JP2009114074A - (Thiophene / phenylene) co-oligomer - Google Patents

Abstract

（式中、Ｒ^１〜Ｒ^５およびＲ^６〜Ｒ^１０は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜１２のアルキル基、炭素数１〜６のアルコキシ基または炭素数１〜６のパーフルオロアルキル基を示す。ｎは、３〜１２の整数を示す。Ｒ^１１〜Ｒ^１２は、それぞれ独立して、水素原子または炭素数１〜１２のアルキル基を示し、ｎ個のＲ^１１は、同一であっても異なっていてもよく、ｎ個のＲ^１２は、同一であっても異なっていてもよい。但し、チオフェン環に結合するｎ個のＲ^１１およびｎ個のＲ^１２のうち少なくとも１個は、炭素数１〜１２のアルキル基である。）で表され、かつ、左右非対称構造を有する（チオフェン／フェニレン）コオリゴマー。
【選択図】なしA (thiophene / phenylene) co-oligomer having a relatively low melting point and excellent solubility in various solvents.
Equation (1):
[Chemical 1]

^(Wherein, R 1 to R ⁵ and ^R 6 ^{to R 10} each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, 1 alkoxy group or a carbon number of 1 to 6 carbon atoms 6 represents a perfluoroalkyl group of 6. n represents an integer of 3 to ^12. R ^{11 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n R ¹¹ may be the same or different, and n R ¹² may be the same or different, provided that n R ¹¹ and n R ¹² bonded to the thiophene ring. (At least one is an alkyl group having 1 to 12 carbon atoms.) And a (thiophene / phenylene) co-oligomer having a left-right asymmetric structure.
[Selection figure] None

Description

The present invention relates to a novel compound (thiophene / phenylene) co-oligomer, an organic semiconductor material and a light emitting material containing the (thiophene / phenylene) co-oligomer, and a method for producing the (thiophene / phenylene) co-oligomer.

In recent years, organic electronic materials such as conductive oligomers and conductive polymers have been proposed as charge transport materials for organic EL elements, organic thin film transistor materials, and light emitting materials for laser oscillation.

These organic electronic materials not only have abundant functions, but also have characteristics such as excellent flexibility and impact resistance, adaptability to large areas, and relatively low manufacturing costs. For example, applications to organic semiconductor lasers, organic LEDs, organic EL displays, organic thin-film solar cells, flexible sheet displays, electronic paper, IC cards, information tags, biosensors, actuators, etc. are being considered. ing.

As such an organic electronic material, various (thiophene / phenylene) co-oligomers have been proposed, and various properties possessed by these have been reported (see Patent Documents 1 and 2 and Non-Patent Document 1). For example, Patent Documents 1 and 2 disclose that specific (thiophene / phenylene) co-oligomers are useful as light emitting materials and laser materials. Non-Patent Document 1 discloses characteristics of a specific (thiophene / phenylene) co-oligomer as a semiconductor material.
JP 2000-26451 A JP 2004-292497 A M. Yoon, A. Facchetti, CEStern, and TJMarks, J. Am. Chem. Soc., 2006, 128, 5792

The use of organic electronic materials will continue to diversify in the future, and the emergence of a wide variety of materials in response to these demands has led to the proposed (thiophene / phenylene) co-oligomer generally having a melting point. However, there is a concern that the range of use is limited due to the relatively high properties and poor solubility in various solvents. For example, for 5,5 ″ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ″ ″-kinquethiophene, the melting point Is as high as 357 ° C., the solubility in organic solvents is less than 0.01 wt% in tetrahydrofuran at 25 ° C., and hardly dissolves in other solvents. These characteristics are, for example, a major obstacle when manufacturing a large screen display panel, and hinder the applicability when adopting various coating methods and printing methods such as inkjet.

The present invention has been made in view of these problems. A (thiophene / phenylene) co-oligomer having a relatively low melting point and excellent solubility in various solvents, and the (thiophene / phenylene) co-oligomer. It is an object of the present invention to provide an organic semiconductor material and a light emitting material, and a method for producing the (thiophene / phenylene) co-oligomer.

（式中、Ｒ^１〜Ｒ^５およびＲ^６〜Ｒ^１０は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜１２のアルキル基、炭素数１〜６のアルコキシ基または炭素数１〜６のパーフルオロアルキル基を示す。ｎは、３〜１２の整数を示す。Ｒ^１１〜Ｒ^１２は、それぞれ独立して、水素原子または炭素数１〜１２のアルキル基を示し、ｎ個のＲ^１１は、同一であっても異なっていてもよく、ｎ個のＲ^１２は、同一であっても異なっていてもよい。但し、チオフェン環に結合するｎ個のＲ^１１およびｎ個のＲ^１２のうち少なくとも１個は、炭素数１〜１２のアルキル基である。）で表され、かつ、左右非対称構造を有する（チオフェン／フェニレン）コオリゴマー。
項２．項１に記載の（チオフェン／フェニレン）コオリゴマーを含む有機半導体材料。
項３．項１に記載の（チオフェン／フェニレン）コオリゴマーを含む発光材料。
項４．式（２）：

（式中、Ｒ^１〜Ｒ^５は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜１２のアルキル基、炭素数１〜６のアルコキシ基または炭素数１〜６のパーフルオロアルキル基を示す。ｍは、０〜１２の整数を示す。Ｒ^１３〜Ｒ^１４は、それぞれ独立して、水素原子または炭素数１〜１２のアルキル基を示し、ｍ個のＲ^１３は、同一であっても異なっていてもよく、ｍ個のＲ^１４は、同一であっても異なっていてもよい。Ｙ^１は、塩素原子、臭素原子またはヨウ素原子とクロスカップリング可能な置換基を示す。）で表される化合物と、式（３）：

（式中、Ｒ^６〜Ｒ^１０は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜１２のアルキル基、炭素数１〜６のアルコキシ基または炭素数１〜６のパーフルオロアルキル基を示す。ｍは、前記式（２）におけるｍと同じ整数を示す。ｎは、３〜１２の整数であって、（ｎ−ｍ）が０以上となる整数を示す。Ｒ^１５〜Ｒ^１６は、それぞれ独立して、水素原子または炭素数１〜１２のアルキル基を示し、（ｎ−ｍ）個のＲ^１５は、同一であっても異なっていてもよく、（ｎ−ｍ）個のＲ^１６は、同一であっても異なっていてもよい。Ｘ^１は、塩素原子、臭素原子またはヨウ素原子を示す。）で表される化合物とを、金属触媒の存在下で反応させることを特徴とする、式（４）：

（式中、Ｒ^１〜Ｒ^５およびＲ^１３〜Ｒ^１４は、それぞれ、前記式（２）におけるＲ^１〜Ｒ^５およびＲ^１３〜Ｒ^１４と同じ基を示し、ｍは、前記式（２）におけるｍと同じ整数を示す。Ｒ^６〜Ｒ^１０およびＲ^１５〜Ｒ^１６は、それぞれ、前記式（３）におけるＲ^６〜Ｒ^１０およびＲ^１５〜Ｒ^１６と同じ基を示し、ｎは、前記式（３）におけるｎと同じ整数を示す。但し、ｍ個のＲ^１３、ｍ個のＲ^１４、（ｎ−ｍ）個のＲ^１５および（ｎ−ｍ）個のＲ^１６のうちの少なくとも１個は炭素数１〜１２のアルキル基である。）で表され、かつ、左右非対称構造を有する（チオフェン／フェニレン）コオリゴマーの製造方法。
項５．

（式中、Ｒ^１〜Ｒ^５は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜１２のアルキル基、炭素数１〜６のアルコキシ基または炭素数１〜６のパーフルオロアルキル基を示す。ｔは、０〜５の整数を示す。Ｒ^１７〜Ｒ^１８は、それぞれ独立して、水素原子または炭素数１〜１２のアルキル基を示し、ｔ個のＲ^１７は、同一であっても異なっていてもよく、ｔ個のＲ^１８は、同一であっても異なっていてもよい。Ｙ^２は、塩素原子、臭素原子またはヨウ素原子とクロスカップリング可能な置換基を示す。）で表される化合物と、式（６）：

（式中、ｔは、前記式（５）におけるｔと同じ整数を示す。ｎは、３〜１２の整数であって、（ｎ−２ｔ）が１以上となる整数を示す。Ｒ^１９〜Ｒ^２０は、それぞれ独立して、水素原子または炭素数１〜１２のアルキル基を示し、（ｎ−２ｔ）個のＲ^１９は、同一であっても異なっていてもよく、（ｎ−２ｔ）個のＲ^２０は、同一であっても異なっていてもよい。但し、（ｎ−２ｔ）個のチオフェン環鎖は左右非対称構造を有する。Ｘ^２およびＸ^３は、それぞれ独立して、塩素原子、臭素原子またはヨウ素原子を示す。）で表される化合物とを、金属触媒の存在下で反応させることを特徴とする、式（７）：

