ORGANIC COMPOUNDS

Abstract

The present invention relates to compounds of formula (I) as defined herein, capable of releasing fragrant compounds in a controlled manner into the surroundings. The present invention also relates to a process for their production, and consumer products comprising them.

Description

ORGANIC COMPOUNDS oonz Ln / Lznz / E / YiAi Description of the Invention The present invention relates to a particular class of compounds capable of releasing fragrant compounds in a controlled manner into the surrounding environment. The present invention also relates to a process for their production and consumer products comprising them. In particular, the present invention relates to damascone-releasing precursors. Damascus DAMASCONAALFA DAMASCONASETA DAMASCONA DELTA 1-(2',6',6'-trimethylcyclohex-2'-en-1'yl)but-2-en-1-one, 1-(2',6',6'-trimethylcyclohex-1'-en-1'yl)but-2-en-l-one, and 1-(2',6',6'-trimethylcyclohex-3'-en-1'yl)but-2-en-l-one are, respectively, a family of desirable fragrance ingredients found in essential oils. They are frequently used in perfumery. There is interest in providing a damascone precursor, that is, a compound that is itself, basically due to its high molecular weight, essentially odorless, but which, under particular circumstances, will decompose to release Ref. 326972 damascone at the desired time. It has now been found that the compound of formula (I) as described below herein, can act as a precursor to the release, by spontaneous oxidation of air, of damascone. Similar compounds are known from international publication WO 01 / 35768, in which certain carbonyl compounds, including damascone, can react with cysteine ​​to provide flavoring products. However, these compounds are not precursors, but integral flavoring materials. oonz Ln / Lznz / E / YiAi Therefore, the use of a compound of formula (I) is provided in one aspect: as a precursor to generate, by spontaneous oxidation of air, a damascone of the formula (II): where one of the dotted lines represents, along with the carbon-carbon bond, a double bond, and each of the other two dotted lines represents, along with the carbon-carbon bond, a single bond. In a preferred embodiment, the compound of formula (I) is a compound in which the dotted line between C3' and C4' represents together with the carbon-carbon bond a double bond (i.e., the compound of formula (I) is ethyl S-(4-oxo4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)bufan-2yl)cysteinate). The activation conditions, which lead to the cleavage step, include the presence of molecular oxygen. The oxygen concentration in the air is sufficient to cleave the compound of formula (I), such that the cleavage products can be detected in ambient air, for example, by smell or GC-MS analysis of headspace samples. The compounds of formula (I) are very stable when not exposed to ambient air, i.e., when stored pure or in a diluent commonly used with odorants such as dipropylene glycol (DPG), isopropyl myristate (IPM), triethyl citrate (TEC), pentane-1,2-diol, and alcohol (e.g., ethanol) and other known odorants. Very good storage stability has also been demonstrated when incorporated into consumer products such as detergent, shampoo, and fabric conditioner. Therefore, the compounds of formula (I) can be used in a wide range of consumer products where a prolonged and defined release of fragrance compounds is desired. In one specific embodiment, the compounds of formula (I) are useful in consumer products, such as detergent products, including powder and liquid detergents or detergents in tablet form, sachets / single doses, soap and washing tablets, fabric softener, including dryer sheets, and odor enhancers (liquid or solid). In another specific embodiment, the compounds of formula (I) are useful in cosmetic products, which include (a) cosmetic skin care products, especially bath products, skin washing and cleansing products, skin care products, eye makeup, lip care products, nail care products, intimate care products, foot care products; (b) cosmetic products with specific effects, especially sunscreens, tanning products, depigmenting products, deodorants, antiperspirants, hair