Perfumes having odor longevity benefits

The present invention relates to perfume or fine fragrance compositions inter alia perfumes, colognes, eau de toilettes, and after shave lotions, comprising pro-accord compounds which release their fragrance raw material components on a delayed basis therefore providing sustained fragrance levels to the user. Typically the pro-accords are comprised of orthoesters, ketals, acetals, orthocarbonates which release two or more fragrance raw materials upon hydrolysis. The present invention also relates to an article of manufacture comprising a first pro-accord containing reservoir and a second fragrance raw material reservoir and a means for admixing and applying the perfume material.

FIELD OF THE INVENTION 
The present invention relates to fine fragrance perfumes, eau de toilettes, 
colognes, after-shave lotions and other fragrance-containing personal 
perfumery compositions for application directly to skin, said compositions 
having increased odor longevity benefits. The odor longevity benefits are 
produced by combining top and middle note pro-fragrances alone or in 
combination with other fragrance raw materials, said pro-fragrances 
releasing volatile top and middle notes at a predetermined rate upon 
contact with skin thereby either maintaining the initial perfume 
characteristics for extended periods or evolving a new fragrance 
characteristic that evolves over time. 
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 
modern chemistry, individual components responsible for the odor 
properties of these resins, gums and oils were isolated and subsequently 
characterized. Modern 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. In addition, fragrances are categorized by the odor they produce; 
some of these descriptors are broad and others are relatively specific. 
For example, "floral" is a term which connotes odors associated with 
flowers while the term "lilac" is more specific. Descriptors used by those 
skilled in the art of perfumes and fine fragrances are inter alia "rose", 
"floral", "green", "citrus", "spicy", "honey", and "musk". 
Top, middle, and base notes each serve a different purpose in the blending 
of fragrances and when properly formulated produce a "balanced fragrance" 
composition. Based on volatility, these notes are described by those 
skilled in the art as: the base notes having the most long lasting aroma; 
the middle notes, have a medium volatility; and the top notes are the most 
volatile. Key to successfully formulating a fragrance-containing 
composition is the precise balance between these three groups of materials 
producing a fragrance-containing composition that diffuses during its 
evaporation in a manner which has an aesthetic quality. 
It is recognized by those skilled in the art that descriptors which relate 
to aesthetic perceptions such as "top", "middle" and "base" notes are 
relative terms. A FRM categorized as a top note by one formulator usually 
has the identical classification among most other Perfumers. The same is 
true for the middle and base notes, however, occasionally one formulator 
may classify a given fragrance raw material as a middle note rather than a 
top note, or vice versa, but this fact does not diminish the utility of a 
given compound or its absolute identity. Top, middle and base notes are 
now combined in a reproducible manner to produce perfumes, colognes, 
after-shave lotions, eau de toilettes, etc. for application to skin, which 
have unique and pleasant odor characteristics. Yet apart from this 
pleasant fragrance, a perfume, cologne, or eau de toilette must meet a 
number of technical requirements. It must be sufficiently strong, it must 
be persistent, and it must retain its "essential character" throughout its 
period of evaporation. It is to these latter two requirements that the 
present invention is directed. 
Due to the uneven rate of evaporation of the components which comprise a 
fine perfume or fragrance, the initial fragrance may be quite different 
than the aroma perceived several hours later. This problem is solved in 
many different ways by the user. One method is to "load up" on the perfume 
initially and rely on the natural evaporation rate to diminish the 
fragrance to a suitable level several hours later when the desired effect 
is needed. Another method which is used 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 "refreshing" of perfume. After 
some time these base notes overwhelm the other fragrance notes and destroy 
the original fragrance balance. 
BACKGROUND ART 
In addition to the above-cited references, the following relate to the 
subject matter of fragrance ingredients. U.S. Pat. No. 5,266,592 Grub et 
al., issued Nov. 30, 1993; U.S. Pat. No. 5,081,111 Akimoto et al., issued 
Jan. 14, 1992; U.S. Pat. No. 4,994,266 Wells, issued Feb. 19, 1991; U.S. 
Pat. No. 3,849,326 Jaggers et al., issued Nov. 19, 1974; U.S. Pat. No. 
3,779,932 Jaggers et al., issued Dec. 18, 1973; JP 07-179,328 published 
Jul. 18, 1995; JP 05-230496 published Sep. 7, 1993; WO 96/14827 published 
May 23, 1996; and WO 95/16660 published Jun. 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 a perfume or fine fragrance can be formulated 
which provides the user with a more enduring fragrance level and more 
sustained fragrance balance. What is meant by a "more enduring fragrance 
level" is that the fragrance raw materials which comprise the scent or 
fragrance accords of the perfume or fine fragrance are present upon the 
skin for a longer period of time than if the fragrance raw materials had 
been applied as an admixture. What is meant by a "more sustained fragrance 
balance" is that the relative proportion of top, middle, and base notes is 
more effectively maintained for a period of time longer than if the 
fragrance raw materials had been applied as an admixture. This increased 
fragrance endurance and balance is achieved by mitigating the loss of 
volatile top and middle note fragrance raw materials due to evaporation. 
The top and middle character notes are delivered via pro-accord compounds 
which do not begin to hydrolyze and release the fragrance raw materials 
until the scent-containing material is applied to human skin. 
The first aspect of the present invention relates to a perfume or fine 
fragrance composition applied to skin having increased fragrance retention 
and fragrance longevity, said compositions are inter alia perfumes, fine 
fragrances, fragrance oils, colognes, eau de toilettes, or after shave 
lotions, comprising: 
A) a pro-accord component comprising: 
i) one or more pro-accords formed from at least one fragrance raw material, 
said pro-accord releasing upon hydrolysis at least two fragrance raw 
materials selected from the group consisting of primary, secondary, and 
tertiary alcohols, aldehydes, ketones, esters, carbonates, and mixtures 
thereof, provided each pro-accord: 
a) is formed from at least one fragrance raw material having a molecular 
weight greater than or equal to about 100 g/mol; 
b) has a molecular weight greater than or equal to about 300 g/mol; 
c) has a molecular weight at least two times greater than the lowest 
molecular weight fragrance raw material which comprises said pro-accord; 
d) 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 measured in 
NaH.sub.2 PO.sub.4 buffer; 
ii) the balance carriers, stabilizers, and other adjunct ingredients 
whereby said pro-accord component is provided with an amount of reserve 
alkalinity equal to at least 0.001 molar NaOH; and 
B) a fragrance raw material component comprising: 
i) a mixture of base note fragrances; 
ii) one or more top and middle note fragrances; 
iii) the balance carriers, fixatives, and other adjunct ingredients. 
It is also an aspect of the present invention to provide an article of 
manufacture which serves to deliver the perfumes and fine fragrances of 
the present invention. These articles can comprise one or more reservoirs 
for storage of the fragrance materials until they are delivered to the 
skin of the user. In addition the articles of the present invention can 
comprise reservoirs which comprise a material having an alkaline or a 
neutralized surface component. 
Another aspect of the present invention is to provide pro-accords which 
provide fragrance raw materials at a level wherein the "odor value" or 
"level of noticeability" is greater than or equal to 1 as define herein. 
It is a further aspect of the present invention to provide a means by which 
a perfume or fine fragrance having a "first fragrance characteristic" has 
this scent replaced by a "second evolving fragrance characteristic". 
It is a yet further aspect of the present invention to provide a means for 
delivering the perfume or fine fragrance material wherein the pro-accord 
material is admixed with other perfume components prior to delivery to the 
skin of the user. 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 (.degree.C.) 
unless otherwise specified. All documents cited arc in relevant part, 
incorporated herein by reference. 
DETAILED DESCRIPTION OF THE INVENTION 
It has now been surprisingly found that certain fragrance raw materials or 
perfume components can be converted into a releasable "pro-fragrance" form 
which allows for the controlled release of the parent fragrance material 
upon exposure to human skin. By understanding the molecular weight 
requirements as well the "Fragrance Release Half-life", t.sub.1/2, 
disclosed within the present invention, the formulator can choose the 
precise "pro-fragrance" form to achieve controlled release of the volatile 
ingredients and therefore maintain the "initial fragrance profile" for 
extended periods of time. In addition, by formulating the proper 
pro-fragrances new characteristics can be caused to evolve over the period 
of use. These discoveries are applicable to perfumes, colognes, 
after-shaves, and other fragrance-containing materials in use today. 
The releasable pro-fragrances suitable for use in the present invention, 
have a molecular weight requirement that has not been realized by others 
who have previously formulated pro-fragrance materials. This molecular 
weight requirement relates to one or more aspects of the pro-fragrance, 
for example, in substantivity differences, volatility differences, etc. 
For example, U.S. Pat. No. 5,378,468 Suffis et al., issued Jan. 3, 1995, 
describes pro-fragrance containing compositions, inter alia, deodorants, 
lotions, and creams, which do not produce fragrances until contacted with 
skin. However, this reference falls short of teaching that certain 
pro-fragrances or pro-fragrance forms, although suitable for use in 
controlling the release rate of fragrance raw materials on the short term, 
are not themselves suitable for use in fine perfumes, colognes, eau de 
toilettes, etc. wherein extended benefits for the wearer are desired. For 
example, certain pro-perfume forms are too volatile for formulation 
according to the present invention because they themselves evaporate as 
fast as, or faster, than the fragrance materials themselves. In addition, 
many volatile pro-fragrances outside the scope of the present invention 
have their own distinguishable odor that is significantly different that 
the odor of the released fragrance. It is therefore not uncommon to have a 
pro-fragrance incompatible with the other perfume components. Many 
pro-fragrances have their own "fragrance" and it is common that the 
"characteristic" of the pro-fragrance odor is not within the same class of 
odors as the target composition. For example, the pro-fragrance may have 
an "herbal" odor but the released fragrance is "rose-like" in character. 
Pro-perfumes which are acid labile (i.e., release their fragrance materials 
in an acid containing medium such as the acid mantle of skin) can be 
suitably formulated into highly alkaline matrices which typically comprise 
roll-on deodorants, creams, lotions, etc. Many of the fragrance 
ingredients which comprise perfumes, colognes, eau de toilettes, 
after-shave lotions, etc. are not suitable for inclusion in an alkaline pH 
environment, for example, many of the commonly known fragrance notes are 
esters and they are susceptible to rapid hydrolysis at pH levels much 
above neutrality. 
The present invention provides releasable pro-fragrances which are 
activated upon contact with the acid mantle of the skin. The 
pro-fragrances of the present invention are acetals, ketals, orthoesters 
and orthocarbonates having a molecular weight of at least 300 g/mol. The 
present invention also provides fine perfumes, eau de toilettes, and 
colognes that comprise a pro-fragrance component in a releasable form such 
that the fragrance is released at a rate which provides extended fragrance 
benefits together with a component comprising free fragrances and other 
middle and base notes that are not stable to alkaline pH. The present 
invention also provides a method for selecting pro-fragrances which 
release their fragrances in a controlled manner allowing for a second 
subsequent fragrance "characteristic" to develop over time as replacement 
for the initial fragrance "characteristic". 
The present invention also provides for pro-accords which are capable of 
releasing fragrance raw materials at a rate which is of utility to the 
formulator of fine fragrances or perfumes. For example, as described 
further herein below, the pro-accords of the present invention have 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. In addition, the 
fragrance raw materials are released at a level wherein the odor value of 
said fragrance raw material is greater than 1. 
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. 
The present invention relates to perfume and fine fragrance compositions 
having scent or odor longevity benefits wherein these benefits are 
achieved by controllably releasing the fragrance components that comprise 
the perfume or fine fragrance. The present invention also relates to 
changing the "characteristic notes" of a fragrance composition by 
releasing new fragrance notes as the original notes evaporate or diffuse 
from the skin. For example, a "melon note" fragrance composition may be 
suitably conveyed to a "rose note" fragrance by the evaporation of the 
original "melon characteristics" and subsequent release of the new "rose 
characteristics". 
Fine perfumes typically comprise components which react with human 
olfactory sites resulting in what is known as "fragrance". Typical 
molecules which comprise perfume fragrances are linear and cyclic alkenes 
(i.e., terpenes), primary, secondary and tertiary alcohols, nitrites, 
ethers, saturated and unsaturated aldehydes, esters, ketones, and mixtures 
thereof. Each of these perfume fragrances can be classified according to 
its volatility into one of three categories; "top note", "middle note", 
and "base note". 
For the purposes of the present invention "top note" fragrances are defined 
as "fragrances having a high vapor pressure, and when applied to a paper 
sachet, vaporization takes place within 2 hours, and no scent remains; 
essentially, the initial impression of the perfume formulation is provided 
by top notes". 
For the purposes of the present invention "middle note" fragrances are 
defined as "fragrances having a medium vapor pressure, and when applied to 
a paper sachet, the scent remains from about 2 to about 6 hours; 
essentially, middle notes provide the skeleton of the perfume 
formulation". 
For the purposes of the present invention "base note" fragrances are 
defined as "fragrances having a low vapor pressure and high retentivity, 
and when applied to a paper sachet, the scent remains for more than about 
6 hours; essentially, base notes provide the characteristic of the perfume 
formulation. 
The terms "top note", "middle note", and "base note" are well recognized by 
those skilled in the art of fragrance-containing compositions. However, 
reference to a specific fragrance raw material as a "top note" within the 
present invention does mean that others skilled in the art of 
fragrance-containing compositions may not categorized the same ingredient 
as a "middle note". The same applies to fragrance raw materials referred 
to as "middle notes" and "base notes". 
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". 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". 
Typically "fragrance raw materials" comprise inter alia alcohols, ketones, 
aldehydes, esters, ethers, nitrites, 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 example, but not by way of limitation, the fragrance accords released 
by the pro-accords of the present invention have a "heart", "character", 
or "note" which is described as inter 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". 
The pro-accords of the present invention are comprised of one or more 
fragrance raw materials. The fragrance raw materials selected to comprise 
the final released accord are converted into a chemical species or 
reactive chemical form which releases the fragrance raw materials once the 
pro-accord is subjected to the proper hydrolysis conditions. Depending 
upon the particular embodiment chosen, the hydrolysis conditions may range 
from the acid mantle of human skin, to the nascent moisture which 
comprises air. These chemically modified forms of the fragrance raw 
materials are the "pro-accords" of the present invention. One principle 
aspect of the present invention is the ability of pro-accords described 
herein to deliver more than one fragrance raw material when the 
"pro-accord" has been formed from only one fragrance raw material. All of 
the pro-accords of the present invention are capable of releasing at least 
two fragrance raw materials (hereinafter "binary accord") upon deposition, 
for example, onto skin or hair. There are two types of pro-accords; 
"symmetrical" pro-accords and "unsymmetrical" pro-accords each described 
herein further below. 
