CN103936720A - Compound containing spirofluorene structural unit, its preparation method and its application - Google Patents

Compound containing spirofluorene structural unit, its preparation method and its application Download PDF

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CN103936720A
CN103936720A CN201310680933.5A CN201310680933A CN103936720A CN 103936720 A CN103936720 A CN 103936720A CN 201310680933 A CN201310680933 A CN 201310680933A CN 103936720 A CN103936720 A CN 103936720A
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compound
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carbon atoms
layer
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CN103936720B (en
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郭剑
隋岩
曹建华
李雅敏
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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Abstract

The invention discloses a compound containing a spirofluorene structural unit, its preparation method and its application. A structural general formula of the compound containing the spirofluorene structural unit is shown as a formula I. The nuclear magnetic detection of the compound is correct. The blue light luminescent material has high efficiency and high stability, the raw material is easily available, the material of the compound is simple to prepare, the total yield is high, and the compound has important application value for researching progress and application of the blue light material.

Description

Compound that contains spiral shell fluorene structural units and preparation method thereof and application
Technical field
The invention belongs to technical field of organic synthesis, relate to a kind of compound that contains spiral shell fluorene structural units and preparation method thereof and application.
Background technology
For organic electroluminescent (being called for short OLED) and relevant research, as far back as people such as pope in 1963, first found the electro optical phenomenon of organic compound single-crystal anthracene.A kind of amorphous membranous type device has been made by the method for evaporation organic molecule by the Kodak of the U.S. in 1987, and driving voltage has been dropped in 20V.This class device owing to thering is ultra-thin, complete solidify, luminous, brightness is high, visual angle is wide, fast response time, driving voltage is low, power consumption is little, bright in luster, contrast gradient is high, technological process is simple, good temp characteristic, can realize the advantages such as softness demonstration, can be widely used in flat-panel monitor and area source, therefore obtain studying widely, develop and used.
Through the development of twenties years, organic EL Material round Realization red, blue, green emitting, Application Areas has also expanded to the fields such as polymer and metal complex from small molecules.Recent years, organic electroluminescent technique of display obtained huge progress, and it is luminous to have realized Red, Blue, Green.But at present known with practical value also very limited with materials potentiality, particularly the organic materials of overall target excellence is badly in need of development and exploitation, green material is with fastest developing speed, substantially can meet the demand of commercialization practicality, and the more problems of red and blue material still has distance from practical application.Therefore, the molecular designing of stable, high-level efficiency Red and blue light material with become important research contents.
Summary of the invention
The object of this invention is to provide a kind of compound that contains spiral shell fluorene structural units and preparation method thereof and application.
The compound that contains spiral shell fluorene structural units provided by the invention, its general structure is suc as formula shown in I,
Formula I
In described formula I, R afor R 1-(Z 1-A 1-Z 2) x-;
R bfor-(Z 3-A 2-Z 4) y-R 2;
Wherein, R 1and R 2all be selected from H ,-F ,-Cl ,-CN ,-CF 3with-OCF 3, the total number of carbon atoms alkyl that is 1-15 of alkyl that the total number of carbon atoms is 1-15, alkoxyl group that the total number of carbon atoms is 1-15, normal olefine base that the total number of carbon atoms is 2-15, fluoro is, any one in the normal olefine base that the total number of carbon atoms of the alkoxyl group that the total number of carbon atoms of fluoro is 1-15 and fluoro is 2-15;
Z 1, Z 2, Z 3and Z 4all be selected from-O-,-S-,-OCO-,-COO-,-CO-,-CH 2o-,-OCH 2-,-CF 2o-,-OCF 2-, the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms is 1-15, normal olefine base that the total number of carbon atoms is 2-15, straight-chain alkynyl that the total number of carbon atoms is 2-15, fluoro is 1-15, fluoro alkylene that is 2-15 and at least one in carbon-carbon single bond;
A 1and A 2all be selected from 1,4-cyclohexylidene, 1,4-phenylene, two phenenyl phosphinyl, N-phenyl-carbazole-2-base, N-phenyl-carbazole-3-base, 9,10-anthryl, 1-naphthyl, 4-triphenylamine base, 2,5-pyrimidyl, 3,9-carbazyl, 2,5-pyridyl, 2,5-tetrahydrochysene-2H-pyranyl, 1,3-diox-2,5-base, 1,2,4-oxadiazole-3,1 of 5-base, fluoro, any one in the Isosorbide-5-Nitrae-phenylene of 4-cyclohexylidene, fluoro, the pyranoid ring of fluoro two bases, cyclic lactone two bases, five yuan of oxa-ring two bases, pentatomic sulphur heterocycle two bases, penta azacyclo two bases and carbon-carbon single bonds;
X and y are the integer of 0-3;
Described x or y are 2 or at 3 o'clock, structural unit Z 1-A 1-Z 2in, Z 1identical or different, A 1identical or different, Z 2identical or different; Structural unit Z 3-A 2-Z 4in, Z 3identical or different, A 2identical or different, Z 4identical or different.
