CN106699731A - Maleic hydrazine derivative and preparation method and application thereof - Google Patents

Maleic hydrazine derivative and preparation method and application thereof Download PDF

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CN106699731A
CN106699731A CN201611102700.7A CN201611102700A CN106699731A CN 106699731 A CN106699731 A CN 106699731A CN 201611102700 A CN201611102700 A CN 201611102700A CN 106699731 A CN106699731 A CN 106699731A
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compound
substitution
alkylidene
maleic acid
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CN106699731B (en
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高自良
石宇
王元勋
胡葆华
孟凡民
张明智
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Valiant Co Ltd
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    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract

The invention belongs to the field of organic photoelectric materials, and particularly relates to maleic hydrazine derivative and a preparation method and application thereof. A structural formula of the maleic hydrazine derivative is shown as follows (shown in the description); in a formula (1), Y is hydrogen, straight-chain alkyl of C1 to 10 and branched-chain alkyl of C1 to 10, Ar1 and Ar2 each independently represent hydrogen, aryl of C5 to 20, Ar-R or -R, the Ar1 and the Ar2 are not hydrogen at the same time, and Ar is phenyl, biphenyl, terphenyl, naphthyl, anthryl or phenanthryl. As maleic hydrazine is utilized as a mother nucleus of the compound, the compound has the characteristics that molecules are not prone to crystallizing and gathering, and good film forming property is achieved. When the compound is utilized as a luminescent layer material of an OLED (organic light emitting diode) luminescent device, the manufactured OLED device has good photoelectric property.

Description

A kind of maleic acid hydrazide analog derivative and its preparation method and application
Technical field
The invention belongs to organic photoelectrical material field, more particularly to a kind of maleic acid hydrazide analog derivative and preparation method thereof and Using.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used to make Make new display product, it is also possible to for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is quite varied.
OLED luminescent devices just as the structure of sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it Between organic functional material, various difference in functionality materials are overlapped mutually according to purposes and collectively constitute together OLED luminescent devices. As current device, when the two end electrodes applied voltage to OLED luminescent devices, and by electric field action organic layer functional material Positive and negative charge in film layer, positive and negative charge is further combined in luminescent layer, that is, produce OLED electroluminescent.
The problems such as current OLED still suffers from life-span and relatively low efficiency, people pass through ultra clean technology, and encapsulation technology is opened Hair has luminescent material of high glass-transition temperature etc. to improve the life-span of device, and doping techniques and exploitation are tied with the two poles of the earth The new material of structure, then be the direction for improving device efficiency.
Doping techniques are reduced by the way that luminescent material (guest materials) is dispersed among other materials (material of main part) The concentration of luminescent material, so as to avoid intermolecular aggregation and concentration quenching, and then realizes improving device efficiency, improves electroluminescent Excitation, extends the purpose of device lifetime.
For the actual demand of current OLED display Lighting Industries, the development of current OLED material is also far from enough, falls After the requirement of panel manufacturing enterprise, OLED optical property is not good enough.
The content of the invention
For above-mentioned problem, the technical problems to be solved by the invention are to provide a kind of maleic acid hydrazide analog derivative And its preparation method and application.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of maleic acid hydrazide analog derivative, its structural formula is as follows：
In formula (1), Y is hydrogen, C1-10Straight chained alkyl, C1-10Branched alkyl；Ar1、Ar2Expression hydrogen independently, C5-20Aryl Ar R or R, and Ar1、Ar2It is asynchronously hydrogen；Ar is phenyl, dibiphenylyl, terphenyl, naphthyl, anthryl or phenanthrene Base；
R is selected from one of formula (2), formula (3), formula (4) or formula (5)：
Wherein, X1It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Alkylidene, the C of straight chained alkyl substitution1-10Branched alkane One kind in the tertiary amine groups that the alkylidene of base substitution, the alkylidene of aryl substitution, alkyl-substituted tertiary amine groups or aryl replace；
R1、R2Selection hydrogen independently, formula (6) or structure shown in formula (7)：
A isX in a2、X3Be respectively and independently selected from is oxygen atom, sulphur atom, C1-10Straight chained alkyl replaces Alkylidene, C1-10Alkylidene, alkyl-substituted tertiary amine groups or aryl substitution that the alkylidene of branched alkyl substitution, aryl replace Tertiary amine groups in one kind；Formula (6), structure shown in formula (7) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2 Key, CL’2-CL’3Key or CL’3-CL’4It is bonded and is connected on formula (2), formula (3), formula (4) or formula (5).
