TW201841923A - Organic semiconductor and manufacturing method thereof - Google Patents

Abstract

The organic semiconductor of the present invention comprises a strain type compound represented by the following formula (1). (In the formula, Z represents an atom selected from group 13 to 16 elements in the periodic table; rings A1 and A2 are rings having at least one carbon-carbon unsaturated bond; R<SP>1a</SP>, R<SP>1b</SP> and R2 are the same or different and each represents a hydrogen atom or a substituent; R3 represents an atom selected from the group 16 element in the periodic table; R<SP>A</SP> and R<SP>B</SP> are the same or different and each represents a hydrogen atom, a substituent or an atom selected from the group 16 element in the periodic table; m represents an integer of 0 to 4; n represents an integer of 0 to 2; p1 and p2 each represents an integer of 0 or more; and represents a single bond or a double bond). The organic semiconductor has high mobility (electrical mobility) and can be easily or efficiently molded by a wet process such as coating.

Description

有機半導體及其製造方法  Organic semiconductor and method of manufacturing same  

本發明係關於包含具有應變型骨架(例如硫雜環庚烯環等7員環骨架)之縮合多環式化合物之有機半導體及其製造方法，以及包含前述有機半導體之電子裝置(例如有機薄膜電晶體等)。 The present invention relates to an organic semiconductor comprising a condensed polycyclic compound having a strain type skeleton (for example, a 7-membered ring skeleton such as a thiene ring), a method for producing the same, and an electronic device comprising the foregoing organic semiconductor (for example, an organic thin film electric device) Crystal, etc.).

縮合多環式化合物為具有在彼此鄰接的2個以上之環中共有2個以上的原子之結構之多環式化合物，已知複數個5或6員環(例如苯環、噻吩環等)進行縮合而得之縮合多環式芳香族化合物(例如并五苯等并苯系化合物等)等。此種化合物係因廣佈於環上之共軛系統而使π電子離域，同時再配合上分子結構較高的平面性而易於提升在分子間之電子傳導性，便顯示出良好的電特性(半導體特性)，故被利用作為有機半導體材料。 The condensed polycyclic compound is a polycyclic compound having a structure in which two or more atoms are shared by two or more rings adjacent to each other, and a plurality of 5- or 6-membered rings (for example, a benzene ring, a thiophene ring, etc.) are known. A condensed polycyclic aromatic compound (for example, an acene compound such as pentacene) obtained by condensation. This kind of compound exhibits good electrical properties due to the conjugated system widely distributed on the ring, which makes the π-electron delocalized, and at the same time, with the higher planarity of the molecular structure, it is easy to improve the electron conductivity between molecules. (Semiconductor characteristics), it is utilized as an organic semiconductor material.

舉例而言，在日本專利特開平5-55568號公報(專利文獻1)中，已揭示使用經施以摻雜之縮合苯環的數量為4以上且13以下之縮合多環芳香族化合物薄膜之有機薄膜電晶體。在此文獻之實施例中，已記載使用并五苯或 二苯并五苯藉由真空蒸鍍法形成薄膜。 For example, in Japanese Laid-Open Patent Publication No. Hei 5-55568 (Patent Document 1), it is disclosed that a condensed polycyclic aromatic compound film having a number of condensed benzene rings doped with 4 or more and 13 or less is used. Organic thin film transistor. In the examples of this document, it has been described that a film is formed by vacuum evaporation using pentacene or dibenzopentabenzene.

另一方面，藉由塗佈法或印刷法(例如旋轉塗佈等)等濕式製程形成有機半導體層之印刷電子術近年來正受到注目。在印刷電子術中，可在不需要高溫製程之情形下輕易地或效率良好地形成有機半導體層，因而可有效地減低製造成本。此外，由於塑膠基板等耐熱性較低的材料亦變得能夠加以利用，因而亦期待拓展至活用輕量性或柔軟性(或可撓性)等特徵之各種用途。 On the other hand, printed electrons which form an organic semiconductor layer by a wet process such as a coating method or a printing method (for example, spin coating or the like) are attracting attention in recent years. In the printed electronics, the organic semiconductor layer can be formed easily or efficiently without requiring a high-temperature process, and thus the manufacturing cost can be effectively reduced. In addition, since materials having low heat resistance such as a plastic substrate can be utilized, it is expected to be expanded to various applications in which characteristics such as light weight or flexibility (or flexibility) are utilized.

然而，專利文獻1中所記載之并五苯等并苯系化合物不僅分子結構的平面性較高，而且受到π-π相互作用等之影響，分子彼此易於凝集，因而對有機溶媒之溶解性係極端地低。因此，應用於藉由濕式製程形成有機半導體層之印刷電子術實屬困難。 However, the acene compound such as pentacene described in Patent Document 1 has high molecular structure and is affected by π-π interaction, etc., and molecules are easily aggregated with each other, so that the solubility to the organic solvent is Extremely low. Therefore, it is difficult to apply to a printed electron for forming an organic semiconductor layer by a wet process.

為了改善此種縮合多環式化合物的溶解性，已採取導入長鏈烷基等作為取代基而使溶解度提升之措施。但是，由於絕緣性較高的長鏈烷基的導入會成為移動度(電移動度(electrical mobility))降低之原因，因而縮合多環式化合物的溶解性與移動度係處於權衡(trade-off)關係，兼顧此等特性係極為困難。 In order to improve the solubility of such a condensed polycyclic compound, measures have been taken to introduce a long-chain alkyl group or the like as a substituent to improve the solubility. However, since the introduction of a long-chain alkyl group having a high insulating property causes a decrease in mobility (electrical mobility), the solubility and mobility of the condensed polycyclic compound are trade-off (trade-off). Relationships, taking into account these characteristics is extremely difficult.

又，若使用具有前述長鏈烷基之化合物形成有機電晶體等元件，則元件的操作電壓會有變高之傾向。即，可能由於前述長鏈烷基係在裝置界面(電極/有機半導體界面等)捕捉載子而使接觸電阻增大，因而特別是在驅動初期(電流上升)之移動度變小，元件的電流注入電阻 增加至數十至數千kΩ‧cm左右。因此，元件的操作電壓高達數十至100V左右，無法減低實用上之操作電壓。 Moreover, when an element such as an organic transistor is formed using a compound having the long-chain alkyl group, the operating voltage of the element tends to be high. In other words, the long-chain alkyl group may increase the contact resistance at the device interface (electrode/organic semiconductor interface, etc.), so that the mobility at the initial stage of driving (current rise) is small, and the current of the element is small. The injection resistance is increased to several tens to several thousands kΩ ‧ cm. Therefore, the operating voltage of the component is as high as several tens to 100 volts, and the practical operating voltage cannot be reduced.

此外，在使用具有前述長鏈烷基之化合物所形成之元件中，移動度亦有易於偏差之傾向。詳細而言，在使用具有烷基之縮合多環式化合物將有機半導體層予以塗佈成形之情況，係由於相分離，而在有機半導體層內形成柔軟的烷基凝集而得之烷基部分以及剛性的縮合環骨架堆疊而得之縮合環骨架部分。前述烷基部分及縮合環骨架部分通常係以交替積層之形態形成，已知儘管在縮合環骨架堆疊之方向(π堆疊方向或結晶生長方向)的導電性(或移動度)優異，但在垂直於前述π堆疊方向之疊層方向(烷基部分與縮合環部分交互排列(累積)之方向或縮合環骨架之面方向)受到烷基部分之影響，移動度極端地降低。由於此移動度的各向異性，難以使移動度三維均勻化，且會依元件使偏差變大。 Further, in the element formed using the compound having the aforementioned long-chain alkyl group, the mobility tends to be liable to be deviated. Specifically, in the case where an organic semiconductor layer is coated and formed by using a condensed polycyclic compound having an alkyl group, an alkyl moiety obtained by forming a soft alkyl group in the organic semiconductor layer due to phase separation and The rigid fused ring skeleton is stacked to obtain a condensed ring skeleton portion. The aforementioned alkyl moiety and condensed ring skeleton moiety are usually formed in the form of alternating laminates, and it is known that although the conductivity (or mobility) in the direction of the condensed ring skeleton stack (the π stacking direction or the crystal growth direction) is excellent, it is vertical. In the lamination direction of the aforementioned π stacking direction (the direction in which the alkyl moiety and the condensed ring portion are alternately aligned (accumulated) or the direction of the surface of the condensed ring skeleton) is affected by the alkyl moiety, and the mobility is extremely lowered. Due to the anisotropy of this mobility, it is difficult to make the mobility three-dimensionally uniform, and the variation is made large by the components.

如此，儘管烷基使半導體特性顯著降低，但由於不具有烷基且不存在溶解(或可製膜)之縮合多環式化合物，故要提升藉由濕式製程所形成之有機半導體的性能係極為困難。 Thus, although the alkyl group significantly degrades the semiconductor characteristics, since there is no alkyl group and there is no dissolved (or film-formable) condensed polycyclic compound, the performance of the organic semiconductor formed by the wet process is improved. Extremely difficult.

另外，在日本特開2009-234958號公報(專利文獻2)中，已揭示2個苯環與7員環進行縮合而得之縮合環化合物(例如二苯并[b,f]硫雜環庚烯衍生物等)之製造方法，在實施例中調製出二苯并[b,f]硫雜環庚烯。但是，在此文獻中，儘管已記載可將所調製之縮合環化合物利用 作為醫藥品的有效成分或其合成中間體，但針對在半導體領域中加以利用則沒有任何揭示。 Further, in Japanese Laid-Open Patent Publication No. 2009-234958 (Patent Document 2), a condensed ring compound obtained by condensing two benzene rings and a 7-membered ring (for example, dibenzo[b,f]thioheptane has been disclosed. In the production method of an olefin derivative or the like, dibenzo[b,f]thiaheptene is prepared in the examples. However, in this document, although it has been described that the condensed ring compound to be prepared can be used as an active ingredient of a pharmaceutical or a synthetic intermediate thereof, it is not disclosed for use in the field of semiconductors.

[先前技術文獻]  [Previous Technical Literature]   [專利文獻]  [Patent Literature]  

[專利文獻1]日本特開平5-55568號公報(申請專利範圍、實施例) [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 5-55568 (Application No. Patent Application, Examples)

[專利文獻2]日本特開2009-234958號公報(段落[0001][0053][0054]、實施例) [Patent Document 2] Japanese Laid-Open Patent Publication No. 2009-234958 (paragraph [0001] [0053] [0054], Examples

從而，本發明之目的係在於提供具有高移動度(電移動度或載子移動度)，同時能夠藉由塗佈等濕式製程進行成形之有機半導體及其製造方法以及包含前述有機半導體之電子裝置。 Accordingly, an object of the present invention is to provide an organic semiconductor having high mobility (electric mobility or carrier mobility) while being capable of being formed by a wet process such as coating, a method of manufacturing the same, and an electron including the foregoing organic semiconductor Device.

本發明之其他目的係在於提供可形成操作電壓(或閾值電壓的絕對值)較低且移動度的偏差小的元件之有機半導體及其製造方法以及包含前述有機半導體之電子裝置。 Another object of the present invention is to provide an organic semiconductor which can form an element having a low operating voltage (or an absolute value of a threshold voltage) and a small variation in mobility, a method of manufacturing the same, and an electronic device including the organic semiconductor.

本發明者等人為了達成前述課題而致力檢討之結果，發現若將相較於5或6員環而言環的應變稍大的7員環骨架(應變型骨架)導入至縮合多環式化合物中，則可在未顯著減低移動度之情形下有效地提升溶解性，遂 完成本發明。 In order to achieve the above-mentioned problems, the inventors of the present invention have conducted a review and found that a 7-membered ring skeleton (strain type skeleton) having a slightly larger strain than a 5- or 6-membered ring is introduced into a condensed polycyclic compound. In the present case, the solubility can be effectively improved without significantly reducing the degree of mobility, and the present invention has been completed.

即，本發明之有機半導體包含：包含下述式(1)所示之化合物之有機半導體。 That is, the organic semiconductor of the present invention contains an organic semiconductor containing a compound represented by the following formula (1).

(式中，Z表示選自週期表第13至16族元素之原子；環A¹及A²係相同或相異且表示具有至少1個碳-碳不飽和鍵之環；R^1a、R^1b及R²係相同或相異且表示氫原子或取代基；R³表示選自週期表第16族元素之原子；R^A及R^B係相同或相異且表示氫原子、取代基或選自週期表第16族元素之原子；m表示0至4的整數；n表示0至2的整數；p1及p2係相同或相異且表示0以上的整數； Wherein Z represents an atom selected from Groups 13 to 16 of the Periodic Table; rings A ¹ and A ² are the same or different and represent a ring having at least one carbon-carbon unsaturated bond; R ^1a , R ^1b And R ² are the same or different and represent a hydrogen atom or a substituent; R ³ represents an atom selected from the group 16 element of the periodic table; R ^A and R ^B are the same or different and represent a hydrogen atom, a substituent or a selected from An atom of a group 16 element of the periodic table; m represents an integer of 0 to 4; n represents an integer of 0 to 2; and p1 and p2 are the same or different and represent an integer of 0 or more;

所示之鍵結表示單鍵或雙鍵)。 The bond shown represents a single or double bond).

在前述式(1)中，環A¹及A²可為可具有雜原子之芳香族環。此外，前述式(1)所示之化合物可為選自下述式(1A)及下述式(1B)所示之化合物之至少1種。 In the above formula (1), the rings A ¹ and A ² may be an aromatic ring which may have a hetero atom. In addition, the compound represented by the above formula (1) may be at least one selected from the group consisting of the compounds represented by the following formula (1A) and the following formula (1B).

(式中，環Ar¹及Ar²係相同或相異且表示芳烴環；R^a及R^b係相同或相異且表示取代基；q1及q2係相同或相異且表示0以上的整數；Z、R^1a、R^1b、R²、R³、m、n係與前述式(1)相同)。 (wherein the rings Ar ¹ and Ar ² are the same or different and represent an aromatic hydrocarbon ring; R ^a and R ^b are the same or different and represent a substituent; and q1 and q2 are the same or different and represent an integer of 0 or more; Z, R ^1a , R ^1b , R ² , R ³ , m, and n are the same as the above formula (1).

(式中，Z¹及Z²係相同或相異且表示選自週期表第13族至16族元素之原子；R^2a、R^2b、R^4a、R^4b、R^5a及R^5b係相同或相異且表示氫原子或取代基；R^3a及R^3b係相同或相異且表示選自週期表第16族元素之原子；m1及m2係相同或相異且表示0至4的整數；n1及n2係相同或相異且表示0至2的整數；Z、R^1a、R^1b、R²、R³、m、n係與前述式(1)相同)。 (wherein Z ¹ and Z ² are the same or different and represent an atom selected from Group 13 to Group 16 elements of the periodic table; R ^2a , R ^2b , R ^4a , R ^4b , R ^5a and R ^5b are the same or Different from each other and representing a hydrogen atom or a substituent; R ^3a and R ^3b are the same or different and represent an atom selected from elements of Group 16 of the periodic table; m1 and m2 are the same or different and represent an integer from 0 to 4; n1 And n2 are the same or different and represent an integer of 0 to 2; Z, R ^1a , R ^1b , R ² , R ³ , m, n are the same as the above formula (1)).

在前述式(1A)中，Z可為選自週期表第14至16族元素之原子(例如選自碳、矽、鍺、錫、氮、磷、 砷、銻、氧、硫、硒及碲之原子；較佳為選自碳、矽、鍺、氮、磷、砷、氧、硫及硒之原子等)；環Ar¹及Ar²可為C_6-18芳烴環(例如C_6-14芳烴環；較佳為萘環等C_6-10芳烴環等)；R^1a、R^1b及R²可為氫原子或烴基(例如氫原子、烷基、環烷基或芳基；較佳係R^1a及R^1b為氫原子或C_1-30烷基，R²為氫原子、C_1-10烷基、C_5-8環烷基或C_6-10芳基等)；R^a及R^b可為烴基(例如烷基、環烷基或芳基)；R³可為氧原子或硫原子(例如氧原子)；m可為0至3左右的整數(例如0至2左右的整數)；q1及q2可為0至8左右的整數(例如0至4左右的整數；較佳為0)。 In the above formula (1A), Z may be an atom selected from elements of Groups 14 to 16 of the periodic table (for example, selected from the group consisting of carbon, germanium, antimony, tin, nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, and antimony). An atom; preferably an atom selected from the group consisting of carbon, ruthenium, osmium, nitrogen, phosphorus, arsenic, oxygen, sulfur, and selenium; and the ring Ar ¹ and Ar ² may be a C _6-18 arene ring (eg, C _6-14) An aromatic hydrocarbon ring; preferably a C _6-10 arene ring such as a naphthalene ring; etc.; R ^1a , R ^1b and R ² may be a hydrogen atom or a hydrocarbon group (for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group; R ^1a and R ^1b are a hydrogen atom or a C _1-30 alkyl group, R ² is a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group or a C _6-10 aryl group, etc.; R ^a and R ^b may be a hydrocarbon group (for example, an alkyl group, a cycloalkyl group or an aryl group); R ³ may be an oxygen atom or a sulfur atom (for example, an oxygen atom); m may be an integer of about 0 to 3 (for example, an integer of about 0 to 2) ;q1 and q2 may be integers from 0 to 8 (for example, an integer of from 0 to 4; preferably 0).

在前述式(1B)中，Z、Z¹及Z²可為選自週期表第14至16族元素之原子(例如選自碳、矽、鍺、錫、氮、磷、砷、銻、氧、硫、硒及碲之原子；較佳係Z為選自碳、矽、鍺、氮、磷、砷、氧、硫及硒之原子，Z及Z²為選自氧、硫及硒之原子等)；R^1a、R^1b、R²、R^2a、R^2b、R^5a及R^5b可為氫原子或烴基(例如氫原子、烷基、環烷基或芳基；較佳係R^1a及R^1b為氫原子或C_1-30烷基，R^5a及R^5b為氫原子，R²、R^2a及R^2b為氫原子、C_1-10烷基、C_5-8環烷基或C_6-10芳基等)；R³、R^3a及R^3b可為氧原子或硫原子(例如氧原子等)；R^4a及R^4b可為氫原子、鹵素原子、烴基、可具有烴基之雜芳基、鋰原子、-B(OH)₂基、-ZnX⁴基(式中，X⁴表示鹵素原子)、-MgX⁵基(式中，X⁵表示鹵素原子)、-Sn(R⁸)₃基(式中，R⁸表示烷基)或-Si(R⁹)₃基(式中，R⁹表示氟、氯或烷基)[例如氫原子、鹵素原子、芳基、烷芳基、 雜芳基或烷基雜芳基；較佳為氫原子、鹵素原子、C_6-14芳基、C_1-20烷基C_6-14芳基、C_4-13雜芳基或C_1-20烷基C_4-13雜芳基等]；m、m1及m2可為0至3左右的整數(例如0至2左右的整數；較佳係m1及m2為0)；n1及n2可為0。另外，在Z、Z¹及Z²皆為硫原子之情況，R^4a及R^4b可為氫原子、鹵素原子、可具有烴基之雜芳基、鋰原子、-B(OH)₂基、-ZnX⁴基(式中，X⁴表示鹵素原子)、-MgX⁵基(式中，X⁵表示鹵素原子)、-Sn(R⁸)₃基(式中，R⁸表示烷基)或-Si(R⁹)₃基(式中，R⁹表示氟、氯或烷基)[例如氫原子、鹵素原子、雜芳基或烷基雜芳基；較佳為氫原子、鹵素原子、C_4-13雜芳基或C_1-20烷基C_4-13雜芳基等]。 In the above formula (1B), Z, Z ¹ and Z ² may be an atom selected from elements of Groups 14 to 16 of the periodic table (for example, selected from the group consisting of carbon, ruthenium, osmium, tin, nitrogen, phosphorus, arsenic, antimony, oxygen). , sulfur, selenium and antimony atoms; preferably Z is an atom selected from the group consisting of carbon, germanium, germanium, nitrogen, phosphorus, arsenic, oxygen, sulfur and selenium, and Z and Z ² are atoms selected from the group consisting of oxygen, sulfur and selenium. And R ^1a , R ^1b , R ² , R ^2a , R ^2b , R ^5a and R ^5b may be a hydrogen atom or a hydrocarbon group (for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group; preferably R ^1a and R ^1b is a hydrogen atom or a C _1-30 alkyl group, R ^5a and R ^5b are a hydrogen atom, and R ² , R ^2a and R ^2b are a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group or C _6-10 aryl, etc.; R ³ , R ^3a and R ^3b may be an oxygen atom or a sulfur atom (for example, an oxygen atom or the like); and R ^4a and R ^4b may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group. An aryl group, a lithium atom, a -B(OH) ₂ group, a -ZnX ⁴ group (wherein X ⁴ represents a halogen atom), a -MgX ⁵ group (wherein, X ⁵ represents a halogen atom), -Sn(R ⁸ ) ₃ group (wherein, R ⁸ represents an alkyl group), or -Si (R ⁹⁾ ₃ group (wherein, R ⁹ represents a fluorine, chlorine or alkyl) [e.g. a hydrogen atom, a halogen atom, an aryl group, alkaryl , Heteroaryl or alkylheteroaryl; is preferably a hydrogen atom, a halogen atom, a C _6-14 aryl group, C _1-20 alkyl C _6-14 aryl, C _4-13 heteroaryl or C _{1 -20} alkyl C _4-13 heteroaryl or the like]; m, m1 and m2 may be an integer of about 0 to 3 (for example, an integer of about 0 to 2; preferably m1 and m2 are 0); n1 and n2 may be Is 0. Further, in the case where Z, Z ¹ and Z ² are each a sulfur atom, R ^4a and R ^4b may be a hydrogen atom, a halogen atom, a heteroaryl group which may have a hydrocarbon group, a lithium atom, a -B(OH) ₂ group, - ZnX ⁴ group (wherein X ⁴ represents a halogen atom), -MgX ⁵ group (wherein, X ⁵ represents a halogen atom), -Sn(R ⁸ ) ₃ group (wherein R ⁸ represents an alkyl group) or -Si (R ⁹ ) ₃ (wherein R ⁹ represents fluorine, chlorine or an alkyl group) [for example, a hydrogen atom, a halogen atom, a heteroaryl group or an alkylheteroaryl group; preferably a hydrogen atom, a halogen atom, or a C _{4- 13} heteroaryl or C _1-20 alkyl C _4-13 heteroaryl, etc.].

此外，在本發明中，亦包括：包含前述式(1)所示之化合物及溶媒之組成物；在基材的至少一面，塗佈前述組成物，並將溶媒去除而製造有機半導體之方法；以及包含前述有機半導體之電子裝置。 Further, the present invention also includes a method comprising the composition of the compound represented by the above formula (1) and a solvent; and coating the composition on at least one side of the substrate, and removing the solvent to produce an organic semiconductor; And an electronic device including the aforementioned organic semiconductor.

在本發明中，由於縮合多環式化合物具有相較於5或6員環而言經少許應變之7員環骨架(應變型骨架)，因而3維偶極(雙極)矩變大，且可能由於在分子間產生間隙，溶媒變得易於滲入，因而即便不具有長鏈烷基等之取代基而對有機溶媒之溶解性較高，故可藉由塗佈等濕式製程而輕易且效率良好地形成有機半導體。且，可能由於前述應變型骨架係經適度地應變，因而不會有阻礙在分子間之電子軌道的重疊之情形，故本發明之有機半導體可 實現較高的移動度(電移動度或載子移動度)。因此，本發明之有機半導體可以更高的程度兼顧成形性及移動度。若使用此種有機半導體，則可形成操作電壓(或閾值電壓的絕對值)較低且移動度的偏差較小的元件。 In the present invention, since the condensed polycyclic compound has a 7-membered ring skeleton (strain type skeleton) which is slightly strained compared to the 5- or 6-membered ring, the 3D dipole (bipolar) moment becomes large, and Since a solvent may be easily infiltrated by a gap between the molecules, the solubility in the organic solvent is high even without a substituent such as a long-chain alkyl group, so that it can be easily and efficiently performed by a wet process such as coating. An organic semiconductor is formed well. Moreover, since the strain-type skeleton is moderately strained, and thus there is no hindrance of overlapping of electron orbitals between molecules, the organic semiconductor of the present invention can achieve higher mobility (electric mobility or carrier). Mobility). Therefore, the organic semiconductor of the present invention can achieve both formability and mobility with a higher degree. When such an organic semiconductor is used, an element having a low operating voltage (or an absolute value of the threshold voltage) and a small variation in mobility can be formed.

[式(1)所示之化合物(亦稱為應變型化合物)] [Compound represented by formula (1) (also called strain type compound)]

本發明之有機半導體中所包含之應變型化合物係由下述式(1)表示。 The strain type compound contained in the organic semiconductor of the present invention is represented by the following formula (1).

(式中，Z表示選自週期表第13至16族元素之原子；環A¹及A²表示具有至少1個碳-碳不飽和鍵之環；R^1a、R^1b及R²係相同或相異且表示氫原子或取代基；R³表示選自週期表第16族元素之原子；R^A及R^B係相同或相異且表示氫原子、取代基或選自週期表第16族元素之原子；m表示0至4的整數；n表示0至2的整數；p1及p2表示0以上的整數； (wherein Z represents an atom selected from the group consisting of elements of Groups 13 to 16 of the periodic table; and rings A ¹ and A ² represent a ring having at least one carbon-carbon unsaturated bond; R ^1a , R ^1b and R ² are the same or Different from each other and representing a hydrogen atom or a substituent; R ³ represents an atom selected from the group 16 element of the periodic table; R ^A and R ^B are the same or different and represent a hydrogen atom, a substituent or an element selected from Group 16 of the periodic table. An atom; m represents an integer from 0 to 4; n represents an integer from 0 to 2; and p1 and p2 represent an integer of 0 or more;

所示之鍵結表示單鍵或雙鍵)。 The bond shown represents a single or double bond).

在前述式(1)中，Z所表示之原子為選自週期表第13族(3B族)元素、第14族(4B族)元素、第15族(5B族)元素及第16族(6B族)元素之原子，作為週期表第13族(3B族)元素，可列舉例如硼(B)、鋁(Al)、鎵(Ga)、銦(In)、鉈(Tl)[較佳為硼、鋁、鎵、銦，更佳為硼、鋁、鎵，特別是硼等]等。 In the above formula (1), the atom represented by Z is selected from the group consisting of Group 13 (Group 3B) elements, Group 14 (Group 4B) elements, Group 15 (Group 5B) elements, and Group 16 (6B) of the periodic table. The atom of the group element, as the group 13 (Group 3B) element of the periodic table, may, for example, be boron (B), aluminum (Al), gallium (Ga), indium (In), or lanthanum (Tl) [preferably boron) , aluminum, gallium, indium, more preferably boron, aluminum, gallium, especially boron, etc.].

作為週期表第14族(4B族)元素，可列舉例如碳(C)、矽(Si)、鍺(Ge)、錫(Sn)、鉛(Pb)[較佳為碳、矽、鍺、錫，更佳為碳、矽、鍺，特別是矽等]等。 Examples of the Group 14 (Group 4B) element of the periodic table include carbon (C), germanium (Si), germanium (Ge), tin (Sn), and lead (Pb) (preferably carbon, germanium, antimony, tin). More preferably, carbon, bismuth, bismuth, especially bismuth, etc.

作為週期表第15族(5B族)元素，可列舉例如氮(N)、磷(P)、砷(As)、銻(Sb)、鉍(Bi)[較佳為氮、磷、砷、銻，更佳為氮、磷、砷，特別是磷等]等。 Examples of the Group 15 (Group 5B) element of the periodic table include nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi) (preferably nitrogen, phosphorus, arsenic, antimony). More preferably, it is nitrogen, phosphorus, arsenic, especially phosphorus, etc.

作為週期表第16族(6B族)元素，可列舉例如氧(O)、硫(S)、硒(Se)、碲(Te)、釙(Po)[較佳為氧、硫、硒、碲，更佳為氧、硫、硒，特別是硫、硒等]等。 Examples of the Group 16 (Group 6B) element of the periodic table include oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and strontium (Po) (preferably oxygen, sulfur, selenium, tellurium). More preferably, it is oxygen, sulfur, selenium, especially sulfur, selenium, etc.].

作為較佳的Z所表示之原子，為選自由週期表第14族元素、第15族元素、第16族元素所組成群組之原子(例如選自碳、矽、鍺、錫、氮、磷、砷、銻、氧、硫、硒及碲之原子等)，更佳係可為選自矽、鍺、氮、磷、砷、氧、硫及硒之原子(例如選自矽、鍺、磷、砷、硫及硒之原子等)等。 The atom represented by the preferred Z is an atom selected from the group consisting of a Group 14 element, a Group 15 element, and a Group 16 element of the periodic table (for example, selected from the group consisting of carbon, ruthenium, osmium, tin, nitrogen, and phosphorus). , atoms of arsenic, antimony, oxygen, sulfur, selenium and tellurium, etc., more preferably atoms selected from the group consisting of ruthenium, osmium, nitrogen, phosphorus, arsenic, oxygen, sulfur and selenium (for example, selected from the group consisting of ruthenium, osmium, and phosphorus) , arsenic, sulfur and selenium atoms, etc.).

Z所表示之原子的各原子價(價數)v為2至6價，滿足v=m+2×n+2。此外，原子價v可因應所對應之原子(Z)的種類而選擇，舉例而言，就週期表第13族元素(例如硼)而言多數情況為3價，就週期表第14族元素(例如碳、矽等)而言多數情況為2價或4價(特別是4價)，就週期表第15族元素(例如氮、磷等)而言多數情況為3至5價，就週期表第16族元素(例如氧、硫、硒等)而言多數情況為2至6價。 The valence (valence) v of each atom of the atom represented by Z is 2 to 6 valence, and satisfies v = m + 2 × n + 2. In addition, the valence v may be selected depending on the type of atom (Z) to which it corresponds, for example, in the case of a group 13 element of the periodic table (for example, boron), most of the cases are trivalent, and elements of the 14th group of the periodic table ( For example, carbon, antimony, etc., in most cases, it is divalent or tetravalent (especially tetravalent), and in the case of elements of Group 15 of the periodic table (such as nitrogen, phosphorus, etc.), most of the cases are 3 to 5, and the periodic table Group 16 elements (eg, oxygen, sulfur, selenium, etc.) are mostly 2 to 6 valences.

A¹及A²所表示之環係共有包含Z原子之7員環之2,3-位及6,7-位的碳原子(C=C鍵)而形成縮合環。因此，環A¹及A²在具有至少1個碳-碳不飽和鍵(C=C鍵)之前提下並無特別限制，可為具有雜原子(例如氮(N)、氧(O)、硫(S)等)之雜環(heterocyclic ring)，亦可為不具有雜原子之烴環。作為此種環，可列舉例如脂肪族環{例如脂肪族烴環[例如環烯環(環戊烯環、環己烯環等)等單環式脂肪族環；橋聯環(莰烯(冰片烯)環、降莰烯環、二環戊二烯環等)等多環式脂肪族環等]；脂肪族雜環[例如3-吡咯啉、二氫哌喃等具有雜原子(氮(N)、氧(O)、硫(S)等)之脂肪族環等]等}；芳香族環等。此等環A¹及A²之中，由電特性(半導體特性)優異之方面而言，通常多數情況為可具有雜原子之芳香族環[例如芳香族烴環(芳烴環)、芳香族雜環(雜芳烴環)等]。 The ring system represented by A ¹ and A ² has a carbon atom (C=C bond) of a 2,3-position and a 6,7-position of a 7-membered ring of a Z atom to form a condensed ring. Therefore, the ring A ¹ and A ² are not particularly limited as long as they have at least one carbon-carbon unsaturated bond (C=C bond), and may have a hetero atom (for example, nitrogen (N), oxygen (O), A heterocyclic ring of sulfur (S) or the like may also be a hydrocarbon ring having no hetero atom. Examples of such a ring include an aliphatic ring (for example, an aliphatic hydrocarbon ring [for example, a monocyclic aliphatic ring such as a cycloolefin ring (cyclopentene ring or a cyclohexene ring); a bridged ring (terpene (borneon) a polycyclic aliphatic ring or the like such as an alkene ring, a decene ring, a dicyclopentadiene ring or the like; an aliphatic heterocyclic ring [for example, a 3-pyrroline, a dihydropyran, etc. having a hetero atom (nitrogen (N) ), an aliphatic ring of oxygen (O), sulfur (S), etc., etc.]; an aromatic ring or the like. Among these rings A ¹ and A ² , in general, in terms of electrical properties (semiconductor properties), an aromatic ring which may have a hetero atom (for example, an aromatic hydrocarbon ring (aromatic hydrocarbon ring) or an aromatic hybrid) is usually used in many cases. Ring (heteroarene ring), etc.].

作為芳香族烴環(芳烴環)，可列舉例如苯環等單環式芳烴環；縮合多環式芳烴環[例如茚環、二氫茚環、 萘環、四氫萘環、薁環、苯并二茚環、乙烯合萘(acenaphthylene)環、聯伸二苯環、茀環、蒽環、菲環、萉(phenalene)環、丙二烯合茀(fluoranthene)環、乙烯合蒽(aceanthrylene)環、乙烯合菲(acephenanthrylene)環、并四苯環、1,2-苯并菲(chrysene)環、芘(pyrene)環、聯伸三苯環、并五苯環、異并五苯(pentaphene)環、苉(picene)環、苝(perylene)環等C_9-30縮合多環式芳烴環，較佳為縮合多環式C_9-26芳烴環等]等。作為較佳的芳香族烴環，可為C_6-22芳烴環(例如C_6-18芳烴環)，更佳為C_6-14芳烴環(例如C_6-10芳烴環)，特別是苯環或萘環(特別是萘環)。 Examples of the aromatic hydrocarbon ring (aromatic hydrocarbon ring) include a monocyclic aromatic hydrocarbon ring such as a benzene ring; and a condensed polycyclic aromatic hydrocarbon ring [e.g., an anthracene ring, an indoline ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, and a benzene group). Diterpene ring, acenaphthylene ring, extended diphenyl ring, anthracene ring, anthracene ring, phenanthrene ring, phenalene ring, fluoranthene ring, aceanthrylene ring , acephenanthrylene ring, tetracene ring, 1,2-benzopyrene ring, pyrene ring, extended triphenyl ring, pentacene ring, pentaphene ring A C _9-30 condensed polycyclic aromatic hydrocarbon ring such as a picene ring or a perylene ring is preferably a condensed polycyclic C _9-26 aromatic hydrocarbon ring or the like. As a preferred aromatic hydrocarbon ring, it may be a C _6-22 arene ring (for example, a C _6-18 arene ring), more preferably a C _6-14 arene ring (for example, a C _6-10 arene ring), particularly a benzene ring. Or a naphthalene ring (especially a naphthalene ring).

作為芳香族雜環(雜芳烴環)，可列舉例如單環式雜芳烴環[例如含氮(N)單環式雜芳烴環(例如吡咯環、咪唑環、吡唑環、吡啶環、吡環、嘧啶環、嗒環等)；含氧(O)單環式雜芳烴環(例如呋喃環、哌喃環等)；含硫(S)單環式雜芳烴環(例如噻吩環等)；含有2種以上雜原子之單環式雜芳烴環(例如唑環、異唑環、噻唑環、異噻唑環、噻環、呋呫環、噻二環等)等C_2-5雜芳烴環，較佳為C_3-5雜芳烴環等]；多環式雜芳烴環[例如含氮(N)多環式雜芳烴環(例如吲環、吲哚環、3H-吲哚環、異吲哚環、1H-吲唑環、嘌呤環、喹啉環、異喹啉環、4H-喹環、呔環、啶環、喹啉環、喹唑啉環、噌啉(cinnoline)環、喋啶環、咔唑環、4aH-咔唑環、β-咔啉環、吖啶環、啡啶環、啡環、啡啉環、呸啶(perimidine)環等)；含氧(O)多環式雜芳烴環(例如苯并呋喃環、異苯并呋喃環、苯并哌喃 (chromene)環、二氫苯并哌喃(chroman)環、異二氫苯并哌喃環、二苯并哌喃(xanthene)環等)；含硫(S)多環式雜芳烴環(例如苯并噻吩環、噻吩并噻吩環、噻嗯環等)；含有2種以上雜原子之多環式雜芳烴環(例如噻吩并呋喃環、咪唑并噻唑環、啡環、啡噻環、啡噻(phenoxathiin)環、啡呻(phenarsazine)環等)等C_6-20雜芳烴環(較佳為C_6-16雜芳烴環)等]等。作為較佳的雜芳烴環，可為C_2-13雜芳烴環(例如含氮(N)單環式或多環式C_2-13雜芳烴環、含硫(S)單環式或多環式C_2-13雜芳烴環等)，更佳為C_3-9雜芳烴環(特別是噻吩環、苯并噻吩環等含硫(S)單環式或多環式C_3-9雜芳烴環等)。 The aromatic heterocyclic ring (heteroaromatic hydrocarbon ring) may, for example, be a monocyclic heteroaromatic ring [for example, a nitrogen-containing (N) monocyclic heteroaromatic ring (for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyridyl ring). Ring, pyrimidine ring, anthracene Ring (etc.); oxygen-containing (O) monocyclic heteroaromatic ring (eg, furan ring, piper ring, etc.); sulfur-containing (S) monocyclic heteroaromatic ring (eg, thiophene ring, etc.); containing more than 2 kinds of heteroatoms Monocyclic heteroaromatic ring (eg Oxazole ring, different Oxazole ring, thiazole ring, isothiazole ring, thiophene Ring, furazan ring, thiazepine a C _2-5 heteroaromatic ring, preferably a C _3-5 heteroaromatic ring, etc.; a polycyclic heteroaromatic ring [eg a nitrogen-containing (N) polycyclic heteroaromatic ring (eg, hydrazine) Ring, anthracene ring, 3H-fluorene ring, isoindole ring, 1H-carbazole ring, anthracene ring, quinoline ring, isoquinoline ring, 4H-quin Ring, 呔 ring, Acridine ring Phytoline, quinazoline ring, cinnoline ring, acridine ring, indazole ring, 4aH-carbazole ring, β-porphyrin ring, acridine ring, pyridine ring, brown Ring, phenanthroline ring, perimidine ring, etc.; oxygen-containing (O) polycyclic heteroaromatic ring (eg benzofuran ring, isobenzofuran ring, chromene ring, dihydrogen) a chroman ring, an iso-dihydrobenzopyran ring, a xanthene ring, etc.; a sulfur-containing (S) polycyclic heteroaryl ring (eg, a benzothiophene ring, thienophene) a thiophene ring, a thiene ring, etc.; a polycyclic heteroaromatic ring containing two or more kinds of hetero atoms (for example, a thienofuran ring, an imidazothiazole ring, a brown Ring, thiophene Ring, brown Thiophene ring, morphine (phenarsazine) ring or the like, a C _6-20 heteroaromatic ring (preferably a C _6-16 heteroaromatic ring), etc.]. As a preferred heteroaromatic ring, it may be a C _2-13 heteroaromatic ring (for example, a nitrogen-containing (N) monocyclic or polycyclic C _2-13 heteroaromatic ring, a sulfur-containing (S) monocyclic or polycyclic ring. a C _2-13 heteroaromatic ring or the like), more preferably a C _3-9 heteroaromatic ring (especially a sulfur-containing (S) monocyclic or polycyclic C _3-9 heteroaromatic hydrocarbon such as a thiophene ring or a benzothiophene ring; Ring, etc.).

