CN109456152B - Method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene - Google Patents
Method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene Download PDFInfo
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- CN109456152B CN109456152B CN201710794505.3A CN201710794505A CN109456152B CN 109456152 B CN109456152 B CN 109456152B CN 201710794505 A CN201710794505 A CN 201710794505A CN 109456152 B CN109456152 B CN 109456152B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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Abstract
The invention discloses a method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene. The method takes transition metal salt and a nitrogen-containing ligand as catalysts, acetonitrile as a solvent, and the p-methoxy toluene is selectively oxidized by liquid phase catalysis to prepare the p-methoxy benzaldehyde. By selecting proper nitrogen-containing ligand and transition metal salt for coordination, the method has the advantages of mild reaction conditions, simple steps and high catalytic efficiency.
Description
Technical Field
The invention relates to the field of chemical engineering, in particular to a method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene.
Background
P-anisaldehyde is also called anisaldehyde and anisaldehyde, is colorless to light yellow liquid at normal temperature, has lasting smell similar to that of hawthorn, is a main spice for preparing hawthorn flower fragrance, has high-value economic benefit, is an important intermediate for organic synthesis, and is widely applied to the fields of essence, medicine, pesticide, industry and the like. The p-methoxybenzaldehyde as the acetal perfume has the characteristics of soft, elegant and lasting fragrance, can be used as a high-grade perfume, has stable chemical property and quick fragrance diffusion, is an important choice in the essence and perfume industry, and attracts more and more attention. In addition, in the field of medicine, the compound can be used as an intermediate for preparing antihistamine medicines and used for preparing medicines such as antibiotic hydroxyaminobenzylpenicillin and the like. Can be used as pesticide, pesticide additive and biological growth inhibitor in the aspect of pesticide. In the industrial aspect, the brightener can be used as a good brightener of an additive for cyanide-free zinc plating, and p-methoxybenzaldehyde can obtain a bright coating in a wider current density, so that the brightener is widely applied to the electroplating industry; in addition, the p-methoxybenzaldehyde can be used for preparing functional polymer materials, and the poly-ferrocene-p-methoxybenzaldehyde has good application prospect in the industry of the functional polymer materials, and not only has special electrical property, but also has good magnetic property.
The synthesis method of p-methoxybenzaldehyde mainly comprises the following methods: (1) prepared by oxidizing p-methoxy toluene; (2) prepared by alkylation reaction of p-hydroxybenzaldehyde and dimethyl sulfate under alkaline condition; (3) prepared by oxidizing p-propenyl anisole; (4) prepared by oxidizing p-methoxy benzyl alcohol; (5) the phenol is methylated by dimethyl sulfate, and then is prepared by chloromethylation and hydrolysis reaction; (6) is prepared from p-methylphenol through methylating and oxidizing.
In the existing preparation methods, some raw materials such as p-methoxybenzyl alcohol are expensive, and some raw materials are easily available, but the steps of the synthetic process are too complex, the reaction is not easy to control, the post-treatment process is complex, and the total yield is low. At present, a plurality of methods for preparing p-methoxybenzaldehyde by using p-methoxytoluene as a raw material exist, but a liquid phase catalytic selective oxidation method is relatively superior.
Disclosure of Invention
A method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene. The method takes transition metal salt and a nitrogen-containing ligand as catalysts, takes acetonitrile as a solvent, and selectively oxidizes p-methoxy toluene under the condition of mild liquid phase catalysis to prepare the p-methoxy benzaldehyde. By selecting proper nitrogen-containing ligand and transition metal salt for coordination, the method has the advantages of mild reaction conditions, simple steps and high catalytic efficiency.
The technical scheme of the invention is as follows:
according to the invention, the method takes the p-methoxy toluene as a substrate, takes the transition metal salt and the nitrogen-containing ligand as catalysts, and prepares the p-methoxy benzaldehyde by catalytic selective oxidation under mild conditions.
The transition metal salt is one or more of cobalt nitrate, cobalt acetate, cobalt chloride, cobalt sulfate, cobalt acetylacetonate, cobalt isooctanoate, cobalt oleate, cobalt neodecanoate, copper nitrate, copper acetate, copper chloride, copper sulfate, copper acetylacetonate, copper isooctanoate, copper oleate, copper neodecanoate, manganese nitrate, manganese acetate, manganese chloride, manganese sulfate, manganese acetylacetonate, manganese isooctanoate, manganese oleate and manganese neodecanoate.
The nitrogen-containing ligand is one or more than two of imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, benzimidazole, 1, 10-phenanthroline, 2, 2' -bipyridine, p-tetramethoxy phenyl porphyrin and p-tetracarboxyphenyl porphyrin.
The concentration of the transition metal salt is from 10 to 2000ppm (calculated as pure metal content), preferably from 200 to 600ppm, and the ratio of the mass of the nitrogen-containing ligand added to the mass of the metal salt is from 0.01 to 10, preferably from 0.2 to 6.
The reaction solvent is acetonitrile, the concentration of a substrate p-methoxytoluene is 2.0mol/L, the reaction temperature is 40-140 ℃, the preferable concentration is 60-110 ℃, the reaction time is 1-12h, the preferable concentration is 4-8h, and the reaction pressure is 0.1-1.0MPa, and the preferable concentration is 0.2-0.6 MPa.
