CN109912494A - It is a kind of using cyano benzene as the compound of core and its application in OLED device - Google Patents
It is a kind of using cyano benzene as the compound of core and its application in OLED device Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 75
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000005401 electroluminescence Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- 239000010410 layer Substances 0.000 claims description 54
- 239000002994 raw material Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 14
- 229910002027 silica gel Inorganic materials 0.000 claims description 14
- 229960001866 silicon dioxide Drugs 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000004653 anthracenylene group Chemical group 0.000 claims description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 239000002346 layers by function Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 43
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 32
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
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- 229960000583 acetic acid Drugs 0.000 description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 4
- SMNRFWMNPDABKZ-WVALLCKVSA-N [[(2R,3S,4R,5S)-5-(2,6-dioxo-3H-pyridin-3-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [[[(2R,3S,4S,5R,6R)-4-fluoro-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-hydroxyphosphoryl]oxy-hydroxyphosphoryl] hydrogen phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OC[C@H]2O[C@H]([C@H](O)[C@@H]2O)C2C=CC(=O)NC2=O)[C@H](O)[C@@H](F)[C@@H]1O SMNRFWMNPDABKZ-WVALLCKVSA-N 0.000 description 4
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
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- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 2
- OMBVEVHRIQULKW-DNQXCXABSA-M (3r,5r)-7-[3-(4-fluorophenyl)-8-oxo-7-phenyl-1-propan-2-yl-5,6-dihydro-4h-pyrrolo[2,3-c]azepin-2-yl]-3,5-dihydroxyheptanoate Chemical compound O=C1C=2N(C(C)C)C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C=3C=CC(F)=CC=3)C=2CCCN1C1=CC=CC=C1 OMBVEVHRIQULKW-DNQXCXABSA-M 0.000 description 2
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 2
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 2
- WFOVEDJTASPCIR-UHFFFAOYSA-N 3-[(4-methyl-5-pyridin-4-yl-1,2,4-triazol-3-yl)methylamino]-n-[[2-(trifluoromethyl)phenyl]methyl]benzamide Chemical compound N=1N=C(C=2C=CN=CC=2)N(C)C=1CNC(C=1)=CC=CC=1C(=O)NCC1=CC=CC=C1C(F)(F)F WFOVEDJTASPCIR-UHFFFAOYSA-N 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- JQUCWIWWWKZNCS-LESHARBVSA-N C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F Chemical compound C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F JQUCWIWWWKZNCS-LESHARBVSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- SPXSEZMVRJLHQG-XMMPIXPASA-N [(2R)-1-[[4-[(3-phenylmethoxyphenoxy)methyl]phenyl]methyl]pyrrolidin-2-yl]methanol Chemical compound C(C1=CC=CC=C1)OC=1C=C(OCC2=CC=C(CN3[C@H](CCC3)CO)C=C2)C=CC=1 SPXSEZMVRJLHQG-XMMPIXPASA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
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- LPOIGVZLNWEGJG-UHFFFAOYSA-N n-benzyl-5-(4-methylpiperazin-1-yl)-2-nitroaniline Chemical compound C1CN(C)CCN1C1=CC=C([N+]([O-])=O)C(NCC=2C=CC=CC=2)=C1 LPOIGVZLNWEGJG-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a kind of using cyano benzene as the compound of core and its application in OLED device, and the compound is using cyano benzene as core, and using carbazole and cyclic group is branch.The compound have the characteristics that it is intermolecular be not easy to crystallize, be not easy to assemble, good film-forming property.The compounds of this invention can be used as emitting layer material applied on organic electroluminescence device, has good photoelectric properties using the organic electroluminescence device of the compounds of this invention, can preferably adapt to and meet the application requirement of panel manufacturing enterprise.
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly, to it is a kind of using cyano benzene as the compound of core and its
Application in OLED device.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make
New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is very extensive.Structure of the OLED luminescent device like sandwich, including electrode material film layer, and it is clipped in different electricity
Organic functional material between the film layer of pole, various different function materials are overlapped mutually depending on the application collectively constitutes OLED hair together
Optical device.As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer function
Positive and negative charge in energy film layer, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Application of the Organic Light Emitting Diode (OLEDs) in terms of large-area flat-plate is shown and is illuminated causes industry and
The extensive concern of art circle.However, traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, device
The internal quantum efficiency of part is lower (up to 25%).External quantum efficiency is generally lower than 5%, and there are also very big with the efficiency of phosphorescent devices
Gap.Although phosphor material can efficiently use electricity since the strong SO coupling in heavy atom center enhances intersystem crossing
The singlet exciton formed and Triplet exciton are excited, makes the internal quantum efficiency of device up to 100%.But phosphor material exists
Expensive, stability of material is poor, and device efficiency tumbles the problems such as serious and limits its application in OLED.Hot activation is prolonged
Slow fluorescence (TADF) material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.It should
Class material generally has poor (the △ E of small singlet-tripletST), triplet excitons can be changed by anti-intersystem crossing
It shines at singlet exciton.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation, device it is interior
Quantum efficiency can achieve 100%.Meanwhile material structure is controllable, and property is stablized, and it is cheap to be not necessarily to precious metal, in OLED
Field has a extensive future.
