MXPA97004709A - Precursors of fragan - Google Patents

Abstract

The present invention relates to fragrance precursors. In particular, the invention relates to the use of various classes of compounds that can act as fragrance precursors, for example in cosmetic products such as deodorants and antiperspirants, and in laundry products such as detergents and fabric softeners. These compounds are normally odorless or almost odorless, pro with the skin conduit as for example in skin care compositions or in personal care compositions, produce fragrances. The compounds also produce fragrances when used in the presence of lipases, for example as those used in detergents (laundry), thus providing an extension of the perfuming effect of the fabrics. The compounds under consideration are the compounds of formula I: (See Formula). Substituents are defined in the specification

Description

PRECURSORS OF FRAGRANCE DESCRIPTION OF THE INVENTION The present invention relates to fragrance precursors. In particular, the invention relates to the use of various classes of compounds that can act as fragrance precursors, for example in cosmetic products such as deodorants and antiperspirants, and in laundry products such as detergents and fabric softeners. These compounds are usually odorless or almost odorless, but on contact with the skin, as for example in skin care compositions or in personal care compositions, they produce fragrances. The compounds also produce fragrances when used in the presence of lipases, for example as those used in detergents (laundry), thereby providing a prolongation of the effect of perfuming the fabrics. One main strategy currently used to impart odors to consumer products is the mixing of the fragrance directly into the product. However, there are several drawbacks to this strategy. The fragrance material can be too volatile, resulting in loss of fragrance during manufacturing, storage, and use. Many fragrance materials are REF: 24975 also unstable over time. This again results in losses during storage. In some cases, the fragrances are microencapsulated or treated with cyclodextrins, to form inclusion complexes, to help reduce volatility and improve stability. However, for a number of reasons these methods are often not successful. In addition, cyclodextrins can be too expensive. In many consumer products it is desirable that the fragrance be released slowly over time. Microencapsulation and cyclodextrins have been used to provide slow release properties, however, they are subject to the same limitations as above. The present invention now provides compounds which exhibit a low level of odor, or are still odorless, before they are applied to the skin, but which release odorant molecules after application to the skin (ie, they provide a delayed release of the fragrance). ), in particular to the skin found in the armpit. The compounds of the present invention also release odorant molecules when used in the presence of products containing lipids, and, thus, provide an extension of the fabric perfuming effect.

