CN105294463A - Triphenylamine derivative and preparation method thereof - Google Patents
Triphenylamine derivative and preparation method thereof Download PDFInfo
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- CN105294463A CN105294463A CN201510514093.4A CN201510514093A CN105294463A CN 105294463 A CN105294463 A CN 105294463A CN 201510514093 A CN201510514093 A CN 201510514093A CN 105294463 A CN105294463 A CN 105294463A
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- triphenylamine
- triphenylamine derivative
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- dicarbaldehyde
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- 0 *c(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound *c(cc1)ccc1N(c1ccccc1)c1ccccc1 0.000 description 1
- VSUKSWCSOBXUFG-UHFFFAOYSA-N O=Cc(cc(c(C=O)c1)Br)c1Br Chemical compound O=Cc(cc(c(C=O)c1)Br)c1Br VSUKSWCSOBXUFG-UHFFFAOYSA-N 0.000 description 1
- FOSFMFPIJSMIGU-UHFFFAOYSA-N O=Cc1cc(-c(cc2)ccc2N(c2ccccc2)c2ccccc2)c(C=O)cc1-c(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound O=Cc1cc(-c(cc2)ccc2N(c2ccccc2)c2ccccc2)c(C=O)cc1-c(cc1)ccc1N(c1ccccc1)c1ccccc1 FOSFMFPIJSMIGU-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a triphenylamine derivative and a preparation method thereof. The synthesis method is simple and is easy to operate, and as compared with an original synthesis process, the reaction time is greatly shortened from the original 48 h to 40 min, the chemical environment is simpler in comparison with a reaction system, nitrogen protection and temperature increment are not needed, even a water solution can exist, and the productivity is relatively high and can reach 90 percent. The triphenylamine derivative (I) has the photoluminescence performance and can serve as a photoluminescence material.
Description
(1) technical field
The present invention relates to a kind of triphenylamine derivative and preparation method thereof.
(2) background technology
Suzuki reaction, also referred to as Suzuki linked reaction, Suzuki-Miyaura reaction (Suzuki-Pu, palace reaction), a newer organometallic coupling reaction, under zeroth order palladium complex catalyst, aryl or ene boric acid or boric acid ester and chlorine, bromine, iodo aromatic hydrocarbon or alkene generation cross-coupling.First this reaction is reported in 1979 by Suzuki chapter, having many uses in organic synthesis, the substrate adaptability that tool is strong and functional group's tolerance, be usually used in synthesizing polyene hydrocarbon, vinylbenzene and connection benzene derivate, thus be applied in the synthesis of numerous natural product, organic materials.
Suzuki reaction is very good to the tolerance of functional group, and reactant can be unaffected with the functional groups such as-CHO ,-COCH3 ,-COOC2H5 ,-OCH3 ,-CN ,-NO2 ,-F carry out reacting.React selective, the activity that the same halogen of different halogen and different positions carries out reacting may have difference.Another substrate is generally aryl boric acid, is reacted prepare by lithium aryl or Grignard reagent and boron alkyl acid esters.These compounds to air and water vapour more stable, easily store.Suzuki reaction is by the palladium catalyst catalysis of a four-coordination, and widely used catalyzer is tetrakis triphenylphosphine palladium (0).
Here conventional is halides, and wherein especially iodo and bromo are the most common, are also that reaction effect is good..SUZUKIcrosscouplingreaction, in the presence not having alkali, be difficult to reaction, even do not react! In reaction, the power of alkali (negative ion) is not only depended in the impact of alkali, and will take into account cationic character.If positively charged ion too little being unfavorable for generates middle transition state ylide (Pd) intermediate.As a rule, large cationic alkali, as Ba, Cs, meeting accelerated reaction, the speed that conductively-closed is reacted when positively charged ion is too little and efficiency will significantly decline.
The advantage of Suzuki linked reaction is exactly the intermediate defining this transition, allows reaction more easily carry out.Aryl boric acid and ester are one therefore its storage will not be problem to the stable material of water and air, and the reactive behavior simultaneously possessed.It is weak acid an about PKa=12, therefore, can reaction aftertreatment in utilize this point, with sodium hydroxide and its salify, organic solvent carry assorted purifying it.Catalyzer is that this reacts the place of most marrow, is also the most challenging up-to-date field.
The catalyzer of Suzuki linked reaction mainly contains two large class Pd classes, Ni class, the former can be used for Aquo System, tolerates a lot of functional groups, the latter's necessarily anhydrous and oxygen-free in the reaction.
