CN107935973B - Preparation method of dibenzofuran - Google Patents
Preparation method of dibenzofuran Download PDFInfo
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- CN107935973B CN107935973B CN201711269156.XA CN201711269156A CN107935973B CN 107935973 B CN107935973 B CN 107935973B CN 201711269156 A CN201711269156 A CN 201711269156A CN 107935973 B CN107935973 B CN 107935973B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
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Abstract
The invention relates to the technical field of chemical materials, and provides a preparation method of dibenzofuran, which comprises the steps of adding ferric salt into diphenyl ether serving as a raw material, and reacting in an inert gas environment to obtain the required dibenzofuran, wherein the reaction temperature is 200-500 ℃, and the reaction time is 1-4 h. The preparation method is simple, low in cost and suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a preparation method of dibenzofuran.
Background
Dibenzofuran is an excellent high-boiling organic solvent, can dissolve various high-molecular compounds, and can also be used as a raw material for medicines, disinfectants, antiseptics, fuels, synthetic resins and high-temperature lubricants, for example, some derivatives of dibenzofuran have anti-inflammatory, analgesic, muscle-relaxing and vasodilating activities. In addition, dibenzofuran and biphenyl can form a eutectic mixture to be used as a heat transfer solvent.
At present, the methods for preparing dibenzofuran have the defects of complex preparation process or high cost, and are not beneficial to industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of dibenzofuran, which is simple, low in cost and suitable for industrial production.
In order to solve the technical problems, the invention adopts the following technical scheme. A preparation method of dibenzofuran comprises the steps of adding iron salt into diphenyl ether serving as a raw material, and reacting in an inert gas environment to obtain the required dibenzofuran, wherein the reaction temperature is 200-500 ℃, and the reaction time is 1-4 h.
Preferably, the mass ratio of the diphenyl ether to the iron salt is (50-200): 1.
preferably, the pressure of the reaction is 1-4 MPa.
Preferably, the inert gas is nitrogen or argon.
Preferably, the iron salt is ferric nitrate.
Preferably, the mass ratio of the diphenyl ether to the ferric salt is (80-150): 1.
preferably, the reaction time is 1-2.5 h.
Preferably, the iron salt is ferric chloride.
Preferably, the mass ratio of the diphenyl ether to the iron salt is (50-120): 1.
preferably, the reaction time is 2-4 h.
The invention has the beneficial effects that:
the invention provides a preparation method of dibenzofuran, which takes diphenyl ether as a raw material, adds ferric salt as a catalyst, and reacts in an inert gas environment to obtain dibenzofuran. The reaction temperature is 200-500 ℃, and the reaction is easy to achieve in industrial production.
Drawings
FIG. 1 is a graph showing the distribution of the product under ferric nitrate in the present invention.
FIG. 2 is a graph showing the distribution of the product under ferric chloride in the present invention.
Detailed Description
For those skilled in the art to more clearly understand the objects, technical solutions and advantages of the present invention, the following description will be further provided in conjunction with the accompanying drawings and examples.
A preparation method of a catalyst comprises the steps of adding iron salt into diphenyl ether serving as a raw material, and reacting in an inert gas environment to obtain the required dibenzofuran, wherein the reaction temperature is 200-500 ℃, and the reaction time is 1-4 h. The preparation method has the advantages of simple process, low cost and suitability for industrial production; the reaction temperature is 200-500 ℃, and the reaction is easy to achieve in industrial production.
It can be understood that when less iron salt is added, the reaction speed is slower, and the required reaction time is longer; when more iron salt is added, other impurities, such as by-products and iron salt itself, are introduced. Preferably, the mass ratio of the diphenyl ether to the iron salt is (50-200): 1. preferably, the pressure of the reaction is 1-4MPa, the reaction can be better carried out under the pressure, and the reaction can be easily achieved in industrial production; more preferably, the pressure of the reaction is 2 to 3 MPa. The inert gas is nitrogen or argon, preferably nitrogen, and is cheap and easy to obtain.
