CN113387784A - Acid-base catalyst and application thereof in delta-damascenone synthesis - Google Patents
Acid-base catalyst and application thereof in delta-damascenone synthesis Download PDFInfo
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Abstract
The invention provides an acid-base catalyst and application thereof in delta-damascenone synthesis. The catalyst is a mesoporous material catalyst which is doped with bimetal and modified by organic base, can catalyze acid-base synergistic reaction, is used for catalytically synthesizing delta-damascone, takes 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and paraldehyde as raw materials, can directly generate the target product delta-damascone by adopting a one-pot method, simplifies reaction steps, is simple in catalyst separation and post-treatment processes after the reaction is finished, has pure product fragrance, saves cost, and is beneficial to industrial mass production. Meanwhile, the catalyst provided by the invention has the advantages of good reusability, good environmental protection, no three wastes, short reaction period, simple reaction and subsequent treatment and optimal yield of more than 90%.
Description
Technical Field
The invention relates to the technical field of synthesis, in particular to an acid-base catalyst and application thereof in delta-damascenone synthesis.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Damascone (also known as damascone) compounds have sweet fruit fragrance and flower fragrance of roses, strawberries, apples and the like, and are important aroma components in cigarette smoke. The perfume products of the damascones obtained from natural plants are very limited and very expensive. The damascenone compounds mainly include several forms of alpha-damascenone, beta-damascenone, delta-damascenone and the like. Wherein the delta-damascone has good fragrance like tobacco leaves, roses, apples and beer, can endow the fragrance of the essence with more delicate and pleasant fragrance, and has wide application prospect. However, relatively few reports of delta-damascone synthesis are currently available.
In the US patent No. 4,198,309, ethyl magnesium bromide and N-methylaniline are used as catalysts, 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and acetaldehyde are synthesized into hydroxyketone, and then the hydroxyketone is dehydrated under the action of p-toluenesulfonic acid to obtain the final product delta-damascenone. The process has the disadvantages of complex operation, no application of catalyst, and harsh reaction conditions, such as requirement of anhydrous and oxygen-free environment. The total cost is high, three wastes are more, and the environment is not friendly.
Dengchang et al (J. Synthesis chemistry, 2004(02):157 and 160.) use 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone as raw material, react with ethyl acetate to synthesize diketone under the action of sodium alkoxide or potassium alkoxide, and then reduce the diketone to hydroxyketone under the action of sodium borohydride. The process has long route and low yield (the yield is lower than 20 percent), and has no industrial application value.
Dauben et al (tetrahedron letters,1975, P515-517) use condensation of isopropylidene malonate with acetone, followed by diene cyclization with piperylene, addition of the cyclization product with organometallic lithium allyl, hydrolysis and decarboxylation to obtain delta-damascone. The process has long route and low reaction yield (the reaction is carried out in five steps, and the highest yield of a single-step reaction is 66%).
The Green biological group CN102531865B mentions that under the action of organic bases such as acid-binding agents triethylamine, pyridine, imidazole, diethylamine, and the like, 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone and dimethylchlorosilane react in an organic solvent to obtain an intermediate containing dimethylsiloxy, then the intermediate and acetaldehyde undergo a condensation reaction under the action of a metal salt catalyst, and finally, the product delta-damascenone is obtained after dehydration, wherein the yield is only 62% and the purity is 95%. The method at least comprises three steps of reaction, the steps are long, and the post-treatment and operation are complex. The organic base is directly added into the reaction system, so that the hidden trouble of corroding production equipment exists.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an acid-base catalyst, a preparation method thereof, application thereof in delta-damascone synthesis, and a method for synthesizing delta-damascone by using the acid-base catalyst as a catalyst. The catalyst is a mesoporous material catalyst doped with bimetal and modified with organic base, can catalyze acid-base synergistic reaction, is simple to prepare, is easy to recover, and has good stability. The catalyst is used for catalytically synthesizing delta-damascenone, 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and paraldehyde are used as raw materials, a target product delta-damascenone can be directly generated by adopting a one-pot method, the process is simplified, the yield is high, the post-treatment is simple, and the catalyst can be recycled.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the present invention, the present invention provides a catalyst which is a bimetallic-doped and organic base-modified mesoporous material catalyst comprising a bimetallic active component, a mesoporous material and an organic base.
