AU2004207775B2

AU2004207775B2 - Improved jasmine aromachemicals

Info

Publication number: AU2004207775B2
Application number: AU2004207775A
Authority: AU
Inventors: Luca Turin
Original assignee: Flexitral Inc
Current assignee: Flexitral Inc
Priority date: 2003-01-21
Filing date: 2004-01-21
Publication date: 2007-12-13
Anticipated expiration: 2024-01-21
Also published as: WO2004067481A3; JP2006519773A; GB2414988A; EP1620424A4; GB2414988B; AU2004207775A1; EP1620424A2; CN1753883A; GB0521305D0; WO2004067481A2; CA2514048A1

Description

Improved Jasmine Aromachemicals The present invention relates generally to the field of fragrances. More 0 particularly, the present invention relates to novel compounds that provide N 5 perfumes and other articles with a mild, sweet, floral odor with herbaceous odor undertones.

Cyclic aldehydes, in particular alkyl cinnamic aldehydes, are a major component C of many perfumes and have a fresh, green floral scent. Many are based on the structure:

C

6

HS-CH=C(CHO)-R

wherein R can be a straight or branched alkyl chain. Examples of commonly used aldehydes are those of the above formula wherein R is a CI-C6 alkyl radical such as, for example amyl cinnamic aldehyde (see US pat. no.

3,953,378). It would be desirable to develop alternative derivatives with improved odorant intensity, while maintaining the fresh, floral character of the cinnamic aldehydes.

The discussion of the background art is included exclusively for the purpose of providing a context for the present invention. It should be appreciated that the discussion is not an acknowledgement or admission that any of the material referred to was common general knowledge in the field relevant to the present invention in Australia or elsewhere before the priority date.

The invention relates to a compound or mixtures of compounds of the formula: cz

S

wherein: R is a branched or straight chain alkyl group containing from 6 to carbon atoms, Z is O or N, and when Z is O, Z is selected from O, an acetal or hemiacetal thereof.

C The invention also provides compositions, products, preparations or articles O having improved aroma, fragrance or odor characteristics containing as active 0 ingredient a compound or mixture of compounds of the above formula.

(N I The invention also provides compositions, products, preparations or articles having improved flavor or taste characteristics containing as active ingredient a compound or mixture of compounds of the above formula.

The invention also provides a method to confer, improve, enhance or modify the taste or flavor property of a composition, product, preparation or article which comprises adding thereto a flavor effective amount of a compound or mixture of compounds of the above formula.

The invention also provides a method to confer, improve, enhance or modify the aroma, fragrance or odor characteristics of compositions, products, preparations or articles which comprise adding thereto an aroma, fragrance or odor effective amount of a compound or mixture of compounds of the above formula.

The invention additionally provides an article of manufacture comprising a packaging material and an aroma, odor, fragrance, taste or flavor enhancing agent contained within said packaging material, wherein said agent is effective for the enhancement of the aroma, odor, fragrance, taste or flavor of a composition, preparation, product or article to which it is added, and wherein said packaging material comprises a label which indicates that the agent can be used for enhancing aroma, odor, fragrance, taste or flavor, and wherein the agent is a compound or mixture of compounds of the above formula.

The present invention is predicated on the discovery of improved fragrances and flavorings that have increased odorant and/or flavorant intensity relative to conventional cinnamic aldehydes. In particular, the compounds of the invention maintain the flavor and/or fragrance characteristics of the analogous cinnamic aldehydes, while increasing the odor intensity relative thereto. Also disclosed are methods of making the compounds, utilizing the derivatives as flavorants and/or fragrances and compositions, products, preparations and articles incorporating the O derivatives. The compounds of the invention find utility in applications requiring 0 jasmine, gardenia, tuberose and magnolia floral themes. The compositions, N, 5 products, preparations and articles in which the compounds of the invention may be incorporated include candles, air fresheners, perfumes, fragrances, colognes, soaps, bath or shower gels, shampoos or other hair care products, cosmetic preparations, body odorants, deodorants or antiperspirants, liquid or solid fabric detergents or softeners, bleach products (hypochlorites), disinfectants, all-purpose household or industrial cleaners, foods, flavorings, beverages such as beer and C1 soda, denture cleansers (tablets), flavored orally-delivered products such as lozenges, candles, chewing gums, matrices, pharmaceuticals and the like.

