MXPA99001723A - Fragrance delivery systems for personal care articles - Google Patents
Fragrance delivery systems for personal care articlesInfo
- Publication number
- MXPA99001723A MXPA99001723A MXPA/A/1999/001723A MX9901723A MXPA99001723A MX PA99001723 A MXPA99001723 A MX PA99001723A MX 9901723 A MX9901723 A MX 9901723A MX PA99001723 A MXPA99001723 A MX PA99001723A
- Authority
- MX
- Mexico
- Prior art keywords
- substituted
- unsubstituted
- dimethyl
- oxo
- fragrance
- Prior art date
Links
- 239000003205 fragrance Substances 0.000 title claims abstract description 154
- 239000000203 mixture Substances 0.000 claims abstract description 211
- 239000002994 raw material Substances 0.000 claims abstract description 114
- 230000001166 anti-perspirative effect Effects 0.000 claims abstract description 7
- 239000003213 antiperspirant Substances 0.000 claims abstract description 7
- -1 spreaders Substances 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000000304 alkynyl group Chemical group 0.000 claims description 18
- 239000002304 perfume Substances 0.000 claims description 15
- 239000003974 emollient agent Substances 0.000 claims description 12
- 239000004615 ingredient Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000004166 Lanolin Substances 0.000 claims description 8
- 125000005275 alkylenearyl group Chemical group 0.000 claims description 8
- 235000019388 lanolin Nutrition 0.000 claims description 8
- 229940039717 lanolin Drugs 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 7
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- RCKQXBGTLGUODO-UHFFFAOYSA-N 2,6-dimethyloct-7-en-2-yl 3-(4-methoxyphenyl)-3-oxopropanoate Chemical compound COC1=CC=C(C(=O)CC(=O)OC(C)(C)CCCC(C)C=C)C=C1 RCKQXBGTLGUODO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- YMXBKCORIPTXIB-UHFFFAOYSA-N 2,6-dimethyloct-7-en-2-yl 3-oxobutanoate Chemical compound C=CC(C)CCCC(C)(C)OC(=O)CC(C)=O YMXBKCORIPTXIB-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003082 abrasive agent Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 3
- 239000003899 bactericide agent Substances 0.000 claims description 3
- 230000008901 benefit Effects 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 239000003349 gelling agent Substances 0.000 claims description 3
- 239000003883 ointment base Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000003380 propellant Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- NSAZFRMABVPCLN-UHFFFAOYSA-N 2,6-dimethyloct-7-en-2-yl 3-naphthalen-2-yl-3-oxopropanoate Chemical compound C1=CC=CC2=CC(C(=O)CC(=O)OC(C)(C)CCCC(C)C=C)=CC=C21 NSAZFRMABVPCLN-UHFFFAOYSA-N 0.000 claims description 2
- RSZWOUVULWCHFO-UHFFFAOYSA-N 3,7-dimethylocta-2,6-dienyl 3-oxodecanoate Chemical compound CCCCCCCC(=O)CC(=O)OCC=C(C)CCC=C(C)C RSZWOUVULWCHFO-UHFFFAOYSA-N 0.000 claims description 2
- FBLNSQMYGLIFII-UHFFFAOYSA-N 3-(4-methoxyphenyl)-3-oxopropanoic acid Chemical compound COC1=CC=C(C(=O)CC(O)=O)C=C1 FBLNSQMYGLIFII-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 6
- UAEHSOYZLMXHSR-UHFFFAOYSA-N 2,6-dimethyloct-7-en-2-yl 3-oxododecanoate Chemical compound CCCCCCCCCC(=O)CC(=O)OC(C)(C)CCCC(C)C=C UAEHSOYZLMXHSR-UHFFFAOYSA-N 0.000 claims 1
- 102000004190 Enzymes Human genes 0.000 claims 1
- 108090000790 Enzymes Proteins 0.000 claims 1
- 239000008186 active pharmaceutical agent Substances 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 claims 1
- 239000002979 fabric softener Substances 0.000 claims 1
- 239000000417 fungicide Substances 0.000 claims 1
- 230000002070 germicidal effect Effects 0.000 claims 1
- 239000003752 hydrotrope Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000006071 cream Substances 0.000 abstract description 13
- 239000006210 lotion Substances 0.000 abstract description 12
- 239000002781 deodorant agent Substances 0.000 abstract description 7
- 230000001815 facial effect Effects 0.000 abstract description 3
- 239000008266 hair spray Substances 0.000 abstract description 3
- 230000002459 sustained effect Effects 0.000 abstract description 2
- 241000195940 Bryophyta Species 0.000 abstract 1
- 230000000386 athletic effect Effects 0.000 abstract 1
- 235000011929 mousse Nutrition 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 83
- 239000000243 solution Substances 0.000 description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 46
- 239000003921 oil Substances 0.000 description 44
- 235000019198 oils Nutrition 0.000 description 43
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 35
- 239000000463 material Substances 0.000 description 33
- 238000007792 addition Methods 0.000 description 31
- 235000019441 ethanol Nutrition 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 21
- 239000012071 phase Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
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- 238000002390 rotary evaporation Methods 0.000 description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 238000010828 elution Methods 0.000 description 14
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- 238000003756 stirring Methods 0.000 description 14
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- 235000007586 terpenes Nutrition 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 12
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- 239000002904 solvent Substances 0.000 description 12
- 150000003505 terpenes Chemical class 0.000 description 12
- 239000012267 brine Substances 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 11
- 150000001298 alcohols Chemical class 0.000 description 10
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 10
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 10
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000005792 Geraniol Substances 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000012230 colorless oil Substances 0.000 description 8
- 229940113087 geraniol Drugs 0.000 description 8
- 150000002576 ketones Chemical class 0.000 description 8
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 8
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- 235000019341 magnesium sulphate Nutrition 0.000 description 7
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- 239000007787 solid Substances 0.000 description 7
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- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000686 essence Substances 0.000 description 6
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- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- XNLBCXGRQWUJLU-UHFFFAOYSA-N naphthalene-2-carbonyl chloride Chemical compound C1=CC=CC2=CC(C(=O)Cl)=CC=C21 XNLBCXGRQWUJLU-UHFFFAOYSA-N 0.000 description 6
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 description 6
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 5
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 241000220317 Rosa Species 0.000 description 5
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
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- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 4
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 description 4
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Abstract
The present invention relates to personal care and personal hygiene articles containing a fragrance delivery system which comprises one or more pro-accords, preferably&bgr;-ketoester pro-accords, which are capable of releasing mixtures of fragrance raw materials. The pro-accords which comprise the fragrance delivery systems are useful in delivering sustained fragrances to personal care items inter alia deodorants, anti-perspirants, suntan lotions, hair sprays, mousses, shaving creams, body lotions and creams, depilitories, facial masks, athletic rubs and creams.
Description
SYSTEMS OF SUPPLY OF FRAGRANCE FOR ARTICLES OF PERSONAL CARE
This application claims priority under Title 35 of United States Code 119 (e) of Provisional Application Serial No. 60 / 024,117, filed on August 19, 1996.
FIELD OF THE INVENTION The present invention relates to fragrance supply supply systems suitable for use in articles of personal hygiene, and for personal care, among other deodorants, antiperspirants, tanning lotions, hair sprays, foams, creams for shaving, lotions and creams for the body, hair removers, facial masks, creams and ointments for athletes. The fragrance delivery systems comprise one or more starting pro-material molecules, each molecule being capable of releasing one or more fragrance raw materials. In addition, each raw material is capable of releasing a different mixture of raw materials ("chord") if it is used at a different time of composition (eg sprays for hair v. Deodorant ball).
P763 BACKGROUND DK THE INVENTION Man has applied essences and fragrances to his skin since antiquity and has used the essences and fragrances to improve the aesthetic quality of his surroundings, among others his wardrobe and the space where he lives. Originally, these aesthetically pleasing materials were commonly isolated in gross form as resins, gums or essential oils from natural sources, among others, barks, roots, leaves and fruits of indigenous plants. These resins, gums and oils were applied directly to the body or diluted with water or another solvent, including in some cases wine. With the advent of modern chemistry, the individual components responsible for the odor properties of these resins, gums and oils were isolated and subsequently characterized. Apart from the articles that have aesthetic purposes, among others the fine perfumes, colognes, toilet waters, aftershave lotions, a wide variety of articles of personal hygiene or for the personal care supply fragrances and essences to the human body. It is well known that mixtures of raw materials for perfumes or fragrances when deposited on the skin or hair lose intensity and can change their character over time, mainly due to factors such as surface penetration and differential evaporation. Many attempts have been made to diminish these problems, but to date there has been no notable success. Particularly, efforts have been made to prolong the diffusion, as well as to improve other characteristics of the fragrance materials, for example, increase the concentration of the fragrance raw material or use additives such as silicones, glycerol, polyethylene glycols, etc. These additions, however, have never been adequate to increase the longevity of the scent of the fragrance. Accordingly, there still remains a need in this field for a fragrance delivery system that can be formulated into any type of product used to deliver an aesthetically pleasing fragrance to the skin or hair by means of an article for personal hygiene or for personal care. , wherein it results that the supply of the fragrance raw material mixes has a lasting impression of the fragrance and therefore the fragrance should be released slowly.
PREVIOUS TECHNIQUE The following documents are related to fragrance ingredients. U.S. Patent Nos. 5,626,852 to Suffis et al. , granted on May 6, 1997; U.S. 5,232,612 Trinh et al. , granted on August 3, 1996; U.S. 5,506,201 to McDermott et al. , granted on April 9, 1996; U.S. 5,378,468 to Suffis et al. , granted on January 3, 1995; U.S. 5,266,592 to Grub et al. , granted on November 30, 1993; U.S. 5,081,111 to Akimoto et al. , granted on January 14, 1992; U.S. 4,994,266 of Wells, granted on February 19, 1991; U.S. 4,524,018 of Yemoto et al. , granted on June 18, 1985; U.S. 3,849,326 to Jaggers et al. , granted on November 19, 1974; U.S. 3,779,932 to Jaggers et al. , granted December 18, 1973; JP 07-179,328 published July 18, 1995; JP 05-230496 published September 7, 1993; WO 96/14827 published May 23, 1996; WO 95/04909 published February 16, 1995; and WO 95/16660 published June 22, 1995. In addition, P.M. Muller, D. Lamparsky Perfumes Art, Science, & Technology Blackie Academic & Professional, (New York, 1994) which are included here as a reference.
