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WO1997034578A1 - Compose precurseur de parfum - Google Patents

Compose precurseur de parfum Download PDF

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Publication number
WO1997034578A1
WO1997034578A1 PCT/US1997/005373 US9705373W WO9734578A1 WO 1997034578 A1 WO1997034578 A1 WO 1997034578A1 US 9705373 W US9705373 W US 9705373W WO 9734578 A1 WO9734578 A1 WO 9734578A1
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WO
WIPO (PCT)
Prior art keywords
pro
fragrance
fragrance compound
parent
alcohols
Prior art date
Application number
PCT/US1997/005373
Other languages
English (en)
Inventor
Lonnie Liddell Bryant, Jr.
Robert Ya-Lin Pan
Original Assignee
The Procter & Gamble Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from PCT/US1996/004060 external-priority patent/WO1997034986A1/fr
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU24322/97A priority Critical patent/AU2432297A/en
Priority to BR9708236A priority patent/BR9708236A/pt
Priority to JP9533806A priority patent/JPH11507397A/ja
Priority to US09/142,888 priority patent/US6096704A/en
Priority to EP97920027A priority patent/EP0904048A1/fr
Publication of WO1997034578A1 publication Critical patent/WO1997034578A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds releasing perfumes by thermal or chemical activation
    • 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

