MXPA99001727A - Hand-wash laundry detergent compositions comprising beta-ketoester pro-fragrances - Google Patents

Abstract

The present invention relates to a fragrance delivery system for use in hand-wash laundry detergent compositions which provides a long lasting"freshness"or"clean"scent to fabric. The compositions described herein deliver highly fabric substantive pro-fragrances to the fabric surface during laundering wherein the pro-fragrances release their fragrance raw materials over an extended period of time depending on the selection of the particular pro-fragrance. The present invention also relates to a method for delivering a pleasurable scent to fabric which has a lasting freshness quality by contacting the fabric with a laundry detergent composition which comprises the fragrance-releasing pro-fragrances.

Description

DETERGENT COMPOSITIONS FOR MANUAL LAUNDRY THAT INCLUDE BETA-CETOESTER PRO-FRAGANCES RELATED REQUEST This application claims priority under title 34, United States Code 119 (e) from provisional application series No. 60 / 024,117, filed on August 19, 1996.

FIELD OF THE INVENTION The present invention relates to laundry detergent compositions useful for manual washing of fabrics, including one or more beta-keto-ester pro-fragrance compounds which release the raw material of the fragrance thus providing a "freshness" or "flavor" aroma. cleaning "to the fabric. The present invention also relates to a method for providing the benefit of the fragrance to washed fabrics by contacting the soiled fabric with a laundry detergent composition described herein.

BACKGROUND OF THE INVENTION In addition to the removal of stains, dirt, dirt, grime and grease from fabrics, laundry detergent formulators have tried to leave a "fresh" or "clean" scent to washed clothes to provide an olfactory aesthetic benefit and to serve as a sign that the product is effective. Laundry detergent compositions, including fabric softeners added during rinsing and substrates added during drying, are usually formulated with perfume ingredients and fragrances, which are aesthetically pleasing to the consumer and which attempt to leave a "fragrance" scent. "or prolonged" pleasant aroma "to fabrics which have been washed in a washing machine. However, many clothes, especially those made of "fine fabric" materials (for example silk) or those that comprise "soft fabric" materials (for example, woolen sweaters) are commonly "hand washed". Typically hand washing limits the temperature at which the fabric is washed, usually within a tolerable range to the person washing the clothes. In addition, a unique aspect of hand washing is the high ratio of dirt to water (a high load of dirt) characterized further because the water can become super saturated with soil and particulate material. Hand washing of the cloth, in general, is not characteristic of any particular geographical region. Although certain areas that have limited access to modern appliances have a high prevalence in terms of hand washing, the need to hand wash at least certain items of clothing appears to be universal. However, hand-washing practices are also related to certain aspects of lifestyle, for example, within some urban areas most of the clothes are washed professionally, typically via dry cleaning, and the rest of the clothes that are not Commanded for professional cleaning consists of "delicate" or "personal" items which typically require "handwashing". Attempts have been made to leave the perfume ingredients, especially the alcohols and ketones of the fragrance raw material, on the fabrics during the limited time of exposure of the hand wash. For example, less dirty items can be exposed to the wash solution for a short period of time relative to the dirtiest clothes. In addition, less substantial perfume materials and fragrances compete with more substantial laundry aids (eg, soil release agents, dye transfer inhibitors) by depositing on the surface of the fabric. In addition, fabric items that are washed first during a common wash session will have a less dirty wash solution to which the fabric is exposed. Accordingly, there still remains a need in the art for a fragrance release system characterized by the fact that the alcohols and ketones of the fragrance raw material are left in the fabric by means of a laundry detergent composition for washing the laundry. hand that comprises a pro-fragrance material that has a high substantivity and dispersing properties of water which provides a fresh or clean scent to clothes or cloth for a prolonged period after washing. The aforementioned laundry detergent compositions are typically granular detergents or laundry bars.TECHNICAL BACKGROUND The following is related to the theme of ingredients for fragrances. E.U.A. 5,626,852 Suffis et al., Issued May 6, 1997; E.U.A. 5,232,612 Trinh et al., Issued August 3, 1996; E.U.A. 5,506,201 McDermott et al., Issued April 9, 1996; E.U.A. 5,378,468 Suffis et al., Issued January 3, 1995; E.U.A. 5,266,592 Grub et al. Issued November 30, 1993; E.U.A. 5,081,111 Akimoto et al., Issued January 14, 1992; E.U.A. 4,994,266 Wells, issued February 19, 1991; E.U.A. 4,524,018 Yemoto et al., Issued June 18, 1985; E.U.A. 3,849,326 Jaggers et al., Issued November 19, 1974; E.U.A. 3,779,932 Jaggers et al., Issued December 18, 1973; JP 07-179,328 published July 18, 1995; JP 05-230496 published September 7, 1993; WO 96/14827 published May 23, 1996; WO 95/04/809 published February 16, 1995; and WO 95/16660 published June 22, 1995. In addition, P. M. Muller, D. Lamparsky Perfumes Art. Science & Technology, Blackie Academic & Professional, (New York, 1994) is included here for reference.

BRIEF DESCRIPTION OF THE INVENTION The present invention satisfies the aforementioned needs in that it has been discovered, surprisingly, that the raw material of the fragrance can be left on the fabric "through washing" during the hand washing of the fabric from a fragrance alone or a molecule of co-profragance that has a high substantivity towards the fabric and so that this compound imparts the benefit of a "fresh" or "clean" aesthetic aroma to the fabric. In addition to the pleasant short-term aroma benefits, the pro-fragrances and co-proforgances according to the present invention continue to release the raw material of their fragrance several weeks later, depending on the structure of the fragrance. The pro-fragrances and co-profragances described herein comprise alcohols of the fragrance raw material in a stable beta-ketoester, releasable form. The laundry detergent compositions of the present invention containing pro-fragrances can comprise any number of pro-fragrances which when put together are capable of releasing complex perfume fragrances. However, the beta-ketoesters of the present invention, which are co-profragances, are capable of undergoing chemical transformation and thus release one or more raw materials of the fragrance in addition to the alcohol of the raw material of the fragrance used to prepare the co-profragancia original father. In addition, the pro-fragrances and co-profragances of the present invention are suitable to release any type of "characteristic" of the fragrance that is desired by the formulator. The first aspect of the present invention relates to a granular or soap bar detergent composition which supplies the hand washed fabrics with an increased fragrance longevity, comprising: (a) at least about 0.01%, preferably from 0.01% to 15%, more preferably from 1% to 5%, more preferably from 0.1% to 1% by weight, of a beta-ketoester having the formula: where R is an alkoxy derived from an alcohol of the fragrance raw material; R1, R2 and R3 are each independently hydrogen, a substituted or unsubstituted linear alkyl of C1-C30, a substituted or unsubstituted branched alkyl of C3-C30, a substituted or unsubstituted cyclic alkyl of C3-C30, a linear alkenyl substituted or unsubstituted C2-30, a substituted or unsubstituted branched alkenyl of c3_c30 'a substituted or unsubstituted cyclic alkenyl of C3-C30, a substituted or unsubstituted linear alkynyl of C2-C30, a substituted or unsubstituted branched alkynyl of C3-C30 / a substituted or unsubstituted aryl of Cg-C30, a substituted or unsubstituted alkylenoxy of C2-C20 a substituted or unsubstituted alkyleneoxyalkyl of C3-C20, a substituted or unsubstituted alkylenearyl of c7 ~ c20 a substituted or unsubstituted alkylenenoxy of Cg-C20, and mixtures thereof; considering that at least one of R1, R or 3 R is a unit that has the formula: wherein R4, R5 and R6 are each independently hydrogen, substituted or unsubstituted linear alkyl of C] _-C3o, substituted or unsubstituted branched alkyl of C3-C30, substituted or unsubstituted cyclic alkyl of C3-C30, linear alkoxy substituted or unsubstituted C1-C3Q, substituted or unsubstituted C3-C30 branched alkoxy, substituted or unsubstituted C3-C30 alkoxy, substituted or unsubstituted linear alkenyl of C2 -C30 'substituted or unsubstituted branched alkenyl of C3 -C30, substituted or unsubstituted C3-C30 cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted C3-C30 alkynyl, substituted or unsubstituted Cg-C3Q alkylenearyl, substituted or unsubstituted aryl substituted of Cg-C3g; or R, R5 and R6 can be taken together to form substituted or unsubstituted C -C3g aryls; and mixtures thereof; (b) at least about 0.01% by weight, preferably from 0.1% to 60%, more preferably from 0.1% to 30% by weight, of a detersive surfactant selected from the group consisting of ampholytic surfactants, zwitterionic, nonionic, cationic, or anionic and mixtures thereof, preferably said surfactant is an anionic surfactant; and (c) the remainder are adjuvants and vehicles, said adjuvant ingredients are chosen from the group consisting of detergency builders, optical brighteners, bleaches, bleach boosters, bleach catalysts, bleach activators, soil release polymers. , dye transfer agents, dispersants, enzymes, foam suppressors, dyes, perfumes, pigments, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelators, stabilizers , anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anticorrosion agents, and mixtures thereof. A further aspect of the present invention relates to methods for providing an extended "fresh" and "clean" aroma to fabrics comprising the steps of washing the fabric in an aqueous solution of a laundry detergent composition comprising one or more beta-ketoesters, pro-professions or co-professions described here. These and other objects, features and advantages will become apparent to those skilled in the art upon reading the following detailed description and the appended claims. All percents, proportions and ratios indicated herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All the documents cited are in a relevant part, incorporated here for reference.

DETAILED DESCRIPTION OF THE INVENTION The laundry detergent compositions of the present invention comprise a fragrance release system which places one or more "pro-fragrance" compounds on the surface of the fabric during a hand wash cycle which are capable of releasing an alcohol from the raw material of the fragrance or in the case of "co-profragancias" the compounds are able to release a mixture of raw materials of the fragrance. The key advantages provided by the "pro-fragrances" of beta-ketoesters or the "co-profragances" of the present invention include chemical stability in the final product matrix, ease of formulation within the product matrix, the ability to deposit on the product. fabric during high loads of dirt from the laundry solution, and a rate of liberation of the alcohol from the raw material of the highly desirable fragrance. The beta-ketoesters of the "pro-fragrances" and the "co-profragancias", of the present invention begin to release the raw materials of the fragrance on the surface of the fabric once the fabric is exposed to the laundry solution. For the purposes of the present invention the term "" pro-fragrance "" is defined as a "beta-ketoester which releases an alcohol from the raw material of the fragrance" while a "co-profragrance" is defined as a " beta-ketoester which releases two or more raw materials of the fragrance. " For the purposes of the present invention, however, since a material that is a "pro-fragrance" in one modality can serve as a "co-profragance" in a different modality, the term "pro-fragrance" is used interchangeably with the term "co-profragance" and any of the terms can be used to equally well represent either the beta-ketoester of the "pro-fragrance" molecules, or the beta-ketoester molecules of the "co-profragance", or both collectively. These "pro-fragrance" compounds are quickly deposited on the surface of the fabric due to the high substantivity of the compounds to the fabric and once deposited, it continues to release the raw material of the fragrance during the drying process. One aspect that is key to the "release method" of the raw materials of the fragrance is the fact that hand-washed items are normally "line-dried", and therefore the prolonged contact of the beta-ketoesters of the present invention with the trapped water of the soaked fabric accentuates the release of the fragrance. This fact allows the formulator to adjust the amount of beta-ketoester "pro-fragrance" in the final product depending on whether the laundry composition is intended for use with high or light wash loads. Since the "pro-fragrance" beta-ketoesters of the present invention generally have a higher molecular weight than the raw materials of the non-combined fragrances, they are less volatile and therefore provide a means to effectively release the raw materials of the fragrance on the surface of the fabric. Once the wash cycle is complete, that is, the clothes or fabric is dry and ready to be used, the "pro-fragrance" continues to release the alcohol from the raw material of the fragrance and since this release of the material is prolonged , the fabric remains smelling "fresh" and "clean" longer. For the purposes of the present invention "fragrance raw materials" are herein defined as compounds that impart an odor, fragrance, perfume or perfume either alone or a combination with other "fragrance raw materials", which is considered as aesthetically pleasing, preferably said compounds have a molecular weight of at least 100 g / mol. The majority of the fragrance raw material alcohols which comprise the "pro-fragrance" beta-ketoesters of the present invention are not releasable as individual compounds to the fabric via the wash cycle either due to the solubility factors (not sufficiently soluble in the liquid laundry solution), factors of substantivity (do not adhere sufficiently to the surface of the fabric), or volatility factors (evaporation during storage). Therefore the "pro-fragrances" described herein are a means to release certain raw materials from the fragrance to the fabric which could not be effectively or efficiently released previously.