（式中、Ｒ^１〜Ｒ^５およびＲ^１７〜Ｒ^１８は、それぞれ、前記式（５）におけるＲ^１〜Ｒ^５およびＲ^１７〜Ｒ^１８と同じ基を示し、Ｒ^１９〜Ｒ^２０は、それぞれ、前記式（６）におけるＲ^１９〜Ｒ^２０と同じ基を示す。ｔは、前記式（５）におけるｔと同じ整数を示し、ｎは、前記式（６）におけるｎと同じ整数を示す。）で表され、かつ、左右非対称構造を有する（チオフェン／フェニレン）コオリゴマーの製造方法。
項６．金属触媒が、ジクロロ[１，３−ビス（ジフェニルホスフィノ）プロパン]ニッケル（ＩＩ）である項４または５に記載の（チオフェン／フェニレン）コオリゴマーの製造方法。 The present invention relates to a (thiophene / phenylene) co-oligomer, an organic semiconductor material and a light emitting material containing the (thiophene / phenylene) co-oligomer, and a method for producing the (thiophene / phenylene) co-oligomer as shown below.
Item 1. Formula (1):

^(Wherein, R 1 to R ⁵ and ^R 6 ^{to R 10} each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, 1 alkoxy group or a carbon number of 1 to 6 carbon atoms 6 represents a perfluoroalkyl group of 6. n represents an integer of 3 to ^12. R ^{11 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n R ¹¹ may be the same or different, and n R ¹² may be the same or different, provided that n R ¹¹ and n R ¹² bonded to the thiophene ring. (At least one is an alkyl group having 1 to 12 carbon atoms.) And a (thiophene / phenylene) co-oligomer having a left-right asymmetric structure.
Item 2. Item 10. An organic semiconductor material containing the (thiophene / phenylene) co-oligomer according to Item 1.
Item 3. Item 6. A light emitting material comprising the (thiophene / phenylene) co-oligomer according to Item 1.
Item 4. Formula (2):

Wherein R ^{1 to} R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms. M represents an integer of 0 to 12. R ^{13 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the m R ^13s are the same. And m R ^{14 s} may be the same or different, and Y ¹ represents a substituent capable of cross-coupling with a chlorine atom, a bromine atom or an iodine atom. A compound represented by formula (3):

(In the formula, R ^{6 to} R ¹⁰ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms. M represents the same integer as m in the formula (2), n represents an integer of 3 to 12, and (n−m) represents an integer of 0 or more, R ^{15 to} R ^16. Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and (n−m) R ^{15 s} may be the same or different, and (n−m) R ¹⁶ may be the same or different, and X ¹ represents a chlorine atom, a bromine atom or an iodine atom), and is reacted in the presence of a metal catalyst. Equation (4):

(Wherein R ^{1 to} R ⁵ and R ^{13 to} R ¹⁴ represent the same groups as R ^{1 to} R ⁵ and R ^{13 to} R ¹⁴ in the formula (2), respectively, and m represents the formula (2). R ^{6 to} R ¹⁰ and R ^{15 to} R ¹⁶ represent the same groups as R ^{6 to} R ¹⁰ and R ^{15 to} R ¹⁶ in the formula (3), respectively, and n represents the same Represents the same integer as n in formula (3), provided that at least one of m R ¹³ , m R ¹⁴ , (n−m) R ^15, and (n−m) R ¹⁶ Each is an alkyl group having 1 to 12 carbon atoms) and a method for producing a (thiophene / phenylene) co-oligomer having a left-right asymmetric structure.
Item 5.

Wherein R ^{1 to} R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms. T represents an integer of 0 to 5. R ^{17 to} R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and t R ^{17 s} are the same. And t R ¹⁸ may be the same or different, and Y ² represents a substituent capable of cross-coupling with a chlorine atom, a bromine atom or an iodine atom.) A compound represented by formula (6):

(In formula, t shows the same integer as t in the said Formula (5). N is an integer of 3-12, Comprising: (n-2t) shows an integer from 1 or more. R < ¹⁹ > -R. ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and (n-2t) R ^{19 s} may be the same or different, and (n-2t) R ²⁰ in the formula may be the same or different, provided that (n-2t) thiophene ring chains have a bilaterally asymmetric structure, X ² and X ³ each independently represent a chlorine atom, A compound represented by formula (7): wherein the compound represented by formula (7):

(Wherein R ^{1 to} R ⁵ and R ^{17 to} R ¹⁸ represent the same groups as R ^{1 to} R ⁵ and R ^{17 to} R ¹⁸ in the formula (5), respectively, and R ^{19 to} R ²⁰ represent And the same group as R ^{19 to} R ²⁰ in the formula (6), t represents the same integer as t in the formula (5), and n represents the same integer as n in the formula (6). And a (thiophene / phenylene) co-oligomer having a left-right asymmetric structure.
Item 6. Item 6. The method for producing a (thiophene / phenylene) co-oligomer according to Item 4 or 5, wherein the metal catalyst is dichloro [1,3-bis (diphenylphosphino) propane] nickel (II).

The (thiophene / phenylene) co-oligomer represented by the formula (4) is the same compound as the (thiophene / phenylene) co-oligomer represented by the formula (1), and is represented by the formula (7) (thiophene). / Phenylene) co-oligomer is a (thiophene / phenylene) co-oligomer in which R ^{6 to} R ¹⁰ are the same groups as R ^{1 to} R ⁵ in the (thiophene / phenylene) co-oligomer represented by the formula (1) It is the same compound.

In the present invention, the left-right asymmetric structure means that a straight line that bisects a row of thiophene rings extending in the left-right direction in the structural formula is a symmetry axis. Specifically, when the total number of thiophene rings is an even number, the symmetry axis is a straight line provided between two adjacent thiophene rings located in the center, and the total number of thiophene rings is an odd number. In this case, the straight line is provided at the center of one thiophene ring located at the center and is perpendicular to the row of thiophene rings.

Hereinafter, the present invention will be described in detail.

The (thiophene / phenylene) co-oligomer according to the present invention is a compound represented by the following formula (1) and has a left-right asymmetric structure.

式中、Ｒ^１〜Ｒ^５およびＲ^６〜Ｒ^１０は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜１２のアルキル基、炭素数１〜６のアルコキシ基または炭素数１〜６のパーフルオロアルキル基を示す。ｎは、３〜１２の整数を示す。Ｒ^１１〜Ｒ^１２は、それぞれ独立して、水素原子または炭素数１〜１２のアルキル基を示し、ｎ個のＲ^１１は、同一であっても異なっていてもよく、ｎ個のＲ^１２は、同一であっても異なっていてもよい。但し、チオフェン環に結合するｎ個のＲ^１１およびｎ個のＲ^１２のうち少なくとも１個は、炭素数１〜１２のアルキル基である。

In the formula, R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Of the perfluoroalkyl group. n shows the integer of 3-12. R ^{11 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the n R ^{11 s} may be the same or different, and the n R ^{12 s} are , May be the same or different. However, at least one of n R ¹¹ and n R ¹² bonded to the thiophene ring is an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- Hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, sec-hexyl, sec-octyl, sec-decyl, sec-dodecyl, t- Examples include a butyl group, a t-hexyl group, a t-octyl group, a t-decyl group, and a t-dodecyl group.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-hexyloxy group, iso -A propoxy group, a sec-butoxy group, a t-butoxy group, a t-hexyloxy group, etc. are mentioned.

Examples of the C 1-6 perfluoroalkyl group represented by R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ include a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, and an n-perfluoroalkyl group. Examples thereof include a fluorobutyl group, an n-perfluoropentyl group, and an n-perfluorohexyl group.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^{11 to} R ¹² include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group. Group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, sec-hexyl group, sec-octyl group, sec-decyl group, sec-dodecyl group, t-butyl group, t-hexyl Group, t-octyl group, t-decyl group, t-dodecyl group and the like.

Among the (thiophene / phenylene) co-oligomers represented by the formula (1), since the production is relatively easy, n pairs of R ¹¹ and R ¹² bonded to the same thiophene ring are in all combinations thereof. A (thiophene / phenylene) co-oligomer in which at least one is a hydrogen atom or the same alkyl group is preferably used.
Specific examples of the (thiophene / phenylene) co-oligomer according to the present invention are shown below.

Since the (thiophene / phenylene) co-oligomer according to the present invention has a left-right asymmetric structure, the melting point is the same or lower than that of a similar (thiophene / phenylene) co-oligomer having a left-right symmetric structure. It has the property that the solubility in various solvents is equal or excellent. Here, examples of the solvent in which the (thiophene / phenylene) co-oligomer according to the present invention has the same or excellent solubility include n-hexane, cyclohexane, heptane, toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, and ethyl acetate. Dimethylformamide, diethyl ether, tetrahydrofuran, dioxane, cyclopentyl methyl ether, dichloromethane, chloroform, acetone and acetonitrile.

