JP2009013109A - Carbazole-containing compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbazole-containing compound having high charge injection function and high thermal stability. <P>SOLUTION: The compound is expressed by general formula (I) (in the formula, A is a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted silicon-containing hydrocarbon group; R<SB>1</SB>to R<SB>14</SB>are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group; Y<SB>1</SB>and Y<SB>2</SB>are each independently a group containing one or more elements selected from oxygen, sulfur, phosphorus, boron, silicon, germanium and tin, a group having a substituted or unsubstituted aromatic group linked to a group containing one or more elements selected from oxygen, sulfur, phosphorus, boron, silicon, germanium and tin, a substituted or unsubstituted aromatic group or a substituted or unsubstituted alkylene group; m and n are each 0 or 1; and the carbazole group bonded through Y<SB>1</SB>is linked to either one of R<SB>5</SB>, R<SB>6</SB>and R<SB>7</SB>, and the carbazole group bonded through Y<SB>2</SB>is linked to either one of R<SB>12</SB>, R<SB>13</SB>and R<SB>14</SB>). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a carbazole-containing compound.

In recent years, organic materials such as pi-conjugated systems have attracted attention as optical / electronic functional materials, and asymmetry identification materials, asymmetric separation materials, polymer semiconductors, polymer conductors, electrochromic materials, electroluminescent materials There have been many reports on research aimed at application to nonlinear optical materials.
For example, as a typical example of an organic electronic device using an organic semiconductor material having a certain degree of carrier mobility, there is an organic electroluminescent element (hereinafter sometimes referred to as “organic EL element”). In addition, as a typical example of an organic electronic device using the organic semiconductor material, an organic solar battery, an organic photographic photoreceptor, and the like can be given.

  In other words, the organic solar cell and the organic photographic photoreceptor utilize a mechanism opposite to that of the organic EL element. That is, the most basic configuration is the same as that of the organic EL element, and is a structure in which an organic thin film having a two-layer structure is sandwiched between electrodes (see, for example, Non-Patent Document 1). Then, an electromotive force can be obtained by utilizing a photocurrent generated by absorbing light into the organic thin film. The current flowing at this time may be considered that carriers generated by light flow using the carrier mobility of the organic material. Therefore, if the charge injection barrier between the organic material and the electrode is reduced, an electromotive force can be obtained more efficiently.

  An organic transistor, which is another typical example of an organic electronic device, is a thin film transistor using an organic semiconductor material composed of a π-conjugated organic polymer or an organic small molecule in a channel region. A general organic transistor includes a substrate, a gate electrode, a gate insulating layer, source / drain electrodes, and an organic semiconductor layer. In an organic transistor, by changing the voltage (gate voltage) applied to the gate electrode, the amount of charge at the interface between the gate insulating film and the organic semiconductor film is controlled, and the current value between the source electrode and the drain electrode is changed. Switch.

However, when an organic semiconductor material is used as the semiconductor film of the organic transistor, there is a large charge injection barrier with the source electrode or the drain electrode, which causes a problem in element driving. Further, if the charge injection barrier between the organic semiconductor layer and the source electrode or the drain electrode is reduced, it is expected that the on-current value of the organic transistor is improved and the device characteristics are stabilized.
Therefore, in the development of organic electronic devices such as organic electroluminescent elements, development of organic electronic materials having a high charge injection function and excellent thermal stability is desired.
Appl. Phys. Lett. , Vol. 51, 913 (1987)

  An object of the present invention is to provide a novel carbazole-containing compound that is easy to produce, has a low charge injection barrier between the electrode and the organic layer, has high charge injection characteristics, and has high thermal stability. is there.

The above-mentioned subject is achieved by the following present invention.
That is, the invention according to claim 1 of the present invention is a carbazole-containing compound represented by the following general formula (I).

In the above general formula (I), A represents a substituted or unsubstituted hydrocarbon group or a hydrocarbon group containing substituted or unsubstituted silicon, and R _{1 to} R ₁₄ are each independently a hydrogen atom, Represents any one of an unsubstituted alkyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted aralkyl group, and Y ₁ and Y ₂ are each independently oxygen, sulfur, phosphorus, boron, silicon, A group having at least one selected from germanium and tin, a substituted or unsubstituted aromatic group and a group having at least one selected from oxygen, sulfur, phosphorus, boron, silicon, germanium and tin are linked Any one of a selected group, a substituted or unsubstituted aromatic group and a substituted or unsubstituted alkylene group, m and n each represents 0 or 1; The carbazole group via Y ₁ is linked to any of R ₅ , R ₆ and R ₇ , and the carbazole group via Y ₂ is linked to any of R ₁₂ , R ₁₃ and R ₁₄ .

