CN108276300B - Method for preparing biphenyl triarylamine compound by using carboxyl as guide group, intermediate and preparation method thereof - Google Patents
Method for preparing biphenyl triarylamine compound by using carboxyl as guide group, intermediate and preparation method thereof Download PDFInfo
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- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/56—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in ortho-position
- C07C229/58—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in ortho-position having the nitrogen atom of at least one of the amino groups further bound to a carbon atom of a six-membered aromatic ring, e.g. N-phenyl-anthranilic acids
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Abstract
The invention relates to a method for preparing biphenyl triarylamine compounds by using carboxyl as a guide group, an intermediate and a preparation method thereof. The intermediate has a structure shown as the following formula:
Description
Technical Field
The invention belongs to the field of synthesis of biphenyl triarylamine compounds, and particularly relates to a method for preparing a biphenyl triarylamine compound by using carboxyl as a guide group, an intermediate and a preparation method thereof.
Background
In the organic hole transport material, the triarylamine compound can form ammonium ion free radicals under the action of an electric field, so that the triarylamine compound has higher hole mobility and good hole transport performance. The triarylamine hole transport materials developed at present mainly include triphenylamine and derivatives thereof, biphenyl type triarylamine compounds, triarylamine compounds containing fluorene rings in the molecules, and other triarylamine compounds. The alkyl substituted biphenyl triarylamine compound has high hole mobility and stability, and has high solubility in resin due to the fact that molecules contain nonpolar groups such as methyl, and the alkyl substituted biphenyl triarylamine compound is not easy to exude from organic resin. Meanwhile, the introduction of alkyl substituent can reduce the symmetry of molecules and increase the number of conformational isomers of the molecules, thereby changing the aggregation mode of the molecules, effectively preventing the crystallization tendency of the molecules, and improving the film forming property of the molecules and the thermal stability of the film. Furthermore, the glass transition temperature (T) of such compoundsg) Are generally higher, and can avoid T due to low materialgThe problems of softening of the transport layer, bleeding of the hole transport material from the organic resin, and deterioration of the transport performance are caused.
As a research hotspot and a focus of hole transport materials, the synthesis of biphenyl triarylamine compounds is always concerned by researchers, and the traditional preparation method mainly adopts an Ullmann reaction method and a Buchwald-Hartwig reaction method. However, in the existing literature, the reaction system for preparing the biphenyl triarylamine compound by the Ullmann reaction method has the advantages of high temperature, long time, low yield and purity, and the high-efficiency ligand can be synthesized only by a complex process; the catalyst used in the Buchwald-Hartwig reaction method is expensive, so that the cost of the prepared biphenyl triarylamine compound is high, and the biphenyl triarylamine compound is not beneficial to popularization and application in the field of hole transport materials.
Patent application publication No. CN1769369A discloses a preparation method of a triarylamine hole transport material, which uses aromatic secondary amine and aromatic iodo-compound as reaction raw materials, and performs reaction preparation under a metal halide/1, 10-phenanthroline/alkali catalytic system, so as to make the reaction conditions of the aromatic secondary amine and the aromatic iodo-compound milder, shorten the reaction time and improve the reaction yield. The main raw material for preparing the biphenyl triarylamine compound by the preparation method is N, N' -diphenyl benzidine, the industrial cost of the raw material is higher, and the preparation method is not beneficial to popularization and application in industrial production of the biphenyl triarylamine compound.
Disclosure of Invention
The invention aims to provide an intermediate for preparing biphenyl triarylamine compounds, so as to solve the problem of high industrial production cost of the existing technical route for synthesizing biphenyl triarylamine compounds.
The second object of the present invention is to provide a process for the preparation of the above intermediates.
The third purpose of the invention is to provide a method for preparing biphenyl triarylamine compounds by using carboxyl as a guide group.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an intermediate for preparing biphenyl triarylamine compounds has a structure shown as a formula (1):
in the formula (1), R is selected from hydrogen, alkyl with 1-10 carbon atoms, halogenated alkyl with 1-5 carbon atoms, alkoxy with 1-5 carbon atoms and aryl.
The intermediate for preparing the biphenyl triarylamine compounds can be prepared and synthesized by utilizing simple and easily obtained raw materials, the biphenyl triarylamine compounds prepared by the intermediate have high purity and yield, the production cost of the biphenyl triarylamine compounds can be obviously reduced, and the intermediate is very suitable for industrial production of the biphenyl triarylamine compounds.