Molecular Weight 
The pro-accords of the present invention generally have a molecular weight 
of at least 300 g/mol, preferably greater than 325 g/mol, more preferably 
greater than 350 g/mol. It is also a condition of the present invention 
that the final molecular weight of the pro-accord is at least 2 times, 
preferably at least 2.25 times, more preferably 2.5 times, most preferably 
at least 2.75 times the molecular weight of the lowest fragrance material 
component. 
For the purposes of the present invention, only fragrance raw materials 
having a molecular weight of at least 100 g/mol are considered "fragrance 
raw materials". Therefore, low molecular weight materials inter alia 
methanol, ethanol, methyl acetate, ethyl acetate, and methyl formate which 
are common components of fragrance accords are excluded from the class of 
compounds defined herein as "fragrance raw materials". However, the 
formulator may wish to deliver these lower molecular weight materials 
(less than a molecular weight of 100 g/mol) as carriers, astringents, 
diluents, balancers, or as other suitable adjunct materials. 
By way of illustration and not limitation, the pro-accord tris(geranyl) 
orthoformate is considered, for the purposes of the present invention to 
be formed from three equivalents of geraniol. This pro-accord releases the 
binary accord geraniol/geranyl formate. This pro-accord has a molecular 
weight of approximately 472 g/mol. The lowest molecular weight fragrance 
raw material which is a component of tris(geranyl)orthoformate is geraniol 
which has a molecular weight of approximately 154 g/mol. Therefore 
tris(geranyl)orthoformate has a molecular weight greater than 3 times the 
molecular weight of the lowest molecular weight fragrance raw material 
component (geraniol) and hence is a most preferred pro-accord. 
For the purposes of the present invention substituted or unsubstituted 
alkyleneoxy units are defined as moieties having the formula: 
##STR1## 
wherein R.sup.5 is hydrogen, methyl, and mixtures thereof, R.sup.6 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: 
##STR2## 
wherein R.sup.5 is hydrogen, C.sub.1 -C.sub.18 alkyl, and mixtures 
thereof; R.sup.6 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: 
##STR3## 
wherein R.sup.5 and R.sup.6 are each independently hydrogen, hydroxy, 
nitrilo, halogen, nitro, carboxyl (--CHO; --CO.sub.2 H; --CO.sub.2 R'; 
--CONH.sub.2 ; --CONHR'; --CONR'.sub.2 ; wherein R' is C.sub.1 -C.sub.12 
linear or branched alkyl), amino, alkylamino, and mixtures thereof, p is 
from 1 to about34. 
For the purposes of the present invention substituted or unsubstituted 
aryloxy units are defined as moieties having the formula: 
##STR4## 
wherein R.sup.5 and R.sup.6 are each independently hydrogen, hydroxy, 
nitro, halogen, nitro, carboxyl (--CHO; --CO.sub.2 H; --CO.sub.2 R'; 
--CONH.sub.2 ; --CONHR'; --CONR'.sub.2 ; wherein R' is C.sub.1 -C.sub.12 
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: 
##STR5## 
wherein R.sup.5 and R.sup.6 are each independently hydrogen, hydroxy, 
nitro, halogen, nitro, carboxyl (--CHO; --CO.sub.2 H; --CO.sub.2 R'; 
--CONH.sub.2 ; --CONHR'; --CONR'.sub.2 ; wherein R' is C.sub.1 -C.sub.12 
linear or branched alkyl), amino, alkylamino, and mixtures thereof, q is 
from 1 about 34. 
For the purposes of the present invention substituted or unsubstituted 
oxyalkylenearyl units are defined as moieties having the formula: 
##STR6## 
wherein R.sup.5 and R.sup.6 are each independently hydrogen, hydroxy, 
nitro, halogen, nitro, carboxyl (--CHO; --CO.sub.2 H; --CO.sub.2 R'; 
--CONH.sub.2 ; --CONHR'; --CONR'.sub.2 ; wherein R' is C.sub.1 -C.sub.12 
linear or branched alkyl), amino, alkylamino, and mixtures thereof, w is 
from 1 about 34. 
Orthoesters 
One class of preferred compounds useful as pro-accords according to the 
present invention are orthoesters having the formula: 
##STR7## 
wherein hydrolysis of the orthoester releases fragrance raw material 
components according to the following scheme: 
##STR8## 
wherein R is hydrogen, C.sub.1 -C.sub.8 linear alkyl, C.sub.4 -C.sub.20 
branched alkyl, C.sub.6 -C.sub.20 cyclic alkyl, C.sub.6 -C.sub.20 branched 
cyclic alkyl, C.sub.6 -C.sub.20 linear alkenyl, C.sub.6 -C.sub.20 branched 
alkenyl, C.sub.6 -C.sub.20 cyclic alkenyl, C.sub.6 -C.sub.20 branched 
cyclic alkenyl, C.sub.6 -C.sub.20 substituted or unsubstituted aryl, 
preferably the moieties which substitute the aryl units are alkyl 
moieties, and mixtures thereof, preferably R is hydrogen, methyl, ethyl, 
and phenyl. R.sup.1, R.sup.2 and R.sup.3 are independently C.sub.1 
-C.sub.20 linear, branched, or substituted alkyl; C.sub.2 -C.sub.20 
linear, branched, or substituted alkenyl; C.sub.5 -C.sub.20 substituted or 
unsubstituted cyclic alkyl; C.sub.6 -C.sub.20 substituted or unsubstituted 
aryl, C.sub.2 -C.sub.40 substituted or unsubstituted alkyleneoxy; C.sub.3 
-C.sub.40 substituted or unsubstituted alkyleneoxyalkyl; C.sub.6 -C.sub.40 
substituted or unsubstituted alkylenearyl; C.sub.6 -C.sub.32 substituted 
or unsubstituted aryloxy; C.sub.6 -C.sub.40 substituted or unsubstituted 
alkyleneoxyaryl; C.sub.6 -C.sub.40 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, nitro, halogen, nitro, carboxyl (--CHO; --CO.sub.2 H; --CO.sub.2 
R'; --CONH.sub.2 ; --CONHR'; --CONR'.sub.2 ; wherein R'is C.sub.1 
-C.sub.12 linear or branched alkyl), amino, C.sub.1 -C.sub.12 mono- and 
dialkylamino, and mixtures thereof. 
Non-limiting examples of R.sup.1, R.sup.2 and R.sup.3 are methyl, 
2,4-dimethyl-3-cyclohexene-1-methyl (Floralol), 2,4-dimethyl cyclohexane 
methyl (Dihydro floralol), 
5,6-dimethyl-1-methylethenyl-bicyclo2.2.1!hept-5-ene-2-methyl (Arbozol), 
2,4,6-trimethyl-3-cyclohexene-1-methyl (Isocyclo geranyl), 
4-(1-methylethyl)cyclohexylmethyl (Mayol), 
.alpha.-3,3-trimethyl-2-norboranylmethyl, 
1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methyl, ethyl, 2-phenylethyl, 
2-cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-methylphenyl)ethyl, 
2-(p-methylphenyl)ethyl, 6,6-dimethylbicyclo3.1.1!hept-2-ene-2-ethyl 
(nopyl), 2-(4-methylphenoxy)ethyl, 3,3-dimethyl-.DELTA..sup.2 
-.beta.-norboranylmethyl, 2-methyl-2-cyclohexylethyl, 
1-(4-isopropylcyclohexyl)ethyl, 1-phenyl-1-hydroxyethyl, 
1,1-dimethyl-2-phenylethyl, 1,1-dimethyl-2-(4-methylphenyl)ethyl, propyl, 
1-phenylpropyl, 3-phenylpropyl, 2-phenylpropyl (Hydrotropic Alcohol), 
2-(cyclododecyl)-propan-1-yl (Hydroxyambran), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-yl (Majantol), 
2-methyl-3-phenylpropyl, 3-phenyl-2-propen-1-yl (cinnamyl alcohol), 
2-methyl-3-phenyl-2-propen-1-yl (methylcinnamyl alcohol), 
.alpha.-n-pentyl-3-phenyl-2-propen-1-yl (.alpha.-amylcinnamyl alcohol), 
ethyl-3-hydroxy-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-1-yl)butyl, 
2-ethyl-4-(2,2,3-trimethylcyclopent-3-enyl)-2-buten-1-yl, 
3-methyl-2-buten-1-yl, 
2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-yl, 
3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 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, cis-3-pentenylt 
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-dimethyltricyclo2.2.1.0(2,6)!hept-3-yl)-2-penten-1-yl 
(santalyl), 4-methyl-1-phenyl-2-pentyl, 
(1-methyl-bicyclo2.1.1!hepten-2-yl)-2-methylpent-1-en-3-yl, 
3-methyl-1-phenylpent-3-yl, 
1,2-dimethyl-3-(1-methylethenyl)cyclopent-1-yl, 2-isopropyl-4-methyl-2-hex 
enyl, cis-3-hexen-1-yl, trans-2-hexen-1-yl, 
2-isopropenyl-5-methyl-4-hexen-1-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-1-yl, 1-methyl-4-isopropenylcyclohex-3-yl, 
4-iso-propyl -1-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, 1-methyl-4-isopropylcyclohex-3-yl (menthol), 
1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-yl, heptyl, 
2,4-dimethylhept-1-yl, 2,4-dimethyl-2,6-heptandienyl, 
6,6-dimethyl-2-oxymethylbicyclo3.1.1!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-dimethyl-3-hydroxy-2-methylenebicyclo3.1.1!-heptyl, 
1,7,7-trimethylbicyclo2.2.1!hept-2-yl, 2,6-dimethylhept-2-yl, 
2,6,6-trimethylbicyclo1.3.3!hept-2-yl, octyl, 2-octenyl, 
2-methyloctan-2-yl, 2-methyl-6-methylene-7-octen-2-yl (myrcenyl), 
7-methyloctan-1-yl, 3,7-dimethyl-6-octenyl, 3,7-dimethyl-7-octenyl, 
3,7-dimethyl-6-octen-1-yl (citronellyl), 3,7-dimethyl-2,6-octadien-1-yl 
(geranyl), 3,7-dimethyl-2,6-octadien-1-yl (neryl), 
3,7-dimethyl-1,6-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-1-octen-3-yl, 7-hydroxy-3,7-dimethyloctanalyl, 3-nonyl, 
6,8-dimethylnonan-2-yl, 3-(hydroxymethyl)-2-nonanone, 2-nonen-1-yl, 
2,4-nonadien-1-yl, 2,6-nonadien-1-yl, cis-6-nonen-1-yl, 
3,7-dimethyl-1,6-nonadien-3-yl, decyl, 9-decenyl, 2-benzyl-M-dioxa-5-yl, 
2-decen-1-yl, 2,4-decadien-1-yl, 4-methyl-3-decen-5-yl, 
3,7,9-trimethyl-1,6-decadien-3-yl (isobutyl linallyl), undecyl, 
2-undecen-1-yl, 10-undecen-1-yl, 2-dodecen-1-yl, 2,4-dodecadien-1-yl, 
2,7,11-trimethyl-2,6,10-dodecatrien-1-yl (farnesyl), 
3,7,11-trimethyl-1,6,10,-dodecatrien-3-yl, 
3,7,11,15-tetramethylhexadec-2-en-1-yl (phytyl), 
3,7,11,15-tetramethylhexadec-1-en-3-yl (iso phytol), benzyl, 
p-methoxybenzyl (anisyl), para-cymen-7-yl (cuminyl), 4-methylbenzyl, 
3,4-methylenedioxybenzyl, 2-(methyl)carboxy-1-hydroxyphenyl, 
2-(benzyl)carboxy-1-hydroxyphenyl, 
2-(cis-3-hexenyl)-carboxy-1-hydroxyphenyl, 
2-(n-pentyl)carboxy-1-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-1-hydroxyphenyl, 4-tert-butyl-1-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-1,3-dihydroxyphenyl, 
5-methoxy-3-methyl-1-hydroxyphenyl, 2-tert-butyl-4-methyl-1-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-1H-inden-5-yl, 
3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-yl, 
2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuranyl, 
.beta.-caryophyllenyl, and mixtures thereof. 
Also R.sup.1, R.sup.2, or R.sup.3 units may serve to link two pro-accords 
for the purpose of providing greater substantivity. An example of 
pro-accord linking by a diol has the following formula: 
##STR9## 
In addition to the releasable alcohols listed herein above, orthoesters 
according to the present invention are also cyclic orthoesters which are 
comprised from at least one diol having the formula: 
##STR10## 
wherein R.sup.8, R.sup.9, R.sup.10, and R.sup.11 are each in dependently 
hydrogen, C.sub.1 -C.sub.20 linear or branched alkyl, C.sub.1 -C.sub.20 
linear or branched alkenyl, C.sub.1 -C.sub.20 linear, branched or cyclic 
alkylenecarboxy, C.sub.1 -C.sub.20 linear, branched, or cyclic 
carboxyalkyl, C.sub.1 -C.sub.20 linear or branched alkyleneamino, C.sub.1 
-C.sub.20 linear or branched aminoalkyl, C.sub.1 -C.sub.20 linear, 
branched, or cyclic alkylenecarboxamido, C.sub.1 -C.sub.20 linear or 
branched carboxamidoalkyl, alkyleneoxy having the formula: 
##STR11## 
wherein R.sup.12 is hydrogen or methyl; R.sup.13 is hydrogen or C.sub.1 
-C.sub.2 alkyl; n is from 0to 4, x is from 1 to about 20, y is from 0 to 
about 20. 
Orthoester Releasable Components: Hydrolysis of the orthoesters of the 
present invention have two types of releasable components, namely alcohols 
and esters. Hydrolysis of an orthoester will yield two equivalents of 
releasable alcohol, preferably a primary or secondary alcohol and one 
equivalent of releasable ester. The released ester, when taken together 
with the released alcohol, forms a binary fragrance accord. For example 
tri-geranyl orthoformate releases the binary accord geraniol/geranyl 
formate. 
