EP1171556A1 - Aldehydes utiles en tant que matieres brutes de parfum et precurseurs de parfum contenant un atome de carbone alpha tertiaire - Google Patents
Aldehydes utiles en tant que matieres brutes de parfum et precurseurs de parfum contenant un atome de carbone alpha tertiaireInfo
- Publication number
- EP1171556A1 EP1171556A1 EP00923404A EP00923404A EP1171556A1 EP 1171556 A1 EP1171556 A1 EP 1171556A1 EP 00923404 A EP00923404 A EP 00923404A EP 00923404 A EP00923404 A EP 00923404A EP 1171556 A1 EP1171556 A1 EP 1171556A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substituted
- unsubstituted
- mixtures
- alkyl
- fragrance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D263/06—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by oxygen atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0007—Aliphatic compounds
- C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances
Definitions
- the present invention relates to novel fragrance pro-accords which release fragrance raw material aldehydes suitable for use in perfume and fine fragrance compositions thereby providing said compositions with endu ⁇ ng fragrance characte ⁇ stics.
- the present invention further relates to a fragrance delivery system which comp ⁇ ses the novel fragrance pro-accords of the present invention m combination with a) one or more pro-accords ter aha acetals, ketals, orthoesters, orthocarbonates, and b) one or more fragrance raw mate ⁇ als.
- fragrance Aside from common "perfume vehicles" inter aha, fine perfumes, colognes, eau de toilettes, and after-shave lotions, a wide va ⁇ ety of personal care or personal hygiene items also deliver for aesthetic reasons fragrance notes, accords, or fragrance "characteristics". It is well known that mixtures of perfume or fragrance raw materials when deposited on the skin lose intensity and may change character with time, mainly due to factors such as differential evaporation and skin penetration. Many attempts have been made to minimize these drawbacks, but so far without notable success. Particularly, efforts have been made to prolong the diffusion, as well as to improve other characte ⁇ stics of fragrance materials, by e.g. increasing the fragrance raw material concentration or by using additives such as silicones, glycerol, polyethylene glycols and so on. Such additions, however, have never been adequate to increase the longevity of the fragrance odor
- aldehydes form the most commonly delivered fragrance raw mate ⁇ als. Alcohols and esters can be suitably released m a delayed manner from an orthoester pro-accord or pro-fragrance.
- the controllable release of these fragrance raw materials thus provides the formulator with a means for delivering these fragrance ingredients, not only as an accord, but m a delayed-releasable manner over a period of time fragrance which is desirable to the fine fragrance and perfume user.
- the primary means for delivering aldehydes in a time-releasable manner has typically been via the acetal pro-fragrance.
- fragrance raw materials are components of a fragrance delivery system which can be formulated into fine fragrances, perfumes, personal care and personal hygiene products. Once formulated therein, the aldehyde fragrance raw material component can be released m a highly controllable manner to provide and additional enhanced fragrance longevity benefit.
