WO2025051973A1

WO2025051973A1 - 3-cyclohexyl-2-methylpropanal as a fragrance

Info

Publication number: WO2025051973A1
Application number: PCT/EP2024/075020
Authority: WO
Inventors: Neil FAIRFAX; Robert BEGBIE; Natalie KEEHAN
Original assignee: Lanxess Chemical Ltd
Current assignee: Lanxess Chemical Ltd
Priority date: 2023-09-07
Filing date: 2024-09-06
Publication date: 2025-03-13
Anticipated expiration: 2026-03-07
Also published as: WO2025051974A1

Abstract

The present invention relates to the use of 3-cyclohexyl-2-methylpropanal according to Formula (I) as a fragrance as well as methods for imparting, modifying and/or enhancing fragrance compositions and consumer product bases.

Description

3-CYCL0HEXYL-2-METHYLPR0PANAL AS A FRAGRANCE

FIELD OF THE INVENTION

The present invention relates to the use of 3-cyclohexyl-2-methylpropanal according to Formula (I)

Formula (I) as a fragrance. Furthermore, the present invention relates to fragrance compositions, their uses, fragranced articles and processes for producing such fragrance and such fragrance compositions as well as methods for imparting, modifying and/or enhancing fragrance compositions and consumer product bases.

BACKGROUND

In the fragrance and flavor industry, perfumers and flavorists are continually looking for new compounds possessing unique odor characteristics which can be used as fragrance. The creation of a new fragrance or fragrance compositions involves a number of significant challenges. Suitable fragrances show a beneficial performance, but in combination with other fragrance ingredients may develop unpleasant and thus detrimental odor aspects, making it difficult to use them for a specific application. It is necessary to select a specific composition of several fragrance ingredients from an almost unlimited number of possible structures known from the prior art, in order to satisfy a specific need of the market and provide a product that matches the specific profile required by the customer.

Following the European Union (EU) ban on the use of 2-(4-tert-butylbenzyl) propionaldehyde (Lilestralis®) in cosmetic products from March 1^st, 2022 and with increasing restrictions on its usage in many fragrance applications, there is a need to identify new fragrance compounds that have multifaceted odor and which can not only provide an odor direction for a fragrance but can also provide a major blooming and freshness impact on a fragrance; organoleptic properties that are typically associated with 2-(4-tert- butylbenzyl) propionaldehyde.

Another important problem concerns the need to provide fragrance compositions that are not only consistent with a particular odor profile, but also possess additional beneficial properties. Indeed, many fragrance compositions known from the market have significant drawbacks in use, such as poor solubility and stability to storage, but also failures in subjective issues such as richness, charisma, and the like. In addition, many known fragrance compositions require high dosages to achieve the desired odor result. Desirable beneficial properties are for the fragrance compound to be stable over time yet be readily biodegradable in the environment.

Apart from the fragrance being appreciated by a consumer, an important technical factor in fragranced articles is the substantivity of the fragrance or fragrance composition to the substrate. Substantivity is an important factor in the persistence of e.g. a fragrance on the skin, a fragrance in shampoos or conditioners on the hair, or a perfume in a detergent or fabric softener on textile fibers. Less substantive fragrance compositions would require a higher amount of fragrance compounds, in order to remain effective for an equal period, but this could lead to too high a concentration of fragrance compounds, resulting in a less pleasant odor.

Fragranced articles, for example perfumed consumer products such as cleaning or laundry products comprising fragrances are well-known in the art. However, it is known that fragrances may be altered when incorporated in certain consumer product bases, where alkalinity, acidity, the presence of oxidizing agents, such as hypochlorite salts, or other base components may lead to chemical degradation of the fragrance. In addition, volatile fragrances tend to be dissipated with time. Furthermore, when used in cleaning or laundry products, the deposition of the fragrance on a treated substrate is diminished by the washing and/or rinsing procedure.

Compounds having structural similarities to 2-(4-tert-butylbenzyl) propionaldehyde and processes for producing such compounds are known in the art, including, amongst many others, 3-cyclohexyl-2-methylpropanal.

Journal of the American Chemical Society (1968), Volume 90(15), pages 4165-4166 discloses 3-cyclohexyl-2-methylpropanal. 3-Cyclohexyl-2-methylpropanal is synthesized by the reaction of 2-methylacrolein with tricyclohexenylborane. Use of 3-cyclohexyl-2- methylpropanal as a fragrance is not disclosed.

Journal of the American Chemical Society (1969), Volume 91(21), pages 5887-5888 discloses the synthesis of 3-cyclohexyl-2-methylpropanal via the reaction of 2-isopropenyl- 4,4,6-trimethyl-5,6-dihydro-1 ,3-4H-oxazine with cyclohexyl magnesium bromide to generate 2-(1-cyclohexyl-2-propyl)-4,4,6-trimethyl-5,6-dihydro-1 ,3-4H-oxazine. This is then further reacted with NaBH4. Use of 3-cyclohexyl-2-methylpropanal as a fragrance is not disclosed. LIS4131623 discloses the production of complex aliphatic, unsaturated and cycloalkane aldehydes, including the production of 3-cyclohexyl-2-methylpropanal. The aldehyde is produced by the reaction of tetrahydro-1 , 3-oxazine and hydrated oxalic acid. The patent mentions the general utility of aldehydes in various industries, including amongst pharmaceuticals and insect repellants and also flavors and perfumes. However, it does not disclose the use of 3-cyclohexyl-2-methylpropanal as a fragrance, nor does it describe any pleasant odor or organoleptic properties of any of 3-cyclohexyl-2-methylpropanal or any of the aldehydes.

Journal of Organic Chemistry (1973), Volume 38(12), pages 2136-2143 discloses 3- cyclohexyl-2-methylpropanal. 2-lsopropenyl-4,4,6-trimethyl-5,6-dihydro-1 ,3-4H-oxazine was reacted with cyclohexyl magnesium bromide at -60°C in tetrahydrofuran to generate 2- (1-cyclohexyl-2-propyl)-4,4,6-trimethyl-5,6-dihydro-1 ,3-4H-oxazine which was then transformed into 3-cyclohexyl-2-methylpropanal using NaBH4. Whilst reaction yields and physical properties of 3-cyclohexyl-2-methylpropanal are quoted, no reference is made to the odor properties of the molecule or its use as a fragrance.

Tetrahedron (2015), Volume 71 (8), pages 1241-1246 discloses 3-cyclohexylpropene as a substrate for the production of 3-cyclohexyl-2-methylpropanal. The synthesis of 3- cyclohexyl-2-methylpropanal is described by the Cobalt catalyzed hydroformylation of 3- cyclohexylpropene. Under this synthetic route, selectivity is significantly directed towards producing the straight chain aldehyde, 4-cyclohexylbutanal, rather than the branched chain aldehyde, 3-cyclohexyl-2-methylpropanal. The use of 3-cyclohexyl-2-methylpropanal as a fragrance is not described.

US6187727 discloses a method of imparting, modifying or enhancing the fragrance of a perfume or perfumed article comprising adding thereto a fragrance-imparting amount of 3- cyclohexyl-2-methylpropanol or esters thereof. 3-cyclohexyl-2-methylpropanal is not disclosed.

US7511001 discloses derivatives of 3-cyclohexyl-propanal, more particularly 3-(3- isopropyl-cyclohexyl)-2-methylpropanal, having olfactory properties, useful for improving, enhancing, or modifying a fragrance formulation. 3-cyclohexyl-2-methylpropanal is not disclosed.

W02022/058019 discloses derivatives of 3-cyclohexyl-propanal, wherein the cyclohexyl group comprises at least one double bond and can be unsubstituted, useful as fragrance substance and useful for imparting, modifying and/or enhancing one or more olfactory notes selected from the group consisting of the notes green, fatty, ozonic, cyclamen-like, dusty, citrus, mandarin, aldehydic, citral, fresh, lily of the valley, Bourgeonal, floral, cucumber, fruity and melon. 3-cyclohexyl-2-methylpropanal is not disclosed.

The prior art does not disclose the use of 3-cyclohexyl-2-methylpropanal as a fragrance compound with particularly pleasant or interesting odor characteristics.

The object of the present invention was to provide an organic compound that possess interesting odor characteristics and may be used as fragrance, while also being readily biodegradable and/or having low human toxicity and/or ecotoxicity and/or being stable over at least 4 weeks. It was further desired to provide a compound that exhibits the blooming effect that 2-(4-tert-butylbenzyl) propionaldehyde provides, particularly in laundry care, where freshness may be imparted.

Surprisingly, the inventors found that 3-cyclohexyl-2-methylpropanal may be used as a fragrance as it provides interesting odor characteristics due to its strength and combination of green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper odor notes and highly diffusive nature, while being readily biodegradable.

SUMMARY

Thus, there is provided with the first aspect of the present invention the use of 3-cyclohexyl- 2-methylpropanal as a fragrance in a fragrance composition.

In accordance with the second aspect of the invention, there is provided the use of 3- cyclohexyl-2-methylpropanal in a fragrance composition to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper.

In accordance with the third aspect of the invention, there is provided the use of 3- cyclohexyl-2-methylpropanal for enhancing the bloom of a fragrance composition.

