CN111909170B - Organic electroluminescent compound, preparation method thereof and organic electroluminescent device comprising organic electroluminescent compound - Google Patents

Organic electroluminescent compound, preparation method thereof and organic electroluminescent device comprising organic electroluminescent compound Download PDF

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CN111909170B
CN111909170B CN202010950526.1A CN202010950526A CN111909170B CN 111909170 B CN111909170 B CN 111909170B CN 202010950526 A CN202010950526 A CN 202010950526A CN 111909170 B CN111909170 B CN 111909170B
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organic electroluminescent
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tetrahydrofuran
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CN111909170A (en
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马晓宇
王进政
张鹤
李贺
李明
姜志远
李建行
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention relates to an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device containing the organic electroluminescent compound, wherein the structural formula of the compound is as follows:

Description

Organic electroluminescent compound, preparation method thereof and organic electroluminescent device comprising organic electroluminescent compound
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device containing the organic electroluminescent compound.
Background
Organic Electroluminescence (EL) refers to a light emitting phenomenon in which an organic material directly converts electric energy into light energy under the action of an electric field. The organic electroluminescent device is a spontaneous light emitting device utilizing the principle, has the characteristics of self luminescence, bright and bright color, thin thickness, light weight, high response speed, wide viewing angle, low driving voltage, harsh natural conditions tolerance, capability of being made into a flexible panel and the like, and is gradually developed into the most advantageous technology in the field of new-generation flat panel display.
The structure of the organic electroluminescent device is specifically as follows: an anode, a cathode, and an organic layer therebetween. In order to improve efficiency and stability of the organic electroluminescent element, the organic material layer includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). Electron transport materials and hole injection materials or hole transport materials are major obstacles to the overall practical use of OLED technology, which directly limit the luminous efficiency, lifetime, operating voltage, etc. of the devices. In order to realize the continuous improvement of the performance of the organic electroluminescent device, it is important to continuously research and innovate an organic electroluminescent compound having high efficiency and long life.
Disclosure of Invention
In view of the above technical problems, it is an object of the present invention to provide an organic electroluminescent compound having a structure of the following formula:
Figure GDA0003679592390000011
in chemical formula 1: r 1 ～R 8 Independently of one another, from hydrogen, deuterium, halogen, cyano, nitro, trifluoromethyl, hydroxyl, sulfonic acid, phosphoric acid, COR 9 Substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, said R 9 Independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; x 1 And X 2 Each independently selected from O, S, Se, S ═ O or SO 2 ；
The halogen comprises fluorine, chlorine, bromine, iodine; preferred are fluorine and chlorine, more preferred is fluorine;
the "substituted or unsubstituted" wherein "substituted" means substituted with at least one of the following substituents: deuterium, halogen, nitrile group, hydroxyl group, carbonyl group, nitro group; preferably, the compound is fully substituted by fluorine, trifluoromethyl or nitrile group.
Further, the organic electroluminescent compound has a structure of chemical formula 2 or chemical formula 3:
Figure GDA0003679592390000021
in chemical formula 2: r 1 ～R 2 Independently of one another, from hydrogen, deuterium, halogen, cyano, nitro, trifluoromethyl, hydroxyl, sulfonic acid, phosphoric acid, COR 9 Substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, R 9 Independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; x 1 And X 2 Each independently selected from O, S, Se, S ═ O or SO 2 ；
In chemical formula 3: r 1 ～R 4 Independently of one another, from hydrogen, deuterium, halogen, cyano, nitro, trifluoromethyl, hydroxyl, sulfonic acid, phosphoric acid, COR 9 Substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, R 9 Independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; x 1 And X 2 Each independently selected from O, S, Se, S ═ O or SO 2 ；
The halogen comprises fluorine, chlorine, bromine, iodine; preferably fluorine and chlorine, more preferably fluorine;
the "substituted or unsubstituted" wherein "substituted" means substituted with at least one of the following substituents: deuterium, halogen, nitrile group, hydroxyl group, carbonyl group, nitro group; preferably, the compound is fully substituted by fluorine, trifluoromethyl or nitrile group.
