JP4883955B2 - Organic semiconductor and electronic device using the same - Google Patents

Description

  The present invention relates to an organic semiconductor and an electronic device using the organic semiconductor.

  Recently, the present inventors have succeeded in synthesizing an organic compound called “Sumanene” (the following formula (84)) for the first time in the world (see Non-Patent Document 1, etc.). This compound is expected to have great applicability not only from an academic point of view but also from an industrial point of view. For example, the possibility of application to electronic materials has attracted attention. Hereinafter, the background that the present inventors came to invent the sumanen and the manufacturing method thereof will be described.

A group of carbon homologues called C ₆₀ (following formula (82)) and various fullerenes including C ₇₀ and carbon nanotubes (hereinafter, these may be collectively referred to as “fullerenes”) It is attracting attention as a next-generation material because of its physical properties. In addition to C ₆₀ and C ₇₀ , fullerenes having various structures are known, and each has specific physical properties. Research that attempts to add more various functions by chemically modifying them has been actively conducted all over the world.

However, at present, the production method of fullerenes is limited to the so-called arc discharge method and C ₆₀ and C ₇₀ can be obtained relatively easily, but other fullerenes can be produced in a very small amount. It is very difficult to obtain. Therefore, even if an attempt is made to produce highly functional materials having various structures by chemically modifying fullerenes, poverty of the kinds of starting materials becomes a problem.

In view of the above circumstances, attempts to chemically synthesize fullerenes have been actively carried out in various parts of the world, but this research has only just begun and no one has been successful. However, according to the organic synthetic chemistry method, the molecular structure of the product can be freely controlled unlike the arc discharge method, etc., and if research proceeds, fullerenes that have been difficult to obtain can be obtained freely. I can expect that. Furthermore, the present invention is not limited to existing fullerenes, and if new fullerenes and derivatives thereof can be synthesized, it is considered that a large air hole will be opened in the design of new materials. For example, the behavior of heterofullerenes in which a part of carbon atoms of fullerenes is replaced with a heteroatom has attracted attention by theoretical research (for example, see Non-Patent Document 2), but C ₅₉ N (Non-Patent Document 3). It has not been manufactured except for a small part of compounds such as reference), and the establishment of the organic chemical synthesis method is expected.

Currently, research is underway in order to synthesize a compound containing a non-planar conjugated carbon skeleton which is a partial structure of C _60. However, conventionally, it has only been reported that a compound called corannulene (the following formula (83)) and a derivative thereof were synthesized in 1966, and only a synthesis at a laboratory level was performed. It wasn't. In 1999, a route was also reported in which corannulene can be synthesized in a relatively large amount under mild conditions in the flask (Non-Patent Document 4).

Corannulene is a compound synthesized for the first time in the world as a compound containing the partial structure of C ₆₀ , and its academic significance is great, but it is difficult from the viewpoint of industrial use. This is because the reactivity is not so high because all the carbon atoms of the skeleton are incorporated into the benzene nucleus. Therefore, Corannulene, said despite containing partial structure of C _60, accompanied by actually difficult to use as a raw material for the synthesis of fullerenes and other compounds, such as C _60. Actually, the corannulene derivatives have only been synthesized with a very limited structure at present.

Among the researchers, in addition to corannulene, another chemical structure that has attracted attention is the sumanene. Corannulene contains a C ₆₀ C ₅ symmetric partial skeleton, whereas Smanen contains a C ₆₀ C ₃ symmetric partial skeleton. Sumanen is different from corannulene in that it contains benzylic carbon at three locations. In general, a compound containing a benzylic carbon is highly valuable as a raw material for synthesis. This is because the benzylic carbon is very active and can generate various active species such as cationic species, anionic species, and carbenes, and can be applied to further bond formation reactions based on the active species. . Therefore, sumanen is much more reactive than corannulene, and it is considered that various functional groups can be directly introduced by, for example, oxidation reaction at the benzyl position to synthesize a wide variety of derivatives. Furthermore, it is expected that various compounds as well as fullerenes can be synthesized using these derivatives as raw materials.

  In addition, the inclusion of benzylic carbon is not only advantageous as a synthetic raw material, but also has great utility value in the active species themselves. For example, since the benzyl anion species of sumanen contains the same structure as the cyclopentadienyl anion, it is considered that it has a metal inclusion ability and the like. Therefore, not only has great industrial applicability in itself, but also development of a metal-encapsulated fullerene compound as a model research compound can be expected.

  In this way, Smanen has tremendous academic value and is expected to have great industrial utility value, so many researchers have been working on its synthesis. However, there were no reports of successful synthesis due to the large molecular strain. There are many documents that describe Sumanen, but all of them were limited to performing theoretical calculations and the like (for example, see Non-Patent Documents 5 and 6).

  A compound in which the benzylic carbon of sumanen is replaced with a sulfur atom (the following formula (85)) has been synthesized (Non-patent Document 7). Although this is an interesting compound itself, synthesis requires a severe condition of 1000 ° C. in a vacuum at present, and it is difficult to mass-produce it and put it on an industrial base. In the first place, the physical properties are very different from Sumanen. For example, the reactivity of the sulfur atom is not as flexible as the benzylic carbon, but seems to be able to add an oxo group or the like. Thus, although the chemical structure and utility of sumanen are expected, there have been no examples of successful synthesis.

  Under the circumstances as described above, as a result of intensive studies, the present inventors have succeeded in synthesizing sumanen for the first time in the world and established a production method thereof as described above. According to this production method, sumanene and its derivatives can be obtained without difficulty using a synthetic organic chemistry technique. For example, it is also possible to synthesize sumanene in as little as 3 steps from mild and readily available norbornadiene in a flask under mild conditions.

Hidehiro Sakurai, Taro Daiko, Toshikazu Hirao, Science, 2003, 301, p.1878. M. Riad Manaa, David W. Sprehn, and Heather A. Ichord, J. Am. Chem. Soc., 2002, 124, p. 13990-13991. Science, 1995, 269, p.1554. Andrzej Sygula and Peter W. Rabideau, J. Am. Chem. Soc., 2000, 122, p.6323-6324. U. Deva Priyakumar and G. Narahari Sastry, J. Phys. Chem. A, 2001, 105, p.4488-4494. U. Deva Priyakumar and G. Narahari Sastry, Tetrahedron Letters, 2001, 42, p.1379-1381. Koichi Imamura, Kazuo Takimiya, Yoshio Aso and Tetsuo Otsubo, Chem. Commun., 1999, p.1859-1860.

  As described above, sumanen and its derivatives have great academic value and are expected to have great industrial utility value. However, since Smanen is the first compound in the world that has just been successfully synthesized, it is also true that there are still many unknowns regarding its physical properties. Therefore, further research on Sumanen is desired from the viewpoint of searching for industrial applicability. On the other hand, in the field of organic semiconductors, development of semiconductors with even better performance is required.

  Therefore, an object of the present invention is to provide a novel organic semiconductor with high performance.

  In order to solve the above problems, the organic semiconductor of the present invention is at least selected from the group consisting of a compound represented by the following general formula (1), a tautomer thereof, a stereoisomer thereof, and a salt thereof. Organic semiconductor including one.

In formula (1), A ^{1 to} A ⁶ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group, or an aromatic hydrocarbon group, and a benzylic hydrogen on A ^{1 to} A ⁶ When an atom is present, the hydrogen atom may be substituted with a substituent,
The substituents on A ^{1 to} A ⁶ may be the same or different, and may be halogen, a linear or branched small molecule or polymer chain (however, in the main chain and side chain, hetero May or may not contain atoms, may or may not contain unsaturated bonds, may or may not contain cyclic structures, carbocycles or heterocycles (but may be monocyclic or fused rings) However, it may be saturated or unsaturated and may or may not have a substituent), an electron donating group or an electron withdrawing group, or the same A ^r (r is any one of 1 to 6) substituents together that binds to Kano integer) is covalently bonded, carbon ring or heterocyclic ring together with a ^r to which they are bonded (although a condensed ring with a single ring may be saturated or unsaturated, a substituent Shape with or without) You may
X ^{1 to} X ³ are the same or different, and are a methylene group (the following formula (2)), a vinylidene group (the following formula (3)), a carbonyl group (the following formula (4)), a thiocarbonyl group (the following formula (5)), an iminomethylene group (the following formula (6)), an imino group (the following formula (7)), or an oxygen atom (the following formula (8)), and a hydrogen atom is present on X ^{1 to} X ^3. If present, the hydrogen atom may be substituted by a substituent,

The substituents on X ^{1 to} X ³ are the same or different from each other, and are halogen, a linear or branched small molecule or polymer chain (however, in the main chain and side chain, hetero groups are May or may not contain atoms, may or may not contain unsaturated bonds, may or may not contain cyclic structures, carbocycles or heterocycles (but may be monocyclic or fused rings) However, it may be saturated or unsaturated and may or may not have a substituent), an electron donating group or an electron withdrawing group, or the same X ^a (a is any one of 1 to 3) And the substituents bonded to each other by a covalent bond, together with the X ^a to which they are bonded, may be ^a carbocyclic or heterocyclic ring (which may be monocyclic or condensed, saturated or unsaturated, Shape with or without) You may make it.

  The organic semiconductor of the present invention includes at least one selected from the group consisting of the compound represented by the general formula (1), a tautomer thereof, a stereoisomer thereof, and a salt thereof. As an excellent performance. In the organic semiconductor of the present invention, the molecule of the compound represented by the formula (1) may be a neutral molecule, but as described above, it is in an ion state having a positive or negative charge. May be.

  Hereinafter, the present invention will be described more specifically.

  The compound represented by the formula (1) (Sumanen and derivatives thereof) and a composition containing the compound are expected to have a great industrial utility value as described above. For example, industrial materials such as various electronic materials Application to various uses such as basic research materials such as model compounds of metal-encapsulated fullerene compounds, photosensitizers, polymerization catalysts, etc. is expected. However, as a result of intensive studies, the present inventors have found that the compound represented by the formula (1) can be preferably used for an organic semiconductor from the viewpoint of its electrical properties and the like. The organic semiconductor of the present invention comprising at least one selected from the group consisting of the compound represented by the general formula (1), a tautomer thereof, a stereoisomer thereof, and a salt thereof is used as a semiconductor. I found it to be high performance.

  The molecular structure in the organic semiconductor of the present invention is not particularly limited. For example, it may have a structure in which molecules or ions of the compound represented by the formula (1) are stacked in the vertical direction. It is preferable from the viewpoint of superiority.

  The molecular structure in the organic semiconductor of the present invention and the reason why the organic semiconductor of the present invention is excellent in electrical properties and the like are not necessarily all clear, but are considered as follows, for example. That is, first, the compound represented by the formula (1) (Sumanen and derivatives thereof) contains a benzene ring structure in its molecular structure and exhibits properties as an aromatic compound as described above. However, in the normal state, the molecular skeleton is not a plane but a slightly curved bowl shape, so that the π electrons are not completely delocalized, and it is considered that a slight charge bias occurs. . Because of this slight charge bias in the molecule, the organic semiconductor of the present invention is presumed to be excellent in electrical properties and the like, and particularly in electrical conductivity and electron mobility. Further, the compound molecule represented by the formula (1) attracts a portion having a high electron density and a portion having a low electron density between the molecules due to the bias of the electric charge, and as a result, a structure in which the layers are regularly stacked in a solid. It is thought to take. As a result of the molecule having such a structure, the π electrons of the aromatic ring are efficiently packed (filled), which also seems to have an advantageous effect on electrical conductivity, electron mobility, and the like. However, this description is an example of a presumed mechanism and does not limit the present invention. Further, as described above, the molecular structure in the organic semiconductor of the present invention is not particularly limited, and is not limited to a structure including a structure in which the compound or ion represented by the formula (1) is stacked in the vertical direction. .

  The organic semiconductor of the present invention may be composed only of the compound represented by the formula (1), a tautomer or stereoisomer thereof, or a salt thereof, but includes other components as necessary. You can leave. Further, the organic semiconductor of the present invention preferably has a crystal structure from the viewpoint of electrical properties and the like, and ideally it may be in a so-called single crystal state, but is not limited thereto, for example, So-called polycrystals and other arbitrary states are possible.

  Such a method for producing an organic semiconductor of the present invention is not particularly limited. For example, from the group consisting of the compound represented by the general formula (1), a tautomer thereof, a stereoisomer thereof, and a salt thereof. At least one selected can be produced by a production method comprising a step of recrystallization after dissolution in a solvent, or solidification after melting. At this time, if necessary, at least one selected from the group consisting of the compound represented by the general formula (1), a tautomer thereof, a stereoisomer thereof, and a salt thereof, Ingredients may be added. However, it is preferable to remove unnecessary impurities that hinder the regular arrangement of molecules in advance by chromatography or the like. In the case of recrystallization, the solvent is not particularly limited, and may be appropriately determined in consideration of the solubility of the compound represented by the formula (1), its tautomer or stereoisomer, or a salt thereof. , For example, aliphatic hydrocarbons such as pentane and hexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, esters such as ethyl acetate, Examples include ethers such as diethyl ether, THF (tetrahydrofuran), dimethoxyethane, and dioxane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohols such as methanol, ethanol, and isopropanol, and these may be used alone. You may use together more than a kind. As a method for precipitating crystals by recrystallization, the difference in solubility depending on temperature is used, and the compound represented by the formula (1), a tautomer or stereoisomer thereof, or a salt thereof and as necessary. Cooling a hot saturated solution containing other components (hereinafter sometimes referred to simply as “solute”), a method of evaporating the solvent from the solution containing solute, and other suitable solutions containing the solute For example, a method of reducing the solubility of the solute by adding an appropriate solvent can be used. In any of the methods, if the time for depositing and growing the crystal is as long as possible, there is an advantage that a large crystal in which molecules are regularly arranged can be obtained. It is preferable to determine appropriately considering also.

  More specifically, as the recrystallization method, for example, the solute is added to an appropriate solvent, heated to the vicinity of the boiling point of the solvent to completely dissolve the solute, and then cooled while standing. For example, a supercooled (supersaturated) solution may be used, and the crystal may be deposited by standing at the same temperature. When standing still, it may stand still at room temperature, for example, and may be cooled with a refrigerator etc. as needed. Although the temperature at the time of standing is not specifically limited, For example, 0-20 degreeC is preferable and, for example, room temperature may be sufficient as above-mentioned. The “room temperature” is not particularly limited in the present invention, but is, for example, 5 to 35 ° C. according to JIS K 0050. In the production of the organic semiconductor of the present invention, for example, the compound represented by the formula (1), a tautomer or stereoisomer thereof, or a salt thereof is mixed with other components as necessary. However, from the viewpoint of regularly arranging molecules in the organic semiconductor due to electrical properties, etc., for example, as described above, a method such as recrystallization or solidification after melting is used. It is preferable.

As described above, the organic semiconductor of the present invention preferably includes a compound molecule represented by the formula (1) or a stacked structure of ions thereof. However, from the viewpoint of electrical conductivity, electron mobility, and the like, More preferably, the compound molecules represented by 1) or ions thereof are laminated in parallel. More specifically, in the compound molecule represented by the formula (1) or an ion thereof, an atom directly bonded to the benzene ring in the sumanene skeleton in the atomic group X ^{1 is} defined as x ^I , and the atomic group X ² the directly bonded to the benzene ring in sumanene backbone at medium atoms and x ^II, the atom directly bonded to the benzene ring in sumanene backbone in atomic group X ³ and x ^III, x ^I, x ^II and the plane containing the 3 atoms x ^III when defined as x plane, the stacked structure of the molecule or ion, more preferably the x plane of the respective molecules or ions are parallel to each other. Further, in the compound molecule represented by the formula (1) or its ion, when a triangle having the three atoms of x ^I , x ^II and x ^III as a vertex is defined, in the laminated structure of the molecule or its ion The triangle in any molecule or ion is 60 ° ± 10 ° or 180 ° ± 10 ° in the x plane with respect to the triangle of the molecule or ion stacked on or under it. Or, it is more preferable to be positioned at an angle rotated by 300 ° ± 10 °. In the case where the compound molecule represented by the formula (1) or its ion has C3 symmetry as in the parent compound, eg, sumanene (formula (84)), the angle is 60 °, The state of 180 ° and the state of 300 ° all refer to the same state. In the present invention, when the compound molecule represented by the formula (1) or its ion is said to be “parallel”, it includes not only a strictly parallel state but also a substantially parallel state.

