Abstract:
The invention relates to fragrance precursors, In particular, the invention relates to the use of several classes of compounds which may act as fragrance precursors, e,g., in cosmetic products such as deodorants and antiperspirants and in laundry products such as detergents and fabric softners. These compounds are odorless, but upon contacting the skin as example, in skin care compositions or in personal care compositions, produce fragrances. The compounds also produce fragrances when used in the presence of lipases, e.g. as used in (laundry) detergents, thus providing a prolongation of the fabric scenting effect. The compounds under consideration are compounds of the formula I:                            
     The substituents are defined in the specification.

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     The present application is a continuation-in-part of U.S. Ser. No. 08/878,923 filed on Jun. 19, 1997, now abandoned, the entire contents of which is hereby incorporated by reference. 
    
    
     FIELD OF THE INVENTION 
     The invention relates to fragrance precursors. In particular, the invention relates to the use of several classes of compounds which may act as fragrance precursors e.g. in cosmetic products such as deodorants and antiperspirants and in laundry products such as detergents and fabric softeners. These compounds are odorless, but upon contacting the skin 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, e.g. as used in (laundry) detergents, thus providing a prolongation of the fabric scenting effect. 
     BACKGROUND OF THE INVENTION 
     A principal strategy currently employed in imparting odors to consumer products is the admixing of the fragrance directly into the product. There are, however, several drawbacks to this strategy. The fragrance material may be too volatile, resulting in fragrance loss during manufacturing, storage, and use. Many fragrance materials are also unstable over time. This again results in loss during storage. 
     In some cases, fragrances are micro-encapsulated or treated with cyclodextrins to form inclusion complexes to help decrease volatility and improve stability. However, these methods are for a number of reasons often not successful. In addition, cyclodextrins may be too expensive for commercial processes. 
     In many consumer products, it is desirable for the fragrance to 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 provides a solution for these and other problems. 
     SUMMARY OF THE INVENTION 
     The present invention provides compounds which are odorless, prior to application to the skin, but which release odorant molecules after application to the skin (that is, they provide a delayed release of the fragrance), in particular to the skin in the axilla. The compounds of the present invention also release odorant molecules when used in the presence of lipase-containing products, and, in this way, provide a prolongation of, e.g., the fabric scenting effect in detergents, fabric softeners, fabric softener sheets, and the like. 
     DETAILED DESCRIPTION OF THE INVENTION 
     In one embodiment of the present invention, a fragrance precursor of the formula I is provided:                           
     wherein 
     X is O or S; 
     m is 0, 1 or 2, and n is 1-20; 
     R 1  is the radical of an alcohol R 1 OH or a mercaptan R 1 SH having more than five carbon atoms; 
     R 2  is the radical of an alcohol R 2 OH or a mercaptan R 2 SH having more than five carbon atoms; or 
     R 2  is a substituted or unsubstituted C 1-40 -alkyl or C 2-40 -alkenyl radical, a carbocyclic radical or an aromatic radical, wherein this R 2  may in addition contain one or more hetero atoms, —COOR 5 , and groups                           
     which groups may further be substituted by —COOR 5 , wherein R 5  is the radical of an alcohol R 5 OH or a mercaptan R 5 SH having more than five carbon atoms, or 
