ORTHOCARBONATE PRO-FRAGRANCES

Abstract: The present invention relates to orthocarbonate pro-fragrances useful for delivery of sustained perfume or fragrance to fabric treated with a laundry detergent composition which comprises the herein described pro-fragrances. The orthocarbonate pro-fragrances are also suitable for use in hard surface cleaning compositions. The orthocarbonate pro-fragrances are further suitable for use in personal care compositions. The present invention also relates to method for delivering a pleasurable scent to fabric which has a lasting freshness quality by contacting the fabric with the fragrance-releasable orthocarbonate pro-fragrances of the present invention.

Description: ORTHOCARBONATE PRO-FRAGRANCES FIELD OF THE INVENTION The present invention relates to orthocarbonate pro-fragrance compounds useful in laundry detergent, hard surface cleaning, and personal care compositions for providing extended fragrance benefits. The orthocarbonates described herein are capable of releasing fragrance raw materials over an extended period of time thereby providing to fabric, hard surfaces, and human skin or hair an extended fragrance benefit. BACKGROUND OF THE INVENTION Humans have applied scents and fragrances to their skin since antiquity. Originally these aesthetically pleasing materials were commonly isolated in raw form as resins, gums or essential oils from natural sources, wter alia, the bark, roots, leaves and fruit of indigenous plants. These resins, gums, and oils were directly applied to the body or diluted with water or other solvent, including in some cases, wine. With the advent of modern chemistry, individual components responsible for the odor properties of these resins, gums and oils were isolated and subsequently characterized. However, formulators continue to search for materials which when applied to human skin or substrates and surfaces used by humans, will provide a pleasurable odor or scent and sustain that odor or scent for a long period of time. With regard to laundry detergent compositions, in addition to the removal of stains, dirt, soil, grime, and grease from fabric, formulators have attempted to deliver a "fresh" or "clean" odor to washed clothing to provide an olfactory aesthetic benefit and to serve as a signal that the product is effective. Laundry compositions, including rinse-added fabric softeners and dryer-added substrates, are currently formulated with perfume and fragrance ingredients which are aesthetically pleasing to the consumer but which fail to deliver a prolonged "fragrance" or "pleasurable smell" to the finished, cleaned fabric. It is well known that mixtures of perfume or fragrance raw materials when deposited on a substrate such as skin or fabric lose intensity and may change character with time, mainly due to factors such as differential evaporation and substrate penetration. Many attempts have been made to minimize these drawbacks, but so far without notable success. Particularly, efforts have been made to prolong the diffusion, as well as to improve other characteristics of fragrance materials, by e.g. increasing the fragrance raw material concentration or by using additives such as silicones, glycerol, polyethylene glycols and so on. Such additions, however, have never been adequate to increase the longevity of the fragrance odor. Accordingly, there remains a need in the art for pro-fragrances compounds which can be formulated into personal use articles, laundry detergent and hard surface cleaning compositions wherein the "perfume character" is released in a manner which provides for fragrance longevity. BACKGROUND ART In addition to the above-cited references, the following relate to the subject matter of fragrance ingredients. U.S. 5,378,468 Suffis et al., issued January 3, 1995; U. S. 5,266,592 Grub et al, issued November 30, 1993; U. S. 5,081,111 Akimoto et al, issued January 14, 1992; U. S. 4,994,266 Wells, issued February 19, 1991 ; U.S. 4,524,018 Yemoto et al, issued June 18, 1985; U. S. 3,849.326 Jaggers et al, issued November 19, 1974; U. S. 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 96/38528 published December 5, 1996; WO 96/14827 published May 23, 1996; WO 95/04809 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 herein by reference. SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in that it has been surprisingly discovered that perfume or fragrance raw materials can be delivered onto fabric "through the wash" via laundry detergent composition or to hard surfaces via a cleaning composition comprising orthocarbonates. In addition, orthocarbonates can be used to suitably deliver perfume and fragrance raw materials to "personal use articles" wter alia deodorants, talcs, lotions, and shampoos. The orthocarbonates are formed from fragrance raw materials and in the case of laundry detergent compositions impart a "fresh" or "clean" aesthetic odor benefit to the fabric. In addition to the short-term pleasurable odor benefits obtainable for fabric or cleaned surfaces, the orthocarbonates according to the present invention continue to release their fragrance raw materials for as long as several weeks depending on the structure of the orthocarbonate. The orthocarbonates described herein comprise fragrance raw materials in a stable, releasable form. The orthocarbonate-containing laundry detergent compositions of the present invention can comprise any number of orthocarbonates which when taken together are capable of releasing complex perfume fragrances. In addition, the orthocarbonates can be combined with other pro-perfumes or pro- fragrances for delivery of any type of fragrance "characteristic" desired by the formulator. The first aspect of the present invention relates to laundry detergent compositions which provide a sustained fragrance and freshness benefit to fabric, comprising: A) at least about 0.01%, preferably from about 0.01% to about 10%, more preferably from about 0.1 % to about 1% by weight, of a fragrance delivery system comprising: i) one or more orthocarbonate pro-fragrances having the formula: OR1 I R4O-C-OR2 I OR3 wherein Rl, R2, R3, and R^ are independently Cj-C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; C5-C20 substituted or unsubstituted aryl, C2- C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxyalkyl; C6-C40 substituted or unsubstituted alkylenearyl; C6-C40 substituted or unsubstituted aryloxy; Cg-C4Q substituted or unsubstituted alkyleneoxyaryl; or two Rl, R^, R3, and R^ are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; provided: a) one R 1 , R^, R3, or R^ comprises a fragrance raw material having a molecular weight greater than or equal to about 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to about 300 g/mol; ii) optionally one or more pro-fragrance materials selected from the group consisting of acetals, ketals, orthoesters, orthophosphates, orthosilicates, and mixtures thereof; iii) optionally one or more fragrance raw materials; B) at least about 0.01% by weight, preferably from about 0.1% to about 60%), more preferably from about 0.1% to about 30% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof, preferably said surfactant is an anionic surfactant; and C) the balance carriers and adjunct ingredients. Another aspect of the present invention relates to hard surface cleaning compositions having increased fragrance retention and fragrance longevity on hard surfaces, comprising: A) at least about 0.01%, preferably from about 0.01% to about 10%, more preferably from about 0.1 % to about 1% by weight, of a fragrance delivery system comprising: i) one or more orthocarbonate pro-fragrances having the formula: OR 1 I R4O—C— OR2 I OR3 wherein Rl, R^, R3, and R^ are independently C1 -C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; Cg-C20 substituted or unsubstituted aryl, C2- C40 substituted or unsubstituted alkyleneoxy; C3-C4Q substituted or unsubstituted alkyleneoxyalkyl; C6-C40 substituted or unsubstituted alkylenearyl; C6-C40 substituted or unsubstituted aryloxy; C6-C40 substituted or unsubstituted alkyleneoxy aryl; or two R^, R R->, and R^ are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; provided: a) at least one R! , R^, R3, or R^ comprises a fragrance raw material having a molecular weight greater than or equal to about 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to about 300 g/mol; ii) optionally one or more pro-fragrance materials selected from the group consisting of acetals, ketals, orthoesters, orthophosphates, orthosilicates, and mixtures thereof; iii) optionally one or more fragrance raw materials; at least about 0.01 % by weight, preferably from about 0.1 % to about 60%), more preferably from about 0.1% to about 30% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof, preferably at least about 0.1% of a sulfosuccinamate having the formula: wherein R! and R^ are hydrogen or -SO3M2 provided R^ does not equal R^; R3 is butyl when R^ is ethyl and R^ is pentyl when R^ is propyl; M and M^ are independently hydrogen or a salt forming cation; at least about 0.1 %>, preferably at least 0.5%> by weight, of a nonionic surfactant having the formula CH 3 (CH2) x CH2θ(CH2CH 2 O) y H wherein x is from about 6 to about 12, y is from about 3.5 to about 10; and C) the balance carriers and adjunct ingredients, said adjunct ingredients are selected from the group consisting of abrasives, builders, bleaches, bleach boosters, dispersents, enzymes, dyes, colorants, filler salts, hydrotropes, enzymes, preservatives, anti-oxidants, chelants, stabilizers, germicides, fungicides, photodisinfectants, and mixtures thereof. A further aspect of the present invention relates to personal care compositions for use on human skin or hair having increased fragrance retention and fragrance longevity, comprising the fragrance delivery system of the present invention together with one or more carriers and adjunct ingredients, said adjunct ingredients selected from the group consisting of surfactants, emollients, bactericides, gelling agents, desiccants, propellants, dyes, colorants, ointment bases, lanolin, sun screens, antiperspirants, mineral oil, talc, abrasives, optical brighteners, phase stabilizing agents, absorbents, UV sun screens, and mixtures thereof. A yet further object of the present invention is to provide orthocarbonate pro- fragrance materials which have a lasting fragrance benefit for an article or substrate inter alia fabric, hair, or human skin. These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to orthocarbonate pro-fragrance compounds and their use in compositions which have extended fragrance benefits. The orthocarbonates of the present invention can be used to provide these extended fragrance benefits to laundry detergent compositions, hard surface cleaning compositions, and personal care compositions. What is meant by personal care compositions are "compositions which are applied to human skin, hair, or delicate under garments (i.e. fine lingerie) which include ter alia shampoos, body lotions, body creams, suntan lotions (sun screens), ointments, medical balms, salves, and cosmetics". In addition, the orthocarbonates, due to their protracted release profiles, are suitable for use in animal odor control devices or compositions. The orthocarbonate pro-fragrances of the present invention have the general formula: ORl I R4O— C-OR2 I OR3 wherein R*, R^, R3 ? and R4 are independently C\ -C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; C6-C20 substituted or unsubstituted aryl, 2-C40 substituted or unsubstituted alkyleneoxy; C3-C4Q substituted or unsubstituted alkyleneoxyalkyl; C6-C40 substituted or unsubstituted alkylenearyl; Cg-C4Q substituted or unsubstituted aryloxy; C6-C40 substituted or unsubstituted alkyleneoxyaryl; any two Rl, R^, R->, and R^ are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; and mixtures thereof; preferably at least two of the moieties R 1 , R^, R3, and R^ are derived from a fragrance raw material alcohol, more preferably at least three of the moieties R% R^, R3 ? and R^ are derived from a fragrance raw material alcohol, most preferably each R*, R2, R3, and R^ is derived from one or more fragrance raw material alcohol. For the purposes of the present invention substituted or unsubstituted alkyleneoxy units are defined as moieties having the formula: R6 I — (CH 2 CHO) X R5 wherein