CN112479844A - Preparation method of pseudo ionone - Google Patents
Preparation method of pseudo ionone Download PDFInfo
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- CN112479844A CN112479844A CN202011302917.9A CN202011302917A CN112479844A CN 112479844 A CN112479844 A CN 112479844A CN 202011302917 A CN202011302917 A CN 202011302917A CN 112479844 A CN112479844 A CN 112479844A
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- activated carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a preparation method of a vitamin A intermediate pseudo ionone. The method relates to a reaction for preparing pseudo ionone by using a novel catalyst to catalyze the condensation of acetone and citral, the use of the novel catalyst can effectively reduce the consumption of acetone in the reaction, reduce the self-polymerization and copolymerization of the citral and the pseudo ionone in the reaction, and improve the reaction selectivity and yield.
Description
Technical Field
The invention belongs to the field of chemical intermediate synthesis, and particularly relates to a preparation method of a heterogeneous catalyst and a method for preparing pseudo ionone by condensation of acetone and citral catalyzed by the heterogeneous catalyst.
Background
Pseudoionone (pseudoionone), namely 6, 10-dimethyl-3, 5, 9-undecatrien-2-one, is an important intermediate for synthesizing important flavors and fragrances alpha-and beta-ionone, vitamin A, E and other pharmaceutical and chemical products. The general method for industrially producing ionone is to make Citral (Citral) and Acetone (Acetone) undergo the ketoaldehyde condensation reaction in the aqueous solution of NaOH to produce pseudo ionone. One molecule of citral and one molecule of acetone are subjected to claisen-Schmidt ketoaldehyde condensation reaction under an alkaline condition to generate one molecule of pseudoionone and one molecule of water. Most of the ketone-aldehyde condensation reactions have lower activation energy, so that the process has more side reactions, poorer selectivity and difficult product purification.
The reported literature relates to a lot of catalysts for condensation reaction of acetone and citral, which are mainly divided into two categories, one category is homogeneous catalyst, such as sodium hydroxide, potassium hydroxide, primary amine, secondary amine and the like, the catalysts can be dissolved in a reaction system and can complete condensation reaction in a short time, but the reaction degree is not controllable, self-polymerization and copolymerization reaction between citral and pseudo ionone are greatly generated in the reaction process, the reaction selectivity is poor, and the general reaction yield is low<80 percent; another class is heterogeneous catalysts using a variety of supports such as molecular sieves, activated carbon, basic Al2O3And ZrO2The catalysts load alkaline hydroxides such as NaOH and LiOH, the reaction time is prolonged, the reaction selectivity is properly improved, but the generation of a large amount of side reactions cannot be avoided, the acetone dosage in the process system is greatly increased, and the reaction selectivity is generally 80-90%.
The above methods all have corresponding defects, and various problems exist when the method is used for industrial amplification, such as excessive acetone consumption, difficult industrial amplification, low reaction selectivity, low product purity and the like. Therefore, it is necessary to develop a new reaction system for catalyzing the condensation of acetone and citral to prepare the pseudo ionone.
Disclosure of Invention
The invention aims to provide a preparation method of pseudo ionone, which is used for preparing the pseudo ionone by condensing acetone and citral under the catalysis of a new catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of pseudo ionone comprises the step of carrying out condensation reaction on acetone and citral under the catalysis of guanidine modified activated carbon as a catalyst to obtain the pseudo ionone.
In the invention, the preparation method of the guanidine modified activated carbon comprises the following steps:
(1) modifying the activated carbon by using guanidinium, and reacting rich acidic functional groups on the surface of the activated carbon with guanidine basic NH bonds to obtain activated carbon with guanidinium;
(2) after the guanidine modified activated carbon is calcined at high temperature and is perforated, ammonia gas is used for activating the catalyst at the temperature of 100-200 ℃ to obtain a novel catalyst;
in the invention, the activated carbon in the step (1) is selected from one or more of shell activated carbon, coconut shell activated carbon and wood activated carbon, and the shell activated carbon is preferred.
