[go: up one dir, main page]

WO1997034986A1 - Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance - Google Patents

Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance Download PDF

Info

Publication number
WO1997034986A1
WO1997034986A1 PCT/US1996/004060 US9604060W WO9734986A1 WO 1997034986 A1 WO1997034986 A1 WO 1997034986A1 US 9604060 W US9604060 W US 9604060W WO 9734986 A1 WO9734986 A1 WO 9734986A1
Authority
WO
WIPO (PCT)
Prior art keywords
acetal
pro
ketal
fragrant
fragrance
Prior art date
Application number
PCT/US1996/004060
Other languages
English (en)
Inventor
Hsiang Kuen Mao
Joseph Paul Morelli
Henry Cheng Na
Robert Ya-Lin Pan
Mark Robert Sivik
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
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to BR9612555A priority Critical patent/BR9612555A/pt
Priority to US09/155,140 priority patent/US6239087B1/en
Priority to CA002249588A priority patent/CA2249588A1/fr
Priority to PCT/US1996/004060 priority patent/WO1997034986A1/fr
Priority to EP96910554A priority patent/EP0888439A1/fr
Priority to JP51657597A priority patent/JP3708129B2/ja
Priority to MXPA98007743A priority patent/MXPA98007743A/es
Priority to AU53720/96A priority patent/AU5372096A/en
Priority to ZA9702404A priority patent/ZA972404B/xx
Priority to PCT/US1997/005372 priority patent/WO1997034989A1/fr
Priority to CN97194763A priority patent/CN1219196A/zh
Priority to EP97920027A priority patent/EP0904048A1/fr
Priority to AU24322/97A priority patent/AU2432297A/en
Priority to CZ983049A priority patent/CZ304998A3/cs
Priority to AU24321/97A priority patent/AU2432197A/en
Priority to CA002249411A priority patent/CA2249411A1/fr
Priority to TR1998/01878T priority patent/TR199801878T2/xx
Priority to BR9708236A priority patent/BR9708236A/pt
Priority to ARP970101159A priority patent/AR006356A1/es
Priority to TR1998/01879T priority patent/TR199801879T2/xx
Priority to CZ982997A priority patent/CZ299798A3/cs
Priority to CN97194595A priority patent/CN1218392A/zh
Priority to JP9533805A priority patent/JPH11507415A/ja
Priority to PCT/US1997/005373 priority patent/WO1997034578A1/fr
Priority to JP9533806A priority patent/JPH11507397A/ja
Priority to CA002249269A priority patent/CA2249269A1/fr
Priority to BR9708576A priority patent/BR9708576A/pt
Priority to EP97920026A priority patent/EP0888442A1/fr
Priority to ZA9702514A priority patent/ZA972514B/xx
Priority to ZA9702512A priority patent/ZA972512B/xx
Publication of WO1997034986A1 publication Critical patent/WO1997034986A1/fr