In accordance with the fourth aspect of the invention, there is provided the use of a fragrance composition comprising 3-cyclohexyl-2-methylpropanal to modify an existing fragrance to provide freshness and/or blooming character and/or to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper. In accordance with the fifth aspect of the invention, there is provided a method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a fragrance composition, comprising the steps of (a) providing a fragrance composition and (b) adding a sensory effective amount, preferably 10 ppm or more, of 3-cyclohexyl-2-methylpropanal to the fragrance composition.

In accordance with the sixth aspect of the invention, there is provided a method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a consumer product base, comprising the steps of (a) providing a consumer product base and (b) adding a sensory effective amount, preferably 10 ppm or more, of 3-cyclohexyl-2-methylpropanal to the consumer product base.

In accordance with the seventh aspect of the invention, there is provided a method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a fragranced article, comprising the following steps: (a) providing a fragranced article and (b) adding a sensory effective amount, preferably 10 ppm or more, of 3-cyclohexyl-2-methylpropanal to the consumer product base.

In accordance with the eighth aspect of the invention, there is provided a fragrance composition comprising 3-cyclohexyl-2-methylpropanal, characterized in that the total amount of 3-cyclohexyl-2-methylpropanal in the fragrance composition is sufficient to provide freshness and/or blooming character and/or to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper.

In accordance with the ninth aspect of the invention, there is provided a fragrance composition according to the eighth aspect of the invention, wherein the total amount of 3- cyclohexyl-2-methylpropanal in the fragrance composition is in the range of from 0.001 to 99.9 wt.-%, preferably in a range of from 0.01 to 99.5 wt.-%, particularly preferably 0.1 to 99 wt.-% and most preferably 0.1 to 10 wt.-%, based on the total weight of the fragrance composition. In accordance with the tenth aspect of the invention, there is provided a fragrance composition according to the eighth or ninth aspect of the invention, that further comprises at least one antioxidant, preferably selected from the group consisting of pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, tris(tetramethylhydroxypiperidinol) citrate, tertbutylhydroquinone, hydroquinone, Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tocopherol, tocopherol acetate, tocopherol palmitate, butylhydroxyanisole and 2,6-bis(1 , 1- dimethylethyl)-4-methylphenol, more preferably tocopherol, tert-butylhydroquinone or Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and most preferably tert-butylhydroquinone.

In accordance with the eleventh aspect of the invention, there is provided a fragrance according to any of the eighth, ninth or tenth aspect of the invention further comprises at least one other fragrance ingredient.

In accordance with the twelfth aspect of the invention, there is provided a process for producing a fragrance composition according to any of the eighth to eleventh aspect of the invention, comprising the step of mixing 3-cyclohexyl-2-methylpropanal to at least one other fragrance ingredient of the fragrance composition.

In accordance with the thirteenth aspect of the invention, there is provided a fragranced article, characterized in that it comprises (a) a consumer product base and (b) 3-cyclohexyl- 2-methylpropanal in a total amount sufficient to modify an existing fragrance to provide freshness and/or blooming character and/or to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper.

In accordance with the fourteenth aspect of the invention, there is provided a fragranced article according to the thirteenth aspect of the invention, wherein the consumer product base is selected from the group consisting of fine perfumery, including perfume, perfume extracts, eau de perfume, eau de toilette, aftershave, eau de cologne, pre-shave products, splash colognes and perfumed refreshing towels, household or home care products, including acidic, alkaline and neutral cleaning agents, including surface cleaner, floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring milk, solid and liquid toilet cleaners, powder and foam carpet cleaners, textile fresheners, ironing aids, liquid detergents, powder detergents, rinse conditioner, personal cleansing composition, personal care products & body-care products, including bath products, toiletries, solid and liquid soaps, cosmetics products including cosmetic emulsions of the oil-in-water, of the water-in-oil and of the water-in-oil-in-water type including skin care products, especially skin washing and cleansing products, shower gels, body lotions, bath oils, skin creams and lotions, face creams and lotions, hand creams and lotions, foot care products including foot creams and lotions, intimate care products; dental care products, especially dental and oral care products, tooth care products, cleaners for dental prostheses, adhesives for dental prostheses; hair care products, including hair sprays, hair gels, setting hair lotions, hair shampoos, hair care products, hair conditioners, hair coloring products including permanent and semi-permanent hair dyes, hair setting products, hair shaping agents including cold waves and hair straighteners, hair lotions and hair creams; and cosmetic products with specific effects, especially sunscreens, sun protection creams and lotions, after-sun creams and lotions, tanning products including tanning creams and lotions, de-pigmenting products, deodorants and antiperspirants including underarm sprays, roll-ons, deodorant sticks and deodorant creams, hair removers and shaving products including shaving soaps, shaving foams, depilatory creams and lotions, aftershave creams and lotions; fabric care and laundry (pretreatment) products, including softener, laundry detergents, bleach, soaking agents, stain removers, fabric softeners, laundry soaps, washing tablets, and disinfectants; products in decorative cosmetics including eye makeup, eye shadow, mascara, nail care products including nail varnish, lip care products including lipsticks; air care products, including products that contain preferably volatile and usually pleasant-smelling compounds which advantageously, even in very small amounts, can mask unpleasant odors including candles, lamp oils, incense sticks, reed diffusers, bakhoors, insecticides, repellants and fuels; air fresheners in liquid, gel-like or applied form on a solid carrier, aerosol sprays, waxes and polishes including furniture polishes, floor waxes and shoe creams.

In accordance with the fifteenth aspect of the invention, there is provided a fragranced article according to the thirteenth or fourteenth aspect of the invention, characterized in that the consumer product base is selected from the group consisting of eau de toilette, powder detergent, liquid detergent, laundry detergent, reed diffuser, body lotion, shower gel and bakhoor.

In accordance with the sixteenth aspect of the invention, there is provided a fragranced article according to any of the thirteenth to fifteenth aspect of this invention, characterized in that the total amount of 3-cyclohexyl-2-methylpropanal in the fragranced article is in a range of from 0.001 to 30 wt.-%, preferably in a range of from 0.001 to 5 wt.-%, particularly preferably 0.001 to 2 wt.-%, based on the total weight of the fragranced article.

In accordance with the seventeenth aspect of the invention, there is provided a fragranced article according to any one of claims thirteenth to sixteenth, characterized in that the pH value of the fragranced article is 3 to 7. DETAILED DESCRIPTION

It must be noted that as used herein, the singular forms “a”, “an” and “the” include plural references and vice versa unless the context clearly indicates otherwise.

Unless otherwise indicated, the term “at least” preceding a series of elements is to be understood to refer to every element in the series. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the present invention.

The term “and/or” wherever used herein Includes the meaning of “and”, “or” and “all or any other combination of the elements connected by said term”. For example, A, B and/or C means A, B, C, A+B, A+C, B+C and A+B+C.

Throughout this specification and the claims, unless the context requires otherwise, the word “comprise” and variations such as “comprises” and “comprising” will be understood to imply the inclusion of a stated integer (or step) or group of integers (or steps). It does not exclude any other integer (or step) or group of integers (or steps). When used herein, the term "comprising" may be substituted with "containing", "composed of', "including", "having" or "carrying. "

When used herein, "consisting of" excludes any integer or step not specified in the claim/item.

Further, in describing representative embodiments of the present invention, the specification may have presented the method and/or process of the present invention as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. As one of ordinary skill in the art would appreciate, other sequences of steps may be possible. Therefore, the particular order of the steps set forth in the specification should not be construed as limitations on the claims. In addition, the claims directed to the method and/or process of the present invention should not be limited to the performance of the steps in the order written, and one skilled in the art may readily appreciate that the sequences may be varied and still remain within the spirit and scope of the present invention. Use of 3-cyclohexyl-2-methylpropanal as a fragrance

The limitations of the prior art are overcome by the use of 3-cyclohexyl-2-methylpropanal as a fragrance.

3-Cyclohexyl-2-methylpropanal possesses unique interesting olfactory properties which clearly differ from and also surpass those of known odoriferous substances. The use of 3- cyclohexyl-2-methylpropanal as a fragrance was previously unknown. It is therefore particularly surprising that in the already well-studied field a fragrance with valuable, interesting and complex olfactory properties could be found.

3-Cyclohexyl-2-methylpropanal (CAS number: 20514-52-7; CAS name: a-methyl- cyclohexanepropanal; chemical formula: CioHisO; molecular mass: 154.25 g/mol) has the following structural Formula (I)

Formula (I)

3-Cyclohexyl-2-methylpropanal is present as two enantiomers in a racemate as shown in the Formulas (Ila) and (lib)

ormu a ( )

3-Cyclohexyl-2-methylpropanal used according to the invention may be present in any stereoisomeric form or may be present as any mixture of stereoisomers. As used herein, 3- cyclohexyl-2-methylpropanal means any isomeric mixture of stereoisomers of 3-cyclohexyl- 2-methylpropanal. What has been said herein for 3-cyclohexyl-2-methylpropanal, in particular the advantages described herein, also apply to any isomeric mixture of stereoisomers of 3-cyclohexyl-2-methylpropanal. In a preferred embodiment, 3-cyclohexyl- 2-methylpropanal is used as a 50:50 racemic mixture. Process for producing 3-cyclohexyl-2-methylpropanal

3-Cyclohexyl-2-methylpropanal is typically produced in a process, comprising the reaction steps of

(a) hydrogenating a-methylcinnamaldehyde to 3-cyclohexyl-2-methyl propanol,

(b) preferably purifying 3-cyclohexyl-2-methylpropanol,

(c) dehydrogenating 3-cyclohexyl-2-methylpropanol to 3-cyclohexyl-2-methylpropanal, and

(d) preferably purifying 3-cyclohexyl-2-methylpropanal.

