Patent Grant
10883066
This application is a U.S. National Phase Application of PCT/EP2018/058205, filed on Mar. 29, 2018, which claims the benefit of priority to European Patent Application Number 17164797.7, filed Apr. 4, 2017, the entire contents of which are hereby incorporated by reference herein.
The present invention relates to the field of perfumery. More particularly, it concerns trans isomers of formula (I) as defined herein below, and their uses as perfuming ingredients, e.g. in consumer products.
The perfumery industry is constantly on the lookout for new ingredients in order to support the creativity of perfumer by diversifying the notes present in their palette. One of the key organoleptic families in perfumery is the woody note which is very important in perfumery creation.
The present invention provides new compounds belonging to this family. Actually, the compound of formula (I) having an anti-configuration between the two methyl groups at carbon 4a and 8 as reported in the present invention provide a very interesting woody note.
FR2203642 and Helvetica Chimica Acta 1972, 55, 2371 report a mixture of 1-((2RS,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2R,4aR,8S,8aS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one as a side product and Tetrahedron 1965, 21(5), 1167 discloses 1-((2SR,4aRS,8RS,8aSR)-4a, 8-dimethyldecahydronaphthalen-2-yl)ethan-1-one. However none of those prior arts mentions the organoleptic properties of said compounds.
To the best of our knowledge, the only related analogue reported in the literature, and described for its odor properties, is 1-[(4aRS,8SR,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydro-2-naphthalenyl]ethanone, i.e a derivative having a syn configuration between the two methyl groups at carbon 4a and 8 (see N. Baldovini et al, in Flavour Frag. J., 2015, 30,26). Said prior art analogue has been defined in nature and described has having a woody-fruity damascone odor, i.e. significantly different from the one of the present compounds.
The prior art documents do not report or suggest any organoleptic properties of the compound of formula (I), or any use of said compound in the field of perfumery.
The invention relates to compound of formula (I) which imparts an odor of woody/rooty and powdery type which is very appreciated in perfumery.
So, a first object of the present invention is a use of a compound of formula
in the form of any one of its stereoisomers or a mixture thereof, and wherein the bold and hatched lines indicate a relative or absolute configuration.
A second object of the invention is a compound of formula
in the form of any one of its stereoisomers or a mixture thereof, wherein the bold and hatched lines indicate a relative or absolute configuration.
A third object of the invention is a perfuming composition comprising
Another object of the invention is a perfumed consumer product comprising at least one compound of formula (I) as defined above or a composition as defined above.
A last object of the invention is a method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least a compound of formula (I) as defined above.
We have now surprisingly discovered that the compound of formula (I) possesses a very interesting odor note of the woody type with powdery connotation. The association of these two notes is original.
So, a first object of the present invention is a compound of formula
in the form of any one of its stereoisomers or a mixture thereof, and wherein the bold and hatched lines indicate a relative or absolute configuration.
Said compound can be used as perfuming ingredient, for instance to impart a powerful odor notes of the woody type in the direction of vetiver/rooty type and also with powdery aspect.
For the sake of clarity, by the expression “any one of its stereoisomers”, or the similar, it is meant the normal meaning understood by a person skilled in the art, i.e. that the invention's compound can be a pure enantiomer or diastereomer (e.g. the hydrogen atom on the carbon 8a in a syn or anti conformation relative to the methyl group in position 4a), provided of course that the two methyl groups at carbon 4a and 8 are in an anti-configuration either relative or absolute.
For the sake of clarity, by the expression “the bold and hatched lines indicate a relative or absolute configuration” or the similar, it is meant the normal meaning understood by a person skilled in the art, i.e. that in the case of a relative configuration compound (I) is in the form of a mixture of stereoisomers comprising more than 50% (w/w) of the (4aRS,8RS) stereoisomer, i.e. a compound having the two methyl groups in a relative trans configuration as shown in formula (I), or in the case of an absolute configuration compound (I) is in the form of a mixture of stereoisomers comprising more than 50% (w/w) of the (4aS,8S) stereoisomer. For the sake of clarity, by the expression “(4aRS,8RS)” it is meant an equimolar mixture of (4aR,8R) and (4aS,8S).
