Patent Description:
More particularly, the present invention relates to <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>H-chromen-<NUM>-one derivatives (formula A) and/or <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>-tetrahydrobenzofuran-<NUM>(<NUM>H)-one derivatives (formula B) (odorants) which are useful as fragrance or flavor materials, in particular, in providing damascone-type, fruity, minty, woody, powdery, ambery and/or tobacco-like notes to perfume, aroma and/or deodorizing/masking compositions.

Increasing limitations on the supply of natural fragrance ingredients have revolutionized the field of synthetic fragrance ingredients. Nowadays, there is an increasing demand for novel odorants/compounds and/or novel fragrance, flavor and/or deodorizing/masking compositions comprising said odorants/compounds.

Various isomeric damascenes are used when fruity and floral notes are required. Typical damascones used include alpha-damascone, beta-damascone and delta-damascone. In addition to the above ingredients, beta-damascenone is also used for its fruity profile. However, all above ingredients are found to be skin sensitizers and therefore IFRA guidelines recommend considerable restrictions on their use in consumer products. Therefore, there has been a constant demand for safe alternatives to damascones.

Damascone-type notes include alpha damascone-type notes (known as fruity, green, seedy, tropical, spicy, apple, woody), beta damascone type notes (known as fruity, floral, currant, black currant, plum, rose, honey, tobacco) and delta damascone-type notes (known as fruity, sweet, rose, natural, petal, currant, bud black currant, bud tobacco). Damascenone-type notes include beta-damascenone-type notes (known as natural sweet, fruity, rose, plum, grape, raspberry, sugar).

An examination of structures of various damascone isomers reveals presence of an alpha-beta unsaturated ketone motif. It is known that alpha-beta unsaturated carbonyl compounds are good Michael acceptors and hence many electrophilic alpha-beta unsaturated carbonyl compounds act as skin sensitizers by reacting with nucloephilic proteins on skin. It is also reported that electron donating substituents such as alkyl groups on alpha C-atom and to a lesser extent on beta C-atom, deactivate the Cβ=Cα bond towards nucleophilic attack.

The article from<NPL>" provides corresponding comparative results of said reduction.

<CIT>) relates to the preparation of bicyclic enol-ethers (X) (where n is from <NUM> to <NUM>, and R<NUM>, R<NUM> and R<NUM> may be H or C<NUM>-C<NUM>-alkyl) by a <NUM>-step sequence involving free radical adduct formation reaction of an allyl ether of general formula (V) (where R<NUM> is tert. -butyl, tetrahydrofuran-<NUM>-yl or tetrahydropyran-<NUM>-yl) with a cyclic ketone (W) to afford a compound of general formula (Y) followed by acid-catalyzed cyclization; said compounds (X) and (Y) being intermediates for the synthesis of musk-like fragrances.

<CIT>) relates to 4a,<NUM>,<NUM>,<NUM>,<NUM>,8a-Hexahydro-<NUM>,<NUM>-dimethyl-<NUM>-<NUM>-benzopyran (formula given below) which is useful as a odoriferous perfume compound, and a method for preparing the same.

<CIT>) relates to compounds of the formula (Z) with R = -H, -methyl, ethyl, O-methyl or O-ethyl, R<NUM> = -H, -methyl, ethyl, O-methyl or O-ethyl and n = <NUM> or <NUM>, their use as fragrances, preferred mixtures, consumer goods containing these compounds and their production.

<CIT>) claims substituted hexahydro-(<NUM>)- <NUM>-benzopyran-<NUM>-one (or hexahydro-(<NUM>)-chromen-<NUM>-one) derivatives and substituted tetrahydro-(<NUM>)-l-benzopyran-<NUM>-one (or tetrahydro-(<NUM>)-chromen-<NUM>-one) derivatives, methods for synthesizing said compounds and perfumery compositions comprising an olfactory acceptable amount of the said compounds.

It was surprisingly found that certain compounds represented by formula A viz <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>H-chromen-<NUM>-one derivatives and formula B viz <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>-tetrahydrobenzofuran-<NUM>(<NUM>H)-one derivatives impart exotic fruity, damascone-like or damascenone-type profile. These compounds do not have any alpha-beta unsaturated ketone group in their structures. These compounds still have the geminal dimethyl group which is a common feature in all damascone isomers. Additionally, in these compounds, the ketone group is present as part of a six membered ring which is fused to a six membered ring (formula A) or a five-membered ring (formula B) containing geminal dimethyl group. The six membered ring (formula A) or five membered ring (formula B) containing the geminal dimethyl group also contains an oxygen atom. Interestingly, many of these compounds of formula A and B also advantageously impart minty, woody, powdery, ambery and/or tobacco-like notes to perfume, aroma and/or deodorizing/masking compositions.

