TW201247688A - Monomer for production of polymer compound and method for producing polymer compound - Google Patents

Abstract

An objective of this invention is to provide a diboronic acid derivative of conjugated polymer compound with high molecular weight capable of being produced by Suzuki coupling method. The present invention provides a compound represent by formula (I). [wherein, A represents an arylene group, a heteroarylene group, -C ≡ C- or -CR31=CR32-. R31 and CR32 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or cyano group. R21, R22, R23, R24, R25, R26, R27 and R28 each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, an alkylthio group, a halogen atom, an aryl group or a heteroaryl group. M1, m2, m3 and m4 each independently represent an integer of 1 to 5. n1, n2, n3 and n4 each independently represent 0 or 1.]

Description

201247688 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a monomer for producing a polymer compound and a method for producing the polymer compound. [Prior Art] The conjugated polymer compound has been reviewed and applied to organic semiconductor devices such as organic transistor devices, organic solar cells, and organic electroluminescent devices, and research and development of various types of conjugated polymer compounds are being actively carried out. . As a main factor which greatly affects the characteristics of the organic semiconductor element, the molecular weight of the total polymer compound is known. For example, when a plurality of organic transistor elements are produced using a polymer compound having a repeating unit represented by the formula (A) and having different molecular weights, a polymer compound having a higher molecular weight is used, and the field effect of the organic transistor is shifted. The higher the electron field-effect mobility.

η-ΟβΗ-ο (A) Further, Non-Patent Document 2 discloses that an organic solar cell element produced by using a molecular compound having a repeating unit represented by the formula (B) and having a high molecular weight is higher than a molecular weight of a low molecular weight. The characteristics of the organic solar cell element produced by the molecular compound are large in the photocurrent (JPh) of the organic solar cell element produced by using the polymer compound having a high molecular weight. 324085 4 201247688

(B) As a method for producing a total of a polymer compound, a ruthenium formula in which an aromatic compound (tetra) m derivative and a di(tetra) compound of an aromatic compound are continuously coupled in the presence of a catalyst is examined. As a method for producing a conjugated polymer compound having a high molecular weight by using an eucalyptus formula, for example, there is a proposal to disclose a method for reducing the amount of an L3-propanediol vinegar derivative of an n-dithioborate and an aromatic compound; A method of reacting a pinion-derivative of a phenanthrene ore with a bidentate of an aromatic compound (Non-Patent Document 3). In the other aspect, Patent Document 1 describes that a boric acid group contained in an organic boric acid is sufficiently protected by N-methyliminodiacetic acid or the like, and an organic shryling is used by using N-mercaptoimido diacetic acid or the like. , reacting with an organic halide (Suzuki even law) to provide cross-coupling ((iv) ss e. 叩Hng) product. (Prior Art Document) Patent Document [Patent Document 1] Japanese Patent Application Publication No. 2010-534240 Non-Patent Document 1 [Non-Patent Document 1] Advanced Materials, 2003, Vol. 15, ρ·1519-1522 324085 5 201247688 [Non-Patent Document 2 Organic Electronics, 2009, Vol. 10, p. 1275-1281 [Non-Patent Document 3] Macromolecules, 2001, Vol. 34, ρ·5386-5393 [Summary of the Invention] In the case where the synthesis can be practically applied to a conjugated polymer compound of an organic semiconductor element, the above-mentioned conventional method has a problem that it is difficult to sufficiently increase the molecular weight of the conjugated polymer compound. More specifically, a co-roller molecular compound is produced by polycondensation of an aromatic compound diboric acid or a derivative thereof with a bidentate of an aromatic compound by using a Suzuki equation, in particular, the aromatic When the compound is a heterocyclic structure, the bond between the aromatic compound and the boron atom is cleaved before the polymerization reaction, and it is difficult to cause a coupling reaction. This is considered to be because the boron atom system of diboric acid has an empty coordination position, and a nucleophile such as water is easily attacked. Further, although the reason is not clear, it is considered that when the organic group of the diboric acid of the organic compound has an aromatic heterocyclic structure, the nucleophilic reagent such as water is more likely to attack the empty coordination position of the boron atom. That is, as shown in Non-Patent Document 3, it is difficult to increase the molecular weight of a common polymer compound by using an alkylene glycol ester derivative of an organic diboric acid and an organic bidentate compound. In the case of an organic heteroaryl group, it is more difficult to increase the molecular weight of a plurality of polymer compounds. Accordingly, the present invention has an object of providing a derivative of a dicarboxylic acid which is capable of producing a molecular weight of a total of a polymer compound by using a eucalyptus formula. 324085 6 201247688 (Means for Solving the Problem) That is, the present invention provides a compound represented by the formula (1),

