CN110922316A - Method for preparing L-menthone from R-citronellal - Google Patents
Method for preparing L-menthone from R-citronellal Download PDFInfo
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Abstract
The invention discloses a method for preparing L-menthone from R-citronellal, wherein under the action of a Pd-Co-MOF-MMT catalyst, the R-citronellal is subjected to a heterogeneous catalytic reaction to generate the L-menthone, the conversion rate of the R-citronellal is 90-99.9%, the yield of the L-menthone can reach 85-98%, and the ee value of the L-menthone can reach 95-99.99%.
Description
Technical Field
The invention relates to a method for preparing L-menthone from R-citronellal, belonging to the field of organic chemical synthesis.
Background
Menthone, also known as menthone, has the cooling characteristic aroma of natural mint. Menthone exists in the form of two stereoisomers: menthone and isomenthone, each of which exists in the form of two enantiomers, are mainly used for preparing mint-type essences, and the preparation methods disclosed at present include the following:
U.S. Pat. No. 3,3124614 reports that menthone can be obtained by hydrogenating thymol under the action of Pd catalyst, but the source of thymol as a raw material is in short supply, which causes great limitation on continuous production, and the reaction has high requirements on equipment materials and harsh reaction conditions, which causes high equipment cost.
Chinese published patent CN104603095A employs a metal complex containing phosphine ligands as a catalyst. The process can achieve a menthone yield of more than 85%, but cannot achieve high revolution per revolution (TON), has short catalyst life, and is not suitable for industrial synthesis of menthone in consideration of high cost of the catalyst.
Chinese published patent CN106068160A describes a ruthenium-phenol catalyst for transfer hydrogenation reaction and the catalyst has excellent performance in transfer hydrogenation reaction, and the catalyst is used for preparing menthone from isopulegol with higher conversion rate and selectivity. However, the process has a limited increase in the number of revolutions per minute (TON), the catalyst life is still short, and a large amount of phenol derivative is used, which has adverse effects on the post-treatment and the environment. Meanwhile, the process cannot well solve the problem of poor purity of the L-menthone, and the complexity of the whole process is increased.
Chinese published patent CN106061933A discloses a method for preparing menthone by contacting isopulegol in gas phase with activated oxidized copper catalyst, firstly, the method needs to activate the copper catalyst in advance, the activation effect has a large influence on the reaction yield, so the quality difference of different batches of products is large, and the process is not suitable for large-scale industrial production.
Therefore, a method which is simple in process, mild in reaction conditions, economical, efficient, environment-friendly and easy to realize industrialization is urgently needed to realize the preparation of menthone.
Disclosure of Invention
The invention aims to provide a method for preparing high-purity L-menthone, so that a plurality of problems in the existing menthone preparation process are solved. The method for directly preparing the L-menthone from the R-citronellal greatly reduces reaction steps, optimizes a reaction process, can recover a catalyst in a convenient mode, has a simpler reaction process, lower reaction cost and good environmental friendliness, does not need hydrogen through a hydrogenation transfer process, and has better process safety and industrial prospect.
If not otherwise specified, the term "menthone" refers to any of the possible stereoisomers, including:
wherein the structure of the R-citronellal is as follows:
the structure of the L-menthone is as follows:
the structure of the D-menthone is as follows:
if not otherwise stated, the term "ee value" means an enantiomeric excess, which means the excess of one enantiomer over the other, and is used herein to refer to the difference in the percentage of L-menthone in the gas phase compared to D-menthone.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing L-menthone from R-citronellal is characterized in that under the action of a Pd-Co-MOF-MMT catalyst, the R-citronellal is subjected to a heterogeneous catalytic reaction to generate the L-menthone.
The ee value range of the R-citronellal is 95-99.99%, and preferably more than 98%.
The high ee value means that the ee value can reach 95-99.99%.
