Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/385—Saturated compounds containing a keto group being part of a ring
  • C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
  • C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
  • C07C49/427—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
  • C07C49/447—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing ten carbon atoms
• • 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
  • A23L27/203—Alicyclic compounds
• • A—HUMAN NECESSITIES
  • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
  • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
  • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
  • A24B15/18—Treatment of tobacco products or tobacco substitutes
  • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
  • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
  • A24B15/34—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring
  • A24B15/345—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring containing condensed rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
  • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
  • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
  • C07C13/72—Spiro hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
  • C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/013—Esters of alcohols having the esterified hydroxy group bound to a carbon atom of a ring other than a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/74—Benzo[b]pyrans, hydrogenated in the carbocyclic ring
• • 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
  • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
  • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
  • C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
  • C11B9/0053—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms both rings being six-membered
• • 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
  • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
  • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
  • C11B9/0057—Spiro compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/93—Spiro compounds
  • C07C2603/94—Spiro compounds containing "free" spiro atoms

Definitions

• ABSTRACT Use of bicycliccompounds, some of which are new, as perfuming the'manufacture of perfumes and perfumed products and/or .in the preparation of artificial flavours for foodstuffs, animal feeds, beverages, pharmaceutical preparations and tobacco products.
• the invention relates to the use of a new class of valuable perfuming and/or flavouring ingredients.
• Said ingredients are bicyclic compounds of formula containing a single or a double bond in the position indicated by the dotted line and wherein the index n represents the integers zero or 1, one of the pairs of symbols X represents, when said symbols are taken together, an oxygen atom or, when said symbols are taken separately, a hydroxyl or an O-acyl group and a hydrogen atom, and the other pair represents two hydrogen atoms and wherein i.
• R and R represents a lower alkyl group and the other is a hydrogen atom and R represents a lower alkyl group when the index n is zero; or ii. each of the symbols R, R, R and and R represents a lower alkyl group or a hydrogen atom provided however that the pairs: R and R and R and R represents a lower alkyl group or a hydrogen atom provided however that the pairs: R and R and R and R respectively, cannot simultaneously comprise more than one alkyl group.
• the invention also relates to new bicyclic compounds of formula ,wherein the pair of symbols X in position 8 is defined as lin formula land the other represents two hydrogen symbols R, R R and R are defined as indicated hereinabove.
• the invention further relates to a process for the preparation of bicyclic compounds of formula I which comprises:
• One of the main objects of the aromatization of foodstuffs for instance is to restore the original quality and nature of the flavour, aroma and taste of a given foodstuff material.
• the organoleptic properties of foodstuffs particularly diminish or are somehow modified in the course of the processes of freezing and storage, or during the modifications, such as cooking or baking, to which the foodstuffs are subjected in order to yield an edible material.
• lower alkyl group is defined to mean a branched or linear alkyl group containing from one to 4 six carbon atoms, as e.g. a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or ter-butyl group.
• the compounds of formula I can improve, enhance or modify various olfactive notes, e.g. woody, earthy or balsamic notes.
• various olfactive notes e.g. woody, earthy or balsamic notes.
• the compounds of formula I it is thus possible to create perfume compositions possessing a modem or more classical new fresh and woody character reminiscent in some instances of the odour of amber, ylang, sandelwood or patchouli for example. It was furthermore noticed that the thus improved or modified woody notes were, in some cases, particularly tenacious.
• the use of the said compounds is also appreciated for the manufacture of perfumed products as e.g. soaps, detergents, waxes, household materials or cosmetic preparations.
• the compounds of formula I are used as perfuming ingredients in perfume compositions the more interesting effects are achieved by the use of proportions comprised between about 0.5 and about 2% of the total weight of the perfumed composition.
• proportions comprised between about 0.5 and about 2% of the total weight of the perfumed composition.
• lower, e.g. of the order of 0.01 or higher concentrations, from about 5 to 10 (parts by weight) can also be used.
• concentrations used can be as high as about of the total weight of the said base.
• the compounds of formula I are also appreciated in the flavour industry. Depending upon the nature of the products in which they are incorporated, the said compounds can improve, enhance or modify various gustative notes such as woody, slightly earthy or balsamic notes, in some instances reminiscent of these of fresh berries. They are particularly appreciated for the preparation of artificial flavours of walnuts, hazelnuts, peanuts or those of citrus fruits as e.g. lemon or grapefruit, or even those of bilberries or cranberries.
• the said compounds can also be used for flavouring tobacco and tobacco products.
• they can improve various woody or amber-like notes pronounced in some instances of the taste of certain oriental tobaccos.
• the proportions used can vary within wide limits and being of the order of 1 ppm to l of the total weight of the flavoured material.
• proportions comprised between about 50 and about ppm of the total weight'of the flavoured product.