According to a particular embodiment of the invention, compound (I) can be a compound of formula
in the form of any one of its stereoisomers or a mixture thereof, wherein the bold, hatched and dotted lines have the meaning indicated in formula (I).
According to a particular embodiment of the invention, compound (II) can be a compound of formula
wherein the bold, hatched and dotted lines have the meaning indicated in formula (I).
According to a particular embodiment of the invention, compound (II) can be a compound of formula
wherein the bold, hatched and dotted lines have the meaning indicated in formula (I).
According to a particular embodiment of the invention, compound (I) can be a compound of formula
in the form of any one of its stereoisomers or a mixture thereof, wherein the bold, hatched and dotted lines have the meaning indicated in formula (I).
According to a particular embodiment of the invention, compound (II) can be a compound of formula
wherein the bold, hatched and dotted lines have the meaning indicated in formula (I).
According to a particular embodiment of the invention, compound (II) can be a compound of formula
wherein the bold, hatched and dotted lines have the meaning indicated in formula (I).
In the present invention the term “compound of formula (I)” is constructed in order to encompass also all composition of matter resulting from the admixture of at least two chemicals responding to formula (I). Said compound of formula (I) can be in the form of a composition of matter comprising, or consisting of 1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aRS)-4a, 8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aSR)-4a, 8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2SR,4aRS,8RS,8aRS)-4a, 8-dimethyldecahydronaphthalen-2-yl)ethan-1-one.
In particular, said compound of formula (I) can be in the form of a composition of matter comprising, or consisting of:
Moreover, said compound of formula (I) can be in the form of a composition of matter comprising mainly compound of formula II″. Said compound of formula (I) can be in the form of a composition of matter comprising, or consisting of:
Preferably, said compound of formula (I) can be in the form of a composition of matter comprising, or consisting of:
According to a particular embodiment, said compound of formula (I) can be in the form of a composition of matter comprising, or consisting of:
According to a particular embodiment, said compound of formula (I) can be in the form of a composition of matter comprising, or consisting of:
As specific examples of the invention's compounds, one may cite, as non-limiting example, a mixture of 1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2SR,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one in a respective molar ratio of 7/9/47/37 (herein after referred to as Mix 1) which has a very good woody odor in the direction of vetiver/rooty type, in addition, a powdery, iris and violet odor and also comprises amber aspects. The powdery/iris character of this ingredient is reminiscent of Myrrhone® (4-(2,2,C-3,T-6-tetramethyl-R-1-cyclohexyl)-3-buten-2-one, trademark and origin: Firmenich SA). This mixture has also very powerful odor.
As another example, one may cite a mixture of 1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2RS,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one in a respective molar ratio of 45/55 (herein after referred to as Mix 2) which has a organoleptic characteristic very close to Mix 1 comprising some aqueous and camphor aspects.
As another example, one may cite a mixture of 1-((2RS,4aRS,8RS,8aS)-4a, 8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2SR,4aRS,8RS,8aRS)-4a, 8-dimethyldecahydronaphthalen-2-yl)ethan-1-one in a respective ratio of 45/55 (herein after referred to as Mix 3), which possesses organoleptic properties in the direction of Mix 1; i.e. powerful, and woody with some powdery and iris aspects and in addition, possesses earthy aspect.
As other specific, but non-limiting, examples of the invention's compounds, one may cite the following ones in Table 1:
According to a particular embodiment of the invention, the compounds of formula (I) are 1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2SR,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and/or mixtures thereof.
When the odor of the invention's compounds is compared with that of the prior art compound 1-[(4aRS,8SR,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydro-2-naphthalenyl]ethanone (i.e. the cis compound), then the invention's compounds distinguish themselves by being largely more powerful and by having a powdery/violet/iris character and also a smoky aspect in addition to the woody note.
Furthermore, the woody note associated with the invention's compounds is of the rooty type, i.e. a warm heavy effect, while the woody note associated with the prior art compounds is of the cedar type, i.e. a resin, sawdust, fresh effect. The odor of the invention's compounds distinguish also themselves from the prior art by lacking, or not possessing significant, fruity notes and damsacone notes, which are characteristic of the prior art compound. Said differences, besides being not foreseeable, lead the invention's compounds and the prior art compound to be each suitable for different uses, i.e. to impart different organoleptic impressions.