In the invention, the molar ratio of palladium element to cobalt element in the Pd-Co-MOF-MMT catalyst is 1: 1-1.5, preferably 1: 1-1.2; the MOF is constructed by using methyl p-aminobenzoate as a monomer, wherein the molar ratio of methyl p-aminobenzoate to palladium element is 1-3: 1, preferably 1.8-2.2: 1, and more preferably 2: 1; the mass ratio of methyl p-aminobenzoate to kaolin is 1-4: 1, preferably 1.5-2: 1. .
In the method, the preparation method of the Pd-Co-MOF-MMT catalyst comprises the following steps:
(1) adding methyl p-aminobenzoate and kaolin into ethanol and water for ultrasonic dissolution, stirring for 20-24 hours at the temperature of 55-65 ℃, then performing suction filtration and washing, and performing vacuum drying to obtain an MMT precursor;
(2) putting the palladium metal precursor, the cobalt metal precursor and the MMT precursor into N, N-dimethylformamide for ultrasonic treatment until all the palladium metal precursor, the cobalt metal precursor and the MMT precursor are dissolved, dropwise adding water, pouring the obtained solution into a reaction kettle, heating for reaction for 45-50 h, carrying out programmed cooling to 0-minus 5 ℃, filtering crystals by using a centrifugal machine, washing, and carrying out vacuum drying to obtain a catalyst finished product.
As a preferable scheme, the preparation method of the Pd-Co-MOF-MMT catalyst comprises the following steps:
adding a proper amount of ethanol and deionized water into methyl p-aminobenzoate and kaolin (MMT) according to a certain proportion, ultrasonically dissolving, stirring for 20-24 h at 55-65 ℃, then carrying out suction filtration and washing, and drying in a vacuum oven at 55-65 ℃ for 5-8 h to obtain the MMT precursor.
Putting a palladium metal precursor, a cobalt metal precursor and an MMT precursor into N, N-dimethylformamide according to a certain proportion, performing ultrasonic treatment until all the precursors are dissolved, dropwise adding a proper amount of deionized water, pouring the obtained solution into a polytetrafluoroethylene-lined high-pressure reaction kettle with a proper volume, screwing, putting into a program-controlled oven, heating and reacting for 45-50 h at a certain temperature, performing temperature programming reduction to 0-minus 5 ℃, filtering crystals by using a centrifugal machine, washing with pure water, drying for 12-15 h at 45-55 ℃ in a vacuum drying oven, and cooling to room temperature to obtain a catalyst finished product.
As a preferable scheme, the mass ratio of the methyl p-aminobenzoate to the kaolin (MMT) is 1-4: 1, preferably 1.5-2: 1.
As a preferable scheme, the mass ratio of the total mass of the methyl aminobenzoate and the kaolin (MMT) to the deionized water is 1: 50-80, and preferably 1: 60-70.
As a preferable scheme, the mass ratio of the total mass of the methyl aminobenzoate and the kaolin (MMT) to the ethanol is 1: 50-80, and preferably 1: 60-70.
Preferably, in the preparation process of the Pd-Co-MOF-MMT catalyst: the palladium metal precursor is selected from one or more of palladium iodide, palladium dibromide, palladium acetate, palladium sulfate, bis (triphenylphosphine) palladium dichloride and benzyl bis (triphenylphosphine) palladium (II) chloride, and preferably palladium dibromide and/or palladium acetate.
The cobalt metal precursor is selected from one or more of cobalt sulfate heptahydrate, anhydrous cobalt chloride, cobalt nitrate hexahydrate, cobalt bromide and cobalt acetate tetrahydrate, and preferably cobalt nitrate hexahydrate and/or cobalt acetate tetrahydrate.
In the method of the present invention, the amount of N, N-dimethylformamide added is 20 to 50ml/1mmol (based on the molar amount of palladium), preferably 20 to 30ml/1mmol (based on the molar amount of palladium).
Water is added dropwise in a ratio of 0.5 to 10ml/100ml of N, N-dimethylformamide, preferably 1 to 6ml/100ml of N, N-dimethylformamide.