The development experience of the catalyzer of Suzuki linked reaction crosses three processes:
(1) simple zeroth order Pd (0) and the salt of Ni (0) and the title complex of phosphorus, reactive behavior is lower as PdCl2, Pd/C etc.
(2) highly active palladium catalyst
(3) high reactivity, the catalyzer that can recycle
We daily many be the first and second classes, be the most common with Pd (PPh3) 4 in the first kind, most wide spectrum is that bromide and iodide are best for substrate, if the condition of reacting for inactive muriate wants harshness a bit.General part is exactly PPh3, PCy3.
The catalyzer of Suzuki linked reaction is all be afraid of oxygen, so it is an indispensable step that middle deoxidation is carried out in reaction, here the catalyzer of the very ironically third generation, it has high reactivity, high-level efficiency, it is that the solid-state therefore post-reaction treatment be insoluble in solvent is gone out by filtration, and recovery is recycled, such system, quaternary ammonium salt of adding some points improves the stability of catalyzer.
Generally speaking the suzuki reaction of C-C coupling generally needs reaction overnight; a reaction site generally needs the 24h even more time, and reaction whole process needs to ensure anaerobic anhydrous state, needs to react under nitrogen protection; otherwise the as easy as rolling off a log inactivation of palladium catalyst, and cause reacting unsuccessfully.Therefore seek one simple to operation, the reaction times is short and the C-C coupling methodology of organic synthesis that condition is not harsh is extremely necessary.
(3) summary of the invention
First object of the present invention is to provide a kind of triphenylamine derivative with criss-cross construction newly.
Second object of the present invention is to provide the method for the described triphenylamine derivative of a kind of simple preparation.
Below technical scheme of the present invention is illustrated.
The invention provides the triphenylamine derivative shown in a kind of formula (I), the chemistry of the triphenylamine derivative shown in described formula (I) 4,4 '-bis-(diphenyl amino) by name entirely-(Isosorbide-5-Nitrae ', 1-biphenyl)-2,5 '-dicarbaldehyde
The present invention also provides the preparation method of the triphenylamine derivative shown in a kind of formula (I), and described method is:
4-boric acid triphenylamine shown in 2,5-dibromobenzenes shown in formula (II)-Isosorbide-5-Nitrae-dicarbaldehyde and formula (III) reacts through Suzuki, the triphenylamine derivative shown in production (I);
The reaction formula of the triphenylamine derivative shown in synthesis type of the present invention (I) is as follows:
Further, described method is shown in formula (II) 2,5-dibromobenzene-1,4-boric acid triphenylamine shown in 4-dicarbaldehyde and formula (III) is under the effect of catalyst acetic acid palladium, basic cpd, in reaction solvent, react 20-45min (preferred 40min) under room temperature in air environment, reaction terminates rear reaction solution separation and purification and obtains the triphenylamine derivative shown in formula (I).
Described basic cpd preferably phosphoric acid tripotassium.
The mixing solutions of the preferred deionized water of described reaction solvent and Virahol, wherein the volume ratio of deionized water, Virahol is preferably 1:3 ~ 3.3.
Described shown in formula (II) 2,5-dibromobenzene-1,4-dicarbaldehyde, the 4-boric acid triphenylamine shown in formula (III), palladium are 1:1.3-2.5:0.05-0.2:1-2.5 with the ratio of the amount of substance that feeds intake of basic cpd, preferred 1:1.6-2.0:0.1:1.
In described reaction solvent, the volumetric usage of Virahol counts 15-35mL/g with the quality of 2, the 5-dibromobenzenes-Isosorbide-5-Nitrae-dicarbaldehyde shown in formula (II).
Concrete, described method can be carried out according to the following steps: 2 shown in formula (II), 5-dibromobenzene-1,4-dicarbaldehyde, the 4-boric acid triphenylamine shown in formula (III), palladium are dissolved in the mixing solutions of deionized water and Virahol volume ratio 1:3 ~ 3.3, then Tripotassium phosphate is added, at room temperature react 20-45min in air ambient, reaction terminates rear reaction solution separation and purification and obtains the triphenylamine derivative shown in formula (I).
Reaction solution purification procedures of the present invention is: after reaction terminates, reaction solution saturated aqueous common salt quencher, be extracted with ethyl acetate again, merge organic phase, use saturated common salt water washing, finally use anhydrous magnesium sulfate drying, filtration, filtrate is through concentrating under reduced pressure, and residuum silica gel column chromatography is separated, with the mixed solvent of sherwood oil, ethyl acetate volume ratio 25:1 for eluent, collect the elutriant containing product, elutriant steams and desolventizes the triphenylamine derivative shown in the formula of obtaining (I).