As mentioned above, the invention concerns the use of a compound of formula (I) as perfuming ingredient. In other words, it concerns a method or a process to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article or of a surface, which method comprises adding to said composition or article an effective amount of at least a compound of formula (I), e.g. to impart its typical note.
By “use of a compound of formula (I)” it has to be understood here also the use of any composition containing a compound (I) and which can be advantageously employed in the perfumery industry.
Said compositions, which in fact can be advantageously employed as perfuming ingredients, are also an object of the present invention.
Therefore, another object of the present invention is a perfuming composition comprising:
By “perfumery carrier” it is meant here a material which is practically neutral from a perfumery point of view, i.e. that does not significantly alter the organoleptic properties of perfuming ingredients. Said carrier may be a liquid or a solid.
As liquid carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in perfumery. A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive. However, one can cite as non-limiting examples, solvents such as butylene or propylene glycol, glycerol, dipropyleneglycol and its monoether, 1,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate 1,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethano, tri-ethyl citrate or mixtures thereof, which are the most commonly used. For the compositions which comprise both a perfumery carrier and a perfumery base, other suitable perfumery carriers than those previously specified, can be also ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar® (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol® (origin: Dow Chemical Company), or hydrogenated castors oils such as those known under the trademark Cremophor® RH 40 (origin: BASF).
Solid carrier is meant to designate a material to which the perfuming composition or some element of the perfuming composition can be chemically or physically bound. In general such solid carriers are employed either to stabilize the composition, or to control the rate of evaporation of the compositions or of some ingredients. The use of solid carrier is of current use in the art and a person skilled in the art knows how to reach the desired effect. However by way of non-limiting example of solid carriers, one may cite absorbing gums or polymers or inorganic material, such as porous polymers, cyclodextrins, wood based materials, organic or inorganic gels, clays, gypsum talc or zeolites.
As other non-limiting examples of solid carriers, one may cite encapsulating materials. Examples of such materials may comprise wall-forming and plasticizing materials, such as mono, di- or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinylalcohols, proteins or pectins, or yet the materials cited in reference texts such as H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualität, Behr's Verlag GmbH & Co., Hamburg, 1996. The encapsulation is a well-known process to a person skilled in the art, and may be performed, for instance, by using techniques such as spray-drying, agglomeration or yet extrusion; or consists of a coating encapsulation, including coacervation and complex coacervation technique.
As non-limiting examples of solid carriers, one may cite in particular the core-shell capsules with resins of aminoplast, polyamide, polyester, polyurea or polyurethane type or a mixture threof (all of said resins are well known to a person skilled in the art) using techniques like phase separation process induced by polymerization, interfacial polymerization, coacervation or altogether (all of said techniques have been described in the prior art), optionally in the presence of a polymeric stabilizer or of a cationic copolymer.
Resins may be produced by the polycondensation of an aldehyde (e.g. formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with an amine such as urea, benzoguanamine, glycoluryl, melamine, methylol melamine, methylated methylol melamine, guanazole and the like, as well as mixtures thereof. Alternatively one may use preformed resins alkylolated polyamines such as those commercially available under the trademark Urac® (origin: Cytec Technology Corp.), Cy Mel® (origin: Cytec Technology Corp.), Urecoll® or Luracoll® (origin: BASF).
Others resins one are the ones produced by the polycondensation of an a polyol, like glycerol, and a polyisocyanate, like a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate or xylylene diisocyanate or a Biuret of hexamethylene diisocyanate or a trimer of xylylene diisocyanate with trimethylolpropane (known with the tradename of Takenate®, origin: Mitsui Chemicals), among which a trimer of xylylene diisocyanate with trimethylolpropane and a Biuret of hexamethylene diisocyanate.
