Compounds having a sweet, cooling, honey-like aroma, methods for their preparation, and fruity odoriferous bases

Abstract

The present application relates to the field of essence and flavor technology, and particularly relates to a compound with honey sweet and cool fragrance, a preparation method thereof and a fruity fragrance base. The compound with honey sweet and cool fragrance has the following structural formula: The compound with honey sweet and cool fragrance prepared by the present application is 1,5,5-trimethyl-12-oxabicyclo[6.3.2]trideca-2,7-diene-11-ol, the compound has a caramel sweet smell, a special aromatic fragrance and a guaiac wood note, the fragrance is elegant and has a long lingering time. The preparation method of the compound is simple in process, easy to operate and control, high in production efficiency and suitable for industrial production. The fruity fragrance base prepared by the present application is added with the compound with honey sweet and cool fragrance, compared with the fruity fragrance base without the compound, the fruity fragrance is more outstanding, the cool honey sweet fragrance is more outstanding, the base has a slightly elegant agarwood note, and the quality of the base fragrance is obviously improved.

Description

Technical Field

[0001] This invention relates to the field of fragrance and flavor technology, specifically to a compound with a honey-sweet and refreshing aroma, its preparation method, and a fruity aroma base. Background Technology

[0002] In existing technologies, fragrances and flavorings are commonly used as fixatives, harmonizers, or flavoring agents to enhance the aroma and sensory experience of products, improve product quality, and meet the needs of different consumers. Therefore, developing new fragrance compounds with unique aromas and sensory experiences suitable for use as flavorings and flavorings, enriching the variety of fragrances and flavorings, further enhancing the aroma and sensory experience of products, and promoting the development of the fragrance and flavor industry and other related fields are of great significance. In view of this, this invention has developed a compound with a woody fruity aroma, giving the compound an agarwood-like fragrance, an elegant aroma, and a long-lasting scent. Currently, no fragrance and flavor companies, both domestically and internationally, have launched this compound. Therefore, this compound has important applications and broad market prospects in the field of perfumery. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies of the existing technology, the purpose of this invention is to provide a compound with a sweet and refreshing aroma, which has a caramel sweetness, a special aromatic fragrance, and a guaiac wood aroma. Its fragrance is elegant and has a long-lasting scent, and it has important application value and market prospects in the field of perfumery.

[0004] Another objective of this invention is to provide a method for preparing a compound with a sweet and refreshing aroma. The preparation method is simple, easy to operate and control, has high production efficiency, and is suitable for industrial production.

[0005] Another object of the present invention is to provide a fruity fragrance base, wherein the fruity fragrance base is added with the above-mentioned compound having a honey-sweet and cool aroma, and compared with the fruity fragrance base without the addition of the compound, it has a more prominent fruity aroma, a more prominent cool and honey-sweet aroma, and a slightly elegant agarwood aroma, and the fragrance base aroma quality is significantly improved.

[0006] The objective of this invention is achieved through the following technical solution: a compound with a sweet and refreshing aroma, having the following structural formula:

[0007] .

[0008] The compound having a sweet and refreshing aroma can be named: 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol.

[0009] The compound of the present invention has a sweet and refreshing aroma, which has a refreshing, woody, sweet and sour fruity aroma, and a sandalwood fragrance, and has important uses in the field of daily chemical fragrance.

[0010] Another objective of this invention is achieved through the following technical solution: a method for preparing a compound with a sweet and refreshing aroma, comprising the following steps:

[0011] Step 1: Using caryophyllin oxide as the raw material, 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol was prepared. The structural formula of caryophyllin oxide is shown below:

[0012] ;

[0013] The structural formula of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol is shown below:

[0014] ;

[0015] Step 2: Using 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodec-4,8-diene-4-methanol obtained in Step 1 as the raw material, and after separation and purification, a compound with a honey-sweet and refreshing aroma is obtained. The compound with a honey-sweet and refreshing aroma is 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadeca-2,7-diene-11-ol.

[0016] Furthermore, in step one, the preparation method of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol includes the following steps:

[0017] A1. Place caryophyllin oxide in a reaction vessel, add acetone to dissolve it, add some freshly prepared NBS and glacial acetic acid at room temperature, and keep stirring under light-protected conditions. When 60-70% of the caryophyllin oxide has been converted, add some more freshly prepared NBS and glacial acetic acid to make the caryophyllin oxide completely converted.