- a first aspect of the present invention relates to novel fragrance raw material aldehydes which comp ⁇ se a tertiary ⁇ -carbon having at least one alkyl group, preferably a methyl group, said fragrance raw mate ⁇ als having the formula:
- R and R' are each independently: a) C r C 10 substituted or unsubstituted linear alkyl; b) C 3 -C 15 substituted or unsubstituted branched alkyl, c) C 2 -C, 5 substituted or unsubstituted linear alkenyl; d) C 3 -C, 5 substituted or unsubstituted branched alkenyl; e) C 3 -C 15 substituted or unsubstituted cycloalkyl; f) C 4 -C 15 substituted or unsubstituted branched cycloalkyl; g) C 4 -C 15 substituted or unsubstituted cycloalkenyl; h) C 5 -C 15 substituted or unsubstituted branched cycloalkenyl;
- R 3 is hydrogen, C,-C 15 substituted or unsubstituted linear alkyl, C,- C 15 substituted or unsubstituted branched alkyl, C 2 -C 22 substituted or unsubstituted linear alkenyl, C 3 -C 22 substituted or unsubstituted branched alkenyl, or mixtures thereof;
- R 4 is hydrogen, C r C 6 substituted or unsubstituted linear alkyl, C 3 -C 6 substituted or unsubstituted branched alkyl, or mixtures thereof;
- R 9 ⁇ s: i) hydrogen; n) C,-C 4 alkyl;
- R 5 and R 6 can be taken together to form a C 3 -C 6 spiroannulated ring, carbonyl unit, or mixtures thereof; y has the value from 0 to 10, z has the value from 1 to 50; r) R and R 1 can be taken together to form: l) a C 3 -C 6 substituted or unsubstituted spiroannulated ring; n) a substituted or unsubstituted non-aromatic ring comprising from 5 to 7 atoms in the ring; in) a substituted or unsubstituted non-aromatic heterocyclic ring comp ⁇ sing from 5 to 7 atoms in the ring; IV) a substituted or unsubstituted fused ring system comprising from 5 to 20 atoms; and
- the present invention further relates to fragrance raw material releasing pro-fragrances or pro-accords which comp ⁇ se the novel aldehydes of the present invention.
- the present invention also relates to fragrance raw material delivery systems, said delivery systems comp ⁇ sing:
- pro-accord 1) at least 1% by weight, of an ⁇ -tertiary carbon aldehyde releasing pro- fragrance component: n) optionally from about 1% by weight, of one or more pro-accords formed from at least one fragrance raw material, wherein said pro-accord is selected from the group consisting of acetals, ketals, orthoesters, orthocarbonates, and mixtures thereof, each pro-accord releasing upon hydrolysis said fragrance raw material from which it is formed, said fragrance raw materials selected from the group consisting of pnmary, secondary, and tertiary alcohols, aldehydes, ketones, esters, carbonates, and mixtures thereof, provided each pro-accord: a) is formed from at least one fragrance raw material having a molecular weight greater than or equal to about 100 g/mol; b) has a fragrance release half- life of greater than or equal to about
- a fragrance raw material component comprising:
- the present invention relates to novel aldehyde fragrance raw materials and pro- fragrances which are capable of releasing said aldehyde fragrance raw materials.
- the novel aldehydes and pro-fragrances comprise a fragrance delivery system which can be suitably formulated into fine fragrances, eau de toilettes, body washes, perfumes, deodorants, and other personal care and personal hygiene articles Aldehyde Fragrance Raw Mate ⁇ als
- novel aldehydes of the present invention which function as fragrance raw materials have the general formula: wherein R is independently. a) C,-C,o substituted or unsubstituted linear alkyl; b) C 3 -C 15 substituted or unsubstituted branched alkyl; c) C 2 -C 15 substituted or unsubstituted linear alkenyl; d) C 3 -C, 5 substituted or unsubstituted branched alkenyl; e) C 3 -C, 5 substituted or unsubstituted cycloalkyl; f) C 4 -C 15 substituted or unsubstituted branched cycloalkyl; g) C 4 -C 1S substituted or unsubstituted cycloalkenyl; h) C 5 -C 15 substituted or unsubstituted branched cycloalkenyl; l) C 6 -C 15 substituted or unsubstituted
- each R 5 , R 6 , and R 7 is independently; l) hydrogen; n) -OH; m) C,-C 4 alkyl;
- R 8 ⁇ s: ⁇ ) hydrogen; n) C,-C 4 alkyl; in) or mixtures thereof;
- R 9 ⁇ s: l) hydrogen; n) C,-C 4 alkyl; m) or mixtures thereof;
- R 5 and R 6 can be taken together to form a C 3 -C 6 spiroannulated ring, carbonyl unit, or mixtures thereof; y has the value from 0 to 10, z has the value from 1 to
