CA2207457C - Coolant compositions - Google Patents

Coolant compositions

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Publication number
CA2207457C
CA2207457C CA002207457A CA2207457A CA2207457C CA 2207457 C CA2207457 C CA 2207457C CA 002207457 A CA002207457 A CA 002207457A CA 2207457 A CA2207457 A CA 2207457A CA 2207457 C CA2207457 C CA 2207457C
Authority
CA
Canada
Prior art keywords
coolant
selected
products
succinate
monomenthyl succinate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CA002207457A
Other languages
French (fr)
Other versions
CA2207457A1 (en
Inventor
Jean Mane
Jean-Louis Ponge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
V MANE FILS SA
Original Assignee
V. MANE FILS S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US08/520399 priority Critical
Priority to US08/520,399 priority patent/US5725865A/en
Priority to US08/629598 priority
Priority to US08/629,598 priority patent/US5843466A/en
Priority to US08/701,141 priority patent/US5752529A/en
Priority to US08/701,141 priority
Application filed by V. MANE FILS S.A. filed Critical V. MANE FILS S.A.
Publication of CA2207457A1 publication Critical patent/CA2207457A1/en
Application granted granted Critical
Publication of CA2207457C publication Critical patent/CA2207457C/en
Anticipated expiration legal-status Critical
Application status is Expired - Lifetime legal-status Critical

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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/36Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G4/00Chewing gum
    • A23G4/06Chewing gum characterised by the composition containing organic or inorganic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A23B - A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20Synthetic spices, flavouring agents or condiments
    • A23L27/203Alicyclic compounds
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/14Use of materials for tobacco smoke filters of organic materials as additive
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/24Thermal properties
    • A61K2800/244Endothermic; Cooling; Cooling sensation

Abstract

The invention relates to refreshing compositions, flavouring compositions and ingestible and topical compositions containing at least a refreshing compound selected amongst monomenthyl succinate, alcaline metal salts of monomenthyl succinate, alcaline-earth metal salts of monomenthyl succinate and mixtures thereof. Said compositions provide a durable, bitterness-free, pleasant and refreshing effect, and said refreshing feel is different from that of other known refreshing agents. Consequently, a complementary or synergic effect can be obtained by combination with other refreshing agents. Furthermore, the succinate-based refreshing compounds according to the invention provide for an increase of alcohol feel in alcoholic drinks. Finally, the succinate-based refreshing compounds provide a refreshing taste when they are applied to filters, combustible papers and sheets for wrapping tobacco products for smoking and when they are incorporated into tobacco products for chewing or snuffing.

Description

CA 022074~7 1997-06-10 COOLANT COMPOSITIONS

This invention relates to coolant compositions having a unique cooling perception that provides the user with a pleasing cooling effect without bitterness.
The invention also relates to products containillg one or more coolant cornpounds.
A variety of compounds are known which provide a cooling sensation when ingested or contacted with the body. Perhaps the best known of these compounds is menthol. It is believed that menthol acts on the cold receptors at the nerve endings in order to provide this cooling effect. Since menthol has a strong minty odor and high relative volatility, several other coolant compounds have been developed and reported in the technical literature as potential flavorants or odorants in a variety of topical and ingestible compositions. For example, U.S. Patent No. 5,009,893 proposes the use of menthol in combination with N-subsliluted-p-menthane carboxamide compounds as coolant compositions in edible products.
International Patent application publication No. W093/23005 proposes coolant compositions for edible or topical products which comprise a ketal and a secondary coolant which may be selected from menthol, carboxamides and mixtures thereof.
Several other references are mentioned therein which disclose compounds which have a flavor resembling menthol including menthyl carbinol, saccharide esters of menthol and a varietv of amides. Also, 2,3-p-menthane diol has been reported as having a sharp cooling taste.
German Patent application 2 339 661 discloses aromatic compositions which include menthol or menthol esters of heterocyclic carboxylic acids. The preferred ester is menthyl-2-pyrrolidone-5-carbo~ylic acid ester.