Further, a isAnd and CL4-CL5Key or CL‘4-CL’5It is bonded when connecing, X1And X2Location overlap, only Retain one of them；X3It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Alkylidene, the C of straight chained alkyl substitution1-10Branched alkane One kind in the tertiary amine groups that the alkylidene of base substitution, the alkylidene of aryl substitution, alkyl-substituted tertiary amine groups or aryl replace.
Further, the R-portion structure is as follows：
A kind of preparation method of maleic acid hydrazide analog derivative, comprises the following steps：Chemical compounds I is taken with compound ii Generation reaction, obtains product I, as shown in Equation 1；Or be there is into substitution reaction in compound III and compound ii, product II is obtained, such as formula Shown in 2；
Bromo compound, R-H that maleic acid hydrazide is core are weighed as described in formula 1 or formula 2, is dissolved with toluene；Add Pd2 (dba)3, tri-tert phosphorus, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95- 100 DEG C, react 10-24 hours, cooling, filtering reacting solution, filtrate revolving crosses silicagel column, obtains target product；The chemical combination Thing I is 1 with the mol ratio of compound ii:(2.0-6.0), compound III is 1 with the mol ratio of compound ii:(2.0-6.0)； Pd2(dba)3With maleic acid hydrazide for the mol ratio of the bromide of core is (0.006-0.04):1, tri-tert phosphorus and maleic acid hydrazide For the mol ratio of the bromide of core is (0.006-0.04):1, sodium tert-butoxide and maleic acid hydrazide for the bromide of core mole Than being (1.0-6.0):1.
A kind of application of maleic acid hydrazide analog derivative in electroluminescent organic material.
A kind of organic electroluminescence device, using maleic acid hydrazide analog derivative as the organic electroluminescence device hair Light layer material.
Further, the organic electroluminescence device is OLED.
The part-structure of the maleic acid hydrazide analog derivative of present invention synthesis is as follows：
The beneficial effects of the invention are as follows：Use with maleic acid hydrazide as parent, with it is intermolecular be difficult to crystallize, be difficult aggregation, The characteristics of with good filming；It is generally rigid radical in molecule, with good heat endurance；With suitable HOMO and Lumo energy, can apply in OLED luminescent devices as luminescent layer.
Such material of the invention can be applied to the making of OLED luminescent devices, and can obtain good device performance, institute When stating compound and being used as the emitting layer material of OLED luminescent devices, the device of making has good photoelectric properties.This hair The bright compound has good application effect in OLED luminescent devices, with good industrialization prospect.
Brief description of the drawings
Fig. 1 is a kind of maleic acid hydrazide analog derivative OLED emitting device structure schematic diagrames of the invention.
In accompanying drawing, the list of parts representated by each label is as follows：
1st, transparent substrate layer, 2, ito anode layer, 3, hole injection layer, 4, hole transport/electronic barrier layer, 5, luminescent layer, 6th, hole barrier/electron transfer layer, 7, electron injecting layer, 8, negative electrode reflection electrode layer.
Specific embodiment
Principle of the invention and feature are described below in conjunction with accompanying drawing, example is served only for explaining the present invention, and It is non-for limiting the scope of the present invention.
The preparation of the compound C01 of embodiment 1
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 1,0.03mol compound M01, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.5%, yield 76.84%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C40H26N4O4, theoretical value 626.1954, test value 626.1950。
Elementary analysis (C40H26N4O4)：Theoretical value C：76.67, H：4.18, N：8.94, O：10.21, test value：C： 76.64, H：4.19, N：8.95, O：10.22.
The preparation of the compound C03 of embodiment 2
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 1,0.03mol compound M02, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.2%, yield 73.24%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C46H38N4O4, theoretical value 678.2995, test value 678.2991。
Elementary analysis (C46H38N4O4)：Theoretical value C：81.39, H：5.64, N：8.25, O：4.71, test value：C： 81.37, H：5.63, N：8.28, O：4.72.
The preparation of the compound C09 of embodiment 3
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 1,0.03mol compound M03, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.0%, yield 65.28%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C58H42N4O4, theoretical value 858.3206, test value 858.3210。
Elementary analysis (C58H42N4O4)：Theoretical value C：81.10, H：4.93, N：6.52, O：7.45, test value：C： 81.13, H：4.95, N：6.50, O：7.42.
