CN1298378A - Tertiary alcohol fragrance raw material delivery system - Google Patents

Abstract

This invention relates to pre-fragrances suitable for providing tert-ol flavorings to human skin. The invention also relates to systems for providing flavor in fragrance and flavor compositions, said systems comprising at least one pre-fragrance providing a tert-ol flavoring and a balanced proportion of other pre-fragrance agents.

Description

Tertiary mellow raw material feeding system

Field of Invention

The present invention relates to proaccords capable of releasing tertiary aroma raw materials, especially linalool, tetrahydrolinalool, ethyl linalool and dihydromyrcenol. The present invention also relates to a fragrance providing system comprising said pro-accord, thereby providing a method of providing a tertiary aroma raw material to a certain site, preferably human skin. The present invention also relates to essences and fragrances comprising a fragrance imparting system releasing said tertiary alcohol. The fragrance-providing systems described herein also provide long-lasting fragrance.

Background of the Invention

Since ancient times, people have applied scents and aromas to the skin. Originally, these aesthetically pleasing substances were usually in crude form isolated from natural sources, especially the bark, roots, leaves and fruits of some indigenous plants, such as resins, gums or essential oils. These resins, gums, and essential oils are applied directly to the body or diluted with water or other solvents, including, in some cases, wine. With the advent of modern chemistry, the components responsible for the odorant properties of these resins, gums and essential oils were isolated and then characterized. Today's fragrances include artificially combined fragrances to obtain new fragrance compositions with defined "characteristics".

Many of today's fragrances are no longer obtained from natural raw materials, but are synthesized by today's chemical methods, and they are high-purity fragrance raw materials (FRM). These FRMs are commonly formulated into perfumes, colognes, toilet waters, after-shave lotions and other personal fragrance compositions. Those skilled in the art of preparing these perfume-containing compositions classify perfumes into three categories according to their relative volatility: top notes, middle notes, and base notes.

A disadvantage of general fragrances and fragrances is that once the fragrance or fragrance is applied to the human skin, the original fragrance balance in the fragrance raw materials begins to change. This loss of fragrance balance is partly due to the differential evaporation of volatile top notes and the adsorption of other components to the skin surface. Users of flavors and fragrances have attempted to correct this problem in a number of ways. One way is to start "loading" a certain amount of fragrance and depending on the natural rate of evaporation, after a few hours, when the desired effect is achieved, reduce the fragrance to the appropriate level. Another method that is commonly used is to continue replenishing the fragrance by delivering small amounts of fragrance to the skin for a short period of time. None of these approaches is sufficient to overcome the reduction in volume of top and middle notes over time. In fact, due to the low volatility, the base notes that remain after a long period of time start to aggregate with the respective "newer" fragrances, and after a while, the base notes start to overlay the other notes and disrupt the original fragrance balance.

Recently, it has been found that some fragrance raw materials can be provided to human skin by pro-perfume. These pro-perfume compounds include acid-labile acetals, ketals, and orthoesters that decompose upon contact with human skin surfaces at acidic pHs to release fragrance raw materials. In general, acetals release aldehydes, ketals release ketones, and orthoesters release alcohols. However, formulators are limited in their use by the fact that some pro-perfumes, although acid labile, have a fragrance release half-life (rate of hydrolysis) that exceeds their usage time in a fragrance or fragrance composition. Additionally, the prior art does not disclose pro-perfumes suitable for releasing tertiary aroma raw materials.

It has now been surprisingly found that certain ortho-acid pro-fragrances provide one or more tertiary aroma raw materials at a rate which provides a suitable means of delivering these desired fragrance raw materials to human skin. In addition, the pro-accords described herein can variably provide tertiary alcohols at a rate preferred by the formulator.

Summary of Invention

The present invention fulfills said need in that it was surprisingly found that certain orthoesters comprising at least one tertiary alcohol aroma raw material can be prepared which release said tertiary alcohol at a rate adjusted to meet the specific requirements of the formulator. For example, the extended release of a fragrance ingredient provides formulators with a means of extending an existing blend of fragrance ingredients or an initial fragrance profile. By using the pro-accords of the present invention, formulators can now control the release of tertiary aroma raw materials. This controlled release is a means of maintaining the tertiary alcohol perfume durably on human skin.

其中各-OR¹、-OR²和-OR³部分是衍生自醇的烷氧基单元，使得各R¹、R²和R³独立地为取代或未取代的C₁-C₂₂直链烷基、C₃-C₂₀支链烷基、C₃-C₂₀环烷基、C₄-C₂₀支链环烷基、C₃-C₂₀直链烯基、C₄-C₂₀支链烯基、C₃-C₂₀环状链烯基、C₄-C₂₀支链环状链烯基、C₆-C₂₀芳基、C₆-C₂₀亚烷基芳基、C₆-C₂₀亚烷基氧基烷基、C₆-C₂₀亚烷基氧基芳基和其混合物；或任何两个R¹、R²或R³可结合形成具有5-8个原子的环，所说的环还任选地被一个或多个C₁-C₂₂烷基、C₁-C₂₂链烯基、C₆-C₁₂芳基、C₆-C₂₂亚烷基芳基单元和其混合物取代；R是氢、取代或未取代的C₁-C₂₀直链烷基、C₃-C₂₀支链烷基、C₃-C₂₀环烷基、C₃-C₂₀支链环烷基、C₃-C₂₀直链烯基、C₄-C₂₀支链烯基、C₃-C₂₀环状链烯基、C₄-C₂₀支链环状链烯基、C₆-C₂₀芳基、C₆-C₂₀亚烷基芳基、C₆-C₂₀亚烷基氧基烷基、C₆-C₂₀亚烷基氧基芳基和其混合物；或任何R¹、R²或R³可与R结合形成具有5-8个原子的环，所说的环还任选地被一个或多个C₁-C₂₂烷基、C₁-C₂₂链烯基、C₆-C₁₂芳基、C₆-C₂₂亚烷基芳基单元和其混合物取代；条件是至少一个R¹、R²或R³单元衍生自叔醇香原料，所说的前谐香剂在pH5.3下具有香味释放半衰期大于或等于0.1小时和在pH2.5下低于或等于12小时，所说的香味释放半衰期是在所说pH的NaH₂PO₄缓冲液中测定的。A first aspect of the present invention relates to pro-accords having the formula:

wherein each -OR ¹ , -OR ² and -OR ³ moiety is an alkoxy unit derived from an alcohol such that each R ¹ , R ² and R ³ is independently a substituted or unsubstituted C ₁ -C ₂₂ linear alkane C ₃ -C ₂₀ branched chain alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ branched cycloalkyl, C ₃ -C ₂₀ straight chain alkenyl, C ₄ -C ₂₀ branched alkenyl C ₃ -C ₂₀ cyclic alkenyl, C ₄ -C ₂₀ branched cyclic alkenyl _, C ₆ -C ₂₀ aryl, C 6 -C ₂₀ alkylene aryl, C ₆ -C ₂₀ Alkyleneoxyalkyl, C ₆ -C ₂₀ alkyleneoxyaryl and mixtures thereof; or any two of R ¹ , R ² or R ³ may combine to form a ring having 5-8 atoms, said The ring of is also optionally surrounded by one or more C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ alkenyl, C ₆ -C ₁₂ aryl, C ₆ -C ₂₂ alkylene aryl units and mixtures thereof Substitution; R is hydrogen, substituted or unsubstituted C ₁ -C ₂₀ straight chain alkyl, C ₃ -C ₂₀ branched chain alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ branched chain cycloalkyl , C ₃ -C ₂₀ straight chain alkenyl, C ₄ -C ₂₀ branched alkenyl, C ₃ -C ₂₀ cyclic alkenyl, C ₄ -C ₂₀ branched cyclic alkenyl, C ₆ -C ₂₀ Aryl, C ₆ -C ₂₀ alkylene aryl, C ₆ -C ₂₀ alkylene oxyalkyl, C ₆ -C ₂₀ alkylene oxyaryl and mixtures thereof; or any of R ¹ , R ² Or R ³ can be combined with R to form a ring having 5-8 atoms, said ring is also optionally surrounded by one or more C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ alkenyl, C ₆ - C ₁₂ aryl, C ₆ -C ₂₂ alkylene aryl units and mixtures thereof are substituted; provided that at least one R ¹ , R ² or R ³ unit is derived from a tertiary alcohol fragrance raw material, said pro-accord is at pH 5. 3 have a fragrance release half-life greater than or equal to 0.1 hour and less than or equal to 12 hours at pH 2.5, said fragrance release half-life being measured in NaH ₂ PO ₄ buffer at said pH.

The present invention also relates to a fragrance providing system comprising at least one pro-accord as described herein capable of suitably releasing tertiary aroma raw materials and one or more pro-accords, especially orthoesters, ketals, Combinations of acetals, orthocarbonates, preferably having a fragrance release half-life greater than or equal to 0.1 hour at pH 5.3 and less than or equal to 12 hours at pH 2.5, said fragrance release half-life being at said pH measured in NaH ₂ PO ₄ buffer.

The present invention also relates to fragrances and essences comprising, in addition to the fragrance-providing systems described herein, other fragrance raw materials and co-components. 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, proportions and ratios herein are by weight unless otherwise specified. All temperatures are in degrees Celsius (° C.) unless otherwise stated. All documents cited are, in relevant part, incorporated herein by reference.

Detailed description of the invention

The present invention relates to new compositions of matter, namely orthoesters capable of releasing tertiary alcohol aroma raw materials. As described herein, the rate of release of the tertiary alcohol, hereinafter referred to as the "half-life of fragrance release", can be manipulated to release the tertiary alcohol in a manner consistent with the particular requirements of the fragrance-containing composition.

A compound releasing a tertiary aroma raw material is referred to in this specification as a pro-perfume, a pro-perfume or preferably a pro-accord, and these terms are used jointly and/or interchangeably to denote a compound capable of releasing at least one tertiary aroma raw material. orthoester.

For the purposes of the present invention, the terms "perfume" and "perfume" are essentially synonymous and are used together or interchangeably in this specification, as the terms are used to refer to a more concentrated form of a perfume-containing composition. Aspects of the present invention apply to "fragrance", so it applies equally to "fragrance", and vice versa. Typically, examples of cologne, toilet water, aftershave and other fragrance-containing products are fragrances or essences in relatively large dilutions, usually with a volatile carrier such as ethanol.

Those skilled in the art of flavors and fragrances call fragrance mixtures "accords." The term "accord" as used herein is defined as "a mixture of two or more 'fragrance materials' which have been artificially combined to produce a pleasant aroma, fragrance, aroma or fragrance character". The fragrance providing system of the present invention comprises at least one pro-accord capable of releasing at least one tertiary alcohol and one or more other "pro-accords" preferably capable of releasing a mixture of fragrance raw materials or "accords". For the purposes of the present invention, "perfume raw materials" are defined herein as compounds, preferably having a molecular weight of at least 100 g/mol, which are used alone or in combination with other "perfume raw materials" for producing aroma, aroma or fragrance. However, as the term "fragrance raw material" relates to pro-accords which release tertiary alcohols, the molecular weight of the auxiliary alcohols which combine with tertiary alcohols to form pro-accords may be below 100 g/mol. For example, as described further below, low molecular weight alcohols, especially ethanol, can be used as the alcohol component of the orthoesters in order to produce the desired fragrance release half-life.

Generally, the "perfume raw materials" constituting the non-tertiary alcohol releasing pro-accords of the presently provided fragrance systems include, inter alia, alcohols, ketones, aldehydes, esters, ethers, nitriles and olefins such as terpenes. Lists of common "perfume raw materials" can be found in various references, such as "Perfume and Flavor Chemicals", Volumes I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfume: Technology, Science and Technology" (Pefumes: Art, Science and Technology); Muller, P.M. and Lamparsky, D., Blackie Academic and Professional (1994), both of which are incorporated herein by reference.

For the purposes of the present invention, a substituted or unsubstituted alkyleneoxy unit is defined as a segment having the formula: Wherein ^R is hydrogen, methyl and mixtures thereof; ^R is hydrogen, methyl, ethyl and mixtures thereof; subscript x is 1 to about 20.

其中R⁵是氢、C₁-C₁₈烷基和其混合物；R⁶是氢、甲基、乙基和它们的混合物；下标x是1-约20，下标y是2-约18。For the purposes of the present invention, a substituted or unsubstituted alkyleneoxyalkyl unit is defined as a segment having the formula:

wherein R ⁵ is hydrogen, C ₁ -C ₁₈ alkyl and mixtures thereof; R ⁶ is hydrogen, methyl, ethyl and mixtures thereof; subscript x is 1 to about 20, and subscript y is 2 to about 18.

For the purposes of the present invention, substituted or unsubstituted alkylene aryl units are defined as segmental moieties having the formula: Wherein R ⁵ and R ⁶ are each independently hydrogen, hydroxyl, nitrilo, halogen, nitro, carboxyl (-CHO; -CO ₂ H, -CO ₂ R'; -CONH ₂ ; -CONHR';-CONR' ₂ , wherein R' is C ₁ -C ₁₂ linear or branched chain alkyl), amino, alkylamino and mixtures thereof, and p is 1 to about 14.

其中R⁵和R⁶各自独立地为氢、羟基、次氮基、卤素、硝基、羧基(-CHO；-CO₂H,-CO₂R’；-CONH₂；-CONHR’；-CONR’₂；其中R’是C₁-C₁₂直链或支链烷基)、氨基、烷基氨基和它们的混合物，q是1-约14。释放叔醇的前谐香剂For the purposes of the present invention, substituted or unsubstituted alkyleneoxyaryl units are defined as segmental moieties having the formula:

Wherein R ⁵ and R ⁶ are each independently hydrogen, hydroxyl, nitrilo, halogen, nitro, carboxyl (-CHO; -CO ₂ H, -CO ₂ R'; -CONH ₂ ; -CONHR';-CONR'₂; wherein R' is C ₁ -C ₁₂ linear or branched chain alkyl), amino, alkylamino and mixtures thereof, and q is 1 to about 14. pro-accords releasing tertiary alcohols

The pro-accord of the present invention that releases at least one tertiary mellow raw material has the formula: Wherein the ortho ester is hydrolyzed according to the following diagram to release the fragrance raw material components: Two equivalents of alcohol and one equivalent of ester are thereby liberated.