31 [12, wherein A represents an extended aryl group, a heteroaryl group, a C = C_ or a CR ^ R group and a fluorene group each independently represents a hydrogen atom, an alkyl group, an aryl group: a cyano group or a cyano group. R" and Rl2 each independently represent a nitrogen atom, an alkyl group, an aryl group or a heteroaryl group. R21, R22, r23, r24, r25, r26, r27 and R each independently represent a hydrogen atom, a pyridyl group, an alkoxy group, a sulfur-burning group, a tooth ', an aryl group or a heteroaryl group. When R21 is plural, the numbers may be the same or different. When R22 is plural, the numbers may be the same or different. When π is plural, the materials may be the same or different. When r24 is plural, the numbers may be the same or different. When r25 is plural, the same can be the same ^ can be different. (9) When there are a plurality of numbers, the items may be the same or different. When R27 is plural, these may be the same or different. When r28 is plural, these may be the same or different, and each of them may independently represent an integer of 1 to 5. The ηb, π3, and n4 systems each independently represent 0 or 1]. Further, the present invention provides a method for producing a polymer compound comprising a repeating unit represented by the formula (6) and a repeating unit represented by the formula (Ό), which is carried out in the presence of a transition metal complex and a base in 324085 201247688, The compound is polymerized with the compound represented by the formula (5); 'X1——E——X2 (5) [wherein, E represents an aryl group, a heteroaryl group, a 戋~CR91=CR92-.... and ^ each independently represents a hydrogen atom, an alkane A, an aryl group, a heteroaryl group or a cyano group, each independently representing an atom, a decyl sulfonate group, an aryl sulfonate group]; 1 + A+ such as (6) (7) In the formulas (6) and (7), 'A and E are the same meanings as described above.' (Effect of the invention) According to the present invention, since a polymer compound having a high molecular weight can be produced by using Suzuki's law, the present invention [Embodiment] The present invention is described below. In the compound represented by the formula (1), the A system represents an exoaryl group, a heteroaryl group, -c^c- or a CR31=CR32-. Rw another p32 "K and R each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or The cyano group n R, 2 each independently represents an ammonia atom, an alkyl group, an aryl group or a heteroaryl group. r21, r22, r23, r24, r25, ruthenium 26, r and each independently represent a hydrogen atom, a burnt group, and a record. Base, sulphur 324085 201247688 di-atomic, aryl or heteroaryl. When r21 is plural, these can be different, and when H is plural, these can be (four) or not plural. The same may or may not be plural, and the same may or may not be different. When r25 is plural, the same may be the same. 卩26 is a plural _, and the material may be different or different. These may be the same or different. When the π system is plural, the material may be (4) or m m3 and (4) each independently represent an integer of 1 to 5. ", ^(6) and (4) each independently represent 〇 or 1. The group which is represented by A, which is an aryl group which removes two hydrogen atoms of a carbon atom of an aromatic ring from an aromatic hydrocarbon compound, includes a benzene ring-containing group, a condensed ring-containing group, and contains two The basis of the structure in which the above-mentioned independent aromatic % or condensed ring is directly bonded. The aryl group may have a carbon number of usually 6 to 6 Å, preferably 6 to 2 Å, and the carbon number does not include the carbon number of the substituent which the aryl group has. Specific examples of the aryl group include a phenylene group, a naphthyldiyl group, a fluorenyldiyl group, a phenanthrenyl group, a fused tetraphenyldiyl group, a fluorenyldiyl group, a fused pentaphenyldiyl group, a fluorenyldiyl group, a fluorenyldiyl group, and a hydrazine group. a benzenediyl group, a bistriphenyldiyl group, a bistetraphenyldiyl group. The heteroaryl group represented by A removes two hydrogens directly bonded to an atom constituting an aromatic ring from an aromatic heterocyclic compound. The atomic group after the atom includes a monocyclic group-containing condensed ring-containing group, and a structure in which two or more independent aromatic rings or condensed rings are directly bonded. The heteroaryl group may also have a substituent. The heteroaryl group has a carbon number of usually 2 to 60, preferably 2 to 20. The carbon number does not include the carbon number of the substituent of 324085 9 201247688 of the heteroaryl group. Specific examples of the heteroaryl group include a geminodisyl group, an indenyldiyl group, a sedanyl group, an anthraquinone diyl group, an inosine diyl group, a dithiophenediyl group, a trithiophenediyl group, and a tetrathiophene. Diyl, pyrrole diyl, furandiyl, selenophenediyl, pyridyldiyl, pyridinium, octapeptide, diterpene, benzophenanyl, benzodi A benzofurandiyl group, a quinolinediyl group, an isoquinolinyldiyl group, a thienothiophenediyl group, a benzothiadiazolediyl group, a benzodithiophenediyl group, a cyclopentadithiophenediyl group.

