WO2004108867A2 - Cyclohexene carboamides et carbothioamides - Google Patents

Cyclohexene carboamides et carbothioamides Download PDF

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Publication number
WO2004108867A2
WO2004108867A2 PCT/US2004/017321 US2004017321W WO2004108867A2 WO 2004108867 A2 WO2004108867 A2 WO 2004108867A2 US 2004017321 W US2004017321 W US 2004017321W WO 2004108867 A2 WO2004108867 A2 WO 2004108867A2
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WO
WIPO (PCT)
Prior art keywords
product
article
preparation
composition
compound
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.)
Ceased
Application number
PCT/US2004/017321
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English (en)
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WO2004108867A3 (fr
Inventor
Luca Turin
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.)
Flexitral Inc
Original Assignee
Flexitral Inc
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
Application filed by Flexitral Inc filed Critical Flexitral Inc
Publication of WO2004108867A2 publication Critical patent/WO2004108867A2/fr
Publication of WO2004108867A3 publication Critical patent/WO2004108867A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/58—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/38—Amides of thiocarboxylic acids
    • C07C327/46—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates generally to the field of fragrances. More particularly, the present invention relates to novel aromachemicals that provide perfumes and other articles with unique properties and advantages not shared by other aromachemicals. These derivatives find utility in any and all applications requiring certain aroma themes. The invention also relates to mixtures of these derivatives, methods for their preparation and their use as perfume materials for application to a variety of substrates.
  • fragrances used as ingredients in perfumes and in a varied range of other products.
  • perfumes for application in laundry detergents, fabric softeners, rinse conditioners and other products intended for use on textile fibers primarily contain fragrances.
  • fragrance chemicals Under current legislation there are no restrictions on the quantities or combinations of fragrance chemicals that may be used in cosmetics. When fragrance chemicals are added, the law requires only that the label on a cosmetic or toiletry includes the word 'Parfum' in the EU or 'Fragrance' in the USA. There are no requirements to name individual fragrance chemicals in the list of ingredients. This is because a typical perfume contains a mixture of a large number of fragrance chemicals, often between 50 and 100 and it would be impossible to list them all on a small label. This creates a problem for people who are sensitive or allergic to a particular fragrance chemical. Buying cosmetics becomes a lottery for them because they can never know if the offending chemical has been used in a product or not.
  • Damascones have been found to be responsible for patient's contact allergy to a number of commercial products. These substances contain chemical structural alerts giving them antigenic ability. [A. Gimenez-Arnau et al, "Principles and methodology for identification of fragrance allergens in consumer products", Contact Dermatitis, Volume 47, Issue 6, Page 345, 2002].
  • damascones are highly renowned because of their highly desirable fragrance characteristics. It is an object of the invention to provide novel aromachemical compounds and compositions that possess many of the desirable fragrance characteristics of the damascones but which do not cause allergic reactions in most mammals and which are very inexpensive to synthesize.
  • Novel fragrance and flavor aromachemicals are disclosed herein as well as methods of making the derivatives, uses of the aromachemicals and articles of manufacture including the aromachemicals. These novel derivatives find utility in any and all applications requiring certain aroma themes.
  • the invention also relates to mixtures of these derivatives, methods for their preparation and their use as perfume materials for application to a variety of substrates.
  • R is a straight or branched chain, saturated or unsaturated hydrocarbyl group; preferably, alkyl or alkenyl, having 1-8 carbon atoms;
  • Ri is a straight or branched chain, saturated or unsaturated hydrocarbyl group; preferably, alkyl or alkenyl, having 1-8 carbon atoms; x is an integer from 1 to 8; y is an integer from 0 to 4, and Z is O or S.
  • a preferred carboamide is 2,6,6-trimethyl-cyclohex-3-enemethylcarboxamide having the formula:
  • a preferred carbothioamide is 2,6,6-trimethyl-cyclohex-3-ene-t-butylcarboxthioamide having the formula:
  • a second embodiment of the invention concerns compositions, products, preparations or articles having improved aroma, fragrance or odor characteristics containing as active ingredient a compound described above or a mixture thereof.
  • compositions, products, preparations or articles having improved flavor or taste characteristics containing as active ingredient a compound described above or a mixture thereof.