Some of the seminal literature related to the encapsulation of perfumes by polycondensation of amino resins, namely melamine based resins with aldehydes includes represented by articles such as those published by K. Dietrich et al. Acta Polymerica, 1989, vol. 40, pages 243, 325 and 683, as well as 1990, vol. 41, page 91. Such articles already describe the various parameters affecting the preparation of such core-shell microcapsules following prior art methods that are also further detailed and exemplified in the patent literature. U.S. Pat. No. 4,396,670, to the Wiggins Teape Group Limited is a pertinent early example of the latter. Since then, many other authors have enriched the literature in this field and it would be impossible to cover all published developments here, but the general knowledge in encapsulation technology is very significant. More recent publications of pertinency, which disclose suitable uses of such microcapsules, are represented for example by the article of H. Y.Lee et al. Journal of Microencapsulation, 2002, vol. 19, pages 559-569, international patent publication WO 01/41915 or yet the article of S. Bône et al. Chimia, 2011, vol. 65, pages 177-181.
By “perfumery base” what is meant here is a composition comprising at least one perfuming co-ingredient.
Said perfuming co-ingredient is not of formula (I). Moreover, by “perfuming co-ingredient” it is meant here a compound, which is used in a perfuming preparation or a composition to impart a hedonic effect. In other words such a co-ingredient, to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor.
The nature and type of the perfuming co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the intended use or application and the desired organoleptic effect. In general terms, these perfuming co-ingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin.
In particular one may cite perfuming co-ingredients knows for having a similar olfactive note, such as:
In particular one may cite perfuming co-ingredients which are commonly used in perfume formulations, such as:
A perfumery base according to the invention may not be limited to the above mentioned perfuming co-ingredients, and many other of these co-ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, N.J., USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds.
By “perfumery adjuvant” we mean here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvant commonly used in perfuming composition cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art. One may cite as specific non-limiting examples the following: viscosity agents (e.g. surfactants, thickeners, gelling and/or rheology modifiers), stabilizing agents (e.g. preservatives, antioxidant, heat/light and or buffers or chelating agents, such as BHT), coloring agents (e.g. dyes and/or pigments), preservatives (e.g. antibacterial or antimicrobial or antifungal or anti irritant agents), abrasives, skin cooling agents, fixatives, insect repellants, ointments, vitamins and mixtures thereof.
It is understood that a person skilled in the art is perfectly able to design optimal formulations for the desired effect by admixing the above mentioned components of a perfuming composition, simply by applying the standard knowledge of the art as well as by trial and error methodologies.
An invention's composition consisting of at least one compound of formula (I) and at least one perfumery carrier consists of a particular embodiment of the invention as well as a perfuming composition comprising at least one compound of formula (I), at least one perfumery carrier, at least one perfumery base, and optionally at least one perfumery adjuvant.
According to a particular embodiment, the compositions mentioned above, comprise more than one compound of formula (I) and enable the perfumer to prepare accords or perfumes possessing the odor tonality of various compounds of the invention, creating thus new building block for creation purposes.
For the sake of clarity, it is also understood that any mixture resulting directly from a chemical synthesis, e.g. a reaction medium without an adequate purification, in which the compound of the invention would be involved as a starting, intermediate or end-product could not be considered as a perfuming composition according to the invention as far as said mixture does not provide the inventive compound in a suitable form for perfumery. Thus, unpurified reaction mixtures are generally excluded from the present invention unless otherwise specified.
The invention's compound can also be advantageously used in all the fields of modern perfumery, i.e. fine or functional perfumery, to positively impart or modify the odor of a consumer product into which said compound (I) is added. Consequently, another object of the present invention consists of by a perfumed consumer product comprising, as a perfuming ingredient, at least one compound of formula (I), as defined above.
The invention's compound can be added as such or as part of an invention's perfuming composition.
For the sake of clarity, “perfumed consumer product” is meant to designate a consumer product which delivers at least a pleasant perfuming effect to the surface or space to which it is applied (e.g. skin, hair, textile, or home surface). In other words, a perfumed consumer product according to the invention is a perfumed consumer product which comprises a functional formulation, as well as optionally additional benefit agents, corresponding to the desired consumer product, and an olfactive effective amount of at least one invention's compound. For the sake of clarity, said perfumed consumer product is a non-edible product.
