Patent Description:
Although many perfumes are already available, in the perfume industry there is still a general demand for new perfumes especially for perfumes with musk fragrance notes, which are able (in perfume compositions) to produce, in addition to a musk fragrance note, other interesting odor notes and/or odor impressions and, with their novel or original fragrance properties, to expand the possibilities of the perfumer. In particular there is interest in perfumes with musk fragrance notes that are able to form a harmonious combination with perfumes with a flowery fragrance. Preferably there should be an overlapping of the different olfactory aspects and notes, so as to produce a complex overall odor impression.

The area of perfume chemistry can be considered to be well-researched in the prior art. In the area of musk perfumes, we may mention in particular Helvetolide/Serenolide, Romandolide and Appelide and derivatives thereof.

Musk perfumes from the stated groups are described in documents <CIT>, <CIT>,.

<CIT>, <CIT>, <CIT>, <CIT>, <CIT> and <CIT>.

The odor descriptions of the known perfumes, from our own investigations and from the patent literature, can be summarized as follows:.

Work on these classes of compounds relating to derivatization of the side chain was not pursued further in the prior art. This can probably be attributed to the earlier teaching that perfumes with a molecular weight above <NUM> (exception: Serenolide with <NUM>) are not of interest as perfumes (see G. Ohloff Scent and Fragrances, the Fascination of Odors and their Chemical Perspectives, Springer Verlag Berlin <NUM> p. A person skilled in the art would therefore assume that other derivatives of these basic structures, with higher molecular weight, lead to impairment of the olfactory properties.

The search for suitable perfumes, which led to the present invention, was made difficult by the following circumstances:.

The success of a search for suitable perfumes is therefore strongly dependent on the intuition of the person conducting the search.

Against this background, the problem to be solved by the present invention was to provide perfume compounds which, as well as a musk note, also possess fruity notes (aspects) and/or intensify such notes.

A further problem to be solved by the present invention was to provide perfume compounds with a high stability under specified conditions of use.

In addition to these main problems, the perfume compounds that are to be provided preferably have, as well as their primary (olfactory) properties, an additional or more preferably more than one additional positive secondary properties, for example good adherence, high substantivity, a booster effect also for other than flowery perfumes, a strong blooming and/or the property of imparting and/or intensifying other desirable (subsidiary) odor notes or odor impressions.

According to the invention, the primary problem is solved with a compound selected from the group consisting of <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxopentanoate, <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-methylpropyl tetra-hydrofuran-<NUM>-carboxylate, <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxoheptanoate, <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxooctanoate and <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-oxoethyl <NUM>-oxopentanoate.

The compounds according to the invention are shown in the following table <NUM>:.

A compound according to the invention is especially preferred that is selected from the group consisting of <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-methylpropyl tetrahydrofuran-<NUM>-carboxylate, <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxoheptanoate, <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxooctanoate, and <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-oxoethyl <NUM>-oxopentanoate.

As well as the odor notes and olfactory properties described above, musk and fruity, the especially preferred compounds possess in particular the further odor notes / olfactory properties mentioned in Table <NUM>.

The compounds according to the invention can be in optically active form and even in isomerically pure form. They can, however, also be used as any mixture of the stereoisomers, in particular also as racemates.

The compounds according to the invention can be used in combination with one or more of the following compounds (<NUM>) to (<NUM>):
<CHM>
<CHM>
wherein R3 has the following general formula (IV)
<CHM>
and wherein o is <NUM> or <NUM>, X is O or methylene, R and R1 are each methyl or form together with the carbon atom attached to a carbonyl group, and R2 is methyl, ethyl, propyl, butyl, butan-<NUM>-one-<NUM>-yl, tetrahydrofuran-<NUM>-yl, or tetrahydrofuran-<NUM>-yl.

Mixtures of compounds according to the invention and one or more of the compounds (<NUM>) to (<NUM>) can be used to enhance, modify or impart a musk and fruity odor.

The various olfactory properties could not be predicted for the compounds according to the invention from the prior art. This applies in particular to the combination of musk notes, fruity aspects (notes).