Although theoretically 100% exciton utilization rate may be implemented in TADF material, following problem there are in fact: (1)
T1 the and S1 state for designing molecule has strong CT feature, very small S1-T1 state energy gap, although can realize by TADF process
High T1→S1State exciton conversion ratio, but low S1 state radiation transistion rate is also resulted in, consequently it is difficult to have both (or realizing simultaneously)
High exciton utilization rate and high fluorescent radiation efficiency；(2) even if having used doping device to mitigate T exciton concentration quenching effect, greatly
Efficiency roll-off is serious at higher current densities for the device of most TADF materials.Current OLED is shown to the actual demand of Lighting Industry
For, the development of OLED material is also far from enough at present, lags behind the requirement of panel manufacturing enterprise, more as material enterprise development
High performance organic functional material is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provide it is a kind of using cyano benzene as the compound of core and
Its application in OLED device.The compounds of this invention is based on TADF mechanism using cyano benzene as core, answers as emitting layer material
For Organic Light Emitting Diode, the device that the present invention makes has good photoelectric properties, can satisfy panel manufacturing enterprise
It is required that.
Technical scheme is as follows: a kind of using cyano benzene as the compound of core, the structure of the compound is such as logical
Shown in formula (1):
In general formula (1), X1、X2And X3Independently be expressed as cyano or hydrogen atom；X1、X2And X3It is not former for hydrogen simultaneously
Son；
In general formula (1), R1、R2Independently be expressed as hydrogen atom, substituted or unsubstituted C6-60Aryl contains one
Or multiple heteroatomic substituted or unsubstituted 5-60 unit's heteroaryls；The hetero atom is nitrogen, oxygen or sulphur；R1With R2It is not simultaneously
Hydrogen atom；
In general formula (1), Ar is expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains one or more hetero atoms
Substituted or unsubstituted 5-60 member heteroarylidene；The hetero atom is nitrogen, oxygen or sulphur；
In general formula (1), R3It is expressed as structure shown in general formula (2) or general formula (3)；R4It is expressed as structure shown in general formula (2)；
In general formula (3), X4It is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, the aryl of linear or branched alkyl group substitution take
One of the imido grpup that the alkylidene in generation, alkyl-substituted imido grpup or aryl replace；
General formula (2) passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL'2-CL’3Key or CL’3-CL’4Key and
General formula (1) and ring connection；
General formula (3) passes through CL’1-CL’2Key, CL'2-CL’3Key or CL’3-CL’4Key is connected with general formula (1) and ring.
On the basis of above scheme, the present invention can also do following improvement.
Preferably, a kind of using cyano benzene as the compound of core, the structure of the compound such as general formula (4) or general formula (5)
It is shown:
Preferably, a kind of using cyano benzene as the compound of core, the R1、R2Independently be expressed as hydrogen atom, benzene
Base, xenyl, naphthalene or anthryl；The Ar is expressed as one kind of singly-bound, phenylene, biphenylene, naphthylene or anthrylene.
Preferably, a kind of using cyano benzene as the compound of core, in general formula (1)It indicates are as follows:
In it is any
It is a kind of.
Preferably, a kind of using cyano benzene as the compound of core, it is describedIt indicates are as follows:
In any one.
Preferably, a kind of using cyano benzene as the compound of core, the concrete structure formula of the compound are as follows:
In any one.
The application also provides a kind of using cyano benzene as the preparation method of the compound of core, to occur in preparation process reaction
Equation is:
When Ar indicates singly-bound:
Specific preparation step are as follows:
Raw material bromo-derivative E1 and intermediate M1 are dissolved in dry toluene, Pd is added after deoxygenation2(dba)3And tri-tert
Phosphorus, under an inert atmosphere 95~110 DEG C of 10~24 hours of reaction constantly monitor reaction process with TLC in reaction process, to original
After expecting fully reacting, filtrate is rotated and removes dry toluene by cooling, filtering, and crude product crosses silicagel column, obtains target compound；
The dosage of the dry toluene is that every gram of intermediate M1 uses 30~50mL toluene, and bromo-derivative E1 and the molar ratio of intermediate M1 are
1:1.0~1.5, Pd2(dba)3Molar ratio with bromo-derivative E1 is 0.006~0.02:1, and tri-tert-butylphosphine rubs with bromo-derivative E1's
, than being 0.006~0.02:1, the molar ratio of sodium tert-butoxide and bromo-derivative E1 are 2.0~3.0:1 for you；
When Ar does not indicate singly-bound:
Intermediate M2 and raw material E2 are dissolved in the mixed solution of toluene and ethyl alcohol, Pd (PPh is added after deoxygenation3)4With
K2CO3, 95~110 DEG C of 10~24 hours of reaction under an inert atmosphere constantly monitor reaction process with TLC in reaction process, to
After raw material fully reacting, filtrate is rotated the mixed solution for removing toluene and ethyl alcohol by cooling, filtering, and crude product is crossed silicagel column, obtained
To target compound；The dosage of the toluene and ethyl alcohol is that every gram of intermediate M2 uses 30~50mL toluene and 5~10mL second
The molar ratio of alcohol, raw material E2 and intermediate M2 are (1~1.5): 1, Pd (PPh3)4With the molar ratio of intermediate M2 be (0.006~
0.02): 1, K2CO3Molar ratio with intermediate M2 is (1.5~2): 1.
