A method for extracting muscone

Abstract

This invention discloses a method for extracting musk ketone, belonging to the field of pharmaceutical technology. The method includes the following steps: musk powder is enzymatically hydrolyzed with lipase and trypsin to obtain an aqueous enzymatic hydrolysate; the aqueous enzymatic hydrolysate and an extraction solvent are mixed and the organic phase is collected to obtain an organic extract; a composite extractant and p-toluenesulfonic acid are dispersed in the organic extract and stirred to obtain a ketone-containing complex; the ketone-containing complex is dispersed in a mixed solvent and continuously stirred under ultraviolet light irradiation, followed by separation and purification to obtain an oily liquid, which is the musk ketone. This invention achieves musk ketone capture through covalent bonding, and then utilizes light energy and an acidic environment to promote the breaking of chemical bonds to complete the release of musk ketone, effectively solving the problem of easy adsorption and difficult desorption of traditional adsorption materials; the composite extractant after releasing musk ketone can be regenerated and reused after simple treatment, reducing resource waste.

Description

Technical Field

[0001] This invention relates to the field of pharmaceutical technology, and specifically to a method for extracting musk ketone. Background Technology

[0002] Musk, a rare natural resource possessing both medicinal and fragrance value, holds an irreplaceable position in the pharmaceutical, cosmetic, and fragrance industries due to the unique physiological activity and aromatic properties of its core active ingredient, muscone. In the pharmaceutical field, muscone has been proven to have cardiotonic, blood-activating, and mind-clearing effects, making it a key component of many precious traditional Chinese medicines. In the fragrance industry, its excellent fixative properties and long-lasting aromatic expression make it an indispensable raw material in the formulation of high-end perfumes and fragrances. Therefore, achieving efficient extraction and purification of muscone is of great significance for fully realizing the value of musk resources and meeting the needs of high-quality development in related industries.

[0003] However, current technologies for extracting muscone from musk still face numerous bottlenecks that urgently need to be overcome. Regarding extraction efficiency, traditional methods such as solvent extraction and steam distillation generally suffer from lengthy extraction cycles, leading not only to low production efficiency and high equipment occupancy rates, but also the potential for degradation or isomerization of some muscone due to factors like temperature and light during prolonged processing, further impacting product quality. In terms of purity control, musk is complex, containing impurities such as cholesterol, fatty acid esters, and polypeptides in addition to muscone. Existing extraction processes struggle to achieve effective separation, resulting in low purity muscone in the final product. This often necessitates multiple subsequent purification steps, increasing production costs and potentially causing additional losses of the target component during purification. More critically, constrained by both extraction efficiency and separation effectiveness, the yield of muscone using current technologies is generally low. For musk, which is already a scarce resource, this undoubtedly exacerbates resource waste and the supply-demand imbalance, severely limiting the large-scale development of industries centered around muscone.

[0004] Patent CN 106349038 B discloses a method for preparing muscone. This method involves extracting muscone through multi-step solvent extraction, hot pressure distillation, centrifugal purification, and spray drying. However, this method requires repeated soaking and reflux extraction, and multiple solid-liquid separations can easily cause loss of the target substance and reduce the yield.

[0005] Therefore, providing a method for extracting muscone with high yield and high purity is an important problem that urgently needs to be solved in this field. Summary of the Invention

[0006] To address the problems of low yield and low purity in existing muscone extraction techniques, this invention provides a method for extracting muscone. Specifically, the technical solution of this invention includes the following: A method for extracting muscone, the method comprising the following steps: Musk powder was hydrolyzed by lipase and trypsin to obtain an aqueous enzymatic hydrolysate; The organic phase is collected by mixing the aqueous enzymatic hydrolysate and the extraction solvent to obtain the organic extract. The compound extractant and p-toluenesulfonic acid were dispersed in an organic extract and stirred to obtain a ketone-containing complex. The ketone-containing complex was dispersed in a first mixed solvent and reacted under continuous stirring under ultraviolet light irradiation. The musk ketone was then obtained by separation and purification.

[0007] Furthermore, the weight ratio of the musk powder, lipase, and trypsin is 100:0.8~1.2:0.8~1.2.

[0008] Furthermore, the conditions for the enzymatic hydrolysis treatment include an enzymatic hydrolysis pH of 7.0 to 8.0, an enzymatic hydrolysis temperature of 38 to 42°C, and an incubation time of 10 to 14 hours.

[0009] Furthermore, the extraction solvent is ethyl acetate or 2-methyltetrahydrofuran.

[0010] Furthermore, the weight ratio of the aqueous enzymatic hydrolysate to the extraction solvent is 100:20~50.

[0011] Furthermore, the preparation method of the composite extractant includes the following steps: A photosensitive extractant was obtained by reacting zirconium tetrachloride, azobenzene-4,4'-dicarboxylic acid and terephthalic acid. Succinic anhydride and tert-butyloxycarbonylhydrazine were mixed and stirred to produce an acylhydrazine modifier; The photosensitive extractant was vacuum activated to obtain the activated extractant, and the activated extractant and the acyl hydrazine modifier were mixed and stirred to obtain the modified extractant; The composite extractant is prepared by mixing and stirring the modified extractant and the deprotecting agent.

[0012] Further, the weight ratio of zirconium tetrachloride, azobenzene-4,4'-dicarboxylic acid and terephthalic acid is 2.25~2.45:0.55~0.75:1.33~1.53.

[0013] Furthermore, the reaction conditions for the mixture of zirconium tetrachloride, azobenzene-4,4'-dicarboxylic acid and terephthalic acid include a reaction temperature of 100~120℃ and a reaction time of 24~36h.

[0014] Furthermore, the weight ratio of succinic anhydride to tert-butyloxycarbonyl hydrazine is 7.5~11.5:9~10.

[0015] Furthermore, the conditions for the mixed stirring reaction of succinic anhydride and tert-butyloxycarbonyl hydrazine include a reaction temperature of 23-25°C and a reaction time of 12-14 h.

[0016] Furthermore, the conditions for vacuum activation include an activation temperature of 110~130℃ and an activation time of 4~6h.

[0017] Furthermore, the weight ratio of the activating extractant to the acylhydrazine modifier is 1:1~2.

[0018] Furthermore, the conditions for the mixing and stirring reaction of the activating extractant and the acylhydrazine modifier include a reaction temperature of 65-80°C and a reaction time of 23-25 ​​h.