  In addition, the structure of each molecule | numerator in the organic semiconductor of this invention, the positional relationship between each molecule | numerator, etc. can be confirmed using instrumental analysis methods, such as X-ray structural analysis, for example. As described above, the molecular structure in the organic semiconductor of the present invention preferably includes a compound molecule represented by the formula (1) or a stacked structure of ions thereof, because it is further excellent in electrical properties and the like. It is not limited to a structure including a layered structure of the compound molecule represented by the formula (1) or ions thereof. For example, if the molecules or ions thereof are regularly arranged in the direction parallel to the x-plane of each molecule or ion, it is considered that the electric conductivity, electron mobility, etc. in the direction parallel to the x-plane are excellent. Moreover, even if the molecules or ions thereof are not necessarily arranged regularly, good electrical conductivity, electron mobility, and the like can be obtained.

  The organic semiconductor of the present invention can be used in various electronic devices, and is particularly useful as an organic transistor material. Although the shape of the organic semiconductor of this invention is not specifically limited, When using for an electronic device etc., it is preferable that it is a thin film form, for example. In addition, the organic semiconductor of the present invention can be produced by, for example, the recrystallization method as described above, but in the case of a thin film, it can be produced by the following method, for example.

  The method for producing the thin-film organic semiconductor comprises thin film forming at least one selected from the group consisting of the compound represented by the general formula (1), a tautomer thereof, a stereoisomer thereof, and a salt thereof. Forming the shape. The method of forming the thin film is not particularly limited, and a known film forming method can be used. For example, the method is selected from the group consisting of a vapor deposition method, a chemical vapor deposition method, a spin coating method, and a printing method. It is preferable that it is at least one. Moreover, when forming into a thin film form, components other than the compound represented by the general formula (1), a tautomer, a stereoisomer, and a salt thereof may be appropriately used as necessary. good. According to such a manufacturing method, for example, by appropriately setting manufacturing conditions, an organic semiconductor having a structure in which the compound molecules or ions represented by the formula (1) are regularly stacked in the upper and lower methods can be easily manufactured. Is also possible.

  Further, the organic semiconductor of the present invention may further contain a dopant for the purpose of bringing the conductivity into a desired range. A dopant is a substance added for the purpose of improving the conductivity of a semiconductor, for example, and can also be added for the purpose of improving the conductivity of an organic material such as a conductive polymer.

  The dopant contained in the organic semiconductor of this invention is not specifically limited, A well-known dopant etc. can be used suitably, For example, the following can be used. For example, examples of the electron donating compound include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as calcium, strontium and barium, lanthanoids such as europium, ammonium salts and phosphonium salts. As an electron-accepting compound, a compound containing a halogen and a halogen element such as chlorine, bromine, iodine, etc., a Lewis acid such as phosphorus pentafluoride, arsenic pentafluoride, antimony pentafluoride, boron trifluoride, boron trichloride, Inorganic acids such as hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid and perchloric acid, various organic acids, amino acids, iron trichloride, titanium tetrachloride, zirconium tetrachloride, niobium pentachloride, tantalum pentachloride, cerium trichloride and other transition metals Examples thereof include electrolytes such as compounds, chloride ions, bromine ions, and iodine ions. Various metals such as yttrium (Y), samarium (Sm), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr ), Molybdenum (Mo), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), iridium (Ir), cobalt (Co), rhodium (Rh), W (tungsten), Ni (nickel) ), Transition metals such as Pd (palladium), Pt (platinum), and osmium (Os). The doping method is not particularly limited, and a known method such as voltage application or laser light irradiation can be appropriately used.

  The organic semiconductor of the present invention is, for example, from the viewpoint of electrical conductivity, electron mobility, etc., the purity of the compound represented by the general formula (1), its tautomer, its stereoisomer, and their salts Is preferably high. Specifically, for example, in the portion excluding the mass of the dopant from the mass of the organic semiconductor of the present invention, the compound represented by the general formula (1), its tautomer, its stereoisomer, and those The salt content is preferably 10% by mass or more, more preferably 50% by mass or more, still more preferably 90% by mass or more, and ideally 100% by mass. For example, when the compound represented by the general formula (1) contains a large amount of impurities, the purity can be increased by a method such as vapor deposition or chemical vapor deposition. However, the organic semiconductor of the present invention is not necessarily required to have high purity of the compound represented by the general formula (1), its tautomer, its stereoisomer, and salts thereof. For example, the organic semiconductor of the present invention may contain, as necessary, a substance selected from the group consisting of the compound represented by the general formula (1), a tautomer, a stereoisomer, and a salt thereof. In addition, other substances exhibiting properties as organic semiconductors may be included as appropriate.

  The electronic device of the present invention, particularly the transistor, has excellent performance by including the organic semiconductor of the present invention. The configuration of the transistor of the present invention is not particularly limited, and an arbitrary configuration is possible. For example, a configuration including the organic semiconductor of the present invention may be used instead of or in addition to a known semiconductor portion of a transistor. Specifically, as the transistor of the present invention, for example, a thin film transistor (also referred to as a thin film transistor or a thin film capacitor) is more preferable from the viewpoint of thinning. The transistor of the present invention may be a so-called bipolar transistor or a field effect transistor (also referred to as a field effect capacitor), but particularly in the case of a thin film transistor, from the viewpoint of ease of manufacture and the like. A field effect transistor is more preferable.

  The configuration of the transistor of the present invention may be, for example, a configuration including a gate electrode, a source electrode, a drain electrode, and an insulating layer in addition to the organic semiconductor layer formed from the organic semiconductor of the present invention. Each of these components may be formed on an insulating substrate, for example. The positional relationship between these components may be the same as that of a conventional transistor, for example, for example, the organic semiconductor layer and the gate electrode are separated by the insulating layer, and the source electrode and the drain electrode are It may be in direct contact with the organic semiconductor layer. Furthermore, the material and size of each component other than the organic semiconductor layer are not particularly limited, and may be the same as that of a conventional transistor, for example. Further, the structure of the transistor of the present invention is not limited to this, and any structure is possible as described above. Furthermore, the method for producing the transistor of the present invention is not particularly limited, and may be the same as, for example, a conventional transistor. More specifically, for example, the organic semiconductor layer is formed by the vapor deposition method, chemical vapor deposition method, It may be formed by a spin coating method or a printing method, and the other components may be formed in the same manner as in the past.

  Next, the compound represented by the formula (1) and the production method thereof will be described in more detail.

  As described above, the present inventors have succeeded in synthesizing sumanen for the first time in the world. And the compound (namely, sumanen and its derivative) of this invention represented by the said General formula (1) and its manufacturing method were established.

  The method for producing the compound represented by the general formula (1), a tautomer or stereoisomer thereof, or a salt thereof is not particularly limited and may be produced by any method. It is preferable to manufacture by the manufacturing method demonstrated to (1). According to this production method, sumanene and its derivatives can be obtained without difficulty using a synthetic organic chemistry technique. For example, as shown in Scheme 1 below, the parent compound, sumanen, may be synthesized from norbornadiene (formula (86) below) that is inexpensive and easily available in only 3 steps in a flask under mild conditions. Is possible.

  Hereinafter, the manufacturing method will be described more specifically. That is, first, a compound represented by the following formula (76) is prepared. This compound and its salt are novel compounds according to the inventors' invention, and can be further converted to sumanen and its derivatives via an oxidation (dehydrogenation) reaction.

In formula (76), R ^{1 to} R ⁶ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group, or an aromatic hydrocarbon group, preferably a hydrogen atom, 6 straight-chain or branched alkyl groups, phenyl groups, or naphthyl groups. X ¹¹ , X ²¹ and X ³¹ are the same or different and each represents a methylene group, an imino group or an oxygen atom. In the case of an imino group, the hydrogen atom may be substituted with a protecting group. Hereafter, the manufacturing method of this compound is demonstrated.

  Although the manufacturing method of the compound represented by said Formula (76) and its salt is not specifically limited, The manufacturing method including the metathesis reaction of the compound represented by following formula (77) is more preferable. This manufacturing method is a novel manufacturing method according to the inventors' invention. The metathesis reaction is a well-known reaction, but the present inventors have found that it applies to a compound represented by the following formula (77). By inventing this method, it was possible to obtain sumanen and its derivatives without difficulty.

In the formula (77), R ^{1 to} R ⁶ , X ¹¹ , X ²¹ and X ³¹ are the same as those in the formula (76).

The conditions for the metathesis reaction are not particularly limited and can be carried out in the same manner as in the conventional metathesis reaction, but it is preferably carried out using a catalyst. The said catalyst is not specifically limited, What is normally used as what is called a metathesis catalyst can be used, and it may be used independently and may be used together 2 or more types. More preferably, the catalyst contains at least one element selected from the group consisting of ruthenium, aluminum, titanium, molybdenum and tungsten, for example. Many such metathesis catalysts, particularly catalysts containing ruthenium and molybdenum, have been developed. Specific examples of the catalyst used in the present invention include (PCy ₃ ) ₂ RuCl ₂ = CHPh, that is, bis (tricyclohexylphosphino) benzylidene ruthenium (II) chloride, Al (C ₂ H ₅ ) _3- It is particularly preferable to include at least one selected from the group consisting of TiCl ₄ , Al (C ₂ H ₅ ) ₃ —MoCl ₃ , and Al (C ₂ H ₅ ) ₃ —WCl _6, but is not limited thereto. It is not a thing. The amount of the catalyst used is not particularly limited, and may be appropriately adjusted in consideration of reaction efficiency, cost, etc. For example, a so-called stoichiometric amount or less is preferable. The appropriate amount of the catalyst used varies depending on the type of catalyst, reaction scale, etc., and is not constant, but in a flask level reaction, for example, about 5 mol% with respect to the compound represented by the formula (77). . In general, in a catalytic reaction, as the reaction scale increases, the amount of catalyst used tends to be relatively reduced (that is, the ratio of the amount of catalyst used to the base mass can be reduced).

  The metathesis reaction is preferably performed using another olefin that reacts with the compound of the formula (77) from the viewpoint of reaction efficiency and yield. The olefin in this case is not particularly limited, but for example, ethylene is more preferable from the viewpoint of reaction efficiency, cost, ease of handling, and the like.

  The operation and reaction principle in the case of using the other type of olefin, for example, ethylene, is explained as follows, for example. That is, first, the compound of the formula (77) and ethylene are combined by a metathesis reaction to open the olefin bond portion in the compound of the formula (77). And the compound represented by said Formula (76) is produced | generated by carrying out the metathesis reaction of the reaction product, and ring-closing. This ring closure reaction produces ethylene again and is finally removed from the system. In this way, the compound represented by the formula (76) can be obtained more efficiently.

Other substances used and reaction conditions in the metathesis reaction are not particularly limited, and may be set as appropriate with reference to a conventional metathesis reaction or the like. Solvents include, for example, aromatic hydrocarbons such as toluene and xylene, halides such as dichloromethane, chloroform and dichloroethane, ether solvents such as diethyl ether, dimethoxyethane and tetrahydrofuran, and highly polar solvents such as acetonitrile and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more. The reaction temperature and reaction time are also not particularly limited, and may be appropriately set depending on the structure of R ^{1 to} R ⁶ , X ¹¹ , X ²¹ and X ^{31 in} the formula (77), the reaction scale, and the like. Further, the method for separating and purifying the reaction product is not particularly limited, and it can be carried out by appropriately using known means such as column chromatography or GPC.

  As described above, the compound of the formula (76) can be produced from the compound of the formula (77). The method for producing the compound represented by the formula (77) is not particularly limited, but the method includes halogenation of compounds represented by the following formulas (78) to (80) and further cyclization by Wurtz-type coupling. The method is preferred.

However, R < ¹ > -R < ⁶ >, X < ¹¹ >, X < ²¹ > and X < ³¹ > are the same as said Formula (77) in Formula (78)-(80), respectively.

  Wurtz-type coupling is known as a coupling reaction between halides, and the present inventors have found that this reaction is used for the production of the compound of the formula (77). Examples of the halogen include fluorine, chlorine, bromine and iodine. Among these, bromine is more preferable. The reaction is carried out in the presence of an alkali metal such as metallic sodium or metallic lithium, or a catalyst, and examples of the catalyst include a copper catalyst, a nickel catalyst, and a palladium catalyst. More preferred. Alternatively, the halide may be prepared in an isolated state and coupled. However, the halide may be produced in the reaction system and coupled (without isolation) in the same reaction system. Also good. In the present invention, specific operations and reaction conditions of the Wurtz-type coupling are not particularly limited, but are as follows, for example. That is, first, the compounds of the above formulas (78) to (80) (hereinafter sometimes simply referred to as “diene”), potassium t-butoxide, n-butyllithium hexane solution, 1,2-dibromoethane, iodine Prepare copper (I) and THF as a solvent, and thoroughly dry all these reactants and solvent and the reaction vessel. The amount of the substance other than the diene and the solvent is not particularly limited, but it is more preferable to use the same chemical equivalent in order to suppress side reactions and the like. Next, the inside of the reaction vessel is replaced with an inert gas, and t-BuOK and THF are added and dissolved. Thereafter, the reaction system temperature is lowered to −78 ° C., diene is added, and a hexane solution of n-BuLi is added dropwise over 2 hours. After completion of the dropwise addition, the temperature of the reaction system is raised to minus 40 ° C., and further stirred for 30 minutes. Then, the temperature of the system is lowered to minus 78 ° C., 1,2-dibromoethane is added, and the temperature is raised again to minus 40 ° C., followed by stirring for one and a half hours. Next, after returning the temperature of the system to minus 78 ° C., copper (I) iodide is added. Then, after stirring at minus 78 ° C. for 4 hours, the cooling is stopped, and the mixture is further stirred for 7 hours while gradually returning to room temperature. Then, it works up by a conventional method and obtains the target compound represented by the formula (77).

Substances used in this reaction, reaction temperature, reaction time, and the like are not limited to those described above, and can be appropriately set with reference to a conventional Wurtz-type coupling reaction or the like. In the formulas (78) to (80), when any one of the X ^{11 to} X ³¹ is an imino group, the hydrogen atom is substituted with a protecting group to suppress side reactions and the like. It is more preferable. Is not particularly limited as protecting groups, but may be appropriately used a known protecting group, for example, Greene and Wuts al "Protective Groups in Organic Synthesis", etc. protecting groups described mentioned second edition (2 ^nd Edition) Specifically, there are t-butoxycarbonyl group (Boc), acetyl group (Ac), benzyloxycarbonyl group (Z), benzyl group (Bz) and the like.

In addition, although the compound of the said Formula (77) is a syn isomer, it is normally obtained as a mixture with the anti isomer which is the isomer. These can be separated by commonly used means such as GPC. Furthermore, when all of X ^{11 to} X ³¹ are not the same, a number of by-products can be obtained in addition to the target compound of the formula (77). These can also be obtained by means such as column chromatography and GPC. Can be separated.