removal products and shaving products; € cosmetic products for dental care, especially dental and oral care products, dental care products, denture cleaners, denture adhesives; and oonz Ln / Lznz / E / YiAi (d) cosmetic products for hair care, especially hair shampoos, hair care products, hair fixing products, hair shaping products and hair dyeing products. Therefore, in another aspect of the present invention, a consumer product is provided comprising a compound of formula (I) and a product base. As used herein, consumer product base means a composition for use as a consumer product to perform specific actions, such as cleaning, softening, and caring for, or the like. Examples of such products include fine perfumery, e.g., perfume and eau de toilette; fabric care, household, and personal care products, such as cosmetics, laundry detergents, rinse-off conditioner, personal cleansing compositions, dishwashing detergent, and surface cleaner; laundry products, e.g., fabric softener, bleach, and detergent; body care products, e.g., shampoo and shower gel; and air care products (including products containing compounds that are preferably volatile and generally pleasant-smelling, which can advantageously mask unpleasant odors even in very small quantities).Home air fresheners contain, in particular, natural and synthetic essential oils, such as pine needle oil, citrus oil, eucalyptus oil, lavender oil, and the like. In one embodiment, the compounds of formula (I) are especially useful as part of fragrances for use in laundry products, where they can release damask with use. However, under certain conditions, the scent profile is perceived as a fruity berry with a slightly plastic note. Surprisingly, it was found that when combined with a second class of compounds, the resulting combination produces a scent profile that is essentially free of undesirable plastic notes. Therefore, in a further aspect of the present invention, a combination of the compound of formula (I) with a compound of formula (III) is provided: where the dotted lines represent a double bond located at one of the alpha, beta, or delta positions in each of the cyclohexene rings. These compounds, which are bis-adducts, are described in International Publication WO 2008 / 154765. It was found that when a combination of a compound of formula (I) with a compound of formula (III) was used in laundry products, the deposition rate was improved. It was also found that, when using a combination of a compound of formula (I) with a compound of formula (III), a continuous release of compounds of formula (II) was noticeable from an early stage to several days (e.g., when used in a detergent product, already on wet fabric). In a preferred embodiment, the compound of formula (III) is a compound in which the dashed lines represent a double bond located in the delta position in each of the cyclohexane rings (i.e., the compound of formula (III) is N,S-bis(4-oxo-4-(2',6',6' trimethylcyclohex-3'-en-1'-yl)butan-2-yl)ethylcysteinate)). In another preferred embodiment, a mixture of a compound of formula (I) and a compound of formula (III) is provided in a ratio of 1:40 to 40:1, including a ratio of 1:20 to 1:10, for example, 1:15 to 1:11. In one particular embodiment, a mixture of ethyl S-(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)butan-2-yl)cysteinate and ethyl N / S-bisti-oxo-yl' / o' / o'trimethylcyclohex-3'-en-1'-yl)butan-2-yl)cysteinate is provided, preferably in a ratio of 1:40 to 40:1, including a ratio of 1:20 to 1:10, for example, 1:15 to 1:11. The compounds of formula (I), or a mixture of a compound of formula (I) and a compound of formula (III), may be used alone or in combination with other fragrance ingredients and / or precursors thereof. Such fragrance ingredients are described, for example, in Perfume and Flavor Chemicals, S. Arctander, Ed., Vol. I and II, Allured Publishing Corporation, Carol Stream, USA, 2003, and include fragrance compounds of natural or synthetic origin and essential oils. The following list comprises examples of known fragrance ingredients, which can be combined with the compounds in formula (I): - essential oils and