In some embodiments of the invention, the mesoporous material is a mesoporous silica molecular sieve selected from the group consisting of SBA-15, MCM-41, MCM-48, KIT-6, HMS, FDU-1, MSU-1, ZSM-5. In the embodiments of the present invention, the inventors have also tried to use non-silicon-based mesoporous materials, which mainly include metal oxides, phosphates, sulfides, etc., but in research, it was found that such mesoporous materials have poor thermal stability, and the pore structure is easy to collapse after calcination, and in particular, it is difficult to achieve acid-base co-modification of non-silicon-based mesoporous molecular sieves; compared with the mesoporous silicon molecular sieve, the mesoporous silicon molecular sieve has good mechanical stability and thermal stability, and acid-base modification is easy to realize and operate.
In some embodiments of the invention, the bimetallic active component is selected from any one of the following metal combinations: La-Ti, Nb-V, V-Ti, V-Zr, Ti-Bi, Ti-Sn, Ti-Al, Zr-Al, Zr-Mn, Ti-Mn. The bimetal is mixed in a ratio of 0.5-2: the mole ratio of 1 is combined, so that inorganic functionalization of the mesoporous material can be better realized, and particularly, when the ratio is 1:1, the effect is better. In some embodiments of the present invention, the amount of doping of the selectable bimetal is 5-15% of the molar amount (calculated by silicon) of the mesoporous silicon molecular sieve.
In some embodiments of the invention, the organic base is selected from one or more of Triazabicyclo (TBD), Tetramethylguanidine (TMG), urea (BUN), Ethylenediamine (EDA), Benzylamine (BZA), imidazole (Im), piperazine (PIP), pyrrole (Pyr), adenine (Ade), guanine (Gua), thymine (Thy), cytosine (Cyt), uracil (Ura). The organic base contains nitrogen-containing organic groups, and the nitrogen-containing organic groups can be introduced into the mesoporous material by the organic base modified catalyst to provide basic sites. In some embodiments of the present invention, the organic base can be selectively supported in an amount of 3 to 10% by mole (based on silicon) of the mesoporous silica molecular sieve.
The inventor finds in research that the selection of metal and organic base is most critical to the influence of the catalyst, and particularly the catalyst of the invention has the best catalytic effect when being applied to the reaction of catalyzing the synthesis of delta-damascone by taking 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone and paraldehyde as raw materials and jointly modifying the catalyst by adopting bimetallic doping and organic base.
In a second aspect of the present invention, the present invention provides a method for preparing the catalyst described in the first aspect above, comprising: under an acidic condition, synthesizing the bimetal-doped mesoporous material by one step through an in-situ hydrothermal method, realizing inorganic functionalization of the mesoporous material, and obtaining the bimetal-doped mesoporous material; by a post-grafting method, nitrogen-containing organic groups in organic alkali are introduced into the bimetal-doped mesoporous material to synthesize the bifunctional mesoporous material with a skeleton acid site and a pore passage basic site.
In some embodiments, the methods of the invention comprise: mixing and stirring raw materials for preparing the mesoporous molecular sieve and a metal precursor under an acidic condition for reaction to obtain a bimetal-doped mesoporous material; and (2) performing radical activation on the obtained bimetallic-doped mesoporous material, for example, reacting a chloropropyl-containing substance with the mesoporous material to obtain a chloropropyl-modified mesoporous material, drying the activated and modified material, placing the dried material into a solution containing organic base, stirring and refluxing under the protection of nitrogen, and introducing nitrogen-containing organic radicals into the mesoporous material to obtain the organic base-modified bimetallic-doped mesoporous material.
In the embodiments of the present invention, the inventors found that a bimetal doped mesoporous material is prepared by directly mixing and reacting a molded mesoporous silicon molecular sieve as a raw material with a metal precursor under an acidic condition (such an operation mode belongs to a post-grafting method), in the process, an active component (metal) and the mesoporous material are combined by a silicon hydroxyl group on the surface of the material, a metal atom is loaded on the surface of the molecular sieve through intermolecular force, the combination mode is unstable and easy to run off, and the post-grafting process is easy to cause the blockage and collapse of a pore channel. And the active metal component can be introduced in one step by adopting the in-situ hydrothermal method for direct synthesis, the metal atoms are combined with the mesoporous material through covalent bonds, the operation is simple and easy to implement, and most metal ions can be controlled to enter the framework of the material and be uniformly dispersed.