Preferably, R is H, methyl, butyl, trifluoromethyl, methoxy or phenyl.
The technical scheme adopted by the preparation method of the intermediate for preparing the biphenyl triarylamine compound is as follows:
a preparation method of an intermediate for preparing biphenyl triarylamine compounds comprises the following steps: reacting substituted diphenylamine, 4' -dihalobiphenyl, metal carbonate and a first catalyst in a first solvent at the temperature of 150-200 ℃ to obtain the catalyst; the structural formula of the substituted diphenylamine is as follows:
wherein R is selected from hydrogen, alkyl with 1-10 carbon atoms, halogenated alkyl with 1-5 carbon atoms, alkoxy with 1-5 carbon atoms and aryl.
In the substituted diphenylamine, R is preferably H, methyl, butyl, trifluoromethyl, methoxy or phenyl.
The metal carbonate is one or more of potassium carbonate, sodium bicarbonate and cesium carbonate.
The first catalyst is copper and/or copper oxide.
Preferably, the ratio of the amounts of the substituted diphenylamine, the 4, 4' -dihalobiphenyl, the metal carbonate, and the first catalyst is 1: (0.4-0.5): (2-4): 0.04. further preferably, the first catalyst is a mixture of copper and copper oxide in a mass ratio of 1: 1. The reaction time is 2-10h at 150-200 ℃.
The first solvent is one of N, N-dimethylaniline, diethylene glycol ethyl ether, nitrobenzene and dimethyl sulfoxide. Preferably, the ratio of the amounts of the substituted diphenylamine, the 4, 4' -dihalobiphenyl, the metal carbonate, the copper oxide, and the first solvent is 1: (0.4-0.5): (2-4): 0.02: 0.02: (3-10).
The structural formula of the 4, 4' -dihalobiphenyl is as follows:
wherein X is one of Cl, Br and I.
The substituted diphenylamine can be prepared by an Ullmann reaction, and preferably, the substituted diphenylamine is prepared by a method comprising the following steps of: reacting substituted aniline, o-chlorobenzoic acid, metal carbonate and a second catalyst in a second solvent at 100-120 ℃ to obtain the catalyst(ii) a The structural formula of the substituted aniline is as follows:
wherein R is selected from hydrogen, alkyl with 1-10 carbon atoms, halogenated alkyl with 1-5 carbon atoms, alkoxy with 1-5 carbon atoms and aryl. R is preferably H, methyl, butyl, trifluoromethyl, methoxy or phenyl.
The second catalyst is one or the combination of more of copper, cupric oxide and cuprous oxide.
The mass ratio of the substituted aniline to the o-chlorobenzoic acid to the metal carbonate to the second catalyst is (0.5-0.8): 1: (1-3.5): (0.01-0.1). The second catalyst is preferably a mixture of copper and copper oxide in a mass ratio of 1: 1.
The second solvent is one of dimethyl sulfoxide, N-dimethylformamide, water, N-dimethylacetamide and cyclohexanone. The mass ratio of the substituted aniline to the second solvent is (0.5-0.8): (1-10).
The preparation method of the intermediate takes carboxyl as a guiding group, so that the reaction conditions of the substituted diphenylamine and the halogenated biphenyl are reduced, the used catalyst is simple and easy to obtain, the purity and the yield of the reaction product are high, the industrial manufacturing cost of the intermediate is reduced, and good conditions are created for reducing the industrial production cost of the biphenyl triarylamine compound.
The method for preparing the biphenyl triarylamine compound by taking carboxyl as a guide group adopts the technical scheme that:
a method for preparing biphenyl triarylamine compounds by taking carboxyl as a guide group comprises the following steps: and (3) performing decarboxylation reaction on the intermediate, the third catalyst and the ligand in a third solvent at 140-200 ℃ to obtain the catalyst.
The third catalyst is cuprous oxide. The ligand is N, N ' -dimethyl piperazine, triethylamine, phenanthroline, substituted phenanthroline, N, N, N ', N ' -tetramethyl ethylenediamine, N, N-dimethylaniline or N, N-diisopropyl. The mass ratio of the intermediate, the third catalyst and the ligand is 1: (0.01-0.1): (0.01-0.05).
The third solvent is one of N-methyl pyrrolidone and dimethyl sulfoxide. The mass ratio of the intermediate to the third solvent is 1: (3-6).
The decarboxylation reaction time is 4-8 h.