R-> is hydrogen; RP is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 20. For the purposes of the present invention substituted or unsubstituted alkyleneoxyalkyl are defined as moieties having the formula: R6 -(CH 2 CHO) x (CH 2 ) y R5 wherein R^ is hydrogen, C1 -C1 g alkyl, C1-C4 alkoxy, and mixtures thereof; R6 is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 20 and the index y is from 2 to about 30. For the purposes of the present invention substituted or unsubstituted alkylenearyl units are defined as moieties having the formula: wherein R-> and R° are each independently hydrogen, hydroxy, C1-C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO 2 H; -CO 2 R'; -CONH 2 ; -CONHR; - CONR'2; wherein R is Cj-Ci 2 linear or branched alkyl), amino, alkylamino, and mixtures thereof, p is from 1 to about 34. For the purposes of the present invention substituted or unsubstituted aryloxy units are defined as moieties having the formula: wherein R^ and R^ are each independently hydrogen, hydroxy, Ci -C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO2H; -CO2 ; -CONH ; -CONHR; - CONR'2; wherein R is C1-C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof. For the purposes of the present invention substituted or unsubstituted alkyleneoxyaryl units are defined as moieties having the formula: wherein R^ and R6 are each independently hydrogen, hydroxy, Ci -C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO 2 H; -CO R; -CONH 2 ; -CONHR; - CONR'2; wherein R is C\-C\2 linear or branched alkyl), amino, alkylamino, and mixtures thereof, q is from 1 to about 34. For the purposes of the present invention substituted or unsubstituted oxyalkylenearyl units are defined as moieties having the formula: wherein R 3 and R" are each independently hydrogen, hydroxy, Ci -C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO2H; -CO2 ; -CONH 2 ; -CONHR; - CONR'2; wherein R is C1 -C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof, w is from 1 to about 34. Non-limiting examples of R*, R^, R , and R^ are methyl, 2,4-dimethyl-3- cyclo-hexene-1 -methyl (Floralol), 2,4-dimethyl cyclohexane methyl (Dihydro floralol), 5 ,6-dimethyl- 1 -methylethenyl-bicyclo [2.2.1 ]hept-5-ene-2-methyl (Arbozol), 2,4,6-trimethyl-3-cyclohexene-l -methyl (Isocyclo geranyl), 4-(l- methylethyl)cyclohexylmethyl (Mayol), α-3,3-trimethyl-2-norboranylmethyl, 1,1- dimethyl-l-(4-methylcyclohex-3-enyl)methyl, ethyl, 2-phenylethyl, 2- cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-methylphenyl)ethyl, 2-(p- methylphenyl)ethyl, 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-ethyl (nopyl), 2-(4- methylphenoxy)ethyl, 3,3-dimethyl-Δ 2 -β-norbornanylethyl, 2-methyl-2- cyclohexylethyl, l-(4-isopropylcyclohexyl)ethyl, 1-phenyl-l -hydroxy ethyl, 1,1- dimethyl-2-phenylethyl, l,l-dimethyl-2-(4-methylphenyl)ethyl, propyl, 1- phenylpropyl, 3-phenylpropyl, 2-phenylpropyl (Hydrotropic Alcohol), 2- (cyclododecyl)-propan-l-yl (Hydroxyambran), 2,2-dimethyl-3-(3- methylphenyl)propan-l-yl (Majantol), 2-methyl-3-phenylpropyl, 3-phenyl-2-propen- 1-yl (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-l-yl (methylcinnamyl alcohol), -n-pentyl-3-phenyl-2-propen-l-yl ( -amylcinnamyl alcohol), ethyl-Shy droxy-3-phenyl propionate, 2-(4-methylphenyl)-2-propyl, butyl, 3-methylbutyl, 3- (4-methylcyclohex-3-ene)butyl, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-l- yl)butyl, 2-ethyl-4-(2,2,3-trimethylcyclopent-3-enyl)-2-buten-l-yl, 3-methyl-2- buten-1-yl, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-l-yl)-2-buten-l-yl, 3- hydroxy-2-butanone, ethyl 3 -hydroxy butyrate, 4-phenyl-3-buten-2-yl, 2-methyl-4- phenylbutan-2-yl, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3- methoxyphenyl)butan-2-one, pentyl, cw-3-pentenyl, 3-methylpentyl, 3-methyl-3- penten-1-yl, 2-methyl-4-phenylpentyl (Pamplefleur), 3-methyl-5-phenylpentyl (Phenoxanyl), 2-methyl-5-phenylpentyl, 2-methyl-5-(2,3-dimethyltricyclo- [2.2.1.0(2,6)]hept-3-yl)-2-penten-l-yl (santalyl), 4-methyl-l-phenyl-2-pentyl, (1- methyl-bicyclo [2.1.1 ]hepten-2-yl)-2-methylpent- 1 -en-3 -yl, 3 -methyl- 1 -phenylpent- 3-yl, l,2-dimethyl-3-(l-methylethenyl)cyclopent-l-yl, 2-isopropyl-4-methyl-2- hexenyl, c/5-3-hexen-l-yl, trαrø-2-hexen-l-yl, 2-isopropenyl-5-methyl-4-hexen-l-yl (Lavandulyl), 2-ethyl-2-prenyl-3 -hexenyl (silwanol), 2-ethylhexyl, 1- hydroxymethyl-4-isopropenyl- 1 -cyclohexenyl (Dihydrocuminyl), 1 -methyl-4- isopropenylcyclohex-6-en-2-yl (carvenyl), 6-methyl-3-isopropenylcyclohex-l-yl, 1- methyl-4-isopropenylcyclohex-3-yl, 4-iso-propyl-l-methylcyclohex-3-yl, 4-tert- butylcyclohexyl, 2-tert-butylcyclohexyl, 2-tert-butyl-4-methylcyclohexyl, 4- isopropylcyclohexyl, 4-methyl- 1 -( 1 -methylethyl)-3-cyclohexen- 1 -yl, 2-(5,6,6- trimethyl-2-norbornyl)cyclohexyl, isobornylcyclohexyl, 3 ,3 ,5-trimethylcyclohexyl, l-methyl-4-isopropylcyclohex-3-yl (menthol), l,2-dimethyl-3-(l-methylethyl)- cyclohexan-1-yl, heptyl, 2,4-dimethylhept-l-yl, 2,4-dimethyl-2,6-heptandienyl, 6,6- dimethyl-2-oxymethylbicyclo [3.1.1 ]hept-2-en- 1 -yl (myrtenyl), 4-methyl-2,4- heptadien-1-yl, 3,4,5,6, 6-pentamethyl-2 -heptyl, 3,6-dimethyl-3-vinyl-5-hepten-2-yl, 6,6-dimethy 1-3 -hydroxy-2-methy lenebicyclo [3.1.1] -heptyl, 1 ,7,7-trimethylbicyclo- [2.2.1]hept-2-yl, 2,6-dimethylhept-2-yl, 2,6,6-trimethylbicyclo[l .3.3]hept-2-yl, octyl, 2-octenyl, 2-methyloctan-2-yl, 2-methyl-6-methylene-7-octen-2-yl (myrcenyl), 7-methyloctan-l-yl, 3,7-dimethyl-6-octenyl, 3,7-dimethyl-7-octenyl, 3,7-dimethyl-6-octen-l-yl (citronellyl), 3,7-dimethyl-2,6-octadien-l-yl (geranyl), 3,7-dimethyl-2,6-octadien-l-yl (neryl), 3,7-dimethyl-l,6-octadien-3-yl (linalyl), 3,7- dimethyloctan-1-yl (pelagryl), 3,7-dimethyloctan-3-yl (tetrahydrolinalyl), 2,4- octadien-1-yl, 3,7-dimethyl-6-octen-3-yl, 2,6-dimethyl-7-octen-2-yl, 2,6-dimethyl- 5,7-octadien-2-yl, 4,7-dimethyl-4-vinyl-6-octen-3-yl, 3-methyloctan-3-yl, 2,6- dimethyloctan-2-yl, 2,6-dimethyloctan-3-yl, 3,6-dimethyloctan-3-yl, 2,6-dimethyl-7- octen-2-yl, 2,6-dimethyl-3,5-octadien-2-yl (mugyl), 3-methyl-l-octen-3-yl, 7- hydroxy-3,7-dimethyloctanalyl. 3-nonyl, 6,8-dimethylnonan-2-yl, 3- (hydroxymethyl)-2-nonanone, 2-nonen-l-yl, 2,4-nonadien-l-yl, 2,6-nonadien-l-yl, cis-6-nonen-l-yl, 3,7-dimethyl-l,6-nonadien-3-yl, decyl, 9-decenyl, 2-benzyl-M- dioxa-5-yl, 2-decen-l-yl, 2,4-decadien-l-yl, 4-methyl-3-decen-5-yl, 3,7,9-trimethyl- l,6-decadien-3-yl (isobutyl linallyl), undecyl, 2-undecen-l-yl, 10-undecen-l-yl, 2- dodecen-1-yl, 2,4-dodecadien-l-yl, 2,7,1 l-trimethyl-2, 6,10-dodecatrien-1-yl (farnesyl), 3,7,1 l-trimethyl-l,6,10,-dodecatrien-3-yl, 3,7,11,15-tetramethylhexadec- 2-en-l-yl (phytyl), 3,7,1 l,15-tetramethylhexadec-l-en-3-yl (iso phytol), benzyl, p- methoxybenzyl (anisyl), τ?αrα-cymen-7-yl (cuminyl), 4-methylbenzyl, 3,4- methylenedioxybenzy 1, 2-(methy l)carboxy- 1 -hydroxyphenyl, 2-(benzyl)carboxy- 1 - hydroxyphenyl, 2-(cw-3-hexenyl)-carboxy-l -hydroxyphenyl, 2-(n-pentyl)carboxy-l - hydroxyphenyl, 2-(2-phenylethyl)carboxy- 1 -hydroxyphenyl, 2-(n-hexyl)carboxy- 1 - hydroxyphenyl, 2-methyl-5-isopropyl- 1 -hydroxyphenyl, 4-ethyl-2-methoxyphenyl, 4-allyl-2-methoxy- 1 -hydroxyphenyl (eugenyl), 2-methoxy-4-( 1 -propenyl)- 1 - hydroxyphenyl (isoeugenyl), 4-allyl-2,6-dimethoxy-l -hydroxyphenyl, 4-tert-butyl-l- hydroxyphenyl, 2-ethoxy-4-methyl- 1 -hydroxyphenyl, 2-methyl-4-vinyl- 1 - hydroxyphenyl, 2-isopropyl-5 -methyl- 1 -hydroxyphenyl (thymyl), 2-(isopentyl)- carboxy- 1 -hydroxyphenyl, 2-(ethyl)carboxy- 1 -hydroxyphenyl, 6-(methyl)carboxy- 2,5-dimethyl-l,3-dihydroxyphenyl, 5-methoxy-3-methyl-l-hydroxyphenyl, 2-tert- butyl-4-methyl-l -hydroxyphenyl, 1 -ethoxy-2-hydroxy-4-propenylphenyl, 4-methyl- 1 -hydroxyphenyl, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4- hydroxybenzaldehyde, decahydro-2-naphthyl, 2,5,5-trimethyl-octahydro-2-naphthyl, 1 ,3,3-trimethyl-2-norbornyl (fenchyl), 3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7- methano-lH-inden-5-yl, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-lH- inden-5-yl, 2-methyl-2-vinyl-5-( 1 -hydroxy- 1 -methylethyl)tetrahydrofuranyl, β- caryophyllenyl, and mixtures thereof. Preferred Rl, R^, R , and R^ are 4-(l-methylethyl)cyclohexanemethyl (mayol), 2,4-dimethyl-3-cyclohexen-l-ylmethyl (floralol), 2,4-dimethylcyclohex-l- ylmethyl (dihydrofloralol), 2,4,6-trimethyl-3-cyclohexen- 1 -ylmethyl (isocyclogeraniol), 2-phenylethyl, 1 -(4-isopropylcyclohexyl)ethyl (mugetanol), 2-(o- methylphenyl)ethyl, 2-(m-methylphenyl)ethyl, 2-(p-methylphenyl)ethyl, 2,2- dimethyl-3 -(3 -methylphenyl)propan- 1 -yl (maj antol), 3 -phenyl-2-propen- 1 -yl (cinnamic alcohol), 2-methyl-4-(2,2,3-trimethyl-3 -cyclopenten- l-yl)-2-buten-l-yl (santalaire), 3-methyl-5-phenylpentan-l-yl (phenoxanol), 3-methyl-5-(2,2,3- trimethyl-3 -cyclopenten- 1 -yl)-4-penten-2-yl (ebanol), 2-methyl-4-phenylpentan- 1 -yl (pamplefleur), -3-hexen-l-yl, 3,7-dimethyl-6-octen-l-yl (citronellol), 3,7- dimethyl-2,6-octadien-l-yl (geraniol, nerol or mixtures thereof), 7-methoxy-3,7- dimethyloctan-2-yl (osyrol), 6,8-dimethylnonan-2-ol, c/s-6-nonen-l-yl, 2,6- nonadien-1-ol, 4-methyl-3-decen-5-yl (undecavertol), benzyl, 2-methoxy-4-(l- propenyl)phenyl (isoeugenol), 2-methoxy-4-(2-propenyl)phenyl (eugenol), 4- hydroxy-3-methoxybenzaldehyde (vanillin), and mixtures thereof. The orthocarbonate pro-fragrances of the present invention undergo hydrolysis according to the following scheme: ORi O R4O— C— OR2 *► R4o— C— ORl + R 2 OH + R 3 OH OR3 and therein release one equivalent of a carbonate pro-fragrance and two equivalents of one or more fragrance raw materials. In addition to the initial release of two equivalents of alcohol by the scheme depicted herein above, the carbonate pro-fragrance materials which are released by the orthocarbonates can continue to hydrolyze and further release two equivalents of one or more fragrance raw material alcohol according to the following scheme: O R4θ— C— ORl » ► R4θH + R OH thereby providing up to four equivalents of fragrance raw material alcohol per equivalent of delivered orthocarbonate. The carbonate pro-fragrance which is released by the orthocarbonate may itself be a fragrance raw material in addition to being a pro-fragrance, preferably the carbonate which is released serves as a fragrance raw material. An orthocarbonate which comprises four different fragrance raw materials will always release a carbonate that is a pro-accord (hydrolyzes to release a binary accord) in addition to any further fragrance properties attributable to the carbonate. The alcohols which are released by the orthocarbonate pro-fragrances of the present invention may be "fragrance raw material alcohols", astringent alcohols, disinfectant alcohols, or carrier alcohols. For the purposes of the present invention "fragrance raw material alcohols" are defined herein as "alcohols having a molecular weight greater than or equal to 100 g/mol and which when used alone or in combination with other fragrance raw material alcohols have a generally pleasurable odor". Non limiting examples of alcohols which can be suitably released by the orthocarbonate pro-fragrances of the present invention are methanol, 2,4-dimethyl-3- cyclohexene-1 -methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro floralol), 5 ,6-dimethyl- 1 -methylethenylbicyclo [2.2.1 ]hept-5 -ene-2-methanol (Arbozol), 2,4,6-trimethyl-3-cyclohexene-l -methanol (Isocyclo geraniol), 4-(l- methylethyl)cyclohexanemethanol (Mayol), α-3,3-trimethyl-2-norborane methanol, l,l-dimethyl-l-(4-methylcyclohex-3-enyl)methanol, ethanol, 2-phenylethanol, 2- cyclohexyl ethanol, 2-(o-methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, 2-(p- methylphenyl)ethanol, 6,6-dimethylbicyclo-[3.1.1]hept-2-ene-2-ethanol (nopol), 2- (4-methylphenoxy)ethanol, 3,3-dimethyl-Δ 2 -β-norbornane ethanol, 2-methyl-2- cyclohexylethanol, l-(4-isopropylcyclohexyl)-ethanol, 1 -phenylethanol, 1,1- dimethyl-2-phenylethanol, l,l-dimethyl-2-(4-methyl-phenyl)ethanol, n-propanol, 2- propanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic Alcohol), 2-(cyclododecyl)propan-l-ol (Hydroxy-ambran), 2,2-dimethyl-3-(3- methylphenyl)propan-l-ol (Majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2- propen-1-ol (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-l-ol (methylcinnamyl alcohol), -n-pentyl-3-phenyl-2-propen-l-ol (α-amyl-cinnamyl alcohol), ethyl-3- hydroxy-3-phenyl propionate, 2-(4-methylphenyl)-2-propanol, n-butanol, 2-butanol, 3-methylbutanol, 