CA 022074~7 1997-06-10 German Patent application 26 08 226 discloses a composition which exhibits a physiological cooling effect. The cooling compounds disclosed include menthol esters of naturally occurring hydro~ycarboxylic acids having 2-6 carbon atoms which are esterified with a Cl-C4 alkyl group. Menthyl acetate and menthyl lactate are the most preferred cooling compounds of this disclosure. Finally, another commercially available coolant compound is 3-menthu~y~lo~ane-1,2 diol.
Thus, a variety of compounds are known which provide cooling properties and are useful in a wide variety of products. However, there is still a need to provide coolant compositions having an i~ ov~d cooling effect and/or taste perception.
Accordingly, it is an object of the present invention to provide hll~roved coolant compositions.
It is a further object of the present invention to provide coolant compositions having a unique cooling sensation and taste perception.
It is a still further object of the present invention to provide coolant compositions including two or more cooling agents which provide a complementary cooling sensation and taste perception.
It is a still further object of the present invention to provide a novel coolant composition which employs a non-toxic coolant having a unique cooling sensation and taste perception.
In a first aspect, the present invention relates to a composition selected from topical products, oral care products, nasal care products, toilet articles, ingestible products, chewing gum and smoking, chewing tobacco, moist snuff and snuff tobacco products which include a product base and an effective amount of a cooling CA 022074~7 1997-06-10 compound selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate.
In a second aspect, the present invention relates to a composition including a coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate formulated with a diluent selected from the group of flavors, sweetening syrups, navo~ g syrups, ~v(~ g oils and herbal oils.
The present invention also relates to coolant compositions which include a primary coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate, and at least one secondary coolant component.
Monomenthyl succinate is a known compound having Chemical Abstracts no.
77341-67-4. It has been used, for example, in smoking tobacco as is disclosed in U.S.
Patent No. 3,111,127. In particular, this patent discloses smoking tobacco which incorporates a monoester of synthetic or natural menthol and a saturated or unsaturated aliphatic or aromatic polycarboxylic acid or a subsliluled analog of such an acid. These tobacco products were evaluated and observed to burn slower at smolder than a comparable control product, to have increased firmness, and to require more puffs under a controlled smoking regime. Further, when tested organoleptically, these products were found to deliver smoke having the pleasing and cooling taste and aroma characteristic of menthol. Among the polycarboxylic acid esters are mentioned methylsuccinic acid ester, mono menthylsuccinate, monomenthyl-a-a-dimethylsuccinate and mono menthol-menthylsuccinate.

CA 022074~7 1997-06-10 The article, "A Molecular Approach to Flavor Synthesis. I. Menthol Esters of Varying Size and Polarity," Jabloner, H. and Dunbar, B.I., J. of Polymer Science, Vol.
18, pages 2933-40 (1980) discloses a method for the synthesis of monomenthyl succinate as well as monomenthyl sodium succinate and other menthol esters derived from monomenthyl succinate. Solutions of 5% by weight of several of these menthol esters in mineral oil or water were tasted by a nine person taste panel. 5% of dimenthyl succinate in mineral oil was found to be odorless and tasteless, 5~o sodium monomenthyl succinate in water was found to be vile and bitter and monomenthyl succinate itself was not tasted.
It has been surprisingly found that monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate used in a variety of ingestible and topical products at low concentrations of up to 1% by weight, give a pleasing, long-lasting cooling effect rather than the vile and bitter taste observed by the taste panel in the Jabloner article.
The present invention relates to an end use composition selected from topical products, oral care products, nasal care products, toilet articles, ingestible products, chewing gums, chewing tobacco, moist snuff or snuff tobacco products, and smoking tobacco products which include a product base and an effective amount of a cooling compound selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate (hereinafter collectively referred to as "succinate-based coolant compounds").
More preferably, the coolant employed in the compositions of the present invention is selected from monomenthyl succinate, monomenthyl sodium succinate, monomenthyl potassium succinate, monomenthyl lithium succinate, monomenthyl CA 022074~7 1997-06-10 calcium succinate, monomenthyl magnesium succinaee and monomenthyl barium succinate, as well as mixtures thereof.
It has been ,ul~lisillgly found that these succinate-based coolant compounds, when used in low concentrations of up to 1% by weight based on the total weight of the end use composition into which they are incorporated, provide a pleasing and/or long-lasting cooling effect without the bitterness which would be expected from the prior art. Further, at concentrations of up to 1% by weight, the succinate-based coolant compounds do not develop a strong minty taste in the mouth or throat as do other coolants such as menthol.
The succinate-based coolant compounds of the present invention also provide a cooling effect in a dirrerent area of the mouth and throat when ingested than, for example, menthol or carboxamide-based coolant compounds. As a result, the succinate-based coolants of the present invention provide a complementary or synergistic cooling effect when combined with at least one secondary coolant compound.
Further, the succinate-based coolant compounds of the present invention enhance the taste sensation of alcohol in alcoholic beverages. As a result, alcoholic beverages COl~ g the succinate-based coolant compounds of the present invention taste like they have a higher alcohol content than equally strong alcoholic beverages without the succinate-based coolant compound.
The choice of the succinate-based coolant compound for use in the coolant composition will depend, to some extent, on the solubility characteristics which are desired of the compound. For example, monomenthyl succinate is sparingly soluble in water and more soluble in oil. Thus, monomenthyl succinate is particularly suitable CA 022074~7 1997-06-10 for environments where oil solubility is advantageous, although monomenthyl suceinate can be used in aqueous environments if a concentration below the water solubility limit is employed. The alkali metal and alkaline earth metal salts of monomenthyl succinate are substantially more soluble in water and, as a result, are most useful in products where water solubility is advantageous.
The end use eompositions in whieh the sueeinate-based eoolant eompounds may be employed include a wide variety of ingestible eompositions and topieal compositions for applieation to the human or animal body. Ingestible eompositions inelude foodstuffs for human or animal con~ulll~lion, beverages and other orally ingested eo~ iLions for humans or ~nim~l~ sueh as medieaments, antaeids and laxatives, as well as ehewing gum compositions. Topical eompositions include a wide variety of eompositions for application to humans or ~nim~l~ sueh as toiletries, oral care products, nasal eare products, lotions, oils and ointments. Tobaeeo produets inelude ehewing tobaeeo, moist snuff, snuff tobacco, as well as filters, combustible papers and leaf wrappers used in smoking tobaeeo produets.
In formulating the compositions of the present invention, the eoolant eompound ean be employed in the form of a eoolant eomposition, a flavoring eomposition and/or the coolant compound, composition or flavoring eomposition may be incorporated into a carrier material whieh may be inert or may eontain other aetive ingredients of the end use composition. A wide variety of earrier materials ean be employed ineluding, for example, polar solvents, oils, fats, finely divided solids, maltodextrins, eyclodextrins, gums, natural or synthetic resins and any other known carrier materials for coolant or flavoring compositions.