The method for preparing the biphenyl triarylamine compound by using the carboxyl as the guide group uses the intermediate to react in the presence of the catalyst and the ligand, the reaction process is mild and easy to control, the purity and the yield of the product are high, the industrial manufacturing cost of the biphenyl triarylamine compound is obviously reduced, and the method has good industrial application value. The product purity of the preparation method is more than 99.5 percent, the reaction yield is more than 82 percent, the reaction for synthesizing the substituted diphenylamine can use environment-friendly water as a solvent, and the post-treatment is simple.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
Example 1
The intermediate for preparing biphenyl triarylamine compound of this example has the structural formula shown in formula (2):
the process route of the preparation of biphenyl triarylamine compounds with carboxyl as a guiding group in this example is as follows:
the method comprises the following specific steps:
1) synthesis of intermediates
Adding 4.00kg of water into a reactor with a thermometer and a reflux device, sequentially adding 2.00kg of o-chlorobenzoic acid, 2.00kg of potassium carbonate, 0.02kg of copper oxide and 1.00kg of 3-methylaniline (1a) while stirring, heating the system to 100 ℃ for reaction, monitoring the reaction to the end point by TLC, and stopping heating; cooling the system to 60 ℃, adding 0.16kg of active carbon for decoloring, continuously stirring until the system is uniform, filtering, adding concentrated hydrochloric acid with the concentration of 30-36% to adjust the pH value of the filtrate to 1, separating out a product, filtering, washing and drying the separated out matter to obtain 2.83kg of substituted diphenylamine 2a for later use, wherein the yield is 97.5%.
Adding substituted diphenylamine 2a (2.83kg,12.47mol), 4, 4' -diiodobiphenyl (2.02kg, 4.98mol), potassium carbonate (3.45kg,24.96mol), copper powder (0.016kg,0.25mol), copper oxide (0.02kg,0.25mol) and nitrobenzene (4.60kg,37.36mol) into a reactor, installing an oil-water separator, heating to 150 ℃ after 1h, carrying out heat preservation reaction for 10h, and monitoring the reaction to an end point by TLC; evaporating nitrobenzene under reduced pressure, adding water and 3mol/L hydrochloric acid to adjust the pH value of the system to be 2, pouring out a water phase, centrifuging solid materials to spin dry the water, adding 2.5L chloroform to mix uniformly (dissolving the solid materials), then adding dilute ammonia water with the mass concentration of 5% to repeatedly wash an organic phase until the washing water phase is colorless (washing to remove 2a and impurities), refluxing and stirring the washed organic phase at the temperature higher than the boiling point of the chloroform for 2h, cooling to 20-25 ℃, standing for 6h (refluxing and cooling is a recrystallization process), filtering, and drying to obtain an intermediate 3a (2.75kg,4.55mol), the purity is 96.0%, and the yield is 91.4%. The solvent used in the step is recycled. The product was characterized as:1H NMR(400MHz，CDCl3):7.91(d,2H),7.37(d,2H),7.32(m,4H),7.19(m,2H),7.17(m,2H),7.08(m,2H),6.97(m,4H),6.69(m,6H),2.31(s,6H)。
2) synthesis of target compound N, N '-bis (3-methyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (4 a):
2.75kg of intermediate 3a, 0.02kg (0.14mol) of cuprous oxide, 0.02kg (0.11mol) of phenanthroline and 1.35kg (13.65mol) of NMP are added into a reactor with a thermometer and a reflux device, the mixture is reacted for 8 hours at the temperature of 140 ℃, NMP solvent is evaporated after the reaction, 1.5L of water is added and mixed evenly, a black crude product is obtained by filtering, and the black crude product is recrystallized by cyclohexane to obtain 2.17kg of white crystal N, N '-bis (3-methyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (4a), the purity is 99.6 percent, and the yield is 92.3 percent. The product was characterized as:1H NMR(400MHz，CDCl3):7.49(d,J＝9.0Hz,4H),7.29(dd,J＝7.5Hz,4H),7.19(dd,J＝8.0Hz,2H),6.84–7.17(m,16H),2.31(s,6H)。
example 2
The intermediate for preparing biphenyl triarylamine compound in this example has the same structural formula as in example 1.
