Preparation method of sedge aldehyde

Abstract

The present invention relates to a method for preparing cypermethrin aldehyde, comprising: providing cuminol; adding chloride to a preparation of cuminol, reacting the cuminol with the chloride under the action of a catalyst to obtain an intermediate with a structural formula as shown in formula (1); adding a compound with a structural formula as shown in formula (2) to the preparation of the intermediate in batches, wherein R is an alkyl group; reacting the intermediate with the compound under the action of a catalyst to obtain cypermethrin aldehyde. The method for preparing cypermethrin aldehyde of the present invention is simple to operate, has little environmental pollution, and has a high yield of cypermethrin aldehyde.

Description

Technical Field

[0001] The invention relates to the technical field of spices, and in particular to a method for preparing serrata aldehyde. Background Art

[0002] Syringaldehyde is a synthetic fragrance that has never been found in nature. It has a unique sweetness and fragrance of fresh fruits and can release the fragrance of flowers such as syringa, lilac, lily, and lily of the valley. It has a fragrance similar to antelope vanillin, and the fragrance is long-lasting and has a strong ability to fix fragrance. It can be matched with many types of flavors, so it is widely used in cosmetics, food and various detergents.

[0003] There are several traditional methods for preparing cinnamaldehyde. The first is the Bouchet method: condensing diethyl methylmalonate with p-isopropylbenzyl chloride to obtain the corresponding acid, which is then converted into cinnamaldehyde. However, the operation steps of this method are complicated. The second is the trifluoroacetic acid acetic anhydride catalytic method: under the action of trifluoroacetic acid acetic anhydride, a benzene derivative reacts with an α-olefinic aldehyde or an alkenyl-2-methylene diacylated compound to prepare cinnamaldehyde, a dihydrocinnamaldehyde derivative. However, the cinnamaldehyde prepared by this method has more impurities and the production process is not environmentally friendly. The third is tetrachloroacetic acid catalytic method. Titanium tetrachloride-boron trifluoride etherate catalysis method: isopropylbenzene reacts with methacrolein under the catalysis of titanium tetrachloride-boron trifluoride etherate to prepare cypermethrin, but the yield of cypermethrin in this method is low, and a large amount of wastewater is generated, which is not environmentally friendly; the fourth method uses cuminaldehyde as a raw material, and condenses it with propionaldehyde under the catalysis of a large amount of alkali to obtain dehydrogenated cypermethrin, and then hydrogenates and distills the dehydrogenated cypermethrin to prepare cypermethrin, but this method requires the use of a large amount of strong alkali, and cypermethrin is very easy to condense with propionaldehyde to generate by-products, and the by-products are not easy to separate from cypermethrin, affecting the yield and quality. Summary of the invention

[0004] Based on this, it is necessary to provide a method for preparing pyralidium aldehyde in response to the above problems. The preparation method is simple to operate, has little pollution to the environment, and has a high yield of pyralidium aldehyde.

[0005] A method for preparing sedge aldehyde comprises the following steps:

[0006] Provide cuminol;

[0007] Adding chloride to the cuminol preparation, allowing the cuminol and the chloride to react under the action of a catalyst to obtain an intermediate having a structural formula as shown in formula (1);

[0008] Adding the compound with the structural formula (2) to the intermediate preparation in batches, so that the intermediate and the compound react under the action of a catalyst to obtain saxifragine aldehyde;

[0009]

[0010] In formula (2), R is an alkyl group.

[0011] In one embodiment, the chloride is selected from at least one of thionyl chloride, phosphorus trichloride, and phosphorus pentachloride.

[0012] In one embodiment, the molar ratio of the chloride to the cuminol is 1:1-1.5:1.

[0013] In one embodiment, in the step of adding chloride to the cuminol preparation, the chloride is added to the cuminol preparation in batches.

[0014] In one embodiment, in the step of reacting the cuminol and the chloride under the action of a catalyst, the reaction temperature is 80° C.-100° C.

[0015] In one embodiment, the molar ratio of the compound to the intermediate is 1:1-2:1.

[0016] In one embodiment, in the step of adding the compound having the structural formula (2) to the preparation of the intermediate in batches, the adding time is 1 h to 10 h.