Preferred esters which are releasable components of the orthoesters of the 
present invention included but are not limited to 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-2-yl formate, 
decahydro-.beta.-naphthyl formate, 4-isopropylcyclohexylmethyl formate, 
linalyl formate, lavandulyl formate, citronellyl formate, .alpha.-terpinyl 
formate, nopyl formate, isobornyl formate, bornyl formate, isobornyl 
formate, guaiyl formate, 2-tert-butylyclohexyl formate, 
4-tert-butylcyclohexyl formate, decahydro-p-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, 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-.beta.-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, .alpha.-terpinyl 
acetate, nopyl acetate, isobornyl acetate, bornyl acetate, isobornyl 
acetate, guaiyl acetate, 2-tert-butylyclohexyl acetate, 
4-tert-butylcyclohexyl acetate, decahydro-.beta.-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, 
.alpha.,.alpha.-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 alcohols suitably released by the hydrolysis of 
the orthoester pro-accords include methanol, 
2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethyl cyclohexane 
methanol (Dihydro floralol), 
5,6-dimethyl-1-methylethenylbicyclo2.2.1!hept-5-ene-2-methanol (Arbozol), 
2,4,6-trimethyl-3-cyclohexene-1-methanol (Isocyclo geraniol), 
4-(1-methylethyl)cyclohexanemethanol (Mayol), 
.alpha.-3,3-trimethyl-2-norborane methanol, 
1,1-dimethyl-1-(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-.DELTA..sup.2 -.beta.-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, n-propanol, 2-propanol, 
1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic 
Alcohol), 2-(cyclododecyl)propan-1-ol (Hydroxy-ambran), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majantol), 
2-methyl-3-phenylpropanol, 3-phenyl-2-propen-1-ol (cinnamyl alcohol), 
2-methyl-3-phenyl-2-propen-1-ol (methylcinnamyl alcohol), 
(.alpha.-n-pentyl-3-phenyl-2-propen-1-ol (.alpha.-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-1-yl)butanol, 
2-ethyl-4-(2,2.3-trimethyl-cyclopent-3-enyl)-2-buten-1ol, 
3-methyl-2-buten-1-ol, 
2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-1-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, pentanol, cis-3-pentenol, 
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-dimethyltricyclo2.2.1.0(2,6)!hept-3-yl)-2-penten-1-ol 
(santalol), 4-methyl-1-phenyl-2-pentanol, 
(1-methyl-bicyclo2.1.1!hepten-2-yl)-2-methylpent-1-en-3-ol, 
3-methyl-1-phenylpentan-3-ol, 
1,2-dimethyl-3-(1-methylethenyl)cyclopentan-1-ol, 
2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 
2-isoproenyl-4-methyl-4-hexen-1-ol (Lavandulol), 
2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-cyclohexene 
(Dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-ol 
(carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol, 
1-methyl-4-iso-propenylcyclohexan-3-ol, 
4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclo-hexanol, 
2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 
4-isopropyl-cyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol, 
2-(5,6,6-trimethyl-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 
3,3,5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, 
1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-ol, heptanol, 
2,4-dimethylheptan-1-ol, 2,4-dimethyl-2,6-heptandienol, 
6,6-dimethyl-2-oxymethylbicyclo3.1.1!hept-2-ene (myrtenol), 
4-methyl-2,4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 
3,6-dimethyl-3-vinyl-5-hepten-2-ol, 
6,6-dimethyl-3-hydroxy-2-methylenebicyclo3.1.1!heptane, 
1,7,7-trimethylbicyclo2.2.1!heptan -2-ol, 2,6-dimethylheptan-2-ol, 
2,6,6-trimethylbicyclo1.3.3!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-1-ol 
(geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol), 
3,7-dimethyl-1,6-octadien-3-ol (linalool), 3,7-dimethyloctan-1ol 
(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, 
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-1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6-nonadien-3-ol, decanol, 
9-decenol, 2-benzyl-M-dioxa-5-ol, 2-decen-1-ol, 2,4-decadien-1-ol, 
4-methyl-3-decen-5-ol, 3,7,9-trimethyl-1,6-decadien-3-ol (isobutyl 
linallol), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 
2,4-dodecadien-1-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-tetramethylhexadec-1-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-methoxy-1-methylbenzene, 
2-tert-butyl-4-methyl-1-hydroxybenzene, 
1-ethoxy-2-hydroxy-4-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,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1H-inden-5-ol, 
3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-ol, 
2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuran, 
.beta.-caryophyllene alcohol, and mixtures thereof. 
Preferred alcohols released by the orthoesters of the present invention are 
4-(1-methylethyl)cyclohexanemethanol (mayol), 
2,4-dimethyl-3-cyclohexen-1-ylmethanol (floralol), 
2,4-dimethylcyclohex-1-ylmethanol (dihydrofloralol), 
2,4,6-trimethyl-3-cyclohexen-1-ylmethanol (isocyclogeraniol), 
2-phenylethanol, 1-(4-isopropylcyclohexyl)ethanol (mugetanol), 
2-(o-methylphenyl)ethanol (ortho-hawthanol), 2-(m-methylphenyl)ethanol 
(meta-hawthanol), 2-(p-methylphenyl)-ethanol (para-hawthanol), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (majantol), 
3-phenyl-2-propen-1-ol (cinnamic alcohol), 
2-methyl-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-1-yl)-4-penten-2-ol (ebanol), 
2-methyl-4-phenylpentan-1-ol (pamplefleur), cis-3-hexen-1-ol, 
3,7-dimethyl-6-octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol 
(geraniol, nerol or mixtures thereof), 7-methoxy-3,7-dimethyloctan-2-ol 
(osyrol), 6,8-dimethylnonan-2-ol, cis-6-nonen-1-ol, 2,6-nonadien-1-ol, 
4-methyl-3-decen-5-ol (undecavertol), benzyl alcohol, 
2-methoxy-4-(1-propenyl)phenol (isoeugenol), 
2-methoxy-4-(2-propenyl)phenol (eugenol), 4-hydroxy-3-methoxybenzaldehyde 
(vanillin), and mixtures thereof. 
Non-limiting examples of orthoester pro-fragrances according to the present 
invention are tris-geranyl orthoformate, 
tris(cis-3-hexen-1-yl)orthoformate, tris(phenylethyl)orthoformate, 
bis(citronellyl) ethyl orthoacetate, tris(citronellyl)orthoformate, 
tris(cis-6-nonenyl)orthoformate, tris(phenoxyethyl)orthoformate, 
tris(geranyl, neryl)orthoformate (70:30 geranyl:neryl), 
tris(9-decenyl)orthoformate, tris(3-methyl-5-phenylpentanyl)orthoformate, 
tris(6-methylheptan-2-yl)orthoformate, 
tris(4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-yl!orthoformate, 
tris3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-yl!orthofo 
rmate, trismenthyl orthoformate, 
tris(4-isopropylcyclohexylethyl-2-yl)orthoformate, 
tris-(6,8-dimethylnonan-2-yl)orthoformate, tris-phenylethyl orthoacetate, 
tris(cis-3-hexen-1-yl)orthoacetate, tris(cis-6-nonenyl)orthoacetate, 
tris-citronellyl orthoacetate, bis(geranyl)benzyl orthoacetate, 
tris(geranyl)orthoacetate, tris(4-isopropylcyclohexylmethyl)orthoacetate, 
tris(benzyl)orthoacetate, tris(2,6-dimethyl-5-heptenyl)orthoacetate, 
bis(cis-3-hexen-1-yl)amyl orthoacetate, and neryl citronellyl ethyl 
orthobutyrate. Orthoester pro-accords can be used to deliver inter alia 
binary fragrance accords, fragrance accords having a "binary 
characteristic" accord component in combination with a modifier accord, 
and fragrance accords comprising astringents, fixatives, or diluents. 
Another class of orthoesters suitable for use as pro-accords according to 
the present invention are cyclic orthoesters having the formula: 
##STR12## 
wherein R.sup.14 and R.sup.15 are derived from the same fragrance raw 
material alcohols described herein above, each R.sup.16 is independently 
hydrogen, C.sub.1 -C.sub.22 linear or branched alkyl, C.sub.2 -C.sub.22 
linear or branched alkenyl, C.sub.6 -C.sub.22 substituted or unsubstituted 
aryl, and mixtures thereof, Y is --CR.sup.17 R.sup.18 --, C.dbd.O, and 
mixtures thereof, wherein R.sup.17 and R.sup.18 are independently 
hydrogen, hydroxyl, nitro, nitro, C.sub.1 -C.sub.30 substituted or 
unsubstituted linear alkyl, C.sub.3 -C.sub.30 substituted or unsubstituted 
branched alkyl, C.sub.3 -C.sub.30 substituted or unsubstituted cyclic 
alkyl, C.sub.2 -C.sub.30 substituted or unsubstituted linear alkenyl, 
C.sub.3 -C.sub.30 substituted or unsubstituted branched alkenyl, C.sub.3 
-C.sub.30 substituted or unsubstituted cyclic alkenyl, C.sub.2 -C.sub.30 
substituted or unsubstituted linear alkynyl, C.sub.3 -C.sub.30 substituted 
or unsubstituted branched alkynyl, C.sub.6 -C.sub.30 substituted or 
unsubstituted alkylenearyl, C.sub.6 -C.sub.30 substituted or unsubstituted 
aryl, C.sub.2 -C.sub.20 substituted or unsubstituted alkyleneoxy, C.sub.3 
-C.sub.20 substituted or unsubstituted alkyleneoxyalkyl, C.sub.7 -C.sub.20 
substituted or unsubstituted alkylenearyl, C.sub.6 -C.sub.20 substituted 
or unsubstituted alkyleneoxyaryl, and mixtures thereof, or R.sup.17 and 
R.sup.18 can be taken together to form a spiroannulated ring or taken 
together with any R.sup.16 to form a fused ring, said spiroannulated or 
fused ring having from 3 to 8 carbons and optionally one or more 
heteroatoms in said ring, said ring further optionally substituted by one 
or more C.sub.1 -C.sub.22 alkyl, C.sub.1 -C.sub.22 alkenyl, C.sub.6 
-C.sub.12 aryl, C.sub.6 -C.sub.22 alkylenearyl units, and mixtures 
thereof; n is from 0 to 3. 
Acetals and ketals 
Another class of compound useful as pro-accords according to the present 
invention are acetals and ketals having the formula: 
##STR13## 
wherein hydrolysis of the acetal or ketal releases one equivalent of 
aldehyde or ketone and two equivalents of alcohol according to the 
following scheme: 
##STR14## 
wherein R is C.sub.1 -C.sub.20 linear alkyl, C.sub.4 -C.sub.20 branched 
alkyl, C.sub.6 -C.sub.20 cyclic alkyl, C.sub.6 -C.sub.20 branched cyclic 
alkyl, C.sub.6 -C.sub.20 linear alkenyl, C.sub.6 -C.sub.20 branched 
alkenyl, C.sub.6 -C.sub.20 cyclic alkenyl, C.sub.6 -C.sub.20 branched 
cyclic alkenyl, C.sub.6 -C.sub.20 substituted or unsubstituted aryl, 
preferably the moieties which substitute the aryl units are alkyl 
moieties, and mixtures thereof. R.sup.1 is hydrogen, R, or in the case 
wherein the pro-accord is a ketal, R and R.sup.1 can be taken together to 
form a ring. R.sup.2 and R.sup.3 are independently selected from the group 
consisting of C.sub.5 -C.sub.20 linear, branched, or substituted alkyl; 
C.sub.4 -C.sub.20 linear, branched, or substituted alkenyl; C.sub.5 
-C.sub.20 substituted or unsubstituted cyclic alkyl; C.sub.6 -C.sub.20 
substituted or unsubstituted aryl, C.sub.2 -C.sub.40 substituted or 
unsubstituted alkyleneoxy; C.sub.3 -C.sub.40 substituted or unsubstituted 
alkyleneoxyalkyl; C.sub.6 -C.sub.40 substituted or unsubstituted 
alkylenearyl; C.sub.6 -C.sub.32 substituted or unsubstituted aryloxy; 
C.sub.6 -C.sub.40 substituted or unsubstituted alkyleneoxyaryl; C.sub.6 
-C.sub.40 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, nitro, halogen, nitro, 
carboxyl (--CHO; --CO.sub.2 H; --CO.sub.2 R'; --CONH.sub.2 ; --CONHR'; 
--CONR'.sub.2 ; wherein R' is C.sub.1 -C.sub.12 linear or branched alkyl), 
amino, C.sub.1 -C.sub.12 mono- and dialkylamino, and mixtures thereof. 
