A method for preparing high-purity all-cis-jasmone
By depositing a catalyst of composite metal oxide iron oxide and nickel oxide on the nano-silica support, problems such as low yield and low purity in jasmonone synthesis are solved, and high efficiency of high purity cismonone is achieved.
Patent Information
- Application Number
- CN202411762706.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-03
- Publication Date
- 2025-07-08
- Estimated Expiration
- 2044-12-03
AI Technical Summary
The existing jasmonone synthesis process has problems such as low yield, complex process, expensive raw material prices and low product purity, making it difficult to achieve large-scale and mass production.
Using nanosilicon dioxide as a support, a catalyst of composite metal oxide iron oxide and nickel oxide was deposited on the surface, and a metal alloy catalyst was formed by hydrogen reduction, and amorphous carbon was deposited on the surface to improve catalytic activity and reaction selectivity, and high-purity cis jasminone was prepared.
The yield and selectivity of jasmonone are improved, the product is purified, the preparation conditions are mild, and the reaction method is simple.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organic chemistry, and particularly relates to a method for preparing high-purity all-cis-jasmone. Background Art
[0002] Jasmone is a natural substance present in jasmine flowers, spearmint, bergamot, mint, tea leaves and various other flowers. Jasmone exists in two different isomeric forms around the pentenyl double bond, namely all-cis-jasmone and trans-jasmone. Among them, all-cis-jasmone has fruity, floral and jasmine flower odors. The natural jasmone component is mainly all-cis-jasmone. Synthetic jasmone contains both, but still mainly all-cis-jasmone.
[0003] Jasmone is widely present in jasmine flowers, spearmint and bergamot. With its unique odor, jasmone can be formulated into jasmine essence and widely used in the fields of organic chemistry, edible flavors, etc. In addition, jasmone also has the function of anti-nematodes and has broad application prospects in the agricultural field. With the upgrading of consumption and the green development of pesticides, the future market development potential of jasmone is relatively large.
[0004] The extraction methods of all-cis-jasmone mainly include distillation method, extraction method and crystallization method. Among them, the distillation method is one of the most commonly used extraction methods, mainly by distilling to extract the volatile components in jasmine flowers. The extraction method is to soak jasmine flowers in an organic solvent and then extract them by extraction. The crystallization method is to crystallize the jasmone solution obtained by extraction to obtain all-cis-jasmone with higher purity. Natural jasmone can be prepared by decarboxylation reaction of jasmonic acid of plants. Natural jasmone exists in jasmine oil, neroli oil, bergamot oil, etc. The synthetic processes of jasmone are diverse. Currently, there are more than 200 published synthetic routes for jasmone. However, due to problems such as low yield, complex process, high price of raw materials, etc. in the synthetic processes, it is difficult to produce jasmone on a large scale and in batches. These existing methods all have problems such as long synthetic process routes, low product yields, large amounts of waste and difficult to treat, and low product purity. Summary of the Invention
[0005] The purpose of the present invention is to provide a method for preparing high-purity all-cis-jasmone, which greatly improves the activity and reaction selectivity of the catalyst, enables the reaction to generate cis-jasmone, has high yield, good selectivity, mild preparation conditions, simple reaction method and high product purity.
[0006] The technical solution of the present invention is realized as follows:
[0007] The present invention provides a method for preparing high-purity all-cis-jasmone. Sodium amide is prepared by reacting sodium with liquid ammonia, a catalyst is added, and the reaction is stirred. The solvent is removed under reduced pressure. Under the protection of an inert gas and in an ice-water bath, 2-formylmethyl-3-methyl-cyclopentene-2-one and toluene are added, and the reaction is heated and stirred. After cooling to room temperature, the product is collected by distillation under reduced pressure to obtain high-purity all-cis-jasmone.
[0008] As a further improvement of the present invention, the mass-volume ratio of sodium to liquid ammonia is 1-1.5:200 g / mL, the addition amount of the catalyst is 2-3 wt% of the total mass of the system, and the mass ratio of sodium to 2-formylmethyl-3-methyl-cyclopentene-2-one is 1-1.5:5-7; the temperature of the distillation under reduced pressure is 70-75 °C, the stirring reaction time is 0.5-1 h, the temperature of the heating and stirring reaction is 100-120 °C, and the time is 30-50 min.