The application also provides a kind of organic electroluminescence device, and the organic electroluminescence device includes at least one layer of function
Layer is containing described a kind of using cyano benzene as the compound of core.
Preferably, a kind of organic electroluminescence device, including luminescent layer, the luminescent layer contain described one kind with cyano
Benzene is the compound of core.
The application also provides a kind of illumination or display element, including the organic electroluminescence device.
The present invention is beneficial to be had the technical effect that
For the compounds of this invention using cyano benzene as parent nucleus, cyano-phenyl group is in approximately the same plane, has stronger rigidity, more
Good film forming；Cyano-phenyl group is strong electron-withdrawing group group, and with carbazole and ring class group can form stronger electric charge transfer, and have
There is the energy level difference of lesser S1 state and T1 state, so that reversed intersystem crossing is realized under the conditions of thermostimulation, in the item that energy level meets
There is bipolarity and TADF effect simultaneously under part；Simultaneously because the chemical stability and thermal stability of cyano, cyano benzene have compared with
Good prospects for commercial application is suitable as the use of luminescent layer material of main part.Further, the difference designed according to material molecule,
The dopant material that such compound can also be used as emitting layer material uses.
The compounds of this invention as OLED luminescent device emitting layer material in use, device current efficiency, power effect
Rate and external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly.Compound material of the present invention
Material has good application effect in OLED luminescent device, has good industrialization prospect.
Detailed description of the invention
Fig. 1 is the device architecture schematic diagram of the compounds of this invention application；
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transmission layer, and 5 be luminous
Layer, 6 be electron transfer layer, and 7 be electron injecting layer, and 8 be cathode reflection electrode layer；
Fig. 2 is current efficiency variation with temperature curve.
Specific embodiment
Embodiment 1:
It provides in general formula (1) firstSynthetic route are as follows:
It weighs raw material I to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, be slowly added dropwise to
In acetic acid solution containing nitro compound raw material I, reaction is stirred at room temperature 6~12 hours, after reaction, sodium hydroxide is added dropwise
Aqueous solution makes the aobvious neutrality of reaction solution, is extracted with dichloromethane, organic phase is taken to filter, and filtrate decompression is rotated to no fraction, crosses silica gel
Column obtains intermediate S1；In above-mentioned reaction, the molar ratio of raw material I and bromine is 1:1~3；Every gram of raw material I uses 30~50mL
Acetic acid；
Weigh raw material II and intermediate S1, dissolved with toluene, under an inert atmosphere, be added potassium carbonate, tetra-triphenylphosphine palladium,
The mixed solution of second alcohol and water, stirring are warming up to 110~120 DEG C, react 10~24 hours, after reaction, are cooled to room temperature,
Filtering, filtrate layered take organic phase vacuum rotary steam to no fraction, cross silicagel column, obtain intermediate S2；It is intermediate in above-mentioned reaction
The molar ratio of body S1 and raw material II is 1:1~2；The molar ratio of intermediate S1 and potassium carbonate is 1:1~3；Intermediate S1 and four or three
The molar ratio of Phenylphosphine palladium is 1:0.01~0.05；Every gram of intermediate S1 uses 30~50mL toluene；Every gram of intermediate S1 is used
The mixed liquor that 15~25mL water and ethyl alcohol volume ratio are 1:1；
Under an inert atmosphere, intermediate S2 is dissolved in o-dichlorohenzene, adds triphenylphosphine, stirred at 170~190 DEG C
It mixes reaction 12~16 hours, is cooled to room temperature after reaction, filter, filtrate decompression is rotated to no fraction, is crossed silicagel column, is obtained
Intermediate M1；In above-mentioned reaction, intermediate S2 and triphenylphosphine molar ratio are 1:1~2；Every gram of intermediate S2 uses 30~50mL
O-dichlorohenzene；
Under nitrogen protection, intermediate M1, raw material III, sodium tert-butoxide, Pd are successively weighed2(dba)3, tri-tert-butylphosphine, use
Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, is sampled contact plate, and display is remaining without intermediate M1,
Fully reacting；Cooled to room temperature, filtering, filtrate carry out vacuum rotary steam to no fraction, cross neutral silica gel column, obtain intermediate
M2.In above-mentioned reaction, intermediate M1 and III molar ratio of raw material are 1:1~2；The molar ratio of intermediate M1 and sodium tert-butoxide is 1:1
~3；Intermediate M1 and Pd2(dba)3Molar ratio be 1:0.01~0.05；The molar ratio of intermediate M1 and tri-tert-butylphosphine is 1:
0.01~0.05；Every gram of intermediate M1 uses 30~50mL toluene.
