CN106349212A - Naphtho-thioxanthene derivative as well as preparation method and application thereof - Google Patents
Naphtho-thioxanthene derivative as well as preparation method and application thereof Download PDFInfo
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- 0 *(C=CC=C1c2cccc3cccnc23)c(cc2)c3c4cc1ccc4ccc3c2-c1cccc2c1nccc2 Chemical compound *(C=CC=C1c2cccc3cccnc23)c(cc2)c3c4cc1ccc4ccc3c2-c1cccc2c1nccc2 0.000 description 3
- UZMYMPRKHHCWJD-UHFFFAOYSA-N Brc(c1c2c(Sc3ccc4)ccc1)cc1c2-c3c4C(Br)=CC1 Chemical compound Brc(c1c2c(Sc3ccc4)ccc1)cc1c2-c3c4C(Br)=CC1 UZMYMPRKHHCWJD-UHFFFAOYSA-N 0.000 description 1
- BFXWWYIYIUNGAX-UHFFFAOYSA-N C(C(C1)c(c(cc2)c34)ccc3Sc(cc3)c5c4c2ccc5c3-c2nc(cccc3)c3[s]2)c2c1cccc2 Chemical compound C(C(C1)c(c(cc2)c34)ccc3Sc(cc3)c5c4c2ccc5c3-c2nc(cccc3)c3[s]2)c2c1cccc2 BFXWWYIYIUNGAX-UHFFFAOYSA-N 0.000 description 1
- CQUWJSDDCYJDLQ-UHFFFAOYSA-N C(C1=CC=CC2C11)c3cccc(c(-c4cccc5c4cccc5)c4)c3c1c4C=C2c1cccc2cccnc12 Chemical compound C(C1=CC=CC2C11)c3cccc(c(-c4cccc5c4cccc5)c4)c3c1c4C=C2c1cccc2cccnc12 CQUWJSDDCYJDLQ-UHFFFAOYSA-N 0.000 description 1
- OOARAKDWRYXTNS-UHFFFAOYSA-N C(CC(C=C(C1C=CC=C(C2)C11)C3=[I]c(cccc4)c4N3c3ccccc3)=C1c1c2cccc1)C1=Nc2ccccc2C1C1C=CC=CC1 Chemical compound C(CC(C=C(C1C=CC=C(C2)C11)C3=[I]c(cccc4)c4N3c3ccccc3)=C1c1c2cccc1)C1=Nc2ccccc2C1C1C=CC=CC1 OOARAKDWRYXTNS-UHFFFAOYSA-N 0.000 description 1
- WPHMSPNDQMOJAY-KGHBKMJJSA-N C/N=C(\CCC(c1ccccc1)=C)/c1c(cccc2Sc3ccc4)c2c2c3c4c(-c3nnc(-c4ccccc4)[nH]3)cc2c1 Chemical compound C/N=C(\CCC(c1ccccc1)=C)/c1c(cccc2Sc3ccc4)c2c2c3c4c(-c3nnc(-c4ccccc4)[nH]3)cc2c1 WPHMSPNDQMOJAY-KGHBKMJJSA-N 0.000 description 1
- RIQSYHGUXKHXGD-UGBIASQWSA-N CC/C(/c1ccccc1)=N\N=C(/C)\c(cc1cc(C2=NN=C(c3ccccc3)[ClH]2)c2ccc3)c4c5c1c2c3Oc5ccc4 Chemical compound CC/C(/c1ccccc1)=N\N=C(/C)\c(cc1cc(C2=NN=C(c3ccccc3)[ClH]2)c2ccc3)c4c5c1c2c3Oc5ccc4 RIQSYHGUXKHXGD-UGBIASQWSA-N 0.000 description 1
- UIHPBXMZSJHXCJ-UHFFFAOYSA-N Cc(cc1)c2c3ncccc3ccc2c1C(C(C1C23)C=CC2C=C2)=CCC1Sc(cc1)c3c2c1-c1c(ccc2cccnc22)c2ncc1 Chemical compound Cc(cc1)c2c3ncccc3ccc2c1C(C(C1C23)C=CC2C=C2)=CCC1Sc(cc1)c3c2c1-c1c(ccc2cccnc22)c2ncc1 UIHPBXMZSJHXCJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a naphtho-thioxanthene derivative as well as a preparation method and application thereof, belonging to the technical field of organic optoelectronic materials. The material takes naphtho-thioxanthene groups as a center for connecting two conjugate non-planar structures, thus having good electron transmission ability and greatly improving luminous efficiency; therefore, the material can be used for preparing an organic light-emitting device (OLED), and more particularly, the OLED taking the material as an electron transport material or a light-emitting layer main body material is superior to the existing commonly-used OLED. The invention also provides the preparation method of the naphtho-thioxanthene derivative; the preparation method is simple, thus being suitable for industrial production.
Description
Technical field
The present invention relates to organic photoelectrical material technical field is and in particular to a kind of naphtho- thia anthracene derivant and its preparation side
Method and application.
Background technology
Organic Light Emitting Diode (organic light emitting diode, abbreviation oled) is a kind of with organic material
As the current-driven luminescent device of active material, specifically refer to organic semiconducting materials and luminous organic material in electric field
Under driving, by the technology of carrier injection and composite guide photoluminescence.The research of organic electroluminescent phenomenon starts from 20th century 60
Age.Pope of New York Univ USA in 1963 et al. by the voltage of hundreds of volts by anthracene crystal when observe luminescence phenomenon, but
Because driving voltage is too high too low with luminous efficiency, this technology was not taken seriously at that time.Kodak in 1987
C.w.tang et al. first hole transmission layer is incorporated in organic luminescent device, they adopt vacuum evaporation technology alq3
It is made for a kind of amorphous membranous type device of bilayer organic material structure with tpd plated film, so far, oled just causes common people to pay close attention to
(us4356429).This kind of device has frivolous, high brightness, rich color, low power consumption and other advantages, can be widely used for flat luminous
Element such as flat faced display and area source.This research indicates that organic electroluminescent research enters practical stage.1998
Forrest of Princeton university et al. is found that electrophosphorescence phenomenon so that organic electroluminescence device is studied
Enter new period.