[0009] As a further improvement of the present invention, the preparation method of the catalyst is as follows:
[0010] S1. Add silane coupling agent KH550 and silane coupling agent KH560 to dichloromethane, stir the reaction, add thionyl chloride dropwise, heat and stir the reaction, heat to remove the excess thionyl chloride, and dry to obtain a modifier.
[0011] S2. Add nano-silica to water, add nickel salt and iron salt, stir the reaction, adjust the pH value of the solution, heat and crystallize, and calcine to obtain composite metal oxide / nano-silica.
[0012] S3. Place the composite metal oxide / nano-silica in the heat preservation area of a tubular furnace, heat to a first temperature under the protection of an inert gas, change to introduce hydrogen, heat to a second temperature, then introduce n-hexane, keep the reaction at a constant temperature, and then cool to room temperature under the protection of an inert gas to obtain composite nano-spheres.
[0013] S4. Add the composite nano-spheres to ethanol, add the modifier, heat and stir the reaction, centrifuge, wash, and dry to obtain modified nano-silica.
[0014] S5. Add triphenylphosphine to toluene, add the modified nano-silica, heat and stir the reaction, centrifuge, wash, and dry to obtain the catalyst.
[0015] As a further improvement of the present invention, in step S1, the mass ratio of silane coupling agent KH550, silane coupling agent KH560, and thionyl chloride is 5-7:1-2:2-3, and the temperature of the heating and stirring reaction is 40-50 °C, and the time is 4-6 h.
[0016] As a further improvement of the present invention, in step S2, the mass ratio of the nano-silica, nickel salt and iron salt is 10:1 - 2:0.5 - 1.5, the stirring reaction time is 20 - 40 min, the pH value of the solution is adjusted to 9 - 10, the heating crystallization temperature is 85 - 95 °C, the time is 1 - 3 h, and the calcination temperature is 400 - 600 °C, the time is 2 - 4 h.
[0017] As a further improvement of the present invention, in step S3, when the ventilation rate of n-hexane is 0.3 - 0.5 mL / min, the ventilation rate of hydrogen is 1 - 2 mL / min, the heat preservation reaction time is 20 - 40 min, the first temperature is 420 - 450 °C, and the second temperature is 650 - 670 °C.
[0018] As a further improvement of the present invention, in step S4, the mass ratio of the composite nanospheres to the modifier is 10:2 - 3, and the heating and stirring reaction temperature is 40 - 50 °C, and the time is 1 - 2 h.
[0019] As a further improvement of the present invention, in step S5, the mass ratio of triphenylphosphine to modified nano-silica is 2 - 4:10, and the heating and stirring reaction temperature is 80 - 90 °C, and the time is 2 - 4 h.
[0020] The present invention further protects a high-purity all-cis jasmon obtained by the above preparation method.
[0021] The present invention further protects a catalyst, and the preparation method includes the following steps:
[0022] S1. Add 5 - 7 parts by weight of silane coupling agent KH550 and 1 - 2 parts by weight of silane coupling agent KH560 to dichloromethane, stir and react, dropwise add 2 - 3 parts by weight of thionyl dichloride, heat to 40 - 50 °C, stir and react for 4 - 6 h, heat to remove the excessive thionyl dichloride, and dry to obtain a modifier;
[0023] S2. Add 10 parts by weight of nano-silica to water, add 1 - 2 parts by weight of nickel salt and 0.5 - 1.5 parts by weight of iron salt, stir and react for 20 - 40 min, adjust the pH value of the solution to 9 - 10, heat to 85 - 95 °C, crystallize for 1 - 3 h, and calcine at 400 - 600 °C for 2 - 4 h to obtain composite metal oxide / nano-silica;
[0024] S3. Place the composite metal oxide / nano-silicon oxide in the heat preservation zone of a tubular furnace. Under the protection of an inert gas, heat it up to 420 - 450 °C, then change to introduce hydrogen with a gas flow rate of 1 - 2 mL / min, heat it up to 650 - 670 °C, then introduce n-hexane with a gas flow rate of 0.3 - 0.5 mL / min, keep the temperature for reaction for 20 - 40 min, and then cool it to room temperature under the protection of an inert gas to obtain composite nano-spheres;
[0025] S4. Add 10 parts by weight of the composite nano-spheres to ethanol, add 2 - 3 parts by weight of a modifier, heat it to 40 - 50 °C, stir and react for 1 - 2 h, centrifuge, wash, and dry to obtain modified nano-silicon oxide;
[0026] S5. Add 2 - 4 parts by weight of triphenylphosphine to toluene, add 10 parts by weight of the modified nano-silicon oxide, heat it to 80 - 90 °C, stir and react for 2 - 4 h, centrifuge, wash, and dry to obtain a catalyst.
