Patent Publication Number: US-2023146062-A1

Title: Fragrance compositions containing norbornene derivatives for personal care products

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is a divisional of U.S. application Ser. No. 17/149,912, filed Jan. 15, 2021, now allowed, which claims the benefit of U.S. Provisional Application No. 62/961,300, filed Jan. 15, 2020, both of which are incorporated herein by reference in their entirety. 
    
    
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
     Embodiments in accordance with the present invention relate generally to a variety of norbornene ester and/or carbonate derivatives exhibiting olfactive properties and are suitable as fragrance ingredients. More specifically, this invention relates to various fragrance compositions containing a variety of functionalized norbornene (NB) ester and carbonate compounds for use as perfume augmenting, modifying, enhancing, and imparting compositions. The compositions of this invention are therefore useful in a variety of perfumed products including but not limited to a variety of persona care products including shampoo, lotions, soaps, deodorants, skin care products, hair products, sanitary products, and the like. 
     Description of the Art 
     A variety of fragrance compounds are used as perfumes in the market, several of which are derived from natural sources. However, a key drawback of such natural sources is continuous sustained availability of the raw materials. Another drawback is that there is always a batch to batch variation in the quality of the products. A further drawback of such naturally occurring fragrance compounds is the high cost associated with their purification because of low yield of isolation from their natural sources. It should also be noted that some of the naturally occurring fragrance compounds may be toxic to animals and people in their natural state requiring tedious methodologies for their isolation and purification. See, for example, H. M. Berven, Fragrance, Vol. 42, 46-64 (2017). 
     As a result, there has been considerable research efforts to find new cost effective synthetic, non-toxic fragrance compounds and compositions that can meet the ever growing demand for such compounds/compositions. More importantly, such synthetically made fragrance compounds/compositions are expected to maintain uniform product quality with no batch to batch variations, and can be tailored to be environmentally friendly. As a result, such synthetic fragrance compounds/compositions may thus provide solution to changing environmental landscape, and may alleviate some of the environmental concerns by reducing waste generated by currently used purification processes to make naturally occurring fragrance compounds. 
     U.S. Pat. No. 4,119,577 discloses certain substituted norbornane perfume compositions. U.S. Pat. No. 4,374,054 discloses a variety of norbornene and norbornane carboxylic acid derivatives useful as perfumery components. U.S. Pat. No. 4,128,509 discloses a fragrance composition containing 1-(norborn-2-yl)-2-methyl-butan-3-ol, which supposedly exhibits similar odor as that of a naturally occurring mixture of α- and β-santalol, commonly found in sandalwood oil. See also, U.S. Pat. No. 4,229,600. U.S. Pat. No. 4,218,347 discloses methyl substituted or unsubstituted norbornene aldehyde carboxylic acid esters suitable as a perfuming and/or a flavoring ingredient. U.S. Pat. No. 4,351,748 discloses a series of norbornane and norbornene derivatives having epoxy carboxylic acid ester side chain, which are useful as perfuming ingredients. Finally, U.S. Pat. No. 4,132,677 discloses perfume compositions containing cyanoethylidenenorbornenes. 
     Thus, it is an object of this invention to provide a variety of functionalized norbornene derivatives useful as fragrance components in a variety of perfumed products and perfumery applications. 
     Other objects and further scope of the applicability of the present invention will become apparent from the detailed description that follows. 
     SUMMARY OF THE INVENTION 
     It has now been found that a fragrance composition can be made using a variety of functionalized norbornene compounds of formulae (IA) or (IB). Accordingly, there is provided a fragrance composition for personal care product, said composition comprising: 
     a) an olfactory acceptable amount of at least one compound in the form of any one of its enantiomers or a mixture thereof, which is selected from the group consisting of: 
     a compound of formula (IA): 
     
       
         
         
             
             
         
       
     
     and 
     a compound of formula (IB): 
     
       
         
         
             
             
         
