JP2010168347A - Method for producing carbazole derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a carbazole derivative suitable as an organic solid laser material simply and safely. <P>SOLUTION: This method for producing a compound expressed by formula (1) [wherein Z is a carbon atom or silicon atom] is provided by reacting a specific compound A with a specific compound B in the presence of a palladium catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a carbazole derivative. More specifically, the present invention relates to a method for easily and safely producing a carbazole derivative that exhibits semiconductor characteristics and can be suitably used for an organic solid-state laser material having a very low ASE threshold.

At present, inorganic semiconductor lasers based on inorganic materials are widely used as semiconductor lasers.
As described above, there are only expensive methods for producing the laser material, and it is difficult to further reduce the cost. In addition, with inorganic materials, fine adjustment of the laser wavelength is very difficult and limited. Laser oscillation is possible only in the wavelength region. In addition, toxic substances such as arsenic are also used, which is not preferable from the viewpoint of global environmental conservation.

  In order to solve these problems, organic solid-state lasers based on organic materials such as spirofluorene, oligothiophene, and carbazole have been actively developed (see Non-Patent Documents 1 to 3). Among them, it has been found that a compound of the following structural formula (I) in which carbazole is bonded to both ends of a biphenylene group via a vinyl group has a relatively low ASE threshold and has excellent characteristics as a laser active material. (Refer nonpatent literature 4).

  The inventors who developed the compound proposed in Non-Patent Document 4 seem to have continued research and development of the compound and its peripheral compounds, and then show semiconductor characteristics and have a very low ASE threshold. And succeeded in developing a compound of the following structural formula (II), which is a general formula, having a structure common to that of the compound (Patent Document 1).

JP 2008-106032 A

Appl. Phys. Lett. 2004, 85, 1659. Adv. Mater. 2005, 17, 2073. Appl. Phys. Lett. , 2004, 84, 2724. Appl. Phys. Lett. 2004, 86, 071110.

  The present inventors are also researching and developing carbazole derivatives for use in EL devices, and as such, are disclosed in the compounds of the structural formula (II) that are the same carbazole derivatives, particularly in the examples of Patent Document 1. 9,9 ′-[spiro-9,9′-bifluorene-2,7-diylbis (ethene-2,1-diyl-4,1-phenylene)] bis (9H-carbazole) , Simply abbreviated as “spiroSBCz”), and earnestly studied. As a result, the number of steps in the manufacturing process is great, but a reagent that is careful in handling in the manufacturing process is used. I found out.

  That is, the production method described in Example 1 of the Patent Document 1 (hereinafter simply referred to as a prior production method) includes 4- (9H-carbazol-9-yl) benzaldehyde (hereinafter referred to as a first starting material), 2 , 7-dibromo-spiro-9,9′-bifluorene (hereinafter referred to as the second starting material) to obtain intermediates and react the obtained intermediates with each other. “Spiro SBCz” is manufactured. In addition, it is necessary to use a substance that requires careful handling in the process of producing an intermediate using 2,7-dibromo-spiro-9,9'-bifluorene as a starting material.

  Specifically, in the process using 4- (9H-carbazol-9-yl) benzaldehyde as a starting material, the final intermediate {4- (9H-carbazol-9-yl) benzyl is passed through a two-step intermediate. } N-butyllithium used to produce diethyl phosphate, and to produce intermediates using 2,7-dibromo-spiro-9,9′-bifluorene as a starting material, which requires careful handling. Thus, 2,7-diformyl-spiro-9,9′-bifluorene, which is an intermediate, is produced.

  As described above, in the prior production method, the final intermediate obtained in the former {4- (9H-carbazol-9-yl) benzyl} phosphoric acid diethyl ester and the intermediate obtained in the latter are used. The target substance “spiro SBCz” is produced by reacting with a certain 2,7-diformyl-spiro-9,9′-bifluorene, and it is necessary to involve many production processes and substances requiring careful handling. Become.

The inventors of the present invention reduce the number of steps and take care in handling in order to take advantage of the properties of the above-described compound of structural formula (II), particularly “spiro SBCz” disclosed in the Examples of Patent Document 1. It is the present invention that the inventors of the present invention have sought to research and develop a method capable of producing a compound of the structural formula (II) such as “spiro SBCz” without using a substance, and as a result, succeeded in the development.
Accordingly, an object of the present invention is to provide a method for easily and safely producing spiroSBCz and a compound having the same structure and properties as that of spiroSBCz.