3-(4-methylcyclohex-3-ene)butanol, 2-methyl-4-(2,2,3-trimethyl- 3-cyclopenten-l-yl)butanol, 2-ethyl-4-(2,2,3-trimethyl-cyclopent-3-enyl)-2-buten-l- ol, 3-methyl-2-buten-l-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-l-yl)-2-buten- l-ol, 3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2- methyl-4-phenylbutan-2-ol, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3- methoxyphenyl)butan-2-one, pentanol, cw-3-pentenol, 3-methyl-pentanol, 3-methyl- 3-penten-l-ol, 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-yl)-2-penten-l-ol (santalol), 4-methyl-l-phenyl- 2-pentanol, (l-methyl-bicyclo[2.1.l]hepten-2-yl)-2-methylpent-l-en-3-ol, 3-methyl- l-phenylpentan-3-ol, l,2-dimethyl-3-(l-methylethenyl)cyclopentan-l-ol, 2- isopropyl-5-methyl-2-hexenol, cw-3-hexen-l-ol, trans-2-hexen-\-o\, 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-l -ol, l-methyl-4-iso-propenylcyclohexan-3-ol, 4-isopropyl-l-methylcyclohexan-3-ol, 4- tert-butylcyclo-hexanol, 2-tert-butylcyclohexanol, 2-tert-butyl-4- methylcyclohexanol, 4-isopropyl-cyclohexanol, 4-methyl-l-(l-methylethyl)-3- cyclohexen-1-ol, 2-(5,6,6-trimethyl-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-trimethylcyclohexanol, l-methyl-4- isopropylcyclohexan-3-ol, l,2-dimethyl-3-(l-methylethyl)cyclohexan-l-ol, heptanol, 2,4-dimethylheptan- 1 -ol, 2,4-dimethyl-2,6-heptandienol, 6,6-dimethyl-2- oxymethylbicyclo[3.1.l]hept-2-ene (myrtenol), 4-methyl-2,4-heptadien-l-ol, 3,4,5,6, 6-pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6,6-dimethy- 3-hydroxy-2-methylenebicyclo[3.1.1]heptane, l,7,7-trimethylbicyclo[2.2.1]heptan- 2-ol, 2,6-dimethylheptan-2-ol, 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol, octanol, 2- octenol, 2-methyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol (myrcenol), 7- methyloctan-1-ol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-6- octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-l-ol (geraniol), 3,7-dimethyl-2,6- octadien-1-ol (nerol), 3,7-dimethyl-l,6-octadien-3-ol (linalool), 3,7-dimethyloctan- l-ol (pelagrol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-l-ol, 3,7- dimethyl-6-octen-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-5,7-octadien-2-ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-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 (muguol), 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-decenol, 2-benzyl-M-dioxa-5-ol, 2- decen-1-ol, 2,4-decadien-l-ol, 4-methyl-3-decen-5-ol, 3,7,9-trimethyl-l,6-decadien- 3-ol (isobutyl linallol), undecanol, 2-undecen-l-ol, 10-undecen-l-ol, 2-dodecen-l-ol, 2,4-dodecadien-l-ol, 2,7,1 l-trimethyl-2,6,10-dodecatrien-l-ol (farnesol), 3,7,1 1 - trimethyl-l,6,10,-dodecatrien-3-ol, 3,7,1 l,15-tetramethylhexadec-2-en-l-ol (phytol), 3,7,l l,15-tetramethylhexadecl-en-3-ol (iso phytol), benzyl alcohol, p-methoxy benzyl alcohol (anisyl alcohol), />αra-cymen-7-ol (cuminyl alcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxy benzyl 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-(l-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-ort/rø-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, 1 -ethoxy-2- hydroxy-4-propenylbenzene, 4-hydrozy toluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro- 2-naphthol, l,3,3-trimethyl-2-norbornanol (fenchol), 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- 1 H-inden-5-ol, 2-methyl-2-vinyl-5-( 1 -hydroxy- 1 - methylethyl)tetrahydrofuran, β-caryophyllene alcohol, and mixtures thereof. Preferred alcohols released by the orthocarbonate pro-fragrances of the present invention are 4-(l-methylethyl)cyclohexanemethanol (mayol), 2,4-dimethyl- 3-cyclohexen- 1 -ylmethanol (floralol), 2,4-dimethylcyclohex- 1 -ylmethanol (dihydrofloralol), 2,4,6-trimethyl-3-cyclohexen-l -ylmethanol (isocyclogeraniol), 2- phenylethanol, l-(4-isopropylcyclohexyl)ethanol (mugetanol), 2-(o-methylphenyl)- ethanol, 2-(m-methylphenyl)ethanol, 2-(p-methylphenyl)ethanol, 2,2-dimethyl-3-(3- methylphenyl)propan-l-ol (majantol), 3-phenyl-2-propen-l-ol (cinnamic alcohol), 2- methy l-4-(2,2,3 -trimethyl-3 -cyclopenten- 1 -yl)-2-buten- 1 -ol (santalaire), 3 -methyl-5 - phenylpentan-1-ol (phenoxanol), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-l-yl)-4- penten-2-ol (ebanol), 2-methyl-4-phenylpentan-l-ol (pamplefleur), cw-3-hexen-l-ol, 3,7-dimethyl-6-octen-l-ol (citronellol), 3,7-dimethyl-2,6-octadien-l-ol (geraniol, nerol or mixtures thereof), 7-methoxy-3,7-dimethyloctan-2-ol (osyrol), 6,8- dimethylnonan-2-ol, c/s-ό-nonen-l-ol, 2,6-nonadien-l-ol, 4-methyl-3-decen-5-ol (undecavertol), benzyl alcohol, 2-methoxy-4-(l-propenyl)phenol (isoeugenol), 2- methoxy-4-(2-propenyl)phenol (eugenol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), and mixtures thereof. The orthocarbonates of the present invention are surprisingly suitable for release of one or more tertiary alcohol fragrance raw materials. Non-limiting examples of tertiary alcohol fragrance raw materials include α,α-dimethyl phenethyl alcohol (dimethyl benzyl carbinol), α,α-4-trimethyl-3-cyclohexene-l -methanol (α- terpineol), , -4-trimethyl benzene ethanol (p-methyl dimethyl benzyl carbinol), 2- (4-methylphenyl)-2-propanol (Cymenol), 2-methyl-4-phenyl-2-butanol (phenyl ethyl dimethyl carbinol), 3-methyl-l-phenyl-3-pentanol (phenylethyl methylethyl carbinol), l,2-dimethyl-3-(l-methylethenyl) cyclopentanol (plinol), l,2-dimethyl-3- (1-methylethenyl) cyclohexanol l-methyl-4-isopropyl cyclohexan-8-ol (dihydrote ineol), 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene- 1 -carboxaldehyde (Lyral; Kovanol), 2,6-dimethyl-heptan-2-ol (Dimetol, Freesiol, Lolitol), 2,6,6- trimethylbicyclo[1.3.3]heptan-2-ol (cis-2-pinanol), 2,6,6- trimethylbicyclo[1.3.3]heptan-2-ol (cis and trans-2-pinanol), 2,6-dimethyl-2-octanol (tetrahydromyrcenol), 2-methyl-2-octanol (methyl octanol), 2,6-dimethyl-7-octen-2- ol (dihydromyrcenol), 2,6-dimethyl-7-octen-2-ol (lymolene), 2,6-dimethyl-3,5- octadien-2-ol (Muguol), 2-methyl-6-methylene-7-octen-2-ol (myrcenol), 2,6- dimethyl-5,7-octadien-2-ol (ocimenol), 3,6-dimethyl-3-octanol, 3-methyl-3-octanol (Aprol 161), 3, 7-dimethyl-3 -octanol and 2,6-dimethyl-2-octanol (tetrahydromuguol; tetralol; linacsol), 3,7-dimethyl-6-octen-3-ol (dihydrolinalool), 3,7-dimethyl-3- octanol (tetrahydrolinalool), 3-methyl-l-octen-3-ol (Aprol 160), 7-hydroxy-3,7- dimethyl octanol (hydrolene), 3,7-dimethyl-l,6-octadien-3-ol (linalool), 7-hydroxy- 3,7-dimethyl octanal (hydroxycitronellal; laurinal), 7-hydroxy-3,7-dimethyl octanal dimethyl acetal (hydroxycitronellal dimethyl acetal), 3,7-dimethyl-l,6-nonadien-3-ol (Ethyl Linalool), 2,5,5-trimethyl-octahydro-2-naphthalenol (Ambrinol), 2-Methyl-2- vinyl-5-(l -hydroxy- 1 -methyl-ethyl) tetrahydrofuran (cis and trans) (Linalool Oxide), 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-l -carboxaldehyde (Lyral; Kovanol), 4-methyl- 1 -( 1 -methylethyl)-3 -cyclohexen- 1 -ol, 3 ,7,9-trimethyl- 1 ,6-decadien-3 -ol (Isobutyl Linalool), 3,7,1 1,15-tetramethyl hexadec-l-en-3-ol (Iso phytol), Cedrol, and β-caryophyllene alcohol (caryophyllenol). In addition to fragrance raw materials, the orthocarbonate pro-fragrance compounds of the present invention may comprise alcohols which supply the orthocarbonates with increase fabric substantivity, skin lubricity, or a disinfectant component, for example release of a disinfectant alcohol (e.g. triclosan). In addition to the releasable alcohols listed herein above, orthocarbonates according to the present invention are also cyclic orthocarbonates which are comprised from at least one diol having the formula: wherein R^, R^, R10, and R! 1 are each independently hydrogen, Ci -C20 linear or branched alkyl, C1-C20 linear or branched alkenyl, Ci -C20 linear, branched or cyclic alkylenecarboxy, Ci -C20 linear, branched, or cyclic carboxyalkyl, Ci -C20 linear or branched alkyleneamino, Ci -C20 linear or branched aminoalkyl, Ci -C20 linear, branched, or cyclic alkylenecarboxamido, C1-C20 linear or branched carboxamidoalkyl, alkyleneoxy having the formula: Rl3 — (OCH 2 CH) χ (CH 2 ) yR 12 wherein Rl2 is hydrogen or methyl; R 3 is hydrogen or Ci -C2 alkyl; or any two R8, R9, R10 ? and R! 1 units can be taken together to form a fused ring or spiroannulated ring having from 3 to 8 carbons and optionally one or more heteroatoms in said ring, said ring is optionally further substituted by one or more C,-C 22 alkyl; n is from 0 to 4, x is from 1 to about 20, y is from 0 to about 20. An example of a cyclic orthocarbonate having one R° or R° unit which is a Ci -C20 linear, branched, or cyclic alkyl has the formula: wherein R - and R3 are each cis-3 -hexenyl. An example of a cyclic orthocarbonate having one R^ or R^ unit which is a Ci -C20 linear, branched, or cyclic alkylenecarboxy has the formula: FL C0 2 H C> .O ,o O. wherein R 2 and R3 are each citronellyl. An example of a cyclic orthocarbonate having one R° or R^ unit which is a Ci -C20 linear, branched, or cyclic alkylenecarboxy has the formula: wherein R 2 and R3 are each 2-phenylethyl. An example of a cyclic orthocarbonate having one R? or R^ unit which is a Ci -C20 linear, branched, or cyclic alkyleneamido has the formula: wherein R 2 and R are each vanillyl bis(methoxy) acetal. An example of a cyclic orthocarbonate having one R^ or R^ unit which is a C1-C20 linear, branched, or cyclic alkyleneamino has the formula: wherein x and R are each c/-s , -3-hexenyl. A further preferred orthocarbonate has the R^ or R^ unit taken together to form a spiro bis(orthocarbonate) an example of which has the formula: wherein the R 2 and R3 units of each orthoester is a 2-phenylethyl moiety. In addition, an R , R2, R3, or R^ unit may serve to link two pro-fragrances for the purpose of providing greater substantivity. An example of pro-fragrance linking by a diol has the following formula: Non-limiting examples of preferred orthocarbonate pro-fragrances according to the present invention include: bis(ethyl) bis(geranyl) orthocarbonate, bis(ethyl) bis(phenylethyl) orthocarbonate, bis(ethyl) bis(c/-s , -3-hexenyl) orthocarbonate, bis(ethyl) bis(citronellyl) orthocarbonate, bis(ethyl) bis(linalyl) orthocarbonate, bis(ethyl) bis(menthyl) orthocarbonate, bis(dodecyl) bis(geranyl) orthocarbonate, bis(dodecy) bis(phenylethyl) orthocarbonate. The more preferred orthocarbonate pro-fragrances of the present invention comprise at least three of the Rl, R2, R3 ; and R^ moieties which are derived from a fragrance raw material alcohol, thereby the preferred pro-fragrances have a molecular weight which is at least 3 times the molecular weight of the lowest "fragrance raw material alcohol" which comprises the orthocarbonate pro-fragrance. Further, the more preferred orthocarbonate pro-fragrances have a molecular weight which is greater than or equal to 325 g/mol. Non-limiting examples of more preferred orthocarbonate pro-fragrances according to the present invention include: methyl tris(geranyl) orthocarbonate, ethyl tris(geranyl) orthocarbonate, methyl tris(phenyethy) orthocarbonate, ethyl tris(phenylethyl) orthocarbonate, methyl tris(cis-3 -hexenyl) orthocarbonate, ethyl tris(cw-3 -hexenyl) orthocarbonate, methyl tris(citronellyl) orthocarbonate, ethyl tris(citronellyl) orthocarbonate, methyl tris(linalyl) orthocarbonate, ethyl tris(linalyl) orthocarbonate, methyl tris(menthyl) orthocarbonate, ethyl tris(menthyl) orthocarbonate, dodecyl tris(geranyl) orthocarbonate, dodecyl tris(phenylethyl) orthocarbonate. The most preferred orthocarbonate pro-fragrances of the present invention have each of the Rl, R2, R3, and R^ moieties derived from a fragrance raw material alcohol, thereby the preferred pro-fragrances have a molecular weight which is at least 4 times the molecular weight of the lowest "fragrance raw material alcohol" which comprises the orthocarbonate pro-fragrance. Further, the preferred orthocarbonate pro-fragrances have a molecular weight which is greater than or equal to 350 g/mol. Non-limiting examples of most preferred orthocarbonate pro-fragrances according to the present invention include: tetrakis(geranyl) orthocarbonate, tetrakis(phenylethyl) orthocarbonate, tetrakis(c.