Patent Description:
Typically, many odorants that are presently utilized in the perfumery industry and/or the flavor industry are synthetic molecules. In particular, there is a high demand and need for novel odorants/compounds and/or for novel fragrance, flavor and/or deodorizing/masking compositions comprising said odorants/compounds.

<CIT> discloses fragrance compositions which contain an ether with interesting odor notes, e.g. intense floral, but at the same time very natural-looking green, with a spicy character, which are very suitable for perfuming soaps and detergents.

<CIT> discloses a process for the production of unsaturated ethers exhibiting different reminiscent smells scents (inter alia bergamot oil, bitter almonds, cherries, jasmine, cardamom, angelica root, coriander, vetiver, lilies, galbanum, balsamic, bois de rose, cinnamon,.

<CIT>) is directed to <NUM>-hexenyl-<NUM>-methylallyl ether and its use in creating perfumes and scents in such items as perfumes, colognes, toilet water and personal care products.

<NUM>-(<NUM>-propenoxy)-<NUM>-tert-butyl-<NUM>-propene is cited in the article of <NPL> which relates to a study of the photochemistry of ten <NUM>,<NUM>-hexadien-<NUM>-ones in methanol over the wavelength range of <NUM>-<NUM>, by using monochromatic light. As indicated on page <NUM> of this article, <NUM>-(<NUM>-propenoxy)-<NUM>-tert-butyl-<NUM>-propene is recited as an intermediate chemical compound during the preparation of <NUM>-tert-Butyl-<NUM>,<NUM>-hexadien-<NUM>-one (<NUM>) from <NUM>,<NUM>,<NUM>-trimethyl-<NUM>-butene. No fragrance, flavor and/or deodorizing/masking compositions are disclosed in this article and there is absolutely no evidence nor any suggestion of the existence of any olfactive property associated with compound <NUM>-(<NUM>-propenoxy)-<NUM>-tert-butyl-<NUM>-propene.

Allyl <NUM>-pentyl allyl ether is cited in the article of<NPL> which relates to a new route to substituted alkenediols by reacting dihydrofuran and dihydropyran epoxides to a stereospecilic alkylative double ring-opening with organolithiums. As indicated on page <NUM> of this article, Allyl <NUM>-pentyl allyl ether is recited as an intermediate chemical compound during the preparation of substituted alkenediols from trisubstituted epoxide (scheme <NUM>). No fragrance, flavor and/or deodorizing/masking compositions are disclosed in this article and there is absolutely no evidence nor any suggestion of the existence of any olfactive property associated with compound Allyl <NUM>-pentyl allyl ether.

It is an advantage of one or more of the embodiments of the present invention that the odorants/compounds can impart and/or accentuate particular olfactory notes, in particular providing green, fruity, pear and/or waxy olfactory notes to fragrance, flavor and/or deodorizing/masking compositions.

This invention is defined in claims <NUM> to <NUM>.

This invention discloses novel fragrance, flavor and/or deodorizing/masking compositions comprising a <NUM>- and/or <NUM>-substituted <NUM>-(allyloxy)propene of formula (I)
<CHM>
as defined in claims <NUM> to <NUM>.

For the avoidance of doubt, radicals R<NUM> and R<NUM> are separated radicals, i.e. they do not form together a ring. In another embodiment the compounds of this invention can be chiral, e.g. they can be used as stereoisomeric mixtures, more specifically as mixture of enantiomers; R isomer, S isomer, a racemic mixture and/or a non-racemic mixture of R and S isomers can also be advantageously used.

The term "odorant" characterizing the compounds according to the present invention means that in humans it triggers an odor sensation which is preferably pleasant; it is therefore conventionally used for perfuming industrial and sanitary articles, washing agents, cleaning agents, personal hygiene products, cosmetics and the like. For the purposes of the present invention and appended claims, the term "odorant" includes "aroma substances". Aroma substances is the term usually used to designate substances which provide odor and/or flavor to foodstuffs.

The compounds of formula (I) may be used alone, as mixtures thereof, or in combination with a base material.

As used herein, the "base material" includes all known fragrance/flavor materials selected from the extensive range of natural products like: essential oils, extracts, resinoids or isolates and synthetic materials currently available, such as: hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes or heterocycles, and/or in admixture with one or more ingredients or excipients/adjuvants conventionally used in conjunction with odorants in fragrance and/or flavor compositions, for example: solvents/diluents, stabilizers, carrier materials, and other auxiliary agents commonly used in the art.