Each of R ¹ , R ² and R ³ is independently substituted or unsubstituted C ₁ -C ₂₀ straight chain alkyl, C ₃ -C ₂₀ branched chain alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ branched cyclic alkenyl, C ₃ -C ₂₀ straight chain alkenyl, C ₄ -C ₂₀ branched alkenyl, C ₃ -C ₂₀ cyclic alkenyl, C ₄ -C ₂₀ branched cyclic alkenyl , C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ alkylene aryl, C ₆ -C ₂₀ alkyleneoxyalkyl, C ₆ -C ₂₀ alkylene oxyaryl and mixtures thereof; preferably Substituted or unsubstituted C ₁ -C ₁₀ straight chain alkyl, C ₃ -C ₁₀ branched chain alkyl, C ₃ -C ₁₀ cycloalkyl, C ₄ -C ₁₀ branched chain cycloalkyl, C ₃ -C ₁₀ Straight chain alkenyl, C ₄ -C ₁₀ branched alkenyl, C ₃ -C ₁₀ cyclic alkenyl, C ₄ -C ₁₀ branched cyclic alkenyl and mixtures thereof; or any two of R ¹ , R ² or R ³ can be combined to form a ring with 5-8 atoms, said ring is also optionally replaced by one or more C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ alkenyl, C ₆ -C Substitution by ₁₂ aryl, _C6 - _C22 alkylene aryl units and mixtures thereof; with the proviso that at least one of the ^R1 , ^R2 and ^R3 units is derived from a tertiary alcohol.

Non-limiting examples of tertiary aroma raw materials include α,α-dimethylphenethyl alcohol (dimethylbenzylmethanol), α,α-4-trimethyl-3-cyclohexene-1-methanol (α-terpene pinol), a,a-4-trimethylphenethyl alcohol (p-methyldimethylbenzylmethanol), 2-(4-methylphenyl)-2-propanol (carvacrol), 2- Methyl-4-phenyl-2-butanol (phenylethyldimethylmethanol), 3-methyl-1-phenyl-3-pentanol (phenylethylmethylethylmethanol), 1 ,2-Dimethyl-3-(1-methylvinyl)cyclopentanol (plinol), 1,2-dimethyl-3-(1-methylvinyl)cyclohexanol, 1-methyl -4-isopropylcyclohexan-8-ol (dihydroterpineol), 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde (Lyral; Kovanol), 2,6-Dimethylheptan-2-ol (Dimetol, Freesiol, Lolitol), 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol (cis-2-pinanol), 2 ,6,6-Trimethylbicyclo[1.3.3]heptan-2-ol (cis and trans-2-pinanol), 2,6-Dimethyl-2-octanol (tetrahydromyrcenol) , 2-methyl-2-octanol (methyl octanol), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), 2,6-dimethyl-7 -Octen-2-ol (lymolene), 2,6-dimethyl-3,5-octadien-2-ol (Muguol), 2-methyl-6-methylene-7-octene- 2-alcohol (myrcenol), 2,6-dimethyl-5,7-octadien-2-ol (ocimenol), 3,6-dimethyl-3-octanol, 3-methyl- 3-octanol (Aprol 160), 3,7-dimethyl-3-octanol and 2,6-dimethyl-2-octanol (tetrahydromuguol; tetralol; linacsol), 3,7-dimethyl -6-octen-3-ol (dihydrolinalool), 3,7-dimethyl-3-octanol (tetrahydrolinalool), 3-methyl-1-octen-3-ol (Aprol 160), 7-hydroxy-3,7-dimethyloctanol (hydrolene), 3,7-dimethyl-1,6-octadien-3-ol (linalool), 7-hydroxy -3,7-Dimethyloctanal (hydroxycitronellal; laurinal), 7-hydroxy-3,7-dimethyloctanal dimethyl acetal (hydroxycitronellal dimethyl acetal), 3 ,7-Dimethyl-1,6-nonadien-3-ol (ethyllinalol), 2,5,5-trimethyl-octahydro-2-naphthol (Ambrinol), 2-methyl Base-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuran (cis and trans) (linalol oxide), 4-(4-hydroxy-4-methylpentyl )-3-cyclohexene-1-carbaldehyde (Lyral; Kovanol), 4-methyl-1-(1-methylethyl)-3-cyclohexene-1-ol, 3,7,9-tri Methyl-1,6-Decadien-3-ol (Isobutyllinalool), 3,7,11,15-Tetramethylhexadec-1-en-3-ol (Isophytol), Cedar alcohol and b-syringenol (syringenol).

Non-limiting examples of preferred tertiary aroma materials include those wherein the ^R1 , ^R2 and ^R3 units are linalyl, tetrahydrolinalyl, ethyllinalyl, dihydromyrcenyl, and mixtures thereof resulting in the release of linalool , tetrahydrolinalool, ethyllinalool, and dihydromyrcenol.

R is hydrogen, substituted or unsubstituted C ₁ -C ₂₀ straight chain alkyl, C ₃ -C ₂₀ branched chain alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ branched chain cycloalkyl, C ₃ -C ₂₀ straight chain alkenyl, C ₄ -C ₂₀ branched alkenyl, C ₃ -C ₂₀ cyclic alkenyl, C ₄ -C ₂₀ branched cyclic alkenyl, C ₆ -C ₂₀ aryl , C ₆ -C ₂₀ alkylene aryl, C ₆ -C ₂₀ alkylene oxyalkyl, C ₆ -C ₂₀ alkylene oxyaryl and mixtures thereof; or any of R ¹ , R ² or R ³ can be combined with R to form a ring with 5-8 atoms, and said ring is optionally replaced by one or more C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ alkenyl, C ₆ -C ₁₂ Substitution by aryl, _C6 - _C22 alkylene aryl units and mixtures thereof. Preferably R is hydrogen, substituted or unsubstituted C ₁ -C ₁₀ straight chain alkyl, C ₃ -C ₁₀ branched chain alkyl, C ₃ -C ₁₀ straight chain alkenyl, C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ alkylene aryl; more preferably R is selected from hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, benzyl and mixtures thereof.

The term "substitution" herein means "a compatible moiety that replaces a hydrogen atom". Non-limiting examples of substituents are hydroxyl, nitrilo, halogen, nitro, carboxyl (-CHO; -CO ₂ H, -CO ₂ R'; -CONH ₂ ; -CONHR';-CONR'₂; where R' is C ₁ -C ₁₂ linear or branched chain alkyl), amino, C ₁ -C ₁₂ mono and dialkylamino, and mixtures thereof. Fragrance-providing systems and related compositions

The present invention also relates to a fragrance providing system comprising:

a) at least one pro-accord releasing tertiary aroma raw material as described herein; and

b) A balancing amount of one or more pro-accords suitable for providing one or more fragrance raw materials.

When formulated into a fragrance-providing system, the orthoesters of the present invention that release tertiary aroma raw materials comprise from about 0.1% to about 99%, preferably from about 1% to 50%, of the fragrance-providing system.

The fragrance providing system of the present invention preferably comprises one or more pro-accords as described hereinafter. When present, said accords, alone or in admixture, comprise from 0.1% to about 99%, preferably from about 1% to about 50%, of the fragrance-providing system.

The present invention also relates to a fragrance or essence with increased fragrance persistence for application to human skin, comprising:

a) 0.1% - 99.9% by weight of at least one pro-accord releasing a tertiary alcoholic aroma raw material, provided that said pro-accord has a fragrance release half-life greater than or equal to 0.1 hour at pH 5.3, and at pH 2.5 Below or equal to 12 hours, said fragrance release half-life is measured in NaH ₂ PO ₄ buffer at said pH;

b) 0.1%-99.9% by weight of one or more aroma raw materials; and

c) Balanced amounts of carrier and auxiliary components.