The preparation of the compound C13 of embodiment 4
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 1,0.03mol compound M04, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.1%, yield 64.58%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C58H42N4O4, theoretical value 858.3206, test value 858.3203。
Elementary analysis (C58H42N4O4)：Theoretical value C：81.10, H：4.93, N：6.52, O：7.45, test value：C： 81.07, H：4.96, N：6.53, O：7.44.
The preparation of the compound C18 of embodiment 5
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 1,0.03mol compound M04, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.1%, yield 64.58%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C58H42N4O4, theoretical value 826.3308, test value 826.3313。
Elementary analysis (C58H42N4O4)：Theoretical value C, 84.24；H,5.12；N,6.77；O, 3.87, test value：C, 84.34；H,5.10；N,6.74；O,3.82.
The preparation of the compound C19 of embodiment 6
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 1,0.03mol compound M06, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.7%, yield 67.39%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C52H36N6O2, theoretical value 776.2900, test value 776.2907。
Elementary analysis (C52H36N6O2)：Theoretical value C：80.39, H：4.67, N：10.82, O：4.12, test value：C： 80.42, H：4.65, N：10.83, O：4.10.
The preparation of the compound C23 of embodiment 7
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol 1- (4- bromophenyls) -2- phenyl -1,2- bis- Hydrogen pyridazine -3,6- diketone, 0.03mol compounds M07,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10- 4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 hours, sample point plate, and reaction is complete；Natural cooling, filtering, filtrate Revolving, column chromatography obtains target product, HPLC purity 99.8%, yield 70.49%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C41H29N3O2, theoretical value 595.2260, test value 598.2264。
Elementary analysis (C41H29N3O2)：Theoretical value C, 82.67；H,4.91；N,7.05；O, 5.37, test value：C, 82.70；H,4.88；N,7.03；O,5.39.
The preparation of the compound C27 of embodiment 8
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 2,0.03mol compound M02, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.1%, yield 65.88%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C46H38N4O2, theoretical value 678.2995, test value 678.2992。
Elementary analysis (C46H38N4O2)：Theoretical value C：81.39, H：5.64, N：8.25, O：4.71, test value：C： 81.37, H：5.66, N：8.24, O：4.73.
The preparation of the compound C31 of embodiment 9
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 2,0.03mol compound M08, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.2%, yield 60.47%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C52H30N4O6, theoretical value 806.2165, test value 806.2167。
Elementary analysis (C52H30N4O6)：Theoretical value C：77.41, H：3.75, N：6.94, O：11.90, test value：C： 77.43, H：3.76, N：6.96, O：11.85.
The preparation of the compound C37 of embodiment 10
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 2,0.03mol compound M09, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.4%, yield 63.59%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C58H42N4O4, theoretical value 858.3206, test value 858.3207。
Elementary analysis (C58H42N4O4)：Theoretical value C：81.10, H：4.93, N：6.52, O：7.45, test value：C： 81.14, H：4.91, N：6.50, O：7.45.
The preparation of the compound C40 of embodiment 11
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 2,0.03mol compound M10, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.5%, yield 68.52%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C52H30N4O4, theoretical value 774.2267, test value 774.2264。
Elementary analysis (C52H30N4O4)：Theoretical value C：80.61, H：3.90, N：7.23, O：8.26, test value：C： 80.63, H：3.91, N：7.25, O：8.21.
The preparation of the compound C45 of embodiment 12
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 2,0.03mol compound M11, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.4%, yield 64.27%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C52H32N6O4, theoretical value 804.2485, test value 804.2488。
Elementary analysis (C52H32N6O4)：Theoretical value C：77.60, H：4.01, N：10.44, O：7.95, test value：C： 77.63, H：4.00, N：10.42, O：7.95.
The preparation of the compound C52 of embodiment 13
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 3,0.03mol compound M12, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.8%, yield 70.88%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C48H30N4O2, theoretical value 694.2369, test value 694.2366。
Elementary analysis (C48H30N4O2)：Theoretical value C：82.98, H：4.35, N：8.06, O：4.61, test value：C： 82.95, H：4.36, N：8.08, O：4.61.
The preparation of the compound C64 of embodiment 14
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 3,0.03mol compound M10, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.5%, yield 64.73%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C60H34N4O4, theoretical value 874.2580, test value 874.2583。
Elementary analysis (C60H34N4O4)：Theoretical value C：82.37, H：3.92, N：6.40, O：7.31, test value：C： 82.38, H：3.93, N：6.39, O：7.30.