The compounds according to formula (I) may be used in a broad range of fragrance applications, e.g. in any field of fine and functional perfumery, such as perfumes, air care products, household products, laundry products, body care products and cosmetics. The compounds can be employed in widely varying amounts, depending upon the specific application and on the nature and quantity of other odorant ingredients.

According to a preferred embodiment of the invention, the fragrance, flavor and/or deodorizing/masking composition according to the present invention contains at least one compound according to formula (I) as previously described, in quantities between <NUM> and <NUM> wt. %, for example between <NUM> and <NUM> wt. %, preferably between <NUM> and <NUM> wt. %, more advantageously between <NUM> and <NUM> wt. %, in particular between <NUM> and <NUM> wt. %, in each case relative to the entire composition.

According to a particularly preferred embodiment of the invention, in addition to the compound of formula (I) according to the present invention, the fragrance, flavor and/or deodorizing/masking composition according to the present invention contains additional odorants, for example in a quantity of <NUM> to <NUM> wt. %, preferably <NUM>-<NUM> wt. %, in particular <NUM>-<NUM> wt. %, relative to the entire fragrance and/or flavor composition.

The compounds of formula (I) as described hereinabove may be employed in a consumer product base simply by directly mixing at least one compound of formula (I), or a fragrance composition comprising said compound of formula (I) with the consumer product base; or they may, in an earlier step, be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and/or nanocapsules, liposomes, film formers, absorbents such as active carbon or zeolites, cyclic oligosaccharides and mixtures of two or more thereof, or they may be chemically bonded to substrates, which are adapted to release the fragrance molecule upon application of an external stimulus such as light, high temperature, enzyme, air, water or the like, and then mixed with the consumer product base.

Thus, the invention can be useful for existing methods of manufacturing a fragrance, flavor and/or deodorizing/masking composition, comprising the incorporation of a compound of formula (I), as a fragrance, flavor and/or deodorizing/making ingredient, either by directly admixing the compound to the consumer product base or by admixing a fragrance, flavor and/or deodorizing/masking composition comprising said compound of formula (I), which may then be mixed with a consumer product base, using conventional techniques and methods. Through the addition of an olfactory-acceptable amount of at least one compound of formula (I) of the present invention as hereinabove described, the odor notes of a consumer product base can be improved, enhanced, and/or modified.

The present invention provides fragrance, flavor and/or deodorizing/masking compositions comprising a compound of formula (I)
<CHM>
as defined in claims <NUM> to <NUM>.

In an embodiment according to the present invention, the fragrance, flavor and/or deodorizing/masking composition comprises the compound of formula (I) which is <NUM>-((allyloxy)methyl)hex-<NUM>-ene.

In an embodiment, the present invention also claims novel compounds of formula (I) useful in a fragrance, flavor and/or deodorizing/masking composition,
<CHM>
as defined in claims <NUM>-<NUM>.

In an embodiment, the compound of formula (I) useful in a fragrance, flavor and/or deodorizing/masking composition is <NUM>-((allyloxy)methyl)hex-<NUM>-ene.

The Applicants have also discovered that, from an olfactory perspective, the compounds of formula (I) have a distinctly green, fruity, pear and/or waxy profile that lends itself directly to use in fruity compositions such as for example pear, quince, kiwi, and/or pineapple. Indeed, the compounds of formula (I) exhibit more waxy characteristics, reminiscent of the entire natural fruit. It is also more versatile, with easily recognizable applications toward related fruits (quince/apple) as well as unrelated fruits (kiwi/pineapple). Furthermore, compared to other odorants like e.g. Pear Ester, the compounds of formula (I) have greater depth and presence together with an additional property which makes it very valuable, i.e. their greater stability in various application media in particular basic media. For example, when R<NUM> is selected as an alkyl group having <NUM> carbon atoms, the Applicants have discovered that a very diffusive, green, fruity, and pear oriented olfactive note could be obtained.

The compounds of formula (I) can advantageously be prepared from corresponding <NUM>-and/or <NUM>-substituted allyl alcohols of formula (II)
<CHM>
wherein R<NUM> is either an alkyl group having up to <NUM> carbon atoms or an alkenyl group having up to <NUM> carbon atoms and R<NUM> is hydrogen or an alkyl or alkenyl group having up to <NUM> carbon atoms by using a Williamson ether synthesis step, for example by reacting the alcohols of the formula (II) with an allyl bromide and/or an allyl chloride in presence of a base such as sodium hydride and/or sodium hydroxide and/or potassium hydroxide. The resulting ethers are then preferably purified by distillation.