[0027] The present invention has the following beneficial effects:
[0028] The present invention prepares a catalyst. Using nano-silicon dioxide as a carrier, composite metal oxides iron oxide and nickel oxide are deposited on the surface, and after crystallization, an anionic layered material with a similar structure is formed. Due to the influence of the lowest lattice energy effect, lattice positioning effect, and covalent interaction between components, the metal elements in the layer board are uniform in composition and structure at the molecular level. After high-temperature treatment, the layered structure is lost, forming uniformly dispersed composite metal oxides. After hydrogen reduction, chemical vapor deposition occurs, forming a metal alloy catalyst on the one hand, improving the catalytic activity. At the same time, amorphous carbon is deposited on the surface by chemical vapor deposition, greatly increasing the specific surface area of the carrier, facilitating modification with the modifier.
[0029] The preparation of the modifier in the present invention is to react the silane coupling agent KH550 with an amino group and the silane coupling agent KH560 with an epoxy group. The amino group and the epoxy group react, and the amino group is in a small amount. Under the action of thionyl chloride, a chlorosilane coupling agent is formed, which reacts with the modified nano-silicon oxide on the one hand and with triphenylphosphine on the other hand to form coupled triphenylphosphonium bromide, greatly improving the activity and reaction selectivity of the catalyst, enabling the reaction to produce cis-jasmone with a high yield, good selectivity, mild preparation conditions, a simple reaction method, and high product purity. Detailed implementation manners
[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.
[0031] The average particle size of the nano-silica is 150 ± 50 nm.
[0032] Preparation Example 1
[0033] A catalyst, the preparation method comprising the following steps:
[0034] S1. Add 5 g of silane coupling agent KH550 and 1 g of silane coupling agent KH560 to 200 mL of dichloromethane, stir and react, dropwise add 2 g of thionyl chloride, heat to 40 °C, stir and react for 4 h, heat to remove the excess thionyl chloride, dry to obtain a modifier;
[0035] S2. Add 10 g of nano-silica to 200 mL of water, add 1 g of nickel chloride and 0.5 g of ferric chloride, stir and react for 20 min, adjust the pH value of the solution to 9, heat to 85 °C, crystallize for 1 h, calcine at 400 °C for 2 h to obtain composite metal oxide / nano-silica;
[0036] S3. Place the composite metal oxide / nano-silica in the heat preservation zone of a tubular furnace, heat up to 420 °C under nitrogen protection, change to pass hydrogen, the gas flow rate is 1 mL / min, heat up to 650 °C, then pass in n-hexane, the gas flow rate is 0.3 mL / min, keep warm and react for 20 min, then cool to room temperature under nitrogen protection to obtain composite nano-spheres;
[0037] S4. Add 10 g of the composite nano-spheres to 200 mL of ethanol, add 2 g of the modifier, heat to 40 °C, stir and react for 1 h, centrifuge, wash, and dry to obtain modified nano-silica;
[0038] S5. Add 2 g of triphenylphosphine to 200 mL of toluene, add 10 g of the modified nano-silica, heat to 80 °C, stir and react for 2 h, centrifuge, wash, and dry to obtain the catalyst.