CA 022074~7 1997-06-10 Ingestible compositions in accordance with the present invention include, but are not limited to, alcoholic and non-alcoholic beverages, confectionery compositions including confectionery tablets, hard-boiled candies, chewing gums, pectin-based candies, chewy candies, cream-centered candies and fondants; carbonated beverages, powdered beverage mixes, distilled beverages, alcoholic beverages, non-alcoholic beverages, mineral waters, baked goods, dairy products, fruit ices, jams, jellies, gelatins, puddings and animal feeds.
Another type of ingestible composition in accordance with the present invention is sugarless candies. Sugarless candies typically have higher boiling points than the corresponding candies including sugar and thus any flavors added thereto must be stable at higher temperatures in order to be successfully added to the sugarless candy. Sugarless candies may include hard-boiled candies, pectin-based candies, chewy candies and cream-centered candies. In addition, sugarless chewing gums may also be made in accordance with the present invention. The amount of cooling composition incorporating in sugarless candies and/or sugarless gums is the same as would be used for the corresponding candies and/or gums including sugar.
The topical compositions of the present invention include, but are not limited to, toiletries such as face creams, talcum powders, hair oils, shampoos, bath oils and salts, toilet soaps, cologne, antiperspirants, toilet water, perfume, shaving lotions and creams, soaps, creams, dentifrices, mouthwashes, hair tonics and other similar products.
The succinate-based coolant of the present invention may also be incorporated into ingestible or topical medicaments such as cough drops, antacids, lozenges, anti-irritants, ointments, lotions, oral analgesics and other similar products. Further, other CA 022074~7 1997-06-10 compositions such as adhesives for a variety of uses where taste perception is a concern can incorporate the cooling and flavorant compositions of the present invention.
The succinate-based coolant compounds are incorporated in a variety of tobacco products in accordance with the present invention. In one embodiment, the succinate-based coolant compounds are incorporated into chewing tobacco, moist snuff or snuff tobacco. In another embodiment, the succinate-based coolant compositions are associated with smoking tobacco products either by incorporating the succinate-based coolant compounds into the combustible paper, leaf wrapper or filter of the smoking tobacco products or by applying the succinate-based cooling compositions to surface of the combustible paper, leaf wrapper and/or filter of smoking tobacco products.
By tobacco products is meant products such as cigarettes, cigars, chewing tobacco, moist snuff and snuff tobacco which include as a component tobacco, or a tobacco derivative product. For example, clove cigarettes and cigars as well as flavored chewing tobaccos and the like are included within the scope of tobacco products in accordance with the present invention. Moist snuff is a form of snuff which is placed in the mouth either in a hand-made pellet form or contained in a sachet of high porosity paper.
The succinate-based coolant compounds of the present invention provide a refreshing aftertaste when employed in certain tobacco products. Further, when used in combination with a compound material such as menthol, the succinate-based coolant compounds provide a complementary cooling effect without undesirably enhancing the minty flavor of the menthol.