In the embodiment of the invention, taking SBA-15 and bimetal Nb-V as an example, the method comprises dissolving P123 in 30ml of deionized water, stirring, adding hydrochloric acid into the mixed system, fully stirring, premixing precursors of metal Nb such as butyl niobate and metal V such as vanadium oxychloride and ethyl orthosilicate (TEOS), dropping into the vigorously stirred solution drop by drop, and continuing stirring; and then transferring the formed gel liquid into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven for standing, taking out, performing suction filtration, washing the gel liquid to be neutral by using deionized water, and drying the gel liquid at room temperature. And then roasting the mixture for 4 hours at 550 ℃ in air by using a muffle furnace (the heating rate is 10 ℃/min) to remove the template agent, thus obtaining the bimetal doped mesoporous material, which is recorded as Nb-V-SBA-15. Wherein, P123 (template agent) and Tetraethoxysilane (TEOS) are raw materials for preparing the mesoporous silicon molecular sieve SBA-15. When other mesoporous silicon molecular sieves such as MCM-41, MCM-48, KIT-6, HMS, FDU-1, MSU-1 and ZSM-5 are needed based on the method of the invention, the template agent and raw materials suitable for the mesoporous silicon molecular sieves can be correspondingly selected, and the template agent and the raw materials are all known in the field, and the knowledge in the field is combined on the basis of the disclosure of the invention, so that the method does not need additional creative labor for the technicians in the field.
In the embodiment of the present invention, the catalyst is named in the form of bimetal-mesoporous material-organic base, for example, when the bimetal is Nb-V, the mesoporous material is MCM-41, and the organic base is Ade, the catalyst prepared therefrom is named as Nb-V-MCM-41-Ade.
In a third aspect of the invention, the invention provides the use of a catalyst as described in the first aspect above. The catalyst is a bifunctional mesoporous material simultaneously having a skeleton acid site and a pore passage basic site, and can be applied to catalyzing acid-base synergistic reaction. In some embodiments of the invention, the catalyst of the invention can be applied to catalytic synthesis of delta-damascone, especially to catalytic synthesis of delta-damascone by using 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone and paraldehyde as raw materials.
The catalyst of the invention has the advantages of simple preparation, easy recovery, good stability and no three wastes basically. Especially, when the catalyst is applied to catalytic reaction, especially catalytic synthesis of delta-damascone, the catalyst has the advantages of high reaction activity, short reaction period, simple post-treatment, high yield and high yield of more than 90 percent. In some embodiments of the present invention, the present invention researches the application of the catalyst, and the catalyst of the present invention can still have good catalytic activity after being applied 17 times without any treatment (including regeneration or simple cleaning), and under the same catalytic conditions, the reaction conversion rate and the product yield are almost unchanged compared with the initial application, the variation range is within the allowable error range of manual operation or equipment, and the yield can still achieve more than 90%.
In addition, in still other embodiments of the present invention, the present invention also considers the regeneration of the catalyst, and those skilled in the art know that, in the process of catalysis using mesoporous materials, there may be residues of reactants, impurities, product molecules, etc. in the mesoporous channels of the catalyst, and when the catalyst is recycled, the residues make the reactant molecules less accessible to the catalytically active sites. Thus, if a decrease in activity (e.g., a conversion of 60% or less, 70% or 80% or less, as the case may be) is observed over a period of time during which the catalyst is used, the channels of the catalyst are cleaned, which is generally referred to in the art as catalyst treatment or regeneration. In the present invention, there is provided a catalyst treatment method for the catalyst of the present invention, comprising: centrifugally collecting the used catalyst, heating and washing the catalyst by absolute ethyl alcohol, drying the catalyst, and then adding the dried catalyst into N2And (3) roasting at high temperature under protection, for example, roasting at 300 ℃ for 2h, wherein the residual organic molecules in the mesoporous channels of the catalyst can be removed in the treatment process. In some embodiments of the invention, the invention demonstrates that after 17 consecutive uses, the treated product is treated in the above mannerThe result of the catalytic condition of the catalyst when continuously sleeved shows that the reaction conversion rate and the product yield are almost unchanged compared with the initial application after continuously sleeved for more than 35 times, the change range is within the allowable error range of manual operation or equipment, and the yield can still reach more than 90%. Based on such excellent stability and simple treatment mode, the catalyst provided by the invention can be continuously used in industrial application, so that the process flow is simplified, and the process cost is greatly reduced.
