JP2012158581A - Substituted benzochalcogenoacene compound - Google Patents

Abstract

（式中、Ｅはそれぞれ独立に、硫黄またはセレン原子を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、分岐状のアルキル基を有するアリール基、又は、分岐状のアルキル基を有するヘテロアリール基を表す。前記の分岐状のアルキル基を有するアリール基の合計炭素数は９〜３０であり、前記の分岐状のアルキル基を有するアリール基は、置換基を有していてもよい。前記の分岐状のアルキル基を有するヘテロアリール基の合計炭素数は７〜３０であり、前記の分岐状のアルキル基を有するヘテロアリール基は、置換基を有していてもよい。
Ｒ^１及びＲ^２の少なくとも一方は、前記の分岐状のアルキル基を有するアリール基、又は、前記の分岐状のアルキル基を有するヘテロアリール基である。）
で表される置換ベンゾカルコゲノアセン化合物。
【選択図】なしThere is a need for new compounds that can provide thin films of organic semiconductor active layers.
SOLUTION: Formula (1)

(In the formula, each E independently represents a sulfur or selenium atom.
R ¹ and R ² each independently represent a hydrogen atom, an aryl group having a branched alkyl group, or a heteroaryl group having a branched alkyl group. The total number of carbon atoms of the aryl group having a branched alkyl group is 9 to 30, and the aryl group having the branched alkyl group may have a substituent. The total carbon number of the heteroaryl group having the branched alkyl group is 7 to 30, and the heteroaryl group having the branched alkyl group may have a substituent.
At least one of R ¹ and R ² is the aryl group having the branched alkyl group or the heteroaryl group having the branched alkyl group. )
The substituted benzochalcogenoacene compound represented by these.
[Selection figure] None

Description

  The present invention relates to a substituted benzochalcogenoacene compound and the like.

  Organic transistors, which are one type of organic semiconductor device, are used as elements such as electronic paper and large screen flat panel displays. Such an organic transistor is composed of members such as an organic semiconductor active layer, a substrate, an insulating layer, and an electrode. As a compound that gives an organic semiconductor active layer, Patent Literature 1 describes pentacene, and it is also known that a thin film obtained by vacuum-depositing pentacene is used for the organic semiconductor active layer.

JP 2008-85250 A (Example 1)

  Under such circumstances, a novel compound capable of providing a thin film of an organic semiconductor active layer is demanded.

（式中、Ｅはそれぞれ独立に、硫黄またはセレン原子を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、分岐状のアルキル基を有するアリール基、又は、分岐状のアルキル基を有するヘテロアリール基を表す。前記の分岐状のアルキル基を有するアリール基の合計炭素数は９〜３０であり、前記の分岐状のアルキル基を有するアリール基は、置換基を有していてもよい。前記の分岐状のアルキル基を有するヘテロアリール基の合計炭素数は７〜３０であり、前記の分岐状のアルキル基を有するヘテロアリール基は、置換基を有していてもよい。
Ｒ^１及びＲ^２の少なくとも一方は、分岐状のアルキル基を有するアリール基、又は、分岐状のアルキル基を有するヘテロアリール基を表す。）
で表される置換ベンゾカルコゲノアセン化合物。
＜２＞ 式（１）におけるＥが、全て硫黄原子であることを特徴とする＜１＞記載の化合物。
＜３＞ 式（１）におけるＲ^１及びＲ^２が、それぞれ独立に、前記の分岐状のアルキル基を有するアリール基、又は、水素原子であることを特徴とする＜１＞又は＜２＞記載の化合物。
＜４＞ 式（１）におけるＲ^１及びＲ^２が、それぞれ独立に、前記の分岐状のアルキル基を有するアリール基であることを特徴とする＜１＞又は＜２＞記載の化合物。 In order to solve this problem, the present inventor has intensively studied, and as a result, has reached the following present invention.
<1> Formula (1)

(In the formula, each E independently represents a sulfur or selenium atom.
R ¹ and R ² each independently represent a hydrogen atom, an aryl group having a branched alkyl group, or a heteroaryl group having a branched alkyl group. The total number of carbon atoms of the aryl group having a branched alkyl group is 9 to 30, and the aryl group having the branched alkyl group may have a substituent. The total carbon number of the heteroaryl group having the branched alkyl group is 7 to 30, and the heteroaryl group having the branched alkyl group may have a substituent.
At least one of R ¹ and R ² represents an aryl group having a branched alkyl group or a heteroaryl group having a branched alkyl group. )
The substituted benzochalcogenoacene compound represented by these.
<2> The compound according to <1>, wherein all Es in the formula (1) are sulfur atoms.
<3><1> or <2> description, wherein R ¹ and R ² in formula (1) are each independently an aryl group having a branched alkyl group or a hydrogen atom Compound.
<4> The compound according to <1> or <2>, wherein R ¹ and R ² in formula (1) are each independently an aryl group having the branched alkyl group.

（式中、Ｅ、Ｒ^１及びＲ^２は前記と同じ意味を表す。）
で表される化合物であることを特徴とする＜１＞〜＜４＞のいずれか記載の化合物。
＜６＞式（２）におけるＥが、全て硫黄であることを特徴とする＜５＞記載の化合物。
＜７＞ 式（２）におけるＲ^１及びＲ^２が、それぞれ独立に、前記の分岐状のアルキル基を有するアリール基、又は、水素原子であることを特徴とする＜５＞又は＜６＞記載の化合物。
＜８＞ 式（２）におけるＲ^１及びＲ^２が、いずれも前記の分岐状のアルキル基を有するアリール基であることを特徴とする＜５＞又は＜６＞記載の化合物。 <5> The compound represented by the formula (1) is represented by the formula (2).

(In the formula, E, R ¹ and R ² represent the same meaning as described above.)
<1> to <4>, wherein the compound is represented by the formula:
<6> The compound according to <5>, wherein all Es in the formula (2) are sulfur.
<7><5> or <6> description, wherein R ¹ and R ² in formula (2) are each independently an aryl group having a branched alkyl group or a hydrogen atom Compound.
<8> The compound according to <5> or <6>, wherein R ¹ and R ² in the formula (2) are both aryl groups having the branched alkyl group.

<9> A thin film containing the compound according to any one of <1> to <8>.
<10> A thin film comprising the compound according to any one of <1> to <8>.
<11> An organic semiconductor device containing the thin film according to <9> or <10>.
<12> An organic transistor containing the thin film according to <9> or <10>.

  According to the present invention, a novel compound capable of providing an organic semiconductor active layer can be provided.

It is sectional drawing explaining one aspect | mode of the organic transistor in this invention. It is sectional drawing explaining one aspect | mode of the organic transistor in this invention.

で表される置換ベンゾカルコゲノアセン化合物（以下、化合物（１）と記すことがある）である。
式（１）におけるＥは、それぞれ独立に、硫黄またはセレン原子を表す。 The present invention relates to formula (1)

A substituted benzochalcogenoacene compound represented by the formula (hereinafter sometimes referred to as compound (1)).
E in Formula (1) represents a sulfur or a selenium atom each independently.

R ¹ and R ² in Formula (1) are each independently a hydrogen atom, an aryl group having a branched alkyl group (hereinafter sometimes referred to as a branched alkyl-substituted aryl group), or a branched alkyl group. Represents a heteroaryl group having the formula (hereinafter sometimes referred to as a branched alkyl-substituted heteroaryl group).
At least one of R ¹ and R ² is a branched alkyl-substituted aryl group or a branched alkyl-substituted heteroaryl group.
The branched alkyl-substituted aryl group and the branched alkyl-substituted heteroaryl group may have a substituent.
The total carbon number of the branched alkyl-substituted aryl group is 9 to 30 including the substituent, and the total carbon number of the branched alkyl-substituted heteroaryl group is 7 to 30 including the substituent.

  Examples of the branched alkyl group contained in the branched alkyl-substituted aryl group and the branched alkyl-substituted heteroaryl group include i-propyl group, i-butyl group, s-butyl group, t-butyl group, neopentyl group, t- Pentyl group, 1-methylbutyl group, 1-methylpentyl group, 1-methylhexyl group, 1-methylheptyl group, 1-methyloctyl group, 1-methylnonyl group, 1-methyldecyl group, 1-methylundecyl group, 1 -Methyldodecyl group, 1-methyltridecyl group, 1-methyltetradecyl group, 1-methylpentadecyl group, 1-methylhexadecyl group, 1-methylheptadecyl group, 1-methyloctadecyl group, 1-methylnonadecyl group 1-methylicosyl group, 1-ethylpropyl group, 1-ethylbutyl group, 1-ethylpentyl group, 1-ethyl Xyl group, 1-ethylheptyl group, 1-ethyloctyl group, 1-ethylnonyl group, 1-ethyldecyl group, 1-ethylundecyl group, 1-ethyldodecyl group, 1-ethyltridecyl group, 1-ethyltetradecyl group Group, 1-ethylpentadecyl group, 1-ethylhexadecyl group, 1-ethylheptadecyl group, 1-ethyloctadecyl group, 1-ethylnonadecyl group, 1-ethylicosyl group, 1-propylbutyl group, 1-propylpentyl group 1-propylhexyl group, 1-propylheptyl group, 1-propyloctyl group, 1-propylnonyl group, 1-propyldecyl group, 1-propylundecyl group, 1-propyldodecyl group, 1-propyltridecyl group 1-propyltetradecyl group, 1-propylpentadecyl group, 1-propylhexadecyl group, 1 Propylheptadecyl group, 1-propyloctadecyl group, 1-propylnonadecyl group, 1-propylicosyl group, 1-butylpentyl group, 1-butylhexyl group, 1-butylheptyl group, 1-butyloctyl group, 1 -Butylnonyl group, 1-butyldecyl group, 1-butylundecyl group, 1-butyldodecyl group, 1-butyltridecyl group, 1-butyltetradecyl group, 1-butylpentadecyl group, 1-butylhexadecyl group, 1-butylheptadecyl group, 1-butyloctadecyl group, 1-butylnonadecyl group, 1-butylicosyl group, 1-pentylhexyl group, 1-pentylheptyl group, 1-pentyloctyl group, 1-pentylnonyl group, 1-pentyl Decyl group, 1-pentylundecyl group, 1-pentyldodecyl group, 1-pentyltridecyl group 1-pentyltetradecyl group, 1-pentylpentadecyl group, 1-pentylhexadecyl group, 1-pentylheptadecyl group, 1-pentyloctadecyl group, 1-pentylnonadecyl group, 1-pentylicosyl group, 1 -Hexyl heptyl group, 1-hexyl octyl group, 1-hexyl nonyl group, 1-hexyl decyl group, 1-hexyl undecyl group, 1-hexyl decyl group, 1-hexyl tridecyl group, 1-hexyl tetradecyl group, 1-hexylpentadecyl group, 1-hexylhexadecyl group, 1-hexylheptadecyl group, 1-hexyloctadecyl group, 1-hexylnonadecyl group, 1-hexylicosyl group,

