TW201219382A - Method for producing condensed ring compound and material compound used in this method - Google Patents

Abstract

Provided is a method for producing a dithienothiophene derivative with high yield. This method comprises the following step: reacting a compound represented by formula (1) and a compound represented by formula (2), in the presence of a transition metal complex, to produce a compound represented by formula (3). [ring A and ring B represent aromatic ring, X<SP>1</SP> and X<SP>2</SP> represent halogen atom, etc.] M<SP>1</SP>M<SP>2</SP>Y(Z)m (2)[wherein, Y represents element of group 15 or 16, M<SP>1</SP> and M<SP>2</SP> represent alkali metal, etc., Z represents hydrogen atom, etc., m represents 1 or 2.] [ring A, ring B, Y, Z and m represent the same meaning as the above mentioned.].

Description

201219382 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a condensed ring compound, and a raw material compound used in the method. [Prior Art] A dithienothiophene derivative as an organic semiconductor material was reviewed. Manufacturing two. The method of the phenanthrene derivative is proposed by the following two steps (Non-Patent Document 1): 3,3'-dibromo-2, 2'-bithiophene (3, 3'-dibromo) -2, 2'-bithiophene) derivative 1 step of dilithiolation; and reacting the product formed in the first step with bis(phenyl sulfonyl) sulfide (bis(phenyl sulfonyl)sulfide) Step 2. [Prior Art Document] [Non-Patent Document] [Non-Patent Document 1] Advanced Materials, 2007, vol. 19, 3008. [Summary of the Invention] (The subject of the invention is to be solved) However, it is derived from the thienothiophene of the prior art. There is a problem in that the yield of the phenanthrene derivative is too low. Accordingly, an object of the present invention is to provide a high-yield production method for producing a condensed cyclic compound of a dithienothiophene derivative as a representative example. (Method for Solving the Problem) 4 323286 201219382 . That is, the present invention * provides a method for producing a compound of the formula (3): the method comprises the following reaction steps: in the presence of a transition metal complex The compound represented by the formula (1) is allowed to react with the compound represented by the formula (2).

(wherein the A ring and the B ring each independently represent an aromatic ring. γ represents a 15th = a di- or a group 16 element. The oxime each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. m represents G or When by is a group 15 element, the melon is 1; when it is a group 16 element, m is 〇.) X1 X2 (1) (wherein the A ring and the B ring system have the same meaning as described above. X1 and X2 are independent tables respectively. Not a 4-atom atom, an aikyi sulfonate group or an aryl sulfonate group.) M, V) m (2) (wherein Μ1 represents an alkali metal atom or a magnesium halide group. Μ2 represents a base A metal atom, a magnesium halide group or a hydrogen atom. The ruthenium, osmium and m groups have the same meanings as described above.) Further, the present invention provides a process for producing a compound represented by the formula (3), which comprises the following reaction steps: In the presence of a complex, the compound represented by the formula (4) is subjected to an intramolecular cyclization reaction of 5 323286 201219382.

(wherein the A ring and the β ring each independently represent an aromatic ring. γ represents a Group 15 element or a Group 16 element. The oxime each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. m represents ruthenium or osmium. When 〇γ is a group 15 element, 111 is j, and Y is a group 16 element, and m is 〇.)

(4) (wherein M3 represents a typical metal atom or a toothed singular group. χ2 represents a functional element atom, a decyl acrylate group or an aryl acid vine group. Anthracene ring, anthracene ring, γ, hydrazine and melon The same meaning as the above ^) Further, the present invention provides a compound represented by the formula (4). (Z)m ΥΜ3 γ2

(4) (In the formula, Μ represents an atypical metal atom or a magnesium halide group. The anthracene ring and the β ring each represent an aromatic ring. X2 represents a dentate atom, an alkyl sulfonate group or an aromatic 6 323286 201219382 Acid ester group. Y represents a Group 15 element or a Group 16 element. Z represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. m represents 〇 or 1»Y is a Group 15 70 molecule, m is 1, When Υ is a Group 16 element, m is 0.) Further, the present invention provides a compound represented by the formula (5). (?)m

(In the formula, the A ring and the B ring each independently represent an aromatic ring. χ 2 represents a halogen atom, an alkyl sulfonate group or an aryl sulfonate group. Υ represents a Group 15 element or a 16th no τ 素. Independently represents a hydrogen atom, a pyridyl group, an aryl group or a heteroaryl group. m represents 〇 or γ is a group 15 element, and 4 i, γ is a group μ element, m is 〇.) (Effect of the invention) The present invention can produce a condensed ring compound of a dinonphene porphin derivative as a representative example in a high yield. [Embodiment] Hereinafter, embodiments of the present invention will be described. &lt;First Manufacturing Method of the Invention&gt; The f manufacturing method is a compound represented by the above formula (3), which comprises the following steps: in the presence of a transition metal complex, = (1) silk compound (four) pre-material (2) Compounds &lt;Compounds represented by formula (1)&gt; 323286 7 201219382 In the above formula (1), the A ring and the B ring each independently represent an aromatic ring. The aromatic ring may have a substituent. The aromatic ring preferably has a carbon number of from 2 to 60, more preferably from 2 to 22, still more preferably from 3 to 14. The carbon number of the substituent having an aromatic ring is not included in the carbon number. Examples of the aromatic ring include a stupid ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, an anthracene ring, an anthracene ring, a ring, an oxadiazol ring, and a oxodiazole ( Thiadidiazole ring, mouth, etc. 0 guole ring, porphin ring, α ratio p ring, astringent ring, pyrabit, pyrazine ring, pyrimidine ring, triazine Cyclothiophene ring, benzothiophene ring, benzopyrene ring, benzoheptane ring, quinolone ring, isoquinol ring, thieno[3,2-b]thiophene ring, porphin [2, 3-b] thiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring and the like. The A ring and the B ring system may form a multi-ring structure via a ring. Examples of such compounds are the compounds of the formula (1-2) and the compounds of the formula (1-34) described below. The aforementioned A ring and B ring are each independently, and are preferably an aromatic five-membered heterocyclic ring. The five-membered heterocyclic ring may also be condensed with other rings. In the above formula (1), examples of the halogen atom represented by X1 and X2 include a fluorine atom, a gas atom, a bromine atom, and an iodine atom. In the above formula (1), the alkyl sulfonate group represented by X1 and X2 may, for example, be a methanesulfonate or a trifluoromethane ester group. In the above formula (1), the arylsulfonate group represented by X1 and X2 may, for example, be a sulfonate group or a para-toluene sulfonate. In the above formula (1), from the viewpoint of the reaction yield, X1 and X2 are preferably a gas atom, a bromine atom or an iodine atom, more preferably a bromine atom or an iodine atom. 8 323286 201219382 The compound represented by the formula (1) is preferably a compound represented by the formula (A) and a compound represented by the formula (1B).

In the formula (1A), R each independently represents an alkyl group, an alkoxy group, a thiol group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amine group, a substituted amine group, a fluorenyl group, a substituted hydrazine. a group, a halogen atom, a fluorenyl group, a decyloxy group, a decylamino group, a heteroaryl group, a carboxyl group, a substituted carboxy group, a nitro group or a cyano group. η represents an integer of 0 to 2. The two n's may be the same or different. When Ri is a plural, it may be the same or different from each other. "At 2 o'clock, regardless of the aforementioned meaning of Ri, the adjacent R1 may be bonded to each other, and together with the carbon atoms of the respective bonds, form a residual structure. E each independently represents _Q_, 令, 备, or N (R)-.R each independently represents an alkyl group, an aryl group or a heteroaryl group. The two e's may be the same or different. The oxime 1 and the X2 are the same as defined above. The cyclic structure is equivalent to saturated or unsaturated. Monocyclic or polycyclic slope % or rotation. Examples thereof include a benzene ring, a (tetra) ring, an epoch ring, a pyrrole ring, a naphthalene ring, a thienothiophene ring, a stupid thiophene ring, a cyclopentane ring. , cyclohexane ring, and the like.

