Patent Description:
Perfumery industry and/or the flavor industry mainly utilize synthetic molecules as raw ingredients. Especially, the introduction of novel odorants/compounds and/or for novel fragrance, flavor and/or deodorizing/masking compositions comprising said odorants/compounds is desirable.

For industrial applications it is beneficial when various products can be derived from one basic scaffold/raw material. It becomes even more beneficial if the raw material is exclusive in certain aspects. <NUM>,<NUM>-Dimethylbutenes (<NUM>) and (<NUM>) are almost exclusively used for production of substituted tetralines (<NUM>) and in particular in production of Tonalid (<NUM>).

Therefore, in the course of their research and development activities, the Applicants started to develop products based on <NUM>,<NUM>-dimethylbutenes (<NUM>) and (<NUM>) as a raw material(s) for novel odorants. It is an advantage of one or more of the embodiments of the present invention that the claimed odorants/compounds derived from <NUM>,<NUM>-dimethybutenes can impart and/or accentuate particular olfactory notes, in particular providing natural piney olfactory notes with a complex odorous profile to fragrance, flavor and/or deodorizing/masking compositions, and also confer to said compositions one or more of the following advantages/properties: cooling-effect properties similar to menthol but with a more natural impression, high diffusivity, and/or solubility.

The article by <NPL>) discloses methods for methylation of isovalerone. On pages <NUM>-<NUM>, the authors describe the synthesis of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexamethylheptan-<NUM>-one (tetramethylisovalerone). Since the newly synthesized tetramethylisovalerone did not form oximes nor semicarbazones (in other words, the compound did not undergo characteristic reactions for qualitative analysis of carbonyl compounds used in the days before spectroscopic methods were available) the authors decided to reduce the putative ketone to an alcohol which by reacting with phenyl isocyanate should form a respective phenyluretane thus proving the successful synthesis of the desired tetramethylisovalerone. The intermediate alcohol synthesized for analytical purposes (<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexamethylheptan-<NUM>-ol), exhibited a strong borneol-like odor.

The article from <NPL>), respectively discloses <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexamethylhepta-<NUM>,<NUM>-dien-<NUM>-ol and <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethylocta-<NUM>,<NUM>-dien-<NUM>-ol obtained by double addition of Grignard reagents to methyl formate.

The article by <NPL>), discloses <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhex-<NUM>-en-<NUM>-ol and <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhept-<NUM>-en-<NUM>-ol in the context of their studies on the coupling of <NUM>,<NUM>-dienes with aldehydes in order to realise coupling reactions without the use of transition-metal catalysts.

The article by <NPL>), discloses <NUM>,<NUM>,<NUM>-trimethylpent-<NUM>-en-<NUM>-ol and <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhept-<NUM>-en-<NUM>-ol obtained via an ene reactions of aliphatic and aromatic aldehydes mediated by dimethylaluminum chloride. The article by<NPL> discloses <NUM>,<NUM>,<NUM>-trimethylhex-<NUM>-en-<NUM>-ol.

This invention relates to alcohols useful in fragrance, flavor and/or deodorizing/masking compositions wherein the alcohols are selected from compounds of formula (<NUM>) or of formula (<NUM>)
<CHM>
wherein R is an alkyl group having from <NUM> to <NUM> carbon atoms or an alkenyl group having from <NUM> to <NUM> carbon atoms as defined in the claims.

In an embodiment the compounds of this invention can be chiral, e.g. they can occur 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 and they can also be advantageously used in pure form or as mixtures.

In another embodiment the compounds of this invention in which the R group is an alkenyl can occur as isomeric mixtures, more specifically as Z isomer, E isomer, and/or a mixture of Z and E isomers and they can also be advantageously used in pure form or as mixtures.

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 alcohol compounds of formula (<NUM>) or of formula (<NUM>) 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, 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 alcohol compounds according to formula (<NUM>) or to formula (<NUM>) 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 alcohol compound according to formula (<NUM>) or formula (<NUM>) as previously described, in quantities between <NUM> and <NUM> wt. %, for example 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 (<NUM>) or of formula (<NUM>) 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 (<NUM>) or of formula (<NUM>) as described hereinabove may be employed in a consumer product base simply by directly mixing at least one compound of formula (<NUM>) or of formula (<NUM>), or a fragrance composition comprising said compound of formula (<NUM>) or of formula (<NUM>) 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, cyclic glycourils, 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, 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 (<NUM>) or of formula (<NUM>), 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 (<NUM>) or of formula (<NUM>), 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 (<NUM>) or of formula (<NUM>) 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 an alcohol selected from compounds of formula (<NUM>) or of formula (<NUM>)
<CHM>.

In an embodiment according to the present invention, the fragrance, flavor and/or deodorizing/masking composition comprises the compound of formula (<NUM>) or of formula (<NUM>) which is selected from any of the compounds named or drawn in the following table.

and/or a mixture of two or more of the said compounds.

The Applicants have also discovered that, from an olfactory perspective, the compounds of formula (<NUM>) or of formula (<NUM>) have a distinctly natural piney profile that lends itself directly to use in herbal, aromatic and citrus compositions without a 'synthetic' effect. The compounds of formula (<NUM>) or of formula (<NUM>) provide sparkling freshness to the compositions and exhibit cooling-effect properties similar to menthol but with a more natural impression. For example, when R is selected as ethyl in the compound (<NUM>), the Applicants have discovered that from an olactory perspective, the compound has a distinct natural quality reminding fir-needle and peppermint oil combined, together with a cooling sensation. Furthermore, compared to other odorants like e.g. borneol, this compound has greater diffusivity, adding even further to the natural effect.

The present invention also provides new compounds of formula (<NUM>) useful in the perfume, aroma and/or deodorizing/masking compositions of the present invention
<CHM>
wherein R is ethyl, n-propyl, n-butyl, s-butyl, t-butyl, <NUM>-methylprop-<NUM>-en-<NUM>-yl, n-pentyl, <NUM>-pentyl, <NUM>-pentyl, n-hexyl, <NUM>-hexyl, <NUM>-hexyl, vinyl, <NUM>-propenyl, prop-<NUM>-en-<NUM>-yl, allyl, <NUM>-butenyl, <NUM>-butenyl, but-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, or hex-<NUM>-en-<NUM>-yl.

The present invention also provides new compounds of formula (<NUM>) useful in the perfume, aroma and/or deodorizing/masking compositions of the present invention
<CHM>
wherein R is ethyl, n-propyl, n-butyl, s-butyl, t-butyl, i-butyl, n-pentyl, <NUM>-pentyl, <NUM>-pentyl, n-hexyl, <NUM>-hexyl, <NUM>-hexyl, <NUM>-propenyl, prop-<NUM>-en-<NUM>-yl, allyl, <NUM>-butenyl, <NUM>-butenyl, but-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-l-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, or hex-<NUM>-en-<NUM>-yl.

In an embodiment according to the present invention, the new compounds of formula (<NUM>) and/or of formula (<NUM>) useful in the perfume, aroma and/or deodorizing/masking compositions of the present invention are selected from any of the compounds named or drawn in the following table.

The compounds of formula (<NUM>) and/or of formula (<NUM>) can advantageously be prepared from <NUM>,<NUM>-dimethylbutene(s) via a sequence of acylation, optional hydrogenation and carbonyl reduction reactions sequence as illustrated hereafter. <CHM>
wherein R is an alkyl group having from <NUM> to <NUM> carbon atoms or an alkenyl group having from <NUM> to <NUM> carbon atoms.