In a fourth aspect of the invention, the invention provides a method of synthesizing delta-damascone comprising: the delta-damascenone is synthesized by using the catalyst in the first aspect of the invention and 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and paraldehyde as raw materials.
In the embodiment of the invention, the paraldehyde is used for replacing acetaldehyde to directly participate in the reaction without being specially depolymerized into acetaldehyde, so that the paraldehyde serving as a raw material is more stable, easy to store, simple and convenient to operate and cost-saving.
In an embodiment of the invention, the synthesis of delta-damascone is performed in a solvent selected from one or more of acetonitrile, ethyl acetate, ethanol, n-hexane, cyclohexane, n-heptane, methyl tert-butyl ether and toluene. Among the above solvents, the synthesis of delta-damascone can be smoothly performed, and particularly, when toluene is selected as a solvent, the synthesis of delta-damascone has excellent reaction conversion rate and yield.
Further, in the embodiment of the invention, the synthesis method of the delta-damascone is a one-pot method, and comprises the steps of mixing reaction raw materials, a catalyst and a solvent, reacting, and directly producing the target product delta-damascone through condensation and dehydration reactions. The reaction mode of the one-pot method greatly simplifies the reaction steps, the separation and post-treatment processes of the catalyst after the reaction are finished are simple, the synthesized delta-damascone product has pure fragrance, and the excellent characteristics of the catalyst greatly save the process cost and are beneficial to industrial mass production.
In the embodiment of the invention, the synthesis temperature of the delta-damascone is 180-260 ℃, and the reaction time is 5-10 h. The choice of different catalysts, solvents, the optimum temperature and time parameters of which are within the above ranges, can be chosen by the person skilled in the art on a case-by-case basis according to the disclosure of the present invention. For example, in some embodiments of the present invention, the catalyst is Nb-V-MCM-41-Ade, and the solvent is toluene, the synthesis temperature is preferably 200 ℃ or higher, such as 200 ℃ or 260 ℃, more preferably 220 ℃ or 260 ℃, and the reaction time is preferably 7 hours or longer, such as 7 hours to 10 hours.
In some embodiments of the present invention, the present invention provides a ratio relationship between the catalyst, the solvent and the raw material, when the mass ratio of the catalyst to the 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone is 0.01-0.05: 1, the mass ratio of the solvent to the 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone is 4-8: 1, the catalyst of the present invention can achieve a good yield, which can be maintained at 80% or more. The ratio parameters provided by the present invention are to give certain research guidance, and those skilled in the art can pursue higher yields and reaction conversions under the disclosure of the present invention, and it should be understood that improvements within the scope of the present invention, without the need for inventive work, should be considered to be within the scope of the present invention.
The invention provides a method for synthesizing delta-damascone, which is simpler and more suitable for industrial production, and the inventor finds that the selection of a catalyst has important influence on the reaction through the reaction in research, particularly, when a mesoporous material catalyst is adopted, the inventor tries different metals and modifiers, and finds that the catalytic effect is optimal when the catalyst is jointly modified by bimetal and organic base (particularly when the bimetal and the organic base are selected within the range disclosed by the invention), which indicates that the synthetic reaction of the delta-damascone provided by the invention can be a process of synergistic acid-base catalysis. The present invention attempts to make two hypotheses about the reaction mechanism: (1) firstly, weak acid site activates carbonyl of 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone and polarizes C-O bond, positive charge on carbonyl carbon is increased, attack in enol intermediate formed by acetaldehyde activated at base site is facilitated, addition product is generated, and finally, the addition product is directly dehydrated under high temperature condition to form more stable delta-damascenone. (2) Firstly, activating carbonyl of 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone at weak acid position, polarizing C-O bond, then generating imine from carbonyl carbon atom under organic base condition, and then removing alpha-hydrogen atom. The carbon-carbon double bond in the enamine then attacks the carbonyl carbon atom in the acetaldehyde adsorbed by the acid center in an affinity addition. And the finally generated addition product is directly dehydrated under the high temperature condition to generate more stable delta-damascone.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst of the invention has the advantages of simple preparation, easy recovery, good stability, good environmental protection and no three wastes basically. The method has the advantages of high reaction activity, short reaction period, simple post-treatment, good reusability, high yield and optimal yield of more than 90%.
The method uses the paraldehyde to replace acetaldehyde to directly participate in the reaction without special depolymerization to acetaldehyde, so that the paraldehyde serving as a raw material is more stable and easy to store, the operation is simple and convenient, and the cost is saved.