Beta-ketoesters of "pro-fragrances" The compositions according to the present invention comprise one or more of the beta-ketoesters having the formula: wherein R is an alkoxy derivative of an alcohol of the fragrance raw material, non-limiting examples of preferred alcohols of the fragrance raw material include 2,4-dimethyl-3-cyclohexen-1-methanol (Floralol), , 4-dimethylcyclohexane-methanol (dihydro floralol), 5,6-dimethyl-l-methyletenyl-bicyclo [2.2.1] hept-5-en-2-methanol (Arbozole), alpha, alpha-4-trimethyl-3- cyclohexen-l-methanol (alpha-terpineol), 2,, 6-trimethyl-3-cyclohexen-1-methanol (geraniol isoccycle), 4- (1-methylethyl) -cyclohexanmethanol (Mayol), alpha, 3 -3 -trimethyl-2-norboranmethanol, 1,1-dimethyl-1- (4-methylcyclohex-3-enyl) methanol, 2-phenylethanol, 2-cyclohexyl ethanol, 2- (o-methylphenyl) -ethanol, 2- (methylphenyl) ) -ethanol, 2- (p-methylphenyl) ethanol, 6,6-dimethylbicyclo- [3.1.1] hept-2-in-2-ethanol (nopol), 2- (4-methylphenoxy) -ethanol, 3-3 -dimethyl-delta-2-beta-norbornanetanol (Patchomint), 2-methyl-2-cyclohexyl-ethanol, 1- (4-isopropylcyclohexyl) -ethanol, 1-phenylethanol, 1,1-dimethyl-2-phenylethanol 1, 1-dimethyl -2- (4 -met il-phenyl) ethanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (hydrotropic alcohol), 2- (cyclododecyl) propan-1-ol (Hydroxy-ambran), 2,2-dimethyl-3- (3-methylphenyl) ) -propan-1-ol (Majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2-propen-l-ol (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-l-ol (methyl methyl alcohol), alpha-n-pentyl-3-phenyl-2-propen-l-ol (alpha-amilcinyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2- (4-methylphenyl) -2- propanol, 3- (4-methylcyclohex-3-ene) butanol, 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) butanol, 2-ethyl-4- (2, 2, 3-trimethyl-cyclopent-3-enyl) -2-buten-l-ol, 3-methyl-2-buten-l-ol (prenyl), 2-methyl-4- (2, 2, 3-trimethyl) -3-cyclopenten-1-yl) -2-buten-1-ol, ethyl 3-hydroxy-butyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol, - (4-hydroxyphenyl) butan-2-one, 4- (4-hydroxy-3-methoxyphenyl) -butan-2-one, 3-methyl-pentanol, 3-methyl-3-penten-1-ol, 1- (2-propenyl) -cyclopentan-1-ol (plinol), 2-methyl-4-phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol (Phenoxanol), 2-methyl-5-phenylpentanol, 2-methyl-5- (2, 3-dimethyltricyclo [2.2.1.0 (2,6)] hept-3-il ) -2-penten-l-ol (santalol), 4-methyl-l-phenyl-2-pentanol, 5- (2, 2, 3 -trimethyl-3-cyclopentenyl) -3-methylpentan-2-ol (saldalore) ), (1-methyl-bicyclo [2.1.1] hepten-2-yl) -2-metiIpent-1-en-3-ol, 3-methyl-1-phenylpentan-3-ol, 1, 2-dimethyl- 3- (1-Methylethyl) cyclopentan-1-ol, 2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 2-isoproenyl-4 -methyl-4-hexen-l-ol (Lavandulol), 2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-cyclohexene (dihydrocuminyl alcohol), l-methyl-4- isopropenylcyclohex-6-en-2-ol (carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol (dihydro-carveol), l-methyl-4-iso-propenylcyclohexan-3-ol, 4-isopropyl-l- methylcyclohexan-3-ol, 4-tert-butylcyclohexanol, 2-tert-butyl-cyclohexanol, 2-tert-butyl-4-methylcyclohexanol (rootanol), 4-isopropyl-cyclohexanol, 4-methyl-1- (1- methylethyl) -3-cyclohexen-lo l, 2- (5,6,6-trimethyl-2-norbornyl) cyclohexanol, isobornyl-cyclohexanol, 3,3,5-trimethylcyclohexanol, l-methyl-4-isopropyl-cyclohexan-3-ol, 1-methyl-4 -isopropylcyclohexan-8-ol (dihydro-erpineol), 1,2-dimethyl-3- (1-methylethyl) -cyclohexan-1-ol, heptanol, 2,4-dimethylheptan-1-ol, 6-heptyl-5-hepten -2-ol (isolinalool), 2,4-dimethyl-2,6-hep andienol, 6,6-dimethyl-2-oxymethyl-bicyclo- [3.1.1] hept-2-ene (myrtenol), 4-methyl -2, 4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6,6-dimethyl -3-hydroxy-2-methylenebicyclo [3.1.1] heptane, 1,7,7-trime-ilbicyclo [2.2.1.] Heptan-2-ol, 2,6-dimethylheptan-2-ol (dimethyl), 2, 6,6-dimethylbicyclo [1.3.3] heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol (myrcenol), -methyl-octane-l-ol, 3, 7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3, 7-dimethyl-6-octen-l-ol (citronellol), 3,7-dimethyl-2,6-octadien-l-ol (geraniol), 3, 7 -dimethyl-2,6-octadien-l-ol (nerol), 3,7-dimethyl-7-methoxyoctan-2-ol (osyrol), 3,7-dimethyl-1,6-octadien-3-lol (linalool) ), 3, 7-dimethyloctan-l-ol (pelargol), 3, 7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-1-ol, 3, 7-dimethyl-6-octen-3 ol (dihydrolinalool), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), 2,6-dimethyl-5,7-octadien-2-ol, 4,7-dimethyl-4-vinyl-6- octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyl-octan-2-ol, 2,6-dimethyloctan-3-ol, 3,6-dimethyloctan-3-ol, 2, 6 dimethyl-7-octen-2-ol, 2,6-dimethyl-3,5-octadien-2-ol (uguol), - 3 -methyl-l-octen-3-ol, 7-hydroxy-3, 7- dimethyloctanal, 3 -nonanol, 2,6-nonadien-l-ol, cis-6-nonen-l-ol, 6, 8-dimethylnonan-2-ol, 3- (hydroxymethyl) -2 -nonanone, 2-nonen- l-ol, 2, 4-nonadien-l-ol, 3, 7-dimethyl-l, 6-nonadien-3-ol, decanol, 9-decene, 2-benzyl-M-dioxa-5-ol, 2 - decen-1-ol, 2, 4 -decadien-1-ol , 4-methyl-3-decen-5-ol, 3, 7, 9-trimethyl-l, 6-decadien-3-ol (isobutyl-linanole), undecanol, 2-undecen-l-ol, 10-undecen-l -ol, 2-dodecen-l-ol, 2, 4-dodecadien-l-ol, 2, 7, 11-trimethyl-2, 6, 10-dodecatrien-l-ol (farnesol), 3, 7, 11- trimethyl-l, 6, 10, -dodecatrien-3-ol (nerolidol), 3, 7, 11, 15-tetra-methylhexadec-2-en-l-ol (phytol), 3, 7, 11, 15-tetramethylhexadec -l-en-3 -ol (iso phytol), benzyl alcohol, p-methoxybenzyl alcohol (anisyl alcohol), para-cyme-7-ol (cuminyl alcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxybenzyl alcohol, methyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, n-pentyl salicylate, 2-phenylethyl salicylate, n-hexyl salicylate, 2-methyl-5-isopropylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4- (1-propenyl) phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-tert-butylphenol, 2-ethoxy-4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl, 5-methylphenol (thymol), pentyl -orto-hydroxy benzoate, ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-5-methoxy-1-methylbenzene, 2-tert-butyl-4-methyl-1- hydroxybenzene, l-ethoxy-2-hydroxy-4-propenylbenzene, 4-hydroxytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy 4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro-2 -naphthol, 1, 3, 3 -trimethyl-2-norbornazol (phenchol), 3a, 4, 5, 6, 7, 7a-hexahydro-2,4-dimethyl-4,7-methano-lH-inden-5- ol, 3a, 4, 5, 6, 7, 7a-hexahydro-3,4-dimethyl-4,7-methano-lH-inden-5-ol, 2-methyl-2-vinyl-5- (1-hydroxy) -l-methylethyl) tetrahydrofuran, beta-caryophyllene alcohol, vanillin, ethyl vanillin and mixtures thereof. More preferably, the alcohol of the fragrance raw material is selected from the group consisting of cis-3-hexen-1-ol, hawthanol [mixture of 2- (o-methylphenyl) -ethanol, 2- (m-methylphenyl) ) ethanol, and 2- (p-methylphenyl) ethanol], heptan-1-ol, decan-1-ol, 2,4-dimethylcyclohexane methanol, 4-methylbutan-1-ol, 2,4,6-trimethyl- 3-cyclohexen-1-methanol, 4- (1-methylethyl) -cyclohexane-methanol, 3- (hydroxy-methyl) -2-nonanone, octan-1-ol, 3-phenylpropanol, Rhodinol 70 [3,7-dimethyl mixture] -7-octenol, 3, 7-dimethyl-6-octenol], 9-decen-lol, alpha-3,3-trimethyl-2-norboran methanol, 3-cyclohexylpropan-l-ol, 4-methyl-1-phenyl -2-pentanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, phenyl ethyl methanol; propyl benzyl methanol, l-methyl-4-isopropenylcyclohexan-3-ol, 4-isopropyl-1-methylcyclohexan-3-ol (menthol), 4-tert-butyl-cyclohexanol, 2-tert-butyl-4-methylcyclohexanol, -isopropylcyclohexanol, trans-decahydro-beta-naphthol, 2-tert-butylcyclohexanol, 3-phenyl-2-propen-1-ol, 2,7, 11-trimethyl-2, 6, 10-dodecatrien-1-ol , 3, 7-dimethyl-2,6-octadien-1-ol (geraniol), 3, 7-dimethyl-2,6-octadien-l-ol (nerol), 4-methoxybenzyl alcohol, benzyl alcohol, 4-allyl-2-methoxyphenol, 2-methoxy-4- (1-propenyl) phenol, vanillin, and mixtures thereof. R, R and R are each independently hydrogen, unsubstituted or substituted linear alkyl of C] _-C30, substituted or unsubstituted branched alkyl of C3-C30, substituted or unsubstituted cyclic alkyl of C3-C3Q, substituted linear alkenyl or unsubstituted C2-C3Q, substituted or unsubstituted C3-C30 alkenyl, substituted or unsubstituted C3-C30 alkenyl, unsubstituted or substituted C2-C3Q linear alkynyl, substituted or unsubstituted branched alkynyl of C3-C3Q substituted or unsubstituted C -C3Q aryl, substituted or unsubstituted C2-C20 substituted or unsubstituted C2-20 alkylene oxide, unsubstituted or substituted C7-C20 substituted or unsubstituted C7-C20 alkylene aryl or C-C2u / Y mixtures thereof; considering that at least one of R 1, R9 or R3, is a unit that has the formula: where R, R, and R are independently hydrogens, substituted or unsubstituted C 1 -C 30 linear alkyl, substituted or unsubstituted C 3 -C 30 branched alkyl, substituted or unsubstituted C 3 -C 30 cyclic alkyl, substituted or unsubstituted linear alkoxy of C1-C3O 'substituted or unsubstituted C3-C30 branched alkoxy, substituted or unsubstituted C3-C30 alkoxy, substituted or unsubstituted C2-C30 linear alkenyl, substituted or unsubstituted branched alkenyl of C3-C30, alkenyl substituted or unsubstituted C3-C30 cyclic, substituted or unsubstituted C2-C30 linear alkynyl, unsubstituted or substituted C3-C30 alkynyl, unsubstituted or substituted C-C3 aryl alkylene, unsubstituted or substituted C5 aryl -C30; or R, R and R can be taken together to form a substituted or unsubstituted aryl of C -C3Q; and mixtures thereof. Preferably at least two units R, R, or R are hydrogen. In one embodiment of the present invention the R, R, and R units are preferably each hydrogen. Further, preferably when two units R 4, R, and R are hydrogens, the remaining unit is a substituted or unsubstituted linear alkyl of C] _-C 20 'a substituted or unsubstituted branched alkyl of C 3 -C 3 Q, a substituted cyclic alkyl or unsubstituted C3-C20g. ; more preferably methyl. Further preferably R, R, and R are taken together to form an unsubstituted or substituted Cg-C30 aryl unit, preferably a substituted or unsubstituted naphthyl or phenyl. For the purposes of the present invention the term "substituted" as applied to linear alkyls, branched alkyls, cyclic alkyls, linear alkenyls, branched alkenyls, cyclic alkenyls, branched alkoxies, cyclic alkoxides, alkynyl, and branched alkynyl units are defined as "carbon chains which comprise substituents other than the branches of the carbon atom chain", for example, other than the branches of the alkyl units (for example isopropyl, isobutyl). Non-limiting examples of "substituents" include hydroxy, alkoxides cl ~ cl2 'preferably methoxides; C3-C1.2 branched alkoxides / preferably isopropoxide; C3-C12 cyclic alkoxides; nitrile; halogens, preferably chlorine and bromine, more preferably chlorine; nitro, morpholino; cyano; carboxyl, non-limiting examples of which are -CHO; -C? 2 ~ M +, -CO2; -CONH2; -CONHR9; -CONR92; where R9 is a branched or linear alkyl C ^ C ^; -S03-M +; -OS03-M +; -N (R10) 2; and N + (R10) 3X- wherein each R ° independently hydrogen or a C1-C4 alkyl; and mixtures thereof; where M is hydrogen or a water-soluble cation; and X is chlorine, bromine, iodine or other water-soluble anion. For the purposes of the present invention the substituted or unsubstituted alkylene oxide units are defined as having the formula: R8 where R 7 is hydrogen; Rff is hydrogen, methyl, ethyl, and mixtures thereof; the index x ranges from 1 to 10. For the purposes of the present invention the substituted or unsubstituted alkylenoxyalkyls are defined as portions having the formula: wherein R7 is hydrogen, C1-C18 alkyl, C1-C4 alkoxide, and mixtures thereof; R8 is hydrogen, methyl, ethyl, and mixtures thereof; the index X ranges from 1 to 10 and the index ranges from 2 to 18. For the purposes of the present invention the substituted or unsubstituted aryl units are defined as phenyl parts having the formula: or alpha and beta-naphthyl portions having the formula: wherein R 7 and Rff can be substituted in any of the rings, together or in combination, and R 7 and Rff ° are each hydrogens independently, hydroxyl, C ^ -Cg alkyl , C2_2 alkenyl, C1-C4 alkoxide, C3_C branched alkoxide, nitrile, halogens, nitros, morpholino, cyano, carboxyls (-CHO; -C02"+; -C02R9; -CONH2; -CONHR9; -CONR92; where R9 is a linear branched alkyl Cj-C ^), -S03 ~ M + '"OS03 ~ M +, -N (R10) 2, and N + (R) 3X" "wherein each R is independently hydrogen, C1-C4 alkyl , or mixtures thereof; and mixtures thereof, R 7 and Rfi are preferably hydrogen, alkyl C] _ Cg, C02 ~ M +, -S03"M +, -OS? 3_M +, and mixtures thereof, more preferably R 7 or Rff is hydrogen and the other portion is Cj_- Cg, where M is hydrogen or a cation soluble in water and X is chloride, bromide, iodide, or other water-soluble anion.