Moreover, the manufacturing method of the compound of the said Formula (77) is not limited to the said Wurtz type coupling method, It can also synthesize | combine by a well-known method. These known methods are described, for example, in “Giuseppe Borsato, Ottorino De Lucchi, Fabrizio Fabris, Luca Groppo, Vittorio Lucchini, and Alfonso Zambon, J. Org. Chem., 2002, 67, p.7894-7897”. And the method of cross-coupling of selected halides with organometallic reagents, "Harold Hart, Abdollah Bashir-Hashemi, Jihmei Luo and Mary Ann Meador, Tetrahedron, 1986, 42, p.1641-1654.", "Harold Hart, Chung-yin Lai, Godson Chukuemeka Nwokogu and Shamouil Shamouilian, Tetrahedron, 1987, 43, p.5203-5224. "And" Francisco Raymo, Franz H. Kohnke and Francesca Cardullo, Tetrahedron, 1992, 48, p.6827-6838. There is a synthesis method described in " However, if the Wurtz-type coupling method is used, for example, as described above, the compounds represented by the formulas (78) to (80) are halogenated and then isolated in the same reaction system as the halogenation (isolation). Cyclization can also be carried out (without). This is preferable because the compound of the formula (77) can be easily synthesized from the compounds of the formulas (78) to (80) in one step, and all of the X ^{11 to} X ³¹ are methylene groups. It is especially effective in some cases.

  And if the compound of the said Formula (77) is obtained, the compound of the said Formula (76) will be obtained by the metathesis reaction of this compound as above-mentioned.

  In addition, as a method for obtaining the compound of the formula (76) from the compound of the formula (77), there is also the following production method in addition to the metathesis reaction. That is, first, the compound represented by the formula (77) is subjected to ozonolysis to obtain a compound represented by the following formula (77 ′). The conditions for this ozonolysis are not particularly limited, and can be appropriately set with reference to a known ozonolysis reaction or the like.

In formula (77 ′), R ^{1 to} R ⁶ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group, or an aromatic hydrocarbon group, and X ¹¹ , X ^21, and X ³¹ are Each is the same or different and is a methylene group, an imino group or an oxygen atom. In the case of an imino group, the hydrogen atom may be substituted with a protecting group.

Ozonolysis is known as a reaction in which a compound having a carbon-carbon unsaturated bond is ozonized and further decomposed to obtain a carbonyl compound. As a method for decomposing an ozonide (ozonide) to obtain a carbonyl reaction, for example, there are a method of decomposing with water and a method of using a reducing agent. More specifically, for example, Zn-H ₂ O in the presence of acetic acid. Examples thereof include a reduction method, a catalytic reduction method using hydrogen in the presence of a platinum catalyst or a palladium catalyst, a reduction method using Raney nickel, and the like. There are many references describing ozonolysis, such as "PS Bailely, Chem. Rev., 1958, 58, p.925." And "RW Murray, Acc. Chem. Res., 1968, 1, p .313. "Etc.

  The compound represented by the formula (77 ′) and a salt thereof are novel compounds according to the present invention, and are preferably produced by a production method including ozonolysis of the compound represented by the formula (77). However, it is not limited to this manufacturing method and may be manufactured by any method.

And if the compound represented by said Formula (77 ') is obtained, the compound represented by said Formula (76) will be obtained by the intramolecular coupling reaction. The conditions for this intramolecular coupling reaction are not particularly limited, and can be appropriately set by referring to known reactions. The intramolecular coupling reaction is preferably a reductive coupling reaction using a transition metal element, and more preferably the transition metal element contains titanium. Note that the reductive coupling of carbonyl compounds using low-valent titanium is known as the McMurry reaction. As the low-valent titanium, for example, a method in which TiCl ₃ or TiCl ₃ (DME) _1.5 complex (DME represents dimethoxyethane) is reduced and generated in a reaction system is often used. For example, Zn (Cu) or C ₈ K (potassium graphite) is used. There are many references describing the McMurry reaction. For example, "JE McMurry, Acc. Chem. Res., 1974, 7, p.281.", "JE McMurry, Acc. Chem. Res., 1983, 16, p .405. "," JE McMurry and KL Kees, J. Org. Chem., 1977, 42, p.2655. "And" DLJ Clive et al., J. Am. Chem. Soc., 1988, 110, p .6914. "Etc.

  When the compound represented by the chemical formula (76) is prepared as described above, it is oxidized to produce a compound represented by the following formula (81).

In formula (81), R ^{1 to} R ⁶ , X ¹¹ , X ²¹ and X ³¹ are the same as those in formula (76), respectively.

  The conditions for the oxidation reaction are not particularly limited, and the oxidation reaction can be performed under the same conditions as in the conventional dehydrogenation reaction. For example, an oxidizing agent such as DDQ or chloranil may be used, but industrially a catalyst is preferably used. The catalyst is not particularly limited, and those usually used for dehydrogenation can be used. For example, Pd—C (palladium carbon), platinum, rhodium, metal sulfur, metal selenium, and the like can be used. These catalysts may be used alone or in combination of two or more.

  Other substances used and reaction conditions are not particularly limited, and can be appropriately set by referring to a conventional dehydrogenation reaction. When using an oxidizing agent such as DDQ or a catalyst such as Pd-C, the reaction solvent can be, for example, an aromatic hydrocarbon such as toluene or xylene, or an ether solvent such as dioxane or dimethoxyethane. A solvent may be used independently or may be used together 2 or more types. The reaction temperature and reaction time in this case are also not particularly limited, and may be appropriately selected depending on the type of reactant.

Then, the When compound obtained of the formula (81), and substituted optionally the benzylic hydrogen atoms on X ¹¹ to X a hydrogen atom and R ¹ on ³¹ to R ^6, the formula (1 The compound of this invention represented by this can be obtained. When any one of X ^{11 to} X ³¹ is an imino group and the hydrogen atom is substituted with a protecting group, the imino group may be deprotected as necessary and then substituted again. The deprotection method is not particularly limited, and a known method may be appropriately used depending on the kind of the protecting group.

The method for substituting hydrogen atoms on X ^{11 to} X ³¹ is not particularly limited, and various substituents can be introduced by the same method as the substitution reaction of diphenylmethane, fluorene, carbazole and the like having a similar chemical structure. It is. For example, when any of X ^{11 to} X ³¹ is a methylene group, in order to alkylate the methylene group, hydrogen of the methylene group is eliminated with butyllithium or the like to generate a carbanion, and A method such as adding an alkyl halide or the like can be used. In order to perform alkoxylation, a method usually used for alkoxylation at the benzyl position, for example, a method in which an alcoholysis reaction is carried out after halogenation can be used. Further, when a benzylic hydrogen atom is present on R ^{1 to} R ⁶ , the method for substituting the hydrogen atom is not particularly limited, and the reaction can be carried out in the same manner as a general benzylic substitution reaction. For example, the same method as described above can be used for substitution with an alkyl group or an alkoxy group.

  If it does as mentioned above, the compound represented by the said Formula (1) can be obtained without difficulty by an organic synthetic chemistry method. However, the method for producing the compound represented by the formula (1) is not limited to this, and any method may be used.

  And the organic semiconductor of this invention can be obtained by the above-mentioned manufacturing method, for example using the compound represented by said Formula (1).

  The organic semiconductor of the present invention has two groups derived from the compound molecule represented by the formula (1) in place of or in addition to the compound molecule represented by the formula (1) or ions thereof. One or more compound molecules having a structure linked by at least one of a covalent bond and a crosslinked chain, or ions thereof (hereinafter sometimes simply referred to as “crosslinked body”) may be included. However, the structures of the two or more groups may be the same or different from each other. In the case of producing such an organic semiconductor, the crosslinked body can be used in place of or in addition to the compound molecule represented by the formula (1) or ions thereof. The crosslinked chain is not particularly limited, and may be, for example, an alkylene group, a polyene, a crosslinked chain containing an ester bond, an ether bond, or the like. Among these, for example, an alkylene group is preferable, and a methylene group or a polymethylene group having 2 to 10 carbon atoms is more preferable. The two or more groups each preferably contain at least one benzylic carbon, and the binding site with the covalent bond or the crosslinking chain is preferably the benzylic carbon.

  The method for producing such a crosslinked product is not particularly limited, and a known method can be used as appropriate according to the structure of the intended crosslinked product, and examples thereof include the following methods. That is, first, the benzyl position of sumanen (compound of the above formula (84)) is monohalogenated at one position, and a coupling reaction is carried out with a halogenated alkylene such as 1,4-dibromobutane. Although this method is not particularly limited, for example, there is a method in which metal Mg is added to the sumanene monohalide to form a Grignard reagent, and then 1,4-dibromobutane is added to perform coupling. In this way, a compound in which the benzylic positions of sumanene are linked by a tetramethylene group is obtained. Further, if necessary, a substituent is introduced into the remaining benzyl position by the above-described method or the like to obtain a target crosslinked product.

  Further, when an isomer such as a tautomer, stereoisomer, or optical isomer is present in the compound molecule represented by the formula (1) or an ion or a crosslinked product thereof, the organic semiconductor of the present invention is Instead of or in addition to the compound molecule represented by the formula (1) or its ion or cross-linked product, it may contain the isomer. Furthermore, when the compound of the formula (1) and other compounds according to the present invention can form a salt, the organic semiconductor of the present invention may be an organic semiconductor containing the salt. The salt is not particularly limited, and may be, for example, an acid addition salt or a base addition salt. Further, the acid forming the acid addition salt may be an inorganic acid or an organic acid, and the base forming the base addition salt may be an inorganic base. An organic base may be used. Although it does not specifically limit as said inorganic acid, For example, a sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, etc. are mention | raise | lifted. The organic acid is not particularly limited, and examples thereof include p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, and acetic acid. The inorganic base is not particularly limited, and examples thereof include ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, carbonates and hydrogen carbonates, and more specifically, for example, Examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydroxide and calcium carbonate. The organic base is not particularly limited, and examples thereof include ethanolamine, triethylamine, and tris (hydroxymethyl) aminomethane.

  The method for producing the salt of the compound represented by the formula (1) is not particularly limited, and for example, the above acid or base is appropriately added to the compound represented by the formula (1) by a known method. It can be manufactured by a method such as

In the organic semiconductor of the present invention, in the formula (1), it is preferable that the substituents on A ^{1 to} A ⁶ and the X ^{1 to} X ³ satisfy the following conditions.

(Conditions for substituents on A ^{1 to} A ⁶ and the above X ^{1 to} X ³ )
Each of A ^{1 to} A ⁶ is the same or different and is a hydrogen atom, a linear or branched alkyl group, or an aromatic hydrocarbon group, and when a benzylic hydrogen atom is present on A ^{1 to} A ⁶ The hydrogen atom may be substituted by a substituent,
The substituents on A ^{1 to} A ⁶ may be the same or different, and may be halogen, a linear or branched small molecule or polymer chain (however, in the main chain and side chain, hetero A carbocyclic ring having 3 to 20 ring constituent atoms, which may or may not contain an atom, may or may not contain an unsaturated bond, and may or may not contain a cyclic structure) Heterocycle (however, it may be monocyclic or condensed, saturated or unsaturated, may or may not have a substituent), saturated or unsaturated hydrocarbon group, hydroxy group, alkoxy group, alkanoyloxy group Amino group, oxyamino group, alkylamino group, dialkylamino group, alkanoylamino group, cyano group, nitro group, sulfo group, alkyl group substituted with one or more halogens, alkoxy group Nyl groups (wherein the alkyl group may be substituted with one or more halogens), alkylsulfonyl groups (wherein the alkyl group may be substituted with one or more halogens), sulfamoyl group, alkylsulfamoyl group, a carboxyl group, a carbamoyl group, an alkylcarbamoyl group, an alkanoyl group or an alkoxymethyl or a carbonyl group, or, bind to the same a ^r (any integer r is from 1 to 6), substituents together for is covalently attached, their binding carbocyclic or heterocyclic ring together with a ^r to (although a condensed ring be monocyclic, be saturated may be unsaturated, or not containing a substituent May be formed)
The substituents on X ^{1 to} X ³ are the same as or different from each other;
When the bonded X ^a (a is any integer from 1 to 3) is a methylene group or a vinylidene group, halogen, a linear or branched small molecule or polymer chain (however, its main chain) The chain and the side chain may or may not contain a hetero atom, may or may not contain an unsaturated bond, and may or may not contain a cyclic structure) A carbocyclic or heterocyclic ring having a ring number of 3 to 20 (however, it may be monocyclic or condensed, saturated or unsaturated, may or may not have a substituent), saturated or unsaturated hydrocarbon group, Hydroxy, alkoxy, alkanoyloxy, amino, oxyamino, alkylamino, dialkylamino, alkanoylamino, cyano, nitro, sulfo, and one or more halogens Alkyl group, alkoxysulfonyl group (wherein the alkyl group may be substituted with one or more halogens), alkylsulfonyl group (wherein the alkyl group is substituted with one or more halogens) ), A sulfamoyl group, an alkylsulfamoyl group, a carboxyl group, a carbamoyl group, an alkylcarbamoyl group, an alkanoyl group, or an alkoxycarbonyl group, or the same X ^a (a is any one of 1 to 3) And the substituents bonded to each other by a covalent bond, together with the X ^a to which they are bonded, may be ^a carbocyclic or heterocyclic ring (which may be monocyclic or condensed, saturated or unsaturated, May or may not have),
When the X ^{a to} be bonded is an iminomethylene group or an imino group, halogen, a linear or branched small molecule or polymer chain (however, the main chain and side chain contain a heteroatom. A carbocyclic ring or a heterocyclic ring having 3 to 20 ring atoms (which may or may not include an unsaturated bond and may or may not include a cyclic structure). However, it may be monocyclic or condensed, saturated or unsaturated, may or may not have a substituent), saturated or unsaturated hydrocarbon group, hydroxy group, alkoxy group, alkanoyloxy group, one An alkyl group, a carboxyl group, a carbamoyl group, an alkylcarbamoyl group, an alkanoyl group, or an alkoxycarbonyl group substituted with the above halogen.

Further, in the formula ^{(1), A 1 ~A 6} , and the substituent on the X ¹ to X ³ satisfy the condition it is more preferable below.

