A clean and sweet bean-flavored compound, a preparation method thereof and a clean and sweet bean-flavored flavoring base

Abstract

The present application relates to the field of essence and flavor technology, and particularly relates to a clear and sweet bean fragrance compound, a preparation method thereof and a clear and sweet bean fragrance base, the clear and sweet bean fragrance compound has the following structural formula: The clear and sweet bean fragrance compound prepared by the present application 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 woody, light powder fragrance and a little amber fragrance, the fragrance is elegant, the fragrance retention time is long, and the clear and sweet bean fragrance compound has a good application prospect in the field of flavor modulation. The preparation method of the clear and sweet bean fragrance compound is convenient to operate and control, high in production efficiency and beneficial to industrial production. The clear and sweet bean fragrance base prepared by the present application has more outstanding clear and sweet bean fragrance by adding the clear and sweet bean fragrance compound, has elegant woody, powder and sweet fragrance, and the fragrance quality of the base is significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of essence and flavor technology, and particularly relates to a sweet and clean bean fragrance compound, a preparation method thereof and a sweet and clean bean fragrance base. BACKGROUND

[0002] Flavor is a kind of substance that can be smelled by olfactory or tasted by taste. With the development of science and technology and the improvement of people's living standards, the flavor and essence industry has developed rapidly, and the variety of natural flavor and synthetic flavor has increased day by day, and the flavor blending technology has been improved. Different consumers have different needs and preferences for different flavor smells. At present, essence and flavor with sweet and clean bean fragrance and powdery fragrance are favored by people because of their unique fragrance and are widely used as fixatives, harmonizers and flavoring agents. However, under the existing conditions, there are few compounds with sweet and clean bean fragrance and powdery fragrance suitable for being used as essence and flavor, and the fragrance is relatively single. Therefore, it is of great significance to develop new compounds with sweet and clean bean fragrance and elegant and unique fragrance, increase the variety of essence and flavor, and promote the development of the flavor and essence industry to meet the market demand. SUMMARY

[0003] In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present application is to provide a sweet and clean bean fragrance compound, which has woody, light powdery fragrance and a little amber fragrance, has elegant fragrance and long-lasting fragrance, and has good application prospect in the field of flavor blending.

[0004] Another purpose of the present application is to provide a preparation method of the sweet and clean bean fragrance compound, which is convenient to operate and control, has high production efficiency, is beneficial to industrial production, and the prepared compound has woody, light powdery fragrance and a little amber fragrance.

[0005] Still another purpose of the present application is to provide a sweet and clean bean fragrance base, which has more prominent sweet and clean bean fragrance and slightly elegant woody, powdery and sweet fragrance by adding the sweet and clean bean fragrance compound, and the quality of the fragrance base is significantly improved.

[0006] The purpose of the present application is achieved by the following technical scheme: a sweet and clean bean fragrance compound has the following structural formula:

[0007]

[0008] The sweet and clean bean fragrance compound can be named as 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.

[0009] The sweet bean fragrance compound provided by the application has woody, light powder fragrance and a little amber fragrance, and has important use in the field of daily chemical fragrance.

[0010] Another object of the application is achieved by a preparation method of the sweet bean fragrance compound, comprising the following steps.

[0011] Step one: preparing 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol; the structural formula is shown in the following formula:

[0012]

[0013] Step two: 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; the structural formula is shown in the following formula:

[0014]

[0015] Step three: reacting 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 prepared in step two under the action of dichloromethane and boron tribromide, and obtaining the sweet bean fragrance compound after separation and purification; the sweet bean fragrance 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.

