Fragrance Precursors

Abstract

The compound of formula (I) is capable of releasing fragrant compounds into the environment in a controlled manner. JPEG2026508427000006.jpg20115, wherein A and R have the same meanings as given herein. A group of compounds represented by the formula:

Description

[Technical Field]

[0001] Technical Field The present invention generally relates to fragrance precursors that release odorous compounds. The present invention also relates to fragrance compositions and consumer products comprising said precursors. The present invention further relates to methods of making said fragrance precursors, fragrance compositions and consumer products. [Background technology]

[0002] background Consumer products, such as fabric care products containing fragrances, are well known in the art. However, over the past few years, interest in precursor technology has been significantly revived, particularly in relation to claims support and customer demand for long-term sustainability in challenging applications. Furthermore, several opportunities, such as future plastic legislation in Europe (which may threaten the use of synthetic microcapsules), may benefit precursor technology. However, new developments should take into account customer and consumer demand for "green" alternatives (considering sustainability, recyclability, and biodegradability).

[0003] Textile cleaning and softening is a particular field where there is a certain need for the effects of active substances, especially fragrance compositions, to remain effective for a certain period after washing, softening, and drying. Indeed, many fragrances particularly suitable for this type of application are known to lack adhesion to laundry or not remain on laundry after rinsing, resulting in their scent effect being experienced only temporarily and not very strong. Considering the importance of this type of application in the perfume industry, research in this field continues, especially with the aim of finding new and more effective solutions to the aforementioned problems. Although the use of fragrance precursors in consumer products is known, there is still room for improvement in terms of odor profile and / or deposition profile. In particular, it is desired to provide compounds that retain long-lasting freshness. Summary of the Invention

[0004] overview According to a first aspect of the present invention there is provided a compound of formula (I): [ka] During the ceremony A is selected from the group consisting of anisyl and naphthyl, and R is selected from C6-C8 alkyl.

[0005] According to a second aspect of the present invention, there are provided fragrance compositions and consumer products comprising compounds of the first aspect of the present invention.

[0006] According to a third aspect of the present invention there is provided the use of a compound of the first aspect as a fragrance precursor, in particular as a precursor capable of releasing a watery, aldehydic, green olfactory impression when exposed to ambient atmosphere.

[0007] According to a fourth aspect of the present invention there is provided a method of making a consumer product comprising incorporating a compound of formula (I) into a consumer product base.

[0008] According to a fifth aspect of the invention there is provided a method of imparting, enhancing, improving or modifying the hedonic properties of a substrate, the method comprising contacting the substrate with a product comprising a compound of the first aspect of the invention.

[0009] Certain embodiments of any aspect of the present invention may provide one or more of the following advantages: ●Balanced odor profile Good deposition properties on the substrate ●Biodegradable Stability in aggressive media

[0010] The details, examples, and preferences provided in connection with any particular one or more of the described aspects of the invention are further described herein and apply equally to all aspects of the invention. Any combination of the embodiments, examples, and preferences described herein, in all their possible variations, is covered by the present invention unless otherwise indicated herein or clearly contradicted by context. DETAILED DESCRIPTION OF THE INVENTION

[0011] Detailed Description The present invention is based on the surprising discovery that compounds of formula (I) as defined herein can serve as fragrance precursors capable of releasing a watery, aldehydic, green odor profile over an extended period of time when exposed to ambient air, which odor profile equates to freshness, a highly sought-after odor impression, especially in fabric care products.

[0012] To that end, compounds of formula (I) are provided herein. [ka] During the ceremony A is selected from the group consisting of anisyl and naphthyl, and R is selected from C6-C8 alkyl (linear or branched).

[0013] In one specific embodiment, the compound of formula (I) is one in which A is anisyl. In another specific embodiment, compounds of formula (I) are those where A is naphthyl. In another specific embodiment, the compound of formula (I) is one in which R is selected from 6-methyl-hept-2-yl, n-hexyl, and n-heptyl.