- R 1 is independently: a) C,-C 10 substituted or unsubstituted linear alkyl; b) C 3 -C, 0 substituted or unsubstituted branched alkyl, c) C 2 -C 10 substituted or unsubstituted linear alkenyl; d) C 3 -C 10 substituted or unsubstituted branched alkenyl; e) C 3 -C 15 substituted or unsubstituted cycloalkyl; f) C 4 -C, 5 substituted or unsubstituted branched cycloalkyl; g) C 4 -C 15 substituted or unsubstituted cycloalkenyl; h) C 5 -C 1S substituted or unsubstituted branched cycloalkenyl;
- R 5 and R 6 can be taken together to form a C 3 -C 6 spiroannulated ⁇ ng, carbonyl unit, or mixtures thereof; y has the value from 0 to 10, z has the value from 1 to
- R and R' can be taken together to form:
- a substituted or unsubstituted non-aromatic heterocyclic ⁇ ng system comprising from 5 to 7 atoms;
- a substituted or unsubstituted fused ring system comprising from 5 to 20 atoms, for example, a fragrance raw material aldehyde having the formula ⁇
- fragrance raw material aldehydes according to the present invention: 2,2,6,10-tetramethyl-9-undecenal; 2-ethyl-2,6, 10-t ⁇ methyl-9-undecenal;
- the present invention further relates to pro-fragrances which release the aldehydes of the present invention.
- the pro-fragrances are suitable for use in the fragrance delivery system which is further described herein below.
- Key to the aldehyde releasing pro-fragrances of the present invention is the ability of the formulator to prepare a compound pro-fragrance which has a specific release rate of aldehyde fragrance raw material.
- the formulator may design pro- fragrances to release at any rate which the formulator finds useful to the consumer.
- the formulator is able to make a side by side comparison of structurally dissimilar molecules and evaluate their relative fragrance raw material release patterns. In this way not only can the formulator determine with minimal experimentation whether a compound is suitable for use as a pro- fragrance, but also determine the release profile of the molecule. Therefore, a slight structural modification can result m a more finely tuned fragrance delivery system.
- the aldehyde releasing pro-fragrances of the present invention are preferably preferaby oxazolidmes, tertahydro-lJ-oxazmes, thiazolidines, or tetrahydro-lJ-thiazines, more preferably oxazolidmes, or tertahydro-lJ-oxazmes, most preferably oxazolidmes having the formula:
- R, R 1 , and n are the same as defined herein above X is oxygen or sulfur, each R 2 , R 3 , R 6 and each R 4 and R 5 pair are independently. a) hydrogen; b) R; c) hydroxyl; d) a carbonyl comprising unit having the formula: wherein R 7 is:
- C 15 preferably C 3 -C 10 , more preferably C 3 -C 4 substituted or unsubstituted branched alkyl; C 2 -C 22 , preferably C 2 -C 10 , more preferably C 2 -C 4 substituted or unsubstituted linear alkenyl; C 3 -C 22 substituted or unsubstituted branched alkenyl, or mixtures thereof; in) -N(R 9 ) 2 in the case of amides wherein each R 9 is independently hydrogen; C r C, 5 , preferably C C 10 , more preferably C,-C 4 substituted or unsubstituted linear alkyl; C 3 -C 15 , preferably C 3 -C 10 , more preferably C 3 - C 4 substituted or unsubstituted branched alkyl; or mixtures thereof; iv) C,-C 22 , preferably C,-C 5 substituted or unsubstituted linear alkyl; v
- each R ( 10 , D Rl l , an ,dA ⁇ R> n is independently;
- R 10 , R 11 , and R 12 are each hydrogen; l) hydrogen; n) C,-C 4 alkyl, preferably methyl; 111) or mixtures thereof; preferably R 13 is methyl or hydrogen, more preferably hydrogen; R ,4 ⁇ s:
- R 10 and R u can be taken together to form a C 3 -C 6 spiroannulated ring, carbonyl unit, or mixtures thereof; y has the value from 0 to 10, z has the value from 1 to 50; f) any two R 2 , R 3 , R 4 , R 5 , or R 6 units can be taken together, and where feasible, combined to form: l) a carbonyl moiety; n) a C 3 -C 6 spiroannulated ring; m) a heterocyclic aromatic ring comprising from 5 to 7 atoms; iv) a non-heterocychc aromatic ring comprising from 5 to 7 atoms; v) a heterocyclic ⁇ ng comprising from 5 to 7 atoms; vi) a non-heterocychc ring comprising from 5 to 7 atoms; vn) or mixtures thereof; g) and mixtures thereof; the index y is an integer from 1 to 3,
- the present invention further relates to fragrance delivery systems which are suitable for use in delivering an enhanced duration aesthetic benefit.