In a first reaction step (a), a-methylcinnamaldehyde (alpha-methylcinnamaldehyde; 2- methyl-3-phenylprop-2-enal; Cyprinal; Chemical formula: C10H10O; molecular weight: 146.19 g/mol) is fully hydrogenated to 3-cyclohexyl-2-methylpropanol (Chemical formula: C10H20O; molecular weight: 156.27 g/mol) in the presence of a catalyst, as shown in Reaction (I).

Reaction (I)

The a-methylcinnamaldehyde may be present in trans-form, cis-form or any isomeric mixture thereof. Processes to provide the starting compound a-methylcinnamaldehyde are disclosed for example in US4486607 (e.g., the reaction of benzaldehyde with propanal in the presence of NaOH/MeOH (25-30 °C) to a-methylcinnamaldehyde). a- Methylcinnamaldehyde is commercially available under the name Cyprinal at LANXESS. Processes to provide 3-cyclohexyl-2-methylpropanol from a-methylcinnamaldehyde are disclosed in the W001/04253.

In a preferred embodiment, the catalyst used in step (a) is a supported Nickel catalyst.

In a preferred embodiment, the reaction takes place in the presence of a co-catalyst.

The reaction temperature is typically elevated, preferably from 140 to 200°C.

In a second reaction step (c), 3-cyclohexyl-2-methylpropanol is dehydrogenated to produce 3-cyclohexyl-2-methylpropanal in the presence of a catalyst as shown in Reaction (II).

Reaction (II)

The reaction temperature is typically elevated, preferably from 190 to 260 °C.

In a preferred embodiment, the 3-cyclohexyl-2-methyl propanol provided by reaction (I) is purified in a purification step (b) and the 3-cyclohexyl-2-methylpropanal provided by reaction (II) is purified in a purification step (d).

In an alternative embodiment of the process for the production of 3-cyclohexyl-2- methylpropanal, the process comprises as the step (a), the step of hydrogenating 2-methyl- 3-phenylpropanol to 3-cyclohexyl-2-methylpropanol as shown in Reaction (III).

Reaction (III)

Processes to provide 2-methyl-3-phenylpropanol are disclosed in the prior art, for example in US4486607. The hydrogenation of 2-methyl-3-phenylpropanol to 3-cyclohexyl-2- methylpropanol is disclosed in LIS6187727. 2-Methyl-3-phenylpropanol is typically hydrogenated in the presence of a hydrogenation catalyst and hydrogen in a solvent to produce 3-cyclohexyl-2-methyl-propanol.

Use of 3-cyclohexyl-2-methylpropanal in a fragrance composition

The present invention further provides the use of 3-cyclohexyl-2-methylpropanal as a fragrance in a fragrance composition. Further preferred is the use of 3-cyclohexyl-2- methylpropanal in a fragrance composition to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper.

In a preferred embodiment according to the invention, 3-cyclohexyl-2-methylpropanal is used in a fragrance composition to impart, modify and/or enhance one or more fragrance notes selected from the group consisting of the notes: grass, vegetable and cucumber.

In another preferred embodiment according to the invention, 3-cyclohexyl-2-methylpropanal is used in a fragrance composition to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: marine and ozonic. In another preferred embodiment according to the invention, 3-cyclohexyl-2-methylpropanal is used in a fragrance composition to impart, modify and/or enhance one or more fragrance notes selected from the group consisting of the notes: grapefruit, orange and lemon.

In another preferred embodiment according to the invention, 3-cyclohexyl-2-methylpropanal is used in a fragrance composition to impart, modify and/or enhance one or more fragrance notes selected from the group consisting of the notes: cinnamon and pepper.

3-Cyclohexyl-2-methylpropanal brings a sparkling and blooming character and a natural freshness to a fragrance composition. When used in a fragrance composition, 3-cyclohexyl- 2-methylpropanal adds a bloom in the top note which is sparkling and bright.

Thus, in another embodiment of the invention, 3-cyclohexyl-2-methylpropanal is used for enhancing the bloom of a fragrance composition.

Beyond olfactory properties, 3-cyclohexyl-2-methylpropanal possesses other properties, in particular a high biodegradability (readily biodegradable). Moreover, it has a high substantivity when used in a fragranced article compared to other fragrance ingredients with similar olfactory properties and has a high stability in consumer product bases.

In accordance with another embodiment of the present invention, there is provided a method for imparting, modifying and/or enhancing the fragrance of a fragrance composition, comprising the step of mixing 3-cyclohexyl-2-methylpropanal with at least one other fragrance ingredient.

Another preferred embodiment of the present invention comprises the use 3-cyclohexyl-2- methylpropanal as a perfuming ingredient, to impart, modify and/or enhance fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper, of a composition of matter comprising 10 ppm or more 3-cyclohexyl-2-methylpropanal.

According to the present invention, 3-cyclohexyl-2-methylpropanal may be used as a fragrance alone or in combination with one or more fragrance ingredients such as: known odorant molecules selected from the extensive range of natural products, and synthetic molecules currently available, such as extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams or tinctures, hydrocarbons, alcohols, aldehydes and their acetals, ketones and their oximes, ethers, esters and lactones, sulfur- containing compounds, nitriles, macrocycles and heterocycles, and/or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorants in fragrance compositions, such as base materials, carrier materials, and other auxiliary agents commonly used in the art.

Fragrance composition & process for producing a fragrance composition

In a further aspect of the present invention, there is provided a fragrance composition comprising 3-cyclohexyl-2-methylpropanal.

In one aspect of the present invention, the total amount of 3-cyclohexyl-2-methylpropanal in the fragrance composition is sufficient to provide freshness and/or blooming character and/or to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper.

In another aspect of the present invention, the total amount of 3-cyclohexyl-2- methylpropanal in the fragrance composition is in the range of from 0.001 to 99.9 wt.-%, preferably in a range of from 0.01 to 99.5 wt.-%, particularly preferably 0.1 to 99 wt.-% and most preferably 0.1 to 10 wt.-%, based on the total weight of the fragrance composition.

As used herein, “fragrance composition” means any composition comprising at least one odorant molecule.

The following list comprises examples of known odorant molecules as fragrance ingredients, which may be combined with 3-cyclohexyl-2-methylpropanal in the fragrance composition according to the present invention: extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams or tinctures such as: Ambergris tincture; Amyris oil; Angelica seed oil; Angelica root oil; Anise oil; Valerian oil; Basil oil; Tree moss absolute; By oil; Bay leaf oil; Benzoeresin; Bergamot oil; Beeswax absolue; Birch tar oil; Bitter almond oil; Savory oil; Bucco leaf oil; Cabreuva oil; Cade oil; Calmus oil; Calamus oil; Chamomile oil blue; Chamomile oil roman; Carrot seed oil; Cascarilla oil; Camphor oil; Cananga oil; Cardamom oil; Caraway oil; Cascarilla oil; Cassia oil; Cassie-absolute; Castoreum-absolute; Cedar leaf oil; Cedarwood oil; Celery seed oil; Cistus oil; Citronella oil; Citron oil; Civet-absolute; Cinnamon leaf oil; Cinnamon bark oil; Copaiva balsam; Copaiva balsam oil; Coriander oil; Costus root oil; Cumin oil; Cypress oil; Davana oil; Dill herb oil; Dill seed oil; Eau de brouts- absolute; Elemi oil; Tarragon oil; Eucalyptus citriodora oil; Eucalyptus oil; Fennel oil; Spruce needle oil; Galbanum oil; Galbanum resin; Geranium oil; Grapefruit oil; Guaiac wood oil; Gurjun balsam; Gurjun balsam oil; Helichrysum absolute; Helichrysum oil; Ginger oil; Iris root absolute; Iris root oil; Jasmine absolute; Jasmine oil; Labdanum oil; labdanum absolute; labdanum resin; Lavandin absolute; Lavandin oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Lime oil distilled; Lime oil pressed; Linaloe oil; Litsea cubeba oil; Mace oil; Marjoram oil; Mandarin oil; Massoir bark oil; Mimosa absolute; Mugwort oil; Musk grain oil; Musk tincture; Muscat sage oil; Nutmeg oil; Myrrh absolute; Myrrh oil; Myrtle oil; Clove leaf oil; Clove flower oil; Neroli oil; Oak moss absolute; Olibanum absolute; Olibanum oil; Opopanax oil; Orange blossom absolute; Orange oil; Origanum oil; Palmarosa oil; Patchouli oil; Perilla oil; Perubalsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; Allspice oil; Pine oil; Pine needle oil; Poley oil; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Sage oil Dalmatian; Sage oil Spanish; Sandalwood oil; Spearmint oil; Spicy lavender oil; Star anise oil; Styrax oil; Tagetes oil; Fir needle oil; Tea tree oil; Turpentine oil; Thyme oil; Tolu balsam; Tonka absolute; Tuberose-absolute; Vanilla extract; Violet leaf-absolute; Verbena oil; Vetiver oil; Juniper berry oil; Wine yeast oil; Wormwood oil; Wintergreen oil; Ylang ylang oil; Hyssop oil and fractions thereof, or ingredients isolated therefrom; hydrocarbons, such as 3-carene; a-pinene; p-pinene; a-terpinene; y-terpinene; p- cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1 ,3,5-undecatriene; styrene; diphenylmethane; aliphatic alcohols, such as hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2- methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; 1-octen-3-ol; mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan- 2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10- undecenol; 4-methyl-3-decen-5-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); Super Muguet™ ((E)-6-ethyl-3-methyloct-6-en-1-ol); cyclic alcohols, such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3- isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2- isobutyl-4-methyltetrahydro-2H-pyran-4-ol; 4-cyclohexylbutan-2-ol; cycloaliphatic alcohols, such as alpha-3, 3-trimethylcyclohexylmethanol; 1-(4- isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; Sandalore™ (3-methyl- 5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol); Ebanol™ ((E)-3-methyl-5-(2,2,3- trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol); 3,3-dimethyl-5-(2,2,3-trimethyl-3- cyclopent- 1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; Timberol™ (1-(2,2,6-trimethylcyclohexyl)hexan-3-ol); [1-methyl-2-(5-methylhex-4-en-2- yl)cyclopropyl]-methanol; araliphatic alcohols, such as benzyl alcohol; phenyl ethyl alcohol (2-phenylethanol);

