JP7206219B2 - Reduction of organic hydroperoxides in perfume raw materials and food raw materials - Google Patents

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62/502,156, filed May 5, 2017, and European Patent Application No. 17176476.4, filed June 16, 2017 and the entire contents of which are incorporated by reference herein in their entireties.

Various embodiments described herein reduce the peroxide value of perfume ingredients, perfume formulations, formulated body care products, formulated skin care products, formulated home care products, essential oils, food ingredients, formulated foodstuffs, and natural extracts. It relates to methods and compositions for reducing.
BACKGROUND OF THE INVENTION Perfume formulations, body care products, home care products, perfume ingredients (such as essential oils, natural extracts, and synthetic ingredients), and food ingredients (such as oils and fats from animal or vegetable sources, and derivatives thereof). monoglycerides, diglycerides, lecithins, phosphatidylethanolamines, or other phospholipids, and modified triglycerides) can be oxidized, resulting in peroxides, organic hydroperoxides, Species such as peroxyhemiacetal can be generated.

Peroxide Value (POV) is defined as the equivalent of potential oxidation per kg of material and is an indication of the degree of oxidation. POV of perfume formulations, body care products and perfume ingredients are or may be restricted by regulation due to skin sensitization concerns, eg contact dermatitis. For example, a perfume ingredient may fail a quality control test due to an unacceptably high POV and thus be considered unusable. In another example, an unacceptably high POV may cause food ingredients to have an unpleasant off-taste.

Therefore, reducing the POV of perfume formulations, body care products, home care products, cosmetics, and perfume ingredients causes the perfume formulations, body care products, and perfume ingredients to fail quality control tests, or It is necessary to reduce the causes of skin irritation. There is also a need to reduce the occurrence of off-taste in food ingredients by reducing the POV of the food ingredients.
SUMMARY OF THE INVENTION One aspect described herein provides a method of reducing the POV of a perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient, comprising: The method comprises adding an alpha-oxocarboxylic acid to the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient having a first POV level; - oxocarboxylic acid in said perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient, said first POV level to a predetermined lower second POV level. and mixing for a time sufficient to reduce the

One aspect described herein is skin irritation in a subject in need of reducing, preventing, or alleviating skin irritation induced by perfume formulations, body care products, home care products, cosmetics, or perfume ingredients. (a) the perfume formulation, body care product, home care product, cosmetic product, or perfume ingredient having a first POV level and (b) adding said α-oxocarboxylic acid to said perfume formulation, body care product, home care product, cosmetic product, or perfume ingredient to said first POV level. mixing for a time sufficient to reduce to a predetermined lower second POV level, wherein the predetermined lower POV level is applied to the perfume formulation, body care product, home care product, sufficient to reduce, prevent, or alleviate irritation of the subject's skin induced by cosmetic or perfume ingredients.

In one aspect, the perfume raw material is selected from the group consisting of synthetic ingredients, natural products, essential oils, and natural extracts.

In one aspect, the body care product is a skin cream.

In one aspect, the food ingredient is selected from the group consisting of fats, oils, or derivatives thereof.

In one aspect, the derivatives are selected from the group consisting of monoglycerides, diglycerides and phospholipids.

In one aspect, the phospholipid is selected from the group consisting of lecithin, phosphatidylethanolamine, and modified triglycerides.

In one aspect, the perfume raw material is treated prior to being blended into the perfume.

In one aspect, the perfume raw material is processed after it has been incorporated into the perfume.

In one aspect, the food ingredients are treated prior to being incorporated into the flavored article.

In one aspect, the food ingredients are processed after being formulated into the flavored article.

In one aspect, the concentration of α-oxocarboxylic acid after addition to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients is between 0.001 and 10% by weight. Range.

In one aspect, the α-oxocarboxylic acids are pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutarate, 2-oxopentane. The group consisting of dioates, indole-3-pyruvate, 2-thiopheneglyoxylate, trimethylpyruvate, 2-oxoadipate, 4-hydroxyphenylpyruvate, phenylpyruvate, 2-oxooctanoate, and mixtures thereof more selected.

In one aspect, the perfume raw material is a citrus oil.

In one aspect, the food ingredient is a cooking oil.

In one aspect, the predetermined lower second POV level is 5-20 mmol/L.

In one aspect, the predetermined lower second POV level is 0-6 mmol/L.

In one aspect, the method further comprises removing excess α-oxocarboxylic acid from a perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient having a predetermined second lower POV level. Including removing acid.

In one aspect, excess α-oxocarboxylic acid is removed from perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients by liquid-liquid extraction.

In one aspect, the method further comprises treating the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient after removing the alpha-oxocarboxylic acid to produce a perfume formulation. , reducing the acidity of body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients.

In one aspect, a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient is treated with a carbonate to produce a perfume formulation, body care product, cosmetic, home care product, Reduces the acidity of perfume ingredients, flavored articles, or food ingredients.

One aspect described herein is a composition comprising (a) a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient, and (b) an α-oxocarboxylic acid wherein the α-oxocarboxylic acid is present in the composition in an amount sufficient to reduce the POV from a first POV level to a predetermined lower second POV level; A composition is provided.

One aspect described herein is a composition comprising (a) a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient, and (b) an α-oxocarboxylic acid wherein the alpha-oxocarboxylic acid reduces, prevents, or increases the POV of the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient; A composition is provided which is present in the composition in an amount sufficient to provide relief.

In one aspect, the α-oxocarboxylic acid is added to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients at concentrations ranging from 0.001 to 10% by weight. be done.

In one aspect, the perfume raw material is a citrus oil.

In one aspect, the α-oxocarboxylic acid is present in the composition in an amount sufficient to prevent the predetermined lower second POV level from changing over time.

In one aspect, the concentration of α-oxocarboxylic acid in the composition ranges from 0.001 to 10% by weight.

In one aspect, the α-oxocarboxylic acid is added to the perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient as an inorganic salt.

In one aspect, the α-oxocarboxylic acid is present in the composition as an inorganic salt.

In one aspect, the salt converts the α-oxocarboxylic acid from 2-(dimethylamino)ethanol, N,N-dimethyldodecylamine, tris[2-(2-(methoxyethoxy)ethyl]amine, and N-methyldiethanolamine. is an ammonium salt formed by reacting with a compound selected from the group

In one aspect, the α-oxocarboxylic acid is added to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients as salts of monovalent or divalent cations. be.

In one aspect, the α-oxocarboxylic acid is present in the composition as a salt of a monovalent or divalent cation.

In one aspect, the α-oxocarboxylic acids are pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutarate, 2-oxopentane. The group consisting of dioates, indole-3-pyruvate, 2-thiopheneglyoxylate, trimethylpyruvate, 2-oxoadipate, 4-hydroxyphenylpyruvate, phenylpyruvate, 2-oxooctanoate, and mixtures thereof more selected.

FIG. 2 is a diagram of reactions of α-oxocarboxylic acids and organic hydroperoxides presented as examples, according to certain embodiments described herein. FIG. 3 illustrates the rate of reduction of POV in perfume raw materials according to certain aspects described herein. FIG. 3 shows a POV of a skin cream according to methods according to certain aspects described herein. FIG. 3 shows a POV of a skin cream according to methods according to certain aspects described herein. FIG. 10 illustrates the change in POV of a model perfume treated with a method according to certain aspects described herein. FIG. 10 illustrates the change in POV of a model perfume treated with a method according to certain aspects described herein. FIG. 3 shows the POV of liquid soap formulations treated with methods according to certain aspects described herein. FIG. 3 shows the percent reduction in POV of liquid soap formulations treated with methods according to certain aspects described herein. FIG. 3 shows the POV of shampoo formulations treated with methods according to certain aspects described herein. FIG. 3 shows the percent reduction in POV for shampoo formulations treated with methods according to certain aspects described herein. FIG. 3 shows the POV of an all-purpose cleaner spray formulation treated with a method according to certain aspects described herein. FIG. 3 shows the reduction in POV of an all-purpose cleaner spray formulation treated with a method according to certain aspects described herein. FIG. 3 shows the POV of skin cream formulations treated with methods according to certain aspects described herein. FIG. 3 shows the percent reduction in POV for skin cream formulations treated with methods according to certain aspects described herein. FIG. 3 shows the POV of antiperspirant stick formulations treated with methods according to certain aspects described herein. FIG. 3 shows the percent reduction in POV for antiperspirant stick formulations treated with methods according to certain aspects described herein. DETAILED DESCRIPTION In the following description, references are made to specific embodiments that may be implemented, and these are presented for purposes of illustration. These embodiments are described in detail to enable those skilled in the art to practice the invention described herein, understand that other embodiments may be utilized, and that the aspects described herein may It should be understood that necessary changes may be made without deviation. Therefore, the following description of example embodiments should not be taken in a limiting sense, and the scope of the various aspects described herein is intended to be defined by the appended claims.

The Abstract complies with 37 CFR §1.72(b) and is provided to allow the reader to quickly ascertain the nature and gist of this technical disclosure. The Abstract is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims.

Many perfume formulations, body care products, home care products, and perfume ingredients (such as essential oils, natural extracts, and synthetic ingredients) can oxidize, resulting in peroxides, organic hydroperoxides, peroxy Chemical species such as hemiacetal are produced. Also, many food ingredients, such as fats or their derivatives, are known to undergo autoxidation processes that result in the formation of intermediate species of glyceride hydroperoxides. Glyceride hydroperoxides can be further degraded to aldehydes and ketones. While not intending to be bound by any particular theory, autoxidation processes can cause an unpleasant and unpalatable rancidity or scalding of food ingredients.

Peroxide Value (POV) is defined as the equivalent of potential oxidation per kg of material and is an indication of the degree of oxidation. POV of perfume formulations, body care products, home care products, cosmetics, and perfume ingredients are restricted by regulation due to skin sensitization concerns, eg contact dermatitis. For example, a perfume ingredient may fail a quality control test due to an unacceptably high POV and thus be considered unusable. In another example, food ingredients or formulated food products (also referred to herein as flavored articles) may have an off-taste due to an unacceptably high POV.

Skin exposure can be the result of accidental exposure (eg, exposure to hard surface cleaners or hand dish soap when the user is not wearing gloves when using these products). Alternatively, skin exposure can be the result of prolonged or intentional exposure (such as exposure to shampoos or skin moisturizers).

As used herein, the term "peroxide value" or "POV" refers to the equivalent of potential oxidation per kg of material. Without intending to be bound by any particular theory, the POV of a material is analytically determined. The term "POV" does not refer to a compound or group of compounds, but is often used loosely interchangeably with auto-oxidation products in a sample responsible for responses in POV tests. These autoxidation products vary with the particular substance tested. Many compound classes, including, but not limited to, organic and inorganic hydroperoxides, organic and inorganic peroxides, peroxyhemiacetals, peroxyhemiketals, and hydrogen peroxide itself produce responses in the POV test.

Illustratively, one POV test is the iodine redox titration method. All POV-responsive compounds share the property of being capable of oxidizing iodine ions to molecular iodine within the specified time period of the test. In fact, the iodine oxidation reaction is the basis of this test. Thus, "POV" is a number representing the molar summation of all iodine oxidizing species in a particular sample.

By way of illustration, limonene and linalool are unsaturated terpenes commonly found as major constituents in many essential oils. Both limonene and linalool are readily oxidized by ambient oxygen to form hydroperoxides. Hydroperoxides of limonene and linalool are known sensitizers that can cause contact dermatitis. Limonene and limonene-containing natural products can therefore only be used as perfume raw materials if the recommended organic hydroperoxide level is less than 20 mmol/L (or 10 mEq/L). Similarly, essential oils and isolates from the Pinaceae family, including Pinus and Fir, should only be used as perfume ingredients if the recommended organic hydroperoxide level is less than 10 mmol/L (or 5 mEQ/L). be able to.

As another example, fats and oils or their derivatives are known to undergo an autoxidation process resulting in an unpleasant and unpalatable rancidity or scalding. Without intending to be bound by any particular theory, glyceride hydroperoxides are intermediate species in the autoxidation process and are further broken down into off-flavoring aldehydes and ketones.

The POV of a perfume raw material can be determined by any method readily selected by those skilled in the art. Non-limiting examples include iodine titration, high performance liquid chromatography, and the like.

An example of a method for determining the POV of perfume raw materials is disclosed in Calandra et al., Flavor and Fragr. J. (2015), 30, p 121-130.

Perfume ingredients include, but are not limited to, essential oils, natural extracts, and synthetic ingredients.

The POV of perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients can be determined by any method readily selectable by one skilled in the art. Non-limiting examples include iodine titration, high performance liquid chromatography, and the like.