- the fragrance delivery systems are suitable for use and are compatible with any composition which may require a fragrance inter aha fine fra rances, perfumes, personal care products, deodorants, shampoos, laundry detergents, malodor masking agents.
- compositions of the present invention comprise from about 0.01%, preferably from about 0.05%, more preferably from about 0.1%, most preferably from about 0.5% to about 10%, preferably to about 7%, more preferably to about 5%, most preferably to about 3% by weight, of a fragrance delivery system.
- the fragrance delivery systems comprise-
- A) from about 1%, preferably from about 10%, more preferably from about 25% to about 100%, preferably to about 90%, more preferably to about 75%, most preferably to about 50% by weight, of a pro-fragrance component comprising: 1) at least 1% by weight (10 ppb of the composition which employs the fragrance delivery system), of an ⁇ -tertiary carbon comp ⁇ sing aldehyde releasing pro-fragrance component according to the present invention as desc ⁇ bed herein; n) optionally at least 1% by weight (10 ppb of the composition which employs the fragrance delivery system), of one or more pro-accords formed from at least one fragrance raw material, wherein said pro-accord is selected from the group consisting of acetals, ketals, orthoesters, orthocarbonates, and mixtures thereof, each pro-accord releasing upon hydrolysis said fragrance raw material from which it is formed, said fragrance raw materials selected from the group consisting of primary, secondary, and tertiary alcohols, aldehydes, ketones, esters, carbonates
- compositions according to the present invention are fine fragrances or perfumes. These embodiments typically comp ⁇ se only fragrance raw materials, pro-fragrances, pro-accords, carriers, and stabilizers.
- the fine fragrance and perfume compositions which utilize the cyclic pro-fragrances of the present invention comprise a) at least 0.01%, preferably from about 0.1%, more preferably from about 5%, most preferably from about 20% to about 100%, preferably to about 75%, more preferably to 50% by weight, of an ⁇ -tertiary carbon comprising aldehyde releasing pro-fragrance component according to the present invention; b) optionally from about 1%, preferably from about 25% to about 99.99%, preferably to about 99.9%, more preferably to about 95%, most preferably to about 50%) by weight, of one or more pro-accords which comprise n fragrance raw materials but which release n+1 fragrance raw materials, preferably orthoesters, orthocarbonates, ⁇ -ketoesters, and mixtures thereof; c) optionally from about 1%
- the carriers, fixatives, or stabilizers will comprise the balance of the compositions.
- Typical carriers are methanol, ethanol (preferred), iso-propanol, polyethylene glycol, as well as water in some instances, especially as a vehicle to deliver materials which provide reserve alkalinity to the fragrance delivery system.
- Fixatives serve to lower the volatility of certain top and middle notes in order to extend their contact time on skin.
- Adjunct ingredients include perfume raw material components which are essential oils and are therefore not a single chemical entity.
- the adjunct ingredients may be mixtures of materials which serve a purpose m addition to providing a pleasurable odor (i.e., an astringent in a personal hygiene article).