Examples of other water-soluble anions include organic species such as fumarate, succinate, tartrate, oxalate and the like, inorganic species include sulfate, bisulfate, phosphate and the like. For the purposes of the present invention the substituted or unsubstituted alkylenearyl units are defined as portions having the formula: wherein R 7 and Rff are each independently hydrogen, hydroxyl, CX-C4 alkoxide, nitrile, halogens, nitro, carboxyl (-CHO; -C02"M +; -C02R9; -CONH2; -CONHR9; -CONR92; R is a branched or linear alkyl C] _ Cj_2) amino, alkylamino, and mixtures thereof, ranging from 1 to 14, M is hydrogen or a water-soluble cation For the purposes of the present invention the alkylene units substituted or unsubstituted oxyaryls are defined as portions having the formula: wherein R and R are independently hydrogen, hydroxyl, C1-C4 alkoxide, nitrile, halogens, nitro, carboxyls (-CHO; -C02 ~ M +; -C02R9; -CONH2; -CONHR9; -CONR92; Q wherein R is a branched or linear alkyl C] _- C-2 ^ 'amino, alkylamino, and mixtures thereof, ranging from 1 to 14; M is hydrogen or a water-soluble cation, non-limiting examples of ketones which are releasable by the co-profragances of the fragrance release systems of the present invention are alpha-damascone, beta-damascone, delta-damascone, beta-damascenone, muscone, 3,3-dimethylbutanone, methylphenyl ketone (acetophenone), 4-phenylbutan -2-one (benzyl acetone), 2-acetyl-3, 3-dimethyl norbornane (camek dh), 6, 7-dihydro-l, 1, 2, 3, 3-pentamethyl-4 (5H) indanone (cashmeran), 4- (1,3) -benzodioxol-5-yl-3-buten-2-one (cassiona ), 4- (3,4-methylenedioxyphenyl) -2-butanone (dulcinil), 3-octanone, 6-acetyl-1,2,3,4-tetrahydronaphthalene ketone (florantone t), ethyl-2-n-hexylacetoacetate (gelsone), 2,6-dimethylundeca-2,6-di-10-one, 6,10-dimethyl-5,9-undecadien-2-one, 3,3-dimethylcyclohexylmethyl ketone (herbac), 4- (2, 6,6-trimethyl-1-cyclohexen-1-yl) -3-buten-2-one (beta-ionone), 4- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3- buten-2 -one (alpha-ionone), 3-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -3-buten-2-one (delta-methylionone), 4- (2, 6, 6-trimethyl-2-cyclohexen-1-yl) -3-methyl-3-buten-2-one (gamma-methyl-ionone), 3-methyl-4- (2,6-trimethyl-) 2-cyclohexen-1-yl) -3-buten-2-one (irisantem), 4- (2,3,5-trimethyl-4-cyclohexen-1-yl) -3-buten-2-one (iritone ), 4-methyl- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) -3-buten-2 -one (alpha-ionone), 1,2,3,4,5,6 , 7, 8-octa hydro-2, 3,8,8-tetramethyl-2-acetonaphthone (iso-cyclomone e), 7-acetyl-l, 2, 3, 4, 5, 6, 7, 8-octahydro-1, 1,6, 7-tetramethyl naphthalene (Iso E SuperR), acetyl • n-diisoamylene (Koavone), methylamyl ketone, 2-acetonaphthone cedr-8-enyl methyl ketone (methyl cedrilone), 2,3,6-trimethyl-cyclohexen-4-yl-1 -methyl ketone (methylcyclocitrona), hexahydroacetophenone (methylcyclohexyl ketone), 6-methyl-3,5-heptadien-2-one, 6-methyl-5-hepten-2 -one, 2-octanone, 3- (hydroxymethyl) -2- nonanone, 4-acetyl-1,1-dimethyl-6-tert-butyl indan (mustard indanone), 2-6-dinitro-3,5-dimethyl-4-acetyl-tert-butyl benzene (muskyl ketone), l-para-menten-6-yl propanone (nerona), para-methoxyacetophenone (acetanisol), 6- p-acetyl-1,2,3,3,5-hexamethyl indan (Phantolid?), 7-acetyl-1 , 1, 3, 4,4, 6-hexamethyl tetralin (Tonalid®, Musk Plus®), 5- p-acetyl-3-isopropyl-1,2,6-tetramethyl indan (Traseolide 70, methyl-2, 6, 10 -trimethyl -2,5,9-cyclododecatrieno-l-yl ketone (Trimofix 0R) , methyl cedrilone (Vertoxi Coeur), 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, c_is-jasmona, dihydrojasmone, alpha-ionone, beta-ionone, dihydro-beta-ionone, 4- (4-hydroxyphenyl) ) butan-2-one, -carvone, 5-cyclohexadecen-l-one, decatone, 2- [2- (4-me-il-3-cyclohexenyl-1-yl) propyl] cyclopentan-2-one, 2- sec-butylcyclohexanone, allylonone, alpha-ketone, geranyl acetone, 1- (2-methyl-5-isopropyl-2-cyclohexenyl) -1-propanone, acetyl diisoamylene, methyl cyclocitron, 4-t.pentyl cyclohexanone, pt-butylcyclohexanone, ot-butylcyclohexanone, menthone, methyl-7, 3-dihydro-2H-1, 5-benzodioxepin-3 -one, fenchone, methyl hydroxynaphthyl ketone, and mixtures thereof. According to the present invention all isomers of a pro-fragrance precursor material whether it is in the form of a pro-fragrance or as the raw material of the fragrance released, are suitable for use in the present invention. When there are possibilities of optical isomers, the raw materials of the fragrance can be included either as the separate chemical isomer or as a combined racemic mixture. For example, 3, 7-dimethyl-6-octen-1-ol, commonly known to those skilled in the art as beta-citronellol or cefrole, includes a pair of optical isomers, R- (+) - beta-citronellol and S- (-) -beta-citronellol. Each of these materials separately or as a racemic pair are suitable for use as raw materials for the fragrance in the present invention. However, those skilled in the art of fragrances, by use of the present invention, should not overlook the olfactory differences imparted by the individual optical isomers, mixture of optical isomers or mixtures of positional isomers. By way of example, carvone 2-methyl-5- (1-methylethyl) -2-cyclohexen-1-one exists as two isomers; d-carvona and 1-carvona. d-Carvona is found in caraway oil and provides a completely different fragrance than the .1-carvone which is found in the peppermint oil. According to the present invention a pro-fragrance which releases d-carvone will result in a different essence or fragrance than one which liberates 1.-carvone. The same applies to the -carvona. In addition, isomers such as the cis / trans isomers, for example nerol (3,7-dimethyl-cis-2,6-octadien-1-ol) and geraniol (3,7-dimethyl-trans-2,6-octadien- 1-ol), are well known to those skilled in the art of perfumery and these two terpene alcohols, which are commonly presented as a mixture, have different fragrant characteristics.

Therefore, when formulating the fragrance raw materials which comprise mixtures of isomers such as nerol / geraniol, the formulator must also take into account whether different sources of the raw material have different proportions in the composition of isomers. An example of a preferred pro-fragrance is 3,7-dimethyl-1,6-octadien-3-yl 3 - (beta-naphthyl) -3-oxo-propionate having the formula: which releases at least alcohol from the raw material of the fragrance, linalool, which has the formula: and the ketone of the raw material of the fragrance, methylnaphthyl ketone, which has the formula: A further example of a preferred pro-fragrance includes 2,6-dimethyl-7-octen-2-yl-3- (4-methoxyphenyl) -3-oxo-propionate which has the formula: which liberates at least alcohol from the raw material of the fragrance, dihydromircenol, which has the formula: and the ketone of the raw material of the fragrance, methyl-4-methoxyphenyl ketone, which has the formula: Further non-limiting examples of preferred pro-fragrances include 3,7-dimethyl-l, 6-octadien-3-yl 3- (alpha-naphthyl) -3-oxo-propionate, [linalyl (1-naphthoyl) acetate], which has the formula: 2, 6-dimethyl-7-octen-2-yl 3 - (-methoxyphenyl) -3-oxo-propionate, [3- (4-methoxyphenyl) -3-oxo-propionic acid dihydromyrcenyl ester], which has the formula 2,6-dimethyl-7-octen-2-yl 3- (4-nitrophenyl) -3-oxo-propionate, [3- (4-nitrophenyl) -3-oxo-propionic acid dihydromircenyl ester], which has the formula: 2,6-dimethyl-7-octen-2-yl 3- (beta-naphthyl) -3-oxo-propionate, [dihydromyrcenyl (2-naphthoyl) acetate], which has the formula: 3, 7-dimethyl-l, 6-octanedin-3-yl 3- [4-methoxyphenyl] -3-oxo-propionate, [3- (4-methoxyphenyl) -3-oxo-propionic acid] linalinic ester], which has the formula: (alpha, alpha-4-trimethyl-3-cyclohexenyl) methyl 3- (beta-naphthyl) -3-oxo-propionate, [alpha-erpinyl (2-naphthoyl) acetate], which has the formula: 9-decen-l-yl 3- (beta-naphthyl) -3 -oxo-propionate, [9-decen-l-yl (2-naphthoyl) acetate], alternatively known as, 2'-acetonaphthone rosalva, which has the formula: 3, 7-dimethyl-l, 6-octanedin-3-yl 3- (nonanyl) -3 -oxo-propionate, [linalyl (nonanoyl) acetate], alternatively known as octyl [(linalyl) alpha-acetyl] ketone, which has the formula: Further non-limiting examples of preferred pro-fragrances which comprise the fragrance release systems of the present invention include cis 3-hexen-l-yl 3- (beta-naphthyl) -3 -oxo-propionate, 2,6-dimethyl -7-octen-2-yl 3- (nonanil) -3 -oxo-propionate, 2,6-dimethyl-7-octen-2-yl-3-oxo-butyrate, 3,7-dimethyl-l, 6-octane -3-yl-3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3- (beta-naphthyl) -3 -oxo-2-methylpropionate, 3, 7-dimethyl-l, 6-octadien-3-yl 3- (beta-naphthyl) -3-oxo-2,2-dimethyl-propionate, 3,7-dimethyl-l, 6-octadien-3-yl 3- (beta-naphthyl) -3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3- (beta-naphthyl) -3-oxo-propionate, 3,7-dimethyl-2,6 -octadienyl 3-heptyl-3 -oxo-propio-nato, and mixtures thereof. The formulator is not limited to the release of a single type of fragrance, for example a note of the raw material of the high, medium, or base fragrance. On the other hand, a mixture of high notes, a mixture of central and high notes, or any combination of high and central base notes can be released in any proportion. As described above, those skilled in the art of preparing compositions containing fragrances have cataloged the fragrances into three types based on their relative volatility; as high, central, and base notes. In addition, fragrances are classified by the smell they produce; some of these descriptors are broad and others are relatively specific. For example, "floral" is a term which refers to aromas associated with flowers while the term "lilac" is more specific. The descriptors used by those qualified in the technique of perfumes and fragrances are inter alia "rose", "floral", "green", "citrus", "spicy", "honey", and "musk". The sources of these notes are not limited to a single chemical class; alcohols can produce aromas of "rose", "green" and "musk", while "rose" aromas can include alcohols, ketones, terpenes, aldehydes, etc. The high, central and base notes each serve a different purpose in mixing the fragrances and when properly formulated they produce a "balanced fragrance". Based on volatility, these notes are described by those skilled in the art as: the base notes have the most lasting aroma; the central notes have an average volatility; and high notes are the most volatile. The compositions described hereinafter, as well as others chosen by the formulator, comprise a fragrance release system which utilizes the pro-fragrances of the invention herein to successfully leave a profile of a "balanced fragrance". It is further recognized by those skilled in the art that descriptors that refer to aesthetic perceptions such as "high", "central" and "base" are relative terms. A fragrance raw material categorized as a high note by a formulator usually has the same classification among most perfume manufacturers. The same is true for core and base notes, however, occasionally a formulator may classify a raw material of a given fragrance as a central note rather than a high note, or vice versa, but this fact does not diminish the usefulness of a combined compound or its absolute identity. The high, central and base notes are now combined in a reproducible way to produce perfumes, colognes, aftershave lotions, toilet lotions, etc., to be applied to the skin, which have pleasant and unique smelling characteristics. However, apart from this pleasant fragrance, a fragrance release system which is used to leave a scent to a perfume, cologne, personal items, laundry detergent compositions or hard surface cleaners must meet a number of requirements technicians It must be strong enough, it must be persistent, and it must retain its "essential character" throughout its period of evaporation. Apart from the changes made to the pro-fragrance molecules for the purpose of modifying the fragrance profiles which provide the fragrance release system of the present invention, modifications to these pro-fragrances can be made for the purpose of increasing the substantivity of the materials. The formulator in selecting an appropriate unit R, R or R or on the selection of R4, R5 and R, can influence the degree and speed at which the pro-fragrance is deposited on the fabric or other surface. Those skilled in the art of formulating detergent compositions will recognize that the terms "noun and substantivity" refer to the propensity of a compound to adhere to something, to associate with or, to deposit on a surface, preferably the surface of the fabric. Therefore, compounds that are more substantive, more easily adhere to the surface of the fabric. However, the substantive compounds, in general, do not react with the surface on which they are deposited. An example of a pro-fragrance which has been modified to provide a greater substantivity to the fabric is 2,6-dimethyl-7-octen-2-yl 3- (beta-naphthyl) -2- (methoxypentanethylene-oxyl) -3 -oxo-propionate, [dihydromyrcenyl (2-naphthoyl) (2-E5methoxy) -acetate], which has the formula In addition to the substitution at the beta carbon atom, the substitution can be made at other sites of the co-profragance molecule, for example, 3,7-dimethyl-l, 6-octadien-3-yl 3- (methoxytriethyleneoxy) - 3 -oxo-butyrate, [linalyl- (methoxyE3) -acetate] which has the formula which is a molecule co-profragancia modified to increase the substantivity towards the fabric.

Laundry detergent compositions The present invention relates to laundry detergent compositions which are typically granulated or in the form of wash sticks or soap bars suitable for hand washing fabrics. Compositions of granular detergents or bar soaps which provide the hand washed fabric with increased fragrance duration, include: a) at least about 0.01%, preferably 0.01% up to 15%, more preferably 1 % up to 5%, even more preferably from 0.1% to 1% by weight, of one or more beta-ketoester pro-fragrances described above; b) at least about 0.01% by weight, preferably from 0.1% to 60%, more preferably from 0.1% to 30% by weight of a detersive surfactant selected from the group comprising zwitterionic, nonionic, cationic or anionic ampholytic surfactants , and mixtures thereof, preferably said surfactant is an anionic surfactant; and c) the remaining vehicles and adjunct ingredients, said adjunct ingredients are chosen from the group consisting of detergency builders, optical brighteners, bleaches, bleach boosters, bleach catalysts, bleach activators, dirt release polymers, transfer agents of the pigment, dispersants, enzymes, foam suppressors, pigments, perfumes, dyes, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelating agents, stabilizers, anti-aging agents shrinkage, and anti-wrinkle agents, germicides, fungicides, anti-corrosive agents, and mixtures thereof.