Concrete, R afor
R bfor or naphthyl;
Shown in described formula I, compound is specially any one in following compound:
Compound shown in described formula I is also for being prepared as follows the compound obtaining.
The method of the described formula I compound of preparation provided by the invention, comprises the steps: that the pH value in reaction system is 8-14 and Pd (PPh 3) 4under the condition existing as catalyzer, compound shown in formula VII compound and formula VIII is carried out to Suzuki cross-coupling reaction, obtain after completion of the reaction compound shown in formula I;
Formula VII
R A-B(OH) 2
Formula VIII
Described formula VII to formula VIII, R aand R bdefinition all identical with the definition in aforementioned formula I.
Shown in above-mentioned preparation formula I, the reaction equation of compound method is as follows:
In aforesaid method, described formula VII compound and R a-B (OH) 2mol ratio be 1:1～2, specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.1; Formula VII compound and Pd (PPh 3) 4molar ratio be 1:0.002～0.05, specifically can be 1:0.002,1:0.005,1:0.01,1:0.02,1:0.05, preferably 1:0.05;
In actually operating, can select Na 2cO 3regulating the pH value of reaction system is 8～14, formula VII compound and Na 2cO 3mol ratio be 1:1～3, specifically can be 1:1,1:1.5,1:2,1:2.5,1:3, preferably 1:3;
In described Suzuki cross-coupling reaction step, temperature is 60 ℃～160 ℃, specifically can be 60 ℃～80 ℃, 80 ℃～100 ℃, 100 ℃～120 ℃, 120 ℃～140 ℃, 140 ℃～160 ℃, preferably 80 ℃～100 ℃; Reaction times is 4～10 hours, is preferably 6～8 hours;
Described Suzuki cross-coupling reaction carries out in solvent;
Described solvent is specifically selected from least one in tetrahydrofuran (THF), hexane, acetic acid, dimethylbenzene, ethanol, toluene, water, orthodichlorobenzene, acetic acid and Isosorbide-5-Nitrae-dioxane;
The reaction atmosphere of described Suzuki cross-coupling reaction is inert atmosphere, preferably argon gas atmosphere.
