TERTIARY ALCOHOL FRAGRANCE RAW MATERIAL DELIVERY SYSTEMS FIELD OF THE INVENTION The present invention relates to pro-accords which are capable of releasing tertiary alcohol fragrance raw materials inter alia linalool, tertahydrolinalool, ethyllinalool, and dihydromyrcenol. The present invention also relates to fragrance delivery systems which comprise said pro-accords thereby providing a means for delivering tertiary alcohol fragrance raw materials to a situs, preferably human skin. The present invention further relates to fine fragrances and perfumes which comprise said tertiary alcohol releasing fragrance delivery systems. The fragrance delivery systems described herein also provide for fragrance longevity.

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, inter 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 modem chemistry, individual components responsible for the odor properties of these resins, gums and oils were isolated and subsequently characterized. Modem perfumery involves the artful compounding of fragrance materials to achieve novel fragrance compositions having defined "characteristics".

Many modem fragrances are no longer derived from natural sources but are synthesized by modem chemical methods as highly pure fragrance raw materials (FRM).

These FRM's are currently formulated to produce fine perfumes, colognes, eau de toilettes, after-shave lotions, and other personal fragrance compositions. Those skilled in the art of preparing these fragrance-containing compositions have categorized fragrances into three types based on their relative volatility; top, middle, and base notes.

A drawback of typical fine fragrances and perfumes is that the original scent, which is a balance of fragrance raw materials, begins to change once the perfume or fragrance has been applied to human skin. This loss of fragrance balance is in part due to differential evaporation of the more volatile top notes, and to absorption of other ingredients into the skin surface. Users of perfumes and fine fragrances have attempted to rectify this problem in

many ways. One method is to initially"load up"on the amount of perfume and rely upon the natural evaporation rate to diminish the fragrance to a suitable level several hours later when the desired effect is needed. Another method commonly employed is to continually renew the fragrance by reapplying small amounts of the perfume to the skin at short time intervals.

Neither of these solutions is adequate to overcome the diminishing level of top and middle notes over time. In fact, base notes which are present over a protracted period by virtue of their low volatility, begin to accumulate with each"re-freshing"of perfume and after a time the base notes begin to overwhelm the other fragrance notes and destroy the original fragrance balance.

Recently it has been discovered that some fragrance raw materials can be delivered to human skin via pro-perfumes. These pro-perfume compounds include acid labile acetals, ketals, and orthoesters which breakdown upon contact with the acidic pH on the human skin surface resulting in the release of fragrance raw materials. In general, acetals release aldehydes, ketals release ketones, and orthoesters release alcohols. However, the formulator has been limited by the fact that some pro-perfumes, although acid labile, have a fragrance release half-life (hydrolysis rate) which is beyond the time which is of utility for use in fine fragrances or perfume compositions. Also, the prior art does not disclose pro-perfumes which suitably release tertiary alcohol fragrance raw materials.

It has now been surprisingly discovered that certain orthoester pro-accords are capable of delivering one or more tertiary alcohol fragrance raw materials at a rate which provides a useful means for delivering these desirable fragrance raw materials to human skin.

In addition, the pro-accords described herein are modifiable to deliver tertiary alcohols at rates which are preferred by the formulator.

SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in that it has been surprisingly discovered that certain orthoesters comprising at least one tertiary alcohol fragrance raw material can be prepared which release said tertiary alcohol at a rate which can be adjusted to meet the specific needs of the formulator. For example, the protracted release of fragrance raw materials provides the formulator with a means of extending the original perfume raw material blend, or initial fragrance note. By utilizing the pro-accords of the present invention the formulator can now controllably release tertiary alcohol fragrance raw materials. This controlled release is a means for providing longevity of tertiary alcohol fragrances on human skin.

A first aspect of the present invention relates to pro-accords having the formula:

wherein each-OR',-OW, and-OR3 moiety is an alkoxy unit derived from an alcohol such that each R', R2, and R3 is independently substituted or unsubstituted Cl-C20 linear alkyl, C3- C2o branched alkyl, C3-C20 cyclic alkyl, C4-C20 branched cyclic alkyl, C3-C20 linear alkenyl, C4-C20 branched alkenyl, C3-C20 cyclic alkenyl, C4-C20 branched cyclic alkenyl, C6-C2o aryl, C6-C20 alkylenearyl, C6-C20 alkyleneoxyalkyl, C6-C20 alkyleneoxyaryl, and mixtures thereof ; or any two R', R2, or R3 can be taken together to form a ring having from 5 to 8 atoms, said ring is optionally further substituted by one or more Cl-C22 alkyl, C,-C22 alkenyl, C6-Ci2 aryl, C6-C22 alkylenearyl units, and mixtures thereof ; R is hydrogen, substituted or unsubstituted C,-C20 linear alkyl, C3-C20 branched alkyl, C3-C20 cyclic alkyl, C3-C20 branched cyclic alkyl, C3-C20 linear alkenyl, C4-C20 branched alkenyl, C3-C20 cyclic alkenyl, C4-C20 branched cyclic <BR> <BR> <BR> alkenyl, C6-C20 aryl, C6-C20 alkylenearyl, C6-C20 alkyleneoxyalkyl, C6-C20 alkyleneoxyaryl, and mixtures thereof ; or any R', R2, or R3 can be taken together with R to form a ring having from 5 to 8 atoms, said ring is optionally further substituted by one or more Cl-C22 alkyl, C- C22 alkenyl, C6-C, 2 aryl, C6-C22 alkylenearyl units, and mixtures thereof ; provided at least one R', R2, or R3 unit is derived from a tertiary fragrance raw material alcohol, and said pro- accord has a fragrance release half-life of greater than or equal to 0.1 hours at pH 5.3 and less than or equal to 12 hours at pH 2.5 when said fragrance release half-life is measured in a NaH2PO4 buffer at said pH.