The preparation method of the Pd-Co-MOF-MMT catalyst comprises the following steps: in the step (2), the reaction temperature in the reaction kettle is 130-150 ℃, and the temperature is reduced to 0-5 ℃ at the speed of 0.5-2 ℃/min.
In the invention, the dosage of the Pd-Co-MOF-MMT catalyst is 0.01-0.5 mol%, preferably 0.1-0.3 mol% of the amount of R-citronellal calculated by the molar amount of palladium element.
In some preferred embodiments, the heterogeneously catalyzed reaction is carried out at atmospheric pressure and is divided into two stages;
the first stage reaction temperature is-30-15 ℃, preferably 0-10 ℃, and the reaction time is 2-8 hours, preferably 4-6 hours;
the second-stage reaction temperature is 50-100 ℃, preferably 70-90 ℃, and the reaction time is 0-24 hours, preferably 6-12 hours;
in the method, in the process of generating the L-menthone by the heterogeneous catalytic reaction of the R-citronellal, the R-citronellal is subjected to cyclization reaction to prepare the L-isopulegol, and then the generated L-isopulegol is subjected to intramolecular hydrogenation transfer reaction to generate the L-menthone.
According to the method, the conversion rate of the raw material R-citronellal is 98-99.9%, and the yield of the final product L-menthone of the heterogeneous catalytic reaction is 90-98%.
The method for preparing L-menthone from R-citronellal adopts Pd-Co-MOF-MMT for catalysis, kaolin has the characteristics that a stable layered structure supported catalyst has high catalytic performance and good cyclic utilization rate, after methyl p-aminobenzoate is modified, a crystalline MOF material can uniformly and regularly grow, and meanwhile, a formed space aperture structure is favorable for changing Pd and Co ions from a free state to a fixed state. Meanwhile, preferably, the MOF material can be controlled to grow according to the designed size by adjusting factors such as solvent, temperature and crystallization conditions, and the utilization rate of the catalyst is more favorable. Meanwhile, the methyl p-aminobenzoate has a good effect on inhibiting cyclization side reactions, and the catalytic performance of the methyl p-aminobenzoate is further improved.
The method has the advantages that:
1) under the action of a Pd-Co-MOF-MMT catalyst, high-purity L-menthone can be efficiently prepared from R-citronellal with high yield under mild reaction conditions, and the method has remarkable operability and economy, reduces the process flow, improves the economic benefit, and reduces the investment of equipment, public engineering and the like.
2) The reaction system does not need to add a solvent, so that the introduction of other impurities is avoided, and the generated waste liquid is less and has good environmental friendliness.
3) The L-isopulegol is subjected to intramolecular hydrogenation transfer to generate the L-menthone, so that hydrogen is prevented from being introduced as a hydrogen source, oxidation operation is not required, and the process safety is greatly improved.
4) The adopted Pd-Co-MOF-MMT catalyst has higher catalytic activity in both aqueous phase and organic phase solvents, and has the advantages of easy recovery, high catalytic activity and the like.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Firstly, the main raw materials used in the embodiment of the invention are described as follows:
palladium acetate, alatin, product number P111486, purity 99.98%;
palladium dibromide, alatin, product number P100503, purity 99%;
cobalt acetate tetrahydrate, alatin, product number C11085, purity 99.5%;
cobalt nitrate hexahydrate, alatin, product number C112729, purity 99%;
p-aminobenzoic acid methyl ester, alatin, product number P108506, purity 99%;
n, N dimethylformamide, alatin, product number D112002, purity 99.9%;
kaolin, alatin, product number K100133;
r-citronellal, Wuhan, is far from the Co-creation science and technology Limited company, the chemical purity is more than 99%, and the ee value range is 95-100%.
