CN102924534A - 4,4'-diamido-4''-ferrocenyl triphenylamine and preparation method thereof - Google Patents
4,4'-diamido-4''-ferrocenyl triphenylamine and preparation method thereof Download PDFInfo
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Abstract
The invention provides 4,4'-diamido-4''-ferrocenyl triphenylamine and a preparation method of 4,4'-diamido-4''-ferrocenyl triphenylamine, belonging to the technical field of triphenylamine. The preparation method comprises the steps of taking 4-fluoronitrobenzene and 4-aminophenyl ferrocene as raw materials, adding a certain dose of catalyst, reacting for 12-72h at 110-180 DEG C to obtain 4,4'-binitro-4''-ferrocenyl triphenylamine, and then reducing dinitro-compound to 4,4'-diamido-4''-ferrocenyl triphenylamine by using target carbon as the catalyst and hydrazine hydrate as a reducing agent. 4,4'-diamido-4''-ferrocenyl triphenylamine provided by the invention is simple in synthetic process, low in requirements for the equipment, and high in yield, and the compound is not easy to be oxidized during the preparation process, thereby being suitable for mass production.
Description
Technical field
The invention belongs to the organic synthesis field, be specifically related to a kind of two amino aromatic structure organic compound that contains simultaneously fluorine-triphenylamine structure and ferrocene structure and preparation method thereof.
Background technology
Triphenylamine (Triphenylamine, TPA) and derivative have unique free radical character, as a kind of stable free radical source, can be used for studying other free radical and polyradical character, can also be as the catalyzer of electrochemical reaction and gentle selective oxidation reagent etc.The simultaneously conjugation of lone-pair electron in its structure because on three phenyl ring and the nitrogen-atoms that is connected them, present the large π-electron cloud of typical electron rich resonance structure, this is so that the organic compound that contains fluorine-triphenylamine structure all shows typical to electronic behavior, as one of putative most important electron donor(ED) structure in group electricity consideration convey moves process with the energy level coupling usually.The compound that contains fluorine-triphenylamine structure has obtained very wide practical application and development space in organic synthesis, functional organic material and functional polymer polymer materials design preparation field at present, it is the preparation charge transfer material, the important raw and processed materials of electroluminescent material etc. also can be made organic dye and medicine intermediate simultaneously.Although fluorine-triphenylamine structure is simple, exist complicated process of preparation, in air the easy problem such as oxidation, therefore design the compound that contains fluorine-triphenylamine structure of composite structure novelty, expand its Application Areas is the direction of research always.As with fluorine-triphenylamine structure as the electron donor(ED) unit, then it being combined with the method for electron acceptor(EA) unit by physics or chemistry obtains important application and the research field that functional materials is triphenylamine compound.
Can there be two kinds of different steady states in the organic materials with electric bistable performance that contains simultaneously electron donor(ED) and electron acceptor(EA) in the molecular chain under electric field action be low resistance state (conductive state) and high-resistance state (insulation attitude), the low resistance state of material and high-impedance state are equivalent to " 1 " and " 0 " in the Computer Storage, thereby can realize switch and information storage function, in order to exploitation in future new high-density canned data material and corresponding memory technology.The organic compound and the polymkeric substance thereof that contain fluorine-triphenylamine structure have the following advantages as storage medium: apparatus structure is simple, dimensional stability is good, and is with low cost, and operating voltage is lower, have accessibility, the good and storage capacity of three-dimensional dimension stacking performance is larger etc.Simultaneously, the diamino triphenylamine can also be as diamine monomer synthesis of polyimides/polyamide material.