     R 2  is a polyalcohol radical or a sugar radical, of which one or more of the hydroxyl functions may be substituted as carbonates containing R 1  and/or R 2 ; 
     wherein at least one of R 1 OH, R 1 SH, R 2 OH, R 2 SH, R 5 OH and R 5 SH has fragrance properties; 
     R 3  and R 4  are H or C 1-6 alkyl or 
     R 3  and R 4  form a carbocyclic or heterocyclic ring. 
     In another embodiment of the present invention there is provided a compound of formula                           
     wherein 
     X is O or S; 
     m is 0, 1 or 2, and n is 1-20; 
     R 1  is the radical of an alcohol R 1 OH or a mercaptan R 1 SH having more than five carbon atoms; 
     R 2  is the radical of an alcohol R 2 OH or a mercaptan R 2 SH having more than five carbon atoms; or 
     R 2  is a substituted or unsubstituted C 1-40 -alkyl or C 2-40 -alkenyl radical, a carbocyclic radical or an aromatic radical, wherein this R 2  may in addition contain one or more hetero atoms, —COOR 5 , and groups                           
     which groups may further be substituted by —COOR 5 , wherein R 5  is the radical of an alcohol R 5 OH or a mercaptan R 5 SH having more than five carbon atoms, or 
     R 2  is a polyalcohol radical or a sugar radical, of which one or more of the hydroxyl functions may be substituted as carbonates containing R 1  and/or R 2 ; 
     wherein at least one of R 1 OH, R 1 SH, R 2 OH, R 2 SH, R 5 OH and R 5 SH has fragrance properties; 
     R 3  and R 4  are H or C 1-6 alkyl or 
     R 3  and R 4  form a carbocyclic or heterocyclic ring. 
     Another embodiment of the present invention is process for prolonging the effect of diffusion of the characteristic odor of an odoriferous alcohol or mercaptan as defined above which includes applying to the skin a fragrance precursor as defined above. 
     Another embodiment of the invention is a method of suppressing human body malodor by means of the fragrance precursors set forth above. This process includes applying to human skin a composition set forth above in a cosmetically acceptable carrier. 
     Examples of alcohols R 1 OH or R 2 OH are primary or secondary alcohols or phenols, such as for example: 
     hexyl alcohol* 
     2-hexyl alcohol* 
     heptyl alcohol* 
     octyl alcohol* 
     nonyl alcohol* 
     decyl alcohol* 
     undecyl alcohol* 
     lauryl alcohol* 
     myristic alcohol 
     3-methyl-1-pentanol 
     cis-3-hexenol* 
     cis-4-hexenol* 
     3,5,5-trimethyl hexanol 
     3,4,5,6,6-pentamethylheptan-2-ol (KOHINOOL, International Flavors &amp; Fragrances)* 
     citronellol* 
     geraniol* 
     oct-1-en-3-ol 
     2,5,7-trimethyl octan-3-ol (CORPS ABRICOT, Givaudan-Roure) 
     2-cis-3,7-dimethyl-2,6-octadien-1-ol 
     6-ethyl-3-methyl-5-octen-1-ol (MEO PARF, Givaudan-Roure)* 
     3,7-dimethyl-oct-3,6-dienol* 
     3,7-dimethyloctanol (PELARGOL, Givaudan-Roure)* 
     7-methoxy-3,7-dimethyl-octan-2-ol (OSYROL, BBA)* 
     cis-6-nonenol* 
     5-ethyl-2-nonanol 
     6,8-dimethyl-2-nonanol (NONADYL, Givaudan-Roure)* 
     2,2,8-trimethyl-7 (8)-nonene-3-ol (CORPS LAVANDE, Givaudan-Roure) 
     nona-2,6-dien-1-ol 
     4-methyl-3-decen-5-ol (UNDECAVERTOL, Givaudan-Roure)* 
     dec-9-en-1-ol 
     benzylalcohol 
     2-methyl undecanol 
     10-undecen-1-ol 
     1-phenyl ethanol* 
     2-phenyl ethanol* 
     2-methyl-3-phenyl-3-propenol 
     2-phenyl propanol* 
     3-phenyl propanol* 
     4-phenyl-2-butanol 
     2-methyl-5-phenyl pentanol (ROSAPHEN, H+R)* 
     2-methyl-4-phenyl-pentanol (PAMPLEFLEUR, International Flavors &amp; Fragrances)* 
     3-methyl-5-phenyl-pentanol (PHENOXANOL, International Flavors &amp; Fragrances)* 
     2-(2-methylphenyl)-ethanol* 
     4-(1-methylethyl)benzene methanol 
     4-(4-hydroxyphenyl)butan-2-one* 
     2-phenoxy ethanol* 
     4-(1-methylethyl)-2-hydroxy-1-methyl benzene 