In the formula (1Β), ρ represents an integer from 〇 to 4. The two ρ can be the same or different. R2 each independently represents alkyl, alkoxy, alkylthio, aryl, aryloxy 9 323286 201219382, arylthio, dilute, fast radical, amine, substituted amine, fragment, substituted a functional atom, a fluorenyl group, a decyloxy group, a decylamino group, a heteroaryl group, a thiol group, a substituted carboxy group, a nitro group or a cyano group. When R2 is plural, they may be the same or different from each other. When the carbon atoms adjacent to each other in the benzene ring have a group represented by R2, R2 of the adjacent carbon atoms may be bonded to each other without forming the ring structure, and the adjacent carbon atoms may form a ring structure. E each independently represents _0_, _S-, _Se_ or _N(R3)_. R3 each independently represents a non-alkyl group, an aryl group, and a heteroaryl group. The two Es can be the same or different. X1 and X2 have the same meaning as described above. The cyclic structure corresponds to a saturated or unsaturated monocyclic or polycyclic hydrocarbon ring or heterocyclic ring. Examples thereof include a benzene ring, a sigma ring, a porphin ring, an 11-pyrrole ring, a naphthalene ring, a thienothiophene ring, a benzothiophene ring, a cyclopentane ring, a cyclohexane ring and the like. Here, the alkyl group has a carbon number of usually from 1 to 60, preferably from 1 to 20. The alkyl group may, for example, be an alkyl group, an ethyl group, a n-propyl group, a n-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecanyl group or a tetradecyl group. , 16 yards, octadecyl, decyl, trifluoromethyl, perfluorohexyl, perfluorooctyl and so on. The alkoxy group has a carbon number of usually from 1 to 60, preferably from 1 to 20. The alkoxy group may, for example, be an methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, a decyloxy group, or twelve. Alkoxy, trifluoromethoxy, perfluorohexyloxy, perfluorooctyloxy, methoxydecyloxy, 2-ethoxyethyloxy, and the like. The alkylthio group has a carbon number of usually 1 to 60, preferably 1 to 20. The alkylthio group 10 323286 .201219382 may, for example, be a butylthio group, a hexylthio group, an octylthio group or a dodecylthio group. The aryl group is an atomic group which removes a hydrogen atom bonded to a ring carbon atom from an aromatic hydrocarbon, and includes a group having a benzene ring and a group having a condensed ring. The aryl group may have a substituent, and the aryl group other than the substituent has a carbon number of usually 6 to 6 Å, preferably 6 to 20. Examples of the aryl group include a phenyl group, a naphthyl group, a 2-naphthyl group, a diterpene group, a 2-fluorenyl group, a 9-fluorenyl group, a 4-tetracenyl group, a 2-fold fused tetraphenyl group, a 5-fused tetraphenyl group, and a diphenyl group. , 2_fluorenyl, 4_fluorenyl, 2_mercapto, 3-indenyl, 2-gyl, 3-gyl, 4-indenyl, 1-extended biphenyl U-biPhenyienyi), 2-stretch Biphenyl, 2_phenanthryl, 9-phenanthryl and the like. The aryloxy group may have a substituent, and the carbon number of the aryloxy group other than the substituent is from 6 to 6 G ', preferably from 6 to 20. The aryloxy group may, for example, be a phenoxy group, a naphthyloxy group, a 2-naphthyloxy group or a pentafluorophenoxy group. The arylthio group may have a substituent, and the carbon number of the substituted filamentary base is from 6 to 60 Å, preferably from 6 to 2 Å. Examples of the arylthio group include a phenylthio group, a naphthylthio group, a 2-naphthylthio group, a pentafluorophenylthio group and the like. The number of carbon atoms of the alkenyl group other than the substituent is usually . The alkenyl group may be an ethylene group, a octenyl group, or an alkenyl group which may have a substituent, and is 2 to 60, preferably 2 to 2 fluorene 2-stene vinyl group or the like. = base can be (four) take the lead, minus the material outside the new (four) is usually 2 to +60, preferably 2 to 2 〇. Examples of the block group include an ethyl bromide group, a 2-phenylethynyl group, a tri-indenyl ethynyl group, and the like. The carbon number of the soil is usually from 〇 to 6〇'. (1) The group of the wind can be exemplified by a 1 group amino group, a dimethylamino group, an ethylamino group, a diethyl 323286 11 201219382 amine group, dipropylamine a group, a phenylamino group, a diphenylamino group, a methyl phenyl 2-naphthylamino group, a pentafluorophenylamino group, and a tetraamine-based amine. The carbon number of the base group and the substituted fluorenyl group is usually For the 丨 〇 〇 〇 〇 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳Examples of the halogen atom include a fluorine atom, a gas atom, and a sulfonium sulfonium group, and the carbon number is usually 2 to 20. The fluorenyl group may be a fluorene atom. The aryl group, the triethylene ethane group, and the five gas group: The carbon number of the diyl group and the ethoxy group is usually 2 to 20. The decyloxy group may be exemplified by a group, a propenyloxy group, a taurotyl group, a (tetra)oxy group, a trifluoropyroxyfluorobenzyloxy group, or the like. The inverse number of the base and the saponin is usually 2 to 2 〇. 醯 可 可 、, 乙 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺Amidino-tris(10)amino group, = guanylamino group, etc. The one heteroaryl group may have a substituent, and the carbon number of the substituent group is usually from 3 to 60', preferably from 3 to 2%. The heteroaryl group may be a 3-carbenyl group, an anthranyl group, 2_ squara, 3_^nanyl, 2-oxazolyl, 2-thiazolyl, 2-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-benzofuranyl, 2 -benzothiophenyl, 2-thienothiophenyl, etc. The carbon number of the substituted carboxylic acid group is usually from 2 to 20. The substituted carboxylic acid group may be exemplified by a carboxylic acid hydrazine vine group, a certain acid ethyl acetonate group, and a slow acid benzene group. 12 323286 201219382 In the above formula (1A), E is independent, preferably -0-, -S-, -Se-, more preferably -S-. In the formula (1B), E is independent, It is preferably -0-, -S---Se-, more preferably -S-. Examples of the compound represented by the above formula (1) include the following compounds.