In the invention, in the step (1), the guanidine salt is selected from one or more of guanidine hydrobromide, guanidine hydroiodide, aminoguanidine nitrate, guanidine sulfate, guanidine phosphate and guanidine carbonate, preferably guanidine carbonate, and the mass ratio of guanidine salt to activated carbon is (0.1-1): 1, preferably (0.3-0.5): 1.
in the invention, because the acidic functional groups on the surface of the activated carbon comprise carboxyl and hydroxyl, the guanidine salt is used for modifying the activated carbon in a segmented way in the step (1), wherein the modification temperature of the carboxyl functional groups can be-30-0 ℃, preferably-10-5 ℃, and the modification time is 1-5h, preferably 2-3 h; the modification temperature of the hydroxyl functional group needs to be carried out at a higher temperature, preferably 80-120 ℃, more preferably 100-110 ℃, and the modification time is 10-20h, preferably 15-18 h.
In the present invention, preferably, the modification of the activated carbon by the guanidine salt in step (1) needs to be performed in a solvent selected from the group consisting of toluene, xylene, ethylene glycol, N-dimethylformamide and alkanes having more than 8 carbon atoms, preferably N, N-dimethylformamide. The mass ratio of the solvent to the active carbon is (10-50): 1, preferably (15-20): 1.
in the invention, the guanidine-modified activated carbon in the step (2) needs to be calcined at a high temperature of 500-800 ℃, preferably 600-650 ℃ for opening the pores; the calcination time is 8-20h, preferably 10-15 h.
In the invention, after the guanidine modified activated carbon in the step (2) is calcined and perforated, NH is carried out when the guanidine modified activated carbon is hot3Activating, and performing programmed cooling on the calcined activated carbon at a cooling rate of 5-10 ℃/min, preferably 6-8 ℃/min;cooling to 100-200 deg.C, preferably 120-150 deg.C for NH3Activating; NH (NH)3The flow rate is 0.5-3mL/min, preferably 1-2 mL/min; the activation time is 5-15h, preferably 8-10 h.
In the condensation reaction of acetone and citral, the mass ratio of the catalyst to the citral is (0.01% -1%): 1, preferably (0.05% to 0.1%): 1.
in the invention, the molar ratio of acetone to citral in the condensation reaction of acetone and citral is (2-5): 1, preferably (3-3.5): 1.
in the present invention, the reaction temperature for the condensation reaction of acetone and citral is 20-100 deg.C, preferably 40-60 deg.C; the reaction time is 1-5h, preferably 2-3 h.
In the invention, after the condensation reaction of acetone and citral is finished, the reaction solution is filtered, and the catalyst can be continuously reused after being washed by acetone.
The invention has the positive effects that:
the use of the novel catalyst allows the acetone consumption in the condensation reaction of acetone and citral to be greatly reduced, preferably to be less than 3.5:1 for acetone and citral, significantly lower than the molar ratio of > 10:1 in the known art, and the self-polymerization and copolymerization reactions of citral and pseudoionone are inhibited, with a substantial increase in the reaction selectivity and yield (> 95%).
Detailed Description
The technical solutions of the present invention are further described below, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the scope of the technical solutions of the present invention.
Gas chromatographic analysis: the chromatographic type is as follows: shimadzu WAX 1701.42249; carrier gas: high-purity nitrogen; sample introduction mode: an autosampler; nitrogen flow rate: 65.0 ml/min; vaporization chamber temperature: 260 ℃; split-flow sample introduction, split-flow ratio: 1: 30, of a nitrogen-containing gas; sample introduction amount: 0.5 mul; the column flow rate was 1.5 ml/min; column temperature: first-order temperature programming, wherein the initial temperature is 80 ℃, the temperature is kept for 2 minutes, then the temperature is increased to 220 ℃ at the speed of 10 ℃/min, and the temperature is kept for 15 minutes; the total running time is 28.66 min; the temperature of the detector is 280 ℃; and (4) quantifying by using an internal standard method, namely tetradecane serving as an internal standard substance.
