CN101525292A - Preparation method of paranitrobenzoic acid - Google Patents
Preparation method of paranitrobenzoic acid Download PDFInfo
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- CN101525292A CN101525292A CN200910048761A CN200910048761A CN101525292A CN 101525292 A CN101525292 A CN 101525292A CN 200910048761 A CN200910048761 A CN 200910048761A CN 200910048761 A CN200910048761 A CN 200910048761A CN 101525292 A CN101525292 A CN 101525292A
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- nitrotoluene
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method of paranitrobenzoic acid. The method comprises the following steps: adding metal phthalocyanine and hydrophobic ionic liquid at a mass ratio of 1:40-200, nitrotroluene and NaOH or KOH at the mass ratio of 1:1-3 to a reaction kettle, and evenly mixing; charging oxygen at the pressure of 0.5-2.5MPa into the reaction kettle, placing the reaction kettle in water bath with the temperature of 60-100 DEG C for thermostatic reaction for 4-12 hours, and cooling to the room temperature; adding deionized water, stirring and keeping standing for layering, and taking supernatant; adding 0.5-3.0mol/L diluted acid solution to the supernatant until the supernatant is acidic, and separating a product out by precipitation; and obtaining the paranitrobenzoic acid after filtrating and vacuum drying. The preparation method has the advantages of low preparation cost, easy separation of a catalytic system from a reaction system, recycled catalyst, and easy separation of the paranitrobenzoic acid from the system without organic solvent.
Description
Technical field
The present invention relates to technical field of organic synthesis, specifically a kind of method for preparing p-nitrobenzoic acid by molecular oxygen catalysis oxidation para-nitrotoluene.
Background technology
P-nitrobenzoic acid is a kind of important medicine intermediate and organic synthesis raw material, can be used for producing medicine and active rich look red M-8B, reactive red-violet X-2R such as vovocan, procaine amide hydrochloride, folic acid (vitamin Bc), Benzocaine, cefazolin, treatment hypertension, p-nitrobenzoic acid also is the important source material of plant growth regulator ' Inshuzhi ' simultaneously, industrial being in great demand.The method of traditional preparation process p-nitrobenzoic acid is that used oxygenant mainly contains potassium permanganate, potassium bichromate, hypohalous acid sodium etc. with high price inorganic metal salt oxidation para-nitrotoluene.This traditional method cost height, serious to equipment corrosion, and produce a large amount of waste liquids, contaminate environment has been subjected to the restriction of various countries.Recently along with the development of Green Chemistry and the enhancing of people's Environmental awareness, traditional high price inorganic metal salt oxidizing agent is substituted by eco-friendly oxygenant such as hydrogen peroxide and molecular oxygen gradually.Professor She Yuanbin of Beijing University of Technology equal 2006 in the world well-known periodical " Organic Process Research; Development " the 10th volume 757-761 page or leaf reported that with the metalphthelein mountain valley with clumps of trees and bamboo be catalyzer, prepared p-nitrobenzoic acid with molecular oxygen as oxygenant, productive rate is 90.4%, volatile organic reagent methyl alcohol is arranged in a large number as solvent but used in this technology, in pure oxygen environment, have the potential safety hazard of blast.
Summary of the invention
It is simple that a kind of reaction conditions of providing at the deficiencies in the prior art is provided, environmental friendliness, efficient height, the method for preparing p-nitrobenzoic acid that green degree is high.
The concrete technical scheme that realizes the object of the invention is:
A kind of preparation method of p-nitrobenzoic acid is to be raw material with the para-nitrotoluene, is catalyzer with hydrophobic ionic liquid dissolved metal phthalocyanine, oxygen is oxygenant, react in autoclave, prepare p-nitrobenzoic acid, it comprises following concrete steps:
A), be 1: 40～200 to put into reactor with metal phthalocyanine and hydrophobic ionic liquid by mass ratio, be 1: 1～3 to put into reactor with para-nitrotoluene and NaOH or KOH by the amount of substance ratio again, and para-nitrotoluene and hydrophobic ionic liquid mass ratio are 1: 1～5, mix.
B), will charge into oxygen through the reactor of a step process, oxygen pressure is 0.5～2.5Mpa, then reactor being placed temperature is 60～100 ℃ of water-bath isothermal reactions 4～12 hours, is cooled to room temperature; Add the deionized water and stirring standing demix, get supernatant liquid; The dilute acid soln that adds 0.5～3.0mol/L in the clear liquid is acidity up to supernatant liquor, and product is separated out with precipitation; Suction filtration, vacuum-drying obtain p-nitrobenzoic acid.
