CN110105218A - A kind of method that para-nitrotoluene prepares paranitrobenzaldehyde - Google Patents
A kind of method that para-nitrotoluene prepares paranitrobenzaldehyde Download PDFInfo
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- CN110105218A CN110105218A CN201910472332.2A CN201910472332A CN110105218A CN 110105218 A CN110105218 A CN 110105218A CN 201910472332 A CN201910472332 A CN 201910472332A CN 110105218 A CN110105218 A CN 110105218A
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- nitrotoluene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The present invention relates to a kind of methods that para-nitrotoluene prepares paranitrobenzaldehyde to sequentially add organic solvent and para-nitrotoluene in reactor using polyoxometallate as catalyst, it is eventually adding oxidant, at 50~80 DEG C, is stirred to react, 12~48h, isolated para-nitrotoluene.Compared with prior art, operation of the present invention is simple, mild condition, it is a kind of preparation method with Atom economy, the paranitrobenzaldehyde of environment friendly, the conversion ratio of para-nitrotoluene and the selectivity of paranitrobenzaldehyde are high, catalyst has the characteristics that green high-efficient and is easily recycled have the value of utilization and extention.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of to use polyoxometallate efficient catalytic para-nitrotoluene
The method for preparing paranitrobenzaldehyde.
Background technique
Paranitrobenzaldehyde is important organic intermediate, can be used for the industries such as medicine, fragrance, dyestuff, food, pesticide,
Due to its being widely used industrially, so that people widely pay close attention to its synthesis.
It is raw material that traditional synthetic method, which is mostly used para-nitrotoluene and acetic anhydride, is oxidation with potassium bichromate or potassium permanganate
Agent obtains para-nitrotoluene through oxide side chain and hydrolysis.But the method condition is stringent, poor selectivity, low yield, and generates
It is a large amount of intractable extremely serious containing acid waste waters, environmental pollutions such as chromium.Using benzyl chloride as raw material, through nitrification, hydrolysis and oxidation
Obtain target product.The raw material first step nitration reaction of the method uses the mixture of nitric acid and solid super-strong acid niobium pentaoxide
As nitrating agent, the more traditional nitric acid-sulfuric acid mixed acid system of para-selectivity is improved.But the route is to the water of nitrobenzyl chloride
Solution condition is harsher, is easy to cause the generation of by-product benzyl ether.
The direct oxidation of para-nitrotoluene is paranitrobenzaldehyde, and oxygen source is air or oxygen, and by-product is water, is had
The environmentally protective advantage without chlorine impurity, synthetic route is short, advantage at low cost, is the mainstream work of paranitrobenzaldehyde production
Skill.
Yu Yuanbin et al. replaces conventional catalyst using metalloporphyrin class bionic catalyst, is replaced with cleaning cheap air
The inorganic salt oxidizing agent of environmental pollution replaces the acid medium of equipment seriously corroded, with methanol-alkaline medium with para-nitrotoluene
For raw material, synthesize paranitrobenzaldehyde (CN1271040C).But the selectivity and yield of the method paranitrobenzaldehyde are very low,
More by-product is formed, does not have environmental economy meaning.
2013 Nian Peng Xinhua et al. propose using para-nitrotoluene as raw material, carry out bromination, hydrolysis, oxidation and separation etc.
Operation, has obtained paranitrobenzaldehyde (CN102126960B).This method mild condition, selective preferable, high income.But
Method is too cumbersome, and introduces bromide, is unfavorable for industrial production.
There is presently no a kind of green, environmental protection, the single method for generating paranitrobenzaldehyde of catalysis oxidation para-nitrotoluene.
Polyoxometallate (polyacid) is a kind of novel efficient multifunction catalyst, that is, has acid catalytic property, and have
There is redox catalysis performance, and stability is fine, can both make homogeneous reaction, heterogeneous reaction can also be made, or even phase can be made and turned
Shifting catalyst, is a kind of very promising green, environmental protection catalyst, is widely used in catalysis, analysis, drug, electrochemistry, photochemical
It learns and the fields such as petrochemistry.With high activity, highly selective, high stability, recyclable advantage.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind have high activity and
Highly selective, reaction condition is mild, green and environmental protection, catalyst can recycle, and has great industrial production potential
The para-nitrotoluene method for preparing paranitrobenzaldehyde.