[0014] Specific examples of the compound represented by formula (I) may include 1-(5-(hexyloxy)pent-1-en-1-yl)-4-methoxybenzene, 1-methoxy-4-(5-((6-methylheptan-2-yl)oxy)pent-1-en-1-yl)benzene, 2-(5-(hexyloxy)pent-1-en-1-yl)naphthalene, and 1-(5-(heptyloxy)pent-1-en-1-yl)-4-methoxybenzene.

[0015] The compound of formula (I) exists in two different isomeric forms. In one specific embodiment, the compound of formula (I) is a compound in which the double bond is in the E-configuration.

[0016] Furthermore, compounds of formula (I) may have one or more stereocenters and therefore may exist as different stereoisomers (e.g., diastereomers or enantiomers), all of which are encompassed by the present invention. Chiral compounds of formula (I) may be enantiomerically pure, enriched, or racemic. When multiple stereocenters are present, the compounds are either diastereomeric mixtures, diastereomerically enriched, or pure diastereomers.

[0017] The inventors have surprisingly discovered that compounds of formula (I) as defined herein have particularly good deposition properties on fabrics and are therefore substantially retained on the fabrics throughout the entire wash cycle, in other words, are not significantly lost during the rinsing procedure, e.g., in a washing machine.

[0018] Thus, in a further aspect of the present invention there is provided a method of imparting, enhancing, improving or modifying the hedonic properties of a substrate, the method comprising contacting said substrate with a rinse-off product comprising a compound of formula (I) as defined herein.

[0019] As used herein, the term "rinse-off product" refers to a product that comes into contact with the treated substrate for a short period of time and is then rinsed off with water. Examples include cleaning products such as detergents (e.g., liquid or powder laundry detergents) and finishes, including fabric softeners. Further examples are typically shower baths, cosmetics such as shampoos and cleaners, which come into contact with the skin for a short period of time and are then rinsed off with water.

[0020] In one particular embodiment, the substrate to be treated is a fabric.

[0021] Due to their good deposition properties, the compounds of formula (I) are not significantly lost during the rinsing procedure but remain on the substrate (fabric, skin, or hair) to which the rinse-off product has been applied, and when a substrate to which a rinse-off product containing a compound of formula (I) has been applied is then exposed to ambient air, a pronounced watery, aldehydic, green olfactory impression is observed.

[0022] Thus, in a further aspect of the present invention, a compound of formula (I) [ka] During the ceremony A is selected from the group consisting of anisyl and naphthyl, and R is selected from C6-C8 alkyl (linear or branched) of a compound represented by Use is provided as a fragrance precursor, in particular as a precursor capable of releasing a watery, aldehydic, green olfactory impression when exposed to ambient air.

[0023] Exposure to ambient air refers to exposure to molecular oxygen, which may cause oxidative cleavage of the compound of formula (I). The oxygen concentration in air is sufficient to cleave the compound of formula (I), and the cleavage products can be detected in ambient air, for example, by olfaction or GC-MS analysis of organic volatiles collected from the precursor headspace.

[0024] The cleavage products of the compound of formula (I) were noticeable for extended periods of time (at least 3 days or more (e.g., 4, 5, 6, or 7 days)). The watery, aldehydic, green olfactory impression was quite noticeable even 4 days after washing the fabrics.

[0025] The compounds of formula (I) are highly stable when stored in their original form in a suitable container protected from air or when stored in a suitable solvent, such as ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, isopropyl myristate, triethyl citrate, diethyl phthalate, triacetin, and / or diacetin. The compounds of formula (I) exhibit high stability even when incorporated into aggressive consumer product bases such as liquid detergents and / or liquid fabric softeners. Thus, the compounds of formula (I) have the potential to be used in a wide range of consumer products.

[0026] By "aggressive medium" is meant in the context of the present invention a composition with a non-neutral pH, for example a pH below 5 or above 9.

[0027] The compounds of formula (I) may be used alone or in combination with additional fragrance precursors and / or odorants well known in the art.

[0028] The odorant(s) may be selected from essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, the wide range of natural products and synthetic molecules currently available, and / or may be mixed with one or more ingredients or excipients conventionally used in conjunction with odorants in perfume compositions, such as carrier materials and other adjuvants commonly used in the art.