The compounds under consideration are compounds of the formula I wherein R1 and R2, which may be the same or different, are the fragrant alcohol or fragrant mercaptan radicals RXXH and R2XH and, if only one of the radicals R1 and R2 is a fragrant alcohol, the other radical R1 or R2 is an alkyl radical of 1 to 40 carbon atoms or alkenyl of 2 to 40 optionally substituted carbon atoms, a carbocyclic or aromatic radical, whereby this radical R 1 or R 2 may additionally contain one or more heteroatoms, such as O, N, S, P, and groups such as (OCH2CH2) n, and -C (O) -, -COOR5 and / or substituents -OH, -CÍO) -, -COOR5 or -NH2, or is a polyalcohol or a sugar radical, of which one or more of the hydroxyl functions may be substituted as carbonates XR1 and / or XR2 as described above, and R3 or R4, which are the same or different, are H, alkyl of 1 to 6 carbon atoms, or together they form a carbocyclic or heterocyclic ring, and R5 is R1 or R2, X = O or S, m = O, 1 or 2, and n is 1-20. Examples of alcohols R XH and R2XH are primary or secondary alcohols, or phenols such as: amyl alcohol hexyl alcohol * 2-hexyl alcohol * heptylic alcohol * octyl alcohol * nonyl alcohol * decyl alcohol * undecylic alcohol * lauryl alcohol * myristic alcohol 3- methyl-but-2-en-l-ol * 3-methyl-l-pentanol cis-3-hexenol * cis-4-hexenol * 3,5,5-trimethylhexanol 3, 4, 5, 6, 6-pentamethylheptan- 2-ol (Kohinool, International Flavors &Fragrances) * citronellol * geraniol * oct-l-en-3-ol 2, 5, 7-trimethyl-octan-3-ol (Corps Abricot, Givaudan-Roure) 2-cis -3, 7-dimethyl-2, β-octadien-1-ol 6-ethyl-3-methyl-5-octen-l-ol (Meo Parf, Givaudan-Roure) * 3, 7-dimethyl-oct-3, ß-dienol * 3, 7-dimethyloctanol (Pelargol, Givaudan-Roure) * 7-methoxy-3, 7-dimethyl-octan-2-ol (Osyrol, BBA) * cis- β-nonenol * 5-ethyl-2-nonanol 6,8-dimethyl-2-nonanol (Nonadyl, Givaudan-Roure) * 2, 2, 8-trimethyl-7 (8) -nonen-3-ol (Corps Lavande, Givaudan-Roure) nona-2, 6-dien-l-lo 4-methyl-3-decen-5-lo (Undecavertol, Givaudan-Roure) * dec-9-en-l-lo benzyl alcohol 2-methyl-undecanol 10-undecen-l-lo 1-phenylethanol * 2-phenylethanol * 2-methyl-3-phenyl-3-propenyl 2-phenylpropanol * 3-phenylpropanol * 4-phenyl-2-butanol 2-methyl-5-phenylpentanol (Rosaphen , H + R) * 2-methyl-4-phenylpentanol (Pamplefleur, International Flavors & Fragrances) * 3-methyl-5-phenylpentanol (Phenoxanol, International Flavors & Fragrances) * 2- (2-methylphenyl) -ethanol * 4- (1-methylethyl) benzenemethanol (International Flavors & Fragrances) * 4- (4-hydroxyphenyl) butan-2-one * 2-phenoxyethanol * 4- (1-methylethyl) -2-hydroxy-l-methylbenzene 2-me oxy-4-methylphenol 4-methylphenol anisic alcohol * alcohol p-tololic * cinnamic alcohol * vanillin * ethyl vanillin * eugenol * isoeugenol * thymol anethole * decahydro-2-naphthalenol borneol * cedrenol (Givaudan-Roure) * farnesol * fenchyl alcohol * menthol * 3, 7, ll-trimethyl-2, 6, 10-dodecatrien-l-ol alpha ionol * tetrahydro ionol * 2- (1,1-dimethylethyl) cyclohexanol * 3- (1,1-dimethylethyl) cyclohexanol * 4- (1,1-dimethylethyl) cyclohexanol * 4- isoproyl-cyclohexanol (Folrosia® Givaudan-Roure) 6, 6-dimethylbicyclo [3.3. l] hept-2-en-2-ethanol (Diheptol, Dragoco) 6, 6-dimethylbicyclo [3.1. l] hept-2-en-methanol (Mirtenol, BBA) * p-ment-8-en-3-ol (Isopulegol, Givaudan-Roure) * 3, 3, 5-trimethylcyclohexanol 2,4,6-trimethyl-3 -cyclohexenylmethanol * 4- (1-methylethyl) cyclohexylmethanol (Mayol, Firmenich) * 4- (1,1-dimethylethyl) cyclohexane 2- (1,1-dimethylethyl) -cyclohexanol (Verdol, International Flavors &Fragrances) 2.2 , ß-trimethyl-alpha-propylcyclohexanepropanol (Timberol, Dragoco) * 5- (2, 2, 3-trimethyl-3-cyclopentenyl) -3-methylpentan-2-ol (Sandalore ""! R, Givaudan-Roure) * 3-methyl-5- (2,2, 3 -trimethylcyclopentyl-3-enyl) pent-4-en-2-ol (Ebanol, Givaudan-Roure) * 2-ethyl-4- (2,2,3-trimethylcyclopentyl-3-enyl) but-2-en-1 -ol (Radjanol, Givaudan-Roure) * 4- (5, 5, 6-trimethylbicyclo [2.2.l] hept-2-yl) -cyclohexanol (Sandela, Givaudan-Roure) * 2- (2-methylpropyl) -4 -hydroxy-4-methyltetrahydropyran * (Florosa Q, Quest) * 2-cyclohexylpropanol * 2- (1,1-dimethylethyl) -4-methylcyclohexanol (Rootanol, BASF) * 1- (2-tert-butylcyclohexyloxy) -2- butanol (Amber Core, Kao) * 1- (4-isopropylcyclohexyl) ethanol (Mugetanol, H &R) * etc. Examples of thiols R: XH or R2XH are: 3-mercapto-1-hexanol 2- (1-mercapto-l-methylethyl) -5-methylcyclohexanone methoxy-4-methyl-2-butan-2-thiol thiogeraniol thioterpineol * preferred alcohols It is a routine thing, that it is not possible to give a complete list of the RXXH odoriferous alcohols and mercaptans and R2XH, these alcohols and mercaptans are released as a result of the desired hydrolysis of the carbonates I by bacteria, in particular axillary bacteria, or lipases, and these alcohols are then able to impart pleasant odors. The skilled artisan is, however, very aware of those alcohols and mercaptans, which provide a positive contribution to the compositions of the fragrance.

