Bis(acetylthio)methane as a fragrance ingredient, a fragrance and a perfumed product comprising the same

Abstract

Use of bis(acetylthio)methane as a flavor ingredient, flavor comprising such flavor ingredient, and flavored product comprising bis(acetylthio)methane in an effective flavoring amount. Also use of it in combination with S,S-ethylidene ethylenedithioacetate, flavor and flavored product comprising the same.

Description

[0001] This application claims the benefit of European patent application EP23383224, filed on November 28, 2023. Technical Field

[0002] This invention relates to the field of fragrance ingredients, as well as fragrance-enhancing compositions and products containing them. Background Technology

[0003] Currently, fragrances are widely used in a large number of common consumer products, such as fine fragrances, personal care products, home care products, and air fresheners. This makes the fragrance industry increasingly in need of new fragrance ingredients that can provide new olfactory benefits.

[0004] A wide variety of scented materials are known for use in perfumes, including, for example, alkenes, alcohols, aldehydes, ketones, esters, ethers, nitriles, amines, oximes, acetals, ketals, thiols, thioketones, imines, etc.

[0005] US5871721 discloses S,S-ethylidene dithioacetate as an active flavoring ingredient and as a flavoring agent for various products such as food, beverages, chewing gum, toothpaste, or pharmaceutical preparations. According to the document, it has a natural sulfurous odor and possesses an appealing herbal quality and a leathery edge. The compound is described as a multi-scented product that also produces notes of garlic, onion, galbanum, or bergamot, reminiscent of bergamot leaf absolute, with a strong odor that can be used at very dilute concentrations and is also long-lasting.

[0006] In the fragrance industry, there is a continuous demand for new fragrance ingredients with novel olfactory properties that can produce interesting olfactory experiences and expand the possibilities of perfume production. Furthermore, when combined with other fragrance ingredients, those that achieve this primary function should preferably contribute to olfactory properties such as high intensity, long duration, high substantiality, odor-eliminating effects, or fragrance-enhancing properties, thereby obtaining new sensory effects from the fragrance composition.

[0007] Di(acetylthio)methane is known from polymer production and has also been used in the condiment industry. EP1090557A1 discloses a mixture of at least two sulfur molecules to obtain a meaty, savory condiment. The first molecule is a 2-methyl-3-furan-thio moiety. The second molecule is a molecule having the structure U-CH2-ST, which includes bis(acetylthio)methane, etc. As seen in Example 10 of this document, they are each present at a concentration of 1600 ppm in the condiment formulation. This is much higher than the amount used in spice formulations. The combined effect of the two groups of sulfur compounds in the final food results in a food with a strong flavor reminiscent of beef broth. It appears that the role of bis(acetylthio)methane in this combination is to enhance the meaty, beefy, savory effect of the 2-methyl-3-furan-thio moiety. However, those skilled in the art who wish to obtain a potent flavoring that can be used at very low concentrations will not find literature describing savory condiments, as the described sensory effects are far removed from those desired in spices. Furthermore, many flavoring molecules are simply not worth considering in terms of spices.

[0008] Finally, one phenomenon that severely disrupts attempts to correlate odor properties with molecular structure is that a given structural modification can cause a significant change in odor properties in one case, while having little or no effect in another. Therefore, despite extensive research on structure-odor relationships to date, predicting the odor of novel molecules remains a statistical endeavor, and models only provide probabilities of characteristics, thresholds, and intensities. Unexpected occurrences are still common, and serendipitous discoveries remain a significant factor in the discovery of novel aromatic molecules (see C.S. Sell, “On the Unpredictability of Odor”, Angew. Chem. Int-Ed. 2006, vol. 45, pp. 6254-6261). Summary of the Invention

[0009] The inventors have discovered that bis(acetylthio)methane (BATM) possesses unexpected perfume-making properties (contributing to descriptive terms such as hemp and sage) and intense strength at very low concentrations, making it effective as a fragrance ingredient. The compound is described individually by terms such as hemp, sage, mocha, fresh, yeasty, fermented, spicy, and leathery. The value of this compound lies in its ability to be used at very low doses while simultaneously possessing a very strong aroma and fragrance.

[0010] As shown in the examples, it has a very low odor threshold, and most importantly, it still has sensory effects when applied to fragrances; that is, this means that the fragrance benefits can be perceived when the compound is incorporated into fragrances at very low doses. Furthermore, its use at very low doses is advantageous because of its small volume, and because the product can be used as a concentrate, which can then be reformulated.

[0011] Although bis(acetylthio)methane can be considered structurally similar to S,S-dithioacetate ethylene, which has been described as an active flavoring or flavoring ingredient in US5871721, no successful expectation is made that bis(acetylthio)methane may have flavoring properties, because it is well known in the fragrance industry that it is very difficult to correlate olfactory properties with molecular structures, as small structural differences can have huge and unpredictable effects on the activity of compounds.

[0012] Furthermore, the olfactory properties of di(acetylthio)methane (with hemp and green notes) are very different from those of S,S-dithioacetate (a tropical, sulfurous odor with hints of garlic, onion, galbanum, or bergamot, reminiscent of lemon leaf), and this difference cannot be predicted by differences in molecular structure. The fact that di(acetylthio)methane possesses an unexpectedly strong odor (much stronger than most known fragrance ingredients) is even more unpredictable, not to mention the effect on sensory perception when applied in very low doses to fragrances.

[0013] Therefore, a first aspect of the present invention relates to the use of bis(acetylthio)methane (BATM) as a flavoring ingredient, particularly, said flavoring ingredient having a hemp and green aroma. It has the following CAS registration number: 1618-26-4, and the following formula (I):

[0014] (I)

[0015] As a fragrance component, bis(acetylthio)methane can be used alone as an olfactory active compound that exhibits such hemp and green aromas.

[0016] The inventors also discovered that when S,S-dithioethyl acetate (SSEDT) of formula (II) is added to the fragrance ingredients, an aroma adjustment is observed. A minty / fresher scent emerges, and the "hemp" characteristic is described as more authentic.

[0017]

[0018] (II)

[0019] Therefore, the use of the combination of bis(acetylthio)methane and S,S-dithioacetate ethylene ester (SSEDT) of formula (II) as a fragrance ingredient is also part of this invention. This use includes using a fragrance ingredient comprising both components simultaneously, or using two separate fragrance ingredients targeting each individual component. S,S-dithioacetate ethylene ester acts to modulate the odor of bis(acetylthio)methane in the fragrance ingredient, providing the fragrance with a hemp-like aroma and a minty / fresher note.

[0020] Another aspect of the invention relates to a fragrance ingredient comprising bis(acetylthio)methane and S,S-dithioacetate ethylene. Both compounds act as olfactory active compounds.

[0021] Another aspect of the invention relates to a fragrance comprising at least two fragrance components, wherein one of the fragrance components comprises bis(acetylthio)methane, and optionally, the other fragrance component comprises ethylene S,S-dithioacetate. The invention also relates to a fragrance comprising at least two fragrance components, wherein one of the fragrance components comprises both bis(acetylthio)methane and ethylene S,S-dithioacetate.