-y-3 -hexenyl) orthocarbonate, bis(geranyl) bis(c/-s , -3 -hexenyl) orthocarbonate, bis(phenylethyl) bis(cis-3 -hexenyl) orthocarbonate, tetrakis(citronellyl) orthocarbonate, tetrakis(linalyl) orthocarbonate, bis(linallyl) bis(geranyl) orthocarbonate, tetrakis(myrcenyl) orthocarbonate, tetrakis(cinnamyl) orthocarbonate. ClogP of Orthocarbonates The preferred pro-fragrances, especially those useful in laundry detergent and hard surface cleaning compositons of the invention, are also characterized by their octanol/water partition coefficient P. The octanol/water partition coefficient of a pro-fragrance is the ratio between its equilibrium concentration in octanol and in water. Since the partition coefficients of the pro-fragrance compounds are large, they are more conveniently given in the form of their logarithm to the base 10, logP. The logP of many compounds have been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP" program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database. The "calculated logP" (CLogP) is determined by the fragment approach of Hansch and Leo (cf, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J.B. Taylor and CA. Ramsden, Eds., p. 295, Pergamon Press, 1990). The fragment approach is based on the chemical structure of a compound and takes into account the numbers and type of atoms, the atom connectivity, and chemical bonding. The CLogP values, which are the most reliable and widely used estimates for this physicochemical property, can be used instead of the experimental logP values in the selection of pro-fragrances. The pro-fragrances of the present invention have a ClogP greater than or equal to 2, preferably greater than or equal to 3, more preferably greater than or equal to 4, most preferably greater than or equal to 5. Laundry Detergent Compositions The laundry detergent compositions of the present invention comprise a fragrance delivery system which lays down one or more orthocarbonate pro- fragrance compounds onto the fabric surface during the laundry wash cycle. Because the orthocarbonate pro-fragrances have a higher molecular weight than the fragrance raw materials from which they are derived and a ClogP greater than or equal to about 2, they are highly fabric substantive and therefore remain on the fabric surface even through the heating which occurs during automatic dryer usage. Once the laundry cycle is complete, the orthocarbonate pro-fragrance begins to release the fragrance raw materials and because this release of fragrance raw material is protracted, the fabric remains "fresh" and "clean" smelling longer. However, orthocarbonate pro-fragrances according to the present invention can also be designed to be "heat activated" so as to release a "freshening scent" to the fabric during drying. Therefore, heat-activated orthocarbonates can be delivered to the fabric surface. This results in a fabric having high "initial scent" as well as the lower "clean" and "fresh" scent obtained by the protracted release of non-activated orthocarbonate pro-fragrances. What is meant herein by "heat activated" pro- fragrances are compounds which have a higher release rate of their fragrance materials at elevated temperatures. Therefore the formulator may achieve an initial high fragrance delivery coupled with the longer term sustained release. The orthocarbonate pro-fragrances of the present invention are therefore a means for delivering two or more fragrance raw materials onto fabric and thereby providing the fabric with a longer and more sustained "fresh" or "clean" smell. Mixtures of two or more released fragrance raw materials are known by those skilled in the art of fragrances and perfumes as "accords", therefore orthocarbonates which release two or more complimentary fragrance raw materials are also considered to by "pro-accords". The term "accord" as used herein is defined as "mixtures of two or more 'fragrance raw materials' which are combined to impart a pleasurable scent, odor, or fragrance characteristic". For the purposes of the present invention "fragrance raw materials" are herein defined as compounds having a molecular weight of at least 100 g/mol and which are useful in imparting an odor, fragrance, essence, or scent either alone or in combination with other "fragrance raw materials". Most of the fragrance raw materials which comprise the pro-fragrances of the present invention are not deliverable as individual compounds to fabric via the laundry cycle either due to solubility factors (lost or rinsed away during the laundry cycles), substantivity factors (do not sufficiently adhere to fabric surface), of volatility factors (evaporation during the drying cycle). Therefore, the pro- fragrances described herein are a means for delivering certain fragrance raw materials to fabric which could not have previously been effectively or efficiently delivered. For example, but not by way of limitation, the fragrance accords released by the pro-fragrances of the present invention have a "heart", "character", or "note" which is described as ter alia rose, jasmin, lilac, lily of the valley, violet, orange, peach, watermelon, and lemon. The accord may be further "modified" or "twisted" by the use of modifier top or middle notes which, as an additional benefit afforded by the present invention, can be incorporated into the pro-accord. For example, a "rose essence" may be combined with a "green" modifier to "shift the fragrance accord character". For the purposes of the present invention the terms "fresh", "fresh-like", "fresh smelling", "clean", "clean-like" and "clean smelling" are terms used to describe the sensory effect produced by the release of the fragrance raw materials which comprise the pro-fragrances of the present invention. The presence of perfume components and fragrance raw materials upon a fabric up to two weeks after washing are regarded as imparting the aforementioned sensory effects. Laundry Detergent Compositions Laundry detergent compositions according to the present invention comprise: A) at least about 0.01 %, preferably from about 0.01 % to about 10%, more preferably from about 0.1%) to about 1% by weight, of a fragrance delivery system comprising: i) one or more orthocarbonate pro-fragrances having the formula: OR l I R4O— C-OR2 I OR3 wherein Rl, R2, R , and R^ are independently Ci -C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; C6-C20 substituted or unsubstituted aryl, C2- C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxyalkyl; C6-C40 substituted or unsubstituted alkylenearyl; C6-C40 substituted or unsubstituted aryloxy; C6-C40 substituted or unsubstituted alkyleneoxy aryl; or two R , R 2 , R3, and R^ are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; provided: a) one R , R2, R 5 0 r R^ comprises a fragrance raw material having a molecular weight greater than or equal to about 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to about 300 g/mol; ii) optionally one or more pro-fragrance materials selected from the group consisting of acetals, ketals, orthoesters, orthophosphates, orthosilicates, and mixtures thereof; iii) optionally one or more fragrance raw materials; B) at least about 0.01%> by weight, preferably from about 0.1 %> to about 60%), more preferably from about 0.1% to about 30%> by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof, preferably said surfactant is an anionic surfactant; and C) the balance carriers and adjunct ingredients, said adjunct ingredients are selected from the group consisting of abrasives, builders, bleaches, bleach boosters, dispersents, enzymes, dyes, colorants, filler salts, hydrotropes, enzymes, preservatives, anti-oxidants, chelants, stabilizers, germicides, fungicides, photodisinfectants, and mixtures thereof. The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. Granular Compositions The pro-fragrance orthocarbonates of the present invention can be used in both low density (below 550 grams/liter) and high density granular compositions in which the density of the granule is at least 550 grams/liter. Granular compositions are typically designed to provide an in the wash pH of from about 7.5 to about 11.5, more preferably from about 9.5 to about 10.5. Low density compositions can be prepared by standard spray-drying processes. Various means and equipment are available to prepare high density compositions. Current commercial practice in the field employs spray-drying towers to manufacture compositions which have a density less than about 500 g/1. Accordingly, if spray-drying is used as part of the overall process, the resulting spray-dried particles must be further densified using the means and equipment described hereinafter. In the alternative, the formulator can eliminate spray-drying by using mixing, densifying and granulating equipment that is commercially available. The following is a nonlimiting description of such equipment suitable for use herein. Various means and equipment are available to prepare high density (i.e., greater than about 550, preferably greater than about 650, grams/liter or "g/1"), high solubility, free-flowing, granular detergent compositions according to the present invention. Current commercial practice in the field employs spray-drying towers to manufacture granular laundry detergents which often have a density less than about 500 g/1. In this procedure, an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of about 175°C to about 225°C. However, if spray drying is used as part of the overall process herein, additional process steps as described hereinafter must be used to obtain the level of density (i.e., > 650 g/1) required by modern compact, low dosage detergent products. For example, spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and or subjecting them to one or more high speed mixer/densifiers. A suitable high speed mixer/densifier for this process is a device marketed under the tradename "Lδdige CB 30" or "Lδdige CB 30 Recycler" which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon. In use, the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See Jacobs et al, U.S. Patent 5,149,455, issued September 22, 1992. The preferred residence time in the high speed mixer/densifier is from about 1 to 60 seconds. Other such apparatus includes the devices marketed under the tradename "Shugi Granulator" and under the tradename "Drais K-TTP 80). Another process step which can be used to densify further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower intraparticle porosity. Equipment such as that marketed under the tradename "Lδdige KM" (Series 300 or 600) or "Lδdige Ploughshare" mixer/densifiers are suitable for this process step. Such equipment is typically operated at 40-160 rpm. The residence time of the detergent ingredients in the moderate speed mixer/densifier is from about 0.1 to 12 minutes. Other useful equipment includes the device which is available under the tradename "Drais K-T 160". This process step which employs a moderate speed mixer/densifier (e.g. Lόdige KM) can be used by itself or sequentially with the aforementioned high speed mixer/densifier (e.g. Lόdige CB) to achieve the desired density. Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942. While it may be more suitable to use the high speed mixer/densifier followed by the low speed mixer/densifier, the reverse sequential mixer/densifier configuration is also contemplated by the invention. One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules in the process of the invention. By way of example, see the processes in Appel et al, U.S. Patent 5,133,924, issued July 28, 1992 (granules are brought into a deformable state prior to densification); Delwel et al, U.S. Patent 4,637,891, issued January 20, 1987 (granulating spray- dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate). In those situations in which particularly heat sensitive or highly volatile detergent ingredients are to be incorporated into the final detergent composition, processes which do not include spray drying towers are preferred. The formulator can eliminate the spray-drying step by feeding, in either a continuous or batch mode, starting detergent ingredients directly into mixing/densifying equipment that is commercially available. One particularly preferred embodiment involves charging a surfactant paste and an anhydrous builder material into a high speed mixer/densifier (e.g. Lδdige CB) followed by a moderate speed mixer/densifier (e.g. Lδdige KM) to form high density detergent agglomerates. See Capeci et al, U.S. Patent 5,366,652, issued November 22, 1994 and Capeci et al, U.S. Patent 5,486,303, issued January 23, 1996. Optionally, the liquid/solids ratio of the starting detergent ingredients in such a process can be selected to obtain high density agglomerates that are more free flowing and crisp. Optionally, the process may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer/densifiers for further agglomeration or build-up. The oversized particles produced by this process can be sent to grinding apparatus and then fed back to the mixing/densifying equipment. These additional recycle process steps facilitate build-up agglomeration of the starting detergent ingredients resulting 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, U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996. Other suitable processes which do not call for the use of spray-drying towers are described by Bollier et al, U.S. Patent 4,828,721, issued May 9, 1989; Beerse et al, U.S. Patent 5,108,646, issued April 28, 1992; and, Jolicoeur, U.S. Patent 5,178,798, issued January 12, 1993. In yet another embodiment, the high density detergent composition of the invention can be produced using a fluidized bed mixer. In this process, the various ingredients of the finished composition are combined in an aqueous slurry (typically 80%) solids content) and sprayed into a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, this process can optionally include the step of mixing the slurry using the aforementioned Lόdige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can be used in such processes. Another suitable process which can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients. Optionally, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e.g. Lόdige KM) for further agglomeration resulting in the finished high density detergent composition. See Appel et al, U.S. Patent 5,164,108, issued November 17, 1992. Hard Surface Cleaning Compositions The orthocarbonate pro-fragrances are useful for delivering a pleasurable scent or fragrance to a hard surface which has been cleaned. The slow release of the fragrance raw material provides for a protracted sense of "freshness". The hard surface cleaners of the present invention can be in any form inter alia liquid, semi-solid, gelatinous, or solid. The cleaner may be a scouring cleaner and therefore comprise an abrasive material. Hard surface cleaning compositions according to the present invention having enhanced perfume retention as well as high surface shine and low streaking, comprises: A) at least about 0.01 %, preferably from about 0.01 %> to about 10%, more preferably from about 0.1%) to about 1% by weight, of a fragrance delivery system comprising: i) one or more orthocarbonate pro-fragrances having the formula: OR l I R4O— C-OR2 I OR3 wherein R , R 2 , R3 ? and R^ are independently C1 -C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; Cg-C20 substituted or unsubstituted aryl, C2- C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxyalkyl; C5-C40 substituted or unsubstituted alkylenearyl; C6-C40 substituted or unsubstituted aryloxy; C6-C40 substituted or unsubstituted alkyleneoxyaryl; or two R , R2, R3, and R^ are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; provided: a) at least one R , R 2 , R3, or R^ comprises a fragrance raw material having a molecular weight greater than or equal to about 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to about 300 g/mol; ii) optionally one or more pro-fragrance materials selected from the group consisting of acetals, ketals, orthoesters, orthophosphates, orthosilicates, and mixtures thereof; iii) optionally one or more fragrance raw materials; B) at least 0.01%> by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; and C) the balance carriers and adjunct ingredients, said adjunct ingredients selected from the group consisting of abrasives, builders, bleaches, bleach boosters, clays, detersive surfactants, thickeners, dispersents, enzymes, dyes, colorants, filler salts, hydrotropes, enzymes, preservatives, anti-oxidants, chelants, stabilizers, germicides, fungicides, solvents, photodisinfectants, and mixtures thereof. This example of a preferred hard surface cleaning composition according to the present invention described above comprises either the dianionic surfactant N-2- ethylhexyl sulfosuccinamate, N-2-propylheptyl sulfosuccinamate, or mixtures thereof having the formula: wherein R and R 2 are selected from hydrogen or the moiety -SO3M2, provided however that R and R 2 are not the same, that is when R is hydrogen, R 2 must be -SO3M2 and vice versa. M and yfi are independently selected from hydrogen or a salt forming cation. Three carbon atoms in the above molecule are chiral centers, that is they individually have the capacity to form optical isomers or enantiomers. In addition, when two or more of these chiral carbons are taken together they may form diasteriomeric pairs or combinations. For the purposes of the present invention the N-2-ethylhexyl sulfosuccinamate is drawn such that each chiral center is shown in its racemic form. For the purposes of the present invention all isomeric forms of N- 2-ethylhexyl sulfosuccinamate are suitable for use in the compositions of the present invention. M and M 2 may be hydrogen or a salt forming cation depending upon the method of synthesis chosen and the pH of the final hard surface cleaner. Examples of salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula R3 R6— N-R4 wherein R , R4, R5 and R are independently hydrogen, C1-C22 alkylene, C4-C22 branched alkylene, C1 -C5 alkanol, C1 -C22 alkenylene, C4-C22 branched alkenylene, and mixtures thereof. A different salt forming cation may be chosen for the carboxylate moiety (-CO2 " ) than is chosen for the sulfonate moiety (-SO3"). Preferred cations are ammonium (R3, R4, R5 an d R6 equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof. The monoalkanol ammonium compounds of the present invention have R3 equal to Ci - Cg alkanol, R4, R5 and R^ equal to hydrogen; dialkanol ammonium compounds of the present invention have R3 and R4 equal to Ci -Cg alkanol, R? and R° equal to hydrogen; trialkanol ammonium compounds of the present invention have R , R4 and R5 equal to Cj-Cg alkanol, R^ equal to hydrogen. Preferred alkanol ammonium salts of the present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas: H 3 N + CH 2 CH2OH, H 2 N + (CH2CH 2 OH)2, HN+(CH2CH 2 OH) 3 . Preferred M and M 2 are hydrogen, sodium, potassium and the C2 alkanol ammonium salts listed above; most preferred are hydrogen and sodium. Nonionic surfactant The hard surface cleaning compositions of the present invention preferably further comprises a nonionic surfactant having the formula CH3(CH 2 ) x CH2θ(CH2CH 2 O) y H wherein x is from about 6 to about 12, preferably from about 8 to about 10; y is from about 3.5 to about 10, preferably from about 4 to about 7. For the purposes of the present invention the index y refers to the average degree of ethoxylation obtained when contacting a suitable alcohol with a source of ethyleneoxy moieties, and therefore represents all fractional parts within the range 3.5 to 10. Other preferred hard surface cleaning compositions include solid scouring powders having abrasives such as perlite or sodium carbonate, foam cleaners, and liquids wherein the carrier material may comprise liquids other than water. Personal Care Compositions The personal care compositions of the present invention comprise at least about 0.01%, preferably from about 0.01%) to about 10%>, more preferably from about 0.1%) to about 1% by weight, of the fragrance delivery system of the present invention. An example of a personal care compositions of the present invention is the following skin care composition which comprises an ester having a total number of carbon atoms in excess of about 28, for example lauryl laurate, lauryl myristate, myristyl myristate, behenyl.caprate, cetearyl palmitate, behenyl stearate, more preferably cetearyl palmitate and cetyl stearate. The present compositions in addition to the esters described herein above, contain an emollient material in an amount such that the amount of ester plus emollient is from about 0.2%> to about 25%) of the total composition, preferably from about 4% to about 18%. One function of the emollient is to ensure that the ester is plasticized sufficiently to allow it to be in a film-like state on the skin. The emollient in the present compositions is selected from the group consisting of fatty alcohols, esters having fewer than about 24 total carbon atoms (e.g. isopropyl palmitate), branched chain esters having greater than about 24 total carbon atoms (e.g. cetearyl octonate), squalane, liquid or solid paraffins, mixtures of fatty acids and squalane, mixtures of fatty acids and liquid or solid paraffins and mixtures thereof. The aforementioned esters, those having fewer than 24 carbon atoms or branched and having more than 24 carbon atoms, if used as an emollient should preferably be used in an mount equal to about a third of the long chain ester. The particular emollient selected depends in part on the particular ester selected since proper plasticization, as indicated above, is desired. The emollient for the esters having more than 28 carbon atoms is preferably selected from the group consisting of squalane, liquid or solid paraffins and mixtures of fatty alcohols with squalane or paraffins. Typical fatty alcohols and fatty acids useful in the present compositions include those having from 12-22 carbon atoms such as cetyl alcohol, myristyl alcohol, stearyl alcohol, stearic acid and palmitic acid. Paraffins include, for example, mineral oil, petrolatum and paraffin wax. Water It is preferred that distilled water be used in the present compositions. OPTIONAL COMPONENTS Oil Phase Components In addition to the long chain esters, emollients and emulsifiers described previously, the oil phase of the present compositions may contain a variety of materials including: (a) Esters not meeting the requirements for the long chain ester and not present as an emollient, supra, such as oleyl oleate, isostearyl isostearate, isopropyl lanolate, isopropyl myristate, butyl stearate, myristyl lactate and 2-ethyl hexyl palmitate; (b) Oils such as castor oil, jojoba oil, cottonseed oil, peanut oil and sesame oil; (c) Waxes such as ceresin wax, carnuba wax, beeswax and castor wax; (d) Lanolin, its derivatives and components such as acetylated lanolin, lanolin alcohols and lanolin fatty acids. Lanolin fatty acids are described in U.S. Pat. No. Re. 29,814, Oct. 24, 1978 to W. E. Snyder incorporated herein by reference. (e) Polyalkylenes such as hydrogenated polyisobutene and polyethylene; and (f) Sterols such as cholesterol and phytosterol. These optional oil phase materials may comprise up to about 80%> of the oil phase, preferably up to about 35%>. When used at these levels, the optional components do not impair the occlusive nature of the compositions and add to the composition's total cosmetic performance. Water Phase Components The water phase of the compositions may contain many different materials including: (a) Humectants, such as sorbitol, glycerine, propylene glycol, alkoxylated glucose and hexanetriol at a level of from about 1%> to about 20%). (b) Thickening agents such as carboxyvinyl polymers, ethyl cellulose, polyvinyl alcohol, carboxymethyl cellulose, vegetable gums and clays such as Veegum.RTM. (magnesium aluminum silicate, R. T. Vanderbilt, Inc.) at a level of from about 0.01% to about 6%; (c) Proteins and polypeptides at a level of from about 0.1%> to about 3%; (d) Preservatives such as the methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid (Parabens-Mallinckrodt Chemical Corporation) EDTA and imidazolidinyl urea (Germall 115-Sutton Laboratories) at a level of from about 0.2% to about 2.5%>; and (e) An alkaline agent such as sodium hydroxide to neutralize, if desired, part of the fatty acids or thickener which may be present. All of the percentages of these additional water phase components are of the total composition. The present compositions may also contain agents suitable for aesthetic purposes such as dyes. The compositions of the present invention are preferably substantially free of materials which adversely affect their performance. Therefore, such things as polyethylene glycols are preferably present only at levels below about 1%) of the total composition. The pH of the present