Fresh and sweet bean fragrance compound, preparation method thereof and fresh and sweet bean fragrance base

Abstract

The invention relates to the technical field of flavors and fragrances, in particular to a fresh and sweet bean-flavor compound, a preparation method thereof and a fresh and sweet bean-flavor base, and the fresh and sweet bean-flavor compound has the following structural formula: # imgabs0 #. The prepared fresh and sweet bean flavor compound is 8-ethyl-9, 10-dihydroxy-4, 4, 6a, 11b-tetramethyl-2, 3, 4, 4a, 5, 6, 6a, 11, 11a, 11b-decahydro-1H-benzo [a] fluorene, has wood and light powder fragrance, has a little amber note, is elegant in fragrance and long in fragrance holding time, and has a good application prospect in the field of flavor blending. The preparation method of the fresh and sweet bean flavor compound is convenient to operate and control, high in production efficiency and beneficial to industrial production. According to the prepared fresh and sweet bean fragrance base, the fresh and sweet bean fragrance compound is added, so that the fresh and sweet bean fragrance base has more prominent fresh and sweet bean fragrance and elegant wood powder fragrant and sweet fragrance, and the fragrance quality of the base is remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of flavors and fragrances, and in particular to a sweet bean-scented compound and a preparation method thereof and a sweet bean-scented aroma base. Background Art

[0002] Spices are substances that can be smelled or tasted. With the development of science and technology and the improvement of people's living standards, the flavor and fragrance industry has developed rapidly, with the increasing variety of natural and synthetic flavors and the improvement of perfume making skills. Different consumers have different needs and preferences for different flavors. At this stage, flavors and fragrances with sweet bean and powdery aromas are loved by people because of their unique aromas and are widely used. They can be used as fixatives, coordinators and flavoring agents. However, under the current conditions, there are few types of compounds with sweet bean and powdery aromas that are suitable for use as flavors and fragrances, and the fragrance is relatively single. Therefore, it is of great significance to develop new compounds with sweet bean fragrances, elegant and unique aromas, increase the variety of flavors and fragrances, and promote the development of the flavor and fragrance industry to meet market demand. Summary of the invention

[0003] In order to overcome the shortcomings and deficiencies in the prior art, the object of the present invention is to provide a sweet bean-scented compound, which has a woody, light pink aroma and a little amber fragrance. The fragrance is elegant and lasts for a long time, and has good application prospects in the field of perfumery.

[0004] Another object of the present invention is to provide a method for preparing a sweet bean-scented compound. The method is easy to operate and control, has high production efficiency, and is conducive to industrial production. The prepared compound has a woody, light powdery aroma and a slight amber scent.

[0005] Another object of the present invention is to provide a sweet bean fragrance base, which has a more prominent sweet bean aroma and a slightly elegant wood powder sweet aroma by adding sweet bean fragrance compounds, and the aroma quality of the fragrance base is significantly improved.

[0006] The object of the present invention is achieved by the following technical solution: A sweet bean-scented compound having the following structural formula: .

[0007] The sweet bean-scented compound can be named: 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0008] The sweet bean-scented compound of the invention has woody and light powdery aromas and a little amber fragrance, and has important uses in the field of daily chemical perfumery.

[0009] Another object of the present invention is achieved by the following technical solution: a method for preparing a sweet bean-flavored compound, comprising the following steps: Step 1: Preparation of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol; Its structural formula is shown below:

[0010] Step 2: Prepare 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, the structural formula of which is shown below:

[0011] Step 3: reacting the 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in step 2 with dichloromethane and boron tribromide, and obtaining the sweet bean-scented compound according to claim 1 after separation and purification, wherein the sweet bean-scented compound is 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0012] Furthermore, in the step 1, the preparation method of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol comprises the following steps: A1. Pd2(dba)3, sodium tert-butyl alcohol, Ruphos, a borate compound and an iodobenzene compound are placed in a reaction container in sequence, and the reaction system is protected by argon; tert-butyl alcohol and water are then added to the reaction system in sequence; the reaction system is heated and stirred for reaction; the structural formula of the borate compound is shown below: ; The structural formula of iodobenzene compound is shown below: ; A2. After the reaction is completed, the reaction system is diluted with ethyl acetate, and washed with water and a saturated sodium chloride solution in sequence; the organic phase is dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol.

