CN102603447A - Method for preparing organic lactone - Google Patents

Abstract

The invention provides a method for preparing organic lactone. It is characterized in that cubic cobalt tetroxide is used as catalyst, and the catalyst is prepared by hydrothermal method; organic ketone is used as substrate, oxygen or air is used as oxygen source, organic aldehydes are used as reducing agent, and organic solvent is added to the reaction system. The method has the advantages of simple preparation of the catalyst; mild reaction conditions, safety, reliability, and environmental protection; the selectivity and yield of the obtained target product are close to 100%; the catalyst can be reused many times. The method solves the disadvantages of poor safety and low yield in the traditional preparation process of lactone, and has good industrial application prospects.

Description

A kind of method for preparing organic lactone

【Technical field】

The invention relates to the field of industrial catalysis in the petrochemical industry, in particular to a catalytic method for preparing organic lactones by oxidation of organic ketones.

【Background technique】

Organic lactone is an important organic synthesis intermediate, mainly used in the synthesis of polyester and copolymerization or blending modification with other esters, for example, polyε-caprolactone (PCL) is derived from ε-caprolactone (CL ) Linear aliphatic polyester obtained by ring-opening polymerization. Lactone can also be used as a strong solvent to dissolve many polymer resins, and has good solubility for some insoluble resins. For example, caprolactone can dissolve chlorinated polyolefin resins and "ESTANE" polyurethane resins.

So far, the synthesis of organic lactones has problems in raw material quality, production safety and product stability, and the synthesis technology is difficult. Currently, only a few companies in the United States, Britain, Japan and other countries are producing, and my country mainly relies on imports.

In recent years, with the continuous expansion of the application fields of organic lactones (especially ε-caprolactone), the market demand has also been increasing, and the development of lactone synthesis technology has also received more and more attention. The synthesis methods of organic lactones reported in the literature mainly include peroxyacid oxidation, low concentration H2O2, O2/air, etc. as oxidants to oxidize cyclohexanone to synthesize lactones and biological oxidation. However, these methods generally do not use catalysts, and the efficiency is very low; even if some catalysts are used, the activity and selectivity of the catalysts are very low, and the catalysts are difficult to recycle.

In view of the shortcomings of the existing organic lactone synthesis process, the industry is focusing on the design and development of an efficient method and catalyst for the oxidation of organic ketones to prepare organic lactones with strong development and application prospects.

【Content of invention】

The object of the present invention is to provide a method for preparing organic lactones by catalytic oxidation of organic ketones, so as to overcome the above-mentioned defects in the prior art.

In order to achieve the purpose of the invention, the present invention proposes the following technical solutions:

A method for preparing organic lactones by catalytically oxidizing organic ketones, comprising the steps of: taking a reaction amount of catalyst, organic ketones, organic aldehydes and organic solvents and mixing them in a reactor; introducing oxygen, stirring at room temperature to After reacting at 100°C for 0.5-10 hours, the target product lactone can be obtained.

In the above method for preparing organic lactones, the catalyst used is cubic cobalt tetroxide.

In the above-mentioned organic lactone preparation method, also comprise the step of pre-preparing catalyst cubic cobalt trioxide, comprising:

S1. get the inorganic alkaline substance (such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, ammoniacal liquor, sodium hydroxide, potassium hydroxide) and P123 template agent (ie EO ₂₀ PO ₇₀ EO ₂₀ , wherein EO is ethoxy, PO is propoxy) dissolved in deionized water to form a solution;

S2. get the cobalt salt of reaction amount (as cobalt nitrate, cobalt chloride, cobalt acetate etc.) be dissolved in deionized water and be made into the aqueous solution containing cobalt ion;

S3. Under vigorous stirring, add the aqueous solution containing cobalt ions dropwise into the solution containing template agent and inorganic base (pH=7 or so after dropping), and continue stirring for 0.5 hours after dropping;

S4. Pour the above solution into a reaction kettle, and crystallize at 180° C. for 24 hours;

S5. Wash the precipitate three times with deionized water, dry it at 80° C., and calcinate it at 300° C. for 2 hours to obtain the catalyst.

In the above-mentioned organic lactone preparation method, organic ketone refers to cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, etc.

In the above-mentioned preparation method of organic lactone, organic aldehyde refers to acetaldehyde, butyraldehyde, benzaldehyde, o-chlorobenzaldehyde, p-chlorobenzaldehyde and the like.

In the above method for preparing organic lactones, the organic solvent refers to acetonitrile, ethyl acetate, 1,2-dichloroethane, chloroform, tetrachloromethane and the like.