2-methylbutyl group, 2-methylpentyl group, 2-methylhexyl group, 2-methylheptyl group, 2-methyloctyl group, 2-methylnonyl group, 2-methyldecyl group, 2-methylundecyl group, 2-methyldodecyl group Group, 2-methyltridecyl group, 2-methyltetradecyl group, 2-methylpentadecyl group, 2-methylhexadecyl group, 2-methylheptadecyl group, 2-methyloctadecyl group, 2-methylnonadecyl group, 2- Methyl icosyl group,
2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethylheptyl group, 2-ethyloctyl group, 2-ethylnonyl group, 2-ethyldecyl group, 2-ethylundecyl group, 2-ethyldodecyl group 2-ethyltridecyl group, 2-ethyltetradecyl group, 2-ethylpentadecyl group, 2-ethylhexadecyl group, 2-ethylheptadecyl group, 2-ethyloctadecyl group, 2-ethylnonadecyl group, 2-ethylicosyl Group, 2-propylpentyl group, 2-propylhexyl group, 2-propylheptyl group, 2-propyloctyl group, 2-propylnonyl group, 2-propyldecyl group, 2-propylundecyl group, 2-propyldodecyl group 2-propyltridecyl group, 2-propyltetradecyl group, 2-propylpentadecyl group, - propyl hexadecyl group, 2-propyl heptadecyl group, 2-propyl octadecyl group, 2-propyl nonadecyl group, 2-propyl icosyl group,
2-butylhexyl group, 2-butylheptyl group, 2-butyloctyl group, 2-butylnonyl group, 2-butyldecyl group, 2-butylundecyl group, 2-butyldodecyl group, 2-butyltridecyl group, 2- Butyltetradecyl group, 2-butylpentadecyl group, 2-butylhexadecyl group, 2-butylheptadecyl group, 2-butyloctadecyl group, 2-butylnonadecyl group, 2-butylicosyl group, 2-pentylheptyl group, 2- Pentyloctyl group, 2-pentylnonyl group, 2-pentyldecyl group, 2-pentylundecyl group, 2-pentyldodecyl group, 2-pentyltridecyl group, 2-pentyltetradecyl group, 2-pentylpentadecyl group, 2-pentylhexadecyl group, 2-pentylheptadecyl group, 2-pentyloctadecyl group, Tyrnonadecyl group, 2-pentylicosyl group, 2-hexyloctyl group, 2-hexylnonyl group, 2-hexyldecyl group, 2-hexylundecyl group, 2-hexyldecyl group, 2-hexyltridecyl group, 2- Hexyltetradecyl group, 2-hexylpentadecyl group, 2-hexylhexadecyl group, 2-hexylheptadecyl group, 2-hexyloctadecyl group, 2-hexylnonadecyl group, 2-hexylicosyl group,

3-methylbutyl group, 3-methylpentyl group, 3-methylhexyl group, 3-methylheptyl group, 3-methyloctyl group, 3-methylnonyl group, 3-methyldecyl group, 3-methylundecyl group, 3-methyldodecyl group Group, 3-methyltridecyl group, 3-methyltetradecyl group, 3-methylpentadecyl group, 3-methylhexadecyl group, 3-methylheptadecyl group, 3-methyloctadecyl group, 3-methylnonadecyl group, 3- Methylicosyl group, 3-ethylpentyl group, 3-ethylhexyl group, 3-ethylheptyl group, 3-ethyloctyl group, 3-ethylnonyl group, 3-ethyldecyl group, 3-ethylundecyl group, 3-ethyldodecyl group, 3 -Ethyltridecyl group, 3-ethyltetradecyl group, 3-ethylpentadecyl group, 3-ethylhexadecyl group 3-ethylheptadecyl group, 3-ethyloctadecyl group, 3-ethylnonadecyl group, 3-ethylicosyl group, 3-propylhexyl group, 3-propylheptyl group, 3-propyloctyl group, 3-propylnonyl group, 3- Propyldecyl group, 3-propylundecyl group, 3-propyldodecyl group, 3-propyltridecyl group, 3-propyltetradecyl group, 3-propylpentadecyl group, 3-propylhexadecyl group, 3-propylheptadecyl group Group, 3-propyloctadecyl group, 3-propylnonadecyl group, 3-propylicosyl group, 3-butylheptyl group, 3-butyloctyl group, 3-butylnonyl group, 3-butyldecyl group, 3-butylundecyl group 3-butyldodecyl group, 3-butyltridecyl group, 3-butyltetradecyl group, 3 Butylpentadecyl group, 3-butylhexadecyl group, 3-butylheptadecyl group, 3-butyloctadecyl group, 3-butylnonadecyl group, 3-butylicosyl group, 3-pentyloctyl group, 3-pentylnonyl group, 3-pentyl Decyl group, 3-pentylundecyl group, 3-pentyldodecyl group, 3-pentyltridecyl group, 3-pentyltetradecyl group, 3-pentylpentadecyl group, 3-pentylhexadecyl group, 3-pentylheptadecyl group 3-pentyloctadecyl group, 3-pentylnonadecyl group, 3-pentylicosyl group, 3-hexylnonyl group, 3-hexyldecyl group, 3-hexylundecyl group, 3-hexyldecyl group, 3-hexyltri Decyl group, 3-hexyltetradecyl group, 3-hexylpentadecyl group, 3-hexyl Ruhexadecyl group, 3-hexylheptadecyl group, 3-hexyloctadecyl group, 3-hexylnonadecyl group, 3-hexylicosyl group,

4-methylpentyl group, 4-methylhexyl group, 4-methylheptyl group, 4-methyloctyl group, 4-methylnonyl group, 4-methyldecyl group, 4-methylundecyl group, 4-methyldodecyl group, 4-methyl Tridecyl group, 4-methyltetradecyl group, 4-methylpentadecyl group, 4-methylhexadecyl group, 4-methylheptadecyl group, 4-methyloctadecyl group, 4-methylnonadecyl group, 4-methylicosyl group, 4- Ethylhexyl group, 4-ethylheptyl group, 4-ethyloctyl group, 4-ethylnonyl group, 4-ethyldecyl group, 4-ethylundecyl group, 4-ethyldodecyl group, 4-ethyltridecyl group, 4-ethyltetradecyl group Group, 4-ethylpentadecyl group, 4-ethylhexadecyl group, 4-ethylheptadecyl group, 4-ethylthio Tadecyl group, 4-ethylnonadecyl group, 4-ethylicosyl group, 4-propylheptyl group, 4-propyloctyl group, 4-propylnonyl group, 4-propyldecyl group, 4-propylundecyl group, 4-propyldodecyl group, 4-propyltridecyl group, 4-propyltetradecyl group, 4-propylpentadecyl group, 4-propylhexadecyl group, 4-propylheptadecyl group, 4-propyloctadecyl group, 4-propylnonadecyl group, 4- Propylicosyl group, 4-butyloctyl group, 4-butylnonyl group, 4-butyldecyl group, 4-butylundecyl group, 4-butyldodecyl group, 4-butyltridecyl group, 4-butyltetradecyl group, 4- Butylpentadecyl group, 4-butylhexadecyl group, 4-butylheptadecyl group, 4-butylo Tadecyl group, 4-butylnonadecyl group, 4-butylicosyl group, 4-pentylnonyl group, 4-pentyldecyl group, 4-pentylundecyl group, 4-pentyldodecyl group, 4-pentyltridecyl group, 4-pentyltetradecyl group Group, 4-pentylpentadecyl group, 4-pentylhexadecyl group, 4-pentylheptadecyl group, 4-pentyloctadecyl group, 4-pentylnonadecyl group, 4-pentylicosyl group, 4-hexyldecyl group, 4 -Hexylundecyl group, 4-hexyldecyl group, 4-hexyltridecyl group, 4-hexyltetradecyl group, 4-hexylpentadecyl group, 4-hexylhexadecyl group, 4-hexylheptadecyl group, 4-hexyl Octadecyl group, 4-hexylnonadecyl group, 4-hexylukosyl group,

5-methylhexyl group, 5-methylheptyl group, 5-methyloctyl group, 5-methylnonyl group, 5-methyldecyl group, 5-methylundecyl group, 5-methyldodecyl group, 5-methyltridecyl group, 5- Methyltetradecyl group, 5-methylpentadecyl group, 5-methylhexadecyl group, 5-methylheptadecyl group, 5-methyloctadecyl group, 5-methylnonadecyl group, 5-methylicosyl group, 5-ethylheptyl group, 5- Ethyloctyl group, 5-ethylnonyl group, 5-ethyldecyl group, 5-ethylundecyl group, 5-ethyldodecyl group, 5-ethyltridecyl group, 5-ethyltetradecyl group, 5-ethylpentadecyl group, 5- Ethylhexadecyl group, 5-ethylheptadecyl group, 5-ethyloctadecyl group, 5-ethylnonadecyl group, 5-e Luicosyl group, 5-propyloctyl group, 5-propylnonyl group, 5-propyldecyl group, 5-propylundecyl group, 5-propyldodecyl group, 5-propyltridecyl group, 5-propyltetradecyl group, 5- Propylpentadecyl group, 5-propylhexadecyl group, 5-propylheptadecyl group, 5-propyloctadecyl group, 5-propylnonadecyl group, 5-propylicosyl group, 5-butylnonyl group, 5-butyldecyl group, 5 -Butylundecyl group, 5-butyldodecyl group, 5-butyltridecyl group, 5-butyltetradecyl group, 5-butylpentadecyl group, 5-butylhexadecyl group, 5-butylheptadecyl group, 5-butyl Octadecyl group, 5-butylnonadecyl group, 5-butylicosyl group, 5-pentyldecyl group, 5-pen Luundecyl group, 5-pentyldodecyl group, 5-pentyltridecyl group, 5-pentyltetradecyl group, 5-pentylpentadecyl group, 5-pentylhexadecyl group, 5-pentylheptadecyl group, 5-pentyloctadecyl group, 5-pentylnonadecyl group, 5-pentylicosyl group, 5-hexylundecyl group, 5-hexyldecyl group, 5-hexyltridecyl group, 5-hexyltetradecyl group, 5-hexylpentadecyl group, 5- Hexylhexadecyl group, 5-hexylheptadecyl group, 5-hexyloctadecyl group, 5-hexylnonadecyl group, 5-hexylicosyl group,

6-methylheptyl group, 6-methyloctyl group, 6-methylnonyl group, 6-methyldecyl group, 6-methylundecyl group, 6-methyldodecyl group, 6-methyltridecyl group, 6-methyltetradecyl group, 6 -Methylpentadecyl group, 6-methylhexadecyl group, 6-methylheptadecyl group, 6-methyloctadecyl group, 6-methylnonadecyl group, 6-methylicosyl group, 6-ethyloctyl group, 6-ethylnonyl group, 6-ethyldecyl group Group, 6-ethylundecyl group, 6-ethyldodecyl group, 6-ethyltridecyl group, 6-ethyltetradecyl group, 6-ethylpentadecyl group, 6-ethylhexadecyl group, 6-ethylheptadecyl group, 6-ethyloctadecyl group, 6-ethylnonadecyl group, 6-ethylicosyl group,
6-propylnonyl group, 6-propyldecyl group, 6-propylundecyl group, 6-propyldodecyl group, 6-propyltridecyl group, 6-propyltetradecyl group, 6-propylpentadecyl group, 6-propylhexadecyl group Decyl group, 6-propylheptadecyl group, 6-propyloctadecyl group, 6-propylnonadecyl group, 6-propylicosyl group, 6-butyldecyl group, 6-butylundecyl group, 6-butyldodecyl group, 6- Butyltridecyl group, 6-butyltetradecyl group, 6-butylpentadecyl group, 6-butylhexadecyl group, 6-butylheptadecyl group, 6-butyloctadecyl group, 6-butylnonadecyl group, 6-butylicosyl group, 6 -Pentylundecyl group, 6-pentyldodecyl group, 6-pentyltridecyl group, 6-pentylte Radecyl group, 6-pentylpentadecyl group, 6-pentylhexadecyl group, 6-pentylheptadecyl group, 6-pentyloctadecyl group, 6-pentylnonadecyl group, 6-pentylicosyl group, 6-hexyldecyl group, 6-hexyltridecyl, 6-hexyltetradecyl, 6-hexylpentadecyl, 6-hexylhexadecyl, 6-hexylheptadecyl, 6-hexyloctadecyl, 6-hexylnonadecyl, Hexylukosyl group,

1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2, 2,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-methyl-1-propylpentyl group, 1-ethyl-1-methylpentyl group, 1-butyl-1-methylpentyl group, 1, 2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5- Dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,2,4-trimethylhexyl group, 2,4,4- Limethylhexyl group, 1,2-dimethylheptyl group, 1,3-dimethylheptyl group, 1,4-dimethylheptyl group, 1,5-dimethylheptyl group, 1,6-dimethylheptyl group, 2,3-dimethylheptyl group Group, 2,4-dimethylheptyl group, 2,5-dimethylheptyl group, 2,6-dimethylheptyl group, 3,4-dimethylheptyl group, 3,5-dimethylheptyl group, 3,6-dimethylheptyl group, 4,5-dimethylheptyl group, 4,6-dimethylheptyl group, 2,2-dimethylheptyl group, 2,2,4-trimethylheptyl group, 2,4,4-trimethylheptyl group, 1,2-dimethyloctyl Group, 1,3-dimethyloctyl group, 1,4-dimethyloctyl group, 1,5-dimethyloctyl group, 1,6-dimethyloctyl group, 1,7-dimethyl Octyl group, 2,3-dimethyloctyl group, 2,4-dimethyloctyl group, 2,5-dimethyloctyl group, 2,6-dimethyloctyl group, 2,7-dimethyloctyl group, 3,4-dimethyloctyl group 3,5-dimethyloctyl group, 3,6-dimethyloctyl group, 3,7-dimethyloctyl group, 4,5-dimethyloctyl group, 4,6-dimethyloctyl group, 5,6-dimethyloctyl group, 5 , 7-dimethyloctyl group, 2,2-dimethyloctyl group, 2,2,4-trimethyloctyl group, 2,4,4-trimethyloctyl group and the like.

