CN106892796A - A kind of new OLED intermediary material preparation methods - Google Patents
A kind of new OLED intermediary material preparation methods Download PDFInfo
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- CN106892796A CN106892796A CN201510963782.3A CN201510963782A CN106892796A CN 106892796 A CN106892796 A CN 106892796A CN 201510963782 A CN201510963782 A CN 201510963782A CN 106892796 A CN106892796 A CN 106892796A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
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Abstract
The invention belongs to electroluminescent organic material technical field, disclose a kind of new OLED intermediary material preparation methods, specially a kind of 4', 4 " ' (1 (4 iodophenyl) ethyl 1, 12 two) double (4 bromines 1, 1' diphenyl) synthetic method, the present invention with 4 nitro-acetophenones and phenol be raw material, synthetic product reacts with trifluoromethyl sulfonic acid anhydride in the presence of pyridine, obtain product and the reaction of duplex pinacol borate, product and 4 bromo-iodobenzenes are obtained to be reacted by suzuki, product is obtained by iron powder and concentrated hydrochloric acid, product is obtained by Iod R in diazotising, obtain final goal product.Raw material of the present invention is simple, be easily achieved industrialized production, with short production cycle；Can further improve its dissolubility and heat endurance by introducing Br groups in organic matter, be easy to organic matter further to react the generation more preferable material of photoelectric properties.
Description
Technical field
The invention belongs to electroluminescent organic material technical field, it is related in the middle of a kind of new OLED
Body material preparation method, specially a kind of 4', 4 " '-(1- (4- iodophenyls) ethyl -1,1-2- bis-) double (4- bromo- 1,1'-
Diphenyl) synthetic method.
Background technology
The material commonly used in organic electroluminescence device has：Electrode material, injection material, transmission material
Material, barrier material, luminescent material.Electrode material includes anode electrode material and cathode electrode material；
Injection material includes hole-injecting material and electron injection material；Transmission material includes hole mobile material
And electron transport material；Barrier material includes the resistance of hole barrier materials, electron-blocking materials and exciton
Obstructing material；Luminescent material includes luminous organic material, Phosphorescent guest materials and material of main part.It is empty
Hole transport materials HTM (HTM, Hole Transport Materials) is mainly improves device hole
Injection and the balance of transmission, improve the luminous efficiency of device and the life-span of device.As hole transmission layer,
It must is fulfilled for following condition：(1) there is preferable mobility, it is ensured that have good hole transport performance；
(2) with good film forming and heat endurance, the life-span of device is improved；(3) with suitable
Low start voltage, drops in HOMO energy levels, it is ensured that hole can be efficiently injected into；(4) after evaporation or spin coating
There is the pattern form of preferable stabilization.
Conventional hole mobile material is triphenylamine compound, and they are initially used in duplicator,
Used as charge transport materials, they have good mobility, about 10-3cm2/Vs.TAPC is
With triphen amine hole mobile material earlier, it has hole mobility very high, be 1.0 ×
10-2cm2/Vs.C.W.Tang is exactly initially (Tang, the C. for being treated as hole mobile material to use
W.；VanSlyke S.A.“Organic electroluminescent diodes”,Appl.Phys.Lett.
1987,51,913.), up to now, still it is widely used.It is found that with biphenyl as core later
Triaryl amine can greatly improve (VanSlyke after the stability of luminous efficiency and device as hole transmission layer
S.A.,Tang C.T.；O’Brien,M.E.；Chen,C.H.“Electroluminescent device
With organic electroluminescent medium ", US 5061569,1991.), most sky
Hole transport materials all include this part-structure.Compound with carbazole structure is also relatively good hole
Transmission material.If PVK (PVK) is exactly typical high-molecular hole conduction material.It is empty
Hole transport materials usually have triphenylamine and carbazole structure, and they are mainly the organic semiconductor of p-type,
Its transporting mechanism be lone pair electrons on nitrogen-atoms when there is the transmission of great-jump-forward in the presence of electric field,
Molecule has reformed into corresponding hole, transmits in the opposite direction.On hole mobile material, Japan
Shirota et al. carried out systematic research (Shirota, Y.；Okumoto,K.“Charge-transport
properties”,Proc.SPIE.2001,4105,159.)。
The content of the invention
It is an object of the invention to provide a kind of preparation method it is simple, be easy to quantify the new organic of production
Electroluminescent material and preparation method thereof, substep it is synthetically prepared go out 4', 4 " '-(1- (4- iodophenyls) ethyl -1,1-2-
Two) double (bromo- 1, the 1'- diphenyl of 4-), while introducing Br groups in organic matter, can further to improve its molten
Solution property and heat endurance, are easy to organic matter further to react the generation more preferable material of photoelectric properties.