The present invention, by nucleus magnetic resonance (NMR), gas chromatography mass spectrometry (GC-MS), elemental analysis triphenylamine derivative (I), characterizes the crystalline structure of triphenylamine derivative (I) by X-ray diffraction (XRD).
Triphenylamine derivative of the present invention (I) has the molecular structure of right-angled intersection.
Triphenylamine derivative shown in formula provided by the invention (I) has photoluminescence performance, can at ultra violet lamp fluoresces, can apply as organic molecule embedded photoluminescent material, concrete, triphenylamine derivative is dissolved in Conventional solvents, as chloroform, methylene dichloride, tetrahydrofuran (THF), ethyl acetate etc., emission wavelength, at 400-700nm, can be used for manufacturing photodiode, electroluminescent device, embedded photoluminescent material and other electrooptical devices.
Compared with prior art, beneficial effect of the present invention is: the invention provides a kind of synthetic technology with the organic molecule triphenylamine derivative (I) of the molecular structure of new right-angled intersection, this synthetic method is simple to operation, compared to original synthesis technique, reaction times shortens greatly, shorten to 40min from original 48h, and the chemical environment of relative response system is simpler, protect without the need to nitrogen and heat up, even can there is the existence of the aqueous solution, and productive rate is higher, can 90% be reached.And obtained triphenylamine derivative (I) has luminescent properties.
(4) accompanying drawing explanation
Fig. 1 is the fluorescence photo of pressed powder (I) after being dissolved in dichloromethane solvent under ultraviolet lamp and liquid fluorescent spectrogram in the embodiment of the present invention 4.
(5) embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment 1
By 2,5-dibromobenzene-1,4-dicarbaldehyde (II) 1.46g (5mmol), 4-boric acid triphenylamine 3.46g (12mmol), palladium 0.1122g (0.5mmol) are dissolved in deionized water 8mL/ Virahol 25mL solution, add Tripotassium phosphate 1.05g (5mmol).In air ambient, room temperature reaction 40min.Reaction, with after saturated aqueous common salt quencher, is extracted with ethyl acetate three times, and merge organic phase, saturated common salt water washing, finally uses anhydrous magnesium sulfate drying.Filter, filtrate is through concentrating under reduced pressure, and residuum silica gel column chromatography is separated, the volume ratio of petrol ether/ethyl acetate is the mixed solvent wash-out of 25:1, collect the elutriant containing product, obtain orange powder product (I) 2.71g after elutriant solvent evaporated under reduced pressure, yield is 90%.The structural confirmation of material characterizes as follows:
1hNMR (500MHz, DMSO) δ 10.07 (s, 2H), 7.95 (s, 2H), 7.44 (d, J=8.6Hz, 4H), 7.42-7.26 (dd, 8H), 7.15 (d, J=8.7Hz, 12H), 7.08 (dd, J=8.6Hz, 4H) .MSm/z:620.2
Embodiment 2
By 2,5-dibromobenzene-1,4-dicarbaldehyde (II) 1.46g (5mmol), 4-boric acid triphenylamine 2.31g (8mmol), palladium palladium 0.11g (0.5mmol) are dissolved in deionized water 8mL/ Virahol 25mL solution, add Tripotassium phosphate 1.05g (5mmol).In air ambient, room temperature reaction 40min.Reaction, with after saturated aqueous common salt quencher, is extracted with ethyl acetate three times, and merge organic phase, saturated common salt water washing, finally uses anhydrous magnesium sulfate drying.Filter, filtrate is through concentrating under reduced pressure, and residuum silica gel column chromatography is separated, the volume ratio of petrol ether/ethyl acetate is the mixed solvent wash-out of 25:1, collect the elutriant containing product, obtain orange powder product (I) 1.48g after elutriant solvent evaporated under reduced pressure, yield is 60%.
Embodiment 3
The pressed powder (I) embodiment 1 obtained is dissolved in deuterochloroform, does hydrogen nuclear magnetic resonance detection, determines its molecular structure.Find that the hydrogen atom chemical shiftsum numbers of hydrogen atoms on nmr spectrum is consistent with simulated data.
Embodiment 4
The pressed powder (I) embodiment 1 obtained is dissolved in methylene dichloride, and concentration is 1.0*10
-5mol/L, the fluorescence spectrum of test soln, obtains its characteristic fluorescence utilizing emitted light spectrogram, as shown in Figure 1, confirms that it possesses photoluminescence performance.