[0022] The fragrance ingredients according to the invention are suitable for use in both fine perfumes and functional applications as flavor enhancers. Therefore, a final aspect of the invention relates to flavor enhancers comprising an effective amount of the fragrance ingredient as defined above, more specifically, an effective amount of a fragrance ingredient comprising bis(acetylthio)methane, optionally comprising an effective amount of another fragrance ingredient comprising S,S-dithioacetate ethylene, or alternatively, an effective amount of a fragrance ingredient comprising both bis(acetylthio)methane and S,S-dithioacetate ethylene. Attached Figure Description

[0023] Figure 1 The dose-response curves for the receptor TRPA1 and its mimic are shown. They represent the change in fluorescence signal (receptor activation) as the concentration of BATM in the culture medium increases. For TRPA1, EC... 50 = 4.2 µm and E max Start from 11.7 µm. Detailed Implementation

[0024] definition: As used herein, the term "olfactory active compound" is synonymous with "fragrance active compound" or "odor active compound" and refers to a compound that provides a desired odor.

[0025] The term "fragrance ingredient," also synonymous with "perfume ingredient," is understood to refer to any single material containing one or more olfactory active compounds to produce a desired pleasant effect. A fragrance ingredient itself may comprise a number of individual organic chemical compounds, some of which may or may not be considered olfactory active compounds for the desired effect. For the purposes of this invention, the fragrance ingredient comprises bis(acetylthio)methane as an olfactory active compound, or bis(acetylthio)methane in combination with S,S-dithioacetate ethylene as an olfactory active compound. These olfactory active compounds are responsible for producing the desired pleasant odor of the fragrance according to the invention.

[0026] The terms “fragrance” and “perfume” are used interchangeably herein, and they refer to mixtures of olfactory active compounds that may, if desired, contain auxiliary substances such as additives or carriers. In the context of this invention, the terms “fragrance” and “perfume” refer to mixtures of fragrance ingredients according to the invention, which may contain other olfactory active compounds and may also contain auxiliary substances such as additives or carriers.

[0027] As used herein, "fragrance-enhancing product" or "consumer product" means a product intended for use or consumption in its present form, not for modification for subsequent commercial manufacture or resale. Fragrance-enhancing products according to the invention can be fine fragrances, air care products, cosmetics, personal care products (e.g., body sprays), detergents and fabric softeners, carpet cleaners, air fresheners, textiles and soft furnishings, deodorizing or odor-eliminating products, odor-controlling products, or scented articles.

[0028] The flavoring ingredients of this invention are not intended for use in consumer products intended to be ingested (e.g., food or beverages), nor are they intended for use in consumer products that may be partially ingested due to the method of use (e.g., toothpaste or mouthwash), nor are they intended for use in products that may be accidentally ingested (e.g., chewing gum).

[0029] As used herein, "effective flavoring amount of a flavoring ingredient" refers to the amount of flavoring ingredient that provides the desired pleasant odor when included in a consumer flavoring product. The specific amount of the flavoring ingredient according to the invention will, of course, be determined by the specific consumer product containing the flavoring ingredient, which may be a single olfactory active compound or a combination of olfactory active compounds that provide the desired pleasant odor. In the context of the invention, when the flavoring ingredient contains only bis(acetylthio)methane, the desired pleasant odor is a hemp and green aroma, or when the flavoring ingredient also contains ethylene dithioacetate, the desired pleasant odor is a hemp and minty / fresher note. Thus, in both cases, the flavoring ingredient of the invention provides a distinctive hemp aroma.

[0030] As used in this article, the term "hemp" refers to a variant of the genus *Hydrocotyle*.

[0031] As mentioned above, the use of di(acetylthio)methane as a fragrance ingredient constitutes part of this invention. As noted in the examples, the most frequently repeated descriptive terms perfumers use for this fragrance ingredient are hemp, green, mocha, fresh, yeasty / fermented, spicy, and leathery. In specific embodiments of the use, the fragrance ingredient exhibits hemp and green aromas. This aspect of the invention can be expressed as a method of providing a hemp and green aroma to a fragrance or flavoring product, said method comprising adding an olfactorily effective amount of di(acetylthio)methane as a fragrance ingredient.

[0032] As shown in the example, bis(acetylthio)methane (BATM) has the ability to activate the trigeminal nerve. These nerves transmit somatic sensory information from the face (including the mouth and nose) to the brain. They are responsible for detecting sensations such as temperature, texture, or pain. These receptors can be activated by chemical compounds, a process known as chemesthesis or chemical touch, which can significantly contribute to the overall odor experience. Specifically, this molecule has the ability to activate the trigeminal receptor TRPA1 (transient receptor potential cation channel subfamily A, member 1), whose relationship with the generation of some somatic sensations in the nose and mouth (e.g., tingling or irritation) has been described (see Nilius, Bernd; Flockerzi, Veit. (2014). [Handbook of Experimental Pharmacology] Mammalian Transient Receptor Potential (TRP) Cation Channels Volume 223 || TRPs in Taste and Chemesthesis (Chapter 5), 827–871). This compound can modulate olfactory signals and alter the odor experience. Furthermore, this compound has high specificity and potency for TRPA1, and no off-target effects were observed. This indicates that BATM can activate the trigeminal receptor TRPA1 associated with nasal tingling (see Example 5).

[0033] Therefore, in a particular embodiment of the use of bis(acetylthio)methane of formula (I) as a fragrance ingredient, in combination with any of the embodiments above or below, bis(acetylthio)methane of formula (I) also acts to activate the trigeminal nerve receptor TRPA1 associated with tingling sensation in the nose.

[0034] The compound also enhanced the freshness of various odor materials and the olfactory intensity of various odor materials (e.g., lemon oil, spearmint oil, clove oil, and basil oil). (See Examples 6 and 7).

[0035] Therefore, in a specific embodiment of the use of bis(acetylthio)methane of formula (I) as a fragrance ingredient, bis(acetylthio)methane of formula (I) has an enhancing effect on freshness.

[0036] In another specific embodiment of the use of bis(acetylthio)methane of formula (I) as a fragrance ingredient, in combination with any of the embodiments above or below, bis(acetylthio)methane of formula (I) enhances the olfactory intensity of other odorous materials, or both. In a more specific embodiment, the odorous material is selected from lemon oil, spearmint oil, clove oil, and basil oil.

[0037] The fragrance ingredient may also contain S,S-dithioacetate ethylene ester. The use of such a fragrance ingredient comprising bis(acetylthio)methane and S,S-dithioacetate ethylene ester, as well as combinations of bis(acetylthio)methane and S,S-dithioacetate ethylene ester, as a fragrance ingredient is also part of this invention, wherein said use includes the combined use of a fragrance ingredient comprising both components, or the use of two separate fragrance ingredients targeting each individual component. This final aspect of the invention can also be expressed as a method of providing a hemp scent and a minty / fresher fragrance to a fragrance or flavoring product, said method comprising adding an olfactorily effective amount of bis(acetylthio)methane and S-dithioacetate ethylene ester as a fragrance ingredient, wherein said method includes the use of a fragrance ingredient comprising both components simultaneously, or the use of two separate fragrance ingredients targeting each individual component.

