JP2002504532A - Tertiary alcohol fragrance raw material delivery system - Google Patents

Abstract

  (57) [Summary] The present invention relates to a professional fragrance suitable for use in delivering tertiary alcohol fragrance ingredients to human skin. The present invention also relates to a fragrance delivery system suitable for use in fine fragrance and perfume compositions, the system comprising at least one pro-perfume for delivering tertiary fragrance raw material alcohols, and the remainder of the other pro-accords. In.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION

The present invention relates to pro-accords capable of releasing tertiary alcohol fragrance raw materials, in particular linalool, tetrahydrolinalool, ethyl linalool and dihydromyrcenol. The present invention also relates to a fragrance delivery system containing the proaccord, thus providing a means for delivering tertiary alcohol fragrance ingredients to the right place, preferably human skin. The present invention further relates to fine fragrances and fragrances containing the above tertiary alcohol releasing fragrance delivery system. The fragrance delivery systems described here also increase the fragrance life.

[0002]

BACKGROUND OF THE INVENTION

Humans have applied scents and fragrances to the skin since ancient times. Originally, these aesthetically pleasing substances were usually isolated unpurified as resins, gums or essential oils from natural sources, especially the bark, roots, leaves and fruits of native plants. These resins, rubbers and oils were applied directly to the body or diluted with water or other solvents, including wine in some cases. With the advent of modern chemistry, the individual components involved in the aroma of these resins, rubbers and oils were isolated and later characterized. Current perfume traders are artificially formulating fragrance materials to achieve new fragrance compositions with distinct "features".

[0003] Many current fragrances are no longer derived from natural sources and are synthesized by modern chemical methods as highly pure fragrance raw materials (FRMs). These FR
M is now formulated to make fine perfumes, colons, eau de toilette, aftershave lotions and other personal fragrance compositions. Manufacturers of these fragrance-containing compositions classify fragrances into three types based on their relative volatility: top, middle and base notes.

A disadvantage of typical fine fragrances and fragrances is that when a fragrance or fragrance is applied to human skin, the original fragrance, which is based on the balance of the fragrance ingredients, begins to change. This loss of fragrance balance is due in part to the different evaporation of highly volatile top notes and the absorption of other components to the skin surface. Fragrance and fine fragrance users have attempted to solve this problem in a number of ways. One way is to initially "perfume the fragrance" to the fragrance and reduce the fragrance to an appropriate level after a few hours when the desired effect is needed, depending on the natural rate of evaporation. Another commonly used method is to reapply a small amount of perfume to the skin at short intervals to continuously update the fragrance. Neither of these solutions is sufficient to compensate for the decreasing levels of top and middle notes over time. In fact, base notes that exist for a long period of time due to low volatility begin to accumulate with each "refreshing" of the perfume, after which the base notes begin to outpace other fragrance notes, breaking the original fragrance balance.

[0005] Recently, it has been discovered that some fragrance ingredients can be delivered to human skin via professional fragrances. These professional fragrance compounds include human skin surface and acidic pH
Acid labile acetal, which decomposes on contact resulting in release of fragrance raw materials,
There are ketals and orthoesters. Generally, acetal releases aldehydes, ketals release ketones, and orthoesters release alcohols. However, while being acid labile, some pro-perfumes have a fragrance release half-life outside the useful period of use as a fine fragrance or perfume composition (
(Hydrolysis rate), the supplier was limited. Moreover, the prior art does not disclose a professional fragrance that properly releases a tertiary alcohol fragrance material.

[0006] It has been unexpectedly found that certain orthoester proaccords can deliver one or more tertiary alcohol fragrance ingredients at a rate that can provide a useful means for delivering these desirable fragrance ingredients to human skin. Was also found. In addition, the proaccords described herein are tailored to deliver tertiary alcohols at a rate preferred by the trader.

[0007]

[Summary of the Invention]

It has been surprisingly discovered that certain orthoesters containing at least one tertiary alcohol fragrance ingredient that release tertiary alcohol at a rate that can be adjusted to meet the particular needs of the trader can be produced. Thus, the present invention satisfies the above needs. For example, prolonged release of fragrance ingredients provides merchants with a means to last the original perfume ingredient blend or original fragrance notes. With the use of the proaccord of the present invention, merchants can control and release tertiary alcohol fragrance ingredients. This controlled release is a means to prolong the life of tertiary alcohol fragrances on human skin.

[0008] A first aspect of the invention relates to a proaccord having the formula:

Embedded imageIn the above formula, each -OR¹, -OR²And -OR³The part is each R¹, R²And R ³ Is independently substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C₂₀Branch
Luquil, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl, C₃-C ₂₀ Straight chain alkenyl, C₄-C₂₀Branched alkenyl, C₃-C₂₀Cyclic alkene
Le, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆-C₂₀A
Luylene aryl, C₆-C₂₀Alkyleneoxyalkyl, C₆-C₂₀Al
Derived from alcohols to be kilenoxyaryl and their mixtures
An alkoxy unit; or any two R¹, R²Or R³Is
Together, they may form a ring having 5 to 8 atoms, where the ring is one or more.
C₁-C₂₂Alkyl, C₁-C₂₂Alkenyl, C₆-C₁₂Aryl, C ₆ -C₂₂Optionally further substituted with alkylenearyl units and mixtures thereof
R is hydrogen, substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-
C₂₀Branched alkyl, C₃-C₂₀Cyclic alkyl, C₃-C₂₀Branched cyclic alk
Le, C₃-C₂₀Straight chain alkenyl, C₄-C₂₀Branched alkenyl, C₃-C₂₀ Cyclic alkenyl, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀Aryl, C ₆ -C₂₀Alkylenearyl, C₆-C₂₀Alkyleneoxyalkyl, C₆ -C₂₀Alkyleneoxyaryl and mixtures thereof; or
R¹, R²Or R³Together with R form a ring with 5 to 8 atoms
(The ring may have one or more C₁-C₂₂Alkyl, C₁-C₂₂Al
Kenil, C₆-C₁₂Aryl, C₆-C₂₂Alkylenearyl units and their
Optionally further substituted with these mixtures), provided that at least one R¹,
R²Or R³Units are derived from tertiary fragrance raw material alcohols;
Proacord has a fragrance release half-life of NaH₂PO₄Measured in buffer
At pH 5.3 and at pH 2.5 for 12 hours or less.
Has a glance release half-life.

The present invention preferably provides 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 the fragrance release half-life is measured in NaH ₂ PO ₄ buffer. At least one proaccord, as described herein, which is capable of releasing tertiary alcohol fragrance raw materials as appropriate, comprising one or more proacords, especially orthoesters, ketals, acetals, ortho It also relates to fragrance delivery systems, including with carbonates.