The process route of the preparation of biphenyl triarylamine compounds with carboxyl as a guiding group in this example is as follows:
the method comprises the following specific steps:
1) synthesis of intermediates
Adding 10.05kg of water into a reactor with a thermometer and a reflux device, sequentially adding 2.00kg of o-chlorobenzoic acid, 4.50kg of sodium carbonate, 0.11kg of copper oxide and 1.30kg of 3-methylaniline (1a) while stirring, heating the system to 103 ℃ for reaction, monitoring the reaction by TLC to the end point, and stopping heating; cooling the system to 70 ℃, adding 0.20kg of active carbon, continuously stirring until the system is uniform, filtering, then adding 35% concentrated hydrochloric acid to adjust the pH value of the filtrate to 1, separating out a product at the moment, filtering, washing and drying the precipitate to obtain 2.80kg of substituted diphenylamine (2a) for later use, wherein the yield is 96.8%.
Adding 2.80kg (12.33mol) of substituted diphenylamine (2a), 2.25kg (5.54mol) of 4, 4' -diiodobiphenyl, 5.11kg (48.21mol) of sodium carbonate, 0.016kg (0.25mol) of copper powder, 0.02kg (0.25mol) of copper oxide and 9.86kg (80.09mol) of nitrobenzene into a reactor, installing an oil-water separator, heating to 175 ℃ after 1 hour, keeping the temperature for reaction for 6 hours, and monitoring the reaction end point by TLC; evaporating nitrobenzene under reduced pressure, adding water and 3mol/L hydrochloric acid solution to adjust the pH value to be 2, pouring out a water phase, centrifuging a solid material to spin-dry water, adding 2.5L of chloroform for uniform mixing, then adding diluted ammonia water with the mass concentration of 5% to repeatedly wash an organic phase until the washing water phase is colorless, refluxing and stirring the washed organic phase for 2 hours, cooling to 25 ℃, standing for 6 hours, filtering and drying to obtain an intermediate 3a 3.13kg, wherein the purity is 99.5% and the yield is 93.4%. The solvent used in the step is recycled.
2) Synthesis of target compound N, N '-bis (3-methyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (4 a):
3.13kg (5.18mol) of the intermediate 3a, 0.04kg (0.28mol) of cuprous oxide, 0.037kg (0.21mol) of phenanthroline and 2.56kg (25.86mol) of NMP are added into a reactor with a thermometer and a reflux device, the mixture reacts for 6h at 170 ℃, NMP solvent is evaporated after the reaction, 1.5L of water is added for even mixing, a black crude product is obtained by filtering, and the black crude product is recrystallized by cyclohexane to obtain 2.43kg of white crystal N, N '-bis (3-methyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (4a), the purity is 99.6 percent, and the yield is 90.7 percent. Characterization data for compound 4a are the same as in example 1.
Example 3
The intermediate for preparing biphenyl triarylamine compound in this example has the same structural formula as in example 1.
The process route of the preparation of biphenyl triarylamine compounds with carboxyl as a guiding group in this example is as follows:
the method comprises the following specific steps:
1) synthesis of intermediates
Adding 20.00kg of water into a reactor with a thermometer and a reflux device, sequentially adding 2.00kg of o-chlorobenzoic acid, 7.00kg of cesium carbonate, 0.10kg of copper powder, 0.10kg of copper oxide and 1.60kg of 3-methylaniline (1a) while stirring, heating the system to 105 ℃ for reaction, monitoring the reaction by TLC to an end point, and stopping heating; cooling the system to 80 ℃, adding 0.24kg of active carbon, continuously stirring until the system is uniform, filtering, then adding 36% concentrated hydrochloric acid to adjust the pH value of the filtrate to 1, separating out a product at the moment, filtering, washing and drying the precipitate to obtain 2.85kg of substituted diphenylamine (2a) for later use, wherein the yield is 98.3%.
Adding 2.85kg (12.55mol) of substituted diphenylamine (2a), 2.55kg (6.28mol) of 4, 4' -diiodobiphenyl, 16.36kg (50.21mol) of cesium carbonate, 0.016kg (0.25mol) of copper powder, 0.02kg (0.25mol) of copper oxide and 15.44kg (125.50mol) of nitrobenzene into a reactor, installing an oil-water separator, heating to 200 ℃ after 1 hour, keeping the temperature for reaction for 2 hours, and monitoring the reaction end point by TLC; evaporating nitrobenzene under reduced pressure, adding water and 3mol/L hydrochloric acid solution to adjust the pH value to be 2, pouring out a water phase, centrifuging a solid material to spin-dry water, adding 2.5L of chloroform for uniform mixing, then adding dilute ammonia water with the mass concentration of 5% to repeatedly wash an organic phase until the washing water phase is colorless, refluxing and stirring the washed organic phase for 1h, cooling to 25 ℃, standing for 6h, filtering and drying to obtain an intermediate 3a3.61kg, wherein the purity is 96.0%, and the yield is 95.0%. The solvent used in the step is recycled.
