High-quality geranyl acetone composition and application

Abstract

According to the high-quality geranyl acetone composition provided by the invention, when the geranyl acetone composition provided by the invention is used as a raw material for synthesizing nerolidol, the yield of a product can be improved, and the composition has high-quality aroma and antibacterial characteristics. The composition mainly comprises two isomers of (E) and (Z)-geranyl acetone, four main components of hydrogenated geranyl acetone and alpha, gamma-unsaturated dienone and other impurities, the sum of the mass contents of the isomers of (E) and (Z)-geranyl acetone is larger than 98%, and the mass content ratio of (E)-geranyl acetone to (Z)-geranyl acetone meets the condition that (E) / (Z) is larger than or equal to 1.15 and smaller than or equal to 1.75. The mass content of hydrogenated geranyl acetone is less than 0.5%, and the mass content of alpha, gamma-unsaturated dienone is less than 0.1%. The fragrance characteristic of the composition is purer, and the composition has higher application value.

Description

Technical Field

[0001] The invention belongs to the field of fragrance synthesis, and particularly relates to a high-quality geranyl acetone composition and application thereof. Background Art

[0002] Geranyl acetone, also known as potassium dihydrogen ionone, has a scientific name of 3,7-dimethyl-2,6-octadienyl acetone. It is a precious spice with the aroma of magnolia, usually appearing as a colorless or light yellow oily liquid, with a fresh, light floral aroma, slightly sweet and rose-like flavor. Geranyl acetone can be dissolved in organic solvents such as ethanol and acetone, and is naturally present in plants such as fennel, tomatoes, and tea leaves.

[0003] In addition, geranyl acetone also has a good free radical scavenging mechanism, a wide range of odors and good bactericidal and antibacterial properties. Its aroma is similar to that of raw pears, apples and tropical fruits, so it is widely used in cosmetics, perfumes, medicine, tobacco and other industries. In the pharmaceutical field, geranyl acetone is also an important intermediate for the synthesis of vitamin E, K1 and other substances.

[0004] The market demand for geranyl acetone is increasing with the expansion of the global market and the improvement of technology. At present, it is widely used in the pharmaceutical field, and its use as a pharmaceutical intermediate is expanding. According to statistics, the global geranyl acetone market size has reached hundreds of tons, and it is expected to maintain steady growth in the next few years.

[0005] From the preparation point of view, geranyl acetone can be synthesized by a variety of chemical methods. For example, it can be prepared by the reaction of linalool and ethyl acetoacetate under the action of a catalyst, or by linalool and alkoxypropylene under an acidic environment. Geranyl acetone is a key raw material for the synthesis of nerolidol, and its product quality also has a significant impact on the quality of nerolidol.

[0006] Geranyl acetone has two main configurations, and their content and the ratio of the two have a certain impact on its downstream applications. If the quality of geranyl acetone can be further improved, it will have better economic value and wider application value. Summary of the invention

[0007] The object of the present invention is to provide a high-quality geranylacetone composition, which has high-quality aroma and antibacterial properties. The geranylacetone composition mainly comprises four main components, namely, two isomers of (E) and (Z)-geranylacetone, hydrogenated geranylacetone and α,γ-unsaturated diene ketone, wherein the sum of the mass contents of the (E) and (Z)-geranylacetone isomers is greater than 98%. The aroma characteristics of the composition are purer, the application value is higher, and as a raw material, it has a significant promoting effect on the synthesis of nerolidol.

[0008] To achieve the above purpose, the technical solution adopted by the present invention specifically includes the following contents:

[0009] A high-quality geranylacetone composition mainly comprises two isomers of (E) and (Z)-geranylacetone, hydrogenated geranylacetone and α,γ-unsaturated diene ketone, wherein the sum of the mass contents of the (E) and (Z)-geranylacetone isomers is greater than 98%, and the mass content ratio of (E)-geranylacetone to (Z)-geranylacetone satisfies 1.15≤(E) / (Z)≤1.75; in addition, the mass content of hydrogenated geranylacetone is less than 0.8%, the mass content of α,γ-unsaturated diene ketone is less than 0.4%, and the mass content of hydrogenated geranylacetone is greater than or equal to 2×the mass content of α,γ-unsaturated diene ketone.

[0010] In some embodiments, the (E)-geranyl acetone has a mass content of ≥52%, preferably a mass content of ≥54%;

[0011] In some embodiments, the mass content ratio of (E)-geranyl acetone to (Z)-geranyl acetone satisfies 1.15≤(E) / (Z)≤1.75, preferably 1.25≤(E) / (Z)≤1.65;

[0012] In some embodiments, the mass content of the hydrogeranylacetone is preferably less than 0.6%, for example: 0.5%, 0.4%, 0.35%, 0.3%, 0.25%, 0.2%, 0.15%, 0.1%, 0.05%, 0.