The purpose of the present invention can be achieved through the following technical solutions: a kind of para-nitrotoluene prepares paranitrobenzaldehyde
Method, which is characterized in that using polyoxometallate as catalyst, be placed in reactor, by organic solvent and para-nitrotoluene
It sequentially adds in reactor, is eventually adding oxidant, at 50~80 DEG C, be stirred to react, 12~48h, it is isolated to nitro
Benzaldehyde.
The reaction equation for the para-nitrotoluene oxidation being related in the present invention is expressed as
Further, the catalyst be Keggin-type, Dawson type, Silverton type, Waugh type,
The polyoxometallate of Lindquist type or Anderson type.
Preferably, the catalyst is the more metals of Anderson type centered on Fe, Al, Cr, Ni, Mn, Cu or Co
Oxygen hydrochlorate.
Further, the organic solvent uses aprotic polar solvent, including acetonitrile, acetic acid, Isosorbide-5-Nitrae-dioxy six
Ring or benzene.Preferably, the organic solvent is CH3CN, preferably 75 DEG C of reaction temperature.
Further, the oxidant is hydrogen peroxide, air or oxygen.The preferred hydrogen peroxide of oxidant, peroxidating
The dosage of hydrogen is 2.0~6.0 equivalents；Preferably, the dosage of the hydrogen peroxide is 4 equivalents；
Further, the dosage of the catalyst are as follows: the molar ratio of catalyst and para-nitrotoluene be 0.001~
0.05:3；Preferably, the dosage of the catalyst are as follows: the molar ratio of catalyst and para-nitrotoluene is 0.01:3；
Further, the dosage of the organic solvent are as follows: the molal volume of para-nitrotoluene and organic solvent ratio are as follows: 3:
(2~6) (mol/L).Preferably, the dosage of the organic solvent are as follows: the molal volume of para-nitrotoluene and organic solvent ratio
Are as follows: 1:1 (mol/L).
Recycling and reusing, the method for recycling and reusing are carried out after the catalyst reaction are as follows: after reaction, institute
It obtains solution to be filtered, filters out polyoxometallate, be recycled after processing, filtrate is cooled to room temperature, wherein to nitro
Benzaldehyde product is precipitated, and the polyacid that surplus solution contains is recycled in the oxidation reaction of para-nitrotoluene.To reaction system into
Row post-processing obtains the paranitrobenzaldehyde (95%) of high yield.90% or more the conversion ratio of para-nitrotoluene is selectively about
100%.
Using the method for control variable to the solvent of reaction, temperature, additive, the amount of additive, the amount of catalyst, oxidation
The amount of agent is screened, and optimal reaction condition is obtained.
Compared with prior art, the invention has the following advantages that preparation is simple, product yield high, no three wastes, production cost
The features such as low is that a kind of Atom economy is high, the environmentally friendly method for preparing paranitrobenzaldehyde.Catalyst used is
Repeatedly reaction can also be recycled in a kind of new catalyst --- polyoxometallate (heteropoly acid) after simple process
It does not need additionally to add acid in the process, be controlled in terms of corrosivity, this is advantageous to industrial production, therefore the invention has
Potential application prospect.
Detailed description of the invention
Fig. 1 is the carbon-13 nmr spectra of paranitrobenzaldehyde13C NMR(CDCl3)；
Fig. 2 is the nuclear magnetic resonance spectroscopy of paranitrobenzaldehyde1H NMR(CDCl3)。
Specific embodiment
In order to which the present invention is further described in detail, several specific implementation cases are given below, still, the present invention
It is not limited to these examples.Each polyoxometallate used in the examples (Keggin-type, Dawson type, Silverton type,
Waugh type, Lindquist type, Anderson type) catalyst is polyoxometallate commonly used in the art, pass through existing literature
The method of report is made or is obtained by commercially available method.