By taking intermediate M2-1 as an example:
In the there-necked flask of 250ml, raw material I-1,100ml acetic acid of 0.04mol is added, stirring and dissolving is dropped with ice salt bath
Temperature is to 0 DEG C；Weigh 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise into above-mentioned reaction system, is dripped
It after adding, is warmed to room temperature, is stirred to react 12 hours；Contact plate is sampled, display is remaining without raw material I-1, fully reacting；Add NaOH water
Solution makes the aobvious neutrality of reaction solution, is extracted with dichloromethane, is layered, organic phase is taken to filter, and filtrate decompression is rotated to no fraction, excessively in
Property silicagel column, obtains intermediate S1-1；Elemental analysis structure C10H6BrNO2: theoretical value C, 47.65；H,2.40；Br,31.70；
N,5.56；Test value: C, 47.65；H,2.40；Br,31.70；N,5.55；ESI-MS (m/z) (M+): theoretical value 250.96,
Measured value is 251.66.
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.05mol intermediate S1-1,0.06mol raw material II -1,
100ml toluene, is stirred, and adds 0.0025mol Pd (PPh3)4, 0.075mol potassium carbonate, 50ml water and ethyl alcohol volume ratio
For the mixed liquor of 1:1, stirring is warming up to 120 DEG C, back flow reaction 24 hours, samples contact plate, display is remaining without intermediate S1-1, instead
It should be complete；Cooled to room temperature, filtering, filtrate layered take organic phase vacuum rotary steam to no fraction, cross neutral silica gel column, obtain
To intermediate S2-1；Elemental analysis structure C20H13NO2: theoretical value C, 80.25；H,4.38；N,4.68；Test value: C, 80.25；
H,4.38；N,4.69；ESI-MS (m/z) (M+): theoretical value 299.09, measured value 299.88.
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.04mol intermediate S2-1,0.05mol triphenylphosphine,
100ml o-dichlorohenzene, is stirred, and is heated to 180 DEG C, reacts 12 hours, samples contact plate, and display is remaining without intermediate S2-1,
Fully reacting；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain intermediate M1-
1；Elemental analysis structure C20H13N: theoretical value C, 89.86；H,4.90；N,5.24；Test value: C, 89.85；H,4.90；N,
5.25；ESI-MS (m/z) (M+): theoretical value 267.10, measured value 267.75.
In the there-necked flask of 250ml, lead under nitrogen protection, 0.03mol intermediate M1-1,0.036mol Isosorbide-5-Nitrae-two is added
Bromobenzene, 150ml toluene, are stirred, and add 0.09mol sodium tert-butoxide, 0.002molPd2(dba)3, the tertiary fourth of 0.002mol tri-
Base phosphine is heated with stirring to 115 DEG C, back flow reaction 24 hours, samples contact plate, display is remaining without intermediate M1-1, fully reacting；From
It is so cooled to room temperature, filters, filtrate decompression is rotated to no fraction, is crossed neutral silica gel column, is obtained intermediate M2-1；Elemental analysis knot
Structure C26H16BrN: theoretical value C, 73.94；H,3.82；Br,18.92；N,3.32；Test value: C, 73.94；H,3.82；Br,
18.93；N,3.31；ESI-MS (m/z) (M+): theoretical value 421.05, measured value 421.88.
Intermediate M1 and M2 are prepared by the synthetic schemes of intermediate M2-1；Specific structure employed in preparation process is such as
Shown in table 1:
Table 1
Embodiment 2: the synthesis of compound 7:
0.01mol intermediate M2-1 and 0.012mol raw material E2-1 is dissolved in the 150mL (V of toluene and ethyl alcoholToluene: VEthyl alcohol
=5:1) in mixed solution, 0.0002mol Pd (PPh is added after deoxygenation3)4With 0.02mol K2CO3, under an inert atmosphere 110
DEG C 24 hours of reaction, reaction process constantly are monitored with TLC in reaction process, after raw material fully reacting, cooling, filtering will
Filtrate revolving removes solvent, and crude product crosses silicagel column, obtains intermediate target product；Elemental analysis structure (molecular formula
C45H28N2): theoretical value C, 90.58；H,4.73；N,4.69；Test value: C, 90.58；H,4.74；N,4.68；ESI-MS(m/z)
(M+): theoretical value 596.23, measured value 596.88.
Embodiment 3: the synthesis of compound 16:
The preparation method of compound 16 is with embodiment 2, the difference is that replacing intermediate M2-1 using intermediate M2-3.
Elemental analysis structure (molecular formula C45H28N2): theoretical value C, 90.58；H,4.73；N,4.69；Test value: C, 90.59；H,4.73；
N,4.68。ESI-MS(m/z)(M+): theoretical value 596.23, measured value 596.29.
Embodiment 4: the synthesis of compound 28:
The preparation method of compound 28 is with embodiment 2, the difference is that replacing intermediate M2-1 using intermediate M2-4.