But fluorine-triphenylamine structure is too single, has problems such as being easy to oxidation in air, and in order to expand the diversity of its structure, and also in order to obtain better to Electronic Performance, and in conjunction with the advantage of other organic group structures, we introduce the ferrocene structure.Ferrocene is the representative of sandwich compound, it is a kind of orange prism-shaped crystal, have two parallel cyclopentadienide anions, an iron (II) ion is being inlayed in the centre, being clipped between two luxuriant plane of a loops of iron ion symmetry, it is typical electron rich body, its chemical property is highly stable, is difficult for occuring addition and reduction reaction on the luxuriant ring, but electrophilic substitution reaction occurs easily, have outstanding aromaticity, therefore the difference according to substitution reaction can access thousands of kinds of derivatives.Just because of its unique molecular structure and outstanding aromatic character thereof, ferrocene and derivative thereof have many special performances, have set foot in modification and biochemistry and medicine and other fields in asymmetric organic catalyst compound, combustion controlling agent or conditioning agent, photosensitizers, stablizer, modifying agent, electrode for their applied research.
Ferrocene is introduced in the structure of diamino triphenylamine, expectation is attached to the property of ferrocene structure in the diamino triphenylamine, realizes that it is having larger application prospect aspect organic catalyst compound, organic dye, medicine intermediate and the specific function material.This structure yet there are no bibliographical information.
Summary of the invention
The object of the present invention is to provide the binary amine compound 4 that contains simultaneously two kinds of electronic donor groups (being triphenylamine and ferrocene), 4 '-diamino-4 "-ferrocenyl triphenylamine and preparation method.Provided by the present invention 4,4 '-diamino-4 "-the route of synthesis productive rate of ferrocenyl triphenylamine is high, and compound is difficult for oxidized, and synthesis technique is simple, need not complicated equipment.
Compound 4,4 '-diamino-4 that the present invention synthesized "-chemical structural formula of ferrocenyl triphenylamine is as follows:
Provided by the present invention 4,4 '-diamino-4 "-preparation method of ferrocenyl triphenylamine, may further comprise the steps:
(1) 4,4 '-dinitrobenzene-4 "-preparation of ferrocenyl triphenylamine:
With 4-ferrocenyl aniline, to fluoronitrobenzene and catalyzer, by the mol ratio 2～4:1 to fluoronitrobenzene and 4-ferrocenyl aniline, catalyzer with the mol ratio 2～3:1 of fluoronitrobenzene is joined in the organic solvent after the dissolving, 110～180 ° of C reactions 12～72 hours, after being cooled to room temperature, the washed reaction product is that eluent is dry after post separates with ethyl acetate/petroleum ether (1:5) after filtering gets 4,4 '-dinitrobenzene-4 "-the ferrocenyl triphenylamine.Shown in reaction equation (1):
(2) 4,4 '-diamino-4 "-preparation of ferrocenyl triphenylamine:
With 4,4 '-dinitrobenzene-4 "-the ferrocenyl triphenylamine is dissolved in the organic solvent; take palladium carbon as catalyzer, its consumption is 4,4 '-dinitrobenzene-4 "-ferrocenyl triphenylamine quality 5～40%, under stirring and reflux condition, slowly drip hydrazine hydrate, reflux after for some time, some plate monitoring reaction process is until till reaction finishes, heat is filtered, is revolved steaming, the gained precipitation is obtained target product 4 with drying behind the ethyl alcohol recrystallization, 4 '-diamino-4 "-the ferrocenyl triphenylamine.Shown in reaction equation (2):
Wherein, catalyzer is carbonic acid compounds and cesium fluoride in the step 1), such as Anhydrous potassium carbonate, anhydrous sodium carbonate, cesium fluoride etc.
The preferred aprotic polar solvent of organic solvent in the step 1) is such as dimethyl sulfoxide (DMSO) (DMSO), DMF (DMF), N,N-dimethylacetamide (DMAc) etc.
Preferably reaction system was heated 12～48 hours in 130～150 ° of C in the step 1).
Step 2) organic solvent described in is ethanol or Virahol.
5%～10% palladium carbon (the quality percentage composition of palladium is 5%～10%) is catalyzer, and its consumption is 4,4 '-dinitrobenzene-4 "-ferrocenyl triphenylamine quality 5～40%,
Step 2) consumption of hydrazine hydrate is the volume (ml) and 4 of hydrazine hydrate in, 4 '-dinitrobenzene-4 "-ratio of the mole number (mmol) of ferrocenyl triphenylamine is 15～20:1.
