CN115215739A - Method for preparing p-toluic acid by oxidizing p-xylene through synergistic catalytic system - Google Patents
Method for preparing p-toluic acid by oxidizing p-xylene through synergistic catalytic system Download PDFInfo
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- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
The invention relates to a method for preparing p-toluic acid by oxidizing p-xylene with a synergistic catalytic system, which comprises the following steps: taking p-xylene, NHPI and CoPc (CONH) 2 ) 4 Dispersing in organic solvent, and reacting under oxygen condition to obtain the target product. The invention is in NHPI/CoPc (CONH) 2 ) 4 Under the synergistic catalytic action of (1) and in the presence of molecular oxygen, the reaction uses NHPI/CoPc (CONH) 2 ) 4 The synergistic catalytic system is used as a catalyst, a one-pot synthesis method is adopted, the preparation steps are fewer, the catalyst is added into a reaction system, the conversion rate of p-xylene is greatly improved, byproducts are hardly generated in the reaction, the used oxidant oxygen is wide in source, cheap and easy to obtain, the reaction cost is reduced, and the preparation method realizes that the catalyst is usedGreen chemistry of the reaction. Compared with the prior art, the catalyst used in the invention is environment-friendly, has low cost, good catalytic effect, high yield of the p-toluic acid and mild reaction conditions.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and relates to a method for preparing p-toluic acid by oxidizing p-xylene with a synergistic catalytic system.
Background
Paraxylene is an important petrochemical product raw material, and has wide application in polyester and fine organic chemical industries. The products produced by the liquid-phase oxidation of p-xylene usually include p-methylbenzyl alcohol, p-methylbenzaldehyde, p-methylbenzoic acid and terephthalic acid, wherein the p-methylbenzoic acid can be applied to organic pigments, medicines and photosensitive materials, and can also be further processed into the terephthalic acid. Terephthalic acid is an important raw material in the polyester industry and is widely used in the industries of fibers, films, plastics and the like. The production mode of the traditional process for preparing p-toluic acid and terephthalic acid by catalytic oxidation of p-xylene at present is limited to the pressure of environmental and energy crisis, and changes are urgently needed, so that the development of green oxidant and catalyst system for replacing the existing production process is very necessary.
The liquid phase oxidation of p-xylene to p-methylbenzoic acid is generally accompanied by normal pressure and pressure oxidation of p-xylene, in addition to the obsolete earlier nitric acid oxidation processes. The normal pressure method is to react for 24 hours at about 110 ℃, and about 5 percent of p-xylene is converted into p-methylbenzoic acid by using cobalt naphthenate as a catalyst. The pressure oxidation method is that cobalt naphthenate is used as a catalyst to react for 6.0 hours at 125 ℃ and 0.25MPa, the conversion rate of p-xylene is about 30 percent, and the selectivity of p-toluic acid is 60 to 70 percent. Both processes have the following common disadvantages: firstly, the conversion per pass is not high, and the yield of finished products is low; secondly, the conversion number of the catalyst is low, and the concentration of the catalyst is usually over 1000 ppm. In order to improve the conversion rate of p-xylene and the selectivity of p-toluic acid, a promoter such as bromide or metal salt is added or the concentration of the catalyst is increased, but the emission of pollutants is increased to a certain extent, and meanwhile, the introduction of the strong acid substance bromine easily causes the corrosion of equipment, so that the cost is increased. The preparation of p-toluic acid by catalytic oxidation of p-xylene with hydroxylamine-based cobalt complexes has been reported by Lixian et al. At a reaction temperature of 110 ℃ and a catalyst concentration of 1.0X 10 -3 mol/L, reaction time of 6h, p-xylene conversion of 33.9 percent and maximum selectivity of p-toluic acid86.2%, increasing the catalyst concentration and increasing the temperature both reduce the catalyst activity, and the water content in the system also has a very important influence on the oxidation reaction. The disadvantage of this catalytic system is that the catalyst is expensive and requires a relatively large catalyst concentration (Chenjun et al. Molecular catalysis, 2002, 16 (2): 81-86).