     2-methoxy-4-methyl phenol 
     4-methyl phenol 
     anisic alcohol* 
     p-tolyl alcohol* 
     cinnamic alcohol* 
     vanillin* 
     ethyl vanillin* 
     eugenol* 
     isoeugenol* 
     thymol 
     anethol* 
     decahydro 2-naphthalenol 
     borneol* 
     cedrenol (Givaudan-Roure)* 
     farnesol* 
     fenchyl alcohol* 
     menthol* 
     3,7,11-trimethyl-2,6,10-dodecatrien-1-ol 
     alpha ionol* 
     tetrahydro ionol* 
     2-(1,1-dimethylethyl)cyclohexanol* 
     3-(1,1-dimethylethyl)cyclohexanol* 
     4-(1,1-dimethylethyl)cyclohexanol* 
     4-isopropyl cyclohexanol (FOLROSIA® Givaudan-Roure) 
     6,6-dimethyl-bicyclo [3.3.1]hept-2-ene-2-ethanol (DIEPTOL, Dragoco) 
     6,6-dimethyl-bicyclo [3.1.1]hept-2-ene-methanol (MYRTENOL, BBA)* 
     p-menth-8-en-3-ol (ISOPULEGOL, Givaudan-Roure)* 
     3,3,5-trimethyl cyclohexanol 
     2,4,6-trimethyl-3-cyclohexenyl-methanol* 
     4-(1-methylethyl)cyclohexyl-methanol (MAYOL, Firmenich)* 
     4-(1,1-dimethylethyl)cyclohexanol 
     2-(1,1-dimethylethyl)-cyclohexanol (VERDOL, International Flavors &amp; Fragrances) 
     2,2,6-trimethyl-alpha-propyl cyclohexane propanol (TIMBEROL, Dragoco)* 
     5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methyl pentan-2-ol (SANDALORE® Givaudan-Roure)* 
     3-methyl-5-(2,2,3-trimethyl cyclopentyl-3-enyl)pent-4en-2-ol(EBANOL, Givaudan-Roure)* 
     2-ethyl-4(2,2,3-trimethyl cyclopentyl-3-enyl)but-2-en-1-ol (RADJANOL, Givaudan-Roure)* 
     4-(5,5,6-trimethylbicyclo[2.2.1]hept-2-yl)-cyclohexanol (SANDELA, Givaudan-Roure)* 
     2-(2-methylpropyl)-4-hydroxy-4-methyl-tetrahydropyran* (FLOROSA Q, Quest)* 
     2-cyclohexyl propanol* 
     2-(1,1-dimethylethyl)-4-methyl cyclohexanol (ROOTANOL, BASF)* 
     1-(2-tert-butyl-cyclohexyloxy)-2-butanol (AMBER CORE, Kao)* 
     1-(4-isoporpyl-cyclohexyl)-ethanol (MUGETANOL, H&amp;R)* 
     Examples of thiols R 1 XH or R 2 XH are: 
     3-mercapto-1-hexanol 
     2-(1-mercapto-1-methylethyl)-5-methylcyclohexanone 
     methoxy-4-methyl-2-butane-2-thiol 
     thiogeraniol 
     thioterpineol. 
     6 *preferred alcohols 
     It is a matter of course, that it is not possible to give a complete list of the odoriferous alcohols and mercaptans R 1 XH and R 2 XH, which alcohols and mercaptans are liberated as a result of the desired cleavage of the carbonates of formula I by bacteria, in particular axilla bacteria, or lipases and which alcohols are then capable of imparting agreeable odors. 
     The skilled artisan is, however, quite aware of those alcohols and mercaptans, which provide a positive contribution to the fragrance compositions. 
     Examples of vinyl derivatives are derivatives of acrylic acid, etc. 
     The carbocycles encompass in particular, optionally substituted 
     cycloalkanes, 
     cycloalkenes, 
     polycycloalkanes, and 
     polycycloalkenes. 
     The aromatic rings encompass in particular, optionally substituted 
     one or more benzene rings, and 
     naphthalene. 
     The heterocycles encompass in particular, optionally substituted 
     pyridine, 
     pyrrole, 
     pyrrolidine, 
     pyrimidine, 
     furane, 
     thiophene, 
     dihydrofuran, 
     dihydropyran, 
     tetrahydrofuran, 
     tetrahydropyran, 
     quinoline, 
     furanose, and 
     pyranose. 
     Examples of polyalcohols are diols, e.g., diethylene glycol, propylene glycol, triethylene glycol, polyglycols; and triols, e.g. glycerol. 
     Examples of sugars are furanoside and pyranoside sugars, e.g. glucose and fructose. 