In above-mentioned preparation method, shown in initial reactant formula VII, compound obtains for being prepared as follows:
1) by shown in formula II 1,1 '-'-dibromobiphenyl carries out negative ionization with n-Butyl Lithium and reacts, add again after completion of the reaction dibenzosuberenone shown in formula III to carry out substitution reaction, rise to after completion of the reaction room temperature and 6N hydrochloric acid carries out ring closure reaction, obtain compound shown in formula IV;
2) in reaction system, use Na 2cO 3as alkali, system pH is 9-14 and Pd (PPh 3) 4under the condition existing as catalyzer, compound shown in compound shown in step 1) gained formula IV and formula IX is carried out to substitution reaction, react the complete compound shown in formula V that obtains;
Formula V
R B-B(OH) 2
Formula IX
3) by step 2) compound shown in gained formula V and benzene seleninic acid acid anhydride carry out oxidizing reaction, obtains after completion of the reaction compound shown in formula VI;
Formula VI
4) compound shown in step 3) gained formula VI is carried out to clasp with p-tert-butyl-aniline, p-bromobenzaldehyde and ammonium acetate and react, react the complete compound shown in formula VII that obtains;
Formula VII
In the step 1) of aforesaid method; the mol ratio of formula II compound and dibenzosuberenone is 1:0.5～1.5; specifically can be 1:0.5,1:0.6,1:0.7,1:0.8,1:0.9,1:1.0,1:1.1,1:1.2,1:1.3,1:1.4,1:1.5, preferably 1:0.7; The molar ratio of formula II compound and n-Butyl Lithium is 1:1～2, specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.0; The mol ratio of formula II compound and 6N hydrochloric acid is 1:2～8, specifically can be 1:2,1:3,1:4,1:5,1:6,1:7,1:8, preferably 1:5;
In described reactions steps, negative ionization temperature of reaction is-80 ℃～0 ℃, specifically can be-80 ℃～-60 ℃ ,-60 ℃～-40 ℃ ,-40 ℃～-20 ℃ ,-20 ℃～0 ℃, preferably-80 ℃～-60 ℃; Reaction times is 1～6 hour, is preferably 1～2 hour; Substitution reaction temperature is-60 ℃～20 ℃, and-60 ℃～-40 ℃ ,-40 ℃～-20 ℃ ,-20 ℃～0 ℃, 0 ℃～20 ℃, preferably 0 ℃～20 ℃, the concrete reaction times is 1～6 hour, is preferably 1～2 hour; Ring closure reaction temperature is 0 ℃～120 ℃, and 0 ℃～30 ℃, 30 ℃～60 ℃, 60 ℃～90 ℃, 90 ℃～120 ℃, preferably 90 ℃～120 ℃, the concrete reaction times is 1～6 hour, is preferably 1～2 hour;
Described step 2) in, described formula IV compound and R b-B (OH) 2mol ratio be 1:1～2, specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.1; Formula IV compound and Pd (PPh 3) 4molar ratio be 1:0.002～0.05, specifically can be 1:0.002,1:0.005,1:0.01,1:0.02,1:0.05, preferably 1:0.05; Select Na 2cO 3regulating the pH value of reaction system is 8～14, formula IV compound and Na 2cO 3mol ratio be 1:1～3, specifically can be 1:1,1:1.5,1:2,1:2.5,1:3, preferably 1:3; In described reactions steps, temperature is 60 ℃～160 ℃, specifically can be 60 ℃～80 ℃, 80 ℃～100 ℃, 100 ℃～120 ℃, 120 ℃～140 ℃, 140 ℃～160 ℃, preferably 80 ℃～100 ℃; Reaction times is 4～10 hours, is preferably 6～8 hours;
In described step 3), the mol ratio of described formula V compound and benzene seleninic acid acid anhydride is 1:1～2, specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.1; In described reactions steps, temperature is 80 ℃～180 ℃, specifically can be 80 ℃～100 ℃, 100 ℃～120 ℃, 120 ℃～140 ℃, 140 ℃～160 ℃, 160 ℃～180 ℃, preferably 140 ℃～160 ℃; Reaction times is 12～24 hours, is preferably 16～18 hours;
In described step 4), the mol ratio of described VI compound and p-bromobenzaldehyde is 1:1～2, specifically can be 1:1.0,1:1.2,1:1.4,1:1.6,1:1.8,1:2.0, preferably 1:1.0; The mol ratio of the compound shown in formula VI and ammonium acetate is 1:1～15, specifically can be 1:3,1:6,1:9,1:12,1:15, preferably 1:12; The mol ratio of the compound shown in formula VI and p-tert-butyl-aniline is 1:1～2, specifically can be 1:1.0,1:1.2,1:1.4,1:1.6,1:1.8,1:2.0, preferably 1:1.2; In described reactions steps, temperature is 80 ℃～130 ℃, specifically can be 80 ℃～90 ℃, 90 ℃～100 ℃, 100 ℃～110 ℃, 110 ℃～120 ℃, 120 ℃～130 ℃, preferably 110 ℃～120 ℃; Time is 12～36 hours, is preferably 18～24 hours;
In addition, the application of compound in preparing luminescent material shown in the luminescent material that contains compound shown in the formula I that the invention described above provides and this formula I, also belongs to protection scope of the present invention; Wherein, the fluorescent emission wavelength of described luminescent material is specially 414-461nm, is more specifically 414,426,435,445,454,461 or 426-454nm;