[0038] In a specific embodiment of the use as defined above, the fragrance ingredient is encapsulated. Encapsulation can be used to protect the ingredient from interacting with other ingredients in the product (e.g., bleach) or to control the delivery of the fragrance, thereby providing the consumer with a better experience through the use of the product. Capsules containing the ingredient can be prepared by any generally known technique, such as spray drying as described in WO2014118354, interfacial reactions (e.g., amine-aldehyde polycondensation) as described in US6261483, free radical polymerization as described in EP2234712, or aggregation of polymers with opposite charges as described in US2800457.

[0039] Depending on the ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene, the flavoring ingredient produces different aroma notes, and while some ratios may be more suitable for certain flavoring products, others may be better suited for others. Therefore, this flavoring ingredient offers an interesting olfactory profile, with a green / hemp character as the primary aspect, which can be further adjusted as needed by varying the ratio between the two olfactory active compounds to produce other aroma notes such as "spicy," "leather," "mint," "grapefruit," or "cassis."

[0040] In a particular embodiment, the fragrance component comprising the composition according to the invention is a fragrance component wherein S,S-dithioacetate ethylene ester comprises 5% to 95% of the total weight of the fragrance component. In another particular embodiment, S,S-dithioacetate ethylene ester comprises 5% to 17% of the total weight of the fragrance component. In yet another particular embodiment, S,S-dithioacetate ethylene ester comprises 10% to 12% of the total weight of the fragrance component.

[0041] In a specific embodiment, the weight ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene ester in the fragrance component is from 19:1 to 1:19. In another specific embodiment, the weight ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene ester is from 7.5:1 to 1:7.5. In another specific embodiment, the weight ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene ester is from 7.5:1 to 1:6. In another specific embodiment, the weight ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene ester is from 7.5:1 to 1:1. In another specific embodiment, the weight ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene ester is from 6:1 to 1:1. In another specific embodiment, the weight ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene ester is 7.5:1. In another specific embodiment, the weight ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene is 1:1.

[0042] The fragrance components of the present invention, which contain only bis(acetylthio)methane or also S,S-dithioacetate ethylene, can be used to produce very broad-spectrum fragrances by mixing them with other compounds having olfactory properties and optional additives or carriers.

[0043] Alternatively, a fragrance comprising at least two fragrance components, wherein one of the fragrance components comprises bis(acetylthio)methane, and optionally, other fragrance components comprise S,S-dithioacetate ethylene ester, or alternatively, a fragrance comprising at least two fragrance components, wherein one of the fragrance components comprises bis(acetylthio)methane and S,S-dithioacetate ethylene ester, is part of this invention.

[0044] In a particular embodiment, the fragrance according to the invention is a fragrance that contains a fragrance ingredient, wherein the fragrance ingredient contains bis(acetylthio)methane as the sole olfactory active ingredient.

[0045] In another specific embodiment, the fragrance according to the invention is a fragrance comprising one fragrance ingredient and another fragrance ingredient, wherein the one fragrance ingredient comprises bis(acetylthio)methane as the sole olfactory active ingredient, and the other fragrance ingredient comprises S,S-dithioacetate ethylene ester as the sole olfactory active ingredient.

[0046] In another specific embodiment, the fragrance according to the invention is a fragrance containing a fragrance ingredient comprising bis(acetylthio)methane and S,S-dithioacetate ethylene ester as the sole olfactory active ingredient.

[0047] In another specific implementation, in combination with any of the above implementations, the flavoring contains suitable additives or carriers.

[0048] The fragrance of the present invention may contain additional olfactory active compounds. A wide variety of olfactory active compounds are known to be used in perfumery applications, including a broad range of currently available natural and synthetic products, such as alcohols, aldehydes, ketones, essential oils, ethers and acetals, esters, lactones, macrocyclic compounds, heterocyclic compounds, alkenes, ethers, nitriles, amines, oximes, ketals, thiols, thioketones, imines, and mixtures thereof.

[0049] To avoid limitations, compounds containing fragrance ingredients typically have a molecular weight of less than 325 atomic mass units, preferably less than 300 atomic mass units, and more preferably less than 275 atomic mass units, to ensure sufficient volatility to be detectable. Furthermore, the compounds have a molecular weight greater than 75 atomic mass units, preferably greater than 100 atomic mass units, because lower masses may be too volatile. It is further preferred that the boiling point of each fragrance ingredient is between 80°C and 400°C, for example, between 100°C and 350°C, when measured at 760 mm Hg. The fragrance ingredients do not contain strongly ionized functional groups (e.g., sulfonates, sulfates, or quaternary ammonium ions) or halogen atoms.

[0050] The fragrances of the present invention may optionally contain other natural extracts, such as essential oils. Natural extracts are produced by subjecting suitable natural materials (e.g., plant components: leaves, flowers, seeds, roots, or stems) to an extraction process. Extraction processes are well known to those skilled in the art. Essential oils may undergo additional processes to distill and purify the oil, for example, by removing terpene components via a “head cut” and / or wax components via a “tail cut.” Such natural extracts include, but are not limited to, those obtained from citrus fruits, such as lemon, orange, mandarin orange, grapefruit, and other unsightly fruits; from species such as fennel, cinnamon, clove, herbs such as basil, peppermint, lavender, bright lavender, thyme, rosemary; or various plants such as bay leaves, various roses, lemongrass, cypress, eucalyptus, Peru balsam, camphor, sandalwood, ylang-ylang, cedar, and mixtures thereof.

[0051] Perfume compositions can be relatively simple, containing at least two fragrance ingredients, or they can comprise a highly complex mixture of natural and synthetic chemical compounds selected to provide any desired scent. For creative purposes, it is preferred if the perfume composition contains more than five fragrance ingredients, and more preferably, it contains more than ten fragrance ingredients. Fragrance ingredients are well known in the art.