An example of a method for determining the POV of perfume formulations is disclosed in Calandra et al., Flavor and Fragr. J. (2015), 30, p 121-130.

The POV of a formulated body care product can be determined by any method readily selectable by one skilled in the art. Non-limiting examples include iodine titration, high performance liquid chromatography, and the like.

An example of a method for determining the POV of a formulated body care product is disclosed in Calandra et al., Flavor and Fragr. J. (2015), 30, p 121-130.

Without intending to be bound by any particular theory, the POV of a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient may be the perfume formulation, body care product, It is reduced by treating cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients with α-oxocarboxylic acids. α-Oxocarboxylic acids react with organic hydroperoxides by oxidative decarboxylation, thereby consuming the organic hydroperoxide and reducing the oxidizability of the organic hydroperoxide. The resulting reaction results in the oxidation of the α-oxocarboxylic acid to its carboxylic acid with one less carbon atom and carbon dioxide and the reduction of the organic hydroperoxide to its organic alcohol. A reaction presented as an example using pyruvic acid as the α-oxocarboxylic acid and limonene-hydroperoxide as the organic hydroperoxide is shown in FIG.

Accordingly, one aspect described herein provides a method of reducing the POV of a perfume raw material, the method comprising adding an alpha-oxocarboxylic acid to the perfume raw material having a first POV level. and mixing the α-oxocarboxylic acid with the perfume raw material for a time sufficient to reduce the first POV level to a predetermined lower second POV level.

An alternative embodiment described herein provides a method of reducing, preventing or alleviating skin irritation in a subject in need of reducing, preventing or alleviating perfume ingredient induced skin irritation. the method comprising the steps of: (a) adding an α-oxocarboxylic acid to the perfume raw material having a first POV level; and (b) adding the α-oxocarboxylic acid to the perfume raw material to the mixing for a time sufficient to reduce the first POV level to a second predetermined lower POV level, wherein the second predetermined lower POV level is induced in the perfume raw material. sufficient to reduce, prevent, or alleviate inflammation of the subject's skin.

One aspect described herein provides a method of reducing the POV of a perfume formulation, the method comprising adding an alpha-oxocarboxylic acid to the perfume formulation having a first POV level and mixing the α-oxocarboxylic acid into the perfume formulation for a period of time sufficient to reduce the first POV level to a predetermined lower second POV level.

An alternative embodiment described herein provides a method of reducing, preventing or alleviating skin irritation in a subject in need of reducing, preventing or alleviating perfume formulation induced skin irritation. (a) adding an alpha-oxocarboxylic acid to the perfume formulation having a first POV level; and (b) adding the alpha-oxocarboxylic acid to the perfume formulation. and mixing for a time sufficient to reduce the first POV level to a predetermined lower second POV level, wherein the predetermined lower POV level reduces the perfume formulation. is sufficient to reduce, prevent, or alleviate inflammation of the subject's skin induced by

One aspect described herein provides a method of reducing the POV of a formulated personal care product, the method comprising adding an alpha-oxocarboxylic acid to the formulated personal care product having a first POV level. and mixing the α-oxocarboxylic acid into the formulated personal care product for a time sufficient to reduce the first POV level to a predetermined lower second POV level. include.

One alternative embodiment described herein provides a method of reducing, preventing or alleviating skin irritation in a subject in need of reducing, preventing or alleviating skin irritation induced by a formulated personal care product. (a) adding an alpha-oxocarboxylic acid to the formulated personal care product having a first POV level; and (b) adding the alpha-oxocarboxylic acid to the formulation. admixing the personal care product for a time sufficient to reduce the first POV level to a second predetermined lower POV level, wherein the predetermined lower second POV level reduces the sufficient to reduce, prevent, or alleviate irritation of the subject's skin induced by the formulated personal care product.

One aspect described herein provides a method of reducing the POV of a formulated cosmetic product, the method comprising the steps of adding an α-oxocarboxylic acid to the formulated cosmetic product having a first POV level; and the α-oxocarboxylic acid into the formulated cosmetic for a period of time sufficient to reduce the first POV level to a predetermined lower second POV level.

One alternative aspect described herein provides a method of reducing, preventing, or alleviating skin irritation in a subject in need of reducing, preventing, or alleviating skin irritation induced by formula cosmetics. wherein the method comprises the steps of: (a) adding an α-oxocarboxylic acid to the formulated cosmetic having a first POV level; and (b) adding the α-oxocarboxylic acid to the formulated cosmetic to the mixing for a time sufficient to reduce the first POV level to a predetermined lower second POV level, wherein the predetermined lower POV level is induced in the formulated cosmetic. sufficient to reduce, prevent, or alleviate inflammation of the subject's skin.

One aspect described herein provides a method of reducing the POV of a formulated home care product, the method comprising adding an alpha-oxocarboxylic acid to the formulated home care product having a first POV level. and mixing the α-oxocarboxylic acid into the formulated home care product for a time sufficient to reduce the first POV level to a predetermined lower second POV level. include.

One alternative embodiment described herein provides a method of reducing, preventing or alleviating skin irritation in a subject in need of reducing, preventing or alleviating skin irritation induced by a formulated home care product. (a) adding an alpha-oxocarboxylic acid to the formulated home care product having a first POV level; and (b) adding the alpha-oxocarboxylic acid to the formulated admixing the home care product for a time sufficient to reduce the first POV level to a second predetermined lower POV level, wherein the predetermined lower second POV level reduces the sufficient to reduce, prevent, or alleviate irritation of the subject's skin induced by the formulated home care product.

In one aspect, the method is performed at room temperature. In one aspect, the method is carried out at a temperature in the range of -20°C to 78°C.

In one aspect, the perfume raw material is selected from the group consisting of synthetic ingredients, natural products, essential oils, and natural extracts.

In one aspect, the perfume raw material is a citrus oil.

In one aspect, the perfume raw material is treated prior to inclusion in the perfume.

In one aspect, the perfume raw material is processed after being included in the perfume.

In one aspect, the predetermined lower second POV level is 5-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 19 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 18 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 17 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 16 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 15 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 14 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 13 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 12 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 5 and 11 mmol/L. In one alternative aspect, the predetermined lower second POV level is 5-10 mmol/L. In one alternative aspect, the predetermined lower second POV level is 5-9 mmol/L. In one alternative aspect, the predetermined lower second POV level is 5-8 mmol/L. In one alternative aspect, the predetermined lower second POV level is 5-7 mmol/L. In one alternative aspect, the predetermined lower second POV level is 5-6 mmol/L.

In one aspect, the predetermined lower second POV level is 6-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 7 and 20 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 8 and 20 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 9 and 20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 10-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 11 and 20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 12-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 13-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 14-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 15-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 16-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 17-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 18-20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 19-20 mmol/L.

In one aspect, the predetermined lower second POV level is 20 mmol/L. In one alternative aspect, the predetermined lower second POV level is 19 mmol/L. In one alternative aspect, the predetermined lower second POV level is 18 mmol/L. In one alternative aspect, the predetermined lower second POV level is 17 mmol/L. In one alternative aspect, the predetermined lower second POV level is 16 mmol/L. In one alternative aspect, the predetermined lower second POV level is 15 mmol/L. In one alternative aspect, the predetermined lower second POV level is 14 mmol/L. In one alternative aspect, the predetermined lower second POV level is 13 mmol/L. In one alternative aspect, the predetermined lower second POV level is 12 mmol/L. In one alternative aspect, the predetermined lower second POV level is 11 mmol/L. In one alternative aspect, the predetermined lower second POV level is 10 mmol/L. In one alternative aspect, the predetermined lower second POV level is 9 mmol/L. In one alternative aspect, the predetermined lower second POV level is 8 mmol/L. In one alternative aspect, the predetermined lower second POV level is 7 mmol/L. In one alternative aspect, the predetermined lower second POV level is 6 mmol/L. In one alternative aspect, the predetermined lower second POV level is 5 mmol/L. In one alternative aspect, the predetermined lower second POV level is 4 mmol/L. In one alternative aspect, the predetermined lower second POV level is 3 mmol/L. In one alternative aspect, the predetermined lower second POV level is 2 mmol/L. In one alternative aspect, the predetermined lower second POV level is 1 mmol/L. In one alternative aspect, the predetermined lower second POV level is less than 1 mmol/L.

In one aspect, the predetermined lower second POV level is a 10% reduction in POV. In an alternative aspect, the predetermined lower second POV level is 20%, or 30%, or 40%, or 50%, or 60%, or 70%, or 80%, or 90% of the POV, or 100% reduction.

One aspect described herein provides a method of reducing the POV of a food ingredient, the method comprising the steps of adding an alpha-oxocarboxylic acid to the food ingredient having a first POV level; and said α-oxocarboxylic acid into said food ingredient for a time sufficient to reduce said first POV level to a predetermined lower second POV level.

One aspect described herein provides a method of reducing the POV of a flavored article, the method comprising adding an α-oxocarboxylic acid to the flavored article having a first POV level and mixing the α-oxocarboxylic acid into the flavored article for a time sufficient to reduce the first POV level to a predetermined lower second POV level.

Without intending to be bound by any particular theory, reducing the POV of a flavored article or food ingredient prevents and reduces the formation of intermediate glyceride hydroperoxides in the flavored article or food ingredient, Or hinder. reducing or inhibiting or preventing the formation of intermediate glyceride hydroperoxides in a flavored article or food ingredient thereby preventing, reducing rancidity or scorching in said flavored article or food ingredient; Or delay is possible.

Flavored articles include, for example, foodstuffs (eg, beverages), sweeteners such as natural or artificial sweeteners, pharmaceutical compositions, dietary supplements, functional foods, dental hygiene compositions, and cosmetics. Flavored articles may further comprise at least one flavorant.

In some aspects, the at least one flavoring agent can further modify the taste profile or taste attributes of the flavored article.

In some embodiments, the flavored article is a food product, such as, but not limited to, fruits, vegetables, juices, meat products such as ham and bacon, sausages, egg products, fruit juice concentrates, gelatin and jams and jellies. , candied and other gelatin-like products; dairy products and sherbets such as ice cream and sour cream; and products, cakes, cookies and confectionery such as candies and gummies, fruit flavored drops and chocolates, chewing gums, mints, creams, pies and breads.

In some aspects, the food product is a beverage, including, but not limited to, juices, juice-containing beverages, coffee, tea, carbonated beverages such as COKE and PEPSI, still soft drinks and other fruit beverages; Examples include sports drinks such as GATORADE, and alcoholic beverages such as beer, wine, and liqueurs.

Flavored goods may also include packaged processed products, such as granular flavor mixes that can be reconstituted with water to form non-carbonated beverages, instant pudding mixes, instant coffee and tea, coffee fresh, malted milk mixes. , pet food, livestock feed, tobacco, and baking ingredients such as powdered baking mixes for making bread, cookies, cakes, pancakes, donuts, and the like.

Flavored articles may also include diet or low calorie foods and beverages containing little or no sucrose. Flavored items may also include seasonings such as herbs, spices, condiments, umami seasonings (eg monosodium glutamate), dietary sweeteners, and liquid sweeteners.

In some aspects, the flavored article is a pharmaceutical composition, nutraceutical, functional food, dental hygiene composition, or cosmetic.

Dental hygiene compositions are known in the art and include, but are not limited to, toothpaste, mouthwash, plaque rinse, dental floss, tooth pain relievers (such as ANBESOL), and the like. In some aspects, the dental hygiene composition comprises one natural sweetener. In some aspects, the dental hygiene composition comprises two or more natural sweeteners. In some embodiments, the dental hygiene composition comprises sucrose and corn syrup or sucrose and aspartame.

In some aspects, cosmetics include, for example, but are not limited to, face creams, lipsticks, lip glosses, and the like. Other suitable cosmetics for use in the present disclosure include lip balms such as CHAPSTICK or BURT'S BEESWAX Lip Balm.

One alternative embodiment described herein provides a method for extending the shelf life of a food ingredient, the method comprising adding an alpha-oxocarboxylic acid to the food ingredient having a first POV level. and mixing the α-oxocarboxylic acid into the food ingredient for a time sufficient to reduce the first POV level to a predetermined lower second POV level. Without intending to be bound by any particular theory, reducing the first POV level to a predetermined lower second POV level prevents the formation of intermediate glyceride hydroperoxides in the food ingredient. , reduce or inhibit, such that the occurrence of rancidity or scalding in the food material is prevented, reduced or inhibited.

Without intending to be bound by any particular theory, the food ingredient may be used as a solvent for flavoring ingredients, or alternatively, the food ingredient itself may be the flavoring ingredient.

