JP2005272351A - Styryl derivative and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new styryl derivative, a compound useful as an emissive substance for organic EL(electroluminescent) devices emitting at longer wavelengths compared to blue color ones, therefore useful as an organic EL material, and to provide a method for producing the new styryl derivative. <P>SOLUTION: The styryl derivative is represented by general formula(1)[ wherein, R<SP>1</SP>and R<SP>2</SP>are each CH<SB>3</SB>-(CH<SB>2</SB>)<SB>x</SB>-CH(CH<SB>3</SB>)-(CH<SB>2</SB>)<SB>y</SB>-CH<SB>2</SB>or CH<SB>3</SB>-(CH<SB>2</SB>)<SB>x</SB>-CH(CH<SB>3</SB>)-(CH<SB>2</SB>)<SB>y</SB>-CH<SB>2</SB>-O( wherein, x is an integer of 0-7; and y is an integer of 0-7 ), wherein it is especially preferable that R<SP>2</SP>is isobutyl or R<SP>1</SP>and R<SP>2</SP>are both isobutyloxy groups ]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel styryl derivative useful as an organic electroluminescence material and a method for producing the same.

  An inorganic electroluminescence element using an inorganic phosphor as a light emitting material is used in a display device such as a planar light source as a backlight or a flat panel display. Inorganic electroluminescent elements require high voltage alternating current to emit light. In recent years, an organic electroluminescent element having a dual structure in which an organic fluorescent dye is used as a light emitting layer and an organic charge transporting compound used in an electrophotographic photoreceptor is laminated (hereinafter referred to as “organic EL element”). .) Has been proposed. Since organic EL elements have the characteristics that light emission of a large number of colors can be easily obtained in addition to low-voltage driving and high luminance, compared to inorganic electroluminescent elements, element structures, organic fluorescent dyes, and organic charge transport compounds A number of compounds have been proposed.

  The organic EL element has a structure in which an organic light emitting layer is sandwiched between two electrodes, and holes injected from the anode and electrons injected from the cathode recombine in the light emitting layer to emit light. There are two types of organic EL elements. One is a fluorescent dye added to the charge transport layer. The other is to use a fluorescent dye alone. The latter element improves the light emission efficiency when a hole transport layer that transports only holes whose fluorescent dye is one of charges and / or an electron transport layer that transports only electrons is laminated. It is known. A wide variety of materials are known as hole transport materials used in organic EL elements, mainly triphenylamine derivatives. Surprisingly, however, there are few proposals regarding electron transport materials.

  Examples of electron transport materials that have been proposed so far include metal complexes of oxine derivatives, compounds having a plurality of oxadiazole rings, and quinoxaline derivatives. In addition, various proposals have been made to use a bisstyryl derivative represented by the following general formula (6) in a light-emitting layer (see, for example, Patent Documents 1 and 2), and the present inventor has also proposed one type (for example, Patent Documents). 3). According to this bisstyryl derivative, blue light emission with a wavelength of 435 nm is possible. However, development of a luminescent material that emits light at a longer wavelength has been desired.

JP-A-2-222484 JP-A-2-247277 JP 2004-6271 A J. Appl. Phys., 65, 3610. 1989 Jpn. J. Appl. Phys., 27, L269, 1988

  Accordingly, an object of the present invention is to provide a light emitting material for an organic EL element that emits light at a longer wavelength than blue.

  The present invention achieves the object by providing a styryl derivative represented by the following general formula (1).

  Further, in the present invention, as a preferable production method of the styryl derivative, a 4-styrylbenzaldehyde compound represented by the following general formula (3) and the following general formula (4), respectively, and a p- represented by the following general formula (5): The present invention provides a production method comprising reacting xylene bis- (triphenylphosphonium halogen).

  According to the present invention, a novel styryl derivative and a method for producing the same are provided. Such a styryl derivative is particularly useful as a light-emitting substance for an organic EL device that emits light at about 450 nm.

  The styryl derivative of the present invention is a compound having a long linear conjugated structure portion. The styryl derivative of the present invention is characterized by the fact that the repeating unit of the styryl group is 4 in the general formula (1). Based on this feature, the present inventor has found that the styryl derivative of the present invention emits light with a green color of 450 nm when used as a light-emitting substance for an organic EL device. A compound having the same basic skeleton as in the general formula (1) and having a repeating unit of a styryl group other than 4 emits blue light, for example, and does not emit green light.