     The compounds of formula I may preferably be used as sustained release odorants but may also be used to mask or attenuate undesirable odors or to provide additional odors not initially present in consumer products, such as for example, cosmetic products destined for application to human skin. Non-limiting examples of such consumer products which are classified herein as “personal care products” include underarm deodorants or antiperspirants or other deodorants contacting the body, in hand lotions, baby powders, baby lotions, ointments, foot products, facial cleansers, body wipes, facial make-up, colognes, after-shave lotions, or shaving creams. Additional applications which may be classified herein as “home care products” include laundry detergents, fabric softeners, fabric softener sheets, automatic dishwasher detergents, and other lipase-containing consumer products. 
     Thus, as used herein, the phrase “consumer products” has its art recognized meaning. In the present invention, the phrase “consumer products” is intended to mean both “personal care products” and “home care products.” 
     The compounds of formula I are odorless under normal temperature and atmospheric conditions (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, they undergo a transformation in which the fragrant alcohol is released. 
     The compounds of formula I are not limited to any particular isomers. Thus, all possible stereo- and geometric isomers, as well as mixtures thereof are included within the scope of formula I. 
     The compounds of formula I, upon cleavage, provide alcohols having organoleptic properties and therefore permit the development of methods useful in enhancing the odor of consumer products. These compounds may be used individually in an amount effective to enhance the characteristic odor of a material. More commonly, however, the compounds are mixed with other fragrance components in an amount sufficient to provide the desired odor characteristics. 
     The amount required to produce the desired, overall effect varies depending upon the particular compounds of formula I chosen, the product in which it will be used, and the particular effect desired. 
     For example, depending upon the selection and concentration of the specific compound chosen, when it is added either singly or as a mixture e.g. to a deodorant or laundry product composition, at levels ranging from about 0.1 to about 10% by weight, or most preferred about 0.25 to about 4% by weight, an odorant, i.e. an odoriferous alcohol in an “organoleptically effective amount” is released when the product is used. This newly formed odorant serves to enhance the odor of the fragrance. 
     The compounds of formula I may accordingly be used in the manufacture of odorant compositions used in the preparation of cosmetic and laundry products. Such products include, for example, deodorants, antiperspirants, laundry detergents, and fabric softeners. As is evident from the above compilation, a broad range of known odorants or odorant mixtures may be used. In the manufacture of such compositions, the known odorants or odorant mixtures set forth above may be used according to methods known to the perfumer, such as, for example, those methods found in W.A. Poucher, Perfumes, Cosmetics, Soaps, 2, 7th Edition, Chapman and Hall, London 1974. 
     The compounds of formula I may be prepared by using standard methods known to the skilled chemist. These standard methods may be found in the chemical literature. For example, carbonates may be synthesized by reaction of a carbonic acid equivalent, e.g., phosgene, or a chemical equivalent of phosgene, with one or more alcohols or mercaptans in the presence of a base. Alternatively, reaction of a chloroformate which is another such carbonic acid equivalent. and an alcohol or mercaptan R 1 XH or R 2 XH, in the presence of base, also yields a carbonate. This reaction is the substitution of a chloroformate by R 1 X or R 2 X; see Comprehensive Organic Chemistry, Vol. 2 D. Barton, W. D. Ollis, Ed. p. 1070. 
     The vinyl carbonates may be prepared by β-addition of mercaptans or alcohols to propiolic acid esters, preferentially catalyzed by tertiary amines, such as trimethylamine or triethylamine, etc. 
    