Step 2) reflux time in is 24～48 hours.
Compared with prior art, the present invention has following beneficial effect:
1) provided by the present invention 4,4 '-diamino-4 "-the ferrocenyl fluorine-triphenylamine structure is novel, contains simultaneously two kinds of electronic donor groups; productive rate higher (60%～75%), oxidation in air is difficult for, and relative 4; 4 '-diamino triphenylamine is more stable, be applicable to mass-producing and prepare.
2) synthesis technique provided by the present invention is simple, and is easy and simple to handle, need not complex apparatus, and without waste residue and discharge of wastewater.
3) the present invention synthesized 4,4 '-diamino-4 "-design that the ferrocenyl triphenylamine can be functional organic material and macromolecule polymer material provides new monomer; as can be used for syntheticly containing ferrocene structure and synthetic polymeric amide and the polyimide material that contains the Electron donor acceptor structure, and be with a wide range of applications in the numerous areas such as dyestuff, medicine, agrochemicals, additive, sequestrant, linking agent, protective agent as arylamine.
Description of drawings
Fig. 1. 4 of embodiment 1 preparation, 4 '-dinitrobenzene-4 "-infrared spectrum of ferrocenyl triphenylamine;
Fig. 2. 4 of embodiment 1 preparation, 4 '-dinitrobenzene-4 "-the hydrogen nuclear magnetic spectrogram of ferrocenyl triphenylamine;
Fig. 3. 4 of embodiment 1 preparation, 4 '-diamino-4 "-infrared spectrum of ferrocenyl triphenylamine;
Fig. 4. 4 of embodiment 1 preparation, 4 '-diamino-4 "-the hydrogen nuclear magnetic spectrogram of ferrocenyl triphenylamine;
Fig. 5. 4 of embodiment 1 preparation, 4 '-diamino-4 "-the DSC spectrogram of ferrocenyl triphenylamine;
Fig. 6. 4 of embodiment 1 preparation, 4 '-diamino-4 "-mass spectrum of ferrocenyl triphenylamine;
Fig. 7 is the infrared figure of embodiment 5 polyimide.
Specific embodiment
A) 4,4 '-dinitrobenzene-4 "-preparation of ferrocenyl triphenylamine:
In the 100ml single port flask of reflux condensation mode and magneton is housed, add 4-ferrocenyl aniline 2.21g, to fluoronitrobenzene 2.26g and Anhydrous potassium carbonate 4.42g, and adding 30ml DMSO is solvent, open magnetic agitation and water of condensation, and be heated to 130 ° of C with constant temperature oil bath, reacted 24 hours, reaction is cooled to room temperature after finishing, pour into reaction soln in the 800ml deionized water and precipitate 24 hours, remove supernatant liquid, obtain the thick precipitation of garnet.Adopt the post partition method to purify, eluent is ethyl acetate and sherwood oil, and ratio is 1:5, and after revolving the inspissation contracting in 60 ° of C vacuum drying ovens dry 12 hours, obtaining the red solid powder was final product 4,4 '-dinitrobenzene-4 "-the ferrocenyl triphenylamine.The product quality that obtains is 2.90g.
Productive rate 70.0%, fusing point: 263 ° of C(DSC); Infrared (KBr compressing tablet): 3100cm
-1(phenyl ring C-H stretching vibration), the luxuriant ring of 2918-2850cm-1(C-H stretching vibration), 1580cm
-1And 1308cm
-1(nitro N-O stretching vibration); Nuclear-magnetism (
1H-NMR, DMSO-d6,400MHz), δ (ppm): 4.09 (5H), 4.40 (2H), 4.82 (2H), 7.18 (2H), 7.25 (4H), 7.65 (2H), 8.21 (4H).