Accordingly, Examples of -R1 and R2 are alkyl radicals of 1 to 40 carbon atoms, namely linear or branched, are in particular any of these alkyl radicals which are the subject of the above molecules. -alkenyl of 2 to 40 carbon atoms, namely linear or branched, with one or more unsaturations, are in particular any of these alkenyls described above. -alloy of 1 to 6 carbon atoms is any linear or branched alkyl radical. Examples of vinyl derivatives are derivatives of acrylic acid, etc. Carbocycles include in particular the following optionally substituted compounds: cycloalkane cycloalkene polycycloalkane polycycloalkene.

The aromatic rings comprise, in particular, one or more optionally substituted naphthalene benzene rings. The heterocycles include, in particular, the following optionally substituted compounds: pyridine pyrrole pyrrolidine pyrimidine furan thiophene dihydrofuran dihydropyran tetrahydrofuran tetrahydropyran quinoline furanose pyranose, etc. Examples of polyalcohols are diols, for example: diethylene glycol, propylene glycol, triethylene glycol, polyglycols, triols, for example glycerol, etc. Examples of sugars are the sugars of furanoside and pyranoside, for example glucose, fructose, etc.

The compounds I can preferably be used as sustained release odorants, but also to mask or attenuate undesirable odors, or to provide additional odors that were not initially present in the consumer products, ie, cosmetic products intended for application to the skin human, such as underarm deodorants or antiperspirants, or other deodorants that come in contact with the body, or in hand lotions, baby powder, baby lotions, ointments, foot care products, facial cleansers, body cleansing towels, facial makeup, colognes, after shave lotions, shaving creams, etc. Additional applications include laundry detergents, fabric softeners, fabric softeners, dishwashing detergents, and other consumer products containing lipase. The compounds I are virtually odorless under normal temperature and atmospheric conditions, i.e., about 10-50 degrees Celsius and about 20 to 100% relative humidity. However, when applied to the body, or when used in an application in the presence of lipases, undergo a transformation in which the fragrant alcohol is released.

The compounds I are not limited to any particular isomer, all possible stereo-, as well as geometric isomers, as well as mixtures thereof are thus included within the scope of formula I. Compounds I, with hydrolysis , provide alcohols that have organoleptic properties, and therefore allow the development of useful methods to improve the odor of consumer products. These compounds can be used individually, in an amount effective to improve the characteristic odor of a material. More commonly, however, the compounds are mixed with other components of the fragrance, in an amount sufficient to provide the desired odor characteristics. The amount required to produce the desired overall effect varies depending on the particular selected compounds I, the product in which it will be used, and the particular effect desired. For example, depending on the selection and concentration of the selected compound, when I is added either individually or as a mixture for example to a deodorant or laundry product composition, at levels that are in the range from about 0.1 to about 10% by weight, or more preferred from about 0.25 to about 4% by weight, an odorant, ie an odoriferous alcohol, is released in an "organoleptically effective amount" when the product is used. This newly formed odorant serves to improve the smell of the fragrance. The compounds I can therefore be used in the manufacture of odorant compositions used in the preparation of cosmetic and laundry products, for example deodorants, antiperspirants, laundry detergents, fabric softeners, and as is evident from the compilation above, can a wide range of known odorants or mixtures of odorants be used. In the manufacture of such compositions, the odorants or mixtures of odorants known above may be used according to methods known to the perfumer, such as, for example, those of WA Poucher, Perfumes, Cosmetics, Soaps, 2, 7th Edition, Chap an and Hall, London 1974. The compounds I can be prepared using standard methods known to the skilled chemist. These standard methods can be found in the chemical literature. For example, carbonates can be synthesized by the reaction of one equivalent of carbonic acid, phosgene, or a chemical equivalent of phosgene, with one or more alcohols or mercaptans in the presence of base.