此等環A¹及A²之中，較佳為C_6-30芳烴環或C_2-20雜芳烴環，該等之中，較佳為C_6-14芳烴環或C_2-13雜芳烴環，特別是C_6-10芳烴環或C_4-8雜芳烴環(例如苯環、萘環、噻吩環、苯并噻吩環，特別是萘環或噻吩環)。此外，環A¹及A²的種類可相異，但通常大多係相同。另外，在環A¹及A²中，縮合位置(共有包含Z原子之7員環之2,3-位及6,7-位的碳原子(C=C鍵)之位置)並無特別限制。 Among these rings A ¹ and A ² , a C _6-30 aromatic hydrocarbon ring or a C _2-20 hetero arene ring is preferred, and among these, a C _6-14 aromatic hydrocarbon ring or a C _2-13 heteroaromatic hydrocarbon is preferred. Ring, especially a C _6-10 arene ring or a C _4-8 heteroarene ring (for example a benzene ring, a naphthalene ring, a thiophene ring, a benzothiophene ring, in particular a naphthalene ring or a thiophene ring). Further, the types of the rings A ¹ and A ² may be different, but usually they are usually the same. Further, in the rings A ¹ and A ² , the condensation position (the position of the carbon atom (C=C bond) of the 2,3-position and the 6,7-position of the 7-membered ring containing the Z atom is not particularly limited). .

作為R^1a及R^1b所表示之取代基，可列舉例如烴基{例如烷基(例如甲基、乙基、丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正己基、正辛基、2-乙基己基、正癸基、正十二烷基(月桂基)等直鏈狀或分枝鏈狀C_1-30烷基，較佳為直鏈狀或分枝鏈狀C_1-20烷基等)；環烷基(例如環戊基、環己基等C_5-10環烷基等)；芳基(例 如苯基、聯苯基、萘基等C_6-12芳基等)；將此等基組合2個以上而得之基[例如芳烷基(例如苯甲基、苯乙基等C_6-12芳基-C_1-10烷基等)；烷芳基(例如甲苯基(甲基苯基)、二甲苯基(二甲基苯基)等單至五(C_1-20烷基)C_6-12芳基等)等]等}；-OR基(式中，R表示上述例示之烴基)[例如烷氧基(例如甲氧基、乙氧基、丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、正十二烷氧基等直鏈狀或分枝鏈狀C_1-20烷氧基等)；環烷氧基(例如環己氧基等C_5-10環烷氧基等)；芳氧基(例如苯氧基等C_6-12芳氧基等)；芳烷氧基(例如苯甲氧基等C_6-12芳基-C_1-10烷氧基等)；烷芳氧基(例如甲苯氧基、二甲苯氧基等單至五(C_1-20烷基)C_6-12芳氧基等)等]；-SR基(式中，R表示上述例示之烴基)[例如烷硫基(例如甲硫基、乙硫基、丙硫基、正丁硫基、正丁硫基、正十二烷硫基等C_1-20烷硫基等)；環烷硫基(例如環己硫基等C_5-10環烷硫基等)；芳硫基(例如苯硫基等C_6-12芳硫基等)；芳烷硫基(例如苯甲硫基等C_6-12芳基-C_1-10烷硫基等)；烷芳硫基(例如甲苯硫基、二甲苯硫基等單至五(C_1-20烷基)C_6-12芳硫基等)等]；羥基；甲醯基；醯基(例如乙醯基、苯甲醯基等C_1-10醯基等)；烷氧羰基(例如甲氧羰基、乙氧羰基等C_1-12烷氧羰基等)；羧基；硝基；氰基；胺基；經取代之胺基[例如二烷胺基(例如二甲胺基等二C_1-6烷胺基等)；二醯基胺基(例如二乙醯基胺基等二C_1-10醯基胺基等)等]；硫醇基；磺酸基(磺基)；鹵素原子(例如氟原子、氯原子、溴原子、碘原子)等]等。 Examples of the substituent represented by R ^1a and R ^1b include a hydrocarbon group {e.g., an alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third group). a linear or branched chain C _1-30 alkyl group such as butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl or n-dodecyl (lauryl), preferably linear a branched or branched chain C _1-20 alkyl group; a cycloalkyl group (e.g., a C _5-10 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group); an aryl group (e.g., a phenyl group, a biphenyl group, a naphthyl group) _{Or a} C _6-12 aryl group or the like; a group obtained by combining two or more of these groups [for example, an aralkyl group (for example, a benzyl group, a phenethyl group or the like, a C _6-12 aryl-C _1-10 alkyl group) And the like; an alkaryl group (e.g., tolyl (C _1-20 alkyl) C _6-12 aryl, etc.) such as tolyl (methylphenyl) or xylyl (dimethylphenyl), etc.] }; -OR group (wherein R represents the above-exemplified hydrocarbon group) [e.g., alkoxy group (e.g., methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, second butoxy) , tert-butoxy, n-dodecyloxy group linear or branched chain C _1-20 alkoxy group, etc.); cycloalkyl group (e.g. cyclohexyl, etc. C _5-10 cycloalkyl group, Yl, etc.); aryloxy (e.g. phenoxy group, etc. C _6-12 aryloxy group); aralkyloxy group (e.g. benzyloxy etc. -C _1-10 aryl-C _6-12 alkoxy group) Alkaryloxy (e.g., tolyl (C _1-20 alkyl) C _6-12 aryloxy, etc. such as tolyloxy, _xyloxy ), etc.]; -SR group (wherein R represents the above exemplified a hydrocarbon group) [e.g., an alkylthio group (e.g., a methylthio group, an ethylthio group, a propylthio group, a n-butylthio group, a n-butylthio group, a n-dodecylthio group, or the like, a C _1-20 alkylthio group, etc.); An alkylthio group (e.g., a C _5-10 cycloalkylthio group such as a cyclohexylthio group); an arylthio group (e.g., a C _6-12 arylthio group such as a phenylthio group, etc.); an aralkylthio group (e.g., a thiophenyl group) Such as C _6-12 aryl-C _1-10 alkylthio, etc.); alkylarylthio (such as toluenethio, xylylthio, etc., one to five (C _1-20 alkyl) C _6-12 aromatic sulfur Base; etc.]; hydroxy; mercapto; fluorenyl (e.g., acetonitrile, benzhydryl, etc. C _1-10 fluorenyl, etc.); alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, etc. C _{1- 12} alkoxycarbonyl, etc.; carboxyl group; nitro group; cyano group; amine group; substituted amine group [for example, dialkylamino group (for example, di-C _1-6 alkylamino group such as dimethylamino group); Amino group (e.g., diethylamino group) Equivalent to a di-C _1-10 fluorenylamino group, etc.]; a thiol group; a sulfonic acid group (sulfo group); a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.).

R^1a及R^1b基的種類可彼此相異，但通常多數情況係相同。作為較佳的R^1a及R^1b基，為氫原子或烴基(例如烷基(例如C_1-30烷基等)、環烷基、芳基等)，更佳係可為氫原子、C_1-25烷基、C_5-10環烷基或C_6-12芳基(例如氫原子、C_1-20烷基、C_5-8環烷基或C_6-10芳基等)，特別是氫原子、C_4-18烷基或C_6-10芳基(例如氫原子、C_6-16烷基，特別是氫原子)。 The types of R ^1a and R ^1b groups may be different from each other, but in most cases they are the same. Preferred R ^1a and R ^1b groups are a hydrogen atom or a hydrocarbon group (e.g., an alkyl group (e.g., a C _1-30 alkyl group, etc.), a cycloalkyl group, an aryl group, etc.), more preferably a hydrogen atom, C _{1 . a -25} alkyl group, a C _5-10 cycloalkyl group or a C _6-12 aryl group (for example, a hydrogen atom, a C _1-20 alkyl group, a C _5-8 cycloalkyl group or a C _6-10 aryl group, etc.), especially A hydrogen atom, a C _4-18 alkyl group or a C _6-10 aryl group (for example, a hydrogen atom, a C _6-16 alkyl group, particularly a hydrogen atom).

作為R²所表示之取代基，可列舉例如與前述R^1a及R^1b基同樣的取代基等。作為較佳的R²基，為氫原子或烴基(例如烷基(例如C_1-30烷基，較佳為C_1-20烷基等)、環烷基、芳基、芳烷基、烷芳基，較佳為烷基、環烷基、芳基等)，更佳係可為氫原子、C_1-16烷基、C_5-10環烷基或C_6-12芳基(例如氫原子、C_1-10烷基、C_5-8環烷基或C_6-10芳基等)，特別是氫原子、C_1-6烷基或C_6-10芳基(特別是氫原子、C_1-4烷基(甲基等)或C_6-8芳基(苯基等))。另外，在取代數m為2以上之情況，2個以上R²基的種類可彼此相同或相異。 Examples of the substituent represented by R ² include the same substituents as the above R ^1a and R ^1b groups. Preferred R ² groups are a hydrogen atom or a hydrocarbon group (e.g., an alkyl group (e.g., a C _1-30 alkyl group, preferably a C _1-20 alkyl group, etc.), a cycloalkyl group, an aryl group, an aralkyl group, an alkane. An aryl group, preferably an alkyl group, a cycloalkyl group, an aryl group or the like), more preferably a hydrogen atom, a C _1-16 alkyl group, a C _5-10 cycloalkyl group or a C _6-12 aryl group (for example, hydrogen) An atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group or a C _6-10 aryl group, etc., particularly a hydrogen atom, a C _1-6 alkyl group or a C _6-10 aryl group (especially a hydrogen atom, C _1-4 alkyl (methyl or the like) or C _6-8 aryl (phenyl, etc.)). Further, when the substitution number m is 2 or more, the types of the two or more R ² groups may be the same or different from each other.

R²基的取代數m可為例如0至3的整數，較佳為0至2的整數。此外，取代數m可因應所對應之R²基所鍵結之Z原子的原子價v而選擇，舉例而言，在原子價為2價之情況，取代數m為0，在原子價為3價之情況，取代數m為1，在原子價為4價之情況，取代數m為0或2，在原子價為5價之情況，取代數m為1或3，在原子價為6價之情況，取代數m大多為0、2或4(例如0或 2，特別是0)。 The substitution number m of the R ² group may be, for example, an integer of 0 to 3, preferably an integer of 0 to 2. Further, the substitution number m may be selected in accordance with the atomic valence v of the Z atom to which the corresponding R ² group is bonded, for example, in the case where the valence is 2 valence, the substitution number m is 0, and the valence is 3 In the case of a valence, the substitution number m is 1, and when the valence is 4, the substitution number m is 0 or 2. When the valence is 5, the substitution number m is 1 or 3, and the valence is 6 valence. In the case where the substitution number m is mostly 0, 2 or 4 (for example, 0 or 2, particularly 0).

作為R³所表示之週期表第16族(6B族)元素，係與例如前述Z中所例示之第16族元素相同。作為較佳的R³，為選自氧、硫、硒及碲之原子，更佳係可為選自氧、硫及硒之原子(例如氧原子[或側氧基(=O)]或硫原子[或硫酮基(=S)])，特別是氧原子。在取代數n為2之情況，2個R³原子的種類可彼此相同或相異。 The Group 16 (Group 6B) element of the periodic table represented by R ³ is the same as the Group 16 element exemplified in the above Z, for example. Preferred R ³ is an atom selected from the group consisting of oxygen, sulfur, selenium and tellurium, and more preferably an atom selected from the group consisting of oxygen, sulfur and selenium (for example, an oxygen atom [or a pendant oxy group (=O)] or sulfur. Atom [or thioketone (=S)]), especially an oxygen atom. In the case where the substitution number n is 2, the types of the two R ³ atoms may be the same or different from each other.

原子R³的取代數n可因應所對應之R³原子所鍵結之Z原子的原子價v而選擇，舉例而言，在原子價為2價或3價之情況，取代數n為0，在原子價為4價或5價之情況，取代數n為0或1，在原子價為6價之情況，取代數n大多為0至2的整數(例如1或2，特別是2)。 The substitution number n of the atom R ³ may be selected in accordance with the atomic valence v of the Z atom to which the corresponding R ³ atom is bonded. For example, in the case where the valence is 2 or 3, the substitution number n is 0. In the case where the valence is 4 or 5, the substitution number n is 0 or 1, and in the case where the valence is hexavalent, the substitution number n is mostly an integer of 0 to 2 (for example, 1 or 2, particularly 2).

在R^A及R^B中，作為選自週期表第16族元素之原子，可列舉與前述R³(或Z中所例示之第16族元素)同樣的原子，作為取代基，可列舉與前述R^1a及R^1b基同樣的取代基、含金屬(或半金屬)之基等。 In the case of R ^A and R ^B , examples of the atom selected from the group 16 element of the periodic table include the same atom as the above R ³ (or the group 16 element exemplified in Z), and examples of the substituent include the above. The same substituents, metal-containing (or semi-metal) groups, and the like of R ^1a and R ^1b are used.

作為含金屬(或半金屬)之基，在包含金屬原子或半金屬原子(例如矽、硼等)之前提下，並無特別限制，代表性而言，可列舉例如鋰原子(鋰基)、-B(OH)₂基、-ZnX⁴基(式中，X⁴表示鹵素原子)、-MgX⁵基(式中，X⁵表示鹵素原子)、-Sn(R⁸)₃基(式中，R⁸表示烷基)、-Si(R⁹)₃基(式中，R⁹表示氟原子、氯原子或烷基)等。 The metal (or semi-metal)-containing group is not particularly limited as long as it contains a metal atom or a semi-metal atom (for example, ruthenium, boron, etc.), and typically, for example, a lithium atom (lithium group), -B(OH) ₂ group, -ZnX ⁴ group (wherein X ⁴ represents a halogen atom), -MgX ⁵ group (wherein, X ⁵ represents a halogen atom), and -Sn(R ⁸ ) ₃ group (wherein, R ⁸ represents an alkyl group or a -Si(R ⁹ ) ₃ group (wherein R ⁹ represents a fluorine atom, a chlorine atom or an alkyl group).

作為X⁴及X⁵所表示之鹵素原子，可列舉例如氯、溴、碘等。作為R⁸及R⁹所表示之烷基，可列舉例 如甲基、正丁基等C_1-6烷基(較佳為甲基等C_1-4烷基等)等。3個R⁸基可彼此相同或相異，3個R⁹基亦可彼此相同或相異。 Examples of the halogen atom represented by X ⁴ and X ⁵ include chlorine, bromine, and iodine. Examples of the alkyl group represented by R ⁸ and R ⁹ include a C _1-6 alkyl group such as a methyl group or a n-butyl group (preferably a C _1-4 alkyl group such as a methyl group). The three R ⁸ groups may be the same or different from each other, and the three R ⁹ groups may be the same or different from each other.

R^A及R^B的取代數p1及p2可因應所對應之環A¹及A²的種類而選擇，可為例如0至12(例如0至8)左右的整數，較佳為0至6(例如0至4)左右的整數，更佳為0至3(例如0至2)左右的整數，特別是0或1。在取代數p1及p2為2以上之情況，2個以上之R^A及R^B的種類各自可彼此相同或相異，通常係相同。另外，實施例及虛線所示之鍵結在R^A及R^B為氫原子或取代基(例如烴基等)之情況為單鍵，在R^A及R^B為選自第16族元素之原子(例如氧原子)之情況則多數情況係表示雙鍵。 The substitution numbers p1 and p2 of R ^A and R ^B may be selected depending on the types of the rings A ¹ and A ² corresponding thereto, and may be, for example, an integer of from 0 to 12 (for example, from 0 to 8), preferably from 0 to 6 ( For example, an integer of about 0 to 4), more preferably an integer of about 0 to 3 (for example, 0 to 2), particularly 0 or 1. When the substitution numbers p1 and p2 are 2 or more, the types of two or more R ^A and R ^B may be the same or different from each other, and are generally the same. Further, the bond shown in the examples and the broken line is a single bond in the case where R ^A and R ^B are a hydrogen atom or a substituent (for example, a hydrocarbon group or the like), and R ^A and R ^B are atoms selected from the group 16 element ( In the case of, for example, an oxygen atom, in most cases, a double bond is indicated.

另外，在前述式(1)所示之化合物(亦包含後述之式(1A)及式(1B)所示之化合物)中，若為A¹及A²、R^1a及R^1b、R^A及R^B以及p1及p2各自彼此相同之化合物，即，具有在紙面上以通過Z之縱線為軸之線對稱的結構之化合物，則可能由於分子彼此易於排列(或易於堆疊)，因而可提升電特性(移動度等)，故較佳。 Further, in the compound represented by the above formula (1) (including the compound represented by the formula (1A) and the formula (1B) to be described later), A ¹ and A ² , R ^1a , R ^1b and R ^A and A compound in which R ^B and p1 and p2 are each identical to each other, that is, a compound having a structure which is symmetrical on the paper surface by the longitudinal line of Z, may be improved because molecules are easily arranged (or easily stacked) with each other. It is preferable to have electrical characteristics (movability, etc.).

作為前述式(1)所示之化合物，代表性而言，可列舉式(1A)及式(1B)所示之化合物等。 The compound represented by the above formula (1) is typically a compound represented by the formula (1A) and the formula (1B).

(式(1A)所示之化合物) (compound represented by formula (1A))

(式中，環Ar¹及Ar²表示芳烴環；R^a及R^b係相同或相異且表示取代基；q1及q2表示0以上的整數；Z、R^1a、R^1b、R²、R³、m、n係亦包含較佳態樣在內並與前述式(1)相同)。 (wherein the rings Ar ¹ and Ar ² represent an aromatic hydrocarbon ring; R ^a and R ^b are the same or different and represent a substituent; q1 and q2 represent an integer of 0 or more; Z, R ^1a , R ^1b , R ² , R ³ , m, n are also included in the preferred embodiment and are the same as the above formula (1).

在前述式(1A)中，作為Ar¹及Ar²所表示之芳烴環，可列舉前述式(1)之環A¹及A²之段落中所例示之芳香族烴環等。作為較佳的芳烴環，可為C_6-22芳烴環(例如C_6-18芳烴環)，更佳為C_6-14芳烴環(例如苯環或萘環等C_6-10芳烴環)，特別是萘環。此外，環Ar¹及Ar²的種類可彼此相同或相異，通常大多係相同。另外，在環Ar¹及Ar²中，縮合位置(共有包含Z原子之7員環之2,3-位及6,7-位的碳原子(C=C鍵)之位置)並無特別限制。 In the above formula (1A), examples of the aromatic hydrocarbon ring represented by Ar ¹ and Ar ² include an aromatic hydrocarbon ring exemplified in the paragraphs of the rings A ¹ and A ² of the above formula (1). As a preferred aromatic hydrocarbon ring, it may be a C _6-22 arene ring (for example, a C _6-18 arene ring), more preferably a C _6-14 arene ring (for example, a C _6-10 arene ring such as a benzene ring or a naphthalene ring). Especially the naphthalene ring. Further, the kinds of the rings Ar ¹ and Ar ² may be the same or different from each other, and are usually mostly the same. Further, in the rings Ar ¹ and Ar ² , the condensation position (the position of the carbon atom (C=C bond) of the 2,3-position and the 6,7-position of the 7-membered ring containing the Z atom is not particularly limited). .

作為R^a及R^b所表示之取代基，可列舉前述式(1)之R^A及R^B之段落中所例示之取代基(與R^1a及R^1b基同樣的取代基、含金屬(或半金屬)之基)等。R^a及R^b基的種類可彼此相異，但通常多數情況係相同。作為較佳的R^a及R^b基，為烴基(例如烷基(例如C_1-30烷基，較佳為C_1-20烷基等)、環烷基、芳基等)、含金屬(或半金屬)之基，更佳係可為C_1-16烷基、C_5-10環烷基或C_6-12芳基(例如C_1-12烷 基、C_5-8環烷基或C_6-10芳基等)、含金屬(或半金屬)之基[例如鋰原子(鋰基)、-B(OH)₂基、鹵鋅基(溴鋅基等)、鹵鎂基(溴鎂基等)、三烷基錫烷基(三甲基錫烷基等三C_1-6烷基錫烷基等)、三鹵矽基(三氟矽基、三氯矽基等)、三烷基矽基(三甲基矽基等三C_1-6烷基矽基等)等]，特別是C_4-10烷基或C_6-10芳基。 Examples of the substituent represented by R ^a and R ^b include the substituents exemplified in the paragraphs of R ^A and R ^B of the above formula (1) (the same substituents as the R ^1a and R ^1b groups, and a metal-containing group (or The base of semi-metal) and so on. The types of R ^a and R ^b groups may differ from each other, but in most cases they are the same. Preferred R ^a and R ^b groups are a hydrocarbon group (e.g., an alkyl group (e.g., a C _1-30 alkyl group, preferably a C _1-20 alkyl group, etc.), a cycloalkyl group, an aryl group, etc.), a metal-containing ( Or a semi-metal group, more preferably C _1-16 alkyl, C _5-10 cycloalkyl or C _6-12 aryl (eg C _1-12 alkyl, C _5-8 cycloalkyl or a C _6-10 aryl group or the like, a metal (or semimetal) group (for example, a lithium atom (lithium group), a -B(OH) ₂ group, a halozinc group (bromozinc group, etc.), a halomagnesium group (bromine) ), trialkyl stannyl (trimethylstannyl magnesium group and other three C _1-6 alkyltin group, etc.), trihalo silicon based (trifluoromethyl silicon based, silicon based trichloromethyl, etc.), tris An alkyl fluorenyl group (such as a tri-C _1-6 alkyl fluorenyl group such as trimethyl fluorenyl) or the like], particularly a C _4-10 alkyl group or a C _6-10 aryl group.

R^a及R^b基的取代數q1及q2表示0以上的整數，可因應環Ar¹及Ar²的種類而選自例如0至14左右的範圍，可為例如0至12(例如0至8)左右的整數，較佳為0至6(例如0至4)左右的整數，更佳為0至3(例如0至2)左右的整數，特別是0或1(特別是0)。在取代數q1及q2為2以上之情況，2個以上之R^a及R^b的種類各自可彼此相同或相異，通常係相同。 The substitution numbers q1 and q2 of the R ^a and R ^b groups represent an integer of 0 or more, and may be selected from the range of, for example, about 0 to 14 depending on the kind of the rings Ar ¹ and Ar ² , and may be, for example, 0 to 12 (for example, 0 to 8). The left and right integers are preferably integers of about 0 to 6 (e.g., 0 to 4), more preferably integers of about 0 to 3 (e.g., 0 to 2), particularly 0 or 1 (particularly 0). When the number of substitutions q1 and q2 is 2 or more, the types of two or more of R ^a and R ^b may be the same or different from each other, and are generally the same.

作為前述式(1A)所示之化合物，具體而言，可列舉例如環Ar¹及Ar²為C_6-14芳烴環(例如苯環、萘環、蒽環、菲環等)，R^1a及R^1b基為氫原子或烷基(例如C_1-30烷基等)，q1及q2為0之化合物(例如下述表1中所記載之化合物等)。 Specific examples of the compound represented by the above formula (1A) include the ring Ar ¹ and Ar ² being a C _6-14 arene ring (for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc.), R ^1a and The R ^1b group is a hydrogen atom or an alkyl group (for example, a C _1-30 alkyl group), and a compound in which q1 and q2 are 0 (for example, a compound described in Table 1 below).

在前述式(1A)中，作為環Ar¹及Ar²為C_6-14芳烴環(例如苯環、萘環、蒽環、菲環等)，R^1a及R^1b基為氫原子或C_1-25烷基，q1及q2為0之化合物，更具體而言，可列舉例如(1A-a)Z為硫原子之化合物、(1A-b)Z為硒原子之化合物、(1A-c)Z為磷原子之化合物、(1A-d)Z為矽原子之化合物、(1A-e)Z為氧原子之化合物、(1A-f)Z為碳原子之化合物等。 In the above formula (1A), the ring Ar ¹ and Ar ² are a C _6-14 arene ring (for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc.), and the R ^1a and R ^1b groups are a hydrogen atom or C _{1 . a} compound having a _-25 alkyl group, q1 and q2 being 0, and more specifically, for example, (1A-a) Z is a compound of a sulfur atom, (1A-b) Z is a compound of a selenium atom, (1A-c) Z is a compound of a phosphorus atom, (1A-d) Z is a compound of a ruthenium atom, (1A-e) Z is a compound of an oxygen atom, and (1A-f) Z is a compound of a carbon atom.

作為(1A-a)Z為硫原子之化合物，可列舉例如(1A-a1)二芳烴并硫雜環庚烯類[例如二苯并[b,f]硫雜環庚烯、二萘并硫雜環庚烯(例如二萘并[2,3-b：2,3-f]硫雜環庚烯、二萘并[2,1-b：2,3-f]硫雜環庚烯、二萘并[1,2-b：2,3-f]硫雜環庚烯、二萘并[1,2-b：1,2-f]硫雜環庚烯、二萘并[1,2-b：2,1-f]硫雜環庚烯、二萘并[2,1-b：1,2-f]硫雜環庚烯等)、菲并萘并硫雜環庚烯(例如菲并[2,1-b]萘并[1,2-f]硫雜環庚烯等)、二菲并硫雜環庚烯(例如二菲并[2,1-b：1,2-f]硫雜環庚烯等)等二C_6-14芳烴并硫雜環庚烯，較佳為二C_6-10芳烴并硫雜環庚烯等]；(1A-a2)對應於前述(1A-a1)中所例示之化合物之S-氧化物體(亞磺醯基體)或S,S-二氧化物體(磺醯基體)(例如5,5-二側氧基-二苯并[b,f]硫雜環庚烯、6,6-二側氧基-二萘并[2,3-b：2,3-f]硫雜環庚烯等)等。 The compound (1A-a) wherein Z is a sulfur atom may, for example, be a (1A-a1) di arene and thiaheptene [e.g., dibenzo[b,f]thiaheptene, dinaphthofluorene. Heterocyclic heptene (for example, dinaphtho[2,3-b:2,3-f]thiene, dinaphtho[2,1-b:2,3-f]thiaheptene, Dinaphtho[1,2-b:2,3-f]thiene, dinaphtho[1,2-b:1,2-f]thiepine, dinaphthyl[1, 2-b: 2,1-f]thiazepine, dinaphtho[2,1-b:1,2-f]thiaheptene, etc.), phenanthrinthylenethioheptene ( For example, phenanthro[2,1-b]naphtho[1,2-f]thiaheptene, etc., diphenanthroline (for example, diphenanthrene [2,1-b:1,2 -f]thiazepine, etc.), etc., a di-C _6-14 arene and a thioheptene, preferably a di-C _6-10 arene and a thioheptene, etc.; (1A-a2) corresponds to the aforesaid An S-oxide (sulfinium sulfonate) or S,S-dioxide (sulfonyl sulfonate) of the compound exemplified in (1A-a1) (for example, 5,5-di-oxy-dibenzo[b] , f] thiaheptene, 6,6-di-oxy-dinaphtho[2,3-b:2,3-f]thiepine, etc.).

作為(1A-b)Z為硒原子之化合物，可列舉例如對應於前述(1A-a)Z為硫原子之化合物，並將Z之硫原子置換成硒原子而得之化合物(1A-b1)[例如二萘并[2,1-b： 1,2-f]硒雜環庚烯等]至(1A-b2)[例如Se,Se-二側氧基-二萘并[2,1-b：1,2-f]硒雜環庚烯等]等。 The compound (1A-b) wherein Z is a selenium atom, for example, a compound corresponding to the above (1A-a) Z is a sulfur atom, and a sulfur atom of Z is replaced by a selenium atom. [e.g., dinaphtho[2,1-b: 1,2-f]lenecycloheptene, etc.] to (1A-b2) [e.g., Se, Se-di-oxy-naphtho[2,1- b: 1,2-f] selenylheptene, etc.].

作為(1A-c)Z為磷原子之化合物，可列舉(1A-c1)二芳烴并磷雜環庚烯類[例如二苯并磷雜環庚烯類(例如二苯并[b,f]磷雜環庚烯；P-甲基-二苯并[b,f]磷雜環庚烯等P-C_1-4烷基-二苯并[b,f]磷雜環庚烯；P-苯基-二苯并[b,f]磷雜環庚烯等P-C_6-10芳基-二苯并[b,f]磷雜環庚烯等)；二萘并磷雜環庚烯類(例如二萘并[2,1-b：1,2-f]磷雜環庚烯、二萘并[2,3-b：2,3-f]磷雜環庚烯等二萘并磷雜環庚烯；P-甲基-二萘并[2,1-b：1,2-f]磷雜環庚烯、P-甲基-二萘并[2,3-b：2,3-f]磷雜環庚烯等P-C_1-4烷基-二萘并磷雜環庚烯；P-苯基-二萘并[2,1-b：1,2-f]磷雜環庚烯、P-苯基-二萘并[2,3-b：2,3-f]磷雜環庚烯等P-C_6-10芳基-二萘并磷雜環庚烯等)；菲并萘并磷雜環庚烯類(例如菲并[2,1-b]萘并[1,2-f]磷雜環庚烯等菲并萘并磷雜環庚烯；P-甲基-菲并[2,1-b]萘并[1,2-f]磷雜環庚烯等P-C_1-4烷基-菲并萘并磷雜環庚烯；P-苯基-菲并[2,1-b]萘并[1,2-f]磷雜環庚烯等P-C_6-10芳基-菲并萘并磷雜環庚烯等)；二菲并磷雜環庚烯類(例如二菲并[2,1-b：1,2-f]磷雜環庚烯等二菲并磷雜環庚烯；P-甲基-二菲并[2,1-b：1,2-f]磷雜環庚烯等P-C_1-4烷基-二菲并磷雜環庚烯；P-苯基-二菲并[2,1-b：1,2-f]磷雜環庚烯等P-C_6-10芳基-二菲并磷雜環庚烯等二C_6-14芳烴并磷雜環庚烯類，較佳為二C_6-10芳烴并磷雜環庚烯類等)；(1A-c2)對應於前述(1A-c1)中所例示之化合物之P-氧化物 體(例如P-側氧基-P-苯基-二苯并[b,f]磷雜環庚烯等)等。 The compound (1A-c) wherein Z is a phosphorus atom may, for example, be a (1A-c1) di arene and a heterocycloheptene [e.g., a dibenzophosphole (for example, dibenzo[b,f]). Phosphocycloheptene; PC- _1-4 alkyl-dibenzo[b,f]phospholeene; P-phenyl; P-methyl-dibenzo[b,f]phospholeene -Dibenzo[b,f]phospholeene and other PC _6-10 aryl-dibenzo[b,f]phospholeene, etc.); dinaphthophosphoranes (for example, two Naphthophosphonate such as naphtho[2,1-b:1,2-f]phosphole, dinaphtho[2,3-b:2,3-f]phospholeene Alkene; P-methyl-dinaphtho[2,1-b:1,2-f]phosphole, P-methyl-dinaphtho[2,3-b:2,3-f] PC _1-4 alkyl-dinaphthophosphonate, etc.; P-phenyl-dinaphtho[2,1-b:1,2-f]phosphole, P -Phenyl-naphtho[2,3-b:2,3-f]phospholeene, etc. PC _6-10 aryl-di-naphthacene heterocycloheptene, etc.; phenanthrene naphthacene Cycloheptenes (for example, phenanthro[2,1-b]naphtho[1,2-f]phospholeene and the like phenanthrinophthylphosphonium; P-methyl-phenanthrene[2, 1-b] naphtho [1,2-f] hept-phospholene-ene PC _1-4 alkyl - naphthalene and phenanthrene and phospholene heptene; the P-phenyl - phenanthro [2,1-b] And [1,2-f] hept-phospholene-ene PC _6-10 aryl group - phenanthrene and naphthalene phospholene heptene and the like); and two phenanthrene phospholene heptenes (e.g. two phenanthro [2, 1-b:1,2-f] phenanthroline and other phenanthrene; P-methyl-diphenanthrene [2,1-b:1,2-f]phosphonium PC _1-4 alkyl-diphenanthroline heptene such as olefin; PC _6-10 aryl such as P-phenyl-phenanthro[2,1-b:1,2-f]phospholeene a di-C _6-14 arene and a heterocycloheptene such as a bis-phenanthrene and a heterocycloheptene, preferably a di-C _6-10 arene and a heterocycloheptene, etc.; (1A-c2) The P-oxide body of the compound exemplified in the above (1A-c1) (for example, P-sideoxy-P-phenyl-dibenzo[b,f]phospholeene, etc.) or the like.