Definitions

  • the present invention relates to an acetal or a ketal pro-fragrance compound.
  • Acetals and ketals have long been known in perfumery. See Steffen Arctander, "Perfume and Flavor Chemicals," Arctander, N.J., 1969. The majority of these are methyl and ethyl types, and molecular weights may range widely. See, for example, Arctander abstract numbers 6, 11 , 210, 651 , 689, 1697, 1702, 2480, 2478. However, the known acetals and ketals are generally not desirable for use in laundry products. For 2478, which is phenylacetaldehyde dicitronellyl acetal, molecular weight 414.7, Arctander reports " .
  • Carrier mechanisms for perfume delivery are also known in the art. See for example, U.S. Patent 5,188,753, issued Feb. 23, 1993.
  • compositions such as deodorant sticks, comprising "body- activated" fragrances are also known.
  • the term apparently refers to the previously known tendency of materials such as acetals derived from perfume alcohols to hydrolyze under acidic pH conditions thereby releasing fragrance. See, for example, U.S. Patent 5,378,468, issued Jan. 3, 1995 and U.S. Patent 3,932,520, issued January 13, 1976.
  • Potential fragrance materials for use in such personal care compositions include particular acetals and ketals, exemplified by propylene glycol vanillin acetal.
  • the materials exemplified apparently are rather hydrophilic short chain alcohol or diol derivatives of fragrance aldehydes and upon hydrolysis, deliver one mole of the aldehyde per mole of the potential fragrance material.
  • This development is designed to be incorporated with a personal care product vehicle, resulting in clear deodorant sticks and the like and the compositions containing the potential fragrance materials are applied directly to the substrate (i.e. skin); therefore, the deposition problems resulting from the dilution, rinsing, etc., associated with the laundry process are not at issue.
  • Laundry detergents are used in dilute aqueous form and contain numerous detergent adjuncts such as synthetic detergents, builders, enzymes and the like which are capable of micellizing, or solubilizing the pro-fragrance. Further, the laundry process includes rinsing, and sometimes drying with tumbling machines after washing. The rinsing tends to remove the useful pro- fragrance material deposited. The tumble-drying further exacerbates the problem of delivering adequate residual fragrance to textile fabric surfaces.
  • the pro-fragrance compounds of the present invention can be used for a variety of products wherein the conventional fragrances are used. These are, for example, such as shampoos, conditioners, detergent hard surface cleaner, deodorants, cat litter, and the like.
  • pro-fragrance compound with improved dispersability in aqueous solutions.
  • pro-fragrance compound used for detergent composition further can be enhanced deposition on fabric surfaces in the wash solution, and enhanced retention on the washed surface during rinsing. None of the existing art provides all of the advantages and benefits of the present invention.
  • the present invention is directed to a pro-fragrance compound selected from the group consisting of an acetal, a ketal, and mixtures thereof, wherein at least one of a parent aldehyde, ketone, or alcohol of the pro-fragrance acetal or ketal is a fragrance compound, having a CLogP of less than about 4.
  • the CLogP is the logarithm to base 10 of the Octanol/Water Partition Coefficient of the pro-fragrances.
  • pro-fragrance compound means a compound which may or may not be odoriferous in itself but which, upon hydrolysis, produces a desirable odor which is characteristic of one or more of its hydrolysis products. This term includes mixtures of pro-fragrance compounds and further encompasses the term “pro-perfume.”
  • Acetals and Ketals can be considered as derivable from aldehydes or ketones in combination with alcohols. These aldehydes, ketones and alcohols are herein termed “parents” or “parent compounds” of the acetal or ketal. At least one parent of any of the instant acetals or ketais is a fragrance compound.
  • the pro-fragrance compound of this present invention has CLogP of less than about 4, wherein the CLogP is the logarithm to base 10 of the Octanol/Water Partition Coefficient of the pro-fragrance compound.
  • the pro- fragrances having the CLogP of less than about 4 give good dispersibility in the aqueous solution. Without being bound by theory, it is believed that the CLogP, as described herein, can be lower when the number of alkoxy moiety included in the pro-fragrance compound is increased.
  • These pro-fragrance compounds can further be characterized as having a molecular weight of at least about 170 and a half-life of less than 60 minutes when measured at pH 0 by the Hydrolysis Half-life (t-1/2) Test as described herein.
  • the preferred pro-fragrances can be cyclic or acyclic having at least 3 oxygens.
  • the cyclic pro-fragrance compound has at least two alkoxylate moiety and the acyclic pro-fragrance compound has at least 4 alkoxylate moiety.
  • pro-fragrance compounds herein are those derived from a fragrance or non-fragrance alcohol, particularly C6-C20 (preferably C11-C20. more preferably C14-C18 alcohols) saturated or unsaturated, linear or branched aliphatic alcohols, commonly referred to as detergent alcohols and a fragrant C9- or higher unsaturated aldehyde or a fragrance ketones.
  • a fragrance or non-fragrance alcohol particularly C6-C20 (preferably C11-C20. more preferably C14-C18 alcohols) saturated or unsaturated, linear or branched aliphatic alcohols, commonly referred to as detergent alcohols and a fragrant C9- or higher unsaturated aldehyde or a fragrance ketones.
  • parent alcohols of the present invention have at least one alkoxy moiety. Due to increasing the member of alkoxy moiety as described above, the pro-fragrances having the CLogP of less than about 4 give good dispersibility in detergent solution.
