Preparation method of high-purity all-cis jasmonone

Abstract

The invention provides a preparation method of high-purity all-cis jasmone, and belongs to the technical field of organic chemistry. The preparation method comprises the following steps: reacting sodium with liquid ammonia to prepare sodium amide, adding a catalyst, stirring to react, reducing pressure to remove a solvent, adding 2-formylmethyl-3-methyl-cyclopentene-2-ketone and methylbenzene under the protection of inert gas and under the condition of ice-water bath, heating and stirring to react, cooling to room temperature, and performing reduced pressure distillation to collect a product, thereby obtaining the high-purity all-cis-jasmonone. According to the method disclosed by the invention, the activity and reaction selectivity of the catalyst are greatly improved, the cis-jasmonone is generated through the reaction, the yield is high, the selectivity is good, the preparation condition is mild, the reaction method is simple, and the product purity is high.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemistry, and in particular to a method for preparing high-purity all-cis-jasmone. Background Art

[0002] Jasmone is a natural substance found in jasmine, spearmint, bergamot, mint, tea and many kinds of flowers. Jasmone exists in two different isomers around the pentenyl double bond, namely all-cis-jasmone and trans-jasmone. All-cis-jasmone has fruity, floral and jasmine scents. The main component of natural jasmone is all-cis-jasmone, while synthetic jasmone contains both, but all-cis-jasmone is still the main one.

[0003] Jasmone is widely found in jasmine, spearmint, and bergamot. With its unique smell, jasmone can be used to prepare jasmine essence and is widely used in organic chemistry, food flavors and other fields. In addition, jasmone also has anti-nematode function and has broad application prospects in the agricultural field. With the upgrading of consumption and the green development of pesticides, the jasmone market has great potential for development in the future.

[0004] The extraction methods of all-cis-jasmone mainly include distillation, extraction and crystallization. Among them, distillation is one of the most commonly used extraction methods, which mainly extracts the volatile components in jasmine flowers by distillation. The extraction method is to soak jasmine flowers in organic solvents 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 obtained by decarboxylation reaction of jasmonic acid in plants. Natural jasmone exists in jasmine oil, orange blossom oil, bergamot oil, etc. The preparation process of synthetic jasmone is diverse. At present, there are more than 200 published synthetic routes for jasmone. However, due to the problems of low yield, complex process, expensive raw materials, etc. in most synthetic processes, it is difficult to produce jasmone on a large scale and in batches. These existing methods have problems such as long synthetic process route, low product yield, large amount of waste and difficult to handle, 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 of the catalyst and the reaction selectivity, so that the reaction generates cis-jasmone with high yield and good selectivity, and the preparation conditions are mild, the reaction method is simple, and the product purity is high.

[0006] The technical solution of the present invention is achieved in this way:

[0007] The invention provides a preparation method of high-purity all-cis-jasmone. The method comprises the following steps: reacting sodium and liquid ammonia to obtain sodium amide, adding a catalyst, stirring the reaction, removing the solvent under reduced pressure, adding 2-formylmethyl-3-methyl-cyclopentene-2-one and toluene under the protection of an inert gas and in an ice-water bath, heating and stirring the reaction, cooling to room temperature, and collecting the product by reduced pressure distillation to obtain high-purity all-cis-jasmone.

[0008] As a further improvement of the present invention, the mass volume ratio of the sodium and liquid ammonia is 1-1.5:200 g / mL, the added amount of the catalyst is 2-3wt% 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 reduced pressure distillation is 70-75°C, the time of the stirring reaction is 0.5-1h, and the temperature of the heated stirring reaction is 100-120°C, and the time is 30-50min.