Disclosure of Invention
The invention aims to provide a method for preparing p-toluic acid by oxidizing p-xylene with a synergistic catalytic system, so as to overcome the defects that the method for preparing p-toluic acid from p-xylene in the prior art is low in yield, the added cocatalyst is not environment-friendly, the cost is high, or the reaction conditions are harsh and the like.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing p-toluic acid by oxidizing p-xylene with a synergistic catalytic system comprises the following steps:
taking p-xylene, N-hydroxyphthalimide (NHPI) and cobalt tetraamido phthalocyanine [ CoPc (CONH) 2 ) 4 ]Dispersing in organic solvent, and reacting under oxygen condition to obtain the target product.
Further, the organic solvent is acetic acid or acetonitrile.
Further, the NHPI, coPc (CONH) 2 ) 4 The amounts of addition of (A) and (B) are respectively 2mol% and 0.8-1.6 mol% of the amount of addition of p-xylene.
Further, the NHPI, coPc (CONH) 2 ) 4 The amounts of addition of (B) were 2mol% and 0.8mol%, respectively, based on the amount of addition of p-xylene.
Further, during the reaction, the rate of oxygen gas introduction was 16ml/min.
Furthermore, the reaction temperature is 70-90 ℃, the reaction time is 0-24h, and the reaction time is not 0.
Further, the reaction temperature was 75 ℃ and the reaction time was 24 hours.
Furthermore, the molar volume ratio of the paraxylene to the organic solvent is 1mmol (1-2) ml.
Further, the molar volume ratio of the p-xylene to the organic solvent was 1mmol.
Further, the reaction was carried out under normal pressure.
Small molecule organic compounds NHPI and their analogs are widely used as chemical oxidations or catalysts in organic reactions. NHPI can achieve catalytic oxidation of many organic compounds under mild conditions of 25-100 ℃ at normal pressure, particularly when transition metal salts are added. The NHPI system has the characteristics of high catalytic efficiency, wide oxidation range, environmental friendliness, mild conditions, simple catalyst synthesis and the like. In the case of catalysts required for the oxidation of p-xylene, metals and metal oxides are relatively easy to prepare but have poor catalytic efficiency, and metal complexes have relatively high catalytic efficiency. The invention combines metal phthalocyanine and NHPI as a synergistic catalytic system for the oxidation of paraxylene.
The invention is in NHPI/CoPc (CONH) 2 ) 4 Under the synergistic catalytic action of (1) and in the presence of molecular oxygen, the reaction uses NHPI/CoPc (CONH) 2 ) 4 As a catalyst, in which CoPc (CONH) is present 2 ) 4 The catalyst is prepared by a one-pot synthesis method, the preparation steps are fewer, the conversion rate of p-xylene is greatly improved by adding the catalyst into a reaction system, byproducts are hardly generated in the reaction, the subsequent separation operation is simple, the oxygen source is wide, the price is low, the oxygen source is easy to obtain, the reaction cost is reduced, and the green chemical process of the reaction is realized.
The invention uses an organic catalyst NHPI and macrocyclic compound tetraamido cobalt phthalocyanine CoPc (CONH) 2 ) 4 The p-methyl benzoic acid is prepared by the catalytic oxidation of p-xylene in a liquid phase under the synergetic catalysis. The method takes paraxylene as a starting material, and NHPI/[ CoPc (CONH) is added 2 ) 4 ]And as a synergistic catalytic system, introducing oxygen into the reaction system, and carrying out one-pot reaction under the normal pressure condition to obtain the p-toluic acid with higher yield. The invention first utilizes NHPI and CoPc (CONH) 2 ) 4 The method of the invention overcomes the problem of using bromide or metal salt as a promoter in the conventional methodThe catalyst has the defects of green, environmental protection and easy obtainment of the used oxidant oxygen.
