CN109824513B - Method for preparing carboxylic ester by direct alcohol oxidation esterification method - Google Patents
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Abstract
The invention discloses a method for preparing carboxylic ester by an alcohol direct oxidation esterification method, which comprises the steps of taking an aromatic alcohol compound or saturated straight-chain fatty alcohol as a reaction substrate, taking an Au-Co composite particle load as a catalyst, adding a low-catalytic amount of alkali, reacting for 0.5-15h in a methanol solvent at 25-150 ℃ in the atmosphere of air or oxygen or a mixture of the air and the oxygen, and carrying out post-treatment to obtain a target product carboxylic ester. The preparation method of the invention shortens the process steps, has mild conditions, less catalyst consumption, high atom economy, simple operation, wide application range of the substrate and industrial practicability.
Description
Technical Field
The invention relates to a method for preparing carboxylic ester by using an alcohol direct oxidation esterification method, in particular to a method for preparing carboxylic ester from alcohol by using an Au-Co composite particle loading substance as a catalyst.
Background
The organic methyl carboxylate is a very important chemical product and an organic synthesis intermediate, and is widely applied to the fields of food, organic synthesis, paint, spice, cosmetics, medicine, high polymer materials and the like. The industrial synthesis method of the organic methyl carboxylate mainly comprises five types: 1) reacting the alcohol phenol with various acylating agents to prepare ester; 2) transesterification of carboxylic acids with alcohols, acids, esters; 3) cross-coupling halogenated hydrocarbon, CO and alcohol to generate ester; 4) oxidizing aldehyde in one step to generate ester; 5) and oxidizing the alcohol in one step to generate ester.
Both in the process of ester exchange and reaction of alcohol and acylating agent, chloride is easily generated to pollute the environment. In the cross coupling reaction of aromatic halide and CO, the high temperature and high pressure reaction conditions and the existence of chloride ions are unfavorable for the environment, and the reaction result is greatly influenced by the CO pressure and is difficult to control. Since aldehydes are generally prepared by oxidation of alcohols, the reaction of producing esters in one step by oxidation of alcohols is more advantageous than the reaction of producing esters directly from aldehydes.
Alcohols as base compounds have the following advantages: compared with carbonyl compounds, the compound is more green, has multiple compound types, is stable in the air, is easy to obtain in commerce, has low price and low toxicity, and is simple to operate. From the economic and environmental point of view, air or oxygen is an ideal oxidant, which is not only cheap and abundant, but also water is the byproduct after oxidation. Therefore, from the perspective of atom economy and energy efficiency utilization, the direct oxidative esterification of alcohol to synthesize ester substances in one step is a very worthy research method, the method is simple to operate, saves cost, meets the requirements of current green, environmental protection and sustainable development, and has industrial application value,
at present, the catalysts for synthesizing esters by catalytic oxidation of alcohols in one step by taking oxygen as a terminal oxidant reported in the literature are mainly Pd and Au.
The use of Pd as a catalyst in alcohol oxidation esterification is mainly a homogeneous catalytic system and has been reported in a few days.
2011 Matthias Beller et al in Angew. chem. int. Ed.2011, 50, 5139-2As catalyst, nBuP (l-adamantyl)2 as ligand, and AgPF is added6And K2CO3As an additive, the yield of the product under the optimal condition is 54-88%. The method realizes the oxidation esterification reaction of alcohol catalyzed by Pd for the first time. Almost simultaneously, in 2011 Lei aiwei et al in Angew. chem. int. Ed.2011, 50, 5144-2(CH3CN)2]As the catalyst, AgBF4 and NaOtBu are used as additives, so that the synthesis of benzyl alcohol with para-position and meta-position substituents and corresponding methyl ester compounds such as furancarbinol, thiophenemethanol and the like which are difficult to react in a methanol solvent is realized, and the product yield is 55-89%. When other short-chain fatty alcohols (such as n-propanol, n-butanol, etc.) are used as solvents, P-olefin is required to be added as a ligand, and Ag is required to be added2CO3And K3PO4As additives to achieve other ester compoundsThe product is synthesized, and the product yield is 41-84%.