[0019] Furthermore, the deprotecting agent is prepared by mixing trichloroacetic acid and dichloromethane in a volume ratio of 1:9.

[0020] Furthermore, the weight ratio of the modified extractant to the deprotectant is 5:30~50.

[0021] Furthermore, the conditions for mixing and stirring the modified extractant and the deprotecting agent include a reaction temperature of 0~5℃ and a reaction time of 1.5~2.5h.

[0022] Furthermore, the weight ratio of the composite extractant, p-toluenesulfonic acid, and organic extract is 20~30:0.01~0.02:300~500.

[0023] Furthermore, the conditions for the reaction of the composite extractant and p-toluenesulfonic acid dispersed in the organic extract liquid and stirred include a reaction temperature of 23-25°C and a reaction time of 10-14 h.

[0024] Furthermore, the first mixed solvent is prepared by mixing 2-methyltetrahydrofuran and a pH 3.5 acetic acid buffer at a volume ratio of 20:4~6.

[0025] Furthermore, the conditions for ultraviolet irradiation include an irradiation wavelength of 365 nm and an irradiation power of 10~20 W / cm². 2 .

[0026] Furthermore, the conditions for the stirring reaction include a reaction temperature of 25-30°C and a reaction time of 4-6 hours.

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) In this invention, zirconium tetrachloride is used as the metal source, and azobenzene-4,4'-dicarboxylic acid and terephthalic acid are used as ligands to obtain a photosensitive extractant with photosensitive properties through a solvothermal reaction; then, the carbonyl group on the succinic anhydride molecule is reacted with the hydrazine group of tert-butyloxycarbonylhydrazine to obtain an acylhydrazine modifier with a carboxyl group at one end and a tert-butyloxycarbonyl group at the other end; after the above photosensitive extractant is activated, it is combined with the acylhydrazine modifier through coordination to obtain a modified extractant; then the modified extractant is treated with a deprotecting agent to finally obtain a composite extractant rich in acylhydrazine groups and photosensitive azobenzene units.

[0028] (2) In the musk ketone extraction process of this invention, lipase and trypsin are first used to pretreat the musk powder: the fat and protein matrix in the musk powder are decomposed by enzymes, so that the musk ketone molecules that were originally encapsulated or adsorbed are fully released to form an aqueous enzymatic hydrolysate; then, based on the principle of like dissolves like, the transfer and concentration of musk ketone from the aqueous phase to the organic phase are achieved by organic extraction to obtain an organic extract; subsequently, the hydrazide group on the composite extractant reacts with the carbonyl group in the musk ketone molecule to form a hydrazone compound to obtain a ketone-containing complex containing musk ketone; ultraviolet light irradiation of the ketone-containing complex will excite the azobenzene unit in the photosensitive extractant, causing its molecular configuration to change from trans to cis. This configurational change will cause physical disturbance inside the pores of the photosensitive extractant, and this disturbance will be transmitted to the hydrazone bonds in the pores, reducing the stability of the hydrazone bonds. Combined with the acidic environment, the hydrazone bond hydrolysis reaction proceeds in the forward direction, and finally the efficient release of the ketone mixture is achieved. The ketone mixture is then simply separated and purified to achieve the goal of high yield and high purity extraction of musk ketone.

[0029] (3) This invention achieves highly selective capture of muscone through covalent bonding, and then uses light energy and acidic environment to trigger the breaking of chemical bonds to complete the release of muscone, forming a staged and controllable operation of capture and release, which effectively solves the problem of easy adsorption and difficult desorption of traditional adsorption materials; at the same time, the composite extractant after the release of muscone can be regenerated and reused after simple treatment, reducing resource waste and combining economy and environmental protection. Detailed Implementation

[0030] The technical solution of the present invention will be clearly and completely described below through embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] Unless otherwise stated, all raw materials and reagents used in this invention are commercially available or can be prepared by known methods.

[0032] Preparation Example 1: The preparation method of the compound extractant includes the following steps: 2.25 parts by weight of zirconium tetrachloride, 0.55 parts by weight of azobenzene-4,4'-dicarboxylic acid, and 1.33 parts by weight of terephthalic acid are dispersed in 500 parts by weight of a second mixed solvent (V N,N-二甲基甲酰胺 V 乙酸 In a mixture of 4:1, after ultrasonic treatment for 15 minutes, the mixture was transferred to a high-pressure reactor lined with polytetrafluoroethylene and reacted at 100°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, centrifuged to collect the solid, washed three times alternately with N,N-dimethylformamide and ethanol, and then vacuum dried at 80°C for 8 hours to obtain the photosensitive extractant. 7.5 parts by weight of succinic anhydride were dispersed in 100 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a succinic anhydride solution. 9 parts by weight of tert-butyloxycarbonylhydrazine were dispersed in 20 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a tert-butyloxycarbonylhydrazine solution. Under nitrogen protection, the tert-butyloxycarbonylhydrazine solution was added dropwise to the succinic anhydride solution. The reaction was carried out at 23 °C and stirred at 200 r / min for 12 h. After the reaction was completed, most of the anhydrous tetrahydrofuran solvent was removed by vacuum distillation at 40 °C to obtain a white oily substance. 100 parts by weight of anhydrous diethyl ether was added to the white oily substance, and the mixture was stirred at 600 r / min for 30 min to obtain a mixture. The mixture was stirred at 0 °C for 1 h. After stirring, the white crystals were collected by filtration, washed three times with pre-cooled anhydrous diethyl ether, and dried under vacuum at 40 °C for 8 h to obtain the acylhydrazine modifier. The photosensitive extractant was activated under nitrogen protection at 110℃ for 4 h to obtain the activated extractant. 1 part by weight of the activated extractant and 1 part by weight of the acylhydrazine modifier were dispersed in 50 parts by weight of N,N-dimethylformamide. After ultrasonic treatment for 10 min, the mixture was heated to 65℃ and stirred for 23 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, the solid was collected by filtration, and washed three times alternately with N,N-dimethylformamide and ethanol. The solid was then dried under vacuum at 60℃ for 12 h to obtain the modified extractant. 5 parts by weight of the modified extractant are dispersed in 30 parts by weight of the deprotectant (V 三氟乙酸 V 二氯甲烷 After ultrasonic treatment for 5 min in a 1:9 ratio, the mixture was stirred at 0 °C for 1.5 h under a nitrogen atmosphere. Then, 2 parts by weight of diisopropylethylamine were added dropwise to neutralize the acidity of the system. Stirring was continued for 20 min to ensure complete neutralization. The solid was collected by filtration and washed three times with pre-cooled dichloromethane and anhydrous ethanol. The mixture was then vacuum dried at 50 °C for 6 h to obtain the composite extractant.