    
     The following examples are set forth to illustrate the synthesis of the compositions of the present invention. These examples are provided for purposes of illustration only and are not intended to be limiting in any sense. 
     EXAMPLE 1 
     Carbonic acid bis-(2-phenyl-ethyl)ester 
     To a solution of 10.72 g triphosgene in 80 ml dichloromethane, 26.51 g phenethyl alcohol was added. While cooling in an ice bath, 17.16 g pyridine was dropped in over 45 minutes. Then, the reaction was stirred at room temperature for 62 hours. The reaction was diluted with dichloromethane, 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 hexanes and then a second time from hexane:methyl t.-butyl ether (50 ml:50 ml) to yield 15.48 g of colorless crystals. 
     NMR (CDCl 3 )δ7.34-7.18 (m,10H), 4.31 (t, J=7.18 Hz,4H), 3.00 (t, J=7.17 Hz,4H). 
     EXAMPLE 2 
     Carbonic acid 2,3-bis-hex-3-enloxycarbonyloxy-propyl ester hex-3-enyl ester 
     To a solution of 32.30 g triphosgene in 100 ml dichloromethane, 34.45 g cis-3-hexenol was dropped in over 10 minutes while cooling in an ice/salt-bath. Then, 26.46 g pyridine was dropped in over 1 h 45 min. After stirring the reaction for 21 hours at room temperature the mixture was diluted with 200 ml pentane, filtered and evaporated to dryness to yield 51.14 g of a yellow oil. The raw product was then dropped in an ice cooled solution of 4.8 g glycerine and 30 ml pyridine in 100 ml dichloromethane over 1 h 45 min. After stirring the reaction for 48 h at room temperature, it was diluted with 200 ml ether and washed with 2×200 ml HCl 2N. The water phase was extracted with ether, then the combined organic phases were washed with NaHCO 3  and brine, dried and evaporated to dryness. The residue was purified by distilling off starting material first and then silica gel chromatography to yield 19.5 g of an oil. 
     NMR (CDCl 3 )δ5.60-5.25 (m,6H), 5.16-5.06 (m,1H), 4.47-4.23 (m,4H), 4.18-407 (m,6H), 2.48-2.37 (m,6H), 2.13-1.99 (m,6H), 0.97 (t, J=7.48 Hz, 9H). 
     EXAMPLE 3 
     Carbonic acid 2,3-bis-phenethyloxycarbonyloxy-propyl ester phenethyl ester 
     According to the procedure of Example 2, Carbonic acid 2,3-bis-phenethyloxycarbonyloxy-propyl ester phenethyl ester was prepared starting from phenethyl alcohol and glycerol. 
     NMR (CDCl 3 )δ7.35-7.20 (m,15H), 5.13-5.03 (m,1H),4.41-4.19 (m,10H), 2.97 (t, J=7.17 Hz,6H). 
     EXAMPLE 4 
     Carbonic acid benzyl ester phenethyl ester 
     To a mixture of 29.96 g phenethyl alcohol and 30 ml pyridine in 150 ml dichloromethane, 60.5 g benzylchloroformate was dropped in over 1 h 45 min while cooling in an ice-bath. After stirring over night at room temperature, the reaction was diluted with ether, washed with 2N HCl, NaHCO 3 , and water. After extraction with ether, the combined. organic layers were dried and evaporated to dryness. The residue was purified by silica gel chromatography to yield the product: 52.5 g of a colorless oil. 
     NMR (CDCl 3 ) d 7.37-7.16 (m,10OH), 5.13 (s,2H), 4.34 (t, J=7.17 Hz, 2H), 2.96 (t, J=7.17 Hz, 2H). 
     According to the procedure of Example 4, the compounds set forth in Examples 5-9 were prepared from the starting materials indicated below: 
     EXAMPLE 5 
     Carbonic acid benzyl ester hex-3-enyl ester 
     Starting Material: cis-3-hexenol and benzylchloroformate. 
     NMR (CDCl 3 )δ7.41-7.29 (m,5H), 5.58-5.44 (m,2H), 5.15 (s, 2H), 4.13 (t, J=7.02, 2H), 2.47-2.36 (m,2H), 2.11-1.97 (m,2H), 0.95 (t, J=7.5 Hz,3H). 
     EXAMPLE 6 
     Carbonic acid benzyl ester dec-9-enyl ester 
     Starting Material: dec-9-en-1-ol and benzyl chloroformate. 
     EXAMPLE 7 
     Carbonic acid 4-Allyl-2-methoxy-phenyl ester benzyl ester 
     Starting Material: Eugenol and benzyl chloroformate. 
     NMR (CDCl 3 ) d 7.44-7.26 (m,5H), 7.04-6.70 (m,3H), 6.03-5.83 (m,1H), 5.24 (s,2H), 5.14-5.02 (m,2H), 3.75 (s,3H), 3.34 (d, J=6.71 Hz,2H). 
     EXAMPLE 8 
     Carbonic acid hex-3-enyl ester 2-(2-hex-3-enyloxy-carbonyloxy-ethoxy)-ethyl ester 