[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 excess thionyl chloride, and dry to obtain a modifier;

[0011] S2. Add nano-silicon oxide to water, add nickel salt and iron salt, stir the reaction, adjust the pH value of the solution, heat for crystallization, and calcine to obtain a composite metal oxide / nano-silicon oxide;

[0012] S3. The composite metal oxide / nano-silicon oxide is placed in a tubular furnace insulation zone, heated to a first temperature under inert gas protection, hydrogen is introduced, the temperature is raised to a second temperature, and then n-hexane is introduced, the reaction is kept warm, and then cooled to room temperature under inert gas protection to obtain composite nanospheres;

[0013] S4. The composite nanospheres are added to ethanol, a modifier is added, the reaction is heated and stirred, centrifuged, washed, and dried to obtain modified nano-silicon oxide;

[0014] S5. Add triphenylphosphine into toluene, add modified nano-silicon oxide, heat and stir to react, centrifuge, wash, and dry to obtain a 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 dichlorothionyl 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 hours.

[0016] As a further improvement of the present invention, the mass ratio of nano-silicon oxide, nickel salt and iron salt in step S2 is 10:1-2:0.5-1.5, the stirring reaction time is 20-40 minutes, the pH value of the adjusted solution is 9-10, the heating crystallization temperature is 85-95°C, the time is 1-3 hours, and the calcination temperature is 400-600°C, and the time is 2-4 hours.

[0017] As a further improvement of the present invention, the ventilation rate of n-hexane in step S3 is 0.3-0.5 mL / min, the ventilation rate of hydrogen is 1-2 mL / min, the insulation 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, the temperature of the heating and stirring reaction 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-silicon oxide is 2-4:10, the temperature of the heating and stirring reaction is 80-90° C., and the time is 2-4 hours.

[0020] The present invention further protects high-purity all-cis-jasmone prepared by the above preparation method.

[0021] The present invention further protects a catalyst, the preparation method of which comprises the following steps:

[0022] S1. 5-7 parts by weight of silane coupling agent KH550 and 1-2 parts by weight of silane coupling agent KH560 are added to dichloromethane, stirred for reaction, 2-3 parts by weight of thionyl chloride are added dropwise, heated to 40-50 ° C, stirred for reaction for 4-6h, heated to remove excess thionyl chloride, and dried to obtain a modifier;

[0023] S2. 10 parts by weight of nano-silicon oxide was added to water, 1-2 parts by weight of nickel salt and 0.5-1.5 parts by weight of iron salt were added, the reaction was stirred for 20-40 min, the pH value of the solution was adjusted to 9-10, heated to 85-95 ° C, crystallized for 1-3 h, calcined at 400-600 ° C for 2-4 h to obtain a composite metal oxide / nano-silicon oxide;

[0024] S3. The composite metal oxide / nano-silicon oxide is placed in a tubular furnace insulation zone, heated to 420-450°C under inert gas protection, hydrogen is introduced at a flow rate of 1-2mL / min, the temperature is raised to 650-670°C, n-hexane is then introduced at a flow rate of 0.3-0.5mL / min, the reaction is kept warm for 20-40min, and then cooled to room temperature under inert gas protection to obtain composite nanospheres;

[0025] S4. Add 10 parts by weight of the composite nanospheres to ethanol, add 2-3 parts by weight of a modifier, heat to 40-50 ° C, stir the reaction for 1-2h, 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 modified nano-silicon oxide, heat to 80-90°C, stir to react for 2-4h, centrifuge, wash, and dry to obtain a catalyst.

[0027] The present invention has the following beneficial effects:

[0028] The invention prepares a catalyst, which uses nano silicon dioxide as a carrier, deposits composite metal oxides such as iron oxide and nickel oxide on the surface, forms anionic layered materials with similar structures after crystallization, and the metal elements in the layered plates have uniform composition and structure at the molecular level due to the influence of the minimum lattice energy effect, the lattice positioning effect and the covalent action between components. After high-temperature treatment, the layered structure is lost to form uniformly dispersed composite metal oxides. After hydrogen reduction, chemical vapor deposition is catalyzed to form a metal alloy catalyst and improve the catalytic activity. At the same time, amorphous carbon is deposited on the surface by chemical vapor deposition, which greatly improves the specific surface area of ​​the carrier and is convenient for modification with a modifier.

