A fragrant composition with a refreshing or subtle aroma, its preparation method and application method thereof.

Abstract

This invention relates to an aromatic composition having a distinctive, refreshing or subtle fragrance that is long-lasting. The invention also relates to a method for preparing the aromatic composition.

Description

Technical Field

[0001] This invention belongs to the field of daily cosmetics technology and relates to an aromatic composition having a special, refreshing or subtle fragrance that is long-lasting and suitable for the needs of "minimalist fragrance" and "subtle fragrance". This invention also relates to a method for preparing and using the aromatic composition. Background Technology

[0002] In the fragrance and flavor industry, the classification of floral fragrances follows the classic Ye Xinong fragrance classification system in the domestic perfumery industry. This system divides floral fragrances into four basic fragrance categories: fresh, sweet, umami, and subtle, as well as four compound fragrance categories: fresh-sweet, sweet-umami, umami-subtle, and subtle-fresh. Among them, fresh and subtle-fresh floral fragrances are characterized by good diffusion, soft aroma, and low olfactory threshold. They can impart a fresh and clean subtle fragrance effect to daily chemical products with low addition amounts. They are widely applicable to the development of fragrance formulations in areas such as fabric care, personal care, and home fragrances, and are one of the mainstream R&D directions in the industry that align with the current consumer trends of "minimalist fragrance" and "subtle fragrance".

[0003] However, the current perfumery system suffers from a severe lack of readily applicable fresh and delicate floral monomers, with the core being a limited number of classic synthetic monomers such as methyl dihydrojasmonate, lily of the valley aldehyde, and hydroxycitronellol. From the perspective of natural fragrance supply, the natural extracts of these fragrances are constrained by factors such as raw material origin, harvesting period, and extraction process, generally resulting in low yield, high cost, easy variation in aroma components, and poor stability, making it difficult to meet the requirements of large-scale industrial production. From the perspective of synthetic fragrances, existing product portfolios largely focus on strong floral monomers such as sweet and delicate notes, while commercially available fresh and delicate synthetic fragrances suffer from technical shortcomings such as limited aroma profiles, insufficient longevity, and poor compatibility with other fragrance monomers. Long-term reliance on a limited number of classic monomers for formulation not only leads to severe homogenization of end-product aromas and market olfactory fatigue, but also makes it difficult to meet the industry's stringent requirements for natural equivalent fragrances and "clean label" standards.

[0004] Therefore, developing novel aromatic compositions with novel structures, aroma characteristics that closely match natural fresh and subtle floral fragrances, excellent stability, long-lasting fragrance, and controllable production costs is of great practical significance for enriching the product matrix of floral fragrances, expanding the innovative dimensions of fragrance formulations, breaking through the application bottlenecks of existing fresh or subtle floral fragrances, and promoting the development of the fragrance and flavor industry towards high quality and differentiation. Summary of the Invention

[0005] The inventors of this invention unexpectedly discovered that the compounds obtained by further alkylating known daumatone compounds have a special aromatic odor, and this aromatic odor is significantly different from that of the original daumatone compounds. The aromatic compositions formulated in this way can meet the industry's demand for fresh and delicate floral fragrances, and are particularly suitable for making perfumes with the corresponding fragrance.

[0006] Specifically, daumatone compounds are characterized by a rich, sweet rose scent, combined with fresh berry notes and warm woody aromas. They possess high aroma recognition and excellent diffusion, presenting a sweet and floral fragrance. In contrast, the compound obtained in this invention exhibits a unique aroma profile distinct from daumatone compounds—the sweetness is more restrained and soft, the berry notes are delicate and elegant, and the woody notes transform into a velvety, warm texture. Overall, it presents a typical, clean, and subtly complex floral fragrance with harmonious and natural layers. Furthermore, the aroma release curve of this compound differs from that of daumatone compounds; even at low concentrations, it can produce a long-lasting, subtle fragrance with excellent retention. It also possesses unique advantages in compatibility with commonly used fragrance monomers, including but not limited to its ability to effectively complement the application scenarios of daumatone compounds.