     Starting Material: cis-3-hexenol and diethylene glycol-bis-chloroformate. 
     NMR (CDCl 3 ) d 5.59-5.25 (m,4H), 4.30-4.25 (m,4H), 4.12 (t, J=7.01 Hz,4H), 3.78-3.70 (m,4H), 2.47-2.37 (m,4H), 2.13-1.99 (m,4H), 0.97 t, J=7.63 Hz,6H). 
     EXAMPLE 9 
     Carbonic acid 3,7-dimethyl-oct-6-enyl ester 2-[2-(3,7-dimethyl-oct-6-enyloxycarbonyloxy)-ethoxy]-ethyl ester 
     Starting Material: citronellol and diethylene glycol-bis-chloroformate. 
     NMR (CDC3)δ5.12-5.04 (m, 2H), 4.30-4.14 (m, 8H), 3.75-3.70 (m, 4H), 2.04-1.91 (m, 4H), 1.74-1.15 (m, 22H), 0.92 (d, J=6.5 Hz, 6H). 
     EXAMPLE 10 
     (E)-3-Phenylethyloxy-acrylic acid ethyl ester 
     The reaction was performed in standard glassware under an atmosphere of N 2 . To 100 ml of diethylether were added 9.8 g (0.1 mol) of propiolic acid ethyl ester, 12.2 g (0.1 mol) phenylethanol and 10.1 g (0.1 mol) of N-methylmorpholine. This solution was kept without stirring at room temperature for 24 hours. The mixture was evaporated under vacuum and the residue purified by bulb to bulb distillation (bp: 70-75° C., 0.006 mbar) to yield 15.7 g (88%) of an oil. 
     NMR (CDCl 3 )δ7.57 (d, 1H); 7.37-7.13 (m, 5H); 5.20 (d, 1H); 4.15 (q, 2H); 4.04(t, 2H); 3.00 (t, 2H); 1.26 (t,3H). 
     EXAMPLE 11 
     (E)-Hex-(Z)-3-enyloxy-acrylic acid ethyl ester 
     The reaction was performed in standard glassware under an atmosphere of N 2 . To 100 ml of diethylether were added 9.8 g (0.1 mol) propiolic acid ethyl ester, 10.2 g (0.1 mol) (Z)-3-hexenol and 10.1 g (0.1 mol) N-methylmorpholine. This solution was kept without stirring at room temperature for 24 hours. The mixture was evaporated under vacuum and the residue purified by bulb to bulb distillation (bp: 60-65° C.; 0.006 mbar) to yield 17.5 g (88%) of an oil. 
     NMR (CDCl 3 )δ7.59 (d, 1H); 5.65-5.45 (m, 1H); 5.41-5.24 (m, 1H); 5.10 (d, 1H); 4.17 (q, 2H); 3.83 (t, 2H); 2.46 (q, 2H); 2.06 (qui, 2H); 1.28 (t, 3H); 0.98 (t, 3H). 
     In the same way, 3-phenethyloxy-acrylic acid phenethyl ester was obtained from phenethyl alcohol and propiolic acid phenethyl ester. 
     EXAMPLE 12 
     (E)-3-(3,7-Dimethyl-oct-6-enyloxy)-acrylic acid ethyl ester 
     The reaction was performed in standard glassware under an atmosphere of N 2 . To 100 ml of diethylether were added 8.0 g (0.82 mol) propiolic acid ethyl ester, 12.8 g (0.82 mol) 3,7-dimethyl-oct-6-en1-ol and 8.3 g (0.82 mol) N-methylmorpholine. This solution was kept without stirring at room temperature for 24 hours. The mixture was evaporated under vacuum and the residue purified by bulb to bulb distillation (bp: 70-75° C.; 0.006 mbar) to yield 19.4 g (76%) of an oil. 
     NMR (CDCl 3 )δ7.58 (d, 1H); 5.20 (d, 1H); 5.14-4.98 (m, 1H); 4.16 (q, 2H), 3.89 (t, 2H); 2.10-1.00 (m, 7H), overlapped: 1.69 (s, 3H); 1.60 (s, 3H), 1.28 (t, 3H); 0.92 (d, 3H). 
     EXAMPLE 13 
     (E)-3-Dec-9-enyloxy-acrylic acid ethyl ester 
     The reaction was performed in standard glassware under an atmosphere of N 2 . To 150 ml of diethylether were added 9.8 g (0.1 mol) propiolic acid ethyl ester, 15.6g (0.1 mol) dec-9-en-1-ol and 10.1 g (0.1 mol) N-methylmorpholine. This solution was kept without stirring at room temperature for 24 hours. The mixture was evaporated under vacuum and the residue purified by bulb to bulb distillation (bp: 85-90° C.; 0.006 mbar) to yield 23.2 g (916%) of an oil. 
     NMR (CDCl 3 )δ7.59 (d, 1H); 5.92-5.70 (m, 1H); 5.18 (d, 1H); 5.06-4.87 (m, 2H); 4.16 (q, 2H); 3.83 (t, 2H); 2.12-1.96 (m, 2H); 1.80-1.58 (m. 2H); 1.50-1.16 (m. 13H). 
     EXAMPLE 14 
     The following sulfur compounds were prepared: 
     Thiocarbonic acid 0-ethyl ester S-[1-methyl-1-(4methyl-2-oxo-cyclohexyl)-ethyl]ester from thio-dihydro-carvon and chloro formic acid ethylester. 
     4-Propyl-[1,3]oxathian-2-one from 3-mercapto-hexanol-1 and phosgene. 
     Carbonic acid 3-ethoxycarbonylsulfanyl-hexyl ester ethyl ester from 3-mercapto-hexanol-1 and chloro formic acid ethyl ester. 
     Additionally, the compounds listed below were prepared: 
     
