Mushroom aroma compounds and methods for their preparation

Abstract

The present application relates to the field of perfume technology, and particularly relates to a mushroom aroma compound and a preparation method thereof, which has the following structural formula: The compound of the present application presents mushroom characteristic aroma, has important use in the field of daily chemical perfumery, and has the characteristics of long-lasting aroma; the method for preparing the mushroom aroma compound is simple and efficient, operation control is convenient, the product produced has high quality, low cost, and is beneficial to industrial production; meanwhile, the compound prepared presents mushroom aroma, the aroma is obvious, the molecular weight is high, the aroma lasts for a long time, has important use in the field of perfumery, and can well meet the needs of the field of daily chemical perfumery.

Description

Technical Field

[0001] This invention relates to the field of fragrance technology, specifically to a mushroom aroma compound and its preparation method. Background Technology

[0002] Mushrooms, as fungi widely found in nature, possess rich ecological and nutritional value, thus playing an important role in the ecosystem and being widely used as food ingredients. In the fields of food flavoring and cosmetics flavoring, the aroma characteristic of mushrooms is also widely utilized. For example, mushroom-flavored food flavorings can enhance the mushroom characteristics of seasoning products, adding a rich and mellow mushroom aroma, and giving them a more delicious, appealing, and naturally authentic taste, thereby providing consumers with a pleasant sensory experience. Therefore, mushroom-flavored food flavorings are widely used in industries such as sauces, convenience foods, and condiments. Some commonly used compounds in existing mushroom flavorings, such as mushroom alcohol, 3-octanone, and 1-octen-3-one, all possess mushroom aroma characteristics. Due to their small molecular weight, these compounds have good volatility and usually perform well in the top notes of flavorings. However, as they evaporate, their aroma becomes less pronounced in the body and base notes of the flavoring, causing the richness and naturalness of the mushroom flavoring to become unbalanced over time. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies of the existing technology, the present invention aims to provide a mushroom aroma compound that exhibits the characteristic aroma of mushrooms, has important uses in the field of daily chemical fragrance, and has the characteristic of long-lasting fragrance.

[0004] Another objective of this invention is to provide a method for preparing a mushroom aroma compound. This method is simple and efficient, easy to operate and control, produces high-quality products at low cost, and is suitable for industrial production. At the same time, the compound obtained exhibits a mushroom aroma with a distinct fragrance, high molecular weight, and long-lasting aroma. It has important and beneficial applications in the field of fragrance blending and can well meet the needs of the daily chemical fragrance industry.

[0005] The objective of this invention is achieved through the following technical solution: a mushroom aroma compound having the following structural formula:

[0006] The mushroom aroma compound can be named ethyl 6-methyl-8-phenyl-2-nonenoate.

[0007] The compounds of this invention exhibit a mushroom-like aroma, have important applications in the field of daily chemical fragrance, and have the characteristic of long-lasting fragrance.

[0008] A method for preparing a mushroom aroma compound includes the following steps:

[0009] S1. Prepare a dry four-port reaction apparatus equipped with a thermometer, a stirring device and a reflux device for later use.

[0010] S2. Add triphenylphosphine and N,N-dimethylformamide to a dry four-port reaction apparatus under a nitrogen atmosphere. Cool the apparatus to below 0°C in an ice-water bath. Begin to add bromine dropwise while maintaining the temperature below 10°C. The dropwise addition should be completed within half an hour. Then stir the mixture at room temperature for 50-70 minutes to obtain the reaction solution for later use.

[0011] S3. Take 6,8-dimethyl-2-nonanol and pyridine. Add 6,8-dimethyl-2-nonanol to pyridine and mix well. Then add the mixture to the reaction solution obtained in step S2. Heat to 115-125℃ and reflux for 1.8-2.2 hours. Then perform vacuum distillation and collect the fraction with a pressure of 200 Pa and an air temperature of 80-110℃. Wash the fraction with a 4-6% sodium bicarbonate solution until nearly neutral, and then wash once with an 8-12% sodium chloride solution. Separate the liquid to obtain the organic layer. Then extract with diethyl ether multiple times, recover the solvent, and perform vacuum distillation again. Collect the fraction with a pressure of 200 Pa and an air temperature of 80-110℃ to obtain a colorless liquid, which is (5-bromo-4-methylpentan-2-yl)benzene, for later use. The structural formula of (5-bromo-4-methylpentan-2-yl)benzene is as follows:

[0012] S4. Add dry magnesium shavings (with the surface oxide layer removed) and anhydrous diethyl ether to a dry four-port reaction apparatus. Then, add 2-3 drops of 1,2-dibromoethane while stirring rapidly. Slightly heat the reaction apparatus in a water bath. Slowly add a mixture of (5-bromo-4-methylpentan-2-yl)benzene and anhydrous diethyl ether to initiate the reaction. Remove the water bath and continue adding the mixture dropwise at a rate that allows the diethyl ether to slightly reflux. After the addition is complete, continue the reaction for 1.8-2.2 hours to obtain magnesium bromide Grignard reagent for later use.