The catalyst provided by the invention directly generates the target product delta-damascone through condensation and dehydration reaction by a one-pot method, so that the reaction steps are simplified, the catalyst separation and post-treatment processes after the reaction are simple, the product has pure fragrance, the cost is saved, and the industrial mass production is facilitated.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Example 1
1. Synthesizing a mesoporous material Nb-V-SBA-15-Ade jointly modified by bimetal doping and organic alkali
(1) Synthesis of bimetal doped mesoporous material
4g P123 was dissolved in 30ml of deionized water and stirred at 25 ℃ for 4 hours, and then 70g of 0.2M hydrochloric acid was added to the mixed system and stirred well at 40 ℃ for 2 hours. Butyl niobate and vanadium oxychloride (taking the molar ratio of Nb/V as 1 and the molar ratio of Nb + V)/Si as 10 percent) and 9g of Tetraethoxysilane (TEOS) are premixed and then dropwise added into the vigorously stirred solution, and stirring is continued for 2 hours at the temperature of 40 ℃. And then transferring the formed gel liquid into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, standing for 24 hours at 100 ℃, taking out, carrying out suction filtration, washing with deionized water to be neutral, and drying at room temperature. The template is removed by air roasting at 550 ℃ for 4 hours in a muffle furnace (the heating rate is 10 ℃/min) to obtain the bimetallic doped mesoporous material, which is recorded as Nb-V-SBA-15. According to the method, the active metal component is directly synthesized by an in-situ hydrothermal method in one step, the metal atoms are combined with the mesoporous material through covalent bonds, the operation is simple and easy to implement, and various metal ions can be well controlled to enter the framework of the material and be uniformly dispersed.
Meanwhile, a post-grafting method is also adopted to prepare the Nb-V-SBA-15, namely the finished product SBA-15 is directly adopted in the preparation process, and the result shows that in the process, the combination of the metal active component and the mesoporous material is combined by silicon hydroxyl on the surface of the material, metal atoms are loaded on the surface of the molecular sieve through intermolecular force, and the method is unstable and easy to run off, and the blockage and collapse of a pore channel are easily caused, so the method is not considered.
(2) Organic alkali is used for modifying the bimetal doped mesoporous material
Weighing the synthesized Nb-V-SBA-15 mesoporous material, drying the material for 3h in vacuum at 150 ℃, putting the material into a three-neck flask with a spherical condenser tube, adding 100mL of dry toluene containing gamma-chloropropyltrimethoxysilane (accounting for 6% of the molar weight of the synthesized mesoporous material Si), and performing magnetic stirring reflux for 12h under the protection of nitrogen by taking triethylamine as a catalyst. And after the reaction is finished, quickly performing vacuum filtration, drying for 8 hours in a vacuum oven at the temperature of 60 ℃, performing Soxhlet extraction for 12 hours by using dichloromethane and acetone respectively, and performing vacuum drying to obtain the chloropropyl modified mesoporous material, wherein the mark is Nb-V-SBA-15-Cl.
Adenine (Ade) in an amount equal to the molar amount of gamma-chloropropyltrimethoxysilane is added into 30mL of absolute ethanol, the mixture is placed in a three-neck flask provided with a spherical condenser tube, and the mixture is stirred and refluxed for 30min under the protection of nitrogen. And (2) placing the synthesized Nb-V-SBA-15-Cl in a vacuum oven for drying at 60 ℃ for 3h, placing the obtained product in an ethanol solution dissolved with adenine, stirring and refluxing for 12h under the protection of nitrogen, after the reaction is finished, quickly filtering and washing the product with absolute ethanol, and placing the product in the vacuum oven for drying at 60 ℃ for 8h to obtain an adenine-based modified mesoporous material, which is recorded as Nb-V-SBA-15-Ade.
2. Preparation of delta-damascone
16.6g of 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone, four times the mass of toluene (66.4g), 0.50g (3%) of a catalyst Nb-V-SBA-15-Ade and 8.8g of paraldehyde are added into a reaction kettle, stirred, heated to 180 ℃ for reaction, cooled after the reaction is carried out for 5 hours under heat preservation, and 91.0g of reaction liquid is extruded. Filtering and recovering the catalyst, removing the solvent from the filtrate, and performing reduced pressure rectification to respectively recover 5.6g of unreacted 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and 11.0g of the finished product of delta-damascenone (the gas phase content is 99.5 percent), wherein the yield is 86 percent. The results are shown in Table 1.