[0052] Examples of fragrance ingredients include, but are not limited to: hydrocarbons such as 3-carene; α-pinene; ββ-pinene; α-terpinene; γ-terpinene; p-isopropyltoluene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; or (E,Z)-1,3,5-undecanetriene; aliphatic alcohols such as hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol; (E)-2-hexenol; (E)-3-hexenol and (Z)-3-hexenol; 1-octen-3-ol; 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methylene Mixtures of methylhept-2-ols; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoct-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; aliphatic aldehydes and their acetals, such as hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronelloloxyacetaldehyde; aliphatic ketones and Oximes, such as 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; aliphatic sulfur-containing compounds, such as 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexylbutyrate; 3-acetylthiohexyl acetate; 1-menthol-8-thiol; aliphatic nitriles, such as 2-nonenonitrile; 2-tridecenoenonitrile; 2,12-tridecenoenonitrile; 3,7-dimethyl-2,6-octadienonitrile; 3,7-dimethyl-6-octenonitrile; aliphatic carboxylic acids and their esters, such as (E)-3-hexenyl formate and (Z)-3-hexenyl formate; ethyl acetoacetate Esters; Isoamyl acetate; Hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)-hexenyl acetate and (Z)-3-hexenyl acetate; Octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; Ethyl butyrate; Butyl butyrate; Isoamyl butyrate; Hexyl butyrate; (E)-3-hexenyl isobutyrate and (Z)-3-hexenyl isobutyrate; Hexyl crotonate; Ethyl isovalerate; Ethyl-2-methylvalerate; Ethyl hexanoate; Allyl hexanoate; Ethyl heptaate; Allyl heptaate; Ethyl octanoate; (E,Z)-2,4-decadienoate; Methyl 2-octynoate; Methyl 2-nonynoate; 2-isopentyloxyallylic acetate.3,7-Dimethyl-2,6-octadienoic acid methyl ester; terpene alcohols, such as citronellol; geraniol; nerol; linalool; lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloct-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octtrien-3-ol; 2,6-dimethyl-2,5,7-octtrien-1-ol; and their formate, acetate, propionate, and isocyanate esters. Butyrate, butyrate, isovalerate, valerate, hexanoate, crotonate, terpenoid, and 3-methyl-2-butenoate; terpenoid aldehydes and ketones, such as geranialdehyde; neraldehyde; citronellol; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geraniol; and dimethyl acetals and diethyl acetals of geranialdehyde, neraldehyde, and 7-hydroxy-3,7-dimethyloctanal; cyclic terpenoid alcohols, such as menthol; isopreneol; α-terpineol; terpinenol-4; menthane-8-ol; menthane-1-ol; menthane-7-ol; borneol; isoborneol; linalool oxide; noberol; cedrol; ambroxol; vetiverol; guaiacol; and others. Formate, acetate, propionate, isobutyrate, butyrate, isovalerate, valerate, hexanoate, crotonate, terpene acid ester, and 3-methyl-2-butenoate; cyclic terpenoids and ketones, such as menthone; isomenthone; 8-mercaptomenthane-3-one; carvone; camphor; anisone; α-ionone; β-ionone; α-n-methylionone; β-ethylionone; α-isomethylionone; β-isomethylionone; α-irisone; α-dihydrodamasone; β-dihydrodamasone; β-damasenoene; γ-dihydrodamasone; δ-dihydrodamasone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro -1,1,5,5-Tetramethyl-2H-2,4a-methylenenaphthalene-8(5H)-one; Nocacolone; Dihydronocacolone; α-Sweet Orange Aldehyde; β-Sweet Orange Aldehyde; Methyl Citrullone; Cyclic alcohols, such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocampylcyclohexanol; 2,6,9-trimethyl-(Z2,Z5,E9)-cyclododecanetrien-1-ol; 2-Isobutyl-4-methyltetrahydro-2H-pyran-4-ol; From alicyclic alcohols, such as α,3,3-trimethyl-cyclohexylmethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopentan-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopentan-1-yl)-2-buten-1-ol;2-Ethyl-4-(2,2,3-trimethyl-3-cyclopentan-1-yl)-2-buten-1-ol; 3-Methyl-5-(2,2,3-trimethyl-3-cyclopentan-1-yl)-pentan-2-ol; 3-Methyl-5-(2,2,3-trimethyl-3-cyclopentan-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopentan-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; cyclic ethers, such as eucalyptol; methyl cedarwood ether; cyclododecyl methyl ether; (ethoxymethoxy)cyclododecane; α-cedrene epoxide; 3a, 6,6,9a-Tetramethyldodecanonaphtho[2,1-b]furan; 3a-Ethyl-6,6,9a-Trimethyldodecanonaphtho[2,1-b]furan; 1,5,9-Trimethyl-13-oxabicyclo[10.1.0]tetrazol-4,8-diene; Rosine; 2-(2,4-Dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane; Cyclic ketones, such as 4-tert-butylcyclohexanone; 2,2,5-Trimethyl-5-pentylcyclopentanone; 2-Heptylcyclopentanone; 2-Pentylcyclopentanone; 2-Hydroxy-3-methyl-2-cyclopenten-1-one; 3-Methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-Methyl-2-penten-1-one 2-Cyclopenten-1-one; 3-Methyl-4-cyclopentadecenone; 3-Methyl-5-cyclopentadecenone; 3-Methylcyclopentadecenone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 9-cycloheptadecene-1-one; cyclopentadecenone; cyclohexadecone; alicyclic aldehydes, such as 2,4-dimethyl-3-cyclohexenaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenaldehyde; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenaldehyde; 4-(4-methyl-3-penten-1-yl)- 3-Cyclohexenaldehyde; alicyclic ketones, such as 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthylmethyl ketone; 2,6,10-trimethyl-2,5,9-cyclododecathitrylmethyl ketone; 2,4-dimethyl-3-cyclohexen-1-yl tert-butyl ketone; esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate;Decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-bridged methylene-3a,4,5,6,7,7a-hexahydro-5- or -6-indanyl acetate; 4,7-bridged methylene-3a,4,5,6,7,7a-hexahydro-5- or -6-indanylpropionate; 4,7-bridged methylene-3a,4,5,6,7,7a-hexahydro-5- or -6-indanyl isobutyrate; 4,7-bridged methylene octahydro-5- or -6-indanyl acetate; esters of alicyclic carboxylic acids, such as allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl dihydrojasmonate; methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate. ; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-ethyl acetate; aromatic hydrocarbons, such as styrene and diphenylmethane; aryl aliphatic alcohols, such as benzyl alcohol; 1-phenylethanol; 2-phenylethanol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol; aryl aliphatic alcohols and aliphatic carboxyl groups Esters of acids, such as benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; α-trichloromethylbenzyl acetate; α,α-dimethylphenylethyl acetate; α,α-dimethyl-phenylethylbutyrate; cinnamic acid ester; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; aryl ethers, such as 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl-1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydrogenated atroaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4 a,5,9b-tetrahydroindo[1,2-c]-me-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindo[1,2-d]-me-dioxin; aromatic aldehydes and aliphatic aldehydes, such as benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydrogenated atroaldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; α-butylcinnamaldehyde; α-pentylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde;4-Hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal; aromatic ketones and aliphatic ketones, such as acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)ethyl ketone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanylmethyl ketone; 142,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl) )-1H-indanyl ethyl ketone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-naphthyl ethyl ketone; aromatic carboxylic acids and aryl aliphatic carboxylic acids and their esters, such as benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenyl acetate; ethyl phenyl acetate; geranyl phenyl acetate; phenylethyl phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenoxyacetic acid allyl ester; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; 2,4-dihydroxy-3,6-dimethylbenzoate; 3- Ethyl phenylglycine; 3-methyl-3-phenylglycine; nitrogen-containing aromatic compounds, such as 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 5-phenyl-3-methyl-2-pentenonitrile; 5-phenyl-3-methylpentenonitrile; methyl anthranilate; N-methyl anthranilate; Schiff base of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexene-carboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; indole; methylindole; 2-methoxy-3-isopropylpyrazine; 2- Isobutyl-3-methoxypyrazine; 4-(4,8-dimethyl-3,7-nonadienyl)pyridine; phenols, phenyl ethers and phenyl esters, such as artemisia argyi; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthylmethyl ether; β-methylethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenol acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-tolylphenyl acetate; from heterocyclic compounds, such as 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one;2-Ethyl-3-hydroxy-4H-pyran-4-one; lactones, such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-lactone; 1,4-undecanelide; 1,4-dodecanelide; 1,5-decanelide; 1,5-dodecanelide; 1,15-pentadecanolate; cis- and trans-11-pentadecane-1,15-lactone; cis- - and trans-12-pentadecane-1,15-lactone; 1,16-hexadecyl lactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecyl lactone; 11-oxa-1,16-hexadecyl lactone; 12-oxa-1,16-hexadecyl lactone; ethylene-1,12-dodecanoic acid ester; ethylene glycol 1,13-tetrazanoic acid; coumarin; 2,3-dihydrocoumarin; or octahydrocoumarin.