extracts, for example, castoreum, costus root oil, oakmoss absolute, geranium oil, tree moss absolute, basil oil, fruit oils such as bergamot oil and mandarin oil, myrtle oil, palmarosa oil, patchouli oil, pumpkin seed oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil and / or ylang-ylang oil; alcohols, for example, cinnamic alcohol (β-3-phenylprop-2-en-l-ol); cis-3-hexenol ((Z)-hex-3-en-l-ol); citronellol (3,7-dimethyloct-6-en-l-ol); dihydromyrcenol (2,6-dimethyloct-7-en-2-ol); Ebony1™ (€-3-methyl-5-(2,2,3ooz Ln / Lznz / E / YiAi trimethylcyclopent-3-en-l-yl)pent-4-en-2-ol); eugenol (4-allyl2-methoxyphenol); ethyl linalool (€-3,7-dimethylnona-l,6-diene-3ol); farnesol ((2E,6Z)-3,7,ll-trimethyldodeca-2,6,10-trien-lol); geraniol (€-3,7-dimethylocta-2,6-diene-l-ol); Super Muguet™ (€-6-ethyl-3-methyloct-6-en-l-ol); linalool (3,7-dimethylocta1,6-diene-3-ol); menthol (2-isopropyl-5-methylcyclohexanol); Nerol (3,7-dimethyl-2, 6-octadien-l-ol) ; phenylethyl alcohol (2-phenylethanol) ; Rhodinol™ (3,7-dimethyloct-6-en-l-ol); Sandalore™ (3-methyl-5-(2,2,3-trimethylcyclopent-3-en-l11)pentan-2-ol); terpineol (2-(4-methylcyclohex-3-en-lyl)propan-2-ol); o Timberol™ (1-(2,2,6trimethylcyclohexyl)hexan-3-ol); 2,4,7-trimethylocta-2,6-dienl-ol y / o [l-methyl-2(5-methylhex-4-en-2-yl)ciclopropyl]methanol; - aldehydes and cetonas, for example, anisaldehido (4metoxybenzaldehido) ; alpha amyl cinámico aldehyde (2bencilidenheptanal) ; Damascona delta ((2E)-1-(2,6,6trimethylcyclohex-2-en-l-yl)but-2-en-l-ona); Georgywood™ (1(1,2,8,8-tetramethy1-1,2,3,4,5,6,7,8-octahidronaphthalene-2yl)ethanone); hidroxicitronelal (7-hidroxi-3,7-dimethyloctanal); Iso E Super® (1-(2,3,8,8-tetramethyl1,2,3,4,5,6,7, 8-octahidronaphthalene-2-yl)ethanone) ; Isoraldeine® (€-3-methyl1-4-(2,6,6-trimethylcyclohex-2-en-l-yl)but-3-en-2one); Hedione® (3-oxo-2-pentylcyclopentaneacetate de methyl); 3-(4-isobutyl-2-methylphenyl)propanal; maltol; methyl cedryl ααηζ Ln / Lznz / B / YiAi cetone; methylionone; verbenone; y / o vainillin; ethers and acetals, for example, Ambrox® (3a,6,6,9-atetramethyl-2,4,5,5a,7,8,9,9b-octahydro-lHbenzo[e][1]benzofuran); geranyl methyl ether ((2E)-l-methoxy3,7-dimethylocta-2,6-diene); rose oxide (4-methyl-2-(2-methylprop-l-en-l-yl)tetrahydro-2H-pyran); and / or Spirambrene® (2',2',3,7,7-pentamethylspiro[bicyclo[4.10]heptan-2,5'[1,3]dioxane]); - esters and lactones, for example, benzyl acetate; cedryl acetate ((1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methaneazulen-6-yl acetate); and- decalactone (6-pentyltetrahydro-2H-pyran-2-one); Helvetolide® (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl propionate); γ-undecalactone (5-heptiloxolan-2-one); and / or vetiveryl acetate ((4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulen-6-yl acetate); - macrocycles, for example, Ambrettolide ((Z)oxacycloheptadedec-10-en-2-one); ethylene brasylate (1,4-dioxacycloheptadecan-5,17-dione); and / or Exaltolide® (16-oxacyclohexadecan-1-one); and heterocycles, for example, isobutylquinoline (2-isobutylquinoline). In one particular embodiment, the compound of formula (I), or the mixture of a compound of formula (I) and a compound of formula (III), can be used in combination with other fragrance precursors, including l-butoxy-3((1E,4Z)-hepta-1,4-dien-1-yl)benzene, (4-(dodecylthio)-4-methylpentan-2-one, 2-ethoxy-4-((1E,4Z)-hepta-1,4-dien-lyl)phenol and ethyl 2-acetyl-4-methyltridec-2-enoate. The amounts in which the compounds of formula (I), or the mixture of a compound of formula (I) and the compound of formula (III), may be incorporated into different consumer products vary within a wide range. The amounts depend on the nature of the product to which the compounds of formula (I), or the mixture of a compound of formula (I) and the compound of formula (III), are added, and the desired olfactory effect. The amounts used also depend on the co-ingredients in a given composition when the compounds of formula (I), or the mixture of a compound of formula (I) and the compound of formula (III), are used in combination with perfume co-ingredients, solvents, or adjuvants. Typical concentrations range from 0.0001 to 5 percent by weight of