Alternatively, the reaction of a coroformate, which is another equivalent of carbonic acid and an alcohl or mercaptan R: XH or R "XH, in the presence of a base, also produces a carbonate.This reaction is the substitution of a chloroformate for R "X or R'X; see Comprehensive Organic Chemistry, Vol. 2 D. Barton, WD Ollis, Ed. Page 1070. Vinyl glycosides can be prepared by the addition of β of mercaptans or alcohols to propiolic acid esters, preferably catalyzed by tertiary amines, such as trimethylamine. or triethylamine, etc. Suitable methods are described in the Examples. Example 1 Bis- (2-phenylethyl) carbonic acid ester To a solution of 10.72 g of triphosgene in 80 ml of dichloromethane, 26.51 g of phenethyl alcohol were added. While cooling in an ice bath, 17.16 g of pyridine were added dropwise over 45 minutes. Then the reaction mixture was stirred at room temperature for 62 hours. The reaction was diluted with dichloromethane, and washed with aqueous HCl and aqueous NaHCO 3. The organic phase was dried, filtered and evaporated to dryness. The resulting crystals were recrystallized from 60 ml of hexane, and then a second time from hexane: methyl t-butyl ether (50 ml: 50 ml) to provide 15.48 g of lean crystals.

NMR (CDCl) d: 7.34-7.18 (m, 10 H), 4.31 (t, J = 7.18 Hz, 4 H), 3.00 (t, J = 7.17 Hz, 4 H). Example 2 Ester 2, 3-bis-hex-3-enyloxycarbonyloxyproicyl, hex-3-enyl ester of carbonic acid To a solution of 32.30 g of triphosgene in 100 ml of dichloromethane was added dropwise 34.45 g of cis-3-hexenol for 10 minutes, while cooling in an ice / salt bath. Then 26.46 g of pyridine were added dropwise over 1 hour 45 minutes.After stirring the reaction mixture for 21 hours at room temperature, it was diluted with 200 ml of pentane, filtered and evaporated to dryness to give 51.14 g. of a yellow oil.

The crude product was added dropwise to an ice-cooled solution of 4.8 g of glycerin and 30 ml of pyridine in 100 ml of dichloromethane for 1 hour 45 minutes. After stirring the reaction mixture for 48 hours at room temperature, it was diluted with 200 ml of ether, and washed with 2 x 200 ml of 2N HCl. The aqueous phase was extracted with ether, then the organic phases. The combined extracts were washed with NaHCO 3 and saturated saline, dried and evaporated to dryness. The residue was purified by first distilling off the raw material, and then by chromatography on silica gel, to provide 19.5 g of an oil. NMR (CDCl;) d: 5.60-5.25 (m, 6 H), 5.16-5.06 (m, 1 H), 4.47-4.23 (m, 4 H), 4.18-4.07 (m, 6 H), 2.48-2.37 (m, 6 H), 2.13-1.99 (, 6 H), 0.97 (t, J = 7.48 Hz, 9 H). According to the same procedure, the following compounds were prepared: Example 3 Ester 2, 3-bis-phenethyloxycarbonyloxy-propyl, phenethyl ester of carbonic acid Starting from phenethyl alcohol and glycerol; NMR (CDCl;) d: 7.35-7.20 (m, 15 H), 5.13-5.03 (m, 1 H), 4.41-4.19 (m, 10 H), 2.97 (t, J = 7.17 Hz, 6 H). EXAMPLE 4 Benzyl ester, phenethyl ester of carbonic acid To a mixture of 29.9.6 g of phenethyl alcohol and 30 ml of pyridine in 150 ml of dichloromethane was added dropwise 60.5 g of benzyl chloroformate for 1 hour 45 minutes. After stirring the reaction mixture overnight at room temperature, it was diluted with ether, and washed with 2 N HCl, NaHCO 3 and water. After extraction with ether, the combined organic layers were dried and evaporated to dryness. The residue was purified by chromatography on silica gel, to give the product: 52.5 g of a colorless oil. NMR 'CDCl) d: 7.3 ^ -7.16 (m, 10 H), 5.13 (s, 2 H), 4.34 (t, J = 7.17 Hz, 2 H), 2.96 (t, J = 7.17 Hz, 2 H) . The following compounds were prepared according to the same procedure: Example 5: Benzyl ester, hex-3-enyl ester of carbonic acid Starting of cis-3-hexenol and benzyl chloroformate; l? ' NMR (CDC1-) d: 7.41-7.29 (m, 5 H), 5.58-5.44 (m, 2 H), 5.15 (s, 2 H), 4.13 (t, J = 7.02 Hz, 2 H), 2.47- 2.36 (m, 2 H), 2.11-1.97 (m, 2 H), 0.95 (t, J = 7.5 Hz, 3 H). Example 6: Benzyl ester, dec-9-enyl ester of carbonic acid Starting from dec-9-en-l-ol and benzyl chloroformate; Example 7 4-Allyl-2-methoxyphenyl ester, benzyl ester of carbonic acid Starting from eugenol and benzyl chloroformate; 20 NMR (CDC13) d: 7.44-7.26 (, 5 H), 7.04-6.70 (m, 3 H), 6.03-5.83 (m, 1 H), 5.24 (s, 2 H), 5.14-5.02 (m, 2 H), 3.75 (s, 3 H), 3.34 (d, J = 6.71 Hz, 2 H).