Non-limiting examples of R.sup.2 and R.sup.3 include methyl, 
2,4-dimethyl-3-cyclohexene -1-methyl (Floralol), 2,4-dimethyl cyclohexane 
methyl (Dihydro floralol), 
5,6-dimethyl-1-methylethenyl-bicyclo2.2.1!hept-5-ene-2-methyl (Arbozol), 
2,4,6-trimethyl-3-cyclohexene-1-methyl (Isocyclo geranyl), 
4-(1methylethyl)cyclohexylmethyl (Mayol), 
.alpha.-3,3-trimethyl-2-norboranylmethyl, 
1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methyl, ethyl, 2-phenylethyl, 
2-cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-methylphenyl)ethyl, 
2-(p-methylphenyl)ethyl, 6,6-dimethylbicyclo3.1.1!hept-2-ene-2-ethyl 
(nopyl), 2-(4-methylphenoxy)ethyl, 3,3-dimethyl-.DELTA..sup.2 
-.beta.-norboranylmethyl, 2-methyl-2-cyclohexylethyl, 
1-(4-isopropylcyclohexyl)ethyl, 1phenyl-1-hydroxyethyl, 
1,1-dimethyl-2-phenylethyl, 1,1-dimethyl-2-(4-methylphenyl)ethyl, propyl, 
1-phenylpropyl, 3-phenylpropyl, 2-phenylpropyl (Hydrotropic Alcohol), 
2-(cyclododecyl)-propan-1-yl (Hydroxyambran), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-yl (Majantol), 
2-methyl-3-phenylpropyl, 3-phenyl-2propen-1-yl (cinnamyl alcohol), 
2-methyl-3-phenyl-2-propen-1-yl (methylcinnamyl alcohol), 
.alpha.-n-pentyl-3-phenyl-2-propen-1-yl (.alpha.-amylcinnamyl alcohol), 
ethyl-3-hydroxy-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-1-yl)butyl, 
2-ethyl-4-(2,2,3-trimethylcyclopent-3-enyl)-2-buten-1-yl, 
3-methyl-2-buten-1-yl, 
2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-yl, 
3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 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, cis-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-dimethyltricyclo2.2.1.0(2,6)!hept-3-yl)-2-penten-1-yl 
(santalyl), 4-methyl-1-phenyl-2-pentyl, 
(1-methyl-bicyclo2.1.1!hepten-2-yl)-2-methylpent-1-en-3-yl, 
3-methyl-1-phenylpent-3-yl, 
1,2-dimethyl-3-(1-methylethenyl)cyclopent-1-yl, 2-isopropyl-4-methyl-2-hex 
enyl, cis-3-hexen-1-yl, trans-2-hexen-1-yl, 
2-isopropenyl-5methyl-4-hexen-1-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-1-yl, 1-methyl-4-isopropenylcyclohex-3-yl, 
4-iso-propyl-1-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, 1-methyl-4-isopropylcyclohex-3-yl (menthol), 
1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-yl, heptyl, 
2,4-dimethylhept-1-yl, 2,4-dimethyl-2,6-heptandienyl, 
6,6-dimethyl-2-oxymethylbicyclo3.1.1!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-dimethyl-3-hydroxy-2-methylenebicyclo3.1.1!-heptyl, 
1,7,7-trimethylbicyclo2.2.1!hept-2-yl, 2,6-dimethylhept-2-yl, 
2,6,6-trimethylbicyclo1.3.3!hept-2-yl, octyl, 2-octenyl, 
2-methyloctan-2-yl, 2-methyl-6-methylene-7-octen-2-yl (myrcenyl), 
7-methyloctan-1-yl, 3,7-dimethyl-6-octenyl, 3,7-dimethyl-7-octenyl, 
3,7-dimethyl-6-octen-1-yl (citronellyl), 3,7-dimethyl-2,6-octadien-1-yl 
(geranyl), 3,7-dimethyl-2,6-octadien-1-yl (neryl), 
3,7-dimethyl-1,6-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-1-octen-3-yl, 
7-hydroxy-3,7-dimethyloctanalyl, 3-nonyl, 6,8-dimethylnonan-2-yl, 
3-(hydroxymethyl)-2-nonanone, 2-nonen-1-yl, 2,4-nonadien-1-yl, 
2,6-nonadien-1-yl, cis-6-nonen-1-yl, 3,7-dimethyl-1,6-nonadien-3-yl, 
decyl, 9-decenyl, 2-benzyl-M-dioxa-5-yl, 2-decen-1-yl, 2,4-decadien-1-yl, 
4-methyl-3-decen-5-yl, 3,7,9-trimethyl-1,6-decadien-3-yl (isobutyl 
linallyl), undecyl, 2-undecen-1-yl, 10-undecen-1-yl, 2-dodecen-1-yl, 
2,4-dodecadien-1-yl, 2,7,11-trimethyl-2,6,10-dodecatrien-1-yl (farnesyl), 
3,7,11-trimethyl-1,6,10,-dodecatrien-3-yl, 
3,7,11,15-tetramethylhexadec-2-en-1-yl (phytyl), 
3,7,11,15-tetramethylhexadec-1-en-3-yl (iso phytol), benzyl, 
p-methoxybenzyl (anisyl), para-cymen-7-yl (cuminyl), 4-methylbenzyl, 
3,4-methylenedioxybenzyl, 2-(methyl)carboxy-1-hydroxyphenyl, 
2-(benzyl)carboxy-1-hydroxyphenyl, 
2-(cis-3-hexenyl)-carboxy-1-hydroxyphenyl, 
2-(n-pentyl)carboxy-1-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-1-hydroxyphenyl, 4-tert-butyl-1-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-1,3-dihydroxyphenyl, 5-methoxy-3-methyl-i 
-hydroxyphenyl, 2-tert-butyl-4-methyl-1-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-1H-inden-5-yl, 
3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-yl, 
2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuranyl, 
.beta.-caryophyllenyl, and mixtures thereof. 
Acetal Releasable Components: The acetals of the present invention have two 
types of releasable components, namely alcohols and aldehydes. Hydrolysis 
of an acetal will yield two equivalents of releasable alcohol and one 
equivalent of releasable aldehyde. The released aldehyde, when taken 
together with the released alcohol, forms a binary fragrance accord. For 
example bis(cis-3-hexenyl) vanillin acetal releases the binary accord 
vanillin/cis-3-hexenol. 
When R.sup.1 is hydrogen the pro-accords are capable of releasing an 
aldehyde component. Preferred aldehydes which are releasable components of 
the acetals of the present invention include but are not limited to 
phenylacetaldehyde, p-methyl phenylacetaldehyde, p-isopropyl 
phenylacetaldehyde, methylnonyl acetaldehyde, phenylpropanal, 
3-(4-t-butylphenyl)-2-methyl propanal (Lilial), 
3-(4-t-butylphenyl)propanal (Bourgeonal), 
3-(4-methoxyphenyl)-2-methylpropanal (Canthoxal), 
3-(4-isopropylphenyl)-2-methylpropanal (Cymal), 
3-(3,4-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, .alpha.-amylcinnamaldehyde, .alpha.-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 (Triplal), 
1-methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyde (Vernaldehyde), 
p-methylphenoxyacetaldehyde (Xi aldehyde), and mixtures thereof. 
More preferably the aldehydes released by the acetals of the present 
invention are 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde 
(lyral), phenylacetaldehyde, methylnonyl acetaldehyde, 2-phenylpropan-1-al 
(hydrotropaldehyde), 3-phenylprop-2-en-1-al (cinnamaldehyde), 
3-phenyl-2-pentylprop-2-en-1-al (.alpha.-amylcinnamaldehyde), 
3-phenyl-2-hexylprop-2-enal(.alpha.-hexylcinnamaldehyde), 
3-(4-isopropylphenyl)-2-methylpropan-1-al (cyclamen aldehyde), 
3-(4-ethylphenyl)-2,2-dimethylpropan-1-al (floralozone), 
3-(4-tert-butylphenyl)-2-methylpropanal, 
3-(3,4-methylenedioxyphenyl)-2-methylpropan-1-al (helional), 
3-(4-ethylphenyl)-2,2-dimethylpropanal, 3-(3-isopropylphenyl)butan-1-al 
(florhydral), 2,6-dimethylhep-5-en-1-al (melonal), n-decanal, n-undecanal, 
n-dodecanal, 3,7-dimethyl-2,6-octadien-1-al (citral), 
4-methoxybenzaldehyde (anisaldehyde), 3-methoxy-4-hydroxybenzaldehyde 
(vanillin), 3-ethoxy-4-hydroxybenzaldehyde (ethyl vanillin), 
3,4-methylenedioxybenzaldehyde (heliotropin), 3,4-dimethoxybenzaldehyde. 
Ketal Releasable Components: The ketals of the present invention have two 
types of releasable components, namely alcohols and ketones. Hydrolysis of 
a ketal will yield two equivalents of releasable alcohol and one 
equivalent of releasable ketone. The released ketone, when taken together 
with the released alcohol, forms a binary fragrance accord. For example 
di-linalyl .beta.-ionone ketal releases the binary accord 
linalool.beta.-ionone. 
When R.sup.1 is a moiety as described herein above other than hydrogen, the 
pro-accords are capable of releasing an ketone component. Preferred 
ketones which are releasable components of the ketals of the present 
invention include but are not limited to .alpha.-damascone, 
.beta.-damascone, .delta.-damascone, .beta.-damascenone, muscone, 
6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone (cashmeran), cis-jasmone, 
dihydrojasmone, .alpha.-ionone, .beta.-ionone, dihydro-.beta.-ionone, 
.gamma.-methyl ionone, .alpha.-iso-methyl ionone, 
4-(3,4-methylenedioxyphenyl)butan-2-one, 4-(4-hydroxyphenyl)butan-2-one, 
methyl .beta.-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, .beta.-dihydro ionone, allyl ionone, 
.alpha.-irone, .alpha.-cetone, .alpha.-irisone, acetanisole, geranyl 
acetone, 1-(2-methyl-5-isopropyl-2-cyclohexenyl)-1-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. 
More preferably the ketones which are released by the ketals of the present 
invention are .alpha.-damascone, .beta.-damascone, .delta.-damascone, 
.beta.-damascenone, muscone, 
6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone (cashmeran), cis-jasmone, 
dihydrojasmone, .alpha.-ionone, .beta.-ionone, dihydro-.beta.-ionone, 
.delta.-methyl ionone, (.alpha.-iso-methyl ionone, 
4-(3,4-methylenedioxyphenyl)butan-2-one, 4-(4-hydroxyphenyl)-butan-2-one, 
methyl .beta.-naphthyl ketone, methyl cedryl ketone, 6-acetyl 
-1,1,2,4,4,7-hexamethyltetralin (tonalid), l-carvone, 
5-cyclohexadecen-1-one, and mixture thereof. 
Non-limiting examples of alcohols suitably released by the hydrolysis of 
the acetal and ketal pro-accords include methanol, 
2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethyl cyclohexane 
methanol (Dihydro floralol), 
5,6-dimethyl-1-methylethenylbicyclo2.2.1!hept-5-ene-2-methanol (Arbozol), 
2,4,6-trimethyl-3-cyclohexene-1-methanol (Isocyclo geraniol), 
4-(1-methylethyl)cyclohexanemethanol (Mayol), 
.alpha.-3,3-trimethyl-2-norborane methanol, 
1,1-dimethyl-1-(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-.DELTA..sup.2 -.beta.-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, n-propanol, 2-propanol, 
1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic 
Alcohol), 2-(cyclododecyl)propan-1-ol (Hydroxy-ambran), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majantol), 
2-methyl-3-phenylpropanol, 3-phenyl-2-propen-1-ol (cinnamyl alcohol), 
2-methyl-3-phenyl-2-propen-1-ol (methylcinnamyl alcohol), 
(.alpha.-n-pentyl-3-phenyl-2-propen-1-ol (.alpha.-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-1-yl)butanol, 
2-ethyl-4-(2,2,3-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, pentanol, cis-3-pentenol, 
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-dimethyltricyclo2.2.1.0(2,6)!hept-3-yl)-2-penten-1-ol 
(santalol), 4-methyl-1-phenyl-2-pentanol, 
(1-methyl-bicyclo2.1.1!hepten-2-yl)-2-methylpent-1-en-3-ol, 
3-methyl-1-phenylpentan-3-ol, 
1,2-dimethyl-3-(1-methylethenyl)cyclopentan-1-ol, 
2-isopropyl-5-methyl-2-hexcnol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 
2-isoproenyl-4-methyl-4-hexen-1-ol (Lavandulol), 
2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-cyclohexene 
(Dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-ol 
(carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol, 
1-methyl-4-iso-propenylcyclohexan-3-ol, 
4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclo-hexanol, 
2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 
4-isopropyl-cyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol, 
2-(5,6,6-trimethyl-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 
3,3,5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, 
1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-ol, heptanol, 
2,4-dimethylheptan-1-ol, 2,4-dimethyl-2,6-heptandienol, 
6,6-dimethyl-2-oxymethylbicyclo3.1.1!hept-2-ene (myrtenol), 
4-methyl-2,4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 
3,6-dimethyl-3-vinyl-5-hepten-2-ol, 
6,6-dimethyl-3-hydroxy-2-methylenebicyclo3.1.1!heptane, 
1,7,7-trimethylbicyclo2.2.1!heptan -2-ol, 2,6-dimethylheptan-2-ol, 
2,6,6-trimethylbicyclo1.3.3!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-1-ol 
(geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol), 
3,7-dimethyl-1,6-octadien-3-ol (linalool),3,7-dimethyloctan-1ol 
-(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, 
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-1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6=-nonadien-3-ol, decanol, 
9-decenol, 2benzyl-M-dioxa-5-ol, 2-decen-1-ol, 2,4-decadien-1-ol, 
4-methyl-3-decen-5-ol, 3,7,9-trimethyl-1,6-decadien-3-ol (isobutyl 
linallol), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 
2,4-dodecadien-1-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-tetramethylhexadec 1-en-3-ol (iso phytol), benzyl alcohol, 
p-methoxy benzyl alcohol (anisyl alcohol), para-cymen-7-ol (cuminyl 
alcohol), 4methyl 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-methoxy-1-methylbenzene, 
2-tert-butyl-4-methyl-1-hydroxybenzene, 
1-ethoxy-2-hydroxy-4-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,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1H-inden-5-ol, 
3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-ol, 
2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuran, 
.beta.-caryophyllene alcohol, and mixtures thereof. 
Preferred alcohols which are released by the acetals and ketals of the 
present invention are 4-(1-methylethyl)cyclohexanemethanol (mayol), 
2,4-dimethyl-3-cyclohexen-1-ylmethanol (floralol), 
2,4-dimethylcyclohex-1-ylmethanol (dihydrofloralol), 
2,4,6-trimethyl-3-cyclohexen-1-ylmethanol (isocyclogeraniol), 
2-phenylethanol, 1(4-isopropylcyclohexyl)ethanol (mugetanol), 
2-(o-methylphenyl) ethanol (ortho-hawthanol), 2-(m-methylphenyl)ethanol 
(meta-hawthanol), 2-(p-methylphenyl)ethanol (para-hawthanol), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (majantol), 
3-phenyl-2-propen-1-ol (cinnamic alcohol), 
2-methyl-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-1-yl)-4-penten-2-ol (ebanol), 
2-methyl-4-phenylpentan-1-ol (pamplefleur), cis-3-hexen-1-ol, 
3,7-dimethyl-6-octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol 
(geraniol, nerol or mixtures thereof), 7-methoxy-3,7-dimethyloctan-2-ol 
(osyrol), 6,8-dimethylnonan-2-ol, cis-6-nonen-1-ol, 2,6-nonadien-1-ol, 
4-methyl-3-decen-5-ol (undecavertol), benzyl alcohol, 
2-methoxy-4-(1-propenyl)phenol (isoeugenol), 
2-methoxy-4-(2-propenyl)phenol (eugenol), 4-hydroxy-3-methoxybenzaldehyde 
(vanillin), and mixtures thereof. 