Compound shown in the formula I that the invention described above provides, preparing luminescent material or organic electroluminescence device or being prepared with the application in OLED and the luminescent material that contains compound shown in formula I or organic electroluminescence device or Organic Light Emitting Diode, also belongs to protection scope of the present invention; Wherein, the fluorescent emission wavelength of described luminescent material is specially 414-461nm, is more specifically 414,426,435,445,454,461 or 426-454nm;
Wherein, described organic electroluminescence device specifically can be following structure:
By transparent substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer, formed successively from the bottom to top;
Wherein, the material that forms described transparent substrate is glass or flexible substrate, and flexible substrate adopts a kind of material in polyester, polyimide compounds;
The material that forms described anode layer is inorganic materials or organic conductive polymkeric substance; Wherein, described inorganic materials is tin indium oxide (being called for short ITO), zinc oxide, stannic oxide, gold and silver or copper; Described organic conductive polymkeric substance is selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material that forms described hole injection layer is TDATA;
The structural formula of described TDATA is as follows:
The material that forms described hole transmission layer is NPB;
The structural formula of described NPB is as follows:
The material that forms described organic luminous layer is compound shown in formula I provided by the invention;
The material that forms described electron transfer layer is Alq3, Gaq3 or BPhen;
Wherein, the structural formula of Alq3, BPhen and Gaq3 is as follows successively:
The material that forms described cathode layer is selected from any one or the alloy of any two kinds of compositions or the fluorochemical of following element in following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.
The thickness of described hole injection layer is 30-50nm, is specially 40nm;
The thickness of described hole transmission layer is 5-15nm, is specially 10nm;
The thickness of described organic luminous layer is 10-100nm, is specially 40nm;
The thickness of described electron transfer layer is 40-60nm, is specially 50nm;
The thickness of described cathode layer is 90-110nm, is specially 100nm.
Compound provided by the invention, nuclear-magnetism detects correct.This blue light emitting material has advantages of high-level efficiency, high stability, and raw material is easy to get, and prepares easyly, and overall yield is high, and the development and application for research blue light material, has important using value.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
Testing tool and method that following embodiment carries out performance test to OLED material and device are as follows:
Emission wavelength and tristimulus coordinates: use spectrum scanner PhotoResearch PR-655 test;
Current density and a bright voltage: use digital sourcemeter Keithley 2420 tests;
Power efficiency: use NEWPORT 1931-C test.
Following embodiment 1 initial reactant 1e used is prepared as follows and obtains:
Step 1: synthetic
In 500mL reaction flask, drop into 1 of 30mmol, the tetrahydrofuran (THF) of 1 '-'-dibromobiphenyl and 100mL, liquid nitrogen ethanol bath is cooled to-78 ℃.Drip the hexane solution of the n-Butyl Lithium of 30mmol, drip off rear maintenance-78 ℃ reaction 1 hour.Then drip the 80mL tetrahydrofuran solution of the dibenzosuberenone of 20mmole, drip off rear maintenance-78 ℃ reaction 1 hour.Slowly rise to room temperature reaction 1 hour, then add the saturated sodium-chloride water solution of 30mL, use 15mL dichloromethane extraction three times, be spin-dried for to obtain white solid.In the round-bottomed bottle of another 500mL, add the white solid obtaining, then add the acetic acid stirring and dissolving of 50mL, add the concentrated hydrochloric acid of 10mL, back flow reaction 1 hour.System is cooled to room temperature, suction filtration, water and sherwood oil drip washing filter cake, obtain white solid product, yield: 59% respectively.