The compounds of the invention can be viewed as cinnamic aldehydes or derivatives thereof wherein the phenyl ring of the cinnamic derivative has been replaced by a thiophene ring. Thus, the 2- and 3- thiophene compounds of the invention have the formula: cZ

S

wherein: R is a branched or straight chain alkyl group containing from 6 to 10 carbon atoms, Z is O or N, and when Z is O, Z is selected from O, an acetal or hemiacetal thereof. The compounds of the invention have odor/flavorant characteristics that are similar to the cinnamic aldehydes, but which have increased intensities compared thereto and can be used, for example, as fragrances and/or flavorants. This unique property of the compounds of the invention is apparent in two contexts: first, the presence of even low concentrations of the improved derivative gives greater depth, definition and radiance to fragrance compositions of different types.

0 Second, prolonged smelling of even low concentrations of the improved derivative

O

CI heightens the sense of smell to all ambient olfactory stimuli.

O

For the purposes of description herein, the compounds of the invention are C 5 referred to as jasphene derivatives or "jasphenes". Furthermore, it will also be understood by those skilled in the art that the aldehyde group of the derivatives exemplified hereinbelow can be replaced with acetal or nitrile provided, of course, that the functional group does not substantially interfere with the odorant or other C1 desired properties of the derivative. The jasphene derivatives can be prepared S 10 employing the method exemplified below.

EXAMPLE

Following is the equation of a typical reaction scheme: To the solution of octanal (2.6 mL, 17.1 mmol) and 2-thiophene-carboxaldehyde (1.8 mL, 19.6 mmol) in ethanol (20 mL) and water (100 mL) was added NaOH mL, 10% aq. solution) and the mixture was stirred at room temperature for 2 days.

The mixture was acidified by acetic acid and extracted with ether. The combined organic layers were washed with water (2 x 50 mL) and saturated sodium hydrogen carbonate solution, dried over sodium WO 2004/067481 PCT/US2004/001304 sulfate and evaporated in vacuo to give a crude product with the alkene ratio of 5:8. Flash column chromatography using petroleum ether/ethyl acetate afforded the product [2hexyl-3-thiophen-2-yl propenal] as a colorless liquid. The process may be repeated employing 3-thiophene-carboxaldehyde to produce the [2-hexyl-3-thiophen-3-yl propenal] product.

The jasphene derivatives can be included in virtually compositions product, preparation or articles compatible therewith, including other fragrances, whether natural or artificial. Examples include bleach, detergents, flavorings and fragrances, beverages, including alcoholic beverages, and the like. The jasphene 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. Of course, the use of the compounds is not limited to the above-mentioned products, as they can also be used in other applications, 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% 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.

WO 2004/067481 PCT/US2004/001304 In all cited applications, the jasphene derivatives can be used alone or in admixture with other compatible 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 without undue experimentation and based on the nature of the product to be scented and/or flavored and on the desired olfactive/flavor effect.

Typical perfuming ingredients, for example, 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. A large number of these ingredients described in reference textbooks such as the book of S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, USA, the contents and disclosure of which are incorporated herein by reference in its entirety, or its more recent versions, or in other works of similar nature.

The proportions in which the jasphene derivatives can be incorporated in the various products vary within a large range of values. These values depend on the nature of the composition, preparation, article or product that one desires to perfume or flavor and the odor or flavor effect intended, as well as on the nature of the co-ingredients in a given composition when the compounds are used in admixture with co-ingredients, solvents or adjuvants of current use in the art.

As an example, the jasphene 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 listed hereinabove.

WO 2004/067481 PCT/US2004/001304 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. The compounds can also be used in body deodorants and antiperspirants, for example, those containing aluminum salts. These embodiments are described in more detail below.