(1-5)

Br Br

(1-18) (1-19) 13 323286 201219382

0·20) (1-21) (1.22)

Br Br

(1-31)

(1'32)

(1-36) Among the compounds of the formula (1-1) to the formula (1-37), preferred are the formula (1-8) to the formula (1-21), the formula (1-24) to the formula (1-26) a compound of the formula (1-31) to (1-33), a formula (1_&quot; 36), more preferably a formula (1-11) to a formula 〇20), a formula (丨24), a formula (1- 32), a compound of the formula (1-33), the formula (1-36), more preferably a compound of the formula (1 - to the formula (1-20). 323286 14 201219382 &lt;a compound represented by the formula (2)&gt; In the above formula (2), examples of the alkali metal atom represented by M1 include a lithium genus, a nano atom, a clock atom, and the like. In the above formula (2), a magnesium chloride group represented by M1 may be exemplified by a magnesium chloride group. In the above formula (2), the alkali metal atom represented by M2 may, for example, be a lithium atom, a nano atom, or a trait atom. In the above formula (2), M2 represents The functional magnesium group can be exemplified by magnesium chloride group, desert magnesium base, bismuth base group, etc. M2 is preferably a metal atom and a halogenated town base. From the viewpoint of easy availability of raw materials and easy preparation of raw materials, M1 and M2 is preferably the same. In the above formula (2), the 15th element represented by Y In the above formula (2), the group 16 element represented by Y may be, for example, oxygen, sulfur or lithene. Y is preferably a group 16 element, more preferably sulfur. In the above formula (2), the definition of the nodal group, the aryl group, and the heteroaryl group represented by Z, and the specific examples are the definitions and specific examples of the alkyl group, the aryl group, and the heteroaryl group represented by R1 in the above formula (1A). In the above formula (2), m represents 0 or 1. When 丫 is a group 15 element, m is 1; when Y is a group 16 element, m is 0. The compound represented by the above formula (2) may be An anhydrate or a hydrate. For example, sodium sulphide sulphate and sodium sulphide sulphide are also included in the compound represented by formula (2): 15 323286 201219382. In the production method of the present invention, relative to the above formula (1) The compound represented by the above formula (2) is used in an amount of 1 mol or more, preferably 1 to 100 mol, more preferably 1 to 10 mol, relative to the compound represented by the formula (1). When the compound represented by the formula (2) is used in an amount of 1 mol or less, the amount of Y used to form the condensed ring is insufficient, and the condensed cyclized product is obtained. The compound represented by the above formula (2) is exemplified by the following compounds: ϋ2Ρ~0 LiaAs—(2-1) (2-2) (2-3) Na20 Na2S Na2S· 5H20 Na2S*9H20 (24) ( 2-5) (2-6) (2-7) Li2Se Na2Se Na2Se· 5 HjO Na2Se- 9 H2〇(2-8) (2-9). (2-10) (2-11) NaOH NaSH NaSeH LiSeH (2-12) (2-13) (2-14) (2-15) 〇(MgCI)2 〇(MgBr)2 S(MgBr)2 Se(MgBr&gt;2 (2-16) (2-17) (2-18) (2-19) Among the compounds of the formula (2-1) to the formula (2-19), a compound of the formula (2-1) to the formula (2-11) is preferred, and more preferably a formula (2-4) The compound of the formula (2-11), more preferably a compound of the formula (2-5) to the formula (2-7). &lt;Compound represented by formula (3)&gt; In the above formula (3), the A ring, the B ring, the Y, Z, and m are the same as the A ring, the B ring, the Y, Z, and m of the above formula (1). significance. 16 323286 201219382 The compound represented by the formula (3A) can be produced by reacting a compound represented by the above formula (1A) with a compound represented by the above formula (2) in the presence of a transition metal.

In the formula (3), 1^, 11, ¥, 2, 111, and £ have the same meanings as described above. The compound represented by the formula (3B) can be produced by reacting a compound represented by the above formula (1B) with a compound represented by the above formula (2) in the presence of a transition metal.

In the formula (3B), R2, p, Y, Z, m and E have the same meanings as described above. Examples of the compound represented by the above formula (3) include the following compounds. 17 323286 201219382

(3-11)

(3·13) (3-12)

(3-16) 2. In the first production method of the present invention, when the oxime of the compound represented by the formula (2) is a hydrogen atom, the compound represented by the formula (2) and the above formula are present in the presence of a transition metal. The compound represented by the formula (5) can be obtained by the reaction of the compound represented by (1). 18 323286 201219382

(Z)m

(5) &lt;Compound represented by formula (5)&gt; Formula (5). The A ring, the B ring, the oxime 2, the γ, the z, and the like are the same as those described above. The preferred form of the compound represented by the above formula (5) is a compound represented by the formula (10) represented by the formula (5B). (Z)m YH X2 (SA)—In the formula (5A), 'R1 independently represents an alkyl group, an alkoxy group, a sulfur group, a aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, or an amine group. , substituted amino group, f group, substituted fragment, im group atom, acid group, decyloxy group, arylamino group, heteroaryl group, carboxyl group, substituted carboxyl group, nitro group or cyano group. n represents the integer from 〇 to 2. The two η can be the same or different. When f is plural, the same can be different. When η is 2, regardless of the above definition of R, adjacent Κ may be mutually bonded, and together with the carbon atoms bonded to the respective R, form a cyclic structure. Ε Each independently represents -〇---s~, -Se- or -N(R3)~. Y々人 ^ κ each independently represents an alkyl group, an aryl group, and a heterocyclic group. The two Es can be the same or different. γ z m and X 2 have the same meanings as described above. 323286 19 201219382

In the formula (5B), p represents an integer of 0 to 4. Both ps may be the same or different. R2 each independently represents an alkyl group, an alkoxy group, a thiol group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amine group, a substituted amine group, a fluorenyl group, a substituted fluorenyl group, a halogen atom, or a hydrazine. A group, a decyloxy group, a decylamino group, a heteroaryl group, a carboxyl group, a substituted carboxyl group, a nitro group or a cyano group. When R2 is plural, the numbers may be the same or different. When the carbon atoms adjacent to each other in the benzene ring have a group represented by R2, the definition of R2 is not limited, and R2 of the adjacent carbon atoms may be bonded to each other to form a cyclic structure together with the adjacent carbon atoms. E each independently represents -〇-, -S-, -Se- or -N(R3)-R3 represents an alkyl group, an aryl group or a heteroaryl group. The two Es can be the same or different. Y, Z, m and X2 have the same meanings as described above. In the above formula (5A), E is independently independent, and preferably _0_, _S_, _Se_' is more preferably -S-. In the above formula (5B), E is each independently, preferably -0---S---Se-, more preferably -S-. Examples of the compound represented by the above formula (5) include the following compounds. 20 323286 201219382 SH Br (5-1) SH Br

(5-6) (5-7) OH Br

SH Br

丨丨八丨丨 (5-8) SH Br

(5-9) SH Br

(5*10) SH Br SH Br SH Br

(S-18) (5-19) 21 323286 201219382

(5-20)

(5-22)

Among the compounds represented by the formulae (5-1) to (5-28), preferred are the formulae (5-8) to (5-21) and (5-24) to (5-26). The compound represented by the formula (5-11) to the formula (5-20), the compound represented by the formula (5-24), and more preferably the formula (5-11) to the formula (5-20). Expressed as a compound. The compound represented by the formula (4) can be selected by grouping the compound represented by the above formula (5) with, for example, a metal group, a metal hydride, an alkylmetal, and a halogenated group. The reaction substance is obtained by reaction. (Z)m