(Conditions for substituents on A ^{1 to} A ⁶ and the above X ^{1 to} X ³ )
A ^{1 to} A ⁶ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group, and a benzylic hydrogen on A ^{1 to} A ⁶ When an atom is present, the hydrogen atom may be substituted with a substituent,
Substituents on A ^{1 to} A ⁶ are the same or different and are halogen, saturated or unsaturated linear or branched hydrocarbon chain having or not having substituent, conjugated polymer chain or oligomer Chain, carbocyclic or heterocyclic ring having 3 to 20 ring atoms (however, it may be monocyclic or condensed, saturated or unsaturated, may or may not have a substituent), hydroxy group A linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, 6 straight-chain or branched alkanoyloxy groups, amino groups, oxyamino groups, straight-chain or branched alkylamino groups having 1 to 6 carbon atoms, and dialkylamino groups (wherein the alkyl group is a straight chain having 1 to 6 carbon atoms) Chain or A straight-chain or branched alkanoylamino group having 1 to 6 carbon atoms, a cyano group, a nitro group, a sulfo group, or a linear or branched chain having 1 to 6 carbon atoms substituted with one or more halogen atoms. A branched alkyl group, a straight chain or branched alkoxysulfonyl group having 1 to 6 carbon atoms (wherein the alkyl group may be substituted with one or more halogen atoms), a straight chain or branched chain having 1 to 6 carbon atoms. Branched alkylsulfonyl group (wherein the alkyl group may be substituted with one or more halogens), sulfamoyl group, linear or branched alkylsulfamoyl group having 1 to 6 carbon atoms, carboxyl group, carbamoyl A linear or branched alkylcarbamoyl group having 1 to 6 carbon atoms, a linear or branched alkanoyl group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms Turkey carboxymethyl or a carbonyl group, or a substituted group together to bind to (any integer of r from 1 to 6) identical A ^r is covalently bonded, carbon ring together with A ^r to which they are bonded Alternatively, it may form a heterocycle (however, it may be monocyclic or condensed, saturated or unsaturated, and may or may not have a substituent)
The substituents on X ^{1 to} X ³ are the same as or different from each other;
When the bonded X ^a (a is any integer from 1 to 3) is a methylene group or a vinylidene group, it is a saturated or unsaturated linear or branched hydrocarbon which may or may not have a halogen or a substituent. Chain, conjugated polymer chain or oligomer chain, carbocycle or heterocycle having 3 to 20 ring members (however, it may be monocyclic or condensed, saturated or unsaturated, and has a substituent) Or a hydroxy group, a straight chain or branched alkyl group having 1 to 6 carbon atoms, a straight chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms, a straight chain having 1 to 6 carbon atoms, or A branched alkoxy group, a linear or branched alkanoyloxy group having 1 to 6 carbon atoms, an amino group, an oxyamino group, a linear or branched alkylamino group having 1 to 6 carbon atoms, a dialkylamino group (however, its alkyl Group is a linear or branched alkyl group having 1 to 6 carbon atoms), a linear or branched alkanoylamino group having 1 to 6 carbon atoms, a cyano group, a nitro group, a sulfo group, one or more halogens. A substituted or straight chain or branched alkyl group having 1 to 6 carbon atoms, or a straight chain or branched alkoxysulfonyl group having 1 to 6 carbon atoms (however, the alkyl group may be substituted with one or more halogen atoms). ), A linear or branched alkylsulfonyl group having 1 to 6 carbon atoms (wherein the alkyl group may be substituted with one or more halogens), a sulfamoyl group, and a linear chain having 1 to 6 carbon atoms. Or a branched alkylsulfamoyl group, a carboxyl group, a carbamoyl group, a linear or branched alkylcarbamoyl group having 1 to 6 carbon atoms, a linear or branched alkanoyl group having 1 to 6 carbon atoms, or Substituents each other or a straight or branched alkoxycarbonyl group having 1 to 6 carbon atoms, or, (in a any integer from 1 to 3) same X ^a binding to, covalently attached And may form a carbocycle or a heterocycle (however, it may be monocyclic or condensed, saturated or unsaturated, and may or may not have a substituent) together with X ^a to which they are bonded. ,
When X ^{a to} be bonded is an iminomethylene group or an imino group, halogen, a saturated or unsaturated linear or branched hydrocarbon chain having or not having a substituent, a conjugated polymer chain or an oligomer chain, a ring A carbocyclic or heterocyclic ring having 3 to 20 atoms (however, it may be monocyclic or condensed, saturated or unsaturated, may or may not have a substituent), hydroxy group, carbon number Straight chain or branched alkyl group having 1 to 6 carbon atoms, straight chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms, straight chain or branched alkoxy group having 1 to 6 carbon atoms, straight chain having 1 to 6 carbon atoms A chain or branched alkanoyloxy group, a linear or branched alkyl group having 1 to 6 carbon atoms substituted with one or more halogens, a carboxyl group, a carbamoyl group, a linear or branched alkyl group having 1 to 6 carbon atoms Bamoiru group, a linear or branched alkanoyl group or a linear or branched alkoxycarbonyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms.

In the formula (1), it is more preferable that the substituents on A ^{1 to} A ⁶ and X ^{1 to} X ³ satisfy the following conditions.

(Conditions for substituents on A ^{1 to} A ⁶ and the above X ^{1 to} X ³ )
A ^{1 to} A ⁶ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group, and a benzylic hydrogen on A ^{1 to} A ⁶ When an atom is present, the hydrogen atom may be substituted with a substituent,
The substituents on A ^{1 to} A ⁶ are the same or different and are each a halogen or a linear hydrocarbon group having 1 to 3000 carbon atoms (particularly preferably 1 to 300, most preferably 1 to 30). However, each bond in the main chain may be a saturated bond or an unsaturated bond, and a hydrogen atom on the main chain may be optionally substituted with a halogen or a methyl group), a conjugated polymer chain or an oligomer chain, A cyclic substituent having a structure in which any one hydrogen is removed from the compound of any one of the following formulas (9) to (75) (provided that the cyclic substituent is further substituted with one or more substituents) The substituents may be the same or different from each other, and the substituent is a halogen, a methyl group, a hydroxy group, a methoxy group, an oxo group, or an amino group),

Hydroxy group, straight chain or branched alkyl group having 1 to 6 carbon atoms, straight chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms, straight chain or branched alkoxy group having 1 to 6 carbon atoms, carbon number 1 to 6 linear or branched alkanoyloxy group, amino group, oxyamino group, 1 to 6 carbon straight chain or branched alkylamino group, dialkylamino group (wherein the alkyl group has 1 to 6 carbon atoms) A linear or branched alkyl group of 1 to 6 carbon atoms, a linear or branched alkanoylamino group having 1 to 6 carbon atoms, a cyano group, a nitro group, a sulfo group, 1 to 6 carbon atoms substituted with one or more halogen atoms. A linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxysulfonyl group having 1 to 6 carbon atoms (however, the alkyl group may be substituted with one or more halogen atoms), and 1 to 6 carbon atoms. Straight chain Or a branched alkylsulfonyl group (wherein the alkyl group may be substituted with one or more halogens), a sulfamoyl group, a linear or branched alkylsulfamoyl group having 1 to 6 carbon atoms, carboxyl A group, a carbamoyl group, a linear or branched alkylcarbamoyl group having 1 to 6 carbon atoms, a linear or branched alkanoyl group having 1 to 6 carbon atoms, or a linear or branched alkoxycarbonyl group having 1 to 6 carbon atoms there, or, another substituent (the r any integer from 1 to 6) identical a ^r bind to is covalently bonded, carbon ring or heterocyclic ring together with a ^r to which they are bonded (except A monocyclic ring or a condensed ring, which may be saturated or unsaturated, and may or may not have a substituent,
The substituents on X ^{1 to} X ³ are the same as or different from each other;
When the X ^{a to be} bonded (a is any integer from 1 to 3) is a methylene group or a vinylidene group, halogen, 1 to 3000 carbon atoms (particularly preferably 1 to 300, most preferably 1 to 30) ) Linear hydrocarbon groups (wherein the bonds in the main chain may be saturated bonds or unsaturated bonds, respectively, and hydrogen atoms on the main chain may be optionally substituted with halogen or methyl groups), A conjugated polymer chain or an oligomer chain, a cyclic substituent having a structure in which any one hydrogen is removed from the compound of any one of the above formulas (9) to (75) (however, the cyclic substituent is one Or may be further substituted with a plurality of substituents, and the substituents may be the same or different from each other, and the substituent may be a halogen, a methyl group, a hydroxy group, a methoxy group, an oxo group, or an amino group. A hydroxy group, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms. A linear or branched alkanoyloxy group having 1 to 6 carbon atoms, an amino group, an oxyamino group, a linear or branched alkylamino group having 1 to 6 carbon atoms, or a dialkylamino group (wherein the alkyl group has 1 to 6 linear or branched alkyl groups), 1 to 6 carbon straight or branched alkanoylamino groups, cyano groups, nitro groups, sulfo groups, carbon atoms substituted with one or more halogen atoms A linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxysulfonyl group having 1 to 6 carbon atoms (provided that the alkyl group may be substituted with one or more halogen atoms), carbon number 1-6 A linear or branched alkylsulfonyl group (wherein the alkyl group may be substituted with one or more halogens), a sulfamoyl group, a linear or branched alkylsulfamoyl group having 1 to 6 carbon atoms, A carboxyl group, a carbamoyl group, a linear or branched alkylcarbamoyl group having 1 to 6 carbon atoms, a linear or branched alkanoyl group having 1 to 6 carbon atoms, or a linear or branched alkoxycarbonyl group having 1 to 6 carbon atoms Or the substituents bonded to the same X ^a (a is any integer from 1 to 3) are bonded by a covalent bond, and together with the bonded X ^a carbocycle or heterocycle ( However, it may be monocyclic or condensed, saturated or unsaturated, and may or may not have a substituent.
When the X ^{a to} be bonded is an iminomethylene group or an imino group, a halogen, a linear hydrocarbon group having 1 to 3000 carbon atoms (particularly preferably 1 to 300, most preferably 1 to 30) (however, the main Each bond in the chain may be a saturated bond or an unsaturated bond, and a hydrogen atom on the main chain may be optionally substituted with a halogen or a methyl group), a conjugated polymer chain or an oligomer chain, the above formula ( 9)-(75) a cyclic substituent having a structure in which any one hydrogen is removed from the compound (provided that the cyclic substituent may be further substituted with one or more substituents) The substituents may be the same or different from each other, and the substituent is a halogen, a methyl group, a hydroxy group, a methoxy group, an oxo group, or an amino group), a hydroxy group, 1 to 6 carbon atoms Straight chain or branched alkyl group, straight chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms, straight chain or branched alkoxy group having 1 to 6 carbon atoms, straight chain or branched chain having 1 to 6 carbon atoms An alkanoyloxy group, a linear or branched alkyl group having 1 to 6 carbon atoms substituted with one or more halogens, a carboxyl group, a carbamoyl group, a linear or branched alkylcarbamoyl group having 1 to 6 carbon atoms, a carbon number A linear or branched alkanoyl group having 1 to 6 carbon atoms, or a linear or branched alkoxycarbonyl group having 1 to 6 carbon atoms.

  In the present invention, “halogen” refers to any halogen element, and examples thereof include fluorine, chlorine, bromine and iodine. The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The same applies to a group containing an alkyl group in its structure (for example, an alkoxy group, an alkylamino group, an alkoxycarbonyl group, etc.). The unsaturated hydrocarbon group is not particularly limited, and examples thereof include a vinyl group, 1-propenyl group, allyl group, propargyl group, isopropenyl group, 1-butenyl group, and 2-butenyl group. The alkanoyl group is not particularly limited, and examples thereof include a formyl group, an acetyl group, a propionyl group, an isobutyryl group, a valeryl group and an isovaleryl group, and a group containing an alkanoyl group in the structure (alkanoyloxy group, alkanoylamino group). The same applies to the group or the like. Further, an alkanoyl group having 1 carbon atom means a formyl group, and the same applies to a group containing an alkanoyl group in its structure.

  The conjugated polymer chain or oligomer chain includes polyphenylene, oligophenylene, polyphenylene vinylene, oligophenylene vinylene, polyene, oligovinylene, polyacetylene, oligoacetylene, polypyrrole, oligopyrrole, polythiophene, oligothiophene, polyaniline and oligoaniline (however, These are more preferably at least one selected from the group consisting of one or more substituents which may or may not be substituted. In this case, the substituent is a halogen atom. Particularly preferred is at least one selected from the group consisting of a methyl group, a hydroxy group, a methoxy group, an oxo group, and an amino group. Further, the conjugated polymer chain or oligomer chain preferably has a formula weight in the range of 30 to 30,000. The formula weight is particularly preferably 50 to 5000, optimally 50 to 1000.

In the formula (1), a substituent bonded to the same A ^r (r is any integer from 1 to 6) or the same X ^a (a is any integer from 1 to 3). each other are coupled by a covalent bond, a ^r or X ^a together with the carbon ring or heterocyclic ring which they are bonded (although, in fused ring be monocyclic, be saturated may be unsaturated, may not have a substituent And the substituent is selected from the group consisting of a halogen, a methyl group, a hydroxy group, a methoxy group, an oxo group, and an amino group. It is preferable that it is at least one.

In the formula (1), at least one of the substituents on X ^{1 to} X ³ forms a conjugated system integrally with the bonded X ^a and further the benzene nucleus to which the X ^a is bonded. If it has, it can use more preferably for the use of an organic semiconductor from viewpoints, such as electrical conductivity and electron mobility. There are many such compounds, for example, compounds represented by the following formulas (89) to (91). However, the compounds of formulas (89) to (91) are merely examples and are not limited thereto.

In the formula (1), the compound in which no substituent on X ^{1 to} X ³ is present (that is, any hydrogen atom on X ^{1 to} X ³ is not substituted with the substituent) is used as it is. Although it may be used as a raw material for the organic semiconductor of the present invention, it can be easily used as a raw material for synthesis of other derivatives. The A ¹ to A ^6, that are all hydrogen atom, Similarly, it may be preferable easier to use in the organic semiconductor material of synthetic raw materials and the invention of other derivatives, A ¹ to A ⁶ is An alkyl group or an aromatic hydrocarbon group may be included.

In the formula (1), X ^{1 to} X ³ are preferably at least one selected from the group consisting of a methylene group, a vinylidene group, an imino group, and an oxygen atom, for example, X ^{1 to} X ³ More preferably, all are methylene groups. In particular, a compound in which all of A ^{1 to} A ⁶ are hydrogen atoms and all of X ^{1 to} X ³ are methylene groups, all of which are not substituted, that is, the parent compound, sumanene, is a derivative of various derivatives. Not only is it easy to use as a synthetic raw material, it is suitable as an organic semiconductor material.

Furthermore, the inventors of the compound represented by the general formula (1), tautomers and stereoisomers thereof, and salts thereof, X ^{1 to} X ³ are vinylidene groups, and X ¹ to X ³ is each at least one substituent selected from the group consisting of a phenyl group, a thienyl group and an oligothiophene chain (the substituent is further substituted with one or more electric donating groups or electric withdrawing groups) And the tautomers and stereoisomers thereof, and salts thereof can be preferably used for the organic semiconductor of the present invention. The degree of polymerization of the oligothiophene chain is not particularly limited, but is 2 to 8, for example. Examples of the electron donating group include an alkyl group (preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group) and an alkoxy group (preferably having a carbon number of 1 to 6). 6 is a straight-chain or branched alkoxy group, particularly preferably a methoxy group, and examples of the electron-withdrawing group include halogen and halogenated alkyl groups (preferably a straight chain having 1 to 6 carbon atoms). A chain or branched alkyl group, particularly preferably a trifluoromethyl group). Among these compounds, compounds represented by any one of the following formulas (101) to (109), tautomers and stereoisomers thereof, and salts thereof are particularly preferable.

  Examples of the reason why these compounds can be preferably used in the organic semiconductor of the present invention include the following reasons. That is, first, since the vinylidene group and the phenyl group, thienyl group or oligothiophene chain bonded to the benzene nucleus of the Smanen structure form a conjugated system, as described above, electrical conductivity, electron mobility, etc. From the viewpoint of In addition, by being excellent in solubility in a solvent, for example, operations such as recrystallization and thin film formation can be easily performed, and an organic semiconductor can be easily produced. Furthermore, for example, by replacing the phenyl group, thienyl group or oligothiophene chain with an electron donating group or an electrophilic group, the band gap energy is further reduced, and the electrical conductivity, electron mobility, etc. are further improved. It is possible.

  In the formulas (101) to (109), the bond represented by the wavy line indicates that the bond may be on any side of the vinylidene group. For example, the compound of the formula (101) may be a symmetric compound represented by the following formula (101-1) or an asymmetric compound represented by the following formula (101-2). good. The same applies to the compounds of the formulas (102) to (109).