       
     
     wherein: 
     each m is independently an integer from 0 to 4; 
     each R 1  and R 2  is independently selected from the group consisting of: hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 5 )alkyl, hydroxymethyl, hydroxyethyl and linear or branched hydroxy(C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 5 )alkoxy, perfluoro(C 1 -C 12 )alkyl, substituted or unsubstituted (C 3 -C 5 )cycloalkyl, substituted or unsubstituted (C 3 -C 5 )cycloalkyl(C 1 -C 5 )alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted phenyl(C 1 -C 5 )alkyl; 
     each R 3  is independently selected from the group consisting of: hydrogen, methyl, ethyl, linear or branched (C 3 -C 5 )alkyl, perfluoro(C 1 -C 12 )alkyl, substituted or unsubstituted (C 3 -C 5 )cycloalkyl, substituted or unsubstituted (C 3 -C 5 )cycloalkyl(C 1 -C 5 )alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted phenyl(C 1 -C 5 )alkyl; 
     b) at least one of a fragrance carrier and a fragrance base selected from the group consisting of alpha-isomethyl ionone, aphermate, bacdanol, 6,7-dihydo-1,1,2,3,3-pentamethyl-4(5H)-indanone (cashmeran), cedarwood oil, galaxolide, hexyl cinnamic aldehyde, citronellol, kohinool, linalool, linalyl acetate, styrallyl acetate, lilial, triplal, orange terpenes, musk ketone, ethylene brassylate, ethyl vanillin, coumarin, helional, hedione, exaltolide, patchouli oil, ambroxan, beta-ionone, geraniol, cyclamen aldehyde, phenyl ethyl alcohol, benzyl acetate, benzaldehyde, allyl cyclohexyl propionate, cis-3-hexenol, cis-3-hexenyl acetate, hexyl acetate and ethyl alcohol; and 
     c) optionally at least one fragrance adjuvant. 
     In another aspect of this invention there is further provided 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 one compound of formulae (IA) or (IB) in the form of any one of their enantiomers or stereoisomers or a mixture thereof. 
    