compositions is preferably in the range of about 7.5-10. The present invention also relates to a process for preparing unsymmetrical orthocarbonate pro-accords comprising the step of admixing two or more fragrance raw material alcohols with an orthocarbonate producing agent. METHOD OF MANUFACTURE The personal care compositions of the present invention generally have a lotion consistency and may be in the form of oil-in- water or water-in-oil emulsions with the former being preferred because of their more pleasing cosmetic properties. The compositions of the present invention are preferably made by the method comprising the steps of; a) preparing the oil phase; b) preparing the water phase; and c) adding the oil phase to the water phase. Step (a) is carried out by heating the oil phase materials to a temperature of about 75° C to about 100° C. Step (b) is carried out by heating the water phase materials to a temperature about the same as that of the oil phase. The emulsion is formed by slowly adding the oil phase prepared in step (a) to the water phase prepared in step (b) with stirring. Other ingredients may be added to the phase in which they are soluble prior to the mixing of the two phases or added directly to the mixed water and oil phases. Animal Odor Control Compositions In addition to the fragrance-containing compositions for use on human skin, the pro-accords of the present invention are also suitable for use in any odor controlling or fragrance mediating application. A example is animal litter and odor control articles useful in lining the cages, stalls, and other living areas of domesticated animals. For example, U.S. 5,339,769 Toth et al., issued August 23, 1994 describes a process for making an absorbent composition which can well accommodate the pro-accord materials of the present invention. An example of a suitable litter material which comprises the pro-accords of the present invention can be formed by the following process. A Glatt fluid bed granulator is charged with 1,0000 g of bentonite clay (90 %> of the particles being greater than 420 microns) and 10 g of a cellulose ether (Methocel ™ K15M Premium, a cellulose ether having a viscosity of 15,000 centipoise (cps) as a 2 % aqueous solution). The granulator is started an the product temperature is brought up to about 40° C (outlet temperature). When the outlet temperature reaches about 40° C, atomized water is sprayed onto the moving powders within the granulator, During the granulation process, inlet air temperature is maintained at 70° C to 80° C; air atomization pressure is 28-35 psi; and the spraying cycle is for 45 seconds with a 15 second shaking time. The clay/cellulose ether agglomerates swell over time. The water hydrates the cellulose ether polymer which produces adhesion to form the granule. At this time it is more advantageous to introduce the pro-accord materials of the present invention. The formation of the granule promotes aggregation of the small sized particles of the inert substrate, e.g. clay particles of about 50 to 600 microns. The formation of a granule significantly reduces the quality of dust in the final product while the litter forms an agglomerate when wetted. In an alternative embodiment of the clay-based litter box articles/pro-accord admixture, once the clay articles have been formed, a concentrated solution, or an carrier alcohol-based admixture of the pro-accords may be delivered to the surface of the granule by a suitable means. ADJUNCT INGREDIENTS The following are non-limiting examples of adjunct ingredients suitable for use in the present invention. Surfactant systems The instant cleaning compositions contain at least about at least about 0.01%> by weight, preferably from about 0.1% to about 60%>, more preferably from about 0.1%) to about 30%) by weight, of a surfactant selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surface active agents. Preferably the solid (i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems of the present invention, surfactant is preferably present to the extent of from about 0.1 %> to 30 %> by weight of the composition. Prefered detersive surfactants are anionic surfactants. Nonlimiting examples of surfactants useful herein typically at levels from about 1%) to about 55%>, by weight, include the conventional C \ -Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C\ 0-C20 alkyl sulfates ("AS"), the Cι ø-Cι g secondary (2,3) alkyl sulfates of the formula CH3(CH2)χ(CHOSO 3 " M + ) CH3 and CH 3 (CH2) y (CHOSO 3 " M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the alkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates), Cio-Cjg alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Ci Q-lg glycerol ethers, the C\ Q-C\ $ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C^- alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C^-Cjg alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-Ci 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C^-Cj betaines and sulfobetaines ("sultaines"), C^Q-CI g amine oxides, and the like, can also be included in the overall compositions. The Cjo-Cig N-alkyl polyhydroxy fatty acid amides are highly preferred, especially the C^-Cjg N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cio-Cjg N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl Ci 2-Cjg glucamides can be used for low sudsing. C J Q-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are described further herein and are listed in standard texts. Anionic surfactants can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. ( Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut alcohols) and about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to 12 carbon atoms; the reaction products of fatty acids are derived from coconut oil sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms. Additionally, secondary alkyl sulfates may be used by the formulator exclusively or in conjunction with other surfactant materials and 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 (AS), such as those illustrated above, have the general formula ROSO3-M+ wherein R is typically a linear C8-22 hydrocarbyl group and M is a water solublizing cation. Branched chain primary alkyl sulfate surfactants (i.e., branched-chain "PAS") having 8-20 carbon atoms are also know; see, for example, Eur. Pat. Appl. 439,316, Smith et al., filed January 21, 1991. Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure CH 3 (CH2)n(CHOSO3-M+)(CH2) m CH 3 wherein m and n are integers of 2 of greater and the sum of m + n is typically about 9 to 17, and M is a water-solublizing cation. The aforementioned secondary alkyl sulfates are those prepared by the addition of H2SO4 to olefins. A typical synthesis using alpha olefins and sulfuric acid is disclosed in U.S. Pat. No. 3,234,258, Morris, issued February 8, 1966 or in U.S. Pat. No. 5,075,041, Lutz, issued December 24,1991. See also U.S. Patent 5,349,101, Lutz et al., issued September 20, 1994; U.S. Patent 5,389,277, Prieto, issued February 14, 1995. The laundry detergent compositions of the present invention also comprise at least about 0.01% by weight, preferably from about 0.1 % to about 60%>, more preferably from about 0.1 %> to about 30%> by weight, of an nonionic detersive surfactant. Preferred nonionic surfactants such as Ci2-C] alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C^ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensate of Cg to Ci 2 alkyl phenols, alkylene oxide condensates of C -C22 alkanols and ethylene oxide/propylene oxide block polymers (Pluronic™ -BASF Corp.), as well as semi polar nonionics (e.g., amine oxides and phosphine oxides) can be used in the present compositions. An extensive disclosure of these types of surfactants is found in U.S. Pat. 3,929,678, Laughlin et al., issued December 30, 1975, incorporated herein by reference. Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 Llenado (incorporated herein by reference) are also preferred nonionic surfactants in the compositions of the invention. More preferred nonionic surfactants are the polyhydroxy fatty acid amides having the formula: O R8 n 'I I R7— C-N-Q wherein R' is C5-C31 alkyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C\ \-C\ 5 alkyl or alkenyl, or mixtures thereof; R° is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, preferably methyl or ethyl, more preferably methyl. Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof. 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 xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Q. It should be understood that it is by no means intended to exclude other suitable raw materials. Q is more preferably selected from the group consisting of -CH2(CHOH) n CH2OH, - CH(CH 2 OH)(CHOH) n _ιCH 2 OH, -CH2(CHOH)2-(CHOR')(CHOH)CH 2 OH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R is hydrogen or a cyclic or aliphatic monosaccharide. Most preferred substituents for the Q moiety are glycityls wherein n is 4, particularly -CH2(CHOH)4CH2OH. R7C0-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. 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-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1 -deoxymaltotriotityl, etc. A particularly desirable surfactant of this type for use in the compositions herein is alkyl-N -methyl glucomide, a compound of the above formula wherein R^ is alkyl (preferably C\ \-C\ ), Rβ, is methyl and Q is 1-deoxyglucityl. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cjo-Ci N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl Ci 2-Cjg glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Cjg soaps may be used. ADJUNCT INGREDIENTS Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Formulations typically comprise from about 5%> to about 50%>, more typically about 5% to about 30%>, by weight, of detergent builder. Granular formulations typically comprise from about 10%> to about 80%), more typically from about 15%) to about 50%) by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded. Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function suφrisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders. Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2SiO5 moφhology form of layered silicate. 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 such layered silicates, such as those having the general formula NaMSi x θ2 x +ι -y^O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2Siθ5 (NaSKS-6 form) is most preferred for use herein. 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 bleaches, and as a component of suds control systems. Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: [M z (zAlO 2 ) y ]-xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amoφhous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Naι 2 [(AlO 2 )i2(SiO 2 )i2]-xH2θ wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic detergent builders suitable for the puφoses of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. 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 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322. Fatty acids, e.g., Ci 2-C^g monocarboxylic acids, can also be incoφorated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, 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 used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021 ; 3,400,148 and 3,422,137) can also be used. Clay Soil Removal/Anti-redeposition Agents The compositions of the present invention can also optionally contain water- soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01%) to about 5%>. The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art. Other Ingredients - A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solid fillers for bar compositions, etc. Other optional ingredients include enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners, hydrolyzable surfactants, optical brighteners, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, soil release agents, germicides, fungicides, and anti corrosion agents. If high sudsing is desired, suds boosters such as the CI Q-CI g alkanolamides can be incoφorated into the compositions, typically at 1%-10%> levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl2, MgSO4, an d the like, can be added at levels of, typically, 0.1%>-2%>, to provide additional suds and to enhance grease removal performance. Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%>-5% of C \2_\ 5 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosity in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, 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 will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. Granular Compositions The orthocarbonate pro-fragrance containing laundry detergent compositions of the present invention can be used in both low density (below 550 grams/liter) and high density granular compositions in which the density of the granule is at least 550 grams/liter. Granular compositions are typically designed to provide an in the wash pH of from about 7.5 to about 11.5, more preferably from about 9.5 to about 10.5. Low density compositions can be prepared by standard spray-drying processes. Various means and equipment are available to prepare high density compositions. Current commercial practice in the field employs spray-drying towers to manufacture compositions which have a density less than about 500 g/1. Accordingly, if spray-drying is used as part of the overall process, the resulting spray-dried particles must be further densified using the means and equipment described hereinafter. In the alternative, the formulator can eliminate spray-drying by using mixing, densifying and granulating equipment that is commercially available. The following is a nonlimiting description of such equipment suitable for use herein. Various means and equipment are available to prepare high density (i.e., greater than about 550, preferably greater than about 650, grams/liter or "g/1"), high solubility, free-flowing, granular detergent compositions according to the present invention. Current commercial practice in the field employs spray-drying towers to manufacture granular laundry detergents which often have a density less than about 500 g/1. In this procedure, an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of about 175°C to about 225°C. However, if spray drying is used as part of the overall process herein, additional process steps as described hereinafter must be used to obtain the level of density (i.e., > 650 g/1) required by modern compact, low dosage detergent products. For example, spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers. A suitable high speed mixer/densifier for this process is a device marketed under the tradename "Lϋdige CB 30" or "Lόdige CB 30 Recycler" which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon. In use, the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 φm to provide thorough mixing/densification. See Jacobs et al, U.S. Patent 5,149,455, issued September 22, 1992. The preferred residence time in the high speed mixer/densifier is from about 1 to 60 seconds. Other such apparatus includes the devices marketed under the tradename "Shugi Granulator" and under the tradename "Drais K-TTP 80). Another process step which can be used to densify further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower intraparticle porosity. Equipment such as that marketed under the tradename "Lόdige KM" (Series 300 or 600) or "Lόdige Ploughshare" mixer/densifiers are suitable for this process step. Such equipment is typically operated at 40-160 φm. The residence time of the detergent ingredients in the moderate speed mixer/densifier is from about 0.1 to 12 minutes. Other useful equipment includes the device which is available under the tradename "Drais K-T 160". This process step which employs a moderate speed mixer/densifier (e.g. Lόdige KM) can be used by itself or sequentially with the aforementioned high speed mixer/densifier (e.g. Lόdige CB) to achieve the desired density. Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942. While it may be more suitable to use the high speed mixer/densifier followed by the low speed mixer/densifier, the reverse sequential mixer/densifier configuration is also contemplated by the invention. One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules in the process of the invention. By way of example, see the processes in Appel et al, U.S. Patent 5,133,924, issued July 28, 1992 (granules are brought into a deformable state prior to densification); Delwel et al, U.S. Patent 4,637,891, issued January 20, 1987 (granulating spray- dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate). In those situations in which particularly heat sensitive or highly volatile detergent ingredients are to be incoφorated into the final detergent composition, processes which do not include spray drying towers are preferred. The formulator can eliminate the spray-drying step by feeding, in either a continuous or batch mode, starting detergent ingredients directly into mixing/densifying equipment that is commercially available. One particularly preferred embodiment involves charging a surfactant paste and an anhydrous builder material into a high speed mixer/densifier (e.g. Lϋdige CB) followed by a moderate speed mixer/densifier (e.g. Lδdige KM) to form high density detergent agglomerates. See Capeci et al, U.S. Patent 5,366,652, issued November 22, 1994 and Capeci et al, U.S. Patent 5,486,303, issued January 23, 1996. Optionally, the liquid/solids ratio of the starting detergent ingredients in such a process can be selected to obtain high density agglomerates that are more free flowing and crisp. Optionally, the process may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer/densifiers for further agglomeration or build-up. The oversized particles produced by this process can be sent to grinding apparatus and then fed back to the mixing/densifying equipment. These additional recycle process steps facilitate build-up agglomeration of the starting detergent ingredients resulting 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, U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996. Other suitable processes which do not call for the use of spray-drying towers are described by Bollier et al, U.S. Patent 4,828,721, issued May 9, 1989; Beerse et al, U.S. Patent 5,108,646, issued April 28, 1992; and, Jolicoeur, U.S. Patent 5,178,798, issued January 12, 1993. In yet another embodiment, the high density detergent composition of the invention can be produced using a fluidized bed mixer. In this process, the various ingredients of the finished composition are combined in an aqueous slurry (typically 80%) solids content) and sprayed into a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, this process can optionally include the step of mixing the slurry using the aforementioned Lδdige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can be used in such processes. Another suitable process which can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients. Optionally, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e.g. Lόdige KM) for further agglomeration resulting in the finished high density detergent composition. See Appel et al, U.S. Patent 5,164,108, issued November 17, 1992. METHOD OF USE The present invention also relates to a method for using the orthocarbonate pro-fragrances of the present invention to provide extended fragrance benefits to fabric, hard surfaces, human skin or hair. The method includes the step of contacting fabric with an aqueous solution of the orthocarbonate pro-fragrances of the present invention. The method also includes contacting a hard surface, for example, enamel, metal, ceramic, wood, with an aqueous solution of the orthocarbonate pro-fragrances described herein. The present invention also relates to a method for providing lasting fragrance to human skin which includes contacting a personal care article to human skin or human hair which comprises one or more orthocarbonate pro-fragrances according to the present invention. EXAMPLE 1 Preparation of tetrakis(phenylethyl) orthocarbonate: To a 250 mL three neck flask equipped with a rubber septum fitted with a needle, a drying tube charged with Drierite, a stopper, and equipped with a magnetic stirrer, is added phenylethyl alcohol (36.7 g), tretraethylorthocarbonate (9.84 g) andpara- toluenesulfonic acid monohydrate (0.21 g). Nitrogen is slowly bubbled through the solution while stirring over 36 hr to remove the ethanol which is produced. The mixture is then diluted with diethyl ether (300 mL) and washed three times with saturated aqueous sodium carbonate. The organic phase is dried over magnesium sulfate, filtered, and concentrated. The product is purified by Kugelrohr distillation wherein the fraction above 100° C, 0.1 mm Hg is retained to yield 12.8 g (50%>) of a clear oil. H NMR (CDCI3) δ 7.2 (m, 16H); 3.6 (t, 8H); and 2.8 (t, 8H); 13 C NMR (CDCl 3 ) δ 138.84, 128.89, 128.11, 126.03, 119.57, 63.75, and 35.8. In addition to the above procedure, suitable methods for preparing the orthocarbonate pro-fragrances of the present invention can be found in "Synthesis of Carboxylic and Carbonic Orthoesters", R. H. DeWolfe, Synthesis, pg. 153, (1974) and "Synthesis of Aryl Carbonates", N. Narasimhamurthy and A. G. Samuelson, Tetrahedron Letters, vol. 27, pg., 991, (1986). EXAMPLES 2 - 5 The following are examples of granular detergent compositions comprising orthocarbonate pro-fragrances. TABLE I weight % Ingredient 2 3 4 5 1. Soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., issuec November 6, 1990. 2. Soil release polymer according to U.S. Patent 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. 3. Soil release polymer according to U.S. Patent 4,702,857, Gosselink, issued October 27, 1987. 4. Pro-accord according to Example I. 5. Balance to 100%> can, for example, include minors like optical brightener, perfume, suds suppresser, soil dispersant, protease, lipase, cellulase, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO3, talc, silicates, etc. EXAMPLES 6-10 The following are examples of liquid laundry detergent compositions comprising orthocarbonate pro-fragrances. TABLE II Ingredients Weight % 6 7 8 9 10 1. C12-C13 alkyl E9 ethoxylate as sold by Shell Oil Co. 2. Bacillus amyloliquefaciens subtilisin as described in WO 95/10615 published April 20, 1995 by Genencor International. 3. Derived from Humicola lanuginosa and commercially available from Novo. 4. Disclosed in WO 9510603 A and available from Novo. 5. Pro-fragrance according to Example I. 6. Terephthalate co-polymer as disclosed in U.S. Patent 4,968,451 , Scheibel et al. , issued November 6, 1990. EXAMPLES 10-12 A deodorant gel stick of the present invention having the composition given below, and being essentially free of water, is prepared as follows. TABLE III Weight % Ingredients 10 11 12 1. Powder form commercially available from Olin. 2. Pro-fragrance according to Example I. All of the above materials, except the pro-fragrance, are vigorously mixed and heated to about 121° C until the mixture is clear. The mixture is them cooled to about 80° C and the pro-accord is added with stirring. The mixture is poured into stick molds and cooled to room temperature forming the deodorant gel stick compositions of the present invention. EXAMPLES 13 - 16 A personnel cleanser composition is prepared by combining the following ingredients using conventional mixing techniques. TABLE IV Weight % 1. Available as Pemulen® from B. F. Goodrich Coφoration. 2. Available as Carbomer® 954 from B. F. Goodrich Coφoration. 3. As a 50%) aqueous solution. 4. Light mineral oil available as Drakeol 5 from Penreco, Dickenson, TX. 5. Pro-fragrance according to Example I. The above Examples 13-16 can be suitably prepared as follows. In a suitable vessel, the Phase A ingredients are admixed at room temperature to form a dispersion and heated with stirring to 70-80° C. In a separate vessel, the Phase B ingredients are heated with stirring to 70-80° C. Phase B is then added to Phase A with mixing to form the emulsion. Next, Phase C is added to neutralize the composition. The Phase D ingredients are added with mixing, followed by cooling to 45-50° C. The Phase E ingredients are then added with stirring, followed by cooling to 40° C. Phase F is heated with mixing to 40° C. and added to the emulsion, which is cooled to room temperature. The resulting cleansing composition is useful for cleansing the skin. The emulsion de-emulsifies upon contact with the skin. EXAMPLES 17-20 The followng are non-limiting examples of hard surface cleaners according to the present invention. TABLE V Weight % 1. SOKALAN CP-9. 2. Pro-fragrance according to Example I.