The essential structure of electroluminescent device is simple " sandwich style " device.Electro-conductive glass substrate is revolved
Painting, dip-coating or vacuum thermal evaporation luminous organic material, are then plated with cathode material, connect power supply and constitute organic electroluminescence
Part.In order to improve recombination probability and luminous quantum efficiency in organic electroluminescence device luminescent layer, electronics and hole should be made
Injection reaches balance.Introduce electron transfer layer (etl) or/and hole transmission layer (htl) in organic electroluminescence device, formed
Multiple structure device, contributes to electronics and the balance of hole injection, improves the performance of device.
The machine luminescent material of common are has: hole-injecting material, hole mobile material, hole barrier materials, electron injection
Material, electron transport material, electron-blocking materials and light emitting host material and light-emitting guest etc..
With developing rapidly of photoelectric communication in recent years and MultiMedia Field, luminous organic material has become modern society's letter
Breath and the core of electronic industry.Therefore, with the high speed development in field, luminous organic material be it is also proposed in performance higher
Requirement.
In view of this, how to find a kind of luminous organic material with more preferable performance, improve the luminous effect of luminescent device
Rate and service life, always this area research worker problem demanding prompt solution.
Content of the invention
In view of this, it is an object of the invention to provide a kind of naphtho- thia anthracene derivant and its preparation method and application, adopt
The organic electroluminescence device luminous efficiency of the naphtho- thia anthracene derivant preparation being provided with the present invention is high, preparation method is simple,
It is electron transport material or the light emitting host material of function admirable.
The invention provides a kind of naphtho- thia anthracene derivant, structural formula is:
Or
Wherein, r1、r2、r3、r4The independent aryl selected from c6-c50, the fused ring aryl of c10-c50, c7-c50 thick miscellaneous
Cyclophane base or the nitrogenous heteroaryl of c5-c50.
Preferably, described r1、r2、r3、r4The independent aryl selected from c6-c30, the fused ring aryl of c10-c30, c7-c30
Condensed hetero ring aryl or c5-c30 nitrogenous heteroaryl.
Preferably, described r1、r2、r3、r4The independent aryl selected from c6-c20, the fused ring aryl of c10-c20, c7-c20
Condensed hetero ring aryl or c5-c20 nitrogenous heteroaryl.
Preferably, described r1、r2、r3、r4Independent selected from phenyl, xenyl, naphthyl, anthryl, phenanthryl, pyrenyl, fluorenyl,
Carbazyl, pyridine radicals, pyridinylphenyl, quinolyl, imidazole radicals, thiazolyl or oxazolyl.
Preferably, described r1With r2Identical, described r3With r4Identical.
Preferably, any one in structure shown in following m1～m40 of described naphtho- thia anthracene derivant:
The present invention also provides a kind of preparation method of naphtho- thia anthracene derivant, comprising:
Under nitrogen protection, by the compound shown in formula a or the compound shown in formula b through coupling reaction obtain formula or
Naphtho- thia anthracene derivant shown in formula；
Wherein, r1、r2、r3、r4The independent aryl selected from c6-c50, the fused ring aryl of c10-c50, c7-c50 thick miscellaneous
Cyclophane base or the nitrogenous heteroaryl of c5-c50.
The present invention also provides application in organic electroluminescence device for the described naphtho- thia anthracene derivant.
Preferably, described organic electroluminescence device includes anode, negative electrode and organic matter layer, and organic matter layer comprises hole note
Enter layer, hole transmission layer, electronic barrier layer, organic luminous layer, hole blocking layer, electron transfer layer, in electron injecting layer extremely
Few one layer, described luminescent layer includes material of main part and dopant dye；
At least one of which in described organic matter layer contains described naphtho- thia anthracene derivant.
Preferably, described naphtho- thia anthracene derivant is used for preparing organic electroluminescence device electron transport material or luminous
Material of main part.
Beneficial effects of the present invention:
Present invention firstly provides a kind of naphtho- thia anthracene derivant, this naphtho- thia anthracene derivant has formula or formula institute
Show structure.This material, centered on naphtho- thioxanthene class group, connects two conjugation nonplanar structures, has excellent electronics and pass
Movement Capabilities, substantially increase luminous efficiency；Therefore, this material can be used for preparing organic electroluminescence device, especially as having
Electron transport material in organic electroluminescence devices or luminescent layer material of main part, better than existing conventional oled device.Above-mentioned device
Can be used for the applications such as flat faced display, lighting source, mobile phone screen, signal lighties.The present invention also provides a kind of naphtho- thia
The preparation method of anthracene derivant, using classical coupling reaction method synthesis, preparation method is simple, is suitable for industry metaplasia for this material
Produce.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment, the preferred embodiment of the invention is described, but
It should be appreciated that these descriptions are simply 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 naphtho- thia anthracene derivant, structural formula is:
Or
Wherein, r1、r2、r3、r4The independent aryl selected from c6-c50, the fused ring aryl of c10-c50, c7-c50 thick miscellaneous
Cyclophane base or the nitrogenous heteroaryl of c5-c50.Be preferably the aryl of c6-c30, the fused ring aryl of c10-c30, c7-c30 thick miscellaneous
Cyclophane base or the nitrogenous heteroaryl of c5-c30.More preferably the aryl of c6-c20, the fused ring aryl of c10-c20, c7-c20 thick
Heterocyclic aryl or the nitrogenous heteroaryl of c5-c20.It is further preferably phenyl, xenyl, naphthyl, anthryl, phenanthryl, pyrenyl, fluorenyl, click
Oxazolyl, pyridine radicals, pyridinylphenyl, quinolyl, imidazole radicals, thiazolyl or oxazolyl.Most preferably described r1With r2Identical, institute
State r3With r4Identical.Specifically, described naphtho- thia anthracene derivant be preferably selected from any one in structure shown in following m1～m40
Kind:
The present invention also provides a kind of preparation method of naphtho- thia anthracene derivant, comprising:
Under nitrogen protection, the compound shown in the compound shown in intermediate formula a or intermediate formula b is anti-through being coupled
The naphtho- thia anthracene derivant shown in formula or formula should be obtained；
Described r1、r2、r3、r4The selection of group is all same as above, will not be described here.