[0007] Therefore, a first aspect of the present invention relates to an aromatic composition comprising a compound of formula I or an isomer or salt thereof: I Among them, R1, R2, R3, R4, and R5 are each independently selected from straight chains or branched chains C. 1-6 Alkyl groups, preferably selected from straight-chain or branched C4 groups. 1-4 Alkyl groups, more preferably selected from methyl, ethyl, n-propyl, and isopropyl, and even more preferably methyl; and Indicates a single or double bond, and three There must be at least one double bond and at most two double bonds. When there are two double bonds, the two double bonds are not adjacent to each other. The aromatic composition described therein is a perfume.

[0008] In a preferred embodiment, the compound of formula I or an isomer or salt thereof is selected from the following compounds or isomers or salts thereof: .

[0009] In a preferred embodiment, the aromatic composition further comprises one or more of the following: antioxidants, chelating agents, opacifiers, preservatives, solubilizers, fixatives, colorants, pearlescent agents, and humectants.

[0010] In a preferred embodiment, the aromatic composition also contains other fragrance ingredients.

[0011] In a preferred embodiment, the aromatic composition contains 0.1%-30% by weight of the compound of formula I or its isomers or salts, preferably 0.2%-20%, more preferably 0.3%-10%, more preferably 0.5%-5%, and more preferably 1%-3%.

[0012] A second aspect of the present invention relates to a method for preparing the aforementioned aromatic composition, comprising the following steps: (1) Preparation of a compound of formula I or an isomer or salt thereof, comprising the step of reacting a compound of formula II or an isomer or salt thereof with a Grignard reagent: II, Among them, R1, R2, R3, R4 and The definition is the same as in Equation I; and (2) Mixing the compound of formula I or its isomers or salts with other components of the aromatic composition (i.e., solvents and optional antioxidants, chelating agents, opacifiers, preservatives, solubilizers, fixatives, colorants, pearlescent agents, humectants and other fragrance components).

[0013] Specifically, the compound of formula II or its isomers or salts may be the following compounds of formula II-1 or II-2 or their isomers or salts: .

[0014] More specifically, the compound of formula II or its isomers or salts are selected from the following compounds or their isomers or salts: β-D-stakhone; Alpha-tacrotone; β-Turkeyone; Tufyrenone.

[0015] The Grignard reagent may be, for example, R5-MgCl or R5-Li, wherein the definition of R5 is the same as in Formula I.

[0016] A third aspect of the invention relates to a method for obtaining or enhancing a fresh or subtle aromatic atmosphere, comprising using the aforementioned aromatic composition. Detailed Implementation

[0017] The terms solvent, antioxidant, chelating agent, opacifier, preservative, solubilizer, fixative, colorant, pearlescent agent, humectant, and other fragrance components (i.e., fragrance components other than the compound of formula I or its isomers or salts) used in this specification are all commonly used component types in aromatic compositions, and the meanings of these terms are well known to those skilled in the art. This invention does not impose any special limitations on these components that can be used in aromatic compositions. Those skilled in the art can select and determine the specific types and contents of these components according to actual conditions without inventive effort. For example, the weight percentage of the solvent in the aromatic composition described in this invention can be 50%-98%, 60%-95%, or 70-90%; the weight percentage of other fragrance components (if any) can be 0.1%-30%, 0.2-20%, 0.5-15%, 1%-10%, or 5-15%; and the weight percentage of other types of components (if any) can be 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%. The above values ​​are for illustrative purposes only and do not constitute a limitation on the content of each component in the aromatic composition.

[0018] In one embodiment, the solvent is selected from water, ethanol, propylene glycol, dipropylene glycol, butylene glycol, glycerol, or mixtures thereof. Its weight percentage in the aromatic composition of the present invention may be 50%-98%, 60%-95%, or 70-90%.

[0019] In one embodiment, the antioxidant is selected from butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), α-tocopherol (vitamin E), ascorbyl palmitate, tert-butylhydroquinone (TBHQ), or mixtures thereof. The weight percentage of such components (if present) in the aromatic composition of the present invention may be, for example, 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%.

[0020] In one embodiment, the chelating agent is selected from ethylenediaminetetraacetic acid (EDTA) salts (e.g., disodium EDTA, tetrasodium EDTA), sodium phytate, hydroxyethyl phosphate, sodium citrate, or mixtures thereof. The weight percentage of such components (if present) in the aromatic composition of the present invention may be, for example, 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%.

