KR20060032136A - Novel fragrance derivatives - Google Patents

Abstract

A method for derivatizing aromachemical or fragrance compound containing at least one double bond in the molecular structure thereof to enhance the binding characteristics of the aromachemical or fragrance compound to metal ions without significantly affecting the odor characteristics thereof comprising converting the at least one double bond to an oxirane or thiirane group.

Description

Novel Aroma Derivatives {NOVEL FRAGRANCE DERIVATIVES}

The present invention generally relates to the field of fragrance FRAGRANCE. In particular, the present invention relates to traditional aromatic chemicals, ie improved derivatives of aromatic compounds, which provide perfumes and other products with properties and advantages different from traditional derivatives. These derivatives are used for the needs of all applications which are met by the traditional direction in which they are derived. The present invention also relates to mixtures of these derivatives, methods of preparation and their use as perfume substances for application to various substrates.

There are many known aromas that are used as ingredients in perfumes and in a wide range of other products. For example, laundry detergents, fabric softeners, rinse conditioners and other products for use in textile fibers, which contain fragrances in principle.

Improved fragrances and flavor derivatives are disclosed that have a similar or improved odor intensity to known fragrances prior to induction. In particular, derivatives are disclosed which retain the flavor and / or aromatic properties of aromatic molecules containing covalent double bonds. Also disclosed are methods of making such derivatives and articles comprising the derivatives.

[Summary of invention]

The present invention relates to the derivation of aromatic molecules or aromatic chemical molecules with one or more double bonds. Wherein at least one double bond is converted to oxirane or thiirane. The method can be described by the conversion of a double bond to an oxirane group. Then, if necessary, it is converted into a tee group by the following scheme. :

The present invention is due to the discovery that replacing the double bond of an aromatic compound with an oxirane or tyrane group can allow binding to metal ions without changing the odor characteristics of the molecule. The calculation shows that the group of tee is optimal at this point. The ability to bind metal ions is desirable because the receptor protein responsible for the detection of odors incorporates zinc ions at the binding site. The metal-binding ability thus increases the affinity of the derivative for the receptor and therefore increases its ability as an odorant. The electronic structure of oxygen, and especially sulfur, allows them to coordinate with metal ions. The conversion of the double bond to oxirane is obtained by oxidation. For example, in the presence of Ti (IV) isopropoxide, with an Ag catalyst or t-butyl hydroperoxide, such as meta-chloroperbenzoic acid (mCPBA), peroxybenzoic acid, peracids such as oxygen By reaction (Sharpless reaction). The oxirane can then be used to prepare the corresponding tyrane by reacting it with triphenylphosphine sulfide-picric acid, thiourea, potassium thiocyanate on silica gel. Alternatively, thiirane can be prepared directly from the double bond by reacting with succinimide-N-sulphenyl-chloride as shown below:

Examples of suitable products into which the derivatives of the present invention are incorporated include perfumes and colognes, candles, air fresheners, detergent compositions and fungicides.

1 illustrates the structure of various thiiranes that may be prepared in accordance with the present invention.

Detailed description of the invention

Derivatives of the invention can be used, for example, as aroma in any application to which the original aroma from which they are derived applies.

Derivatives of the present invention may be included in virtually any product that may include traditional aromas, including natural or artificial. Examples include bleach, detergents, flavors and aromas, beverages including alcoholic beverages, and the like. These derivatives can be used in applications such as soaps, shampoos, deodorants and antiperspirants, solid or liquid detergents for textile processing, fabric softeners, detergent compositions and / or household and industrial multi-purpose cleaners for cleaning various surfaces. Of course, the use of this compound is not limited to the above-mentioned products, but the fragrance of fragrances, ie soaps and shower gels, hygiene or hair-care products, as well as of deodorants, air fresheners and cosmetic preparations, and of high-quality fragrances, ie perfumes and colognes. It can also be used for other known uses. These uses are described in more detail below.