The (thiophene / phenylene) co-oligomer according to the present invention has a relatively low melting point, excellent solubility in various solvents, high carrier injection / transport functions, and high brightness. Since it can emit light, it can be used as an organic semiconductor material and a light-emitting material having a wide range of application by using the compound alone or in combination with any other compound. By using the (thiophene / phenylene) co-oligomer according to the present invention, it becomes easy to perform vapor deposition, sputtering and thermal transfer on various substrates, facilitating application to coating methods and printing methods such as inkjet, Since kneading with various resins becomes easy, various devices can be easily manufactured.
The (thiophene / phenylene) co-oligomer according to the present invention is represented by the formula (1) and has a left-right asymmetric structure. The (thiophene / phenylene) co-oligomer represented by the formula (1) is Also, it can be expressed as the following formula (4). The (thiophene / phenylene) co-oligomer represented by the formula (4) reacts, for example, a compound represented by the following formula (2) and a compound represented by the following formula (3) in the presence of a metal catalyst. Can be manufactured.

Wherein ^(4), R 1 ^{to R 10,} respectively, showing the same group as ^R 1 ^{to R 10} in the formula (1). Moreover, n shows the same integer as n in Formula (1), m is an integer of 0-12, Comprising: (nm) shows an integer from 0 or more. R ¹⁴ and R ¹⁵ correspond to R ¹¹ in the formula (1), and R ¹³ and R ¹⁶ correspond to R ¹² in the formula (1). m R ¹³ , m R ¹⁴ , (nm) R ¹⁵ , and (nm) R ¹⁶ may be the same or different from each other. However, when m R ¹³ and m R ¹⁴ are all hydrogen atoms, at least one of (nm) R ¹⁵ and (nm) R ¹⁶ bonded to the thiophene ring. Each is an alkyl group having 1 to 12 carbon atoms. In addition, when (nm) R ¹⁵ and (nm) R ¹⁶ are all hydrogen atoms, at least one of m R ¹³ and m R ¹⁴ bonded to the thiophene ring. Each is an alkyl group having 1 to 12 carbon atoms.

In formula (2), R ^{1 to} R ⁵ and R ^{13 to} R ¹⁴ represent the same groups as R ^{1 to} R ⁵ and R ^{13 to} R ¹⁴ in formula (4), respectively. m represents the same integer as m in Formula (4). Y ¹ represents a substituent capable of cross-coupling with a chlorine atom, a bromine atom or an iodine atom.

Y ¹ represents a substituent capable of cross-coupling with a chlorine atom, bromine atom or iodine atom, and specific examples thereof include a boron derivative group, a halogenated metal group and a trialkyltin group. Examples of the boron derivative group include a boronic acid group, a dimethylborane group, a diethylborane group, a diphenylborane group, a pinacolylborane group, a catecholborane group, a 9-borabicyclo [3,3,1] nonyl group, and a trifluoroboron group. . Examples of the metal halide group include a magnesium chloride group, a magnesium bromide group, a magnesium iodide group, a zinc chloride group, a zinc bromide group, and a zinc iodide group. Examples of the trialkyltin group include a trimethyltin group, a triethyltin group, and a tributyltin group.

In formula (3), R ^{6 to} R ¹⁰ and R ^{15 to} R ¹⁶ represent the same groups as R ^{6 to} R ¹⁰ and R ^{15 to} R ¹⁶ in formula (4), respectively. n and m represent the same integer as n and m in formula (4). X ¹ represents a chlorine atom, a bromine atom or an iodine atom.

As the compounds represented by the formulas (2) and (3), commercially available products may be used, or those produced as necessary by a known method and a method based thereon may be used.

As a manufacturing method of the compound represented by Formula (2), for example, m in Formula (2) is 1, R ^{1 to} R ⁵ and R ^{13 to} R ¹⁴ are all hydrogen atoms, and Y ¹ is 2- (5-Phenylthienyl) magnesium iodide, which is a magnesium iodide group, reacts 2-phenylthiophene and N-iodosuccinimide to produce 2-iodo-5-phenylthiophene, and further reacts with magnesium It can manufacture by well-known methods, such as the method (refer patent document 1). In the formula (2), 2- (5-phenylthienyl) -4, wherein m is 1, R ^{1 to} R ⁵ and R ^{13 to} R ¹⁴ are all hydrogen atoms, and Y ¹ is a pinacolylborane group. 4,5,5-tetramethyl-1,3,2 dioxaborane is a method in which 2-bromo-5-phenylthiophene is reacted with n-butyllithium and trimethyl borate sequentially, and further reacted with pinacol (JJ Apperloo, LBGroenendaal, H. Verheyen, M. Jayakannan, RAJJassen, A. Dkhissi, D. Beljonne, R. Lazzaroni, and JLBredas, Chem. Eur. J. 2002, 8, 2384). Furthermore, pentafluorophenylmagnesium bromide in which m in the formula (2) is 0, R ^{1 to} R ⁵ are all fluorine atoms, and Y ¹ is a magnesium bromide group includes bromopentafluorobenzene and magnesium. It can be produced by a known method such as a reaction method (Org. Synth., Coll. Vol. 6, p. 875 (1988); Vol. 59, p. 122 (1979)). Moreover, as represented by the following formula (8), m in the formula (2) is 4, R ¹⁴ bonded to a thiophene ring bonded to Y ¹ among four thiophene rings, and a benzene ring R ¹³ bonded to the thiophene ring bonded to each other is an n-hexyl group, the other three R ¹³ and three R ¹⁴ bonded to the thiophene ring and R ^{1 to} R ⁵ are all hydrogen atoms, 5-tributylstannyl-5 ′ ″-phenyl-3,3 ′ ″-dihexyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″ − where Y ¹ is a tributyltin group Quaterthiophene is a reaction of 5-bromo-3,3 ′ ″-dihexyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene with phenylboronic acid. 5-phenyl-3,3 ′ ″-dihexyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene, and n -Method of sequentially reacting butyllithium and tributyltin chloride (N.Negishi, Y.Ie, M.Taniguchi, T.Kawai, H.Tada, T.Kandeda, and Y.Aso, Org. Lett., 2007, 9, 829) and the like.

As a manufacturing method of the compound represented by Formula (3), for example, (nm) in Formula (3) is 1, and R ^{6 to} R ¹⁰ and R ^{15 to} R ¹⁶ are all hydrogen atoms. 2-bromo-5-phenylthiophene in which X ¹ is a bromine atom can be produced by a known method such as a method of reacting 2-phenylthiophene with N-bromosuccinimide (see Patent Document 1). . In the formula (3), (nm) is 2, 2 R ¹⁵ , 2 R ¹⁶ , and R ^{6 to} R ¹⁰ are all hydrogen atoms, and X ¹ is a bromine atom. -Bromo-5'-phenyl-2,2'-bithiophene is prepared by reacting 2,2'-bithiophene with N-bromosuccinimide to produce 5-bromo-2,2'-bithiophene. A method of reacting boronic acid to 5-phenyl-2,2′-bithiophene and further reacting with N-bromosuccinimide (S. Hotta, T. Katagiri, Heterocyclic Chem., 2003, 40, 845), etc. It can manufacture by the method of. Furthermore, as represented by the following formula (9), (nm) in the formula (3) is 3, and among the three thiophene rings, R ¹⁵ and R ¹⁶ bonded to the central thiophene ring. Are both n-butyl groups, the other two R ¹⁵ and two R ^{16 and} R ^{6 to} R ¹⁰ bonded to the thiophene rings on both sides are all hydrogen atoms, and X ¹ is a bromine atom. -Bromo-3 ′, 4′-dibutyl-5 ″ -phenyl-2,2 ′: 5 ′, 2 ″ -terthiophene is 3 ′, 4′-dibutyl-5-phenyl-2,2 ′: It can be produced by a known method such as a method of reacting 5 ′, 2 ″ -terthiophene and N-bromosuccinimide (MJCoster, JJDe Voss, Org. Lett., 2002, 4, 3043).

Production of (thiophene / phenylene) co-oligomer represented by formula (4), wherein the compound represented by formula (2) and the compound represented by formula (3) are reacted in the presence of a metal catalyst. In the method, the use ratio of the compound represented by the formula (2) is not particularly limited, but is preferably a ratio of 0.5 to 10 mol with respect to 1 mol of the compound represented by the formula (3). The ratio is more preferably 0.8 to 2 mol. When the ratio of the compound represented by formula (2) is less than 0.5 mol, the yield may be reduced. Moreover, when the usage-amount of the compound represented by Formula (2) exceeds 10 mol, there is no effect corresponding to the usage-amount and it is not economical.