[0039] Preparation Example 2
[0040] A catalyst, the preparation method comprising the following steps:
[0041] S1. Add 7 g of silane coupling agent KH550 and 2 g of silane coupling agent KH560 to 200 mL of dichloromethane, stir and react, dropwise add 3 g of thionyl chloride, heat to 50 °C, stir and react for 6 h, heat to remove the excess thionyl chloride, dry to obtain a modifier;
[0042] S2. Add 10 g of nano-silica to 200 mL of water, add 2 g of nickel chloride and 1.5 g of ferric chloride, stir and react for 40 min, adjust the pH value of the solution to 10, heat to 95 °C, crystallize for 3 h, calcine at 600 °C for 4 h to obtain composite metal oxide / nano-silica;
[0043] S3. Place the composite metal oxide / nano-silica in the heat preservation zone of a tubular furnace. Under nitrogen protection, heat it to 450 °C, then change to introducing hydrogen with a gas flow rate of 2 mL / min, heat it to 670 °C, then introduce n-hexane with a gas flow rate of 0.5 mL / min, keep the temperature for reaction for 40 min, and then cool it to room temperature under nitrogen protection to obtain composite nano-spheres;
[0044] S4. Add 10 g of the composite nano-spheres to 200 mL of ethanol, add 3 g of the modifier, heat to 50 °C, stir and react for 2 h, centrifuge, wash, and dry to obtain modified nano-silica;
[0045] S5. Add 4 g of triphenylphosphine to 200 mL of toluene, add 10 g of the modified nano-silica, heat to 90 °C, stir and react for 4 h, centrifuge, wash, and dry to obtain the catalyst.
[0046] Preparation Example 3
[0047] A catalyst, the preparation method includes the following steps:
[0048] S1. Add 6 g of silane coupling agent KH550 and 1.5 g of silane coupling agent KH560 to 200 mL of dichloromethane, stir and react, dropwise add 2.5 g of thionyl chloride, heat to 45 °C, stir and react for 5 h, heat to remove the excessive thionyl chloride, and dry to obtain the modifier;
[0049] S2. Add 10 g of nano-silica to 200 mL of water, add 1.5 g of nickel chloride and 1 g of iron chloride, stir and react for 30 min, adjust the pH value of the solution to 9.5, heat to 90 °C, crystallize for 2 h, and calcine at 500 °C for 3 h to obtain the composite metal oxide / nano-silica;
[0050] S3. Place the composite metal oxide / nano-silica in the heat preservation zone of a tubular furnace. Under nitrogen protection, heat it to 430 °C, then change to introducing hydrogen with a gas flow rate of 1.5 mL / min, heat it to 660 °C, then introduce n-hexane with a gas flow rate of 0.4 mL / min, keep the temperature for reaction for 30 min, and then cool it to room temperature under nitrogen protection to obtain composite nano-spheres;
[0051] S4. Add 10 g of the composite nano-spheres to 200 mL of ethanol, add 2.5 g of the modifier, heat to 45 °C, stir and react for 1.5 h, centrifuge, wash, and dry to obtain modified nano-silica;
[0052] S5. Add 3 g of triphenylphosphine to 200 mL of toluene, add 10 g of the modified nano-silica, heat to 85 °C, stir and react for 3 h, centrifuge, wash, and dry to obtain the catalyst.
[0053] Comparative Preparation Example 1
[0054] Compared with Preparation Example 3, the difference lies in that nickel chloride was not added in Step S2.
[0055] Specifically as follows:
[0056] S1. Add 6 g of silane coupling agent KH550 and 1.5 g of silane coupling agent KH560 to 200 mL of dichloromethane, stir and react, add 2.5 g of thionyl chloride dropwise, heat to 45 °C, stir and react for 5 h, heat to remove the excess thionyl chloride, and dry to obtain a modifier.
[0057] S2. Add 10 g of nano-silica to 200 mL of water, add 2.5 g of ferric chloride, stir and react for 30 min, adjust the pH value of the solution to 9.5, heat to 90 °C, crystallize for 2 h, and calcine at 500 °C for 3 h to obtain metal oxide / nano-silica.