Orthocarbonates 
Another class of preferred compounds useful as pro-accords according to the 
present invention are orthocarbonates having the formula: 
##STR15## 
wherein hydrolysis of the orthoester releases the fragrance raw material 
components according to the following scheme: 
##STR16## 
wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently C.sub.1 
-C.sub.20 linear, branched, or substituted alkyl; C.sub.2 -C.sub.20 
linear, branched, or substituted alkenyl; C.sub.5 -C.sub.20 substituted or 
unsubstituted cyclic alkyl; C.sub.6 -C.sub.20 substituted or unsubstituted 
aryl, C.sub.2 -C.sub.40 substituted or unsubstituted alkyleneoxy; C.sub.3 
-C.sub.40 substituted or unsubstituted alkyleneoxyalkyl; C.sub.6 -C.sub.40 
substituted or unsubstituted alkylenearyl; C.sub.6 -C.sub.32 substituted 
or unsubstituted aryloxy; C.sub.6 -C.sub.40 substituted or unsubstituted 
alkyleneoxyaryl; C.sub.6 -C.sub.40 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, nitro, halogen, nitro, carboxyl (--CHO; --CO.sub.2 H; --CO.sub.2 
R'; --CONH.sub.2 ; --CONHR'; --CONR'.sub.2 ; wherein R' is C.sub.1 
-C.sub.12 linear or branched alkyl), amino, C.sub.1 -C.sub.12 mono- and 
dialkylamino, and mixtures thereof. 
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: 
##STR17## 
wherein R.sup.8, R.sup.9, R.sup.10, and R.sub.11 are each independently 
hydrogen, C.sub.1 -C.sub.20 linear or branched alkyl, C.sub.1 -C.sub.20 
linear or branched alkenyl, C.sub.1 -C.sub.20 linear, branched or cyclic 
alkylenecarboxy, C.sub.1 -C.sub.20 linear, branched, or cyclic 
carboxyalkyl, C.sub.1 -C.sub.20 linear or branched alkyleneamino, C.sub.1 
-C.sub.20 linear or branched aminoalkyl, C.sub.1 -C.sub.20 linear, 
branched, or cyclic alkylenecarboxamido, C.sub.1 -C.sub.20 linear or 
branched carboxamidoalkyl, alkyleneoxy having the formula: 
##STR18## 
wherein R.sup.12 is hydrogen or methyl; R.sup.13 is hydrogen or C.sub.1 
-C.sub.2 alkyl; n is from 0 to 4, x is from 1 to about 20, y is from 0 to 
about 20. 
In addition to the initial release of two equivalents of alcohol and one 
equivalent of carbonate by the scheme depicted herein above, the carbonate 
pro-fragrances 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: 
##STR19## 
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. 
Non-limiting examples of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 include 
methyl, 2,4-dimethyl-3-cyclo-hexene-1-methyl (Floralol), 2,4-dimethyl 
cyclohexane methyl (Dihydro floralol), 
5,6-dimethyl-1-methylethenyl-bicyclo2.2.1!hept-5-ene-2-methyl (Arbozol), 
2,4,6-trimethyl-3-cyclohexene-1-methyl (Isocyclo geranyl), 
4-(1-methylethyl)cyclohexylmethyl (Mayol), 
.alpha.-3,3-trimethyl-2-norboranylmethyl, 
1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methyl, ethyl, 2-phenylethyl, 
2-cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-methylphenyl)ethyl, 
2-(p-methylphenyl)ethyl, 6,6-dimethylbicyclo3.1.1!hept-2-ene-2-ethyl 
(nopyl), 2-(4-methylphenoxy)ethyl, 3,3-dimethyl-.DELTA..sup.2 
-.beta.-norboranylmethyl, 2-methyl-2-cyclohexylethyl, 
1-(4-isopropylcyclohexyl)ethyl, 1-phenyl-1-hydroxyethyl, 
1,1-dimethyl-2-phenylethyl, 1,1-dimethyl-2-(4-methylphenyl)ethyl, propyl, 
1-phenylpropyl, 3-phenylpropyl, 2-phenylpropyl (Hydrotropic Alcohol), 
2-(cyclododecyl)-propan-1-yl (Hydroxyambran), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-yl (Majantol), 
2-methyl-3-phenylpropyl, 3-phenyl-2-propen-1-yl (cinnamyl alcohol), 
2-methyl-3-phenyl-2-propen-1-yl (methylcinnamyl alcohol), 
(.alpha.-n-pentyl-3-phenyl-2-propen-1-yl (.alpha.-amylcinnamyl alcohol), 
ethyl-3-hydroxy-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-1-yl)butyl, 
2-ethyl-4-(2,2,3-trimethylcyclopent-3-enyl)-2-buten-1-yl, 
3-methyl-2-buten-1-yl, 
2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-yl, 
3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 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, cis-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-dimethyltricyclo2.2.1.0(2,6)!hept-3-yl)-2-penten-1-yl 
(santalyl), 4-methyl-1-phenyl-2-pentyl, 
(1-methyl-bicyclo2.1.1!hepten-2-yl)-2-methylpent-1-en-3-yl, 
3-methyl-1-phenylpent-3-yl, 
1,2-dimethyl-3-(1-methylethenyl)cyclopent-1-yl, 2-isopropyl-4-methyl-2-hex 
enyl, cis-3-hexen-1-yl, trans-2-hexen-1-yl, 
2-isopropenyl-5-methyl-4-hexen-1-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-1-yl, 1-methyl-4-isopropenylcyclohex-3-yl, 
4-iso-propyl-1-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, 1-methyl-4-isopropylcyclohex-3-yl (menthol), 
1,2-dimethyl-3-(1-methylethyl) -cyclohexan-1-yl, heptyl, 
2,4-dimethylhept-1-yl, 2,4-dimethyl-2,6-heptandienyl, 
6,6-dimethyl-2-oxymethylbicyclo3.1.1!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-dimethyl-3-hydroxy-2-methylenebicyclo3.1.1!-heptyl, 
1,7,7-trimethylbicyclo2.2.1!hept-2-yl, 2,6-dimethylhept-2-yl, 
2,6,6-trimethylbicyclo1.3.3!hept-2-yl, octyl, 2-octenyl, 
2-methyloctan-2-yl, 2-methyl-6-methylene-7-octen-2-yl (myrcenyl), 
7-methyloctan-1-yl, 3,7-dimethyl-6-octenyl, 3,7-dimethyl-7-octenyl, 
3,7-dimethyl-6-octen-1-yl (citronellyl), 3,7-dimethyl-2,6-octadien-1-yl 
(geranyl), 3,7-dimethyl-2,6-octadien-1-yl (neryl), 
3,7-dimethyl-1,6-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-1-octen-3-yl, 
7-hydroxy-3,7-dimethyloctanalyl, 3-nonyl, 6,8-dimethylnonan-2-yl, 
3-(hydroxymethyl)-2-nonanone, 2-nonen-1-yl, 2,4-nonadien-1-yl, 
2,6-nonadien-1-yl, cis-6-nonen-1-yl, 3,7-dimethyl-1,6-nonadien-3-yl, 
decyl, 9-decenyl, 2-benzyl-M-dioxa -5-yl, 2-decen-1-yl, 2,4-decadien-1-yl, 
4-methyl-3-decen-5-yl, 3,7,9-trimethyl-1,6-decadien-3-yl (isobutyl 
linallyl), undecyl, 2-undecen-1-yl, 10-undecen-1-yl, 2-dodecen-1-yl, 
2,4-dodecadien-1-yl, 2,7,11-trimethyl-2,6,10-dodecatrien-1-yl (farnesyl), 
3,7,11-trimethyl-1,6,10,-dodecatrien-3-yl, 
3,7,11,15-tetramethylhexadec-2-en-1-yl (phytyl), 
3,7,11,15-tetramethylhexadec-1-en-3-yl (iso phytol), benzyl, 
p-methoxybenzyl (anisyl), para-cymen-7-yl (cuminyl), 4-methylbenzyl, 
3,4-methylenedioxybenzyl, 2-(methyl)carboxy-1-hydroxyphenyl, 
2-(benzyl)carboxy-1-hydroxyphenyl, 
2-(cis-3-hexenyl)-carboxy-1-hydroxyphenyl, 
2-(n-pentyl)carboxy-1-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-1-hydroxyphenyl, 4-tert-butyl-1-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-1,3-dihydroxyphenyl 
5-methoxy-3-methyl-1-hydroxyphenyl, 2-tert-butyl-4-methyl-1-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-1H-inden-5-yl, 
3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-yl, 
2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuranyl, 
.beta.-caryophyllenyl, and mixtures thereof. 
Orthocarbonate Releasable Components: The initial hydrolysis of the 
orthocarbonates of the present invention release two types of components, 
alcohols and carbonates. As indicated herein above, the carbonates can 
further break down to release further alcohols. The first hydrolysis of an 
orthocarbonate pro-accord releases two equivalents of alcohol and one 
equivalent of carbonate. The released carbonate, when taken together with 
the released alcohol, forms a binary fragrance accord. For example 
tetra-geranyl orthocarbonate releases the binary accord 
geraniol/di-geranyl carbonate. Non-limiting examples of alcohols suitably 
released by the hydrolysis of the orthocarbonate pro-accords include 
methanol, 2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethyl 
cyclohexane methanol (Dihydro floralol), 
5,6-dimethyl-1-methylethenylbicyclo2.2.1!hept-5-ene-2-methanol (Arbozol), 
2,4,6-trimethyl-3-cyclohexene-1-methanol (Isocyclo geraniol), 
4-(1-methylethyl)cyclohexanemethanol (Mayol), 
.alpha.-3,3-trimethyl-2-norborane methanol, 
1,1-dimethyl-1-(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-.DELTA.2-.beta.-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, n-propanol, 2-propanol, 
1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic 
Alcohol), 2-(cyclododecyl)propan-1-ol (Hydroxy-ambran), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majantol), 
2-methyl-3-phenylpropanol, 3-phenyl-2-propen-1-ol (cinnamyl alcohol), 
2-methyl-3-phenyl-2-propen-1-ol (methylcinnamyl alcohol), 
.alpha.-n-pentyl-3-phenyl-2-propen-1-ol (.alpha.-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-1-yl)butanol, 
2-ethyl-4-(2,2,3-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, pentanol, cis-3-pentenol, 
3-methyl-pentanol, 3-methyl-3-penten-1-ol, 2-methyl-4-phenylpentanol 
(Pamplefleur), 3-methyl-5phenylpentanol (Phenoxanol), 
2-methyl-5-phenylpentanol, 
2-methyl-5-(2,3-dimethyltricyclo2.2.1.0(2,6)!hept-3-yl)-2-penten-1-ol 
(santalol), 4-methyl-1-phenyl-2-pentanol, 
(1-methyl-bicyclo2.1.1!hepten-2-yl)-2-methylpent-1-en-3-ol, 
3-methyl-1-phenylpentan-3-ol, 
1,2-dimethyl-3-(1methylethenyl)cyclopentan-1-ol, 
2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 
2-isoproenyl-4-methyl-4-hexen-1-ol (Lavandulol), 
2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-cyclohexene 
(Dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-ol 
(carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol, 
1-methyl-4-iso-propenylcyclohexan-3-ol, 
4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclo-hexanol, 
2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 
4-isopropyl-cyclohexanol, 4-methyl-1-(1methylethyl)-3-cyclohexen-1-ol, 
2-(5,6,6-trimethyl-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 
3,3,5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, 
1,2-dimethyl-3-(1methylethyl)cyclohexan-1-ol, heptanol, 
2,4-dimethylheptan-1-ol, 2,4-dimethyl-2,6-heptandienol, 
6,6-dimethyl-2-oxymethylbicyclo3.1.1!hept-2-ene (myrtenol), 
4-methyl-2,4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 
3,6-dimethyl-3-vinyl-5-hepten-2-ol, 
6,6-dimethyl-3-hydroxy-2-methylenebicyclo3.1.1!heptane, 
1,7,7-trimethylbicyclo2.2.1!heptan-2-ol, 2,6-dimethylheptan-2-ol, 
2,6,6-trimethylbicyclo1.3.3!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-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, 
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-1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6-nonadien-3-ol, decanol, 
9-decenol, 2-benzyl-M-dioxa-5-ol, 2-decen-1-ol, 2,4-decadien-1-ol, 
4-methyl-3-decen-5-ol, 3,7,9-trimethyl-1,6-decadien-3-ol (isobutyl 
linallol), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 
2,4-dodecadien-1-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-tetramethylhexadec 1-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-methoxy-1-methylbenzene, 
2-tert-butyl-4-methyl-1-hydroxybenzene, 
1-ethoxy-2-hydroxy-4-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,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1H-inden-5-ol, 
3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-ol, 
2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuran, 
.beta.-caryophyllene alcohol, and mixtures thereof. 
Preferred alcohols released by the orthocarbonate pro-accords of the 
present invention are 4-(1-methylethyl)cyclohexanemethanol (mayol), 
2,4-dimethyl-3-cyclohexen-1-ylmethanol (floralol), 
2,4-dimethylcyclohex-1-ylmethanol (dihydrofloralol), 
2,4,6-trimethyl-3-cyclohexen-1-ylmethanol (isocyclogeraniol), 
2-phenylethanol, 1-(4-isopropylcyclohexyl)ethanol (mugetanol), 
2-(o-methylphenyl)ethanol (ortho-hawthanol), 2-(m-methylphenyl)ethanol 
(meta-hawthanol), 2-(p-methylphenyl)ethanol (para-hawthanol), 
2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (majantol), 
3-phenyl-2-propen-1-ol (cinnamic alcohol), 
2-methyl-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-1-yl)-4-penten-2-ol (ebanol), 
2-methyl-4-phenylpentan-1-ol (pamplefleur), cis-3-hexen-1-ol, 
3,7-dimethyl-6-octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol 
(geraniol, nerol or mixtures thereof), 7-methoxy-3,7-dimethyloctan-2-ol 
(osyrol), 6,8-dimethylnonan-2-ol, cis-6-nonen-1-ol, 2,6-nonadien-1-ol, 
4-methyl-3-decen-5-ol (undecavertol), benzyl alcohol, 
2-methoxy-4-(1-propenyl)phenol (isoeugenol), 
2-methoxy-4-(2-propenyl)phenol (eugenol), 4-hydroxy-3-methoxybenzaldehyde 
(vanillin), and mixtures thereof. 