The filaments represented by Ru, R12, R21, R22, R23, R24, 俨, r26, r27, r28, r31 and R32 may be either money or branched, or may be a cyclic alkyl group. The silk may also have a substituent. The material usually has a carbon number of from 1 to 60, preferably from 1 to 20. The carbon number does not include the carbon number of the substituent of the alkyl group. Specific examples of the alkyl group include a direct bond group such as a mercapto group, an ethyl group, a n-propyl group, a n-butyl group, a n-hexyl group, an n-octyl group, a n-dodecyl group, and an n-octadecyl group; Isobutyl, t-butyl, tert-butyl, 2-=hexyl, 3,7-dimethyloctyl alicyclic, isocyclic alkyl. R32/'R,2'r2,'r22'r23'r24^25^26>r^r^r^ aryl' is removed from the aromatic hydrocarbon compound and bonded directly to the composition: i hydrogen of the fragrant carbon atom The atomic group after the atom, including the i ring of the benzene ring = the ring group of the ring, contains two or more independent aromatic rings or a y bond direct bond "is a (four) structure. The aryl group has a substituent. The carbon number of the :: is usually 6 s 60 ', preferably 6 to 2. The carbon ' does not include the carbon number of the substituent which the aryl group has. Specific examples of the aryl group can be exemplified. , 1-naphthyl, 2-naphthyl, diterpene, 2-indenyl, 9-324085 201247688 fluorenyl, 1-youji, 2-yanoyl, 4-yl, 4-phenylphenyl. 4--R11, R12 , R21, R22, p23 R, R, R, R26, R27, R28, R31 = the surface of the miscellaneous silk is removed from the aromatic heterocyclic compound, and the atom directly bonded to the aromatic ring of the structure is removed. The atomic group after the atom includes a monocyclic group, a condensed ring-containing group, a structure having two or more independent heteroaromatic rings or a fused ring directly bonded. The heteroaryl f may have a substituent. Heteroaryl has (4) Usually 2 to 〇' is preferably 2 to 20. The carbon number does not include the carbon number of the substituent which the heteroaryl group has. Specific examples of the heteroaryl group include 20 south bases and 3 bites. Cyclol, 2-♦ phenyl, phenyl, 2, cyclinyl, 3-mercapto, 2-indolyl, 2-propenyl, 2-indenyl, 2-indenyl, 3-indenyl, 4_. , 2-benzo(tetra)yl, 2L-thenyl, 2-year-old fluorenyl, and R22, R23, R24, R25, and (d) are alkoxy groups, which may be linear or branched. The ' can also be a cyclic alkoxy group. The alkoxy group may also have a substituent. The alkoxy group has a carbon number of usually 1 to 6 Å, preferably 1 to 20. The carbon number does not contain an alkoxy group. The inverse of the stone having a substituent. Specific examples of the alkoxy group include a methoxy group, a n-butoxy group, a n-hexyloxy group, a 2-ethylhexyloxy group, and a 3,7-dimethyl group. An oxy group, n-dodecyloxy group, etc. ^ an alkylthio group represented by R2i, R22, R23, R24, R25, p and r28, which may be either a straight chain or a branched chain, or a cycloalkyl sulfide. The alkylthio group may also have a substituent. The alkylthio group usually has a carbon number It is preferably from 1 to 20. The carbon number does not include the carbon number of the substituted 324085 201247688 group of the alkylthio group. Specific examples of the alkylthio group include n-butylthio group and n-hexyl sulfide. a base, 2-ethylhexylthio, 3,7-didecyloctylthio, n-dodecylthio, etc. as a halogen atom represented by R21, R22, R23, R24, R25, R26, R27 and R28 Examples thereof include a fluorine atom, a chlorine atom, a molybdenum atom, and a moth atom. The A system is preferably an aryl group, a benzoheptazol diyl group, a "epi-diyl group, and a diophene diyl group. It is preferred that the three-degree diphene diyl group and the tetra-β-sentene diyl group are preferred. From the viewpoint of easiness of synthesis of the compound represented by the formula (1), R11 and R12 are preferably an alkyl group. From the viewpoint of easiness of synthesis of the compound represented by the formula (1), R21, R22, R23, R24, R25, R26, R27 and R28 are preferably a hydrogen atom or an alkyl group, and a hydrogen atom is preferred. The compound represented by the formula (1), the nitrogen atom represented by fluorene in the formula (1) may be coordinately bonded to the boron atom represented by fluorene in the formula (1). When there is a coordination bond of a boron atom (Β) by a nitrogen atom (Ν), since the nitrogen atom (Ν) protects the empty coordination position of the boron atom (Β), the compound represented by the formula (1) is polymerized. When the monomer to be reacted is used, the ratio of the bond between the group represented by ruthenium and the boron atom (Β) before the polymerization reaction can be suppressed. When the nitrogen atom protects the vacancy position of the boron atom, when the aryl group represented by A is extended, the effect of suppressing the bond between the group represented by A and the boron atom (B) can be effectively exhibited. . From the viewpoint of forming a coordination bond of a nitrogen atom (N) to a halogen atom (B), the sum of ml and nl is 2, the sum of m2 and n2 is 2, and the sum of m3 and n3 is 2, and The sum of m4 and n4 is preferably 2; and ml, nl, m2, n2, 324085 12 201247688 m3, n3, m4 and n4 are preferably 1. The compound represented by the formula (1) is, for example, a compound represented by the formula (U0D to the formula (1-041)), wherein a compound represented by the formula (〇__〇14) to the formula (1_〇39) is preferred. .

G

R R R R

(1-004) (1-005) (1-001) (1-002) (1-003)

R R G Λ ,R R" V r1 , R G R R (1-008) RRRpd p p ^ ^ «

324085 13 201247688

R N—N N_N N~/ G 乂. ^G 乂 S^O (1-014) (1-015) G G (1-016) (1-017)

R R R

(1-018)

R R

(1-019)

(1-020) (1-021) (1-022) (1-023) (1-024)

RRRR RRRRRR RRRRRRRR

(1-025) (1-026) (1-027)

RR (1-037) . (1-038) (1-039) (1-040) (1-041) In the formula (1-001) to the formula (1-041), R represents a hydrogen atom or an alkyl group. , alkoxy, alkylthio, aryl or heteroaryl. The existence of a complex R system can be different from 14 324085 201247688. IT is a currency atom, an alkyl group, an aryl group or a heteroaryl group. The number of turns can be the same or different. ...r denotes the burning of the US square, and the specific examples are the same as the definitions and specific examples of the earth, square and hetero groups represented by the above r2i. The definitions and specific examples are the same as the definitions and specific examples of the firing group, the sulfur-burning group, the examples, the (iv) r group, and the sulfur-burning group. G is a formula (G__ to ^ (equivalent unit.) From the viewpoint of easiness of the compound represented by the compound (1), the structural unit represented by the formula (G, 4) is preferred. The formula (G-_) The structural unit is represented, and the structural unit in which R is a gas atom and Ra is a methyl group is preferably one or more, and may be the same or different. 〇4r N-Ra % (G>0〇1)

R

R

-B

R R R O

R \ N-|

Ra -B rR bv%a

(G-002) (G-003) -B, N-Ra°ltR (G-004)

R R R R

0 —B v o R RR R (G-005)

O R R

R R (G-006) R

R N-Ra R In the formula (1-GG1) to the formula (Bu Q31), the R and Ra systems represent the former thinking and meaning. A preferred aspect of one of the formulas in (1) is shown in Table (2). Table 324085 15 201247688 Λ

In the formula (2), 'R and R42 each independently represent a gas atom, an alkyl group, an alkoxy group, a thiol group, an aryl group, a heteroaryl group, a south atom, an aryl group or a nitro group. The carbon atom of ^: and the carbon atom in P may also be bonded to form a cyclic structure. The two filaments are -s-, _〇_, -Se-, -NR51- or -cr6i=cr62 R, R and R62 each independently represent a gas atom or a heteroaryl group. R41 and R42 represent a decyl group, an alkoxy group, a thiol group, an aryl group, a heteroaryl group, a self-atomic mosquito, and a specific example, and the above R21 represents a (tetra) group, an alkoxy group, a sulfur-burning group, a silk, a hetero group. The aryl group, the definition of the atom, the specific example phase, the definition of the heterocyclic group, the definition of the compound, the heterocyclic group, the alkyl group and the aryl group represented by R51, R61 and R62, and the alkyl group represented by the above R21, The aryl matrix is the same. The compound represented by the formula (2) includes, for example, a compound represented by the formula: n_Q28) to (1-032) and a compound represented by the formula (1-037). Another preferred aspect of A in the formula (1) is a group represented by the formula (3). 324085 16 201247688

In the formula (3), R71 and R72 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a heteroaryl group. u is an integer of 1 to 5. When R71 is plural, the systems may be the same or different. When R72 is plural, the systems may be the same or different. R71 and R72 in which two carbon atoms directly bonded to each other are bonded to each other, and a carbon atom in R71 and a carbon atom in R72 may be bonded to each other to form a cyclic structure. The definitions and specific examples of the alkyl group, the pendant oxy group, the thiol group, the aryl group and the heteroaryl group represented by R71 and R72 are the alkyl group, the alkoxy group, the alkylthio group, the aryl group represented by the above R21, The definition and specific examples of the heteroaryl group are the same. Examples of the compound represented by the formula (3) of the formula A include a compound represented by the formula (1-019), a compound represented by the formula (1-025) to the formula (1-027), and a formula (1-038). The compound represented by the formula and the compound represented by the formula (1-039). Another preferred aspect of A in the formula (1) is a group represented by the formula (4).