[0021] In one embodiment, the light-blocking agent is selected from ethylhexyl methoxycinnamate, diethylaminohydroxybenzoylhexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, methylene bis-benzotriazolyl tetramethylbutylphenol, or mixtures thereof. The weight percentage of such components (if present) in the aromatic composition of the present invention may, for example, be 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%.

[0022] In one embodiment, the preservative is selected from phenoxyethanol, benzyl alcohol, methylparaben, propylparaben, potassium sorbate, sodium benzoate, chlorphenesin, ethylhexylglycerin, or mixtures thereof. The weight percentage of such components (if any) in the aromatic composition of the present invention may be, for example, 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%.

[0023] In one embodiment, the solubilizer is selected from polyethylene glycol hydrogenated castor oil derivatives (such as PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil), polyether polyols / polyoxyethylene ethers (such as PPG-26-butanol polyether-26), polyethylene glycol fatty acid esters (such as PEG-40 stearate), polysorbates (Tween derivatives, such as Tween 20, Tween 80) or mixtures thereof. The weight percentage of such components (if any) in the aromatic composition of the present invention may, for example, be 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%.

[0024] In one embodiment, the fixative is selected from triethyl citrate, santalol, benzoin extract, cyclopentadecanol, or mixtures thereof. The weight percentage of such components (if any) in the aromatic composition of the present invention may be, for example, 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%.

[0025] In one embodiment, the colorant is selected from CI 19140 (tartrazine), CI 15985 (sunset yellow), CI 16035 (allure red), CI 16255 (carmine), CI 42090 (brilliant blue), CI 60730 (acid violet 43), CI 47005 (quinoline yellow), CI 77891 (titanium dioxide), or mixtures thereof. The weight percentage of such components (if any) in the aromatic composition of the present invention may, for example, be 0.001%-10%, 0.01-5%, 0.05-1%, or 0.1%-0.5%.

[0026] In one embodiment, the pearlescent agent is selected from ethylene glycol distearate, ethylene glycol monostearate, PEG-150 distearate, mica, titanium dioxide-coated mica, magnesium stearate, or mixtures thereof. The weight percentage of such components (if any) in the aromatic composition of the present invention may be, for example, 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%.

[0027] In one embodiment, the moisturizer is selected from glycerin, propylene glycol, 1,3-propanediol, butylene glycol, 1,2-pentanediol, polyethylene glycol-400, trehalose, betaine, panthenol, sodium hyaluronate, or mixtures thereof. The weight percentage of such components (if any) in the aromatic composition of the present invention may, for example, be 0.01%-20%, 0.1-10%, 0.2-5%, or 0.5%-1%.

[0028] Other fragrance components used in this invention can be substances with a clean or subtle fragrance profile similar to the compound of Formula I or its isomers or salts, thereby enhancing the clean or subtle aromatic effect. Other fragrance components can also have other fragrance profiles, such as fruit, wood, or aquatic. Since the clean or subtle fragrance profile of the compound of Formula I or its isomers or salts does not conflict with these other fragrance profiles, such a combination can achieve complementary fragrance notes, rich layers, and synergistic aroma enhancement. Those skilled in the art can select according to actual needs.

[0029] In one embodiment, the other fragrance components are selected from natural fragrances or synthetic fragrances or mixtures thereof, wherein the natural fragrances include: rose absolute, ylang-ylang oil, jasmine absolute, neroli oil, bergamot oil, lavender oil, sweet orange oil, patchouli oil, vetiver oil, sandalwood essential oil, osmanthus extract, rosemary oil, peppermint oil, and benzoin resin; the synthetic fragrances include: fatty aldehyde fragrances (including C6-C13 fatty aldehydes, such as decanal or undecaldehyde), lily of the valley aldehyde, rose alcohol, musk (such as galomel, tuna, etc.), linalool, phenethyl alcohol, geraniol, citronellol, leaf alcohol, linalyl acetate, benzyl acetate, citral, ionone, orrisone, coumarin, vanillin, benzyl salicylate, benzyl benzoate, leaf alcohol acetate, methyl dihydrojasmonate, methyl cedryne, ambroxol, and ambroxol. The weight percentage of other fragrance components (if any) in the aromatic composition described in this invention may be, for example, 0.1%-30%, 0.2-20%, 0.5-15%, 1%-10%, or 5-15%. It should be noted that some other fragrance components (such as benzyl benzoate, benzyl salicylate, patchouli oil, vetiver oil, methyl cedarwood ketone, gallocha, etc.) can also objectively act as fixatives, and therefore can also be classified as fixatives.