       
         
               
               
               
             
           
               
                   
               
               
                   
                 Synthesis 
                   
               
               
                 R 1 OH 
                 via Example x from: 
                 Product 
               
               
                   
               
             
             
               
                 cis-3-hexenol 
                 x = 1 
                 Carbonic acid dihex-3-enyl 
               
               
                   
                 cis-3-hexenol; triphosgene 
                 ester 
               
               
                 citronellol 
                 x = 1 
                 Carbonic acid bis-(3,7- 
               
               
                   
                 citronellol; triphosgene 
                 dimethyl-oct-6-enyl)ester 
               
               
                 Rosalva 
                 x = 1 
                 Carbonic acid didec-9-enyl 
               
               
                 (dec-9-en-1-ol) 
                 dec-9-en-1-ol; triphosgene 
                 ester 
               
               
                 phenylethyl 
                 x = 4 
                 Carbonic acid 4-tert-butyl- 
               
               
                 alcohol 
                 phenylethyl alcohol; 
                 cyclohexyl ester phenethyl 
               
               
                   
                 4-tert-butyl-cyclohexyl 
                 ester 
               
               
                   
                 chloroformate 
               
               
                 geraniol 
                 x = 4 
                 Carbonic acid 4-tert-butyl- 
               
               
                   
                 geraniol; 4-tert-butyl- 
                 cyclohexyl ester 3,7- 
               
               
                   
                 cyclohexyl 
                 dimethyl-octa-2,6-dienyl 
               
               
                   
                 chloroformate 
                 ester 
               
               
                 geraniol 
                 x = 8 
                 Carbonic acid 3,7-dimethyl- 
               
               
                   
                 geraniol; diethylene 
                 octa-2,6-dienyl ester 2-[ 
               
               
                   
                 glycol-bis- 
                 (3,7-dimethyl-octa-2,6- 
               
               
                   
                 chloroformate 
                 dienyloxy-carbonyloxy) 
               
               
                   
                   
                 ethoxy]-ethyl ester 
               
               
                 phenylethyl 
                 x = 4 
                 Carbonic acid butyl ester 
               
               
                 alcohol 
                 phenylethyl alcohol; butyl 
                 phenethyl ester 
               
               
                   
                 chloroformate 
               
               
                 cis-3-hexenol 
                 x = 4 
                 Carbonic acid butyl ester 
               
               
                   
                 cis-3-hexenol; butyl 
                 hex-3-enyl ester 
               
               
                   
                 chloroformate 
               
               
                 geraniol 
                 x = 4 
                 Carbonic acid butyl ester 
               
               
                   
                 geraniol; butyl 
                 3,7-dimethyl-oct-2,6-dienyl 
               
               
                   
                 chloroformate 
                 ester 
               
               
                 benzyl alcohol 
                 x = 4 
                 Carbonic acid benzyl ester 
               
               
                   
                 1,6-hexanediol; benzyl 
                 6-benzyloxycarbonyloxy- 
               
               
                   
                 chloroformate 
                 hexyl ester 
               
               
                 ethyl vanillin 
                 x = 7 
                 Carbonic acid benzyl ester 
               
               
                   
                 ethyl vanillin; benzyl- 
                 2-ethoxy-4-formylphenyl 
               
               
                   
                 chloroformate 
                 ester 
               
               
                   
               
             
          
         
       
     
     EXAMPLE 16 
     Test cloth was washed with a lipase-containing detergent to which one or more delayed release fragrances of the present invention had been added. Headspace analysis of the wet and dry laundry indicated the presence of the fragrant alcohols. The alcohol level was higher than when the test cloth was washed with a lipase-containing detergent to which one or more fragrant alcohols were added. 
     EXAMPLE 17 
     Test cloth was washed with a lipase-containing detergent. Then, a fabric softener, containing one or more delayed release fragrances of the present invention, was added to the rinse cycle. Headspace analysis of the wet and dry laundry indicated the presence of the fragrant alcohols. The alcohol level was higher than when the test cloth was washed with a lipase-containing detergent and then a fabric softener, containing one or more delayed fragrant alcohols, was added to the rinse cycle. 
     EXAMPLE 18 
     Axilla bacteria cultures containing 0.1% precursor according to formula I were incubated for 20 hours at 30° C. After filtration from the cells, the presence of the parent alcohol was in each case detected by headspace-GC techniques and/or the majority of an 18 member panel. 
     The same tests were carried out with inactivated cultures (85°/20 min). The odor of the parent alcohols could not be detected after incubation, excluding therefore a hydrolysis by the medium or the culture. 
     EXAMPLE 19 
     The following set forth examples 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, e.g. colorants, opacifiers, buffers, antioxidants, vitamins, emulsifiers, UV absorbers, silicones and the like. All products may also be buffered to the desired pH. All values are % w/w. 
     
       
         
               
               
               
               
               
             
           
               
                   
               
             
             
               
                 Deo-colognes 
                   
                   
                   
                   
               
               
                 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 to 
                 100 
                 100 
                 100 
                 100 
               
               
                 Deo-Sticks: 
               