[0029] The following non-limiting list includes examples of known odorants that can be combined with compounds of formula (I) in fragrance compositions: • Essential oils and extracts, for example castoreum, costus root oil, oakmoss absolute, geranium oil, tree moss absolute, fruit oils such as basil oil, bergamot oil and mandarin oil, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil and / or ylang-ylang oil;

[0030] Alcohols, such as cinnamic alcohol ((E)-3-phenylprop-2-en-1-ol); cis-3-hexenol ((Z)-hex-3-en-1-ol); citronellol (3,7-dimethyloct-6-en-1-ol); dihydromyrcenol (2,6-dimethyloct-7-en-2-ol); Ebanol TM ((E)-3-Methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol); Eugenol (4-allyl-2-methoxyphenol); Ethyl linalool ((E)-3,7-dimethylnona-1,6-dien-3-ol); Farnesol ((2E,6Z)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol); Geraniol ((E)-3,7-dimethylocta-2,6-dien-1-ol); Super Muguet TM ((E)-6-Ethyl-3-methyloct-6-en-1-ol); Linalool (3,7-dimethylocta-1,6-dien-3-ol); Menthol (2-isopropyl-5-methylcyclohexanol); Nerol (3,7-dimethyl-2,6-octadien-1-ol); Phenylethyl alcohol (2-phenylethanol); Rhodinol TM (3,7-dimethyloct-6-en-1-ol); Sandalore TM(3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohex-3-en-1-yl)propan-2-ol); or Timberol TM (1-(2,2,6-trimethylcyclohexyl)hexan-3-ol); 2,4,7-trimethylocta-2,6-dien-1-ol, and / or [1-methyl-2(5-methylhex-4-en-2-yl)cyclopropyl]-methanol;

[0031] Aldehydes and ketones, such as anisaldehyde (4-methoxybenzaldehyde); alpha-amyl cinnamic aldehyde (2-benzylideneheptanal); and Georgywood TM (1-(1,2,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); Hydroxycitronellal (7-hydroxy-3,7-dimethyloctanal); Iso E Super (R) (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone);Isoraldeine (R) ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one);Hedione (R) (Methyl 3-oxo-2-pentylcyclopentaneacetate); Nympheal (3-(4-isobutyl-2-methylphenyl)propanal); Mahonial (5,9-dimethyl-9-hydroxy-decen-4-al); Maltol; Methyl cedryl ketone; Methyl ionone; Verbenone; and / or Vanillin;

[0032] Ethers and acetals, e.g., Ambrox (R)(3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran); geranyl methyl ether ((2E)-1-methoxy-3,7-dimethylocta-2,6-diene); rose oxide (4-methyl-2-(2-methylprop-1-en-1-yl)tetrahydro-2H-pyran); and / or Spirambrene (R) (2',2',3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5'-[1,3]dioxane]);

[0033] Esters and lactones, such as benzyl acetate; cedryl acetate ((1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methanoazulen-6-yl acetate); decalactone (6-pentyltetrahydro-2H-pyran-2-one); Helvetolide (R) (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl)propionate; -undecalactone (5-heptyloxolan-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)

[0034] Macrocycles, e.g., ambrettolide ((Z)-oxacycloheptadecan-10-en-2-one); ethylene brassylate (1,4-dioxacycloheptadecan-5,17-dione); and / or exaltolide (R) (16-oxacyclohexadecan-1-one); and • Heterocycles, for example, isobutylquinoline (2-isobutylquinoline).

[0035] The compounds of formula (I), as defined herein above, are particularly suitable for use in rinse-off products, although they may of course be used in any type of consumer product. Thus, in a further aspect of the present invention there is provided a consumer product comprising a compound of formula (I) and a consumer product base.