Further, the organic electroluminescent compound is represented by any one of the following formulas 1 to 40:
Figure GDA0003679592390000031
another object of the present invention is to provide a method for preparing an organic electroluminescent compound represented by chemical formula 2, which comprises the following synthetic route:
Figure GDA0003679592390000041
the preparation method comprises the following specific steps:
(1) preparation of intermediate C: respectively dissolving a compound A and a compound B in a small amount of tetrahydrofuran solvent, adding lithium hydride into the tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound B into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, then dripping the tetrahydrofuran solution containing the compound A into the reaction system, heating the reaction system to 25 ℃ after dripping, and reacting for 15 h; then pouring the reacted solution into ice water, adjusting the pH value of the reacted solution to about 1.0 by using concentrated hydrochloric acid, extracting for three times by using ethyl acetate, combining and uniformly mixing the extracted organic phases, washing by using saturated saline solution, water and sodium bicarbonate aqueous solution in sequence, drying by using sodium sulfate, and removing the solvent to obtain a compound C;
(2) synthesis of the final product, chemical formula 2: adding the intermediate C into a dichloromethane solvent, adding [ bis (trifluoroacetoxy) iodine ] benzene, stirring at room temperature for 10 hours, concentrating the reaction solution in vacuum after the reaction is finished, dropwise adding the concentrated solution into cold ethanol while stirring, carrying out suction filtration, washing and drying on the precipitated solid, and finally carrying out toluene recrystallization and vacuum sublimation on the dried solid to obtain the organic electroluminescent compound shown in chemical formula 2.
The third object of the present invention is to provide a method for preparing an organic electroluminescent compound represented by chemical formula 3, which comprises the following synthetic route:
Figure GDA0003679592390000042
the preparation method comprises the following specific steps:
(1) synthesis of intermediate F: respectively dissolving the compound D and the compound E in a small amount of tetrahydrofuran solvent, adding lithium hydride into the tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound E into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, dripping a tetrahydrofuran solution containing a compound D into the reaction system, heating the temperature of the reaction system to 25 ℃ after dripping, and reacting for 15 h; then pouring the reaction system into ice water, adjusting the pH value of the solution after reaction to about 1.0 by using concentrated hydrochloric acid, extracting for three times by using ethyl acetate, combining and uniformly mixing the extracted organic phases, washing by using saturated saline solution, water and sodium bicarbonate aqueous solution in sequence, drying by using sodium sulfate, and removing the solvent in the solution after reaction to obtain a compound F;
(2) synthesis of intermediate G: dissolving the intermediate F in a tetrahydrofuran solvent, cooling to-78 ℃, dropping n-butyllithium while stirring, stirring for 1 hour at-78 ℃, slowly raising the reaction temperature to room temperature, keeping the temperature at the room temperature for 15 minutes, cooling the reaction liquid to-78 ℃ again, and keeping the temperature for 30 minutes; cooling tetrahydrofuran solvent solution containing iodine to-78 deg.c, adding into the reaction liquid, cooling and stirring overnight; carrying out quenching reaction on a reaction system which is subjected to reaction overnight by using a saturated ammonium chloride solution, extracting a water layer by using a dichloromethane solvent, combining organic phases, washing by using a sodium thiosulfate aqueous solution and sodium chloride aqueous solution in sequence, drying by using magnesium sulfate, concentrating in vacuum until a little dichloromethane solvent remains, dropwise adding the concentrated solution into cold ethanol while stirring, and carrying out suction filtration, washing and drying on a solid precipitated from the ethanol to obtain a compound G;
(3) synthesis of intermediate H: respectively dissolving the intermediate G and the compound I in a small amount of tetrahydrofuran solvent, adding lithium hydride into the tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound I into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, dripping the tetrahydrofuran solution containing an intermediate G into the reaction system, heating to 25 ℃ after dripping, and reacting for 15 h; then pouring the reaction system into ice water, adjusting the pH value of the solution after reaction to about 1.0 by using concentrated hydrochloric acid, extracting for three times by using ethyl acetate, combining and uniformly mixing the extracted organic phases, washing by using saturated saline solution, water and sodium bicarbonate aqueous solution in sequence, drying by using sodium sulfate, and removing the solvent to obtain a compound H:
(4) synthesis of the final product, chemical formula 3: adding the intermediate H into a dichloromethane solvent, adding [ bis (trifluoroacetoxy) iodine ] benzene, stirring at room temperature for 10 hours, then carrying out vacuum concentration on a reaction solution until a little dichloromethane solvent remains, dropwise adding the concentrated solution into cold ethanol while stirring, carrying out suction filtration, washing and drying on a precipitated solid, and finally carrying out toluene recrystallization and vacuum sublimation on the dried solid to obtain the organic electroluminescent compound shown in chemical formula 3.