Although supported palladium nano-structured catalytic systems are capable of achieving oxidative esterification of alcohols, there are a number of disadvantages: complex ligands and a large amount of additives are required to be added in the reaction, the reaction conditions are complicated, and the yield of the product is low.
Hutchings and Corma et al, when studying the reaction of gold-catalyzed oxidation of alcohol (Catal. Lett.,2005,103,43-52. and Angew chem. int. Ed.,2005,44,4066-4069.), found that ester is generated in the reaction, after analysis, the gold catalyst is considered to have not only catalytic oxidation ability but also acid catalytic performance, which provides theoretical guidance for gold catalysis of the reaction of alcohol oxidation esterification to carboxylic ester.
Nielsen et al, Catal.Lett.,2007,116,1-2, disclose Au/TiO compounds2Is a catalyst, n-hexanol is a main substrate, and reaction results under different additives. The results show that: without or with addition of 0.2 mol% or 2 mol% NaOCH3The conversion rate and the selectivity of the reaction are both more than 90 percent when the additive is used; the optimum ratio of n-hexanol to the solvent methanol was found to be 1:4, where the conversion and selectivity of the reaction was the best. Klitgaard et al, Catal.Lett.,2008,126,213-2172Ti6O13The nano-gold catalyst loaded by the nano-wire is proved to have obviously higher catalytic activity than Au/TiO by tests2。
In conclusion, Au is used as a catalyst in the alcohol oxidation esterification reaction, mainly takes the form that nano-gold is loaded on a solid material as the catalyst, and Al is also available in addition to the solid material reported in the literature2O3，TiO2，CeO2，MOF，Ga2O3，SiO2And polymers and the like as carriers. Although catalytic systems composed of supported gold nanoparticles are capable of achieving oxidative esterification of alcohols, there are a number of disadvantages: complicated material preparation process and fussy nano-gold loading process, nano-gold particles are easy to aggregate into large particles with low activity, and some multi-phase systems cannot be effectively recycled.
Disclosure of Invention
The invention provides a method for synthesizing carboxylic ester by directly oxidizing and esterifying alcohol under mild conditions, which overcomes the defects of the prior art, improves the stability of a catalyst and the selectivity of reaction, and widens the scope of substrates.
The technical scheme adopted by the invention is as follows: in the atmosphere of air or oxygen or the mixture of the air and the oxygen, Au-Co composite particle load is used as a catalyst, an aromatic alcohol compound or a saturated straight-chain aliphatic alcohol compound is used as a substrate, methanol is used as a solvent, the reaction is carried out for 0.5 to 15 hours at the temperature of between 25 and 150 ℃ in the presence of an alkaline additive, and the carboxylic ester is obtained after the reaction and the post-treatment.
The catalyst in the technical scheme is an Au-Co composite particle load with a core-shell structure.
In the Au-Co composite particle load, the composite particles are particles formed by taking Au as a core and coating the surface of the core by cobalt in an oxidized state; the composite particles are loaded in a granular carrier; the composite particle load is sequentially a shell layer area, a load area and a non-load area from outside to inside, wherein the shell layer area and the non-load area do not contain composite particles, and the composite particles are distributed in the composite particle load area.
The Au-Co composite particle load is characterized in that the shell layer region is doped or not doped with one or more of Be, Al, Ti, V, Fe, Zn, Ge, Ce, Zr, Sn, Cr and Mn, and the doped metal accounts for 0-10% of the mass of the carrier, preferably 0.01-6%.
The Au-Co composite particle carrier is a silica-based composition, contains silica, and further contains one or more compounds selected from magnesium oxide, aluminum oxide, zirconium dioxide, cerium dioxide, titanium dioxide and gallium oxide metal compounds.
In the technical scheme, the alkaline additive is one or more of sodium acetate, potassium acetate, lithium acetate, sodium carbonate, potassium carbonate or cesium carbonate, and preferably potassium carbonate is used as the alkaline additive.