Prepare according to method as follows according to intermediate a of the present invention:
(1) be there is nitration reaction with nitric acid in the thioxanthone shown in formula a-1, obtain the disubstituted nitro shown in formula a-2
Compound；
(2) by compound shown in formula a-2 and carbon tetrabromide, in the presence of triphenylphosphine, there is corey-fuchs dibromo alkene
Glycosylation reaction, obtains the dibromoalkene compound shown in formula a-3；
(3) under nitrogen protection, by compound shown in formula a-3 and trimethylsilyl acetylene in pdcl2(pph3)2Exist with cui
Lower generation sonogashira reaction, then carries out being catalyzed de- trimethyl silicon substrate and obtains the double alkine compounds shown in formula a-4；
(4) under nitrogen protection, compound shown in formula a-4 is dissolved in dry toluene, adds ptcl2Occur cyclization anti-
Should, obtain compound shown in formula a-5；
(5) compound shown in formula a-5 is dissolved in ethanol and thf mixed solvent, carries out catalytic hydrogenation in the presence of pd/c
Nitro is reduced into amido, then carries out diazotising-bromination reaction and obtain intermediate formula a.
The present invention has no particular limits to the reaction condition in step in said method (1)～(5), using this area skill
Reaction condition known to art personnel.
Prepare according to method as follows according to intermediate b of the present invention:
(1) by the thioxanthone shown in formula b-1 and carbon tetrabromide, in the presence of triphenylphosphine, occur dibromo alkenyl anti-
Should, obtain the dibromoalkene compound shown in formula b-2；
(2) pass through pd (pph3)4The b-2 of catalysis and reformasky reagent cross-coupling reaction, obtain double shown in b-3
Ester group compound；
(3) by compound shown in b-3 through basic hydrolysiss, chloride, obtain compound shown in formula b-4；
(4) by compound shown in formula b-4 through alcl3The ring closure reaction of catalysis obtains the bisphenol compound shown in formula b-5；
(5) by compound shown in formula b-5 through br2-pph3Reagent acts on, and obtains compound shown in intermediate formula b.
The present invention has no particular limits to the reaction condition in step in said method (1)～(5), using this area skill
Reaction condition known to art personnel.
According to the present invention, the compound shown in the compound shown in intermediate formula a or intermediate formula b is protected in nitrogen
Under, obtain the naphtho- thia anthracene derivant shown in formula or formula through coupling reaction, the present invention does not have spy to described coupling reaction
Different restriction, using coupling reaction well-known to those skilled in the art, this preparation method is simple, and raw material is easy to get.
The present invention also provides application in organic electroluminescence device for the above-mentioned naphtho- thia anthracene derivant, described Organic Electricity
Electroluminescence device includes anode, negative electrode and organic matter layer, and organic matter layer comprises hole injection layer, hole transmission layer, electronic blocking
At least one of which in layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；In described organic matter layer at least one
Layer is containing naphtho- thia anthracene derivant described above；Preferably described naphtho- thia anthracene derivant can be used as preparing organic electroluminescence
The electron transport layer materials of luminescent device or luminescent layer material of main part.The device architecture adopting in the present invention is: is attached to glass
Or indium stannum oxygen (ito) on plastic base is as anode；Hole injection layer material selects 2-tnata；Hole transmission layer is preferable
N, n '-diphenyl-n, n '-two (1- naphthyl) -1,1 '-xenyl -4,4 '-diamidogen (npb)；On hole transmission layer, vacuum is steamed
Plating material of main part and dopant ir (ppy)3(main body and dopant mass ratio are 100:9) is as the luminescent layer of device, main body material
Material selects n, n '-two carbazole -1,1 '-xenyl -4,4 '-diamidogen (cbp) or the naphtho- thia anthracene derivant of the present invention；Electronics passes
Defeated layer choosing alq3The naphtho- thia anthracene derivant of (quinoline aluminum) or the present invention；Lif is as electron injecting layer；Metal al is as the moon
Pole.Described organic electroluminescence device can be used for the applications such as flat faced display, lighting source, direction board, signal lighties.
Unless otherwise indicated, the present invention to the raw material employed in following examples and is commercial goods or adopts ability
Preparation method known to field technique personnel prepares.
Embodiment 1: the preparation of intermediate a
(1) synthesis of compound a -2: add 150ml fuming nitric aicd in 500ml reaction bulb, be cooled to about 5 with ice-water bath
DEG C, it is dividedly in some parts 21.2g (0.1mol) thioxanthone (a-1 compound) under stirring, controlling reaction temperature is less than 10 DEG C, add
Keep reacting liquid temperature at 5 DEG C after reactant, react about 30min.Reactant is poured in frozen water and is stirred vigorously, sucking filtration.Filter cake
Through washing, it is dried, after recrystallization, obtains a-2 compound, yield 80%.
(2) add 22.6g compound a -2 (0.075mol) in the reaction bulb that the synthesis of compound a -3: 500ml is dried,
50g carbon tetrabromide (0.15mol), reaction system is evacuated-and after nitrogen replaces, add 250ml dry benzene, stir 5min, plus
Enter 78.6g triphenylphosphine (0.3mol).Stirring reaction mixture at 150 DEG C, reacts 48h, after the cooling of question response system, adds
Q. s. methylene chloride dissolves.Crude by column chromatography separates and obtains a-3 compound, yield 62%.
(3) synthesis of compound a -4: under nitrogen protection, add 100ml front three containing 5.7ml silicon in 250ml reaction bulb
The triethylamine solution of ethyl-acetylene (0.04mol), adds 4.6g compound a -3 (0.01mol), 0.7g pdcl2(pph3)2
(0.001mol) with 0.38g cui (0.002mol), reactant mixture is heated to 100 DEG C, reacts 20h at this temperature.Treat
After reaction system cooling, add q. s. methylene chloride dissolving, washed respectively with saturated ammonium chloride solution and water, be dried, crude product
Obtain brown solid, yield 73% through column chromatography for separation.