It is a final object of the present invention to provide an organic electroluminescent device comprising the above organic electroluminescent compound.
The invention has the following beneficial effects:
(1) the preparation method of the organic electroluminescent compound has the advantages of simple synthesis steps, easy product purification, high purity and high yield.
(2) By using the organic electroluminescent compound provided by the invention as a hole injection layer material, the driving voltage of the prepared organic electroluminescent device is obviously reduced, and the luminous efficiency and the driving service life are obviously improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
EXAMPLE preparation of organic photoelectric Material
Example 1
An organic electroluminescent compound 1, namely a compound numbered as 1, has a chemical synthesis reaction formula as follows:
Figure GDA0003679592390000061
the specific preparation steps of the organic electroluminescent compound 1 are as follows:
(1) synthesis of intermediate C-1: dissolving 32.9mmol of the compound A-1 in 30ml of tetrahydrofuran solvent, dissolving 131.6mmol of the compound B-1 in 300ml of tetrahydrofuran solvent, adding 131.6mmol of lithium hydride in 300ml of tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound B-1 into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, dripping the tetrahydrofuran solution containing a compound A-1 into the reaction system, heating the reaction system to 25 ℃ after dripping, and reacting for 15 h; then leading the reacted solution into ice water, adjusting the pH value of the reacted solution to about 1.0 by using concentrated hydrochloric acid, extracting for three times by using ethyl acetate, combining and uniformly mixing the extracted organic phases, washing by using saturated saline solution, water and sodium bicarbonate aqueous solution in sequence, drying by using sodium sulfate, and removing the solvent to obtain 11.19g of compound C-1, wherein the yield is 85%;
(2) synthesis of the final product compound 1: adding 27.0mmol of intermediate C-1 into 300ml of dichloromethane solvent, then adding 64.8mmol of [ bis (trifluoroacetoxy) iodine ] benzene, stirring at room temperature for 10 hours, then concentrating the reaction solution in vacuum until a little of dichloromethane solvent remains, dropwise adding the concentrated solution into cold ethanol while stirring, carrying out suction filtration, washing and drying on the precipitated solid, and finally carrying out toluene recrystallization and vacuum sublimation on the dried solid to obtain 7.62g of organic electroluminescent compound 1, wherein the product yield is 72%.