To achieve these goals, the technical solution adopted in the present invention is：A kind of new OLED
Intermediary material preparation method, comprises the following steps：
Step 1, with 4- nitro-acetophenones and phenol as raw material, reacts in the presence of p-methyl benzenesulfonic acid
Generation 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol；
Step 2, in the presence of pyridine, 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenols and three
Methyl fluoride sulfonic acid anhydride reactant, generates TFMS -4- [1- (4- nitrobenzene) -1- (4- fluoroform sulphonyl oxygen
Base benzene) ethyl] phenyl ester；
Step 3, TFMS -4- [1- (4- nitrobenzene) -1- (4- trifluorometanesulfonyloxies benzene) ethyl]
Phenyl ester is with duplex pinacol borate in potassium acetate, Pd2(dba)3Obtained with reaction in the presence of X-Phos
2,2'- (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes)) double (4,4,5,5- tetramethyls -1,3,2-
The ring of dioxy boron penta)；
Step 4,2,2'- (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes)) double (4,4,5,5- tetra-
Methyl isophthalic acid, the ring of 3,2- dioxies boron penta) and 4- bromo-iodobenzenes in potassium carbonate, TBAB and Pd (PPh3)4's
The lower reaction by suzuki of effect obtains 4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] nitrobenzene；
Step 5,4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] nitrobenzene passes through reduced iron powder and concentrated hydrochloric acid also
Original, obtains 4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] aniline；
Step 6,4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] aniline is obtained most by Iod R in diazotising
Whole target product；Synthetic route is as follows：
The target product is that can be used for the new compound of OLED intermediary materials for 4', 4 " '-(1- (4-
Iodophenyl) ethyl -1,1-2- bis-) double (bromo- 1, the 1'- diphenyl of 4-), molecular formula is C32H23Br2I。
A kind of above-mentioned new OLED intermediary material preparation methods, the step 1 is protected in nitrogen
Under carry out, wherein, 4- nitro-acetophenones described in step 1, phenol and p-methyl benzenesulfonic acid mole
Than being 1: 5: 4；65~80 DEG C of reaction temperature, 10~18h of reaction time；The step 1 is anti-after terminating
Liquid is answered to wash with water, anhydrous magnesium sulfate is dried, concentration, petroleum ether and dichloromethane are filtered, done after purification
It is dry to obtain final product high-purity 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol.
A kind of above-mentioned new OLED intermediary material preparation methods, the step 2 is protected in nitrogen
Under carry out；Wherein, 4,4'- described in step 2 (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol, three
The mol ratio 1: 5: 5 of methyl fluoride sulphonic acid anhydride and pyridine；10~15 DEG C of reaction temperature, reaction time 4h；
Solvent toluene is 12ml with the adding proportion of 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol:
1g；The trifluoromethyl sulfonic acid anhydride dropping temperature control is in 0~10 DEG C, time for adding 1.5h；The step
Reaction solution is washed with water after rapid 2 end, and anhydrous magnesium sulfate is dried, concentration, filtered after normal heptane purification,
It is drying to obtain high-purity TFMS -4- [1- (4- nitrobenzene) -1- (4- trifluorometanesulfonyloxies benzene) second
Base] phenyl ester.
A kind of above-mentioned new OLED intermediary material preparation methods, the step 3 is protected in nitrogen
Under carry out；[1- (4- nitrobenzene) -1- (the 4- trifluorometanesulfonyloxies of TFMS -4- described in step 3
Benzene) ethyl] phenyl ester, duplex pinacol borate, potassium acetate, Pd2(dba)3(three (dibenzalacetones)
Two palladiums) and X-Phos (2- dicyclohexyl phosphorus -2', 4', 6'- tri isopropyl biphenyl) mol ratio 1: 2.36:
6.11∶0.004∶0.008；80~85 DEG C of reaction temperature, reaction time 12h；Solvent is DMF, its
Middle DMF and TFMS -4- [1- (4- nitrobenzene) -1- (4- trifluorometanesulfonyloxies benzene) ethyl] phenyl ester
Adding proportion be 15ml: 1g；Reaction solution dichloroethanes and washing, nothing after step 3 end
Water magnesium sulfate is dried, concentration, is filtered after ethyl acetate purification, is drying to obtain high-purity 2,2'- (4,4'- (1- (4-
Nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes)) double (rings of 4,4,5,5- tetramethyl -1,3,2- dioxies boron penta).