Non-limiting examples of preferred orthocarbonate pro-accords according to 
the present invention include: bis(ethyl) bis(geranyl)orthocarbonate, 
bis(ethyl) bis(phenylethyl)orthocarbonate, bis(ethyl) 
bis(cis-3-hexenyl)orthocarbonate, bis(ethyl) 
bis(citronellyl)orthocarbonate, bis(ethyl) bis(linalyl)orthocarbonate, 
bis(ethyl) bis(menthyl)orthocarbonate, bis(dodecyl) 
bis(geranyl)orthocarbonate, and bis(dodecyl) 
bis(phenylethyl)orthocarbonate. 
The more preferred orthocarbonate pro-accords of the present invention 
comprise at least three of the R.sup.1, R.sup.2, R.sup.3, and R.sup.4 
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-accords 
according to the present invention include: methyl 
tris(geranyl)orthocarbonate, ethyl tris(geranyl)orthocarbonate, methyl 
tris(phenylethyl)orthocarbonate, ethyl tris(phenylethyl)orthocarbonate, 
methyl tris(cis-3-hexenyl)orthocarbonate, ethyl 
tris(cis-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, 
and dodecyl tris(phenylethyl) orthocarbonate. 
The most preferred orthocarbonate pro-accords of the present invention have 
each of the R.sup.1, R.sup.2, R.sup.3, and R.sup.4 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-accord. Further, the preferred orthocarbonate pro-accords have a 
molecular weight which is greater than or equal to 350 g/mol. 
Non-limiting examples of most preferred orthocarbonate pro-accords 
according to the present invention include: tetra-geranyl orthocarbonate, 
tetra phenylethyl orthocarbonate, 
tetrakis(3-methyl-5-phenylpentyl)orthocarbonate, 
tetrakis(cis-3-hexenyl)orthocarbonate, bis(geranyl) bis(cis-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. 
Fragrance Release Half-life 
The pro-accords useful in the perfume and fine fragrance compositions of 
the present invention generally have a delayed release of final fragrance 
accord in order to achieve the increased fragrance longevity benefits 
described herein. However, the pro-accords generally also deliver the 
fragrance accords during a time period useful to the formulator, for 
example, within a time period desirable to the consumer. 
For the purposes of the present invention the pro-accords generally have a 
"Fragrance Release Half-life" of less than or equal to 12 hours when 
measured in NaH.sub.2 PO.sub.4 buffer at pH 2.5 and greater than or equal 
to 0.1 hour when measured in NaH.sub.2 PO.sub.4 buffer at pH 5.3. 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: 
EQU Pro-Accord.fwdarw.Accord 
wherein the accord which is released may be a binary accord or a multiple 
fragrance raw material accord. 
The rate at which the accord is released is defined by the formula: 
EQU Rate=kPro-accord! 
and can be further expressed by the formula: 
##EQU1## 
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", t.sub.1/2 is related to the release rate 
constant by the formula: 
##EQU2## 
and this relationship is used for the purposes of the present invention to 
determine the "fragrance Release Half-life" (FRHL). 
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 (H.sub.3 PO.sub.4) and 24 g of sodium dihydrogen phosphate (NaH.sub.2 
PO.sub.4) 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.degree. 
C. 
Table 1 lists several pro-accords according to the present invention with 
their corresponding t.sub.1/2 values. 
TABLE I 
______________________________________ 
Pro-accord t.sub.1/2 * 
______________________________________ 
tris(phenylethyl) orthoformate 
5.9 
tetrakis(phenylethyl) orthocarbonate 
4.8 
______________________________________ 
*t.sub.1/2 for the purposes of the present invention is measured in hours 
 
As indicated in the table above tris(phenylethyl)orthoformate is suitable 
for use as a pro-fragrance for delivering a "rose-floral" character note 
to an accord having enhance longevity. In some instances, it is desirable 
to formulate pro-accords having one or more pro-fragrances which deliver a 
rapid release of fragrance raw material in addition to the delayed onset 
of a fragrance. In such cases the hydrolysis rate, and therefore the 
determination of t.sub.1/2 must be measured in a buffer system which can 
accommodate this more rapid hydrolysis rate. For example, the 
pro-fragrance tris-(phenylethyl)orthoacetate is used to deliver a rapid 
onset of a "rose-floral" middle note by releasing the fragrance raw 
material phenylethyl alcohol. The relative release rate of this pro-accord 
can be suitably determined by substituting a phosphate buffer comprising 
4.6 g of sodium dihydrogen phosphate (NaH.sub.2 PO.sub.4) and 7.9 g of 
disodium hydrogen phosphate (Na.sub.2 HPO.sub.4) admixed with 1 liter of 
water for the phosphate buffer described herein above, then 10 mL of this 
solution is added to 90 mL of dioxane. Alternatively, the phosphate 
buffered water is prepared by admixing 3.95 mL of 85% phosphoric acid 
(H.sub.3 PO.sub.4) and 24 g of sodium dihydrogen phosphate (NaH.sub.2 PO4) 
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. 
Therefore, by admixing sufficient quantities of tris(phenylethyl) 
orthoformate and tris(phenylethyl)orthoacetate into a pro-accord the 
formulator can achieve a rapid as well as delayed onset of the 
"rose-floral" character note provided by the perfume raw material 
phenylethyl alcohol. 
Odor Value 
The pro-accords of the present invention typically have an Odor Value 
greater than or equal to about 1, preferably greater than or equal to 
about 5, more preferably greater than or equal to about 10. The term "Odor 
Value" is defined by the following formula: 
##EQU3## 
wherein OV is the odor value of the fragrance raw material released upon 
the skin by the pro-accord. The odor value is the concentration of the 
fragrance raw material, FRM, on the skin surface divided by the Odor 
Detection Threshold, ODT. The term "level of noticeability" is often 
applied to and substituted for the term "odor value". 
Odor Detection Threshold 
For the purposes of the present invention the term "odor detection 
threshold" is defined as the level at which a fragrance raw material is 
perceptible to the average human. The odor detection threshold (ODT) of 
the compositions of the present invention are preferably measured by 
carefully controlled gas chromatograph (GC) conditions as described 
hereinbelow. The preferred fragrance raw materials of the present 
invention have an ODT of at least about 100 part per billion (ppb), more 
preferably 10 ppb, most preferably 1 ppb. Fragrance raw materials having 
an ODT greater than 10 parts per million (ppm) are typically avoided 
unless useful as an adjunct ingredient, for example, as an adjunct alcohol 
when adjusting the fragrance release half-life of an orthoester. 
Determination of Odor Detection Thresholds is as follows. A gas 
chromatograph is characterized to determine the exact volume of material 
injected by a syringe, the precise split ratio, and the hydrocarbon 
response using a hydrocarbon standard of known concentration and 
chain-length distribution. The air flow rate in accurately measured and, 
assuming the duration of a human inhalation to last 0.02 minutes, the 
sampled volume is calculated. Since the precise concentration at the 
detector at any point in time is known, the mass per volume inhaled is 
known and hence the concentration of material. To determine whether a 
material has a threshold below 10 ppb, solutions are delivered to the 
sniff port at the back-calculated concentration. A panelist sniffs the GC 
effluent and identities the retention time when odor is notice. The 
average over all panelists determines the threshold of noticeability or 
ODT. The necessary amount of analyte is injected onto the column to 
achieve a 10 ppb concentration at the detector. Typical gas chromatograph 
parameters for determining odor detection thresholds are listed below. 
GC: 5890 Series II with FID detector 7673 Autosampler 
Column: J&W Scientific DB-1, length 30 m, i.d. 0.25 mm, film thickness 1 
.mu.m. 
Split Injection: 17/1 split ratio 
Autosampler: 1.13 .mu.l/injection 
Column flow: 1.10 mL/min 
Air flow: 345 mL/min 
Inlet temperature: 245.degree. C. 
Detector temperature: 285.degree. C. 
Temperature Information: 
Initial temperature: 50.degree. C. 
Rate: 5.degree. C./min 
Final temperature: 280.degree. C. 
Final time: 6 min 
Leading assumptions: 0.02 minutes per sniff and that GC air adds to sample 
dilution. 
Symmetrical Pro-accords 
Symmetrical pro-accords release the same fragrance raw materials regardless 
of hydrolysis pathway. An example of a symmetrical pro-accord is 
tris(phenylethyl) orthoacetate which releases a binary accord having a 
"rose" characteristic comprising 2 parts phenylethyl alcohol and 1 part 
phenylethyl acetate according to the following scheme: 
##STR20## 
The phenylethyl alcohol/phenylethyl acetate (2:1) simple accord is useful 
in delivering to fabric a rose or rose/floral characteristic. These are 
the only fragrance raw materials which are releasable by the pro-accord 
regardless of hydrolysis pathway. 
Unsymmetrical Pro-accords 
Unsymmetrical pro-accords have the capacity to release fragrance accords 
more complex than the binary fragrance accords released by symmetrical 
pro-accords. The composition of the released accord depends on the route 
of pro-accord hydrolysis. An unsymmetrical pro-accord can be designed by 
the formulator to release different ratios of fragrance raw materials 
based not only on the composition of the pro-accord but on the reactivity 
as well. In addition, unsymmetrical pro-accords can also be used to 
produce "adjunct pro-accords" useful for releasing low molecular weight 
modifiers or astringents in addition to fragrance raw materials. 
An example of an unsymmetrical pro-accord is di-citronellyl benzyl acetate 
capable of releasing the binary fragrance accord of 
citronellol/citronellyl acetate having a "rose" characteristic together 
with the benzyl alcohol/benzyl acetate "jasmin" modifiers according to the 
following scheme: 
##STR21## 
The above accord can be suitably modified by the formulator to adjust the 
relative proportions of the accord ingredients. For example, more of the 
"sweet" diluent benzyl alcohol can be delivered by adjusting the 
proportion of citronellol and benzyl alcohol used in the pro-accord. 
Di-benzyl citronellyl orthoacetate delivers the same fragrance raw 
materials as di-citronellyl benzyl orthoacetate, only the relative amounts 
of the released materials differ. 
As described herein above, a principle aspect of the present invention is 
the ability of certain pro-accords to deliver more than one fragrance raw 
material when the "pro-accord" has been formed from only one fragrance raw 
material. These pro-accords, which preferably include the formate, 
acetate, propionate, benzoate, and phenylacetate orthoesters of fragrance 
raw material alcohols can be summarized as: 
a) said pro-accord is formed from n number of fragrance raw materials; 
b) said pro-accord contains n number of fragrance raw materials in a 
releasable form; and 
c) said pro-accord when releasing the fragrance raw materials releases at 
least n+1 fragrance raw materials. 
According to the present invention all isomers of a fragrance raw material 
whether in the form of the pro-accord or the released fragrance raw 
material, are suitable for use in the present invention. When optical 
isomers are possible fragrance raw materials may be included as either the 
separate chemical isomer or as the combined racemic mixture. For example, 
3,7-dimethyl-6-octen-1-ol, commonly known by those of ordinary skill in 
the art as .beta.-citronellol or cephrol, comprises a pair of optical 
isomers, R-(+)-.beta.-citronellol and S-(-)-.beta.-citronellol. Each of 
these materials separately or as a racemic pair are suitable for use as 
fragrance raw materials in the present invention. However, those skilled 
in the art of fragrances, by utilization of the present invention, should 
not disregard the olfactory differences that individual optical isomers 
impart. By way of example, carvone, 
2-methyl-5-(1-methylethenyl)-2-cyclohexene-1-one exists as two isomers; 
d-carvone and l-carvone. d-Carvone is found in oil of caraway and renders 
a completely different fragrance from l-carvone which is found in 
spearmint oil. According to the present invention a pro-accord which 
releases d-carvone will result in a different accord than one which 
releases l-carvone. The same applies to l-carvone. 
The pro-accords of the present invention are acetals, ketals, orthoesters, 
and orthocarbonates which are formed from fragrance raw materials that are 
selected from the group consisting of primary, secondary, and tertiary 
alcohols, preferably primary and secondary alcohols, aldehydes, ketones, 
esters, and mixtures thereof. The pro-accords of the present invention 
release the fragrance raw materials upon contact with skin or hair, an 
acid forming, or an acid containing medium. 
Human skin exhibits a "buffer capacity" which vigorously maintains a 
constant pH value. This buffer capacity is referred to as "the acid 
mantle". Human skin acts rapidly to neutralize acidic or alkaline insults 
outside this constant pH value. Utilizing this recognition of the "buffer 
capacity" of the skin, the pro-accords of the present invention which are 
labile to acid media, can be applied to skin and the acidic nature of said 
skin can then be effectively used as the acid catalyst to release the 
parent fragrance raw materials. Therefore, the pro-accords of the present 
invention which are acid labile generally retain their chemical form at 
alkaline pH's, preferably at pH greater than 8. What is meant by the term 
"pro-accords must maintain their chemical form" is that a pro-accord which 
is in an acid labile form inter alia acetal, ketal, orthoester, or 
orthocarbonate will not hydrolyze and release the fragrance raw materials 
at an alkaline pH. 
The pro-accord component of the present invention, as described herein 
above, must have a reserve alkalinity equivalent to at least 0.001 molar 
(1 millimolar) sodium hydroxide. This generally serves to prevent 
premature release of the fragrance raw materials which comprise acid 
labile pro-accords prior to exposure of the pro-accords to skin. For the 
purposes of the present invention the term "a reserve alkalinity of at 
least 0.001 molar" is defined as "the amount of alkaline material present 
in one liter of the first fragrance oil component that is placed in an 
equivalent volume of water, would produce a hydroxide ion equivalent of 
0.001 moles or greater". By way of illustration, 0.0004 g of NaOH present 
in a 10 mL aliquot of the first fragrance oil component would produce a 
reserve alkalinity of at least 0.001 molar. 