Step 2: synthetic
In 250mL reaction flask, drop into step 1 gained compound 1a, the 1b of 9.5mmol of 7.9mmol, the sodium carbonate of 31.6mmol, the Pd (PPh of 0.4mmol 3) 4, then drop into the water of the toluene of 80mL, the ethanol of 15mL and 15mL, 100 ℃ of reactions 8 hours.The ethyl acetate that adds saturated aqueous common salt and the 50mL of 50mL to system, stirs separatory, 20mL ethyl acetate extraction 2 times for water, and 20mL saturated common salt washing 2 times for organic phase, merges organic phase, after being spin-dried for, obtains black solid.Cross silicagel column, sherwood oil: ethyl acetate=6:1 drip washing obtains white solid product, yield: 76%
Step 3: synthetic
In 100mL reaction flask, drop into the adjacent nitro bromobenzene of step 2 gained compound 1b, the 2.6mmol of 2.4mmol, the salt of wormwood of 7.2mmol, the Pd (PPh of 0.12mmol 3) 4, then drop into the water of the toluene of 30mL, the ethanol of 10mL and 10mL, 100 ℃ of reactions 8 hours.The ethyl acetate that adds saturated aqueous common salt and the 20mL of 20mL to system, stirs separatory, 20mL ethyl acetate extraction 2 times for water, and 20mL saturated common salt washing 2 times for organic phase, merges organic phase, after being spin-dried for, obtains black solid.Cross silicagel column, sherwood oil: methylene dichloride=6:1 drip washing obtains white solid product, yield: 82%.
Step 4: synthetic
In 250mL reaction flask, drop into step 3 gained compound 1d, the p-tert-butyl-aniline of 2.2mmol, the ammonium acetate of the p-bromobenzaldehyde of 1.8mmol, 21.9mmol and the acetic acid of 20mL of 1.8mmol, 110 ℃ are reacted 24 hours.System is cooling, to pour in the methyl alcohol of 100mL, suction filtration, obtains gray solid.Orthodichlorobenzene, 140 ℃ are reacted 4 hours.After being drained, system obtains yellow black solid.Cross silicagel column, sherwood oil: methylene dichloride=2:1 drip washing obtains white solid product, yield: 27%.
Following embodiment 2 initial reactant 2e used is prepared as follows and obtains:
Step 1: synthetic
Step 1 with aforementioned preparation 1e method.
Step 2: synthetic
Step 2 according to aforementioned preparation 1e method, replaces with 2b by 1b, obtains target compound, yield: 88%.
Step 3: synthetic
Step 3 according to aforementioned preparation 1e method, replaces with 2c by 1c, obtains target compound, yield: 77%.
Step 4: synthetic
Step 4 according to aforementioned preparation 1e method, replaces with 2d by 1d, obtains target compound, yield: 35%.
Following embodiment 3 initial reactant 3e used is prepared as follows and obtains:
Step 1: synthetic
Step 1 with aforementioned preparation 1e method.
Step 2: synthetic
Step 2 according to aforementioned preparation 1e method, replaces with 3b by 1b, obtains target compound, yield: 69%.
Step 3: synthetic
Step 3 according to aforementioned preparation 1e method, replaces with 3c by 1c, obtains target compound, yield: 81%.
Step 4: synthetic
Step 4 according to aforementioned preparation 1e method, replaces with 3d by 1d, obtains target compound, yield: 44%.
Following embodiment 4 initial reactant 4e used is prepared as follows and obtains:
Step 1: synthetic
Step 1 with aforementioned preparation 1e method.
Step 2: synthetic
Step 2 according to aforementioned preparation 1e method, replaces with 4b by 1b, obtains target compound, yield: 77%.
Step 3: synthetic
Step 3 according to aforementioned preparation 1e method, replaces with 4c by 1c, obtains target compound, yield: 72%.
Step 4: synthetic
Step 4 according to aforementioned preparation 1e method, replaces with 4d by 1d, obtains target compound, yield: 52%.
Following embodiment 5 initial reactant 5e used is prepared as follows and obtains:
Step 1: synthetic
Step 1 with aforementioned preparation 1e method.
Step 2: synthetic
Step 2 according to aforementioned preparation 1e method, replaces with 5b by 1b, obtains target compound, yield: 79%.
Step 3: synthetic
Step 3 according to aforementioned preparation 1e method, replaces with 5c by 1c, obtains target compound, yield: 82%.
Step 4: synthetic
Step 4 according to aforementioned preparation 1e method, replaces with 5d by 1d, obtains target compound, yield: 55%.
Following embodiment 6 initial reactant 6e used is prepared as follows and obtains:
Step 1: synthetic
Step 1 with aforementioned preparation 1e method.
Step 2: synthetic
Step 2 according to aforementioned preparation 1e method, replaces with 5b by 1b, obtains target compound, yield: 79%.