The iron salt can be ferric chloride, ferric nitrate, ferric sulfate or ferric hydroxide and the like. In some embodiments, the iron salt is ferric nitrate and the reaction mechanism is:
preferably, the mass ratio of the diphenyl ether to the ferric salt is (80-150): 1, namely the mass ratio of the diphenyl ether to the ferric nitrate is (80-150): 1; more preferably, the mass ratio of the diphenyl ether to the iron salt is (100- & ltSUB & gt 150-): 1, optimally, the mass ratio of the diphenyl ether to the ferric salt is 120: 1. when the iron salt is ferric nitrate, the reaction time is preferably 1-2.5 hours, and most preferably 2 hours.
In a specific embodiment, the mass ratio of diphenyl ether to ferric nitrate is 100: 1, the reaction temperature is 300 ℃, the inert gas is nitrogen, the reaction pressure is 2MPa, and the reaction time is 2 hours. The obtained reaction product was analyzed by using a two-dimensional GC-MS to obtain a distribution diagram of the product under ferric nitrate, as shown in FIG. 1. Wherein, the reference numeral 1 is raw diphenyl ether, the reference numeral 2 is target product dibenzofuran, and the content of dibenzofuran is 12.3% (vol).
In other embodiments, the iron salt is ferric chloride and the reaction mechanism is:
preferably, the mass ratio of the diphenyl ether to the iron salt is (50-120): 1, namely the mass ratio of the diphenyl ether to the ferric chloride is (50-120): 1; more preferably, the mass ratio of the diphenyl ether to the ferric salt is (80-120): 1, optimally, the mass ratio of the diphenyl ether to the ferric salt is 100: 1. when the iron salt is ferric chloride, the reaction time is preferably 2-4h, and most preferably 2.5 h.
In a specific embodiment, the mass ratio of diphenyl ether to ferric chloride is 100: 1, the reaction temperature is 300 ℃, the inert gas is nitrogen, the reaction pressure is 2MPa, and the reaction time is 2.5 h. The obtained reaction product was analyzed by a full two-dimensional gas chromatograph-mass spectrometer to obtain a product distribution map under ferric chloride, as shown in fig. 2. Wherein, the reference numeral 1 is raw diphenyl ether, the reference numeral 2 is target product dibenzofuran, and the content of dibenzofuran is 9.8% (vol).
Some experimental groups are provided below
Weighing 8g of diphenyl ether as a raw material and 0.1g of ferric nitrate, adding into a reaction kettle, and introducing N2The pressure in the reaction kettle is 2Mpa, and the reaction kettle is heated to 300 ℃ to react for 2h to obtain a reaction product.
Experimental group 2
10g of diphenyl ether is weighed as raw material and 0.1g of ferric nitrate are added into a reaction kettle, and then N is introduced2The pressure in the reaction kettle is 2Mpa, and the reaction kettle is heated to 300 ℃ to react for 2h to obtain a reaction product.
Experimental group 3
Weighing 12g of diphenyl ether as a raw material and 0.1g of ferric nitrate, adding into a reaction kettle, and introducing N2The pressure in the reaction kettle is 2Mpa, and the reaction kettle is heated to 300 ℃ to react for 2h to obtain a reaction product.
Experimental group 4
Weighing 15g of diphenyl ether as a raw material and 0.1g of ferric nitrate, adding into a reaction kettle, and introducing N2The pressure in the reaction kettle is 2Mpa, and the reaction kettle is heated to 300 ℃ to react for 2h to obtain a reaction product.
Experimental group 5
5g of diphenyl ether is weighed as raw material and 0.1g of ferric chloride are added into a reaction kettle, and then N is introduced2The pressure in the reaction kettle is 2Mpa, and the reaction product is obtained after the reaction is heated to 300 ℃ and reacted for 2.5 h.
Experimental group 6
8g of diphenyl ether are weighedAdding raw materials and 0.1g of ferric chloride into a reaction kettle, and then introducing N2The pressure in the reaction kettle is 2Mpa, and the reaction product is obtained after the reaction is heated to 300 ℃ and reacted for 2.5 h.