The oxidation of p-xylene in the reaction system of the present invention follows a radical mechanism, NHPI first passing through CoPc (CONH) 2 ) 4 Activating and self-decomposing to generate a PINO free radical, wherein the PINO free radical abstracts hydrogen on a methyl group of p-xylene to generate a carbon free radical; the carbon free radical can be captured by molecular oxygen to obtain a peroxy radical, which is then combined with another molecule of p-xylene to produce the product p-toluic acid.
The invention is used for NHPI and CoPc (CONH) 2 ) 4 The addition amount of (2) is limited, and under the condition, the reaction benefit value is higher and the reaction is smoother. If CoPc (CONH) 2 ) 4 The addition amount of (A) is too high, the macrocyclic complex is likely to aggregate, resulting in poor oxidation effect; if the addition amount of NHPI is too low, the activated NHPI is not enough, the reaction benefit is also reduced, and the yield of p-toluic acid is reduced. The oxidation benefit generated by introducing oxygen in the reaction process finally depends on the amount of dissolved oxygen in the system, and when the introduction rate of the oxygen is 16ml/min, the value of the dissolved oxygen in the system is the highest, and the oxidation benefit is the best.
Compared with the prior art, the invention has the following advantages:
(1) The invention introduces the use of NHPI/CoPc (CONH) for the first time 2 ) 4 The catalyst is used as a synergistic catalytic system for preparing p-toluic acid by catalytic oxidation of p-xylene, avoids the defect that bromide or metal salts are used as a cocatalyst in the traditional process, is environment-friendly, has low cost and good catalytic effect, and has high yield of p-toluic acid;
(2) The environment-friendly oxygen is used as an oxidant, the oxygen source is wide, the price is low, the oxygen is easy to obtain, the reaction cost is reduced, and the oxidizing effect on the substrate p-xylene is good;
(3) Compared with the reaction conditions of industrial production, the method obviously reduces the reaction temperature, does not need pressurization reaction, namely the reaction is carried out under mild conditions, thereby having good application prospect.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the product prepared in example 2;
FIG. 2 is a nuclear magnetic carbon spectrum of the product prepared in example 2;
FIG. 3 is an infrared spectrum of the product prepared in example 2.
Detailed Description
The invention is described in detail below with reference to the figures and the 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 scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the materials or processing techniques are those conventionally used in the art.
In the following examples, the conversion of p-xylene and the yield of p-toluic acid were determined by Gas Chromatography (GC) based standard curve method for GC assay calculation.
Example 1:
the preparation method of the tetra-amido cobalt phthalocyanine catalyst comprises the following steps:
the invention relates to a method for synthesizing tetraamido cobalt phthalocyanine (yankee, north-east Master-and-university newspaper (natural science edition), 2008, 40 (4): 93-96), which is referred to as the method in this example to prepare 4-carboxy phthalic anhydride (27.5 g), cobalt chloride (CoCl) 2 ) Urea (the molar ratio of the three is 4. Washing with acetone and methanol for 3 times, and drying to obtain blue-black solid, i.e. tetra-amido cobalt phthalocyanine [ CoPc (CONH) 2 ) 4 ]。
Example 2:
the proportion of the paraxylene and the acetonitrile in the embodiment is calculated according to the molar volume ratioThe amount of p-xylene and acetonitrile is 1.5mL; with NHPI/CoPc (CONH) 2 ) 4 The catalyst system is used as a catalyst, wherein the dosage of NHPI is 2mol percent of catalytic amount, and CoPc (CONH) 2 ) 4 In a catalytic amount of 0.8mol%, NHPI/CoPc (CONH) 2 ) 4 Catalyst-to-xylene molar ratio of 7.
