, tris(2,5-xylyl)phosphine, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and the like.

Iridium complexes are preferred because of their good yield, and (1,5-cyclooctadiene)(methoxy)iridium(I) (dimer) is more preferred.

There is no limit to the amount of transition metal catalyst used, but in terms of good yield, it is preferably in the range of 0.00005 to 0.5 molar equivalents per molar equivalent of compound (Pub-H), and more preferably in the range of 0.0005 to 0.1 molar equivalents.

These transition metal catalysts may be used alone or in combination with a bipyridine compound, a tertiary phosphorus compound, or a carbene compound. Examples of bipyridine compounds that can be used include 6,6'-dimethyl-bipyridyl, 6,6'-dimethyl-bipyridyl, 4,4'-dimethyl-bipyridyl, 4,4'-dinonyl-bipyridyl, and 4,4'-di(tert-butyl)-bipyridyl. Examples of the tertiary phosphorus compound that can be used include triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tri-o-tolylphosphine, trioctylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)butane, 1,6-bis(diphenylphosphino)butane, 1,7-bis(diphenylphosphino)butane, 1,8-bis(diphenylphosphino)butane, 1,9-bis(diphenylphosphino)butane, 1,10-bis(diphenylphosphino)butane, 1,11-bis(diphenylphosphino)butane, 1,12-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,13-bis(diphenylphosphino)butane, 1,14-bis(diphenylphosphino)butane, 1,15-bis(diphenylphosphino)butane, 1,16-bis(diphenylphosphino)butane, 1,17-bis(diphenylphosphino)butane, 1,18-bis(diphenylphosphino)butane, 1,19-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)butane, 1,2-bis(diphenylpho Examples of such phosphino derivatives include 1'-bis(diphenylphosphino)ferrocene, tert-butyldiphenylphosphine, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, bis(diphenylphosphino)methane, 1,4-bis(diphenylphosphino)butane, tri(2-furyl)phosphine, tris(2,5-xylyl)phosphine, (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl. Examples of carbene compounds that can be used include 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene, 1,3-di-tert-butylimidazol-2-ylidene, and 1,3-dimesitylimidazol-2-ylidene. Bipyridine compounds are preferred in terms of good reaction yield, with 6,6'-dimethyl-bipyridyl, 6,6'-dimethyl-bipyridyl, 4,4'-dimethyl-bipyridyl, 4,4'-dinonyl-bipyridyl, and 4,4'-di(tert-butyl)-bipyridyl being more preferred, and 4,4'-dimethyl-bipyridyl, 4,4'-dinonyl-bipyridyl, and 4,4'-di(tert-butyl)-bipyridyl being even more preferred.

The manufacturing method (D) can be carried out in a solvent. Examples of solvents that can be used include the solvents exemplified in the explanation of the manufacturing method (B). In terms of good reaction yields, aliphatic hydrocarbon solvents, ether solvents, aromatic hydrocarbon solvents, mixed solvents of aliphatic hydrocarbon solvents and ether solvents, or mixed solvents of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred, ether solvents are more preferred, and THF is even more preferred.

There is no particular limit to the amount of solvent used, but it is preferably in the range of 0.1 to 100 mL/mg, and more preferably in the range of 0.1 to 10 mL/mg, based on the weight of the compound (Pub-H) used.

It is preferable to carry out production method (D) under an inert gas atmosphere such as argon gas or nitrogen gas in terms of good yield.

There is no limit to the reaction temperature at which production method (D) is carried out, but it is preferably carried out in the range of -78°C to 200°C, and more preferably in the range of 60°C to 180°C.

Production method (D) can also be carried out using a microwave reaction apparatus. The reaction time varies depending on the type of compound (Pub-H), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 78 hours.

The compound (mono-nuc) of this embodiment can be obtained by carrying out the usual treatment after the completion of the production method (D). If necessary, it may be purified by precipitation, filtration, dialysis, column chromatography, preparative HPLC, Soxhlet extraction, etc.

The compound represented by the general formula (Pub-H) used in the manufacturing method (D) may be obtained by any method, but may be manufactured by referring to, for example, the method described in the literature (The Journal of American Chemical Society, Vol. 143, pp. 4281-4289, 2021, etc.). Commercially available products may also be used.

<Manufacturing method (E)>
The production method (E) is a method for producing the compound of the present embodiment represented by the general formula (mono-nuc) by reacting the compound represented by the general formula (Pub-H) with a boron compound or a tin compound in the presence of a base.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , M ^1-mono-nuc and M ^2-mono-nuc have the same meanings as defined above.)

The boron compounds that can be used in the manufacturing method (E) are not particularly limited, but examples include compounds (Brea-1) to (Brea-9).

In terms of good reaction yield, it is preferable to use (Brea-1), (Brea-2), (Brea-3), (Brea-4), (Brea-5) or (Brea-6), with (Brea-5) being more preferable.

There is no particular limit to the amount of boron compound used, but in terms of good reaction yield, it is preferably in the range of 1 to 10 molar equivalents per molar equivalent of compound (Pub-H), and more preferably in the range of 2 to 8 molar equivalents.

The tin compounds that can be used are not particularly limited, but examples include (Snrea-1) to (Snrea-3). It is preferable to use (Snrea-1) because it has a good reaction yield.

There is no particular limit to the amount of tin compound used, but in terms of good reaction yield, it is preferably in the range of 1 to 10 molar equivalents relative to 1 molar equivalent of compound (Pub-H), more preferably in the range of 2 to 8 molar equivalents, and even more preferably in the range of 2 to 5 molar equivalents.