Suitable sources of alkalinity are the alkali metal and alkali earth 
hydroxides. For example, sodium hydroxide, potassium hydroxide, lithium 
hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, 
potassium carbonate, and sodium silicate. However, other suitable sources 
of alkalinity can be used which are compatible with the pro-accords of the 
"pro-accord component". 
The "fragrance raw material component" of the compositions of the present 
invention may contain top and middle note as well as base note fragrances. 
The top and middle notes which comprise this component may be the same or 
different notes which are released by the pro-accords which comprise the 
"pro-accord component". 
In addition, carriers, fixatives, and other adjunct ingredients may be 
added to the pro-accord component and the fragrance raw material 
component. Typical carriers are methanol, ethanol (preferred), 
iso-propanol, polyethylene glycol, as well as water in some instances, 
especially as a vehicle to deliver materials which provide reserve 
alkalinity to the pro-accord component. 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 purpose in addition to 
providing a pleasurable odor. 
The following are non-limiting examples which illustrate the types of 
accords which are releasable by the pro-fragrances of the present 
invention. The examples listed herein below are suitably stabilized under 
the alkaline conditions described herein above. 
The following is an example of the release of the binary accord 
geraniol/geranyl formate by the pro-accord tris(geranyl)orthoformate: 
##STR22## 
The following is an example of the release of the binary accord 
citronellol/citronellyl propionate by the pro-accord 
tris(citronellyl)orthopropionate: 
##STR23## 
The following is an example of the release of the binary accord 
cis-6-nonenol/cis-6-nonenyl acetate by the pro-accord 
tris(cis-6-nonenyl)orthoacetate: 
##STR24## 
The following is an example of the release of the binary accord phenylethyl 
alcohol/phenylethyl benzoate, which comprises a base note, by the 
pro-accord tris(phenylethyl)orthobenzoate: 
##STR25## 
The following is an example of the release of the binary accord modifiers 
benzyl alcohol/benzyl salicylate by the pro-accord 
tris(benzyl)orthosalicyclate: 
##STR26## 
The following is an example of the release of the fragrance accord which 
comprises cis-3-hexenol, cis-3-hexenyl acetate, 5-phenyl-3-methylpentanol 
and 5-phenyl3-methylpentyl acetate by the pro-accord 
bis(5-phenyl-3-methylpentyl)cis-3-hexenyl orthoacetate: 
##STR27## 
Non-preferred orthoesters which are encompassed within the definition of 
"orthoesters" hereinabove are orthoesters comprising R units which are 
hydrogen (formate), methyl (acetate), phenyl (benzoate), benzyl 
(phenylacetate), phenethyl (phenylpropionate), phenylpropyl 
(phenylbutyrate), cis-3-hexenyl, or santalyl (.alpha. or .beta.) when 
R.sup.1, R.sup.2, and R.sup.3 comprise only the alcohols selected from 
group consisting of methanol, phenylethanol, phenylpropanol, cinnamyl 
alcohol, benzyl alcohol, geraniol, citronellol, .alpha.-santalol, 
.beta.-santalol, and cis-3-hexenol. Especially non-preferred pro-accords 
are those wherein two R.sup.1, R.sup.2, or R.sup.3 units are methanol 
which is not a fragrance raw material alcohol. For example, dimethyl 
geranyl orthoformate, typically releases two equivalents of methanol and 
one equivalent of geranyl formate. The formulator will recognize that 
methanol has no intrinsic fragrance value, that an excess of the 
pro-perfume will need to be released to provide the an odor benefit, and 
that the pro-perfume itself may be too volatile in some applications and 
therefore, will evaporate prior to release of the constituent ingredients. 
However, if these alcohols are combined with an alcohol not of this group, 
for example, nerol, osyrol, Mayol, these alcohols are suitable as 
components of a preferred pro-accord. 
Changing Fragrance Characteristic 
The present invention is also directed to a method which uses the selective 
release of fragrances to alter or modify the fragrance or scent 
"characteristic" over the usage time. For example, a perfume, cologne, eau 
de toilette, after-shave, or other fragrance-containing composition may 
have an initial smell that is characterized as "raspberry". This 
composition will typically comprise many components that are middle and 
base notes and therefore may remain constant. However, the several 
component fragrance raw materials responsible for the "raspberry" notes 
may be allowed to diffuse and evaporate while the first fragrance oil 
component comprises pro-fragrances that release "lilac" notes. After a 
period of time, the necessary middle and base notes are present but the 
volatile "raspberry notes" are replaced by "lilac notes" that have been 
released from pro-fragrances. 
An example of a preferred embodiment of the present invention comprises: 
a) a first component comprising: 
i) from about 0.1% to about 50% by weight, one or more fragrance raw 
materials; 
ii) the balance carriers and adjunct ingredients; 
b) a second component comprising: 
i) from about 0.5% to about 5% by weight, of nonadyl orthoformate; 
ii) from about 1.5% to about 5% by weight, of mugetanol orthoformate; 
iii) from about 1.5% to about 5% by weight, of osyrol orthoformate; 
iv) from about 1% to about 10% by weight, of one or more pro-accord 
orthoesters having the formula: 
##STR28## 
wherein R is hydrogen, C.sub.1 -C.sub.8 linear alkyl, C.sub.4 -C.sub.20 
branched alkyl, C.sub.6 -C.sub.20 cyclic alkyl, C.sub.6 -C.sub.20 branched 
cyclic alkyl, C.sub.6 -C.sub.20 linear alkenyl, C.sub.6 -C.sub.20 branched 
alkenyl, C.sub.6 -C.sub.20 cyclic alkenyl, C.sub.6 -C.sub.20 branched 
cyclic alkenyl, C.sub.6 -C.sub.20 substituted or unsubstituted aryl, and 
mixtures thereof, R.sup.1, R.sup.2 and R.sup.3 are independently C.sub.1 
-C.sub.20 linear, branched, or substituted alkyl; C.sub.2 -C.sub.20 
linear, branched, or substituted alkenyl; C.sub.5 -C.sub.20 substituted or 
unsubstituted cyclic alkyl; C.sub.6 -C.sub.20 substituted or unsubstituted 
aryl, C.sub.2 -C.sub.40 substituted or unsubstituted alkyleneoxy; C.sub.3 
-C.sub.40 substituted or unsubstituted alkyleneoxyalkyl; C.sub.6 -C.sub.40 
substituted or unsubstituted alkylenearyl; C.sub.6 -C.sub.32 substituted 
or unsubstituted aryloxy; C.sub.6 -C.sub.40 substituted or unsubstituted 
alkyleneoxyaryl; C.sub.6 -C.sub.40 oxyalkylenearyl, and mixtures thereof; 
and 
v) the balance carriers and adjunct ingredients. 
The second component of this example of a preferred embodiment of the 
fragrance delivery systems of the present invention comprises the 
following pro-accords. 
Nonadyl orthoformate. This example of a preferred embodiment of the present 
invention comprises from about 0.5% to about 5% by weight, of nonadyl 
orthoformate having the formula: 
##STR29## 
preferably the compositions comprise 0.8% to about 1.6% by weight, of 
nonadyl orthoformate. 
Mugetanol orthoformate. This example of a preferred embodiment of the 
present invention comprises from about 1.5% to about 5% by weight, of 
mugetanol orthoformate having the formula: 
##STR30## 
preferably the compositions comprise from about 2.1% to about 4.2% by 
weight, of mugetanol orthoformate. 
Osyrol orthoformate. This example of a preferred embodiment of the present 
invention comprises from about 1.5% to about 5% by weight, of osyrol 
orthoformate having the formula: 
##STR31## 
preferably the compositions comprise from about 2.3% to about 4.6% by 
weight, of osyrol orthoformate. 
Orthoesters 
This example of a preferred embodiment of the present invention also 
comprises from about 1% to about 10% by weight, of one or more orthoester 
pro-accords wherein preferably R is hydrogen, methyl, ethyl, propyl, 
phenyl, benzyl, and mixtures thereof. 
Examples of suitable alcohols and esters released by the preferred 
pro-accords of the present invention are described hereinabove. An example 
of a preferred orthoester for use in the fragrance delivery systems of the 
present invention is benzyl orthoacetate. 
Article of Manufacture for Dispensing a Pro-accord Containing Perfume 
The present invention further relates to an article of manufacture for 
dispensing a perfume or fine fragrance which comprises a first reservoir 
for the pro-accords described herein above. In addition to the 
pro-accords, the reservoir, container, pouch or chamber may contain 
carriers, stabilizers, and other adjunct material suitable for use in 
perfumes, fine fragrances, colognes, eau de toilettes, after-shave lotions 
and the like. Generally, one or more of the pro-accords may be susceptible 
to acid catalyzed hydrolysis and therefore to protect from premature 
release of the fragrance raw materials the pro-accord reservoir contains 
sufficient basic material to provide an amount of reserve alkalinity equal 
to at least 0.001 molar NaOH. 
The article of manufacture for delivering the pro-accord containing 
fragrance materials of the present invention has a second reservoir which 
contains any base note fragrance raw materials or those top and middle 
note fragrance raw materials which are not suitable for exposure to the 
alkaline environment which is found in some embodiments of the pro-accord 
reservoir. In addition, the second reservoir may contain carriers, 
fixatives, and other adjunct ingredients suitable for use in the 
fragrance-containing compositions described herein above. 
In addition to the first reservoir containing the pro-accord material and 
the second reservoir containing the balance of the perfume ingredients, 
the article of manufacture comprises a mixing chamber, mixing tube, 
delivery tube or other modification which provides for efficient admixing 
of the material from each reservoir prior to delivering the fragrance 
material to human skin. The contents may be delivered via squeezing the 
contents onto the skin wherein the user admixes the contents of the two 
reservoirs as the materials is worked into the skin. This admixing can be 
accomplished by means of an "actuating device" wherein the admixture is 
formed by squeezing a "triggering " device which delivers measured amounts 
of each reservoir directly to the skin. Alternatively, a mixing chamber or 
a means for mixing the two components may be incorporated into the article 
of manufacture. Embodiments which have a "single use" amount of the 
fragrance material may have a collapsible membrane which separates the 
contents of the first reservoir from the second reservoir. For example, 
the user may squeeze a perfume containing pouch and admix the contents by 
working a flexible container with the fingers prior to opening and 
application to the skin. 
A further embodiment of the article of manufacture of the present invention 
encompasses a reservoir, container chamber or the like which holds the 
pro-accord component, said reservoir having an alkaline surface. This 
embodiment also includes surfaces which are typically a source of acid but 
which are modified to overcome or remove the acid source. An example of a 
surface which has been modified includes a glass surface wherein the 
surface silanols are capped with a non-acidic capping group. 
For example, an article of manufacture for dispensing a perfume or fine 
fragrance, said article comprising a reservoir for containing a perfume or 
fine fragrance wherein said reservoir comprises at least one material 
which provides said liquid perfume or fine fragrance which is contained 
within said reservoir, and which contacts a surface of said reservoir, 
with a neutral or alkaline pH, said liquid perfume or fine fragrance 
comprising one or more of the pro-accords as described herein above.

The following are general, non-limiting examples of procedures for 
preparing pro-accords. Unless otherwise indicated, the materials obtained 
from the following examples are not preferred pro-accords nor pro-accords 
suitable for use in the preferred embodiments described herein. 
EXAMPLE 1 
Preparation of tris(phenylethyl)orthoformate 
To a 500 mL single neck flask assembled with a short path distillation head 
and a magnetic stirrer is combined phenylethyl alcohol (66 g), triethyl 
orthoformate (20.2 g) and 3 drops of concentrated sulfuric acid under a 
nitrogen atmosphere. The reaction mixture is heated for 3 hr at 
100.degree. C. to distill over ethanol. The reaction progress is monitored 
by the amount of ethanol generated and by silica gel thin layer 
chromatography (TLC) eluting with 4% ethyl acetate/petroleum ether and 
development with iodine stain. Upon completion, the reaction mixture is 
diluted with diethyl ether (200 mL) and the organic phase washed three 
times with saturated aqueous sodium carbonate. The organic phase is dried 
over magnesium sulfate, filtered, and the resulting clear solution is 
concentrated in vacuo. The product is purified by kugelrohr distillation 
wherein the fraction in the range 120-140.degree. C., at 0.1 mm Hg is 
collected to yield 47 g (91%). .sup.1 H NMR (CDCl.sub.3); .delta. 7.2 (m, 
15H); 5.0 (s, 1H); 3.6 (t, 6H); and 2.8 (t, 6H); .sup.13 C NMR 
(CDCl.sub.3); .delta. 138.61, 128.81, 128.17, 126.10, 112.52, 64.76, and 
35.89. 
EXAMPLE 2 
Preparation of tris(9-decenyl)orthoformate 
The procedure described above is suitable for use in preparing 
tris(9-decenyl)orthoformate using 9-decenol (42.5 g, Rosalva-IFF), and 
triethyl orthoformate (10 g), to yield 27g (83%) of a clear oil isolated 
by kugelrohr distillation within the range 140-150.degree. C., at 0.1 mm 
Hg. .sup.1 H NMR (CDCl.sub.3).delta. 5.8 (m, 3H); 5.1 (s, 1H); 4.9 (m, 
6H); 3.5 (t, 6H); 2.0 (m, 6H); 1.6 (m, 6H); and 1.35 (m, 30H); .sup.13 C 
NMR (CDCl.sub.3) .delta. 138.87, 113.89, 112.47, 67.74, 33.56, 29.28, 
29.19, 29.15, 28.84, 28.68, and 25.52. 
EXAMPLE 3 
Preparation of tris(cis-3-hexenyl)orthoformate 
The procedure described above is suitable for use in preparing 
tris(cis-3-hexenyl)orthoformate using cis-3-hexenol (115 g), and triethyl 
orthoformate (42.7 g) to yield 79 g (88%) of a clear oil isolated by 
kugelrohr distillation at 100.degree. C., 0.1 mm Hg. .sup.1 H NMR 
(CDCl.sub.3) .delta. 5.45 (m, 3H); 5.35 (m, 3H); 5.2 (s, 1H); 3.5 (t, 6H) 
2.35 (d, t, 6H); 2.05 (d, t, 6H), and 1.0 (t, 9H); .sup.13 C NMR 
(CDCl.sub.3) .delta. 133.57, 124.46, 112.31, 63.51, 27.36, 20.39, and 
13.99. 