[0036] For example, the consumer product according to the invention is selected from the group consisting of detergents and cleaning agents, hygiene or care products, preferably body care and hair care, cosmetics and household sectors, preferably selected from the group consisting of fragrance extracts, eau de parfum, eau de toilette, aftershave lotions, eau de cologne, pre-shave products, splash cologne, scented refreshing wipes, acidic, alkaline or neutral detergents, textile fresheners, ironing aids, liquid detergents, washing powders, laundry pre-treatments, fabric softeners, laundry sheets, cleaning soaps, cleaning tablets, dish soap bars, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, body care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, suntan creams and lotions, hair care products (liquid or solid), dry shampoo, deodorants, antiperspirants, decorative cosmetic products, candles, lamp oil, incense, insecticides, insect repellents and fuel.

[0037] The consumer product may be selected from, for example, fine fragrances, personal care products (body care products, hair care products, cosmetics), fabric care products, home care products, and air care products. As used herein, "consumer product base" means a composition for use as a consumer product to perform a specific function, such as cleaning, softening, and caring, or the like.

[0038] The personal care products that can be added with the compound of formula (I) include, for example, all kinds of body care products.Products that are particularly interesting are, for example, hair care products such as shampoo, conditioner and hairspray, and skin care products such as lotion and cream.Furthermore, the compound of formula (I) can be added to soap, bath and shower gel and deodorant.

[0039] Home care products to which the compounds of formula (I) can be added include all types of detergents, window cleaners, hard surface cleaners, all-purpose cleaners, and furniture polishes. In one specific embodiment, the product is a liquid, for example, a fabric detergent or conditioner composition.

[0040] The compounds of formula (I) may be used in a wide range of consumer products across the fine and functional fragrance spectrum, including, for example, perfumes, air care products, household products, laundry products, body care products, and cosmetics. The compounds may be employed in a wide variety of amounts, depending on the specific product and the nature and amount of other odorant ingredients. The proportion of formula (I) is typically 0.001 to 5% by weight of the product. In one embodiment, the compounds of formula (I) may be employed in fabric softeners in an amount of 0.01 to 0.5% by weight (e.g., 0.05 to 0.1%, including 0.2%). In another embodiment, the compounds of formula (I) may be employed in laundry detergents in an amount of 0.01 to 0.5% by weight (e.g., 0.1 to 0.3%, including 0.2%) based on the final product. In another embodiment, the compounds of formula (I) may be used in fine fragrances in an amount of 0.001 to 30% by weight (e.g., up to about 10% or up to 20% by weight), more preferably between 0.01 and 5% by weight. However, these values ​​are given only as an example, since a skilled perfumer may also achieve effects or realize novel accords at lower or higher concentrations.

[0041] The compounds of formula (I) may be incorporated into the consumer product base by simply directly mixing the compound of the present invention, or a fragrance composition comprising a compound of formula (I), with the consumer product base, or may be encapsulated in a previous step with an encapsulating material, such as, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film-forming agents, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the consumer product base. The consumer product base may further comprise an encapsulating material capable of releasing other fragrance compounds.

[0042] Thus, there is provided a method for producing a consumer product that includes the incorporation of a compound of formula (I) by directly incorporating it into the consumer product base using conventional techniques and methods, or by mixing a fragrance composition that includes a compound of formula (I), which may then be mixed with the consumer product base.

[0043] The compounds of formula (I) may be prepared starting from an aldehyde A-CHO, where A has the same meaning as given for formula (I), by reacting with a Grignard reagent prepared from a chloride Cl-CHCHCHCHOR, where R has the same meaning as given for formula (I), using methods known to those skilled in the art, such as reacting the halide with magnesium turnings in a suitable solvent (e.g., THF (tetrahydrofuran)) at elevated temperature (e.g., 60°C), followed by slow addition of the aldehyde (A-CHO) at reduced temperature (e.g., -20°C). The resulting carbinol A-CH(OH)CHCHCHCHOR can be converted to the compound of formula (I) by dehydration, which can be achieved, for example, by treatment with a catalytic amount of acid (e.g., para-toluenesulfonic acid or sulfuric acid) in a suitable solvent (e.g., toluene), optionally at elevated temperatures (e.g., 110°C), optionally removing the generated water by azeotropic distillation (e.g., using a Dean-Stark apparatus). Other methods for the synthesis of the compound of formula (I) exist and will be apparent to those skilled in the art.

