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US20030114352A1 - Depot preparations - Google Patents

Depot preparations Download PDF

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Publication number
US20030114352A1
US20030114352A1 US10/222,301 US22230102A US2003114352A1 US 20030114352 A1 US20030114352 A1 US 20030114352A1 US 22230102 A US22230102 A US 22230102A US 2003114352 A1 US2003114352 A1 US 2003114352A1
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Prior art keywords
carboxylic acids
formula
aldehyde
oil
compound
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US10/222,301
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English (en)
Inventor
Marcus Eh
Horst Surburg
Steffen Sonnenberg
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Symrise AG
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Symrise AG
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Assigned to HAARMANN & REIMER GMBH reassignment HAARMANN & REIMER GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EH, MARCUS, SONNENBERG, STEFFEN, SURBURG, HORST
Publication of US20030114352A1 publication Critical patent/US20030114352A1/en
Assigned to SYMRISE GMBH & CO. KG reassignment SYMRISE GMBH & CO. KG MERGER (SEE DOCUMENT FOR DETAILS). Assignors: HAARMANN & REIMER GMBH
Priority to US11/325,941 priority Critical patent/US8268772B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/16—Acetic acid esters of dihydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/28—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with dihydroxylic compounds

Definitions

  • the present invention relates to depot preparations or delivery systems for the targeted release of an aldehyde with two carboxylic acids.
  • the released aldehydes are organoleptic substances, which are useful as fragrances or flavorings.
  • the depot preparations can be prepared by reacting aldehydes with carboxylic anhydrides.
  • the method for perfuming consumer articles involves mixing the perfume oil containing fragrances directly with the product.
  • the problems, which arise with this process, are that readily volatile substances are partially or completely lost as a result of evaporation during incorporation into the product or during storage.
  • numerous substances, and aldehydes in particular, are unstable under the given conditions, which leads to partial or complete decomposition of these molecules.
  • all substances, which underlie the problems described above, can, in sensory terms, only be weakly perceived or cannot be perceived at all. In some cases this may lead to a change in the overall odor impression of the composition.
  • WO 94/06441 discloses acetals, ketals and specific ortho esters as depot preparations, which are stable in basic media.
  • acidic media such as, for example, upon contact with the skin, hydrolysis occurs, releasing alcohols and ketones.
  • a depot preparation for the release of aldehydes, specifically citral, in foods and here specifically in alcoholic or nonalcoholic beverages is described in WO 00/04009. These are dicarboalkoxydioxolans, which are obtainable by acetylation from an aldehyde and a tartaric acid derivative. In aqueous acidic alcoholic and nonalcoholic beverages these preparations have a longer half-life than comparable acetals.
  • WO 00/38616 discloses a cyclic dioxaketone, which, after hydrolysis, simultaneously releases an aldehyde or ketone and a hydroxy-carboxylic acid. These compounds are prepared by reacting the corresponding hydroxycarboxylic acid with the aldehyde or ketone with the addition of catalytic amounts of acid in the water separator. Preference is given to aldehydes or ketones with fragrance properties and ⁇ -hydroxy-carboxylic acids or ring-substituted benzoic acids.
  • the present invention provides depot preparations containing at least one compound of the formula (I)
  • R 1 , R 2 and R 3 are an organic radical having 1 to 30 carbon atoms, and the compound of the formula (I), after hydrolysis or enzymatic cleavage, releases an aldehyde and two carboxylic acids.
  • the present inventions contains compounds of the formula (I) in which
  • R 1 is a saturated or unsaturated, linear or branched, alicyclic or aromatic radical having 1 to 18 carbon atoms, which may optionally also contain heteroatoms,
  • R 2 and R 3 are a saturated or unsaturated, linear or branched, alicyclic or aromatic radical having 1 to 22 carbon atoms, which may optionally also contain heteroatoms and which may optionally be substituted by ionic substituents,
  • R 2 and R 3 together form a saturated or unsaturated, branched or unbranched, carbocyclic or aromatic ring of 3 to 10 carbon atoms, preferably of 4 to 8 carbon atoms.