作為(1A-d)Z為矽原子之化合物，可列舉例如(1A-d1)二芳烴并矽雜環庚烯類[例如二苯并矽雜環庚烯類(例如二苯并[b,f]矽雜環庚烯；Si-甲基-二苯并[b,f]矽雜環庚烯等Si-C_1-4烷基-二苯并[b,f]矽雜環庚烯；Si-苯基-二苯并[b,f]矽雜環庚烯等Si-C_6-10芳基-二苯并[b,f]矽雜環庚烯；Si,Si-二甲基-二苯并[b,f]矽雜環庚烯等Si,Si-二C_1-4烷基-二苯并[b,f]矽雜環庚烯；Si-甲基-Si-苯基-二苯并[b,f]矽雜環庚烯等Si-C_1-4烷基-Si-C_6-10芳基-二苯并[b,f]矽雜環庚烯；Si,Si-二苯基-二苯并[b,f]矽雜環庚烯等Si,Si-二C_6-10芳基-二苯并[b,f]矽雜環庚烯等)；二萘并矽雜環庚烯類(例如二萘并[2,1-b：1,2-f]矽雜環庚烯、二萘并[2,3-b：2,3-f]矽雜環庚烯等二萘并矽雜環庚烯；Si-甲基-二萘并[2,1-b：1,2-f]矽雜環庚烯、Si-甲基-二萘并[2,3-b：2,3-f]矽雜環庚烯等Si-C_1-4烷基-二萘并矽雜環庚烯；Si-苯基-二萘并[2,1-b：1,2-f]矽雜環庚烯、Si-苯基-二萘并[2,3-b：2,3-f]矽雜環庚烯等Si-C_6-10芳基-二萘并矽雜環庚烯；Si,Si-二甲基-二萘并[2,1-b：1,2-f]矽雜環庚烯、Si,Si-二甲基-二萘并[2,3-b：2,3-f]矽雜環庚烯等Si,Si-二C_1-4烷基-二萘并矽雜環庚烯；Si-甲基-Si-苯基-二萘并[2,1-b：1,2-f]矽雜環庚烯、Si-甲基-Si-苯基-二萘并[2,3-b：2,3-f]矽雜環庚烯等Si-C_1-4烷基-Si-C_6-10芳基-二萘并矽雜環庚烯；Si,Si-二苯基-二萘并[2,1-b：1,2-f]矽雜環庚烯、Si,Si-二苯基-二萘并[2,3-b：2,3-f]矽雜環庚烯等Si,Si-二C_6-10芳基- 二萘并矽雜環庚烯等)；菲并萘并矽雜環庚烯類(例如菲并[2,1-b]萘并[1,2-f]矽雜環庚烯等菲并萘并矽雜環庚烯；Si-甲基-菲并[2,1-b]萘并[1,2-f]矽雜環庚烯等Si-C_1-4烷基-菲并萘并矽雜環庚烯；Si-苯基-菲并[2,1-b]萘并[1,2-f]矽雜環庚烯等Si-C_6-10芳基-菲并萘并矽雜環庚烯；Si,Si-二甲基-菲并[2,1-b]萘并[1,2-f]矽雜環庚烯等Si,Si-二C_1-4烷基-菲并萘并矽雜環庚烯；Si-甲基-Si-苯基-菲并[2,1-b]萘并[1,2-f]矽雜環庚烯等Si-C_1-4烷基-Si-C_6-10芳基-菲并萘并矽雜環庚烯；Si,Si-二苯基-菲并[2,1-b]萘并[1,2-f]矽雜環庚烯等Si,Si-二C_6-10芳基-菲并萘并矽雜環庚烯等)；二菲并矽雜環庚烯類(例如二菲并[2,1-b：1,2-f]矽雜環庚烯等二菲并矽雜環庚烯；Si-甲基-二菲并[2,1-b：1,2-f]矽雜環庚烯等Si-C_1-4烷基-二菲并矽雜環庚烯；Si-苯基-二菲并[2,1-b：1,2-f]矽雜環庚烯等Si-C_6-10芳基-二菲并矽雜環庚烯；Si,Si-二甲基-二菲并[2,1-b：1,2-f]矽雜環庚烯等Si,Si-二C_1-4烷基-二菲并矽雜環庚烯；Si-甲基-Si-苯基-二菲并[2,1-b：1,2-f]矽雜環庚烯等Si-C_1-4烷基-Si-C_6-10芳基-二菲并矽雜環庚烯；Si,Si-二苯基-二菲并[2,1-b：1,2-f]矽雜環庚烯等Si,Si-二C_6-10芳基-二菲并矽雜環庚烯等)等二C_6-14芳烴并矽雜環庚烯類，較佳為二C_6-10芳烴并矽雜環庚烯類等。 The compound (1A-d) wherein Z is a halogen atom may, for example, be a (1A-d1) di arene and a heterocycloheptene [e.g., a dibenzofluorene heterocycloheptene (for example, dibenzo[b,f] a heterocyclic heptene; Si-C _1-4 alkyl-dibenzo[b,f]fluorene heterocycloheptene; Si such as Si-methyl-dibenzo[b,f]fluorene heterocycle -Phenyl-dibenzo[b,f]fluorene heterocycloheptene, etc. Si-C _6-10 aryl-dibenzo[b,f]fluorene heterocycleheptene; Si,Si-dimethyl-di Si,Si-di-C _1-4 alkyl-dibenzo[b,f]fluorene heterocycloheptene such as benzo[b,f]fluorene heterocyclenene; Si-methyl-Si-phenyl-di Si-C _1-4 alkyl-Si-C _6-10 aryl-dibenzo[b,f]fluorene heterocycloheptene such as benzo[b,f]fluorene heterocyclehene; Si,Si-di Si, Si-di C _6-10 aryl-dibenzo[b,f]fluorene heterocycloheptene, etc.; phenyl-dibenzo[b,f]fluorene heterocycleheptene; Cycloheptenes (for example, dinaphtho[2,1-b:1,2-f]indeneheptene, dinaphtho[2,3-b:2,3-f]indene heteroheptene, etc. Di-naphthoquinone heterocycloheptene; Si-methyl-dinaphtho[2,1-b:1,2-f]indene heterocycle, Si-methyl-dinaphtho[2,3-b :2,3-f]Si-C _1-4 alkyl-dinaphthoquinone heterocycloheptene such as heterocyclic heptene; Si-phenyl-dinaphtho[2,1-b:1,2- f] 矽 heterocyclic Si-C _6-10 aryl-dinaphthoquinone heterocycloheptene such as heptene, Si-phenyl-dinaphtho[2,3-b:2,3-f]antheneheptene; Si, Si-dimethyl-dinaphtho[2,1-b:1,2-f]indene heterocycle, Si,Si-dimethyl-dinaphtho[2,3-b:2,3- f] Si, Si-di-C _1-4 alkyl-dinaphthoquinone heterocycloheptene such as heterocyclic heptene; Si-methyl-Si-phenyl-dinaphtho[2,1-b:1 , 2-f] anthracene heptene, Si-methyl-Si-phenyl-dinaphtho[2,3-b:2,3-f]fluorene heterocycloheptene, etc. Si-C _1-4 alkane s-Si-C _6-10 aryl-dinaphthoquinone heterocycloheptene; Si,Si-diphenyl-dinaphtho[2,1-b:1,2-f]indene heteroheptene, Si,Si-di-C _6-10 aryl-di-naphthacene heterocycloheptene such as Si, Si-diphenyl-dinaphtho[2,3-b:2,3-f]-heterocycloheptene Anthracene; naphthoquinone-heterocyclic heptenes (for example, phenanthroline [2,1-b]naphtho[1,2-f]indeneheptene and the like phenanthrinophthalene heterocycloheptene; Si -Methyl-phenanthro[2,1-b]naphtho[1,2-f]fluorene heterocycloheptene, etc. Si-C _1-4 alkyl-phenanthrinohinofluorene heterocycle heptene; Si-benzene Si-C _6-10 aryl-phenanthrinophthalene heterocycloheptene such as ketophenanthro[2,1-b]naphtho[1,2-f]fluorene heterocyclenene; Si, Si-di Si, Si-di C, such as methyl-phenanthro[2,1-b]naphtho[1,2-f]fluorene heterocycle _1-4 alkyl-phenanthrinophthoquinone heterocycloheptene; Si-methyl-Si-phenyl-phenanthro[2,1-b]naphtho[1,2-f]indene heteroheptene Si-C _1-4 alkyl-Si-C _6-10 aryl-phenanthrinophthoquinone heterocycloheptene; Si,Si-diphenyl-phenanthro[2,1-b]naphtho[1, 2-f] 矽 heterocyclic heptene, etc. Si, Si-di C _6-10 aryl-phenanthrinophthoquinone heterocycloheptene, etc.; diphenanthrene fluorene heterocycle heptene (eg diphenanthrene [2] , 1-b: 1,2-f] fluorene heterocycloheptene and other diphenanthrene heptane heptene; Si-methyl-diphenanthrene [2,1-b:1,2-f]fluorene heterocycle Si-C _1-4 alkyl-diphenanthrene heterocycloheptene such as heptene; Si-phenyl-diphenanthrene [2,1-b:1,2-f]indene heteroheptene and the like Si- C _6-10 aryl-diphenanthrene heterocycloheptene; Si, Si-dimethyl-diphenanthrene [2,1-b:1,2-f] anthracene heptene, etc. Si, Si- Di-C _1-4 alkyl-diphenanthrene heterocycloheptene; Si such as Si-methyl-Si-phenyl-diphenanthroline [2,1-b:1,2-f]indene heterocyclene -C _1-4 alkyl-Si-C _6-10 aryl-diphenanthrene heterocycloheptene; Si,Si-diphenyl-diphenanthrene[2,1-b:1,2-f] a di-C _6-14 arene and a heterocyclic heptene such as a heterocyclic heptene such as Si, a Si-di C _6-10 aryl-diphenanthrene heterocycloheptene or the like, preferably a di C _{6- group. 10} and silicon aromatic heterocyclic heptenes like

作為(1A-e)Z為氧原子之化合物，可列舉例如對應於前述(1A-a1)二芳烴并硫雜環庚烯類中所例示之化合物，並將Z之硫原子置換成氧原子而得之化合物 (1A-e1)[例如二萘并[2,1-b：1,2-f]氧雜環庚烯等]等。 Examples of the compound in which (1A-e)Z is an oxygen atom include, for example, a compound exemplified in the above-mentioned (1A-a1) di arene and thiaheptene, and a sulfur atom of Z is replaced with an oxygen atom. The obtained compound (1A-e1) [e.g., dinaphtho[2,1-b:1,2-f]oxacycloheptene, etc.] and the like.

作為(1A-f)Z為碳原子之化合物，可列舉例如對應於作為前述(1A-d)Z為矽原子之化合物所例示之化合物，並將Z之矽原子置換成碳原子而得之化合物(1A-f1)[例如7,7-二甲基-二萘并[1,2-a：2,1-d]環庚烯等]等。 The compound (1A-f) wherein Z is a carbon atom, for example, a compound exemplified as a compound which is a ruthenium atom of the above (1A-d)Z, and a compound obtained by substituting a ruthenium atom of Z with a carbon atom. (1A-f1) [e.g., 7,7-dimethyl-dinaphtho[1,2-a:2,1-d]cycloheptene, etc.].

另外，在前述(1A-a)至(1A-f)中，係針對R^1a及R^1b基為氫原子之化合物進行例示，但亦包含對應於前述例示化合物，且R^1a及R^1b基為烷基(例如C_1-25烷基，較佳為C_1-20烷基等)之化合物。 Further, in the above (1A-a) to (1A-f), the compounds in which the R ^1a and R ^1b groups are a hydrogen atom are exemplified, but also include the compounds exemplified above, and the R ^1a and R ^1b groups are A compound of an alkyl group (e.g., a C _1-25 alkyl group, preferably a C _1-20 alkyl group, etc.).

此等化合物(1A-a)至(1A-f)之中，較佳為化合物(1A-a)、(1A-b)、(1A-c)、(1A-d)[例如化合物(1A-a)、(1A-b)、(1A-c)]，特佳為化合物(1A-a)。 Among these compounds (1A-a) to (1A-f), preferred are the compounds (1A-a), (1A-b), (1A-c), (1A-d) [for example, the compound (1A-- a), (1A-b), (1A-c)], particularly preferably the compound (1A-a).

(式(1B)所示之化合物) (compound represented by formula (1B))

(式中，Z¹及Z²係相同或相異且表示選自週期表第13族至16族元素之原子；R^2a、R^2b、R^4a、R^4b、R^5a及R^5b係相同或相異且表示氫原子或取代基；R^3a及R^3b係相同或相異且表示選自週期表第16族元素之原子；m1及 m2係相同或相異且表示0至4的整數；n1及n2係相同或相異且表示0至2的整數；Z、R^1a、R^1b、R²、R³、m、n係亦包含較佳態樣在內並與前述式(1)相同。另外，在本說明書及申請專利範圍中，式(1B)之縮合環中之位置編號係示於式(1B)右側之式)。 (wherein Z ¹ and Z ² are the same or different and represent an atom selected from Group 13 to Group 16 elements of the periodic table; R ^2a , R ^2b , R ^4a , R ^4b , R ^5a and R ^5b are the same or Different from each other and representing a hydrogen atom or a substituent; R ^3a and R ^3b are the same or different and represent an atom selected from elements of Group 16 of the periodic table; m1 and m2 are the same or different and represent an integer from 0 to 4; n1 And n2 are the same or different and represent an integer of 0 to 2; Z, R ^1a , R ^1b , R ² , R ³ , m, n are also included in the preferred embodiment and are the same as the above formula (1). Further, in the specification and the patent application, the position number in the condensation ring of the formula (1B) is shown in the formula on the right side of the formula (1B).

在前述式(1B)中，作為Z¹及Z²所表示之原子，可列舉與前述式(1)之Z中所例示之原子同樣的原子。此等Z、Z¹及Z²所表示之原子的種類可彼此相異，但通常多數情況係Z¹及Z²至少相同。作為較佳的Z¹及Z²所表示之原子，為選自由週期表第14族元素、第15族元素、第16族元素所組成群組之原子(例如選自碳、氮、磷、氧、硫、硒及碲之原子等)，更佳係可為週期表第16族元素(例如選自氧、硫及硒之原子，特別是硫等)等。 In the above formula (1B), examples of the atom represented by Z ¹ and Z ² include the same atoms as those exemplified in Z of the above formula (1). The types of atoms represented by these Z, Z ¹ and Z ² may be different from each other, but in most cases, Z ¹ and Z ^{2 are} at least the same. Preferred atoms represented by Z ¹ and Z ² are atoms selected from the group consisting of Group 14 elements, Group 15 elements, and Group 16 elements of the periodic table (for example, selected from the group consisting of carbon, nitrogen, phosphorus, and oxygen). More preferably, it may be a group 16 element of the periodic table (for example, an atom selected from oxygen, sulfur, and selenium, particularly sulfur, etc.).

另外，在Z¹及Z²兩者為硫原子之情況，Z多數情況為例如選自硒、磷、砷、矽及鍺之原子(例如選自硒、磷及矽之原子)。 Further, in the case where both Z ¹ and Z ² are sulfur atoms, Z is usually, for example, an atom selected from the group consisting of selenium, phosphorus, arsenic, antimony and bismuth (for example, an atom selected from the group consisting of selenium, phosphorus and antimony).

Z、Z¹及Z²所表示之原子的各原子價(價數)v、v1及v2係彼此相同或相異且為2至6價，各自滿足v=m+2×n+2、v1=m1+2×n1+2及v2=m2+2×n2+2。此外，各原子價v、v1及v2可因應各自所對應之原子的種類而選擇，舉例而言，就週期表第13族元素(例如硼)而言多數情況為3價，就週期表第14族元素(例如碳、矽等)而言多數情況為2價或4價(特別是4價)，就週期表第15族元素(例如氮、磷等)而言多數情況為3至5價，就週 期表第16族元素(例如氧、硫、硒等)而言多數情況為2至6價。 The valences (valences) v, v1, and v2 of the atoms represented by Z, Z ¹ and Z ² are the same or different from each other and are 2 to 6 valences, each satisfying v=m+2×n+2, v1 =m1+2×n1+2 and v2=m2+2×n2+2. Further, each of the valences v, v1, and v2 may be selected depending on the type of atom to which they correspond, for example, in the case of a group 13 element of the periodic table (for example, boron), most cases are trivalent, and the 14th periodic table is Group elements (such as carbon, ruthenium, etc.) are mostly divalent or tetravalent (especially tetravalent), and most of the elements of the 15th group of the periodic table (such as nitrogen, phosphorus, etc.) are 3 to 5, In the case of elements of Group 16 of the periodic table (eg, oxygen, sulfur, selenium, etc.), most cases are from 2 to 6 valence.

作為R^2a及R^2b所表示之取代基，可列舉例如與前述式(1)之R²基(或R^1a及R^1b基)之段落中所例示之取代基同樣的取代基等。R²、R^2a及R^2b基的種類可彼此相異，但通常多數情況係R^2a及R^2b基至少相同。作為較佳的R^2a及R^2b基，可為與前述式(1)之R²基同樣者。另外，在取代數m1及m2為2以上之情況，2個以上之R^2a及R^2b基的種類可彼此相同或相異。 Examples of the substituent represented by R ^2a and R ^2b include the same substituents as those exemplified in the paragraphs of the R ² group (or R ^1a and R ^1b groups) of the above formula (1). The types of the R ² , R ^2a and R ^2b groups may be different from each other, but in most cases, the R ^2a and R ^2b groups are at least the same. The preferred R ^2a and R ^2b groups may be the same as the R ² group of the above formula (1). Further, when the number of substitutions m1 and m2 is 2 or more, the types of the two or more R ^2a and R ^2b groups may be the same or different from each other.

R²、R^2a及R^2b基的各取代數m、m1及m2係彼此相同或相異，可為例如0至3的整數，較佳為0至2的整數。此外，取代數m、m1及m2可因應所對應之R²、R^2a及R^2b基所鍵結之Z、Z¹及Z²的各原子價v、v1及v2而選擇，舉例而言，在原子價為2價之情況，取代數m、m1及m2為0，在原子價為3價之情況，取代數m、m1及m2為1，在原子價為4價之情況，取代數m、m1及m2為0或2，在原子價為5價之情況，取代數m、m1及m2為1或3，在原子價為6價之情況，取代數m、m1及m2大多為0、2或4(例如0或2，特別是0)。另外，取代數m、m1及m2可彼此相異，但通常多數情況係m1及m2至少相同，舉例而言，m1及m2可為0。 The respective substitution numbers m, m1 and m2 of the R ² , R ^2a and R ^2b groups are the same or different from each other, and may be, for example, an integer of 0 to 3, preferably an integer of 0 to 2. Further, the substitution numbers m, m1, and m2 may be selected according to the respective atomic valences v, v1, and v2 of Z, Z ^{1 ,} and Z ² to which the corresponding R ² , R ^{2a ,} and R ^2b groups are bonded, for example, When the valence is 2, the substitution number m, m1, and m2 are 0. When the valence is 3, the substitution number m, m1, and m2 are 1, and when the valence is 4, the substitution number m , m1 and m2 are 0 or 2, and when the valence is 5, the substitution number m, m1, and m2 are 1 or 3. When the valence is 6 valence, the substitution number m, m1, and m2 are mostly 0. 2 or 4 (eg 0 or 2, especially 0). Further, the substitution numbers m, m1, and m2 may be different from each other, but in most cases, m1 and m2 are at least the same, and m1 and m2 may be 0, for example.

作為R^3a及R^3b所表示之週期表第16族(6B族)元素，可列舉例如前述式(1)之R³之段落中所例示之原子等，亦包含較佳態樣在內為同樣者。R³、R^3a及R^3b的種 類可彼此相異，但通常多數情況係R^3a及R^3b至少相同。在取代數n1及n2為2之情況，2個R^3a及R^3b基的種類可彼此相同或相異。 Examples of the Group 16 (Group 6B) element of the periodic table represented by R ^3a and R ^3b include, for example, the atoms exemplified in the paragraph of R ³ of the above formula (1), and the same applies to the preferred embodiment. By. The kinds of R ³ , R ^3a and R ^3b may be different from each other, but in most cases, R ^3a and R ^{3b are} at least the same. In the case where the substitution number n1 and n2 are 2, the types of the two R ^3a and R ^3b groups may be the same or different from each other.

R³、R^3a及R^3b原子的各取代數n、n1及n2可因應所對應之R³、R^3a及R^3b原子所鍵結之Z、Z¹及Z²的各原子價v、v1及v2而選擇，舉例而言，在原子價為2價或3價之情況，取代數n、n1及n2為0，在原子價為4價或5價之情況，取代數n、n1及n2為0或1，在原子價為6價之情況，取代數n、n1及n2大多為0至2的整數(例如1或2，特別是2)。另外，取代數n、n1及n2可彼此相異，但通常多數情況係n1及n2至少相同，舉例而言，n1及n2可為0。 R ^3, R ^3a and R ^3b atoms each substituted with the number n, n1 and n2 may, upon corresponding to the R ^3, the bonding of R ^3a and R ^3b atom Z, each of valence v Z ¹ and Z ² is, v1 And v2, for example, in the case where the valence is 2 or 3, the substitution number n, n1, and n2 are 0, and when the valence is 4 or 5, the substitution numbers n, n1, and n2 are substituted. In the case of 0 or 1, in the case where the valence is 6 valence, the substitution numbers n, n1 and n2 are mostly integers of 0 to 2 (for example, 1 or 2, particularly 2). Further, the substitution numbers n, n1, and n2 may be different from each other, but in many cases, n1 and n2 are at least the same, and for example, n1 and n2 may be zero.

作為R^4a及R^4b所表示之取代基，可列舉例如前述式(1)之R^A及R^B基之段落中所例示之取代基(與前述R^1a及R^1b基同樣的取代基、含金屬(或半金屬)之基)、可具有烴基之雜芳基等。此等取代基之中，通常多數情況為鹵素原子、烴基、可具有烴基之雜芳基、含金屬(或半金屬)之基等。 Examples of the substituent represented by R ^4a and R ^4b include a substituent exemplified in the paragraphs of R ^A and R ^B groups of the above formula (1) (the same substituents as the above R ^1a and R ^1b groups, and the a metal (or a semimetal) group, a heteroaryl group which may have a hydrocarbon group, or the like. Among these substituents, a halogen atom, a hydrocarbon group, a heteroaryl group which may have a hydrocarbon group, a metal-containing (or semimetal) group, and the like are usually used in many cases.

作為鹵素原子，可列舉例如氟、氯、溴、碘(較佳為氯、溴、碘，更佳為溴)。 The halogen atom may, for example, be fluorine, chlorine, bromine or iodine (preferably chlorine, bromine or iodine, more preferably bromine).

作為烴基，可列舉例如烷基(例如甲基、乙基、丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正己基、正辛基、2-乙基己基、正癸基、正十二烷基(月桂基)等直鏈狀或分枝鏈狀C_1-20烷基等)；環烷基(例如環 戊基、環己基等C_5-10環烷基等)；芳基；將此等基組合2個以上而得之基[例如芳烷基(例如苯甲基、苯乙基等C_6-12芳基-C_1-10烷基等)；烷芳基等]等。此等烴基之中，較佳為芳基、烷芳基。 The hydrocarbon group may, for example, be an alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, n-hexyl group, n-octyl group, 2- a linear or branched chain C _1-20 alkyl group such as ethylhexyl, n-decyl or n-dodecyl (lauryl); cycloalkyl (for example, C ₅ such as cyclopentyl or cyclohexyl) _{a 10-} cycloalkyl group or the like; an aryl group; a group obtained by combining two or more of these groups [for example, an aralkyl group (for example, a C _6-12 aryl-C _1-10 alkyl group such as a benzyl group or a phenethyl group) Etc); alkaryl, etc.]. Among these hydrocarbon groups, an aryl group or an alkylaryl group is preferred.

作為芳基，可列舉例如苯基、聯苯基、萘基、聯萘基、蒽基、菲基等C_6-20芳基，較佳為C_6-14芳基，更佳為C_6-10芳基等。 The aryl group may, for example, be a C _6-20 aryl group such as a phenyl group, a biphenyl group, a naphthyl group, a binaphthyl group, an anthracenyl group or a phenanthryl group, preferably a C _6-14 aryl group, more preferably a C _6- group. ₁₀ aryl and the like.

作為烷芳基，可列舉例如甲苯基(甲基苯基)、二甲苯基(二甲基苯基)、正己基苯基、正辛基苯基、2-乙基己基-苯基、正癸基苯基、正十二烷基苯基等單至五(C_1-20烷基)C_6-20芳基，較佳為單至三(C_1-16烷基)C_6-14芳基(例如單或二(C_4-12烷基)C_6-12芳基等)，更佳為C_6-10烷基C_6-10芳基等。 Examples of the alkaryl group include tolyl (methylphenyl), xylyl (dimethylphenyl), n-hexylphenyl, n-octylphenyl, 2-ethylhexyl-phenyl, and anthracene. Mono- to penta(C _1-20 alkyl) C _6-20 aryl group such as phenyl or n-dodecylphenyl group, preferably mono to tri(C _1-16 alkyl) C _6-14 aryl (e.g., mono or di(C _4-12 alkyl) C _6-12 aryl, etc.), more preferably C _6-10 alkyl C _6-10 aryl or the like.

作為雜芳基，可大致區別成例如單環式雜芳基及多環式雜芳基，作為單環式雜芳基，可列舉例如含氮(N)單環式雜芳基(例如吡咯基、2H-吡咯基、咪唑基、吡唑基、吡啶基、吡基、嘧啶基、嗒基等)；含氧(O)單環式雜芳基(例如呋喃基、哌喃基等)；含硫(S)單環式雜芳基(例如噻吩基(2-噻吩基、3-噻吩基)等)；含有2種以上雜原子之單環式雜芳基(例如唑基、異唑基、噻唑基、異噻唑基、噻基、呋呫基、噻二唑基、噻二基、噻***基等)等C_1-5雜芳基(較佳為C_3-5雜芳基)等。 As the heteroaryl group, for example, a monocyclic heteroaryl group and a polycyclic heteroaryl group can be roughly distinguished, and as the monocyclic heteroaryl group, for example, a nitrogen-containing (N) monocyclic heteroaryl group (for example, pyrrolyl group) can be cited. , 2H-pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime An oxygen-containing (O) monocyclic heteroaryl group (e.g., furanyl, piperidyl, etc.); a sulfur-containing (S) monocyclic heteroaryl group (e.g., thienyl (2-thienyl, 3-thiophene) a monocyclic heteroaryl group containing two or more kinds of hetero atoms (for example) Azolyl, different Azyl, thiazolyl, isothiazolyl, thia Base, furazinyl, thiadiazolyl, thiadipine A C _1-5 heteroaryl group (preferably a C _3-5 heteroaryl group), etc., such as a thiolazolyl group or the like.

作為多環式雜芳基，可列舉例如含氮(N)多環式雜芳基(例如吲基、吲哚基、3H-吲哚基、異吲哚基、 1H-吲唑基、嘌呤基、喹啉基、異喹啉基、4H-喹基、呔基、啶基、喹啉基、喹唑啉基、噌啉基(cinnolinyl)、喋啶基、咔唑基、4aH-咔唑基、β-咔啉基、吖啶基、啡啶基、啡基、啡啉基、呸啶基(perimidinyl)等)；含氧(O)多環式雜芳基(例如苯并呋喃基、異苯并呋喃基、苯并哌喃基(chromenyl)、二苯并哌喃基(xanthenyl)等)；含硫(S)多環式雜芳基(例如噻吩并噻吩基、噻嗯基等)；含有2種以上雜原子之多環式雜芳基(例如啡基、啡噻基、啡噻基(phenoxathiinyl)、啡呻基(phenarsazinyl)等)等C_6-13雜芳基(較佳為C_6-9雜芳基)等。 As the polycyclic heteroaryl group, for example, a nitrogen-containing (N) polycyclic heteroaryl group (for example, hydrazine) may be mentioned. Base, fluorenyl, 3H-fluorenyl, isodecyl, 1H-carbazolyl, fluorenyl, quinolinyl, isoquinolinyl, 4H-quina Base base, Pyridyl, quin Lolinyl, quinazolinyl, cinnolinyl, acridinyl, oxazolyl, 4aH-carbazolyl, β-carboline, acridinyl, phenanthryl, brown Alkyl, morpholinyl, perimidinyl, etc.; oxygenated (O) polycyclic heteroaryl (eg benzofuranyl, isobenzofuranyl, chromenyl, diphenyl) And xanthenyl, etc.; sulfur-containing (S) polycyclic heteroaryl (such as thienothiophenyl, thiophene, etc.); polycyclic heteroaryl containing two or more heteroatoms (such as brown Thiophene Base Phenoxoxin, morphine A C _6-13 heteroaryl group (preferably a C _6-9 heteroaryl group), etc., such as a phenarsazinyl group.

此等雜芳基之中，由可以較高的程度兼顧溶解性及電特性之方面而言，較佳為單環式雜芳基，該等之中，較佳為含氮(N)單環式雜芳基、含硫(S)單環式雜芳基，特佳為噻吩基等含硫(S)單環式雜芳基。 Among these heteroaryl groups, a monocyclic heteroaryl group is preferred from the viewpoint of a high degree of compatibility between solubility and electrical properties, and among these, a nitrogen-containing (N) monocyclic ring is preferred. A heteroaryl group, a sulfur-containing (S) monocyclic heteroaryl group, particularly preferably a sulfur-containing (S) monocyclic heteroaryl group such as a thienyl group.

作為在前述雜芳基中進行取代之烴基，可列舉例如上述例示之烴基(例如烷基、環烷基、芳基等)等。此外，取代數並無特別限制，可因應雜芳基而選擇，可為例如0至5左右的整數，較佳為0至3(例如0至2)左右的整數，更佳為0或1左右。因此，作為經烴基取代之雜芳基，可列舉例如烷基-雜芳基、環烷基-雜芳基、芳基-雜芳基等，通常多數情況為C_1-20烷基-C_1-13雜芳基、C_6-12芳基-C_1-13雜芳基(例如C_1-16烷基-C_3-9雜芳基，特別是C_1-12烷基-C_3-5雜芳基)。 The hydrocarbon group substituted in the above heteroaryl group may, for example, be a hydrocarbon group (for example, an alkyl group, a cycloalkyl group or an aryl group) exemplified above. Further, the number of substitutions is not particularly limited and may be selected depending on the heteroaryl group, and may be, for example, an integer of about 0 to 5, preferably an integer of about 0 to 3 (for example, 0 to 2), more preferably about 0 or 1. . Therefore, examples of the heteroaryl group substituted with a hydrocarbon group include an alkyl-heteroaryl group, a cycloalkyl-heteroaryl group, an aryl-heteroaryl group and the like, and in most cases, a C _1-20 alkyl group-C _{1 -13} heteroaryl, C _6-12 aryl-C _1-13 heteroaryl (eg C _1-16 alkyl-C _3-9 heteroaryl, especially C _1-12 alkyl-C _3-5 Heteroaryl).

作為含金屬(或半金屬)之基，可列舉例如與 前述R^A及R^B基之段落中所例示之基同樣的基等。作為含金屬(或半金屬)之基，多數情況為例如鋰原子(鋰基)、-B(OH)₂基、鹵鋅基(溴鋅基等)、鹵鎂基(溴鎂基等)、三烷基錫烷基(三甲基錫烷基等三C_1-6烷基錫烷基等)、三鹵矽基(三氟矽基、三氯矽基等)、三烷基矽基(三甲基矽基等三C_1-6烷基矽基等)等。 Examples of the metal-containing (or semimetal) group include the same groups as those exemplified in the paragraphs of the above R ^A and R ^B groups. Examples of the metal-containing (or semi-metal) group include, for example, a lithium atom (lithium group), a -B(OH) ₂ group, a halozinc group (bromozinc group, etc.), a halomagnesium group (bromomagnesium group, etc.), a trialkylstannyl group (such as a tri-C _1-6 alkyl tin alkyl group such as a trimethylstannyl group), a trihalofluorenyl group (trifluoroindolyl group, a trichloroindenyl group, etc.), or a trialkyl fluorenyl group ( A tri-C _1-6 alkyl fluorenyl group such as a trimethyl fluorenyl group or the like).

此等R^4a及R^4b基之中，較佳為氫原子、鹵素原子、芳基(例如C_6-14芳基等)、烷芳基(例如C_1-20烷基C_6-14芳基等)、雜芳基(例如C_4-13雜芳基等)、烷基雜芳基(例如C_1-20烷基C_4-13雜芳基等)，該等之中，特佳為氫原子、鹵素原子(例如氯、溴、碘，特別是溴)、C_6-12芳基(特別是C_6-10芳基)、C_1-16烷基C_6-12芳基(例如C_1-12烷基C_6-10芳基)、C_4-9雜芳基(例如C_4-5雜芳基)、C_1-16烷基C_4-9雜芳基(例如C_1-12烷基C_4-5雜芳基)。另外，R^4a及R^4b基的種類可彼此相異，但通常多數情況係相同。 Among these R ^4a and R ^4b groups, preferred are a hydrogen atom, a halogen atom, an aryl group (e.g., a C _6-14 aryl group, etc.), an alkaryl group (e.g., a C _1-20 alkyl C _6-14 aryl group). And the like, a heteroaryl group (for example, a C _4-13 heteroaryl group, etc.), an alkylheteroaryl group (for example, a C _1-20 alkyl C _4-13 heteroaryl group, etc.), among which, particularly preferably hydrogen Atom, a halogen atom (for example, chlorine, bromine, iodine, especially bromine), a C _6-12 aryl group (especially a C _6-10 aryl group), a C _1-16 alkyl C _6-12 aryl group (for example, C _{1 -12} alkyl C _6-10 aryl), C _4-9 heteroaryl (eg C _4-5 heteroaryl), C _1-16 alkyl C _4-9 heteroaryl (eg C _1-12 alkane) Base C _4-5 heteroaryl). Further, the kinds of the R ^4a and R ^4b groups may be different from each other, but usually they are usually the same.

此外，在Z、Z¹及Z²皆為硫原子之情況，R^4a及R^4b可為氫原子、鹵素原子、可具有烴基之雜芳基、鋰原子、-B(OH)₂基、-ZnX⁴基、-MgX⁵基、-Sn(R⁸)₃基或-Si(R⁹)₃基，較佳係多數情況為氫原子、鹵素原子、雜芳基(例如C_4-13雜芳基等)或烷基雜芳基(例如C_1-20烷基C_4-13雜芳基等)。 Further, in the case where Z, Z ¹ and Z ² are each a sulfur atom, R ^4a and R ^4b may be a hydrogen atom, a halogen atom, a heteroaryl group which may have a hydrocarbon group, a lithium atom, a -B(OH) ₂ group, - ZnX ⁴ -based, -MgX ⁵ -based, -Sn(R ⁸ ) ₃ -based or -Si(R ⁹ ) ₃ -based, preferably in most cases a hydrogen atom, a halogen atom, a heteroaryl group (for example, C _4-13 heteroaryl) Or an alkylheteroaryl group (e.g., a C _1-20 alkyl C _4-13 heteroaryl group, etc.).

作為R^5a及R^5b所表示之取代基，可列舉例如與前述式(1)之R^1a及R^1b基之段落中所例示之取代基同樣的取代基等。R^5a及R^5b基的種類可彼此相異，但通常多 數情況係R^5a及R^5b基至少相同。作為較佳的R^5a及R^5b基，為氫原子或烴基(例如烷基、環烷基、芳基、芳烷基、烷芳基，較佳為烷基、環烷基、芳基等)，更佳係可為氫原子、C_1-16烷基、C_5-10環烷基或C_6-12芳基(例如氫原子、C_1-10烷基、C_5-8環烷基或C_6-10芳基等)，特別是氫原子、C_1-6烷基或C_6-10芳基(特別是氫原子)。 Examples of the substituent represented by R ^5a and R ^5b include the same substituents as those exemplified in the paragraphs of R ^1a and R ^{1b of the} above formula (1). The types of the R ^5a and R ^5b groups may be different from each other, but in most cases, the R ^5a and R ^5b groups are at least the same. Preferred R ^5a and R ^5b groups are a hydrogen atom or a hydrocarbon group (e.g., an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkylaryl group, preferably an alkyl group, a cycloalkyl group, an aryl group, etc.). More preferably, it may be a hydrogen atom, a C _1-16 alkyl group, a C _5-10 cycloalkyl group or a C _6-12 aryl group (for example, a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group or C _6-10 aryl, etc.), especially a hydrogen atom, a C _1-6 alkyl group or a C _6-10 aryl group (particularly a hydrogen atom).

作為前述式(1B)所示之應變型化合物，代表性而言，可列舉例如對應於前述表1中所記載之Z、R²、m、R³及n之組合，且Z¹及Z²為硫原子，m1及m2以及n1及n2為0，R^1a及R^1b基為氫原子或烷基(例如C_1-30烷基等)，R^5a及R^5b基為氫原子，R^4a及R^4b基為氫原子、鹵素原子、C_6-14芳基、C_1-20烷基C_6-14芳基、C_4-13雜芳基、C_1-20烷基C_4-13雜芳基、鋰原子、-B(OH)₂基、鹵鋅基(溴鋅基等)、鹵鎂基(溴鎂基等)、三烷基錫烷基(三甲基錫烷基等三C_1-4烷基錫烷基等)、三鹵矽基(三氟矽基、三氯矽基等)或三烷基矽基(三甲基矽基等三C_1-4烷基矽基等)之化合物等。 The strain type compound represented by the above formula (1B) is typically represented by, for example, a combination of Z, R ² , m, R ³ and n described in Table 1 above, and Z ¹ and Z ^{2 .} Is a sulfur atom, m1 and m2 and n1 and n2 are 0, R ^1a and R ^1b are a hydrogen atom or an alkyl group (for example, a C _1-30 alkyl group), and R ^5a and R ^5b are a hydrogen atom, R ^4a and The R ^4b group is a hydrogen atom, a halogen atom, a C _6-14 aryl group, a C _1-20 alkyl C _6-14 aryl group, a C _4-13 heteroaryl group, a C _1-20 alkyl C _4-13 heteroaryl group. group, a lithium atom, -B (OH) ₂ group, a halogen group of zinc (zinc-bromo-yl, etc.), halomagnesium (magnesium bromo-yl, etc.), trialkyl stannyl (trimethylstannyl other three C _{1 a -4} alkylstannyl group, etc., a trihalofluorenyl group (such as a trifluoroindenyl group, a trichloroindenyl group) or a trialkylsulfonyl group (a tri-C _1-4 alkyl fluorenyl group such as a trimethyl fluorenyl group) Compounds and the like.

在前述式(1B)中，作為Z¹及Z²為硫原子，m1及m2以及n1及n2為0，R^1a及R^1b基以及R^5a及R^5b基為氫原子之應變型化合物，更具體而言，可列舉例如(1B-a)Z為硫原子之化合物、(1B-b)Z為硒原子之化合物、(1B-c)Z為磷原子之化合物、(1B-d)Z為矽原子之化合物、(1B-e)Z為氧原子之化合物、(1B-f)Z為碳原子之化合物等。 In the above formula (1B), as a strain type compound in which Z ¹ and Z ² are a sulfur atom, m1 and m2, and n1 and n2 are 0, R ^1a and R ^1b groups, and R ^5a and R ^5b groups are a hydrogen atom, Specifically, for example, (1B-a) Z is a compound of a sulfur atom, (1B-b) Z is a compound of a selenium atom, (1B-c) Z is a compound of a phosphorus atom, and (1B-d)Z is A compound of a halogen atom, a compound of (1B-e)Z being an oxygen atom, a compound of (1B-f)Z being a carbon atom, or the like.

