CN112047819B - Preparation method of 2-cyclohexene-1-ketone - Google Patents
Preparation method of 2-cyclohexene-1-ketone Download PDFInfo
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Abstract
The invention relates to a preparation method of 2-cyclohexene-1-ketone, which comprises the following steps: step one, cyclohexene, an oxidant, an accelerant, alkali and a solvent are subjected to oxidation reaction under a mild condition, and the accelerant can improve the oxidation efficiency and the reaction selectivity so that the reaction can be carried out under the mild condition; secondly, adding a reducing agent into the mixed solution obtained in the first step, stirring and filtering; and thirdly, treating the filtrate by using a cracking agent to promote partial reaction intermediates to be further converted into the product 2-cyclohexene-1-ketone, improving the reaction yield, and finally carrying out reduced pressure distillation to obtain the 2-cyclohexene-1-ketone. The method for synthesizing 2-cyclohexene-1-ketone has the advantages of high yield, good product purity, mild reaction conditions, less waste water, safety, environmental protection and great market competitive advantage.
Description
Technical Field
The invention belongs to the technical field of fine chemical preparation, and particularly relates to a preparation method of 2-cyclohexene-1-ketone.
Background
2-cyclohexene-1-ketone (common name cyclohexenone) is an important fine organic chemical intermediate and is widely applied to the fields of medicines, pesticides, spices, surfactants, high polymer materials and the like. At present, several methods for synthesizing cyclohexenone exist, but the methods have industrial prospects and mainly comprise a cyclohexene oxidation method, a cyclohexanone bromination method and a phenol hydrogenation method. The cyclohexene oxidation method is currently researched more, mainly uses air or hydrogen peroxide as an oxidant, but has harsh reaction conditions, more byproducts and low selectivity. In addition, some catalysts used are complex to prepare, poor in reusability and expensive in catalyst cost. The cyclohexanone bromination method needs to use liquid bromine, belongs to a process with high safety risk, has serious environmental pollution, and is being eliminated. Moreover, the cyclohexenone obtained by the bromination method has darker color and low product quality. The phenol can also be used for preparing cyclohexenone in the hydrogenation reaction, the preparation requirement on the catalyst is strict, the reduction degree needs to be accurately controlled in the reaction, and excessive reduction is prevented. In addition, the equipment investment of the method is large, and no report for industrial production of cyclohexenone is found. Substituted dihydropyrane obtained by the reaction of three components of ethyl acetoacetate, formaldehyde and alkyl vinyl ether is used as a raw material to prepare cyclohexenone. However, the method needs to use a large amount of alcohol solvent, and the recovery of the solvent consumes energy and time, so that the synthesis efficiency of the cyclohexenone is not high. In addition, patent CN 106883111B reports that cyclohexenone is prepared by using 2-methoxypropene and acrolein, but the preparation method requires a higher reaction temperature and a certain high-pressure environment, and in addition, a large amount of phosphoric acid is used, so that the yield is low. Therefore, a cyclohexenone synthesis method which is environment-friendly, mild in reaction conditions, simple and convenient to operate, low in cost and good in product quality is urgently needed in the current industry.
Disclosure of Invention
Aiming at the defects and improvement requirements of the prior art, the invention aims to provide a preparation method of 2-cyclohexene-1-ketone, which improves the reaction efficiency and can be recycled by improving the formula and the composition of an accelerant, and saves the cost of the catalyst. Meanwhile, the formula improvement of the accelerant promotes the rapid conversion of some intermediates in the oxidation process into target products, and the step of cracking the peroxy intermediate is added to promote the conversion into the product 2-cyclohexene-1-ketone. Compared with the traditional 2-cyclohexene-1-ketone synthesis method, the method has the advantages of high reaction selectivity, simple and convenient operation conditions, mild reaction conditions, less environmental pollution and great industrialization prospect.
In order to achieve the purpose, the invention provides a preparation method of 2-cyclohexene-1-ketone, which comprises the following steps:
(1) cyclohexene is stirred and reacts with an accelerator, an oxidant, alkali and a solvent in the presence of the oxidant, the alkali and the solvent to obtain a reaction mixed solution;
(2) adding a reducing agent into the reaction mixed liquid in the step (1), stirring for reaction, and filtering to obtain filtrate and filter residue;
(3) and (3) adding a cracking agent into the filtrate obtained in the step (2), and stirring and reacting in the air or oxygen atmosphere to obtain a reaction solution containing the required product 2-cyclohexene-1-ketone.
Further, the stirring reaction temperature in the step (1) is 0-80 ℃, and the stirring reaction time is 20-30 hours.