The molar ratio of the dosage of the catalyst to the substrate alcohol compound is 0.01:100-3.0: 100; the molar ratio of the dosage of the alkaline additive to the substrate alcohol compound is 1:100-30: 100; the molar ratio of the methanol to the substrate alcohol compound is 5:1-200: 1.
Aromatic alcohol compound, specifically one of benzyl alcohol, substituted aromatic benzyl alcohol, cinnamyl alcohol and furfuryl alcohol; the substituent on the benzene ring of the aromatic benzyl alcohol with the substituent is one or more than two of methyl, methoxy, chlorine, bromine and nitro, the number of the substituent on the benzene ring is 1-3, and the position of the substituent is at one or more than two of ortho-position, para-position and meta-position of the benzyl alcohol. The unsaturated carboxylic ester compounds corresponding to the compounds are one or more than two of methyl benzoate, methyl cinnamate or methyl furoate.
Saturated straight chain fatty alcohol compound, specifically one or more of n-butanol, n-pentanol, n-hexanol, n-heptanol and n-octanol; the saturated carboxylic ester compounds respectively corresponding to the saturated carboxylic ester compounds are one or more than two of methyl n-butyrate, methyl n-valerate, methyl n-hexanoate, methyl n-heptanoate and methyl n-octanoate.
The invention preferably has the reaction temperature of 25-150 ℃, the reaction time of 0.5-15h and the reaction pressure of 0.1-2.0 MPa. Wherein, the aromatic alcohol compound is used as a substrate, the reaction temperature is preferably 50-100 ℃, the reaction time is 1-8h, and the reaction pressure is 0.1-0.5 MPa; the saturated straight-chain fatty alcohol compound is used as a substrate, the reaction temperature is preferably 80-150 ℃, the reaction time is 4-15h, and the reaction pressure is 0.3-2.0 MPa.
Due to the application of the scheme, compared with the prior art, the invention has the following advantages:
1. the invention adopts alcohol to synthesize ester compound by direct oxidation and esterification, which shortens the process steps.
2. The catalytic system adopted by the invention has mild reaction conditions, simple operation and higher yield.
3. The amount of metal substances of the Au-Co composite particle load of the catalytic system catalyst can be as low as one thousandth of that of a substrate, so that the reaction cost is reduced, and the catalyst has potential due value.
4. The catalytic system of the invention is a heterogeneous catalytic system, and the catalyst is simple to recover and is environment-friendly.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
The Au-Co composite particle supported catalysts in the following examples all had a theoretical loading of 1.0% (weight percent)
Preparation of Au-Co composite particle load carrier:
after 10g of 30% silica sol (pH 4.5), 3.0g of aluminum nitrate, 1.2g of magnesium hydroxide, 2.0g of zirconium nitrate, 3g of 65% concentrated nitric acid in mass concentration and 100mL of deionized water were mixed uniformly, the mixture was stirred and aged at 50 ℃ for 24 hours to obtain a solid solution suspension, water was removed by rotary evaporation, and the solid was obtained by vacuum drying at 80 ℃. Placing the solid in a tubular furnace, carrying out temperature programming roasting in the air, uniformly heating at 30-300 ℃ for 3h, keeping at 300 ℃ for 4h, uniformly heating at 300-600 ℃ for 3h, and keeping at 600 ℃ for 4 h. Naturally cooling to obtain SiO2-MgO-Al2O3-ZrO2A metal composite oxide support.
Preparation of Au-Co composite particle load:
1g of SiO was added to the reactor in succession2-MgO-Al2O3-ZrO2The carrier, 0.3g of urea, 21.0mg of chloroauric acid, 0.18g of cobalt nitrate and 70mL of deionized water are uniformly mixed, stirred and reacted for 0.5h at 80 ℃, the mixture is cooled to room temperature, the solid obtained by filtering is dried for 1h at 80 ℃ in vacuum, and then the mixture is placed in a muffle furnace and calcined for 3h at 450 ℃. And naturally cooling to obtain the Au-Co composite particle load.