SUMMARY OF THE INVENTION The present invention meets the aforementioned needs as it has been surprisingly discovered that a mixture of raw materials for perfumes or fragrances (in English called "accords") can be released from a precursor molecule pro-raw materials and that these pro Raw materials can serve as a fragrance delivery system, where a variable fragrance mix is released depending on the structure and design of the pro-raw material molecule.These pro-raw materials provide a sustained ratio of perfume and fragrance when applied to human skin, either directly or through an item for personal care or hygiene, items for personal care or hygiene include, among others, deodorants, antiperspirants, tanning lotions, dews for hair, foams, shaving creams, lotions and body creams, depilating agents, facial masks, cre more and ointments for athletes, ointments, balms, ointments, antiseptic creams or shampoos. The pro-raw materials described herein comprise fragrances in a form of releasable and stable "pro-fragrances". In addition, the formulator can design compounds according to the present invention that can supply different fragrance raw materials depending on the conditions of use. The pro-raw materials can be formulated in any type of product available, either directly or indirectly, to the human skin or hair, with which an aesthetically pleasing essence is desired. Once in contact with human skin or hair, the pro-raw materials are converted into a blend of fragrance raw materials to a cup that provides fragrance benefits in a prolonged manner. The fragrance delivery systems of the present invention can consist of a mixture of any number of pro-raw materials and can cover any fragrance "characteristics" or desired fragrance volatility. The first aspect of the present invention relates to compositions that are applied to human hair or skin, the composition has increased fragrance longevity and fragrance retention. Suitable compositions of the present invention are, among others, deodorants, antiperspirants, tanning lotions, hair sprays, foams, shaving creams, lotions and body creams, hair removers, face masks, creams and ointments for athletes, ointments, balsams, ointments, antiseptic creams or shampoos, and comprise: a) at least about 0.01%, preferably from about 0.01% to about 15%, more preferably about 1% to about 5%, still more preferably about 0.1 % to about 1% of a β-ketoester having the formula:
wherein R is alkoxy derived from an alcohol of fragrance raw material; R1, R2 and R3 are each independently hydrogen, substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cyclic alkyl, substituted or unsubstituted C2-C30 linear alkenyl C3-C30 substituted or unsubstituted branched alkenyl, substituted or unsubstituted C3-C30 cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted C3-C30 branched alkynyl, substituted or unsubstituted C6-C30 alkylenearyl, C6-C30 substituted or unsubstituted aryl, substituted or unsubstituted C2-C20 alkyleneoxy, substituted or unsubstituted C3-C20 alkylene-alkyl, substituted or unsubstituted C7-C20 alkylenearyl, substituted or unsubstituted C6-C20 alkylenenoxy, and mixtures thereof; provided that at least one of R1, R2 or R3 is a unit that has the formula:
wherein R4, R5 and R6 are each independently hydrogen, substituted or unsubstituted Cx-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkylC3-C30 substituted or unsubstituted cyclic alkyl, substituted or unsubstituted C1-C30 linear alkoxy, substituted or unsubstituted C3-C30 branched alkoxy, substituted or unsubstituted C3-C30 cyclic alkoxy, substituted or unsubstituted C2-C30 linear alkenyl , substituted or unsubstituted C3-C30 branched alkenyl, substituted or unsubstituted C3-C30 cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted C3-C30 branched alkynyl, substituted or unsubstituted C6-C30 alkylenearyl; or R4, R5 and R6 taken together can form a substituted or unsubstituted C6-C30 aryl, and mixtures thereof; b) at least about 0.01% by weight of one or more adjunct ingredients selected from the group consisting of surfactants, emollients, bactericides, gelling agents, desiccants, propellants, colorants, dyes, ointment bases, lanolin, antiperspirants, mineral oil, talc, abrasives, optical brighteners, phase stabilizing agents, absorbers, active pharmaceutical compounds and mixtures thereof; and c) the rest are carriers. The present invention relates to methods for providing a mixture of fragrance raw materials to human hair or skin, comprising the step of contacting human skin or hair with the fragrance delivery system of the present invention. All percentages, proportions and ratios given herein are given by weight unless otherwise specified. All temperatures are given in degrees Celsius (° C) unless otherwise specified. All the cited documents are a relevant part and are considered part of this, by reference.
DETAILED DESCRIPTION OF THE INVENTION The present invention comprises a fragrance delivery system that deposits one or more "pro-raw material" fragrance compounds on human hair or skin, during use. Because the promateria prime compounds comprising the fragrance delivery of the present invention generally have molecular weights
P763 are superior to those of the non-combined fragrance raw materials and to other "pro-fragrance" type compounds (ie pro-fragrances that only supply a single equivalent of a fragrance raw material, are a means to effectively deliver two or more fragrance raw materials, which results in an improved longevity of fragrance raw materials on a substrate.Mixes of fragrance materials are known to those skilled in the art of fragrances and perfumes as "accords". in English "accord" referred to herein is defined as "a mixture of two or more 'fragrance raw materials' which are ingeniously combined to impart a characteristic fragrance, odor, scent or pleasing aroma." For the purposes of This invention "fragrance raw materials" are defined herein as compounds that impart odor, fragrance, essence or aroma, either alone or in combination with others " raw fragrance materials "which are considered aesthetically pleasing, preferably these compounds have a molecular weight of at least 100 g / mol. Typically, "raw fragrance materials" comprise inter alia, cyclic and acyclic alcohols, ketones, aldehydes, esters, ethers, nitriles and alkenes, especially terpenes. A common list of
P763"raw fragrance materials" can be found in several reference sources, for example in "Perfume and Flavor Chemicals", Vols., I and II; Steffen Arctander Allured Pub. Co. (1994) and in "Perfumes: Art. Science and Technology"; Müller, P.M. and Lamparsky, D., Blackie Academic and Professional (1994) both are considered here incorporated as reference. For example, only in an illustrative manner, the fragrance accords (fragrance raw materials) that are released by pro-accords (pro-mixture of raw materials) of the present invention have an "essence," "character," or "note." which is described, among others such as rose, jasmine, lilac, lily of the valley, violet, orange, peach, melon and lemon or the pro-mix of raw materials (pro-accord) can supply fragrance raw materials that provide a note of "freshness" or "cleanliness", for example, linalool or dihydromyrcenol. The mixture of raw materials can also be "modified" or "varied" by the inclusion of pro-mixes of raw materials that supply high or medium intensity modifier notes which, as an additional benefit achieved by the present invention, can be incorporated into the product. - Mix of raw materials. For example, an "essence of roses" can be combined with a "green" modifier or "displace or change the fragrance character of the raw material mix".
P763 For the purposes of the present invention, only fragrance raw materials or raw fragrance materials having a molecular weight of at least 100 g / mmol are considered as "fragrance raw materials" in accordance with the present invention . Therefore, low molecular weight materials, among others methanol, ethanol, methyl acetate, ethyl acetate, and methyl formate which are common components of fragrance raw material mixtures are excluded from the class of compounds defined herein. as "fragrance raw materials". However, the formulating technician may wish to supply these low molecular weight materials (molecular weight less than 100 g / mol) as carriers, astringents, diluents, equilibrators, fixatives or as other suitable adjuncts. For the purposes of the present invention the term "pro-fragrance" is defined as "a β-ketoester that releases an alcohol from fragrance raw material" while a "pro-accord or raw material mixture" is defined as a "ß-ketoester that releases two or more fragrance raw materials". For the purposes of the present invention, as a material that is a "pro-fragrance" in one modality can serve as a "pro-mix of raw materials" in a different modality, the term "pro-fragrance" is used interchangeably with the term "pro-fragrance".
P763 mixture of raw materials "and any of the terms may be used to refer equally to β-ketoester profragance molecules, pro-mixture molecules of β-ketoester raw materials, or collectively to both For the purposes of the present invention the materials "High intensity" type fragrance premiums are defined as "fragrances that have a high vapor pressure and when applied to a paper sachet, the vaporization takes place within 2 hours, and there is no fragrance left, substantially Initial printing of the perfume formulation is provided by "high intensity" fragrances. For the purposes of the present invention the "medium intensity" fragrance raw material materials are defined as "fragrances having an average vapor pressure and when applied to a paper sachet, the aroma remains for approximately 2 to 6 hours Essentially, 'medium intensity' fragrances provide the skeleton of the perfume formulation. " For the purposes of the present invention the "base intensity" fragrance raw materials are defined as "fragrances having a low vapor pressure and high retentivity, and when applied to a paper sachet the aroma remains for more than about 6 hours, essentially the fragrances of
P763 base intensity provide the characteristic of the perfume formulation. The terms "high intensity", "medium intensity" and "base intensity" are well recognized by those skilled in the art of compositions containing fragrances. However, the reference to specific fragrance raw materials as "high intensity" which are used in the present invention does not mean that other experts in the fragrance-containing composition art can not characterize the same ingredient as "medium intensity" type. " The same applies to fragrance raw materials referred to as "medium intensity" and "base intensity".