    
     DETAILED DESCRIPTION 
     The terms as used herein have the following meanings: 
     As used herein, the articles “a,” “an,” and “the” include plural referents unless otherwise expressly and unequivocally limited to one referent. 
     Since all numbers, values and/or expressions referring to quantities of ingredients, reaction conditions, etc., used herein and in the claims appended hereto, are subject to the various uncertainties of measurement encountered in obtaining such values, unless otherwise indicated, all are to be understood as modified in all instances by the term “about.” 
     Where a numerical range is disclosed herein such range is continuous, inclusive of both the minimum and maximum values of the range as well as every value between such minimum and maximum values. Still further, where a range refers to integers, every integer between the minimum and maximum values of such range is included. In addition, where multiple ranges are provided to describe a feature or characteristic, such ranges can be combined. That is to say that, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. For example, a stated range of from “1 to 10” should be considered to include any and all sub-ranges between the minimum value of 1 and the maximum value of 10. Exemplary sub-ranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, etc. 
     As used herein, the bond symbol “ ” in various structures shown below denotes that the stereochemistry at this position is not determined and may constitute all possible stereoisomers, including “exo” or “endo” isomers. Accordingly, whenever a structure shown with the symbol “ ” means that it includes all possible stereoisomers at that configuration. 
     The expression “stereoisomers” is a general term used for all isomers of the individual molecules that differ only in the orientation of their atoms in space. Typically, it includes mirror image isomers that are usually formed due to at least one asymmetric center, (enantiomers). In addition, as noted above, the compounds of formulae (IA) to (IC) may exist in two different forms “exo” and “endo” configurations merely because of their spatial orientation. Where the compounds according to the invention possess two or more asymmetric centers, they may additionally exist as diastereoisomers, also certain individual molecules may exist as geometric isomers (cis/trans). Similarly, certain compounds of this invention may exist in a mixture of two or more structurally distinct forms that are in rapid equilibrium, commonly known as tautomers. Representative examples of tautomers include keto-enol tautomers, phenol-keto tautomers, nitroso-oxime tautomers, imine-enamine tautomers, etc. It is to be understood that all such isomers and mixtures thereof in any proportion are encompassed within the scope of the present invention. 
     As used herein, the expression “alkyl” means a saturated, straight-chain or branched-chain hydrocarbon substituent having the specified number of carbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyl, tert-butyl, and so on. Derived expressions such as “alkoxy”, “thioalkyl”, “alkoxyalkyl”, “hydroxyalkyl”, “alkylcarbonyl”, “alkoxycarbonylalkyl”, “alkoxycarbonyl”, “diphenylalkyl”, “phenylalkyl”, “phenylcarboxyalkyl” and “phenoxyalkyl” are to be construed accordingly. 
     As used herein, the expression “cycloalkyl” includes all of the known cyclic groups. Representative examples of “cycloalkyl” includes without any limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derived expressions such as “cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl” are to be construed accordingly. 
     As used herein, the expression “perfluoroalkyl” means that all of the hydrogen atoms in said alkyl group are replaced with fluorine atoms, again having the specified number of carbon atoms. Illustrative examples include trifluoromethyl and pentafluoroethyl, and straight-chained or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl groups. The derived expression, “perfluoroalkoxy”, is to be construed accordingly. It should further be noted that certain of the alkyl groups as described herein, such as for example, “alkyl” may partially be fluorinated, that is, only portions of the hydrogen atoms in said alkyl group are replaced with fluorine atoms and shall be construed accordingly. 
     As used herein, the expression “aryl” means substituted or unsubstituted aromatic groups such as phenyl, naphthyl, anthracenyl, and the like. Specific examples of substituted phenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. “Substituted phenyl” or “substituted naphthyl” also include any of the possible substituents as further defined herein or one known in the art. 
     As used herein, the expression “arylalkyl” means that the aryl as defined herein is further attached to alkyl as defined herein. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like. 
     As used herein, the expression “alkenyl” means a non-cyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, and includes ethenyl and straight-chained or branched propenyl, butenyl, pentenyl and hexenyl groups. Derived expression, “arylalkenyl” and five membered or six membered “heteroarylalkenyl” is to be construed accordingly. Illustrative examples of such derived expressions include furan-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like. 
     As used herein the expression “acyl” shall have the same meaning as “alkanoyl”, which can also be represented structurally as “R—CO—,” where R is an “alkyl” as defined herein having the specified number of carbon atoms. Additionally, “alkylcarbonyl” shall mean same as “acyl” as defined herein. Specifically, “(C 1 -C 4 )acyl” shall mean formyl, acetyl or ethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as “acyloxy” and “acyloxyalkyl” are to be construed accordingly. 
     “Halogen” or “halo” means chloro, fluoro, bromo, and iodo. 
     In a broad sense, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a few of the specific embodiments as disclosed herein, the term “substituted” means substituted with one or more substituents independently selected from the group consisting of (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 1 -C 6 )perfluoroalkyl, phenyl, hydroxy, —CO 2 H, an ester, an amide, (C 1 -C 6 )alkoxy, (C 1 -C 6 )thioalkyl and (C 1 -C 6 )perfluoroalkoxy. However, any of the other suitable substituents known to one skilled in the art can also be used in these embodiments. 
     It should be noted that any atom with unsatisfied valences in the text, schemes, examples and tables herein is assumed to have the appropriate number of hydrogen atom(s) to satisfy such valences. 
     By the term “fragrance” or “fragrance compound” or “fragrance composition” is meant a compound or a composition that exhibits pleasant, lasting floral, fruity, woody, spicy, nutty, herbal aroma, which is useful in the preparation of fragrance compositions and perfumed products. 
     By the term “effective olfactory” or “effective olfactive” or “effective odoriferous” amount of a compound is meant a sufficient amount of the compound to impart desirable sense of smell to the composition. 
     As used herein, the expression “fragrance carrier” or “fragrance base” means a non-toxic solvent, dispersant, excipient, adjuvant, or other material which is mixed with the compounds of formulae (IA) or (IB) as described herein in order to permit the formation of a fragrance composition, as further disclosed herein. 
     Accordingly, in accordance with the practice of this invention there is provided a fragrance composition for personal care product, said composition comprising: 
     a) an olfactory acceptable amount of at least one compound in the form of any one of its enantiomers or a mixture thereof, which is selected from the group consisting of: 
     a compound of formula (IA): 
     
       
         
         
             
             
         
       
     
     and 
     a compound of formula (IB): 
     
       
         
         
             
             
         