Example 1: synthesis of methyl benzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 108mg benzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after the oxygen is replaced for three times, the reaction is carried out for 5 hours at 80 ℃, the reaction is carried out to the room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, the residue column chromatography is carried out, and the product of 123.7mg of methyl benzoate and colorless liquid are obtained, and the yield is 91%.1H NMR(400M,CDCl3)δppm:3.91(s,3H)，7.43(t,J＝7.6Hz,2H)，7.55(t,J＝8.0Hz,1H)，8.04(d,J＝7.6Hz,2H)；13C NMR(100M，CDC13)δppm:167.1，132.9，130.2，129.6，128.3，52.0。
Example 2: synthesis of methyl p-methylbenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 122mg of p-methylbenzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 7 hours at 80 ℃, the reaction is carried out to room temperature, air is slowly released and the pressure is reduced, a catalyst is filtered, filtrate is subjected to rotary evaporation and concentration, and residue column chromatography is carried out to obtain a product, namely, the methyl p-methylbenzoate is 135.9mg and a yellowish liquid, wherein the yield is 91%.1H NMR(400M,CDCl3)δppm:2.38(s,3H)，3.89(s,3H)，7.28-7.35(m,2H)，7.82-7.85(m,2H)；13C NMR(100M,CDCl3)δppm:167.1，143.5，129.6，129.0，127.4，51.8，21.6。
Example 3: synthesis of methyl o-methylbenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 122mg of o-methylbenzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out at 80 ℃ for 7 hours, the reaction is cooled to room temperature, the gas is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary mode, the residue column chromatography is carried out, and then the product of o-methyl benzoate 140.3mg and colorless liquid are obtained, and the yield is 94%.1H NMR(400M,CDCI3)δppm:2.60(s,3H)，3.88(s,3H)，7.21-7.24(m,2H)，7.36-7.40(m,1H)，7.89-7.91(m,1H)；13C NMR(100M,CDCl3)δppm:168.1，140.2，132.0，131.7，130.6，129.6，125.7，51.8，21.7。
Example 4: synthesis of methyl m-methylbenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 122mg of m-methylbenzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out at 80 ℃ for 7 hours, the temperature is cooled to room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the residue is subjected to column chromatography to obtain 129.7mg of m-methyl benzoate, a colorless liquid and the yield is 86%.1H NMR(400M,CDCl3)δppm:2.38(s,3H)，3.89(s,3H)，7.28-7.35(m,2H)，7.82-7.85(m,2H)；13C NMR(100M,CDCl3)δppm:167.2，138.1，133.6，130.1，128.2，126.7，52.0，21.2。
Example 5: synthesis of methyl 3, 4-dimethylbenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 136mg3, 4-dimethylbenzyl alcohol (lmmol) and 4mL methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 12h at 80 ℃, the reaction is carried out after the temperature is cooled to the room temperature, air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary mode, the colorless liquid product 3, 4-dimethylbenzyl methyl benzoate 154.9mg is obtained through residue column chromatography, and the yield is 94%.1H NMR(400M,CDCl3)δppm:2.27(s,6H)，3.87(s,3H)，7.16(d,J＝8.0Hz,1H)，7.75(d,J＝8.8Hz,1H)，7.80(s,3H)；13C NMR(100M,CDC13)δppm:167.9，142.7，137.2，131.2，130.2，128.3，127.7，52.4，20.5，20.2。
Example 6: synthesis of methyl p-methoxybenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 138mg of p-methoxybenzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 7h at 80 ℃, the reaction is carried out to the room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the white solid product, namely the methyl p-methoxybenzoate, is obtained after the residue column chromatography, and the yield is 84%. The melting point is 48-51 ℃.1H NMR(400M,CDCl3)δppm:3.85(s,3H)，3.88(s,3H)，6.91(d,J＝8.8Hz,2H)，7.99(d,J＝8.8Hz,2H)；13C NMR(100M,CDCl3)δppm:166.9,163.4，131.6，122.6，113.6，55.4，51.9。