  As the “aryl group” in the branched alkyl-substituted aryl group, for example, a monocyclic, bicyclic or tricyclic aryl group can be exemplified, and specifically, expressed as an aryl group having no branched alkyl group. Examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, and a 2-anthracenyl group.

When the “heteroaryl group” in the branched alkyl-substituted heteroaryl group is expressed as a heteroaryl group having no branched alkyl group, for example, a thienyl group, a furyl group, a thiazolyl group, a thieno [3,2-b] thienyl group , Fluoro [3,2-b] furyl group, thieno [3,2-b] furyl group, benzo [b] thienyl group, benzo [b] furyl group, bisthieno [3,2-b: 2 ′, 3 ′ -D] and a thiophenyl group. Preferably, a group represented by the following formula (thienyl group, thieno [3,2-b] thienyl group, benzo [b] thienyl group, benzo [b] furyl group, bisthieno [3,2-b: 2 ′ from the left] , 3′-d] thiophenyl group) and the like.

  Examples of the substituent that the branched alkyl-substituted aryl group and the branched alkyl-substituted heteroaryl group may have include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, an alkoxy group having 1 to 20 carbon atoms, and a carbon number. Examples thereof include an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, and a heteroaralkyl group having 5 to 20 carbon atoms. A group in which a hydrogen atom contained in the substituents exemplified above is replaced with a fluorine atom may also be included as a substituent.

（式中、Ｅは前記と同じ意味を表す。）
の破線）に対して、線対称の位置関係を意味する。すなわち、化合物（１）のベンゾカルコゲノアセン骨格における対称な位置に結合したＲ^１及びＲ^２とは、Ｒ^１がａの炭素原子に結合しＲ^２はａ’の炭素原子に結合する場合、Ｒ^１がｂの炭素原子に結合しＲ^２はｂ’の炭素原子に結合する場合、Ｒ^１がｃの炭素原子に結合しＲ^２はｃ’の炭素原子に結合する場合、Ｒ^１がｄの炭素原子に結合しＲ^２はｄ’の炭素原子に結合する場合のいずれかのＲ^１及びＲ^２である。 The bonding position of R ¹ and R ² bonded to the benzochalcogenoacene skeleton contained in the compound (1) is preferably a symmetric position. Here, the symmetrical position means a center line of the benzochalcogenoacene skeleton contained in the compound (1) (the following formula

(In the formula, E represents the same meaning as described above.)
This means a line-symmetric positional relationship with respect to (a broken line). That is, R ¹ and R ² bonded at symmetrical positions in the benzochalcogenoacene skeleton of compound (1) are when R ¹ is bonded to the carbon atom of a and R ² is bonded to the carbon atom of a ′, When R ¹ is bonded to the carbon atom of b and R ² is bonded to the carbon atom of b ′, when R ¹ is bonded to the carbon atom of c and R ² is bonded to the carbon atom of c ′, R ¹ is d R ² is any one of R ¹ and R ² when bonded to the carbon atom of d ′.

（式中、Ｅ、Ｒ^１、及びＲ^２は前記と同じ意味を表す。）
で表される化合物、または、Ｒ^１がｄの炭素原子に結合しＲ^２はｄ’の炭素原子に結合する場合、すなわち、式（３）

（式中、Ｅ、Ｒ^１、及びＲ^２は前記と同じ意味を表す。）
で表される化合物を挙げることができる。 Preferably, R ¹ is bonded to the carbon atom of b and R ² is bonded to the carbon atom of b ′, ie, the formula (2)

(In the formula, E, R ¹ and R ² have the same meaning as described above.)
Or when R ¹ is bonded to the carbon atom of d and R ² is bonded to the carbon atom of d ′, that is, the formula (3)

(In the formula, E, R ¹ and R ² have the same meaning as described above.)
The compound represented by these can be mentioned.

  Specific examples of the compound (1) of the present invention include the compounds exemplified below.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する

A wavy line means a bond

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

The compound (1) is preferably a compound in which all three Es in the compound (1) are sulfur atoms.
In particular, the following compound (1) having a compound number in the table is preferable.
1, 2, 3, 5, 7, 8, 11, 13, 14, 16, 18, 20, 22, 24, 26, 29, 31, 32, 35, 36, 37, 38, 39, 43, 45, 51, 58, 57, 62, 64, 66, 67, 70, 73, 79, 84, 85, 86, 87, 89, 93, 95, 98, 107, 108, 112, 116, 119, 123, 124, 127, 130, 136, 140, 141, 142, 145, 153, 156, 158, 160, 165, 170, 171, 172, 180, 182, 184, 186, 187, 191, 196, 198, 200, 204, 206, 207, 212, 219, 221, 226, 227, 228, 232, 235, 240, 243, 248, 250, 251, 253, 256, 258, 264, 268, 27 276, 279, 281, 284, 287, 289, 291, 292, 298, 301, 303, 306, 309, 312, 314, 317, 318, 323, 326, 328, 331, 333, 339, 343, 348 349, 351, 354, 355, 358, 361, 362, 363, 364, 368, 371

More preferably, the compound number in the table is the following compound (1).
2, 7, 8, 13, 16, 18, 20, 24, 26, 29, 31, 35, 36, 37, 38, 39, 43, 45, 58, 64, 67, 84, 85, 86, 87, 89, 93, 107, 108, 112, 116, 119, 123, 124, 140, 141, 142, 145, 153, 156, 158, 170.171, 172, 180, 186, 187, 191, 196, 198, 200,204,206,207,212,219,221,226,228,235,243,251,256,258,264,268,276,281,284,289,291,301,306,314,318, 326, 331, 349, 351, 362, 364

Since the compound (1) of the present invention tends to be excellent in solubility in an organic solvent, the compound (1) tends to be easily handled and tends to be easily purified.
Moreover, the solution which melt | dissolved the compound (1) in the organic solvent can apply | coat and dry and can form a thin film.
Furthermore, the compound (1) can provide a thin film exhibiting high carrier mobility, as will be described later.

（式中、Ｒ^１及びＲ^２は前記と同じ意味を表す。Ｘはハロゲン原子、好ましくは臭素原子を表す。）
で表されるジアセチレン化合物（以下、化合物（５−１）と記すことがある）を得、次いで、有機金属塩基を用いたハロゲン−メタル交換反応によりジメタル化した（以下、この反応を「本第１反応」という。）後、硫黄又はセレンを作用させることにより、式（４−１）

（式中、Ｅ、Ｒ^１及びＲ^２は前記と同じ意味を表す。）
で表されるジカルコゲンイン化合物（化合物（４−１）と記すことがある）を得（以下、この反応を「本第２反応」という。）、
次いで、得られた化合物（４−１）と、ビスシクロオクタジエニル白金（Ｐｔ（ＣＯＤ）_２）などの白金化合物又は銅粉末などの銅化合物と、を無溶媒で加熱する方法（以下、「第３−１反応」と記すことがある）、
また、同様にして得られる化合物（４−１）と、ビスシクロオクタジエニルニッケル（Ｎｉ（ＣＯＤ）_２）などのニッケル化合物とホスフィン化合物とを、溶媒の存在下で加熱攪拌する方法（以下、「第３−２反応」と記すことがある）、
等を挙げることができる。 Next, the manufacturing method of a compound (1) is demonstrated.
As this manufacturing method, for example, formula (5-1)

(In the formula, R ¹ and R ² have the same meaning as described above. X represents a halogen atom, preferably a bromine atom.)
And then dimetallated by halogen-metal exchange reaction using an organometallic base (hereinafter, this reaction is referred to as “this” It is referred to as “first reaction”.) After that, by reacting sulfur or selenium, the formula (4-1)

(In the formula, E, R ¹ and R ² represent the same meaning as described above.)
A dichalcogenin compound represented by the formula (sometimes referred to as compound (4-1)) (hereinafter, this reaction is referred to as “the second reaction”),
Next, a method of heating the obtained compound (4-1) and a platinum compound such as biscyclooctadienylplatinum (Pt (COD) ₂ ) or a copper compound such as copper powder in the absence of a solvent (hereinafter, “ 3-1 reaction "),
In addition, a compound (4-1) obtained in the same manner, a nickel compound such as biscyclooctadienyl nickel (Ni (COD) ₂ ), and a phosphine compound are heated and stirred in the presence of a solvent (hereinafter, May be described as "3-2 reaction"),
Etc.

Examples of the organometallic base used in the first reaction include methyl lithium (MeLi), n-butyl lithium (n-BuLi), sec-butyl lithium (sec-BuLi), and tert-butyl lithium (t-BuLi). Although organomagnesium compounds such as organolithium compounds and alkyl Grignard compounds can be used, organolithium compounds are preferred as the organometallic base from the viewpoint of good reactivity of the halogen-metal exchange reaction, For example, butyl lithium (BuLi) is used, and more preferably t-BuLi is used.
As usage-amount of an organometallic base, the range of 4-20 mol can be mentioned with respect to 1 mol of compounds (5-1) (for 1 mol of halogen atoms contained in a compound (5-1)). 2 to 10 mol), preferably 6 to 14 mol (range 3 to 7 mol relative to 1 mol of halogen atom contained in compound (5-1)), more preferably 7 to 10 mol. (The range of 3.5-5 mol with respect to 1 mol of halogen atoms contained in a compound (5-1)). When the usage-amount of an organometallic base is 4 mol or more with respect to 1 mol of compounds (5-1), the unreacted compound (5-1) will be reduced and the yield of the compound (4-1) obtained will be increased. There is a tendency to improve. When the amount used is 20 mol or less with respect to 1 mol of the compound (5-1), the progress of the side reaction tends to be suppressed and the purification of the compound (4-1) tends to be facilitated.

The first reaction and the subsequent second reaction are preferably performed in the presence of a solvent.
The solvent used is selected from those that do not significantly disturb the progress of the first reaction and the second reaction. For example, aliphatic hydrocarbon solvents such as pentane, hexane, and heptane, and aromatics such as benzene, toluene, and xylene. An aromatic hydrocarbon solvent, an ether solvent such as diethyl ether and tetrahydrofuran (THF), or a mixed solvent of two or more selected from these. A preferred solvent is an ether solvent.

This first reaction is carried out, for example, at a reaction temperature of −20 ° C. or lower, preferably −40 ° C. or lower, more preferably −60 ° C. or lower. Although the reaction time of this 1st reaction can be adjusted with the kind of organometallic base and solvent to be used, or reaction temperature, it is the range of about 10 minutes to 5 hours.
Following this first reaction, sulfur or selenium is added to the reaction mixture to perform the second reaction. Sulfur (or selenium) to be used may be used as a solid, or may be added as a solution or suspension dissolved or suspended in the solvent used in the first reaction. After adding sulfur (or selenium), the reaction temperature may be maintained at the same level as in the first reaction, or may be heated as long as it is within the boiling point of the solvent used. Preferably, the reaction temperature is raised until reaching the range of 0 to 40 ° C., and the temperature is kept at the temperature within the same range. An example of the reaction time is 30 minutes to 72 hours.

  As sulfur or selenium used in the second reaction, crystalline, powdery, colloidal sulfur (or selenium) or the like can be used. As usage-amount of sulfur (or selenium), the range of 4-20 mol can be mentioned with respect to 1 mol of compounds (5-1), Preferably it is the range of 6-14 mol, More preferably, it is 7- A range of 10 moles is mentioned. When the amount of sulfur (or selenium) used is 4 mol or more, it is preferable because the yield of the compound (4-1) tends to improve, and when it is 20 mol or less, the progress of side reactions is suppressed, This is preferable because the compound (4-1) tends to be easily purified.