One alternative embodiment described herein provides a method for extending the shelf life of a flavored article, the method comprising adding an α-oxocarboxylic acid to the flavored article having a first POV level. and mixing the α-oxocarboxylic acid into the flavored article for a time sufficient to reduce the first POV level to a predetermined lower second POV level. . Without intending to be bound by any particular theory, reducing the first POV level to a predetermined lower second POV level prevents the formation of intermediate glyceride hydroperoxides in the flavored article. abolish, reduce or inhibit such that rancidity or scorching in the flavored article is prevented, reduced or inhibited.

In one aspect, the food ingredient is selected from the group consisting of fats, oils, or derivatives thereof. In one aspect, said derivatives thereof are selected from the group consisting of monoglycerides, diglycerides and phospholipids. In one aspect, the phospholipid is selected from the group consisting of lecithin, phosphatidylethanolamine, and modified triglycerides.

In one aspect, the food ingredients are treated prior to inclusion in the flavored article. In one alternative, the food ingredient is included after it has been included in the flavored article.

In one aspect, the food ingredient is a cooking oil. Examples of suitable cooking oils to be treated according to embodiments described herein include, but are not limited to, olive oil, palm oil, soybean oil, canola oil (rapeseed oil), corn oil, peanut oil, other vegetable oils, and Oils of animal origin, such as butter or lard, may be mentioned.

In one aspect, the method is performed at room temperature. In one aspect, the method is carried out at a temperature in the range of -20°C to 78°C.

In one aspect, the predetermined lower second POV level is 0-6 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 0 and 5 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0-4 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0-3 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 0 and 2 mmol/L. In one alternative aspect, the predetermined lower second POV level is between 0 and 1 mmol/L.

In one aspect, the predetermined lower second POV level is 1-6 mmol/L. In one alternative aspect, the predetermined lower second POV level is 2-5 mmol/L. In one alternative aspect, the predetermined lower second POV level is 3-5 mmol/L. In one alternative aspect, the predetermined lower second POV level is 4-5 mmol/L.

In one aspect, the predetermined lower second POV level is 5 mmol/L. In one alternative aspect, the predetermined lower second POV level is 4 mmol/L. In one alternative aspect, the predetermined lower second POV level is 3 mmol/L. In one alternative aspect, the predetermined lower second POV level is 2 mmol/L. In one alternative aspect, the predetermined lower second POV level is 1 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.9 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.8 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.7 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.6 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.5 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.4 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.3 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.2 mmol/L. In one alternative aspect, the predetermined lower second POV level is 0.1 mmol/L. In one alternative, the predetermined lower second POV level is 0 mmol/L.

In one aspect, the predetermined lower second POV level is a 10% reduction in POV. In an alternative aspect, the predetermined lower second POV level is 20%, or 30%, or 40%, or 50%, or 60%, or 70%, or 80%, or 90% of the POV, or 100% reduction.

In one aspect, the α-oxocarboxylic acid has FEMA-GRAS status. In one aspect, the α-oxocarboxylic acids are pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutarate, 2-oxopentane. The group consisting of dioates, indole-3-pyruvate, 2-thiopheneglyoxylate, trimethylpyruvate, 2-oxoadipate, 4-hydroxyphenylpyruvate, phenylpyruvate, 2-oxooctanoate, and mixtures thereof more selected.

In some aspects, the at least one α-oxocarboxylic acid is added as a salt to the perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient. Salts can be formed by reacting the at least one α-oxocarboxylic acid with an organic base.

In embodiments in which at least one α-oxocarboxylic acid is a monovalent acid, the resulting salt can be a monosalt. In embodiments where at least one α-oxocarboxylic acid is a diacid, the resulting salt may be a monosalt or a disalt.

Examples of suitable organic bases include, but are not limited to, the organic bases described in Examples 7-11 below, polymeric amines, polyethylamines, and the like.

Alternatively, the salt may be formed by reacting at least one α-oxocarboxylic acid with a cation selected from the group consisting of Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ .

An example of an ammonium salt includes an ammonium salt formed by reacting at least one α-oxocarboxylic acid with N-methyldiethanolamine.

In some aspects, the molar ratio of at least one α-oxocarboxylic acid to N-methyldiethanolamine can be 1:2, or 1:1, or 2:1.

In some aspects, at least one ammonium salt of an α-oxocarboxylic acid has surfactant properties. While not intending to be bound by any particular theory, generally molecules that produce surface-active properties contain ionic and/or highly polar functional groups and one or more spaced apart long hydrophobic segments. is a molecule. When a hydrophobic moiety such as an alkyl group with a sufficient number of carbons (eg 8-24) is attached to at least one ammonium salt of α-oxocarboxylic acid, the resulting molecule exhibits surfactant properties. can be done.

Without intending to be bound by any particular theory, it is believed that at least one ammonium salt of an α-oxocarboxylic acid having surface active properties or being ionic and highly polar is in contact with the user's skin during use. can be useful in a variety of home care and body care consumer products.

An example of an ammonium salt of at least one α-oxocarboxylic acid with surfactant properties includes, but is not limited to, diammonium made from a 1:2 molar ratio of α-ketoglutaric acid and N,N-dimethyldodecylamine. salts and monoammonium salts made with a 1:1 molar ratio of α-ketoglutaric acid and N,N-dimethyldodecylamine.

In some aspects, at least one ammonium salt of an α-oxocarboxylic acid has softening properties. Without intending to be bound by any particular theory, it is generally believed that mostly hydrophobic and inert molecules with low melting points (relative to body temperature) give rise to softening properties, such as softeners. can act. Useful emollients have oily or grease-like properties and act as emollients and/or moisture barriers when applied to the skin. Although the ammonium salt of at least one α-oxocarboxylic acid mentioned above is characterized as being ionic and highly polar, a sufficient amount of the at least one ammonium salt of α-oxocarboxylic acid is hydrophobic If moieties can be included, the resulting molecule can exhibit softening characteristics.

One approach is to use an amine with three long hydrophobic or oily substituents as the basic building block of at least one ammonium salt of an α-oxocarboxylic acid. Such molecules may have hydroperoxide consuming/POV reducing properties and softening properties, thus providing additional benefits to the user. They are useful in a variety of body care consumer products that, upon use, are placed on the skin and left on for some period of time to moisturize, protect, or soften the user's skin.

Examples of at least one ammonium salt of an α-oxocarboxylic acid having softening properties include, but are not limited to, α-ketoglutarate and tris[2-(2-(methoxyethoxy)ethyl in a molar ratio of 1:2. ] diammonium salts made with amines.

In some embodiments, at least one α-oxocarboxylic acid is dissolved in a solvent such as acetone, and N-methyldiethanolamine is added to the solution to convert at least one α-oxocarboxylic acid to N - can be reacted with methyldiethanolamine. The opaque white emulsion so obtained is then agitated, during which the second phase is allowed to coalesce. The mixture is then placed in the freezer for at least 30 minutes, whereupon the bottom phase thickens to a waxy solid. The top layer can then be easily removed by decantation while still cold and discarded. Residual acetone can be removed from the bottom product layer by a stream of nitrogen followed by room temperature treatment in a vacuum oven, yielding a pale yellow, highly viscous oil at room temperature containing the diammonium salt. be able to.

Other compounds suitable for forming ammonium salts by reaction with at least one α-oxocarboxylic acid include 2-(dimethylamino)ethanol and N,N-dimethyldodecylamine.

In one aspect, the salt converts the α-oxocarboxylic acid from 2-(dimethylamino)ethanol, N,N-dimethyldodecylamine, tris[2-(2-(methoxyethoxy)ethyl]amine, and N-methyldiethanolamine. is an ammonium salt formed by reacting with a compound selected from the group consisting of

Without intending to be bound by any particular theory, the at least one ammonium salt of an alpha-oxocarboxylic acid may be used in treated perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, Or, the occurrence of acid-catalyzed chemical reactions that can harm and/or degrade food ingredients can be prevented. Alternatively, the ammonium salt of at least one α-oxocarboxylic acid can improve the solubility of the at least one α-oxocarboxylic acid. Alternatively, at least one ammonium salt of an α-oxocarboxylic acid can provide emulsifying action.

Without intending to be bound by any particular theory, the at least one alpha-oxocarboxylic acid salt may be used in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. can be an emulsifier when added to an aqueous system containing Such compositions may be useful in salad dressings, marinades, sauces, and the like.

In one aspect, the at least one ammonium salt of an α-oxocarboxylic acid may be further combined with at least one other drug. In one aspect, the at least one other agent is chitosan.

In one aspect, α-ketoglutarate is added to a mixture of palmitic acid and chitosan. Such compositions can be emulsifiers for edible oils in aqueous systems and can be useful in salad dressings, marinades, sauces and the like.

In one aspect, the time sufficient to reduce the POV to a predetermined lower second POV level is 30 days, or 29 days, or 28 days, or 27 days, or 26 days, or 25 days, or 24th or 23rd or 22nd or 21st or 20th or 19th or 18th or 17th or 16th or 15th or 14th or 13th or 12th , or 11 days, or 10 days, or 9 days, or 8 days, or 7 days, or 6 days, or 5 days, or 4 days, or 3 days, or 2 days, or 1 day.

In one aspect, the time period sufficient to reduce the POV to the predetermined lower second POV level is greater than 24 hours. In one aspect, the time sufficient to reduce the POV to the predetermined lower second POV level is 48 hours, or 47 hours, or 46 hours, or 45 hours, or 44 hours, or 43 hours, or 42 hours, or 41 hours, or 40 hours, or 39 hours, or 38 hours, or 37 hours, or 36 hours, or 35 hours, or 34 hours, or 33 hours, or 32 hours, or 31 hours, or 30 hours or 29 hours or 28 hours or 27 hours or 26 hours or 25 hours or 24 hours or 23 hours or 22 hours or 21 hours or 20 hours or 19 hours or 18 hours, or 17 hours, or 16 hours, or 15 hours, or 14 hours, or 13 hours, or 12 hours, or 11 hours, or 10 hours, or 9 hours, or 8 hours, or 7 hours, or 6 hours, or 5 hours , or 4 hours, or 3 hours, or 2 hours, or 1 hour.

In one aspect, the time sufficient to reduce the POV to the predetermined lower second POV level is 60 minutes or less. In one aspect, the time sufficient to reduce the POV to the predetermined lower second POV level is 60 minutes, or 50 minutes, or 40 minutes, or 30 minutes, or 20 minutes, or 10 minutes, or 9 minutes, or 8 minutes, or 7 minutes, or 6 minutes, or 5 minutes, or 4 minutes, or 3 minutes, or 2 minutes, or 1 minute.

Without intending to be bound by any particular theory, the amount of alpha-oxocarboxylic acid added to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients and/or Alternatively, the rate is controlled so that excess α-oxocarboxylic acid does not accumulate. Excessive accumulation of α-oxocarboxylic acids can result in, for example, acid-catalyzed damage to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients.

The amount of alpha-oxocarboxylic acid added to perfume formulations, body care products, perfume ingredients, flavored articles, or food ingredients depends on several factors, including, but not limited to, alpha - Stability of oxocarboxylic acids in solution, solubility of alpha-oxocarboxylic acids in perfume formulations, body care products, perfume ingredients, flavored articles or food ingredients, pKa of alpha-oxocarboxylic acids, rate of POV reduction , the effect of α-oxocarboxylic acids on the olfactory properties and/or taste of perfume formulations, body care products, perfume ingredients, flavored articles, or food ingredients.

By way of example, pyruvate, phenylpyruvate, and 2-oxovaleric acid have strong aromas and are used as FEMA-GRAS perfume constituents. In these aspects, for example, the characteristic odor of α-oxocarboxylic acids may alter the organoleptic properties of perfume formulations or be incompatible.

Instead of using an odorless α-oxocarboxylic acid in the embodiment described herein, it generates an odor-friendly carboxylic acid that is odor-friendly in perfumes and when consumed in reaction with hydroperoxides. An α-oxocarboxylic acid is used that allows By way of example, indole-3-pyruvate can be used to reduce the POV of fragrances with indole-based characteristics (ie containing perceptible amounts of indole and/or skatole).

Examples of odorless α-oxocarboxylic acids include α-ketoglutaric acid. While not intending to be bound by any particular theory, it is believed that odorless α-oxocarboxylic acids are more suitable for use in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, than scented α-oxocarboxylic acids. It has less effect on the organoleptic properties of flavored articles or food ingredients and can reduce POV of perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles or food ingredients.