2) Synthesis of target compound N, N '-bis (3-methyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (4 a):
3.61kg (5.97mol) of the intermediate 3a, 0.08kg (0.56mol) of cuprous oxide, 0.03kg (0.26mol) of TMEDA and 3.55kg (35.85mol) of NMP are added into a reactor with a thermometer and a reflux device, the mixture is reacted for 4h at 200 ℃, NMP solvent is evaporated after the reaction, 1.5L of water is added for even mixing, a black crude product is obtained by filtering, and the black crude product is recrystallized by cyclohexane to obtain 2.88kg of white crystal N, N '-bis (3-methyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (4a), the purity is 99.6 percent, and the yield is 93.5 percent. Characterization data for compound 4a are the same as in example 1.
Example 4
The intermediate for preparing the biphenyl triarylamine compound of this example has a structural formula shown in formula (3):
the process route of the preparation of biphenyl triarylamine compounds with carboxyl as a guiding group in this example is as follows:
the method comprises the following specific steps:
1) synthesis of intermediates
Adding 4.00kg of water into a reactor with a thermometer and a reflux device, sequentially adding 1.56kg of o-chlorobenzoic acid, 3.12kg of sodium carbonate, 0.04kg of copper powder, 0.04kg of copper oxide and 1.09kg of 4-methylaniline (1b) while stirring, heating the system to 105 ℃ for reaction, monitoring the reaction by TLC to an end point, and stopping heating; cooling the system to 70 ℃, adding 0.16kg of active carbon, continuously stirring until the system is uniform, filtering, then adding 33% concentrated hydrochloric acid to adjust the pH value of the filtrate to 1, at the moment, precipitating a product, filtering, washing and drying the precipitate to obtain 2.22kg (9.78mol) of substituted diphenylamine (2b), wherein the yield is 97.9%.
Adding 2.22kg of substituted diphenylamine (2b), 1.79kg (4.41mol) of 4, 4' -diiodobiphenyl, 3.11kg (29.34mol) of sodium carbonate, 12.54g (0.196mol) of copper powder, 15.68g (0.196mol) of copper oxide and 6.01kg (48.82mol) of nitrobenzene into a reactor, installing an oil-water separator, heating to 170 ℃ after 1 hour, keeping the temperature for reaction for 10 hours, and monitoring the reaction to an end point by TLC (thin layer chromatography); evaporating nitrobenzene under reduced pressure, adding water and 3mol/L hydrochloric acid solution to adjust the pH value to be 2, pouring out a water phase, centrifuging a solid material to spin-dry water, adding 2.5L of chloroform for uniform mixing, then adding dilute ammonia water with the mass concentration of 5% to repeatedly wash an organic phase until the washing water phase is colorless, refluxing and stirring the washed organic phase for 2 hours, cooling to 25 ℃, standing for 6 hours, filtering and drying to obtain an intermediate 3b 2.51kg, wherein the purity is 96.0% and the yield is 94.0%. The solvent used in the step is recycled. The product was characterized as:1H NMR(400MHz,CDCl3):8.0(d,2H)7.54(d,2H),7.32(m,4H),7.27(m,2H),7.23(m,2H),7.13(m,2H),6.95(m,4H),6.80(m,6H),2.32(s,6H)。
2) synthesis of target compound N, N '-bis (4-methyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (4 b):
adding 2.51kg (4.15mol) of intermediate 3b, 0.03kg (0.21mol) of cuprous oxide, 0.02kg (0.17mol) of TMEDA and 2.05kg (20.75mol) of NMP into a reactor with a thermometer and a reflux device, reacting for 4h at 180 ℃, evaporating NMP solvent after reaction, adding 1.5L of water, uniformly mixing, filtering to obtain a black crude product, and adding cyclohexane to the black crude product to obtain a black crude productRecrystallization gave 1.98kg (3.83mol) of N, N '-bis (4-methyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (4b) as white crystals with a purity of 99.6% and a yield of 92.3%. The product was characterized as:1H NMR(400MHz,CDCl3):7.42(d,J＝8.8Hz,4H),7.21-7.24(m,4H),7.02-7.12(m,16H),6.98(t,J＝7.4Hz,2H),2.32(s,6H)。
examples 5 to 9
The intermediates of examples 5-9, of which the structural formulae are shown in Table 1, can be used separately
The substituted aniline 1b was replaced as in example 4 and the intermediates listed in Table 1 were synthesized in sequence.