EXAMPLE 4 
Preparation of tris(geranyl/neryl) orthoformate 
To a 500 mL single neck flask equipped with a short path distillation head 
and a magnetic stirrer is combined a mixture of geraniol and nerol (52 g, 
Bush Boake Allen 70/30), triethyl orthoformate (10 g) and anhydrous citric 
acid (0.66 g) under a nitrogen atmosphere. (The use of citric acid 
prevents undesired decomposition of the product). The reaction mixture is 
heated for 4 hr at 100.degree. C. during which time ethanol is removed via 
distillation. The reaction progress is monitored by the amount of ethanol 
generated and by silica gel thin layer chromatography (TLC) eluting with 
4% ethyl acetate/petroleum ether and development with iodine stain. Upon 
completion, the reaction mixture is diluted with diethyl ether (200 mL) 
and the organic phase washed three times with saturated aqueous sodium 
carbonate. The organic phase was dried over magnesium sulfate, filtered, 
and the resulting clear solution is concentrated in vacuo. The product is 
purified by kugelrohr distillation wherein the fraction in the range 
140--150.degree. C., at 0.1 mm Hg is collected to yield 23.5 g (73%). 
.sup.1 H NMR (CDCl.sub.3) .delta. 5.35 (m, 3H); 5.25 (m, 1H); 5.1 (m, 3H); 
4.15 (m, 6H); 2.1 (m, 12H); and 1.8-1.6 (m, 27H); .sup.13 C NMR 
(CDCl.sub.3) .delta. 139.96, 139.75, 131.53, 131.25, 123.73, 123.59, 
120.97, 119.99, 111.01, 60.40,60.05, 39.31, 31.97, 26.48, 26.12, 25.39, 
23.19, 17.37, and 16.14. 
EXAMPLE 5 
Preparation of tris(phenylethyl)orthoacetate 
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 (100 g), 
trimethylorthoacetate (30 g) and 3 drops of concentrated sulfuric acid. 
Nitrogen is slowly bubbled through the solution over a 4 day period to 
remove the methanol which is produced. The mixture is then diluted in 
diethyl ether (300 mL) and washed three times with saturated aqueous 
sodium carbonate. The organic phase is dried over magnesium sulfate, 
filtered, and the resulting clear solution is concentrated. The product is 
purified by kugelrohr distillation wherein the fraction in the range 
150-170.degree. C., at 0.1 mm Hg is collected to yield 72 g (74%). .sup.1 
H NMR (CDCl.sub.3) .delta. 7.2 (m, 15H); 3.6 (t, 6H); 2.8 (t, 6H); and 1.4 
(s, 3H); .sup.13 C NMR (CDCl.sub.3) .delta. 138.92, 128.93, 128.15, 
126.07, 114.18, 63.01, 36.26, and 20.20. 
EXAMPLE 6 
Preparation of tris(cis-3-hexenyl)orthoacetate 
The procedure described above is suitable for use in preparing 
tris(cis-3-hexenyl)orthoacetate using cis-3-hexenol (65 g) and trimethyl 
orthoacetate (22.2 g) and para-toluenesulfonic acid monohydrate (0.35 g) 
over 5 days, to yield 38.6 g (64%) of a clear oil isolated by kugelrohr 
distillation within the range 110-120.degree. C., at 0.1 mm Hg. .sup.1 H 
NMR (CDCl.sub.3) .delta. 5.3 (m, 6H), 3.4 (t, 6H), 2.25 (d, t, 6H); 2.0 
(d, t, 6H); 1.4 (s, 3H); and 0.9 (t, 9H); .sup.13 C NMR (CDCl.sub.3) 
.delta. 133.73, 125.03, 113.80, 61.48, 27.54, 20.29, 19.92, and 13.94. 
EXAMPLE 7 
Preparation of bis(geranyl/neryl) vanillin acetal 
To a 1 L single-neck flask equipped with a Dean-Stark trap, condenser, and 
magnetic stirrer under a nitrogen atmosphere is added vanillin (60 g), 
geraniol/nerol (182 g, Bush Boake Allen 70/30), anhydrous citric acid 
(3.78 g) and 400 mL benzene. The mixture is refluxed for 24 hr during 
which time 4 mL of water is isolated in the Dean-Stark trap. The trap is 
replaced with a Soxhlet extractor having a cup containing 300 mL of 
activated molecular sieves (3 .ANG.) and the reaction is refluxed for an 
addition 24 hr. The reaction mixture is cooled and washed four times with 
saturated aqueous sodium carbonate. The organic phase is dried over 
magnesium sulfate, filtered, and the resulting clear solution is 
concentrated in vacuo. The product is purified by kugelrohr distillation 
wherein the fraction above 80.degree. C., at 0.1 mm Hg is retained to 
yield 111 g (84%) of a yellow oil comprising three isomers. .sup.1 H NMR 
(CDCl.sub.3) .delta. 7.1-6.9 (m, 3H); 5.75 (s,b, 1H); 5.5 (s, 1H); 5.35 
(m, 2H); 5.10 (m, 2H); 4.1 (m, 4H), 3.85 (s, 3H); 2.1 (m, 8H); and 
1.75-1.60 (ms, 18H); .sup.13 C NMR (CDCl.sub.3) .delta. 146.25, 145.47, 
140.21, 139.93, 131.63, 131.36, 130.93, 123.78, 123.63, 121.34, 120.39, 
119.82, 113.64, 108.83, 100.04, 61.66, 61.55, 61.36, 55.66, 39.39, 32.04, 
26.54, 26.17, 25.44, 23.28, 17.44, and 16.23. 
EXAMPLE 8 
Preparation of bis(phenylethyl)benzaldehyde acetal 
To a 1 L single-neck flask equipped with a Dean-Stark trap, condenser, and 
magnetic stirrer under a nitrogen atmosphere is added benzaldehyde (31.5 
g), phenylethyl alcohol (159.5 g), and para-toluenesulfonic acid 
monohydrate (1.46 g) and 320 mL toluene. The mixture is refluxed for 3 hr 
during which time 5 mL of water is isolated in the Dean-Stark trap and TLC 
analysis (4% ethyl acetate/petroleum ether as the eluent) indicates all of 
the benzaldehyde is consumed. Upon completion, the reaction mixture is 
diluted with diethyl ether (200 mL) and the organic phase washed three 
times with saturated aqueous sodium carbonate. The organic phase is dried 
over magnesium sulfate, filtered, and the resulting clear solution is 
concentrated in vacuo. The product is purified by kugelrohr distillation 
wherein the fraction above 70.degree. C., 0.3 mm Hg is retained and yields 
58.6 g (59%) of a clear-yellow oil. The material obtained is further 
purified by chromatography over silica gel (Merck 230-400 mesh) eluting 
with 4% ethyl acetate/1% triethyl amine/petroleum ether to give a clear 
oil. .sup.1 H NMR (CDCl.sub.3) .delta. 7.3 (m, 115H); 5.5 (s, 1H); 3.6 (t, 
4H); and 2.8 (t, 4H). .sup.13 C NMR (CDCl.sub.3) .delta. 139.07, 128.97, 
128.27, 128.10, 126.70, 126.15, 101.44, 66.08, and 36.34. 
EXAMPLE 9 
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) and para-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.degree. C., 0.1 mm 
Hg is retained to yield 12.8 g (50%) of a clear oil. .sup.1 H NMR 
(CDCl.sub.3) .delta. 7.2 (m, 16H); 3.6 (t, 8H); and 2.8 (t, 8H); .sup.13 C 
NMR (CDCl.sub.3) .delta. 138.84, 128.89, 128.11, 126.03, 119.57, 63.75, 
and 35.8. 
Perfume Compositions 
The following are examples of fine fragrance compositions which comprise 
pro-accords according to the present invention. 
EXAMPLE 10 
______________________________________ 
Ingredients weight % 
______________________________________ 
Pro-Accord Component.sup.1 
Tris(geranyl) orthoformate.sup.2 
2.2 
Tris(geranyl) orthoacetate.sup.3 
1.8 
Tris(phenylethyl) orthoformate 
1.2 
cis-Jasmone bis(phenylethyl) acetal 
2.3 
Potassium carbonate.sup.4 ethanol.sup.5 
3.2 
Fragrance Raw Material Component 
Phenyl acetaldehyde 0.2 
Base notes.sup.6 83.9 
Adjuncts.sup.7 0.6 
Ethanol.sup.8 balance 
______________________________________ 
.sup.1 Proaccord having a "rose" characteristic. 
.sup.2 The tenn "geranyl" refers to a mixture of "geranyl and neryl". 
.sup.3 The term "geranyl" refers to a mixture of "geranyl and neryl". 
.sup.4 Sufficient to provide 1 millimolar potassium carbonate reserve 
alkalinity. 
.sup.5 Ethanol carrier contains less than 1% water. 
.sup.6 Fragrance raw material base notes which includes polyethylene 
glycol as carrier. 
.sup.7 Jasmin Absolute derived from Jasminum grandiflorum L. (Oreaceae). 
.sup.8 Anhydrous ethanol. 
EXAMPLE 11 
______________________________________ 
Ingredients weight % 
______________________________________ 
Pro-Accord Component.sup.1 
Tris(geranyl) orthoformate 
0.9 
Tris(benzyl) orthoacetate 
0.8 
Tris(cis-3-hexenyl) orthoformate 
0.6 
Tris(9-decen-1-ol) orthoformate 
0.4 
Tris(phenylethyl) orthoformate 
0.5 
cis-Jasmone bis(phenylethyl) acetal 
1.1 
Potassium carbonate.sup.2 ethanol.sup.3 
3.4 
Fragrance Raw Material Component 
Phenyl acetaldehyde 0.2 
Base, middle and top notes.sup.4 
8.2 
Adjuncts.sup.5 0.3 
Ethanol.sup.6 balance 
______________________________________ 
.sup.1 Proaccord having a "modified rose" characteristic. 
.sup.2 Sufficient to provide 1 millimolar potassium carbonate reserve 
alkalinity. 
.sup.3 Ethanol carrier contains less than 1% water. 
.sup.4 Fragrance raw material base, middle and top notes which includes 
polyethylene glycol as carrier and anhydrous ethanol as a diluent. 
.sup.5 Mixture of synthetic ()-cis and ()-trans-4-methyl-2-(2-methyl-1 
propenyl)tetrahydropyran; rose oxide. 
.sup.6 Anhydrous ethanol. 
EXAMPLE 12 
______________________________________ 
Ingredients weight % 
______________________________________ 
Pro-Accord Component.sup.1 
Tris(citronellyl) orthoformate 
1.1 
Tris(benzyl) orthoacetate 
0.8 
Tris(cis-3-hexenyl) orthoformate 
0.6 
Citronellyloxyacetaldehyde bis(citronellyl) acetal 
0.7 
Tris(phenylethyl) orthoacetate 
0.6 
.alpha.-Hexylcinnamaldehyde bis(phenylethyl) acetal 
0.6 
Potassium carbonate.sup.2 ethanol.sup.3 
3.4 
Fragrance Raw Material Component 
Phenyl acetaldehyde 0.2 
Base notes and fragrance raw materials.sup.4 
78.4 
Adjuncts.sup.5 2.1 
Ethanol.sup.6 balance 
______________________________________ 
.sup.1 Proaccord having a "muguet" characteristic. 
.sup.2 Sufficient to provide 1 millimolar potassium carbonate reserve 
alkalinity. 
.sup.3 Ethanol carrier contains less than 1% water. 
.sup.4 Fragrance raw material base, middle and top notes which includes 
polyethylene glycol as carrier and anhydrous ethanol as a diluent. 
.sup.5 Diethyl phthalate as a fixative. 
.sup.6 Anhydrous ethanol. 
EXAMPLE 13 
______________________________________ 
Ingredients weight % 
______________________________________ 
Pro-Accord Component 
Bis(citronellyl) linalyl orthoacetate 
6.0 
Tris(geranyl) orthoacetate 
0.4 
cis-Jasmone bis(phenylethyl) acetal 
0.3 
Potassium carbonate.sup.1 ethanol.sup.2 
2.2 
Fragrance Raw Material Component 
Coriander 0.2 
Methyl phenylcarbinyl acetate 
0.2 
Benzyl acetate 1.5 
Galbanum oil.sup.3 0.2 
Citrolal PG 2.5 
Triplal.sup.4 0.2 
Ethyl acetoacetate 0.8 
Lindenol 0.5 
.gamma.-Methyl ionone 2.0 
Cyclogalbanate 0.2 
P. T. Bucinal 3.5 
Iso E super 2.5 
Galaxolide 50 DEP 22.0 
Methyl dihydrojasmonate 
23.0 
Exaltolide 3.5 
Hexyl cinnamic aldehyde 
2.0 
Helional 1.5 
Ethyl brassylate 9.0 
Ambrettolide 0.2 
cis-3-Hexenyl salicylate 
2.5 
Lemon Wescorps XC 0.2 
Indole.sup.4 0.5 
Cetalox.sup.4 1.0 
Dipropylene glycol 8.0 
Violet Leaf Absolute.sup.3 
1.0 
Calone 1951.sup.4 0.5 
Phenyl acetaldehyde.sup.5 
0.2 
Mayol 2.0 
Ethanol.sup.6 balance 
______________________________________ 
.sup.1 Sufficient to provide 1 millimolar potassium carbonate reserve 
alkalinity. 
.sup.2 Ethanol carrier contains less than 1% water. 
.sup.3 1% solution in dipropylene glycol carrier. 
.sup.4 10% solution in dipropylene glycol carrier. 
.sup.5 10% solution in polyethylene alcohol carrier. 
.sup.6 Anhydrous ethanol carrier. 
TABLE II 
______________________________________ 
weight % 
Ingredients 14 15 
______________________________________ 
Component 1 
Fragrance accord.sup.1 
14 28 
Ethanol balance balance 
Component 2 
Nonadyl orthoformate 0.8 1.6 
Mugetanol orthoformate 
2.1 4.2 
Osyrol orthoformate 2.3 4.6 
Benzyl orthoacetate 3.7 7.4 
1 mM potassium carbonate in ethanol 
balance balance 
______________________________________ 
.sup.1 A proprietary fragrance accord comprising one or more fragrance ra 
materials selected from the group consisting of alcohols, esters, ketones 
aldehydes, alkenes, ethers, and mixtures thereof.