Above-mentioned brown solid is dissolved in 30ml dichloromethane, is slowly added dropwise 15ml tetrabutyl ammonium fluoride containing 10g three hydration
The dichloromethane solution of thing, adds stirring under rear room temperature, reacts 1h.Reaction solution silica gel funnel concentrates after filtering after removing solvent and obtains
To compound a -4, yield 97%.
(4) synthesis of compound a -5: under nitrogen protection, 2.8g compound a -4 (0.008mol) is dissolved in 50ml dry toluene
In, add 0.1gptcl2.Back flow reaction 6h, activated carbon decolorizing, obtain compound a -5, yield 52%.
(5) synthesis of intermediate a: 1.31g compound a -5 is dissolved in 10ml ethanol and the 1:1 mixed solvent of thf, plus
Enter 1g 10%pd/c, system is replaced as hydrogen, and keep system for ortho-hydrogen pressure by hydrogen balloon, stir under room temperature, reaction
10h, Filtration of catalyst, filtrate is concentrated to give faint yellow solid, yield 97%.
Above-mentioned faint yellow solid is dissolved in 15ml 48% hydrobromic acid, ice-water bath maintains the temperature at less than 5 DEG C, slow
Plus 10ml contains 2.1gnano2(0.03mol) aqueous solution, keeps not higher than 10 DEG C of system temperature, drips off follow-up during Deca
Continue in 5 DEG C of 0.5h stirred below.It is subsequently adding 5gcubr-48%hbr solution, system is heated to 80 DEG C, stir 3h, use dichloromethane
Alkane extracts, and point liquid is dried, and column chromatography for separation obtains intermediate a, yield 76%.Mass spectrum m/z:416.13 (value of calculation: 415.87).
Theoretical elemental content (%) c18h8br2S:c, 51.95；h,1.94；br,38.40；s,7.71；Actual measurement constituent content (%): c,
51.89；h,1.92；br,38.44；s,7.75.The above results confirm that obtaining product is target product.
Embodiment 2: the preparation of intermediate b
(1) synthesis of compound b-2: this step is essentially identical with the step (2) in embodiment 1, difference is to use
Compound b-1 substitutes a-2, yield 68%.
(2) synthesis of compound b-3: under nitrogen protection, in 250ml reaction bulb, add 2.6g zinc powder (0.04mol), few
Measure the dmf that iodine and 100ml are dried, add 5g bromoacetate (0.03mol) after stirring, be heated to 60 DEG C, stir 3h, by solution
Filter to another 250ml reaction bulb, add 3.68g compound b-2 (0.01mol) and 0.55gpd (pph3)4(5%eq.), plus
Heat, to 120 DEG C, reacts 15h.It is extracted with ethyl acetate, point liquid is dried, and obtains compound b-3, yield 60% after column chromatography.
(3) preparation of compound b-4: 38.2g compound b-3 (0.1mol) is dissolved in 100mlthf, adds 100ml to contain
The aqueous solution of 12glioh (0.5mol), stirs to clarify under room temperature.Concentrating under reduced pressure volume, to 50ml, uses dilute salt under ice bath
Ph to 1 is adjusted in acid, after separating out a large amount of solids, filters, washing, is dried to obtain white solid, yield 97%.
Above-mentioned white solid 32g is dissolved in 100ml dichloromethane, adds 40mlsocl2, it is heated to reflux 3h.Vacuum distillation
Remove solvent, obtain compound b-4.
(4) synthesis of compound b-5: 36.2g compound b-4 (0.1mol) is dissolved in 200ml carbon tetrachloride, system is cold
But to 0 DEG C, it is slowly added to 40g powdery alcl3(0.3mol), not higher than 10 DEG C of controlling reaction temperature, after adding, react 30min,
Reactant is poured in frozen water, is extracted with ethyl acetate product, point liquid is dried.This crude product passes through alkali tune-acidization purification, weight
Compound b-5, yield 85% is obtained after crystallization.
(5) preparation of intermediate b: add triphenylphosphine in 250ml reaction bulb and acetonitrile is dried, slowly drip under ice-water bath
Liquid feeding bromine, controls temperature to be less than 40 DEG C.Plus change ice bath after bromine for oil bath, then Deca 50ml compound containing 29g b-5 (0.1mol)
Acetonitrile solution, after adding, reaction system is reacted at 60-70 DEG C 30min, then change distilling apparatus, acetonitrile is evaporated off.Again
With electric heating bag reacting by heating system to 300 DEG C, and keep this temperature to stopping release hbr.Cooling system, adds petroleum ether, obtains
Filter to precipitation, petroleum ether.Filtrate is washed with sodium hydroxide solution, is dried, and column chromatography obtains compound b, yield 55%.
Mass spectrum m/z:416.13 (value of calculation: 415.87).Theoretical elemental content (%) c18h8br2S:c, 51.95；h,1.94；br,
38.40；s,7.71；Actual measurement constituent content (%): c, 51.99；h,1.90；br,38.44；s,7.67.The above results confirm to obtain
Product is target product.
Embodiment 3: the synthesis of compound m1:
Under nitrogen protection, by 4.2g intermediate a (0.01mol), 3.0g phenylboric acid (0.025mol) and 30ml toluene add
In 250ml reaction bulb, add 20ml ethanol, 30ml saturated sodium carbonate solution and 232mgpd (pph3)4(2%eq.), stir and return
Stream reaction.Filtered while hot after reaction, is washed with 50ml dichloromethane, and vacuum distillation removes solvent, crude product petroleum ether post layer
Analysis obtains compound m1, yield 65%.Mass spectrum m/z:410.52 (value of calculation: 410.11).Theoretical elemental content (%) c30h18S:
c,87.77；h,4.42；s,7.81；Actual measurement constituent content (%): c, 87.71；h,4.46；s,7.83.The above results confirm to obtain
Product is target product.