[0013] S5. In a separate dry, nitrogen-atmospheric four-port reaction apparatus, add an appropriate amount of anhydrous diethyl ether. Cool to below -5°C in an ice-water bath, then slowly introduce dry ethylene oxide gas, keeping the temperature below 5°C. Stop introducing the gas when the temperature remains constant. Add magnesium bromide Grignard reagent dropwise, keeping the temperature below 10°C. After the addition is complete, allow the mixture to react at room temperature for 3-5 hours. After the reaction is complete, quench the reaction mixture in ice-cooled 4-6% dilute hydrochloric acid. Separate the organic layer and wash it with 4-6% sodium bicarbonate solution until nearly neutral, then wash it once with 8-12% sodium chloride solution. Separate the organic layer and extract it multiple times with diethyl ether. After recovering the solvent, perform vacuum distillation and collect the fraction at a pressure of 200 Pa and an air temperature of 130-150°C to obtain a colorless liquid, which is 4-methyl-6-phenyl-1-heptanol, for later use. The structural formula of 4-methyl-6-phenyl-1-heptanol is as follows:

[0014] S6. Add 4-methyl-6-phenyl-1-heptanol and dimethyl sulfoxide to a dry three-necked flask equipped with a stirrer, followed by 2-iodobenzoic acid and ethoxyformylmethylenetriphenylphosphine. Stir and react at 30-40°C for 18-22 hours. After the reaction, add toluene and water, stir for 15-30 minutes, and then filter. Separate the filtrate to obtain organic layer 1 and an aqueous layer. Extract the aqueous layer with a suitable amount of toluene multiple times to obtain organic layer 2. Combine organic layers 1 and 2, and wash the combined organic layer once with a suitable amount of 8-12% sodium chloride solution. Separate the organic layer, recover the solvent, and then perform vacuum distillation. Collect the fraction at a pressure of 180 Pa and an air temperature of 150-175°C to obtain the mushroom aroma compound, namely ethyl 6-methyl-8-phenyl-2-nonenoate. The structural formula of ethyl 6-methyl-8-phenyl-2-nonenoate is as follows:

[0015] The method for preparing mushroom aroma compounds in this invention is simple, efficient, and easy to operate and control. The produced products are of high quality and low cost, making them suitable for industrial production. The resulting compounds exhibit a distinct mushroom aroma, high molecular weight, and long-lasting fragrance, making them valuable for use in the fragrance industry and well-suited to the needs of the daily chemical fragrance sector. Specifically, controlling the reaction of 6,8-dimethyl-2-nonanol and pyridine in step S3 at 115-125°C optimizes the forward reaction. Furthermore, the use of N,N-dimethylformamide further promotes the forward reaction and increases the conversion rate of the reactants.

[0016] Preferably, the molar ratio of the amounts of triphenylphosphine, bromine, 6,8-dimethyl-2-nonanol and pyridine is 0.4-0.6:0.4-0.6:0.39-0.59:0.39-0.59.

[0017] Preferably, in step S2, the mass ratio of triphenylphosphine to N,N-dimethylformamide is 0.1-0.2:0.3-0.5.

[0018] Preferably, in step S4, the molar ratio of the magnesium shavings to (5-bromo-4-methylpentan-2-yl)benzene is 0.27-0.47:0.26-0.46.

[0019] Preferably, in step S4, the mass ratio of the magnesium shavings to anhydrous diethyl ether is 0.08-0.1:0.5-0.8.

[0020] Preferably, in step S4, the mass ratio of (5-bromo-4-methylpentan-2-yl)benzene to anhydrous diethyl ether is 0.6-1:1.3-1.5.

[0021] Preferably, in step S6, the molar ratio of the amounts of 4-methyl-6-phenyl-1-heptanol, 2-iodobenzoic acid and ethoxyformylmethylenetriphenylphosphine is 0.14-0.34:0.26-0.46:0.26-0.46.

[0022] Preferably, in step S6, the mass ratio of 4-methyl-6-phenyl-1-heptanol to dimethyl sulfoxide is 0.03-0.05:0.6-1.0.

[0023] Preferably, in step S6, the mass ratio of 2-iodobenzoic acid, toluene, and water is 0.8-1.2:2.3-2.7:2.8-3.2.

[0024] The beneficial effects of the present invention are as follows: the compound of the present invention exhibits a mushroom-like aroma, has important applications in the field of daily chemical fragrance, and has the characteristic of long-lasting fragrance.