1-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2- dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1 , 1-dimethyl-

2-phenylethyl alcohol; 1 ,1-dimethyl-3-phenylpropanol; 1 -ethyl- 1-methyl-3- phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; cinnamic alcohol ((E)-3-phenylprop-2-en-1-ol); 4-methoxybenzyl alcohol; 1-(4- lsopropylphenyl)ethanol; Eugenol (4-allyl-2-methoxyphenol); acyclic terpene alcohols, such as geraniol ((E)-3,7-dimethylocta-2,6-dien-1-ol); nerol (3,7-dimethyl-2,6-octadien-1-ol); lavadulol; nerolidol; farnesol ((2E,6Z)-3,7,11- trimethyldodeca-2,6, 10-trien-1-ol); tetrahydrolinalool; tetrahydrogeraniol; 2,2- dimethyl-3-(3-methylphenyl)propan-1-ol; 2,6-dimethyl-7-octen-2-ol; 2,6- dimethyloctan-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; Rhodinol™ (3,7-dimethyloct-6-en-1-ol); (2E)-3,7-dimethylocta-2,6-dien-1-ol; 2,4,7- trimethylocta-2,6-dien-1-ol; 3,7-dimethyl-1 ,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7- octatrien-1-ol; linalool (3,7-dimethylocta-1 ,6-dien-3-ol); ethyl linalool ((E)-3,7- dimethylnona-1 ,6-dien-3-ol); and their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates; cyclic terpene alcohols, such as menthol (2-isopropyl-5-methylcyclohexanol); isopulegol; a-terpineol; terpinen-4-ol (2-(4-methylcyclohex-3-en-1-yl)propan-2-ol); menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiaol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates; aliphatic aldehydes and their acetals, such as hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; 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-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanaldiethyl acetal; 1 , 1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; 1-(1-methoxypropoxy)-(E/Z)-3-hexene; cycloaliphatic aldehydes, such as 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2- butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3- penten-1-yl)-3-cyclohexenecarbaldehyde; aromatic and araliphatic aldehyde, such as a-amyl cinnamic aldehyde (2- benzylideneheptanal); 3-(4-isobutyl-2-methylphenyl)propanal; vanillin (4-Hydroxy- 3-methoxybenzaldehyde); acyclic terpene aldehydes and ketones, such as citronellal (3,7-dimethyl-6-octen-1- al); Hydroxycitronellal (7-hydroxy-3,7-dimethyloctanal); 7-methoxy-3,7- dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethylacetals of geranial; neral; cyclic terpene aldehydes and ketones, such as menthone; isomenthone; 8- mercaptomenthan-3-on; carvone; camphor; fenchone; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; betaisomethylionone; alpha-irone; beta-damascenone; 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- methanonaphthalen-8(5H)-on; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2- butenal; nootkatone; dihydronootkatone; 4,6,8-megastigmatriene-3-on; alpha- sinensal; beta-sinensal; acetylated cedarwood oil (methylcedrylketone); aliphatic ketones and their 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; 6-methyl-5-hepten-2-one; cyclic and macrocyclic 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-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3- methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1 -ethoxyvinyl)- 3,3,5,5-tetramethylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexadecen- 1-one; 6,7-dihydro-1 ,1 ,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecen-1- one; 9-cycloheptadecen-1-or); cyclopentadecanone; cyclohexadecanone; Isoraldeine® ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one); methyl cedryl ketone (1-((3R,3aR,7R,8aS)-3,6,8,8-tetramethyl-2,3,4,7,8,8a- hexahydro-1 H-3a,7-methanoazulen-5-yl)ethan-1-one); verbenone (4,6,6-Trimethyl- bicyclo[3.1.1]hept-3-en-2-one), cycloaliphatic ketones, such as 1-(3,3-dimethylcyclohexyl)-4-penten-1-on; 2,2- dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanon; 1-(5,5-dimethyl-1- cyclohexen-1-yl)-4-penten-1-on; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7, 8-octahydro-2- naphthalenyl methyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert.-butyl-(2,4-dimethyl-3-cyclohexen-1-yl)ketone; aromatic and araliphatic ketones, such as acetophenone; 4-methylacetophenone;

4-methoxyacetophenone; 4-tert.-butyl-2,6-dimethylacetophenone; 4-phenyl-2- butanone; Frambinone (4-(4-hydroxyphenyl)-2-butanone); 1-(2-naphthalenyl)- ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert. butyl-1 , 1-di- methyl-4-indanyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methyl- ethyl)-1H-5-indenyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2- aceto-naphthone; Georgywood™ (1-(1 ,2,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro- naphthalen-2-yl)ethanone); Iso E Super® (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8- octahydronaphthalen-2-yl)ethanone); aliphatic ethers, such as geranyl methyl ether ((2E)-1-methoxy-3,7-dimethylocta- 2,6-diene); cyclic and cycloaliphatic ethers, such as cineol; cedryl methyl ether; cyclododecyl methyl ether; 1,1 -di methoxycyclododecane; (ethoxymethoxy)cyclo-dodecane; alpha-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydro-naphtho[2,1-b]furan; 3a-ethyl-6,6,9atrimethyldodecahydronaphtho[2,1b]furan; 1 ,5,9-tri-methyl-13- oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-