Links

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

Definitions

  • the present invention relates to detergent compositions containing acetal or ketal pro- fragrance compounds and methods for accomplishing the delivery of such organic pro-fragrance compounds to textile articles and other surfaces washed with said compositions, and in certain preferred pro-fragrance compounds which are believed to be novel. More particularly, the invention relates to laundry detergent composiuons in which there is a delayed release of fragrances from surfaces washed in an aqueous bath in the presence of conventional detergent ingredients. The fragrance is released in fragrance-active fo ⁇ n when the surface is in contact with a lower pH environment such as contact with water, carbon dioxide gas, humid air, or the like.
  • 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. For 2478, which is phenylacetaldehyde dicitronellyl acetal, molecular weight 414.7, Arctander reports ' ... and it is not exaggerated to say that this acetal is practically abandoned and obsolete in today's perfumery".
  • the selected potential fragrance materials described by Suffis et al 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.
  • hydrophilic acetal or ketal materials i.e., those having a CLogP value (described hereafter) of less than 4 have at best limited usefulness in laundry detergent compositions.
  • the Suffis et al development is designed to be incorporated with a personal care product vehicle, resulting in clear deodorant sticks and the like.
  • compositions containing the potential fragrance materials are applied directly to the substrate (i.e. skin); therefore, the deposition problems resulting from dilution, rinsing, etc. 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, in order to remove detergent adjuncts and the soils displaced by detergent adjuncts from the fabrics, the latter are rinsed after washing. The rinsing tends to remove th useful pro- fragrance material deposited. Thus both the detergent adjuncts and the essential steps of the wash process itself all work against the effective delivery of pro-fragrances to the fabrics being washed. Moreover, high-efficiency pro-fragrant systems are desired for laundry purposes.
  • objects of the present invention include the provision of such pro- fragrance types and the corresponding detergent compositions and methods. While the present invention is primarily directed to the laundering of fabrics, the compositions of the present invention are also useful in the washing of other surfaces (e.g. hard surfaces such as floors, walls, and dishes) when it is desired to impart residual fragrances to the washed surface.
  • pro-fragrance herein, it is meant 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.
  • pro-fragrance compounds can also be considered a pro-fragrance.
  • the present invention relates to a detergent composition for imparting residual fragrance to surfaces washed with aqueous solutions of said detergent, said detergent comprising: (a) a pro-fragrant compound selected from the group consisting of acetals, ketals, and mixtures thereof, wherein at least one of the parent aldehydes, ketones, or alcohols of said pro-fragrant acetal or ketal is a fragrance compound, said pro- fragrant compound having; (i) a molecular weight of at least about 350, (ii) a CLogP of at least about 4, preferably about 6 or higher, more preferably about 10 or higher, wherein CLogP is the logarithm to base 10 of the octanol/water partition coefficient of said pro-fragrant compound, and (iii) a half-life of less than 60 minutes, when measured at pH 0 by the Pro- Fragrant Hydrolysis Test; and (b) a detersive surfactant; wherein said detergent composition has a
  • the present invention also relates to a method of delivering residual fragrances to a washed surface. All percentages, ratios, and proportions herein are on a weight basis unless otherwise indicated. All documents cited are hereby incorporated by reference.
  • the pro-fragrances of this invention are acetals, ketals, or mixtures thereof, provided that compounds from which they are formed comprise at least one fragrance compound.
  • Acetals and ketals may in general 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 ketals is a fragrance compound.
  • any pro-fragrance compound of the inventive compositions has the following properties:
  • CLogP of at least about 4, (preferably at least 6, more preferably at least 10) wherein CLogP is the logarithm to base 10 of the octanol/water partition coefficient of said pro-fragrant compound, and (iii) a half-life of less than 60 minutes, when measured at pH 0 by the Pro-Fragrant
  • 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 13, and during solution-use of such products. Due to their high molecular weight and hydrophobicity, these pro-fragrance compounds give reasonably good deposition from a laundering solution onto fabrics. Because the pro-fragrant compounds are subject to hydrolysis when the pH is reduced, they hydrolyze to release their component fragrance compounds when the fabrics upon which they have been deposited are exposed even to reduced pH such as present in rinse water, air and humidity.
  • the reduction in pH should be at least 0.1, preferably at least about 0.5 units. Preferaby 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 in which the fabric (or other surface) is washed is alkaline.
  • An important class of preferred acetals herein are those derived from parent aldehydes other than those which possess both of the following characteristics: (a) low molecular weight and (b) contain a CgHs moiety which has no substituent groups other than the aldehyde itself.
  • Such relatively undesirable acetals for the present purposes are those derived from benzaldehyde and phenylacetaldehyde. More preferably, acetals herein, when they comprise an aromatic moiety, will be derived from a parent aldehyde having molecular weight above about 125, more preferably above about 140.
  • acetals herein are those derived from a fragrant Co- or higher unsaturated aldehyde and a fragrant or non-fragrant alcohol particularly the -C20 (preferably C1 1 -C20. more preferably C j 4-C ⁇ g) saturated or unsaturated, linear or branched aliphatic alcohols, commonly referred to as detergent alcohols.
  • said alcohols can be alkoxylated with 1 to 30 moles of ethylene oxide propylene oxide or mixtures thereof.
  • Preferred alcohols in the above group are illustrated by OXO alcohols and Guerbet alcohols.
  • Aromatic or aliphatic alcohols can be used. Alternately, though less desirably, other hydrophobic non-fragrant alcohols may be substituted for the above-identified alcohols while remaining within the spirit and scope of the invention.
  • acetals and ketals are included within the invention.
  • the acetals and ketals are derived from an aldehyde or ketone and an alcohol, at least one of which is a fragrance compound.
  • Many fragrant aldehydes, ketones, and alcohols which are suitable parent compounds for the present acetals and ketals are known to the art. See, for example, Arctander's compilation referenced hereinabove for fragrant parent compounds.
  • Specific fragrant parent aldehydes include but are not limited by the following examples: hydratropaldehyde, p-t-bucinal, FloralozoneTM, cyclamal, triplal, helional, hexylcinnamic aldehyde, vanillin, citral, citronellal, dodecanal, decanal, hydroxycitronellal, and octanal.
  • the aldehyde can be non-fragrant.
  • Nonfragrant aldehydes include 1 ,4-terephthalyl dicarboxaldehyde or other aldehydes having low volatility by virtue of incorporation of bulky polar moieties.
  • Specific parent alcohols of fragrant types suitable herein are likewise given in Arctander and include but are not limited by phenylethyl alcohol, geraniol, nerol, citronellol, linalool, tetrahydroiinalool, dihydromyrcenol, dimethylcarbitol, 9-decen-l-ol, phenylpropyl alcohol, phenylhexylalcohol (phenoxanol or 3-n.ethyl-5-pl.enyl pentanol), ocimenol, patchone, and 2- (5,6,6-trimethyl-2-norbornyl) cyclohexanol.
  • parent alcohols which can be used include ethanol, propanol, butanol, lauryl alcohol, myristyl alcohol, and 2-ethylhexanol; parent alcohols having very low odor or alcohols which are essentially non-fragrant, include stearyl and behenyl alcohols.
  • a preferred group of alcohols includes the detergent alcohols and their alkoxylates. Ketones herein may likewise vary in wide ranges.
  • Suitable fragrant ketone parent compounds for the instant acetals and ketals include benzylacetone, methyl dihydrojasmonate, methyl amyl ketone, methyl nonyl ketone, carvone, geranylacetone, alpha-ionone, beta-ionone, gamma-methyl ionone, damascenone, cis-jasmone, methyl-beta-naphthyl ketone.
  • Other suitable ketones include dike tones, e.g. 2,4-pentadione.
  • Acetals suitable in the present invention have the following structure:
  • Such acetals can be used to deliver fragrance aldehydes, fragrance alcohols, or both.
  • Ri and the H are derived from a starting aldehyde.
  • the parent aldehyde is a fragrant aldehyde when no alcohol parent is fragrant, or can be a fragrant or non-fragrant aldehyde when a fragrant alcohol has been incorporated into the acetal structure.
  • Preferred acetals include those in which Ri comprises a Cg or larger alkyl or alkenyl moiety.
  • the non-fragrant aldehyde can contain one or more aldehyde functional groups for derivatization, in which case the acetal can be either monomeric or polymeric.
  • acetals herein are mono-acetals and di-acetals, most preferably monoacetals.
  • the present compositions can optionally include hemiacetals, but hemi-acetals are by definition not acetals herein and can not be used as the essential pro-fragrant component.
  • both fragrant and non-fragrant aldehydes incorporated 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.