The present invention further relates to a fragrance delivery system which comprises at least one pro-accord as described herein capable of suitably releasing a tertiary alcohol fragrance raw material together with one or more pro-accords inter alia orthoesters, ketals, acetals, orthocarbonates, preferably having a fragrance release half-life of greater than or equal to 0.1 hours at pH 5.3 and less than or equal to 12 hours at pH 2.5 when said fragrance release half-life is measured in a NaH2PO4 buffer at said pH.

The present invention also relates to perfume and fine fragrances which comprise, in addition to the fragrance delivery systems described herein, other fragrance raw materials and adjunct ingredients. 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 novel compositions of matter, namely, orthoesters capable of releasing tertiary alcohol fragrance raw materials. As described herein, this rate of tertiary alcohol release, hereinafter known as the"fragrance release half-life", can be manipulated in order to provide release of the tertiary alcohol in a manner which corresponds to the specific requirements of a fragrance containing composition.

The tertiary fragrance raw material releasing compounds are referred to throughout the present specification as pro-perfumes, pro-fragrances, or, preferably, as pro-accords, and these terms are used collectively and/or interchangeably to signify orthoesters capable of releasing at least one tertiary alcohol fragrance raw material.

For the purposes of the present invention the terms"perfume"and"fine fragrance" are essentially synonymous and are used collectively or interchangeably throughout the present specification and are taken to mean the more concentrated forms of fragrance- containing compositions. Aspects of the present invention which apply to"perfumes"will therefore apply equally to"fine fragrances"and vice versa. Typically, colognes, eau de toilettes, after shaves, and other fragrance-containing embodiments are perfumes or fine fragrances which have a greater degree of dilution, usually by a volatile carrier such as ethanol.

Mixtures of fragrance materials are known by those skilled in the art of fragrances and perfumes as"accords". The term"accord"as used herein is defined as"a mixture of two or more'fragrance raw materials'which are artfully combined to impart a pleasurable scent, odor, essence, or fragrance characteristic". Fragrance delivery systems of the present invention comprise at least one pro-accord capable of releasing at least one tertiary alcohol as well as one or more other"pro-accords"which are preferably capable of releasing a mixture of fragrance raw materials or"accords". For the purposes of the present invention"fragrance raw materials"are herein defined as compounds preferably have 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". However, as the term "fragrance raw material"relates to tertiary alcohol-releasing pro-accords, the molecular

weight of adjunct alcohols, which together with the tertiary alcohols form the pro-accord, may have molecular weights less than 100 g/mol. For example, as further described herein below, lower molecular weight alcohols inter alia ethanol may be used as an orthoester alcohol component in order to produce the desired fragrance release half-life.

Typically the"fragrance raw materials"which make up the non-tertiary alcohol- releasing pro-accords of the fragrance delivery systems of the present invention comprise inter alia alcohols, ketones, aldehydes, esters, ethers, nitriles, and alkenes such as terpenes.

A listing of common"fragrance raw materials"can be found in various reference sources, for example,"Perfume and Flavor Chemicals", Vols. I and II; Steffen Arctander Allured Pub.

Co. (1994) and"Perfumes: Art, Science and Technology" ; Muller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) both incorporated herein by reference.

For the purposes of the present invention substituted or unsubstituted alkyleneoxy units are defined as moieties having the formula: wherein R5 is hydrogen, methyl, and mixtures thereof ; R6 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: wherein R5 is hydrogen, C l-C 1g alkyl, and mixtures thereof ; R6 is hydrogen, methyl, ethyl, and mixtures thereof ; the index x is from I to about 20 and the index y is from 2 to about 18.

For the purposes of the present invention substituted or unsubstituted alkylenearyl units are defined as moieties having the formula: wherein R5 and R6 are each independently hydrogen, hydroxy, nitrilo, halogen, nitro, carboxyl wherein R'is Ci-cl linear or branched alkyl), amino, alkylamino, and mixtures thereof, p is from 1 to about 14.

For the purposes of the present invention substituted or unsubstituted alkyleneoxyaryl units are defined as moieties having the formula:

wherein R5 and R6 are each independently hydrogen, hydroxy, nitrilo, halogen, nitro, carboxyl wherein R'is Cl-cl linear or branched alkyl), amino, alkylamino, and mixtures thereof, q is from I to about 14.