  After completion of the second reaction, the solvent is concentrated if necessary, and an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution is added to the obtained reaction mixture, and then the obtained compound (4-1) To extract. When the solvent used in the first reaction and the second reaction is insoluble in water, the extraction solution can be used as the extraction solvent as it is, but preferred extraction solvents are halogenated compounds such as dichloromethane and chloroform. A hydrocarbon solvent is mentioned. After separating into an organic phase and an aqueous phase, the aqueous phase is separated, an aqueous hexacyanoferrate solution such as potassium ferricyanate is added to the aqueous phase, and the compound (4-1) is added from the aqueous phase. Extraction is performed using an organic solvent such as the extraction solvent. The compound (4-1) thus obtained may be further purified by an operation such as column chromatography or recrystallization, if necessary.

In the present 3-1 reaction, for example, 0.5 to 20 mol, preferably 1 to 10 mol, more preferably 2 to 7 mol of a copper compound or a platinum compound is used with respect to 1 mol of the compound (4-1). It is done. Examples of the copper compound include copper powder, and examples of the platinum compound include biscyclooctadienyl platinum (Pt (COD) ₂ ).
The reaction temperature of this 3-1 reaction can mention the range of 150-400 degreeC, for example, Preferably the range of 200-370 degreeC is mentioned. The reaction time of this 3-1 reaction is within 1 hour, preferably within 30 minutes. After completion of the reaction, the reaction mixture is cooled to room temperature, and insoluble impurities are filtered off using a solvent capable of dissolving compound (1), such as chloroform and dichloromethane, and the filtrate is concentrated. If necessary, column chromatography is performed. By performing operations such as recrystallization, compound (1) is obtained.

In the present 3-2 reaction, the nickel compound used is preferably a zerovalent nickel compound such as biscyclooctadienyl nickel (Ni (COD) ₂ ). This third reaction generates zero-valent nickel compounds in the system by reacting bisacetylacetonate nickel (Ni (acac) ₂ ), which is a divalent nickel compound, with a reducing agent such as diisobutylaluminum hydride. You may let them.
As the usage-amount of a nickel compound, the range of 0.5-5 mol can be mentioned with respect to 1 mol of compounds (4-1), Preferably it is the range of 0.7-3 mol.

Examples of the phosphine compound include triphenylphosphine, tricyclohexylphosphine, tri (o-tolyl) phosphine, trimethylphosphine, tri-t-butylphosphine, 1,2- (diphenylphosphino) ethane, and 1,3- (diphenyl). Phosphino) propane, 1,4- (diphenylphosphino) butane, 1,1-bis (diphenylphosphino) ferrocene, and the like, and triphenylphosphine is preferable.
As a usage-amount of a phosphine compound, the range of 0.5-20 mol etc. of a phosphine compound can be mentioned with respect to 1 mol of nickel compounds, Preferably, the range of 0.7-10 mol is mentioned.

Examples of the solvent used in the present 3-2 reaction include aliphatic hydrocarbon solvents such as pentane, hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and halogenated hydrocarbons such as dichloromethane and chloroform. A solvent etc. can be mentioned. These solvents may be used alone or as a mixed solvent of two or more.
As the solvent, an aromatic hydrocarbon solvent is preferable, and toluene is more preferable.
Examples of the reaction temperature of the present 3-2 reaction include a range from 10 ° C to the boiling point of the solvent.
The reaction time of the present 3-2 reaction depends on the reaction temperature, but is preferably within 72 hours.
After the completion of the reaction of this 3-2 reaction, filtration is performed with heating as necessary to remove insoluble impurities, and then the filtrate is concentrated, and purification operations such as column chromatography and recrystallization are performed as necessary. Thus, the target compound (1) can be obtained.

  Specific examples of the compound (5-1) used in the first reaction are illustrated in the following table.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する

A wavy line means a bond

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

  Specific examples of the compound (4-1) obtained by the second reaction include the following.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する

A wavy line means a bond

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

（式中、Ｒは、Ｒ^１及びＲ^２と同じ意味を表し、Ｘはハロゲン原子、好ましくは臭素原子を表す。）
で表される化合物を用いて、いわゆる、グラーゼル反応（Glaser Reaction）、エグリントンカップリング（Eglinton Coupling）又はヘイカップリング（Hay Coupling、好ましくは、ヨウ化銅などの銅化合物を用いるヘイカップリング）によって調製することができる。
ヘイカップリングは、例えば、下記に示すように、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（TMEDA）及びヨウ化銅などの銅化合物の存在下で行うことができる。

式（６−１）の化合物は、例えば、置換基Ｒを有するアニリンをＮ−ブロモコハク酸イミド等でアミノ基のα位をブロモ化し、得られた化合物のアミノ基をザンドマイヤー反応（Sandmeyer Reaction）等でヨード基に変換し、得られたヨード基含有化合物のヨード基を薗頭クロスカップリング反応等のエチニル化反応でエチニル化する方法等が挙げられる。 As an example of the method for producing the compound (5-1) used in the first reaction, R ¹ and R ² contained in the compound (5-1) are the same type of group (hereinafter, sometimes referred to as R). As a manufacturing method in a certain case, for example, formula (6-1)

(Wherein R represents the same meaning as R ¹ and R ^2, and X represents a halogen atom, preferably a bromine atom.)
By the so-called Glaser Reaction, Eglinton Coupling, or Hay Coupling (preferably Hay Coupling using a copper compound such as copper iodide). Can be prepared.
Hay coupling can be performed in the presence of a copper compound such as N, N, N ′, N′-tetramethylethylenediamine (TMEDA) and copper iodide, as shown below.

The compound of formula (6-1) is obtained by, for example, brominating an aniline having a substituent R with α-position of amino group with N-bromosuccinimide or the like, and converting the amino group of the obtained compound into a Sandmeyer reaction. And the like, and a method of ethynylating the iodo group of the obtained iodo group-containing compound by an ethynylation reaction such as a Sonogashira cross-coupling reaction.

  Specific examples of the compound represented by the formula (6-1) are illustrated in the following table.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する

A wavy line means a bond

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

波線は結合手を意味する。

A wavy line means a bond.

For example, Non-Patent Document 1 (Advanced Materials, 19 , 3008-3011 (2007)) describes a production method in the case where R ¹ and R ² contained in the compound (1) are the same or different groups. The manufacturing method can be mentioned according to the described method. That is, as shown in the following formula, after bromination of benzo [b] thiophene having R ¹ or R ² with bromine, lithium diisopropylamide (LDA) was allowed to act on the obtained brominated product, and then copper chloride Next, butyllithium (BuLi) and bis (phenylsulfonyl) sulfide ((C ₆ H ₅ SO ₂ ) ₂ S) are allowed to act on the obtained coupling product to produce compound (1). It is a method to do.

The compound (1) of the present invention is a material that can be used for the organic semiconductor active layer (hereinafter, such a material may be referred to as an organic semiconductor material). Furthermore, the compound (1) is an organic semiconductor material soluble in an organic solvent. Examples of the organic solvent for dissolving the compound (1) include aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1 ′, 2 Halogenated aliphatic hydrocarbon solvents such as 2,2'-tetrachloroethane and carbon tetrachloride, ether solvents such as tetrahydrofuran and dioxane, and aliphatic hydrocarbon solvents such as pentane, hexane, pentane, octane and cyclohexane Can do. Preferably, toluene, xylene, o-dichlorobenzene, dichloromethane, chloroform, tetrahydrofuran, hexane and the like are mentioned. Two or more organic solvents can be used as a mixed solvent.
As a density | concentration of the compound (1) in the solution which melt | dissolved the compound (1), the range of 0.001-50 mass% can be mention | raise | lifted, for example, Preferably it is 0.01-10 mass%, More preferably, it is 0.8. 1-5 mass% etc. are mentioned.

Next, the thin film and organic semiconductor device of this invention are demonstrated.
The thin film of the present invention contains compound (1). Since the thin film exhibits high carrier mobility, it is suitable as a material for an organic semiconductor device having the thin film as an organic semiconductor active layer.
Moreover, the organic-semiconductor device of this invention contains the thin film of this invention. As an organic semiconductor device of this invention, an organic transistor, an electroluminescent element, a solar cell etc. can be mentioned, for example. Moreover, the organic transistor of this invention can be used for an electronic paper, a flexible display, an IC tag, a sensor, etc., for example.

Examples of the method for forming a thin film of the present invention include a coating film forming process. Here, as described above, the coating film forming process means a film forming process including a step of dissolving the compound (1) in a solvent and applying the obtained solution to a substrate or an insulator layer.
Examples of the coating method include a casting method, a dip coating method, a die coater method, a roll coater method, a bar coater method, a spin coating method, an ink jet method, a screen printing method, an offset printing method, and a micro contact printing method. These methods may be used alone or in combination of two or more.

In the solution containing the compound (1) and the organic solvent, the compound (1) may be used alone, or if it is within a range that does not significantly impair the carrier mobility of the thin film (organic semiconductor active layer) described later. You may mix with an organic semiconductor material different from an inhibitor, a stabilizer, a compound (1), an organic insulating material, etc.
The organic semiconductor material different from the compound (1) may be a low molecular material or a high molecular material. The polymer material may be one obtained by crosslinking a polymer. Preferably, a polymer material is used. Specific examples include polyacetylene and derivatives thereof, polythiophene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyphenylene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polypyrrole and derivatives thereof, polyaniline and derivatives thereof, polytriarylamine and derivatives thereof. Derivatives, polyquinoline and derivatives thereof, perylene and derivatives thereof, tetracene and derivatives thereof, pentacene and derivatives thereof, phthalocyanine and derivatives thereof, and the like. In the thin film of the present invention, the content of the compound (1) is preferably 10% by mass or more and more preferably 20% by mass or more with respect to 100% by mass in total of the organic semiconductor material different from the compound (1) and the compound (1). preferable.

The organic insulating material may be a low molecular material. The polymer material may be a polymer obtained by crosslinking a polymer. Preferably, a polymer material is used. Specific examples include polystyrene, polycarbonate, polydimethylsiloxane, nylon, polyimide, cyclic olefin copolymer, epoxy polymer, cellulose, polyoxymethylene, polyolefin polymer, polyvinyl polymer, polyester polymer, polyether polymer, polyamide polymer. , Fluoropolymers, biodegradable plastics, phenolic resins, amino resins, unsaturated polyester resins, diallyl phthalate resins, epoxy resins, polyimide resins, polyurethane resins, silicone resins, and copolymers combining various polymer units. . In the thin film of the present invention, the content of the compound (1) with respect to the total of 100% by mass of the organic insulating material and the compound (1) is preferably 10% by mass or more, and more preferably 20% by mass or more.
In addition, preparation of this solution composition can be obtained by melt | dissolving compound (1) in a solvent at 10-200 degreeC, for example, Preferably it is about 20-150 degreeC.

  A solution containing the compound (1) thus obtained and an organic solvent is applied to a substrate or an insulating layer to form a coating film, and then the solvent contained in the coating film is removed to remove the solvent on the substrate or the insulating layer. A thin film is formed on the layer. For the removal of the organic solvent, natural drying treatment, heat treatment, decompression treatment, ventilation treatment or a combination of these treatments is employed, but natural drying treatment or heat treatment is preferred in terms of simple operation. Briefly describing the conditions relating to this treatment, there may be mentioned the conditions of standing in the atmosphere or heating the substrate with a hot plate (for example, 40 to 250 ° C., preferably 50 to 200 ° C.).

The thin film of the present invention can also be formed by coating film formation using a dispersion in which compound (1) is dispersed in a solvent. In this case, the above-described coating film forming process can be easily performed by replacing the solution with the dispersion. In this case, the solvent may be water in addition to the organic solvent.
Thus, the thin film of the present invention can be formed by a simple method such as the above-described coating film forming process.

  As a different example of the method for forming a thin film of the present invention, there can be mentioned a method for forming a thin film by subjecting the compound (1) to a vacuum process such as a vacuum deposition method, a sputtering method, a CVD method, a molecular beam epitaxial growth method or the like. .