（但し、式中、Ｚは炭素原子又は珪素原子を表す。Ｒ¹及びＲ²は、それぞれ独立に置換基を有していてもよい炭素数６〜１８の芳香族炭化水素基、置換基を有していてもよい炭素数３〜１３の芳香族複素環基、又は置換基を有していてもよい主鎖の炭素数が１〜１０のアルキル基を表し、Ｒ¹とＲ²は、直接もしくは置換基を介して環を形成していてもよい。Ｘ¹及びＸ²は、それぞれ独立にハロゲン原子を表す。） This invention provides the method of manufacturing the carbazole derivative of the compound C shown by following General formula (1) which solved the said subject, The manufacturing method is the compound A shown in following Structural formula (2), and A compound B represented by the following general formula (3) is reacted in the presence of a palladium catalyst.

(However, in the formula, Z represents a carbon atom or a silicon atom. R ¹ and R ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms and a substituent which may have a substituent. An aromatic heterocyclic group having 3 to 13 carbon atoms which may have, or an alkyl group having 1 to 10 carbon atoms in the main chain which may have a substituent, R ¹ and R ² are A ring may be formed directly or through a substituent, and X ¹ and X ² each independently represent a halogen atom.)

In the present invention, the following is further preferable.
(1) Compound A and Compound B are mixed and reacted so that Compound A is 2 equivalents or more with respect to Compound B.
(2) The reaction between compound A and compound B is performed by heating.
(3) The reaction is performed in the presence of a base.
(4) The palladium catalyst is a catalyst in which a phosphine-based ligand and a zero-valent or divalent palladium complex are mixed.
(5) X ¹ and X ² are each independently a bromine atom or an iodine atom.
(6) X ¹ and X ² represent the same atom.
(7) Z is a carbon atom.

The present invention is excellent in that it can provide a method for easily and safely producing “spiro SBCz” and a compound having the same structure and properties. In this regard, a case where “spiroSBCz” is manufactured will be described in detail below.
In the prior production method described in Patent Document 1, 4- (9H-carbazol-9-yl) benzaldehyde as a first starting material and 2,7-dibromo-spiro-9,9′-bifluorene as a second starting material are used. The intermediates are once produced in each starting material, and the resulting intermediates are reacted to produce “spiro SBCz” which is the final target substance.

  In particular, from the first starting material, 4- (9H-carbazol-9-yl) benzyl alcohol and 9- {4- (bromomethyl) phenyl} -9H-carbazole are prepared through a two-step intermediate, and then the final intermediate. {4- (9H-carbazol-9-yl) benzyl} phosphoric acid diethyl ester is produced from the second starting material and is an intermediate 2,7-diformyl-spiro-9,9 ′ -By producing bifluorene and reacting the final intermediate from the first starting material and the intermediate from the second starting material, "spiroSBCz", which is the target substance, is produced in the prior production method.

For this reason, the number of reaction steps is increased in the prior production method, and n-butyl lithium, which requires careful handling, is required in the step of producing an intermediate from the second starting material.
In contrast, in the present invention, 9- (4-vinylphenyl) produced in a one-step reaction process using 4- (9H-carbazol-9-yl) benzaldehyde, which is the first starting material of the preceding production method. By using -9H-carbazole as the first production raw material and using the same compound as the second starting raw material in the preceding production method as the second production raw material, the final target substance “spiro SBCz” can be produced simply by reacting both compounds. It is.

As described above, in the present invention, the number of reaction steps until the final target substance is produced is reduced to half or less of the prior production method, and the intermediate for the second production raw material is the same as in the prior production method. Since it is not necessary to manufacture, the use of n-butyllithium which requires careful handling at that time is also unnecessary.
Therefore, the present invention is excellent in that it can provide a method for easily and safely producing spiroSBCz and a compound having the same structure and properties as described above.

The figure which shows the NMR chart of obtained spiroSBCz. The figure which shows the solution absorption spectrum of the spiroSBCz. The figure which shows the solution emission spectrum of the spiroSBCz. The figure which shows the thin film absorption spectrum of the spiroSBCz. The figure which shows the thin film emission spectrum of the spiroSBCz. The figure which shows the emission spectrum at the time of irradiating the nitrogen laser to the thin film which co-deposited the spiroSBCz and CBP. The figure which shows the relationship between the excitation light intensity | strength at the time of irradiating a nitrogen laser to the thin film which co-deposited the spiroSBCz and CBP, and emitted light intensity.

