CN103992231B - A kind of method of synthesizing triaryl amine - Google Patents
A kind of method of synthesizing triaryl amine Download PDFInfo
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Abstract
The invention discloses a kind of method of synthesizing triaryl amine, namely with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, under the existence of lithiumbromide, with diaryl-amine, ethylmagnesium bromide, aryl bromide or chlorinated aromatic hydrocarbons for Material synthesis triaryl amine.The method of structure triaryl amine provided by the invention has clear and definite structure and the ionic iron of air-stable (III) title complex is catalyzer, overcomes the oxidizable or unfavorable factor such as easy deliquescence and assorted metal interference of the catalyzer directly brought for catalyzer with iron or iron trichloride; Secondly, chlorinated aromatic hydrocarbons cheap and easy to get is introduced in this synthetic method by method provided by the invention first, the consumption of catalyzer and lithiumbromide is also only 0.3mol% and 10mol% of halogenated aryl hydrocarbon respectively, compared with the synthetic method of bibliographical information, there is higher catalytic efficiency and wider substrate applicability.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to the method for ionic iron (III) the title complex synthesis tri-arylamine group compound utilized containing bisphenol functionalized Imidazole cation.
Background technology
As a kind of hole mobile material popular at present, tri-arylamine group compound has been widely used in organic photoconductor, Organic Light Emitting Diode, organic/numerous areas such as polymer solar battery, photochromic material (see: ShirotaY.,
j.Mater.Chem., 2005, 15,75).
At present, the reaction of the aryl amination of the halohydrocarbon of transition-metal catalyst catalysis is the method that a class of synthesis triaryl amine generally adopts, as Buchwald Hartwig react and Ullmann react (see 1. Surry, D.S., Buchwald, S.L.,
chem.Sci., 2011, 2,27; 2. Monnier, F., Taillefer, M.,
angew.Chem.Int.Ed., 2009, 48,6954. 3. Rauws, T.R.M., Maes, B.U.W.,
chem.Soc.Rev., 2012, 41,2463).But these synthetic methods generally need to use expensive palladium series catalyst or virose Cu-series catalyst.Along with the intensification that people are familiar with chemical industry Sustainable development, develop inexpensive, low toxicity or nontoxic novel green catalyzer is obviously very required.Iron be on the earth content the abundantest, be the most also one of nontoxic metal, Fe-series catalyst is considered to the Critical policies (Correa, the A. that develop green high-efficient catalyzer because having the features such as cheapness, low toxicity, environmental friendliness, Manche o, O.G., Bolm, C.
chem.Soc.Rev., 2008, 37,1108).
2012, the people such as Nakamura report the synthesis of the triaryl amine of the first Fe-series catalyst catalysis, namely under lithiumbromide exists, with iron or iron trichloride be catalyzer, the reaction of amido Grignard reagent that formed by aryl bromide and diaryl-amine and ethylmagnesium bromide original position prepares triaryl amine (see Hatakeyama, T., Nakamura, M.
j.Am.Chem.Soc., 2012, 134,20262).Fe-series catalyst is used in the synthesis of triaryl amine by the method first, that one of the synthetic method that prior document is reported is improved greatly, but also there is obvious drawback in the method, mainly contain: (1) iron is very easily oxidized, iron trichloride is deliquescence very easily, operation inconvenience, and the purity of these molysite is often mixed with other metal (as copper) of denier by its commercial source difference thus causes the instability of catalytic performance; (2) need to add a large amount of lithiumbromides, in amount of substance, the consumption of lithiumbromide reaches 4.0 times of aryl bromide consumption; (3) reaction substrate is confined to aryl bromide, has obvious price advantage and diversity, has more the chlorinated aromatic hydrocarbons of commercial application prospect and do not have and relate to.
Therefore, use structure is clear and definite, the Fe-series catalyst of air-stable, and the novel method that triaryl amine is more efficiently and economically synthesized in exploitation is significant.