  • X and Y in the above general structure represent independently variable alkoxy moieties derived from alcohols that can be either fragrant alcohols or non-fragrant alcohols, provided that when no fragrant aldehyde is incorporated into the acetal, at least one fragrant alcohol is incorporated.
  • 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, propoxylation or butoxylation.
  • 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.
  • Preferred polyols useful as parent alcohols for making acetals or ketals herein which are especially useful in heavy-duty laundry granules include those which are not able to form 5 or 6 membered cyclic acetals or ketals, such as 1,4-dimethylolcyclohexane or 1 , 12-dihydroxy dodecane.
  • acetals herein when formed using polyols, can be cyclic or acyclic acetals derivatizing one or more aldehydes.
  • 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 acetals herein derived from polyols 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 refer to the presence or absence of a covalent bond connecting moieties
  • X and Y of the acetal are typically connected to form a ring comprising 2 or more carbons (n >_ 2).
  • Certain cyclic acetals can be connected by two carbons to form a five-membered dioxolane ring, as shown in (IT), or three carbons can be connected, to form a six-membered dioxane ring, as shown in (III); larger cyclic acetals are also known.
  • Tbe laundry compositions of the present invention encompass many acetals termed "acyclic * because moieties X and Y are not covalently bonded to form an acetal of ring-type. Such acyclic acetals may in general nonetheless contain one or more cyclic moieties in any of R, X and Y. Many pro-fragrant acetals especially preferred for liquid detergent compositions herein are acyclic.
  • a preferred class of pro- fragrant acetals are the acyclic dialkyl acetals derived from fragrant aldehydes that are aliphatic in structure. These acetals exhibit improved stability in conventional HDL formulations.
  • acetals For heavy-duty granular detergent (HDG) compositions, a preferred class of acetals is the acyclic dialkyl acetals derived from fragrance aldehydes. Such acetals that are allylic or benzylic in structure are more preferred. These materials more readily hydrolyze delivering bigger odor benefits at lower levels.
  • HDG heavy-duty granular detergent
  • pro-fragrant acetal compounds are nonlimitingly illustrated by the following: digeranyl citral acetal; di(dodecyl) citral acetal; digeranyl vanillin acetal; didecyl hexyl cinnamaldehyde acetal; didecyl ethyl citral acetal; di(dodecyl) ethyl citral; didecyl anisaldehyde acetal; di(phenylethyl) ethyl vanillin acetal; digeranyl p-t-bucinal acetal; didecyl triplal acetal; di(dodecyl) triplal acetal; digeranyl decanal acetal; di(dodecyl) decanal acetal; dicitronellyl laural acetal; di(tetradecyl) laural acetal; di(octadect
  • pro-fragrant acetals illustrate incorporation of structural features such as inclusion of fatty (i.e., detergent) alcohols and fatty alcohol ethoxylates into the pro-fragrant acetal; as well as the formation of pro-fragrant mixed acetals.
  • acetals herein include: acetal of p-t-bucinal and ISOFOL or other branched detergent alcohols (Condea); acetal of triplal and two moles of
  • suitable acetals herein are cyclic acetals derived from the reaction of fragrance aldehydes with poylhydroxyglucosides, including the polyhydroxyamides.
  • suitable polyhydroxy amides include the N-methylglucamides.
  • sugar-derived acetal or ketal parent compounds herein include the N-alkoxy polyhydroxy fatty acid amides, such as Ct Q -Ci g N-(3-metboxyprop l) glucamide.
  • suitable ketals herein can be constructed using structural principles analogous to those used in discussing acetals supra. More particularly, suitable ketals have the following structure:
  • Ketals can be used to deliver fragrance ketones, fragrance alcohols, or both.
  • R2 and R3 are derived from the parent ketone, and can be the same or different, and X and Y are de ⁇ ved from alcohols.
  • the alcohols incorporated need not be fragrant; reciprocally, when at least one fragrant alcohol is incorporated, the ketones may be non-fragrant.
  • R2 + R3 contain eight or more carbons.
  • 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. Exemplary diketals are shown below:
  • R'O is derived from a perfume alcohol
  • both fragrant and non-fragrant ketones can be aliphatic, allylic or benzylic.
  • the ketones can be saturated, unsaturated, linear, branched, or cyclic.
  • R2 and R3 can include alkyl, alkenyl, or aryl moieties as well as other functional groups including amides, amines, ethers, or esters.
  • X and Y for ketals are alkoxy groups derived from alcohols that can be either fragrant alcohols or non-fragrant alcohols.
  • X and Y can be the same or different, allowing tbe delivery of more than one type of fragrant alcohol.
  • suitable parent alcohols for ketals include 5-C20 (preferably Ci 1-C20) alcohols such as fatty alcohols and their ethoxylated, propoxylated and butoxylated derivatives. It is preferred in the present ketals to incorporate alcohols that are fatty alcohols.
  • Suitable ketals derived from polyols can be cyclic or acylic ketals, derivatizing one or more ketones.
  • alcohols can be saturated, unsaturated, linear or branched, alkyl, alkenyl, alkylaryl, alkylakoxylate 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.
  • X and Y can be simple alcohols containing a single OH group or polyols containing 2 or more OH groups.
  • Specific preferred pro-fragrant ketal compounds are nonlimitingly illustrated by the following: di(phenyl ethyl) alpha ionone ketal; di(dodecyl) alpha ionone ketal; di (phenyl hexyl) beta ionone ketal; di (citronellyl) gamma methyl ionone ketal; di(tetradecyl) gamma methyl ionone ketal; didecyl methyl beta naphthyl ketal; dioctadecyl cis jasmone ketal; digeranyl damascenone ketal; d ⁇ (c ⁇ s-3-hexenyl) methyl dihydrojasmonate ketal, d ⁇ (dodecyl) methyl dihydro j as onate ke l; didecyl benzyl acetone ketal; d ⁇ (2-ethy
  • the preferred ketals mclude cyclic and acyclic aliphatic ketals More preferred are acyclic aliphatic ketals.
  • Va ⁇ ations of the present mvention mclude laundry detergents which incorporate acetals or ketals wherem the parent alcohol is a polymer such as polyvinyl alcohol, starch or synthetic copolymers incorporating tn or polyhydnc alcohols as monomers.
  • the essential pro-fragrance component herein can be used at widely ranging levels.
  • a pro-fragrent acetal, ketal or mixture thereof is formulated in the present 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 % .
  • a pro-fragrance can be used as the sole fragrance component of the present detergent compositions, or in combmation with other pro-fragrances and/or in combmation with other fragrance mate ⁇ als, extenders, fixatives, diluents and the like.
  • incorporation of the pro-fragrant matenal mto a waxy substance, such as a fatty tnglycende may further improve storage stability of the present pro-fragrant compounds in granular laundry detergents, especially those comp ⁇ smg bleach.
  • hydrophobic liquid extenders, diluents or fixatives can be used to fo ⁇ n an emulsion wherem the pro-fragrant compound is further stabilized by separating it from the aqueous phase.
  • stabilizing materials include dipropylene glycol, diethyl phthalate and acetyl triethyl citrate.
  • hydrophobic perfumery ingredients which can be used to stabilize the pro- fragrant material
  • detergency ingredients which also have a perfume stabilizing effect and can be formulated with the pro-fragrant material.
  • Such ingredients include fatty acid amines, low foaming waxy nonionic materials commonly used in automatic dishwashing detergents, and the like.
  • pro-fragrances be added separately from the other fragrance materials. 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,
  • TM or supported sulfonic acid catalysts e.g., AMBERLYST 15 See Meskens, F., Synthesis, (7) 501 (1981) and Meskens, F., Jannsen Chim Ada (1) 10 (1983).
  • 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, /. Org. Chem. (44), 3238, (1978), and Cort, O., et al, J. Org. Chem. (51), 1310 (1986).
  • the present invention also includes novel pro-fragrance compounds. These can be broadly described as being selected from the group consisting of pro-fragrant acetals, and ketals wherein at least one of the parent aldehydes, ketones, or alcohols of said pro-fragrant acetal or ketal is a fragrance compound, said pro-fragrant compound having: (i) a molecular weight of at least about 350, (ii) a CLogP of at least about 4 (preferably at least about 6, most preferably at least about 10), wherein CLogP is the logarithm to base 10 of the Octanol Water Partition Coefficient of said pro-fragrant compound, and (iii) a half-life of less than 60 minutes, when measured at pH 0 by the Pro-Fragrant Hydrolysis Test; provided that said parent aldehyde, ketone or alcohol of said acetal or ketal comprises at least one compound selected from the group consisting of a) aldehydes, ketones and alcohols containing at least one aromatic moiety
  • parent ketones for these novel compounds are: benzyl acetone, ⁇ /p/i ⁇ -ionone, beta-ioooae, gamma-methyl ionone, irone alpha, methyl dihydrojasmonate, c ⁇ -jasmone, methyl amyl ketone, methyl heptyl ketone, methyl hexyl ketone, methyl nonyl ketone, carvone, damascenone, ⁇ pA ⁇ -damascone, methyl vr ⁇ -napthyl ketone, cassione, menthone.
  • TM modified alkyl ethoxylates
  • polyhyd ⁇ c alcohols are glycerol, mannitol, sorbitol and glucose, as well as substituted polyhyd ⁇ c alcohols such as glycerol laurate, glycerol monooleate, sorbitan laurate, sorbitan oleate, , sucrose dioleate, N-dodecyl glucosamine and dodecyl glucose.
  • Additional examples mclude Ci ⁇ -Ci N-alkyl polyhydroxy fatty acid amides See WO 9,206,154.
  • the pro-fragrances of the mvention are characte ⁇ zed by their octanol/water partition coefficient P.