  The invention according to claim 2 is the carbazole-containing compound according to claim 1, wherein A in the general formula (I) has a trifluoromethyl group.

According to the invention of claim 1 of the present invention, a carbazole-containing compound that is easy to manufacture, has a low charge injection barrier between the electrode and the organic layer, has high charge injection characteristics, and has high thermal stability. Can be provided.
According to the invention which concerns on Claim 2, the carbazole containing compound which was more excellent in the charge injection characteristic can be provided.

Hereinafter, the present invention will be described in detail.
The carbazole-containing compound of the present invention is represented by the following general formula (I).

In the above general formula (I), in general formula (I), A represents a substituted or unsubstituted hydrocarbon group or a hydrocarbon group containing substituted or unsubstituted silicon, and R _{1 to} R ₁₄ are Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, Y ₁ and Y ₂ are each independently oxygen, A group having at least one selected from sulfur, phosphorus, boron, silicon, germanium and tin, a substituted or unsubstituted aromatic group and oxygen, sulfur, phosphorus, boron, silicon, germanium and tin Represents any one of a group linked to a group having one or more, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted alkylene group, and m and n each represents 0 or 1 . The carbazole group via Y ₁ is linked to any of R ₅ , R ₆ and R ₇ , and the carbazole group via Y ₂ is linked to any of R ₁₂ , R ₁₃ and R ₁₄ .

As described above, an object of the present invention is to obtain a novel compound having excellent charge injection properties and excellent thermal stability as compared with conventional organic semiconductor materials.
With regard to the charge injection property, it has been conventionally known that a carbazole-containing compound such as polyvinyl carbazole has better consistency with an ITO electrode or a gold electrode than other organic materials. On the other hand, for example, a compound containing a diaryl structure generally has a high melting point and good thermal stability. Therefore, if these are combined, a novel compound having both characteristics can be obtained.

However, since the compound represented by the general formula (I) is structurally bulky, it is originally a compound that is difficult to synthesize stably. For example, a carbazole group is simply represented by R ₁ or R _2. Even if it tried to connect, the target product was not able to be obtained.

As a result of intensive studies by the present inventors, as will be described later, a desired novel compound can be stably obtained by employing a method of synthesizing a carbazole ring by a reaction of a primary amine and an aryl dihalide. It was found.
Further, as described later, the novel compound of the present invention obtained as described above is excellent in charge injection property and thermal stability. In addition, it is represented by the general formula (I) of the present invention. The compound has a large number of substituents such as R _{1 to} R ₁₄ , and the characteristics of the compound can be changed variously by combining them. Therefore, the characteristics change such as charge injection property and thermal stability can be easily and varied. This also has the effect that it can be achieved.

Hereinafter, the compound represented by the general formula (I) will be specifically described with reference to embodiments.
In the general formula (I), the substituted or unsubstituted hydrocarbon group represented by A or the hydrocarbon group containing a substituted or unsubstituted silicon preferably has a trifluoromethyl group. For example, it is selected from the structures shown in the following (a-1) to (a-30).
In the structures below, (a-1) to (a-15) are examples of substituted or unsubstituted hydrocarbon groups, and (a-16) to (a-30) are substituted or unsubstituted silicate groups. Examples of hydrocarbon groups containing silicon are shown. Also, in these, the terminal methyl group is omitted except for both ends linked to the central aryl group. The same applies to the following.

  Among these, A is particularly preferably a group having a structure represented by (a-1), (a-16), or the like.

In general formula (I), R _{1 to} R ₁₄ are each independently any of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group. Represents.
The alkyl group is preferably a linear alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms, and the linear alkyl group has 1 to 6 carbon atoms. As the range and the branched alkyl group, those having 1 to 6 carbon atoms are more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group.

  The aryl group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms. Specific examples include a phenyl group and a toluyl group.

  As the aralkyl group, those having 6 to 20 carbon atoms are preferable, and those having 6 to 12 carbon atoms are more preferable. Specific examples include a benzyl group and a phenethyl group.