In said alcohols compounds of formula (II), R<NUM> is either an alkyl group having up to <NUM> carbon atoms or an alkenyl group having up to <NUM> carbon atoms and R<NUM> is hydrogen or and alkyl or alkenyl group having up to <NUM> carbon atoms; both R<NUM> and R<NUM> can be straight chain and/or branched alkyls.

In an embodiment, the alcohols as defined in formula (II) can advantageously be synthesized from <NUM>-substituted acroleins of formula (III)
<CHM>
wherein R<NUM> is either an alkyl group having up to <NUM> carbon atoms or an alkenyl group having up to <NUM> carbon atoms,
either by reduction, for example with sodium borohydride or lithium aluminum hydride or by nucleophilic addition of organometallic reagent, for example an appropriate alkyl magnesium halide, R<NUM>MgX e.g. MeMgCl.

In an embodiment, the acroleins of formula (III) can advantageously be synthesized via a reaction of an aldehyde of formula (IV) with formaldehyde (or a formaldehyde source)
<CHM>
wherein R<NUM> is either an alkyl group having up to <NUM> carbon atoms (straight chain and/orbranched alkyl) or an alkenyl group having up to <NUM> carbon atoms, for example by using formaldehyde (e.g. <NUM>% aqueous formaldehyde) or formaldehyde source (e.g. paraformaldehyde) and boric acid and secondary amine combination, for example the combination of boric acid and secondary amine such as diethanolamine; in an embodiment, an acid base combination of <NUM>-methoxybenzoic acid and di-n-butyl amine could also be used for the reaction of aldehydes with formaldehyde. The above reaction of aldehydes with formaldehyde results in formation of <NUM>-substituted acroleins of formula (III) as defined above.

In an embodiment, the compounds of formula (I) can advantageously be prepared by the three following consecutive steps:.

An illustrative scheme of the synthesis of the compounds of formula (I) is represented below
<CHM>
wherein aldehydes with two hydrogens in alpha position are converted into acroleins by reaction with formaldehyde (in form of paraformaldehyde or formalin); acroleins are reduced with sodium borohydride to the corresponding allyl alcohols; allyl alcohols are subjected to Williamson synthesis using for instance allyl chloride to form the bis allyl ethers.

In an embodiment, the aldol condensation, in particular the reaction of aldehydes with formaldehyde (first preparation step) is performed in the presence of a catalyst based on boric acid and a secondary amine, preferably diethanolamine. By developing this specific preparation step, the Applicants have significantly improved the overall preparation process thanks to low odor impact of the catalyst, e.g. when compared to other catalytic systems for aldol condensation which use strongly smelling amines like diethylamine, dibutyl amine, piperidine or pyrrolidine or unpleasantly smelling acids like fatty acids and low catalyst load when comparing to similar catalytic system like for instance dibuthyl amine/hexanoic acid or piperidine/stearic acid. Combination of availability, low cost of the components of the said catalytic system, and relatively low molecular mass of boric acid compared to other acids with similar pKa is particularly advantageous as it positively influences economic aspect of the methylenation process using the said catalytic system.

In an embodiment there is also provided a process for reacting an aldehyde of formula (IV)-(a)
<CHM>.

In an embodiment, the alkyl, alkenyl, alkynyl and oxo-alkyl groups of the aldehyde of formula (IV)-(a) can be linear, branched or cyclic. In an embodiment R<NUM> of the aldehyde of formula (IV)-(a) can be ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, i-butyl, <NUM>-pentyl, <NUM>-pentyl, <NUM>-pentyl, <NUM>-hexyl, <NUM>- hexyl, <NUM>-hexyl, <NUM>-heptyl, <NUM>-heptyl, <NUM>-heptyl, <NUM>- heptyl, <NUM>-octyl, <NUM>-octyl, <NUM>-octyl, <NUM>-octyl, <NUM>-nonyl, <NUM>-nonyl, <NUM>-nonyl, <NUM>-nonyl, <NUM>-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, <NUM>-(cyclohexylmethyl), (methoxy)methyl, (ethoxy)methyl, vinyl, <NUM>-propenyl, <NUM>-isobutenyl, <NUM>-butenyl, <NUM>-(<NUM>-methylpent-<NUM>-en)yl, <NUM>-penten-<NUM>-enyl, <NUM>-pent-<NUM>-enyl, <NUM>-(<NUM>-methylpent-<NUM>-en)yl, <NUM>-(<NUM>,<NUM>-dimethylhex-<NUM>-en)yl, <NUM>,<NUM>,<NUM>-trimethylcyclopent-<NUM>-en-<NUM>-yl, benzyl, phenyl, or <NUM>-methoxyphenyl.

