A preparation method of 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl)acetic acid methyl ester

Abstract

The present invention provides a method for preparing 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the preparation method comprising the following steps: ordinary methyl dihydrojasmonate and isopropenyl acetate are reacted under a composite catalyst to obtain the 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the composite catalyst being composed of a transition metal salt and a layered zirconium phosphate. The method of the present invention has simple operation steps, mild reaction conditions, high yield and easy separation. The environmental protection risks caused by waste salt and waste water generated by quenching and repeated washing due to the use of an acidic catalyst reaction in the prior art are solved, and the problem of equipment corrosion is not only reduced in environmental protection and equipment investment, but also simplified in production process, which is conducive to industrialized mass production of products.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemicals, and in particular relates to a method for preparing 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate. Background Art

[0002] Methyl Dihydrojasmonate (MDJ) is a colorless or light yellow transparent liquid belonging to the jasmone class of compounds. It has a fresh and elegant jasmine aroma and a comfortable and soft lemon-like fruity aroma. Its long-lasting fragrance is highly favored by perfumers and is a rare and important artificial chemical synthetic fragrance compound. It is widely used in high-end perfume flavors, cosmetic flavors, food flavors and daily detergent flavors.

[0003] In the 1970s, Naoshima et al. found that there are four isomers of dihydrojasmonate, A, B, C, and D, and the aroma characteristics and aroma intensity of the four isomers are different. Later, after detailed research by flavor chemists, it was found that the threshold of the trans isomer is 1.85ng / L, while the threshold of the cis isomer is only 0.028ng / L. The aroma intensity of the C isomer is more than 70 times that of A and about 1,000 times that of the other two configurations. It has the purest aroma, with an elegant and soft jasmine fragrance and a comfortable lemon-like fruity aroma. The whole aroma is light and elegant. Later, this isomer was called paradise ketone. At present, most of the manufacturers of high-quality cis-dihydrojasmonate are abroad, mainly IFF in the United States, Firmenich in Switzerland, and ZEON in Japan.

[0004]

[0005] In current technology, there are two main methods for preparing high-proportion cis-dihydrojasmonate: one is to directly subject dehydrogenated dihydrojasmonate to asymmetric catalytic hydrogenation to prepare high-cis-dihydrojasmonate; the other is to use cyclopentenone as a raw material to synthesize high-cis-dihydrojasmonate. For example, Firmenich has achieved asymmetric catalytic hydrogenation of dehydrogenated dihydrojasmonate based on the ruthenium-catalyzed asymmetric catalytic hydrogenation reaction technology developed, and industrially produced high cis-(1R,2S)-dihydrojasmonate with an ee value of 65-88%, and the ratio of cis-trans isomers can reach 96:4. There are also reports that dehydrogenated dihydrojasmonate is directly catalytically hydrogenated with a Pd / C catalyst to prepare dihydrojasmonate, and its cis isomer accounts for 30-40%. The key intermediate for synthesizing high cis-dihydrojasmonate using cyclopentenone as raw material is 2-pentyl-2-cyclopentenone, which is subjected to an asymmetric Michael addition reaction and then converted to obtain high cis-dihydrojasmonate. However, these synthetic processes all have certain industrial production problems, such as the complicated catalyst preparation process and high cost; the low proportion of cis-isomers, especially (1R, 2S) configuration isomers, resulting in low industrial value of the product; harsh reaction conditions, long process routes, and not in line with the concept of green development.

[0006] EP399788 introduces the process of adding 1% carbonate by weight of methyl dihydrojasmonate to ordinary methyl dihydrojasmonate, reacting for several hours under the protection of nitrogen and at a temperature of 180°C, directly preparing cis-methyl dihydrojasmonate, the content of which is generally about 10%, and then rectifying the 10% methyl dihydrojasmonate to obtain methyl dihydrojasmonate with a cis-methyl dihydrojasmonate content of 20-50%. However, the reaction and rectification temperatures are relatively high, and part of the cis-methyl dihydrojasmonate will undergo decarboxylation and conversion to dihydrojasmone, as well as carbonization of organic matter, which reduces the yield and affects the aroma stability of the product, and also fails to obtain a high-content cis-methyl dihydrojasmonate product.