The manufacturing method (E) can be carried out in the presence of a base. Examples of bases that can be used include the bases exemplified in the explanation of the manufacturing method (B). In terms of good reaction yield, alkyl lithium is preferred, methyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium are more preferred, and n-butyl lithium is even more preferred.

There is no limit to the amount of base used, but in terms of good yield, 1 to 10 molar equivalents per molar equivalent of compound (Pub-H) is preferred, more preferably 2 to 5 molar equivalents, and even more preferably 2 to 3 molar equivalents.

The manufacturing method (E) can be carried out in a solvent. Examples of solvents that can be used include the solvents exemplified in the explanation of the manufacturing method (B). In terms of good reaction yield, aliphatic hydrocarbon solvents, ether solvents, aromatic hydrocarbon solvents, mixed solvents of aliphatic hydrocarbon solvents and ether solvents, or mixed solvents of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred, ether solvents are more preferred, and THF is even more preferred.

There are no particular limitations on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL/mg, more preferably in the range of 0.001 to 10 mL/mg, even more preferably in the range of 0.005 to 1.0 mL/mg, and most preferably in the range of 0.01 to 1.0 mL/mg, relative to the weight of the compound (Pub-H) used.

It is preferable to carry out production method (E) under an inert gas atmosphere such as argon gas or nitrogen gas in terms of good yield.

There is no limit to the reaction temperature at which production method (E) is carried out, but it is preferably carried out in the range of -78°C to 100°C, and more preferably -78°C to 30°C.

The reaction time varies depending on the type of compound (Pub-H), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 78 hours, even more preferably 1 to 48 hours, and most preferably 1 to 24 hours.

The compound (mono-nuc) of this embodiment can be obtained by carrying out normal treatment after completion of production method (E). If necessary, it may be purified by recrystallization, precipitation, filtration, dialysis, column chromatography, preparative HPLC, Soxhlet extraction, etc.

The compound represented by the general formula (Pub-H) used in the manufacturing method (E) may be obtained by any method, but may be produced by referring to, for example, the method described in the literature (The Journal of American Chemical Society, Vol. 143, pp. 4281-4289, 2021, etc.). Commercially available products may also be used.

<Manufacturing method (F)>
The production method (F) is a method for producing the compound of the present embodiment represented by the general formula (mono-hal) by reacting the compound represented by the general formula (Pub-H) with a halogenating agent.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , M ^1-mono-hal and M ^2-mono-hal are as defined above.)

Halogenating agents that can be used in production method (F) are not particularly limited, but examples include succinimide-based halogenating agents such as N-bromosuccinimide, and halogenating agents such as bromine and iodine. In terms of good reaction yield, it is preferable to use succinimides such as N-bromosuccinimide, bromine, or iodine.

There is no particular limit to the amount of boron compound used, but in terms of good reaction yield, it is preferably in the range of 1 to 10 molar equivalents per molar equivalent of compound (Pub-H), and more preferably in the range of 2 to 8 molar equivalents.

When the halogenating agent used is iodine, production method (F) can be carried out in the presence of a base. Examples of bases that can be used include the bases exemplified in the explanation of production method (B). In terms of good reaction yield, alkyl lithium is preferred, methyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium are more preferred, and n-butyl lithium is even more preferred.

There is no limit to the amount of base used, but in terms of good yield, 1 to 10 molar equivalents per molar equivalent of compound (Pub-H) is preferred, more preferably 2 to 5 molar equivalents, and even more preferably 2 to 3 molar equivalents.

The manufacturing method (F) can be carried out in a solvent. Examples of solvents that can be used include the solvents exemplified in the explanation of the manufacturing method (B). In terms of good reaction yield, aliphatic hydrocarbon solvents, ether solvents, aromatic hydrocarbon solvents, mixed solvents of aliphatic hydrocarbon solvents and ether solvents, or mixed solvents of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred, ether solvents are more preferred, and THF is even more preferred.

There are no particular limitations on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL/mg, more preferably in the range of 0.001 to 10 mL/mg, even more preferably in the range of 0.005 to 1.0 mL/mg, and most preferably in the range of 0.01 to 1.0 mL/mg, relative to the weight of the compound (Pub-H) used.

It is preferable to carry out production method (F) under an inert gas atmosphere such as argon gas or nitrogen gas in terms of good yield.

There is no limit to the reaction temperature at which production method (F) is carried out, but it is preferably carried out in the range of -78°C to 100°C, and more preferably -78°C to 30°C.

The reaction time varies depending on the type of compound (Pub-H), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 78 hours, even more preferably 1 to 48 hours, and most preferably 1 to 24 hours.

The compound (mono-hal) of this embodiment can be obtained by carrying out normal treatment after completion of production method (F). If necessary, it may be purified by recrystallization, precipitation, filtration, dialysis, column chromatography, preparative HPLC, Soxhlet extraction, etc.

[Conjugated Polymers]
By copolymerizing the compound of this embodiment with a compound represented by the following general formula (mono-X ¹ ), a conjugated polymer composed of a structural unit represented by the following general formula (poly) and a structural unit represented by the following general formula (poly-X1) can be obtained.

（式中、Ｘ^１は炭素数１～５０のアルキル基又は炭素数１～５０のアルコキシ基で置換されていてもよい２価の複素芳香族環連結基を表す。Ｍ^{３－ｈａｌ}及びＭ^{４－ｈａｌ}は各々独立にハロゲン原子を表す。）

(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms. ^M3-hal and M4 ^-hal each independently represent a halogen atom.)

（式中、Ｒ^１は前記と同様の意味を表す。）

(In the formula, ^R1 has the same meaning as above.)