Some of the reagent specifications and sources in the examples and comparative examples
| Name of reagent | Reagent specification | Manufacturer of the product |
| Husk activated carbon | Industrial grade | Carbot (Cabot) |
| Guanidine carbonate, guanidine phosphate, guanidine hydrobromide | AR | Aladdin reagent |
| Acetone, N-dimethylformamide and toluene | AR | Reagent for treating west longas |
Example 1
(1) Modification of activated carbon: adding 10g of activated carbon, 150g N, N-dimethylformamide and magnetons into a 500mL three-neck flask, cooling to-10 ℃, adding 3g of guanidine carbonate, stirring at-10 ℃ for 2h, heating to 100 ℃, reacting at 100 ℃ for 15h, cooling to room temperature after the reaction is finished, filtering, and washing the activated carbon with 50mL of N, N-dimethylformamide.
(2) Activating modified activated carbon:
and (2) putting 10g of modified activated carbon into a muffle furnace, calcining at 600 ℃ for 10h, then carrying out programmed cooling, wherein the cooling rate is 6 ℃/min, cooling to 120 ℃, keeping the temperature of 120 ℃, introducing ammonia gas, introducing 1mL/min of ammonia gas flow, activating for 8h, cooling the muffle furnace to room temperature, replacing the interior of the muffle furnace with nitrogen gas, and taking out the catalyst for later use.
Condensation reaction:
100g (0.657mol) of citral, 114.3g (1.971mol) of acetone and 0.05g of catalyst are added into a 500mL three-neck flask, the reaction solution is heated to 40 ℃ and reacts for 2 hours at 40 ℃, and a sample is taken for gas phase analysis, so that the conversion rate of the citral is 99.88%, the selectivity of the pseudo violet is 96.74% and the yield is 96.62%.
The catalyst is mechanically used:
the reaction solution was filtered, and the catalyst was washed with 20mL of acetone, and then the catalyst was used as a catalyst for further experiments, and the results were repeated 10 times as follows:
| number of times of application | Citral conversion/%) | Pseudoionone selectivity/%) | Yield/% |
| 0 | 99.88 | 96.74 | 96.62 |
| 1 | 99.79 | 96.74 | 96.54 |
| 2 | 99.77 | 97.23 | 97.01 |
| 3 | 99.73 | 98.01 | 97.75 |
| 4 | 99.80 | 96.89 | 96.70 |
| 5 | 99.88 | 97.77 | 97.65 |
| 6 | 99.91 | 97.22 | 97.13 |
| 7 | 99.70 | 97.54 | 97.25 |
| 8 | 99.65 | 98.54 | 98.20 |
| 9 | 99.69 | 98.09 | 97.79 |
| 10 | 99.83 | 98.84 | 98.67 |
Example 2
(1) Modification of activated carbon: adding 10g of activated carbon, 200g N, N-dimethylformamide and magnetons into a 500mL three-neck flask, cooling to-5 ℃, adding 5g of guanidine carbonate, stirring at-5 ℃ for 3h, heating to 110 ℃, reacting at 110 ℃ for 18h, cooling to room temperature after the reaction is finished, filtering, and washing the activated carbon with 50mL of N, N-dimethylformamide.
(2) Activating modified activated carbon:
and (2) putting 10g of modified activated carbon into a muffle furnace, calcining at 650 ℃ for 15h, then carrying out programmed cooling at a cooling rate of 8 ℃/min to 150 ℃, keeping the temperature at 150 ℃, introducing ammonia gas at a flow rate of 2mL/min, activating for 10h, cooling the muffle furnace to room temperature, replacing the interior of the muffle furnace with nitrogen gas, and taking out the catalyst for later use.