ß-ketoester fragrance delivery system The fragrance delivery systems of the present invention comprise one or more pro-mixes of raw materials having the formula:
wherein R is an alkoxy derived from an alcohol of fragrance raw material. Non-limiting examples of
P763 Preferred fragrance raw material alcohols include 2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethyl cydohexane methanol (Dihydrofloralol), 5,6-dimethyl-1-methylethylbicyclo [2.2. l] hept-5-ene-2-methanol (Arbozole), a, a, -4-trimethyl-3-cyclohexen-l-methanol (a-terpineol), 2,4,6-trimethyl-3-cyclohexene-1 -methanol (Isocyclo geraniol), 4-1-methylethyl) cydohexane methanol (Mayol), a-3, 3-trimethyl-2-norborane methanol, 1,1-dimethyl-1- (4-methylcyclohex-3-enyl) ethanol , 2-phenylethanol, 2-cyclohexyl ethanol, 2- (o-methylphenyl) -ethanol, 2- (m-methylphenyl) ethanol, 2- (p-methylphenyl) ethanol, 6,6-dimethylbicyclo- [3.1. l] hept-2-ene-2-ethanol (nopol), 2- (4-methylphenoxy) -ethanol, 3,3-dimethyl-? 2-b-norbornene ethanol (patchomint), 2-methyl-2-cyclohexylethanol, 1- (4-isopropylcyclohexyl) -ethanol, 1-phenylethanol, 1,1-dimethyl-2-phenylethanol, 1, l-dimethyl-2- (4-methyl-phenyl) ethanol, 1-phenylpropanol, 3-phenylpropanol, 2 -phenylpropanol (Hydrotropic Alcohol), 2- (cyclododecyl) propan-l-ol (Hydroxy-ambran), 2,2-dimethyl-3- (3-methylphenyl) -propan-1-ol (Majantol), 2-methyl- 3-phenylpropanol, 3-phenyl-2-propen-l-ol (alcohol cinnamyl), 2-methyl-3-phenyl-2-propen-l-ol (methyl methyl alcohol), an-pentyl-3-phenyl-2- propen-l-ol (a-amyl-cinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2- (4-methylphenyl) -2-propanol, 3- (4-methylcyclohex-3-ene) butanol, 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) butanol, 2-ethyl-4- (2, 2, 3-trimethyl-cyclopent-3-enyl) -2-buten -l-ol, 3-
P763 methyl-2-buten-l-ol (prenol), 2-methyl-4- (2, 2, 3-trimethyl-3-cyclopenten-1-yl) -2-buten-l-ol, ethyl 3-hydroxybutyrate , 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol, 4- (4-hydroxyphenyl) butan-2-one, 4- (4-hydroxy-3-methoxyphenyl) -butan-2-one, 3-methyl-pentanol, 3-methyl-3-penten-l-ol, l- (2-propenyl) cyclopentan-1-ol ( plinol), 2-methyl-4-phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol (Phenoxanol), 2-methyl-5-phenylpentanol, 2-methy1-5- (2,3-dimethyltricyclo [2.2.1.0 ( 2,6)] hept-3-yl) -2-penten-l-ol (santalol), 4-methyl-l-phenyl-2-pentanol, 5- (2, 2, 3-trimethyl-3-cyclopentenyl) -3-methylpentan-2-ol (sandalore), (1-methyl-bicyclo [2.1. L] hepten-2-yl) -2-metiIpent-1-en-3-ol, 3-methy1-l-phenylpentan- 3-ol, 1, 2-dimethyl-3- (1-methylethyl) cyclopentan-1-ol, 2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen -l-ol, 2-isoproenyl-4-methyl-4-hexen-l-ol (Lavandulol), 2-ethyl-2-preni-3-hexene, 1-hydroxymethyl-1-4-iso-propenyl-1-cyclohexene ( alcohol dihydrocuminyl), l-methyl-4-isopropenylcyclohex-6-en-2-ol (carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol (dihydrocarvol), 1-methyl-iso-propenylcyclohexan-3-ol, 4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclohexanol, 2-tert-butyl cyclohexanol, 2-tert-butyl-4-methylcyclohexanol (rootanol), 4-isopropyl-cyclohexanol, 4-methyl-1- (1-methylethyl) -3-cyclohexen-1-ol, 2- (5,6, 6- trimethyl-2-norbomyl) cyclohexanol,
P763 isobomylcyclohexanol, 3, 3, 5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, l-methyl-4-isopropylcyclohexan-8-ol (dihydroterpineol), 1,2-dimethyl-3- (1-methylethyl) ) cyclohexan-1-ol, heptanol, 2,4-dimethylheptan-l-ol, 6-heptyl-5-hepten-2-ol (isolinalool), 2,4-dimethyl-2,6-heptanedienol, 6,6-dimeti1- 2-oxymethyl-bicyclo [3.1. l] hept-2-ene (mirtenol), 4-methyl-2,4-heptadien-l-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5 -hepten-2-ol, 6, 6-dimethyl-3-hydroxy-2-methylenebicyclo [3.1.1] heptane, 1, 7,7-trimethylbicyclo [2.2. l] heptan-2-ol, 2,6-dimethylheptan-2-ol (dimethylol), 2,6,6-trimethylbicyclo [1.3.3] heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2 -ol, 2-methyl-6-methylene-7-octen-2-ol (mircenol), 7-methyloctan-l-ol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octen-l-ol (citronellol), 3,7-dimethyl-2,6-octadien-l-ol (geraniol), 3,7-dimethyl-2,6-octadien-l- ol (nerol), 3, 7-dimethyl-7-methoxyoctan-2-ol (osirol), 3, 7-dimethyl-l, 6-octadien-3-ol (linalool), 3, 7-dimethyloctan-l-ol (pelargol), 3,7-dimethyloctane-3-ol (tetrahydrolinalool), 2,4-octadien-1-ol. 3,7-dimethyl-6-octen-3-ol (dihydrolinalool), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), 2,6-dimethyl-5,7-octadien-2-ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol, 2,6-dimethyloctan-3-ol, 3,6- dimethyloctan-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-3, 5-octadien-2-ol (muguol), 3-methyl-l-octen-3-ol 7-
P763 hydroxy-3, 7-dimethyloctanal, 3-nonanol, 2,6-nonadien-l-ol, cis-6-nonen-l-ol, 6, 8-dimethylnonan-2-ol, 3- (hydroxymethyl) -2 -nonanone, 2-nonen-l-ol, 2, 4-nonadien-l-ol, 3,7-dimethyl-1, 6-nonadien-3-ol, decanol, 9-decenol, 2-benzyl-M-dioxa -5-ol, 2-decen-l-ol, 2, 4-decadien-l-ol, 4-methyl-3-decen-5-ol, 3, 7, 9-trimethyl-l, 6-decadien-3 -ol (isobutyl linalool), undecanol, 2-undecen-l-ol, 10-undecen-l-ol, 2-dodecen-l-ol, 2,4-dodecadien-l-ol, 2,7, 11-trimeti1 -2, 6, 10-dodecatrien-l-ol (farnesol), 3, 7, 11-trimethyl-l, 6, 10, -dodecatrien-3-ol (nerolidol), 3, 7, 11, 15-tetramethylhexadec- 2-en-l-ol (phytol), 3, 7, 11, 15-tetramethylhexadec-l-en-3-ol (iso phytol), benzyl alcohol, p-methoxy benzyl alcohol (anisyl alcohol), para-citrate 7-ol (cuminyl alcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxy benzyl alcohol, methyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, n-pentyl salicylate, 2-phenylethyl salicylate, n-hexyl salicylate, 2-methyl-5-iso propylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4- (1-propenyl) phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, -tert-butylphenol, 2-ethoxy-4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl-5-methylphenol (thymol), pentyl-ortho-hydroxybenzoate, ethyl 2-hydroxy-benzoate, methyl-2,4 -dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-5-methoxy-1-methylbenzene, 2-tert-butyl-4-methyl-l-hydroxybenzene, 1-ethoxy-2-hydroxy-4-propenylbenzene, 4-hydroxytoluene , 4-
P763 hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro-2-naphthol, 1,3,3-trimethyl-2-norbomanol (phenol), 3a, 4,5,6,7, 7a-hexahydro-2,4-dimethyl-4,7-methano-lH-inden-5-ol, 3a, 4, 5, 6, 7, 7a-hexahydro-3, 4-dimethyl-4,7-methano-lH-inden-5-ol, 2-methy1-2-vinyl-5- (1-hydroxy-1-methylethyl) tetrahydrofuran, β-caryophyl alcohol, vanillin and mixtures of the same. More preferably, the fragrance raw material alcohol is also selected from the group consisting of cis-3-hexen-1-ol, hawthanol [mixture of 2- (o-methylphenyl) -ethanol, 2- (m-methylphenyl) ethanol, and 2- (p-methylphenyl) ethanol], heptan-1-ol, decan-1-ol, 2,4-dimethyl-cyclohexane-methanol, 4-methylbutan-1-ol, 2, 4, 6-trimethyl-3 -cyclohexene-1-methanol, 4- (1-methylethyl) cyclohexane methanol, 3- (hydroxymethyl) -2-nonanone, octan-1-ol, 3-phenylpropanol, Rhodinol 70 [mixture of 3, 7-dimethyl- 7-octenol, 3,7-dimethyl-6-octenol], 9-decen-l-ol, a-3, 3-trimeti1-2-norborane methanol, 3-cyclohexylpropan-l-ol, 4-methyl-l- phenyl-2-pentanoi, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, phenyl ethyl methanol; propyl benzyl methanol, l-methyl-4-isopropenylcyclohexan-3-ol, 4-isopropyl-l-methylcyclohexan-3-ol (menthol), 4-tert-butylcyclohexanol, 2-tert-butyl-1-methylcyclohexanol, 4-isopropyl-cyclohexanol , trans-decahydro-ß-naphthol, 2-tert-butylcyclohexanol, 3-phenyl-2-
P763 propen-1-ol, 2, 7, ll-trimethyl-2, 6, 10-dodecatrien-l-ol, 3,7-dimethyl-2,6-octadien-l-ol (geraniol), 3, 7- dimethyl-2, 6-octadien-1-ol (nerol), 4-methoxybenzyl alcohol, benzyl alcohol, 4-allyl-2-methoxyphenol, 2-methoxy-4- (1-propenyl) phenol, vanillin, ethyl vanillin, and mixtures thereof. R1, R2 and R3 are each independently hydrogen, substituted or unsubstituted C-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cyclic alkyl, substituted C2-C30 linear alkenyl or non-substituted substituted, substituted or unsubstituted C3-C30 branched alkenyl, substituted or unsubstituted C3-C30 cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted C3-C30 branched alkynyl, substituted or unsubstituted C6-C30 aryl , substituted or unsubstituted c2-c2o alkyleneoxy, substituted or unsubstituted C3-C20 alkyleneoxyalkyl, substituted or unsubstituted C7-C20 alkylenearyl, substituted or unsubstituted C6-C20 alkylenenoxyaryl, and mixtures thereof; as long as at least one of
R1, R2 or R3 is a unit that has the formula:
P763 wherein R4, R5 and Rd are each independently hydrogen, substituted or unsubstituted C-C- C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cyclic alkyl, linear alkoxy ^ - C ^ substituted or unsubstituted, substituted or unsubstituted C3-C30 branched alkoxy, substituted or unsubstituted C3-C30 cyclic alkoxy, substituted or unsubstituted C2-C30 linear alkenyl, substituted or unsubstituted C3-C30 branched alkenyl, cyclic alkenyl C3 -C30 substituted or unsubstituted, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted C3-C30 branched alkynyl, substituted or unsubstituted C6-C30 alkylenearyl, substituted or unsubstituted C6-C30 aryl; or R4, R5 and R6 taken together can form a substituted or unsubstituted C6-C30 aryl, and mixtures thereof. Preferably, at least two units R1, R2 or R3 are hydrogen. In one embodiment of the present invention, preferably R4, R5 and R6 are hydrogen. Further, preferably when two units R 4, R 5 and R 6 are hydrogen, the remaining unit is Cj-C ^ substituted or unsubstituted linear alkyl, substituted or unsubstituted C3-C20 branched alkyl, substituted or unsubstituted C3-C20 cyclic alkyl; more preferably methyl. Also preferably R4, R5 and R6 taken together form a
P763 substituted or unsubstituted C6-C30 aryl unit, preferably phenyl and substituted or unsubstituted naphthyl. For the purposes of the present invention the term "substituted" as applied to linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl, branched alkenyl, cyclic alkenyl, branched alkoxy, cyclic alkoxy, alkynyl and branched alkynyl is defined as "chains" of carbon comprising substituents other than those of the branching of the carbon atom chain ", for example, different from the branches of the alkyl units (for example isopropyl, isobutyl). Non-limiting examples of "substituents" include hydroxy, Cj-C ^ alkoxy, preferably methoxy; C3-C12 branched alkoxy, preferably isopropoxy; cyclic C3_Ci2 alkoxy; nitrile; halogen, preferably chlorine and bromine, more preferably chlorine; nitro; morpholino; cyano; carboxyl, the non-limiting examples are: -CHO; -C02"M +, -C02R9; -CONH2; -CONHR9; -CONR92; wherein R9 is straight or branched CrC12 alkyl; -S03" M +; -OS03"M +; -N (RlO) 2; and -N + (R10) 3X ~ wherein each R10 is independently hydrogen or C1-C4 alkyl, and mixtures thereof, wherein M is hydrogen or a water-soluble cation and X is chlorine, bromine, iodine, or other water-soluble anions For the purposes of the present invention, substituted or unsubstituted alkyleneoxy units are
P763 define as entities that have the formula:
wherein R7 is hydrogen; R8 is hydrogen, methyl, ethyl, and mixtures thereof; the index x ranges from 1 to about 10. For the purposes of the present invention, substituted or unsubstituted alkylenoxyalkyl is defined as entities having the formula: R8 - (CH2CHO) x (CH2) and R7 wherein R7 is hydrogen, alkyl C. -C ^, C1-C4 alkoxy and mixtures thereof; R8 is hydrogen, methyl, ethyl and mixtures thereof; the index x ranges from 1 to approximately 10 and the index ranges from 2 to approximately 18. For the purposes of the present invention the substituted or unsubstituted aryl units are defined as phenyl entities having the formula:
or α and β-naphthyl entities having the formula:
P763
wherein R7 and R8 may be substituted in any of the rings, alone or in combination, and R7 and R8 are each independently hydrogen, hydroxy, Ci-C1 alkyl, C2-C6 alkenyl, C1-C4 alkoxy, C3 alkoxy -C6 branched, nitrile, halogen, nitro, morpholino, cyano, carboxyl (-CHO; -C02"M +; -C02R9; -CONH2; -CONHR9; -CONR92; wherein R9 is linear or branched C.-C ^ alkyl) , -S03"M \ -OS03" M +, -N (R10) 2, and -N + (R10) 3X- wherein each R10 is independently hydrogen, C-C4 alkyl or mixtures thereof, and mixtures of R7 and R8 are preferably hydrogen, C alquilo-C6 alkyl, -C02 MJ -S03"M +, -OS03" M + and mixtures thereof, more preferably R7 or R8 is hydrogen and the other entity is C1-C1, where M is hydrogen or a water-soluble cation and X is chlorine, bromine, iodine or other water-soluble anions Examples of water-soluble anions include organic species such as fumarate, succinate, tartrate, oxalate and the like, inorganic species they include sulfate, acid sulfate, phosphate and the like. For the purposes of the present invention the substituted or unsubstituted alkylenearyl units are defined as entities having the formula:
P763 wherein R7 and R8 are each independently hydrogen, hydroxy, C1-C1-alkoxy, nitrile, halogen, nitro, carboxyl (-CHO; -C02"M +; -C02R9; -CONH2; -CONHR9; -C0NR92; where R9 is linear or branched C ^ C ^ alkyl), amino, alkylamino and mixtures thereof, p is from 1 to about 14, M is hydrogen or a water-soluble cation For the purposes of the present invention, substituted alkylenediaryl units or unsubstituted are defined as entities that have the formula:
wherein R7 and R8 are each independently hydrogen, hydroxy, Cj-C4 alkoxy, nitrile, halogen, nitro, carboxyl (-CH0; -C02M +; -C02R9; -CONH2; -CONHR9; -CONR92; wherein R9 is C-alkyl ^ C ^ linear or branched), amino, alkylamino and mixtures thereof, q is from 1 to about 14; M is hydrogen or water-soluble cation. Surprisingly, the pro-mix of raw materials comprising the fragrance delivery systems of the present invention are capable of releasing
P763 at least one fragrance raw material, preferably the pro-mix of raw materials releases two or more fragrance raw materials. For example, the pro-mixture of raw materials 3, 7-dimethyl-l, 6-octadien-3-yl-3 (β-naphthyl) -3-oxo-propionate has the formula:
and releases, depending on the conditions of use, at least two fragrance raw materials, inter alia, linalool, ß-naphthyl methyl ketone, myrcene, α-terpinolene and β-3-carene. The premixes of raw materials comprising the fragrance delivery systems of the present invention are capable of releasing their fragrance compounds by more than one simple chemical mechanism, a point that is key to the variety of fragrance raw materials that they are released from a single compound of pro-mix of raw materials. Therefore, depending on the wishes of the formulator, the raw material mixture of the present invention is capable of releasing a different mixture of fragrance raw materials depending on the release medium. For example, the pro-mixture of 3, 7-dimethyl-l, 6-octadien-3-yl 3-
P763 (ß-naphthyl) -3-oxo-propionate produces a different mixture of raw materials when the release of fragrance raw materials is done on the skin than when it is done on the hair. Typically, the raw material mixture of the present invention releases a mixture of alcohols, esters, ketones, hydrocarbyl materials, especially terpenes, which have aesthetically pleasing qualities, and mixtures thereof. For the purposes of the present invention the term "hydrocarbyl material" is defined as a compound essentially comprising only carbon and hydrogen, inter alia, alkanes, alkenes and alkynes, whether linear, cyclic, branched or combinations thereof. " An example of a hydrocarbyl material that is capable of being released by a mixture of raw materials of the present invention is mircene For the purposes of the present invention the term "terpene" is used to designate hydrocarbons, inter alia myrcene, limonene However, those skilled in the art of perfumes as well as organic chemistry will recognize that geraniol and nerol that are listed as "fragrance raw material alcohols" above are also terpenes. specification the term "terpene" is used interchangeably with "hydrocarbyl" and when "terpene" is used broadly, it refers to alcohols,
P763 ketones, alkenes, etc., which are generally considered to be terpenes, and when the term "terpene" is used in a reduced sense it refers mainly to alkanes, alkenes, etc. which typically have 10 carbon atoms (terpenes) or 15 carbon atoms (sesquiterpenes). Examples of alcohols releasable by the raw material mixture are described above and are typically fragrance raw material alcohols that are used to form the original compounds. However, during the process of releasing the fragrance raw material, these fragrance raw material alcohols are also capable of undergoing a modification, which includes isomerization and / or rearrangement. Therefore, in addition to the original alcohol used to form the original mixed raw material ester, other alcohols can be formed by transformations that occur during the release process. Depending on the selection made by the formulator technician when designing the molecules of the raw material mix, to formulate a fragrance delivery system according to the present invention, these transformations take place to a greater or lesser degree. Non-limiting examples of releasable terpenes by the premix of raw materials of the present invention include hydrocarbyl materials such as myrcene,
P763 ocimeno, β-farnesene, cis-Achillene, trans-Achillene, carvomentene, limonene, a-terpinene, β-terpinene, terpinolene, α-fellandrene, β-fellandrene, 2-carene, 3-carene, α-pinene, β -pinene, campeno and other terpenes, for example (-) - (2S, 4R) -2- (2-methyl-1-propenyl) -4-methyltetrahydropyran (cis pink oxide), (-) - (2S, 4S) -2- (2-methyl-1-propenyl) -4-methyltetrahydropyran (trans-pink oxide), 2-methyl-2-vinyl-5- (α-hydroxy-isopropyl) tetrahydrofuran (linalool oxide) and mixtures thereof . Non-limiting examples of ketones that are releasable by the raw material mixtures of the fragrance delivery systems of this invention are a-damascone, ß-damascone, d-damascone, ß-damaseenone, muscone, 3, 3- dimethylbutanone, methylphenyl ketone
(acetophenone), 4-phenylbutan-2-one (benzyl acetone), 2-acetyl-3, 3-dimethylnorbornane (camek dh), 6,7-dihydro- 1, 1, 2, 3, 3-pentamethyl-4 (5H ) indanone (cashmeran), 4- (1,3) -benzodioxol-5-yl-3-buten-2-one (cassione), 4- (3,4-methylenedioxyphenyl) -2-butanone (dulcinyl), 3-octanone , 6-acetyl-1, 2, 3, 4-tetrahydronaphthalencetona (florantone t), ethyl-2-n-hexyl acetoacetate (gelsone), 2,6-dimethylundeca-2,6-dien-10-one, 6, 10 -dimethyl-5, 9-undecadien-2-one, 3,3-dimethylcyclohexyl methyl ketone (herbac), 4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -3-buten-2-one (ß-ionone), 4- (2,6,6-
P763 trimethyl-2-cyclohexen-1-yl) -3-buten-2-one (α-ionone), 3-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -3 -buten-2-one
(d-methyl-ionone), 4- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-methyl-3-but-2-one (? -methyl-ionone), 3-methyl -4- (2, 6, -trimeti1-2-cyclohexen-1-yl) -3-buten-2-one (irisantheme), 4- (2,3,5-trimethyl-4-cyclohexen-1-yl) -3-buten-2-one (iritone),
4-methyl- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) -3-buten-2-one (a-ionone), 1, 2, 3, 4, 5, 6, 7 , 8-octahydro-2, 3, 8, 8-tetramethyl-2-acetonaphthone (iso cyclomone e), 7-acetyl-1, 2, 3, 4, 5, 6, 7, 8-octahydro-l, 1, 6,7-tetramethyl naphthalene (Iso E Super®), acetyl diisoamylene (Koavone®), methyl amyl ketone, 2-acetonaphthone cedr-8-enyl methyl ketone (methyl cedrilone), 2,3,6-trimethyl-cyclohexane-4-yl -l-methylcentone methyl cyclo citrona), hexahydroacetophenone (methyl cyclohexyl ketone), 6-methyl-3,5-heptadien-2-one, 6-methyl-5-hepten-2-one, 2-octanoe, 3- (hydroxymethyl) ) -2-nonanone, 4-acetyl-1, l-dimethyl-6-tert-butyl indane (mustard indanone), 2,6-dinitro-3,5-dimethyl-4-acetyl-tert-butylbenzene (musk ketone), l-para-menten-6-yl propanone (nerona), for methoxy acetophenone (acetanisole), 6-acetyl-1, 1, 2, 3, 3, 5-hexamethyl indan (Phantolid®), 7-acetyl-1, 1, 3, 4, 4, 6-hexamethyl tetralin (Tonalid®, Musk Plus®), 5-acetyl-3-isopropyl-l, 1,2,6-tetramethyl indan (Traseolid e 70®), methyl-2, 6, 10-trimethyl-2, 5, 9-cyclododecatrieno-l-yl-ketone (Trimofix 0®), methyl cedrilone (Vertofix Coeur®), 4-
P763 (4-hydroxy-3-methoxyphenyl) -2-butanone, cis-jasmone, dihydrojasmone, α-ionone, β-ionone, dihydro-β-ionone, 4- (4-hydroxyphenyl) butan-2-one, 1- carvone, 5-cyclohexadecen-l-one, decatone, 2- [2- (4-methyl-3-cyclohexenyl-l-yl) propyl] cyclopentan-2-one, 2-sec-butylcyclohexanone, allyl ionone, a-ketone , geranyl acetone, 1- (2-methyl-5-isopropyl-2-cyclohexenyl) -1-propanone, acetyl diisoamylene, methyl cyclocitron, 4-t-pentylcyclohexanone, pt-butylcyclohexanone, ot-butylcyclohexanone, methane, methyl-7 , 3-dihydro-2H-1, 5-benzodioxepin-3-one, fenchone, methyl hydroxynaphthyl ketone and mixtures thereof. According to the present invention, all isomers of fragrance raw materials either in the form of pro-mixtures of raw materials or of the fragrance raw material released, are suitable for the use of the present invention. When the presence of optical isomers is possible, the fragrance raw materials can be included either as the separated chemical isomers or as the combined racemic mixture. For example, 3,7-dimethyl-6-octen-1-ol, commonly known to those skilled in the art as β-citronellol or cefrole, comprises a pair of optical isomers, R- (+) - β-citronellol and S - (-) - ß-citronellol. Each of these materials separately or as a racemic pair are suitable for use as fragrance raw materials in the present invention. Without
However, those skilled in the art of fragrances, by use of the present invention, should not fail to take into account the olfactory differences that individual optical isomers, mixtures of optical isomers or mixtures of positional isomers impart. By way of example, carvone, 2-methyl-5- (1-methyletenyl) -2-cyclohexene-1-one exists as two isomers; d-carvone and 1-carvone. d-Carvona is found in caraway oil and provides a completely different fragrance to 1-carvone, which is found in spearmint oil. According to the present invention, a mixture of raw materials releasing d-carvone will result in a different aroma or fragrance than that released by 1-carvone. The same applies to 1-carvona. In addition, the isomers such as the cis / trans isomers, for example nerol (3,7-dimethyl-cis-2,6-octadien-1-ol) and geraniol (3,7-dimethyl-trans-2,6-octadiene) -l-ol) are well known to those skilled in the art of perfumery and these two terpene alcohols, which are commonly presented as a mixture, have different fragrance characteristics. Therefore, when raw fragrance materials are formulated to comprise mixtures of isomers such as nerol / geraniol, the formulator must also take into account whether these different sources of raw materials have different proportions of isomers.