In an embodiment the alkyl, alkenyl, alkynyl and oxo-alkyl groups of the <NUM>-substituted acroleins of formula (III)-(a) can be linear, branched or cyclic. In an embodiment R<NUM> of the <NUM>-substituted acroleins of formula (III)-(a) is ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, i-butyl, <NUM>-pentyl, <NUM>-pentyl, <NUM>-pentyl, <NUM>-hexyl, <NUM>- hexyl, <NUM>-hexyl, <NUM>-heptyl, <NUM>-heptyl, <NUM>-heptyl, <NUM>- heptyl, <NUM>-octyl, <NUM>-octyl, <NUM>-octyl, <NUM>-octyl, <NUM>-nonyl, <NUM>-nonyl, <NUM>-nonyl, <NUM>-nonyl, <NUM>-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, <NUM>-(cyclohexylmethyl), (methoxy)methyl, (ethoxy)methyl, vinyl, <NUM>-propenyl, <NUM>-isobutenyl, <NUM>-butenyl, <NUM>-(<NUM>-methylpent-<NUM>-en)yl, <NUM>-penten-<NUM>-enyl, <NUM>-pent-<NUM>-enyl, <NUM>-(<NUM>-methylpent-<NUM>-en)yl, <NUM>-(<NUM>,<NUM>-dimethylhex-<NUM>-en)yl, <NUM>,<NUM>,<NUM>-trimethylcyclopent-<NUM>-en-<NUM>-yl, benzyl, phenyl, or <NUM>-methoxyphenyl.

The process is characterised in that this reaction (Step I) is performed in the presence of boric acid and a secondary amine (e. dibutylamine, preferably diethanolamine).

In an embodiment the synthesis of acroleins of the formula (III)-(a) (for example those of formula (III)), that is the reaction of aldehydes with formaldehyde (Step I), can advantageously be performed by reacting aldehyde of formula (IV)-(a) (for example those of formula (IV)) with aqueous formaldehyde (or an alternative source of formaldehyde, e.g. paraformaldehyde) in the presence of a dialkylamine and boric acid when the molar ratio of dialkylamine to the intermediate aldehyde of formula (IV)-(a) is between <NUM> and <NUM>, for example between <NUM> and <NUM>; and/or the molar ratio of boric acid to the intermediate aldehyde of formula (IV)-(a) is between <NUM> and <NUM>, for example between <NUM> and <NUM>.

In an embodiment the synthesis of acroleins of the formula (III)-(a) (Step I) is preferentially performed without addition of additional solvents, however any suitable polar on non-polar, protic or non-protic solvent can be used.

In an embodiment the synthesis of acroleins of the formula (III)-(a) is performed between <NUM> and <NUM>, more preferably between <NUM> and <NUM>.

In an embodiment of the present invention, the claimed fragrance, flavor and/or deodorizing/masking composition is advantageously used as a perfumery composition. Perfumery compositions according to the present invention generally include a perfume, a cologne, an eau du toilette, and/or an eau de parfum. In an embodiment of the present invention, the claimed fragrance, flavor and/or deodorizing/masking composition is advantageously used in a cosmetic formulation, a personal care product, a cleansing product, a fabric softener, and/or air freshener, and the like. Furthermore, it is within the purview of embodiments of the invention that the novel fragrance, flavor and/or deodorizing/masking composition(s) and/or novel compound(s) of formula (I) described herein may be integrated into building materials, wall and floor coverings, vehicle components, and the like.

In general, in addition to the novel odorant and/or fragrance, flavor and/or deodorizing/masking compositions described herein, suitable fragrance, flavor or deodorizing compositions may advantageously include conventional ingredients such as, for example, solvents, carriers, stabilizers, emulsifiers, moisturizers, dispersants, diluents, thickeners, thinners, other odorants, and/or adjuvants, and the like.