[0017] In one embodiment, in the step of reacting the intermediate with the compound in the presence of a catalyst, the reaction temperature is 25°C-35°C.

[0018] In one embodiment, in the step of providing cuminol, the cuminol is obtained by reducing cuminaldehyde with a reducing agent.

[0019] In one embodiment, in the step of performing the reduction reaction, the reaction temperature is 50° C.-120° C., and the mass ratio of the borohydride salt to the cuminaldehyde is 1:2-1:10.

[0020] In the method for preparing pyralidinaldehyde of the present invention, cuminol reacts with chloride to generate an intermediate, and then the intermediate reacts with a compound having a structural formula as shown in formula (2) to generate pyralidinaldehyde. The operation steps are simple. In addition, a large amount of strong alkali is not required in the process of preparing pyralidinaldehyde, so the wastewater generated has little environmental pollution.

[0021] In addition, adding chloride to cuminol can make the chloride and cuminol react more fully, and in the intermediate and compound reaction step, limiting the order and method of adding the intermediate and the compound can reduce the self-polymerization of the compound, so that less impurities are generated during the reaction of the intermediate and the compound. At the same time, the cypermethrin aldehyde obtained by the reaction does not react with the intermediate, and the intermediate can be completely reacted into cypermethrin aldehyde, so that the yield of cypermethrin aldehyde is high. DETAILED DESCRIPTION

[0022] For ease of understanding of the present invention, the present invention will be described more fully below with reference to relevant embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0024] The preparation method of sedge aldehyde provided by the present invention comprises the following steps:

[0025] S1, provides cuminol.

[0026] The present invention does not limit the source of cuminol, and commercially available cuminol can be directly purchased, or it can be obtained by reaction with cuminol aldehyde. When cuminol is obtained by reaction with cuminol aldehyde, cuminol can be obtained by reduction reaction of cuminol aldehyde and borohydride salt, or by hydrogenation reaction of hydrogen in the presence of a catalyst.

[0027] In one embodiment, cuminol is obtained by reducing cuminaldehyde with a borohydride salt, wherein the borohydride salt is selected from at least one of sodium borohydride or potassium borohydride. The specific steps of reacting cuminaldehyde with a borohydride salt include:

[0028] Cumaldehyde is added into a reaction kettle, stirring is started, the temperature is raised to 50°C-120°C, and then borohydride salt is added for reaction. When the cumaldehyde content is ≤0.5% by gas chromatography analysis, a crude cuminol product is obtained and the crude product is distilled to obtain cuminol.

[0029] Taking sodium borohydride as an example, the reaction formula of cuminaldehyde and sodium borohydride is:

[0030]

[0031] In order to better reduce cuminaldehyde to cuminol, in one embodiment, the mass ratio of borohydride salt to cuminaldehyde is 1:2-1:10, preferably 3:10-1:5, and the reaction temperature is preferably 70°C-90°C.

[0032] S2, adding chloride to the cuminol preparation, allowing the cuminol and the chloride to react under the action of a catalyst to obtain an intermediate with a structural formula as shown in formula (1),

[0033]

[0034] The cuminol configuration further includes a solvent and a catalyst. In one embodiment, the solvent is selected from at least one of chloroform, petroleum ether, and dichloromethane, preferably petroleum ether; the catalyst is selected from at least one of N,N-dimethylformamide (DMF), n-dodecyltrimethylammonium chloride (DTMAC), pyridine, and triethylamine, preferably N,N-dimethylformamide (DMF).

[0035] Adding chloride to the cuminol preparation can make the chloride and cuminol react more fully, and the yield of the obtained intermediate is higher. In one embodiment, the addition is done in batches, preferably dropwise.

[0036] In one embodiment, the chloride is selected from at least one of thionyl chloride, phosphorus trichloride, and phosphorus pentachloride, preferably thionyl chloride.

[0037] Taking thionyl chloride as an example, the reaction equation of cuminol and thionyl chloride is:

[0038]

[0039] In order to better generate the intermediate with the structural formula shown in formula (1), in one embodiment, the molar ratio of the chloride to the cuminol is 1:1-1.5:1, preferably 1.1:1-1.2:1.