Elemental analysis structure (molecular formula C47H28N2O): theoretical value C, 88.66；H,4.43；N,4.40；Test value: C, 88.66；H,
4.43；N,4.41.ESI-MS(m/z)(M+): theoretical value 636.75, measured value 636.75.
Embodiment 5: the synthesis of compound 34:
0.01mol raw material E1-1 and 0.012mol intermediate M1-4 are dissolved in 150mL dry toluene, are added after deoxygenation
0.0005mol Pd2(dba)3, 0.015mol tri-tert phosphorus and 0.02mol sodium tert-butoxide, 110 DEG C of reactions under an inert atmosphere
24 hours constantly monitor reaction process with TLC in reaction process, and after raw material fully reacting, filtrate is revolved in cooling, filtering
Solvent is evaporated off, crude product crosses silicagel column, obtains intermediate target product；Elemental analysis structure (molecular formula C44H30N2): it is theoretical
Value C, 90.07；H,5.15；N,4.77；Test value: C, 90.08；H,5.15；N,4.77；ESI-MS (m/z) (M+): theoretical value is
586.24 measured value 586.88.
Embodiment 6: the synthesis of compound 41:
The preparation method of compound 41 is with embodiment 2, the difference is that replacing intermediate M2-1 using intermediate M2-6.
Elemental analysis structure (molecular formula C50H34N2): theoretical value C, 90.60；H,5.17；N,4.23；Test value: C, 90.61；H,5.17；
N,4.22。ESI-MS(m/z)(M+): theoretical value 662.27, measured value 662.91.
Embodiment 7: the synthesis of compound 49:
The preparation method of compound 49 is with embodiment 5, the difference is that replacing intermediate M1-4 using intermediate M1-6.
Elemental analysis structure (molecular formula C47H29N3): theoretical value C, 88.79；H,4.60；N,6.61；Test value: C, 88.78；H,4.60；
N,6.62。ESI-MS(m/z)(M+): theoretical value 635.24, measured value 635.24.
Embodiment 8: the synthesis of compound 54:
The preparation method of compound 54 is with embodiment 5, the difference is that replacing intermediate M1-4 using intermediate M1-7.
Elemental analysis structure (molecular formula C47H29N3): theoretical value C, 88.79；H,4.60；N,6.61；Test value: C, 88.78；H,4.60；
N,6.62。ESI-MS(m/z)(M+): theoretical value 635.24, measured value 635.75.
Embodiment 9: the synthesis of compound 64:
The preparation method of compound 64 is with embodiment 2, the difference is that replacing raw material E2-1 using raw material E2-2.Element
Analyze structure (molecular formula C45H28N2): theoretical value C, 90.58；H,4.73；N,4.69；Test value: C, 90.59；H,4.73；N,
4.68。ESI-MS(m/z)(M+): theoretical value 596.23, measured value 596.81.
Embodiment 10: the synthesis of compound 82:
The preparation method of compound 82 is with embodiment 2, the difference is that intermediate M2-1 is replaced using intermediate M2-7,
Raw material E2-2 replaces raw material E2-1.Elemental analysis structure (molecular formula C47H28N2O): theoretical value C, 88.66；H,4.43；N,4.40；
Test value: C, 88.66；H,4.43；N,4.41.ESI-MS(m/z)(M+): theoretical value 636.22, measured value 636.35.
Embodiment 11: the synthesis of compound 90:
The preparation method of compound 90 is with embodiment 5, the difference is that intermediate M1-4 is replaced using intermediate M1-9,
Raw material E1-2 replaces raw material E1-1.Elemental analysis structure (molecular formula C44H30N2): theoretical value C, 90.07；H,5.15；N,4.77；
Test value: C, 90.07；H,5.15；N,4.78.ESI-MS(m/z)(M+): theoretical value 586.24, measured value 586.61.