(4) In the formula (4), R81, R82, R83 and R84 each independently represent a hydrogen atom, 324085 17 201247688 alkyl group, alkoxy group, alkylthio group, aryl group or heteroaryl group. v is an integer from 1 to 5. When R81 is plural, the systems may be the same or different. When R82 is plural, the systems may be the same or different. When R83 is plural, the systems may be the same or different. When R84 is plural, the systems may be the same or different. The carbon atoms in R81 and the carbon atoms in R82 may bond together to form a cyclic structure in R81 and R82 in which two carbon atoms directly bonded to each other are bonded. The carbon atoms in R83 and the carbon atoms in R84 may bond together to form a cyclic structure in R83 and R84 in which two carbon atoms directly bonded to each other are bonded. The definitions and specific examples of the alkyl group, the alkoxy group, the alkylthio group, the aryl group and the heteroaryl group represented by R81, R82, R83 and R84 are the alkyl group, the alkoxy group, the alkylthio group and the aromatic group represented by the above R21. The definitions and specific examples of the base and the heteroaryl group are the same. The compound represented by the formula (4) is, for example, a compound represented by the formula (1-001), a compound represented by the formula (1-012), and a compound represented by the formula (1-013). The compound represented by the formula (1) can be produced, for example, in the following manner. That is, the organic diboric acid represented by the following formula is used:

HO\ OH

B_A_B

HO OH (8) [wherein, the A system has the same meaning as described above], and the boric acid protecting compound represented by the following formula: 324085 18 201247688 〇 〇21 R11 r23 〇

R22 R24 (9) [wherein R11, R21, R22, R23, R24, ml, m2, nl and n2 are the same as defined above], and/or a boronic acid protecting compound represented by the following formula: 0 R25 R12 R27 Ο

(10) wherein R12, R25, R26, R27, R28, m3, m4, n3 and n4 are reacted in the same sense as described above. The reaction is carried out, for example, by dissolving the two compounds in an appropriate amount and a suitable solvent and heating for a certain period of time. The conditions for carrying out the reaction of the boric acid group with the boric acid protecting compound are known, and are described in Patent Document 1. However, the amount of the reaction between the organic diboric acid and the boric acid protecting compound is adjusted so that the amount of the organic boric acid group does not remain (the amount of the organic diboric acid) / (the amount of the boric acid protecting compound) is 1/2 in terms of the molar ratio. The amount below. <Method for Producing Polymer Compound> The method for producing a polymer compound of the present invention is a method for producing a polymer compound comprising a repeating unit represented by the formula (6) and a repeating unit represented by the formula (7), which is a transition metal The compound represented by the formula (1) 324085 19 201247688 is polymerized with the compound represented by the formula (5) in the presence of a complex and a base. <Compound represented by the formula (5)> In the formula (5), the E system represents an exoaryl group, a heteroaryl group C- or a CR91=CR92-. R91 and R92 each independently represent a hydrogen atom, an alkyl group, a \ group, a heteroaryl group or a cyano group. X1 and χ2 are each independently a (iv) a primary sulfonate group or an aryl sulfonate group. The definition and specific examples of the stretched yarn and the stretched yarn indicated by Ε are the same as those of the extended aryl group and the heteroaryl group represented by the above Α, and the specific examples are the same. From the viewpoint of the molecular weight of the high-A compound produced by Tienan, it is preferable that E is an aryl group or a heteroaryl group. And the definition, specific examples of the alkyl group, the aryl group and the heteroaryl group represented by R92,

糸 is identical to the definition of silk, aryl, and heteroaryl represented by the former phase R21. In the formula (5), examples of the atom represented by X1 and χ2 include a gas atom, a gas atom, a bromine atom, and an iodine atom. In the formula (5), the alkylsulfonate group represented by X1 and X2 may be an oxime sulfonate group or a trifluorosulfonate group. In the formula (5), the aryl group of the acid sulfonate group represented by &amp; χ2 may, for example, be a perester group or a p-toluenesulfonate group. The molecular weight of the polymer compound produced from the oxime In the case of χι and r', it is preferable that the gas atom, the atom, and the atom to be broken are preferably a ruthenium atom or an iodine atom. Examples of the compound represented by the formula (5) include a formula (5 side) to a formula (5 to 〇41). ) indicates the compound. 324085 20 •r*

R R R R

(5-008)

R R R

201247688

R R R X X R x_^^x x-^H^r

R R R R R R (5-001) (5-002) (5-003)

R X R

(5-009) R R R R

R X R R R R R, X- l Λ R R X R (5-012)

R R R R R R

(5-014) (5-015) (5-016) (5-017) (5-018) (5-019)

(5-020) (5-021) (5-022) {5-023) (5-024) 324085 21 201247688

(5*025&gt; (5-026)

X

(5-032)