[0040] Since the halogenation reaction is a violently exothermic reaction, in order to better avoid overheating of the reaction due to excessively high temperature in the step of adding chloride, the temperature is controlled at 60°C-80°C in the step of adding chloride to the cuminol preparation, and the temperature is increased to react after the addition is completed. In the reaction step, the temperature is 80°C-100°C.

[0041] S3, adding the compound with the structural formula shown in formula (2) to the preparation of the intermediate in batches, so that the intermediate and the compound react under the action of a catalyst to obtain sylvaline aldehyde,

[0042]

[0043] In formula (2), R is an alkyl group, and the alkyl group is preferably a methyl group, an ethyl group, a propyl group, etc., and more preferably a methyl group.

[0044] The intermediate preparation also includes a solvent and a catalyst. The solvent can be a mixture of organic matter and water, preferably a mixture of xylene and water; the catalyst is a weakly alkaline organic salt or inorganic salt, preferably at least one of sodium carbonate and diethanolamine.

[0045] Since the compound shown in formula (2) will produce self-polymerization, the present invention adds the compound shown in formula (2) to the preparation of the intermediate in batches, so that the compound can react with the intermediate at the same time as it is added, thereby reducing the situation where the compound does not react with the intermediate in time and thus causes the compound to self-polymerize. Therefore, less impurities are generated during the reaction process. At the same time, the pyralidone produced by the reaction of the compound with the intermediate will not react with the intermediate that has not yet reacted to generate by-products. The intermediate can be completely reacted into pyralidone, thereby ensuring the yield of pyralidone.

[0046] The reaction equation between the intermediate and the compound is:

[0047]

[0048] In order to reduce the generation of by-products, in one embodiment, the molar ratio of the compound to the intermediate is 1:1-2:1, preferably 1.1:1-1.3:1.

[0049] In order to reduce the self-polymerization of the compound during the reaction with the intermediate, the compound having the structural formula (2) is added to the preparation of the intermediate in batches, and the addition time is 1h-10h, preferably 2h-4h, and the batch addition method is preferably dropwise addition.

[0050] In order to be more conducive to the production of serrata aldehyde, in one embodiment, in the step of reacting the intermediate with the compound under the action of a catalyst, the reaction temperature is 25° C.-35° C.

[0051] It should be noted that the intermediate reacts with the compound under the action of a catalyst to obtain a crude product of pyralidin, and the crude product of pyralidin can be used to obtain pyralidin by vacuum distillation or the like.

[0052] In the method for preparing pyralidinaldehyde of the present invention, cuminol reacts with chloride to generate an intermediate, and then the intermediate reacts with a compound having a structural formula as shown in formula (2) to generate pyralidinaldehyde. The operation steps are simple. In addition, a large amount of strong alkali is not required in the process of preparing pyralidinaldehyde, so the wastewater generated has little environmental pollution.

[0053] Hereinafter, the preparation method of the sedge aldehyde will be further described through the following specific examples.

[0054] Example 1

[0055] 150g of cuminol was put into a reaction kettle and stirred, and then 100g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 142.8g of thionyl chloride was uniformly added dropwise into the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 85°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. Samples were taken during the reaction and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0056] 179g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 30°C, and 93.6g of propenyl methyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0057] Example 2

[0058] 150g of cuminol was put into a reaction kettle and stirred, and then 100g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 130.9g of thionyl chloride was uniformly added dropwise into the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 85°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. Samples were taken during the reaction and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0059] 180g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 30°C, and 79.2g of propenyl methyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0060] Example 3

[0061] 150g of cuminol was put into a reaction kettle and stirred, and then 100g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 142.8g of thionyl chloride was uniformly added dropwise into the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 85°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. Samples were taken during the reaction and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0062] 178g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 30°C, and 86.4g of propenyl methyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0063] Example 4

[0064] 150g of cuminol was put into a reactor and stirred, and then 100g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 119g of thionyl chloride was uniformly added dropwise to the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 85°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. During the reaction, samples were taken and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0065] 201g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 30°C, and 72g of propenyl methyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0066] Example 5