the article. In one embodiment, the compounds of the present invention may be used in a fabric softener in an amount of 0.0001 to 2 percent by weight.In another embodiment, the compounds of the present invention can be used in a detergent in an amount of 0.0001 to 4 percent by weight. In another embodiment, the compounds of the present invention can be used in fine perfumery in amounts of 0.001 to 10 percent by weight (for example, up to approximately 5 percent by weight), more preferably between 0.02 and 4 percent by weight. However, these values ​​are given only as examples, since an experienced perfumer can also achieve effects or create new accords with lower or higher concentrations. The compounds of formula (I) are novel in their own right. Therefore, in a further aspect of the invention, a compound of formula (I) is provided: where one of the dotted lines represents, along with the carbon-carbon bond, a double bond, and each of the other two dotted lines represents, along with the carbon-carbon bond, a single bond. The compounds of formula (I) can be prepared by a 1,4 addition of cysteine ​​ethyl ester to damascone in a suitable solvent, such as tetrahydrofuran, dimethylformamide, ethanol, or water, and in the presence of an organic or inorganic base, such as N-ethyldiisopropylamine, triethylamine, potassium or sodium carbonate or hydroxide. Other conditions for the formation of thioethers can be used that are known to those experienced in the technique of organic synthesis. A mixture of a compound of formula (I) and a compound of formula (III) can be prepared by mixing the two compounds in the desired proportion after each has been prepared independently of the other. Alternatively, the mixture can be prepared in situ, for example, by following the process described in the Examples. The invention is now further described with reference to the following non-limiting examples. These examples are for illustrative purposes only, and it is understood that a person skilled in the art may make variations and modifications. EXAMPLES Example 1: Ethyl S-(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-l'yl)butan-2-yl)cysteinate In a 250 mL two-necked round-bottom flask, β-1-(2',6',6'-trimethylcyclohex-3'-en-1'-11)but-2en-1-one (10 g, 52.0 mmol) and L-cysteine ​​ethyl ester hydrochloride (15 g, 81 mmol) were placed in water (100 mL). With stirring at room temperature, potassium carbonate (8 g, 57.9 mmol) was added in a portion, and the resulting mixture was stirred overnight at room temperature. MTBE (50 mL) was added to the mixture, which was then stirred for a further hour. The mixture was transferred to a separatory funnel, the phases were separated, and the aqueous phase was extracted with MTBE (2 x 50 mL). The organic phases were combined and washed with water (3x50 mL), water / brine (20 mL / 30 mL) and brine (50 mL), dried over MgS4, filtered and the solvent evaporated to give S-(4-oxo-4(2', 6', 6'-trimethylcyclohex-3'-en-1'-yl)butan-2-yl)-L-ethyl cysteinate (16.91 g, 49.5 mmol, 95% yield) as a mixture of four isomers and as a light yellow oil. Description of the smell (drying of a 10% DPG solution after 24 hours in an olfactory strip): fruity berry, reminiscent of stewed apple, slightly plastic, chemical. NMR-!H (CDCI3, 400 MHz): δ = 5.57-5.51 (m, 1H) , 5.44 (br d, J = 10 Hz, 1H), 4.20 (br q, J = 7.1 Hz, 2H), 3.71-3.63 (m, 13.3 Hz), 3.38 (m, 1H). 1H), 3.00-2.88 (m, 1.5H), 2.83-2.77 (m, 1H), 2.73-2.71 (m, 1H), 2.56-2.48 (m, 1.5H), 2.22 (d, J = 10.5 Hz, 0.5 Hz), (d, 1.2 Hz, 1.2 Hz). 0.5H), 1.97 (br d, J = 17.6 Hz, 1H), 1.8 (br s, 2H), 1.70 (br d, J = 17.6 Hz, 1H), 1.32-1.30 (m, 3H), 1.29 (t, J = 7.1 Hz, 3H), 9H) ppm. NMR-13C (CDCI3, 100 MHz): δ = 211.91, 211.80, 173.76, 131.59, 131.57, 131.51, 131.48, 124.04, 123.92, 13.9, 62.6,62. 