The nature and type of the constituents of the perfumed consumer product do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the nature and the desired effect of said product.
Non-limiting examples of suitable perfumed consumer product include a perfume, such as a fine perfume, a splash or eau de parfum, a cologne or a shave or after-shave lotion; a fabric care product, such as a liquid or solid detergent, a fabric softener, a liquid or solid scent booster, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product; a body-care product, such as a hair care product (e.g. a shampoo, a coloring preparation or a hair spray, a color-care product, a hair shaping product, a dental care product), a disinfectant, an intimate care product; a cosmetic preparation (e.g. a skin cream or lotion, a vanishing cream or a deodorant or antiperspirant (e.g. a spray or roll on), a hair remover, a tanning or sun or after sun product, a nail product, a skin cleansing, a makeup); or a skin-care product (e.g. a soap, a shower or bath mousse, oil or gel, or a hygiene product or a foot/hand care products); an air care product, such as an air freshener or a “ready to use” powdered air freshener which can be used in the home space (rooms, refrigerators, cupboards, shoes or car) and/or in a public space (halls, hotels, malls, etc.); or a home care product, such as a mold remover, a furnisher care product, a wipe, a dish detergent or a hard-surface (e.g. a floor, bath, sanitary or a window-cleaning) detergent; a leather care product; a car care product, such as a polish, a wax or a plastic cleaner.
Some of the above-mentioned perfumed consumer products may represent an aggressive medium for the invention's compounds, so that it may be necessary to protect the latter from premature decomposition, for example by encapsulation or by chemically binding it to another chemical which is suitable to release the invention's ingredient upon a suitable external stimulus, such as an enzyme, light, heat or a change of pH.
The proportions in which the compounds according to the invention can be incorporated into the various aforementioned products or compositions vary within a wide range of values. These values are dependent on the nature of the article to be perfumed and on the desired organoleptic effect as well as on the nature of the co-ingredients in a given base when the compounds according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art.
For example, in the case of perfuming compositions, typical concentrations are in the order of 0.001% to 50% by weight, or even more, of the compounds of the invention based on the weight of the composition into which they are incorporated. In the case of perfumed consumer product, typical concentrations are in the order of 0.1% to 20% by weight, or even more, of the compounds of the invention based on the weight of the consumer product into which they are incorporated.
The invention will now be described in further detail by way of the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade (° C.); NMR spectra were acquired using either a Bruker Avance II Ultrashield 400 plus operating at 400 MHz, (1H) and 100 MHz (13C) or a Bruker Avance III 500 operating at 500 MHz (1H) and 125 MHz (13C) or a Bruker Avance III 600 cryoprobe operating at 600 MHz (1H) and 150 MHz (13C), the chemical shifts δ are indicated in ppm with respect to TMS as standard, the coupling constants J are expressed in Hz.
A mixture of the 1-((4aRS,8RS,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one, 1-((4aRS,8RS,8aRS)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one, 1-((4aRS,8RS,8aSR)-4a,8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one and 1-((4aRS,8RS,8aRS)-4a, 8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one (20:12:39:28, 30 g, 72.7 mmol) and Pd/C (5%) (250 mg) were placed in an autoclave, purged with hydrogen gas (10 bar) and then pressurized with hydrogen gas at 50 bars and stirred at r.t. for 4 hours. The reaction was stopped, filtered, rinsed with ether, concentrated under reduced pressure and the resulting reaction mixture was purified by bulb to bulb distillation (Kügelrohr 150° C./0.1 mbar) to yield the saturated ketone, 28.7 g (97%) as colourless oil consisting of a mixture of 4 isomers: 1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2SR,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one (7%, 9%, 47% and 37% resp.) (Mix 1).
The above ketones were separated into pairs after purification by CC/SiO2 (cyclohexane/AcOEt 249:1) to afford a first mixture consisting of 1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2RS,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one (Mix 2) (45/55 resp.) and a second mixture consisting of 1-((2RS,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2SR,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one (Mix 3) (45/55 resp.) as colourless oils.