[0067] 150g of cuminol was put into a reaction kettle and stirred, and then 100g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 130.9g of thionyl chloride was uniformly added dropwise into the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 85°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. Samples were taken during the reaction and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0068] 179g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 30°C, and 95g of propenyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0069] Example 6

[0070] 150g of cuminol was put into a reaction kettle and stirred, and then 100g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 249g of phosphorus pentachloride was uniformly added dropwise to the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 85°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. Samples were taken during the reaction and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0071] 178g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 30°C, and 144g of propenyl methyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0072] Example 7

[0073] 150g of cuminol was put into a reaction kettle and stirred, and then 119g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 166.6g of dichlorothionyl was uniformly added dropwise into the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 85°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. Samples were taken during the reaction and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0074] 189g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 25°C, and 88.8g of propenyl methyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0075] Example 8

[0076] 150g of cuminol was put into a reactor and stirred, and then 100g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 119g of thionyl chloride was uniformly added dropwise into the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 80°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. During the reaction, samples were taken and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0077] 204g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 30°C, and 129.6g of propenyl methyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0078] Example 9

[0079] 148 g of cuminaldehyde was put into a reaction kettle and stirred. The temperature was raised to 80° C., and 140 g of 30% liquid sodium borohydride was added for reaction. During the reaction, samples were taken for gas chromatography analysis. When the content of cuminaldehyde was ≤0.5%, the reaction was stopped. After standing and stratification, the oil layer was removed, and then washed with water and then stood and stratified. The oil layer was retained and subjected to vacuum distillation to obtain cuminol.

[0080] 150g of cuminol was put into a reaction kettle and stirred, and then 100g of petroleum ether and 3g of N,N-dimethylformamide were added and stirred to obtain a cuminol preparation. The temperature of the preparation was controlled to be 70°C, and 140g of dichlorothionyl was uniformly added dropwise into the cuminol preparation for 2h. After the addition was completed, the temperature was raised to 85°C, and the mixture was reacted for 2h under the action of catalyst N,N-dimethylformamide. Samples were taken during the reaction and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution to neutrality, and dried with a desiccant to obtain an intermediate.

[0081] 178g of the intermediate obtained above, 180g of toluene and 20g of water were put into a reactor, and stirring was started. Then 25g of sodium carbonate was added to obtain the intermediate configuration. The temperature of the reactor was controlled to 30°C, and 79.2g of propenyl methyl ether was uniformly added dropwise to the intermediate configuration for 2h. After the addition was completed, the reaction was continued for 2h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped. The reactant was washed with water and then allowed to stand for stratification. The oil layer was retained and vacuum distilled to obtain sedge aldehyde.

[0082] Comparative Example 1

[0083] 150 g of cuminol was put into a reaction kettle and stirred, and then 2.5 g of anhydrous zinc bromide was added and stirred evenly to obtain a cuminol preparation. The temperature in the reaction kettle was controlled to be 20° C. 330 g of 36% hydrochloric acid was uniformly added dropwise to the cuminol preparation for 2 hours. After the addition was completed, the mixture was reacted for 2 hours under the action of anhydrous zinc bromide. Samples were taken during the reaction and analyzed by gas chromatography. When the content of cuminol was ≤1%, the reaction was stopped, and the reactant was washed with saturated brine and 5% sodium hydroxide solution in turn until neutral, and dried with a desiccant to obtain an intermediate.

[0084] Comparative Example 2

[0085] Comparative Example 2 was carried out with reference to Example 1, except that: 86.4 g of allyl methyl ether, 180 g of toluene and 20 g of water were put into a reactor, stirring was started, and then 25 g of sodium carbonate was added to obtain a configuration of allyl methyl ether. The temperature of the reactor was controlled to 30°C, and 179 g of the intermediate obtained above was uniformly added dropwise to the configuration of allyl methyl ether for 2 h. After the addition was completed, the reaction was continued for 2 h. Samples were taken during the reaction and analyzed by gas chromatography. When the content of the intermediate was ≤1%, the reaction was stopped, the reactant was washed with water and then allowed to stand for stratification, the oil layer was retained, and vacuum distillation was performed to obtain sedge aldehyde.