In addition, the present inventors have found a method capable of efficiently converting a methylene group into a vinylidene group when at least one of X ^{1 to} X ³ of the compound represented by the general formula (1) is a methylene group. . According to the method for producing an organic compound of the present invention using this method, the compounds represented by the formulas (101) to (109) can be produced efficiently. More specifically, the production method of the present invention is a method for producing an organic compound, wherein among the compounds represented by the formula (1), at least one of X ^{1 to} X ³ is a methylene group. A production method comprising a step of reacting with an aldehyde or a ketone in the presence of an inorganic base and a phase transfer catalyst to obtain a product in which the methylene group is converted to a vinylidene group (which may or may not be substituted by a substituent). It is. Even if a lithiation reagent such as butyl lithium is used in place of the inorganic base and the phase transfer catalyst, at least one methylene group among X ^{1 to} X ³ can be efficiently converted to a vinylidene group. However, according to the production method of the present invention using an inorganic base and a phase transfer catalyst, the conversion reaction to the vinylidene group can be performed very efficiently.

When the hydrogen atom of the vinylidene group in the product is substituted with a substituent, the substituent is not particularly limited. For example, in the case where X ^{1 to} X ³ in the formula (1) are vinylidene groups, The preferred substituents described above may be used. For example, if an aldehyde or a ketone having a structure corresponding to these substituents is used, a compound having these substituents can be easily produced.

  In the method for producing an organic compound of the present invention, the aldehyde or ketone is an aromatic aldehyde in which a formyl group is directly bonded to an aromatic ring, the reactivity is high, the electrical conductivity of the product, the electron mobility, etc. Is preferable for reasons such as being good. More preferably, the aromatic ring of the aromatic aldehyde is a phenyl group, a thienyl group, or an oligothiophene chain, and the phenyl group, thienyl group, or oligothiophene chain is formed by one or more electric donating groups or electric withdrawing groups. Further, it may be substituted. Examples of the electron donating group include an alkyl group (preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group) and an alkoxy group (preferably having 1 to 6 carbon atoms). A linear or branched alkoxy group, particularly preferably a methoxy group, and examples of the electron withdrawing group include a halogen and a halogenated alkyl group (preferably a linear or branched group having 1 to 6 carbon atoms). A branched halogenated alkyl group, and particularly preferably a trifluoromethyl group).

In the method for producing an organic compound of the present invention, other electrophiles may be used in place of the aldehyde or ketone. As a product in this case, a product corresponding to the electrophile can be obtained in place of the product obtained by converting at least one methylene group of X ^{1 to} X ³ into a vinylidene group. For example, a halogenated hydrocarbon or a derivative thereof can be used as the electrophile to obtain a product in which the hydrogen atom of the methylene group is substituted with a hydrocarbon group or a group derived from the hydrocarbon group. . The halogenated hydrocarbon is not particularly limited. For example, a saturated hydrocarbon group such as an alkyl group may be substituted with a halogen, or an unsaturated hydrocarbon group such as an aromatic hydrocarbon group may be substituted with a halogen. Among these, halogenated unsaturated hydrocarbons such as allyl halide and benzyl halide are preferable from the viewpoint of high reactivity. As an example, when an allyl halide such as 3-bromopropene is used, a product in which a hydrogen atom in at least one methylene group among X ^{1 to} X ³ is substituted with an allyl group can be obtained.

In the method for producing an organic compound of the present invention, the inorganic base is not particularly limited. For example, from the viewpoint of reactivity or the like, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate is used. And at least one selected from the group consisting of alkaline earth metal carbonates, alkali metal hydrogen carbonates, and alkaline earth metal hydrogen carbonates. The phase transfer catalyst is not particularly limited, but from the viewpoint of reactivity and the like, for example, it preferably includes at least one of an ammonium salt and a phosphonium salt, and the ammonium salt is more preferably a quaternary alkyl ammonium salt, for example. Examples of the phase transfer catalyst include n-Bu ₄ NBr, n-Bu ₄ NI, n-Bu ₄ NCl, n-Bu ₄ NHSO ₄ , n-Bu ₄ NF, n-Bu ₄ NOH, n-Bu ₄ NBF. _{4, n-Bu 4 NPF 6} -, Me 4 NBr, Me 4 NI, Me 4 NCl, Me 4 NHSO 4, M e4 NF, Me 4 NOH, Me 4 NBF 4, Me 4 NPF 6 -, Et 4 NBr, _{Et 4 NI, Et 4 NCl,} Et 4 NHSO 4, Et 4 NF, Et 4 NOH, Et 4 NBF 4, Et 4 NPF 6 -, (nC 3 H 7) 4 NBr, (nC 3 H 7) 4 NI, (nC ₃ H ₇ ) ₄ NCl, (nC ₃ H ₇ ) ₄ NHSO ₄ , (nC ₃ H ₇ ) ₄ NF, (nC ₃ H ₇ ) ₄ NOH, (nC ₃ H ₇ ) ₄ NBF ₄ , (nC _{3 ^{H 7) 4 NPF 6 -,}} (iC 3 H 7) 4 NBr, (iC 3 H 7) 4 NI, (iC 3 H 7) 4 NCl, (iC 3 H 7) 4 NHSO 4, (iC 3 H 7 _{) 4 NF, (iC 3 H} 7) 4 NOH, (iC 3 H 7) 4 NBF 4, (iC 3 H 7) 4 NPF 6 -, (nC 5 H 11) 4 NBr, (nC 5 H 11) 4 NI, (nC ₅ H ₁₁ ) ₄ NCl, (nC ₅ H ₁₁ ) ₄ NHSO ₄ , (nC ₅ H ₁₁ ) ₄ NF, (nC ₅ H ₁₁ ) ₄ NOH, (nC ₅ H ₁₁ ) ₄ NBF ₄ , ( _{nC 5 H 11) 4 NPF 6} -, (nC 6 H 13) 4 NBr, (nC 6 H 13) 4 NI, (nC 6 H 13) 4 NCl, (nC 6 H 13) 4 NHSO 4, (nC 6 _{H 13) 4 NF, (nC} 6 H 13) 4 NOH, (nC 6 H 13) 4 NBF 4, (nC 6 H 13) 4 NPF 6 -, (nC 7 H ₁₅ ) ₄ NBr, (nC ₇ H ₁₅ ) ₄ NI, (nC ₇ H ₁₅ ) ₄ NCl, (nC ₇ H ₁₅ ) ₄ NHSO ₄ , (nC ₇ H ₁₅ ) ₄ NF, (nC ₇ H ₁₅ ) ₄ NOH _{, (nC 7 H 15) 4} NBF 4, (nC 7 H 15) 4 NPF 6 -, (nC 8 H 17) 4 NBr, (nC 8 H 17) 4 NI, (nC 8 H 17) 4 NCl, ( _{nC 8 H 17) 4 NHSO 4} , (nC 8 H 17) 4 NF, (nC 8 H 17) 4 NOH, (nC 8 H 17) 4 NBF 4, (nC 8 H 17) 4 NPF 6 -, (nC ₉ H ₁₉ ) ₄ NBr, (nC ₉ H ₁₉ ) ₄ NI, (nC ₉ H ₁₉ ) ₄ NCl, (nC ₉ H ₁₉ ) ₄ NHSO ₄ , (nC ₉ H ₁₉ ) ₄ NF, (nC ₉ H ₁₉ ) _{4 NOH, (nC 9 H 19} ) 4 NBF 4, (nC 9 H 19) 4 NPF 6 -, (nC 10 H 21) 4 NBr, (nC 10 H 21) 4 NI, (nC 10 H 21) 4 NCl _{, (nC 10 H 21) 4} NHSO 4, (nC 10 H 21) 4 NF, (nC 10 H 21) 4 NOH, (nC 10 H 21) 4 NBF 4, (nC 10 H 21) 4 NPF 6 -, (nC ₁₁ H ₂₃ ) ₄ NBr, (nC ₁₁ H ₂₃ ) ₄ NI, (nC ₁₁ H ₂₃ ) ₄ NCl, (nC ₁₁ H ₂₃ ) ₄ NHSO ₄ , (nC ₁₁ H ₂₃ ) ₄ NF, (nC ₁₁ H _{23) 4 NOH, (nC 11} H 23) 4 NBF 4, (nC 11 H 23) 4 NPF 6 -, (nC 12 H 25) 4 NBr, (nC 12 H 25) 4 NI, (nC 12 H 25) ₄ NCl, (nC ₁₂ H ₂₅ ) ₄ NHSO ₄ , (nC ₁₂ H ₂₅ ) ₄ NF, (nC ₁₂ H ₂₅ ) ₄ NOH, (nC ₁₂ H ₂₅ ) _{4 NBF 4, (nC 12 H} 25) 4 NPF 6 -, Bn 4 NBr, Bn 4 NI, Bn 4 NCl, Bn 4 NHSO 4, Bn 4 NF, Bn 4 NOH, Bn 4 NBF 4, Bn 4 NPF 6 - _{, BnMe 3 NBr, BnMe 3 NI} , BnMe 3 NCl, BnMe 3 NHSO 4, BnMe 3 NF, BnMe 3 NOH, BnMe 3 NBF 4, BnMe 3 NPF 6 -, BnEt 3 NBr, BnEt 3 NI, BnEt 3 NCl, BnEt _{3 NHSO 4, BnEt 3 NF,} BnEt 3 NOH, BnEt 3 NBF 4, and BnEt ₃ NPF ₆ ^- and particularly preferably includes at least one selected from the group consisting of. The reaction temperature, reaction time, solvent used, etc. are not particularly limited, and may be set as appropriate according to, for example, the type of raw material, or set as appropriate with reference to a conventional organic synthesis reaction using a phase transfer catalyst. You may do it. The reaction temperature is, for example, 3 to 150 ° C., preferably 10 to 35 ° C., particularly preferably 20 to 30 ° C., and the reaction time is, for example, 0.1 to 72 hours, preferably 1 to 24 hours, particularly Preferably it is 1-3 hours. Examples of the solvent used include ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane and dioxane, amides such as N, N-dimethylformamide, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, anisole, Aromatic solvents such as chlorobenzene, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, aliphatic hydrocarbons such as hexane and pentane, halogenated solvents such as methylene chloride and chloroform, methanol, ethanol, 2-propanol, t-butanol, Examples include alcohols such as ethylene glycol, and water.

  The compound represented by the formula (1) and the production method thereof have been described above.

  Furthermore, the organic semiconductor of the present invention may be an organic semiconductor containing a complex formation structure of the compound of the present invention represented by the formula (1) or a cross-linked product thereof and a metal element, and the formula (1) Or a cross-linked product thereof may be a tautomer or stereoisomer thereof. The metal element may be a single metal element or two or more kinds of metal elements. For example, the metal element preferably contains a transition metal element, and the transition metal is yttrium (Y) or samarium (Sm). , Titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), manganese (Mn), rhenium (Re) , Iron (Fe), ruthenium (Ru), iridium (Ir), cobalt (Co), rhodium (Rh), W (tungsten), Ni (nickel), Pd (palladium), Pt (platinum) and osmium (Os) More preferably, at least one selected from the group consisting of:

  As described above, the organic semiconductor of the present invention includes at least one selected from the group consisting of the compound represented by the formula (1), a tautomer, a stereoisomer, and a salt thereof. Therefore, it has high performance and can be used for various electronic devices such as organic transistors. In addition, the organic semiconductor of the present invention is not limited to an organic transistor, and can be used for any other electronic device. For example, an electronic device using a known organic device, organic semiconductor, conductive polymer, etc. It can be used for electronic devices of the same type as, and more specifically, for example, it can be used for electronic devices such as capacitors, capacitors, batteries, organic EL, fuel cells, and organic solar cells.

  Next, examples of the present invention will be described.

(Measurement conditions, etc.)
The nuclear magnetic resonance (NMR) spectrum was measured using an instrument called Mercury 300 (trade name) manufactured by Varian (300 MHz at the time of ¹ H measurement). Chemical shifts are expressed in parts per million (ppm). Tetramethylsilane (TMS) was used for the internal standard of 0 ppm. Coupling constants (J) are shown in hertz and the abbreviations s, d, t, q, m and br are singlet, doublet, triplet, quadruple, respectively. Represents a quartet, a multiplet, and a broad line. High resolution mass spectrometry (HRMS) was measured by an electron impact method or chemical ionization method using JMS-DX-303 (trade name) manufactured by JEOL. The ultraviolet-visible absorption spectrum and emission spectrum (UV-VIS) of the solution were measured using U-3500 (trade name) manufactured by Hitachi, Ltd. The measured value (wavelength) is expressed in nm. The UV-VIS spectrum of the solid (thin film) was measured using a spectrophotometer Agilent8453 (trade name) manufactured by Agilent Technologies. The measured value (wavelength) is expressed in nm. The infrared absorption spectrum (IR) was measured by KBr method using FT / IR 480 plus (trade name) manufactured by JASCO Corporation. The measured value (wave number) is expressed in cm ⁻¹ , and the abbreviations m and w represent medium and weak, respectively. The melting point was measured using a Yanagimoto MicroPoint Apparatus (trade name) manufactured by Yanagimoto Seisakusho Co., Ltd. Elemental analysis values were measured using CHN-Corder PERKIN-ELMER 240C (trade name) manufactured by Perkin-Elmer. X-ray structural analysis was performed using Mo-Kα rays monochromatized with graphite using an AFCC5R (trade name) X-ray diffractometer manufactured by Rigaku Corporation. The electrical conductivity was measured using an electrometer 6517 (trade name) manufactured by Keithley Instruments. For column chromatography separation, silica gel (trade name Wakogel CF-200, Wako Pure Chemical Industries, Ltd.) was used. As a plate for thin layer chromatography (TLC), Wakogel BF-5 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. was used. GPC was performed using LC-908 (trade name) manufactured by Nippon Analytical Industrial Co., Ltd. All chemicals are reagent grade. Norbornadiene was purchased from Tokyo Chemical Industry Co., Ltd. (500 mL, 16000 yen). The hexane solution of n-BuLi is from Kanto Chemical Co., Inc., (PCy ₃ ) ₂ RuCl ₂ = CHPh is from Aldrich, ethylene is from Osaka Oxygen Industry Co., Ltd., t-BuOK, 1,2-dibromoethane, copper iodide (I), toluene and DDQ were purchased from Wako Pure Chemical Industries, Ltd.

[Example 1: Organic semiconductor using sumanen]
In this example, as shown below, the sumanene represented by the formula (84) was synthesized, an organic semiconductor was produced using it, and the electrical properties of the organic semiconductor were measured.

(Synthesis of sumanen)
According to Scheme 1, sumanene was synthesized. Scheme 1 is reprinted below.

Hereinafter, specific operations and procedures will be described.