5-methyl-5-(1 -methyl propyl)-1,3-dioxane; Spirambrene® (2',2',3,7,7- pentamethylspiro[bicyclo[4.1.0]heptane-2,5'-[1,3]dioxane]); araliphatic ethers, such as 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropic aldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9btetra-hydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethyl- indeno[1,2-d]-m-dioxin; of aromatic and araliphatic aldehydes such as benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropic aldehyde; 4- methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2- dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4- isobutylphenyl)propanal; 3-(4-tert. butylphenyl)propanal; cinnamaldehyde; alpha- butylcinnamaldehyde; alphahexylcinnamaldehyde; 3-methyl-5-phenylpentanal; anisaldehyde (4-methoxybenzaldehyde); 4-hydroxy-3-methoxybenzaldehyde; 4- hydroxy-3-ethoxybenzaldehyde; methylenedioxybenzaldehyde; 3,4-dimethoxy- benzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylene- dioxyphenyl)propanal; Ambrox® (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b- octahydro-1 H-benzo[e][1]benzofuran); esters of aliphatic carboxylic acids, such as (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; Octyl acetate; 3-octyl acetate; 1-octene-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate; Hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octinate; methyl 2-noninate; allyl 2-isoamyloxyacetate; M ethyl-3,7-dimethyl-2,6-octadiene- oate;4-methyl-2-pentyl crotonate; esters of cycloaliphatic carboxylic acids, such as allyl 3-cyclohexyl propionate; allyl cyclohexyloxy acetate; cis and trans-methyl dihydrojasmonate; cis and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentane carboxylate; ethyl 2-ethyl-6,6- dimethyl-2-cyclohexene carboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexene carboxylate; ethyl 2-methyl-1 ,3-dioxolane-2-acetate; Hedione™ (methyl 3-oxo-2- pentylcyclopentaneacetate); cedryl acetate ((1 S,6R,8aR)-1 , 4,4,6- tetramethyloctahydro-1 H-5,8a-methanoazulen-6-yl acetate); vetiveryl acetate ((4,8- dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1 H-azulen-6-yl) acetate); esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate; 4-tert- butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3, 5-trimethylcyclohexyl acetate; decahyd ro-2-naphthyl acetate; 2-cyclo- pentylcyclopentyl crotonate; 3-pentyl tetrahydro-2H-pyran-4-yl acetate; decahydro- 2,5, 5, 8atetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexa-hydro-5, or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenyl isobutyrate; 4,7- methanooctahydro-5, or 6-indenyl acetate; esters of cycloaliphatic alcohols, such as 1 -cyclohexylethyl crotonate; Helvetolide® (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl propionate); esters of araliphatic alcohols and aliphatic carboxylic acids, such as benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2- phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenyl ethyl isovalerate; 1- phenylethyl acetate; a-trichloromethyl benzyl acetate; a,a-dimethylphenyl ethyl acetate; a,a-dimethylphenyl ethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; aromatic and araliphatic 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; phenyl ethyl phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenyl ethyl cinnamate; cinnamyl cinnamate; allyl phenoxy acetate; methyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenyl ethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenyl glycidate; ethyl 3-methyl-3-phenyl glycidate; lactones, such as b-decalactone (6-pentyltetrahydro-2H-pyran-2-one); 6- undecalactone (5-heptyloxolan-2-one); 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1 ,4-decanolide; 8-decen-1 , 4-olide; 1 ,4-undecanolide; 1,4- dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1 ,15- pentadecanolide; 1 ,16-hexadecanolide; Ambrettolide (7-hexadecene-1 , 16-olide); 10-oxa- 1 , 16-hexadecanolide; 11 -oxa- 1 , 16-hexadecanolide; 12-oxa- 1,16- hexadecanolide; ethylene- 1 , 12-dodecanedioate; ethylene- 1 , 13-tridecanedioate; 2,3-dihydrocoumarin; octahy d roco u m a ri n ; aliphatic sulfur-containing compounds, such as 3-methylthiohexanol; 3- methylthiohexyl acetate; 3-mercaptohexanol; 3- mercaptohexyl acetate; 3- mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthen-8-thiol; aliphatic nitriles, such as 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2- tridecenoic acid nitrile; 3, 12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6-octadienoic acid nitrile; 3,7-dimethyl-6-octenoic acid nitrile; macrocycles, such as Ambrettolide ((Z)-oxacycloheptadec-10-en-2-one); (E)- oxacycloheptadec-10-en-2-one, ethylene brassylate (1,4-dioxacycloheptadecane- 5, 17-dione); and I or Exaltolide® (16-oxacyclohexadecan-1-one); and heterocycles, such as isobutylquinoline (2-isobutylquinoline); 2,5-dimethyl-4- hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; maltol (3- Hydroxy-2-methyl-pyran-4-one); 2-ethyl-3-hydroxy-4H-pyran-4-one. The fragrance composition according to one embodiment of the invention comprises of 3- cyclohexyl-2-methylpropanal and at least one other fragrance ingredient. Preferably, the fragrance composition according to the invention comprises of 3-cyclohexyl-2- methylpropanal and two or more other fragrance ingredients. More preferably, the fragrance composition according to the invention comprises of 3-cyclohexyl-2-methylpropanal and three or more other fragrance ingredients. Most preferably, the fragrance composition according to the invention comprises of 3-cyclohexyl-2-methylpropanal and four or more other fragrance ingredients.

In another embodiment, the fragrance composition according of the invention consists of 3- cyclohexyl-2-methylpropanal and one other fragrance ingredient. Preferably, the fragrance composition according to the invention consists of 3-cyclohexyl-2-methylpropanal and two other fragrance ingredients. More preferably, the fragrance composition according to the invention consists of 3-cyclohexyl-2-methylpropanal and three other fragrance ingredients. Most preferably, the fragrance composition according to the invention consists of 3- cyclohexyl-2-methylpropanal and four other fragrance ingredients.

Examples of fragrance ingredients which may advantageously be combined with 3- cyclohexyl-2-methylpropanal in the context of the present invention may be found, for example, in S. Arctander, Perfume and Flavor Materials, Vol. I and II, Montclair, N. J. 1969, self-published, or K. Bauer et al., Common Fragrance and Flavor Materials, 4^th Edition, Wiley- CH, Weinheim 2001.

In another embodiment, the present invention relates to a process for producing a fragrance composition comprising 3-cyclohexyl-2-methylpropanal, comprising the step of mixing 3- cyclohexyl-2-methylpropanal with at least one other fragrance ingredient.

As used herein, the term “base material” according to the present invention refers to a diluent conventionally used in conjunction with odorants, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentane-1 ,2-diol, triethyl citrate (TEC) and alcohol (such as ethanol).

As used herein, the term “auxiliary agent” according to the present invention refers to ingredients that might be employed in a fragrance composition for reasons not specifically related to the olfactive performance of said composition. For example, an auxiliary agent may be an ingredient that acts as an aid to processing a fragrance ingredient or ingredients, or a composition containing said ingredient(s), or it may improve handling or storage of a fragrance ingredient or composition containing same. It may be an ingredient that provides additional benefits such as imparting color or texture. It may also be an ingredient that imparts light resistance or chemical stability to one or more ingredients contained in a fragrance composition. A detailed description of the nature and type of adjuvants commonly used in fragrance compositions containing same cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.

Optionally, the fragrance composition may comprise an antioxidant adjuvant. In a preferred embodiment of the present invention, the fragrance composition comprises at least one antioxidant. In a preferred embodiment, said antioxidant is selected from Tinogard® TT (INCI: Pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate; BASF), Tinogard® Q (INCI: Tris(Tetramethylhydroxypiperidinol) Citrate (and) Aqua (and) Alcohol; BASF), hydroquinone (CAS 121-31-9) and tert-butylhydroquinone (TBHQ; CAS No. 1948-33-0), Tinuvin® 770 (CAS No. 52829-07-9; Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate; Merck) tocopherol (including its isomers, CAS 59-02-9; 364-49-8; 18920-62-2; 121854-78-2), tocopherol acetate, tocopherol palmitate, butylhydroxyanisole, 2,6-bis(1 , 1-dimethylethyl)-4- methylphenol (butylated hydroxytoluene, BHT, CAS 128-37-0) and related phenols.

In a more preferred embodiment of the present invention, the at least one antioxidant is selected from the group consisting of pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, tris(tetramethylhydroxypiperidinol) citrate, tert-butylhydroquinone (TBHQ), hydroquinone, Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770), tocopherol, tocopherol acetate, tocopherol palmitate, butylhydroxyanisole and 2,6-bis(1 , 1- dimethylethyl)-4-methylphenol (BHT).

In an even more preferred embodiment, the at least one antioxidant is selected from the group consisting of tert-butylhydroquinone, Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770) or alpha-tocopherol (CAS 59-02-9), more preferably tert-butylhydroquinone or Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770) and most preferably tert- butylhydroquinone.

Preferably, the fragrance composition comprises 0.05 wt% to 0.2 wt% antioxidant. The fragrance compositions according to the invention may also be microencapsulated, spray- dried, as inclusion complexes or as extrusion products and added in this form to a product to be perfumed, for example.

Furthermore, fragrance compositions according to the present invention may be adsorbed on a carrier material, which ensures both a fine distribution of the fragrance ingredients in the product and a controlled release during use.

As used herein, “carrier material" means a material which is practically neutral from a odorant point of view, i.e. a material that does not significantly alter the organoleptic properties of odorants. Such carrier materials may be porous inorganic materials such as light sulfate, silica gels, zeolites, plasters, clays, clay granules, aerated concrete, etc. or organic materials such as wood, cellulose-based substances, sugar, dextrins (such as maltodextrin) or plastics such as Pt/C, polyvinyl acetates or polyurethanes. The resulting combination of fragrance compositions according to the invention and carrier substance is also to be understood as a fragrance composition according to the invention.

If necessary, the properties of the fragrance compositions may be further optimized by so- called "coating" with suitable materials with a view to a more targeted release of fragrances, for which purpose waxy plastics such as polyvinyl alcohol are preferably used. The resulting products in turn represent fragranced articles according to the invention.

A further aspect of the present invention relates to the use of a fragrance composition of the present invention comprising 3-cyclohexyl-2-methylpropanal to modify an existing fragrance to provide freshness and/or blooming character and/or to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper. Preferred embodiments listed above also apply to the use of the fragrance composition.

The present invention also relates to a method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a fragrance composition, comprising the steps of (a) providing a fragrance composition and (b) adding a sensory effective amount, preferably 10 ppm or more, of 3-cyclohexyl-2-methylpropanal to the fragrance composition.

Fragranced articles & process for producing a fragranced article

3-cyclohexyl-2-methylpropanal and fragrance compositions comprising 3-cyclohexyl-2- methylpropanal may be used in a broad range of fragranced articles, preferably in articles of fine and functional perfumery, such as perfumes, air care products, household or home care products, laundry products, body care products and cosmetics.

3-cyclohexyl-2-methylpropanal may be employed in a consumer product base simply by directly mixing 3-cyclohexyl-2-methylpropanal, or a fragrance composition comprising 3- cyclohexyl-2-methylpropanal, with the consumer product base, or it may, in an earlier step, be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the consumer product base.

In one embodiment, the invention provides a method of manufacturing a fragranced article, comprising the step of mixing 3-cyclohexyl-2-methylpropanal, or a fragrance composition comprising 3-cyclohexyl-2-methylpropanal with a consumer product base.