(5-038) (5-039) (5-040) The 'r and V' lines in the formula (5-001) to the formula (5-041) have the same meanings as described above. X represents a _ atom, an alkyl sulfonate group or an aryl sulfonate group. The X systems in the plural may be the same or different. The definition and specific examples of the tooth atom, the alkyl sulfonate group, and the aryl sulfonate group represented by X are the definitions of the halogen atom 'alkyl sulphonate group and the aryl sulfonate group represented by the above X1. The specific examples are the same. <Test> The test used in the method for producing a polymer compound of the present invention may be an inorganic test or an organic test, but it is preferably an inorganic test. 324085 22 201247688 As an inorganic test, metal oxides such as sodium hydroxide and potassium hydrogen hydride; metallurgical metal hydroxides such as ammonium hydroxide; acetates such as sodium acetate and potassium acetate, sodium carbonate, a carbonate such as potassium carbonate or cesium carbonate; a phosphate such as sodium phosphate or potassium phosphate; or a fluoride such as sodium fluoride or potassium fluoride. Among the inorganic bases, carbonates such as sodium carbonate and potassium carbonate; and phosphates such as sodium phosphate and potassium phosphate are preferred. Preferred inorganic bases are sodium carbonate and potassium phosphate. Examples of the organic test include tetrahydrogen hydroxide and tetrabutylammonium hydroxide. The amount of the base to be used is preferably from 2 to 20 mols with respect to the compound 1 mol represented by the formula (1), and is preferably from 2 to 1 mol. <Transition Metal Complex> The transition metal complex used in the method for producing a polymer compound of the present invention is preferably a transition metal complex containing an element of Group 8 to 1 steroid, and contains 10th. A transition metal complex of the element of the group is preferred, and a complex compound or a nickel complex is more preferred to provide a complex compound. The above transition metal complex is preferably one having at least one phosphine ligand. The aforementioned transition metal complex also includes a transition metal complex precursor. Here, the transition metal complex precursor is a composition which can be converted into a transition metal complex in the reaction system. The composition may, for example, be a composition containing a transition metal complex for a precursor, a phosphine ligand or a scale salt. Examples of the palladium complex compound include ruthenium (triphenylphosphine)palladium (ruthenium) and iridium (dimethylphenylphosphine)palladium (ruthenium) (including various substituted isomers of ortho, meta and para). , bis(triphenylphosphine) di-palladium (11), bis(tricyclohexylphosphine) digas 324085 23 201247688 (π), bis(triethylphosphine)palladium dichloride (0), [込^ bis(diphenylphosphino) phenylene] di-palladium (u), [丨, Γ_bis(diphenylphosphino)ferrocene] palladium dichloride (ruthenium), bis(acetonitrile) Dihydrogenated palladium (II), and bis (benzonitrile) gasification (II). Wherein 'palladium (triphenylphosphine) palladium (0), bis(triphenylphosphine) di-palladium (palladium), [1,1'-bis(diphenylphosphino)ferrocene] Palladium (11) is preferred. Examples of the nickel complex compound include ruthenium (triphenylphosphine) nickel (ruthenium), bis(diphenylphosphine) nickel dihydride (丨1), and [丨, 2_bis (diphenylphosphino). Ethane] nickel (II), [1,3-bis(diphenylphosphino)propane]nickel dichloride (11), [1,4-bis(diphenylphosphino)butane ] Nickel dichloride (〗), [〗, 丨, _ bis (diphenylphosphino) ferrocene] nickel (II) and other gases. Examples of the transition metal complex for the precursor include Pd2(dba)3 (here, dba means trans, trans-dibenzylidene acetone), and Pd2 ( Dba) 2, acetic acid (Π), bis (1,5-cyclooctadiene) nickel (〇) and the like. Among them, Pd2(dba)3, Pd2(dba)2, and palladium acetate (π) are preferred. By phosphine ligand is meant a compound capable of being coordinated to a transition metal. Examples of the phosphine ligand include trialkylphosphines such as tri-n-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, and tribenzylphosphine; or diphenyl Phosphine, triphenylphosphine (including various substituted isomers in the ortho, meta and para), ginsyl (methoxyphenyl) phosphine (including ortho, meta and para) Triarylphosphines such as diarylphosphines, dicyclohexylphenylphosphines such as diphenylcyclohexylphosphine, (2-biphenyl)di-tert-butylphosphine, etc. 324085 201247688 Dioxane Alkylphosphines; 1,2-bis(diphenylphosphino)ethane, 13-bis(diphenylphosphino)propane, 1,2-bis(diphenylphosphino)cyclohexane, 13 —Bidentate ligand phosphines such as bis(diphenylphosphino)phenyl, 1,1'-bis(diphenylphosphino)ferrocene. Among them, tri-tert-butylphosphine, tricyclohexylphosphine, triterpene phosphine (including various substituted isomers of ortho, meta and para), ginseng (methoxyphenyl) phosphine (including Preferably, the various substituted isomers of the ortho, meta and para are preferred. The above-mentioned scale salt is a salt obtained from the above phosphine ligand, HBF4, HPF6, or the like, and examples thereof include tri-n-butyl fluorene tetrafluoroborate, tri-tert-butyl quaternary tetrafluoroborate, and the like. Stupid hexafluoroborate, triptypic hexafluoroantimonate, and the like. When a scale salt is used in the production method of the present invention, the scale salt can be converted into a phosphine ligand by the base present in the reaction liquid. When the scale salt is used in the production method of the present invention, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, sodium hydride, sodium hydride, and sodium phosphate are used as the base. It is better to use sodium carbonate, carbonic acid clock, cesium carbonate, sodium sulphate or potassium sulphate. The transition metal complex is preferably used in an amount of 0.0001 to 10 mols, preferably 0.001 to 1 mol, based on the compound 1 mole represented by the formula (1). 001至第一摩尔 is preferred, with respect to the compound 1 mole represented by the formula (1), the amount of the transition metal complex compound used in the precursor is preferably 0.001 to 10 moles, and preferably 0.001 to 1 mole. The amount of transition metal complex 1 molar 'phosphine ligand relative to the precursor is 324085 25 201247688. The amount used is preferably 1 to 10 moles, preferably 1 to 4 moles. Preferably, the scale salt is used in an amount of from 1 to 10 moles, preferably from 1 to 4 moles, per mole of the transition metal complex of the precursor. Further, the transition metal complexes may be used alone or in combination of two or more. <Polymerization reaction conditions> In the method for producing a polymer compound of the present invention, the polymerization reaction temperature is preferably 20 to 200 °C. From the viewpoint of efficiently conducting the polymerization reaction, it is preferably 50 ° C or more, more preferably 80 ° C or more. Further, from the viewpoint of suppressing side reactions, it is preferably 180 ° C or lower, more preferably 160 ° C or lower. The polymerization time is usually from 1 minute to 200 hours. From the viewpoint of allowing the polymerization reaction to proceed sufficiently, it is preferably 1 hour or longer. The above polymerization reaction may be carried out in the absence of a solvent or in the presence of a solvent, but it is preferably carried out in the presence of a solvent. When the solvent is used, the solvent to be used may be any solvent which is inert to the reaction, and may be used singly or as a mixed solvent. Examples of the solvent include aliphatic hydrocarbon solvents such as cyclohexane and nonylcyclohexane; aromatic hydrocarbon solvents such as benzene and toluene; and ether solvents such as tetrahydrofuran and anisole; and 1-mercapto-2-pyrrole. An aprotic polar solvent such as ketone, N, N-dimercaptoamine, N,N-dimercaptoacetamide, dimercaptosulfoxide, acetonitrile; and water, aromatic hydrocarbon solvent, ether system A solvent or an aprotic polar solvent is preferred. The polymerization reaction may be carried out in the air or in an inert atmosphere of 324085 26 201247688, but it is preferably carried out under an inert gas atmosphere such as nitrogen or argon. <Organic transistor> The organic transistor includes a source electrode and a drain electrode, an active layer, and a gate electrode, wherein the active layer serves as a current between the source electrode and the drain electrode. The path includes the polymer compound of the present invention; and the gate electrode controls the amount of current passing through the current path. As the organic transistor having such a structure, for example, a field effect type organic transistor can be cited. The field effect type organic transistor is usually an organic transistor having a source 'electrode and> and a pole electrode, an active layer, a gate electrode, and an insulating layer, wherein the active layer is between the source electrode and the drain electrode The current path is included in the polymer compound of the present invention; the gate electrode controls the amount of current passing through the current path; and the insulating layer is disposed between the active layer and the gate electrode. In particular, it is preferable that the source electrode and the drain electrode are provided in contact with the active layer, and the gate electrode is provided with an electromechanical crystal interposed between the insulating layers connected to the active layer. Fig. 1 is a schematic cross-sectional view showing an example of an organic transistor (field effect type organic transistor). The organic transistor 100 shown in Fig. 1 includes a gate electrode 3, an insulating layer 2 formed on the gate electrode 3, an active layer 1 formed on the insulating layer 2, and an active layer formed at a predetermined interval. The source electrode 4 and the drain electrode 5 on the layer 1. EXAMPLES Hereinafter, the present invention will be described in further detail with reference to the examples, 324085 27 201247688, but the present invention is not limited thereto. (Molecular weight analysis) The number average molecular weight and the weight average molecular weight of the polymer compound were determined by using a gel permeation chromatography (GPC, manufactured by Shimadzu Corporation, trade name: LC-10AD). The polymer compound thus measured was dissolved in tetrahydrofuran, and the mobile phase system injected into GPOGPC was tetrahydrofuran. For the column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A UV detector (manufactured by Shimadzu Corporation, trade name: 〇A) was used for the detector. (NMR analysis) The NMR measurement was carried out by dissolving the compound in dimethyl sulfoxide and using an NMR apparatus (manufactured by Varian Co., Ltd., INOVA300). Example 1 (Synthesis of Compound A)

