CN103992231A - Method for synthesizing triarylated amine - Google Patents
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Abstract
The invention discloses a method for synthesizing a triarylated amine. The method is used for synthesizing the triarylated amine from a raw material diarylamine, ethylmagnesium bromide, bromoaromatic hydrocarbon or chloroaromatic hydrocarbon in the presence of lithium bromide by taking an ionic (III) complex as a catalyst, wherein the molecular formula of the ionic (III) complex is [(ArNCH2CH2CH2NAr)CH][FeCl4], and Ar represents 3,5-bis-[C(CH3)3]-2-(OH)-C6H2. The method for constructing the triarylated amine is characterized in that the ionic (III) complex having a clear structure and air stability is taken as the catalyst, and consequently, adverse factors such as easy catalyst oxidation or deliquescence and metal interference due to a fact that ferrous dichloride or ferric trichloride is directly taken as the catalyst are avoided; next, the method has the advantages that the cheap and easily available chloroaromatic hydrocarbon is introduced into the synthesis method for the first time, and the dosage of the catalyst and the dosage of lithium bromide are only 0.3mol% and 10mol% of that of the chloroaromatic hydrocarbon, respectively, and therefore, compared with document reported synthesis methods, the method has higher catalytic efficiency and better substrate applicability.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to utilize the method containing the synthetic tri-arylamine group compound of ionic iron (III) title complex of bisphenol functionalized Imidazole cation.
Background technology
As current popular a kind of hole mobile material, tri-arylamine group compound be widely used in the numerous areas such as organic photoconductor, Organic Light Emitting Diode, organic/polymer solar battery, photochromic material (referring to Shirota Y.,
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 synthetic three arylamine generally adopts, as Buchwald Hartwig reaction and Ullmann react (referring to 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 be used expensive palladium series catalyst or virose Cu-series catalyst.Along with the intensification of people to chemical industry Sustainable development understanding, it is obviously very essential developing inexpensive, low toxicity or nontoxic novel green catalyzer.Iron be on the earth content the abundantest, be the most also one of nontoxic metal, Fe-series catalyst is considered to develop a Critical policies (Correa, the A. of 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 have reported three arylamine synthetic of the first Fe-series catalyst catalysis, under lithiumbromide exists, the reacting of the amido Grignard reagent forming with ethylmagnesium bromide original position taking dichloride ferrous iron or iron trichloride as catalyzer, by aryl bromide and diaryl-amine prepared three arylamine (referring to Hatakeyama, T., Nakamura, M.
j. Am. Chem. Soc., 2012, 134,20262).The method is the synthesizing for three arylamine by Fe-series catalyst first, it is an improvement greatly of the synthetic method to previous bibliographical information, but also there is obvious drawback in the method, mainly contain: (1) dichloride ferrous iron is very easily oxidized, iron trichloride is deliquescence very easily, operation inconvenience, and the purity of these molysite be subject to its commercial source difference to tend to be mixed with other metal (as copper) of denier thus cause the unstable of catalytic performance; (2) need to add a large amount of lithiumbromides, in amount of substance, the consumption of lithiumbromide has reached 4.0 times of aryl bromide consumption; (3) reaction substrate is confined to aryl bromide, and the chlorinated aromatic hydrocarbons that have obvious price advantage and diversity, has more commercial application prospect does not have and relates to.
Therefore, use structure is clear and definite, the Fe-series catalyst of air-stable, and the exploitation more efficiently and economically novel method of synthetic three arylamine is significant.
Summary of the invention
The object of the present invention is to provide a kind of method of synthetic three arylamine, taking molecular formula as [(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 reacting of amido Grignard reagent forming with diaryl-amine and ethylmagnesium bromide original position by aryl bromide or chlorinated aromatic hydrocarbons synthesized three arylamine, 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 is to utilize 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 the synthetic single-component catalyst of three arylamine, its synthetic method is that prior art is (referring to Xia Chongliang, modify synthetic, sign and the catalytic applications of the ionic iron title complex of Imidazole cation and derivative carbene compound thereof containing bis-phenol, University Of Suzhou's master thesis, 2013), and through ultimate analysis characterize.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, catalysis aryl bromide or chlorinated aromatic hydrocarbons comprise the following steps with the method for reacting synthetic three arylamine of the amido Grignard reagent that diaryl-amine and ethylmagnesium bromide original position form:
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 to 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) cooling, use deionized water termination reaction, obtain product three arylamine.
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), preferably ether; Step 2) described in catalyzer be ionic iron (III) title complex as described above; Described solvent B is toluene or dimethylbenzene, preferably 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 halogenated aryl hydrocarbon 0.3%; 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, 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 halogenated aryl hydrocarbon 0.5%; 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, the reaction times is 24 hours.
Principle of the present invention is: first, diaryl-amine reacts original position and has generated amido Grignard reagent with ethylmagnesium bromide, this Grignard reagent can be activated by lithiumbromide, and have an effect and generate the iron active intermediate of lower valency with ionic iron (III) title complex, can efficient catalytic amido Grignard reagent and the catalyzer of halogenated aryl hydrocarbon cross-coupling reaction thereby described ionic iron (III) title complex containing bisphenol functionalized Imidazole cation is changed at reaction system situ.