  Among the various linking groups, from the viewpoint of the balance between the ease of synthesis, the reactivity, the good yield, and the characteristics such as the optoelectronic properties and thermal stability of the compound, the hydrogen atom, the carbon number of 1 to 4 A linear alkyl group or a branched alkyl group having 1 to 4 carbon atoms is preferred. More specifically, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, and a tert-butyl group are more preferable.

In the general formula (I), Y ₁ and Y ₂ have, for example, a structure selected from the structures shown below. In the following, (y-1) to (y-20) are examples of groups having one or more selected from oxygen, sulfur, phosphorus, boron, silicon, germanium and tin, (y-21) to (Y-26) is an example of a group in which a substituted or unsubstituted aromatic group and a group having one or more selected from oxygen, sulfur, phosphorus, boron, silicon, germanium and tin are linked (y -27) to (y-29) are examples of substituted or unsubstituted aromatic groups, and (y-30) are examples of substituted or unsubstituted alkylene groups.

Among these, Y ₁ and Y ₂ are particularly preferably groups having a structure represented by (y-1), (y-24), or the like.
In general formula (I), the carbazole group via Y ₁ is any of R ₅ , R ₆ and R ₇ , and the carbazole group via Y ₂ is any of R ₁₂ , R ₁₃ and R ₁₄ M and n are each 0 or 1, and when 0, it means that the carbazole group is directly bonded to these groups not via Y ₁ and Y ₂ .

In this embodiment, the compound represented by the general formula (I) may have a bilaterally symmetric structure or an asymmetrical structure via A, but in view of easiness of synthesis and purification, a symmetric structure It is desirable that
Hereinafter, Tables 1 to 3 show exemplary compounds 1 to 23 as specific examples of the carbazole-containing compound of the present embodiment, which is a compound having a structure represented by the general formula (I), but the present embodiment is limited to these. Is not to be done. In addition, the specific example of Tables 1-3 is a compound of a left-right symmetric structure centering on A of the center. In Table 1, the leftmost column (structure No.) indicates the exemplified compound number, the second column from the left indicates the structure of A in the general formula (I), and the third column from the left indicates the general formula. The structures of Y ₁ and Y ₂ in (I) (shown as Y in the table because they are the same structure) are shown. Further, the fourth column from the left shows the structure of the entire compound represented by the general formula (I) including the bonding positions of Y ₁ and Y ₂ .

The ionization potential of the carbazole-containing compound of this embodiment is preferably from 5.2 eV to 6.2 eV, more preferably from 5.4 eV to 6.1 eV. The melting point is preferably 100 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower. In addition, the said ionization potential can be calculated | required by measuring the photoelectron emission characteristic of a compound with an atmospheric-atmosphere type ultraviolet photoelectron spectrometer (the Riken Keiki Co., Ltd. make, AC-2).
The carbazole-containing compound of this embodiment having such characteristics is useful for organic electronic devices such as electrophotographic photosensitive members, organic electroluminescent elements (organic EL elements), organic solar cells, and organic transistors.

The carbazole-containing compound of the present embodiment can be produced by various general synthetic techniques, but according to the following production methods (1) and (2) (synthesis methods), the carbazole-containing compound can be efficiently produced. This is preferable because it is possible.
(1) A method of synthesizing a carbazole ring by a reaction between a primary amine and an aryl dihalide.
(2) A method of synthesis by directly reacting an aryl halide and carbazole.

  In particular, in this embodiment, since the diaryl skeleton at the central portion of the compound represented by the general formula (I) and the carbazole skeletons on both sides are bulky, it may be difficult to directly bond them. In this respect, the synthesis by the production method (1) above with respect to the production method (2) is preferred because the target compound can be obtained in a relatively high yield.

Hereinafter, the method for producing the carbazole-containing compounds (1) and (2) will be specifically described.
First, regarding the production method of (1), in this embodiment, for example, an amine compound represented by the following general formula (II) and a dihalogen compound represented by the following general formula (III) are coupled with a palladium catalyst. Thus, a carbazole ring can be synthesized (see, for example, “Angew. Chem. Int. Ed. 2003, 42, 2051-2053” for details).
When the structure of the dihalogen compound represented by the general formula (III) is different between (a) and (b), the dihalogen compound represented by the general formula (III) used in the reaction includes (a) and (b ) In an equimolar amount. In this case, (a) and (b) may be mixed and reacted together with the amine compound represented by the general formula (II), or one amino group of the amine compound represented by the general formula (II) may be reacted. After reacting either (a) or (b), either the remaining may be reacted with the other amino group.