B) 4,4 '-diamino-4 "-preparation of ferrocenyl triphenylamine:
In the 100ml there-necked flask of reflux condensation mode and constant pressure funnel is housed, add 4,4'-dinitrobenzene-4 " ferrocenyl triphenylamine 0.733g, 5%～10% palladium carbon 0.21g and ethanol 30ml; In dropping funnel, add the 20ml hydrazine hydrate.The oil bath heating, temperature of reaction is 90 ℃, drips hydrazine hydrate under the reflux temperature of ethanol.Reacted 72 hours.After reaction finishes, heat filtering fast reduces pressure, remove palladium carbon, revolve steam 4,4'-diamino-4 " be that the mixing solutions of 4:1 carries out recrystallization with the ratio of second alcohol and water behind the crude product of ferrocenyl triphenylamine, and in 60 ° of C vacuum drying ovens dry 12 hours, finally obtain 4; 4 '-diamino-4 "-the ferrocenyl triphenylamine is the orange tabular crystal, quality is 0.500g.
Productive rate 77.0%, fusing point: 211 ° of C(DSC); Infrared (KBr compressing tablet): 3450-3200cm
-1(N-H stretching vibration peak); Nuclear-magnetism (
1H-NMR, DMSO-d
6, 400MHz), δ (ppm): 4.01 (5H), 4.24 (2H), 4.59 (2H), 4.96 (4H), 6.55 (6H), 6.80 (4H), 7.24 (2H); Ultimate analysis C-73.62%, H-5.652%, N-8.881%, Fe-11.847%; Mass spectrum (m/z): [M+H+] measured value 460.6.
A) 4,4 '-dinitrobenzene-4 "-preparation of ferrocenyl triphenylamine
In the 250ml single port flask of reflux condensation mode and magneton is housed, add 4-ferrocenyl aniline 6.9g, to fluoronitrobenzene 10.58g and Anhydrous potassium carbonate 20.7g, and adding 100ml DMSO is solvent, open magnetic agitation and water of condensation, and being heated to 150 ° of C reaction 48 hours with constant temperature oil bath, reaction is cooled to room temperature after finishing, and pours into reaction soln in the 1600ml deionized water and precipitates 24 hours, remove supernatant liquid, obtain the thick precipitation of garnet.Adopt the post partition method to purify, eluent is ethyl acetate and sherwood oil, and ratio is 1:5, and after revolving the inspissation contracting in 60 ° of C vacuum drying ovens dry 12 hours, obtaining the red solid powder was final product 4,4 '-dinitrobenzene-4 "-the ferrocenyl triphenylamine.The product quality that obtains is 9.76g;
Productive rate 75.4%, fusing point: 263 ° of C(DSC); Infrared (KBr compressing tablet): 3100cm
-1(phenyl ring C-H stretching vibration), the luxuriant ring of 2918-2850cm-1(C-H stretching vibration), 1580cm
-1And 1308cm
-1(nitro N-O stretching vibration); Nuclear-magnetism (
1H-NMR, DMSO-d6,400MHz), δ (ppm): 4.09 (5H), 4.40 (2H), 4.82 (2H), 7.18 (2H), 7.25 (4H), 7.65 (2H), 8.21 (4H).
B) 4,4 '-diamino-4 "-preparation of ferrocenyl triphenylamine:
In the 250ml there-necked flask of reflux condensation mode and constant pressure funnel is housed, add 4,4'-dinitrobenzene-4 " ferrocenyl triphenylamine 2.58g, 5%～10% palladium carbon 1.00g and Virahol 100ml; In dropping funnel, add the 20ml hydrazine hydrate.The oil bath heating, temperature of reaction is 90 ℃, drips hydrazine hydrate under the reflux temperature of ethanol.Reacted 24 hours, and dripped the 55ml hydrazine hydrate with dropping funnel more midway.After reaction finishes, heat filtering fast reduces pressure, repeated multiple times until Ex-all palladium carbon, revolve steam 4,4'-diamino-4 " be that the mixing solutions of 4:1 carries out recrystallization with the ratio of second alcohol and water behind the crude product of ferrocenyl triphenylamine, and in 60 ° of C vacuum drying ovens dry 12 hours, finally obtain 4; 4 '-diamino-4 "-the ferrocenyl triphenylamine is the orange tabular crystal, quality is 1.82g.