[0058] S3. Place the metal oxide / nano-silica in the heat preservation zone of a tubular furnace, heat up to 430 °C under nitrogen protection, change to introduce hydrogen, with a gas flow rate of 1.5 mL / min, heat up to 660 °C, then introduce n-hexane, with a gas flow rate of 0.4 mL / min, keep the temperature for reaction for 30 min, and then cool to room temperature under nitrogen protection to obtain composite nano-spheres.
[0059] S4. Add 10 g of the composite nano-spheres to 200 mL of ethanol, add 2.5 g of the modifier, heat to 45 °C, stir and react for 1.5 h, centrifuge, wash, and dry to obtain modified nano-silica.
[0060] S5. Add 3 g of triphenylphosphine to 200 mL of toluene, add 10 g of the modified nano-silica, heat to 85 °C, stir and react for 3 h, centrifuge, wash, and dry to obtain a catalyst.
[0061] Comparative Preparation Example 2
[0062] Compared with Preparation Example 3, the difference lies in that ferric chloride was not added in Step S2.
[0063] Specifically as follows:
[0064] S1. Add 6 g of silane coupling agent KH550 and 1.5 g of silane coupling agent KH560 to 200 mL of dichloromethane, stir and react, add 2.5 g of thionyl chloride dropwise, heat to 45 °C, stir and react for 5 h, heat to remove the excess thionyl chloride, and dry to obtain a modifier.
[0065] S2. Add 10 g of nano-silica to 200 mL of water, add 2.5 g of nickel chloride, stir and react for 30 min, adjust the pH value of the solution to 9.5, heat to 90 °C, crystallize for 2 h, and calcine at 500 °C for 3 h to obtain metal oxide / nano-silica.
[0066] S3. Place the metal oxide / nanosilica in the heat preservation zone of the tubular furnace. Under nitrogen protection, heat it up to 430 °C, then change to introduce hydrogen with a gas flow rate of 1.5 mL / min, heat it up to 660 °C, then introduce n-hexane with a gas flow rate of 0.4 mL / min, keep the temperature for reaction for 30 min, and then cool it to room temperature under nitrogen protection to obtain composite nanospheres;
[0067] S4. Add 10 g of the composite nanospheres to 200 mL of ethanol, add 2.5 g of the modifier, heat to 45 °C, stir and react for 1.5 h, centrifuge, wash, and dry to obtain modified nanosilica;
[0068] S5. Add 3 g of triphenylphosphine to 200 mL of toluene, add 10 g of the modified nanosilica, heat to 85 °C, stir and react for 3 h, centrifuge, wash, and dry to obtain the catalyst.
[0069] Comparative Preparation Example 3
[0070] Compared with Preparation Example 3, the difference lies in that steps S2 and S3 are not carried out.
[0071] Specifically as follows:
[0072] S1. Add 6 g of silane coupling agent KH550 and 1.5 g of silane coupling agent KH560 to 200 mL of dichloromethane, stir and react, dropwise add 2.5 g of thionyl chloride, heat to 45 °C, stir and react for 5 h, heat to remove the excessive thionyl chloride, and dry to obtain the modifier;
[0073] S2. Add 10 g of nanosilica to 200 mL of ethanol, add 2.5 g of the modifier, heat to 45 °C, stir and react for 1.5 h, centrifuge, wash, and dry to obtain modified nanosilica;
[0074] S3. Add 3 g of triphenylphosphine to 200 mL of toluene, add 10 g of the modified nanosilica, heat to 85 °C, stir and react for 3 h, centrifuge, wash, and dry to obtain the catalyst.
[0075] Comparative Preparation Example 4
[0076] Compared with Preparation Example 3, the difference lies in that step S4 is not carried out.