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing triaryl amine, namely with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, under the existence of lithiumbromide, the Reactive Synthesis triaryl amine of the amido Grignard reagent formed by aryl bromide or chlorinated aromatic hydrocarbons and diaryl-amine and ethylmagnesium bromide original position, and first chlorinated aromatic hydrocarbons has been incorporated in this synthetic method.
For achieving the above object, the technical solution used in the present invention utilizes a kind of ionic iron (III) title complex [(ArNCH containing bisphenol functionalized Imidazole cation
2cH
2nAr) CH] [FeCl
4] (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) as triaryl amine synthesis single-component catalyst, its synthetic method is that prior art is (see Xia Chongliang, the synthesis of the ionic iron title complex of Imidazole cation and derivative carbene compound thereof, sign and catalytic applications is modified containing bis-phenol, University Of Suzhou's master thesis,, and characterize through ultimate analysis 2013).It can be represented by the following chemical structure formula:
。
Above-mentioned using iron (III) title complex as single-component catalyst, under the existence of lithiumbromide, the method for the Reactive Synthesis triaryl amine of the amido Grignard reagent that catalysis aryl bromide or chlorinated aromatic hydrocarbons and diaryl-amine and ethylmagnesium bromide original position are formed comprises the following steps:
1) under anhydrous and oxygen-free condition, in inert gas atmosphere, successively diaryl-amine, solvent orange 2 A, ethylmagnesium bromide are joined in reaction vessel, stirring reaction 1 ~ 3 hour at 25 ~ 45 DEG C;
2) drain solvent orange 2 A, successively catalyzer, lithiumbromide, solvent B, halogenated aryl hydrocarbon are added in reaction vessel, stirring reaction 10 ~ 48 hours at 120 ~ 150 DEG C;
3) cool, use deionized water termination reaction, obtain product triaryl amine.
In technique scheme, rare gas element described in step 1) is nitrogen or argon gas, preferred nitrogen; Described solvent orange 2 A is ether or tetrahydrofuran (THF), preferred ether; Step 2) described in catalyzer be ionic iron (III) title complex as described above; Described solvent B is toluene or dimethylbenzene, preferred dimethylbenzene, and described dimethylbenzene is the mixture of its three kinds of isomerss; Described halogenated aryl hydrocarbon is aryl bromide or chlorinated aromatic hydrocarbons.
In preferred technical scheme, when described halogenated aryl hydrocarbon is aryl bromide, in amount of substance, the consumption of diaryl-amine and ethylmagnesium bromide is 1.1 times of halogenated aryl hydrocarbon, and the consumption of lithiumbromide is 10% of halogenated aryl hydrocarbon, and the consumption of catalyzer is 0.3% of halogenated aryl hydrocarbon; In step 1), temperature of reaction is 40 DEG C, and the reaction times is 2 hours; Step 2) in, temperature of reaction is 140 DEG C, and the reaction times is 12 hours.
In preferred technical scheme, when described halogenated aryl hydrocarbon is chlorinated aromatic hydrocarbons, in amount of substance, the consumption of diaryl-amine and ethylmagnesium bromide is 1.5 times of halogenated aryl hydrocarbon, and the consumption of lithiumbromide is 10% of halogenated aryl hydrocarbon, and the consumption of catalyzer is 0.5% of halogenated aryl hydrocarbon; In step 1), temperature of reaction is 40 DEG C, and the reaction times is 2 hours; Step 2) in, temperature of reaction is 140 DEG C, and the reaction times is 24 hours.