In another embodiment, the invention provides a method of manufacturing a fragranced article, comprising the step of mixing a fragrance composition comprising 3-cyclohexyl-2- methylpropanal, with a consumer product base. Mixing is typically performed by using conventional techniques and methods. Fragrance compositions according to the invention may advantageously be used in concentrated form, in solutions or in modified form for the production of fragranced articles according to the invention.

3-cyclohexyl-2-methylpropanal may be employed in widely varying amounts, depending upon the specific article and on the nature and quantity of other fragrance ingredients. The proportion is typically from 0.001 to 3 wt.% of the fragranced article. In one embodiment, 3- cyclohexyl-2-methylpropanal may be employed in a fabric softener in an amount from 0.001 to 0.3 wt.%, preferably 0.01 to 0.1 wt.%. In another embodiment, 3-cyclohexyl-2- methylpropanal may be used in fine perfumery in amounts from 0.01 to 30 wt.%, preferably 0.01 to 20 wt.%, more preferably from 0.01 to 5 wt.%, particularly preferably 0.01 to 0.1 wt.%. However, these values are given only by way of example, since the experienced perfumer may also achieve effects or may create novel accords with lower or higher concentrations of 3-cyclohexyl-2-methylpropanal.

In one embodiment there is provided a fragrance composition or fragranced article comprising a sensory effective amount of 3-cyclohexyl-2-methylpropanal. Fragrance compositions or fragranced articles comprising 10 ppm (0.001 wt.-%) or more 3-cyclohexyl- 2-methylpropanal show a sensory effect. For example, the fragrance composition or fragranced article may comprise 0.001 wt.% to 90 wt.% (including 0.001 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.5 wt.%, 1 wt.%, 5 wt.%, 8 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 50 wt.%, 60 wt.%, 65 wt.%) of 3-cyclohexyl-2-methylpropanal based on the total amount of the fragrance composition or fragranced article.

In a preferred embodiment of the present invention, 3-cyclohexyl-2-methylpropanal is used in a sensory effective amount, i.e. , in a total amount in which it exerts a sensory effect. In a particularly preferred embodiment of the present invention, 3-cyclohexyl-2-methylpropanal is used in a fragrance composition or in a fragranced article in a fragrance-imparting amount of 10 ppm or more. In a preferred embodiment of the present invention, the fragranced article comprises a consumer product base and 3-cyclohexyl-2-methylpropanal in a total amount sufficient to modify an existing fragrance to provide freshness and/or blooming character and/or to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper, preferably in a total amount in a range of from 0.001 to 30 wt.-%, preferably in a range of from 0.001 to 5 wt.-%, particularly preferably 0.001 to 2 wt.-%, based on the total weight of the fragranced article.

Through the addition of a fragrance-imparting amount of 3-cyclohexyl-2-methylpropanal, or a fragrance composition comprising 3-cyclohexyl-2-methylpropanal, to a consumer product base, the odor notes of a consumer product base may be improved, modified, or enhanced. Thus, the invention furthermore provides a method for improving, modifying and/or enhancing the fragrance of a consumer product base, comprising the steps of: (a) providing a consumer product base, and (b) adding 3-cyclohexyl-2-methylpropanal or a fragrance composition comprising 3-cyclohexyl-2-methylpropanal, to the consumer product base in a sensory effective amount sufficient to modify the existing fragrance of the consumer product base.

The present invention also relates to a method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a consumer product base, comprising the steps of (a) providing a consumer product base and (b) adding a sensory effective amount, preferably 10 ppm or more, of 3-cyclohexyl-2- methylpropanal to the consumer product base.

As used herein, “consumer product base” means a composition for use as a consumer product to fulfill specific actions, such as cleaning, softening, and caring or the like. Examples of such consumer products include

• fine perfumery, such as perfume, perfume extracts, eau de perfume, eau de toilette, aftershave, eau de cologne, pre-shave products, splash colognes and perfumed refreshing towels;

• household or home care products, such as acidic, alkaline and neutral cleaning agents such as surface cleaner, floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring milk, solid and liquid toilet cleaners, powder and foam carpet cleaners, textile fresheners, ironing aids, liquid detergents, powder detergents, rinse conditioner, personal cleansing composition;

• personal care products & body-care products, such as bath products, toiletries, solid and liquid soaps, cosmetics products including cosmetic emulsions of the oil-in- water, of the water-in-oil and of the water-in-oil-in-water type such as, for example, o skin care products, especially skin washing and cleansing products, shower gels, body lotions, bath oils, skin creams and lotions, face creams and lotions, hand creams and lotions, foot care products such as foot creams and lotions, intimate care products; o dental care products, especially dental and oral care products, tooth care products, cleaners for dental prostheses, adhesives for dental prostheses; o hair care products, such as hair sprays, hair gels, setting hair lotions, hair shampoos, hair care products, hair conditioners, hair coloring products such as permanent and semi-permanent hair dyes, hair setting products, hair shaping agents such as cold waves and hair straighteners, hair lotions and hair creams; and o cosmetic products with specific effects, especially sunscreens, sun protection creams and lotions, after-sun creams and lotions, tanning products such as tanning creams and lotions, de-pigmenting products, deodorants and, antiperspirants such as underarm sprays, roll-ons, deodorant sticks and deodorant creams, hair removers and shaving products such as shaving soaps, shaving foams, depilatory creams and lotions, aftershave creams and lotions;

• fabric care and laundry (pretreatment) products, such as softener, laundry detergents, bleach; soaking agents, stain removers, fabric softeners, laundry soaps, washing tablets, and disinfectants;

• products in decorative cosmetics such as eye makeup, eye shadow, mascara, nail care products such as nail varnish, lip care products such as lipsticks; air care products, including products that contain preferably volatile and usually pleasant-smelling compounds which advantageously, even in very small amounts, can mask unpleasant odors such as candles, lamp oils, incense sticks, reed diffusers, bakhoor, insecticides, repellants and fuels;

• air fresheners in liquid, gel-like or applied form on a solid carrier, aerosol sprays, waxes and polishes such as furniture polishes, floor waxes and shoe creams.

Thus, a further aspect of the present invention relates to a fragranced article comprising (a) a consumer product base and (b) 3-cyclohexyl-2-methylpropanal.

In a preferred embodiment, the consumer product base of the fragranced article is a perfume, a fabric care product, a body-care product, a cosmetic product, a skin care product, an air care product or a home care product.

In another preferred embodiment, the consumer product base of the fragranced article according to the present invention is selected from the group consisting of eau de toilette, powder detergent, liquid detergent, laundry detergent, reed diffuser, body lotion, shower gel and bakhoor.

In a more preferred embodiment, the consumer product base of the fragranced article is selected from a group consisting of detergent powder, liquid detergent and laundry detergent.

In a particularly preferred embodiment, the consumer product base of the fragranced article is a laundry detergent.

As 3-cyclohexyl-2-methylpropanal is an aldehyde, it is hypothesized that an extreme acid pH (e.g., lower than 3) and extreme alkaline pH (e.g. higher than 10) of the fragranced article (such as in bleach and peroxide-based cleaners) might accelerate the reaction to 3- cyclohexyl-2-methylpropanol or 3-cyclohexyl-2-methylpropionic acid.

In a preferred embodiment of the present invention, the pH value of the fragranced article is 10 or lower, preferably 3 to 9 and more preferably 3 to 7.

3-Cyclohexyl-2-methylpropanal with its multifaceted odor provides not only an odor direction for a fragrance but also provides a major blooming and freshness impact for a fragranced article.

The present invention also relates to a method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a fragranced article, comprising of the following steps (a) providing a fragranced article and (b) adding a sensory effective amount, preferably 10 ppm or more, of 3-cyclohexyl-2- methylpropanal to the consumer product base.

Substantivity of a compound is a term used in relation to the degree of the attractive and repulsive forces between said compound and the solid support or substrate upon which it has been deposited. The degree of substantivity is affected by the way in which the perfume is delivered to the surface, e.g. in a washing/laundering process. This delivery can give rise to extra barriers. The degree of substantivity of a compound depends on both the capability of the compound to cross delivery barriers and how well the compound retains on a substrate after delivery. The latter effect, referred to as retention, is sometimes also used to indicate how well a fragrance composition sticks to a substrate, but retention only relates to the behavior of a perfume after it has successfully adhered to the substrate. In contrast to substantivity, retention does not include an indication of how well the delivery barriers are crossed by a fragrance compound or composition. Hence, a compound may - despite a good retention - be a poor fragrance compound in e.g., a personal care product, or a washing or laundering product if it does not manage to cross the barrier from product to substrate sufficiently, i.e. if it has too low a substantivity. Examples of applications in which a fragrance composition has to take such barriers are the washing of laundry, hair, skin or surfaces. This involves the perfume transfer from an aqueous detergent solution or dispersion to a substrate, such as skin, hair, a textile, a ceramic or a surface. The nature of a substrate also influences substantivity; under comparable conditions of application, perfumes are in general a lot less substantive on nylon than on wool; cotton occupies an intermediate position. Substantivity can further be complicated by several factors, including temperature during washing and thereafter, pH value and the presence of other compounds.