In addition to the primary (olfactory) properties, the compounds according to the invention possess additional positive secondary properties. In particular, relative to similar compounds from the prior art, we may mention improved adherence and high substantivity.

Many of the compounds according to the invention have a molecular weight above <NUM>, so that for the reasons stated above, the industry assumed that molecules of this size do not include any suitable fragrances.

Compounds according to the invention with a molecular weight (MW) ≥ <NUM> are preferred in many cases. These compounds possess surprisingly strong olfactory properties, with excellent adherence and/or high substantivity.

Especially <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-methylpropyl tetrahydrofuran-<NUM>-carboxylate (compound <NUM>) with an molecular weight of <NUM>/mol shows a very strong musk odor and is the highest molecular weight alicyclic musk known until now.

It is also surprising that the compounds according to the invention and in particular the aforementioned preferred compounds according to the invention show an enhanced stability in comparison with romandolide as a benchmark under normal use condition of perfuming compounds.

It has also been surprisingly found that the compounds according to the invention and in particular the aforementioned preferred compounds according to the invention show long lasting tenacity of above <NUM>.

Furthermore, it is surprising that the compounds according to the invention possess positive properties such as substantivity, adhesion and biodegradability, but at the same time do not have any unpleasant odor notes, even as a result of hydrolysis.

These properties, too, could not be predicted based on the modifications, which were undertaken contrary to the prior art.

Further aspects of the invention can be seen from the following description, the examples, and the appended patent claims.

The present invention also relates to a use of a compound selected from the group consisting of <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxopentanoate, <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-methylpropyl tetra-hydrofuran-<NUM>-carboxylate, <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxoheptanoate, <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxooctanoate and <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-oxoethyl <NUM>-oxopentanoate, as a perfuming ingredient.

A perfuming ingredient is, in the context of the present text, any substance that is suitable for being used for bringing about an olfactory impression, i.e. for imparting an olfactory impression, or for altering (modifying or intensifying) the olfactory perception of another substance.

"Impart" a note or an odor characteristic is to be understood as follows, in the sense of this application:
A perfume mixture does not possess the note to be imparted or an odor characteristic to be imparted. Following addition of a sufficient amount of the compound according to the invention or of a mixture of the compounds according to the invention, the corresponding notes (the corresponding odor characteristic) are sensorially perceptible. In this case an imparting is present.

"Intensify" is to be understood as follows:
The comparative mixture V already possesses a corresponding note / a corresponding odor characteristic. On adding the compound according to the invention or a mixture of compounds according to the invention in a sufficient amount, the corresponding odor characteristic / the corresponding odor note is sensorially perceptibly intensified.

In case of doubt, the presence of imparting and/or intensifying is to be established by a panel of experts (e.g. <NUM> experts) with sensory training. Intensification or imparting of an impression is present when a corresponding effect is established sensorially, reproducibly by at least <NUM>% of the panellists.

The use according to the invention is preferred, for enhancing, modifying or imparting a musk odor and/or for enhancing, modifying or imparting a fruity odor.

In accordance with the foregoing, another aspect of the invention relates in particular to a perfume composition comprising at least one compound according to the present invention.

Perfume compositions according to the invention are usually liquid at <NUM> and 1013hPa and normally are homogeneous solutions.

Perfume compositions often comprise synthetic or natural (preferably) taste and odor neutral carrier oils, which contain the scent or fragrance substance (as artificial or natural substances) in highly concentrated form (as well as perfumistic solvents and/or auxiliary materials, if applicable). The same applies accordingly to the perfume compositions according to the invention described herein.

Preferably, the perfume composition according to the invention comprises one or more additional fragrance ingredients.

Examples for fragrance ingredients that generally preferably can be used as component of a perfume composition according to the invention can be found for example in <NPL>on or <NPL>.

