EP2046772A1 - Salicylate de thiophénéméthyle et composés parents en tant que arômes et parfums - Google Patents

Salicylate de thiophénéméthyle et composés parents en tant que arômes et parfums

Info

Publication number
EP2046772A1
EP2046772A1 EP07766258A EP07766258A EP2046772A1 EP 2046772 A1 EP2046772 A1 EP 2046772A1 EP 07766258 A EP07766258 A EP 07766258A EP 07766258 A EP07766258 A EP 07766258A EP 2046772 A1 EP2046772 A1 EP 2046772A1
Authority
EP
European Patent Office
Prior art keywords
composition
compounds
compound
article
product
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.)
Withdrawn
Application number
EP07766258A
Other languages
German (de)
English (en)
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
Priority claimed from US11/738,919 external-priority patent/US20080260669A1/en
Application filed by Flexitral Inc filed Critical Flexitral Inc
Publication of EP2046772A1 publication Critical patent/EP2046772A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • 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

Definitions

  • the present invention relates generally to the field of fragrances and flavours. More particularly, the present invention concerns thiophenemethyl salicylate and related compounds that provide perfumes, flavourants and other articles with properties and advantages not shared by other chemicals. These components find utility in an ⁇ ' and all applications requiring certain aroma and flavour themes.
  • the invention also relates to mixtures of these compounds, methods for their preparation and their use as odourant and flavourant materials for application to a variety of substrates.
  • fragrances and flavourants used as ingredients in perfumes and in a varied range of other products.
  • aromachemicals include double bonds and/or other reactive groups that are potentially susceptible to reaction and may result in a limited useful lifetime.
  • essential oil fragrances have recently been determined to cause allergic reactions, and it is becoming increasingly difficult to bring products containing such fragrances/flavours to market.
  • benzyl salicylate which has the chemical structure shown below
  • has a slight odour and is used as a solvent for synthetic musks and a fixer in perfume compositions.
  • benzyl salicylate has a very faint odour which not everyone can smell. Moreover, benzyl salicylate is though to be allergenic.
  • the present invention addresses the foregoing deficiencies by providing the compounds, use, methods, substrate, composition, product, preparation or article, beverage composition, flavouring composition, food composition, chewing gum composition pharmaceutical composition, orally deliverable matrix and article of manufacture as defined in the claims.
  • the present invention provides compounds of formula (I):
  • linear or branched C ⁇ alkyl we mean methyl, ethyl, «-propyl, z-propyl, n- butyl, z-butyl, s-butyl or z * -butyl. If n > 1, each R 1 group may be the same or different. If m > 1, each R 2 group also may be the same or different.
  • the invention relates to the thiophenemethyl salicylate compounds having the formula:
  • a preferred group of compounds of the invention are those in which the salicylate- type group is attached to the 2-position of the thiophene ring.
  • Specific examples of such compounds include 2-thiopene methanol salicylate ester illustrated above.
  • the present invention provides a method for the preparation of a compound of
  • the CH 2 OH group of the compound of formula "' may be attached to the 2- or 3 -position of the thiophene ring (preferably the 2-position).
  • X -OMe.
  • the reaction is carried out in the presence of an acid or base catalyst (e.g. sodium methoxide).
  • reaction scheme :
  • the compounds of the invention may be isolated from their reaction mixtures using conventional techniques including, for example, recrystallisation, filtration, column chromatography and distillation.
  • the compounds of the invention possess an odour profile which is sweet- floral, green, and pronounced of benzyl salicylate.
  • the compounds of the invention have an odour which is about 3 times stronger than benzyl salicylate. Moreover, the compounds of the invention are believed not to be allergenic.
  • 2- thiopene methanol salicylate ester possesses sweet, floral and mild balsamic notes and has excellent blending capabilities. It may be used as the foundation for heavy florals such as ylang, gardenia, etc.
  • the present invention provides the use of a compound or mixture of compounds of the invention as a flavour and/or fragrance.
  • the present invention also provides 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 of the invention as described above.
  • composition, product preparation or article may be in the form of a beverage, a flavouring, a food, a chewing gum, a pharmaceutical or an orally deliverable matrix.
  • the present invention further provides 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 composition or mixture of compounds of the invention.
  • composition product, preparation or article may be in the form of a perfume, a body odorant, deodorant or antiperspirant, a detergent, a bleach product or a disinfectant.
  • the present invention provides a substrate treated with a compound or mixture of compounds of the invention and a method for treating a substrate with a compound or mixture of compounds of the invention.
  • the present invention also provides compositions, products, preparations or articles containing as a flavour and/or fragrance ingredient a compound or mixture of compounds of the invention as described above.
  • the compounds of the invention can be included in virtually any article of manufacture that can include fragrance or flavourant compounds.
  • Examples include hypochlorite (bleach) compositions, detergents, flavourings and fragrances, beverages, including alcoholic beverages, and the like.
  • the compounds of the invention can be used in applications like soaps, shampoos, denture cleanser tablets, 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 of the invention is not limited to the above-mentioned products, as they may 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.
  • the compounds of the invention also find utility in foods, flavourings, beverages such as beer and soda, denture cleansers (tablets), flavoured orally-delivered products such as lozenges, candies, chewing gums, matrices, pharmaceuticals and the like. These uses are described in more detail below.
  • the compounds of the invention can be used as perfuming ingredients, as single compounds or as mixtures thereof.
  • the compounds can 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 compounds of the invention can be used alone, in admixture with each other, or in admixture with other perfuming ingredients, solvents or adjuvants of current use in the art.
  • 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 their 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 compounds of the invention 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 odour 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 compounds of the invention are typically present at concentrations between about 0.01 and about 30% (e.g. 0.1 to 20%), or even more, by weight of these compounds relative to the weight of the composition, product or article in which they are incorporated. It will be appreciated that the amount by weight of a compound of the invention in a particular composition or product will depend on the nature of the composition. For example, a washing powder will typically contain less than 1 % by weight of a compound of the invention while a fine fragrance may contain more than 20 % by weight of a compound of the invention.
  • the compounds may be used in detergents such as those 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.
  • body deodorants and antiperspirants for example, those containing aluminum salts.
  • the compositions described herein may 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.).
  • 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 described 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 compounds of the invention can be incorporated into beverages and impart various flavourings 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 flavoured beverage.
  • the beverage compositions can be in liquid or powdered form.
  • the beverage compositions can also include one or more flavouring agents; artificial colorants; vitamin additives; preservatives; caffeine additives; water; acidulants; thickeners; buffering agents; emulsifiers; and/or fruit juice concentrates.
  • Artificial colorants that may be used include caramel color, yellow 6 and yellow 5.
  • 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 that 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 may, for example, be 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: Flavour Concentrate, including one or more of the compounds of the invention 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
  • 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.
  • Flavoured food and pharmaceutical compositions including one or more of the compounds of the invention can also be prepared.
  • the compounds of the invention can be incorporated into conventional foodstuffs using techniques well known to those of skill in the art.
  • the compounds 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 compounds of the invention can be released into the orally-deliverable polymeric matrix material as the composition is chewed and held in the mouth, thus prolonging the flavour of the composition.
  • the flavour 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.
  • Flavoured compositions of the invention may include 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 compounds of the invention entrapped within the internal pore networks.
  • the compounds of the invention 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 flavourless gum base can be combined with a compound or a mixture of compounds of the invention to a desired flavour concentration.
  • a blade mixer is heated to about 110 0 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 compound or compounds of the invention are 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 compounds of the invention may be incorporated into a system that can release a fragrance in a controlled manner.
  • These include substrates such as air fresheners, laundry detergents, fabric softeners, deodourants, lotions, and other household items.
  • the fragrances are generally one or more derivatives of essential oils as described herein, each present in different quantities.
  • US Patent No. 4,587,129 the contents of which are hereby incorporated by reference in their entirety, describes a method for preparing gel articles that 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.
  • the present invention is illustrated by the following non-limiting example.
  • methyl salicylate 33g, 0.22 mol
  • 2-methanol-thiophene 25g, 0.22 mol
  • sodium methoxide 0.5g, 0.02 mol
  • the reaction was followed by 1 H NMR.
  • the mixture was taken into dichloromethane, filtered and after evaporation of the solvent, the crude product was purified by column chromatography on silica gel eluting with ethyl acetate/hexane (l %/99%) to give the desired product and methyl salicylate which was removed under distillation (122 0 CC at 15mbar).
  • 2-thiophene methanol salicylate ester crystallised as a white solid (13.8g, 59 mmol).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Confectionery (AREA)