  • the octanol/water partition coefficient of a pro-fragrance is the ratio between its equilib ⁇ um concentration in octanol and in water. Smce the partition coefficients of the pro- fragrance compounds are large, they are more conveniently given in the form of their loganthm to the base 10, logP.
  • the logP of many compounds have been reported; for example, the Pomona92 database, available from Daylight Chemical Info ⁇ nation Systems, Inc. (Daylight CIS), contains many, along with citations to the ongmal literature.
  • CLogP The "calculated logP” (CLogP) is determmed 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 mto account the numbers and type of atoms, the atom connectivity, and chemical bonding.
  • 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-fragrant compounds of the mvention have a half-life of less than 60 nunutes, under the desenbed hydrolysis conditions at pH 0.
  • pro- fragrances of the mvention have a half-life at pH 2 of less than 60 nunutes
  • the more reactive pro-fragrances that is, those with half-life at pH 2 of less than one minute, are most suitable, although those havmg a half-life of less than 60 nunutes at pH 0 are also useful.
  • pro-fragrances havmg a half-life of less than 60 nunutes at pH 0, and half-life greater than one minute at pH 2 should preferably be used. Hydrolysis half-life is determmed by UV/Vis spectroscopy in a 90/10 dioxane/water system at 30°C by followmg the appearance of the carbonyl absorbance. Because of the hydrophobicity of the pro-fragrance compounds of the mvention, 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 HCl. The concentration of the pro-fragrance in the dioxane/water system can be adjusted to achieve convenient, measurable absorbance changes.
  • 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 (AQ) 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 ( QDS ) is determined by slope of the line provided by plotting the following function vs time (min):
  • 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 ODS ) by the following function:
  • compositions herein include a detersive surfactant and optionally, one or more additional detergent ingredients, including 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., perfumes, colorants, dyes, etc.).
  • additional detergent ingredients including 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., perfumes, colorants, dyes, etc.).
  • additional detergent ingredients including 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., perfumes, colorants, dyes, etc.).
  • additional detergent ingredients including 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., perfumes, colorants, dyes, etc.).
  • the following are illustrative examples of detersive surfactants and other detergent ingredients.
  • the conventional nonionic and amphoteric surfactants such as the C
  • the C j ⁇ -Cig N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the N-methylglucamides.
  • sugar-derived surfactants include the N -alkoxy polyhydroxy fatty acid amides, such as CJQ- C j g N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl glucamides can be used for low sudsing.
  • 10-C20 conventional soaps may also be used, however synthetic detergents are preferred. If high sudsing is desired, the branched-chain Ci ⁇ -Cig soaps may 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, Norris, issued May 23, 1972.
  • compositions incorporating only synthetic detergents have a detergent level of from about 0.5% to 50%.
  • Compositions containing soap preferably comprise from about 10% to about 90% soap.
  • detergent compositions herein can consist of only detersive surfactant and pro-fragrance, the said compositions preferably contain other ingredients commonly used in detergent products.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • 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. Liquid formulations typically comprise from about 5% to about 50% , more typically about 5% to about 30% , by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80% , more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or detergent builders include, but are not limited to phosphate builders such as, the alkali metal, ammonium and alkanolammonium salts of poly phosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, and phytic acid, and non-phosphorous builders such as silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • Non-phosphate builders are required in some locales.
  • Organic builders suitable for use herein include polycarboxylate builders such as disclosed in U.S. Patent 3,308,067, Diehl issued March 7, 1967; 4, 144,226, Crutchfield issued March 13, 1979 and 4,246,495, Crutchfield, issued March 27, 1979. Soil Release Agents Soil Release agents are desirably used in laundry detergents of the instant invention.
  • Suitable soil release agents include those of U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink: such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • Gosselink et al for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g. , PEG 3400.
  • Another preferred soil release agent is a sulfonated end-capped type described in US 5,415,807.
  • 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.
  • the pH of the detergent composition is that which is measured at 1 % concentration of the detergent composition in distilled-water at 20°C.
  • the detergent compositions herein 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.
  • 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-fragranced detergent base comprising one or more synthetic detergents, (b) one or more pro-fragrant acetals or ketals in accordance with the invention and (c) a fully-formulated fragrance.
  • a non-fragranced detergent base comprising one or more synthetic detergents
  • pro-fragrant 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.
  • the fully-formulated fragrance can be prepared using numerous known odorant ingredients of natural or synthetic origin.
  • the range of the natural raw substances can embrace not only readily-volatile, but also moderately-volatile and slightly-volatile components and that of the synthetics can include representatives from practically all classes of fragrant substances, as will be evident from the following illustrative compilation: natural products, such as tree moss absolute, basil oil, citrus fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil, alcohols, such as famesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, aldehydes, such as citral, HelionalTM, alpha-hexyl- cinnamaldehyde, hydroxycitronellal, Liliai
  • butyl-alpha -methyldihydrocinnamaldehyde methylnonylacetaldehyde
  • ketones such as allylionone, aipha-ionone, beta -ionone, isoraldein (isomethyl- alpha -ionone), methylionone
  • esters such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxolate, decyl acetate, dimethylbenzylcarbinyl acetate, dimetbylbenzylcarbinyl butyrate, ethyl acetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc., lactones, such as
  • any conventional fragrant acetal or ketal known in the art can be added to the present composition as an optional component of the conventionally formulated perfume (c).
  • Such conventional fragrant acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those comprising phenylethyl moieties, or more recently developed specialties such as those described in a United States Patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-Indanes, see U.S. Pat. No. 5 ,084,440, issued January 28, 1992, assigned to Givaudan Corp.
  • 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 aluminium alkoxides such as isobutylaluminium diferanylate as disclosed in U.S. Pat. 4,055,634, issued October 25, 1977 and assigned to Hoffman-La Roch; or the known titanate and zirconate esters or oligoesters of fragrant materials such as those disclosed in U.S. Pat. 3,947,574, Jaggers et al, issued March 30, 1976 and U.S. 3,779,932, Jaggers, issued December 18, 1973.
  • organoaluminium, organotitanium or organozinc derivatives they may be inco ⁇ orated into the present formulations at their art-known levels. Methods of Use In its method aspect, the present invention can be described as:
  • a method of delivering residual fragrance to a washed surface which comprises the steps of
  • CLogP is the logarithm to base 10 of the octanol/water partition coefficient of said pro- fragrant compound
  • a detersive surfactant wherein said detergent composition has a pH of at least 7.1 when measured as a 1 % solution in distilled-water at 20°C;
  • citral dimethyl acetal 4.1.0 g, 0.21 mol
  • geraniol 100 g
  • the product is then further purified by column chromatography on 230-400 mesh 60 A silica gel eluting with 2% ethyl acetate/ 1 % triethylamine/ petroleum ether yielding a yellow oil (59 g, 67 % yield), t 1 2 at 0 pH is less than one minute.
  • CLogP is 9.75.
  • a laundry detergent composition is prepared by weighing 98 grams of laundry detergent according to Example 6 with the exception that perfume and pro-fragrance are not inculded; admixing to said composition 2 grams 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:
  • 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.beta.-H-isolongifolane and 5b is 5-ethylenedioxy-3. alpha. -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. Pat. No. 5,426,095, issued June 20, 1995 to Brunke and Schatkowski, assigned to Dragoco.
  • Example 2 1.0 grams of a pro-fragrance according to Example 2 is mixed into the powdered, perfume-free detergent composition. Finally, about 1.5 grams of the above perfume composition is sprayed onto the mixture of detergent and pro-fragrance, to complete the fragranced, pro- fragranced laundry detergent composition.
  • the said composition has a floral-woody character and leaves an improved, long-lasting scent on textile fabrics washed therewith.
  • EXAMPLE 8 Detergent having the form of a Laundry Bar Comprising Pro-Fragrance
  • Neodol 23-9 Nonionic surfactant 2.0%
  • ⁇ Minors include brightner and enzymes
  • the practioner 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.