[0013] Furthermore, in the step A1, 30.004-0.006 mmol of catalyst Pd2(dba), 0.9-1.1 mmol of sodium tert-butyl alcohol, 0.009-0.011 mmol of Ruphos, 0.28-0.32 mmol of borate compound and 0.24-0.26 mmol of iodobenzene compound are placed in a reaction vessel in sequence, and the reaction system is protected by argon; then 0.9-1.1 mL of tert-butyl alcohol and 0.08-0.12 mL of water are added to the reaction system in sequence; the reaction system is heated to 95-100° C. and stirred for 17-19 hours.

[0014] Furthermore, in step A2, after the reaction is completed, the reaction system is diluted with 4-6 mL of ethyl acetate, and washed with 4-6 mL of water and 4-6 mL of saturated sodium chloride solution in sequence; the organic phase is dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol.

[0015] Furthermore, in the step 2, the method for preparing 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene comprises the following steps: B1. Dissolve the 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol prepared in step 1 in anhydrous dichloromethane, cool to -1~1°C and add the dichloromethane solution of SnCl4; continue the reaction for 50-70 minutes after the addition, dilute the system with dichloromethane and pour the reaction system into ice water, separate the liquids and extract the aqueous phase with dichloromethane; B2. The combined organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0016] Furthermore, in the step B1, 0.18-0.22 mmol of (4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol is dissolved in 5-7 mL of anhydrous dichloromethane, cooled to 0°C, and then a dichloromethane solution of SnCl4 is slowly added, wherein the concentration of SnCl4 in the dichloromethane solution is 0.9-1.1 mol / L, and the amount added is 0.9-1.0 mmol.

[0017] Furthermore, in step 3, the preparation method of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene comprises the following steps: C1. Dissolve the 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in step 2 in anhydrous dichloromethane, then add a dichloromethane solution of boron tribromide at room temperature, and keep stirring until all the 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene disappears as detected by TLC, quench the reaction with a saturated sodium bicarbonate solution, and extract the separated organic phase with dichloromethane; C2. The obtained organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0018] Furthermore, in the step C1, 0.23-0.25 mmol of 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene is dissolved in 4-6 mL of anhydrous dichloromethane, and then a dichloromethane solution of boron tribromide is added at room temperature, and stirring is maintained until all the raw materials disappear, and the reaction is quenched with 9-11 mL of a saturated sodium bicarbonate solution.

[0019] Another object of the present invention is achieved by the following technical scheme: a sweet bean fragrance base, comprising the following raw materials in parts by weight: 8-12 parts of ethyl maltol, 4-6 parts of ethyl acetate, 28-32 parts of isoamyl acetate, 4-6 parts of hexyl acetate, 1.5-2.5 parts of geranyl acetate, 3-5 parts of ethyl acrylate, 16-20 parts of ethyl butyrate, 3-5 parts of isoamyl acetate, 90-110 parts of γ-caprolactone, 23-27 parts of ethyl caproate, 70-90 parts of methyl hexanoate, 7-9 parts of allyl hexanoate, 21-25 parts of ethyl heptanoate, 2.5-3.5 parts of 3-cyclohexyl propyl acrylate, 6-8 parts of allyl phenoxyacetate, 45-55 parts of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, and 620-700 parts of propylene glycol.

[0020] The beneficial effects of the present invention are as follows: the sweet bean-scented compound prepared by the present invention is 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, which has a woody, light powdery aroma, and a little amber fragrance, and has an elegant fragrance and a long lasting fragrance, and has a good application prospect in the field of perfumery. The preparation method of the sweet bean-scented compound is convenient to operate and control, has high production efficiency, and is conducive to industrial production.

[0021] The sweet bean fragrance base prepared by the invention has a more prominent sweet bean aroma by adding a sweet bean fragrance compound, and has an elegant sweet wood powder fragrance, and the aroma quality of the fragrance base is significantly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the hydrogen spectrum of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in Example 1.