[0086] Comparative Example 3

[0087] Comparative Example 3 was carried out with reference to Example 1, except that: 179 g of the intermediate obtained above, 180 g of toluene and 20 g of water were put into a reactor, stirring was started, and then 25 g of sodium carbonate was added to obtain a configuration of the intermediate, the temperature of the reactor was controlled to 30°C, 93.6 g of propenyl methyl ether was added to the configuration of the intermediate at one time, and the reaction was carried out for 2 hours. During the reaction, samples were taken for gas chromatography analysis. When the content of the intermediate was ≤1%, the reaction was stopped, the reactant was washed with water and then allowed to stand for stratification, the oil layer was retained, and vacuum distillation was performed to obtain sedge aldehyde.

[0088] The results of Examples 1-9 and Comparative Examples 1-3 are shown in Table 1.

[0089] Table 1

[0090]

[0091] It can be seen from Examples 1-9 and Comparative Examples 2 and 3 that when the compound represented by formula (2) is added to the intermediate in batches, the content of the obtained silymarin aldehyde is higher. It can be seen from Examples 1-9 and Comparative Example 1 that the content of the intermediate generated by the reaction of cuminol and chloride is higher. It can be seen from Examples 1, 2, 3, 5, 6, 9 and Examples 4, 7, 8 that when the molar ratio of chloride to cuminol is 1.1:1-1.2:1, the content of the intermediate obtained is higher. It can be seen from Examples 1, 2, 3, 5, 7, 9 and Examples 4, 6, 8 that when the molar ratio of the intermediate to the compound represented by formula (2) is in the range of 1:1.3-1:1.1, the content of the obtained crude silymarin aldehyde is higher.

[0092] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0093] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing sedge aldehyde, characterized in that: The steps include: Provide cuminol; Adding chloride to the cuminol preparation, allowing the cuminol and the chloride to react under the action of a catalyst to obtain an intermediate having a structural formula as shown in formula (1), wherein in the step of allowing the cuminol and the chloride to react under the action of a catalyst, the catalyst is selected from at least one of N,N-dimethylformamide, n-dodecyltrimethylammonium chloride, pyridine, and triethylamine; Adding the compound of the structural formula (2) to the preparation of the intermediate in batches, and reacting the intermediate with the compound under the action of a catalyst to obtain sylvataldehyde, wherein in the step of reacting the intermediate with the compound under the action of a catalyst, the catalyst is selected from a weakly alkaline organic salt or an inorganic salt; In formula (2), R is an alkyl group.

2. The method for preparing sedge aldehyde according to claim 1, characterized in that: The chloride is selected from at least one of thionyl chloride, phosphorus trichloride and phosphorus pentachloride.

3. The method for preparing sedge aldehyde according to claim 1, characterized in that: The molar ratio of the chloride to the cuminol is 1:1-1.5:

1.

4. The method for preparing sedge aldehyde according to claim 1, characterized in that: In the step of adding chloride to the cuminol preparation, the chloride is added to the cuminol preparation in batches.

5. The method for preparing sedge aldehyde according to claim 1, characterized in that: In the step of reacting the cuminol and the chloride under the action of a catalyst, the reaction temperature is 80° C.-100° C.

6. The method for preparing sedge aldehyde according to claim 1, characterized in that: The molar ratio of the compound to the intermediate is 1:1-2:

1.

7. The method for preparing sedge aldehyde according to claim 1, characterized in that: In the step of adding the compound having the structural formula (2) to the intermediate preparation in batches, the adding time is 1 hour to 10 hours.

8. The method for preparing sedge aldehyde according to claim 1, characterized in that: In the step of reacting the intermediate with the compound in the presence of a catalyst, the reaction temperature is 25°C-35°C.

9. The method for preparing sedge aldehyde according to any one of claims 1 to 8, characterized in that: In the step of providing cuminol, the cuminol is obtained by reducing cuminaldehyde with a borohydride salt.

10. The method for preparing sedge aldehyde according to claim 9, characterized in that: In the step of reducing cuminaldehyde with borohydride salt, the reaction temperature is 50° C.-120° C., and the mass ratio of the borohydride salt to the cuminaldehyde is 1:2-1:10.

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