This compound may be used as the fragrance component, as a single compound or mixtures thereof, preferably in the range of at least about 30 wt% of the perfume composition, more preferably at least about 60 wt% of the composition. This compound can be used even in the pure state or as a mixture, without added components. In addition, the olfactive properties of the individual compounds are also present in the mixture, and mixtures of these compounds can be used as flavoring ingredients. This would be particularly desirable if a separation and / or purification step can be avoided by using a mixture of compounds.

In all mentioned uses, these derivatives can be used alone or as a mixture with other perfume ingredients, solvents or adjuvants currently used in the art. The inherent nature and variety of these co-components need not be described in detail here, and furthermore, there will be no end, and a person skilled in the art will be able to select according to the action of the product properties and the desired aroma effect through general knowledge.

These perfume ingredients may belong to various chemical classes of natural or synthetic essential oils as well as alcohols, aldehydes, ketones, esters, ethers, acetates, nitrites, terpene hydrocarbons, sulfur- and nitrogen-containing heterocyclic compounds. will be. Many of these components are described in textbooks such as book of S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, NJ, USA, which documents and their recent editions or other similar documents are incorporated herein by reference in their entirety. It is incorporated.

These derivatives can be incorporated into a wide variety of products in a wide range of values. These values depend on the fragrance and odor the product seeks, as well as the nature of the co-component of a given composition when used in admixture with co-fragrance components, solvents or auxiliaries used in this field.

By way of example, these derivatives are generally present at a concentration of about 0.1 to about 10%, or more, by weight of these compounds relative to the weight of the fragrance composition to which they are incorporated. If the compound is applied directly for the flavoring of the various consumer products mentioned above, it can be used at much lower concentrations.

This compound can also be used to include deodorants and antiperspirants such as aluminum salts. These embodiments are described in more detail below.

In addition to the derivatives described herein, the composition includes a cleaning surfactant and optionally a substance for the treatment of the substrate to be cleaned, for aiding or enhancing the cleaning performance or for changing the aesthetics of the cleaning composition (eg, perfumes, colorants, Dyes and the like) one or more additional cleaning components. Synthetic cleansing surfactants useful herein are, but are not limited to, from about 0.5 wt% to about 90 wt%, with traditional C 1-18 alkyl benzene sulfonates ("LAS") and primary, branch-chain and random C10-20 alkyl sulfates ("AS"), and the like.

Preferred compositions incorporating only synthetic detergents have a detergent concentration of about 0.5% to 50%. The soap containing composition preferably comprises about 10% to about 90% soap.

The compositions herein may contain other ingredients such as enzymes, bleaches, fabric softeners, dye transfer inhibitors, suds suppressors, and chelating agents known in the art.

The derivatives described herein can be incorporated into beverages and impart various flavors to the beverages. The beverage composition may be a cola beverage composition and may be coffee, tea, dairy beverages, fruit juice drinks, orange drinks, lemon-lime drinks, beer, malt drinks or other flavored beverages. The beverage may be in liquid or powder form. The beverage composition may also comprise one or more flavoring agents; Artificial pigments; Vitamin additives; Preservatives; Caffeine additives; water; Acidulants; Thickeners; Buffering agents; Emulsifiers; And or fruit juice concentrates.

Artificial pigments may include caramel pigments, 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 including sodium, potassium and magnesium chloride can be used. Exemplary emulsifiers are gum arabic and purity gum, and useful thickeners are pectin. Suitable acidulants include citric acid, phosphoric acid and malic acid, and possible buffering agents include sodium and potassium citrate.

In one embodiment, the beverage is a carbonated cola beverage. The pH is generally about 2.8 and the following ingredients can be used to prepare syrups for these compositions. : Flavor Concentrate (22.22 ml), 80% Phosphoric Acid (5.55 g), Citric Acid (0.267 g), Caffeine (1.24 g), Artificial Sweeteners, Sugar or Corn Syrup (In Real Sweeteners) According to taste) and potassium citrate (4.07 g). This beverage composition can be prepared, for example, by mixing the above syrup in a ratio of carbonated water and 50 ml syrup to 250 ml of carbonated water.