Claims: What is claimed is: 1. A laundry detergent composition having increased fragrance retention and fragrance longevity on fabric, comprising: A) at least 0.01% by weight, of a fragrance delivery system comprising: i) one or more orthocarbonate pro-fragrances having the formula: wherein R , R^, R3, and R4 are independently C1-C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; C -C20 substituted or unsubstituted aryl, C2-C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxyalkyl; C -C4Q substituted or unsubstituted alkylenearyl; C -C4o substituted or unsubstituted aryloxy; C -C4Q substituted or unsubstituted alkyleneoxyaryl; or two R*, R^, R3, and R4 are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; provided: a) one R , R2, R3 ; or R comprises a fragrance raw material having a molecular weight greater than or equal to 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to 300 g/mol; ii) optionally one or more pro-fragrance materials selected from the group consisting of acetals, ketals, orthoesters, orthophosphates, orthosilicates, and mixtures thereof; iii) optionally one or more fragrance raw materials; B) at least 0.01% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof, preferably said surfactant is an anionic surfactant; and C) the balance carriers and adjunct ingredients. 2. A composition according to Claim 1 wherein the adjunct ingredients are selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach catalysts, bleach activators, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof. 3. A composition according to either Claim 1 or 2 wherein said orthocarbonate fragrance has the formula: wherein at least one -OR^ or -OR3 is derived from a fragrance raw material alcohol having a molecular weight of greater than or equal to 100 g/mol; R°, R9, R!0, and Rl are each independently hydrogen, Cj-C20 linear or branched alkyl, C2-C20 linear or branched alkenyl, C1-C20 linear, branched or cyclic alkylenecarboxy, C1-C20 linear, branched, or cyclic carboxyalkyl, C1-C20 linear or branched alkyleneamino, C1-C20 linear or branched aminoalkyl, C]-C20 linear, branched, or cyclic alkylenecarboxamido, C\- C20 linear or branched carboxamidoalkyl, alkyleneoxyalkyl having the formula: Rl3 -(CH.C 1 HO CH^R^ wherein R 2 j s hydrogen or methyl; Rl3 is hydrogen or C1-C2 alkyl, x is from 1 to 20, y is from 0 to 20; or R 0 and Rl 1 are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; and mixtures thereof; n is from 0 to 2. 4. A hard surface cleaning composition having increased fragrance retention and fragrance longevity on hard surfaces, comprising: A) at least 0.01%> by weight, of a fragrance delivery system comprising: i) one or more orthocarbonate pro-fragrances having the formula: wherein Rl, R^, R , and R4 are independently Ci -C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; C -C20 substituted or unsubstituted aryl, C2-C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxyalkyl; C6-C40 substituted or unsubstituted alkylenearyl; C -C4o substituted or unsubstituted aryloxy; C -C4o substituted or unsubstituted alkyleneoxyaryl; or two Rl, R^, R3, and R are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; provided: a) at least one R , R^, R3 ? or R comprises a fragrance raw material having a molecular weight greater than or equal to 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to 300 g/mol; ii) optionally one or more pro-fragrance materials selected from the group consisting of acetals, ketals, orthoesters, orthophosphates, orthosilicates, and mixtures thereof; iii) optionally one or more fragrance raw materials; B) at least 0.01% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; and C) the balance carriers and adjunct ingredients. 5. A composition according to Claim 4 wherein the adjunct ingredients are selected from the group consisting of abrasives, builders, bleaches, bleach boosters, dispersents, enzymes, dyes, colorants, filler salts, hydrotropes, enzymes, preservatives, anti-oxidants, chelants, stabilizers, germicides, fungicides, photodisinfectants, and mixtures thereof. 6. A composition according to either Claim 4 or 5 wherein said orthocarbonate fragrance has the formula: wherein at least one -OR^ or -OR is derived from a fragrance raw material alcohol having a molecular weight of greater than or equal to 100 g/mol; R°, R9, R!0, and R 1 are each independently hydrogen, Cj-C20 linear or branched alkyl, C2-C20 linear or branched alkenyl, C1-C20 linear, branched or cyclic alkylenecarboxy, C \ -C20 linear, branched, or cyclic carboxyalkyl, 1-C20 linear or branched alkyleneamino, C1-C20 linear or branched aminoalkyl, C1-C20 linear, branched, or cyclic alkylenecarboxamido, C\- C20 linear or branched carboxamidoalkyl, alkyleneoxyalkyl having the formula: Rl3 — (CH^HO CH^R^ wherein R i 2 is hydrogen or methyl; R 3 is hydrogen or C1-C2 alkyl, x is from 1 to 20, y is from 0 to 20; or R O and Rl 1 are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; and mixtures thereof; n is from 0 to 2. 7. A hard surface cleaning composition having increased fragrance retention and fragrance longevity on hard surfaces, comprising: A) at least 0.1% by weight, of a sulfosuccinamate having the formula: wherein Rl and R^ are hydrogen or -SO3M2 provided Rl does not equal R^; R3 is butyl when R is ethyl and R3 is pentyl when R is propyl; M and M^ are independently hydrogen or a salt forming cation; B) at least 0.1%> by weight, of a nonionic surfactant having the formula CH 3 (CH 2 ) x CH 2 O(CH 2 CH2θ) y H wherein x is from 6 to 12, y is from 3.5 to 10; C) at least 0.01%o by weight, of a fragrance delivery system comprising: i) one or more orthocarbonate pro-fragrances having the formula: wherein R , R2, R ; and R4 are independently C ] -C 2 o linear, branched, or substituted alkyl; C -C 2 Q linear, branched, or substituted alkenyl; C5- 20 substituted or unsubstituted cyclic alkyl; Cg-C 2 o substituted or unsubstituted aryl, C2-C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxyalkyl; C -C40 substituted or unsubstituted alkylenearyl; Cg-C4o substituted or unsubstituted aryloxy; C -C4o substituted or unsubstituted alkyleneoxyaryl; or two R , R^, R , and R are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; provided: a) at least one Rl, R^, R3 ? or R4 comprises a fragrance raw material having a molecular weight greater than or equal to 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to 300 g/mol; ii) optionally one or more pro-fragrance materials selected from the group consisting of acetals, ketals, orthoesters, orthophosphates, orthosilicates, and mixtures thereof; iii) optionally one or more fragrance raw materials; and D) the balance carriers and adjunct ingredients, said adjunct ingredients selected from the group consisting of abrasives, builders, bleaches, bleach boosters, clays, detersive surfactants, thickeners, dispersents, enzymes, dyes, colorants, filler salts, hydrotropes, enzymes, preservatives, anti-oxidants, chelants, stabilizers, germicides, fungicides, solvents, photodisinfectants, and mixtures thereof. 8. A personal care composition for use on human skin or hair having increased fragrance retention and fragrance longevity on hard surfaces, comprising: A) at least 0.01% by weight, of a fragrance delivery system comprising: i) one or more orthocarbonate pro-fragrances having the formula: wherein R , R^, R ; and R4 are independently Cj-C o linear, branched, or substituted alkyl; C -C 2 Q linear, branched, or substituted alkenyl; C5-C 2 o substituted or unsubstituted cyclic alkyl; Cg-C 2 o substituted or unsubstituted aryl, C2-C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxyalkyl; C6-C40 substituted or unsubstituted alkylenearyl; C6-C40 substituted or unsubstituted aryloxy; C -C4o substituted or unsubstituted alkyleneoxyaryl; or two R , R?-, R , and R are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; provided: a) at least one Rl, R^, R ; or R comprises a fragrance raw material having a molecular weight greater than or equal to 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to 300 g/mol; ii) optionally one or more pro-fragrance materials selected from the group consisting of acetals, ketals, orthoesters, orthophosphates, orthosilicates, and mixtures thereof; iii) optionally one or more fragrance raw materials; B) at least 0.01%ι by weight, of one or more adjunct ingredients selected from the group consisting of surfactants, emollients, bactericides, gelling agents, desiccants, propellants, dyes, colorants, ointment bases, lanolin, antiperspirants, mineral oil, talc, abrasives, optical brighteners, phase stabilizing agents, absorbents, and mixtures thereof; and C) the balance carriers. 9. An orthocarbonate pro-fragrance compound having the formula: wherein R* and R^ are independently C]-C 2 o linear, branched, or substituted alkyl; C 2 -C 2 Q linear, branched, or substituted alkenyl; C5-C 2 o substituted or unsubstituted cyclic alkyl; Cg-C 2 o substituted or unsubstituted aryl, C 2 -C4Q substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxyalkyl; C -C4Q substituted or unsubstituted alkylenearyl; C -C4o substituted or unsubstituted aryloxy; Cg-C4Q substituted or unsubstituted alkyleneoxyaryl; provided: a) at least one Rl or R^ comprises a fragrance raw material having a molecular weight greater than or equal to 100 g/mol; b) said orthocarbonate pro-fragrance has a molecular weight greater than or equal to 300 g/mol; and c) R is not equal to R^. 10. An orthocarbonate pro-fragrance compound having the formula: wherein at least one -OR2 or -OR is derived from a fragrance raw material alcohol having a molecular weight of greater than or equal to 100 g mol; R^, R , R! 0, and Rl are each independently hydrogen, Ci -C 2 o linear or branched alkyl, C 2 -C 2 o linear or branched alkenyl, C ] -C Q linear, branched or cyclic alkylenecarboxy, C j -C Q linear, branched, or cyclic carboxyalkyl, Cj-C 2 o linear or branched alkyleneamino, Cj-C 2 o linear or branched aminoalkyl, C J -C 2 Q linear, branched, or cyclic alkylenecarboxamido, C\- C linear or branched carboxamidoalkyl, alkyleneoxyalkyl having the formula: wherein R 2 is hydrogen or methyl; Rl3 is hydrogen or Cι-C 2 alkyl, x is from 1 to 20, y is from 0 to 20 or any two R^, R^, R 0, and Rl 1 units can be taken together to form a fused ring or spiroannulated ring having from 3 to 8 carbons and optionally one or more heteroatoms in said ring, said ring is optionally further substituted by one or more Cι-C 2 alkyl; n is from 0 to 2.

Inventors: GRAY LON MONTGOMERY, JONES KYLE DAVID, MIRACLE GREGORY SCOT, MORELLI JOSEPH PAUL, PRICE KEN NATHAN, GRAY, LON, MONTGOMERY, JONES, KYLE, DAVID, MIRACLE, GREGORY, SCOT, MORELLI, JOSEPH, PAUL, PRICE, KEN, NATHAN
Applicants: GRAY LON MONTGOMERY, JONES KYLE DAVID, MIRACLE GREGORY SCOT, MORELLI JOSEPH PAUL, PRICE KEN NATHAN, PROCTER & GAMBLE, GRAY, LON, MONTGOMERY, JONES, KYLE, DAVID, MIRACLE, GREGORY, SCOT, MORELLI, JOSEPH, PAUL, PRICE, KEN, NATHAN, THE PROCTER & GAMBLE COMPANY
Application year: 1998
Main classification: C11D3
IPC codes: C11D3