Step 3: synthetic
Step 3 according to aforementioned preparation 1e method, replaces with 5c by 1c, obtains target compound, yield: 82%.
Step 4: synthetic
Step 4 according to aforementioned preparation 1e method, replaces with 5d by 1d, obtains target compound, yield: 55%.
Embodiment 1, compound preparation
In 100mL reaction flask, drop into the triphenylamine boric acid of compound 1e, 0.49mmol of 0.45mmol, the Pd (PPh of 0.02mmol 3) 4na with 1.8mmol 2cO 3, then system drops into the water of the toluene of 50mL, the ethanol of 10mL and 10mL, is then heated to 110 ℃ of backflows and carries out Suzuki cross-coupling reaction 6 hours.To system, add the ethyl acetate of 30mL and the water of 30mL, stir separatory, 30mL ethyl acetate extraction 2 times for water, 30mL saturated common salt washing 2 times for organic phase, merges organic phase, after being spin-dried for, obtains yellow solid.Cross silicagel column, sherwood oil: methylene dichloride=4:1 drip washing obtains white solid product, yield: 89%.
1H?NMR(CDCl 3,300MHz):δ=8.48-8.49(d,1H),8.10-8.12(m,2H),7.85-7.89(m,5H),7.06-7.66(m,28H),7.04-7.06(d,2H),6.94-6.95(d,1H),6.81-6.84(m,2H),6.63-6.69?(m,6H),6.04-6.06(d,2H),1.35(s,9H)。
Second-order transition temperature Tg:267 ℃;
Uv-absorbing wavelength: 255nm, 275nm, 315nm;
Fluorescent emission wavelength: 426nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 2, compound synthetic
Step according to embodiment 1, only replaces with 2e by 1e, obtains target compound, yield: 82%.
1H?NMR(CDCl 3,300MHz):δ=7.85-7.87(t,3H),7.16-7.66(m,32H),6.81-6.84(t,4H),6.63-6.69(t,12H),1.35(s,9H)。
Second-order transition temperature Tg:288 ℃;
Uv-absorbing wavelength: 260nm, 285nm, 310nm;
Fluorescent emission wavelength: 435nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 3, compound synthetic
Step according to embodiment 1, only replaces with 3e by 1e, obtains target compound, yield: 88%.
1H?NMR(CDCl 3,300MHz):δ=7.85-7.91(t,6H),7.10-7.68(m,34H),6.81-6.82(m,2H),6.62-6.68(t,6H),1.31(s,9H)。
Second-order transition temperature Tg:244 ℃;
Uv-absorbing wavelength: 265nm, 270nm, 305nm;
Fluorescent emission wavelength: 445nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 4, compound synthetic
Step according to embodiment 1, only replaces with 4e by 1e, obtains target compound, yield: 91%.
1H?NMR(CDCl 3,300MHz):δ=8.50-8.52(d,1H),7.85-7.91(t,6H),7.10-7.68(m,32H),7.00-7.02(m,1H),6.81-6.83(t,2H),6.62-6.68(t,6H),1.35(s,9H)。
Second-order transition temperature Tg:272 ℃;
Uv-absorbing wavelength: 265nm, 290nm, 315nm;
Fluorescent emission wavelength: 454nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 5, compound synthetic
Step according to embodiment 1, only replaces with 5e by 1e, and the consumption of triphenylamine boric acid replaces with 5g, obtains target compound, yield: 78%.
1H?NMR(CDCl 3,300MHz):δ=8.55-8.57(d,2H),8.42(d,1H),8.04-8.08(m,2H),7.85-7.94(m,4H),7.77(s,1H),7.20-7.62(m,31H),1.35(s,9H)。
Second-order transition temperature Tg:265 ℃;
Uv-absorbing wavelength: 265nm, 315nm;
Fluorescent emission wavelength: 461nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 6, compound synthetic
Step according to embodiment 1, only replaces with 5e by 1e, and the consumption of triphenylamine boric acid replaces with 6g, obtains target compound, yield: 68%.