       
     
     wherein: 
     each m is independently an integer from 0 to 4; 
     each R 1  and R 2  is independently selected from the group consisting of: hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 5 )alkyl, hydroxymethyl, hydroxyethyl and linear or branched hydroxy(C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 5 )alkoxy, perfluoro(C 1 -C 12 )alkyl, substituted or unsubstituted (C 3 -C 5 )cycloalkyl, substituted or unsubstituted (C 3 -C 5 )cycloalkyl(C 1 -C 5 )alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted phenyl(C 1 -C 5 )alkyl; 
     each R 3  is independently selected from the group consisting of: hydrogen, methyl, ethyl, linear or branched (C 3 -C 5 )alkyl, perfluoro(C 1 -C 12 )alkyl, substituted or unsubstituted (C 3 -C 5 )cycloalkyl, substituted or unsubstituted (C 3 -C 5 )cycloalkyl(C 1 -C 5 )alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted phenyl(C 1 -C 5 )alkyl; 
     b) at least one of a fragrance carrier and a fragrance base selected from the group consisting of alpha-isomethyl ionone, aphermate, bacdanol, cashmeran, cedarwood oil, galaxolide, hexyl cinnamic aldehyde, citronellol, kohinool, linalool, linalyl acetate, styrallyl acetate, lilial, triplal, orange terpenes, musk ketone, ethylene brassylate, ethyl vanillin, coumarin, helional, hedione, exaltolide, patchouli oil, ambroxan, beta-ionone, geraniol, cyclamen aldehyde, phenyl ethyl alcohol, benzyl acetate, benzaldehyde, allyl cyclohexyl propionate, cis-3-hexenol, cis-3-hexenyl acetate, hexyl acetate and ethyl alcohol; and 
     c) optionally at least one fragrance adjuvant. 
     The compounds employed in the composition of this invention are themselves known in the literature or can be prepared by any of the known methods in the art to make such or similar types of compounds. In general, the compounds of formulae (IA) or (IB) can be prepared by employing cyclopentadiene and a suitable substituted olefin of formula (IC), where Z is any one of the side chains as represented in structural formulae (IA) or (IB), and reacting them together under Diels Alder reaction conditions to form a compound of formulae (IA) or (IB) as summarized in Scheme I. 
     
       
         
         
             
             
         
       
     
     The Diels Alder reaction is generally carried out at higher temperatures in a closed reactor by mixing suitable amounts of cyclopentadiene with a desirable substituted olefin of formula (IC) which facilitates the (4n+2n) addition of the double bonds to form the compounds of formula (IA) or (IB). Generally, such reactions are carried out in an autoclave at higher temperatures and optionally in the presence of a suitable solvent. The resulting product is generally a mixture of exo- and endo-isomers of formulae (IA) or (IB). These isomers may exhibit different olfactive properties and therefore, in some embodiments only one of the isomers may be more suitable in the fragrance compositions of this invention. In some other embodiments both exo and endo isomers may be employed equally readily to form the olfactively effective fragrance compositions of this invention. 
     In some embodiments the fragrance composition according to the present invention contains one or more compounds of formulae (IA) or (IB), wherein m is 1 or 2; each of R 1  and R 2  is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, phenoxy, hydroxymethyl and hydroxyethyl; R 3  is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl. 
     Non-limiting examples of such compounds of formulae (IA) or (IB) that can be employed in the fragrance composition of this invention include all geometric and stereoisomers of the following: 
     
       
         
         
             
             
         
       
     