Pure ketone 1-((2RS,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one was obtained by H2 cat. hydrogenation as described above from 1-((4aRS,8RS,8aSR)-4a,8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one, to afford mixture of 1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2RS,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one (18% and 82% resp.) (99% yield.). Purification by CC/SiO2 (cyclohexane/AcOEt 249:1) gave pure ketone 1-((2RS,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one.
13C NMR (125 MHz, CDCl3): δ 16.3 (q), 20.0 (q), 21.5 (t), 21.6 (t), 25.1 (t), 27.8 (q), 31.3 (d), 33.7 (s), 36.6 (t), 38.4 (t), 41.8 (t), 47.6 (d), 48.0 (d), 211.7 (s) ppm.
13C NMR (125 MHz, CDCl3): δ 19.8 (q), 21.0 (q), 21.8 (q), 22.1 (t), 27.6 (q), 27.8 (q), 28.2 (t), 28.8 (t), 29.5 (d), 33.4 (s), 37.5 (t), 42.5 (d), 47.6 (d), 211.6 (s) ppm.
1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2RS,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one (Mix 2) (45% and 55% Mixt. Resp.)
1H NMR (500 MHz, CDCl3): δ 0.69-0.73 (m, 1H); 0.89 (d, J 7.0, 3H), 0.845 (s, 3H), 0.86 (d, J 7.0, 3H); 0.91 (s, 3H); 0.92-1.13 (m, 2H); 1.15-1.25 (m, 2H), 1.25-1.35 (m, 2H), 1.40-1.46 (m, 1H), 1.49-1.57 (m, 2H), 1.60-1.77 (m, 2H), 1.90-2.00 (m, 2H), 2.137 (s, 3H); 2.15 (s, 3H) 2.57-2.61 (m, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 0.75 (ddd J 13, 10.8, 3.2, 1H), 0.82 (s, 3H); 0.83 (d, J6.5 Hz, 3H); 0.95 (qd J 13.4, 4.1, 1H); 1.08 (m, 1H); 1.09 (m, 1H); 1.14 (td, J 13.4; 4.2, 1H); 1.31 (m, 1H); 1.36 (bd, J 13.5, 1H); 1.44 (m, 1H); 1.47 (m, 1H); 1.57 (m, 2H); 1.68 (m, 2H); 1.82 (bd, J 13.5, 1H); 2.15 (s, 3H); 2.33 (tt, J 12.4, 4, 1H).
13C NMR (125 MHz, CDCl3): δ 16.7 (q), 20.1 (q), 21.6 (t), 23.7 (t), 26.2 (t), 28.0 (q), 31.3 (d), 33.6 (s), 36.7 (t), 41.3 (s), 41.7 (t), 50.9 (d), 52.5 (d), 212.4 (s) ppm.
1H NMR (500 MHz, CDCl3): δ 0.84 (d, J 6.5, 3H); 0.85 (m, 1H), 0.88 (m, 1H), 0.98 (s, 3H); 1.05-1.46 (m, 9H), 1.5-1.54 (m, 2H); 1.98 (m, 1H); 2.148 (s, 3H); 2.27 (m, 1H)
13C NMR (125 MHz, CDCl3): δ 19.9 (q), 22.1 (t), 22.6 (t), 23.9 (t), 27.6 (q), 28.2 (t), 28.5 (d), 29.2 (t), 29.8 (d), 33.4 (s), 41.0 (t), 46.3 (d), 52.1 (d), 212.8 (s) ppm.
Epimerisation/equilibration of the above mixture (2 g, 9.6 mmol) in ether (10 mL), with MeONa (21% EtOH) (0.5 mL, 1.7 mmol) heated at reflux for 2 hours gave the ketones 1-((2SR,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, 1-((2RS,4aRS,8RS,8aSR)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2SR,4aRS,8RS,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one, in following ratio of isomers 4%, 6%, 51% and 39% resp. No further modification of the isomers ratio was observed after longer reaction times.
Conditions of hydrogenation reaction as reported in example 1a) has been applied to 200 mg of a mixture of 1-[(4aRS,8SR,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydro-2-naphthalenyl]ethanone and 1-((4aR,8S,8aR)-4a,8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one in a respective molar ratio of 22:78 providing a mixture of 1-((2RS,4aRS,8SR,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one and 1-((2SR,4aRS,8SR,8aRS)-4a,8-dimethyldecahydronaphthalen-2-yl)ethan-1-one in a respective molar ration of 35:65 (yield 99%).