Tertiary Alcohol-Releasing Pro-Accords The pro-accords of the present invention which release at least one tertiary alcohol fragrance raw material have the formula:

wherein hydrolysis of the orthoester releases fragrance raw material components according to the following scheme:

thereby releasing two equivalents of alcohol and one equivalent of ester.

Each R', R2, and R3 is independently substituted or unsubstituted CrCzo linear alkyl, C3-C20 branched alkyl, C3-C20 cyclic alkyl, C4-C20 branched cyclic alkyl, C3-C20 linear alkenyl, C4-C20 branched alkenyl, C3-C20 cyclic alkenyl, C4-C20 branched cyclic alkenyl, C6- C20 aryl, C6-C20 alkylenearyl, C6-C20 alkyleneoxyalkyl, C6-C2o alkyleneoxyaryl, and mixtures thereof ; preferably substituted or unsubstituted C,-Cl0 linear alkyl, C3-Clo branched alkyl, C3- <BR> <BR> <BR> Cl0 cyclic alkyl, C4-Cl0 branched cyclic alkyl, C3-Clo linear alkenyl, C4-Clo branched alkenyl, C3-Cl0 cyclic alkenyl, C4-Cl0 branched cyclic alkenyl, and mixtures thereof ; or any two R', , or R3 can be taken together to form a ring having from 5 to 8 atoms, said ring is optionally further substituted by one or more Cl-C22 alkyl, Cl-C22 aikenyl, C6-C, 2 aryl, C6-C22

alkylenearyl units, and mixtures thereof ; provided at least one of the R', R, and R3 units is derived from a tertiary alcohol.

Non-limiting examples of tertiary alcohol fragrance raw materials includea, a- dimethyl phenethyl alcohol (dimethyl benzyl carbinol), a, a-4-trimethyl-3-cyclohexene-1- methanol (a-terpineol), a, a-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-1-phenyl-3-pentanol (phenylethyl methylethyl carbinol), 1,2- <BR> <BR> <BR> <BR> dimethyl-3- (1-methylethenyl) cyclopentanol (plinol), 1, 2-dimethyl-3- (1-methylethenyl)<BR> <BR> <BR> <BR> <BR> <BR> <BR> cyclohexanol 1-methyl-4-isopropyl cyclohexan-8-ol (dihydroterpineol), 444-hydroxy-4- methyl pentyl)-3-cyclohexene-1-carboxaldehyde (Lyral; Kovanol), 2,6-dimethyl-heptan-2-ol (Dimetol, Freesiol, Lolitol), 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-1, 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-1, 6-nonadien-3-ol (Ethyl Linalool), 2,5,5-trimethyl-octahydro-2-naphthalenol (Ambrinol), 2-Methyl-2-vinyl-5- (1-hydroxy-1-methyl-ethyl) tetrahydrofuran (cis and trans) (Linalool Oxide), 4- (4-hydroxy-4- methyl pentyl)-3-cyclohexene-1-carboxaldehyde (Lyral; Kovanol), 4-methyl-1- (1- methylethyl)-3-cyclohexen-l-ol, 3,7,9-trimethyl-1, 6-decadien-3-ol (Isobutyl Linalool), 3,7,1 1, 15-tetramethyl hexadec-1-en-3-ol (Iso phytol), Cedrol, and b-caryophyllene alcohol (caryophyllenol).

Non-limiting examples of preferred tertiary alcohol fragrance raw materials include R', R2, and R3 units which are linalyl, tetrahydrolinalyl, ethyllinalyl, dihydromyrcenyl, and mixtures thereof resulting in the release of linalool, tetrahydrolinalool, ethyllinalool, and dihydromyrcenol.

R is hydrogen, substituted or unsubstituted C-C20 linear alkyl, C3-C2o branched alkyl, C3-C20 cyclic alkyl, C4-C2o branched cyclic alkyl, C3-C20 linear alkenyl, C4-C20 <BR> <BR> <BR> branched alkenyl, C3-C20 cyclic alkenyl, C4-C20 branched cyclic alkenyl, C6-C20 aryl, C6-C20

alkylenearyl, C6-C20 alkyleneoxyalkyl, C6-C2o alkyleneoxyaryl, and mixtures thereof ; or any R', R2, or R3 can be taken together with R to form a ring having from 5 to 8 atoms, said ring is optionally further substituted by one or more C,-C22 alkyl, C,-C22 alkenyl, C6-Ci2 aryl, C6- C22 alkylenearyl units, and mixtures thereof. Preferably R is hydrogen, substituted or unsubstituted C,-C, o linear alkyl, C3-Clo branched alkyl, C3-Clo linear alkenyl, C6-C, o aryl, C6-Clo alkylenearyl; more preferably R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, t-butyl, phenyl, benzyl, and mixtures thereof.

By the term"substituted"herein is meant"compatible moieties which replace a hydrogen atom". Non-limiting examples of substituents are hydroxy, nitrilo, halogen, nitro, carboxyl wherein R'is Cl-Cl2 linear or branched alkyl), amino, C 1-C 12 mono-and dialkylamino, and mixtures thereof.