The present invention also relates to perfumes and fine fragrances which, in addition to the fragrance delivery systems described herein, also contain other fragrance ingredients and auxiliary ingredients. These and other objects, features and advantages will become apparent to those skilled in the art from a reading of the following specific description and the appended claims. All percentages, ratios and proportions herein are by weight unless otherwise indicated. All temperatures are in degrees Celsius (° C) unless otherwise noted. All documents cited are, in relevant part, incorporated herein by reference;

[0011]

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel compositions of the present invention, that is, orthoesters capable of releasing tertiary alcohol fragrance raw materials. This tertiary alcohol release rate, as described herein, is known below as the "fragrance release half-life", but provides for the release of tertiary alcohols to the particular requirements of fragrance-containing compositions. It can be operated to be adjusted.

[0012] Tertiary fragrance raw material releasing compounds are referred to throughout the specification as pro-perfumes, pro-fragrances or, preferably, pro-accords, which terms refer to ortho-alcohols that can release at least one tertiary alcohol fragrance raw material. Used generically and / or interchangeably to represent an ester.

For the purposes of the present invention, the terms “perfume” and “fine fragrance” are synonymous in nature and are used generically or interchangeably throughout this specification to include more concentrated forms of fragrance-containing Used to mean composition. Thus, aspects of the invention that apply to "fragrances" apply equally to "fine fragrances" and vice versa. Typically, colons, eau de toilette, aftershave and other fragrance containing embodiments are fragrances or fine fragrances, usually with greater dilution by volatile carriers such as ethanol.

A mixture of fragrance materials is known to fragrance and perfume traders as “accords”. As used herein, the term "accord" refers to "pleasant scent,
2 Artificially combined to impart aroma, extract or fragrance characteristics
The fragrance delivery system of the present invention is defined as a mixture of one or more 'fragrance ingredients'. At least one proaccord capable of releasing at least one tertiary alcohol, and preferably a fragrance ingredient or' It contains one or more other "pro-accords" capable of releasing a mixture of "accords." For the purposes of the present invention, the "fragrance raw material" preferably has a molecular weight of at least 100 g / mol. , Alone or in combination with other “fragrance ingredients” are defined herein as compounds that are useful in imparting aroma, fragrance, extract or aroma, however, the term “fragrance ingredients” refers to tertiary alcohol releasing pro-codes. The molecular weight of the associated alcohol, which together with the tertiary alcohol forms a pro-accode May have a molecular weight of less than 100 g / mol.
As described further below, low molecular weight alcohols, especially ethanol, are used as the orthoester alcohol component so as to exhibit the desired fragrance release half-life.

Typically, the “fragrance raw materials” that make up the non-tertiary alcohol releasing proaccord of the fragrance delivery system of the present invention include, in particular, alcohols, ketones, aldehydes, esters, ethers, nitriles and alkenes such as terpenes. is there. A list of common "fragrance ingredients" can be found in various references, such as "Perfume and Flavor Chemicals", Vols. Ian, both of which are incorporated herein by reference.
d II, Steffen Arctander Allured Pub. Co. (1994) and “Perfumes: Art, Science
and Technology ”, Muller, PMand Lamparsky, D., Blackie Academic and Profe
Seen in ssional (1994).

For the purposes of the present invention, a substituted or unsubstituted alkyleneoxy unit is defined as a moiety having the formula:

Embedded image Wherein R ⁵ is hydrogen, methyl and mixtures thereof; R ⁶ is hydrogen, methyl, ethyl and mixtures thereof; index x is from 1 to about 20.

For the purposes of the present invention, a substituted or unsubstituted alkyleneoxyalkyl is defined as a moiety having the formula:

Embedded imageIn the above formula, R⁵Is hydrogen, C₁-C₁₈Alkyl and mixtures thereof; R ⁶ Is hydrogen, methyl, ethyl and mixtures thereof;
About 20, and the index y is 2 to about 18.

For the purposes of the present invention, a substituted or unsubstituted alkylenearyl unit is defined as a moiety having the formula:

Embedded imageIn the above formula, R⁵And R6 are each independently hydrogen, hydroxy, nitrilo, halogeno
, Nitro, carboxyl (-CHO, -CO₂H, -CO₂R ', -CONH ₂ , -CONHR ', -CONR'₂R 'is C₁-C₁₂Linear or branched al
Kill)), amino, alkylamino and mixtures thereof;
It is about 14.

For the purposes of the present invention, a substituted or unsubstituted alkyleneoxyaryl unit is defined as a moiety having the formula:

Embedded imageIn the above formula, R⁵And R6 are each independently hydrogen, hydroxy, nitrilo, halogeno
, Nitro, carboxyl (-CHO, -CO₂H, -CO₂R ', -CONH ₂ , -CONHR ', -CONR'₂R 'is C₁-C₁₂Linear or branched al
Alkyl), amino, alkylamino and mixtures thereof;
It is about 14.

Tertiary Alcohol Release Proaccord The proaccord of the present invention which releases at least one tertiary alcohol fragrance raw material has the formula:

Embedded image The hydrolysis of the orthoester releases the fragrance ingredients according to the following scheme:

Embedded image Thus, 2 equivalents of alcohol and 1 equivalent of ester are released.

Each R¹, R²And R³Is independently substituted or unsubstituted C₁-C₂₀Linear alk
Le, C₃-C₂₀Branched alkyl, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branch
Cyclic alkyl, C₃-C₂₀Straight chain alkenyl, C₄-C₂₀Branched alkenyl, C ₃ -C₂₀Cyclic alkenyl, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀A
Reel, C₆-C₂₀Alkylenearyl, C₆-C₂₀Alkyleneoxyal
Kill, C₆-C₂₀Alkyleneoxyaryl and mixtures thereof, preferably
Is substituted or unsubstituted C₁-C₁₀Linear alkyl, C₃-C₁₀Branched alkyl, C ₃ -C₁₀Cyclic alkyl, C₄-C₁₀Branched cyclic alkyl, C₃-C₁₀Straight chain
Lucenyl, C₄-C₁₀Branched alkenyl, C₃-C₁₀Cyclic alkenyl, C₄-
C₁₀Branched cyclic alkenyl and mixtures thereof; or any two of them
R¹, R²Or R³Together form a ring with 5 to 8 atoms
(The ring is one or more C₁-C₂₂Alkyl, C₁-C₂₂Alkenyl,
C₆-C₁₂Aryl, C₆-C₂₂Alkylenearyl units and their mixtures
Optionally further substituted with a compound of the formula¹, R²And R³Out of units
At least one is derived from a tertiary alcohol.