TABLE 1 structural formulas of intermediates of examples 5-9
On the basis of the above intermediates, the corresponding biphenyl triarylamine compounds can be synthesized according to the method of example 4.
In other preparation examples of the intermediate of the present invention, the first solvent, the second solvent, and the third solvent may be replaced by the types of the solvents defined in the present invention, the types of the ligands, the amounts of the raw materials for each step, and the specific reaction conditions may be adaptively adjusted within the ranges defined in the present invention, and the effects equivalent to those of the examples may be achieved.
Claims (10)
1. An intermediate for preparing biphenyl triarylamine compounds is characterized by having structures shown as a formula (1) and a formula (4):
in the formula (1), R is selected from hydrogen, alkyl with 1-10 carbon atoms, halogenated alkyl with 1-5 carbon atoms and alkoxy with 1-5 carbon atoms.
2. A process for the preparation of an intermediate as claimed in claim 1, comprising: reacting substituted diphenylamine, 4' -dihalobiphenyl, metal carbonate and a first catalyst in a first solvent at the temperature of 150-200 ℃ to obtain the catalyst; the structural formula of the substituted diphenylamine is as follows:
wherein R is selected from hydrogen, alkyl with 1-10 carbon atoms, halogenated alkyl with 1-5 carbon atoms and alkoxy with 1-5 carbon atoms.
3. The method of claim 2, wherein the metal carbonate is a combination of one or more of potassium carbonate, sodium bicarbonate, cesium carbonate.
4. The method of claim 2, wherein the first catalyst is copper and/or copper oxide.
5. The production method according to claim 2, 3 or 4, wherein the ratio of the amounts of the substances of the substituted diphenylamine, the 4, 4' -dihalobiphenyl, the metal carbonate, the first catalyst is 1: (0.4-0.5): (2-4): 0.04.
6. the method according to claim 5, wherein the first catalyst is a mixture of copper and copper oxide in a mass ratio of 1: 1.
7. A process according to claim 2, wherein the substituted diphenylamine is prepared by a process comprising the steps of: reacting substituted aniline, o-chlorobenzoic acid, metal carbonate and a second catalyst in a second solvent at 100-120 ℃ to obtain the compound; the structural formula of the substituted aniline is as follows:
wherein R is selected from hydrogen, alkyl with 1-10 carbon atoms, halogenated alkyl with 1-5 carbon atoms and alkoxy with 1-5 carbon atoms.
8. A method for preparing biphenyl triarylamine compounds by taking carboxyl as a guide group is characterized by comprising the following steps: performing decarboxylation reaction on the intermediate, a third catalyst and a ligand in a third solvent at 140-200 ℃ to obtain the intermediate; the intermediate is the intermediate of claim 1.
9. The method for preparing a biphenyl triarylamine compound having a carboxyl group as a targeting group as claimed in claim 8, wherein the ligand is N, N '-dimethylpiperazine, triethylamine, phenanthroline, substituted phenanthroline, N' -tetramethylethylenediamine or N, N-dimethylaniline.
10. The method for preparing a biphenyl triarylamine compound having a carboxyl group as a directing group according to claim 8 or 9, wherein the ratio of the amounts of the intermediate, the third catalyst and the ligand is 1: (0.01-0.1): (0.01-0.05).
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| CN1769369A (en) * | 2005-10-20 | 2006-05-10 | 复旦大学 | Novel preparation method for triarylamine analog hole transport materials |
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Non-Patent Citations (4)
| Title |
|---|
| 《Copper-Catalyzed Protodecarboxylation of Aromatic Carboxylic Acids》;Lukas J. Gooben，等;《Advanced Synthesis & Catalysis》;20071019;第349卷(第14-15期);第2243页表格2，第2243页左栏图1，第2245页左栏图2 * |
| 《三芳胺类空穴传输材料及其中间体的合成研究》;薛金强;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20060615(第6期);第19页第2段，第20页最后1段，第42页 * |
| 《乌尔曼缩合法合成N-苯基邻氨基苯甲酸的研究》;胡孝伦,等;《精细石油化工进展》;20160528;第17卷(第3期);第56页右栏第2.1节，第57页左栏表1 * |
| 《铜催化的乌尔曼缩合反应的研究》;陶传洲;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20090615(第6期);第2页最后1段,示意图1.3，第4页第3-5行 * |
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