  • the preferred parent alcohols can include the alkoxylates of detergent alcohols, mono-alkyl ethers of short-chain polyalkoxylates, polyols including those which are alkoxylated with 1 to 30 groups of ethylene oxide or propylene oxide.
  • Preferred parent aldehydes or ketones herein, will be derived from a parent aldehyde having molecular weight above about 80.
  • acetals and ketals are included within the invention.
  • Many fragrant aldehydes, ketones, and alcohols which are suitable parents for the present acetals and ketals are known to the art. See, for example, Arctander's compilation referenced hereinabove for fragrant parents. These will be also obtainable commercially from perfume houses such as IFF, Firmenich, Takasago, H&R, Givaudan-Roure, Dragoco, Aldrich, Quest, and others.
  • Acetals The pro-fragrances of the present invention include an acetal.
  • the acetal can be used to deliver fragrance aldehydes, fragrance alcohols, or both, preferably to deliver fragrance aldehydes derived from parent aldehydes.
  • Acetals suitable in the present invention include the following structure:
  • X and Y are derived from a starting alcohol and R-
  • X and Y in the above general structure which can be either fragrant alcohols or non-fragrant alcohols includes variable alkoxy moieties.
  • X and Y can be the same or different allowing the delivery of more than one type of fragrant alcohol.
  • the alcohols are non-fragrant alcohols, it is preferred that they are C6-C20 alcohols, especially fatty alcohols, which may optionally be modified by ethoxylation or propoxylation.
  • X and Y can be simple alcohols containing a single OH group, or can be polyols containing 2 or more OH groups, more preferably, diols.
  • alcohols can be saturated, unsaturated, linear or branched, alkyl, alkenyl, alkylaryl, alkylalkoxylate derivatives with one or more alcohol groups.
  • the alcohols may contain additional functionality such as amines, amides, ethers, or esters as a part of their structure.
  • the acetal of the present invention can be cyclic or acyclic, and may contain one or more acetal groups through derivatizing one or more aldehydes.
  • the terms cyclic and acyclic in this context refers to the presence or absence of a covalent bond connecting moieties X and Y of the acetal.
  • X and Y of the cyclic acetals form a ring structure and have at least two alkoxylate moieties.
  • the preferred acyclic acetals having at least four alkoxylate moieties incorporate linear alcohols.
  • the cyclic acetals are derived from polyols.
  • Preferred polyols include those which are alkoxylated with 1 to 30 units of ethylene oxide or propylene oxide.
  • Nonlimiting examples of the polyols include, for example, sorbitol, glucose, sucrose, and other saccharides.
  • the acyclic acetals are derived from mono-alcohols.
  • Preferred mono- alcohols containing a single OH group can include the alkoxylates of detergent alcohols and mono-alkyl ethers of short-chain polyalkoxylates.
  • the mono-alkyl ethers of short-chain polyalkoxylates include C-J-C5 alkyl moiety.
  • Nonlimiting examples of the parents alcohols include ethyl alcohol, propyl alcohol, butyl alcohol, lauryl alcohol, and myristyl alcohol.
  • R- and the H of the above general structure are is derived from a starting aldehyde.
  • both fragrant and non-fragrant aldehydes inco ⁇ orated into the instant acetals can be aliphatic, allylic or benzylic.
  • the aldehydes can be saturated, unsaturated, linear, branched, or cyclic.
  • the structures can include alkyl, alkenyl, or aryl moieties, as well as additional functional groups such as alcohols, amines, amides, esters, or ethers.
  • acetals herein will be derived from a parent aldehyde having molecular weight above about 80.
  • Nonlimiting examples of the fragrant parent aldehydes include but are not limited by the following examples: hydratropaldehyde, p-t-bucinal, FioralozoneTM, phenylpropanal, anisaldehyde, cymal, cyclamal, triplal, helional, hexylcinnamic aldehyde, vanillin, ethyl vanillin, citral, ethyl citral, citronellal, methyl octyl acetaldehyde, methyl nonyl acetaldehyde, octanal, decanal, dodecanal, lauric aldehyde, chrysanthaUsosyslocitral, melonal, trans-4
  • pro-fragrance acetal compounds are nonlimitingly illustrated by the following:
  • acyclic acetals useful herein include:
  • suitable acetals herein are cyclic acetals derived from the reaction of fragrance aldehydes with polyhydroxyglucosides, including the polyhydroxyamides.
  • suitable polyhydroxy amides include the C-12-C18 N-methylglucamides. See WO 9,206,154.
  • Other sugar-derived acetal or ketal parent compounds herein include the N-alkoxy polyhydroxy fatty acid amides, such as C10- 18 N-(3-methoxypropyl) glucamide.
  • Ketals The pro-fragrance compound of the present invention includes a ketal.
  • the ketal can be used to deliver a fragrance ketone.
  • the discussion for the ketals herein can be constructed using structural principles analogous to those used in discussing acetals supra.
  • Ketals suitable in the present invention include the following structure:
  • X and Y are derived from alcohols or polyols and R2 and R3 are derived from the parent ketone, and can be the same or different.
  • X and Y for Ketals in the above general structure which can be either fragrant alcohols or non-fragrant alcohols including variable alkoxy moieties.
  • the parent alcohols for the ketals can include, but are not limited to, those described as the parent alcohols of the acetals in the section of acetals.
  • alcohols can be saturated, unsaturated, linear or branched, alkyl, alkenyl, alkylaryl, alkylalkoxylate derivatives with one or more alcohol groups.
  • the parent alcohols may contain additional functionality such as amines, amides, ethers, or esters as a part of their structure.
  • R2 and R3 of the above general structure are derived from the parent ketone.