• the said compounds When the said compounds are used as ingredients for I the preparation of artificial flavours, they can be used in proportions comprised between about 0.1 and about 15 of the total weight of the said flavouring composition, the proportions preferably used being of the order of l to 10 Owing to the presence of various substituents in the positions 2, 6 and 10 or 6, 8 and 10 of the spiranic skeleton, more precisely defined as a spiro[4.5]decane skeleton, the formula I can represent several stereoisomeric forms of the given compound. As a consequence it is necessary to use a specific nomenclature in order to define these particular bicyclic derivatives.
• the alkyl substituents in position 6 or 10 can by all evidence possess a cisor a transconfiguration relative to the said C .C bond.
• the possible hydroxyl or O-acyl group in position 8 may have an axial or an equatorial configuration.
• the possible hydroxyl or O-acyl group in position 2 can possess a cisor transconfiguration relative to the C -C bond. Therefore the said formula represents either an individual stereoisomer or any possible arrangement of the said stereoisomeric forms.
• the formula I is deemed to represent either meso, racemic or optically active compounds.
• the compounds of formula I can be used in a pure isomeric form.
• mixtures of stereoisomers as directly obtained by the process of the invention can also be used.
• some of the compounds of formula I can be prepared by oxidizing compounds of formula II.
• the said process may formally be visualized as an oxidative splitting of the exocyclic double bond of said compounds of formula 11.
• Such a splitting can be effected either according to the conventional methods used to split a carbon-carbon double bond [see e.g. L.F. Fieser and M. Fieser, Reagents for Organic Chemistry, Vol. I, p. 773, John Wiley & Sons, New York, 1967], or by means of an alkali metal metaperiodate in the presence of a catalytic amount of osmium tetroxide [see e.g. op. cit.', p. 812], or by means of a metal oxide such as CrO or of an oxidized metal derivative such as an alkali metal chromate or permanganate in the presence of a strong mineral acid.
• the splitting of the said exocyclic double bond can also be achieved by treating the compound of formula II with a peracid, hydrolizing the thus obtained epoxyde and subsequently oxidizing the obtained diol.
• Suitable organic peracids include performic, peracetic, trifluoroperacetic, perphthalic or m-chloroperbenzoic acid.
• the said peracid preferably reacts with the higher substituted double bond [see Organic Reactions 7, 378 (1953), .I. Wiley & Sons, New York], i.e., the exocyclic doublehbolndlolthc compound offormula ll.Th e subse- Th6 Said rcductim can be effected by means of a a?
• the oxidation of the thus obtained diol may be effected by means of a strong oxidizing 5 agent, e.g. lead tetraacctate or periodic acid [sec e.g. L. F. Fieser and M. Fieser. Reagents for Organic Chem istry, vol. I, p. 546 and 816. J. Wiley & Sons. New York, l967].
• the oxidative splitting of the exocyclic double bond of the compound of formula ll can also be effected by means of singlet oxygen and subsequent treatment of the obtained oxidation mixture with an means of an alkal' metal alummumhydndes acidic reagent.
• Singlet oxygen can be generated by dyeof boronhydt'ldes Such as NaBH4 for example sensitized photooxygenation.
• a dyestuff such as por- Tetrahedron 22, 487
• an of tion can also be effected by means of a reactant such as hydrazine, in the presence of a base such as an alkali metal hydroxide, and a polar solvent possessing a high boiling point such as e.g. ethylene glycol, according to the Huang-Minlons method [see L. F. Fieser & M. m Fieser, Reagents for Organic Chemistry, Vol. I, p. 435, John Wiley & Sons, New York, 1967].
• the reduction of the above bicyclic ketones can moreover be effected via the corresponding tosylhydrazone, by
• an oxidizing agent such as tervents include water, an aqueous organic solvent, an arbutyl chromate or a CrO -pyridine complex may also omatic or aliphatic hydrocarbon such as e.g. benzene, be used [see J. Org. Chem. 34, 3587 (1969)]. toluene or n-hexane, an alcohol. e.g. methyl or ethyl alcohol. an ether such as e.g.
• Lewis acids can be conveniently used.
• a metalhalide such as AlCl ZnCl SnCl or FeCl can be employed.
• BF is however preferred.
• a base perfume composition of the Chypre type was prepared by admixing the following ingredients (parts by weight):
• a base pc rfume composition for a masculine Eau de Cologne was prepared by admixing the following ingredients (parts by weight) Sage oil Lavender oil I50 Synthetic bergamot Z00 Lemon oil I40 Sweet orange oil 40 Synthetic galhanum l0'/I* 20 Muscone 1092* 50 Methyl 1-pentyl-3-oxo-cyclopentylacetate 10 l l l)imethylJi-ter-butyl-4- acetylindane l0 a-lsomethylioimne 50 Synthetic ylang 80 Synthetic jasmine Synthetic geranium 50 Synthetic ncroli I00 ('oriander oil 5 Total 950 in diethyl phthalate By adding to 95 g of the above base composition 5 g of a 10% solution of 6.10 cis-dimethyl-(5rC)- spiro
• a base perfume composition for after-shave lotion was prepared by admixing the following ingredients (parts by weight) i Menthol l0 Hugenol 50 ('oumarin 20 Mnscone l0'/l* Z0 Phenylethyl alcohol 120 Lavender oil 210 Pimento oil 40 ('innanion oil 5 Synthetic hergamot Z ('ychipentadecanone l0'/1 3t) Methyl Z-pcntyl-3-tixo-eyclopentylacetate 10 Ahsolute oak moss l5 "007)1 salic 'late 20 lsobutyl salrcylute 30 (ieranium liourhon oil 70 Musk ketone 20 Total "50 in 15% eth ⁇ l alcohol By adding to g of the above base composition 5 g of a l0% ethanolic solution of 6.