Examples 2 to 28
The mesoporous material catalyst doped with Nb-V metal and modified with organic base adenine is used to prepare δ -damascone under conditions of different metal ratios, different base loadings, etc. (other experimental operations and reaction conditions are the same as in example 1), and the experimental results are listed in table 1.
TABLE 1 comparison table of reaction of different mesoporous material modified catalysts under different reaction conditions
Remarking: the amounts of catalyst and solvent used are based on the mass of 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone (the same applies below); the yield calculation method comprises the following steps: the amount of the resulting delta-damascone product/{ actual reaction amount of 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone/166 × 192}, and the actual reaction amount of 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone was the amount charged minus the amount recovered.
The results show that the delta-damascone is synthesized by adopting the catalysts listed in the table 1 according to the method of the invention, the product yield can be stably kept above 80%, and the parameter adjustment yield can be up to above 90%.
Example 29
1. Synthesizing the mesoporous material modified by bimetal doping and organic alkali
The experimental operation and reaction conditions were the same as those of example 1 except for the kind of the mesoporous material in step (1) and the kind of the organic base in step (2). And synthesizing to obtain the dual-functional mesoporous material with a framework acid site and a pore channel alkaline site, and recording the dual-functional mesoporous material as Nb-V-MCM-41-Im.
2. Preparation of delta-damascone
16.6g of 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone, 5 times of toluene (16.6 multiplied by 5), 2.5 percent of catalyst Nb-V-MCM-41-Im (16.6 multiplied by 2.5 percent) and 8.8g of paraldehyde are added into a reaction kettle in sequence, then the temperature is increased to 220 ℃ for reaction for 7 hours, the reaction solution is cooled, the reaction solution is pressed out, the catalyst is recovered by filtration, the solvent is removed from the filtrate, and the unreacted 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone (8.5g) and the delta-damascenone finished product (7.9 g, the gas phase content is 99.5 percent) are respectively recovered by reduced pressure rectification, and the yield is 84 percent. The results are shown in Table 2.
Examples30-56
Preparation of mesoporous material catalyst doped with different metals and modified by different organic bases adenine: the delta-damascone is prepared under different metal combinations (1: 1 in bimetallic case) and different organic base loading conditions (wherein, the specific operation of preparing the mesoporous material is different from the selection of the metal and the selection of the organic base, other experimental operation and reaction conditions are the same as the steps (1) and (2) of the example 1, the preparation of the delta-damascone is the same as the example 29 except that the catalyst is different), and the experimental results are shown in the table 2.
TABLE 2 comparison table of catalytic reactions of mesoporous material catalysts modified by different doping metals and different organic bases
Note: -represents unreacted.
As a result, it was found that when a bimetal is used and modified with an organic base, it has a good catalytic effect. While the choice of bimetallic, as well as organic base, will affect the catalytic conversion.
Examples 56 to 75
The lifetime of the catalyst was examined using Nb-V-MCM-41-Ade as an example:
preparation of delta-damascone:
adding 16.6g of 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone, 5 times of toluene (16.6 multiplied by 5), 2.5 percent of catalyst Nb-V-MCM-41-Ade (16.6 multiplied by 2.5) and 8.8g of paraldehyde into a reaction kettle in sequence, then heating to 220 ℃ for reaction for 7 hours, cooling, pressing out reaction liquid, filtering and recovering the catalyst, removing the solvent from the filtrate, and decompressing and rectifying to respectively recover the unreacted 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and the delta-damascenone finished product. The results are shown in Table 4.
Table 4 comparative table of catalyst application reaction
As a result, it was found that: under the condition of no treatment, the catalyst is mechanically used for 17 times, the catalyst still has good catalytic activity, the reaction conversion rate and the product yield are not changed much compared with the initial mechanical use under the same catalytic condition, the conversion rate can reach 87%, and the yield can still reach about 90%.
Examples 76 to 90
Investigation of catalyst regeneration:
the treatment process of the catalyst comprises the following steps: the catalyst used in example 75 was collected by centrifugation, washed with anhydrous ethanol under heating, dried, and then washed with N2Protecting and roasting at 300 ℃ for 2h to remove organic molecules remained in the mesoporous pore channel.