作為(1B-a)Z為硫原子之化合物，可列舉例如(1B-a1)二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a2)2,6-二氯-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-二溴-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-二碘-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-二鹵-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a3)2,6-二萘基-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-二C_6-10芳基-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a4)2,6-雙(4-己基苯基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-雙(4-癸基苯基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-雙(3-癸基苯基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-雙(C_1-12烷基C_6-10芳基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a5)2,6-二(2-噻吩基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-二C_4-9雜芳基-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a6)2,6-雙(5-己基-2-噻吩基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-雙(C_1-12烷基C_4-9雜芳基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a7)2,6-二鋰基-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a8)2,6-雙(二羥基氧硼基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a9)2,6-雙(氯鋅基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-雙(溴鋅基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-雙(碘鋅基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-雙(鹵鋅基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a10)2,6-雙(氯鎂基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-雙(溴鎂基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、 2,6-雙(碘鎂基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-雙(鹵鎂基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a11)2,6-雙(三甲基錫烷基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-雙(三正丁基錫烷基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-雙(三C_1-4烷基錫烷基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a12)2,6-雙(三氟矽基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-雙(三氯矽基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-雙(三鹵矽基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a13)2,6-雙(三甲基矽基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯、2,6-雙(三正丁基矽基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等2,6-雙(三C_1-4烷基矽基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯；(1B-a14)對應於此等(1B-a1)至(1B-a13)中所例示之化合物之S-氧化物體(亞磺醯基體)或S,S(或4,4)-二氧化物體(磺醯基體)(例如4,4-二側氧基-二噻吩并[3,2-b：2,3-f]硫雜環庚烯等)等]等。此等(1B-a)Z為硫原子之化合物之中，多數情況為化合物(1B-a1)至(1B-a2)及化合物(1B-a5)至(1B-a14)。 The compound (1B-a) wherein Z is a sulfur atom may, for example, be (1B-a1)dithieno[3,2-b:2,3-f]thiepine; (1B-a2)2, 6-Dichloro-dithieno[3,2-b:2,3-f]thiene, 2,6-dibromo-dithieno[3,2-b:2,3-f] 2,6-dihalo-dithieno[3,2-, such as thiaheptene, 2,6-diiodo-dithieno[3,2-b:2,3-f]thiene b: 2,3-f]thiazepine; (1B-a3) 2,6-dinaphthyl-dithieno[3,2-b:2,3-f]thiepinee, etc. 2 , 6-di-C _6-10 aryl-dithieno[3,2-b:2,3-f]thiepine; (1B-a4) 2,6-bis(4-hexylphenyl) -dithieno[3,2-b:2,3-f]thiene, 2,6-bis(4-mercaptophenyl)-dithieno[3,2-b:2,3 -f]thiazide, 2,6-bis(3-mercaptophenyl)-dithieno[3,2-b:2,3-f]thiatene, etc. 2,6-double (C _1-12 alkyl C _6-10 aryl)-dithieno[3,2-b:2,3-f]thiatene; (1B-a5)2,6-di(2- 2,6- _diC 4-9heteroaryl-dithieno[3,2-b:2], such as thienyl)-dithieno[3,2-b:2,3-f]thiepine , 3-f]thiazepine; (1B-a6) 2,6-bis(5-hexyl-2-thienyl)-dithieno[3,2-b:2,3-f]thiazepine cycloheptene like 2,6-bis (C _1-12 C _4-9 heteroaryl group) - di-thieno [3,2-b: 2,3-f ] thietanyl heptene; (1B-a7) 2,6- dilithium group - two-thieno [3 , 2-b: 2,3-f]thiazepine; (1B-a8) 2,6-bis(dihydroxyboroboryl)-dithieno[3,2-b:2,3-f Thioheptene; (1B-a9) 2,6-bis(chlorozincyl)-dithieno[3,2-b:2,3-f]thiepine, 2,6-double (bromozinc)-dithieno[3,2-b:2,3-f]thiene, 2,6-bis(iodozincyl)-dithieno[3,2-b:2 , 3,6-bis(halozinc-yl)-dithieno[3,2-b:2,3-f]thiaheptene; (1B-a10)2 ,6-bis(chloromagnesium)-dithieno[3,2-b:2,3-f]thiene, 2,6-bis(bromomagnesium)-dithieno[3,2 -b: 2,3-f]thiazepine, 2,6-bis(iodomagnesium)-dithieno[3,2-b:2,3-f]thiene, etc. 2, 6-bis(halomagnesium)-dithieno[3,2-b:2,3-f]thiepine; (1B-a11)2,6-bis(trimethylstannyl)- Dithieno[3,2-b:2,3-f]thiene, 2,6-bis(tri-n-butylstannyl)-dithieno[3,2-b:2,3-f 2,6-bis(tris(C) _1-4 alkylstannyl)-dithieno[3,2-b:2,3-f]thiepinee; (1B-) A12) 2,6-bis(trifluoromethyl) )-dithieno[3,2-b:2,3-f]thiene, 2,6-bis(trichloroindenyl)-dithieno[3,2-b:2,3- f] 2,6-bis(trihaloindenyl)-dithieno[3,2-b:2,3-f]thiepinee; (1B-a13) 2,6 - bis(trimethyldecyl)-dithieno[3,2-b:2,3-f]thiepine, 2,6-bis(tri-n-butyldecyl)-dithieno[ 2,6-bis(3C _1-4 alkylmercapto)-dithieno[3,2-b:2,3-f such as 3,2-b:2,3-f]thenylene a thiaheptene; (1B-a14) corresponds to the S-oxide (sulfinyl) or S, S (or 4) of the compound exemplified in (1B-a1) to (1B-a13) 4)-dioxide (sulfonyl sulfonate) (for example, 4,4-di-oxy-dithieno[3,2-b:2,3-f]thiaheptene, etc.), etc.]. Among the compounds in which (1B-a) Z is a sulfur atom, in many cases, the compounds (1B-a1) to (1B-a2) and the compounds (1B-a5) to (1B-a14).

作為(1B-b)Z為硒原子之化合物，可列舉例如對應於前述(1B-a)Z為硫原子之化合物中所例示之化合物(1B-a1)至(1B-a14)，並將Z自硫原子置換成硒原子而得之化合物(1B-b1)至(1B-b14)(例如(1B-b1)硒雜環庚烯并[3,2-b：6,7-b’]二噻吩等)等。 The compound (1B-a1) to (1B-a14) exemplified as the compound corresponding to the above (1B-a) Z is a sulfur atom, and the compound (1B-b) wherein Z is a selenium atom, and Z a compound (1B-b1) to (1B-b14) obtained by substituting a sulfur atom for a selenium atom (for example, (1B-b1) selenium heptene [3,2-b:6,7-b'] Thiophene, etc.).

作為(1B-c)Z為磷原子之化合物，可列舉例如(1B-c1)磷雜環庚烯并[3,2-b：6,7-b’]二噻吩類(例如磷雜 環庚烯并[3,2-b：6,7-b’]二噻吩；4-甲基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩等4-C_1-4烷基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩；4-苯基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩等4-C_6-10芳基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩等)；對應於前述(1B-a)Z為硫原子之化合物之段落中所例示之化合物(1B-a2)至(1B-a13)，並將二噻吩并[3,2-b：2,3-f]硫雜環庚烯環置換成前述(1B-c1)磷雜環庚烯并[3,2-b：6,7-b’]二噻吩類而得之化合物(1B-c2)至(1B-c13)[例如(1B-c2)2,6-二鹵-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩類(例如2,6-二溴-4-苯基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩等2,6-二鹵-4-C_6-10芳基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩等)；(1B-c14)對應於此等(1B-c1)至(1B-c13)中所例示之化合物之P-氧化物體(例如4-側氧基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩等)等。 The compound (1B-c) wherein Z is a phosphorus atom may, for example, be a (1B-c1)phospholeene [3,2-b:6,7-b']dithiophene (for example, a phosphonium 4-O-[3,2-b:6,7-b']dithiophene;4-methyl-phospholeepeno[3,2-b:6,7-b']dithiophene, etc. 4-C _1-4 alkyl-phosphole hepteno[3,2-b:6,7-b']dithiophene; 4-phenyl-phospholeene [3,2-b:6,7 -b'] 4-C _6-10 aryl-phospholeene [3,2-b:6,7-b']dithiophene, etc.); corresponding to the above (1B-a)Z a compound (1B-a2) to (1B-a13) exemplified in the paragraph of the compound of a sulfur atom, and a dithieno[3,2-b:2,3-f]thenyl ring is substituted Compounds (1B-c2) to (1B-c13) obtained by the above (1B-c1)phosphorane[3,2-b:6,7-b']dithiophene [for example, (1B-c2) 2,6-dihalo-phosphacyclohepta[3,2-b:6,7-b']dithiophenes (eg 2,6-dibromo-4-phenyl-phosphole) And [3,2-b:6,7-b']dithiophene, etc. 2,6-dihalo-4-C _6-10 aryl-phospholeene [3,2-b:6,7 -b']dithiophene or the like); (1B-c14) corresponds to a P-oxide body of the compound exemplified in (1B-c1) to (1B-c13) (for example, 4-side oxy-phosphorus heterocycle) Heptene[3,2-b:6 , 7-b'] dithiophene, etc.).

作為(1B-d)Z為矽原子之化合物，可列舉例如(1B-d1)矽雜環庚烯并[3,2-b：6,7-b’]二噻吩類(例如矽雜環庚烯并[3,2-b：6,7-b’]二噻吩；4-甲基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩等4-C_1-4烷基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩；4-苯基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩等4-C_6-10芳基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩；4,4-二甲基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩等4,4-二C_1-4烷基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩；4-甲基-4-苯基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩等4-C_1-4烷基-4-C_6-10芳基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩；4,4-二苯基-矽 雜環庚烯并[3,2-b：6,7-b’]二噻吩等4,4-二C_6-10芳基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩等)；對應於前述(1B-a)Z為硫原子之化合物之段落中所例示之化合物(1B-a2)至(1B-a13)，並將二噻吩并[3,2-b：2,3-f]硫雜環庚烯環置換成前述(1B-d1)矽雜環庚烯并[3,2-b：6,7-b’]二噻吩類而得之化合物(1B-d2)至(1B-d13)[例如(1B-d2)2,6-二鹵-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩類(例如2,6-二溴-4,4-二甲基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩等2,6-二鹵-4,4-二C_1-4烷基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩等)等。 The compound (1B-d) wherein Z is a halogen atom may, for example, be a (1B-d1) anthracene heptene [3,2-b:6,7-b']dithiophene (for example, anthracene 4-O-[3,2-b:6,7-b']dithiophene; 4-methyl-fluorene heteroheptene[3,2-b:6,7-b']dithiophene, etc. 4-C _1-4 alkyl-fluorene heterocyclohepteno[3,2-b:6,7-b']dithiophene; 4-phenyl-fluorene heterocycleheptene[3,2-b:6,7 -b']dithiophene and the like 4-C _6-10 aryl-fluorene heterocyclohepten[3,2-b:6,7-b']dithiophene; 4,4-dimethyl-anthracene heterocycle 4,4-diC _1-4 alkyl-fluorene heterocycloheptene [3,2-b:6,7-b], hepteno[3,2-b:6,7-b']dithiophene ']Dithiophene; 4-methyl-4-phenyl-fluorene heterocycloheptene [3,2-b:6,7-b']dithiophene, etc. 4-C _1-4 alkyl-4-C _6-10 aryl-fluorene heterocycloheptylene [3,2-b:6,7-b']dithiophene; 4,4-diphenyl-fluorene heterocycleheptene [3,2-b: 6,7-b']dithiophene, etc. 4,4-di C _6-10 aryl-fluorene heterocycloheptene [3,2-b:6,7-b']dithiophene, etc.); corresponding to the foregoing (1B-a) Compounds (1B-a2) to (1B-a13) exemplified in the paragraph of the compound in which Z is a sulfur atom, and dithieno[3,2-b:2,3-f]thiazepine The cycloheptene ring is substituted with the aforementioned (1B-d1) anthracene heptene [3,2-b:6,7-b']dithiazide Ordinary compounds (1B-d2) to (1B-d13) [eg (1B-d2) 2,6-dihalo-fluorene heterocyclenene [3,2-b:6,7-b'] Dithiophenes (for example, 2,6-dihalo such as 2,6-dibromo-4,4-dimethyl-fluorene heterocyclohepta[3,2-b:6,7-b']dithiophene- 4,4-DiC _1-4 alkyl-fluorene heterocyclohepteno[3,2-b:6,7-b']dithiophene, etc.).

作為(1B-e)Z為氧原子之化合物，可列舉例如對應於前述(1B-a)Z為硫原子之化合物中所例示之化合物(1B-a1)至(1B-a13)，並將Z自硫原子置換成氧原子而得之化合物(1B-e1)至(1B-e13)(例如(1B-e1)二噻吩并[3,2-b：2,3-f]氧雜環庚烯等)等。 The compound (1B-a1) to (1B-a13) exemplified in the compound corresponding to the above (1B-a) Z is a sulfur atom, and the compound (1B-e) wherein Z is an oxygen atom, and Z a compound (1B-e1) to (1B-e13) obtained by substituting a sulfur atom for an oxygen atom (for example, (1B-e1) dithieno[3,2-b:2,3-f]oxacycloheptene and many more.

作為(1B-f)Z為碳原子之化合物，可列舉例如對應於作為前述(1B-d)Z為矽原子之化合物所例示之化合物(1B-d1)至(1B-d13)，並將Z之矽原子置換成碳原子而得之化合物(1B-f1)至(1B-f13)[例如4,4-二甲基-環庚[1,2-b：5,4-b’]二噻吩等]等。 The compound (1B-d1) to (1B-d13) exemplified as the compound of the above (1B-d)Z is a ruthenium atom, and the compound (1B-f) is a compound of a carbon atom. a compound (1B-f1) to (1B-f13) obtained by substituting a halogen atom into a carbon atom [for example, 4,4-dimethyl-cyclohepta[1,2-b:5,4-b']dithiophene and many more.

另外，在前述(1B-a)至(1B-f)中，係針對R^1a及R^1b基為氫原子之化合物進行例示，但亦包含對應於前述例示化合物，且R^1a及R^1b基為烷基(例如C_1-25烷基，較佳為C_1-20烷基等)之化合物。 Further, in the above (1B-a) to (1B-f), the compounds in which the R ^1a and R ^1b groups are a hydrogen atom are exemplified, but also include the compounds exemplified above, and the R ^1a and R ^1b groups are A compound of an alkyl group (e.g., a C _1-25 alkyl group, preferably a C _1-20 alkyl group, etc.).

此等化合物(1B-a)至(1B-f)之中，較佳為化 合物(1B-a)、(1B-b)、(1B-c)、(1B-d)[例如化合物(1B-b)、(1B-c)、(1B-d)]。 Among these compounds (1B-a) to (1B-f), preferred are the compounds (1B-a), (1B-b), (1B-c), (1B-d) [for example, the compound (1B-) b), (1B-c), (1B-d)].

前述式(1)所示之化合物亦可包含前述式(1A)及式(1B)所示之化合物以外之化合物(例如硫雜環庚烯并[3,2-e：6,7-e’]二[1]苯并噻吩、硫雜環庚烯并[3,2-e：6,7-e’]二[1]苯并呋喃、硫雜環庚烯并[3,2-e：6,7-e’]二吲哚等硫雜環庚烯并二苯并雜芳烴等)。 The compound represented by the above formula (1) may further contain a compound other than the compound represented by the above formula (1A) and formula (1B) (for example, thiaheptene [3,2-e: 6,7-e'二[1]benzothiophene, thiaheptene[3,2-e:6,7-e']bis[1]benzofuran, thiepene[3,2-e: 6,7-e'] dithizone and other thiae-heterobibenzoheteroaryl, etc.).

此等前述式(1)所示之化合物亦可單獨地或組合2種以上使用。前述式(1)所示之化合物之中，較佳為包含選自前述式(1A)及式(1B)所示之化合物之至少1種化合物者，該等之中，較佳為至少包含式(1B)所示之化合物者。 The compounds represented by the above formula (1) may be used singly or in combination of two or more. Among the compounds represented by the above formula (1), at least one compound selected from the compounds represented by the above formula (1A) and formula (1B) is preferably contained, and among these, at least the formula is preferably contained. The compound shown in (1B).

本發明之有機半導體係只要至少包含前述式(1)所示之應變型化合物即可，前述應變型化合物亦可單獨地或組合2種以上使用。 The organic semiconductor system of the present invention may contain at least the strain type compound represented by the above formula (1), and the strain type compounds may be used singly or in combination of two or more.

在本發明之有機半導體中，應變型化合物即便不具有長鏈烷基等取代基，亦可能由於7員環骨架(應變型骨架)而顯示出較高的溶解性，可兼顧溶解性及移動度。因此，應變型化合物對甲苯之溶解度可為例如0.01重量%以上(例如0.05至30重量%左右)，較佳為0.1重量%以上(例如0.15至10重量%左右)，更佳為0.2重量%以上(例如0.2至1重量%左右)。另外，溶解度可藉由後述之實施例中所記載之方法予以測定。 In the organic semiconductor of the present invention, the strain-type compound may exhibit high solubility due to a 7-membered ring skeleton (strain type skeleton) even if it does not have a substituent such as a long-chain alkyl group, and can simultaneously satisfy solubility and mobility. . Therefore, the solubility of the strain-type compound to toluene may be, for example, 0.01% by weight or more (e.g., about 0.05 to 30% by weight), preferably 0.1% by weight or more (e.g., about 0.15 to 10% by weight), and more preferably 0.2% by weight or more. (for example, about 0.2 to 1% by weight). Further, the solubility can be measured by the method described in the examples below.

此外，在本發明之有機半導體中，應變型 化合物儘管具有較高的溶解性，卻仍具有較高的移動度(電移動度或載子移動度)。因此，使用前述應變型化合物製作場效型電晶體之情況之移動度可為例如0.001至0.5cm²/Vs，較佳為0.01至0.3cm²/Vs，更佳為0.02至0.25cm²/Vs(例如0.05至0.2cm²/Vs)左右。另外，移動度可藉由後述之實施例中所記載之方法予以測定。 Further, in the organic semiconductor of the present invention, the strain-type compound has a high mobility (electric mobility or carrier mobility) despite having high solubility. Therefore, the mobility of the case of producing the field effect type transistor using the strain type compound may be, for example, 0.001 to 0.5 cm ² /Vs, preferably 0.01 to 0.3 cm ² /Vs, more preferably 0.02 to 0.25 cm ² /Vs. (for example, 0.05 to 0.2 cm ² /Vs). Further, the degree of mobility can be measured by the method described in the examples below.

若以本發明之有機半導體形成裝置元件(例如有機薄膜電晶體等)，則可減低操作電壓。舉例而言，在由前述應變型化合物所形成之裝置元件中，閾值電壓的絕對值可為例如100V以下(例如0.1至70V左右)，較佳為50V以下(例如1至40V左右)，更佳為30V以下(例如3至20V左右)。 When the device of the present invention (for example, an organic thin film transistor) is formed by the organic semiconductor of the present invention, the operating voltage can be reduced. For example, in the device element formed of the strain type compound, the absolute value of the threshold voltage may be, for example, 100 V or less (for example, about 0.1 to 70 V), preferably 50 V or less (for example, about 1 to 40 V), more preferably It is 30V or less (for example, about 3 to 20V).

此外，在前述裝置元件中，移動度不易偏差，可減低各向異性。因此，即便使結晶生長方向(或π堆疊方向)與自源極電極朝向汲極電極之方向(或載子移動之方向)所成之角度產生變化而形成元件，亦可減低移動度的偏差，裝置元件(例如有機薄膜電晶體等)製作中之再現性較高。 Further, in the above-described device elements, the mobility is not easily deviated, and the anisotropy can be reduced. Therefore, even if the crystal growth direction (or the π stacking direction) is changed from the angle formed by the direction from the source electrode toward the gate electrode (or the direction in which the carrier moves) to form an element, the deviation of the mobility can be reduced. Reproducibility in the fabrication of device components (eg, organic thin film transistors, etc.) is high.

[式(1)所示之應變型化合物之製造方法] [Method for Producing Strain Type Compound of Formula (1)]

前述式(1)所示之應變型化合物之製造方法並無特別限制，可依照例如下述反應式(方法A)予以調製。 The method for producing the strain type compound represented by the above formula (1) is not particularly limited, and can be prepared, for example, according to the following reaction formula (Method A).

(式中，X^1a、X^1b及X²表示鹵素原子，Ph表示苯基，L¹表示鹵素原子或-SO₂R⁶基(R⁶表示烴基或氟烴基)，Z、A¹、A²、R^1a、R^1b、R²、R³、R^A、R^B、m、n、p1及p2係各自亦包含較佳態樣在內並與前述式(1)之記載相同)。 (wherein, X ^1a , X ^1b and X ² represent a halogen atom, Ph represents a phenyl group, L ¹ represents a halogen atom or a -SO ₂ R ⁶ group (R ⁶ represents a hydrocarbon group or a fluorohydrocarbon group), Z, A ¹ , A ² R ^1a , R ^1b , R ² , R ³ , R ^A , R ^B , m, n, p1 and p2 each contain a preferred embodiment and are the same as described in the above formula (1).

(方法A) (Method A)

<式(3)所示之化合物的合成(還原反應)> Synthesis (reduction reaction) of the compound represented by the formula (3) >

前述式(3)所示之羥基化合物可藉由將式(2a)所示之羰基化合物利用還原劑進行還原而予以調製。 The hydroxy compound represented by the above formula (3) can be prepared by reducing a carbonyl compound represented by the formula (2a) by a reducing agent.

在前述式(2a)中，作為X^1a所表示之鹵素原子，可列舉例如氯、溴、碘等，較佳為溴。作為式(2a)所示之羰基化合物，只要是對應於前述式(1)所示之應變型化合物之羰基化合物即可，通常多數情況係R^1a為氫原子。作為式(2a)所示之羰基化合物，代表性而言，可為例如醛類[例如o-溴-苯甲醛、2-溴-1-萘甲醛、3-溴-2-萘甲醛等鹵基-甲醯基芳烴；3-溴吡咯-2-甲醛、3-溴呋喃-2-甲醛、3-溴噻吩-2-甲醛、3-溴硒吩-2-甲醛等3-鹵基-雜芳烴-2-甲醛等]；酮類[例如o-溴-庚醯基-苯、2-溴-1-十一烷醯基-萘、3-溴-2-十七烷醯基萘等鹵基-C_2-31烷醯基-芳烴；3-溴-2-庚醯基-吡咯、3-溴-2-十一烷醯基-呋喃、3-溴-2-十七烷醯基-噻吩、3-溴-2-庚醯基-硒吩等3-鹵基-2-C_2-31烷醯基-雜芳烴等]等。此等式(2a)所示之羰基化合物之中，較佳為鹵基-甲醯基芳烴、3-鹵基-雜芳烴-2-甲醛等醛類。式(2a)所示之羰基化合物可購自市面，亦可藉由慣用的方法(例如將二鹵-芳烴環等進行甲醯化之方法等)予以調製。 In the above formula (2a), examples of the halogen atom represented by X ^1a include chlorine, bromine, and iodine, and bromine is preferred. The carbonyl compound represented by the formula (2a) may be a carbonyl compound corresponding to the strain type compound represented by the above formula (1), and in many cases, R ^1a is usually a hydrogen atom. The carbonyl compound represented by the formula (2a) may, for example, be an aldehyde (for example, a halogen group such as o-bromo-benzaldehyde, 2-bromo-1-naphthaldehyde or 3-bromo-2-naphthaldehyde). -Methylmercaptoarene; 3-bromopyrrole-2-carbaldehyde, 3-bromofuran-2-carbaldehyde, 3-bromothiophene-2-carboxaldehyde, 3-bromoselenophene-2-carboxaldehyde, etc. 3-halo-heteroarene -2-formaldehyde, etc.; ketones [eg o-bromo-heptyl-benzene, 2-bromo-1-undecyl-naphthalene, 3-bromo-2-heptadecanonaphthalene, etc. -C _2-31 alkyl nonyl- arene; 3-bromo-2-heptanyl-pyrrole, 3-bromo-2-undecylfluorenyl-furan, 3-bromo-2-heptadecanoyl-thiophene And 3-bromo-2-C _2-31 alkylnonyl-heteroaryl hydrocarbon, etc., such as 3-bromo-2-heptyl-selenium. Among the carbonyl compounds represented by the formula (2a), an aldehyde such as a halo-methyl decyl arene or a 3-halogeno-heteroaryl hydrocarbon-2-carbaldehyde is preferred. The carbonyl compound represented by the formula (2a) can be purchased from the market, and can also be prepared by a conventional method (for example, a method of isomerizing a dihalogen-aromatic ring or the like).

作為還原劑，並無特別限制，可列舉慣用的還原劑，例如硼氫化鋰(LiBH₄)、硼氫化鈉(NaBH₄)、氫化鋁鋰(LiAlH₄)等。還原劑的使用比率係相對於式(2a)所示之羰基化合物1莫耳而言，可為例如0.1至5莫耳，較佳為1至3莫耳，更佳為1.5至2莫耳左右。還原劑亦可單獨地或組合2種以上使用。 The reducing agent is not particularly limited, and examples thereof include a conventional reducing agent such as lithium borohydride (LiBH ₄ ), sodium borohydride (NaBH ₄ ), lithium aluminum hydride (LiAlH ₄ ), and the like. The use ratio of the reducing agent may be, for example, 0.1 to 5 moles, preferably 1 to 3 moles, more preferably 1.5 to 2 moles, relative to the carbonyl compound 1 mole represented by the formula (2a). . The reducing agents may be used singly or in combination of two or more.

反應可在對反應呈惰性的溶媒的存在下施行。作為溶媒，並無特別限制，可為慣用的有機溶媒，例如芳香族烴類(苯、甲苯、二甲苯等)、鹵烴類(二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等)、醇類(甲醇、乙醇等)、醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)等。此等溶媒亦可單獨地或組合2種以上使用。此等溶媒之中，通常多數情況係使用乙醇等醇類。 The reaction can be carried out in the presence of a solvent inert to the reaction. The solvent is not particularly limited, and may be a conventional organic solvent such as an aromatic hydrocarbon (benzene, toluene, xylene, etc.) or a halogen hydrocarbon (dichloromethane, chloroform, 1,2-dichloroethane, chlorine). Benzene, etc., alcohols (methanol, ethanol, etc.), ethers (chain ethers such as diethyl ether, tetrahydrofuran, two A cyclic ether such as an alkane or the like). These solvents may be used singly or in combination of two or more. Among these solvents, alcohols such as ethanol are usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可為例如-20至40℃，較佳為-10至30℃(通常為0℃至室溫)左右。反應時間可為例如1至48小時，較佳為12至36小時左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, about -20 to 40 ° C, preferably about -10 to 30 ° C (usually 0 ° C to room temperature). The reaction time may be, for example, from 1 to 48 hours, preferably from about 12 to 36 hours. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

<式(5)所示之化合物的合成(鏻鹽的合成)> Synthesis of a compound represented by the formula (5) (synthesis of a phosphonium salt) >

前述式(5)所示之鏻鹽可藉由使前述式(3)所示之羥基化合物與前述式(4)所示之三苯基膦鹵化氫鹽進行反應而予以調製。 The onium salt represented by the above formula (5) can be prepared by reacting a hydroxy compound represented by the above formula (3) with a triphenylphosphine hydrogen halide represented by the above formula (4).

在前述式(4)中，作為X²所表示之鹵素原子，可列舉例如氯、溴、碘等，較佳為溴。作為前述式(4)所示之三苯基膦鹵化氫鹽，可列舉例如三苯基膦氯化氫鹽、三苯基膦溴化氫鹽、三苯基膦碘化氫鹽等。前述式(4)所示之三苯基膦鹵化氫鹽亦可單獨地或組合2種以上使用。前述式(4)所示之三苯基膦鹵化氫鹽可使用市售品。式(4)所示之 三苯基膦鹵化氫鹽的使用比率係相對於前述式(3)所示之羥基化合物1莫耳而言，可為例如1至3莫耳，較佳為1至2莫耳左右，通常可為1莫耳左右。 In the above formula (4), examples of the halogen atom represented by X ² include chlorine, bromine, and iodine, and bromine is preferred. Examples of the triphenylphosphine hydrogen halide salt represented by the above formula (4) include triphenylphosphine hydrogen chloride salt, triphenylphosphine hydrogen bromide salt, and triphenylphosphine hydrogen iodide salt. The triphenylphosphine hydrogen halide salt represented by the above formula (4) may be used singly or in combination of two or more. A commercially available product can be used as the triphenylphosphine hydrogen halide salt represented by the above formula (4). The use ratio of the triphenylphosphine hydrogen halide salt represented by the formula (4) may be, for example, 1 to 3 moles, preferably 1 to 1 to the hydroxy compound 1 mole represented by the above formula (3). 2 moles around, usually about 1 mole.

反應可在對反應呈惰性的溶媒的存在下施行。作為溶媒，可為例如芳香族烴類(苯、甲苯、二甲苯等)、鹵烴類(二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等)、醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)。溶媒亦可單獨地或組合2種以上使用。此等溶媒之中，通常多數情況係使用氯仿等鹵烴類。 The reaction can be carried out in the presence of a solvent inert to the reaction. The solvent may be, for example, an aromatic hydrocarbon (benzene, toluene, xylene, etc.), a halogen hydrocarbon (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.) or an ether (diethyl). Chain ether such as ether, tetrahydrofuran, two a cyclic ether such as an alkane or the like). The solvent may be used singly or in combination of two or more. Among these solvents, halogen hydrocarbons such as chloroform are usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可為例如40至100℃，較佳為50至70℃左右，反應可在回流條件下施行。反應時間可為例如1至40小時，較佳為10至30小時左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, 40 to 100 ° C, preferably about 50 to 70 ° C, and the reaction can be carried out under reflux. The reaction time may be, for example, from 1 to 40 hours, preferably from about 10 to 30 hours. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

<式(6)所示之化合物的合成(Wittig反應)> <Synthesis of a compound represented by formula (6) (Wittig reaction)>

前述式(6)所示之二鹵化合物可藉由使前述式(5)所示之鏻鹽與前述式(2b)所示之羰基化合物在鹼的存在下進行反應而予以調製。 The dihalogen compound represented by the above formula (6) can be prepared by reacting the onium salt represented by the above formula (5) with the carbonyl compound represented by the above formula (2b) in the presence of a base.

在前述式(2a)中，作為X^1b所表示之鹵素原子，可例示亦包含較佳態樣在內並與前述X^1a同樣的原子。此外，作為式(2b)所示之化合物，只要是對應於前述式(1)所示之應變型化合物之羰基化合物即可，通常經常使用R^1b 為氫原子之化合物。作為式(2b)所示之化合物，可例示與前述式(2a)所例示之化合物同樣者。此外，前述式(2a)及(2b)所示之化合物大多為同一化合物。 In the above formula (2a), as the halogen atom represented by X ^1b , the same atom as the above X ^1a including the preferred embodiment can be exemplified. In addition, as the compound represented by the formula (2b), a carbonyl compound corresponding to the strain type compound represented by the above formula (1) may be used, and a compound in which R ^1b is a hydrogen atom is usually used. The compound represented by the formula (2b) is the same as the compound exemplified in the above formula (2a). Further, the compounds represented by the above formulas (2a) and (2b) are mostly the same compound.

式(5)所示之鏻鹽的使用比率係相對於式(2b)所示之羰基化合物1莫耳而言，可為例如1至1.5莫耳，較佳為1.05至1.2莫耳左右。 The use ratio of the onium salt represented by the formula (5) is, for example, from 1 to 1.5 mol, preferably from about 1.05 to 1.2 mol, based on the carbonyl compound 1 mol shown by the formula (2b).

作為鹼，可列舉例如金屬氫氧化物(氫氧化鈉、氫氧化鈣等鹼金屬氫氧化物或鹼土金屬氫氧化物等)、金屬碳酸鹽(碳酸鈉、碳酸氫鈉等碳酸鹼金屬或鹼土金屬碳酸鹽等)、金屬烷氧化物(甲氧化鈉、乙氧化鈉、第三丁氧化鉀等鹼金屬C_1-6烷氧化物等)等無機鹼；胺類(三乙基胺等三烷基胺、苯甲基二甲基胺等芳香族三級胺、吡啶等雜環式三級胺等)等有機鹼等。鹼可單獨地或組合二種以上。此等鹼之中，通常多數情況係使用第三丁氧化鉀等金屬烷氧化物。鹼的使用比率係相對於前述式(5)所示之鏻鹽1當量而言，可為例如1至5當量，較佳為2至4當量左右。 Examples of the base include metal hydroxides (alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, and alkaline earth metal hydroxides), and metal carbonates (alkali or alkaline earth metals such as sodium carbonate or sodium hydrogencarbonate). An inorganic base such as a carbonate or the like, a metal alkoxide (an alkali metal C _1-6 alkoxide such as sodium methoxide, sodium ethoxide or a third potassium oxychloride); an amine (a trialkyl group such as triethylamine) An organic base such as an aromatic tertiary amine such as an amine or benzyldimethylamine or a heterocyclic tertiary amine such as pyridine. The base may be used alone or in combination of two or more. Among these bases, a metal alkoxide such as potassium third potassium hydride is usually used in many cases. The use ratio of the base is, for example, 1 to 5 equivalents, preferably 2 to 4 equivalents, per equivalent of the onium salt represented by the above formula (5).

反應可在對反應呈惰性的溶媒的存在下施行。作為溶媒，可為例如芳香族烴類(苯、甲苯、二甲苯等)、鹵烴類(二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等)、醇類(甲醇、乙醇等)、醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)，通常多數情況係使用四氫呋喃等醚類。 The reaction can be carried out in the presence of a solvent inert to the reaction. Examples of the solvent include aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogen hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.), and alcohols (methanol, ethanol). Etc.), ethers (chain ethers such as diethyl ether, tetrahydrofuran, two In the case of a cyclic ether such as an alkane or the like, an ether such as tetrahydrofuran is usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可為例如-20至50℃，較佳為-10至30℃(通常為0℃至室溫)左右。反應時間可為例如1至 100小時，較佳為24至72小時左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, about -20 to 50 ° C, preferably about -10 to 30 ° C (usually 0 ° C to room temperature). The reaction time may be, for example, from 1 to 100 hours, preferably from about 24 to 72 hours. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

<式(1)所示之應變型化合物的合成(鋰化反應以及環化或閉環反應)> Synthesis of a strain-type compound represented by the formula (1) (lithiation reaction and cyclization or ring closure reaction)>

前述式(1)所示之應變型化合物可藉由使將前述式(6)所示之二鹵化合物及鋰化劑進行反應(鋰化反應)所生成之鋰化物，與前述式(7)所示之化合物(閉環劑)進行反應(環化反應)而予以調製。 The strain-type compound represented by the above formula (1) can be obtained by reacting (lithiation reaction) of the dihalogen compound represented by the above formula (6) with a lithiating agent, and the above formula (7) The compound (ring-ring agent) shown is subjected to a reaction (cyclization reaction) to prepare it.

(鋰化反應) (lithiation reaction)

作為鋰化劑，並無特別限制，可列舉慣用的鋰化劑，例如烷基鋰(例如甲基鋰、正丁基鋰、第二丁基鋰、第三丁基鋰等C_1-4烷基鋰等)、芳基鋰(苯基鋰等)、鋰胺類(鋰二異丙基胺(LDA)、鋰-2,2,6,6-四甲基哌啶(LiTMP)、鋰-雙(三甲基矽基)胺基鋰(LHMDS)等)等。此等鋰化劑亦可單獨地或組合2種以上使用。此等鋰化劑之中，通常係使用正丁基鋰等烷基鋰。鋰化劑的使用比率係相對於前述式(6)所示之二鹵化合物1莫耳而言，可為例如2至5莫耳，較佳為2至3莫耳左右，通常可為2莫耳左右。 The lithiating agent is not particularly limited, and examples thereof include a conventional lithiating agent such as an alkyl lithium (for example, a C _1-4 alkane such as methyllithium, n-butyllithium, a second butyllithium or a third butyllithium). Lithium base, etc., aryl lithium (phenyl lithium, etc.), lithium amines (lithium diisopropylamine (LDA), lithium-2,2,6,6-tetramethylpiperidine (LiTMP), lithium- Bis(trimethyldecyl)amino lithium (LHMDS), etc.). These lithiation agents may be used singly or in combination of two or more. Among these lithiation agents, an alkyl lithium such as n-butyllithium is usually used. The use ratio of the lithiating agent may be, for example, 2 to 5 moles, preferably 2 to 3 moles, and usually 2 moles, relative to the dihalogen compound 1 mole represented by the above formula (6). Around the ear.

反應可在對反應呈惰性的溶媒的存在下施行。作為溶媒，可為例如醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)等，通常多數情況係使用二乙基醚等。 The reaction can be carried out in the presence of a solvent inert to the reaction. As the solvent, for example, an ether (chain ether such as diethyl ether, tetrahydrofuran, or two) may be used. In the case of a cyclic ether such as an alkane or the like, diethyl ether or the like is usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體 等)環境下施行。反應溫度可為例如-100至-50℃，較佳為-80至-70℃左右。反應時間可為例如1至120分鐘，較佳為30至90分鐘左右。反應終了後，可在未藉由慣用的分離精製手段予以精製之情形下，視需要將包含前述鋰化物之反應液供予下一環化反應。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, -100 to -50 ° C, preferably about -80 to -70 ° C. The reaction time may be, for example, from 1 to 120 minutes, preferably from about 30 to 90 minutes. After the completion of the reaction, the reaction solution containing the lithium compound may be supplied to the next cyclization reaction, if it is not purified by a conventional separation and purification means.