     In general, the fragrance compositions in accordance with the present invention encompass at least one of the above described compounds of formulae (IA) or (IB) and if needed additional one or more compounds of formulae (IA) or (IB) in order to provide the intended olfactive property to such embodiments that are appropriate and desirable for the use for which such embodiments are directed, thus such embodiments are tailorable to a variety of specific applications. 
     For example, as already discussed above, proper combination of distinctive monomers of formulae (IA) or (IB) makes it possible to tailor a composition having the desirable olfactive property having utility in different fragrance compositions. That is, depending upon the intended applications, including perfumed products, such as, perfumes, colognes, soaps, detergents, candles, air fresheners, trash bags, tissues, deodorants, lotions, skin care products, hair products, sanitary products, cleaning products, etc., the compositions can be tailored to provide such intended benefits. 
     Any of the amounts of one or more compounds of formulae (IA) or (IB) can be employed in the perfuming composition of this invention. Generally, such desired olfactory effects can be brought about by employing even less than one part by weight of any one of the compounds of formulae (IA) to (IB) in one hundred parts of the perfuming composition. 
     Accordingly, in some embodiments the fragrance composition of this invention contains at least one compound of formula (IA) or one compound of formula (IB), which is present in the composition at less than one parts by weight per one hundred parts by weight of the total composition. 
     In some other embodiments, the fragrance composition of this invention contains at least one compound of formula (IA) or one compound of formula (IB) at least in the amount of about one parts by weight per one hundred parts by weight of the total composition. 
     In yet some other embodiments the fragrance composition according to this invention contains at least one compound of formula (IA) or one compound of formula (IB) at least in the amount of about two parts by weight per one hundred parts by weight of the total composition. 
     In some other embodiments the fragrance composition according to this invention contains at least one compound of formula (IA) or one compound of formula (IB) at less than three parts by weight per one hundred parts by weight of the total composition. 
     Accordingly, there is further provided a perfuming composition comprising i) at least one compound of formula (IA) or at least one compound of formula (IB), as defined herein; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and iii) optionally at least one perfumery adjuvant. 
     In some other embodiments, there is also provided a perfuming consumer product comprising: i) at least one compound of formula (IA) or at least one compound of formula (IB), as defined herein; and ii) a perfumery consumer base. 
     Any of the known perfumery consumer base that provides the intended benefit for such compositions can be employed in the perfuming consumer product according to the present invention. Exemplary perfumery consumer base include but not limited to a perfume, a fabric care product, a body-care product, an air care product or a home care product. 
     In a further non-limiting examples of a perfuming consumer product according to the present invention encompasses a perfumery consumer base selected from a fine perfume, a cologne, an after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a shampoo, a coloring preparation, a hair spray, a vanishing cream, a deodorant or antiperspirant, a perfumed soap, shower or bath mousse, oil or gel, a hygiene product, an air freshener, a “ready to use” powdered air freshener, a wipe, a dish detergent or hard-surface detergent. 
     In an additional aspect of this invention there is further provided 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 one compound of formulae (IA) to (IB), as defined herein, including the form of any one of its enantiomers or a mixture thereof. 
     Any one or more of the specific compounds of formulae (IA) to (IB) as described hereinabove can be used in the method according to the present invention. 
     In a further embodiment of this invention, the composition contains any of the fragrance carrier and a fragrance base and optionally at least one fragrance adjuvant that would bring about the intended benefit. Generally, such suitable fragrance carriers include a suitable gaseous or liquid carriers, among others. Gaseous carriers are generally used in aerosol compositions and are inert to compositions of this invention. Non-limiting examples of gaseous carriers include air, nitrogen, carbon dioxide, any suitable organic solvent, water, and the like. 
     The compounds of formulae (IA) to (IB) may be used alone, as mixtures thereof, in combination with a fragrance carrier and/or a fragrance base material. As used herein, the “fragrance base material” includes all known odorant molecules selected from the extensive range of natural products, and synthetic molecules currently available, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and/or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorants in fragrance compositions, for example, carrier materials, and other auxiliary agents commonly used in the art. 
     As used herein, “fragrance composition” means any composition comprising at least one compound of formulae (IA) to (IB) and a fragrance base material and/or a fragrance carrier. For example, a diluent conventionally used in conjunction with odorants, such as dipropylene glycol (DPG), isopropyl myristate (IPM), triethyl citrate (TEC), alcohol (e.g., ethanol), and the like may be used as fragrance carrier. 