62.59, 61.00, 60.97, 55.03, 54.91, 54.89, 54.82, 54.32, 54.30, 54.06, 41.53, 41.50, 36.07, 36.03, 35.93, 35.86, 34.71, 34.67, 34.41, 32.97, 32.94, 32.92, 32.87, 31.57, 31.52, 31.43, 31.38, 29.65, 29.61, 29.58, 21.76, 21.74, 21.56, 21.50, 20.55, 20.53, 19.73, 19.68 ppm. MS (El, 70 eV) : 341 ([M]+', 2), 123 (67), 117 (69), 102 (65), 81 (51), 76 (49), 75 (80), 69 (100), 43 (60), 41 (58), 29 (56). Example 2: S-(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-l)butan-2-yl)ethyl cysteinate (GR-87-1182-2) y N,S-bis(4oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)bufan-2yl)ethyl cysteinate In a 1500 mL sulfonation flask, β-1(2',6',6'-trimethylcyclohex-3'-en-1'-yl)but-2-en-l-one (200 g, 1.04 mol) and L-cysteine ​​ethyl ester hydrochloride (98.1 g, 0.53 mol) were placed in water (520 mL). Under stirring at room temperature, potassium carbonate (72.16 g, 0.52 mol) was added in a portion. The reaction mixture was then stirred overnight at room temperature. The solution was transferred to a separatory funnel, MTBE (100 mL) was added, the phases were separated, and the aqueous phase was extracted with MTBE (100 mL). The phases were combined and washed with brine (250 mL), dried over MgSCh, filtered, and the solvent evaporated to give a light yellow oil containing a mixture of ethyl S-(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-l'yl)butan-2-yl)-L-cysteinate isomers and N,S-bis(4-oxo-4(2',6',6'-trimethylcyclohex-3'-en-1'-yl)butan-2-yl)-L-cysteinate isomers in a ratio of 1:14 (255.39 g, 0.48 mol, 92% yield) Description of the odor of the mixture obtained (drying of a 10% DPG solution after 24 hours on an olfactory strip): fruity, similar to apricot, stewed apple, clean, pleasant. The activation conditions for releasing compounds from Formula II comprise a combination of pH change, elevated temperature, and exposure to air. This combination of triggering conditions has the advantage of the continuous release of odorous compounds from Formula II from an early stage (e.g., on damp fabric during detergent application) for several days. Example 3: Ethyl N-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-l-yl)but2-en-2-yl)-S-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-lyl)butan-2-yl)cysteinate) Step 1: In a 250 mL sulfonation flask fitted with a Dean-Stark trap, 3-hydroxy-l-(2,6,6-trimethylcyclohex-3-en-l-yl)but-2-en-l-onediketone (5.1 g, 24.5 mmol) and L-cysteine ​​ethyl ester hydrochloride (4.6 g, 24 mmol) were suspended in toluene (50 mL). Acetic acid (10 mL, 175 mmol) was added, and the mixture was heated under reflux (To = 130°C) overnight. The mixture was transferred to a separatory funnel, and a water / brine mixture (20 mL / 30 mL) was added. The phases were separated, and the aqueous phase was washed with MTBE (30 mL). The organic phases were combined, washed with saturated aqueous NazCOs (50 mL), brine / water (20 mL / 10 mL) and brine (30 mL), dried over MgSCh, filtered and the solvent evaporated to give ethyl-(4-oxo-4-(2,6,6-trimethylcyclohex-3en-l-yl)but-2-en-2-yl)cysteinate (8.3 g, 24.5, quantitative yield) as a yellow oil. MS (El, 70 eV): 339 ([M]+', 4), 216 (94), 174 (100), 142 (65), 116 (42), 107 (27), 84 (41), 67 (36), 58 (39), 41 (33), 29 (67). Step 2: Ethyl-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-2-yl)cysteinate (3 g, 8.8 mmol) was placed in a 100 mL two-necked round-bottom flask along with ε-1(2',6',6'-trimethylcyclohex-3'-en-1'-11)but-2-en-1-one (1.7 g, 8.8 mmol). Water (50 mL), THE (10 mL), and potassium carbonate (1.2 g, 8.7 mmol) were added, and the mixture was stirred at room temperature for three days. The orange mixture was transferred to a separatory funnel, the phases were separated, and the aqueous phase was washed with MTBE (2 x 30 mL). The organic phases were combined and washed with water / brine (2x20 mL / 10 mL) and brine (20 mL), dried over MgSO4, filtered and the solvent was evaporated to give a yellow oil which was further purified by chromatography (eluent: heptane / MTBE, 8 / 2) to give ethyl-N-(4-oxo-4-(2',6',6'-trimethylcyclohex-3,en-1'-yl)but-2-en-2-yl)-S-(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)butan-2-yl)cysteinate (1.54 g, 29 mmol, yield of 32.8%) as a mixture of isomers and a light yellow oil. Scent description (dried from a 10% DBG solution after 24 hours on a scent strip): licorice, sweet, damask. oonz Ln / Lznz / E / YiA 13C-NMR (CDC13, 100 MHz): δ = 211.98, 211.95, 211.93, 211.90, 211.89, 211.84, 200.41, 200.37, 200.35, 170.32, 170.30, 170.28, 170.18, 170.15, 159.97, 159.86, 159.78, 