In a preferred embodiment, the compounds of formula (<NUM>) and/or of formula (<NUM>) can advantageously be prepared from <NUM>,<NUM>-dimethylbut-<NUM>-en via a sequence of acylation, optional hydrogenation and carbonyl reduction reactions sequence as illustrated hereafter.

In an embodiment, the trimethyl alkenol of formula (<NUM>) and the trimethyl alkanol of formula (<NUM>) can advantageously be prepared from the corresponding ketones <NUM> or <NUM> respectively by reducing the carbonyl group of compounds of formula (<NUM>) or of formula (<NUM>). Any appropriate carbonyl reduction process can be used. In an embodiment, sodium borohydride in ethanol and water mixture is advantageously used.

In another embodiment, the the trimethyl alkanol of formula (<NUM>) can advantageously be prepared from the corresponding ketone <NUM> by directly reducing both the carbonyl group and the double bond of compounds of formula <NUM>. Any appropriate reduction process can be used. In an embodiment, hydrogen in presence of Pt/C can be advantageously used.

The table below illustrates the said corresponding ketones (identified as "parent" ketone in this description and appended claims) represented by general formula <NUM> or <NUM>.

The <NUM>,<NUM>-dimethylbutenes compounds according to the present invention can be selected from <NUM>,<NUM>-dimethyl-<NUM>-butene, <NUM>,<NUM>-dimethyl-<NUM>-butene, or a mixture thereof; preferably from <NUM>,<NUM>-dimethyl-<NUM>-butene or from a mixture of <NUM>,<NUM>-dimethyl-<NUM>-butene and <NUM>,<NUM>-dimethyl-<NUM>-butene.

In an embodiment, an isomerisation step is preferably performed in order to convert <NUM>,<NUM>-dimethyl-<NUM>-butene into <NUM>,<NUM>-dimethyl-<NUM>-butene. This isomerisation step is preferably performed for example when the starting material is <NUM>,<NUM>-dimethyl-<NUM>-butene or when the starting material is a mixture of <NUM>,<NUM>-dimethyl-<NUM>-butene and <NUM>,<NUM>-dimethyl-<NUM>-butene having a content of <NUM>,<NUM>-dimethyl-<NUM>-butene superior to the content of <NUM>,<NUM>-dimethyl-<NUM>-butene. Any appropriate olefin isomerisation process can be used; as illustrative and non-restricting examples, base-catalysed and/or acid-catalysed isomerisation process can advantageously be used. In an embodiment, an ion-exchange resin acid catalyst, e.g. an Amberlyst catalyst in the acid form is advantageously used.

Thus, in an embodiment, the <NUM>,<NUM>-dimethylbutene(s) are subjected to an acylation synthesis step to form the ketones of formula (<NUM>) which can be represented by the following formula
<CHM>
wherein R is an alkyl group having from <NUM> to <NUM> carbon atoms or an alkenyl group having from <NUM> to <NUM> carbon atoms.

In an embodiment of the present invention, the product is obtained by reacting <NUM>,<NUM>-dimethylbutene(s) with acyl anhydride or acyl chloride, preferably followed by usual workup (e.g. aqueous wash, removal of unreacted reactants and/or solvents and distillation). In an embodiment according to the present invention, R is ethyl, n-propyl, n-butyl, s-butyl, t-butyl, <NUM>-methylprop-<NUM>-en-<NUM>-yl, n-pentyl, <NUM>-pentyl, <NUM>-pentyl, n-hexyl, <NUM>-hexyl, <NUM>-hexyl, vinyl, <NUM>-propenyl, prop-<NUM>-en-<NUM>-yl, allyl, <NUM>-butenyl, <NUM>-butenyl, but-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-l-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, or hex-<NUM>-en-<NUM>-yl. Any appropriate acylation process leading to the above ketones compounds of formula (<NUM>) can be used; as illustrative and non-restricting examples, the acylation is performed in the presence of <NUM>,<NUM>-dimethylbutene(s) and a carboxylic acid anhydride, for example acetic anhydride or propionic anhydride. This process step can advantageously be operated in the presence of an acid catalyst.

This process step can advantageously be operated in the presence of a Lewis or Bronsted acid catalyst, for example zinc chloride, methanesulfonic acid, trifluoromethanesulfonic acid, etc. This process step can advantageously be operated either neat or with the use of a suitable aprotic, polar solvent (e.g.dichloromethane).

In an embodiment, the acylation step is preferably followed by an alkylation step; e.g. the <NUM>,<NUM>-dimethylbutene(s) are subjected to an acylation synthesis step to form the lower alkyl ketone compounds which are then converted into the desired higher alkyl ketones. In an embodiment according to the present invention, the acylation step is preferably followed by an alkylation step; e.g. the <NUM>,<NUM>-dimethylbutene(s) are subjected to an acylation synthesis step to form the compounds of formula (5a) as represented by the following formula (5a, i.e. wherein R=CH<NUM>)
<CHM>
which is then converted into compounds of formula (5b) as represented by the following formula
<CHM>
wherein R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, OR an oxo-alkyl group having up to <NUM> carbon atoms.

Compound of the formula (5b) which can be obtained either by subjecting <NUM>,<NUM>-dimethylbutene(s) to an acylation synthesis step to form directly the compounds of formula (5b) or by subjecting compounds of formula (5a) to an alkylation step can be further alkylated to form compound of formula (5c). <CHM>
wherein R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and the sum of carbon atoms present in radicals R<NUM> and R<NUM> is not more than <NUM>.

Compound of the formula (5c) which can be obtained either by subjecting <NUM>,<NUM>-dimethylbutene(s) to an acylation synthesis step to form directly the compounds of formula (5c) or by subjecting compounds of formula (5b) to an alkylation step or by subjecting compound (5a) to a double alkylation step can be further alkylated to form compound of formula (5d). <CHM>
wherein R<NUM> an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, and the sum of carbon atoms present in radicals R<NUM>, R<NUM> and R<NUM> is not more than <NUM>.

When compounds of formula (5c) and (5d) have at least two of the R<NUM>, R<NUM> or R<NUM> groups identical, the introduction of these identical groups can be performed in a single alkylation step.

An advantage of the acylation step of the synthesis process - when <NUM>,<NUM>-dimethyl-<NUM>-butene is the starting material - is that it can tolerate the presence of <NUM>,<NUM>-dimethyl-<NUM>-butene. Consequently, whilst the present invention preferentially uses pure <NUM>,<NUM>-dimethyl-<NUM>-butene for the acylation step, it can also advantageously tolerate as starting materials molar ratios of <NUM>,<NUM>-dimethyl-<NUM>-butene to <NUM>,<NUM>-dimethyl-<NUM>-butene which is lower than <NUM>%, for example lower than <NUM>%; said molar ratio is preferably higher than <NUM>%, for example higher than <NUM>%, or even higher than <NUM>%.

In another embodiment, the acylation step is preferably performed starting from pure <NUM>,<NUM>-dimethylbut-<NUM>-ene. In an alternative embodiment, the acylation step is preferably followed by an aldol condensation step; e.g. the <NUM>,<NUM>-dimethylbutene(s) are subjected to an acylation synthesis step to form the compounds of formula (5a) as represented by the following formula (5a, i.e. wherein R=CH<NUM>)
<CHM>
which is then converted into compounds of formula (5e) as represented by the following formula
<CHM>
wherein R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and the sum of carbon atoms present in radicals R<NUM> and R<NUM> is not more than <NUM>.