In addition, the fragrance or fragrance composition of the present invention also includes carriers, fixatives and other auxiliary components, which can be added to the tertiary alcohol-releasing orthoesters or pro-accords in any suitable amount or ratio, and they constitute the fragrance-providing system. balance object. Typical carriers are methanol, ethanol (preferred), isopropanol, polyethylene glycol and in some cases water. Fixatives act to reduce the volatility of certain top and middle notes so that they last longer in contact with the skin. Auxiliary components include perfume raw components, which are essential oils and therefore not a single chemical entity. In addition, auxiliary components may be synthetic mixtures of fragrance raw materials which serve other functions besides providing a pleasant fragrance. Ortho ester

其中R是氢、取代或未取代的C₁-C₂₀直链烷基、C₃-C₂₀支链烷基、C₃-C₂₀环烷基、C₄-C₂₀支链环烷基、C₃-C₂₀直链烯基、C₄-C₂₀支链烯基、C₃-C₂₀环状链烯基、C₄-C₂₀支链环状链烯基、C₆-C₂₀芳基、C₆-C₂₀亚烷基芳基、C₆-C₂₀亚烷基氧基烷基、C₆-C₂₀亚烷基氧基芳基和其混合物；优选氢、取代或未取代的C₁-C₁₀直链烷基、C₃-C₁₀支链烷基、C₃-C₁₀直链烯基、C₆-C₁₀芳基、C₆-C₁₀亚烷基芳基；更优选R选自氢、甲基、乙基、丙基、异丙基、叔丁基、苯基、苄基和其混合物。A preferred class of compounds for use as pro-accords according to the invention are orthoesters having the formula: Wherein the ortho ester is hydrolyzed according to the following diagram to release the fragrance raw material components:

Wherein R is hydrogen, substituted or unsubstituted C ₁ -C ₂₀ straight chain alkyl, C ₃ -C ₂₀ branched chain alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ branched chain cycloalkyl, C ₃ -C ₂₀ straight chain alkenyl, C ₄ -C ₂₀ branched alkenyl, C ₃ -C ₂₀ cyclic alkenyl, C ₄ -C ₂₀ branched cyclic alkenyl, C ₆ -C ₂₀ aromatic C ₆ -C ₂₀ alkylene aryl, C ₆ -C ₂₀ alkylene oxyalkyl, C ₆ -C ₂₀ alkylene oxyaryl and mixtures thereof; preferably hydrogen, substituted or unsubstituted C ₁ -C ₁₀ straight chain alkyl, C ₃ -C ₁₀ branched chain alkyl, C ₃ -C ₁₀ straight chain alkenyl, C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ alkylene aryl; more Preferably R is selected from hydrogen, methyl, ethyl, propyl, isopropyl, t-butyl, phenyl, benzyl and mixtures thereof.

Each of R ¹ , R ² and R ³ is independently substituted or unsubstituted C ₁ -C ₂₀ straight chain alkyl, C ₃ -C ₂₀ branched chain alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ branched cyclic alkenyl, C ₃ -C ₂₀ straight chain alkenyl, C ₄ -C ₂₀ branched alkenyl, C ₃ -C ₂₀ cyclic alkenyl, C ₄ -C ₂₀ branched cyclic alkenyl , C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ alkylene aryl, C ₆ -C ₂₀ alkyleneoxyalkyl, C ₆ -C ₂₀ alkylene oxyaryl and mixtures thereof; preferably Substituted or unsubstituted C ₁ -C ₁₀ straight chain alkyl, C ₃ -C ₁₀ branched chain alkyl, C ₃ -C ₁₀ cycloalkyl, C ₄ -C ₁₀ branched chain cycloalkyl, C ₃ -C ₁₀ Straight chain alkenyl, C ₄ -C ₁₀ branched alkenyl, C ₃ -C ₁₀ cyclic alkenyl, C ₄ -C ₁₀ branched cyclic alkenyl and mixtures thereof. The term "substituted" means herein "a compatible moiety that replaces a hydrogen atom". Non-limiting examples of substituents are hydroxyl, nitrilo, halogen, nitro, carboxyl (-CHO; -CO ₂ H, -CO ₂ R'; -CONH ₂ ; -CONHR';-CONR'₂; where R' is C ₁ -C ₁₂ linear or branched chain alkyl), amino, C ₁ -C ₁₂ mono and dialkylamino, and mixtures thereof. Acetals and Ketals

其中R是C₁-C₂₀直链烷基、C₃-C₂₀支链烷基、C₃-C₂₀环烷基、C₄-C₂₀支链环烷基、C₃-C₂₀直链烯基、C₃-C₂₀支链烯基、C₃-C₂₀环状链烯基、C₄-C₂₀支链环状链烯基、C₆-C₂₀取代或未取代的芳基，优选取代芳基单元的部分是烷基和其混合物。R¹是氢，R，或在前谐香剂是酮缩醇的情况下，R和R¹可结合在一起形成环。R²和R³独立地选自C₅-C₂₀直链、支链或取代的烷基；C₄-C₂₀直链、支链或取代的链烯基；C₅-C₂₀取代或未取代的环烷基；C₆-C₂₀取代或未取代的芳基；C₂-C₄₀取代或未取代的亚烷基氧基；C₃-C₄₀取代或未取代的亚烷基氧基烷基；C₅-C₄₀取代或未取代的亚烷基芳基；C₆-C₃₂取代或未取代的芳基氧基；C₆-C₄₀取代或未取代的亚烷基氧基芳基；C₆-C₄₀氧基亚烷基芳基和其混合物。术语“取代”在这里的意思是“代替氢原子的可相容部分”。取代基的非限制实例是羟基、次氮基、卤素、硝基、羧基(-CHO；-CO₂H,-CO₂R’；-CONH₂；-CONHR’；-CONR’₂；其中R’是C₁-C₁₂直链或支链烷基)、氨基、C₁-C₁₂单和二烷基氨基，和其混合物。原碳酸酯Another class of compounds useful as pro-accords according to the invention are acetals and ketals having the formula: Wherein the acetal or ketal is hydrolyzed according to the following diagram to release one equivalent of aldehyde or ketone and two equivalents of alcohol:

Where R is C ₁ -C ₂₀ straight chain alkyl, C ₃ -C ₂₀ branched chain alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ branched cycloalkyl, C ₃ -C ₂₀ straight chain Alkenyl, C ₃ -C ₂₀ branched alkenyl, C ₃ -C ₂₀ cyclic alkenyl, C ₄ -C ₂₀ branched cyclic alkenyl, C ₆ -C ₂₀ substituted or unsubstituted aryl, Preferred moieties substituted for aryl units are alkyl groups and mixtures thereof. ^R1 is hydrogen, R, or where the proaccord is a ketal, R and ^R1 may be joined together to form a ring. R ² and R ³ are independently selected from C ₅ -C ₂₀ straight chain, branched or substituted alkyl; C ₄ -C ₂₀ straight chain, branched or substituted alkenyl; C ₅ -C ₂₀ substituted or unsubstituted Substituted cycloalkyl; C ₆ -C ₂₀ substituted or unsubstituted aryl; C ₂ -C ₄₀ substituted or unsubstituted alkyleneoxy; C ₃ -C ₄₀ substituted or unsubstituted alkyleneoxy Alkyl; C ₅ -C ₄₀ substituted or unsubstituted alkylene aryl; C ₆ -C ₃₂ substituted or unsubstituted aryloxy; C ₆ -C ₄₀ substituted or unsubstituted alkylene oxyaryl groups; C ₆ -C ₄₀ oxyalkylene aryl groups and mixtures thereof. The term "substituted" means herein "a compatible moiety that replaces a hydrogen atom". Non-limiting examples of substituents are hydroxyl, nitrilo, halogen, nitro, carboxyl (-CHO; -CO ₂ H, -CO ₂ R'; -CONH ₂ ; -CONHR';-CONR'₂; where R' is C ₁ -C ₁₂ linear or branched chain alkyl), amino, C ₁ -C ₁₂ mono and dialkylamino, and mixtures thereof. orthocarbonate