The compounds of formula (I) combine with numerous known natural or synthetic fragrance, flavor and/or deodorizing/masking materials, whereby the range of the natural ingredients can embrace not only readily-volatile but also semi-volatile and slightly-volatile components and the range of the synthetic ingredients can embrace representatives from many classes of substances, such as described in<NPL>; <NPL>or <NPL>and as will be evident from the following nonlimitting compilation:
Natural products such as:
Ajowan oil, Amyris oil, Armoise oil, Artemisia oil, Basil oil, Bees wax absolute, Bergamot oil, Birch tar oil, Black pepper oil, Black pepper oleoresin, Camphor oil, Cananga oil, Caraway oil, Cardamom oil, Carrot seed oil, Castoreum absolute, Cedar leaf oil, Cedarwood oil, Celery seed oil, Chamomile oil, Cinnamon bark oil, Cinnamon leaf oil, Cistus absolute, Cistus oil, Citronella oil, Citronella terpenes, Clary sage oil, Clove oil rectified, Cognac oil white, Coriander seed oil, Cumin seed oil, Cypress oil, Davana oil, Dill seed oil, Elemi oil, Elemi resinoid, Eucalyptus oil, Fir needle oil, Galbanum oil, Geranium oil, Ginger oil Indian, Grapefruit oil, Guaiacwood oil, Gurjun balsam, Jasmin absolute, Jatamansi oil, Juniper berry oil, Juniper leaf oil, Kachur oil, Labdanum absolute, Labdanum resinoid, Lavender oil, Lemon oil, Lemon oil terpenes, Lemongrass oil, Lime oil, Litsea cubeba oil, Litsea cubeba terpenes, Lobhan choya resinoid, Mandarin oil, Mentha arvenis oil, Mentha citrata oil, Mimosa absolute, Myrrh resinoid, Nagarmotha oil, Nutmeg oil, Oakmoss absolute, Oakmoss resinoid, Olibanum oil, Olibanum resinoid, Orange oil, Origanum oil, Palma rosa oil, Patchouli oil, Peppermint oil, Peru Balsam resinoid, Petitgrain oil, Pine needle oil, Pink pepper oil, Rose absolut, Rose oil, Rosemary oil, Sandalwood oil, Seaweed absolute, Spearmint oil, Sugandh kokila oil, Sugandh mantri oil, Tagete oil, Tolu Balsam resinoid, Tuberose absolute, Turmeric oil, Turpentine oil, Valerian oil, Vetiver oil, Vetiver terpenes.

The compounds of formula (I) can accordingly be used for the production of compositions and, as will be evident from the foregoing compilation, a wide range of known odorants/ fragrance, flavor and/or deodorizing/masking materials. In the production of such compositions, the known fragrance, flavor and/or deodorizing/masking materials referred to earlier can be used according to methods which are known to the perfumer such as, for example, according to W. Poucher, Perfumes, Cosmetics and Soaps <NUM>, 7th Edition, Chapman and Hall, London <NUM>.

In an embodiment of the present invention, the claimed fragrance, flavor and/or deodorizing/masking composition comprises in addition to the allyl ethers at least one ester and/or one alcohol, preferably at least a mixture of ester and alcohol; the said ester and/or alcohol are preferably selected from the list defined herein above. In an embodiment of the present invention, the claimed odorant composition is characterised by a total content of the compound(s) of formula (I) together with the ester(s) and/or alcohol(s) which is superior to <NUM> wt%, preferably superior to 50wt%, for example superior to 75wt%, or even superior to 90wt%.

In another embodiment of the present invention, the claimed fragrance, flavor and/or deodorizing/masking composition comprises in addition to the allyl ethers their respective parent alcohol of general formula (II). In an embodiment of the present invention, the claimed odorant composition is characterized by a total content of the allyl ethers of general formula (I) together with their respective parent alcohol of formula (II) which is superior to <NUM> wt%, e.g. superior to <NUM> wt%, preferably superior to <NUM> wt%, for example superior to <NUM> wt%, or even superior to <NUM> wt%.

The disclosure is further illustrated by the following examples which in no way should be construed as being further limiting. One skilled in the art will readily appreciate that the specific methods and results described are merely illustrative.