The metal catalyst is not particularly limited, and examples thereof include a palladium catalyst and a nickel catalyst. Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), bis (tricyclohexylphosphine) palladium (0), bis (tributylphosphine) palladium (0). , Dichlorobis (acetonitrile) palladium (II), palladium (0) carbon, dichlorobis (triphenylphosphine) palladium (II), dibromobis (triphenylphosphine) palladium (II), dichloro [1,4-bis (diphenylphosphino) Butane] palladium (II), dichloro [1,2-bis (diphenylphosphino) ethane] palladium (II), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (II), para acetate Um (II), diacetobis (triphenylphosphine) palladium (II), diacet [1,4-bis (diphenylphosphino) butane] palladium (II), diacet [1,3-bis (diphenylphosphino) propane] palladium (II), diaceto [1,2-bis (diphenylphosphino) ethane] palladium (II), diaceto [1,1′-diphenylphosphino] ferrocene] palladium (II), and the like.

Examples of the nickel catalyst include dichloro [1,1′-bis (diphenylphosphino) ferrocene] nickel (II), dichloro [1,4-bis (diphenylphosphino) butane] nickel (II), dichloro [1 , 3-bis (diphenylphosphino) propane] nickel (II), dichloro [1,2-bis (diphenylphosphino) ethane] nickel (II), dichlorobis (triphenylphosphine) nickel (II), dibromo [1, 1′-bis (diphenylphosphino) ferrocene] nickel (II), dibromo [1,4-bis (diphenylphosphino) butane] nickel (II), dibromo [1,3-bis (diphenylphosphino) propane] nickel (II), dibromo [1,2-bis (diphenylphosphino) ethane] nickel (II), dichloro Lobis (triphenylphosphine) nickel (II) and the like can be mentioned.

Among these metal catalysts, tetrakis (triphenylphosphine) palladium (0), dichlorobis (triphenylphosphine) palladium (II), dichloro [1,3-bis (diphenylphosphino) propane] from the viewpoint of high reactivity Nickel (II) and dibromo [1,3-bis (diphenylphosphino) propane] nickel (II) are preferably used.

Although the usage-amount of a metal catalyst is not specifically limited, It is preferable that it is a ratio of 0.001-0.5 mol with respect to 1 mol of compounds represented by Formula (3), 0.01-0.15 A molar ratio is more preferable. When the use ratio of the metal catalyst is less than 0.001 mol, the reaction may be difficult to complete. Moreover, when the usage-amount of a metal catalyst exceeds 0.5 mol, there is no effect corresponding to the usage-amount and it is not economical.

Although it does not specifically limit as a reaction solvent used for reaction with the compound represented by Formula (2), and the compound represented by Formula (3), For example, pentane, n-hexane, cyclohexane, heptane, octane etc. Hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene, toluene, chlorobenzene, dichlorobenzene, and trichlorobenzene; ester solvents such as ethyl acetate and isopropyl acetate; amides such as dimethylformamide, dimethylacetamide, and hexamethylphosphoramide Solvents: Ether solvents such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and cyclopentyl methyl ether; Halogen solvents such as dichloromethane and chloroform; Ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Nitrile, propionitrile, include nitriles such as butyronitrile and the like. Of these, hexane, trichlorobenzene, tetrahydrofuran and cyclopentyl methyl ether are preferably used.

Although the usage-amount of the said reaction solvent is not specifically limited, It is preferable that it is 20-20000 weight part with respect to 100 weight part of compounds represented by Formula (3), and it is more preferable that it is 100-10000 weight part. preferable. When the amount of the reaction solvent used is less than 20 parts by weight, the reaction product may be precipitated and stirring may be difficult. Moreover, when the usage-amount of a reaction solvent exceeds 20000 weight part, there is no effect commensurate with the usage-amount and volume efficiency deteriorates and it is not economical.

The reaction temperature is usually −80 to 200 ° C., preferably −20 to 150 ° C., more preferably −10 to 120 ° C. When the reaction temperature is less than −80 ° C., the reaction may take a long time. Moreover, when reaction temperature exceeds 200 degreeC, there exists a possibility that a by-product may increase. Moreover, although reaction time changes with reaction temperature, it is 0.5 to 50 hours normally.

The (thiophene / phenylene) co-oligomer thus obtained can be easily isolated by a method of concentrating the reaction solution to precipitate a solid, a method of cooling the reaction solution to precipitate a solid, and then filtering.

The (thiophene / phenylene) co-oligomer according to the present invention is represented by the formula (1) and has a left-right asymmetric structure, but the (thiophene / phenylene) co-oligomer represented by the formula (1) Among them, (thiophene / phenylene) co-oligomer in which R ^{6 to} R ¹⁰ are the same groups as R ^{1 to} R ⁵ can also be expressed as the following formula (7). The (thiophene / phenylene) co-oligomer represented by the formula (7) reacts, for example, a compound represented by the following formula (5) and a compound represented by the following formula (6) in the presence of a metal catalyst. Can be manufactured.

Wherein ^(7), R 1 to R ^5, respectively, showing the same group as ^R 1 to R ⁵ in Formula (1). Moreover, n shows the same integer as n in Formula (1), t is an integer of 0-5, (n-2t) shows the integer from 1 or more. R ¹⁷ and R ¹⁸ correspond to R ¹¹ or R ¹² in Formula (1), and R ¹⁹ and R ²⁰ correspond to R ¹¹ and R ¹² in Formula (1), respectively. 2t R ¹⁷ , 2t R ¹⁸ , (n−2t) R ¹⁹ , and (n−2t) R ²⁰ may be the same or different. However, (n-2t) thiophene ring chains have an asymmetric structure.

In formula (5), R ^{1 to} R ⁵ and R ^{17 to} R ¹⁸ represent the same groups as R ^{1 to} R ⁵ and R ^{17 to} R ¹⁸ in formula (7), respectively. t shows the same integer as t in Formula (7). Y ² represents a substituent capable of cross-coupling with a chlorine atom, a bromine atom or an iodine atom.

Specific examples of the substituent that can be cross-coupled to a chlorine atom, bromine atom, or iodine atom represented by Y ² include cross-linking with a chlorine atom, bromine atom, or iodine atom represented by Y ¹ in the formula (2). The same group as the specific example of the substituent which can be coupled can be mentioned.

In Formula (6), R ^{19 to} R ²⁰ each represent the same group as R ^{19 to} R ²⁰ in Formula (7). n and t show the same integer as n and t in Formula (7). X ² and X ³ each independently represent a chlorine atom, a bromine atom or an iodine atom.

As the compounds represented by formula (5) and formula (6), commercially available products may be used, or those produced as necessary by a known method and a method based thereon may be used.

As a manufacturing method of the compound represented by Formula (5), the method similar to the manufacturing method of the compound represented by said Formula (2) can be mentioned.

As a method for producing the compound represented by the formula (6), for example, (n-2t) in the formula (6) is 2, and one R ¹⁹ located on the other adjacent thiophene ring side is 5,5′-dibromo-3-methyl-2,2 ′, which is a methyl group, another R ¹⁹ and two R ²⁰ are all hydrogen atoms, and both X ² and X ³ are bromine atoms -Bithiophene reacts 2-bromo-3-methylthiophene with 2-thienylmagnesium bromide to produce 3-methyl-2,2'-bithiophene (A. Burkhardt, A. Nkansah, R. Shabana, A Galal, Phosphorus, Sulfur Silicon Relat. Elem., 1989, 42, 63), and a known method such as a method of further reacting this with N-bromosuccinimide. In formula (6), (n-2t) is 3, and among the three thiophene rings, one R ¹⁹ bonded to the central thiophene ring is an n-dodecyl group, and three R 5,5 ″ -dibromo-3′-dodecyl-2,2 in which ²⁰ and the other two R ¹⁹ bonded to the thiophene rings on both sides are all hydrogen atoms, and X ² and X ³ are both bromine atoms ': 5', 2 ''-Terthiophene is prepared by reacting 3-dodecylthiophene and N-bromosuccinimide to produce 2,5-dibromo-3-dodecylthiophene, to which 2-thienylmagnesium bromide is added. A method of reacting to 3′-dodecyl-2,2 ′: 5 ′, 2 ″ -terthiophene and further reacting with N-bromosuccinimide (P. Baeuerle, F. Pfau, H. Schlupp, F. Wuerthner) , K. Gaudi, J. Chem. Soc. Perkin Trans. 2, 1993, 3, 489) It can be prepared by methods known. In addition, as represented by the following formula (10), (n-2t) in the formula (6) is 5, and one R ¹⁹ bonded to the central thiophene ring among the five thiophene rings. Is an n-hexyl group, 5 R ²⁰ and 4 R ¹⁹ bonded to the other thiophene ring on both sides are all hydrogen atoms, and X ² and X ³ are both bromine atoms. '''-Dibromo-3''-hexyl-2,2': 5 ', 2'':5'',2''': 5 ''',2''''-kinquethiophene is 5 -Bromo-2,2'-bithiophene and magnesium are reacted to produce 5- (2,2'-bithienyl) magnesium bromide, which is reacted with 2,5-dibromo-3-hexylthiophene to give 3 ”-Hexyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ″ ″-kinquethiophene, and N-bromoco It can be produced by a known method such as a method of reacting succinimide (KYMusick, Q. Hu, L. Pu, Macromolecules, 1998, 31, 2933).

