JPH0393736A - New diolefin aromatic compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X<1> and X<2> are monovalent group in which one H is removed from pyrene molecule). EXAMPLE:1,4-Bis[2-(1-pyrenyl)vinyl]benzene. USE:An organic luminous material, organic coloring matter, etc. PREPARATION:A phosphorus compound expressed by formula II [Y<1> and Y<2> are diphenylphosphonium halide group expressed by formula III (X<-> is halide ion) or dialkyl phosphonate group expressed by formula IV (R is lower alkyl) is reacted with a pyrenecarbaldehyde compound expressed by formula V (X is monovalent group in which one H is removed from pyrene molecule) in the presence of a basic catalyst at ambient temperature to 100 deg.C to provide the compound expressed by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel diolefin aromatic compound and a method for producing the same, and more specifically, the present invention relates to a novel diolefin aromatic compound and a method for producing the same. It has excellent characteristics as a light emitting material, such as a high melting point and excellent thermal stability, and is also excellent as an organic dye. This article relates to a novel diolefin aromatic compound that can be advantageously used in the fields of materials application, organic dye application, etc., and a practically advantageous production method thereof. [Prior Art] Research has been conducted for a long time to construct devices that utilize electroluminescence (EL) of organic compounds, focusing on the high luminous quantum efficiency and excellent formability of organic compounds, especially the formability of thin films. It is being said. For example, h. Helfr
ish et al. obtained blue light emission using anthracene crystals (J. Chew. Phys. +44.2902
(1966)). Also, Vincet and Burl
o- et al. are attempting to fabricate a light-emitting device driven by low voltage by forming a thin film of a condensed polycyclic aromatic material using a vacuum evaporation method [
Thin Solid Films. 94, 171
(1982)) - However, in all of these, the driving voltage is high (IOOV to several KV), and only low luminance and low efficiency can be obtained. Relatively recently, C. H. Tang et al. used tetraphenylbutadiene as a luminescent material and
(Japanese Unexamined Patent Publication No. 194393/1983)
．． In addition, using a fluorescent metal chelate complex material and a hole-conducting diamine compound, the 1.000 cd/n? We have obtained an organic thin film electroluminescent device that exhibits high luminance as above and emits light below IOV (App
l. Phys. Lett. ．． 51.913 (19
B? )) However, although these devices can produce high-brightness light at low voltage, the 1.1
, 4,4-tetraphenyl-1,3-butadiene and 8-
Problems include the fact that the aluminum complex of hydroxyquinoline easily thermally decomposes at temperatures above 300°C, and the low thermal stability of such luminescent materials causes the luminescence to deteriorate easily, making it impossible to create a stable EL device. There is. In addition, the fluorescence of pyrene is high in a solution state, but it decreases markedly in a solid state.On the other hand, 0-methyldistyrylbenzene, which has a 1,4-distyrylbenzene skeleton and is famous as a laser dye, has high fluorescence. Although it is promising as a light-emitting material for EL devices, it has drawbacks such as a low melting point of 173°C and poor thermal stability. Although there are many highly luminescent substances, there are no known organic luminescent materials that have high fluorescence in the solid state and have sufficiently high melting points and thermal stability. Even if the molecular weight is increased, it is generally difficult to raise the melting point while maintaining high fluorescence in the solid state. In other words, in the field of application of organic light-emitting materials such as organic EL devices, there is a strong need for the development of new materials that exhibit high luminescence (fluorescence) in the solid state, have a high melting point, and have excellent thermal stability. It had been. [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances. The object of the present invention is to have excellent properties as an organic luminescent material, such as exhibiting high luminescence (fluorescence) even in a solid state, a high melting point, and excellent thermal stability, and also as an excellent organic dye. It is an object of the present invention to provide a novel diolefin aromatic compound which has high utility value, such as a diolefin aromatic compound, and a method for producing the same which is practically advantageous.