All stereoisomers of the compounds of the instant disclosure are contemplated, either in admixture or in pure or substantially pure form. The compounds of the present disclosure can have asymmetric centers at any of the carbon atoms, consequently, claimed compounds can exist in enantiomeric, or diastereomeric forms, or in mixtures thereof. The processes for preparation can utilize racemates, (pure) enantiomers, nonracemic mixtures of enantiomers, diastereomers or mixtures of diasteremers as starting materials. When diastereomeric or enantiomeric products are obtained as mixtures, they can be separated by conventional methods for example, chromatographic separation or fractional crystallization or through diastereomeric salt formation. When intended, a desired enantiomer or diastereomer can also be obtained by following appropriate enantioselective or diastereoselective reactions.

Hexanal (<NUM>, <NUM> mol, <NUM> eq. ) was added to a mixture of aqueous <NUM>% formaldehyde (<NUM>, <NUM> mol, <NUM> eq. ), di-n-butylamine (<NUM>, <NUM> mol, <NUM> eq. ) and p-anisic acid (<NUM>, <NUM> mol, <NUM> eq. ) at <NUM>-<NUM> over a period of <NUM> while stirring. After completion of addition, the reaction mixture was stirred for <NUM> at <NUM>. Subsequently, the reaction mixture was cooled to <NUM>, organic phase was separated, washed with water (<NUM> x <NUM>) and dried over sodium sulfate (<NUM>). The crude product was distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>-methylenehexanal (<NUM>, <NUM>%) as a colorless liquid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> (s, <NUM>).

<NUM>C NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

Sodium borohydride (<NUM>, <NUM> mol, <NUM> meq. ) was added to a mixture of <NUM>-methylenehexanal (<NUM>, <NUM> mol, <NUM> eq. ) and water (<NUM>) at <NUM>-<NUM> over a period of <NUM> while stirring. Then the reaction mixture was stirred for <NUM> at <NUM>. Subsequently, the reaction mixture was quenched with aqueous <NUM>% hydrogen chloride (<NUM>). The organic phase was separated and was successively washed with water (<NUM> × <NUM>), aqueous <NUM>% sodium carbonate (<NUM> × <NUM>) and brine (<NUM> × <NUM>). The organic phase (<NUM>) was distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>-methylenehexan-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (m, <NUM>).

Powdered potassium hydroxide (<NUM>, <NUM> mol, <NUM> eq. ) was added to a mixture of <NUM>-methylenehexan-<NUM>-ol (<NUM>, <NUM> mol, <NUM> eq. ) and tetra-n-butyl ammonium bromide (<NUM>, <NUM> mmol, <NUM> eq. ) at <NUM> over a period of <NUM>. Then allyl chloride (<NUM>, <NUM> mol) was added at <NUM>-<NUM> over a period of <NUM> while stirring. The reaction mixture was stirred at <NUM> for <NUM>. Subsequently, the reaction mixture was filtered through a Büchner funnel and the solid was washed with methyl tert-butyl ether (<NUM>). The filtrate was successively washed with water (<NUM>), aqueous <NUM>% hydrogen chloride (<NUM>), aqueous <NUM>% sodium carbonate (<NUM>) and brine (<NUM>). The volatiles were removed under reduced pressure (<NUM>/ <NUM> mbar). The residue (<NUM>) was distilled in vacuo (<NUM>-<NUM>/ <NUM> mbar) to afford <NUM>-((allyloxy)methyl)hex-<NUM>-ene (<NUM>, <NUM>%) as a colorless liquid. GC purity <NUM> %.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>).

<NUM>C NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

<NUM>-Methylbutanal (<NUM>, <NUM> mol) was added to a mixture of aqueous <NUM>% formaldehyde (<NUM>, <NUM> mol), di n-butylamine (<NUM>, <NUM> mmol) and p-anisic acid (<NUM>, <NUM> mmol) while stirring. Then the mixture was stirred at <NUM> for <NUM>. Subsequently, the reaction mixture was cooled to <NUM> and aqueous saturated sodium hydrogen carbonate was added. The organic phase was separated and the crude product purified by distillation (<NUM>-<NUM>, <NUM> bar) to afford <NUM>-methyl-<NUM>-methylenebutanal (<NUM>, <NUM> %) as a colorless liquid.