In the above-mentioned organic lactone preparation method, the mass ratio of catalyst and organic ketone is [0.01-0.2]: 1, the molar ratio of organic aldehyde and organic ketone is [1-4]: 1, and the molar ratio of oxygen and organic ketone is [ 1-50]:1.

Preferably, in the above method for preparing the organic lactone, the temperature of the reaction system is controlled at 30-80° C. and the reaction is continued for 2-5 hours.

The method for preparing lactone by catalytic oxidation of ketone provided by the invention has a mild and easy-to-control reaction process. While obtaining high yield and selectivity, the method is safe, environmentally friendly, and the catalyst used is cheap, simple to prepare, high in stability, and can be reused many times, so it has good industrial application prospects.

【Brief description of the drawings】

Figure 1 is an electron micrograph of cubic cobalt tetroxide provided in the present invention.

【Detailed ways】

The present invention will be further described below in conjunction with the embodiments of the present invention and comparative examples:

1. Catalyst preparation

The catalyst used in the following examples of the present invention is all prepared by following method:

Dissolve 7.56 g of sodium bicarbonate and 4 g of template agent P123 in 600 ml of deionized water to form a solution; dissolve 26.2 g of cobalt nitrate hexahydrate in 240 ml of deionized water to form a cobalt nitrate solution. Under vigorous stirring, the cobalt nitrate solution was added dropwise to the solution containing the P123 template agent and sodium bicarbonate (pH = about 7 after the drop), and continued to stir for 0.5 hours after the drop. Then it was poured into the reactor and crystallized at 180°C for 24 hours. Finally, the precipitate was washed three times with deionized water, dried at 80°C, and calcined at 300°C for 2 hours to obtain cubic cobalt tetroxide. The electron micrograph is shown in Figure 1.

In the above steps, other inorganic bases such as potassium bicarbonate, potassium carbonate, sodium carbonate, ammonia, sodium hydroxide, potassium hydroxide, etc. can be used to replace sodium bicarbonate; other cobalt salts such as cobalt chloride, cobalt acetate, etc. can also be used to replace Cobalt nitrate can also be prepared into cubic cobalt tetroxide.

2. Testing and Analysis

The structural analysis of the reaction product in the following examples and comparative examples of the present invention adopts the gas phase-mass spectrometer coupled instrument GC/MS (6890N/ 5973N). The analysis of target product selectivity and yield was carried out by Agilent GC 7820A gas chromatograph equipped with hydrogen flame detector and AB-FFAP capillary column (30m×0.25mm×0.25μm) produced by Agilent.

3. Embodiment

Example 1

In the three-necked glass bottle, add successively 0.5 grams of the above-mentioned cubic cobalt tetraoxide catalyst synthesized, 10 grams of cyclopentanone, 10 grams of benzaldehyde and 200 milliliters of carbon tetrachloride, feed oxygen, and the flow rate of oxygen is 100 milliliters/minute, while stirring After reacting at 40° C. for 3 hours, gas chromatography-mass spectrometry analysis results showed that the product was the target product valerolactone, and gas chromatography analysis results showed that the selectivity and yield of valerolactone were 100% and 99%, respectively. After the catalyst was recycled 10 times, the selectivity and yield of valerolactone were still 100% and 99.2%, respectively.

Example 2

Add 0.2 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of cyclohexanone, 20 grams of butyraldehyde and 200 milliliters of 1,2-dichloroethane in the three-necked glass bottle successively, and feed oxygen at a flow rate of 200 milliliters/ Minutes, after stirring for 1 hour at 80°C, the gas chromatography-mass spectrometry analysis results showed that the product was the target product caprolactone, and the gas chromatography analysis results showed that the selectivity and yield of caprolactone were 100% respectively and 99.5%.

Example 3

Add 0.8 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of 2-methylcyclohexanone, 40 grams of p-chlorobenzaldehyde and 200 milliliters of acetonitrile into the three-necked glass bottle successively, and feed oxygen at a flow rate of 400 milliliters/minute , after reacting at 30°C under stirring for 9 hours, the gas chromatography-mass spectrometry analysis results showed that the product was the target product 2-methylcaprolactone, and the gas chromatography analysis results showed that the selectivity of 2-methylcaprolactone and yields are both 100%.

Example 4

Add 1.0 g of the above-mentioned cubic cobalt tetroxide catalyst, 10 g of 3-methylcyclohexanone, 30 g of p-chlorobenzaldehyde, and 200 ml of acetonitrile into the three-necked glass bottle, and feed oxygen at a flow rate of 300 ml/min. , after reacting at 60°C under stirring for 5 hours, the gas chromatography-mass spectrometry analysis results showed that the product was the target product 3-methylcaprolactone, and the gas chromatography analysis results showed that the selectivity of 3-methylcaprolactone and yields were 100% and 99.6%, respectively.