Example 7: synthesis of methyl m-methoxybenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 138mg of m-methoxybenzyl alcohol (lmmol), 4mL of methanol were added in successionThe mixture is put into a pressure kettle with a 25mL glass liner, the pressure is increased to 0.lMPa after the oxygen is replaced for three times, the mixture reacts for 7 hours at the temperature of 80 ℃, the mixture is cooled to the room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary mode, the colorless liquid product methyl m-methoxybenzoate is obtained after the residue column chromatography, and the yield is 87%.1H NMR(400M,DMSO)δppm:3.77(s,3H)，3.81(s,3H)，7.17-7.20(m,1H)，7.37-7.41(m,2H)，7.51(d，J＝7.6Hz,1H)；13C NMR(100M,DMSO)δppm:166.1，159.3，131.0，129.9，121.4，119.3，113.8，55.3，52.2。
Example 8: synthesis of methyl p-chlorobenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 142.5mg p-chlorobenzyl alcohol (lmmol) and 4mL methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 10h at 80 ℃, the temperature is cooled to room temperature, air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the white solid product, namely the methyl p-chlorobenzoate, is obtained after the residue column chromatography, with the yield of 95%. Melting point 42-44 ℃.1H NMR(400M,CDCl3)δppm:3.86(s,3H)，7.91(d,J＝8.0Hz,2H)，7.35(d,J＝8.4Hz,2H)；13C NMR(100M,CDCl3)δppm:166.1，139.3，130.9，128.6，128.5，52.2。
Example 9: synthesis of methyl m-chlorobenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 142.5mg of m-chlorobenzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 10h at 80 ℃, the reaction is cooled to room temperature, air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the yellowish liquid product, namely methyl m-chlorobenzoate, is obtained after the residue column chromatography, wherein the yield is 90%.1H NMR(400M,CDCl3)δppm:3.92(s,3H)，7.37(t,J＝8.0Hz,1H)，7.52(d,J＝8.0Hz,1H)，7.92(d,J＝7.6Hz,1H)，8.02(s,1H)；13C NMR(100M,CDCl3)δppm:165.9,134.6,133.0，131.9，129.7，127.8，122.0，52.5。
Example 10: synthesis of o-chlorobenzoic acid methyl ester
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 142.5mg of o-chlorobenzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 10h at 80 ℃, the reaction is cooled to room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is concentrated by rotary evaporation, and the yellowish liquid product, namely the o-chlorobenzoic acid methyl ester, is 159.6mg after the residue column chromatography is carried out, and the yield is 90%.1H NMR(400M,CDCl3)δppm:3.91(s,3H)，7.29-7.31(m,1H)，7.37-7.44(m,2H)，7.79-7.81(m,1H)；13C NMR(100M,CDCl3)δppm:166.1，133.7，132.6，131.4，131.1，130.1，126.6，52.4。
Example 11: synthesis of methyl 1-naphthoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 142.5mg of 1-naphthyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 10h at 80 ℃, the reaction is carried out for cooling to the room temperature, air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary mode, and the colorless liquid product 1-methyl naphthoate, 141.2mg and the yield is 77 percent are obtained after the residue column chromatography.1H NMR(400M,CDCl3)δppm:4.01(s,1H)，7.48-7.56(m,1H)，7.60-7.64(m,1H)，7.89(d,J＝8.4Hz,1H)，8.02(d,J＝8.4Hz,1H)，8.20(d,J＝7.2Hz,1H)，8.92(d,J＝8.4Hz,1H)；13C NMR(100M,CDCl3)δppm:168.1，133.9，133.4，131.4，130.3，128.6，127.8，127.2，126.3，125.9，124.6，52.2。
Example 12: synthesis of methyl 3, 4-dimethoxybenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 168.0mg 3, 4-dimethoxy benzyl alcohol (lmmol) and 4mL methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 12h at 80 ℃, the temperature is cooled to room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, the residue is subjected to column chromatography, and the residue is subjected to the filtration176.9mg of 3, 4-dimethoxybenzoic acid methyl ester as a white solid product is obtained, and the yield is 92%. Melting point 59-62 ℃.1H NMR(400M,CDCl3)δppm:3.88(s,3H)，3.92(s,6H)，6.88(d,J＝8.4Hz,1H)，7.53(d,J＝l.6，1H)，7.67(dd,J1＝J2＝1.6Hz,1H)；13C NMR(100M,CDCl3)δppm:167.4，153.5,149.2，124.1，123.2，112.5，110.8，56.6，52.6。