[0018] A2. After the reaction is complete, filter the solution with silica gel to remove unreacted NBS and solid succinimide; dry the filtrate with anhydrous sodium sulfate and remove the solvent under reduced pressure to obtain an oily product; dissolve the product in an aqueous acetonitrile solution, add potassium carbonate, and heat to 78-82℃ and react overnight.

[0019] A3. After the reaction was completed, the system was cooled to room temperature, diluted with water, and extracted with ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by silica gel column chromatography to obtain a colorless oily liquid, namely 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol.

[0020] Further, in step A1, 4.3-4.7 mmol of caryophyllin oxide is placed in a reaction vessel and dissolved in 28-32 mL of acetone; at room temperature, 8.8-9.2 mmol of freshly prepared NBS and 8.8-9.2 mmol of glacial acetic acid are slowly added, and stirring is maintained under light-protected conditions. After stirring for 3.5-4.5 h, when 60-70% of the caryophyllin oxide has been converted, 8.8-9.2 mmol of freshly prepared NBS and 8.8-9.2 mmol of glacial acetic acid are added again to ensure complete conversion of the raw materials.

[0021] Furthermore, in step A2, the oily product is dissolved in an acetonitrile aqueous solution, wherein the volume ratio of acetonitrile to water in the acetonitrile aqueous solution is 0.9-1.1:0.9-1.1, and 9.5-10.5 mmol of potassium carbonate is added.

[0022] Furthermore, in step two, the preparation method of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol includes the following steps:

[0023] B1. Place 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol in a reaction vessel and dissolve it in dichloromethane; then add Sc(OTf)3 at room temperature. After the reaction is complete, wash the reaction solution with water, separate the liquid phase, and extract the aqueous phase with dichloromethane.

[0024] B2. The combined organic phases were dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by silica gel column chromatography to obtain a colorless solid, which is the preparation of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol.

[0025] Further, in step B1, 0.40-0.44 mmol of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol was placed in a reaction vessel and dissolved in 9.5-12 mL of dichloromethane; then 3.038-0.042 mmol of Sc(OTf) was added at room temperature. The reaction was detected by TLC and found to be completed within 5 min. The reaction solution was washed with water, and the aqueous phase was extracted with dichloromethane after separation.

[0026] Another objective of the present invention is achieved through the following technical solution: a fruity aroma base, comprising the following raw materials in parts by weight: guaiacol 45-55 parts, ethyl acetate 4-6 parts, nonanol 16-20 parts, heptanal 13-17 parts, geraniol acetate 20-24 parts, anisaldehyde 37-43 parts, ethyl butyrate 16-20 parts, ethyl malt powder 36-40 parts, ethyl hexanoate 4-6 parts, paeonol 23-27 parts, allyl hexanoate 7-9 parts, ethyl heptanate 65-75 parts, propyl 3-cyclohexyl acrylate 1.5-2.5 parts, cyclohexyl acrylate 7-9 parts, 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol 30-40 parts, and propylene glycol 620-700 parts.

[0027] The beneficial effects of this invention are as follows: The compound with a honey-sweet and refreshing aroma obtained by this invention is 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol. This compound has a caramel-sweet aroma, a unique aromatic fragrance, and a guaiac wood note. Its fragrance is elegant and has a long-lasting effect, making it of significant application value and market potential in the perfumery field. The preparation method of this compound is simple, easy to operate and control, and has high production efficiency, making it suitable for industrial production. The fruity fragrance base obtained by this invention, with the addition of the above-mentioned compound with a honey-sweet and refreshing aroma, has a more prominent fruity aroma and a more pronounced refreshing honey-sweet fragrance compared to fruity fragrance bases without this compound, and also has a slightly elegant agarwood note, significantly improving the quality of the fragrance base aroma. Attached Figure Description

[0028] Figure 1 The hydrogen spectrum of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-diene-11-ol prepared in Example 1.

[0029] Figure 2 The carbon spectrum of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol prepared in Example 1.

[0030] Figure 3 The gas chromatogram of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol prepared in Example 1 is shown. Detailed Implementation

[0031] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to embodiments and accompanying drawings. The content mentioned in the embodiments is not intended to limit the present invention.