In general formula (1), R ¹ and R ² are the same or different linear or branched alkyl groups, linear or branched alkoxy groups, or unsaturated bonds represented by general formula (2). It is group which has. As the alkyl group, those having 1 to 18 carbon atoms are preferably used. Specific examples include a methyl group, an ethyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a pentadecyl group, and an octadecyl group. Among these, a C4-C18 alkyl group is preferable. In particular, the alkyl group has the general formula CH ₃ — (CH ₂ ) _x —CH (CH ₃ ) — (CH ₂ ) _y —CH ₂ — (wherein x is an integer of 0 to 7, y is an integer of 0 to 7) Is preferable, since the solubility in various solvents can be improved. In particular, an isobutyl group in which x = 0 and y = 0 is preferable.

The alkoxy group, the general formula C _n H _{2n +} 1 O- represented by integers n in the formula is 1 to 20, particularly preferably an integer of 4 to 18. In particular, the alkoxy group is represented by the general formula CH ₃ — (CH ₂ ) _x —CH (CH ₃ ) — (CH ₂ ) _y —CH ₂ —O— (wherein x is an integer of 0 to 7 and y is 0 to 7). Is preferable because the solubility in various solvents can be improved. In particular, an isobutyloxy group in which x = 0 and y = 0 is preferable.

R ^{3 in the} group having an unsaturated bond represented by the general formula (2) represents a hydrogen atom or a methyl group. B represents — (CH ₂ ) _m —, — (CH ₂ ) _m —O—, —CO—O— (CH ₂ ) _m —, —CO—O— (CH ₂ ) _m —O—, —C _6. H ₄ —O— and —CO— are shown. m is preferably an integer of 1 to 18, particularly an integer of 6 to 14.

In the styryl derivative represented by the general formula (1), R ¹ and R ² may be the same group or different groups. In particular, R ¹ and R ² are preferably the same group. In particular, it is preferable that R ¹ and R ² are both isobutyl groups, or R ¹ and R ² are both isobutyloxy groups.

  The styryl derivative represented by the general formula (1) may be a cis isomer or a trans isomer, or a mixture of both.

  The styryl derivative represented by the general formula (1) includes a 4-styrylbenzaldehyde compound represented by the general formula (3) and the general formula (4) and p-xylene bis- ( It is preferably produced by reacting triphenylphosphonium halogen).

For example, when obtaining a styryl derivative in which R ¹ and R ² are both isobutyloxy groups in the general formula (1), 4- (4-isobutyloxystyryl) benzaldehyde is represented as the general formulas (3) and (4). It is sufficient to use a Br salt as the general formula (5). In the case of obtaining a styryl derivative in which R ¹ and R ² are both isobutyl groups in the general formula (1), 4- (4-isobutylstyryl) benzaldehyde is used as the general formulas (3) and (4), A Br salt may be used as the general formula (5).

Specifically, when obtaining a styryl derivative in which R ¹ and R ² are both isobutyloxy groups in the general formula (1), 4-hydroxybenzyl alcohol is used as a starting material, according to the following reaction scheme 1 ( The target substance can be obtained by synthesizing the compounds of 10) to (16).

  In Reaction Scheme 1, first, isobutyl bromide is allowed to act on 4-hydroxybenzyl alcohol in dimethylformamide at 40 ° C. to obtain 4-isobutyloxybenzyl alcohol (10). The resulting 4-isobutyloxybenzyl alcohol (10) is reacted with phosphorus tribromide in benzene at room temperature to give 4-isobutyloxybenzyl bromide (11). The compound (11) is allowed to react with triphenylphosphine in benzene at room temperature to obtain 4-isobutyloxybenzphosphonium bromide (12). Terephthalaldehyde is allowed to act on compound (12) in methanol at 50 ° C. to give 4- (4-isobutyloxystyryl) benzaldehyde (13).

  The obtained compound (13) is a mixture of a cis isomer and a trans isomer. While this mixture is refluxed in toluene, iodine is allowed to act to obtain a trans isomer (14). In this case, the amount of iodine added is preferably 0.001 to 0.1 times mol, more preferably 0.005 to 0.01 times mol with respect to compound (13), and the heat treatment temperature is 100 to 180 ° C. The temperature is preferably 130 to 150 ° C.

By allowing p-xylene bis- (triphenylphosphonium bromide) to act in the presence of a base while refluxing the obtained trans isomer (14) in toluene, R ¹ and R ² in general formula (1) are In any case, a styryl derivative (15) which is an isobutyloxy group is obtained. The addition amount of the trans isomer (14) is preferably 2 to 4 times mol, more preferably 2 to 2.5 times mol for p-xylene bis- (triphenylphosphonium bromide).