其中原酸酯根据以下图示水解释放香原料组分：

其可根据以下图示继续水解并进一步释放两当量一种或多种香原料醇：

由此每当量供给的原碳酸酯提供最多至4当量香原料醇，其中R¹、R²、R³和R⁴独立地为C₁-C₂₀直链、支链或取代的烷基；C₂-C₂₀直链、支链或取代的链烯基；C₃-C₂₀取代或未取代的环烷基；C₆-C₂₀取代或未取代的芳基；C₂-C₄₀取代或未取代的亚烷基氧基；C₃-C₄₀取代或未取代的亚烷基氧基烷基；C₆-C₄₀取代或未取代的亚烷基芳基；C₆-C₃₂取代或未取代的芳基氧基；C₆-C₄₀取代或未取代的亚烷基氧基芳基；C₆-C₄₀氧基亚烷基芳基和其混合物。术语“取代”在这里的意思是“代替氢原子的可相容部分”。取代基的非限制实例是羟基、次氮基、卤素、硝基、羧基(-CHO；-CO₂H,-CO₂R’；-CONH₂；-CONHR’；-CONR’₂；其中R’是C₁-C₁₂直链或支链烷基)、氨基、C₁-C₁₂单和二烷基氨基，和其混合物。Another class of preferred compounds for use as pro-accords according to the invention are orthocarbonates having the formula:

Wherein the ortho ester is hydrolyzed according to the following diagram to release the fragrance raw material components:

It can continue to hydrolyze and release two equivalents of one or more aroma raw alcohols according to the following scheme:

Thereby providing up to 4 equivalents of aroma raw alcohol per equivalent of supplied orthocarbonate, wherein R ¹ , R ² , R ³ and R ⁴ are independently C ₁ -C ₂₀ linear, branched or substituted alkyl; C ₂ -C ₂₀ straight chain, branched or substituted alkenyl; C ₃ -C ₂₀ substituted or unsubstituted cycloalkyl; C ₆ -C ₂₀ substituted or unsubstituted aryl; C ₂ -C ₄₀ substituted or Unsubstituted alkyleneoxy; C ₃ -C ₄₀ substituted or unsubstituted alkyleneoxyalkyl; C ₆ -C ₄₀ substituted or unsubstituted alkylene aryl; C ₆ -C ₃₂ substituted or Unsubstituted aryloxy; C ₆ -C ₄₀ substituted or unsubstituted alkyleneoxyaryl; C ₆ -C ₄₀ oxyalkylenearyl and mixtures thereof. The term "substituted" means herein "a compatible moiety that replaces a hydrogen atom". Non-limiting examples of substituents are hydroxyl, nitrilo, halogen, nitro, carboxyl (-CHO; -CO ₂ H, -CO ₂ R'; -CONH ₂ ; -CONHR';-CONR'₂; where R' is C ₁ -C ₁₂ linear or branched chain alkyl), amino, C ₁ -C ₁₂ mono and dialkylamino, and mixtures thereof.

Non-limiting examples of perfume raw material alcohols suitable for delivery by the pro-accords of the present invention include 2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethylcyclohexanemethanol ( Dihydro floralol), 5,6-dimethyl-1-methylvinylbicyclo[2.2.1]hept-5-ene-2-methanol (Arbozol), 2,4,6-trimethyl-3-cyclo Hexene-1-methanol (isocyclogeraniol), 4-(1-methylethyl)cyclohexanemethanol (Mayol), α-3,3-trimethyl-2-norbornanemethanol, 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-D ² -b-norbornaneethanol, 2-methyl-2-cyclohexylethanol, 1-(4-isopropylcyclohexyl ) ethanol, 1-phenylethanol, 1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-2-(4-methylphenyl)ethanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (solubilizing alcohol), 2-(cyclododecyl)propan-1-ol (hydroxyambran), 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), α-n-pentyl-3-phenyl-2-propen-1-ol (α-pentylcinnamyl alcohol), 3-hydroxy- Ethyl 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-trimethylcyclopent-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-phenyl Butan-2-ol, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)butan-2-one, 3-methyl-pentanol, 3-methyl-3-penten-1-ol, 2-methyl-4-phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol (Phenoxanol), 2-methyl-5 -Phenylpentanol, 2-methyl-5-(2,3-dimethyltricyclo[2.2.1.0(2,6)]hept-3-yl)-2-penten-1-ol Fragrant alcohol), 4-methyl-1-phenyl-2-pentanol, (1-methylbicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-ol , 3-methyl-1-phenylpentan-3-ol, 1,2-dimethyl-3-(1-methylvinyl)cyclopent-1-ol, 2-isopropyl-5-methanol Ethyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 2-isopropenyl-4-methyl-4-hexen-1-ol (Lavandulol), 2-ethyl-2-isopentenyl-3-hexenol, 1-hydroxymethyl-4-isopropenyl-1-cyclohexene (dihydrocuminol), 1-methyl 4-isopropenylcyclohex-6-en-2-ol (carvrenol), 6-methyl-3-isopropenylcyclohex-1-ol, 1-methyl-4-isopropene Cyclohexan-3-ol, 4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclohexanol, 2-tert-butylcyclohexanol, 2-tert-butyl-4-methyl Cyclohexanol, 4-isopropylcyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol, 2-(5,6,6-trimethyl base-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, 1 ,2-Dimethyl-3-(1-methylethyl)cyclohexane-1-ol, heptanol, 2,4-dimethylhept-1-ol, 2,4-dimethyl-2 ,6-Heptadienol, 6,6-Dimethyl-2-oxomethyl-bicyclo[3.1.1]hept-2-ene (myrtenol), 4-methyl-2,4- Heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6 ,6-Dimethyl-3-hydroxy-2-methylenebicyclo[3.1.1]heptane, 1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2,6- Dimethylheptan-2-ol, 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2-ol, 2 -Methyl-6-methylene-7-octen-2-ol (myrcenyl alcohol), 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-octadiene- 1-alcohol (geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol), 3,7-dimethyl-1,6-octadiene- 3-alcohol (linalool), 3,7-dimethyloctan-1-ol (geranium alcohol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4- octadien-1-ol, 3,7-dimethyl-6-octen-3-ol, 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), 2 ,6-Dimethyl-5,7-octadien-2-ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol , 2,6-Dimethyloctan-2-ol, 2,6-Dimethyloctan-3-ol, 3,6-Dimethyloctan-3-ol, 2,6-Dimethyloctan-7-ol Octen-2-ol, 2,6-Dimethyl-3,5-octadien-2-ol (alloocimenol), 3-methyl-1-octen-3-ol, 7-hydroxyl -3,7-Dimethyloctanal, 3-nonanol, 2,6-nonadien-1-ol, cis-6-nonen-1-ol, 6,8-dimethylnonan-2- Alcohol, 3-(hydroxymethyl)-2-nonanone, 2-nonen-1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6-nonanedi En-3-ol (Ethyl Linalool), Decyl Alcohol, 9-Decenol, 2-Benzyl-M-dioxan-5-ol, 2-Decen-1-ol, 2,4- Decen-1-ol, 4-methyl-3-decen-5-ol, 3,7,9-trimethyl-1,6-decadien-3-ol (isobutyllinalool ), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 2,4-dodecadiene- 1-alcohol, 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-tetramethyldeca Hexa-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-phenyl salicylate ethyl ethyl ester, 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-ethyl Oxy-4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl-5-methylphenol (thymol), amyl o-hydroxybenzoate, ethyl 2-hydroxybenzoate Esters, 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-trimethyloctahydro-2-naphthol, 1,3,3-trimethyl-2-norbornanol (feminyl alcohol), 3a,4,5 ,6,7,7a-hexahydro-2,4-dimethyl-4,7-methylene-1H-inden-5-ol, 3a,4,5,6,7,7a-hexahydro-3 ,4-Dimethyl-4,7-methylene-1H-indene-5-ol, 2-methyl-2-vinyl-5-(1-hydroxyl-1-methylethyl)tetrahydrofuran, b - Caryophyllenol and mixtures thereof.