This invention discloses novel fragrance, flavor and/or deodorizing/masking compositions comprising compounds of formula (I) with n being <NUM> or <NUM>
<CHM>
wherein R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM> are independently selected from a group consisting of hydrogen, C1 to C5 alkyl (for example methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, isobutyl, n-pentyl, cyclopropylmethyl, cyclobutylmethyl, cyclobutyl or cyclopentyl) or C1 to C5 alkenyl (for example an allyl group, <NUM>-methylbut-<NUM>-en-<NUM>-yl, <NUM>-methylbut-<NUM>-en-<NUM>-yl, but-<NUM>-en-<NUM>-yl or <NUM>-methylallyl), with the proviso that.

For the avoidance of doubt, following pairs of radicals viz, R<NUM> and R<NUM>, R<NUM> and R<NUM>, R<NUM> and R<NUM> , R<NUM> and R<NUM> , R<NUM> and R<NUM> are separated radicals, i.e. they do not form together a ring. The exclusion of the four above compounds is justified by the findings that they did not impart the olfactive properties according to the objectives of the present invention.

In an embodiment, the present invention relates to novel fragrance, flavor and/or deodorizing/masking compositions comprising compounds of formula (I) with n being <NUM> or <NUM>
<CHM>
wherein R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM> are independently selected from a group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl or t-butyl groups, with the proviso that.

General formula (I) has been used to denote compounds represented by formula A viz <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>H-chromen-<NUM>-one derivatives and/or formula B viz <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>-tetrahydrobenzofuran-<NUM>(<NUM>H)-one derivatives, wherein R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM> are independently selected from a group as defined hereinabove.

Compounds of formula B do not contain R<NUM> and R<NUM> groups since n = <NUM> in general formula (I).

In an embodiment, the present invention relates to compounds of formula A or of formula B
<IMG>.

wherein R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM> are independently selected from a group consisting of hydrogen, C1 to C5 alkyl (for example methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, isobutyl, n-pentyl, cyclopropylmethyl, cyclobutylmethyl, cyclobutyl or cyclopentyl) or C1 to C5 alkenyl (for example an allyl group, <NUM>-methylbut-<NUM>-en-<NUM>-yl, <NUM>-methylbut-<NUM>-en-<NUM>-yl, but-<NUM>-en-<NUM>-yl or <NUM>-methylallyl), with the proviso that.

wherein R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM> are independently selected from a group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl or t-butyl groups, with the proviso that.

In another embodiment, the present invention relates to fragrance, flavor and/or deodorizing/masking compositions comprising compounds of formula A or of formula B
<IMG>.

In another embodiment of this invention, compounds of general formula (I) may contain one or more chiral centres and can be chiral, e.g. they can be used as stereoisomeric (enantiomeric or diastereomeric) mixtures. In another embodiment, compounds of the formula (I) can also be advantageously used in pure enantiomeric or diastereomeric form.

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 A or B 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 of formula A or B 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 A or B 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 according to formula A or B 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 A or B as described hereinabove may be employed in a consumer product base simply by directly mixing at least one compound of formula (A) and/or at least one compound of formula (B) or a fragrance composition comprising said compound or compounds of formula (A) and/or (B) 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 one or more compounds of formula (A) and/or (B), as a fragrance, flavor and/or deodorizing/masking 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 one or more compounds of formula (A) and/or (B), 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 (A) and/or (B), 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 discloses novel fragrance, flavor and/or deodorizing/masking compositions comprising substituted <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>H-chromen-<NUM>-one derivatives (formula A) and/or <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>-tetrahydrobenzofuran-<NUM>(<NUM>H)-one derivatives (formula B). as defined hereinabove.

In a particular embodiment according to the present invention, the compounds of formulae (A) and/or (B) as defined hereinabove are claimed; said compounds being useful in the perfume, aroma and/or deodorizing/masking compositions of the present invention.

In an embodiment, a compound of formula (A) useful in a fragrance, flavor and/or decolorizing/masking composition is selected from the following compounds:.