(4) (Z)m ΥΗ X2

Alkali metal, alkali metal hydride, alkyl metal, alkyl hydrazine, etc. 22 323286 201219382 In the formula (4), M3 represents a typical metal atom or a magnesium halide group, and the X2, anthracene ring and an anthracene ring system have the same meaning as described above. m, the metal can be enumerated: lithium, sodium, and the like. Examples of the alkali metal hydride include lithium hydride, sodium hydride, and the like. The alkyl metal hydride may, for example, be a mercapto-based magnesium such as a mercaptolithium or a butyl group, and examples thereof include mercapto-calcium oxide, ethyl-mercapto-magnesium bromide, and ethylmagnesium bromide. ~1:1 money, A The compound represented by the above formula (4) can be used to produce a compound. In the second production method of the present invention, the formula (3) will be described later, and in the compound represented by the formula (4), "is an alkali metal". The compound of the group is produced by the method of the invention of the present invention or the magnesium intercalation. In the second reaction method of the present invention, the second production method of the present invention is a production method according to the above formula (3), which comprises the Q substance in the presence of a transition metal. The step of the compound undergoing an intramolecular cyclization reaction. (A compound represented by the formula (4) is represented by the above formula (4), and the metal of the above formula (4) is a substrate. The alkali metal atom may be a lithium atom or an alkali metal. In the above formula (4), M3 represents Chemical, potassium atom, etc. Magnesium, molybdenum magnesium ^ Self-financing list: magnesium chloride, filling: the compound represented by the pound is better than the compound, the compound represented by the formula (4Β). 323286 23 201219382

In formula (4), R1 each independently represents alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, alkenyl, alkynyl, amine, substituted amine, sand, substituted stone An oxime group, a halogen atom, a brewing group, a decyloxy group, a arylamino group, a heteroaryl group, a carboxyl group, a substituted carboxyl group, a nitro group or a cyano group. η represents an integer of 0 to 2. The two η can be the same or different. When R1 is plural, the same may be the same or different. When η is 2, R1 may be bonded to each other regardless of the definition of R1, and a ring structure may be formed together with the carbon atoms bonded to the respective R1. Ε Each independently represents -0, -S~, -se~ or -N(R3)-. R3 each independently represents a substituent, an aryl group, and a heteroaryl group. The two towns are the same or different. Y, Μ3, Z, m and X2 have the same meanings as described above.

In the formula (4B), p represents an integer of 0 to 4. Both ps may be the same or different. R 2 each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryl group, an arylthio group, a dilute group, an alkynyl group, an amine group, a substituted amine group, a fluorenyl group, a substituted fluorenyl group, a halogen atom, Alkyl, decyloxy, decylamino, heteroaryl, hydrazine or substituted carbonyl, nitro or cyano. When R2 is plural, the terms may be the same or different. When the adjacent carbon atoms in the benzene ring respectively have a group represented by R, the shovel 323286 24 201219382 is defined in R. The R2 of the adjacent carbon atoms may be bonded to each other, and the adjacent carbon is The atoms together form a ring structure. E each independently represents -0, -s-, -Se- or -W)_. R3 each independently represents an alkyl group, an aryl group, or a heteroaryl group. The two Es can be the same or different. The γ, M3, z, m &amp; χ2 series have the same meanings as described above. In the description (4Α), ’ is independent, preferably _〇---s---Se, more preferably _S-. In the above formula (4B), 'E' is independent, preferably _〇---s---Se_, more preferably -S-. The compound represented by the above formula (4) is exemplified by the following compounds.

SNa Br

(4-10) 323286 25 201219382

(4-11&gt; SNa Br

(4-12)

ΌΌ4Η9

SMgBr

(4-20) (4-21) (4-22)

(4-23)

SeU I

(4-24)

(4_27) (4-28) Among the compounds of the formulae (4-1) to (4-28), preferred are the formula (4-8) to the formula (4-21), the formula (4-24) to the formula The compound of (4-26) is more preferably a compound of the formula (4_ιι) to the formula (4_2〇), the formula (4-24), still more preferably a compound of the formula (411) to the formula (4-20). 323286 26 201219382 &lt;Transition metal complex&gt; The transition metal complex according to the first production method and the second production method of the present invention is preferably a transition metal complex containing a Group 8 to 10 element. More preferably, it is a transition metal complex containing a Group 10 element, more preferably a palladium complex, a nickel complex, and particularly preferably a palladium complex. The aforementioned transition metal complex preferably has at least one phosphine ligand. The transition metal complex also contains a transition metal complex precursor. Here, the transition metal complex precursor means a composition converted into a transition metal complex in the reaction system, which is a composition containing a transition metal complex of a precursor and a phosphine ligand or a scale salt. Other examples include: hydrazine (triphenylphosphine) palladium (0), hydrazine (triphenylphosphine) palladium (0) (including ortho, meta, and various substituted isomers), double ( Triphenylphosphine) palladium(II) dichloride, bis(tricyclohexylphosphine)palladium dichloride (11), bis(diethylphosphine) di-palladium (palladium), [1,2-double ( Diphenylphosphino)ethane]palladium dichloride (11), [丨,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride ([1,1 -bis( Diphenylphosphino) ferrocene] palladlum (1)) dichloride), bis(acetonitrile) dichloride (1)), and bis(benzonitrile) palladium dichloride (ruthenium). Among them, ruthenium (triphenylphosphine) is preferably substituted for (ruthenium) and osmium (trimethylphosphine) (including ortho, meta, and various substituted isomers). The nickel complex compound may be exemplified by ruthenium (triphenylphosphine) nickel (ruthenium), bis(triphenylphosphine) nickel dihydride (ruthenium), and [1,2-bis(diphenylphosphino)ethane. Nickel dichloride (11), [1,3~bis(diphenylphosphino)propane] nickel (II), [1,4- 27 323286 201219382 bis(diphenylphosphino)butane Di-vaporized nickel (II), [1, bis-bis(diphenylphosphino)ferrocene] nickel (II), etc. The transition metal complex of the foregoing precursor may be exemplified by Pd2(dba)3 (where dba represents trans, trans'dibenzylideneacetone), Pd(dba)2, palladium acetate (II), bis(1,5-cyclooctadiene)nickel (0), and the like. Among them, Pd2(dba)3, Pd(dba)2, and acetic acid le(II) are preferred. The foregoing phosphine ligand may, for example, be a trialkylphosphine such as tri(n-butyl)phosphine, tri(tert-butyl)phosphine, :1⁄4-hexyl scale, tricyclopentylphosphine or trisylphosphine; a phosphine, dimethylphenylphosphine (including ortho, meta, and various substituted isomers thereof), methoxyphenyl phosphine (including ortho, meta, and various substituted isomers thereof); Diarylsilylphosphines such as diphenylcyclohexylphosphine; dialkylhexylphenylphosphines, dialkylarylphosphines such as (2~biphenyl)bis(t-butyl)phosphine, 'bis(diphenyl) Phosphine) ethane, 1,3-bis(diphenylphosphino)propane, hydrazine, bis(diphenylphosphino)cyclohexane, 1,3-bis(diphenylphosphino)benzene, 1,1,-double ^ A class of bidentate phosphines such as ferric iron. 1. The cross is preferably a di(t-butyl)phosphine, a tricyclohexylphosphine, or a (2-butyryl) bis(t-butyl)phosphine. The squamous salt is the above-mentioned phosphine ligand and the likes of HBFo HPF6, HSbFe and the like, which can be listed as 崴··/ 孤卜. Di(n-butyl) squamous tetrafluoroborate, tris(tert-butyl) scale : Fluorine micro-salt, three stupid base, six gas _ acid salt, triphenyl squamous hexafluoride acid sputum. Among them, tris(t-butyl)sulphate tetrafluoroborate is preferred. When the scale salt is used, in order to convert the scale salt into a phosphine 28 323286 201219382 ligand in the reaction solution, the test may be added. • Examples of the base include sodium hydroxide, potassium argon oxide, sodium acetate, acetic acid 'unloading, sodium carbonate, carbonic acid, carbonic acid, sodium fluoride, potassium fluoride, sodium citrate, and acid clock. Among them, sodium carbonate, potassium carbonate, and carbonic acid planing are preferred. The transition metal complex is adjusted to the amount of transition metal complex used in the precursor to provide an appropriate amount of transition metal in the reaction system. The suitable amount of transition metal in the compound 1 molar reaction system represented by the above formula (1), formula (1A), formula (1B), formula (4), formula (4A) or formula (4B) is 〇 〇〇〇1 to 10 mol' is preferably from 0.001 to 1 mol, more preferably from 1 to 0.5 mol. The amount of the transition metal complex is preferably used in comparison with the compound represented by the above formula (1), formula (1A), formula (1B), formula (4), formula (4A) or formula (4B). It is from 0.0001 to 10 m, more preferably from 1 to i. The precursor is a transition metal complex with respect to the compound represented by the above formula (1), formula (1A), formula (1B), formula (4), formula (4A) or formula (4B). The amount used is preferably 0.0001 to 1 Torr, more preferably 〇〇〇. The phosphine ligand is preferably used in an amount of from 1 to 10 moles, more preferably from i to 4 moles, per mole of the transition metal complex i mole relative to the precursor. The scale salt is preferably used in an amount of from 1 to 10 moles, more preferably from 1 to 4 moles, per mole of the transition metal complex of the precursor. The base is preferably used in an amount of from 1 to 5 moles, more preferably from 1 to 5 moles, per mole of the scale salt. ' 323286 29 201219382 and the 'transition metal complexes may be used alone or in combination of two or more. The amount of the transition metal complex added to the reaction system can be divided into plural-human's and added one by one. In the production method of the present invention, after the addition of the transition metal complex, the reaction rate decreases after a certain period of time, but the reaction rate can be increased when the transition metal complex is recombined in this state. &lt;Reaction conditions&gt; In the first production method and the second production method of the present invention, the reaction temperature is preferably from 300 c to 300 c. From the viewpoint of efficient reaction, it is more preferably 50 C or more and more preferably 8 c or more. Further, from the viewpoint of suppressing side reactions, it is more preferably 25 (Tc or less, more preferably c. or less. The time is usually 丨 to 2 GM, and it is preferable from the viewpoint that the reaction is sufficiently carried out. The reaction is carried out in the presence of a solvent, but it is preferably carried out in the presence of a solvent. ^ _ 疋仃 When a solvent is used, the solvent is a reaction inert solvent; Or use a mixture of a plurality of solvents. Aromatic hydrocarbon solvents such as aromatic jr ^ hexane, methyl ring, etc.; benzene, nitrogen soluble odor, stupid one