[0044] The present invention will now be further described with reference to the following non-limiting examples, which are intended for illustrative purposes only and it will be understood that variations and modifications may occur to those skilled in the art.

[0045] Example 1: 1-(5-(hexyloxy)pent-1-en-1-yl)-4-methoxybenzene A flask was charged with magnesium turnings (7.23 g, 297 mmol) and slowly treated with a solution of 1-(4-chlorobutoxy)hexane (57.3 g, 297 mmol) in THF (148 mL) over 30 min to ensure the Grignard reaction was initiated. The resulting mixture was heated to reflux (oil bath at 120 °C) and the reaction was continued for 12 h. The resulting solution was cooled to room temperature and slowly added to a cooled (-20 °C) solution of anisaldehyde (40.4 g, 297 mmol) in THF (35 mL), maintaining the temperature below -15 °C, and then stirred for 1 h. The resulting mixture was poured into ice-cold 2N H2SO4 solution (pH 1), stirred for 10 min, extracted with MTBE (methyl tert-butyl ether), washed with brine, dried over MgSO4, and evaporated. The resulting mixture was taken up in toluene (300 mL), treated with 62% H2SO4 (0.47 g, 2.97 mmol), and refluxed using a Dean-Stark apparatus to remove water. After complete dehydration (30 min), the mixture was cooled to room temperature, poured into saturated aqueous NaHCO3 solution, extracted twice with MTBE, dried over MgSO4, evaporated, and purified by wipe-film distillation to give the crude product: 1-(5-(hexyloxy)pent-1-en-1-yl)-4-methoxybenzene (64.7 g, 75% yield, 96% purity) as a pale yellow oil.

[0046] 1H NMR (400 MHz, CDCl3, 298 K) δ (ppm) = 7.30 - 7.23 (m, 2H), 6.86 - 6.80 (m, 2H), 6.34 (d, J = 15.9 Hz, 1H), 6.07 (td, J = 7.0, 15.8 Hz, 1H), 3.79 (s, 3H), 3.44 (t, J = 6.5 Hz, 2H), 3.40 (t, J = 6.7 Hz, 2H), 2.31 - 2.20 (m, 2H), 1.79 - 1.68 (m, 2H), 1.63 - 1.51 (m, 2H), 1.39 - 1.25 (m, 6H), 0.95 - 0.84 (m, 3H). 13 C NMR (101 MHz, CDCl3, 298 K) δ (ppm) = 158.7, 130.7, 129.5, 128.2, 127.0, 113.9, 71.0, 70.1, 55.3, 31.7, 29.8, 29.6, 29.5, 25.9, 22.7, 14.1. MS (EI, 70 eV): 276 (15, [M + *]), 176 (33), 174 (62), 159 (54), 147 (100), 121 (59). Odor description (1% solution in EtOH, on blotting paper, 24h): floral, watery, aldehydic, green, powdery.

[0047] Example 2: 1-Methoxy-4-(5-((6-methylheptan-2-yl)oxy)pent-1-en-1-yl)benzene Example 2a: 2-(4-chlorobutoxy)-6-methylheptane: A flask was charged with tetrahydrofuran (15.0 g, 208 mmol) and 6-methylheptan-2-ol (27.1 g, 208 mmol). The mixture was cooled to 5 °C and then treated dropwise with thionyl chloride (SOCl) (29.7 g, 18 mL, 250 mmol). After the addition, the cooling bath was removed, and the reaction mixture was slowly heated to 120 °C for 6 h and then cooled to room temperature. The reaction mixture was poured into ice-cold 2 M NaOH, extracted twice with MTBE, washed with water and brine until neutral, dried over MgSO, filtered, and concentrated. The crude material was purified by Kugelrohr distillation to give 2-(4-chlorobutoxy)-6-methylheptane (13.26 g, 60.1 mmol, 29% yield) as a colorless oil.