A

In the flask, '1,5 〇g (6.70 mmol) of 2,1,3-benzoindene dioxin-4,7-diboronic acid, 2.07 g (14. lmmol) of N-methyliminodi Acetic acid, 30 mL of toluene' was refluxed for 5 hours. Next, the produced precipitate was filtered and taken out, and the precipitate was washed with water. Thereafter, the precipitate was dried to obtain Compound A. The yield of the compound A was 2.75 g' yield of 92%. Ή-NMR (300MHz, DMS0-d6) δ7. 92 (s, 2H), 4. 28-4. 5 6 (m, 8H), 2. 57 (s, 6 H) 324085 28 201247688 Example 2 (Compound Synthesis of B)

In the flask, 1.50 (6.2 〇 111111 〇 1) biphenyl-4,4,-diboronic acid, 1.91 g (1. Ommol) N-mercaptoimido diacetic acid, and 30 mL of stupid were added to make it Reflux for 5 hours. Thereafter, the formed precipitate was taken out by filtration, washed with water, and then washed with methanol. It was dried to obtain Compound B. The yield of the compound B was 2.59 g, and the yield was 90 〇/〇. 1 H-NMR (3 Ο OMH z, DMS Od 6) S 7. 7 Ί (d, 4 Η), 7. 5 6 (d, 4 Η) , 4. 1 4 - 4 4 2 (m, 8 Η ), 2. 5 7 (s, 6 Η) Example 3 (Synthesis of Compound C)

c In a flask, add 1.50 g (8. 73 mmol) of sinter-2, 5-di-decanoic acid, 2. 70 g (18.3 mmol) of N-mercaptoimido diacetic acid, and 3 〇mL of hydrazine to make it Reflux for 5 hours. Thereafter, the formed precipitate was taken out by filtration, washed with water, and washed with decyl alcohol. It was dried to give Compound C. The yield of the compound C was 3.16 g, and the yield was 92%. 324085 29 201247688 1H-NMR (3 00MHz, DMSO — d6) δ7· 30 (s, 2H), 4. 00 — 4. 41 (m, 8 H) , 2. 60 (s, 6H) Example 4 (High Synthesis of molecular compound D)

Ch3 n-s, n h3c,

A

Pd(OAc)2

5克(0. 112mmol) Compound A, 61.5 mg (0. 112 mmol) 2,7-dibromo-9,9-dioctylhydrazine, 50 mL four were added to the flask of the gas in the flask. Hydrogen D-propanol, 0.25 mg of acetic acid, and 0.779 mg of bis(2-methoxyphenyl)phosphine were stirred. Into the reaction mixture, a solution obtained by dissolving 11911 (0.561111111〇1) of acid-dissolved in 1〇1111 water was added dropwise thereto, and the mixture was refluxed for 9 hours to obtain a polymer compound D. lxlO4。 The weight average molecular weight of the converted polystyrene is 6. lxlO4. Comparative Example 1 (Synthesis of Polymer Compound E) I %