In addition to the derivatives described herein, the detergent and cleanser compositions according to the invention 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 perfumes, colorants, dyes, etc.). Non-limiting examples of synthetic detersive surfactants useful herein typically at levels from about 0.5% to about by weight, include the conventional C1-18 alkyl benzene sulfonates and primary, branch-chain and random CIO-20 alkyl sulfates and the like.

Preferred compositions incorporating only synthetic detergents have a detergent level of from about 0.5% to 50%. Compositions containing soap preferably comprise from about to about 90% soap.

The detergent/cleaner formulations can also contain other ingredients such as enzymes, bleaches, fabric softening agents, dye transfer inhibitors, suds suppressors, and chelating agents, all well known in the art.

The jasphene derivatives described herein can be incorporated into beverages and impart various flavorings thereto. 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 beverage, or other flavored beverage. The beverage can be in liquid or powdered form. The beverage composition can also include one or more flavoring WO 2004/067481 PCT/US2004/001304 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 Useful vitamin additives include vitamin B2, vitamin B6, vitamin B 12, 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.

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 make the syrup for these compositions: Flavor Concentrate, including one or more of the derivatives described herein (22.22 ml), Phosphoric Acid (5.55 Citric Acid (0.267 Caffeine (1.24 artificial sweetener, sugar or com syrup (to taste, depending on the actual sweetener) and Potassium Citrate (4.07 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 carbonated water.

In another embodiment, the beverage is a beer or malt beverage. Advantageously, the flavorings include jasphene 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.

Alternatively, the derivatives can be incorporated within polymeric particles, which can, in WO 2004/067481 PCTIUS2004/001304 turn, be dispersed within and/or over a surface of an orally-deliverable matrix material, which is usually a solid or semi-solid substrate. When used in chewable compositions, 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.

In the case of dried powders and mixes, the flavor can be made available as the product is consumed or be released into the matrix material as the composition is further processed.

When two flavors are combined with the polymeric particles, the relative amounts of the additives can be selected to provide simultaneous release and exhaustion of the compounds.

In one embodiment, 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.

A flavorless gum base can be combined with a jasphene or other suitable derivative as described herein to a desired flavor concentration. Typically, a blade mixer is heated to about 1100 F, 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.

WO 2004/067481 PCT/US2004/001304 In one embodiment, 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 or essential oils as described herein, each present in different quantities. U.S. Pat. No. 4,587,129, the contents and disclosure of which are incorporated herein by reference in their entirety, describes a method for preparing gel articles which contain up to 90% 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, they release the fragrance component continuously over a long period of time.

Advantageously, 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.

Having hereby disclosed the subject matter of the present invention, it should be apparent that many modifications, substitutions, and variations of the present invention are possible in light thereof. It is to be understood that the present invention can be practiced other than as specifically described. Such modifications, substitutions and variations are intended to be within the scope of the present application.