Into a three-necked flask, 0.0594g of CoPc (CONH) prepared in example 1 was charged in order 2 ) 4 0.0335g NHPI, 1.0620g paraxylene and 15mL acetonitrile, then introducing 16mL/min oxygen under normal pressure, stirring at 75 ℃ for 24h at constant temperature, then centrifuging the mixture obtained after the reaction (2000rpm, 5 min), adding Na into the solution obtained by centrifugation 2 CO 3 The method comprises the steps of saturating an aqueous solution to obtain a mixed solution A, adjusting the pH value of the mixed solution A to be 8, then filtering to obtain a filtrate, extracting the obtained filtrate with ethyl acetate to obtain a water phase, and adjusting the pH value of the water phase to be about 2 with dilute hydrochloric acid to obtain a mixed solution B. And extracting the mixed solution B by using ethyl acetate, drying an organic phase obtained by extraction by using magnesium sulfate, and then carrying out rotary evaporation concentration at the rotary evaporation temperature of 30 ℃ and the rotary evaporation pressure of-0.09 MPa to finally obtain a product.
And performing nuclear magnetic resonance hydrogen spectrum and carbon spectrum analysis and infrared spectrum analysis on the obtained product. As shown in FIG. 1, in the NMR spectrum of the product, there was a peak at 7 to 8ppm, indicating the presence of H on the benzene ring and H at the ortho position to the methyl group. There was a peak at 2.34ppm indicating the presence of H on the methyl group. Nuclear magnetic hydrogen spectrum data: 1 h NMR (500mhz, dmso) δ 12.78 (s, 1H), 7.83 (d, J =8.1hz, 2h), 7.30 (d, J =8.0hz, 2h), 2.36 (s, 3H). As shown in fig. 2, the nmr data is the nmr spectrum of the product: 13 c NMR (125MHz, DMSO). Delta.167.32, 143.04,129.34,129.14,128.03,21.13. As shown in FIG. 3, in the IR spectrum of the product, it was at about 3454cm -1 The strong absorption peak appears at the position, which can be judged to be caused by O-H vibration and is located at 1682cm -1 The peak at (a) can be judged as the vibration of unsaturated C = O. The results of nuclear magnetic hydrogen spectrum analysis, carbon spectrum analysis and infrared spectrum analysis are combined, so that the successful synthesis of the p-toluic acid can be judged.
Finally, the conversion rate of p-xylene is 79.69 percent and the yield of p-toluic acid is 67.74 percent by GC detection and analysis.
Example 3:
the mixture ratio of p-xylene to acetic acid in the embodiment is calculated according to the molar volume ratio, namely that the ratio of p-xylene to acetic acid is 1mmol; with NHPI/CoPc (CONH) 2 ) 4 The catalyst system is used as a catalyst, wherein the dosage of NHPI is 2mol percent of catalytic amount, and CoPc (CONH) 2 ) 4 In a catalytic amount of 1.6mol%, NHPI/CoPc (CONH) 2 ) 4 Catalyst-to-xylene molar ratio 9.
Into a three-necked flask, 0.1192g of CoPc (CONH) prepared in example 1 was charged in order 2 ) 4 0.0338g of NHPI, 1.0620g of paraxylene and 15mL of acetic acid, introducing 16mL/min of oxygen under normal pressure, stirring at the constant temperature of 75 ℃ for 24 hours, centrifuging the mixture obtained after the reaction (2000rpm, 5 min), adding Na into the solution obtained by centrifugation 2 HCO 3 The method comprises the steps of saturating an aqueous solution to obtain a mixed solution A, adjusting the pH value of the mixed solution A to 8, then filtering to obtain a filtrate, extracting the obtained filtrate with ethyl acetate to obtain a water phase, and adjusting the pH value of the water phase to about 2 with dilute hydrochloric acid to obtain a mixed solution B. And extracting the mixed solution B by using ethyl acetate, drying an organic phase obtained by extraction by using magnesium sulfate, and then carrying out rotary evaporation concentration at the rotary evaporation temperature of 30 ℃ and the rotary evaporation pressure of-0.09 MPa to finally obtain a product.
Finally, GC detection and analysis show that the conversion rate of the p-xylene is more than 99 percent, and the yield of the p-toluic acid is 48.53 percent.