[0016] Further, in step one, the preparation method of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol comprises the following steps:

[0017] A1, Pd2(dba)3, sodium t-butoxide, Ruphos, borate compound and iodobenzene compound are sequentially placed in a reaction container, and the reaction system is protected by using argon; then t-butyl alcohol and water are sequentially added into the reaction system; the reaction system is heated and stirred; the structural formula of the borate compound is shown in the following formula:

[0018]

[0019] The structural formula of the iodobenzene compound is shown in the following formula:

[0020]

[0021] A2, after the reaction, the reaction system is diluted with ethyl acetate, and is sequentially washed with water and saturated sodium chloride solution; the organic phase is dried over anhydrous sodium sulfate, and is concentrated by rotary evaporation; 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol is obtained by silica gel column chromatography.

[0022] Further, in the step A1, the catalyst Pd2(dba)30.004-0.006 mmol, sodium tert-butoxide 0.9-1.1 mmol, Ruphos 0.009-0.011 mmol, borate compound 0.28-0.32 mmol and iodobenzene compound 0.24-0.26 mmol are sequentially placed in the reaction container, 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 sequentially added to the reaction system; the reaction system is heated to 95-100°C, and stirred for 17-19 h.

[0023] Further, in the step A2, after the reaction, the reaction system is diluted with 4-6 mL of ethyl acetate, and is sequentially washed with 4-6 mL of water and 4-6 mL of saturated sodium chloride solution; the organic phase is dried over anhydrous sodium sulfate, and is concentrated by rotary evaporation; 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol is obtained by silica gel column chromatography.

[0024] Further, in the step two, the preparation method 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 comprises the following steps:

[0025] B1, 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol prepared in step one is dissolved in anhydrous dichloromethane, cooled to -1-1°C, and then SnCl4 dichloromethane solution is added; after adding, continue to react for 50-70 min, and after the end, dilute the system with dichloromethane and pour the reaction system into ice water, separate the liquid, and extract the aqueous phase with dichloromethane;

[0026] B2, the combined organic phase is washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and 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 obtained by silica gel column chromatography.

[0027] Further, in step B1, (4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol 0.18-0.22 mmol is dissolved in anhydrous dichloromethane 5-7 mL, cooled to 0°C, and then slowly added with SnCl4 in dichloromethane solution, the concentration of SnCl4 in dichloromethane solution is 0.9-1.1 mol / L, and the amount of SnCl4 added is 0.9-1.0 mmol.

[0028] Further, in step three, 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:

[0029] C1, 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 prepared in step two is dissolved in anhydrous dichloromethane, then a solution of boron tribromide in dichloromethane is added at room temperature, stirring is 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 disappears completely, saturated sodium bicarbonate solution is used to quench the reaction, and the separated organic phase is extracted with dichloromethane;

[0030] C2, the obtained organic phase is washed with saturated sodium chloride and dried with anhydrous sodium sulfate, then rotary evaporation is performed for concentration, and 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 is obtained by silica gel column chromatography.

[0031] Further, in step C1, 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 0.23-0.25 mmol is dissolved in anhydrous dichloromethane 4-6 mL, then a solution of boron tribromide in dichloromethane is added at room temperature, stirring is maintained until the raw material disappears completely, and saturated sodium bicarbonate solution 9-11 mL is used to quench the reaction.

[0032] A further object of the present application is achieved by the following technical solution: a clean and sweet bean fragrance base, comprising the following raw materials in parts by weight: ethyl maltol 8-12 parts, ethyl acetate 4-6 parts, isoamyl acetate 28-32 parts, hexyl acetate 4-6 parts, geranyl acetate 1.5-2.5 parts, ethyl acrylate 3-5 parts, ethyl butyrate 16-20 parts, isoamyl acetate 3-5 parts, gamma-hexalactone 90-110 parts, ethyl hexanoate 23-27 parts, methyl hexanoate 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, and propylene glycol 620-700 parts.

[0033] The present application has the following beneficial effects: the clean and sweet bean fragrance compound prepared by the present application 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 fragrance with a little amber fragrance, elegant fragrance, and long-lasting fragrance, and has a good application prospect in the field of fragrance modulation. The preparation method of the clean and sweet bean fragrance compound is easy to operate and control, has high production efficiency, and is beneficial to industrial production.