Preferred ethereal oils, concretes, absolutes, resins, resinoids, balsams and/or tinctures, that can be a fragrance ingredient of a perfume composition according to the invention are preferably to be selected from the group consisting of:
Ambergris tincture; amyris oil; angelica seed oil; angelica root oil; aniseed oil; valerian oil; basil oil; tree moss absolute; bay oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch tee oil; bitter almond oil; savory oil; bucco leaf oil; cabreuva oil; cade oil; calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassie absolute; castoreum absolute; cedar leaf oil; cedar wood oil; cistus oil; citronella oil; citrus oil; copaiva balsam; copaiva balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill weed oil; dill seed oil; eau de brouts absolute; oakmoss absolute; elemi oil; estragon oil; eucalyptus citriodora oil; eucalyptus oil; fennel oil; spruce needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiacwood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calamus oil; chamomile oil blue; chamomile oil roman; carrot seed oil; cascarilla oil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; lime oil distilled; lime oil squeezed; linaloe oil; litsea cubeba oil; bay leaf oil; macis oil; Marjoram oil; mandarin oil; massoia bark oil; mimosa absolute; musk seed oil; musk tincture; muscatel sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; carnation leaf oil; carnation blossom oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange blossom absolute; orange oil; origanum oil; palmarosa oil; patchouli oil; perilla oil; peru balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; allspice oil; pine oil; poley oil; rose absolute; rosewood oil; rose oil; rosemary oil; sage oil Dalmatian; sage oil Spanish; sandalwood oil; celery seed oil; spike lavender oil; star aniseed oil; styrax oil; tagetes oil; fir needle oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; wine yeast oil; vermouth oil; wintergreen oil; ylang oil; ysop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil.

Preferred single fragrance substances that can be preferably used as fragrance ingredients of a perfume composition according to the invention are selected from the group of.

The special properties of the compounds according to the invention can - as already mentioned - be exploited particularly well in order to produce interesting and desirable fragrance notes/properties in perfume compositions according to the invention.

The compounds according to the invention are usually employed in sensorially effective amounts. In perfume compositions, the compounds according to the invention are mixed with further perfumes. These further perfumes can in principle be any known perfumes.

A perfume composition according to the invention is preferred in which the mass ratio of the total of the perfumes according to the invention to the total of the further perfumes contained in the perfume mixture is <NUM>:<NUM> to <NUM>:<NUM>, preferably <NUM>:<NUM> to <NUM>:<NUM>.

At this ratio, the advantages of the compounds according to the invention can be exploited particularly well.

A perfume composition according to the invention in which the proportion of the total of the perfumes according to the invention is <NUM> to <NUM> wt. %, preferably <NUM> to <NUM> wt. % and especially preferably <NUM> to <NUM> wt. %, relative to the total weight of the perfume composition, is further preferred according to the invention.

Accordingly, another aspect of the present invention relates to a perfumed product. A perfumed product according to the invention comprises at least one compound according to the present invention, preferably in a sensorially effective amount.

Preferred perfumed products according to the invention are detergents and cleaning products, hygiene or care products, especially products from the area of body and hair care, cosmetics and household products.

Preferred products are for example perfume extraits, eau de parfums, eau de toilettes, aftershaves, eau de colognes, pre-shave products, splash colognes and perfumed refreshing tissues as well as perfumed or to be perfumed acidic, alkaline and neutral detergents, such as e.g. floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring agent, solid or liquid toilet cleaners, toilet sticks, toilet stones (liquid or solid), powdery or foamy carpet cleaners, liquid detergents, powdery detergents, laundry pretreatment agents such as bleaches, soaking agents and stain removers, fabric softeners, laundry soaps, laundry tablets, disinfectants, surface disinfectants as well as air improvers in liquid or gel-like form or applied to a solid carrier, particularly for deodorization of exhaust air from air conditioning and industrial processes, as well as air improvers in the form of aerosol or pump sprays, waxes and polishes such as furniture polishes, floor waxes, shoe creams, strengthening, impregnating or deodorizing textile treatment agents, diapers, sanitary towels, panty liners, plasters, as well as personal care agents such as e.g. solid and liquid soaps, shower gels, shampoos, shaving soap, shaving foams, bathing oils, damp cleaning cloths, cosmetic emulsion of the oil-in-water, water-in-oil and water-in-oil-in-water type such as e.g. skin creams and lotions, face creams and lotions, sun protection creams and lotions, after sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products such as e.g. hair sprays, hair gels, strengthening hair lotions, hair conditioners, permanent or semi-permanent hair dyes, hair forming agents such as cold waves and hair smoothing agents, hair tonics, hair creams and lotions, deodorants and antiperspirants such as e.g. armpit sprays, roll-ons, deo sticks, deo creams, products for decorative cosmetic such as e.g. eyeshadow, makeups, lipsticks, mascara as well as candles, lamp oils, incense sticks, animal litter, cat litter, insecticides, repellents, liquid and gaseous fuels, heating oils and heating gases.