[0007] CN113929575B discloses that methyl dihydrojasmonate, isopropenyl acetate and p-toluenesulfonic acid (p-TSA) catalyst are mixed, slowly heated to 85-95°C and kept warm for 6-8h; after the reaction is completed, the resulting product system is naturally cooled to room temperature, quenched by adding a saturated NaHCO3 aqueous solution, and then extracted with ethyl acetate; the organic phase is collected, and the aqueous phase is repeatedly extracted with ethyl acetate for multiple times; multiple organic phases are combined, and successively dried, concentrated under reduced pressure and separated by a column to obtain 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate. This method is cumbersome to operate and does not utilize large-scale industrial production. Summary of the invention

[0008] In view of the deficiencies in the prior art, the object of the present invention is to provide a method for preparing 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate. In the method of the present invention, a composite catalyst is used to catalyze the preparation of 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, and the method has simple operation steps, mild reaction conditions, high yield and easy separation. The environmental protection risks caused by the need for quenching and repeated washing of waste salts and wastewater generated by the reaction using an acidic catalyst (such as sulfuric acid, hydrochloric acid, phosphoric acid, organic carboxylic acid, sulfonic acid, etc.) in the prior art, as well as the problem of equipment corrosion, not only reduce environmental protection and equipment investment, but also simplify the production process, which is conducive to the industrialized mass production of products.

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] In one aspect, the present invention provides a method for preparing methyl 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl)acetate, the preparation method comprising the following steps:

[0011] Ordinary methyl dihydrojasmonate and isopropenyl acetate react under the catalysis of a composite catalyst to obtain the methyl 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) acetate, and the composite catalyst consists of a transition metal salt and layered zirconium phosphate.

[0012] The reaction equation of the reaction of the present invention is as follows:

[0013] .

[0014] Preferably, the transition metal salt is any one of nitrates, sulfates, chlorides, acetates, hydroxides or hydrates thereof containing Fe, Cu, Zn, Ni, Co, Zr, Nb or Mo, or a combination of at least two thereof.

[0015] Further preferably, the transition metal salt is FeCl3·6H2O, Fe(NO3)3·9H2O, FeSO4·7H2O, ferric acetylacetonate, Zn(NO3)2·6H2O, CuSO4·5H2O, NiSO4·6H2O, Co(OAc)2·4H2O, Zr(NO3)4·5H2O, NbCl5 or (NH4)6Mo7O 24 Any one or a combination of at least two of 4H2O.

[0016] Preferably, the layered zirconium phosphate is selected from one or a combination of at least two of α-ZrP, Cu-α-ZrP, Mg-α-ZrP, and Ni-α-ZrP.

[0017] Preferably, the amount of the transition metal salt is such that the metal ion content in the transition metal salt is 1%-9% of the mass of the layered zirconium phosphate, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5% or 9%, preferably 5%-7%.

[0018] In the present invention, the preparation method of the composite catalyst is as follows:

[0019] (1) Adsorption: Add transition metal salt and layered zirconium phosphate into the solvent and disperse them evenly;

[0020] (2) Drying: removing excess water and drying to obtain a precursor;

[0021] (3) Calcination: calcining the precursor to obtain the composite catalyst.

[0022] Preferably, the solvent in step (1) is selected from an organic solvent or water, preferably one that can dissolve the transition metal salt, such as ethanol, methanol, etc., which is not required here.

[0023] In step (1), the adsorption time is 2-6 h, for example, 2 h, 3 h, 4 h, 5 h or 6 h, preferably 4-6 h; the adsorption temperature is 30-60 ° C, for example, 30 ° C, 33 ° C, 35 ° C, 38 ° C, 40 ° C, 45 ° C, 48 ° C, 50 ° C, 55 ° C, 58 ° C or 60 ° C, preferably 30-50 ° C.

[0024] In step (3), the calcination time is 3-6 h, for example, 3 h, 4 h, 5 h or 6 h, preferably 4-6 h; the calcination temperature is 300-500 ° C, for example, 300 ° C, 350 ° C, 380 ° C, 400 ° C, 450 ° C, 480 ° C or 500 ° C, preferably 300-400 ° C.

[0025] Preferably, the amount of the composite catalyst is 1%-10% of the mass of ordinary methyl dihydrojasmonate, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, preferably 5%-7%.

[0026] Preferably, the mass ratio of ordinary methyl dihydrojasmonate to isopropenyl acetate is 1:1-2, for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, preferably 1:1.2-1.6.

[0027] Preferably, the reaction temperature is 80-160°C, for example 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C or 160°C, preferably 100-120°C.