Pd(OAc)z

In addition to the use of 43.5 mg (0·112 mmol) of 4,7-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan-2-yl)-2, 1,3-Benzothiadiazole 324085 30 201247688 A polymer compound E was obtained in the same manner as in Example 4 except for the compound A. The amount of the polymer compound E is converted to a polystyrene. The average molecular weight is 7. 4xl03, and the weight average molecular weight of the converted polystyrene is 1.5 χ 104. Comparative Example 2 (Synthesis of Polymer Compound F)

Pd(OAc)2

Polymer compound F was obtained in the same manner as in Example 4 except that 25. lmg (0. 112 mmol) of 2,1 -benzothiadiazole -4,7-diboronic acid was used instead of compound A. The number average molecular weight of the polystyrene converted from the polymer compound F was 4, 8 x 10 3, and the weight average molecular weight of the converted polystyrene was 6.8 x 10 3 . Example 5 (Synthesis of Polymer Compound G)

Pd(OAc)2

In a flask in which the gas in the flask was replaced with nitrogen, 50. 0 mg (0. 112 mmol) of Compound A, 61, 5 mg (0. 112 mmol) 2, 7-di- -9, 9-dioctyl hydrazine, 50 mL of 4 was added. Hydroquinone e, 〇 · 25 mg of acetic acid, 0. 79 mg 324085 31 201247688 ginseng (2-decyloxyphenyl) phosphine and stirred. A solution obtained by dissolving 59.4 mg (0.561 mmol) of sodium carbonate in i〇mL of water was added dropwise to the reaction mixture, and the mixture was refluxed for 9 hours to be added to the south molecular compound .G. The number average molecular weight of the converted polystyrene of the polymer compound G was 3.OxlO4, and the weight average molecular weight of the converted polystyrene was 1.5x105. Comparative Example 3 (Synthesis of polymer compound hydrazine)

In addition to the use of 43.5 mg (0. 112 mmol) of 4,7-bis(4,4,5,5-tetradecyl-1,3,2-oxo-poor oxazol-2-yl)-2,1 The polymer compound oxime was obtained in the same manner as in Example 5 except that the compound was reacted in the same manner as in Example 5. The number of converted polystyrenes of the polymer compound 平均 is 1·7χ104, and the weight average molecular weight of the converted polystyrene is 5. lxlO4. Comparative Example 4 (Synthesis of Polymer Compound I)

Pd(OAc)2

P(o-MeOC6H4)3 fci,S,N

Νθ2〇〇3

THF Η20 was obtained in the same manner as in Example 5 except that 25.1 mg (0. 112 mmol) of 2,1,3-1,3-benzothiadiazole 324085 32 201247688 -4, 7-diboronic acid was used instead of compound A Molecular compound I. 2xl03。 The weight average molecular weight of the polystyrene is 7. 2xl03. Example 6 (Synthesis of Polymer Compound J)

B

Pd(OAc)2

50 mg (0. 108 mmol) of compound B, 59. 24 24 mg of acetic acid la, 〇. 60 mg of ginseng (2-decyloxyphenyl) phosphine and stirred. A solution obtained by dissolving 57' lmg (0.539 mmol) of sodium carbonate in 1 Torr of water was added dropwise to the reaction liquid, and the mixture was refluxed for 9 hours to obtain a polymer compound ja polymer compound j. The number average molecular weight of ethylene is 5.6 χ 1 〇 4, and the weight average molecular weight of the converted polystyrene is 1.5 χΐ〇 5. Comparative Example 5 (Synthesis of 13⁄4 molecular compound hydrazine) 324085 33 201247688

(h〇)2b〇〇-b(〇h&gt;2 + ^-^ULXJ

CgH^ CgHu

Pd(OAc)2

The polymer compound K was obtained in the same manner as in Example 6 except that 26. lmg (0. 108 minol) of biphenyl-4,4'-dibromo compound was used instead of the compound B. The number of polystyrenes in the conversion of the polymer compound K is an average molecular weight of 5. 6x103, and the weight average molecular weight of the polystyrene is 1. lxlO4. Example 7 (Synthesis of Polymer Compound L)

Pd(OAc)2 P(o-MeOCBH4)3 Ν32〇〇3

THF HzO

In a flask in which the gas in the flask was replaced with nitrogen, 50. 0 mg (0·127 mmol) of compound C, 69. 6 mmol (〇. 127 mmol) of 5,5,-dibromo-4,4'-di(tetradecyl) was added. 2,2'-di-epex, 5〇1111 tetrahydrofuran, 0. 28 mg of acetic acid I bar, 〇. 71 mg of ginseng (2-decyloxyphenyl)phosphine and stirred. A solution obtained by dissolving 67.3 mg (0.635 mmol) of sodium carbonate in 10 mL of water was added dropwise to the reaction liquid, and the mixture was refluxed for 9 hours to obtain a polymer compound L. The number average molecular weight of the polystyrene compound L converted polystyrene 324085 34

201247688 The weight average molecular weight of polystyrene converted to 3. 7x104' is 8 Comparative Example 6 (Synthesis of polymer compound hydrazine)