Production of (thiophene / phenylene) co-oligomer represented by formula (7), wherein the compound represented by formula (5) is reacted with the compound represented by formula (6) in the presence of a metal catalyst. In the method, the use ratio of the compound represented by the formula (5) is not particularly limited, but is preferably a ratio of 0.5 to 20 mol with respect to 1 mol of the compound represented by the formula (6). A ratio of 1.6 to 4 mol is more preferable. When the ratio of the compound represented by formula (5) is less than 0.5 mol, the yield may be reduced. Moreover, when the usage-amount of the compound represented by Formula (5) exceeds 20 mol, there is no effect corresponding to the usage-amount and it is not economical.

Examples of the metal catalyst include the same metal catalysts as those used in the reaction of the compound represented by the formula (2) and the compound represented by the formula (3).

Although the usage-amount of a metal catalyst is not specifically limited, It is preferable that it is a ratio of 0.002-1 mol with respect to 1 mol of compounds represented by Formula (6), and is 0.02-0.3 mol. A ratio is more preferable. When the use ratio of the metal catalyst is less than 0.002 mol, the reaction may be difficult to complete. Moreover, when the usage-amount of a metal catalyst exceeds 1 mol, there is no effect corresponding to the usage-amount and it is not economical. The reaction solvent used for the reaction between the compound represented by the formula (5) and the compound represented by the formula (6) is represented by the above-described compound represented by the formula (2) and the formula (3). Examples thereof include the same reaction solvents used for the reaction with the compound.

Although the usage-amount of the said reaction solvent is not specifically limited, It is preferable that it is 20-20000 weight part with respect to 100 weight part of compounds represented by Formula (6), and it is more preferable that it is 100-10000 weight part. preferable. When the amount of the reaction solvent used is less than 20 parts by weight, the reaction product may be precipitated and stirring may be difficult. Moreover, when the usage-amount of a reaction solvent exceeds 20000 weight part, there is no effect commensurate with the usage-amount and volume efficiency deteriorates and it is not economical.

The reaction temperature is usually −80 to 200 ° C., preferably −20 to 150 ° C., more preferably −10 to 120 ° C. When the reaction temperature is less than −80 ° C., the reaction may take a long time. Moreover, when reaction temperature exceeds 200 degreeC, there exists a possibility that a by-product may increase. Moreover, although reaction time changes with reaction temperature, it is 0.5 to 50 hours normally.

The (thiophene / phenylene) co-oligomer thus obtained can be easily isolated by a method of concentrating the reaction solution to precipitate a solid, a method of cooling the reaction solution to precipitate a solid, and then filtering.

According to the present invention, a (thiophene / phenylene) co-oligomer having a relatively low melting point and excellent solubility in various solvents, an organic semiconductor material and a light-emitting material containing the (thiophene / phenylene) co-oligomer, and the ( A method for producing a thiophene / phenylene) co-oligomer can be provided.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Production Example 1 (5-bromo-3,4′-dihexyl-5 ′ ″-phenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene)

In a 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 5-bromo-3-hexyl-5 ″ -phenyl-2,2 ′: 5 ′ represented by the following formula (11) , 2 ″ -terthiophene 9.8 g (20 mmol), dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) 0.54 g (1 mmol) and cyclopentyl methyl ether 100 mL were charged at room temperature under a nitrogen atmosphere. Below, 48 ml (24 mmol) of 0.5M cyclopentyl methyl ether solution of 3-hexyl-2-thienylmagnesium bromide represented by the following formula (12) was added dropwise over 1 hour, followed by stirring for 2 hours.

Next, 50 ml of 5% hydrochloric acid was added and stirred for 30 minutes, followed by liquid separation to obtain an organic layer. To this was added 50 ml of water, and the mixture was further stirred for 30 minutes, followed by liquid separation. Concentrated to precipitate a solid. This was purified by silica gel column chromatography, filtered, and dried under reduced pressure to obtain orange crystals of 3,4′-dihexyl-5 ′ ″-phenyl-2,2 represented by the following formula (13). ': 5', 2 '': 5 '', 2 '''-quaterthiophene 9.6 g (17 mmol) was obtained. The resulting 3,4′-dihexyl-5 ′ ″-phenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene 5-bromo-3-hexyl- The yield based on 5 ″ -phenyl-2,2 ′: 5 ′, 2 ″ -terthiophene was 83%.

Next, 6.5 g (10 mmol) of 3,4′-dihexyl-5 ′ ″-phenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene obtained And dimethylformamide (50 mL) were charged into a 300 mL four-necked flask equipped with a stirrer, thermometer and condenser, and 1.8 g (10 mmol) of N-bromosuccinimide was added in small portions at room temperature under a nitrogen atmosphere. It was. After stirring for 2 hours, 50 ml of n-heptane and 50 ml of water were added and stirred for another 30 minutes, followed by liquid separation to obtain an organic layer, to which 20 ml of water was added and stirred for 30 minutes. The organic layer thus obtained is separated, and the obtained organic layer is concentrated and purified using silica gel column chromatography to obtain orange crystal 5-bromo-3,4′-dihexyl represented by the following formula (14). 5.9 ′ (9 mmol) of −5 ′ ″-phenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene was obtained. The yield based on 3,4′-dihexyl-5 ′ ″-phenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene was 90%.

Production Example 2 (5-bromo-3-butyl-5 ′-(4-methoxyphenyl) -2,2′-bithiophene)

To a 300 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 5.4 g (20 mmol) of 5-bromo-2- (4-methoxyphenyl) thiophene represented by the following formula (15), dichloromethane [1,3-bis (diphenylphosphino) propane] nickel (II) 0.54 g (1 mmol) and cyclopentylmethyl ether 40 mL were charged, and 3-butyl represented by the following formula (16) at room temperature in a nitrogen atmosphere 48 ml (24 mmol) of a 0.5 M cyclopentyl methyl ether solution of 2-thienylmagnesium bromide was added dropwise over 1 hour, followed by stirring for 2 hours.

Next, 100 ml of 2.5% hydrochloric acid was added and stirred for 30 minutes, followed by liquid separation to obtain an organic layer. To this was added 20 ml of water, and the mixture was further stirred for 30 minutes, followed by liquid separation. The layer was concentrated and purified using silica gel column chromatography to give yellow crystalline 3-butyl-5 ′-(4-methoxyphenyl) -2,2′-bithiophene represented by the following formula (17). 4.7 g (14 mmol) was obtained. The yield based on 5-bromo-2- (4-methoxyphenyl) thiophene was 72%.

Next, 3.9 g (12 mmol) of 3-butyl-5 ′-(4-methoxyphenyl) -2,2′-bithiophene obtained and 50 mL of dimethylformamide were added to 300 mL equipped with a stirrer, a thermometer and a condenser. The N-bromosuccinimide (2.5 g, 14 mmol) was added in small portions at room temperature under a nitrogen atmosphere. After stirring for 2 hours, 80 ml of n-heptane and 50 ml of water were added and stirred for another 30 minutes, followed by liquid separation to obtain an organic layer, to which 20 ml of water was added and stirred for 30 minutes. This was separated, the obtained organic layer was concentrated, and recrystallized from methanol to give yellow crystals of 5-bromo-3-butyl-5 ′-(4- 4.0 g (10 mmol) of methoxyphenyl) -2,2′-bithiophene was obtained. The yield based on 3-butyl-5 ′-(4-methoxyphenyl) -2,2′-bithiophene was 82%.

Production Example 3 (5,5 ″ ″-dibromo-3,3 ″, 3 ″ ″-trihexyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 '' ', 2' '' '-Synthesis of quinquethiophene)

In a 300 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 5,5 ″ -dibromo-3′-hexyl-2,2 ′: 5 ′ represented by the following formula (19) 9.8 g (20 mmol) of 2 ″ -terthiophene, 0.54 g (1 mmol) of dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) and 80 mL of cyclopentyl methyl ether were charged at room temperature under a nitrogen atmosphere. Then, 48 ml (24 mmol) of a 0.5 M cyclopentylmethyl ether solution of 3-hexyl-2-thienylmagnesium bromide represented by the following formula (12) was added dropwise over 1 hour, followed by stirring for 2 hours.