[0028] Preferably, the reaction time is 2-6 h, such as 2 h, 3 h, 4 h, 5 h or 6 h, preferably 3-5 h.

[0029] In the present invention, the reaction can be carried out in the form of a batch reaction in a kettle or a continuous reaction by distillation, and a batch reaction in a kettle is preferred.

[0030] As a preferred technical solution, the preparation method comprises the following steps:

[0031] Ordinary methyl dihydrojasmonate and isopropenyl acetate are reacted at 80-160° C. for 2-6 hours under the catalysis of a composite catalyst to obtain the methyl 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) acetate; the amount of the composite catalyst is 1%-10% of the mass of ordinary methyl dihydrojasmonate, and the mass ratio of ordinary methyl dihydrojasmonate to isopropenyl acetate is 1:1-2;

[0032] The composite catalyst is composed of a transition metal salt and layered zirconium phosphate; the content of the transition metal salt is 1%-9% of the mass of the layered zirconium phosphate, and the composite catalyst is prepared by the following preparation method:

[0033] (1) Adsorption: Add transition metal salt and layered zirconium phosphate into solvent at 30-60°C, disperse evenly, and the adsorption time is 2-6 hours;

[0034] (2) Drying: removing excess water and drying to obtain a precursor;

[0035] (3) Calcination: calcining the precursor at 300-500° C. for 3-6 hours to obtain the composite catalyst.

[0036] Since the composite catalyst is used in the reaction of the present invention, there is no need to add alkaline substances for quenching and repeated washing after the reaction is completed, not only no waste salt and waste water are generated, but also the large-scale production operation process is simplified; and the composite catalyst can be recycled and reused.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The present invention utilizes a composite catalyst to catalyze the reaction of common methyl dihydrojasmonate and isopropenyl acetate, achieves a high conversion rate and a high selectivity of the reaction under relatively mild reaction conditions, does not require the addition of alkaline substances for quenching and repeated washing after the reaction is completed, not only does no waste salt and waste water generate, but also simplifies the large-scale production operation process; meanwhile, the catalyst is easy to separate and recycle, thereby reducing the catalyst cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is an electron microscope photograph of the catalyst CAT6# prepared in Example 6;

[0040] Figure 2 is the gas phase spectrum of the product obtained by using Example 3;

[0041] Figure 3 The mass spectrum of the product obtained by using Example 3 is shown in FIG. DETAILED DESCRIPTION

[0042] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0043] Ordinary methyl dihydrojasmonate is produced by the company itself and has a content of 98.5%.

[0044] Isopropenyl acetate, Aladdin, content>99%.

[0045] Example 1

[0046] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Mg-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT1# and used for later use.

[0047] Example 2

[0048] 3.617 g of Fe(NO3)3·9H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Mg-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT2# and kept aside.

[0049] Example 3

[0050] 2.489 g of FeSO4·7H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Mg-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT3# and used for standby.

[0051] Example 4

[0052] Add 2.489g of Fe(acac)3 (ferric acetylacetonate) to 10mL of ethanol, and after it is completely dissolved, add 30mL of deionized water, stir evenly, add 10g of Mg-α-ZrP, raise the temperature to 50°C, keep warm and adsorb for 5 hours, and remove water by vacuum rotary evaporation to obtain a precursor. Then, place the obtained precursor in a muffle furnace, raise the temperature to 400°C, calcine for 5 hours, and cool to room temperature to obtain a catalyst, which is recorded as CAT4# and set aside.

[0053] Example 5

[0054] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT5# and used for standby.

[0055] Example 6

[0056] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT6# and used for standby.

[0057] The CAT6# was characterized using a scanning electron microscope (Japan JEOL, model: JSM-6701F). Figure 1 As shown, it can be seen that the support material still maintains its original lamellar structure without collapse, which makes the catalyst have higher activity and selectivity.

[0058] Example 7

[0059] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Ni-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT7# and used for later use.

[0060] Example 8

[0061] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 2 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT8# and used for later use.

[0062] Example 9

[0063] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 3 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT9# and used for standby.

[0064] Example 10

[0065] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 4 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT10# and used for later use.

[0066] Embodiment 11

[0067] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT11# and used for later use.

[0068] Example 12

[0069] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 6 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT12# and used for standby.

[0070] Example 13

[0071] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 30°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT13# and used for later use.