（式中、Ｘ^１は前記と同様の意味を表す。）

(In the formula, ^X1 has the same meaning as above.)

Specific examples of conjugated polymers composed of structural units represented by the general formula (poly) and structural units represented by the general formula (poly-X1) include conjugated polymers represented by structural units represented by formulas (3-1) to (3-680).

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

The compounds obtained in the examples were subjected to structural analysis by ¹ H-NMR measurement. The molecular weight and molecular weight distribution of the conjugated polymers obtained in the examples were estimated by gel permeation chromatography (GPC) measurement. Commercially available reagents were used.

<NMR measurement conditions>
Measurement equipment: Bruker ASCEND ^™ ADVANCE III HD (400 MHz)
Measurement solvent: deuterated chloroform (CDCl ₃ ), deuterated dimethyl sulfoxide (DMSO-d ₆ ), deuterated benzene (C ₆ D ₆ )
Internal standard: tetramethylsilane (TMS)

<GPC measurement conditions>
Measurement equipment: Tosoh Corporation High-speed GPC equipment HLC-8320GPC EcoSEC
Column: TSKgel SuperMultiporeHZ-H, TSKgel SuperHZ2000
Measurement solvent: THF
Measurement temperature: 25℃
Calibration curve: polystyrene standards

<High-temperature GPC measurement conditions>
Measurement equipment: Tosoh Corporation high temperature GPC equipment HLC-8321GPC/HT
Column: TSKgel GMH _HR -H(20)HT
Measurement solvent: 1,2,4-trichlorobenzene (TCB)
Measurement temperature: 140℃
Calibration curve: polystyrene standards

<TGA measurement conditions>
Measuring device: SII Corporation EXSTAR6000 TGA/DTA6200
Sample container: aluminum pan Measurement atmosphere: nitrogen Flow rate: 50 mL/min
Heating rate: 10° C./min
T _d3 , T _d5 and T _d10 represent the 3%, 5% and 10% weight loss temperatures, respectively.

<DSC measurement conditions>
Measuring device: SII Corporation EXSTAR6000 DSC6220
Sample container: Aluminum pan Measurement conditions: Nitrogen atmosphere, 10°C/min, 0 to 300°C, results obtained from the third HeatingScan.

[Reference example 1]

A hexane solution of n-butyllithium (2.3 mL, 3.56 mmol) was added to a mixture of thieno[3,2-b]thiophene (500 mg, 3.56 mmol) and tetrahydrofuran (35 mL) at 0° C., and the mixture was stirred for 1 hour. Then, triisopropylsilyl chloride (0.83 mL, 756 mg, 3.92 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction solution, and the mixture was extracted with hexane. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain a colorless solid 2-triisopropylsilylthieno[3,2-b]thiophene (924 mg, 88%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.39 (d, J=5.2Hz, 1H), 7.37 (d, J=0.4Hz, 1H), 7.25 (dd, J= 5.2Hz, 0.4Hz, 2H), 1.37 (sep, J=7.6Hz, 3H), 1.13 (d, J=7.6Hz, 18H).

[Reference example 2]

N-bromosuccinimide (660 mg, 3.71 mmol) was added to a mixture of 2-triisopropylsilylthieno[3,2-b]thiophene (1.00 g, 3.37 mmol) obtained in Reference Example 1 and THF (34 mL), and the mixture was stirred at room temperature for 22.5 hours. Water was added to the resulting mixture, which was then extracted with hexane. The collected organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (900 mg, 71%) as a colorless solid.
¹ H-NMR (DMSO-d6, 400MHz) δ7.66 (s, 1H), 7.56 (s, 1H), 1.40-1.30 (m, 3H), 1.08 (d, J = 7.6Hz, 18H).

[Reference example 3]

Ethynylmagnesium bromide (100 mL, 50.0 mmol) was added dropwise to a mixture of 11-heneicosanone (12.9 g, 41.7 mmol) and tetrahydrofuran (83 mL) at 0°C and stirred at room temperature for 22.5 hours. A saturated aqueous solution of ammonium chloride was added to the resulting mixture and extracted with diethyl ether. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered. The solvent was distilled off under reduced pressure to obtain 11-ethynyl-heneicosan-11-ol (14.0 g) as a pale yellow liquid.

A mixture of 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (3.75 g, 10.0 mmol) obtained in Reference Example 2, 11-ethynyl-heneicosan-11-ol (3.70 g), and triethylamine (200 mL) was bubbled with argon for 30 minutes. To this mixture, copper (I) iodide (190 mg, 1.00 mmol) and Pd(PPh ₃ ) ₄ (578 mg, 0.500 mmol) were added under an argon stream, and the mixture was stirred at 100° C. for 107 hours. The resulting mixture was cooled to room temperature, and then a saturated aqueous ammonium chloride solution was added and extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=4/1→3/1→2/1) to give a pale yellow liquid of 11-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethynyl)-heneicosan-11-ol (5.05 g, 80%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.31 (d, J=0.8Hz, 1H), 7.28 (d, J=0.4Hz, 1H), 1.77-1.70 (m, 4H), 1.5 6-1.51 (m, 4H), 1.43-1.27 (m, 31H), 1.12 (d, J=7.2Hz, 18H), 0.90-0.86 (m, 6H).

[Reference example 4]

To a mixture of 11-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethynyl)-heneicosan-11-ol (2.71 g, 4.29 mmol) obtained in Reference Example 3 and dichloromethane (86 mL), iodine (1.63 g, 6.44 mmol) was added at −15° C., and the mixture was stirred at −15° C. for 5 hours. A saturated aqueous solution of sodium thiosulfate was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain a reddish brown liquid of 2-triisopropylsilyl-5,6-diiodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (2.87 g, 77%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.40 (s, 1H), 1.94-1.86 (m, 2H), 1.68-1.61 (m, 2H), 1.43-1.11 (m, 47H), 0.90-0.84 (m, 10H), 0.61-0.55 (m, 2H).

