CN115073258A - Polyacid catalytic preparation method of biphenyl - Google Patents
Polyacid catalytic preparation method of biphenyl Download PDFInfo
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- CN115073258A CN115073258A CN202210155818.5A CN202210155818A CN115073258A CN 115073258 A CN115073258 A CN 115073258A CN 202210155818 A CN202210155818 A CN 202210155818A CN 115073258 A CN115073258 A CN 115073258A
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- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/323—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a nitrogen atom
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Abstract
The invention relates to a polyacid catalytic preparation method of biphenyl, which comprises the following steps: putting catalyst polyoxometallate and an additive into a clean and dry reactor; sequentially adding aniline, acid and an organic solvent into a reactor; heating, stirring and reacting, and separating to obtain the biphenyl. Compared with the prior art, the method has the advantages of simple operation and mild conditions, is a preparation method of biphenyl with atom economy and environmental friendliness, has the characteristics of extremely high reaction activity, good specificity, easiness in recycling and the like, is environment-friendly, and has popularization and utilization values.
Description
Technical Field
The invention relates to the field of catalytic synthesis, in particular to a polyacid catalytic preparation method of biphenyl.
Background
Fossil energy is decreasing day by day, and human consumption is increasing day by day, also brings a series of environmental problems simultaneously. The production of chemical products and fuels from biomass has become a hot spot in current scientific research.
Biphenyl is an important substance for synthesizing organic compounds, and biaryl compounds are widely applied to the fields of medicines, pesticides, dyes, liquid crystal materials and the like in actual life. Can be used for synthesizing plasticizer and antiseptic, and can also be used for producing fuel, engineering plastics and high-energy fuel, etc. Biphenyl is found in coal tar, crude oil, and natural gas in nature. The application of biphenyl is wide, the synthesis and separation of biaryl compounds become a hotspot problem of current scientific research, and the goal of realizing the reaction of synthesizing biphenyl by efficiently catalyzing aniline is more favorable for industrial production.
The current methods for preparing aryl C-C bonds include common coupling reactions based on transition metal catalysis, such as Mizeroki-Heck, Nigishi, Stille, Ullmann, Gomberg-Buchmann reactions, chemical synthesis methods for preparing biphenyl by benzene pyrolysis, and the like, and separation and extraction methods for preparing biphenyl by various coal tar fractions. The mass fraction of biphenyl in coal tar is 0.20-0.40%, but the synthesis effect is limited due to low yield and poor selectivity.
At present, researchers in the society pursue an environment-friendly and efficient method for catalyzing aniline to generate biphenyl.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing biphenyl by polyacid catalysis, which has high activity, high selectivity, high stability and can be recycled.
The purpose of the invention can be realized by the following technical scheme:
the invention is based on the advantages of polyoxometallate (polyacid), is a novel high-efficiency multifunctional catalyst, has acid catalysis performance, redox catalysis performance and good stability, can be used for homogeneous reaction and heterogeneous reaction, and even can be used as a phase transfer catalyst, is a green and environment-friendly catalyst with wide prospect, and is widely applied to the fields of catalysis, analysis, medicines, electrochemistry, photochemistry, petrochemistry and the like. Has the advantages of high activity, high selectivity, high stability and cyclic utilization.
The method takes aniline as a raw material, polyoxometallate (Keggin type, Lindquist type and Anderson type, wherein Fe, Al, Cr, Ni, Mn, Cu, Co and other central metals of Anderson type frameworks are taken as main catalysts), benzene is taken as a solvent, hydrochloric acid provides an acidic environment for a reaction system, and the method is carried out under the action of an additive sodium nitrite. The catalytic system can catalyze aniline to synthesize biphenyl, has high activity and high selectivity, mild reaction conditions, greenness and environmental protection, can recycle the catalyst, has great industrial production potential, and has the following specific scheme:
a method for preparing biphenyl by polyacid catalysis is characterized by comprising the following steps:
putting catalyst polyoxometallate and an additive into a clean and dry reactor;
sequentially adding aniline, acid and an organic solvent into a reactor;
after heating and stirring reaction, biphenyl is obtained by separation, and the total reaction formula is as follows:
further, the polyoxometallate comprises a Keggin type, Lindquist type or Anderson type polyoxometallate, and the central metal of the catalyst comprises Fe, Al, Cr, Ni, Mn, Cu or Co.