The solubility of α-oxocarboxylic acids can vary in different formulations of compositions containing α-oxocarboxylic acids. Taking α-ketoglutarate as an example, the solubility of this α-oxocarboxylic acid may be low in perfume raw materials such as citrus oils. However, the addition of perfume raw materials to a hydroalcoholic perfume base (an aqueous solution containing 80%-90% ethanol) can increase the solubility of this α-oxocarboxylic acid. In these embodiments, if the α-oxocarboxylic acid is a strong acid, in solution in the hydroalcoholic perfume base, to prevent acid-catalyzed degradation of the perfume raw material from altering the organoleptic properties of the perfume raw material or perfume formulation. It may be necessary to limit the amount of α-oxocarboxylic acid.

An example of how an α-oxocarboxylic acid may be labile in solution is oxaloacetic acid, which is labile in aqueous solution. In these embodiments, oxaloacetate decomposes to pyruvate and carbon dioxide. In these aspects, the POV reduction of the perfume formulation, body care product, perfume ingredient, flavored article, or food ingredient is obtained with oxaloacetate, pyruvate, or any combination thereof.

In some embodiments, the α-oxocarboxylic acid has low solubility in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. By way of example, at the lower limit of solubility, an α-oxocarboxylic acid can be virtually insoluble in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. In contrast, at the upper limit of solubility, α-oxocarboxylic acids may be fully miscible in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients.

Examples of low solubility embodiments of α-oxocarboxylic acids in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients include, but are not limited to: pyruvic acid. In these embodiments, the α-oxocarboxylic acid can be added in concentrations above its solubility, thus forming a two-phase system, one phase consisting of the α-oxocarboxylic acid. While not intending to be bound by any particular theory, the components of perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients consist of this α-oxocarboxylic acid. can enter the phase. Perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients exposed to a phase consisting of an α-oxocarboxylic acid resulting in a perfume formulation, body care product, Acid-sensitive compounds in cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients can be chemically altered/damaged.

Illustratively, essential oils are rich in terpene compounds. As a class, terpenes are generally susceptible to acid-catalyzed rearrangements. Thus, exposure of a component of a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient to a phase consisting of alpha-oxocarboxylic acids may result in a perfume formulation, body care product, Acid sensitive compounds in products, cosmetics, home care products, perfume ingredients, flavored articles or food ingredients may be chemically altered/damaged and thus perfume formulations, body care products, cosmetics, home care products, perfumes The organoleptic properties of an ingredient, flavored article, or food ingredient may vary.

Thus, in some aspects described herein, the α-oxocarboxylic acid is added at a rate to minimize or prevent the formation of a second phase of α-oxocarboxylic acid. Such addition rates may equal chemical reaction rates that reduce the POV of perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. While not intending to be bound by any particular theory, adding the α-oxocarboxylic acid at the same rate as the chemical reaction rate can prevent the accumulation of the α-oxocarboxylic acid and thus the second phase. Volume can be minimized and perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients can be prevented from entering the highly acidic phase of α-oxocarboxylic acids. .

Alternatively, α-oxocarboxylic acids can be effectively dispersed in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients to form two phase systems. Due to the increased surface area that the phases come in contact with, chemical reaction rates that reduce the POV of perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients can be increased.

Examples of embodiments in which α-oxocarboxylic acids are not poorly soluble in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients include, but are not limited to, 2-oxocarboxylic acids. valeric acid. While not intending to be bound by any particular theory, embodiments in which alpha-oxocarboxylic acids are not poorly soluble in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. can result in the formation of a single phase. In that case, the added α-oxocarboxylic acid is soluble in the perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient being treated, and thus after addition Diluted immediately. In this case, if the rate of addition is close to the rate of reaction, the α-oxocarboxylic acid is also consumed as it is being added. The concentration of α-oxocarboxylic acid remains low and acid-induced changes are minimized.

In one alternative embodiment, the concentration of unreacted α-oxocarboxylic acid is minimized through the use of buffers and the α-oxocarboxylic acid is present as a deprotonated anion.

The anionic forms of α-oxocarboxylic acids are less reactive with hydroperoxides than the protonated acidic forms. However, when the acidic form is consumed in reaction with the hydroperoxide, the equilibrium of the α-oxocarboxylic acid-base pair is quickly restored according to the pKa of the α-oxocarboxylic acid, and the anionic form immediately scavenges protons from the medium. As a result, the acid forms of hydroperoxide-reactive α-oxocarboxylic acids are further produced. This ensures that the overall pH of the medium is at a moderate pH level that does not cause acid damage to the components of perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. Maintains acidity. At the same time, however, α-oxocarboxylic acids in reactive protonated form are present in relatively low but constant concentrations, and they are compensated from the sink of the relatively inert anionic form at the end where they are consumed.

For example, taking pyruvic acid for illustrative purposes only, pyruvic acid has a pKa of 2.50 and is used in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients at a pH of 5.5. Buffering to 5 (a difference of 3 log units) increases the concentration of pyruvate anions by a factor of 10 ³ (or 1000) compared to pyruvate (according to the Henderson-Hasselbalch equation).

In one aspect, the concentration of α-oxocarboxylic acid after addition to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients is between 0.001 and 10% by weight. Range. In one aspect, the concentration of α-oxocarboxylic acid after addition to the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient is 10% by weight. Alternatively, the concentration of α-oxocarboxylic acid after addition to the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient is 9% by weight, or 8% by weight, or 7% by weight, or 6% by weight, or 5% by weight, or 4% by weight, or 3% by weight, or 2% by weight, or 1% by weight, or 0.9% by weight, or 0.8% by weight, or 0.7 wt%, or 0.6 wt%, or 0.5 wt%, or 0.4 wt%, or 0.3 wt%, or 0.2 wt%, or 0.1 wt%, or 0 0.09 wt%, or 0.08 wt%, or 0.07 wt%, or 0.06 wt%, or 0.05 wt%, or 0.04 wt%, or 0.03 wt%, or 0. 02 wt%, or 0.01 wt%, or 0.009 wt%, or 0.008 wt%, or 0.007 wt%, or 0.006 wt%, or 0.005 wt%, or 0.004 % by weight, or 0.003% by weight, or 0.002% by weight, or 0.001% by weight.

The α-oxocarboxylic acid may be added as such to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients, or alternatively Acids may be diluted prior to addition to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. Any diluent that can be used in the perfumery industry may be used. Suitable diluents include, but are not limited to, isopropanol, ethanol, diglyme, triethylene glycol, and the like. The α-oxocarboxylic acid can be diluted 1:1, or 1:2, or 1:3, or 1:4 or more with a diluent.

While not intending to be bound by any particular theory, the choice of diluent may also be added to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. The amount of carboxylic acid can be affected. The choice of diluent can also affect the rate at which the α-oxocarboxylic acid is added to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. For example, using pyruvate as the α-oxocarboxylic acid and ethanol as the solvent, pyruvate should be added in an amount and/or rate that minimizes ester formation with ethanol.

The α-oxocarboxylic acid can be added to any volume of perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient. For example, the α-oxocarboxylic acid is used in 1000 ml of perfume formulations, body care products or perfume raw materials, or 900 ml, or 800 ml, or 700 ml, or 600 ml, or 500 ml, or 400 ml, or 300 ml, or 200 ml, or 100 ml, or 90ml, or 80ml, or 70ml, or 60ml, or 50ml, or 40ml, or 30ml, or 20ml, or 10ml, or 9ml, or 8ml, or 7ml, or 6ml, or 5ml, or 4ml, or 3ml, or 2ml , or 1 ml of perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients.

In one aspect, the α-oxocarboxylic acid may be added to a perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient over 80 minutes. Alternatively, alpha-oxocarboxylic acids can be added to perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients for 70 minutes, or 60 minutes, or 50 minutes, or 40 minutes. , or 30 minutes, or 20 minutes, or 10 minutes, or 9 minutes, or 8 minutes, or 7 minutes, or 6 minutes, or 5 minutes, or 4 minutes, or 3 minutes, or 2 minutes, or 1 minute may be added.

In one aspect, the α-oxocarboxylic acid is added to the perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient at a rate of 0.25 ml/min. In some aspects, the addition rate is higher than 0.25 ml/min. In some aspects, the addition rate is less than 0.25 ml/min.

In some aspects, the rate at which the α-oxocarboxylic acid is added to the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient is constant. In some aspects, the rate at which the α-oxocarboxylic acid is added to the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient is varied. In one aspect, the α-oxocarboxylic acid is used in perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients at a rate equal to the rate at which the α-oxocarboxylic acid is oxidized. is added to In some aspects, the rate at which an α-oxocarboxylic acid is oxidized can be determined by measuring the POV of a treated perfume formulation, body care product, or perfume raw material. Referring to FIGS. 2-4, by way of example, the POV reduction rate can have a first rate, which is faster than the second rate. In an exemplary aspect, the duration of the first speed is shorter than the duration of the second speed.

In one alternative embodiment, the α-oxocarboxylic acid may be added and quenched after a period of time. Alpha-oxocarboxylic acids may be quenched 80 minutes after addition to the material. Alternatively, the α-oxocarboxylic acid is added to the substance 70 minutes, or 60 minutes, or 50 minutes, or 40 minutes, or 30 minutes, or 20 minutes, or 10 minutes, or 9 minutes, or 8 minutes, or 7 minutes, or 6 minutes, or 5 minutes, or 4 minutes, or 3 minutes, or 2 minutes, or 1 minute.

In one aspect, the method further comprises extracting excess alpha - including removing the oxocarboxylic acid.

In one aspect, excess α-oxocarboxylic acid is removed from perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients by liquid-liquid extraction.

In one aspect, excess alpha-oxocarboxylic acid is removed from perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients by liquid-liquid extraction with water. .

In one aspect, other byproducts of the reaction that reduce the POV of the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient to a predetermined lower second POV level. is also removed by liquid-liquid extraction. All by-products, or alternatively some by-products, can be removed.

In one aspect, the method further comprises treating the perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient after removing excess α-oxocarboxylic acid to Including reducing the acidity of the substance. In some aspects, treatment includes addition of a buffer such as, for example, triethanolamine, or N-methyldiethanolamine.

In one aspect, substances are treated with carbonates to reduce the acidity of perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients.

In one aspect, a method of reducing the POV of a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient comprises:
a) introducing a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article or food ingredient into a reactor, said perfume formulation, body care product, cosmetic, home care a step in which the product, perfume ingredient, flavored article or food ingredient is under an inert gas, for example argon;
b) introducing an α-oxocarboxylic acid into the perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient at a rate of 0.25 ml/min, The alpha-oxocarboxylic acid is diluted 1:4 with a diluent and the alpha-oxocarboxylic acid is added to the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient. constantly stirring during introduction, step;
c) introducing water and anhydrous sodium carbonate to the mixture and allowing the reaction to continue until there is no visible _CO2 evolution; obtaining a perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient having a POV;
including.

Examples of methods according to the above aspects are described in Examples 1-4 below.

In some aspects, the second phase of the α-oxocarboxylic acid in the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient is It is a "dwelling" composition. Without intending to be bound by any particular theory, it is believed that the amount of α-oxocarboxylic acid present in the two phases is in equilibrium and that the reduction in POV results in a Carboxylic acids can migrate into phases containing perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. An example of this aspect is described in Example 5 below.

In some embodiments, the “dwell” composition of α-oxocarboxylic acid is combined into a single phase composition with perfume formulations, body care products, cosmetics, home care products, perfume ingredients, flavored articles, or food ingredients. include. In these embodiments, the composition further comprises a buffer and the pH is set to maintain the α-oxocarboxylic acid present predominantly in the unprotonated form, wherein the unprotonated form of the composition is It cannot react with POV-causing chemical species (peroxides, organic hydroperoxides, peroxyhemiacetals, etc.). Without intending to be bound by any particular theory, the amount of α-oxocarboxylic acid present in unprotonated form is in equilibrium with the amount of α-oxocarboxylic acid present in protonated form, and the POV The reduction can result in a shift of the α-oxocarboxylic acid from the unprotonated to the protonated form. An example of this aspect is described in Example 4 below.

In these examples, "dwelling" compositions of α-oxocarboxylic acids can reduce POV over time.

Accordingly, one aspect described herein is the use of (a) a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient, and (b) an α-oxocarboxylic acid. wherein the α-oxocarboxylic acid is present in the composition in an amount sufficient to reduce the POV from a first level to a predetermined lower second POV level , to provide the composition.

In one aspect, the α-oxocarboxylic acid is present in the composition in an amount sufficient to prevent the predetermined lower second POV level from changing over time. The time may be hours, days, weeks, or longer.