Sodium borohydride (<NUM>, <NUM> mmol) was added portion wise to a mixture of <NUM>-methyl-<NUM>-methylenebutanal (<NUM>, <NUM> mmol) in dichloromethane (<NUM>) and methanol (<NUM>) at <NUM> while stirring. Then, the reaction mixture was stirred at <NUM> for <NUM>. , followed by stirring at <NUM> for <NUM>. Subsequently, aqueous <NUM> hydrogen chloride was added until gas formation faded. Then, sodium chloride (<NUM>, <NUM> mmol) was added. The mixture was diluted with water and extracted with methyl tert-butyl ether. The organic phase was separated, washed with brine, dried over sodium sulfate and the volatiles were removed under reduced pressure (<NUM>, <NUM> mbar). The residue was distilled by bulb-to-bulb distillation to afford <NUM>-methyl-<NUM>-methylenebutan-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquide.

A suspension of sodium hydride <NUM>% in mineral oil, (<NUM>, <NUM> mmol) was added portion wise to a solution of <NUM>-methyl-<NUM>-methylenebutan-<NUM>-ol (<NUM>, <NUM> mmol) in tetrahydrofurane (<NUM>) at <NUM> under nitrogen atmosphere. Then allyl bromide (<NUM>, <NUM> mmol) was added at <NUM>. The reaction mixture was stirred at <NUM> for <NUM> days. Then isopropanol (<NUM>) was added followed by water (<NUM>). The organic phase was separated and the aqueous phase was extracted with methyl tert-butyl ether (<NUM> x). The organic phases were combined and volatiles were removed under reduced pressure (<NUM>, <NUM> mbar). The residue (<NUM>) was purified by bulb-to-bulb distillation (<NUM>, <NUM> mbar) to afford <NUM>-((allyloxy)methyl)-<NUM>-methylbut-<NUM>-ene (<NUM>, <NUM> %) as a colorless liquid.

<NUM>-Methylbutanal (<NUM>, <NUM> mol, <NUM> eq. ) was added to a mixture of aqueous <NUM>% formaldehyde (<NUM>, <NUM> mol, <NUM> eq. ), di-n-butylamine (<NUM>, <NUM> mmol, <NUM> eq. ) and p-anisic acid (<NUM>, <NUM> mmol, <NUM> eq. ) at <NUM> over a period of <NUM> and then the reaction mixture was heated at <NUM> for <NUM>. The reaction mixture was cooled to <NUM> and the organic phase was separated, washed with water (<NUM> x <NUM>) and dried over sodium sulfate (<NUM>). The crude mixture was distilled in vacuo (<NUM>-<NUM>/ <NUM> mbar) to afford <NUM>-methyl-<NUM>-methylenebutanal (<NUM>, <NUM>%) as a colorless liquid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>).

<NUM>C NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

A solution of <NUM>-methyl-<NUM>-methylenebutanal (<NUM>, <NUM> mol, <NUM> eq. ) in tetrahydrofuran (<NUM>) was added to a precooled (-<NUM>) solution of ethyl magnesium chloride <NUM> in tetrahydrofurane (<NUM>, <NUM> mol, <NUM> eq. ) at <NUM> over a period of <NUM> while stirring. The reaction mixture was warmed to <NUM> over <NUM> and then stirred at <NUM> for <NUM>. Subsequently, aqueous <NUM>% ammonium chloride (<NUM>) was added followed by methyl tert-butyl ether (<NUM>) while stirring. Then, the organic phase was separated and aqueous phase was extracted with methyl tert-butyl ether (<NUM> × <NUM>). Combined organic phases were washed with brine (<NUM>) and dried over sodium sulfate (<NUM>). Volatiles were removed under reduced pressure and the residue was distilled in vacuo (<NUM>-<NUM>/<NUM>-<NUM> mbar) to afford <NUM>-methyl-<NUM>-methylenehexan-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (t, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>).

<NUM>C NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

Powdered potassium hydroxide (<NUM>, <NUM> mol, <NUM> eq. ) was added to a mixture of <NUM>-methyl-<NUM>-methylenehexan-<NUM>-ol (<NUM>, <NUM> mol, <NUM> eq. ) and tetra-n-butyl ammonium bromide (<NUM>, <NUM> mmol, <NUM> meq. ) at <NUM> over a period of <NUM> while stirring. Then allyl chloride (<NUM>, <NUM> mol, <NUM> eq. ) was added at <NUM>-<NUM> over a period of <NUM>. The reaction mixture was stirred at <NUM> for <NUM>. Subsequently, water (<NUM>) was added followed by methyl tert-butyl ether (<NUM>). Organic phase was separated, washed with water (<NUM> x <NUM>) and dried over sodium sulfate (<NUM>). Volatiles were removed under reduced pressure. The residue was distilled in vacuo (<NUM>-<NUM>/<NUM>-<NUM> mbar) to afford <NUM>-(allyloxy)-<NUM>-methyl-<NUM>-methylenehexane (<NUM>, <NUM>%) as a colorless liquid. GC purity = <NUM>%.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (t, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>).