[0033] Preparation Example 2: The preparation method of the compound extractant includes the following steps: 2.3 parts by weight of zirconium tetrachloride, 0.6 parts by weight of azobenzene-4,4'-dicarboxylic acid, and 1.38 parts by weight of terephthalic acid are dispersed in 500 parts by weight of a second mixed solvent (V N,N-二甲基甲酰胺 V 乙酸 In a mixture of 4:1, after ultrasonic treatment for 17 minutes, the mixture was transferred to a high-pressure reactor lined with polytetrafluoroethylene and reacted at 105°C for 27 hours. After the reaction was completed, the mixture was cooled to room temperature, centrifuged to collect the solid, washed three times alternately with N,N-dimethylformamide and ethanol, and then vacuum dried at 80°C for 9 hours to obtain the photosensitive extractant. 8.5 parts by weight of succinic anhydride were dispersed in 100 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a succinic anhydride solution. 9.2 parts by weight of tert-butyloxycarbonylhydrazine were dispersed in 20 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a tert-butyloxycarbonylhydrazine solution. Under nitrogen protection, the tert-butyloxycarbonylhydrazine solution was added dropwise to the succinic anhydride solution. The reaction was carried out at 23.5 °C and 250 r / min for 13 h. After the reaction was completed, most of the anhydrous tetrahydrofuran solvent was removed by vacuum distillation at 40 °C to obtain a white oily substance. 100 parts by weight of anhydrous diethyl ether was added to the white oily substance and the mixture was stirred at 600 r / min for 30 min to obtain a mixture. The mixture was stirred at 1 °C for 1.2 h. After stirring, the white crystals were collected by filtration, washed three times with pre-cooled anhydrous diethyl ether, and dried under vacuum at 40 °C for 9 h to obtain the acylhydrazine modifier. The photosensitive extractant was activated under nitrogen protection at 115℃ for 4.5 h to obtain the activated extractant. 1 part by weight of the activated extractant and 1.2 parts by weight of the acylhydrazine modifier were dispersed in 50 parts by weight of N,N-dimethylformamide. After ultrasonic treatment for 12 min, the mixture was heated to 70℃ and stirred for 23.5 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, the solid was collected by filtration, and washed three times alternately with N,N-dimethylformamide and ethanol. The solid was then dried under vacuum at 60℃ for 12 h to obtain the modified extractant. 5 parts by weight of the modified extractant are dispersed in 35 parts by weight of the deprotectant (V 三氟乙酸 V 二氯甲烷 After ultrasonic treatment for 6 min in a 1:9 ratio, the mixture was stirred at 1 °C for 1.7 h under a nitrogen atmosphere. Then, 2.2 parts by weight of diisopropylethylamine was added dropwise to neutralize the acidity of the system. Stirring was continued for 22 min to ensure complete neutralization. The solid was collected by filtration and washed three times with pre-cooled dichloromethane and anhydrous ethanol. The mixture was then vacuum dried at 52 °C for 6.5 h to obtain the composite extractant.

[0034] Preparation Example 3: The preparation method of the compound extractant includes the following steps: 2.35 parts by weight of zirconium tetrachloride, 0.65 parts by weight of azobenzene-4,4'-dicarboxylic acid, and 1.43 parts by weight of terephthalic acid are dispersed in 500 parts by weight of a second mixed solvent (VN,N-二甲基甲酰胺 V 乙酸 In a mixture of 4:1, after 20 min of ultrasonic treatment, the mixture was transferred to a high-pressure reactor lined with polytetrafluoroethylene and reacted at 110 °C for 30 h. After the reaction was completed, the mixture was cooled to room temperature, centrifuged to collect the solid, washed three times alternately with N,N-dimethylformamide and ethanol, and then vacuum dried at 80 °C for 10 h to obtain the photosensitive extractant. 9.5 parts by weight of succinic anhydride were dispersed in 100 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a succinic anhydride solution. 9.5 parts by weight of tert-butyloxycarbonylhydrazine were dispersed in 20 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a tert-butyloxycarbonylhydrazine solution. Under nitrogen protection, the tert-butyloxycarbonylhydrazine solution was added dropwise to the succinic anhydride solution. The reaction was carried out at 24 °C and stirred at 300 r / min for 14 h. After the reaction was completed, most of the anhydrous tetrahydrofuran solvent was removed by vacuum distillation at 40 °C to obtain a white oily substance. 100 parts by weight of anhydrous diethyl ether was added to the white oily substance and stirred at 600 r / min for 30 min to obtain a mixture. The mixture was stirred at 2 °C for 1.5 h. After stirring, the white crystals were collected by filtration, washed three times with pre-cooled anhydrous diethyl ether, and dried under vacuum at 40 °C for 10 h to obtain the acylhydrazine modifier. The photosensitive extractant was activated under nitrogen protection at 120℃ for 5 h to obtain the activated extractant. 1 part by weight of the activated extractant and 1.5 parts by weight of the hydrazide modifier were dispersed in 50 parts by weight of N,N-dimethylformamide. After ultrasonic treatment for 15 min, the mixture was heated to 75℃ and stirred for 24 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, the solid was collected by filtration, and washed three times alternately with N,N-dimethylformamide and ethanol. The solid was then dried under vacuum at 60℃ for 12 h to obtain the modified extractant. 5 parts by weight of the modified extractant are dispersed in 40 parts by weight of the deprotectant (V 三氟乙酸 V 二氯甲烷 After ultrasonic treatment for 7 min in a 1:9 ratio, the mixture was stirred at 2 °C for 2 h under a nitrogen atmosphere. Then, 2.5 parts by weight of diisopropylethylamine was added dropwise to neutralize the acidity of the system. Stirring was continued for 25 min to ensure complete neutralization. The solid was collected by filtration and washed three times with pre-cooled dichloromethane and anhydrous ethanol. The mixture was then vacuum dried at 55 °C for 7 h to obtain the composite extractant.