Next, 100 ml of 2.5% hydrochloric acid was added and stirred for 30 minutes, followed by liquid separation to obtain an organic layer. To this was added 20 ml of water, and the mixture was further stirred for 30 minutes, followed by liquid separation. The layer was concentrated and purified using silica gel column chromatography to obtain 3,3 ″, 3 ″ ″-trihexyl-2,2 ′: 5 of orange crystals represented by the following formula (20). “, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ″ ″-kinquethiophene 8.0 g (12 mmol) was obtained. The yield based on 5,5 ″ -dibromo-3′-hexyl-2,2 ′: 5 ′, 2 ″ -terthiophene was 60%.

Next, the obtained 3,3 ″, 3 ″ ″-trihexyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ′ ″ '-Kinquethiophene (8.0 g, 12 mmol) and dimethylformamide (50 mL) were charged into a 300 mL four-necked flask equipped with a stirrer, thermometer and condenser, and N-bromosuccinimide was added at room temperature under a nitrogen atmosphere. 3 g (24 mmol) was added in small portions. After stirring for 2 hours, 100 ml of n-heptane and 100 ml of water were added and stirred for another 30 minutes, followed by liquid separation to obtain an organic layer, to which 20 ml of water was added and stirred for 30 minutes. The obtained organic layer was separated, and the resulting organic layer was concentrated and purified using silica gel column chromatography to obtain orange crystals of 5,5 ″ ″-dibromo- represented by the following formula (21). 3,3 ″, 3 ″ ″-trihexyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ″ ″-kinquethiophene 9 0.0 g (11 mmol) was obtained. 3,3 ″, 3 ″ ″-trihexyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ″ ″-against quinquethiophene The yield was 91%.

Example 1 (4 ′, 4 ″ -dihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 '' '' -Kinkuethiophene)

5-Bromo-3,4′-dihexyl-5 ′ ″-phenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene 3 obtained in Production Example 1 .3 g (5 mmol), dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) 0.14 g (0.25 mmol) and cyclopentyl methyl ether 20 mL 200 mL equipped with stirrer, thermometer and condenser In a 4-necked flask with a volume of 12 ml (6 mmol) of a 0.5M cyclopentylmethyl ether solution of 5-phenyl-2-thienylmagnesium bromide represented by the following formula (22) in a nitrogen atmosphere at room temperature over 1 hour. Then, the mixture was stirred for 2 hours.

Next, 10 ml of 2.5% hydrochloric acid was added and stirred for 30 minutes. Thereafter, liquid separation was performed to obtain an organic layer, and 20 ml of water was added thereto and stirred for 30 minutes. This was separated, and the resulting organic layer was concentrated and purified using silica gel column chromatography to obtain 4 ′, 4 ″ -dihexyl-5 of orange crystals represented by the following formula (23). , 5 ″ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ″ ″-kinquethiophene 3.0 g (4 mmol) Got. Obtained 4 ′, 4 ″ -dihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ′ '''-Kinquethiophene5-bromo-3,4'-dihexyl-5'''-phenyl-2,2':5', 2 '': 5 '', 2 '''-quaterthiophene The yield with respect to was 82%.

The resulting orange crystals are 4 ′, 4 ″ -dihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ″. It was confirmed by the following analysis results that it was', 2 '' ''-kinquethiophene.

Melting point: 138 ° C

¹ H-NMR (400 MHz, THF-d ₈ ): δ 0.91 (t, 6H), 1.33-1.36 (m, 8H), 1.43-1.48 (m, 4H), 1.69-1.74 (m, 4H), 2.84 ( t, 4H), 7.08 (s, 1H), 7.13 (d, 1H), 7.16 (s, 1H), 7.21 (d, 1H), 7.23-7.28 (m, 4H), 7.34-7.40 (m, 6H) , 7.62-7.66 (m, 4H)

Example 2 (3′-butyl-5- (4-methoxyphenyl) -5 ″ -phenyl-2,2 ′: 5 ′, 2 ″ -terthiophene)

3.3 g (5 mmol) of 5-bromo-3-butyl-5 ′-(4-methoxyphenyl) -2,2′-bithiophene obtained in Production Example 2, dichloro [1,3-bis (diphenylphosphino) Propane] Nickel (II) 0.14 g (0.25 mmol) and cyclopentyl methyl ether 20 mL were charged into a 200 mL four-necked flask equipped with a stirrer, thermometer and condenser, and the following formula 12 ml (6 mmol) of a 0.5 M cyclopentylmethyl ether solution of 5-phenyl-2-thienylmagnesium bromide represented by (22) was added dropwise over 1 hour, followed by stirring for 2 hours.

Next, 50 ml of cyclopentyl methyl ether and 10 ml of 2.5% hydrochloric acid were added and stirred for 30 minutes. Thereafter, liquid separation was performed to obtain an organic layer, and 20 ml of water was added thereto and stirred for 30 minutes. The obtained organic layer was separated, and the obtained organic layer was concentrated and purified by silica gel column chromatography, whereby 3′-butyl-5- (4- Methoxyphenyl) -5 ″ -phenyl-2,2 ′: 5 ′, 2 ″ -terthiophene 2.0 g (4 mmol) was obtained. The obtained 3′-butyl-5- (4-methoxyphenyl) -5 ″ -phenyl-2,2 ′: 5-bromo-3-butyl-5 ′-(5 ′, 2 ″ -terthiophene The yield based on 4-methoxyphenyl) -2,2′-bithiophene was 82%.

According to the following analysis results, the obtained orange crystals are 3′-butyl-5- (4-methoxyphenyl) -5 ″ -phenyl-2,2 ′: 5 ′, 2 ″ -terthiophene. confirmed.

Melting point: 181 ° C

¹ H-NMR (400 MHz, THF-d ₈ ): ^TM 0.96 (t, 3H), 1.45 (sextet, 2H), 1.69 (quintet, 2H), 2.82 (t, 2H), 3.80 (s, 3H), 6.93 (d, 2H), 7.11 (d, 1H), 7.15 (s, 1H), 7.20 (d, 1H), 7.23-7.27 (m, 2H), 7.33-7.39 (m, 3H), 7.56 (d, 2H ), 7.63 (d, 2H)

Example 3 (3'-hexyl-5,5 "-diphenyl-2,2 ': 5', 2" -terthiophene)

In a 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 6.6 g (20 mmol) of 2,5-dibromo-3-hexylthiophene represented by the following formula (25), dichloro [1, 3-bis (diphenylphosphino) propane] nickel (II) 0.54 g (1 mmol) and 100 mL of cyclopentylmethyl ether were charged, and 5-phenyl-2-phenyl represented by the following formula (22) under a nitrogen atmosphere at room temperature. 40 ml (20 mmol) of a 0.5 M cyclopentyl methyl ether solution of thienylmagnesium bromide was added dropwise over 1 hour, followed by stirring for 2 hours.

Next, 50 ml of 5% hydrochloric acid was added to the reaction solution and stirred for 30 minutes. Thereafter, liquid separation was performed to obtain an organic layer, and 50 ml of water was added thereto and stirred for 30 minutes. This was separated, and the obtained organic layer was concentrated to precipitate a solid. After recrystallization using methanol, it was filtered off and dried under reduced pressure to give yellow crystal 3′-hexyl-5,5 ″ -diphenyl-2,2 ′ represented by the following formula (26). : 9.2 g (19 mmol) of 5 ′, 2 ″ -terthiophene was obtained. The yield of the obtained 3′-hexyl-5,5 ″ -diphenyl-2,2 ′: 5 ′, 2 ″ -terthiophene relative to 2,5-dibromo-3-hexylthiophene was 95%. .

The obtained yellow crystals were confirmed to be 3'-hexyl-5,5 "-diphenyl-2,2 ': 5', 2" -terthiophene by the following analysis results.

Melting point: 124 ° C

¹ H-NMR (400 MHz, CDCl ₂ ): ^TM 0.91 (t, 3H), 1.32-1.38 (m, 4H), 1.41-1.48 (m, 2H), 1.71 (quintet, 2H), 2.81 (t, 2H) , 7.10 (s, 1H), 7.14 (d, 1H), 7.18 (d, 1H), 7.28 (d, 1H), 7.28-7.32 (m, 2H), 7.32 (d, 1H), 7.38-7.43 (m , 4H), 7.61-7.66 (m, 4H)

Example 4 (4′-hexyl-5,5 ′ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene)

To a 2000 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 8.2 g of 5,5′-dibromo-3-hexyl-2,2′-bithiophene represented by the following formula (27) ( 20 mmol), 0.54 g (1 mmol) of dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) and 100 mL of cyclopentyl methyl ether, and represented by the following formula (22) at room temperature under a nitrogen atmosphere. Then, 40 ml (20 mmol) of a 0.5 M cyclopentylmethyl ether solution of 5-phenyl-2-thienylmagnesium bromide was added dropwise over 1 hour, followed by stirring for 2 hours.