[0030] The isomers described in this specification include tautomers (e.g., tautomers resulting from keto-enol tautomerism of the carbonyl group of Formula I or II) and stereoisomers (e.g., E / Z isomers of the compound of Formula II). The salts described in this specification include alkoxides or oxonium salts formed from the enol configuration when keto-enol tautomerism occurs.

[0031] The preparation of compound I, or its isomers or salts, can be carried out according to the process and mechanism shown in reaction formula 1. Taking R5-MgCl as the Grignard reagent as an example, the α,β-unsaturated ketone structure in formula II undergoes a 1,4-addition with R5-MgCl to form the transition state of formula III, which is then reacted with hydrated hydrogen ions (H3O). + Compound of formula I is formed under the action of ).

[0032] The inventors of this invention unexpectedly discovered a breakthrough in the inherent rules of this type of reaction during the alkylation reaction of daumatones using Grignard reagents. In conventional understanding within the field of organic synthesis, the addition reaction of Grignard reagents with α,β-unsaturated ketones preferentially proceeds via 1,2-addition due to the significantly higher electrophilicity of the carbonyl carbon compared to the β-unsaturated carbon, generating allyl alcohol derivatives. This reaction orientation has been confirmed by extensive experimental data and authoritative literature in the vast majority of Grignard addition systems of α,β-unsaturated ketones and is a typical characteristic of this type of reaction.

[0033] The reaction system for constructing daumatone compounds in this invention does not require the introduction of special ligands, noble metal catalysts, or extreme reaction conditions. It only uses the specific reaction substrate structure of this invention and relatively mild reaction conditions to unexpectedly achieve a 1,4-addition selectivity of over 99%, generating alkylated ketone products in a near-directional manner. Even more surprisingly, this highly selective 1,4-addition product is not a trace byproduct that is difficult to avoid in traditional synthesis, but a target derivative with a special aromatic odor, whose aroma characteristics are significantly different from those of the original daumatone compounds.

[0034] Reaction 1

[0035] As those skilled in the art will understand, the chemical formulas (e.g., formula II or III) in this specification... Indicates a single bond with unspecified direction, that is, for The double bonds are not limited to E / Z configuration.

[0036] The aromatic composition described in this application refers to a composition having a specific aroma and / or fragrance, formulated from fragrance ingredients and / or flavoring additives. Perfume is a specific form of aromatic composition, and given that the compounds described in this invention are particularly suitable for making perfumes with corresponding fragrance profiles, perfume is also a preferred form of the aromatic composition of this invention.

[0037] The aromatic compositions of the present invention can be prepared using methods known in the art. The preparation method includes the step of mixing a compound of formula I or its isomers or salts with other components of the aromatic composition. This mixing can be either a direct mixing of the components in the aromatic composition, or the preparation of a portion of the components into a premix, followed by mixing the premix with the other components. After mixing, the final aromatic composition or fragrance product can be obtained through conventional methods such as stirring, aging, filtration, and filling. Those skilled in the art are fully capable of selecting appropriate methods to prepare the aromatic compositions based on the actual situation.

[0038] The following examples are used to explain and illustrate the present invention, but should not be construed as limiting the scope of protection of the patent application.

[0039] Example The starting reactants used in the examples were obtained as follows: β-takidomone (1-(2,6,6-trimethylcyclohex-3-enyl)but-2-en-1-one) was obtained according to the methods of Examples 2 and 5 of Chinese Patent CN102531865A; α-takidomone (1-(2,6,6-trimethyl-cyclohex-2-enyl)-2-buten-1-one) and β-takidomone (1-(2,6,6-trimethyl-cyclohex-1-enyl)-2-buten-1-one) were obtained according to the method of Example 1 of Chinese Patent CN104844431A; and dafurenone was obtained according to the method of Example 2 of Chinese Patent CN114573439A.

[0040] Other raw materials used in the examples are conventional reagents or materials, all of which are obtained through commercial channels.

[0041] The NMR spectra of the products obtained from each step of the reaction in the examples were determined by the following proton NMR spectroscopy method, using a Bruker Avance NMR spectrometer (500MHz), deuterated chloroform (CDCl3) as solvent, tetramethylsilane (TMS) as internal standard, 32 scans, 10ppm spectral width, and chemical shifts recorded using the δ-ppm scale.