Non-limiting examples of tertiary alcohol fragrance raw materials include a, a-dimethylphenethyl alcohol (dimethylbenzylcarbinol), a, a, 4-trimethyl-3
-Cyclohexene-1-methanol (a-terpineol), a, a, 4-trimethylbenzylethanol (p-methyldimethylbenzylcarbinol), 2-
(4-methylphenyl) -2-propanol (simenol), 2-methyl-4-
Phenyl-2-butanol (phenylethyldimethylcarbinol), 3-methyl-1-phenyl-3-pentanol (phenylethylmethylethylcarbinol), 1,2-dimethyl-3- (1-methylethenyl) cyclopentanol (Purinol), 1,2-dimethyl-3- (1-methylethenyl) cyclohexanol, 1-methyl-4-isopropylcyclohex-8-ol (dihydroterpineol), 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde (Lilal; Covanol), 2,6-dimethylheptane-2-ol (dimetol, freesyol, loritol), 2,6,6
-Trimethylbicyclo [1.3.3] heptan-2-ol (cis-2-pinanol), 2,6,6-trimethylbicyclo [1.3.3] heptan-2-ol (cis and trans-2- Pinanol), 2,6-dimethyl-2-octanol (tetrahydromyrcenol), 2-methyl-2-octanol (methyloctanol), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol) , 2,6-dimethyl-7-octen-2-ol (limolene), 2,6-
Dimethyl-3,5-octadien-2-ol (Muguol), 2-methyl-6
-Methylene-7-octen-2-ol (myrcenol), 2,6-dimethyl-
5,7-octadien-2-ol (oximenol), 3,6-dimethyl-3-
Octanol, 3-methyl-3-octanol (Aprol 161), 3,7-dimethyl-3-octanol and 2,6-dimethyl-2-octanol (tetrahydromugool, tetralol, linaxol), 3,7-dimethyl -6-octen-3-ol (dihydrolinalool), 3,7-dimethyl-3-octanol (
Tetrahydrolinalool), 3-methyl-1-octen-3-ol (Aprol 16
0), 7-hydroxy-3,7-dimethyloctanol (hydrolen), 3,7-dimethyl-1,6-octadien-3-ol (linalool), 7-hydroxy-3,7-dimethyloctanal (hydroxycitro Neral, laurinal), 7-hydroxy-3,7-dimethyloctanal dimethyl acetal (hydroxycitronellal dimethyl acetal), 3,7-dimethyl-1,6-nonadien-3-ol (ethyl linalool), 2, 5,5-trimethyloctahydro-2-naphthalenol (ambrinol), 2-methyl-2-vinyl-5- (
1-hydroxy-1-methylethyl) tetrahydrofuran (cis and trans) (linalool oxide), 4- (4-hydroxy-4-methylpentyl) -3
-Cyclohexene-1-carboxaldehyde (Lilal; Covanol), 4-
Methyl-1- (1-methylethyl) -3-cyclohexen-1-ol, 3,7
, 9-Trimethyl-1,6-decadien-3-ol (isobutyl linalool)
, 3,7,11,15-Tetramethylhexadec-1-en-3-ol (isophytol), cedrol and b-caryophyllene alcohol (caryophyllenol).

Non-limiting examples of preferred tertiary alcohol fragrance ingredients include linalool, tetrahydrolinalyl, ethyl linalyl, dihydromyrcenyl and mixtures thereof having R ¹ , R ² and R ³ units, linalool, There are compounds that result in the release of tetrahydrolinalool, ethyl linalool and dihydromyrcenol.

R is hydrogen, substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C₂₀Branch
Luquil, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl, C₃-C ₂₀ Straight chain alkenyl, C₄-C₂₀Branched alkenyl, C₃-C₂₀Cyclic alkene
Le, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆-C₂₀A
Luylene aryl, C₆-C₂₀Alkyleneoxyalkyl, C₆-C₂₀Al
Alkylene aryl and mixtures thereof; or¹,
R²Or R³May form a ring having 5 to 8 atoms together with R
The ring has one or more C₁-C₂₂Alkyl, C₁-C₂₂Alkenyl, C₆ -C₁₂Aryl, C₆-C₂₂Alkylenearyl units and their mixtures
And is optionally further substituted. Preferably, R is hydrogen, substituted or unsubstituted
C₁-C₁₀Linear alkyl, C₃-C₁₀Branched alkyl, C₃-C₁₀Linear al
Kenil, C₆-C₁₀Aryl, C₆-C₁₀Alkylenearyl, and
Preferably R is hydrogen, methyl, ethyl, propyl, isopropyl, t-butyl,
It is selected from the group consisting of phenyl, benzyl and mixtures thereof.

As used herein, the term “substituted” means “a compatible moiety that replaces a hydrogen atom”. Non-limiting examples of substituents include hydroxy, nitrilo, halogen, nitro, carboxyl (
-CHO, -CO ₂ H, -CO ₂ R ', -CONH ₂ , -CONHR', -CO
NR ′ ₂ ; R ′ is C ₁ -C ₁₂ straight or branched alkyl), amino, C ₁ -C ₁₂ mono- and dialkylamino and mixtures thereof.

Fragrance Delivery System and Related Compositions The present invention provides: a) at least one tertiary alcohol fragrance raw material release proaccord as described above; and b) the delivery of the remaining one or more fragrance raw materials. It also relates to a fragrance delivery system comprising one or more proaccords suitable for use in fragrances. When formulated in a fragrance delivery system, the tertiary alcohol fragrance raw material release orthoester of the present invention is from about 0.1 to about 99% by weight of the fragrance delivery system, preferably from about 1 to about 50%. The fragrance delivery system of the present invention preferably comprises one or more proaccords described below. When present, the proaccord, alone or as a mixture, is from 0.1% to about 99%, preferably from about 1% to about 50%, by weight of the fragrance delivery system.

The present invention provides: a) 0.1 to 99.9% by weight of at least one proaccord releasing tertiary alcohol fragrance raw material, provided that the proaccord has a fragrance release half-life of NaH ₂ PO ₄ 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 a buffer); b) one or more fragrance ingredients 0.1 -99.9% by weight; and c) The fragrance or fine fragrance for application to human skin, having a long fragrance life, consisting of the balance carrier and auxiliary ingredients. In addition, the fragrance or fine fragrance composition of the present invention may comprise a carrier, a volatile retention agent (e.g., a tertiary alcohol-releasing orthoester or proaccord, which may be added in any suitable amount or ratio to the remainder of the delivery system. Fixative) and other additional ingredients. Typical carriers are methanol, ethanol (preferred), isopropanol, polyethylene glycol, and in some cases water. Volatile retention agents serve to reduce the volatility of certain top and middle notes and prolong contact time with the skin. Auxiliary components include perfume raw materials, which are not single chemicals because they are essential oils. In addition, the auxiliary component may be a mixture of synthetic fragrance ingredients, which serves other purposes besides emitting a pleasant aroma.