  Hereinafter, various embodiments of the present invention including the best mode for carrying out the present invention will be described in detail. However, the present invention is not limited to the description. Therefore, those skilled in the art can easily understand that the modes and details can be variously changed without departing from the spirit and scope of the present invention.

（式中、Ｚは炭素原子又は珪素原子を表す。Ｒ¹及びＲ²は、それぞれ独立に置換基を有していてもよい炭素数６〜１８の芳香族炭化水素基、置換基を有していてもよい炭素数３〜１３の芳香族複素環基、又は置換基を有していてもよい主鎖の炭素数が１〜１０のアルキル基を表し、Ｒ¹とＲ²は、直接もしくは置換基を介して環を形成していてもよい。Ｘ¹及びＸ²は、それぞれ独立にハロゲン原子を表す。） The method for producing the carbazole derivative which is the compound C represented by the following general formula (1) of the present invention is represented by the first production raw material compound A represented by the following structural formula (2) and the following general formula (3) as described above. The second production raw material compound B is reacted in the presence of a palladium catalyst.

(In the formula, Z represents a carbon atom or a silicon atom. R ¹ and R ² each independently have an aromatic hydrocarbon group having 6 to 18 carbon atoms and a substituent which may have a substituent. Represents an optionally substituted aromatic heterocyclic group having 3 to 13 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in the main chain which may have a substituent, and R ¹ and R ² may be directly or A ring may be formed via a substituent, and X ¹ and X ² each independently represent a halogen atom.)

The reaction formula is as shown in the following reaction formula (1).

R ¹ and R ² will be described in more detail below.
Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent in R ¹ and R ² include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), An anthryl group (preferably a 2-anthryl group), a phenanthryl group, a fluorenyl group and the like may be mentioned, and these may have a substituent. Examples of the substituent that may be included in that case include an alkyl group, an alkoxyl group, and a fluorine atom.

  Examples of the aromatic heterocyclic group having 3 to 13 carbon atoms which may have a substituent include a 6-membered monocyclic substituent such as a pyridine ring, a pyrimidine ring and a pyrazine ring; a thiophene ring, a furan ring, 5-membered monocyclic substituents such as imidazole ring and thiazole ring; 6-membered condensed ring substituents such as quinoline ring, isoquinoline ring and acridine ring; 6- and 5-membered rings such as indole ring and benzothiophene Substituents of condensed ring; and tricyclic aromatic substituents such as carbazole fused with 6-membered ring and 5-membered ring. Examples of the substituent that they may have include an alkyl group, an alkoxyl group, and a fluorine atom.

  Examples of the alkyl group having 1 to 10 carbon atoms in the main chain which may have a substituent include a methyl group, an ethyl group, a butyl group, a hexyl group, and an octyl group. Examples of the substituent that these alkyl groups may have include an alkyl group.

Examples of R ¹ and R ² forming a ring directly or through a substituent include a heterocyclic ring containing “Z” in which “R ¹ ” and “R ² ” are bonded in the general formula (1). The structural part is represented by the following structural formula (4).

The part of “*” in the structural formula (4) corresponds to the part of “*” in the general formula (4). That is, an example in which the ring is formed includes a structure in which the portion of the general formula (4) in the general formula (1) is substituted with the structural formula (4).
R ¹ and R ² may be the same or different, but are preferably the same in terms of ease of synthesis. Furthermore, R ¹ and R ² are preferably aromatic hydrocarbon groups from the electrochemical stability of the compound.

In the production method of the present invention, the compound A is preferably mixed so that the compound A is 2 equivalents or more with respect to the compound B and the compound A and the compound B are reacted. However, specifically, it is preferable that the compound A is mixed and reacted so as to be 2 to 3 equivalents relative to the compound B, and further mixed so as to be 2 to 2.5 equivalents. It is more preferable to react.
The reaction temperature in that case is not specifically limited, It is good to carry out in the range of room temperature to 200 degreeC, Preferably it is good to carry out by heating and 60-150 degreeC is good.