The preparation of the compound C72 of embodiment 15
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 3,0.03mol compound M7, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.6%, yield 66.18%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C74H50N4O2, theoretical value 1026.3934, test value 1026.3930。
Elementary analysis (C74H50N4O2)：Theoretical value C：86.52, H：4.91, N：5.45, O：3.12, test value：C： 86.50, H：4.92, N：5.47, O：3.11.
The preparation of the compound C75 of embodiment 16
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 4,0.03mol compound M02, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.4%, yield 65.58%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C58H46N4O2, theoretical value 830.3621, test value 830.3624。
Elementary analysis (C58H46N4O2)：Theoretical value C：83.83, H：5.58, N：6.74, O：3.85, test value：C： 83.81, H：5.59, N：6.77, O：3.83.
The preparation of the compound C83 of embodiment 17
In the there-necked flask of 250ml, lead under nitrogen protection, add 0.01mol compound 4,0.03mol compound M04, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 100ml toluene is heated to reflux 20 Hour, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, column chromatography obtains target product, HPLC purity 99.2%, yield 64.87%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C70H50N4O4, theoretical value 1010.3822, test value 1010.3820。
Elementary analysis (C70H50N4O4)：Theoretical value C：83.15, H：4.98, N：5.54, O：6.33, test value：C： 83.12, H：4.96, N：5.57, O：6.35.
The compounds of this invention can be as emitting layer material, to the compounds of this invention C3, compound C23, current material CBP The test of hot property, luminescent spectrum, fluorescence quantum efficiency and cyclic voltammetric stability is carried out, testing result is as shown in table 1.
Table 1
Compound Tg(℃) Td(℃) λPL(nm) Φf Cyclic voltammetric stability
Compound C3 131 382 408 63.8 It is excellent
Compound C23 125 371 412 61.7 It is excellent
Material C BP 113 353 369 26.1 Difference
Note：Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimetries Instrument) determine, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is in nitrogen atmosphere weightless 1% temperature, public in Japanese Shimadzu It is measured on the TGA-50H thermogravimetric analyzers of department, nitrogen flow is 20mL/min；λPLIt is sample solution fluorescence emission wavelengths, General health SR-3 spectroradiometers are opened up using Japan to determine；Φ f are that solid powder fluorescence quantum efficiency (utilizes U.S.'s marine optics Maya2000Pro fiber spectrometers, Lan Fei companies of the U.S. C-701 integrating spheres and marine optics LLS-LED light sources composition Test solid fluorescence quantum efficiency test system, reference literature Adv.Mater.1997,9,230-232 method is measured).
Cyclic voltammetric stability is identified by the redox characteristic of cyclic voltammetry test material；Test-strips Part：It is 2 that test sample is dissolved in volume ratio:1 dichloromethane and acetonitrile mixed solvent, concentration 1mg/mL, electrolyte is 0.1M The organic solution of tetrabutyl ammonium tetrafluoroborate or hexafluorophosphate.Reference electrode is Ag/Ag+ electrodes, is titanium to electrode Plate, working electrode is ITO electrode, and cycle-index is 20 times.
From upper table data, the compounds of this invention has suitable luminescent spectrum, and Φ f higher are suitable as lighting Layer material；Meanwhile, the compounds of this invention has preferable oxidation-reduction stability, heat endurance higher so that apply this hair The OLED efficiency of bright compound and life-span get a promotion.
Device embodiments：
Describe the compound conduct in the devices of present invention synthesis in detail below by way of device embodiments 1-10 and comparative example 1 The application effect of the dopant material of luminescent layer.Device embodiments 2-10 of the present invention, comparative example 1 are compared with device embodiments 1 The manufacture craft of the device is identical, and employed identical baseplate material and electrode material, the film of electrode material Thickness is also consistent, except that being converted to the dopant material of the luminescent layer in device.The composition structure of each device As shown in table 2.The test result of device is shown in Table 3.
Device embodiments 1
Ito anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transport/electronic barrier layer 4 (CBP and compound C03 are according to 100 for (TAPC, thickness 40nm)/luminescent layer 5：7 weight is than blending, thickness：30nm)/hole resistance Gear/electron transfer layer 6 (TPBI, thickness 40nm)/LiF/Al
Specific preparation process is as follows：
Ito anode 2 (thickness is 150nm) of layer are washed, i.e., is carried out successively after neutralizing treatment, pure water, drying again Ultraviolet-ozone washing is carried out to remove the organic residue on transparent ITO surfaces.