Second, reaction product testing apparatus and method in the examples:
gas chromatograph: shimadzu GC-2010plus, chromatographic column DB-WAX UI, injection port temperature: feeding 0.1 mu L at 220 ℃; the split ratio is 100: 1; carrier gas flow: 1.0 ml/min; temperature rising procedure: keeping the temperature at 80 ℃ for 2min, heating to 150 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 10min, and measuring the temperature of a detector: at 250 ℃ to obtain a mixture. Hydrogen flow rate: 40mL/min, air flow rate: 400mL/min, tail-blow flow rate: 30 mL/min.
ICP-AES (inductively coupled plasma emission Spectroscopy), Optima 2000 DV.
Example 1
Adding 1.249g of methyl p-aminobenzoate and 0.6245g of kaolin (MMT) into 112g of ethanol and 112g of deionized water, ultrasonically dissolving, stirring for 24 hours at 55 ℃, then carrying out suction filtration washing, and drying for 5 hours at 55 ℃ in a vacuum oven. Named MMT precursor.
Putting 1g of palladium dibromide, 1.09g of cobalt nitrate hexahydrate and the obtained MMT precursor into 75ml of N, N-dimethylformamide for ultrasonic treatment until all the palladium dibromide, dripping 34.5ml of deionized water, pouring the obtained solution into a reaction kettle with a 250ml of polytetrafluoroethylene lining, screwing the solution, putting the solution into a program-controlled oven, heating and reacting the solution at 130 ℃ for 45 hours, cooling the solution to 0 ℃ at the speed of 0.5 ℃/min, filtering crystals by using a centrifugal machine, washing the crystals by using the deionized water, drying the crystals in a vacuum drying oven at 45 ℃ for 12 hours, cooling the crystals to room temperature, and weighing to obtain 3.22g of the catalyst. The load amount of palladium element detected by ICP was 9.92 wt%, the load amount of cobalt element was 5.49 wt%, and the molar ratio of palladium element to cobalt element was 1:1.
Example 2
1.02g of methyl p-aminobenzoate and 0.681g of kaolin (MMT) are added into 110g of ethanol and 110g of deionized water for ultrasonic dissolution, stirred for 22h at 60 ℃, then filtered, washed and dried for 6.5h in a vacuum oven at 60 ℃. Named MMT precursor.
1g of palladium dibromide, 1.127g of cobalt acetate, tetrahydrate and the obtained MMT precursor are placed in 112ml of N, N-dimethylformamide to be subjected to ultrasonic treatment until the palladium dibromide, the cobalt acetate, the tetrahydrate and the obtained MMT precursor are completely dissolved, 1.12ml of deionized water is dropwise added, the obtained solution is poured into a reaction kettle with a 250ml of polytetrafluoroethylene lining, the reaction kettle is screwed up and placed into a program-controlled oven, the reaction kettle is heated at 150 ℃ for 50 hours, the temperature is reduced to minus 5 ℃ at the speed of 2 ℃/min, crystals are filtered by a centrifugal machine, the crystals are washed by the deionized water, dried in a vacuum drying oven at 55 ℃. The load amount of palladium element detected by ICP is 10.178 wt%, the load amount of cobalt element is 6.764 wt%, and the molar ratio of palladium element to cobalt element is 1: 1.2.
Example 3
1.347g of methyl p-aminobenzoate and 0.77g of kaolin (MMT) are added into 137.5g of ethanol and 137.5g of deionized water for ultrasonic dissolution, stirred for 20 hours at 65 ℃, then filtered and washed, and dried for 8 hours at 65 ℃ in a vacuum oven. Named MMT precursor.