[0013] The mass content of α,γ-unsaturated diene ketone is preferably less than 0.2%, for example: 0.15%, 0.1%, 0.05%, 0;

[0014] In some embodiments, the mass content of α,γ-unsaturated diene ketone is >0;

[0015] In some embodiments, the geranylacetone composition contains less than 0.3 wt % of other impurities.

[0016] In some embodiments, preferably, the mass content of hydrogenated geranylacetone is ≥ the mass content of α,γ-unsaturated diene ketone×2.6.

[0017] The structures of the components of the geranyl acetone composition are shown below:

[0018]

[0019] As a specific embodiment, the preparation method of the high-quality geranyl acetone composition comprises the following steps:

[0020] (1) using linalool and 2-methoxypropylene as raw materials, and obtaining a geranylacetone reaction solution under the catalytic action of an acid catalyst;

[0021] (2) The geranyl acetone reaction solution is adjusted in pH value and then subjected to preliminary impurity removal, rectification and decolorization to obtain a geranyl acetone composition that meets the requirements.

[0022] Preferably, in step (1), the molar ratio of linalool to 2-methoxypropylene is 1:2-3;

[0023] The reaction temperature is 120-150°C, the reactor is a tubular reactor, and the reaction time is 2h-3h;

[0024] Preferably, in step (1), the acid catalyst is selected from one or more of phosphoric acid, dimethyl phosphate, dimethyl phosphite, and diethyl phosphate;

[0025] Preferably, the amount of the catalyst is 0.05 to 0.2 mol % of linalool.

[0026] Preferably, in step (2), after adjusting the pH value, the alkalinity of the solution is controlled to be below 15 ppm (in terms of hydroxide content), preferably below 10 ppm (in terms of hydroxide content), for example 2-8 ppm.

[0027] In the step (2), the primary impurity removal is to remove the remaining 2-methoxypropylene and the generated by-products in the reaction solution, which can be carried out by extraction, simple distillation and the like.

[0028] Preferably, the distillation in step (2) is vacuum distillation, the tower top temperature is 80-120°C, the tower bottom temperature is 100-140°C, the vacuum distillation pressure is 100-800Pa, the distillation tower uses a packed tower, the packing material is 316L or 904, the equivalent number of plates is 16-40, and the distillation residence time is less than 5h, for example, 4.5h, 4h, 3h, 2h, 1h.

[0029] Preferably, the refractive index of geranyl acetone after the treatment in step (2) is between 1.459 and 1.472.

[0030] The geranylacetone composition can be used in cosmetics, perfumes and tobacco.

[0031] Furthermore, the present invention also relates to the application of the geranyl acetone composition in the synthesis of nerolidol.

[0032] The geranylacetone composition is used as a raw material to continue to react with acetylene and hydrogen to catalytically synthesize nerolidol;

[0033] As a specific embodiment, the temperature of the ethynylation reaction is 0 to 30° C., the molar ratio of acetylene to geranyl acetone is 1 to 5, and the catalyst is a metal hydroxide;

[0034] The acetylation product is separated by distillation and then subjected to hydrogenation reaction. The temperature of the hydrogenation reaction is 30-60°C, the catalyst is a noble metal catalyst such as nickel and palladium, and the reaction pressure is 1-4MPa.

[0035] The total molar yield of the hydrogenated product nerolidol is above 94% (relative to geranyl acetone), preferably above 96%.

[0036]

[0037] The positive effects of the present invention are:

[0038] (1) The present invention provides a high-quality geranylacetone composition, which can not only improve its aroma quality, but also has a significant promoting effect on increasing the synthesis yield of nerolidol and is more economical.

[0039] (2) The present invention only uses simple traditional separation means to prepare a high-quality geranyl acetone composition, and improves product quality by controlling process parameters, saving equipment investment and device energy consumption. DETAILED DESCRIPTION

[0040] The present invention will be further described below by means of specific examples, but the present invention is not limited to the following examples.

[0041] Drugs used:

[0042] Reaction materials: Wanhua Chemical;

[0043] Catalyst: Sigma reagent;

[0044] The gas chromatography test conditions of the present invention are as follows:

[0045] Instrument model: Agilent 7890B

[0046] Chromatographic column: DB-5 (30m×0.25mm×0.25μm)

[0047] Heating program: starting temperature 30℃, heating to 180℃ at 15℃ / min, holding for 5min, then heating to 280℃ at 20℃ / min, holding for 5min

[0048] Inlet temperature: 280°C

[0049] FID detector temperature: 280℃

[0050] Split injection, split ratio 30:1

[0051] Injection volume: 1.0 μL

[0052] Air flow: 400ml / min

[0053] H2 flow rate: 30ml / min.