The method of forming a thin film by the vacuum evaporation method is to use compound (1) and, if necessary, other organic semiconductor material under vacuum in a crucible or a metal boat under vacuum, and evaporate the organic semiconductor material such as compound (1) as a substrate. Or it is the method of vapor-depositing on an insulator material. The degree of vacuum at the time of vapor deposition is usually 1 × 10 ⁻¹ Pa or less, preferably 1 × 10 ⁻³ Pa or less. The substrate temperature at the time of vapor deposition is usually 0 ° C to 300 ° C, preferably 20 ° C to 200 ° C. Examples of the deposition rate include a range of 0.001 nm / sec to 10 nm / sec, preferably 0.01 nm / sec to 1 nm / sec.

  The film thickness of the thin film containing the compound (1) obtained by the coating film forming process or the vacuum process can be adjusted as appropriate depending on the element structure of the organic transistor, for example, but is preferably 1 nm to 10 μm, and more preferably Is 5 nm to 1 μm.

Examples of the organic transistor of the present invention include an organic field effect transistor (OFET).
The structure of the organic field effect transistor is usually such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer comprising the thin film of the present invention, and an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. It is only necessary that a gate electrode be provided with a gap therebetween. As the element structure, for example,
(1) Structure of substrate / gate electrode / insulator layer / source electrode / drain electrode / organic semiconductor active layer,
(2) Structure of substrate / gate electrode / insulator layer / organic semiconductor active layer / source electrode / drain electrode (see FIG. 1)
(3) Structure of substrate / organic semiconductor active layer + source electrode / drain electrode / insulator layer / gate electrode (see FIG. 2),
(4) A structure of substrate / source electrode (or drain electrode) / organic semiconductor active layer + insulator layer + gate electrode / drain electrode (or source electrode) is exemplified. At this time, a plurality of source electrodes, drain electrodes, and gate electrodes may be provided. Moreover, you may provide a some organic-semiconductor active layer in the same plane, and may provide it by laminating | stacking.

Next, other structural components of the organic transistor of the present invention will be described with specific examples.
In the production of the organic transistor in the present invention, the material for forming the source electrode, the drain electrode, and the gate electrode is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, Antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, molybdenum oxide, tungsten, tin oxide / antimony oxide, indium tin oxide (ITO), fluorine doped zinc oxide, zinc, carbon, Graphite, glassy carbon, silver paste and carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, Gnesium, lithium, aluminum, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, lithium / aluminum mixture, etc. are used, especially platinum, gold, silver, Molybdenum oxide, indium, ITO, and carbon are preferable. Alternatively, a known conductive polymer whose conductivity is improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, or the like is also preferably used. Among them, those having low electrical resistance at the contact surface with the semiconductor layer are preferable. These conductive materials may be used alone or in combination of two or more. Although the film thickness of an electrode changes with materials, Preferably it is 0.1 nm-10 micrometers, More preferably, it is 0.5 nm-5 micrometers, More preferably, it is 1 nm-3 micrometers. Moreover, when it serves as a gate electrode and a board | substrate, it may be larger than said film thickness.

  The source electrode and drain electrode used in the organic transistor of the present invention may be subjected to surface treatment. It is preferable that the surface of the electrode in contact with the thin film (organic semiconductor active layer) of the present invention is subjected to surface treatment because the transistor characteristics of the organic transistor including the thin film tend to be improved. Examples of the surface treatment include saturated hydrocarbon compounds having a thiol group such as 1-octylthiol, 1-perfluorooctylthiol, 1-octadecylthiol, and 1-perfluorooctadecylthiol, such as benzenethiol and perfluorobenzenethiol. A thiol compound such as a heterocyclic aromatic compound having a thiol group such as thienyl thiol or perfluorothienyl thiol is used as a solution together with an alcohol or the like, and the electrode is immersed in the solution. For example, a method for modifying the surface of the electrode can be used.

  The electrode can be formed by various methods using the raw materials. Specific examples include a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, and a sol-gel method. It is preferable to perform patterning as needed during film formation or after film formation. Various methods can be used as the patterning method. Specifically, a photolithographic method combining photoresist patterning and etching may be used. In addition, printing methods such as ink jet printing, screen printing, offset printing, letterpress printing, and soft lithography techniques such as a microcontact printing method are also included. These methods may be used alone, or two or more types may be mixed and patterned.

Various insulating films can be used as the insulator layer. Examples of the material for the insulating film include inorganic oxides, inorganic nitrides, and organic compounds.
Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, yttrium trioxide, etc., preferably silicon oxide, aluminum oxide, tantalum oxide, oxide Titanium. Examples of the inorganic nitride include silicon nitride and aluminum nitride. Examples of the organic compound include polyimide, polyamide, polyester, polyacrylate, photocurable resin obtained by photoradical polymerization or photocationic polymerization, a copolymer containing an acrylonitrile component, polyvinylphenol, polyvinyl alcohol, novolak resin, cyanoethyl pullulan. Preferably, polyimide, polyvinyl phenol, and polyvinyl alcohol are used. These insulator layer materials may be used alone or in combination of two or more.
Although the film thickness of an insulator layer changes with materials, Preferably it is 0.1 nm-100 micrometers, More preferably, it is 0.5 nm-50 micrometers, More preferably, it is 5 nm-10 micrometers.

The insulator layer can be formed by various methods using the above raw materials.
Specifically, spin coating, spray coating, dip coating, casting, bar coating, blade coating, screen printing, offset printing, inkjet, vacuum deposition, molecular beam epitaxial growth, ion cluster beam method, ion plating method, sputtering And dry process methods such as atmospheric pressure plasma method and CVD method. Other examples include a sol-gel method, alumite on aluminum, and a method of forming an oxide film on a metal such as a thermal oxide film of silicon.

  Examples of the material for the substrate include glass, paper, quartz, ceramic, resin sheet, and the like. Specific examples of the resin sheet material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, and polyimide. , Carbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like. The thickness of the substrate is preferably 1 μm to 10 mm, more preferably 5 μm to 5 mm.

  A surface treatment may be performed on the insulator layer or the substrate in the portion of the insulator layer or the substrate in contact with the thin film of the present invention (hereinafter sometimes referred to as an organic semiconductor active layer). By performing the surface treatment on the insulator layer on which the organic semiconductor active layer is laminated, the transistor characteristics of the organic transistor can be improved. Specifically, the surface treatment includes hydrophobization treatment with hexamethyldisilazane, octadecyltrichlorosilane, octyltrichlorosilane, phenethyltrichlorosilane, acid treatment with hydrochloric acid, sulfuric acid, hydrogen peroxide water, sodium hydroxide, water, etc. Alkaline treatment with potassium oxide, calcium hydroxide, ammonia, etc., ozone treatment, fluorination treatment, plasma treatment with oxygen, argon, etc., Langmueller / Blodgett film formation process, other insulator and semiconductor thin film formation process, Examples thereof include mechanical treatment, electrical treatment such as corona discharge, and rubbing treatment using fibers.

  Examples of the method for performing the surface treatment include a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, and the like.

Moreover, you may provide the protective film which consists of resin or an inorganic compound on an organic-semiconductor active layer.
By forming the protective film, the influence of outside air can be suppressed and the driving of the transistor can be stabilized.

  Since the thin film of the present invention contains compound (1), it exhibits high carrier mobility. Therefore, the thin film of the present invention is useful as an organic semiconductor active layer in an organic transistor, and an organic transistor having an organic semiconductor active layer containing the thin film of the present invention exhibits excellent transistor characteristics. It will be useful.

Hereinafter, the present invention will be described in more detail with reference to examples.

還流管を具備した反応容器中に、切削片状のマグネシウム（０．９６ｇ、３９．６ｍｍｏｌ）とテトラヒドロフラン（５．５ｍＬ）とを混合し、該反応容器を窒素置換した後、室温（約２５℃）にて、ジブロモエタン（約０．２ｍＬ）を加えた。さらに、テトラヒドロフラン（２２ｍＬ）を加えたのち、１−ブロモ−２−ヘキシルデカン（１０．１ｇ、３３．０ｍｍｏｌ）を含むテトラヒドロフラン（６ｍＬ）溶液を滴下した。次に、反応容器内を加熱し、テトラヒドロフランを還流させ、還流下４時間、反応容器内を攪拌し、グリニャール試薬を調製した。
窒素雰囲気下の別の反応容器に、ＺｎＣｌ_２を１．０ｍｏｌ／Ｌの濃度で含有するジエチルエーテル溶液（シグマアルドリッチ（株）製、３３．０ｍＬ、３３．０ｍｍｏｌ）に、室温にて、上記で得たグリニャール試薬を加え、２時間３０分間攪拌し、グリニャール試薬のマクネシウムが亜鉛にトランスメタル化されたもの（以下、亜鉛試薬と記すことがある）を調製した。該亜鉛試薬をＳｙｎｔｈｅｓｉｓ、Ｖｏｌ．５，Ｐ．８９０，（２００６）に準じて滴定したところ、０．２０４ｍｏｌ／Ｌであった。
窒素を流通させた反応容器に、４−ブロモアニリン（関東化学（株）製、３．３７ｇ、１９．６ｍｍｏｌ）、酢酸パラジウム（０．０４４ｇ、０．２０ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，６’−ジメトキシビフェニル（０．１６ｇ、０．３９ｍｍｏｌ）及びテトラヒドロフラン（３０ｍＬ）を混合し、得られた混合液に、室温下、該亜鉛試薬（９６ｍＬ、１９．６ｍｍｏｌ）を滴下し、室温で１３時間３０分間攪拌した。得られた反応溶液に、塩化アンモニウム水溶液及びジエチルエーテルを加えて攪拌し、有機層と水層とに分液した。得られた有機層を水および飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥し、エバポレーターにて濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィー（展開溶媒；ヘキサン：酢酸エチル＝８：１）によって精製することにより、式Ｃで表される化合物（４−（２−ヘキシルデシル）アニリン）を得た。（５．５７ｇ、１７．５ｍｍｏｌ、収率８９％）
式Ｃで表される化合物の^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：６．９２（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、６．６１（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、３．５３（ｓ，２Ｈ）、２．４１（ｄ，Ｊ＝７．０Ｈｚ，２Ｈ）、１．５６−１．４７（ｍ、１Ｈ）、１．３５−１．１５（ｍ、２４Ｈ）、０．９０−０．８５（ｍ、６Ｈ）
式Ｃで表される化合物のＨＲＭＳ（ＥＩ）：３１７．３０７１（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_２２Ｈ_３９Ｎ_１：３１７．３０８３． <Production Example 1: Synthesis of compound represented by formula C (4- (2-hexyldecyl) aniline)>

In a reaction vessel equipped with a reflux tube, chopped magnesium (0.96 g, 39.6 mmol) and tetrahydrofuran (5.5 mL) were mixed, and the reaction vessel was purged with nitrogen, followed by room temperature (about 25 ° C. ) Was added dibromoethane (approximately 0.2 mL). Furthermore, after adding tetrahydrofuran (22 mL), a tetrahydrofuran (6 mL) solution containing 1-bromo-2-hexyldecane (10.1 g, 33.0 mmol) was added dropwise. Next, the inside of the reaction vessel was heated to reflux tetrahydrofuran, and the inside of the reaction vessel was stirred for 4 hours under reflux to prepare a Grignard reagent.
In a separate reaction vessel under a nitrogen atmosphere, in a diethyl ether solution (Sigma Aldrich, 33.0 mL, 33.0 mmol) containing ZnCl ₂ at a concentration of 1.0 mol / L, at room temperature, the above The obtained Grignard reagent was added, and the mixture was stirred for 2 hours and 30 minutes to prepare a product in which the Grignard reagent Mcnesium was transmetalated to zinc (hereinafter sometimes referred to as a zinc reagent). The zinc reagent was synthesized by Synthesis, Vol. 5, P. 890, (2006), the titration was 0.204 mol / L.
In a reaction vessel in which nitrogen was circulated, 4-bromoaniline (manufactured by Kanto Chemical Co., Inc., 3.37 g, 19.6 mmol), palladium acetate (0.044 g, 0.20 mmol), 2-dicyclohexylphosphino-2 ′ , 6′-dimethoxybiphenyl (0.16 g, 0.39 mmol) and tetrahydrofuran (30 mL) are mixed, and the zinc reagent (96 mL, 19.6 mmol) is added dropwise to the resulting mixture at room temperature. Stir for 13 hours and 30 minutes. To the resulting reaction solution, an aqueous ammonium chloride solution and diethyl ether were added and stirred, and the mixture was separated into an organic layer and an aqueous layer. The obtained organic layer was washed with water and saturated brine, dried over sodium sulfate, and concentrated with an evaporator. The obtained concentrate was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 8: 1) to obtain a compound represented by the formula C (4- (2-hexyldecyl) aniline). . (5.57 g, 17.5 mmol, 89% yield)
¹ H-NMR (CDCl ₃ , δ ppm) of the compound represented by formula C: 6.92 (d, J = 8.1 Hz, 2H), 6.61 (d, J = 8.1 Hz, 2H), 3 .53 (s, 2H), 2.41 (d, J = 7.0 Hz, 2H), 1.56-1.47 (m, 1H), 1.35-1.15 (m, 24H), 0 .90-0.85 (m, 6H)
HRMS (EI) of compound represented by formula C: 317.3071 (M +). Calcd for C ₂₂ H ₃₉ N ₁ : 317.3083.