A kind of above-mentioned new OLED intermediary material preparation methods, the step 4 is protected in nitrogen
Under carry out；2,2'- described in step 4 (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes))
Double (rings of 4,4,5,5- tetramethyl -1,3,2- dioxies boron penta), 4- bromo-iodobenzenes, potassium carbonate, TBAB and
Pd(PPh3)4Mol ratio 1: 2.49: 4.03: 0.4: 0.01；70~75 DEG C of reaction temperature, during reaction
Between 7h；Solvent be toluene, ethanol and water mixed solvent, wherein, toluene, ethanol and water volume ratio are
1∶1∶1；Reaction solution petroleum ether and washing after step 4 end, filtering, toluene purification, mistake
Insulation silicagel column removes catalyst, is drying to obtain high-purity 4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] nitre
Base benzene.
A kind of above-mentioned new OLED intermediary material preparation methods, [1,1- is double for 4- described in step 5
(4'- bromo biphenyl -4- bases) ethyl] nitrobenzene, reduced iron powder and concentrated hydrochloric acid mol ratio be 1: 8.92: 35；
75~80 DEG C of reaction temperature, reaction time 7h；Reaction solution is through filtering, dichloro after step 5 end
Ethane and washing, concentrate, are drying to obtain high-purity 4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] aniline.
A kind of above-mentioned new OLED intermediary material preparation methods, [1,1- is double for 4- described in step 6
(4'- bromo biphenyl -4- bases) ethyl] aniline, NaNO2, the concentrated sulfuric acid and KI mol ratio 1: 1.21: 5.04:
1.5；Reaction temperature -5~0 DEG C, reaction time 3h；Solvent is THF；Wherein, 4- [1,1- double (4'- bromines connection
Benzene -4- bases) ethyl] adding proportion of aniline and THF is 1g: 10ml；The NaNO2It was added dropwise program control
0~5 DEG C of temperature processed, time for adding 10min；KI is added dropwise -5 DEG C of process control temp~0 DEG C, time for adding
20min；Reaction solution dichloroethanes and washing after step 6 end, add sodium hydrogensulfite to remove
Iodine in course of reaction, anhydrous magnesium sulfate is dried, filtering, hexamethylene purification, is crossed insulation silicagel column and is removed
Remove mechanical admixture, be drying to obtain the 4' of high-purity, 4 " '-(1- (4- iodophenyls) ethyl -1,1-2- two) double (4- bromines
- 1,1'- diphenyl).
Beneficial effects of the present invention：Synthesis material of the present invention is simple, cheap, building-up process operation
Simply, industrialized production, with short production cycle, the 4' of preparation, 4 are easily achieved " '-(1- (4- iodophenyls) ethyl
- 1,1-2- bis-) double (bromo- 1, the 1'- diphenyl of 4-) products have heat endurance higher, can be used for prepare OLED
The organic electroluminescence devices such as material, while introducing Br groups in organic matter, can further to improve its molten
Solution property and heat endurance, are easy to organic matter further to react the generation more preferable material of photoelectric properties.
Brief description of the drawings
The present invention is specifically described below by accompanying drawing and in conjunction with the embodiments, wherein content is only used shown in accompanying drawing
In explanation of the present invention, without constituting to the limitation gone up in all senses of the invention.