  The base is not particularly limited. For example, metal hydrides such as sodium hydride, amines such as trimethylamine and triethylamine, alkali hydroxides such as potassium hydroxide and sodium hydroxide, sodium methoxide, potassium methoxide and sodium Examples thereof include alkoxides such as ethoxide and potassium ethoxide, piperidine, pyridine, potassium cresolate, and alkyl lithium. These are used alone or in combination of two or more.

  The addition amount of the base is 1 to 5 times mol, preferably 3.5 to 4.5 times mol, of p-xylene bis- (triphenylphosphonium bromide). The reaction temperature is preferably 0 to 100 ° C., more preferably 20 to 50 ° C., and the reaction time is preferably 0.5 to 50 hours, more preferably 5 to 30 hours. After completion of the reaction, filtration, washing as required, and drying to obtain a styryl derivative (15).

  This styryl derivative (15) is a mixture of a cis isomer and a trans isomer. While this mixture is refluxed in toluene, iodine is allowed to act to obtain a trans isomer (16) as a target substance. The reaction conditions at this time can be the same as in the case of trans-conversion described above.

In the case of obtaining a styryl derivative in which R ¹ and R ² are both isobutyl groups in the general formula (1), 4-isobutylbenzaldehyde is used as a starting material, and (17) to (17)-( The target substance can be obtained by synthesizing the compound of 23).

  As is apparent from Reaction Scheme 2, the reaction after 4-isobutylbenzaldehyde is allowed to react with sodium borohydride to give 4-isobutylbenzalcohol (17) is basically the same as Reaction Scheme 1 described above. It is. Therefore, for the details of the reaction after obtaining 4-isobutylbenzalcohol (17) in Reaction Scheme 2, the explanation for Reaction Scheme 1 is applied as appropriate.

  The various styryl derivatives thus obtained emit light in a green color of about 450 nm when used as a light emitting material for an organic EL device. In addition, this styryl derivative is a photosensor utilizing a charge transport property, a photoconductor, a spatial modulation element, a thin film transistor, a charge transport material for an electrophotographic photoreceptor, a photolithographic, a solar cell, a nonlinear optical material, an organic semiconductor capacitor, It can also be used as a material for other sensors.

  The organic EL element has a structure comprising two layers of an organic phosphor thin film and an organic hole transport layer laminated between a metal electrode as a cathode and a transparent electrode as an anode, or an organic electron transport layer, an organic phosphor It has a structure including a thin film and an organic hole transport layer, and the styryl derivative of the present invention is used as a constituent material of the organic phosphor thin film.

  The present invention will be specifically described below with reference to examples. However, the scope of the present invention is not limited to such examples.

[Example 1]
Compound (16) was synthesized according to the following procedure according to Reaction Scheme 1 described above.

Synthesis of 4-isobutyloxybenzyl alcohol (10) 4.0 g / 0.1 mol of sodium hydroxide is dissolved in 50 ml of ethanol. Next, 12.5 g / 0.1 mol of 4-hydroxybenzyl alcohol is dissolved in 100 ml of ethanol. These two are combined and stirred for 1 hour, and ethanol is removed under reduced pressure. The residue is dissolved in 100 ml of dimethylformamide, and 13.7 g / 0.1 mol of 1-bromo-2-methylpropane dissolved in 30 ml of dimethylformamide is added dropwise. This is reacted at 40 ° C. for 18 hours. Thereafter, a 10% cold dilute hydrochloric acid aqueous solution is added to the reaction solution, extracted with ether, and further washed with distilled water. The obtained ether layer is dehydrated with anhydrous sodium sulfate, and after filtration, the ether is removed under reduced pressure. Add 150 ml of hexane to the residue to obtain a hexane soluble part. The hexane-insoluble part is separated by column chromatography (Wakogel C-300, 15 g, ether: hexane = 1: 3) to obtain the desired product (Rf value: 0.76). The yield was 8.5 g, the yield was 47.2%, and the properties were a reddish brown liquid. As identification data, analytical data of ¹ H-NMR (CDCl ₃ ) and FT-IR (KBr) are shown in Table 1 and Table 2, respectively.

Synthesis of 4-isobutyloxybenzyl bromide (11) 7.2 g / 0.04 mol of 4-isobutyloxybenzyl alcohol and 0.4 g of pyridine were dissolved in 80 ml of benzene, and 10.8 g / 0.04 mol of phosphorus tribromide was dissolved in 20 ml of benzene. A solution dissolved in is dropped. This is allowed to react for 18 hours. Thereafter, 300 g of ice water is added to the reaction solution, extracted with ether and washed several times with distilled water. Anhydrous sodium sulfate is added to the obtained ether layer and dehydrated overnight. After filtration, the ether is removed under reduced pressure to obtain the desired product. The yield was 9.23 g, the yield was 95%, and the properties were a red-orange liquid. As identification data, analytical data of ¹ H-NMR (CDCl ₃ ) and FT-IR (KBr) are shown in Table 3 and Table 4, respectively.