- a "pro-accord which comprises n fragrance raw materials but which releases n+1 fragrance raw materials” is defined as "a compound which is prepared from one or more fragrance raw mate ⁇ als, said fragrance raw material being chemically transformed into a "releasable form” such that when said releasable form breaks down, the original fragrance raw mate ⁇ al is released as well as at least one other fragrance raw material which was not a starting material used in forming the releasable form”
- Pro-accords of this type are suitably described in U.S. Patent Application Serial Number 09/028,823 filed February 24, 1998.
- an optional component of the fragrance delivery systems of the present invention are pro-fragrances or pro-accords which are not heterocyclic aldehyde releasing pro-fragrances.
- the optional pro-accords or pro-fragrances are equally functional in either personal care compositions inter aha lotions, creams, deodorants or personal fragrance compositions inter aha fine fragrances, perfumes.
- Preferred optional pro-accords and/or pro-fragrances include, but are not limited to, orthoesters, orthocarbonates, acetals, ketals, ortholactones, and ⁇ -ketoesters.
- Non-limiting examples of optional orthoesters which are suitable for use in the fragrance delivery systems of the present invention include t ⁇ s-geranyl orthoformate, t ⁇ s(cz.s-3-hexen-l-yl) orthoformate, t ⁇ s(phenylethyl) orthoformate, b ⁇ s(c ⁇ tronellyl) ethyl orthoacetate, t ⁇ s(c ⁇ tronellyl) orthoformate, t ⁇ s(cz.s'-6-nonenyl) orthoformate, t ⁇ s(phenoxyethyl) orthoformate, t ⁇ s(geranyl, neryl) orthoformate (70:30 geranyhneryl), t ⁇ s(9-decenyl) orthoformate, t ⁇ s(3-methyl-5- phenylpentanyl) orthoformate, t ⁇ s(6-methylheptan-2-yl) orthoformate, t ⁇ s([4-(2,2,6-t ⁇ methyl
- Non-limiting examples of optional orthocarbonates which are suitable for use in the fragrance delivery systems of the present invention include b ⁇ s(ethyl) b ⁇ s(geranyl) orthocarbonate, b ⁇ s(ethyl) b ⁇ s(phenylethyl) orthocarbonate, b ⁇ s(ethyl) b ⁇ s(c/5-3-hexenyl) orthocarbonate, b ⁇ s(ethyl) b ⁇ s(c ⁇ tronellyl) orthocarbonate, b ⁇ s(ethyl) b ⁇ s(hnalyl) orthocarbonate, b ⁇ s(ethyl) b ⁇ s(menthyl) orthocarbonate, b ⁇ s(dodecyl) b ⁇ s(geranyl) orthocarbonate, and b ⁇ s(dodecyl) b ⁇ s(phenylethyl) orthocarbonate
- optional acetals which are suitable for use m the fragrance delivery systems of the present invention
- Non-limitmg examples of optional ketals which are suitable for use m the fragrance delivery systems of the present invention include b ⁇ s(hnalyl) ⁇ -ionone ketal, b ⁇ s(d ⁇ hydromyrcenyl) ⁇ -damascone ketal, b ⁇ s(hnalyl) 6,7-d ⁇ hydro-lJ,2,3,3-pentamethyl-4(5H)- mdanone ketal, b ⁇ s(d ⁇ hydromyrcenyl) ⁇ -ionone ketal, and b ⁇ s(c ⁇ tronellyl) czs-jasmone ketal
- Non-limiting examples of optional ⁇ -ketoesters which are suitable for use in the fragrance delivery systems of the present invention include 2,6-d ⁇ methyl-7-octen-2-yl 3 -(4- methoxyphenyl)-3-oxo-prop ⁇ onate, 3,7-d ⁇ methyl-l,6-octad ⁇ en-3-yl 3-( ⁇ -naphthyl)-3-oxo- propionate, 2,6-d ⁇ methyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-prop ⁇ onate, cis 3-hexen-l-yl 3-( ⁇ -naphthyl)-3-oxo-prop ⁇ onate, 2,6-d ⁇ methyl-7-octen-2-yl 3-(nonanyl)-3-oxo-prop ⁇ onate, 2,6- d ⁇ methyl-7-octen-2-yl 3-oxo-butyrate, 3,7-d ⁇ methyl-l,6-oc
- One aspect of the present invention which is a key element in providing the formulator with a method for determining the manner in which a pro-fragrance according to the present invention releases its fragrance raw material, is the measurement of the pro-fragrance "Fragrance Release Half-Life, (FRHL).