EXAMPLE 8 Hex-3-enyl ester, 2- (2-hex-3-enyloxycarbonyloxy-2-ethoxy-2-ethyl-ester of carbonic acid Starting from cis-3-hexenol and diethylene glycol bis-chloroformate; NMR (CDCl; ) d: 5.59-5.25 (, 4 H), 4.30-4.25 (, 4 H), 4.12 (t, J = 7.01 Hz, 4 H), 3.78-3.70 (m, 4 H), 2.47-2.37 (m, 4 H), 2.13-1.99 (, 4 H), 0.97 (t, J = 7.63 Hz, 6 H) Example 9 Ester 3, 7-dimethyl-oct-6-enyl, ester 2- [2- (3, 7-dimethyl-oct-6-enyloxycarbonyloxy) -ethoxy] -ethyl acid of carbonic acid Starting from citrone and diethylene glycol bis-chloroformate; NMR (CDCl;.) d: 5.12-5.04 (m, 2 H), 4.30-4.14 (m, 8 H), 3. 75-3.70 (m, 4 H), 2.04-1.91 (m, 4 H), 1.74-1.15 (m, 22 H), 0.92 (d, J = 6.5 Hz, 6 H). Example 10 (E) -3-phenylethyloxyacrylic acid ethyl ester The reaction was carried out in standard glass material under a nitrogen atmosphere. To 100 ml of diethyl ether were added 9.8 g (0.1 mole) of ethyl ester of propiolic acid, 12.2 g (0.1 mole) of fexxiletanol and 10.1 g (0.1 mole) of N-methylmorpholm. This solution was maintained without agitation at room temperature for 24 hours. The mixture was evaporated under vacuum, and the residue was purified by bulb-to-bulb distillation (eg: 70-75 ° C, 6.1 x 10"kg / cur, 0.006 mbar) to provide 15.7 g (88%) of an oil NMR (CDCl) d: 7.57 (d, 1 H), 7.37-7.13 (m, 5 H), 5.20 (d, 1 H), 4.15 (q, 2 H), 4.04 (t, 2 H), 3.00 (t, 2 H), 1.26 (t, 3 H) Example 11 Ethyl ester of (E) -hex- (Z) -3-en-loxyacrylic acid The reaction was carried out in standard glass material ba or a Nitrogen atmosphere To 100 ml of diethyl ether was added 9.8 g (0.1 mole) of ethyl ester of propiolic acid, 10.2 g (0.1 mole) of (Z) -3-hexenol and . 1 g (0.1 moles) of N-methylmorpholine. This solution was maintained without agitation at room temperature for 24 hours.

The mixture was evaporated under vacuum, and the residue was purified by bulb-to-bulb distillation (eg: 60-65 ° C, 6.1 x 10"6 kg / cm2, 0.006 mbar) to provide 17.5 g (88%) of an oil NMR (CDClj) d: 7.59 (d, 1 H), 5.65-5.45 (m, 1 H), 5.41-5.24 (m, 1 H), 5.10 (d, 1 H), 4.17 (q, 2 H) , 3.83 (t, 2 H), 2.46 (q, 2 H), 2.06 (qui, 2 H), 1.28 (t, 3 H), 0.98 (t, 3 H) In the same way, phenethyl ester was obtained of 3-phenethyloxyacrylic acid from phenethyl alcohol and phenethyl ester of propiolic acid Example 12 (E) -3- (3,7-Dimethyl-oct-6-enyloxy) -acrylic acid ethyl ester The reaction was carried out in standard glass material under a nitrogen atmosphere To 100 ml of diethyl ether were added 8 g (0.082 mole) of ethyl ester of propiolic acid, 12.8 g (0.082 mole) of 3,7-dimethyl-oct-6- in-l-ol and 8.3 g (0.082 moles) of N-methylmorpholine.

This solution was maintained without agitation at room temperature for 24 hours. The mixture was evaporated under vacuum, and the residue was purified by bulb to bulb distillation (eg: 70-75 ° C, 6.1 x 10"6 kg / cm2, 0.006 mbar) to provide 19.4 g (76%) of an oil NMR (CDC13) d: 7.58 (d, 1 H), 5.20 (d , 1 H), 5.14-4.98 (m, 1 H), 4.16 (q, 2 H), 3.89 (t, 2 H), 2.10-1.00 (m, 7 H), transposed: 1.69 (s, 3 H) , 1.60 (s, 3 H), 1.28 (t, 3 H), 0.92 (d, 3 H).