Further, the stirring reaction temperature in the step (2) is 0-80 ℃, and the stirring reaction time is 1-20 hours.
Further, the stirring reaction temperature in the step (3) is 0-80 ℃, and the stirring reaction time is 1-20 hours.
Further, the oxidant in the step (1) is hydrogen peroxide (H)2O2) At least one of perbenzoic acid, peracetic acid, m-chloroperoxybenzoic acid, t-butyl peroxy, benzoyl peroxy, and oxygen (1-10 atmospheres).
Further, the base in the step (1) is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, lithium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium carbonate, potassium phosphate, sodium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, pyridine, 4-methylpyridine, trimethylamine, triethylamine, tributylamine, azamethylmorpholine, diisopropylethylamine, and 1, 8-diazabicycloundecan-7-ene.
Further, the equivalent ratio of the alkali to the cyclohexene in the step (1) is 0.1: 1-10: 1; preferably, the equivalent ratio of base to cyclohexene is 1: 1.
Further, the solvent in step (1) is water, methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, acetonitrile, acetone, butanone, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, benzene, toluene, xylene, tetrahydrofuran, 1, 4-dioxane, -ethylene glycol dimethyl ether, Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO).
Further, the equivalent ratio of the cyclohexene to the oxidant in the step (1) is 1: 1-1: 20.
Further, the weight ratio of the accelerator to the cyclohexene in the step (1) is 1: 100-20: 100; preferably, the weight ratio of accelerator to cyclohexene is 1: 10.
Further, the preparation method of the accelerator in the step (1) comprises the following steps:
the palladium carbon (wherein the palladium content is 1-10% by mass) and an additive are uniformly mixed, then the mixture is heated for 0.5-24 hours under the anaerobic condition, the temperature range is 25-300 ℃, and then the mixture is cooled to room temperature for later use, wherein the additive comprises at least one of ferric oxide, ferrous oxide, ferroferric oxide, copper oxide, cuprous oxide, titanium dioxide, cerium dioxide, nickel oxide, cobaltous oxide, vanadium pentoxide, chromium trioxide, manganese dioxide, potassium permanganate, silver oxide, silica gel, kieselguhr, kaolin, montmorillonite and bentonite, and the weight ratio of the palladium carbon to the additive is 1: 100-100: 100.
Further, the reducing agent in the step (2) is at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite and sodium sulfide; the equivalent ratio of the cyclohexene to the reducing agent is 1: 2-1: 10.
Further, in the step (3), the cracking agent is at least one of 4-dimethylaminopyridine, pyridine, 2, 6-dimethylpyridine, 2, 6-di-tert-butylpyridine, 4-methylpyridine, trimethylamine, triethylamine, tributylamine, N-methylmorpholine, diisopropylethylamine, 1, 8-diazabicycloundec-7-ene, 1, 4-diazabicyclo [2.2.2] octane, tetramethylethylenediamine, hexamethylenetetramine, trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine.
Further, the filter residue in the step (2) is washed by a solvent and then is used as a reaction promoter for repeated use, and washing liquid is combined with the filtrate.
Further, carrying out reduced pressure rectification on the reaction liquid in the step (3), and collecting to obtain the 2-cyclohexene-1-ketone.
Compared with the prior art, the invention has the following advantages and effects:
1. the method has the advantages of easily available raw material sources, simple and convenient operation conditions, mild reaction conditions, no need of high-pressure equipment, low cost, less waste water and environmental protection.
2. The product obtained by the invention has high yield and high purity, and can be separated and purified by simple reduced pressure distillation.
3. The accelerant used in the invention can be repeatedly used for several times, thereby further saving the cost.
Detailed Description
The practice of the present invention is further illustrated, but is not intended to be limited, by the following examples.
Example 1:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (120 ml, 30% by mass), cyclohexene/oxidant (1/1) in an equivalent ratio, and sodium carbonate (106g) were stirred and reacted with dichloromethane (1 l) at 40 ℃ for 24 hours to obtain a reaction mixture. The preparation method of the accelerant comprises the following steps: palladium carbon (1 g, wherein palladium is 2% by mass) and cuprous oxide (10 g) kaolin (90 g) are mixed, heated at 150 ℃ for 0.5 hour under oxygen-free conditions, and then cooled to room temperature to obtain the accelerator. To the above reaction was added a saturated solution of sodium sulfite as a reducing agent (208 g of sodium sulfite prepared as a saturated solution). Stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and stirred with 4-dimethylamino pyridine (20 g) as a cracking agent for reaction for 10 hours at 40 ℃ in the air or oxygen atmosphere, thus obtaining the final reaction solution. And (3) carrying out reduced pressure distillation on the final reaction liquid to collect 81.6 g of the required product 2-cyclohexene-1-ketone with the yield of 69%.