Flavored food and pharmaceutical compositions can also be prepared comprising one or more derivatives disclosed herein. These derivatives can be incorporated into traditional food ingredients using techniques known to those skilled in the art. Alternatively, this derivative may be incorporated into the polymer particles. It may again be dispersed in and / or on the surface of the oral-delivery matrix material which is generally a solid or semi-solid substrate. When used in chewable compositions, these derivatives can be released into the oral-delivery polymer matrix material as the composition is chewed and retained in the mouth, thus maintaining the flavor of the composition. In the case of dried powders and mixes, the flavor may be made such that the flavor is utilized as the composition is further processed and the product is consumed or released into the matrix material. When the two flavors are combined into polymer particles, the relative dose of the additive can be selected to provide simultaneous release and consumption of the compound.

In one embodiment, the flavor composition comprises an oral-delivery matrix material; A plurality of water soluble polymer particles dispersed in an oral-delivery matrix material, wherein the polymer particles individually define a network of internal pores and are non-degradable in the digestive tract; And one or more derivatives disclosed herein captured in an internal pore network. The derivative is released as the matrix is chewed and subjected to further processing selected from the group consisting of melting in the mouth or liquid addition, dry mixing, stirring, mixing, heating, baking and cooking. Oral-delivery matrix materials include gum, latex, crystallized sugars, amorphous sugars, fondants, nougat, jams, jelly, pastes, powders, dry blends, dehydrated food mixes , Baked products, batters, doughs, tablets and lozenges.

A flavorless gum base can be combined with the appropriate derivatives disclosed herein for the desired flavor concentration. In general, the blade mixer is heated to about 11OF and the gum base is preheated and softened. The gum base is then added to the mixer and mixed for approximately 30 seconds. The flavor derivative is then added to the mixer and mixed for a suitable time. The black is then separated from the mixer and rolled to a stick thickness on wax paper during warming.

In one embodiment, the derivatives disclosed herein incorporate a system capable of emitting fragrance in a controlled manner. This includes substrates such as air fresheners, laundry detergents, fabric softeners, deodorants, lotions and other household items. Aromas are generally derivatives of one or more essential oils disclosed herein, each of which is present in different doses. The contents of U.S. Patent No. 4,587,129 are incorporated herein by reference in their entirety, and discloses a process for preparing gel products containing up to 90 wt% of fragrance or perfume oils. This gel is a polymer having hydroxy (lower alkoxy) 2-alkeneoate, hydroxy (lower alkoxy) lower alkyl 2-alkeneoate, or hydroxy poly (lower alkoxy) lower alkyl 2-alkeneoate And polyethylenically unsaturated crosslinking agents. These materials have continuous sustained release properties. That is, they continue to emit fragrant components for a long time. Preferably, all or some of these derivatives, including aldehyde groups, can be modified to contain acetal groups, which can induce the agent to release fragrance over an extended period of time since the acetal is hydrolyzed to form aldehyde compounds.

Example 1

The method of the present invention has been applied to citronellol isomers as follows:

In a 500-mL round bottom flask containing alpha and beta citronellol (5 mL) in dichloromethane (200 mL) mCPBA (11.0 g, 50-85%) was added over a 45 minute portion in a portionwise 5 hour period. Was stirred.

The mixture was washed with saturated Na ₂ SO ₃ (70 mL) solution and then with brine (3 × 70 mL). The organic phase was dried over Na ₂ SO ₄ , filtered and the solvent was evaporated to give the pure desired product as a colorless oil. (5.5g).

The second stage of the process follows the plan. :

Thiourea (1.0 g) was added to a pure mixture of the corresponding epoxides from alpha and beta-citronellol in ethanol (5 mL) and water (3 mL) and the reaction was stirred overnight under a nitrogen atmosphere. The solvent was evaporated in vacuo. Flash column chromatography from a mixture using dichloromethane / ethyl acetate (3: 2) gave the pure desired mixture of tyrane as a colorless oil.

Alternatively, a mixture of epoxides (1 equiv), potassium thiocyanate (3 equiv) and ceric ammonium nitrate (5-100 mol%) are combined with tert-butanol or iso-propanol at an appropriate temperature. It was stirred in the same solvent. When the reaction was judged complete (TLC), the mixture was concentrated and the residue was extracted with dichloromethane. Tyran was pure enough for later use or further purified if necessary.

