CN109942456B - Method for synthesizing p-benzoquinone monoimine from p-aminophenol - Google Patents
Method for synthesizing p-benzoquinone monoimine from p-aminophenol Download PDFInfo
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Abstract
The invention discloses a method for synthesizing p-benzoquinone monoimine by p-aminophenol, which directly adopts coupling dehydrogenation oxidation of p-aminophenol and phenylboronic acid to prepare the p-benzoquinone-p-benzoquinone monoimine by a one-step method, has simple operation, does not need multi-step reaction, shortens the reaction time, has cheap raw materials and low production cost, avoids the use of explosive oxidant, and overcomes the defects of complicated multi-step operation, high possibility of explosion, high pollution of heavy metal ions, high cost and the like of the prior art.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing p-benzoquinone monoimine from p-aminophenol.
Background
Quinoneimine type compounds are generally colorful compounds, can exist in plant pigments, dyes, indicators and other substances, and are important organic analyte reagents. Some quinoneimine dyes also have strong fluorescence, such as safranine T, phenol safranine, and the like, so that the content of certain metal ions can be detected and analyzed by utilizing the strong fluorescence characteristics of the dyes. For some quinoneimine dyes with weak fluorescence, such as neutral red, but with dark color, a catalytic kinetic spectrophotometry can be used for carrying out metal ion catalytic fading reaction, so as to realize detection and analysis of metal ions. In addition, the structure of p-benzoquinone single benzene imine exists in the structure of many antitumor drugs, and especially plays an important role in the structure of actinomycin.
Currently, p-benzoquinone mono-phenylimine is synthesized by preparing N-phenyl-p-aminophenol or N-phenyl-p-aminophenol ether through p-aminophenol coupling, and then preparing the p-benzoquinone mono-phenylimine compound through oxidative dehydrogenation:
the p-benzoquinone mono-benzene imine compound is prepared by catalytic oxidation of N-phenyl-p-aminophenol or N-phenyl-p-aminophenol ether by proper silver salt (such as silver carbonate and silver oxide) and mercury oxide under the protection of nitrogen, but the method needs nitrogen protection, has expensive raw materials and high cost, needs the catalysis of heavy metal silver salt and mercury salt, and has great environmental pollution.
The p-benzoquinone monoimine is prepared by oxidizing N-phenyl-p-aminophenol by hypochlorite, the N-phenyl-p-aminophenol is used as a raw material, the price is high, the production cost is high, and the strong oxidant hypochlorite is used, so that the oxidation reduction reaction is easy to occur with organic compounds, and unsafe factors occur in production.
Under the condition of high-iodine dess-martin oxidant (DMP), p-methoxy diphenylamine is oxidized to synthesize p-benzoquinone monophenylimine, but the reaction raw material is expensive, the production cost is high, the dess-martin oxidant has potential explosion possibility, and a large amount of organic by-product o-phenoxybenzoic acid is generated in the reaction process.
Disclosure of Invention
The invention aims to: aiming at the problems, the p-benzoquinone single phenylimine is prepared by directly coupling, dehydrogenating and oxidizing p-aminophenol and phenylboronic acid through a one-step method, the operation is simple, multi-step reaction is not needed, the reaction time is shortened, the raw materials are cheap, the production cost is low, and the use of explosive oxidants is avoided.
The technical scheme adopted by the invention is as follows:
a method for synthesizing p-benzoquinone monoimine by p-aminophenol comprises the following steps: under the alkaline condition, the raw materials of aminophenol and phenylboronic acid are subjected to catalytic coupling and dehydrogenation oxidation reaction by adopting a catalyst and a catalytic auxiliary agent, so that benzoquinone monoimine is synthesized in one step.
Further, the method comprises the following specific steps: p-aminophenol, phenylboronic acid, a catalyst, a catalytic assistant and an alkaline reagent are dissolved in a solvent for reaction.
Further, the reaction conditions were: reflux reaction is carried out for 6 to 18 hours at 65 to 90 ℃.
Further, cooling and filtering after the reaction is finished, distilling under reduced pressure, recrystallizing the distillation product, filtering after recrystallization, and washing for 2-5 times by adopting recrystallization mother liquor.
Further, the solvent is ethyl acetate, potassium carbonate or potassium acetate solution is used under alkaline condition, the catalyst is copper acetate or copper chloride, and the catalytic assistant is benzoic acid.
The invention adopts cupric salt as catalyst under alkaline condition, uses benzoic acid as catalytic auxiliary agent, and makes p-aminophenol and phenylboronic acid undergo the processes of catalytic coupling and oxidative dehydrogenation so as to obtain p-benzoquinone monophenylimine.