Landscapes

  • 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)
  • Fats And Perfumes (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des compositions détergentes contenant certains acétals ou cétals qui s'hydrolysent à l'exposition de surfaces lavées dans une solution desdites compositions pour réduire le pH, libérant de ce fait une fragrance qui est caractéristique d'un ou plusieurs des produits d'hydrolyse. Les acétals et cétals font eux-mêmes partie de l'invention. Ils ont une masse moléculaire d'au moins environ 350, un ClogP d'environ 4 et une demi-vie de moins de 60 minutes lorsque celle-ci est mesurée à un pH = 0 par le test hydrolitique pro-fragrant.
PCT/US1996/004060 1996-03-22 1996-03-22 Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance WO1997034986A1 (fr)

Priority Applications (30)

Application Number Priority Date Filing Date Title
BR9612555A BR9612555A (pt) 1996-03-22 1996-03-22 Composições de detergente que contêm precursores de fragância e os precursores de fragância dessas composições
US09/155,140 US6239087B1 (en) 1996-03-22 1996-03-22 Detergent compositions containing fragrance precursors and the fragrance precursors themselves
CA002249588A CA2249588A1 (fr) 1996-03-22 1996-03-22 Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance
PCT/US1996/004060 WO1997034986A1 (fr) 1996-03-22 1996-03-22 Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance
EP96910554A EP0888439A1 (fr) 1996-03-22 1996-03-22 Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance
JP51657597A JP3708129B2 (ja) 1996-03-22 1996-03-22 洗剤組成物およびフレグランス前駆体の分配のための使用法
MXPA98007743A MXPA98007743A (es) 1996-03-22 1996-03-22 Composiciones detergentes que contienen precursores de fragancia, y los propios precursores de fragancia.
AU53720/96A AU5372096A (en) 1996-03-22 1996-03-22 Detergent compositions containing fragrance precursors and the fragrance precursors themselves
ZA9702404A ZA972404B (en) 1996-03-22 1997-03-19 Detergent compositions and method of use for the delivery of fragrance precursors.
PCT/US1997/005372 WO1997034989A1 (fr) 1996-03-22 1997-03-21 Compositions detergentes comprenant un compose precurseur de parfum
CN97194763A CN1219196A (zh) 1996-03-22 1997-03-21 含有香料前体化合物的洗涤剂组合物
EP97920027A EP0904048A1 (fr) 1996-03-22 1997-03-21 Compose precurseur de parfum
AU24322/97A AU2432297A (en) 1996-03-22 1997-03-21 Pro-fragrance compound
CZ983049A CZ304998A3 (cs) 1996-03-22 1997-03-21 Pro-vonná sloučenina
AU24321/97A AU2432197A (en) 1996-03-22 1997-03-21 Detergent compositions comprising pro-fragrance compound
CA002249411A CA2249411A1 (fr) 1996-03-22 1997-03-21 Compose precurseur de parfum
TR1998/01878T TR199801878T2 (xx) 1996-03-22 1997-03-21 �n-rayiha bile�i�i ihtiva eden deterjan terkipleri.
BR9708236A BR9708236A (pt) 1996-03-22 1997-03-21 Composto pró-fragrância
ARP970101159A AR006356A1 (es) 1996-03-22 1997-03-21 Composicion detergente para impartir fragancia residual, un compuesto profragante para dicha composicion y un metodo para suministrar fraganciaresidual
TR1998/01879T TR199801879T2 (xx) 1996-03-22 1997-03-21 Koku yerine ge�en bile�ikler.
CZ982997A CZ299798A3 (cs) 1996-03-22 1997-03-21 Čistící prostředky obsahující pro-vonnou sloučeninu
CN97194595A CN1218392A (zh) 1996-03-22 1997-03-21 香料前体化合物
JP9533805A JPH11507415A (ja) 1996-03-22 1997-03-21 プロフレグランス化合物を含んだ洗剤組成物
PCT/US1997/005373 WO1997034578A1 (fr) 1996-03-22 1997-03-21 Compose precurseur de parfum
JP9533806A JPH11507397A (ja) 1996-03-22 1997-03-21 プロフレグランス化合物
CA002249269A CA2249269A1 (fr) 1996-03-22 1997-03-21 Compositions detergentes comprenant un compose precurseur de parfum
BR9708576A BR9708576A (pt) 1996-03-22 1997-03-21 Composicões detergentes compreendendo composto profragráncia
EP97920026A EP0888442A1 (fr) 1996-03-22 1997-03-21 Compositions detergentes comprenant un compose precurseur de parfum
ZA9702514A ZA972514B (en) 1996-03-22 1997-03-24 Pro-fragrance compound.
ZA9702512A ZA972512B (en) 1996-03-22 1997-03-24 Detergent compositions comprising pro-fragrance compound.

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
CA002249588A CA2249588A1 (fr) 1996-03-22 1996-03-22 Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance

Publications (1)

Publication Number Publication Date
WO1997034986A1 true WO1997034986A1 (fr) 1997-09-25

Family

ID=25680542

Family Applications (1)

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

Country Status (2)

Country Link
CA (1) CA2249588A1 (fr)
WO (1) WO1997034986A1 (fr)