Orthoesters One class of preferred compounds useful as proaccords according to the present invention are orthoesters having the formula:

Embedded image The hydrolysis of the orthoester releases the fragrance ingredients according to the following scheme:

Embedded imageIn the above formula, R is hydrogen, substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C_{2 0} Branched alkyl, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl,
C₃-C₂₀Straight chain alkenyl, C₄-C₂₀Branched alkenyl, C₃-C₂₀Cyclic
Alkenyl, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆-
C₂₀Alkylenearyl, C₆-C₂₀Alkyleneoxyalkyl, C₆-C ₂₀ Alkyleneoxyaryl and mixtures thereof; preferably hydrogen, substituted or
Or unsubstituted C₁-C₁₀Linear alkyl, C₃-C₁₀Branched alkyl, C₃-C_{1 0} Straight chain alkenyl, C₆-C₁₀Aryl, C₆-C₁₀With alkylenearyl
More preferably, R is hydrogen, methyl, ethyl, propyl, isopropyl,
selected from the group consisting of t-butyl, phenyl, benzyl and mixtures thereof
You. Each R¹, R²And R³Is independently substituted or unsubstituted C₁-C₂₀Linear alk
Le, C₃-C₂₀Branched alkyl, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branch
Cyclic alkyl, C₃-C₂₀Straight chain alkenyl, C₄-C₂₀Branched alkenyl, C ₃ -C₂₀Cyclic alkenyl, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀A
Reel, C₆-C₂₀Alkylenearyl, C₆-C₂₀Alkyleneoxyal
Kill, C₆-C₂₀Alkyleneoxyaryl and mixtures thereof; preferably
Is substituted or unsubstituted C₁-C₁₀Linear alkyl, C₃-C₁₀Branched alkyl, C ₃ -C₁₀Cyclic alkyl, C₄-C₁₀Branched cyclic alkyl, C₃-C₁₀Straight chain
Lucenyl, C₄-C₁₀Branched alkenyl, C₃-C₁₀Cyclic alkenyl, C₄-
C₁₀Branched cyclic alkenyl and mixtures thereof. Here, "replace"
The term means "a compatible moiety replacing a hydrogen atom". Non-limiting examples of substituents are
Roxy, nitrile, halogen, nitro, carboxyl (-CHO, -CO₂H,
-CO₂R ', -CONH₂, -CONHR ', -CONR'₂R 'is C₁-
C₁₂Linear or branched alkyl), amino, C₁-C₁₂Mono- and di
Alkylamino and mixtures thereof.

Acetals and Ketals Another class of preferred compounds useful as proaccords according to the present invention are acetal or ketals having the formula:

Embedded image The hydrolysis of an acetal or ketal releases one equivalent of an aldehyde or ketone and two equivalents of an alcohol according to the following scheme:

Embedded imageIn the above formula, R is C₁-C₂₀Linear alkyl, C₃-C₂₀Branched alkyl, C₃-
C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl, C₃-C₂₀Straight-chain arche
Nil, C₃-C₂₀Branched alkenyl, C₃-C₂₀Cyclic alkenyl, C₄-C_{2 0} Branched cyclic alkenyl, C₆-C₂₀A substituted or unsubstituted aryl (preferably,
The moiety that replaces the aryl unit is an alkyl moiety) and mixtures thereof.
You. R¹Is hydrogen, R, or, if the proaccord is a ketal,
R and R¹May together form a ring. R²And R³Is German
Stand up C₅-C₂₀Linear, branched or substituted alkyl, C₄-C₂₀Straight or branched
Or substituted alkenyl, C₅-C₂₀Substituted or unsubstituted cyclic alkyl, C₆-C_{2 0} Substituted or unsubstituted aryl, C₂-C₄₀Substituted or unsubstituted alkyleneoxy
, C₃-C₄₀Substituted or unsubstituted alkyleneoxyalkyl, C₆-C₄₀Replace
Or unsubstituted alkylenearyl, C₆-C₃₂Substituted or unsubstituted aryloxy
Si, C₆-C₄₀Substituted or unsubstituted alkyleneoxyaryl, C₆-C₄₀Oh
Selected from the group consisting of xylalkylenearyls and mixtures thereof. here
As used herein, the term "substituted" means "a compatible moiety that replaces a hydrogen atom." Substituent
Non-limiting examples include hydroxy, nitrilo, halogen, nitro, carboxyl (-CH
O, -CO₂H, -CO₂R ', -CONH₂, -CONHR ', -CONR' ₂ R 'is C₁-C₁₂Linear or branched alkyl), amino, C₁-C_{1 2} Mono- and dialkylamino and their mixtures.

Orthocarbonate Another class of preferred compounds useful as proaccords according to the present invention are orthocarbonates having the formula:

Embedded image The hydrolysis of the orthoester releases the fragrance ingredients according to the following scheme:

Embedded image Subsequent hydrolysis further releases two equivalents of one or more fragrance raw alcohols according to the following scheme:

Embedded imageThus, up to 4 equivalents per equivalent of delivered orthocarbonate
Supply the raw material alcohol; where R¹, R², R³And R⁴Is
Independently C₁-C₂₀Linear, branched or substituted alkyl, C₂-C₂₀Linear, branched
Or substituted alkenyl, C₃-C₂₀Substituted or unsubstituted cyclic alkyl, C₆-C ₂₀ Substituted or unsubstituted aryl, C₂-C₄₀Substituted or unsubstituted alkyleneoxy
Si, C₃-C₄₀Substituted or unsubstituted alkyleneoxyalkyl, C₆-C₄₀Place
Substituted or unsubstituted alkylenearyl, C₆-C₃₂Substituted or unsubstituted aryl
Kissi, C₆-C₄₀Substituted or unsubstituted alkyleneoxyaryl, C₆-C₄₀ Oxyalkylenearyl and mixtures thereof. Here, "replace"
The term means "a compatible moiety replacing a hydrogen atom". Non-limiting examples of substituents are
Roxy, nitrile, halogen, nitro, carboxyl (-CHO, -CO₂H,
-CO₂R ', -CONH₂, -CONHR ', -CONR'₂R 'is C₁-
C₁₂Linear or branched alkyl), amino, C₁-C₁₂Mono- and di
Alkylamino and mixtures thereof.