Fig. 1 is embodiment of the present invention 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol reaction solution liquid
Phase chromatogram (LC) figure；
Fig. 2 is embodiment of the present invention TFMS -4- [1- (4- nitrobenzene) -1- (4- fluoroform sulphonyl oxygen
Base benzene) ethyl] phenyl ester reaction solution liquid chromatogram (LC) figure；
Fig. 3 is embodiment of the present invention 2,2'- (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes))
Double (ring of 4,4,5,5- tetramethyl -1,3,2- dioxies boron penta) reaction solution liquid chromatogram (LC) figures；
Fig. 4 is embodiment of the present invention 4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] nitrobenzene reaction solution liquid phase
Chromatogram (LC) figure；
Fig. 5 is embodiment of the present invention 4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] aniline reaction liquid liquid phase color
Spectrum (LC) figure；
Fig. 6 is embodiment of the present invention final product 4', 4 " '-(1- (4- iodophenyls) ethyl -1,1-2- two) double (4-
Bromo- 1,1'- diphenyl) reaction solution liquid chromatogram (LC) figure；
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is being with technical solution of the present invention
Under the premise of implemented, give detailed implementation method and specific operating process.It should be understood that
It is to those skilled in the art, without departing from the inventive concept of the premise, may be used also
To make some variations and modifications, these belong to the scope of the present invention.
A kind of new OLED intermediary material preparation methods of the present invention, specially a kind of 4', 4 " '-(1- (4-
Iodophenyl) ethyl -1,1-2- two) double (the bromo- 1,1'- diphenyl of 4-) building-up process specific embodiment it is as follows：
1) synthetic operation of 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol：Under nitrogen protection,
Successively to stirring, 4- nitro-acetophenone 100.0g are added in the 1L there-necked flasks of thermometer and condenser pipe,
Phenol 224.0g, p-methyl benzenesulfonic acid 300.0g, open heating, when temperature rises to 60 DEG C~70 DEG C
When, dissolution of raw material opens stirring, and one is taken every 1h after being continuously heating to 65 DEG C~80 DEG C reaction 10h
Secondary sample；As main content LC>75%, as raw material 4- nitro-acetophenones LC<5% stops reaction (see accompanying drawing
1, LC=77.6519%, raw material LC=4.5257%)；Reaction equation is as follows：
Post processing：When reaction temperature is down to 50 DEG C~60 DEG C, reaction solution is poured slowly into 2.0L's
In deionization hot water, 5min is stirred, stand 0.5h, separate upper strata aqueous phase, add 2.0L deionizations
Hot water, stirs 5min, stands 0.5h, separates upper strata aqueous phase, and 1.0L dichloros are added in lower floor's organic phase
Ethane, neutrality, organic phase 20.0g anhydrous slufuric acids are washed till with 1.0L deionized waters (15 DEG C~25 DEG C)
Magnesium dries 4h, and filtering is drained, and filter cake abandons it, concentration filtrate (- 0.08MPa~-0.09MPa, 40 DEG C~
45 DEG C) when being about 250ml~300ml to concentrate is remaining, stop concentration, concentrate under agitation, delays
It is slow inwardly to add 200ml petroleum ethers, (65 DEG C~70 DEG C) 0.5h is heated to reflux, stop heating, it is naturally cold
But to room temperature (10 DEG C~15 DEG C), filtering is drained, and obtains faint yellow solid 180.0g.
Purifying：Above-mentioned 180.0g faint yellow solids are heated to reflux (30 DEG C with 900ml dichloromethane
~35 DEG C) boil and wash 1h, under stirring, room temperature (10 DEG C~15 DEG C) is cooled to, 5h is placed, filtering is drained,
(- 0.08MPa, 55 DEG C, 4h) are dried with vacuum drying oven, 167.0g light yellow products is obtained as high-purity
4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol of degree.