[Means to solve the problem]

The present inventors have conducted extensive research to solve the above problems, and as a result, a novel aromatic compound having a specific structure has become an excellent organic light-emitting material that satisfies the above objectives, and is suitable as an organic dye. As a result of various studies on the production method of the new aromatic compound, it was discovered that a method of reacting specific compounds with each other is particularly advantageous in practice, and the present invention has been developed. It has been completed. That is, the first invention of the present invention is based on the following general formula! ' −
CH=lJ@CH鴬Cl−X冨 (1) (However,
X' and X- in formula (1) each independently represent a monovalent group obtained by removing F hydrogen atoms from a pyrene molecule. ) The second invention of the present invention is an invention relating to a preferred method for producing the diolefin aromatic compound, which is the first invention, and comprises the following: General formula (However, Yl and Y in formula (If) are each independently,
The following general formula -p''he○)s Z- (II a) (
However, 2- in formula (IIa) represents a halogen ion. ) Diphenylphosphonium halide group represented by the formula or the following general formula -PO(OR)z (I
I b ) (However, R in formula (Ilb) represents a lower alkyl group.) It represents a dialkylphosphonate group represented by the following formula. ] and the following general formula X-CIO (I[
l) (However, X in the formula (I[[) represents a monovalent group obtained by removing one hydrogen atom from a pyrene molecule.) The following general formula xI-cu=co@co-
co-xz (1:+ (However, X1 and Xt in formula CI each independently represent a monovalent group obtained by removing one hydrogen atom from a birene molecule.) The present invention provides a method for producing olefin aromatic compounds. The diolefin aromatic compound represented by the formula El) is
It has two linear vinylene (-CB/CH-) units in its molecule, and there are four combinations depending on the geometric isomerism of the vinylene units: cis-cis, trans-cis, cis-trans, and trans-trans combinations. , the diolefin aromatic compound of the present invention may be any of them, or a mixture thereof in any proportion. Particularly preferred are all trans isomers. In addition, x1 and XN in formula (1) each represent a monovalent group obtained by removing one hydrogen atom from a birene molecule as described above, and specifically, x1 and
-yl group, ie, pyren-2-yl group, or pyren-4-yl group. χ1 and X2 in formula (1) may be the same group or different groups, so X' and χ2 in the diolefin aromatic compound represented by formula CI) There are nine combinations, and considering the isomer factor of the vinylene unit and the symmetry factor of the entire molecule, the diolefin aromatic compound of the present invention can be substituted with isotopes or modified. If not, a total of 18 isomers are present. The diolefin aromatic compound in the present invention may be any one of these diolefin aromatic compounds alone,
Alternatively, it may be a mixture of any two or more of these in any proportion. Particularly preferred are all trans isomers. There are no particular limitations on the method for producing the diolefin aromatic compound represented by the formula (1), and it can be produced by various methods using various organic synthesis techniques. It can be advantageously manufactured using the manufacturing method of Below, the manufacturing method of the second invention will be explained in detail.

Z- in the diphenylphosphonium halide group represented by the formula (Ila) is F-, CI-Br-,
and I-. Among these, CI- is particularly preferred. R in the dialkylphosphonate group represented by the above formula (nb) is a lower alkyl group, and this lower alkyl group is an alkyl group having a linear or branched or ring structure having 1 to 6 carbon atoms. group, cycloalkyl group, or aromatic alkyl group. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl groups and ethyl groups are particularly preferred. Note that the two R's in formula (flb) may be the same group or may be different groups. In the phosphorus compound represented by the formula (II), Y' and Y2 are each the diphenylphosphonium halide group or the dialkylphosphonate group, and these may be the same as each other. , or different groups may be used, but from the viewpoint of ease of synthesis, a bisphosphonium-type phosphorus compound in which Y1 and Y2 are both diphenylphosphonium halide groups, or a bisphosphonate-type phosphorus compound in which both Y1 and Y2 are dialkylphosphonate groups. Phosphorus compounds, especially those having the same group, can be suitably used. Note that these phosphorus compounds may be used alone or in combination of two or more, if necessary.