  The reaction is preferably performed in the presence of a base in order to trap the acid generated in the reaction. The base is not particularly limited, and various inorganic and organic bases can be used. Potassium etc. can be illustrated as a suitable thing. In this case, the amount of base used is preferably 1 to 5 equivalents, more preferably 3 to 4 equivalents, relative to the halogenated fluorene derivative.

  The palladium catalyst used at that time is preferably a divalent or zero-valent complex of palladium, and is preferably a complex produced by mixing it with a phosphine-based ligand, that is, a complex. A generally available divalent or zero-valent complex can be used as the palladium complex, but palladium acetate is preferably used. The amount of palladium complex to be used is preferably 0.001 to 1 equivalent, more preferably 0.01 to 0.1 equivalent, relative to the halogenated fluorene derivative. As the phosphine-based ligand, it is desirable to use available tris (ortho-tolyl) phosphine or tristar butyl phosphine. The phosphine-based ligand used is preferably 1 to 5 equivalents, more preferably 3 to 4 equivalents, relative to the palladium complex.

As for the compound B as the second production raw material, various compounds can be used without particular limitation as long as it is a compound in the category represented by the general formula (3). Preferably, X ¹ and X ² are Each is preferably a bromine atom or an iodine atom, and more preferably X ¹ and X ² are the same atom. Furthermore, Z is preferably a carbon atom.
In addition, it is because the characteristic of the target substance obtained is excellent about the compound B that the thing of the said range is preferable.

[Method for Producing Compound A as First Production Raw Material]
A method for producing Compound A, which is the first production raw material in the production method of the present invention, will be described below. The compound A can be produced from 4- (9H-carbazol-9-yl) benzaldehyde, which is the first starting material in the prior production method, and in this case, 4- (9H- It can be produced by using a Wittig reaction using carbazol-9-yl) benzaldehyde as a raw material.

  This Wittig reaction is a reaction that produces an alkene from a phosphorus ylide and a carbonyl compound, which is called a Wittig reagent. In the present invention, the Wittig reaction can be performed by a general method in the Wittig reaction. That is, triphenylphosphonium methylide is generated by reacting methyltriphenylphosphonium bromide with a base at a low temperature in a solvent, the first starting material is added thereto, and the reaction is allowed to proceed for an appropriate time. Compound A as a raw material is produced. From this, the solvent is removed, and the compound A crystals can be obtained by purification by column chromatography or the like.

  The solvent used at that time is preferably a highly polar solvent capable of dissolving methyltriphenylphosphonium bromide. Specifically, dimethylformamide, tetrahydrofuran or the like is used. Triphenylphosphonium methylide is generated by adding a base to this solution. The amount of base added is preferably 1 to 3 equivalents, more preferably 1.5 to 2 equivalents, based on methyltriphenylphosphonium bromide. The reaction temperature is preferably from -30 ° C to room temperature, more preferably from -10 ° C to 10 ° C. The base may be a common one, and sodium methoxide is preferred.

  After generating triphenylphosphonium methylide in this way, 4- (9H-carbazol-9-yl) benzaldehyde as the first starting material is added to the system. The amount of the first starting material to be added is preferably 0.1 to 1.5 equivalents, more preferably 0.5 to 1.0 equivalents, based on methyltriphenylphosphonium bromide. The reaction temperature at the time of addition is preferably from -30 ° C to room temperature, more preferably from -10 ° C to 10 ° C. The reaction time is not particularly limited, but is usually completed within several hours. In this way, 9- (4-vinylphenyl) -9H-carbazole, which is the first production raw material of the present invention, is produced.

[Specific production process of compound C such as spiroSBCz]
The production process of the compound C such as spiroSBCz which is the objective production substance of the present invention will be described in detail below.
In this production process, compound A produced from 4- (9H-carbazol-9-yl) benzaldehyde, which is the first starting material used in the preceding production method, and second starting material used in the preceding production method, 2 In this step, compound B such as, 7-dibromo-spiro-9,9′-bifluorene is coupled by Mizorogi-Heck reaction using a palladium catalyst to produce compound C.

  This Mizorogi-Heck reaction is a known reaction in which a substituted olefin is synthesized by cross-coupling an aryl halide with a terminal olefin in the presence of a palladium catalyst, and can also be carried out by a general technique in the present invention. That is, a halogenated fluorene derivative and 9- (4-vinylphenyl) -9H-carbazole are mixed in an appropriate solvent in an appropriate solvent, a palladium catalyst, a ligand and a base are added, and heated moderately. React for an appropriate time. After the reaction, the reaction solution is recrystallized as it is, or purified by column chromatography or the like, and then recrystallized to obtain a crystal of compound C.