Fragrance Delivery System and Related Compositions The present invention further relates to fragrance delivery systems comprising: a) at least one tertiary alcohol fragrance raw material-releasing pro-accord as described herein; and b) the balance one or more pro-accords suitable for use in delivering one or more fragrance raw materials.

When formulated into a fragrance delivery system, the tertiary alcohol fragrance raw material-releasing orthoesters of the present invention will comprise from about 0.1% to about 99%, preferably from about I% to about 50% by weight, of said fragrance delivery system.

The fragrance delivery systems of the present invention preferably comprise one or more pro-accords described herein below. When present, said pro-accords comprise, alone or as an admixture, from 0.1% to about 99%, preferably from about 1% to about 50% by weight, of the fragrance delivery system.

The present invention further relates to a perfume or fine fragrance for application to human skin having increased fragrance longevity comprising: a) from 0.1 % to 99.9% by weight, of at least one pro-accord which releases a tertiary alcohol fragrance raw material, provided said pro-accord has a fragrance release half-life of greater than or equal to 0.1 hours at pH 5.3 and less than or equal to 12 hours at pH 2.5 when said fragrance release half-life is measured in a NaH2P04 buffer at said pH; b) from 0.1% to 99.9% by weight, of one or more fragrance raw materials; and

c) the balance carriers and adjunct ingredients.

In addition, the perfume or fine fragrance compositions of the present invention further comprise carriers, fixatives, and other adjunct ingredients which can be added in any suitable amount or ratio to the tertiary alcohol-releasing orthoesters or the pro-accords which comprise the balance of the delivery system. Typical carriers are methanol, ethanol (preferred), iso-propanol, polyethylene glycol, as well as water in some instances. Fixatives serve to lower the volatility of certain top and middle notes in order to extend their contact time on skin. Adjunct ingredients include perfume raw material components which are essential oils and are therefore not a single chemical entity. In addition, the adjunct ingredients may be mixtures of synthetic fragrance raw materials which serve a further purpose in addition to providing a pleasurable odor.

Orthoesters One class of preferred compounds useful as pro-accords according to the present invention are orthoesters having the formula: wherein hydrolysis of the orthoester releases fragrance raw material components according to the following scheme: wherein R is hydrogen, substituted or unsubstituted Cl-C20 linear akl, C3-C20 branched alkyl, C3-C20 cyclic alkyl, C4-C2o branched cyclic alkyl, C3-C20 linear alkenyl, C4-C20 branched alkenyl, C3-C20 cyclic alkenyl, C4-C20 branched cyclic alkenyl, C6-C20 aryl, C6-C20 alkylenearyl, C6-C20 akieneoxyalkyl, C6-C20 alkyleneoxyaryl, and mixtures thereof ; <BR> <BR> preferably hydrogen, substituted or unsubstituted C-C, 0 linear alkyl, C3-CIo branched alkyl,<BR> <BR> C3-Clo linear alkenyl, C6-C, o aryl, C6-C, o alkylenearyl; more preferably R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, t-butyl, phenyl, benzyl, and mixtures thereof.

Each R', R², and R3 is independently substituted or unsubstituted Cl-C20 linear alkyl, C3-C20 branched alkyl, C3-C20 cyclic alkyl, C4-C2o branched cyclic alkyl, C3-C20 linear alkenyl, C4-C2o branched alkenyl, C3-C20 cyclic alkenyl, C4-C20 branched cyclic alkenyl, C6- <BR> <BR> <BR> C20 aryl, C6-C2o alkylenearyl, C6-C20 alkyleneoxyalkyl, C6-C20 alkyleneoxyaryl, and mixtures thereof ; preferably substituted or unsubstituted Cl-Cl0 linear alkyl, C3-Clo branched alkyl, C3- <BR> <BR> <BR> C, 0 cyclic alkyl, C4-CIo branched cyclic alkyl, C3-Cl0 linear alkenyl, C4-CIo branched alkenyl, C3-Clo cyclic alkenyl, C4-Cl0 branched cyclic alkenyl, and mixtures thereof. By the term "substituted"herein is meant"compatible moieties which replace a hydrogen atom". Non- limiting examples of substituents are hydroxy, nitrilo, halogen, nitro, carboxyl (-CHO;- C02H;-C02R' ;-CONH2 ;-CONHR' ;-CONR'2; wherein R'is C 1-C 12 linear or branched alkyl), amino, C 1-C 12 mono-and dialkylamino, and mixtures thereof.