[Reference example 5]

To a mixture of 2-triisopropylsilyl-5,6-diiodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (551 mg, 0.636 mmol) obtained in Reference Example 4 and tetrahydrofuran (6.4 mL), a hexane solution of n-butyllithium (0.40 mL, 0.636 mmol) was added at −78° C., and the mixture was stirred for 1.5 hours. Then, 11-heneicosanone (237 mg, 0.763 mmol) was added, and the mixture was stirred at room temperature for 2 hours. A saturated aqueous ammonium chloride solution was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/chloroform=10/1→5/1→2/1→1/1) to obtain a colorless solid, 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-iodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (431 mg, 64%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.36 (s, 1H), 2.39-2.32 (m, 2H), 1.84-1.77 (m, 2H), 1.70-1. 58 (m, 4H), 1.47-1.10 (m, 81H), 0.87-0.84 (m, 14H), 0.57-0.48 (m, 2H).

[Reference example 6]

A mixture of 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-iodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (2.04 g, 1.94 mmol) obtained in Reference Example 5, thieno[3,2-b]thiophene-2-boronic acid (714 mg, 3.88 mmol), 1,2-dimethoxyethane (49 mL), and 2M aqueous potassium carbonate solution (19 mL, 38 mmol) was bubbled with argon for 30 minutes. To this mixture, (AMPHOS) ₂ PdCl ₂ (69 mg, 97 μmol) was added under an argon stream, and the mixture was stirred at 100° C. for 37.5 hours. The resulting mixture was cooled to room temperature, and then a saturated aqueous ammonium chloride solution was added, followed by extraction with ethyl acetate. The collected organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform = 10/1 → 5/1 → 2/1) to obtain a yellow solid, 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (1.06 g, 52%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.41 (s, 1H), 7.38 (d, J=5.2Hz, 1H), 7.27-7.26 (m, 1H), 7.00 (s, 1H), 1.93-1.83 (m, 4H), 1.76-1.69 (m, 2H), 1.64-1.57 (m, 2H), 1.47-1.14 (m, 83H), 0.88-0.84 (m, 12H), 0.72-0.69 (m, 2H).

[Reference example 7]

A 1M solution of tetrabutylammonium fluoride in tetrahydrofuran (1.5 mL, 1.5 mmol) was added to a mixture of 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (1.30 g, 1.22 mmol) obtained in Reference Example 6 and tetrahydrofuran (24 mL), and the mixture was stirred at room temperature for 22 hours. Water was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=5/1→2/1) to obtain a yellow solid of 5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (0.995 g, 90%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.39 (d, J=5.2Hz, 1H), 7.31 (s, 2H), 7.27-7.26 (m, 1H), 6.70 (s, 1H), 1.89-1.60 (m, 8H), 1.51-1.13 (m, 60H), 0.88-0.84 (m, 14H), 0.74-0.63 (m, 2H).

[Reference example 8]

To a mixture of 5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (300 mg, 0.330 mmol) obtained in Reference Example 7 and tetrahydrofuran (6.6 mL), N-bromosuccinimide (129 mg, 0.727 mmol) was added at 0° C. and stirred at room temperature for 23 hours. A saturated aqueous solution of sodium thiosulfate was added to the resulting mixture, which was then extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=5/1→2/1) to give a yellow solid, 2-bromo-5-(1-decyl-1-hydroxyundecyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (268 mg, 76%).
¹ H-NMR (C ₆ D ₆ , 400MHz) δ7.00 (s, 1H), 6.74 (s, 1H), 6.67 (s, 1H), 2.00-1.80 (m, 6H), 1.69-1.47 (m, 8H), 1.33-1.21 (m, 54H), 0.92-0.89 (m, 16H).

[Example 1]

A mixture of 2-bromo-5-(1-decyl-1-hydroxyundecyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (114 mg, 0.107 mmol) obtained in Reference Example 8 and dichloromethane (4.3 mL) was freeze-degassed. To this mixture, a dichloromethane solution of tin tetrachloride (1 M, 100 μL, 100 μmol) was added under an argon stream, and the mixture was stirred at −15° C. for 5 hours. A saturated aqueous solution of sodium bicarbonate was added to the resulting mixture, and the mixture was extracted with hexane. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain (mono-hal-28) as a red solid (78 mg, 70%).
¹ H-NMR (C ₆ D ₆ , 400 MHz) δ6.69 (s, 2H), 2.11-2.03 (m, 8H), 1.28-1.08 (m, 62H), 0.91-0.87 (m, 14H).

[Example 2]

A hexane solution of n-butyllithium (0.27 mL, 0.420 mmol) was added to a mixture of (mono-hal-28) (200 mg, 0.191 mmol) obtained in Example 1 and tetrahydrofuran (3.8 mL) at 0° C., and the mixture was stirred for 3 hours. Then, trimethyltin chloride (91.3 mg, 0.458 mmol) was added, and the mixture was stirred at room temperature for 22 hours. Water was added to the reaction solution, and the mixture was extracted with hexane. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by reprecipitation (acetone), and a red solid (mono-Sn-28) was obtained (131 mg, 56%).
¹ H-NMR (C ₆ D ₆ , 400MHz) δ6.87 (s, 2H), 2.17-2.07 (m, 8H), 1.28-1.23 (m, 4H), 1.07-0.95 (m, 60H), 0.69 (t, J=7.0Hz, 12H), 0.07 (s, 18H).