Productive rate 79.3%, fusing point: 211 ° of C(DSC); Infrared (KBr compressing tablet): 3450-3200cm
-1(N-H stretching vibration peak); Nuclear-magnetism (
1H-NMR, DMSO-d
6, 400MHz), δ (ppm): 4.01 (5H), 4.24 (2H), 4.59 (2H), 4.96 (4H), 6.55 (6H), 6.80 (4H), 7.24 (2H); Ultimate analysis C-73.62%, H-5.652%, N-8.881%, Fe-11.847%; Mass spectrum (m/z): [M+H+] measured value 460.6.
A) 4,4 '-dinitrobenzene-4 "-preparation of ferrocenyl triphenylamine:
In the 100ml single port flask of reflux condensation mode and magneton is housed, add 4-ferrocenyl aniline 2.21g, to fluoronitrobenzene 2.26g and cesium fluoride 3.65g, and adding 30ml DMF is solvent, open magnetic agitation and water of condensation, and be heated to 130 ° of C with constant temperature oil bath, reacted 24 hours, reaction is cooled to room temperature after finishing, pour into reaction soln in the 800ml deionized water and precipitate 24 hours, remove supernatant liquid, obtain the thick precipitation of garnet.Adopt the post partition method to purify, eluent is ethyl acetate and sherwood oil, and ratio is 1:5, and after revolving the inspissation contracting in 60 ° of C vacuum drying ovens dry 12 hours, obtaining the red solid powder was final product 4,4 '-dinitrobenzene-4 "-the ferrocenyl triphenylamine.The product quality that obtains is 2.84g;
Productive rate 68.4%, fusing point: 263 ° of C(DSC); Infrared (KBr compressing tablet): 3100cm
-1(phenyl ring C-H stretching vibration), the luxuriant ring of 2918-2850cm-1(C-H stretching vibration), 1580cm
-1And 1308cm
-1(nitro N-O stretching vibration); Nuclear-magnetism (
1H-NMR, DMSO-d6,400MHz), δ (ppm): 4.09 (5H), 4.40 (2H), 4.82 (2H), 7.18 (2H), 7.25 (4H), 7.65 (2H), 8.21 (4H).
B) 4,4 '-diamino-4 "-preparation of ferrocenyl triphenylamine:
In the 100ml there-necked flask of reflux condensation mode and constant pressure funnel is housed, add 4,4'-dinitrobenzene-4 " ferrocenyl triphenylamine 0.733g, 5%～10% palladium carbon 0.30g and ethanol 30ml; In dropping funnel, add the 25ml hydrazine hydrate.The oil bath heating, temperature of reaction is 90 ℃, drips hydrazine hydrate under the reflux temperature of ethanol.Reacted 48 hours.After reaction finishes, heat filtering fast reduces pressure, repeated multiple times until Ex-all palladium carbon, revolve steam 4,4'-diamino-4 " be that the mixing solutions of 4:1 carries out recrystallization with the ratio of second alcohol and water behind the crude product of ferrocenyl triphenylamine, and in 60 ° of C vacuum drying ovens dry 12 hours, finally obtain 4; 4 '-diamino-4 "-the ferrocenyl triphenylamine is the orange tabular crystal, quality is 0.523g.
Productive rate 80.6%, fusing point: 211 ° of C(DSC); Infrared (KBr compressing tablet): 3450-3200cm
-1(N-H stretching vibration peak); Nuclear-magnetism (1H-NMR, DMSO-d
6, 400MHz), δ (ppm): 4.01 (5H), 4.24 (2H), 4.59 (2H), 4.96 (4H), 6.55 (6H), 6.80 (4H), 7.24 (2H); Ultimate analysis: C-73.62%, H-5.652%, N-8.881%, Fe-11.847%; Mass spectrum (m/z): [M+H+] measured value 460.6.