[0042] The mass spectrometry of the products obtained from each step of the reaction in the examples was determined by the following gas chromatography-mass spectrometry (GC-MS): Instrument model: Agilent 8860-5977C GC-MS; Column: HP-FFAP; Injector temperature: 250℃; Carrier gas: High-purity helium (purity >99.999%); Carrier gas flow rate: 1.2 mL / min; Injection volume: 0.1 μL; Temperature program: Initial temperature 70℃ (hold for 2 min), then increase to 200℃ at 10℃ / min (hold for 20 min); Ion source: Electron impact ionization (EI); Ionization energy: 70 eV; Source temperature: 230℃; Scan mode: Full scan; Scan range: m / z 30-500; Data acquisition mode: Positive ion mode; Split ratio: 60:1; Solvent delay time: 4.5 min.

[0043] The purity of the products obtained from each step of the reaction in the examples was determined by the following gas chromatography method: using an Agilent 8860 gas chromatograph and an HP-FFAP column, the temperature was maintained at 70°C for 2 min, increased to 200°C at a rate of 10°C / min, and maintained at 200°C for 18 min. The purity was determined by the gas chromatography peak area normalization method, which is a commonly used method for determining purity in the fragrance and flavor industry.

[0044] Since the effects of aroma cannot be measured or evaluated using physicochemical parameters, the usual practice in this field is for professional fragrance evaluators to conduct sensory evaluations. In this application's embodiments, the sensory evaluation of the products obtained from each reaction step was performed by a senior and authoritative fragrance evaluator with over twenty years of experience. This evaluator has extensive expertise in fragrance sensory evaluation, formulation development, and quality control, and possesses high authority in the industry due to solid theoretical knowledge and a wealth of practical experience. Their evaluation conclusions are highly credible and widely accepted. The fragrance evaluation experiments were conducted in a professional fragrance evaluation laboratory that meets industry standards. Before the experiment, the laboratory underwent comprehensive ventilation and purification to completely eliminate environmental odors, dust, and other interference. During the experiment, the laboratory temperature was kept constant at 22±2℃, and the relative humidity was maintained at 50±5%. The room was free from direct airflow and external noise, and the lighting was soft and uniform, providing a standardized testing environment for the fragrance evaluation work. The experiment used standard fragrance evaluation paper (purchased from Guangzhou Zhengmao Printing Co., Ltd.) as the core evaluation medium. The sample of the aromatic composition to be tested was precisely dipped into the standard marking line on the evaluation paper. The paper, now dipped in the sample, was placed in front of the fragrance evaluator's nose at an appropriate position, and the top notes, middle notes, and base notes were evaluated one by one. The aroma type, intensity, harmony, longevity, and potential off-odors were systematically recorded. After each sample evaluation, sufficient olfactory recovery time was allowed before testing the next sample to avoid olfactory fatigue affecting the accuracy of the evaluation results. The evaluation method for longevity was as follows: the standard evaluation paper was dipped into the sample to be tested, and the initial time was recorded. The paper was then placed in a standard environment and allowed to stand. Professional fragrance evaluators smelled the paper at regular intervals, recording the changes in aroma until no obvious target aroma remained. Parallel tests were conducted, and the average value was taken to ensure accurate results.

[0045] Example 1: Synthesis of 3-methyl-1-(2,6,6-trimethylcyclohexyl-3-enyl)but-1-one and perfume formulation

[0046] 3-Methyl-1-(2,6,6-trimethylcyclohexyl-3-enyl)but-1-one 765 mL (2.30 mol) of methyl magnesium chloride solution (3 M in THF) was added to a 5000 mL four-necked flask equipped with a thermometer, mechanical stirrer, reflux condenser and drying tube. The mixture was heated to 35 °C with stirring, and 367 g (1.91 mol) of butyl dacrotone was added dropwise. The reaction temperature was controlled at 35-40 °C during the dropwise addition. After the dropwise addition was completed, the reaction was continued at 35-40 °C for 1 h.

[0047] Cool to below 30℃, add 2500g (1.28mol) of 5% sulfuric acid dropwise, stir for 30 minutes and let stand to remove the aqueous phase; wash the organic phase with 500mL of water 3-4 times, and rotary evaporate to obtain the crude product with a gas chromatographic purity of 97.98%.