2) TFMS -4- [1- (4- nitrobenzene) -1- (4- trifluorometanesulfonyloxies benzene) ethyl] phenyl ester
Synthetic operation：Under nitrogen protection, successively to stirring, the 3L there-necked flasks of thermometer and condenser pipe
4,4'- of middle addition (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol 170.0g, toluene 2040ml, pyridine
160.0g, opens stirring, is cooled to 0 DEG C~10 DEG C, and fluoroform is inwardly added dropwise by constant pressure funnel
Base sulphonic acid anhydride 510.0g, is added dropwise process control temp at 0 DEG C~10 DEG C, about 1.5h completion of dropping, from
After being so warming up to (10 DEG C~15 DEG C) reaction 4h of room temperature a sample is taken every 1h；As main content LC>90%,
Raw material 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol LC<2% stopping reaction (see accompanying drawing 2,
LC=94.1276%, raw material LC=1.1107%)；Reaction equation is as follows：
Post processing：To 2.0L deionized waters are added in reaction solution, 5min is stirred, stand 0.5h, point liquid,
Upper organic phase is washed with deionized water to neutrality, and organic phase dries 0.5h, mistake with 50.0g anhydrous magnesium sulfates
Filter, removes drier, and filtrate concentration (- 0.08MPa~-0.09MPa, 50 DEG C~55 DEG C) is molten to not distillating
Stop concentration during agent, to 500ml normal heptanes are added in concentrate, be heated to reflux (90 DEG C~98 DEG C) 0.5h,
Under stirring, room temperature (10 DEG C~15 DEG C) is naturally cooled to, there are a large amount of white solids to separate out, filtering is used
Filter cake of 100ml normal heptanes drip washing, drains, product with vacuum drying oven dry (- 0.08MPa, 55 DEG C,
4h), TFMS -4- [1- (4- nitrobenzene) -1- (4- of 280.0g off-white powders as high-purity are obtained
Trifluorometanesulfonyloxy benzene) ethyl] phenyl ester.
3) 2,2'- (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes)) double (4,4,5,5- tetramethyls
The ring of -1,3,2- dioxies boron penta) synthetic operation：Under nitrogen protection, successively to stirring, thermometer
And TFMS -4- [1- (4- nitrobenzene) -1- (4- fluoroforms are sequentially added in the 10L there-necked flasks of condenser pipe
Alkane sulfonyloxy benzene) ethyl] phenyl ester 300.0g, duplex pinacol borate 300.0g, potassium acetate 300.0g,
DMF 4.5L, Pd2(dba)32.0g, X-Phos 2.0g, open stirring, are heated to 80 DEG C~85 DEG C instead
After answering 12h a sample is taken every 1h；As main content LC>65%, raw material TFMS -4- [1- (4-
Nitrobenzene) -1- (4- trifluorometanesulfonyloxies benzene) ethyl] phenyl ester LC<1% stopping reaction (see accompanying drawing 3,
LC=67.7867%, raw material LC=0.4332%)；Reaction equation is as follows：
Post processing：To 4.5L dichloroethanes and 4.5L deionized waters is added in reaction solution, 5min is stirred,
0.5h is stood, point liquid, lower floor's organic phase is washed with deionized water to neutrality, and organic phase is anhydrous with 100.0g
Magnesium sulfate dries 4h, filtering, removing drier, filtrate concentration (- 0.08MPa~-0.09MPa, 50 DEG C~
55 DEG C) to residue about 500ml solvents when, stop concentration, in concentrate addition 200ml petroleum ethers,
0.5h is sufficiently stirred for, is filtered, drained, obtain 192.0g crude products.
Purifying：Above-mentioned 192.0g crude products are heated to reflux (60 DEG C~70 DEG C) 0.5h with 672ml ethyl acetate,
Dissolving crude product, is down to room temperature (10 DEG C~15 DEG C) naturally, places 5h, and filtering is drained, and product is with very
Empty oven for drying (- 0.08MPa, 55 DEG C, 4h), obtains off-white powder 158.0g as high-purities
2,2'- (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes)) double (4,4,5,5- tetramethyls -1,3,2-
The ring of dioxy boron penta).
4) synthetic operation of 4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] nitrobenzene：Under nitrogen protection,
Successively to stirring, 2,2'- (4,4'- (1- (4- are sequentially added in the 3L there-necked flasks of thermometer and condenser pipe
Nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes)) double (rings of 4,4,5,5- tetramethyl -1,3,2- dioxies boron penta)
135.0g, 4- bromo-iodobenzene 171.0g, potassium carbonate 135.0g, TBAB 31.5g, toluene 675ml, ethanol
675ml, deionized water 675ml, Pd (PPh3)42.7g, opens stirring, is heated to reflux (70 DEG C~75 DEG C)
After reaction 7h a sample is taken every 1h；As main content LC>80%, raw material 2,2'- (4,4'- (1- (4- nitros
Benzene) ethane -1,1- diyls) double (4,1- penylenes)) double (rings of 4,4,5,5- tetramethyl -1,3,2- dioxies boron penta)
LC<0.5% stops reaction (see accompanying drawing 4, LC=80.2049%, raw material LC=0.3141%)；Reaction side
Formula is as follows：
Post processing：To 300ml deionized waters and 300ml petroleum ethers is added in reaction solution, 0.5h is stirred,
Filtering, filter cake deionized water drip washing to neutrality, is drained with 200ml petroleum ether drip washing filter cake once,
Obtain 158.0g off-white powders.