[0077] Specifically as follows:
[0078] S1. Add 6 g of silane coupling agent KH550 and 1.5 g of silane coupling agent KH560 to 200 mL of dichloromethane, stir and react, dropwise add 2.5 g of thionyl chloride, heat to 45 °C, stir and react for 5 h, heat to remove the excessive thionyl chloride, and dry to obtain the modifier;
[0079] S2. Add 10 g of nano-silica into 200 mL of water, add 1.5 g of nickel chloride and 1 g of iron chloride, stir and react for 30 min, adjust the pH value of the solution to 9.5, heat to 90 °C, crystallize for 2 h, and calcine at 500 °C for 3 h to obtain composite metal oxide / nano-silica;
[0080] S3. Place the composite metal oxide / nano-silica in the heat preservation zone of a tubular furnace, heat up to 430 °C under nitrogen protection, change to introduce hydrogen, with a gas flow rate of 1.5 mL / min, heat up to 660 °C, then introduce n-hexane, with a gas flow rate of 0.4 mL / min, keep warm and react for 30 min, and then cool to room temperature under nitrogen protection to obtain composite nano-spheres;
[0081] S4. Add 3 g of triphenylphosphine into 200 mL of toluene, add 10 g of composite nano-spheres, heat to 85 °C, stir and react for 3 h, centrifuge, wash, and dry to obtain the catalyst.
[0082] Comparative Preparation Example 5
[0083] Compared with Preparation Example 3, the difference is that step S5 is not carried out.
[0084] Specifically as follows:
[0085] S1. Add 6 g of silane coupling agent KH550 and 1.5 g of silane coupling agent KH560 into 200 mL of dichloromethane, stir and react, dropwise add 2.5 g of thionyl chloride, heat to 45 °C, stir and react for 5 h, heat to remove the excessive thionyl chloride, and dry to obtain the modifier;
[0086] S2. Add 10 g of nano-silica into 200 mL of water, add 1.5 g of nickel chloride and 1 g of iron chloride, stir and react for 30 min, adjust the pH value of the solution to 9.5, heat to 90 °C, crystallize for 2 h, and calcine at 500 °C for 3 h to obtain composite metal oxide / nano-silica;
[0087] S3. Place the composite metal oxide / nano-silica in the heat preservation zone of a tubular furnace, heat up to 430 °C under nitrogen protection, change to introduce hydrogen, with a gas flow rate of 1.5 mL / min, heat up to 660 °C, then introduce n-hexane, with a gas flow rate of 0.4 mL / min, keep warm and react for 30 min, and then cool to room temperature under nitrogen protection to obtain composite nano-spheres;
[0088] S4. Add 10 g of composite nano-spheres into 200 mL of ethanol, add 2.5 g of the modifier, heat to 45 °C, stir and react for 1.5 h, centrifuge, wash, and dry to obtain modified nano-silica, which is the catalyst.
[0089] Test Example 1
[0090] The specific surface area of the catalysts prepared in Preparation Examples 1-3 and Comparative Preparation Examples 1-5 was measured using a high-throughput gas adsorption instrument. The results are shown in Table 1.
[0091] Table 1
[0092]
[0093]
[0094] As can be seen from the above table, the catalysts prepared in Preparation Examples 1-3 of the present invention have a good specific surface area.
[0095] The preparation method of 2-formylmethyl-3-methyl-cyclopentene-2-one refers to Yoshiaki Nakahara, et al. Agr. Biol. Chem., 39(9), 1887-1888(1975).
[0096] Example 1
[0097] This example provides a method for preparing high-purity all-cis-jasmone. Sodium amide was prepared by reacting 1 g of sodium with 200 mL of liquid ammonia, and the catalyst prepared in Preparation Example 1 was added. The addition amount of the catalyst was 2 wt% of the total mass of the system. The reaction was stirred for 0.5 h, and the solvent was removed under reduced pressure. Under nitrogen protection and in an ice-water bath, 5 g of 2-formylmethyl-3-methyl-cyclopentene-2-one and toluene were added, heated to 100 °C, stirred for 30 min, cooled to room temperature, heated to 70 °C, and the product was collected by vacuum distillation to obtain high-purity all-cis-jasmone.
