Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
  • C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/20—Synthetic spices, flavouring agents or condiments
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/20—Synthetic spices, flavouring agents or condiments
  • A23L27/203—Alicyclic compounds
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/20—Synthetic spices, flavouring agents or condiments
  • A23L27/205—Heterocyclic compounds
  • A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
  • C07C47/105—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing rings
  • C07C47/11—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing rings monocyclic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
  • C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
  • C07C47/225—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/28—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
  • C07C47/293—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings with three- or four-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/28—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
  • C07C47/34—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings polycyclic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/38—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
  • C07C47/45—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings having unsaturation outside the rings
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0069—Heterocyclic compounds
  • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
  • C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes

Definitions

• the present invention relates generally to the field of flavorings and fragrances. More particularly, the present invention relates to citral derivatives that provide beverages and other food products, as well as perfumes and other fragrant articles with a lemony scent, while at the same time overcoming the stability limitations of the native citral compound.
• Citral (3,7 dimethyl 2,6 octadienal) is a major component of lemon smell, and has the sweet-acidulated character of natural lemon.
• lemon smell has become ' associated with freshness and cleanliness, both in drinks and in household products, and in fragrances and flavorings, generally.
• Lemon drinks, whether natural or synthetic, are naturally acid, which causes rapid degradation of citral to unpleasant-smelling products like cresol. This means that the shelf life of lemonade is correspondingly short, creating an expensive logistical problem.
• the problem is of a different nature.
• In order to associate bacteriological cleanliness with the smell of lemon these products frequently use lemon-scented bleach (hypochlonte).
• Citral is unstable in bleach, and cannot therefore be used. Instead, its nitrile analogue, geranyl nitrile, with its less satisfactory oily-metallic lemon note has to be used.
• citral derivatives The chemical instability of citral is largely due to the two double bonds and an aldehyde group, all of which are potentially susceptible to reaction, particularly when used in harsh environments, such as lemon-scented bleach. It would be desirable to develop citral derivatives with improved useful lifetimes, and, preferably, improved odor intensity, while maintaining the lemon note of citral.
• the present invention provides such citral derivatives.
• citral derivatives that maintain the fragrance characteristics and lemony flavor of citral, while lowering the allergic properties, providing a longer shelf-life than citral, and/or increasing the odor intensity relative to citral are disclosed. Also disclosed are methods of making the derivatives, and articles of manufacture including the derivatives.
• the citral derivatives are prepared by replacing one or more double bonds in the parent molecule with a cyclopropyl group, which can be unsubstituted, or substituted with one or two lower alkyl, preferably methyl groups.
• the alkyl groups can optionally be substituted, for example, with electron donating groups, electron withdrawing groups, groups which increase the hydrophilicity or hydrophobocity, and the like.
• the derivatives are prepared by replacing ' one or more aldehyde groups in citral with a nitrile, methyl ether or acetal group.
• the acetal groups can provide the compounds with a long lasting flavor or fragrance, where the acetals slowly hydrolyze to provide the parent aldehyde compounds.
• suitable derivatives are prepared such that the aldehyde and at least one double bond functional group is derivatized as described herein.
• suitable articles of manufacture include candles, air fresheners, perfumes, disinfectant compositions, hypochlorite (bleach) compositions, beverages such as beer and soda, denture cleanser tablets as described, for example, in U.S. Patent No. 5,571,519, the contents of which are hereby incorporated by reference in their entirety, and flavored orally-delivered products such as lozenges, candies, and the like.
• citral derivatives which can be used, for example, as fragrances and flavorings that have a longer useful shelf life than citral, are disclosed.
• the citral derivatives have a similar odor to citral and also have improved physical and/or chemical properties relative to citral. These improved properties include increased stability to high pH, low pH, improved half-life, lower likelihood of causing allergic reactions, and/or increased odor intensity.
• the compounds of Formulas 2-4 described herein have one or more double bonds of citral or the citral derivatives in Formula 1 replaced with a suitable three membered ring.
• the compounds, and mixtures thereof are stable in various media in which citral itself is relatively unstable and also have unstable, and also have odor characteristics which are very similar to that of citral.