               
                 Antiperspirant 
               
               
                 Ethylene Glycol Monostearate 
                 7.0 
               
               
                 Shea butter 
                 3.0 
               
               
                 Neobee 1053 (PVO International) 
                 12.0 
               
               
                 Generol 122 (Henkel) 
                 5.0 
               
               
                 Kesscowax B (Akzo) 
                 17.0 
               
               
                 Dimethicone Dow Corning 345 
                 35.0 
               
               
                 Aluminum Sesquichlorhydrate 
                 20.0 
               
               
                 Delayed Release Fragrances 
                 0.5 
               
               
                 Fragrance 
                 0.5 
               
               
                 Antiperspirant 
               
               
                 Steary Alcohol 
                 17.0 
               
               
                 Castor Wax 
                 3.0 
               
               
                 Talc 
                 5.0 
               
               
                 Aluminum Zirconium 
                 20.0 
               
               
                 Tetrachlorhydrate 
               
               
                 Delayed Release Fragrances 
                 1.0 
               
               
                 Fragrance 
                 1.0 
               
               
                 Dimethicone Dow 245 
                 to 100.0 
               
               
                 Clear Deodorant Stick 
               
               
                 Witconol APM 
                 43.0 
               
               
                 Propylene Glycol 
                 20.0 
               
               
                 Alcohol 39C 
                 20.0 
               
               
                 Demin water 
                 7.0 
               
               
                 Monamid 150ADD 
                 5.0 
               
               
                 Millithix 925 
                 2.0 
               
               
                 Ottasept Extra 
                 0.5 
               
               
                 Delayed Release Fragrances 
                 0.75 
               
               
                 Fragrance 
                 0.75 
               
               
                 Deodorant Stick 
               
               
                 Propylene Glycol 
                 69.0 
               
               
                 Demin Water 
                 21.8 
               
               
                 Triclosan 
                 0.2 
               
               
                 Sodium Stearate 
                 8.0 
               
               
                 Delayed Release Fragrances 
                 0.5 
               
               
                 Fragrance 
                 0.5 
               
               
                 Alcohol free Deodorant Stick 
               
               
                 PPG-3 Myristyl Ether (Witconol APM) 
                 36.0 
               
               
                 Propylene Glycol 
                 36.0 
               
               
                 Demin Water 
                 19.0 
               
               
                 Triclosan 
                 0.25 
               
               
                 Sodium Stearate 
                 7.75 
               
               
                 Delayed Release Fragrances 
                 0.5 
               
               
                 Fragrance 
                 0.5 
               
               
                 Antiperspirant Aerosol 
               
               
                 Absolute Ethanol 
                 15.0 
               
               
                 Zirconium Aluminum 
                 5.0 
               
               
                 tetrachlorhydrate 
               
               
                 Bentone 38 
                 1.5 
               
               
                 Delayed Release Fragrances 
                 0.75 
               
               
                 Fragrance 
                 0.75 
               
               
                 S-31 Hydocarbon propellant 
                 to 100.0 
               
               
                 Antiperspirant Pump 
               
               
                 Demin water 
                 57.5 
               
               
                 Aluminum Sesquichlorhydrate 
                 20.0 
               
               
                 Triton X-102 (Union Carbide) 
                 2.0 
               
               
                 Dimethyl Isosorbide (ICI) 
                 20.0 
               
               
                 Delayed Release Fragrances 
                 0.25 
               
               
                 Fragrance 
                 0.25 
               
               
                 Roll-On 
               
               
                 Dimethicone DC 354 (Dow Corning) 
                 69.0 
               
               
                 Bentone 38 
                 10.0 
               
               
                 Rezal 36 GP (Reheis Chem. Co.) 
                 20.0 
               
               
                 Delayed Release Fragrances 
                 0.5 
               
               
                 Fragrance 
                 0.5 
               
               
                   
               
             
          
         
       
     
     In the above, the following components were used: 
     
       
         
               
               
             
           
               
                   
               
             
             
               
                 Triclosan 
                 5-chloro-2-(2,4-dichlorophenoxy)phenol 
               
               
                 Neobee 1053 
                 glycerol tricaprate/caprylate 
               
               
                 Generol 122 
                 soya sterol 
               
               
                 Kesscowax B 
                 cetyl alcohol and glycol polymer 
               
               
                 Witconol APM 
                 polypropylene glycol-3 myristyl ether 
               
               
                 Monamid 150 ADD 
                 cocoamide diethanolamine 
               
               
                 Millithix 925 
                 dibenzylidene sorbitol 
               
               
                 Ottasept Extra 
                 quaternium 18 hectorite 
               
               
                 Bentone 38 
                 quaternium 18 hectorite 
               
               
                 Triton X-102 
                 octoxynol-13 
               
               
                 Dimethicone DC 354 
                 mixture of fully methylated linear siloxane 
               
               
                   
                 polymers end-blocked with trimethylsiloxy 
               
               
                   
                 units 
               
               
                 Rezal 36 GP 
                 Aluminium zirconium tetrachlorohydrexglycine 
               
               
                   
               
             
          
         
       
     
     The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention and all such modifications are intended to be included within the scope of the following claims.