[0025] The present invention provides a simple and efficient method for preparing a mushroom aroma compound, which is easy to operate and control, produces high-quality products at low cost, and is conducive to industrial production. At the same time, the obtained compound exhibits a mushroom aroma, with a distinct fragrance, high molecular weight, and long-lasting aroma. It has important and beneficial applications in the field of fragrance blending and can well meet the needs of the daily chemical fragrance industry. Attached Figure Description

[0026] Figure 1 This is a gas chromatogram of the mushroom aroma compound obtained in Example 4 of the present invention. Detailed Implementation

[0027] To facilitate understanding by those skilled in the art, the following description is provided in conjunction with embodiments and appendices. Figure 1 The invention will be further described below, and the content mentioned in the embodiments is not intended to limit the invention.

[0028] Example 1

[0029] A mushroom aroma compound has the following structural formula:

[0030]

[0031] A method for preparing a mushroom aroma compound includes the following steps:

[0032] S1. Prepare a dry four-port reaction apparatus equipped with a thermometer, a stirring device and a reflux device for later use.

[0033] S2. Triphenylphosphine and N,N-dimethylformamide are added to a dry four-port reaction apparatus under a nitrogen atmosphere. The mixture is cooled to below 0°C in an ice-water bath. Bromine is then added dropwise while maintaining the temperature below 10°C. The addition is completed within half an hour. The mixture is then stirred at room temperature for 50 minutes to obtain the reaction solution for later use.

[0034] S3. Take 6,8-dimethyl-2-nonanol and pyridine. Add 6,8-dimethyl-2-nonanol to pyridine and mix well. Then add the mixture to the reaction solution obtained in step S2. Heat to 115℃ and reflux for 2.2 hours. Then perform vacuum distillation and collect the fraction with a pressure of 200 Pa and an air temperature of 80-110℃. Wash the fraction with a 4% sodium bicarbonate solution until nearly neutral, and then wash it once with an 8% sodium chloride solution. Separate the liquid to obtain the organic layer. Then extract with diethyl ether multiple times, recover the solvent, and perform vacuum distillation again. Collect the fraction with a pressure of 200 Pa and an air temperature of 80-110℃ to obtain a colorless liquid, which is (5-bromo-4-methylpentan-2-yl)benzene, for later use. The structural formula of (5-bromo-4-methylpentan-2-yl)benzene is as follows:

[0035] S4. Add dry magnesium shavings (with the surface oxide layer removed) and anhydrous diethyl ether to a dry four-port reaction apparatus. Then, add 2-3 drops of 1,2-dibromoethane while stirring rapidly. Heat the reaction apparatus slightly in a water bath. Slowly add a mixture of (5-bromo-4-methylpentan-2-yl)benzene and anhydrous diethyl ether to initiate the reaction. Remove the water bath and continue adding the mixture dropwise, with the rate of addition being such that the diethyl ether slightly refluxes. After the addition is complete, continue the reaction for 1.8 hours to obtain magnesium bromide Grignard reagent for later use.

[0036] S5. In a separate dry, nitrogen-atmospheric four-port reaction apparatus, add an appropriate amount of anhydrous diethyl ether. Cool to below -5°C in an ice-water bath, then slowly introduce dry ethylene oxide gas, keeping the temperature below 5°C. Stop introducing the gas when the temperature remains constant. Add magnesium bromide Grignard reagent dropwise, keeping the temperature below 10°C. After the addition is complete, allow the mixture to react at room temperature for 3 hours. After the reaction is complete, quench the reaction mixture in ice-cooled 4% dilute hydrochloric acid. Separate the organic layer and wash it with 4% sodium bicarbonate solution until nearly neutral, then wash it once with 8% sodium chloride solution. Separate the organic layer and extract it multiple times with diethyl ether. After recovering the solvent, perform vacuum distillation and collect the fraction at a pressure of 200 Pa and an air temperature of 130-150°C to obtain a colorless liquid, which is 4-methyl-6-phenyl-1-heptanol, for later use. The structural formula of 4-methyl-6-phenyl-1-heptanol is as follows:

[0037] S6. Add 4-methyl-6-phenyl-1-heptanol and dimethyl sulfoxide to a dry three-necked flask equipped with a stirrer, followed by 2-iodobenzoic acid and ethoxyformylmethylenetriphenylphosphine. Stir the mixture at 30°C for 18 hours. After the reaction, add toluene and water, stir for 15 minutes, and then filter. Separate the filtrate to obtain organic layer 1 and an aqueous layer. Extract the aqueous layer with toluene multiple times to obtain organic layer 2. Combine organic layers 1 and 2, and wash the combined organic layers once with an 8% sodium chloride solution. Separate the organic layers, recover the solvent, and then perform vacuum distillation. Collect the fraction at a pressure of 180 Pa and an air temperature of 150-175°C to obtain the mushroom aroma compound, namely ethyl 6-methyl-8-phenyl-2-nonenoate. The structural formula of ethyl 6-methyl-8-phenyl-2-nonenoate is as follows:

[0038] The molar ratio of triphenylphosphine, bromine, 6,8-dimethyl-2-nonanol and pyridine is 0.4:0.4:0.39:0.39.

[0039] In step S2, the mass ratio of triphenylphosphine to N,N-dimethylformamide is 0.1:0.3.