  • Preferred heteroatoms include oxygen and sulfur. More preferably the heteroatoms are oxygen.
  • Examples of ionic substituents include —CO 2 M or —OCO 2 M, where M is an alkali metal.
  • the acylals of the formula (I), according to the present invention decompose after aqueous hydrolysis, preferably in alkaline aqueous medium with a pH of ⁇ 8, and also in acidic aqueous medium with a pH of ⁇ 3, more preferably the alkaline hydrolysis has a pH range from 9 to 13 and the acidic hydrolysis has a pH range from 0 to 2.5, so that an aldehyde and two carboxylic acids can be released which in turn releases the fragrance or flavoring and then can adhere to substrates.
  • the acylals of the formula (I), according to the present invention decompose after enzymatic cleavage, releasing an aldehyde and two carboxylic acids, which in turn releases the fragrance, or flavoring and then can attach to substrates.
  • the release rate can be controlled via the radicals R 2 and R 3 , depending on R 1 , such that acylals with small and narrow radicals R 2 and R 3 have short half-lives, while voluminous and long-chain radicals R 2 and R 3 increase the half-life of the acylals.
  • This is significant in as much as acylals of the formula (I) with different release profiles can thus be prepared.
  • the depot preparation and the formulation can be matched to one another as regards respective radicals or ingredients in order to achieve an application-oriented release as a result of controlled release or controlled adhesion/transfer.
  • the enzymatic cleavage can preferably be carried out by esterases or lipases.
  • the aldehyde released from the compound of the formula (I) has a molecular weight of from 100 to 350 g/mol and more preferably from 120 to 270 g/mol. It is also preferred if the released aldehyde is a fragrance or flavoring.
  • Nonlimiting examples of aldehydes which can be released following cleavage of the depot preparation according to the present invention include: phenylacetaldehyde, p-methylphenylacetaldehyde, p-isopropyl-phenylacetaldehyde, methylnonylacetaldehyde, phenylpropanal, 3-(4-t-butylphenyl)-2-methylpropanal (lilial), 3-(4-t-butylphenyl)propanal ( horreonal), 3-(4-methoxyphenyl)-2-methylpropanal (canthoxal), 3-(4-isopropylphenyl)-2-methylpropanal (cymal), 3-(3,4-methylenedioxyphenyl)-2-methylpropanal (helional), 3-(4-ethylphenyl)-2,2-dimethylpropanal (floralozone), phenylbutanal, 3-methyl-5-phenylpent
  • Nonlimiting examples of carboxylic acids which can be released following cleavage of the depot preparation according to the present invention include: unsubstituted saturated monocarboxylic acids (e.g. acetic acid, propionic acid, butyric acid, valeric acid, capric acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid); dialkyl-substituted acetic acids (e.g. 2-butyloctanoic acid, 2-butyldecanoic acid, 2-hexyloctanoic acid, 2-hexyldecanoic acid); mono- or polyunsaturated monocarboxylic acids (e.g.
  • unsubstituted saturated monocarboxylic acids e.g. acetic acid, propionic acid, butyric acid, valeric acid, capric acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid,
  • oleic acid linoleic acid, ( ⁇ -linolenic acid, ( ⁇ -linolenic acid); alkyne-, alkadiyne- or alkatriyne carboxylic acids (e.g.
  • non-8-ynoic acid dec-9-ynoic acid, tridec-9-ynoic acid, 13-methyltetradec-9-ynoic acid, pentadec-6-ynoic acid, pentadec-7-ynoic acid, hexadec-9-ynoic acid, 15-methylhexadec-9-ynoic acid, heptadec-2-ynoic acid, heptadec-9-ynoic acid, octadec-12-ynoic acid, octadec-6,12-diynoic acid, nonadec-9-ynoic acid); ⁇ -hydroxycarboxylic acids (e.g.