Example 2
An organic electroluminescent compound 2, namely a compound numbered 2, has the following chemical synthesis reaction formula:
Figure GDA0003679592390000071
the specific preparation steps of the organic electroluminescent compound 2 are as follows:
(1) synthesis of intermediate C-2: dissolving 32.9mmol of the compound A-2 in 30ml of tetrahydrofuran solvent, dissolving 131.6mmol of the compound B-2 in 300ml of tetrahydrofuran solvent, adding 131.6mmol of lithium hydride in 300ml of tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound B-2 into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, dripping the tetrahydrofuran solution containing a compound A-2 into the reaction system, heating the reaction system to 25 ℃ after dripping, and reacting for 15 h; then the solution after reaction is led into ice water, the pH value of the solution after reaction is adjusted to about 1.0 by concentrated hydrochloric acid, then ethyl acetate is used for extraction for three times, the extracted organic phases are combined and mixed evenly, and the organic phases are washed by saturated saline solution, water and sodium bicarbonate aqueous solution in sequence, dried by sodium sulfate and removed of solvent to obtain 19.55g of compound C-2, and the yield is 83.44%;
(2) synthesis of the final product compound 2: adding 27.0mmol of intermediate C-2 into 300ml of dichloromethane solvent, then adding 64.8mmol of [ bis (trifluoroacetoxy) iodine ] benzene, stirring at room temperature for 10 hours, then concentrating the reaction solution in vacuum until a little of dichloromethane solvent remains, dropwise adding the concentrated solution into cold ethanol while stirring, carrying out suction filtration, washing and drying on the precipitated solid, and finally carrying out toluene recrystallization and vacuum sublimation on the dried solid to obtain 17.2g of organic electroluminescent compound 2, wherein the product yield is 92.1%.
Example 3
An organic electroluminescent compound 8, namely a compound numbered 8, has the following chemical synthesis reaction formula:
Figure GDA0003679592390000072
the specific preparation steps of the organic electroluminescent compound 8 are as follows:
(1) synthesis of intermediate F-8: dissolving 66.7mmol of compound D-8 in 40ml of tetrahydrofuran solvent, 133.4mmol of compound E-8 in 400ml of tetrahydrofuran solvent, 133.4mmol of lithium hydride in 400ml of tetrahydrofuran solvent, cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound E-8 into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, dripping the tetrahydrofuran solution containing a compound D-8 into the reaction system, heating the temperature of the reaction system to 25 ℃ after dripping, and reacting for 15 h; then the reaction system was poured into ice water, the pH of the reacted solution was adjusted to about 1.0 with concentrated hydrochloric acid, and then extracted three times with ethyl acetate, and the extracted organic phases were combined and mixed well, washed with saturated brine, water, and aqueous sodium bicarbonate solution in this order, dried with sodium sulfate, and the solvent in the reacted solution was removed to obtain 16.6g of compound F-8 with a yield of 91.5%.
(2) Synthesis of intermediate G-8: dissolving 60mmol of compound F-8 in 40ml of tetrahydrofuran solvent, cooling to-78 ℃, dropping 52.8ml of n-butyllithium while stirring, stirring at-78 ℃ for 1 hour, slowly raising the reaction temperature to room temperature, keeping the temperature at the room temperature for 15 minutes, then cooling the reaction liquid to-78 ℃ again, and keeping the temperature for 30 minutes; cooling 10ml tetrahydrofuran solvent solution containing 30mmol iodine to-78 deg.c, adding into the reaction liquid, cooling and stirring overnight; and (2) carrying out quenching reaction on a reaction system which is subjected to reaction overnight by using a saturated ammonium chloride solution, extracting a water layer by using a dichloromethane solvent, combining organic phases, washing by using a sodium thiosulfate aqueous solution and sodium chloride aqueous solution in sequence, drying by using magnesium sulfate, concentrating in vacuum until a little dichloromethane solvent remains, dropwise adding the concentrated solution into 200ml of cold ethanol while stirring, and carrying out suction filtration, washing and drying on a solid precipitated from the ethanol to obtain 25.1G of a compound G-8 with the yield of 79.86%.
(3) Synthesis of intermediate H-8: dissolving 45.0mmol of the compound G-8 in 40ml of tetrahydrofuran solvent, 133.4mmol of the compound I-8 in 400ml of tetrahydrofuran solvent, adding 133.4mmol of lithium hydride to 400ml of tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound I-8 into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, dripping the tetrahydrofuran solution containing a compound G-8 into the reaction system, heating to 25 ℃ after dripping, and reacting for 15 h; then the reaction system was poured into ice water, the pH of the reacted solution was adjusted to about 1.0 with concentrated hydrochloric acid, then extracted three times with ethyl acetate, and the extracted organic phases were combined and mixed well, washed with saturated brine, water, and aqueous sodium bicarbonate solution in this order, dried with sodium sulfate, and the solvent was removed to give 22.05g of compound H-8 with a yield of 85.37%.