[0034] The clean and sweet bean fragrance base prepared by the present application has more outstanding clean and sweet bean fragrance, elegant woody, powdery and sweet fragrance, and the fragrance quality of the base is significantly improved. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 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 prepared in Example 1.

[0036] Figure 2 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 prepared in Example 1.

[0037] Figure 3 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 prepared in Example 1. DETAILED DESCRIPTION

[0038] For the convenience of those skilled in the art, the following embodiments and the accompanying drawings are combined to further illustrate the present application. Figure 1 The present application is further illustrated by the following embodiments, which are not intended to limit the present application.

[0039] In some embodiments of the present application, a sweet and clean bean flavor compound has the following structural formula:

[0040]

[0041] The sweet and clean bean flavor compound can be named as 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] In some embodiments of the present application, a method for preparing a sweet and clean bean flavor compound comprises the following steps:

[0043] Step one: preparing 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol, which has the following structural formula:

[0044]

[0045] Step two: 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, which has the following structural formula:

[0046]

[0047] Step three: reacting 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 prepared in step two under the action of dichloromethane and boron tribromide, and then separating and purifying to obtain the sweet and clean bean flavor compound, which 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.

[0048] In some embodiments of the present application, the method for preparing 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol in step one comprises the following steps:

[0049] A1, Pd2(dba)3, sodium tert-butyl alcohol, ligand Ruphos, borate compound and iodobenzene compound are sequentially placed in a reaction container, and the reaction system is protected with argon; then sodium tert-butyl alcohol and water are sequentially added to the reaction system; the reaction system is heated and stirred; the structure of the borate compound is as follows:

[0050]

[0051] The structure of the iodobenzene compound is as follows:

[0052]

[0053] A2, after the reaction is completed, the reaction system is diluted with ethyl acetate, and then washed with water and saturated sodium chloride solution; the organic phase is dried over anhydrous sodium sulfate, and then concentrated by rotary evaporation; 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol is obtained by silica gel column chromatography.

[0054] Further, in step A1, the catalyst Pd2(dba)3 0.004-0.006mmol, sodium tert-butyl alcohol 0.9-1.1mmol, Ruphos 0.009-0.011mmol, borate compound 0.28-0.32mmol and iodobenzene compound 0.24-0.26mmol are sequentially placed in a reaction container, and the reaction system is protected with argon; then sodium tert-butyl alcohol 0.9-1.1mL and water 0.08-0.12mL are sequentially added to the reaction system; the reaction system is heated to 95-100℃, and stirred for 17-19h.

[0055] In some embodiments of the present application, in step A2, after the reaction is completed, the reaction system is diluted with 4-6mL of ethyl acetate, and then washed with 4-6mL of water and 4-6mL of saturated sodium chloride solution; the organic phase is dried over anhydrous sodium sulfate, and then concentrated by rotary evaporation; 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol is obtained by silica gel column chromatography.

[0056] In some embodiments of the present application, in step two, 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:

[0057] B1, dissolve 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol prepared in step one in anhydrous dichloromethane, cool to -1-1℃, then add SnCl4 solution in dichloromethane; after adding, continue to react for 50-70 min, after the end, dilute the system with dichloromethane and pour the reaction system into ice water, after separation, extract the aqueous phase with dichloromethane;

[0058] B2, wash the combined organic phase with saturated sodium chloride, dry with anhydrous sodium sulfate, then rotary evaporate and concentrate, separate 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.

[0059] In some embodiments of the present application, in step B1, 0.18-0.22 mmol of (4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol is dissolved in 5-7 mL of anhydrous dichloromethane, then SnCl4 solution in dichloromethane is slowly added after cooling to 0℃, the concentration of SnCl4 is 1 mol / L, and the amount of SnCl4 added is 0.9-1.0 mmol.