<NUM>C NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

<NUM>-(allyloxy)-<NUM>-methyl-<NUM>-methylenepentane is prepared by following similar process steps as in example <NUM>. For Step-<NUM>, MeMgCl was used instead of EtMgCl. Yield <NUM>%.

<NUM>-((allyloxy)methyl)hept-<NUM>-ene is prepared according to the procedure described in example <NUM>. Yield <NUM>%.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (br. t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (quint, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (br. d, J = <NUM>, <NUM>), <NUM> (ddt, J = <NUM>, <NUM>, <NUM>, <NUM>).

<NUM>-((allyloxy)methyl)oct-<NUM>-ene is prepared according to the procedure described in example <NUM>. Yield <NUM>%.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (br. t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (quint, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (br. d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (br. dd, J = <NUM>, <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>).

Undecanal (<NUM>, <NUM> mol) was added to a mixture of aqueous <NUM>% formaldehyde (<NUM>, <NUM> mol), diethanolamine (<NUM>, <NUM> mol) and boric acid (<NUM>, <NUM> mmol). The mixture was stirred at <NUM> for <NUM>. Then the mixture was cooled to <NUM> and washed with aqueous <NUM> hydrochloric acid (<NUM>), aqueous sodium hydrogen carbonate (<NUM>), and brine (<NUM>). The crude product was purified by distillation in vacuo (<NUM>-<NUM>/ <NUM> mbar) to afford <NUM>-methylene-<NUM>-undecanal (<NUM>, <NUM> %) as a colorless liquid. Step-<NUM>: <NUM>-((allyloxy)methyl)undec-<NUM>-ene is prepared according to the procedure described in example <NUM>. Yield <NUM>%.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (br. t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (br. ddd, J = <NUM>, <NUM>, <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>).

<NUM>C NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

Citronellal (<NUM>, <NUM> mol) was added to the mixture of paraformaldehyde (<NUM>, <NUM> mol), diethanolamine (<NUM>, <NUM> mmol) and benzoic acid (<NUM>, <NUM> mmol) while stirring. Then the mixture was stirred at <NUM> for <NUM>. Subsequently, brine was added and the organic phase separated to afford the crude <NUM>,<NUM>-dimethyl-<NUM>-methyleneoct-<NUM>-enal (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (br. q, J = <NUM>, <NUM>), <NUM> (sext, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (br. t, J = <NUM>, <NUM>), <NUM> (br. dd, J = <NUM>, <NUM>, <NUM>), <NUM> (br. dd, J = <NUM>, <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>). <NUM>C NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

The olfactory properties of the above compounds are given in the below table.

In the following examples <NUM> to <NUM>, the compound of example <NUM> was included in <NUM> different compositions. Olfactory evaluations were made from a shower gel, dosed at <NUM>. 3wt% perfume composition.

Examples <NUM> and comparative <NUM> - Spicy composition:.

The addition of <NUM>. 0wt% of the example <NUM> compound rendered the spicy composition significantly more performant and diffusive, accentuating the natural cinnamon character and rounding the harsh nitrile aspect. Additionally, a fresh, fruity character was introduced that integrated the various spice characters in the mixture.

Examples <NUM> and comparative example <NUM> - Fougere Composition:.

Adding only <NUM>. 5wt% of the example <NUM> compound to the fougere composition boosted the performance and diffusivity of the composition, blending seamlessly to soften the camphoraceous character of the Lavendin Grosso Oil. The complexity of the composition was significantly enhanced. While the fruity/green character of the target was not specifically apparent the freshness and "clean" impression of the composition was greatly enhanced.

Examples <NUM> and comparative example <NUM> - Citrus Composition:.

Claim 1:
Fragrance, flavor and/or deodorizing/masking composition comprising at least one <NUM>- and/or <NUM>-substituted <NUM>-(allyloxy)propene of formula (I)
<CHM>
wherein R<NUM> is an alkyl group having <NUM> carbon atoms and R<NUM> is hydrogen or an alkyl or alkenyl group having up to <NUM> carbon atoms,
with the proviso that when R2 is hydrogen, R1 can't be tert-butyl.