Cited By (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998047996A1 (fr) * 1997-04-24 1998-10-29 The Procter & Gamble Company Compositions de detergents a lessive renfermant des composes diffuseurs de parfum
WO1998047995A1 (fr) * 1997-04-24 1998-10-29 The Procter & Gamble Company Precurseurs de parfums orthocarbonates
WO1999000347A1 (fr) * 1997-06-27 1999-01-07 The Procter & Gamble Company Acetals et cetals lineaires precurseurs de parfum
WO2000024721A3 (fr) * 1998-10-23 2000-08-24 Procter & Gamble Precurseurs d'accords de parfum et bibliotheques de parfums a base d'aldehyde et de cetone
US6117833A (en) * 1998-12-16 2000-09-12 Lever Brothers Company Bleaching compositions and method for bleaching substrates directly with air
US6140298A (en) * 1998-12-16 2000-10-31 Lever Brothers Company, Division Of Conopco, Inc. Bleaching compositions based on air, uncomplexed transition metal ions and aromatic aldehydes
EP1184448A1 (fr) * 2000-08-30 2002-03-06 Clariant GmbH Liquides aqueux contenant un agent tensio actif et un acetal
US6454876B1 (en) 1999-12-22 2002-09-24 The Clorox Company Method for eliminating malodors
WO2002077074A1 (fr) 2001-03-27 2002-10-03 Firmenich Sa Composes servant a effectuer la liberation controlee de composes actifs
WO2002083620A1 (fr) * 2001-04-10 2002-10-24 The Procter & Gamble Company Pro-parfums photoactives
US6506793B2 (en) 2000-10-13 2003-01-14 Kao Corporation Citral acetal
US6677297B2 (en) 1999-10-18 2004-01-13 Firmenich Sa Esters comprising a secondary carbamoyl function and their use as odorant alcohol precursors
WO2004039158A1 (fr) * 2002-10-31 2004-05-13 Franz Bencsits Acetals comme agents insectifuges
WO2004047788A3 (fr) * 2002-11-25 2004-09-02 Colgate Palmolive Co Precurseurs fonctionnels de parfums
US6956013B2 (en) 2001-04-10 2005-10-18 The Procter & Gamble Company Photo-activated pro-fragrances
US7041279B1 (en) 1999-11-01 2006-05-09 The Clorox Company Method and product for mitigating pet malodors
US7109153B2 (en) 2000-11-08 2006-09-19 Procter & Gamble Company Photo-labile pro-fragrance conjugates
EP0977548B2 (fr) † 1997-04-24 2008-03-26 The Procter & Gamble Company Precurseurs d'accords de parfum
EP2008637A1 (fr) 2007-06-18 2008-12-31 Firmenich Sa Compositions d'annihilation malodorantes et leur procédé d'utilisation
WO2009156278A1 (fr) * 2008-06-27 2009-12-30 Henkel Ag & Co. Kgaa Pro-fragrance polymère
US7723285B2 (en) * 2004-07-20 2010-05-25 Michigan Molecular Institute Beneficial agent delivery systems
US8022030B2 (en) 2006-10-10 2011-09-20 Firmenich Sa Polymer conjugates for a controlled release of active molecules
WO2012146623A1 (fr) * 2011-04-29 2012-11-01 Basf Se Composition contenant un pesticide et un solvant acétalique
US8399499B2 (en) 2007-05-22 2013-03-19 Firmenich Sa 3- to 7-membered 1,3-diaza-4-OXO-heterocyclic derivatives capable of releasing active aldehydes or ketones
WO2013139766A1 (fr) 2012-03-20 2013-09-26 Firmenich Sa Composés pour une libération contrôlée de molécules parfumantes actives
WO2014029695A1 (fr) 2012-08-21 2014-02-27 Firmenich Sa Procédé d'amélioration des performances de fragrances encapsulées
WO2015032885A1 (fr) 2013-09-09 2015-03-12 Firmenich Sa Dérivés de thioéther comme précurseurs pour une libération contrôlée de molécules actives
WO2016091815A1 (fr) 2014-12-10 2016-06-16 Firmenich Sa Polysiloxanes en tant que systèmes de libération de parfum en parfumerie fine
US9585382B2 (en) 2011-04-29 2017-03-07 Basf Se Composition comprising a pesticide and an acetal solvent
US9765282B2 (en) 2013-06-19 2017-09-19 Firmenich Sa Polysiloxane conjugates as fragrance delivery systems
WO2018002214A1 (fr) 2016-06-30 2018-01-04 Firmenich Sa Microcapsules à noyau et enveloppe composite
DE102016223412A1 (de) 2016-11-25 2018-05-30 Henkel Ag & Co. Kgaa Cyclische Ketale als Duftstoffvorläuferverbindungen
US10034819B2 (en) 2012-09-24 2018-07-31 Firmenich Sa Multilayered core/shell microcapsules
US10323127B2 (en) 2015-02-17 2019-06-18 Firmenich Sa Poly(aspartic acid) derived co-polymers for a controlled release of perfuming ingredients
US10377965B2 (en) 2015-01-21 2019-08-13 Firmenich Sa Photolabile acetal and ketal compounds for the controlled release of active volatile carbonyl compounds
WO2019243369A1 (fr) 2018-06-21 2019-12-26 Firmenich Sa Composés destinés à fournir une odeur de fraise de longue durée
WO2020127708A1 (fr) 2018-12-20 2020-06-25 Firmenich Sa Pro-parfum d'alkylénoléther
WO2021023670A1 (fr) 2019-08-08 2021-02-11 Firmenich Sa Composés destinés à fournir une odeur de menthe de longue durée
DE102019125579A1 (de) * 2019-09-24 2021-03-25 Henkel Ag & Co. Kgaa Ketal-basierte duft- und insektenabwehrmittelvorläuferverbindungen
WO2021110680A1 (fr) 2019-12-03 2021-06-10 Firmenich Sa Pro-parfum d'énoléther
WO2021123144A1 (fr) 2019-12-20 2021-06-24 Firmenich Sa Compositions de proparfum
WO2021122997A1 (fr) 2019-12-19 2021-06-24 Firmenich Sa Composés destinés à fournir une odeur florale et fruitée de longue durée
WO2021209396A1 (fr) 2020-04-14 2021-10-21 Firmenich Sa Composés destinés à fournir une odeur de longue durée
WO2021250164A1 (fr) 2020-06-12 2021-12-16 Firmenich Sa Pro-parfum d'éther énolique
WO2022084437A1 (fr) 2020-10-21 2022-04-28 Firmenich Sa Compositions conférant une fraîcheur améliorée
WO2023067072A1 (fr) 2021-10-20 2023-04-27 Firmenich Sa Compositions de parfum améliorées comprenant des composés de précurseur de parfum contenant du soufre
WO2023067063A1 (fr) 2021-10-20 2023-04-27 Firmenich Sa Compositions de parfum améliorées comprenant des composés pro-parfum contenant du soufre
WO2023078909A1 (fr) 2021-11-03 2023-05-11 Firmenich Sa Acétals et cétals cycliques pour la libération induite par la lumière d'aldéhydes et de cétones actifs
WO2023111006A1 (fr) 2021-12-14 2023-06-22 Firmenich Sa Pro-parfum d'éther énolique
WO2024218086A1 (fr) 2023-04-17 2024-10-24 Firmenich Sa Acétals et cétals cycliques photolabiles pour distribution induite par la lumière d'aldéhydes et de cétones actifs
WO2025093456A1 (fr) 2023-11-03 2025-05-08 Firmenich Sa Proparfums de thiazolidine-4-carboxylate
WO2025153685A1 (fr) 2024-01-18 2025-07-24 Firmenich Sa Pro-parfums de 3-acyl-oxazolidin-5-one
WO2025157960A1 (fr) 2024-01-26 2025-07-31 Firmenich Sa Composés neutralisant les mauvaises odeurs
WO2025160319A1 (fr) 2024-01-26 2025-07-31 The Procter & Gamble Company Produits de consommation comprenant des composés neutralisant les mauvaises odeurs
WO2025190760A2 (fr) 2024-03-13 2025-09-18 Firmenich Sa Proparfums libérant de l'oxyde de mésityle

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111635826A (zh) * 2020-06-11 2020-09-08 成都中展科技有限公司 一种留香的组合物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2448660A (en) * 1947-10-30 1948-09-07 Rohm & Haas Preparation of ether acetals
US2490337A (en) * 1949-12-06 Preparation of ketals
US2668862A (en) * 1954-02-09 Process for acetal preparation
US5500154A (en) * 1994-10-20 1996-03-19 The Procter & Gamble Company Detergent compositions containing enduring perfume
US5500138A (en) * 1994-10-20 1996-03-19 The Procter & Gamble Company Fabric softener compositions with improved environmental impact

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2490337A (en) * 1949-12-06 Preparation of ketals
US2668862A (en) * 1954-02-09 Process for acetal preparation
US2448660A (en) * 1947-10-30 1948-09-07 Rohm & Haas Preparation of ether acetals
US5500154A (en) * 1994-10-20 1996-03-19 The Procter & Gamble Company Detergent compositions containing enduring perfume
US5500138A (en) * 1994-10-20 1996-03-19 The Procter & Gamble Company Fabric softener compositions with improved environmental impact

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
E. S. ROTHMAN ET AL: "Enol Esters XVI: Enol Esters in Synthesis", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, vol. 49, June 1972 (1972-06-01), pages 376 - 377, XP000611903 *
W.J. DEJARLAIS ET AL: "Preparation of Some Ethyl Higher-Alkyl Acetals and Their Conversion to Vinyl Ethers", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, vol. 38, May 1961 (1961-05-01), pages 241 - 243, XP000611904 *