[0035] Preparation Example 4: The preparation method of the compound extractant includes the following steps: 2.4 parts by weight of zirconium tetrachloride, 0.7 parts by weight of azobenzene-4,4'-dicarboxylic acid, and 1.48 parts by weight of terephthalic acid are dispersed in 500 parts by weight of a second mixed solvent (V N,N-二甲基甲酰胺 V 乙酸In a mixture of 4:1, after ultrasonic treatment for 25 minutes, the mixture was transferred to a high-pressure reactor lined with polytetrafluoroethylene and reacted at 115°C for 33 hours. After the reaction was completed, the mixture was cooled to room temperature, centrifuged to collect the solid, washed three times alternately with N,N-dimethylformamide and ethanol, and then vacuum dried at 80°C for 11 hours to obtain the photosensitive extractant. 10.5 parts by weight of succinic anhydride were dispersed in 100 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a succinic anhydride solution. 9.8 parts by weight of tert-butyloxycarbonylhydrazine were dispersed in 20 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a tert-butyloxycarbonylhydrazine solution. Under nitrogen protection, the tert-butyloxycarbonylhydrazine solution was added dropwise to the succinic anhydride solution. The reaction was carried out at 24.5 °C and stirred at 350 r / min for 15 h. After the reaction was completed, most of the anhydrous tetrahydrofuran solvent was removed by vacuum distillation at 40 °C to obtain a white oily substance. 100 parts by weight of anhydrous diethyl ether was added to the white oily substance, and the mixture was stirred at 600 r / min for 30 min to obtain a mixture. The mixture was stirred at 3 °C for 1.7 h. After stirring, the white crystals were collected by filtration, washed three times with pre-cooled anhydrous diethyl ether, and dried under vacuum at 40 °C for 11 h to obtain the acylhydrazine modifier. The photosensitive extractant was activated under nitrogen protection at 125℃ for 5.5 h to obtain the activated extractant. 1 part by weight of the activated extractant and 1.7 parts by weight of the hydrazide modifier were dispersed in 50 parts by weight of N,N-dimethylformamide. After ultrasonic treatment for 18 min, the mixture was heated to 78℃ and stirred for 24.5 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, the solid was collected by filtration, and washed three times alternately with N,N-dimethylformamide and ethanol. The solid was then dried under vacuum at 60℃ for 12 h to obtain the modified extractant. 5 parts by weight of the modified extractant are dispersed in 45 parts by weight of the deprotectant (V 三氟乙酸 V 二氯甲烷 After ultrasonic treatment for 8 min in a 1:9 ratio, the mixture was stirred at 4 °C for 2.5 h under a nitrogen atmosphere. Then, 2.8 parts by weight of diisopropylethylamine was added dropwise to neutralize the acidity of the system. Stirring was continued for 27 min to ensure complete neutralization. The solid was collected by filtration and washed three times with pre-cooled dichloromethane and anhydrous ethanol. The mixture was then vacuum dried at 58 °C for 7.5 h to obtain the composite extractant.

[0036] Preparation Example 5: The preparation method of the compound extractant includes the following steps: 2.45 parts by weight of zirconium tetrachloride, 0.75 parts by weight of azobenzene-4,4'-dicarboxylic acid, and 1.53 parts by weight of terephthalic acid are dispersed in 500 parts by weight of a second mixed solvent (V N,N-二甲基甲酰胺 V 乙酸In a mixture of 4:1, after ultrasonic treatment for 30 min, the mixture was transferred to a high-pressure reactor lined with polytetrafluoroethylene and reacted at 120 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, centrifuged to collect the solid, washed three times alternately with N,N-dimethylformamide and ethanol, and then vacuum dried at 80 °C for 12 h to obtain the photosensitive extractant. 11.5 parts by weight of succinic anhydride were dispersed in 100 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a succinic anhydride solution. 10 parts by weight of tert-butyloxycarbonylhydrazine were dispersed in 20 parts by weight of anhydrous tetrahydrofuran and stirred for 10 min to obtain a tert-butyloxycarbonylhydrazine solution. Under nitrogen protection, the tert-butyloxycarbonylhydrazine solution was added dropwise to the succinic anhydride solution. The reaction was carried out at 25 °C and stirred at 400 r / min for 16 h. After the reaction was completed, most of the anhydrous tetrahydrofuran solvent was removed by vacuum distillation at 40 °C to obtain a white oily substance. 100 parts by weight of anhydrous diethyl ether was added to the white oily substance and stirred at 600 r / min for 30 min to obtain a mixture. The mixture was stirred at 5 °C for 2 h. After stirring, the white crystals were collected by filtration, washed three times with pre-cooled anhydrous diethyl ether, and dried under vacuum at 40 °C for 12 h to obtain the acylhydrazine modifier. The photosensitive extractant was activated under nitrogen protection at 130℃ for 6 h to obtain the activated extractant. 1 part by weight of the activated extractant and 2 parts by weight of the hydrazide modifier were dispersed in 50 parts by weight of N,N-dimethylformamide. After ultrasonic treatment for 20 min, the mixture was heated to 80℃ and stirred for 25 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, the solid was collected by filtration, and washed three times alternately with N,N-dimethylformamide and ethanol. The solid was then dried under vacuum at 60℃ for 12 h to obtain the modified extractant. 5 parts by weight of the modified extractant are dispersed in 50 parts by weight of the deprotectant (V 三氟乙酸 V 二氯甲烷 After ultrasonic treatment in a solution of 1:9 for 10 min, the mixture was stirred at 5 °C for 2.5 h under a nitrogen atmosphere. Then, 3 parts by weight of diisopropylethylamine were added dropwise to neutralize the acidity of the system. Stirring was continued for 30 min to ensure complete neutralization. The solid was collected by filtration and washed three times with pre-cooled dichloromethane and anhydrous ethanol. The mixture was then vacuum dried at 60 °C for 8 h to obtain the composite extractant.

[0037] Preparation Example 6: The preparation method of the compound extractant includes the following steps: Remove azobenzene-4,4'-dicarboxylic acid from Preparation Example 5, and keep all other operations the same as in Preparation Example 5.