Embodiment 12: the synthesis of compound 101:
The preparation method of compound 101 is with embodiment 2, the difference is that replacing intermediate M2- using intermediate M2-8
1, raw material E2-2 replace raw material E2-1.Elemental analysis structure (molecular formula C50H34N2): theoretical value C, 90.60；H,5.17；N,
4.23；Test value: C, 90.59；H,5.17；N,4.24.ESI-MS(m/z)(M+): theoretical value 662.27, measured value are
662.72。
Embodiment 13: the synthesis of compound 113:
The preparation method of compound 113 is with embodiment 2, the difference is that replacing intermediate M2- using intermediate M2-9
1, raw material E2-2 replace raw material E2-1.Elemental analysis structure (molecular formula C53H33N3): theoretical value C, 89.42；H,4.67；N,
5.90；Test value: C, 89.42；H,4.67；N,5.91.ESI-MS(m/z)(M+): theoretical value 711.27, measured value are
711.91。
Embodiment 14: the synthesis of compound 127:
The preparation method of compound 127 is with embodiment 2, the difference is that replacing intermediate M2- using intermediate M2-2
1, raw material E2-3 replace raw material E2-1.Elemental analysis structure (molecular formula C46H27N3): theoretical value C, 88.86；H,4.38；N,
6.76；Test value: C, 88.85；H,4.38；N,6.77.ESI-MS(m/z)(M+): theoretical value 621.22, measured value are
621.41。
Embodiment 15: the synthesis of compound 134:
The preparation method of compound 134 is with embodiment 5, the difference is that using intermediate using intermediate M1-11 replacement
Body M1-4, raw material E1-3 replace raw material E1-1.Elemental analysis structure (molecular formula C42H23N3O): theoretical value C, 86.13；H,3.96；
N,7.17；Test value: C, 86.13；H,3.96；N,7.16.ESI-MS(m/z)(M+): theoretical value 585.18, measured value are
585.79。
Embodiment 16: the synthesis of compound 147:
The preparation method of compound 147 is with embodiment 5, the difference is that replacing intermediate M1- using intermediate M1-9
4, raw material E1-3 replace raw material E1-1.Elemental analysis structure (molecular formula C45H29N3): theoretical value C, 88.35；H,4.78；N,
6.87；Test value: C, 88.34；H,4.78；N,6.88.ESI-MS(m/z)(M+): theoretical value 611.24, measured value are
611.88。
Embodiment 17: the synthesis of compound 162:
The preparation method of compound 162 is with embodiment 2, the difference is that replacing intermediate M2- using intermediate M2-10
1, raw material E2-3 replace raw material E2-1.Elemental analysis structure (molecular formula C51H33N3): theoretical value C, 89.05；H,4.84；N,
6.11；Test value: C, 89.04；H,4.84；N,6.12.ESI-MS(m/z)(M+): theoretical value 687.27, measured value are
687.71。
Embodiment 18: the synthesis of compound 172:
The preparation method of compound 172 is with embodiment 5, the difference is that intermediate M1-1 replaces intermediate M1-4, it is former
Expect that E1-4 replaces raw material E1-1.Elemental analysis structure (molecular formula C41H22N4): theoretical value C, 86.30；H,3.89；N,9.82；It surveys
Examination value: C, 86.30；H,3.89；N,9.81.ESI-MS(m/z)(M+): theoretical value 570.18, measured value 570.84.
Embodiment 19: the synthesis of compound 184:
The preparation method of compound 184 is with embodiment 2, the difference is that replacing intermediate M2- using intermediate M2-2
1, raw material E2-4 replace raw material E2-1.Elemental analysis structure (molecular formula C47H26N4): theoretical value C, 87.28；H,4.05；N,
8.66；Test value: C, 87.28；H,4.05；N,8.67.ESI-MS(m/z)(M+): theoretical value 646.22, measured value are
646.51。
Embodiment 20: the synthesis of compound 198:
The preparation method of compound 198 is with embodiment 2, the difference is that replacing intermediate M2- using intermediate M2-11
1, raw material E2-4 replace raw material E2-1.Elemental analysis structure (molecular formula C49H26N4O): theoretical value C, 85.70；H,3.82；N,
8.16；Test value: C, 85.70；H,3.82；N,8.17.ESI-MS(m/z)(M+): theoretical value 686.21, measured value are
686.77。
Embodiment 21: the synthesis of compound 211:
The preparation method of compound 211 is with embodiment 2, the difference is that replacing intermediate M2- using intermediate M2-5
1, raw material E2-4 replace raw material E2-1.Elemental analysis structure (molecular formula C52H32N4): theoretical value C, 87.62；H,4.52；N,
7.86；Test value: C, 87.63；H,4.52；N,7.85.ESI-MS(m/z)(M+): theoretical value 712.26, measured value are
712.86。
Embodiment 22: the synthesis of compound 220:
The preparation method of compound 220 is with embodiment 5, the difference is that replacing intermediate M1- using intermediate M1-6
4, raw material E1-4 replace raw material E1-1.Elemental analysis structure (molecular formula C49H27N5): theoretical value C, 85.82；H,3.97；N,
10.21；Test value: C, 85.81；H,3.97；N,10.22.ESI-MS(m/z)(M+): theoretical value 685.23, measured value are
685.53。
The compounds of this invention can be used as emitting layer material use, to the compounds of this invention 34, compound 54, compound
162, current material CBP carries out the test of hot property, luminescent spectrum and cyclic voltammetric stability, and test result is as shown in table 2.
Table 2
| Compound | Td(℃) | λPL(nm) | Cyclic voltammetric stability |
| Compound 34 | 422 | 470 | It is excellent |
| Compound 54 | 430 | 460 | It is excellent |
| Compound 162 | 444 | 474 | It is excellent |
| Material C BP | 353 | 369 | Difference |
Note: thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in the TGA-50H heat of Japanese Shimadzu Corporation
It is measured on weight analysis instrument, nitrogen flow 20mL/min；λPLIt is sample solution fluorescence emission wavelengths, opens up Pu Kang using Japan
The measurement of SR-3 spectroradiometer；Cyclic voltammetric stability be by cyclic voltammetry observe material redox characteristic come into
Row identification；Test condition: test sample is dissolved in the methylene chloride and acetonitrile mixed solvent that volume ratio is 2:1, concentration 1mg/mL, electricity
Solving liquid is the tetrabutyl ammonium tetrafluoroborate of 0.1M or the organic solution of hexafluorophosphate.Reference electrode is Ag/Ag+ electricity
Pole is titanium plate to electrode, and working electrode is ITO electrode, and cycle-index is 20 times.