Non-limiting examples of esters suitable for release from the pro-accords of the present invention include geraniyl formate, citronellol formate, phenethyl formate, phenoxyethyl formate, trans-2-hexenyl formate, formic acid cis-3-hexenyl, cis-6-nonenyl formate, 9-decenyl formate, 3,5,5-trimethylhexyl formate, 3-methyl-5-phenylpentyl formate ester, 6-methylhept-2-ol formate, 4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-butene-2-ol formate, formic acid 3-Methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol ester, 4-isopropylcyclohexylethyl-2 formic acid -alcohol ester, 6,8-dimethylnonan-2-ol formate, decahydro-b-naphthol formate, 4-isopropylcyclohexylmethyl formate, linaloyl formate, lavender formate Alcohol esters, citronellol formate, a-terpineol formate, nobutyl formate, isobornyl formate, bornyl formate, isobornyl formate, guaiacol formate, 2-tert-butylcyclohexyl formate ester, 4-tert-butylcyclohexyl formate, decahydro-b-naphthyl formate, menthyl formate, p-menthyl formate, neryl formate, cinnamyl formate, ethyl acetate, butyl acetate , isoamyl acetate, hexyl acetate, 3,5,5-trimethylhexyl acetate, geranyl acetate, citronellol acetate, phenylethyl acetate, phenoxyethyl acetate, trans- 2-Hexenyl, cis-3-hexenyl acetate, cis-6-nonenyl acetate, 9-decenyl acetate, 3-methyl-5-phenylpentyl acetate, 6-methyl acetate Hept-2-ol, 4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-butene-2-ol, 3-methyl-5 -(2,2,3-Trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol ester, decahydro-b-naphthol acetate, menthyl acetate, benzyl acetate ester, 4-isopropylcyclohexylethan-2-ol acetate, 6,8-dimethylnon-2-ol acetate, 1-phenylethyl acetate, 4-isopropylcyclohexylmethyl acetate , Linalyl Acetate, Lavenderyl Acetate, Citronellol Acetate, a-Terpineol Acetate, Nobolyl Acetate, Isobornyl Acetate, Bornyl Acetate, Isobornyl Acetate, Guaiacyl Acetate Wood alcohol ester, 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, decahydro-b-naphthol acetate, menthyl acetate, p-menthyl acetate, neryl acetate, acetic acid Cinnamyl alcohol ester, ethyl propionate, ethyl butyrate, butyl butyrate, isopentyl butyrate, hexyl butyrate, cis-3-hexenyl butyrate, cis-3-hexyl isobutyrate Enyl ester, ethyl isovalerate, 2-methyl butyrate, ethyl caproate, 2-propenyl caproate, ethyl heptanoate, 2-propenyl heptanoate, ethyl octanoate, 2-trans-4 -Ethyl cis-decadienoate, methyl 2-nonanoate, benzyl propionate, benzyl isovalerate, phenylethyl isobutyrate, phenylethyl isovalerate, butyrate a,a- Dimethylphenyl ethyl ester, methyl benzoate, hexyl benzoate, benzyl benzoate, ethyl phenylacetate, geraniol phenylacetate, 1-phenylethyl phenylacetate, methyl cinnamate Esters, Benzyl Cinnamate, Phenylethyl Cinnamate, Geraniyl Propionate, Geraniyl Isobutyrate, Geranyl Isovalerate, Linalyl Propionate, Linalyl Butyrate , linalyl isobutyrate, citronellol propionate, citronellol isobutyrate, citronellol isovalerate, citronellol tiglic acid, allyl 3-cyclohexyl propionate, Methyl dihydrojasmonate, methyl 2-hexyl-3-oxocyclopentacarboxylate and mixtures thereof.

Non-limiting examples of aldehydes released by the pro-accords of the present invention include phenylacetaldehyde, p-methylphenylacetaldehyde, p-cymenealdehyde, methylnonylacetaldehyde, phenylpropanal, 3-(4- tert-butylphenyl)-2-methylpropanal (liral), 3-(4-tert-butylphenyl)propanal (Bourgeonal), 3-(4-methoxyphenyl)-2- Methylpropanal (Canthoxal), 3-(4-isopropylphenyl)-2-methylpropanal (Cymal), 3-(3,4-methylenedioxyphenyl)-2-methanal Helional, 3-(4-ethylphenyl)-2,2-dimethylpropanal (Floralozone), phenylbutyraldehyde, 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-octyl Dien-1-al, 3,7-dimethyl-1,6-octadiene-3-al, 3,7-dimethyl-6-octenal (citronellal), 3,7- Dimethyl-7-hydroxyoct-1-al (hydroxycitronellal), nonanal, 6-nonenal, 2,4-nonadienal, 2,6-nonadienal, decanal, 2 -Methyldecenal, 4-decenal, 9-decenal, 2,4-decadienal, undecanal, 2-methyldecenal, 2-methylundecenal, 2, 6,10-trimethyl-9-undecenal (Adoxal), undec-10-enal, undec-8-enal, dodecanal, tridecanal, tetradecane Aldehydes, anisaldehyde, bourgenonal, cinnamaldehyde, a-amylcinnamaldehyde, a-hexylcinnamaldehyde, methoxycinnamaldehyde, isocyclic citral, citronellyl oxoacetaldehyde, cortexaldehyde, cumin Aldehydes, cyclamenaldehyde, florhydral, piperonal, water-solubilizing aldehydes, vanillin, ethyl vanillin, benzaldehyde, p-tolualdehyde, 3,4-dimethoxybenzaldehyde, 3 - and 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde (nelial), 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (Triplal), 1-methyl-3-(4-methylpentyl)-3-cyclohexenecarbaldehyde (Vernaldehyrde), p-methylphenoxyacetaldehyde (Xialdehyde), and mixtures thereof.