[0072] Embodiment 14

[0073] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 40°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT14# and used for later use.

[0074] Embodiment 15

[0075] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT15# and used for later use.

[0076] Example 16

[0077] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 60°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT16# and used for later use.

[0078] Embodiment 17

[0079] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 3 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT17# and used for standby.

[0080] Embodiment 18

[0081] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 7 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT18# and used for later use.

[0082] Embodiment 19

[0083] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 9 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT19# and used for standby.

[0084] Embodiment 20

[0085] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 300°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT20# and used for later use.

[0086] Embodiment 21

[0087] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 500°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT21# and used for standby.

[0088] Embodiment 22

[0089] 0.484 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT22# and used for standby.

[0090] Embodiment 23

[0091] 1.452 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT23# and used for later use.

[0092] Embodiment 24

[0093] 3.388 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT24# and used for standby.

[0094] Embodiment 25

[0095] 4.356 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT25# and used for later use.

[0096] Embodiment 26

[0097] 1.965 g of Zn(NO3)2·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT26# and used for later use.

[0098] Embodiment 27

[0099] 1.965 g of CuSO4·5H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT27# and used for standby.

[0100] Embodiment 28

[0101] 2.239 g of NiSO4·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT28# and used for later use.

[0102] Embodiment 29

[0103] 2.113 g of Co(OAc)2·4H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT29# and used for later use.

[0104] Embodiment 30

[0105] 2.353 g of Zr(NO3)4·5H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours for adsorption. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT30# and used for later use.

[0106] Embodiment 31

[0107] 1.454 g of NbCl5 was added to 10 mL of ethanol. After it was completely dissolved, 30 mL of deionized water was added. After stirring evenly, 10 g of Cu-α-ZrP was added, the temperature was raised to 50 ° C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400 ° C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT31# and used for standby.

[0108] Embodiment 32

[0109] 6.441 g of (NH4)6Mo7O24 ·4H2O was added to 40mL of deionized water. After it was completely dissolved, 10g of Cu-α-ZrP was added, the temperature was raised to 50°C, and the mixture was kept warm for 5 hours. The water was removed by vacuum rotary evaporation to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as CAT32# and kept aside.

[0110] Comparative Example 1

[0111] 10 g of Cu-α-ZrP was placed in a muffle furnace, heated to 400° C., calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as comparative catalyst #1 and kept for later use.

[0112] Comparative Example 2

[0113] 2.420 g of FeCl3·6H2O was added to 40 mL of deionized water. After it was completely dissolved, 10 g of ZSM-5 was added, the temperature was raised to 50°C, and the mixture was adsorbed for 5 hours under reduced pressure and evaporated to remove water to obtain a precursor. The obtained precursor was then placed in a muffle furnace, heated to 400°C, calcined for 5 hours, and cooled to room temperature to obtain a catalyst, which was recorded as comparative catalyst 2# and used for standby.

[0114] Application Example 1

[0115] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (1.132g, 1.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.44g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.28%.

[0116] Application Example 2

[0117] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (3.3948g, 3.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.22g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.86%.

[0118] Application Example 3

[0119] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain the product 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate 132.22g, content>99%, and the calculated yield is 98.61%.

[0120] The product was tested by gas chromatography (gas chromatograph: Fuli 9790; chromatographic column DB-17, 50m×0.25mm×0.25μm; detection conditions: constant temperature at 220℃); the results are as follows Figure 2 As shown, the product peak position is 11.828min and the content is 98.61%.

[0121] The product was detected by mass spectrometry (Agilent 7890B-5977B), and the results were as follows Figure 3 As shown, the product peak is at m / z 268.1. Comparison with the standard spectrum library shows that the experimental product is 2-(3-acetoxy-2-pentylcyclopent-2-en-1-yl)acetate methyl ester.

[0122] Application Example 4

[0123] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (7.921g, 7.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.41g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.75%.

[0124] Application Example 5

[0125] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (10.184g, 9.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.50g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.82%.

[0126] Application Example 6

[0127] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 80°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.24g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.13%.

[0128] Application Example 7

[0129] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 120°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.34g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.70%.

[0130] Application Example 8

[0131] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 140°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.37g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.72%.

[0132] Application Example 9

[0133] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 160°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.87g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.35%.

[0134] Application Example 10

[0135] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (113.16g, 1.130mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.01g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.45%.