[0023] Figure 2 This is the carbon spectrum of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in Example 1.

[0024] Figure 3 This is the gas chromatogram of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in Example 1. DETAILED DESCRIPTION

[0025] In order to facilitate the understanding of those skilled in the art, the following embodiments and attached Figure 1 The present invention is further described, and the contents mentioned in the implementation modes are not intended to limit the present invention.

[0026] In an embodiment of the present invention, a sweet bean-scented compound has the following structural formula: .

[0027] The sweet bean-scented compound can be named: 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0028] In some embodiments of the present invention, a method for preparing a sweet bean-flavored compound comprises the following steps: Step 1: Preparation of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol; Its structural formula is shown below:

[0029] Step 2: Prepare 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, the structural formula of which is shown below:

[0030] Step 3: reacting the 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in step 2 with dichloromethane and boron tribromide, and obtaining the sweet bean-scented compound according to claim 1 after separation and purification, wherein the sweet bean-scented compound is 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0031] In some embodiments of the present invention, in step 1, the preparation method of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol comprises the following steps: A1. Pd2(dba)3, sodium tert-butyl alcohol, ligand Ruphos, borate compound and iodobenzene compound are placed in a reaction container in sequence, and the reaction system is protected by argon; then tert-butyl alcohol and water are added to the reaction system in sequence; the reaction system is heated and stirred for reaction; the structural formula of the borate compound is shown as follows: ; The structural formula of iodobenzene compound is shown below: ; A2. After the reaction is completed, the reaction system is diluted with ethyl acetate, and washed with water and a saturated sodium chloride solution in sequence; the organic phase is dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol.

[0032] Furthermore, in the step A1, 30.004-0.006 mmol of catalyst Pd2(dba), 0.9-1.1 mmol of sodium tert-butyl alcohol, 0.009-0.011 mmol of Ruphos, 0.28-0.32 mmol of borate compound and 0.24-0.26 mmol of iodobenzene compound are placed in a reaction vessel in sequence, and the reaction system is protected by argon; then 0.9-1.1 mL of tert-butyl alcohol and 0.08-0.12 mL of water are added to the reaction system in sequence; the reaction system is heated to 95-100° C. and stirred for 17-19 hours.

[0033] In some embodiments of the present invention, in step A2, after the reaction is completed, the reaction system is diluted with 4-6 mL of ethyl acetate, and washed with 4-6 mL of water and 4-6 mL of saturated sodium chloride solution in sequence; the organic phase is dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol.

[0034] In some embodiments of the present invention, in step 2, the method for preparing 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene comprises the following steps: B1. Dissolve the 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol prepared in step 1 in anhydrous dichloromethane, cool to -1~1°C and add the dichloromethane solution of SnCl4; continue the reaction for 50-70 minutes after the addition, dilute the system with dichloromethane and pour the reaction system into ice water, separate the liquids and extract the aqueous phase with dichloromethane; B2. The combined organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0035] In some embodiments of the present invention, in step B1, 0.18-0.22 mmol of (4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol is dissolved in 5-7 mL of anhydrous dichloromethane, cooled to 0°C, and then a dichloromethane solution of SnCl4 is slowly added, the concentration of SnCl4 is 1 mol / L, and the amount added is 0.9-1.0 mmol.

[0036] In some embodiments of the present invention, in step 3, the method for preparing 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene comprises the following steps: C1, dissolving the 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in step 2 in anhydrous dichloromethane, then adding a dichloromethane solution of boron tribromide at room temperature, maintaining stirring until all the raw materials disappear as detected by TLC, quenching the reaction with a saturated sodium bicarbonate solution, and extracting the separated organic phase with dichloromethane; C2. The obtained organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0037] In some embodiments of the present invention, in step C1, 0.23-0.25 mmol of 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene is dissolved in 4-6 mL of anhydrous dichloromethane, and then a dichloromethane solution of boron tribromide is added at room temperature. The stirring is maintained until all the raw materials disappear according to TLC detection, and the reaction is quenched with 9-11 mL of saturated sodium bicarbonate solution.