Non-limiting examples of fragrance raw material alcohols that can be suitably released by the proaccord of the present invention include 2,4-dimethyl-3-cyclohexene-1-methanol (floralol), 2,4-dimethylcyclohexanemethanol (dihydro Floralol), 5,6-dimethyl-1-methylethenylbicyclo [2.2.1] hept-5-ene-2-methanol (arbazole), 2,4,6-trimethyl-3-
Cyclohexene-1-methanol (isocyclogeraniol), 4- (1-methylethyl) cyclohexanemethanol (Mayor), α, 3,3-trimethyl-2-norboranemethanol, 1,1-dimethyl-1- (4- Methylcyclohex-3-enyl) methanol, 2-phenylethanol, 2-cyclohexylethanol, 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-cyclohexyl ethanol, 1- (4-isopropyl-cyclohexyl) ethanol, 1-phenylethanol, 1,1-dimethyl - 2-phenylethanol, 1,1-dimethyl-2- (4-methylphenyl) ethanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (hydrotropic alcohol), 2- (cyclododecyl) propane-1 -Ol (hydroxyamblane), 2,2-dimethyl-3- (3-methylphenyl) propan-1-ol (magentol), 2-methyl-3-phenylpropanol, 3-phenyl-2-propene- 1-ol (cinnamyl alcohol), 2-me -3-phenyl-2-propen-1-ol (methyl cinnamyl alcohol), alpha-n-pentyl-3-phenyl-2-propen-1-
All (α-amylcinnamyl alcohol), ethyl 3-hydroxy-3-phenylpropionate, 2- (4-methylphenyl) -2-propanol, 3- (4
-Methylcyclohex-3-ene) butanol, 2-methyl-4- (2,2,3
-Trimethyl-3-cyclopenten-1-yl) butanol, 2-ethyl-4-
(2,2,3-trimethylcyclopenta-3-enyl) -2-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-4- (2,2,3-trimethyl -3-cyclopenten-1-yl) -2-buten-1-ol, 3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4- Phenylbutan-2-ol, 4- (4-hydroxyphenyl) butan-2-one, 4- (4-hydroxy-3-methoxyphenyl) butan-2-one, 3-methylpentanol, 3-methyl-3 -Penten-1-ol, 2-methyl-4-phenylpentanol (Panprefluor)
3-methyl-5-phenylpentanol (phenoxanol), 2-methyl-
5-phenylpentanol, 2-methyl-5- (2,3-dimethyltricyclo [
2.2.1.0 ^(2,6) ] Hept-3-yl) -2-penten-1-ol (centalol), 4-methyl-1-phenyl-2-pentanol, (1-methylbicyclo [2.2.1] Hepten-2-yl) -2-methylpenta-1-en-3-
All, 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-isopropenyl-4-methyl-4-hexen-
1-ol (lavandulol), 2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-isopropenyl-1-cyclohexene (dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohexene Sa-6-
En-2-ol (carbenol), 6-methyl-3-isopropenylcyclohexane-1-ol, 1-methyl-4-isopropenylcyclohexane-3-ol, 4-isopropyl-1-methylcyclohexane-3-ol, 4-tert-
Butylcyclohexanol, 2-tert-butylcyclohexanol, 2-tert-
Butyl-4-methylcyclohexanol, 4-isopropylcyclohexanol, 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-isopropylcyclohexane-3-ol, 1,2-dimethyl-
3- (1-methylethyl) cyclohexane-1-ol, heptanol, 2,4
-Dimethylheptane-1-ol, 2,4-dimethyl-2,6-heptanedienol, 6,6-dimethyl-2-oxymethylbicyclo [3.1.1] hepta-2
-Ene (mirtenol), 4-methyl-2,4-heptadien-1-ol, 3
, 4,5,6,6-pentamethyl-2-heptanol, 3,6-dimethyl-3-
Vinyl-5-hepten-2-ol, 6,6-dimethyl-3-hydroxy-2-
Methylenebicyclo [3.1.1] heptane, 1,7,7-trimethylbicyclo [
2.2.1] heptane-2-ol, 2,6-dimethylheptane-2-ol,
2,6,6-trimethylbicyclo [1.3.3] heptane-2-ol, octanol, 2-octenol, 2-methyloctane-2-ol, 2-methyl-6
-Methylene-7-octen-2-ol (myrcenol), 7-methyloctane-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-dimethyloctane-1-ol (pelargol), 3,7-dimethyloctane-3-ol (tetrahydrolinalool), 2,4-octadiene- 1-all, 3,7
-Dimethyl-6-octen-3-ol, 2,6-dimethyl-7-octen-2
-Ol (dihydromyrcenol), 2,6-dimethyl-5,7-octadien-2-ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol,
-Methyloctane-3-ol, 2,6-dimethyloctane-2-ol, 2,
6-dimethyloctane-3-ol, 3,6-dimethyloctane-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-nonene-
1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6-nonadien-3-ol (ethyl linalool), decanol, 9-decenol, 2
-Benzyl-m-dioxa-5-ol, 2-decen-1-ol, 2,4-decadien-1-ol, 4-methyl-3-decene-5-ol, 3,7,9-trimethyl-1 , 6-Decadien-3-ol (isobutyl linalool), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-
Dodecene-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 (isophytol), benzyl alcohol, p-methoxybenzyl alcohol (anisyl alcohol), p-cymen-7-ol (cuminyl) Alcohol), 4-methylbenzyl alcohol, 3,4-methylenedioxybenzyl alcohol, methyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, n-
Pentyl salicylate, 2-phenylethyl salicylate, n-hexyl salicylate, 2-methyl-5-isopropylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4- (1-propenyl) phenol (isoeugenol), 4-allyl-
2,6-dimethoxyphenol, 4-tert-butylphenol, 2-ethoxy-
4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl-5-methylphenol (thymol), pentyl o-hydroxybenzoate, 2-
Ethyl hydroxybenzoate, 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-hydroxytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro-2-naphthol, 1,3 , 3-Trimethyl-2-norbornanol (fencol), 3a,
4,5,6,7,7a-Hexahydro-2,4-dimethyl-4,7-methano-1
H-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, β
-Caryophyllene alcohols and their mixtures.

Non-limiting examples of esters suitably released by the proaccord of the present invention include geranyl formate, citronellyl formate, phenylethyl formate, phenoxyethyl formate, trans-2-hexenyl formate, cis -3-hexenyl formate, cis-6-nonenyl formate, 9-decenyl formate,
3,5,5-trimethylhexyl formate, 3-methyl-5-phenylpentanyl formate, 6-methylheptane-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, dehydro-b-naphthyl formate, 4-isopropylcyclohexylmethyl formate, linalylform Mate, lavandulyl formate, citronellyl formate, a-terpinyl formate, nopyr formate, isobornyl formate,
Bornyl formate, isobornyl formate, guayl formate, 2-ter
t-butylcyclohexyl formate, 4-tert-butylcyclohexyl formate, decahydro-b-naphthyl formate, menthyl formate, p-menthanyl formate, neryl formate, cinnamyl formate, ethyl acetate, butyric acetate, acetic acid Isoamyl, 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-methylheptane-2-yl acetate, 4- (2,2,6- Trimethyl-2-cyclohexene-
1-yl) -3-buten-2-yl acetate, 3-methyl-5- (2,2,3
-Trimethyl-3-cyclopenten-1-yl) -4-penten-2-yl acetate, decahydro-b-naphthyl acetate, menthyl acetate, benzyl acetate,
4-isopropylcyclohexyleth-2-yl acetate, 6,8-dimethylnonane-2-yl acetate, 1-phenylethyl acetate, 4-isopropylcyclohexylmethyl acetate, linalyl acetate, lavandulyl acetate, citronellyl acetate, a-tel Pinyl acetate, nopyr acetate, isobornyl acetate, bornyl acetate, isobornyl acetate, guayyl acetate, 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, decahydro-b-naphthyl acetate, menthyl Acetate, p-menthanyl acetate, neryl acetate, cinnamyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, cis-3-hexyl Cenylbutyrate, cis-3-hexenylisobutyrate, ethyl isovalerate, 2-methylbutyrate, ethylhexanoate, 2-propenylhexanoate, ethylheptanoate, 2-propenylheptanoate, ethyloctanoate Ethyl 2-trans-4-cis-decadienoate, 2
-Methyl nononate, Benzyl propionate, Benzyl isovalerate, Phenylethylisobutyrate, Phenylethylisovalerate, a, a-Dimethylphenylethylbutyrate, Methyl benzoate, Hexyl benzoate, Benzyl benzoate, Phenylacetic acid Ethyl, geranyl phenylacetate, 1-phenylethylphenylacetate, methyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, geranyl propionate, geranyl isobutyrate, geranyl isovalerate, linalyl propionate, linalyl butyrate, linalyl butyrate , Linalyl isobutyrate, citronellyl propionate, citronellyl isobutyrate, citronellyl isovalate, citronellyl tiglate, 3-cyclohexyl allyl propionate, methyldimethyl Mud jasmonate, 2-hexyl-3-oxo-cyclopentanecarboxylic acid methyl and mixtures thereof.