[0040] In step S4, the molar ratio of magnesium shavings to (5-bromo-4-methylpentan-2-yl)benzene is 0.27:0.26.

[0041] In step S4, the mass ratio of magnesium shavings to anhydrous diethyl ether is 0.08:0.5.

[0042] In step S4, the mass ratio of (5-bromo-4-methylpentan-2-yl)benzene to anhydrous diethyl ether is 0.6:1.3.

[0043] In step S6, the molar ratio of 4-methyl-6-phenyl-1-heptanol, 2-iodobenzoic acid, and ethoxyformylmethylenetriphenylphosphine is 0.14:0.26:0.26.

[0044] In step S6, the mass ratio of 4-methyl-6-phenyl-1-heptanol to dimethyl sulfoxide is 0.03:0.6.

[0045] In step S6, the mass ratio of 2-iodobenzoic acid, toluene, and water is 0.8:2.3:2.8.

[0046] Example 2

[0047] A mushroom aroma compound has the following structural formula:

[0048]

[0049] A method for preparing a mushroom aroma compound includes the following steps:

[0050] S1. Prepare a dry four-port reaction apparatus equipped with a thermometer, a stirring device and a reflux device for later use.

[0051] S2. Triphenylphosphine and N,N-dimethylformamide are added to a dry four-port reaction apparatus under a nitrogen atmosphere. The apparatus is cooled to below 0°C in an ice-water bath. Bromine is then added dropwise while maintaining the temperature below 10°C. The addition is completed within half an hour. The mixture is then stirred at room temperature for 60 minutes to obtain the reaction solution for later use.

[0052] S3. Take 6,8-dimethyl-2-nonanol and pyridine. Add 6,8-dimethyl-2-nonanol to pyridine and mix well. Then add the mixture to the reaction solution obtained in step S2. Heat to 120°C and reflux for 2 hours. Then perform vacuum distillation and collect the fraction with a pressure of 200 Pa and an air temperature of 80-110°C. Wash the fraction with a 5% sodium bicarbonate solution until nearly neutral, and then wash it once with a 10% sodium chloride solution. Separate the liquid to obtain the organic layer. Then extract with diethyl ether multiple times, recover the solvent, and perform vacuum distillation again. Collect the fraction with a pressure of 200 Pa and an air temperature of 80-110°C to obtain a colorless liquid, which is (5-bromo-4-methylpentan-2-yl)benzene, for later use. The structural formula of (5-bromo-4-methylpentan-2-yl)benzene is as follows:

[0053] S4. Add dry magnesium shavings (with the surface oxide layer removed) and anhydrous diethyl ether to a dry four-port reaction apparatus. Then, add 2-3 drops of 1,2-dibromoethane while stirring rapidly. Heat the reaction apparatus slightly in a water bath. Slowly add a mixture of (5-bromo-4-methylpentan-2-yl)benzene and anhydrous diethyl ether to initiate the reaction. Remove the water bath and continue adding the mixture dropwise, with the rate of addition being such that the diethyl ether slightly refluxes. After the addition is complete, continue the reaction for 2 hours to obtain magnesium bromide Grignard reagent for later use.

[0054] S5. In a separate dry, nitrogen-atmospheric four-port reaction apparatus, add an appropriate amount of anhydrous diethyl ether. Cool to below -5°C in an ice-water bath, then slowly introduce dry ethylene oxide gas, keeping the temperature below 5°C. Stop introducing the gas when the temperature remains constant. Add magnesium bromide Grignard reagent dropwise, keeping the temperature below 10°C. After the addition is complete, allow the mixture to react at room temperature for 4 hours. After the reaction is complete, quench the reaction mixture in ice-cooled 5% dilute hydrochloric acid. Separate the organic layer and wash it with 5% sodium bicarbonate solution until nearly neutral, then wash it once with 10% sodium chloride solution. Separate the organic layer and extract it multiple times with diethyl ether. After recovering the solvent, perform vacuum distillation and collect the fraction at a pressure of 200 Pa and an air temperature of 130-150°C to obtain a colorless liquid, which is 4-methyl-6-phenyl-1-heptanol, for later use. The structural formula of 4-methyl-6-phenyl-1-heptanol is as follows:

[0055] S6. Add 4-methyl-6-phenyl-1-heptanol and dimethyl sulfoxide to a dry three-necked flask equipped with a stirrer, followed by 2-iodobenzoic acid and ethoxyformylmethylenetriphenylphosphine. Stir the mixture at 35°C for 20 hours. After the reaction, add toluene and water, stir for 25 minutes, and then filter. Separate the filtrate to obtain organic layer 1 and an aqueous layer. Extract the aqueous layer with toluene multiple times to obtain organic layer 2. Combine organic layers 1 and 2, and wash the combined organic layers once with a 10% sodium chloride solution. Separate the organic layers, recover the solvent, and then perform vacuum distillation. Collect the fraction at a pressure of 180 Pa and an air temperature of 150-175°C to obtain the mushroom aroma compound, namely ethyl 6-methyl-8-phenyl-2-nonenoate. The structural formula of ethyl 6-methyl-8-phenyl-2-nonenoate is as follows:

[0056] The molar ratio of triphenylphosphine, bromine, 6,8-dimethyl-2-nonanol and pyridine is 0.5:0.5:0.49:0.49.