P763 An example of a preferred raw material mixture is 3,7-dimethyl-l, 6-octdien-3-yl 3- (β-naphthyl) -3-oxo-propionate having the formula:
which releases at least one fragrance raw material alcohol, linalool, which has the formula:
and a fragrance raw material, ketone, methyl naphthyl ketone, having the formula:
An additional example of a preferred raw material blend includes 2,6-dimethyl-7-octen-2-yl 3- (4-methoxyphenyl) -3-oxo-propionate having the formula:
P763 which releases at least alcohol from fragrance raw material, dihydromyrcenol, which has the formula:
and the fragrance raw material ketone, methyl 4-methoxyphenyl ketone, which has the formula:
Other non-limiting examples of preferred raw material mixes include 3,7-dimethyl-l, 6-octadien-3-yl 3- (a-naphthyl) -3-oxo-propionate, [linalyl (l-naphthoyl) -acetate) ], which has the formula:
2, 6-dimethyl-7-octen-2-yl 3- (4-methoxyphenyl) -3-oxo-propionate, [3- (4-methoxyphenyl) -3-oxo-propionic acid] dihydromyrcenylester, which has the formula :
P763
2, 6-dimethyl-7-octen-2-yl 3- (4-nitrophenyl) -3-oxo-propionate, [3- (4-nitrophenyl) -3-oxo-propionic acid] dihydromyrcenylester, which has the formula :
2, 6-dimethyl-7-octen-2-yl 3- (ß-naphthyl) -3-oxo-propionate, [dihydromyrcenyl (2-naphthoyl) acetate], having the formula:
3, 7-dimethyl-l, 6-octadien-3-yl 3- (4-methoxyphenyl) -3-oxo-propionate, [3- (4-methoxyphenyl) -3-oxo-propionic acid linalylester], which has the formula:
P763 (α, α-4-trimethyl-3-cyclohexenyl) methyl 3- (β-naphthyl) -3-oxo-propionate, [α-terpinyl (2-naphthoyl) acetate], having the formula:
9-decen-l-yl 3- (ß-naphthyl) -3-oxo-propionate, [9-decen-l-yl (2-naphthoyl) acetate], alternatively known as rosalva '-acetonaphthone, having the formula :
3, 7-dimethyl-l, 6-octadien-3-yl 3- (nonanyl) -3-oxo-propionate, [linalyl (nonanoyl) acetate], alternatively known as octyl [(linalyl) a-acetyl] ketone, which has the formula:
3, 7-dimethyl-l, 6-octadien-3-yl 3-oxo-butyrate, alternatively known as linalyl acetoacetate, having the formula:
P763
2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, [dihydromyrcenyl acetoacetate], having the formula:
Other non-limiting examples of preferred fragrances comprising the fragrance delivery systems of this invention include cis 3-hexen-l-yl 3- (β-naphthyl) -3-oxo-propionate, 2,6-dimethyl- 7-octen-2-yl 3- (nonanil) -3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-l, 6-octadien- 3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3- (ß-naphthyl) -3-oxo-2-methylpropionate, 3,7-dimethyl-l, 6-octadien- 3-yl 3- (ß-naphthyl) -3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixtures thereof. Without wishing to be bound by theory, the process by which the fragrance mixes of the present invention release their fragrance raw materials is not limited to one route. In fact, the same molecule under identical conditions may have several equal routes by which some same or different compounds are released. For example, both nerol and geraniol can
P763 is released from an ester that is formed only by geraniol, as long as the conditions under which the transformation of geraniol to nerol occurs are present during use. These conditions can be built into the molecule by the formulator or can be provided by the surrounding environment (ie, the formulation). In addition, during the process of releasing the fragrance raw material, both the keto portion and the alcohol portion of the raw material mixture is capable of undergoing chemical transformations that provide a mixture of fragrance characteristics not subject to inclusion in the pro-mixes of original raw materials. For example, a raw material ester ester comprising the citronellol fragrance raw material alcohol can potentially release a mixture of rose oxides with the following scheme:
as long as the proper re-arrangement conditions are present during use.
P763 The formulator is not limited to the supply of a type of fragrance, for example a characteristic of high intensity, medium intensity or base intensity of the fragrance raw material. On the contrary, high intensity characteristics, a mixture of high and medium intensity characteristics or combinations of high, medium and base intensities can be supplied in any suitable proportion. As described above, those skilled in the field of fragrance-containing composition have categorized the fragrances into three types based on their relative volatility: high intensity, medium and high. In addition, fragrances are divided into categories by the smell they produce, some of these descriptors are broad and others are relatively specific. For example "floral" is a term that connotes smells associated with flowers, while the term "lilac" is more specific. The descriptors used by experts in this field of perfumes and fragrances are, among others "rose" "floral" "green" "citrus" "spice" "honey" "musk". The sources of these characteristics are not limited to a single chemical class; the alcohols can produce aromas of "rose" "green" "musk", while the "rose" flavor may comprise alcohols, ketones, terpenes, aldehydes, etc.
P763 The upper, middle and base intensity characteristics each serve a different purpose in fragrance mixing and when formulated properly they produce a "balanced fragrance" composition. Based on volatility, these characteristics are described by experts in this field as: base features that have the most lasting aroma; medium intensity characteristics that have a medium volatility, and high intensity characteristics and that are the most volatile. The compositions described below, as well as others chosen by the formulator, comprise a fragrance delivery system that utilizes the premix mixtures of the present invention to successfully deliver a "balanced fragrance" profile. It is also recognized by experts in this field that descriptors that relate to aesthetic perceptions such as intensity "high", "medium", "base" are relative terms. A fragrance raw material that falls into the category of "high intensity" characteristic by the formulator technician, usually has an identical classification among most other Perfumers. The same happens also for the average and base intensities, however, occasionally a formulator can classify a fragrance
P763 specific as medium intensity instead of high intensity, or vice versa, but this fact does not diminish the utility of a specific compound or its absolute identity. The high, medium and base intensities are now combined in a reproducible manner to produce perfumes, colognes, aftershave lotions, toilet waters, etc., to be applied to the skin, with unique and pleasing odor characteristics. In addition to this pleasing fragrance, a fragrance delivery system that is used to deliver a scent to a personal care item must meet several technical requirements. It must be strong enough. It must be persistent and must retain its "essential character" throughout its period of evaporation. In addition to the changes made to the raw material molecules for the purpose of modifying the fragrance profiles provided by the fragrance delivery systems of the present invention, modifications can be made to the pre-mixes of raw materials in order to increase the ability to formulate materials. The formulator, by selecting a suitable unit R1, R2 or R3 or by selecting R4, Rs and Rd, can influence the degree and rate at which the mixture of raw materials is deposited on the hair or skin or the way in which the fragrance supply system is
P763 disperses within a composition. The following examples illustrate the β-ketoesters and compositions comprising the fragrance delivery system of this invention, but are not intended to be limited thereto.
EXAMPLE 1 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3- (ß-naphthyl) -3-o-? O-propionate Lithium diisopropylamide (101.0 mL of a 2.0 M, 0.202 solution is placed mol) in a 500 mL three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is placed in a dry ice-acetone bath. Dissolve 3, 7-dimethyl-l, 6-octadien-3-yl acetate
(linalyl acetate) in the amount of (18.66 g, 0.095 mol) in THF (5 mL) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for an additional 15 minutes, before being treated with a solution of 2-naphthoyl chloride in the amount of (17.43 g, 0.090 mol) dissolved in THF (25 mL) over a period of time. 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (53 mL). The mixture is poured into a separating funnel
P763 containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. The purity of the product is determined by thin layer chromatography and GC analysis and the structure was confirmed by mass spectroscopy, H and 13C NMR.