Non-limiting examples of aldehydes released by the proaccord of the present invention include: phenylacetaldehyde, p-methylphenylacetaldehyde, p-isopropylphenylacetaldehyde, methylnonylacetaldehyde, phenylpropanal, 3- (4-t- (Butylphenyl) -2-methylpropanal (lilyal)
3- (4-t-butylphenyl) propanal (bourgeonal), 3- (4
-Methoxyphenyl) -2-methylpropanal (cantoxal), 3- (4
-Isopropylphenyl) -2-methylpropanal (cymar), 3- (3
, 4-Methylenedioxyphenyl) -2-methylpropanal (Helional)
3,3- (4-ethylphenyl) -2,2-dimethylpropanal (floralozone), phenylbutanal, 3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-3-hexenal, 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-
Octadiene-1-al, 3,7-dimethyl-1,6-octadiene-3-al, 3,7-dimethyl-6-octenal (citronellal), 3,7-dimethyl-7-hydroxyoctane-1-al ( Hydroxycitronellal), nonanal, 6-nonenal, 2,4-nonadienal, 2,6-nonadienal, decanal, 2-methyldecanal, 4-decenal, 9-decenal, 2,
4-Decadienal, undecanal, 2-methyldecanal, 2-methylundecanal, 2,6,10-trimethyl-9-undecenal (Adoxal)
, Undeca-10-enyl aldehyde, undeca-8-enanal, dodecanal, tridecanal, tetradecanal, anisaldehyde, buldinonal,
Cinnamic aldehyde, a-amylcinnamaldehyde, a-hexylcinnamaldehyde, methoxycinnamaldehyde, isocyclocitral, citronellyloxyacetaldehyde, cortexaldehyde, cinnamic aldehyde, cyclamenaldehyde, florhydral, heliotropin, hydrotropic aldehyde, vanillin , Ethyl vanillin, benzaldehyde, p-methylbenzaldehyde, 3,4-dimethoxybenzaldehyde, 3- and 4- (4-hydroxy-4
-Methylpentyl) -3-cyclohexene-1-carboxaldehyde (liral) 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (tripral), 1-methyl-3- (4-methylpentyl) -3 -Cyclohexenecarboxaldehyde (vernaldehyde), p-methylphenoxyacetaldehyde (
Xi aldehydes) and mixtures thereof.

Non-limiting examples of ketones released by the proaccords of the present invention include: a-damascon, b-damascon, d-damascon, b-damassenone, muscone, 6,7-
Dihydro-1,1,2,3,3-pentamethyl-4 (5H) -indanone (cashmelan), cis-jasmon, dihydrojasmon, a-yonone, b-yonone, dihydro-b-yonone, g-methylyonone, a-isomethylyonone, 4- (
3,4-methylenedioxyphenyl) butan-2-one, 4- (4-hydroxyphenyl) butan-2-one, methyl b-naphthyl ketone, methylseryl ketone, 6-acetyl-1,1,2,2 4,4,7-hexamethyltetralin (tonalide), 1-carboxyl, 5-cyclohexadecene-1-one, acetophenone, decatone, 2- [2- (4-methyl-3-cyclohexenyl-1-yl) propyl Cyclopentan-2-one, 2-sec-butylcyclohexanone, b-dihydroyonone, allylyonone, a-iron, a-cetone, a-irison, acetoanisole, geranylacetone, 1- (2-methyl-5-isopropyl -2-cyclohexenyl) -1-propanone, acetyldiisoamylene, methylcyclocitron, 4-t-pentylci Rohekisanon, p-t- butyl cyclohexanone, o-
t-butylcyclohexanone, ethyl amyl ketone, ethyl pentyl ketone, menthone, methyl-7,3-dihydro-2H-1,5-benzodioxepin-3-
There are ON, Feng Chong and their mixtures.

Fragrance Release Half-Life Tertiary alcohol releasing pro-perfumes and other pro-accords useful in the fragrance delivery system of the present invention hydrolyze upon contact with human skin to release fragrance ingredients. However, in order to meet the needs of the trader, the proaccord must release the perfume ingredients at a rate useful for maintaining fragrance levels.

The operation of measuring the release rate of proaccord in human skin is cumbersome and has many variations. Thus, it has been surprisingly discovered that the proaccord can be evaluated without contact with human skin, but the method directly demonstrates its suitability for use as a tertiary alcohol releasing proaccord. This procedure can be used with any professional fragrance suitable for use in the fragrance delivery system of the present invention.

[0037] taken for the purposes of the present invention, _NaH 2 PO ₄ buffer for 12 hours when measured at pH2.5 or less, and _NaH 2 PO ₄ 0 when measured in buffer pH5.3
. Proaccords having a "fragrance release half-life" of 1 hour or more are suitable as tertiary alcohol releasing orthoesters or proaccords useful in the fragrance delivery systems of the present invention. "Fragrance release half-life" is defined as follows. Proaccord delivers a fragrance ingredient or a corresponding mixture of fragrance accords according to the following formula: Proaccord → Accord In the above, the released accord may in some cases consist of a single fragrance ingredient, Preferably, it is a binary accord or a multiple fragrance raw material accord. The rate at which the accord is released is defined as: rate = k [pro accord] which can be further expressed as:-d [pro accord] / dt = k [pro accord] where k is the release rate. Where [proacord] is the concentration of proaccord. For the purposes of the present invention, the “fragrance release half-life” t _1/2 is related to the release rate constant by the formula: t _1/2 = 0.693 / k This relationship is for the purposes of the present invention to be “fragrance release half-life”. Used to determine the release half-life "(FRHL).

[0038] Due in part to the hydrophobicity of the proaccord, 90/10 dioxane / phosphate buffered water
T in the mixture_1/2And measurements of k need to be made. Suitability of ProAcord for use in fragrance delivery systems at pH 2.5
An example of the operation used to check is as follows. 85% phosphate buffered water
Acid (H₃PO₄3.95 ml) and sodium dihydrogen phosphate (NaH₂PO ₄ ) Prepare by mixing 24 g with 1 L of water. The pH of this solution is about 2.5
. Then mix 10 ml of phosphate buffer with 90 ml of dioxane, and mix
Add low fragrance. The hydrolysis kinetics were then determined by conventional HPLC at 30 ° C.
Monitor.