[0038] In some embodiments of the present invention, a sweet bean fragrance base comprises the following raw materials in parts by weight: 8-12 parts of ethyl maltol, 4-6 parts of ethyl acetate, 28-32 parts of isoamyl acetate, 4-6 parts of hexyl acetate, 1.5-2.5 parts of geranyl acetate, 3-5 parts of ethyl acrylate, 16-20 parts of ethyl butyrate, 3-5 parts of isoamyl acetate, 90-110 parts of γ-caprolactone, 23-27 parts of ethyl caproate, methyl caproate 70-90 parts, allyl hexanoate 7-9 parts, ethyl heptanoate 21-25 parts, 3-cyclohexyl propyl acrylate 2.5-3.5 parts, allyl phenoxyacetate 6-8 parts, 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene 45-55 parts, propylene glycol 620-700 parts.

[0039] In a typical embodiment of the present invention, a sweet bean fragrance base comprises the following raw materials in parts by weight: 10 parts of ethyl maltol, 5 parts of ethyl acetate, 30 parts of isoamyl acetate, 5 parts of hexyl acetate, 2 parts of geranyl acetate, 4 parts of ethyl acrylate, 18 parts of ethyl butyrate, 4 parts of isoamyl acetate, 100 parts of γ-caprolactone, 25 parts of ethyl caproate, 80 parts of methyl caproate, 8 parts of allyl caproate, 23 parts of ethyl heptanoate, 3 parts of 3-cyclohexylpropyl acrylate, 7 parts of allyl phenoxyacetate, 50 parts of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, and 626 parts of propylene glycol.

[0040] Example 1 This embodiment provides a sweet bean-scented compound having the following structural formula: .

[0041] The chemical name of the sweet bean-scented compound is: 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

[0042] The preparation method of the sweet bean-scented compound comprises the following steps: Step 1: Preparation of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol. The chemical reaction formula for the preparation of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol is as follows:

[0043] A1. Catalyst Pd2(dba)3 (4.6 mmol, 0.005 mmol, 2 mol%), sodium tert-butyl alcohol (96 mg, 1 mmol, 4 equiv), Ruphos (4.7 mg, 0.01 mmol, 4 mol%), borate compound (117.6 mg, 0.3 mmol, 1.2 equiv) and iodobenzene compound (69 mg, 0.25 mmol, 1.0 equiv) were placed in a 10 mL Schlenk reaction tube, and the reaction system was protected by argon; tert-butyl alcohol (1.0 mL) and water (0.1 mL) were then added to the reaction system; the reaction system was heated to 100°C and stirred vigorously for 18 h; the structural formula of the borate compound is shown in Formula 1; the structural formula of the iodobenzene compound is shown in the following formula: ; A2. After the reaction is completed, the reaction system is diluted with 5 mL of ethyl acetate, and washed with 5 mL of water and 5 mL of saturated sodium chloride solution in sequence; the organic phase is dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography (200-300 mesh silica gel, n-hexane / ethyl acetate = 5:1) to obtain 98 mg of a white solid, namely 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol, with a yield of 95%; the structural formula of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol is shown in Formula 2, and it has the following NMR spectrum characteristics: 1 H NMR (400 MHz, CDCl3) δ 6.65 (d, J = 2.0 Hz, 1H), 6.56 (d, J = 2.0 Hz,1H), 3.83 (s, 6H), 2.82 (dd, J= 14.4, 5.4 Hz, 1H), 2.62 - 2.51 (m, 3H), 1.87 -1.75 (m, 2H), 1.66 - 1.52 (m, 3H), 1.47 - 1.30 (m, 4H), 1.28 (s, 3H), 1.26 -1.23 (m, 1H), 1.22 (t, J = 7.6 Hz, 3H), 1.14 - 1.05 (m, 2H), 0.96 - 0.91 (m,1H), 0.90 (s, 3H), 0.85 (s, 3H), 0.80 (s, 3H); 13 C NMR (101 MHz, CDCl3) δ 152.30, 144.20, 140.07, 137.68, 121.98,109.50, 73.70, 62.89, 60.63, 56.07, 55.63, 43.67, 41.78, 40.31, 39.42, 33.50,33.34, 28.83, 25.29, 24.28, 21.59, 20.29, 18.63, 15.82, 15.46.