[0057] In step S2, the mass ratio of triphenylphosphine to N,N-dimethylformamide is 0.15:0.4.

[0058] In step S4, the molar ratio of magnesium shavings to (5-bromo-4-methylpentan-2-yl)benzene is 0.37:0.36.

[0059] In step S4, the mass ratio of magnesium shavings to anhydrous diethyl ether is 0.09:0.6.

[0060] In step S4, the mass ratio of (5-bromo-4-methylpentan-2-yl)benzene to anhydrous diethyl ether is 0.8:1.4.

[0061] In step S6, the molar ratio of 4-methyl-6-phenyl-1-heptanol, 2-iodobenzoic acid, and ethoxyformylmethylenetriphenylphosphine is 0.24:0.36:0.36.

[0062] In step S6, the mass ratio of 4-methyl-6-phenyl-1-heptanol to dimethyl sulfoxide is 0.04:0.8.

[0063] In step S6, the mass ratio of 2-iodobenzoic acid, toluene, and water is 1.0:2.5:3.0.

[0064] Example 3

[0065] A mushroom aroma compound has the following structural formula:

[0066]

[0067] A method for preparing a mushroom aroma compound includes the following steps:

[0068] S1. Prepare a dry four-port reaction apparatus equipped with a thermometer, a stirring device and a reflux device for later use.

[0069] S2. Triphenylphosphine and N,N-dimethylformamide are added to a dry four-port reaction apparatus under a nitrogen atmosphere. The apparatus is cooled to below 0°C in an ice-water bath. Bromine is then added dropwise while maintaining the temperature below 10°C. The addition is completed within half an hour. The mixture is then stirred at room temperature for 70 minutes to obtain the reaction solution for later use.

[0070] S3. Take 6,8-dimethyl-2-nonanol and pyridine. Add 6,8-dimethyl-2-nonanol to pyridine and mix well. Then add the mixture to the reaction solution obtained in step S2. Heat to 125℃ and reflux for 1.8h. Then perform vacuum distillation and collect the fraction with a pressure of 200Pa and an air temperature of 80-110℃. Wash the fraction with a 6% sodium bicarbonate solution until nearly neutral, and then wash it once with a 12% sodium chloride solution. Separate the liquid to obtain the organic layer. Then extract with diethyl ether multiple times, recover the solvent, and perform vacuum distillation again. Collect the fraction with a pressure of 200Pa and an air temperature of 80-110℃ to obtain a colorless liquid, which is (5-bromo-4-methylpentan-2-yl)benzene, for later use. The structural formula of (5-bromo-4-methylpentan-2-yl)benzene is as follows:

[0071] S4. Add dry magnesium shavings (with the surface oxide layer removed) and anhydrous diethyl ether to a dry four-port reaction apparatus. Then, add 2-3 drops of 1,2-dibromoethane while stirring rapidly. Slightly heat the reaction apparatus in a water bath and slowly add a mixture of (5-bromo-4-methylpentan-2-yl)benzene and anhydrous diethyl ether to initiate the reaction. After initiating the reaction, remove the water bath and continue adding the mixture dropwise at a rate that allows the diethyl ether to slightly reflux. After the addition is complete, continue the reaction for 2.2 hours to obtain magnesium bromide Grignard reagent for later use.

[0072] S5. In a separate dry, nitrogen-atmospheric four-port reaction apparatus, add an appropriate amount of anhydrous diethyl ether. Cool to below -5°C in an ice-water bath, then slowly introduce dry ethylene oxide gas, keeping the temperature below 5°C. Stop introducing the gas when the temperature remains constant. Add magnesium bromide Grignard reagent dropwise, keeping the temperature below 10°C. After the addition is complete, allow the mixture to react at room temperature for 5 hours. After the reaction is complete, quench the reaction mixture in ice-cooled 6% dilute hydrochloric acid. Separate the organic layer and wash it with 6% sodium bicarbonate solution until nearly neutral, then wash it once with 12% sodium chloride solution. Separate the organic layer and extract it multiple times with diethyl ether. After recovering the solvent, perform vacuum distillation and collect the fraction at a pressure of 200 Pa and an air temperature of 130-150°C to obtain a colorless liquid, which is 4-methyl-6-phenyl-1-heptanol, for later use. The structural formula of 4-methyl-6-phenyl-1-heptanol is as follows:

[0073] S6. Add 4-methyl-6-phenyl-1-heptanol and dimethyl sulfoxide to a dry three-necked flask equipped with a stirrer, followed by 2-iodobenzoic acid and ethoxyformylmethylenetriphenylphosphine. Stir the mixture at 40°C for 22 hours. After the reaction, add toluene and water, stir for 30 minutes, and then filter. Separate the filtrate to obtain organic layer 1 and an aqueous layer. Extract the aqueous layer with a suitable amount of toluene multiple times to obtain organic layer 2. Combine organic layers 1 and 2, and wash the combined organic layers once with a suitable amount of 12% sodium chloride solution. Separate the organic layers, recover the solvent, and then perform vacuum distillation. Collect the fraction at a pressure of 180 Pa and an air temperature of 150-175°C to obtain the mushroom aroma compound, namely ethyl 6-methyl-8-phenyl-2-nonenoate. The structural formula of ethyl 6-methyl-8-phenyl-2-nonenoate is as follows:

[0074] The molar ratio of triphenylphosphine, bromine, 6,8-dimethyl-2-nonanol and pyridine is 0.6:0.6:0.59:0.59.

[0075] In step S2, the mass ratio of triphenylphosphine to N,N-dimethylformamide is 0.2:0.5.

[0076] In step S4, the molar ratio of magnesium shavings to (5-bromo-4-methylpentan-2-yl)benzene is 0.47:0.46.

[0077] In step S4, the mass ratio of magnesium shavings to anhydrous diethyl ether is 0.1:0.8.

[0078] In step S4, the mass ratio of (5-bromo-4-methylpentan-2-yl)benzene to anhydrous diethyl ether is 1:1.5.

[0079] In step S6, the molar ratio of 4-methyl-6-phenyl-1-heptanol, 2-iodobenzoic acid, and ethoxyformylmethylenetriphenylphosphine is 0.34:0.46:0.46.

[0080] In step S6, the mass ratio of 4-methyl-6-phenyl-1-heptanol to dimethyl sulfoxide is 0.05:1.0.

[0081] In step S6, the mass ratio of 2-iodobenzoic acid, toluene, and water is 1.2:2.7:3.2.

[0082] Example 4

[0083] A mushroom aroma compound has the following structural formula:

[0084]

[0085] A method for preparing a mushroom aroma compound includes the following steps:

[0086] S1. Prepare a dry four-port reaction apparatus equipped with a thermometer, a stirring device and a reflux device for later use.

[0087]

[0088] S2. Add 131.0 g of triphenylphosphine and 500 mL of N,N-dimethylformamide to a dry four-port reaction apparatus under a nitrogen atmosphere. Cool the apparatus to below 0°C in an ice-water bath. Begin adding 80.0 g of bromine dropwise while maintaining the temperature below 10°C. The addition should be completed within half an hour. Then, stir the mixture at room temperature for 60 minutes to obtain the reaction solution for later use.

[0089] S3. Take 84.4g of 6,8-dimethyl-2-nonanol and 38.8g of pyridine. Add 6,8-dimethyl-2-nonanol to the pyridine and mix well. Then add the mixture to the reaction solution obtained in step S2. Heat to 120℃ and reflux for 2 hours. Then perform vacuum distillation and collect the fraction with a pressure of 200 Pa and an air temperature of 80-110℃. Wash the fraction with a 5% sodium bicarbonate solution until nearly neutral, and then wash once with 200mL of a 10% sodium chloride solution. Separate the layers to obtain the organic layer. Then extract with 600mL of diethyl ether three times. After recovering the solvent, perform vacuum distillation again and collect the fraction with a pressure of 200 Pa and an air temperature of 80-110℃ to obtain a colorless liquid, which is (5-bromo-4-methylpentan-2-yl)benzene, for later use. The structural formula of (5-bromo-4-methylpentan-2-yl)benzene is as follows:

[0090]

[0091] S4. Add 9.0 g of dried magnesium shavings with the surface oxide layer removed and 100 mL of anhydrous diethyl ether to a dry four-port reaction apparatus. Then, add 2-3 drops of 1,2-dibromoethane while stirring rapidly. Heat the reaction apparatus slightly in a water bath and slowly add a mixture of 86.8 g of (5-bromo-4-methylpentan-2-yl)benzene and 200 mL of anhydrous diethyl ether to initiate the reaction. After initiating the reaction, remove the water bath and continue adding the mixture dropwise at a rate that allows the diethyl ether to slightly reflux. After the addition is complete, continue the reaction for 2 hours to obtain magnesium bromide Grignard reagent for later use.