Abstract

La présente invention concerne un composé ou un mélange de composés répondant à la formule (I) : dans laquelle R1 et R2 représentent, indépendamment, un groupe alkyle linéaire ou ramifié en C1 à C4, n vaut de 0 à 4 et m de 0 à 3, et leur utilisation en tant qu'arômes et/ou parfums. L'invention concerne également des procédés pour conférer, améliorer, augmenter ou modifier une propriété de goût ou de saveur ou les caractéristiques d'arôme, de parfum ou d'odeur d'une composition, d'un produit, d'une préparation ou d'un article. La présente invention concerne en outre des compositions, des produits, des préparations ou des articles contenant en tant qu'ingrédient d'arôme et/ou de parfum un composé ou un mélange des composés de l'invention tels que décrits ci-dessus.
EP07766258A 2006-07-17 2007-07-17 Salicylate de thiophénéméthyle et composés parents en tant que arômes et parfums Withdrawn EP2046772A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US83122906P 2006-07-17 2006-07-17
US11/738,919 US20080260669A1 (en) 2007-04-23 2007-04-23 Aromachemicals
PCT/GB2007/002687 WO2008009914A1 (fr) 2006-07-17 2007-07-17 Salicylate de thiophénéméthyle et composés parents en tant que arômes et parfums

Publications (1)

Publication Number Publication Date
EP2046772A1 true EP2046772A1 (fr) 2009-04-15

Family

ID=38691691

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07766258A Withdrawn EP2046772A1 (fr) 2006-07-17 2007-07-17 Salicylate de thiophénéméthyle et composés parents en tant que arômes et parfums

Country Status (2)

Country Link
EP (1) EP2046772A1 (fr)
WO (1) WO2008009914A1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2519383A (en) * 1946-10-30 1950-08-22 Monsanto Chemicals Thenyl esters and miticide compositions containing the same
DE3400342A1 (de) * 1984-01-07 1985-07-18 Henkel KGaA, 4000 Düsseldorf Verwendung von salicylsaeureestern als riechstoffe, diese enthaltende riechstoffkompositionen, sowie neue salicylsaeureester
FR2740450B1 (fr) * 1995-10-27 2001-09-28 Rhone Poulenc Chimie Procede d'obtention de compositions parfumantes et de produits parfumes et produits ainsi obtenus
JP2006503794A (ja) * 2001-12-19 2006-02-02 フレキシトラル・インコーポレイテツド チオフェン誘導体および芳香剤としてのその使用
CN1753883A (zh) * 2003-01-21 2006-03-29 弗莱克特瑞尔公司 改进的茉莉合成香料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008009914A1 *

Also Published As

Publication number Publication date
WO2008009914A1 (fr) 2008-01-24

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