Particularly preferred perfumed products according to the invention are selected from the group consisting of perfume extraits, eau de perfumes, eau de toilettes, aftershaves, eau de colognes, pre-shave products, splash colognes, perfumed refreshing tissues, acidic, alkaline and neutral detergents, textile fresheners, ironing aids, liquid detergents, powdery detergents, laundry pretreatment agents, fabric softeners, laundry soaps, laundry tablets, disinfectants, surface disinfectants, air improvers, aerosol sprays, waxes and polishes, personal care agents, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants and antiperspirants, products for decorative cosmetic, candles, lamp oils, incense sticks, insecticides, repellents and fuels.

For purposes of clarification it has to be mentioned that (perfumed) products according to the invention within the scope of the present text are to be understood as products that have been caused or produced on purpose, but not as naturally occurring substance mixtures, for example such as the ones that can be obtained from plant-based starting materials by means of extraction.

The compounds according to the present invention are preferably a constituent of a perfume composition according to the invention. Therefore, in a preferred embodiment, a perfumed product comprises a perfume composition according to the invention, and a carrier or a substrate, wherein the carrier or the substrate is in direct contact with said perfume composition. The substrate is for example a solid substrate or the carrier is for example a solid carrier. The carrier or substrate guarantees a fine distribution of the perfume composition inside the product as well as a controlled release during application. Such carriers may be porous inorganic materials such as silica gels, zeolites, gypsums, clay, clay granules, aerated concrete etc. or organic materials such as woods and cellulose-based substances.

The compounds according to the present invention to be used according to the invention or perfume compositions according to the present invention may also be present in microencapsulated or spray-dried form, as inclusion complexes or as extrusion products and can be added to a product in this form.

If applicable, the properties of compounds according to the present invention to be used according to the invention or of perfume compositions according to the present invention can be further optimized by means of so-called "coating" with suitable materials with regard to a more targeted release, wherein preferably wax-like plastic materials such as e.g. polyvinyl alcohol are used.

A microencapsulation of the compounds according to the present invention to be used according to the invention or perfume compositions according to the present invention can take place, for example, by means of the so-called coacervation process with the aid of capsule materials, e.g. of polyurethane-like substances or soft gelatin. Spray-dried compounds according to the present invention can be produced, for example, by means of spray-drying of a compound according to the invention, i.e. of an emulsion or dispersion containing a compound according to the present invention or a perfume compositions according to the present invention, wherein modified starches, proteins, dextrins and/or plant-based gums can be used as carrier substance. Inclusion complexes can be produced, for example, by means of addition of dispersions, which are or comprise a compound according to the present invention or a perfume compositions according to the present invention, and cyclodextrins or urea derivatives into a suitable solvent, e.g. water. Extrusion products can take place by means of fusion of a compound according to the present invention or a perfume compositions according to the present invention with a suitable wax-like substance and extrusion with subsequent solidification, in a suitable solvent, e.g. isopropanol, if applicable.