Incidentally, in the general formula _{(II), A, R 5} ~R 7, R 12 ~R 14, Y 1, Y 2 are, _A in formula _{(I), R 5 ~R 7} , R 12 ~R 14 , Y ₁ and Y ₂ are the same. Further, in the general formula _{(III), R 1 ~R 4} , R 8 ~R 11 is the same as _{R 1 ~R 4, R 8 ~R} 11 in the general formula (I), _{X 1} is halogen Indicates. The halogen atom is not particularly limited, but iodine, bromine, chlorine and fluorine are preferably iodine and bromine, and particularly preferably bromine.

Regarding the production method of (2) above, a coupling reaction is carried out between a halogen compound represented by the following general formula (IV) and a carbazole compound represented by the following general formula (V) using a palladium catalyst or a copper catalyst. Thus, a carbazole-containing compound can be obtained.
Also in this synthesis, when the structure of the dihalogen compound represented by the general formula (V) is different between (a) and (b), as the carbazole compound represented by the general formula (V) used in the reaction, (a) And (b) are preferably reacted in equimolar amounts. In this case, (a) and (b) may be mixed and reacted together with the halogen compound represented by the general formula (IV), or one halogen group of the halogen compound represented by the general formula (IV) may be reacted. After reacting either (a) or (b), either the remaining may be reacted with the other halogen group.

In the general formula (IV), R _{5 to} R ₇ and R _{12 to} R ₁₄ are the same as R _{5 to} R ₈ and R _{12 to} R ₁₄ in the general formula (I), and X ₂ is a halogen element. Indicates. The halogen atom is not particularly limited, but iodine, bromine, chlorine, and fluorine are preferably iodine and bromine, and particularly preferably iodine. Further, in the general formula _{(V), R 1 ~R 4} , R 8 ~R 11 is the same as _{R 1 ~R 4, R 8 ~R} 11 in the general formula (I).

Next, the production method (synthesis method) of (1) is specifically shown below.
When the carbazole-containing compound represented by the general formula (I) is synthesized by the production method of (1), the diamine compound represented by the general formula (II) and the dihalogen compound represented by the general formula (III) Is reacted in the presence of a tertiary phosphine, a palladium compound, and a base.
The amount of the diamine compound represented by the general formula (II) is preferably in the range of 0.1 to 0.7 times in terms of molar ratio with respect to the dihalogen compound represented by the general formula (III), more preferably The range is 0.3 to 0.5 times.

  The tertiary phosphines are not particularly limited, and are triphenylphosphine, tri (tertiarybutyl) phosphine, tri (p-tolylphosphine), tri (m-tolylphosphine), triisobutylphosphine, tricyclohexyl. Tertiary alkyl phosphines such as phosphine and triisopropylphosphine can be mentioned, and tri (tertiary butyl) phosphine is preferable. The amount of tertiary phosphine used is not particularly limited, but is preferably in the range of 0.5 to 10 times in molar ratio with respect to the palladium compound, more preferably in the molar ratio of 2.0 to 2.0 with respect to the palladium compound. The range is 8.0 times.

  The palladium compound is not particularly limited, and is a divalent palladium compound such as palladium acetate (II), palladium chloride (II), palladium bromide (II), palladium trifluoroacetate (II), etc. And tris (dibenzylideneacetone) dipalladium (0), (dibenzylideneacetone) dipalladium (0), tetrakis (triphenylphosphine) palladium (0), and zero-valent palladium compounds such as palladium-carbon; Particularly preferable are palladium acetate and trisdibenzylideneacetone dipalladium (0). Although the usage-amount of a palladium compound is not specifically limited, It is the range of 0.001-10 mol% in conversion of palladium with respect to the diamine compound shown by general formula (II), More preferably, conversion of palladium In the range of 0.01 to 5.0 mol%.

  The base is not particularly limited, but potassium carbonate, rubidium carbonate, cesium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, tertiary butoxy potassium, tertiary butoxy sodium, sodium metal, potassium metal, hydrogen Examples thereof include potassium fluoride, and preferred are rubidium carbonate and tertiary butoxy sodium. The amount of these bases to be used is in the range of 1.0 to 10 times, more preferably in the range of 3.0 to 6.0 times in terms of molar ratio with respect to the diamine compound represented by the general formula (II). .

