CN106279184A - A kind of pyridazine class derivant and its preparation method and application - Google Patents

A kind of pyridazine class derivant and its preparation method and application Download PDF

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CN106279184A
CN106279184A CN201610653152.0A CN201610653152A CN106279184A CN 106279184 A CN106279184 A CN 106279184A CN 201610653152 A CN201610653152 A CN 201610653152A CN 106279184 A CN106279184 A CN 106279184A
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unsubstituted
substituted
pyridazine class
ring
derivant
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刘喜庆
郭建华
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Changchun Haipurunsi Technology Co Ltd
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Changchun Haipurunsi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/06—Peri-condensed systems
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

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  • Electroluminescent Light Sources (AREA)

Abstract

The present invention provides a kind of pyridazine class derivant and its preparation method and application, relates to organic photoelectrical material technical field.By optimizing Molecular Design, pyridazine class derivant obtained by the present invention has good cavity transmission ability, can be used for preparing organic electroluminescence device, especially as the hole mobile material in organic electroluminescence device, show high efficiency, high brightness, long-life advantage, be better than existing conventional OLED.The present invention also provides for the preparation method of a kind of pyridazine class derivant, and this preparation method is simple, raw material is easy to get.

Description

A kind of pyridazine class derivant and its preparation method and application
Technical field
The present invention relates to organic photoelectrical material technical field, be specifically related to a kind of pyridazine class derivant and preparation method thereof and Application.
Background technology
1987, Tang of Kodak et al. used 8-hydroxyquinoline to close aluminum (Alq3) as luminescent material first Prepare Organic Light Emitting Diode (OLEO), start electroluminescent organic material and the new situation of device research.Owing to OLED has Have that high brightness, wide vision, fast response time, image stabilization, luminous color are abundant, resolution is high, driving voltage is low and all solidstate, The advantage such as ultra-thin, it has also become the focus of current display device research.Along with OLED technology development and properties of product improve constantly, OLED is the most gradually widely used in the fields such as business, communication, computer, electronic product and traffic.
In the more than ten years in past, the research unit of the nearlyest thousand and enterprise join grinding of Organic Light Emitting Diode In Faing, it is greatly promoted the fast development of OLED.Luminous organic material is broadly divided into two classes at present: a class is small molecule material (organic small molecules), such as Alq3, fluorescent dye etc., mainly prepares device by the method for vacuum evaporation；Separately One class is polymeric material (polymers), such as p-phenylene vinylene (PPV) and derivant thereof, mainly passes through spin coated or ink-jet The legal system preparation photospheres such as technique.
All in all, the direction of following OLED be development high efficiency, high brightness, the long-life, the white light parts of low cost and Full color display device, but this technological industrialization process still faces many key issues, how to design new performance more preferable Material is adjusted, always those skilled in the art's problem demanding prompt solution.
Summary of the invention
It is an object of the invention to provide a kind of pyridazine class derivant and its preparation method and application, it is organic that the present invention provides Compound thermal stability is high, good film-forming property, and preparation method is simple, and the organic luminescent device being made up of this compound shows High efficiency, high brightness, long-life advantage, be the luminous organic material of function admirable.
Present invention firstly provides a kind of pyridazine class derivant, structural formula is:
Wherein, R1、R2The independent aryl selected from substituted or unsubstituted C6～C50, substituted or unsubstituted C10～C30 Condensed ring, substituted or unsubstituted five-ring heterocycles, substituted or unsubstituted hexa-member heterocycle, substituted or unsubstituted C8～C30 Condensed hetero ring；
Or described R1、R2Substituted or unsubstituted condensed hetero ring is formed with the nitrogen-atoms at place.
Preferably, described R1、R2The independent aryl selected from substituted or unsubstituted C6～C30, substituted or unsubstituted The condensed ring of C10～C30, substituted or unsubstituted five-ring heterocycles, substituted or unsubstituted hexa-member heterocycle, substituted or unsubstituted C8 ～the condensed hetero ring of C20.
Preferably, described R1、R2The independent aryl selected from substituted or unsubstituted C6～C18, the condensed ring of C10～C22, Five-ring heterocycles, hexa-member heterocycle, the condensed hetero ring of C8～C20.
Preferably, described R1、R2Independent selected from phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, xenyl, terphenyl, indenes Base, pyrrole radicals, pyridine radicals, thienyl, furyl, indyl, benzothienyl, benzofuranyl, quinolyl, imidazole radicals, thiophene Oxazolyl, oxazolyl or fluorenyl.