Example  2

Similarly, this method has been applied to geraniol:

Example 3

Similarly, the method of Example 1 was applied to lavandulol.

Example 4

Similarly, the method of Example 1 was applied to linalool and diH-linalol. See Figure 1

Example 5

Similarly, the same method was applied to myrcenol and diH- myrsenol. See Figure 1

Example 6

Similarly, the same method was applied to ocimenol and diH-osimenol. See Figure 1

The present invention is equally applicable to all unsaturated cyclic or non-cyclic aromatic compounds such as terpenes and their aldehyde and ketone derivatives.

Although the subject matter of the present invention has been disclosed herein, it is apparent that many modifications, substitutions, and variations are possible within the spirit of the invention. It is to be understood that the invention may be practiced other than as specifically described herein. Such modifications, substitutions and variations are within the scope of the present invention.

Claims (55)

Binding properties to metal ions without significantly affecting the odor characteristics of the aromatic chemical or aromatic compound, including the conversion of one or more double bonds in the molecule to an oxirane or thiirane group. Methods of Deriving Aromatic Chemicals or Aromatic Compounds Containing One or More Double Bonds in the Molecular Structure to Promote The method of claim 1, comprising inducing the aromatic chemical or aromatic compound to produce an oxirane. 3. The method of claim 2, wherein the induction comprises oxidizing the at least one double bond to an oxirane group. 4. The method of claim 3, wherein the oxidation is by reaction of the at least one double bond with peracid, oxygen or hydroperoxide. 5. The method of claim 4, wherein the peracid is m-chloroperbenzoic acid or peroxybenzoic acid. 5. A process according to claim 4, wherein the reaction with oxygen takes place in the presence of a catalyst. 7. A process according to claim 6, wherein the catalyst is an Ag catalyst. The method of claim 4 wherein the hydroperoxide is t-butyl hydroperoxide. Method for inducing aromatic chemicals or aromatic compounds, characterized in that 5. The method of claim 4, wherein the reaction with the hydroperoxide takes place in the presence of Ti (IV) isopropoxide. 3. The method of claim 2, comprising converting the oxirane group to a thiirane group. The method of claim 10, wherein the oxirane group is converted into the thiirane group by reaction with an episulfidating agent. 12. The method of claim 11, wherein the episulfating agent is sulfide, thiourea or thiocyanate. 13. The method of claim 12, wherein the sulfide comprises a mixture of triphenylphosphine sulfide and picric acid. 14. A process according to claim 13, wherein said thiocyanate is potassium thiocyanate. The method of claim 1, comprising inducing the aromatic chemical or aromatic compound to produce thiirane. 16. The method of claim 15, wherein the thiirane is produced by the reaction of the at least one double bond with an episulfating agent. 17. The method of claim 16, wherein the thiirane is produced by reduction of the reaction product after reaction of the at least one double bond with succinimide-N-sulphenyl halide. 18. The method of claim 17, wherein the reduction occurs by reaction of the reaction product with lithium aluminum hydride. A product prepared by the method of inducing the aromatic chemical or aromatic compound of claim 1 A composition comprising a product prepared by the method of claim 1 together with other perfume ingredients, solvents, or auxiliaries currently used in perfume technology. The composition of claim 20, wherein the product is present at a dose of at least 30 wt%. 6. A composition according to claim 5, wherein said product is present at a dose of at least 60 wt%. Perfume composition or perfume product comprising as a perfume component a product prepared according to the method of claim 1 or a mixture thereof 24. A perfume composition or perfume product according to claim 23, wherein said product or mixture of products is present in a mixture with other perfume ingredients, solvents, or adjuvants currently used in the art. The preparation according to claim 23, which is in the form of a perfume or cologne, soap, bath or shower gel, shampoo or other hair care product, cosmetic preparation, deodorant or antiperspirant, air freshener, textile detergent or softener or multi-purpose household cleaner. Flavoring products. Deodorant or antiperspirant according to claim 25 27. The deodorant or antiperspirant of claim 26, wherein the product or mixture of products is present as a mixture of other perfume ingredients, solvents, or adjuvants currently used in the art. Detergent according to claim 25 29. The detergent of claim 28, wherein the product or mixture of products is present as a mixture of other perfume ingredients, solvents, or adjuvants currently used in the art. Bleaching composition comprising the product according to claim 19 Beverages comprising the product according to claim 19 A method of improving, enhancing or modifying the odor of a perfume composition or perfume product comprising adding an effective dose of the product of claim 19 or a mixture thereof to the perfume composition or perfume product. 