Preparation of delta-damascone:
adding 16.6g of 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and 5 times of toluene (16.6 multiplied by 5) in a reaction kettle in sequence, heating the regenerated catalyst Nb-V-MCM-41-Ade and 8.8g of paraldehyde to 220 ℃, reacting for 7 hours, cooling, pressing out reaction liquid, removing the solvent from the filtrate, and performing reduced pressure rectification to respectively recover the unreacted 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and delta-damascone finished products. The reaction conditions for regenerating and recycling the catalyst are shown in Table 5.
TABLE 5 comparison table of catalyst regeneration reaction conditions
As a result, the reaction conversion rate and the product yield are almost unchanged compared with the initial application, and the yield can still reach more than 90 percent when the catalyst is continuously applied for more than 35 times. Based on such excellent stability and simple treatment mode, the inventor believes that the catalyst of the invention can realize continuous use in industrial application, simplify the process flow and greatly reduce the process cost.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing delta-damascone is characterized in that 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone and paraldehyde are used as raw materials to synthesize the delta-damascone.
2. The synthesis method according to claim 1, characterized in that the synthesis uses as catalyst a mesoporous material doped in bimetallic manner and modified in organic base, said catalyst comprising a bimetallic active component, a mesoporous material and an organic base.
3. The synthesis method according to claim 1 or 2, wherein the mesoporous material is a mesoporous silica molecular sieve selected from the group consisting of SBA-15, MCM-41, MCM-48, KIT-6, HMS, FDU-1, MSU-1, ZSM-5;
preferably, the bimetallic active component is selected from any one of the following metal combinations: La-Ti, Nb-V, V-Ti, V-Zr, Ti-Bi, Ti-Sn, Ti-Al, Zr-Al, Zr-Mn, Ti-Mn;
preferably, the organic base is selected from one or more of triazabicyclo, tetramethylguanidine, urea, ethylenediamine, benzylamine, imidazole, piperazine, pyrrole, adenine, guanine, thymine, cytosine, uracil.
4. The synthesis method according to claim 1 or 2, characterized in that the synthesis is carried out in a solvent selected from one or more of acetonitrile, ethyl acetate, ethanol, n-hexane, cyclohexane, n-heptane, methyl tert-butyl ether and toluene;
preferably, the synthesis of the delta-damascone adopts a one-pot method, and comprises the step of mixing reaction raw materials, a catalyst and a solvent and then reacting to obtain the delta-damascone.
5. The synthesis method as claimed in claim 4, wherein the synthesis reaction temperature is 180-260 ℃ and the reaction time is 5-10 h;
preferably, the mass ratio of the catalyst to 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone is 0.01-0.05: 1;
preferably, the mass ratio of the solvent to 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone is 4-8: 1.
6. the catalyst is characterized in that the catalyst is a bimetal-doped mesoporous material catalyst modified by organic alkali, and the mesoporous material is a mesoporous silicon molecular sieve selected from SBA-15, MCM-41, MCM-48, KIT-6, HMS, FDU-1, MSU-1 and ZSM-5;
the bimetallic active component is selected from any one of the following metal combinations: La-Ti, Nb-V, V-Ti, V-Zr, Ti-Bi, Ti-Sn, Ti-Al, Zr-Al, Zr-Mn, Ti-Mn;
the organic base is selected from one or more of triazabicyclo, tetramethylguanidine, urea, ethylenediamine, benzylamine, imidazole, piperazine, pyrrole, adenine, guanine, thymine, cytosine and uracil.
7. The catalyst of claim 6, wherein the doping amount of the bimetal is 5-15% of the molar weight (calculated by silicon) of the mesoporous silicon molecular sieve;
preferably, the loading amount of the organic base is 3-10% of the molar weight (calculated by silicon) of the mesoporous silicon molecular sieve.
8. A process for preparing the catalyst of claim 6 or 7, characterized in that it comprises: under an acidic condition, synthesizing the bimetal-doped mesoporous material by one step through an in-situ hydrothermal method, realizing inorganic functionalization of the mesoporous material, and obtaining the bimetal-doped mesoporous material; by a post-grafting method, nitrogen-containing organic groups in organic alkali are introduced into the bimetal-doped mesoporous material to synthesize the bifunctional mesoporous material with a skeleton acid site and a pore passage basic site.
9. Use of the catalyst of claim 6 or 7 for catalyzing an acid-base co-reaction.
10. Use of a catalyst according to claim 6 or 7 for the catalytic synthesis of delta-damascone;
preferably, the synthesis of the delta-damascone takes 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone and paraldehyde as raw materials.
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