[0029] The preparation of the modifier of the invention is that a silane coupling agent KH550 with an amino group and a silane coupling agent KH560 with an epoxy group are reacted, the amino group reacts with the epoxy group, and the amino group is small, and under the action of thionyl chloride, a chlorosilane coupling agent is formed, which reacts with the modified nano silicon oxide on one hand, and reacts with triphenylphosphine on the other hand to form coupled triphenylphosphonium bromide, which greatly improves the activity and reaction selectivity of the catalyst, so that the reaction generates cis-jasmone, the yield is high, the selectivity is good, the preparation conditions are mild, the reaction method is simple, and the product purity is high. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] The average particle size of nano-silicon oxide is 150±50nm.

[0032] Preparation Example 1

[0033] A catalyst, the preparation method comprises 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 to react, dropwise add 2 g of thionyl chloride, heat to 40 ° C, stir to react for 4 h, heat to remove excess thionyl chloride, and dry to obtain a modifier;

[0035] S2. 10 g of nano-silicon oxide was added to 200 mL of water, 1 g of nickel chloride and 0.5 g of ferric chloride were added, the reaction was stirred for 20 min, the pH value of the solution was adjusted to 9, heated to 85 ° C, crystallized for 1 h, and calcined at 400 ° C for 2 h to obtain a composite metal oxide / nano-silicon oxide;

[0036] S3. The composite metal oxide / nano-silicon oxide was placed in a tubular furnace insulation zone, heated to 420°C under nitrogen protection, hydrogen was introduced at a flow rate of 1 mL / min, the temperature was raised to 650°C, and then n-hexane was introduced at a flow rate of 0.3 mL / min, the reaction was kept warm for 20 min, and then cooled to room temperature under nitrogen protection to obtain composite nanospheres;

[0037] S4. 10 g of the composite nanospheres were added to 200 mL of ethanol, 2 g of the modifier was added, the mixture was heated to 40° C., stirred for 1 h, centrifuged, washed, and dried to obtain modified nano-silica;

[0038] S5. Add 2 g of triphenylphosphine into 200 mL of toluene, add 10 g of modified nano-silicon oxide, heat to 80°C, stir to react for 2 h, centrifuge, wash, and dry to obtain a catalyst.

[0039] Preparation Example 2

[0040] A catalyst, the preparation method comprises 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 to react, add 3 g of thionyl chloride dropwise, heat to 50 ° C, stir to react for 6 h, heat to remove excess thionyl chloride, and dry to obtain a modifier;

[0042] S2. 10 g of nano-silicon oxide was added to 200 mL of water, 2 g of nickel chloride and 1.5 g of ferric chloride were added, the reaction was stirred for 40 min, the pH value of the solution was adjusted to 10, heated to 95 ° C, crystallized for 3 h, and calcined at 600 ° C for 4 h to obtain a composite metal oxide / nano-silicon oxide;

[0043] S3. The composite metal oxide / nano-silicon oxide was placed in a tubular furnace insulation zone, heated to 450°C under nitrogen protection, hydrogen was introduced at a flow rate of 2 mL / min, the temperature was raised to 670°C, and then n-hexane was introduced at a flow rate of 0.5 mL / min, the reaction was kept warm for 40 min, and then cooled to room temperature under nitrogen protection to obtain composite nanospheres;

[0044] S4. 10 g of the composite nanospheres were added to 200 mL of ethanol, 3 g of the modifier was added, the mixture was heated to 50 ° C, stirred for 2 h, centrifuged, washed, and dried to obtain modified nano-silica;

[0045] S5. Add 4 g of triphenylphosphine into 200 mL of toluene, add 10 g of modified nano-silicon oxide, heat to 90°C, stir to react for 4 h, centrifuge, wash, and dry to obtain a catalyst.