[0092] S5. In a separate dry, nitrogen-atmospheric four-port reaction apparatus, add 200 mL of anhydrous diethyl ether. Cool to below -5°C in an ice-water bath, then slowly introduce dry ethylene oxide gas, keeping the temperature below 5°C. Stop introducing the gas when the temperature remains constant. Add magnesium bromide Grignard reagent dropwise, keeping the temperature below 10°C. After the addition is complete, allow the mixture to react at room temperature for 4 hours. After the reaction is complete, quench the reaction mixture in ice-cooled 5% dilute hydrochloric acid. Separate the organic layer and wash it with 5% sodium bicarbonate solution until nearly neutral, then wash it once with 200 mL of 10% sodium chloride solution. Separate the organic layer and extract it three times with 600 mL of diethyl ether. After recovering the solvent, perform vacuum distillation and collect the fraction at a pressure of 200 Pa and an air temperature of 130-150°C to obtain a colorless liquid, which is 4-methyl-6-phenyl-1-heptanol, for later use. The structural formula of 4-methyl-6-phenyl-1-heptanol is as follows:

[0093]

[0094] S6. Add 49.5 g of 4-methyl-6-phenyl-1-heptanol and 800 mL of dimethyl sulfoxide to a dry three-necked flask equipped with a stirrer. Then add 100.8 g of 2-iodobenzoic acid and 125.4 g of ethoxyformylmethylenetriphenylphosphine. Stir the mixture at 35 °C for 20 h. After the reaction is complete, add toluene and water, stir for 20 min, and then filter. Separate the filtrate to obtain organic layer 1 and an aqueous layer. Extract the aqueous layer three times with 600 mL of toluene to obtain organic layer 2. Combine organic layers 1 and 2, and wash the combined organic layers once with 1000 mL of 10% sodium chloride solution. Separate the organic layers, recover the solvent, and then perform vacuum distillation. Collect the fraction at a pressure of 180 Pa and an air temperature of 150-175 °C to obtain the mushroom aroma compound, namely ethyl 6-methyl-8-phenyl-2-nonenoate. The structural formula of ethyl 6-methyl-8-phenyl-2-nonenoate is as follows:

[0095]

[0096] The prepared ethyl 6-methyl-8-phenyl-2-nonenoate has the following NMR spectral characteristics:

[0097] 1 H NMR(400MHz,CD3Cl)δ7.32-7.20(m,5H),6.92(m,1H),5.88(t,1H),4.11(q,2H),2.54(m,1H) ,1.94(m,2H),1.56(m,2H),1.50(m,2H),1.41(m,1H),1.22(t,3H),1.16(d,3H),0.87(d,3H).

[0098] 13 C NMR (100MHz, CD3Cl) δ167.3,150.5,148.6,128.9,128.8,128.7,128.4,127.6,122.7,61.8,43.0,36.9,35.6,31.1,30.9,21.5,21.4,13.9.

[0099] The mass spectrometry analysis data are as follows:

[0100] MS(ESI, m / z) 297.2(M+Na) + ); The theoretical calculation data for high-resolution electrospray ionization mass spectrometry are [C 18 H 26 NaO2] + (M+Na + The actual measured value was 297.1835, not 297.1830.

[0101] The following is the test section:

[0102] 1. Aroma Evaluation:

[0103] Eleven perfumers with more than five years of experience evaluated the aroma of the compound as follows: 10 perfumers believed that the compound exhibited a mushroom-like aroma, 6 perfumers believed that the compound also had an earthy note, 4 perfumers believed that the compound had a green aroma, and 3 perfumers believed that the compound had a herbal aroma.

[0104] 2. Fragrance retention test:

[0105] Take one scent test strip and dip it in 0.5g of ethyl 6-methyl-8-phenyl-2-nonenoate. Place the test strip on a scent rack and have 10 perfumers smell it every 4 hours. When two or more perfumers cannot detect the scent on the test strip, record the lasting fragrance time.

[0106] Fragrance retention tests showed that ethyl 6-methyl-8-phenyl-2-nonenoate had a fragrance retention time of 220 hours.