Preferably the laundry detergent compositions of the present invention include a high foaming surfactant, preferably a linear sodium alkylbenzenesulfonate and a phosphate-based builder, for which a non-limiting example is sodium tripolyphosphate. (STPP). Preferred compositions of granular detergents and laundry bar soaps of the present invention, comprise: a) at least 0.01%, preferably from 0.01% to 15%, more preferably from 1% to 5%, more preferably from 0.1% to 1% by weight of one or more of the beta-ketoester pro-fragrances described above; b) at least 0.01% by weight, preferably from 0.1% to 60%, more preferably from 0.1% to 30% by weight, of a detersive surfactant chosen from the group comprising ampholytic, zwitterionic, nonionic, cationic surfactants , anionic, and mixtures thereof, preferably said surfactant is an anionic surfactant, more preferably linear sodium alkylbenzenesulfonate (LAS); c) at least 0.01% by weight of a peroxygen bleach system which includes a bleach activator and an appropriate source of hydrogen peroxide, preferably NOBS / perborate; and d) the remainder are vehicles and adjunct ingredients, said adjunct ingredients are chosen from the group comprising detergency builders, optical brighteners, bleach boosters, bleach catalysts, bleach activators, soil release polymers, pigment transfer agents, dispersants, enzymes, foam suppressors, dyes, perfumes, pigments, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolysable surfactants, preservatives, antioxidants, chelating agents, stabilizers, anti-shrinking agents, anti-wrinkle agents, germicides, fungicides, anti-corrosion agents, and mixtures thereof. The present invention also relates to a method for releasing the benefits of a prolonged fragrance in the fabric by contacting the fabric with a laundry detergent composition for hand washing that includes the beta-ketoester pro-fragrance materials of the present invention. In its basic form, the present invention relates to a method for providing enduring fragrance benefits to the fabric by contacting said fabric with a laundry composition suitable for use in hand washable fabrics, which include: a) at least 0.01% , preferably from 0.01% to 15%, more preferably from 1% to 5%, more preferably still from 0.1% to 1% by weight of a beta-ketoester having the formula: wherein R is a substituted or unsubstituted linear alkyl of Cl "c30 'a substituted or unsubstituted branched alkyl of C3-C30, a substituted or unsubstituted cyclic alkyl of C3-C30, a substituted or unsubstituted linear alkenyl of C2- C30, a substituted or unsubstituted branched alkenyl of C3-C30, a substituted or unsubstituted cyclic alkenyl of C3-C3Q, a substituted or unsubstituted linear alkynyl of C2-C30, an unsubstituted or substituted C30-branched alkynyl of C3-C30, a substituted or unsubstituted aryl of Cg-C3O 'a substituted or unsubstituted aryl of g-C3Q, and mixtures thereof; R is an alkoxide unit derived from an alcohol 3 of the raw material of the fragrance; are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl of C_-C20 'substituted or unsubstituted branched alkyl of C3-C20 substituted or unsubstituted alkylene oxide of C2-C20 alkylenoxyalkylene the substituted or unsubstituted substituted or unsubstituted C3-C2O 'substituted or unsubstituted C7-C2O' alkylenearyl substituted or unsubstituted alkylenearyl of Cg-C2o 'and mixtures thereof; b) at least about 0.1% by weight, preferably from 0.01% to 60%, more preferably from 0.1% to 30% by weight, of a detersive surfactant chosen from the group consisting of ampholytic, zwitterionic surfactants, not ionic, cationic, anionic, and mixtures thereof, preferably said surfactant is an anionic surfactant; and c) the remainder are vehicles and / or adjunct ingredients.

Surfactant Systems The instant cleansing compositions may contain at least 0.01% by weight of a surfactant selected from the group comprising zwitterionic and ampholytic, nonionic, cationic, anionic surfactants. Preferably the surfactant, in both the granular and the bar form, is present to the extent of 0.1% to 60%, more preferably 0.1% to 30% by weight of the composition. Non-limiting examples of surfactants useful here typically at levels of 1% to 55% by weight, include conventional alkylbenzene sulphonates Cn-C_8 ("LAS") which are the preferred primary surfactants, alkyl sulphates C] _ o_c20 with branched chains and random ("AS") secondary alkylsulfates? or ~ ci8 (2.3 of the formula CH3 (CH2) x (CHOS03"M +) CH3 and CH3 (CH2) and (CHOS03 ~ M +) CH2CH3 where xy (y +1) are whole of at least 7, preferably 9, and M is a water-soluble cation, especially sodium, unsaturated sulfates such as oleyl sulfate, Ci0-18 alkylalkoxy sulfates ("" AEXS "), especially EO 1-7 ethoxysulfates ), alkylalkoxycarboxylatos C] _o ~ cl8 (especially the ethoxycarboxylates EO 1-5), the ethers of glycerol C? o ~ c18 '° S alkyl polyglycosides Ci0 ~ c18' And their corresponding sulfated polyglycosides, and the esters of fatty acids alpha -sulfonated C] _2 ~ ci8- if desired, amphoteric nonionic surfactants Conventional coss such as the alkylethoxylates ci2"c18 (" AE ") include the so-called narrow peak alkyl ethoxylates and the C-C2 alkylphenylalkoxylates (especially mixed ethoxylates and ethoxy / propoxy), beta-C ^ -C ^ s and sulfobetaines (" sultaines "), to inoxides C; ¡_Q-C] _g, and the like, can be included in the total compositions. The fatty acid amides of the N-alkyl polyhydroxyl C? Or c18 are highly preferred, especially the N-methylglucamides] _2_C18- See WO 9,206,154. Other surfactants derived from sugars include the fatty acid amides of N-alkoxy polyhydroxy, such as the N- (3-methoxypropyl) glucamide C 10 -C 18- The glucamides C 1 - ^ g of N-propyl to N-hexyl can be used for low foam formation. The conventional C1Q-C20 soaps can also be used. If high foaming is desired, the branched chain soaps C] _Q-C] _ can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other useful conventional surfactants are described hereinafter and are listed in standard texts. The anionic surfactants can be broadly described as the water soluble salts, particularly the alkali metal salts, of organic reaction products with sulfuric acid having in its molecular structure an alkyl radical containing from 8 to 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and an ester radical of sulfuric acid. (Included in the term alkyl is the alkyl portion of higher acyl radicals). Important examples of synthetic anionic detergents which can form the surfactant component of the compositions of the present invention are potassium or sodium alkyl sulphates, especially those obtained by sulfation of higher alcohols (Cg to C) _g carbon atoms) produced by the reduction of tallow glycerides from coconut oil; the sodium or potassium alkylbenzenesulfonates, in which the alkyl group contains from 9 to 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); the alkylglyceryl ether sodium sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; the sodium sulfates and sulphonates of the monoglycerides of the fatty acids of coconut oil; the sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of a (e.g. alcohols tallow or coconut) higher fatty alcohol and 1 to 10 moles of ethylene oxide; the sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to 10 ethylene oxide units per molecule and in which the alkyl radicals contain from 8 to 12 carbon atoms; the reaction products of fatty acids are derived from potassium salts and sodium coconut oil of fatty acid amides of a tauride which methyl fatty acids, for example, are derived from coconut oil and beta acetoxy or beta acetamido alcansulfonates of sodium or potassium where the alkane has 8 to 22 carbon atoms. Additionally, secondary alkyl can be used by the formulator exclusively or in conjunction with other surfactant materials and agents the following identifies and illustrates the differences between sulfated surfactants and otherwise conventional alkyl sulfate surfactants. Non-limiting examples of such ingredients are as follows. Conventional primary alkyl sulfates Alkyl (AS), such as those illustrated above, have the general formula ROS03-M + wherein R is typically a linear C8-22 hydrocarbyl group and is a solubilising cation water. The branched chain primary alkyl sulfate surfactants (e.g., branched chain "PAS") having 8 to 20 carbon atoms are also known; see for example, European Patent Application 439,316, Smith et al., issued January 21, 1991.

Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate portion distributed randomly along the hydrocarbyl backbone of the molecule. Such materials can be represented by the structure CH3 (CH2) n (CHOS03_M +) (CH2) mCH3 wherein m and n are integers of 2 or larger and the sum of m + n is typically about 9 to 17, and M is a cation solubilizing in water. The aforementioned secondary alkyl sulphates are those prepared by the addition of H2SO4 to the olefins. A typical synthesis using alpha-olefins and sulfuric acid is described in US Pat. No. 3,234,258, Morris, issued February 8, 1966 or in U.S. Patent No. 5,075,041, Lutz, issued December 24, 1991. See also US Patent 5,349,101, Lutz et al., Issued September 20, 1994.; Patent E.U.A- 5,389,277, Prieto, issued February 14, 1995. The preferred surfactants of the present invention are anionic surfactants, however, other useful surfactants are described hereinafter. The blends of the present invention may also comprise at least about 0.01%, preferably at least 0.1%, more preferably from 1% to 30%, of a nonionic detersive surfactant. Preferred nonionic surfactants such as the alkyl ethoxylates Ci2_ci8 ("AE") including the so-called narrow peak alkyl ethoxylates and the alkyl phenol alkoxylates Cg-C_2 (especially the ethoxylates and the mixed ethoxy / propoxy), oxide block condensates alkylene oxide of alkyl phenols c6 ~ c12 'alkylene oxide condensates of Cg-C22 alkanols and polymers of ethylene oxide / propylene oxide block (Pluronic TM-BASF Corp.), as well as also non-ionic semipolar (e.g., amino oxides and phosphine oxides) can be used in the present compositions. An extensive description of these types of surfactants is found in U.S. Patent No. 3,929,678, Laughlin et al., Issued December 30, 1975, incorporated herein by reference. Alkylpolysaccharides such as those described in Patent E.U.A. 4,565,647 Filling (incorporated herein by reference), are also preferred nonionic surfactants in the compositions of the invention. The most preferred nonionic surfactants are the polyhydroxy fatty acid amides having the formula O Rc R; C II N wherein R7 is a C5-C31 alkyl, an alkyl or alkenyl preferably having a C7-C19 straight chain, more preferably straight-chain C9-C17 alkyls or alkenyls, more preferably still straight-chain alkyls or alkenyls or c5-cl5 ° mixtures thereof; R is selected from the group consisting of hydrogen, C1-C4 alkyls, hydroxyalkyl C] _-C, preferably methyl or ethyl, more preferably methyl. Q is a polyhydroxyalkyl portion having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; the preferred alkoxide may be ethoxide or propoxide, and mixtures thereof. The preferred Q is derived from a reducing sugar in a reductive amination reaction. More preferably Q is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xyloses. As raw materials, high dextrose corn syrups, high fructose corn syrups, and high maltose corn syrups can be used as well as the individual sugars listed above. These corn syrups can provide a mixture of sugar components for Q. It should be understood that this by no means is intended to exclude other suitable raw materials. Q is more preferably selected from the group consisting of -CH2 (CHOH) nCH2OH, -CH (CH20H) (CHOH) n_O ^ OH, -CH2 (CHOH) 2- (CHORX (CHOH) CH2OH, and alkoxylated derivatives thereof wherein n is an integer ranging from 3 to 5, inclusive, and R 'is hydrogen or a cyclic or aliphatic monosaccharide The most preferred substituents for the Q portion are glycityls wherein n is 4, particularly -CH2 (CHOH) CH2OH.R CO-N <; it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide, etc. Q R, can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl, or 2-hydroxy propyl. Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltytyl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyanityl, 1-deoxymalototriotityl, etc. A particularly suitable surfactant of this type for use in the compositions herein is alkyl-N-methyl glucomide, a compound of the above formula wherein R 7 is an alkyl (preferably C _] _ C] _7), Rff, is methyl and Q is 1-deoxyglucityl. Other surfactants derived from sugars include the N-alkoxy polyhydroxyl fatty acid amides, such as the glucamide of N- (3-methoxypropyl) C10-C18- The glucamides C] _2 ~ C18 of N-propyl to N-hexyl can be used for low foam formation. The conventional soaps C] _Q-C20 can also be used.

If a high foaming is desired, branched-chain soaps C1g-C1g can be used.

AUXILIARY INGREDIENTS The following are non-limiting examples of auxiliary ingredients useful in the granular and soap bar compositions of the present invention, said auxiliary ingredients include builders, optical brighteners, bleach boosters, bleach catalysts, bleach activators, release polymers of dirt, pigment transfer agents, dispersants, enzymes, foam suppressors, pigments, perfumes, dyes, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelating agents , stabilizers, anticaking agents, anti-wrinkle agents, germicides, fungicides, anticorrosive agents, and mixtures thereof.