     Non-limiting examples of known odorant molecules, which may be combined with the compounds of formulae (IA) to (IB) as herein defined include the following: essential oils and extracts, e.g. castoreum, costus root oil, oak moss absolute, geranium oil, tree moss absolute, basil oil, fruit oils, such as bergamot oil and mandarine oil, myrtle oil, palmarose oil, patchouli oil, petitgrain oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil or ylang-ylang oil; alcohols, e.g. cinnamic alcohol, cis-3-hexenol, citronellol, EBANOL™, eugenol, farnesol, geraniol, SUPER MUGUET™, linalool, menthol, nerol, phenylethyl alcohol, rhodinol, SANDALORE™, terpineol or TIMBEROL™. Various known aldehydes and ketones used as fragrance compounds and/or fragrance enhancing compounds, including but not limited to AZURONE® [7-(3-methylbutyl)-1,5-benzodioxepin-3-one], anisaldehyde, α-amylcinnamaldehyde, GEORGYWOOD™, hydroxycitronellal, ISO E® Super, ISORALDEINE®, HEDIONE®, LILIAL®, maltol, methyl cedryl ketone, methylionone, verbenone, or vanillin. Various known ether and acetals used as fragrance compounds and/or fragrance enhancing compounds, including but not limited to AMBROX®, geranyl methyl ether, rose oxide, or SPIRAMBRENE®. Various known esters and lactones used as fragrance compounds and/or fragrance enhancing compounds, including but not limited to benzyl acetate, cedryl acetate, γ-decalactone, HELVETOLIDE®, γ-undecalactone or vetivenyl acetate; macrocycles, e.g., Ambrettolide, ethylene brassylate or EXALTOLIDE®. Various known heterocycles are used as fragrance compounds and/or fragrance enhancing compounds, including but not limited to isobutylchinoline. 
     The compounds according to formulae (IA) to (IB) may be used in a broad range of perfumed products, 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, if employed. The proportion is typically from 0.1 to 10 weight percent of the application. In one embodiment, compounds of the present invention may be employed in a fabric softener in an amount of from 0.001 to 0.1 weight percent. In another embodiment, compounds of the present invention may be used in fine perfumery in amounts from 0.01 to 20 weight percent (e.g., up to about 10 weight percent). In some other embodiments, between 0.01 and 5 weight percent. It should be noted however that these values are given only by way of example, since the experienced perfumer may also achieve effects or may create intended benefit with lower or higher concentrations. 
     The compounds as described hereinabove may be employed in a consumer product base simply by directly mixing at least one compound of formulae (IA) to (IB), or a fragrance composition with the consumer product base, or they may, in an earlier step, be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures 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, or the like, and then mixed with the consumer product base. 
     Thus, the invention additionally provides a method of manufacturing a perfumed product, comprising the incorporation of a compound of formulae (IA) to (IB), as a fragrance ingredient, either by directly admixing the compound to the consumer product base or by admixing a fragrance composition comprising a compound of formulae (IA) to (IB), 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 the present invention as hereinabove described the odor notes of a consumer product base will be improved, enhanced, or modified. 
     Thus, the invention furthermore provides a method for improving, enhancing or modifying a consumer product base by means of the addition thereto of an olfactively acceptable amount of at least one compound of formulae (IA) to (IB). 
     The invention also provides a perfumed product comprising: a) as odorant at least one compound of formulae (IA) to (IB); and b) a consumer product base. 
     As used herein, “consumer product base” means a composition for use as a consumer product to fulfill specific actions, such as cleaning, softening, and caring or the like. Examples of such products include fine perfumery, e.g., perfume and eau de toilette; fabric care, household products and personal care products such as laundry care detergents, rinse conditioner, personal cleansing composition, detergent for dishwasher, surface cleaner; laundry products, e.g., softener, bleach, detergent; body-care products, e.g., shampoo, shower gel; air care products and cosmetics, e.g., deodorant, vanishing cream or lotion. This list of products is given by way of illustration, and is not to be regarded as being in any way limiting. 
     Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature. In addition, one of skill in the art will readily appreciate that any such material be non-toxic especially in a household product and otherwise non-deleterious particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used is not caused to have unacceptable aroma and taste nuances. Such materials may in general be characterized as flavoring adjuvants or vehicles comprising broadly stabilizers, thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers. 
     Stabilizer compounds include preservatives, for example, sodium chloride; antioxidants, such as for example, calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene (2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like and sequestrants, e.g., citric acid. 
     Thickener compounds include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, e.g., agar agar, carrageenan; cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth; gelatin, proteinaceous materials; lipids; carbohydrates; starches, pectins and emulsifiers, e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose corn syrup and the like. 
     Surface active agents include emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid, myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like. 