In an embodiment, compound of the formula (5b) which can be obtained either by subjecting <NUM>,<NUM>-dimethylbutene(s) to an acylation synthesis step to form directly the compounds of formula (5b) or by subjecting compounds of formula (5a) to an alkylation step can be subjected to an aldol condensation step to form compound of formula (5f). <CHM>
wherein R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and the sum of carbon atoms present in radicals R<NUM> and R<NUM> and R<NUM> is not more than <NUM>.

In an embodiment, the acylation step is preferably followed by hydrogenation step and an optional alkylation step; e.g. the <NUM>,<NUM>-dimethylbutene(s) are subjected to an acylation synthesis step followed by hydrogenation synthesis step to form the saturated ketones of formula (<NUM>) according to the present invention.

In an embodiment, the acylation step is preferably followed by hydrogenation step and an alkylation step; e.g. the <NUM>,<NUM>-dimethylbutene(s) are subjected to an acylation synthesis step followed by hydrogenation synthesis step to form the compounds of formula (6a) as represented by the following formula (6a, i.e. wherein R=CH<NUM>)
<CHM>
which is then converted into compounds of formula (6b) as represented by the following formula
<CHM>
wherein R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms.

In an embodiment, compound of the formula (5b) which can be obtained either by subjecting <NUM>,<NUM>-dimethylbutene(s) to an acylation synthesis step to form directly the compounds of formula (5b) or by subjecting compounds of formula (6a) to an alkylation step can be further alkylated to form compound of formula (6c). <CHM>
wherein R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, an oxo-alkyl group having up to <NUM> carbon atoms, and the sum of carbon atoms present in radicals R<NUM> and R<NUM> is not more than <NUM>.

In an embodiment, compound of the formula (6c) which can be obtained either by subjecting <NUM>,<NUM>-dimethylbutene(s) to an acylation synthesis step to form directly the compounds of formula (6c) or by subjecting compounds of formula (6b) to an alkylation step or by subjecting compound (6a) to a double alkylation step can be further alkylated to form compound of formula (6d). <CHM>
wherein R<NUM> an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, R<NUM> is selected from an alkyl group having from <NUM> to <NUM> carbon atoms, an alkenyl group containing only one carbon-carbon double bond and having up to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, and the sum of carbon atoms present in radicals R<NUM>, R<NUM> and R<NUM> is not more than <NUM>.

When compounds of formula (6c) and (6d) have at least two of the R<NUM>, R<NUM> or R<NUM> groups identical, the introduction of these identical groups can be performed in a single alkylation step.

In an embodiment, the acylation step followed by a hydrogenation step is preferably followed by an aldol condensation step; e.g. the <NUM>,<NUM>-dimethylbutene(s) are subjected to an acylation synthesis step followed by a hydrogenation step to form the compounds of formula (6a) as represented by the following formula (6a, i.e. wherein R=CH<NUM>)
<CHM>
which is then converted into compounds of formula (6e) as represented by the following formula
<CHM>
wherein R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, and the sum of carbon atoms present in radicals R<NUM> and R<NUM> is not more than <NUM>.

In an embodiment, compound of the formula (6b) which can be obtained either by subjecting <NUM>,<NUM>-dimethylbutene(s) to an acylation synthesis step to form directly the compounds of formula (6b) or by subjecting compounds of formula (6a) to an alkylation step can be subjected to an aldol condensation step to form compound of formula (6f). <CHM>
wherein R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, and R<NUM> is selected from hydrogen, an alkyl group having from <NUM> to <NUM> carbon atoms, or an oxo-alkyl group having up to <NUM> carbon atoms, and the sum of carbon atoms present in radicals R<NUM> and R<NUM> and R<NUM> is not more than <NUM>.

The synthesis of ketones (<NUM>) and (<NUM>) can be thus advantageously realized according to the following schemes:
<CHM>.

Any appropriate alkylation process leading to compounds of formula (5b-d) and (6b-d) respectively can be used; as illustrative and non-restricting examples, the alkylation is performed in the presence of the products of acylation of <NUM>,<NUM>-dimethylbutenes with the general structure (<NUM>) or (<NUM>) and an alkyl halide or alkyl sulfate (methyl iodide, dimethyl sulfate, etc) in the presence of a base (potassium hydroxide, potassium tertbutoxide, etc). Any appropriate aldol condensation process leading to compounds of formula (5e-f) and (6e-f) respectively can be used; as illustrative and non-restricting examples, the aldol condensation is performed in the presence of the products of acylation of <NUM>,<NUM>-dimethylbutenes with the general structure (<NUM>) or (<NUM>) and an aldehyde or ketone in the presence of a base (potassium hydroxide, potassium tertbutoxide, etc) or in the presence of an acid (hydrochloric acid, sulfuric acid etc.).

The synthesis of saturated ketones can be thus advantageously realized according to the following scheme:
<CHM>.

In an embodiment according to the present invention, the compounds of formula (<NUM>) can advantageously be prepared by the following consecutive steps:.

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

An advantage of the carbonyl reduction step of the synthesis process is that it can tolerate the presence of the reactants of the previous synthesis step, i.e. the reactants coming either from the acylation step and/or from the combined acylation/alkylation or from the combined acylation/aldol condensation step as described hereinabove. Consequently, in an embodiment, the acylation step can advantageously be performed when.

In an embodiment, the carbonyl reduction step can also advantageously be performed when.

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 (<NUM>) or of formula (<NUM>) 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 (<NUM>) and/or (<NUM>) 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, 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.