Detergency testers. - Detergency builders may optionally be included in the compositions described herein to assist in the control of mineral hardness. Both inorganic and organic builders can be used. Detergency builders are typically used in fabric washing compositions that aid in the removal of dirt particles. The level of the builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1% of the detergency builder. The formulations typically comprise from 5% to 50%, more typically from 5% to 30%, by weight, of the builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergency builder. However, higher or lower levels of the detergency builder should not be excluded. Inorganic or phosphorus-containing builders include, but are not limited to, alkali metals, ammonium and alkanolammonium salts of polyphosphates (exemplified by tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. For the purposes of the present invention, phosphate builders are one of the preferred builders. However, non-phosphate improvers are required in some places. Importantly, the compositions shown here work surprisingly even in the presence of so-called weak detergency builders (when compared to phosphates) such as citrate, or in the so-called sub-builder situation that can occur with zeolite or with Detergents based on layered silicates. Examples of silicate-based detergency builders are the silicates of the alkali metals, particularly those having a SiO2: Na2 ratio. in the range 1.6: 1 to 3.2: 1 and layered silicates, such as the sodium layered silicates described in U.S. Patent No. 4,664,839, issued May 12, 1987 to H.P. Rieck NaSKS-6 is a registered trademark of a crystalline layered silicate sold by Hoechst (commonly abbreviated here as "SKS-6"). Unlike zeolite-based builders, Na SKS-6 silicate builders do not contain aluminum. The NaSKS-6 has the morphology of stratified silicate delta-Na2Si? 5. It can be prepared by methods such as those described in German DE-A-3, 417, 649 and DE-A-3, 742, 043. SKS-6 is a highly preferred layered silicate for use herein, but other layered silicates , such as those that have the general formula NaMSix? 2X +? • y ^ O where M is sodium or hydrogen, x is a number ranging from 1.9 to 4, preferably 2, and "y" is a number ranging from 0 to 20, preferably 0 can be used here. Several other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, such as the alpha, beta and gamma forms. As mentioned above, the delta form of Na2Si? 5 (NaSKS-6 form) is most preferred to be used here. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen-based bleaches, and as a component of foam control systems. Examples of carbonate-based builders are the alkali metal and alkaline earth metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. The aluminosilicate-based builders are useful in the present invention. Said builders are of great importance in most heavy duty granular detergent compositions currently sold, and can also be a significant detergency builder ingredient in liquid detergent formulations. The detergents based on aluminosilicates include those that have the empirical formula: [Mz (zAl02) and] .xH20 where z and "y" are integers of at least 6, the molar ratio of z a and is in the range of 1.0 to 0.5, and x is an integer of about 15 to 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in their structure and can be aluminosilicates that occur naturally or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in US Patent 3,985,669, Krummel, et al., Issued October 12, 1976. The preferred and useful synthetic crystalline aluminosilicate ion exchange materials herein are available under the designations Zeolite. A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment the crystalline aluminosilicate ion exchange material has the formula: Na12 [(A102) 12 (Si02) 12] .xH20 where x goes from 20 to 30, especially near 27. This material is known as zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders appropriate for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylated compounds. As used herein, "polycarboxylate" refers to compounds having a diversity of carboxylated groups, preferably at least 3 carboxylates. The polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the neutralized salt form. When used in saline, salts of the alkali metals such as sodium, potassium and lithium or alkanolammonium are preferred. Included within the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders includes polycarboxylate ethers, including oxydisuccinate, as described in Berg, US Patent 3,128,287, issued April 7, 1964, and Lamberti et al., US Patent 3,635,830, issued on January 18, 1972. See also detergent builders "TMS / TDS" of U.S. Patent 4,663,071, issued to Bush et al., May 05, 1987. Suitable polycarboxylate ethers also include cyclic compounds, particularly alicyclic compounds, such as those described in the American patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4, 102, 903. Other useful builders include hydroxypolycarboxylate ethers, maleic anhydride copolymers with vinyl methyl ether or ethylene, 1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitriltriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene acid 1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and the soluble salts thereof. Citrate-based detergency builders, eg, citric acid and its soluble salts (particularly the sodium salt), are polycarboxylate builders of particular importance for heavy-duty liquid detergent formulations because of their availability from from renewable sources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the, 3-dicarboxy-4-oxa-1, 6-hexanedioates and the related compounds described in US Patent No. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include alkyl succinic and alkenyl acids succinic C5-C20 and? US salts. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of the succinate builders include lauryl succinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in European patent application 86200690.5 / 0,200,263, published on November 05, 1986. Other suitable polycarboxylates are described in US Pat. No. 4,144,226, Crutchfield et al., Issued on March 13, 1979, and in US Patent 3,308,067, Diehl, issued on March 7, 1967. See also Diehl US Patent 3,723,322. The fatty acids, v.gr, monocarboxylic acids, can also be incorporated into the compositions by themselves, or in combination with the detergency builders mentioned above, especially the builders of succinate and / or citrate, to provide an enhancing activity of additional detergency. Such use of fatty acids will generally result in a decrease in foaming, which should be taken into account by the formulator. In situations where phosphorus-based builders can be used, and especially in the formulation of bars for hand washing operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonates-based builders such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, for example, US Patents 3,159,581).; 3,213,030; 3,422,021; 3, 400, 148 and 3, 422, 137).

Dispersants' The compositions of the present invention may also optionally include at least about 0.1% by weight, preferably from 0.1% to 10%, more preferably from 0.5% to 5% by weight, of a modified or modified unmodified polyalkyleneimine dispersant or Without replacing water soluble, said dispersant includes a polyamine backbone, preferably said backbone has a molecular weight of 100 to 3000 daltons with the formula: H [H2N-R] n + 1- [N-R] m- [N-R] n-NH2 wherein R is preferably a C2-C alkylene, m is from 3 to 70, n goes from 0 to 35, one or more of the hydrogens of the NH units of the polyamine skeleton are "substituted", this is replaced with a substituent which increases the hydrophilic or hydrophobic dispersancy of said polyamine, preferably one or more skeleton hydrogens, more preferably all hydrogens are replaced by a propyleneoxy / ethyleneoxy unit having the formula: - (CH2CHR, 0) and (CH2CH2?) XH wherein R1 is methyl or ethyl, x and y are preferably from 0 to 50, providing that x + y is at least 1; and wherein subsequently each nitrogen comprised in the polyalkyleneimine backbone can be optionally "modified" by quaternization or by oxidation to the N-oxide. A subsequent description of the polyalkyleneimine dispersants is found in E.U.A. 4,597,898, VanderMeer, issued July 1, 1986; European Patent Application 111,965, Oh and Gosselink, published June 27, 1984; European patent application 111,984, Gosselink, published June 27, 1984; European Patent Application 112,592, Gosselink, published July 04, 1984; E.U.A. 4,548,744, Connor, issued October 22, 1985; and E.U.A. 5,565,145 Watson et al., Issued October 15, 1996; of which all are included here for reference. However, any anti-redeposition agent or clay or dirt dispersant can be used in the laundry compositions of the present invention.

Dirt releasing agents Any polymeric soil release agent known to those skilled in the art can optionally be used in the compositions and methods of this invention. The polymeric soil release agents are characterized by having both hydrophilic segments to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, as hydrophobic segments, to deposit on the hydrophobic fibers and remain stuck there until the end of the cycles of washing and rinsing and, in this way, serve as an anchor for the hydrophilic segments. This can cause stains that appear subsequent to treatment with the soil release agent to be removed and cleaned more easily in subsequent washing procedures. The polymeric soil release agents useful herein especially include those soil release agents having: a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not include any oxypropylene unit unless it is attached to segments adjacent to each end by ether linkages, or (iii) a mixture of oxyalkylene units including oxyethylene and from one to 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophilic component has a hydrophilicity large enough to increase the hydrophilicity of the polyester fiber surfaces Conventional synthetics by depositing the soil release agent on said surface, said hydrophilic segments preferably include at least 25% oxyethylene units and more preferably, especially for such components to have about 20 to 30 oxypropylene units, at least about 50 % of oxyethylene units; or b) one or more hydrophobic components comprising (i) segments of C3 oxyalkylene terephthalate, wherein if said hydrophobic component further includes oxyethylene terephthalate, the ratio of oxyethylene terephthalate: to the C3 oxyalkylene terephthalate units is about 2. : 1 or lower, (ii) C4-C alkylene segments or C-C10 oxy-alkylene, or mixtures thereof, (iii) segments of poly (vinyl ester) preferably polyvinyl acetate) having a degree of polymerization of minus 2, or (iv) C 1 -C 4 alkyl ethers or C 4 hydroxyalkyl ether substituents or mixtures thereof, wherein said substituents are present in the form of C 1 -C 4 alkyl ether or cellulose derivatives and C 4 hydroxyalkyl ether, or mixtures thereof, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C4 hydroxyalkyl ether units and / or C1-C4 alkyl ether to be deposited on the surfaces of synthetic fibers. of conventional polyester and of retaining a sufficient level of hydroxyls, once they adhere to said surface of the conventional synthetic fiber, to increase the hydrophilicity of the surface of the fiber, or a combination of (a) and (b). Typically, the polyoxyethylene segments of (a) (i) will have a degree of polymerization of 200, although at higher levels they may be used, preferably from 3 to 150, more preferably from 6 to 100. Suitable hydrophobic 4-C-oxyalkylene segments include, but are not limited to a, end blockers of polymeric mughre release agents such as MO3S (CH2) nOCH2CH2? -, where M is sodium and n is an integer from 4 to 6, as described in the US Patent 4,721,580, issued on January 26, 1988 to Gosselink. The polymeric soil release agents useful in the present invention also include cellulose derivatives such as cellulosic polymers hydroxyethers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or propylene oxide terephthalate, and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1 -C 4 alkyl cellulose and C 4 hydroxyalkyl cellulose; see Patent E.U.A- 4,000,093, issued December 28, 1976 to Nicol, and others. Dirt release agents characterized by hydrophobic poly (vinyl ester) segments include graft copolymers of poly (vinyl ester) e.g., vinyl esters Cj_-Cg, preferably poly (vinyl acetate) grafted onto polyalkylene oxide backbones , such as polyethylene oxide skeletons. See European patent application 0 219 048, published April 22, 1987 by Kud et al. Commercially available dirt release agents of this type include SOKALAN material type eg, SOKALAN HP-22, available from BASF (West Germany). One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate (PEO). The molecular weight of this polymeric soil release agent is in the range of 25,000 to 55,000. See Patent E.U.A. 3,959,230 to Hays, issued May 25, 1976 and Patent E.U.A. 3,893,929 to Basadur issued July 08, 1975. Another preferred polymeric soil release agent is a polyester with repeating units of ethylene terephthalate units containing 10 to 15% by weight of ethylene terephthalate units together with 90 to 80 % by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol, of average molecular weight from 300 to 5,000. Examples of these polymers include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also Patent E.U.A. 4,702,857 issued on October 27, 1987 to Gosselink. Another preferred polymeric soil release agent is a sulfonated product of a substantially linear oligomeric ester formed from an oligomeric terephthaloyl ester backbone and repeated oxyalkylenoxide units and end portions covalently attached to the backbone. These soil release agents are fully described in US Pat. 4,968,451 issued November 06, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include terephthalate polyesters of US Pat. 4,711,730, issued December 08, 1987 to Gosselink et al., The anionic oligomeric esters blocked at the end of US Patent E.U.A. 4,721,580, issued January 26, 1988 to Gosselink, and block oligomeric polyester compounds, from US Patent E.U.A. 4,702,857, issued on October 27, 1987 to Gosselink. Preferred polymeric soil release agents also include the soil release agents of US Pat. 4,877,896, issued October 31, 1989 to Maldonado et al., Which describes anionic esters, especially sulfoaroyl esters, of terephthalate with blocked ends. Still another preferred soil release agent is an oligomer with repeating units of terephthaloyl units, sulfoisoterephthaloyl, oxyethyleneoxypropylene units, and oxy-1,2-propylene. The repeating units form the skeleton of the oligomer and are preferably terminated with end blockers modified with isothionate. A particularly preferred soiling agent of this type comprises a sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy units and oxy-1,2-propylene oxide in a ratio of about 1.7 to 1.8 and two end blocking units of 2- ( Sodium 2-hydroxyethoxy) -ethansulfonate. Said soil release agents also comprise from about 0.5% to 20% by weight of the oligomer, of a crystalline reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, eumeno sulfonate, toluene sulfonate, and mixtures thereof. same. The most preferred soil release agents comprise about 25% to 100% by weight of an ester having the formula (CAP) x (EG / PG) and (T) z wherein (CAP) represents the sodium salt of a substantially linear polyethoxy / propoxy sulfonated end block blocking unit of the formula (M03S) (CH2) m (CH2CH20) - (RO) n- where M is sodium, m is 0 or 1, R is ethylene, propylene or a mixture from both; and n goes from 0 to 2, - (EG / PG) represents the ratio between the oxyethyleneoxy unit, oxy-1, 2-propyleneoxy and poly (oxyethylene) oxide, (T) represents the terephthalate units and x ranges from 1 to 2 , and goes from 0.5 to 7, z goes from 1.5 to about 7 and x, y and z represent the relative numbers of moles of each unit per mole of ester; as described in the patent E.U.A. 5,415,807 Gosselink et al., Issued May 16, 1995, included herein for reference. If used, the soil release agents will generally comprise from 0.01% to 10.0% by weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3%.

Other Ingredients A wide variety of other ingredients useful in detergent compositions can be included in the compositions described herein, including other active ingredients, carriers, hydrotropes, process aids, dyes or pigments, solid fillers for stick compositions, etc. Other optional ingredients include enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners, hydrolyzable surfactants, optical brighteners, preservatives, antioxidants, chelators, stabilizers, anticaking agents, anti-wrinkle agents, release agents dirt, germicides, fungicides and anticorrosive agents. If high foaming is desired, foam enhancers such as the alkanolamides C] _Q to C ^ g can be incorporated into the compositions, typically at levels of 1% to 10%. The monoethanol amides C] _Q to cn and diethanol illustrate a typical class of such foam enhancers. The use of such foam enhancers with high foaming auxiliary surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, the soluble magnesium salts such as MgCl 2, MgSO 4 and the like can be added at levels of, typically, 0.1% to 2% to provide additional foam and to increase fat removal performance. Various detersive ingredients used in the present compositions optionally can be further stabilized by absorption of said ingredients in a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate to the aqueous wash solution, where it begins to develop its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (registered trademark SIPERNAT DIO, DeGussa) is mixed with a proteolytic enzyme solution containing 3% to 5% of a nonionic surfactant of ethoxylated alcohol C13-C15 (EO 7 ). Typically, the surfactant / enzyme solution is 2.5X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oils can be used whose viscosity is in the range of 500 to 12,500). The resulting dispersion in silicone oil is emulsified or in another form added to the final detergent matrix. By this means, ingredients such as the above-mentioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, pigments, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergent compositions. The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water has a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. The techniques to control the pH to the recommended levels of use include the use of regulators, alkalis, acids, etc. and they are well known to those skilled in the art.

Granulated compositions The co-profragancias of the present invention can be used both in low density (below 550 grams / liter) and high density granular compositions in which the granule density is at least 550 grams / liter.

The granular compositions are typically designed to provide a pH of 7.5 to 11.5 during the wash, more preferably from 9.5 to 10.5. The low density compositions can be prepared by standard spray drying processes. Various media and equipment are available to prepare high density compositions. Current commercial practice in the field uses spray-drying towers to manu- facture compositions having a density of less than 500 g / 1. Agree, if spray drying is used as part of the process in general, the particles resulting from spray drying should be subsequently densified using the means and equipment described below. In the alternative, the formulator can eliminate spray drying using commercially available mixing, densifying and granulating equipment. The following is a non-limiting description of such appropriate equipment for use herein. Various means and equipment are available for preparing high-solubility, high-density, free-flowing granular detergent compositions (e.g., greater than 550, preferably greater than 650, grams / liter or "g / 1"), in accordance to the present invention. In current commercial practice in the field, spray-drying towers are used to manufacture granular laundry detergents, which often have a density less than 500 g / 1. In this process, an aqueous suspension of various heat-stable ingredients in the final detergent mixture are formed as homogeneous granules by passing them through a spray-drying tower, using conventional techniques at temperatures of about 175 ° C to 225 ° C. . However, if spray drying is used as part of the entire process here, additional steps of the procedure should be used as described below to obtain the density level (eg, >; 650 g / 1) required by modern compact, low-dose detergent products.