The metal phthalocyanine in the described a step and the mass ratio of hydrophobic ionic liquid are 1: 50～200, and para-nitrotoluene is 1: 1～1.5 with NaOH by the amount of substance ratio, and para-nitrotoluene and ion liquid mass ratio are 1: 1.5～4.
Bath temperature in the described b step is 70～90 ℃.
Isothermal reaction in the described b step is 8～12 hours.
Oxygen pressure in the described b step is 1.0～2.0Mpa.
Dilute acid soln in the described b step is that concentration is HCl solution or the H of 1.5～2.0mol/L
2SO
4Solution.
The present invention compared with prior art has following remarkable advantage:
(1), production cost is low, employed oxygenant is a molecular oxygen cheap and easy to get.
(2), catalyst system easily separates with reaction system, catalyzer can recycle.
(3), p-nitrobenzoic acid is not easy to separate from system, and not with an organic solvent.
Embodiment
Embodiment 1
A), 0.050g cobalt phthalocyanine and 2.0g para-nitrotoluene are dissolved in 10.0g[HMIM] PF
6In the ionic liquid, and add 0.58g NaOH in reactor, mix, charge into the oxygen of 0.5Mpa again.
B), the reactor of handling through previous step is placed temperature is 60 ℃ of water bath with thermostatic control isothermal reactions 4 hours, reaction finishes, and leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, adds rare HCl solution of 0.5mol/L, becomes acid up to solution, separates out product.Filter, vacuum-drying obtains p-nitrobenzoic acid.
C), get catalyst system and reuse, do not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 2
A), 0.150g copper phthalocyanine and 6.0g para-nitrotoluene are dissolved in 6.0g[OMIM] BF
6In the ionic liquid, and add 5.25gKOH in reactor, mix, charge into the oxygen of 1.0Mpa again.
B), the reactor of handling through previous step is placed temperature is 70 ℃ of waters bath with thermostatic control reactions 8 hours, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, adds rare H of 2mol/L
2SO
4Solution becomes acid up to solution, separates out product.Filter, vacuum-drying obtains p-nitrobenzoic acid.
C), get catalyst system and reuse, do not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 3
A), 0.150g cobalt phthalocyanine and 4.0g para-nitrotoluene are dissolved in 8.5g[HMIM] BF
6In the ionic liquid, and add 4.0gKOH in reactor, mix, charge into the oxygen of 1.5Mpa again.
B), the reactor of handling through previous step is placed temperature is 90 ℃ of waters bath with thermostatic control reactions 6 hours, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, adds rare HCl solution of 3mol/L, becomes acid up to solution, separates out product.Filter, vacuum-drying obtains p-nitrobenzoic acid.
C), get catalyst system and reuse, do not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 4
A), 0.10g iron-phthalocyanine and 5.0g para-nitrotoluene are dissolved in 8.5g[OMIM] BF
6In the ionic liquid, and add 3.5gNaOH in reactor, mix, charge into the oxygen of 2.0Mpa again.
B), the reactor of handling through previous step is placed temperature is 80 ℃ of waters bath with thermostatic control reactions 10 hours, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, adds rare HCl solution of 1.0mol/L, becomes acid up to solution, separates out product.Filter, vacuum-drying obtains p-nitrobenzoic acid.
C), get catalyst system and reuse, do not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 5
A), 10g cobalt phthalocyanine and 200g para-nitrotoluene are dissolved in 800g[BMIM] PF
6In the ionic liquid, and add 70gNaOH solution in reactor, mix, charge into the oxygen of 2.5Mpa again.
B), the reactor of handling through previous step is placed temperature is 90 ℃ of waters bath with thermostatic control reactions 10 hours, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, adds rare H of 2mol/L
2SO
4, become acid up to solution, separate out product.Filter, vacuum-drying obtains p-nitrobenzoic acid.
C), get catalyst system and reuse, do not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 6
A), 15g copper phthalocyanine and 250g para-nitrotoluene are dissolved in 950g[HMIM] PF
6In the ionic liquid, and add 145gNaOH in reactor, mix, charge into the oxygen of 2.0Mpa again.
B), the reactor of handling through previous step is placed temperature is 100 ℃ constant temperature oil bath reaction 12 hours, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, adds rare H of 1.5mol/L
2SO
4Solution becomes acid up to solution, separates out product.Filter, vacuum-drying obtains p-nitrobenzoic acid.