In an embodiment, a compound of formula (B) useful in a fragrance, flavor and/or decolorizing/masking composition is selected from the following compounds:.

In an embodiment according to the present invention, the fragrance, flavor and/or deodorizing/masking composition comprises a compound of formula (A) or of formula (B) which is selected from any of the compounds and/or from a mixture of two or more of the said compounds given above.

The applicants have surprisingly discovered that from an olfactory perspective, the compounds of formula (A) have damascone-type or damascenone-type odor profile. In fact, many compounds of formula (A) display exotic fruity and minty notes. Many compounds of formula (A) and (B) also exhibit woody, powdery, ambery and/or tobacco-like notes. In fact, some compounds of formula (A) also display sandalwood profile. The compounds (A) and (B) are very retentive on a blotter; for more than <NUM> days. Indeed, compounds of formula (A) and (B) perform extremely well in woody, fougere and rose accords.

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 (A) or of formula (B) 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 (A) or of formula (B) 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:.

The compounds of formula (A) or of formula (B) 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 compound(s) of formula (A) or of formula (B), 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 (A) or of formula (B) 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%.

As reported in <NPL>, compound of formula (A), for example, <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one was synthesized by LiAlH<NUM>-mediated or NaBH<NUM>-mediated reduction of <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>,<NUM>,<NUM>-tetrahydro-<NUM>-chromene-<NUM>,<NUM>(<NUM>)-dione, which in turn was synthesized by dimedone and either alkylidene-substituted Meldrum's acid or substituted acryloyl chlorides.

We envisaged a different approach wherein we synthesized compounds of formula (A) or (B) either in one step (Method P) or in two steps (methods Q or R). However, we needed a method that will selectively furnish <NUM>-substituted-<NUM>,<NUM>,-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one derivatives. Since method Q did not furnish the desired <NUM>-substituted derivative selectively, in that it also gave an inseparable <NUM>-substituted derivative; we also invented a new synthetic approach (Method S) that gave only <NUM>-substituted-<NUM>,<NUM>,-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one derivatives.

In a preferred embodiment according to the present invention, the compounds represented by the general formula (A) and/or (B) can be advantageously synthesized in one step from corresponding cyclohexanediones formula (I) and an alcohol of formula (II) in the presence of an acid, for example in presence of p-toluenesulfonic acid acid (<NUM> equivalents), using toluene as solvent, at a temperature of <NUM>-<NUM>.

In another preferred embodiment according to the present invention, the compounds of formula (A) can be advantageously prepared in two steps from cyclohexanediones (I) and a homoallylic alcohol of formula (III). The first step in this scheme is the reaction of cyclohexanedione (<NUM>) with alcohol (III) in presence of iodine/toluene/THF to afford vinylogous ester (IV). In the second step, compound (IV) is subjected to AlCl<NUM>-mediated cyclization in ethylene dichloride (EDC) to afford product (A) and/or (B).

In another preferred embodiment according to the present invention, the compounds of formula (A) and/or (B) can be advantageously prepared in two steps from cyclohexanediones (I) and an allylic alcohol of formula (II). The first step in this scheme is the reaction of cyclohexanedione (I) with alcohol (II) in presence of iodine/toluene/THF to afford vinylogous ester (V). In the second step, compound (V) is subjected to AlCl<NUM>-mediated cyclization in ethylene dichloride (EDC) to afford products (A) and/or (B).

In another preferred embodiment according to the present invention, if <NUM>-alkylcyclohexan-<NUM>,<NUM>-diones (XI) and isoprenol were treated with iodine/toluene/THF as per method Q, then two isomers (XII) and (XIII) were obtained. This isomeric mixture was subjected to AlCl<NUM>-mediated cyclization to afford products (A<NUM>) and (A<NUM>). The two isomers can be separated by column chromatography but often are not separable by fractional distillation as they have very close boiling points.

Hence, a method that will selectively afford A<NUM> was also desirable.

Ethyl acetotacetate was alkylated using base and alkyl iodidie (R<NUM>-I). The resulting alkyl derivative (XIV) on treatment with methyl acrylate in presence of potassium tertiary butoxide in THF at <NUM> yielded <NUM>,<NUM>,- ethoxycarbonyl-alkyl-substituted cyclohexan-<NUM>,<NUM>-dione (XV), Surprisingly, we found that compound (XV) reacted with isoprenol in presence of iodine/Toluene/THF to afford only one regioisomer (XVI). LiCl-mediated decarboxylation in DMSO at <NUM> afforded vinylogous ester (XII) selectively and subsequent AlCl<NUM>-mediated cyclization of (XII) afforded only A<NUM>.