  • a further embodiment of the invention concerns methods 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 described above or a mixture thereof.
  • a still further embodiment of the invention relates to a method to confer, improve, enhance or modify the aroma, fragrance or odor characteristics of compositions, products, preparations or articles which comprises adding thereto an aroma, fragrance or odor effective amount of a compound described above or a mixture thereof.
  • An additional embodiment of the invention concerns articles of manufacture comprising a compound described above or a mixture thereof.
  • the aromachemicals of the invention may be prepared according to the reaction schemes set forth in the drawing which outlines the syntheses of the above-noted preferred compounds.
  • the aromachemicals of the invention possess the odor profile: woody, ambery.
  • suitable articles of manufacture in which the derivatives of the invention may be incorporated include perfumes and colognes, candles, air fresheners, detergent compositions and disinfectants.
  • the aromachemicals of the invention can be included in virtually any article of manufacture that can include conventional fragrances, whether natural or artificial. Examples include bleach, detergents, flavorings and fragrances, beverages, including alcoholic beverages, and the like.
  • the 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 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.
  • the 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.
  • the proportions in which the 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 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 can also be used in body deodorants and antiperspirants, for example, those containing aluminum salts. These embodiments are described in more detail below.
  • 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.).
  • Non-limiting examples of synthetic detersive surfactants useful herein typically at levels from about 0.5% to about 90%, by weight, include the conventional Cl-18 alkyl benzene sulfonates ("LAS") and primary, branch-chain and random CIO-20 alkyl sulfates ("AS”), 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 10% to about 90% soap.
  • 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 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 com 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 com 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
  • 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.
  • a flavorless gum base can be combined with a suitable derivative as described herein to a desired flavor concentration.
  • a blade mixer is heated to about 11 OF, 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% 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.
  • Still other preferred aroma chemicals are those of the formula:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un composé ou un mélange de composés, comprenant un composé de produits appartenant à la chimie des arômes et parfums, de formule (I), dans laquelle Q désigne (II) ou (III), R désigne une chaîne linéaire ou ramifiée, un groupe hydrocarbyle saturé ou insaturé ; de préférence, un alkyle ou un alcényle ayant de 1 à 8 atomes de carbone ; R1 désigne une chaîne linéaire ou ramifiée, un groupe hydrocarbyle saturé ou insaturé ; de préférence un alkyle ou un alcényle ayant de 1 à 8 atomes de carbone ; x est un nombre entier compris entre 1 et 8 ; y est un nombre entier compris entre 0 et 4, et Z désigne un O ou un S. L'invention concerne en outre des compositions, préparations ou articles présentant des caractéristiques d'arôme, de fragrance ou d'odeur, contenant comme ingrédient actif, un composé ou un mélange de composés précités.
PCT/US2004/017321 2003-06-02 2004-06-02 Cyclohexene carboamides et carbothioamides Ceased WO2004108867A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US47462403P 2003-06-02 2003-06-02
US60/474,624 2003-06-02
US50140503P 2003-09-10 2003-09-10
US60/501,405 2003-09-10
US51791703P 2003-11-07 2003-11-07
US60/517,917 2003-11-07

Publications (2)

Publication Number Publication Date
WO2004108867A2 true WO2004108867A2 (fr) 2004-12-16
WO2004108867A3 WO2004108867A3 (fr) 2005-02-03

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PCT/US2004/017321 Ceased WO2004108867A2 (fr) 2003-06-02 2004-06-02 Cyclohexene carboamides et carbothioamides

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WO (1) WO2004108867A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9562022B2 (en) 2009-06-16 2017-02-07 Bikam Pharmaceuticals, Inc. Opsin-binding ligands, compositions and methods of use

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6174885B1 (en) * 1998-03-03 2001-01-16 Shiseido Co., Ltd. [6-(substituted-methyl)-3-cyclohexenyl] formamide derivative, hair growth promoter and external composition for skin

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9562022B2 (en) 2009-06-16 2017-02-07 Bikam Pharmaceuticals, Inc. Opsin-binding ligands, compositions and methods of use

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WO2004108867A3 (fr) 2005-02-03

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