3-cyclohexyl-2-methylpropanal has a higher substantivity to the substrate of the fragranced articles when compared to similar fragrances.

Apart from the fragrance being appreciated by a consumer, an important technical factor in fragranced articles is the substantivity of the fragrance or fragrance composition to the substrate.

The invention is now further described with reference to the following non-limiting examples. These examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art. EXAMPLES

Reaction step (a). Hydrogenation of a-methylcinnamaldehyde to 3-cyclohexyl-2-

In a first reaction step (a), a-methylcinnamaldehyde was fully hydrogenated in the presence of hydrogen to produce 3-cyclohexyl-2-methylpropanol according to the process disclosed in W001/04253 A1.

Reaction (I)

Analysis of the a-methylcinnamaldehyde feed, showed 97.45% trans-isomer and 1 .70% cisisomer. In the laboratory, a batch hydrogenation was run using a slurried, supported Nickel catalyst.

The reactor contents were heated to 170 °C and 21 bar(g) hydrogen pressure. The hydrogenation took 16 hours before hydrogenation was complete. After filtration of the catalyst, a yield of 86.0% was observed. The crude 3-cyclohexyl-2-methylpropanol was then fractionally distilled at reduced pressure, purification step (b), to produce high quality 3- cyclohexyl-2-methylpropanol at 99.5% assay, with an 89.4% recovery of active achieved in the single pass distillation.

Reaction step (c). Dehydrogenation of 3-cyclohexyl-2-methyl propanol to 3-cyclohexyl-2-

In a second reaction step (c), 3-cyclohexyl-2-methyl propanol was dehydrogenated to produce 3-cyclohexyl-2-methylpropanal as shown in Reaction (II).

Reaction (II)

In the laboratory, a dehydrogenation was run using a slurried copper catalyst. The contents of the reactor were heated to 230 °C at reduced pressure and 3-cyclohexyl-2- methylpropanol was added at a controlled rate. Upon dehydrogenation, the lower boiling 3- cyclohexyl-2-methylpropanal was collected at an assay of 99.5%, with a molar yield of 97.7%.

The crude 3-cyclohexyl-2-methylpropanal was then fractionally distilled at reduced pressure, purification step (d), to produce high odor quality 3-cyclohexyl-2-methylpropanal at 99.7% assay, with an 86.7% recovery of active achieved in the single pass distillation.

Rotation Results Optical rotation testing was completed on an Anton Paar Modular compact polarimeter (MCP) 150 (a = -0.003 °; A = 589 nanometers (the sodium D line); I = 100 mm pathlength equivalent to 1 decimeter; p = Density @ 20 °C = 0.901 ; T = 20.0°C). The measured optical rotation was -0.003°, indicating a 50:50 racemic mixture of isomers.

UV-Vis UV-Vis spectra at two different concentrations showed a peak consistent with a carbonyl transition. No absorption maxima were detected in 400 - 800 nm range. The observed absorption strength values in acetonitrile of 3-cyclohexyl-2-methylpropanal ([1]: c = 3.97 mg/mL; c = 2.57E-2 mol/L; A_max = 293.7 nm, A = 0.7; I = 1.00 cm; £ = 27 M’¹cm-¹; [2]: c = 0.547 mg/mL; c = 3.55E-3 mol/L; _max = 293.8 nm, A = 0.7; I = 1.00 cm; £ = 28 M'¹crrr¹) was consistent with the upper range of absorption strength for n — > TT* transition of the carbonyl group. All spectra were recorded in absorbance mode against a reference cell filled with the solvent (Instrument: Perkin Elmer Lambda 25; scan range: 190-800 nm; Scan speed: 240 nm/min; slit width: 1 nm; solvent: acetonitrile (LCMS grade); cuvettes: quartz,

1cm). Maxima were determined using cubic interpolation. The 190 -200 nm region deviated from Beer-Lambert Law (background solvent absorption too large for meaningful compensation).

FTIR-ATR FTIR peaks were consistent with a fully saturated aliphatic aldehyde, without the presence of major impurities. The two peaks at 2920 and 2850 cm^-1 were from C-H stretch. The peak at 1724 cm^-1 was assigned to the C=O stretch of a saturated aliphatic aldehyde. The peak at 1448 cm^-1 was C-H bend.

1 H-NMR Hydrogen NMR confirmed that the number and arrangement of the hydrogens in the sample substance matched the theoretical arrangement of the 3-cyclohexyl-2- methylpropanal target molecule. ¹H-NMR (500 MHz, CDCh, TMS): 0.85-0.93 ppm (m, 2H), 1.06-1.08 ppm (d, 3H), 1.13-1.32 ppm (m, 5H), 1.57-1.71 ppm (m, 6H), 2.42-2.46 ppm (m, 1 H), 9.59 ppm (d, 1 H) 13C-NMR Carbon NMR confirmed that the arrangement of the carbon backbone in the sample substance matched the theoretical arrangement of the 3-cyclohexyl-2- methylpropanal target molecule.

¹³C-NMR (126 MHz, CDCI₃, TMS): 13.80 ppm, 26.21 ppm, 26.27 ppm, 26.53 ppm, 33.03 ppm, 33.70 ppm, 35.03 ppm, 38.29 ppm, 43.77 ppm, 205.36 ppm

GC/MS All major peaks in the mass spectrum could be assigned to an ion that matches the theoretical structure of the product, either directly or through common ion rearrangements. The molecular ion can be seen at m/z 154. (GC: Agilent 7890B; Agilent 5977A, 70 eV El ionization source).

GC-MS (El) m/z (%): 154 (1 , [M]⁺), 136 (5), 121 (10), 111 (12), 97 (90), 96 (82), 83 (33), 81 (55), 79 (12), 69 (35), 68 (14), 67 (36), 58 (43), 57 (14), 55 (100), 54 (13), 53 (13), 43 (10), 41 (49), 39 (23)

Conclusion of analytical results

UV-Vis showed a peak consistent with the upper range of absorption strength for n — > TT* transition of the carbonyl group. FTIR confirmed the presence of a fully saturated hydrocarbon with a carbonyl functional group. ¹³C NMR confirmed the arrangement of the carbon backbone and ¹H NMR confirmed the number and placement of hydrogens matches with the theoretical prediction, taking into account that the sample is a 50:50 racemic mixture of stereoisomers. GCMS showed very little contamination by impurities (assay 99.2% 3- cyclohexyl-2-methylpropanal), with the main impurities coming from structurally similar molecules and oxidative degradation products of the 3-cyclohexyl-2-methylpropanal target molecule.

Readily biodegradable are those test materials giving a result of at least 60 % biodegradation within 28 days. This pass level must be reached within the 10 days immediately following the attainment of 10 % biodegradation (10-day window).

Determination of ‘Ready’ biodegradability of 3-cyclohexyl-2-methylpropanal was performed by a manometric respirometry test in an aerobic aqueous medium with microbial activity introduced by inoculation with activated sludge in compliance with OECD Guideline 301 F, Section 3. Degradation and Accumulation. "Ready Biodegradability: Manometric Respirometry Test", (adopted July 17, 1992) and ISO International Standard 10634. "Water Quality - Preparation and treatment of poorly water-soluble organic compounds for the subsequent evaluation of their biodegradability in an aqueous medium", (2018).

Over 28 days, 3-cyclohexyl-2-methylpropanal reached 85-91 % biodegradation, with 80% biodegradation reached between 14-21 days.

The partition coefficient LogP (i.e. decadic logarithm of the octanol/water partition coefficient) was determined to be 4.03 - 4.30 (+/- 0.5 log units). A reversed-phase high performance liquid chromatography (HPLC) method using recommended reference substances, with preliminary established values of LogPow as per OECD Test No.117, was used to determine the LogP. A LogP (octanol/water partition coefficient) between 3 and 5 is beneficial. A LogP above 5 often relates to molecules of toxicological concern. A LogP lower than 3 is undesired for laundry perfumes as such a compound would become relatively more hydrophilic and would disappear with the wash cycle with the surfactant. studies

Odor Detection Limit: For the assessment of the odor detection limit, 8 trained panelists were used. The term odor detection limit (ODL) as used herein is defined as the average concentration above which at least 50 % of the panelists are able to perceive a difference between the sample and the control. Various concentrations of 3-cyclohexyl-2- methylpropanal in diethylene glycol were tested. Panel testing has indicated that the detection limit for 3-cyclohexyl-2-methylpropanal is 10 ppm.

Odor description of 3-cyclohexyl-2-

note green (grass) vegetable (cucumber) aquatic (marine/ozonic), citrus (grapefruit, orange, lemon) and spicy (cinnamon, pepper) odor notes.

24h drydown: green, fatty

Perfumer comments #1 3-Cyclohexyl-2-methylpropanal has an interesting combination of notes, especially the citrus nitrile type facet and the strength and potency of the product. It is also very diffusive in the air with a fascinating creamy lactonic coconut backnote. Its odor profile is not comparable to other compounds.