One aspect described herein is a composition comprising (a) a perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient, and (b) an α-oxocarboxylic acid wherein the alpha-oxocarboxylic acid reduces, prevents, or increases the POV of the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient; A composition is provided which is present in the composition in an amount sufficient to provide relief.

In one aspect, the concentration of α-oxocarboxylic acid in the composition ranges from 0.001 to 10% by weight.

In one aspect, the α-oxocarboxylic acids are pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutarate, 2-oxopentane. The group consisting of dioates, indole-3-pyruvate, 2-thiopheneglyoxylate, trimethylpyruvate, 2-oxoadipate, 4-hydroxyphenylpyruvate, phenylpyruvate, 2-oxooctanoate, and mixtures thereof more selected.

In one aspect, the perfume raw material is a citrus oil.

An example of a composition according to the above embodiments is described in Example 5 below.

In some embodiments, at least one α-oxocarboxylic acid or salt thereof may be applied to or contained in or covalently attached to the solid phase substrate, wherein at least one α-oxocarboxylic acid or The solid phase substrate containing the salt is used for processing perfume formulations, body care products, cosmetics, perfume ingredients, flavored articles, or food ingredients.

Any inert, finely divided or high surface area material can be used as the solid support. Examples include, but are not limited to, metals, glasses, foamed ceramics, plastics, or inorganic solids. The solid phase support may also comprise the bottom and/or walls of a container containing perfume formulations, body care products, cosmetics, perfume ingredients, flavored articles, or food ingredients.

In some aspects, the solid phase support has a high surface area:volume ratio. Examples of such solid phase supports include, but are not limited to, steel wool. An example of a composition processed by embodiments using the solid support described above is described in Example 24 below.

The invention is best illustrated by, but not limited to, the examples below.

EXAMPLES Example 1: Reduction of POV of Citrus Oils Using Pyruvate According to One Embodiment Described herein Placed in a 100 mL round bottom flask with stir bar and blanket of argon gas.

A 4:1 v/v isopropanol/pyruvic acid solution was made. 20 mL of this pyruvic acid solution was added dropwise to the stirred citrus oil at a rate of 0.25 mL/min using a syringe pump.

Once the addition was complete, 10 mL of water and 100 mg of anhydrous sodium carbonate were added to the flask and stirring continued. When visible CO ₂ evolution ceased (approximately 2-4 minutes), the aqueous layer was removed with a pipette and discarded. POV measurements of mixed citrus oils were performed before and after pyruvate treatment.

The POV before treatment was 27.261 mEq/L and the POV after treatment was 4.786 mEq/L. /L. This was an approximately 82% reduction in POV.

Example 2: Reduction of POV of limonene using 2-oxo-valeric acid according to one aspect described herein 10 mL of autoxidized limonene was added to a 30 mL glass vial at room temperature with a stir bar and a blanket of argon gas. I put it in. 100 μL of 2-oxovaleric acid was added. The vial was shaken once and left for 50 minutes. No further treatment was performed prior to POV testing. POV measurements of limonene were performed before and after 2-oxovaleric acid treatment. Pre-treatment POV was 65.97 mEq. /L and post-treatment POV was 17.21 mEq. /L. This was an approximately 74% reduction in POV.

Example 3: Reduction of POV of limonene using 2-oxo-butyric acid according to one aspect described herein 20 mL of autoxidized limonene was placed in a 30 mL glass vial at room temperature with a stir bar and a blanket of argon gas. rice field. 250 μL of 2-oxobutyric acid was added. The vials were shaken once and left to monitor POV values as a function of time. The data collected are shown in the table below.

The results showed that the POV decreased sharply at first, after which the rate of POV decrease slowed down. Although this may be due to reagent depletion, the reduction in POV on a molar basis is insufficient for the total amount of 2-oxobutyric acid added. It may be that some hydroperoxides break down very quickly, while others break down much more slowly. An additional 500 μL of 2-oxobutyric acid was added and the sample was allowed to stand for an additional 24 hours before measurement, giving a POV of 8.577 mEq. /L (87.1% reduction in total).

Example 4: Reduction of POV of limonene using 2-phenylglyoxylic acid according to one embodiment described herein 20 mL of autoxidized limonene was placed in a 30 mL glass vial at room temperature with a stir bar and a blanket of argon gas. rice field. 200 mg of phenylglyoxylic acid was added and dissolved. The vials were shaken once and left to monitor POV values as a function of time. The data collected are shown in the table below.

Example 5: Reduction of POV of limonene using 2-oxo-2-furanacetic acid according to one aspect described herein 20 mL of mixed citrus oil was added to a 30 mL glass at room temperature with a stir bar and a blanket of argon gas. placed in a vial. 400 mg of α-oxo-2-furanacetic acid was added. The vials were shaken once and left to monitor POV values as a function of time. Since most of the added α-oxo-2-furanacetic acid did not dissolve, the limited solubility of this acid is believed to serve as a controlled release mechanism. Thus, it is believed that as α-oxo-2-furanacetic acid in solution is consumed by hydroperoxide, it becomes more soluble according to the solubility constant. The undissolved solids thus act as a sink to maintain a stable low concentration of dissolved α-oxo-2-furanacetic acid in the mixed citrus oil.

In this case, the time between measurements was relatively long (days instead of minutes), so it is possible that the untreated mixed citrus oil was further oxidized during the course of the experiment. Therefore, the POV of the treated oil was compared to the POV of the untreated oil, but the untreated oil measurement at each point was redetermined (rather than using only a single initial value). The data collected are shown in the table below.

Example 6: Reduction of POV of skin cream formulations using 2-oxovaleric acid or phenylglyoxylic acid according to one embodiment described herein 0.5 parts cetylstearyl alcohol, 6.0 parts wool wax alcohol, and A skin cream formulation consisting of 93.5 parts of white petrolatum was made according to German Pharmacopoeia DAB 2008.

This skin cream was divided into two separate preparations. A high limonene oxide sample was added to both preparations so that the concentration of limonene oxide in the first preparation was approximately one-third the concentration of limonene oxide in the second preparation. Analysis of the limonene oxide sample showed that the sample contained a mixture of isomers of limonene hydroperoxide.

The initial POV of the first and second skin cream preparations were each measured and then treated with 2-oxovaleric acid or phenylglyoxylic acid as follows: 2 preparation) or phenylglyoxylic acid (first preparation) were mixed in thoroughly. The POV of the preparation was measured during the addition of 2-oxovaleric acid. Once the addition of 2-oxovaleric acid or phenylglyoxylic acid was complete, the treated preparation was allowed to stand at room temperature. The POV data obtained were corrected for the exact weight of the aliquot of cream titrated at each time point and normalized to the starting POV as a percentage value.

A second preparation containing a larger amount of the limonene oxide sample was treated with approximately 2.3% w/w of 2-oxovaleric acid. The results are shown in Figure 3 below.

A first preparation containing a smaller amount of the limonene oxide sample was treated with approximately 3.9% w/w of 2-phenylglyoxylic acid. The results are shown in Figure 4 below.

Example 7: Reaction of α-ketoglutarate (CAS#328-50-7) with N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a 1:2 molar ratio to form a diammonium salt α - 1.461 g (0.01 mol) of ketoglutaric acid was dissolved in 10 mL of dry acetone to give a clear solution. This solution was added in one portion to 2.384 g (0.02 mol) of neat NMDEA. The opaque white emulsion was stirred vigorously for 3-4 minutes during which time the second phase coalesced. When the mixture was placed in the freezer for at least 30 minutes, the bottom phase thickened to a waxy solid. While cold, the top layer was easily removed by decantation or pipette and discarded. Residual acetone was removed from the bottom product layer by a stream of nitrogen followed by room temperature treatment in a vacuum oven. This gave a clear pale yellow highly viscous oil containing the diammonium salt (AKG-DiNMDEA salt).

A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent (6 mL oil to 25 mL solvent) at approximately 19.4% v/v. Approximately 400 mg (2.0% w/v) of AKG-DiNMDEA salt was dissolved in 20 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

These data show an approximately 94% reduction in POV 24 hours after the addition of AKG-DiNMDEA salt.

In addition to the above treatments for the model perfumes, similar experiments were performed with mixed citrus oils. Mixed citrus oil samples were made by combining lime oil, orange oil, grapefruit oil, lemon oil, mandarin oil, tangerine oil, and bergamot oil, so the various terpene hydroperoxides were present in the treated mixtures tested. I decided to Approximately 200 mg (1.0% w/v) of AKG-DiNMDEA salt was added to 20 mL of mixed citrus oil. Even with vigorous mixing, the salt did not appear to have completely dissolved. Nevertheless, the POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated mixed citrus oil samples were manipulated and tested similarly to the treated oils. Results are shown in the table below.

According to this, the improvement in the POV condition of the oil is only moderate to good, with a 59% reduction in a full day after treatment. This is probably due to the low solubility of 2-oxoacid salts in citrus oils.

Example 8: By reaction of α-ketoglutarate (CAS#328-50-7) and N,N-dimethyldodeclyamine (DiMeC12A, CAS#112-18-5) at a 1:2 molar ratio Diammonium Salt Formation 1.461 g (0.01 mol) of α-ketoglutaric acid was dissolved in 6 mL of dry acetone. This solution was added dropwise with stirring over 1-2 minutes to another solution of 4.268 g (0.02 mol) of N,N-dimethyldodecylamine in 6 mL of dry acetone. No visible signs of reaction were observed except that the combined solution warmed to about 35-40°C. The mixture was shaken briefly but vigorously and then cooled in the freezer for 30 minutes. No precipitation of the product occurred even at low temperatures, but when the mixture was shaken again the whole mass solidified almost instantaneously to a solid white waxy material. The solid was warmed to 30-35° C. to reliquefy the product so that entrapped acetone could be removed by nitrogen flow followed by room temperature treatment in a vacuum oven. This gave a white waxy solid containing the diammonium salt (AKG-DiMeC12A salt).

A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent (6 mL oil to 25 mL solvent) at approximately 19.4% v/v. Approximately 400 mg (2.0% w/v) of AKG-DiMeC12A salt was dissolved in 20 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

In addition to the above treatments for the model perfumes, similar experiments were performed with mixed citrus oils. Mixed citrus oil samples were made by combining lime oil, orange oil, grapefruit oil, lemon oil, mandarin oil, tangerine oil, and bergamot oil, so the various terpene hydroperoxides were present in the treated mixtures tested. I decided to Approximately 200 mg (1.0% w/v) of AKG-DiMeC12A salt was dissolved in 20 mL of mixed citrus oil and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated mixed citrus oil samples were manipulated and tested similarly to the treated oils. Results are shown in the table below.

These data show an 89.0% reduction in POV within 72 hours (3 days) after AKG-DiMeC12A addition. After the 260 min time point, no further reaction occurred over time, indicating that AKG-DiMeC12A may have been depleted.

Surface tension measurement of aqueous AKG-DiMeC12A: To evaluate the surfactant properties of AKG-DiMeC12A, the reduction in surface tension it produces in aqueous solution was measured against pure water. Measurements were carried out on a Kruss DSA100S tensiometer by the hanging drop method. A 0.14% by weight aqueous solution of AKG-DiMeC12A was used for the measurement. This concentration was chosen to allow comparison of the results with the known detergent sodium dodecyl sulfate (SDS) 5 mM literature value of approximately 0.15% by weight. The results show that AKG-DiMeC12A has remarkable surfactant properties:
Pure water -71.57 mN/m
AKG-DiMeC12A-32.08mN/m
For comparison, at 273 K, the air-water surface tension of a 5 mM concentration of SDS (approximately 0.15 wt%, very close to the 0.14 wt% used here) varies from 33.5 to 35.5 mN/m (see Hernainz, F. et al, Colloids Surf. A, 2002, 196, 19-24).

Example 9: Diammonium salt by reaction of α-ketoglutarate (CAS#328-50-7) and 2-(dimethylamino (ethanol (Deanol, CAS#108-01-0)) in a 1:2 molar ratio 1.461 g (0.01 mol) of α-ketoglutaric acid was dissolved in 10 mL of dry acetone to give a clear solution which was added to 1.783 g (0.01 mol) of neat 2-dimethylaminoethanol (“Deanol”). .02 mol) over 1-2 minutes with stirring.The opaque white emulsion was stirred vigorously for 1 minute during which time the second phase coalesced.The mixture was placed in the freezer overnight and the bottom phase thickened to a very viscous, cloudy oil.While cold, the top layer was easily removed by decantation or pipette and discarded.From the bottom product layer, a stream of nitrogen followed by a vacuum oven. Residual acetone was removed by room temperature treatment with , which gave a clear, colorless, viscous oil at room temperature containing the diammonium salt (AKG DiDeanol salt).