Synthesis of 4-isobutyloxybenzphosphonium bromide (12) 7.29 g / 0.03 mol of 4-isobutyloxybenzyl bromide is dissolved in 20 ml of benzene, and 13.1 g / 0.05 mol of triphenylphosphine is added. This is allowed to react for 48 hours at room temperature under a nitrogen atmosphere. Thereafter, a precipitate is obtained by centrifugation. This is washed with ether to obtain the desired product. The yield was 11.49 g, the yield was 75.8%, the property was a white solid, and the melting point was 248-252 ° C. As identification data, analytical data of ¹ H-NMR (CDCl ₃ ) and FT-IR (KBr) are shown in Table 5 and Table 6, respectively.

Synthesis of 4- (4-isobutyloxystyryl) benzaldehyde (13) Mixing 7.06 g / 0.01 mol of 4-isobutyloxybenzphosphonium bromide and 1.88 g / 0.014 mol of terephthalaldehyde with CHCl ₃ : EtOH = 1: 3 Dissolve in 60 ml of solvent. This liquid is called A liquid. 0.5 g / 0.022 mol of sodium is dissolved in 40 ml of EtOH to obtain NaOEt. This liquid is designated as B liquid. B liquid is dripped slowly into A liquid, and this is stirred at 50 degreeC under nitrogen atmosphere for 24 hours. After the reaction, 300 g of a cold dilute aqueous hydrochloric acid solution is added to the reaction solution, followed by extraction with chloroform. Add anhydrous sodium sulfate to the chloroform layer and dehydrate overnight. This is filtered and chloroform is removed under reduced pressure. 160 ml of ether is added to the obtained residue to obtain an ether-soluble part. Ether is removed, and the residue is separated by column chromatography (Wakogel C-300 30 g, ether: hexane = 1: 3) to obtain the desired product (Rf value: 0.29 to 0.57). The yield was 2.24 g, the yield was 57.1%, and the properties were a pale yellow solid. As identification data, analytical data of ¹ H-NMR (CDCl ₃ ) and FT-IR (KBr) are shown in Table 7 and Table 8, respectively.

Synthesis of 4- (4-isobutyloxystyryl) benzaldehyde (14) 2.02 g / 7.21 mmol of 4- (4-isobutyloxystyryl) benzaldehyde and 0.041 g / 0.16 mmol of iodine were placed in a 50 ml round bottom flask. Add 12 ml of p-xylene to reflux for 4 hours. After the reaction, it is cooled to room temperature and the precipitate is filtered. The filtrate is concentrated and the precipitate is filtered. The obtained precipitate is washed with cold ethanol to obtain the desired product. The yield was 1.66 g, the recovery rate was 82.3%, the property was a pale yellow solid, and the melting point was 166-167 ° C. As identification data, analytical data of ¹ H-NMR (CDCl ₃ ) and FT-IR (KBr) are shown in Table 9 and Table 10, respectively.

Synthesis of Compound (15) 40 ml of a mixed solvent of CHCl ₃ : EtOH = 1: 3 was added to 0.45 g / 0.57 mmol of p-xylene bis- (triphenylphosphonium bromide), and the mixture was cooled to −20 ° C. with acetone cooled by a freeze trap. Allow to cool. 4- (4-Isobutyloxystyryl) benzaldehyde 0.32 g / 1.14 mmol is added to this. This is A liquid. To solution A, 0.4 g / 2.1 mmol of 28% sodium methoxide methanol solution is slowly added dropwise at -20 ° C. This is refluxed for 10 hours. Then, it cools to room temperature and filters a deposit. The obtained precipitate is ultrasonically washed with 100 ml of 60% aqueous methanol solution and 40 ml of methanol and filtered. Finally, ether washing is performed to obtain the desired product. The yield was 0.23 g, the yield was 63.9%, and the property was a yellow solid. As identification data, analytical data of ¹ H-NMR (CDCl ₃ ) and FT-IR (KBr) are shown in Table 11 and Table 12, respectively.