Next, 1000 ml of cyclopentyl methyl ether and 100 ml of 2.5% hydrochloric acid were added to the reaction solution and stirred for 30 minutes. Thereafter, liquid separation was performed to obtain an organic layer, and 100 ml of water was added thereto, followed by stirring for 30 minutes. This was separated, and the obtained organic layer was cooled to 5 ° C. to precipitate a solid, which was then filtered off and dried under reduced pressure to obtain 4 ′ of orange crystals represented by the following formula (28). 9.1 g (16 mmol) of hexyl-5,5 ′ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene was obtained. 5,5′-dibromo-3 of the obtained 4′-hexyl-5,5 ′ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene The yield based on -hexyl-2,2′-bithiophene was 90%.

The following orange crystals are 4′-hexyl-5,5 ′ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene. This was confirmed by the analysis results.

Melting point: 150 ° C

¹ H-NMR (400 MHz, THF-d ₈ ) ^TM 0.91 (t, 3H), 1.33-1.38 (m, 4H), 1.41-1.48 (m, 2H), 1.70 (m, 2H), 2.82 (t, 2H ), 7.13 (d, 1H), 7.16 (s, 1H), 7.22 (d, 1H), 7.24-7.28 (m, 4H), 7.34-7.39 (m, 6H), 7.62-7.66 (m, 4H)

Example 5 (3 ″ -hexyl-5,5 ″ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ′ ″ '-Kinkuethiophene)

To a 2000 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 5,5 ″ -dibromo-3′-hexyl-2,2 ′: 5 ′ represented by the following formula (29) 9.8 g (20 mmol) of 2 ″ -terthiophene, 0.54 g (1 mmol) of dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) and 100 mL of cyclopentyl methyl ether were charged at room temperature under a nitrogen atmosphere. Then, 40 ml (20 mmol) of a 0.5 M cyclopentylmethyl ether solution of 5-phenyl-2-thienylmagnesium bromide represented by the following formula (22) was added dropwise over 1 hour, followed by stirring for 2 hours.

Next, 1000 ml of cyclopentyl methyl ether and 100 ml of 2.5% hydrochloric acid were added to the reaction solution and stirred for 30 minutes. Thereafter, liquid separation was performed to obtain an organic layer, and 100 ml of water was added thereto, followed by stirring for 30 minutes. This was separated, and the obtained organic layer was cooled to 5 ° C. to precipitate a solid, which was then filtered off and dried under reduced pressure to obtain 3 ′ of orange crystals represented by the following formula (30). '-Hexyl-5,5 ""-diphenyl-2,2': 5 ', 2 ": 5", 2'": 5 '", 2 ""-kinquethiophene 11 Obtained .4 g (18 mmol). The obtained 3 "-hexyl-5,5""-diphenyl-2, 2 ': 5', 2": 5 ", 2 '": 5'",2"" -The yield of quinquethiophene based on 5,5 "-dibromo-3'-hexyl-2,2 ': 5', 2" -terthiophene was 90%.

The obtained orange crystals are 3 ″ -hexyl-5,5 ″ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 '' '' -Kinquethiophene was confirmed by the following analysis results.

Melting point: 196 ° C

¹ H-NMR (400 MHz, THF-d ₈ ) ^TM 0.91 (t, 3H), 1.34-1.49 (m, 6H), 1.68-1.71 (m, 2H), 2.82 (t, 2H), 7.13 (d, 1H ), 7.16 (s, 1H), 7.18 (d, 1H), 7.20 (d, 1H), 7.22-7.24 (m, 5H), 7.34-7.39 (m, 6H), 7.63-7.66 (m, 4H)

Example 6 (3,3 ″, 3 ″ ″-trihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 '' ', 2' '' '-kinquethiophene)

5,5 ″ ″-Dibromo-3,3 ″, 3 ″ ″-trihexyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ″ obtained in Production Example 3 ': 5''', 2 ''''-kinquethiophene 4.1 g (5 mmol), dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) 0.14 g (0.25 mmol) and 50 mL of cyclopentyl methyl ether was charged into a 500 mL four-necked flask equipped with a stirrer, thermometer and condenser, and 0.5 M cyclopentyl of phenylmagnesium bromide represented by the following formula (31) under a nitrogen atmosphere at room temperature. 30 ml (15 mmol) of methyl ether solution was added dropwise over 1 hour, followed by stirring for 2 hours.

Next, 100 ml of 2.5% hydrochloric acid was added to the reaction solution and stirred for 30 minutes. Thereafter, liquid separation was performed to obtain an organic layer, and 20 ml of water was added thereto and stirred for 30 minutes. This was separated, and the obtained organic layer was concentrated and purified using silica gel column chromatography to obtain 3,3 ″, 3 ′ ″ of orange crystals represented by the following formula (32). '-Trihexyl-5,5 ""-diphenyl-2,2': 5 ', 2 ": 5", 2 "': 5 '", 2 ""-kinquethiophene 3 Obtained .4 g (4 mmol). The resulting 3,3 ″, 3 ″ ″-trihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ '', 2 ''''-kinquethiophene 5,5 ''''-dibromo-3,3'', 3 ''''-trihexyl-2,2':5', 2 '': 5 ”, 2 ′ ″: The yield based on 5 ″ ′, 2 ″ ″-kinquethiophene was 83%.

The resulting orange crystals were 3,3 ″, 3 ″ ″-trihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ″. ': 5' '', 2 '' ''-kinquethiophene was confirmed by the following analysis results.

Melting point: 98 ° C

¹ H-NMR (400 MHz, THF-d ₈ ) ^TM 0.91 (t, 9H), 1.33-1.39 (m, 12H), 1.41-1.49 (m, 6H), 1.68-1.76 (m, 6H), 2.81-2.85 (m, 6H), 7.11 (d, 1H), 7.16 (d, 3H), 7.21 (d, 1H), 7.24 (t, 2H), 7.31 (d, 2H), 7.35 (t, 4H), 7.62 ( m, 4H)

Example 7 (4 ′, 3 ′ ″, 3 ′ ″ ″-trihexyl-5,5 ″ ″ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ″, 2 '' ': 5' '', 2 '' '': 5 '' '', 2 '' '' ': 5' '' '', 2 '' '' ''-septithiophene)

5,5 ″ ″-Dibromo-3,3 ″, 3 ″ ″-trihexyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ″ obtained in Production Example 3 ': 5''', 2 ''''-kinquethiophene 4.1 g (5 mmol), dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) 0.14 g (0.25 mmol) and 5-Phenyl-2-thienylmagnesium represented by the following formula (22) is charged in a 1000 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser under a nitrogen atmosphere at room temperature. After adding 20 ml (10 mmol) of a 0.5M cyclopentyl methyl ether solution of bromide dropwise over 1 hour, the mixture was stirred for 2 hours.

Next, after adding 500 ml of cyclopentyl methyl ether to the reaction solution, 100 ml of 2.5% hydrochloric acid was further added and stirred for 30 minutes. Thereafter, liquid separation was performed to obtain an organic layer, and 20 ml of water was added thereto and stirred for 30 minutes. This was separated, and the obtained organic layer was cooled to 5 ° C. to precipitate a solid, which was filtered off and dried under reduced pressure to obtain 4 ′ of reddish brown crystals represented by the following formula (33). , 3 ′ ″, 3 ′ ″ ″-trihexyl-5,5 ″ ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ '', 2 '''': 5 '''', 2 ''''':5''''', 2 ''''''-4.3 g (4 mmol) of septithiophene were obtained. 4 ', 3''', 3 '''''-trihexyl-5,5''''''-diphenyl-2,2': 5 ', 2'':5'',2' obtained '': 5 ''',2'''':5'''',2''''': 5 ''''',2''''''-5,5' of septithiophene '''-Dibromo-3,3'',3''''-trihexyl-2,2': 5 ', 2'':5'',2''': 5 ''',2''' The yield based on '-quinquethiophene was 88%.

The obtained red crystals are 4 ′, 3 ′ ″, 3 ′ ″ ″-trihexyl-5,5 ″ ″ ″-diphenyl-2,2 ′: 5 ′, 2 ″: 5 ′. ', 2' '': 5 '' ', 2' '' ': 5' '' ', 2' '' '': 5 '' '' ', 2' '' '' '-Septithiophene It was confirmed by the following analysis results.