  The carbazole cyclization reaction is usually performed in an inert solvent. As a solvent that can be used, any solvent that does not significantly inhibit this reaction may be used. Aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ether solvents such as diethyl ether, tetrahydrofuran, dioxane, acetonitrile, dimethylformamide, dimethyl A sulfoxide etc. can be illustrated. Of these, more preferred are aromatic hydrocarbon solvents such as toluene and xylene.

  The amination reaction is carried out under an atmospheric pressure and an inert gas atmosphere such as nitrogen or argon, but can also be carried out under a pressurized condition. The reaction is carried out in the range of 20 to 300 ° C, more preferably in the range of 50 to 180 ° C. Although reaction time changes with reaction conditions, what is necessary is just to select from the range of several minutes-20 hours.

  After the reaction, the reaction solution is subjected to cerite filtration to remove inorganic substances, then diluted with a solvent such as toluene, washed in order of dilute hydrochloric acid and water until neutral, and dried with a drying agent such as magnesium sulfate. After removing the desiccant by filtration, the solvent is distilled off under reduced pressure. If the resulting crude product is column purified with silica gel, alumina, etc., or an adsorbent such as activated clay or activated carbon is added to adsorb unnecessary components, and the reaction product is crystalline Can be synthesized by recrystallization from an appropriate solvent such as hexane, methanol, acetone, ethanol, ethyl acetate, toluene, etc. to purify the carbazole-containing compound represented by the general formula (I).

Next, the production method (synthesis method) of (2) is specifically shown below.
When the carbazole-containing compound represented by the general formula (I) is synthesized by the production method (2), the dihalogen compound represented by the general formula (IV) and the carbazole compound represented by the general formula (V) are prepared. , A copper catalyst and a coupling reaction in the presence of a base.
The amount of the carbazole compound represented by the general formula (V) in the above reaction is preferably in the range of 2.0 to 3.0 equivalents, more preferably relative to 1 equivalent of the dihalogen compound represented by the general formula (IV). The range is from 2.0 to 2.4 equivalents.

  Examples of the copper catalyst include, but are not limited to, copper powder, copper (I) oxide, copper (II) sulfate, copper (III) acetate, and copper (I) iodide, preferably sulfuric acid. Copper (II). The amount used is preferably in the range of 0.001 to 3 parts by mass, more preferably in the range of 0.01 to 2 parts by mass with respect to 1 part by mass of the dihalogen compound represented by the general formula (IV).

  Although it does not specifically limit as said base, Potassium phosphate, sodium carbonate, potassium carbonate, rubidium carbonate, potassium hydrogen carbonate etc. are mentioned, Preferably it is potassium carbonate. The amount used is preferably in the range of 1 to 6 equivalents, more preferably in the range of 2.0 to 4.0 equivalents, relative to 1 equivalent of the dihalogen compound represented by the general formula (IV).

  A solvent may be used as necessary, and the reaction may be carried out without a solvent. Although not particularly limited, preferred are high-boiling water-insoluble hydrocarbon solvents such as n-tridecane, tetralin, p-cymene and terpinolene, and high-boiling waters such as o-dichlorobenzene and chlorobenzene. A halogen-based solvent is mentioned, and it is preferably used in a range of 0.1 to 3 parts by mass, more preferably in a range of 0.2 to 2 parts by mass with respect to 1 part by mass of the dihalogen compound represented by the general formula (IV). The This reaction is sufficiently efficient in an inert gas atmosphere such as nitrogen or argon, preferably in the range of 100 to 300 ° C, more preferably in the range of 150 to 270 ° C, and still more preferably in the range of 180 to 250 ° C. It is preferable to carry out the reaction while stirring and further to remove water generated during the reaction.

  After completion of the reaction, the reaction product is dissolved in a solvent such as toluene, isopar, n-tridecane, etc., and if necessary, unnecessary substances are removed by washing with water or filtration, and column purification with silica gel or alumina is performed. Add these adsorbents to the solution with activated clay, activated carbon, etc., and perform treatments such as adsorption of unnecessary components, and recrystallize from an appropriate solvent such as ethanol, ethyl acetate, toluene, etc. .