[0054] The following examples are all preparation processes of the geranyl acetone composition, and the samples of the examples are uniformly evaluated in Table 1.

[0055] Example 1

[0056] Linalool and 2-methoxypropene were used as raw materials (molar ratio 1:2.6), and the reaction was carried out at 130°C for 2 hours under the catalytic action of a phosphoric acid catalyst (the addition amount was 0.05 mol% of linalool). The geranyl acetone reaction liquid was adjusted to a base value of 7 ppm using NaOH, and then the reaction liquid was distilled to remove the remaining 2-methoxypropene and the generated by-product 2,2-dimethoxypropane in the reaction liquid, and the obtained crude geranyl acetone entered the distillation system for further purification. The distillation tower uses a 316L material packing tower with an equivalent number of plates of 20, a pressure setting of 400 Pa, a top temperature of 109°C, a bottom temperature of 119°C, a distillation residence time of 4h, and the geranyl acetone extracted from the top of the tower is decolorized by activated carbon adsorption for 0.5h to obtain a total geranyl acetone solution with a purity of 99.3wt% and a refractive index of 1.466, wherein the content of (E)-geranyl acetone is 57.1wt%, the content of hydrogenated geranyl acetone is 0.46wt%, and the content of α,γ-unsaturated diene ketone is 0.20wt%.

[0057] Example 2

[0058] Linalool and 2-methoxypropylene were used as raw materials (molar ratio 1:3), and the reaction was carried out at 130°C for 2 hours under the catalytic action of a phosphoric acid catalyst (the addition amount was 0.05 mol% of linalool) to obtain a geranyl acetone reaction solution. The alkali value of the geranyl acetone reaction solution was adjusted to 3 ppm using NaOH, and then the reaction solution was distilled to remove the remaining 2-methoxypropylene and the generated by-product 2,2-dimethoxypropane in the reaction solution, and the obtained crude geranyl acetone entered the distillation system for further purification. The distillation tower uses a 316L material packing tower with an equivalent number of plates of 26, a pressure setting of 300 Pa, a top temperature of 104°C, a bottom temperature of 115°C, a distillation residence time of 2h, and the geranyl acetone extracted from the top of the tower is decolorized by activated carbon adsorption for 0.5h to obtain a total geranyl acetone solution with a purity of 99.6wt% and a refractive index of 1.467, wherein the content of (E)-geranyl acetone is 59.2wt%, the content of hydrogenated geranyl acetone is 0.21wt%, and the content of α,γ-unsaturated diene ketone is 0.07wt%.

[0059] Example 3

[0060] Linalool and 2-methoxypropene were used as raw materials (molar ratio 1:2), and the reaction was carried out at 140°C for 3 hours under the catalytic action of a phosphoric acid catalyst (the addition amount was 0.1 mol% of linalool) to obtain a geranyl acetone reaction solution. The alkali value of the geranyl acetone reaction solution was adjusted to 3 ppm using NaOH, and then the reaction solution was distilled to remove the remaining 2-methoxypropene and the generated by-product 2,2-dimethoxypropane in the reaction solution, and the obtained crude geranyl acetone was further purified by entering the distillation system. The distillation tower uses a 316L material packing tower with an equivalent number of plates of 26, a pressure setting of 200 Pa, a top temperature of 96°C, a bottom temperature of 105°C, a distillation residence time of 2h, and the geranyl acetone extracted from the top of the tower is decolorized by activated carbon adsorption for 0.5h to obtain a total geranyl acetone solution with a purity of 99.5wt%, a refractive index of 1.465, of which the (E)-geranyl acetone content is 62wt%, the hydrogenated geranyl acetone content is 0.28wt%, and the α,γ-unsaturated diene ketone content is 0.10wt%.

[0061] Example 4

[0062] Linalool and 2-methoxypropene were used as raw materials (molar ratio 1:2.6), and the reaction was carried out at 140°C for 3 hours under the catalytic action of dimethyl phosphate catalyst (the addition amount was 0.05 mol% of linalool) to obtain geranyl acetone reaction liquid. The alkali value of the geranyl acetone reaction liquid was adjusted to 5 ppm using NaOH, and then the reaction liquid was distilled to remove the remaining 2-methoxypropene and the generated by-product 2,2-dimethoxypropane in the reaction liquid, and the obtained crude geranyl acetone entered the distillation system for further purification. The distillation tower uses a 316L material packing tower with an equivalent number of plates of 20, a pressure setting of 200 Pa, a top temperature of 96°C, a bottom temperature of 105°C, a distillation residence time of 4h, and the geranyl acetone extracted from the top of the tower is decolorized by activated carbon adsorption for 0.5h to obtain a total geranyl acetone solution with a purity of 99.4wt% and a refractive index of 1.464, wherein the content of (E)-geranyl acetone is 60.5wt%, the content of hydrogenated geranyl acetone is 0.39wt%, and the content of α,γ-unsaturated diene ketone is 0.15wt%.