[0053] In another specific embodiment, the fragrance also includes a suitable carrier or additive. A suitable carrier or additive refers to a conventional additive or carrier used in the fragrance. Examples of additives are surfactants, UV stabilizers, or antioxidants.

[0054] Examples of surfactants used to dissolve fragrances into some products include alcohol ethoxylates, sugar ethers and sugar esters, alkyl glycerides and amine oxides.

[0055] Examples of UV stabilizers include butyl methoxybenzoylmethane; bis(ethylhexyloxyphenol)methoxyphenyltriazine; those marketed under the trade name Uvinol (registered trademark), such as Uvinul D50 [bis(2,4-dihydroxyphenyl)-methyl ketone], Uvinul MC80 (ethylhexyl methoxycinnamate), and Uvinul M40 (benzophenone-3); those marketed under the trade name Parsol (registered trademark), such as Parsol MCX (the same product as Uvinul MC80) and Parsol 1789 (butyl methoxybenzoylmethane); and those marketed under the trade name Tinogard (registered trademark), such as Tinogard TT (pentaerythritol tetra(-di-tert-butylhydroxyhydrocinnamate) ester).

[0056] Examples of antioxidants include hindered phenols, such as butylated hydroxytoluene, butylated hydroxyanisole, tocopherols and their derivatives (e.g., α-tocopheryl acetate (vitamin E)), alkyl gallate esters (e.g., propyl gallate), and 3,5-di-tert-butyl-4-hydroxycinnamate.

[0057] Examples of suitable carriers are solvents, such as alcohols, including ethanol, propanol, isopropanol, butanol, dipropylene glycol, diethyl phthalate, benzyl benzoate, isopropyl myristate, glyceryl triacetate, and triethyl citrate (TEC). Other examples of suitable solvents include hydrocarbons, such as those sold under the trade name Isopar (registered trademark); ethers, such as those sold under the trade name Dowanol (registered trademark): benzyl benzoate; isopropyl myristate; dialkyl adipate; dialkyl succinate; dialkyl glutarate, such as dimethyl glutarate sold under the trade name Flexisolv (registered trademark); citrates, such as triethyl citrate and acetyl tributyl citrate; diethyl phthalate; diethylene glycol monoethyl ether; 3-methoxy-3-methyl-1-butanol; dipropylene glycol; and isopropylglycerin sold under the trade name Augeo (registered trademark) Clean Multi.

[0058] These solvents can be used alone or in combination. Typically, the solvents are odorless or have a very low odor and contribute little to the overall aroma of the fragrance.

[0059] Flavoring products containing the following ingredients are part of this invention: an effective amount of flavoring ingredient as defined above, more specifically, an effective amount of flavoring ingredient containing bis(acetylthio)methane, optionally containing an effective amount of another flavoring ingredient containing S,S-dithioacetate ethylene ester, or alternatively, an effective amount of flavoring ingredient containing both bis(acetylthio)methane and S,S-dithioacetate ethylene ester.

[0060] Fragrance-enhancing products can be selected from fine fragrances, air care products, cosmetics, personal care products, detergents and fabric conditioners, household cleaners, carpet cleaners, air fresheners, textiles and soft furnishings, deodorizing or odor-eliminating products, odor control products, and scented items.

[0061] The amount of the fragrance ingredient (bis(acetylthio)methane alone or also containing S,S-dithioacetate ethylene) in the flavoring product according to the invention can be selected based on the intended use of the flavoring product and the desired aroma of the product. In a particular embodiment, the flavoring product according to the invention is a product in which the fragrance ingredient according to the invention is present in an amount equal to or less than 10 ppm. In another particular embodiment, the flavoring product according to the invention is a product in which the fragrance ingredient is present in an amount equal to or less than 5 ppm. In yet another particular embodiment, the flavoring product according to the invention is a product in which the fragrance ingredient is present in an amount equal to or less than 1 ppm.

[0062] In another specific embodiment, the flavoring product according to the invention is a product in which the flavoring ingredient is present in an amount of 0.005 ppm to 10 ppm, particularly 0.01-5 ppm. These amounts are the effective amounts that provide the desired aroma described by the flavoring ingredient of the invention.

[0063] In a particular embodiment, the flavoring product according to the invention is a product in which the flavoring ingredient of the invention is added in the form of a flavoring, the flavoring comprising the flavoring ingredient and other olfactory active compounds, and optionally comprising additives or carriers.

[0064] Such fragrance products include, but are not limited to, fine fragrances such as eau de parfum and cologne; household cleaning products; air care products; cosmetic products; personal care products; detergents and fabric conditioners; carpet cleaners; air fresheners such as in-place air fresheners and aerosol products; textiles and soft furnishings; deodorizing or olfactory removal products; odor control products; and scented items.

[0065] Fine fragrances contain fragrance components in a solvent and are typically applied to the skin via some form of spray applicator. A more concentrated solution of fine fragrance is called eau de toilette, which typically contains up to 20% of the fragrance composition. Eau de Toilette typically contains up to 15% of the fragrance composition, and body spray typically contains up to 5%.

[0066] Specific examples or fragrance products are products and / or methods used for and / or involving the treatment of hair (human, dog and / or cat), including bleaching, coloring, dyeing, conditioning, shampooing, styling; products applied to the skin, including eau de toilette, cologne, body spray, deodorant and antiperspirant; personal hygiene products, such as bar soaps, liquid soaps, shower gels, body washes and scrubs; cosmetics left on the skin for skin care, including creams, lotions, coloring cosmetics and other topical products; and shaving products.

[0067] Specific examples of personal care products include, for example, shampoos and hair conditioners, shower gels (such as exemplified shower gels), liquid soaps, soap bars, deodorant sprays (such as exemplified roll-on and stick deodorants), and wipes (including baby wipes, rinseable wet toilet paper, and skin cleansing or refreshing wipes). Formulations and ingredients of personal care products in which the fragrances of this invention may be used are well known to those skilled in the art.

[0068] Fabric products include those used in laundry detergents and garment care products, such as powdered, liquid, and unit-dose detergents, detergent additives, fabric softeners, drum dryer sheets, ironing sprays, and fabric fresheners; and products for treating soft household furnishings, such as carpet cleaners and deodorizers. Products for hard surfaces include manual and machine dishwashing products, hard surface cleaners for floors, walls, windows, and mirrors, and bathroom cleaners.

[0069] Specific examples of laundry detergents and conditioners include detergent powders, tablets, non-soap detergent bars and hard soap bars, concentrated detergent powders, liquid detergents, concentrated liquid detergents, non-aqueous liquid detergents, and unit-dose liquid detergent sachets. Other post-wash fabric treatments include tumble dry sheets or ironing water. The formulation of laundry products is familiar to those skilled in the art.