1H?NMR(CDCl 3,300MHz):δ=8.55-8.57(d,2H),8.42-8.44(d,1H),8.04-8.08(m,2H),7.85-7.87(m,3H),7.15-7.62(m,28H),2.71-2.73(m,2H),1.61-1.82(m,8H),1.35(s,9H)。
Second-order transition temperature Tg:215 ℃;
Uv-absorbing wavelength: 275nm, 295nm;
Fluorescent emission wavelength: 414nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 7, be prepared with organic electroluminescence devices OLED-1～OLED-6
1) by the glass substrate that has been coated with ITO conductive layer supersound process 30 minutes in clean-out system, in deionized water, rinse, in acetone/ethanol mixed solvent ultrasonic 30 minutes, under clean environment, be baked to complete drying, with UV-light cleaning machine, irradiate 10 minutes, and with low energy positively charged ion bundle bombarded surface.
2) the above-mentioned ito glass substrate of handling well is placed in vacuum chamber, is evacuated to 1 * 10 -5～9 * 10 -3pa continues difference evaporation compound TDATA as hole injection layer on above-mentioned anode tunic, and evaporation speed is 0.1nm/s, and evaporation thickness is 40nm;
Wherein, the structural formula of TDATA is as follows:
3) on above-mentioned hole injection layer film, continuing evaporation NPB is hole transmission layer, and evaporation speed is 0.1nm/s, and evaporation thickness is 10nm;
Wherein, the structural formula of NPB is as follows:
4) on hole transmission layer, continue that shown in evaporation one laminar I, compound 1f, 2f, 3f, 4f, 5f or 6f are as the organic luminous layer of device, evaporation speed is 0.1nm/s, and evaporation thickness is 40nm;
5) on organic luminous layer, continue evaporation one deck Alq3 material as the electron transfer layer of device, evaporation speed is 0.1nm/s, and evaporation thickness is 50nm;
Wherein, the structural formula of Alq3 is as follows:
6) on above-mentioned electron transfer layer successively evaporation magnesium/ag alloy layer as the cathode layer of device, wherein the evaporation speed of magnesium/ag alloy layer is 2.0～3.0nm/s, evaporation thickness is 100nm, magnesium and silver-colored mass ratio are 1:9, obtain successively organic electroluminescent device OLED-1～OLED-6 provided by the invention.
The performance test results of gained OLED-1 to OLED-6 is as shown in table 1.
The performance test results of table 1, OLED-1 to OLED-6
As from the foregoing, utilize the organic luminescent device that shown in formula I provided by the invention, compound is made, current density is higher, power efficiency, and photochromic be blue.
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to above-described embodiment, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.

Claims (10)

1. compound shown in formula I:
Formula I
In described formula I, R afor R 1-(Z 1-A 1-Z 2) x-;
R bfor-(Z 3-A 2-Z 4) y-R 2;
Wherein, R 1and R 2all be selected from H ,-F ,-Cl ,-CN ,-CF 3with-OCF 3, the total number of carbon atoms alkyl that is 1-15 of alkyl that the total number of carbon atoms is 1-15, alkoxyl group that the total number of carbon atoms is 1-15, normal olefine base that the total number of carbon atoms is 2-15, fluoro is, any one in the normal olefine base that the total number of carbon atoms of the alkoxyl group that the total number of carbon atoms of fluoro is 1-15 and fluoro is 2-15;
Z 1, Z 2, Z 3and Z 4all be selected from-O-,-S-,-OCO-,-COO-,-CO-,-CH 2o-,-OCH 2-,-CF 2o-,-OCF 2-, the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms is 1-15, normal olefine base that the total number of carbon atoms is 2-15, straight-chain alkynyl that the total number of carbon atoms is 2-15, fluoro is 1-15, fluoro alkylene that is 2-15 and at least one in carbon-carbon single bond;
A 1and A 2all be selected from 1,4-cyclohexylidene, 1,4-phenylene, two phenenyl phosphinyl, N-phenyl-carbazole-2-base, N-phenyl-carbazole-3-base, 9,10-anthryl, 1-naphthyl, 4-triphenylamine base, 2,5-pyrimidyl, 3,9-carbazyl, 2,5-pyridyl, 2,5-tetrahydrochysene-2H-pyranyl, 1,3-diox-2,5-base, 1,2,4-oxadiazole-3,1 of 5-base, fluoro, any one in the Isosorbide-5-Nitrae-phenylene of 4-cyclohexylidene, fluoro, the pyranoid ring of fluoro two bases, cyclic lactone two bases, five yuan of oxa-ring two bases, pentatomic sulphur heterocycle two bases, penta azacyclo two bases and carbon-carbon single bonds;
X and y are the integer of 0-3;
Described x or y are 2 or at 3 o'clock, structural unit Z 1-A 1-Z 2in, Z 1identical or different, A 1identical or different, Z 2identical or different; Structural unit Z 3-A 2-Z 4in, Z 3identical or different, A 2identical or different, Z 4identical or different.