159.72, 159.64, 132.55, 132.51, 131.71, 131.61, 124.17, 124.02, 123.89, 123.85, 100.21, 100.14, 62.81, 62.78, 62.73, 62.72, 62.56, 61.65, 61.63, 56.92, 56.82, 56.76, 56.69, 56.66, 55.28, 55.20, 55.13, 55.09, 55.07, 55.05, 55.01, 42.12, 41.67, 41.65, 41.62, 35.33, 35.26, 35.20, 35.12, 34.35, 34.27, 34.16, 33.97, 33.87, 33.82 33.74, 33.06, 33.04, 32.69, 31.80, 31.67, 31.65, 31.56, 31.53, 31.05, 31.02, 30.04, 30.01, 29.74, 29.69, 28.94, 22.62, 21.98, 21.95, 21.82, 21.77, 21.75, 21.72, 21.59, 21.53, 21.19, 20.66, 20.63, 20.08, 20.04, 19.85, 19.80, 19.34, 19.31, 19.29 19.27, 14.05, 14.04 ppm. MS (El, 70 eV): 408 ([C22H34NO4S]+, 2), 123 (100), 110 (36), 107 (32), 84 (44), 83 (34), 81 (95), 69 (54), 67 (43), 55 (27), 41 (26). Example 4: Odor evaluation Wet Dried after 24 hours Dried after 3 days Compound A Pleasant, fruity, damask with a light plastic note fruity berry, reminiscent of stewed apple, slightly plastic, chemical Damask, fresh Wet Dried after Dried after 3 24 hours days Compound B fruity, apricot, sweet Fruity, clean apricot, Fruity, sweet apricot, Compound A + Compound B (1:4 ratio) Apricot, stewed apple, fruity strawberry, similar to apricot, stewed apple, clean, pleasant apricot oonz Ln / Lznz / E / YiA Compound A: Ethyl S-(4-oxo-4-(2',6',6'-trimethylcyclohex-3' en-1'-yl)butan-2-yl)oysteinate Compound B: Ethyl N,S-bis(4-oxo-4-(2,,6,,6,-trimethylcyclohex3'-en-1'-yl)butan-2-yl)cysteinate As can be seen from the description of the odor above, when the compound of formula (I) is combined with a compound of formula (III), the plastic note disappears. Example 5: Fragrance comprising a compound of formula (I) Compound / Ingredient Parts by Weight 1 / 1000 2-Methyl-1-phenylpropan-2-yl acetate 20 4-(tert-butyl)cyclohexyl acetate 50 (2-(1-ethoxyethoxy)ethyl)benzene 2 AGRUMEX (2-(tert-butyl)cyclohexyl acetate) 25 2-Phenylethanol-1-ol 10 Compuesto / ingrediente parts en peso 1 / 1000 €-2-bencilidenoctanal 100 2-methylundecanal 1 AMBROFIX 2-aminobenzoato de (3a,6,6,9a- tetramethyldodecahidronafto[2,1b]furan)methyl 1 2-aminobenzoato de methyl 2 AUBEPINE PARA CRESOL (4- metoxibenzaldehyde) 3 terpenos de limon 10 Citronelol 80 Damascona delta 2 DIHIDRO MIRCENOL 100 OXIDO DE DIFENILO 10 DUPICAL (4-(octahidro-5H-4,7- metanoinden-5-i1iden)butanal) 2 EUCALYPTOL NATURAL 3 FLOROCICLENO (propionate of 3a,4,5,6,7,7a-hexahido-lH-4,7- metañoinden-6-ilo) 75 GARDENOL (acetato of 1phenyletilo) 20 ISO E SUPER 100 ααηζ Ln / Lznz / Β / γΐΛΐ ISORALDEINE 25 Compound / ingredient parts by weight 1 / 1000 JAVANOL @ 10% DPG 5 LEMONILE (3,7-dimethylnonone-2,6dienenitrile) 2 METHYL ACETOPHENONE (l-(ptolyl)etan-l-one) 2 4- (tert-butyl)cyclohexan-1-ol 10 PATCHOULI ESS SANS FER INDONESIE ORPUR 3 PHARAONE (2-cyclohexylhepta-l,6- dien-3-one) 10% / DPG 5 Hexyl salicylate 75 SERENOLIDE (2—(1 — (3,3-dimethylcyclohexyl)-2- methylpropyl cyclopropancarboxylate) 30 S PIROGALBANONE (1(spiro[4.5]dec-6 / 7-en-7yl)pent-4-en-l-one 1 STEMONE ((Z)-5-methylheptan-3-one oxime) 1 TETRAHYDRO LINALOLOL 50 UNDECAVERTOL 10 ααηζ Ln / Lznz / Β / γΐΛΐ Dipropylene glycol (DPG) 165 Total: 1000 The composition of the above fragrance is a fresh, green floral accord, reminiscent of fresh green lily of the valley. This fragrance can be applied, for example, in high-density liquid detergent (HDLD) at 0.1–1.5% by weight (e.g., 0.6% by weight). Replacing 45 parts of DPG from the previous arrangement with a mixture of ethyl S-(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-11)butan-2-yl)cysteinate and ethyl N,S-bis(4oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)butan-211)cysteinate (ratio of approximately 1:14), the overall character is now milder and fruitier, reminiscent of apples stewed on dry cloth. The fresh fruitiness is clearly enhanced over time and lasts for several days. Replacing 55 parts of DPG from the above agreement with a mixture comprising S-(4-oxo-4-(2',6',6'trimethylcyclohex-3'-en-1'-yl)butan-2-yl)ethyl cysteinate (2.7 parts), N,S-bis(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)butan-2-yl)ethyl cysteinate (37.3 parts) and an additional precursor (4-(dodecylthio)-4-methylpentan-2-one (15 parts)), a very unusual and pleasing effect is the