Condensation reaction:
100g (0.657mol) of citral, 133.35g (2.30mol) of acetone and 0.10g of catalyst are added into a 500mL three-neck flask, the reaction solution is heated to 60 ℃ and reacts for 3 hours at 60 ℃, and sampling gas-phase analysis shows that the conversion rate of the citral is 99.69%, the selectivity of the pseudo-violet is 97.33% and the yield is 97.03%.
Example 3
(1) Modification of activated carbon: adding 10g of activated carbon, 100g of toluene and magnetons into a 500mL three-neck flask, cooling to-30 ℃, adding 1g of guanidine phosphate, stirring at-30 ℃ for 5h, heating to 120 ℃, reacting at 120 ℃ for 20h, cooling to room temperature after the reaction is finished, filtering, and washing the activated carbon with 50mL of toluene.
(2) Activating modified activated carbon:
and (2) putting 10g of modified activated carbon into a muffle furnace, calcining for 8h at 500 ℃, then carrying out programmed cooling, wherein the cooling rate is 5 ℃/min, cooling to 100 ℃, keeping the temperature at 100 ℃, introducing ammonia gas, the ammonia gas flow is 0.5mL/min, activating for 5h, cooling the muffle furnace to room temperature, replacing the interior of the muffle furnace with nitrogen gas, and taking out the catalyst for later use.
Condensation reaction:
100g (0.657mol) of citral, 76.2g (1.314mol) of acetone and 0.01g of catalyst are added into a 500mL three-neck flask, the reaction solution is heated to 100 ℃ and reacts for 1 hour at 100 ℃, and a sample is taken for gas phase analysis, so that the conversion rate of the citral is 99.74 percent, the selectivity of the pseudo violet is 98.00 percent, and the yield is 97.75 percent.
Example 4
(1) Modification of activated carbon: adding 10g of activated carbon, 500g of dimethylbenzene and magnetons into a 1000mL three-neck flask, cooling to 0 ℃, adding 10g of guanidine hydrobromide, stirring at 0 ℃ for 1h, heating to 80 ℃, reacting at 80 ℃ for 10h, cooling to room temperature after the reaction is finished, filtering, and washing the activated carbon with 50mL of dimethylbenzene.
(2) Activating modified activated carbon:
and (2) putting 10g of modified activated carbon into a muffle furnace, calcining at 800 ℃ for 20h, then carrying out programmed cooling, wherein the cooling rate is 10 ℃/min, cooling to 200 ℃, keeping the temperature at 200 ℃, introducing ammonia gas, the flow of the ammonia gas is 3mL/min, activating for 15h, cooling the muffle furnace to room temperature, replacing the interior of the muffle furnace with the nitrogen gas, and taking out the catalyst for later use.
Condensation reaction:
100g (0.657mol) of citral, 190.5g (3.284mol) of acetone and 1.0g of catalyst are added into a 500mL three-neck flask, the reaction solution is kept at the temperature of 20 ℃ and reacts for 5 hours at the temperature of 20 ℃, and a sample is taken for gas phase analysis, so that the conversion rate of the citral is 99.79 percent, the selectivity of the pseudo-violet is 97.44 percent, and the yield is 97.24 percent.
Comparative example 1
In contrast to example 1, the condensation reaction of citral and acetone was carried out directly using guanidine carbonate as catalyst.
A500 mL three-necked flask was charged with 100g (0.657mol) of citral, 114.3g (1.971mol) of acetone and 0.05g of guanidine carbonate, the reaction mixture was heated to 40 ℃ and reacted at 40 ℃ for 2 hours, and a sample was sampled and analyzed by gas phase analysis to show that the conversion of citral was 99.72%, the selectivity of pseudo violet was 76.74% and the yield was 76.52%.
The comparison shows that when guanidine carbonate is directly used as a catalyst, the conversion rate of citral is similar in the same time, but the selectivity and yield of pseudo violet are greatly reduced, and the gas phase analysis shows that the content of the self-polymerization products of the citral and the pseudo violet is greatly increased.