2. compound according to claim 1, is characterized in that: in described formula I, and R afor
R bfor or naphthyl;
Shown in described formula I, compound is specially any one in following compound:
3. a method of preparing compound shown in the arbitrary described formula I of claim 1 or 2, comprises the steps:
PH value in reaction system is 8-14 and Pd (PPh 3) 4under the condition existing as catalyzer, compound shown in formula VII compound and formula VIII is carried out to Suzuki cross-coupling reaction, obtain after completion of the reaction compound shown in formula I;
R A-B(OH) 2
Formula VIII
Formula VII
Described formula VII to formula VIII, R aand R bdefinition all identical with claim 1.
4. method according to claim 3, is characterized in that: shown in compound shown in described formula VII and formula VIII, the mol ratio of compound is 1:1～2, preferably 1:1.1;
Compound shown in formula VII and Pd (PPh 3) 4molar ratio be 1:0.002～0.05, preferred 1:0.05.
5. according to the arbitrary described method of claim 3-4, it is characterized in that: in described Suzuki cross-coupling reaction step, temperature is 60 ℃～160 ℃, preferably 80 ℃～100 ℃;
Time is 4～10 hours, is preferably 6～8 hours.
6. according to the arbitrary described method of claim 3-5, it is characterized in that: described Suzuki cross-coupling reaction carries out in solvent;
Described solvent is specifically selected from least one in tetrahydrofuran (THF), hexane, acetic acid, dimethylbenzene, ethanol, toluene, water, orthodichlorobenzene, acetic acid and Isosorbide-5-Nitrae-dioxane.
7. according to the arbitrary described method of claim 3-6, it is characterized in that: the reaction atmosphere of described Suzuki cross-coupling reaction is inert atmosphere, preferably argon gas atmosphere.
8. compound shown in the arbitrary described formula I of claim 1 or 2 is being prepared luminescent material or organic electroluminescence device or is being prepared with the application in OLED;
Wherein, the fluorescent emission wavelength of described luminescent material is specially 414-461nm.
9. the luminescent material or organic electroluminescence device or the Organic Light Emitting Diode that contain compound shown in the arbitrary described formula I of claim 1 or 2;
Wherein, the fluorescent emission wavelength of described luminescent material is specially 414-461nm.
10. application according to claim 8 or organic electroluminescence device claimed in claim 9, is characterized in that:
Described organic electroluminescence device is comprised of transparent substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer from the bottom to top successively;
Wherein, the material that forms described transparent substrate is glass or flexible substrate;
The material that forms described anode layer is inorganic materials or organic conductive polymkeric substance; Wherein, described inorganic materials is tin indium oxide, zinc oxide, stannic oxide, gold and silver or copper; Described organic conductive polymkeric substance is selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material that forms described hole injection layer is TDATA;
The structural formula of described TDATA is as follows:
The material that forms described hole transmission layer is NPB;
The structural formula of described NPB is as follows:
The material that forms described organic luminous layer is compound shown in the arbitrary described formula I of claim 1 or 2;
The material that forms described electron transfer layer is Alq3, Gaq3 or BPhen;
Wherein, the structural formula of Alq3, BPhen and Gaq3 is as follows successively:
The material that forms described cathode layer is selected from any one or the alloy of any two kinds of compositions or the fluorochemical of following element in following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin;
The thickness of described hole injection layer is 30-50nm, is specially 40nm;
The thickness of described hole transmission layer is 5-15nm, is specially 10nm;
The thickness of described organic luminous layer is 10-100nm, is specially 40nm;
The thickness of described electron transfer layer is 40-60nm, is specially 50nm;
The thickness of described cathode layer is 90-110nm, is specially 100nm.
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