overall elevation and brightness of the perfume on dry fabric; with this combination, the fresh fruitiness is not only enhanced and prolonged, but also has improved volume and elevation. Example 6: Precursor deposition studies in cotton with high-strength liquid detergent application A liquid detergent composition (4.0 mg) was prepared using a perfume-free heavy-duty liquid detergent (HDLD) base containing 0.2% w / w of a mixture from Example 2. This liquid detergent composition was dissolved in 1 L of cold tap water to produce a wash liquor containing the precursor. The wash liquor (100 mL) was placed in a 150 mL conical flask along with two cotton pads (10 x 10 cm², each weighing 2.5 g). The flask was sealed with a screw stopper and shaken on a thermostatically controlled shaker at 200 rpm and 40°C for 1 h. The liquids were discarded, and the cotton pads (wet weight 4.5 g) were wrung out and placed back into the conical flasks. After adding 75 mL of cold tap water, rinsing was performed with shaking for 30 minutes at room temperature.The cotton pads were wrung out and extracted using an accelerated solvent extractor (CH3CN, 60°C, 1,500 psi), and the extracts (15–20 mL, precisely determined) were subjected to quantitative analysis by HPLC. The above process was repeated, except that the towels were extracted after a 24-h period of line drying in ambient air. The two previous processes were repeated with a liquid detergent composition containing 0.2% δ-Damascone instead of the mixture in Example 2. The quantification of δ-Damascone as such and its precursors in cotton pad extracts was performed by HPLC-UV with external calibration (0.3-20 ppm) of reference materials in CH3CN. The results are shown in the table below. oonz Ln / Lznz / E / YiAi HLDL Mixture of Example 2 (δ-Damascone precursor + released δ-Damascone) δ-Damascone (comparison) wet (9+2) % 6% 24 h line drying (6+1) % 0.7% The results show that the mixture in Example 2, containing a blend of bis- and mono-add, leads to the release of a perceptible amount of δ-Damascone even in the wet stage. After 24 h of line drying, the amount of δ-Damascone released from the precursor exceeded the amount when using free δ-Damascone. Furthermore, a large precursor reservoir is available for the continuous and sustained release of the odorant. Overall, the amount of bound and free δ-Damascone released from the precursor on dry fabric is more than five times greater than when using free δ-Damascone. The results also suggest that a combination of free δ-damascone and its precursor may produce advantageous effects. Example 7: Precursor deposition studies on cotton in the application of high-strength liquid detergent Example 6 was repeated, replacing the unscented heavy-duty liquid detergent base with an unscented fabric conditioner base. The application involved a single agitation cycle at 200 rpm at room temperature for 20 min, followed by draining the cotton pads and extraction using an ASE (accelerated solvent extractor). The quantification of δ-Damascone as such and its precursors in cotton pad extracts was performed by HPLC-UV with external calibration (0.3-20 ppm) of reference materials in CH3CN. The results are shown in the table below. ααηζ Ln / Lznz / B / YiAi Fabric conditioner Mixture of Example 2 (δ-damascone precursor + released damascone) δ-damascone (comparison) wet (43+7) % 14% 24 h drying (34+1.3) % 1.1% online The results show that the mixture in Example 2, containing a blend of bis- and mono-add, leads to the release of a noticeable amount of δ-Damascone even in the wet state. After 24 h of line drying, the amount of δ-Damascone released from the precursor slightly exceeded the amount released when free δ-Damascone was used. Overall, the amount of bound and free δ-Damascone released from the precursor in wet fabric was 2.6 times greater than when free δ-Damascone was used and more than 25 times greater in dry fabric. The results also suggest that a combination of free δ-Damascone and the precursor may produce advantageous effects. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is the one that is clear from the present description of the invention.