Preferably, R1、R2With the condensed hetero ring that the nitrogen-atoms at place forms substituted or unsubstituted C12～C30.
Preferably, any one in described pyridazine class derivant structure shown in following TM1～TM47:
The present invention also provides for the preparation method of a kind of pyridazine class derivant, and syntheti c route is as follows:
Wherein, R1、R2Independent selected from replace or unsubstituted C6～C50 aryl, substituted or unsubstituted C10～C30 Condensed ring, substituted or unsubstituted five-ring heterocycles, substituted or unsubstituted hexa-member heterocycle, substituted or unsubstituted C8～C30 Condensed hetero ring；
Or described R1, R2 forms substituted or unsubstituted condensed hetero ring with the nitrogen-atoms at place.
The present invention also provides for the application in organic electroluminescence device of the pyridazine class derivant.
Preferably, described organic electroluminescence device includes anode, negative electrode and organic matter layer, and organic matter layer comprises hole note Enter at least in layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer Layer；
At least one of which in described organic matter layer contains described pyridazine class derivant.
Preferably, described pyridazine class derivant is for preparing the hole transmission layer of organic electroluminescence device.
Beneficial effects of the present invention:
Present invention firstly provides a kind of pyridazine class derivant, this pyridazine class derivant has structure shown in Formulas I, by introducing Condensed ring class rigidity, close packed structure, make the pyridazine class derivant thermal stability height obtained by the present invention, good film-forming property, can be used for Prepare organic electroluminescence device, especially as the hole mobile material in organic electroluminescence device, show high efficiency, High brightness, longevity advantage, be better than existing conventional OLED.The present invention also provides for the preparation side of a kind of pyridazine class derivant Method, this preparation method is simple, raw material is easy to get, it is possible to meet the needs of industrialization development.Pyridazine class derivant of the present invention is at OLED Luminescent device has good application effect, there is good industrialization prospect.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but Should be appreciated that these describe simply as to further illustrate the features and advantages of the present invention rather than to the claims in the present invention Limit.
Present invention firstly provides a kind of pyridazine class derivant, structural formula is:
Wherein, R1、R2The independent aryl selected from substituted or unsubstituted C6～C50, substituted or unsubstituted C10～C30 Condensed ring, substituted or unsubstituted five-ring heterocycles, substituted or unsubstituted hexa-member heterocycle, substituted or unsubstituted C8～C30 Condensed hetero ring；
Or described R1、R2Substituted or unsubstituted condensed hetero ring is formed with the nitrogen-atoms at place.
It is preferably R1、R2The independent aryl selected from substituted or unsubstituted C6～C30, substituted or unsubstituted C10～ The condensed ring of C30, substituted or unsubstituted five-ring heterocycles, substituted or unsubstituted hexa-member heterocycle, substituted or unsubstituted C8～C20 Condensed hetero ring.
According to the present invention, described substituted aryl, substituted five-ring heterocycles, substituted hexa-member heterocycle, substituted thick miscellaneous In ring, substituent group independence selected from alkyl, alkoxyl, amino, halogen, cyano group, nitro, hydroxyl or sulfydryl.
Further preferably R1、R2The independent aryl selected from substituted or unsubstituted C6～C18, the condensed ring of C10～C22, five yuan miscellaneous Ring, hexa-member heterocycle, the condensed hetero ring of C8～C20.
Most preferably R1、R2Independent selected from phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, xenyl, terphenyl, indenyl, pyrrole Cough up base, pyridine radicals, thienyl, furyl, indyl, benzothienyl, benzofuranyl, quinolyl, imidazole radicals, thiazolyl, Oxazolyl or fluorenyl.
According to the present invention, described R1、R2Substituted or unsubstituted condensed hetero ring can also be formed, preferably with the nitrogen-atoms at place , R1、R2With the condensed hetero ring that the nitrogen-atoms at place forms substituted or unsubstituted C12～C30.
Concrete, described pyridazine class derivant be preferably selected from structure shown in following TM1～TM47 any one:
The present invention also provides for the preparation method of a kind of pyridazine class derivant, and syntheti c route is as follows:
Wherein, R1、R2Independent selected from replace or unsubstituted C6～C50 aryl, substituted or unsubstituted C10～C30 Condensed ring, substituted or unsubstituted five-ring heterocycles, substituted or unsubstituted hexa-member heterocycle, substituted or unsubstituted C8～C30 Condensed hetero ring；
Or described R1、R2Substituted or unsubstituted condensed hetero ring is formed with the nitrogen-atoms at place.