前項に準じて調製された４−（２−ヘキシルデシル）アニリン（８．０ｇ、２５．２ｍｍｏｌ）とアセト二トリル１７６ｍＬとの混合液に、室温下、塩酸（２Ｍ：１７６ｍＬ）を加えた後、−２〜０℃に冷却した。亜硫酸ナトリウム（２．２６ｇ、３２．８ｍｍｏｌ）水溶液（水２５ｍＬ）を上記混合液に滴下し、さらに、−２〜０℃にて２時間攪拌した。得られた反応溶液にヨウ化カリウム（４１．８ｇ、２５１．９ｍｍｏｌ）を加えた後、室温まで昇温し、室温下でさらに１６時間攪拌した。その後、室温下、この反応溶液に、亜硫酸ナトリウム水溶液及び酢酸エチルを混合し、有機層と水層とに分液した。得られた有機層を水および飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥し、エバポレーターにて濃縮した。得られた濃縮物をシリカゲルカラム（展開溶媒；ヘキサン）によって精製することにより、式Ｄで表される化合物（１−ヨード−４−（２−ヘキシルデシル）ベンゼン）を得た。（９．７０ｇ、２２．６ｍｍｏｌ、収率９０％）
式Ｄで表される化合物の^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．５７（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、６．８９（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、２．４６（ｄ，Ｊ＝７．０Ｈｚ，２Ｈ）、１．６０−１．５０（ｍ、１Ｈ）、１．３３−１．１６（ｍ、２４Ｈ）、０．９１−０．８５（ｍ、６Ｈ）
式Ｄで表される化合物のＨＲＭＳ（ＥＩ）：４２８．１９０１（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_２２Ｈ_３７Ｉ_１：４２８．１９４０． <Production Example 2: Synthesis of compound represented by formula D (1-iodo-4- (2-hexyldecyl) benzene)>

After adding hydrochloric acid (2M: 176 mL) at room temperature to a mixture of 4- (2-hexyldecyl) aniline (8.0 g, 25.2 mmol) and acetonitryl 176 mL prepared according to the previous section, Cooled to −2 to 0 ° C. A sodium sulfite (2.26 g, 32.8 mmol) aqueous solution (water 25 mL) was added dropwise to the above mixture, and the mixture was further stirred at −2 to 0 ° C. for 2 hours. After adding potassium iodide (41.8 g, 251.9 mmol) to the obtained reaction solution, the temperature was raised to room temperature, and the mixture was further stirred at room temperature for 16 hours. Thereafter, this reaction solution was mixed with an aqueous sodium sulfite solution and ethyl acetate at room temperature, and separated into an organic layer and an aqueous layer. The obtained organic layer was washed with water and saturated brine, dried over sodium sulfate, and concentrated with an evaporator. The obtained concentrate was purified by a silica gel column (developing solvent: hexane) to obtain a compound represented by the formula D (1-iodo-4- (2-hexyldecyl) benzene). (9.70 g, 22.6 mmol, 90% yield)
¹ H-NMR (CDCl ₃ , δ ppm) of the compound represented by Formula D: 7.57 (d, J = 8.1 Hz, 2H), 6.89 (d, J = 8.1 Hz, 2H), 2 .46 (d, J = 7.0 Hz, 2H), 1.60-1.50 (m, 1H), 1.33-1.16 (m, 24H), 0.91-0.85 (m, 6H)
HRMS (EI) of the compound represented by the formula D: 428.9011 (M +). Calcd for C ₂₂ H ₃₇ I ₁ : 428. 1940.

前項で得られた式Ｄで表される化合物（１．０ｇ、２．３３ｍｍｏｌ）、式Ｅで表される４−アミノフェニルボロン酸ピナコールエステル（東京化成工業（株）製、０．７１６ｇ、３．２７ｍｍｏｌ）、２．０Ｍの炭酸カリウム水溶液（５．８ｍＬ）及びジオキサン（２００ｍＬ）の混合液を３０分間窒素バブリングした後、該混合液に、室温下、酢酸パラジウム（０．０２６ｇ、０．１１６ｍｍｏｌ）および２−ジシクロヘキシルホスフィノ−２’，６’−ジメトキシビフェニル（０．０９６ｇ、０．２３４ｍｍｏｌ）を加えた後、ジオキサンが還流するまで加熱し、さらに、６．５時間還流させた。その後、反応溶液を室温に冷却し、この反応溶液に、塩化アンモニウム水溶液及び酢酸エチルを混合し、有機層と水層とに分液した。得られた有機層を水で洗浄した後、硫酸ナトリウムで乾燥し、エバポレーターにて濃縮した。得られた濃縮物ををシリカゲルカラム（展開溶媒；クロロホルム）によって精製することにより、式Ｆで表される化合物（４−アミノ−４’−（２−ヘキシルデシル）ビフェニル）０．７６８ｇ（１．９５ｍｍｏｌ、収率８４％）を得た。
式Ｆで表される化合物の^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．４４（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、７．４１（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、７．１６（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、６．７５（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、３．６９（ｓ，２Ｈ）、２．５３（ｄ，Ｊ＝６．８Ｈｚ，２Ｈ）、１．６８−１．５８（ｍ、１Ｈ）、１．３６−１．１９（ｍ，２４Ｈ）、０．８８（ｔ，Ｊ＝７．０Ｈｚ，６Ｈ）
式Ｆで表される化合物のＨＲＭＳ（ＥＩ）：３９３．３３９１（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_２８Ｈ_４３Ｎ_１：３９３．３３９６． <Production Example 3: Synthesis of compound represented by formula F (4-amino-4 '-(2-hexyldecyl) biphenyl)>

The compound represented by Formula D (1.0 g, 2.33 mmol) obtained in the previous section, 4-aminophenylboronic acid pinacol ester represented by Formula E (manufactured by Tokyo Chemical Industry Co., Ltd., 0.716 g, 3 .27 mmol), 2.0M aqueous potassium carbonate solution (5.8 mL) and dioxane (200 mL) were bubbled with nitrogen for 30 minutes, and then palladium acetate (0.026 g, 0.116 mmol) was added to the mixture at room temperature. ) And 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (0.096 g, 0.234 mmol), and then heated until the dioxane was refluxed, and further refluxed for 6.5 hours. Thereafter, the reaction solution was cooled to room temperature, and this reaction solution was mixed with an aqueous ammonium chloride solution and ethyl acetate, and separated into an organic layer and an aqueous layer. The obtained organic layer was washed with water, dried over sodium sulfate, and concentrated with an evaporator. The obtained concentrate is purified by a silica gel column (developing solvent; chloroform) to give 0.768 g (1. 4-amino-4 ′-(2-hexyldecyl) biphenyl) represented by the formula F. 95 mmol, 84% yield).
¹ H-NMR (CDCl ₃ , δ ppm) of the compound represented by Formula F: 7.44 (d, J = 8.1 Hz, 2H), 7.41 (d, J = 8.1 Hz, 2H), 7 .16 (d, J = 8.1 Hz, 2H), 6.75 (d, J = 8.1 Hz, 2H), 3.69 (s, 2H), 2.53 (d, J = 6.8 Hz, 2H), 1.68-1.58 (m, 1H), 1.36-1.19 (m, 24H), 0.88 (t, J = 7.0 Hz, 6H)
HRMS (EI) of compound represented by formula F: 393.3391 (M +). Calcd for C ₂₈ H ₄₃ N ₁ : 393.3396.

前項と同様に調製された式Ｆで表される化合物（４−アミノ−３−ブロモ−４’−（２−ヘキシルデシル）ビフェニル）５．３０ｇ（１３．４６ｍｍｏｌ）、酢酸アンモニウム（０．１０４ｇ、１．３５ｍｍｏｌ）及びアセト二トリル８１ｍＬの混合物を０℃に冷却し、Ｎ−ブロモコハク酸イミド（２．５２ｇ、１４．１ｍｍｏｌ）を加えた。次に、室温まで昇温した後、さらに２時間攪拌した。得られた反応溶液に、水及び酢酸エチルを混合し、有機層と水層とに分液した。得られた有機層を水で洗浄した後、硫酸ナトリウムで乾燥し、エバポレーターにて濃縮した。得られた濃縮物をシリカゲルカラム（展開溶媒；ヘキサン：クロロホルム＝１：１）によって精製することにより、４−アミノ−３−ブロモ−４’−（２−ヘキシルデシル）ビフェニルを得た。（５．０１ｇ、１０．６ｍｍｏｌ、収率７９％）
式Ｇで表される化合物の^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．６６（ｄ，Ｊ＝１．８Ｈｚ，１Ｈ）、７．４０（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、７．３５（ｄｄ，Ｊ＝８．４Ｈｚ，２．１Ｈｚ，１Ｈ）、７．１６（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、６．８２（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ）、４．１１（ｓ，２Ｈ）、２．５４（ｄ，Ｊ＝６．９Ｈｚ，２Ｈ）、１．６８−１．５８（ｍ、１Ｈ）、１．３４−１．１８（ｍ，２４Ｈ）、０．８８（ｔ，Ｊ＝６．９Ｈｚ，６Ｈ）
式Ｇで表される化合物のＭＳ：４７１（Ｍ＋）． <Production Example 4: Synthesis of compound represented by formula G (4-amino-3-bromo-4 '-(2-hexyldecyl) biphenyl)>

5.30 g (13.46 mmol) of a compound represented by the formula F (4-amino-3-bromo-4 ′-(2-hexyldecyl) biphenyl) prepared in the same manner as in the previous section, ammonium acetate (0.104 g, 1.35 mmol) and 81 mL of acetonitryl were cooled to 0 ° C. and N-bromosuccinimide (2.52 g, 14.1 mmol) was added. Next, after heating up to room temperature, it stirred for further 2 hours. Water and ethyl acetate were mixed with the obtained reaction solution, and the mixture was separated into an organic layer and an aqueous layer. The obtained organic layer was washed with water, dried over sodium sulfate, and concentrated with an evaporator. The obtained concentrate was purified by a silica gel column (developing solvent; hexane: chloroform = 1: 1) to obtain 4-amino-3-bromo-4 ′-(2-hexyldecyl) biphenyl. (5.01 g, 10.6 mmol, yield 79%)
¹ H-NMR (CDCl ₃ , δ ppm) of the compound represented by formula G: 7.66 (d, J = 1.8 Hz, 1H), 7.40 (d, J = 8.1 Hz, 2H), 7 .35 (dd, J = 8.4 Hz, 2.1 Hz, 1H), 7.16 (d, J = 8.1 Hz, 2H), 6.82 (d, J = 8.4 Hz, 1H), 4. 11 (s, 2H), 2.54 (d, J = 6.9 Hz, 2H), 1.68-1.58 (m, 1H), 1.34-1.18 (m, 24H), 0. 88 (t, J = 6.9 Hz, 6H)
MS for compound of formula G: 471 (M +).