Example 2:
cyclohexene (82 g), an accelerator (8.2g), an oxidant tert-butyl peroxy ether (219 g), sodium carbonate (106g) and dichloromethane (1L) were stirred and reacted at 40 ℃ for 24 hours to obtain a reaction mixture. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein the mass percent of palladium is 2%) and cuprous oxide (10 g) kaolin (90 g) are mixed uniformly, then heated for 10 hours at 150 ℃ under the anaerobic condition, and then cooled to room temperature to obtain the accelerator. A saturated solution of sodium sulfite as a reducing agent (408 g of sodium sulfite was prepared as a saturated solution) was added to the above reaction, and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with 4-dimethylamino pyridine (20 g) as a cracking agent for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. And distilling the final reaction liquid under reduced pressure to collect 76.8 g of the required product 2-cyclohexene-1-ketone with the yield of 80%.
Example 3:
cyclohexene (82 g), an accelerator (8.2g), an oxidant tert-butyl peroxy ether (152 g), sodium carbonate (106g) and dichloromethane (1L) were stirred and reacted at 40 ℃ for 24 hours to obtain a reaction mixture. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein the mass percent of palladium is 1%) and cuprous oxide (10 g) kaolin (40 g) are mixed uniformly, then heated for 20 hours at 150 ℃ under the anaerobic condition, and then cooled to obtain the accelerator. A saturated solution of sodium sulfite as a reducing agent (608 g of sodium sulfite was prepared as a saturated solution) was added to the above reaction, and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with 4-dimethylamino pyridine (20 g) as a cracking agent for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. 74.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 78%.
Example 4:
cyclohexene (82 g) and accelerator (8.2g), oxidant tert-butanol peroxide (225 g) and sodium carbonate (106g) were reacted with dichloromethane (1 l) at 40 ℃ with stirring for 24 hours to obtain a reaction mixture. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein the mass percent of palladium is 2%) and cuprous oxide (2 g) kaolin (20 g) are mixed uniformly, then heated for 24 hours at 150 ℃ under the anaerobic condition, and then cooled to obtain the accelerator. A saturated solution of sodium sulfite as a reducing agent (1040 g of sodium sulfite was prepared as a saturated solution) was added to the above reaction, and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with 4-dimethylamino pyridine (20 g) as a cracking agent for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. And distilling the final reaction liquid under reduced pressure to collect 82.6 g of the required product 2-cyclohexene-1-ketone with the yield of 86%.
Example 5:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (2400 ml, 30% by mass, equivalent ratio cyclohexene/oxidant: 1/20), sodium carbonate (106g) and dichloromethane (1 l) were stirred and reacted at 40 ℃ for 24 hours to obtain a reaction mixture. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein the mass percent of palladium is 2 percent) and ferric oxide (3 g) kaolin (20 g) are mixed uniformly, then heated for 10 hours at 150 ℃ under the anaerobic condition, and then cooled to obtain the accelerator. A saturated solution of sodium sulfite as a reducing agent (808 g of sodium sulfite prepared as a saturated solution) was added to the above reaction, and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with 4-dimethylamino pyridine (20 g) as a cracking agent for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. 78.7 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 89%.
Example 6:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), cyclohexene/oxidant (1/4 equivalent ratio), sodium carbonate (106g) and dichloromethane (1 l) were stirred and reacted at 40 ℃ for 24 hours to obtain a reaction mixture. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein the mass percent of palladium is 2 percent) and cobaltous oxide (3.5 g) kaolin (20 g) are mixed uniformly, then heated for 10 hours at 150 ℃ under the anaerobic condition, and then cooled to obtain the accelerator. A saturated solution of sodium sulfite as a reducing agent (1040 g of sodium sulfite was prepared as a saturated solution) was added to the above reaction, and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with 4-dimethylamino pyridine (20 g) as a cracking agent for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. And distilling the final reaction liquid under reduced pressure to collect 80.6 g of the required product 2-cyclohexene-1-ketone, wherein the yield is 84%.
Example 7:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium-carbon (10 g, containing 5% palladium by mass) and silica gel (20 g) were mixed, heated at 150 ℃ for 10 hours in the absence of oxygen, and then cooled to obtain an accelerator. A saturated solution of sodium sulfite as a reducing agent (340 g of sodium sulfite was prepared as a saturated solution) was added to the above reaction, and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with 4-dimethylamino pyridine (20 g) as a cracking agent for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. And distilling the final reaction liquid under reduced pressure to collect 79.7 g of the required product 2-cyclohexene-1-ketone, wherein the yield is 83%.