Embodiment 1
It is the Anderson type multi-metal oxygen of center metal by the Fe of the para-nitrotoluene of 411.3g, 0.1~5.0mol%
The hydrogen peroxide of hydrochlorate, 2.0~6.0equiv, the solvent acetonitrile of 2.0~6.0L are put into dry reaction pipe, are covered on reaction tube
Balloon, reaction temperature control at 50~80 DEG C, insulation reaction for 24 hours after, stop reaction, be cooled to room temperature, GC-MS inspection is done in sample preparation
It surveys, GC-MS result is that reaction substrate conversion ratio is 95%.Nuclear-magnetism test is carried out after separating-purifying, and number is composed by resulting hydrogen spectrum, carbon
It is demonstrated that it is paranitrobenzaldehyde, as shown in Figs. 1-2.
Embodiment 2
It is the Anderson type multi-metal oxygen of center metal by the Al of the para-nitrotoluene of 411.3g, 0.1~5.0mol%
The hydrogen peroxide of hydrochlorate, 2.0~6.0equiv, the solvent acetonitrile of 2.0~6.0L are put into dry reaction pipe, are covered on reaction tube
Balloon, reaction temperature control at 50~80 DEG C, insulation reaction for 24 hours after, stop reaction, be cooled to room temperature, GC-MS inspection is done in sample preparation
It surveys, GC-MS result is that reaction substrate conversion ratio is 93%.Nuclear-magnetism test is carried out after separating-purifying, and number is composed by resulting hydrogen spectrum, carbon
It is demonstrated that it is paranitrobenzaldehyde.
Embodiment 3
It is the Anderson type multi-metal oxygen of center metal by the Cr of the para-nitrotoluene of 411.3g, 0.1~5.0mol%
The hydrogen peroxide of hydrochlorate, 2.0~6.0equiv, the solvent acetonitrile of 2.0~6.0L are put into dry reaction pipe, are covered on reaction tube
Balloon, reaction temperature control at 50~80 DEG C, insulation reaction for 24 hours after, stop reaction, be cooled to room temperature, GC-MS inspection is done in sample preparation
It surveys, GC-MS result is that reaction substrate conversion ratio is 97%.Nuclear-magnetism test is carried out after separating-purifying, and number is composed by resulting hydrogen spectrum, carbon
It is demonstrated that it is paranitrobenzaldehyde.
Embodiment 4
It is the Anderson type multi-metal oxygen of center metal by the Ni of the para-nitrotoluene of 411.3g, 0.1~5.0mol%
The hydrogen peroxide of hydrochlorate, 2.0~6.0equiv, the solvent acetonitrile of 2.0~6.0L are put into dry reaction pipe, are covered on reaction tube
Balloon, reaction temperature control at 50~80 DEG C, insulation reaction for 24 hours after, stop reaction, be cooled to room temperature, GC-MS inspection is done in sample preparation
It surveys, GC-MS result is that reaction substrate conversion ratio is 95%.Nuclear-magnetism test is carried out after separating-purifying, and number is composed by resulting hydrogen spectrum, carbon
It is demonstrated that it is paranitrobenzaldehyde.
Embodiment 5
It is the Anderson type multi-metal oxygen of center metal by the Mn of the para-nitrotoluene of 411.3g, 0.1~5.0mol%
The hydrogen peroxide of hydrochlorate, 2.0~6.0equiv, the solvent acetonitrile of 2.0~6.0L are put into dry reaction pipe, are covered on reaction tube
Balloon, reaction temperature control at 50~80 DEG C, insulation reaction for 24 hours after, stop reaction, be cooled to room temperature, GC-MS inspection is done in sample preparation
It surveys, GC-MS result is that reaction substrate conversion ratio is 95%.Nuclear-magnetism test is carried out after separating-purifying, and number is composed by resulting hydrogen spectrum, carbon
It is demonstrated that it is paranitrobenzaldehyde.
Embodiment 6
It is the Anderson type multi-metal oxygen of center metal by the Co of the para-nitrotoluene of 411.3g, 0.1~5.0mol%
The hydrogen peroxide of hydrochlorate, 2.0~6.0equiv, the solvent acetonitrile of 2.0~6.0L are put into dry reaction pipe, are covered on reaction tube
Balloon, reaction temperature control at 50~80 DEG C, insulation reaction for 24 hours after, stop reaction, be cooled to room temperature, GC-MS inspection is done in sample preparation
It surveys, GC-MS result is that reaction substrate conversion ratio is 95%.Nuclear-magnetism test is carried out after separating-purifying, and number is composed by resulting hydrogen spectrum, carbon
It is demonstrated that it is paranitrobenzaldehyde.