[0048] 1 H NMR (400 MHz, CDCl3, 298 K) δ (ppm) = 3.62 - 3.56 (m, 2H), 3.55 - 3.50 (m, 1H), 3.42 - 3.33 (m, 2H), 1.94 - 1.84 (m, 2H), 1.76 - 1.67 (m, 2H), 1.61 - 1.46 (m, 2H), 1.42 - 1.27 (m, 3H), 1.22 - 1.15 (m, 2H), 1.14 (d, J = 6.4 Hz, 3H), 0.89 (d, J = 6.6 Hz, 6H). 13 C NMR (101 MHz, CDCl3, 298 K) δ (ppm) = 75.5, 67.4, 45.0, 39.0, 36.9, 29.7, 28.0, 27.6, 23.3, 22.6, 22.6, 19.7.

[0049] Example 2b: 1-Methoxy-4-(5-((6-methylheptan-2-yl)oxy)pent-1-en-1-yl)benzene: Prepared in a manner similar to Example 1 using 2-(4-chlorobutoxy)-6-methylheptane (16.1 g, 72.7 mmol), magnesium turnings (1.77 g, 72.7 mmol), and anisaldehyde (9.0 g, 66 mmol), followed by dehydration of pTSA (using para-toluenesulfonic acid instead of sulfuric acid used in Example 1) (1.26 g, 6.6 mmol) to give 1-methoxy-4-(5-((6-methylheptan-2-yl)oxy)pent-1-en-1-yl)benzene (11.1 g, 98% purity, 54% yield) as a pale yellow oil.

[0050] 1 H NMR (400 MHz, CDCl3, 298 K) δ (ppm) = 7.30 - 7.23 (m, 2H), 6.86 - 6.79 (m, 2H), 6.34 (d, J = 15.9 Hz, 1H), 6.07 (td, J = 6.9, 15.8 Hz, 1H), 3.79 (s, 3H), 3.52 (td, J = 6.4, 9.2 Hz, 1H), 3.43 - 3.30 (m, 2H), 2.31 - 2.22 (m, 2H), 1.77 - 1.63 (m, 2H), 1.59 - 1.47 (m, 2H), 1.46 - 1.26 (m, 4H), 1.22 - 1.14 (m, 2H), 1.12 (d, J = 6.1 Hz, 3H), 0.87 (d, J = 6.6 Hz, 6H). 13 C NMR (101 MHz, CDCl3, 298 K) δ (ppm) = 158.7, 130.7, 129.5, 128.3, 127.0, 113.9, 75.5, 67.7, 55.3, 39.1, 37.0, 29.9, 29.7, 28.0, 23.4, 22.7, 22.6, 19.8. MS (EI, 70 eV): 304 (2, [M +*]), 191 (11), 176 (39), 159 (22), 147 (100), 121 (56). Odor description (1% solution in EtOH, on blotting paper, 24 h): aldehyde, watery, green, metallic, marine, powdery.

[0051] Example 3: 2-(5-(hexyloxy)pent-1-en-1-yl)naphthalene Prepared as in Example 1, substituting 2-naphthaldehyde for anisaldehyde, to give 2-(5-(hexyloxy)pent-1-en-1-yl)naphthalene as a pale yellow oil.

[0052] 1 H NMR (400 MHz, CDCl3, 298 K - ca. 1:1 mixture of E and Z isomers) δ (ppm) = 7.93 - 7.66 (m, 4H), 7.65 - 7.38 (m, 3H), 6.74 - 6.50 (m, 1H), 6.50 - 5.68 (m, 1H), 3.62 - 3.31 (m, 4H), 2.59 - 2.31 (m, 2H), 1.88 - 1.75 (m, 2H), 1.69 - 1.50 (m, 2H), 1.45 - 1.23 (m, 6H), 0.97 - 0.86 (m, 4H). 13 C NMR (101 MHz, CDCl3, 298 K - ca. 1:1 mixture of E and Z isomers) δ (ppm) = 135.3, 135.2, 133.7, 133.4, 132.9, 132.7, 132.2, 130.9, 130.3, 129.3, 128.0, 127.9, 127.8, 127.6, 127.6, 127.4, 127.2, 126.1, 126.0, 125.6, 125.5, 125.4, 123.6, 120.0, 71.1, 70.1, 31.9, 31.7, 31.7, 29.8, 29.8, 29.8, 25.9, 25.9, 25.4, 22.7, 22.7, 22.6, 14.1, 14.1, 14.1. MS (EI, 70 eV): 296 (11, [M + *]), 212 (1), 194 (56), 179 (100), 167 (66), 165 (81), 152 (36), 141 (45), 128 (38), 43 (31). Odor description (1% solution in EtOH, on blotting paper, 24 h): aldehyde, green, metallic, ozonic.