[Reference example 9]

Ethynylmagnesium bromide (30.0 mL, 15.0 mmol) was added dropwise to a mixture of 7-tridecanone (2.00 g, 10.0 mmol) and tetrahydrofuran (20 mL) at 0°C and stirred at room temperature for 19 hours. A saturated aqueous solution of ammonium chloride was added to the resulting mixture and extracted with diethyl ether. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered. The solvent was distilled off under reduced pressure to obtain 11-ethynyl-heneicosan-11-ol (1.51 g) as a pale yellow liquid.

A mixture of 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (2.30 g, 6.12 mmol) obtained in Reference Example 2, 7-ethynyl-tridecan-7-ol (1.51 g, 6.73 mmol), and triethylamine (123 mL) was bubbled with argon for 30 minutes. To this mixture, copper (I) iodide (116 mg, 612 μmol) and Pd(PPh ₃ ) ₄ (354 mg, 306 μmol) were added under an argon stream, and the mixture was stirred at 100° C. for 65 hours. The resulting mixture was cooled to room temperature, and then a saturated aqueous ammonium chloride solution was added and extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane → hexane/chloroform = 1/1) to give a yellow liquid of 7-(5-triisopropylsilyl-thieno[2,3-d]thiophen-2-ylethynyl)-tridecan-7-ol (2.80 g, 88%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.31 (s, 1H), 7.28 (s, 1H), 2.03 (s, 1H), 1.76-1.71 (m, 4H), 1.58- 1.51 (m, 4H), 1.40-1.26 (m, 15H), 1.12 (d, J=7.4Hz, 18H), 0.91-0.88 (m, 6H).

[Reference example 10]

To a mixture of 7-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethynyl)-tridecan-7-ol (2.65 g, 5.11 mmol) obtained in Reference Example 9 and dichloromethane (103 mL), iodine (1.94 g, 7.66 mmol) was added at −15° C., and the mixture was stirred at −15° C. for 5 hours. A saturated aqueous sodium thiosulfate solution was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain 2-triisopropylsilyl-5,6-diiodo-7,7-dihexyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (3.21 g, 83%) as a reddish brown liquid.
¹ H-NMR (CDCl ₃ , 400MHz) δ7.40 (s, 1H), 1.95-1.85 (m, 2H), 1.68-1.61 (m, 2H), 1.43-1.11 (m, 31H), 0.90-0.75 (m, 10H), 0.61-0.52 (m, 2H).

[Reference example 11]

To a mixture of 2-triisopropylsilyl-5,6-diiodo-7,7-dihexyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (3.06 g, 4.06 mmol) obtained in Reference Example 10 and tetrahydrofuran (41 mL), a hexane solution of n-butyllithium (2.60 mL, 4.06 mmol) was added at −78° C., and the mixture was stirred for 1.5 hours. Then, 7-tridecanone (966 mg, 4.87 mmol) was added, and the mixture was stirred at room temperature for 2 hours. A saturated aqueous ammonium chloride solution was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=9/1) to give 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyhexyl)-6-iodo-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (2.04 mg, 61%) as a brown liquid.
¹ H-NMR (CDCl ₃ , 400MHz) δ7.37 (s, 1H), 2.40-2.33 (m, 2H), 2.04 (s, 1H), 1.85-1.77 (m, 2H), 1 70-1.58 (m, 4H), 1.46-1.09 (m, 49H), 0.90-0.75 (m, 14H), 0.52-0.48 (m, 2H).

[Reference example 12]

A mixture of 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyheptyl)-6-iodo-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.57 g, 1.90 mmol) obtained in Reference Example 11, thieno[3,2-b]thiophene-2-boronic acid (699 mg, 3.80 mmol), 1,2-dimethoxyethane (47 mL), and 2M aqueous potassium carbonate solution (19 mL, 38 mmol) was bubbled with argon for 30 minutes. To this mixture, (AMPHOS) ₂ PdCl ₂ (67.3 mg, 95.0 μmol) was added under an argon stream, and the mixture was stirred at 100° C. for 72 hours. The resulting mixture was cooled to room temperature, and then a saturated aqueous ammonium chloride solution was added, followed by extraction with ethyl acetate. The collected organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform = 4/1 → 1/1) to obtain a yellow solid, 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.34 g, 84%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.41 (s, 1H), 7.38 (d, J=5.2Hz, 1H), 7.27-7.26 (m, 1H), 7.00 (s, 1H), 2.15 (s, 1H), 1.94-1.84 ( m, 4H), 1.76-1.69 (m, 2H), 1.65-1.58 (m, 2H), 1.48-1.14 (m, 50H), 0.85-0.77 (m, 12H), 0.75-0.68 (m, 3H).

[Reference example 13]

1M tetrabutylammonium fluoride tetrahydrofuran solution (2.2mL, 2.2mmol) was added to a mixture of 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophene-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.42g, 1.70mmol) obtained in Reference Example 12 and tetrahydrofuran (34mL), and the mixture was stirred at room temperature for 17 hours. Water was added to the resulting mixture, which was then extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=7/3) to give a yellow-brown liquid of 5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (0.995 g, 90%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.39 (d, J=5.2Hz, 1H), 7.31 (s, 2H), 7.27 (d, J=5.2Hz, 1H), 7.00 (s, 1H), 2.14 (s, 1H), 1.92-1.71 (m, 6H), 1.65-1.55 (m, 2H), 1.49-1.44 (m, 2H), 1.33-1.13 (m, 28H), 0.85-0.78 (m, 12H), 0.69-0.66 (m, 2H).