The method selects the proper nitrogen-containing ligand to perform the coordination action with the transition metal salt, so that the reaction condition is mild, the steps are simple, and the efficiency of catalyzing the oxidation of the p-methoxytoluene is high.
Detailed Description
The process provided by the present invention is described in detail below with reference to examples, but the present invention is not limited thereto in any way.
Example 1:
to a 60mL autoclave containing a polytetrafluoroethylene liner, 10mL of a cobalt nitrate acetonitrile solution containing p-methoxytoluene (2.0mol/L) in which the concentration of cobalt nitrate was 400ppm (calculated as Co content) was added, and 80mg of p-tetramethoxyphenylporphyrin was added. And (3) sealing the high-pressure reaction kettle, stirring, heating to 80 ℃, charging 0.4MPa of oxygen, and reacting for 8 hours. After the reaction, the reaction product was checked by GC to find that the conversion of p-methoxytoluene was 38.1% and the selectivity of p-methoxybenzaldehyde was 42.3%.
Examples 2 to 5: the reaction procedure of example 1 was repeated except that the reaction conditions were different from those of the transition metal salt used. The specific reaction conditions and results of the examples are shown in table 1.
Table 1, examples 2 to 5 specific reaction conditions
The result shows that the metal manganese salt and the nitrogen-containing ligand have better catalytic activity for oxidizing the p-methoxytoluene.
Example 6:
adding 10mL of manganese isooctanoate acetonitrile solution containing p-methoxytoluene (2.0mol/L) into 60mL of a high-pressure reaction kettle containing a polytetrafluoroethylene lining, wherein the concentration of manganese isooctanoate is 200ppm (calculated by Mn content), and adding 100mg of 1, 10-phenanthroline. And (3) sealing the high-pressure reaction kettle, stirring, heating to 100 ℃, charging 0.6MPa of oxygen, and reacting for 8 hours. After the reaction, the reaction product was checked by GC, and the conversion of p-methoxytoluene was 48.3% and the selectivity of p-methoxybenzaldehyde was 56.2%.
Examples 7 to 10: the procedure of example 6 was repeated except that the reaction conditions were different from those of the nitrogen-containing ligand used. The specific substrates for each example are listed in Table 2
Table 2, examples 7 to 10 concrete reaction conditions
The result shows that the porphyrin nitrogen-containing ligand and the metal salt jointly catalyze p-methoxytoluene to have better catalytic activity.
Claims (4)
1. A method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene is characterized by comprising the following steps: the method takes transition metal salt and a nitrogen-containing ligand as catalysts, oxygen as an oxygen source and acetonitrile as a solvent, and prepares p-methoxybenzaldehyde by selectively oxidizing p-methoxytoluene through liquid phase catalysis; the transition metal salt is one or more than two of cobalt nitrate, cobalt acetate, copper nitrate, manganese acetate, manganese isooctanoate and manganese neodecanoate; the nitrogen-containing ligand is one or more than two of 2-ethyl-4-methylimidazole, 1, 10-phenanthroline, 2, 2' -bipyridyl, p-tetramethoxy phenyl porphyrin and p-tetracarboxyl phenyl porphyrin;
the concentration of transition metal salt in the system is 10-2000ppm by pure transition metal, and the ratio of the mass of the added nitrogen-containing ligand to the mass of the metal salt is 0.01-10; the concentration of the p-methoxytoluene is 0.1-8.0 mol/L, and the reaction temperature is 40-140oC, the reaction time is 1-12 h; the reaction pressure is 0.1-1.0 MPa.
2. The method of claim 1, wherein: the concentration of the transition metal salt in the system is 200-600ppm calculated by pure transition metal, and the ratio of the mass of the added nitrogen-containing ligand to the mass of the metal salt is 0.2-6.
3. The method of claim 1, wherein: the concentration of the p-methoxytoluene is 1.0-5.0 mol/L, and the reaction temperature is 60-110oAnd C, the reaction time is 4-8 h.
4. The method of claim 1, wherein: the reaction pressure is 0.2-0.6 MPa.
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| CN112778106B (en) * | 2019-11-05 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
| CN112079707B (en) * | 2020-09-23 | 2021-06-01 | 中国科学院大连化学物理研究所 | Method for preparing carboxylic acid and co-producing alpha-olefin by catalytic oxidation of primary alcohol with cobalt salt |
Citations (3)
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| CN1695806A (en) * | 2004-05-13 | 2005-11-16 | 中国科学院大连化学物理研究所 | Catalysis system in use for oxidation reaction of toluene in liquid phase |
| CN107011151A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that benzaldehyde selectivity is improved during toluene liquid phase catalytic oxidation |
| CN107011152A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
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Patent Citations (3)
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| CN1695806A (en) * | 2004-05-13 | 2005-11-16 | 中国科学院大连化学物理研究所 | Catalysis system in use for oxidation reaction of toluene in liquid phase |
| CN107011151A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that benzaldehyde selectivity is improved during toluene liquid phase catalytic oxidation |
| CN107011152A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
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