- the pro-fragrances useful in the personal care compositions of the present invention generally have a delayed release of final fragrance raw material in order to achieve the increased fragrance longevity benefits described herein.
- the pro-fragrances generally also deliver the fragrance raw materials du ⁇ ng a time period useful to the formulator, for example, within a time period desirable to the consumer.
- the pro-accords generally have a FRHL of less than or equal to 12 hours when measured in NaH2P04 buffer at pH 2.5 and greater than or equal to 0J hour when measured in NaH2PO4 buffer at pH 5.3.
- the "Fragrance Release Half-life” is defined herein as follows.
- Pro-fragrances deliver their corresponding mixture of fragrance raw materials or fragrance accords according to the equation:
- fragrance raw material which is released may be released as a single component or a multiple fragrance raw material accord
- the rate at which the fragrance is released is defined by the formula:
- Rate k[Pro-fragrance] and can be further expressed by the formula-
- the phosphate buffered water is prepared by admixing 3.95 mL of 85% phosphoric acid (H3PO4) and 24 g of sodium dihydrogen phosphate (NaH2PU4) with one liter of water. The pH of this solution is approximately 2.5. Next 10 mL of the phosphate buffer is admixed with 90 mL of dioxane and the pro-fragrance to be analyzed is added. The hydrolysis kinetics are then monitored by conventional HPLC at 30° C.
- a fragrance delivery system having one or more pro-fragrances which deliver a rapid release of fragrance raw mate ⁇ al in addition to the delayed onset of a fragrance.
- the hydrolysis rate, and therefore the determination of t j 2 must be measured in a buffer system which can accommodate this more rapid hydrolysis rate.
- the pro-fragrances of the present invention are stable under pH conditions encountered in the formulation and storage of fine perfume, personal care and personal hygiene articles which have a pH of from about 7J to 11.5, and during solution-use of such products. Due to their high molecular weight and hydrophobicity, these pro-fragrances and/or pro-accords remain deposited upon skm even when exposed to water (i.e. when formulated into a sun screen). Because the pro- fragrances are subject to hydrolysis when the pH is reduced, they hydrolyze to release their component fragrance compounds when applied to skm or are exposed even to reduced pH such as present in air and humidity The reduction in pH should be at least 0 1 , preferably at least about 0.5 units.
- the pH is reduced by at least 0.5 units to a pH of 7.5 or less, more preferably 6.9 or less.
- the solution m which the pro-accord is applied is alkaline Odor Value
- the pro-fragrances of the present invention typically have an Odor Value greater than or equal to about 1, preferably greater than or equal to about 5, more preferably greater than or equal to about 10.
- OV is the odor value of the fragrance raw material released upon the skm by the pro- accord.
- the odor value is the concentration of the fragrance raw material, FRM, on the skm surface divided by the Odor Detection Threshold, ODT.
- level of noticeability is often applied to and/or substituted for the term "odor value" Odor Detection Threshold
- odor detection threshold is defined as the level at which a fragrance raw material is perceptible to the average human.
- the odor detection threshold (ODT) of the compositions of the present invention are preferably measured by carefully controlled gas chromatograph (GC) conditions as described herembelow.
- the preferred fragrance raw materials of the present invention have an ODT of at least about 100 part per billion (ppb), more preferably 10 ppb, most preferably 1 ppb. Fragrance raw mate ⁇ als having an ODT greater than 10 parts per million (ppm) are typically avoided unless useful as an adjunct ingredient, for example, as an adjunct alcohol when adjusting the fragrance release half-life of an orthoester.