  • both fragrant and non-fragrant ketones can be aliphatic, allylic or benzylic.
  • the ketones can be saturated, unsaturated, linear, branched, or cyclic, preferably including alkyl, alkenyl, or aryl moieties as well as other functional groups including amides, amines, ethers, or esters.
  • ketals herein will be derived from a parent ketone having molecular weight above about 80.
  • Nonlimiting examples of the parent ketones include, for example, irone alpha, a/pia-ionone, beta-ionone, gamma-methyl ionone, methyl bet ⁇ -naphthyl ketone, c/s-jasmone, damascenone, a/p #a-damascenone, benzylacetone, methyl dihydrojasmonate, methyl amyl ketone, methyl heptyl ketone, methyl hexyl ketone, methyl nonyl ketone, carvone, cassione, menthone, and geranylacetone.
  • Other suitable ketones include diketones, e.g. 2,4-pentadione.
  • the non-fragrant ketone can contain one or more ketone functional groups and such groups can be further derivatized so that the ketal is polymeric. While polyketals are included herein, they are less preferred than mono- and di-ketals. Monoketals are most preferred.
  • pro-fragrance ketal compounds are nonlimitingly illustrated by the following:
  • acyclic ketals which is derived from a/p ra-ionone and tripropylene glycol.
  • the pro-fragrance compounds of the present invention can be used for a variety of products wherein the conventional fragrances are used. These are, for example, such as shampoos, conditioners, detergent hard surface cleaner, deodorants, cat litter, and the like. Synthesis of pro-fragrances
  • Acetals and ketals can be prepared by the acid-catalyzed reaction of an aldehyde or ketone with an alcohol (or diol), using conventional acid catalysis such as HCI or p-toluenesulfonic acid, or supported sulfonic acid catalysts e.g., AMBERLYST 15TM.
  • acid catalysis such as HCI or p-toluenesulfonic acid, or supported sulfonic acid catalysts e.g., AMBERLYST 15TM.
  • HCI HCI
  • p-toluenesulfonic acid or supported sulfonic acid catalysts e.g., AMBERLYST 15TM.
  • Many aldehyde, ketone and alcohols useful in the synthesis of acetal and ketal pro-fragrances of the present invention are sensitive to strong acid conditions and can undergo undesirable side reactions. See Bunton, CA. et al, J. Org.
  • Another technique of avoiding side reactions in preparing acetals and ketals of acid sensitive material, such as geraniol, is by transacetalization of a dimethyl acetal or ketal with a higher molecular weight alcohol, using a mild Lewis acid such as titanium isopropoxide or boron trifluoride etherate as the catalyst.
  • a mild Lewis acid such as titanium isopropoxide or boron trifluoride etherate
  • the pro-fragrances of the invention are characterized by their octanol/water partition coefficient P.
  • the octanol/water partition coefficient of a pro-fragrance is the ratio between its equilibrium concentration in octanol and in water. Since the partition coefficients of the pro-fragrance compounds are large, they are more conveniently given in the form of their logarithm to the base 10, logP.
  • CLOGP CLOGP program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database.
  • the "calculated logP” (CLogP) is determined by the fragment approach of Hansch and Leo (cf, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J.B. Taylor and CA. Ramsden, Eds., p. 295, Pergamon Press, 1990).
  • the fragment approach is based on the chemical structure of a compound and takes into account the numbers and type of atoms, the atom connectivity, and chemical bonding.
  • the CLogP values which are the most reliable and widely used estimates for this physicochemical property, can be used instead of the experimental logP values in the selection of pro-fragrances. Determination of Hydrolysis Half-life (t-1/2)
  • Hydrolysis half-life is the measurement used to determine the ease with which the pro-fragrance compound undergoes acid hydrolysis and thereby releases its fragrance component(s) upon exposure to acid conditions.
  • the pro- fragrance compounds of the invention have a half-life of less than 60 minutes, under the described hydrolysis conditions at pH 0.
  • pro-fragrances of the invention have a half-life at pH 2 of less than 60 minutes.
  • the more reactive pro-fragrances that is, those with half-life at pH 2 of less than one minute, are most suitable, although those having a half-life of less than 60 minutes at pH 0 are also useful.
  • pro-fragrances having a half-life of less than 60 minutes at pH 0, and half-life greater than one minute at pH 2 should preferably be used.
  • Hydrolysis half-life is determined by UV/V is spectroscopy in a 90/10 dioxane/water system at 30OC by following the appearance of the carbonyl absorbance. Because of the hydrophobicity of the pro-fragrance compounds of the invention, a high dioxane/water ratio is needed to ensure solubility of the pro- fragrance.
  • the pH of the water used is achieved by using aqueous HCI.
  • the concentration of the pro-fragrance in the dioxane/water system can be adjusted to achieve convenient, measurable absorbance changes. All measurements are carried out using a Hewlett Packard 8452 A Diode
  • Array Spectrophotometer using quartz 1 cm path length cuvette cells Materials used include 1 ,4-dioxane HPLC Grade 99.9% (Sigma-Aldrich), 1N HCI volumetric solution (J.T. Baker), deionized water filtered with MilliQPIus (Millipore) at resistivity of 18.2 M Ohm cm. The pH's are measured using an Orion 230 A standardized with pH 4 and pH 7 buffers. The 1N HCI standard is used directly for pH 0 conditions. For pH 2 conditions, 1 N HCI is diluted with deionized water.