[Step a: Synthesis of syn-benzotris (norbornadiene) (the above formula (87)]]
First, a 1 L three-necked flask was vacuum-heated and dried, and purged with argon. To this, 180 mL of t-BuOK (120 mmol, 13.5 g) and dehydrated THF were added and stirred. Next, after reducing the temperature of the reaction system to −78 ° C., norbornadiene (2,5-norbornadiene, 240 mmol, 22.1 g), which is a compound represented by the above formula (86), was added while continuing stirring. N-BuLi in hexane (concentration 1.56 mol / L, equivalent to n-BuLi 120 mmol) was added dropwise over 2 hours. After completion of the dropwise addition, the temperature of the reaction system was raised to minus 40 ° C. and further stirred for 30 minutes. Then, after the temperature of the system was lowered again to minus 78 ° C., 1,2-dibromoethane (60 mmol, 11.3 g) was added, and then the temperature was raised again to minus 40 ° C., followed by stirring for 1.5 hours. Next, the temperature of the system was again returned to minus 78 ° C., and then copper (I) iodide (120 mmol, 22.9 g) was added. Then, after stirring at −78 ° C. for 4 hours, the cooling was stopped, and the mixture was further stirred for 7 hours while gradually returning to room temperature. Thereafter, the reaction was stopped using a saturated aqueous ammonium chloride solution, and filtered through Celite. The filtrate was extracted with ether, and the remaining aqueous layer was further extracted with ether. The combined organic layers were washed with water and dried over MgSO ₄ . After distilling off the solvent under reduced pressure, the residue was separated by silica gel column chromatography (hexane: dichloromethane = 4: 1), syn-benzotris (norbornadiene) (syn-benzotris (norbornadiene)) and anti-benzotris ( A diastereomeric mixture of anti-benzotris (norbornadiene) was obtained. Further, the mixture was separated by GPC, and the target product syn-benzotris (norbornadiene) (yield 108 mg, isolated yield 2%) and anti-benzotris (norbornadiene) (yield 270 mg, isolated yield 5) %) And obtained. The physical property values of these compounds are shown below.

syn-benzotris (norbornadiene): HRMS: 270.1403, melting point: 195 ° C (dec), ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 6.57 (t, J = 1.8 Hz, 6 H), 3.90-3.87 ( m, 6 H), 2.22 (dt, J = 7.2, 1.5 Hz, 3H), 2.08 (dt, J = 7.2, 1.5 Hz, 3 H); ¹³ C-NMR (75 MHz, CDCl ₃ ): 141.59, 137.66 , 66.73, 17.44 ppm.
anti-benzotris (norbornadiene): ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 6.68 (t, J = 1.8 Hz, 2 H), 6.65 (dd, J = 5.4, 3.0 Hz, 2 H), 6.59 (dd, J = 5.4, 3.0 Hz, 2 H), 3.90-3.87 (m, 2 H), 3.87-3.85 (m, 4 H), 2.05 (dt, J = 7.2 1.5 Hz, 4 H), 2.00 ( (dt, J = 7.2, 1.5 Hz, 4 H)

[Step b: Synthesis of Hexahydrosmanen (Formula (88))]
First, the 200 mL three-necked flask was vacuum-dried and purged with argon, and a solution obtained by dissolving syn-benzotris (norbornadiene) (0.074 mmol, 20 mg) in 100 mL of toluene was added thereto. Next, the temperature of the system was lowered to minus 78 ° C., and ethylene gas was bubbled and introduced sufficiently to make the inside of the system under an ethylene atmosphere. Thereafter, the temperature of the system was returned to room temperature, (PCy ₃ ) ₂ RuCl ₂ = CHPh (0.0037 mmol, 3 mg, 5 mol%) was added, and the mixture was stirred at room temperature for 24 hours while maintaining the ethylene atmosphere. Further, the system was placed in an argon atmosphere and heated to reflux for 48 hours, and then the reaction mixture was filtered through silica gel. The filtrate was evaporated under reduced pressure, and the resulting crude product was isolated by thin-layer chromatography (hexane: toluene = 5: 1) and finally purified by GPC to obtain the target compound hexahydrosuma Nene (hexahydrosumanene) was obtained (yield 4 mg, isolated yield 20%). The physical property values of this compound are shown below.

HRMS: Found: m / z = 270.1412, Calcd for C ₂₁ H ₁₈ : M = 270.1408, melting point: 180 ° C (dec), ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 5.69 (s, 6 H) , 3.81 (dd, 6 H, J = 9.9 and 7.2 Hz), 2.78 (dt, 3 H, J = 11.4 and 7.2 Hz), 1.01 (dt, 3H, J = 9.9 and 11.4 Hz); ¹³ C-NMR ( 75 MHz, CDCl ₃ ): 141.91, 129.28, 43.66, 40.35 ppm, IR (KBr): ν = 3010 (m), 2919 (m), 2814 (m), 1595 (w), 1445 (w), 1260 (w) cm ^-1 , UV-VIS (CH ₂ Cl ₂ ): Maximum absorption wavelength (Absorption λ _max ) = 240 nm, Maximum emission wavelength (Emission λ _max ) = 331 nm (Excitation λ) = 240 nm )

[Step c: Synthesis of Sumanen (Formula (84))]
First, a 10 mL two-necked flask was vacuum-heated and dried and then purged with argon. Next, a solution obtained by dissolving hexahydrosmanene (0.011 mmol, 3 mg) in 2 mL of toluene is added by syringe, and then DDQ (0.0385 mmol, 9 mg) is added, and then at 110 ° C. for 20 hours. Heated. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was separated by thin layer chromatography (hexane) to obtain the target compound, sumanene (yield 2 mg, isolated yield 67%). The physical property values of this compound are shown below. 1 to 5 show UV-VIS absorption spectrum diagrams of this compound. The solvent used is cyclohexylamine (CHA) in FIG. 1, tetrahydrofuran (THF) in FIG. 2, acetonitrile (CH ₃ CN) in FIG. 3, and dichloromethane (CH ₂ Cl ₂ ) in FIG. 1.0 × 10 ⁻⁴ M. FIG. 5 is a diagram showing all the spectrum diagrams of FIGS.

Elemental analysis: Found; C; 95.22, H; 4.77%; Calcd for C ₂₁ H ₁₂ : C; 95.42, H; 4.58%, HRMS: Found: m / z = 264.0923, Calcd for C ₂₁ H ₁₂ : M = 264.0939, melting point: 115 ° C (in air),> 290 ° C (in nitrogen-filled capillary), ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 7.01 (s, 6 H), 4.71 (d, J = 19.5 Hz, 3 H), 3.42 (d, J = 19.5 Hz, 3 H); ¹³ C-NMR (75 MHz, CDCl ₃ ): 148.78, 148.60, 123.15, 41.77 ppm., IR (KBr): ν = 2950 ( m), 2922 (s), 2852 (m), 1653 (m), 1558 (m), 1260 (w), 803 (s) cm ^-1 , UV-VIS (cyclohexylamine (CHA), 1.0 × 10 ^{− 4} M): Maximum absorption wavelength (Absorption λ _max ) = 279 nm (log ε = 4.56), UV-VIS (tetrahydrofuran (THF), 1.0 × 10 ^-4 M): Maximum absorption wavelength (Absorption λ _max ) = 278 nm ( logε = 4.62), UV-VIS (acetonitrile (CH ₃ CN), 1.0 × 10 ⁻⁴ M): maximum absorption wavelength (Absorption λ _max ) = 276 nm (logε = 4.25), UV-VIS (CH ₂ Cl ₂ ) : Maximum absorption wavelength (Absorption λ _max ) = 278 nm (log ε = 4.52), Maximum emission wavelength (Emission λ _max ) = 376 nm (Excitation wavelength (Exci tation λ) = 278 nm)
When temperature variable ¹ H-NMR (300 MHz, d ₁₀ -p-xylene) was measured from 25 ° C. to 140 ° C., the critical temperature Tc was 140 ° C. or higher, and the inversion energy ΔG ‡ It was calculated to be 19.4 kcal / mol or more from the shift value and coupling constant J.

  As described above, it was possible to synthesize sumanene in only three steps from norbornadiene which is inexpensive and easily available. In addition, all the steps are extremely mild and can be easily industrialized and mass-synthesized by, for example, using a dehydrogenation catalyst instead of DDQ.

  In addition, benzotris (norbornadiene) can be used in place of the above-mentioned step a. It was also possible to synthesize using the cross-coupling method of the halide and the organometallic reagent described in "-7897.", That is, the method of the following scheme 2. Furthermore, the step b could be performed without separating benzotris (norbornadiene) into a syn isomer and an anti isomer. Same as above except that in step b, a mixture of syn and anti forms is used as a raw material instead of syn-benzotris (norbornadiene), and the purification method of hexahydrosmanene is changed from GPC to silica gel column chromatography. As a result of the synthesis, the target compound, sumanen, was obtained in a yield of 2.2% from a mixture of syn-benzotris (norbornadiene) and anti-benzotris (norbornadiene).

(Production and structural analysis of crystals)
A sumanen crystal was produced as follows and its structure was analyzed. That is, first, sumanene produced as described above was dissolved in tetrahydrofuran and recrystallized to obtain colorless plate crystals (0.80 mm × 0.40 mm × 0.30 mm).

  Next, the structure of this crystal was analyzed by X-ray structural analysis. Hereinafter, this X-ray structural analysis will be specifically described.

[Data collection]
All measurements were performed with an AFCC5R (trade name) X-ray diffractometer manufactured by Rigaku Corporation equipped with the sumanen crystal on a glass fiber and equipped with graphite monochromated Mo-Kα radiation and a rotating anode generator.

  The cell constant and orientation matrix for data collection were 25 carefully focused reflections in the 28.55 <2θ <29.49 ° range corresponding to rhombohedral (hexagonal axis) hexagonal cells (Laue class: −3 ml). Obtained from the least squares method using the mounting angle. And the lattice parameter was determined as follows (Formula 1).

z = 6 and FW = 264.33, and the calculated density is 1.42 g / cm ³ . Based on the extinction rule of (Equation 2) below, packing consideration, statistical analysis of strength distribution, structural analysis and optimization, and space group were determined as shown in (Equation 3) below.

  The data was collected at a temperature of 23 ± 1 ° C. using the ω-2θ scan technique with a maximum 2θ value of 55.0 °. Prior to data collection, several strongly reflective omega scans had an average width of half the height of 0.32 ° with a take-off angle of 6.0 °. The (1.68 + 0.30tanθ) ° scan was performed at a speed of 16.0 ° / min (in omega). Weak reflections (I <10.0σ (I)) were rescanned (up to 5 scans) and the counts were accumulated to ensure good coefficient statistics. A static background coefficient was recorded on each side of the reflection. The ratio of peak coefficient time to background coefficient time was 2: 1. The diameter of the incident beam collimator was 1.0 mm, the distance from the crystal to the detector was 258 mm, and the diameter of the detector was 9.0 × 13.0 mm (horizontal × vertical).

[Data reduction]
Of the 1063 reflections collected by the method described above, 525 were special (R _int = 0.016). Three typical reflection intensities were measured after every 150 reflections. With the progress of data collection, the standard increased by 2.5%. A straight line correction factor was added to the data to explain this phenomenon.

The absorption coefficient μ of the straight line of Mo-Kα radiation is 0.8 cm ⁻¹ . Empirical absorption correction based on several reflection azimuth scans results in transmittance distributed from 0.96 to 0.99.

[Structural analysis and optimization]
The structure was analyzed by the direct method (Reference 1 below) and expanded using the Fourier method (Reference 2 below). Non-hydrogen atoms were optimized by anisotropy, and hydrogen atoms were optimized by isotropic properties. The final cycle of full matrix least squares optimization (reference 3 below) is based on 493 observed reflections (I> 2σ (I)) and 80 variable parameters, Aggregated factors with consistent increases.

The standard deviation of unit weight observation (Reference Document 4 below) was 1.22. Maximum and minimum peak of the final difference Fourier synthesis diagrams respectively 0.36 and -0.65E ^- corresponds to / Å ^3. All calculations were performed using Molecular Structure Corporation's teXsan (Ref. 5) crystallography software package.

References
(1) SIR92: Altomare, A., Burla, MC, Camalli, M., Cascarano, M., Giacovazzo, C., Guagliardi, A., Polidori, G., (1994). J. Appl. Cryst. 27 435.
(2) DIRDIF94: Beurskens, PT, Admiraal, G., Beurskens, G., Bosman, WP, de Gelder, R., Israel, R. and Smits, JMM (1994) .The DIRDIF-94 Program System, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands.
(3) SHELXL-97: Sheldrick, GM (1997). Program for crystal structure optimization University of Goettingen, Germany.
(4) Standard deviation of unit weight observation:
(5) teXsan: Crystal Structure Analysis Package, Molecular Structure Corporation (1985 & 1999)

Experimental data obtained by the X-ray structural analysis performed as described above are shown in the following (Equation 6) to (Equation 8) and (Table 1) to (Table 9). The molecular formula of sumanen is C ₂₁ H ₁₂ , but since the molecule has C3 symmetry, the numbers given to each atom are C (1) to C (7) and H ( 1) to H (4). One inch is equal to 0.1 nm (10 ⁻¹⁰ m).

  6 and 7 show schematic views of the sumanen crystal structure analyzed by the X-ray structural analysis. FIG. 6 is a schematic view of the molecular arrangement in the sumanen crystal as seen from the molecular side, and FIG. 7 is a schematic view of the molecular arrangement in the sumanen crystal as seen from the top of the molecule. As shown in the figure, in the obtained crystal, the sumanene molecules have a bowl-like structure, and the secondary array was packed so that the bowls overlapped in parallel to form a laminate. Further, each sumanene molecule was positioned at an angle obtained by rotating the sumanene molecule which is substantially 60 ° shifted, that is, the sumanene molecule which is laminated in contact with the sumanene molecule by 60 °. Although expressed as “at an angle rotated by 60 °”, since the sumanen molecule has C3 symmetry, the same state is expressed even if the angle is expressed as “180 °” or “300 °”.

Furthermore, the bond length between carbon atoms in the sumanene molecule shown in the table is shown in the following chemical formula. The unit is Å. As described above, 1 前述 is equal to 0.1 nm (10 ⁻¹⁰ m). As shown in the figure, in the benzene ring structure in the sumanen molecule analyzed by the X-ray structure analysis, particularly in the benzene ring structure in the central part, a slight difference is observed between the bond lengths. This is considered to reflect a slight bias of charge. And since each of the sumanene molecules attracts the high electron density portion and the low electron density portion, as described above, each molecule is substantially 60 ° (or 180 ° or 300 ° with the molecule on or below it). ) It is presumed that the π electrons of the aromatic ring are packed efficiently and packed in parallel while being displaced. However, this description is an example of a presumed mechanism and does not limit the present invention.

  Next, the electrical conductivity and electron mobility of such a Smanen crystal were measured, and it was confirmed that the crystal exhibited excellent electrical conductivity and electron mobility as an organic semiconductor.

(Measurement of electric conductivity of sumanen crystal)
First, the sumanene produced as described above was recrystallized in tetrahydrofuran in the same manner as in the X-ray structural analysis measurement to obtain colorless plate crystals. Next, this was cut into a sample size having a cross-sectional area of 0.00044 cm and a crystal length of 0.10 cm to obtain a semiconductor sample. Using this sample, the electrical conductivity was measured under an argon atmosphere. The conductivity was 7 × 10 ⁻¹⁰ S / cm.

(Sumanen's electron mobility)
When the electron mobility of the same sumanene single crystal (semiconductor) as described above was measured, it showed a large electron mobility useful as an organic transistor material, particularly as a field effect transistor or a thin film transistor material.

(Thin film transistor)
Further, a field effect type thin film transistor having an organic semiconductor layer formed from sumanen was prepared using sumanen synthesized as described above. When the performance of the thin film transistor was evaluated, the electrical conductivity and the electron mobility were high, and the transistor had excellent performance.

  In addition, although the above-mentioned Example is an example of the semiconductor which used the single crystal of the sumanen molecule | numerator, this invention is not limited to this, For example, the semiconductor using the sumanen which is not a crystal | crystallization, or its derivative (s) may be used.

[Examples 2 to 19: Organic semiconductor using sumanene derivative]
The compounds represented by the formulas (101) to (109) were synthesized and their spectroscopic behavior was measured. Furthermore, an organic semiconductor was manufactured using each compound, and the electrical property was measured. The structural formulas (101) to (109) are listed below again. Hereinafter, the compound of the formula (101) may be referred to as su-ph or S-Ph. Similarly, hereinafter, the compound (102) is su-ph-Me or S-Ph-Me, the compound (103) is su-ph-OMe or S-Ph-OMe, and the compound (104) is su- ph-Cl or S-Ph-Cl or the like, compound (105) as su-ph-CF ₃ or S-Ph-CF ₃ or the like, compound (106) as su-1T or S-Th or the like, compound ( 107) may be referred to as su-2T or S-2Th, and the compound (108) may be referred to as su-3T or S-3Th.