Claims (8)
1. the triphenylamine derivative shown in a formula (I):
2. the preparation method of the triphenylamine derivative shown in formula (I) as claimed in claim 1, is characterized in that described method is:
4-boric acid triphenylamine shown in 2,5-dibromobenzenes shown in formula (II)-Isosorbide-5-Nitrae-dicarbaldehyde and formula (III) reacts through Suzuki, the triphenylamine derivative shown in production (I);
3. method as claimed in claim 2, it is characterized in that described method for:: 2 shown in formula (II), 5-dibromobenzene-1,4-boric acid triphenylamine shown in 4-dicarbaldehyde and formula (III) is under the effect of catalyst acetic acid palladium, basic cpd, in reaction solvent, react 20-45min under room temperature in air environment, reaction terminates rear reaction solution separation and purification and obtains the triphenylamine derivative shown in formula (I).
4. method as claimed in claim 3, is characterized in that described basic cpd is Tripotassium phosphate.
5. method as claimed in claim 3, it is characterized in that described reaction solvent is the mixing solutions of deionized water and Virahol, wherein the volume ratio of deionized water, Virahol is 1:3 ~ 3.3.
6. method as claimed in claim 3, it is characterized in that described shown in formula (II) 2,5-dibromobenzene-Isosorbide-5-Nitrae-dicarbaldehyde, the 4-boric acid triphenylamine shown in formula (III), palladium are 1:1.3-2.5:0.05-0.2:1-2.5 with the ratio of the amount of substance that feeds intake of basic cpd.
7. method as claimed in claim 3, it is characterized in that described method is carried out according to the following steps: 2 shown in formula (II), 5-dibromobenzene-1,4-dicarbaldehyde, the 4-boric acid triphenylamine shown in formula (III), palladium are dissolved in the mixing solutions of deionized water and Virahol volume ratio 1:3 ~ 3.3, then Tripotassium phosphate is added, at room temperature react 20-45min in air ambient, reaction terminates rear reaction solution separation and purification and obtains the triphenylamine derivative shown in formula (I); Described 2,5-dibromobenzenes shown in formula (II)-Isosorbide-5-Nitrae-dicarbaldehyde, the 4-boric acid triphenylamine shown in formula (III), palladium are 1:1.3-2.5:0.05-0.2:1-2.5 with the ratio of the amount of substance that feeds intake of Tripotassium phosphate.
8. the triphenylamine derivative shown in formula (I) as claimed in claim 1 is as the application of embedded photoluminescent material.
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| CN201510514093.4A CN105294463A (en) | 2015-08-20 | 2015-08-20 | Triphenylamine derivative and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125820A (en) * | 2007-08-10 | 2008-02-20 | 中国科学院长春光学精密机械与物理研究所 | Trianiline derivative used for light color conversion material and its preparation method and use |
| CN101948366A (en) * | 2010-07-31 | 2011-01-19 | 大连理工大学 | Method for preparing 4-(diphenylamino)biaryl compound in water phase |
| WO2013064794A1 (en) * | 2011-11-02 | 2013-05-10 | Cambridge Display Technology Limited | Polymer, light emitting device, and method |
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- 2015-08-20 CN CN201510514093.4A patent/CN105294463A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125820A (en) * | 2007-08-10 | 2008-02-20 | 中国科学院长春光学精密机械与物理研究所 | Trianiline derivative used for light color conversion material and its preparation method and use |
| CN101948366A (en) * | 2010-07-31 | 2011-01-19 | 大连理工大学 | Method for preparing 4-(diphenylamino)biaryl compound in water phase |
| WO2013064794A1 (en) * | 2011-11-02 | 2013-05-10 | Cambridge Display Technology Limited | Polymer, light emitting device, and method |
Non-Patent Citations (3)
| Title |
|---|
| LIU, CHUN等: "Very Fast, Ligand-Free and Aerobic Protocol for the Synthesis of 4-Aryl-Substituted Triphenylamine Derivatives", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| SUN, JINGWEI等: "A donor-acceptor cruciform ð-system: high contrast mechanochromic properties and multicolor electrochromic behavior", 《JOURNAL OF MATERIALS CHEMISTRY C: MATERIALS FOR OPTICAL AND ELECTRONIC DEVICES》 * |
| SUN, JINGWEI等: "A donor-acceptor cruciform ð-system: high contrast mechanochromic properties and multicolor electrochromic behavior", 《OURNAL OF MATERIALS CHEMISTRY C: MATERIALS FOR OPTICAL AND ELECTRONIC DEVICES》 * |
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Application publication date: 20160203 |