[0038] Preparation Example 7: The preparation method of the compound extractant includes the following steps: Remove the hydrazide modifier from Preparation Example 5, and keep the other operations the same as in Preparation Example 5.

[0039] Preparation Example 8: The preparation method of the compound extractant includes the following steps: The vacuum activation step of the photosensitizing extractant in Preparation Example 5 was removed, while other operations remained the same as in Preparation Example 5.

[0040] Preparation Example 9: The preparation method of the compound extractant includes the following steps: V in the deprotectant of Preparation Example 5 三氟乙酸 V 二氯甲烷 =1:9 replaced with V 三氟乙酸 V 二氯甲烷 The ratio was 2:3, and other operations were the same as in Preparation Example 5.

[0041] Example 1: A method for extracting muscone includes the following steps: 100 parts by weight of musk powder were dispersed in 1000 parts by weight of pH 7.5 phosphate buffer, 0.8 parts by weight of lipase and 0.8 parts by weight of trypsin were added, and the mixture was stirred at 150 r / min for 10 h at 38 °C. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 15 min, and the supernatant was collected to obtain an aqueous enzymatic hydrolysate containing musk ketone. The aqueous enzymatic hydrolysate was transferred to a separatory funnel, and ethyl acetate equivalent to 0.2 times the weight of the aqueous enzymatic hydrolysate was added. The mixture was shaken and mixed at 25°C for 15 min. After standing and separating the layers, the upper organic phase was collected. 10 parts by weight of anhydrous magnesium sulfate were added to the organic phase and dried for 15 min. After filtration, the organic extract was obtained. 20 parts by weight of the composite extractant prepared in Example 1 and 0.01 parts by weight of p-toluenesulfonic acid were added to 300 parts by weight of organic extract. The mixture was stirred at 23°C in the dark for 10 h. After the reaction was completed, the solid was collected by filtration, washed three times with ethyl acetate, and dried under vacuum at 35°C for 12 h to obtain a ketone-containing complex. The ketone-containing complex was dispersed in 300 parts by weight of a first mixed solvent (V 2-甲基四氢呋喃 V pH3.5乙酸缓冲液 =20:4), in an environment of 25℃, using 365nm ultraviolet light at 10mW / cm². 2 Irradiated with high power and stirred for 4 hours. After the reaction was completed, the mixture was allowed to stand and separate into layers. The 2-methyltetrahydrofuran phase was collected to obtain the 2-methyltetrahydrofuran eluent containing muscon. The above 2-methyltetrahydrofuran eluent was transferred to a rotary evaporator and concentrated under reduced pressure in a 40°C water bath to completely recover the 2-methyltetrahydrofuran solvent, yielding a concentrated crude ketone oil. 150-200 parts by weight of 200-mesh chromatographic grade silica gel was weighed as the stationary phase, and gradient elution was performed using a petroleum ether / ethyl acetate mixed solvent system. The elution program started with pure petroleum ether to wash away non-polar impurities, then gradually increased the polarity of ethyl acetate, using petroleum ether / ethyl acetate ratios of 50:1, 30:1, 15:1, and 10:1 (v / v) for gradient elution. The crude ketone oil was dissolved in a small amount of dichloromethane and then eluted with silica gel. After sample loading, elution was performed according to the set program, and the fractions were closely monitored using thin-layer chromatography. Fractions with consistent Rf values ​​and showing a single main spot were combined to obtain a semi-pure eluent rich in muscone. The combined muscone-rich eluent was concentrated again under reduced pressure to dryness. 30-50 parts by weight of anhydrous ethanol were added to this concentrate, and the mixture was heated to 40°C to completely dissolve it and form a homogeneous solution. This homogeneous solution was sealed and placed at 4°C for 12 hours. The precipitated pure crystals were collected by filtration and washed three times with 5 parts by weight of pre-cooled anhydrous ethanol. The resulting wet crystals were placed in a vacuum drying oven and dried at 35°C for 8 hours to obtain muscone.

[0042] Example 2: A method for extracting muscone includes the following steps: 100 parts by weight of musk powder were dispersed in 1000 parts by weight of pH 7.5 phosphate buffer, 0.9 parts by weight of lipase and 0.9 parts by weight of trypsin were added, and the mixture was stirred at 150 r / min for 11 h at 39 °C. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 15 min, and the supernatant was collected to obtain an aqueous enzymatic hydrolysate containing musk ketone. The aqueous enzymatic hydrolysate was transferred to a separatory funnel, and ethyl acetate equivalent to 0.25 times the weight of the aqueous enzymatic hydrolysate was added. The mixture was shaken and mixed at 27°C for 17 min. After standing and separating into layers, the upper organic phase was collected. 10.5 parts by weight of anhydrous magnesium sulfate was added to the organic phase and dried for 16 min. After filtration, the organic extract was obtained. 22 parts by weight of the composite extractant prepared in Example 2 and 0.012 parts by weight of p-toluenesulfonic acid were added to 350 parts by weight of organic extract. The mixture was stirred at 23.5°C in the dark for 11 h. After the reaction was completed, the solid was collected by filtration, washed three times with ethyl acetate, and dried under vacuum at 35°C for 12.5 h to obtain a ketone-containing complex. The ketone-containing complex was dispersed in 300 parts by weight of a first mixed solvent (V 2-甲基四氢呋喃 V pH3.5乙酸缓冲液 =20:4.5), in an environment of 26℃, using 365nm ultraviolet light at 15mW / cm 2The mixture was irradiated with high power and stirred for 4.5 h. After the reaction was completed, the mixture was allowed to stand and separate into layers. The 2-methyltetrahydrofuran phase was collected to obtain the 2-methyltetrahydrofuran eluent containing muscon. The above 2-methyltetrahydrofuran eluent was transferred to a rotary evaporator and concentrated under reduced pressure in a 40°C water bath to completely recover the 2-methyltetrahydrofuran solvent, yielding a concentrated crude ketone oil. 150-200 parts by weight of 200-mesh chromatographic grade silica gel was weighed as the stationary phase, and gradient elution was performed using a petroleum ether / ethyl acetate mixed solvent system. The elution program started with pure petroleum ether to wash away non-polar impurities, then gradually increased the polarity of ethyl acetate, using petroleum ether / ethyl acetate ratios of 50:1, 30:1, 15:1, and 10:1 (v / v) for gradient elution. The crude ketone oil was dissolved in a small amount of dichloromethane and then eluted with silica gel. After sample loading, elution was performed according to the set program, and the fractions were closely monitored using thin-layer chromatography. Fractions with consistent Rf values ​​and showing a single main spot were combined to obtain a semi-pure eluent rich in muscone. The combined muscone-rich eluent was concentrated again under reduced pressure to dryness. 30-50 parts by weight of anhydrous ethanol were added to this concentrate, and the mixture was heated to 40°C to completely dissolve it and form a homogeneous solution. This homogeneous solution was sealed and placed at 4°C for 12 hours. The precipitated pure crystals were collected by filtration and washed three times with 5 parts by weight of pre-cooled anhydrous ethanol. The resulting wet crystals were placed in a vacuum drying oven and dried at 35°C for 8 hours to obtain muscone.