A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent (6 mL oil to 25 mL solvent) at approximately 19.4% v/v. Approximately 200 mg (1.0% w/v) of AKG DiDeanol salt was dissolved in 20 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

Example 10: Formation of ammonium salt by reaction of pyruvic acid (CAS#328-50-7) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a 1:1 molar ratio. 642 g (0.03 mol) was dissolved in 5 mL of dry acetone to give a clear solution. This solution was added dropwise over 1-2 minutes with stirring to a second solution made up of 3.575 g (0.03 mol) of NMDEA and 5 mL of dry acetone. The resulting mixture became warm (approximately 35-45° C.) and cloudy upon addition of the acid solution. The cloudy emulsion was stirred vigorously for 1 minute during which time the second phase coalesced. When the mixture was placed in the freezer for at least one hour, the bottom phase became considerably more viscous, but did not solidify. While cold, the top layer was easily removed by decantation or pipette and discarded. Residual acetone was removed from the bottom product layer by a stream of nitrogen followed by room temperature treatment in a vacuum oven. This gave a clear, golden, highly viscous oil at room temperature containing the diammonium salt (PA-NMDEA salt).

A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of lime oil, orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent at approximately 16.7% v/v (40 mL of oil loaded into 200 mL of solvent, 240 mL of perfume combined). Approximately 150 mg (1.0% w/v) of PA-NMDEA salt was dissolved in 15 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

These data indicate that PA-NMDEA was depleted at 73.3 hours. This is because after that, the POV of the sample never decreased even if the reaction time was long. This represents a greater than 90% reduction in POV. The untreated oil averaged after 3 days was (6.66 + 6.58)/2 = 6.62 mmol/L, so 0.58/6.62 x 100 = 8.76% remained, or a POV of 91.2%. reduced).

Example 11: Formation of ammonium salt by reaction of phenylglyoxylic acid (PhGA, CAS#611-73-4) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a 1:1 molar ratio PhGA 1.501 g (0.01 mol) was dissolved in 5 mL of dry acetone to give a clear solution. This solution was added all at once to a second solution made up of 1.192 g (0.01 mol) of NMDEA and 5 mL of dry acetone. The resulting mixture became warm (approximately 30-35° C.) and pale yellow with no cloudiness or precipitate. The solution was agitated for 1 minute and then placed in the freezer for 30 minutes. Still no precipitate or second layer formed, but the solution was apparently supersaturated. Attempts were made to remove the solvent acetone with a stream of nitrogen, but a viscous paste of white crystalline material formed almost instantaneously when the stream of nitrogen touched the solution. The crystals began to dissolve in acetone again as the mixture warmed to room temperature. The product was refrozen to reprecipitate the highly crystalline product, and the supernatant acetone was pipetted off as much as possible while still cold. Residual acetone was then removed with a stream of nitrogen to yield pure white needles. The crystalline product containing the diammonium salt (PhGA-NMDEA salt) is extremely hygroscopic and liquefies rapidly upon exposure to the ambient atmosphere. Or it had to be placed under a strong nitrogen blanket. Weight/yield was not given due to hygroscopicity.

A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of lime oil, orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent at approximately 16.7% v/v (40 mL of oil loaded into 200 mL of solvent, 240 mL of perfume combined). Approximately 150 mg (1.0% w/v) of PhGA-NMDEA salt was dissolved in 15 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

These data indicate that the phenylglyoxylic acid moiety does lower the POV of the model perfume, but is less reactive than the non-aryl pyruvates tested. This reactivity difference can be useful in some cases.

Example 12: Reduction of POV of Sunflower Oil Using 2-Oxovaleric Acid According to One Embodiment Described herein At room temperature, opening 25 mL of sunflower oil (stock with approximately 25% atmospheric gas phase fraction) from a 1 quart container; shelf life unknown) was placed in a 30 mL vial. 250 μL of 2-oxovaleric acid was added. The vial was shaken and left on the benchtop under laboratory lighting at ambient temperature. No further treatment was performed prior to POV testing.

POV measurements of sunflower oil were performed before and after 2-oxovaleric acid treatment. Untreated oil was also remeasured periodically for comparison, since opening the bottle replenishes the gas phase portion of the atmosphere and can raise the POV of the bottle contents. Percentage reductions were always calculated relative to the most recent POV value for untreated oil, and where there were multiple measurements, the average value (shown in parentheses) was used in the calculation. Results are shown in the table below.

Ｎ／Ａ＝該当なし

N/A = Not applicable

The untreated sunflower oil was only left in the bottle at room temperature for 15 days, except that the gas phase portion was replenished with ambient air during the brief bottle opening required each time the sample was taken. POV increased by almost 40% (12.30/8.81 mmol/L x 100 = 139.6%).

On the other hand, sunflower oil treated with 0.83% v/v 2-oxovaleric acid versus untreated oil resulted in an 82.9% reduction in POV after 15 days.

Example 13: Formation of ammonium salt by reaction of phenylpyruvic acid (CAS#156-06-9) and N,N-dimethyldecylamine (DiMeC10A, CAS#1120-24-7) in a 1:1 molar ratio 3.707 g (0.02 mol) of phenylpyruvic acid was dissolved in 10 mL of dry acetone to give a clear solution. Another solution was made with 3.283 g (0.02 mol) of N,N-dimethyldecylamine in 10 mL of dry acetone. The amine solution was added dropwise to the phenylpyruvate solution over a period of 2-3 minutes while stirring. No visible signs of reaction were observed and there was no particular rise in temperature. The mixture was shaken briefly but vigorously and then chilled in the freezer for 30 minutes. A dense network of white, flocculent fine crystals was formed and a small amount of acetone was decanted off the solid mass while cold and discarded. Most of the solvent acetone appeared to be entrapped within the crystalline network and was removed by a nitrogen stream followed by room temperature treatment in a vacuum oven. This gave a slightly off-white fluffy crystalline solid in quantitative yield.

Reduction of sunflower oil POV using a diammonium salt (referred to herein as DiMeC10A-PhPA) formed by the reaction of phenylpyruvic acid and N,N-dimethyldecylamine according to one aspect described herein : 15 mL of sunflower oil that had been stored in a plastic bottle at room temperature for 1 year but had never been opened during this storage period was placed in a 30 mL glass vial, to which 0.3032 g of DiMeC10A-PhPA was added. Most of the salt dissolved, but some undissolved solid remained. The mixture was left on the benchtop at room temperature in the room light of the laboratory and POV measurements were taken periodically. Results are shown in the table below.

（＊）‐ブランクと区別できず

(*) - indistinguishable from blank

This phenyl pyruvate salt provided a very fast reduction of the POV of sunflower oil.

Reduction of model perfume POV using a diammonium salt (referred to herein as DiMeC10A-PhPA) formed by the reaction of phenylpyruvic acid and N,N-dimethyldecylamine according to one embodiment described herein. : A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of lime oil, orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent at approximately 16.7% v/v (40 mL of oil loaded into 200 mL of solvent, 240 mL of perfume combined). Approximately 164 mg (1.1% w/v) of PhPA-DiMeC10A salt was dissolved in 15 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

According to the results shown above, 7 days after the addition of PhPA-DiMeC10A, the POV is reduced by 87.2% relative to the untreated control.

Example 14: Reaction of α-oxo-2-furanacetic acid (CAS#1467-70-5) with N,N-dimethyldecylamine (DiMeC10A, CAS#1120-24-7) in a 1:1 molar ratio 2.114 g (0.015 mol) of α-oxo-2-furanacetic acid were dissolved in 10 mL of dry acetone. The α-oxo-2-furanacetic acid was used as received from the commercial supplier (grey-tan crystalline solid) to give a dark brown solution with a small amount of undissolved floc. It was determined that a preliminary screen was performed using the "as is" material and depending on the results, the purified starting material could be made later.

Another solution was made with 2.780 g (0.015 mol) of N,N-dimethyldecylamine in 10 mL of dry acetone. This amine solution was added dropwise to the crude α-oxo-2-furanacetic acid solution over 5 minutes with stirring. No visible signs of reaction were observed and there was no particular rise in temperature. The mixture was shaken briefly but vigorously and then chilled in the freezer for 30 minutes. No precipitation of the product occurred even at low temperatures, so the acetone was removed by a nitrogen stream followed by room temperature treatment in a vacuum oven. This gave a brown viscous oil in quantitative yield which crystallized to a brown solid after several days at freezer temperatures.

Sunflower with a diammonium salt (referred to herein as FAA-DiMeC10A) formed by the reaction of α-oxo-2-furanacetic acid and N,N-dimethyldecylamine according to one embodiment described herein Reduction of POV of oil: 15 mL of sunflower oil that had been stored in a plastic bottle at room temperature for 1 year but had never been opened during this storage period was placed in a 30 mL glass vial to which 0.3358 g of FAA-DiMeC10A was added. . Most of the salt dissolved, but a small amount of dark brown insoluble droplets remained. The mixture was left on the benchtop at room temperature in the room light of the laboratory and POV measurements were taken periodically. Results are shown in the table below.

（＊）‐ブランクと区別できず

(*) - indistinguishable from blank

Model using a diammonium salt (referred to herein as FAA-DiMeC10A) formed by the reaction of α-oxo-2-furanacetic acid with N,N-dimethyldecylamine according to one embodiment described herein Perfume POV Reduction: A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of lime, orange, grapefruit and bergamot oils as perfume oil. This mixed citrus oil was loaded into the solvent at approximately 16.7% v/v (40 mL of oil loaded into 200 mL of solvent, 240 mL of perfume combined). Approximately 150 mg (1.0% w/v) of FAA-DiMeC10A salt was dissolved in 15 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

According to the results shown above, 7 days after the addition of FAA-DiMeC10A, the POV is reduced by 40.0% relative to the untreated material. The α-oxo-2-furanacetic acid moiety does lower the POV of the model perfume, but appears to be less reactive/slower than the non-aryl α-oxocarboxylic acids tested.

Example 15: A 1:2 molar ratio of α-ketoglutarate (CAS#328-50-7) and tris[2-(2-(methoxyethoxy)ethyl]amine (CAS#70384-51-9) Formation of diammonium salt by reaction 2.922 g (0.02 mol) of α-ketoglutaric acid was dissolved in 10 mL of dry acetone.Tris[2-(2-(methoxyethoxy)ethyl]amine (TMEAA) in 5 mL of dry acetone. ) 12.937 g (0.04 mol) of the amine solution was added dropwise to the AKG solution over a period of 2 minutes with stirring.No visible signs of reaction were observed. The resulting mixture became slightly warm (approximately 35-45° C.) The mixture was shaken briefly but vigorously and then chilled in the freezer for 30 minutes No precipitation of the product occurred even at low temperatures, so nitrogen was added. Acetone was removed by flow followed by room temperature treatment in a vacuum oven, which gave a clear, golden-brown, slightly viscous oil in quantitative yield.

The diammonium salt (referred to herein as AKG-diTMEAA) formed by the reaction of α-ketoglutarate and tris[2-(2-(methoxyethoxy)ethyl]amine according to one embodiment described herein Reduction of POV of sunflower oil used: 15 mL of sunflower oil that had been stored in a plastic bottle at room temperature for 1 year but was never opened during this storage period was placed in a 30 mL glass vial to which 0.5081 g of AKG-diTMEAA was added. A higher than usual weight was used due to the very high molecular weight of this compound (792.96 g/mole).The salt dissolved completely to give a clear golden brown oil. were left on the bench top at room temperature in the room light of the laboratory and POV measurements were taken periodically, the results are shown in the table below.

Example 16: Reaction of α-ketoglutarate (CAS#328-50-7) with N,N-dimethyldodecylamine (CAS#112-18-5) in a 1:2 molar ratio to form a diammonium salt 1.461 g (0.01 mol) of α-ketoglutaric acid was dissolved in 6 mL of dry acetone. This solution was added dropwise with stirring over 1-2 minutes to another solution of 4.268 g (0.02 mol) of N,N-dimethyldodecylamine in 6 mL of dry acetone. No visible signs of reaction were observed except that the combined solution warmed to about 35-40°C. The mixture was shaken briefly but vigorously and then chilled in the freezer for 30 minutes. No precipitation of the product occurred even at low temperatures, but when the mixture was shaken again the whole mass solidified almost instantaneously to a solid white waxy material. The solid was warmed to 30-35° C. to reliquefy the product so that entrapped acetone could be removed by nitrogen flow followed by room temperature treatment in a vacuum oven. This gave a white waxy solid in quantitative yield.