Acetals and ketals Another class of compound useful as pro-accords according to the present invention are acetals and ketals having the formula: wherein hydrolysis of the acetal or ketal releases one equivalent of aldehyde or ketone and two equivalents of alcohol according to the following scheme: wherein R is C 1-C20 linear alkyl, C3-C20 branched alkyl, C3-C20 cyclic alkyl, C4-C20 branched cyclic alkyl, C3-C20 linear alkenyl, C3-C20 branched alkenyl, C3-C20 cyclic alkenyl, C4-C20 branched cyclic alkenyl, C6-C20 substituted or unsubstituted aryl, preferably the moieties which substitute the aryl units are alkyl moieties, and mixtures thereof. R¹ is hydrogen, R, or in the case wherein the pro-accord is a ketal, R and R1 can be taken together to form a ring. R2 and R3 are independently selected from the group consisting of C-C20 linear, branched, or substituted alkyl; C4-C20 linear, branched, or substituted alkenyl; C-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;C-C substituted or unsubstituted aryloxy; C6-C40 substituted or unsubstituted alkyleneoxyaryl; C6-C40 oxyalkylenearyl; and mixtures thereof. By the term"substituted"herein is meant "compatible moieties which replace a hydrogen atom". Non-limiting examples of substituents are hydroxy, nitrilo, halogen, nitro, carboxyl -CONR'2; wherein R'is C 1-C 12 linear or branched alkyl), amino, Cl-C12 mono-and dialkylamino, and mixtures thereof.

Orthocarbonates Another class of preferred compounds useful as pro-accords according to the present invention are orthocarbonates having the formula: wherein hydrolysis of the orthoester releases the fragrance raw material components according to the following scheme: which can continue to hydrolyze and further release two equivalents of one or more fragrance raw material alcohol according to the following scheme: thereby providing up to four equivalents of fragrance raw material alcohol per equivalent of delivered orthocarbonate, wherein R I, R2, R3, and R4 are independently C 1-C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C3-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-C32 substituted or _ unsubstituted aryloxy; C6-C40 substituted or unsubstituted alkyleneoxyaryl; C6-C40 oxyalkylenearyl; and mixtures thereof. By the term"substituted"herein is meant"compatible moieties which replace a hydrogen atom". Non-limiting examples of substituents are hydroxy, nitrilo, halogen, nitro, carboxyl CONR'2; wherein R'is C 1-C 12 linear or branched alkyl), amino, C 1-C 12 mono-and dialkylamino, and mixtures thereof.

Non-limiting examples of fragrance raw material alcohols which can be suitably released by the pro-accords of the present invention include 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- 1-methanol (Isocyclo geraniol), 4- (l-methylethyl) cyclohexanemethanol (Mayol), a-3,3- trimethyl-2-norborane methanol, 1,1-dimethyl-1- (4-methylcyclohex-3-enyl) methanol, 2- phenylethanol, 2-cyclohexyl ethanol, 2- (o-methylphenyl)-ethanol, 2- (m-methylphenyl) ethanol, 2- (p-methylphenyl) ethanol, 1] hept-2-ene-2-ethanol (nopol), 2- (4- methylphenoxy) ethanol, 3,3-dimethyl-D2-b-norbornane ethanol, 2-methyl-2- cyclohexylethanol,1-(4-isopropylcyclohexyl)-ethanol, 1-phenylethanol, 1, 1-dimethyl-2- phenylethanol, 1,1-dimethyl-2- (4-methyl-phenyl) ethanol, 1-phenylpropanol, 3- phenylpropanol, 2-phenylpropanol (Hydrotropic Alcohol), 2-(cyclododecyl) propan-1-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-1-ol (methylcinnamyl alcohol), a-n-pentyl-3-phenyl-2-propen-1-ol (a-amyl-cinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2- (4-methylphenyl)-2-propanol, 3- (4-methylcyclohex- 3-ene) butanol, 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) butanol, 2-ethyl-4- (2,2,3- <BR> <BR> <BR> trimethyl-cyclopent-3-enyl)-2-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-4- (2,2,3-trimethyl- 3-cyclopenten-1-yl)-2-buten-1-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, 3-methyl-pentanol, 3-methyl-3-penten-1-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-1-phenyl-2-pentanol, (1-methyl-bicyclo [2.1.1] hepten-2-yl)-2-methylpent- <BR> <BR> <BR> I-en-3-ol, 3-methyl-l-phenylpentan-3-ol, 1, 2-dimethyl-3- (I-methylethenyl) cyclopentan-l-ol,<BR> <BR> <BR> <BR> <BR> 2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 2-isoproenyl-4-methyl-