Non-limiting examples of ketones released by the pro-accords of the present invention include alpha-damascenone, b-damascenone, d-damascenone, b-damascenone, muscone, 6, 7-dihydro-1,1,2,3,3-pentamethyl-4(5H)indanone (cashmeran), cis-jasmone, dihydrojasmone, α-ionone, b-ionone, Dihydro_b-ionone, g-methylionone, α-isomethylionone, 4-(3,4-methylenedioxyphenyl)butan-2-one, 4-(4- hydroxyphenyl)butan-2-one, methyl-b-naphthyl ketone, methyl cedryl ketone, 6-acetyl-1,1,2,4,4,7-hexamethyl-1,2,3, 4-tetralin (musk tuna), 1-carvone, 5-cyclohexadecen-1-one, acetophenone, decanone, 2-[2-(4-methyl-3-cyclo Hexen-1-yl)propyl]cyclopent-2-one, 2-sec-butylcyclohexanone, b-dihydroionone, allyl ionone, α-methylionone, methyl-2 -Ionone, α-Ionone, Acetylanisole, Geranylacetone, 1-(2-Methyl-5-isopropyl-2-cyclohexenyl)-1-propanone, Acetyldiisoamyl , methyl cyclocitrone, 4-tert-amylcyclohexanone, p-tert-butylcyclohexanone, o-tert-butylcyclohexanone, ethyl amyl ketone, ethyl amyl ketone, menthone, methyl-7,3- Dihydro-2H-1,5-benzodioxepine-3-one, fennelone and mixtures thereof. Fragrance release half-life

The pro-fragrances releasing tertiary alcohols, and other pro-accords used in the fragrance system provided by the present invention are hydrolyzed to release fragrance raw materials upon contact with human skin. However, in order to meet the needs of formulators, pro-accords must release their perfume components at an appropriate rate to provide a sustainable fragrance profile.

The task of determining the release rate of pro-accords on human skin is cumbersome and prone to variability. It has thus surprisingly been found that pro-accords can be evaluated in a manner which does not involve contact with human skin, which is a direct indication of their suitability for use as a tertiary alcohol-releasing pro-accord. This method can also be applied to all pro-perfumes suitable for use in the present invention to provide a fragrance system.

For the purposes of the present invention, have a "fragrance release half-life" lower than or equal to 12 _hours when measured in _NaH2PO4 buffer at pH 2.5, and when measured in _NaH2PO4 buffer at pH _5.3 , pro-accords having a "fragrance release half-life" greater than or equal to 0.1 hour are suitable as orthoesters releasing tertiary alcohols or pro-accords used in the present invention to provide fragrance systems. "Fragrance release half-life" is defined herein as follows.

Pro-accords release their corresponding fragrance raw material mixtures or fragrance-accords according to the following equation:

Proaccord → Accord wherein the released accord may in some cases comprise a single fragrance raw material, but is preferably a binary or multiple fragrance raw material accord.

The rate of fragrance accord release is defined by the following formula:

其中k是释放速率常数，[前谐香剂]是前谐香剂的浓度。对于本发明目的，“香味释放半衰期”，t_1/2，与释放速率常数有下式的关系： $t_{1/2}=\frac{0.693}{k}$ 此关系式用于本发明目的，确定“香味释放半衰期”(FRHL)。Rate = k[pre-accord] and can also be represented by:

where 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 _1/2 , has the following relationship to the release rate constant: $t_{1/2}=\frac{0.693}{k}$ This relationship is used for the purposes of the present invention to determine the "Fragrance Release Half-Life" (FRHL).

Due to the hydrophobic nature of some pro-accords, measurements of t _1/2 and k in a 90/10 dioxane/phosphate buffered water mixture were required.

An example of a method used to determine the suitability of a pro-accord for use in a fragrance delivery system at pH 2.5 is as follows. Phosphate buffered water was prepared by mixing 3.95 mL of 85% phosphoric acid (H ₃ PO ₄ ) and 24 g of monobasic sodium phosphate (NaH ₂ PO ₄ ) with 1 liter of water. The pH of this solution is approximately 2.5. Next, 10 mL of phosphate buffer was mixed with 90 mL of dioxane, and the pro-perfume to be analyzed was added. The hydrolysis kinetics were then monitored at 30°C by conventional HPLC methods.

Di(n-pentyl)dihydromyrcenyl orthoformate is measured at pH 5.3 under the above-mentioned conditions, and has a fragrance release half-life of about 1.3 hours, so it is the tertiary alcohol dihydromyrcenol and used in the present invention. Suitable ortho esters to provide fragrance systems.

Embodiment 1 two (phenylethyl) orthoformates one (dihydromyrcenyl alcohol) ester

Tris(phenylethyl)orthoformate (1 equivalent), dihydromyrcenol (3 equivalents) and an acid catalyst [eg, 2,4,6-trimethylbenzoic acid, 2,6-dichlorobenzene Formic acid or tetrabutylammonium hydrogensulfate, 1-2 mol%] was stirred at 40° C. under high vacuum (<0.25 mmHg) for 5 days. The reaction mixture was then diluted with 2 volumes of ether, washed with saturated sodium carbonate solution, dried, evaporated and flash chromatographed to give analytically pure bis(phenylethyl)mono(dihydromyrcenol)orthoformate.

The following are examples of fragrance-providing systems of the present invention.

Example 2 components weight% Pro-accord components releasing tertiary alcohols Pre-accord ¹ 5.1 Potassium Carbonate ² Ethanol ³ 12.4 Other pre-accords Tris(citronellyl)orthoformate 8.1 Citronellyloxyacetaldehyde bis(citronellyl)acetal 4.7 Fragrance ingredients Phenylacetaldehyde 0.7 Base fragrance and incense raw materials ⁴ 61.4 Auxiliary ⁵ 2.1 Ethanol ⁶ Balance

1. Bis(phenylethyl)mono(dihydromyrcenyl)orthoformate

2. Sufficient to provide 1 mM of potassium carbonate reserve alkalinity.

3. The ethanol vehicle contains less than 1% water.

4. Fragrance raw materials are base incense, middle incense and top incense, which include polyethylene glycol as a carrier and absolute ethanol as a diluent.

5. Diethyl phthalate as a fixative.

6. absolute ethanol.