Embodiment 4: the synthesis of compound m2:
Under nitrogen protection, by 4.2g intermediate b (0.01mol), 3.0g phenylboric acid (0.025mol) and 30ml toluene add
In 250ml reaction bulb, add 20ml ethanol, 30ml saturated sodium carbonate solution and 232mgpd (pph3)4(2%eq.), stir and return
Stream reaction.Filtered while hot after reaction, is washed with 50ml dichloromethane, and vacuum distillation removes solvent, crude product petroleum ether post layer
Analysis obtains compound m1, yield 67%.Mass spectrum m/z:410.52 (value of calculation: 410.11).Theoretical elemental content (%) c30h18S:
c,87.77；h,4.42；s,7.81；Actual measurement constituent content (%): c, 87.71；h,4.46；s,7.83.The above results confirm to obtain
Product is target product.
Embodiment 5: the synthesis of compound m3:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 4- biphenylboronic acid, obtains compound
M3, yield 66%.Mass spectrum m/z:562.72 (value of calculation: 562.18).Theoretical elemental content (%) c42h26S:c, 89.64；h,
4.66；s,5.70；Actual measurement constituent content (%): c, 89.68；h,4.64；s,5.68.The above results confirm that obtaining product is target
Product.
Embodiment 6: the synthesis of compound m4:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 4- biphenylboronic acid, obtains compound
M4, yield 65%.Mass spectrum m/z:562.72 (value of calculation: 562.18).Theoretical elemental content (%) c42h26S:c, 89.64；h,
4.66；s,5.70；Actual measurement constituent content (%): c, 89.68；h,4.64；s,5.68.The above results confirm that obtaining product is target
Product.
Embodiment 7: the synthesis of compound m5:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 3,5- diphenyl benzene boric acid, is changed
Compound m5, yield 70%.Mass spectrum m/z:714.88 (value of calculation: 714.24).Theoretical elemental content (%) c54h34S:c, 90.72；
h,4.79；s,4.49；Actual measurement constituent content (%): c, 90.68；h,4.81；s,4.51.The above results confirm that obtaining product is mesh
Mark product.
Embodiment 8: the synthesis of compound m6:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 3,5- diphenyl benzene boric acid, is changed
Compound m6, yield 69%.Mass spectrum m/z:714.88 (value of calculation: 714.24).Theoretical elemental content (%) c54h34S:c, 90.72；
h,4.79；s,4.49；Actual measurement constituent content (%): c, 90.68；h,4.81；s,4.51.The above results confirm that obtaining product is mesh
Mark product.
Embodiment 9: the synthesis of compound m7:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 2- naphthalene boronic acids, obtains compound m7,
Yield 66%.Mass spectrum m/z:510.65 (value of calculation: 510.14).Theoretical elemental content (%) c38h22S:c, 89.38；h,4.34；
s,6.28；Actual measurement constituent content (%): c, 89.46；h,4.30；s,6.24.The above results confirm that obtaining product is target product.
Embodiment 10: the synthesis of compound m8:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 2- naphthalene boronic acids, obtains compound m8,
Yield 65%.Mass spectrum m/z:510.65 (value of calculation: 510.14).Theoretical elemental content (%) c38h22S:c, 89.38；h,4.34；
s,6.28；Actual measurement constituent content (%): c, 89.46；h,4.30；s,6.24.The above results confirm that obtaining product is target product.
Embodiment 11: the synthesis of compound m9:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 1- naphthalene boronic acids, obtains compound m9,
Yield 56%.Mass spectrum m/z:510.65 (value of calculation: 510.14).Theoretical elemental content (%) c38h22S:c, 89.38；h,4.34；
s,6.28；Actual measurement constituent content (%): c, 89.46；h,4.30；s,6.24.The above results confirm that obtaining product is target product.
Embodiment 12: the synthesis of compound m10:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 1- naphthalene boronic acids, obtains compound m10,
Yield 55%.Mass spectrum m/z:510.65 (value of calculation: 510.14).Theoretical elemental content (%) c38h22S:c, 89.38；h,4.34；
s,6.28；Actual measurement constituent content (%): c, 89.46；h,4.30；s,6.24.The above results confirm that obtaining product is target product.
Embodiment 13: the synthesis of compound m11:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 9- anthracene boric acid, obtains compound m11,
Yield 51%.Mass spectrum m/z:610.72 (value of calculation: 610.18).Theoretical elemental content (%) c46h26S:c, 90.46；h,4.29；
s,5.25；Actual measurement constituent content (%): c, 90.48；h,4.25；s,5.27.The above results confirm that obtaining product is target product.
Embodiment 14: the synthesis of compound m12:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 9- anthracene boric acid, obtains compound m12,
Yield 52%.Mass spectrum m/z:610.72 (value of calculation: 610.18).Theoretical elemental content (%) c46h26S:c, 90.46；h,4.29；
s,5.25；Actual measurement constituent content (%): c, 90.48；h,4.25；s,5.27.The above results confirm that obtaining product is target product.
Embodiment 15: the synthesis of compound m13:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 9- phenanthrene boric acid, obtains compound m13,
Yield 60%.Mass spectrum m/z:610.76 (value of calculation: 610.18).Theoretical elemental content (%) c46h26S:c, 90.46；h,4.29；
s,5.25；Actual measurement constituent content (%): c, 90.48；h,4.25；s,5.27.The above results confirm that obtaining product is target product.
Embodiment 16: the synthesis of compound m14:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 9- phenanthrene boric acid, obtains compound m14,
Yield 58%.Mass spectrum m/z:610.76 (value of calculation: 610.18).Theoretical elemental content (%) c46h26S:c, 90.46；h,4.29；
s,5.25；Actual measurement constituent content (%): c, 90.48；h,4.25；s,5.27.The above results confirm that obtaining product is target product.