4-hexen-l-ol (Lavandulol), 2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-l- cyclohexene (Dihydrocuminyl alcohol), l-methy!-4-isopropenylcyclohex-6-en-2-ol(carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol, 1-methyl-4-iso-propenylcyclohexan-3-ol, 4- isopropyl-I-methylcyclohexan-3-ol, 4-tert-butylcyclo-hexanol, 2-tert-butylcyclohexanol, 2- <BR> <BR> <BR> <BR> tert-butyl-4-methylcyclohexanol, 4-isopropyl-cyclohexanol, 4-methyl-1- (I-methylethyl)-3- cyclohexen-l-ol, 2- (5,6,6-trimethyl-2-norbomyl) cyclohexanol, isobomylcyclohexanol, 3,3,5- trirnethylcycloheacanol, 1-methyl-4-isopropylcyclohexan-3-ol, 1, 2-dimethyl-3- (1- methylethyl) cyclohexan-1-ol, heptanol, 2,4dimethylheptan-1-ol, 2,4-dimethyl-2,6- heptandienol, 6,6-dimethyl-2-oxymethylbicyclo [3.1.1] 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 7-trimethylbicyclo [2.2.1] heptan-2- ol, 2,6-dimethylheptan-2-ol, 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-1-ol (geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol), 3,7-dimethyl- 1,6-octadien-3-ol (linalool), 3,7-dimethyloctan-1-ol (pelagrol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-1-ol, 3,7-dimethyl-6-octen-3-ol, 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), 2,6-dimethyl-5, 7-octadien-2-ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol, 3- methyloctan-3-ol, 2,6-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-1-octen-3-ol, 7-hydroxy-3,7-dimethyloctanal, 3-nonanol, 2,6-nonadien-1-ol, cis-6-nonen-1-ol, 6,8- dimethylnonan-2-ol, 3- (hydroxymethyl)-2-nonanone, 2-nonen-l-ol, 2,4-nonadien-l-ol, 3,7- dimethyl-1,6-nonadien-3-ol (ethyllinalool), decanol, 9-decenol, 2-benzyl-M-dioxa-5-ol, 2- decen-l-ol, 2,4-decadien-1-ol, 4-methyl-3-decen-5-ol, (isobutyl linallol), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 2,4- dodecadien-l-ol, 2, 7, 11-trimethyl-2,6,10-dodecatrien-1-ol (farnesol), 3,7,11-trimethyl- 1,6,10,-dodecatrien-3-ol, 3,7,11, 15-tetramethylhexadec-2-en-1-ol (phytol), 3,7,11,15- tetramethylhexadecl-en-3-ol (iso phytol), benzyl alcohol, p-methoxy benzyl alcohol (anisyl alcohol), para-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- (1-propenyl) phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-tert-butylphenol, 2-ethoxy-4-methylphenol, 2- methyl-4-vinylphenol, 2-isopropyl-5-methylphenol (thymol), pentyl-ortho-hydroxy benzoate,

ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-5- <BR> <BR> <BR> <BR> methoxy-1-methylbenzene, 2-tert-butyl-4-methyl-1-hydroxybenzene, I-ethoxy-2-hydroxy-4-<BR> <BR> <BR> <BR> <BR> <BR> propenylbenzene, 4-hydrozytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4- hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro-2-naphthol, 1,3,3- trimethyl-2-norbornanol (fenchol), 3a, inden-5-ol, 3a, 4,5,6,7,7a-hexahydro-3,4-dimethyl-4, 7-methano-lH-inden-5-ol, 2-methyl-2- vinyl-5- (1-hydroxy-1-methylethyl) tetrahydrofuran, b-caryophyllene alcohol, and mixtures thereof.

Non-limiting examples of esters suitably released by the pro-accords of the present invention include geranyl formate, citronellyl formate, phenylethyl formate, phenoxyethyl formate, trans-2-hexenyl formate, cis-3-hexenyl formate, cis-6-nonenyl formate, 9-decenyl formate, 3,5,5-trimethylhexyl formate, 3-methyl-5-phenylpentanyl formate, 6-methylheptan- 2-yl formate, 4- (2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-yl formate, 3-methyl-5-(2,2,3- trimethyl-3-cyclopenten-1-yl)-4-penten-2-yl formate, 4-isopropylcyclohexyleth-2-yl formate, 6,8-dimethylnonan-2yl formate, decahydro-b-naphthyl formate, 4-isopropylcyclohexylmethyl formate, linalyl formate, lavandulyl formate, citronellyl formate, a-terpinyl formate, nopyl formate, isobornyl formate, bornyl formate, isobornyl formate, guaiyl formate, 2-tert- butylyclohexyl formate, 4-tert-butylcyclohexyl formate, decahydro-b-naphthyl formate, menthyl formate, p-menthanyl formate, neryl formate, cinnamyl formate, ethyl acetate, butyl acetate, isoamyl acetate, hexyl acetate, 3,5,5-trimethylhexyl acetate, geranyl acetate, <BR> <BR> <BR> <BR> citronellyl acetate, phenylethyl acetate, phenoxyethyl acetate, trans-2-hexenyl acetate, cis-3- hexenyl acetate, cis-6-nonenyl acetate, 9-decenyl acetate, 3-methyl-5-phenylpentanyl acetate, 6-methyl-heptan-2-yl acetate, 4- (2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-yl acetate, 3- methyl-5- (2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-yl acetate, decahydro-b-naphthyl acetate, menthyl acetate, benzyl acetate, 4-isopropylcyclohexyleth-2-yl acetate, 6,8- dimethylnonan-2-yl acetate, 1-phenylethyl acetate, 4-isoproylcyclo-hexylmethyl acetate, linalyl acetate, lavandulyl acetate, citronellyl acetate, a-terpinyl acetate, nopyl acetate, isobornyl acetate, bornyl acetate, isobornyl acetate, guaiyl acetate, 2-tert-butylyclohexyl acetate, 4-tert-butylcyclohexyl acetate, decahydro-b-naphthyl acetate, menthyl acetate, p- menthanyl acetate, neryl acetate, cinnamyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, cis-3-hexenyl butyrate, cis-3-hexenyl isobutyrate, ethyl isovalerate, 2-methylbutyrate, ethyl hexanoate, 2-propenyl hexanoate, ethyl heptanoate, 2-propenyl heptanoate, ethyl octanoate, ethyl 2-trans-4-cis-decadienoate, methyl 2- nonynoate, benzyl propionate, benzyl isovalerate, phenylethyl isobutyrate, phenylethyl