(環化反應) (cyclization reaction)

在前述式(7)中，作為L¹所表示之鹵素原子，可列舉例如氯、溴、碘等(特別是氯)。 In the above formula (7), examples of the halogen atom represented by L ¹ include chlorine, bromine, iodine, and the like (particularly chlorine).

在L¹所表示之-SO₂R⁶基中，作為R⁶所表示之烴基，可列舉例如前述R^1a及R^1b基之段落中所例示之烴基等。作為R⁶所表示之氟烴基，可列舉將前述烴基中之氫原子的一部分或全部進行氟化而得之基，例如三氟甲基等氟烷基、五氟苯基等氟芳基等。 In the -SO ₂ R ⁶ group represented by L ¹ , the hydrocarbon group represented by R ⁶ may, for example, be a hydrocarbon group exemplified in the paragraphs of the above R ^1a and R ^1b groups. The fluorocarbon group represented by R ⁶ may be a group obtained by fluorinating a part or all of hydrogen atoms in the hydrocarbon group, for example, a fluoroalkyl group such as a trifluoromethyl group or a fluoroaryl group such as pentafluorophenyl group.

作為L¹所表示之-SO₂R⁶基，代表性而言，可列舉例如烷基磺醯基(甲基磺醯基(甲磺醯基)等C_1-6烷基磺醯基等)；芳基磺醯基(苯基磺醯基等C_6-10芳基磺醯基等)；烷基芳基磺醯基(對甲苯磺醯基(甲苯磺醯基)等C_1-6烷基C_6-10芳基磺醯基等)；硝基芳基磺醯基(鄰硝基苯磺醯基等硝基C_6-10芳基磺醯基等)；氟烷基磺醯基(三氟甲烷磺醯基等氟化C_1-6烷基磺醯基等)等。 The -SO ₂ R ⁶ group represented by L ¹ is, for example, an alkylsulfonyl group (such as a C _1-6 alkylsulfonyl group such as a methylsulfonyl group or a methylsulfonyl group). ; aryl sulfonic acyl group (acyl phenyl sulfonic and other C _6-10 aryl sulfonic acyl group and the like); alkylaryl sulfonic acyl (C _1-6 alkyl p-toluene sulfonic acyl (acyl-toluenesulfonyl) and the like a C _6-10 arylsulfonyl group, etc.; a nitroarylsulfonyl group (nitro-C _6-10 arylsulfonyl group such as o-nitrophenylsulfonyl); a fluoroalkylsulfonyl group ( A fluorinated C _1-6 alkylsulfonyl group such as a trifluoromethanesulfonyl group or the like).

2個L¹基可彼此相異，但通常可相同。此等L¹基之中，多數情況係利用鹵素原子(例如氯等)、芳基磺醯基(例如苯磺醯基等)等。 The two L ¹ groups may be different from each other, but may generally be the same. Among these L ¹ groups, a halogen atom (for example, chlorine or the like), an arylsulfonyl group (for example, a benzenesulfonyl group) or the like is used in many cases.

前述式(7)所示之化合物(閉環劑)可對應於 式(1)所示之應變型化合物而選擇，代表性而言，可列舉例如苯硫磺酸酐((PhSO₂)₂S)等磺酸酐；二氯化硒(SeCl₂)、二甲基二氯矽烷、苯基二氯膦等二鹵化物等。此等式(7)所示之化合物可使用市售品。 The compound (closed-loop agent) represented by the above formula (7) can be selected according to the strain-type compound represented by the formula (1), and typically, for example, a sulfonate such as phenylsulfuric anhydride ((PhSO ₂ ) ₂ S) may be mentioned. An acid anhydride; a dihalide such as selenium dichloride (SeCl ₂ ), dimethyl dichlorodecane or phenyl dichlorophosphine. A commercially available product can be used as the compound represented by the formula (7).

前述式(7)所示之化合物(閉環劑)的使用比率係相對於供予前述鋰化反應之式(6)所示之二鹵化合物1莫耳而言，可為例如1至1.5莫耳，較佳為1.05至1.2莫耳左右。 The use ratio of the compound (closed ring agent) represented by the above formula (7) is, for example, 1 to 1.5 mol per mol of the dihalogen compound 1 mol represented by the formula (6) to which the aforementioned lithiation reaction is carried out. Preferably, it is from about 1.05 to about 1.2 moles.

反應可在對反應呈惰性的溶媒的存在下施行，亦可對前述鋰化反應之反應液進一步添加溶媒。作為溶媒，可為例如醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)等，通常多數情況係使用四氫呋喃等。 The reaction may be carried out in the presence of a solvent inert to the reaction, or a solvent may be further added to the reaction solution of the lithiation reaction. As the solvent, for example, an ether (chain ether such as diethyl ether, tetrahydrofuran, or two) may be used. In the case of a cyclic ether such as an alkane or the like, tetrahydrofuran or the like is usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可為例如-100至50℃，較佳為-90至30℃(通常為-78℃至室溫)左右。反應時間可為例如1至12小時，較佳為6至10小時左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, -100 to 50 ° C, preferably -90 to 30 ° C (generally -78 ° C to room temperature). The reaction time may be, for example, from 1 to 12 hours, preferably from about 6 to 10 hours. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

(方法B) (Method B)

本發明之應變型化合物亦可依照下述反應式(方法B)予以調製。就方法B而言，在反應步驟數少於前述方法A之方面較有利。此外，有用於將烴基(例如烷基等)導入至R^1a及R^1b基中之情況。 The strain-type compound of the present invention can also be prepared according to the following reaction formula (Method B). In the case of method B, it is advantageous in that the number of reaction steps is less than that of the aforementioned method A. Further, there are cases in which a hydrocarbon group (e.g., an alkyl group or the like) is introduced into the R ^1a and R ^1b groups.

(式中，Z、A¹、A²、R^1a、R^1b、R²、R³、R^A、R^B、m、n、p1、p2及 (wherein Z, A ¹ , A ² , R ^1a , R ^1b , R ² , R ³ , R ^A , R ^B , m, n, p1, p2 and

所示之鍵結係各自亦包含較佳態樣在內並與前述式(1)之記載相同；X^1a及X^1b係各自亦包含較佳態樣在內並與前述式(2a)之記載相同；-Sn(R⁸)₃基係亦包含較佳態樣在內並與前述含金屬(或半金屬)之基之段落之記載相同)。 Each of the bonding systems shown also includes the preferred embodiment and is the same as described in the above formula (1); each of X ^1a and X ^1b also includes a preferred embodiment and is described in the above formula (2a). The same; the -Sn(R ⁸ ) ₃ group also contains the preferred embodiment and is identical to the description of the aforementioned metal-containing (or semi-metal) group.

<式(10)所示之化合物的合成(史帝勒偶合(Stille coupling))> <Synthesis of a compound represented by the formula (10) (Stille coupling)>

在式(2a)及式(2b)中，A¹及A²、R^1a及R^1b、R^A及R^B、X^1a及X^1b以及p1及p2可各自相同或相異，但通常多數情 況係相同。 In the formulas (2a) and (2b), A ¹ and A ² , R ^1a and R ^1b , R ^A and R ^B , X ^1a and X ^{1b ,} and p1 and p2 may be the same or different, but usually in many cases. The same.

作為式(2a)及式(2b)所示之化合物，可列舉例如與前述式(2a)所示之化合物同樣的化合物。此等式(2a)及式(2b)所示之化合物亦可單獨地或組合2種以上使用，但通常多數情況係單獨地使用。此外，在方法B中，由可將烴基(例如烷基等)輕易地或效率良好地導入至R^1a及R^1b基中之方面而言，此等式(2a)及式(2b)所示之化合物之中，較佳為鹵基-C_2-31烷醯基-芳烴(例如2-溴-1-十七烷醯基-萘等)；3-鹵基-2-烷醯基-雜芳烴(例如3-溴-2-庚醯基-噻吩等)等酮類。 The compound represented by the formula (2a) and the formula (2b) may, for example, be the same compound as the compound represented by the above formula (2a). The compounds represented by the above formulas (2a) and (2b) may be used singly or in combination of two or more kinds, but in many cases, they are usually used alone. Further, in the method B, the hydrocarbon group (for example, an alkyl group or the like) can be easily or efficiently introduced into the R ^1a and R ^1b groups, as shown in the equations (2a) and (2b). Among the compounds, a halo-C _2-31 alkanoyl-arene (e.g., 2-bromo-1-heptadecanoyl-naphthalene, etc.); 3-halo-2-alkylindenyl-hetero is preferred. A ketone such as an aromatic hydrocarbon (e.g., 3-bromo-2-heptanyl-thiophene, etc.).

式(2a)及式(2b)所示之化合物可購自市面，亦可藉由慣用的方法，例如使3-鹵基-雜芳烴與烷醯氯或烷酸酐在氯化鋁等路易斯酸(Lewis acid)觸媒的存在下進行反應(夫里德耳-夸夫特(Friedel-Crafts)醯化反應)之方法等予以調製。另外，在藉由前述方法予以調製之情況，式(2a)及式(2b)所示之化合物可在未完全去除副生成物(例如在鄰接於X^1a及X^1b之取代位置以外之位置取代有烷醯基之化合物等)之情形下供予與式(9)所示之化合物之反應，並在前述反應終了後予以精製。 The compound represented by the formula (2a) and the formula (2b) can be commercially available, and a Lewis acid such as aluminum chloride can be also obtained by a conventional method such as a 3-halogeno-heteroarene and an alkane chloride or an alkanoic anhydride. The Lewis acid) is prepared by a method such as a reaction (Friedel-Crafts deuteration reaction) in the presence of a catalyst. Further, in the case of being prepared by the aforementioned method, the compound represented by the formula (2a) and the formula (2b) can be substituted without completely removing the by-product (for example, at a position other than the substitution position of X ^1a and X ^1b) . In the case of a compound having an alkyl fluorenyl group or the like, a reaction with a compound represented by the formula (9) is carried out, and after the completion of the above reaction, it is purified.

在式(9)中，6個R⁸基的種類可彼此相異，但通常多數情況係相同。作為式(9)所示之化合物，代表性而言，可列舉例如雙(三烷基錫)硫化物(或雙(三烷基錫烷基)硫化物)[例如雙(三甲基錫)硫化物、雙(三丁基錫)硫化物等雙(三C_1-4烷基錫)硫化物等]；或雙(三烷基錫)氧化物 (或雙(三烷基錫)醚)[例如雙(三丁基錫)氧化物等雙(三C_1-4烷基錫)氧化物等]；雙(三烷基錫)硒化物[例如雙(三丁基錫)硒化物等雙(三C_1-4烷基錫)硒化物等]，較佳為雙(三丁基錫)硫化物等雙(三烷基錫)硫化物。此等式(9)所示之化合物可購自市面。 In the formula (9), the kinds of the six R ⁸ groups may be different from each other, but in most cases, they are the same. Typical examples of the compound represented by the formula (9) include bis(trialkyltin) sulfide (or bis(trialkylstannyl) sulfide) [for example, bis(trimethyltin). a bis(tri-C _1-4 alkyl tin) sulfide such as a sulfide or bis(tributyltin) sulfide; or a bis(trialkyltin) oxide (or bis(trialkyltin) ether) [for example] bis (tributyltin) oxide bis (tri C _1-4 alkyl tin) oxide]; bis bis (trialkyltin) selenide [e.g. bis (tributyltin) selenide, and the like (C _1-4 three The alkyltin) selenide or the like] is preferably a bis(trialkyltin) sulfide such as bis(tributyltin) sulfide. The compound represented by the formula (9) can be purchased from the market.

式(2a)及式(2b)所示之化合物的總量之比率係相對於式(9)所示之化合物1莫耳而言，可為例如2至3莫耳，較佳為2.05至2.5莫耳(通常為2.1至2.2莫耳)左右。 The ratio of the total amount of the compound represented by the formula (2a) and the formula (2b) is, for example, 2 to 3 moles, preferably 2.05 to 2.5, relative to the compound 1 mole represented by the formula (9). Moore (usually 2.1 to 2.2 moles) or so.

反應可在觸媒的存在下施行。作為觸媒，可列舉例如鈀觸媒[鈀(0)觸媒(例如醋酸鈀、參(二苯亞甲基丙酮)二鈀(0)氯仿錯合物、肆(三苯基膦)鈀(0)等)等鈀錯合物]等。 The reaction can be carried out in the presence of a catalyst. The catalyst may, for example, be a palladium catalyst [palladium (0) catalyst (for example, palladium acetate, stilbene (diphenylmethyleneacetone) dipalladium (0) chloroform complex, ruthenium (triphenylphosphine) palladium ( 0) etc.) Palladium complex] and the like.

觸媒的使用比率係相對於式(9)所示之化合物1莫耳而言，可為例如0.01至0.2莫耳，較佳為0.05至0.15莫耳(通常為0.1至0.12莫耳)左右。 The use ratio of the catalyst may be, for example, 0.01 to 0.2 mol, preferably 0.05 to 0.15 mol (usually 0.1 to 0.12 mol), relative to the compound 1 mole represented by the formula (9).

反應可在對反應呈惰性的溶媒的存在下施行。作為溶媒，可為例如醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)、芳香族烴類(苯、甲苯、二甲苯等)等。此等溶媒亦可單獨地或組合2種以上使用。此等溶媒之中，通常多數情況係使用甲苯等。 The reaction can be carried out in the presence of a solvent inert to the reaction. As the solvent, for example, an ether (chain ether such as diethyl ether, tetrahydrofuran, or two) may be used. An aromatic hydrocarbon (such as a cyclic ether such as an alkane) or an aromatic hydrocarbon (such as benzene, toluene or xylene). These solvents may be used singly or in combination of two or more. Among these solvents, toluene or the like is usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下(或氣流下)施行。反應溫度可為例如80至200℃，較佳為100至150℃(通常為110至130℃)左右。反應時間可為例如1至48小時，較佳為12至24小時左右。反 應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium, argon, etc.) (or under a gas stream). The reaction temperature may be, for example, about 80 to 200 ° C, preferably about 100 to 150 ° C (generally about 110 to 130 ° C). The reaction time may be, for example, from 1 to 48 hours, preferably from about 12 to 24 hours. After the reaction is completed, it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification.

<式(1)所示之化合物的合成(麥克默里偶合(McMurry coupling))> Synthesis of a compound represented by the formula (1) (McMurry coupling)>

可藉由利用低原子價鈦(例如Ti(I)、Ti(0)等)的還原作用將式(10)所示之化合物進行分子內偶合(或環化反應)，而調製式(1)所示之化合物。 The compound represented by the formula (10) can be intramolecularly coupled (or cyclized) by reduction with a low valence valent titanium (for example, Ti(I), Ti(0), etc.), and the formula (1) can be prepared. The compound shown.

低原子價鈦係藉由在氬等惰性氣體環境下，將鈦化合物以還原劑進行還原而生成，通常多數情況係在包含式(10)所示之化合物之反應系統內生成。作為前述鈦化合物，可列舉例如氯化鈦(III)(TiCl₃)、氯化鈦(IV)(TiCl₄)等鹵化鈦等。前述鈦化合物可與配位基(二甲氧基乙烷等)共同形成錯合物。 The low valence titanium is produced by reducing a titanium compound with a reducing agent in an inert gas atmosphere such as argon, and is usually produced in a reaction system containing a compound represented by the formula (10). Examples of the titanium compound include titanium halides such as titanium (III) chloride (TiCl ₃ ) and titanium (IV) chloride (TiCl ₄ ). The aforementioned titanium compound may form a complex with a ligand (dimethoxyethane or the like).

作為前述還原劑，可列舉鋰(Li)、鉀(K)等鹼金屬；氫化鋁鋰(LiAlH₄)等氫化鋁化合物；鋅(Zn)或含鋅化合物(或合金)[例如鋅(Zn)-銅(Cu)偶合物等]等，通常大多係利用鋅(Zn)或含鋅化合物(例如鋅(Zn))。 Examples of the reducing agent include alkali metals such as lithium (Li) and potassium (K); aluminum hydride compounds such as lithium aluminum hydride (LiAlH ₄ ); zinc (Zn) or zinc-containing compounds (or alloys) such as zinc (Zn). - Copper (Cu) conjugate, etc., etc., usually use zinc (Zn) or a zinc-containing compound (for example, zinc (Zn)).

鈦化合物的比率係相對於式(10)所示之化合物1莫耳而言，可為例如1至20莫耳(例如5至10莫耳)，較佳為7至9莫耳(通常為7.5至8.5莫耳)左右。還原劑的比率係相對於鈦化合物1莫耳而言，可為例如1至5莫耳(例如1.8至3莫耳)，較佳為1.5至2.5莫耳(通常為1.8至2.2莫耳)左右。 The ratio of the titanium compound may be, for example, 1 to 20 moles (e.g., 5 to 10 moles), preferably 7 to 9 moles (usually 7.5) with respect to the compound 1 mole represented by the formula (10). Up to 8.5 m). The ratio of the reducing agent may be, for example, 1 to 5 moles (e.g., 1.8 to 3 moles), preferably 1.5 to 2.5 moles (usually 1.8 to 2.2 moles), relative to the titanium compound 1 mole. .

反應可在對反應呈惰性的溶媒的存在下施 行。作為溶媒，並無特別限制，可為慣用的有機溶媒，例如芳香族烴類(苯、甲苯、二甲苯等)、鹵烴類(二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等)、醚類(二乙基醚、二甲氧基乙烷等鏈狀醚、四氫呋喃、二烷等環狀醚等)等。此等溶媒亦可單獨地或組合2種以上使用。此等溶媒之中，通常多數情況係使用甲苯等芳香族烴類、四氫呋喃等醚類、此等之混合溶媒等。 The reaction can be carried out in the presence of a solvent inert to the reaction. The solvent is not particularly limited, and may be a conventional organic solvent such as an aromatic hydrocarbon (benzene, toluene, xylene, etc.) or a halogen hydrocarbon (dichloromethane, chloroform, 1,2-dichloroethane, chlorine). Benzene, etc., ethers (diethyl ether, dimethoxyethane and other chain ethers, tetrahydrofuran, two A cyclic ether such as an alkane or the like). These solvents may be used singly or in combination of two or more. Among these solvents, an aromatic hydrocarbon such as toluene, an ether such as tetrahydrofuran, or a mixed solvent thereof is usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可為例如30至100℃，較佳為40至80℃(通常為50至70℃)左右。另外，式(1)所示之化合物、鈦化合物及還原劑的混合(或反應初期)可在低溫環境下施行，亦可為例如-30至10℃，較佳為-20至0℃(通常為-15至-5℃)左右。反應時間可為例如1至30小時，較佳為12至18小時左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, about 30 to 100 ° C, preferably about 40 to 80 ° C (usually 50 to 70 ° C). Further, the mixture of the compound represented by the formula (1), the titanium compound and the reducing agent (or the initial stage of the reaction) may be carried out in a low temperature environment, and may be, for example, -30 to 10 ° C, preferably -20 to 0 ° C (usually It is about -15 to -5 ° C). The reaction time may be, for example, from 1 to 30 hours, preferably from about 12 to 18 hours. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

另外，在如此所獲得之式(1)[包含式(1A)及式(1B)]所示之應變型化合物中，R^1a、R^1b、R²、R³、R^A及R^B(包含R^a、R^b、R^2a、R^2b、R^3a、R^3b、R^4a、R^4b、R^5a及R^5b)所表示之取代基及原子可藉由將藉由環化反應所獲得之應變型化合物供予慣用的化學反應(修飾反應)而予以導入。作為此種修飾反應，並無特別限制，代表性而言，可列舉例如鹵化反應、交叉偶合反應、氧化反應、含金屬(或半金屬)之基之導入反應等。 Further, in the strain type compound represented by the formula (1) [including the formula (1A) and the formula (1B)] thus obtained, R ^1a , R ^1b , R ² , R ³ , R ^A and R ^B (including The substituents and atoms represented by R ^a , R ^b , R ^2a , R ^2b , R ^3a , R ^3b , R ^4a , R ^4b , R ^5a and R ^5b ) can be obtained by the strain obtained by the cyclization reaction The compound is introduced by a conventional chemical reaction (modification reaction). The modification reaction is not particularly limited, and examples thereof include a halogenation reaction, a cross-coupling reaction, an oxidation reaction, and a metal-containing (or semi-metal)-based introduction reaction.

<鹵化反應> <halogenation reaction>

在鹵化反應中，可調製例如式(1B)中之R^4a及R^4b為鹵素原子之化合物(下述式(1b)所示之化合物)。作為此種反應，舉例而言，可使將藉由前述環化反應所調製而得之R^4a及R^4b為氫原子之化合物(下述式(1a)所示之化合物)與鋰化劑進行反應所生成之鋰化物，與鹵化劑進行反應而進行調製。 In the halogenation reaction, for example, a compound of the formula (1B) wherein R ^4a and R ^4b are a halogen atom (a compound represented by the following formula (1b)) can be prepared. As such a reaction, for example, a compound (a compound represented by the following formula (1a)) in which R ^4a and R ^4b obtained by the above cyclization reaction are hydrogen atoms can be used as a lithiation agent. The lithium compound formed by the reaction is reacted with a halogenating agent to prepare a lithium compound.

(式中，X^3a及X^3b表示鹵素原子，Z、Z¹、Z²、R^1a、R^1b、R²、R^2a、R^2b、R³、R^3a、R^3b、R^5a、R^5b、m、m1、m2、n、n1及n2係各自亦包含較佳態樣在內並與前述式(1B)之記載相同)。 (wherein X ^3a and X ^3b represent a halogen atom, and Z, Z ¹ , Z ² , R ^1a , R ^1b , R ² , R ^2a , R ^2b , R ³ , R ^3a , R ^3b , R ^5a , R ^5b Each of m, m1, m2, n, n1, and n2 also includes a preferred embodiment and is the same as described in the above formula (1B).

作為鋰化劑，可利用前述鋰化反應中所記載之慣用的鋰化劑，通常大多係使用鋰-2,2,6,6-四甲基哌啶(LiTMP)等鋰醯胺類。鋰化劑的使用比率係相對於前述式(1a)所示之化合物1莫耳而言，可為例如2至5莫耳，較佳為2至3莫耳左右。 As the lithiating agent, a conventional lithiating agent described in the above lithiation reaction can be used, and in general, lithium amide such as lithium-2,2,6,6-tetramethylpiperidine (LiTMP) is usually used. The use ratio of the lithiating agent may be, for example, 2 to 5 moles, preferably about 2 to 3 moles, relative to the compound 1 mole represented by the above formula (1a).

與鋰化劑之反應可在對反應呈惰性的溶媒的存在下施行。作為溶媒，可為例如醚類(二乙基醚等鏈狀 醚、四氫呋喃、二烷等環狀醚等)等，通常多數情況係使用四氫呋喃等。 The reaction with the lithiating agent can be carried out in the presence of a solvent inert to the reaction. As the solvent, for example, an ether (chain ether such as diethyl ether, tetrahydrofuran, or two) may be used. In the case of a cyclic ether such as an alkane or the like, tetrahydrofuran or the like is usually used in many cases.

與鋰化劑之反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可為例如-100至-50℃，較佳為-80至-70℃左右。反應時間可為例如1至300分鐘，較佳為60至180分鐘左右。反應終了後，可在未藉由慣用的分離精製手段予以精製之情形下，視需要將反應液供予與鹵化劑之反應。 The reaction with the lithiating agent can be carried out in an environment of an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, -100 to -50 ° C, preferably about -80 to -70 ° C. The reaction time may be, for example, from 1 to 300 minutes, preferably from about 60 to 180 minutes. After the completion of the reaction, the reaction solution may be supplied to the halogenating agent as needed without being purified by a conventional separation and purification means.

在前述式(1b)中，作為X^3a及X^3b所表示之鹵素原子，可列舉例如氯、溴、碘等(特別是溴)。另外，X^3a及X^3b所表示之鹵素原子可彼此相異，但通常係相同。 In the above formula (1b), examples of the halogen atom represented by X ^3a and X ^3b include chlorine, bromine, iodine and the like (particularly bromine). Further, the halogen atoms represented by X ^3a and X ^3b may be different from each other, but are usually the same.

作為鹵化劑，並無特別限制，可為慣用的鹵化劑，例如鹵素單質(氯(Cl₂)、溴(Br₂)、碘(I₂)等)、鹵烴(例如1,2-二溴乙烷、1,2-二溴-1,1,2,2-四氯乙烷等鹵化C_2-6烷烴等)等。鹵化劑的使用比率係相對於供予前述與鋰化劑之反應之式(1a)所示之化合物1莫耳而言，可為例如2至5莫耳，較佳為2至3莫耳左右。 The halogenating agent is not particularly limited, and may be a conventional halogenating agent such as a halogen element (chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ), etc.), a halogen hydrocarbon (for example, 1,2-dibromo). Ethane, halogenated C _2-6 alkane such as 1,2-dibromo-1,1,2,2-tetrachloroethane, etc.). The use ratio of the halogenating agent may be, for example, 2 to 5 moles, preferably 2 to 3 moles, per mole of the compound 1 mole represented by the formula (1a) to be reacted with the lithiating agent. .

反應可在對反應呈惰性的溶媒的存在下施行，亦可對前述鋰化反應之反應液進一步添加溶媒。作為溶媒，可為例如醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)等，通常多數情況係使用四氫呋喃等。 The reaction may be carried out in the presence of a solvent inert to the reaction, or a solvent may be further added to the reaction solution of the lithiation reaction. As the solvent, for example, an ether (chain ether such as diethyl ether, tetrahydrofuran, or two) may be used. In the case of a cyclic ether such as an alkane or the like, tetrahydrofuran or the like is usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可為例如-100至50℃，較佳為-90至30℃(通常為-78℃至室溫)左右。反應時間可為例如 1至48小時，較佳為12至24小時左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, -100 to 50 ° C, preferably -90 to 30 ° C (generally -78 ° C to room temperature). The reaction time may be, for example, from 1 to 48 hours, preferably from about 12 to 24 hours. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

<交叉偶合反應> <cross coupling reaction>

在交叉偶合反應中，舉例而言，可調製式(1B)中之R^4a及R^4b為烴基或可具有烴基之雜芳基之化合物(下述式(1c)所示之化合物)。作為此種反應，並無特別限制，代表性而言，可列舉例如鈴木-宮浦偶合、根岸偶合、檜山偶合、熊田-玉尾偶合、小杉-右田-史帝勒(Stille)偶合等。更具體而言，式(1c)所示之化合物可藉由例如使藉由前述鹵化反應所調製而得之R^4a及R^4b為鹵素原子之化合物(下述式(1b)所示之化合物)與下述式(8)所示之化合物進行反應而予以調製。 In the cross-coupling reaction, for example, a compound of the formula (1B) wherein R ^4a and R ^4b are a hydrocarbon group or a heteroaryl group which may have a hydrocarbon group (a compound represented by the following formula (1c)) can be prepared. The reaction is not particularly limited, and examples thereof include Suzuki-Miyaura coupling, Root-shore coupling, Lushan coupling, Kudada-Jade tail coupling, and Komatsu-Ryota-Stille coupling. More specifically, the compound represented by the formula (1c) can be, for example, a compound obtained by the above halogenation reaction, wherein R ^4a and R ^4b are a halogen atom (a compound represented by the following formula (1b)) It is prepared by reacting with a compound represented by the following formula (8).

(式中，R⁷表示烴基或可具有烴基之雜芳基，L²表示-B(OH)₂基、-ZnX⁴基(式中，X⁴表示鹵素原子)、-MgX⁵基(式中，X⁵表示鹵素原子)、-Sn(R⁸)₃基(式中，R⁸表示烷基)、-Si(R⁹)₃基(式中，R⁹表示氟、氯或烷基)，Z、Z¹、Z²、R^1a、R^1b、R²、R^2a、R^2b、R³、R^3a、R^3b、R^5a、R^5b、 m、m1、m2、n、n1及n2係各自亦包含較佳態樣在內並與前述式(1B)之記載相同，X^3a及X^3b係亦包含較佳態樣在內並與前述式(1b)之記載相同)。 (wherein R ⁷ represents a hydrocarbon group or a heteroaryl group which may have a hydrocarbon group, L ² represents a -B(OH) ₂ group, a -ZnX ⁴ group (wherein X ⁴ represents a halogen atom), and -MgX ⁵ group (wherein , X ⁵ represents a halogen atom), -Sn(R ⁸ ) ₃ group (wherein R ⁸ represents an alkyl group), and -Si(R ⁹ ) ₃ group (wherein R ⁹ represents fluorine, chlorine or an alkyl group), Z, Z ¹ , Z ² , R ^1a , R ^1b , R ² , R ^2a , R ^2b , R ³ , R ^3a , R ^3b , R ^5a , R ^5b , m , m1 , m2 , n , n1 and n2 Each of them also contains a preferred embodiment and is the same as the above formula (1B), and X ^3a and X ^3b also contain the preferred embodiment and are the same as described in the above formula (1b).

在前述式(8)中，作為R⁷所表示之烴基及可具有烴基之雜芳基，係亦包含較佳態樣在內並與前述R^4a及R^4b之段落中所例示之烴基及可具有烴基之雜芳基相同。 In the above formula (8), the hydrocarbon group represented by R ⁷ and the heteroaryl group which may have a hydrocarbon group also include a preferred embodiment and a hydrocarbon group exemplified in the above paragraphs of R ^4a and R ^4b and The heteroaryl group having a hydrocarbon group is the same.

作為X⁴及X⁵所表示之鹵素原子以及R⁸及R⁹所表示之烷基，可包含較佳態樣在內並與前述R^A及R^B基之段落中所例示之含金屬(或半金屬)之基中之記載相同。 The halogen atom represented by X ⁴ and X ⁵ and the alkyl group represented by R ⁸ and R ⁹ may contain a preferred embodiment and include the metal as exemplified in the above paragraphs of R ^A and R ^B (or The description of the base of the semimetal is the same.

前述式(8)所示之化合物並無特別限制，可列舉例如對應於導入至式(1c)所示之化合物中之R⁷基之硼酸化合物、鋅鹵化物化合物(鋅氯化物等)、格林納試劑(Grignard reagent)、三烷基錫烷基化合物、三烷基矽基化合物等。此等之中，通常係利用硼酸化合物、鋅鹵化物化合物等。 The compound represented by the above formula (8) is not particularly limited, and examples thereof include a boronic acid compound, a zinc halide compound (zinc chloride, etc.) corresponding to the R ⁷ group introduced into the compound represented by the formula (1c), and Green. Grignard reagent, trialkylstannyl compound, trialkylsulfonyl compound, and the like. Among these, a boric acid compound, a zinc halide compound, or the like is usually used.

作為前述式(8)所示之化合物，更具體而言，可列舉芳基硼酸(例如苯基硼酸等C_6-14芳基硼酸、4-己基苯基硼酸等C_1-20烷基C_6-14芳基硼酸等)、雜芳基硼酸(例如2-噻吩基硼酸等C_4-13雜芳基硼酸等)等硼酸化合物；芳基鋅鹵化物(例如苯基鋅氯化物等C_6-14芳基鋅鹵化物、4-癸基苯基鋅氯化物等C_1-20烷基C_6-14芳基鋅鹵化物等)、雜芳基鋅鹵化物(例如2-噻吩基鋅氯化物等C_4-13雜芳基鋅鹵 化物等)等鋅鹵化物化合物等。 More specifically, examples of the compound represented by the above formula (8) include arylboronic acid (for example, C _6-14 arylboronic acid such as phenylboric acid, and C _1-20 alkyl C ₆ such as 4-hexylphenylboronic acid _; Boric acid compound such as _-14 arylboronic acid or the like, heteroarylboronic acid (for example, C _4-13 heteroarylboronic acid such as 2- _{thienylboronic} acid); aryl zinc halide (for example, C _6- such as phenyl zinc chloride) ₁₄ aryl zinc halide, 4-nonylphenyl zinc chloride, etc., C _1-20 alkyl C _6-14 aryl zinc halide, etc.), heteroaryl zinc halide (eg 2-thienyl zinc chloride) A zinc halide compound or the like such as a C _4-13 heteroaryl zinc halide or the like.

前述式(8)所示之化合物的使用比率係相對於前述式(1b)所示之鹵化物1莫耳而言，可為例如2至5莫耳，較佳為2.5至3.5莫耳左右。 The use ratio of the compound represented by the above formula (8) may be, for example, 2 to 5 moles, preferably about 2.5 to 3.5 moles, relative to the halide 1 mole represented by the above formula (1b).

反應通常可在觸媒的存在下施行。觸媒的種類可因應L²基而選擇，可列舉例如鈀觸媒[鈀(0)觸媒(例如醋酸鈀、參(二苯亞甲基丙酮)二鈀(0)氯仿錯合物)等鈀錯合物]、鎳觸媒(鎳(0)觸媒等鎳錯合物)、鐵觸媒(鐵(III)觸媒等鐵錯合物)等過渡金屬錯合物等。此等觸媒之中，多數情況為鈀觸媒、鎳觸媒(特別是鈀觸媒)。觸媒的使用量係相對於前述式(1b)所示之鹵化物1莫耳而言，可為例如0.001至1莫耳，較佳為0.01至0.5莫耳(通常為0.02至0.2莫耳)左右。 The reaction can usually be carried out in the presence of a catalyst. The type of the catalyst can be selected depending on the L ² group, and examples thereof include a palladium catalyst [palladium (0) catalyst (for example, palladium acetate, diphenylmethyleneacetone) dipalladium (0) chloroform complex), and the like. A transition metal complex such as a palladium complex], a nickel catalyst (a nickel complex such as a nickel (0) catalyst), an iron catalyst (an iron complex such as an iron (III) catalyst), or the like. Among these catalysts, palladium catalyst and nickel catalyst (especially palladium catalyst) are often used. The amount of the catalyst used may be, for example, 0.001 to 1 mol, preferably 0.01 to 0.5 mol (usually 0.02 to 0.2 mol), relative to the halide 1 mol represented by the above formula (1b). about.

在反應中，可添加能夠配位於觸媒而形成錯合物之配位基。作為配位基，可列舉例如三(第三丁基)膦、1,3-雙(二苯基膦基)丙烷(dppp)、1,1’-雙(二苯基膦基)二茂鐵等膦系配位基等。此等配位基可以鹽(例如與四氟硼酸鹽等陰離子之鏻鹽等)之形式進行添加。配位基的使用量可因應觸媒的種類而選擇，相對於觸媒1莫耳而言，可為例如1至10莫耳，較佳為1.1至5莫耳左右。 In the reaction, a ligand capable of being coordinated to form a complex to form a complex may be added. Examples of the ligand include tris(t-butyl)phosphine, 1,3-bis(diphenylphosphino)propane (dppp), and 1,1'-bis(diphenylphosphino)ferrocene. A phosphine ligand or the like. These ligands may be added in the form of a salt (for example, an anthracene salt such as an anion such as tetrafluoroborate). The amount of the ligand to be used may be selected depending on the kind of the catalyst, and may be, for example, 1 to 10 moles, preferably about 1.1 to 5 moles, relative to the catalyst 1 mole.

反應可因應L²基，在鹼的存在下或不存在下施行。作為鹼，可列舉例如前述Wittig反應之段落中所例示之鹼等。鹼可單獨地或組合二種以上。此等鹼之中，通常多數情況係使用氫氧化鈉等金屬氫氧化物。鹼的使用 比率係相對於前述式(1b)所示之鹵化物1莫耳而言，可為例如1至10莫耳，較佳為3至5莫耳左右。 The reaction can be carried out in the presence or absence of a base in response to the L ² group. Examples of the base include, for example, a base exemplified in the above paragraph of the Wittig reaction. The base may be used alone or in combination of two or more. Among these bases, a metal hydroxide such as sodium hydroxide is usually used in many cases. The use ratio of the base may be, for example, 1 to 10 moles, preferably about 3 to 5 moles, relative to the halide 1 mole shown by the above formula (1b).

反應可在溶媒的存在下施行。作為溶媒，可為例如醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)、水等，通常多數情況係使用四氫呋喃、水等。 The reaction can be carried out in the presence of a solvent. As the solvent, for example, an ether (chain ether such as diethyl ether, tetrahydrofuran, or two) may be used. In the case of a cyclic ether such as an alkane or the like, water or the like, tetrahydrofuran, water or the like is usually used in many cases.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可因應L²基而選擇，可為例如10至100℃，較佳為20至70℃(通常為室溫至50℃)左右。反應時間可為例如1至24小時，較佳為3至20小時左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be selected depending on the L ² group, and may be, for example, about 10 to 100 ° C, preferably 20 to 70 ° C (usually room temperature to 50 ° C). The reaction time may be, for example, from 1 to 24 hours, preferably from about 3 to 20 hours. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

<氧化反應> <oxidation reaction>

在氧化反應中，舉例而言，可調製式(1B)中之R³、R^3a及R^3b為氧原子之化合物(下述式(1e)所示之化合物)。式(1e)所示之化合物可藉由例如使藉由前述環化反應所調製而得之n、n1及n2為0之化合物(下述式(1d)所示之化合物)與氧化劑進行反應而予以調製。 In the oxidation reaction, for example, a compound of the formula (1B) wherein R ³ , R ^3a and R ^3b are an oxygen atom (a compound represented by the following formula (1e)) can be prepared. The compound of the formula (1e) can be reacted with an oxidizing agent by, for example, a compound obtained by the above-mentioned cyclization reaction, wherein n, n1 and n2 are 0 (a compound represented by the following formula (1d)). Modulate.