According to the present invention, the compound shown in intermediate A prepares according to method as follows:
Under nitrogen protection, palladium and tri-butyl phosphine are catalyst, in the case of sodium tert-butoxide is alkali, by amine and institute Show that halides is reacted, obtain intermediate A；
According to the present invention, by the compound shown in intermediate A and shown halogenated pyridazine under nitrogen protection through coupling Reaction obtains shown pyridazine class derivant, and the present invention does not has special restriction to described coupling reaction, uses art technology Coupling reaction known to personnel, this preparation method is simple, and raw material is easy to get.
The present invention also provides for the application in organic electroluminescence device of the described pyridazine class derivant, the pyridazine class of the present invention Derivant can be applied in terms of organic electroluminescence device as hole mobile material, described organic electroluminescence device Including anode, negative electrode and organic matter layer, organic matter layer comprise hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, At least one of which in hole blocking layer, electron transfer layer, electron injecting layer；At least one of which in described organic matter layer contains above-mentioned Described pyridazine class derivant.Described pyridazine class derivant specifically can be as the hole transport preparing organic electroluminescence device Layer.The device architecture used is preferably particularly as follows: EML is used as luminescent layer material, and 2-TNATA is used as hole injection layer material, described Pyridazine class derivant be used as hole transmission layer material, in order to manufacture the organic luminescent device of following same configuration: ITO/2- Pyridazine class derivant (30nm)/EML (30nm)/Alq3 (30nm)/LiF (the 0.5nm)/Al of TNATA (80nm)/described (60nm).Described organic electroluminescence device can be used for the applications such as flat faced display, lighting source, direction board, signal lights.
Raw material employed in following example is had no particular limits by the present invention, can be commercially available prod or employing Preparation method well-known to those skilled in the art prepares.
Embodiment A:
The preparation of intermediate A 4
By tri-butyl phosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium (0.4g, 1.83mmol) and sodium tert-butoxide (52.7g, 549mmol) add to aniline (17.0g, 183mmol) and bromobenzene (31.6g, 201mmol) the solution in degassed toluene (500mL), and this mixture is heated 2 hours under reflux.This reaction is mixed Compound is cooled to room temperature, filters by dilution with toluene and via kieselguhr.This filtrate water is diluted, and with methylbenzene extraction, and And merging organic facies, it is evaporated under vacuo.This residue is filtered via silica gel, in being then recrystallized to give Mesosome A4 (26.3g, theoretical value 85%).
Mass spectrum m/z:169.20 (value of calculation: 169.22).Theoretical elemental content (%) C12H11N:C, 85.17；H,6.55； N, 8.28 actual measurement constituent content (%): C, 85.18；H,6.52；N,8.29.The above results confirms that obtaining product is target product.
Obtain following midbody compound in a similar fashion:
Embodiment A5: mass spectrum m/z:197.25 (value of calculation: 197.28).Theoretical elemental content (%) C14H15N:C, 85.24；H,7.66；N, 7.10 actual measurement constituent content (%): C, 85.25；H,7.68；N,7.13.The above results confirms to obtain produces Thing is target product.
Embodiment A6: mass spectrum m/z:321.40 (value of calculation: 321.41).Theoretical elemental content (%) C24H19N:C, 89.68；H,5.96；N, 4.36 actual measurement constituent content (%): C, 89.65；H,5.99；N,4.37.The above results confirms to obtain produces Thing is target product.
Embodiment A7: mass spectrum m/z:271.35 (value of calculation: 271.36).Theoretical elemental content (%) C20H17N:C, 88.52；H,6.31；N, 5.16 actual measurement constituent content (%): C, 88.54；H,6.31；N,5.13.The above results confirms to obtain produces Thing is target product.
Embodiment A8: mass spectrum m/z:269.35 (value of calculation: 269.34).Theoretical elemental content (%) C20H15N:C, 89.19；H,5.61；N, 5.20 actual measurement constituent content (%): C, 89.17；H,5.61；N,5.22.The above results confirms to obtain produces Thing is target product.
Embodiment A9: mass spectrum m/z:245.35 (value of calculation: 245.32).Theoretical elemental content (%) C18H15N:C, 88.13；H,6.16；N, 5.71 actual measurement constituent content (%): C, 88.15；H,6.14；N,5.71.The above results confirms to obtain produces Thing is target product.