Synthetic raw materials for instance:
Esters such as: Aldehyde C16, Allyl amyl glycolate, Allyl caproate, Allyl cyclohexyl propionate, Allyl heptoate, Allyl phenoxy acetate, Amyl acetate iso, Amyl benzoate, Amyl butyrate, Amyl caproate, Amyl cinnamate, Amyl isovalerate, Amyl phenyl acetate, Amyl propionate, Amyl salicylate iso, Amyris acetate, Anisyl acetate, Benzyl acetate, Benzyl benzoate, Benzyl butyrate, Benzyl cinnamate, Benzyl formate, Benzyl isobutyrate, Benzyl isoeugenol, Benzyl propionate, Benzyl salicylate, Benzyl tiglate, Butyl acetate, Butyl butyrate, Butyl butyryl lactate, Caryophyllene acetate, Cedryl acetate, Cinnamyl acetate, Cinnamyl butyrate, Cis-<NUM>-hexenyl acetate, Cis-<NUM>-hexenyl benzoate, Cis-<NUM>-hexenyl caproate, Cis-<NUM>-hexenyl formate, Cis-<NUM>-hexenyl isobutyrate, Cis-<NUM>-hexenyl-<NUM>-methyl butyrate, Cis-<NUM>-hexenyl propionate, Cis-<NUM>-hexenyl salicylate, Cis-<NUM>-hexenyl tiglate, Citronellyl acetate, Citronellyl butyrate, Citronellyl formate, Citronellyl isobutyrate, Citronellyl propionate, Citronellyl tiglate, Cyclabute, Cyclogalbanate, Cyclohexyl ethyl acetate, Decyl acetate, Dibutyl phthalate, Diethyl malonate, Diethyl phthalate, Dihydromyrcenyl acetate, Dimethyl octanyl acetate, Dimethyl phenyl ethyl carbinyl acetate, Dioctyl adipate, Dioctyl phthalate, Dimethyl benzyl carbinyl acetate, Dimethyl benzyl carbinyl butyrate, Ethyl linalyl acetate, Ethyl <NUM>-methyl butyrate, Ethyl <NUM>-phenyl propionate, Ethyl acetate, Ethyl acetoacetate, Ethyl benzoate, Ethyl butyrate, Ethyl caprate C10, Ethyl caproate C6, Ethyl caprylate C8, Ethyl cinnamate, Ethyl heptoate, Ethyl hexyl acetate, Ethyl isobutyrate, Ethyl laurate, Ethyl pelargonate, Ethyl phenoxy acetate, Ethyl phenyl acetate, Ethyl phenyl glycidate, Ethyl propionate, Ethyl safranate, Ethyl salicylate, Ethyl valerate, Eugenyl acetate, Evernyl, Fenchyl acetate, Floramat, Frescolat ML, Fructone, Fruitate, Geranyl acetate, Geranyl butyrate, Geranyl formate, Geranyl propionate, Geranyl tiglate, Givescone, Guaiol acetate, Hedionate, Hedione, Helvetolide, Herbanate, Hexyl acetate, Hexyl benzoate, n-Hexyl butyrate, Hexyl caproate, Hexyl isobutyrate, Hexyl propionate, Hexyl salicylate, Isobomyl acetate, Isobutyl acetate, Isobutyl phenyl acetate, Isobutyl salicylate, Isoeugenyl acetate, Isononyl acetate, Isopentyrate, Isopropyl <NUM>-methyl butyrate, Isopropyl myristate, Jasmonyl, Liffarome, Linalyl acetate, Mahagonate, Manzanate, Menthanyl acetate, Menthyl acetate, Methyl benzoate, <NUM>-Methyl butyl acetate, Methyl camomille, Methyl cinnamate, Methyl cyclogeranate, Methyl heptine carbonate, Methyl laurate, Methyl octine carbonate, Methyl phenyl acetate, Methyl salicylate, Methyl-<NUM>-methyl butyrate, Neofolione, Nopyl acetate, Octenyl acetate, Octyl acetate, Octyl isobutyrate, Para cresyl acetate, Para cresyl isobutyrate, Para cresyl phenyl acetate, Pear ester, Peranat, Phenoxy ethyl isobutyrate, Phenyl ethyl acetate, Phenyl ethyl butyrate, Phenyl ethyl formate, Phenyl ethyl isobutyrate, Phenyl ethyl phenyl acetate, Phenyl ethyl propionate, Phenyl ethyl salicylate, Phenyl ethyl tiglate, Phenyl propyl isobutyrate, Prenyl acetate, Romandolide, Sagecete, Styrallyl acetate, Styrallyl propionate, Tangerinol, Terpinyl acetate, Thesaron, Trans-<NUM>-hexenyl acetate, Tropicate, Verdox, Verdyl acetate, Verdyl propionate, Vertenex, Vetikol acetate, Vetiveryl acetate, Yasmolys.

Lactones such as: Ambrettolide, Arova N, Celeriax, Decalactone delta, Decalactone gamma, Dodecalactone delta, Dodecalactone gamma, Ethylene brassylate, Exaltolide, Heptalactone gamma, Hexalactone delta, Hexalactone gamma, Methyl laitone, Methyl octalactone, Nonalactone delta, Nonalactone gamma, Octahydrocoumarine, Octalactone delta, Octalactone gamma, Rootylone, Silvanone supra, Undecalactone delta, Undecalactone gamma, Valerolactone gamma, <NUM>-Oxa HexaDecanolide (OHD musk), Coumarin, Habanolide, Jasmolactone.

Aldehydes such as: Acetaldehyde, Adoxal, Aldehyde C10, Aldehyde C11 iso, Aldehyde C11 moa, Aldehyde C11 undecylenic, Aldehyde C11 undecylic, Aldehyde C12 lauric, Aldehyde C12 MNA, Anisaldehyde, Amyl cinnamaldehyde, Benzaldehyde, Bourgeonal, Campholenaldehyde, Cantonal, Cetonal, Cinnamic aldehyde, Cis-<NUM>-decenal, Cis-<NUM>-nonenal, Citral, Citronellal, Citronellyl oxyacetaldehyde, Cocal, Cuminaldehyde, Curgix, Cyclal C, Cyclamen aldehyde, Cyclomyral, Cyclovertal, Decenal <NUM>, Dupical, Empetal, Ethyl vanillin, Floralozone, Florhydral, Geraldehyde, Helional, Heliotropin, Heptanal, Hexanal, Hexyl cinnamaldehyde, Hivernal neo, Hydratropaldehyde, Hydroxycitronellal, Intreleven aldehyde, Isobutavan, Isocyclocitral, Isovaleraldehyde, Lilial, Limonenal, Maceal, Mefranal, Melonal, Methyl cinnamaldehyde, Nonadien-al trans-<NUM> cis-<NUM>, Nonanal, Octanal, Oncidal, Para tolyl aldehyde, Phenyl acetaldehyde, Phenyl propyl aldehyde, Precyclemone B, Safranal, Salicylaldehyde, Scentenal, Syringa aldehyde, Trans-<NUM>-decenal, Trans-<NUM>-dodecenal, Trans-<NUM>-hexenal, Trans-<NUM>-nonenal, Trifernal, Vanillin, Veratraldehyde, Vernaldehyde.

Ketones such as: Acetanisol, Acetoin, Acetophenone, Aldron, Allyl ionone, Benzophenone, Benzyl acetone, Calone, Camphor, Carvone d-, Carvone <NUM>-, Cashmeran, Cedryl methyl ketone, Cepionate, Claritone, Cosmone, Crysolide, Cyclotene, Damascenone, Damascone alpha, Damascone beta, Damascone delta, Damascone gamma, Diacetyl, Dihydro beta ionone, Dihydro isojasmonate, Dimethyl octenone, Dynascone, Ethyl amyl ketone, Ethyl maltol, Fenchone, Filbertone, Geranyl acetone, Globanone, Heptyl cyclopentanone, Ionone alpha, Ionone beta, Ionone pure, Iriswood, Irone alpha, Iso E Super, Isofenchone, Isojasmone T, Isolone K, Isomenthone, Isophorone, Jasmone cis-, Kambernoir, Kephalis, Koavone, Lavendinal, Maltol, Menthone, Methyl acetophenone, Methyl amyl ketone, Methyl heptenone, Methyl hexyl ketone, Methyl ionone gamma, Methyl naphthyl ketone beta, Methyl nonyl ketone, Muscenone, Muscone, Nectaryl, Orinox, OTBC Ketone, Para tertbutylcyclohexanone, Patchwood, Phantolid, Pharaone, Piperitone, Plicatone, Raspberry ketone, Raspberry ketone methyl ether, Safraleine, Spirogalbanone pure, Tonalid, Trimofix O, Veloutone, Vetikon.

Alcoholos such as: Alcohol oxo C13, Amber core, Ambermax, Ambrinol, Amyl vinyl carbinol, Anisic alcohol, Bacdanol, Benzyl alcohol, Butanol, Cedrol crystals, Cinnamic alcohol, Citronellol, Coranol, Decanol, Dimethyl benzyl carbinol, Dimethyl octanol, Dimethyl phenyl ethyl carbinol, Dimetol, Fenchol, Hexanol, Isoborneol, Isobomyl cyclohexanol, Javanol, Keflorol, Kohinool, Lauryl alcohol, Lilyflore, Linalool oxide, Mayol, Menthol, Norlimbanol, Octanol, Osyrol, Para tertbutylcyclohexanol, Phenoxanol, Phenoxyethanol, Phenyl ethyl alcohol, Phenyl propyl alcohol, Propylene glycol, Rosaphen, Rose glycol, Styrallyl alcohol, Tricyclodecane dimethanol, Tetrahydro linalool, Tetrahydro myrcenol, Timberol, Undecavertol, Cis-<NUM>-hexenol, Citronellol laevo, Cyclofloranol, Dihydrolinalool, Dihydromyrcenol, Dimyrcetol, Ebanol, Geraniol, Isopulegol, Linalool, Nerol, Nerolidol, Nonadien-ol trans-<NUM> cis-<NUM>, Polysantol, Rosalva, Sandalmysore core, Sandalore, Terpinen-<NUM>-ol, Terpineol, Trans-<NUM>-hexenol
Phenols such as: Butylated hydroxyanisole, Dihydroeugenol, Dimethyl hydroquinone, Dimethyl resorcinol, Eugenol pure, Guaiacol, Isoeugenol, Meta cresol, Methyl diantilis, Para cresol, Propenyl guaethol, Thymol, Ultravanil.