[0044] The mass spectrometry data are as follows: HRMS (ESI / [M + Na] + ): High-resolution mass spectrometry theoretical calculation data is C 25 H 40 NaO3: 411.2870, actual measured value 411.2867 (HRMS (ESI / [M + Na] + ) calculated for C 25 H 40 NaO3: 411.2870, found 411.2867).

[0045] Step 2: Prepare 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene. The chemical reaction formula for its preparation is as follows:

[0046] B1. Dissolve 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol (84 mg, 0.2 mmol, 1.0 equiv) prepared in step 1 in anhydrous dichloromethane (6 mL). After cooling to 0°C, slowly add a dichloromethane solution of SnCl4 (1.0 mmol, 1M, 5 equiv). After the addition, continue the reaction for 1 h. After the reaction is completed, dilute the system with 20 mL of dichloromethane and pour the reaction system into ice water. After separation, extract the aqueous phase with dichloromethane (3×10 mL). B2, the organic phase merged was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated by spin drying. By silica gel column chromatography (200-300 mesh, n-hexane / ethyl acetate = 5: 1), 61 mg of white solid was obtained, which was 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11, 11a,11b-decahydro-1H-benzo [a] fluorene, and the yield was 76%; the structural formula of 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11, 11a,11b-decahydro-1H-benzo [a] fluorene was as shown in Formula 3, and it had the following NMR spectrum characteristics: 1 H NMR (400 MHz, CDCl3) δ 6.50 (s, 1H), 3.83 (s, 3H), 3.80 (s, 3H), 2.76 - 2.65 (m, 2H), 2.63 - 2.46 (m, 2H), 2.42 - 2.34 (m, 1H), 1.82 - 1.61 (m,4H), 1.59 - 1.52 (m, 2H), 1.47 - 1.37 (m, 2H), 1.23 (t, J = 7.6 Hz, 3H), 1.15(dd, J = 13.3, 4.2 Hz, 1H), 1.10 (s, 3H), 1.03 (s, 3H), 1.02 - 0.94 (m, 2H), 0.88 (s, 6H).

[0047] 13C NMR (101 MHz, CDCl3) δ 150.34, 144.79, 143.45, 135.89, 133.82,110.90, 64.31, 60.44, 57.09, 55.92, 47.87, 42.53, 40.16, 39.27, 37.09, 33.43,33.10, 25.28, 24.74, 21.37, 21.16, 19.70, 18.35, 16.17, 16.12.

[0048] The mass spectrometry data are as follows: HRMS (ESI / [M + H] + ): High-resolution mass spectrometry theoretical calculation data is C 25 H 39 O2: 371.2945, actual measured value 371.2944 (HRMS (ESI / [M + H] + ) calculated for C 25 H 39 O2: 371.2945, found371.2944).

[0049] Step 3: Preparation of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a, 11b-decahydro-1H-benzo[a]fluorene, the chemical reaction formula for its preparation is as follows:

[0050] C1. Dissolve 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene (88 mg, 0.237 mmol, 1.0 equiv) prepared in step 2 in anhydrous dichloromethane (5 mL), and then slowly add a dichloromethane solution of boron tribromide (0.36 mL, 2.0 M in CH2Cl2, 0.72 mmol) at room temperature, i.e., the concentration of boron tribromide is 2.0 mol / L and the amount added is 0.72 equiv. mmol; Stirring was maintained until 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene disappeared completely by TLC. The reaction was quenched with saturated sodium bicarbonate solution (10 mL), and the separated organic phase was extracted with dichloromethane (3×10 mL); C2. The combined organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography (200-300 mesh, n-hexane / ethyl acetate = 3: 1) to obtain 70 mg of a white solid, namely 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, with a reaction yield of 86%.