Embodiment 7
It is the Anderson type multi-metal oxygen of center metal by the Cu of the para-nitrotoluene of 411.3g, 0.1~5.0mol%
The hydrogen peroxide of hydrochlorate, 2.0~6.0equiv, the solvent acetonitrile of 2.0~6.0L are put into dry reaction pipe, are covered on reaction tube
Balloon, reaction temperature control at 50~80 DEG C, insulation reaction for 24 hours after, stop reaction, be cooled to room temperature, GC-MS inspection is done in sample preparation
It surveys, GC-MS result is that reaction substrate conversion ratio is 95%.Nuclear-magnetism test is carried out after separating-purifying, and number is composed by resulting hydrogen spectrum, carbon
It is demonstrated that it is paranitrobenzaldehyde.Processing recycling is carried out to the catalyst after reaction.
Embodiment 8
Reaction step with example 1, the differ in that, used catalyst is the 1st use after recycling, GC-MS point
Analysis learns that the conversion ratio of para-nitrotoluene is greater than 95%, and separating-purifying obtains product, and nuclear-magnetism is confirmed as paranitrobenzaldehyde, yield
95%.
Embodiment 9
Reaction step with example 1, the differ in that, used catalyst is the 2nd use after recycling, GC-MS point
Analysis learns that the conversion ratio of para-nitrotoluene is greater than 95%, and separating-purifying obtains product, and nuclear-magnetism is confirmed as paranitrobenzaldehyde.
Embodiment 10
Reaction step with example 1, the differ in that, used catalyst is the 3rd use after recycling, GC-MS point
Analysis learns that the conversion ratio of para-nitrotoluene is 93%, and separating-purifying obtains product, and nuclear-magnetism is confirmed as paranitrobenzaldehyde.
Embodiment 11
Reaction step with example 1, the differ in that, used catalyst is that the 4th uses after recycling, GC-MS point
Analysis learns that the conversion ratio of para-nitrotoluene is 93%, and separating-purifying obtains product, and nuclear-magnetism is confirmed as paranitrobenzaldehyde.
Embodiment 12
Reaction step with example 1, the differ in that, in the reaction be added 4- butylammonium bromide 4.8g
(0.5mol%), GC-MS analysis learn that lower than 90%, catalyst solid is obtained by filtration in the conversion ratio of para-nitrotoluene, and washing is dry
It is dry, it collects and recycles, filtrate separating-purifying is obtained into white product, is confirmed through nuclear-magnetism, is paranitrobenzaldehyde.
Embodiment 13
Reaction step with example 1, the differ in that, used catalyst be Keggin-type polyoxometallate catalysis
Agent, the conversion ratio of para-nitrotoluene are 95%, and selectivity is 100%.
Embodiment 14
Reaction step with example 1, the differ in that, used catalyst be Dawson type polyoxometallate catalysis
Agent, the conversion ratio of para-nitrotoluene are 93%, and selectivity is 100%.
Embodiment 15
Reaction step with example 1, the differ in that, used catalyst be Silverton type polyoxometallate
Catalyst, the conversion ratio of para-nitrotoluene are 97%, and selectivity is 100%.
Embodiment 16
Reaction step with example 1, the differ in that, used catalyst be Waugh type polyoxometallate catalysis
Agent, the conversion ratio of para-nitrotoluene are 90%, and selectivity is 100%.
Embodiment 17
Reaction step with example 1, the differ in that, used catalyst be Lindquist type polyoxometallate
Catalyst, the conversion ratio of para-nitrotoluene are 92%, and selectivity is 100%.
All above-mentioned embodiments, there is no the other forms that this new product or new method are implemented in setting.This field
Technical staff will utilize this important information, above content modification, to realize similar executive condition.But it all gives
Modification or transformation of the invention belongs to the right that the present invention retains.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of method that para-nitrotoluene prepares paranitrobenzaldehyde, which is characterized in that using polyoxometallate as catalyst,
Organic solvent and para-nitrotoluene are sequentially added in reactor, oxidant is eventually adding, at 50~80 DEG C, is stirred to react,
12~48h, isolated paranitrobenzaldehyde.