Example 13: synthesis of methyl 3,4, 5-trimethoxybenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 198.0mg of 3,4, 5-trimethoxy benzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 12h at 80 ℃, the temperature is cooled to room temperature, air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the residue column chromatography is carried out to obtain 169.5mg of white solid product 3,4, 5-trimethoxy methyl benzoate, wherein the yield is 78%. Melting point 82-84 ℃.1H NMR(400M，CDCl3)δppm:3.89(s,12H)，7.29(s,2H)；13C NMR(100M,CDC13)δppm:166.8，153.0，142.2，125.2，106.8，103.1，61.0，56.3，52.3。
Example 14: synthesis of methyl p-bromobenzoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 187.0mg of p-bromobenzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 10 hours at 80 ℃, the reaction is cooled to the room temperature, the gas is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the white solid product, namely methyl p-bromobenzoate, 64.5mg of white solid is obtained after the residue column chromatography, and the yield is 30%. The melting point is 77-81 ℃.1H NMR(400M,DMSO)δppm:3.83(s,3H)，7.71(d,J＝8.8Hz,2H),7.85(d,J＝8.4Hz,2H)；13C NMR(100M,DMSO)δppm:166.6，133.0，132.1，129.8，128.4，51.4。
Example 15: synthesis of methyl p-nitrobenzoate
20mg of Au-Co composite particle support (0.1 mol%)，13.8mg K2CO3(10 mol%), 153.0mg of p-nitrobenzyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 10 hours at 80 ℃, the reaction is cooled to room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary mode, and the white solid product, namely methyl p-bromobenzoate, is obtained after the residue column chromatography, with the yield of 50%. The melting point is 94-96 ℃.1H NMR(400M,CDCl3)δppm:2.38(s,3H)，3.89(s,3H)，7.28-7.35(m,2H)，7.82-7.85(m,2H)；13C NMR(100M,CDCl3)δppm:167.1，143.5，129.6，129.0，127.4，51.8，21.6。
Example 16: synthesis of methyl cinnamate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 134.0mg cinnamyl alcohol (lmmol) and 4mL methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 10h at 80 ℃, the reaction is carried out to room temperature, air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the residue column chromatography is carried out to obtain a yellowish solid product, namely methyl cinnamate 64.8mg, and the yield is 40%. Melting point 34-36 ℃.1H NMR(400M,CDCl3)δppm:3.81(s,3H)，6.45(d,J＝16Hz,1H)，7.39(s,3H)，7.52(s,2H)，7.70(d,J＝16Hz,1H)；13C NMR(100M,CDCl3)δppm:167.5，145.0，134.4，130.4，129.0，128.1，117.9，51.8。
Example 17: synthesis of methyl furoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 98.0mg furfuryl alcohol (lmmol) and 4mL methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.lMPa after three times of oxygen replacement, the reaction is carried out for 10h at 80 ℃, the reaction is carried out to the room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the colorless liquid product, namely the methyl furoate, is obtained after the residue column chromatography, with the yield of 40%.1H NMR(400MHz,CDCl3)δppm:3.87(s,3H)，6.80(dd,J1＝l.8Hz,J2＝3.3Hz,1H)，7.17(d,J＝3.6Hz,1H)，7.58(d,J＝0.6Hz,1H)；13C NMR(100MHz,CDCl3)δppm:159.8,146.8，144.6，118.3，112.3，52.2。
Example 18: synthesis of methyl n-butyrate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 74.1mg of n-butyl alcohol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.6MPa after three times of oxygen replacement, the reaction is carried out for 7h at 130 ℃, the reaction is cooled to room temperature, air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the residue column chromatography is carried out to obtain 45.9mg of methyl n-butyrate, a colorless liquid and the yield is 45%.1H NMR(400M,CDCl3)δppm:0.88(t,3H)，1.35–1.45(m,2H)，2.01(t,2H)，3.45(s,3H)；13C NMR(100M，CDC13)δppm:174.07，51.36，36.09，18.58，13.73。