[0136] Application Example 11

[0137] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (124.48g, 1.243mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.18g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.58%.

[0138] Application Example 12

[0139] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (181.056g, 1.808mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.60g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.89%.

[0140] Application Example 13

[0141] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (226.32g, 2.260mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.58g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.13%.

[0142] Application Example 14

[0143] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 2 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 128.88g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 96.12%.

[0144] Application Example 15

[0145] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 3 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.14g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.80%.

[0146] Application Example 16

[0147] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 5 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.45g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.78%.

[0148] Application Example 17

[0149] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 6 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.48g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.80%.

[0150] Application Example 18

[0151] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (203.688g, 2.034mol), CAT6# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.95g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.41%.

[0152] Application Example 19

[0153] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT1# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.96g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.67%.

[0154] Application Example 20

[0155] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT2# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.00g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.70%.

[0156] Application Example 21

[0157] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT3# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.97g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.68%.

[0158] Application Example 22

[0159] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT4# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.15g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.81%.

[0160] Application Example 23

[0161] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT5# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 129.96g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 96.92%.

[0162] Application Example 24

[0163] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT7# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.95g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.41%.

[0164] Application Example 25

[0165] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT8# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.79g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.54%.

[0166] Application Example 26

[0167] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT9# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.66g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.19%.

[0168] Application Example 27

[0169] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT10# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.02g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.46%.

[0170] Application Example 28

[0171] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT11# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.25g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.63%.

[0172] Application Example 29

[0173] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT12# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.07g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.50%.

[0174] Application Example 30

[0175] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT13# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.17g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.57%.

[0176] Application Example 31

[0177] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT14# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.15g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.81%.

[0178] Application Example 32

[0179] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT15# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction solution to recover the catalyst, collect the reaction solution, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 129.10g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 96.28%.

[0180] Application Example 33

[0181] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT16# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.37g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.72%.

[0182] Application Example 34

[0183] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT17# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.17g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.57%.

[0184] Application Example 35

[0185] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT18# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.55g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.36%.

[0186] Application Example 36

[0187] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT19# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.42g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.01%.

[0188] Application Example 37

[0189] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT20# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.48g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.31%.

[0190] Application Example 38

[0191] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT21# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.75g ​​of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.26%.

[0192] Application Example 39

[0193] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT22# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.45g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.78%.

[0194] Application Example 40

[0195] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT23# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.72g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.98%.

[0196] Application Example 41

[0197] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT24# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.19g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.59%.

[0198] Application Example 42

[0199] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT25# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 132.05g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.48%.

[0200] Application Example 43

[0201] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT26# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.56g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.12%.

[0202] Application Example 44

[0203] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT27# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.40g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.25%.

[0204] Application Example 45

[0205] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT28# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 130.24g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.13%.

[0206] Application Example 46

[0207] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT29# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.83g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 98.32%.

[0208] Application Example 47

[0209] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), CAT30# (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 131.30g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, the content is>99%, and the calculated yield is 97.92%.

[0210] Application Comparative Example 1

[0211] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), comparative catalyst 1 (5.658g, 5.0% of the mass of methyl dihydrojasmonate), mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, cool naturally after recovery, and set aside. Finally, distill to obtain 43.12g of the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate, with a calculated yield of 32.16%.

[0212] Application Comparative Example 2

[0213] At room temperature, in a three-necked flask, add ordinary methyl dihydrojasmonate (113.16g, 0.5mol), isopropenyl acetate (135.792g, 1.356mol), and comparative catalyst 2 (5.658g, 5.0% of the mass of methyl dihydrojasmonate) in sequence, mix well, heat to 100°C and keep warm for 4 hours, cool naturally to room temperature after the reaction, filter the reaction liquid to recover the catalyst, collect the reaction liquid, and distill and recover the excess isopropenyl acetate under vacuum conditions, control the temperature not to exceed 80°C, and cool naturally after recovery for use. Finally, distillation gave the intermediate 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) methyl acetate 91.63g, with a calculated yield of 68.34%.

[0214] Catalyst application experiment

[0215] The catalyst recovered in Application Example 3 was used in an application experiment. The reaction conditions and operation were the same as those in Application Example 1 (the amount of catalyst was 1% of the mass of methyl dihydrojasmonate). The experimental results are shown in Table 1.

[0216] Table 1 Summary of catalyst application experimental results

[0217]

[0218] It can be seen that the composite catalyst of the present invention can be reused many times and has good catalytic activity.