Purifying：Above-mentioned 158.0g off-white powders are heated to 80 DEG C~90 DEG C with 1264ml toluene,
About 0.5h, dissolving crude product, excessively insulation silicagel column, the excessively concentration of post liquid (- 0.08MPa~-0.09MPa,
65 DEG C~70 DEG C) to residue about 600ml solvents when, stop concentrate, naturally cool to (10 DEG C of room temperature
~15 DEG C), place 5h, filtering, drain, product with vacuum drying oven dry (- 0.08MPa, 65 DEG C,
4h), white solid 121.0g as high-purity product 4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] are obtained
Nitrobenzene.
5) synthetic operation of 4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] aniline：Successively to stirring,
4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] nitre is sequentially added in the 1L there-necked flasks of thermometer and condenser pipe
Base benzene 50.0g, ethanol 800ml, reduced iron powder 31.6g, watery hydrochloric acid 120ml (concentrated hydrochloric acid 60ml+60ml
Deionized water), stirring is opened, after being heated to reflux (75 DEG C~80 DEG C) reaction 1h, add watery hydrochloric acid
36.6ml, continues to take a sample every 1h after reacting 6h；As main content LC>90%, raw material 4- [1,1-
Double (4'- bromo biphenyl -4- bases) ethyls] nitrobenzene LC<0.5% stopping reaction (see accompanying drawing 5, LC=93.5221%,
Raw material LC=0.2132%)；Reaction equation is as follows：
Post processing：After reaction solution is down to room temperature (10 DEG C~15 DEG C), directly filter, filter off unreacted complete
Iron powder, in filtrate add 800ml dichloroethanes and 800ml deionized waters, stir 5min, stand
10min, point liquid, organic phase is washed with deionized water to neutrality, and organic phase continues to use 10.0g anhydrous slufuric acids
Magnesium dries 2h, filtering, removing drier, filtrate concentration (50 DEG C~55 DEG C, -0.08MPa~-0.09MPa)
When extremely remaining concentrate is 50ml~60ml, stop concentration, to addition 200ml petroleum ethers in concentrate,
Stirring 0.5h, filtering is drained, and product vacuum drying oven dries (- 0.08MPa, 65 DEG C, 4h), obtains
Off-white powder 41.0g is 4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] aniline of high-purity.
6) synthetic operation of 4', 4 " '-(1- (4- iodophenyls) ethyl -1,1-2- two) double (the bromo- 1,1'- diphenyl of 4-)：
Successively to stirring, sequentially added in the 500mL there-necked flasks of thermometer and constant pressure funnel
4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] aniline 20.0g, THF 200ml, after stirring and dissolving, adds
56.8g dilute sulfuric acids, after being cooled to 0 DEG C~5 DEG C, NaNO are inwardly added dropwise by constant pressure funnel2's
The aqueous solution, is added dropwise process temperature control in 0 DEG C~5 DEG C, about 10min completion of dropping, in 0 DEG C~5 DEG C insulations
0.5h, ice-water bath is cooled to -5 DEG C~0 DEG C, starts that the aqueous solution of KI is inwardly added dropwise, and process temperature control is added dropwise
At -5 DEG C~0 DEG C, about 20min completion of dropping, timing maintains temperature to continue to react at -5 DEG C~0 DEG C
A sample is taken every 1h after 2h, as main content LC>50%, raw material 4- [1,1- double (4'- bromo biphenyl -4- bases)
Ethyl] aniline LC<1% stops reaction (see accompanying drawing 6, LC=53.3436%, raw material LC=0.6269%)；
Reaction equation is as follows：
Post processing：To addition 200ml dichloroethanes and 200ml deionized waters in reaction solution, under stirring,
5.0g sodium hydrogensulfites are added, continues to stir 0.5h, stand 5min, point liquid, lower floor's organic phase spends
Ion is washed to neutrality, and organic phase dries 5h with 5.0g anhydrous magnesium sulfates, filtering, removes drier,
Filtrate concentration (40 DEG C~45 DEG C, -0.08MPa~-0.09MPa) distillated to solvent-free, obtain 22.0g
Concentrate.