The orthoester bis (n-pentyl) dihydromyrcenyl orthoformate has a fragrance release half-life of about 1.3 hours as measured at the above conditions at pH 5.3, and therefore a tertiary alcohol dihydro An orthoester suitable for delivering myrcenol and for use in the fragrance delivery system of the present invention.

Example 1 Bis (phenylethyl) mono (dihydromyrcenol) orthoformate Tris (phenylethyl) orthoformate (1 equivalent), dihydromyrcenol (3 equivalents) and an acid catalyst [eg 2,4 , 6-Trimethylbenzoic acid, 2,6
-Dichlorobenzoic acid or tetrabutylammonium hydrogensulfate, 1-2 mol%] under high vacuum (<0.25 mmHg) at 40 ° C. for 5 days. The reaction mixture is then diluted with twice the volume of ether, washed with saturated sodium carbonate solution, dried,
Evaporate and flash chromatograph to obtain analytically pure bis (phenylethyl) mono (dihydromyrcenol) orthoformate.

The following are examples of the fragrance delivery system of the present invention. Example 2 Ingredients Weight% Tertiary alcohol releasing proaccord component Proaccord ¹ 5.1 Potassium carbonate ² Ethanol ³ 12.4 Other proaccord Tris (citronellyl) orthoformate 8.1 Citronellyloxyacetaldehyde bis (citronellyl) 4 1.7 Acetal fragrance raw material components Phenylacetaldehyde 0.7 Base notes and fragrance raw materials ⁴ 61.4 Additives ⁵ 2.1 Ethanol ⁶ balance 1. 2. Bis (phenylethyl) mono (dihydromyrcenol) orthoformate 2.1 mmol Potassium carbonate Amount sufficient to provide pre-alkali 3. Ethanol carrier contains less than 1% water. 4. Fragrance raw material base, middle and top notes containing polyethylene glycol as carrier and absolute ethanol as diluent 5. Diethyl phthalate as a volatile retention agent Absolute ethanol

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] December 9, 1999 (1999.12.29)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image[Wherein X is oxygen, sulfur, nitrogen and mixtures thereof; each R¹, R ² And R³Is independently substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C ₂₀ Branched alkyl, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl
, C₃-C₂₀Straight chain alkenyl, C₄-C₂₀Branched alkenyl, C₃-C₂₀ring
Formula alkenyl, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆ -C₂₀Alkylenearyl, C₆-C₂₀Alkyleneoxyalkyl, C₆-
C₂₀Alkyleneoxyaryl and mixtures thereof; or any
Or two R¹, R²Or R³Together form a ring having 5 to 8 atoms
(The ring may have one or more C₁-C₂₂Alkyl, C₁-C₂₂Arche
Nil, C₆-C₁₂Aryl, C₆-C₂₂Alkylenearyl unit and it
R is hydrogen, substituted or unsubstituted C. ₁ -C₂₀Linear alkyl, C₃-C₂₀Branched alkyl, C₃-C₂₀Cyclic alk
Le, C₄-C₂₀Branched cyclic alkyl, C₃-C₂₀Straight chain alkenyl, C₃-C_{2 0} Branched alkenyl, C₃-C₂₀Cyclic alkenyl, C₄-C₂₀Branched cyclic arche
Nil, C₆-C₂₀Aryl, C₆-C₂₀Alkylenearyl, C₆-C₂₀ Alkyleneoxyalkyl, C₆-C₂₀Alkyleneoxyaryl and it
Or a mixture of any of R¹, R²Or R³Is with R
To form a ring having 5 to 8 atoms (the ring may have one or more C atoms).₁-C ₂₂ Alkyl, C₁-C₂₂Alkenyl, C₆-C₁₂Aryl, C₆-C₂₂ Optionally further substituted by alkylenearyl units and mixtures thereof
); Provided that at least one R¹, R²Or R³The unit is tertiary fragrance raw material
Derived from alcohol; the proaccord described above has a fragrance release half-life of N
aH₂PO₄0.1 hours or more at pH 5.3 when measured in buffer and
It has a fragrance release half-life of less than 12 hours at pH 2.5].

Embedded image(In the above formula, at least one -OR¹, -OR²And -OR³Alkoxy unit
Is derived from a fragrance material that is a tertiary alcohol; R is independently hydrogen,
Substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C₂₀Branched alkyl, C₃ -C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl, C₃-C₂₀Linear al
Kenil, C₄-C₂₀Branched alkenyl, C₆-C₂₀Cyclic alkenyl, C₆-C ₂₀ Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆-C₂₀Alkylene ant
, C₆-C₂₀Alkyleneoxyalkyl, C₆-C₂₀Alkyleneoxy
Aryl and mixtures thereof; provided that the above-mentioned pro-accord is
The half-life of release of NaH₂PO₄0 at pH 5.3 when measured in buffer.
. Has a fragrance release half-life of 1 hour or more and 12 hours or less at pH 2.5
And b) a fragrance delivery system comprising the remaining one or more proaccords.

Embedded image(In the above formula, each R¹, R²And R³Is independently substituted or unsubstituted C₁-C ₂₀ Linear alkyl, C₃-C₂₀Branched alkyl, C₃-C₂₀Cyclic alkyl, C ₄ -C₂₀Branched cyclic alkyl, C₃-C₂₀Straight chain alkenyl, C₄-C₂₀Branch
Alkenyl, C₃-C₂₀Cyclic alkenyl, C₄-C₂₀Branched cyclic alkenyl,
C₆-C₂₀Aryl, C₆-C₂₀Alkylenearyl, C₆-C₂₀Archi
Lenoxyalkyl, C₆-C₂₀Alkyleneoxyaryl and mixtures thereof
R is hydrogen, substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C ₂₀ Branched alkyl, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl
, C₃-C₂₀Straight chain alkenyl, C₃-C₂₀Branched alkenyl, C₃-C₂₀ring
Formula alkenyl, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆ -C₂₀Alkylenearyl, C₆-C₂₀Alkyleneoxyalkyl, C₆-
C₂₀Alkyleneoxyaryl and mixtures thereof).
Composition.