[0098] Example 2
[0099] This example provides a method for preparing high-purity all-cis-jasmone. Sodium amide was prepared by reacting 1.5 g of sodium with 200 mL of liquid ammonia, and the catalyst prepared in Preparation Example 2 was added. The addition amount of the catalyst was 3 wt% of the total mass of the system. The reaction was stirred for 1 h, and the solvent was removed under reduced pressure. Under nitrogen protection and in an ice-water bath, 7 g of 2-formylmethyl-3-methyl-cyclopentene-2-one and toluene were added, heated to 120 °C, stirred for 50 min, cooled to room temperature, heated to 75 °C, and the product was collected by vacuum distillation to obtain high-purity all-cis-jasmone.
[0100] Example 3
[0101] This embodiment provides a method for preparing high-purity all-cis jasmonone. 1.2 g of sodium is reacted with 200 mL of liquid ammonia to prepare sodium amide, and the catalyst prepared in Preparation Example 3 is added. The addition amount of the catalyst is 2.5 wt% of the total mass of the system. Stir and react for 1 h, remove the solvent under reduced pressure. Under nitrogen protection and in an ice-water bath, 6 g of 2-formylmethyl-3-methyl-cyclopentene-2-one and toluene are added, heated to 110 °C, stirred and reacted for 40 min, cooled to room temperature, heated to 72 °C, and the product is collected by vacuum distillation to obtain high-purity all-cis jasmonone.
[0102] Comparative Example 1
[0103] Compared with Example 3, the difference lies in that the catalyst is prepared from Comparative Preparation Example 1.
[0104] Comparative Example 2
[0105] Compared with Example 3, the difference lies in that the catalyst is prepared from Comparative Preparation Example 2.
[0106] Comparative Example 3
[0107] Compared with Example 3, the difference lies in that the catalyst is prepared from Comparative Preparation Example 3.
[0108] Comparative Example 4
[0109] Compared with Example 3, the difference lies in that the catalyst is prepared from Comparative Preparation Example 4.
[0110] Comparative Example 5
[0111] Compared with Example 3, the difference lies in that the catalyst is prepared from Comparative Preparation Example 5.
[0112] Test Example 2
[0113] The methods in Examples 1-3 and Comparative Examples 1-5 of the present invention were evaluated, and the results are shown in Table 2.
[0114] Table 2
[0115] Group Yield of jasmonone (%) Purity of cis-jasmonone in the product (%) Example 1 79.5 99.2 Example 2 80.2 99.5 Example 3 80.7 99.7 Comparative Example 1 70.2 98.2 Comparative Example 2 68.9 97.8 Comparative Example 3 63.8 92.5 Comparative Example 4 65.5 94.3 Comparative Example 5 60.9 92.7
[0116] As can be seen from the above table, the methods in Examples 1-3 of the present invention have high yields and high purities of cis-jasmonone.
[0117] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
Claims
1. A method for preparing high-purity all-cis jasmonone, characterized in that, Sodium and liquid ammonia are reacted to obtain sodium amide. A catalyst is added, and the reaction is stirred. The solvent is removed under reduced pressure. Under the protection of an inert gas and in an ice-water bath, 2-formylmethyl-3-methyl-cyclopentene-2-one and toluene are added, and the reaction is heated and stirred. It is cooled to room temperature, and the product is collected by vacuum distillation to obtain high-purity all-cis jasmon; The preparation method of the catalyst is as follows: S1. Silane coupling agent KH550 and silane coupling agent KH560 are added to dichloromethane, and the reaction is stirred. Thionyl chloride is added dropwise, and the reaction is heated and stirred. The excess thionyl chloride is removed by heating, and it is dried to obtain a modifier; S2. Nano-silica is added to water, nickel salt and iron salt are added, and the reaction is stirred. The pH value of the solution is adjusted, and it is heated and crystallized, and calcined to obtain composite metal oxide / nano-silica; S3. The composite metal oxide / nano-silica is placed in the heat preservation zone of a tubular furnace. Under the protection of an inert gas, it is heated to a first temperature, then hydrogen is introduced, and it is heated to a second temperature. Then n-hexane is introduced, and the reaction is kept warm. Then it is cooled to room temperature under the protection of an inert gas to obtain composite nano-spheres; S4. The composite nano-spheres are added to ethanol, the modifier is added, and the reaction is heated and stirred. It is centrifuged, washed, and dried to obtain modified nano-silica; S5. Triphenylphosphine is added to toluene, the modified nano-silica is added, and the reaction is heated and stirred. It is centrifuged, washed, and dried to obtain a catalyst.