Synthesis of Compound (16) 0.23 g / 0.37 mmol of Compound (15) and 1.4 mg / 0.0056 mmol of iodine are placed in a 50 ml round bottom flask, 30 ml of p-xylene is added, and this is refluxed for 4 hours. Thereafter, the reaction solution is cooled to room temperature and the precipitate is filtered. This is washed with ethanol and ether to obtain the desired product. The yield was 0.21 g, the recovery rate was 91.9% (isomerization), the yield was 58.3% (reaction to obtain compound (16) from compound (14)), and the property was a fluorescent yellow solid. It was. Table 13 shows the elemental analysis data. The fluorescence spectrum is shown in FIG.

[Example 2]
Compound (23) was synthesized according to the following procedure according to Reaction Scheme 2 described above.

Synthesis of 4-isobutylbenzyl alcohol (17) 1.5 g of sodium hydroxide is dissolved in 50 ml of methanol, and 2.9 g / 0.077 mol of sodium borohydride is added thereto with cooling. To this solution, 44.17 g / 0.27 mol of 4-isobutylbenzaldehyde dissolved in 20 ml of methanol is slowly added dropwise. Thereafter, 150 ml of 1N sodium hydroxide is added to the reaction solution and stirred. This solution is put into a separating funnel to obtain an oil layer. Chloroform is added to this oil layer to obtain a chloroform soluble part. To this is added anhydrous sodium sulfate and dehydrated overnight. This is filtered and chloroform is removed under reduced pressure to obtain the desired product. The yield was 39.5 g, the yield was 89.3%, and the property was an orange liquid. As identification data, analytical data of ¹ H-NMR (CDCl ₃ ) and FT-IR (KBr) are shown in Table 14 and Table 15, respectively.

Compound (23) was synthesized according to Reaction Scheme 2 using 4-isobutylbenzyl alcohol obtained by the above method. The specific synthesis method was the same as in Example 1. The property of the obtained compound (23) was a yellow powder. As identification data, analytical data of ¹ H-NMR (CDCl ₃ ) and FT-IR (KBr) are shown in Table 16 and Table 17, respectively. The fluorescence spectrum is shown in FIG.

[Comparative Example 1]
The following trans, trans-1,4-bis (4 ′-(isobutyl) styryl) benzene was synthesized by the following procedure. The fluorescence spectrum of the obtained compound is shown in FIG.

In a 300 ml four-necked flask, 6.49 g / 40 mmol of 4-isobutylbenzaldene and 15.77 g / 20 mmol of p-xylylenebis- (triphenylphosphonium bromide) were suspended in 150 ml of methanol, and this was 28% sodium methylate at room temperature. 11.78 g / (61.1 mmol) was added dropwise. Thereafter, the mixture was aged at 30 ° C for 1 hour and then aged at room temperature for 18 hours. Methanol was distilled off, 200 ml of water was added to the residue, and the precipitate was filtered after stirring. This precipitate was filtered and washed with 200 ml of water. Further, the operation of filtration and washing with 100 ml of acetone was repeated twice. The precipitate was dried to obtain an isomer mixture. The yield was 6.12 g / 15.5 mmol, the yield was 77.5%, and the properties were green powder. Further, this was thermally isomerized by adding 1 mol% of iodine under a p-xylene solvent to obtain trans, trans-1,4-bis (4 ′-(isobutyl) styryl) benzene. The yield was 5.00 g / 12.7 mmol, the yield was 63.3%, and the properties were green powder. As identification data, ¹ H-NMR (CDCl ₃ ) analysis data is shown in Table 18.

2 is a graph showing the fluorescence spectrum of the compound obtained in Example 1. FIG. 2 is a graph showing the fluorescence spectrum of the compound obtained in Example 2. FIG. 3 is a graph showing the fluorescence spectrum of the compound obtained in Comparative Example 1.

Claims (5)

A styryl derivative represented by the following general formula (1):

CH ₃ — (CH ₂ ) _x —CH (CH ₃ ) — (CH ₂ ) _y —CH ₂ — or CH ₃ — (CH ₂ ) _x in which R ¹ and R ² in the general formula (1) are the same or different. _{-CH (CH 3) - (CH} 2) ( wherein, x is an integer of 0 to 7, y is an integer of 0~7) _y -CH ₂ -O- or branched alkyl group represented by The styryl derivative according to claim 1, which is an alkoxy group. The styryl derivative according to claim 2, wherein R ¹ and R ² in the general formula (1) are both isobutyl groups, or R ¹ and R ² are both isobutyloxy groups.   The styryl derivative according to any one of claims 1 to 3, which is used as an organic electroluminescence material. Reacting a 4-styrylbenzaldehyde compound represented by the following general formula (3) and the following general formula (4) with p-xylenebis- (triphenylphosphonium halogen) represented by the following general formula (5). The method for producing a styryl derivative according to claim 1.

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