[0046] Preparation Example 3

[0047] A catalyst, the preparation method comprises 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 to react, add 2.5 g of thionyl chloride dropwise, heat to 45 ° C, stir to react for 5 h, heat to remove excess thionyl chloride, and dry to obtain a modifier;

[0049] S2. 10 g of nano-silicon oxide was added to 200 mL of water, 1.5 g of nickel chloride and 1 g of ferric chloride were added, the reaction was stirred for 30 min, the pH value of the solution was adjusted to 9.5, heated to 90 ° C, crystallized for 2 h, and calcined at 500 ° C for 3 h to obtain a composite metal oxide / nano-silicon oxide;

[0050] S3. The composite metal oxide / nano-silicon oxide was placed in a tubular furnace insulation zone, heated to 430°C under nitrogen protection, hydrogen was introduced at a flow rate of 1.5 mL / min, the temperature was raised to 660°C, and then n-hexane was introduced at a flow rate of 0.4 mL / min, the reaction was kept warm for 30 min, and then cooled to room temperature under nitrogen protection to obtain composite nanospheres;

[0051] S4. 10 g of the composite nanospheres were added to 200 mL of ethanol, 2.5 g of the modifier was added, the mixture was heated to 45 ° C, stirred for 1.5 h, centrifuged, washed, and dried to obtain modified nano-silica;

[0052] S5. Add 3 g of triphenylphosphine into 200 mL of toluene, add 10 g of modified nano-silicon oxide, heat to 85°C, stir to react for 3 h, centrifuge, wash, and dry to obtain a catalyst.

[0053] Comparative Preparation Example 1

[0054] Compared with Preparation Example 3, the difference is that nickel chloride is not added in step S2.

[0055] The details are 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 to react, add 2.5 g of thionyl chloride dropwise, heat to 45 ° C, stir to react for 5 h, heat to remove excess thionyl chloride, and dry to obtain a modifier;

[0057] S2. 10 g of nano-silicon oxide was added to 200 mL of water, 2.5 g of ferric chloride was added, the reaction was stirred for 30 min, the pH value of the solution was adjusted to 9.5, heated to 90 ° C, crystallized for 2 h, and calcined at 500 ° C for 3 h to obtain metal oxide / nano-silicon oxide;

[0058] S3. The metal oxide / nano-silicon oxide was placed in a tubular furnace insulation zone, heated to 430°C under nitrogen protection, hydrogen was introduced at a flow rate of 1.5 mL / min, the temperature was raised to 660°C, and then n-hexane was introduced at a flow rate of 0.4 mL / min, the reaction was kept warm for 30 min, and then cooled to room temperature under nitrogen protection to obtain composite nanospheres;

[0059] S4. 10 g of the composite nanospheres were added to 200 mL of ethanol, 2.5 g of the modifier was added, the mixture was heated to 45 ° C, stirred for 1.5 h, centrifuged, washed, and dried to obtain modified nano-silica;

[0060] S5. Add 3 g of triphenylphosphine into 200 mL of toluene, add 10 g of modified nano-silicon oxide, heat to 85°C, stir to 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 is that ferric chloride is not added in step S2.

[0063] The details are 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 to react, add 2.5 g of thionyl chloride dropwise, heat to 45 ° C, stir to react for 5 h, heat to remove excess thionyl chloride, and dry to obtain a modifier;

[0065] S2. 10 g of nano-silicon oxide was added to 200 mL of water, 2.5 g of nickel chloride was added, the reaction was stirred for 30 min, the pH value of the solution was adjusted to 9.5, heated to 90 ° C, crystallized for 2 h, and calcined at 500 ° C for 3 h to obtain metal oxide / nano-silicon oxide;

[0066] S3. The metal oxide / nano-silicon oxide was placed in a tubular furnace insulation zone, heated to 430°C under nitrogen protection, hydrogen was introduced at a flow rate of 1.5 mL / min, the temperature was raised to 660°C, and then n-hexane was introduced at a flow rate of 0.4 mL / min, the reaction was kept warm for 30 min, and then cooled to room temperature under nitrogen protection to obtain composite nanospheres;

[0067] S4. 10 g of the composite nanospheres were added to 200 mL of ethanol, 2.5 g of the modifier was added, the mixture was heated to 45 ° C, stirred for 1.5 h, centrifuged, washed, and dried to obtain modified nano-silica;

[0068] S5. Add 3 g of triphenylphosphine into 200 mL of toluene, add 10 g of modified nano-silicon oxide, heat to 85°C, stir to react for 3 h, centrifuge, wash, and dry to obtain a catalyst.