４−アミノ−３−ブロモ−４’−（２−ヘキシルデシル）ビフェニル（４．０ｇ、８．５ｍｍｏｌ）、アセト二トリル（５９ｍＬ）及び塩酸水溶液（２Ｍ：５９．３ｍＬ）を混合し、０℃まで冷却した。冷却された混合液に、亜硝酸ナトリウム（０．７６ｇ、１１．０ｍｍｏｌ）水溶液（水１２ｍＬ）を滴下し、０〜１℃にて２時間攪拌し、続いて、同温度にてヨウ化カリウム（１４．１ｇ、８４．６ｍｍｏｌ）を加えた後、室温（約２５℃）まで昇温させ、室温にて１８時間攪拌した。室温下、得られた溶液を亜硫酸ナトリウム水溶液に注ぎ込み、酢酸エチルを加え、水および飽和食塩水により洗浄した。有機層を硫酸ナトリウムで乾燥し、エバポレーターにて濃縮することにより粗生成物を得た。これをシリカゲルカラム（展開溶媒；ヘキサン）によって精製することにより、３−ブロモ−４−ヨード−４’−（２−ヘキシルデシル）ビフェニル（化合物Ｈ、３．０６ｇ、５．２４ｍｍｏｌ、収率６２％）を得た。
化合物Ｈの物性は以下のとおりであった。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．８８（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ）、７．８５（ｄ，Ｊ＝２．１Ｈｚ，１Ｈ）、７．４４（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、７．２３−７．２０（ｍ，３Ｈ）、２．５６（ｄ，Ｊ＝６．９Ｈｚ，２Ｈ）、１．６７−１．５９（ｍ、１Ｈ）、１．３２−１．２１（ｍ，２４Ｈ）、０．８８（ｔ，Ｊ＝６．９Ｈｚ，６Ｈ）
ＨＲＭＳ（ＥＩ）：５８２．１３４８（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_２８Ｈ_４０Ｂｒ_１Ｉ_１：５８２．１３５８． <Production Example 5: Synthesis of compound represented by formula H (compound H)>

4-amino-3-bromo-4 ′-(2-hexyldecyl) biphenyl (4.0 g, 8.5 mmol), acetonitryl (59 mL) and aqueous hydrochloric acid (2M: 59.3 mL) were mixed and mixed at 0 ° C. Until cooled. An aqueous solution of sodium nitrite (0.76 g, 11.0 mmol) (water 12 mL) was added dropwise to the cooled mixture, and the mixture was stirred at 0 to 1 ° C. for 2 hours, followed by potassium iodide ( 14.1 g, 84.6 mmol) was added, the temperature was raised to room temperature (about 25 ° C.), and the mixture was stirred at room temperature for 18 hours. The resulting solution was poured into an aqueous sodium sulfite solution at room temperature, ethyl acetate was added, and the mixture was washed with water and saturated brine. The organic layer was dried over sodium sulfate and concentrated with an evaporator to obtain a crude product. This was purified by a silica gel column (developing solvent; hexane) to give 3-bromo-4-iodo-4 ′-(2-hexyldecyl) biphenyl (Compound H, 3.06 g, 5.24 mmol, yield 62%). )
The physical properties of Compound H were as follows.
¹ H-NMR (CDCl ₃ , δ ppm): 7.88 (d, J = 8.4 Hz, 1H), 7.85 (d, J = 2.1 Hz, 1H), 7.44 (d, J = 8 .1 Hz, 2H), 7.23-7.20 (m, 3H), 2.56 (d, J = 6.9 Hz, 2H), 1.67-1.59 (m, 1H), 1.32. -1.21 (m, 24H), 0.88 (t, J = 6.9 Hz, 6H)
HRMS (EI): 582.1348 (M +). Calcd for C ₂₈ H ₄₀ Br ₁ I ₁ : 582.1358.

室温下、ジクロロビス（トリフェニルホスフィン）パラジウム（０．０２４ｇ、０．０３４ｍｍｏｌ）、ヨウ化銅（０．０１３ｇ、０．０７ｍｍｏｌ）、３−ブロモ−４−ヨード−４’−（２−ヘキシルデシル）ビフェニル（化合物Ｈ、２．６７ｇ、４．５８ｍｍｏｌ）、トルエン（１４ｍＬ）およびジイソプロピルアミン（１４ｍＬ）の混合物を２０分間窒素バブリングして脱気し、続いて、トリメチルシリルアセチレン（０．３６ｇ、３．７ｍｍｏｌ）のジイソプロピルアミン（５ｍＬ）溶液を室温にて滴下し、室温にてさらに３時間攪拌した。得られた反応混合物をセライトでろ過し、得られた濾液をエバポレーターにより溶媒を留去し、粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）により精製することにより３−ブロモ−４−エチニルトリメチルシリル−４’−（２−ヘキシルデシル）ビフェニルを得た（化合物Ｉ １．９２ｇ、３．４７ｍｍｏｌ、７６％）。
化合物Ｊの物性は以下のとおり。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．８２（ｄ，Ｊ＝１．２Ｈｚ，１Ｈ）、７．５３（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ）、７．４８−７．４５（ｍ，３Ｈ）、７．２１（ｄ，Ｊ＝７．８Ｈｚ，２Ｈ）、２．５６（ｄ，Ｊ＝６．９Ｈｚ，２Ｈ）、１．６８−１．５９（ｍ、１Ｈ）、１．３４−１．２１（ｍ，２４Ｈ）、０．９０−０．８５（ｍ，６Ｈ）、０．２９（ｓ，９Ｈ）
ＨＲＭＳ（ＥＩ）：５５２．２７９８（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_３３Ｈ_４９Ｂｒ_１Ｓｉ_１：５５２．２７８７． <Production Example 6: Synthesis of Compound represented by Formula I (Compound I)>

Under room temperature, dichlorobis (triphenylphosphine) palladium (0.024 g, 0.034 mmol), copper iodide (0.013 g, 0.07 mmol), 3-bromo-4-iodo-4 ′-(2-hexyldecyl) A mixture of biphenyl (Compound H, 2.67 g, 4.58 mmol), toluene (14 mL) and diisopropylamine (14 mL) was degassed by bubbling with nitrogen for 20 minutes, followed by trimethylsilylacetylene (0.36 g, 3.7 mmol). ) Was added dropwise at room temperature, and the mixture was further stirred at room temperature for 3 hours. The obtained reaction mixture was filtered through Celite, and the solvent was distilled off from the obtained filtrate using an evaporator to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane) to give 3-bromo-4-ethynyltrimethylsilyl-4 ′-(2-hexyldecyl) biphenyl (Compound I 1.92 g, 3. 47 mmol, 76%).
The physical properties of Compound J are as follows.
¹ H-NMR (CDCl ₃ , δ ppm): 7.82 (d, J = 1.2 Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 7.48-7.45 (m , 3H), 7.21 (d, J = 7.8 Hz, 2H), 2.56 (d, J = 6.9 Hz, 2H), 1.68-1.59 (m, 1H), 1.34 -1.21 (m, 24H), 0.90-0.85 (m, 6H), 0.29 (s, 9H)
HRMS (EI): 552.2798 (M +). _{Calcd for C 33 H 49 Br 1} Si 1: 552.2787.

窒素気流下、３−ブロモ−４−エチニルトリメチルシリル−４’−（２−ヘキシルデシル）ビフェニル（化合物Ｉ、２．４３ｇ、４．３９ｍｍｏｌ）をテトラヒドロフラン（１２ｍＬ）およびメタノール（１２ｍＬ）に溶解させた。得られた溶解液に、室温にて炭酸カリウム（０．０６１ｇ、０．４３９ｍｍｏｌ）を加え、さらに１５時間３０分攪拌した。得られた反応生成物からエバポレーターにより溶媒を留去し、粗生成物を得た。粗生成物に飽和塩化アンモニウム水溶液およびエーテルを加え、分液した。得られた有機層を水で洗浄後、硫酸マグネシウムで乾燥し、エバポレーターでエーテルを留去することにより、３−ブロモ−４−エチニル−４’−（２−ヘキシルデシル）ビフェニルを得た（化合物Ｊ、２．１１ｇ、４．３８ｍｍｏｌ、収率９９％）。
化合物Ｊの物性は以下のとおり。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．８３（ｄ，Ｊ＝１．５Ｈｚ，１Ｈ）、７．５７（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ）、７．４９（ｄｄ，Ｊ＝７．８，１．８Ｈｚ，１Ｈ）、７．４７（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、７．２２（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、３．４１（ｓ、１Ｈ）、２．５７（ｄ，Ｊ＝６．９Ｈｚ，２Ｈ）、１．６７−１．５９（ｍ，１Ｈ）、１．３１−１．２１（ｍ，２４Ｈ）、０．８８（ｔ，Ｊ＝６．９Ｈｚ，６Ｈ）
ＨＲＭＳ（ＥＩ）：４８０．２３８５（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_３０Ｈ_４１Ｂｒ_１：４８０．２３９２． <Production Example 7: Synthesis of compound represented by formula J (compound J)>

Under a nitrogen stream, 3-bromo-4-ethynyltrimethylsilyl-4 ′-(2-hexyldecyl) biphenyl (Compound I, 2.43 g, 4.39 mmol) was dissolved in tetrahydrofuran (12 mL) and methanol (12 mL). To the resulting solution, potassium carbonate (0.061 g, 0.439 mmol) was added at room temperature, and the mixture was further stirred for 15 hours and 30 minutes. The solvent was distilled off from the obtained reaction product by an evaporator to obtain a crude product. A saturated aqueous ammonium chloride solution and ether were added to the crude product, followed by liquid separation. The obtained organic layer was washed with water, dried over magnesium sulfate, and the ether was distilled off with an evaporator to obtain 3-bromo-4-ethynyl-4 ′-(2-hexyldecyl) biphenyl (compound J, 2.11 g, 4.38 mmol, 99% yield).
The physical properties of Compound J are as follows.
¹ H-NMR (CDCl ₃ , δ ppm): 7.83 (d, J = 1.5 Hz, 1H), 7.57 (d, J = 8.1 Hz, 1H), 7.49 (dd, J = 7 .8, 1.8 Hz, 1H), 7.47 (d, J = 8.1 Hz, 2H), 7.22 (d, J = 8.1 Hz, 2H), 3.41 (s, 1H), 2 .57 (d, J = 6.9 Hz, 2H), 1.67-1.59 (m, 1H), 1.31-1.21 (m, 24H), 0.88 (t, J = 6. 9Hz, 6H)
HRMS (EI): 480.2385 (M +). Calcd for C ₃₀ H ₄₁ Br ₁ : 480.2392.