Example 5

Add 1.5 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of 4-methylcyclohexanone, 20 grams of butyraldehyde and 200 milliliters of chloroform into the three-necked glass bottle successively, and feed oxygen at a flow rate of 150 milliliters/ Minutes, after reacting for 10 hours at 40°C under stirring, the gas chromatography-mass spectrometry analysis results showed that the product was the target product 4-methylcaprolactone, and the gas chromatography analysis results showed that the selection of 4-methylcaprolactone The yield and yield were 100% and 99.8%, respectively.

Example 6

Add 1.2 grams of the above-mentioned cube-shaped cobalt tetroxide catalyst, 10 grams of 2-methylcyclopentanone, 20 grams of benzaldehyde and 200 milliliters of 1,2-dichloroethane in sequence in the three-necked glass bottle, and feed oxygen at a rate of Be 50 milliliters/minute, after reacting at 80 ℃ under stirring for 2 hours, gas chromatography-mass spectrometry analysis result shows that product is target product 2-methylvalerolactone, and gas chromatography analysis result shows that 2-methylvalerolactone The selectivity and yield of lactone were 100% and 99.5%, respectively.

Example 7

Add 0.4 g of the above-mentioned cubic cobalt tetroxide catalyst, 10 g of 3-methylcyclopentanone, 30 g of p-benzaldehyde, and 200 ml of carbon tetrachloride in sequence in a three-necked glass bottle, and feed oxygen at a flow rate of 140 ml. /min, after reacting at 60 DEG C under stirring for 3 hours, the gas chromatography-mass spectrometry analysis result shows that the product is the target product 3-methylvalerolactone, and the gas chromatography analysis result shows that the content of 3-methylvalerolactone Both selectivity and yield are 100% and 100%.

Example 8

Add 0.3 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of 4-methylcyclopentanone, 30 grams of o-benzaldehyde and 200 milliliters of ethyl acetate in the three-necked glass bottle successively, and feed oxygen at a flow rate of 250 milliliters/ Minutes, after reacting for 2 hours at 50°C under stirring, the gas chromatography-mass spectrometry analysis results showed that the product was the target product 4-methylvalerolactone, and the gas chromatography analysis results showed that the selection of 4-methylvalerolactone The yield and yield were 100% and 99.5%, respectively. After the catalyst was recycled 10 times, the selectivity and yield of 4-methylvalerolactone were still 100% and 99.4%, respectively.

Example 9

In the three-necked glass bottle, add 0.4 grams of the above-mentioned synthesized cubic cobalt trioxide catalyst, 10 grams of 2-methylcyclopentanone, 20 grams of butyraldehyde and 200 milliliters of carbon tetrachloride, and feed oxygen at a flow rate of 150 milliliters/ Minutes, after reacting for 3 hours at 60°C under stirring, the gas chromatography-mass spectrometry analysis results showed that the product was the target product 2-methylvalerolactone, and the gas chromatography analysis results showed that the selection of 2-methylvalerolactone The yield and yield were 100% and 99.4%, respectively.

Example 10

Add 0.5 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of 3-methylcyclopentanone, 25 grams of p-chlorobenzaldehyde and 200 milliliters of acetonitrile into the three-necked glass bottle successively, and feed oxygen at a flow rate of 300 milliliters/minute , after reacting at 80°C under stirring for 2 hours, the gas chromatography-mass spectrometry analysis results showed that the product was the target product 3-methylvalerolactone, and the gas chromatography analysis results showed that the selectivity of 3-methylvalerolactone and yields were 100% and 99.4%, respectively.

Example 11

Add successively 1.2 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of cyclopentanone, 15 grams of benzaldehyde and 200 milliliters of acetonitrile in the three-necked glass bottle, feed oxygen, and the oxygen flow rate is 120 milliliters/minute, under stirring at 70 After reacting at ℃ for 2 hours, the gas chromatography-mass spectrometry analysis results showed that the product was the target product valerolactone, and the gas chromatography analysis results showed that the selectivity and yield of valerolactone were 100% and 99.6%, respectively.

Example 12

Add 0.9 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of cyclopentanone, 8 grams of acetaldehyde and 200 milliliters of 1,2-dichloroethane in the three-necked glass bottle successively, and feed oxygen at an oxygen flow rate of 80 milliliters/ Minutes, after reacting at 50 DEG C under stirring for 4 hours, gas chromatography-mass spectrometry analysis results showed that the product was the target product valerolactone, and the gas chromatography analysis results showed that the selectivity and yield of valerolactone were 100%. .