On ito anode layer 2 after above-mentioned washing has been carried out, using vacuum deposition apparatus, evaporation thickness is 10nm's Molybdenum trioxide MoO3Used as hole injection layer 3, be and then deposited with the TAPC of 40nm thickness as hole transport/electronic blocking Layer 4.
After above-mentioned hole transport/electronic blocking layer material evaporation terminates, the luminescent layer 5 of OLED luminescent devices is made, used Used as material of main part, used as dopant material, dopant material doping ratio is 7% weight ratio to the compounds of this invention C03 to CBP, is lighted Tunic thickness is 30nm.
After above-mentioned luminescent layer 5, it is TPBI to continue vacuum evaporation hole barrier/electron transport layer materials, the material Vacuum evaporation thickness is 40nm, and this layer is hole barrier/electron transfer layer 6.
On hole barrier/electron transfer layer 6, by vacuum deposition apparatus, it is the lithium fluoride (LiF) of 1nm to make thickness Layer, this layer is electron injecting layer 7.
On electron injecting layer 7, by vacuum deposition apparatus, it is aluminium (Al) layer of 80nm to make thickness, and this layer is negative electrode Reflection electrode layer 8 is used.The composition structure of obtained device is as shown in table 2.
After completing OLED luminescent devices as described above, anode and negative electrode are coupled together with known drive circuit, surveyed The I-E characteristic of the luminous efficiency of metering device, luminescent spectrum and device.The test result of obtained device is shown in Table 3.
Table 2
Table 3
Device code name Current efficiency Color The LT95 life-spans
Device embodiments 1 1.2 Blue light 1.8
Device embodiments 2 1.4 Blue light 2.7
Device embodiments 3 1.3 Blue light 1.2
Device embodiments 4 1.4 Blue light 2.8
Device embodiments 5 1.5 Blue light 1.8
Device embodiments 6 1.4 Blue light 2.0
Device embodiments 7 1.3 Blue light 1.5
Device embodiments 8 1.4 Blue light 1.2
Device embodiments 9 1.2 Blue light 1.9
Device embodiments 10 1.3 Blue light 1.3
Device comparative example 1 1.0 Blue light 1.0
Note：Using comparative example 1 as reference, the device property indices of comparative example 1 are set to 1.0 to device detection performance.Compare The current efficiency of example 1 is 10.8cd/A (@10mA/cm2)；CIE chromaticity coordinates is (0.14,0.32)；The LT95 life-spans under 1500 brightness Decay to 2.2Hr.
Below by way of the device embodiments 11-18 explanations compound for synthesizing of the invention in the devices as luminous layer main body material The application effect of material.The manufacture craft of device embodiments 11-18 devices compared with device embodiments 1 of the present invention is complete Identical, and employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, except that Material of main part to the luminescent layer 5 in device is transformed to the compounds of this invention, and dopant material uses GD19.As a comparison, compare Material of main part uses CBP, dopant material to use GD19 in luminescent device described in example 2.The structure composition of each embodiment obtained device As shown in table 4.The performance test results of each device are shown in Table 5.
Table 4
Table 5
Device embodiments Current efficiency Color The LT95 life-spans
Device embodiments 11 2.8 Green glow 3.3
Device embodiments 12 3.2 Green glow 3.2
Device embodiments 13 3.2 Green glow 2.8
Device embodiments 14 2.9 Green glow 3.2
Device embodiments 15 3.3 Green glow 3.0
Device embodiments 16 2.8 Green glow 2.7
Device embodiments 17 3.5 Green glow 2.9
Device embodiments 18 3.8 Green glow 3.2
Device comparative example 1 1.0 Green glow 1.0
Note：Using device comparative example 1 as reference, the device property indices of comparative example 1 are set to 1.0 to device detection performance. The current efficiency of comparative example 1 is 6.5cd/A (@10mA/cm2)；CIE chromaticity coordinates is (0.32,0.61)；The LT95 longevity under 5000 brightness Life decays to 3.8Hr.
Table 3 and the result of table 5 can be seen that compound of the present invention can apply with OLED luminescent devices make, and with than Compared compared with example, either efficiency or life-span are than the larger change of acquisition of known OLED material.Material of the present invention is in OLED There is good application effect, with good industrialization prospect in luminescent device.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.