To a mixture of cyclohexane-<NUM>,<NUM>-dione (<NUM>, <NUM> mmol, <NUM> equiv) in toluene (<NUM>) were added <NUM>-methylbut-<NUM>-en-<NUM>-ol (<NUM>, <NUM> mmol, <NUM> equiv) and iodine (<NUM>, <NUM> mmol, <NUM> eqiv). After stirring the reaction mixture for <NUM>, the reaction was quenched with <NUM> of <NUM>% sodium thiosulfate solution. Then toluene layer was separated and the aqueous layer was extracted with ethylacetate (<NUM> x <NUM>). The combined organic layer was washed with water ( <NUM>× <NUM>) and dried over anhydrous sodium sulfate. The organic solvent was evaporated on a rotary evaporator to afford <NUM> gm of crude mass which on flash chromatography afforded <NUM> of <NUM>-((<NUM>-methylbut-<NUM>-en-<NUM>-yl)oxy)cyclohex-<NUM>-en-<NUM>-one (<NUM>%). <NUM>H-NMR (<NUM>, CDCl<NUM>): δ <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>).

Method Q: To a stirred solution of AlCl<NUM> (<NUM>, <NUM> mol, <NUM> equiv ) in <NUM>,<NUM>-dichloroethane (<NUM>) was added a solution of <NUM>-((<NUM>-methylbut-<NUM>-en-<NUM>-yl)oxy)cyclohex-<NUM>-en-<NUM>-one (<NUM>, <NUM> mol, <NUM> equiv ) in EDC (<NUM> ) dropwise at <NUM>. The reaction mixture was warmed to <NUM> and stirred for <NUM>. The reaction was mixture was slowly poured into ice water under vigorous stirring. The aqueous layer was separated and extracted with DCM (<NUM>). The combined organic layer was washed with water (<NUM> × <NUM>) and then stirred with aqueous sodium bicarbonate solution (<NUM>) for one hour. This was repeated twice. The organic layer was separated and dried over sodium sulfate and concentrated on a rotary evaporator to afford <NUM> of crude product. The crude was purified by fractional distillation (<NUM>-<NUM>/<NUM>) to afford <NUM> of pure <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one (<NUM>%).

<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>C-NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. Odor profile: tobacco, leathery, fruity, woody.

To a solution of ethyl <NUM>-methyl-<NUM>-oxobutanoate (<NUM>, <NUM> mmol, <NUM> equiv) in tetrahydrofuran (<NUM>) was added potassium tert-butoxide (<NUM>, <NUM> mmol, <NUM> equiv) at room temperature. The reaction mixture was cooled to <NUM> followed by addition of methyl acrylate (<NUM>, <NUM> mmol, <NUM> equiv). After stirring the reaction mixture for <NUM>, <NUM> HCl was added to adjust the pH to <NUM>-<NUM> and the mixture was extracted with EtOAc (<NUM> × <NUM>). The organic layer was washed with water, brine and then concentrated to give crude material which was purified by column chromatography using <NUM>-<NUM>% EtOAc in hexanes to give ethyl <NUM>-methyl-<NUM>,<NUM>-dioxocyclohexane-<NUM>-carboxylate (<NUM>, <NUM>%).

To a solution of ethyl <NUM>-methyl-<NUM>,<NUM>-dioxocyclohexane-<NUM>-carboxylate (<NUM>, <NUM> mmol) in toluene (<NUM>) at <NUM> were added <NUM>-methylbut-<NUM>-en-<NUM>-ol (<NUM>, <NUM> mmol) and <NUM>-methylbenzenesulfonic acid (<NUM>, <NUM> mmol). After stirring the reaction mixture <NUM> for <NUM>, it was quenched with saturated solution of NaHCO<NUM>. The mixture was extracted with EtOAc (<NUM> x <NUM>) and the combined organic layer was washed with brine, dried with anhydrous Na<NUM>SO<NUM> and filtered. The organic layer concentrated to afford crude ethyl <NUM>-methyl-<NUM>-((<NUM>-methylbut-<NUM>-en-<NUM>-yl)oxy)-<NUM>-oxocyclohex-<NUM>-ene-<NUM>-carboxylate (<NUM>) which was used as such in the next reaction.