2. The preparation method according to claim 1, characterized in that, The mass-volume ratio of the sodium and the liquid ammonia is 1-1.5:200 g / mL, the addition amount of the catalyst is 2-3 wt% of the total mass of the system, and the mass ratio of the sodium and 2-formylmethyl-3-methyl-cyclopentene-2-one is 1-1.5:5-7; the temperature of the vacuum distillation is 70-75 °C, the time of the stirring reaction is 0.5-1 h, the temperature of the heating and stirring reaction is 100-120 °C, and the time is 30-50 min.
3. The preparation method according to claim 1, characterized in that, In step S1, the mass ratio of the silane coupling agent KH550, the silane coupling agent KH560, and thionyl chloride is 5-7:1-2:2-3, the temperature of the heating and stirring reaction is 40-50 °C, and the time is 4-6 h.
4. The preparation method according to claim 1, characterized in that, In step S2, the mass ratio of the nano-silica, the nickel salt, and the iron salt is 10:1-2:0.5-1.5, the time of the stirring reaction is 20-40 min, the pH value of the solution is adjusted to 9-10, the temperature of the heating and crystallization is 85-95 °C, the time is 1-3 h, and the temperature of the calcination is 400-600 °C, and the time is 2-4 h.
5. The preparation method according to claim 1, wherein In step S3, the ventilation rate of the n-hexane is 0.3-0.5 mL / min, the ventilation rate of the hydrogen is 1-2 mL / min, the time of the heat preservation reaction is 20-40 min, the first temperature is 420-450 °C, and the second temperature is 650-670 °C.
6. The preparation method according to claim 1, wherein In step S4, the mass ratio of the composite nano-spheres and the modifier is 10:2-3, the temperature of the heating and stirring reaction is 40-50 °C, and the time is 1-2 h.
7. The preparation method according to claim 1, characterized in that In step S5, the mass ratio of triphenylphosphine to modified nano-silica is 2 - 4:10, the temperature of the heating and stirring reaction is 80 - 90 °C, and the time is 2 - 4 h.
8. A catalyst, characterized in that, The preparation method comprises the following steps: S1. Add 5 - 7 parts by weight of silane coupling agent KH550 and 1 - 2 parts by weight of silane coupling agent KH560 into dichloromethane, stir and react, dropwise add 2 - 3 parts by weight of thionyl chloride, heat to 40 - 50 °C, stir and react for 4 - 6 h, heat to remove the excessive thionyl chloride, and dry to obtain a modifier; S2. Add 10 parts by weight of nano-silica into water, add 1 - 2 parts by weight of nickel salt and 0.5 - 1.5 parts by weight of iron salt, stir and react for 20 - 40 min, adjust the pH value of the solution to 9 - 10, heat to 85 - 95 °C, crystallize for 1 - 3 h, and calcine at 400 - 600 °C for 2 - 4 h to obtain composite metal oxide / nano-silica; S3. Place the composite metal oxide / nano-silica in the heat preservation zone of a tube furnace, heat up to 420 - 450 °C under the protection of an inert gas, then change to introduce hydrogen with a gas flow rate of 1 - 2 mL / min, heat up to 650 - 670 °C, then introduce n-hexane with a gas flow rate of 0.3 - 0.5 mL / min, keep the temperature and react for 20 - 40 min, and then cool to room temperature under the protection of an inert gas to obtain composite nano-spheres; S4. Add 10 parts by weight of the composite nano-spheres into ethanol, add 2 - 3 parts by weight of the modifier, heat to 40 - 50 °C, stir and react for 1 - 2 h, centrifuge, wash, and dry to obtain modified nano-silica; S5. Add 2 - 4 parts by weight of triphenylphosphine into toluene, add 10 parts by weight of the modified nano-silica, heat to 80 - 90 °C, stir and react for 2 - 4 h, centrifuge, wash, and dry to obtain a catalyst.