Example 13 (E) -3-dec-9-enyloxyacrylic acid ethyl ester The reaction was carried out in standard glass material under a nitrogen atmosphere. To 150 ml of diethyl ether was added 9.8 g (0.1 mole) of ethyl ester of propiolic acid, 15.6 g (0.1 mole) of dec-9-en-1-ol and . 1 g (0.1 moles) of N-methylmorpholine. This solution was maintained without agitation at room temperature for 24 hours.

The mixture was evaporated under vacuum, and the residue was purified by bulb-to-bulb distillation (eg: 85-90 ° C, 6.1 x 10"6 kg / cpr, 0.006 mbar) to provide 23.2 g (91.6%) of an oil NMR (CDCl;.) d: 7.59 (d, 1 H), 5.92-5.70 (m, 1 H), 5.18 (d, 1 H), 5.06-4.87 (m, 2 H), 4.16 (q, 2). H), 3.83 (t, 2 H), 2.12-1.96 (m, 2 H), 1.80-1.58 (m, 2 H), 1.50-1.16 (m, 13 H) Example 14 The foing sulfur compounds were prepared : O-ethyl ester, S- [l-methyl-l- (4-methyl-2-oxo-cyclohexyl) -Jetyl ester from thio-dihydro-carvone and chloroformic acid ethyl ester, 4-Propyl- [l, 3] oxatian-2-one from 3-mercapto-l-hexanol and phosgene. 3-Ethoxycarbonylsulfanylhexyl, ethyl ester of carbonic acid from 3-mercato-l-hexanol and chloroformic acid ethyl ester. In addition, the compounds listed below were prepared: Example 15 R ^ H Synthesis via Example x Product from: cis-3-hexenol x = 1 Ester dihex-3-cis-3-hexenol; enyl of the triphosgene carbonic acid citronellol x = 1 ester bis (3,7-di-citronellol; triphosgene methyl oct-6-enyl carbonic acid Rosalva x = 1 ester didec-9- (dec-9-en-l-ol ) dec-9-en-l-ol; en-triphosgene of carbonic acid alcohol x = 4-tert-butyl phenethyl ester phenethyl alcohol; cyclohexyl; phenethyl ester chloroformate 4-t-butyl-cyclohexyl of carbonic acid geraniol x = 4 ester 4-t-butyl-geraniol; cyclohexyl chloroformate, 4-t-butyl-cyclohexyl ester 3,7-dimethyl-octa-2,6-dienyl carbonic acid geraniol x = 8-ester 3,7-dime - geraniol; bis-chloroformate til-octa-2, 6- diethylene glycol dienyl, ester 2- [(3,7-dimethyl-octa-2,6-dienyl-oxycarbonyloxy) -ethoxy-ethyl alcoholic acid alcohol x = 4 butyl ester, phenethyl alcohol phenethyl ester, phenethyl ester butyl chloroformate charcoal acid cis-3-hexenol x = 4 butyl ester cis-3-hexenol, butyl hex-3-chloroformate ester carbonic acid glycan geraniol x = 4 geraniol butyl ester; 3-7-dimethylochloroformate butyl-octyl-2,6-di-enyl ester of carbonic acid alcohol x = 4 benzyl benzyl ester 1,6-hexanediol; 6-benzoyl chloroformate benzyl oxycarbonyloxyhexyl ester of ethyl acid ethyl x = 7 benzyl ester vanillin ethyl vanillin; 2-ethoxy-chloroformate benzyl 4-formylphenyl ester of carbonic acid Example 16 Test fabrics were washed with a detergent containing lipase, to which one or more delayed-release fragrances had been added. The headspace analysis of the wet and dry cloth indicated the presence of fragrant alcohols. The level of alcohol was higher than when the test cloth was washed with a detergent containing lipase to which one or more fragrant alcohols were added.

Example 17 The test cloth was washed with a detergent containing lipase and then a fabric softener containing one or more delayed release fragrances was added to the rinse cycle. The headspace analysis of the wet and dry cloth indicated the presence of fragrant alcohols. The level of alcohol was higher than when the test cloth was washed with a detergent containing lipase and then a fabric softener containing one or more fragrant slow-release alcohols was added to the rinse cycle. Example 18 Cultures of armpit bacteria containing 0.1% precursor I were incubated for 20 hours at 30 ° C. After filtration of the cells, the presence of the parent alcohol was detected in each case by GC space-spacing techniques. head and / or the majority of a panel of 18 members. The same tests were carried out with inactivated cultures (85 ° / 20 minutes). The odor of the parent alcohol could not be detected after incubation, thus precluding hydrolysis by the culture medium.