Cited By (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998047996A1 (fr) * 1997-04-24 1998-10-29 The Procter & Gamble Company Compositions de detergents a lessive renfermant des composes diffuseurs de parfum
WO1998047995A1 (fr) * 1997-04-24 1998-10-29 The Procter & Gamble Company Precurseurs de parfums orthocarbonates
EP0977548B2 (fr) † 1997-04-24 2008-03-26 The Procter & Gamble Company Precurseurs d'accords de parfum
US6177389B1 (en) 1997-04-24 2001-01-23 The Procter & Gamble Company Detergent compositions comprising orthocarbonate pro-fragrances
WO1999000347A1 (fr) * 1997-06-27 1999-01-07 The Procter & Gamble Company Acetals et cetals lineaires precurseurs de parfum
US6316397B1 (en) 1997-06-27 2001-11-13 The Procter & Gamble Co. Pro-fragrance linear acetals and ketals
US6677491B2 (en) 1997-06-27 2004-01-13 Procter & Gamble Company Pro-fragrance linear acetals and ketals
WO2000024721A3 (fr) * 1998-10-23 2000-08-24 Procter & Gamble Precurseurs d'accords de parfum et bibliotheques de parfums a base d'aldehyde et de cetone
US7018978B2 (en) 1998-10-23 2006-03-28 Procter & Gamble Company Fragrance pro-accords and aldehyde and ketone fragrance libraries
US6140298A (en) * 1998-12-16 2000-10-31 Lever Brothers Company, Division Of Conopco, Inc. Bleaching compositions based on air, uncomplexed transition metal ions and aromatic aldehydes
US6117833A (en) * 1998-12-16 2000-09-12 Lever Brothers Company Bleaching compositions and method for bleaching substrates directly with air
US6677297B2 (en) 1999-10-18 2004-01-13 Firmenich Sa Esters comprising a secondary carbamoyl function and their use as odorant alcohol precursors
US7041279B1 (en) 1999-11-01 2006-05-09 The Clorox Company Method and product for mitigating pet malodors
US6454876B1 (en) 1999-12-22 2002-09-24 The Clorox Company Method for eliminating malodors
EP1184448A1 (fr) * 2000-08-30 2002-03-06 Clariant GmbH Liquides aqueux contenant un agent tensio actif et un acetal
US6506793B2 (en) 2000-10-13 2003-01-14 Kao Corporation Citral acetal
US7534751B2 (en) 2000-11-08 2009-05-19 The Procter & Gamble Company Photo-labile pro-fragrance conjugates
US7368415B2 (en) 2000-11-08 2008-05-06 Procter & Gamble Company Photo-labile pro-fragrance conjugates
US7109153B2 (en) 2000-11-08 2006-09-19 Procter & Gamble Company Photo-labile pro-fragrance conjugates
US7262156B2 (en) 2000-11-08 2007-08-28 Procter & Gamble Company Photo-labile pro-fragrance conjugates
WO2002077074A1 (fr) 2001-03-27 2002-10-03 Firmenich Sa Composes servant a effectuer la liberation controlee de composes actifs
WO2002083620A1 (fr) * 2001-04-10 2002-10-24 The Procter & Gamble Company Pro-parfums photoactives
US6956013B2 (en) 2001-04-10 2005-10-18 The Procter & Gamble Company Photo-activated pro-fragrances
AU2003283331B2 (en) * 2002-10-31 2007-08-30 Franz Bencsits Acetals as insect repellant agents
AU2003283331B8 (en) * 2002-10-31 2008-02-21 Franz Bencsits Acetals as insect repellant agents
US8642663B2 (en) 2002-10-31 2014-02-04 Franz Bencsits Acetals as insect repellant agents
WO2004039158A1 (fr) * 2002-10-31 2004-05-13 Franz Bencsits Acetals comme agents insectifuges
EA008175B1 (ru) * 2002-10-31 2007-04-27 Франц Бенкзитс Ацетали в качестве репеллентов от насекомых
US8901068B2 (en) 2002-11-25 2014-12-02 Colgate-Palmolive Company Functional fragrance precursor
US8906843B2 (en) 2002-11-25 2014-12-09 Colgate-Palmolive Company Functional fragrance precursor
AU2009240838B2 (en) * 2002-11-25 2011-09-29 Colgate-Palmolive Company Functional fragrance precursor
AU2009239944B2 (en) * 2002-11-25 2011-09-29 Colgate-Palmolive Company Functional fragrance precursor
US8895495B2 (en) 2002-11-25 2014-11-25 Colgate-Palmolive Company Functional fragrance precursor
EP2353653A3 (fr) * 2002-11-25 2013-02-13 Colgate-Palmolive Company Precurseurs fonctionnels de parfums
US8895496B2 (en) 2002-11-25 2014-11-25 Colgate-Palmolive Company Functional fragrance precursor
US8592361B2 (en) 2002-11-25 2013-11-26 Colgate-Palmolive Company Functional fragrance precursor
WO2004047788A3 (fr) * 2002-11-25 2004-09-02 Colgate Palmolive Co Precurseurs fonctionnels de parfums
US7723285B2 (en) * 2004-07-20 2010-05-25 Michigan Molecular Institute Beneficial agent delivery systems
US8022030B2 (en) 2006-10-10 2011-09-20 Firmenich Sa Polymer conjugates for a controlled release of active molecules
US8399499B2 (en) 2007-05-22 2013-03-19 Firmenich Sa 3- to 7-membered 1,3-diaza-4-OXO-heterocyclic derivatives capable of releasing active aldehydes or ketones
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
WO2009156278A1 (fr) * 2008-06-27 2009-12-30 Henkel Ag & Co. Kgaa Pro-fragrance polymère
CN103501597A (zh) * 2011-04-29 2014-01-08 巴斯夫欧洲公司 包含农药和缩醛溶剂的组合物
WO2012146623A1 (fr) * 2011-04-29 2012-11-01 Basf Se Composition contenant un pesticide et un solvant acétalique
CN103501597B (zh) * 2011-04-29 2016-02-17 巴斯夫欧洲公司 包含农药和缩醛溶剂的组合物
US9585382B2 (en) 2011-04-29 2017-03-07 Basf Se Composition comprising a pesticide and an acetal solvent
WO2013139766A1 (fr) 2012-03-20 2013-09-26 Firmenich Sa Composés pour une libération contrôlée de molécules parfumantes actives
US11155772B2 (en) 2012-03-20 2021-10-26 Firmenich Sa Compounds for a controlled release of active perfuming molecules
WO2014029695A1 (fr) 2012-08-21 2014-02-27 Firmenich Sa Procédé d'amélioration des performances de fragrances encapsulées
US9487733B2 (en) 2012-08-21 2016-11-08 Firmenich Sa Method to improve the performance of encapsulated fragrances
US10034819B2 (en) 2012-09-24 2018-07-31 Firmenich Sa Multilayered core/shell microcapsules
US9765282B2 (en) 2013-06-19 2017-09-19 Firmenich Sa Polysiloxane conjugates as fragrance delivery systems
WO2015032885A1 (fr) 2013-09-09 2015-03-12 Firmenich Sa Dérivés de thioéther comme précurseurs pour une libération contrôlée de molécules actives
US9758749B2 (en) 2013-09-09 2017-09-12 Firmenich Sa Thioether derivatives as precursors for a controlled release of active molecules
US9902920B2 (en) 2014-12-10 2018-02-27 Firmenich Sa Polysiloxanes as fragrance delivery systems in fine perfumery
WO2016091815A1 (fr) 2014-12-10 2016-06-16 Firmenich Sa Polysiloxanes en tant que systèmes de libération de parfum en parfumerie fine
US10377965B2 (en) 2015-01-21 2019-08-13 Firmenich Sa Photolabile acetal and ketal compounds for the controlled release of active volatile carbonyl compounds
US10508252B2 (en) 2015-01-21 2019-12-17 Firmenich Sa Photolabile acetal and ketal compounds for the controlled release of active volatile carbonyl compounds
US10323127B2 (en) 2015-02-17 2019-06-18 Firmenich Sa Poly(aspartic acid) derived co-polymers for a controlled release of perfuming ingredients
WO2018002214A1 (fr) 2016-06-30 2018-01-04 Firmenich Sa Microcapsules à noyau et enveloppe composite
EP4272861A2 (fr) 2016-06-30 2023-11-08 Firmenich SA Un produit de consommation comprenant des microcapsules avec enveloppe à noyau composite
US11179302B2 (en) 2016-06-30 2021-11-23 Firmenich Sa Core-composite shell microcapsules
WO2018095814A1 (fr) 2016-11-25 2018-05-31 Henkel Ag & Co. Kgaa Cétals cycliques et leur utilisation comme composés précurseurs odoriférants
DE102016223412A1 (de) 2016-11-25 2018-05-30 Henkel Ag & Co. Kgaa Cyclische Ketale als Duftstoffvorläuferverbindungen
US10941156B2 (en) 2016-11-25 2021-03-09 Henkel Ag & Co. Kgaa Cyclic ketals as fragrance precursor compounds
WO2019243369A1 (fr) 2018-06-21 2019-12-26 Firmenich Sa Composés destinés à fournir une odeur de fraise de longue durée
WO2020127708A1 (fr) 2018-12-20 2020-06-25 Firmenich Sa Pro-parfum d'alkylénoléther
WO2021023670A1 (fr) 2019-08-08 2021-02-11 Firmenich Sa Composés destinés à fournir une odeur de menthe de longue durée
EP3800184A1 (fr) * 2019-09-24 2021-04-07 Henkel AG & Co. KGaA Composés précurseurs d'agent odoriférant et insectifuge à base d'acétal / de cétal
DE102019125579A1 (de) * 2019-09-24 2021-03-25 Henkel Ag & Co. Kgaa Ketal-basierte duft- und insektenabwehrmittelvorläuferverbindungen
WO2021110680A1 (fr) 2019-12-03 2021-06-10 Firmenich Sa Pro-parfum d'énoléther
WO2021122997A1 (fr) 2019-12-19 2021-06-24 Firmenich Sa Composés destinés à fournir une odeur florale et fruitée de longue durée
WO2021123144A1 (fr) 2019-12-20 2021-06-24 Firmenich Sa Compositions de proparfum
WO2021209396A1 (fr) 2020-04-14 2021-10-21 Firmenich Sa Composés destinés à fournir une odeur de longue durée
WO2021250164A1 (fr) 2020-06-12 2021-12-16 Firmenich Sa Pro-parfum d'éther énolique
WO2022084437A1 (fr) 2020-10-21 2022-04-28 Firmenich Sa Compositions conférant une fraîcheur améliorée
WO2023067072A1 (fr) 2021-10-20 2023-04-27 Firmenich Sa Compositions de parfum améliorées comprenant des composés de précurseur de parfum contenant du soufre
WO2023067063A1 (fr) 2021-10-20 2023-04-27 Firmenich Sa Compositions de parfum améliorées comprenant des composés pro-parfum contenant du soufre
WO2023078909A1 (fr) 2021-11-03 2023-05-11 Firmenich Sa Acétals et cétals cycliques pour la libération induite par la lumière d'aldéhydes et de cétones actifs
WO2023111006A1 (fr) 2021-12-14 2023-06-22 Firmenich Sa Pro-parfum d'éther énolique
WO2024218086A1 (fr) 2023-04-17 2024-10-24 Firmenich Sa Acétals et cétals cycliques photolabiles pour distribution induite par la lumière d'aldéhydes et de cétones actifs
WO2025093456A1 (fr) 2023-11-03 2025-05-08 Firmenich Sa Proparfums de thiazolidine-4-carboxylate
WO2025153685A1 (fr) 2024-01-18 2025-07-24 Firmenich Sa Pro-parfums de 3-acyl-oxazolidin-5-one
WO2025157960A1 (fr) 2024-01-26 2025-07-31 Firmenich Sa Composés neutralisant les mauvaises odeurs
WO2025160319A1 (fr) 2024-01-26 2025-07-31 The Procter & Gamble Company Produits de consommation comprenant des composés neutralisant les mauvaises odeurs
WO2025190760A2 (fr) 2024-03-13 2025-09-18 Firmenich Sa Proparfums libérant de l'oxyde de mésityle