Melting point: 191 ° C

¹ H-NMR (400 MHz, THF-d ₈ ): ^TM 0.91 (t, 9H), 1.33-1.39 (m, 12H), 1.41-1.49 (m, 6H), 1.68-1.76 (m, 6H), 2.81- 2.85 (m, 6H), 7.12 (d, 1H), 7.16-7.17 (m, 5H), 7.21-7.23 (m, 3H), 7.25 (t, 2H), 7.34 (d, 2H), 7.36 (t, 4H), 7.63 (d, 4H)

Comparative Example 1 (3 ″, 4 ″ -dihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ""-kinquethiophene)

5,5 ″ ″-dibromo-3 ″, 4 ″ -dihexyl-2,2 ′: 5 ′ represented by the following formula (34) produced according to the description in WO 2005/092947 pamphlet 2 ″: 5 ″, 2 ′ ″: 5 ′ ″, 2 ″ ″ — 3.7 g (5 mmol) of quinquethiophene, dichloro [1,3-bis (diphenylphosphino) propane] nickel ( II) 0.14 g (0.25 mmol) and 50 mL of cyclopentyl methyl ether were charged into a 500 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, and at room temperature under a nitrogen atmosphere, the following formula (31) 20 ml (10 mmol) of a 0.5M cyclopentyl methyl ether solution of phenylmagnesium bromide represented was added dropwise over 1 hour, and then stirred for 2 hours.

Next, 100 ml of 2.5% hydrochloric acid was added to the reaction solution and stirred for 30 minutes. Thereafter, liquid separation was performed to obtain an organic layer, and 20 ml of water was added thereto and stirred for 30 minutes. This was separated, and the obtained organic layer was cooled to 5 ° C. to precipitate a solid, which was then filtered off and dried under reduced pressure to obtain 3 ′ of orange crystals represented by the following formula (35). ', 4''-Dihexyl-5,5''''-Diphenyl-2,2': 5 ', 2'':5'',2''': 5 ''',2''''- 3.2 g (4 mmol) of quinquethiophene was obtained. The obtained 3 ", 4" -dihexyl-5,5 ""-diphenyl-2, 2 ': 5', 2 ": 5", 2 '": 5'", 2 ″ ″ -Kinquethiophene 5,5 ″ ″-dibromo-3 ″, 4 ″ -dihexyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: The yield based on 5 ′ ″, 2 ″ ″-kinquethiophene was 87%.

The resulting orange crystals were 3 ″, 4 ″ -dihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′. It was confirmed by the following analysis results that it was '', 2 '' ''-kinquethiophene.

Melting point: 157 ° C

¹ H-NMR (400 MHz, THF-d ₈ ): ^TM 0.92 (t, 6H), 1.33-1.41 (m, 8H), 1.45-1.53 (m, 4H), 1.59-1.67 (m, 4H), 2.80 ( t, 4H), 7.12 (d, 2H), 7.22-7.28 (m, 6H), 7.34-7.39 (m, 6H), 7.63-7.66 (m, 4H)

Evaluation [melting point and solubility in solvent]

4 ′, 4 ″ -dihexyl-5,5 ″ ″-diphenyl-2, 2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ″ obtained in Example 1 ', 2 ″ ″-kinquethiophene and 3 ″, 4 ″ -dihexyl-5,5 ″ ″-diphenyl-2,2 ′ obtained in Comparative Example 1: 5 ′, 2 ″ : 5 ″, 2 ′ ″: 5 ′ ″, 2 ″ ″ — The melting point of quinquethiophene and the solubility in tetrahydrofuran at 25 ° C. were measured. Each measurement result is shown in Table 1.

From Table 1, the (thiophene / phenylene) co-oligomer having a left-right asymmetric structure obtained in Example 1 and the (thiophene / phenylene) co-oligomer not having a left-right asymmetric structure obtained in Comparative Example 1 Although the structure is very close, it can be seen that the (thiophene / phenylene) co-oligomer obtained in Example 1 has a low melting point and excellent solubility in tetrahydrofuran.
[Luminescent characteristics]

The (thiophene / phenylene) co-oligomer obtained in Examples 1 to 7 was evaluated for usefulness as a luminescent material. As an evaluation method, several pieces of each crystal product obtained in Examples 1 to 7 were put in a sample tube and sealed, and irradiated with ultraviolet light (365 nm) from the outside of the sample tube, the fluorescence emitted from the crystal product was observed. The color tone was visually observed. These results are shown in Table 2.

From Table 2, it can be seen that the (thiophene / phenylene) co-oligomer obtained in Examples 1 to 7 is useful as a light emitting material.
[Semiconductor characteristics]

The carrier mobility of the (thiophene / phenylene) co-oligomer obtained in Examples 3 and 4 was measured. In the measurement, a comb-type Au electrode (thickness 50 nm, width 40 μm, channel length 10 μm, channel width 8 cm) on a gate insulating layer on which a thermal oxide film having a thickness of 300 nm was formed using a Si wafer having a resistance value of 1 Ω · cm Further, each of the (thiophene / phenylene) co-oligomers obtained in Examples 3 and 4 was vapor-deposited or dissolved in an organic solvent and then applied to prepare an organic thin film transistor, which was used as a measurement sample. The carrier mobility was determined from the saturation region of the IV characteristic under a vacuum of 10 ⁻³ Pa for the measurement sample. These results are shown in Table 3.

From Table 3, it can be seen that the (thiophene / phenylene) co-oligomer obtained in Examples 3 and 4 is useful as an organic semiconductor material.

Claims (6)

Formula (1):

^(Wherein, R 1 to R ⁵ and ^R 6 ^{to R 10} each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, 1 alkoxy group or a carbon number of 1 to 6 carbon atoms 6 represents a perfluoroalkyl group of 6. n represents an integer of 3 to ^12. R ^{11 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n R ¹¹ may be the same or different, and n R ¹² may be the same or different, provided that n R ¹¹ and n R ¹² bonded to the thiophene ring. (At least one is an alkyl group having 1 to 12 carbon atoms.) And a (thiophene / phenylene) co-oligomer having a left-right asymmetric structure.   An organic semiconductor material comprising the (thiophene / phenylene) co-oligomer according to claim 1.   A luminescent material comprising the (thiophene / phenylene) co-oligomer according to claim 1. Formula (2):

Wherein R ^{1 to} R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms. M represents an integer of 0 to 12. R ^{13 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the m R ^13s are the same. And m R ^{14 s} may be the same or different, and Y ¹ represents a substituent capable of cross-coupling with a chlorine atom, a bromine atom or an iodine atom. A compound represented by formula (3):

(In the formula, R ^{6 to} R ¹⁰ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms. M represents the same integer as m in the formula (2), n represents an integer of 3 to 12, and (n−m) represents an integer of 0 or more, R ^{15 to} R ^16. Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and (n−m) R ^{15 s} may be the same or different, and (n−m) R ¹⁶ may be the same or different, and X ¹ represents a chlorine atom, a bromine atom or an iodine atom), and is reacted in the presence of a metal catalyst. Equation (4):

(Wherein R ^{1 to} R ⁵ and R ^{13 to} R ¹⁴ represent the same groups as R ^{1 to} R ⁵ and R ^{13 to} R ¹⁴ in the formula (2), respectively, and m represents the formula (2). R ^{6 to} R ¹⁰ and R ^{15 to} R ¹⁶ represent the same groups as R ^{6 to} R ¹⁰ and R ^{15 to} R ¹⁶ in the formula (3), respectively, and n represents the same Represents the same integer as n in formula (3), provided that at least one of m R ¹³ , m R ¹⁴ , (n−m) R ^15, and (n−m) R ¹⁶ Each is an alkyl group having 1 to 12 carbon atoms) and a method for producing a (thiophene / phenylene) co-oligomer having a left-right asymmetric structure.

Wherein R ^{1 to} R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms. T represents an integer of 0 to 5. R ^{17 to} R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and t R ^{17 s} are the same. And t R ¹⁸ may be the same or different, and Y ² represents a substituent capable of cross-coupling with a chlorine atom, a bromine atom or an iodine atom.) A compound represented by formula (6):

(In formula, t shows the same integer as t in the said Formula (5). N is an integer of 3-12, Comprising: (n-2t) shows an integer from 1 or more. R < ¹⁹ > -R. ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and (n-2t) R ^{19 s} may be the same or different, and (n-2t) R ²⁰ in the formula may be the same or different, provided that (n-2t) thiophene ring chains have a bilaterally asymmetric structure, X ² and X ³ each independently represent a chlorine atom, A compound represented by formula (7): wherein the compound represented by formula (7):

(Wherein R ^{1 to} R ⁵ and R ^{17 to} R ¹⁸ represent the same groups as R ^{1 to} R ⁵ and R ^{17 to} R ¹⁸ in the formula (5), respectively, and R ^{19 to} R ²⁰ represent And the same group as R ^{19 to} R ²⁰ in the formula (6), t represents the same integer as t in the formula (5), and n represents the same integer as n in the formula (6). And a (thiophene / phenylene) co-oligomer having a left-right asymmetric structure.   The method for producing a (thiophene / phenylene) co-oligomer according to claim 4 or 5, wherein the metal catalyst is dichloro [1,3-bis (diphenylphosphino) propane] nickel (II).