The compounds according to the present invention or perfume compositions according to the present invention can be used in many preparations or products, wherein they are preferably combined with one or several of the following excipients or active ingredients:
Preserving agents, abrasives, anti-acne agents, agents against skin aging, antibacterial agents, anticellulite agents, antidandruff agents, anti-inflammatory agents, irritation preventing agents, irritation inhibiting agents, antimicrobial agents, antioxidants, astringents, sweat inhibiting agents, antiseptic agents, antistatic agents, binders, buffers, carrier materials, chelate builders, cell stimulants, cleaning agents, caring agents, depilatory agents, surface active agents, deodorizing agents, antiperspirants, plasticizers, emulsifiers, enzymes, ethereal oils, fibres, fixators, foam builders, foam stabilizers, substances to prevent foaming, foam boosters, fungicides, gelatinizing agents, gelforming agents, hair care products, hair forming products, smoothing agents, moisturizing agents, dampening substances, moist-keeping substances, bleaching agents, (textile-)strengthening agents, stain removing agents, optical brightening agents, impregnating agents, dirt-repellent agents, friction-lowering agents, lubricants, moisturizing creams, ointments, opacifiers, plasticizing agents, covering agents, polish, glazing agents, polymers, powders, proteins, regreasing substances, abrasive agents, silicones, skin soothing agents, skin cleaning agents, skin caring agents, skin healing agents, skin lightening agents, skin protecting agents, skin softening agents, cooling agents, skin cooling agents, warming agents, skin warming agents, stabilizers, UV-absorbing agents, UV-filters, detergents, fabric softeners, suspending agents, skin tanning agents, thickening agents, vitamins, oils, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, α-hydroxy acids, polyhydroxy fatty acids, liquefying agents, dyes, color-protecting agents, pigments, anticorrosives, aromas, flavorings, aromatic substances, polyols, surfactants, electrolytes, organic solvents or silicon derivatives.

According to one embodiment of the present invention a preferred product according to the invention, particularly a deodorant or the like, additionally contains (depending on the desired mode of action) one or several of the following active substances:.

The present invention also relates to a method for producing a perfumed product, particularly a perfumed product according to the invention, comprising the following steps:.

The present invention also relates to a method of imparting and/or increasing musk and/or floral odor characteristics to a perfumed product comprising the step of adding thereto a compound according to the invention or a perfume composition according to the invention.

In the following, the present invention will be illustrated in more detail by means of selected examples. Unless otherwise stated, all specifications thereby relate to the weight.

A mixture of Cyclodumol (<NUM>, <NUM> mmol), Levulinic acid (<NUM>, <NUM> mmol) in toluene (<NUM>) was added catalytic amount of pTs (<NUM>). This mixture was refluxed for about <NUM>, after the reaction completion, at room temperature this reaction mixture was washed with water (2x <NUM>) and the organic layer was concentrated on a rotary evaporator which gave crude material (<NUM>). Crude material was purified by Kügelrohr distillation (KRD)/bulb to bulb distillation, <NUM>, <NUM> mbar to provide <NUM>-(<NUM>,<NUM>-Dimethylcyclohexyl)ethyl <NUM>-oxopentanoate (<NUM>, <NUM>%), as mixture of isomers. By PGC individual isomers were also identified and confirmed by NMR.

<NUM>H NMR (<NUM>, Benzene-d<NUM>) δ <NUM> (p, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (td, J = <NUM>, <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (dddd, J = <NUM>, <NUM>, <NUM>, <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (tt, J = <NUM>, <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (td, J = <NUM>, <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (qd, J = <NUM>, <NUM>, <NUM>).

<NUM>C NMR (<NUM>, Benzene-d<NUM>) δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

To a mixture of tetrahydrofuran-<NUM>-carboxylic acid (<NUM>, <NUM> mmol), <NUM>-[<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy]-<NUM>-methyl-propan-<NUM>-ol (Lit: <CIT>) (<NUM>, <NUM><NUM> mmol) in DCM (<NUM>) was added <NUM>-DMAP (<NUM>, <NUM> mmol) and by portion wise <NUM>,<NUM> Dicyclohexylcarbodiimide (DCC) (<NUM>, <NUM> mmol). This reaction mixture was stirred at room temperature overnight. This reaction mixture was filtered, washed with DCM (<NUM>) and the filtrate was concentrated on a rotary evaporator to get crude product (<NUM>), which was purified by KRD, <NUM>, <NUM> mbar (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, Chloroform-d) δ <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (dtd, J = <NUM>, <NUM>, <NUM>, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (dddd, J = <NUM>, <NUM>, <NUM>, <NUM>, <NUM>), <NUM> - <NUM> (m, <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> (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>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