[0048] The crude product was distilled under reduced pressure (<3 mmHg) in a precision distillation column, and the fraction collected at 103~108℃ was used to obtain 370 g of 3-methyl-1-(2,6,6-trimethylcyclohexyl-3-enyl)but-1-one, with a purity of 99.53% and a yield of 93.06%.

[0049] Product mass spectra (m / z): 208 (M+, 18), 123 (55), 107 (14), 91 (12), 85 (100), 81 (36), 57 (61), 43 (11), 41 (22).

[0050] Product NMR: 1H NMR (500 MHz, CDCl3) δ 5.46 (ddt, J = 9.9, 5.2, 2.2 Hz, 1H), 5.38 (ddt, J = 10.0, 3.1, 1.5 Hz, 1H), 2.45 (ddtt, J = 13.4, 6.7, 4.5, 2.1 Hz, 1H), 2.38 (dd, J = 18.0, 7.2 Hz, 1H), 2.23 (dd, J = 18.0, 6.0 Hz, 1H), 2.18 – 2.08 (m, 2H), 1.94 – 1.87 (m, 1H), 1.62 (ddt, J = 17.6, 5.4, 1.7Hz, 1H). 0.92 – 0.88 (m, 6H), 0.86 (dd, J = 6.8, 5.0 Hz, 6H), 0.81 (d, J =7.0 Hz, 3H).

[0051] Perfume Formulation: In this embodiment, the perfume, based on a total weight of 100 parts, comprises 12 parts of a fragrance base mixture, 0.5 parts of an antioxidant stabilizer, 22 parts of deionized water, and 65.5 parts of anhydrous ethanol. The fragrance base mixture consists of 3.5 parts of 3-methyl-1-(2,6,6-trimethylcyclohexyl-3-enyl)but-1-one, 2.0 parts of citronellol, 3.0 parts of phenylethyl alcohol, 1.5 parts of linalool, 1.5 parts of galena, and 0.5 parts of ambroxol. The antioxidant stabilizer consists of 0.3 parts of butylated hydroxytoluene and 0.2 parts of α-tocopherol. The preparation process involves accurately weighing each raw material according to its weight percentage. The entire fragrance base mixture is stirred at 25 rpm for 10 minutes to obtain a fragrance base premix. Two antioxidant stabilizer components are stirred at 20 rpm for 15 minutes to obtain a stabilizer premix. The two premixes are then added to anhydrous ethanol and stirred at 25 rpm for 25 minutes at 15°C to obtain an alcohol phase mixture. After being sealed and allowed to stand at room temperature for 48 hours, deionized water is added and stirred until homogeneous. The mixture is then aged in a sealed environment at 2°C for 3 weeks. Finally, it is filtered through an ultrafiltration membrane and bottled.

[0052] Fragrance Evaluation: This example is a pure, subtle, and minimalist fragrance. 3-Methyl-1-(2,6,6-trimethylcyclohexyl-3-enyl)but-1-one fully presents its elegant and gentle original scent, while simultaneously fulfilling the triple functions of setting the tone, blending the fragrance, and providing long-lasting fragrance. The overall fragrance is clean and transparent, without any sweet or powdery notes, closely resembling natural body odor, perfectly suited for the needs of a minimalist and subtle fragrance. The fragrance lasts up to 3 days.

[0053] Example 2: Synthesis of 3-methyl-1-(2,6,6-trimethylcyclohexyl-2-enyl)but-1-one and perfume formulation

[0054] 3-Methyl-1-(2,6,6-trimethylcyclohexyl-2-enyl)but-1-one The same synthesis steps as in Example 1 were followed, using methyl-Takitone as the reactant.

[0055] Product mass spectra (m / z): 208 (M+, 20), 123 (43), 91 (11), 85 (100), 81 (27), 57 (70), 41 (20).