By upper table data it is found that the compounds of this invention has preferable oxidation-reduction stability, higher thermal stability is closed
Suitable luminescent spectrum, so that getting a promotion using the compounds of this invention as the OLED device efficiency of emitting layer material and service life.
By the following examples 1~21 and Comparative Examples 1 and 2,3 the present invention will be described in detail synthesis compounds be used as luminescent layer in the devices
The application effect of material of main part.The structure composition of each embodiment obtained device is as shown in table 3.The test result of obtained device is shown in Table
Shown in 4.
Device embodiments 1
2/ hole injection layer of transparent substrate layer 1/ITO anode layer, 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4
(the weight ratio blending of compound 34 and GD19 according to 100:5, thickness the 30nm)/electronics of (TAPC, thickness 80nm)/luminescent layer 5 passes
Defeated 6 (TPBI, thickness 40nm)/electron injecting layer of layer, 7 (LiF, thickness 1nm)/cathode reflection electrode layer 8 (Al).The material being related to
Expect that structural formula is as follows:
Specific preparation process is as follows:
Transparent substrate layer 1 is transparent substrate, such as transparent PI film, glass.Ito anode layer 2 (film thickness 150nm) is carried out
Washing successively carries out neutralizing treatment, pure water, drying, then carry out ultraviolet-ozone washing to remove the transparent surface ITO
Organic residue.On having carried out the ito anode layer 2 after above-mentioned washing, using vacuum deposition apparatus, vapor deposition film thickness is 10nm
Molybdenum trioxide MoO3It is used as hole injection layer 3.And then the TAPC of 80nm thickness is deposited as hole transmission layer 4.On
After stating hole mobile material vapor deposition, the luminescent layer 5 of OLED luminescent device is made, structure includes that OLED luminescent layer 5 is made
Use material compound 34 as material of main part, for GD19 as dopant material, dopant material doping ratio is 5% weight ratio, is shone
Tunic thickness is 40nm.After above-mentioned luminescent layer 5, continuation vacuum evaporation electron transport layer materials are TPBI.The vacuum of the material
Vapor deposition film thickness is 40nm, this layer is electron transfer layer 6.On electron transfer layer 6, by vacuum deposition apparatus, making film thickness is
Lithium fluoride (LiF) layer of 1nm, this layer are electron injecting layer 7.On electron injecting layer 7, by vacuum deposition apparatus, film is made
Thickness is aluminium (Al) layer of 80nm, this layer is the use of cathode reflection electrode layer 8.After completing OLED luminescent device as described above, use
Well known driving circuit connects anode and cathode, the current efficiency of measurement device and the service life of device.
Table 3
Table 4
Illustrate: the current efficiency of comparative example 1 is 6.5cd/A (@10mA/cm2)；LT95 life time decay under 5000nit brightness
For 3.8Hr.The current efficiency of comparative example 2 is 24.6cd/A (@10mA/cm2)；LT95 life time decay is under 5000nit brightness
4.3Hr.The current efficiency of comparative example 3 is 25.1cd/A (@10mA/cm2)；LT95 life time decay is under 5000nit brightness
7.8Hr.Life-span test system is owner of the present invention and the OLED device life-span tester that Shanghai University is studied jointly.
By the result of table 4 can be seen that compound of the present invention can be applied to OLED luminescent device production, and with than
It is compared compared with example 1,2,3, the driving service life that either efficiency or service life obtain larger change, especially device obtains biggish
It is promoted.
From the point of view of the test data provided by the embodiment, the compounds of this invention is as emitting layer material in OLED luminescent device
In have good application effect, have good industrialization prospect.The OLED device of further material preparation of the present invention exists
Efficiency is also more stable when low operating temperatures, by device embodiments 1,12,20 and device comparative example 1, comparative example 2, comparative example 3
Efficiency test is carried out in -10~80 DEG C of sections, acquired results are as shown in table 5 and Fig. 2.
Table 5
From the data of table 5 and Fig. 2 it is found that device embodiments 1,12,20 are material of the present invention and the device that known materials are arranged in pairs or groups
Part structure is compared with device comparative example 1, comparative example 2, comparative example 3, and not only Efficiency at Low Temperature is high, but also in temperature elevation process,
Efficiency steadily increases.
Although disclosing the present invention by embodiment and preferred embodiment, it should be appreciated that it is public that the present invention is not limited to institutes
The embodiment opened.On the contrary, it will be understood by those skilled in the art that it is intended to various modifications and similar arrangement.Therefore, institute
Attached the scope of the claims should be consistent with widest explanation to cover all such modifications and similar arrangement.