[0051] The 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11, 11a,11b-decahydro-1H-benzo[a]fluorene prepared in this example has the following NMR spectrum characteristics: 1 H NMR (500 MHz, CDCl3) δ 6.48 (s, 1H), 4.98 (d, J = 12.7 Hz, 2H), 2.67- 2.54(m, 2H), 2.52 - 2.38 (m, 2H), 2.38 - 2.33 (m, 1H), 1.80 - 1.63 (m, 5H),1.62 - 1.50 (m, 2H), 1.44 - 1.37 (m, 2H), 1.16 (t, J = 7.5 Hz, 3H), 1.08 (s, 3H), 1.02 (s, 3H), 0.99 - 0.93 (m, 2H), 0.86 (s, 3H), 0.85 (s, 3H); 13 C NMR (126 MHz, CDCl3) δ 144.92, 141.45, 137.96, 131.00, 128.69,113.71, 64.65, 57.14, 48.16, 42.58, 40.18, 39.31, 37.13, 33.48, 33.16, 24.57,24.27, 21.44, 21.21, 19.76, 18.44, 16.26, 16.07.

[0052] The mass spectrometry data are as follows: HRMS (ESI / [M - H] - ): The theoretical calculation data of high-resolution mass spectrometry in negative ion mode is calculated for C 23 H 33O2: 341.2486, actual measured value is 341.2483 (HRMS (ESI / [M - H] - ) calculated for C 23 H 33 O2: 341.2486, found 341.2483).

[0053] Example 2 The 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a, 5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene prepared in Example 1 was subjected to aroma rating, aroma retention test and aroma base aroma test. The test results are as follows: (1) Aroma evaluation: Twelve perfumers with more than five years of experience gave the following evaluation of the aroma of the compound: All twelve perfumers agreed that in addition to the characteristic sweet bean aroma, the compound also has a sweet woody powder aroma and an amber scent.

[0054] (2) Fragrance test: Use diethyl phthalate (DEP) as solvent to prepare a 10% mass fraction of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene solution. Use a scent strip to dip a small amount of the solution and place the test paper on a scent rack. Three perfumers will smell it every 2 hours. When more than two perfumers cannot perceive the fragrance of the scent test paper, the fragrance retention time will be recorded.

[0055] The fragrance retention test shows that the sweet bean aroma of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene has a lasting time of 14 hours, and the powdery amber aroma has a lasting time of 20 hours.

[0056] (3) Fragrance base aroma test: The fragrance base formula is shown in the following table:

[0057] According to the formula in the above table, fragrance base A and fragrance base B are prepared, and 50 parts of the target product of the present invention, 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, are added to fragrance base B. Eight perfumers with more than 5 years of working experience evaluate the fragrance base and make the following comments: The eight perfumers unanimously agree that fragrance base B has a more prominent sweet bean aroma than fragrance base A, with a slightly elegant sweet woody powder aroma, and the aroma quality of the fragrance base is significantly improved.

[0058] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention may also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the protection scope of the present invention.

Claims

1. A sweet bean-scented compound, characterized in that: It has the following structural formula: 。 2. A method for preparing the sweet bean-scented compound according to claim 1, characterized in that: The steps include: Step 1: Preparation of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol; Its structural formula is shown below: ； Step 2: Prepare 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, the structural formula of which is shown below: ； Step 3: reacting the 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in step 2 with dichloromethane and boron tribromide to obtain the sweet bean-scented compound after separation and purification. The sweet bean-scented compound is 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

3. The method for preparing the sweet bean-scented compound according to claim 2, characterized in that: In the step 1, the preparation method of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol comprises the following steps: A1. Pd2(dba)3, sodium tert-butyl alcohol, ligand Ruphos, borate compound and iodobenzene compound are placed in a reaction container in sequence, and the reaction system is protected by argon; then tert-butyl alcohol and water are added to the reaction system in sequence; the reaction system is heated and stirred for reaction; the structural formula of the borate compound is shown as follows: ； The structural formula of iodobenzene compound is shown below: ； A2. After the reaction is completed, the reaction system is diluted with ethyl acetate, and washed with water and a saturated sodium chloride solution in sequence; the organic phase is dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol.