CA 022074~7 1997-06-10 In m~king the tobacco products of the present invention, the coolant compound can be employed in the form of a coolant composition or the coolant compound or composition may be incorporated into a carrier material which may be inert or may col,taill other active ingredients of the end use composition. A wide variety of carrier m~teri~l~ can be employed including, for example, polar solvents, oils, fats, finely divided solids, maltodextrins, cyclodextrins, gums, natural or synthetic resins and any other known carrier materials for such compositions.
The amount of coolant composition incorporated in each of the tobacco products of the invention will vary depending upon the particular compound, the degree of cooling effect desired and the strength of other coolants in the composition.
Typically, the succinate-based coolant compound will make up from 0.01 to 0.5% by weight of the tobacco product. More preferably, the succinate-based coolant compound makes up 0.02 to 0.3~o by weight, based on the total weight of the tobacco product.
The succinate-based coolant compounds are applied directly to tobacco in any conventional manner such as by spraying, brushing or injection, for example. When applied to the combustible paper, leaf wrapper or the filter of smoking tobacco products, the succinate-based coolant compounds may be sprayed or brushed on or, in the case of filters, may be injected in the filter. Any other suitable means can be employed.
The present invention also relates to tobacco products including a combination of a primary cooling agent selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl succinate and mixtures thereof, with at least one secondary coolant component. Generally, the level CA 022074~7 1997-06-10 of the secondary coolant compounds in the tobacco products of the present invention is from about 10% by weight to about 700% by weight, more preferably from about 20% by weight to about 650% by weight, and most preferably from about 30% by weight to about 500% by weight, based on the weight of the primary cooling agent.
Other preferred compositions which incorporate the succinate-based coolant of the present invention are pressed confectionery tablets, hard-boiled candies, chewing gums, chewy candies, pectin candies, cream-centered candies, fon~1~nt, toothpastes, mouthwashes, breath fresheners, alcoholic and non-alcoholic beverages, carbonated beverages and dry beverage mixes.
The amount of coolant composition incorporated in each of these end use compositions will vary depending upon the particular compound, the degree of cooling effect desired and the strength of other flavorants in the composition. Typically, the succinate-based coolant compound will make up from 0.001-1.0% by weight of the end use composition. More preferably, the succinate-based coolant compound makes up 0.005-0.5% by weight, based on the total weight of the end use composition.
In a second aspect, the present invention relates to a flavoring composition including a succinate-based coolant and a diluent selected from flavorants. This composition is particularly useful as a flavoring composition In a variety of ingestible compositions and/or compositions destined for contact with the human or animal body.
The flavorants may be selected from fruit flavors such as strawberry flavor, herbal oils such as eucalyptus oil, peppermint oil, spearmint oil, as well as other known flavors or flavoring oils which are conventionally employed in ingestible compositions and compositions designed for contact with human or animal bodies CA 022074~7 1997-06-10 including flavors such as flavoring syrups such as sorbitol syrup or other sweetening or flavoring syrups.
These flavoring compositions can be optionally diluted with a polar solvent such as, for example, ethyl alcohol, ethyl acetate, propylene glycol, isopropyl alcohol and ~lycerin. The solvent functions as a carrier material which aids in incorporating the flavoring composition into the product. The diluent may optionally comprise one or more additional co"ve"lional components selected from the group co"si~li"g of colorants, lubricants, thickeners, emulsifiers, plasticizers and encapsulating agents such as gums, starches, dextrins and cyclodextrins.
Typically the flavoring composition will include 1-80% by weight of the succinate-based coolant compound and from 20-99% by weight of the flavorant diluent and optional polar solvent. More preferred flavorant compositions comprise 5-50% by weight of the succinate-based coolant compound and 50-95% by weight of the flavorant diluent and optional polar solvent.
The present invention also relates to a combination of a primary cooling agent selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl succinate and mixtures thereof, with at least one secondary coolant component.
Secondary coolant components which may be used in combination with the primary coolant of the present invention include menthol, carboxamides, ketals, menthyl acetate, menthyl lactate, 3-menthoxypropane-1,2 diol and ll~ ules thereof.
The carboxamide and ketal coolant compositions are known from the prior art and can be found, for example, in U.S. Patent No. 5,009,893 and international patent application publication No. W0-93/23005, the disclosures of which are hereby CA 022074~7 1997-06-10 incorporated by reference. The remaining secondary coolants are known cooling agents, some of which are commercially available.
More particularly, the carboxamide secondary coolants are selected from N-substituted-p-menthane-3-carboxamides of the formula:

~CONR'R"

wherein R', when taken separately, is hydrogen or an aliphatic radical containing up to 25 carbon atoms; R" when taken separately is hydlu~y or an aliphatic radical containing up to 25 carbon atoms, with the proviso that when R' is hydrogen R" may also be an aryl radical of up to 10 carbon atoms and selected from the group consisting of substituted phenyl, phenylalkyl, substituted phenylalkyl, naphthyl, substituted naphthyl and pyridyl; and R' and R", when taken together with the nitrogen atom to which they are attached, represent a cyclic or heterocylic group of up to 25 carbon atûms;
acyclic tertiary and secondary carboxamides of the formula:
Rl l R2----f*----CONR'R"

where R' and R", when taken separately, are each hydrogen, C1-Cs alkyl or C1-C8 hydlu~yalkyl and provide a total of no more than 8 carbon atoms, with the proviso that when R' is hydrogen R" may also be alkylcarboxyalkyl of up to 6 carbon atoms;
R' and R", when taken together, represent an alkylene group of up to 6 carbon atoms, the opposite ends of which group are attached to the amide nitrogen atom thereby to CA 022074~7 1997-06-10 form a nitrogen heterocycle, the carbon chain of which may optionally be interrupted by oxygen; R1 is hydrogen or Cl-Cs alkyl; and R2 and R3 are each C1-Cs alkyl; with the provisos that (i) R1, R2, and R3 together provide a total of at least 5 carbon atoms, preferably from 5-10 carbon atoms; and (ii) when R1 is hydrogen, R2 is C2-C5 alkyl and R3 is C2-Cs alkyl and at least one of R2 and R3 is branched, ~referably in an alpha or beta position relative to the carbon atom marked (*) in the formula; and n~ lules thereo~
The ketal coolant compositions may be represented by the formula:

in which R1 represents a C2-C6-alkylene radical having at least 1, but not more than 3, hydlu~yl group(s), and either R2 and R3 independently of one another represent C1-C1O-alkyl which is optionally substituted by 1 to 3 radicals selected from the group colllylisillg hydl~yl, amino and halogen, Cs-C7-cycloalkyl, prefelably cyclohexyl, and C6-C12-aryl, prerelably phenyl, with the proviso that the total of the C atoms of R2 and R3 is not less than 3, or R2 and R3 together represent an alkylene radical which, together with the carbon atom which carries the radicals R2 and R3, forms a 5-7 membered ring, optionally substituted by Cl-C6-allyl groups.
The relative amounts of the primary and secondary coolants in the composition of the present invention may be varied over a wide range of compositions depending upon the particular flavor desired. For example, when the strong minty taste of menthol is desirable, a combination of a large quantity of menthol with a relatively small quantity of the succinate-based coolant of the present invention may be CA 022074~7 1997-06-10 desirable. Other potential combinations of the primary coolant with one or more secondary coolant components will be apparent to the man of skill in the art.
Generally, the level of the secondary coolant component in the coolant composition of the present invention is from about 0.055~ by weight to about 95~o by weight, more ~rerelably from about 0.1% by weight to about 70% by weight, and most ~refel~bly from about 0.5% by weight to about 50% by weight, based on the total weight of the composition. Typically, the coolant compositions are made by mixing the primary and secondary coolants together in a con~elllional manner.
Certain compositions of the present invention are illustrated by the following examples.

Experimental Procedure for the Examples For each of examples 1-10 given below, a taste panel composed of 10-12 persons tasted the materials. The tasters were instructed to give information on the cooling effect, any unpleasant tastes and any other comments they might have. The following results were obtained from these tests.

Example 1- Hard Candy A hard candy formulation was made up from 120 grams of sugar, 30 grams of water, 80 grams of corn syrup and 0.1% by weight, based on the weight of the composition, of cinnamon flavor (control formulation). The formulation was divided into three parts. 0.05% by weight, based on the weight of the composition, of monomenthyl succinate was added to one of the hard candy formulations and 0.05~o by weight, based on the weight of the composition of a commercially available coolant CA 022074~7 1997-06-10 composition (WS3tm) from Wilkinson-Sword) was added to the other hardy candy formulation for the purpose of comparison.
The taste panel found that the hard candy forrnulation containing the monomenthyl succinate provided a long-lasting, pleasant c-ooling effect whereas no cooling effect was present in the control. No minty flavor was noticed by the tasting panel. The hard candy formulation co~ g WS3tm also provided a cooling effect although the taste panel concluded that the cooling effect of WS3tm manifested itself in a different area of the mouth and throat than the cooling effect of the monomenthyl succinate of the invention.

Example 2 - Pressed Tablets Royal Ttm Dextrose (tabletting sugar) was pressed into two tablets, one contai~ g only dextrose (control) and one containing 0.1% by weight of monomenthyl succinate. The taste panel noticed a pleasant cooling effect from the tablet containing the monomenthyl succinate and no cooling effect was obtained from the dextrose control tablet.

Example 3 - Mouthwash Four samples of a mouthwash formulation having the following composition were tasted, cetyl pyridinium chloride 0.757 grams sodium saccharin 1.75 grams Tweentm 80 0.5 fluid ozs.
D&C Green #5 (0.1% soln. in propylene glycol) 0.8 fluid ozs.
D&C Yellow #10 (0.1 soln. in propylene glycol) 0.2 fluid ozs.
Flavor N&A Mint Blend (0.2% soln.) 0.25 fluid ozs. -~
Specially denatured alcohol 31.0 fluid ozs.

CA 022074~7 1997-06-10 These ingredients were blended together until dissolved and then 96 fluid ozs. of water were added to provide a mouthwash formulation. The coolant compounds were then added to the mouthwash formulation in the amounts specified below.
The four mouthwash formulations tested were as follows: one containing no additives (control), one col~tainillg .004% by weight of monomenthyl succinate, one conlai~ g .004% by weight of WS3tm and one col~lainillg .002% by weight of monomenthyl succinate and .002% by weight of WS3'm .
The taste panel noted a cooling effect in all three compositions although the taste panel concluded that each of the four mouthwash samples had a different taste and that the cooling effect of the monomenthyl succinate manifested itself in a different area of the mouth and throat than the cooling effect of WS3tm and the mouthwash. The cooling effects of the monomenthyl succinate, mouthwash mint flavor and WS3tm were found to be complementary in the fourth sample which contained all three coolants.