Purifying：Above-mentioned 22.0g concentrates are heated to reflux (75 DEG C~80 DEG C) 0.5h with 440ml hexamethylenes,
Cross heat-insulation column, cross post liquid concentration (- 0.08MPa~-0.09MPa, 55 DEG C~60 DEG C) to not going out solvent
When, concentrate is dope, to 20ml ethanol is added in concentrate, is heated to reflux (65 DEG C~70 DEG C)
Boil and wash 0.5h, naturally cool to room temperature (10 DEG C~15 DEG C), filter, drain, baking material (- 0.08MPa,
65 DEG C, 4h), obtain 20.0g off-white powders；
By 20.0g off-white powders re crystallization from toluene four times, 5.2g white solids are obtained as high-purity
Degree fine work final product 4', 4 " '-(1- (4- iodophenyls) ethyl -1,1-2- two) double (the bromo- 1,1'- diphenyl of 4-).
The above is preferred exemplary applications of the invention, not limitation of the present invention, every basis
Simple modification that technical key point is made, structure change change belong to protection scope of the present invention
Within.
Claims (7)
1. a kind of new OLED intermediary material preparation methods, it is characterised in that including following step
Suddenly：
Step 1, with 4- nitro-acetophenones and phenol as raw material, reacts in the presence of p-methyl benzenesulfonic acid
Generation 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenol；
Step 2, in the presence of pyridine, 4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) biphenols and three
Methyl fluoride sulfonic acid anhydride reactant, generates TFMS -4- [1- (4- nitrobenzene) -1- (4- fluoroform sulphonyl oxygen
Base benzene) ethyl] phenyl ester；
Step 3, TFMS -4- [1- (4- nitrobenzene) -1- (4- trifluorometanesulfonyloxies benzene) ethyl]
Phenyl ester is with duplex pinacol borate in potassium acetate, Pd2(dba)3Obtained with reaction in the presence of X-Phos
2,2'- (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes)) double (4,4,5,5- tetramethyls -1,3,2-
The ring of dioxy boron penta)；
Step 4,2,2'- (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1- penylenes)) double (4,4,5,5- tetra-
Methyl isophthalic acid, the ring of 3,2- dioxies boron penta) and 4- bromo-iodobenzenes in potassium carbonate, TBAB and Pd (PPh3)4's
The lower reaction by suzuki of effect obtains 4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] nitrobenzene；
Step 5,4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] nitrobenzene passes through reduced iron powder and concentrated hydrochloric acid also
Original, obtains 4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] aniline；
Step 6,4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] aniline is obtained most by Iod R in diazotising
Whole target product；Synthetic route is as follows：
The target product is that can be used for the new compound of OLED intermediary materials for 4', 4 " '-(1- (4-
Iodophenyl) ethyl -1,1-2- bis-) double (bromo- 1, the 1'- diphenyl of 4-), molecular formula is C32H23Br2I。
2. a kind of new OLED intermediary material preparation methods according to claim 1, its
It is characterised by, the step 1 is carried out under nitrogen protection, wherein, 4- nitrobenzene described in step 1
The mol ratio of ethyl ketone, phenol and p-methyl benzenesulfonic acid is 1: 5: 4；65~80 DEG C of reaction temperature, reaction
10~18h of time；Reaction solution is washed with water after the step 1 terminates, and anhydrous magnesium sulfate is dried, concentration,
Petroleum ether and dichloromethane are filtered, are drying to obtain high-purity 4,4'- (1- (4- nitrobenzene) ethane -1,1- after purification
Diyl) biphenol.
3. a kind of new OLED intermediary material preparation methods according to claim 1, its
It is characterised by, the step 2 is carried out under nitrogen protection；Wherein, the (1- (4- of 4,4'- described in step 2
Nitrobenzene) ethane -1,1- diyls) biphenol, trifluoromethyl sulfonic acid anhydride and pyridine mol ratio 1: 5: 5；
10~15 DEG C of reaction temperature, reaction time 4h；Solvent toluene and 4,4'- (1- (4- nitrobenzene) ethane -1,1-
Diyl) biphenol adding proportion be 12ml: 1g；The trifluoromethyl sulfonic acid anhydride dropping temperature control exists
0~10 DEG C, time for adding 1.5h；Reaction solution is washed with water after the step 2 terminates, and anhydrous magnesium sulfate is done
Dry, concentration is filtered after normal heptane purification, is drying to obtain high-purity TFMS -4- [1- (4- nitros
Benzene) -1- (4- trifluorometanesulfonyloxies benzene) ethyl] phenyl ester.