• Formula 1 represents citral and citral derivatives that can be modified using the chemistry described herein to replace one or both of the double bonds with appropriate ring structures, thus improving the various physical and/or chemical properties of the molecule.
• R 1-6 can be, independently, H, C 1-5 alkyl, substituted C 1-5 alkyl, halo, hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid, urea, and thiourea, where the substituents on the alkyl groups are selected from halo, hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid, urea, thiourea, and the like.
• the double bond adjacent to the aldehyde group in citral is saturated (i.e., citronellal), and the derivatives are the same but for the saturated double bond at this position.
• Formulas 2-4 below represent citral derivatives as described herein, where one or both of the double bonds are replaced with a suitable three membered ring.
• Z is O, S, or C(R) 2 ,
• R is H, C 1-5 alkyl, such as methyl, or C 1-5 substituted alkyl, and
• R 1-4 represent hydrogen
• R 5-6 represent methyl
• Z represents C(R) 2 .
• one or more R groups are methyl, with the other R groups representing hydrogen.
• one Z can represent saturation at both carbons to which it is bound (i.e., no double bond or cyclopropane, oxirane or thiirane ring), so long as one Z is O, S or C(R) 2 .
• citral can be cyclopropanated in one or both of the positions, corresponding to the two double bonds of the molecule. Including stereoisomers, there are thus five CP- variations on citral, shown below.
• the cyclopropane rings can include a CH 2 moiety, or can be substituted with one or two . 5 alkyl (i.e., methyl) groups.
• the methyl or dimethyl analogues have a tunnelling vibrational spectrum that more closely matches citral than the unsubstituted cyclopropane derivatives, and has a sweeter smell than the unsubstituted cyclopropyl derivatives.
• citral derivatives described herein include derivatives in which one or both of the double bonds is replaced with a (unsubstituted, monoalkyl or dialkyl, where alkyl can be substituted or unsubstituted, and is preferably methyl) cyclopropyl group.
• the compounds can include, in combination with or in place of a cyclopropyl group, the replacement of the aldehyde with a methyl ether, a nitrile or an acetal group.
• citral derivatives of Formulas 2-4 can be prepared using any of the citral derivatives described above in Formula 1, to the extent that the synthetic route is not incompatible with any of the substituents that may be present.
• citral (or citronellal) is used as a starting material to prepare various citral (or citronellal) derivatives described in Formulas 2-4 where R 1- are hydrogen and R 5-6 are methyl.
• methyl, dimethyl or unsubstituted cyclopropane derivatives involves, for example, bromoform reaction to form the dibromocyclopropane derivative, followed by stoichiometric reaction with methyl lithium.
• the aldehyde group is typically protected as an acetal during the reaction, and deprotected as desired after the reactions take place. In one embodiment, however, the acetals (for example, dimethyl, diethyl, or ethylene glycol) are not deprotected to the aldehyde, such that the flavoring or fragrance includes a portion or entirely the acetals.
• citral derivatives including one or two cyclopropane rings, can also include a nitrile or methyl ether group as a replacement for the aldehyde group.
• Citral derivatives can further be prepared in which one or more a double bonds are converted to (unsubstituted, methyl or dimethyl) cyclopropyl derivatives that also include a nitrile group in place of the aldehyde using the chemistry described above.
• the citral derivatives can be included in virtually any article of manufacture that can include citral, or for that matter, other lemon fragrances, whether natural or artificial. Examples include bleach, detergents, flavorings and fragrances, beverages, including alcoholic beverages, and the like.
• the citral derivatives can be used in applications like soaps, shampoos, body deodorants and antiperspirants, solid or liquid detergents for treating textiles, fabric softeners, detergent compositions and/or all-purpose cleaners for cleaning dishes or various surfaces, for both household and industrial use.
• the use of the compounds is not limited to the above- mentioned products, as they be used in other current uses in perfumery, namely the perfuming of soaps and shower gels, hygiene or hair-care products, as well as of body deodorants, air fresheners and cosmetic preparations, and even in fine perfumery, namely in perfumes and colognes. These uses are described in more detail below.
• the compounds can be used as perfuming ingredients, as single compounds or as mixture thereof, preferably at a range of at least about 30% by weight of the perfume composition, more preferably at a range of at least about 60%o by weight of the composition.