  • Pro-fragrance is weighed out in a 10ml volumetric flask using an analytical balance (Mettler AE 200) Precision is 1/10 mg. The weighed material is dissolved in about 8ml dioxane. Both the dioxane solution of pro-fragrance and aqueous acid solution prepared as described supra are pre-heated in their separate containers to a temperature of 30 + 0.25°C by means of a water-bath. 1.000ml of aqueous acid solution is added to the pro-fragrance solution by means of an Eppendorf pipetter. This is followed by diluting to the 10ml mark with dioxane. Hydrolysis time is measured, starting upon addition of the acid.
  • the pro-fragrance solution is mixed for 30 seconds by shaking, and the solution is transferred to a quartz cuvette.
  • the absorbance of the pro-fragrance solution (At) is followed at a regular series of time intervals, and the cuvette is kept in the water-bath at the above-indicated temperature between measurements.
  • Initial absorbance (Ao) measurements are carried out using an equal concentration of pro-fragrance in a 90/10 v/v dioxane - deionized water solution, and final absorbance (Af) measurements are taken using the hydrolyzed pro-fragrance solution after the hydrolysis is complete.
  • the wavelength at which the hydrolysis is followed is chosen at the wavelength of the absorbance maximum of the parent aldehyde or ketone. Reaction half-lifes are determined using conventional procedures.
  • the observed first-order rate constant ( 0 b s ) is determined by slope of the line provided by plotting the following function vs time (min): Ln [(A 0 - Af)/ (A t - Af)] wherein said function is the natural log of the ratio between the absorbance difference at initial time (A 0 ) and final time (Af) over the absorbance difference at time t (At) and final time (Af).
  • Half-life as defined herein is the time required for half of the pro-fragrance to be hydrolyzed, and is determined from the observed rate constant (k 0DS ) by the following function:
  • the pro-fragrance compound of the present invention can be used for a detergent composition.
  • the pro-fragrance acetal, ketal or mixture thereof can be formulated in the detergent compositions at levels in the general range about 0.0001% to about 10%, more preferably from about 0.001% to 5%, more preferably still, from about 0.01% to about 1%.
  • the pro-fragrance compounds are stable under pH conditions encountered in the formulation and storage of detergent products which have a pH of from about 7.1 to about 13, and during solution-use of such products. Due to hydrophilicity and high degree of heteroatom inco ⁇ oration, these pro- fragrance compounds give reasonably good deposition from a laundering solution onto fabrics. Because the pro-fragrance compounds are subject to hydrolysis when the pH is reduced, they hydrolyze to release their component fragrance compounds when the fabrics (or other surface) upon which they have been deposited are exposed even to reduced pH such as is present in rinse water, air and humidity. Such a reduction in pH should be at least about 0.1 , preferably at least about 0.5 units. Preferably the pH is reduced by at least about 0.5 units to a pH of about 7.5 or less, more preferably about 6.9 or less. Preferably, the solution in which the fabric (or other surface) is washed is alkaline.
  • the pro-fragrance compound can be used as the sole fragrance compound of the present detergent compositions, or in combination with other pro-fragrances and/or in combination with other fragrance materials, extenders, fixatives, diluents and the like.
  • incorporation of the pro-fragrance material into a waxy substance, such as a fatty triglyceride may further improve storage stability of the present pro-fragrance compounds in granular laundry detergents, especially those comprising bleaches.
  • hydrophobic liquid extenders, diluents or fixatives can be used to form an emulsion wherein the pro-fragrance compound is further stabilized by separating it from the aqueous phase.
  • Nonlimiting examples of such stabilizing materials include dipropylene glycol, diethyl phthalate and acetyl triethyl citrate.
  • hydrophobic perfumery ingredients which can be used to stabilize the pro-fragrance material
  • detergency ingredients which also have a perfume stabilizing effect and can be formulated with the pro-fragrance material.
  • Such ingredients include fatty acid amines, low foaming waxy nonionic materials commonly used in automatic dishwashing detergents, and the like.
  • pro-fragrances are used along with other fragrance materials in detergent compositions herein, it is preferred that the pro-fragrance be added separately from the other fragrance materials.
  • compositions inco ⁇ orating synthetic detergent surfactants have a detergent level of from about 0.5% to about 50%, by weight.
  • Compositions containing soap preferably comprise from about 10% to about 90% soap.
  • detergent surfactants which are conventinal for detergent surfactants can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. See also U.S. Patent 3,664,961, issued May 23, 1972.
  • the detergent compositions herein preferably, have a pH of from about 7.1 to about 13, more typically from about 7.5 to about 9.5 for liquid detergents and from about 8 to about 12 for granular detergents when measured at 1% concentration of the distilled water at 20°C Additional Detergent Ingredients
  • pro-fragrance compounds herein may further include one or more additional detergent ingredients, commonly used in detergent products, such as materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., conventional perfumes, colorants, dyes, etc.).
  • additional detergent ingredients are known to those of skill in the art. The following are illustrative examples of other detergent ingredients.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness and in the removal of particulate soils.
  • Suitable builders include those of U.S. Patent 3,308,067, issued Mar. 7, 1967; 4,144,226, issued Mar. 13, 1979 and 4,246,495, issued
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Prferebly, liquid formulations typically comprise from about 5% to about 50%, and granular formulations typically comprise from about 10% to about 80%. Lower or higher levels of builder, however, are not meant to be excluded.