(4) Synthesis of the final product compound 8: adding 38mmol of compound H-8 into 200ml of dichloromethane solvent, then adding 91.2mmol of [ bis (trifluoroacetoxy) iodine ] benzene, stirring for 10 hours at room temperature, then concentrating the reaction solution in vacuum until a little of dichloromethane solvent remains, dropwise adding the concentrated solution into 200ml of cold ethanol while stirring, carrying out suction filtration, washing and drying on the precipitated solid, and finally recrystallizing and sublimating the dried solid in vacuum through toluene to obtain 18.5g of organic electroluminescent compound 8, wherein the yield is 92.33%.
Examples 4 to 9
The preparation methods of the organic electroluminescent compounds 3, 9, 11, 16, 18, and 20 are the same as those in the above embodiments, and are not repeated herein, and the mass spectrometry detection results in each embodiment are shown in table 1 below:
TABLE 1
Compound (I) Molecular formula Calculated mass spectrum Mass spectrometric test values
Compound 3 C 14 F 4 N 4 S 2 363.95 363.88
Compound 9 C 28 F 10 N 6 S 2 673.95 673.98
Compound 16 C 22 F 4 N 12 S 2 571.97 571.83
Compound 18 C 26 F 12 N 12 S 2 771.96 771.91
Compound 20 C 38 H 12 F 8 N 4 S 2 740.04 740.10
EXAMPLE two preparation of organic electroluminescent device
Example 10 preparation of organic electroluminescent device 1
The method comprises the following specific steps:
(1) coating thickness of Fisher company of
Figure GDA0003679592390000091
The ITO glass substrate is placed in distilled water for cleaning for 3 times, ultrasonic cleaning is carried out for 30min, then the ITO glass substrate is repeatedly cleaned for 3 times by the distilled water, the ultrasonic cleaning is carried out for 15min, after the cleaning by the distilled water is finished, the ITO glass substrate is sequentially subjected to ultrasonic cleaning by isopropanol, acetone and methanol, then drying is carried out, the ITO glass substrate is transferred to a plasma cleaning machine for cleaning for 5min, and the substrate is cleaned for 5 min;
(2) loading the anode (indium tin oxide (ITO) electrode) bottom plate obtained in the step (1) into a vacuum evaporation machine, and carrying out vacuum evaporation on the compound 1 and N '-diphenyl-N, N' -di (1-naphthyl) -1, 1 '-biphenyl-4, 4' -diamine on the anode (indium tin oxide (ITO) electrode) according to the weight ratio of 1:9, wherein the evaporation speed is kept
Figure GDA0003679592390000092
Forming a hole injection layer about 45nm thick;
(3) performing vacuum evaporation on the vacuum injection layer obtained in the step (2) to form a hole transport layer with the thickness of about 50nm by using [ di- [4- (N, N-xylyl-amino) -phenyl ] cyclohexane;
(4) vacuum evaporating an organic light-emitting layer with the thickness of about 10nm on the hole transport layer obtained in the step (3), wherein 90% of 4, 4' -bis (carbazole-9-yl) -biphenyl is used as a light-emitting host material, and a light-emitting material doped with 10% of bis (1-phenyl-isoquinoline) (acetylacetone) iridium (III) (Ir (ppy)2(acac)) is adopted;
(5) vacuum evaporating a compound Alq3 on the organic light-emitting layer obtained in the step (4) at an evaporation speed of
Figure GDA0003679592390000093
Forming an electron transport layer of about 35 nm;
(6) and (5) evaporating a cathode in vacuum on the electron transport layer obtained in the step (5), wherein the cathode is aluminum with the thickness of about 100nm, and thus obtaining the organic electroluminescent device.