[0032] In an embodiment of the present invention, a compound having a sweet and refreshing aroma has the following structural formula:

[0033] .

[0034] The compound having a sweet and refreshing aroma can be named: 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol.

[0035] In an embodiment of the present invention, a method for preparing a compound having a sweet and refreshing aroma includes the following steps:

[0036] Step 1: Using caryophyllin oxide as the raw material, 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol was prepared. The structural formula of caryophyllin oxide is shown below:

[0037] ;

[0038] The structural formula of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol is shown below:

[0039] ;

[0040] Step 2: Using 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodec-4,8-diene-4-methanol obtained in Step 1 as the raw material, and after separation and purification, a compound with a honey-sweet and refreshing aroma is obtained. The compound with a honey-sweet and refreshing aroma is 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadeca-2,7-diene-11-ol.

[0041] Furthermore, in step one, the preparation method of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol includes the following steps:

[0042] A1. Place caryophyllin oxide in a reaction vessel, add acetone to dissolve it, add some freshly prepared NBS and glacial acetic acid at room temperature, and keep stirring under light-protected conditions. When 60-70% of the caryophyllin oxide has been converted, add some more freshly prepared NBS and glacial acetic acid to make the caryophyllin oxide completely converted.

[0043] A2. After the reaction is complete, filter the solution with silica gel to remove unreacted NBS and solid succinimide; dry the filtrate with anhydrous sodium sulfate and remove the solvent under reduced pressure to obtain an oily product; dissolve the product in an aqueous acetonitrile solution, add potassium carbonate, and heat to 78-82℃ and react overnight.

[0044] A3. After the reaction was completed, the system was cooled to room temperature, diluted with water, and extracted with ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by silica gel column chromatography to obtain a colorless oily liquid, namely 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol.

[0045] Further, in step A1, 4.3-4.7 mmol of caryophyllin oxide is placed in a reaction vessel and dissolved in 28-32 mL of acetone; at room temperature, 8.8-9.2 mmol of freshly prepared NBS and 8.8-9.2 mmol of glacial acetic acid are slowly added, and stirring is maintained under light-protected conditions. After stirring for 3.5-4.5 h, when 60-70% of the caryophyllin oxide has been converted, 8.8-9.2 mmol of freshly prepared NBS and 8.8-9.2 mmol of glacial acetic acid are added again to ensure complete conversion of the raw materials.

[0046] Furthermore, in step A2, the oily product is dissolved in an acetonitrile aqueous solution, wherein the volume ratio of acetonitrile to water in the acetonitrile aqueous solution is 0.9-1.1:0.9-1.1, and 9.5-10.5 mmol of potassium carbonate is added.

[0047] Furthermore, in step two, the preparation method of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol includes the following steps:

[0048] B1. Place 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol in a reaction vessel and dissolve it in dichloromethane; then add Sc(OTf)3 at room temperature. After the reaction is complete, wash the reaction solution with water, separate the liquid phase, and extract the aqueous phase with dichloromethane.

[0049] B2. The combined organic phases were dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by silica gel column chromatography to obtain a colorless solid, which is the preparation of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol.

[0050] Further, in step B1, 0.40-0.44 mmol of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol was placed in a reaction vessel and dissolved in 9.5-12 mL of dichloromethane; then 0.038-0.042 mmol of Sc(OTf)3 was added at room temperature. The reaction was detected by TLC and found to be completed within 5 min. The reaction solution was washed with water, and the aqueous phase was extracted with dichloromethane after separation.

[0051] In some embodiments of the present invention, a fruity flavor base comprises the following raw materials in parts by weight: 3.5-4.5 parts of ethyl 2-methylbutyrate, 4-6 parts of ethyl propionate, 9-11 parts of isoamyl acetate, 4-6 parts of hexyl acetate, 18-22 parts of geraniol acetate, 3.5-4.5 parts of ethyl acrylate, 13-17 parts of geraniol, 27-33 parts of isoamyl butyrate, 36-44 parts of cyclohexane, 23-27 parts of ethyl hexanoate, 26-30 parts of daumarenone, 7-9 parts of allyl hexanoate, 21-25 parts of phenethyl alcohol, 11-15 parts of white lemon oil, 44-50 parts of linalool, 35-45 parts of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol, and 650-750 parts of propylene glycol.