テトラメチルエチレンジアミン（ＴＭＥＤＡ、０．０６ｍＬ、０．４２ｍｍｏｌ）、ヨウ化銅（０．０４ｇ、０．２０８ｍｍｏｌ）及びアセトンを含む溶液（１６ｍＬ）を室温にて、空気でバブリングし、バブリングしている該溶液に、３−ブロモ−４−エチニル−４’−（２−ヘキシルデシル）ビフェニル（化合物Ｊ、２．０ｇ、４．２ｍｍｏｌ）を含むアセトン溶液（２ｍL）を滴下した。続いて、室温にて空気バブリングしながら、さらに１８時間攪拌した。得られた反応溶液からエバポレーターにて溶媒を留去し、得られた残渣に１Ｍ塩酸及びヘキサンを加えた。得られたヘキサン層を水および飽和食塩水で洗浄後、硫酸マグネシウムで乾燥した後、ヘキサンを留去し粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）にて精製することで、式Ｋで表される化合物（化合物Ｋ）の白色粉末 １．８５ｇ（１．９２ｍｍｏｌ、収率９３％）を得た。白色粉末の物性は以下のとおりであった。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．８５（ｄ，Ｊ＝１．５Ｈｚ，２Ｈ）、７．６２（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）、７．５２（ｄｄ，Ｊ＝８．１，１．５Ｈｚ，２Ｈ）、７．４８（ｄ，Ｊ＝８．１Ｈｚ，４Ｈ）、７．２３（ｄ，Ｊ＝８．１Ｈｚ，４Ｈ）、２．５７（ｄ，Ｊ＝６．９Ｈｚ，４Ｈ）、１．６９−１．５９（ｍ、２Ｈ）、１．３６−１．２０（ｍ，４８Ｈ）、０．８８（ｔ，Ｊ＝６．９Ｈｚ，１２Ｈ）
ＨＲＭＳ（ＥＩ）：９５８．４５６３（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_６０Ｈ_８０Ｂｒ_２：９５８．４６２７． <Production Example 8: Synthesis of compound represented by formula K (compound K)>

A solution (16 mL) containing tetramethylethylenediamine (TMEDA, 0.06 mL, 0.42 mmol), copper iodide (0.04 g, 0.208 mmol) and acetone is bubbled with air at room temperature and bubbled. An acetone solution (2 mL) containing 3-bromo-4-ethynyl-4 ′-(2-hexyldecyl) biphenyl (Compound J, 2.0 g, 4.2 mmol) was added dropwise to the solution. Subsequently, the mixture was further stirred for 18 hours while bubbling air at room temperature. The solvent was distilled off from the obtained reaction solution with an evaporator, and 1M hydrochloric acid and hexane were added to the obtained residue. The obtained hexane layer was washed with water and saturated brine, dried over magnesium sulfate, and then hexane was distilled off to obtain a crude product. The crude product is purified by silica gel column chromatography (developing solvent: hexane) to obtain 1.85 g (1.92 mmol, 93% yield) of a white powder of the compound represented by formula K (compound K). It was. The physical properties of the white powder were as follows.
¹ H-NMR (CDCl ₃ , δ ppm): 7.85 (d, J = 1.5 Hz, 2H), 7.62 (d, J = 8.1 Hz, 2H), 7.52 (dd, J = 8 .1, 1.5 Hz, 2H), 7.48 (d, J = 8.1 Hz, 4H), 7.23 (d, J = 8.1 Hz, 4H), 2.57 (d, J = 6. 9 Hz, 4H), 1.69-1.59 (m, 2H), 1.36-1.20 (m, 48H), 0.88 (t, J = 6.9 Hz, 12H)
HRMS (EI): 958.4563 (M +). Calcd for C ₆₀ H ₈₀ Br ₂ : 958.4627.

窒素雰囲気下、製造例８で得られた化合物Ｋ（２００ｍｇ、０．２０８ｍｍｏｌ）及びテトラヒドロフラン（５ｍＬ）を混合し、−７８℃まで冷却した。同温度にて得られた混合液にｔ−ＢｕＬｉを１．５９Ｍ含むペンタン溶液を０．５８ｍＬ（ｔ−ＢｕＬｉとして０．９１６ｍｍｏｌ）を滴下し、同温度にてさらに１時間攪拌し、続いて、硫黄粉末（２９ｍｇ、０．９１６ｍｍｏｌ）を加えた後、同温度にて５分間攪拌した。その後、緩やかに室温まで昇温しそのまま２時間攪拌した。別途、窒素バブリングした１M水酸化ナトリウム水溶液（１０ｍL）とＫ_３Ｆｅ（ＣＮ）_６（０．４１ｇ、１．２ｍｍｏｌ）とを、得られた反応溶液に加えて攪拌した後、分液し、得られた有機層をエバポレーターにより濃縮した。濃縮残渣を水および飽和食塩水で洗浄し、クロロホルムにより抽出、硫酸マグネシウムで乾燥後、エバポレーターにより溶媒を留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）にて精製することにより、式Ｌで表される化合物を９１ｍｇ（化合物Ｌ、０．０９８ｍｍｏｌ、４７％）。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：８．０５（ｄ，Ｊ＝１．２Ｈｚ，２Ｈ）、７．８５（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ）、７．７２（ｄｄ，Ｊ＝８．１，１．５Ｈｚ，２Ｈ）、７．５９（ｄ，Ｊ＝８．４Ｈｚ，４Ｈ）、７．２６（ｄ，Ｊ＝８．１Ｈｚ，４Ｈ）、２．５９（ｄ，Ｊ＝６．９Ｈｚ，４Ｈ）、１．７１−１．６３（ｍ，２Ｈ）、１．３３−１．２４（ｍ，４８Ｈ）、０．８８（ｔ，Ｊ＝６．６Ｈｚ，１２Ｈ）
ＨＲＭＳ（ＥＩ）：９２８．５１３６（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_６０Ｈ_８０Ｓ_４：９２８．５１４３． <Production Example 9: Synthesis of compound represented by formula L (compound L)>

Under a nitrogen atmosphere, Compound K (200 mg, 0.208 mmol) obtained in Production Example 8 and tetrahydrofuran (5 mL) were mixed and cooled to -78 ° C. To the mixture obtained at the same temperature, 0.58 mL (0.916 mmol as t-BuLi) of a pentane solution containing 1.59 M of t-BuLi was dropped, and the mixture was further stirred for 1 hour at the same temperature. After adding sulfur powder (29 mg, 0.916 mmol), the mixture was stirred at the same temperature for 5 minutes. Thereafter, the temperature was gradually raised to room temperature and stirred for 2 hours. Separately, nitrogen bubbling 1M aqueous sodium hydroxide solution (10 mL) and K ₃ Fe (CN) ₆ (0.41 g, 1.2 mmol) were added to the obtained reaction solution and stirred, and then separated. The obtained organic layer was concentrated by an evaporator. The concentrated residue was washed with water and saturated brine, extracted with chloroform, dried over magnesium sulfate, and then the solvent was distilled off with an evaporator. By refine | purifying the obtained crude product with silica gel column chromatography (developing solvent: hexane), 91 mg (compound L, 0.098 mmol, 47%) of compounds represented by Formula L are obtained.
¹ H-NMR (CDCl ₃ , δ ppm): 8.05 (d, J = 1.2 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H), 7.72 (dd, J = 8 .1, 1.5 Hz, 2H), 7.59 (d, J = 8.4 Hz, 4H), 7.26 (d, J = 8.1 Hz, 4H), 2.59 (d, J = 6. 9Hz, 4H), 1.71-1.63 (m, 2H), 1.33-1.24 (m, 48H), 0.88 (t, J = 6.6Hz, 12H)
HRMS (EI): 928.5136 (M +). Calcd for C ₆₀ H ₈₀ S ₄ : 928.5143.

窒素雰囲気下、化合物Ｌ（８２ｍｇ、０．０８８ｍｍｏｌ）、ビス（１、５−シクロオクタジエン）ニッケル（０）（２７ｍｇ、０．１４５ｍｍｏｌ）およびトリフェニルホスフィン（５１ｍｇ、０．１９ｍｍｏｌ）にトルエン（６ｍｌ）加え、室温にて１時間攪拌した。得られた反応溶液を１２０℃まで昇温し、同温度にて１０時間攪拌した後、室温まで冷却し、冷却液をセライト濾過した。トルエンを用いてセライトを洗浄し、ろ液をエバポレーターにて濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）にて精製することにより、式Ｍで表される化合物（化合物Ｍ、５１ｍｇ、０．０５７ｍｍｏｌ、６５％）を得た。化合物Ｍの物性は以下のとおりであった。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：８．１１（ｄ，Ｊ＝０．９Ｈｚ，２Ｈ）、７．９３（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ）、７．７１（ｄｄ，Ｊ＝８．４，１．５Ｈｚ，２Ｈ）、７．６０（ｄ，Ｊ＝８．４Ｈｚ，４Ｈ）、７．２６（ｄ，Ｊ＝８．４Ｈｚ，４Ｈ）、２．５９（ｄ，Ｊ＝６．９Ｈｚ，４Ｈ）、１．７１−１．６２（ｍ、２Ｈ）、１．３３−１．２１（ｍ，４８Ｈ）、０．９０−０．８６（ｍ，１２Ｈ）
ＨＲＭＳ（ＥＩ）：８９６．５４２３（Ｍ＋）．Ｃａｌｃｄ ｆｏｒ Ｃ_６０Ｈ_８０Ｓ_３：８９６．５４２２． <Example 1: Synthesis of compound represented by formula M (compound M)>

Under nitrogen atmosphere, compound L (82 mg, 0.088 mmol), bis (1,5-cyclooctadiene) nickel (0) (27 mg, 0.145 mmol) and triphenylphosphine (51 mg, 0.19 mmol) in toluene (6 ml) ) And stirred at room temperature for 1 hour. The resulting reaction solution was heated to 120 ° C., stirred at the same temperature for 10 hours, cooled to room temperature, and the cooling liquid was filtered through Celite. Celite was washed with toluene, and the filtrate was concentrated with an evaporator. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane) to obtain a compound represented by formula M (compound M, 51 mg, 0.057 mmol, 65%). The physical properties of Compound M were as follows.
¹ H-NMR (CDCl ₃ , δ ppm): 8.11 (d, J = 0.9 Hz, 2H), 7.93 (d, J = 8.4 Hz, 2H), 7.71 (dd, J = 8 .4, 1.5 Hz, 2H), 7.60 (d, J = 8.4 Hz, 4H), 7.26 (d, J = 8.4 Hz, 4H), 2.59 (d, J = 6. 9Hz, 4H), 1.71-1.62 (m, 2H), 1.33-1.21 (m, 48H), 0.90-0.86 (m, 12H)
HRMS (EI): 896.5423 (M +). Calcd for C ₆₀ H ₈₀ S ₃ : 896.5422.

Example 2 Production Example 1 of Organic Transistor Using Thin Film and Organic Semiconductor Layer as Thin Film>
Compound M produced in Example 1 is dissolved in o-xylene to prepare an organic solution having a concentration of Compound M of 0.3% by weight.
An organic solution is dropped onto an n-doped silicon wafer with a SiO ₂ thermal oxide film that has been subjected to phenethyltrichlorosilane treatment to form a thin film made of the compound M by spin coating.
Subsequently, a metal mask for forming the source electrode and the drain electrode is placed on the surface of the organic semiconductor layer, and a gold layer having a thickness of 40 nm is formed on the organic semiconductor layer by vacuum deposition, and the source electrode and the drain electrode are formed. An electrode can be formed and an organic transistor as shown in FIG. 2 can be manufactured.

  According to the present invention, a novel organic semiconductor material can be provided.

DESCRIPTION OF SYMBOLS 11 Substrate 12 Gate electrode 13 Gate insulating film 14 Source electrode 15 Drain electrode 16 Organic semiconductor active layer 21 Substrate 22 Source electrode 23 Drain electrode 24 Gate insulating film 25 Gate electrode 26 Organic semiconductor active layer

Claims (12)

Formula (1)

(In the formula, each E independently represents a sulfur or selenium atom.
R ¹ and R ² each independently represent a hydrogen atom, an aryl group having a branched alkyl group, or a heteroaryl group having a branched alkyl group. The total number of carbon atoms of the aryl group having a branched alkyl group is 9 to 30, and the aryl group having the branched alkyl group may have a substituent. The total carbon number of the heteroaryl group having the branched alkyl group is 7 to 30, and the heteroaryl group having the branched alkyl group may have a substituent.
At least one of R ¹ and R ² is the aryl group having the branched alkyl group or the heteroaryl group having the branched alkyl group. )
The substituted benzochalcogenoacene compound represented by these.   2. The compound according to claim 1, wherein all Es in the formula (1) are sulfur atoms. The compound according to claim 1 or 2, wherein R ¹ and R ² in the formula (1) are each independently an aryl group having the branched alkyl group or a hydrogen atom. The compound according to claim 1 or 2, wherein R ¹ and R ² in formula (1) are each independently an aryl group having a branched alkyl group. The compound represented by the formula (1) is represented by the formula (2)

(In the formula, E, R ¹ and R ² represent the same meaning as described above.)
The compound according to claim 1, wherein the compound is represented by the formula:   6. The compound according to claim 5, wherein E in the formula (2) is all sulfur. The compound according to claim 5 or 6, wherein R ¹ and R ² in the formula (2) are each independently an aryl group having a branched alkyl group or a hydrogen atom. 7. The compound according to claim 5, wherein R ¹ and R ² in the formula (2) are both aryl groups having the branched alkyl group.   The thin film containing the compound in any one of Claims 1-8.   A thin film comprising the compound according to claim 1.   The organic-semiconductor device containing the thin film of Claim 9 or 10.   The organic transistor containing the thin film of Claim 9 or 10.

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