Further, the additive comprises sodium nitrite, sodium sulfite, sodium carbonate or sodium bicarbonate, preferably sodium nitrite.
Further, the organic solvent is an aprotic polar solvent, including acetonitrile, acetic acid, 1, 4-dioxane, benzene, toluene or methanol, preferably benzene.
Further, the acid includes hydrochloric acid, sulfuric acid or nitric acid.
Furthermore, the addition amount of the catalyst is 0.1-5.0 mol% of aniline.
Further, the additive is added in an amount of 1.0 to 3.0 equivalents based on the reaction amount, i.e., the molar ratio of the additive to aniline is (1.0 to 3.0):1, preferably 1.0 equivalent; the acid is added in an amount of 0.5 to 2.0 equivalents based on the reaction amount, i.e., the molar ratio of acid to aniline is (0.5 to 2.0):1, preferably 0.7 equivalents.
Further, the ratio of the solvent to the aniline is (1.0-5.0) mL:0.5 mmol.
Further, the heating temperature is 40-80 ℃, preferably 60 ℃, and the reaction time is 1-12 hours, preferably 6 hours.
Further, the method comprises the following steps: and (3) extracting and filtering the system after the reaction is finished, taking the lower-layer water phase, treating the water phase, recovering, and reusing the recovered polyoxometallate in the catalytic reaction of aniline.
Compared with the prior art, the invention has the following advantages:
(1) the method has the characteristics of simple preparation, high product yield, low production cost and the like, and is an environment-friendly preparation method with high atom economy;
(2) the catalyst used in the invention is a novel catalyst, namely polyoxometallate (polyacid), and can be recycled for multiple times after simple treatment, so that the harm to equipment is obviously reduced, and the corrosivity is controlled, thus being very beneficial to industrial production and having potential application prospect.
Drawings
FIG. 1 is the NMR carbon spectrum of biphenyl in example 1 13 C NMR(CDCl 3 )；
FIG. 2 is the NMR hydrogen spectrum of biphenyl in example 1 1 H NMR(CDCl 3 )。
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
A method for preparing biphenyl by polyacid catalysis is characterized by comprising the following steps:
putting catalyst polyoxometallate and an additive into a clean and dry reactor; the polyoxometallate comprises polyoxometallate of Keggin type, Lindquist type or Anderson type, and the central metal of the catalyst comprises Fe, Al, Cr, Ni, Mn, Cu or Co. The additive comprises sodium nitrite, sodium sulfite, sodium carbonate or sodium bicarbonate, preferably sodium nitrite. The addition amount of the catalyst is 0.1-5.0 mol% of the aniline. The additive is added in an amount of 1.0 to 3.0 equivalents based on the reaction amount, i.e., the molar ratio of additive to aniline is (1.0 to 3.0):1, preferably 1.0 equivalent; the acid is added in an amount of 0.5 to 2.0 equivalents based on the reaction amount, i.e., the molar ratio of acid to aniline is (0.5 to 2.0):1, preferably 0.7 equivalents. The ratio of solvent to aniline was (1.0-5.0) mL:0.5 mmol.
Sequentially adding aniline, acid and an organic solvent into a reactor; the organic solvent is aprotic polar solvent, including acetonitrile, acetic acid, 1, 4-dioxane, benzene, toluene or methanol, preferably benzene. The acid includes hydrochloric acid, sulfuric acid or nitric acid. The heating temperature is 40-80 deg.C, preferably 60 deg.C, and the reaction time is 1-12h, preferably 6 h.
After heating and stirring reaction, biphenyl is obtained by separation, and the total reaction formula is as follows:
in addition, the system after the reaction is finished can be extracted and filtered, the lower-layer water phase is taken out, the water phase is recovered after being treated, and the recovered polyoxometallate can be reused for the catalytic reaction of the aniline.
For further detailed description of the present invention, several specific examples are given below, wherein examples of the polyoxometallate catalysts are Keggin type, Lindquist type and Anderson type centered on different metal atoms, wherein the central metals of Fe, Al, Cr, Ni, Mn, Cu and Co of Anderson type skeleton are the main metals
Example 1
0.0466g of aniline, 0.1 mol% of Anderson type polyoxometallate with Co as a central metal, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid (equivalent is calculated by HCl), and 2 mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, the reaction is stopped after heat preservation reaction is carried out for 6 hours, and the reaction is cooled to room temperature, wherein the reaction formula is as follows:
and performing GC-MS detection on the prepared sample, wherein the GC-MS result shows that the conversion rate of the reaction substrate is 96%. After separation and purification, a nuclear magnetic test is carried out, as shown in figures 1-2, and the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used as the magnetic material.