Principle of the present invention is: first, diaryl-amine and ethyl phosphonium bromide reactive magnesium in-situ preparation amido Grignard reagent, this Grignard reagent can be activated by lithiumbromide, and have an effect with ionic iron (III) title complex and generate the iron active intermediate of lower valency, thus described ionic iron (III) title complex containing bisphenol functionalized Imidazole cation is changed at reaction system situ can the catalyzer of efficient catalytic amido Grignard reagent and halogenated aryl hydrocarbon cross-coupling reaction.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention has clear and definite structure and the ionic iron of air-stable (III) title complex is catalyzer, overcomes the oxidizable or unfavorable factor such as easy deliquescence and assorted metal interference of the catalyzer directly brought for catalyzer with iron or iron trichloride; And this title complex synthetic method is simple, be conducive to synthesizing use on a large scale;
2. in amount of substance, the consumption of method provided by the invention not only catalyzer can be reduced to the 0.3mol% of halogenated aryl hydrocarbon, obvious reduction is had compared with the consumption of the 5.0mol% in document, and the consumption of additive lithiumbromide is also reduced to 10% of halogenated aryl hydrocarbon, there has also been great reduction compared with the consumption of 4.0 in document times, save raw materials cost;
3. preparation method disclosed by the invention has universality to multiple reaction substrate, not only to the aryl amination reaction that aryl bromide participates in, there is very high catalytic activity, be significantly higher than the most high catalytic activity of the molysite system of current bibliographical information, but also can some chlorinated aromatic hydrocarbons of efficient catalytic participate in aryl amination reaction, raw material sources are relatively easy, cost is low, are conducive to the suitability for industrialized production of triaryl amine.
Embodiment
The present invention is set forth further below in conjunction with specific embodiment.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by pentanoic, ethylmagnesium bromide, Reactive Synthesis triaryl amine to methoxybromobenzene.
Under anhydrous and oxygen-free condition, at inert gas atmosphere (N
2) in, successively pentanoic (0.1859 gram, 1.1 mmoles), ether (2.0 milliliters), ethylmagnesium bromide (0.99 milliliter, 1.1 mmoles) are joined in reaction vessel, stirring reaction 2 hours at 40 DEG C.Drain solvent ether, successively by catalyzer (0.0021 gram, 0.3% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), dimethylbenzene (4.0 milliliters) with to methoxybromobenzene (125 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 12 hours at 140 DEG C.Cooling, using deionized water termination reaction, is 98% by the productive rate of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):3.79(3H,s),6.83-6.85(2H,d),6.92-6.96(2H,t),7.03-7.09(6H,m),7.19-7.28(4H,m)。
Embodiment 2: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, adjacent methyl bromobenzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), successively by pentanoic (0.1859 gram, 1.1 mmoles), tetrahydrofuran (THF) (2.0 milliliters), ethylmagnesium bromide (0.99 milliliter, 1.1 mmoles) join in reaction vessel, stirring reaction 3 hours at 25 DEG C.Drain solvents tetrahydrofurane, successively by catalyzer (0.0021 gram, 0.3% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), toluene (4.0 milliliters) and adjacent methyl bromobenzene (120 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 48 hours at 120 DEG C.Cooling, uses deionized water termination reaction, by the productive rate 72% of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):2.07(3H,s),6.93-6.96(2H,t),6.99-7.01(4H,d),7.14-7.28(8H,m)。
Embodiment 3: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, a methyl bromobenzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), successively by pentanoic (0.1859 gram, 1.1 mmoles), ether (2.0 milliliters), ethylmagnesium bromide (0.99 milliliter, 1.1 mmoles) join in reaction vessel, reaction 2 hours under stirring at 40 DEG C.Drain solvent ether, successively by catalyzer (0.0021 gram, 0.3% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), toluene (4.0 milliliters) and methyl bromobenzene (121 microlitre, 1 mmole) be added in reaction vessel, stirring reaction 18 hours at 130 DEG C.Cooling, uses deionized water termination reaction, by the productive rate 89% of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):2.28(3H,s),6.85-6.87(1H,d),6.90-6.93(1H,d),6.94(1H,s),6.98-7.03(2H,t),7.09-7.11(4H,d),7.13-7.17(1H,t),7.24-7.29(4H,m)。
Embodiment 4: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, bromobenzene.