[0069] Comparative Preparation Example 3

[0070] Compared with Preparation Example 3, the difference is that steps S2 and S3 are not performed.

[0071] The details are 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 to react, add 2.5 g of thionyl chloride dropwise, heat to 45 ° C, stir to react for 5 h, heat to remove excess thionyl chloride, and dry to obtain a modifier;

[0073] S2. 10 g of nano-silicon oxide was added to 200 mL of ethanol, 2.5 g of a modifier was added, the mixture was heated to 45 ° C, stirred for 1.5 h, centrifuged, washed, and dried to obtain modified nano-silicon oxide;

[0074] S3. Add 3 g of triphenylphosphine into 200 mL of toluene, add 10 g of modified nano-silicon oxide, heat to 85°C, stir to react for 3 h, centrifuge, wash, and dry to obtain a catalyst.

[0075] Comparative Preparation Example 4

[0076] Compared with Preparation Example 3, the difference is that step S4 is not performed.

[0077] The details are 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 to react, add 2.5 g of thionyl chloride dropwise, heat to 45 ° C, stir to react for 5 h, heat to remove excess thionyl chloride, and dry to obtain a modifier;

[0079] S2. 10 g of nano-silicon oxide was added to 200 mL of water, 1.5 g of nickel chloride and 1 g of ferric chloride were added, the reaction was stirred for 30 min, the pH value of the solution was adjusted to 9.5, heated to 90 ° C, crystallized for 2 h, and calcined at 500 ° C for 3 h to obtain a composite metal oxide / nano-silicon oxide;

[0080] S3. The composite metal oxide / nano-silicon oxide was placed in a tubular furnace insulation zone, heated to 430°C under nitrogen protection, hydrogen was introduced at a flow rate of 1.5 mL / min, the temperature was raised to 660°C, and then n-hexane was introduced at a flow rate of 0.4 mL / min, the reaction was kept warm for 30 min, and then cooled to room temperature under nitrogen protection to obtain composite nanospheres;

[0081] S4. Add 3 g of triphenylphosphine into 200 mL of toluene, add 10 g of composite nanospheres, heat to 85°C, stir to react for 3 h, centrifuge, wash, and dry to obtain a catalyst.

[0082] Comparative Preparation Example 5

[0083] Compared with Preparation Example 3, the difference is that step S5 is not performed.

[0084] The details are as follows:

[0085] S1. Add 6 g of silane coupling agent KH550 and 1.5 g of silane coupling agent KH560 to 200 mL of dichloromethane, stir to react, add 2.5 g of thionyl chloride dropwise, heat to 45 ° C, stir to react for 5 h, heat to remove excess thionyl chloride, and dry to obtain a modifier;

[0086] S2. 10 g of nano-silicon oxide was added to 200 mL of water, 1.5 g of nickel chloride and 1 g of ferric chloride were added, the reaction was stirred for 30 min, the pH value of the solution was adjusted to 9.5, heated to 90 ° C, crystallized for 2 h, and calcined at 500 ° C for 3 h to obtain a composite metal oxide / nano-silicon oxide;

[0087] S3. The composite metal oxide / nano-silicon oxide was placed in a tubular furnace insulation zone, heated to 430°C under nitrogen protection, hydrogen was introduced at a flow rate of 1.5 mL / min, the temperature was raised to 660°C, and then n-hexane was introduced at a flow rate of 0.4 mL / min, the reaction was kept warm for 30 min, and then cooled to room temperature under nitrogen protection to obtain composite nanospheres;

[0088] S4. Add 10 g of composite nanospheres to 200 mL of ethanol, add 2.5 g of modifier, heat to 45°C, stir to react for 1.5 h, centrifuge, wash, and dry to obtain modified nano-silicon oxide, which is a catalyst.