Claims (10)
1. A preparation method of pseudo ionone is characterized in that acetone and citral are subjected to condensation reaction under the catalysis of guanidine modified activated carbon as a catalyst to obtain the pseudo ionone.
2. The method of claim 1, wherein the guanidine-modified activated carbon is prepared by the steps of:
(1) modifying the activated carbon by using guanidinium, and reacting rich acidic functional groups on the surface of the activated carbon with guanidine basic NH bonds to obtain activated carbon with guanidinium;
(2) after guanidine modified active carbon is calcined at high temperature and is holed, ammonia gas is used for activating the catalyst at 100-200 ℃, and the novel catalyst is obtained.
3. The method according to claim 2, wherein the activated carbon in the step (1) is one or more selected from the group consisting of husk activated carbon, coconut shell activated carbon and wood activated carbon, preferably husk activated carbon.
4. The preparation method according to claim 2 or 3, wherein the guanidine salt in step (1) is selected from one or more of guanidine hydrobromide, guanidine hydroiodide, aminoguanidine nitrate, guanidine sulfate, guanidine phosphate and guanidine carbonate, preferably guanidine carbonate, and/or the mass ratio of guanidine salt to activated carbon is (0.1-1): 1, preferably (0.3-0.5): 1.
5. the process according to any one of claims 2 to 4, wherein in step (1), the modification is carried out in stages, first at-30 to 0 ℃, preferably-10 to-5 ℃, for 1 to 5 hours, preferably 2 to 3 hours; then modified at 80-120 deg.C, more preferably 100-110 deg.C for 10-20h, preferably 15-18 h.
6. The method according to any one of claims 2 to 4, wherein in the step (1), the modification of the activated carbon by the guanidine salt is carried out in a solvent selected from the group consisting of toluene, xylene, ethylene glycol, N-dimethylformamide and alkanes having a carbon number greater than 8, preferably N, N-dimethylformamide; and/or the mass ratio of the solvent to the activated carbon is (10-50): 1, preferably (15-20): 1.
7. the preparation method according to any one of claims 2-6, characterized in that the calcination temperature of the high-temperature calcination in step (2) is 500-800 ℃, preferably 600-650 ℃; the calcination time is 8-20h, preferably 10-15 h.
8. The process according to any one of claims 2 to 7, wherein the calcined activated carbon in step (2) is subjected to programmed cooling at a cooling rate of 5 to 10 ℃/min, preferably 6 to 8 ℃/min; cooling to 100-200 deg.C, preferably 120-150 deg.C for NH3Activating; NH (NH)3The flow rate is 0.5-3mL/min, preferably 1-2 mL/min; the activation time is 5-15h, preferably 8-10 h.
9. The process according to any one of claims 1 to 8, characterized in that the mass ratio of the catalyst used to the citral is (0.01% to 1%): 1, preferably (0.05% to 0.1%): 1.
10. the process according to any one of claims 1 to 9, wherein the molar ratio of acetone to citral is (2-5): 1, preferably (3-3.5): 1; and/or the reaction temperature of the condensation reaction is 20-100 ℃, preferably 40-60 ℃; the reaction time is 1-5h, preferably 2-3 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113372210A (en) * | 2021-06-08 | 2021-09-10 | 万华化学集团股份有限公司 | Preparation method of beta-ionone |
| CN113698284A (en) * | 2021-09-02 | 2021-11-26 | 上海万香日化有限公司 | Synthesis method of pseudo ionone |
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2020
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113372210A (en) * | 2021-06-08 | 2021-09-10 | 万华化学集团股份有限公司 | Preparation method of beta-ionone |
| CN113372210B (en) * | 2021-06-08 | 2022-04-19 | 万华化学集团股份有限公司 | Preparation method of beta-ionone |
| CN113698284A (en) * | 2021-09-02 | 2021-11-26 | 上海万香日化有限公司 | Synthesis method of pseudo ionone |
| CN113698284B (en) * | 2021-09-02 | 2023-12-12 | 上海万香日化有限公司 | Synthesis method of pseudo ionone |
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