──────────────────────────────────────────────────続 き Continuation of the front page (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Kenneth, Nathan, Price United States Ohio, Wyoming, Compton, Road, 265 ( 72) Inventor Ron, Montgomery, Gray Florentine, Promontory, Drive, Kentucky, USA, 1806 (72) Inventor Scott, William, Wight, Ohio, United States of America, Cincinnati, Elkwood, Drive, 12175 F-term (reference) 4H006 AA01 AB14 GP01 GP02 GP50 4H059 BA15 BA17 BA42 BA43 BA64 BA65 BB02 BB03 BB13 BB14 DA09 EA31

Claims (10)

[Claims] 1. A proaccord having the following formula:[Wherein X is oxygen, sulfur, nitrogen and mixtures thereof; each R¹, R ² And R³Is independently substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C ₂₀ Branched alkyl, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl
, C₃-C₂₀Straight chain alkenyl, C₄-C₂₀Branched alkenyl, C₃-C₂₀ring
Formula alkenyl, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆ -C₂₀Alkylenearyl, C₆-C₂₀Alkyleneoxyalkyl, C₆-
C₂₀Alkyleneoxyaryl and mixtures thereof; or any
Or two R¹, R²Or R³Together form a ring having 5 to 8 atoms
(The ring may have one or more C₁-C₂₂Alkyl, C₁-C₂₂Arche
Nil, C₆-C₁₂Aryl, C₆-C₂₂Alkylenearyl unit and it
R is hydrogen, substituted or unsubstituted C. ₁ -C₂₀Linear alkyl, C₃-C₂₀Branched alkyl, C₃-C₂₀Cyclic alk
Le, C₄-C₂₀Branched cyclic alkyl, C₃-C₂₀Straight chain alkenyl, C₃-C_{2 0} Branched alkenyl, C₃-C₂₀Cyclic alkenyl, C₄-C₂₀Branched cyclic arche
Nil, C₆-C₂₀Aryl, C₆-C₂₀Alkylenearyl, C₆-C₂₀ Alkyleneoxyalkyl, C₆-C₂₀Alkyleneoxyaryl and it
Or a mixture of any of R¹, R²Or R³Is with R
To form a ring having 5 to 8 atoms (the ring may have one or more C atoms).₁-C ₂₂ Alkyl, C₁-C₂₂Alkenyl, C₆-C₁₂Aryl, C₆-C₂₂ Optionally further substituted by alkylenearyl units and mixtures thereof
); Provided that at least one R¹, R²Or R³The unit is tertiary fragrance raw material
Derived from alcohol; the proaccord described above has a fragrance release half-life of N
aH₂PO₄0.1 hours or more at pH 5.3 when measured in buffer and
It has a fragrance release half-life of less than 12 hours at pH 2.5]. 2. Each R ¹ , R ² and R ³ is independently substituted or unsubstituted C ₁ -C ₁₂ straight chain alkyl, C ₃ -C ₁₂ branched alkyl, C ₃ -C ₁₂ cyclic alkyl, C ₄ -C ₁₂ branched cyclic alkyl, C ₃ -C ₁₂ linear alkenyl, C ₄ -C ₁₂ branched alkenyl, C ₃ -C ₁₂ cyclic alkenyl, C ₄ -C ₁₂ branched cyclic alkenyl and mixtures thereof. The compound according to claim 1, wherein: 3. The compound according to claim ¹ , wherein at least one of R ¹ , R ² or R ³ is linalyl, tetrahydrolinalyl, ethyllinalyl, dihydromyrcenyl and mixtures thereof. 4. The proaccord is linalool, tetrahydrolinalool, ethyl linalool,
The compound according to any one of claims 1 to 3, which is capable of releasing a tertiary alcohol selected from the group consisting of dihydromyrcenol and mixtures thereof. 5. A) at least one proaccord having the formula:(In the above formula, at least one -OR¹, -OR²And -OR³Alkoxy unit
Is derived from a fragrance material that is a tertiary alcohol; R is independently hydrogen,
Substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C₂₀Branched alkyl, C₃ -C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl, C₃-C₂₀Linear al
Kenil, C₄-C₂₀Branched alkenyl, C₆-C₂₀Cyclic alkenyl, C₆-C ₂₀ Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆-C₂₀Alkylene ant
, C₆-C₂₀Alkyleneoxyalkyl, C₆-C₂₀Alkyleneoxy
Aryl and mixtures thereof; provided that the above-mentioned pro-accord is
The half-life of release of NaH₂PO₄0 at pH 5.3 when measured in buffer.
. Has a fragrance release half-life of 1 hour or more and 12 hours or less at pH 2.5
And b) a fragrance delivery system comprising the remaining one or more proaccords. 6. The proaccord of (b) comprises: a) formed from at least one fragrance raw material having a molecular weight of at least 100 g / mol; b) having a molecular weight of at least 300 g / mol; Has a molecular weight at least twice as large as the lowest molecular weight fragrance raw material that constitutes the proaccord; and d) the fragrance release half-life when measured in NaH ₂ PO ₄ buffer,
6. The composition of claim 5, having a fragrance release half-life of greater than or equal to 0.1 hours at pH 5.3 and less than or equal to 12 hours at pH 2.5. 7. a) 0.1 to 99.9% by weight of at least one proaccord releasing a tertiary alcohol fragrance raw material, provided that the proaccord has a fragrance release half-life of NaH ₂ PO ₄ buffer. Has a fragrance release half-life of not less than 0.1 hours at pH 5.3 and not more than 12 hours at pH 2.5), b) one or more fragrance raw materials 0.1-99. Perfume or fine fragrance for application to human skin, having a long fragrance life, comprising: 0.9% by weight; and c) balance carrier and auxiliary ingredients. 8. The at least one proaccord which releases a tertiary alcohol fragrance raw material,
An orthoester proaccord having the formula:(In the above formula, each R¹, R²And R³Is independently substituted or unsubstituted C₁-C ₂₀ Linear alkyl, C₃-C₂₀Branched alkyl, C₃-C₂₀Cyclic alkyl, C ₄ -C₂₀Branched cyclic alkyl, C₃-C₂₀Straight chain alkenyl, C₄-C₂₀Branch
Alkenyl, C₃-C₂₀Cyclic alkenyl, C₄-C₂₀Branched cyclic alkenyl,
C₆-C₂₀Aryl, C₆-C₂₀Alkylenearyl, C₆-C₂₀Archi
Lenoxyalkyl, C₆-C₂₀Alkyleneoxyaryl and mixtures thereof
R is hydrogen, substituted or unsubstituted C₁-C₂₀Linear alkyl, C₃-C ₂₀ Branched alkyl, C₃-C₂₀Cyclic alkyl, C₄-C₂₀Branched cyclic alkyl
, C₃-C₂₀Straight chain alkenyl, C₃-C₂₀Branched alkenyl, C₃-C₂₀ring
Formula alkenyl, C₄-C₂₀Branched cyclic alkenyl, C₆-C₂₀Aryl, C₆ -C₂₀Alkylenearyl, C₆-C₂₀Alkyleneoxyalkyl, C₆-
C₂₀Alkyleneoxyaryl and mixtures thereof).
Composition. 9. The proaccord of (a) is capable of releasing a tertiary alcohol selected from the group consisting of linalool, tetrahydrolinalool, ethyl linalool, dihydromyrcenol and mixtures thereof. 9. The composition according to 8. 10. The composition according to claim 7, further comprising a reserve alkali in an amount corresponding to at least 0.001 mol NaOH.