[0060] In some embodiments of the present application, in step three, 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 includes the following steps:

[0061] 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 prepared in step two in anhydrous dichloromethane, then add boron tribromide solution in dichloromethane at room temperature, maintain stirring until the original material disappears according to TLC detection, quench the reaction with saturated sodium bicarbonate solution, and extract the separated organic phase with dichloromethane;

[0062] C2, wash the obtained organic phase with saturated sodium chloride, dry with anhydrous sodium sulfate, then rotary evaporate and concentrate, separate 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.

[0063] In some embodiments of the present application, in step C1, 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 0.23-0.25 mmol is dissolved in anhydrous dichloromethane 4-6 mL, then a solution of boron tribromide in dichloromethane is added at room temperature, maintaining stirring until the disappearance of the starting material is detected by TLC, and the reaction is quenched with saturated sodium bicarbonate solution 9-11 mL.

[0064] In some embodiments of the present application, a clean and sweet bean fragrance base comprises the following raw materials by weight: ethyl maltol 8-12 parts, ethyl acetate 4-6 parts, isoamyl acetate 28-32 parts, hexyl acetate 4-6 parts, geranyl acetate 1.5-2.5 parts, ethyl acrylate 3-5 parts, ethyl butyrate 16-20 parts, isoamyl acetate 3-5 parts, gamma-hexalactone 90-110 parts, ethyl hexanoate 23-27 parts, methyl hexanoate 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.

[0065] In a typical embodiment of the present application, a clean and sweet bean fragrance base comprises the following raw materials by weight: ethyl maltol 10 parts, ethyl acetate 5 parts, isoamyl acetate 30 parts, hexyl acetate 5 parts, geranyl acetate 2 parts, ethyl acrylate 4 parts, ethyl butyrate 18 parts, isoamyl acetate 4 parts, gamma-hexalactone 100 parts, ethyl hexanoate 25 parts, methyl hexanoate 80 parts, allyl hexanoate 8 parts, ethyl heptanoate 23 parts, 3-cyclohexyl propyl acrylate 3 parts, allyl phenoxyacetate 7 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 50 parts, propylene glycol 626 parts.

[0066] Example 1

[0067] This example provides a clean and sweet bean fragrance compound having the following structural formula:

[0068]

[0069] The chemical name of the clean and sweet bean fragrance 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.

[0070] The method for preparing the sweet and clean bean flavor compound comprises the following steps:

[0071] Step one: preparation of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol, the chemical reaction formula for preparing 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol is as follows:

[0072]

[0073] A1, the catalyst Pd2(dba)3 (4.6 mmol, 0.005 mmol, 2 mol%), sodium tert-butoxide (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) are sequentially placed in a 10 mL Schlenk reaction tube, and the reaction system is protected with argon; then, tert-butyl alcohol (1.0 mL) and water (0.1 mL) are sequentially added to the reaction system; the reaction system is heated to 100°C, and the reaction is stirred vigorously for 18 h; the structure of the borate compound is shown in formula 1; the structure of the iodobenzene compound is shown in the following formula:

[0074]

[0075] A2, after the reaction is completed, the reaction system is diluted with 5 mL of ethyl acetate, and then washed with 5 mL of water and 5 mL of saturated sodium chloride solution; the organic phase is dried over anhydrous sodium sulfate, and then concentrated by rotary evaporation; white solid 98 mg is obtained by silica gel column chromatography (200-300 mesh silica gel, n-hexane / ethyl acetate = 5:1), which is 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol, and the yield is 95%; the structure of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol is shown in formula 2, which has the following NMR spectral characteristics:

[0076] 1H NMR (400 MHz, CDC13) 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);

[0077] 13 C NMR (101 MHz, CDC13) 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.

[0078] Mass spectrometry data are as follows:

[0079] HRMS (ESI / [M+Na] + ): High resolution mass spectrometry theoretical calculation data for C 25 H 40 Na03: 411.2870, actual measured value 411.2867 (HRMS (ESI / [M+Na] + ) calculated for C 25 H 40 Na03: 411.2870, found 411.2867).