[Reference example 14]

To a mixture of 5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.02 g, 1.51 mmol) obtained in Reference Example 13 and tetrahydrofuran (31 mL), N-bromosuccinimide (591 mg, 3.32 mmol) was added at 0° C. and stirred at room temperature for 15 hours. A saturated aqueous solution of sodium thiosulfate was added to the resulting mixture, which was then extracted with ethyl acetate. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/chloroform=85/15→1/1) to obtain a yellow solid, 2-bromo-5-(1-hexyl-1-hydroxyheptyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene.
¹ H-NMR (C ₆ D ₆ , 400MHz) δ 7.04 (s, 1H), 6.81 (s, 1H), 6.71 (s, 1H), 2.04-1.83 (m, 6H), 1.72-1.54 (m, 8H), 1.40-1.18 (m, 26H), 0.99-0.88 (m, 12H).

[Example 3]

A mixture of 2-bromo-5-(1-hexyl-1-hydroxyheptyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (100 mg, 119 μmol) obtained in Reference Example 14 and dichloromethane (4.8 mL) was freeze-degassed. To this mixture, 1M tin tetrachloride dichloromethane solution (130 μL, 130 μmol) was added under an argon stream and stirred at −15° C. for 1 hour. A saturated aqueous solution of sodium bicarbonate was added to the resulting mixture and extracted with hexane. The collected organic layer was washed with water and saturated saline, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give (mono-hal-16) as a red solid (85 mg, 87%).
¹ H-NMR (C ₆ D ₆ , 400 MHz) δ6.67 (s, 2H), 2.09-1.98 (m, 8H), 1.28-1.03 (m, 32H), 0.79-0.75 (m, 12H).

[Polymerization Reference Example 1]

A mixture of (mono-hal-28) (100 mg, 95.5 μmol) obtained in Example 1, 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (37.0 mg, 68.3 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.1 mL), and 1M aqueous sodium carbonate solution (0.64 mL, 0.64 mmol) was bubbled with argon for 30 minutes. To this mixture, Pd ₂ (dba) _{3.CHCl 3} (2.0 mg, 1.9 μmol) and tri(o-tolyl)phosphine (2.3 mg, 7.6 μmol) were added and stirred at 120° C. for 60 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/15 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in n-decane. The obtained mixture was concentrated under reduced pressure, and precipitated in methanol to filter the precipitated solid. The obtained solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid (3-10) (65.3 mg, 67%).
GPC (THF): Mn=10500g/mol, Mw=17800g/mol, PDI=1.69.
GPC (TCB, 120°C): Mn=3800g/mol, Mw=13000g/mol, PDI=3.3.
T _d3 = 396°C, T _d5 = 403°C, T _d10 = 417°C.
No phase transition was observed by DSC.

[Polymerization reference example 2]

A mixture of (mono-Sn-28) (100 mg, 82.3 μmol) obtained in Example 2, 4,7-dibromo-2,1,3-benzothiadiazole (24.2 mg, 82.3 μmol), and tetralin (2.5 mL) was bubbled with argon for 30 minutes. Pd ₂ (dba) ₃ ·CHCl ₃ (1.7 mg, 1.6 μmol) and tri(o-tolyl)phosphine (2.0 mg, 6.6 μmol) were added to this mixture, and the mixture was stirred at 180°C for 2 hours using a microwave reactor. Thereafter, 2-(tributylstannyl)thiophene (0.23 mL, 276 mg, 0.74 mmol) was added to the reaction solution, and the mixture was stirred at 180°C for 10 minutes using a microwave reactor. Further, 2-bromothiophene (0.08 mL, 134 mg, 0.82 mmol) was added and stirred at 180° C. for 10 minutes using a microwave reactor. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/15 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in chloroform. The obtained mixture was concentrated under reduced pressure, and precipitated in methanol to filter the precipitated solid. The obtained solid was washed with methanol and then dried under reduced pressure at 90° C. to obtain a black solid (3-10) (60 mg, 71%).
GPC (THF): Mn=21000g/mol, Mw=34000g/mol, PDI=1.62.
T _d3 = 364°C, T _d5 = 381°C, T _d10 = 397°C.
No phase transition was observed by DSC.

[Polymerization Reference Example 3]

A mixture of (mono-hal-28) (100 mg, 95.5 μmol) obtained in Example 1, 2,5-bis(2-octyldodecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (106 mg, 95.5 μmol), tetrahydrofuran (1.9 mL), and 2M aqueous potassium carbonate solution (1.0 mL, 2.0 mmol) was bubbled with argon for 30 minutes. To this mixture, bis(tri-t-butylphosphine)palladium(0) (2.4 mg, 4.8 μmol) was added and stirred at 80° C. for 62 hours. Thereafter, 2-thiopheneboronic acid (110 mg, 860 μmol) was added to the reaction solution and stirred at 80° C. for 4 hours. Furthermore, 2-bromothiophene (92 μL, 950 μmol) was added and stirred at 80° C. for 4 hours. The resulting mixture was cooled to room temperature, and then precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/15 mL) and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and precipitated in methanol and the precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90° C. to obtain a black solid (3-650) (105 mg, 63%).
GPC (THF): Mn=24400g/mol, Mw=41500g/mol, PDI=1.70.