  • Soil Release Agents are desirably used in laundry detergents of the instant invention.
  • Suitable soil release agents include those of U.S. Patent 4,968,451 , issued Nov. 6, 1990; the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. Patent 4,711 ,730, Dec. 8, 1987; the partly- and fully- anionic-end-capped oligomeric esters of U.S. Patent 4,721,580, issued Jan. 26, 1988; the nonionic-capped block polyester oligomeric compounds of U.S. Patent 4,702,857, issued Oct. 27, 1987; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • compositions herein can contain other ingredients such as enzymes, bleaches, fabric softening agents, dye transfer inhibitors, suds suppressors, and chelating agents, all well known within the art.
  • pro-fragrances of the present invention can be used alone and simply mixed with essential detergent ingredient, most notably surfactant, they can also be desirably combined into three-part formulations which combine (a) a non-fragrance detergent base comprising one or more synthetic detergents, (b) one or more pro-fragrance acetals or ketals in accordance with the invention and (c) a fully-formulated fragrance.
  • a non-fragrance detergent base comprising one or more synthetic detergents
  • pro-fragrance acetals or ketals in accordance with the invention
  • a fully-formulated fragrance The latter provides desirable in-package and in- use (wash-time) fragrance, while the pro-fragrance provides a long-term fragrance to the laundered textile fabrics. It is preferred that the pro-fragrance compound be added separately from the conventional fragrances to the detergent compositions.
  • Formulation with other Special-Purpose Fragrance Delivering Compounds may further, optionally, if desired, contain other known compounds having the capability to enhance substantivity of a fragrance.
  • Such compounds include, but are not limited to, the aluminum alkoxides such as isobutylaluminium diferanylate as disclosed in U.S. Patent 4,055,634, issued Oct. 25, 1977; or the known titanate and zirconate esters or oligoesters of fragrant materials such as those disclosed in U.S. Patent 3,947,574, issued March 30, 1976 and U.S. Patent 3,779,932, issued Dec. 18, 1973.
  • organoaluminium, organotitanium or organozinc derivatives they may be incorporated into the detergent compositions of the present invention described herein at their art-known levels.
  • a method of delivering residual fragrance to a washed surface which comprises the steps of
  • the detergent compositioms shown below can be prepared by any conventional method well known in the art.
  • a suitable method and formulation are as follows: 17
  • reaction mixture Upon cooling, the reaction mixture is washed several times with saturated sodium carbonate and water followed by drying with sodium sulfate. The solvent is removed in vacuo and unreacted parent aldehyde is removed under bulb-to-bulb distillation at 250°C, 0.2mmHg to yield 19.6g of pale brown oil (80%) identified spectroscopically at the desired material.
  • the Clop of resulting acetal is less than 4.
  • a laundry detergent composition is prepared by weighing 98g of laundry detergent according to Example 4 with the exception that perfume and pro- fragrance are not included; admixing to said composition 2g of a perfume of flowery-woody type made up of a mixture of a first premix and a conventional ketal (not in accordance with essential pro-fragrance as defined herein) as follows: First Premix:
  • BrahmanolTM F (c) 2.0 g Benzyl Salicylate 2.0 g cis-3-Hexenyl Salicylate 1.0 g
  • the first perfume premix is modified by adding to it 32 parts by weight of
  • 5a/5b (80:20) wherein 5a is 5-ethylenedioxy-3 bet ⁇ -H-isolongifolane and 5b is 5- ethylenedioxy-3 a/p ⁇ a-H-isolongifolane; these two compounds being conventional perfume ketals not in accordance with the present invention, and their synthesis is described in "CYCLIC ISOLONGIFOLANONE-KETALS - THEIR MANUFACTURE AND THEIR APPLICATION", U.S. Patent 5,426,095, issued June 20, 1995 to Brunke and Schatkowski, assigned to Dragoco.
  • Example 2 1.0g of a pro-fragrance according to Example 2 is mixed into the powdered, perfume-free detergent composition. Finally, about 1.5g of the above perfume composition is sprayed onto the mixture of detergent and pro-fragrance, to complete the fragrance, pro-fragrance laundry detergent composition.
  • the said composition has a floral-woody character and leaves an improved, long- lasting scent on textile fabrics washed therewith.
  • the practi ⁇ ner will minimize the molecular weight while still seeking the advantages of the invention, for example by selecting pro-fragrances at-1/2 of less than one minute at pH 0.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne un composé précurseur de parfum sélectionné dans le groupe constitué par un acétal, un cétal et leurs mélanges, au moins un élément choisi parmi un aldéhyde, une cétone et un alcool parents de l'acétal ou du cétal précurseurs de parfum étant un composé de parfum dont la valeur CLogP est inférieure à 4. Le CLogP est le logarithme de base 10 du coefficient de séparation de l'octanol et de l'eau des précurseurs de parfum. Elle concerne également des compositions détergentes contenant le composé précurseur de parfum et des tensioactifs détersifs.
PCT/US1997/005373 1996-03-22 1997-03-21 Compose precurseur de parfum WO1997034578A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU24322/97A AU2432297A (en) 1996-03-22 1997-03-21 Pro-fragrance compound
BR9708236A BR9708236A (pt) 1996-03-22 1997-03-21 Composto pró-fragrância
JP9533806A JPH11507397A (ja) 1996-03-22 1997-03-21 プロフレグランス化合物
US09/142,888 US6096704A (en) 1997-03-21 1997-03-21 Pro-fragrance compound
EP97920027A EP0904048A1 (fr) 1996-03-22 1997-03-21 Compose precurseur de parfum