[0070] Specific examples of household cleaners include liquid and spray hard surface cleaners that can be applied directly to surfaces, diluted liquids such as those for cleaning floors or dishes and cooking utensils, and single-dose solid or liquid sachets or sheets, such as products for machine washing and specialized cleaners for glass and mirrors. These products are available in various forms, such as sprays, mousses, liquids, liquids containing suspended solids, soaked wipes, sachets, multi-compartment sachets, and single-dose devices. Bathroom fixture cleaners include limescale removers, tank blocks, toilet bowl blocks, liquid toilet bowl blocks, and mixed products.

[0071] Specific examples of air-care products that introduce fragrance into the ambient air of enclosed spaces (such as rooms, vehicles, closets, boxes, drawers, etc.) can typically be in the form of sprays, candles, gels, membrane permeation devices, plug-in electrical devices, battery-powered devices, or liquid wicking devices. Sprays can be water-based or non-water-based and are pressurized using compressed gas or pump action. Candles and gels can be opaque, translucent, or transparent and can be molded or packaged or contain additional ingredients to enhance their appearance. Plug-in and battery-powered devices can include those that evaporate fragrance through heating, evaporation, or atomization.

[0072] Other products used to freshen or fragrance general ambient air, neutralize odors, or repel insects include devices that operate without a power source and by diffusion (e.g., through a polymer membrane) or by electrically heating a wicking element in contact with a liquid reservoir, thereby allowing control over the release rate of fragrance. Such devices can be electrically powered, i.e., so-called plug-in air fresheners, or battery-powered, and therefore portable or for use in motor vehicles.

[0073] Specific examples of carpet cleaners come in several forms: powder, liquid, foam, and spray treatment. Many of these products must be used in conjunction with specific cleaning machines, especially when dealing with large areas. However, the desired property for cleaning carpets is to reduce odor and leave a pleasant scent, and such products typically contain fragrances. The odor-reducing fragrance of the present invention is suitable and ideal for use in carpet cleaning products.

[0074] bis(acetylthio)methane is a known compound that can be prepared, for example, by the reaction of diiodomethane with potassium thioacetate. An example of its preparation is disclosed in Example 1 of EP1090557.

[0075] S,S-dithioacetic acid ethylene ester was first discovered in blood orange. This compound can be prepared by a condensation reaction between thioacetic acid and acetaldehyde. This synthesis is described, for example, by L. Sternson in “1,1-Bis(acylthio)alkanes Formed by Bae-Catalyzed Condensation of Thiol Acids”, J. Org. Chem., 1978, vol. 43, No. 23, in which the condensation reaction between thioacetic acid and acetaldehyde is carried out in an ether containing triethylamine or pyridine (see the experimental section of the aforementioned literature).

[0076] Fragrances and flavoring products containing both bis(acetylthio)methane and S,S-dithioacetate ethylene can be prepared using conventional techniques.

[0077] Fragrances containing two olfactory active compounds can be prepared by mixing these compounds with, optionally, other additives or carriers.

[0078] To prepare flavoring products, bis(acetylthio)methane can be introduced into the flavoring product by mixing it with the other components of the flavoring product.

[0079] When a flavoring product contains two flavorings (bis(acetylthio)methane and S,S-dithioacetate ethylene ester), it can also be prepared by incorporating a flavoring ingredient containing bis(acetylthio)methane and S,S-dithioacetate ethylene ester.

[0080] Throughout the specification and claims, the word "comprising" and variations thereof are not intended to exclude other technical features, additives, components, or steps. Furthermore, the word "comprising" includes cases where it means "composed of...". Other objects, advantages, and features of the invention will become apparent to those skilled in the art upon reading the specification, or may be learned by practicing the invention. The examples below are provided by way of illustration and are not intended to limit the invention. Moreover, the invention covers all possible combinations of the specific embodiments and preferred embodiments described herein.

[0081] Example

[0082] The percentage of components in a flavoring can be determined by gas chromatography with an FID detector.

[0083] ppm refers to parts per million or mg / kg.

[0084] Example 1: Odor Threshold

[0085] The ability of odor molecules to detect odors is measured by their odor threshold. The odor detection threshold is understood as the lowest concentration of a certain odor compound that can be perceived by the human sense of smell.

[0086] The odor threshold (OTV) of bis(acetylthio)methane was calculated in the laboratory. Additionally, the odor thresholds of ethylene dithioacetate and other well-known fragrance molecules were evaluated. Evaluations were conducted following the European standard EN 13725:2003 guidelines and using GC-sniffing equipment. Each molecule was evaluated at different concentration levels. The odor threshold is the lowest concentration detected by at least 50% of the expert panel members.

[0087] These are the calculated OTVs:

[0088] The results showed that BATM has a very low odor threshold, much lower than that of the most common perfume raw materials such as linalool, geraniol, or δ-decanolide. This means that BATM has a strong enough odor to be detected at very low concentrations. Ethyl dithioacetate also has a very low odor threshold, although its odor threshold is 10 times that of BATM.

[0089] Example 2: The role of bis(acetylthio)methane at concentrations below 1 ppm in fragrances

[0090] Bis(acetylthio)methane has a strong odor, therefore it can be used at much lower doses compared to other raw materials while still maintaining sensory effects. Experiments were designed to demonstrate the effects at doses below one part per million (mg / kg). Triangular sensory tests were conducted, and the results showed that BATM had a significant effect on the perception of aromatic odors when applied at 0.1 ppm.

[0091] sample: This test considered two spices with different olfactory characteristics: - “Sidibou”: wooden, sweet, oriental, characteristic (masculine). - "Rouge Magic": Features amber, rose, and oakmoss (unisex) Make two versions of each spice: - One without any additional additives - A >95% BATM containing 0.1 ppm (mg / kg) All these spices are applied in 20% 96% ethanol to obtain the spice application.

[0092] Triangular Sense Test The triangulation test, also known as a discrimination test, was used to compare the odors of each pair of versions (with and without) to detect statistically significant sensory differences between samples. In this test, three coded (three-digit) samples of each spice (Sidibou and Rouge Magic) were presented to each expert panel member. Two samples were identical, and one sample was different. Expert panel members had to smell the samples using olfactory strips and mark the sample they perceived as different. The samples were presented to each expert panel member in a random order. Twenty-two expert panel members evaluated the samples.

[0093] Statistical data processing The number of correct answers (selecting samples with different compositions) is compared to a list of values ​​at a 99% significance level. These list values ​​indicate the minimum number of correct answers required to conclude that there is a significant difference between the samples at that significance level. The list values ​​are based on a χ² distribution that accounts for the expected number of correct answers obtained by chance. These values ​​depend on the significance level and the number of panel members.

[0094] result These are the number of correct and incorrect answers in the triangular test using the spice "Sidibou".

[0095]

[0096] Taking these results into account, a significant difference (99% significance) was detected between the samples' odors. Therefore, 0.1 ppm of BATM makes a significant contribution to the odor of the "Sidibou" fragrance.

[0097] These are the number of correct and incorrect answers in the study using the spice "Rouge Magic".

[0098]

[0099] Taking these results into account, a significant difference (99% significance) was detected between the samples' odors. Therefore, 0.1 ppm of BATM makes a significant contribution to the odor of "Rouge Magic" fragrance.

[0100] in conclusion This study shows that when bis(acetylthio)methane molecules are applied to fragrances at 0.1 ppm, they can exert sensory effects.

[0101] Example 3: The role of bis(acetylthio)methane in fragrances. Sensory testing was conducted.