Because technique scheme is used, the present invention compared with prior art has following advantages:
The present invention be ionic iron (III) title complex with clear and definite structure and air-stable be catalyzer, overcome directly the unfavorable factors such as or easy deliquescence and assorted metal interference oxidizable with dichloride ferrous iron or the iron trichloride catalyzer that to be catalyzer brought; And this title complex synthetic method is simple, be conducive to extensive synthetic use;
2. in amount of substance, the method provided by the invention not only consumption of catalyzer can be reduced to the 0.3mol% of halogenated aryl hydrocarbon, there is obvious reduction 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, also there is great reduction compared with the consumption of 4.0 times in document, saved raw materials cost;
3. preparation method disclosed by the invention has universality to multiple reaction substrate, the aryl amination reaction not only aryl bromide being participated in has very high catalytic activity, be significantly higher than the high catalytic activity of the molysite system of current bibliographical information, but also can efficient catalytic the aryl amination reaction that participates in of some chlorinated aromatic hydrocarbons, raw material sources are relatively easy, cost is low, are conducive to the suitability for industrialized production of three arylamine.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1: under lithiumbromide exists, taking molecular formula as [(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, to synthetic three arylamine of the reaction of methoxyl group bromobenzene.
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 to 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 methoxyl group bromobenzene (125 microlitres, 1 mmole) be added in reaction vessel stirring reaction 12 hours at 140 DEG C.Cooling, use deionized water termination reaction, be 98% by the productive rate of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction of pentanoic, ethylmagnesium bromide, adjacent methyl bromobenzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), successively by (0.99 milliliter of pentanoic (0.1859 gram, 1.1 mmoles), tetrahydrofuran (THF) (2.0 milliliters), ethylmagnesium bromide, 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, use deionized water termination reaction, by the productive rate 72% of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction of pentanoic, ethylmagnesium bromide, a methyl bromobenzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), successively by (0.99 milliliter of pentanoic (0.1859 gram, 1.1 mmoles), ether (2.0 milliliters), ethylmagnesium bromide, 1.1 mmoles) join in reaction vessel, under 40 DEG C of stirrings, react 2 hours.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, use deionized water termination reaction, by the productive rate 89% of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction 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 to 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, use deionized water termination reaction, by the productive rate 93% of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction of pentanoic, ethylmagnesium bromide, p-Fluoro bromo benzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), successively by (0.99 milliliter of pentanoic (0.1859 gram, 1.1 mmoles), ether (2.0 milliliters), ethylmagnesium bromide, 1.1 mmoles) join in reaction vessel, under 40 DEG C of stirrings, react 2 hours.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, use deionized water termination reaction, by the productive rate 85% of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction 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 to 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, use deionized water termination reaction, be 97% by the productive rate of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction 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 to 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 (0.2071 gram of 2-bromonaphthalene, 1 mmole) be added in reaction vessel stirring reaction 12 hours at 140 DEG C.Cooling, use deionized water termination reaction, be 92% by the productive rate of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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, to synthetic three arylamine of the reaction of methoxyl group bromobenzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), successively by 4, (0.2170 gram of 4'-dimethyl pentanoic, 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 methoxyl group bromobenzene (125 microlitres, 1 mmole) be added in reaction vessel stirring reaction 12 hours at 140 DEG C.Cooling, use deionized water termination reaction, be 91% by the productive rate of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction 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 to 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, use deionized water termination reaction, be 55% by the productive rate of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction of pentanoic, ethylmagnesium bromide, chlorobenzene.
Under anhydrous and oxygen-free condition, in inert gas atmosphere (Ar), will add successively (1.35 milliliters of pentanoic (0.2535 gram, 1.5 mmoles), tetrahydrofuran (THF) (2.0 milliliters), ethylmagnesium bromide, 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, use deionized water termination reaction, by the productive rate 40% of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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, taking molecular formula as [(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 synthetic three arylamine of reaction 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 to 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, use deionized water termination reaction, be 52% by the productive rate of gas chromatographic analysis product.
Product is dissolved in to CDCl
3in (approximately 0.4 milliliter), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure characterize.
1H?NMR?(400?MHz,?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 (10)
1. a method for synthetic three arylamine, 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 to 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) cooling, use deionized water termination reaction, obtain product three arylamine;
Catalyzer wherein: step 2) is ionic iron (III) title complex containing bisphenol functionalized Imidazole cation, and 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 or tetrahydrofuran (THF).
5. method according to claim 4, is characterized in that, solvent orange 2 A described in step 1) is ether.
6. method according to claim 1, is characterized in that step 2) described in solvent B be toluene or dimethylbenzene.
7. method according to claim 6, is characterized in that step 2) described in solvent B be dimethylbenzene, described dimethylbenzene is the mixture of its three kinds of isomerss.
8. method according to claim 1, is characterized in that step 2) described in halogenated aryl hydrocarbon be aryl bromide or chlorinated aromatic hydrocarbons.
9. method according to claim 8, it is characterized in that, step 2) described in halogenated aryl hydrocarbon while 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 halogenated aryl hydrocarbon 0.3%; 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, the reaction times is 12 hours.
10. method according to claim 8, it is characterized in that, step 2) described in halogenated aryl hydrocarbon while 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, 0.5 % that the consumption of catalyzer is 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, the reaction times is 24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-05-15 CN CN201410202965.9A patent/CN103992231B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| TAKUJI HATAKEYAMA等: ""Iron-catalyzed aromatic amination for nonsymmetrical triarylamine synthesis"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 134, 26 November 2012 (2012-11-26), pages 20262 - 20265 * |
| 高欢欢等，: "一种新的离子型含咪唑盐的铁（II）配合物的合成、结构及催化性能", 《苏州大学学报（自然科学版）》, vol. 27, no. 1, 31 January 2011 (2011-01-31), pages 70 - 73 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000465A (en) * | 2015-07-27 | 2016-10-12 | 苏州大学 | Method for oxidative coupling reaction of aldehyde and secondary amide |
| CN106000465B (en) * | 2015-07-27 | 2018-07-31 | 苏州大学 | A kind of method of aldehyde and the oxidative coupling reaction of two level amide |
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