[0052] In a typical embodiment of the present invention, a fruity flavor base comprises the following raw materials in parts by weight: 4 parts of ethyl 2-methylbutyrate, 5 parts of ethyl propionate, 10 parts of isoamyl acetate, 5 parts of hexyl acetate, 20 parts of geraniol acetate, 4 parts of ethyl acrylate, 15 parts of geraniol, 30 parts of isoamyl butyrate, 40 parts of cyclogranyl ester, 25 parts of ethyl hexanoate, 28 parts of daumarenone, 8 parts of allyl hexanoate, 23 parts of phenethyl alcohol, 13 parts of white lemon oil, 47 parts of linalool, 40 parts of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol, and 683 parts of propylene glycol.

[0053] Example 1

[0054] This embodiment provides a compound with a sweet and refreshing aroma, having the following structural formula:

[0055] .

[0056] The chemical name of the compound with a sweet and refreshing aroma is: 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol.

[0057] The method for preparing the compound with a sweet and refreshing aroma includes the following steps:

[0058] Step 1: Preparation of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodec-4,8-diene-4-methanol. The chemical reaction formula for the preparation of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodec-4,8-diene-4-methanol is as follows:

[0059]

[0060] A1. Place caryophyllin oxidase (1.0 g, 4.5 mmol) in a flask and dissolve it in 30 mL of acetone. At room temperature, slowly add freshly prepared NBS (1.6 g, 9.0 mmol) and glacial acetic acid (0.51 mL, 9.0 mmol), and stir for 4 hours in the dark. When 60-70% of the caryophyllin oxidase has been converted, add freshly prepared NBS (1.6 g, 9.0 mmol) and glacial acetic acid (0.51 mL, 9.0 mmol) again to ensure complete conversion of the caryophyllin oxidase. The structural formula of caryophyllin oxidase is shown in Formula 1.

[0061] A2. After the reaction was completed, the unreacted NBS and solid succinimide were removed by filtration with a small amount of silica gel. The filtrate was dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation under reduced pressure to obtain an oily product. The product was dissolved in 80 mL of acetonitrile / water (v / v = 1:1) solution, potassium carbonate (1.38 g, 10 mmol) was added, and the mixture was heated to 80 °C and reacted overnight.

[0062] A2. After the reaction was completed, the mixture was cooled to room temperature, diluted with 50 mL of water, and extracted with ethyl acetate (2 × 80 mL). The combined organic phases were dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by silica gel column chromatography (200-300 mesh silica gel, alkalized with 1% triethylamine in cyclohexane solution, cyclohexane / ethyl acetate = 6:1) to obtain 371 mg of a colorless oily liquid, which yielded 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol, with a yield of 35%. 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol is shown in Formula 2 and has the following NMR spectral characteristics:

[0063] 1 H NMR (500 MHz, acetone-d6) δ 5.37 (ddd, J = 15.6, 10.1, 5.2 Hz, 1H),5.22 (d, J = 15.7 Hz, 1H), 5.11 (dd, J = 9.4, 5.5 Hz, 1H), 4.14 (dd, J = 12.3, 5.5Hz, 1H), 4.09 (dd, J = 12.3, 5.5 Hz, 1H), 3.57 (t, J = 5.6 Hz, 1H), 2.58 (dd, J=10.4, 3.6 Hz, 1H), 2.50 (dd, J = 12.2, 5.2 Hz, 1H), 2.43 (dd, J = 10.6, 4.2 Hz,1H), 2.19 – 2.10 (m, 3H), 1.93 (dd, J = 13.5, 4.6 Hz, 1H), 1.55 (t, J = 10.6 Hz,1H), 1.33 – 1.27 (m, 1H), 1.27 (s, 3H), 1.12 (s, 3H), 1.07 (s, 3H);

[0064] 13 C NMR (126 MHz, acetone-d6) δ 142.7, 136.3, 127.7, 122.4, 62.2, 61.2, 58.7, 42.5, 39.3, 36.0, 32.8, 28.4, 25.3, 24.7, 16.5.