Example 4 - Mouthwash Containing Sodium Monomenthyl Succinate The same four mouthwash formulations as were made in Example 3 were taste tested except that sodium monomenthyl succinate was substituted for the monomenthyl succinate in the same amounts. The tasting panel found a pleasant, long-lasting cooling sensation without bitterness for the sodium monomenthyl succinate-containing mouthwashes. The tasting panel also noted that the cooling sensation of sodium monomenthyl succinate was perceived at a point slightly forward of the point in the mouth and throat where the cooling sensation of monomenthyl succinate was perceived in the taste tests of Example 3. The sodium monomenthyl CA 022074~7 1997-06-10 succinate was also found to have a complementary cooling effect when combined with WS3tm Example 5 - Carbonated Beverages Four samples each of lemon-lime carbonated beverage were prepared, one without additives (control), one with .004% by weight of monomenthyl succinate, one with .004% by weight of WS3tm and one with 0.002% by weight of monomenthyl succinate and 0.002% by weight of WS3tm. The carbonated beverage formulation was as follows, with all parts being parts by weight:

High fructose corn syrup 96.00 parts Water 28.90 parts Sodium benzoate (25% solution w/w in water) 0.50 parts Citric acid (50% solution w/w in water) 2.30 parts Flavor N&A lemon-lime 0.30 parts The carbonated beverage was formulated by combining the first three ingredients and mixing thoroughly, adding the citric acid solution and mixing again followed by adding the flavor to provide a beverage syrup. One part of the beverage syrup was then combined with 5 parts of carbonated water to provide the carbonated beverage. The coolant compounds were then mixed into the carbonated beverages om the amounts specified above.
The taste panel concluded that the samples containing monomenthyl succinate and WS3tm provided a cooling effect and that the cooling effect of monomenthyl succinate manifested itself in a different area of the mouth and throat than the cooling effect of WS3tm. In addition, the cooling effect of monomenthyl succinate was found to be pleasing, not minty and long-lasting. Further, the combination of monomenthyl succinate with WS3'm was found to provide a complementary cooling CA 022074~77 1997-06-10 effect since different areas of the mouth and throat were affected by the respective coolants.

Examples 6-8 - Alcoholic Beverages Three dirrelent alcoholic beverages were made by using 17.00 grams of high fructose corn syrup, 140.89 grams of water and 21.05, 42.11 and 84.22 grams of 190 proof alcohol in order to obtain alcoholic drinks of 20, 40 and 80 proof, respectively.
To samples of each of the three alcoholic beverages was added 0.07% by weight of monomenthyl succinate. A cooling effect was noted in the 20 and 40 proof alcoholic beverages contai~ g the monomenthyl succinate but not in the 80 proof beverage.
As a result, a new sample of 80 proof alcoholic beverage was prepared using a higher concentration of monomenthyl succinate and, at this higher concentration level a pleasant, long-lasting cooling effect was noticed by the tasting panel. In addition, the tasting panel concluded that the monomenthyl succinate enhanced the taste sensation of the alcohol in all of the alcoholic beverages and, as a result, the 20, 40 and 80 proof alcoholic beverages including monomenthyl succinate each tasted as if there were a higher alcohol content than the corresponding control beverage having the same alcohol content no coolant compound.

Example 9 - Chewing Gum A conventional chewing gum base was employed for this example. To the chewing gum base was added 1.0% by weight of mixed berry flavoring. Then, to one of the chewing gum samples 0.30% by weight of monomenthyl succinate was added.
A pleasant, long-lasting cooling effect in the back of the mouth and throat was noted CA 022074~7 1997-06-10 by the tasting panel in the chewing gum containing monomenthyl succinate. In addition, no minty taste was apparent.

Example 10 - Sugarless Candy Sugarless deposited sorbitol candy was prepared by heating one kilogram of sorbitol syrup to 170~C, cooling the sorbitol syrup to 135~C, adding 12 grams of citric acid with stirring and cooling this composition down to 110~C. At that point, 20 grams of sorbitol powder and the flavorant including 0.05% by weight, based on the weight of the composition of monomenthyl succinate was added to the sugarless candy formulation by stirring it in slowly. Finally, the candy is deposited and allowed to harden.
A taste panel found that the sugarless hard candy formulation containing the monomenthyl succinate provided a long-lasting, pleasant cooling effect.

Examples 11-14 and Comparative Examples A-B
Mono Menthylsuccinate in Cigarette Filters Combined With Menthol in the Tobacco The tobacco rods of some regular international blended cigarettes and of flue-cured cigarettes were each injected with 20 ,ul of a 10~o solution of menthol crystals in ethanol. The menthol-injected cigarettes were then divided into five sets. 20 ,ul, 30 ,ul, 40 ,ul, and 50 Ill of a 1% solution of mono menthylsuccinate in triacetine were injected into the filters of the first four sets of cigarettes with the fifth set of cigarettes being used as a control. Each set of cigarettes included a control with no menthol and no mono menthylsuccinate, a cigarette including only menthol, a cigarette CA 022074~7 1997-06-10 including only mono menthylsuccinate and a cigarette including both menthol and mono menthylsuccinate.
An expert smoking panel (ESP) lighted, smoked and tasted each set of the test cigarettes and found that at a level of 0.2 ~1 of mono menthylsuccinate and no menthol, there was no cooling effect. At 0.3 ~1 of mono menthylsuccinate with no menthol a slight cooling effect was noted. At a level of 0.4 ,~Ll of mono menthylsuccinate a strong cooling effect with a refreshing aftertaste was noted by the ESP. Further, in combination with menthol in the tobacco at this level, no enhancement of the "mint" flavor note of the menthol by the mono menthylsuccinate was detected by the ESP. At a level of 0.5 ,ul of mono menthylsuccinate the cooling effect was even more evident to the ESP and still no enhancement of the "mint" flavor note of menthol was noted. However, a minor increase in irritation was experienced by the ESP at this level of mono menthysuccinate.
The ESP concluded that the mono menthylsuccinate injected in the filter of cigarettes had a cooling effect on the smoke and provided a lingering refreshing character in the mouth without significantly altering the flavor note of the menthol in the tobacco.