Example 8:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. A saturated solution of sodium sulfite as a reducing agent (208 g of sodium sulfite prepared as a saturated solution) was added to the above reaction, and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with 4-dimethylamino pyridine (20 g) as a cracking agent for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. And (3) carrying out reduced pressure distillation on the final reaction liquid to collect 75.8 g of the required product 2-cyclohexene-1-ketone, wherein the yield is 79%.
Example 9:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein the mass percent of palladium is 2%) and kaolin (10 g) are mixed uniformly, then heated for 10 hours at 25 ℃ under the anaerobic condition, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with 4-dimethylamino pyridine (20 g) as a cracking agent for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. And distilling the final reaction liquid under reduced pressure to collect 76.8 g of the required product 2-cyclohexene-1-ketone with the yield of 80%.
Example 10:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The combined filtrate is stirred and reacted with 2, 6-di-tert-butylpyridine (10 g) as a cracking agent for 10 hours at 40 ℃ in the atmosphere of air or oxygen to obtain the final reaction solution. 74.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 78%.
Example 11:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The combined filtrate is stirred and reacted with a cracking agent N-methylmorpholine (10 g) for 10 hours at 40 ℃ in the air or oxygen atmosphere to obtain the final reaction solution. 78.7 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 82%.
Example 12:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2 percent by mass) and kaolin (20 g) are mixed uniformly, then heated for 10 hours at 100 ℃ under the anaerobic condition, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 10 hours to obtain the final reaction solution. And distilling the final reaction liquid under reduced pressure to collect 76.8 g of the required product 2-cyclohexene-1-ketone with the yield of 80%.
Example 13:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), potassium carbonate (138g) and dichloromethane (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 8 percent by mass) and kaolin (70 g) are mixed uniformly, then heated for 10 hours at 150 ℃ under the anaerobic condition, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 20 hours to obtain the final reaction solution. And (3) carrying out reduced pressure distillation on the final reaction liquid to collect 81.6 g of the required product 2-cyclohexene-1-ketone, wherein the yield is 85%.
Example 14:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium phosphate (164g) and dichloromethane (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 10% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 20 hours to obtain the final reaction solution. 86.4 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 90%.
Example 15:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and tetrahydrofuran (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2 percent by mass) and kaolin (20 g) are mixed uniformly, then heated for 10 hours at 180 ℃ under the anaerobic condition, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 10 hours to obtain the final reaction solution. 78.7 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 82%.
Example 16:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and tert-butyl alcohol (1L) are stirred and reacted for 24 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 10 hours to obtain the final reaction solution. And 3.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 77%.
Example 17:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and tert-butyl alcohol (1L) are stirred and reacted for 20 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 1 hour to obtain the final reaction solution. And 3.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 70%.
Example 18:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and tert-butyl alcohol (1L) are stirred and reacted for 30 hours at 40 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 10 hours to obtain the final reaction solution. 73.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 79%.
Example 19:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and tert-butyl alcohol (1L) are stirred and reacted for 24 hours at 80 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 200 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 10 hours to obtain the final reaction solution. And 3.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 73%.
Example 20:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and tert-butyl alcohol (1L) are stirred and reacted for 24 hours at 80 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the above reaction was added a saturated solution 300 of sodium thiosulfate (a saturated solution was prepared from 300g of sodium thiosulfate) as a reducing agent, and the mixture was stirred at 80 ℃ for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 10 hours to obtain the final reaction solution. And 3.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 74%.
Example 21:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 0 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 250 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at room temperature for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The combined filtrate is reacted with a cracking agent 1, 8-diazabicycloundec-7-ene (10 g) in the air or oxygen atmosphere at 40 ℃ for 1 hour to obtain the final reaction solution. And 3.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 76%.
Example 22:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 0 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at 0 ℃ for 20 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the atmosphere of air or oxygen at 40 ℃ for 10 hours to obtain the final reaction solution. And 3.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 76%.
Example 23:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and dichloromethane (1L) are stirred and reacted for 24 hours at 0 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 300 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at 0 ℃ for 20 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the air or oxygen atmosphere at 0 ℃ for 10 hours to obtain the final reaction solution. And 3.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 71%.