[0043] Example 3: A method for extracting muscone includes the following steps: 100 parts by weight of musk powder were dispersed in 1000 parts by weight of pH 7.5 phosphate buffer, 1.0 part by weight of lipase and 1.0 part by weight of trypsin were added, and the mixture was stirred at 150 r / min for 12 h at 40 °C. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 15 min, and the supernatant was collected to obtain an aqueous enzymatic hydrolysate containing musk ketone. The aqueous enzymatic hydrolysate was transferred to a separatory funnel, and 2-methyltetrahydrofuran equivalent to 0.3 times the weight of the aqueous enzymatic hydrolysate was added. The mixture was shaken and mixed at 30°C for 20 min. After standing and separating the layers, the upper organic phase was collected. 11 parts by weight of anhydrous magnesium sulfate were added to the organic phase and dried for 17 min. After filtration, the organic extract was obtained. 25 parts by weight of the composite extractant prepared in Example 3 and 0.015 parts by weight of p-toluenesulfonic acid were added to 400 parts by weight of organic extract. The mixture was stirred at 24°C in the dark for 12 h. After the reaction was completed, the solid was collected by filtration, washed three times with ethyl acetate, and dried under vacuum at 35°C for 13 h to obtain a ketone-containing complex. The ketone-containing complex was dispersed in 300 parts by weight of a first mixed solvent (V 2-甲基四氢呋喃 V pH3.5乙酸缓冲液=20:5), in an environment of 27℃, using 365nm ultraviolet light at 17mW / cm². 2 Irradiated with high power and stirred for 5 hours. After the reaction was completed, the mixture was allowed to stand and separate into layers. The 2-methyltetrahydrofuran phase was collected to obtain the 2-methyltetrahydrofuran eluent containing muscon. The above 2-methyltetrahydrofuran eluent was transferred to a rotary evaporator and concentrated under reduced pressure in a 40°C water bath to completely recover the 2-methyltetrahydrofuran solvent, yielding a concentrated crude ketone oil. 150-200 parts by weight of 200-mesh chromatographic grade silica gel was weighed as the stationary phase, and gradient elution was performed using a petroleum ether / ethyl acetate mixed solvent system. The elution program started with pure petroleum ether to wash away non-polar impurities, then gradually increased the polarity of ethyl acetate, using petroleum ether / ethyl acetate ratios of 50:1, 30:1, 15:1, and 10:1 (v / v) for gradient elution. The crude ketone oil was dissolved in a small amount of dichloromethane and then eluted with silica gel. After sample loading, elution was performed according to the set program, and the fractions were closely monitored using thin-layer chromatography. Fractions with consistent Rf values ​​and showing a single main spot were combined to obtain a semi-pure eluent rich in muscone. The combined muscone-rich eluent was concentrated again under reduced pressure to dryness. 30-50 parts by weight of anhydrous ethanol were added to this concentrate, and the mixture was heated to 40°C to completely dissolve it and form a homogeneous solution. This homogeneous solution was sealed and placed at 4°C for 12 hours. The precipitated pure crystals were collected by filtration and washed three times with 5 parts by weight of pre-cooled anhydrous ethanol. The resulting wet crystals were placed in a vacuum drying oven and dried at 35°C for 8 hours to obtain muscone.

[0044] Example 4: A method for extracting muscone includes the following steps: 100 parts by weight of musk powder were dispersed in 1000 parts by weight of pH 7.5 phosphate buffer, 1.1 parts by weight of lipase and 1.1 parts by weight of trypsin were added, and the mixture was stirred at 150 r / min for 13 h at 41 °C. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 15 min, and the supernatant was collected to obtain an aqueous enzymatic hydrolysate containing musk ketone. The aqueous enzymatic hydrolysate was transferred to a separatory funnel, and 2-methyltetrahydrofuran equivalent to 0.4 times the weight of the aqueous enzymatic hydrolysate was added. The mixture was shaken and mixed at 32°C for 23 min. After standing and separating the layers, the upper organic phase was collected. 11.5 parts by weight of anhydrous magnesium sulfate was added to the organic phase and dried for 18 min. After filtration, the organic extract was obtained. 28 parts by weight of the composite extractant prepared in Example 4 and 0.017 parts by weight of p-toluenesulfonic acid were added to 450 parts by weight of organic extract. The mixture was stirred at 24.5°C in the dark for 13 h. After the reaction was completed, the solid was collected by filtration, washed three times with ethyl acetate, and dried under vacuum at 35°C for 13.5 h to obtain a ketone-containing complex. The ketone-containing complex was dispersed in 300 parts by weight of a first mixed solvent (V 2-甲基四氢呋喃 V pH3.5乙酸缓冲液 =20:5.5), in an environment of 28℃, using 365nm ultraviolet light at 18mW / cm 2 Irradiated with high power and stirred for 5.5 h. After the reaction was completed, the mixture was allowed to stand and separate into layers. The 2-methyltetrahydrofuran phase was collected to obtain the 2-methyltetrahydrofuran eluent containing muscon. The above 2-methyltetrahydrofuran eluent was transferred to a rotary evaporator and concentrated under reduced pressure in a 40°C water bath to completely recover the 2-methyltetrahydrofuran solvent, yielding a concentrated crude ketone oil. 150-200 parts by weight of 200-mesh chromatographic grade silica gel was weighed as the stationary phase, and gradient elution was performed using a petroleum ether / ethyl acetate mixed solvent system. The elution program started with pure petroleum ether to wash away non-polar impurities, then gradually increased the polarity of ethyl acetate, using petroleum ether / ethyl acetate ratios of 50:1, 30:1, 15:1, and 10:1 (v / v) for gradient elution. The crude ketone oil was dissolved in a small amount of dichloromethane and then eluted with silica gel. After sample loading, elution was performed according to the set program, and the fractions were closely monitored using thin-layer chromatography. Fractions with consistent Rf values ​​and showing a single main spot were combined to obtain a semi-pure eluent rich in muscone. The combined muscone-rich eluent was concentrated again under reduced pressure to dryness. 30-50 parts by weight of anhydrous ethanol were added to this concentrate, and the mixture was heated to 40°C to completely dissolve it and form a homogeneous solution. This homogeneous solution was sealed and placed at 4°C for 12 hours. The precipitated pure crystals were collected by filtration and washed three times with 5 parts by weight of pre-cooled anhydrous ethanol. The resulting wet crystals were placed in a vacuum drying oven and dried at 35°C for 8 hours to obtain muscone.