In the prior art, p-aminophenol or p-aminophenol and halogeno-benzene or phenylboronic acid are coupled to obtain N-phenyl-p-aminophenol or N-phenyl-p-aminophenol ether, and then the N-phenyl-p-aminophenol or N-phenyl-p-aminophenol ether is subjected to catalytic oxidation by using silver salt or is subjected to dehydrogenation oxidation by directly using an oxidant (hypochlorite, a high-iodine dess-martin oxidant) to obtain the product p-benzoquinone single benzimine. The method utilizes the property of catalyzing C-N coupling of copper salt, adopts N-phenyl-p-aminophenol generated by coupling p-aminophenol and phenylboronic acid, utilizes the property of catalyzing oxidation of copper salt in the same system, and reacts with air to obtain the product p-benzoquinone single benzene imine, thereby realizing the continuous process of coupling and dehydrogenation oxidation reaction in the same reaction system and simplifying the operation.
Further, the ratio of the amounts of substances of p-aminophenol, phenylboronic acid, benzoic acid, potassium carbonate or acetate, copper acetate or chloride is: 0.8-1.5:0.8-1.5:0.2-0.5:0.8-1.5:0.1-0.2.
Further, the ratio of the amounts of substances of p-aminophenol, phenylboronic acid, benzoic acid, potassium carbonate or acetate, copper acetate or chloride is: 1:1:0.2:1:0.2.
Further, the ratio of the amounts of substances of p-aminophenol, phenylboronic acid, benzoic acid, potassium carbonate or acetate, copper acetate or chloride is: 1:1:0.5:1:0.1.
Further, the ratio of the amounts of substances of p-aminophenol, phenylboronic acid, benzoic acid, potassium carbonate or acetate, copper acetate or chloride is: 1:1:0.5:1:0.2.
Further, the distillation product was recrystallized using petroleum ether.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the method, a divalent copper salt is used as a catalyst under an alkaline condition, benzoic acid is used as a catalytic auxiliary agent, p-aminophenol and phenylboronic acid are directly coupled and dehydrogenated and oxidized by a one-step method to prepare p-benzoquinone monoimine, the copper salt has a catalytic C-N coupling property, N-phenyl-p-aminophenol generated by coupling p-aminophenol and phenylboronic acid is adopted, the copper salt has a catalytic oxidation property in the same system and reacts with air to obtain the product p-benzoquinone monoimine, the continuous process of coupling and dehydroxidation reaction in the same reaction system is realized, the operation is simplified, multi-step reaction is not needed, the complexity of multi-step operation of the prior art is overcome, the time is shortened, and the efficiency is improved;
2. in the invention, the reaction process does not need gas protection, the raw materials are cheap, the cost is low, no heavy metal ions need to be added, and the environmental pollution is small;
3. according to the invention, the use of explosive oxidant is avoided, and the high risk of explosion is effectively avoided;
4. the method for preparing p-benzoquinone monoimine has the yield of 55-78 percent, obtains higher yield and has good practical application value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Thus, the following detailed description of the embodiments of the invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The method for synthesizing p-benzoquinone monoimine from p-aminophenol provided by the preferred embodiment of the invention comprises the following steps:
adding 150ml of ethyl acetate, 10mmol of aminophenol, 10mmol of phenylboronic acid, 2mmol of anhydrous copper acetate, 10mmol of potassium carbonate and 5mmol of benzoic acid into a four-neck flask provided with a stirring device, a reflux condensing device and a thermometer, and carrying out reflux reaction at 80 ℃ for 8 hours to obtain orange-red liquid; after the reaction is finished, cooling to room temperature, and then filtering; carrying out reduced pressure distillation on the filtrate, and recovering an organic solvent ethyl acetate in the reduced pressure distillation process to obtain a dark orange red solid; recrystallizing the solid with petroleum ether, and then carrying out suction filtration; washing with recrystallization mother liquor for 3 times obtains 1.63g of orange solid product with 89.1 percent of yield.
Example 2
The method for synthesizing p-benzoquinone monoimine from p-aminophenol provided by the preferred embodiment of the invention comprises the following steps:
adding 150ml of ethyl acetate, 10mmol of aminophenol, 10mmol of phenylboronic acid, 2mmol of copper chloride dihydrate, 10mmol of potassium acetate and 5mmol of benzoic acid into a four-neck flask provided with a stirring device, a reflux condensing device and a thermometer, and carrying out reflux reaction at 80 ℃ for 10 hours to obtain orange-red liquid; after the reaction is finished, cooling to room temperature, and then filtering; carrying out reduced pressure distillation on the filtrate, and recovering an organic solvent ethyl acetate in the reduced pressure distillation process to obtain a dark orange red solid; recrystallizing the solid with petroleum ether, and then carrying out suction filtration; washing with recrystallization mother liquor for 2 times obtains 1.42g of orange solid product with yield of 77.6%.
Example 3
The method for synthesizing p-benzoquinone monoimine from p-aminophenol provided by the preferred embodiment of the invention comprises the following steps:
adding 150ml of ethyl acetate, 10mmol of aminophenol, 10mmol of phenylboronic acid, 2mmol of copper acetate monohydrate, 10mmol of potassium acetate and 5mmol of benzoic acid into a four-neck flask provided with a stirring device, a reflux condensing device and a thermometer, and carrying out reflux reaction at 80 ℃ for 10 hours to obtain orange-red liquid; after the reaction is finished, cooling to room temperature, and then filtering; carrying out reduced pressure distillation on the filtrate, and recovering an organic solvent ethyl acetate in the reduced pressure distillation process to obtain a dark orange red solid; recrystallizing the solid with petroleum ether, and then carrying out suction filtration; washing with recrystallization mother liquor for 3 times obtains 1.31g of orange solid product with the yield of 71.6 percent.