4. The method for preparing the sweet bean-scented compound according to claim 3, characterized in that: In the step A1, 0.004-0.006 mmol of catalyst Pd2(dba)3, 0.9-1.1 mmol of sodium tert-butyl alcohol, 0.009-0.011 mmol of Ruphos, 0.28-0.32 mmol of borate compound and 0.24-0.26 mmol of iodobenzene compound are placed in a reaction container in sequence, and the reaction system is protected by argon; then 0.9-1.1 mL of tert-butyl alcohol and 0.08-0.12 mL of water are added to the reaction system in sequence; the reaction system is heated to 95-100° C. and stirred for reaction for 17-19 hours.

5. The method for preparing the sweet bean-scented compound according to claim 3, characterized in that: In the step A2, after the reaction is completed, the reaction system is diluted with 4-6 mL of ethyl acetate, and washed with 4-6 mL of water and 4-6 mL of saturated sodium chloride solution in sequence; the organic phase is dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol.

6. The method for preparing the sweet bean-scented compound according to claim 2, characterized in that: In the step 2, the method for preparing 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene comprises the following steps: B1. Dissolve the 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol prepared in step 1 in anhydrous dichloromethane, cool to -1~1°C and add the dichloromethane solution of SnCl4; continue the reaction for 50-70 minutes after the addition, dilute the system with dichloromethane and pour the reaction system into ice water, separate the liquids and extract the aqueous phase with dichloromethane; B2. The combined organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

7. The method for preparing the sweet bean-scented compound according to claim 6, characterized in that: In the step B1, 0.18-0.22 mmol of (4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalene-2-ol is dissolved in 5-7 mL of anhydrous dichloromethane, cooled to 0° C., and then a dichloromethane solution of SnCl4 is slowly added, wherein the amount of SnCl4 added is 0.9-1.0 mmol.

8. The method for preparing the sweet bean-scented compound according to claim 2, characterized in that: In the step 3, the preparation method of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene comprises the following steps: C1. Dissolve the 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene obtained in step 2 in anhydrous dichloromethane, then add a dichloromethane solution of boron tribromide at room temperature, and stir until the reaction of 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene is complete as detected by TLC, and quench the reaction with a saturated sodium bicarbonate solution. The separated organic phase is extracted with dichloromethane; C2. The obtained organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated by spin drying, and separated by silica gel column chromatography to obtain 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene.

9. The method for preparing the sweet bean-scented compound according to claim 8, characterized in that: In the step C1, 0.23-0.25 mmol of 8-ethyl-9,10-dimethoxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene is dissolved in 4-6 mL of anhydrous dichloromethane, and then a dichloromethane solution of boron tribromide is added at room temperature. The stirring is maintained until all the raw materials disappear according to TLC detection, and the reaction is quenched with 9-11 mL of a saturated sodium bicarbonate solution.

10. A sweet bean fragrance base, characterized in that: The raw materials include the following parts by weight: 8-12 parts of ethyl maltol, 4-6 parts of ethyl acetate, 28-32 parts of isoamyl acetate, 4-6 parts of hexyl acetate, 1.5-2.5 parts of geranyl acetate, 3-5 parts of ethyl acrylate, 16-20 parts of ethyl butyrate, 3-5 parts of isoamyl acetate, 90-110 parts of γ-caprolactone, 23-27 parts of ethyl caproate, 70-90 parts of methyl caproate, 10-20 parts of ethyl hexanoate, 15-20 parts of ethyl hexano ... 7-9 parts of propyl ester, 21-25 parts of ethyl heptanoate, 2.5-3.5 parts of 3-cyclohexyl propyl acrylate, 6-8 parts of allyl phenoxyacetate, 45-55 parts of 8-ethyl-9,10-dihydroxy-4,4,6a,11b-tetramethyl-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-1H-benzo[a]fluorene, and 620-700 parts of propylene glycol.

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