For example spray-dried granules in the tower may be further densified by charging a liquid such as water or a nonionic surfactant into the pores of the granules and / or by subjecting them to one or more high speed densifiers / mixers. A high speed densifier / mixer suitable for this purpose is an apparatus sold under the trademark "Lódige CB 30" or "Lódige CB 30" Recycler which comprises a static cylindrical mixing drum having a central rotary arrow with mixing knives. / cut mounted on it. In use, the ingredients for the detergent composition are introduced into the drum and the arrow / knife assembly is rotated at speeds in the range of 100 to 2500 rpm to provide sufficient mixing / densification. See Jacobs et al. Patent E.U.A. No. 5,149,455, issued September 22, 1992. The preferred residence time in the high speed densifier / mixer ranges from 1 to 60 seconds. Other devices include the artifacts sold under the trademarks "Shugi Granulator" and under the trademark "Drais K-TTP 80. Another process step that can be used to further densify spray-dried granules involves grinding and agglomeration or deformation of spray-dried granules in a moderate speed densifier / mixer to obtain particles with lower intraparticle porosity Mixer / densifier equipment such as those sold under the trade names "Lódige KM" (series 300 or 600) or "Lódige Ploughshare" are appropriate for this step of the procedure, such equipment is typically operated at 40-160 rpm.The residence time of the detergent ingredients in the moderate speed densifier / mixer ranges from 0.1 to 12 minutes. useful includes the artifact that is available under the name "Drais KT 160." This step of the procedure which uses a densifier / moderate speed mixer (v. gr., Lódige KM) can be used by itself or sequentially with the above-mentioned high speed densifier / mixer (v. gr., Lódige CB) to obtain the desired density. Another type of apparatus useful for the manufacture of granules here includes the apparatuses described in US Pat. No. 2,306,898, for GL Heller, December 29, 1942. While it may be more appropriate to use the high speed densifier / mixer followed by the low speed densifier / mixer, the reverse densifier / mixer sequence is also contemplated by the invention. . One or a combination of several parameters including residence times in the mixers / densifiers, operating temperatures of the equipment, temperature and / or composition of the granules, the use of auxiliary ingredients such as liquid builders and flow auxiliaries, they can be used to optimize the densification of the spray-dried granules in the process of the invention. As an example, see the procedures in Appel and other US Patent. 5,133,924, issued July 28, 1992 (the granules are brought to a deformable state before densification); Delwel et al., Patent E.U.A. No. 4,637,891, issued January 20, 1987 (granulation of spray-dried granules with a liquid binder and aluminosilicate); Kruse et al., Patent E.U.A. 4,726,908, issued February 23, 1988 (the granulation of spray-dried granules with a liquid binder and aluminosilicate); and Bortolotti et al. Patent E.U.A. No. 5,160,657, issued November 3, 1992 (coated with densified granules with a liquid binder and aluminosilicate). In those situations in which the co-promotions or detergent ingredients are particularly heat sensitive or highly volatile these will be incorporated into the final detergent composition, processes in which the spray towers are preferred are not included. The formulator can eliminate the step of spray drying by the fact of feeding, either in a continuous or batch form, the detergent start ingredients directly in the commercially available mixing / densification equipment. A particularly preferred embodiment involves charging a paste of the surfactant and an anhydrous builder material in a high speed densifier / mixer (eg, Lódige CB) followed by a moderate speed densifier / mixer (v. ., Lódige KM) to form agglomerates of high density detergent. See Capeci et al., Patent E.U.A. No. 5,366,652, issued November 22, 1994 and Capeci et al., Patent E.U.A. No. 5,486,303, issued January 23, 1996. Optionally, the liquid / solids ratio of the detergent starting ingredients in a process as such can be selected to obtain high density agglomerates that have a freer flow and the granules are more brittle . Optionally, the process can include one or more recycle streams of particles with smaller than desired size produced by the process which are fed back to the mixers / densifiers for subsequent agglomeration or accumulation. Particles with excess size produced by this process can be sent to grinding apparatuses and then returned to the mixing / densification equipment. These steps of the additional recycling process facilitate the agglomeration by accumulation of the detergent starting ingredients which results in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density (>); 550 g / 1). See Capeci et al., Patent E.U.A. No. 5,516,448, issued May 14, 1996 and Capeci et al. Patent E.U.A. No. 5,489,392, issued February 06, 1996. Other suitable methods which do not require the use of spray drying towers are described by Bollier et al., U.S. Pat. No. 4,828,721, issued May 09, 1989; Beerse et al., Patent E.U.A. No. 5,108,646, issued April 28, 1992; and Jolicoeur, Patent E.U.A. 5,178,798, issued January 12, 1993. Still in another embodiment, the high density detergent composition of the invention can be produced using a fluid bed mixer. In this process, the various ingredients of the finished composition are combined in an aqueous suspension (typically 80% solid content) and sprinkled in a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, this method can optionally include the step of mixing the suspension using the above-mentioned Lódige CB densifier / mixer or a "Flexomix 160" densifier / mixer, available from Shugi. The fluidized bed or moveable beds of the type available under the "Escher Wyss" brand can be used in such procedures. Another suitable process which can be used here involves feeding a liquid acid precursor of an anionic surfactant, an inorganic alkaline material (eg, sodium carbonate) and optionally other detergent ingredients in a high speed densifier / mixer. (residence time 5-30 seconds) so as to form agglomerates containing a partially or fully neutralized anionic surfactant salt and the other detergent-onset ingredients. Optionally, the contents in the high speed densifier / mixer can be sent to a moderate speed densifier / mixer (eg, Lódige KM) for subsequent agglomeration which results in the finished high density detergent composition. See Appel et al., Patent E.U.A. No. 5,164,108, issued November 17, 1992. The following examples illustrate the β-keto-esters and compositions of this invention, but are not intended to be limited thereto by them.

EXAMPLE 1 Preparation of 3,7-dimethyl-l, 6-octadien-3-yl 3- (β-naphthyl) -3-oxo-propionate Lithium diisopropylamide (101.0 mL of a 2.0 M solution, 0.202 mol) is placed in a three-necked round bottom flask equipped with a magnetic stirrer, internal thermometer, argon inlet, and an addition funnel. The flask is placed in a dry ice / acetone bath. 3,7-Dimethyl-1,6-octadien-3-yl acetate (linalyl acetate) is dissolved in the amount of (18.66 g, 0.095 mol), in THF (5 mL) and the resulting solution is added to the flask in the course of 45 minutes. Once the addition has been completed, the mixture is stirred for another 15 minutes before starting to be treated with a solution of 2-naphthoyl chloride in amount of (17.43 g, 0.090 mol) dissolved in THF (25 mL) in the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After having warmed to 0 ° C, the mixture is quenched with 20% hydrochloric acid (53 mL). The mixture is then poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL), the combined organic layers are washed with a saturated solution of NaHC 3 (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSO 4. and filtered. The solvent is removed with rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. The purity of the product is determined by thin layer chromatography and GC analysis and the structure confirmed by mass spectrometry, 13C and XH NMR EXAMPLE 2 Preparation of 2,6-dimethyl-7-octen-2-yl 3- (4-methoxyphenyl) -3-oxo-propionate N-isopropylcyclohexylamine (25.00g, 0.177 moles) and THF in the amount of 200 ml are placed in a 1000 ml three-necked round bottom flask fitted with magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in an ice / methanol bath cooled to -5 ° C and its contents treated with n-butyl-lithium (70.8 ml of a 2.50 M solution)., 0.177 moles). The mixture is stirred for 20 minutes and then cooled to -78 ° C. Dissolve 2,6-dimethyl-7-octen-2-yl acetate (hydromircenyl acetate) in the amount of (17.55 g, 0.089 mole) in THF (10 ml) and the resulting solution is added to the flask in the course 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes before starting to be treated with a solution of parametoxybenzoyl chloride in the amount of (15.10 g, 0.090 mol) dissolved in THF (25 ml) in the course 30 minutes and then stirred for 1 hour. The mixture is heated to 0 ° C and then treated with 90 ml of 20% hydrochloric acid 1 hour later. The mixture is poured into a separatory funnel containing ether (100 ml) and water (200 ml). The aqueous layer is extracted with ether (100 ml). The combined organic layers are washed with saturated NaHCO3 solution (2 x 100 ml), water (2 x 100 ml) and brine (100 ml), dried over MgSO4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. The purity of the product is determined by thin layer chromatography and the structure confirmed by 13C and 1H NMR EXAMPLE 3 Preparation of 2,6-imetyl-7-octen-2-yl 3- (4-nitrophenyl) -3-oxo-propionate Lithium diisopropylamide (121.0 ml of a 2.0 M solution, 0.243 mole) is placed in a 500 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a dry ice / acetone bath. 2,6-Dimethyl-7-octen-2-yl acetate (22.66 g, 0.114 mol) is dissolved in THF (5 ml) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes before being treated with a solution of 4-nitrobenzoyl chloride (20.00 g, 0.108 mol) dissolved in THF (25 ml) over the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (70 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous layer is extracted with ether (150 ml). The combined organic layers are washed with saturated solution of N HC 3 (2 x 100 ml), water (2 x 150 ml) and brine (150 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having an NMR spectrum 13 C and 1 H which is consistent with the desired product.

EXAMPLE 4 Preparation of 2,6-imetyl-7-octen-2-yl 3 - (beta-naphthyl) -3-oxo-propionate Lithium diisopropylamide is placed in the amount of (100.0 ml of a 2.0 M solution, 0.201 mol) in a 500 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. . The flask is cooled to -78 ° C. 2,6-Dimethyl-7-octen-2-yl acetate is dissolved in the amount of (18.75 g, 0.095 mole) in THF (5 ml) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes before being treated with a solution of 2-naphthoyl chloride in the amount of (17.00 g, 0.89 mol) dissolved in THF (25 ml) in the course 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (55 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous layer is extracted with ether (150 ml). The combined organic layers are washed with saturated NaHC 3 solution (2 x 10 ml), water (2 x 150 ml) and brine (150 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in petroleum ether) to give an oil. The purity of the product is determined by thin layer chromatography and the structure is confirmed by 13 C and 1 H NMR.

EXAMPLE 5 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3- (4-methoxyphenyl) -3-oxo-propionate Lithium diisopropylamide is placed in the amount of (119.0 ml of a 2.0 M solution, 0.238 mol) in a 500 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. . The flask is cooled to -78 ° C. 3,7-Dimethyl-1,6,6-octadien-3-yl acetate (22.04 g, 0.112 mol) is dissolved in THF (5 ml) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes before being treated with a solution of para-anisoyl chloride (35.00g, 0.106 moles) dissolved in THF (30 ml) over the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (80 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous layer is extracted with ether (150 ml). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 ml), water (2 x 150 ml) and brine (150 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an oil. The oil is purified by column chromatography (elution with 2% ethyl acetate in petroleum ether) to give a colorless oil having a 13 P and 1 H NMR spectrum consistent with the desired product.

EXAMPLE 6 Preparation of (alpha, alpha-4- trimethyl-3-cyclohexenyl) methyl 3- (beta-naphthyl) -3 -oxo-propionate Lithium diisopropylamide is placed in the amount of (171.0 ml of a 2.0 M solution, 0.342 mole) in a 1000 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled to -78 ° C. Acetate (alpha, alpha-4-trimethyl-3-cyclohexenyl) methyl (30.00g, 0.153 mol) is dissolved in THF (10 ml) and the resulting solution is added to the flask in the course of 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes before being treated with a solution of 2-naphthoyl chloride (29.00 g, 0.152 mol) dissolved in THF (50 ml) over the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (105 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous layer is extracted with ether (150 ml). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 ml), water (2 x 150 ml) and brine (150 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an oil. The oil is purified by column chromatography (elution with 2% ethyl acetate in petroleum ether) to give a semi-white solid which is triturated in cold N-pentane to give a white powder having a 13 C NMR spectrum and H consistent with the desired product.

EXAMPLE 7 Preparation of 3, 7-dimethyl-l, 6-octadin-3-yl 3- (alpha-naphthyl) -3-oxo-propionate Diisopropylamide (96.3 ml of a 2.0 M solution, 0.193 mol) is placed in a 500 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled to -78 ° C. 3,7-Dimethyl-1,6-octadin-3-yl acetate (17.81 g, 0.091 mol) is dissolved in THF (5 ml) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes, before starting to be treated with a solution of l-naphthoyl chloride (16.82 g, 0.086 mol) dissolved in THF (25 ml) in the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (53 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous layer is extracted with ether (150 ml). The combined organic layers are washed with saturated NaHC 3 solution (2 x 100 ml), water (2 x 150 ml) and brine (150 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to provide a colorless oil having a 1 H and 13 C NMR spectrum consistent with the desired product.

EXAMPLE 8 Preparation of cis 3-hexen-l-yl 3- (S-naphthyl) -3 -oxo-propionate Lithium diisopropylamide (133.0 ml of a 2.0 M solution, 0.266 mole) is placed in a 500 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, inlet for argon and an addition funnel.

The flask is cooled to -78 ° C. 3-Hexenyl cis acetate (17.80 g, 0.125 mol) is dissolved in THF (10 ml) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes before being treated with a solution of 2-naphthoyl chloride (22.51 g, 0.118 mol) dissolved in THF (30 ml) over the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (70 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous layer is extracted with ether (150 ml). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 ml), water (2 x 150 ml) and brine (150 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having a 1 H and 13 C NMR spectrum consistent with the desired product.

EXAMPLE 9 Preparation of 9-decen-l-yl 3 - (β-naphthyl) -3-oxo-propionate Lithium diisopropylamide (79.8 ml of a 2.0 M solution, 0.160 mol) is placed in a 250 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, inlet for argon and an addition funnel. The flask is cooled to -78 ° C. 9-Decen-1-yl acetate (14.91 g, 0.075 mole) is dissolved in THF (5 ml) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes before being treated with a solution of 2-naphthoyl chloride (13.80 g, 0.071 mol) dissolved in THF (25 ml) over the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (47 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous phase is extracted with ether (150 ml). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 ml), water (2 x 150 ml) and brine (150 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having a 1 H and 1 C NMR spectrum consistent with the desired product.

EXAMPLE 10 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3- (nonanyl) -3 -oxo-propionate Lithium diisopropylamide (133.7 ml of a 2.0 M solution, 0.267 mole) is placed in a 500 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, inlet for argon and an addition funnel. The flask is cooled to -78 ° C. 3,7-Dimethyl-1,6,6-octadien-3-yl acetate (24.73 g, 0.126 mol) is dissolved in THF (40 ml) and the resulting solution is added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for an additional 15 minutes before being treated with a solution of nonanoyl chloride (21.88 g, 0.119 mol) over the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (60 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous layer is extracted with ether (150 ml). The combined organic layers are washed with saturated NaHCO 3 solution (2 x 100 ml), water (2 x 150 ml) and brine (150 ml), dried over MgSO 4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having a 13 JC and 1 H NMR spectrum consistent with the desired product.