/Compound, 1-methyl-2-pyrrolidone Q N,N-dimethylformamide, N,N-7b 2-,1 id_), 4 aprotic polar solvent; water. More w media, non-good polar solvents. The above-mentioned reaction can be carried out in air, but it is preferably carried out under inert gas atmosphere or under inert gas atmosphere. 323286 30 201219382 Next, the specific description is given. In the reaction operation, first, the gas of the entire reaction vessel is replaced with an inert gas, and then the compound represented by the formula (1), the compound represented by the formula (2), the transition metal complex, and the solvent are added to the vessel and mixed. The resulting mixture is reacted at the desired temperature. After the completion of the reaction, the obtained reaction product is directly concentrated, or the reaction mixture is added to water, and extracted with an organic solvent such as toluene, ethyl acetate, diethyl ether or dichloromethane to concentrate the obtained organic layer. The desired compound represented by the formula (3) can be obtained. Further, the compound can be purified by column chromatography, extraction, recrystallization or steaming. &lt;Reaction mechanism&gt; In the present invention, it is estimated that the compound represented by the above formula (3) is produced by the following reaction mechanism. First, the transition metal complex represented by hydrazine is oxidized and added to the compound represented by the above formula (1) to form a compound represented by the following formula (6). The compound represented by the following formula (6) is subjected to a metal substitution reaction with the compound represented by the above formula (2) to produce a compound represented by the following formula (7). The compound represented by the following formula (7) is obtained by reducting the transition metal complex μ and forming a compound represented by the above formula (4) in which the ruthenium 3 is a metal or a magnesium compound. Hey. 31 323286 (2) 201219382 MX2 MX2

(4) wherein M represents a transition metal complex. Μ1, Μ2, Y, Z, m, X1, X2, A ring and B ring system have the same meanings as described above. Then, the transition metal complex represented by ruthenium is oxidized and added to the compound represented by the above formula (4) to form a compound represented by the following formula (8). The compound represented by the following formula (8) undergoes an intramolecular metal displacement reaction to produce a compound represented by the following formula (9). The compound represented by the following formula (9) is subjected to reduction-removal of the transition metal complex oxime to form a compound represented by the above formula (3), and at the same time, a metal complex ruthenium is regenerated. 32 323286 201219382

(9) W (8) where Μ represents a transition metal complex. M^M^Y'Z'm'X1, X2, A ring and B ring system have the same meanings as described above. The compound represented by the above formula (1) and the compound represented by the above formula (2) are reacted in the reaction system with the compound represented by the above formula (4) in the presence of a transition metal complex. The compound represented by the above formula (3) is produced. In other words, the compound represented by the above formula (3) can be produced from the compound represented by the above formula (1) and the compound represented by the above formula (2) in the presence of a transition metal complex, and the above formula (3) The compound represented by the above formula can be produced from the compound represented by the above formula (4) in the presence of a transition metal complex. &lt;Organic film&gt; Next, an organic film containing the compound represented by the above formula (3) obtained by the production method of the present invention will be described. The appropriate thickness of the organic film varies depending on the element to which the organic film is applied, and is usually in the range of lrnn to 100/zin, preferably 2 nm to 33 323286 201219382 lOOOnm, more preferably 5 nm to 500 nm, still more preferably 20 nm. To 200nm. With such an organic film of equal thickness, it is easier to form an organic thin film element having good charge transportability and sufficient strength. The organic film may be a compound represented by the above formula (3) alone or in combination of two or more. When the organic film contains a component other than the compound represented by the above formula (3), it is preferably contained in an amount of 10% by mass or more, more preferably 30% by mass or more, based on the compound represented by the above formula (3). When the content of the compound represented by the above formula (3) is less than 30% by mass, the film formation becomes difficult, and it is difficult to obtain good charge mobility, and the components other than the compound represented by the above formula (3) are preferable. An organic semiconductor material other than the compound represented by the formula (3). &lt;Organic thin film element&gt; Since the organic thin film of the present invention exhibits high charge transportability, it is possible to transport an electric charge injected from an electrode provided in the organic thin film element or an electric charge generated by absorbing light. With these characteristics, it can be suitably used for organic thin film devices such as organic thin film transistors, organic solar cells, light sensors, and organic electroluminescence displays. It is especially suitable for charge transport materials as organic thin film transistors. (Embodiment) Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. (High Performance Liquid Chromatography (HPLC)) In the examples, the HPLC area percentage value was used by high performance liquid chromatography 34 323286 201219382 (HPLC, manufactured by Shimadzu Corporation, trade name: LC-20AD), used at 254 nm. * The value of the chromatogram measured by the wavelength. The test compound * was dissolved in tetrahydrofuran, and the solution obtained by HPLC was injected. 5 a l. HPLC mobile phase system using 0.1% acetic acid aqueous solution (sputum solution) and adding 〇. 1% acetic acid in acetonitrile (sputum solution), at a flow rate of 0.5 mL / min, set to take 6 minutes, so that A liquid for B The volume ratio of the liquid flows as a gradient of (A liquid) / (B liquid) = 80/20 to 0/100. The column was shampooed using Shim-pack XR-0DS 2. 0 mmx length 75 (manufactured by Shimadzu Corporation). The detector uses a light-emitting diode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A). (Quality Analysis) In the examples, the value of the mass analysis was obtained by AccuTOP TLC JMS-T100TD (manufactured by Nippon Electronics Co., Ltd.). (R R analysis) The compound was dissolved in heavy chloroform, and NMR measurement was carried out using an NMR apparatus (manufactured by Varian Co., Ltd., INOVA300). (Example 1) (Synthesis of 嗔-[3,2-b:4, 5-b']dibenzo[b]°Cetene)