Example 4
The method for synthesizing p-benzoquinone monoimine from p-aminophenol provided by the preferred embodiment of the invention comprises the following steps:
adding 150ml of ethyl acetate, 10mmol of aminophenol, 10mmol of phenylboronic acid, 1mmol of anhydrous copper acetate, 10mmol of potassium carbonate and 5mmol of benzoic acid into a four-neck flask provided with a stirring device, a reflux condensing device and a thermometer, and carrying out reflux reaction at 80 ℃ for 15 hours to obtain orange-red liquid; after the reaction is finished, cooling to room temperature, and then filtering; carrying out reduced pressure distillation on the filtrate, and recovering an organic solvent ethyl acetate in the reduced pressure distillation process to obtain a dark orange red solid; recrystallizing the solid with petroleum ether, and then carrying out suction filtration; washing with recrystallization mother liquor for 2 times obtains 1.14g of orange solid product with yield of 62.2%.
Example 5
The method for synthesizing p-benzoquinone monoimine from p-aminophenol provided by the preferred embodiment of the invention comprises the following steps:
adding 150ml of ethyl acetate, 10mmol of aminophenol, 10mmol of phenylboronic acid, 2mmol of anhydrous copper acetate, 10mmol of potassium acetate and 2mmol of benzoic acid into a four-neck flask provided with a stirring device, a reflux condensing device and a thermometer, and carrying out reflux reaction at 80 ℃ for 8 hours to obtain orange-red liquid; after the reaction is finished, cooling to room temperature, and then filtering; carrying out reduced pressure distillation on the filtrate, and recovering an organic solvent ethyl acetate in the reduced pressure distillation process to obtain a dark orange red solid; recrystallizing the solid with petroleum ether, and then carrying out suction filtration; washing with recrystallization mother liquor for 2 times to obtain 1.02g of orange solid product with the yield of 55.7 percent.
And detecting the obtained product, wherein the hydrogen spectrum data of the product is as follows:1HNMR(400MHz,Chloroform-d)δ7.42(t,J＝7.7Hz,2H),7.26(d,J＝13.1Hz,2H),7.12(s,1H),6.92(d,J＝7.7Hz,2H),6.63(d,J＝44.0Hz,2H)。
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A method for synthesizing p-benzoquinone monoimine by p-aminophenol is characterized in that: under the alkaline condition, carrying out catalytic coupling and dehydrogenation oxidation reaction on aminophenol and phenylboronic acid by adopting a catalyst and a catalytic auxiliary agent to synthesize benzoquinone monoimine in one step;
the method specifically comprises the following steps: dissolving p-aminophenol, phenylboronic acid, a catalyst, a catalytic assistant and an alkaline reagent in a solvent for reaction;
the solvent is ethyl acetate, the alkaline condition is potassium carbonate or potassium acetate solution, the catalyst is copper acetate or copper chloride, and the catalytic assistant is benzoic acid.
2. The method for synthesizing p-benzoquinone monoimine according to claim 1, wherein: the reaction conditions are as follows: reflux reaction is carried out for 6 to 18 hours at 65 to 90 ℃.
3. The method for synthesizing p-benzoquinone monoimine according to claim 1, wherein: cooling and filtering after the reaction is finished, distilling under reduced pressure, recrystallizing the distillation product, filtering after recrystallization, and washing for 2-5 times by adopting recrystallization mother liquor.
4. The method for synthesizing p-benzoquinone monoimine according to claim 1, wherein: the mass ratio of p-aminophenol, phenylboronic acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or copper chloride is as follows: 0.8-1.5:0.8-1.5:0.2-0.5:0.8-1.5:0.1-0.2.
5. The method for synthesizing p-benzoquinone monoimine according to claim 4, wherein: the mass ratio of the p-aminophenol, the phenylboronic acid, the benzoic acid, the potassium carbonate or the potassium acetate, and the copper acetate or the copper chloride is as follows: 1:1:0.2:1:0.2.
6. The method for synthesizing p-benzoquinone monoimine according to claim 4, wherein: the mass ratio of the p-aminophenol, the phenylboronic acid, the benzoic acid, the potassium carbonate or the potassium acetate, and the copper acetate or the copper chloride is as follows: 1:1:0.5:1:0.1.
7. The method for synthesizing p-benzoquinone monoimine according to claim 4, wherein: the mass ratio of the p-aminophenol, the phenylboronic acid, the benzoic acid, the potassium carbonate or the potassium acetate, and the copper acetate or the copper chloride is as follows: 1:1:0.5:1:0.2.
8. The method for synthesizing p-benzoquinone monoimine according to claim 3, wherein: and recrystallizing the distillation product by using petroleum ether.
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