A perfuming composition, of the woody type, was prepared by admixing the following ingredients:
1) (−)-(8R)-8,12-epoxy-13,14,15,16-tetranorlabdane a)
2) high cis methyl dihydrojasmonate a)
3) (1S,1′R)-2-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxy]-2-methylpropyl propanoate a)
4) mixture of methylionones isomers a)
5) methyl dihydrojasmonate a)
6) 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one a)
7) 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol a)
a) origin: Firmenich SA, Geneva, Switzerland
The addition of 4000 parts by weight of Mix 1 (as defined in Example 1) to the above-described composition imparted to the latter a reinforced rooty/powdery characters by blending very well with both amber (Ambrox®) and powdery-violet (Iralia® Total) elements present in the original formula.
When instead of Mix 1 was added the same amount of a mixture of 1-((4aRS,8RS,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one, 1-((4aRS,8RS,8aRS)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one, 1-((4aRS,8RS,8aSR)-4a,8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one and 1-((4aRS,8RS,8aRS)-4a,8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one (20:12:39:28), then said ingredient provided a similar effect to the one of Mix 1 with the lighter powdery character. This ingredient is less powerful and more unisex so more versatile.
When instead of Mix 1 was added the same amount of prior art's 1-[(4aRS,8SR,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydro-2-naphthalenyl]ethanone, then this ingredient pushed the fruity-Dasmascone (Damascone Alpha) element (an element not observed with the invention's compounds) and twists the woody accord in a more cedar like direction. This ingredient is the less powerful.
| Number | Date | Country | Kind |
|---|---|---|---|
| 17164797 | Apr 2017 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/058205 | 3/29/2018 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/185012 | 10/11/2018 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4008184 | Maurer | Feb 1977 | A |
| 4396670 | Sinclair | Aug 1983 | A |
| Number | Date | Country |
|---|---|---|
| 2203642 | May 1974 | FR |
| 1411703 | Oct 1975 | GB |
| 0141915 | Jun 2001 | WO |
| Entry |
|---|
| Tebbaa et al, Short and efficient hemisynthesis of alpha-eudesmol and cryptomeridiol, May 11, 2011, Tetrahedron Letters, 52, 3769-3771 (Year: 2011). |
| STIC references, varied sources (Year: 1965). |
| Belhassen et al,“Volatile constutuents of vetiver: a review”, Flavour and Fragrance Journal, Dec. 22, 2014, pp. 26-82, 30-1. |
| International Search Report and Written Opinion for International Application No. PCT/EP2018/058205, dated Jun. 13, 2018, 13 pages. |
| Bone et al, “Microencapsulated Fragrances in Melamine Formaldehyde Resins”, Chimia, 2011, pp. 177-181, 65-3. |
| Lee et al,“Microencapsulation of fragrant oil via in situ polymerization: effects of pH and melamine-fomaldehyde molar ratio”, Journal of Microencapsulation, 2002, pp. 559-569,19-5. |
| Kulkarini et al,“Synthesis of a ketodicarboxylic acid related to elemol and epidihydroeudesmol”, Tetrahedron, 1965, pp. 1167-1173, vol. 21. |
| Maurer et al, “Zur Kennnis der sesquiterpenoiden C12-Ketone des ätherischen Öls von Vetiveria zizanioides (L.) Nash”, Helvetica Chimica Acta, 1972,p. 2371-2382, 55.—English Abstract Only. |
| Dietrich et al, “Amino Resin Microcapsules”, Acta Polymerica, 1989, p. 243-251, vol. 40-4. |
| Dietrich et al, “Amino Resin Microcapsules”, Acta Polymerica, 1990, p. 91, vo1. 41-2. |
| Dietrich et al, “Amino Resin Microcapsules”, Acta Polymerica, 1989, p. 683-690, vol. 40-11. |
| Number | Date | Country | |
|---|---|---|---|
| 20200109348 A1 | Apr 2020 | US |