[0219] The applicant declares that the present invention illustrates the process method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned process steps, that is, it does not mean that the present invention must rely on the above-mentioned process steps to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing methyl 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl)acetate, characterized in that: The preparation method comprises the following steps: Ordinary methyl dihydrojasmonate and isopropenyl acetate react under the catalysis of a composite catalyst to obtain the methyl 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) acetate, wherein the composite catalyst is composed of a transition metal salt and layered zirconium phosphate; The transition metal salt is any one or a combination of at least two of nitrates, sulfates, chlorides, acetates, hydroxides or hydrates thereof containing Fe, Cu, Zn, Ni, Co, Zr, Nb or Mo; The layered zirconium phosphate is selected from one or a combination of at least two of α-ZrP, Cu-α-ZrP, Mg-α-ZrP, and Ni-α-ZrP.

2. The preparation method according to claim 1, characterized in that: The transition metal salt is FeCl3·6H2O, Fe(NO3)3·9H2O, FeSO4·7H2O, ferric acetylacetonate, Zn(NO3)2·6H2O, CuSO4·5H2O, NiSO4·6H2O, Co(OAc)2·4H2O, Zr(NO3)4·5H2O, NbCl5 or (NH4)6Mo7O 24 Any one or a combination of at least two of 4H2O.

3. The preparation method according to claim 1, characterized in that: The amount of the transition metal salt used is such that the content of metal ions in the transition metal salt is 1%-9% of the mass of the layered zirconium phosphate.

4. The preparation method according to claim 1, characterized in that: The preparation method of the composite catalyst is as follows: (1) Adsorption: Add transition metal salt and layered zirconium phosphate into the solvent and disperse them evenly; (2) Drying: removing excess water and drying to obtain a precursor; (3) Calcination: calcining the precursor to obtain the composite catalyst; The solvent in step (1) is selected from an organic solvent or water; In step (1), the adsorption time is 2-6 hours, and the adsorption temperature is 30-60°C; In step (3), the calcination time is 3-6 hours, and the calcination temperature is 300-500°C.

5. The preparation method according to claim 4, characterized in that: In step (1), the adsorption time is 4-6 hours and the adsorption temperature is 30-50°C; In step (3), the calcination time is 4-6 hours, and the calcination temperature is 300-400°C.

6. The preparation method according to claim 1, characterized in that: The amount of the composite catalyst used is 1%-10% of the mass of ordinary methyl dihydrojasmonate; The mass ratio of the common methyl dihydrojasmonate to isopropenyl acetate is 1:1-2; The reaction temperature is 80-160° C., and the reaction time is 2-6 hours.

7. The preparation method according to claim 1, characterized in that: The amount of the composite catalyst used is 5%-7% of the mass of ordinary methyl dihydrojasmonate; The reaction temperature is 100-120° C., and the reaction time is 3-5 h.

8. The preparation method according to claim 1, characterized in that: The preparation method comprises the following steps: Ordinary methyl dihydrojasmonate and isopropenyl acetate are reacted at 80-160° C. for 2-6 hours under the catalysis of a composite catalyst to obtain the methyl 2-(3-acetoxy-2-pentylcyclopent-2-ene-1-yl) acetate; the amount of the composite catalyst is 1%-10% of the mass of ordinary methyl dihydrojasmonate, and the mass ratio of ordinary methyl dihydrojasmonate to isopropenyl acetate is 1:1-2. The composite catalyst is composed of a transition metal salt and a layered zirconium phosphate; the transition metal salt is any one of nitrates, sulfates, chlorides, acetates, hydroxides or hydrates thereof containing Fe, Cu, Zn, Ni, Co, Zr, Nb or Mo, or a combination of at least two thereof; the layered zirconium phosphate is selected from one of α-ZrP, Cu-α-ZrP, Mg-α-ZrP and Ni-α-ZrP, or a combination of at least two thereof; The content of the transition metal salt is 1%-9% of the mass of the layered zirconium phosphate; The composite catalyst is prepared by the following preparation method: (1) Adsorption: Add transition metal salt and layered zirconium phosphate into solvent at 30-60°C, disperse evenly, and the adsorption time is 2-6 hours; (2) Drying: removing excess water and drying to obtain a precursor; (3) Calcination: calcining the precursor at 300-500° C. for 3-6 hours to obtain the composite catalyst.

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