     Conditioners include compounds such as bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like; colorants, e.g., carminic acid, cochineal, turmeric and  curcuma  and the like; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphate; enzymes; yeast foods, e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like. 
     Other flavorants and flavor intensifiers include aldehydes, esters, natural oils, alcohols, sulfides, ketones, lactones, carboxylic acids and hydrocarbons such as heliotropin, terpinenol-4, benzaldehyde, phenyl acetaldehyde, benzyl formate, cis-3-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil, limonene, gum camphor, isobornyl acetate, borneol, cinnamic aldehyde, cuminic aldehyde, furfural, methyl cinnamate,  cassia  oil, parahydroxybenzyl acetate, dimethyl sulfide, alphaionone, acetic acid, isobutyl acetate, acetone, butyric acid, formic acid, valeric acid, amyl acetate, amyl butyrate, anethol, benzyl salicylate, diacetyl, dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate, ethyl valerate, cis-3-hexen-1-ol, 2-hexenyl acetate, 2-hexenyl butyrate, hexyl butyrate, 4-(p-hydroxyphenyl)-2-butanone, betaionone, isobutyl cinnamate, lemon essential oil, methyl butyrate, methyl caproate, methyl disulfide, methyl p-naphthyl ketone, orris butter, rose absolute, terpenyl acetate, gamma-undecalactone, vanilla and alcohol. 
     The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., and should, (i) be organoleptically compatible with the compounds of formulae (IA) to (IB) of this invention by not covering or spoiling the organoleptic properties (aroma and/or taste) thereof; (ii) be non-reactive with the compounds of formulae (IA) to (IB) of this invention and (iii) be capable of providing an environment in which the compounds of formulae (IA) to (IB) of this invention can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the ultimate product to which the flavor and/or aroma are to be imparted, modified, altered or enhanced. 
     Accordingly, there is provided a perfuming consumer product comprising: i) at least one compound of formula (IA), as defined herein; and ii) a perfumery consumer base. 
     In some other embodiments of this invention there is also provided a perfuming consumer product comprising: i) at least one compound of formula (IB), as defined herein; and ii) a perfumery consumer base. 
     In some embodiments, the perfuming consumer product according to this invention is selected from the group consisting of an after-shave lotion, a liquid or solid detergent, toilet water, shampoo, body lotion, sun lotion, a tanning lotion, lip balm, a hair care product, a vanishing cream, a deodorant or antiperspirant, a perfumed soap, shower or bath mousse, oil or gel, a hygiene product, a cosmetic product and a personal care product. 
     In some embodiments the perfuming consumer product comprises: i) at least one compound selected from the group consisting of ethyl 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoate (EPEsNB) and (bicyclo[2.2.1]hept-5-en-2-yl)methyl ethyl carbonate (NBEtCarb); and ii) at least one perfumery consumer base selected from the group consisting of alpha-isomethyl ionone, aphermate, bacdanol, cashmeran, cedarwood oil, galaxolide, hexyl cinnamic aldehyde, citronellol, kohinool, linalool, linalyl acetate, styrallyl acetate, lilial, triplal, orange terpenes, musk ketone, ethylene brassylate, ethyl vanillin, coumarin, helional, hedione, exaltolide, patchouli oil, ambroxan, beta-ionone, geraniol and cyclamen aldehyde. 
     In some other embodiments the perfuming consumer product is selected from the group consisting of shampoo, body lotion, sun lotion, tanning lotion and lip balm. 
     In yet some other embodiments the perfuming consumer product according to this invention contains ethyl 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoate (EPEsNB). 
     In yet some other embodiments the perfuming consumer product according to this invention contains (bicyclo[2.2.1]hept-5-en-2-yl)methyl ethyl carbonate (NBEtCarb). 
     The following examples are detailed descriptions of methods of preparation and use of compositions of the present invention. The detailed preparations fall within the scope of, and serve to exemplify, the more generally described methods of preparation set forth above. The examples are presented for illustrative purposes only, and are not intended as a restriction on the scope of the invention. 
     EXAMPLES 
     The following abbreviations have been used hereinbefore and hereafter in describing some of the compounds, instruments and/or methods employed to illustrate certain of the embodiments of this invention: NBEtCarb—(bicyclo[2.2.1]hept-5-en-2-yl)methyl ethyl carbonate; EPEsNB—ethyl 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoate; BHT—butylated hydroxytoluene; DPG—dipropylene glycol. 
     Various compounds of formulae (IA) to (IB) as described herein are either commercially available or can be readily prepared following the procedures as described herein or following the procedures as reported in literature, see for example, U.S. Pat. No. 4,374,054. 
     Example 1 
     Preparation of a Perfuming Composition Containing EPEsNB 
     A fragrance composition was developed containing EPEsNB and various other components as summarized in Table 1. All of the materials therein were used in parts by weight taken in a suitable container and mixed together slowly while stirring to disperse evenly all of the ingredients. The olfactory effects were then evaluated. The composition exhibited a sweet, tropical, lifting, sunshine, outdoors odor. It is evident from this evaluation that this composition is suitable in a variety of tanning lotions and shampoos. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Material 
                 % w/w 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 alpha-isomethyl ionone 
                 2.09 
               