Ethers such as: Ambroxan, Anethole, Anther, Benzyl isoamyl ether, Benzyl isopropyl ether, Benzyl isovalerate, Boisiris, Cedramber, Cetalox, Decyl methyl ether, Dibenzyl ether, Dihydro rose oxide, Diphenyl oxide, Doremox, Estragole, Ethyl linalool, Eucalyptol, Galaxolide, Gyrane, Herbavert, Lime oxide, Madrox, Methyl isoeugenol, Naphthyl isobutyl ether beta, Nerol oxide, Nerolin bromelia, Para cresyl butyl ether, Para cresyl methyl ether, Petiole, Phenyl ethyl methyl ether, Rhubafuran, Rose oxide, Rosyrane, Trisamber, Vetylbois K, Yara yara
Acetals such as: Acetal CD, Acetal R, Amberketal, Boisambrene forte, Citrathal, <NUM>,<NUM>-Diethoxyethane, Emeraldine, Freshopal, Herboxane, Indoflor, Jacinthaflor, Magnolan, Spirambrene, Viridine, Elintaal, Glycolierral, Karanal, Methyl pamplemousse, Hydrocarbons such as: Bisabolene, Camphene, Carene delta <NUM>, Caryophyllene, Cedrene, Cymene para, Dipentene, Diphenyl methane, Isolongifolene, Limonene d-, Longifolene, Myrcene, Naphthalene, Ocimene, Pinene alpha, Pinene beta, Styrene, Terpinene gamma, Terpinolene, <NUM>,<NUM>,<NUM>-Undecatriene, Verdoracine.

Sulphur compounds such as: Corps cassis, Dibutyl sulphide, Dimethyl sulphide, Exovert, Grapefruit thiol, Oxane, Ribes mercaptan, Sulfurol, Thiocineol.

Nitriles such as: Cinnamyl nitrile, Citronellyl nitrile, Citronitrile, Clonal, Cumin nitrile, Hexyl cyclopentanone, Irisnitrile, Lemonile, Peonile, Tridecyl nitrile, Agrumen nitrile, n-decyl nitrile.

Oximes such as: Buccoxime, Labienoxime, Stemone.

Nitrogen heterocycles such as: <NUM>-acetylpyrazine, <NUM>-acetylpyridine, sec-butylquinoline, Corps racine, <NUM>-ethyl-<NUM>,<NUM>(or <NUM>)-dimethylpyrazine, Furfuryl pyrrole, Indole, Isobutyl quinoline, <NUM>-Isobutyl-<NUM>(or <NUM>)-methoxypyrazine, Isopropyl quinoline, Maritima, p-methyl quinoline, Skatol, <NUM>,<NUM>,<NUM>-trimethylpyrazine.

Schiff bases such as: Aurantiol, Helianthral, Ligantraal, Verdantiol.

Other materials such as: Acetanilide, Gardamide, Paradisamide, Dimethyl anthranilate, Methyl anthranilate, n-Butyric acid, Capric acid, Caproic acid, Caprylic acid, Phenylacetic acid, Caryophyllene oxide, Cedroxyde, Tobacarol.

The compounds of formula (<NUM>) and/or (<NUM>) 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 <NPL>.

In an embodiment of the present invention, the claimed fragrance, flavor and/or deodorizing/masking composition comprises in addition to the alcohols of formula (<NUM>) and/or (<NUM>) 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 characterized by a total content of the compound(s) of formula (<NUM>) or of formula (<NUM>) together with the ester(s) and/or other alcohol(s) which is superior to <NUM> wt%, preferably superior to <NUM> wt%, for example superior to <NUM> wt%, or even superior to <NUM> wt%.

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 diastereomers 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.

In an embodiment of the present invention, the claimed fragrance, flavor and/or deodorizing/masking composition comprises in addition to the alcohols of formula (<NUM>) or of formula (<NUM>) their respective parent ketone of formula (<NUM>) or of formula (<NUM>).

By parent compound is considered here a compound which is an intermediate used in the synthesis.

The present invention also relates to odorant compositions comprising a mixture of alcohol(s) of formula (<NUM>) with its(their) respective parent ketone(s) of formula (<NUM>); in a preferred embodiment, the weight ratio between the parent ketone of formula (<NUM>) and its alcohol of formula (<NUM>) is comprised between <NUM> and <NUM>, and/or the total content in the odorant composition of the alcohols of formula (<NUM>) and of their respective parent ketone of formula (<NUM>) 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%.

In another embodiment of the present invention, the claimed fragrance, flavor and/or deodorizing/masking composition comprises a mixture of the alcohols of formula (<NUM>) and of the alcohols of formula (<NUM>).

The present invention also relates to odorant compositions comprising a mixture of alcohol(s) of formula (<NUM>) and alcohol(s) of formula (<NUM>), optionally and preferably together with their respective parent ketone of formula (<NUM>)/formula (<NUM>); in a preferred embodiment, the weight ratio between the parent ketone and its alcohol is comprised between <NUM> and <NUM>, and/or the total content in the odorant composition of the alcohols of formula (<NUM>) and of formula (<NUM>) and of their respective parent ketone of formula (<NUM>) and of formula (<NUM>) 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 present invention also relates to odorant compositions comprising a mixture of alcohol of formula (7d) optionally and preferably together with one or more alcohols of formula (7a-c) and/or one or more of their respective parent ketones of formula (5a-d).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (7c) optionally and preferably together with one or more alcohols of formula (7a-b) and/or one or more of their respective parent ketones of formula (5a-c).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (7b) optionally and preferably together with alcohol of formula (7a) and/or one or more of their respective parent ketones of formula (5a-b).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (7e) optionally and preferably together with alcohol of formula (7a) and/or one or more of their respective parent ketones of formula (5a, e).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (7f) optionally and preferably together with one or more alcohols of formula (7a-b) and/or one or more of their respective parent ketones of formula (5a-b, f).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8e) optionally and preferably together with alcohol of formula (8a) and/or (7a) and/or their respective parent ketones of formula (6a) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8f) optionally and preferably together with alcohol of formula (8a) and/or (8b) and/or (7a) and/or their respective parent ketones of formula (6f) and/or (6a) and/or (6b) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8f) optionally and preferably together with alcohol of formula (8b) and/or (7b) and/or (7a) and/or their respective parent ketones of formula (6f) and/or (6b) and/or (5b) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8c) optionally and preferably together with alcohol of formula (8b) and/or (8a) and/or (7a) and/or their respective parent ketones of formula (6c) and/or (6b) and/or (6a) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8c) optionally and preferably together with alcohol of formula (8b) and/or (7b) and/or (7a) and/or their respective parent ketones of formula (6c) and/or (6b) and/or (5b) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8c) optionally and preferably together with alcohol of formula (7c) and/or (7b) and/or (7a) and/or their respective parent ketones of formula (6c) and/or (5c) and/or (5b) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8d) optionally and preferably together with alcohol of formula (8c) and/or (8b) and/or (8a) and/or (7a) and/or their respective parent ketones of formula (6d) and/or (6c) and/or (6b) and/or (6a) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8d) optionally and preferably together with alcohol of formula (8c) and/or (8b) and/or (7b) and/or (7a) and/or their respective parent ketones of formula (6d) and/or (6c) and/or (6b) and/or (5b) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8d) optionally and preferably together with alcohol of formula (8c) and/or (7c) and/or (7b) and/or (7a) and/or their respective parent ketones of formula (6d) and/or (6c) and/or (5c) and/or (5b) and/or (5a).