Examples 11-18 preparation of organic electroluminescent devices 2 to 9
The organic electroluminescent devices 2 to 9 were prepared in the same manner as the organic electroluminescent device 1 in example 10 above, except that the compound 1 of the hole injection layer was replaced with the compounds 2, 3, 8, 9, 11, 16, 18 and 20, respectively.
Comparative example 1 preparation of organic electroluminescent device 1
An organic electroluminescent device 1' was fabricated in the same manner as in example 10, except that the compound 1 in the hole injection layer was replaced with an organic electroluminescent compound NDP-9 commonly used in the art, the compound structure of which is shown below:
Figure GDA0003679592390000101
test example 1 organic electroluminescent device luminescence characteristics and service life test
Applying forward DC bias voltage to the organic electroluminescent devices 1-9 and 1', measuring the organic electroluminescent characteristics with PR-650 photometric measuring device of Photo Research, and measuring at 1000cd/m 2 The life of T95 was measured using a life measuring device of McScience.
In the above test examples, the driving voltage, luminance, luminous efficiency and lifetime obtained for each organic electroluminescent device were measured, and the results are shown in table 3 below:
TABLE 2
Figure GDA0003679592390000102
Figure GDA0003679592390000111
As can be seen from table 2, the organic electroluminescent device using the organic electroluminescent compound provided by the present invention as a hole injection layer has significantly reduced driving voltage, significantly improved luminous efficiency and significantly improved lifetime, compared to the organic electroluminescent device prepared from the conventional organic electroluminescent compound NDP-9.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (6)

1. An organic electroluminescent compound, characterized in that it has the following formula:
Figure FDA0003679592380000011
in chemical formula 1: r is 1 ～R 8 Independently of one another, from fluorine, cyano, trifluoromethyl, substituted alkyl, substituted aryl, substituted heteroaryl; x 1 And X 2 Each is independently selected from O or S;
the substitution refers to the complete substitution by fluorine, trifluoromethyl and nitrile groups.
2. An organic electroluminescent compound according to claim 1, wherein: the organic electroluminescent compound has a structure of chemical formula 2 or chemical formula 3:
Figure FDA0003679592380000012
in chemical formula 2: r 1 ～R 2 Independently of one another, from fluorine, cyano, trifluoromethyl, substituted alkyl, substituted aryl, substituted heteroaryl;X 1 and X 2 Each is independently selected from O or S;
in chemical formula 3: r 1 ～R 4 Independently of one another, from fluorine, cyano, trifluoromethyl, substituted alkyl, substituted aryl, substituted heteroaryl; x 1 And X 2 Each independently selected from O or S.
3. An organic electroluminescent compound according to claim 1 or 2, wherein: the organic electroluminescent compound is represented by any one of the following compounds:
Figure FDA0003679592380000013
Figure FDA0003679592380000021
Figure FDA0003679592380000031
4. a method for producing the organic electroluminescent compound according to claim 2, characterized in that: the synthetic route of the organic electroluminescent compound represented by chemical formula 2 is as follows:
scheme 1
Figure FDA0003679592380000032
the preparation method comprises the following specific steps:
(1) preparation of intermediate C: respectively dissolving the compound A and the compound B in a small amount of tetrahydrofuran solvent, adding lithium hydride into the tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound B into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, then dripping the tetrahydrofuran solution containing the compound A into the reaction system, heating the reaction system to 25 ℃ after dripping, and reacting for 15 h; then pouring the reacted solution into ice water, adjusting the pH value of the reacted solution to about 1.0 by using concentrated hydrochloric acid, extracting for three times by using ethyl acetate, combining and uniformly mixing the extracted organic phases, washing by using saturated saline solution, water and sodium bicarbonate aqueous solution in sequence, drying by using sodium sulfate, and removing the solvent to obtain a compound C;
(2) synthesis of the final product, chemical formula 2: adding the intermediate C into a dichloromethane solvent, adding [ bis (trifluoroacetoxy) iodine ] benzene, stirring at room temperature for 10 hours, concentrating the reaction solution in vacuum after the reaction is finished, dropwise adding the concentrated solution into cold ethanol while stirring, carrying out suction filtration, washing and drying on the precipitated solid, and finally carrying out toluene recrystallization and vacuum sublimation on the dried solid to obtain the organic electroluminescent compound shown in chemical formula 2.