Example 4:
the mixture ratio of the p-xylene to the acetic acid in the embodiment is calculated according to the molar volume ratio, namely, the ratio of the p-xylene to the acetic acid is 1mmol; NHPI/CoPc (CONH) 2 ) 4 The catalyst system is used as a catalyst, wherein the dosage of NHPI is 2mol percent of the catalytic amount, coPc (CONH) 2 ) 4 In a catalytic amount of 0.8mol%, NHPI/CoPc (CONH) 2 ) 4 Catalyst-to-xylene molar ratio of 7.
Into a three-necked flask, 0.0597g of CoPc (CONH) prepared in example 1 was charged in order 2 ) 4 、0.0335g NHPI, 1.0620g of p-xylene and 15mL of acetic acid, introducing oxygen at 16mL/min under normal pressure, stirring at the constant temperature of 85 ℃ for 24h, centrifuging the mixture obtained after the reaction (2000rpm, 5 min), and adding Na into the solution obtained by centrifugation 2 CO 3 The method comprises the steps of saturating an aqueous solution to obtain a mixed solution A, adjusting the pH value of the mixed solution A to 8, then filtering to obtain a filtrate, extracting the obtained filtrate with ethyl acetate to obtain a water phase, and adjusting the pH value of the water phase to about 2 with dilute hydrochloric acid to obtain a mixed solution B. And extracting the mixed solution B by using ethyl acetate, drying an organic phase obtained by extraction by using magnesium sulfate, and then carrying out rotary evaporation concentration at the rotary evaporation temperature of 30 ℃ and the rotary evaporation pressure of-0.09 MPa to finally obtain a product.
Finally, GC detection and analysis show that the conversion rate of the p-xylene is more than 99 percent, and the yield of the p-toluic acid is 68.52 percent.
Example 5:
the mixture ratio of p-xylene to acetic acid in the embodiment is calculated according to the molar volume ratio, namely that the ratio of p-xylene to acetic acid is 1mmol; NHPI/CoPc (CONH) 2 ) 4 The catalyst system is used as a catalyst, wherein the dosage of NHPI is 2mol percent of catalytic amount, and CoPc (CONH) 2 ) 4 In a catalytic amount of 0.8mol%, NHPI/CoPc (CONH) 2 ) 4 Catalyst-to-xylene molar ratio of 7.
0.0595g of CoPc (CONH) was added to a three-necked flask in this order 2 ) 4 0.0337g NHPI, 1.0616g paraxylene and 15mL acetic acid, then introducing oxygen 16mL/min under normal pressure, stirring at the constant temperature of 75 ℃ for 24 hours, then centrifuging the mixture obtained after the reaction (2000rpm, 5 min), adding Na into the solution obtained by centrifugation 2 CO 3 The method comprises the steps of saturating an aqueous solution to obtain a mixed solution A, adjusting the pH value of the mixed solution A to 8, then filtering to obtain a filtrate, extracting the obtained filtrate with ethyl acetate to obtain a water phase, and adjusting the pH value of the water phase to about 2 with dilute hydrochloric acid to obtain a mixed solution B. And extracting the mixed solution B by using ethyl acetate, drying an organic phase obtained by extraction by using magnesium sulfate, and then carrying out rotary evaporation concentration at the rotary evaporation temperature of 30 ℃ and the rotary evaporation pressure of-0.09 MPa to finally obtain a product.
Finally, GC detection and analysis show that the conversion rate of the p-xylene is more than 99 percent, and the yield of the p-toluic acid is 83.6 percent.
Example 6:
compared with example 2, most of them are the same except that CoPc (CONH) is used in the present example 2 ) 4 The amount of (A) is changed to 1mol% of the catalytic amount.
Example 7:
compared with example 2, most of the components are the same, except that the stirring at the constant temperature of 75 ℃ for 24 hours is changed into the stirring at the constant temperature of 70 ℃ for 12 hours in the example.
Example 8:
compared with the embodiment 2, the stirring device is mostly the same, except that the stirring at the constant temperature of 75 ℃ for 24 hours is changed into the stirring at the constant temperature of 90 ℃ for 24 hours in the embodiment.
Example 9:
compared with example 2, most of the parts are the same except that the molar volume ratio of p-xylene to acetonitrile in this example is changed to 1mmol.