[0065] The mass spectrometry analysis data are as follows:

[0066] HRMS (ESI / [M + Na] + ); The theoretical calculation data for high-resolution electrospray ionization mass spectrometry is C 15 H 24 NaO2: 259.1669, actual measured value 259.1665 (HRMS (ESI / [M + Na))). + ) calculated forC 15 H 24 NaO2:259.1669, found: 259.1665).

[0067] Step 2: Preparation of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol. The chemical reaction formula for the preparation of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol is as follows:

[0068]

[0069] B1. 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol (100 mg, 0.42 mmol) was placed in a round-bottom flask and dissolved in 10.5 mL of dichloromethane. Then, Sc(OTf)3 (18.5 mg, 0.04 mmol) was added at room temperature. The reaction was monitored by TLC and found to be complete within 5 min. The reaction solution was washed with water, and the aqueous phase was extracted with dichloromethane (10 mL).

[0070] B2. The combined organic phases were dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by silica gel column chromatography (200-300 mesh silica gel, cyclohexane / ethyl acetate = 6:1) to obtain 74 mg of colorless solid, which is 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol, with a yield of 74%.

[0071] The 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol prepared in this example has the following NMR spectral characteristics:

[0072] 1 H NMR (500 MHz, CDCl3) δ 5.24 – 5.10 (m, 3H), 4.51 (d, J = 12.9 Hz, 1H), 3.89 (d, J = 12.9 Hz, 1H), 3.75 – 3.68 (m, 1H), 2.55 (dd, J = 14.3, 10.3 Hz,1H), 2.49 – 2.37 (m,1H), 2.42 (dd, J = 14.4, 3.8 Hz, 1H), 2.23 – 2.12 (m, 2H), 1.87 – 1.76 (m, 1H), 1.76 – 1.62 (m, 2H), 1.27 (s, 3H), 1.11 (s, 3H), 0.90(s, 3H);

[0073] 13 C NMR (126 MHz, CDCl3) δ 142.2, 138.3, 123.6, 123.0, 79.9, 74.5, 67.7, 42.7, 41.2, 38.5, 35.7, 30.6, 30.2, 29.9, 22.3.

[0074] The mass spectrometry analysis data are as follows:

[0075] HRMS (ESI / [M + Na] + The theoretical calculation data for high-resolution electrospray ionization mass spectrometry is C. 15 H 24 NaO2: 259.1669, actual measured value was 259.1673 (HRMS (ESI / [M + Na))). + ) calculated forC 15 H 24 NaO2:259.1669, found:259.1673).

[0076] Example 2

[0077] Aroma rating, longevity test, and base aroma test were performed on 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol prepared in Example 1. The test results are as follows:

[0078] (1) Aroma evaluation: Thirteen perfumers with more than five years of experience made the following evaluation of the aroma of the compound: The 13 perfumers unanimously agreed that in addition to presenting a cool, sweet, and fruity aroma, the compound also has a sweet and mellow agarwood aroma.

[0079] (2) Scent retention test: Prepare a 10% propylene glycol solution by taking 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol. Take a scent test strip, dip it in an appropriate amount of solution, place the test strip on the scent rack, and have 3 perfumers smell it once every 2 hours. When more than 2 perfumers cannot perceive the scent of the scent test strip, record the scent retention time.

[0080] Scent retention tests showed that the cool, honey-sweet fruity aroma of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol had a retention time of 32 hours, while the aroma of agarwood had a retention time of 48 hours.

[0081] (3) Aroma test of the base flavor: The formula of the fruity aroma base is shown in the table below:

[0082]

[0083] Prepare fragrance base A and fragrance base B according to the formula in the table above. The parts of each raw material in the table are by weight. Add 40 parts of the target product of this invention, 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol, to fragrance base B. After evaluating the fragrance base, 9 perfumers with more than 5 years of experience made the following evaluation: The 9 perfumers unanimously agreed that fragrance base B has a more prominent fruity aroma than fragrance base A, a more prominent cool and sweet aroma, and a slightly elegant agarwood aroma. The fragrance base aroma quality is significantly improved.

[0084] 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 compound having a sweet, refreshing aroma, characterized in that: It has the following structural formula: 。 2. A method for preparing a compound with a honey-sweet and refreshing aroma as described in claim 1, characterized in that: Includes the following steps: Step 1: Using caryophyllin oxide as the raw material, 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol was prepared. The structural formula of caryophyllin oxide is shown below: ； The structural formula of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol is shown below: ； Step 2: Using 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodec-4,8-diene-4-methanol obtained in Step 1 as the raw material, and after separation and purification, a compound with a honey-sweet and refreshing aroma is obtained. The compound with a honey-sweet and refreshing aroma is 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadeca-2,7-diene-11-ol.