The present invention also relates to odorant compositions comprising a mixture of alcohol of formula (8d) optionally and preferably together with alcohol of formula (7d) and/or (7c) and/or (7b) and/or (7a) and/or their respective parent ketones of formula (6d) and/or (5d) and/or (5c) and/or (5b) and/or (5a).

As a reminder, the alcohols of formula (<NUM>) and of formula (<NUM>) can advantageously be represented by the following schemes
<CHM>
wherein R is an alkyl group having from <NUM> to <NUM> carbon atoms or an alkenyl group having from <NUM> to <NUM> carbon atoms as defined hereinabove.

As a reminder, the ketones of formula (<NUM>) or of formula (<NUM>) can advantageously be represented by the following schemes
<CHM>
wherein R is an alkyl group having from <NUM> to <NUM> carbon atoms or an alkenyl group having from <NUM> to <NUM> carbon atoms as defined hereinabove.

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.

Methanesulfonic acid (<NUM>, <NUM> mol) was added to a mixture of <NUM>,<NUM>-dimethyl-<NUM>-butene (<NUM>, <NUM> mol, <NUM> equiv) and propionic anhydride (<NUM>, <NUM> mol) at <NUM>, under nitrogen while stirring. The mixture was stirred at <NUM> for <NUM>. Subsequently, the mixture was washed with water (<NUM> x <NUM>) followed by aqueous <NUM>% sodium carbonate solution (<NUM> x <NUM>) and water (<NUM> x <NUM>). The crude product was purified by distillation in vacuo to afford <NUM>,<NUM>,<NUM>-trimethylhex-<NUM>-en-<NUM>-one (<NUM>, <NUM>%).

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

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

Sodium borohydride (<NUM>, <NUM> mol) was added to a mixture of <NUM>,<NUM>,<NUM>-trimethylhex-<NUM>-en-<NUM>-one (<NUM>, <NUM> mol) ethanol (<NUM>) and water (<NUM>) at <NUM>-<NUM> over a period of <NUM> while stirring. Then the mixture was stirred for <NUM> at <NUM>. Subsequently, acetic acid (<NUM>) was added. Organic phase was separated and washed with water (<NUM> x <NUM>), aqueous <NUM>% sodium carbonate solution (<NUM> x <NUM>) and water (<NUM> x <NUM>). The crude product (<NUM>) was distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>,<NUM>,<NUM>- trimethylhex-<NUM>-en-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

<NUM>H NMR (<NUM>, CDCl<NUM>) δ <NUM> (s, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (tdd, J = <NUM>, <NUM>, <NUM>, <NUM>), <NUM> (tdd, J = <NUM>, <NUM>, <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>). <NUM>C NMR (<NUM>, CDCl<NUM>) δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

Raney Ni (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethylhex-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in isopropanol (<NUM>) at <NUM> and the mixture was stirred under hydrogen at <NUM>/<NUM> bar for <NUM>. The mixture was cooled to <NUM>, filtered through a pad of celite and the solvent was removed under reduced pressure to afford <NUM>,<NUM>,<NUM>-trimethylhexan-<NUM>-one (<NUM>, <NUM>%).

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

Sodium borohydride (<NUM>, <NUM> mmol) was added to a mixture of <NUM>,<NUM>,<NUM>-trimethylhexan-<NUM>-one (<NUM>, <NUM> mmol) in ethanol (<NUM>) and water (<NUM>) at <NUM>-<NUM> over a period of <NUM> while stirring. Then the mixture was stirred for <NUM> at <NUM>. Subsequently, acetic acid (<NUM>) was added. Organic phase was separated and washed with water (<NUM> x <NUM>), aqueous <NUM>% sodium carbonate solution (<NUM> x <NUM>) and water (<NUM> x <NUM>). The crude product was distilled in vacuo to afford <NUM>,<NUM>,<NUM>-trimethylhexan-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

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

Methanesulfonic acid (<NUM>, <NUM> mol) was added to a mixture of <NUM>,<NUM>-dimethyl-<NUM>-butene (<NUM>, <NUM> mol) and acetic anhydride (<NUM>, <NUM> mol) at <NUM> under nitrogen while stirring. The mixture was stirred in an ice bath and left to reach <NUM> within <NUM>. Subsequently, water (<NUM>) was added and the mixture was extracted with methyl tert-butyl ether (<NUM> x <NUM>). The combined organic phases were washed successively with water (<NUM> x <NUM>), aqueous saturated sodium carbonate solution till pH <NUM> and brine (<NUM>). The organic phase was dried over Na<NUM>SO<NUM> and volatiles were removed under reduced pressure. The residue (<NUM>) was distilled in vacuo to afford <NUM>,<NUM>,<NUM>-trimethylpent-<NUM>-en-<NUM>-one (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>).

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

Sodium borohydride (<NUM>, <NUM> mol) was added to a mixture of <NUM>,<NUM>,<NUM>-trimethylpentan-<NUM>-one (<NUM>, <NUM> mol) in ethanol (<NUM>) and water (<NUM>) at <NUM>-<NUM> for <NUM> while stirring. Then the mixture was stirred for <NUM> at <NUM>. Subsequently, saturated aqueous ammonium chloride solution was added and the mixture was extracted with ethyl acetate (<NUM> x <NUM>). Mixed extracts were washed with water (<NUM> x <NUM>), aqueous <NUM>% sodium carbonate solution (<NUM> x <NUM>) and water (<NUM> x <NUM>). The volatiles were removed under reduced pressure and the residue (<NUM>) was distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>,<NUM>,<NUM>-trimethylpent-<NUM>-en-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

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

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

Raney Ni (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethylpent-<NUM>-en-<NUM>-one (<NUM>, <NUM> mol) in methanol (<NUM>) and the reactor was flushed with nitrogen. Then the mixture was stirred under hydrogen atmosphere at <NUM>/<NUM> bar for <NUM>. Subsequently, the mixture was cooled to <NUM> and filtered through pad of celite. The filter cake was washed with methanol (<NUM>). Combined filtrates were dried over sodium sulphate (<NUM>) and the volatiles removed under reduced pressure to afford <NUM>,<NUM>,<NUM>-trimethylpentan-<NUM>-one (<NUM>, <NUM>%).