A solution of Methyl-<NUM>-Chloracetat (<NUM>, <NUM> mmol) und Methyl-<NUM>-Oxohexanoate (<NUM>, 170mmol) in THF (<NUM>) was taken in a three-necked round bottom flask, equipped with a reflux condenser. To this reaction mixture, portionwise, was added potassium tert-butoxide (<NUM>, <NUM> mmol) (Exothermic: T<<NUM>) and after the addition, it was refluxed for <NUM>. After the completion of the reaction, reaction mixture temperature was reduced to room temperature and quenched with cold water. Compound was extracted using MTBE (<NUM> x <NUM>) and the organic phase was washed with water (<NUM> x <NUM>), dried over sodium sulphate and the solvent was removed by evaporation (<NUM>, <NUM>-<NUM> mbar) to yield the crude product Dimethyl <NUM>-butanoylbutanedioate (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, Chloroform-d) δ <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (sextet, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>).

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

A solution of Dimethyl <NUM>-butanoylbutanedioate (<NUM>, <NUM> mmol) in water (<NUM>) and methanol (<NUM>) mixture, was taken in a three-necked round bottom flask, equipped with a reflux condenser. By dropwise, added NaOH solution <NUM>% solution in water (<NUM>, <NUM>. 7mmol) and refluxed for ~<NUM> and brought it to room temperature. To this reaction mixture was added H<NUM>SO<NUM> (<NUM>, <NUM>. 6mmol) and refluxed for ~<NUM>-<NUM>. After the completion of the reaction, at room temperature reaction mixture was further diluted with water (<NUM>) and compound was extracted with MTBE (<NUM> x2). Combined organic layer was washed with sat. NaHCO<NUM> solution, water (until neutral), dried over sodium sulphate and the solvent was removed by evaporation (<NUM>, <NUM>-<NUM> mbar) to yield the crude product methyl <NUM>-oxoheptanoate (<NUM>) <NPL>).

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

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

To a mixture of Zirkon-n-propylat (<NUM>) in Cyclodumol (<NUM>, <NUM> mmol), methyl <NUM>-Oxoheptanoate (<NUM>, <NUM> mmol) was added. It was heated to <NUM>-<NUM>, atm. press - <NUM> mbar for ~<NUM> to get the crude product (<NUM>,<NUM>). Crude was purified by bulb-to bulb distillation (T = <NUM>, p = <NUM> mbar) gave <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxoheptanoate (<NUM>, <NUM>%, GC purity <NUM>,<NUM>%).

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

A solution of Methyl-<NUM>-Chloracetat (<NUM>, <NUM> mmol) und Methyl-<NUM>-Oxoheptanoate (<NUM>, <NUM> mmol) in THF (<NUM>) was taken in a three-necked round bottom flask, equipped with a reflux condenser. To this reaction mixture, portion wise, was added potassium tert-butoxide (<NUM>, <NUM> mmol) (Exothermic: T<<NUM>) and after the addition, it was refluxed for <NUM>-<NUM>. After the completion of the reaction, reaction mixture temperature was reduced to room temperature and quenched with cold water. Compound was extracted using MTBE (<NUM> x <NUM>) and the organic phase was washed with water (<NUM> x <NUM>), dried over sodium sulphate and the solvent was removed by evaporation (<NUM>, <NUM>-<NUM> mbar) to yield the crude product, which was further purified by bulb-to bulb distillation (T = <NUM>, p = <NUM> mbar), afforded Dimethyl <NUM>-pentanoylbutanedioate (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, Chloroform-d) δ <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (dt, J = <NUM>, <NUM>, <NUM>), <NUM> (dt, J = <NUM>, <NUM>, <NUM>), <NUM> (mc, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (td, J = <NUM>, <NUM>, <NUM>).