(式中，r表示1或2，r1及r2表示0至2 的整數，Z、Z¹、Z²、R^1a、R^1b、R²、R^2a、R^2b、R^4a、R^4b、R^5a、R^5b、m、m1及m2係各自亦包含較佳態樣在內並與前述式(1B)之記載相同)。 (wherein, r represents 1 or 2, and r1 and r2 represent an integer of 0 to 2, Z, Z ¹ , Z ² , R ^1a , R ^1b , R ² , R ^2a , R ^2b , R ^4a , R ^4b , R ^5a , R ^5b , m, m1 and m2 each also contain a preferred embodiment and are the same as described in the above formula (1B).

在前述式(1e)中，r、r1及r2係滿足v=m+2×r+2、v1=m1+2×r1+2及v2=m2+2×r2+2(式中，v、v1、v2、m、m1及m2係與前述相同)。因此，r、r1及r2可因應各原子價v、v1及v2而選擇，在原子價為4價或5價之情況，r、r1及r2為1，在原子價為6價之情況則為1或2(特別是2)。此外，r、r1及r2可因應Z、Z¹及Z²的種類或氧化劑的種類而選擇，可各自相同或相異。在Z¹及Z²為硫原子之情況，可能由於7員環上之Z方係電子密度較高而易於被氧化，因而多數情況係r1及r2為0。 In the above formula (1e), r, r1 and r2 satisfy v = m + 2 × r + 2, v1 = m1 + 2 × r1 + 2 and v2 = m2 + 2 × r2 + 2 (where v, V1, v2, m, m1, and m2 are the same as described above). Therefore, r, r1, and r2 can be selected according to the valences v, v1, and v2 of each atom. When the valence is 4 or 5, r, r1, and r2 are 1, and when the valence is hexavalent, 1 or 2 (especially 2). Further, r, r1 and r2 may be selected depending on the type of Z, Z ¹ and Z ² or the type of the oxidizing agent, and may be the same or different. In the case where Z ¹ and Z ² are sulfur atoms, the Z-band electron density on the 7-membered ring may be easily oxidized, and in many cases, r1 and r2 are zero.

作為氧化劑(oxygenating agent)(或氧化劑(oxidant))，可列舉例如有機過氧化物[例如氫過氧化物類(例如第三丁基氫過氧化物、1,1,3,3-四甲基丁基氫過氧化物等烷基氫過氧化物、異丙苯氫過氧化物等芳烷基氫過氧化物、二異丙基苯氫過氧化物等芳基羥基過氧化物等)；二烷基過氧化物類(例如二第三丁基過氧化物、二異丙苯基過氧化物等)；過氧羧酸類(例如過氧甲酸、過氧醋酸、過氧丙酸、過氧苯甲酸、間氯過氧苯甲酸、三氟過氧醋酸等)；過氧酯類(例如過氧苯甲酸第三丁酯、過氧醋酸第三丁酯等)；二醯基過氧化物類(例如苯甲醯基過氧化物(BPO)、月桂醯基過氧化物等)；過氧碳酸酯類(例如過氧碳酸O,O-第三丁基-O-異丙酯等過氧單碳酸酯、過氧二碳酸二異丙酯、 過氧二碳酸二(2-乙基己基)酯、過氧二碳酸二環己酯等過氧二碳酸酯等)；酮過氧化物類(例如甲基乙基酮過氧化物、環己酮過氧化物等)；過氧縮酮類(例如1,1-雙(第三丁基過氧基)-3,3,5-三甲基環己烷等)等]；無機過氧化物(例如過氧化氫、過氧化鈉等)等。 As the oxidizing agent (or oxidant), for example, an organic peroxide [for example, a hydroperoxide (for example, a tert-butyl hydroperoxide, 1,1,3,3-tetramethyl group) may be mentioned. An alkyl hydroperoxide such as butyl hydroperoxide, an aralkyl hydroperoxide such as cumene hydroperoxide or an aryl hydroxy peroxide such as diisopropylbenzene hydroperoxide; Alkyl peroxides (eg, di-tert-butyl peroxide, di-cumyl peroxide, etc.); peroxycarboxylic acids (eg, peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxybenzene) Formic acid, m-chloroperoxybenzoic acid, trifluoroperoxyacetic acid, etc.; peroxyesters (eg, tert-butyl peroxybenzoate, tributyl peroxyacetate, etc.); dimercapto peroxides ( For example, benzamyl peroxide (BPO), lauryl peroxide, etc.; peroxycarbonates (such as peroxycarbonic acid, O-O-tert-butyl-O-isopropyl ester, etc. Ester, diisopropyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, peroxydicarbonate such as dicyclohexyl peroxydicarbonate, etc.; ketone peroxides (eg A Ethyl ketone Compound, cyclohexanone peroxide, etc.); peroxyketals (for example, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, etc.); Inorganic peroxides (such as hydrogen peroxide, sodium peroxide, etc.).

此等氧化劑亦可單獨地或組合2種以上使用。此等氧化劑之中，大多係使用間氯過氧苯甲酸等過氧羧酸類。氧化劑的使用比率係相對於前述式(1d)所示之化合物1莫耳而言，可為例如1至5莫耳，較佳為1.3至3莫耳左右。 These oxidizing agents may be used singly or in combination of two or more. Among these oxidizing agents, peroxycarboxylic acids such as m-chloroperoxybenzoic acid are often used. The use ratio of the oxidizing agent may be, for example, 1 to 5 moles, preferably about 1.3 to 3 moles, relative to the compound 1 mole shown by the above formula (1d).

反應可在溶媒的存在下施行。作為溶媒，可為例如鹵烴類(二氯甲烷、氯仿、1,2-二氯乙烷、氯苯等)等，通常多數情況係使用二氯甲烷等。 The reaction can be carried out in the presence of a solvent. The solvent may be, for example, a halogen hydrocarbon (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.), and usually, dichloromethane or the like is used.

反應可在惰性氣體(氮；氦、氬等稀有氣體等)環境下施行。反應溫度可為例如-50至50℃，較佳為-30至30℃(通常為-20℃至室溫)左右。反應時間可為例如30至300分鐘，較佳為120至180分鐘左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, from -50 to 50 ° C, preferably from -30 to 30 ° C (typically from -20 ° C to room temperature). The reaction time may be, for example, 30 to 300 minutes, preferably about 120 to 180 minutes. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

<含金屬(或半金屬)之基之導入反應> <Introduction reaction of metal-containing (or semi-metal) based groups>

含金屬(或半金屬)之基可藉由慣用的方法予以導入，舉例而言，可藉由將前述式(1a)所示之化合物(或將前述式(1a)所示之化合物進行化學修飾而得之化合物)與因應前述基的種類之含金屬(或半金屬)之試劑進行反應之方法等 而予以導入。 The metal (or semimetal)-containing group can be introduced by a conventional method, for example, by chemically modifying the compound represented by the above formula (1a) (or the compound represented by the above formula (1a)) The obtained compound) is introduced by a method of reacting with a metal-containing (or semimetal)-containing reagent of the type of the above-mentioned group.

代表性而言，在例如含金屬之基為鋰原子之情況，可藉由前述鹵化反應之段落中所記載之式(1a)所示之化合物與作為含金屬之試劑之鋰化劑之反應而進行調製。 Typically, for example, in the case where the metal-containing group is a lithium atom, the compound represented by the formula (1a) described in the paragraph of the above halogenation reaction and the lithiating agent as a metal-containing reagent can be reacted. Make modulation.

此外，在含金屬之基為三烷基錫烷基之情況，可藉由前述鹵化反應之段落中所記載之前述式(1a)所示之化合物的鋰化物與作為含金屬之試劑之三烷基錫鹵化物之反應而進行調製。另外，前述鋰化物可在未將鋰化反應後之反應液予以分離精製之情形下，供予與三烷基錫鹵化物之反應。 Further, in the case where the metal group-containing group is a trialkylstannyl group, a lithium compound of the compound represented by the above formula (1a) described in the paragraph of the above halogenation reaction and a trioxane as a metal-containing reagent may be used. The reaction is carried out by the reaction of a tin-tin halide. Further, the lithium compound may be subjected to a reaction with a trialkyltin halide without separating and purifying the reaction liquid after the lithiation reaction.

作為三烷基錫鹵化物，可列舉例如三甲基錫氯化物、三甲基錫溴化物、正丁基錫氯化物等三C_1-6烷基錫鹵化物，較佳為三C_1-4烷基錫鹵化物等。此等三烷基錫鹵化物亦可單獨地或組合2種以上使用。此等三烷基錫鹵化物之中，大多係使用三甲基錫氯化物等三C_1-4烷基錫氯化物。三烷基錫鹵化物的使用比率係相對於鋰化前之前述式(1a)所示之化合物1莫耳而言，可為例如1至5莫耳，較佳為2至3莫耳左右。 The trialkyltin halide may, for example, be a tri-C _1-6 alkyl tin halide such as trimethyltin chloride, trimethyltin bromide or n-butyltin chloride, preferably a tri-C _1-4 alkane. Base tin halides, etc. These trialkyltin halides can also be used individually or in combination of 2 or more types. Among these trialkyltin halides, tri-C _1-4 alkyl tin chloride such as trimethyltin chloride is used. The use ratio of the trialkyltin halide may be, for example, 1 to 5 moles, preferably about 2 to 3 moles, relative to the compound 1 mole shown by the above formula (1a) before lithiation.

反應可在溶媒的存在下施行。作為溶媒，可為例如醚類(二乙基醚等鏈狀醚、四氫呋喃、二烷等環狀醚等)等，通常多數情況係使用四氫呋喃等。溶媒的量並無特別限制，可為例如可將反應系統予以均勻化之程度。 The reaction can be carried out in the presence of a solvent. As the solvent, for example, an ether (chain ether such as diethyl ether, tetrahydrofuran, or two) may be used. In the case of a cyclic ether such as an alkane or the like, tetrahydrofuran or the like is usually used in many cases. The amount of the solvent is not particularly limited, and may be, for example, a degree to which the reaction system can be homogenized.

反應可在惰性氣體(氮；氦、氬等稀有氣體 等)環境下施行。反應溫度可為例如-100至-50℃，較佳為-80至-70℃左右。反應時間可為例如1至300分鐘，較佳為60至180分鐘左右。反應終了後，可視需要藉由洗淨、萃取、乾燥、過濾、濃縮、再結晶、管柱精製等慣用的分離精製手段予以精製。 The reaction can be carried out under an inert gas (nitrogen; rare gas such as helium or argon). The reaction temperature may be, for example, -100 to -50 ° C, preferably about -80 to -70 ° C. The reaction time may be, for example, from 1 to 300 minutes, preferably from about 60 to 180 minutes. After the completion of the reaction, it may be purified by a conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, and column purification as needed.

[有機半導體及其製造方法，以及包含有機半導體之電子裝置] [Organic semiconductor and its manufacturing method, and electronic device including organic semiconductor]

本發明之有機半導體只要至少包含前述式(1)所示之應變型化合物即可，亦可視需要包含慣用的半導體材料。作為此種半導體材料，可列舉例如并苯類(例如并四苯、1,2-苯并菲(chrysene)、芘、并五苯、苉、苝、并六苯、并七苯、二苯并五苯、蔻(coronene)、四苯并五苯、卵苯(ovalene)等)；酞青類(例如酞青(銅酞青等)、萘酞青(naphthalocyanine)、亞酞青(subphthalocyanine)等)；咔唑類[例如1,3,5-參[2,7-(N,N-(對甲氧基苯基)胺基)-9H-咔唑-9-基]苯(SGT405)等]；噻吩類[例如2,5-雙[4-(N,N-雙(對甲氧基苯基)胺基)苯基]-3,4-伸乙二氧基噻吩(H101)、2,3,4,5-肆[4-(N,N-雙(對甲氧基苯基)胺基)苯基]噻吩(H111)等]；四羧酸二醯亞胺類[例如1,4,5,8-萘四羧酸二醯亞胺、2,3,6,7-萘四羧酸二醯亞胺、2,3,6,7-蒽四羧酸二醯亞胺等]；三苯荑(triptycene)類[例如2,6,14-參[5’-(4-(N,N-雙(對甲氧基苯基)胺基)苯基)-噻吩-2’-基]三苯荑(T103)等]等有機低分子半導體材料；聚乙炔(polyacethylene)類(反式聚乙炔等)；聚(對伸苯)類(聚(對伸苯)、聚(對伸苯乙烯)等)；聚吡咯類 (聚(吡咯-2,5-二基)等)；聚噻吩類[例如聚(3-甲基噻吩-2,5-二基)、聚(3-己基噻吩-2,5-二基)(P3HT)、聚[N-9’-十七烷基-2,7-咔唑-alt-5,5-(4’,7’-二-2-噻吩基-2’,1’,3’-苯并噻二唑)](PCDTBT)、聚[N-9’-十七烷基-2,7-咔唑-alt-3,6-雙(噻吩-5-基)-2,5-二辛基-2,5-二氫吡咯并[3,4]吡咯-1,4-二酮](PCBTDPP)、聚[2,6-(4,4-雙-(2-乙基己基)-4H-環戊[2,1-b；3,4-b’]二噻吩)-alt-4,7-(2,1,3-苯并噻二唑)](PCPDTBT)等]；聚三芳基胺類[例如聚[雙(苯-4-基)-(2,4,6-三甲基苯基)-胺](PTAA)、聚[雙(苯-4-基)-(4-丁基苯基)-胺](PolyTPD)等]；聚茀類[例如聚[9,9-二辛基茀-co-雙-N,N’-(4-丁基苯基)-雙-N,N’-苯基-1,4-伸苯二胺](PFB)等]等有機高分子半導體材料；碳材[例如富勒烯類(例如C₆₀富勒烯、C₇₀富勒烯、C₇₆富勒烯、C₇₈富勒烯、C₈₄富勒烯等)、石墨烯類(石墨烯、氧化石墨烯等)、奈米碳管類(單層奈米碳管(SWNT)、多層奈米碳管(MWNT)等)等]等無機半導體材料等。 The organic semiconductor of the present invention may contain at least the strain-type compound represented by the above formula (1), and may optionally contain a conventional semiconductor material. Examples of such a semiconductor material include acenes (for example, naphthacene, 1,2-benzopyrene, anthracene, pentacene, anthracene, anthracene, hexacene, hexacene, and dibenzo). Pentabenzene, coronene, tetrabenzopentabenzene, ovalene, etc.; indigo (such as indigo (copper indigo, etc.), naphthalocyanine, subphthalocyanine, etc. Carbazoles [eg 1,3,5-paran [2,7-(N,N-(p-methoxyphenyl)amino)-9H-carbazol-9-yl]benzene (SGT405), etc. Thiophene [eg 2,5-bis[4-(N,N-bis(p-methoxyphenyl)amino)phenyl]-3,4-extended ethylenedioxythiophene (H101), 2 , 3,4,5-anthracene [4-(N,N-bis(p-methoxyphenyl)amino)phenyl]thiophene (H111), etc.]; tetracarboxylic acid diterpenoids [eg 1, 4,5,8-naphthalenetetracarboxylic acid diimine, 2,3,6,7-naphthalenetetracarboxylic acid diimine, 2,3,6,7-nonanedicarboxylic acid diimine, etc.] ; tritium (triptycene) class [eg 2,6,14-paran [5'-(4-(N,N-bis(p-methoxyphenyl)amino)phenyl)-thiophene-2'- Organic low molecular semiconductor materials such as triphenylsulfonium (T103), polyacetylene (trans-polyacetylene, etc.); poly(p-phenylene) (poly(p-phenylene)), poly(pair) Styrene), etc.; polypyrroles (poly(pyrrole-2,5-diyl), etc.); polythiophenes [eg poly(3-methylthiophene-2,5-diyl), poly(3-hexyl) Thiophene-2,5-diyl)(P3HT), poly[N-9'-heptadecyl-2,7-oxazole-alt-5,5-(4',7'-di-2-thiophene -2',1',3'-benzothiadiazole)](PCDTBT), poly[N-9'-heptadecyl-2,7-oxazole-alt-3,6-bis(thiophene) -5-yl)-2,5-dioctyl-2,5-dihydropyrrolo[3,4]pyrrole-1,4-dione](PCBTDPP), poly[2,6-(4,4 - bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiazepine Oxazole)] (PCPDTBT), etc.; polytriarylamines [eg poly[bis(phenyl-4-yl)-(2,4,6-trimethylphenyl)-amine] (PTAA), poly[double (phenyl-4-yl)-(4-butylphenyl)-amine] (PolyTPD), etc.; polyfluorenes [eg poly[9,9-dioctylfluorene-co-bis-N,N'- Organic polymer semiconductor materials such as (4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylenediamine] (PFB), etc.; carbon materials [for example, fullerenes (for example) C ₆₀ fullerene, C ₇₀ fullerene, C ₇₆ fullerene, C ₇₈ fullerene, C ₈₄ fullerene, etc.), graphenes (graphene, graphene oxide, etc.), carbon nanotubes (single layer of carbon nanotubes (SWNT), multi-layered nanocarbon Inorganic semiconductor materials, etc., such as tubes (MWNT) and the like.

此等慣用的半導體材料亦可單獨地或組合2種以上使用。在本發明之有機半導體中，前述式(1)所示之應變型化合物的比率係相對於半導體材料整體而言，可為例如10重量%以上(例如30至100重量%)，較佳為50重量%以上(例如70至99.9重量%)，更佳為80重量%以上(例如90至99重量%)左右，亦可為實質上100重量%(僅前述式(1)所示之化合物)。 These conventional semiconductor materials may be used singly or in combination of two or more. In the organic semiconductor of the present invention, the ratio of the strain type compound represented by the above formula (1) may be, for example, 10% by weight or more (for example, 30 to 100% by weight), preferably 50%, based on the entire semiconductor material. The weight % or more (for example, 70 to 99.9% by weight), more preferably 80% by weight or more (for example, 90 to 99% by weight), or substantially 100% by weight (only the compound represented by the above formula (1)).

本發明之有機半導體(有機半導體薄膜或有 機半導體層)可藉由真空蒸鍍法、濺鍍法等乾式製程予以形成，但由於前述式(1)所示之應變型化合物顯示出較高的溶劑溶解性，因而亦可藉由濕式製程(塗佈等)予以形成。前述濕式製程包含對基材(或基板)之至少一面，塗佈包含前述有機半導體及溶媒之組成物(或溶液)，並將溶媒去除之製膜步驟。 The organic semiconductor (organic semiconductor thin film or organic semiconductor layer) of the present invention can be formed by a dry process such as a vacuum deposition method or a sputtering method, but the strain type compound represented by the above formula (1) exhibits a high solvent. Solubility can thus also be formed by a wet process (coating, etc.). The wet process includes a film forming step of applying a composition (or solution) containing the organic semiconductor and the solvent to at least one surface of the substrate (or the substrate) and removing the solvent.

作為前述基材(或基板)，並無特別限制，可為例如玻璃板、矽晶圓、塑膠膜(例如聚對酞酸乙二酯膜等透明樹脂膜等)等。此等基材可視需要在表面形成1或複數種機能層(例如ITO等導電層、SiO₂等絕緣層、β-苯乙基三甲氧基矽烷(β-PTS)等自組織化單分子膜(SAM)等)。 The substrate (or substrate) is not particularly limited, and may be, for example, a glass plate, a tantalum wafer, a plastic film (for example, a transparent resin film such as a polyethylene terephthalate film), or the like. These substrates may form one or a plurality of functional layers (for example, a conductive layer such as ITO, an insulating layer such as SiO ₂ or a self-assembled monomolecular film such as β-phenethyltrimethoxydecane (β-PTS)). SAM), etc.).

作為溶媒，可列舉例如芳香族烴類(例如苯、甲苯、二甲苯、大茴香醚、氯苯等)；鹵烴類(例如二氯甲烷、氯仿、1,2-二氯乙烷等鹵C_1-6烷烴)；醇類(例如甲醇、乙醇、2-丙醇、正丁醇、第三丁醇等C_1-6烷烴單醇；乙二醇等C_2-4烷烴二醇等)；醚類(二乙基醚、二異丙基醚等鏈狀醚類、四氫呋喃、二烷等環狀醚類等)；二醇醚類[例如賽路蘇(cellosolve)類(甲基賽路蘇等)、卡必醇(carbitol)類(甲基卡必醇等)、三乙二醇單甲基醚、丙二醇單甲基醚等(聚)C_2-4烷二醇單C_1-4烷基醚；乙二醇二甲基醚、二丙二醇二甲基醚等(聚)C_2-4烷二醇二C_1-4烷基醚等]；二醇醚醋酸酯類[例如賽路蘇醋酸酯類(例如甲基賽路蘇醋酸酯等C_1-4烷基賽路蘇醋酸酯等)、卡必醇醋酸酯類(例如甲基卡必醇醋酸酯等C_1-4烷基卡必醇醋酸酯等)、丙二醇單甲基醚 醋酸酯、二丙二醇單丁基醚醋酸酯等(聚)C_2-4烷二醇單C_1-4烷基醚醋酸酯等]；酮類(丙酮、甲基乙基酮等鏈狀酮、環己酮等環狀酮等)；酯類(醋酸乙酯等醋酸酯、乳酸甲酯等乳酸酯等)；碳酸酯類(碳酸二甲酯等鏈狀碳酸酯、碳酸伸乙酯、碳酸伸丙酯等環狀碳酸酯等)；腈類(乙腈、丙腈、苯甲腈等)；醯胺類(N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等)；亞碸類(二甲基亞碸等)；及此等之混合溶媒等。此等溶媒之中，通常多數情況為甲苯、大茴香醚等芳香族烴類。 Examples of the solvent include aromatic hydrocarbons (for example, benzene, toluene, xylene, anisole, chlorobenzene, etc.); halogen hydrocarbons (for example, halogen C such as dichloromethane, chloroform or 1,2-dichloroethane). _1-6 alkane); alcohol (for example, C _1-6 alkane monoalcohol such as methanol, ethanol, 2-propanol, n-butanol or tert-butanol; C _2-4 alkane diol such as ethylene glycol, etc.); Ethers (chain ethers such as diethyl ether and diisopropyl ether, tetrahydrofuran, two a cyclic ether such as an alkane or the like; a glycol ether (for example, cellosolve (methyl siroliol), carbitol (methyl carbitol, etc.), triethylene hydride (poly)C _2-4 alkanediol mono C _1-4 alkyl ether such as alcohol monomethyl ether or propylene glycol monomethyl ether; ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether or the like (poly) C _2-4 alkanediol di C _1-4 alkyl ether, etc.]; glycol ether acetates [eg, cyprosone acetates (eg, C _1-4 alkyl 赛路苏, such as methyl stilbene acetate) Acetate, etc., carbitol acetate (such as C _1-4 alkyl carbitol acetate such as methyl carbitol acetate), propylene glycol monomethyl ether acetate, dipropylene glycol monobutyl ether acetate (E) C ( _2-4 ) alkanediol mono C _1-4 alkyl ether acetate, etc.; ketones (chain ketones such as acetone and methyl ethyl ketone, cyclic ketones such as cyclohexanone, etc.); Ester (acetate such as ethyl acetate, lactate such as methyl lactate, etc.); carbonate (chain carbonate such as dimethyl carbonate, cyclic carbonate such as ethyl carbonate or propyl carbonate) Nitriles (acetonitrile, propionitrile, benzonitrile, etc.); decylamines (N,N-dimethylformamide, N,N-dimethylacetamide, N- Methyl-2-pyrrolidone, etc.); anthraquinones (dimethyl hydrazine, etc.); and such mixed solvents. Among these solvents, an aromatic hydrocarbon such as toluene or anisole is usually used in many cases.

組成物(或溶液)的濃度(固形分濃度)可因應塗佈方法等而選擇，可為例如0.001至10重量%(例如0.005至5重量%)，較佳為0.01至1重量%(例如0.02至0.5重量%)，更佳為0.03至0.1重量%左右。 The concentration (solid content concentration) of the composition (or solution) may be selected depending on the coating method or the like, and may be, for example, 0.001 to 10% by weight (for example, 0.005 to 5% by weight), preferably 0.01 to 1% by weight (for example, 0.02). Up to 0.5% by weight), more preferably from about 0.03 to 0.1% by weight.

塗佈方法並無特別限制，可採用慣用的塗佈方法，例如氣刀塗佈法、輥塗佈法、凹版塗佈法、刮刀塗佈法、棒塗佈法、模具塗佈法、浸漬塗佈法、噴霧塗佈法、旋轉塗佈法、澆鑄法、邊緣澆鑄法、網版印刷法、噴墨印刷法等。此等塗佈方法之中，通常多數情況係利用旋轉塗佈法、邊緣澆鑄法、噴墨印刷法等。 The coating method is not particularly limited, and a conventional coating method such as an air knife coating method, a roll coating method, a gravure coating method, a knife coating method, a bar coating method, a die coating method, or a dip coating method may be employed. Cloth method, spray coating method, spin coating method, casting method, edge casting method, screen printing method, inkjet printing method, and the like. Among these coating methods, in many cases, a spin coating method, an edge casting method, an inkjet printing method, or the like is used.

可藉由對塗膜以經由自然乾燥、加熱處理之乾燥等慣用的方法去除溶媒而形成有機半導體(層)。前述加熱處理中之溫度可為例如30至100℃，較佳為40至80℃左右。此外，可視需要於減壓下進行乾燥。 The organic semiconductor (layer) can be formed by removing the solvent by a conventional method such as drying by natural drying or heat treatment. The temperature in the aforementioned heat treatment may be, for example, 30 to 100 ° C, preferably about 40 to 80 ° C. In addition, drying may be carried out under reduced pressure as needed.

如此所獲得之有機半導體(層)的厚度係因 應用途，可為例如1至5000nm，較佳為30至1000nm，更佳為50至500nm左右。 The thickness of the organic semiconductor (layer) thus obtained may be, for example, from 1 to 5,000 nm, preferably from 30 to 1,000 nm, more preferably from about 50 to 500 nm, depending on the application.

本發明之有機半導體可為n型半導體、p型半導體，亦可為真性半導體。由於本發明之有機半導體係電子及/或電洞(孔洞)的移動度(載子移動度或電移動度)較高，因而適合作為電子裝置，例如開關元件、整流元件、電晶體等半導體元件的材料。此種有機薄膜電晶體係由閘極電極層、閘極絕緣層、源極/汲極電極層及有機半導體層所構成。依據此等層的積層結構，有機薄膜電晶體可分類成頂閘極型、底閘極型(頂接觸型、底接觸型)。舉例而言，可藉由在閘極電極(形成有氧化膜之p型矽晶圓等)形成有機半導體膜，並在此有機半導體膜上形成源極/汲極電極(金電極)，而製造頂接觸型場效電晶體。此外，亦可在前述源極/汲極電極層與前述有機半導體層之間，形成載子注入層(摻雜物層)。此種載子注入層可由例如四氰基醌二甲烷(TCNQ)、2,3,5,6-四氟四氰基醌二甲烷(F4TCNQ)等TCNQ類、氯化鐵(III)等金屬鹵化物、富勒烯類等所形成。 The organic semiconductor of the present invention may be an n-type semiconductor or a p-type semiconductor, or may be a true semiconductor. Since the organic semiconductor-based electrons and/or holes (holes) of the present invention have high mobility (carrier mobility or electrical mobility), they are suitable as electronic devices, such as switching elements, rectifying elements, and transistors. s material. The organic thin film electro-crystal system is composed of a gate electrode layer, a gate insulating layer, a source/drain electrode layer, and an organic semiconductor layer. According to the laminated structure of these layers, the organic thin film transistor can be classified into a top gate type and a bottom gate type (top contact type, bottom contact type). For example, an organic semiconductor film can be formed on a gate electrode (a p-type germanium wafer formed with an oxide film, etc.), and a source/drain electrode (gold electrode) can be formed on the organic semiconductor film. Top contact type field effect transistor. Further, a carrier injection layer (dopant layer) may be formed between the source/drain electrode layer and the organic semiconductor layer. Such a carrier injection layer may be halogenated by a metal such as TCNQ or iron (III) such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyanoquinodimethane (F4TCNQ). Formed by substances, fullerenes, and the like.

此外，本發明之有機半導體經由光吸收之載子移動度(光電轉換率)較高，具有光電轉換能力。因此，本發明之有機半導體亦適合作為光電轉換裝置或光電轉換元件(太陽能電池元件、有機電致發光(EL)元件等)、整流元件(二極體)的材料。作為代表性的光電轉換裝置之太陽能電池可具有在pn接合型半導體積層有表面電極之結構， 例如在p型矽半導體積層有機半導體層並在此有機半導體層積層透明電極(ITO電極等)而得之結構。此外，有機EL元件可為在透明電極(ITO電極等)形成包含有機半導體之發光層並在此發光層積層電極(金屬電極等)而得之結構，可視需要使電子輸送劑、電洞輸送劑分散於發光層中。 Further, the organic semiconductor of the present invention has a high carrier mobility (photoelectric conversion rate) via light absorption and has photoelectric conversion capability. Therefore, the organic semiconductor of the present invention is also suitable as a material for a photoelectric conversion device or a photoelectric conversion element (a solar cell element, an organic electroluminescence (EL) element, etc.) or a rectifying element (a diode). A solar cell as a representative photoelectric conversion device may have a structure in which a surface electrode is laminated on a pn junction type semiconductor, for example, a p-type germanium semiconductor laminate organic semiconductor layer and a transparent electrode (ITO electrode or the like) laminated thereon. The structure. Further, the organic EL element may have a structure in which a light-emitting layer containing an organic semiconductor is formed on a transparent electrode (ITO electrode or the like), and an electrode (metal electrode or the like) is laminated thereon, and an electron transporting agent or a hole transporting agent may be used as needed. Dispersed in the luminescent layer.

〔實施例〕  [Examples]  

以下，基於實施例更詳細地說明本發明，但本發明不受此等實施例所限定。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples.

[實施例1] [Example 1]

(1)3-溴噻吩-2-甲醛的還原 (1) Reduction of 3-bromothiophene-2-carbaldehyde

在氬環境下，一面將3-溴噻吩-2-甲醛(化合物(2-1)，10g，52.3mmol)/乙醇(EtOH，200mL)溶液於0℃進行攪拌，一面加入硼氫化鈉(NaBH₄，3.4g，90.1mmol)，於室溫攪拌24小時。對將反應液於減壓下進行濃縮所獲得之油狀固體加入氯化銨水溶液，將有機層以醋酸乙酯進行萃取。將萃取液以硫酸鎂進行乾燥，過濾後，將濾液於減壓下進行濃縮而獲得粗生成物。藉由將粗生成物以矽膠管柱層析(醋酸乙酯/己烷(體積比)=2/8)進行精製，而獲得目標化合物3-溴噻吩-2-甲醇(化合物(3-1)，產量9.3g，產 率92%)。 A solution of 3-bromothiophene-2-carbaldehyde (compound (2-1), 10 g, 52.3 mmol) / ethanol (EtOH, 200 mL) was stirred at 0 ° C under argon, and sodium borohydride (NaBH _{4 ) was added.} , 3.4 g, 90.1 mmol), stirred at room temperature for 24 hours. The oily solid obtained by concentrating the reaction liquid under reduced pressure was added to an aqueous ammonium chloride solution, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, and after filtration, the filtrate was concentrated under reduced pressure to give a crude product. The title compound 3-bromothiophene-2-methanol (Compound (3-1) was obtained by purifying the crude product by silica gel column chromatography (ethyl acetate/hexane (volume ratio) = 2/8). , yield 9.3 g, yield 92%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.27(d、1H、J=5.2Hz)、6.96(d、1H、J=5.2Hz)、4.80(d、2H、J=6.0Hz)、1.94(s、br、1H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.27 (d, 1H, J = 5.2 Hz), 6.96 (d, 1H, J = 5.2 Hz), 4.80 (d, 2H, J = 6.0 Hz) , 1.94 (s, br, 1H).

(2)鏻鹽的合成 (2) Synthesis of cerium salt

在氬環境下，一面將3-溴噻吩-2-甲醇(化合物(3-1)，300mg，1.6mmol)/氯仿(CHCl₃，2mL)溶液於室溫進行攪拌，一面加入三苯基膦氫溴酸鹽(化合物(4-1)，533mg，1.6mmol)，在回流條件下攪拌20小時後，回復至室溫，於減壓下進行濃縮，獲得粗生成物。藉由將此粗生成物以再結晶(氯仿/二乙基醚)進行精製，而獲得目標化合物三苯基-(3-溴-2-噻吩基)甲基鏻溴化物(化合物(5-1)，產量9.3g，產率99%)。 3-Bromothiophene-2-methanol (Compound (3-1), 300 mg, 1.6 mmol) / chloroform (CHCl ₃ , 2 mL) was stirred at room temperature under argon, and triphenylphosphine hydrogen was added thereto. The bromate (Compound (4-1), 533 mg, 1.6 mmol) was stirred under reflux for 20 hr, then was taken to room temperature and concentrated under reduced pressure to give a crude product. The crude product was purified by recrystallization (chloroform/diethyl ether) to give the title compound triphenyl-(3-bromo-2-thienyl)methylindole bromide (compound (5-1) ), yield 9.3 g, yield 99%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.76-7.88(m、9H)、7.63-7.73(m、6H)、7.24(td、1H、J=2.8、5.2Hz)、6.82(d、1H、J=5.2Hz)、5.87(d、2H、J=13.2Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.76-7.88 (m, 9H), 7.63-7.73 (m, 6H), 7.24 (td, 1H, J = 2.8, 5.2 Hz), 6.82 (d) , 1H, J = 5.2 Hz), 5.87 (d, 2H, J = 13.2 Hz).

(3)Wittig反應 (3) Wittig reaction

在氬環境下，一面將三苯基-(3-溴-2-噻吩基)甲基鏻溴化物(化合物(5-1)，64.0g，123.5mmol)/四氫呋喃(THF，1L)溶液於0℃進行攪拌，一面加入第三丁氧化鉀(tBuOK，45.7g，407.6mmol)，並於0℃攪拌1小時。再者，加入3-溴噻吩-2-甲醛(化合物(2-1)，21.2g，111.1mmol)。一面使此黑色反應溶液自然地上升至室溫，一面攪拌46小時。對反應溶液加入水，將減壓下經濃縮所獲得之懸浮液以氯仿進行稀釋，進行過濾。將濾液的有機層以氯仿進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷)進行精製，獲得目標化合物的黃色固體1,2-雙(3-溴-2-噻吩基)乙烯(化合物(6-1)，產量17.6g，產率45%)。 A solution of triphenyl-(3-bromo-2-thienyl)methylindole bromide (compound (5-1), 64.0 g, 123.5 mmol) / tetrahydrofuran (THF, 1 L) While stirring at ° C, a third potassium pentoxide (tBuOK, 45.7 g, 407.6 mmol) was added, and stirred at 0 ° C for 1 hour. Further, 3-bromothiophene-2-carbaldehyde (Compound (2-1), 21.2 g, 111.1 mmol) was added. The black reaction solution was allowed to naturally rise to room temperature while stirring for 46 hours. Water was added to the reaction solution, and the suspension obtained by concentration under reduced pressure was diluted with chloroform and filtered. The organic layer of the filtrate was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to obtain the title compound as a yellow solid 1,2-bis(3-bromo-2-thienyl)ethylene (compound) (6-1), yield 17.6 g, yield 45%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.27(d、2H、J=5.2Hz)、6.99(d、2H、J=5.2Hz)、6.71(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.27 (d, 2H, J = 5.2 Hz), 6.99 (d, 2H, J = 5.2 Hz), 6.71 (s, 2H).

(4)經由環化反應之硫雜環庚烯環的形成 (4) Formation of a thioheptene ring via a cyclization reaction

在氬環境下，一面將1,2-雙(3-溴-2-噻吩基)乙烯(化合物(6-1)，5.7g，16.3mmol)/二乙基醚(Et₂O，230mL)溶液於-78℃進行攪拌，一面滴加正丁基鋰(n-BuLi)/己烷溶液(1.63M，20mL，32.6mmol)，於-78℃攪拌1小時。對此綠色懸浮液，於-78℃加入苯硫磺酸酐(化合物(7-1)，5.6g，17.9mmol)/THF(190mL)溶液，一面使其自然地上升至室溫，一面攪拌7.5小時。對反應溶液加入水，以醋酸乙酯進行稀釋後，將有機層以醋酸乙酯進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷)進行精製，獲得目標化合物的黃色固體二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-1)，產量1.3g，產率35%)。 1,2-bis(3-bromo-2-thienyl)ethene (compound (6-1), 5.7 g, 16.3 mmol) / diethyl ether (Et ₂ O, 230 mL) in a argon atmosphere After stirring at -78 ° C, n-butyllithium (n-BuLi) / hexane solution (1.63 M, 20 mL, 32.6 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 1 hour. To the green suspension, a solution of phenylthiosulfonic acid anhydride (Compound (7-1), 5.6 g, 17.9 mmol) / THF (190 mL) was added at -78 ° C, and the mixture was allowed to naturally rise to room temperature while stirring for 7.5 hours. After adding water to the reaction solution and diluting with ethyl acetate, the organic layer was extracted with ethyl acetate, dried over magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to give the title compound as a yellow solid dithiophene[3,2-b:2,3-f] Cycloheptene (compound (1-1), yield 1.3 g, yield 35%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.27(d、2H、J=5.2Hz)、6.99(d、2H、J=5.2Hz)、6.71(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.27 (d, 2H, J = 5.2 Hz), 6.99 (d, 2H, J = 5.2 Hz), 6.71 (s, 2H).