[0056] Perfume Formulation: In this embodiment, the perfume, based on a total weight of 100 parts, comprises 13 parts of a fragrance base mixture, 0.6 parts of an antioxidant stabilizer, 20 parts of deionized water, and 66.4 parts of anhydrous ethanol. The fragrance base mixture consists of 2.5 parts of 3-methyl-1-(2,6,6-trimethylcyclohexyl-2-enyl)but-1-one, 0.8 parts of rose absolute, 2.2 parts of citronellol, 2.5 parts of phenethyl alcohol, 1.2 parts of geraniol, 1.0 part of lily of the valley aldehyde, 1.0 part of methyl dihydrojasmonate, and 1.8 parts of musk. The antioxidant stabilizer consists of 0.3 parts of butylated hydroxytoluene. The mixture consists of 0.3 parts of α-tocopherol. To prepare it, each raw material is accurately weighed according to the specified weight. All components of the fragrance base mixture are stirred at 25 r / min for 12 min to obtain a fragrance base premix. The two components of the antioxidant stabilizer are stirred at 20 r / min for 15 min to obtain a stabilizer premix. Then, the two premixes are added to anhydrous ethanol and stirred at 25 r / min for 30 min at 15℃ to obtain an alcohol phase mixture. After being sealed and allowed to stand at room temperature for 50 h, deionized water is added and stirred until homogeneous. The mixture is then sealed and aged at 2℃ for 4 weeks. Finally, it is filtered through an ultrafiltration membrane and bottled.

[0057] Fragrance Evaluation: This example is a delicate and elegant rose floral scent. 3-Methyl-1-(2,6,6-trimethylcyclohexyl-2-enyl)but-1-one serves as the core fragrance structure, neutralizing the sweet and powdery feel of traditional rose scents and creating a smoother transition between various floral notes. The overall fragrance is delicate and soft, possessing both natural floral texture and a subtle depth. It has stable longevity and is suitable for everyday use. The scent lasts up to 7 days.

[0058] Example 3: Synthesis of 3-methyl-1-(2,6,6-trimethylcyclohexyl-1-enyl)but-1-one and perfume formulation

[0059] 3-Methyl-1-(2,6,6-trimethylcyclohexyl-1-enyl)but-1-one The synthesis was performed using β-takitone as the reactant, following the same synthetic steps as in Example 1.

[0060] Product mass spectra (m / z): 208 (M+, 4), 152 (15), 151 (100), 123 (49), 81 (35), 41 (14).

[0061] Perfume Formulation: In this embodiment, the perfume, based on a total weight of 100 parts, comprises 11 parts of a fragrance base mixture, 0.4 parts of an antioxidant stabilizer, 21 parts of deionized water, and 67.6 parts of anhydrous ethanol. The fragrance base mixture consists of 2.5 parts of 3-methyl-1-(2,6,6-trimethylcyclohexyl-1-enyl)but-1-one, 1.2 parts of patchouli oil, 0.8 parts of vetiver oil, 1.0 part of sandalwood essential oil, 0.5 parts of coumarin, 1.5 parts of benzyl salicylate, 2.5 parts of galena, and 1.0 part of ambroxol. The antioxidant stabilizer consists of 0.2 parts of butylated hydroxytoluene. The mixture consists of 0.2 parts of α-tocopherol. To prepare it, each raw material is accurately weighed according to the specified weight. All components of the fragrance base mixture are stirred at 25 r / min for 15 min to obtain a fragrance base premix. The two components of the antioxidant stabilizer are stirred at 20 r / min for 15 min to obtain a stabilizer premix. Then, the two premixes are added to anhydrous ethanol and stirred at 25 r / min for 25 min at 15℃ to obtain an alcohol phase mixture. After being sealed and allowed to stand at room temperature for 48 h, deionized water is added and stirred until homogeneous. The mixture is then sealed and aged at 2℃ for 3 weeks. Finally, it is filtered through an ultrafiltration membrane and bottled.

[0062] Fragrance Evaluation: This example is a light and refreshing woody fragrance. 3-Methyl-1-(2,6,6-trimethylcyclohexyl-1-enyl)but-1-one breaks away from the heavy and bitter feel of traditional woody scents, giving the woody raw materials a clear and transparent texture, while balancing the fragrance notes and enhancing longevity. The overall fragrance is calm and not overpowering, elegant and sophisticated, suitable for those who seek a restrained and sophisticated fragrance. The scent lasts up to 3 days.

[0063] Example 4: Synthesis of 3-methyl-1-(2,6,6-trimethylcyclohexyl-1,3-dienyl)but-1-one and perfume formulation

[0064] 3-Methyl-1-(2,6,6-trimethylcyclohexyl-1,3-dienyl)but-1-one The synthesis was performed using datumene ketone as a reactant, following the same synthetic steps as in Example 1.