[0080] Step two: preparation 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, the chemical reaction formula for preparation is as follows:

[0081]

[0082] B1, 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol (84 mg, 0.2 mmol, 1.0 equiv) prepared in step one was dissolved in anhydrous dichloromethane (6 mL), cooled to 0 °C, and then slowly added SnCl4 solution in dichloromethane (1.0 mmol, 1 M, 5 equiv); after the addition was completed, the reaction was continued for 1 h, and after the end, the system was diluted with 20 mL of dichloromethane and poured into ice water, and after separation, the aqueous phase was extracted with dichloromethane (3 x 10 mL);

[0083] B2, The combined organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated by rotary evaporation. Silica gel column chromatography (200-300 mesh, n-hexane / ethyl acetate = 5:1) was used to separate and obtain 61 mg of white solid, 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, with a yield of 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 is shown in formula 3, which has the following NMR spectral characteristics:

[0084] 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).

[0085] 13 C 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.

[0086] Mass spectrometry data are as follows:

[0087] HRMS (ESI / [M+H] + ): High resolution mass spectrometry theoretical calculation data for C 25 H 39 O2: 371.2945, found 371.2944 (HRMS (ESI / [M+H] + ) calculated for C 25 H 39 O2: 371.2945, found 371.2944).

[0088] Step three: 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 the preparation is as follows:

[0089]

[0090] C1, 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 two was dissolved in anhydrous dichloromethane (5 mL), then a solution of boron tribromide in dichloromethane (0.36 mL, 2.0 M in CH2Cl2, 0.72 mmol) was slowly added at room temperature, that is, the concentration of boron tribromide is 2.0 mol / L, and the amount of boron tribromide added is 0.72 mmol; maintain stirring until TLC detects that 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 completely disappeared, the reaction was quenched with saturated sodium bicarbonate solution (10 mL), and the separated organic phase was extracted with dichloromethane (3 x 10 mL);

[0091] C2, the combined organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated by rotary evaporation, and then separated by silica gel column chromatography (200-300 mesh, n-hexane / ethyl acetate = 3:1) to obtain 70 mg of white solid, which 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, and the reaction yield is 86%.

[0092] 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 spectral characteristics:

[0093] 1 H NMR (500 MHz, CDC13) 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);

[0094] 13 C NMR (126 MHz, CDC13) 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.

[0095] Mass spectrometry data are as follows:

[0096] HRMS (ESI / [M-H] - ): -ion mode high resolution mass spectrum theoretical calculation data for C 23 H 33 O2: 341.2486, actual measured value is 341.2483 (HRMS (ESI / [M-H] - ) calculated for C 23 H 33 O2: 341.2486, found 341.2483).

[0097] Example 2

[0098] 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, and the test results are as follows:

[0099] (1) Fragrance evaluation:

[0100] 12 perfumers with more than 5 years of work experience evaluated the fragrance of the compound as follows: 12 perfumers unanimously believed that the compound had a sweet and clean bean fragrance, and also had a sweet and woody powder fragrance, and had an amber note.

[0101] (2) Fragrance retention test:

[0102] An 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 with a mass fraction of 10% was prepared using diethyl phthalate (DEP) as a solvent, a few drops of the solution were taken with a smelling strip, the test paper was placed on a smelling rack, and 3 perfumers smelled it every 2 hours. When more than or equal to 2 perfumers could not perceive the fragrance of the smelling test paper, the fragrance retention time was recorded.

[0103] The fragrance retention test showed that the sweet and clean bean fragrance 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 had a fragrance retention time of 14 hours, and the powder and amber fragrance had a fragrance retention time of 20 hours.