Under anhydrous and oxygen-free condition, at inert gas atmosphere (N
2) in, successively pentanoic (0.1859 gram, 1.1 mmoles), tetrahydrofuran (THF) (2.0 milliliters), ethylmagnesium bromide (0.99 milliliter, 1.1 mmoles) are joined in reaction vessel, stirring reaction 1 hour at 45 DEG C.Drain solvents tetrahydrofurane, successively by catalyzer (0.0021 gram, 0.3% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), dimethylbenzene (4.0 milliliters) and bromobenzene (105 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 10 hours at 150 DEG C.Cooling, uses deionized water termination reaction, by the productive rate 93% of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):7.02-7.06(3H,m),7.11-7.13(6H,m),7.26-7.30(6H,m)。
Embodiment 5: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, p-Fluoro bromo benzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), successively by pentanoic (0.1859 gram, 1.1 mmoles), ether (2.0 milliliters), ethylmagnesium bromide (0.99 milliliter, 1.1 mmoles) join in reaction vessel, reaction 2 hours under stirring at 40 DEG C.Drain solvent ether, successively by catalyzer (0.0021 gram, 0.3% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), toluene (4.0 milliliters) and p-Fluoro bromo benzene (110 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 12 hours at 140 DEG C.Cooling, uses deionized water termination reaction, by the productive rate 85% of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):6.96-7.03(4H,m),7.05-7.11(6H,m),7.24-7.28(4H,m)。
Embodiment 6: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, 2-bromopyridine.
Under anhydrous and oxygen-free condition, at inert gas atmosphere (N
2) in, successively pentanoic (0.1859 gram, 1.1 mmoles), ether (2.0 milliliters), ethylmagnesium bromide (0.99 milliliter, 1.1 mmoles) are joined in reaction vessel, stirring reaction 2 hours at 30 DEG C.Drain solvent ether, successively by catalyzer (0.0021 gram, 0.3% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), dimethylbenzene (4.0 milliliters) and 2-bromopyridine (97 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 18 hours at 130 DEG C.Cooling, using deionized water termination reaction, is 97% by the productive rate of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):6.74-6.79(2H,m),7.11-7.15(2H,t),7.17-7.19(4H,d),7.30-7.34(4H,t),7.42-7.46(1H,m),8.23-8.24(1H,m)。
Embodiment 7: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, 2-bromonaphthalene.
Under anhydrous and oxygen-free condition, at inert gas atmosphere (N
2) in, successively pentanoic (0.1859 gram, 1.1 mmoles), ether (2.0 milliliters), ethylmagnesium bromide (0.99 milliliter, 1.1 mmoles) are joined in reaction vessel, stirring reaction 2 hours at 40 DEG C.Drain solvent ether, successively by catalyzer (0.0021 gram, 0.3% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), dimethylbenzene (4.0 milliliters) and 2-bromonaphthalene (0.2071 gram, 1 mmole) be added in reaction vessel, stirring reaction 12 hours at 140 DEG C.Cooling, using deionized water termination reaction, is 92% by the productive rate of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):7.06-7.09(2H,t),7.16-7.18(4H,d),7.28-7.33(5H,m),7.35-7.46(3H,m),7.61-7.63(1H,d),7.74-7.80(2H,q)。
Embodiment 8: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by 4,4'-dimethyl pentanoic, ethylmagnesium bromide, Reactive Synthesis triaryl amine to methoxybromobenzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), successively by 4,4'-dimethyl pentanoic (0.2170 gram, 1.1 mmoles), ether (2.0 milliliters), ethylmagnesium bromide (0.99 milliliter, 1.1 mmoles) join in reaction vessel, stirring reaction 2 hours at 40 DEG C.Drain solvent ether, successively by catalyzer (0.0021 gram, 0.3% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), dimethylbenzene (4.0 milliliters) with to methoxybromobenzene (125 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 12 hours at 140 DEG C.Cooling, using deionized water termination reaction, is 91% by the productive rate of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):2.31(6H,s),3.81(3H,s),6.82-6.85(2H,d),6.94-6.98(4H,m),7.03-7.08(6H,m)。
Embodiment 9: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, PARA NITRO CHLOROBENZENE (PNCB).