Claims (10)

1. the preceding fragrant-inner agent that has following formula: Wherein X is oxygen, sulphur, nitrogen and its mixture; Each R ¹, R ²And R ³Independently for replacing or unsubstituted C ₁-C ₂₀Straight chained alkyl, C ₃-C ₂₀Branched-chain alkyl, C ₃-C ₂₀Cycloalkyl, C ₄-C ₂₀Side chain cycloalkyl, C ₃-C ₂₀Straight-chain alkenyl, C ₄-C ₂₀Branched-chain alkenyl, C ₃-C ₂₀Closed chain thiazolinyl, C ₄-C ₂₀Side chain closed chain thiazolinyl, C ₆-C ₂₀Aryl, C ₆-C ₂₀Alkylidene aryl, C ₆-C ₂₀Alkylidene group oxygen base alkyl, C ₆-C ₂₀Alkylidene group oxygen Ji Fangji and its mixture; Perhaps any two R ¹, R ²Or R ³The ring that can have 5-8 atom in conjunction with formation, said ring are also randomly by one or more C ₁-C ₂₂Alkyl, C ₁-C ₂₂Alkenyl, C ₆-C ₁₂Aryl, C ₆-C ₂₂Alkylidene aryl unit and its mixture replace; R is hydrogen, replacement or unsubstituted C ₁-C ₂₀Straight chained alkyl, C ₃-C ₂₀Branched-chain alkyl, C ₃-C ₂₀Cycloalkyl, C ₄-C ₂₀Side chain cycloalkyl, C ₃-C ₂₀Straight-chain alkenyl, C ₃-C ₂₀Branched-chain alkenyl, C ₃-C ₂₀Closed chain thiazolinyl, C ₄-C ₂₀Side chain closed chain thiazolinyl, C ₆-C ₂₀Aryl, C ₆-C ₂₀Alkylidene aryl, C ₆-C ₂₀Alkylidene group oxygen base alkyl, C ₆-C ₂₀Alkylidene group oxygen Ji Fangji and its mixture; Or any R ¹, R ²Or R ³Can combine the ring that formation has 5-8 atom with R, said ring is also randomly by one or more C ₁-C ₂₂Alkyl, C ₁-C ₂₂Alkenyl, C ₆-C ₁₂Aryl, C ₆-C ₂₂Alkylidene aryl unit and its mixture replace; Condition is at least one R ¹, R ²Or R ³The unit is derived from tertiary alcohol perfume material, said before fragrant-inner agent under pH5.3, have fragrance and discharge the transformation period more than or equal to 0.1 hour with under pH2.5, be less than or equal to 12 hours, it is NaH at said pH that said fragrance discharges the transformation period ₂PO ₄Measure in the damping fluid.

2. according to the compound of claim 1, each R wherein ¹, R ²And R ³Independently for replacing or unsubstituted C ₁-C ₁₂Straight chained alkyl, C ₃-C ₁₂Branched-chain alkyl, C ₃-C ₁₂Cycloalkyl, C ₄-C ₁₂Side chain cycloalkyl, C ₃-C ₁₂Straight-chain alkenyl, C ₄-C ₁₂Branched-chain alkenyl, C ₃-C ₁₂Closed chain thiazolinyl, C ₄-C ₁₂Side chain closed chain thiazolinyl and its mixture.

3. according to the compound of claim 1 or 2, at least one R wherein ¹, R ²Or R ³Be linalyl, tetrahydrochysene linalyl, ethyl linalyl, dihydromyrcene base and its mixture.

4. according to the compound of arbitrary claim 1-3, wherein said preceding fragrant-inner agent can discharge the tertiary alcohol, and this tertiary alcohol is selected from linalool, Tetrahydrolinalool, Ethyl linalool, pure and mild its mixture of dihydromyrcene.

5. system that fragrance is provided, it comprises:

A) at least a preceding fragrant-inner agent with following formula:

Wherein at least a-OR ¹,-OR ²With-OR ³The oxyalkyl units perfume material of the tertiary alcohol of doing for oneself of deriving, R is hydrogen, replacement or unsubstituted C independently ₁-C ₂₀Straight chained alkyl, C ₃-C ₂₀Branched-chain alkyl, C ₃-C ₂₀Cycloalkyl, C ₄-C ₂₀Side chain cycloalkyl, C ₃-C ₂₀Straight-chain alkenyl, C ₄-C ₂₀Branched-chain alkenyl, C ₆-C ₂₀Closed chain thiazolinyl, C ₆-C ₂₀Side chain closed chain thiazolinyl, C ₆-C ₂₀Aryl, C ₆-C ₂₀Alkylidene aryl, C ₆-C ₂₀Alkylidene group oxygen base alkyl, C ₆-C ₂₀Alkylidene group oxygen Ji Fangji and its mixture; Condition be said before fragrant-inner agent under pH5.3, have fragrance and discharge the transformation period more than or equal to 0.1 hour with under pH2.5, be less than or equal to 12 hours, it is NaH at said pH that said fragrance discharges the transformation period ₂PO ₄Measure in the damping fluid; With

B) the preceding fragrant-inner agent of one or more of equal amount.

6. according to the composition of claim 5, wherein (b) described before fragrant-inner agent:

A) form by the perfume material of at least a molecular weight more than or equal to 100g/mol;

B) has molecular weight more than or equal to 300g/mol;

C) molecular weight that is had is at least 2 times of described preceding perfume material fragrant-inner agent, that molecular weight is minimum of composition; With

D) have fragrance under pH5.3 and discharge the transformation period more than or equal to 0.1 hour be less than or equal to 12 hours under pH2.5, it is NaH at said pH that said fragrance discharges the transformation period ₂PO ₄Measure in the damping fluid.

7. spices or essence that is applied to the lasting fragrance increase of human skin, it comprises:

A) at least a preceding fragrant-inner agent of the release tertiary alcohol perfume material of 0.1%-99.9% weight, condition is that described preceding fragrant-inner agent had the fragrance release transformation period more than or equal to 0.1 hour under pH5.3, or under pH2.5, be less than or equal to 12 hours, the said fragrance release transformation period is the NaH at said pH ₂PO ₄Measure in the damping fluid;

B) one or more perfume materials of 0.1%-99.9% weight; With

C) carrier of equal amount and auxiliary component.

8. according to the composition of claim 7, wherein discharge fragrant-inner agent before tertiary alcohol perfume material at least a and be fragrant-inner agent before the ortho ester of following formula:

Each R wherein ¹, R ²And R ³Independently for replacing or unsubstituted C ₁-C ₂₀Straight chained alkyl, C ₃-C ₂₀Branched-chain alkyl, C ₃-C ₂₀Cycloalkyl, C ₄-C ₂₀Side chain cycloalkyl, C ₃-C ₂₀Straight-chain alkenyl, C ₄-C ₂₀Branched-chain alkenyl, C ₃-C ₂₀Closed chain thiazolinyl, C ₄-C ₂₀Side chain closed chain thiazolinyl, C ₆-C ₂₀Aryl, C ₆-C ₂₀Alkylidene aryl, C ₆-C ₂₀Alkylidene group oxygen base alkyl, C ₆-C ₂₀Alkylidene group oxygen Ji Fangji and its mixture; R is hydrogen, replacement or unsubstituted C ₁-C ₂₀Straight chained alkyl, C ₃-C ₂₀Branched-chain alkyl, C ₃-C ₂₀Cycloalkyl, C ₄-C ₂₀Side chain cycloalkyl, C ₃-C ₂₀Straight-chain alkenyl, C ₃-C ₂₀Branched-chain alkenyl, C ₃-C ₂₀Closed chain thiazolinyl, C ₄-C ₂₀Side chain closed chain thiazolinyl, C ₆-C ₂₀Aryl, C ₆-C ₂₀Alkylidene aryl, C ₆-C ₂₀Alkylidene group oxygen base alkyl, C ₆-C ₂₀Alkylidene group oxygen Ji Fangji and its mixture.

9. according to the composition of claim 7 or 8, wherein the preceding fragrant-inner agent of (a) can discharge the tertiary alcohol, and this tertiary alcohol is selected from linalool, Tetrahydrolinalool, Ethyl linalool, pure and mild its mixture of dihydromyrcene.

10. according to the composition of arbitrary claim 7-9, it also comprises the reserve alkalinity that is equivalent at least 0.001 moles of NaOH.