Example 15 Mono Menthylsuccinate Used With WS3tm Coolant in Filters and Menthol in the Tobacco Rod The tobacco rod of selected cigarettes as in Examples 1-4 above was injected with 20 ~l of a 10% solution of menthol crystals in ethanol. The menthol injected cigarettes were divided into two sets. 45 ,ul of a 1% solution of mono menthylsuccinate CA 022074~7 1997-06-10 in triacetine and 15 ,ul of a 1% solution of WS3tm in triacetine were injected into the filter of one set of the cigarettes containing menthol.
The ESP observed an intense cooling effect and a slight enhancement of the mint and aromatic flavor notes of the menthol, as compared to the menthol-containing control. No increase in irritation was found. The panel concluded that at these levels, a synergistic effect occurred between the two cooling agents.

Examples 16-17 Mono Menthylsuccinate in Chewing Tobacco and Snuff Tobacco 0.08% and 0.12% by weight of mono menthylsuccinate were added by injection to chewing tobacco using a 10 ,ul gas chromotography syringe and the same levels of mono menthylsuccinate were added to snuff by spraying using a thin atomizer.
Each sample of the tobacco was kept in the mouth of the ESP members for a one minute test period after which the mouth was cleaned with pure water and a waiting period of five minutes was observed before starting a new evaluation.
At a level of 0.08% by weight, a refreshing effect was observed by the ESP
after a period of 2-3 minutes. At 0.12% by weight an even higher intensity of cooling was observed ap~rr)xi~ tely two minutes after the tobacco was removed from the mouth, whereby the interior of the mouth was judged as being cleaner. Also, the ESP
concluded that a more pleasant refreshing aftertaste was present. The aftertaste lasted for up to five minutes following the removal of the tobacco from the mouth.

Examples 18-19 Mono Menthylsuccinate in Filter Tipping Paper of Indonesian Cigarettes CA 022074~7 1997-06-10 10 ,~Ll and 20 ~1 of a l~o solution of mono menthylsuccinate in triacetine was distributed in the form of a thin film applied with a soft brush over the first third of the mouth end of the filter tipping paper of different types of Kretek cigarettes obtained from the Indonesian market.
At 0.10 ,ul of mono menthylsuccinate, the ESP found a slight refreshing effect on the lips after 2-3 minutes following insertion of the Kretek cigarette in the mouth.
At 20 ,ul a cooling effect associated with a refreshing character started a~pro~",lately one minute after insertion of the Kretek cigarette in the mouth and lasted for up to five minutes on the lips and inner part of the mouth. The ESP concluded that the mono menthylsuccinate had an effect that can be efficaceous in retaining a refreshing, clean character on the lips and inner part of the mouth when applied on the mouth end of a Kretek cigarette.
These examples have been given for the purpose of illustration and description only and are not to be construed as limiting the scope of the invention in any way.
The scope of the invention is to be determined from the claims appended hereto.

Claims (16)