- Odor Detection Thresholds Determination of Odor Detection Thresholds is as follows.
- a gas chromatograph is characterized to determine the exact volume of material injected by a syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution.
- the air flow rate m accurately measured and, assuming the duration of a human inhalation to last 0.02 minutes, the sampled volume is calculated. Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of material.
- solutions are delivered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is notice.
- GC 5890 Series II with FID detector 7673 Autosampler Column J&W Scientific DB-1, length 30 m, l.d 0.25 mm, film thickness 1 ⁇ m.
- Split Injection 17/1 split ratio Autosampler. 1J3 ⁇ l/mjection Column flow: 1 J 0 mL/min Air flow: 345 mL/mm Inlet temperature: 245° C Detector temperature: 285° C Temperature Information - Initial temperature: 50° C
- a pro-fragrance or pro-accord may comprise a fragrance release half-life which ensures delivery of a fragrance raw material during a period of time useful to the formulator, unless the fragrance raw materials which comp ⁇ se said fragrance delivery system have ODT values large enough to be perceived by the user, the formulator will be compelled to use an inordinate amount of material to achieve a suitable fragrance level.
- the pro-fragrances of the present invention have a Skm Performance Index (SPI) greater than or equal to 0J, preferably greater than or equal to 0.5.
- SPI Skm Performance Index
- the Skm Performance Index is defined by the following:
- [Odor Value] * SPI wherein the term [Odor Value]* is the estimated concentration of the fragrance raw material in the headspace above a solution of the fragrance raw material as measured in a 1 % solution of ethanol, and t 1/2 is the fragrance release half-life measured at pH 5.3 m the above described buffer.
- the t, , of the SPI is measured at 5.3 and the value of the fragrance release half-life is preferably from 0J hours to 60 hours.
- the [Odor Value]* is an estimation of the vapor pressure of the fragrance raw material using empirically determined KOVATS indices.
- KOVATS index of a fragrance raw material is obtained from gas chromatographic analysis of the FRM and the experimental index is then used to determine the relative vapor pressure and hence the head space concentration of the fragrance raw mate ⁇ al.
- the formulator is able to fashion an aldehyde or ketone releasing cyclic pro-fragrance.
- the release rate of either an aldehyde or ketone fragrance raw material can be adjusted.
- pro-fragrances which release the same fragrance raw material, but at differing rates or levels, can be admixed to further prolong or extend the period of fragrance raw material delivery. The following is a non-limiting example of a b-amino ketone pro-fragrance according to the present invention.
- Racemic se ⁇ ne methyl ester hydrochlo ⁇ de (1.0 mol) is neutralized by the addition of sodium methoxide (1J mol) as a 25% solution in MeOH. After stirring about 15 minutes, anhydrous Na 2 S0 4 (2 mol) is added followed by ⁇ -methyl melonal (1 mole). The solution is stirred for 24 hr, filtered through a bed of Celite 545 and concentrated under reduced pressure. The resulting residue is taken up in toluene, washed thrice with sodium bicarbonate and concentrated. The resulting oil is stirred 24 hr under a vacuum of 0.2mm Hg to yield the desired product.
- a personnel cleanser composition is prepared by combining the following ingredients using conventional mixing techniques.
- a fragrance delivery system which comprises about 5% by weight of 2-( 1 J ,5-t ⁇ methylhex- 4-enyl)-5-carboxymethyloxazohd ⁇ ne according to Example 1.
- the above Examples 2-5 can be suitably prepared as follows.
- the Phase A ingredients are mixed at room temperature to form a dispersion and heated with stirring to 70-80° C.
- the Phase B ingredients are heated with stirring to 70-80° C.
- Phase B is then added to Phase A with mixing to form the emulsion.
- Phase C is added to neutralize the composition.
- the Phase D ingredients are added with mixing, followed by cooling to 45-50° C.
- the Phase E ingredients are then added with stirring, followed by cooling to 40° C.
- Phase F is heated with mixing to 40° C. and added to the emulsion, which is cooled to room temperature.