Pd(OAc)2 P(o-MeOC6H4)3 (ΗΟ)ζΒ

Β(ΟΗ)2 +

Na2C03 CuHa C„H29 In addition to using 21.8 mg (0.127 μM〇l) porphin and 2,5-di-acid instead of compound C, it reacted with real blue 7 in the same manner to obtain a polymer compound Μ° polymer compound. The number average molecular weight of the polystyrene is 5.4 χ 103'. The weight average molecular weight of the polystyrene is L OxlO4 °. Knife,,,,,,,,,, The solution of compound L is lost, and the organic transistor having the structure represented by the first formula is used as a gate electrode with a high concentration of doping + Βθ beach η-type. The surface of the ruthenium substrate is thermally oxidized to form a ruthenium oxide film (hereinafter referred to as "the function of the known thermal oxide film is used as the insulating layer. The ",, oxide film") °, long time by #丝玄 I丨 ( Phot ο 1 i thography ) The step of cutting the agricultural source electrode and the drain electrode on the thermal oxide film. The source electrode and the drain electrode are from the heat (Cr) layer and the gold (Au) layer, and the channel length is 2G. The film side has a network #m' channel width of 2 mm. The substrate obtained by the thermal oxidation of the % electrode electrode and the electrode electrode was ultrasonically washed with acetone, and subjected to UV ozone treatment with ozone UV cleaning 35 324085 201247688. Thereafter, the surface of the thermal oxide film was modified with /5-phenethyltrichloromethane, and the surface of the source electrode and the drain electrode was modified with pentafluorobenzenethiol. Next, 0.5% by weight of a polymer compound L ortho-dichlorobenzene solution was spin-coated at a number of revolutions of 1000 rpm on the surface-treated thermal oxide film, source electrode and drain electrode to form an organic semiconductor layer. Thereafter, the organic semiconductor layer was heated at 230 ° C for 1 hour to fabricate an electromechanical crystal 1. The gate voltage Vg and the source-electrode voltage Vsd of the obtained organic transistor 1 were changed to measure the transistor characteristics. The field effect mobility is 1. 8x 10_2cm2/Vs. Reference Example 2 (Manufacturing and evaluation of the organic transistor 2) An organic transistor 2 was produced in the same manner as in Reference Example 1 except that the polymer compound Μ was used instead of the polymer compound L. The gate voltage Vg and the source-electrode voltage Vsd of the obtained organic transistor 2 were changed to measure the transistor characteristics. Field effect mobility is 2. Ox 10-3cm2/Vs. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of an organic transistor (field effect type organic transistor). [Main component symbol description] 1 Active layer 2 Insulation layer 3 Gate electrode 4 Source electrode 5 Dip electrode 100 Organic transistor 324085 36

Claims (1)

201247688 VII. Patent application scope: 1. A compound expressed by the formula (1): R23 R24 In the formula L, the A system represents that the aryl group and the heteroaryl group each independently represent a hydrogen atom;; a sea group, a square group, a heteroaryl group or a cyano group, and the R and 2 groups each independently represent a hexafluorene atom, An alkyl group, an aryl group or a heteroaryl group; R21, R22, r23, r24, R25 R, R and R each independently represent a hydrogen atom, an alkyl group, an alkoxythio group, a (tetra), an aryl group or a heteroaryl group. Base; when plural, ^ can be the same or different H, when they are plural, they can be the same or different. When R is plural, they can be the same or different; when π is plural, they can be the same or different; R25 is plural When R26 is plural, it can be the same or different; when R27 is plural, it can be the same or different; when R28 is plural, it can be the same or different; ml,...,... The 蚪 and 蚪 are each independently representing an integer from 1 to 5, and ni, n2, n3 and n4 each independently represent 〇 or 1 ]. The compound of claim 1, wherein the A is a heterocyclic group. 324085 1 201247688 3. The compound according to claim 2, wherein the base of formula A (2) is: (2) wherein R41 and R42 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a sulfur-containing group, an aryl group, a heteroaryl group, a tooth atom, an aryl group or a schlossyl group; and a carbon atom in R41 The carbon atoms in R42 may also be bonded to form a cyclic structure; Y represents an S-, a 0-, - Se_, _NR51-, or -cn-m R62 system, each independently representing a nitrogen atom, an alkyl group, Aryl or heteroaryl]. 4. If the compound described in the application of the patent (4) 2, the towel, the basis of the formula A (3): Wherein R &amp; R each independently represents a gas atom, a pyridyl group, a sulfhydryl group, a thiol group, an aryl group or a heteroaryl group; and a U system represents a plurality of integers R of 1 to 5, It can be the same or different; when it is plural, it can be different (4); it can be directly bonded to each other 2 324085 2 201247688 2 carbon atoms are bonded to each other and R72 is the carbon atom in Rn and R72 The carbon atoms can also be bonded to form a cyclic structure]. 5. The compound of claim 3, wherein the formula A is based on R84 R33 (4) wherein R8i and m眇 each independently represent a gas atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or a heteroaryl group; the lanthanide group represents an integer from '1'; R81 When it is plural, the system may be the same or different. When R2 is plural, the system may be the same or different. When R83 is plural, the system may be the same or different. When R84 is plural, the system may be the same or different. In R81 and R82 in which each of the two carbon atoms directly bonded to each other is bonded, the carbon atom in R81 and the carbon atom in R82 may also depend on the structure of (4); the two carbons directly bonded to each other; In R83 and R84, each of which is bonded to the atomic mountain, the carbon atom in r83 and the carbon atom in R may also be bonded to form a cyclic structure. For example, in the middle π patent $&amp; The compound wherein the sum of ml and η1 is 2, the sum of m2 and η2 is 2, the sum of m3 and η3 is 2, and the sum of m4 and η4 is 2. - a method for producing a repeating unit represented by the formula (6) and a repeating single π molecule compound represented by the formula (7), which is in the presence of a transition metal mismatch 324085 3 201247688 and a base, as in the scope of application The compound according to any one of items 1 to 6 is polymerized with the compound represented by the formula (5); X1 - E - χ 2 (5) [wherein, the lanthanide group represents an aryl group, a heteroaryl group, An esc- or CR-CR-, R91 and R92 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a cyano group; the oxime and the X2 group each independently represent a tooth atom, an alkyl sulfonate group Or aryl sulfonate group]; (6) (7) [In the formulas (6) and (7), the human and the lanthanide are expressed in the same meaning as described above] • The production of the polymer compound as described in claim 7 of the patent application&gt; Aryl or heteroaryl. 9. In the (4) of the polymer compound described in the seventh or eighth aspect of the patent, X, and the r-type chlorine atom are 'atoms or moth atoms'. .::: ΠΓ9 of the ninth, -11, its base, alkali carbonate or phosphate. The method for producing a compound according to any one of claims 7 to 10, wherein the transition metal complex is a palladium error 324085