  The carbazole-containing compound of the present invention has excellent charge transportability, solubility controllability by a substituent such as an alkyl group or a linking group, and charge injection property controllability by a substituent such as a trifluoromethyl group or an alkyl group. Yes. In particular, physical properties such as ionization potential (IP) and glass transition temperature (Tg) can be controlled by introducing various substituents. Therefore, organic photoreceptors, organic solar cells, organic electroluminescent elements, organic It is a very useful compound as a material used in organic electronic devices such as transistors.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
<Example 1>
(Production of Exemplified Compound [1])
Exemplified compound [1] shown in Table 1 was synthesized according to the following reaction formula (I).
First, 5.7 g (18 mmol) of 2,2′-dibromobiphenyl, 255 mg of palladium acetate, 4.0 g (42 mmol) of sodium-t-butoxide and 200 ml of xylene were placed in a 500 ml three-necked flask, and tri-t- 4.0 g (3.6 mmol) of butylphosphine was added and stirred at reflux. Next, 3.08 g (9.0 mmol) of 2,2-bis (4-aminophenyl) hexafluoropropane was dissolved in 100 ml of xylene, and this was dropped into the mixture.

  After stirring with heating for 1 hour, alkali and palladium were removed by Celite filtration. At this time, it was washed with 100 ml of toluene. Then, it was washed with 200 ml of 1N HCl, 200 ml of distilled water twice and once with 200 ml of saturated saline. The organic layer was dried over anhydrous sodium sulfate, the solution obtained by filtration was concentrated with an evaporator, and 100 ml of methanol was added to obtain crude crystals. The obtained crude crystals were recrystallized from toluene / hexane to obtain Exemplified Compound [1] shown in Table 1 with a yield of 32%.

(Characteristics of Exemplified Compound [1])
Each characteristic and structure confirmation were performed about the obtained exemplary compound [1]. The results are as follows.
-Structural analysis-
An infrared absorption (IR) spectrum (KBr method) of the obtained exemplary compound [1] is shown in FIG.

An NMR spectrum ( ¹ H-NMR, solvent: CDCl ₃ ) is shown in FIG. Details of the signal are as follows.
・ NMR spectrum data:
δ 7.32 (ppm) (t, 4H, Ar), δ 7.46 (ppm) (t, 4H, Ar), δ 7.53 (ppm) (d, 4H, Ar), δ 7.6 (ppm) (d , 4H, Ar), δ 7.76 (ppm) (d, 4H, Ar), δ 8.16 (ppm) (d, 4H, Ar)

-Characteristic-
It was 278.8 degreeC when melting | fusing point was measured with the differential scanning calorimeter (DSC) (the Seiko Instruments make, Tg / DTA6200) about exemplary compound [1]. Further, the photoelectron emission characteristics were measured by an atmospheric-type ultraviolet photoelectron spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.), and the ionization potential obtained from the rising irradiation light energy was 6.01 eV.

<Example 2>
(Production of Exemplified Compound [12])
Exemplified compound [12] was synthesized according to the following reaction formula (II).
First, 6.2 g (20 mmol) of 2,2′-dibromobiphenyl, 288 mg (0.50 mmol) of bis (dibenzylideneacetone) palladium (0), 4.3 g (45 mmol) of sodium-t-butoxide, and 80 ml of xylene were added to 300 ml. Into a three-necked flask, under a nitrogen stream, 810 mg (4.0 mmol) of tri-t-butylphosphine was added and stirred at reflux. Next, 3.6 g (10 mmol) of 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane was dissolved in 50 ml of xylene, and this was dropped into the mixture.

  After heating and stirring for 3 hours, alkali and palladium were removed by Celite filtration. At this time, it was washed with 100 ml of toluene. Then, it was washed with 200 ml of 1N HCl, 200 ml of distilled water three times and once with 200 ml of saturated saline. The organic layer was dried over anhydrous sodium sulfate, the solution obtained by filtration was concentrated with an evaporator, and 100 ml of methanol was added to obtain crude crystals. The obtained crude crystals were purified from ethyl acetate / hexane by silica gel column chromatography to obtain Exemplified Compound [12] shown in Table 1 in a yield of 42%.

(Characteristics of Exemplary Compound [12])
Each characteristic and structure confirmation were performed about the obtained exemplary compound [12]. The results are as follows.
-Structural analysis-
FIG. 3 shows an infrared absorption spectrum (KBr method) of the obtained exemplary compound [12].