Also Published As

Publication number Publication date
CA2249588A1 (fr) 1997-09-25

Similar Documents

Publication Publication Date Title
WO1997034986A1 (fr) Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance
EP0888439A1 (fr) Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance
KR100634723B1 (ko) 광-불안정성 방향물 전달 시스템을 포함하는 조성물
US6239087B1 (en) Detergent compositions containing fragrance precursors and the fragrance precursors themselves
US6103688A (en) Aromatic compounds, processes for their preparation and their use in perfumery
KR20160006690A (ko) 향수 성분으로서의 3-(4-이소부틸-2-메틸페닐) 프로판알
KR20090024701A (ko) 향료 화합물
US6949680B2 (en) Ketones as precursors of active compounds
EP2474301B1 (fr) Mélanges de parfum comprenant du cyclopent-2-ényl-éthylester d'acide acétique
AU783151B2 (en) Fragrance precursors
US6096704A (en) Pro-fragrance compound
EP1188433B1 (fr) Utilisation des esters insaturés comme ingrédients parfumants
EP1096004A2 (fr) Précurseurs de parfum
US20050026998A1 (en) Compounds for the controlled release of active aldehydes
US6384269B1 (en) Esters with musky odor and their use in perfumery
US4435331A (en) Methyl carbonate of α,3,3-trimethyl cyclohexane methanol, organoleptic uses thereof and process for preparing same
EP0905115A1 (fr) Procédé pour la préparation de composés d'acétal
MXPA98007736A (en) Detergent compositions that comprise composite of profragan
MXPA98007744A (es) Compuesto de pro-fragancia
US11597895B2 (en) Aromatic substance mixtures containing 8,8-dimethyl-6,10-dioxaspiro[4,5]decane
CN1219195A (zh) 含有香料前体的洗涤剂组合物以及香料前体本身
US4488988A (en) Methyl carbonate of α,3,3-trimethyl cyclohexane methanol, organoleptic uses thereof and process for preparing same
EP0862912A1 (fr) Utilisation de 7-isopropyl-8, 8-dimethyl-6, 10-dioxaspiroundecane pour ses propriétés organoleptiques
DE69633415T2 (de) Duftstoffvorläufer

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 96180300.2

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 1997 516575

Country of ref document: JP

Kind code of ref document: A

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MX NO NZ PL PT RO RU SE SG SI SK TJ TM TR TT UA US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2249588

Country of ref document: CA

Ref document number: 2249588

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 09155140

Country of ref document: US

Ref document number: PA/A/1998/007743

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1996910554

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1996910554

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1996910554

Country of ref document: EP