Putting 1g of palladium acetate, 1.49g of cobalt nitrate, hexahydrate and the obtained MMT precursor into 111.4ml of N, N-dimethylformamide for ultrasonic treatment until all the components are dissolved, dropwise adding 6.68ml of deionized water, pouring the obtained solution into a reaction kettle with a 250ml of polytetrafluoroethylene lining, screwing the solution and putting the solution into a program-controlled oven, heating and reacting the solution at 140 ℃ for 45 hours, cooling the solution to 0 ℃ at 1 ℃/min, filtering crystals by using a centrifugal machine, washing the crystals by using the deionized water, drying the crystals at 55 ℃ for 12 hours in a vacuum drying oven, cooling the crystals to room temperature, and weighing the catalyst to obtain 3.7 g. The load amount of palladium element detected by ICP was 10.252 wt%, the load amount of cobalt element was 6.81 wt%, and the molar ratio of palladium element to cobalt element was 1: 1.2.
Example 4
Adding 141.4g of ethanol and 141.4g of deionized water into 1.212g of methyl p-aminobenzoate and 0.808g of kaolin (MMT), ultrasonically dissolving, stirring for 22h at 60 ℃, then carrying out suction filtration and washing, and drying for 6.5h at 65 ℃ in a vacuum oven. Named MMT precursor.
1g of palladium acetate, 1.331g of cobalt acetate, tetrahydrate and the obtained MMT precursor are placed in 133.6ml of N, N-dimethylformamide to be completely dissolved by ultrasonic wave, 4.67ml of deionized water is dropwise added, the obtained solution is poured into a reaction kettle with a 250ml of polytetrafluoroethylene lining, the reaction kettle is screwed and placed into a program-controlled oven, the reaction kettle is heated at 150 ℃ for 50h, the temperature is reduced to minus 5 ℃ at the speed of 2 ℃/min, crystals are filtered by a centrifugal machine, the crystals are washed by the deionized water, dried in a vacuum drying oven at 55 ℃ for 15h, cooled to room temperature, and 3.577g of the catalyst is obtained by weighing. The load amount of palladium element detected by ICP was 10.6 wt%, the load amount of cobalt element was 7.045 wt%, and the molar ratio of palladium element to cobalt element was 1: 1.2.
Example 5
The reaction kettle is pressed to 0.3MPaG by using nitrogen, the pressure is released to the normal pressure, 3.688g of the catalyst prepared by the method in the embodiment 1 is added into the reaction kettle after the three times of processes, 200g R-citronellal is added into a 500ml closed reaction kettle, the stirring is started, the temperature is reduced to 0 ℃, the reaction temperature is kept stable, and the reaction is continued for 6 hours.
Then, the reaction temperature was raised to 70 ℃ and kept stable for 12 hours.
The chromatographic analysis calculates that the final conversion rate of the R-citronellal reaction is 98.01 percent, the yield of the L-menthone is 97.38 percent, and the ee value of the L-menthone is 99.88 percent
Example 6
The reaction kettle was flushed with nitrogen to 0.3MPaG, vented to atmospheric pressure, and repeated three times, 1.209g of the catalyst prepared as described in example 2 was added to the reaction kettle, 200g R-citronellal was added to a 500ml closed reaction kettle, the stirring was started, the temperature was reduced to 5 ℃, the reaction temperature was kept stable, and the reaction was continued for 5 h.
Then, the reaction temperature was raised to 80 ℃ and kept stable for 9 hours.
The final conversion rate of the R-citronellal reaction is 98.95% and the yield of the L-menthone is 95.8% by chromatographic analysis calculation. The ee value of L-menthone is 99.12 percent
Example 7
The reaction kettle was flushed with nitrogen to 0.3MPaG, vented to atmospheric pressure, and repeated three times, 2.839g of the catalyst prepared by the method described in example 3 was added to the reaction kettle, 200g R-citronellal was added to a 500ml closed reaction kettle, the stirring was started, the temperature was reduced to 10 ℃, the reaction temperature was kept stable, and the reaction was continued for 4 h.
Then, the reaction temperature was raised to 90 ℃ and kept stable for 6 hours.