isovalerate, a, a-dimethyl phenylethyl butyrate, methyl benzoate, hexyl benzoate, benzyl benzoate, ethyl phenylacetate, geranyl phenylacetate, 1-phenylethyl phenylacetate, methyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, geranyl propionate, geranyl isobutyrate, geranyl isovalerate, linalyl propionate, linalyl buryrate, linalyl isobutyrate, citronellyl propionate, citronellyl isobutyrate, citronellyl isovalerate, citronellyl tiglate, allyl 3- cyclohexylpropionate, methyl dihydrojasmonate, methyl 2-hexyl-3-oxocyclopentane- carboxylate, and mixtures thereof.

Non-limiting examples of aldehydes which are released by the pro-accords of the present invention include phenylacetaldehyde, p-methyl phenylacetaldehyde, p-isopropyl phenylacetaldehyde, methylnonyl acetaldehyde, phenylpropanal, 3- (4-t-butylphenyl)-2- <BR> <BR> <BR> <BR> methyl propanal (Lilial), 3- (4-t-butylphenyl)-propanal (Bourgeonal), 3- (4-methoxyphenyl)-2-<BR> <BR> <BR> <BR> <BR> <BR> <BR> methylpropanal (Canthoxal), 3- (4-isopropylphenyl)-2-methylpropanal (Cymal), 3- (3,4-<BR> <BR> <BR> <BR> <BR> <BR> methylenedioxyphenyl)-2-methylpropanal (Helional), 3- (4-ethylpheny)-2, 2-dimethylpropanal (Floralozone), phenylbutanal, 3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-hex- 3-enal, heptanal, cis-4-heptenal, 2-ethyl-2-heptenal, 2,6-dimethyl-5-heptenal (Melonal), 2,4- heptadienal, octanal, 2-octenal, 3,7-dimethyloctanal, 3,7-dimethyl-2, 6-octadien-1-al, 3,7- dimethyl-1, 6-octadien-3-al, 3,7-dimethyl-6-octenal (citronellal), 3,7-dimethyl-7- hydroxyoctan-1-al (hydroxy citronellal), nonanal, 6-nonenal, 2,4-nonadienal, 2,6-nonadienal, decanal, 2-methyl decanal, 4-decenal, 9-decenal, 2,4-decadienal, undecanal, 2-methyldecanal, 2-methylundecanal, 2,6,10-trimethyl-9-undecenal (Adoxal), undec-10-enyl aldehyde, undec- 8-enanal, dodecanal, tridecanal, tetradecanal, anisaldehyde, bourgenonal, cinnamic aldehyde, a-amylcinnam-aldehyde, a-hexyl cinnamaldehyde, methoxy-cinnamaldehyde, isocyclocitral, citronellyl oxyacet-aldehyde, cortexaldehyde, cumminic aldehyde, cyclamen aldehyde, florhydral, heliotropin, hydrotropic aldehyde, vanillin, ethyl vanillin, benzaldehyde, p-methyl benzaldehyde, 3,4-dimethoxybenzaldehyde, 3-and 4- (4-hydroxy-4-methyl-pentyl)-3- cyclohexene-1-carboxaldehyde (Lyral), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Tripial), I-methyl-3- (4-methylpentyl)-3-cyclohexencarboxaldehyde (Vemaldehyde), p- methylphenoxyacetaldehyde (Xi aldehyde), and mixtures thereof.

Non-limiting examples of ketones which are released by the pro-accords of the present invention include a-damascone, b-damascone, d-damascone, b-damascenone, muscone, 3,3-pentamethyl-4 (5H)-indanone (cashmeran), cisjasmone, dihvdrojasmone, a-ionone, b-ionone, dihydro-b-ionone, g-methyl ionone, a-iso-methyl ionone, 4- (3, 4-methylenedioxyphenyl) butan-2-one, 4- (4-hydroxyphenyl) butan-2-one, methyl b- naphthyl ketone, methyl cedryl ketone, 6-acetyl-1,1,2,4,4,7-hexamethyltetralin (tonalid), l-

carvone, 5-cyclohexadecen-1-one, acetophenone, decatone, 2- [2- (4-methyl-3-cyclohexenyl-1- yl) propyl] cyclopentan-2-one, 2-sec-butylcyclohexanone, b-dihydro ionone, allyl ionone, a- irone, a-cetone, a-irisone, acetanisole, geranyl acetone, 1- (2-methyl-5-isopropyl-2- cyclohexenyl)-l-propanone, acetyl diisoamylene, methyl cyclocitrone, 4-t-pentyl cyclohexanone, p-t-butylcyclohexanone, o-t-butylcyclohexanone, ethyl amyl ketone, ethyl pentyl ketone, menthone, methyl-7, 3-dihydro-2H-1,5-benzodioxepine-3-one, fenchone, and mixtures thereof.