Example 24:
cyclohexene (82 g), an accelerator (8.2g), an oxidant hydrogen peroxide (500 ml, 30% by mass), sodium carbonate (106g) and tert-butyl alcohol (1L) are stirred and reacted for 24 hours at 80 ℃ to obtain a reaction mixed solution. The preparation method of the accelerant comprises the following steps: palladium carbon (10 g, wherein palladium is 2% by mass) and kaolin (20 g) are mixed, heated at 150 ℃ for 10 hours under oxygen-free conditions, and then cooled to obtain the accelerator. To the reaction was added a saturated solution of reducing agent sodium thiosulfate (300 g of sodium thiosulfate was prepared as a saturated solution), and the mixture was stirred at 80 ℃ for 10 hours. The mixture is filtered, the filter residue is washed with a solvent, and the filtrate and the washing liquid are combined. The solid filter residue is used as a reaction promoter for recycling. The filtrate is combined and then stirred and reacted with a cracking agent 1, 8-diazabicycloundecen-7-ene (10 g) in the air or oxygen atmosphere at 80 ℃ for 10 hours to obtain the final reaction solution. And 3.9 g of the required product 2-cyclohexene-1-ketone is collected by reduced pressure distillation of the final reaction liquid, and the yield is 73%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of 2-cyclohexene-1-ketone is characterized by comprising the following steps:
(1) cyclohexene is stirred and reacts with an accelerator, an oxidant, alkali and a solvent in the presence of the oxidant, the alkali and the solvent to obtain a reaction mixed solution;
(2) adding a reducing agent into the reaction mixed liquid in the step (1), stirring for reaction, and filtering to obtain filtrate and filter residue;
(3) then adding a cracking agent into the filtrate obtained in the step (2), and stirring and reacting in the air or oxygen atmosphere to obtain a reaction solution containing the required product 2-cyclohexene-1-ketone;
the preparation method of the accelerant comprises the following steps:
uniformly mixing palladium carbon and an additive, heating for 0.5-24 hours under an oxygen-free condition at the temperature of 25-300 ℃, and cooling to room temperature for later use, wherein the additive comprises at least one of ferric oxide, ferrous oxide, ferroferric oxide, copper oxide, cuprous oxide, titanium dioxide, cerium dioxide, nickel oxide, cobaltous oxide, vanadium pentoxide, chromium trioxide, manganese dioxide, potassium permanganate, silver oxide, silica gel, diatomite, kaolin, montmorillonite and bentonite, and the weight ratio of the palladium carbon to the additive is 1: 100-100: 100; the palladium carbon contains 1 to 10 percent of palladium by mass percentage;
the reducing agent is at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite and sodium sulfide; the equivalent ratio of the cyclohexene to the reducing agent is 1: 2-1: 10; the cracking agent is at least one of 4-dimethylamino pyridine, 2, 6-dimethyl pyridine, 2, 6-di-tert-butyl pyridine, 4-methylpyridine, trimethylamine, triethylamine, tributylamine, N-methylmorpholine, diisopropylethylamine, 1, 8-diazabicycloundeca-7-ene, 1, 4-diazabicyclo [2.2.2] octane, tetramethylethylenediamine, hexamethylenetetramine, trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.
2. The preparation method according to claim 1, wherein the stirring reaction temperature in the step (1) is 0 to 80 ℃, and the stirring reaction time is 20 to 30 hours; the stirring reaction temperature of the step (2) is 0-80 ℃, and the stirring reaction time is 1-20 hours; the stirring reaction temperature in the step (3) is 0-80 ℃, and the stirring reaction time is 1-20 hours.
3. The method according to claim 1, wherein the oxidizing agent is at least one of hydrogen peroxide, perbenzoic acid, peracetic acid, m-chloroperbenzoic acid, t-butyl peroxide, benzoyl peroxide, and oxygen, and the oxygen has a gas pressure of 1 to 10 atmospheres.
4. The method according to claim 1, wherein the base is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, lithium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium carbonate, potassium phosphate, sodium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, pyridine, 4-methylpyridine, trimethylamine, triethylamine, tributylamine, azamethylmorpholine, diisopropylethylamine, and 1, 8-diazabicycloundecen-7-ene.
5. The method according to claim 1, wherein the solvent is water, methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, acetonitrile, acetone, butanone, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, benzene, toluene, xylene, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, dimethylformamide, or dimethyl sulfoxide.
6. The preparation method according to claim 1, wherein the equivalent ratio of the cyclohexene to the oxidant is 1: 1-1: 20; the weight ratio of the accelerator to the cyclohexene is 1: 100-20: 100.
7. The method according to claim 1, wherein the residue of step (2) is washed with a solvent and reused as a reaction promoter, and a washing solution is combined with the filtrate.
8. The preparation method according to claim 1, wherein the reaction solution obtained in the step (3) is subjected to vacuum rectification and collected to obtain 2-cyclohexen-1-one.
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