Embodiment 17: the synthesis of compound m15:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 2- pyrene boric acid, obtains compound m15,
Yield 65%.Mass spectrum m/z:658.81 (value of calculation: 658.18).Theoretical elemental content (%) c50h26S:c, 91.15；h,3.98；
s,4.87；Actual measurement constituent content (%): c, 91.11；h,3.92；s,4.87.The above results confirm that obtaining product is target product.
Embodiment 18: the synthesis of compound m16:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 2- pyrene boric acid, obtains compound m16,
Yield 62%.Mass spectrum m/z:658.81 (value of calculation: 658.18).Theoretical elemental content (%) c50h26S:c, 91.15；h,3.98；
s,4.87；Actual measurement constituent content (%): c, 91.11；h,3.92；s,4.87.The above results confirm that obtaining product is target product.
Embodiment 19: the synthesis of compound m17:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 9,9- dimethyl -2- fluorenes boric acid, obtains
To compound m17, yield 79%.Mass spectrum m/z:642.72 (value of calculation: 642.24).Theoretical elemental content (%) c48h34S:c,
89.68；h,5.33；s,4.99；Actual measurement constituent content (%): c, 89.76；h,5.29；s,4.95.The above results confirm to obtain produces
Thing is target product.
Embodiment 20: the synthesis of compound m18:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 9,9- dimethyl -2- fluorenes boric acid, obtains
To compound m18, yield 80%.Mass spectrum m/z:642.72 (value of calculation: 642.24).Theoretical elemental content (%) c48h34S:c,
89.68；h,5.33；s,4.99；Actual measurement constituent content (%): c, 89.76；h,5.29；s,4.95.The above results confirm to obtain produces
Thing is target product.
Embodiment 21: the synthesis of compound m19:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 2- carbazole boric acid, obtains compound
M19, yield 64%.Mass spectrum m/z:588.72 (value of calculation: 588.17).Theoretical elemental content (%) c42h24n2S:c, 85.69；h,
4.11；n,4.76；s,5.45；Actual measurement constituent content (%): c, 85.65；h,4.07；n,4.80；s,5.49.The above results confirm
Acquisition product is target product.
Embodiment 22: the synthesis of compound m20:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 2- carbazole boric acid, obtains compound
M20, yield 66%.Mass spectrum m/z:588.72 (value of calculation: 588.17).Theoretical elemental content (%) c42h24n2S:c, 85.69；h,
4.11；n,4.76；s,5.45；Actual measurement constituent content (%): c, 85.65；h,4.07；n,4.80；s,5.49.The above results confirm
Acquisition product is target product.
Embodiment 23: the synthesis of compound m21:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 3- pyridine boronic acid, obtains compound
M21, yield 60%.Mass spectrum m/z:412.14 (value of calculation: 412.10).Theoretical elemental content (%) c28h16n2S:c, 81.53；h,
3.91；n,6.79；s,7.77；Actual measurement constituent content (%): c, 81.65；h,3.87；n,6.75；s,7.73.The above results confirm
Acquisition product is target product.
Embodiment 24: the synthesis of compound m22:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 3- pyridine boronic acid, obtains compound
M22, yield 58%.Mass spectrum m/z:412.14 (value of calculation: 412.10).Theoretical elemental content (%) c28h16n2S:c, 81.53；h,
3.91；n,6.79；s,7.77；Actual measurement constituent content (%): c, 81.65；h,3.87；n,6.75；s,7.73.The above results confirm
Acquisition product is target product.
Embodiment 25: the synthesis of compound m23:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 5- phenyl 2- pyridine boronic acid, is changed
Compound m23, yield 68%.Mass spectrum m/z:564.72 (value of calculation: 564.17).Theoretical elemental content (%) c40h24n2S:c,
85.08；h,4.28；n,4.96；s,5.68；Actual measurement constituent content (%): c, 85.20；h,4.24；n,4.92；s,5.64.Above-mentioned
Result confirms that obtaining product is target product.
Embodiment 26: the synthesis of compound m24:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 5- phenyl 2- pyridine boronic acid, is changed
Compound m24, yield 66%.Mass spectrum m/z:564.72 (value of calculation: 564.17).Theoretical elemental content (%) c40h24n2S:c,
85.08；h,4.28；n,4.96；s,5.68；Actual measurement constituent content (%): c, 85.20；h,4.24；n,4.92；s,5.64.Above-mentioned
Result confirms that obtaining product is target product.
Embodiment 27: the synthesis of compound m25:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 4- (3- pyridine radicals) phenylboric acid, obtains
Compound m25, yield 72%.Mass spectrum m/z:564.78 (value of calculation: 564.17).Theoretical elemental content (%) c40h24n2S:c,
85.08；h,4.28；n,4.96；s,5.68；Actual measurement constituent content (%): c, 85.20；h,4.24；n,4.92；s,5.64.Above-mentioned
Result confirms that obtaining product is target product.
Embodiment 28: the synthesis of compound m26:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 4- (3- pyridine radicals) phenylboric acid, obtains
Compound m26, yield 72%.Mass spectrum m/z:564.78 (value of calculation: 564.17).Theoretical elemental content (%) c42h24n2S:c,
85.08；h,4.28；n,4.96；s,5.68；Actual measurement constituent content (%): c, 85.20；h,4.24；n,4.92；s,5.64.Above-mentioned
Result confirms that obtaining product is target product.
Embodiment 29: the synthesis of compound m27:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 8-quinolineboronic acid, obtains compound
M27, yield 75%.Mass spectrum m/z:512.62 (value of calculation: 512.13).Theoretical elemental content (%) c36h20n2S:c, 84.35；h,
3.93；n,5.46；s,6.26；Actual measurement constituent content (%): c, 84.65；h,3.83；n,5.36；s,6.16.The above results confirm
Acquisition product is target product.