[0063] Example 5

[0064] Linalool and 2-methoxypropene were used as raw materials (molar ratio 1:3), and the reaction was carried out at 140°C for 3 hours under the catalytic action of dimethyl phosphite catalyst (the addition amount was 0.1 mol% of linalool) to obtain geranyl acetone reaction liquid. The alkali value of the geranyl acetone reaction liquid was adjusted to 3 ppm using NaOH, and then the reaction liquid was extracted with water to remove the remaining 2-methoxypropene and the generated by-product 2,2-dimethoxypropane in the reaction liquid, and the obtained crude geranyl acetone entered the distillation system for further purification. The distillation tower uses a 316L material packing tower with an equivalent number of plates of 20, a pressure setting of 200 Pa, a top temperature of 96°C, a bottom temperature of 105°C, a distillation residence time of 4h, and the geranyl acetone extracted from the top of the tower is decolorized by activated carbon adsorption for 0.5h to obtain a total geranyl acetone solution with a purity of 99.5wt% and a refractive index of 1.466, wherein the content of (E)-geranyl acetone is 55.9wt%, the content of hydrogenated geranyl acetone is 0.30wt%, and the content of α,γ-unsaturated diene ketone is 0.09wt%.

[0065] Example 6

[0066] Linalool and 2-methoxypropylene were used as raw materials (molar ratio 1:3), and the reaction was carried out at 130°C for 2 hours under the catalytic action of a phosphoric acid catalyst (the addition amount was 0.05 mol% of linalool) to obtain a geranyl acetone reaction solution. The alkali value of the geranyl acetone reaction solution was adjusted to 3 ppm using NaOH, and then the reaction solution was distilled to remove the remaining 2-methoxypropylene and the generated by-product 2,2-dimethoxypropane in the reaction solution, and the obtained crude geranyl acetone entered the distillation system for further purification. The distillation tower uses a 316L material packing tower with an equivalent number of 40 plates, a pressure setting of 300 Pa, a top temperature of 104°C, a bottom temperature of 120°C, a distillation residence time of 2h, and the geranyl acetone extracted from the top of the tower is decolorized by activated carbon adsorption for 0.5h to obtain a total geranyl acetone solution with a purity of 99.8wt% and a refractive index of 1.466, wherein the (E)-geranyl acetone content is 59.8wt%, and the contents of hydrogenated geranyl acetone and α,γ-unsaturated diene ketone are both 0.

[0067] Comparative Example 1

[0068] Linalool and 2-methoxypropene were used as raw materials (molar ratio 1:3), and the reaction was carried out at 140°C for 3 hours under the catalytic action of a phosphoric acid catalyst (the addition amount was 0.05 mol% of linalool) to obtain a geranyl acetone reaction solution. Without adjusting the base value, the reaction solution was then distilled to remove the remaining 2-methoxypropene and the generated by-product 2,2-dimethoxypropane in the reaction solution, and the obtained crude geranyl acetone was further purified by entering a distillation system. The distillation tower uses a 316L material packing tower with an equivalent number of plates of 26, a pressure setting of 200 Pa, a top temperature of 96°C, a bottom temperature of 105°C, a distillation residence time of 2h, and the geranyl acetone extracted from the top of the tower is decolorized by activated carbon adsorption for 0.5h to obtain a total geranyl acetone solution with a purity of 98.5wt% and a refractive index of 1.461, wherein the content of (E)-geranyl acetone is 50.1wt%, the content of hydrogenated geranyl acetone is 0.95wt%, and the content of α,γ-unsaturated diene ketone is 0.35wt%.