Example 19 The following examples are set forth for the use of the delayed release fragrances of the present invention in various products. The methods of forming the following compositions are well known to those skilled in the art. All formulations may contain additional ingredients known to those skilled in the art, for example colorants, opacifiers, buffers, antioxidants, vitamins, emulsifiers, U.V. radiation absorbing agents, silicones and the like. All products can also be buffered to the desired pH. All values are in% p / p. Deodorant Colony Delayed Release Fragrances 0.5 1.5 2.5 6.0 Fragrance 0.5 1.5 2.5 6.0 Triclosan (Ciba Geigy) 1.0 0.75 1.0 Alcohol 100 100 100 100 Bar deodorants: Antiperspirant Ethylene glycol monostearate 7.0 Butyrosporum parkii seed butter 3.0 Neobee 1053 (PVO International) 12.0 Generol 122 (Henkel) 5.0 Kesco ax B (Akzo) 17.0 Di ethicone Dow Corning 345 35.0 Aluminum Sesquichlorohydrate 20.0 Delayed Release Fragrance 0.5 Fragrance 0.5 Antiperspirant Stearyl Alcohol 17.0 Castor wax 3.0 Talcum 5.0 Aluminum and zirconium tetrahydrochloride 20.0 Delayed release fragrance 1.0 Fragrance 1.0 Dimethicone Dow 245 to 100.0 Witconol APM 43.0 transparent deodorant stick Propylene glycol 20.0 Alcohol 39C 20.0 Demineralized water 7.0 Monamid 150ADD 5.0 Millithix 925 2.0 Ottasept Extra 0.5 Fragrance delayed release 0.75 Fragrance 0.75 Deodorant bar propylene g -, col 69.0 Demineralized water 21.8 Triclosan 0.2 Sodium stearate 8.0 Delayed release fragrances 0.5 Fragrance 0.5 Alcohol free deodorant stick Miristilic Ether PPG-3 (Witnocol APM) 36.0 Propylene glycol 36.0 Demineralized water 19.0 Triclosan 0.25 Sodium Stearate 7.75 Delayed release fragrances 0.5 Fragrance 0.5 Antiperspirant spray Absolute ethanol 15.0 Zirconium aluminum tetrachloride 5.0 Bentona 38 1.5 Delayed Release Fragrances 0.75 Fragrance 0.75 Hydrocarbon Propellant S-31 to 100.0 Antiperspirant Pump Demineralized Water 57.5 Aluminum Sesquichlorhydrate 20.0 Triton X-102 (Union Carbide) 2.0 Dimethyl Isosorbide (ICI) 20.0 Extended Release Fragrances 0.25 Fragrance 0.25 Deodorant with movable ball Dimethicone DC 354 (Dow Corning) 69.0 Bentona 38 10.0 Rezal 36 GP (Reheis Chem. Co.) 20.0 Delayed Release Fragrances 0.5 Fragrance 0.5 In the above compositions, the following compounds were used: Triclosan 5-chloro-2- ( 2,4-dichlorophenoxy) phenol Neobee 1053 glycerol tricaprate / caprylate Generol 122 soy sterol Kesscowax B cetyl alcohol and glycol polymer Witnocol APM polypropylene glycol myristyl ether 3 Monamid 150 ADD diethanolamine cocoamide Millithix 925 dibenzylidene sorbitol Ottasept Extra quaternium 18 hectorite Bentona 38 quaternium 18 hectorite Triton X -102 octoxynol-13 Dimethicone DC 354 mixture of fully methylated linear siloxane polymers blocked at the end with trimethylsiloxy units Rezal 36 GP tetrachlorohydrexglycine aluminum and zirconium It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (10)