[實施例2]溴化物的合成 [Example 2] Synthesis of bromide

在氬環境下，一面將二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-1)，200mg，0.9mmol)/THF(30mL)溶液於-78℃進行攪拌，一面滴加鋰四甲基哌啶(LiTMP)/THF溶液(0.71M，3.1mL，2.2mmol)，於-78℃攪拌2小時。 對此黃色懸浮液，於-78℃加入1,2-二溴-1,1,2,2-四氯乙烷(703mg，2.2mmol)，一面使其自然地上升至室溫，一面攪拌17小時。對反應溶液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷)進行精製，獲得目標化合物的黃色固體2,6-二溴-二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-2)，產量323mg，產率94%)。 A solution of dithieno[3,2-b:2,3-f]thiene (Compound (1-1), 200 mg, 0.9 mmol) in THF (30 mL) was taken in -78 under argon. After stirring at ° C, a lithium tetramethylpiperidine (LiTMP) / THF solution (0.71 M, 3.1 mL, 2.2 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 2 hours. To the yellow suspension, 1,2-dibromo-1,1,2,2-tetrachloroethane (703 mg, 2.2 mmol) was added at -78 ° C, and the mixture was allowed to naturally rise to room temperature while stirring. hour. After adding water to the reaction solution and diluting with chloroform, the organic layer was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to obtain the title compound as a yellow solid 2,6-dibromo-dithieno[3,2-b:2 , 3-f]thiazepine (compound (1-2), yield 323 mg, yield 94%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)6.71(s、2H)、6.67(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 6.71 (s, 2H), 6.67 (s, 2H).

[實施例3]偶合反應 [Example 3] Coupling reaction

在氬環境下，將2,6-二溴-[3,2-b：2,3-f]硫雜環庚烯(化合物(1-2)，100mg，0.263mmol)/4-己基苯基硼酸(化合物(8-2)，163mg，0.789mmol)/醋酸鈀(Pd(OAc)₂，5.9mg，0.0263mmol)/三第三丁基鏻四氟硼酸鹽(P(tBu)₃HBF₄，8.4mg，0.0289mmol)/THF(8mL)溶液於室溫攪拌15分鐘。對此黑色溶液加入氫氧化鈉(NaOH，42mg，1.05mmol)/水(H₂O，2mL)溶液，進一步於室溫攪拌4小時。對此橙色懸浮液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取。以硫酸鎂進行乾燥後，進行過濾，將 減壓下經濃縮所獲得之粗生成物以矽膠管柱層析(氯仿/己烷(體積比)=15/85)進行精製而獲得目標化合物的橙色固體2,6-雙(4-己基苯基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-3)，產量110mg，產率77%)。 2,6-Dibromo-[3,2-b:2,3-f]thiene (Compound (1-2), 100 mg, 0.263 mmol) / 4-hexylphenyl group under argon atmosphere Boric acid (compound (8-2), 163 mg, 0.789 mmol) / palladium acetate (Pd(OAc) ₂ , 5.9 mg, 0.0263 mmol) / tri-tert-butyl fluorene tetrafluoroborate (P(tBu) ₃ HBF ₄ , A solution of 8.4 mg, 0.0289 mmol) / THF (8 mL) was stirred at room temperature for 15 min. A solution of sodium hydroxide (NaOH, 42 mg, 1.05 mmol) / water (H ₂ O, 2 mL) was added to this black solution, and the mixture was further stirred at room temperature for 4 hours. Water was added to the orange suspension, and after dilution with chloroform, the organic layer was extracted with chloroform. After drying over magnesium sulfate, it was filtered, and the crude product obtained by concentration under reduced pressure was purified by silica gel column chromatography (chloroform/hexane (volume ratio) = 15/85) to obtain orange of the target compound. Solid 2,6-bis(4-hexylphenyl)-dithieno[3,2-b:2,3-f]thiene (compound (1-3), yield 110 mg, yield 77%) ).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.41(d、4H、J=8.4Hz)、7.17(d、4H、J=8.4Hz)、6.92(s、2H)、6.73(s、2H)、2.60(t、4H、J=7.6Hz)、1.57-1.65(m、4H)、1.26-1.37(m、12H)、0.88(t、6H、J=7.2Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.41 (d, 4H, J = 8.4 Hz), 7.17 (d, 4H, J = 8.4 Hz), 6.92 (s, 2H), 6.73 (s, 2H), 2.60 (t, 4H, J = 7.6 Hz), 1.57-1.65 (m, 4H), 1.26-1.37 (m, 12H), 0.88 (t, 6H, J = 7.2 Hz).

[實施例4]偶合反應 [Example 4] Coupling reaction

在氬環境下，一面將4-癸基苯基鋅氯化物(化合物(8-3))/THF(8.6mL，1.58mmol)溶液於0℃進行攪拌，一面依次加入2,6-二溴-[3,2-b：2,3-f]硫雜環庚烯(化合物(1-2)，200mg，0.526mmol)、參(二苯亞甲基丙酮)二鈀(0)氯仿錯合物(Pd₂(dba)₃CHCl₃，13.6mg，0.0132mmol)、三第三丁基鏻四氟硼酸鹽(P(tBu)₃HBF₄，15.3mg，0.0526mmol)。將反應溶液於50℃攪拌15小時。對反應溶液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，以硫酸鎂進行乾燥，過濾後，將減壓下經濃縮所獲得之粗生成物以矽膠管柱層析(氯仿/己烷(體積比)=5/95)進行 精製，獲得目標化合物的褐色固體2,6-雙(4-癸基苯基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-4)，產量77mg，產率22%)。 In a argon atmosphere, a solution of 4-nonylphenyl zinc chloride (compound (8-3)) / THF (8.6 mL, 1.58 mmol) was stirred at 0 ° C while 2,6-dibromo- [3,2-b:2,3-f]thiane (compound (1-2), 200 mg, 0.526 mmol), bis(diphenylmethyleneacetone) dipalladium(0) chloroform complex (Pd ₂ (dba) ₃ CHCl ₃ , 13.6 mg, 0.0132 mmol), tri-tert-butylindole tetrafluoroborate (P(tBu) ₃ HBF ₄ , 15.3 mg, 0.0526 mmol). The reaction solution was stirred at 50 ° C for 15 hours. After adding water to the reaction solution, and diluting with chloroform, the organic layer was extracted with chloroform, and dried over magnesium sulfate. After filtration, the crude product obtained by concentration under reduced pressure was chromatographed on silica gel column chromatography. Purification by hexane (volume ratio) = 5/95) to obtain the title compound as a brown solid 2,6-bis(4-mercaptophenyl)-dithieno[3,2-b:2,3-f] Heterocyclen (compound (1-4), yield 77 mg, yield 22%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.41(d、4H、J=7.6Hz)、7.17(d、4H、J=7.6Hz)、6.92(s、2H)、6.73(s、2H)、2.56(t、4H、J=7.6Hz)、1.56-1.75(m、4H)、1.20-1.38(m、28H)、0.88(t、6H、J=6.8Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.41 (d, 4H, J = 7.6 Hz), 7.17 (d, 4H, J = 7.6 Hz), 6.92 (s, 2H), 6.73 (s, 2H), 2.56 (t, 4H, J = 7.6 Hz), 1.56-1.75 (m, 4H), 1.20 to 1.38 (m, 28H), 0.88 (t, 6H, J = 6.8 Hz).

[實施例5]偶合反應 [Example 5] Coupling reaction

在氬環境下，一面將3-癸基苯基鋅氯化物(化合物(8-4))/THF(8.6mL，1.58mmol)溶液於室溫進行攪拌，一面依次加入2,6-二溴-[3,2-b：2,3-f]硫雜環庚烯(化合物(1-2)，200mg，0.526mmol)、參(二苯亞甲基丙酮)二鈀(0)氯仿錯合物(Pd₂(dba)₃CHCl₃，13.6mg，0.0132mmol)、三第三丁基鏻四氟硼酸鹽(P(tBu)₃HBF₄，15.3mg，0.0526mmol)。將反應溶液於50℃攪拌15小時。對反應溶液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，以硫酸鎂進行乾燥，過濾後，將減壓下經濃縮所獲得之粗生成物以矽膠管柱層析(氯仿/己烷(體積比)=5/95)進行精製，獲得目標化合物的褐色固體2,6-雙(3-癸基苯基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-5)，產量92mg， 產率27%)。 A solution of 3-mercaptophenyl zinc chloride (compound (8-4)) / THF (8.6 mL, 1.58 mmol) was stirred at room temperature under argon, and 2,6-dibromo- [3,2-b:2,3-f]thiane (compound (1-2), 200 mg, 0.526 mmol), bis(diphenylmethyleneacetone) dipalladium(0) chloroform complex (Pd ₂ (dba) ₃ CHCl ₃ , 13.6 mg, 0.0132 mmol), tri-tert-butylindole tetrafluoroborate (P(tBu) ₃ HBF ₄ , 15.3 mg, 0.0526 mmol). The reaction solution was stirred at 50 ° C for 15 hours. After adding water to the reaction solution, and diluting with chloroform, the organic layer was extracted with chloroform, and dried over magnesium sulfate. After filtration, the crude product obtained by concentration under reduced pressure was chromatographed on silica gel column chromatography. Purification by hexane (volume ratio) = 5/95) to obtain the title compound as a brown solid 2,6-bis(3-mercaptophenyl)-dithieno[3,2-b:2,3-f] Heterocyclen (compound (1-5), yield 92 mg, yield 27%).

¹H-NMR(400MHz、TCE-d₂)：δ(ppm)7.24-7.29(m、2H)、7.26(s、2H)、7.23(t、2H、J=7.6Hz)、7.08(d、2H、J=7.6Hz)、6.92(s、2H)、6.69(s、2H)、2.55(t、4H、J=7.6Hz)、1.5-1.62(m、4H)、1.12-1.33、(m、28H)、0.82(t、6H、J=7.6Hz)。 ^{1 H-NMR (400MHz, TCE} -d 2): δ (ppm) 7.24-7.29 (m, 2H), 7.26 (s, 2H), 7.23 (t, 2H, J = 7.6Hz), 7.08 (d, 2H , J = 7.6 Hz), 6.92 (s, 2H), 6.69 (s, 2H), 2.55 (t, 4H, J = 7.6 Hz), 1.5-1.62 (m, 4H), 1.12-1.33, (m, 28H) ), 0.82 (t, 6H, J = 7.6 Hz).

[實施例6]偶合反應 [Example 6] Coupling reaction

在氬環境下，將2,6-二溴-[3,2-b：2,3-f]硫雜環庚烯(化合物(1-2)，90mg，0.24mmol)/2-噻吩基硼酸(化合物(8-5)，91mg，0.71mmol)/醋酸鈀(Pd(OAc)₂，5.3mg，0.024mmol)/三第三丁基鏻四氟硼酸鹽(P(tBu)₃HBF₄，7.6mg，0.026mmol)/THF(8mL)溶液於室溫攪拌15分鐘。對此褐色溶液加入氫氧化鈉(NaOH，38mg，0.95mmol)/水(H₂O，2mL)溶液，進一步於室溫攪拌4小時。對此紅色懸浮液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，將減壓下經濃縮所獲得之粗生成物以矽膠管柱層析(氯仿/己烷(體積比)=15/85)進行精製而獲得目標化合物的紅色固體2,6-二(2-噻吩基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-6)，產量90mg，產率98%)。 2,6-Dibromo-[3,2-b:2,3-f]thiene (Compound (1-2), 90 mg, 0.24 mmol)/2-thienylboronic acid under argon (Compound (8-5), 91 mg, 0.71 mmol) / palladium acetate (Pd(OAc) ₂ , 5.3 mg, 0.024 mmol) / tri-tert-butyl fluorene tetrafluoroborate (P(tBu) ₃ HBF ₄ , 7.6 A solution of mg, 0.026 mmol) / THF (8 mL) was stirred at room temperature for 15 min. A solution of sodium hydroxide (NaOH, 38 mg, 0.95 mmol) / water (H ₂ O, 2 mL) was added to this brown solution, and the mixture was further stirred at room temperature for 4 hours. Water was added to the red suspension, and the mixture was diluted with chloroform. The organic layer was extracted with chloroform, and the crude product obtained by concentration under reduced pressure was chromatographed by column chromatography (chloroform/hexane (volume ratio) = 15/85) Red solid 2,6-bis(2-thienyl)-dithieno[3,2-b:2,3-f]thiene (compound (1) -6), yield 90 mg, yield 98%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.24(dd、 2H、J=5.2、1.2Hz)、7.12(dd、2H、J=3.6、1.2Hz)、7.01(dd、2H、J=5.2、3.6Hz)、6.82(s、2H)、6.71(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.24 (dd, 2H, J = 5.2, 1.2 Hz), 7.12 (dd, 2H, J = 3.6, 1.2 Hz), 7.01 (dd, 2H, J) = 5.2, 3.6 Hz), 6.82 (s, 2H), 6.71 (s, 2H).

[實施例7]氧化反應 [Example 7] Oxidation reaction

在氬環境下，一面將二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-1)，50mg，0.23mmol)/二氯甲烷(CH₂Cl₂，2mL)溶液於-20℃進行攪拌，一面加入間氯過氧苯甲酸(mCPBA，111mg，0.45mmol)，一面使其自然地上升至室溫一面攪拌2.5小時。對反應溶液加入硫代硫酸鈉水溶液，以氯仿進行稀釋後，將有機層以氯仿進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(氯仿)進行精製，獲得白色的目標化合物4,4-二側氧基-二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-7)，產量57mg，產率99%)。 Dithieno[3,2-b:2,3-f]thiene (Compound (1-1), 50 mg, 0.23 mmol) / dichloromethane (CH ₂ Cl ₂ ) under argon The solution was stirred at -20 ° C, and m-chloroperoxybenzoic acid (mCPBA, 111 mg, 0.45 mmol) was added thereto, and the mixture was allowed to naturally rise to room temperature while stirring for 2.5 hours. After adding an aqueous solution of sodium thiosulfate to the reaction solution and diluting with chloroform, the organic layer was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (chloroform) to afford white compound 4,4-di- oxy-dithiophene[3,2-b:2 , 3-f]thiazepine (compound (1-7), yield 57 mg, yield 99%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.63(d、2H、J=5.6Hz)、7.55(d、2H、J=5.6Hz)、7.29(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.63 (d, 2H, J = 5.6 Hz), 7.55 (d, 2H, J = 5.6 Hz), 7.29 (s, 2H).

[實施例8]三甲基錫烷基的導入 [Example 8] Introduction of trimethylstannyl group

在氬環境下，一面將二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-1)，55.6mg，0.25mmol)/THF(1mL)溶液於-78℃進行攪拌，一面滴加正丁基鋰(n-BuLi)/己烷溶液(1.63M，0.37mL，0.6mmol)，於-78℃攪拌1小時後，於-78℃加入三甲基錫氯化物(Me₃SnCl，120mg，0.6mmol)/THF(1mL)溶液，一面使其自然地上升至室溫，一面攪拌2小時。將對反應溶液加入乙醇而得之懸浮液進行過濾，將過濾物以乙腈進行再結晶，而獲得目標化合物2,6-雙(三甲基錫烷基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-8)，產量28.1mg，產率21%)。 In a argon atmosphere, a solution of dithieno[3,2-b:2,3-f]thiene (Compound (1-1), 55.6 mg, 0.25 mmol) / THF (1 mL) After stirring at 78 ° C, n-butyllithium (n-BuLi) / hexane solution (1.63 M, 0.37 mL, 0.6 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 1 hour, then trimethyltin was added at -78 ° C. A solution of chloride (Me ₃ SnCl, 120 mg, 0.6 mmol) / THF (1 mL) was stirred and allowed to rise to room temperature, and stirred for 2 hours. The suspension obtained by adding ethanol to the reaction solution was filtered, and the filtrate was recrystallized from acetonitrile to obtain the target compound 2,6-bis(trimethylstannyl)-dithieno[3,2-b. : 2,3-f]thiazepine (compound (1-8), yield 28.1 mg, yield 21%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.75(s、2H)、6.73(s、2H)、0.34(s、18H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.75 (s, 2H), 6.73 (s, 2H), 0.34 (s, 18H).

[實施例9]經由環化反應之硒雜環庚烯環的形成 [Example 9] Formation of selenium heptane ring via cyclization reaction

在氬環境下，一面將1,2-雙(3-溴-2-噻吩基)乙烯(化合物(6-1)，1.9g，5.4mmol)/Et₂O(70mL)溶液於-78℃進行攪拌，一面滴加正丁基鋰(n-BuLi)/己烷溶液 (1.6M，6.6mL，10.8mmol)，於-78℃攪拌1.5小時。對此綠色懸浮液，於-78℃加入二氯化硒(化合物(7-2))/THF溶液(0.4M，13.3mL，5.4mmol)，攪拌2小時。對反應溶液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷)進行精製，獲得目標化合物的黃色固體硒雜環庚烯并[3,2-b：6,7-b’]二噻吩(或二噻吩并[3,2-b：2,3-f]硒雜環庚烯)(化合物(1-9)，產量166mg，產率11%)。 A solution of 1,2-bis(3-bromo-2-thienyl)ethene (compound (6-1), 1.9 g, 5.4 mmol) / Et ₂ O (70 mL) was taken at -78 ° C under argon. After stirring, n-butyllithium (n-BuLi)/hexane solution (1.6 M, 6.6 mL, 10.8 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 1.5 hours. To the green suspension, selenium dichloride (Compound (7-2)) / THF solution (0.4 M, 13.3 mL, 5.4 mmol) was added at -78 ° C and stirred for 2 hours. After adding water to the reaction solution and diluting with chloroform, the organic layer was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to obtain the yellow solid selenium heptane of the title compound [3,2-b:6,7-b '] Dithiophene (or dithieno[3,2-b:2,3-f]selenocycloheptene) (Compound (1-9), yield 166 mg, yield 11%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.39(d、2H、J=4.8Hz)、6.78(d、2H、J=4.8Hz)、6.76(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.39 (d, 2H, J = 4.8 Hz), 6.78 (d, 2H, J = 4.8 Hz), 6.76 (s, 2H).

另外，二氯化硒(化合物(7-2))/THF溶液可藉由在氬環境下，對硒(1.2g，15mmol)於室溫加入硫醯氯(SO₂Cl₂，1.2mL，15mmol)，攪拌10分鐘後，加入THF(30mL)，於室溫攪拌1小時而予以調製。 In addition, selenium dichloride (compound (7-2)) / THF solution can be added to sulphurium chloride (SO ₂ Cl ₂ , 1.2 mL, 15 mmol) at room temperature by using selenium (1.2 g, 15 mmol) under argon. After stirring for 10 minutes, THF (30 mL) was added, and the mixture was stirred at room temperature for 1 hour to prepare.

[實施例10]溴化物的合成 [Example 10] Synthesis of bromide

在氬環境下，一面將硒雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-9)，95mg，0.35mmol)/THF(12mL)溶液於-78℃進行攪拌，一面滴加鋰四甲基哌啶(LiTMP)/ THF溶液(0.7M，1.2mL，0.85mmol)，於-78℃攪拌5小時。對此橙色懸浮液，於-78℃加入1,2-二溴-1,1,2,2-四氯乙烷(275mg，0.85mmol)，一面使其自然地上升至室溫，一面攪拌15小時。對反應溶液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷)進行精製，獲得目標化合物的黃色固體2,6-二溴-硒雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-10)，產量135mg，產率90%)。 In a argon atmosphere, a solution of selenohepene [3,2-b:6,7-b']dithiophene (compound (1-9), 95 mg, 0.35 mmol) in THF (12 mL) After stirring at 78 ° C, lithium tetramethylpiperidine (LiTMP) / THF solution (0.7 M, 1.2 mL, 0.85 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 5 hours. To the orange suspension, 1,2-dibromo-1,1,2,2-tetrachloroethane (275 mg, 0.85 mmol) was added at -78 ° C, and the mixture was allowed to naturally rise to room temperature while stirring. hour. After adding water to the reaction solution and diluting with chloroform, the organic layer was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentration of the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to obtain the title compound as a yellow solid 2,6-dibromo-selenohepene [3,2- b: 6,7-b']dithiophene (compound (1-10), yield 135 mg, yield 90%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)6.75(s、2H)、6.65(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 6.75 (s, 2H), 6.65 (s, 2H).

[實施例11]偶合反應 [Example 11] Coupling reaction

在氬環境下，將2,6-二溴-硒雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-10)，100mg，0.23mmol)/苯基硼酸(化合物(8-1)，86mg，0.70mmol)/醋酸鈀(Pd(OAc)₂，5.3mg，0.023mmol)/三第三丁基鏻四氟硼酸鹽(P(tBu)₃HBF₄，7.5mg，0.026mmol)/THF(8mL)溶液於室溫攪拌15分鐘。對此褐色溶液加入氫氧化鈉(NaOH，37mg，0.94mmol)/水(H₂O，2mL)溶液，進一步於室溫攪拌2小時。對此橙色懸浮液加入水，以氯仿進行稀釋後，將有機 層以氯仿進行萃取，將減壓下經濃縮所獲得之粗生成物以矽膠管柱層析(氯仿/己烷(體積比)=3/7)進行精製而獲得目標化合物的橙色固體2,6-二苯基-硒雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-11)，產量70mg，產率71%)。 2,6-Dibromo-selenoheptene[3,2-b:6,7-b']dithiophene (compound (1-10), 100 mg, 0.23 mmol) / benzene under argon Boronic acid (compound (8-1), 86 mg, 0.70 mmol) / palladium acetate (Pd(OAc) ₂ , 5.3 mg, 0.023 mmol) / tri-tert-butyl fluorene tetrafluoroborate (P(tBu) ₃ HBF ₄ A solution of 7.5 mg, 0.026 mmol) / THF (8 mL) was stirred at room temperature for 15 min. A solution of sodium hydroxide (NaOH, 37 mg, 0.94 mmol) / water (H ₂ O, 2 mL) was added to this brown solution, and the mixture was further stirred at room temperature for 2 hr. Water was added to the orange suspension, and the organic layer was diluted with chloroform, and the organic layer was extracted with chloroform. The crude product obtained by concentration under reduced pressure was chromatographed by column chromatography (chloroform/hexane (volume ratio) = 3/7) An orange solid 2,6-diphenyl-selenocyclohepten[3,2-b:6,7-b']dithiophene (compound (1-11)) which is purified to obtain the target compound. , yield 70 mg, yield 71%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.51(d、4H、J=7.6Hz)、7.37(t、4H、J=7.6Hz)、7.29(d、2H、J=7.6Hz)、7.02(s、2H)、6.75(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.51 (d, 4H, J = 7.6 Hz), 7.37 (t, 4H, J = 7.6 Hz), 7.29 (d, 2H, J = 7.6 Hz) , 7.02 (s, 2H), 6.75 (s, 2H).

[實施例12]經由環化反應之磷雜環庚烯環的形成 [Example 12] Formation of a heterocycloheptene ring via a cyclization reaction

在氮環境下，一面將1,2-雙(3-溴-2-噻吩基)乙烯(化合物(6-1)，105mg，0.3mmol)/Et₂O(4mL)溶液於-78℃進行攪拌，一面滴加正丁基鋰(n-BuLi)/己烷溶液(1.6M，0.35mL，0.6mmol)，於-78℃攪拌2小時。於-78℃加入苯基二氯膦(化合物(7-3)，44.7μL，0.33mmol，東京化成工業(股)製)，一面使其自然地上升至室溫一面攪拌19小時。對反應溶液加入水，以醋酸乙酯進行稀釋後，將有機層以醋酸乙酯進行萃取，以硫酸鈉進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷/氯仿(體積比)=15/85)進行精製，獲得目標化合 物4-苯基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩(或4-苯基-二噻吩并[3,2-b：2,3-f]磷雜環庚烯)(化合物(1-12)，產量57mg，產率64%)。 A solution of 1,2-bis(3-bromo-2-thienyl)ethene (compound (6-1), 105 mg, 0.3 mmol) / Et ₂ O (4 mL) was stirred at -78 ° C under nitrogen. An n-butyllithium (n-BuLi)/hexane solution (1.6 M, 0.35 mL, 0.6 mmol) was added dropwise and stirred at -78 °C for 2 hr. Phenyldichlorophosphine (Compound (7-3), 44.7 μL, 0.33 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added at -78 ° C, and the mixture was stirred for 19 hours while naturally rising to room temperature. After adding water to the reaction solution and diluting with ethyl acetate, the organic layer was extracted with ethyl acetate, dried over sodium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane/chloroform (volume ratio) = 15/85) to obtain the target compound 4-phenyl-phosphole. [3,2-b:6,7-b']dithiophene (or 4-phenyl-dithieno[3,2-b:2,3-f]phospholeene) (compound (1- 12), yield 57 mg, yield 64%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.47(dd、2H、J=2.8、5.6Hz)、7.33(t、2H、J=5.6Hz)、7.08-7.13(m、3H)、6.79-6.86(m、2H)、6.72(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.47 (dd, 2H, J = 2.8, 5.6 Hz), 7.33 (t, 2H, J = 5.6 Hz), 7.08-7.13 (m, 3H), 6.79-6.86 (m, 2H), 6.72 (s, 2H).

[實施例13]氧化反應 [Example 13] Oxidation reaction

在氮環境下，一面將4-苯基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-12)，250mg，1.7mmol)/二氯甲烷(CH₂Cl₂，25mL)溶液於0℃進行攪拌，一面加入間氯過氧苯甲酸(mCPBA，305mg，2.5mmol)，攪拌2.5小時。對反應溶液加入水，將有機層以醋酸乙酯進行萃取，以硫酸鈉進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(醋酸乙酯)進行精製，獲得目標化合物4-側氧基-4-苯基-磷雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-13)，產量260mg，產率99%)。 4-phenyl-phospholeepeno[3,2-b:6,7-b']dithiophene (compound (1-12), 250 mg, 1.7 mmol) / dichlorobenzene under nitrogen atmosphere The methane (CH ₂ Cl ₂ , 25 mL) solution was stirred at 0 ° C, and m-chloroperoxybenzoic acid (mCPBA, 305 mg, 2.5 mmol) was added and stirred for 2.5 hours. Water was added to the reaction solution, and the organic layer was extracted with ethyl acetate, dried over sodium sulfate and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (ethyl acetate) to give the title compound 4- oxy-4-phenyl-phosphetane [3, 2-b: 6,7-b']dithiophene (compound (1-13), yield 260 mg, yield 99%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.59-7.66(m、2H)、7.39-7.54(m、5H)、7.32(t、2H、J=5.2Hz)、7.02(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.59-7.66 (m, 2H), 7.39-7.54 (m, 5H), 7.32 (t, 2H, J = 5.2 Hz), 7.02 (s, 2H) ).

[實施例14]經由環化反應之矽雜環庚烯環的形成 [Example 14] Formation of a heterocyclic heptene ring via a cyclization reaction

在氬環境下，一面將1,2-雙(3-溴-2-噻吩基)乙烯(化合物(6-1)，1g，2.9mmol)/Et₂O(40mL)溶液於-78℃進行攪拌，一面滴加正丁基鋰(n-BuLi)/己烷溶液(1.6M，3.5mL，5.7mmol)，於-78℃攪拌1.5小時。對此綠色懸浮液，於-78℃加入二甲基二氯矽烷(化合物(7-4)，0.38mL，3.2mmol，東京化成工業(股)製)，一面使其自然地上升至室溫一面攪拌4小時。對反應溶液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷)進行精製，獲得目標化合物4,4-二甲基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩(或4,4-二甲基-二噻吩并[3,2-b：2,3-f]矽雜環庚烯)(化合物(1-14)，產量587mg，產率83%)。 A solution of 1,2-bis(3-bromo-2-thienyl)ethene (compound (6-1), 1 g, 2.9 mmol) / Et ₂ O (40 mL) was stirred at -78 ° C under argon. An n-butyllithium (n-BuLi)/hexane solution (1.6 M, 3.5 mL, 5.7 mmol) was added dropwise and stirred at -78 ° C for 1.5 hours. To the green suspension, dimethyldichloromethane (compound (7-4), 0.38 mL, 3.2 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added at -78 ° C while allowing it to naturally rise to room temperature. Stir for 4 hours. After adding water to the reaction solution and diluting with chloroform, the organic layer was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentration of the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to obtain the title compound 4,4-dimethyl-fluorene heterocycloheptene [3,2-b: 6,7-b']dithiophene (or 4,4-dimethyl-dithieno[3,2-b:2,3-f]indeneheptene) (compound (1-14), yield 587 mg, yield 83%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.41(d、2H、J=5.2Hz)、6.15(d、2H、J=5.2Hz)、6.78(s、2H)、0.45(s、6H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.41 (d, 2H, J = 5.2 Hz), 6.15 (d, 2H, J = 5.2 Hz), 6.78 (s, 2H), 0.45 (s, 6H).

[實施例15]溴化物的合成 [Example 15] Synthesis of bromide

在氬環境下，一面將4,4-二甲基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-14)，200mg，0.81mmol)/THF(30mL)溶液於-78℃進行攪拌，一面滴加鋰四甲基哌啶(LiTMP)/THF溶液(0.71M，2.7mL，1.9mmol)，於-78℃攪拌5小時。對此黑色懸浮液，於-78℃加入1,2-二溴-1,1,2,2-四氯乙烷(629mg，1.9mmol)，一面使其自然地上升至室溫，一面攪拌13小時。對反應溶液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷)進行精製，獲得目標化合物的黃色固體2,6-二溴-4,4-二甲基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-15)，產量143mg，產率90%)。 4,4-Dimethyl-oximehepene [3,2-b:6,7-b']dithiophene (Compound (1-14), 200 mg, 0.81 mmol) under argon The /THF (30 mL) solution was stirred at -78 ° C, and a solution of lithium tetramethylpiperidine (LiTMP) / THF (0.71 M, 2.7 mL, 1.9 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 5 hours. To the black suspension, 1,2-dibromo-1,1,2,2-tetrachloroethane (629 mg, 1.9 mmol) was added at -78 ° C, and the mixture was allowed to naturally rise to room temperature while stirring. hour. After adding water to the reaction solution and diluting with chloroform, the organic layer was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to obtain the title compound as a yellow solid 2,6-dibromo-4,4-dimethyl-indole. Heptene[3,2-b:6,7-b']dithiophene (compound (1-15), yield 143 mg, yield 90%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.03(s、2H)、6.62(s、2H)、0.45(s、6H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.03 (s, 2H), 6.62 (s, 2H), 0.45 (s, 6H).

[實施例16]偶合反應 [Example 16] Coupling reaction

在氬環境下，將2,6-二溴-4,4-二甲基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-15)，60mg，0.15mmol)/苯基硼酸(化合物(8-1)，54mg，0.44mmol)/醋酸鈀(Pd(OAc)₂，3.3mg，0.015mmol)/三第三丁基鏻四氟硼酸鹽(P(tBu)₃HBF₄，4.7mg，0.016mmol)/THF(5mL)溶液於室溫攪拌15分鐘。對此褐色溶液加入氫氧化鈉(NaOH，23.7mg，0.59mmol)/水(H₂O，1.2mL)溶液，進一步於室溫攪拌3.5小時。對此黃色懸浮液加入水，以氯仿進行稀釋後，將有機層以氯仿進行萃取，將減壓下經濃縮所獲得之粗生成物以矽膠管柱層析(氯仿/己烷(體積比)=1/9)進行精製而獲得目標化合物的黃色固體2,6-二苯基-4,4-二甲基-矽雜環庚烯并[3,2-b：6,7-b’]二噻吩(化合物(1-16)，產量40mg，產率67%)。 2,6-Dibromo-4,4-dimethyl-fluorene heterocyclohepte[3,2-b:6,7-b']dithiophene (compound (1-15) under argon atmosphere , 60 mg, 0.15 mmol) / phenylboronic acid (compound (8-1), 54 mg, 0.44 mmol) / palladium acetate (Pd(OAc) ₂ , 3.3 mg, 0.015 mmol) / tri-tert-butyl fluorene tetrafluoroborate (P(tBu) ₃ HBF ₄ , 4.7 mg, 0.016 mmol) / THF (5 mL) was stirred at room temperature for 15 min. A solution of sodium hydroxide (NaOH, 23.7 mg, 0.59 mmol) / water (H ₂ O, 1.2 mL) was added to this brown solution, and the mixture was further stirred at room temperature for 3.5 hours. Water was added to the yellow suspension, and the mixture was diluted with chloroform. The organic layer was extracted with chloroform, and the crude product obtained by concentration under reduced pressure was chromatographed by column chromatography (chloroform/hexane (volume ratio) = 1/9) Purification to obtain the target compound as a yellow solid 2,6-diphenyl-4,4-dimethyl-fluorene heterocyclohepte[3,2-b:6,7-b'] Thiophene (compound (1-16), yield 40 mg, yield 67%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.62(d、4H、J=7.6Hz)、7.38(t、4H、J=7.6Hz)、7.34(s、2H)、7.29(d、2H、J=7.6Hz)、6.75(s、2H)、0.51(s、6H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.62 (d, 4H, J = 7.6 Hz), 7.38 (t, 4H, J = 7.6 Hz), 7.34 (s, 2H), 7.29 (d, 2H, J = 7.6 Hz), 6.75 (s, 2H), 0.51 (s, 6H).

[實施例17] [Example 17]

(1)3-溴-2-萘甲醛(化合物(2-2))的合成 (1) Synthesis of 3-bromo-2-naphthaldehyde (compound (2-2))

在氮環境下，一面將2,3-二溴萘(171mg，0.59mmol)/THF(5mL)溶液於0℃進行攪拌，一面滴加異丙基鎂溴化物(i-PrMgBr)/THF溶液(1.0M，0.89mL，0.87mmol)，於0℃攪拌1小時後，將反應溶液降至-78℃，並進一步攪拌1小時。於-78℃加入N,N-二甲基甲醯胺(DMF，95μL，0.77mmol)，一面使其自然地上升至室溫一面攪拌7小時。對反應溶液加入1N鹽酸水溶液，以醋酸乙酯進行稀釋後，將有機層以醋酸乙酯進行萃取，將所獲得之有機層以水洗淨。以硫酸鈉進行乾燥後，進行過濾，並將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷/甲苯(體積比)=6/4)進行精製，獲得目標化合物3-溴-2-萘甲醛(化合物(2-2)，產量112mg，產率80%)。 Under a nitrogen atmosphere, a solution of 2,3-dibromonaphthalene (171 mg, 0.59 mmol) in THF (5 mL) was stirred at 0 ° C while dropwise adding isopropyl magnesium bromide (i-PrMgBr) / THF solution ( 1.0 M, 0.89 mL, 0.87 mmol), after stirring at 0 ° C for 1 hour, the reaction solution was reduced to -78 ° C and further stirred for 1 hour. N,N-dimethylformamide (DMF, 95 μL, 0.77 mmol) was added at -78 ° C, and the mixture was stirred for 7 hours while naturally rising to room temperature. After the 1N aqueous solution of hydrochloric acid was added to the reaction solution and the mixture was diluted with ethyl acetate, the organic layer was extracted with ethyl acetate, and the obtained organic layer was washed with water. After drying with sodium sulfate, filtration was carried out, and the crude product obtained by concentration under reduced pressure was purified by silica gel column chromatography (hexane/toluene (volume ratio) = 6/4) to obtain the target compound. 3-bromo-2-naphthaldehyde (compound (2-2), yield 112 mg, yield 80%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)10.51(s、1H)、8.47(s、1H)、8.14(s、1H)、7.98(d、1H、J=8.4Hz)、7.80(d、1H、J=8.4Hz)、7.65(t、1H、J=8.4Hz)、7.58(t、1H、J=8.4Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 10.51 (s, 1H), 8.47 (s, 1H), 8.14 (s, 1H), 7.98 (d, 1H, J = 8.4 Hz), 7.80 ( d, 1H, J = 8.4 Hz), 7.65 (t, 1H, J = 8.4 Hz), 7.58 (t, 1H, J = 8.4 Hz).