[0107] The above embodiments are preferred implementations of the present invention. In addition, the present invention can be implemented in other ways. Any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A mushroom aroma compound, characterized in that: It has the following structural formula: 。 2. A method for preparing the mushroom aroma compound as described in claim 1, characterized in that: Includes the following steps: S1. Prepare a dry four-port reaction apparatus equipped with a thermometer, a stirring device and a reflux device for later use. S2. Add triphenylphosphine and N,N-dimethylformamide to a dry four-port reaction apparatus under a nitrogen atmosphere. Cool the apparatus to below 0°C in an ice-water bath. Begin to add bromine dropwise while maintaining the temperature below 10°C. The dropwise addition should be completed within half an hour. Then stir the mixture at room temperature for 50-70 minutes to obtain the reaction solution for later use. S3. Take 6,8-dimethyl-2-nonanol and pyridine. Add 6,8-dimethyl-2-nonanol to pyridine and mix well. Then add the mixture to the reaction solution obtained in step S2. Heat to 115-125℃ and reflux for 1.8-2.2h. Then perform vacuum distillation and collect the fraction with a pressure of 200 Pa and an air temperature of 80-110℃. Wash the fraction with a 4-6% sodium bicarbonate solution until it is nearly neutral, and then wash it once with an 8-12% sodium chloride solution. Separate the liquid to obtain the organic layer. Then extract it with diethyl ether multiple times, recover the solvent, and perform vacuum distillation again. Collect the fraction with a pressure of 200 Pa and an air temperature of 80-110℃ to obtain a colorless liquid, which is (5-bromo-4-methylpentan-2-yl)benzene, for later use. S4. Add dry magnesium shavings (with the surface oxide layer removed) and anhydrous diethyl ether to a dry four-port reaction apparatus. Then, add 2-3 drops of 1,2-dibromoethane while stirring rapidly. Slightly heat the reaction apparatus in a water bath. Slowly add a mixture of (5-bromo-4-methylpentan-2-yl)benzene and anhydrous diethyl ether to initiate the reaction. Remove the water bath and continue adding the mixture dropwise at a rate that allows the diethyl ether to slightly reflux. After the addition is complete, continue the reaction for 1.8-2.2 hours to obtain magnesium bromide Grignard reagent for later use. S5. In a separate dry, nitrogen-atmospheric four-port reaction apparatus, add an appropriate amount of anhydrous diethyl ether, cool to below -5°C in an ice-water bath, and then slowly introduce dry ethylene oxide gas, ensuring the temperature does not exceed 5°C. When the temperature remains constant, stop introducing the gas. Then, add magnesium bromide Grignard reagent dropwise into the apparatus. During the reaction, the temperature should not exceed 10℃. After the addition is complete, the mixture should be placed at room temperature for 3-5 hours. After the reaction is complete, the reaction solution should be quenched in 4-6% dilute hydrochloric acid cooled with ice. The organic layer obtained by separation should be washed with 4-6% sodium bicarbonate solution until it is nearly neutral, and then washed once with 8-12% sodium chloride solution. The organic layer should be separated and then extracted with diethyl ether multiple times. After the solvent is recovered, the mixture should be distilled under reduced pressure. The fraction with a pressure of 200 Pa and an air temperature of 130-150℃ should be collected to obtain a colorless liquid, which is 4-methyl-6-phenyl-1-heptanol, for later use. S6. Add 4-methyl-6-phenyl-1-heptanol and dimethyl sulfoxide to a dry three-necked flask equipped with a stirrer, followed by 2-iodobenzoic acid and ethoxyformylmethylenetriphenylphosphine. Stir the reaction at 30-40℃ for 18-22 hours. After the reaction is complete, add toluene and water and stir for 15-30 minutes. Filter the mixture and separate the filtrate to obtain organic layer 1 and aqueous layer. Extract the aqueous layer with an appropriate amount of toluene multiple times to obtain organic layer 2. Combine organic layer 1 and organic layer 2, and wash the combined organic layer once with an appropriate amount of 8-12% sodium chloride solution. Separate the organic layer, recover the solvent, and then perform vacuum distillation. Collect the fraction with a pressure of 180 Pa and an air temperature of 150-175℃ to obtain the mushroom aroma compound, which is ethyl 6-methyl-8-phenyl-2-nonenoate.

3. The method for preparing a mushroom aroma compound according to claim 2, characterized in that: The molar ratio of triphenylphosphine, bromine, 6,8-dimethyl-2-nonanol and pyridine is 0.4-0.6:0.4-0.6:0.39-0.59:0.39-0.

59.

4. The method for preparing a mushroom aroma compound according to claim 2, characterized in that: In step S2, the mass ratio of triphenylphosphine to N,N-dimethylformamide is 0.1-0.2:0.3-0.

5.

5. The method for preparing a mushroom aroma compound according to claim 2, characterized in that: In step S4, the molar ratio of the magnesium shavings to (5-bromo-4-methylpentan-2-yl)benzene is 0.27-0.47:0.26-0.

46.

6. The method for preparing a mushroom aroma compound according to claim 2, characterized in that: In step S4, the mass ratio of magnesium shavings to anhydrous diethyl ether is 0.08-0.1:0.5-0.

8.

7. The method for preparing a mushroom aroma compound according to claim 2, characterized in that: In step S4, the mass ratio of (5-bromo-4-methylpentan-2-yl)benzene to anhydrous diethyl ether is 0.6-1:1.3-1.

5.

8. The method for preparing a mushroom aroma compound according to claim 2, characterized in that: In step S6, the molar ratio of 4-methyl-6-phenyl-1-heptanol, 2-iodobenzoic acid and ethoxyformylmethylenetriphenylphosphine is 0.14-0.34:0.26-0.46:0.26-0.

46.

9. The mushroom aroma compound according to claim 2, characterized in that: In step S6, the mass ratio of 4-methyl-6-phenyl-1-heptanol to dimethyl sulfoxide is 0.03-0.05:0.6-1.

0.

10. The method for preparing a mushroom aroma compound according to claim 2, characterized in that: In step S6, the mass ratio of 2-iodobenzoic acid, toluene, and water is 0.8-1.2:2.3-2.7:2.8-3.2.

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