Example 2
0.0466g of aniline, 0.1 mol% of Al as central metal, Anderson type polyoxometallate, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid and 2 mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, after the reaction is carried out for 6 hours under heat preservation, the reaction is stopped, the reaction is cooled to room temperature, a sample is prepared and is detected by GC-MS, and the result of GC-MS is that the conversion rate of a reaction substrate is 83%. After separation and purification, a nuclear magnetic test is carried out, and referring to fig. 1-2, the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used.
Example 3
0.0466g of aniline, 0.1 mol% of Anderson type polyoxometallate taking Cr as a central metal, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid and 2.0mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, the reaction is stopped after the heat preservation reaction is carried out for 6 hours, the reaction is cooled to the room temperature, a sample is prepared and subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 93%. After separation and purification, a nuclear magnetic test is carried out, and referring to fig. 1-2, the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used.
Example 4
0.0466g of aniline, 0.1 mol% of Anderson type polyoxometallate taking Ni as a central metal, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid and 2.0mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, the reaction is stopped after the heat preservation reaction is carried out for 6 hours, the reaction is cooled to the room temperature, a sample is prepared and subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 94%. After separation and purification, a nuclear magnetic test is carried out, and referring to fig. 1-2, the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used.
Example 5
0.0466g of aniline, 0.1 mol% of Anderson type polyoxometallate taking Mn as a central metal, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid and 2.0mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, the reaction is stopped after the heat preservation reaction is carried out for 6 hours, the reaction is cooled to the room temperature, a sample is prepared and subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 62%. After separation and purification, a nuclear magnetic test is carried out, and referring to fig. 1-2, the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used.
Example 6
0.0466g of aniline, 0.1 mol% of Cu as central metal, Anderson type polyoxometallate, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid and 2.0mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, the reaction is stopped after the heat preservation reaction is carried out for 6 hours, the reaction is cooled to the room temperature, a sample is prepared and subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 70%. After separation and purification, a nuclear magnetic test is carried out, and referring to fig. 1-2, the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used.
Example 7
0.0466g of aniline, 0.1 mol% of Anderson type polyoxometallate taking Fe as a central metal, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid and 2.0mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, the reaction is stopped after the heat preservation reaction is carried out for 6 hours, the reaction is cooled to the room temperature, a sample is prepared and subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 80%. After separation and purification, a nuclear magnetic test is carried out, and referring to fig. 1-2, the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used. And (4) treating and recycling the catalyst after reaction.
Example 8
0.0466g of aniline, 0.1 mol% of Lindquist type polyoxometallate with Mo as a central metal, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid and 2.0mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, the reaction is stopped after the heat preservation reaction is carried out for 6 hours, the reaction is cooled to the room temperature, a sample is prepared and subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 73%. After separation and purification, a nuclear magnetic test is carried out, and referring to fig. 1-2, the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used. And (4) treating and recycling the catalyst after reaction.
Example 9
0.0466g of aniline, 0.1 mol% of Keggin type polyoxometallate with V as a central metal, 1.0 equivalent of sodium nitrite, 0.7 equivalent of hydrochloric acid and 2.0mL of solvent benzene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled at 60 ℃, the reaction is stopped after the heat preservation reaction is carried out for 6 hours, the reaction is cooled to the room temperature, a sample is prepared and subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 80%. After separation and purification, a nuclear magnetic test is carried out, and referring to fig. 1-2, the obtained hydrogen spectrum and carbon spectrum data prove that the biphenyl is used. And (4) treating and recycling the catalyst after reaction.
Example 10
The reaction procedure is the same as that of example 1, but the difference is that the catalyst used in example 1 is recovered and used for the 1 st time, the GC-MS analysis shows that the conversion rate of the aniline is more than 94%, the product is obtained by separation and purification, the nuclear magnetism confirms that the product is biphenyl, and the yield is 94%.