EXAMPLE 11 Preparation of 2, 6-? Imethyl-7-octen-2-yl 3- (nonanil) -3-oxo-propionate Lithium diisopropylamide (75.7 ml of a 2.0 M solution, 0.151 mol) is placed in a 500 ml three-necked round bottom flask fitted with a magnetic stirrer, internal thermometer, inlet for argon, and an addition funnel. The flask is cooled to -78 ° C. 2,6-Dimethyl-7-octen-2-yl acetate (14.14g, 0.071 mole) was dissolved in THF (20 ml) and the resulting solution was added to the flask within 45 minutes. Once the addition is complete, the mixture is stirred for another 15 minutes before being treated with a solution of nonanoyl chloride (12.38 g, 0.067 mol) over the course of 30 minutes. The mixture is heated to -20 ° C and stirred at that temperature for 18 hours. After heating to 0 ° C, the mixture is quenched with 20% hydrochloric acid (55 ml). The mixture is poured into a separatory funnel containing ether (150 ml) and water (250 ml). The aqueous layer is extracted with ether (150 ml). The combined organic layers are washed with saturated NaHCO3 solution (2 x 100 ml), water (2 x 150 ml) and brine (150 ml), dried over gSO4 and filtered. The solvent is removed by rotary evaporation to give an orange / red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate / petroleum ether) to give a colorless oil having an NMR spectrum 1 C and 1 H consistent with the desired product.

EXAMPLE 12 Preparation of 3,7-dimethyl-l, 6-octadien-3-yl 3-oxo-butyrate A mixture of linalool (5 g, 0.648 moles) and 4-dimethylaminopyridine (0.40 g, 3.20 mmol) are heated in a 500 ml three-necked round bottom flask fitted with a condenser, argon inlet, addition funnel, stirrer magnetic and internal thermometer, at 55 ° C. The diketene (54.50 g, 0. 648 moles) is added dropwise over the course of 30 minutes. The mixture has a slight exotherm and changes from yellow to red during this time. After stirring an additional 1 hour at 50 ° C, the mixture is cooled to room temperature.

At this point, the NMR analysis indicates that the reaction is complete. The material of this lot is taken to the next step. Purification of a previous sample from this route by flash chromatography (elution with dichloromethane) yields the desired product with 92% yield and almost colorless.

EXAMPLE 13 Preparation of 2,6-dimethyl-7-octen-2-yl-3-oxo-butyrate A mixture of dihydromyrcenol (37.88 g, 0.240 mol) and 4-dimethylaminopyridine (0.16 g, 1.30 mmol) is heated to 50-60 ° C in a 100 ml three-necked round bottom flask fitted with a condenser, argon inlet , addition funnel, magnetic stirrer and an internal thermometer. The diketene (20.16 g, 0.240 mol) is added dropwise in the course of 15 minutes. The mixture has a slight exotherm and changes from yellow to red during this time. After stirring an additional hour at 50 ° C, the mixture is cooled to room temperature. At this point, the NMR analysis indicates that the reaction is complete. Purification of the product mixture by flash chromatography (elution with dichloromethane) gives the desired product in 95% yield and as an almost colorless oil.

EXAMPLE 14 Preparation of 3,7-dimethyl-l, 6-octadien-3-yl 3- (beta-naphthyl) -3-oxo-propionate Raw 3,7-dimethyl-l, 6-octadien-3-yl-3-oxo-butyrate from the previous preparation (154.51 g, 0.648 mol) is placed in a 3000 ml three-necked round bottom flask fitted with a condenser , argon inlet, addition funnel, magnetic stirrer, and internal thermometer. The content is dissolved in 350 ml of dichloromethane and treated with calcium hydroxide powder (50.44 g, 0.681 mol). The mixture is stirred at 30 ° C for 30 minutes and then heated to 40 ° C. 2-Naphthoyl chloride (142.12 g, 0.746 mol) dissolved in 20 ml of dichloromethane is added dropwise over the course of 15 minutes. The mixture continues heating at a temperature for one hour. The ammonium chloride (36.41 g, 0.681 mol) dissolved in 250 ml of water is added to the reaction mixture and the pH is adjusted to about 9 with 28% ammonium hydroxide. After stirring 30 minutes at 35 ° C the pH is adjusted to about 1 with 20% HCl. The mixture is transferred to a separatory funnel containing diethyl ether (500 ml) and water (500 ml). The layers are separated and the organic phase is washed with saturated NaHC 3 solution (2 x 500 ml), dried over MgSO 4, filtered and concentrated by rotary evaporation to give a reddish-yellow oil. At this point a pale yellow solid precipitates from the mixture. An equal volume of hexane is added and the solids are collected by filtration and dried. NMR analysis indicates that the solid is 2-naphthoic acid. The eluent is again concentrated by rotary evaporation to give a red oil. The oil is brought to an equal volume of dichloromethane, passed through a plug of silica gel (400 g) and eluted with dichloromethane. The mixture is concentrated by rotary evaporation and cleaned by Kugelrohr distillation (40 ° C, 0.10 mm Hg, 30 minutes) to provide 173.26 g (76.3%) of the product as a red oil; This product is a mixture of linalylacetoacetate with linalyl (2-naphthoyl) acetate in molar ratio of 1:10. A portion of this material is purified by column chromatography (elution with 2.5% ethyl acetate in hexanes) to give the desired product as a light yellow oil.

EXAMPLE 15 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl 3 - (beta-naphthyl) -3-oxo-2,2-dimethylpropionate Sodium hydride (2.30 g, 0.057 mole, 60%) and tetrahydrofuran (50 ml) are placed in a 250 ml three-necked round bottom flask fitted with a magnetic stirrer, ice bath, addition funnel, internal thermometer and entry for argon. The contents of the flask are cooled to 0 ° C. 3, 7-Dimethyl-l, 6-octadien-3-yl 3- (beta-naphthyl) -3-oxo-propionate (8.94 g, 0.025 mole) dissolved in 50 ml of tetrahydrofuran is added to the flask in the course of 30 minutes. During the addition, the mixture releases gas. After stirring for an hour, methyl iodide (7.24 g, 0.051 mol) is added to the reaction mixture. The stirring is continued for 2 hours at 0 ° C and then at room temperature for 18 hours. The mixture is neutralized with 20% HCl and extracted with diethyl ether. The organic layers are washed with saturated NaHCO3 solution, water, dried over MgSO4, filtered, concentrated by rotary evaporation and purified by flash chromatography to give the desired compound. The structure is confirmed by 1 C 1 H NMR.

EXAMPLE 16 Preparation of 3, 7-dimethyl-l, 6-octa-ien-3-yl 3- (beta-naphthyl) -3-oxo-2-ethylpropionate Sodium hydride (3.92 g, 0.098 mol, 60%) and tetrahydrofuran (100 ml) are placed in a 250 ml three-necked round bottom flask fitted with a magnetic stirrer, ice bath, addition funnel, internal thermometer and entry for argon. The contents of the flask are cooled to 0 ° C. 3,7-Dimethyl-l, 6-octadien-3-yl 3- (beta-naphthyl) -3-oxo-propionate (15.28 g, 0.044 mole) dissolved in 50 ml of tetrahydrofuran are added dropwise to the flask. a course of 30 minutes. During the addition, the mixture releases gas. After stirring for 1 hour, methyl iodide (10.65 g, 0.075 mol) is added to the reaction mixture. Stirring continues for 2 hours at 0o and then at room temperature for 18 hours. The mixture is neutralized with 20% HCl and extracted with diethyl ether. The organic layers are washed with saturated NaHC 3 solution, water, dried over MgSO 4, filtered, concentrated by rotary evaporation and purified by flash chromatography to obtain the desired compound. The structure is confirmed by C NMR and H.

EXAMPLE 17 Preparation of 3,7-dimethyl-l, 6-octadien-3-yl 3- (hexyl) -3-oxo-propionate Combine 3, 7-dimethyl-l, 6-octadien-3-yl-3-oxo-butyrate (30.00 g, 0.126 mol), dichloromethane (50 ml) and methyl ethyl ketone (10 ml) in a three-necked round bottom flask. of 500 ml adapted with an internal thermometer, addition funnel, condenser and argon inlet. Calcium hydroxide (9.8 g, 0.132 mol) powder is added to the flask and the suspension is stirred for 1 hour. Heptanoyl chloride (17.84 g, 0.120 mol) is added in 10 ml of dichloromethane over the course of 15 minutes to maintain the reaction temperature between 35-40 ° C. The reaction continues in the agitation at 35 to 40 ° C for 2 hours. Ammonium chloride (7.06 g, 0.132 mol) dissolved in 20 ml of water is added to the flask. After 20 minutes, concentrated ammonium hydroxide is added to the mixture to adjust the pH close to ~ 9.0. After 1 hour, 20% HCl solution is added to lower the pH close to 1. After 1 hour, the sample is poured into 300 ml of dichloromethane. The layers are separated and the aqueous phase is extracted with 100 ml of dichloromethane. The combined organic layers are washed with saturated NaHCO3 solution, water, dried over MgSO4, filtered, concentrated by rotary evaporation and purified by flash chromatography to give the desired compound. The structure is confirmed by 1E and 13C NMR.

EXAMPLE 18 Preparation of 3, 7-dimethyl-l, 6-octadien-3-yl-3-oxo-2-benzylbutyrate Potassium carbonate (3.92 g, 0.028 mol), 3,7-dimethyl-l, 6-octadien-3-yl-3-oxo-butyrate (4.80 g) is placed., 0.030 mole), benzyl chloride (4.80 g, 0.038 mole) and acetone (15 ml) in a 50 ml round bottom flask fitted with magnetic stirrer, condenser and inlet for argon. The mixture is heated under reflux for 18 hours. The cooled mixture is filtered and concentrated by rotary evaporation. The resulting oil is purified on silica gel to give the compound the desired compound. The structure is confirmed by thin layer chromatography and 1 H and 13 C NMR. The following compositions are examples of heavy-duty granular detergents including pro-fragrances of the present invention.

TABLE I % by weight Ingredients 19 20 21 1. DEQUEST 2060 as sold by Monsanto. 2. Sodium noniloxibencenesulfonate. 3. Sulfonated zinc phthalocyanine according to E.U.A. 4,033,718, Holcombe et al., Issued July 5, 1977. 4. Si02 / Na20 ratio of 1.6: 1. 5. Dirt releasing polymer according to the patent E.U.A. 5,415,807, Gosselink et al., Issued May 16, 1995. 6. Propragance according to example 12. The following compositions are later examples of granular laundry detergents according to the present invention.

TABLE II% by weight Ingredients 22 23 24 TABLE II (CONTINUED) 1. DEQUEST 2060 as sold by Monsanto. 2. Sodium noniloxibencenesulfonate. 3. Sulfonated zinc phthalocyanine according to E.U.A. 4,033,718, Holcombe et al., Issued July 5, 1977. 4. Dirt releasing polymer according to the patent E.U.A. 5,415,807, Gosselink et al., Issued May 16, 1995.

. Dispersant based on ethoxylated polylene according to E.U.A. 5,565,145, Watson et al., Issued October 15, 1996. 6. Profragancy according to example 1. 7. Propragance according to example 5. The following compositions are later examples of granular laundry detergents according to the present invention.

TABLE III % by weight Ingredients 25 26 27 TABLE III (CONTINUED) 1. DEQUEST 2060 as sold by Monsanto. 2. Sodium noniloxibencenesulfonate. 3. Sulfonated zinc phthalocyanine according to E.U.A. 4,033,718, Holcombe et al., Issued July 5, 1977. 4. Dirt releasing polymer according to the patent E.U.A. 5,415,807, Gosselink et al., Issued May 16, 1995.

. Dispersant based on ethoxylated polylene according to E.U.A. 5,565,145, Watson et al., Issued October 15, 1996. 6. Propragance according to example 1. 7. Propragance according to example 12. The following compositions are later examples of granular laundry detergents according to the present invention.

TABLE IV % by weight Ingredients 28 29 37 TABLE IV (CONTINUED) 1. DEQUEST 2060 as sold by Monsanto. 2. Sodium nonylloxybenzene sulfonate. 3. Sulfonated zinc phthalocyanine according to E.U.A. 4,033,718, Holcombe et al., Issued July 5, 1977. 4. Dirt releasing polymer according to the patent E.U.A. 5,415,807, Gosselink et al., Issued May 16, 1995.

. Profragrance according to example 12. The following compositions are later examples of granular laundry detergents according to the present invention.