[0102] The aim of this study was to describe the effect of bis(acetylthio)methane when added to flavorings. To this end, a sensory addition test was conducted.

[0103] This study considered six highly experienced evaluators (perfumers). They had to describe the olfactory effects of adding BATM. They smelled the same samples with and without 1 ppm of BATM.

[0104] They then described the effects of adding BATM. They allowed free use of any olfactory descriptor. These are the two sets of samples they had to compare: - Sidibou spice compared to Sidibou spice with 1 ppm BATM - "Rouge Magic" spice compared to Sidibou spice with 1 ppm BATM The fragrance is applied in 20% ethanol at 96% concentration to obtain the fragrance application.

[0105] All samples were presented to the evaluators in identical dark-colored, coded 5 ml containers. They moistened the tip of the olfactory strip in each sample and smelled them.

[0106] result These are summaries of the effects of BATM, as described by perfumers:

[0107] in conclusion As can be seen, BATM's contribution to fragrances is described as natural, fresh, herbal, hemp, woody, and leathery. Furthermore, a stronger scent is noted when BATM is present, especially in the top notes.

[0108] Example 4: Improvement of BATM sensation when combined with ethylene dithioacetate.

[0109] The benefits of combining BATM with ethylene dithioacetate (ETA) were explored. Different ratios were considered, ranging from the absence of ETA to an excess of ETA. Descriptive olfactory evaluations of each combination were conducted by experienced perfumers.

[0110] Six highly experienced evaluators (perfumers) participated in the study. They had to describe the odor of four solutions of BATM in different proportions with ethylene dithioacetate (ETA). They were free to use any olfactory descriptive terms. Solutions were prepared in triethyl citrate as the solvent. These were the samples they had to smell: - BATM 10 ppm (mg / kg) in TEC (ratio 1:0) - BATM 10 ppm + ETA 1.3 ppm in TEC (ratio 7.5:1) - BATM 10 ppm + ETA 10 ppm in TEC (ratio 1:1) - BATM 10 ppm + ETA 7.5 ppm in TEC (ratio 1:7.5) All samples were presented to the evaluators in identical dark-colored, coded 5 ml containers. They moistened the tip of the olfactory strip in each sample and smelled them.

[0111] Results: This is a compilation of the most frequently repeated descriptive terms given by perfumers:

[0112] As can be seen, the individual molecules of BATM exhibit descriptive terms such as "hemp," "green," "mocha," "fresh," "yeast / fermented," "spicy," and "leather." When ethylene dithioacetate (ETA) is added in a low proportion, odor modulation is observed. A minty / fresh scent emerges, and the "hemp" characteristic is described more realistically. When the presence of ETA increases to 1:1, the characteristics change significantly. The scents still considered "green" and "hemp" are perceived as less fresh. The "yeast / fermented" and "spicy" notes disappear. On the other hand, "sulfur-containing," "citrus," "tropical," and "herbal" notes emerge. The mocha scent is enhanced. When excessive ETA is added, the scent is perceived as less green and less natural. The "hemp" scent is perceived as less realistic. The "leather" scent is no longer perceived.

[0113] in conclusionThis experiment demonstrates that the combination of bis(acetylthio)methane and ethylene dithioacetate yields several interesting olfactory notes, which can be adjusted with varying proportions. Other notes, such as "spicy," "leather," "mint," "citrus," or "tropical," can also be produced when the green / hemp characteristics are dominant.

[0114] Example 5: Activation of the trigeminal nerve via diacetylthiomethane

[0115] The ability of the bis(acetylthio)methane (BATM) molecule to activate the trigeminal nerve was tested. Specifically, the ability of this molecule to activate the trigeminal nerve receptor TRPA1 (transient receptor potential cation channel subfamily A, member 1), whose relationship with the generation of some somatosensory sensations in the nose and mouth (e.g., tingling or stimulation) has been described.

[0116] This in vitro assay was performed by the laboratory Axxam (Milan, Italy). The measurement of receptor activation was based on changes in fluorescence measured using imaging techniques with calcium-sensitive dyes.

[0117] HEK293 cells were transiently transfected with TRPA1 plasmid DNA or a plasmid containing the test sequence. The last one, referred to as a "mimetic," is a control discarded during experimental measurements for any effects of substances that differ from receptor activation. Lipofectamine was used. TM Transfection was performed using a 2000 (Thermo Fisher Scientific) transfectant, and then both groups of cells were seeded into 384-well plates. Cells were loaded with the calcium-sensitive dye Cal-520® AM (AATBioquest) and incubated in the dark at room temperature for 4 hours. Fluorescence responses were recorded using a FLIPR Penta reader after BATM injection. Data were analyzed by calculating the maximum and minimum fluorescence values, normalizing to baseline fluorescence (ΔF / F0), and generating dose-response (D / R) curves for the TRPA1 receptor and simulated or control cells.

[0118] result: The dose-response curves of receptor TRPA1 and the mimic are shown in Figure 1The figure shows the change in fluorescence signal (receptor activation) as the concentration of BATM in the culture medium increases. The BATM molecule showed strong dose-dependent activation of TRPA1, with saturation observed in the medium from 3 mM to 10 μM, and a half-maximum effective concentration (EC50) of 4.2 μM. This value is close to that produced by allyl isothiocyanate (4.2 μM), a molecule known for producing a strong tingling sensation in the nose when smelled or tasted. Importantly, even at the highest concentration, no nonspecific activation was detected in cells transfected with the mimic. This indicates that the compound has high specificity and potency for TRPA1, with no off-target effects observed. These results also suggest that BATM can activate the trigeminal nerve receptor TRPA1, which is associated with nasal tingling.

[0119] Example 6: The effect of BATM on enhancing the perceived freshness of scented materials

[0120] Sensory tests were conducted to confirm that BATM, present in odorous mixtures, can enhance the perceived freshness of the mixture.

[0121] Freshness is a very common term in the perfumery industry. Studies have been conducted to define this descriptive term (see M. Zarzo, “What is a Fresh Scent in Perfumery? Perceptual Freshness is Correlated with Substantivity” Sensors 2013, vol. 13, pp. 463-483). Perfumers are well aware that citrus and green scents are perceived as fresh. Furthermore, some spicy scents can be considered fresh. Aquatic or aldehyde scents can also convey a sense of freshness. A special case is menthol (etc.), which has a generally considered fresh scent and can produce a cooling effect through activation of the TRPM8 trigeminal receptor.

[0122] In this study, freshness was defined using the following concept: - Cooling / refreshing effect - A fresh sensation derived from green / vegetal or citrus elements, evoked by the aroma of the evaluated materials. The study was conducted using two distinct groups: a combination of several fragrance ingredients and a single raw material, spearmint oil. Both samples were deemed fresh by perfumers. The amount of BATM added was sufficiently low to preserve the primary olfactory characteristics of the original composition.

[0123] sample: - "Spice 1": Spicy composition.

[0124] - "Spice 2": "Spice 1" (99.999%) + 0.001% BATM

[0125] - "Spearmint 1": Spearmint essential oil

[0126] - "Spearmint 2": "Spearmint 1" (99.995%) + 0.005% BATM

[0127] The composition of the sample is as follows (% w / w units):

[0128] Before evaluation, each sample was diluted to 10% in 96% ethanol.