Embodiment A10: mass spectrum m/z:369.45 (value of calculation: 369.46).Theoretical elemental content (%) C28H19N:C, 91.03；H,5.18；N, 3.79 actual measurement constituent content (%): C, 91.01；H,5.18；N,3.78.The above results confirms to obtain produces Thing is target product.
Embodiment A11: mass spectrum m/z:369.45 (value of calculation: 369.46).Theoretical elemental content (%) C28H19N:C, 91.03；H,5.18；N, 3.79 actual measurement constituent content (%): C, 91.01；H,5.18；N,3.78.The above results confirms to obtain produces Thing is target product.
Embodiment A12: mass spectrum m/z:419.45 (value of calculation: 419.52).Theoretical elemental content (%) C32H21N:C, 91.62；H,5.05；N, 3.34 actual measurement constituent content (%): C, 91.63；H,5.04；N,3.33.The above results confirms to obtain produces Thing is target product.
Embodiment A13: mass spectrum m/z:401.52 (value of calculation: 401.54).Theoretical elemental content (%) C30H27N:C, 89.73；H,6.78；N, 3.49 actual measurement constituent content (%): C, 89.71；H,6.79；N,3.49.The above results confirms to obtain produces Thing is target product.
Embodiment A14: mass spectrum m/z:501.64 (value of calculation: 501.66).Theoretical elemental content (%) C38H31N:C, 90.98；H,6.23；N, 2.79 actual measurement constituent content (%): C, 90.97；H,6.24；N,2.79.The above results confirms to obtain produces Thing is target product.
Embodiment A15: mass spectrum m/z:501.64 (value of calculation: 501.66).Theoretical elemental content (%) C38H31N:C, 90.98；H,6.23；N, 2.79 actual measurement constituent content (%): C, 90.97；H,6.24；N,2.79.The above results confirms to obtain produces Thing is target product.
Embodiment A16: mass spectrum m/z:147.15 (value of calculation: 147.18).Theoretical elemental content (%) C8H9N3: C, 65.29；H,6.16；N, 28.55 actual measurement constituent content (%): C, 65.27；H,6.18；N,28.55.The above results confirms to obtain Product is target product.
Embodiment A17: mass spectrum m/z:149.14 (value of calculation: 149.15).Theoretical elemental content (%) C8H7NO2: C, 64.42；H,4.73；N,9.39；O, 21.45 actual measurement constituent content (%): C, 64.41；H,4.74；N,9.40；O,21.45.On State result and confirm that obtaining product is target product.
Embodiment A18: mass spectrum m/z:181.25 (value of calculation: 181.28).Theoretical elemental content (%) C8H7NS2: C, 53.00；H,3.89；N,7.73；S, 35.38 actual measurement constituent content (%): C, 53.02；H,3.88；N,7.72；S,35.38.On State result and confirm that obtaining product is target product.
Embodiment A19: mass spectrum m/z:171.21 (value of calculation: 171.20).Theoretical elemental content (%) C10H9N3: C, 70.16；H,5.30；N, 24.54 actual measurement constituent content (%): C, 70.15；H,5.33；N,24.52.The above results confirms to obtain Product is target product.
Embodiment A20: mass spectrum m/z:173.12 (value of calculation: 173.17).Theoretical elemental content (%) C8H7N5: C, 55.48；H,4.07；N, 40.44 actual measurement constituent content (%): C, 55.47；H,4.06；N,40.47.The above results confirms to obtain Product is target product.
Embodiment A21: mass spectrum m/z:149.12 (value of calculation: 149.15).Theoretical elemental content (%) C6H7N5: C, 48.32；H,4.73；N, 46.95 actual measurement constituent content (%): C, 48.33；H,4.74；N,46.93.The above results confirms to obtain Product is target product.
Embodiment A22: mass spectrum m/z:151.15 (value of calculation: 151.12).Theoretical elemental content (%) C6H5N3O2: C, 47.69；H,3.33；N,27.81；O, 21.17 actual measurement constituent content (%): C, 47.67；H,3.33；N,27.83；O,21.17. The above results confirms that obtaining product is target product.
Embodiment A23: mass spectrum m/z:271.31 (value of calculation: 271.32).Theoretical elemental content (%) C18H13N3: C, 79.68；H,4.83；N, 15.49 actual measurement constituent content (%): C, 79.66；H,4.84；N,15.50.The above results confirms to obtain Product is target product.