(2)3-溴-2-萘甲醛的還原 (2) Reduction of 3-bromo-2-naphthaldehyde

在氮環境下，一面將3-溴-2-萘甲醛(化合物(2-2)，500mg，2.1mmol)/乙醇(10mL)溶液於0℃進行攪拌，一面加入硼氫化鈉(138mg，3.7mmol)，於室溫攪拌24小時。在反應液於減壓下經濃縮所獲得之油狀固體中加入水，將有機層以醋酸乙酯進行萃取。將萃取液以硫酸鈉進行乾燥後，進行過濾，並將所獲得之濾液於減壓下進行濃縮而獲得粗生成物。藉由將粗生成物以矽膠層析(己烷/醋酸乙酯(體積比)=8/2)進行精製，而獲得目標化合物3-溴-2-羥基甲基萘(化合物(3-2)，產量286mg，產率57%)。 A solution of 3-bromo-2-naphthaldehyde (compound (2-2), 500 mg, 2.1 mmol) / ethanol (10 mL) was stirred at 0 ° C under nitrogen, and sodium borohydride (138 mg, 3.7 mmol) was added. ), stirring at room temperature for 24 hours. Water was added to the oily solid obtained by concentration of the reaction mixture under reduced pressure, and the organic layer was extracted with ethyl acetate. The extract was dried over sodium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure to give a crude product. The title compound 3-bromo-2-hydroxymethylnaphthalene (compound (3-2)) was obtained by purifying the crude product by silica gel chromatography (hexane/ethyl acetate (volume ratio) = 8/2). , yield 286 mg, yield 57%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)8.07(s、1H)、7.93(s、1H)、7.80-7.87(m、1H)、7.72-7.78(m、1H)、7.47-7.55(m、2H)、4.90(d、2H、J=5.6Hz)、2.14(t、1H、J=5.6Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.07 (s, 1H), 7.93 (s, 1H), 7.80-7.87 (m, 1H), 7.72-7.78 (m, 1H), 7.47-7.55 (m, 2H), 4.90 (d, 2H, J = 5.6 Hz), 2.14 (t, 1H, J = 5.6 Hz).

(3)鏻鹽的合成 (3) Synthesis of cerium salt

在氮環境下，一面將3-溴-2-羥基甲基萘(化合物(3-2)，286mg，1.2mmol)/氯仿(1.9mL)溶液於室溫進行攪拌，一面加入三苯基膦氫溴酸鹽(化合物(4-1)，414mg，1.2mmol)，於60℃攪拌12小時後回復至室溫，減壓下經濃縮而獲得粗生成物。藉由將所獲得之粗生成物以再結晶(氯仿/二乙基醚)進行精製，而獲得目標化合物三苯基-(3-溴-2-萘基)甲基鏻溴化物(化合物(5-2)，產量334mg，產率49%)。 3-bromo-2-hydroxymethylnaphthalene (compound (3-2), 286 mg, 1.2 mmol) / chloroform (1.9 mL) was stirred at room temperature under nitrogen, and triphenylphosphine hydrogen was added thereto. The bromate (Compound (4-1), 414 mg, 1.2 mmol) was stirred at 60 ° C for 12 hours, then returned to room temperature, and concentrated under reduced pressure to give a crude product. By purifying the obtained crude product by recrystallization (chloroform/diethyl ether), the objective compound triphenyl-(3-bromo-2-naphthalenyl)methyl phosphonium bromide (compound (5) was obtained. -2), yield 334 mg, yield 49%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)8.10(d、1H、J=3.6Hz)、7.90(s、1H)、7.70-7.84(m、9H)、7.58-7.69(m、8H)、7.43-7.54(m、2H)、5.91(d、2H、J=14.4Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.10 (d, 1H, J = 3.6 Hz), 7.90 (s, 1H), 7.70-7.84 (m, 9H), 7.58-7.69 (m, 8H) ), 7.43 - 7.54 (m, 2H), 5.91 (d, 2H, J = 14.4 Hz).

(4)Wittig反應 (4) Wittig reaction

在氮環境下，一面將三苯基-(3-溴-2-萘基)甲基鏻溴化物(化合物(5-2)，650mg，1.2mmol)/THF(20mL) 溶液於0℃進行攪拌，一面加入第三丁氧化鉀(45.7g，407.6mmol)並攪拌1小時。進一步加入3-溴-2-萘甲醛(化合物(2-2)，245mg，1.0mmol)。一面使此黑色反應溶液自然地上升至室溫，一面攪拌46小時。對反應溶液加入水，將減壓下經濃縮所獲得之懸浮液以氯仿進行稀釋並進行過濾。將濾液的有機層以氯仿進行萃取，以硫酸鎂進行乾燥後，進行過濾。將減壓下此濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷)進行精製，獲得目標化合物的黃色固體1,2-雙(3-溴-2-萘基)乙烯(化合物(6-2)，產量17.6g，產率38%)。 A solution of triphenyl-(3-bromo-2-naphthyl)methyl hydrazine bromide (compound (5-2), 650 mg, 1.2 mmol) in THF (20 mL) was stirred at 0 ° C under nitrogen. A third potassium butoxide (45.7 g, 407.6 mmol) was added and stirred for 1 hour. Further, 3-bromo-2-naphthaldehyde (compound (2-2), 245 mg, 1.0 mmol) was added. The black reaction solution was allowed to naturally rise to room temperature while stirring for 46 hours. Water was added to the reaction solution, and the suspension obtained by concentration under reduced pressure was diluted with chloroform and filtered. The organic layer of the filtrate was extracted with chloroform, dried over magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane) to obtain the title compound as a yellow solid 1,2-bis(3-bromo-2-naphthalenyl)ethylene ( Compound (6-2), yield 17.6 g, yield 38%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)8.12(s、2H)、7.68(d、2H)、7.52(s、2H)、7.39(t、4H、J=6.8Hz)、7.30(d、2H、J=7.6Hz)、6.99(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.12 (s, 2H), 7.68 (d, 2H), 7.52 (s, 2H), 7.39 (t, 4H, J = 6.8 Hz), 7.30 ( d, 2H, J = 7.6 Hz), 6.99 (s, 2H).

(5)經由環化反應之硫雜環庚烯環的形成 (5) Formation of a thiene ring through a cyclization reaction

在氮環境下，一面將1,2-雙(3-溴-2-萘基)乙烯(化合物(6-2)，17mg，0.037mmol)/Et₂O(0.6mL)溶液於-78℃進行攪拌，一面滴加正丁基鋰/己烷溶液(1.6M，48μL，0.078mmol)，於-78℃攪拌1小時。對此黑色懸浮液，於-78℃加入苯硫磺酸酐(化合物(7-1)，13.5mg，0.041mmol) /THF(0.5mL)溶液，一面使其自然地上升至室溫一面攪拌12小時。對反應溶液加入水，以醋酸乙酯進行稀釋後，將有機層以醋酸乙酯進行萃取，以硫酸鈉進行乾燥後，進行過濾。將減壓下濾液經濃縮所獲得之粗生成物以矽膠管柱層析(己烷/氯仿(體積比)=7/3)進行精製，獲得米色固體的目標化合物二萘并[2,3-b：2,3-f]硫雜環庚烯(化合物(1-17)，產量10mg，產率82%)。 A solution of 1,2-bis(3-bromo-2-naphthyl)ethylene (compound (6-2), 17 mg, 0.037 mmol) / Et ₂ O (0.6 mL) was taken at -78 ° C under nitrogen atmosphere. After stirring, a n-butyllithium/hexane solution (1.6 M, 48 μL, 0.078 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 1 hour. To the black suspension, a solution of phenylthiosulfonic acid anhydride (Compound (7-1), 13.5 mg, 0.041 mmol) / THF (0.5 mL) was added at -78 ° C, and the mixture was stirred for 12 hours while naturally rising to room temperature. After adding water to the reaction solution and diluting with ethyl acetate, the organic layer was extracted with ethyl acetate, dried over sodium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane/chloroform (volume ratio) = 7/3) to obtain the target compound dinaphtho[2,3- b: 2,3-f]thiazepine (compound (1-17), yield 10 mg, yield 82%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)8.10(s、2H)、7.76-7.81(m、4H)、7.74(s、2H)、7.41-7.48(m、4H)、7.16(s、2H)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.10 (s, 2H), 7.76-7.81 (m, 4H), 7.74 (s, 2H), 7.41-7.48 (m, 4H), 7.16 (s) 2H).

[實施例18] [Embodiment 18]

(1)夫里德耳-夸夫特(Friedel-Crafts)醯化反應 (1) Friedel-Crafts deuteration reaction

在氬環境下，一面將3-溴噻吩(1g，6.1mmol)/十七烷醯氯(C₁₆H₃₃COCl，1.8g，6.1mmol)/二氯甲烷(CH₂Cl₂，20mL)溶液於室溫進行攪拌，一點一點加入氯化鋁(AlCl₃，817mg，6.1mmol)，於室溫攪拌3小時。對反應液加入冰水，將有機層以二氯甲烷進行萃取。將萃取液以硫酸鎂進行乾燥，過濾後，將濾液於減壓下進行濃縮而獲得粗生成物。藉由將粗生成物以矽膠管柱層析(醋酸乙酯/ 己烷(體積比)=5/95)進行精製，而獲得目標化合物3-溴-2-十七烷醯基-噻吩(化合物(2-3))及副生成物4-溴-2-十七烷醯基-噻吩(化合物(2-3’))之混合物(產量1.8g，化合物(2-3)/化合物(2-3’)(莫耳比)=87/13，產率72%)。 In a argon atmosphere, a solution of 3-bromothiophene (1 g, 6.1 mmol) / heptadecyl chloride (C ₁₆ H ₃₃ COCl, 1.8 g, 6.1 mmol) / dichloromethane (CH ₂ Cl ₂ , 20 mL) After stirring at room temperature, aluminum chloride (AlCl ₃ , 817 mg, 6.1 mmol) was added little by little, and stirred at room temperature for 3 hours. Ice water was added to the reaction mixture, and the organic layer was extracted with dichloromethane. The extract was dried over magnesium sulfate, and after filtration, the filtrate was concentrated under reduced pressure to give a crude product. The target compound 3-bromo-2-heptadecanoyl-thiophene (compound) was obtained by purifying the crude product by silica gel column chromatography (ethyl acetate / hexane (volume ratio) = 5 / 95). (2-3)) and a mixture of the by-product 4-bromo-2-heptadecanoyl-thiophene (compound (2-3')) (yield 1.8 g, compound (2-3) / compound (2- 3') (Morby) = 87/13, yield 72%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)[化合物(2-3)]7.29(d、1H、J=5.2Hz)、7.10(d、1H、J=5.2Hz)、3.02(t、2H、J=7.2Hz)、1.73(quint、2H、J=7.2Hz)、1.20-1.43(m、26H)、0.88(t、3H、J=7.2Hz)；[化合物(2-3’)]7.59(d、1H、J=1.2Hz)、7.51(d、1H、J=1.2Hz)、2.85(t、2H、J=7.2Hz)、1.73(quint、2H、J=7.2Hz)、1.20-1.43(m、26H)、0.88(t、3H、J=7.2Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) [compound (2-3)] 7.29 (d, 1H, J = 5.2 Hz), 7.10 (d, 1H, J = 5.2 Hz), 3.02 (t , 2H, J = 7.2 Hz), 1.73 (quint, 2H, J = 7.2 Hz), 1.20 - 1.43 (m, 26H), 0.88 (t, 3H, J = 7.2 Hz); [compound (2-3') ] 7.59 (d, 1H, J = 1.2 Hz), 7.51 (d, 1H, J = 1.2 Hz), 2.85 (t, 2H, J = 7.2 Hz), 1.73 (quint, 2H, J = 7.2 Hz), 1.20 - 1.43 (m, 26H), 0.88 (t, 3H, J = 7.2 Hz).

(2)史帝勒偶合(Stille coupling) (2) Stiller coupling

在氬環境下，將肆(三苯基膦)鈀(Pd(PPh₃)₄，7mg，0.006mmol)/3-溴-2-十七烷醯基-噻吩(化合物(2-3))及4-溴-2-十七烷醯基-噻吩(化合物(2-3'))之混合物[50mg，0.12mmol，化合物(2-3)/化合物(2-3')(莫耳比)=87/13]/雙(三丁基錫)硫化物(化合物(9-1)，35mg，0.056mmol) /甲苯(1mL)溶液在噴吹氬的同時於室溫攪拌15分鐘後，於120℃攪拌18小時。對反應液加入水，將有機層以二氯甲烷進行萃取。將萃取液以硫酸鎂進行乾燥，過濾後，將濾液於減壓下進行濃縮而獲得粗生成物。藉由將粗生成物以矽膠管柱層析(醋酸乙酯/己烷(體積比)=1/9)進行精製，而獲得目標化合物雙(2-十七烷醯基-噻吩-3-基)硫化物(化合物(10-1)，產量27mg，產率69%)。 Palladium (triphenylphosphine) palladium (Pd(PPh ₃ ) ₄ , 7 mg, 0.006 mmol) / 3-bromo-2-heptadecanoyl-thiophene (compound (2-3)) and under argon atmosphere a mixture of 4-bromo-2-heptadecanoyl-thiophene (compound (2-3')) [50 mg, 0.12 mmol, compound (2-3) / compound (2-3') (mr ratio) = 87/13]/bis(tributyltin) sulfide (compound (9-1), 35 mg, 0.056 mmol) / toluene (1 mL) was stirred at room temperature for 15 minutes while blowing argon, and then stirred at 120 ° C. hour. Water was added to the reaction mixture, and the organic layer was extracted with dichloromethane. The extract was dried over magnesium sulfate, and after filtration, the filtrate was concentrated under reduced pressure to give a crude product. The target compound bis(2-heptadecanodecyl-thiophen-3-yl group) was obtained by purifying the crude product by silica gel column chromatography (ethyl acetate/hexane (volume ratio) = 1/9). Sulfide (Compound (10-1), yield 27 mg, yield 69%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.47(d、2H、J=5.2Hz)、6.79(d、2H、J=5.2Hz)、2.94(t、4H、J=7.2Hz)、1.70(quint、4H、J=7.2Hz)、1.19-1.37(m、52H)、0.88(t、6H、J=7.2Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.47 (d, 2H, J = 5.2 Hz), 6.79 (d, 2H, J = 5.2 Hz), 2.94 (t, 4H, J = 7.2 Hz) 1.70 (quint, 4H, J=7.2 Hz), 1.19-1.37 (m, 52H), 0.88 (t, 6H, J = 7.2 Hz).

(3)環化反應麥克默里偶合(McMurry coupling) (3) cyclization reaction McMurry coupling

在氬環境下，一面將雙(2-十七烷醯基-噻吩-3-基)硫化物(化合物(10-1)，50mg，0.071mmol)/四氫呋喃(5mL)溶液於-10℃進行攪拌，一面滴加四氯化鈦(TiCl₄)/甲苯溶液(1.0M，0.57mL，0.57mmol)及鋅(74.2mg， 1.14mmol)/四氫呋喃(5mL)溶液後，於60℃攪拌15小時。對反應液加入水，將有機層以氯仿進行萃取。將萃取液以硫酸鎂進行乾燥，過濾後，將濾液於減壓下進行濃縮而獲得粗生成物。藉由將粗生成物以矽膠管柱層析(己烷)進行精製，而獲得目標化合物8,9-二(十六烷基)-二噻吩并[3,2-b：2,3-f]硫雜環庚烯(化合物(1-18)，產量27mg，產率57%)。 A solution of bis(2-heptadecanodecyl-thiophen-3-yl) sulfide (compound (10-1), 50 mg, 0.071 mmol) / tetrahydrofuran (5 mL) was stirred at -10 ° C under argon. A solution of titanium tetrachloride (TiCl ₄ ) / toluene (1.0 M, 0.57 mL, 0.57 mmol) and zinc (74.2 mg, 1.14 mmol) / tetrahydrofuran (5 mL) was added dropwise, and the mixture was stirred at 60 ° C for 15 hours. Water was added to the reaction mixture, and the organic layer was extracted with chloroform. The extract was dried over magnesium sulfate, and after filtration, the filtrate was concentrated under reduced pressure to give a crude product. The target compound, 8,9-di(hexadecyl)-dithieno[3,2-b:2,3-f, was obtained by purifying the crude product by silica gel column chromatography (hexane). Thiolene (compound (1-18), yield 27 mg, yield 57%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.24(d、2H、J=5.2Hz)、6.70(d、2H、J=5.2Hz)、2.50-2.65(m、4H)、1.43-1.60(m、4H)、1.27-1.37(m、4H)、1.18-1.28(m、48H)、0.82(t、6H、J=6.8Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.24 (d, 2H, J = 5.2 Hz), 6.70 (d, 2H, J = 5.2 Hz), 2.50 - 2.65 (m, 4H), 1.43 1.60 (m, 4H), 1.27-1.37 (m, 4H), 1.18-1.28 (m, 48H), 0.82 (t, 6H, J = 6.8 Hz).

[比較例1] [Comparative Example 1]

在氬環境下，將2,7-二溴菲(100mg，0.30mmol)/苯基硼酸(化合物(8-1)，109mg，0.89mmol)/醋酸鈀(Pd(OAc)₂，6.7mg，0.030mmol)/三第三丁基鏻四氟硼酸鹽(P(tBu)₃HBF₄，9.5mg，0.033mmol)/THF(8mL)溶液於室溫攪拌15分鐘。對此黑色溶液加入氫氧化鈉(NaOH，48mg，1.2mmol)/水(H₂O，2mL)溶液，進一步於室溫攪拌2小時。對此灰色懸浮液加入甲醇，將進行過濾所獲得之粗生成物以矽膠管柱層析(氯仿/己烷(體積比) =10/90)進行精製而獲得目標化合物2,7-二苯基菲的白色固體(產量65mg，產率66%)。 2,7-dibromophenanthrene (100 mg, 0.30 mmol) / phenylboronic acid (compound (8-1), 109 mg, 0.89 mmol) / palladium acetate (Pd(OAc) ₂ , 6.7 mg, 0.030 under argon atmosphere A solution of mmol/trit-butylphosphonium tetrafluoroborate (P(tBu) ₃ HBF ₄ , 9.5 mg, 0.033 mmol) in THF (8 mL) was stirred at room temperature for 15 min. A solution of sodium hydroxide (NaOH, 48 mg, 1.2 mmol) in water (H ₂ O, 2 mL) was added to this black solution, and the mixture was further stirred at room temperature for 2 hr. To the gray suspension, methanol was added, and the crude product obtained by filtration was purified by silica gel column chromatography (chloroform/hexane (volume ratio) = 10/90) to obtain the target compound 2,7-diphenyl. Phenanthrene white solid (yield 65 mg, yield 66%).

¹H-NMR(400MHz、CDCl₃)：δ(ppm)7.76(d、2H、J=8.4Hz)、8.11(d、2H、J=1.6Hz)、7.93(dd、2H、J=8.4、1.6Hz)、7.83(s、2H)、7.78(d、4H、J=7.6Hz)、7.51(t、4H、J=7.6Hz)、7.40(t、2H、J=7.6Hz)。 ¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.76 (d, 2H, J = 8.4 Hz), 8.11 (d, 2H, J = 1.6 Hz), 7.93 (dd, 2H, J = 8.4, 1.6) Hz), 7.83 (s, 2H), 7.78 (d, 4H, J = 7.6 Hz), 7.51 (t, 4H, J = 7.6 Hz), 7.40 (t, 2H, J = 7.6 Hz).

[溶解度的評估] [Evaluation of Solubility]

計量出實施例及比較例中所獲得之各化合物數mg，於室溫逐次微量地加入甲苯直至溶解為止。將已溶解之濃度(重量%)以n=5進行測定，以其平均值進行評估。將結果示於表2。 The number of each compound obtained in the examples and the comparative examples was measured in mg, and toluene was added in a small amount at room temperature until dissolved. The dissolved concentration (% by weight) was measured at n = 5, and the average value was evaluated. The results are shown in Table 2.

由表2明顯可知，實施例中所獲得之化合物相較於比較例之化合物而言，溶解性較優異。 As is apparent from Table 2, the compound obtained in the examples was superior in solubility to the compound of the comparative example.

[裝置的特性評估] [Feature evaluation of the device]

(移動度及閾值電壓) (movability and threshold voltage)

製作場效型電晶體並評估移動度。詳細而言，將附二 氧化矽(SiO₂)絕緣膜(膜厚500nm)之矽(Si)基板以丙酮及2-丙醇施行各3分鐘超音波洗淨，使其於120℃乾燥30分鐘。接著，施行UV臭氧處理30分鐘。在經洗淨處理之基板表面，以氣相法將β-苯乙基三氯矽烷(β-PTS)之自組織化單分子膜(SAM)進行製膜。在此基板表面，使用實施例及比較例中所獲得之各化合物，藉由邊緣澆鑄法以表3所記載之條件製作塗佈膜。即，在前述基板表面上，滴加經調整成濃度0.05重量%之溶液1滴後，在加熱板上去除溶媒，再者，藉由進行減壓乾燥而形成塗佈膜。在所獲得之塗佈膜的表面設置金屬遮罩，真空蒸鍍四氟四氰基醌二甲烷(F4TCNQ)(膜厚約2nm)作為載子注入層，真空蒸鍍金(膜厚40nm)作為源極電極及汲極電極，製作裝置元件(頂接觸-底閘極型，通道長100μm，通道寬2mm)。針對此裝置元件，使用半導體參數分析儀(型號「keithley 4200」，Keithley Instruments(股)製)，評估移動度及閾值電壓(汲極電壓Vd=-10V、-100V、-150V)。將結果示於表3。 Fabricate field-effect transistors and evaluate mobility. Specifically, a cerium (Si) substrate with a cerium oxide (SiO ₂ ) insulating film (having a film thickness of 500 nm) was ultrasonically washed with acetone and 2-propanol for 3 minutes, and dried at 120 ° C for 30 minutes. . Next, UV ozone treatment was performed for 30 minutes. A self-organized monomolecular film (SAM) of β-phenethyltrichlorodecane (β-PTS) was formed into a film by a vapor phase method on the surface of the substrate to be washed. On the surface of the substrate, the coating film was produced under the conditions described in Table 3 by the edge casting method using each of the compounds obtained in the examples and the comparative examples. That is, one droplet of the solution adjusted to a concentration of 0.05% by weight was dropped on the surface of the substrate, and then the solvent was removed on a hot plate, and further, a coating film was formed by drying under reduced pressure. A metal mask was placed on the surface of the obtained coating film, and tetrafluorotetracyanoquinodimethane (F4TCNQ) (having a film thickness of about 2 nm) was vacuum-deposited as a carrier injection layer, and gold (film thickness: 40 nm) was vacuum-deposited as a source. The electrode and the drain electrode were fabricated into device components (top contact-bottom gate type, channel length 100 μm, channel width 2 mm). For this device component, a mobility parameter and a threshold voltage (bunging voltage Vd = -10 V, -100 V, -150 V) were evaluated using a semiconductor parameter analyzer (model "keithley 4200", manufactured by Keithley Instruments Co., Ltd.). The results are shown in Table 3.

由表3明顯可知，由實施例中所獲得之化合物所形成之元件顯示出較高的移動度，閾值電壓的絕對值(操作電壓)亦較低。相對於此，由比較例中所獲得之化合物所形成之元件並不運作。 As is apparent from Table 3, the elements formed by the compounds obtained in the examples showed a high degree of mobility, and the absolute value (operating voltage) of the threshold voltage was also low. In contrast, the elements formed by the compounds obtained in the comparative examples did not work.

(移動度的偏差的評估) (evaluation of the deviation of mobility)

除了使用實施例11中所獲得之化合物(1-11)2,6-二苯基-硒雜環庚烯并[3,2-b：6,7-b’]二噻吩，以下述記載之條件形成塗佈膜以外，與前述移動度及閾值電壓之段落中所記載之方法同樣地製作裝置元件。另外，以在裝置1至8中，自源極電極朝向汲極電極之方向(載子移動之方向)與前述化合物(1-11)的結晶生長方向(π堆疊方向或塗佈溶液的流動方向)所成之角度成為0°，在裝置9中，前述角度則成為90°之方式進行製作。將所獲得之裝置的移動度及閾值電壓(汲極電壓Vd=100V)示於表4。 Except that the compound (1-11) 2,6-diphenyl-selenocyclohepten[3,2-b:6,7-b']dithiophene obtained in Example 11 was used, as described below. The device element was produced in the same manner as the method described in the paragraph of the above-described mobility and threshold voltage, except for the formation of the coating film under the conditions. Further, in the devices 1 to 8, the crystal growth direction (the stacking direction or the flow direction of the coating solution) of the aforementioned compound (1-11) from the direction of the source electrode toward the gate electrode (the direction in which the carrier moves) The angle formed is 0°, and in the device 9, the angle is 90°. The mobility of the obtained device and the threshold voltage (bungee voltage Vd = 100 V) are shown in Table 4.

<塗佈膜形成條件> <Coating film formation conditions>

溶媒：大茴香醚 Solvent: anisole

溶解溫度：70℃ Dissolution temperature: 70 ° C

濃度：0.1重量% Concentration: 0.1% by weight

加熱板溫度：40℃ Heating plate temperature: 40 ° C

乾燥條件：70℃，24小時。 Drying conditions: 70 ° C, 24 hours.

由表4之結果明顯可知，即便使結晶生長方向與自源極電極朝向汲極電極之方向所成之角度產生變化，移動度的偏差亦較小，裝置元件具有較高的再現性(或較低的各向異性)。 As is apparent from the results of Table 4, even if the angle between the crystal growth direction and the direction from the source electrode toward the gate electrode is changed, the deviation of the mobility is small, and the device element has high reproducibility (or Low anisotropy).

〔產業上之可利用性〕  [Industrial Applicability]  

在本發明中，由於應變型化合物係對有機溶媒之溶解性及電移動度優異，因而包含前述應變型化合物之有機半導體可有效地利用作為各式各樣的電子裝置，例如整流元件(二極體)、開關元件或電晶體(有機薄膜電晶體)[例如接合型電晶體(雙極電晶體)、場效型電晶體(單極電晶體)等]、光電轉換元件(太陽能電池元件、有機EL元件等)等有機半導體裝置。 In the present invention, since the strain type compound is excellent in solubility and electrical mobility to the organic solvent, the organic semiconductor including the strain type compound can be effectively utilized as various electronic devices such as a rectifying element (two-pole Body, switching element or transistor (organic thin film transistor) [eg junction type transistor (bipolar transistor), field effect type transistor (monopolar transistor), etc.), photoelectric conversion element (solar cell element, organic An organic semiconductor device such as an EL element or the like.

Claims (9)

一種有機半導體，其包含下述式(1)所示之化合物： 式中，Z表示選自週期表第13至16族元素之原子；環A ¹及A ²係相同或相異且表示具有至少1個碳-碳不飽和鍵之環；R ^1a、R ^1b及R ²係相同或相異且表示氫原子或取代基；R ³表示選自週期表第16族元素之原子；R ^A及R ^B係相同或相異且表示氫原子、取代基或選自週期表第16族元素之原子；m表示0至4的整數；n表示0至2的整數；p1及p2係相同或相異且表示0以上的整數； 所示之鍵結表示單鍵或雙鍵。 An organic semiconductor comprising a compound represented by the following formula (1): Wherein Z represents an atom selected from Groups 13 to 16 of the Periodic Table; rings A ¹ and A ² are the same or different and represent a ring having at least one carbon-carbon unsaturated bond; R ^1a , R ^1b and R ² is the same or different and represents a hydrogen atom or a substituent; R ³ represents an atom selected from the group 16 element of the periodic table; R ^A and R ^B are the same or different and represent a hydrogen atom, a substituent or a period selected from the group consisting of An atom of a group 16 element; m represents an integer from 0 to 4; n represents an integer from 0 to 2; and p1 and p2 are the same or different and represent an integer of 0 or more; The bond shown is for a single or double button. 如申請專利範圍第1項所述之有機半導體，其中，在式(1)中，環A ¹及A ²為可具有雜原子之芳香族環。 The organic semiconductor according to claim 1, wherein in the formula (1), the rings A ¹ and A ² are aromatic rings which may have a hetero atom. 如申請專利範圍第1或2項所述之有機半導體，其中，式(1)所示之化合物為選自下述式(1A)及下述式(1B)所示之化合物之至少1種； 式中，環Ar ¹及Ar ²係相同或相異且表示芳烴環；R ^a及R ^b係相同或相異且表示取代基；q1及q2表示0以上的整數；Z、R ^1a、R ^1b、R ²、R ³、m、n係與申請專利範圍第1項所述之式(1)相同； 式中，Z ¹及Z ²係相同或相異且表示選自週期表第13族至16族元素之原子；R ^2a、R ^2b、R ^4a、R ^4b、R ^5a及R ^5b係相同或相異且表示氫原子或取代基；R ^3a及R ^3b係相同或相異且表示選自週期表第16族元素之原子；m1及m2係相同或相異且表示0至4的整數；n1及n2係相同或相異且表示0至2的整數；Z、R ^1a、R ^1b、R ²、R ³、m、n係與申請專利範圍第1項所述之式(1)相同。 The organic semiconductor according to claim 1 or 2, wherein the compound represented by the formula (1) is at least one selected from the group consisting of the compounds represented by the following formula (1A) and the following formula (1B); In the formula, the rings Ar ¹ and Ar ² are the same or different and represent an aromatic hydrocarbon ring; R ^a and R ^b are the same or different and represent a substituent; q1 and q2 represent an integer of 0 or more; Z, R ^1a , R ^1b , R ² , R ³ , m, n are the same as the formula (1) described in the first claim; Wherein Z ¹ and Z ² are the same or different and represent an atom selected from Group 13 to Group 16 elements of the periodic table; R ^2a , R ^2b , R ^4a , R ^4b , R ^5a and R ^5b are the same or phase ^X and R ^3b are the same or different and represent an atom selected from the group 16 elements of the periodic table; m1 and m2 are the same or different and represent an integer from 0 to 4; n1 and N2 is the same or different and represents an integer of 0 to 2; Z, R ^1a , R ^1b , R ² , R ³ , m, and n are the same as the formula (1) described in the first item of the patent application. 如申請專利範圍第3項所述之有機半導體，其中，在式(1A)中，Z為選自週期表第14至16族元素之原子；環Ar ¹及Ar ²為C _6-18芳烴環；R ^1a、R ^1b及R ²為氫原子 或烴基；R ^a及R ^b為烴基；R ³為氧原子或硫原子；m為0至3的整數；q1及q2為0至8的整數，在式(1B)中，Z、Z ¹及Z ²為選自週期表第14至16族元素之原子；R ^1a、R ^1b、R ²、R ^2a、R ^2b、R ^5a及R ^5b為氫原子或烴基；R ³、R ^3a及R ^3b為氧原子或硫原子；R ^4a及R ^4b為氫原子、鹵素原子、烴基、可具有烴基之雜芳基、鋰原子、-B(OH) ₂基、-ZnX ⁴基(式中，X ⁴表示鹵素原子)、-MgX ⁵基(式中，X ⁵表示鹵素原子)、-Sn(R ⁸) ₃基(式中，R ⁸表示烷基)或-Si(R ⁹) ₃基(式中，R ⁹表示氟、氯或烷基)；m、m1及m2為0至3的整數。 The organic semiconductor according to claim 3, wherein, in the formula (1A), Z is an atom selected from the group consisting of elements of Groups 14 to 16 of the periodic table; and the rings Ar ¹ and Ar ² are C _6-18 arene rings. ; R ^1a , R ^1b and R ² are a hydrogen atom or a hydrocarbon group; R ^a and R ^b are a hydrocarbon group; R ³ is an oxygen atom or a sulfur atom; m is an integer of 0 to 3; q1 and q2 are integers of 0 to 8, In the formula (1B), Z, Z ¹ and Z ² are atoms selected from elements of Groups 14 to 16 of the periodic table; R ^1a , R ^1b , R ² , R ^2a , R ^2b , R ^5a and R ^5b are hydrogen. An atom or a hydrocarbon group; R ³ , R ^3a and R ^3b are an oxygen atom or a sulfur atom; R ^4a and R ^4b are a hydrogen atom, a halogen atom, a hydrocarbon group, a heteroaryl group which may have a hydrocarbon group, a lithium atom, -B(OH) ₂ a group, a -ZnX ⁴ group (wherein X ⁴ represents a halogen atom), a -MgX ⁵ group (wherein, X ⁵ represents a halogen atom), and a -Sn(R ⁸ ) ₃ group (wherein R ⁸ represents an alkyl group) Or -Si(R ⁹ ) ₃ group (wherein R ⁹ represents fluorine, chlorine or alkyl); m, m1 and m2 are integers from 0 to 3. 如申請專利範圍第3或4項所述之有機半導體，其中，在式(1A)中，Z為選自碳、矽、鍺、錫、氮、磷、砷、銻、氧、硫、硒及碲之原子；環Ar ¹及Ar ²為C _6-14芳烴環；R ^1a、R ^1b及R ²為氫原子、烷基、環烷基或芳基；Ra及Rb為烷基、環烷基或芳基；R ³為氧原子；m為0至2的整數；q1及q2為0至4的整數，在式(1B)中，Z、Z ¹及Z ²為選自碳、矽、鍺、錫、氮、磷、砷、銻、氧、硫、硒及碲之原子；R ^1a、R ^1b、R ²、R ^2a、R ^2b、R ^5a及R ^5b為氫原子、烷基、環烷基或芳基；R ³、R ^3a及R ^3b為氧原子；R ^4a及R ^4b為氫原子、鹵素原子、芳基、烷芳基、雜芳基或烷基雜芳基；m、m1及m2為0至2的整數。 The organic semiconductor according to claim 3 or 4, wherein, in the formula (1A), Z is selected from the group consisting of carbon, germanium, antimony, tin, nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium and Atoms of ruthenium; Rings Ar ¹ and Ar ² are C _6-14 arene rings; R ^1a , R ^1b and R ² are hydrogen atoms, alkyl groups, cycloalkyl groups or aryl groups; Ra and Rb are alkyl groups, cycloalkyl groups Or an aryl group; R ³ is an oxygen atom; m is an integer of 0 to 2; q1 and q2 are integers of 0 to 4, and in the formula (1B), Z, Z ¹ and Z ² are selected from the group consisting of carbon, ruthenium and osmium. , an atom of tin, nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium and tellurium; R ^1a , R ^1b , R ² , R ^2a , R ^2b , R ^5a and R ^5b are a hydrogen atom, an alkyl group, a cycloalkane Or an aryl group; R ³ , R ^3a and R ^3b are an oxygen atom; R ^4a and R ^4b are a hydrogen atom, a halogen atom, an aryl group, an alkylaryl group, a heteroaryl group or an alkylheteroaryl group; m, m1 and M2 is an integer from 0 to 2. 如申請專利範圍第3至5項中任一項所述之有機半導體，其中，在式(1A)中，Z為選自碳、矽、鍺、氮、磷、 砷、氧、硫及硒之原子；環Ar ¹及Ar ²為C _6-10芳烴環；R ^1a及R ^1b為氫原子或C _1-30烷基；R2為氫原子、C _1-10烷基、C _5-8環烷基或C _6-10芳基；q1及q2為0，在式(1B)中，Z為選自碳、矽、鍺、氮、磷、砷、氧、硫及硒之原子；Z ¹及Z ²為選自氧、硫及硒之原子；R ^1a及R ^1b為氫原子或C _1-30烷基；R ^5a及R ^5b為氫原子；R ²、R ^2a、R ^2b為氫原子、C _1-10烷基、C _5-8環烷基或C _6-10芳基；R ^4a及R ^4b為氫原子、鹵素原子、C _6-14芳基、C _1-20烷基C _6-14芳基、C _4-13雜芳基或C _1-20烷基C _4-13雜芳基；m1及m2為0；n1及n2為0。 The organic semiconductor according to any one of claims 3 to 5, wherein, in the formula (1A), Z is selected from the group consisting of carbon, ruthenium, osmium, nitrogen, phosphorus, arsenic, oxygen, sulfur, and selenium. Atom; Rings Ar ¹ and Ar ² are C _6-10 arene rings; R ^1a and R ^1b are a hydrogen atom or a C _1-30 alkyl group; R 2 is a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkane Or a C _6-10 aryl group; q1 and q2 are 0, and in the formula (1B), Z is an atom selected from the group consisting of carbon, ruthenium, rhodium, nitrogen, phosphorus, arsenic, oxygen, sulfur, and selenium; Z ¹ and Z ² is an atom selected from the group consisting of oxygen, sulfur and selenium; R ^1a and R ^1b are a hydrogen atom or a C _1-30 alkyl group; R ^5a and R ^5b are a hydrogen atom; and R ² , R ^2a and R ^2b are a hydrogen atom, C _1-10 alkyl, C _5-8 cycloalkyl or C _6-10 aryl; R ^4a and R ^4b are a hydrogen atom, a halogen atom, a C _6-14 aryl group, a C _1-20 alkyl group C _6-14 Aryl, C _4-13 heteroaryl or C _1-20 alkyl C _4-13 heteroaryl; m 1 and m 2 are 0; n 1 and n 2 are 0. 一種組成物，其包含申請專利範圍第1至6項中任一項所述之式(1)所示之化合物及溶媒。  A composition comprising the compound of the formula (1) according to any one of claims 1 to 6 and a solvent.   一種製造有機半導體之方法，其係在基材的至少一面，塗佈申請專利範圍第7項所述之組成物，並將溶媒去除。  A method of producing an organic semiconductor, which is applied to at least one side of a substrate, and which coats the composition described in claim 7 and removes the solvent.   一種電子裝置，其包含申請專利範圍第1至6項中任一項所述之有機半導體。  An electronic device comprising the organic semiconductor according to any one of claims 1 to 6.