[0053] Example 4: 1-(5-(heptyloxy)pent-1-en-1-yl)-4-methoxybenzene Prepared as in Example 1, substituting 1-(4-chlorobutoxy)heptane for 1-(4-chlorobutoxy)hexane to give 1-(5-(heptyloxy)pent-1-en-1-yl)-4-methoxybenzene as a pale yellow oil.

[0054] 1 H NMR (400 MHz, CDCl3, 298 K) δ (ppm) = 7.35 - 7.22 (m, 2H), 6.93 - 6.80 (m, 2H), 6.37 (d, J = 15.6 Hz, 1H), 6.10 (td, J = 6.9, 15.8 Hz, 1H), 3.89 - 3.77 (m, 3H), 3.47 (t, J = 6.5 Hz, 2H), 3.43 (t, J = 6.7 Hz, 2H), 2.35 - 2.22 (m, 2H), 1.85 - 1.70 (m, 2H), 1.67 - 1.53 (m, 2H), 1.50 - 1.23 (m, 8H), 0.97 - 0.84 (m, 3H). 13 C NMR (101 MHz, CDCl3, 298 K) δ (ppm) = 158.7, 130.7, 129.5, 128.2, 127.0, 113.9, 71.0, 70.1, 55.3, 31.9, 29.8, 29.6, 29.5, 29.2, 26.2, 22.6, 14.1. MS (EI, 70 eV): 290 (12, [M +*]), 192 (2), 174 (70), 159 (52), 147 (100), 121 (65). Odor description (1% solution in EtOH, on blotting paper, 24h): aldehyde, green, floral, watery, lily of the valley.

[0055] Example 5 (Comparative): (6-(6-methylheptan-2-yloxy)hex-2-enyl)benzene A solution of phenethyltriphenylphosphonium bromide (2.20 g, 4.92 mmol, 1.0 equiv.) in THF (10 mL) was cooled to 0 °C. After adding n-BuLi (1.6 M in hexanes, 3.1 mL, 4.92 mmol, 1.0 equiv.) at 0 °C, the red solution was stirred at 60 °C for 1 h. The mixture was recooled to 0 °C, and 4-(6-methylheptan-2-yloxy)butanal (0.86 g, 4.29 mmol, 0.9 equiv.) in THF (5 mL) was added and stirred at 70 °C for 20 h. After adding HO, the aqueous layer was extracted with cyclohexane (2x), and the combined organic phases were washed with brine, dried (MgSO), filtered, and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane / EtOAc 997:3) to give 0.42 g (27%) of the title compound as a yellow oil.

[0056] Odor description (1% solution in EtOH, on blotting paper, 24h): weak, floral, hyacinth, warm, honey, animalic.

[0057] Example 6 (Comparative): (E)-1-(dodec-1-en-1-yl)-4-methoxybenzene The title compound was prepared from anisaldehyde and dodecylaldehyde according to the procedure described in WO2014 / 073003.

[0058] Odor description (1% solution in EtOH, on blotting paper, 24 h): green, anise, metallic, aldehyde.

[0059] Example 7: Application in liquid cleaning agents 0.2 wt. % of 1-(5-(hexyloxy)pent-1-en-1-yl)-4-methoxybenzene (Example 1) was incorporated into the unscented liquid detergent base with magnetic stirring at room temperature for 24 h.

[0060] A 55g sample of the liquid detergent prepared above and a neutral-smelling cotton / elastane blend T-shirt were subjected to a washing machine wash cycle at 40°C. The line-dried fabrics (1 and 3 days) were evaluated for odor intensity and quality by a panel of 4-6 experts. Odor intensity was recorded on an intensity scale from 0 (no odor) to 5 (extremely strong).