5. A method for producing the organic electroluminescent compound according to claim 2, characterized in that: the synthetic route of the organic electroluminescent compound represented by chemical formula 3 is as follows:
Figure FDA0003679592380000041
the preparation method comprises the following specific steps:
(1) synthesis of intermediate F: respectively dissolving the compound D and the compound E in a small amount of tetrahydrofuran solvent, adding lithium hydride into the tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound E into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, dripping a tetrahydrofuran solution containing a compound D into the reaction system, heating the temperature of the reaction system to 25 ℃ after dripping, and reacting for 15 h; then pouring the reaction system into ice water, adjusting the pH value of the solution after reaction to about 1.0 by using concentrated hydrochloric acid, extracting for three times by using ethyl acetate, combining and uniformly mixing the extracted organic phases, washing by using saturated saline solution, water and sodium bicarbonate aqueous solution in sequence, drying by using sodium sulfate, and removing the solvent in the solution after reaction to obtain a compound F;
(2) synthesis of intermediate G: dissolving the intermediate F in a tetrahydrofuran solvent, cooling to-78 ℃, dropwise adding n-butyllithium while stirring, stirring at-78 ℃ for 1 hour, slowly heating the reaction temperature to room temperature, keeping the temperature at the room temperature for 15 minutes, cooling the reaction liquid to-78 ℃ again, and keeping the temperature for 30 minutes; cooling tetrahydrofuran solvent solution containing iodine to-78 deg.c, adding into the reaction liquid, cooling and stirring overnight; carrying out quenching reaction on a reaction system which is subjected to reaction overnight by using a saturated ammonium chloride solution, extracting a water layer by using a dichloromethane solvent, combining organic phases, washing by using a sodium thiosulfate aqueous solution and sodium chloride aqueous solution in sequence, drying by using magnesium sulfate, concentrating in vacuum until a little dichloromethane solvent remains, dropwise adding the concentrated solution into cold ethanol while stirring, and carrying out suction filtration, washing and drying on a solid precipitated from the ethanol to obtain a compound G;
(3) synthesis of intermediate H: respectively dissolving the intermediate G and the compound I in a small amount of tetrahydrofuran solvent, adding lithium hydride into the tetrahydrofuran solvent, and cooling to 0 ℃; slowly dripping a tetrahydrofuran solution containing a compound I into a tetrahydrofuran solution containing lithium hydride at the temperature of 0 ℃, heating to room temperature, reacting for 30min, cooling a reaction system to 0 ℃, dripping the tetrahydrofuran solution containing an intermediate G into the reaction system, heating to 25 ℃ after dripping, and reacting for 15 h; then pouring the reaction system into ice water, adjusting the pH value of the solution after reaction to about 1.0 by using concentrated hydrochloric acid, extracting for three times by using ethyl acetate, combining and uniformly mixing the extracted organic phases, washing by using saturated saline solution, water and sodium bicarbonate aqueous solution in sequence, drying by using sodium sulfate, and removing the solvent to obtain a compound H;
(4) synthesis of the final product, chemical formula 3: adding the intermediate H into a dichloromethane solvent, adding [ bis (trifluoroacetoxy) iodine ] benzene, stirring at room temperature for 10 hours, then carrying out vacuum concentration on a reaction solution until a little dichloromethane solvent remains, dropwise adding the concentrated solution into cold ethanol while stirring, carrying out suction filtration, washing and drying on a precipitated solid, and finally carrying out toluene recrystallization and vacuum sublimation on the dried solid to obtain the organic electroluminescent compound shown in chemical formula 3.
6. An organic electroluminescent device comprising the organic electroluminescent compound according to any one of claims 1 to 3 or the organic electroluminescent compound prepared according to any one of claims 4 to 5.
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