• the compounds can even be used in their pure state or as mixtures, without added components.
• the olfactive characteristics of the individual compounds are also present in mixtures thereof, and mixtures of these compounds can be used as perfuming ingredients. This may be particularly advantageous where separation and/or purification steps can be avoided by using compound mixtures.
• citral derivatives can be used alone or in admixture with other perfuming ingredients, solvents or adjuvants of current use in the art.
• the nature and the variety of these co-ingredients do not require a more detailed description here, which, moreover, would not be exhaustive, and the person skilled in the art will be able to choose the latter through its general knowledge and as a function of the nature of the product to be perfumed and of the desired olfactive effect.
• perfuming ingredients typically belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitrites, terpene hydrocarbons, sulfur- and nitrogen- containing heterocyclic compounds, as well as essential oils of natural or synthetic origin.
• alcohols aldehydes, ketones, esters, ethers, acetates, nitrites, terpene hydrocarbons, sulfur- and nitrogen- containing heterocyclic compounds, as well as essential oils of natural or synthetic origin.
• citral derivatives can be incorporated in the various products vary within a large range of values. These values depend on the nature of the article or product that one desires to perfume and the odor effect searched for, as well as on the nature of the co- ingredients in a given composition when the compounds are used in admixture with perfuming co- ingredients, solvents or adjuvants of current use in the art.
• the citral derivatives are typically present at concentrations between about 0.1 and about 10%, or even more, by weight of these compounds relative to the weight of the perfuming composition in which they are incorporated. Far lower concentrations than those mentioned above can be used when the compounds are directly applied for perfuming the various consumer products cited beforehand.
• the compounds are relatively stable in typically aggressive media for perfumes. Accordingly, they can be used in detergents containing bleaching agents and activators such as, for example, tetraacetylethylenediamine (TAED), hypohalites, in particular hypochlorite, peroxygenated bleaching agents such as, for example, perborates, etc.
• TAED tetraacetylethylenediamine
• hypohalites in particular hypochlorite
• peroxygenated bleaching agents such as, for example, perborates, etc.
• the compounds can also be used in body deodorants and antiperspirants, for example, those containing aluminum salts.
• compositions herein include a detersive surfactant and optionally, one or more additional detergent ingredients, including materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
• additional detergent ingredients including materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
• additional detergent ingredients including materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
• the conventional nonionic and amphoteric surfactants such as the C 12-18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6-12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxylates), C 1 -18 betaines and sulfobetaines ("sultaines"), C 10-18 amine oxides, and the like, can also be included in the overall compositions.
• the C 10- ⁇ 8 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12-18 N-methylglucamides. See WO 9,206,154.
• sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as o- 18 N-(3-methoxypropyl) glucamide.
• the N-propyl through N-hexyl C 12-18 glucamides can be used for low sudsing.
• C 10-2 o conventional soaps may also be used, however synthetic detergents are preferred. If high sudsing is desired, the branched-chain soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
• Other conventional useful surfactants are listed in standard texts. See also U.S. Pat. No. 3,664,961 to Norris.
• compositions incorporating only synthetic detergents have a detergent level of from about 0.5% to 50%>.
• Compositions containing soap preferably comprise from about 10%> to about 90% soap.
• the detergent compositions herein can only only detersive surfactants and the citral derivative(s), the compositions preferably contain other ingredients commonly used in detergent products.
• Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
• the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
• the compositions will typically comprise at least about 1% builder.
• Liquid formulations typically comprise from about 5%> to about 50%>, more typically about 5% to about 30% > , by weight, of detergent builder.
• Granular formulations typically comprise from about 10%) to about 80%>, more typically from about 15%> to about 50% by weight, of the detergent builder.
• Lower or higher levels of builder are not meant to be excluded.
• Inorganic or detergent builders include, but are not limited to phosphate builders such as, the alkali metal, ammonium and allanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, and phytic acid, and non-phosphorous builders such as silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
• Non-phosphate builders are required in some locales.
• Organic builders suitable for use herein include polycarboxylate builders such as disclosed in U.S. Pat. No. 3,308,067 to Diehl; U.S. Pat. No. 4,144,226 to Crutchfield and U.S. Pat. No. 4,246,495 to Crutchfield.