Embodiment 30: the synthesis of compound m28:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 8-quinolineboronic acid, obtains compound
M28, yield 78%.Mass spectrum m/z:512.62 (value of calculation: 512.13).Theoretical elemental content (%) c36h20n2S:c, 84.35；h,
3.93；n,5.46；s,6.26；Actual measurement constituent content (%): c, 84.65；h,3.83；n,5.36；s,6.16.The above results confirm
Acquisition product is target product.
Embodiment 31: the synthesis of compound m29:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 1- isoquinolin boric acid, obtains compound
M29, yield 70%.Mass spectrum m/z:512.62 (value of calculation: 512.13).Theoretical elemental content (%) c36h20n2S:c, 84.35；h,
3.93；n,5.46；s,6.26；Actual measurement constituent content (%): c, 84.47；h,3.89；n,5.42；s,6.22.The above results confirm
Acquisition product is target product.
Embodiment 32: the synthesis of compound m30:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 1- isoquinolin boric acid, obtains compound
M30, yield 68%.Mass spectrum m/z:512.62 (value of calculation: 512.13).Theoretical elemental content (%) c36h20n2S:c, 84.35；h,
3.93；n,5.46；s,6.26；Actual measurement constituent content (%): c, 84.47；h,3.89；n,5.42；s,6.22.The above results confirm
Acquisition product is target product.
Embodiment 33: the synthesis of compound m31:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 4- (1,10)-neighbour's phenanthrene quinoline boric acid,
Obtain compound m31, yield 69%.Mass spectrum m/z:614.72 (value of calculation: 614.16).Theoretical elemental content (%) c42h22n4S:
c,82.06；h,3.61；n,9.11；s,5.22；Actual measurement constituent content (%): c, 82.18；h,3.57；n,9.07；s,5.18.On
State result and confirm that obtaining product is target product.
Embodiment 34: the synthesis of compound m32:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 4- (1,10)-neighbour's phenanthrene quinoline boric acid,
Obtain compound m32, yield 69%.Mass spectrum m/z:614.72 (value of calculation: 614.16).Theoretical elemental content (%) c42h22n4S:
c,82.06；h,3.61；n,9.11；s,5.22；Actual measurement constituent content (%): c, 82.18；h,3.57；n,9.07；s,5.18.On
State result and confirm that obtaining product is target product.
Embodiment 35: the synthesis of compound m33:
Implementation process with embodiment 3, except for the difference that by phenylboric acid change into equimolar (1- phenyl -1h- benzimidazolyl-2 radicals -
Base) boric acid, obtain compound m33, yield 65%.Mass spectrum m/z:642.77 (value of calculation: 642.19).Theoretical elemental content (%)
c44h26n4S:c, 82.22；h,4.08；n,8.72；s,4.99；Actual measurement constituent content (%): c, 82.10；h,4.12；n,8.76；
s,5.03.The above results confirm that obtaining product is target product.
Embodiment 36: the synthesis of compound m34:
Implementation process with embodiment 4, except for the difference that by phenylboric acid change into equimolar (1- phenyl -1h- benzimidazolyl-2 radicals -
Base) boric acid, obtain compound m34, yield 65%.Mass spectrum m/z:642.77 (value of calculation: 642.19).Theoretical elemental content (%)
c44h26n4S:c, 82.22；h,4.08；n,8.72；s,4.99；Actual measurement constituent content (%): c, 82.10；h,4.12；n,8.76；
s,5.03.The above results confirm that obtaining product is target product.
Embodiment 37: the synthesis of compound m35:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar 2-[4-morpholinodithio boric acid, obtains chemical combination
Thing m35, yield 76%.Mass spectrum m/z:524.12 (value of calculation: 524.68).Theoretical elemental content (%) c32h16n2s3: c,
73.25；h,3.07；n,5.34；s,18.33；Actual measurement constituent content (%): c, 73.21；h,3.03；n,5.30；s,18.45.On
State result and confirm that obtaining product is target product.
Embodiment 38: the synthesis of compound m36:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar 2-[4-morpholinodithio boric acid, obtains chemical combination
Thing m36, yield 74%.Mass spectrum m/z:524.12 (value of calculation: 524.68).Theoretical elemental content (%) c32h16n2s3: c,
73.25；h,3.07；n,5.34；s,18.33；Actual measurement constituent content (%): c, 73.21；h,3.03；n,5.30；s,18.45.On
State result and confirm that obtaining product is target product.
Embodiment 39: the synthesis of compound m37:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar (2- oxazolyl phenyl -5- base) boric acid,
Obtain compound m37, yield 72%.Mass spectrum m/z:546.60 (value of calculation: 546.12).Theoretical elemental content (%)
c34h18n4o2S:c, 74.71；h,3.32；n,10.25；o,5.85；s,5.87；Actual measurement constituent content (%): c, 74.65；h,
3.38；n,10.29；o,5.83；s,5.85.The above results confirm that obtaining product is target product.
Embodiment 40: the synthesis of compound m38:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar (2- oxazolyl phenyl -5- base) boric acid,
Obtain compound m38, yield 71%.Mass spectrum m/z:546.60 (value of calculation: 546.12).Theoretical elemental content (%)
c34h18n4o2S:c, 74.71；h,3.32；n,10.25；o,5.85；s,5.87；Actual measurement constituent content (%): c, 74.65；h,
3.38；n,10.29；o,5.83；s,5.85.The above results confirm that obtaining product is target product.
Embodiment 41: the synthesis of compound m39:
Implementation process, with embodiment 3, except for the difference that changes phenylboric acid into equimolar (2- phenyl thiazole -5- base) boric acid,
Obtain compound m39, yield 66%.Mass spectrum m/z:578.73 (value of calculation: 578.07).Theoretical elemental content (%)
c34h18n4s3: c, 70.56；h,3.13；n,9.68；s,16.62；Actual measurement constituent content (%): c, 70.66；h,3.15；n,
9.62；s,16.56.The above results confirm that obtaining product is target product.