Under anhydrous and oxygen-free condition, at inert gas atmosphere (N
2) in, successively pentanoic (0.2535 gram, 1.5 mmoles), ether (2.0 milliliters), ethylmagnesium bromide (1.35 milliliters, 1.5 mmoles) are joined in reaction vessel, stirring reaction 2 hours at 40 DEG C.Drain solvent ether, successively by catalyzer (0.0035 gram, 0.5% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), dimethylbenzene (4.0 milliliters) and PARA NITRO CHLOROBENZENE (PNCB) (118 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 24 hours at 140 DEG C.Cooling, using deionized water termination reaction, is 55% by the productive rate of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):2.35(3H,s),6.99-7.05(4H,m),7.09-7.12(6H,m),7.24-7.28(4H,m)。
Embodiment 10: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, chlorobenzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), pentanoic (0.2535 gram, 1.5 mmoles), tetrahydrofuran (THF) (2.0 milliliters), ethylmagnesium bromide (1.35 milliliters will be added successively, 1.5 mmoles) join in reaction vessel, stirring reaction 1 hour at 45 DEG C.Drain solvents tetrahydrofurane, successively by catalyzer (0.0035 gram, 0.5% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), dimethylbenzene (4.0 milliliters) and chlorobenzene (102 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 12 hours at 150 DEG C.Cooling, uses deionized water termination reaction, by the productive rate 40% of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):7.02-7.06(3H,m),7.11-7.13(6H,m),7.26-7.30(6H,m)。
Embodiment 11: under lithiumbromide exists, with molecular formula for [(ArNCH
2cH
2nAr) CH] [FeCl
4] ionic iron (III) title complex (wherein Ar=3,5-bis--[C (CH
3)
3]-2-(OH)-C
6h
2) be catalyzer, by the Reactive Synthesis triaryl amine of pentanoic, ethylmagnesium bromide, 2-chloropyridine.
Under anhydrous and oxygen-free condition, at inert gas atmosphere (N
2) in, successively pentanoic (0.2535 gram, 1.5 mmoles), ether (2.0 milliliters), ethylmagnesium bromide (1.35 milliliters, 1.5 mmoles) are joined in reaction vessel, stirring reaction 2 hours at 40 DEG C.Drain solvent ether, successively by catalyzer (0.0035 gram, 0.5% mmole), lithiumbromide (0.0086 gram, 0.1 mmole), dimethylbenzene (4.0 milliliters) and 2-chloropyridine (94 microlitres, 1 mmole) be added in reaction vessel, stirring reaction 24 hours at 140 DEG C.Cooling, using deionized water termination reaction, is 52% by the productive rate of gas chromatographic analysis product.
Product is dissolved in CDCl
3in (about 0.4 milliliter), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize.
1HNMR(400MHz,CDCl
3,TMS):6.74-6.79(2H,m),7.11-7.15(2H,t),7.17-7.19(4H,d),7.30-7.34(4H,t),7.42-7.46(1H,m),8.23-8.24(1H,m)。
Claims (8)
1. synthesize a method for triaryl amine, it is characterized in that, said method comprising the steps of:
1) under anhydrous and oxygen-free condition, in inert gas atmosphere, successively diaryl-amine, solvent orange 2 A, ethylmagnesium bromide are joined in reaction vessel, stirring reaction 1 ~ 3 hour at 25 ~ 45 DEG C;
2) drain solvent orange 2 A, successively catalyzer, solvent B, lithiumbromide, halogenated aryl hydrocarbon are added in reaction vessel, stirring reaction 10 ~ 48 hours at 120 ~ 150 DEG C;
3) cool, use deionized water termination reaction, obtain product triaryl amine;
Wherein:
Solvent orange 2 A described in step 1) is ether or tetrahydrofuran (THF);
Step 2) described in solvent B be toluene or dimethylbenzene;
Step 2) described in catalyzer be ionic iron (III) title complex containing bisphenol functionalized Imidazole cation, it is represented by the following chemical structure formula:
。
2. method according to claim 1, is characterized in that, rare gas element described in step 1) is nitrogen or argon gas.