POV of sunflower oil using a diammonium salt (referred to herein as AKG-DiMeC12A) formed by the reaction of α-ketoglutarate and N,N-dimethyldodecylamine according to one embodiment described herein. Reduction: 15 mL of sunflower oil that had been stored in a plastic bottle at room temperature for 1 year but had never been opened during this storage period was placed in a 30 mL glass vial to which was added 0.3062 g of AKG-DiMeC12A. The salt did not dissolve completely and gave a hazy, gel-like suspension with sunflower oil. The mixture was left on the benchtop at room temperature in the room light of the laboratory and POV measurements were taken periodically. Results are shown in the table below.

Example 17: Formation of ammonium salt by reaction of pyruvic acid (CAS#127-17-3) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) in a 1:1 molar ratio. 642 g (0.03 mol) was dissolved in 5 mL of dry acetone to give a clear solution. This solution was added dropwise over 1-2 minutes with stirring to a second solution made up of 3.575 g (0.03 mol) of NMDEA and 5 mL of dry acetone. The resulting mixture became warm (approximately 35-45° C.) and cloudy upon addition of the acid solution. The cloudy emulsion was stirred vigorously for 1 minute during which time the second phase coalesced. When the mixture was placed in the freezer for at least one hour, the bottom phase became considerably more viscous, but did not solidify. While cold, the top layer was easily removed by decantation or pipette and discarded. Residual acetone was removed from the bottom product layer by a stream of nitrogen followed by room temperature treatment in a vacuum oven. This gave a quantitative yield of a clear, golden, highly viscous oil at room temperature.

Reduction of sunflower oil POV using a diammonium salt (referred to herein as PA-NMDEA) formed by the reaction of pyruvic acid and N-methyldiethanolamine according to one embodiment described herein: 1 at room temperature 15 mL of sunflower oil that had been stored in a plastic bottle for a year but had never been opened during this storage period was placed in a 30 mL glass vial, to which 0.2988 g of PA-NMDEA was added. The salt appeared to dissolve and/or disperse, but the resulting mixture was not completely clear and had a translucent colloidal appearance. The mixture was left on the benchtop at room temperature in the room light of the laboratory and POV measurements were taken periodically. Results are shown in the table below.

Example 18: Reduction of POV of Model Perfume Using α-Ketoglutarate According to One Embodiment Described herein It was measured as 1.75. Therefore, the amount of α-ketoglutarate in the hydroalcoholic perfume base solution may need to be limited in order to avoid altering the organoleptic properties of the perfume raw material.

A model perfume was made using 90/10 v/v ethanol/water as a solvent, to which a mixture of orange, grapefruit and bergamot oils was added. This mixed citrus oil was loaded into the solvent (6 mL oil to 25 mL solvent) at approximately 19.4% v/v. Approximately 240 mg (1.2% w/v) of α-ketoglutarate was dissolved in 20 mL of mixed citrus perfume and POV measurements were taken the next day. Results are shown in the table below.

These data show that the POV of the perfume formulation was completely reduced 24 hours after treatment of the perfume formulation with α-ketoglutarate.

Example 19: Reduction of POV of model perfume using oxaloacetic acid according to one embodiment described herein Oxaloacetic acid is known to be unstable in aqueous solution (HA Krebs, Biochemistry (1942) 36, 303-305), resulting in the evolution of carbon dioxide and pyruvate. Nevertheless, oxaloacetate is effective in reducing POV in solutions in which it is dissolved (eg, hydroalcoholic perfumes). However, it is unclear whether the reduction in POV is caused by oxaloacetate itself, by released pyruvate, or by both. Analysis of the reaction products (acetic acid versus malonic acid) could distinguish between the two pathways, but that was not pursued here.

A model perfume was made using 90/10 v/v ethanol/water as a solvent, to which a mixture of orange, grapefruit and bergamot oils was added. This mixed citrus oil was loaded into the solvent (6 mL oil to 25 mL solvent) at approximately 19.4% v/v. Approximately 166 mg (0.83% w/v) of oxaloacetic acid was dissolved in 20 mL of mixed citrus perfume and POV measurements were taken at the times indicated in the table below.

These data show that the POV of the perfume formulation was completely reduced 24 hours after the perfume formulation was treated with oxaloacetic acid.

Example 20: At a 1:1 molar ratio of phenylglyoxylic acid (CAS#611-73-4) and 1-(2-hydroxyethyl)-2-imidazolidinone (HEI, CAS#3699-54-5) 3.003 g (0.02 mol) of phenylglyoxylic acid was dissolved in 10 mL of dry acetone to give a clear solution. Another solution was made with 2.603 g (0.02 mol) of 1-(2-hydroxyethyl)-2-imidazolidinone in 10 mL of dry acetone. Since the 1-(2-hydroxyethyl)-2-imidazolidinone was supplied as a 75% w/w aqueous solution, the amount of this 75% reagent actually used was 3.0 to compensate for the weight of the solvent water. It was 471g. The 1-(2-hydroxyethyl)-2-imidazolidinone amine solution was added dropwise to the phenylglyoxylic acid solution over 3 minutes while stirring. No visible signs of reaction were observed and there was no particular rise in temperature. The mixture was shaken briefly but vigorously and then chilled in the freezer for 30 minutes. No precipitation of the product occurred even at low temperatures, so the acetone was removed by a nitrogen stream followed by room temperature treatment in a vacuum oven. This gave a clear, pale yellow, highly viscous oil in quantitative yield.

Using a diammonium salt (referred to herein as PhGA-HEI) formed by the reaction of phenylglyoxylic acid and 1-(2-hydroxyethyl)-2-imidazolidinone according to one embodiment described herein. Reduction of POV of model perfumes: Model perfumes were made using 90/10 v/v ethanol/water as solvent and a mixture of lime, orange, grapefruit and bergamot oils as perfume oils. This mixed citrus oil was added to the solvent at approximately 16.7% v/v (40 mL oil added to 200 mL solvent for a total of 240 mL perfume). Approximately 150 mg (1.0% w/v) of PhGA-HEI salt was dissolved in 15 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

According to the results shown above, 7 days after addition of PhGA-HEI, the POV decreased by 58.8% relative to the untreated control. The phenylglyoxylic acid moiety does lower the POV of the model perfume, but appears to be less reactive/slower than the non-aryl α-oxocarboxylic acids tested. This reactivity difference can be useful in some cases.

Example 21: 1:2 molar ratio of α-ketoglutarate (CAS#328-50-7) to 1-(2-hydroxyethyl)-2-imidazolidinone (HEI, CAS#3699-54-5) 2.922 g (0.02 mol) of α-ketoglutaric acid (AKG) was dissolved in 10 mL of dry acetone to give a clear solution. A separate solution was made with 5.206 g (0.04 mol) of 1-(2-hydroxyethyl)-2-imidazolidinone (HEI) in 10 mL of dry acetone. HEI was supplied as a 75% w/w aqueous solution, so the actual amount of this 75% reagent used was 6.942 g, compensating for the weight of the solvent water. The HEI amine solution was added dropwise to the AKG solution with stirring over 3 minutes. No visible signs of reaction were observed and there was no particular rise in temperature. The mixture was shaken briefly but vigorously and then chilled in the freezer for 1 hour. No precipitation of the product occurred even at low temperatures, so the acetone was removed by a nitrogen stream followed by room temperature treatment in a vacuum oven. This gave a clear, colorless, highly viscous oil in quantitative yield.

The diammonium salt (referred to herein as AKG-HEI) formed by the reaction of α-ketoglutaric acid and 1-(2-hydroxyethyl)-2-imidazolidinone according to one embodiment described herein Reduction of POV of model perfumes used: Model perfumes were made using 90/10 v/v ethanol/water as solvent and a mixture of lime oil, orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent at approximately 16.7% v/v (40 mL of oil loaded into 200 mL of solvent, 240 mL of perfume combined). Approximately 150 mg (1.0% w/v) of AKG-HEI salt was dissolved in 15 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

According to the results shown above, 7 days after the addition of AKG-DiHEI, the POV is reduced by 92.1% relative to the untreated control.

Example 22: Ammonium salt by reaction of α-ketoglutarate (CAS#328-50-7) and N,N-dimethyldodecylamine (DiMeC12A, CAS#112-18-5) in a 1:1 molar ratio ( Formation of AKG-mono (referred to herein as DiMeC12A)) 2.922 g (0.02 mol) of α-ketoglutarate was dissolved in 12 mL of dry acetone. This solution was added dropwise with stirring over 1-2 minutes to another solution of 4.268 g (0.02 mol) of N,N-dimethyldodecylamine in 6 mL of dry acetone. The mixture was shaken and no visible signs of reaction were observed except that the combined solution warmed to about 35-40°C. The mixture remained clear for several minutes, but when shaken again the whole mass instantly solidified into a solid white crystalline block. The solid was warmed to 30-35° C. to reliquefy the product so that entrapped acetone could be removed by nitrogen flow followed by room temperature treatment in a vacuum oven. This gave a white waxy solid in quantitative yield.

A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent (6 mL oil to 25 mL solvent) at approximately 19.4% v/v. Approximately 200 mg (1.0% w/v) of AKG-monoMe C12A salt was dissolved in 20 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

These data show complete reduction of all POVs within 26 hours after addition of AKG-mono (DiMeC12A).

In addition to the above treatments for the model perfumes, similar experiments were performed with mixed citrus oils. Mixed citrus oil samples were made by combining lime oil, orange oil, grapefruit oil, lemon oil, mandarin oil, tangerine oil, and bergamot oil, so the various terpene hydroperoxides were present in the treated mixtures tested. I decided to Approximately 200 mg (1.0% w/v) of AKG-mono (DiMeC12A) salt was added to 20 mL of mixed citrus oil, most of which did not dissolve. POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated mixed citrus oil samples were manipulated and tested similarly to the treated oil. Results are shown in the table below.

These data show a 94.2% reduction in POV relative to the untreated after 28.0 hours of AKG-mono(DiMeC12A) salt addition.

Surface tension measurement of aqueous AKG-monoDiMeC12A: To evaluate the surfactant properties of AKG-Mono(DiMeC12A), the reduction in surface tension it produces in aqueous solution was measured against pure water. Measurements were carried out on a Kruss DSA100S tensiometer by the hanging drop method. A 0.14% by weight aqueous solution of AKG-Mono (DiMeC12A) was used for the measurement. This concentration was chosen to allow comparison of the results with the known detergent sodium dodecyl sulfate (SDS) 5 mM literature value of approximately 0.15% by weight. The results show that AKG-Mono (DiMeC12A) has remarkable surfactant properties:
Pure water -71.57 mN/m
AKG-monoDiMeC12A-32.93mN/m
For comparison, at 273 K, the air-water surface tension of a 5 mM concentration of SDS (approximately 0.15 wt%, very close to the 0.14 wt% used here) varies from 33.5 to 35.5 mN/m (see Hernainz, F. et al, Colloids Surf. A, 2002, 196, 19-24).

Example 23: Indole-3-pyruvate (I-3-PA, CAS#392-12-1) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) at a 1:1 molar ratio Ammonium Salt Formation by Reaction 0.61 g (0.003 mol) of I-3-PA-NMDEA was placed in 4 mL of methanol, but only partially dissolved. Another mixture was made with 0.357 g (0.003 mol) of NMDEA in 2 mL of acetone, which formed a clear solution. The amine solution was added all at once to the indole-3-pyruvate and stirred vigorously for 1 minute. Some solid remained undissolved, so the mixture was placed in a 40° C. water bath. Upon warming, all material dissolved to form a deep orange clear solution. The mixture was allowed to cool and no precipitate formed. The solution was placed in the freezer for 30 minutes during which time bright pink needles fell. The mother liquor was removed by pipette and was found to contain a significant amount of impure material which could be further recovered by draining the solvent under a stream of nitrogen to give a dark orange solid. For preliminary purposes, the two portions of the product were recombined, awaiting the development of more efficient crystallization procedures. Yields were quantitative.

A model perfume was made using 90/10 v/v ethanol/water as solvent and a mixture of orange oil, grapefruit oil and bergamot oil as perfume oil. This mixed citrus oil was loaded into the solvent (6 mL oil to 25 mL solvent) at approximately 19.4% v/v. Approximately 244 mg (1.2% w/v) of I-3-PA-NMDEA salt was dissolved in 20 mL of mixed citrus perfume and POV was measured as a function of time after addition. Since the POV can spike with manipulation of the sample (opening the bottle, stirring, etc.), the untreated perfume samples were manipulated and tested similarly to the treated perfumes. Results are shown in the table below.

These data show a rapid decrease in POV versus untreated 60 minutes after addition of I-3-PA-NMDEA salt.