[0089] Test Example 1

[0090] The specific surface areas of the catalysts prepared in Preparation Examples 1-3 and Comparative Preparation Examples 1-5 were measured using a high-throughput gas adsorption instrument. The results are shown in Table 1.

[0091] Table 1

[0092]

[0093]

[0094] It can be seen from the above table that 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-cyclopenten-2-one refers to Yoshiaki Nakahara, et al. Agr. Biol. Chem., 39 (9), 1887-1888 (1975).

[0096] Example 1

[0097] The present embodiment provides a method for preparing high-purity all-cis-jasmone. 1 g of sodium and 200 mL of liquid ammonia are reacted to obtain sodium amide, and the catalyst prepared in Preparation Example 1 is added, wherein the amount of the catalyst added is 2 wt% of the total mass of the system. The mixture is stirred for reaction for 0.5 h, and the solvent is 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 are added, and the mixture is heated to 100° C. and stirred for reaction for 30 min. The mixture is cooled to room temperature, heated to 70° C., and the product is collected by distillation under reduced pressure to obtain high-purity all-cis-jasmone.

[0098] Example 2

[0099] The present embodiment provides a method for preparing high-purity all-cis-jasmone. 1.5 g of sodium and 200 mL of liquid ammonia are reacted to prepare sodium amide, the catalyst prepared in Preparation Example 2 is added, and the amount of the catalyst added is 3 wt % of the total mass of the system. The mixture is stirred for reaction for 1 hour, and the solvent is removed under reduced pressure. Under nitrogen protection and ice-water bath conditions, 7 g of 2-formylmethyl-3-methyl-cyclopentene-2-one and toluene are added, and the mixture is heated to 120° C., stirred for reaction for 50 minutes, cooled to room temperature, heated to 75° C., and the product is collected by vacuum distillation to prepare high-purity all-cis-jasmone.

[0100] Example 3

[0101] The present embodiment provides a method for preparing high-purity all-cis-jasmone. 1.2 g of sodium and 200 mL of liquid ammonia are reacted to prepare sodium amide, and the catalyst prepared in Preparation Example 3 is added, wherein the amount of the catalyst added is 2.5 wt% of the total mass of the system. The mixture is stirred for reaction for 1 h, and the solvent is removed 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, and the mixture is heated to 110° C., stirred for reaction for 40 min, cooled to room temperature, heated to 72° C., and the product is collected by distillation under reduced pressure to prepare high-purity all-cis-jasmone.

[0102] Comparative Example 1

[0103] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 1.

[0104] Comparative Example 2

[0105] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 2.

[0106] Comparative Example 3

[0107] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 3.

[0108] Comparative Example 4

[0109] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 4.

[0110] Comparative Example 5

[0111] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 5.

[0112] Test Example 2

[0113] The methods in Examples 1-3 of the present invention and Comparative Examples 1-5 were evaluated, and the results are shown in Table 2.

[0114] Table 2

[0115] Group Jasmone yield (%) Purity of cis-jasmone 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] It can be seen from the above table that the methods in Examples 1-3 of the present invention have high yields and high purity of cis-jasmone.

[0117] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing high-purity all-cis-jasmone, characterized in that: Sodium and liquid ammonia are reacted to obtain sodium amide, a catalyst is added, the reaction is stirred, the solvent is removed under reduced pressure, 2-formylmethyl-3-methyl-cyclopentene-2-one and toluene are added under the protection of inert gas and ice-water bath conditions, the reaction is heated and stirred, the reaction is cooled to room temperature, and the product is collected by reduced pressure distillation to obtain high-purity all-cis-jasmone.

2. The preparation method according to claim 1, characterized in that: The mass volume ratio of the sodium and liquid ammonia is 1-1.5:200 g / mL, the amount of the catalyst added is 2-3wt% 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 reduced pressure distillation is 70-75°C, the time of the stirring reaction is 0.5-1h, and the temperature of the heated stirring reaction is 100-120°C, and the time is 30-50min.