Br Br Pd(PPh3)4

Na2S · 9H20 — _

Ng Ο·”) (3-8) In a 100 mL flask in which the gas in the flask was replaced with nitrogen, 3,3,-dibromo-2,2'-di(benzo[b]thiophene) (0. 10 g, 0·24mmol), sodium sulfide nonahydrate (0. 056g, 〇. 24 〇 〇 1), 肆 (triphenylphosphine) palladium 35 323286 201219382 (0) (Pd (PPh3) 4) (14mg) and 曱 曱 - 2-Pyrrolidone (10 mL), and the mixture was stirred under heating at 160 ° C for 6 hours. The reaction liquid was analyzed by HPLC to obtain an area percentage, the area of the compound (3-8) was 61%, and the area of the compound (1-11) was 25%. (Example 2) Synthesis of oxeno[3,2-b:4,5-b']bisbenzo[b]porphin)

Pd2(dba)3 [PfBuH][BF4]

Na2S · 9H20 K2C03

NMP (1-11) (3-8) In a 100 mL flask in which the gas in the flask was replaced with nitrogen, 3,3'-dibromo-2,2'-di(benzo[b] porphin) was added. 10g, 0. 24mmol), sodium sulphide sulphide (0. 056g, 0.25mmol), potassium carbonate (0.13g, 0.94mmol), ginseng (dibenzylideneacetone) gemini (Pd2(dba)3 (5. 4 mg), tris(t-butyl) scaly tetrafluoroborate (14 mg) and dimercapto-2-pyrrolidone (10 mL) were stirred and heated at 110 Torr for 6 hours. The reaction liquid was analyzed by HPLC to obtain an area percentage, the area of the compound (3-8) was 63%, and the area of the compound (1-11) was 34%. (Example 3) (Synthesis of thieno[3,2-b:4,5-b']bisbenzo[b]thiophene) 36 323286 .201219382

Br Br Pd(PPh3)4

Na2S · 9H20 a ►

NMP was added to a l〇〇mL flask in which the gas in the flask was replaced with nitrogen, and 3, 3, -1 &gt; odor _2, 2 - (the benzo[b] porphin) (〇. 5〇g, 1. 2mmol), sodium sulfide nonahydrate (0.28g, 1.2imnol), pd(PPh3)4 (68mg) and 1-mercapto-2-pyrrolidone (50mL), heated and stirred at 140 °C 1 Hour. Thereafter, Pd(PPh3)4 (68 mg) was added to the flask, and the mixture was heated and stirred at 140 °C for 5 hours. The area of the reaction solution was determined by HPLC to determine the area percentage, the area of the compound (3-8) was 64%, and the area of the compound (1-11) was 〇%. The reaction liquid was poured into 100 mL of water to obtain a precipitate. The precipitate was filtered and washed with methanol to give a solid. The product (3-8) was obtained by the use of a ruthenium. The yield was 53%. 1H _NMR (3 00MHz, CDCI3) S7.89 (m, 4H), 7· 4 7 (m, 2 Η), 7: 3 9 (m, 2H) (mass of the reaction intermediate of compound (3-8) In the third embodiment, the reaction solution after 21 hours from the start of the reaction was subjected to mass spectrometry to obtain a fragment having a m/z of 529.96 and a 〇m/z of 529. 96 was attached to the reaction mechanism. In the case of the compound represented by the above formula (7) and the mass of the compound represented by the above formula (8), the measurement results indicate that the above-mentioned reaction mechanism and intermediate are represented by the above (4). Compound. The structure of the mass detected is a sodium addition represented by the following formula 37 323286 201219382. Both mass numbers are the same as 528.73. It is presumed that in the reaction liquid, the phosphine is coordinated to palladium in the following formula. Fa + Br | Pd 8r SNa Pd j Dec Na JL + Na corresponds to the compound represented by the above formula (7) corresponding to the compound represented by the above formula (8) (Synthesis Example 1) (6-octylbenzo[b]° Synthesis of phenotype) C8H17B(OH)2

PdCI2(dppf) THF n-CeH^^^S7 H2 〇In a 10OmL flask in which the gas in the flask was replaced with IL gas, 6-bromobenzo[b]° thiophene (4. Og, 19 mmol), octylboronic acid was added. (4. 5g, 28mmol), [1, Γ-bis(diphenylphosphino)ferrocene]palladium dichloride (PbCMdppf)) (0. 10g, 0.19mmol) and tetrahydrofuran (120mL) And the aqueous solution of the aqueous solution (2.3 M, 24 mL) was added dropwise while heating under reflux. After the completion of the dropwise addition, the mixture was heated under reflux for 13 hours. The reaction solution was concentrated, terpene and water were added, and a toluene solution was extracted. The toluene solution was concentrated. The 9-octylbenzo[b]thiophene was obtained by the use of a ruthenium tube column. The yield was 52%. 38 323286 201219382

Ή-NMR (300MHz, CDCI3) z, 1 H) , 7· 6 8 (s, 1 H) , 7. 2 • 19 (d, J = 8. 1Hz, 1 H) , 2. H) , 1. 60-1. 7 0 (m, 2H), 1. 20-] Δ n .

1 · 4 〇(m, 1 〇H ), 0. 85 — 0. 94 (m, 3H) (Synthesis Example 2) (6,6 --octyl-2, 2'-di(benzo[b]] Synthesis of porphin) 1) BuLi Et2〇

To a 100 mL flask in which the gas in the flask was replaced with nitrogen, 6-octylbenzo[b]thiophene (1.9 g, 7.6 mmol) and diethyl ether (37 mL) were added. After that, butyllithium (2.6 M, 3.8 mL) was added dropwise to the flask. After the completion of the dropwise addition, the mixture was heated under reflux for 2 hours. The reaction solution was cooled to hydrazine.气, added vaporized copper, llmmol), and then heated to reflux for 2 hours. The reaction solution was filtered, and the organic compound in the filtrate was dissolved in toluene (200mL) and tetrahydrofuran (50mL), and the obtained solution was added to the filtrate. Thereafter, the filtrate was washed with an aqueous acetic acid solution and water. The filtrate was concentrated, and methanol was poured into the concentrate, and the resulting precipitate was filtered. And lg, 6,6, _dioctyl 2,2,_bis(benzo[b]thiophene) 1. lg. The yield was 58%.