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

A solution of Dimethyl <NUM>-pentanoylbutanedioate (<NUM>, <NUM> mmol) in water (<NUM>) and methanol (<NUM>) mixture, was taken in a three-necked round bottom flask, equipped with a reflux condenser. By dropwise, added <NUM>% NaOH solution in water (<NUM>, <NUM> mmol) and refluxed for ~<NUM> and brought it to room temperature. To this reaction mixture was added H<NUM>SO<NUM> (<NUM>, <NUM> mmol) and refluxed for ~<NUM>. After the completion of the reaction, at room temperature reaction mixture was further diluted with water (<NUM>) and compound was extracted with MTBE (<NUM> x2). Combined organic layer was washed with sat. NaHCOs solution, water (until neutral), dried over sodium sulphate and the solvent was removed by evaporation (<NUM>, <NUM>-<NUM> mbar) to yield the crude product methyl <NUM>-oxooctanoate (<NUM>, <NUM>%, GC Purity <NUM>%).

<NUM>H NMR (<NUM>, Chloroform-d) δ <NUM> (s, <NUM>), <NUM> (td, J = <NUM>, <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (m, <NUM>), <NUM> (p, J = <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>.

To a mixture of Zirkon-n-propylat (<NUM>, <NUM> mmol) in Cyclodumol (<NUM>, <NUM> mmol), methyl <NUM>-Oxooctanoate (<NUM>, <NUM> mmol) was added. It was heated to <NUM>-<NUM>, atm. press - <NUM> mbar for ~<NUM> to get the crude product, which was purified by bulb-to bulb distillation (T = <NUM>, p = <NUM>-<NUM> mbar) gave <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxooctanoate (<NUM>, <NUM>%, GC purity <NUM>%).

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

To a solution of Cyclodumol (<NUM>, <NUM> mol), Toluene (<NUM>) and Pyridine (<NUM>, <NUM> mol) at <NUM>, a predissolved solution of Chloroacetyl chloride (<NUM>, <NUM> mol) in toluene (<NUM>) was added dropwise (exothermic reaction). After the addition, the reaction temperature was maintained for another <NUM>-<NUM>. The, reaction mixture was cooled <NUM>-<NUM> and quenched with ice cold water (<NUM>) (slow addition). Organic phase was separated, organic layer washed with water (<NUM> x <NUM>), <NUM>% soda solution (<NUM> x <NUM>) and evaporated (<NUM>/<NUM>-20mbar) to get the crude (<NUM>). Crude was purified using <NUM> Vigreux distillation (Flask temp = <NUM>-<NUM>, Head temp = <NUM>-<NUM>) to afford the title compound <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-chloroacetate (<NUM>, <NUM>%). (Lit: <CIT>).

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

To a mixture of <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-chloroacetate (<NUM>, <NUM> mmol) and NMP (<NUM>) was slowly added Luvilic acid (<NUM>,<NUM>, <NUM> mmol), slight exothermic was observed. Between <NUM>-<NUM>, calcium carbonate (<NUM>,<NUM>, <NUM> mmol) was added portionwise. The reaction mixture was maintained at <NUM>. After the reaction is completed after <NUM>, reaction mixture was quenched by slowly added water (<NUM>) (observed exothermic). Compound was extracted with MTBE (<NUM> x <NUM>). Combined organic layer was washed with <NUM>% NaCl solution (<NUM> X2), dired over Na<NUM>SO<NUM> and evaporated organic layer. To the crude, once again water (<NUM>) water to remove the salt and extracted with Tolune (<NUM> X3). Toluene was evaporated which gave <NUM> of crude product, which upon purification by column chromatography (Cyclohexane: Ethylacetate, <NUM>:<NUM>) gave the title compound (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, Chloroform-d) δ <NUM> (p, J = <NUM>:<NUM>, <NUM>), <NUM> (td, J = <NUM>, <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J =<NUM>, <NUM>), <NUM> (td, J =<NUM>, <NUM>, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <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> (d, J = <NUM>, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> - <NUM> (m, <NUM>).

Claim 1:
Use of a compound selected from the group consisting of <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxopentanoate, <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-methylpropyl tetra-hydrofuran-<NUM>-carboxylate, <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxoheptanoate, <NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethyl <NUM>-oxooctanoate, <NUM>-(<NUM>-(<NUM>,<NUM>-dimethylcyclohexyl)ethoxy)-<NUM>-oxoethyl <NUM>-oxopentanoate,
as a perfuming ingredient.