[Polymerization Reference Example 4]

A mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in Example 3, 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (47.0 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M aqueous sodium carbonate solution (0.81 mL, 0.81 mmol) was bubbled with argon for 30 minutes. Pd ₂ (dba) 3.CHCl ₃ (2.5 mg, 2.4 μmol) and _tri (o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added to this mixture, and the mixture was stirred at 120° C. for 64 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/15 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the residue on the filter was dissolved in chloroform. The obtained mixture was concentrated under reduced pressure, and precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90° C. to obtain a black solid (3-166) (47 mg, 49%).
GPC (THF): Mn=5200g/mol, Mw=11800g/mol, PDI=2.27.

[Polymerization Reference Example 5]

A mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in Example 3, 2,5-bis(2-octyldodecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (135 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M aqueous sodium carbonate solution (0.81 mL, 0.81 mmol) was bubbled with argon for 30 minutes. To this mixture, Pd ₂ (dba) 3.CHCl _{3 (} 2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added and stirred at 120° C. for 66 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/15 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90° C. to obtain a black solid (3-646) (12 mg, 7%).
GPC (THF): Mn=14800g/mol, Mw=30000g/mol, PDI=2.03.

[Polymerization Reference Example 6]

A mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in Example 3, 2,5-bis(2-decyltetradecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (148 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M aqueous sodium carbonate solution (0.81 mL, 0.81 mmol) was bubbled with argon for 30 minutes. To this mixture, Pd ₂ (dba) 3.CHCl _{3 (} 2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added and stirred at 120° C. for 65 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol/concentrated hydrochloric acid (150 mL/15 mL), and the precipitated solid was filtered. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90° C. to obtain a black solid (3-666) (78 mg, 40%).
GPC (THF): Mn=5500g/mol, Mw=8400g/mol, PDI=1.53.

[Semiconductor characteristic example 1]
A composition for forming an organic thin film was prepared by heating a 0.5 wt % o-DCB solution of the conjugated polymer (3-10) synthesized in Polymerization Reference Example 1 in a nitrogen atmosphere in a glove box. After cooling to room temperature, the solution was filtered through a 0.22 μm filter, confirming that the compound remained in solution and was suitable for film formation.

Next, a film of Parylene C was formed on a glass substrate as an underlayer by CVD, and then a shadow mask with a channel length of 100 μm and a channel width of 500 μm was placed on the Parylene C layer, and gold was evaporated under vacuum to form source and drain electrodes. The solution prepared above was spin-coated in a nitrogen atmosphere in a glove box. This was heated to 150°C and held for 15 minutes to create an organic thin film of conjugated polymer (3-10). A film of Parylene C was formed as a gate insulating film by CVD, and then a silver electrode was formed by evaporation, to create a top-gate-bottom-contact type organic thin film transistor element (the gate electrode was silver, the gate insulating layer was Parylene C, and the source and drain electrodes were gold).

The organic thin-film transistor element was connected to a semiconductor parameter analyzer (Keithley, Model 4200A-SCS) in air, and the gate voltage (Vg) was scanned in 1 V increments from +10 to -100 V at a drain voltage (Vd = -100 V) to evaluate the transfer characteristics. The organic thin-film transistor element exhibited p-type characteristics, and the carrier mobility of holes was 0.046 cm ² /Vs. Furthermore, after annealing at 150°C for 15 minutes, the carrier mobility of holes was 0.043 cm ² /Vs. This confirmed that the carrier mobility did not decrease even after heat treatment.

[Semiconductor characteristic example 2]
The same operation as in Semiconductor Characteristics Example 1 was repeated, except that the source electrode and the drain electrode were surface-treated with pentafluorobenzenethiol. The obtained organic thin-film transistor element exhibited p-type characteristics, and the carrier mobility of the positive holes was 0.078 cm ² /Vs. Furthermore, after annealing treatment at 150° C. for 15 minutes, the carrier mobility of the positive holes was 0.074 cm ² /Vs. This confirmed that the carrier mobility did not decrease even after the heat treatment.

[Semiconductor Characteristic Example 3]
The same operations as in Semiconductor Characteristics Example 1 were repeated, except that the conjugated polymer (3-10) synthesized in Polymerization Reference Example 2 was used. The obtained organic thin-film transistor element exhibited p-type characteristics, and the carrier mobility of the holes was 0.077 cm ² /Vs. Furthermore, after annealing at 150° C. for 15 minutes, the carrier mobility of the holes was 0.075 cm ² /Vs. This confirmed that the carrier mobility did not decrease even after heat treatment.

The conjugated polymer provided by this embodiment provides high carrier mobility and has excellent solubility in solvents and heat resistance, and is therefore expected to be used as a semiconductor device material, such as an organic thin-film transistor element and an organic thin-film solar cell.

1 Organic semiconductor layer 2 Substrate 3 Gate electrode 4 Gate insulating layer 5 Source electrode 6 Drain electrode

Claims (26)

A compound represented by the following general formula (mono):

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 50 carbon atoms. R ¹ and R ² may be combined together to form a ring together with the carbon atom to which they are bonded. R ³ and R ⁴ each independently represent an alkyl group having 1 to 50 carbon atoms. ^{R 3} and R ⁴ may be combined together to form a ring together with the carbon atom to which they are bonded. ^{R 5} and R ⁶ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. J ¹ , J ² , J ³ , and J ⁴ each independently represent a chalcogen atom. ^{M 1} and M ² each independently represent a group selected from the group consisting of a halogen atom, a metal-containing group, a boron-containing group, and a tin-containing group ,
The boron-containing group is selected from groups represented by the following formulas (12-1) to (12-6):
The tin-containing group is selected from a trialkylstannyl group, a dialkylarylstannyl group, an alkyldiarylstannyl group, or a triarylstannyl group .