I 1H-NMR (300MHz, CDCI3) 57. 66 (d, J=8. 4H 2H), 7. 44 (s, 2H), 7. 1 8 (d 2. 72 (t, J = 7. 7Hz. 4H),1 . z, 2H), 7. 60 (s, 2H) , J = 8. 4 H z, 2H) , 2. _ 6 0- 1. 7 0 (m, 4 H) , i . 5 -0. 9 4 (m, 6 H) 39 323286 201219382 (Synthesis Example 3) (3, 3' - Erqian-6, 6'-dioctyl-2, 2'-di(benzo[b]pyrene Synthesis of pheno)

Into a 100 mL flask, 6,6'-dioctyl-2,2'-bis(benzo[b]decanophene) (1.0 g, 2.0 mmol) and gas (20 mL) were added. Thereafter, bromine (0.68 g, 4.3 mmol) was added dropwise to the flask. Thereafter, it was stirred at room temperature (25 ° C) for 20 minutes. An aqueous solution of gas and sodium thiosulfate was added to the reaction solution, and the organic layer was extracted. The organic layer was washed twice with water, and then the organic layer was concentrated. The concentrated organic layer was refined using a ruthenium tube column. Thus, 3,3'-dibromo-6,6'-dioctyl-2,2'-bis(benzo[1)]thiophene) 0.7 was obtained. The yield was 53%.

1 H-NMR (3 Ο OMH z, CDC I 3) 5 7. 7 9 (d, J = 8. 1 Η ζ, 2Η), 7. 63 (s, 2Η), 7. 33 (d, J = 8. 1 Hz, 2 Η ), 2. 7 7 (t, J=7. 7 Hz, 4 H) , 1. 6 0-1. 7 0 (m, 4 H), 1. 20-1. 40 (m, 20H), O. 8 5-0. 94 (m, 6H) (Example 4) (2,7-dioctylthieno[3,2-b:4, 5-b']bisbenzene And [b] synthesis of thiophene)

Pd2(dba)3 [PfBuH][B'F4]

n-C$H-j7 (1-12) Γ1-〇8Ηΐ7

n-CgH^ (3-7)

Na2S · 9H2〇 K2CO3

NMP was added to a 100 mL flask in which the gas in the flask was replaced with nitrogen, and 3,3'-di-n-6,6'-dioctyl-2,2'-di(benzo[b]sinter) was added (0. 70 g). , 40 323286 201219382 1. lmmol), sodium sulfide hexahydrate (〇 25g, 1. lmmol), carbonic acid unloading (0. 60g, 4.3mmol), Pd2 (dba) 3 (25mg), three (third butyl ) Scale IV. Fluoride acid salt (63 mg) and 1-methyl-2-indole pirone (50 mL) were mixed and heated at 11 ° C for 3 hours. Thereafter, pd2(dba)3 (25 mg) and tris(t-butyl) scallop tetrafluoroborate (63 mg) were added, and the mixture was stirred under heating at 130 t for 10 hours. Thereafter, the reaction solution was injected into decyl alcohol, and the resulting precipitate was filtered. The precipitate was purified using a ruthenium tube column and recrystallized using toluene and 2-propanol to obtain 2,7-dioctylthieno[3,2-13:4,5-13,]bisbenzene. And [13] thiophene 300mg. The yield was 53%.

'H-NMR (300MHz, CDCI3) 8 7. 77 (d, J=7. 8H z, 2H) , 7. 6 9 (s, 2 H) , 7. 2 7 (d, J = 7. 8Hz, 2 H ), 2. 7 5 (t , J = 7. 7 H z, 4 Η) , 1. 6 5- 1. 7 5 (m, 4 H), 1. 2 0- 1 4 0 (m, 2 Ο H) , 0· 8 5-0. 94 (m, 6 H ) (Comparative Example 1) (嗟 并 [3, 2-1): 4, 5-13,] bisbenzo[13] thiophene Synthesis)

Br Br

Na2S ·9H20 NMP (1·11) (3-8) In a l〇〇mL flask in which the gas in the flask was replaced with nitrogen, 3, 3, -1 odor-2, 2 - 2 (stupid [b] ] 嗟 () 〇. l〇g, 〇. 24mmol), sodium sulphide sulphate (0.056g, 0.24mmol) and 1-methyl-2-0 to 11 ketone (10mL) C was heated and stirred for 6 hours. This reaction was carried out without using a transition metal complex. The reaction liquid was analyzed by HPLC to obtain an area percentage, and the area of the compound (3-8) 41 323286 201219382 was 33%, and the area of the compound (1-11) was 41%. (Comparative Example 2) (Synthesis of epeno[3,2-b:4,5-b'] bisbenzo[b]e phenophene)

Br Br

Et20

BuLi (PhS〇2) 2S

(3-8) 3,3'-Dibromo-2,2'-bis(benzo[b]thiophene) (0.50 g, 1.2 mmol) was added to diethyl ether (15 mL) and stirred and cooled to - 78 ° C. The butyl lithium solution (0.88 mL, 2.7 匪〇1) was added to the solution. Thereafter, the mixture was stirred at -78 ° C for 1 hour, and bis(phenylsulfonyl) sulfide (0.56 g, 1.8 mmol) was added. Stir at -78 ° C for 1 hour. Thereafter, the reaction solution was allowed to reach room temperature (25 ° C), and an aqueous solution of vaporized ammonium was added. Chloroform was added and the organic layer was extracted. The organic layer of chloroform solution was washed with a vaporized aqueous ammonium chloride solution, dried over magnesium sulfate and concentrated. The concentrated solution was poured into a mixed solution of toluene and hexane to reprecipitate, and the resulting precipitate was recrystallized using hot air to obtain °Septene [3, 2-1): 4, 5-13 '] bisbenzo[13] ° phenotype 21111 bogey. The yield was 6%. [Simple description of the diagram] None [Key component symbol description] None 42 323286

Claims (1)