• Soil Release agents are desirably used in laundry detergents of the instant invention.
• Suitable soil release agents include those of U.S. Pat. No. 4,968,451 to Scheibel and Gosselink: such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. Pat. No.
• DMT dimethyl terephthalate
• PG 1,2-propylene glycol
• 4,702,857 to Gosselink for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na- dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. Pat. No.
• compositions herein can contain other ingredients such as enzymes, bleaches, fabric softening agents, dye transfer inhibitors, suds suppressors, and chelating agents, all well known within the art.
• the pH of the detergent composition is that which is measured at 1%> concentration of the detergent composition in distilled-water at 20°C.
• the detergent compositions herein have a pH of from about 7.1 to about 13, more typically from about 7.5 to about 9.5 for liquid detergents and from about 8 to about 12 for granular detergents.
• the derivatives described herein can be used alone and simply mixed with essential detergent ingredient, most notably surfactant, they can also be desirably combined into three-part formulations which combine (a) a non-fragranced detergent base comprising one or more synthetic detergents and (b) one or more of the derivatives described herein.
• both aldehydes and acetals are present, such that the aldehydes provide desirable in-package and in-use (wash-time) fragrance, while the acetals provide a long-term fragrance to the laundered textile fabrics.
• the fully-formulated fragrance can be prepared using numerous known odorant ingredients of natural or synthetic origin.
• the range of the natural raw substances can embrace not only readily-volatile, but also moderately-volatile and slightly-volatile components and that of the synthetics can include representatives from practically all classes of fragrant substances, as will be evident from the following illustrative compilation: natural products, such as tree moss absolute, basil oil, citrus fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil, alcohols, such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, aldehydes, such as citral, HelionalTM, alpha-hexyl-cinnamaldehyde, hydroxycitronellal, Lilial
• any conventional fragrant acetal or ketal known in the art can be added to the present composition as an optional component of the conventionally formulated perfume (c).
• Such conventional fragrant acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those comprising phenylethyl moieties, or more recently developed specialties such as those described in a United States Patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-Indanes, see U.S. Pat. No. 5 ,084,440.
• other recent synthetic specialties can be included in the perfume compositions for fully- formulated detergents.
• Detergents including the derivatives described herein may further, optionally, if desired, contain other known compounds having the capability to enhance substantivity of a fragrance.
• Such compounds include, but are not limited to, the aluminium alkoxides such as isobutylaluminium diferanylate as disclosed in U.S. Pat. No. 4,055,634; or the known titanate and zirconate esters or oligoesters of fragrant materials such as those disclosed in U.S. Pat. No. 3,947,574, and U.S. Pat. No. 3,779,932, the contents of each of which are hereby incorporated by reference in their entirey.
• organoaluminum, organotitanium or organozinc derivatives they may be incorporated into the present formulations at their art-known levels.
• the citral derivatives described herein can be incorporated into beverages and impart various flavorings to the beverages.
• the beverage composition can be a cola beverage composition, and can also be coffee, tea, dairy beverage, fruit juice drink, orange drink, lemon-lime drink, beer, malt beverages, or other flavored beverage.
• the beverages can be in liquid or powdered form.
• the beverage compositions can also include one or more flavoring agents; artificial colorants; vitamin additives; preservatives; caffeine additives; water; acidulants; thickeners; buffering agents; emulsifiers; and or fruit juice concentrates.
• Artificial colorants which may be used include caramel color, yellow 6 and yellow 5.
• Useful vitamin additives include vitamin B2, vitamin B6, vitamin B12, vitamin C (ascorbic acid), niacin, pantothenic acid, biotin and folic acid.
• Suitable preservatives include sodium or potassium benzoate. Salts which may be used include sodium, potassium and magnesium chloride.
• Exemplary emulsifiers are gum arabic and purity gum, and a useful thickener is pectin.
• Suitable acidulants include citric, phosphoric and malic acid, and potential buffering agents include sodium and potassium citrate.
• the beverage is a carbonated cola beverage.