Further, FIG. 4 shows an NMR spectrum ( ¹ H-NMR, solvent: CDCl ₃ ). Details of the signal are as follows.
・ NMR spectrum data:
δ 1.96 (ppm) (s, 6H, CH ₃ ), δ 6.90 (ppm) (d, 4H, Ar), δ 7.28 (ppm) (m, 8H, Ar), δ 7.49 (ppm) ( m, 4H, Ar), δ 7.60 (ppm) (d, 2H, Ar), δ 8.16 (ppm) (d, 4H, Ar)

-Characteristic-
It was 91.2 degreeC when melting | fusing point was measured for the exemplary compound [12] with the said differential scanning calorimeter. The ionization potential determined by the atmospheric-type ultraviolet photoelectron spectrometer was 6.3 eV.

<Example 3>
(Production of Exemplary Compound [5])
Exemplified compound [5] shown in Table 1 was synthesized according to the following reaction formula (III).
First, 3.1 g (10 mmol) of 2,2′-dibromobiphenyl, 56 mg (0.25 mmol) of palladium acetate, 2.1 g (23 mmol) of sodium tert-butoxide and 100 ml of xylene were placed in a 300 ml three-necked flask, , 410 mg (2.0 mmol) of tri-t-butylphosphine was added, and the mixture was stirred at reflux. Next, 3.1 g (10 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane was dissolved in 50 ml of xylene, and this was added dropwise to the mixture.

  After stirring with heating for 1 hour, alkali and palladium were removed by Celite filtration. At this time, it was washed with 50 ml of toluene. Then, it was washed with 100 ml of 1N HCl, 150 ml of distilled water three times, and once with 150 ml of saturated brine. The organic layer was dried over anhydrous sodium sulfate, the solution obtained by filtration was concentrated with an evaporator, and 100 ml of methanol was added to obtain crude crystals. The obtained crude crystals were purified from ethyl acetate / hexane by silica gel column chromatography to obtain Exemplified Compound [5] shown in Table 1 at a yield of 34%.

(Characteristics of Exemplary Compound [5])
Each characteristic and structure confirmation were performed about the obtained exemplary compound [5]. The results are as follows.
-Structural analysis-
An infrared absorption spectrum (KBr method) of the obtained exemplary compound [5] is shown in FIG.

An NMR spectrum ( ¹ H-NMR, solvent: CDCl ₃ ) is shown in FIG. Details of the signal are as follows.
・ NMR spectrum data:
δ 7.12 (ppm) (d, 4H, Ar), δ 7.30 (ppm) (m, 8H, Ar), δ 7.36-7.50 (ppm) (m, 12H, Ar), δ 7.56 ( ppm) (d, 4H, Ar), δ 8.16 (ppm) (d, 4H, Ar)

-Characteristic-
With respect to the exemplified compound [5], the melting point was measured by the differential scanning calorimeter and found to be 100.0 ° C. The ionization potential obtained by the atmospheric-type ultraviolet photoelectron spectrometer was 6.13 (± 0.1) eV.

2 is an IR spectrum of the compound obtained in Example 1. 2 is an NMR spectrum of the compound obtained in Example 1. 2 is an IR spectrum of the compound obtained in Example 2. 2 is an NMR spectrum of the compound obtained in Example 2. 3 is an IR spectrum of the compound obtained in Example 3. 2 is an NMR spectrum of the compound obtained in Example 3.

Claims (2)

A carbazole-containing compound represented by the following general formula (I):

(In General Formula (I), A represents a substituted or unsubstituted hydrocarbon group or a hydrocarbon group containing substituted or unsubstituted silicon, and R _{1 to} R ₁₄ are each independently a hydrogen atom, Represents any one of an unsubstituted alkyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted aralkyl group, and Y ₁ and Y ₂ are each independently oxygen, sulfur, phosphorus, boron, silicon, A group having at least one selected from germanium and tin, a substituted or unsubstituted aromatic group and a group having at least one selected from oxygen, sulfur, phosphorus, boron, silicon, germanium and tin are linked the group represents one of a substituted or unsubstituted aromatic group and a substituted or unsubstituted alkylene group, m, n each represents 0 or 1. also, mosquitoes through Y ₁ Bazoru groups in any of _R 5, _{R 6} and _{R 7,} carbazole group via the _{Y 2} are respectively connected to one of _{R 12, R 13} and _{R 14.)}   The carbazole-containing compound according to claim 1, wherein A in the general formula (I) has a trifluoromethyl group.

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