C), get catalyst system and reuse, do not find obviously that the catalytic activity of catalyzer decreases.
Claims (6)
1, a kind of preparation method of p-nitrobenzoic acid is characterized in that this method is raw material with the para-nitrotoluene, is catalyzer with hydrophobic ionic liquid dissolved metal phthalocyanine, oxygen is oxygenant, react in autoclave, prepare p-nitrobenzoic acid, it comprises following concrete steps:
A), be 1: 40～200 to put into reactor with metal phthalocyanine and hydrophobic ionic liquid by mass ratio, be 1: 1～3 to put into reactor with para-nitrotoluene and NaOH or KOH by the amount of substance ratio again, and para-nitrotoluene and hydrophobic ionic liquid mass ratio are 1: 1～5, mix;
B), will charge into oxygen through the reactor of a step process, oxygen pressure is 0.5～2.5Mpa, then reactor being placed temperature is 60～100 ℃ of water-bath isothermal reactions 4～12 hours, is cooled to room temperature; Add the deionized water and stirring standing demix, get supernatant liquid; The dilute acid soln that adds 0.5～3.0mol/L in the clear liquid is acidity up to supernatant liquor, and product is separated out with precipitation; Suction filtration, vacuum-drying obtain p-nitrobenzoic acid.
2, the preparation method of p-nitrobenzoic acid as claimed in claim 1, it is characterized in that the metal phthalocyanine in the described a step and the mass ratio of hydrophobic ionic liquid are 1: 50～200, para-nitrotoluene is 1: 1～1.5 with the amount of substance ratio of NaOH, and para-nitrotoluene and ion liquid mass ratio are 1: 1.5～4.
3, the preparation method of p-nitrobenzoic acid as claimed in claim 1 is characterized in that the bath temperature in the described b step is 70～90 ℃.
4, the preparation method of p-nitrobenzoic acid as claimed in claim 1 is characterized in that the isothermal reaction in the described b step is 8～12 hours.
5, the preparation method of p-nitrobenzoic acid as claimed in claim 1 is characterized in that the oxygen pressure in the described b step is 1.0～2.0Mpa.
6, the preparation method of p-nitrobenzoic acid as claimed in claim 1 is characterized in that the dilute acid soln in the described b step is that concentration is HCl solution or the H of 1.5～2.0mol/L
2SO
4Solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910048761A CN101525292A (en) | 2009-04-02 | 2009-04-02 | Preparation method of paranitrobenzoic acid |
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| CN200910048761A CN101525292A (en) | 2009-04-02 | 2009-04-02 | Preparation method of paranitrobenzoic acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399633A (en) * | 2015-10-26 | 2016-03-16 | 安徽广信农化股份有限公司 | P-nitrobenzoyl chloride intermediate waste liquid treatment method |
| CN106008220A (en) * | 2016-06-21 | 2016-10-12 | 太仓市东明化工有限公司 | Method for preparing p-nitrobenzoic acid through polystyrene foam |
| CN113735746A (en) * | 2021-09-07 | 2021-12-03 | 三峡大学 | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid |
| CN115197068A (en) * | 2022-06-10 | 2022-10-18 | 浙江优创材料科技股份有限公司 | Continuous step-by-step production process for producing p-nitrobenzoic acid |
-
2009
- 2009-04-02 CN CN200910048761A patent/CN101525292A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399633A (en) * | 2015-10-26 | 2016-03-16 | 安徽广信农化股份有限公司 | P-nitrobenzoyl chloride intermediate waste liquid treatment method |
| CN105399633B (en) * | 2015-10-26 | 2018-05-15 | 安徽广信农化股份有限公司 | A kind of method for treating waste liquid of paranitrobenzoyl chloride intermediate |
| CN106008220A (en) * | 2016-06-21 | 2016-10-12 | 太仓市东明化工有限公司 | Method for preparing p-nitrobenzoic acid through polystyrene foam |
| CN113735746A (en) * | 2021-09-07 | 2021-12-03 | 三峡大学 | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid |
| CN115197068A (en) * | 2022-06-10 | 2022-10-18 | 浙江优创材料科技股份有限公司 | Continuous step-by-step production process for producing p-nitrobenzoic acid |
| CN115197068B (en) * | 2022-06-10 | 2024-01-30 | 浙江优创材料科技股份有限公司 | Production process for continuously and stepwise producing p-nitrobenzoic acid |
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Application publication date: 20090909 |