These phosphorus compounds represented by formula (1) are, for example, corresponding xylylene dihalide compounds (wherein zl and z2 each independently represent a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, (preferably represents a chlorine atom.) and trialkyl phosphite or triphenylphosphine directly or in combination with toluene, xylene,
It can be easily produced by heating in a solvent such as tetrahydrofuran or N,N-dimethylformamide. Here, the alkyl group in trialkyl phosphite is usually the same group as R above. According to the stoichiometry of the phosphorus reaction represented by the general formula [■] thus obtained, it is preferable to set the ratio of the latter to 2 moles or around 2 moles per 1 mole of the former. ) in the presence of a basic catalyst at a temperature from room temperature to about 100°C, the desired diolefin aromatic compound represented by general formula (1) can be obtained. In addition, X in the general formula (III) is the x1 or X
This pyrenecarboxaldehyde compound may be used alone, or two or more types may be used in combination as necessary. In addition, as the basic catalytic reaction, various types can be used, and specifically, for example, basic soda such as caustic soda, basic potash such as caustic potash, sodium amide, sodium hydride, sodium methane, etc. Examples include alcoholates such as alcoholates, potassium t-butoxide, and lithium ethoxide. These may be used alone or in combination of two or more.

Various solvents can be used as the solvent used in the reaction, and specifically, alcohols such as methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, or phenols;
．． 2-dimethoxyethane, bis(2-methoxyethyl)
Ethers such as ether, dioxane and tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, dimethyl sulfoxide, N,N-dimethylformamide,
Examples include inert polar solvents such as N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone. Incidentally, these may be used alone, or two or more may be used in combination as a mixed solvent. The reaction temperature is determined by the stability of the reaction raw materials and raw materials against the basic catalyst used, the raw materials (general formula [■]) and (I[[
Since the preferred range differs depending on the reactivity of the compound), the activity of the basic catalyst and reactivity as a condensing agent, the type of catalyst used, etc., it is desirable to select it appropriately depending on the case. For example, when using polar solvents, typically
It is appropriate to select a temperature within the range of room temperature to 100°C, preferably room temperature to 60°C. However, if the intention is to shorten the reaction time or to use a catalyst (condensing agent) with low activity, it may be more efficient to carry out the reaction at a higher temperature. The diolefin aromatic compound of the present invention synthesized as described above can be recovered as a mixture or a single compound of desired purity by appropriately using conventional separation methods, purification techniques, and other post-treatments. For example, the diolefin aromatic compound of the present invention obtained as described above exhibits high luminescence (fluorescence and electroluminescence) even in the solid state, has a high melting point (for example, 337°C), and is thermally stable. It has excellent properties as a heat-resistant organic light-emitting material (organic phosphor or light-emitting material for organic electroluminescence devices), such as excellent properties such as excellent properties such as excellent physical properties such as thin film formation, etc. It is a highly useful compound with excellent properties as a pigment, and can be advantageously used in various fields of application of organic light-emitting materials, including organic electroluminescence (EL) elements 5, and fields of application of organic dyes. can do. In addition, when finishing a molded product such as a desired organic electroluminescence element using the diolefin aromatic compound of the present invention as a luminescent material, a pigment, or a component thereof, various methods such as known thinning methods may be used. It can be used as appropriate. [Examples] The present invention will be explained in more detail below using Examples and Reference Examples, but the present invention is not limited to these Examples and Reference Examples. Example 1 10.0 g (14.0 mmol) of p-cylene bis(triphenylphosphonium chloride) and 6.6 g (28.5 mmol) of 1-bilene bis(triphenylphosphonium chloride) were dissolved in 200 d of absolute ethanol. 2.7 g (39.0 mmol) of sodium ethoxide was added to this at room temperature. 10
After stirring under reflux for an hour, it was diluted with 100 m of water, the precipitate was filtered, and the filter was washed with water and methanol to obtain a yellow powder. The melting point was 179.0-181.0°C. This was recrystallized by adding toluene and a small amount of iodine to obtain 3.5 g of yellow-orange plate-like crystals (yield: 47%). Melting point is 33
The temperature was 7°C. The results of elemental analysis of this crystal are shown in Table 1 along with the theoretical values. In addition, when the infrared absorption spectrum (Kbr tablet method) of this crystal was measured, absorption based on the C-H out-of-plane bending vibration of the trans-olefin was observed at 9753-'. This infrared absorption spectrum is shown in Figure 1. Furthermore, when mass spectrometry (MS) was performed on this crystal, m / z = 5
3 1. A peak of 0 was observed. This result is the second
It is shown in the figure. The yellow-orange plate-like crystals obtained from the above analysis results were confirmed to be trans-type 1,4-bis(2-(1-pyrenyl)vinyl)benzene.Reference Example 1 25m x 75ugly x 1.1 A transparent support substrate was obtained by forming a film of ITO to a thickness of 100 nm on the glass substrate (2) by vapor deposition method.This transparent support substrate was coated with a commercial vapor deposition apparatus (
N, N-diphenyl N, N' was fixed to a substrate holder manufactured by Japan Vacuum Technology ■ and placed on a resistance heating boat made of molybdenum.
-Bis-(3-methylphenyl)-(1.1'-biphenyl)-4.4-diane (TPDA) was put in 200 μg, and trans-1.4-bis(2 - (1-Vyrenyl)vinyl]benzene (BPV
A Lette vacuum tank containing 200 g of B) was depressurized to IXIO-'Pa.