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

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

Sodium borohydride (<NUM>, <NUM> mmol) was added to a mixture of <NUM>,<NUM>,<NUM>-trimethylpentan-<NUM>-one (<NUM>, <NUM> mol), methanol (<NUM>) and water (<NUM>) at <NUM>-<NUM> over a period of <NUM> while stirring. Then the mixture was stirred at <NUM> for <NUM>. Subsequently, sodium borohydride (<NUM>, <NUM> mmol) was added over a period of <NUM> at <NUM> and the mixture stirred for another <NUM>. Then, aqueous <NUM>% hydrochloric acid solution was added at <NUM>-<NUM> till pH <NUM>. Subsequently, volatiles were removed under reduced pressure, at <NUM> and water (<NUM>) was added. The mixture was extracted with dichloromethane (<NUM> x <NUM>). Combined organic phases were washed with brine (<NUM> x <NUM>) and dried over sodium sulphate (<NUM>). Volatiles were removed under reduced pressure at <NUM> to afford <NUM>,<NUM>,<NUM>-trimethylpentan-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

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

Methane sulfonic acid (<NUM>, <NUM> mmol) was added to a mixture of valeric anhydride (<NUM>, <NUM> mol) and <NUM>,<NUM>-dimethylbut-<NUM>-ene (<NUM>, <NUM> mol) over a period of <NUM> while stirring. Then, the mixture was stirred for <NUM> at <NUM>. Subsequently, aqueous <NUM>% potassium carbonate solution (<NUM>) was added at <NUM> and the mixture stirred for <NUM>. Organic phase was separated and washed with water (<NUM> x <NUM>) till pH <NUM>. Crude product (<NUM>) was distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>, <NUM>, <NUM>-trimethyloct-<NUM>-en-<NUM>-one (<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> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>).

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

Sodium borohydride (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethyloct-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in ethanol (<NUM>) and THF (<NUM>) at <NUM> was added over a period of <NUM> while stirring. Then the mixture was stirred for <NUM> at <NUM>. Subsequently, aqueous <NUM>% hydrogen chloride solution (<NUM>) was added at <NUM>. Organic phase was separated and the aqueous phase was extracted with ethyl acetate (<NUM> x <NUM>). Combined organic phases were washed with water (<NUM> x <NUM>) and the volatiles removed under reduced pressure. Crude product (<NUM>) was distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>,<NUM>,<NUM>-trimethyloct-<NUM>-en-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

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

Raney Ni (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethyloct-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in isopropanol (<NUM>) and the autoclave was flushed with nitrogen. Then the mixture was stirred under hydrogen atmosphere at <NUM>/<NUM> bar for <NUM>. The mixture was cooled to <NUM>, filtered through a pad of celite and the filter cake was washed with isopropanol (<NUM>). The filtrate was dried over sodium sulphate (<NUM>) and volatiles removed under reduced pressure to afford <NUM>,<NUM>,<NUM>-trimethyloctan-<NUM>-one (<NUM>, <NUM>%) as a colorless liquid.

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

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

Sodium borohydride (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethyloctan-<NUM>-one (<NUM>, <NUM> mmol) in ethanol (<NUM>) at <NUM> over a period of <NUM> while stirring. Then the mixture was stirred for <NUM> at <NUM>. Subsequently, ethyl acetate (<NUM>) was added at <NUM> followed by aqueous <NUM> N hydrogen chloride solution (<NUM>). Organic phase was separated, washed with water (<NUM> x <NUM>) and volatiles removed under reduced pressure to afford <NUM>,<NUM>,<NUM>-trimethyloctan-<NUM>-ol (<NUM>, <NUM>%).

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

Methane sulfonic acid (<NUM>, <NUM> mmol) was added to a mixture of caproic anhydride (<NUM>, <NUM> mmol) and <NUM>,<NUM>-dimethylbut-<NUM>-ene (<NUM>, <NUM> mmol) over a period of <NUM> while stirring. Then the mixture was stirred for <NUM> at <NUM>. Subsequently, aqueous <NUM>% sodium carbonate solution (<NUM>) was added at <NUM> and the mixture was stirred for <NUM>. Organic phase was separated and the aqueous phase extracted with ethyl acetate (<NUM> x <NUM>). Combined organic phases were washed with water (<NUM> x <NUM>) till pH <NUM> and volatiles removed under reduced pressure. Crude product was distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>,<NUM>,<NUM>-trimethylnon-<NUM>-en-<NUM>-one (<NUM>, <NUM>%).

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

Sodium borohydride (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethylnon-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in ethanol (<NUM>) at <NUM> over a period of <NUM> while stirring. Then the mixture was stirred for <NUM> at <NUM>. Subsequently, ethyl acetate (<NUM>) was added at <NUM> followed by aqueous <NUM> N hydrogen chloride solution (<NUM>). Separated organic phase was washed with water (<NUM> x <NUM>) and the volatiles removed under reduced pressure to afford <NUM>,<NUM>,<NUM>-trimethylnon-<NUM>-en-<NUM>-ol (<NUM>, <NUM> %) as a colorless liquid.

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

Raney Ni (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethylnon-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in isopropanol (<NUM>) and the autoclave was flushed with nitrogen. Then the mixture was stirred under hydrogen atmosphere at <NUM>/<NUM> bar for <NUM>. The mixture was cooled to <NUM> and filtered through a pad of celite. The filter cake was washed with isopropanol (<NUM>). The combined filtrates were dried over sodium sulphate (<NUM>) and volatiles removed under reduced pressure to afford <NUM>,<NUM>,<NUM>-trimethyloctan-<NUM>-one (<NUM>, <NUM>%) as a colorless liquid.

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

Sodium borohydride (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethylnonan-<NUM>-one (<NUM>, <NUM> mmol) in ethanol (<NUM>) at <NUM> over a period of <NUM> while stirring. Then the mixture was stirred for <NUM> at <NUM>. Subsequently, ethyl acetate (<NUM>) was added at <NUM> followed by aqueous <NUM> N solution of hydrogen chloride (<NUM>). Separated organic phase was washed with water (<NUM> x <NUM>) and volatiles removed under reduced pressure. Crude product was distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>,<NUM>,<NUM>-trimethylnonan-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

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

Potassium <NUM>-methylpropan-<NUM>-olate (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethylhex-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in tetrahydrofuran (<NUM>) at <NUM> over a period of <NUM> under nitrogen atmosphere. Then the mixture was stirred at <NUM>-<NUM> for <NUM>. Subsequently, iodomethane (<NUM>, <NUM> mmol) was added dropwise and then the mixture was stirred at <NUM> for <NUM>. Saturated aqueous solution of ammonium chloride was added and the mixture was extracted with ethyl acetate (<NUM> x <NUM>). Combined organic phases were dried over anhydrous Na<NUM>SO<NUM> and volatiles removed under reduced pressure. Crude product (<NUM>) was purified by fractional distillation using ss-random packed column (<NUM>) to afford <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhex-<NUM>-en-<NUM>-one (<NUM>, <NUM>%) as a colorless liquid.

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

Sodium borohydride (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhex-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in methanol (<NUM>) at <NUM> over a period of <NUM>. Then the mixture was stirred at <NUM> for <NUM> and at <NUM> for <NUM>. Subsequently, aqueous <NUM> % hydrogen chloride solution was added at <NUM> till pH <NUM>. The mixture was extracted with ethyl acetate (<NUM> x <NUM>). The organic phases were combined and volatiles removed under reduced pressure (<NUM>/<NUM> mbar). Crude product (<NUM>) was purified by silicagel chromatography using n-hexane/ethyl acetate (<NUM>/<NUM>) as eluent to afford <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhex-<NUM>-en-<NUM>-ol (<NUM>, <NUM> %) as a colorless mixture.

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

<NUM>,<NUM>-Dimethyl-<NUM>-butene (<NUM>, <NUM> mol) was added to a solution of zinc chloride (<NUM>, <NUM> mol) in butyric anhydride (<NUM>, <NUM> mol) at <NUM> under nitrogen atmosphere while stirring. Then the mixture was warmed to <NUM> within <NUM> and then stirred at <NUM> for <NUM>. Subsequently, water was added (<NUM>). Separated organic phase was washed with water (<NUM> x <NUM>), aqueous saturated sodium carbonate solution till pH <NUM> and brine (<NUM>). The crude product (<NUM>) was purified by distillation in vacuo (<NUM>-<NUM>/ <NUM> mbar) to afford <NUM>,<NUM>,<NUM>-trimethylhept-<NUM>-en-<NUM>-one (<NUM>, <NUM>%) as a colorless liquid.