33. The method of claim 32, wherein the product or mixture thereof is present as a mixture with other perfume ingredients, solvents, or adjuvants currently used in the art. 33. The method of claim 32, wherein the product or mixture thereof is present at a capacity of at least 30 wt%. A fungicide comprising the product of claim 19 or a mixture thereof Article comprising the product of claim 19 or a mixture thereof A method for improving the fragrance properties of a product comprising incorporating an effective dose of the product of claim 19 or a mixture thereof into the product. A method for improving the binding properties of aromatic aromatic chemicals or aromatic compounds to metal ions of one or more double bonds in the molecular structure, comprising converting one or more double bonds in the molecular structure to an oxirane or thiirane group. The method of claim 1 comprising converting the double bond to oxirane. The method of claim 2, wherein said converting oxidizes said at least one double bond to an oxirane group. 41. The method according to claim 40, wherein the oxidation is due to the reaction of the at least one double bond with a peracid, oxygen or hydroperoxide to the metal ion of the aromatic chemical or aromatic compound containing at least one double bond in the molecular structure. To improve binding properties 42. The method of claim 41 wherein the peracid is m-chloroperbenzoic acid or peroxybenzoic acid characterized in that the aromatic chemicals or aromatic compounds containing at least one double bond in the molecular structure to the metal ion binding properties How to improve 42. The method of claim 41, wherein the aromatic chemical or aromatic compound containing at least one double bond in the molecular structure is characterized in that the reaction with oxygen occurs in the presence of a catalyst. The method of claim 43, wherein the aromatic chemical or aromatic compound containing at least one double bond in the molecular structure of the catalyst is an Ag catalyst. 42. The method of claim 41, wherein the aromatic chemical or aromatic compound containing at least one double bond in the molecular structure, characterized in that the hydroperoxide group t-butyl hydroperoxide, is bound to metal ions. 42. A metal ions of aromatic chemicals or aromatic compounds containing at least one double bond in the molecular structure according to claim 41, wherein the reaction with the hydroperoxide takes place in the presence of Ti (IV) isopropoxide. To improve binding properties 40. The method of claim 39, comprising converting the oxirane group to a thiirane group. 48. The method of claim 47, wherein said oxirane group is converted to said thiirane group by reaction with an episulfating agent. 49. The method of claim 48, wherein said episulfating agent is sulfide, thiourea or thiocyanate. 50. The method of claim 49, wherein the sulfide comprises a mixture of triphenylphosphine sulfide and picric acid. 50. The method of claim 49, wherein said thiocyanate is potassium thiocyanate. 39. The aromatic chemical or aromatic compound containing at least one double bond in the molecular structure, wherein the aromatic compound contains at least one double bond in the molecular structure to form a thiirane. How to improve the characteristics The metal ion of an aromatic chemical or aromatic compound containing at least one double bond in the molecular structure of claim 52, wherein the thiirane is produced by the reaction of the at least one double bond with an episulfating agent. To improve binding properties 55. The method of claim 53, wherein the thiirane contains at least one double bond in the molecular structure, characterized in that the at least one double bond is produced by reduction of the reaction product after reaction with the succinimide-N-sulphenyl halide. How to improve the binding properties of aromatic chemicals or aromatic compounds to metal ions 55. The method of claim 54, wherein the reduction is by reaction of the reaction product with lithium aluminum hydride, thereby improving the binding properties of the aromatic chemicals or aromatic compounds to the metal ions of the aromatic compounds containing at least one double bond in the molecular structure. How to let

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