2. the method that a kind of para-nitrotoluene according to claim 1 prepares paranitrobenzaldehyde, which is characterized in that described
Catalyst dosage are as follows: the molar ratio of catalyst and para-nitrotoluene be 0.001~0.05:3；
The oxidant is hydrogen peroxide, and the dosage of hydrogen peroxide is 2.0~6.0 equivalents；
The dosage of the organic solvent are as follows: the molal volume of para-nitrotoluene and solvent ratio are as follows: 3:(2~6) (mol/L).
3. the method that a kind of para-nitrotoluene according to claim 2 prepares paranitrobenzaldehyde, which is characterized in that described
Catalyst dosage are as follows: the molar ratio of catalyst and para-nitrotoluene be 0.01:3；
The oxidant is hydrogen peroxide, and the dosage of hydrogen peroxide is 4 equivalents；
The dosage of the organic solvent are as follows: the molal volume of para-nitrotoluene and solvent ratio are as follows: 1:1 (mol/L).
4. the method that a kind of para-nitrotoluene according to claim 1 prepares paranitrobenzaldehyde, which is characterized in that described
Catalyst be Keggin-type, Dawson type, Silverton type, Waugh type, Lindquist type or Anderson type it is mostly golden
Belong to oxygen hydrochlorate.
5. the method that a kind of para-nitrotoluene according to claim 4 prepares paranitrobenzaldehyde, which is characterized in that described
Catalyst be Anderson type polyoxometallate centered on Fe, Al, Cr, Ni, Mn, Cu or Co.
6. the method that a kind of para-nitrotoluene according to claim 1 prepares paranitrobenzaldehyde, which is characterized in that described
Organic solvent include acetonitrile, acetic acid, 1,4- dioxane or benzene.
7. the method that a kind of para-nitrotoluene according to claim 1 prepares paranitrobenzaldehyde, which is characterized in that described
Oxidant be hydrogen peroxide, air or oxygen.
8. the method that a kind of para-nitrotoluene according to claim 1 prepares paranitrobenzaldehyde, which is characterized in that described
Catalyst reaction after carry out recycling and reusing, the method for recycling and reusing are as follows: after reaction, acquired solution carried out
Filter, filters out polyoxometallate, is recycled after processing, and filtrate is cooled to room temperature, and wherein paranitrobenzaldehyde product is analysed
Out, the polyacid that surplus solution contains is recycled in the oxidation reaction of para-nitrotoluene.
9. the method that a kind of para-nitrotoluene according to claim 1 prepares paranitrobenzaldehyde, which is characterized in that described
Organic solvent be CH3CN, reaction temperature are 75 DEG C.
10. the method that a kind of para-nitrotoluene according to claim 1 prepares paranitrobenzaldehyde, which is characterized in that anti-
For for 24 hours between seasonable.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662180A (en) * | 2020-07-17 | 2020-09-15 | 山东卓俊实业有限公司 | Preparation method of p-nitrobenzaldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126960A (en) * | 2010-12-10 | 2011-07-20 | 合肥工业大学 | High selectivity synthesis method of p-nitrobenzaldehyde |
| CN104418753A (en) * | 2013-08-21 | 2015-03-18 | 南京理工大学 | Method for green-catalytically synthesizing nitrobenzaldehyde |
-
2019
- 2019-05-31 CN CN201910472332.2A patent/CN110105218A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126960A (en) * | 2010-12-10 | 2011-07-20 | 合肥工业大学 | High selectivity synthesis method of p-nitrobenzaldehyde |
| CN104418753A (en) * | 2013-08-21 | 2015-03-18 | 南京理工大学 | Method for green-catalytically synthesizing nitrobenzaldehyde |
Non-Patent Citations (2)
| Title |
|---|
| 滕志君: "Dawson型多金属氧酸盐催化剂的制备及其应用研究", 《兰州理工大学硕士学位论文》 * |
| 范宗良等: "Dawson型杂多酸钕盐催化氧化甲苯制备苯甲醛(英文) ", 《分子催化》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662180A (en) * | 2020-07-17 | 2020-09-15 | 山东卓俊实业有限公司 | Preparation method of p-nitrobenzaldehyde |
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