  • ⁇ -hydroxyvaleric acid ⁇ -hydroxycaproic acid, ⁇ -hydroxycaprylic acid, ⁇ -hydroxypelargonic acid, ⁇ -hydroxycapric acid, ⁇ -hydroxylauric acid, ⁇ -hydroxymyristic acid, ⁇ -hydroxypalmitic acid, ⁇ -hydroxypalmitic acid); unsubstituted ⁇ , ⁇ -alkanedicarboxylic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid).
  • ⁇ , ⁇ -alkanedicarboxylic acids e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid.
  • the depot preparation according to the present invention includes acylals of the formula (I) which have poor solubility in water and thus have a relatively large tendency to attach to substrates, or to accumulate in the headspace above an aqueous solution. Therefore, it is preferable for the acylals of the formula (I) according to the present invention to have a lower solubility in water than the carboxylic acids which are released so that better attachment of the carboxylic acids to the substrate can arise, or accumulation in the headspace above the aqueous phase takes place. Solubilities can be measured directly or can be determined more easily using octanol/water partition coefficients (log P value). The log P value is an established parameter for determining lipophilicity in the literature (A.
  • the transition from an aqueous system to a substrate is difficult as such molecules have a tendency to dissolve and be washed away. This applies to acidic compounds.
  • the present invention can overcome this problem because the transition of the carboxylic acid with a low log P value from the aqueous solution to a substrate takes place in the chemically bonded form of the acylals of the formula (I) according to the present invention having a higher log P value. This means that the transfer of a carboxylic acid following release from the depot preparation takes place at a higher rate than the transfer of the free carboxylic acid. Release takes place after subsequent cleavage of the depot preparation according to the present invention.
  • the controlled release of the aldehyde and of the two carboxylic acids from the depot preparation according to the present invention can be utilized for the treatment (e.g. fragrancing) of a wealth of substrates, such as, for example, hair, human skin, laundry and hard surfaces.
  • fragrances or perfume oils with which the depot preparation according to the present invention can be advantageously combined are given, for example, in S. Arctander, Perfume and Flavour Materials, Vol. I and 11, Montclair, N. J., 1969, published privately or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavour Materials, 3 rd . Ed., Wiley-VCH, Weinheim 1997.
  • Individual examples include: extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures, such as, for example, ambergris tincture; amyris oil; angelica seed oil; angelica root oil; aniseed oil; valerian oil; basil oil; wood moss absolute; bay oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; bucco leaf oil; cabreuva oil; cade oil; calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassia absolute; castoreum absolute; cedar leaf oil; cedarwood oil; cistus oil; citronella oil; lemon oil; copaiva balsam; copaiva balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davan
  • aliphatic alcohols such as, for example, hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixture of 3,4,5,6,6-pentamethyl -3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; of aliphatic aldehydes and 1,4-dioxacycloalken-2-ones thereof, such as, for example, hexan
  • aliphatic ketones and oximes thereof such as, for example, 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl -3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen -3-one; of aliphatic sulphur-containing compounds, such as, for example, 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;
  • aliphatic nitriles such as, for example, 2-nonenenitrile; 2-tridecene-nitrile; 2,12-tridecenenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;
  • aliphatic carboxylic acids and esters thereof such as, for example, (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl
  • acyclic terpene alcohols such as, for example, citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and formates, acetates, propionates, isobutyrate
  • acyclic terpene aldehydes and ketones such as, for example, geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyl-octanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
  • cyclic terpene alcohols such as, for example, menthol; isopulegol; alpha-terpineol; terpinenol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof;
  • cyclic terpene aldehydes and ketones such as, for example, menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-irone; alpha-damascone; beta-damascone; beta-damascenone; delta-damascone; gamma-damascone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one; nootkatone; dihydronootkatone; alpha-s
  • cyclic alcohols such as, for example, 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl -Z2,Z5, E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahyd ro-2H-pyran -4-ol;
  • cycloaliphatic alcohols such as, for example, alpha-3,3-trimethylcyclo-hexylmethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl -3-cyclopent-1-yl)-pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten -2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexy
  • cyclic and cycloaliphatic ethers such as, for example, cineol; cedryl methyl ether; cyclododecyl methyl ether; (ethoxymethoxy)cyclododecane; alpha-cedrene epoxide; 3a,6,6,9a-tetramethyidodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;
  • cyclic ketones such as, for example, 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclo-pentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis -2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1-ethoxyvinyl ) -3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclo-hexadecen-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 5-cyclohex
  • cycloaliphatic aldehydes such as, for example, 2,4-dimethyl -3-cyclo-hexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl) -2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde;
  • cycloaliphatic ketones such as, for example, 1-(3,3-dimethylcyclohexyl) -4-penten-1-one; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl 2,4-dimethyl-3-cyclohexen-1-yl ketone;
  • esters of cyclic alcohols such as, for example, 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl -2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl is
  • esters of cycloaliphatic carboxylic acids such as, for example, allyl 3-cyclohexyl-propionate; allyl cyclohexyloxyacetate; methyl dihydro-jasmonate; methyl jasmonate; methyl 2-hexyl-3-oxocyclopentane-carboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl -1,3-dioxolan-2-acetate;
  • aromatic hydrocarbons such as, for example, styrene and diphenylmethane
  • araliphatic alcohols such as, for example, benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl -3-phenylpropanol; 1-ethyl- -methyl-3-phenylpropanol; 2-methyl -5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;
  • esters of araliphatic alcohols and aliphatic carboxylic acids such as, for example, benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; alpha-trichloromethylbenzyl acetate; alpha,alpha-dimethylphenylethyl acetate; alpha,alpha-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; of araliphatic ethers, such as, for example, 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-
  • aromatic and araliphatic aldehydes such as, for example, benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropaldehyde; 4-methyl benzaldehyde; 4-methyl phenylacetaldehyde; 3-(4-ethylphenyl) -2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl -3-(4-tert-butylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; alpha-butylcinnamaldehyde; alpha-amylcinnamaldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxy-benzaldehyde; 4-hydroxy-3-methoxybenzaldeh
  • aromatic and araliphatic ketones such as, for example, acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl -2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl) -2-butanone; 1-(2-naphthalenyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5′, 6′, 7′, 8′-tetrahydro-3′, 5′, 5′, 6′, 8′, 8′-hexamethyl-2-acetonaphthone;
  • aromatic and araliphatic carboxylic acids and esters thereof such as, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy -3,
  • nitrogen-containing aromatic compounds such as, for example, 2,4,6-trinitro-1,3-dimethyl-5-tert-butyl benzene; 3,5-dinitro-2,6-dimethyl -4-tert-butylacetophenone; cinnamonitrile; 5-phenyl-3-methyl-2-pentenenitrile; 5-phenyl-3-methylpentanenitrile; methyl anthranilate; methyl N-methyl-anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy -3,7-dimethyloctanal; 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl -3-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-meth
  • phenols, phenyl ethers and phenyl esters such as, for example, estragole; anethole; eugenole; eugenyl methyl ether; isoeugenole; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenylacetate;
  • heterocyclic compounds such as, for example, 2,5-dimethyl -4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy -2-methyl-4H-pyran-4-one; 2-ethyl-3-hyd roxy-4H-pyran-4-one;
  • lactones such as, for example, 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1,15-pentade-canolide; cis- and trans-11-pentadecen-1,15-olide; cis- and trans -12-pentadecen-1,15-olide; 1,16-hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene 1,12-dodecanedioate; ethylene 1,13-tridecan
  • Fragrances or perfume oils which contain the depot preparation according to the present invention, can be used in liquid form, undiluted or diluted with a solvent for perfuming.
  • suitable solvents include, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate etc.
  • fragrances or perfume oils which contain the depot preparation according to the present invention, can be adsorbed to a carrier substance which serves both to distribute fragrances finely within the product and to release them in a controlled manner during use.
  • a carrier substance which serves both to distribute fragrances finely within the product and to release them in a controlled manner during use.
  • Such carriers may be porous in organic materials, such as light sulphate, silica gels, zeolites, gypsums, clays, clay granules, gas concrete etc., or organic materials such as wood and cellulose-based substances.