EXAMPLE 2 Preparation of 2,6-dimethyl-7-octen-2-yl 3- (4-methoxyphenyl) -3-o-? O-propionate N-isopropylcyclohexylamine (25.00 g, 0.177 mol) and THF w in the amount of 200 mL are placed in a 1000 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is placed in an ice-methanol bath and cooled to -5 ° C and its contents are treated with n-butyllithium in an amount of (70.8 mL of a 2.50 M solution, 0.177 mol). The mixture is stirred for 20 minutes and then cooled to -78 ° C. Dissolves 2,6-
P763 dimethyl-7-octen-2-yl acetate (dihydromyrcenyl acetate) in an amount of (17.55 g, 0.089 mol) of THF (10 mL) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for an additional 15 minutes, before being treated with a solution of p-methoxybenzoyl chloride in the amount of (15.10 g, 0.090 mol) dissolved in THF (25 mL) in one term 30 minutes and then stirred for 1 hour. The mixture is heated to 0 ° C and then treated with 90 mL of 20% HCl one hour later. The mixture is poured into a separatory funnel containing ether (100 mL) and water (200 mL). The aqueous layer is extracted with ether (100 mL). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 ml), water (2 x 150 ml) and brine (100 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. The purity of the product is determined by thin layer chromatography and analysis of the structure was confirmed by XH and 13C NMR.
P763 EXAMPLE 3 Preparation of 2,6-dimethyl-7-octen-2-yl 3- (4-nitrophenyl) -3-oxo-propionate Lithium diisopropylamide (121.0 mL of a 2.0 M solution, 0.243 mol) is placed in a 500 ml three-necked round bottom flask adapted with a magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is placed in a dry ice-acetone bath. Dissolve 2, 6-dimethyl-7-octen-2-yl acetate (22.66 g, 0.114 mol) in THF (5 mL) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for a further 15 minutes, before being treated with a solution of 4-nitrobenzoyl chloride (20.00 g, 0.108 mol) dissolved in THF (25 mL) within 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (70 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 mL), water
(2 x 150 L) and brine (150 mL), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate).
P763 ethyl / petroleum ether) to give a colorless oil having XH and 13C NMR spectra consistent with the desired product. EXAMPLE 4 Preparation of 2,6-dimethyl-7-octen-2-yl 3- (β-naphthyl) -3-oxo-propionate Lithium diisopropylamide is placed in an amount of (100.0 mL of a 2.0 M solution, 0.201 mol ) in a 500 mL three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is cooled to -78 ° C, 2,6-dimethyl-7-octen-2-yl acetate is dissolved in an amount of (18.75 g, 0.095 mol) and in THF (5 mL) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for an additional 15 minutes, before being treated with a solution of 2-naphthoyl chloride in an amount of (17.00 g, 0.089 mol) dissolved in THF (25 mL) in a 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (55 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL),
P763 is dried over MgSO4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate disulete in petroleum ether) to give an oil. The purity of the product is determined by thin layer chromatography and the structure was confirmed by "H and 13C-NMR.
EXAMPLE 5 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3- (4-methoxyphenyl) -3-oxo-propionate Lithium diisopropylamide (119.0 mL of a 2.0 M solution, 0.238 mol) is placed in a 500 ml three-neck round bottom flask adapted with magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is cooled to -78 ° C. 3,7-Dimethyl-1,6-octadien-3-yl acetate (22.04 g, 0.112 mol) is dissolved in THF (5 mL) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for a further 15 minutes, before being treated with a solution of p-anisoyl chloride (35.00 g, 0.106 mol) dissolved in THF (30 mL) over a period of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (80 mL). The mixture
P763 poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The mixture is poured into a separatory funnel containing ether (250 mL) and water (150 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 mL), water
(2 x 150 mL) and brine (150 mL), dried over MgSO4 and filtered. The solvent is removed by rotary evaporation to give an oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having XH and 13C NMR spectra consistent with the desired product.
EXAMPLE 6 Preparation of (α, α-4-trimethyl-3-cyclohexenyl) methyl 3- (β-naphthyl) -3-oxo-propionate Lithium diisopropylamide (171.0 mL of a 2.0 M solution, 0.242 mol) was placed in a 1000 L three-mouth round bottom fitted with magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is cooled to -78 ° C. Dissolve (a, a-4-trimethyl-3-cyclohexenyl) methyl acetate (30.00 g, 0.152 mol) in THF (10 mL) and the resulting solution is added to the flask within 45 minutes. Once I know
P763 completes the addition, the mixture is stirred for an additional 15 minutes, before being treated with a solution of 2-naphthoyl chloride (29.00 g, 0.152 mol) dissolved in THF (50 mL) within 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (105 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a semi-white solid which is triturated in cold n-pentane to give a white powder having? H and 13C NMR spectra. consistent with the desired product.
EXAMPLE 7 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3- (α-naphthyl) -3-oxo-propionate Lithium diisopropylamide (96.3 mL of a 2.0 M solution, 0.193 mol) is placed in a bottom flask
P763 round, three mouths, 500 mL adapted with magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is cooled to -78 ° C. 3,7-Dimethyl-1,6-octadien-3-yl acetate (17.81 g, 0.091 mol) is dissolved in THF (5 mL) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for an additional 15 minutes before being treated with a solution of 1-naphthoyl chloride (16.82 g, 0.086 mol) dissolved in THF (25 mL) in a term of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (53 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSO4 and filtered. The solvent is removed by rotary evaporation to give an oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having XH and 13C NMR spectra consistent with the desired product.
P763 EXAMPLE 8 Preparation of cis 3-hexen-l-yl 3- (β-naphthyl) -3-oxo-propionate Lithium diisopropylamide (133.0 mL of a 2.0 M solution, 0.266 mol) is placed in a round bottom flask, of three mouths, 500 mL adapted with magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is cooled to -78 ° C. Cis 3-hexenyl acetate (17.80 g, 0.125 mol) is dissolved in THF (10 mL) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for a further 15 minutes before being treated with a solution of 2-naphthoyl chloride (22.51 g, 0.118 mol) dissolved in THF (30 mL) in a term of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (70 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a
P763 colorless oil having XH and 13C NMR spectra consistent with the desired product.
EXAMPLE 9 Preparation of 9-decen-l-yl 3- (ß-naphthyl) -3-oxo-propionate Lithium diisopropylamide (79.8 mL of a 2.0 M solution) is placed., 0.160 mol) in a 250 mL three-necked round bottom flask adapted with magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is cooled to -78 ° C. 9-Dece-1-yl acetate (14.91 g, 0.075 mol) is dissolved in THF (5 mL) and the resulting solution is added to the flask in a period of 45 minutes. Once the addition is complete, the mixture is stirred for a further 15 minutes, before being treated with a solution of 2-naphthoyl chloride (13.80 g, 0.071 mol) is dissolved in THF (25 mL) in a period of 30 minutes . The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (47 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSO4 and filtered. The solvent is removed
P763 by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having H and 13 C NMR spectra consistent with the desired product.
EXAMPLE 10 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3- (nonanyl) -3-oxo-propionate Lithium diisopropylamide (133.7 mL of a 2.0 M solution, 0.267 mol) is placed in a flask round bottom, three mouths, 500 mL adapted with magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is cooled to -78 ° C. 3,7-Dimethyl-1,6-octadien-3-yl acetate (24.73 g, 0.126 mol) is dissolved in THF (40 mL) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for a further 15 minutes before being treated with a solution of nonanoyl chloride (21.88 g, 0.119 mol) over a period of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% HCl (60 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The organic layers
P763 combined are washed with saturated NaHCO3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSO4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having H and 13 C NMR spectra consistent with the desired product.
EXAMPLE 11 Preparation of 2,6-dimethyl-7-octen-2-yl 3- (nonanil) -3-oxo-propionate Lithium diisopropylamide (75.7 mL of a 2.0 M solution, 0.151 mol) is placed in a round bottom flask, of three mouths, 500 mL adapted with magnetic stirrer, internal thermometer, argon inlet and addition funnel. The flask is cooled to -78 ° C. Dissolve 2,6-dimethyl-7, octen-2-yl acetate (14.14 g, 0.071 mol) in THF (20 mL) and add the resulting solution to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for a further 15 minutes before being treated with a solution of nonanoyl chloride (12.38 g, 0.067 mol) in a term of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with HCl at
P763 20% (55 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 L). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having 1 H and 13 C NMR spectra consistent with the desired product.
EXAMPLE 12 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3-oxo-butyrate A mixture of linalool (100 g, 0.648 mol) and 4-dimethylaminopyridine (0.40 g, 3.20 mmol) in a flask of round bottom, three-mouth, 500 mL adapted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal thermometer is heated to 55 ° C. Di-tetene (54.50 g, 0.648 mol) is added dropwise over a period of 35 minutes. The mixture has a light hexotherm and changes from yellow to red in this period. After stirring for one more at 50 ° C, the mixture is cooled to room temperature. At this point, the NMR analysis
P763 indicates that the reaction is terminated. The material of this lot is taken to the next step. Purification of an early sample of this route by rapid chromatography
(elution with dichloromethane) gives the desired product in a yield of 92% and is practically colorless.
EXAMPLE 13 Preparation of 2,6-dimethyl-7-octen-yl 3-oxo-butyrate A mixture of dihydromyrcenol (37.88 g, 0.240 mol) and 4-dimethylaminopyridine (0.16 g, 1.30 mmol) in a round-bottomed flask, of three mouths, 100 mL adapted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal thermometer is heated to 50-60 ° C. Diethylene (20.16 g, 0.240 mol) is added dropwise in a period of 15 minutes. The mixture has a light hexotherm and changes from yellow to red during this period. After stirring for an additional hour at 50 ° C, the mixture is cooled to room temperature. At this point, the NMR analysis indicates that the reaction is terminated. Purification of the product mixture by flash chromatography (elution with dichloromethane) yields a desired product in 95% yield and is a practically colorless oil.
P763 EXAMPLE 14 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3- (β-naphthyl) -3-oxo-propionate 3,7-dimethyl-l, 6-octadien-3-yl 3 Crude oxo-butyrate (154.51, 0.648 mol) from the previous example is placed in a 300 mL three-necked round bottom flask fitted with condenser, argon inlet, addition funnel, magnetic stirrer and internal thermometer. The content is dissolved in 350 mL of dichloromethane and treated with calcium hydroxide powder (50.44 g, 0.681 mol). The mixture is stirred at 30 ° C for 30 minutes and then heated to 40 ° C. 2-Naphthoyl chloride (142.12 g, 0.746 mol) is dissolved in 20 mL of dichloromethane and added dropwise within 15 minutes. The mixture continues to be heated at this temperature for one hour. Ammonium chloride (36.41 g, 0.681 mol) is dissolved in 250 mL of water and added to the reaction mixture and the pH is adjusted to ~ 9 with 20% ammonium hydroxide. After stirring for 30 minutes at 35 ° C, the pH is adjusted to ~ 1 with 20% HCl. The mixture is transferred to a separatory funnel containing diethyl ether (500 mL) and water (500 mL). The layers are separated and the organic phase is washed with saturated NaHCO 3 solution.