Embodiment A24: mass spectrum m/z:247.25 (value of calculation: 247.29).Theoretical elemental content (%) C16H13N3: C, 77.71；H,5.30；N, 16.99 actual measurement constituent content (%): C, 77.70；H,5.32；N,16.98.The above results confirms to obtain Product is target product.
Embodiment A25: mass spectrum m/z:249.21 (value of calculation: 249.26).Theoretical elemental content (%) C16H11NO2: C, 77.10；H,4.45；N,5.62；O, 12.84 actual measurement constituent content (%): C, 77.12；H,4.43；N,5.62；O,12.83.On State result and confirm that obtaining product is target product.
Embodiment A26: mass spectrum m/z:281.43 (value of calculation: 281.40).Theoretical elemental content (%) C16H11NS2: C, 68.29；H,3.94；N,4.98；S, 22.79 actual measurement constituent content (%): C, 68.27；H,3.95；N,4.99；S,22.79.On State result and confirm that obtaining product is target product.
Embodiment A27: mass spectrum m/z:219.23 (value of calculation: 219.28).Theoretical elemental content (%) C16H13N:C, 87.64；H,5.98；N, 6.39 actual measurement constituent content (%): C, 87.66；H,5.97；N,6.37.The above results confirms to obtain produces Thing is target product.
Embodiment A28: mass spectrum m/z:220.23 (value of calculation: 220.27).Theoretical elemental content (%) C16H11NS2: C, 81.79；H,5.49；N, 12.72 actual measurement constituent content (%): C, 81.76；H,5.49；N,12.74.The above results confirms to obtain Product is target product.
Embodiment C: the synthesis of compound TM1:
By tri-butyl phosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium (0.4g, 1.83mmol) add to B bromo pyridazine (43.7g, 183mmol) and A1 carbazole with sodium tert-butoxide (52.7g, 549mmol) (64.2g, 384mmol) solution in degassed toluene (500mL), and this mixture is heated 2 hours under reflux.Should Reactant mixture is cooled to room temperature, filters by dilution with toluene and via kieselguhr.This filtrate water is diluted, and carries with toluene Take, and merge organic facies, it is evaporated under vacuo.This residue is filtered via silica gel, is recrystallized to give Target product TM1 (77.7g, theoretical value 85%).
Mass spectrum m/z:500.65 (value of calculation: 500.55).Theoretical elemental content (%) C33H20N6: C, 79.18；H,4.03； N, 16.79 actual measurement constituent content (%): C, 79.13；H,4.06；N,16.72.The above results confirms that obtaining product is that target is produced Product.
Obtain following compound in a similar fashion:
Embodiment C2: mass spectrum m/z:652.75 (value of calculation: 652.74).Theoretical elemental content (%) C45H28N6: C, 82.80；H,4.32；N, 12.87 actual measurement constituent content (%): C, 82.82；H,4.31；N,12.87.The above results confirms to obtain Product is target product.
Embodiment C3: mass spectrum m/z:584.75 (value of calculation: 584.71).Theoretical elemental content (%) C39H32N6: C, 80.11；H,5.52；N, 14.37 actual measurement constituent content (%): C, 80.10；H,5.52；N,14.38.The above results confirms to obtain Product is target product.
Embodiment C4: mass spectrum m/z:504.52 (value of calculation: 504.58).Theoretical elemental content (%) C33H24N6: C, 78.55；H,4.79；N, 16.66 actual measurement constituent content (%): C, 78.53；H,4.80；N,16.67.The above results confirms to obtain Product is target product.
Embodiment C5: mass spectrum m/z:560.63 (value of calculation: 560.69).Theoretical elemental content (%) C37H32N6: C, 79.26；H,5.75；N, 14.99 actual measurement constituent content (%): C, 79.24；H,5.77；N,14.99.The above results confirms to obtain Product is target product.
Embodiment C6: mass spectrum m/z:808.95 (value of calculation: 808.97).Theoretical elemental content (%) C57H40N6: C, 84.63；H,4.98；N, 10.39 actual measurement constituent content (%): C, 84.61；H,4.99；N,10.40.The above results confirms to obtain Product is target product.
Embodiment C7: mass spectrum m/z:704.87 (value of calculation: 704.82).Theoretical elemental content (%) C49H32N6: C, 83.50；H,4.58；N, 11.92 actual measurement constituent content (%): C, 83.53；H,4.57；N,11.90.The above results confirms to obtain Product is target product.