In that case, the mixing ratio of 9- (4-vinylphenyl) -9H-carbazole and the halogenated fluorene derivative is preferably 2-3: 1, more preferably 2-2.5: 1. The halogenated fluorene derivative is preferably a bromo form or an iodo form from the viewpoint of reaction activity.
Furthermore, the solvent to be used is preferably a solvent having high solubility and high polarity. Specifically, dimethylformamide, tetrahydrofuran or the like is used.

  The palladium catalyst used in this case is preferably a palladium complex (catalyst) formed by mixing a divalent or zero-valent complex and a phosphine-based ligand in the system. A generally available divalent or zero-valent complex can be used as the palladium complex, but palladium acetate is preferably used. The amount of the palladium complex to be used is preferably 0.001 to 1 equivalent, more preferably 0.01 to 0.1 equivalent, relative to the halogenated fluorene derivative. As the phosphine-based ligand, it is desirable to use available tris (ortho-tolyl) phosphine or tristar butyl phosphine. The phosphine-based ligand used is preferably 1 to 5 equivalents, more preferably 3 to 4 equivalents, relative to the palladium complex.

Further, the base at that time is for trapping the acid generated by the reaction. In general, an inorganic base is used, but triethylamine, potassium carbonate and the like are preferably used. The amount of the base used is preferably 1 to 5 equivalents, more preferably 3 to 4 equivalents, based on the halogenated fluorene derivative.
The reaction temperature is preferably from room temperature to 200 ° C, more preferably from 60 to 150 ° C. In general, the higher the reaction temperature, the faster the reaction is completed.

Hereinafter, examples of the method for producing the carbazole derivative of the present invention will be described. However, the present invention is not limited to these examples, and it is understood that the present invention is specified by the description of the scope of claims. Nor.
In this example, a production example using spiroSBCz as a target production compound is shown, but a production example of 9- (4-vinylphenyl) -9H-carbazole as a first production raw material which is one of raw material materials used in this production example. Is also shown.
The structural formula of the spiro SBCz is as shown in the following structural formula (5).

[Step 1] Synthesis of 9- (4-vinylphenyl) -9H-carbazole The reaction formula for this synthesis reaction is as shown in the following reaction formula (2).

Next, the reaction process will be specifically described below.
2.7 g (10 mmol) of 4- (9H-carbazol-9-yl) benzaldehyde and 5.4 g (15 mmol) of methyltriphenylphosphonium bromide were placed in a 100 mL three-necked flask, and the flask was purged with nitrogen, and then 50 mL of tetrahydrofuran was added. . The mixed solution was cooled to −3 ° C. and stirred for 20 minutes, and then a suspension of 1.62 g (30 mmol) of sodium methoxide in 30 mL of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the mixed solution was gradually returned to room temperature and stirred at room temperature for 15 hours.

  The mixed solution was poured into water, the organic layer and the aqueous layer were separated using a separatory funnel, and the aqueous layer was extracted three times with ethyl acetate. The obtained extracted solution and the organic layer were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and this mixture was naturally filtered. The obtained filtrate was concentrated to obtain a yellow powder. The resulting yellow powder was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 4: 1) to obtain 2.33 g (yield 86%) of the compound, which was the target compound 9- (4- It was confirmed by nuclear magnetic resonance (NMR) that it was vinylphenyl) -9H-carbazole.

The measurement data of ¹ H NMR of the obtained compound is as shown below.
¹ H NMR (300 MHz, CDCl 3): δ (ppm) = 5.34 (d, 1H, J = 10 Hz), 5.83 (d, 1H, J = 17 Hz), 6.80 (dd, 1H, J1 = 10 Hz, J2 = 17 Hz), 7.22-7.32 (m, 2H), 7.50 (d, 2H, J = 7.3 Hz), 7.61 (d, 2H, J = 7.3 Hz) 8 .13 (d, 2H, J = 7.3 Hz)

[Step 2] Synthesis of spiroSBCz First, the reaction formula for this synthesis reaction is shown in the following reaction formula (3).

