Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/20—Synthetic spices, flavouring agents or condiments
  • A23L27/204—Aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
  • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
  • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
• • 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

• This invention relates to alkylsulfanyl-benzenes, and in particular those having spicy and anisic odour notes, a method of producing the same and to flavour and fragrance compositions containing one or more of these compounds.
• the invention provides in one of its aspects the use of compound of formula I as flavour or fragrance
• R 1 is methyl, ethyl, / ' -propyl, n-propyl
• R 2 and R 3 are independently hydrogen or methyl
• R 2 and R 3 taken together is a divalent radical (CH 2 ) n , C(CH 3 ) 2 , or CH(CH 3 ) which forms a cycloalkane ring together with the carbon atoms to which it is attached;
• R 4 and R 5 are independently hydrogen or methyl
• R 4 and R 5 taken together is a divalent radical (CH 2 ) n , (CH 2 ) n . 1 CH(CH 3 ) 2 , or which forms a cycloalkane ring together with the carbon atoms to which it is attached; n is an integer of 1 , 2, 3, or 4; and wherein at least one cycloalkane ring is present; or
• R 1 is methyl, ethyl, /-propyl, n-propyl
• R 2 is hydrogen or methyl
• R 3 and R 4 together is hydrogen or methyl
• R 5 is hydrogen, methyl, ethyl, /-propyl, n-propyl, ⁇ -butyl, ferf-butyl or sec-butyl.
• the compounds of formula I may comprise one or more a chiral centres and as such may exist as a mixture of stereoisomers, or they may be resolved as isomerically pure forms. Resolving stereoisomers adds to the complexity of manufacture and purification of these compounds, and so it is preferred to use the compounds as mixtures of their stereoisomers simply for economic reasons. However, if it is desired to prepare individual stereoisomers, this may be achieved according to methodology known in the art, e.g. preparative HPLC and GC or by stereoselective syntheses.
• Particularly preferred compounds of formula I wherein the bond between Ci and C 2 is a single bond are 1-cyclopropylmethyl-4-methylsulfanyl-benzene, 1-cyclobutylmethyl-4- methylsulfanyl-benzene, 1-cyclopentylmethyl-4-methyIsulfanyl-benzene and 1- cyclohexylmethyl-4methylsulfanyl-benzene.
• Particularly preferred compounds of formula I wherein the bond between Ci and C 2 together with the dotted line is a double bond are 1-prop-1-enyl-4-methylsulfanyl- benzene and 1-hex-1-enyl-4-methylsulfanyl-benzene.
• Compounds of formula I may be used alone or as a mixture to form a fragrance composition, which composition forms another aspect of the present invention.
• the compounds may be used in combination with other known flavourant or odourant molecules selected from the extensive range of natural and synthetic molecules currently available and/or in admixture with one or more ingredients or excipients conventionally used in conjugation with odourants or flavourants in fragrance or flavour compositions.
• alcohols farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, (Z)-hex-3-en-1-ol, menthol, ⁇ -terpineol.
• aldehydes citral, ⁇ -hexyl cinnamaldehyde, Lilial, methylionone, verbenone, nootkatone, geranylacetone.
• esters allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, cis-3-hexenyl isobutyrate, cis-3-hexenyl salicylate, linalyl acetate, methyl dihydrojasmonate, styralyl propionate, vetineryl acetate, benzyl acetate, geranyl acetate.
• lactones ⁇ -undecalactone, ⁇ -decalactone, pentadecanolide, 12-oxahexadecanolide.
• acetals Viridine (phenylacetaldehyde dimethylacetal). other components often used in perfumery: indole, p-mentha-8-thiol-3-one, methyleugenol, eugenol, anethol.
• the compounds of the present invention may be used neat and simply admixed to form compositions. Alternatively or additionally however, they may be entrapped with entrapment materials, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, or they may be chemically bound to substrates which are adapted to release the compound of formula 1 upon application of an exogenous stimulus such as light, enzyme, or the like, and these entrapped forms may be used in compositions of the present invention.
• entrapment materials for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, or they may be chemically bound to substrates which are adapted to release the compound of formula 1 upon application of an exogenous stimulus such as light, enzyme, or the like
• compositions may optionally comprise other excipients well known in the art, including anti-foaming agents, anti-oxidant agents, binders, colourants, diluents, disintegrants, emulsifiers, enzymes, fats, flavour-enhancers, flavouring agents, gums, lubricants, polysaccharides, preservatives, proteins, solubilisers, solvents, stabilisers, sugar-derivatives, surfactants, sweetening agents, vitamins, waxes, and the like.
• Solvents which may be used are known to those skilled in the art and include e.g. ethanol, ethylene glycol, propylene glycol, glycerol, triacetin, diethyl phthalate and dimethyl phthalate.
• the compounds of the present invention may be used in fragrance applications, e.g. in any field of fine and functional perfumery, such as perfumes, household products, laundry products, body care products and cosmetics.