Claims (7)

1. a kind of maleic acid hydrazide analog derivative, it is characterised in that structural formula is as follows：
In formula (1), Y is hydrogen, C1-10Straight chained alkyl, C1-10Branched alkyl；Ar1、Ar2Expression hydrogen independently, C5-20 Aryl-Ar-R or-R, and Ar1、Ar2It is asynchronously hydrogen；Ar is phenyl, dibiphenylyl, terphenyl, naphthyl, anthryl or phenanthrene Base；
R is selected from one of formula (2), formula (3), formula (4) or formula (5)：
Wherein, X1It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Alkylidene, the C of straight chained alkyl substitution1-10Branched alkyl takes One kind in the tertiary amine groups that the alkylidene in generation, the alkylidene of aryl substitution, alkyl-substituted tertiary amine groups or aryl replace；
R1、R2Selection hydrogen independently, formula (6) or structure shown in formula (7)：
A isX in a2、X3Be respectively and independently selected from is oxygen atom, sulphur atom, C1-10The Asia of straight chained alkyl substitution Alkyl, C1-10The uncle that the alkylidene of branched alkyl substitution, the alkylidene of aryl substitution, alkyl-substituted tertiary amine groups or aryl replace One kind in amido；Formula (6), structure shown in formula (7) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL’2-CL’3Key or CL’3-CL’4It is bonded and is connected on formula (2), formula (3), formula (4) or formula (5).
2. a kind of maleic acid hydrazide analog derivative according to claim 1, it is characterised in that a isAnd and CL4- CL5Key or CL‘4-CL’5It is bonded when connecing, X1And X2Location overlap, only retain one of them；X3It is expressed as oxygen atom, sulphur atom, selenium Atom, C1-10Alkylidene, the C of straight chained alkyl substitution1-10The alkylidene of branched alkyl substitution, the alkylidene of aryl substitution, alkyl take One kind in the tertiary amine groups of tertiary amine groups or the aryl substitution in generation.
3. a kind of preparation method of maleic acid hydrazide analog derivative as claimed in claim 1, it is characterised in that comprise the following steps： Be there is into substitution reaction in chemical compounds I and compound ii, obtain product I, as shown in Equation 1；Or send out compound III and compound ii Raw substitution reaction, obtains product II, as shown in Equation 2；
4. a kind of preparation method of maleic acid hydrazide analog derivative according to claim 3, it is characterised in that formula 1 exists with formula 2 Reacted under inert atmosphere conditions, its reaction temperature is 95-100 DEG C, the reaction time is 10-24 hours, the chemical compounds I and chemical combination The mol ratio of thing II is 1:(2.0-6.0), compound III is 1 with the mol ratio of compound ii:(2.0-6.0).
5. application of a kind of maleic acid hydrazide analog derivative as described in Claims 1-4 is any in electroluminescent organic material.
6. a kind of organic electroluminescence device, it is characterised in that using the maleic acid hydrazide class as described in Claims 1-4 is any Derivative as the organic electroluminescence device emitting layer material.
7. a kind of organic electroluminescence device according to claim 6, it is characterised in that the organic electroluminescence device It is OLED.
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CN108659010A (en) * 2017-03-27 2018-10-16 北京绿人科技有限责任公司 A kind of organic compound and its application in organic electroluminescence device
CN109535130A (en) * 2018-12-18 2019-03-29 阜阳欣奕华材料科技有限公司 Dihydrobenzo indazole compounds, organic electroluminescence device and display device
CN109608440A (en) * 2018-12-18 2019-04-12 阜阳欣奕华材料科技有限公司 Dihydrobenzo indazole compounds, organic electroluminescence device and display device

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CN103265946A (en) * 2013-05-27 2013-08-28 烟台万润精细化工股份有限公司 Novel OLED (organic light emitting diode) material and application thereof
IN2013MU04030A (en) * 2013-12-24 2015-08-21 M V Ramana Dr M
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CN108659010A (en) * 2017-03-27 2018-10-16 北京绿人科技有限责任公司 A kind of organic compound and its application in organic electroluminescence device
CN109535130A (en) * 2018-12-18 2019-03-29 阜阳欣奕华材料科技有限公司 Dihydrobenzo indazole compounds, organic electroluminescence device and display device
CN109608440A (en) * 2018-12-18 2019-04-12 阜阳欣奕华材料科技有限公司 Dihydrobenzo indazole compounds, organic electroluminescence device and display device

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