R ¹ and R ² each independently represent an alkyl group having 1 to 34 carbon atoms;
R ¹ and R ² may be joined together to form a ring with the carbon atom to which they are attached;
R ³ and R ⁴ each independently represent an alkyl group having 1 to 34 carbon atoms;
R ³ and R ⁴ may be joined together to form a ring with the carbon atom to which they are attached;
R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 34 carbon atoms;
J ¹ , J ² , J ³ and J ⁴ each independently represent an oxygen atom, a sulfur atom or a selenium atom;
2. The compound according to claim 1, wherein ^M1 and ^M2 are each independently a group selected from the group consisting of a bromine atom, an iodine atom, said boron-containing group, and said tin-containing group. ^R5 and ^R6 are hydrogen atoms;
J ¹ , J ² , J ³ and J ⁴ are sulfur atoms;
3. The compound according to claim 1, wherein ^M1 and ^M2 are each independently a group selected from the group consisting of a hydrogen atom, a bromine atom, the boron - containing group, and the tin-containing group. A compound represented by the following general formula (2-hal),

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may combine with the carbon atom to which they are bonded to form a ring. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may combine with the carbon atom to which they are bonded to form a ring. ^R5 and ^R6 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-mono-hal and M2 ^-mono-hal each independently represent a halogen atom.)
A method for producing a compound represented by the following general formula (mono-hal), which comprises reacting with an acid:

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , M ^1-mono-hal , and M ^2-mono-hal are each as defined above.) The method of claim 4, wherein the acid is a Lewis acid. The method according to claim 4 or 5, wherein the acid is tin tetrachloride. A compound represented by the following general formula (mono-hal):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may combine with the carbon atom to which they are bonded to form a ring. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may combine with the carbon atom to which they are bonded to form a ring. ^R5 and ^R6 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-mono-hal and M2 ^-mono-hal each independently represent a halogen atom.)
The method comprises reacting a boron compound or a tin compound in the presence of one or both of a base and a transition metal catalyst,
The boron compound is selected from the compounds represented by the following (Brea-1) to (Brea-9):
The tin compound is selected from the compounds represented by the following (Snrea-1) to (Snrea-3):
A method for producing a compound represented by the following general formula (mono-nuc):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , and J ⁴ are as defined above. M ^1-mono-nuc and M ^2-mono-nuc each independently represent a boron-containing group or a tin-containing group.
The boron-containing group is selected from groups represented by the following formulas (12-1) to (12-6):
The tin-containing group is selected from a trialkylstannyl group, a dialkylarylstannyl group, an alkyldiarylstannyl group, or a triarylstannyl group .

The method according to claim 7, further comprising reacting the compound represented by the general formula (mono-hal) with the base and then reacting the compound with the boron compound. The method according to claim 7, further comprising reacting the compound represented by the general formula (mono-hal) with the tin compound after reacting the compound with the base. The method according to any one of claims 7 to 9, wherein the base is an organometallic reagent. The method according to any one of claims 7 to 10, wherein the base is an alkyl lithium. The method according to claim 7, wherein the compound represented by the general formula (mono-hal) is reacted with the boron compound in the presence of the transition metal catalyst. The method according to claim 7, in which the compound represented by the general formula (mono-hal) is reacted with the tin compound in the presence of the transition metal catalyst. The method according to any one of claims 7, 12 and 13, wherein the transition metal catalyst is a palladium catalyst. A compound represented by the following general formula (Pub-H):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may combine with the carbon atom to which they are bonded to form a ring. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may combine with the carbon atom to which they are bonded to form a ring. ^R5 and ^R6 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom.)
The method includes reacting a boron compound or a tin compound in the presence of a base or a transition metal catalyst,
The boron compound is selected from the compounds represented by the following (BBrea-1) to (BBrea-9):
The tin compound is selected from the compounds represented by the following (SnSnrea-1) to (SnSnrea-2):
A method for producing a compound represented by the following general formula (mono-nuc):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , and J ⁴ are as defined above. M ^1-mono-nuc and M ^2-mono-nuc each independently represent a boron-containing group or a tin-containing group.
The boron-containing group is selected from the boron-containing groups represented by the following formulas (12-1) to (12-6):
The tin-containing group is selected from a trialkylstannyl group, a dialkylarylstannyl group, an alkyldiarylstannyl group, or a triarylstannyl group .

The method according to claim 15, further comprising reacting the compound represented by the general formula (Pub-H) with the base and then reacting the compound with the boron compound. The method according to claim 15, wherein the base is reacted with the compound represented by the general formula (Pub-H) and then the tin compound is reacted with the compound. The method according to any one of claims 15 to 17, wherein the base is an organometallic reagent. The method according to any one of claims 15 to 18, wherein the base is an alkyl lithium. The method according to any one of claims 15 to 18, wherein the base is lithium amide. The method according to claim 15, wherein the compound represented by the general formula (Pub-H) is reacted with the boron compound in the presence of the transition metal catalyst. The method according to claim 15, wherein the compound represented by the general formula (Pub-H) is reacted with the tin compound in the presence of the transition metal catalyst. The method according to any one of claims 15, 21 and 22, wherein the transition metal catalyst is an iridium catalyst. A compound represented by the following general formula (Pub-H):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may combine with the carbon atom to which they are bonded to form a ring. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may combine with the carbon atom to which they are bonded to form a ring. ^R5 and ^R6 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom.)
A method for producing a compound represented by the following general formula (mono-hal), comprising reacting with a halogenating agent:

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , and J ⁴ are as defined above. M ^1-mono-hal and M ^2-mono-hal each independently represent a halogen atom.) The method according to claim 24, wherein the halogenating agent is bromine or iodine. The method of claim 24, wherein the halogenating agent is a succinimide compound.

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