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

Sodium borohydride (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethylhept-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in methanol (<NUM>) for <NUM>. Then, the mixture was stirred at <NUM> for <NUM>. Subsequently, aqueous <NUM> % solution of hydrogen chloride was added till pH <NUM>. The mixture was extracted with ethyl acetate (<NUM> x <NUM>) and the combined extracts were washed with water (<NUM>). Volatiles were removed under reduced pressure to afford <NUM>,<NUM>,<NUM>-trimethylhept-<NUM>-en-<NUM>-ol (<NUM>, <NUM>%) as a colorless liquid.

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

Zinc chloride (<NUM>, <NUM> mol) was added portion-wise to a solution of crotonic anhydride (<NUM>, <NUM> mol) in methylcyclohexane (<NUM>) at -<NUM> and the mixture was stirred for <NUM>. Then <NUM>,<NUM>-dimethylbut-<NUM>-ene (<NUM>, <NUM> mol) was added over a period of <NUM> at -<NUM>. The mixture was stirred for <NUM> at <NUM>. Subsequently, water (<NUM>) was added. Separated organic phase was washed with aqueous <NUM> % solution of sodium hydroxide (<NUM>), water (<NUM>) and brine (<NUM>) and volatiles were removed under reduced pressured. Crude product was purified by distillation in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford (E)-<NUM>,<NUM>,<NUM>-trimethylhepta-<NUM>,<NUM>-dien-<NUM>-one (<NUM>, <NUM>%) as a colorless liquid.

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

<NUM>C NMR (<NUM>, CDCl<NUM>): δ17. <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

Cerium(III) chloride heptahydrate (<NUM>, <NUM> mmol) was added to a solution of (E)-<NUM>,<NUM>,<NUM>-trimethylhepta-<NUM>,<NUM>-dien-<NUM>-one (<NUM>, <NUM> mmol) in methanol (<NUM>) at <NUM>. The mixture was stirred at <NUM> for <NUM>. Subsequently, sodium borohydride (<NUM>, <NUM> mmol) was added at <NUM> and the mixture was stirred for at <NUM> for <NUM>. Water (<NUM>) was added and the mixture extracted with dichloromethane (<NUM> x <NUM>). Combined organic extracts were dried over sodium sulphate and volatiles removed under reduced pressure. Crude product (<NUM>) was purified by silica gel column chromatography using n-hexane/ethyl acetate mixture (<NUM>/<NUM>) as eluent to afford (E)-<NUM>,<NUM>,<NUM>-trimethylhepta-<NUM>,<NUM>-dien-<NUM>-ol (<NUM>, <NUM> %) as colorless liquid.

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

Potassium <NUM>-methylpropan-<NUM>-olate (<NUM>, <NUM> mmol) was added to a solution of <NUM>,<NUM>,<NUM>-trimethylhex-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in tetrahydrofuran (<NUM>) under nitrogen atmosphere at <NUM> over a period of <NUM>. Then, iodoethane (<NUM>, <NUM> mmol) was added dropwise and the mixture was allowed to warm up to <NUM> and stirred for <NUM>. Subsequently, aqueous saturated ammonium chloride solution (<NUM>) was added and the mixture extracted with methyl tert-butyl ether (<NUM> x <NUM>). Combined organic extracts were dried over anhydrous sodium sulphate and volatiles removed under reduced pressure to afford <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhept-<NUM>-en-<NUM>-one (<NUM>, <NUM>%) as a colorless liquid.

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

Sodium borohydride (<NUM>, <NUM> mmol) was added slowly to a solution of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhept-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in methanol (<NUM>) was at <NUM> and the mixture was stirred at <NUM> for <NUM>. Subsequently, aqueous <NUM> N solution of hydrogen chloride (<NUM>) was added till pH <NUM> and the mixture was extracted with ethyl acetate (<NUM> x <NUM>). Combined organic phases were washed with water (<NUM> x <NUM>) and volatiles removed under reduced pressure to afford <NUM>,<NUM>,<NUM>,<NUM>-tetramethylhept-<NUM>-en-<NUM>-ol (<NUM>, <NUM> %) as a colorless liquid (mixture of diastereomers).

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <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>-Dimethyl-<NUM>-butene (<NUM>, <NUM>, <NUM> mol) was added to a solution of trifluoromethanesulfonic acid (<NUM>, <NUM>, <NUM> mmol) in crotonic anhydride (<NUM>, <NUM>, <NUM> mol) at -<NUM> under nitrogen atmosphere. Then the mixture was stirred at <NUM> for <NUM>, and at <NUM> for <NUM>. Subsequently, aqueous <NUM>M sodium hydroxide solution (<NUM>, <NUM> mol) was added, the mixture was stirred at <NUM> for <NUM> hours under nitrogen atmosphere and cooled to <NUM>. Then organic fraction was separated and the aqueous fraction was extracted with methyl tert-butyl ether (<NUM>). The combined organic fractions were washed with brine, and dried over sodium sulphate. The volatiles were removed under reduced pressure and the residue distilled in vacuo (<NUM>-<NUM>/<NUM> mbar) to afford <NUM>,<NUM>,<NUM>,<NUM>-trimethylhepta-<NUM>,<NUM>-dien-<NUM>-one (<NUM>, <NUM>% yield).

The olfactory properties of a selection of the above compounds are given below:.

In the following invention example (A) and comparative examples (B/C/D), the compound of Example <NUM>, and commercial compounds were included in a citrus accord fragrance for use in shampoo (E = blank). DPG = dipropylene glycol.

Comparative studies of different compounds where column E is the blank:
The introduction of <NUM>% by weight of <NUM>,<NUM>,<NUM>-trimethylhex-<NUM>-en-<NUM>-ol enhances the citrus effect giving the fragrance a more sparkling and more natural and fresher character (A).

Compared to this material the following effects are observed with reference materials:
The introduction of <NUM> % by weight of borneol provides this citrus accord with a more piney, albeit noticeably synthetic effect (B).

The introduction of <NUM>% by weight of isobornyl acetate gives no noticeable effect to this citrus accord (C).

Claim 1:
Alcohol useful in a fragrance, flavor and/or deodorizing/masking composition wherein the alcohol is selected from compounds of formula (<NUM>) or of formula (<NUM>)
<CHM>
wherein
- for the compounds of formula (<NUM>), R is ethyl, n-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, <NUM>-methylprop-<NUM>-en-<NUM>-yl, <NUM>-pentyl, <NUM>-pentyl, n-hexyl, <NUM>-hexyl, <NUM>-hexyl, vinyl, <NUM>-propenyl, prop-<NUM>-en-<NUM>-yl, allyl, <NUM>-butenyl, <NUM>-butenyl, but-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, or hex-<NUM>-en-<NUM>-yl, and
- for the compounds of formula (<NUM>), R is ethyl, n-propyl, n-butyl, s-butyl, t-butyl, i-butyl, n-pentyl, <NUM>-pentyl, <NUM>-pentyl, n-hexyl, <NUM>-hexyl, <NUM>-hexyl, <NUM>-propenyl, prop-<NUM>-en-<NUM>-yl, allyl, <NUM>-butenyl, <NUM>-butenyl, but-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-pentenyl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, pent-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, <NUM>-hexenyl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, hex-<NUM>-en-<NUM>-yl, or hex-<NUM>-en-<NUM>-yl.