  • Fragrances or perfume oils which contain the depot preparation according to the present invention, can also be microencapsulated, spray-dried, in the form of inclusion complexes or in the form of extrusion products and can be added in this form to the product to be perfumed.
  • fragrances or perfume oils modified in this way can optionally be “coated” with suitable materials for a more targeted scent release, preferably the oils can be coated with wax-like synthetic materials, such as, for example, polyvinyl alcohol.
  • the microencapsulation of the fragrances or perfume oils can, for example, be carried out by the “coacervation process” using capsule materials made from, for example, polyurethane-like substances or soft gelatines.
  • the spray-dried perfume oils can, for example, be prepared by spray drying an emulsion or dispersion comprising the perfume oil, where the carriers used can be modified starches, proteins, dextrin and vegetable gums.
  • Inclusion complexes can be prepared, for example, by introducing dispersions of the perfume oil and cyclodextrins or urea derivatives into a suitable solvent, e.g. water.
  • Extrusion products can be obtained by melting the perfume oils with a suitable wax-like substance and by extrusion with subsequent solidification, optionally in a suitable solvent, e.g. isopropanol.
  • the amount of depot preparation, according to the present invention, used is 0.01 to 75% by weight, preferably 0.05 to 50% by weight, more preferably 0.5 to 20% by weight, based on the overall perfume oil.
  • Fragrances or perfume oils which comprise the depot preparation according to the present invention, can be used in concentrated form, in solutions or in above-described modified form for the preparation of, for example, cosmetic care products. This is true particularly for washing products or other product applications where a long-lasting odor impression on the skin or the hair is desired.
  • perfume extracts such as, for example, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water type, the water-in-oil type and the water-in-oil-in-water type, such as, for example, skin creams and lotions, face creams and lotions, sunscreen creams and lotions, aftersun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products such as, for example, hairsprays, hair gels, setting hair lotions, hair rinses, permanent and semi-permanent hair colorants, hair shaping compositions, such as cold waves and hair-smoothing compositions, hair
  • Fragrances or perfume oils which contain the depot preparation according to the present invention can preferably be used in concentrated form, in solutions or in the above-described modified form for the preparation of hair care products, deodorants and antiperspirants and here in particular for the preparation of permanent hair colorants.
  • fragrances or perfume oils which contain the depot preparation according to the present invention, can be used in concentrated form, in solutions or in the above-described modified form for the preparation of, for example, household products, such as floor cleaners, window cleaners, dishwashing detergents, bath and sanitary cleaners, scouring milk, solid and liquid WC cleaners, pulverulent and foam carpet cleaners, liquid laundry detergents, pulverulent laundry detergents, laundry pretreatment agents such as bleaches, soaking agents and stain removers, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants.
  • household products such as floor cleaners, window cleaners, dishwashing detergents, bath and sanitary cleaners, scouring milk, solid and liquid WC cleaners, pulverulent and foam carpet cleaners, liquid laundry detergents, pulverulent laundry detergents, laundry pretreatment agents such as bleaches, soaking agents and stain removers, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants.
  • fragrances or perfume oils which contain the depot preparation according to the present invention, can be used in concentrated form, in solutions or in the above-described modified form for the preparation of liquid or pulverulent laundry detergents.
  • the depot preparation according to the present invention can be used for the aromatization of, for example, packing products or foods, and use forms thereof for the use as food for human or animal consumption.
  • Preferred products to be aromatized include, for example, confectionery, bakery goods, chocolates, gelatin goods, sweets, alcoholic beverages, nonalcoholic beverages, ice cream, yogurt, milk drinks, soups, sauces, snacks, chewing gum, mouthwash, meat and sausage goods, vegetable protein goods, fish, cheese and baby food.
  • the aldehyde is reacted with a carboxylic anhydride in the presence of catalytic amounts of acid.
  • Acids which can be used for the reaction include: sulfuric acid, iron chloride, phosphorous trichloride and acidic ion exchangers.
  • the aldehyde can be reacted with a 1:1 mixture of two carboxylic anhydrides in the presence of catalytic amounts of acid.