1. CLAIMS 1. A fragrance precursor composition, preferably a composition for application to human skin, characterized in that it contains an organoleptically effective amount of at least one compound of the formula I: wherein R1 and R2, which may be the same or different, are the fragrant alcohol or fragrant mercaptan radicals RXH and R2XH and, if only one of the radicals R1 and R2 is a fragrant alcohol, the other radical R1 or R2 is an alkyl radical of 1 to 40 carbon atoms or alkenyl of 2 to 40 optionally substituted carbon atoms, a carbocyclic or aromatic radical, whereby this radical R 1 or R 2 may additionally contain one or more heteroatoms, such as O, N, S, P, and groups such as (OCH2CH2) n, and -C (O) -, -COOR5 and / or substituents -OH, -C (O) -, -COOR5 or -NH2, or is a polyalcohol or radical sugar, of which one or more of the hydroxyl functions may be substituted as carbonates XR1 and / or XR2 as described above, and R3 or R4, which are the same or different, are H, alkyl of 1 to 6 carbon atoms , or together they form a carbocyclic or heterocyclic ring, and R "is R1 or R2, X = 0 or S, m = 0, 1 or 2, and n is 1-20 suitably in a po Cosmetically acceptable ingredient 2. A composition according to claim 1, characterized in that in the compounds of formula I, m = 0. 3. A composition according to claim 1 or claim 2, characterized in that the compound of formula I is selected from the group consisting of: Bis- (
2. 2-phenylethyl) ester of carbonic acid Ester 2, 3-bis-hex-3-enyloxycarbonyloxyproicyl, hex-3-enyl ester of carbonic acid Ester 2, 3-bis-phenethyloxycarbonyloxy-propyl , phenethyl ester of carbonic acid Benzyl ester, phenethyl ester of carbonic acid Benzyl ester, hex-
3. 3-enyl ester of carbonic acid Benzyl ester, dec-9-enyl carbonic acid ester
4. 4-allyl-2-methoxyphenyl ester, benzyl ester of carbonic acid, hex-3-enyl ester, 2- (2-hex-3-enyloxy-carbonyloxy-ethoxy) -ethyl ester of carbonic acid Ester 3, 7-dimethyl-oct -6-enyl, 2- [2- (3,7-dimethyl-oct-6-enyloxycarbonyloxy) -ethoxy-ethyl ester of carbonic acid ester (E) -3-phenylethyloxy-acrylic acid ethyl ester (E) - ethyl ester hex- (Z) -3-enyloxyacrylic acid (E) -3- (3,7-dimethyl-oct-6-enyloxy) -acrylic acid ethyl ester (E) -3-dec-9-enyloxy-acrylic acid ethyl ester ester O-ethyl, S- [l-methyl-l- (4-methyl-2-oxo-cyclohexyl) thiocarbonic acid methyl ester 4-Propyl- [1,3] oxatian-2-one. Ethyl ester, 3-ethoxycarbonylsulfanylhexyl ester of carbonic acid. 4. A composition according to claim 1, 2 or 3, characterized in that the compound of formula I is selected from the group consisting of: dihex-3-enyl ester of carbonic acid bis (3,7-dimethyl-oct- 6-enyl carbonic acid didec-9-enyl ester of carbonic acid 4-t-butylcyclohexyl ester, phenethyl ester of carbonic acid 4-t-butyl-cyclohexyl ester, 3,7-dimethyl-octa-2,6-dienyl acid ester carbon 3,7-dimethyl-octa-2,6-dienyl ester, 2 - [(3,7-dimethylocta-2,6-dienyloxycarbonyloxy) ethoxy-ethyl ester of carbonic acid butyl ester, phenethyl ester of carbonic acid butyl ester, hex-3-enyl ester of carbonic acid, butyl ester, 3,7-dimethyl-oct-2,6-dienyl ester of carbonic acid, benzyl ester, 6-benzoyloxycarbonyloxyhexyl ester of carbonic acid, benzyl ester, 2-ethoxy-4-formylphenyl ester 5. A fragrance precursor product, for example a prod cosmetic uct, for example a personal or antiperspirant body deodorant article, characterized in that it contains at least one compound I according to claims 1, 2 or 3. 6. A compound of formula I according to claims 1, 2 or 3, characterized in that it is as illustrated in Examples 1 to 14. 7. A compound of formula I according to claims 1, 2 or 3, characterized by is as illustrated in Example 15. 8. Process for prolonging the smelling effect characteristic of an odoriferous compound RXXH and / or R2XH, preferably on human skin, characterized in that it comprises applying a composition according to claims 1, 2 or 3. 9. A method of suppressing the evil odor of the human body, by means of the compounds of formula I according to claim 1, characterized in that it comprises the application to human skin of a fragrance precursor product, preferably a cosmetic product according to claim 5. 10. The use of a compound I according to claims 1, 2 or 3 as a fragrance precursor composition, characterized in that it is preferably given in a composition for application to human skin, for example in a personal body deodorant or antiperspirant composition .