Embodiment C8: mass spectrum m/z:704.85 (value of calculation: 704.82).Theoretical elemental content (%) C49H32N6: C, 83.50；H,4.58；N, 11.92 actual measurement constituent content (%): C, 83.56；H,4.57；N,11.97.The above results confirms to obtain Product is target product.
Embodiment C9: mass spectrum m/z:656.75 (value of calculation: 656.78).Theoretical elemental content (%) C45H32N6: C, 82.29；H,4.91；N, 12.80 actual measurement constituent content (%): C, 82.27；H,4.91；N,12.82.The above results confirms to obtain Product is target product.
Embodiment C10: mass spectrum m/z:909.11 (value of calculation: 909.09).Theoretical elemental content (%) C65H44N6: C, 85.88；H,4.88；N, 9.24 actual measurement constituent content (%): C, 85.87；H,4.87；N,9.26.The above results confirms to obtain produces Thing is target product.
Embodiment C11: mass spectrum m/z:905.07 (value of calculation: 905.05).Theoretical elemental content (%) C65H40N6: C, 86.26；H,4.45；N, 9.29 actual measurement constituent content (%): C, 86.23；H,4.47；N,9.29.The above results confirms to obtain produces Thing is target product.
Embodiment C12: mass spectrum m/z:1001.15 (value of calculation: 1001.14).Theoretical elemental content (%) C73H40N6: C, 87.58；H,4.03；N, 8.39 actual measurement constituent content (%): C, 87.58；H,4.03；N,8.39.The above results confirms to obtain produces Thing is target product.
Embodiment C13: mass spectrum m/z:969.25 (value of calculation: 969.22).Theoretical elemental content (%) C69H56N6: C, 85.51；H,5.82；N, 8.67 actual measurement constituent content (%): C, 85.53；H,5.84；N,8.63.The above results confirms to obtain produces Thing is target product.
Embodiment C14: mass spectrum m/z:1169.42 (value of calculation: 1169.46).Theoretical elemental content (%) C85H64N6: C, 87.30；H,5.52；N, 7.19 actual measurement constituent content (%): C, 87.32；H,5.52；N,7.16.The above results confirms to obtain produces Thing is target product.
Embodiment C15: mass spectrum m/z:1169.45 (value of calculation: 1169.46).Theoretical elemental content (%) C85H64N6: C, 87.30；H,5.52；N, 7.19 actual measurement constituent content (%): C, 87.33；H,5.51；N,7.16.The above results confirms to obtain produces Thing is target product.
Embodiment C16: mass spectrum m/z:460.42 (value of calculation: 460.49).Theoretical elemental content (%) C25H20N10: C, 65.21；H,4.38；N, 30.42 actual measurement constituent content (%): C, 65.23；H,4.36；N,30.41.The above results confirms to obtain Product is target product.
Embodiment C17: mass spectrum m/z:464.41 (value of calculation: 464.43).Theoretical elemental content (%) C25H16N6O4: C, 64.65；H,3.47；N,18.10；O, 13.78 actual measurement constituent content (%): C, 64.66；H,3.45；N,18.12；O,13.77. The above results confirms that obtaining product is target product.
Embodiment C18: mass spectrum m/z:528.63 (value of calculation: 528.69).Theoretical elemental content (%) C25H16N6S4: C, 56.79；H,3.05；N,15.90；S, 24.26 actual measurement constituent content (%): C, 56.77；H,3.07；N,15.91；S,24.25. The above results confirms that obtaining product is target product.
Embodiment C19: mass spectrum m/z:508.51 (value of calculation: 508.54).Theoretical elemental content (%) C29H20N6: C, 68.49；H,3.96；N, 27.54 actual measurement constituent content (%): C, 68.47；H,3.98；N,27.55.The above results confirms to obtain Product is target product.
Embodiment C20: mass spectrum m/z:512.44 (value of calculation: 512.49).Theoretical elemental content (%) C25H16N14: C, 58.59；H,3.15；N, 38.26 actual measurement constituent content (%): C, 58.56；H,3.17；N,38.27.The above results confirms to obtain Product is target product.
Embodiment C21: mass spectrum m/z:464.41 (value of calculation: 464.45).Theoretical elemental content (%) C21H16N14: C, 54.31；H,3.47；N, 42.22 actual measurement constituent content (%): C, 54.32；H,3.44；N,42.24.The above results confirms to obtain Product is target product.