[0069] Comparative Example 2

[0070] Linalool and 2-methoxypropene were used as raw materials (molar ratio 1:3), and the reaction was carried out at 140°C for 3 hours under the catalytic action of dimethyl phosphite (the addition amount was 0.1 mol% of linalool) to obtain a geranylacetone reaction solution. The alkali value of the geranylacetone reaction solution was adjusted to 3 ppm using NaOH, and then the reaction solution was distilled to remove the remaining 2-methoxypropene and the generated by-product 2,2-dimethoxypropane in the reaction solution, and the obtained crude geranylacetone entered the distillation system for further purification. The distillation tower uses a 316L material packing tower with an equivalent number of plates of 26, a pressure setting of 2000Pa, a top temperature of 145°C, a bottom temperature of 170°C, a distillation residence time of 4h, and the geranyl acetone extracted from the top of the tower is decolorized by activated carbon adsorption for 0.5h to obtain a total geranyl acetone solution with a purity of 99.5wt% and a refractive index of 1.469, wherein the content of (E)-geranyl acetone is 56.1wt%, the content of hydrogenated geranyl acetone is 0.22wt%, and the content of α,γ-unsaturated diene ketone is 0.18wt%.

[0071] Preparation of nerolidol:

[0072] The geranylacetone composition obtained in the above embodiment / comparative example is used as a raw material to continue to react with acetylene, the temperature of the ethynylation reaction is 0°C, the molar ratio of acetylene to geranylacetone is 5, the amount of the catalyst potassium hydroxide is 0.5 mol% of the geranylacetone, and the crude ethynylation product is separated by distillation to obtain dehydrogenated nerolidol; then the dehydrogenated nerolidol is subjected to a hydrogenation reaction, the temperature of the hydrogenation reaction is 40°C, the catalyst is nickel-loaded silica (the amount is 2wt% of the dehydrogenated nerolidol), the hydrogen pressure is 3MPa, and the hydrogenated product is subjected to vacuum distillation to obtain the final product nerolidol, and the total yield is calculated based on the ratio of the nerolidol output to the geranylacetone feed amount.

[0073] The sample evaluation results of the above examples are shown in the following table:

[0074] Table 1 Sample evaluation results

[0075]

[0076] Note: The aroma evaluation score is the average score of 10 perfumers.

Claims

1. A composition of geranyl acetone, characterized in that Including two isomers of (E) and (Z)-geranyl acetone, hydrogenated geranyl acetone and α,γ-unsaturated diene ketone; among which: The sum of the mass contents of the (E) and (Z)-geranylacetone isomers is greater than 98%, and the mass content ratio of (E)-geranylacetone to (Z)-geranylacetone satisfies 1.15≤(E) / (Z)≤1.75; The mass content of hydrogenated geranyl acetone is less than 0.8%, the mass content of α,γ-unsaturated diene ketone is less than 0.4%, and the mass content of hydrogenated geranyl acetone is ≥2×the mass content of α,γ-unsaturated diene ketone.

2. The geranyl acetone composition according to claim 1, characterized in that The mass content of the (E)-geranylacetone is ≥52%, preferably ≥54%.

3. The geranyl acetone composition according to claim 1 or 2, characterized in that The mass content ratio of the (E)-geranyl acetone to the (Z)-geranyl acetone satisfies 1.25≤(E) / (Z)≤1.

65.

4. The geranyl acetone composition according to any one of claims 1 to 3, characterized in that The mass content of the hydrogeranylacetone is less than 0.6%.

5. The geranyl acetone composition according to any one of claims 1 to 4, characterized in that The mass content of the α,γ-unsaturated diene ketone is less than 0.2%.

6. The geranyl acetone composition according to any one of claims 1 to 5, characterized in that The mass content of the hydrogenated geranyl acetone is ≥ the mass content of the α,γ-unsaturated diene ketone×2.

6.

7. A method for preparing a high-quality geranylacetone composition according to any one of claims 1 to 6, comprising the following steps: (1) using linalool and 2-methoxypropylene as raw materials, and obtaining a geranylacetone reaction solution under the catalytic action of an acid catalyst; (2) The geranyl acetone reaction solution is adjusted in pH value and then subjected to preliminary impurity removal, distillation and decolorization.

8. The method according to claim 7, characterized in that In step (1), the molar ratio of linalool to 2-methoxypropylene is 1:2-3; The acid catalyst is selected from phosphoric acid, dimethyl phosphate, dimethyl phosphite, and diethyl phosphate, and the amount of the catalyst is 0.05 to 0.2 mol% of linalool.

9. The method according to claim 7, characterized in that: In step (2), after the pH value of the reaction solution is adjusted, the alkalinity of the solution is controlled to be below 15 ppm, preferably below 10 ppm, in terms of hydroxide content.

10. The method according to claim 7, characterized in that The distillation is vacuum distillation, the tower top temperature is 80-120°C, the tower bottom temperature is 100-140°C, the vacuum distillation pressure is 100-800Pa, the distillation tower uses a packed tower, the packing material is 316L or 904, the equivalent number of tower plates is 16-40, and the distillation residence time is <5h.

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