Next, the reaction process will be specifically described below.
In a 50 mL three-necked flask, 1.8 g (6.6 mmol) (Compound A) of 9- (4-vinylphenyl) -9H-carbazole of the first production raw material produced in Step 1 and 2,7 of the second production raw material were prepared. -Dibromo-spiro-9,9'-bifluorene 1.4 g (3.0 mmol) (compound B), palladium (II) acetate 0.042 g (0.18 mmol, 6 mol%) and tris (ortho-tolyl) phosphine 0.39 g (0.63 mmol) was added, and the atmosphere in the flask was replaced with nitrogen. Then, 15 mL of N, N-dimethylformamide and 7 mL of triethylamine were added, and the mixed solution was stirred at 100 ° C.

  After heating and stirring for 2 hours, disappearance of the raw materials was confirmed on silica gel thin layer chromatography (TLC). The reaction solution was poured into hot toluene, suction filtered, and the precipitate was washed with toluene. The obtained filtrate was washed with a separatory funnel in the order of 1M hydrochloric acid, pure water and saturated brine. The obtained organic layer was dried over anhydrous magnesium sulfate and then evaporated to dryness under reduced pressure to obtain an orange powder. This powder was recrystallized from chloroform to obtain 2.2 g (yield 86%) of a yellow powder.

This yellow powder was confirmed to be the target compound spiroSBCz by ¹ H NMR and MS spectrum (M ⁺ = 851.342).
The measurement data of ¹ H NMR of the obtained compound is as shown below.
¹ H NMR (300 MHz, C ₂ D ₂ Cl ₄ ): δ (ppm) = 6.79 (d, 2H, J = 6.8 Hz), 6.85 (s, 2H), 6.97 (s, 4H ), 7.11 (t, 2H, J = 6.8 Hz), 7.15-7.25 (m, 4H), 7.28-7.44 (m, 14H), 7.54 (d, 6H) , J = 7.8 Hz), 7.81 (d, 2H, J = 7.8 Hz), 7.87 (d, 2H, J = 7.8 Hz), 8.05 (d, 4H, J = 7. 8 Hz).

  An NMR chart of the obtained spiroSBCz is shown in FIG. In FIG. 1, (B) is an enlarged chart of the range of 6.5 ppm to 8.5 ppm in (A). Moreover, the absorption spectrum of the toluene solution of spiroSBCz is shown in FIG. 2, and the emission spectrum is shown in FIG. For these measurements, an ultraviolet visible light spectrophotometer (manufactured by JASCO Corporation, model V550) was used. The solution was placed in a quartz cell for measurement. As for the absorption spectrum, an absorption spectrum obtained by subtracting the absorption spectrum measured only with toluene is shown. Further, the absorption spectrum of the spiro SBCz thin film is shown in FIG. 4, and the emission spectrum is shown in FIG. About the thin film, it vapor-deposited on the quartz substrate, produced the sample, and measured it. Regarding the absorption spectrum, an absorption spectrum obtained by subtracting the absorption spectrum of quartz alone is shown.

  2 and 4, the horizontal axis represents wavelength (nm) and the vertical axis represents absorption intensity (arbitrary unit). 3 and 5, the horizontal axis represents wavelength (nm) and the vertical axis represents emission intensity (arbitrary unit). In the case of this toluene solution, absorption was observed at around 388 nm. The maximum emission wavelength of the toluene solution was 427 nm (excitation wavelength: 388 nm). In the case of the thin film, absorption was observed in the vicinity of 238 nm, 296 nm, 348 nm, and 374 nm. The maximum emission wavelength was 460 nm (excitation wavelength: 370 nm) in the case of the thin film.

[Usage example]
A thin film was produced by co-evaporation using the compound spiroSBCz produced in Example 1, and the characteristics of the thin film were tested. The specific method for producing the thin film is as follows.

[Thin Film Manufacturing Method]
A 180 nm thick thin film in which 10% by weight of the compound spiroSBCz prepared in Example 1 was dispersed in a CBP (4,4 ′-(N, N′-dicarbazolyl) biphenyl) host as a guest molecule was applied to a glass substrate under vacuum. Samples were prepared by co-evaporation.

[Characteristic test method]
The sample was irradiated with a nitrogen gas laser having a wavelength of 337 nm as an excitation light source and photoexcited. The light emission from the sample was observed from the end face of the glass substrate by Multi-channel photodiode (PMA-11 manufactured by Hamamatsu Photonics), which is a multichannel spectrophotometer, and the emission spectrum and the relationship between the excitation light intensity and the emission intensity were determined.