Example 13

In the three-necked glass bottle, add successively 1.5 grams of the above-mentioned cubic cobalt tetraoxide catalyst synthesized, 10 grams of cyclopentanone, 25 grams of p-chlorobenzaldehyde and 200 milliliters of carbon tetrachloride, feed oxygen, and the oxygen flow rate is 250 milliliters/minute, After reacting at 60° C. under stirring for 2 hours, the gas chromatography-mass spectrometry analysis results showed that the product was the target product valerolactone, and the gas chromatography analysis results showed that the selectivity and yield of valerolactone were 100% and 99.8% respectively. %.

Example 14

In the three-necked glass bottle, add 1.0 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of cyclohexanone, 250 grams of benzaldehyde and 200 milliliters of 1,2-dichloroethane successively, and feed oxygen at a flow rate of 150 milliliters/ Minutes, after reacting at 80 ℃ under stirring for 2 hours, gas chromatography-mass spectrometry analysis results show that the product is the target product caprolactone, and gas chromatography analysis results show that the selectivity and yield of caprolactone are 100% respectively and 99.6%.

Example 15

In the three-necked glass bottle, add 0.4 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of 2-methylcyclopentanone, 15 grams of benzaldehyde and 200 milliliters of carbon tetrachloride successively, feed oxygen, and the oxygen flow rate is 100 milliliters/ Minutes, after reacting for 4 hours at 30°C under stirring, the gas chromatography-mass spectrometry analysis results showed that the product was the target product 2-methylvalerolactone, and the gas chromatography analysis results showed that the selection of 2-methylvalerolactone The yield and yield were 100% and 99.5%, respectively.

Example 16

Add 1.2 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of 4-cyclopentanone, 25 grams of p-chlorobenzaldehyde and 200 milliliters of ethyl acetate into the three-necked glass bottle successively, and feed oxygen at an oxygen flow rate of 200 milliliters/minute , after reacting at 60°C under stirring for 2 hours, the gas chromatography analysis results showed that the gas chromatography-mass spectrometry analysis results showed that the product was the target product 4-valerolactone, and the selectivity and yield of 4-valerolactone were respectively for 100% and 99.8%.

Example 17

In the three-necked glass bottle, add successively 0.8 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of cyclohexanone, 30 grams of benzaldehyde and 200 milliliters of carbon tetrachloride, feed oxygen, and the flow rate of oxygen is 120 milliliters/minute. After reacting at 50° C. for 3 hours, gas chromatography-mass spectrometry analysis results showed that the product was the target product caprolactone, and gas chromatography analysis results showed that the selectivity and yield of caprolactone were 100% and 99.8%, respectively.

Example 18

In the three-necked glass bottle, add 1.2 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of 2-methylcyclohexanone, 35 grams of p-chlorobenzaldehyde and 200 milliliters of 2-dichloroethane, and feed oxygen into the three-necked glass bottle. The flow rate of oxygen is 120 ml/min. After reacting at 70° C. for 1 hour under stirring, the gas chromatography-mass spectrometry analysis results show that the product is the target product 2-methylcaprolactone, and the gas chromatography analysis results show that 2-methylcaprolactone The selectivity and yield of caprolactone were 100% and 99.0%, respectively.

Example 19

In the three-necked glass bottle, add 0.4 grams of the above-mentioned cubic cobalt tetraoxide catalyst, 10 grams of 2-methylcyclohexanone, 20 grams of acetaldehyde and 200 milliliters of carbon tetrachloride successively, and feed oxygen at a flow rate of 100 milliliters/ Minutes, after reacting for 3 hours at 50°C under stirring, the target product 2-methylcaprolactone was obtained, and the gas chromatography analysis results showed that the selectivity and yield of 2-methylcaprolactone were 100% and 99.4% respectively. %.

Example 20

Add 0.4 grams of the above-mentioned cubic cobalt tetroxide catalyst, 10 grams of 2-methylcyclohexanone, 25 grams of benzaldehyde, and 200 milliliters of dichlorodiethane into the three-necked glass bottle successively, and feed oxygen at a flow rate of 120 milliliters. /min, after reacting at 45 DEG C under stirring for 7 hours, the gas chromatography-mass spectrometry analysis result shows that the product is the target product 2-methylcaprolactone, and the gas chromatography analysis result shows that the content of 2-methylcaprolactone The selectivity and yield were 100% and 99.6%, respectively.

3. Comparative example

In order to further illustrate the superiority of the catalyst of the present invention, the following catalysts are selected as comparative examples.