The chromatographic analysis calculates that the final conversion rate of the R-citronellal reaction is 99.79 percent, and the yield of the L-menthone is 92.38 percent. The ee value of L-menthone is 97.32%
Example 8
The reaction kettle was flushed to 0.3MPaG with nitrogen, vented to atmospheric pressure, and repeated three times, 1.155g of the catalyst prepared as described in example 4 was added to the reaction kettle, 200g R-citronellal was added to a 500ml closed reaction kettle, the stirring was started, the temperature was reduced to 0 ℃, the reaction temperature was kept stable, and the reaction was continued for 6 h.
Then, the reaction temperature was raised to 90 ℃ and kept stable for 12 hours.
The final conversion rate of the R-citronellal reaction is 98.51% and the yield of L-menthone is 98.822% by chromatographic analysis calculation. The ee value of L-menthone is 97.72%
Example 9
The catalyst was recovered by filtration based on example 6, and was used for 30 times, and the experimental results were as follows:
| group of | R-citronellal conversion/% ] | L-menthone yield/% | L-menthone ee value/% |
| Example 9 | 98.89 | 95.89 | 99.12 |
| Apply it 10 times | 98.81 | 95.91 | 99.06 |
| Apply it 20 times | 98.79 | 94.85 | 99.11 |
| Apply it for 30 times | 98.63 | 94.47 | 99.13 |
COMPARATIVE EXAMPLE 1(CN 104603095 preparation example 4)
Under inert conditions, the mixture is mixed 404mg of [ Ru (PnOct)3)4(H)2]3.6g of isopulegol and 10ml of o-xylene (anhydrous) are weighed into a 50ml glass autoclave. The reaction mixture was then stirred at an oil bath temperature of 130 ℃ under autogenous pressure (0.5 bar positive pressure) for 12 hours. After the reaction, the conversion and yield (% by area) of menthone (sum of isomers) were determined by gas chromatography. Conversion of isopulegol was 64.5%, with a selectivity of menthol (65.8% (-) -menthol, 34.2% (+) -isomenthane isomer mixture) of 46.3%. The selectivity of the secondary components is 30.2 percent of menthol, 14.4 percent of isopulegone and 90.9 percent of the total selectivity (the menthol, the menthol and the isopulegone).
COMPARATIVE EXAMPLE 2(CN 106061933A EXAMPLE 1)
Mixing X540T 1/8(l 50g, 30-40% copper oxide, 10-25% aluminum oxide, 10-25% magnesium oxide and 30-40% aluminum copper (Al)2CuO4) Charged into a gas phase reactor and the catalyst is activated at a temperature of 170-180 ℃ under a specific gas-containing stream (20-40 NL/h). The evaporator and reactor were subsequently operated at a temperature of 170 ℃ and at atmospheric pressure with a nitrogen stream (20 NL/h). Isopulegol (water content 3.7% by weight, 15g/h,97.2mmol/h) is continuously introduced into the evaporator. The product mixture was condensed at the reactor outlet and analyzed for composition using gas chromatography. In each case, after an experimental time of 5 hours, the reactor and evaporator were cooled under a stream of nitrogen (20NL/h), and the experiment was continued after 18h without changing the catalyst.
The reaction of isopulegol is completed over the entire reaction time.
Table 1: conversion, mass balance and product composition in the isopulegol reaction.
Values are based on area percent.
Isopulegol is reacted to menthone in good to very good yields of up to 88.5%. For all experiments, the ratio of menthone to isomenthone was 65/35-70/30 (menthone/isomenthone) (see table 1).
Claims (10)
1. A method for preparing L-menthone from R-citronellal comprises the steps of carrying out heterogeneous catalysis reaction on R-citronellal under the action of a Pd-Co-MOF-MMT catalyst to prepare L-menthone, wherein MMT is kaolin; the ee value range of the R-citronellal is 95-99.99%, and preferably more than 98-99.99%.