[0065] Product mass spectra (m / z): 206 (M+, 20), 150 (11), 149 (100), 122 (14), 121 (93), 120 (12), 105 (39), 91 (29), 85 (32), 79 (15), 77 (18), 57 (42), 41 (16).

[0066] Perfume Formulation: In this embodiment, the perfume, based on a total weight of 100 parts, comprises 10 parts of fragrance base mixture, 0.5 parts of antioxidant stabilizer, 20 parts of deionized water, and 69.5 parts of anhydrous ethanol. The fragrance base mixture consists of 1.5 parts of 3-methyl-1-(2,6,6-trimethylcyclohexyl-1,3-dienyl)but-1-one, 2.0 parts of bergamot oil, 1.2 parts of sweet orange oil, 0.3 parts of leaf ester acetate, 0.2 parts of leaf alcohol, 1.8 parts of linalool, 0.5 parts of citral, 1.0 part of musk, and 1.5 parts of ambroxol. The antioxidant stabilizer is butylated hydroxytoluene. Composed of 0.25 parts of α-tocopherol and 0.25 parts of other ingredients; In preparation, each raw material is accurately weighed according to the weight proportions. All components of the fragrance base mixture are stirred at 25 r / min for 10 min to obtain a fragrance base premix. The two components of the antioxidant stabilizer are stirred at 20 r / min for 15 min to obtain a stabilizer premix. The two premixes are then added to anhydrous ethanol and stirred at 25 r / min for 20 min at 15℃ to obtain an alcohol phase mixture. After standing at room temperature in a sealed container for 48 h, deionized water is added and stirred evenly. The mixture is then placed in a low-temperature environment at 2℃ and aged in a sealed container for 4 weeks. Finally, it is filtered through an ultrafiltration membrane and bottled to obtain the final product.

[0067] Fragrance Evaluation: This example is a crisp, refreshing, and aquatic citrus scent. 3-Methyl-1-(2,6,6-trimethylcyclohexyl-1,3-dienyl)but-1-one overcomes the common problems of short lasting fragrance and aroma gaps in traditional citrus scents, perfectly blending with fresh fruit and aquatic greenery. The overall fragrance is clean, crisp, and vibrant without being overpowering. The scent lasts up to 3 days.

Claims

1. An aromatic composition comprising a compound of formula I or an isomer or salt thereof: I in, R1, R2, R3, R4, and R5 are each independently selected from straight chains or branched chains C. 1-6 Alkyl groups, preferably selected from straight-chain or branched C4 groups. 1-4 Alkyl groups, more preferably selected from methyl, ethyl, n-propyl, and isopropyl, and even more preferably methyl; and Indicates a single or double bond, and three There must be at least one double bond and at most two double bonds. When there are two double bonds, the two double bonds are not adjacent to each other. The aromatic composition described therein is a perfume.

2. The aromatic composition according to claim 1, wherein the compound of formula I or its isomer or salt is selected from the group consisting of: 。 3. The aromatic composition according to claim 1 or 2, wherein the aromatic composition further comprises one or more of the following: antioxidant, chelating agent, opaque agent, preservative, solubilizer, fixative, colorant, pearlescent agent, and humectant.

4. A method for preparing an aromatic composition according to any one of claims 1-3, comprising the following steps: (1) Preparation of a compound of formula I or an isomer or salt thereof, comprising the step of reacting a compound of formula II or an isomer or salt thereof with a Grignard reagent: II, Among them, R1, R2, R3, R4 and The definition is the same as that in claim 1 or 2; as well as (2) Mix the compound of formula I or its isomers or salts with other components in the aromatic composition.

5. The method according to claim 4, wherein the compound of formula II or its isomer or salt is a compound of formula II-1 or formula II-2 or its isomer or salt: 。 6. The method according to claim 4, wherein the compound of formula II or an isomer or salt thereof is selected from the group consisting of: ； ； ； 。 7. The method according to any one of claims 4-6, wherein the Grignard reagent is R5-MgCl or R5-Li, wherein R5 is defined as in claim 1 or 2.

8. A method for obtaining or enhancing a fresh or subtle aromatic atmosphere, comprising using an aromatic composition according to any one of claims 1-3.

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