Embodiment 42: the synthesis of compound m40:
Implementation process, with embodiment 4, except for the difference that changes phenylboric acid into equimolar (2- phenyl thiazole -5- base) boric acid,
Obtain compound m40, yield 65%.Mass spectrum m/z:578.73 (value of calculation: 578.07).Theoretical elemental content (%)
c34h18n4s3: c, 70.56；h,3.13；n,9.68；s,16.62；Actual measurement constituent content (%): c, 70.66；h,3.15；n,
9.62；s,16.56.The above results confirm that obtaining product is target product.
Embodiment 43: the preparation of luminescent device 1
With ito glass as anode, be repeatedly cleaned by ultrasonic ito glass substrate with ethanol, deionized water, after as vacuum tank
Middle drying.It is evacuated to 5 × 10-4pa；On above-mentioned anode substrate, as hole transmission layer, evaporation rate is vacuum evaporation npb
0.1nm/s, evaporation thickness is 40nm.Vacuum evaporation light emitting host material compound m5 on hole transmission layer: dopant ir
(ppy)3(100:9) as device luminescent layer, evaporation rate is 0.005nm/s, and evaporation thickness is 30nm.Vacuum on luminescent layer
As electron transfer layer, evaporation rate is 0.01nm/s to evaporation m31, and evaporation thickness is 20nm.Vacuum is steamed on the electron transport layer
Plating lif is respectively 1.0nm and 100nm as electron injecting layer, al layer as negative electrode, thickness.This requirement on devices brightness 1000cd/
m2, cut-in voltage 6.8v, maximum current efficiency is 35.7cd/a.
Embodiment 44: the preparation of luminescent device 2
With ito glass as anode, be repeatedly cleaned by ultrasonic ito glass substrate with ethanol, deionized water, after as vacuum tank
Middle drying.It is evacuated to 5 × 10-4pa；On above-mentioned anode substrate, as hole transmission layer, evaporation rate is vacuum evaporation npb
0.1nm/s, evaporation thickness is 40nm.Vacuum evaporation light emitting host material compound cbp on hole transmission layer: dopant ir
(ppy)3(100:9) as device luminescent layer, evaporation rate is 0.005nm/s, and evaporation thickness is 30nm.Vacuum on luminescent layer
As electron transfer layer, evaporation rate is 0.01nm/s to evaporation m33, and evaporation thickness is 20nm.Vacuum is steamed on the electron transport layer
Plating lif is respectively 1.0nm and 100nm as electron injecting layer, al layer as negative electrode, thickness.This requirement on devices brightness 1000cd/
m2, cut-in voltage 6.2v, maximum current efficiency is 37.6cd/a.
Result above shows, the naphtho- thia anthracene derivant of the present invention is applied in organic electroluminescence device, starts electricity
Force down, current efficiency is high, luminous efficiency is high, is luminous organic material of good performance.
Obviously, the explanation of above example is only intended to help and understands the method for the present invention and its core concept.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, can also be to this
Bright carry out some improve and modify, these improve and modify also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a kind of naphtho- thia anthracene derivant is it is characterised in that structural formula is:
Or
Wherein, r1、r2、r3、r4The independent aryl selected from c6-c50, the fused ring aryl of c10-c50, the condensed hetero ring aryl of c7-c50
Or the nitrogenous heteroaryl of c5-c50.
2. a kind of naphtho- thia anthracene derivant according to claim 1 is it is characterised in that r1、r2、r3、r4Independent is selected from
The aryl of c6-c30, the nitrogenous heteroaryl of the fused ring aryl of c10-c30, the condensed hetero ring aryl of c7-c30 or c5-c30.
3. a kind of naphtho- thia anthracene derivant according to claim 1 is it is characterised in that r1、r2、r3、r4Independent is selected from
The aryl of c6-c20, the nitrogenous heteroaryl of the fused ring aryl of c10-c20, the condensed hetero ring aryl of c7-c20 or c5-c20.
4. a kind of naphtho- thia anthracene derivant according to claim 1 is it is characterised in that r1、r2、r3、r4Independent is selected from
Phenyl, xenyl, naphthyl, anthryl, phenanthryl, pyrenyl, fluorenyl, carbazyl, pyridine radicals, pyridinylphenyl, quinolyl, imidazole radicals,
Thiazolyl or oxazolyl.
5. a kind of naphtho- thia anthracene derivant according to claim 1 is it is characterised in that described r1With r2Identical, described r3
With r4Identical.
6. a kind of naphtho- thia anthracene derivant according to claim 1 is it is characterised in that described naphtho- thia anthracene derivant
Any one in structure shown in following m1～m40:
.
7. the preparation method of the naphtho- thia anthracene derivant described in any one of claim 1～6 is it is characterised in that protect in nitrogen
Under shield, the compound shown in formula a or the compound shown in formula b are obtained the naphtho- sulfur shown in formula or formula ii through coupling reaction
Miscellaneous anthracene derivant；
Wherein, r1、r2、r3、r4The independent aryl selected from c6-c50, the fused ring aryl of c10-c50, the condensed hetero ring aryl of c7-c50
Or the nitrogenous heteroaryl of c5-c50.
8. application in organic electroluminescence device for the naphtho- thia anthracene derivant described in claim 1～6 any one.
9. application in organic electroluminescence device for the naphtho- thia anthracene derivant according to claim 8, described organic
Electroluminescent device includes anode, negative electrode and organic matter layer, and organic matter layer comprises hole injection layer, hole transmission layer, electronics resistance
At least one of which in barrier, organic luminous layer, hole blocking layer, electron transfer layer, electron injecting layer, described luminescent layer includes leading
Body material and dopant dye；At least one of which in described organic matter layer contains the naphtho- thia described in any one of claim 1～6
Anthracene derivant.
10. application in organic electroluminescence device for the naphtho- thia anthracene derivant according to claim 9, its feature exists
In the naphtho- thia anthracene derivant of described claim 1～6 is used for the electric transmission of organic electroluminescence device for one or more
Layer material or the material of main part of luminescent layer.
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