Example 19: synthesis of methyl n-valerate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 88.2mg of n-pentanol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.6MPa after three times of oxygen replacement, the reaction is carried out for 7h at 130 ℃, the reaction is carried out to the room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the residue column chromatography is carried out to obtain 70.9mg of the product of n-methyl valerate, colorless liquid and the yield is 61%.1H NMR(400M,CDCl3)δppm:0.88-0.99(m,3H)，1.17–1.77(m,4H)，2.24-2.35(m,2H)，3.60(s,3H)；13C NMR(100M，CDC13)δppm:174.23，51.38，33.90，27.21，22.42，13.73。
Example 20: synthesis of methyl hexanoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 102.2mg of n-hexanol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.6MPa after three times of oxygen replacement, the reaction is carried out for 7h at 130 ℃, the reaction is cooled to room temperature, the gas is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the residue column chromatography is carried out to obtain 84.6mg of methyl hexanoate, a colorless liquid and the yield is 65%.1H NMR(400M,CDCl3)δppm:0.82(t,J＝6.9Hz,3H)，1.21-1.26(m,4H)，1.52-1.59(m,2H)，2.23(t,J＝7.6Hz,2H)，3.6(s,3H)；13C NMR(100M，CDC13)δppm:174.3，51.4，34.0，31.3，24.6，22.3，13.9。
Example 21: synthesis of methyl n-heptanoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 116.2mg of n-heptanol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.6MPa after three times of oxygen replacement, the reaction is carried out at 130 ℃ for 7h, the temperature is cooled to room temperature, the air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, the residue is subjected to column chromatography to obtain 50.5mg of the product of methyl n-heptanoate, colorless liquid, and the yield is 35%.1H NMR(400M,CDCl3)δppm:1.25(t,3H,J＝7.1Hz),1.36(m,8H),2.04(s,3H),4.12(dd,2H,J＝7.1Hz)；13C NMR(100M，CDC13)δppm:171.1，60.4，34.8，31.7，30.4，23.8，21.0，14.2。
Example 22: synthesis of methyl n-octanoate
20mg of Au-Co composite particle-supporting substance (0.1 mol%), 13.8mg of K2CO3(10 mol%), 130.2mg of n-octanol (lmmol) and 4mL of methanol are sequentially added into a pressure kettle with a 25mL glass lining, the pressure is increased to 0.6MPa after three times of oxygen replacement, the reaction is carried out for 7h at 130 ℃, the reaction is carried out to the room temperature, air is slowly released and the pressure is reduced, the catalyst is filtered, the filtrate is evaporated and concentrated in a rotary manner, and the residue column chromatography is carried out to obtain 61.7mg of the product of methyl n-octanoate, colorless liquid and the yield is 39%.1H NMR(400M,CDCl3)δppm:0.88(t,J＝6.6Hz,3H)，1.25-1.32(m,8H)，1.59-1.65(m,2H)，2.30(t,J＝7.6Hz,2H)，3.67(s,3H)；13C NMR(100M，CDC13)δppm:174.4，51.5，34.1，31.7，29.2，29.0，25.0，22.6，14.1。
Claims (9)
1. A method for preparing carboxylic ester by an alcohol direct oxidation esterification method is characterized in that: in the atmosphere of air or oxygen or the mixture of the air and the oxygen, reacting for 0.5 to 15 hours at a temperature of between 25 and 150 ℃ in the presence of an alkaline additive by taking an Au-Co composite particle load as a catalyst, an aromatic alcohol compound or saturated linear fatty alcohol as a substrate and methanol as a solvent, and carrying out post-reaction treatment to obtain the carboxylic ester;
the catalyst is an Au-Co composite particle load with a core-shell structure;
in the Au-Co composite particle load, the composite particles are particles formed by taking Au as a core and coating the surface of the core by cobalt in an oxidized state; the composite particles are loaded in a granular carrier; the composite particle load is sequentially a shell layer area, a load area and a non-load area from outside to inside, wherein the shell layer area and the non-load area do not contain composite particles, and the composite particles are distributed in the composite particle load area; the Au-Co composite particle load is characterized in that the shell layer region is not doped or doped with one or more of Be, Al, Ti, V, Fe, Zn, Ge, Ce, Zr, Sn, Cr and Mn, and the doped metal accounts for 0-10% of the mass of the carrier.