  The intensity of the emission spectrum as excitation light was measured by changing the incident light intensity between 0.03 and 100% using an ND filter (neutral density filter) and measuring the emission spectrum as described above. Furthermore, each peak intensity was calculated | required, the relationship between excitation light intensity and light emission intensity was calculated | required, and it put together in the graph.

In this graph, two approximate lines are drawn for a sudden change in peak intensity, and the ASE threshold value is calculated from the intersection.
According to this, assuming that the intensity of 100% of the nitrogen laser is 1, the relative excitation light intensity 0.0008 is obtained as the ASE threshold value, and the ASE threshold value is specifically calculated using this as follows. That is, since the intensity of 100% nitrogen laser is 1.337 mJ / cm ² , the ASE threshold value of spiroSBCz is 1.337 × 0.0008 = about 1.06 μJ / cm ² .

FIG. 6 shows the intensity of the emission spectrum from the substrate end face of the thin film co-deposited with CBP. On the other hand, FIG. 5 shows the emission spectrum of the thin film of spiroSBCz alone, and comparing the two shows that the emission spectrum from the substrate end face of FIG. 6 has a sharper peak than the spectrum of FIG.
This is due to the fact that the emission intensity of a certain wavelength is increased mainly due to the stimulated emission, so that it can be said that ASE oscillation occurs.
It can also be seen from this figure that the ASE oscillation wavelength is 471 nm.

The relationship between the excitation light intensity and the emission intensity described above is shown in FIG.
The intensity of the excited light and the intensity of the light emitted from the material irradiated with the excitation light are generally proportional to each other, that is, if the excitation light intensity is doubled, the emission intensity is also doubled.
On the other hand, it is known that when a laser dye is irradiated with excitation light stronger than a predetermined intensity, a light emission intensity stronger than a proportional one is observed in light emission of a specific wavelength. This is due to the fact that stimulated emission light is obtained.

In other words, in the relationship between the excitation light intensity and the emission intensity in FIG. 7, when the excitation light intensity is gradually changed from low to high, there is a proportional relationship between the low and high excitation light intensity. I understand that there is no. That is, it can be seen that the slope of the graph is different between the portion where the excitation light intensity is low and the portion where the excitation light intensity is high, and the slope is higher at the higher portion.
This can be said to indicate that stimulated emission light is obtained by increasing the excitation light intensity, that is, ASE oscillation is occurring.

Claims (8)

A carbazole derivative which is a compound C represented by the following general formula (1), wherein the compound A represented by the following structural formula (2) and a compound B represented by the following general formula (3) are reacted in the presence of a palladium catalyst. How to manufacture.

(However, in the formula, Z represents a carbon atom or a silicon atom. R ¹ and R ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms and a substituent which may have a substituent. An aromatic heterocyclic group having 3 to 13 carbon atoms which may have, or an alkyl group having 1 to 10 carbon atoms in the main chain which may have a substituent, R ¹ and R ² are A ring may be formed directly or through a substituent, and X ¹ and X ² each independently represent a halogen atom.)   In Claim 1, the compound A shown in the structural formula (2) and the compound B shown in the general formula (3) are mixed and reacted so that the compound A is 2 equivalents or more with respect to the compound B. A method for producing a carbazole derivative, which is Compound C, In claim 1 or claim 2,
A method for producing a carbazole derivative, which is Compound C, characterized by reacting by heating. In any one of Claims 1 thru | or 3,
A method for producing a carbazole derivative, which is Compound C, wherein Compound A and Compound B are reacted in the presence of a base. In any one of Claims 1 thru | or 4,
The method for producing a carbazole derivative, which is Compound C, wherein the palladium catalyst is a catalyst in which a phosphine-based ligand and a zero-valent or divalent palladium complex are mixed. In any one of Claims 1 thru | or 5,
A method for producing a carbazole derivative, which is Compound C, wherein X ¹ and X ² are each independently a bromine atom or an iodine atom. In any one of Claims 1 thru | or 6,
A method for producing a carbazole derivative, which is Compound C, wherein X ¹ and X ² represent the same atom. In any one of Claims 1 thru | or 7,
A method for producing a carbazole derivative, which is Compound C, wherein Z is a carbon atom.

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