Method for catalyzing alcohol, olefin and alkyne to generate organic carboxylic ester
By using ammonium molybdate tetrahydrate catalyst and appropriate solvents and additives, combined with specific reaction conditions, alcohols, olefins, and alkynes compounds were successfully converted into organic carboxylic acid esters, solving the problems of low conversion efficiency and difficult to control reaction conditions in the prior art, and achieving efficient and simple esterification reactions.
Patent Information
- Application Number
- CN202311265941.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-28
- Publication Date
- 2025-03-28
AI Technical Summary
The prior art is difficult to efficiently convert alcohols, olefins, and alkyne compounds into organic carboxylic acid esters, and the reaction conditions are difficult to control and the post-treatment is complicated.
Ammonium molybdate tetrahydrate is used as a catalyst, combined with organic solvents such as ethanol and methanol and alkaline inorganic compound additives, oxygen is used as the oxygen source, and the reaction temperature is controlled at 120℃-170℃, the gas pressure is 0.5-2.5MPa, and the reaction time is 8-48 hours.
It has achieved efficient oxidation and cracking of alcohols, olefins and alkynes, and generated corresponding organic carboxylic acid esters, with high catalyst activity, easy control of reaction conditions, simple post-treatment, and good application prospects.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention belongs to the field of catalysis, and specifically relates to a method for catalyzing the oxidation of alcohols, olefins and alkynes with transition metal materials to generate organic carboxylic acid esters Background Art
[0002] Ester compounds are important organic synthesis intermediates and are widely used in the fields of food, organic synthesis, coatings, fragrances, cosmetics, medicine and polymer materials. Therefore, esterification reaction is an important organic chemical reaction as a general way to prepare ester substances. Alcohols, olefins and alkynes are important organic compounds that can be transformed and synthesized into a variety of organic chemicals. Obtaining esters from alcohols, olefins and alkynes through oxidative cleavage and esterification is an effective way to transform and utilize these compounds. Summary of the invention
[0003] The present invention uses alcohol, olefin and alkyne compounds as substrates, uses ammonium molybdate tetrahydrate as a catalyst, adds solvents and additives, uses oxygen as an oxygen source, introduces a gas pressure of 0.5-2.5MPa (preferably 1.0-2.5MPa), a reaction temperature of 120°C-170°C, and a reaction time of 8-48h to convert alcohol, olefin and alkyne compounds into corresponding esters.
[0004] The amount of catalyst added is equivalent to 1-15 mol% of the molar amount of the substrate.
[0005] The organic solvent is ethanol, methanol, dimethyl carbonate, trimethyl phosphate and trimethyl orthoformate, and the mass ratio of the organic solvent to the substrate is 20:1-200:1.
[0006] The additive is an alkaline inorganic compound, including one or more of potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, and potassium phosphate. The mass ratio of the additive to the substrate is 0.01:1-0.1:1.
[0007] The oxygen source is preferably oxygen gas or oxygen in the air, and the pressure is preferably 1.0-2.5 MPa. The system of the present invention has many advantages such as high catalyst activity, wide application range of the method, easy control of reaction conditions, simple post-treatment, etc., and has good application prospects. DETAILED DESCRIPTION The following examples will help to understand the present invention, but the present invention is not limited thereto. Example 1 Ammonium molybdate tetrahydrate (5 mol% relative to the raw material), phenylethanol (levorotatory or dextrorotatory), styrene or phenylacetylene (0.25 mmol, raw material), 2 mg additive (potassium carbonate), and 2 g solvent (trimethyl orthoformate) were added to a 25 mL reaction bottle in sequence, and then transferred to a stainless steel high-pressure reactor, filled with oxygen pressure to 2.0 MPa, and the reactor was placed in a 160° C. oil bath. The reaction was stirred at 500 rpm for 24 h. After the reaction was completed, the reactor was cooled to room temperature, the reactor was opened, and internal standard biphenyl (15 mg) was added. The qualitative product was detected by gas chromatography-mass spectrometry. The conversion rate of the quantitative substrate phenylethanol, styrene, and