Claims

2. A compound of claim 1 wherein Z is 0 and R is n-hexyl.
3. A compound of claim 2 of the formula: S 0
4. A composition, product, preparation or article containing a compound or mixture of compounds as defined in any preceding claim to provide flavour, taste, aroma, fragrance or odour characteristics. The composition, product, preparation or article of claim 4, wherein the compound or mixture of compounds is present in an amount of at least 30 percent by weight.
6. The composition, product, preparation or article of claim 5, wherein the compound or mixture of compounds is present in an amount of at least 60 percent by weight. C.) 0
7. A composition, product, preparation or article of claim 4 in the form of a perfume, fragrance or cologne, a soap, a bath or shower gel, a shampoo or other Shair care product, a cosmetic preparation, a body odorant, deodorant or antiperspirant, an air freshener, a liquid or solid fabric detergent or softener, bleach product, disinfectant or an all-purpose household or industrial cleaner.
8. A composition, product, preparation or article of claim 7 in the form of a perfume wherein the compound or mixture of compounds is in admixture with other perfuming ingredients, solvents or adjuvants.
9. A composition, product, preparation or article of claim 7 in the form of a body odorant, deodorant or antiperspirant wherein the compound or mixture of compounds is in admixture with other body odorant, deodorant or antiperspirant ingredients, solvents or adjuvants.
10. A composition, product, preparation or article of claim 7 in the form of a detergent wherein the compound or mixture of compounds is in admixture with other detergent ingredients, solvents or adjuvants.
11. A composition, product, preparation or article of claim 7 in the form of a bleach product wherein the compound or mixture of compounds is in admixture with other bleach ingredients, solvents or adjuvants.
12. A composition, product, preparation or article of claim 7 in the form of a disinfectant wherein the compound or mixture of compounds is in admixture with other disinfectant ingredients, solvents or adjuvants.
13. A composition, product, preparation or article of claim 4 in the form of a beverage wherein the compound or mixture of compounds is in admixture with other beverage ingredients, solvents or adjuvants. O
14. A composition, product, preparation or article of claim 4 in the form of a flavouring wherein the compound or mixture of compounds is in admixture with Sother flavouring ingredients, solvents or adjuvants. A composition, product, preparation or article of claim 4 in the form of a food wherein the compound or mixture of compounds is in admixture with other food ingredients, solvents or adjuvants.
16. A composition, product, preparation or article of claim 4 in the form of a chewing gum wherein the compound or mixture of compounds is in admixture with other chewing gum ingredients, solvents or adjuvants.
17. A composition, product, preparation or article of claim 4 in the form of a pharmaceutical wherein the compound or mixture of compounds is in admixture with other pharmaceutical ingredients, solvents or adjuvants.
18. A composition, product, preparation or article of claim 4 in the form of an orally-deliverable matrix material wherein the compound or mixture of compounds is in admixture with other matrix material ingredients, solvents or adjuvants.
19. A method to confer, improve, enhance or modify the taste or flavour property of a composition, product, preparation or article which comprises adding thereto a flavour effective amount of a compound or mixture of compounds as defined in any of claims 1 to 3. The method of claim 19 wherein said composition, product, preparation or article is in the form of a beverage.
21. The method of claim 19 wherein said composition, product, preparation or article is in the form of a flavouring. O 22. The method of claim 19 wherein said composition, product, preparation or article is in the form of a food. S23. The method of claim 19 wherein said composition, product, preparation or article is in the form of a chewing gum.
24. The method of claim 19 wherein said composition, product, preparation or article is in the form of a pharmaceutical. The method of claim 19 wherein said composition, product, preparation or article is in the form of an orally deliverable matrix.
26. A method to confer, improve, enhance or modify the aroma, fragrance or odour characteristics of a composition, product, preparation or article which comprises adding thereto an aroma, fragrance or odour effective amount of a compound or mixture of compounds as defined in any of claims 1 to 3.
27. The method of claim 26 wherein said composition, product, preparation or article is in the form of a perfume.
28. The method of claim 26 wherein said composition, product, preparation or article is in the form of a body odorant, deodorant or antiperspirant.
29. The method of claim 26 wherein said composition, product, preparation or article is in the form of a detergent.
30. The method of claim 26 wherein said composition, product, preparation or article is in the form of a bleach product.
31. The method of claim 26 wherein said composition, product, preparation or article is in the form of a disinfectant. ¢,I O 32. An article of manufacture comprising packaging material and an aroma, odour, fragrance, taste or flavour enhancing agent contained within said packaging material, wherein said agent is effective for the enhancement of the aroma, odour, t fragrance, taste or flavour of a composition, preparation, product or article to which it is added, and wherein said packaging material comprises a label which indicates that said agent can be used for enhancing aroma, odour, fragrance, taste or flavour, and wherein said agent is a compound or mixture of compounds as defined in any of claims 1 to 3.
33. A compound or mixtures of compounds substantially as herein described.
34. A composition, product, preparation or article substantially as herein described. A method to confer, improve, enhance or modify the taste, flavour, aroma, fragrance or odour of a composition, product, preparation or article as substantially herein described.
36. An article of manufacture as substantially herein described.
37. A method for preparing a compound or mixture of compounds as defined in claim 2, comprising reacting 2-thiophene-carboxaldehyde with octanal.
38. A method for preparing a compound or mixture of compounds as defined in claim 3, as described in the Example.