(Synthesis)
Compounds (101) to (109) were synthesized as follows.

(Synthesis of Compound (101))
First, sumenene (5 mg, 0.019 mmol) and n-Bu ₄ NBr (6 mg, 0.0095 mmol) were placed in a 5 mL two-necked eggplant flask, and after vacuum drying, the atmosphere was replaced with argon. Thereto were added 30 wt% aqueous sodium hydroxide solution (1 mL) and THF (0.1 mL) that had been degassed beforehand by argon bubbling. Then, benzaldehyde (0.085 mmol) was added and stirred at room temperature for 2 hours. After completion of the reaction, ether was added, washed and extracted with deionized water, saturated aqueous ammonium chloride solution and saturated brine. The obtained organic layer was dried over magnesium sulfate, concentrated, and further isolated by column chromatography to obtain the target compound (101). The yield and instrumental analysis data of this compound are shown below.

Rf value 0.8 (hexane: toluene = 1: 1), yellow solid 8 mg (yield 79%)
¹ H NMR (600 MHz, CD ₂ Cl ₂ ) δ: 7.93 (3H, dd, J = 7.2 Hz, 3.6 Hz), 7.87 (3H, dd, J = 7.2 Hz, 3.3 Hz), 7.70 (1H, dd, J = 2.7 Hz, 1.5 Hz), 7.55 (1H, dd, J = 3.0 Hz, 1.8 Hz), 7.52-7.42 (18 H, m), 7.39-7.37 (3H, m), 7.22-7.19 (3H, m )
¹³ C NMR (150 MHz, CD ₂ Cl ₂ ) δ: 131.26, 130.05, 130.00, 129.16, 129.12, 129.06, 128.97, 128.90, 128.64, 123.89, 123.76, 121,21, 121,11, 68.39, 39.18, 30.07, 29.32, 24.14, 23.02, 14.24, 11.13
MS (MALDI-TOF): 528 (M) ⁺

(Synthesis of compounds (102) to (106))
Compound (102) was synthesized in the same manner as the synthesis of compound (101) except that p-methylbenzaldehyde was used instead of benzaldehyde. Similarly, compounds (103) to (105) were synthesized using p-methoxybenzaldehyde, p-chlorobenzaldehyde and p-trifluoromethylbenzaldehyde, respectively, instead of benzaldehyde. Furthermore, the compound (106) was synthesized using 2-formylthiophene instead of benzaldehyde. These were all obtained as a mixture of symmetric and asymmetric types. The yields and instrumental analysis data of the compounds (102) to (106) are shown below.

Compound (102) (su-ph-Me):
Rf value 0.6 (hexane: toluene = 1: 1)
Yellow solid 6.9 mg (64% yield)
¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ: 7.83 (3H, dd, J = 6.3 Hz), 7.77 (3H, dd, J = 6.6 Hz), 7.51 (1H, d, J = 2.1 Hz), 7.49 (1H, d, J = 2.1 Hz), 7.41 (2H, s), 7.39 (2H, d, J = 3.9 Hz), 7.33-7.26 (11H, m), 7.20 (1H, d, i = 4.5 Hz ), 7.17 (1H, d, J = 4.5 Hz), 7.12 (1H, s), 2.45 (3H, s), 2.44 (3H, s), 2.41 (3H, s), 2.40 (3H, s)
HRMS (FAB): Calcd for C ₄₅ H ₃₀ 570.2347; Found 570.2336 (M) ⁺

Compound (103) (su-ph-OMe):
Rf value 0.4 (hexane: toluene = 1: 3),
9.5 mg of yellow solid (81% yield)
¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ: 7.90 (3H, dd, J = 8.4 Hz, 5.1 Hz), 7.85 (3H, dd, J = 8.7 Hz, 5.4 Hz), 7.54 (1H, d, J = 1.5 Hz), 7.51 (1H, d, J = 1.5 Hz), 7.41 (2H, d, J = 2.1 Hz), 7.37 (2H, d, J = 3.0 Hz), 7.31 (2H, s), 7.21 (1H, d, J = 4.5 Hz), 7.18 (1H, d, J = 3.9 Hz), 7.05-6.96 (10H, m), 3.90 (3H, s), 3.89 (3H, s), 3.87 (3H, s), 3.86 (3H, s)
HRMS (FAB): Calcd for C ₄₅ H ₃₀ O ₃ 618.2195; Found 618.2186 (M) ⁺

Compound (104) (su-ph-Cl):
Rf value 0.8 (hexane: toluene = 1: 1),
Yellow solid 10.2 mg (85% yield)
¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ: 7.87 (3H, dd, J = 8.4 Hz, 6.0 Hz), 7.81 (3H, dd, J = 8.1 Hz, 5.7 Hz), 7.49-7.36 (12H, m), 7.26-7.08 (10H, m)
HRMS (FAB): Calcd for C ₄₂ H ₂₁ Cl ₃ 630.0709; Found 630.0718 (M) ⁺

Compound (105) (su-ph-CF ₃ ):
Rf value 0.7 (hexane: toluene = 1: 1),
Yellow solid 7.9 mg (57% yield)
¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ: 8.05 (3H, dd, J = 7.5 Hz), 7.98 (3H, dd, J = 7.5 Hz), 7.78-7.71 (6H, m), 7.49-7.37 (6H, m), 7.26-7.08 (10H, m)
HRMS (FAB): Calcd for C ₄₅ H ₂₁ F ₉ 732.1499; Found 732.1502 (M) ⁺

Compound (106) (su-ph-1T):
Rf value 0.4 (hexane: toluene = 1: 1), orange solid 8 mg (yield 72%)
¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ: 8.01 (2H, d, J = 7.8 Hz), 7.91 (2H, s), 7.72-7.69 (4H, m), 7.53-7.50 (6H, m) , 7.37 (2H, s), 7.28 (2H, d, J = 3.3 Hz), 7.26 (2H, d, J = 3.3 Hz), 7.22-7.17 (4H, m) MS (MALDI-TOF): 546 (M ) ⁺

(Synthesis of Compound (108))
A compound (108) in which a trithiophene chain was introduced into sumanen was synthesized as follows.

[Synthesis of 2,2 ': 5', 2 "-terthiophene-5-carboxaldehyde]

First, a 50 mL two-necked eggplant flask equipped with a cooling tube was vacuum dried and purged with argon. Next, 2,2 ': 5', 2 "-terthiophene (1 g, 4 mmol) and DMF (0.36 mL, 4.4 mmol) were dissolved in dichloroethane and added to the eggplant flask. Was cooled with ice-salt, POCl ₃ (0.41 mL, 4.4 mmol) was added, and the mixture was stirred for 1 hour at room temperature and then for 12 hours at 60 ° C. After completion of the reaction, saturated bicarbonate was used with methylene chloride. The organic layer was washed and extracted with an aqueous sodium solution, deionized water and saturated brine, dried over magnesium sulfate, concentrated, and further isolated by column chromatography (hexane: methylene chloride = 1: 1). There was thus obtained 2,2 ': 5', 2 "-terthiophene-5-carboxaldehyde as a yellow solid with an Rf value of 0.4 (methylene chloride). The yield was 552 mg (yield 50%). The instrumental analysis data of this compound is shown below.

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ: 9.85 (1H, s), 7.70 (1H, d, J = 3.9 Hz), 7.32-7.26 (4H, m), 7.17 (1H, J = 3.9 Hz ), 7.06 (1H, dd, J = 5.4 Hz, 3.9 Hz)

[Synthesis of Compound (108)]

First, sumenene (5 mg, 0.019 mmol) and n-Bu ₄ NBr (18 mg, 0.0285 mmol) were placed in a 20 mL two-necked eggplant flask, and the atmosphere was purged with argon after vacuum drying. Thereto were added 30 wt% aqueous sodium hydroxide solution (1 mL) and THF (0.1 mL) that had been degassed beforehand by argon bubbling. Then, 2,2 ': 5', 2 "-terthiophene-5-carboxaldehyde (23.8 mg, 0.086 mmol) was added and stirred for 2 hours at room temperature. After the reaction was completed, ether was added, deionized water, saturated The organic layer was washed and extracted with an aqueous ammonium chloride solution and saturated brine, dried over magnesium sulfate, concentrated, and further isolated by GPC, whereby the target compound (108) as a red solid was obtained. The yield was 10.6 mg (54% yield) The instrumental analysis data of this compound is shown below.

Compound (108) (su-ph-3T):
¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ: 8.11-8.00 (6H, m), 7.71-7.07 (34 H, m)
HRMS (FAB): Calcd for C ₆₀ H ₃₀ S ₉ 1037.9834; Found 1037.9819 (M) ⁺

  In addition, compound (107) (su-ph-2T) was also synthesized in the same manner as described above. Furthermore, the compound (109) which introduce | transduced vinylidene group (allyl group) into sumenen was also synthesize | combined.

[Synthesis of Compound (109)]
First, sumenen (4 mg, 0.015 mmol) and n-Bu ₄ NBr (15 mg, 0.045 mmol) were placed in a 20 mL two-necked eggplant flask, and the atmosphere was purged with argon after vacuum drying. And 30 wt% sodium hydroxide aqueous solution (2 mL) and THF (0.1 mL) which were deaerated beforehand by argon bubbling were added. Then, 3-bromopropene (0.13 ml, 1.5 mmol) was added and stirred at room temperature for 45 hours. After completion of the reaction, ether was added, washed and extracted with deionized water, saturated aqueous ammonium chloride solution and saturated brine. The obtained organic layer was dried over magnesium sulfate, concentrated and isolated by silica gel column chromatography. Thus, the target compound (109) as a white solid was obtained in a yield of 7.2 mg (yield 90%). The instrumental analysis data of this compound is shown below.

Compound (109):
¹ H-NMR (600 MHz): 2.64 (d, J = 6.6 Hz, 6H), 3.09 (d, J = 7.2 Hz, 6H), 3.51 (ddt, J = 17.4 Hz, J = 10.2 Hz, J = 6.6 Hz, 3H), 3.96 (dd, J = 10.2 Hz, J = 1.2 Hz, 3H), 4.26 (dd, J = 17.4 Hz, J = 1.2 Hz, 3H), 5.20 (dd, J = 10.2 Hz, J = 1.2 Hz, 3H), 5.24 (dd, J = 17.4 Hz, J = 1.2 Hz, 3H), 6.23 (ddt, J = 17.4 Hz, J = 10.2 Hz, J = 7.2 Hz,, 3H), 6.98 (s, 6H)
¹³ C-NMR (150 MHz): 39.7, 44.9, 63.0, 116.0, 117.9, 123.2, 133.9, 135.2, 146.8, 153.5

(Spectroscopic behavior of compounds (101) to (108))
The spectroscopic behavior of the compounds (101) to (108) was measured. 8 to 16 and Tables 10 to 14 show the measurement results. Hereinafter, this measurement result will be described more specifically.

  FIG. 8 shows a UV-VIS (ultraviolet-visible) absorption spectrum of the sumanen derivative su-ph (compound (101)) introduced with a benzylidene group, together with the sumanen spectrum. As shown in the figure, Smanen showed an absorption based on the π-π * transition at 278 nm. On the other hand, in su-ph, absorptions with absorption maximum wavelengths were observed at 345 nm and 457 nm, and a long wavelength shift of the absorption spectrum was observed compared with sumanen. Table 10 below shows the solvent dependence of su-ph. As can be seen from Table 10, no change in absorption wavelength according to the polarity of the solvent was observed. From this result, the cause of the long wavelength shift of the absorption spectrum of su-ph is presumed to be that the introduction of the benzylidene group expands the π-conjugated system and shifts the absorption based on the Smanen π-π * transition. In addition, in the solid state, sumanen is a white solid, whereas the obtained su-ph was a yellow solid, which means that su-ph has an expanded π-conjugated system compared to sumanen. Conceivable. The expansion of the π-conjugated system is preferable when used for an electronic material such as an organic semiconductor from the viewpoint of electrical conductivity, electron mobility, and the like.

FIG. 9 shows the fluorescence spectrum of su-ph together with the fluorescence spectrum of sumanene. The vertical axis in FIG. 9 is the fluorescence intensity, and the horizontal axis is the wavelength (nm). The measurement solvent is methylene chloride, the concentration is 1.0 × 10 ⁻⁴ M, and the excitation wavelength is 345 nm. As shown in the figure, fluorescence was observed at 376 nm in sumanen, and fluorescence was observed at 530 nm in su-ph. By introducing a benzylidene group, it is presumed that the π-conjugated system was expanded and a long wavelength shift of the fluorescence wavelength was induced. FIG. 10 also shows the absorption spectrum and fluorescence spectrum of su-ph. In FIG. 10, the vertical axis represents absorbance and fluorescence intensity, and the horizontal axis represents wavelength (nm). The measurement solvent is methylene chloride, the concentration is 1.0 × 10 ⁻⁴ M, and the excitation wavelength of the fluorescence spectrum is 345 nm. As shown in the figure, from the overlap of the absorption spectrum and the fluorescence spectrum, a 0 → 0 transition was observed at 498 nm. Also, the energy difference (ΔE ^0-0 ) between S ₀ and S ₁ corresponding to the energy difference between HOMO-LUMO is 2.5 eV (ΔE ^0-0 = 1 / (498 × 10 ^-7 ) = 20080 cm ^-1 = 2.48 eV). That is, su-ph (compound (101)) is considered to have a small energy difference between HOMO-LUMO. A small energy difference between HOMO-LUMO is preferable when used for an electronic material such as an organic semiconductor from the viewpoint of electrical conductivity, electron mobility, and the like.

FIG. 11 shows the measurement results of the UV-VIS absorption spectra of the derivatives su-ph-Me (compound (102)) and su-ph-OMe (compound (103)) into which an Me-donating group and an OMe group are introduced. Is shown together with the measurement result of su-ph (compound (101)). In FIG. 11, the vertical axis represents absorbance, and the horizontal axis represents wavelength (nm). The measurement solvent is methylene chloride and the concentration is 1.0 × 10 ⁻⁴ M. Table 11 below shows the values of λ _max and log ε of each absorption in this measurement. As shown in FIG. 10 and Table 11, in the derivatives su-ph-Me and su-ph-OMe containing the Me group which is an electron donating group and the OMe group, a long wavelength shift of the absorption wavelength occurred. The correlation between the magnitude of the long wavelength shift and the electron donating ability of the substituent was in good agreement with Hammett's law. A long wavelength shift in the absorption wavelength indicates that the band gap energy has decreased. That is, it can be seen that the band gap energy can be reduced by introducing an electron donating group into the p-position of the terminal phenyl moiety in the sumanen derivative into which the benzylidene substituent is introduced. A small band gap energy is preferable when used for an electronic material such as an organic semiconductor from the viewpoint of electrical conductivity, electron mobility, and the like.

On the other hand, FIG. 12 shows UV-VIS of the derivatives su-ph-Cl (compound (104)) and su-ph-CF ₃ (compound (105)) into which Cl and CF ₃ groups, which are electron withdrawing groups, are introduced. The measurement result of the absorption spectrum is shown together with the measurement result of su-ph (compound (101)). The vertical axis in FIG. 12 is absorbance, and the horizontal axis is wavelength (nm). The measurement solvent is methylene chloride and the concentration is 1.0 × 10 ⁻⁴ M. Table 12 below shows the values of λ _max and log ε of each absorption in this measurement. As shown in FIG. 12 and Table 12, a long wavelength shift of the absorption wavelength occurred in the derivatives su-ph-Cl and su-ph-CF ₃ containing Cl group and CF ₃ group which are electron withdrawing groups. According to the Hammett rule, when an electron withdrawing group is introduced, it is predicted that a short wavelength shift occurs contrary to the electron donating group. That is, the band gap energy can be reduced by introducing not only an electron donating group but also an electron withdrawing group. The cause of this is not necessarily clear, but it is assumed that, for example, planarization of the molecular structure by introducing an electron withdrawing group contributes.