Embodiment 4
A) 4,4 '-dinitrobenzene-4 "-preparation of ferrocenyl triphenylamine:
In the 250ml single port flask of reflux condensation mode and magneton is housed, add 4-ferrocenyl aniline 6.9g, to fluoronitrobenzene 10.58g and cesium fluoride 14.87g, and adding 100ml DMF is solvent, open magnetic agitation and water of condensation, and be heated to 150 ° of C with constant temperature oil bath, reacted 12 hours, reaction is cooled to room temperature after finishing, pour into reaction soln in the 1600ml deionized water and precipitate 24 hours, remove supernatant liquid, obtain the thick precipitation of garnet.Adopt the post partition method to purify, eluent is ethyl acetate and sherwood oil, and ratio is 1:5, and after revolving the inspissation contracting in 60 ° of C vacuum drying ovens dry 12 hours, obtaining the red solid powder was final product 4,4 '-dinitrobenzene-4 "-the ferrocenyl triphenylamine.The product quality that obtains is 9.49g;
Productive rate 73.2%, fusing point: 263 ° of C(DSC); Infrared (KBr compressing tablet): 3100cm
-1(phenyl ring C-H stretching vibration), the luxuriant ring of 2918-2850cm-1(C-H stretching vibration), 1580cm
-1And 1308cm
-1(nitro N-O stretching vibration); Nuclear-magnetism (
1H-NMR, DMSO-d6,400MHz), δ (ppm): 4.09 (5H), 4.40 (2H), 4.82 (2H), 7.18 (2H), 7.25 (4H), 7.65 (2H), 8.21 (4H).
B) 4,4 '-diamino-4 "-preparation of ferrocenyl triphenylamine:
In the 250ml there-necked flask of reflux condensation mode and constant pressure funnel is housed, add 4,4'-dinitrobenzene-4 " ferrocenyl triphenylamine 2.58g, 5%～10% palladium carbon 0.50g and Virahol 100ml; In dropping funnel, add the 20ml hydrazine hydrate.The oil bath heating, temperature of reaction is 90 ℃, drips hydrazine hydrate under the reflux temperature of ethanol.Reacted 12 hours, and dripped the 55ml hydrazine hydrate with dropping funnel more midway.After reaction finishes, heat filtering fast reduces pressure, heat filtering fast reduces pressure, repeated multiple times until Ex-all palladium carbon, revolve steam 4,4'-diamino-4 " be that the mixing solutions of 4:1 carries out recrystallization with the ratio of second alcohol and water behind the crude product of ferrocenyl triphenylamine; and in 60 ° of C vacuum drying ovens dry 12 hours; finally obtain 4,4 '-diamino-4 "-the ferrocenyl triphenylamine is the orange tabular crystal, quality is 1.59g.
Productive rate 69.6%, fusing point: 211 ° of C(DSC); Infrared (KBr compressing tablet): 3450-3200cm
-1(N-H stretching vibration peak); Nuclear-magnetism (
1H-NMR, DMSO-d
6, 400MHz), δ (ppm): 4.01 (5H), 4.24 (2H), 4.59 (2H), 4.96 (4H), 6.55 (6H), 6.80 (4H), 7.24 (2H); Ultimate analysis: C-73.62%, H-5.652%, N-8.881%, Fe-11.847%; Mass spectrum (m/z): [M+H+] measured value 460.6.
With 4,4 '-diamino-4 "-the ferrocenyl triphenylamine is diamine monomer, take hexafluoro sec.-propyl two (Tetra hydro Phthalic anhydride) as the dianhydride monomer synthesis of polyimides.