               
                   
                 Aphermate 
                 0.15 
               
               
                   
                 Bacdanol 
                 1.98 
               
               
                   
                 Benzyl salicylate 
                 1.79 
               
               
                   
                 Bergamot oil 
                 4.58 
               
               
                   
                 beta-ionone 
                 0.55 
               
               
                   
                 Cashmeran 
                 2.04 
               
               
                   
                 Cedarwood oil Chinese 
                 1.7 
               
               
                   
                 cis-3-Hexenyl salicylate 
                 1.09 
               
               
                   
                 Coumarin 
                 1.42 
               
               
                   
                 Dihydro-beta-ionone 
                 1.19 
               
               
                   
                 Dipropylene glycol 
                 18.915 
               
               
                   
                 Ethyl vanillin 
                 0.82 
               
               
                   
                 Ethylene brassylate 
                 1.8 
               
               
                   
                 Florosa 
                 0.56 
               
               
                   
                 Galaxolide 
                 10.24 
               
               
                   
                 Geranium oil Egyptian 
                 0.67 
               
               
                   
                 Hedione 
                 11.68 
               
               
                   
                 Helional 
                 0.68 
               
               
                   
                 Iso-e-super 
                 20.25 
               
               
                   
                 Lilial 
                 4.29 
               
               
                   
                 Linalool 
                 4.05 
               
               
                   
                 Methyl pamplemousse 
                 0.15 
               
               
                   
                 Phenoxanol 
                 1.52 
               
               
                   
                 Phenyl ethyl alcohol 
                 2.38 
               
               
                   
                 Raspberry ketone 
                 0.078 
               
               
                   
                 Styrallyl acetate 
                 0.3 
               
               
                   
                 Vanillin 
                 0.56 
               
               
                   
                 Ethyl acetate (1% in DPG) 
                 0.67 
               
               
                   
                 Ethyl-2-methyl butyrate 
                 0.047 
               
               
                   
                 Cis-3-Hexenyl acetate (1% in DPG) 
                 0.53 
               
               
                   
                 Ethyl linalool 
                 0.4 
               
               
                   
                 EPEsNB 
                 0.83 
               
               
                   
                 Total 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     Example 2 
     Preparation of a Perfuming Composition Containing NBEtCarb 
     A fragrance composition was developed containing NBEtCarb and various other components as summarized in Table 2. All of the materials therein were used in parts by weight taken in a suitable container and mixed together slowly while stirring to disperse evenly all of the ingredients. The olfactory effects were then evaluated. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Material 
                 % w/w 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 Agrumex 
                 5.06 
               
               
                   
                 Ambroxan 
                 0.42 
               
               
                   
                 Benzyl salicylate 
                 4.15 
               
               
                   
                 Bergamot oil 
                 0.97 
               
               
                   
                 beta-Damascone 
                 0.025 
               
               
                   
                 BHT 
                 0.51 
               
               
                   
                 Boisambrene forte 
                 7.28 
               
               
                   
                 Cedramber 
                 0.29 
               
               
                   
                 Dihydromyrcenol 
                 2.18 
               
               
                   
                 Dimethyl benzyl carbinyl butyrate 
                 0.15 
               
               
                   
                 Dipropylene glycol 
                 4.05 
               
               
                   
                 Dynascone 
                 0.51 
               
               
                   
                 Ethyl maitol 
                 1.38 
               
               
                   
                 Ethylene brassylate 
                 0.26 
               
               
                   
                 Galaxolide (50% in IPM) 
                 10.75 
               
               
                   
                 gamma-Nonalactone 
                 0.081 
               
               
                   
                 Hedione 
                 4.46 
               
               
                   
                 Iso E-Super 
                 45.924 
               
               
                   
                 Lilial 
                 0.24 
               
               
                   
                 Linalool 
                 0.21 
               
               
                   
                 Manzanate (1% in DPG) 
                 2.24 
               
               
                   
                 Orange terpenes 
                 2.34 
               
               
                   
                 Patchouli oil 
                 2.94 
               
               
                   
                 Piconia 
                 2.76 
               
               
                   
                 NBEtCarb 
                 0.82 
               
               
                   
                 Total 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     The composition exhibited an intense sweet fruity, particularly that of a pineapple fragrance. It is evident from this evaluation that this composition is suitable in a variety of lotions, including body lotion, sun lotion, shampoos and lip balm. 
     Although the invention has been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.