Example 24: Made with a 1:2 molar ratio of α-ketoglutarate (CAS#328-50-7) and N-methyldiethanolamine (NMDEA, CAS#105-59-9) according to one embodiment described herein Reduction of POV of Model Perfume Using Diammonium Salts Incorporated into Solid Phase Supports Reduction of POV of Citrus Oils Can Be Resulting Even with Alpha-Oxocarboxylate Salts Virtually Insoluble in Treated Citrus Oils It was observed that This observation appeared to hold for both solid and liquid salts (which tend to be highly viscous), although the rate and efficiency of reduction was not as high as for soluble salts. It was hypothesized that the surface area of contact between the α-oxocarboxylate phase and the citrus oil phase might be the limiting factor. Therefore, if that were the case, any method of increasing the contact area should promote a faster and smoother reaction.

To that end, a thin highly dispersed layer of a diammonium salt formed with α-ketoglutarate and two equivalents of N-methyldiethanolamine (AKG-DiNMDEA) was deposited on a chemically inert high surface area solid phase support. Attempts were made to spread to In this example, a commercially available microfine stainless steel household scrubbing pad (Scotch-Brite Scrubby® Pad, manufactured by 3M Company) was used.

Preparation of AKG-DiNMDEA coated pads: One pad was cleaned as follows. The pad was placed in a 250 mL glass beaker and completely covered with pentane. The beaker was sonicated for 3 minutes, the pentane was drained and the same procedure was repeated with acetone. Acetone was also drained and the pad was placed in a vacuum oven to dry at room temperature for 1 hour. The pad weighed 19.229 g both before and after the cleaning procedure, so no appreciable weight loss was observed as a result of cleaning.

A solution was made with 3.0 g of AKG-DiNMDEA and 10 mL of fragrance grade ethanol. The solution was pipetted onto a stainless steel pad to load it and the ethanol was dried off at room temperature in vacuum. This was best done by roughly dividing the solution into three batches, each with a drying step in between. Attempting to do this in one go resulted in partial spillage of the solution, as the pad could not completely hold such a large volume of solution. Once all the ethanol was removed, the viscous AKG-DiNMDEA appeared to stick to the pad sufficiently tightly so that the pad could be transferred between containers without loss of liquid coating.

Mixed Citrus Oil Treatments: Mixed citrus oil samples were made by combining lime, orange, grapefruit, and bergamot oils, resulting in the presence of various terpene hydroperoxides in the treated mixtures tested. rice field. Two separate 250 mL glass bottles were filled with 150 mL each of the mixed citrus oil. This allows a substantial vapor phase portion of the atmosphere to exist within each sealed vial, which is replenished with fresh air/oxygen each time the vial is opened to draw an aliquot of the test. This configuration was designed to mimic oxygen exposure as a result of typical operations in the production of drums of citrus oil feedstock, resulting in realistic levels of autoxidation of the contained oil.

An AKG-DiNMDEA coated pad was placed in one jar (treated sample) and completely immersed therein in the mixed citrus oil. The second bottle contained nothing but mixed citrus oil (untreated sample). These bottles were left on the laboratory bench at ambient temperature and lighting conditions for the duration of the test. Aliquots were removed periodically from each bottle for POV testing. Coating that flowed downward from the pad, as evidenced by the appearance of a pool of AKG-DiNMDEA collecting at the bottom of the container, took several weeks to become noticeable. As this outflow progressed, the contact area between the phases probably decreased and the efficiency of the reduction reaction decreased. Nevertheless, as reported below, the treated citrus oil was considerably protected against autoxidation-induced increases in POV.

Pad replenishment: After 26 days, it was observed that the POV of the treated samples began to increase slightly (see Figure 5). At the same time, the POV reduction of the treated samples started to decrease slightly relative to the untreated samples (see Figure 6). This was taken to mean that the coated pads were ineffective, possibly due to chemical consumption of the AKG-DiNMDEA. Instead, a viscous liquid, believed to be AKG-DiNMDEA, trickled downward from the stainless steel coil of the pad. This creates a pool of low surface area and thus poor contact with the citrus oil, rendering the reagent ineffective.

The pads were removed from the mixed citrus oil and washed sequentially with 100 mL each of acetone, then 95% ethanol, then again acetone. The washed pads were dried in vacuum at room temperature and reloaded with AKG-DiNMDEA. This time we took a simpler procedure to refill/reactivate/reload the Scrubby®. Instead of adding a solution and allowing the solvent to evaporate, the viscous AKG-DiNMDEA oil was simply rubbed onto the steel coil. Approximately 3.2 g of AKG-DiNMDEA was placed on a steel pad surface and kneaded in with gloved hands to distribute the oil as evenly as possible. The replenished Scrubby® was then returned to the treated citrus oil container and POV monitoring continued as before. Time points corresponding to supplementation are indicated by purple vertical lines in FIGS.

Raw POV titration data:

Example 25: Reduction of POV for a Group of Consumer Products According to One Embodiment Described Herein This example reports the processing of an exemplary consumer product formulation. As shown in the table below, the consumer product formulations had measurable oxidation levels as received, but low POV levels, except for the all-purpose cleaner. POV was associated with an autoxidized base component as none of the samples were perfumed. Severely oxidized limonene produced in a photoreactor (POV was 1434 mmol/L) as a source of mixed limonene hydroperoxide isomers was added to five consumer product formulations. Limonene oxide was added to each at a concentration of 10 μL/g, resulting in a POV of approximately 14.3 mmol/L added to the existing POV as received.

In all cases, treatment with α-oxocarboxylic acid ammonium salt resulted in a fast and significant reduction in the POV of the samples. Hydroperoxides present in the sample were consumed/destroyed by controlled and deterministic reactions with α-oxocarboxylic acids to produce harmless and predictable by-products. In some cases, the untreated samples showed a much slower but steady reduction in POV, possibly because the limonene hydroperoxide reacted with the base building blocks and oxidized them, thereby producing unknown by-products. Conceivable. This can often have detrimental effects on the formulation, such as malodour formation, discoloration, and changes in physical properties. Such uncontrolled and unintended reduction in POV is not necessarily positive for the formulation in general, even though the consumption of the sensitizing hydroperoxide reduces the skin sensitizing potential of the sample.

POV of Consumer Product Samples at Acquisition (Before Addition of Limonene Oxide)

Sample preparation: To 40 mL (Sample #3) or 40 g (Samples #1, 2, 4 and 5), 0.4 mL of limonene oxide was added respectively and mixed until homogeneous. Half of each consumer product sample spiked with limonene oxide was transferred to a second container and treated with 0.5-1% (w/w) 2-oxocarboxylic acid ammonium salt as described in the table below. Then mixed until homogeneous. Five pairs of each of the two treated and untreated samples were left on the benchtop at room temperature in the room light of the laboratory and POV measurements were taken periodically. The results are described below.

Sample 1 Hand dishwashing liquid soap (HDLS) - see Figures 7 and 8:

Sample 2 Shampoo - See Figures 9 and 10:

Sample 3 All Purpose Cleaner (APC) - See Figures 11 and 12:

Sample 4 Skin Cream - See Figures 13 and 14:

Sample 5 Antiperspirant Stick (APS) - See Figures 15 and 16:

Example 26: Reduction of POV of a Group of Non-Citrus Sourced Essential Oils According to One Embodiment Described Herein In this example, a series of non-citrus-derived essential oils were combined with AKG-DiTMEA (molar A bilayer made of α-ketoglutarate (AKG, CAS#328-50-7) and tris[2-(2-(methoxyethoxy)ethyl]amine (TMEAA, CAS#70384-51-9) in a 1:2 ratio. ammonium salts).The results show that the treatment is effective on a wide range of essential oils containing a wide range of terpenes and other small organic molecules such as aromatics. A very wide range of organic hydroperoxides are present as autoxidation products in other types of oil, but they are all reduced by 2-oxoacids, in this case especially α-ketoglutarate ammonium salt. it is conceivable that.

The data below shows the nine oils and the POV as obtained from the production inventory obtained for each. 20 mL of each oil was placed in separate 30 mL glass vials, and each day for 8 days the vials were opened to freshen the gas phase portion of the atmosphere, then closed again and shaken to maximize gas-liquid contact before being placed in the laboratory. The procedure was subjected to bench top placement at ambient temperature and lighting conditions. This procedure was designed to mimic container operation at a manufacturing site where the oil is consumed in many small aliquots rather than the entire container at once.

On day 4, each oil sample was split in half, thus placing two 10 mL aliquots in separate vials to create a "treated" sample and an "untreated" sample. AKG-DiTMEA was added to the treated samples of each oil grade according to the dosing table below. Since the POV of pine oil was quite high, the dosing and measurement protocol was somewhat different than the other oils. The daily open bottle, shake, and stand procedure continued for four more days until POV measurements were taken. It can be seen that after 8 days of such manipulation on the untreated oil, the measured POV increased significantly.

Siberian pine oil, when obtained, had an unusually high POV that could lead to stoichiometric depletion of AKG-DiTMEAA. For this reason, two levels of AKG-DiTMEA treatment were tried, 2x and 4x the treatment used for the other oils. The results indicate that larger amounts may be needed to fully improve this pine oil sample. This is because AKG-DiTMEAA has a high molecular weight due to the large amine group and a low stoichiometric capacity to scavenge hydroperoxides per unit weight. Other, lower molecular weight 2-oxoacid salts may be better options.

POV of untreated oil before and after operation:

AKG-DiTMEA administration/treatment to non-citrus essential oils

AKG-DiTMEEA treatment of non-citrus essential oils (4 days)

All publications and the like cited in this document are hereby incorporated by reference. While various aspects of the present invention have been illustrated with reference to examples and preferred embodiments, the scope of the invention is to be properly construed under the principles of patent law and set forth in the following claims rather than the foregoing specification. will be understood to be defined by the range of

Claims (13)

A method of reducing the peroxide value (POV) of a perfume, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient comprising:
a. adding an alpha-oxocarboxylic acid to said perfume, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient having a first POV level; and b. said perfume, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or A method comprising mixing the α-oxocarboxylic acid with a food ingredient. Reduces, prevents, or alleviates skin irritation in subjects in need of reducing, preventing, or alleviating skin irritation induced by perfume formulations, body care products, home care products, cosmetics, or perfume ingredients a method,
a. adding an α-oxocarboxylic acid to a perfume formulation, body care product, home care product, cosmetic product, or perfume ingredient having a first POV level; and b. to the perfume formulation, body care product, home care product, cosmetic product, or perfume ingredient for a time sufficient to reduce the first POV level to a predetermined lower second POV level. admixing an α-oxocarboxylic acid, wherein said predetermined lower second POV level is induced in said perfume formulation, body care product, home care product, cosmetic product, or perfume ingredient; sufficient to reduce, prevent, or alleviate skin irritation of 3. A method according to claim 1 or 2, wherein the perfume raw material is treated prior to being formulated into perfume. 3. A method according to any one of claims 1 or 2, wherein the perfume raw material is processed after being formulated into perfume. 3. The method of any one of claims 1 or 2, wherein the food ingredient is treated prior to incorporation into the flavored article. 3. The method of any one of claims 1 or 2, wherein the food ingredient is processed after being formulated into a flavored article. The concentration of the α-oxocarboxylic acid after addition to the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient is in the range of 0.001 to 10% by weight. 3. The method of any one of claims 1 or 2, wherein The α-oxocarboxylic acid is pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutaric acid, 2-oxopentanedioate, selected from the group consisting of indole-3-pyruvate, 2-thiopheneglyoxylate, trimethylpyruvate, 2-oxoadipate, 4-hydroxyphenylpyruvate, phenylpyruvate, 2-oxooctanoate, and mixtures thereof 3. The method of any one of claims 1 or 2, wherein 3. The method of any one of claims 1 or 2, wherein the predetermined lower second POV level is between 5 and 20 mmol/L. 3. The method of any one of claims 1 or 2, wherein the predetermined lower second POV level is between 0 and 6 mmol/L. removing the α-oxocarboxylic acid from the perfume formulation, body care product, cosmetic product, home care product, perfume ingredient, flavored article, or food ingredient having the predetermined lower second POV level; 3. The method of any one of claims 1 or 2, further comprising: 12. The method of claim 11, wherein removing the alpha-oxocarboxylic acid from the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient comprises liquid-liquid extraction. . After removing the α-oxocarboxylic acid, the perfume formulation, body care product, cosmetic, home care product, perfume ingredient, flavored article, or food ingredient is treated with a carbonate to produce the perfume formulation, body care product. 3. The method of any one of claims 1 or 2, further comprising reducing the acidity of the care product, perfume ingredient, flavored article, or food ingredient.

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