phenylacetylene and the yield of the product methyl benzoate by gas chromatography internal standard method are shown in Tables 2, 3, and 4 below. Example 2-20 Except for the difference in catalyst dosage, pressure and reaction time, the catalyst activity evaluation is the same as that in Example 1. The reaction substrate is mainly phenylethanol, and the catalyst is ammonium molybdate. The influence of reaction conditions on reaction performance is investigated, and the catalytic reaction results are shown in Table 1. It can be seen from Table 1 that the catalyst dosage, the amount of solvent, additives, reaction temperature and reaction time have an influence on the catalytic effect. With the increase of reaction temperature (Examples 3, 4 and 13-16), catalyst dosage (Examples 6-8), reaction time (Examples 2 and 3), the amount of solvent (Examples 5 and 6), and the increase of the amount of additives (Examples 17-20), the yield increases. Table 1 Effect of reaction conditions on reaction performance Embodiment 22-65 Except for the different substrates, the evaluation of catalyst activity was the same as in Example 1. The reaction conditions and catalytic reaction results are shown in Table 2, Table 3 and Table 4. Alcohol, olefin and alkyne substrates can all undergo oxidative cleavage to generate corresponding organic carboxylic acid ester compounds. Table 2 Oxidative cleavage of alkyne substrates Table 3 Oxidative cleavage of olefinic substrates Table 4 Oxidative cleavage of alcohol substrates The invention has high oxidation efficiency, good selectivity and high product yield; it uses oxygen as an oxygen source, is economical and environmentally friendly, and has good application prospects.
Claims
1. A method for catalyzing alcohols, alkenes or alkynes to generate organic carboxylic acid esters, comprising adding one or more raw materials of alcohol, alkenes and alkynes, additives and ammonium molybdate catalyst into a solvent, placing the solvent in a sealed pressure vessel, introducing 0.5-2.5 MPa of oxygen source (oxygen and / or air as the oxygen source) gas, reacting at 120-170° C. for 8-48 hours, thereby oxidizing and breaking one or more of the alcohol, alkenes or alkynes into corresponding ester compounds.
2. The method for preparing ester compounds by oxidative cracking of alcohol, olefin and alkyne compounds according to claim 1, characterized in that: The catalyst is ammonium molybdate tetrahydrate.
3. The method for preparing ester compounds by oxidative cracking of alcohol, olefin and alkyne compounds according to claim 1, characterized in that: The amount of the catalyst used is 1-15 mol% of the molar amount of the substrate.
4. The method for preparing ester compounds by oxidative cracking of alcohol, olefin and alkyne compounds according to claim 1, characterized in that: The additive is an alkaline inorganic compound, including one or more of potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate and potassium phosphate, and the mass ratio of the additive to the substrate is 0.01:1-0.1:
1.
5. The method for preparing ester compounds by oxidative cracking of alcohol, olefin and alkyne compounds according to claim 1, characterized in that: The solvent is one or more of ethanol, methanol, dimethyl carbonate, trimethyl phosphate, and trimethyl orthoformate, and the mass ratio of the organic solvent to the substrate is 20:1-200:1, preferably 1-3 g / 0.25 mmol of the raw material.
6. The method for preparing ester compounds by oxidative cracking of alcohol, olefin and alkyne compounds according to claim 1, characterized in that: The reaction temperature is 120-170° C., preferably 130-160° C.; the gas pressure is 0.5-2.5 MPa, preferably 2.0 MPa; and the reaction time is 8-48 h, preferably 10-24 h.
7. The method for preparing ester compounds by oxidative cracking of alcohol, olefin and alkyne compounds according to claim 1, characterized in that: The alcohol ( left-handed or right-handed), olefins or alkyne In the molecule, there is no or other substituent on the benzene ring, and the other substituent on the benzene ring is one or more of phenyl, naphthyl, furan ring, thiophene ring, pyridine ring, -F, -Cl, -Br, -CF3, -Me, -OMe; in alcohols, olefins, alkynes having other substituents on the benzene ring, the positions of the other substituents are ortho, meta or para; in alcohols, olefins, alkynes having other substituents on the benzene ring, the number of the other substituents is 1, 2, 3, 4 or 5; or the benzene ring can be replaced by a naphthalene ring, a furan ring, a thiophene ring or a pyridine ring.