Example 11
The reaction procedure is the same as that of example 1, but the difference is that the catalyst used in example 1 is recovered and used for the 2 nd time, the GC-MS analysis shows that the conversion rate of the aniline is more than 93%, the product is obtained by separation and purification, and the product is identified as biphenyl by nuclear magnetism.
Example 12
The reaction procedure was the same as in example 1, except that the catalyst used in example 1 was recovered and used for the 3 rd time, the conversion of aniline was 92% by GC-MS analysis, and the product was isolated and purified and confirmed to be biphenyl by nuclear magnetism.
Example 13
The reaction procedure was the same as in example 1, except that the catalyst used in example 1 was recovered and used 4 th time, the conversion of aniline was 90% by GC-MS analysis, and the product was isolated and purified and confirmed to be biphenyl by nuclear magnetism.
All of the above-described embodiments are not intended to be exhaustive or to limit the invention to other forms disclosed herein for carrying out the novel products or processes. Those skilled in the art will take advantage of this important information and the foregoing will be modified to achieve similar performance. However, all modifications or adaptations to the present invention are within the scope of the invention as reserved.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing biphenyl by polyacid catalysis is characterized by comprising the following steps:
putting a catalyst polyoxometallate and an additive into a reactor;
sequentially adding aniline, acid and an organic solvent into a reactor;
heating, stirring and reacting, and separating to obtain the biphenyl.
2. The method of claim 1, wherein the polyoxometallate comprises a Keggin type, Lindquist type or Anderson type polyoxometallate, and the central metal of the catalyst comprises Fe, Al, Cr, Ni, Mn, Cu or Co.
3. The method as claimed in claim 1, wherein the additive includes sodium nitrite, sodium sulfite, sodium carbonate or sodium bicarbonate.
4. The method for preparing biphenyl by polyacid catalysis of claim 1, wherein the organic solvent is aprotic polar solvent, including acetonitrile, acetic acid, 1, 4-dioxane, benzene, toluene or methanol.
5. The method of claim 1, wherein the acid comprises hydrochloric acid, sulfuric acid or nitric acid.
6. The method for preparing biphenyl by polyacid catalysis of claim 1, wherein the amount of the catalyst added is 0.1-5.0 mol% of aniline.
7. The method for preparing biphenyl by polyacid catalysis of claim 1, wherein the additive is added in an amount of 1.0-3.0 equivalents based on the reaction amount; the addition amount of the acid is 0.5-2.0 equivalents of the reaction amount.
8. The method for preparing biphenyl with polyacidic catalysis according to claim 1, wherein the ratio of the solvent to aniline is (1.0-5.0) mL:0.5 mmol.
9. The method for preparing biphenyl by polyacid catalysis of claim 1, wherein the heating temperature is 40-80 ℃, and the reaction time is 1-12 h.
10. The method for the polyacid-catalyzed preparation of biphenyl of claim 1, further comprising the steps of: and (3) extracting and filtering the system after the reaction is finished, taking the lower-layer water phase, treating the water phase, recovering, and reusing the recovered polyoxometallate in the catalytic reaction of aniline.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724025A (en) * | 2021-01-08 | 2021-04-30 | 上海应用技术大学 | Preparation method of N-benzyl benzylamine |
| CN113019449A (en) * | 2020-06-24 | 2021-06-25 | 上海应用技术大学 | Catalytic preparation method of aromatic azoxy compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113019449A (en) * | 2020-06-24 | 2021-06-25 | 上海应用技术大学 | Catalytic preparation method of aromatic azoxy compound |
| CN112724025A (en) * | 2021-01-08 | 2021-04-30 | 上海应用技术大学 | Preparation method of N-benzyl benzylamine |
Non-Patent Citations (2)
| Title |
|---|
| ARTUR KASPRZAK, ET AL: "Ferrocene-Labeled Carbon-Encapsulated Iron Nanoparticles: The First Magnetic Nanocatalysts for C−H Arylation toward 1,1′- Biphenyl Formation" * |
| SURAJ M. SUTAR, ET AL: "1-Aryltriazenes in the Suzuki, Heck, and Sonogashira Reactions in Imidazolium-ILs, with [BMIM(SO3H)][OTf] or Sc(OTf)3 as Promoter, and Pd(OAc)2 or NiCl2·glyme as Catalyst" * |
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