Claims (10)
1. a kind of using cyano benzene as the compound of core, which is characterized in that shown in the structure of the compound such as general formula (1):
In general formula (1), X1、X2And X3Independently be expressed as cyano or hydrogen atom；X1、X2And X3It is not simultaneously hydrogen atom；
In general formula (1), R1、R2Independently be expressed as hydrogen atom, substituted or unsubstituted C6-60Aryl contains one or more
A heteroatomic substituted or unsubstituted 5-60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；R1With R2It is not former for hydrogen simultaneously
Son；
In general formula (1), Ar is expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains one or more heteroatomic substitutions
Or unsubstituted 5-60 member heteroarylidene；The hetero atom is nitrogen, oxygen or sulphur；
In general formula (1), R3It is expressed as structure shown in general formula (2) or general formula (3)；R4It is expressed as structure shown in general formula (2)；
In general formula (3), X4It is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, the aryl of linear or branched alkyl group substitution replace
One of the imido grpup that alkylidene, alkyl-substituted imido grpup or aryl replace；
General formula (2) passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL'2-CL’3Key or CL’3-CL’4Key and general formula
(1) and ring connects；
General formula (3) passes through CL’1-CL’2Key, CL'2-CL’3Key or CL’3-CL’4Key is connected with general formula (1) and ring.
2. according to claim 1 a kind of using cyano benzene as the compound of core, which is characterized in that the knot of the compound
Shown in structure such as general formula (4) or general formula (5):
3. according to claim 1 a kind of using cyano benzene as the compound of core, which is characterized in that the R1、R2It is only respectively
Vertical is expressed as hydrogen atom, phenyl, xenyl, naphthalene or anthryl；The Ar is expressed as singly-bound, phenylene, biphenylene, sub- naphthalene
One kind of base or anthrylene.
4. according to claim 1 a kind of using cyano benzene as the compound of core, which is characterized in that in general formula (1)It indicates are as follows:
In any one.
5. according to claim 1 a kind of using cyano benzene as the compound of core, which is characterized in that describedIt indicates are as follows:
In any one.
6. according to claim 1 a kind of using cyano benzene as the compound of core, which is characterized in that the tool of the compound
Body structural formula are as follows:
In any one.
7. a kind of, to prepare claim 1~6 described in any item a kind of using cyano benzene as the method for the compound of core, feature
It is, the reaction equation occurred in preparation process is:
When Ar indicates singly-bound:
Specific preparation step are as follows:
Raw material bromo-derivative E1 and intermediate M1 are dissolved in dry toluene, Pd is added after deoxygenation2(dba)3With tri-tert phosphorus,
95~110 DEG C of 10~24 hours of reaction under an inert atmosphere constantly monitor reaction process with TLC in reaction process, to raw material
After fully reacting, filtrate is rotated and removes dry toluene by cooling, filtering, and crude product crosses silicagel column, obtains target compound；Institute
The dosage for stating dry toluene is every gram of intermediate M1 using 30~50mL toluene, and the molar ratio of bromo-derivative E1 and intermediate M1 is 1:
1.0~1.5, Pd2(dba)3Molar ratio with bromo-derivative E1 is 0.006~0.02:1, mole of tri-tert-butylphosphine and bromo-derivative E1
Than for 0.006~0.02:1, the molar ratio of sodium tert-butoxide and bromo-derivative E1 are 2.0~3.0:1；
When Ar does not indicate singly-bound:
Intermediate M2 and raw material E2 are dissolved in the mixed solution of toluene and ethyl alcohol, Pd (PPh is added after deoxygenation3)4And K2CO3,
95~110 DEG C of 10~24 hours of reaction under an inert atmosphere constantly monitor reaction process with TLC in reaction process, to raw material
After fully reacting, filtrate is rotated the mixed solution for removing toluene and ethyl alcohol by cooling, filtering, and crude product crosses silicagel column, obtains mesh
Mark compound；The dosage of the toluene and ethyl alcohol is that every gram of intermediate M2 uses 30~50mL toluene and 5~10mL ethyl alcohol, former
The molar ratio for expecting E2 and intermediate M2 is (1~1.5): 1, Pd (PPh3)4Molar ratio with intermediate M2 is (0.006~0.02):
1, K2CO3Molar ratio with intermediate M2 is (1.5~2): 1.
8. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes at least one layer of functional layer
It is described in any item a kind of using cyano benzene as the compound of core containing claim 1~6.
9. a kind of organic electroluminescence device, including luminescent layer, which is characterized in that the luminescent layer contains claim 1~6 times
It is a kind of using cyano benzene as the compound of core described in one.
10. a kind of illumination or display element, which is characterized in that including the organic electroluminescence device as described in claim 8-9.
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| CN113402525A (en) * | 2021-05-21 | 2021-09-17 | 吉林奥来德光电材料股份有限公司 | Compound containing cyano aromatic group, synthetic method thereof, organic material, functional layer and organic electroluminescent device |
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