  • Acids which can be used for the reaction, include those described in the paragraph above.
  • the resulting reaction mixture can be separated very simply by distillation or chromatography.
  • the depot preparations according to the present invention were incorporated into numerous consumer products and their performance properties were investigated using various methods.
  • molar equivalents of the aldehydes were used in the form of the acylals or in the form of the free aldehydes in order to ensure comparability.
  • the storage stability of a fragrance or of a depot preparation is defined by the percentage of substance still present after storage.
  • the depot preparation (DP) consisting of one or more acylals and the corresponding aldehydes (AL) are incorporated into separate samples (S DP and S AL ) of the same formulation of a consumer product, such as, for example, laundry detergent, shampoo or soap.
  • the separate samples are then divided into portions.
  • One portion of the sample S DP and S AL is subjected immediately to a suitable extraction and analytical measurement in order to determine the amount of depot preparation or aldehyde prior to storage.
  • a suitable standard is used for quantification.
  • the second portion is subjected to storage at elevated temperature for a defined period and then extracted and quantified using the same methods.
  • the odor evaluation of a depot preparation per se or in comparison with the corresponding aldehydes is carried out by a group of trained individuals.
  • the odor strength of the consumer product in use with regard to the aldehyde used is assessed.
  • the consumer product is used according to its designation for application to the skin or for the washing of laundry, skin or hair.
  • the consumer product itself, its aqueous solutions, the damp or dry laundry or the damp or dry skin, for example, is then assessed in terms of odor on a scale from 1 (weak odor) to 6 (strong odor).
  • Suitable extractants for liquid-liquid or liquid-solid extractions include, for example, solvents such as, for example, carbon dioxide, ethers, ketones, hydrocarbons, alcohols, water and esters.
  • surface-active adsorbents such as, for example, hair, textiles, ceramic, plastic, activated carbon and also poly-2,6-diphenyl-p-phenylene oxide (Tenax®) and crosslinked porous polymers based on styrene, ethylvinylbenzene, vinylpyrrolidone, vinylpyrridine and ethylene glycol dimethacrylate (Poropax® series), are suitable.
  • the fragrances enriched on these adsorbents are then desorbed by heating (thermo-desorption) or using solvents and can then be analyzed.
  • the storage stability of the free aldehyde after one month was 34%.
  • the acid formed from the free aldehyde produced an unpleasant odor note.
  • the storage stability of the aldehyde in the depot preparation was 93% and was thus significantly higher.
  • the washed textiles A and B were each transferred to separate glass bottles.
  • SPME analysis Solid Phase Microextraction
  • direct headspace analysis was then used to analyze the relative concentration of free aldehyde. More than five times more free aldehyde was found in the headspace above the damp laundry washed with the laundry detergent A. Seven times more aldehyde was found in the headspace above the dry laundry washed with the laundry detergent A.
  • Soaps A, C and E which contain the depot preparations showed no or only a slight color change while soaps D and F had a yellowish or grey coloration, respectively. Color stability is achieved as a result of the use of the depot preparations.
  • the depot preparation was added to a 1% strength aqueous soap solution, and the concentration of the depot preparation or of the free aldehyde was measured by SPME headspace analysis.
  • a delayed or incomplete hydrolysis can also be achieved.
  • some of the depot preparation can then be applied to the skin in the washing process, and then, as a result of the slower cleavage of the acylals, a long-lasting scent impression on the skin can be achieved.
  • the following shampoo formulation can be prepared by generally known methods.
  • the data refer to percentages by weight.
  • TABLE 4 Shampoo formulation Ingredients Composition A B Plantacare PS 10 Sodium Laureth Sulfate (and) 20.000 20.000 (1) Lauryl Glycoside Demineralized Water (Aqua) ad 100% ad 100% water Sodium chloride Sodium Chloride 1.400 1.400 Citric acid 10.0% Citric Acid 1.650 1.650 solution Phenonip (2) Phenoxyethanol (and) Methyl 0.500 0.500 paraben (and) Ethylparaben (and) Propylparaben (and) Butylparaben DP
  • Example 7 (4) 1-(Heptanoyloxy)decyl 0.3 heptanoate Aldehyde C10 (4) Decanal 0.12
  • the resulting shampoos A and B were used for washing hair tresses or in a half-head washing test on test persons.