• fragrance applications e.g. in any field of fine and functional perfumery, such as perfumes, household products, laundry products, body care products and cosmetics.
• the high diffusion and substantivity of compounds according to the present invention are well perceived on fabrics washed with detergent or treated with a softener comprising them.
• the typical spicy anisic odour is already perceived on wet fabric and lingers for long periods, e.g. 2 - 4 days on dry fabric.
• the compounds of formula I may be used in flavour applications and are useful in modifying for example, spicy flavours and seasonings for condiments and meats. They may be used in aromatic, herbal and spicy flavourings, heavy fruit flavours (e.g. raisin, prune) and in flavours for root beer. The compounds are also well suited for mouthwash applications.
• the compounds of the formula I may be present in compositions in amounts ranging from 0.001 to 1000 mg/kg, more preferably from 0.05 to 500 mg/kg.
• compounds of the formula I can be employed in widely ranging amounts depending upon the specific application, for example, from about 0.001 to about 10 weight percent.
• One application may be a fabric softener comprising about 0.001 to 0.05 weight percent.
• Another application may be an alcoholic solution comprising about 0.1 to 10 weight percent.
• the preferred concentrations vary between about 0.1 and 5 weight percent. However, the values are not limiting on the present invention, since the experienced perfumer may also achieve effects with even lower concentrations or may create novel accords with even higher amounts.
• R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as given above with the proviso that if the bond between d and C 2 together with the dotted line represents a double bond, R 1 is ethyl, R z is hydrogen, and R 3 and R 4 together is hydrogen, then R 5 is not hydrogen.
• the compounds of formula I may be synthesised from commonly-available starting materials and reagents according to synthetic protocols known in the art. Benzene-(4- alkylsulfanyl-cycloalkyl) compounds of formula I (i.e.
• R 2 and R 3 forms a cycloalkane ring together with the carbon atoms to which they are attached
• R 2 and R 3 may be synthesised from the corresponding 4-alkylsulfanyl-phenyl carbonyl compound, e.g. 4-methylsulfanyl- benzaldehyde, under Wittig reaction conditions, followed by cycloalkylation of the intermediate alkylsulfanyl alkenyl benzene, e.g. 1-methylsulfanyl-4-propenyl-benzene, under Simmons-Smith reaction conditions, well known in the art.
• Benzene-(4-alkylsulfanyl-cycloalkyl-methyl) compounds of formula I may be synthesised from the corresponding 4-alkylsulfanyl-benzene, e.g. thioanisol (C6H5SCH3), and the corresponding carboxylic acid chloride, e.g. cyclopropanecarboxylic acid chloride, followed by reduction of the intermediate ketone, e.g. cyclopropyl-(4-methylsulfanyl-phenyl)-methanone, under Wolff-Kishner reaction conditions well known in the art.
• R 4 and R 5 forms a cycloalkane ring together with the carbon atoms to which they are attached
• Odor description anisic, minty, anethole
• Example 2 1-Hex-1-enyl-4-methylsulfanyl-benzene Synthesized analogously to the procedure of Example 1.
• Cyclobutane carboxylic acid chloride (4.50g, 38 mmol) dissolved in dichloroethane (10 ml) was added dropwise to a cold (-10°C) suspension of AICI 3 (4.81 g, 38 mmol) in dichloroethane (20 ml). To this solution was added methylsulfanyl-benzene (4.49g, 36 mmol) at such a rate that the temperature did not exceed 10°C. After the mixture was stirred for 45 min in an ice bath, it was poured on water and extracted with dichloroethane. The organic phase was separated, washed with water and brine, dried (MgSO ) and concentrated in vacuo to yield a crystalline solid (6.78g, 91%).
• Example 4 1-Cvclopropylmethyl-4-methylsulfanyl-benzene Synthesized analogously to the procedure of Example 3.
• Odor description fresh, sassafras, tarragon, agrestic
• Example 5 1-Cvclopentylmethyl-4-methylsulfanyl-benzene Synthesized analogously to the procedure of Example 3.
• Odor description floral, sassafras, cinnamic, sweet.
• a woody, spicy fragrance was made with the following ingredients parts per weight

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Polymers & Plastics (AREA)
• Food Science & Technology (AREA)
• Health & Medical Sciences (AREA)
• Nutrition Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Fats And Perfumes (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Cosmetics (AREA)

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• 2002
  • 2002-12-19 GB GBGB0229453.6A patent/GB0229453D0/en not_active Ceased
• 2003
  • 2003-12-12 DE DE60315069T patent/DE60315069T2/de not_active Expired - Lifetime
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  • 2003-12-12 US US10/534,338 patent/US20060014664A1/en not_active Abandoned
  • 2003-12-12 AU AU2003303211A patent/AU2003303211A1/en not_active Abandoned
  • 2003-12-12 ES ES03813507T patent/ES2289366T3/es not_active Expired - Lifetime
  • 2003-12-12 CN CNB2003801049617A patent/CN1307152C/zh not_active Expired - Fee Related
  • 2003-12-12 JP JP2004560977A patent/JP2006510685A/ja active Pending
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  • 2003-12-12 AT AT03813507T patent/ATE367375T1/de not_active IP Right Cessation
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