(2 x 500 mL), dried over MgSO4, filtered and condensed by rotary evaporation to give a reddish yellow oil. At this point a yellow solid precipitates
P763 clear from the mixture. An equal volume of hexane is added and the solids are collected by filtration and dried. NMR analysis indicates that the solid is 2-naphthoic acid. The eluent is again concentrated by rotary evaporation to give a red oil. The oil is recovered in an equal volume of dichloromethane, passed through a plug of silica gel (400 g) and eluted with dichloromethane. The mixture is concentrated by rotary evaporation and purified by Kugelrohr distillation (40 ° C, 0.10 mm Hg, 30 minutes) to give 173.26 g (76.3%) of the product as a red oil; This product is a mixture of a 1:10 molar ratio of acetal of linalyl acetate to linalyl (2-naphthoyl) acetate. A portion of this material is purified by column chromatography (elution with 2.5% ethyl acetate and hexane) to give the desired product as a light yellow oil.
EXAMPLE 15 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3- (β-naphthyl) -3-oxo-2,2-dimethylpropionate Sodium hydride (2.30 g, 0.057 mol
60%) and tertrahydrofuran (50 mL) in a 250 mL three-necked round bottom flask fitted with magnetic stirrer, ice bath, addition funnel, internal thermometer and argon inlet. The contents of the flask are
P763 cooled to 0 ° C. Dissolve 3,7-dimethyl-l, 6-octadien-3-yl 3- (β-naphthyl) -3-oxo-propionate (8.94 g, 0.025 mol) in 50 mL of tetrahydrofuran and add dropwise to the flask in a term of 30 minutes. During the addition, the mixture releases gas. After stirring for one hour, methyl iodide (7.24 g, 0.051 mol) is added to the reaction mixture. Stirring is continued for 2 hours at 0 ° C and then at room temperature for 18 hours. The mixture is neutralized with 20% HCl and extracted with diethyl ether. The organic layers are washed with saturated NaHCO 3 solution, water, dried over MgSO 4, filtered, concentrated by rotary evaporation and purified by flash chromatography to give the desired compound. The structure is confirmed by XH and 13C in NMR.
EXAMPLE 16 Preparation of 3,7-dimethyl-l, 6-octadien-3-yl 3- (β-naphthyl) -3-oxo-2-methylpropionate Sodium hydride (3.92 g, 0.098 mol 60%) and tertrahydrofuran are placed (100 mL) in a 250 mL three-necked round bottom flask fitted with magnetic stirrer, ice bath, addition funnel, internal thermometer and argon inlet. The flask content is cooled to 0 ° C. Dissolve 3,7-dimethyl-l, 6-octadien-3-yl 3- (ß-naphthyl) -3-oxo-propionate (15.28 g, 0.044 mol) in 50 mL
P763 tetrahydrofuran and added dropwise to the flask within 30 minutes. During the addition, the mixture releases gas. After stirring for one hour, methyl iodide (10.65 g, 0.075 mol) is added to the reaction mixture. The stirring is continued for 2 hours at 0 ° C and then at room temperature for 18 hours. The mixture is neutralized with 20% HCl and extracted with diethyl ether. The organic layers are washed with saturated NaHCO3 solution, dried over MgSO4, filtered, concentrated by rotary evaporation and purified by flash chromatography to give the desired compound. The structure is confirmed by XH and 13C in NMR.
EXAMPLE 17 Preparation of 3,7-dimethyl-l, 6-octadien-3-yl 3- (hexyl) -3-oxo-propionate 3,7-Dimethyl-l, 6-octadien-3-yl 3-oxo is added. -butyrate (30.00 g, 0.126 mol), dichloromethane (50 mL) and methyl ethyl ketone (10 mL) combined in a 500 mL round bottom flask, adapted with internal thermometer, addition funnel, condenser and inlet of argon. Calcium hydroxide (9.80 g, 0.132 mol, powder) is added. To the flask and stir the mixture for 1 hour. Heptanoyl chloride (17.84 g, 0.120 mol) in 10 ml of dichloromethane is added within 15 minutes to maintain the
P763 reaction temperature between 35 and 40 ° C. The reaction mixture continues to stir at 35-40 ° C for 2 hours. Ammonium chloride (7.06 g, 0.132 mol) is dissolved in 20 mL of water and added to the flask. After 20 minutes, concentrated ammonium hydroxide is added to the mixture to adjust the pH to ~ 9.0. After 1 hour, 20% HCl is added to lower the pH to ~ 1.0. After 1 hour, the mixture is poured into 300 mL of diclomethane. The layers are separated and the aqueous phase is extracted with 100 mL of dichloromethane. The combined organic layers are washed with saturated NaHCO 3 solution, water, dried over MgSO 4, filtered, concentrated by rotary evaporation and purified by flash chromatography to give the desired compound. The structure is confirmed by XH and 13C NMR.
EXAMPLE 18 Preparation of 3,7-dimethyl-l, 6-octadien-3-yl 3-oxo-2-benzylbutyrate Potassium carbonate (3.92 g, 0.028 mol), 3,7-dimethyl-l, 6-octadiene is placed -3-yl 3-oxo-butyrate (4.80 g,
0. 030 mol), benzyl chloride (4.80 g, 0.038) and acetone
(15 mL) in a 50 mL round bottom flask adapted with magnetic stirrer, condenser and argon inlet. The mixture is heated to reflux for 18 hours. The cooled mixture is filtered and concentrated by evaporation
P763 rotary. The resulting oil is purified on silica gel to give the desired compound. The structure is confirmed by thin layer chromatography and XH and 13C NMR.
Skin Conditioning Lotions An example of a skin care composition of this invention comprises an ester having a total number of carbon atoms greater than about 28, for example lauryl laurate, lauryl myristate, myristyl myristate, behenyl caprate, cetearyl palmitate, behenyl stearate, more preferably cetearyl palmitate and cetyl stearate. The compositions herein in addition to the esters described hereinbefore contain an emollient material in an amount such that the amount of more emollient ester is between about 0.2% and about 25% of the total composition, preferably about 4% to about 18% One function of the emollient is to ensure that the ester is plasticized sufficiently to allow it to be in a film-like state when applied to the skin. The emollient in the compositions herein is selected from the group consisting of fatty alcohols, esters having less than about 24 carbon atoms (e.g., isopropyl palmitate), branched chain esters having more than about 24 carbon atoms in total (e.g., cetearyl octonate), squalene, liquid or solid paraffins , mixture of fatty acids and squalene, mixtures of fatty acids and liquid or solid paraffins and mixtures thereof. The aforementioned esters, those having less than 24 carbon atoms or branched and having more than 24 carbon atoms, if used as emollients, should preferably be used in an amount equal to about one third of the chain length of the ester. The particular emollient selected depends, in part, on the particular ester selected since suitable plasticization is desired, as already mentioned. The emollient for esters having more than 28 carbon atoms is preferably selected from the group consisting of squalene, liquid or solid paraffins and mixtures of fatty alcohols with squalene or paraffins. Typical fatty alcohols and useful fatty acids of the compositions herein include those having from 12 to 22 carbon atoms such as cetyl alcohol, myristyl alcohol, stearyl alcohol, stearic acid and palmitic acid. Paraffins include, for example, mineral oil, petrolatum and paraffin wax. It is preferred that distilled water be used in the compositions herein.
P763 Optional Components Oily Phase Components In addition to the long chain esters of the emollients and emulsifiers described above, the oil phase of the compositions herein may contain a variety of materials, including: ) Esters that do not meet the requirements of the long-chain ester and are not present as an emollient, see above, such as oleyl oleate, isostearyl isostearate, isopropyl lanolate, isopropyl myristate, butyl stearate, myristyl lactate and 2-ethylhexyl palmitate; (b) Oils such as castor oil, jojoba oil, cottonseed oil, peanut oil and sesame oil; (c) Waxes such as ceresin wax, carnuba wax, beeswax and castor wax; (d) Lanolin, its derivatives and components such as acetylated lanolin, lanolin alcohols and lanolin fatty acids. Lanolin fatty acids are described in U.S. Patent No. Re. 29,814, October 24, 1978 to W.E. Snyder, which is taken here as a reference. (e) Polyalkylenes such as hydrogenated polyisobutene and polyethylene, and (f) Esterols such as cholesterol and phytosterol. The optional materials of the oil phase can comprise up to about 80% of the oil phase, preferably up to about 35%. When used at these levels, the optional components do not impair the occlusive nature of the compositions and are added to the overall cosmetic performance of the composition. Components of the Aqueous Phase The aqueous phase of the compositions may contain many different materials, among which are included: (a) Humectants such as sorbitol, glycerin, propylene glycol, alkoxylated glucose and hexanetriol, at a level of about 1% to about 20% . (b) Thickening agents such as carboxyvinyl polymers, ethyl cellulose, polyvinyl alcohol, carboxymethyl cellulose, vegetable gums and vegetable clays such as Veegum.RTM. (Magnesium aluminum silicate, R. T. Vanderbilt, Inc.) at a level of from about 0.01% to about 6%. (c) Proteins and polypeptides at a level of from about 0.1% to about 3%; (d) Preservatives such as methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid (Parabens-
P763 Mallinckrodt Chemical Corporation) EDTA and imidazolidinyl urea (Germall 115-Sutton Laboratories) at a level of from about 0.2% to about 2.5%; and (e) An alkaline agent such as sodium hydroxide to neutralize, if desired, part of the fatty acids or thickeners that may be present. All percentages of these additional aqueous phase components are of the total composition. The compositions herein may also have agents suitable for aesthetic purposes such as for example dyes. The composition of the present invention is preferably free of materials that adversely affect its performance. Therefore, elements such as polyethylene glycols are preferably only present at levels below 1% of the total composition. The pH of the compositions herein, preferably lies in a range of about 7.5 to 10. MANUFACTURING METHOD The compositions of the present invention generally have a lotion consistency and may be in the form of oil-in-water or water-in-oil emulsions, the latter being preferred because of its more pleasing cosmetic properties. The compositions of the present invention are preferably made by the method
P763 comprising the steps of: (a) preparing the oil phase; (b) preparing the aqueous phase; and (c) adding the oil phase to the aqueous phase. Step (a) is carried out by heating the materials of the oil phase to a temperature of about 75 ° C to about 100 ° C. Step (b) is carried out by heating the materials of the aqueous phase to a temperature approximately equal to that of the oil phase. The emulsion is formed by slowly adding the oil phase prepared in step (a) to the aqueous phase prepared in step (b)with agitation. Pro-mixes of raw materials comprising the fragrance delivery system or other ingredients can be added to the phase in which they are soluble before mixing the two phases or can be added directly to the mixed aqueous and oily phases. In addition to the fragrance-containing compositions that are used in human skin, the raw material mixtures of the present invention are suitable for use in any fragrance-mediated or odor-controlling application. An example of this is the ability to control odor in beds for animals and odor control items useful for lining cages, stables and other areas of room for animals
P763 domestic. For example, U.S. Patent No. 5,339,769 to Toth et al. , issued August 23, 1994 describes a process for the preparation of an absorbent composition that can be well adapted to the raw material mix materials of the present invention. An example of a suitable bed material comprising the raw material mixes of the present invention can be formed by the following process. A Glatt type fluidized bed granulator is loaded with 10,000 g of bentonite clay (90% of the particles have a size greater than 420 microns) and 10 g of cellulose ether (Methocel ™ K15M Premium, a cellulose ether having a viscosity of 15,000 centipoise (cps) as a 2% aqueous solution). The granulator starts up and the temperature of the product is brought to 40 ° C (exit temperature). When the outlet temperature reaches approximately 40 ° C, the atomized water is sprayed on the moving powders inside the granulator. During the granulation process, the inlet air temperature is maintained at 70 ° C-80 ° C; the spray pressure is 28-35 psi and the spray cycle is 45 seconds with a stirring time of 15 seconds. The clay agglomerates / cellulose ether swell over time. Water hydrates the ether polymer
P763 cellulose, which produces adhesion to form the granule. At this time it is more advantageous to introduce the materials of the mixture of raw materials and other aesthetic fragrances. The granule formation promotes the aggregation of small size particles of the inert substrate, for example, clay particles of about 50 to 600 microns. The formation of the granules significantly reduces the dust quality in the final product while the bed forms an agglomerate upon wetting. In an alternative embodiment of a hodgepodge of the clay-based pet bedding / raw material bedding articles, once the clay particles have formed, it can be supplied to the surface of the granule, for a suitable medium, a concentrated solution or a mixture based on an alcohol carrier of the pro-mixture of raw materials. A deodorant gel stick of the present invention having the following composition and being essentially free of water, is prepared in the following manner:
P763 TABLE V% by weight
1. In powder form and obtained commercially from Olim.
2. Pro-mix of raw materials comprising 75% of the pro-mix of Example 1 and 25% of the pro-mix of Example 4. All the above materials, except the fragrance promise, are mixed vigorously and heated to approximately 100%. ° C until the mixture becomes clear. The mixture is then cooled to about 80 ° C and the mixture is added with stirring. The mixture is poured into bar molds and cooled to room temperature to form the deodorant gel bar composition of the present invention. A cleansing composition for personal care is prepared by combining the following ingredients, using conventional mixing techniques.
P763 TABLE VI% by weight P763 1. Obtained as Pemulen® from B.F. Goodrich Corporation.
2. Obtained as Carbomer® 954 from B.F. Goodrich Corporation 3. As a 50% aqueous solution. 4. Light mineral oil available as Drakeol 5 from Penreco, Dickenson, TX. 5. Pro-mixture of raw materials according to Example 1.
6. Pro-mix of raw materials according to Example 9.
The above examples 22 to 25 can be suitably prepared in the following manner. In a suitable vessel, the ingredients of Phase A are mixed at room temperature to form a dispersion and heated with stirring at 70-80 ° C. In a separate vessel, the ingredients of Phase B are heated with stirring at 70-80 ° C. Then Phase B is added to Phase A with mixing to form the emulsion. Subsequently, Phase C is added to neutralize the composition. The ingredients of Phase D are added with mixing, then
P763 to cool to 45-50 ° C. The ingredients of Phase A are then added with stirring, and then cooling to 40 ° C. Phase F is heated with mixing at 40 ° C and added to the emulsion, which is cooled to room temperature. The resulting cleaning compositions are useful for cleaning the skin. The emulsion is demulsified on contact with the skin.
P763
Claims (3)
- EIVINICATIONS 1. A composition applied to the skin having improved fragrance and fragrance retention longevity characteristics, comprising: a) at least about 0.01%, preferably from about 0.01% to about 15%, more preferably about 1% to about 5%, still more preferably from about 0.1% to about 1% by weight of a β-ketoester having the formula: wherein R is alkoxy derived from an alcohol of fragrance raw material; R1, R2 and R3 are each independently hydrogen, substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cyclic alkyl, substituted or unsubstituted C2-C30 linear alkenyl , C3-C30 substituted or unsubstituted branched alkenyl, substituted or unsubstituted C3-C30 cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl, branched alkynyl P763 C3-C30 substituted or unsubstituted, substituted or unsubstituted C6-C30 alkylenearyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C20 alkylenenoxy, substituted or unsubstituted C3-C20 alkylene-alkyl, substituted C7-C20 alkylenearyl or unsubstituted, substituted or unsubstituted C6-C20 alkyleneoxyaryl, and mixtures thereof; provided that at least one of R1, R2 or R3 is a unit that has the formula: wherein R4, R5 and R6 are each independently hydrogen, linear alkyl C ^ Cj ---, substituted or unsubstituted, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cyclic alkyl, linear alkoxy Cj -C30 substituted or unsubstituted, substituted or unsubstituted C3-C30 branched alkoxy, substituted or unsubstituted C3-C30 cyclic alkoxy, substituted or unsubstituted C2-C30 linear alkenyl, substituted or unsubstituted C3-C30 branched alkenyl, cyclic alkenyl C3 -C30 substituted or unsubstituted, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted C3-C30 branched alkynyl, substituted or unsubstituted C6-C30 alkylenearyl; or R4, R5 and Rd taken together can form a substituted or unsubstituted C6-C30 aryl, and mixtures thereof; b) at least about 0.01% by weight of one or more adjunct ingredients selected from the group consisting of surfactants, emollients, bactericides, gelling agents, spreaders, propellants, dyes, colorants, ointment bases, lanolin, antiperspirants, mineral oil, talc, abrasives, optical brighteners, phase stabilizing agents, absorbers, and mixtures thereof; and c) the rest are carriers. 2. A composition according to claim 1 wherein R1 has the formula: R2, R3, R4 and R5 are each hydrogen; and R6 is hydrogen, substituted or unsubstituted C-j-C ^ linear alkyl, substituted or unsubstituted C3-C16 branched alkyl, and mixtures thereof. 3. A composition according to claim 1 wherein R1 has the formula: P763 R2 and R3 are each hydrogen, R4, R5 and R6 taken together form C -C phenyl, "substituted or unsubstituted, naphthyl and mixtures thereof. 4. A composition according to claim 1, wherein the β-ketoester is selected from the group consisting of: 3, 7-dimethyl-l, 6-octadien-3-yl 3 (β-naphthyl) -3-oxo-propionate , 2,6-dimethyl-7-octen-2-yl 3- (4-methoxyphenyl) -3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3- (4-methoxyphenyl) -3 -oxo-propionate, 2,6-dimethyl-7-octen-
- 2-yl 3- (ß-naphthyl) -3-oxo-propionate, 3,7-dimethyl-l, 6-octadien-3-yl 3- ( 4-methoxyphenyl) -3-oxo-propionate, (a, a-4-trimethyl-3-cyclohexenyl) methyl 3- (ß-naphthyl) -3-oxo-propionate, 3,7-dimethyl-l, 6-octadien -3-yl 3 (α-naphthyl) -3-oxo-propionate, cis 3-hexen-l-yl 3- (ß-naphthyl) -3-oxo-propionate, 9-decen-l-yl 3- (ß -naphthyl) -3-oxo-propionate, 3, 7-dimethyl-l, 6-octadien-3-yl
- 3- (nonanil) -3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3- (nonanyl) -3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-l, 6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen -2-yl 3- (ß-naphthyl) -3-oxo-2-methylpropionate, 3,7-dimethyl-l, 6-octadien-3-yl 3- (ß-naphthyl) -3-oxo-2-methylpropionate , 3, 7-dimethyl-2, 6-octadienyl 3-heptyl-3-oxo-propionate, and mixtures thereof. A composition according to claim 1, wherein the adjunct ingredients are selected from the group consisting of dispersants, enzymes, dyes, perfumes, dyes, charge-type salts, hydrotropes, fluorescers, fabric conditioners, lanolin, hydrolyzable surfactants, preservatives, antioxidants, chelants, stabilizers, anti-shrinking agents, germicides, fungicides, anti-corrosion agents, active pharmaceutical agents and mixtures thereof. A method for providing the human skin or hair with prolonged fragrance benefits, comprising the steps of contacting the human skin or hair with a composition comprising: a) at least about 0.01%, preferably about 0.01% to about 15%, more preferably from about 1% to about 5%, still more preferably from about 0.1% to about 1% by weight of a β-ketoester having the formula: P763 wherein R is alkoxy derived from an alcohol of fragrance raw material; R1, R2 and R3 are each independently hydrogen, substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cyclic alkyl, substituted or unsubstituted C2-C30 linear alkenyl , C3-C30 substituted or unsubstituted branched alkenyl, substituted or unsubstituted C3-C30 cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl, branched alkynyl C3-C30 substituted or unsubstituted, C6-C, substituted or unsubstituted alkylenearyl, aryl C -C, "substituted or unsubstituted, substituted or unsubstituted C2-C20 alkylene, substituted or unsubstituted C3-C20 alkylene-alkyl, C7-alkylenediary -C20 substituted or unsubstituted, substituted or unsubstituted C6-C20 alkyleneoxyaryl, and mixtures thereof; provided that at least one of R1, R2 or R3 is a unit that has the formula: wherein R4, R5 and R6 are each independently hydrogen, substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cyclic alkyl, substituted C? -C30 linear alkoxy or unsubstituted, substituted or unsubstituted C3-C30 branched alkoxy, substituted or unsubstituted C3-C30 cyclic alkoxy, substituted or unsubstituted C2-C30 linear alkenyl, substituted or unsubstituted C3-C30 branched alkenyl, substituted C3-C30 cyclic alkenyl or unsubstituted, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted C3-C30 branched alkynyl, substituted or unsubstituted C6-C30 alkylenearyl; or R4, R5 and R6 taken together can form a substituted or unsubstituted C6-C30 aryl, and mixtures thereof; b) at least about 0.01% by weight of one or more adjunct ingredients selected from the group consisting of surfactants, emollients, bactericides, gelling agents, spreaders, propellants, dyes, colorants, ointment bases, lanolin, antiperspirants, mineral oil, talc, abrasives, optical brighteners, phase stabilizing agents, absorbers, active pharmaceutical compounds and mixtures thereof; and c) the rest are carriers. P763
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/024.117 | 1996-08-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA99001723A true MXPA99001723A (en) | 1999-09-20 |
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