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/US1996/004060 WO1997034986A1 (fr) 1996-03-22 1996-03-22 Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance
USPCT/US96/04060 1996-03-22

Publications (1)

Publication Number Publication Date
WO1997034578A1 true WO1997034578A1 (fr) 1997-09-25

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US1997/005372 WO1997034989A1 (fr) 1996-03-22 1997-03-21 Compositions detergentes comprenant un compose precurseur de parfum
PCT/US1997/005373 WO1997034578A1 (fr) 1996-03-22 1997-03-21 Compose precurseur de parfum

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/US1997/005372 WO1997034989A1 (fr) 1996-03-22 1997-03-21 Compositions detergentes comprenant un compose precurseur de parfum

Country Status (12)

Country Link
EP (3) EP0888439A1 (fr)
JP (3) JP3708129B2 (fr)
CN (2) CN1218392A (fr)
AR (1) AR006356A1 (fr)
AU (3) AU5372096A (fr)
BR (3) BR9612555A (fr)
CA (2) CA2249411A1 (fr)
CZ (2) CZ304998A3 (fr)
MX (1) MXPA98007743A (fr)
TR (2) TR199801879T2 (fr)
WO (2) WO1997034989A1 (fr)
ZA (3) ZA972404B (fr)

Cited By (14)

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WO1998027190A1 (fr) * 1996-12-19 1998-06-25 The Procter & Gamble Company Conditionnement de tissus active par sechoir et compositions antistatiques dont la tenacite du parfum est amelioree
WO1998047477A1 (fr) * 1997-04-24 1998-10-29 The Procter & Gamble Company Precurseurs d'accords de parfum
WO1998047478A1 (fr) * 1997-04-24 1998-10-29 The Procter & Gamble Company Parfums ayant des caracteristiques de longevite d'odeur
WO1999016735A1 (fr) * 1997-09-26 1999-04-08 The Procter & Gamble Company Procede de production de composes acetaliques
US6165452A (en) * 1999-07-21 2000-12-26 International Flavors & Frangrances Inc. Cyclic trimers of aldehydes, organoletpic uses thereof and process for preparing same
WO2001007095A1 (fr) * 1999-07-21 2001-02-01 Unilever Plc Compositions de traitement contre les mauvaises odeurs
WO2001027234A1 (fr) * 1999-10-08 2001-04-19 Henkel Kommanditgesellschaft Auf Aktien Constituant de detergent a liberation de parfum a double controle
WO2001091712A3 (fr) * 2000-06-01 2002-06-06 Procter & Gamble Systemes de diffusion de parfums a duree accrue dans lesquels le parfum initial n'est pas altere
WO2004047788A3 (fr) * 2002-11-25 2004-09-02 Colgate Palmolive Co Precurseurs fonctionnels de parfums
US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
WO2008155683A1 (fr) * 2007-06-18 2008-12-24 Firmenich Sa Compositions agissant contre les mauvaises odeurs et leur procédé d'utilisation
WO2009156278A1 (fr) * 2008-06-27 2009-12-30 Henkel Ag & Co. Kgaa Pro-fragrance polymère
WO2019121032A1 (fr) * 2017-12-20 2019-06-27 S H Kelkar & Company Limited Acétals odorants de l'éthylvanilline et dérivés de l'éthylvanilline
EP3942009A1 (fr) * 2019-03-20 2022-01-26 Firmenich SA Composés pro-parfum encapsulés

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BR9813898A (pt) * 1997-10-29 2000-09-19 Procter & Gamble Composições para lavanderia com mau cheiro reduzido e métodos de providenciar as mesmas
US6506793B2 (en) 2000-10-13 2003-01-14 Kao Corporation Citral acetal
JP4689106B2 (ja) * 2000-10-13 2011-05-25 花王株式会社 シトラールアセタール
US7838692B2 (en) 2004-02-25 2010-11-23 Idemitsu Kosan Co., Ltd. Alkyl acetal compound, process for producing the same, and lubricating oil composition
US8557262B2 (en) * 2008-09-12 2013-10-15 Firmenich Sa Divinyl ether derivatives capable of releasing active aldehydes and ketones and methods of use for perfuming surfaces
WO2014096063A1 (fr) * 2012-12-18 2014-06-26 Dsm Ip Assets B.V. (6r,10r)-6,10,14-triméthylpentadécan-2-one préparée à partir de 3,7-diméthyloct-2-énal ou 3,7-diméthylocta-2,6-diénal
JP6231378B2 (ja) * 2012-12-28 2017-11-15 花王株式会社 衣料用液体洗浄剤組成物
EP2978831B1 (fr) * 2013-03-28 2020-12-02 The Procter and Gamble Company Compositions de nettoyage contenant une polyétheramine, un polymère de libération des salissures et une carboxyméthylcellulose
DE102016223412A1 (de) 2016-11-25 2018-05-30 Henkel Ag & Co. Kgaa Cyclische Ketale als Duftstoffvorläuferverbindungen
US11667869B2 (en) * 2018-06-22 2023-06-06 Firmenich Sa Enol ether pro perfume

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JPH02276041A (ja) * 1989-04-15 1990-11-09 Tsumura & Co ３―および４―（４―ヒドロキシ―４―メチルペンチル）―３―シクロヘキセン―１―カルボキシアルデヒドのアセタール類並びに該化合物を有する香料組成物
WO1994006441A1 (fr) * 1992-09-22 1994-03-31 The Mennen Company Composition contenant une fragrance activee par le corps destinee a etre appliquee sur la peau et son procede d'utilisation
US5378468A (en) * 1992-09-22 1995-01-03 The Mennen Company Composition containing body activated fragrance for contacting the skin and method of use
US5500138A (en) * 1994-10-20 1996-03-19 The Procter & Gamble Company Fabric softener compositions with improved environmental impact