[0129] Evaluation method: The olfaction strips were moistened in an ethanol dilution of each sample and immediately smelled by members of the expert panel. A group of non-experts evaluated the four samples in two separate pairs. They smelled the combination of Fragrance 1 and Fragrance 2 for one time period and Spearmint 1 and Spearmint 2 for another time period. For each pair, they were asked to answer the question: “Which sample do you find fresher?” (freshness as defined in the “Introduction” section). They had the option to choose a third option: “No difference / Same level of freshness.” A χ² test was applied to determine whether the significant enhancement was caused by the presence of BATM.

[0130] result: The result of the "spice" composition is:

[0131] These results indicate that the addition of 0.001% (10 ppm) of BATM to the composition enhanced the perceived freshness by the specialized panel members, with a significance greater than 95%.

[0132] The result of the spearmint composition is:

[0133] These results indicate that the addition of 0.005% (50 ppm) BATM to spearmint oil enhanced the perceived freshness by the panel members, with a significance level greater than 95%.

[0134] in conclusion: This study shows that BATM can enhance the freshness imparted by the scents of some fragrances that are already considered fresh.

[0135] Example 7: The effect of BATM on enhancing the olfactory intensity of odorous materials

[0136] Sensory tests were conducted to confirm that the presence of BATM can enhance the strength of the material.

[0137] The study investigated BATM in combination with four different spice materials: lemon oil, spearmint oil, clove oil, and basil oil. The amount of BATM added was low enough to maintain the main olfactory properties of the tested spice materials.

[0138] sample: - Clove 1: 100% clove oil - Clove 2: Clove 1 + 0.05% BATM -Spearmint 1: 100% spearmint oil -Spearmint 2: Spearmint 1 + 0.05% BATM - Lemon 1: 100% lemon oil - Lemon 2: Lemon 2 + 0.05% BATM -Basil 1: 100% basil oil -Basil 2: Basil 1 + 0.05% BATM Before evaluation, each sample was diluted to 10% in triethyl citrate.

[0139] Evaluation method: Each olfaction strip was moistened in a diluted solution of the sample and immediately smelled by a panel of experts. A group of non-experts evaluated the samples in individual pairs: clove 1 and clove 2, spearmint 1 and spearmint 2, lemon 1 and lemon 2, and basil 1 and basil 2. Each pair was smelled at different time intervals. For each pair, they were asked to answer the question: “Which sample do you find more refreshing?” They could choose a third option: “Same intensity level.” A χ² test was applied to determine whether a significant increase in intensity was caused by the presence of BATM.

[0140] result: The result of "Lilac" is: One member of the special task force did not find differences in intensity between the samples. These results indicate that the addition of 0.05% (500 ppm) BATM to the composition enhances the strength of clove oil by a significance greater than 95%.

[0141] The result of "spearmint" is: The four members of the special task force did not find any differences in intensity between the samples. These results indicate that the addition of 0.05% (500 ppm) BATM to the composition enhances the strength of spearmint oil by a significance greater than 95%.

[0142] The result of "Lemon" is: The two specialists did not find any differences in intensity between the samples. These results indicate that the addition of 0.05% (500 ppm) BATM to the composition enhances the strength of lemon oil with a significance level of 95%.

[0143] The result for "Basil" is: The five-member expert team found no differences in intensity between the samples. These results indicate that adding 0.05% (500 ppm) of BATM to the composition did not enhance the strength of basil oil, with a significance greater than 95%.

[0144] in conclusion: This study shows that BATM can enhance the olfactory intensity of fragrance raw materials. The degree of effect can vary within a range of aroma types.

[0145] Reference List

[0146] Patent documents

[0147] - US5871721

[0148] - EP1090557

[0149] - WO2014118354

[0150] - US6261483

[0151] - EP2234712

[0152] - US2800457

[0153] Non-patent literature

[0154] - CS Sell in “On the Unpredictability of Odor”, Agnew. Chem. Int-Ed. 2006, vol. 45, pp.6254-6261

[0155] - L Sternson in “1,1-Bis(acylthio)alkanes Formed by Bae-CatalyzedCondensation of Thiol Acids”, J. Org. Chem., 1978, vol. 43, No.23

[0156] - Nilius, Bernd; Flockerzi, Veit . (2014). [Handbook of ExperimentalPharmacology] Mammalian Transient Receptor Potential (TRP) Cation ChannelsVolume 223 || TRPs in Taste and Chemesthesis (Chapter 5), 827–871

[0157] - M. Zarzo, “What is a Fresh Scent in Perfumery? Perceptual Freshnessis Correlated with Substantivity” Sensors 2013, vol. 13, pp. 463-483。

Claims

1. The use of bis(acetylthio)methane of formula (I) as a fragrance ingredient, (I)。 2. The use according to claim 1, wherein the bis(acetylthio)methane of formula (I) is used in combination with S,S-dithioacetate as a flavoring ingredient, wherein the use includes using a flavoring ingredient that contains both components simultaneously, or using two separate flavoring ingredients for each individual component.

3. The use according to any one of claims 1 and 2, wherein the fragrance ingredient is encapsulated.

4. The use according to any one of claims 1 to 3, wherein the bis(acetylthio)methane of formula (I) activates the trigeminal nerve receptor TRPA1 associated with tingling sensation in the nose.

5. The use according to any one of claims 1 to 4, wherein the bis(acetylthio)methane of formula (I) enhances freshness, olfactory intensity of other odorous materials, or both.

6. Fragrance ingredients, including bis(acetylthio)methane and S,S-dithioacetate ethylene.

7. The fragrance ingredient according to claim 6, wherein bis(acetylthio)methane comprises 5% to 95% of the total weight of the fragrance ingredient.

8. The flavoring ingredient according to any one of claims 6 and 7, wherein S,S-dithioacetate is 5% to 95% of the total weight of the flavoring ingredient.

9. The fragrance ingredient according to any one of claims 6 to 8, wherein the weight ratio of bis(acetylthio)methane and S,S-dithioacetate ethylene is 19:1 to 1:

19.

10. A fragrance comprising at least two fragrance components, wherein one of the fragrance components comprises bis(acetylthio)methane, and optionally, the other fragrance component comprises ethylene S,S-dithioacetate; or alternatively, one of the fragrance components is as defined in any one of claims 6 to 9.

11. The flavoring according to claim 10, further comprising suitable additives or carriers.

12. A fragrance-enhancing consumer product comprising an effective amount of a fragrance ingredient comprising bis(acetylthio)methane, optionally having an effective amount of another fragrance ingredient comprising ethylene S,S-dithioacetate, or alternatively, comprising an effective amount of a fragrance ingredient as defined in any one of claims 4 to 7.

13. The fragrance-enhancing consumer product of claim 12, wherein the fragrance component is present in an amount equal to or less than 10 ppm relative to the total weight of the fragrance-enhancing product.

14. The fragrance-enhancing consumer product of claim 13, wherein the fragrance component is present in an amount equal to or less than 1 ppm relative to the total weight of the fragrance-enhancing product.

15. The flavoring consumer product of claim 12, wherein the flavoring ingredient is added in the form of a flavoring as defined in any one of claims 10 and 11.

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