4. a kind of new OLED intermediary material preparation methods according to claim 1, its
It is characterised by, the step 3 is carried out under nitrogen protection；[1- (the 4- of TFMS -4- described in step 3
Nitrobenzene) -1- (4- trifluorometanesulfonyloxies benzene) ethyl] phenyl ester, duplex pinacol borate, potassium acetate,
Pd2(dba)3It is 1: 2.36: 6.11: 0.004: 0.008 with the mol ratio of X-Phos；Reaction temperature
80~85 DEG C, reaction time 12h；Solvent is DMF, wherein DMF and TFMS -4- [1- (4-
Nitrobenzene) -1- (4- trifluorometanesulfonyloxies benzene) ethyl] phenyl ester adding proportion be 15ml: 1g；It is described
Reaction solution dichloroethanes and washing after step 3 end, anhydrous magnesium sulfate are dried, concentration, acetic acid second
Filtered after ester purification, be drying to obtain high-purity 2,2'- (4,4'- (1- (4- nitrobenzene) ethane -1,1- diyls) double (4,1-
Penylene)) double (rings of 4,4,5,5- tetramethyl -1,3,2- dioxies boron penta).
5. a kind of new OLED intermediary material preparation methods according to claim 1, its
It is characterised by, the step 4 is carried out under nitrogen protection；(4,4'- (1- (the 4- nitre of 2,2'- described in step 4
Base benzene) ethane -1,1- diyls) double (4,1- penylenes)) double (rings of 4,4,5,5- tetramethyl -1,3,2- dioxies boron penta), 4- bromines
Iodobenzene, potassium carbonate, TBAB and Pd (PPh3)4Mol ratio 1: 2.49: 4.03: 0.4:
0.01；70~75 DEG C of reaction temperature, reaction time 7h；Solvent be toluene, ethanol and water mixed solvent,
Wherein, toluene, ethanol and water volume ratio are 1: 1: 1；Reaction solution oil after step 4 end
Ether and washing, filtering, toluene purification are crossed insulation silicagel column and remove catalyst, are drying to obtain high-purity
4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] nitrobenzene.
6. a kind of new OLED intermediary material preparation methods according to claim 1, its
It is characterised by, 4- described in step 5 [1,1- double (4'- bromo biphenyl -4- bases) ethyls] nitrobenzene, reduced iron powder
It is 1: 8.92: 35 with the mol ratio of concentrated hydrochloric acid；65 DEG C~80 DEG C of reaction temperature, reaction time 7h；Institute
Reaction solution after step 5 terminates is stated, through filtering, dichloroethanes and washing, to concentrate, be drying to obtain high-purity
4- [double (4'- bromo biphenyl -4- bases) ethyls of 1,1-] aniline.
7. a kind of new OLED intermediary material preparation methods according to claim 1, its
It is characterised by, 4- described in step 6 [1,1- double (4'- bromo biphenyl -4- bases) ethyls] aniline, NaNO2, it is dense
The mol ratio 1: 1.21: 5.04: 1.5 of sulfuric acid and KI；Reaction temperature -5~0 DEG C, reaction time 3h；
Solvent is THF；Wherein, the adding proportion of 4- [1,1- double (4'- bromo biphenyl -4- bases) ethyls] aniline and THF
It is 1g: 10ml；The NaNO20~5 DEG C of process control temp, time for adding 10min is added dropwise；KI
Process control temp -5~0 DEG C, time for adding 20min is added dropwise；Reaction solution uses two after the step 6 terminates
Chloroethanes and washing, the iodine in adding sodium hydrogensulfite to remove course of reaction, anhydrous magnesium sulfate are dried,
Filtering, hexamethylene purification is crossed insulation silicagel column and removes mechanical admixture, is drying to obtain high-purity
4', 4 " '-(1- (4- iodophenyls) ethyl -1,1-2- two) double (the bromo- 1,1'- diphenyl of 4-).
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