2. The method according to claim 1, wherein the molar ratio of palladium element to cobalt element in the Pd-Co-MOF-MMT catalyst is 1:1 to 1.5, preferably 1:1 to 1.2; the MOF is constructed by using methyl p-aminobenzoate as a monomer, the molar ratio of methyl p-aminobenzoate to palladium element is 1-3: 1, preferably 1.8-2.2: 1, and the mass ratio of methyl p-aminobenzoate to kaolin is 1-4: 1, preferably 1.5-2: 1.
3. The method according to claim 1 or 2, wherein the Pd-Co-MOF-MMT catalyst is prepared by:
(1) adding methyl p-aminobenzoate and kaolin into ethanol and water for ultrasonic dissolution, stirring for 20-24 h at 55-65 ℃, then performing suction filtration and washing, and performing vacuum drying to obtain an MMT precursor;
(2) putting the palladium metal precursor, the cobalt metal precursor and the MMT precursor into N, N-dimethylformamide for ultrasonic treatment until all the palladium metal precursor, the cobalt metal precursor and the MMT precursor are dissolved, dropwise adding water, pouring the obtained solution into a reaction kettle, heating for reaction for 45-50 h, carrying out programmed cooling to 0-minus 5 ℃, filtering crystals by using a centrifugal machine, washing, and carrying out vacuum drying to obtain a catalyst finished product.
4. The method according to claim 3, wherein the mass ratio of the methyl p-aminobenzoate to the kaolin in the step (1) is 1-4: 1, preferably 1.5-2: 1; the mass ratio of the total mass of the methyl aminobenzoate and the kaolin to the water is 1: 50-80, preferably 1: 60-70; the mass ratio of the total mass of the methyl aminobenzoate and the kaolin to the mass of the ethanol is 1: 50-80, and preferably 1: 60-70.
5. The method according to claim 3 or 4, wherein, in the step (2),
the palladium metal precursor is selected from one or more of palladium iodide, palladium dibromide, palladium acetate, palladium sulfate, bis (triphenylphosphine) palladium dichloride and benzyl bis (triphenylphosphine) palladium (II) chloride, and preferably palladium dibromide and/or palladium acetate;
the cobalt metal precursor is selected from one or more of cobalt sulfate heptahydrate, anhydrous cobalt chloride, cobalt nitrate hexahydrate, cobalt bromide and cobalt acetate tetrahydrate, and preferably cobalt nitrate hexahydrate and/or cobalt acetate tetrahydrate.
6. The method according to any one of claims 3 to 5, wherein in the step (2), the N, N-dimethylformamide is added in a proportion of 20 to 50ml/1mmol (based on the molar amount of the palladium element), preferably in a proportion of 20 to 30ml/1mmol (based on the molar amount of the palladium element); water is added dropwise in a ratio of 0.5 to 10ml/100ml of N, N-dimethylformamide, preferably 1 to 6ml/100ml of N, N-dimethylformamide.
7. The method according to any one of claims 3 to 6, wherein in the step (2), the reaction temperature in the reaction vessel is 130 to 150 ℃ and is decreased to 0 to-5 ℃ at a rate of 0.5 to 2 ℃/min.
8. The method according to any one of claims 3 to 6, wherein the temperature of the vacuum drying in the step (1) is 55 to 65 ℃ for 5 to 8 hours, and the temperature of the vacuum drying in the step (2) is 45 to 55 ℃ for 12 to 15 hours.
9. The process according to any one of claims 1 to 8, wherein the amount of Pd-Co-MOF-MMT catalyst is 0.01 to 0.5 mol%, preferably 0.1 to 0.3 mol%, based on the molar amount of palladium element, based on the amount of R-citronellal.
10. The method according to any one of claims 1 to 9,
the heterogeneous catalytic reaction is a normal pressure reaction;
the heterogeneous catalytic reaction is divided into two sections; the first stage reaction temperature is-30-15 ℃, preferably 0-10 ℃, and the reaction time is 2-8 hours, preferably 4-6 hours;
the second-stage reaction temperature is 50-100 ℃, preferably 70-90 ℃, and the reaction time is 0-24 hours, preferably 6-12 hours.
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