Example 10:
compared with example 2, most of the results were the same except that the molar volume ratio of p-xylene to acetonitrile in this example was changed to 1mmol 1.5mL to 1mmol 2mL.
Comparative example 1:
compared to example 2, most of them were the same except that NHPI and CoPc (CONH) were not added 2 ) 4 . No formation of p-toluic acid was detected by GC analysis of the product obtained after the reaction.
Comparative example 2:
compared to example 2, most of them were the same except that no oxygen was introduced. No formation of p-toluic acid was detected by GC analysis of the product obtained after the reaction.
Comparative example 3:
compared to example 2, the majority were the same except that CoPc (CONH) was not added 2 ) 4 . No formation of p-toluic acid was detected by GC analysis of the product obtained after the reaction.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for preparing p-toluic acid by oxidizing p-xylene with a concerted catalysis system is characterized by comprising the following steps:
taking p-xylene, NHPI and CoPc (CONH) 2 ) 4 Dispersing in organic solvent, and reacting under oxygen condition to obtain the target product.
2. The method for preparing p-toluic acid by oxidizing p-xylene with a co-catalytic system as claimed in claim 1, wherein the organic solvent is acetic acid or acetonitrile.
3. The method for preparing p-toluic acid by oxidizing p-xylene with a co-catalytic system as claimed in claim 1, wherein said NHPI, coPc (CONH) 2 ) 4 The amounts of the compounds (A) and (B) added are respectively 2mol% and 0.8-1.6 mol% of the amount of p-xylene added.
4. The method for preparing p-toluic acid by oxidizing p-xylene with a concerted catalysis system of claim 1, wherein the NHPI, coPc (CONH) 2 ) 4 The amounts of addition of (B) were 2mol% and 0.8mol%, respectively, based on the amount of addition of p-xylene.
5. The method for preparing p-toluic acid by oxidizing p-xylene with a concerted catalytic system of claim 1, wherein the oxygen is introduced at a rate of 16ml/min during the reaction.
6. The method for preparing p-toluic acid by oxidizing p-xylene with a concerted catalytic system according to claim 1, wherein the reaction temperature is 70-90 ℃, the reaction time is 0-24h, and the reaction time is not 0.
7. The method for preparing p-toluic acid by oxidizing p-xylene with a concerted catalytic system according to claim 1, wherein the reaction temperature is 75 ℃ and the reaction time is 24h.
8. The method for preparing p-toluic acid by oxidizing p-xylene with a concerted catalysis system according to claim 1, wherein the molar volume ratio of the p-xylene to the organic solvent is 1mmol (1-2) ml.
9. The method for preparing p-methylbenzoic acid by oxidizing p-xylene with a co-catalytic system as claimed in claim 1, wherein the molar volume ratio of the p-xylene to the organic solvent is 1mmol.
10. The method for preparing p-toluic acid by oxidizing p-xylene with a concerted catalytic system according to claim 1, wherein the reaction is carried out under normal pressure.
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| CN112079706A (en) * | 2020-08-27 | 2020-12-15 | 上海应用技术大学 | Method for preparing carboxylic acid by green catalytic oxidation of aliphatic primary alcohol |
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| WO2020140675A1 (en) * | 2019-01-03 | 2020-07-09 | 中国科学院大连化学物理研究所 | Preparation method for 2,5-furan diacarboxylic acid |
| CN110483273A (en) * | 2019-08-26 | 2019-11-22 | 上海应用技术大学 | A kind of method that secondary alcohol or primary alconol catalysis oxidation prepare ketone or carboxylic acid |
| CN110452392A (en) * | 2019-08-30 | 2019-11-15 | 湘潭大学 | A kind of preparation method of cobalt-based metal-organic framework materials and its application in p xylene oxidation reaction |
| CN112079706A (en) * | 2020-08-27 | 2020-12-15 | 上海应用技术大学 | Method for preparing carboxylic acid by green catalytic oxidation of aliphatic primary alcohol |
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