TABLE V -s in weight Ingredients 31 32 33 TABLE V (CONTINUED) 1. DEQUEST 2060 as sold by Monsanto. 2. Sodium noniloxibencenesulfonate. 3. Sulfonated zinc phthalocyanine according to E.U.A. 4,033,718, Holcombe et al., Issued July 5, 1977. 4. Dirt releasing polymer according to the patent E.U.A. 5,415,807, Gosselink et al., Issued May 16, 1995. 5. Propragance according to example 1. The above-illustrated compositions of laundry detergents are produced by combining sprinkle-dried granules with agglomerates. The alkybenzenesulfonic acid is neutralized and then placed in the steam jacketed mixer together with other materials. Other materials that can be fed to the steam jacketed mixer include: other anionic surfactants (such as acids or pre-neutralized), nonionic surfactants, cationic surfactants, chelating agents, polymeric dispersing agents, polymeric soil release agents , fillers, softening clays, fotoblanqueadores, phosphates, and optical brighteners. The dry and wet recirculating material can also be fed to the steam jacketed mixer and incorporated into the mix. The dry recirculation material generally comprises fine powders or material with excessive size from previous batches, preferably prepared from mixtures having the same composition of the mixture being prepared. The prepared mixture is spray-dried using conventional spray-drying equipment and proper spray-drying conditions. The mixture is pumped through nozzles to the spray-drying tower where it typically comes in contact with a mixture of air and carbon dioxide in countercurrent flow. The temperature of the air / C02 gaseous mixture enters the spray dryer at a temperature ranging from 200 ° C to 430 ° C. The gas mixture entering the spray dryer is typically with a content of 1% to 2% carbon dioxide. The amount of gas entering the spray dryer is typically between 1.5 and 2% per kg of granules produced. The agglomerates containing sodium carbonate are p produced in a high-cut LODIGE CB mixer and a moderate-speed LODIGE KM mixer is used to produce the agglomerate. The agglomerates are produced by feeding alkylbenzenesulfonic acid, phosphates, carbonates and sulfates to the CB mixer. Shortly after introducing the sodium carbonate into the CB mixer, it is finely ground using a Mikro-ACM CX model 300 mill from Hosokawa, Summit, NJ, such that most of the sodium carbonate particles entering the CB mixer They are under 10 microns in size. The CB mixer is operated at a speed of 275 rpm; the KM mixer is operated at a speed of 60 rpm. A finished laundry detergent product is therefore produced by the combination of spray-dried granules with agglomerates and materials that are added on the fly in a mixer type mixer with baffles. The granules, agglomerates, and enzymes are all introduced to the mixer as particulate solids. The perfume and the profragancia, and the coloring solution are sprayed to the dry materials near the exit of the mixer TABLE VI Detergent compositions that are in the form of a laundry soap that includes profaneness % by weight Ingredients 34 35 36 1. Commercially available from Dow Corning Corp 2. Profragancy according to example 12.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. - A laundry detergent composition comprising: a) At least about 0.01%, preferably from 0.01% to 15%, more preferably from 1% to 5%, more preferably 0.1% 1% by weight, of a β-ketoester which has the formula: wherein R is an alkoxy derivative of an alcohol of the fragrance raw material; R 1, R 2, and R 3 are each independently hydrogen, substituted or unsubstituted linear alkyl of C 1 -C 30, substituted or unsubstituted branched alkyl of C 3 -C 3 Q, substituted or unsubstituted C 3 -C 30 cyclic alkyl, substituted linear alkenyl or unsubstituted 2-C30, substituted or unsubstituted C3-C3Q branched alkenyl, substituted or unsubstituted C3-C3Q cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted branched alkynyl of c3_c30 'alkylenearyl substituted or unsubstituted C -C3Q, substituted or unsubstituted aryl of c6"c30 'a substituted or unsubstituted C2-C20 alkylene oxide substituted or unsubstituted C3-C2O alkylenearyl substituted or unsubstituted C7-C20 alkylenearyl, substituted or unsubstituted alkyleneoxyaryl of C -C20 / Y-1 -> mixtures thereof, providing that at least one R, R, or R is a unit having the formula: wherein R 4, R, and Rfi are each independently hydrogens, substituted or unsubstituted linear alkyl of C1-C30, substituted or unsubstituted branched alkyl of C3-C30, substituted or unsubstituted cyclic alkyl of C3-C30 substituted linear alkoxy or unsubstituted C1-C30, substituted or unsubstituted branched alkoxy of C3-C30, substituted or unsubstituted cycloalkoxy of 3-C30, substituted or unsubstituted linear alkenyl of C2-C30, substituted or unsubstituted branched alkenyl of C3- C30, substituted or unsubstituted C3-C30 cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl, substituted or unsubstituted C3-C30 substituted / unsubstituted Cg-C3Q alkynyl substituted or unsubstituted alkynyl; or R, R, and R can be taken together to form a substituted or unsubstituted aryl of C -C3Q; and mixtures thereof; b) at least about 0.01% by weight, preferably from 0.1% to 60%, more preferably from 0.1% to 30% by weight, of a detersive surfactant selected from the group consisting of ampholytic, zwitterionic, nonionic, cationic surfactants , and anionic, and mixtures thereof, preferably said surfactant is an anionic surfactant; and c) the rest are auxiliary ingredients and vehicles. 2. - A composition according to claim 1 further characterized in that R has the formula:

R, R, R and R are each hydrogen; and R is hydrogen, substituted or unsubstituted linear alkyl of] _-C] _, substituted or unsubstituted branched alkyl of C3-C] _, and mixtures thereof. 3. A composition according to claim 1 further characterized in that R has the formula:

R and R are each hydrogen, R, R and R are taken together to form a substituted or unsubstituted phenyl of C-C3Q, substituted or unsubstituted naphthyl of Cg-C3? and mixtures thereof. 4. - A composition according to claim 1 wherein said β-ketoester is selected from a group consisting of 3,7-dimethyl-l, 6-octadien-3-yl 3- (β-naphthyl) -3 -oxo -propionate, 2,6-dimethyl-7-octen-2-yl 3- (4-methoxyphenyl) -3 -oxo-propionate, 2,6-dimethyl-7-octen-2-yl-3- (4-nitrophenyl) ) -oxo-pro-pionate, 2,6-dimethyl-7-octen-2-yl 3- (ß-naphthyl) -3 -oxo-propionate, 3,7-dimethyl-l, 6-octadien-3-yl 3- (4-methoxyphenyl) -3-oxo-propionate, (O, O-4-trimethyl-3-cyclohexenyl) methyl 3- (ß-naphthyl) -3-oxo-propionate, 3,7-dimethyl- 1, 6-octadien-3-yl 3- (O-naphthyl) -3-oxo-propio-nato, cis 3-hexen-l-yl 3- (ß-naphthyl) -3 -oxo-propionate, 9-decen -l-il 3 - (ß-naphthyl) -3-oxo-propionate, 3,7-dimethyl-l, 6-octadien-3-lyl 3 - (nonanyl) -3 -oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3 - (nonanyl) -3 -oxo-propionate, 2,6-dimethyl-7-octen-2-yl-3-oxo-butyrate, 3,7-dimethyl -1,6-Octadien-3-yl-3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3- (ß-naphthyl) -3 -oxo-2-methylpropionate, 3,7-dimethyl -l, 6-octadien-3-yl 3- (ß-naphthyl) -3-oxo-2,2-dimethylpropio-nato, 3,7-dimethyl-1,6-octadien-3-yl 3- (ß- Naphthyl) -3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3 - (ß-naphthyl) -3 -oxo-propionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl -3-oxo-propionate, and mixtures thereof. 5. A composition according to claim 1 further characterized in that the auxiliary ingredients are selected from a group consisting of detergency builders, optical brighteners, whiteners, bleach boosters, bleach catalysts, bleach activators, release polymers of dirt, pigment transfer agent, dispersants, enzymes, foam suppressors, dyes, perfumes, pigments, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, agents chelators, stabilizers, anti-fouling agents, anti-creasing agents, germicides, fungicides, anticorrosive agents, and mixtures thereof. 6. A composition according to claim 1 which subsequently includes a dispersant having the formula:

H

I I [H2N-R] n + 1- [N-R] m- [N-R] n-NH2 wherein R is C 2 -C alkylene, m is from 3 to 70, n ranges from 0 to 35; and at least one hydrogen of an N-H unit is substituted with a propyleneoxy / ethyleneoxy unit having the formula:

- (CH2CHRO) and (CH2CH2?) XH where R 'is methyl or ethyl, xyy are independent and range from 0 to 50, providing that x + y is at least 1.

7. - A laundry detergent composition in the shape of a laundry bar including a) at least about 0.01%, preferably from 0.01% to 15%, more preferably from about 1% to 5%, and more preferably from about 0.1% to 1% by weight, of a β-ketoester having the formula: wherein R is an alkoxy derived from an alcohol of the material 1 9 3 fragrance bonus; R, R, and R are each independently hydrogenated, substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted branched alkyl of C3-C30, unsubstituted or substituted C3-C30 cyclic alkyl, substituted linear alkenyl or non-substituted C2-C30 substituted, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, substituted or unsubstituted C2-C30 linear alkynyl substituted or unsubstituted C3-C30 alkynyl, alkynylaryl substituted or unsubstituted C-C3Q, substituted or unsubstituted C-C3Q aryl, substituted or unsubstituted C2-C20 alkylene / substituted or unsubstituted C3-C20 alkylene substituted or unsubstituted C7-C20 substituted alkylene-xyryl aryl or unsubstituted of C -C20 and mixtures of the same 1; providing that at least one R, R or R is a unit that has the formula: wherein R 4, R 5 and R 6 are each independently hydrogenated, substituted or unsubstituted linear alkyl of C 1 -C 30, substituted or unsubstituted branched alkyl of C 3 -C 30, substituted or unsubstituted cyclic alkyl of C 3 -C 30"substituted linear alkoxy or unsubstituted C1-C30, substituted or unsubstituted branched alkoxy of C3-C3Q, substituted or unsubstituted cyclic alkoxy of C3-C30, substituted or unsubstituted linear alkenyl of C2-C30, substituted or unsubstituted branched alkenyl of C3-C30, C3-C3Q substituted or unsubstituted cyclic alkenyl, substituted or unsubstituted C2-C3Q linear alkynyl, substituted or unsubstituted C3-C30 alkynyl, substituted or unsubstituted aryl Cg-C3g alkylene; or R, R5 and R6 can be taken together to form a substituted or unsubstituted aryl of C -C3Q; and mixtures thereof; b) at least about 0.01% by weight, preferably from 0.1% to 60%, more preferably from 0.1% to 30% by weight, of a detersive surfactant selected from the group consisting of ampholytic, zwitterionic, nonionic surfactants, cationic, anionic, and mixtures thereof, preferably said surfactant is an anionic surfactant; and c) the rest are auxiliary ingredients and vehicles.

8. A composition according to claim 7, further characterized in that R has the formula: R2, R3, R and R5 are each hydrogen; and R is hydrogen, substituted or unsubstituted linear alkyl of C ^ - C ^ Q, substituted or unsubstituted branched alkyl of C ^ - C ^ Q, and mixtures thereof.

9. A composition according to claim 7, further characterized in that R1 has the formula: R and R are each hydrogen, R, R and R are taken together to form a substituted or unsubstituted phenyl or naphthyl of Cg-C30 and mixtures thereof.

10. A composition according to claim 7, further characterized in that said β-ketoester is selected from a group consisting of 3,7-dimethyl-l, 6-octadien-3-yl 3- (β-naphthyl) - 3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3- (4-methoxyphenyl) -3 -oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3 - (4 -nitrophenyl) -3 -oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3 - (ß-naph il) -3 -oxo-propionate, 3, 7-dimethyl-l, 6-octadien-3-yl 3- (4-methoxyphenyl) -3 -oxo-propionate, (O, O-4-trimethyl-3-cyclohexenyl) methyl 3- (ß-naphthyl) ) -3 -oxo-propionate, 3, 7-dimethyl-l, 6-octadien-3-yl 3- (O-naphthyl) -3 -oxo-propionate, cis 3-hexen-l-yl 3 - (ß- naphthyl) -3 -oxo-propionate, 9-decen-l-yl 3- (ß-naphthyl) -3-oxo-propionate, 3,7-dimethyl-l, 6-octadien-3-yl 3- (nonanil) -3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3- (nonanyl) -3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl-3-oxo-butyrate , 3, 7-dimethyl-l, 6-octadien-3-yl-3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3- (ß-naphthyl) -3 -oxo-2-methyl -propionate, 3, 7-dimethyl-l, 6-octanedien-3-yl 3- (ß-naphthyl) -3 -oxo-2,2-dimethylpropionate, 3,7-dimethyl-l, 6-octadien-3 - il 3 - (ß-naphthyl) -3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3- (ß-naphthyl) -3 -oxo-propionate, 3,7-dimethyl-2, 6-octanedienyl 3-heptyl-3-oxo-pro-pionate, and mixtures thereof.

11. A composition according to claim 7, further characterized in that the auxiliary ingredients are selected from a group consisting of detergency builders, optical brighteners, bleaches, bleach boosters, bleach catalysts, bleach activators, polymers of dirt release, pigment transfer agent, dispersants, enzymes, foam suppressors, pigments, perfumes, dyes, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, agents chelators, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anticorrosion agents, and mixtures thereof.

12. - A composition according to claim 7, which subsequently includes a dispersant having the formula: H [H2N-R] n + 1- [N I-R] m- [NI-R] n ~ NH2 wherein R is C 2 -C alkylene, ranges from 3 to 70, n ranges from 0 to 35; and at least one hydrogen of an N-H unit is substituted with a propyleneoxy / ethyleneoxy unit having the formula: - (CH2CHR'0) and (CH2CH2?) XH wherein R1 is methyl or ethyl, x and y are independent and range from 0 to 50, provided that x + y is at least 1.

13. A method for providing the benefits of the duration of the fragrance to fabrics including the step of contacting the fabric during hand washing with a laundry detergent composition comprising: (a) at least about 0.01%, preferably from 0.01% to 15%, more preferably from 1% to 5%, and more preferably from about 0.1% to 1% by weight of a beta-ketoester having the formula: wherein R is an alkoxide derived from a spirit of the material 1 2 3 fragrance bonus; R, R, and R are each independently hydrogens, substituted or unsubstituted linear alkyl of C] _- C3Q, substituted or unsubstituted branched alkyl of C3-C30, substituted or unsubstituted C3-C30 cyclic alkyl, substituted or unsubstituted C2-C30 linear alkenyl, substituted or unsubstituted C3-C30 alkenyl, unsubstituted or substituted C3-C30 cyclic alkenyl, linear alkynyl substituted or unsubstituted C2-C30, substituted or unsubstituted C3-C30 branched alkynyl, substituted or unsubstituted C4-C3g alkylene aryl; substituted or unsubstituted Cg-C30 aryl; C2-C20 substituted or unsubstituted alkylene oxide substituted or unsubstituted C3_C20 substituted or unsubstituted C7-C20 alkylenearyl substituted or unsubstituted C-C20 alkyl and mixtures of the same; providing that at least R, R, or R is a unit that has the formula wherein R, R5 and R6 are each independently hydrogens, substituted or unsubstituted linear alkyl of 1-C30, substituted or unsubstituted branched alkyl of C3-C3Q, substituted or unsubstituted cyclic alkyl of C3-C30, substituted linear alkoxide or unsubstituted C1-C30, substituted or unsubstituted branched alkoxide of C3-C30, substituted or unsubstituted cyclic alkoxide of C3-C30, substituted or unsubstituted linear alkenyl of C2-C30, substituted or unsubstituted branched alkenyl of C3-C3Q C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, substituted or unsubstituted C-C3Q alkylenearyl; or R, R5 and R can be taken together to form a substituted or unsubstituted aryl of Cg-C3Q; and mixtures thereof; (b) at least about 0.01% by weight, preferably from 0.1% to 60%, more preferably from 0.1% to 30% by weight, of a detersive surfactant selected from the group consisting of ampholytic, zwitterionic, nonionic surfactants, cationic, anionic, and mixtures thereof, preferably said surfactant is an anionic surfactant; and (c) the rest are the auxiliary ingredients and vehicles.