[0104] (3) Fragrance base fragrance test:

[0105] The fragrance base formula is shown in the following table:

[0106] Sweet and clean bean fragrance base

[0107]

[0108] A fragrance base and a B fragrance base were prepared according to the above table, 50 parts of the target product 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 were added to the B fragrance base, and 8 perfumers with more than 5 years of work experience evaluated the fragrance of the above-mentioned fragrance base as follows: 8 perfumers unanimously believed that the B fragrance base had a more prominent sweet and clean bean fragrance than the A fragrance base, and had a slightly elegant woody powder sweet fragrance note, and the fragrance quality of the fragrance base was significantly improved.

[0109] The above examples are preferred implementation schemes of the present application, in addition to this, the present application can also be implemented in other ways, any obvious substitution without departing from the concept of the present application is within the protection scope of the present application.

Claims

1. A clean, sweet, bean-flavored compound, characterized by: has the following structural formula: 。 2. A process for the preparation of a clean bean note compound as claimed in claim 1, characterized in that: comprises the following steps: Step one: preparation of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol; Its structural formula is shown in the following formula: ； Step two: preparation 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, which has the following structural formula: ； Step three: 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 prepared in step two is reacted under the action of dichloromethane and boron tribromide, and after separation and purification, the said clean and sweet bean flavor compound is obtained, which 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 flavor compound according to claim 2, characterized in that: In step one, the preparation method of 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol comprises the following steps: A1, Pd2(dba)3, sodium tert-butyl alcohol, ligand Ruphos, borate compound and iodobenzene compound are sequentially placed in a reaction container, and the reaction system is protected with argon; then tert-butyl alcohol and water are sequentially added to the reaction system; the reaction system is heated and stirred; the structure of the borate compound is shown in the following formula: ； The structure of the iodobenzene compound is shown in the following formula: ； A2, after the reaction is completed, the reaction system is diluted with ethyl acetate, and then washed with water and saturated sodium chloride solution; the organic phase is dried over anhydrous sodium sulfate, and then concentrated by rotary evaporation; 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol is obtained by silica gel column chromatography.

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

5. The method for preparing the sweet bean flavor compound according to claim 3, characterized in that: After the reaction in step A2 is completed, the reaction system is diluted with 4-6 mL of ethyl acetate, and then 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, and then concentrated by rotary evaporation. The concentrated product is separated by silica gel column chromatography to obtain 1-(4-ethyl-2,3-dimethoxybenzyl)-2,5,5,8a-tetramethyldecahydronaphthalen-2-ol.

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

7. The method for preparing the sweet bean flavor compound according to claim 6, characterized in that: In step three, 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 includes the following steps:

8. The method for preparing the sweet bean flavor compound according to claim 2, characterized in that: C1, 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 prepared in step two is dissolved in anhydrous dichloromethane, and then boron tribromide solution in dichloromethane is added at room temperature. Stirring is maintained 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. The reaction is quenched with saturated sodium bicarbonate solution, and the separated organic phase is extracted with dichloromethane. ​ C2, the obtained organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated by rotary evaporation, and then 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 flavor compound according to claim 8, characterized in that: In the step C1, 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 0.23-0.25 mmol was dissolved in anhydrous dichloromethane 4-6 mL, and then a solution of boron tribromide in dichloromethane was added at room temperature, and stirring was maintained until the disappearance of the starting material was detected by TLC, and the reaction was quenched using saturated sodium bicarbonate solution 9-11 mL.

10. A clean, sweet, bean-like flavor base characterized by: The following raw materials were included by weight parts: ethyl maltol 8-12 parts, ethyl acetate 4-6 parts, isoamyl acetate 28-32 parts, hexyl acetate 4-6 parts, geranyl acetate 1.5-2.5 parts, ethyl acrylate 3-5 parts, ethyl butyrate 16-20 parts, isoamyl acetate 3-5 parts, gamma-hexalactone 90-110 parts, ethyl hexanoate 23-27 parts, methyl hexanoate 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.

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