Embodiment C22: mass spectrum m/z:468.35 (value of calculation: 468.38).Theoretical elemental content (%) C21H12N10O4: C, 53.85；H,2.58；N,29.90；S, 13.66 actual measurement constituent content (%): C, 53.87；H,2.56；N,29.91；S,13.66. The above results confirms that obtaining product is target product.
Embodiment C23: mass spectrum m/z:708.75 (value of calculation: 708.77).Theoretical elemental content (%) C45H28N10: C, 76.26；H,3.98；N, 19.76 actual measurement constituent content (%): C, 76.25；H,3.97；N,19.78.The above results confirms to obtain Product is target product.
Embodiment C24: mass spectrum m/z:660.72 (value of calculation: 660.73).Theoretical elemental content (%) C41H28N10: C, 74.53；H,4.27；N, 21.20 actual measurement constituent content (%): C, 74.55；H,4.24；N,21.21.The above results confirms to obtain Product is target product.
Embodiment C25: mass spectrum m/z:664.60 (value of calculation 664.67).Theoretical elemental content (%) C41H24N6O4: C, 74.09；H,3.64；N,12.64；O, 9.63 actual measurement constituent content (%): C, 74.07；H,3.65；N,12.65；S,9.63.On State result and confirm that obtaining product is target product.
Embodiment C26: mass spectrum m/z:728.90 (value of calculation 728.93).Theoretical elemental content (%) C41H24N6S4: C, 67.56；H,3.32；N,11.53；S, 17.60 actual measurement constituent content (%): C, 67.57；H,3.31；N,11.52；S,17.61. The above results confirms that obtaining product is target product.
Embodiment C27: mass spectrum m/z:604.67 (value of calculation 604.70).Theoretical elemental content (%) C41H28N6: C, 81.44；H,4.67；N, 13.90 actual measurement constituent content (%): C, 81.43；H,4.66；N,13.91.The above results confirms to obtain Product is target product.
Embodiment C28: mass spectrum m/z:606.63 (value of calculation 606.68).Theoretical elemental content (%) C39H26N8: C, 77.21；H,4.32；N, 18.47 actual measurement constituent content (%): C, 77.21；H,4.32；N,18.47.The above results confirms to obtain Product is target product.
Comparative example 1
EML is used as luminescent layer material, and 2-TNATA is used as hole injection layer material, and α-NPD is used as hole transmission layer material, In order to manufacture the organic luminescent device of following same configuration: ITO/2-TNATA (80nm)/α-NPD (30nm)/EML (30nm)/ Alq3(30nm)/LiF(0.5nm)/Al(60nm).Anode is healthy and free from worry (Corning) companyITO glass Glass substrate cuts into 50mm*50mm*0.7mm size, and the ultrasound wave that acetone isopropanol respectively carries out in pure water 15 minutes is clear Wash, re-use after the UV ozone clean of 30 minutes.On the glass substrate, 80nm is formed after 2-TANATA is carried out vacuum evaporation thick The hole injection layer of degree.α-NPD is carried out vacuum evaporation by hole injection layer, forms the hole transmission layer of 30nm thickness.? The luminescent layer of 25nm is formed after EML being carried out vacuum evaporation on hole transmission layer above.Then, by Alq3's on luminescent layer Compound carries out vacuum evaporation with the thickness of 30nm, forms electron transfer layer.By LiF 0.5nm on electron transfer layer, (electronics is noted Enter layer) and Al 600nm (negative electrode) successively carry out vacuum evaporation.Make organic luminescent device, be referred to as comparing sample 1
Organic luminescent device is prepared by described pyridazine class derivant:
Replace α-NPD as the compound in hole transmission layer described pyridazine class derivant, use and above-mentioned comparative example 1 Same method manufactured have ITO/2-TNATA (80nm)/for HTL pyridazine class derivant (30nm)/EML (30nm)/ The organic luminescent device of Alq3 (30nm)/LiF (0.5nm)/Al (60nm) structure, referred to as sample 1 to 28.
Evaluation Example 1: compare sample 1 and the characteristics of luminescence evaluation of sample 1～28
To comparing sample 1 and sample 1～25, use Taiwan branch company of US business Keithley instrument limited company Keithley2400 series digit source table, Konica Minolta konica minolta CS-2000, CS-2000A photometer is commented Valency driving voltage, luminosity, luminous efficiency, glow peak are evaluated, and represent the form of result table 1 below, above-mentioned sample Under 456～478nm scopes, blue-light-emitting peak value occurs.