- the resulting cleansing composition is useful for cleansing the skm.
- the emulsion de-emulsifies upon contact with the skm.
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- Fats And Perfumes (AREA)
Abstract
La présente invention concerne des matières brutes de parfum comprenant un atome de carbone alpha tertiaire, des systèmes d'apport de parfum qui contiennent des matières brutes de parfum comportant un atome de carbone alpha tertiaire et des précurseurs de parfum qui sont capables d'apporter ladite matière brute de parfum contenant un atome de carbone alpha tertiaire et de produire un effet accru et prolongé de parfum de nature esthétique. Les composés et les systèmes selon la présente invention sont adaptés pour être utilisés dans des matières odorantes, des parfums et d'autres compositions raffinées de soins personnels.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13012799P | 1999-04-20 | 1999-04-20 | |
US130127P | 1999-04-20 | ||
PCT/US2000/010211 WO2000063329A1 (fr) | 1999-04-20 | 2000-04-14 | Aldehydes utiles en tant que matieres brutes de parfum et precurseurs de parfum contenant un atome de carbone alpha tertiaire |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1171556A1 true EP1171556A1 (fr) | 2002-01-16 |
Family
ID=22443177
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00923404A Withdrawn EP1171556A1 (fr) | 1999-04-20 | 2000-04-14 | Aldehydes utiles en tant que matieres brutes de parfum et precurseurs de parfum contenant un atome de carbone alpha tertiaire |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1171556A1 (fr) |
JP (1) | JP2002542380A (fr) |
AU (1) | AU4353100A (fr) |
WO (1) | WO2000063329A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR9915539A (pt) | 1998-10-23 | 2001-10-16 | Procter & Gamble | Pró-accord de fragrância e bibliotecas de fragrância de aldeìdo e cetona |
EP1764355A1 (fr) * | 2005-09-16 | 2007-03-21 | Givaudan S.A. | 6-Methoxy-2,6-diméthyloctanal et son utilisation en parfumerie |
EP2861567B1 (fr) * | 2012-06-19 | 2016-08-31 | Dow Global Technologies LLC | Composés antimicrobiens |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3225102A (en) * | 1960-12-13 | 1965-12-21 | Eastman Kodak Co | Allenic aldehydes |
US4011233A (en) * | 1973-06-28 | 1977-03-08 | Givaudan Corporation | 2-methyl-2-(4-methyl-3-pentene-1-yl) thiazolidine |
US4010207A (en) * | 1976-01-15 | 1977-03-01 | International Flavors & Fragrances Inc. | Process for the alkylation of α, β-unsaturated aldehydes |
US4068012A (en) * | 1976-11-11 | 1978-01-10 | International Flavors & Fragrances Inc. | Use of 1-(2-propenyl)-3-(4-methyl-3-pentenyl)-Δ3 -cyclohexene-1-carboxaldehyde and 1-(2-propenyl)-4-(4-methyl-3-pentenyl)-Δ3 -cyclohexene-1-carboxaldehyde |
US6013618A (en) * | 1997-04-24 | 2000-01-11 | Procter & Gamble Company | Perfumes having odor longevity benefits |
BR9908220A (pt) * | 1998-02-24 | 2000-10-24 | Procter & Gamble | Sistemas que oferecem matéria-prima de fragância de álcool terciário |
-
2000
- 2000-04-14 EP EP00923404A patent/EP1171556A1/fr not_active Withdrawn
- 2000-04-14 WO PCT/US2000/010211 patent/WO2000063329A1/fr not_active Application Discontinuation
- 2000-04-14 JP JP2000612409A patent/JP2002542380A/ja not_active Withdrawn
- 2000-04-14 AU AU43531/00A patent/AU4353100A/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO0063329A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2002542380A (ja) | 2002-12-10 |
AU4353100A (en) | 2000-11-02 |
WO2000063329A1 (fr) | 2000-10-26 |
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