  • the half-head washing test one half of the hair of the test persons was in each case washed with shampoo A, and the other half of the hair was washed with shampoo B.
  • the formulation of the developer mass typically comprises water, hydrogen peroxide, acids, such as, for example, phosphoric acid, citric acid etc., thickeners, emulsifiers, preservatives, solvents and further auxiliaries. 1% of DP Example 5 is added to the formulation of the developer mass.
  • the developer formulation which comprises 1% of DP Example 5, is stored for one and a half months at room temperature. TABLE 5 Storage stability of depot preparation in developer mass Stability [%] Stability [%] Stability [%] Stability [%] 0 days 13 days 28 days 42 days DP Example 5 100 100 98 100 (4)
  • the depot preparation is color, odor and analytically stable over the period of one and half months.
  • the three depot preparations DP Example 8, DP Example 9 and DP Example 10 were added to the developer mass in a concentration of in each case 0.3%.
  • the ammoniacal dye solution which consists of 2 to 16% ammonia and/or substitutes such as, for example, alkanolamines, in particular monoethanolamine, water, thickeners, emulsifier, bodying agents, reactive dyes, solvents, flexing agents, stabilizers and preservatives, is then added to the developer mass in the ratio 1:1. Samples are then taken from the hair dye solution at defined time intervals, neutralized and extracted with solvent, and the content of depot preparation and released aldehyde is determined by means of gas chromatography using an internal and external standard.
  • the depot preparations in the formulation for hair coloring exhibited, after combining the developer mass with the ammoniacal hair dye solution, spontaneous hydrolysis relative to the corresponding aldehydes. After just 5 minutes the depot preparations were virtually completely hydrolyzed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Medicinal Preparation (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
US10/222,301 2001-08-20 2002-08-16 Depot preparations Abandoned US20030114352A1 (en)

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Cited By (3)

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US20050191384A1 (en) * 2004-02-06 2005-09-01 Bretl Neil A. Hunter's breath masking flavor for use in chewing gum and the like
US20060166855A1 (en) * 2005-01-25 2006-07-27 Howard Murad Fragrance delivery system
US20080255247A1 (en) * 2005-11-22 2008-10-16 Nestec S.A. Oil-In-Water Emulsion and Its Use for the Delivery of Functionality

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US11346404B2 (en) 2018-10-09 2022-05-31 Means Industries, Inc. Coupling and control assembly for use in a motor vehicle

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US3023247A (en) * 1957-08-01 1962-02-27 Rhone Poulenc Sa Alkylaromatic aldehydes and their preparation
US3250681A (en) * 1961-12-04 1966-05-10 Celanese Corp Ethylidene diacetate as bacteriostat in cosmetic and other compositions
US4323466A (en) * 1970-09-15 1982-04-06 Lever Brothers Company Germicide
US3869517A (en) * 1971-04-28 1975-03-04 Rhodia Process for preparing hydroxy citronellal by saponification of the hydroxy ester
US4395430A (en) * 1981-06-24 1983-07-26 Hercules Incorporated Diketone generators
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US20060166855A1 (en) * 2005-01-25 2006-07-27 Howard Murad Fragrance delivery system
US20080255247A1 (en) * 2005-11-22 2008-10-16 Nestec S.A. Oil-In-Water Emulsion and Its Use for the Delivery of Functionality
US8513311B2 (en) * 2005-11-22 2013-08-20 Nestec S.A. Oil-in-water emulsion and its use for the delivery of functionality

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JP2003160793A (ja) 2003-06-06
ATE529394T1 (de) 2011-11-15
US20060111269A1 (en) 2006-05-25
BR0203358A (pt) 2003-05-27
EP1285907B1 (de) 2011-10-19
US8268772B2 (en) 2012-09-18
DE10140786A1 (de) 2003-03-06

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