3. method according to claim 2, is characterized in that, rare gas element described in step 1) is nitrogen.
4. method according to claim 1, is characterized in that, solvent orange 2 A described in step 1) is ether.
5. method according to claim 1, is characterized in that, step 2) described in solvent B be dimethylbenzene, described dimethylbenzene is the mixture of its three kinds of isomerss.
6. method according to claim 1, is characterized in that, step 2) described in halogenated aryl hydrocarbon be aryl bromide or chlorinated aromatic hydrocarbons.
7. method according to claim 6, it is characterized in that, step 2) described in halogenated aryl hydrocarbon when being aryl bromide, in amount of substance, the consumption of diaryl-amine and ethylmagnesium bromide is 1.1 times of halogenated aryl hydrocarbon, the consumption of lithiumbromide is 10% of halogenated aryl hydrocarbon, and the consumption of catalyzer is 0.3% of halogenated aryl hydrocarbon; In step 1), temperature of reaction is 40 DEG C, and the reaction times is 2 hours; Step 2) in, temperature of reaction is 140 DEG C, and the reaction times is 12 hours.
8. method according to claim 6, it is characterized in that, step 2) described in halogenated aryl hydrocarbon when being chlorinated aromatic hydrocarbons, in amount of substance, the consumption of diaryl-amine and ethylmagnesium bromide is 1.5 times of halogenated aryl hydrocarbon, the consumption of lithiumbromide is 10% of halogenated aryl hydrocarbon, and the consumption of catalyzer is 0.5% of halogenated aryl hydrocarbon; In step 1), temperature of reaction is 40 DEG C, and the reaction times is 2 hours; Step 2) in, temperature of reaction is 140 DEG C, and the reaction times is 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410202965.9A CN103992231B (en) | 2014-05-15 | 2014-05-15 | A kind of method of synthesizing triaryl amine |
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| US4764625A (en) * | 1980-12-12 | 1988-08-16 | Xerox Corporation | Process for preparing arylamines |
| CN101671370A (en) * | 2009-09-16 | 2010-03-17 | 苏州大学 | Ionic liquid type iron (III) complex and application thereof |
| CN101676259A (en) * | 2008-09-17 | 2010-03-24 | 中国科学院化学研究所 | Method of synthesizing tertiary aromatic amine through coupling reaction of aryl bromide and secondary aromatic amine under catalysis of nickel |
| CN102887923A (en) * | 2012-10-18 | 2013-01-23 | 苏州大学 | Ionic iron (III) complex containing bisphenol functional imidazoline salt and application thereof |
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| US4764625A (en) * | 1980-12-12 | 1988-08-16 | Xerox Corporation | Process for preparing arylamines |
| CN101676259A (en) * | 2008-09-17 | 2010-03-24 | 中国科学院化学研究所 | Method of synthesizing tertiary aromatic amine through coupling reaction of aryl bromide and secondary aromatic amine under catalysis of nickel |
| CN101671370A (en) * | 2009-09-16 | 2010-03-17 | 苏州大学 | Ionic liquid type iron (III) complex and application thereof |
| CN102887923A (en) * | 2012-10-18 | 2013-01-23 | 苏州大学 | Ionic iron (III) complex containing bisphenol functional imidazoline salt and application thereof |
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