FIG. 13 shows the measurement results of UV-VIS absorption spectra of sumane derivatives su-1T (compound (106)) and su-3T (compound (108)) into which oligothiophene was introduced via a double bond. It shows together with a measurement result. In FIG. 13, the vertical axis represents absorbance, and the horizontal axis represents wavelength (nm). The measurement solvent is methylene chloride and the concentration is 1.0 × 10 ⁻⁴ M. Table 13 below shows the values of λ _max and log ε of each absorption in this measurement. Further, Table 14 below shows the solvent effect of su-1T and su-3T in the UV-VIS absorption spectrum.

  As shown in Fig. 13 and Table 13, absorption was observed at 373 nm and 482 nm for su-1T in which thienylmethylidene group was introduced into sumenen, and at 434 nm and 545 nm in su-3T into which tertienylmethylidene group was introduced. It was done. That is, a long wavelength shift was observed compared to Smanen. The cause of this long wavelength shift is not necessarily clear, but as shown in Table 14, there is no change in the absorption wavelength depending on the polarity of the solvent, so that probably intramolecular charge transfer (ICT) due to the electron donor property of oligothiophene is Presumed not to be the cause. That is, as in su-ph (compound (101)) and the like having a phenylmethylidene group introduced, the introduction of thiophene or oligothiophene through a double bond expands the π-conjugated system, and the π-π * of sumanene It is thought that absorption based on the transition shifted. As described above, the expansion of the π-conjugated system is preferable when used for an electronic material such as an organic semiconductor.

FIG. 14 also shows the measurement results of the su-1T UV-VIS spectrum and fluorescence spectrum. FIG. 15 also shows the measurement results of the su-3T UV-VIS spectrum and fluorescence spectrum. 14 and 15, the vertical axis represents absorbance and fluorescence intensity, and the horizontal axis represents wavelength (nm). The measurement solvent is methylene chloride and the concentration is 1.0 × 10 ⁻⁴ M. The excitation wavelength of the fluorescence spectrum is 373 nm in FIG. 14 (su-1T) and 434 nm in FIG. 15 (su-3T). As shown in FIG. 14, with su-1T, fluorescence was observed at 564 nm. In addition, the 0 → 0 transition is observed at 530 nm from the overlap, and the energy difference (ΔE ^0-0 ) between S ₀ and S ₁ is 2.3 eV (ΔE ^0-0 = 1 / (530 × 10 ^-7 ) = 18868 cm ⁻¹ = 2.33 eV). Further, as shown in FIG. 15, with su-3T, fluorescence was observed at 489 nm and 650 nm. These fluorescences are considered to be the result of excitation of both oligothiophene and sumanen sites because the excitation wavelength is 434 nm, 489 nm fluorescence from oligothiophene, and 650 nm fluorescence from sumanen. It is presumed that it is fluorescence. The 0 → 0 transition is observed at 602 nm from the overlap of the absorption spectrum and the fluorescence spectrum, and the energy difference (ΔE ^0-0 ) between S ₀ and S ₁ is 2.1 eV (ΔE ^0-0 = 1 / (602 × 10 ⁻⁷ ) = 16611 cm ⁻¹ = 2.05 eV). In other words, by introducing thiophene or oligothiophene into Smanen via a double bond, the fluorescence wavelength is shifted by a long wavelength as well as the absorption wavelength, and the result is that the π-conjugated system is more effectively expanded. It was. It was also confirmed that the energy difference between HOMO and LUMO was small.

  FIG. 16 also shows the fluorescence spectra of su-ph (compound (101)), su-1T (compound (106)), and su-3T (compound (108)) for comparison of fluorescence intensities. The vertical axis in FIG. 16 is the fluorescence intensity, and the horizontal axis is the wavelength (nm). Measurement conditions such as measurement solvent, measurement concentration, and excitation wavelength are the same as those in FIGS. As can be seen from the figure, a decrease in fluorescence intensity was observed when a thiophene monomer or trimer was introduced via a double bond. The cause of this is not always clear, but one possibility is that electron transfer from oligothiophene occurs after the sumanen site is excited. As described above, a compound in which thiophene or oligothiophene is introduced into Smanen via a double bond exhibits characteristic electrical properties representing utility as an electronic material such as an organic semiconductor.

(Organic semiconductor)
The organic semiconductors of Examples 2 to 19 were manufactured as follows.

That is, first, a substrate on which an SiO ₂ film (300 nm) is thermally oxidized on an n-type semiconductor Si wafer (Furuuchi Chemical Machinery Co., Ltd., SiN type (100) 0.02 Ω · cm or less, SiO ₂ 300 nm) is formed in a predetermined manner. Cut to size and ultrasonically cleaned in 2-propanol for about 10 minutes. Next, any one of the compounds (101) to (109) is deposited on the SiO ₂ film by a vapor deposition method or a spin coat method to a thickness of 30 nm, and an Au electrode (source / drain) is further formed thereon. Electrode) was formed to a thickness of 30 nm by vacuum deposition. At this time, using a mask, electrodes were formed such that the distance between the electrodes was 20 μm and the electrode length was 5.0 mm. The organic semiconductor formed by the vapor deposition method using each of the compounds (101) to (109) is referred to as Examples 2 to 10 in the order of the compound numbers (101) to (109). Further, organic semiconductors formed by spin coating using each of the compounds (101) to (109) are referred to as Examples 11 to 19 in the order of the compound numbers of (101) to (109).

[Spectroscopic behavior]
For the organic semiconductors (thin films) of Examples 2 to 19 formed as described above, the ionization energy and the UV-VIS absorption spectrum were measured together with the sumanene of Example 1, and the energy level was calculated. The ionization energy was measured with an atmospheric photoelectron spectrometer AC-III (trade name) manufactured by Riken Keiki. The measurement sample was produced by forming a sumanene or its derivative thin film with a film thickness of 30 nm on a glass substrate. FIG. 17 shows the energy levels calculated for the organic semiconductors of Examples 2 to 7 and 9 together with Example 1. FIG. The upper limit of the graph in the figure is the LUMO energy value, and the lower limit is the HOMO energy value. As shown in the figure, the band gap energy was small in any of the examples, and in Examples 2 to 9, a further reduction in the band gap energy was obtained by introducing a substituent to Smanen. Further, FIG. 18 also shows UV-VIS absorption spectra of the organic semiconductors (thin films) of Examples 4 and 6. As shown in the figure, both the case where a methoxy group which is an electron donating group is introduced (Example 4) and the case where a trifluoromethyl group which is an electron withdrawing group is introduced (Example 6) are large in the long wavelength region. Absorption was present.

[Electron mobility]
Electron mobility (hole mobility) was measured for the organic semiconductors (thin films) of Examples 2 to 19 produced as described above. The measurement was carried out in a glove box connected to a vacuum vapor deposition machine used for organic semiconductor production, and everything from organic semiconductor production to electron mobility (hole mobility) measurement was consistently performed in an argon gas atmosphere. Two electrometers (trade name: K2400) manufactured by KEITHLEY were used as measuring instruments. As a measuring method, a field effect transistor evaluation method was used, and hole mobility μ (cm ² · V ⁻¹ · s ⁻¹ ) was calculated by the following formula 9. In Equation 9, W is the channel length (cm) in the field effect transistor, and in this embodiment, W is 20 μm (2.0 × 10 ⁻³ cm). L is the channel width (cm), and in this embodiment, L is 5.0 mm (5.0 × 10 ⁻¹ cm). Ci is the capacitance (F / cm ² ) of the SiO ₂ layer, and in this embodiment, Ci is 11 nF / cm ² (1.1 × 10 ⁻⁸ F / cm ² ). Ids represents a saturation current value between the drain and the source. In the present embodiment, the drain-source current value (Id) at the drain-source voltage of 100 V is regarded as Ids and approximated. Vg represents a gate voltage (V), and Vt represents a threshold voltage (V).

(Equation 9)
Ids ^1/2 = (μWCi / 2L) ^1/2 (Vg-Vt)

In FIG. 19, the measurement result of the said field effect transistor evaluation method in the organic semiconductor (thin film) of Example 13 is shown. In the figure, the horizontal axis represents the drain-source voltage Vd (V), and the vertical axis represents the drain-source current value Id (A). As described above, the organic semiconductor thin film of Example 13 is a thin film in which S-Ph-OCH ₃ (compound (103)) is formed by spin coating. FIG. 20 shows the measurement results of the above-mentioned field effect transistor evaluation method in the organic semiconductor (thin film) of Example 4. In the figure, the horizontal axis represents the drain-source voltage Vd (V), and the vertical axis represents the drain-source current value Id (A). As described above, the organic semiconductor thin film of Example 4 is a thin film in which the same S-Ph-OCH ₃ (compound (103)) as in Example 13 was formed by a vapor deposition method.

As shown in FIGS. 19 and 20, the organic semiconductor thin film of Example 13 formed by the spin coating method and Example 4 formed by the vapor deposition method showed the amplification effect of the p-type characteristics. Further, when the hole mobility μ was calculated based on the above (Equation 9), it was 1.1 × 10 ⁻⁵ (cm ² · V ⁻¹ · s ⁻¹ ) in Example 13, and 7 in Example 4. It was 0.0 × 10 ⁻⁷ (cm ² · V ⁻¹ · s ⁻¹ ), and all showed good values. That is, the organic semiconductor thin films of Examples 4 and 13 all showed useful properties for the use of organic transistors, particularly field effect transistors or thin film transistors.

  As described above, the organic semiconductor of the present invention has high performance and can be used for various electronic devices, and is particularly useful as an organic transistor material. The electronic device of the present invention, particularly the transistor, has excellent performance by including the organic semiconductor of the present invention. The organic semiconductor of the present invention can be particularly preferably used for, for example, a field effect transistor or a thin film transistor. Moreover, the organic semiconductor of this invention is not limited to an organic transistor, It can be used for all other electronic devices. The organic semiconductor of the present invention can be used for electronic devices of the same type as electronic devices in which known organic devices, organic semiconductors, conductive polymers and the like are used, and more specifically, for example, capacitors, It can also be used for electronic devices such as capacitors, batteries, organic EL, fuel cells, and organic solar cells.

It is a UV-VIS spectrum diagram of Smanen, and the solvent used is CHA. It is a UV-VIS spectrum diagram of Smanen, and the solvent used is THF. It is a UV-VIS spectrum diagram of Smanen, and the solvent used is CH ₃ CN. A UV-VIS spectrum of the sumanene, used solvent is CH ₂ Cl _2. It is the figure which put together and showed all the spectrum diagrams of FIGS. It is the schematic which looked at the molecular arrangement | sequence in a sumanen crystal | crystallization from the molecular side. It is the schematic which looked at the molecular arrangement | sequence in a sumanen crystal | crystallization from the molecule | numerator upper surface. It is a UV-VIS absorption spectrum figure of su-ph (compound (101)) and sumanen. It is a fluorescence spectrum figure of su-ph and sumanen. It is a figure which shows UV-VIS absorption spectrum and fluorescence spectrum of su-ph together. It is a UV-VIS absorption spectrum figure of su-ph-Me (compound (102)), su-ph-OMe (compound (103)), and su-ph (compound (101)). su-ph-Cl (Compound (104)), a UV-VIS absorption spectrum of the su-ph-CF ₃ (compound (105)) and su-ph (compound (101)). It is a UV-VIS absorption spectrum figure of su-1T (compound (106)), su-3T (compound (108)), and sumanen. It is a figure which shows together the UV-VIS spectrum and fluorescence spectrum of su-1T. It is a figure which shows the UV-VIS spectrum and fluorescence spectrum of su-3T together. It is a figure which shows collectively the fluorescence spectrum of su-ph (compound (101)), su-1T (compound (106)), and su-3T (compound (108)). It is a figure which shows the energy level of the organic semiconductor of Examples 1-7 and 9. It is a figure which shows collectively the UV-VIS absorption spectrum of the organic-semiconductor thin film of Example 4 and 6. It is a figure which shows the measurement result of the field effect transistor evaluation method in the organic-semiconductor thin film of Example 13. FIG. It is a figure which shows the measurement result of the field effect transistor evaluation method in the organic-semiconductor thin film of Example 4. FIG.

Claims (13)

A transistor comprising an organic semiconductor comprising at least one selected from the group consisting of compounds represented by the following general formula (1), tautomers thereof, stereoisomers thereof, and salts thereof.
In formula (1), A ^{1 to} A ⁶ are hydrogen atoms,
X ^{1 to} X ³ are the same or different and are each a methylene group substituted with an allyl group (the following formula (2)) or a vinylidene group substituted with a phenyl group, a thiophene group or a polythiophene (the following formula (3)) And the phenyl group may be further substituted with one or more substituents, the substituents being the same or different from each other, wherein the substituents are halogen, methyl group, hydroxy group, methoxy A group, an oxo group, an amino group or a trifluoromethyl group.
The transistor containing the organic semiconductor of Claim 1 which has the structure where the molecule | numerator of the compound represented by said Formula (1) or its ion laminated | stacked on the up-down direction. In the compound molecule represented by the formula (1) or an ion thereof, an atom directly bonded to a benzene ring in the sumenene skeleton in the atomic group X ^{1 is} defined as x ^I, and in the atomic group X ² , the atom directly bonded to the benzene ring and x ^II, the atom directly bonded to the benzene ring in sumanene backbone in atomic group X ³ and x ^III, x ^I, the 3 atoms x ^II and x ^III 3. The transistor including an organic semiconductor according to claim 2, wherein the x plane is defined as an x plane, and the x planes of each molecule or ion are parallel to each other in the stacked structure of the molecules or ions thereof. In the compound molecule represented by the formula (1) or an ion thereof, when a triangle having apexes of the three atoms x ^I , x ^II and x ^III is defined, 60 ° ± 10 °, 180 ° ± 10 ° or 300 in the x plane with respect to the triangle of the molecule or ion in which the triangle in any molecule or ion is stacked on or under it The transistor containing the organic semiconductor according to claim 3, which is located at an angle rotated by ± 10 °. The transistor containing the organic semiconductor in any one of Claims 1-4 which has a crystal structure. In the said Formula (1), all of X < ¹ > -X < ³ > is a methylene group, The transistor containing the organic semiconductor in any one of Claims 1-5 . The transistor containing the organic semiconductor in any one of Claims 1-6 containing the complex formation structure of the compound or its tautomer or stereoisomer with the said Formula (1), and a metal element. 8. The transistor including an organic semiconductor according to claim 7, wherein the metal element includes a transition metal element. The transition metal element is yttrium (Y), samarium (Sm), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr). , Molybdenum (Mo), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), iridium (Ir), cobalt (Co), rhodium (Rh), W (tungsten), Ni (nickel) The transistor containing an organic semiconductor according to claim 8 , comprising at least one selected from the group consisting of Pd (palladium), Pt (platinum), and osmium (Os). The transistor containing the organic semiconductor of Claim 1 whose compound represented by said Formula (1) is a compound represented by either of following formula (101)-(109).
The transistor containing the organic semiconductor in any one of Claims 1-10 which further contains a dopant. The transistor comprising the organic semiconductor according to claim 1 , wherein the transistor has a thin film shape. A compound represented by any one of formulas (101) to (109) according to claim 10 , a tautomer or stereoisomer thereof, or a salt thereof.