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Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277796B1 (en) 1996-12-19 2001-08-21 The Procter & Gamble Company Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity
WO1998027190A1 (fr) * 1996-12-19 1998-06-25 The Procter & Gamble Company Conditionnement de tissus active par sechoir et compositions antistatiques dont la tenacite du parfum est amelioree
WO1998047477A1 (fr) * 1997-04-24 1998-10-29 The Procter & Gamble Company Precurseurs d'accords de parfum
WO1998047478A1 (fr) * 1997-04-24 1998-10-29 The Procter & Gamble Company Parfums ayant des caracteristiques de longevite d'odeur
WO1999016735A1 (fr) * 1997-09-26 1999-04-08 The Procter & Gamble Company Procede de production de composes acetaliques
US6165452A (en) * 1999-07-21 2000-12-26 International Flavors & Frangrances Inc. Cyclic trimers of aldehydes, organoletpic uses thereof and process for preparing same
WO2001007095A1 (fr) * 1999-07-21 2001-02-01 Unilever Plc Compositions de traitement contre les mauvaises odeurs
WO2001027234A1 (fr) * 1999-10-08 2001-04-19 Henkel Kommanditgesellschaft Auf Aktien Constituant de detergent a liberation de parfum a double controle
US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
WO2001091712A3 (fr) * 2000-06-01 2002-06-06 Procter & Gamble Systemes de diffusion de parfums a duree accrue dans lesquels le parfum initial n'est pas altere
US6610646B2 (en) 2000-06-01 2003-08-26 The Procter & Gamble Company Enhanced duration fragrance delivery system having a non-distorted initial fragrance impression
US8592361B2 (en) 2002-11-25 2013-11-26 Colgate-Palmolive Company Functional fragrance precursor
US8895495B2 (en) 2002-11-25 2014-11-25 Colgate-Palmolive Company Functional fragrance precursor
US8906843B2 (en) 2002-11-25 2014-12-09 Colgate-Palmolive Company Functional fragrance precursor
US8901068B2 (en) 2002-11-25 2014-12-02 Colgate-Palmolive Company Functional fragrance precursor
AU2003287684B2 (en) * 2002-11-25 2009-09-10 Colgate-Palmolive Company Functional fragrance precursor
RU2338780C2 (ru) * 2002-11-25 2008-11-20 Колгейт-Палмолив Компани Функциональный предшественник ароматизатора, его способ получения и композиция на его основе, используемая в качестве стирального порошка, отдушки, как продукт для личной гигиены или как продукт для ухода за полостью рта или за твердой поверхностью
AU2009240837B2 (en) * 2002-11-25 2011-06-09 Colgate-Palmolive Company Functional fragrance precursor
AU2009239944B2 (en) * 2002-11-25 2011-09-29 Colgate-Palmolive Company Functional fragrance precursor
AU2009240838B2 (en) * 2002-11-25 2011-09-29 Colgate-Palmolive Company Functional fragrance precursor
EP2353653A3 (fr) * 2002-11-25 2013-02-13 Colgate-Palmolive Company Precurseurs fonctionnels de parfums
WO2004047788A3 (fr) * 2002-11-25 2004-09-02 Colgate Palmolive Co Precurseurs fonctionnels de parfums
US8895496B2 (en) 2002-11-25 2014-11-25 Colgate-Palmolive Company Functional fragrance precursor
US8772354B2 (en) 2007-06-18 2014-07-08 Firmenich Sa Malodor counteracting compositions and method for their use
EP2008637A1 (fr) * 2007-06-18 2008-12-31 Firmenich Sa Compositions d'annihilation malodorantes et leur procédé d'utilisation
WO2008155683A1 (fr) * 2007-06-18 2008-12-24 Firmenich Sa Compositions agissant contre les mauvaises odeurs et leur procédé d'utilisation
WO2009156278A1 (fr) * 2008-06-27 2009-12-30 Henkel Ag & Co. Kgaa Pro-fragrance polymère
WO2019121032A1 (fr) * 2017-12-20 2019-06-27 S H Kelkar & Company Limited Acétals odorants de l'éthylvanilline et dérivés de l'éthylvanilline
US11661565B2 (en) 2017-12-20 2023-05-30 S H Kelkar & Company Limited Odorous acetals of ethyl vanillin and ethyl vanillin derivatives
EP3942009A1 (fr) * 2019-03-20 2022-01-26 Firmenich SA Composés pro-parfum encapsulés
US12264295B2 (en) 2019-03-20 2025-04-01 Firmenich Sa Encapsulated pro-perfume compounds

Also Published As

Publication number Publication date
MXPA98007743A (es) 2002-07-22
AR006356A1 (es) 1999-08-25
CN1219196A (zh) 1999-06-09
CZ299798A3 (cs) 1999-03-17
AU2432197A (en) 1997-10-10
EP0904048A1 (fr) 1999-03-31
JPH11513742A (ja) 1999-11-24
BR9708576A (pt) 1999-08-03
AU2432297A (en) 1997-10-10
EP0888439A1 (fr) 1999-01-07
BR9612555A (pt) 1999-07-20
CA2249411A1 (fr) 1997-09-25
JPH11507415A (ja) 1999-06-29
ZA972512B (en) 1997-09-25
TR199801878T2 (xx) 1998-12-21
CA2249269A1 (fr) 1997-09-25
JP3708129B2 (ja) 2005-10-19
CZ304998A3 (cs) 1999-03-17
ZA972404B (en) 1997-09-25
WO1997034989A1 (fr) 1997-09-25
JPH11507397A (ja) 1999-06-29
EP0888442A1 (fr) 1999-01-07
TR199801879T2 (xx) 1998-12-21
CN1218392A (zh) 1999-06-02
BR9708236A (pt) 1999-08-03
AU5372096A (en) 1997-10-10
ZA972514B (en) 1997-09-25

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