Perfumer comments #2 3-Cyclohexyl-2-methylpropanal was described as aldehydic with a lime top note, a green note which was slightly minty along with a light metallic note. The material is extremely powerful and diffusive and shows many facets. Consequently it is not immediately comparable to any existing product, which is interesting because 3-cyclohexyl- 2-methylpropanal provides a real, novel olfactory sensation. Fraqranced articles

Example 1 : Odor description of Eau de Toilette (EdT) after addition of 3-cyclohexyl-2- methylpropanal (Table 1)

Table 1. Eau de Toilette (10 wt.% loading of fragrance)

In a unisex eau de toilette, at a 10% loading of fragrance, the effects of the replacement of only 2 parts per thousand of dipropylene glycol with 3-cyclohexyl-2-methylpropanal are to highlight and boost the citrus fruity sparkling character of the fragrance. This is a significant effect for such a small loading. Example 2: Odor description of bakhoor after addition of 3-cyclohexyl-2-methylpropanal (Table 2)

Table 2. Bakhoor (5 wt.% loading of fragrance)

In Bakhoor, at a 5% fragrance loading, the effects of the replacement of 50 parts per thousand of dipropylene glycol with 3-cyclohexyl-2-methylpropanal are to produce an amazing fruitiness in the direction of apple with no burnt smell. Example 3: Odor description of a detergent powder after addition of 3-cyclohexyl-2- methylpropanal (Table 3)

Table 3. Detergent powder (1 wt.% loading of fragrance)

In a detergent powder, at a 1% loading of fragrance, the effects of the replacement of 20 parts per thousand of dipropylene glycol with 3-cyclohexyl-2-methylpropanal highlighted the natural freshness with the blooming effect it provided. The effect given is comparable to a blend of various ingredients and would allow to simplify the formula by adding complexity with only one ingredient. Example 4: Odor description of a shower gel after addition of 3-cyclohexyl-2- methylpropanal (Table 4)

Table 4. Demonstrated at a 1% fragrance loading in shower gel Citralia

The fragrance base of the shower gel Citralia is a bright, fragrant citrus fragrance dominated by neroli and orange blossom notes.

The effect of the replacement of 20 parts per thousand of DPG with 20 parts of 3-cyclohexyl- 2-methylpropanal is to produce a more functional, almost therapeutic profile which is clean and refreshing. It has less clear neroli but more bergamot and lemon. Example 5. Odor description of a shower gel after addition of 3-cyclohexyl-2- methylpropanal (Table 4)

Table 5. Demonstrated at a 1% fragrance loading in shower gel Zephyr

The fragrance base of the shower gel Zephyr is a modern men’s toiletry style fragrance which has fresh citrus top notes twisted with ozonic and black pepper notes, a floral heart note and a woody base with a contemporary amber depth.

The effects of the replacement of 10 parts per thousand of DPG with 3-cyclohexyl-2- methylpropanal are to energize the whole blend. It has powered the fragrance by emphasizing the woody amber characters which have been brought to the fore. There is also a suggestion that the blend has a more oriental feel.

3-Cyclohexyl-2-methylpropanal, with its multifaceted odor, provides not only an odor direction for a fragrance but provides also a major blooming and freshness impact.

Stability tests

Stability tests were performed of various consumer product bases comprising 3-cyclohexyl- 2-methylpropanal. Applications were made at 1 wt.%. One sample was kept in the fridge at 4°C, one sample was kept at room temperature. Odor assessment and visual inspection were performed at weekly intervals over 8 weeks. Results are shown in Tables 6 to 12.

Table 6. Powder Detergent with 1 wt.% 3-cyclohexyl-2-methylpropanal (5 = good; 4 =

Medium-Good; 3 = Medium; 2 = Medium-Poor; 1 = Poor)

Table 7. Liquid detergent with 1 wt.% 3-cyclohexyl-2-methylpropanal

Table 8. Shower gel unperfumed with 1 wt.% 3-cyclohexyl-2-methylpropanal

Table 9. Eau de Toilette with 1 wt.% 3-cyclohexyl-2-methylpropanal

Table 10. Reed Diffusor DPM with 1 wt.% 3-cyclohexyl-2-methylpropanal

Table 11. Bakhoor with 1 wt.% 3-cyclohexyl-2-methylpropanal

Table 12. Bodylotion with 1 wt.% 3-cyclohexyl-2-methylpropanal

Odor stability testing of 3-cyclohexyl-2-methylpropanal was done in several personal care and home care bases. Results in Table 6 to 12 show that, shower gel, eau de toilette, reed diffuser, bakhoor, powder and liquid detergents were stable for 6 weeks at RT. pH Aging Study

To test whether the pH of the product might play a role in the product degradation, 0.1 wt.% 3-cyclohexyl-2-methylpropanal was added to a simple laundry detergent mimic at a range of pH values and aged for 6 weeks at 40 °C. A very simple surfactant solution was made as the simulated laundry detergent base - 20% sodium lauryl sulfate (SLS) in water. 3- Cyclohexyl-2-methylpropanal was added to this solution at 0.1 wt.% and pH adjusted to various pHs between 3 and 10. Scintillation vials were aged for 6 weeks in a 40 °C oven. Odor was assessed at 1 , 3, 4, and 6 weeks. The results of odor testing are shown in Table 13.

Table 13. Odor testing results for 0.1 wt.% 3-cyclohexyl-2-methylpropanal in 20% SLS at 40 °C for 6 weeks.

All pH samples were essentially the same as the starting material for the first 3 weeks. On week 4, the highest pH sample began to display a weak, plastic off-odor. This off-note became stronger in the headspace of the high-pH samples 8-10 at week 6. Interestingly, in lower concentrations on the blotters, the plastic off-note became fruity/juicy. This is somewhat characteristic of sulfur compounds, which are added at very low concentrations to some fruit flavors and fragrances for naturalness. Oxidative stability

23 g of the test substance (3-cyclohexyl-2-methylpropanal with or without antioxidants) were placed into a 30 ml clear bottles (diameter of the opening 2.0 cm, height 7.5 cm, width of the body 3.2 cm). The assay of the initial sample was determined by GC analysis. The open-topped bottles were placed in a darkened oven for approximately 450 hours at 40°C and exposed to an air atmosphere. Periodic, thoroughly mixed samples were removed for analysis. 0.5 g of each sample (accurately weighed to 4 decimal places) were added to a 25 ml volumetric flask and then filled to the graduation mark with toluene

After mixing, the resultant solutions were analyzed by GC in duplicate/triplicate at the calculated concentration. Based on a fixed volume injection and using the area count, the assay of each sample was determined.

GC Method:

GC Column - Agilent DB-5 GC Column length 30 m, diameter 0.25 mm and film thickness 0.25 pm (part number 122-5032)

Instrument used: Agilent 8860 with autosampler

1 pl Injection volume onto an inert wool liner (SGE Trajan TAPFOCUS 4mm P/N 092011) at 175°C and a 100:1 split ratio.

Carrier gas: Nitrogen @ 52.2 ml/min (constant flow 2.4849 ml/min)

Various amounts of TBHQ (tert-butylhydroquinone), Tinuvin® 770 (Bis(2,2,6,6-tetramethyl- 4-piperidyl) sebacate) or alpha-tocopherol (CAS 59-02-9) were added to 3-cyclohexyl-2- methylpropanal.

Source of TBHQ was OQEMA/Chemcare.

Source of Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770, CAS 52829-07-9) was Sigma Aldrich (Merck).

Source of alpha-Tocopherol was DSM.

The results of the oxidation assays are shown in Table 14. Table 14. Stability of 3-cyclohexyl-2-methylpropanal measured via GC at 40°C uncovered and exposed to air (no mixing) with and without antioxidants.

Table 14 shows that the antioxidant TBHQ shows better stabilizing performance of 3- cyclohexyl-2-methylpropanal than Tinuvin® 770 and alpha-tocopherol at the same concentration over a duration of 20 days.

Claims

Claims:

1. Use of 3-cyclohexyl-2-methylpropanal as a fragrance in a fragrance composition.

2. Use of 3-cyclohexyl-2-methylpropanal according to claim 1 in a fragrance composition to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper.

3. Use of 3-cyclohexyl-2-methylpropanal according to claim 1 or 2 for enhancing the bloom of a fragrance composition.

4. Use of a fragrance composition comprising 3-cyclohexyl-2-methylpropanal to modify an existing fragrance to provide freshness and/or blooming character and/or to impart, modify and/or enhance one or more of the fragrance notes selected from the group consisting of the notes: green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper.

5. A method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a fragrance composition, comprising the steps of:

(a) providing a fragrance composition and

(b) adding a sensory effective amount, preferably 10 ppm or more, of 3-cyclohexyl- 2-methylpropanal to the fragrance composition.

6. A method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a consumer product base, comprising the steps of:

(a) providing a consumer product base and

(b) adding a sensory effective amount, preferably 10 ppm or more, of 3-cyclohexyl- 2-methylpropanal to the consumer product base.

7. A method for providing freshness and/or blooming character and/or imparting, modifying and/or enhancing one or more of the fragrance notes selected from the group consisting of the notes green, grass, vegetable, cucumber, aquatic, marine, ozonic, citrus, grapefruit, orange, lemon, spicy, cinnamon and pepper of a fragranced article, comprising of the following steps:

(a) providing a fragranced article and