After that, the boat containing TPDA was heated to 215-220℃.
TPDA is heated to a deposition rate of 0. 1-0.3nm
A hole injecting and transporting layer with a thickness of 60 nm was formed by vapor deposition on a transparent support substrate at a rate of 100 nm/sec. The substrate temperature at this time was room temperature. Without taking it out of the vacuum chamber, BPVB was deposited as a light-emitting layer on the hole injection transport layer using a single boat to a thickness of 60 nm. The deposition conditions were a boat temperature of 350 to 355°C and a deposition rate of 0.1.
~0.3 nm/sec, and the substrate temperature was room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on top of the light emitting layer, and it was fixed to the substrate holder again. Next, put 1g of magnesium ribbon into the molybdenum resistance heating port, put indium 500cm into the other molybdenum resistance heating boat, and then turn the vacuum chamber 2X.
After reducing the pressure to 10-'Pa, indium was deposited at a rate of 0.1 nnn/sec by resistance heating, and at the same time magnesium was deposited at 1.7 mm from a molybdenum boat by resistance heating.
Deposition started at a deposition rate of ~2.8 nm/sec. The temperature of the boat was approximately 800°C for indium and 500°C for magnesium. Under the above conditions, a mixed metal electrode of magnesium and indium was placed on the light emitting layer for 100 m
A stack of nanometers was deposited and used as a counter electrode. When a direct current of 12 V was applied to this device using an ITO electrode as an anode and a mixed metal electrode of magnesium and indium as a cathode, a current of 20 mA/C4 flowed and yellow-green light was emitted. The emission wavelength range was 450 to 620 nm based on spectroscopic measurements. The peak wavelength was 530 nm, and the luminance was 50 cd/ryf, both of which showed good values. [Effects of the Invention] According to the present invention, it exhibits high luminescence (fluorescence and electroluminescence) even in a solid state, and has a high melting point.
It has excellent properties as an organic light-emitting material (organic phosphor or light-emitting material for organic electroluminescence devices), such as excellent thermal stability and excellent formability such as thin film formation.
In addition, it is a highly useful compound that has excellent properties as an organic dye, and is advantageous in the fields of application of various organic light-emitting materials, including organic electroluminescence (EL) devices, and the field of application of organic dyes. It is possible to provide a novel diolefin aromatic compound that can be used and a method for producing the same that is practically advantageous.

Claims (2)

[Claims] 1. The following general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ [I] (However, in the formula [I], X^1 and X^2 each independently remove one hydrogen atom from the birene molecule A novel diolefin aromatic compound represented by: 2. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, Y^1 and Y^2 in formula [II] are each independently the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. There is a diphenylphosphonium halide group represented by ▼ [IIa] (however, Z^- in formula [IIa] represents a halogen ion) or the following general formula -PO(OR)_2 [IIb] ( However, R in formula [IIb] represents a lower alkyl group.) represents a dialkylphosphonate group represented by X in [III] represents a monovalent group obtained by removing one hydrogen atom from a pyrene molecule. , chemical formulas, tables, etc.▼ [I] (However, X^1 and X^2 in formula [I] each independently represent a monovalent group obtained by removing one hydrogen atom from a pyrene molecule. A method for producing a diolefin aromatic compound represented by