Comparative example 1

Add 0.4 grams of commercially available cobalt trioxide catalyst, 10 grams of 2-methylcyclohexanone, 20 grams of acetaldehyde and 200 milliliters of 1,2-dichloroethane in turn into a three-necked glass bottle, and feed oxygen at a flow rate of 100 milliliters /min, after reacting at 50 DEG C under stirring for 3 hours, the gas chromatography-mass spectrometry analysis result showed that the product was the target product 2-methylcaprolactone, and the gas chromatography analysis result showed that the content of 2-methylcaprolactone The selectivity and yield were 95% and 65%, respectively.

Comparative example 2

Add 0.4 grams of commercially available antimony trioxide, 10 grams of 2-methylcyclohexanone, 20 grams of acetaldehyde and 200 milliliters of 1,2-dichloroethane successively into a three-necked glass bottle, and feed oxygen at a flow rate of 100 ml/min, after stirring at 50 DEG C for 3 hours, the gas chromatography-mass spectrometry analysis result showed that the product was the target product 2-methylcaprolactone, and the gas chromatography analysis result showed that 2-methylcaprolactone The selectivity and yield of ester were 95% and 30.6%, respectively.

Comparative example 3

Add 0.4 grams of commercially available dichromium trioxide, 10 grams of 2-methylcyclohexanone, 20 grams of acetaldehyde and 200 milliliters of 1,2-dichloroethane successively in the three-necked glass bottle, feed oxygen, and the flow rate of oxygen is 100 ml/min, after stirring at 50 DEG C for 3 hours, the gas chromatography-mass spectrometry analysis result showed that the product was the target product 2-methylcaprolactone, and the gas chromatography analysis result showed that 2-methylcaprolactone The selectivity and yield of ester were 90% and 20.6%, respectively.

Can find out by above-mentioned embodiment and comparative example, do not adopt in the comparative example of catalyst of the present invention, the selectivity and yield of target product lactone are all lower, and adopt catalyst of the present invention, have reduced reaction condition, make reaction process Gentle and easy to control. In addition, the catalyst is cheap and easy to obtain, simple to prepare, high in stability, and can be repeatedly used to reduce costs.

The above-mentioned embodiments only express several implementation modes of the present invention, and the description thereof is relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (8)

1. A method for preparing organic lactones by catalytic oxidation of organic ketones, comprising the steps of: Get the catalyst of reaction amount, organic ketone, organic aldehyde and organic solvent and place in reaction container, mix; Introduce oxygen into the reaction system, and react at 25-100° C. for 0.5-10 hours under stirring to obtain the obtained product. 2. The method for preparing organic lactones by catalytic oxidation of organic ketones according to claim 1, wherein the catalyst is cubic cobalt tetroxide. 3. the method for preparing organic lactone by organic ketone catalytic oxidation according to claim 2, is characterized in that, also comprises the step of pre-preparing catalyst cubic cobalt trioxide, comprising: S1. Dissolve the inorganic alkaline substance and P123 template agent of the reaction amount in deionized water to form a solution; S2. take the cobalt salt of reaction amount and be dissolved in deionized water and be made into the aqueous solution containing cobalt ion; S3. Under vigorous stirring, the aqueous solution containing cobalt ions is added dropwise to the solution containing template agent and inorganic base; S4. Pour the above solution into the reaction kettle for crystallization; S5. The precipitate is washed with deionized water, dried and calcined to obtain the catalyst. 4. according to the method for preparing organic lactone by organic ketone catalytic oxidation described in any one of claim 1-3, it is characterized in that, described organic ketone is cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone Cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone or 4-methylcyclohexanone. 5. according to the method for preparing organic lactone by organic ketone catalytic oxidation described in any one of claim 1-3, it is characterized in that, described organic aldehyde is acetaldehyde, butyraldehyde, benzaldehyde, o-chlorobenzaldehyde or p- Chlorobenzaldehyde. 6. according to the method for preparing organic lactone by organic ketone catalytic oxidation described in any one of claim 1-3, it is characterized in that, described organic solvent is acetonitrile, ethyl acetate, 1,2-dichloroethane, Chloroform or tetrachloromethane. 7. The method for preparing organic lactones by catalytic oxidation of organic ketones according to any one of claims 1-3, characterized in that the mass ratio of the catalyst to the organic ketones is [0.01-0.2]: 1, and the organic aldehyde The molar ratio of oxygen to organic ketone is [1-4]:1, and the molar ratio of oxygen to organic ketone is [1-50]:1. 8. The method for preparing organic lactones by catalytic oxidation of organic ketones according to any one of claims 1-3, characterized in that the temperature of the reaction system is preferably controlled at 30-80°C and the reaction is continued for 2-5 hours.

Images