Fragrance Release Half-life The tertiary alcohol-releasing pro-perfumes, as well as other pro-accords useful in the fragrance delivery systems of the present invention, hydrolyze upon contact with human skin to release fragrance raw materials. However, in order to meet the needs of the formulator, the pro-accords must release their perfume ingredients at a rate useful for providing a sustainable fragrance level.

The task of measuring the release rate of pro-accords on human skin is cumbersome and prone to variation. It has therefore been surprisingly discovered that pro-accords can be evaluated in a manner not involving contact with human skin, a method which directly indicates their suitability for use as tertiary alcohol-releasing pro-accords. This procedure also is applicable to all pro-perfumes suitable for use in the fragrance delivery systems of the present invention.

For the purposes of the present invention pro-accords which have a"Fragrance Release Half-life"of less than or equal to 12 hours when measured in NaH2PO4 buffer at pH 2.5 and greater than or equal to 0.1 hour when measured in NaH2PO4 buffer at pH 5.3 are suitable as tertiary alcohol-releasing orthoesters or as pro-accords useful in the fragrance delivery systems of the present invention. The"Fragrance Release Half-life"is defined herein as follows.

Pro-accords deliver their corresponding mixture of fragrance raw materials or fragrance accords according to the equation: Pro-Accord o Accord wherein the accord which is released, may in some instances comprise a single fragrance raw material, but is preferably a binary accord or a multiple fragrance raw material accord.

The rate at which the accord is released is defined by the formula: Rate = k [Pro-accord] and can be further expressed by the formula: <BR> <BR> -= k [Pro-accord]<BR> <BR> dt

wherein k is the release rate constant and [Pro-accord] is the concentration of pro-accord.

For the purposes of the present invention the"Fragrance Release Half-life", tlx2, is related to the release rate constant by the formula: 0.0. 693 tl/2-k and this relationship is used for the purposes of the present invention to determine the "fragrance Release Half-life" (FRHL).

Due to the hydrophobic nature of some pro-accords, it is necessary to conduct the determination of tl/2 and k in a mixture of 90/10 dioxane/phosphate buffered water.

An example of the procedure used to measure the suitability of a pro-accord for use in the fragrance delivery systems at pH 2.5 is as follows. The phosphate buffered water is prepared by admixing 3.95 mL of 85% phosphoric acid (H3P04) and 24 g of sodium dihydrogen phosphate (NaH2P04) with one liter of water. The pH of this solution is approximately 2.5. Next 10 mL of the phosphate buffer is admixed with 90 mL of dioxane and the pro-fragrance to be analyzed is added. The hydrolysis kinetics are then monitored by conventional HPLC at 30° C.

The orthoester bis (n-pentyl) dihydromyrcenyl orthoformate has a fragrance release half-life, as measured at pH 5.3 under the above described conditions, of approximately 1.3 hrs and is, therefore, a suitable orthoester for delivering the tertiary alcohol dihydromyrcenol and for use in the fragrance delivery systems of the present invention.

EXAMPLE 1 Bis (phenvlethvl) mono (dihvdromvrcenol) orthoformate Tris (phenylethyl) orthoformate (1 equiv), dihydromyrcenol (3 equiv), and an acid catalyst [for example, 2,4,6-trimethylbenzoic acid, 2,6-dichlorobenzoic acid, or tetrabutylammonium hydrogen sulfate, 1-2 mol %], are stirred under high vacuum (< 0.25 mm Hg) at 40 °C for 5 days. The reaction mixture is then diluted with 2 volumes of ether, washed with a saturated solution of sodium carbonate, dried, evaporated, and subjected to

flash chromatography to afford analytically pure bis (phenylethyl) mono (dihydromyrcenol) orthoformate.

The following is an example of the fragrance delivery system of the present invention.

EXAMPLE 2 Ingredients weight % Tertiary Alcohol-Releasing Pro-Accord Component Pro-Accord'5.1 Potassium carbonate 2 ethanol 3 12.4 Other Pro-Accords Tris (citronellyl) orthoformate 8.1 Citronellyloxyacetaldehyde bis (citronellyl) acetal 4.7 Fragrance Raw Material Component Phenyl acetaldehyde 0.7 Base notes and fragrance raw materials 4 61. 4 Adjuncts5 2.1 Ethanol 6 balance 1. Bis (nhenvlethvl) mono (dihvdromvrcenol) orthoformate.

2. Sufficient to provide 1 millimolar potassium carbonate reserve alkalinity.

3. Ethanol carrier contains less than 1% water.

4. Fragrance raw material base, middle and top notes which includes polyethylene glycol as carrier and anhydrous ethanol as a diluent.

5. Diethyl phthalate as a fixative.

6. Anhydrous ethanol.