• the pH is generally about 2.8 and the following ingredients can be used to make the syrup for these compositions: Flavor Concentrate, including one or more of the derivatives described herein (22.22 ml), 80%) Phosphoric Acid (5.55 g), Citric Acid (0.267 g), Caffeine (1.24 g), artificial sweetener, sugar or corn syrup (to taste, depending on the actual sweetener) and Potassium Citrate (4.07 g).
• Flavor Concentrate including one or more of the derivatives described herein (22.22 ml), 80%) Phosphoric Acid (5.55 g), Citric Acid (0.267 g), Caffeine (1.24 g), artificial sweetener, sugar or corn syrup (to taste, depending on the actual sweetener) and Potassium Citrate (4.07 g).
• the beverage composition can be prepared, for example, by mixing the foregoing syrup with carbonated water in a proportion of 50 ml syrup to 250 ml of
• the beverage is a beer or malt beverage.
• Preferred flavorings for beer and malt beverages include lemon, lime and lemon-lime.
• the flavorings include citral derivatives in which one of both of the double bonds are replaced with a cyclopropane group, where the cyclopropane groups can, independently, be unsubstituted, or include one or two alkyl or substituted alkyl groups, preferably methyl groups. The amount of flavoring can be adjusted according to taste.
• Flavored food and pharmaceutical compositions including one or more of the derivatives described herein can also be prepared.
• the derivatives can be incorporated into conventional foodstuffs using techniques well known to those of skill in the art.
• the derivatives can be incorporated within polymeric particles, which can, in turn, be dispersed within and/or over a surface of an orally-deliverable matrix material, which is usually a solid or semi-solid substrate.
• the derivatives can be released into the orally-deliverable polymeric matrix material as the composition is chewed and held in the mouth, thus prolonging the flavor of the composition.
• the flavor can be made available as the product is consumed or be released into the matrix material as the composition is further processed.
• the relative amounts of the additives can be selected to provide simultaneous release and exhaustion of the compounds.
• the flavored composition includes an orally-deliverable matrix material; a plurality of water insoluble polymeric particles dispersed in the orally-deliverable matrix material, where the polymeric particles individually define networks of internal pores and are non-degradable in the digestive tract; and one or more derivatives as described herein entrapped within the internal pore networks.
• the derivatives are released as the matrix is chewed, dissolved in the mouth, or undergoes further processing selected from the group consisting of liquid addition, dry blending, stirring, mixing, heating, baking, and cooking.
• the orally-deliverable matrix material can be selected from the group consisting of gums, latex materials, crystallized sugars, amorphous sugars, fondants, nougats, jams, jellies, pastes, powders, dry blends, dehydrated food mixes, baked goods, batters, doughs, tablets, and lozenges. Chewing Gum
• a flavorless gum base can be combined with a citral or other suitable derivative as described herein to a desired flavor concentration.
• a blade mixer is heated to about 110F, the gum base is preheated so that it is softened, and the gum base is then added to the mixer and allowed to mix for approximately 30 seconds.
• the flavored derivative is then added to the mixer and mixed for a suitable amount of time.
• the gum can be then removed from the mixer and rolled to stick thickness on waxed paper while warm.
• the derivatives described herein are incorporated into a system which can release a fragrance in a controlled manner.
• These include substrates such as air fresheners, laundry detergents, fabric softeners, deodorants, lotions, and other household items.
• the fragrances are generally one or more derivatives of essential oils as described herein, each present in different quantities.
• U.S. Pat. No. 4,587,129 the contents of which are hereby incorporated by reference in their entirety, describes a method for preparing gel articles which contain up to 90%o by weight of fragrance or perfume oils.
• the gels are prepared from a polymer having a hydroxy (lower alkoxy) 2-alkeneoate, a hydroxy (lower alkoxy) lower alkyl 2-alkeneoate, or a hydroxy poly (lower alkoxy) lower alkyl 2-alkeneoate and a polyethylenically unsaturated crosslinking agent.
• These materials have continuous slow release properties, i.e., they release the fragrance component continuously over a long period of time.
• all or a portion of those derivatives that include an aldehyde group can be modified to include an acetal group, which can cause the formulations to release fragrance over a period of time as the acetal hydrolyzes to form the aldehyde compound.

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• 2002
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