[0061] T-shirts washed with 1-(5-(hexyloxy)pent-1-en-1-yl)-4-methoxybenzene were found to exhibit an aldehyde, watery, metallic, and powdery odor with an intensity of 2.6 after one day and 3.2 after three days.

[0062] Example 8 (comparison): Application to liquid detergents 0.2 wt. % of (E)-1-(dodec-1-en-1-yl)-4-methoxybenzene (Example 6) was incorporated into the unscented liquid detergent base with magnetic stirring at room temperature for 24 h. A 55g sample of the liquid detergent prepared above and a neutral-smelling cotton / elastane blend T-shirt were subjected to a washing machine wash cycle at 40°C. The line-dried fabrics (1 and 3 days) were evaluated for odor intensity and quality by a panel of 4-6 experts. Odor intensity was recorded on an intensity scale from 0 (no odor) to 5 (extremely strong).

[0063] No noticeable odor was observed on the T-shirt, which was consistently below 1 after 1 and 3 days, respectively.

[0064] (E)-1-(dodec-1-en-1-yl)-4-methoxybenzene was clearly perceived on the blotter paper after 24 h (Example 6), but not on the dry cloth after washing (Example 8), and was therefore (mostly) lost during the wash cycle, confirming the good deposition properties of the compound of formula (I) as defined herein.

Claims

1. Formula (I): 【Chemistry 1】 During the ceremony, A is selected from the group consisting of anisyl and naphthyl, and R is C ６ -C ８ selected from alkyl, A compound represented by the formula:

2. 2. The compound of claim 1, selected from the group consisting of 1-(5-(hexyloxy)pent-1-en-1-yl)-4-methoxybenzene, 1-methoxy-4-(5-((6-methylheptan-2-yl)oxy)pent-1-en-1-yl)benzene, 2-(5-(hexyloxy)pent-1-en-1-yl)naphthalene, and 1-(5-(heptyloxy)pent-1-en-1-yl)-4-methoxybenzene.

3. 3. The compound of claim 1 or 2, wherein the double bond is in the E-configuration.

4. The compound is 1-(5-(hexyloxy)pent-1-en-1-yl)-4-methoxybenzene, (E)-1-(5-(hexyloxy)pent-1-en-1-yl)-4-methoxybenzene, 1-methoxy-4-(5-((6-methylheptan-2-yl)oxy)pent-1-en-1-yl)benzene, (E)-1-methoxy-4-(5-((6-methylheptan-2-yl)oxy)pent-1-en-1-yl)benzene 4. The compound of claim 1, wherein the compound is selected from the group consisting of benzene, 2-(5-(hexyloxy)pent-1-en-1-yl)naphthalene, (E)-2-(5-(hexyloxy)pent-1-en-1-yl)naphthalene, 1-(5-(heptyloxy)pent-1-en-1-yl)-4-methoxybenzene, and (E)-1-(5-(heptyloxy)pent-1-en-1-yl)-4-methoxybenzene.

5. A fragrance composition comprising a compound of formula (I) as defined in claims 1 to 4, or a mixture thereof.

6. A consumer product comprising a compound of formula (I) as defined in claims 1 to 4 or a fragrance composition as defined in claim 5, and a consumer product base.

7. 7. The consumer product of claim 6, wherein the product is selected from the group consisting of rinse-off products.

8. 8. The consumer product of claim 7, wherein the rinse-off product is selected from the group consisting of fabric care and personal care products.

9. 9. The product of claim 8, wherein the fabric care product is selected from laundry detergent and fabric softener products.

10. A method of imparting, enhancing, improving or modifying the hedonic properties of fabrics, comprising contacting the fabrics with a rinse-off product comprising a compound of formula (I) as defined in claims 1 to 4, or a mixture thereof.

11. 11. The method of claim 10, wherein the rinse-off product is selected from the group consisting of fabric care and personal care products.

12. Use of a compound of formula (I) as defined in claims 1 to 4 as a fragrance precursor.

13. 13. Use according to claim 12, wherein the compound of formula (I) is capable of releasing a watery, aldehydic, green olfactory impression when exposed to ambient air.

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