Claims

1. Compound of formula (I): characterized in that one of the dotted lines represents together with the carbon-carbon bond a double bond and each of the other two dotted lines represents together with the carbon-carbon bond a single bond.

2. Mixture, characterized in that it comprises a compound of formula (I) according to claim 1 and a compound of formula (III) wherein the dotted lines represent a double bond located in one of the alpha, beta or delta positions in each of the cyclohexene rings.

3. Mixture according to claim 2, characterized in that the mixture comprises a compound of formula (I) and a compound of formula (II) in a ratio of 1:40 to 40:

1.

4. Mixture according to claim 3, characterized in that the compound of formula (I) is S— (4 — oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)butan-2-yl) ethyl cysteineate and the compound of formula (III) is N,Sbis(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)butan-2-yl) ethyl cysteineate.

5. Mixture according to any of claims 2 to 4, characterized in that it further comprises a compound of formula (IV): oonz Ln / Lznz / E / YiAi wherein the dotted lines represent a double bond located in one of the alpha, beta or delta positions in each of the cyclohexene rings.

6. Mixture according to claim 5, characterized in that the compound of formula (IV) is N-(4-oxo-4-(2', 6', 6'-trimethylcyclohex-3'-en-1'-yl)but-2-en-2-yl)S-(4-oxo-4-(2',6',6'-trimethylcyclohex-3'-en-1'-yl)butan-2-yl) ethyl cysteineate.

7. Use of a compound of formula (I): ααηζ Ln / Lznz / B / YiAi O' NH2 (i) 10 as a precursor to generate, by spontaneous oxidation of air, a damascone of formula (II): sz O where one of the dotted lines represents together with the carbon-carbon bond a double bond and each of the other two dotted lines represents together with the carbon-carbon bond a single bond.

8. Method for generating a compound of formula (II): characterized in that the compound of formula (I), according to claim 1, is exposed to oxygen.

9. Consumer product, characterized in that it comprises a compound of formula (I) according to claim 1 or a mixture according to any of claims 2 to 6 and a consumer product base.

10. Product according to claim 9, characterized in that the consumer product is not a food product, an oral hygiene product, a tobacco product, a confectionery product or a pharmaceutical product.

11. Product according to claim 10, characterized in that the consumer product is a detergent or fabric softener.