[0045] Example 5: A method for extracting muscone includes the following steps: 100 parts by weight of musk powder were dispersed in 1000 parts by weight of pH 7.5 phosphate buffer, 1.2 parts by weight of lipase and 1.2 parts by weight of trypsin were added, and the mixture was stirred at 150 r / min for 14 h at 42 °C. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 15 min, and the supernatant was collected to obtain an aqueous enzymatic hydrolysate containing musk ketone. The aqueous enzymatic hydrolysate was transferred to a separatory funnel, and 2-methyltetrahydrofuran equivalent to 0.5 times the weight of the aqueous enzymatic hydrolysate was added. The mixture was shaken and mixed at 35°C for 25 min. After standing and separating the layers, the upper organic phase was collected. 12 parts by weight of anhydrous magnesium sulfate were added to the organic phase and dried for 20 min. After filtration, the organic extract was obtained. 30 parts by weight of the composite extractant prepared in Example 5 and 0.02 parts by weight of p-toluenesulfonic acid were added to the above organic extract. The mixture was stirred at 25°C in the dark for 14 h. After the reaction was completed, the solid was collected by filtration, washed three times with ethyl acetate, and dried under vacuum at 35°C for 14 h to obtain a ketone-containing complex. The ketone-containing complex was dispersed in 300 parts by weight of a first mixed solvent (V 2-甲基四氢呋喃 V pH3.5乙酸缓冲液 =20:6), in an environment of 30℃, using 365nm ultraviolet light at 20mW / cm². 2 Irradiated with high power and stirred for 6 hours. After the reaction was completed, the mixture was allowed to stand and separate into layers. The 2-methyltetrahydrofuran phase was collected to obtain the 2-methyltetrahydrofuran eluent containing muscon. The above 2-methyltetrahydrofuran eluent was transferred to a rotary evaporator and concentrated under reduced pressure in a 40°C water bath to completely recover the 2-methyltetrahydrofuran solvent, yielding a concentrated crude ketone oil. 150-200 parts by weight of 200-mesh chromatographic grade silica gel was weighed as the stationary phase, and gradient elution was performed using a petroleum ether / ethyl acetate mixed solvent system. The elution program started with pure petroleum ether to wash away non-polar impurities, then gradually increased the polarity of ethyl acetate, using petroleum ether / ethyl acetate ratios of 50:1, 30:1, 15:1, and 10:1 (v / v) for gradient elution. The crude ketone oil was dissolved in a small amount of dichloromethane and then eluted with silica gel. After sample loading, elution was performed according to the set program, and the fractions were closely monitored using thin-layer chromatography. Fractions with consistent Rf values ​​and showing a single main spot were combined to obtain a semi-pure eluent rich in muscone. The combined muscone-rich eluent was concentrated again under reduced pressure to dryness. 30-50 parts by weight of anhydrous ethanol were added to this concentrate, and the mixture was heated to 40°C to completely dissolve it and form a homogeneous solution. This homogeneous solution was sealed and placed at 4°C for 12 hours. The precipitated pure crystals were collected by filtration and washed three times with 5 parts by weight of pre-cooled anhydrous ethanol. The resulting wet crystals were placed in a vacuum drying oven and dried at 35°C for 8 hours to obtain muscone.

[0046] Comparative Example 1: A method for extracting muscone includes the following steps: The composite extractant prepared in Example 5 was replaced with the composite extractant prepared in Example 6, and all other operations were the same as in Example 5.

[0047] Comparative Example 2: A method for extracting muscone includes the following steps: The composite extractant prepared in Example 5 was replaced with the composite extractant prepared in Example 7, and all other operations were the same as in Example 5.

[0048] Comparative Example 3: A method for extracting muscone includes the following steps: The composite extractant prepared in Example 5 was replaced with the composite extractant prepared in Example 8, and all other operations were the same as in Example 5.

[0049] Comparative Example 4: A method for extracting muscone includes the following steps: The composite extractant prepared in Example 5 was replaced with the composite extractant prepared in Example 9, and all other operations were the same as in Example 5.

[0050] Comparative Example 5: A method for extracting muscone includes the following steps: The ultraviolet light irradiation treatment in Example 5 was removed, and other operations remained the same as in Example 5.

[0051] Performance testing: Muscone extraction rate and purity test: The extraction rate and purity of muscone obtained in Examples 1-5 and Comparative Examples 1-5 were analyzed by chromatography; Number of times the compound extractant is recycled: After completing one extraction-elution process, the used compound extractant is subjected to 450nm visible light at 80mW / cm. 2 After being irradiated with high power for 60 minutes, the material was regenerated by washing and vacuum drying before being used in the next extraction experiment. The number of times the material could be used was recorded until the extraction rate dropped below 85% of the initial value. The test results are shown in Table 1.