Table 1
Result above shows, the pyridazine class derivant of the present invention is applied in organic electroluminescence device, especially as Hole mobile material, shows high efficiency, high brightness, long-life advantage, is luminous organic material of good performance.
Obviously, the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.Should refer to Go out, for the those of ordinary skill of described technical field, under the premise without departing from the principles of the invention, it is also possible to this Bright carrying out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.

Claims (10)

1. a pyridazine class derivant, it is characterised in that structural formula shown in formula I:
Wherein, R1、R2The independent aryl selected from substituted or unsubstituted C6～C50, substituted or unsubstituted C10～C30 thick Ring, substituted or unsubstituted five-ring heterocycles, substituted or unsubstituted hexa-member heterocycle, substituted or unsubstituted C8～C30 thick miscellaneous Ring；
Or described R1、R2Substituted or unsubstituted condensed hetero ring is formed with the nitrogen-atoms at place.
A kind of pyridazine class derivant the most according to claim 1, it is characterised in that R1、R2Independent being selected from replaces or does not takes The aryl of C6～C30 in generation, the condensed ring of substituted or unsubstituted C10～C30, substituted or unsubstituted five-ring heterocycles, replacement or Unsubstituted hexa-member heterocycle, the condensed hetero ring of substituted or unsubstituted C8～C20.
A kind of pyridazine class derivant the most according to claim 1, it is characterised in that R1、R2Independent being selected from replaces or does not takes The aryl of C6～C18 in generation, the condensed ring of C10～C22, five-ring heterocycles, hexa-member heterocycle or the condensed hetero ring of C8～C20.
A kind of pyridazine class derivant the most according to claim 1, it is characterised in that R1、R2Independent selected from phenyl, naphthyl, Anthryl, phenanthryl, pyrenyl, xenyl, terphenyl, indenyl, pyrrole radicals, pyridine radicals, thienyl, furyl, indyl, benzo thiophene Fen base, benzofuranyl, quinolyl, imidazole radicals, thiazolyl, oxazolyl or fluorenyl.
A kind of pyridazine class derivant the most according to claim 1, it is characterised in that R1、R2Formed with the nitrogen-atoms at place and take Generation or the condensed hetero ring of unsubstituted C12～C30.
A kind of pyridazine class derivant the most according to claim 1, it is characterised in that described pyridazine class derivant is selected from as follows Any one in structure shown in TM1～TM47:
。
7. the preparation method of the pyridazine class derivant described in any one of claim 1-6, it is characterised in that closed by following route Become and obtain described pyridazine class derivant:
Wherein, R1、R2Independent selected from replace or unsubstituted C6～C50 aryl, substituted or unsubstituted C10～C30 thick Ring, substituted or unsubstituted five-ring heterocycles, substituted or unsubstituted hexa-member heterocycle, substituted or unsubstituted C8～C30 thick miscellaneous Ring；
Or described R1、R2Substituted or unsubstituted condensed hetero ring is formed with the nitrogen-atoms at place.
8. the application in organic electroluminescence device of the pyridazine class derivant described in claim 1-6 any one.
The pyridazine class derivant the most according to claim 8 application in organic electroluminescence device, it is characterised in that institute State organic electroluminescence device and include anode, negative electrode and organic matter layer, organic matter layer comprise hole injection layer, hole transmission layer, At least one of which in electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；
At least one of which in described organic matter layer contains the pyridazine class derivant described in any one of claim 1～6.
The pyridazine class derivant the most according to claim 9 application in organic electroluminescence device, it is characterised in that Described pyridazine class derivant is for preparing the hole transmission layer of organic electroluminescence device.
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CN107698486A (en) * 2017-10-09 2018-02-16 长春海谱润斯科技有限公司 A kind of benzo carbazole organic compound and its organic luminescent device
CN107698488A (en) * 2017-10-09 2018-02-16 长春海谱润斯科技有限公司 A kind of benzo carbazole analog derivative and its organic luminescent device

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Publication number Priority date Publication date Assignee Title
CN107602440A (en) * 2017-10-09 2018-01-19 长春海谱润斯科技有限公司 A kind of benzo carbazole class electroluminescent organic material and its organic luminescent device
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CN107698486A (en) * 2017-10-09 2018-02-16 长春海谱润斯科技有限公司 A kind of benzo carbazole organic compound and its organic luminescent device
CN107698488A (en) * 2017-10-09 2018-02-16 长春海谱润斯科技有限公司 A kind of benzo carbazole analog derivative and its organic luminescent device

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