201219382 VII. Patent Application Range: 1. A method for producing a compound represented by the formula (3), which comprises: expressing a compound represented by the formula (1) and the formula (2) in the presence of a transition metal complex The steps of the compound reaction: (wherein the 'A ring and the β ring each independently represent an aromatic ring; γ represents a Group 15 element or a Group 16 element; ζ each independently represents a hydrogen atom, a aryl group, an aryl group or a heteroaryl group; m represents 〇 or 1 When γ is a group 15 element, m is 1, and when Υ is a group 16 element, m is 0), (wherein the A ring and the B ring system have the same meanings as defined above; X1 and X2 each independently represent a halogen atom, an alkyl suifonate group or an aryl sulfonate group), M1M2Y(Z)m ( 2) (In the formula, Μ1 represents an alkali metal atom or a magnesium halide group; Μ2 represents an alkali metal atom, a halogenated ity group or a hydrogen atom; Υ, Ζ and m are the same meanings as described above). 2. The production method according to the first aspect of the invention, wherein the compound represented by the formula (1) is a compound represented by the formula (1A), and the compound represented by the formula (3) is a formula (3A). Compound represented, 1 323286 201219382 (wherein 'R1 each independently denotes a group, an alkoxy group, a thiol group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amine group, a substituted amine group, a fluorenyl substituted fluorenyl group, and an auxin group. Atom, fluorenyl, decyloxy, decylamino, heteroaryl, sulfhydryl, substituted, nitro or cyano; n each independently represents an integer from 〇 to 2; when η is 2, the above definition is not limited to R1 The adjacent Rs may be bonded to each other, and together with the carbon atoms bonded by the respective RIs form a ring structure; E each independently represents -〇-, -S-, or -N(R3)-. R3 Each independently represents an alkyl group, an aryl group, or a heteroaryl group; the χ1&amp; χ2 system has the same meaning as described above), (wherein '1^, 11, ¥, 2, 111, and £ are in the same meaning as described above). 3. The production method according to the first aspect or the second aspect of the invention, wherein the compound represented by the formula (1) is a compound represented by the formula (3), and the compound represented by the above formula (3) a compound represented by the formula (3Β), 2 323286 201219382 • (wherein, p each independently represents an integer of 〇 to 4; R 2 each independently represents an alkyl group, an alkoxy group, a thiol group, an aryl group, an aromatic group, an arylthio group, a dilute group, an alkynyl group , amine group, substituted amine group, dream group, substituted group, dentate atom, fluorenyl group, decyloxy group, decylamino group, heteroaryl group, carboxyl group, substituted carboxyl group, Wei Qianji; benzene ring capped carbon porch When subgroup (4) has a radical 2 represented by r2, R does not depend on the above definition, and R of adjacent carbon atoms may be bonded to each other, and together with the adjacent carbon atoms form a cyclic structure; E each independently represents -〇 _, _s_, _hn(r3)_; R each independently represents a decentral, aryl, heteroaryl; χ1&amp;χ2 is of the same meaning as previously described;), (3Β) (wherein R2, ρ, Υ, Ζ, m, and Ε are in the same meaning as described above). The production method according to any one of the above-mentioned formula (1), wherein the compound represented by the above formula (2) is used with respect to the compound represented by the above formula (1). The amount is 丨 to 1〇莫耳. The manufacturing method according to any one of the items 1 to 4, wherein X1 and X2 each independently represent a gas atom, a bromine atom or an iodine atom. 6. A method for producing a compound represented by the formula (3), which comprises the step of subjecting a compound represented by the formula (4) to an intramolecular cyclization reaction in the presence of a transition metal complex, 323286 3 (2) ), 201219382 The loquat and the B ring each independently represent an aromatic ring; the gamma surface is a group 15 element or a hexadecane broadly 'γ^diyl, aryl or heteroaryl A.... represents a hydrogen atom, a calcined &amp; , m is not 0 or 1; when Y is a group 15 element, m is 1, when Υ is a group 16 element, ^ is 〇), (4) (wherein M3 represents a typical metal atom or a dentate group; X2 represents a dentate atom, an alkyl sulfonate group or an aryl sulfonate group; and A ring, B ring, γ, Ζ and m are The same meaning as above). 7. The production method according to the sixth aspect of the invention, wherein the compound represented by the formula (4) is a compound represented by the formula (4/〇, and the compound represented by the above formula (3) (3A) ) the compound represented, (wherein R1 each independently represents alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, alkenyl, alkynyl, amine, substituted amine, fluorenyl, 4 323286 201219382 substituted a mercapto group, a halogen atom, a fluorenyl group, a decyloxy group, a decylamino group, a heteroaryl group, a carboxyl group, a substituted carboxyl group, a nitro group or a cyano group; η each independently represents an integer of 0 to 2; when η is 2, it is not limited to R1 In the foregoing definition, adjacent R1 may be bonded to each other, and together with the carbon atoms bonded to the respective R1, form a ring structure; Ε each independently represents -0, -S-, -Se-, or - N(R3)-, R3 each independently represents an alkyl group, an aryl group, a heteroaryl group; Y, M3, Z, m and X2 are the same as defined above), (wherein, 1^, 11, 丫, 2, 111, and £ are in the same meaning as described above). 8. The production method according to the above formula (4), wherein the compound represented by the formula (4) is a compound represented by the formula (4B), and the compound represented by the formula (3) is a compound of the formula (3). a compound represented by the formula (3B), (wherein P each independently represents an integer of 0 to 4; and R2 each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amine group, a substituent Amine, fluorenyl, substituted fluorenyl, halogen atom, fluorenyl, aryloxy, decylamino, heteroaryl, thiol, substituted thiol, 5 323286 201219382 nitro or cyano; benzene When the sub-representation has the basis of r2, regardless of the above definition of R2, R of adjacent carbon atoms may be bonded to each other, and together with the adjacent carbon atoms form a ring structure; E each independently represents _〇 , _s_, 奋 or, 3), · 'each independently represents silk, aryl, heteroaryl; γ, Μ3, ζ, Μ X2 are the same meaning as above), , K, p, Y, Z, m and lanthanide have the same meaning as described above). 9. The manufacturing method according to the sixth aspect of the invention, wherein the typical metal atom is an alkali metal atom. 10. The method according to any one of claims 6 to 9, wherein X2 is a gas atom, a bromine atom or an iodine atom. The manufacturing method according to any one of the preceding claims, wherein the transition metal complex is a metal complex containing a Group 10 element β 12 · as claimed in the patent application The method according to the item 11, wherein the transition metal complex is a palladium complex. The production method according to claim 12, wherein the transition metal complex is a palladium complex having at least one phosphine ligand. The manufacturing method as described in any one of claims 1 to 13, wherein the γ is a Group 16 element. 6 323286 201219382 15. The manufacturing method described in claim 14 of the patent application, which is gamma-based sulfur. 16. The manufacturing method as described in any one of claims 2 to 5, wherein the items are independently represented by _〇_, or -Se-. 17. The manufacturing method of claim 16, wherein both E are -S-. 18. The method of manufacture according to any one of the preceding claims, wherein the transition metal complex is added sequentially. A compound represented by the formula (4), GMS (4) (wherein M3 represents a typical metal atom or a dentate magnesium group; the a ring and the 8 ring each independently represent an aromatic ring; and χ 2 represents a halogen atom, an alkyl group; Sulfonate or aryl acid vine; γ represents a Group 15 element or a Group 16 element; Ζ each independently represents a hydrogen atom, a county, a green or a heteroaryl group; m represents 0 or 1; Y is the 15th For a group element, 41; when γ is a group 16 element, m is 〇). A compound of the formula (10) described in the patent Lull No. 19, not a compound, 323286 7 201219382 (4B) (wherein P each independently represents an integer of 〇 to 4; and R2 each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amine Base, substituted amine group, fluorenyl group, substituted fluorenyl group, halogen atom, fluorenyl group, decyloxy group, decylamino group, heteroaryl group, carboxyl group, substituted carboxyl group, nitro group or cyano group; adjacent carbon atom in benzene ring When R12 has a group represented by R2, R2 of adjacent carbon atoms may be bonded to each other, and carbon atoms together with the adjacent carbon atoms form a ring structure; E each independently represents -〇, , _Se_4_N(R3)_; \ each independently represents an alkyl group, an aryl group, a heteroaryl group; Y, M3, z, m&amp; X2 are the same as defined above). 21. A compound represented by the formula (5), 323286 8 201219382 22. A compound as described in claim 21, which is a compound represented by the formula (5B), (wherein P each independently represents an integer of 0 to 4; and R2 each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amine group, a substituent An amine group, a fluorenyl group, a substituted fluorenyl group, a hydrazine group, a fluorenyl group, a decyloxy group, a decylamino group, a heteroaryl group, a carboxyl group, a substituted carboxy group, a nitro group or a cyano group; the adjacent carbon atoms in the benzene ring respectively have R2 The base time indicated is not limited to the above definition of R2, and R2 of adjacent carbon atoms may be bonded to each other, and together with the adjacent carbon atoms form a ring structure; E each independently represents _0_, -S_, _Se- or -N(R3)-; R3 each independently represents an alkyl group, an aryl group, a heteroaryl group; Y, Z, m and X2 are the same meanings as described above). 9 323286 201219382 IV. Designation of representative drawings: - (1) The representative representative of the case is: (). (There is no picture in this case) (2) Brief description of the symbol of the representative figure: (none) 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: This case does not represent the chemical formula 3 323286