" ferrocenyl triphenylamine, 88.84mg hexafluoro tetracarboxylic acid dianhydride (6FDA) add 5ml meta-cresol, 500 μ l isoquinoline 99.9, magnetic agitation under the nitrogen protection condition to prop up adding 91.87mg 4 in mouthful bottle, 4'-diamino-4 in the 25ml pyriform.React in 190 ℃ of oil bath pans after 12 hours, the polyimide solution that obtains is slowly poured in the beaker that 200ml methyl alcohol is housed precipitated, repeatedly clean the polyimide precipitation with methyl alcohol afterwards, and drying got final product in 24 hours in 100 ℃ of vacuum drying ovens.Reaction equation is as shown below:
Infrared (KBr compressing tablet): 1782cm
-1(C-O asymmetrical stretching vibration peak); 1724cm
-1(C-O symmetrical stretching vibration peak); 1375cm
-1(C-N stretching vibration peak); 721cm
-1(C-O rocking vibration peak).
Claims (8)
1.4,4 '-diamino-4 "-the ferrocenyl triphenylamine, chemical structural formula is as follows:
2.4,4 '-diamino-4 "-preparation method of ferrocenyl triphenylamine, it is characterized in that, may further comprise the steps:
(1) 4,4 '-dinitrobenzene-4 "-preparation of ferrocenyl triphenylamine:
With 4-ferrocenyl aniline, to fluoronitrobenzene and catalyzer, by the mol ratio 2～4:1 to fluoronitrobenzene and 4-ferrocenyl aniline, catalyzer with the mol ratio 2～3:1 of fluoronitrobenzene is joined in the organic solvent after the dissolving, 110～180 ° of C reactions 12～72 hours, after being cooled to room temperature, the washed reaction product, be that the ethyl acetate/petroleum ether of 1:5 is that eluent is dry after post separates must 4 with volume ratio after filtering, 4 '-dinitrobenzene-4 "-the ferrocenyl triphenylamine, shown in reaction equation (1):
(2) 4,4 '-diamino-4 "-preparation of ferrocenyl triphenylamine:
With 4,4 '-dinitrobenzene-4 "-the ferrocenyl triphenylamine is dissolved in the organic solvent; take palladium carbon as catalyzer; stir and the reflux condition under drip hydrazine hydrate; reflux; until till reaction finishes, the heat filter, revolve steaming, gained is precipitated obtain target product 4 with drying behind the ethyl alcohol recrystallization, 4 '-diamino-4 "-the ferrocenyl triphenylamine.
3. according to the method for claim 2, it is characterized in that catalyzer is Carbon Dioxide compounds and cesium fluoride in the step (1).
4. according to the method for claim 2, it is characterized in that organic solvent is aprotic polar solvent in the step (1); Step 2) organic solvent described in is ethanol or Virahol.
5. according to the method for claim 2, it is characterized in that palladium carbon is 5%～10% palladium carbon, its consumption is 4,4 '-dinitrobenzene-4 "-ferrocenyl triphenylamine quality 5～40%.
6. according to the method for claim 2, it is characterized in that reaction system was in 130～150 ° of C heating 12～48 hours in the step (1).
7. according to the method for claim 2, it is characterized in that the consumption of hydrazine hydrate is the volume ml and 4 of hydrazine hydrate in the step (2), 4 '-dinitrobenzene-4 "-ratio of the mole number mmol of ferrocenyl triphenylamine is 15～20:1.
8. according to the method for claim 2, it is characterized in that the reflux time in the step (2) is 24～48 hours.
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| CN106317129A (en) * | 2015-07-01 | 2017-01-11 | 郑建鸿 | Amino ferrocene derivative and organic light emitting diode |
| CN107056845A (en) * | 2017-04-25 | 2017-08-18 | 衡阳师范学院 | Triaryl amine and ferrocene end group compound of phenyl bridging and its preparation method and application |
| CN112920228A (en) * | 2021-02-01 | 2021-06-08 | 衡阳师范学院 | Aromatic ring bridged ferrocene and diphenylamine compound as well as preparation method and application thereof |
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| CN107056845B (en) * | 2017-04-25 | 2019-01-18 | 衡阳师范学院 | Triaryl amine and ferrocene end group compound of phenyl bridging and its preparation method and application |
| CN112920228A (en) * | 2021-02-01 | 2021-06-08 | 衡阳师范学院 | Aromatic ring bridged ferrocene and diphenylamine compound as well as preparation method and application thereof |
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