Experimental group 7
Weighing 10g of diphenyl ether as a raw material and 0.1g of ferric chloride, adding into a reaction kettle, and introducing N2The pressure in the reaction kettle is 2Mpa, and the reaction product is obtained after the reaction is heated to 300 ℃ and reacted for 2.5 h.
Experimental group 8
Weighing 12g of diphenyl ether as a raw material and 0.1g of ferric chloride, adding into a reaction kettle, introducing N2 to ensure that the pressure in the reaction kettle is 2Mpa, heating to 300 ℃, and reacting for 2.5h to obtain a reaction product.
Aiming at the reaction products obtained from the experimental groups 1-8, the reaction products are analyzed by using a full two-dimensional gas chromatograph-mass spectrometer to obtain the content of dibenzofuran in the reaction products obtained from each experimental group, and the results are shown in the following table:
from the above table it can be seen that:
(1) compared with ferric chloride, ferric nitrate is used as the ferric salt, and the content of dibenzofuran in the obtained reaction product is higher;
(2) when the ferric salt is ferric nitrate, the mass ratio of the diphenyl ether to the ferric salt is 120: 1, the content of dibenzofuran in the reaction product is highest;
(3) when the ferric salt is ferric chloride, the mass ratio of the diphenyl ether to the ferric salt is 100: 1, the dibenzofuran content in the reaction product was the highest.
Claims (7)
1. A preparation method of dibenzofuran is characterized by comprising the following steps: adding iron salt into diphenyl ether as a raw material, and reacting in a nitrogen or inert gas environment to obtain the required dibenzofuran, wherein the reaction temperature is 200-500 ℃, and the reaction time is 1-4 h; the ferric salt is ferric nitrate or ferric chloride; the pressure of the reaction is 1-4 MPa.
2. The process for producing dibenzofuran of claim 1, wherein: the mass ratio of the diphenyl ether to the ferric salt is (50-200): 1.
3. the process for producing dibenzofuran of claim 1, wherein: the inert gas is argon.
4. A process for the preparation of dibenzofurans according to any one of claims 1 to 3, characterized in that: the ferric salt is ferric nitrate, and the mass ratio of the diphenyl ether to the ferric salt is (80-150): 1.
5. the process for producing dibenzofuran of claim 4, wherein: the reaction time is 1-2.5 h.
6. A process for the preparation of dibenzofurans according to any one of claims 1 to 3, characterized in that: the ferric salt is ferric chloride, and the mass ratio of the diphenyl ether to the ferric salt is (50-120): 1.
7. the process for producing dibenzofuran of claim 6, wherein: the reaction time is 2-4 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951918A (en) * | 1962-11-06 | 1976-04-20 | Imperial Chemical Industries Limited | Manufacture of polysulphones |
| CN104387351A (en) * | 2014-11-11 | 2015-03-04 | 常州大学 | Synthesis method of 4,4'-difluoro dibenzofuran |
| CN105348240A (en) * | 2015-11-13 | 2016-02-24 | 中节能万润股份有限公司 | A preparing method of a dibenzofuran compound |
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- 2017-12-05 CN CN201711269156.XA patent/CN107935973B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951918A (en) * | 1962-11-06 | 1976-04-20 | Imperial Chemical Industries Limited | Manufacture of polysulphones |
| CN104387351A (en) * | 2014-11-11 | 2015-03-04 | 常州大学 | Synthesis method of 4,4'-difluoro dibenzofuran |
| CN105348240A (en) * | 2015-11-13 | 2016-02-24 | 中节能万润股份有限公司 | A preparing method of a dibenzofuran compound |
Non-Patent Citations (3)
| Title |
|---|
| Silicon-Directed Nazarov Cyclizations. 8. Stereoelectronic Control of Torquoselectivity;Scott E. Denmark等;《J. Org. Chem.》;19901012;第55卷(第21期);第5543-5544页 * |
| The reaction of pyrite with diphenyl ether;Peter A. S. Smith等;《Tetrahedron Letters》;19841231;第25卷(第28期);第2949页第10行-第2952页第10行，Table I * |
| 基于铁催化的C-H键活化构建C-C键的研究进展;牛坡等;《中国科学：化学》;20111231;第41卷(第6期);第943-955页 * |
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