[0052] Table 1. Performance test results of the examples and comparative examples Example 1 92.4±0.5 99.5±0.3 ≥10 Example 2 92.7±0.3 99.5±0.2 ≥10 Example 3 92.9±0.4 99.5±0.2 ≥10 Example 4 93.1±0.6 99.6±0.1 ≥10 Example 5 93.6±0.2 99.7±0.1 ≥10 Comparative Example 1 60.3±0.7 90.2±0.5 ≤3 Comparative Example 2 55.9±0.4 85.7±0.6 ≤2 Comparative Example 3 70.8±0.5 93.1±0.4 ≤5 Comparative Example 4 75.6±0.3 94.8±0.3 ≤6 Comparative Example 5 12.8±0.6 80.5±0.7 ≥10 Based on the test results in Table 1, the following conclusions can be drawn: (1) The musk ketones extracted by the methods in Examples 1 to 5 of the present invention have good yield and purity, and the composite extractants in Examples 1 to 5 have good regeneration and recycling performance. However, the musk ketones extracted by the methods in Comparative Examples 1 to 5 have reduced yield and purity, and the composite extractants in some comparative examples have poor regeneration and recycling performance. (2) The reason for the performance reduction of Comparative Example 1 may be that after removing azobenzene-4,4'-dicarboxylic acid, during the release stage, due to the lack of azobenzene units, ultraviolet light cannot induce the molecular configuration to change from trans to cis, and cannot physically disturb the hydrazone bonds in the pores. The hydrazone bond breakage between the muscone molecule and the composite extractant is affected, thus affecting the desorption process and reducing the muscone extraction rate; the material regeneration is difficult, resulting in a reduction in the number of times it can be recycled. (3) The reason for the performance reduction of Comparative Example 2 may be that the removal of the hydrazide modifier resulted in the loss of the key functional group that covalently binds with the ketone group of muscone. Relying solely on the physical adsorption of the photosensitive extractant, the selectivity in complex organic extracts is extremely poor, the adsorption amount is low, and it is easily competitively adsorbed by other impurities, which leads to a decrease in both extraction rate and purity. The physical adsorption force is weak and it is easily contaminated and poisoned by impurities, resulting in poor stability and a reduced number of recycling cycles. (4) The reason for the performance reduction of Comparative Example 3 may be the removal of the vacuum activation step of the photosensitive extractant. The purpose of vacuum activation is to remove adsorbed water and impurities on the surface of the photosensitive extractant and expose more metal active sites so as to combine with the acyl hydrazine modifier. After the activation step is removed, the active sites on the surface of the photosensitive extractant are blocked, and the acyl hydrazine modifier cannot effectively coordinate and bind, resulting in a reduction in the number of acyl hydrazine groups in the composite extractant and a weakening of the ability to capture muscone. With fewer active sites, the selectivity of the extractant for muscone is reduced, a small amount of impurities are adsorbed, and the purity is slightly reduced. Insufficient active sites lead to a reduction in the amount of muscone captured in each cycle, and the unactivated extractant is prone to adsorbing impurities. The partially blocked pores also affect the cycling performance of the material. (5) The reason for the performance reduction of Comparative Example 4 may be that the ratio of deprotecting agent was inappropriate, the acid concentration was increased, and the excessively strong acidic conditions may cause certain damage to the structure of the photosensitive extractant. It may also cause excessive side reactions of the hydrazide group during the removal of the tert-butyloxycarbonyl protecting group, thereby reducing its ability to capture muscone molecules. Partial damage to the structure of the composite extractant may have an adverse effect on its service life. (6) The reason for the performance reduction of Comparative Example 5 may be that the ultraviolet light irradiation treatment was removed during the application stage, which made the entire photo-triggered release mechanism unable to start; the composite extractant successfully captured muscone molecules, but lacked light energy input, the azobenzene unit maintained the trans configuration, and there was no physical disturbance in the pores. Although it was in an acidic environment, the hydrolysis rate of the hydrazone bond was slow, the release efficiency of muscone molecules was reduced, and some muscone remained in the composite extractant, resulting in a reduction in its extraction rate and purity; although the number of recycling cycles was high, the extraction efficiency of each cycle was extremely low, which could not meet the application requirements.

[0053] The embodiments described above provide a detailed explanation of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed.

Claims

1. A method for extracting muscone, characterized in that, The method includes the following steps: Musk powder was hydrolyzed by lipase and trypsin to obtain an aqueous enzymatic hydrolysate; The organic phase is collected by mixing the aqueous enzymatic hydrolysate and the extraction solvent to obtain the organic extract. The compound extractant and p-toluenesulfonic acid were dispersed in an organic extract and stirred to obtain a ketone-containing complex. The ketone-containing complex was dispersed in a first mixed solvent and reacted under continuous stirring under ultraviolet light irradiation, followed by separation and purification to obtain the muscone. The extraction solvent is ethyl acetate or 2-methyltetrahydrofuran; The preparation method of the composite extractant includes the following steps: A photosensitive extractant was obtained by reacting zirconium tetrachloride, azobenzene-4,4'-dicarboxylic acid and terephthalic acid. Succinic anhydride and tert-butyloxycarbonylhydrazine were mixed and stirred to produce an acylhydrazine modifier; The photosensitive extractant is activated under vacuum to obtain an activated extractant, and the activated extractant and the acyl hydrazine modifier are mixed and stirred to obtain a modified extractant; The composite extractant is prepared by mixing and stirring the modified extractant and the deprotecting agent; The deprotectant is prepared by mixing trichloroacetic acid and dichloromethane in a volume ratio of 1:

9.

2. The method for extracting muscone as described in claim 1, characterized in that, The weight ratio of zirconium tetrachloride, azobenzene-4,4'-dicarboxylic acid, and terephthalic acid is 2.25~2.45:0.55~0.75:1.33~1.

53.

3. The method for extracting muscone as described in claim 1, characterized in that, The weight ratio of succinic anhydride to tert-butyloxycarbonyl hydrazine is 7.5~11.5:9~10.

4. The method for extracting muscone according to claim 1, characterized in that, The weight ratio of the activating extractant to the acylhydrazine modifier is 1:1~2.

5. The method for extracting muscone as described in claim 1, characterized in that, The weight ratio of the modified extractant to the deprotectant is 5:30~50.

6. The method for extracting muscone as described in claim 1, characterized in that, The weight ratio of the composite extractant, p-toluenesulfonic acid, and organic extract is 20~30:0.01~0.02:300~500.

7. The method for extracting muscone as described in claim 1, characterized in that, The first mixed solvent was prepared by mixing 2-methyltetrahydrofuran and a pH 3.5 acetic acid buffer at a volume ratio of 20:4~6.

8. The method for extracting muscone as described in claim 1, characterized in that, The conditions for ultraviolet irradiation include an irradiation wavelength of 365 nm and an irradiation power of 10~20 W / cm². 2 .