3. The preparation method according to claim 1, characterized in that: The preparation method of the catalyst is as follows: 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 excess thionyl chloride, and dry to obtain a modifier; S2. Add nano-silicon oxide to water, add nickel salt and iron salt, stir the reaction, adjust the pH value of the solution, heat for crystallization, and calcine to obtain a composite metal oxide / nano-silicon oxide; S3. The composite metal oxide / nano-silicon oxide is placed in a tubular furnace insulation zone, heated to a first temperature under inert gas protection, hydrogen is introduced, the temperature is raised to a second temperature, and then n-hexane is introduced, the reaction is kept warm, and then cooled to room temperature under inert gas protection to obtain composite nanospheres; S4. Adding the composite nanospheres to ethanol, adding a modifier, heating and stirring the reaction, centrifuging, washing, and drying to obtain modified nano-silicon oxide; S5. Add triphenylphosphine into toluene, add modified nano-silicon oxide, heat and stir to react, centrifuge, wash, and dry to obtain a catalyst.

4. The preparation method according to claim 3, characterized in that: In step S1, the mass ratio of silane coupling agent KH550, silane coupling agent KH560 and dithionyl 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 hours.

5. The preparation method according to claim 3, characterized in that: The mass ratio of nano silicon oxide, nickel salt and iron salt in step S2 is 10:1-2:0.5-1.5, the stirring reaction time is 20-40min, the pH value of the solution is adjusted to 9-10, the heating crystallization temperature is 85-95°C, the time is 1-3h, and the calcination temperature is 400-600°C, and the time is 2-4h.

6. The preparation method according to claim 3, characterized in that: In step S3, the ventilation rate of n-hexane is 0.3-0.5 mL / min, the ventilation rate of hydrogen is 1-2 mL / min, the insulation reaction time is 20-40 min, the first temperature is 420-450° C., and the second temperature is 650-670° C.

7. The preparation method according to claim 3, characterized in that: In step S4, the mass ratio of the composite nanospheres to 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.

8. The preparation method according to claim 3, characterized in that: In step S5, the mass ratio of triphenylphosphine to modified nano-silicon oxide is 2-4:10, the temperature of the heating and stirring reaction is 80-90° C., and the time is 2-4 hours.

9. A high-purity all-cis-jasmone prepared by the preparation method according to any one of claims 1 to 8.

10. A catalyst, characterized in that The preparation method comprises the following steps: S1. 5-7 parts by weight of silane coupling agent KH550 and 1-2 parts by weight of silane coupling agent KH560 are added to dichloromethane, stirred for reaction, 2-3 parts by weight of thionyl chloride are added dropwise, heated to 40-50 ° C, stirred for reaction for 4-6h, heated to remove excess thionyl chloride, and dried to obtain a modifier; S2. 10 parts by weight of nano-silicon oxide was added to water, 1-2 parts by weight of nickel salt and 0.5-1.5 parts by weight of iron salt were added, the reaction was stirred for 20-40 min, the pH value of the solution was adjusted to 9-10, heated to 85-95 ° C, crystallized for 1-3 h, calcined at 400-600 ° C for 2-4 h to obtain a composite metal oxide / nano-silicon oxide; S3. The composite metal oxide / nano-silicon oxide is placed in a tubular furnace insulation zone, heated to 420-450°C under inert gas protection, hydrogen is introduced at a flow rate of 1-2mL / min, the temperature is raised to 650-670°C, n-hexane is then introduced at a flow rate of 0.3-0.5mL / min, the reaction is kept warm for 20-40min, and then cooled to room temperature under inert gas protection to obtain composite nanospheres; S4. Add 10 parts by weight of the composite nanospheres to ethanol, add 2-3 parts by weight of a modifier, heat to 40-50 ° C, stir the reaction for 1-2h, centrifuge, wash, and dry to obtain modified nano-silicon oxide; S5. Add 2-4 parts by weight of triphenylphosphine to toluene, add 10 parts by weight of modified nano-silicon oxide, heat to 80-90°C, stir to react for 2-4h, centrifuge, wash, and dry to obtain a catalyst.

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