1. A composition selected from topical products for humans and animals, oral care products, nasal care products, toilet articles, filters, combustible papers and leaf wrappers for smoking tobacco products, chewing tobacco products, snuff tobacco products and chewing gum which comprises a product base and an effective amount of a coolant selected from the group consisting of monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl succinate and mixtures thereof.
2. A composition as claimed in claim 1 wherein the products are selected from topical products for humans and animals, oral care products, nasal care products and toilet articles.
3. A composition as claimed in claim 1 wherein the products are selected from chewing tobacco products, moist snuff tobacco products and snuff tobacco products and the filters of smoking tobacco products.
4. An ingestible product for humans and animals which is selected from the group consisting of baked goods, dairy products, fruit ices, confectionery products, jams, jellies, gelatins, puddings, animal feeds, lozenges, cough mixtures, decongestants, anti-irritants, antacids, anti-indigestion preparations, oral analgesics, pressed confectionery tablets, hard boiled candies, chewing gums, pectin-based candies, chewy candies, cream-centered candies, fondants, toothpastes, mouthwashes, breath fresheners, carbonated beverages, mineral waters, powdered beverage mixes, non-alcoholic beverages, alcoholic beverages and distilled beverages, which comprises a product base and an effective amount of a coolant selected from the group consisting of monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl succinate and mixtures thereof, with the proviso that when said ingestible product is selected from the group consisting of alcoholic beverages and distilled beverages the amount of the coolant is from 0.001-1.0% by weight, based on the total weight of the ingestible product.
5. A product as claimed in claim 4 wherein the ingestible product is a foodstuff selected from baked goods, dairy products, fruit ices, confectionery products, sugarless candies, jams, jellies, gelatins, puddings and animal feeds.
6. A product as claimed in claim 4 wherein the ingestible product is selected from lozenges, cough mixtures, decongestants, anti-irritants, antacids, anti-indigestion preparations and oral analgesics.
7. A product as claimed in claim 4 wherein the ingestible product is selected from pressed confectionery tablets, hard boiled candies, chewing gums, pectin-based candies, chewy candies, creme-centered candies, fondants sugarless hard-boiled candies, sugarless pectin-based candies, sugarless chewy candies, sugarless cream-centered candies, toothpastes, mouthwashes, breath fresheners, alcoholic beverages, carbonated beverages, mineral waters, powdered beverage mixes, non-alcoholic beverages, and distilled beverages.
8. A composition as claimed in any one of claims 1-7 which comprises from 0.001-1.0% by weight, based on the total weight of the product, of said coolant.
9. A flavoring composition which comprises from 1-80% by weight of a coolant selected from the group consisting of monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl succinate and mixtures thereof and 20-99 % by weight of a flavorant diluent which comprises at least one flavorant selected from the group consisting of fruit flavours, herbal oils, sweetening syrups, flavoring syrups and flavoring oils.
10. A flavoring composition as claimed in claim 9 which comprises from 5-50 % by weight of the coolant and from 50-95 % of the flavorant diluent.
11. A flavoring composition as claimed in any one of claims 9-10 wherein the flavorant diluent further comprises a polar solvent selected from ethanol, ethyl acetate, propylene glycol, isopropyl alcohol and glycerin.
12. A flavoring composition as claimed in any one of claims 9-10 which further comprises at least one secondary coolant component.
13. A coolant composition which comprises an effective amount of at least one primary coolant selected from the group consisting of monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate, and at least one secondary coolant component.
14. A coolant composition as claimed in any one of claims 12-13 wherein the secondary coolant component is selected from the group consisting of menthol, carboxamides, ketals, menthyl acetate, menthyl lactate, 3-menthoxypropane-1,2 diol and mixtures thereof.
15. A coolant composition as claimed in claim 14 wherein the carboxamide coolant component is selected, from the group consisting of:

where R', when taken separately, is hydrogen or an aliphatic radical containing up to 25 carbon atoms; R" when taken separately is hydroxy, or an aliphatic radical containing up to 25 carbon atoms, with the proviso that when R' is hydrogen R" may also be an aryl radical of up to 10 carbon atoms and selected from the group consisting of substituted phenyl, phenalkyl, substituted phenalkyl, naphthyl, substituted naphthyl and pyridyl; and R' and R", when taken together with the nitrogen atom to which they are attached, represent a cyclic or heterocylic group of up to 25 carbon atoms;
acyclic tertiary and secondary carboxamides of the formula:

where R' and R", when taken separately, are each hydrogen, C1-C5 alkyl or C1-C8 hydroxyalkyl and provide a total of no more than 8 carbon atoms, with the proviso that when R' is hydrogen R" may also be alkylcarboxyalkyl of up to 6 carbon atoms;
R' and R", when taken together, represent an alkylene group of up to 6 carbon atoms, the opposite ends of which group are attached to the amide nitrogen atom thereby to form a nitrogen heterocycle, the carbon chain of which may optionally be interrupted by oxygen; R1 is hydrogen or C1-C5 alkyl; and R2 and R3 are each C1-C5 alkyl; with the provisos that (i) R1, R2, and R3 together provide a total of at least 5 carbon atoms; and (ii) when R1 is hydrogen, R2 is C2-C5 alkyl and R3 is C2-C5 alkyl and at least one of R2 and R3 is branched and mixtures thereof.
16. A coolant composition as claimed in claim 14 wherein the ketal coolant component is selected from the group consisting of:

in which R1 represents a C2-C6-alkylene radical having at least 1, but not more than 3, hydroxyl group(s), and either R2 and R3 independently of one another represent C1-C10-alkyl which is optionally substituted by 1 to 3 radicals selected from the group comprising hydroxyl, amino, halogen, C5-C7-cycloalkyl, C6-C12-aryl, with the proviso that the total of the C atoms of R2 and R3 is not less than 3, or R2 and R3 together represent an alkylene radical which, together with the carbon atom which carries the radicals R2 and R3, forms a 5-7 membered ring, optionally substituted by C1-C6-alkyl groups.
CA002207457A 1995-08-29 1996-08-29 Coolant compositions Expired - Lifetime CA2207457C (en)

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US08/520399 1995-08-29
US08/520,399 US5725865A (en) 1995-08-29 1995-08-29 Coolant compositions
US08/629598 1996-04-09
US08/629,598 US5843466A (en) 1995-08-29 1996-04-09 Coolant compositions
US08/701,141 US5752529A (en) 1996-08-21 1996-08-21 Tobacco products containing coolant compositions
US08/701,141 1996-08-21

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