3. The method for preparing the compound with a sweet and refreshing aroma according to claim 2, characterized in that: In step one, the preparation method of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol includes the following steps: A1. Place caryophyllin oxide in a reaction vessel, add acetone to dissolve it, add some freshly prepared NBS and glacial acetic acid at room temperature, and keep stirring under light-protected conditions. When 60-70% of the caryophyllin oxide has been converted, add some more freshly prepared NBS and glacial acetic acid to make the caryophyllin oxide completely converted. A2. After the reaction is complete, filter the solution with silica gel to remove unreacted NBS and solid succinimide; dry the filtrate with anhydrous sodium sulfate and remove the solvent under reduced pressure to obtain an oily product; dissolve the product in an aqueous acetonitrile solution, add potassium carbonate, and heat to 78-82℃ to react. A3. After the reaction was completed, the system was cooled to room temperature, diluted with water, and extracted with ethyl acetate. The combined organic phases were dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by silica gel column chromatography to obtain a colorless oily liquid, namely 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol.

4. The method for preparing the compound with a sweet and refreshing aroma according to claim 3, characterized in that: In step A1, 4.3-4.7 mmol of caryophyllin oxide is placed in a reaction vessel and dissolved in 28-32 mL of acetone. At room temperature, 8.8-9.2 mmol of freshly prepared NBS and 8.8-9.2 mmol of glacial acetic acid are added, and stirring is maintained under light-protected conditions. After stirring for 3.5-4.5 h, when 60-70% of the caryophyllin oxide has been converted, 8.8-9.2 mmol of freshly prepared NBS and 8.8-9.2 mmol of glacial acetic acid are added again to ensure complete conversion of the raw materials.

5. The method for preparing the compound with a sweet and refreshing aroma according to claim 3, characterized in that: In step A2, the oily product is dissolved in an acetonitrile aqueous solution, wherein the volume ratio of acetonitrile to water in the acetonitrile aqueous solution is 0.9-1.1:0.9-1.1, and 9.5-10.5 mmol of potassium carbonate is added.

6. The method for preparing the compound with a sweet and refreshing aroma according to claim 2, characterized in that: In step two, the preparation method of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetadecan-2,7-dien-11-ol includes the following steps: B1. Place 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol in a reaction vessel and dissolve it in dichloromethane; then add Sc(OTf)3 at room temperature. After the reaction is complete, wash the reaction solution with water, separate the liquid phase, and extract the aqueous phase with dichloromethane. B2. The obtained organic phase was dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by silica gel column chromatography to obtain a colorless solid, which is the preparation of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol.

7. The method for preparing the compound with a sweet and refreshing aroma according to claim 6, characterized in that: In step B1, 0.40-0.44 mmol of 7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodecane-4,8-diene-4-methanol was placed in a reaction vessel and dissolved in 9.5-12 mL of dichloromethane. Then, 0.038-0.042 mmol of Sc(OTf)3 was added at room temperature. The reaction was detected by TLC and found to be completed within 5 min. The reaction solution was washed with water, and the aqueous phase was extracted with dichloromethane after separation.

8. A fruity flavor base, characterized in that: The raw materials include the following parts by weight: 3.5-4.5 parts of ethyl 2-methylbutyrate, 4-6 parts of ethyl propionate, 9-11 parts of isoamyl acetate, 4-6 parts of hexyl acetate, 18-22 parts of geraniol acetate, 3.5-4.5 parts of ethyl acrylate, 13-17 parts of geraniol, 27-33 parts of isoamyl butyrate, 36-44 parts of cyclohexane, 23-27 parts of ethyl hexanoate, 26-30 parts of dafuronone, 7-9 parts of allyl hexanoate, 21-25 parts of phenethyl alcohol, 11-15 parts of white lemon oil, 44-50 parts of linalool, 35-45 parts of 1,5,5-trimethyl-12-oxabicyclo[6.3.2]tetane-2,7-dien-11-ol, and 650-750 parts of propylene glycol.

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