2. The method of claim 1, wherein: the doped metal in the shell layer region of the Au-Co composite particle load is 0.01-6% of the mass of the carrier.
3. The method of claim 1, wherein: the particulate carrier is a silica-based composition containing silica and one or more of magnesium oxide, aluminum oxide, zirconium dioxide, cerium dioxide, titanium dioxide and gallium oxide metal compounds.
4. The method of claim 1, further comprising: the alkaline additive is one or more than two of sodium acetate, potassium acetate, lithium acetate, sodium carbonate, potassium carbonate or cesium carbonate.
5. The method of claim 4, further comprising: the alkaline additive is potassium carbonate.
6. The method of claim 1, further comprising: the molar ratio of the dosage of the catalyst to the substrate alcohol compound is 0.01:100-3.0: 100; the molar ratio of the dosage of the alkaline additive to the substrate alcohol compound is 1:100-30: 100; the molar ratio of the methanol to the substrate alcohol compound is 5:1-200: 1.
7. The method of claim 1, further comprising: the aromatic alcohol compound is one of benzyl alcohol, substituted aromatic benzyl alcohol, cinnamyl alcohol and furfuryl alcohol; the substituent on the benzene ring of the aromatic benzyl alcohol with the substituent is one or more than two of methyl, methoxy, chlorine, bromine and nitro, the number of the substituents on the benzene ring is 1-3, and the position of the substituent is at one or more than two of ortho-position, para-position and meta-position of the benzyl alcohol.
8. The method of claim 1, further comprising: the saturated straight-chain fatty alcohol compound is specifically one of n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol or n-octyl alcohol.
9. The method of claim 1, further comprising: the reaction temperature for preparing the carboxylic ester by the alcohol direct oxidation esterification method is 25-150 ℃, the reaction time is 0.5-15h, and the reaction pressure is 0.1-2.0Mpa, wherein the aromatic alcohol compound is used as a substrate, the reaction temperature is 50-100 ℃, the reaction time is 1-8h, and the reaction pressure is 0.1-0.5 MPa; the saturated straight-chain fatty alcohol compound is used as a substrate, the reaction temperature is 80-150 ℃, the reaction time is 4-15h, and the reaction pressure is 0.3-2.0 MPa.
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| CN104292106A (en) * | 2013-07-17 | 2015-01-21 | 中国科学院大连化学物理研究所 | One-pot method for preparing organic carboxylic ester |
| CN104945210A (en) * | 2014-03-28 | 2015-09-30 | 中国科学院大连化学物理研究所 | Method for preparing esters through primary alcohol oxidation |
| CN105214683A (en) * | 2007-08-13 | 2016-01-06 | 旭化成化学株式会社 | The manufacture method of carboxylate catalyst for producing, its manufacture method and carboxylate |
| WO2017084969A1 (en) * | 2015-11-19 | 2017-05-26 | Evonik Röhm Gmbh | Gold-based catalyst for oxidative esterification of aldehydes to carboxylic acid esters |
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| CN105214683A (en) * | 2007-08-13 | 2016-01-06 | 旭化成化学株式会社 | The manufacture method of carboxylate catalyst for producing, its manufacture method and carboxylate |
| CN104292106A (en) * | 2013-07-17 | 2015-01-21 | 中国科学院大连化学物理研究所 | One-pot method for preparing organic carboxylic ester |
| CN104945210A (en) * | 2014-03-28 | 2015-09-30 | 中国科学院大连化学物理研究所 | Method for preparing esters through primary alcohol oxidation |
| WO2017084969A1 (en) * | 2015-11-19 | 2017-05-26 | Evonik Röhm Gmbh | Gold-based catalyst for oxidative esterification of aldehydes to carboxylic acid esters |
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