To a stirred solution of crude ethyl <NUM>-methyl-<NUM>-((<NUM>-methylbut-<NUM>-en-<NUM>-yl)oxy)-<NUM>-oxocyclohex-<NUM>-ene-<NUM>-carboxylate (<NUM>, <NUM> mmol) in DMSO (<NUM>) and water (<NUM>) was added lithium chloride (<NUM>, <NUM> mmol). The reaction mixture was stirred at <NUM> for <NUM>. The reaction mixture was diluted with water and then extracted with EtOAc (<NUM> x <NUM>). The combined organic layer was washed with brine, fitered and concentrated to get crude residue that was purified with column chromatography to afford <NUM>-methyl-<NUM>-((<NUM>-methylbut-<NUM>-en-<NUM>-yl)oxy)cyclohex-<NUM>-en-<NUM>-one (<NUM>, <NUM>%).

To a stirred solution of <NUM>-methyl-<NUM>-((<NUM>-methylbut-<NUM>-en-<NUM>-yl)oxy)cyclohex-<NUM>-en-<NUM>-one (<NUM>, <NUM> mmol) in <NUM>,<NUM>-dichloroethane (<NUM>) was added aluminum trichloride (<NUM>, <NUM> mmol) at <NUM>. The reaction was stirred at <NUM> for <NUM>. The reaction mixture was added to ice-water slowly and the mixture was stirred for <NUM>, followed by its extraction with methylene dichloride (<NUM> × <NUM>). The comboined organic layer was washed with brine, dried over anhydrous Na<NUM>SO<NUM> and filtered. The organic layer was concentrated and the resulting crude compound was purified by column chromatography using <NUM>% EtOAc in hexane to give <NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one (<NUM>, <NUM>%).

<NUM>H-NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (overlapping m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>). <NUM>C-NMR (<NUM>, CDCl<NUM>): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>
Odor profile: exotic fruity, delta-damascone type, woody.

Synthesized from ethyl <NUM>-ethyl-<NUM>-oxobutanoate in <NUM> steps as per method S.

<NUM>H-NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (overlapping m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (t, J = <NUM>, <NUM>). Odor profile: fruity, plum, woody, beta-damascone like.

Synthesized in <NUM> steps from cyclohexane-<NUM>,<NUM>-dione and <NUM>,<NUM>,<NUM>-trimethylpent-<NUM>-en-<NUM>-ol as per method Q.

<NUM>H-NMR (<NUM>, CDCl<NUM>): δ <NUM> (q, J = <NUM>, <NUM>), <NUM>-<NUM> (overlapping m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <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>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. Odor profile: Fruity, woody, Cashmeran-type (Cashmeran includes floral fruity notes).

Synthesized in <NUM> steps from cyclohexane-<NUM>,<NUM>-dione and <NUM>-methyl-<NUM>-methylenebutan-<NUM>-ol as per method Q. Odor profile: Strong minty, woody, animalic in background.

Synthesized from <NUM>,<NUM>-dimethylcyclohexane-<NUM>,<NUM>-dione and <NUM>-methylbut-<NUM>-en-<NUM>-ol as per method Q. Odor profile: minty, dry, woody.

Synthesized in one step from <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one and (bromomethyl)cyclopropane.

Synthesized in one step from <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one and <NUM>-bromo-<NUM>-methylpropane, yield = <NUM> %.

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

In the following invention, example (A) containing the compound from Example <NUM> (<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one) and a comparative example B containing commercial compound ethyl safranate illustrate composition evaluation study in a woody accord fragrance for use in shampoo ( C = blank), IPM = Isopropyl myristate.

Introduction of <NUM>% weight by weight of <NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexahydro-<NUM>-chromen-<NUM>-one as <NUM>% w/w solution in IPM gives nice rounded, powerful woody effect. On the other hand, when ethyl safranate <NUM>% weight by weight in IPM is used in the above accord, only an average rosy effect is observed.

Claim 1:
Compounds of formula A or of formula B
<IMG>
wherein R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM>, R<NUM> , R<NUM> are independently selected from a group consisting of hydrogen, C1 to C5 alkyl or C1 to C5 alkenyl, with the proviso that
- compounds of formula A don't include compound of formula A-exc, and
<CHM>
- compounds of formula B don't include compounds of formulae B-exc1, B-exc2 and B-exc3
<CHM>