• a base flavouring composition of the Tutti-Frutti type was prepared by admixing the following ingredients (parts by weight) Vanillin 25 Allyl caproate l0 (itral l5 Amyl butyrate 35 Sweet orange oil 50 l-ithyl butyrate 75 Ethyl acetate 150 Amy] acetate I50 Lemon oil 250 Orange tcrpenes 240 Total I000 Two flavouring compositions were then prepared as indicated below (parts by weight) A (test) ll (control) Base composition I00 (1.10 cis-l)inieth ⁇ 'l-(SrL spirol 4.5 ldec-h-en-Z-one I00 )5'71 Ethyl alcohol 800 900 Total I000 [000 Both mixtures A and B were then used for the preparation of the following foodstuffs.
• EXAMPLE 5 A commercial bilberries jam was flavoured with a ethanolic solution of 6,10 cis-dimethyl-(5rC spiro[4.5]dec-6-en-3-one, in the proportions of 10 ml of said ethanolic solution per 100 kg of flavoured material. The thus flavoured foodstuff was then compared by a panel of flavour experts with an unflavoured jam containing ethyl alcohol in the above given proportions. It was declared that the flavoured jam possessed a woody, slightly balsamic taste reminiscent of that of fresh bilberries.
• EXAMPLE 6 To 1 liter of an acidulour sugar syrup (prepared by diluting 650 g of sucrose and 10 ml of a 50% aqueous solution of citric acid in 1000 ml of water), flavoured with lemon or grapefruit oil in the proportion of 30 g of the said oil per 100 l of syrup, there was added 1 ml of a 1% ethanolic solution of 6,10 cis-dimethyl-(SrCU- spiro[4.5 ]dec-6-en-2-one. The thus flavoured beverage was then compared with an unflavoured syrup by a panel of flavour experts. These latter declared that the flavoured syrup as compared with the unflavoured one, possessed a more marked and very pleasant fruity taste with a slightly woody character.
• EXAMPLE 7 7 g of a 1% ethanolic solution of 6,10 cis-dimethyl- (5rC)-spiro[4.5]dec-6-en-2-one were sprayed onto 100 g of an american b1endtobacco mixture.
• the tobacco'thus flavoured was used for the manufacture of test cigarettes, the smoke of which was then subjected to organic evaluation by comparison with unflavoured control cigarettes.
• the tobacco used to prepare the control cigarettes was preliminary treated with a corresponding amount of ethyl alcohol.
• a panel of flavour experts defined the taste of the smoke of the test cigarettes as being more rounded than that of the controlcigarettes, the said smoke possessing moreover a more marked woody character.
• EXAMPLE 8 6, l 0-Dimethyl-cis-( 5rC )-spiro[4.5 dec-6-en-2-one
• EXAMPLE ll 6 1 0-transDi methyl-( 5 rC )-spiro[4.5 ]dec-6-en-2-one 2.8 g (28 mM) of CrO have been added to a solution of 4.5 ml of pyridine in 65 ml of CHgClg, whereupon 0.85 g (ca. 4.7 mM) of 6,1 O-trans-dimethyl-(SrC -spiro[4.5]dec-6-en-2-ol 7 ml of CH- CI were slowly added thereto under stirring and at room temperature and finally left 1 hr at this temperature. The reaction mixture was then poured onto ice and extracted with n-pentane.
• the isomeric saturated hydrocarbons used as starting materials in the hereinabove preparation were synthesized as follows:
• the mixture used as starting material in the hereinabove process can be prepared as follows:
• EXAMPLE 18 6,10 trans-Dimethy1-( 5rC)-spiro[4.5]dec-6-en-8-o1
• 610 trans-dimethyl-(5rC spiro[4.5]dec-6-en-8-one see Example 14
• EXAMPLE 19 6, l trans-Dimethyl-( rC 1 )-8-acetoxy-spiro[ 4.5 ]dec-6-ene
• the unsaturated alcohol obtained according to Example 18 was esterified by means of acetic anhydride in pyridine in order to give the title compound in 85 yield.
• index n represents the integers zero or 1 and wherein: i. one of the symbols R and R represents a lower alkyl group and the other is a hydrogen atom and R represents a lower alkyl group when the index n is zero; or ii. each of the symbols R, R R and R represents a lower alkyl group or a hydrogen atom provided however that the pairs R and R and R and R respectively, cannot simultaneously have more than one alkyl group.

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• 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)
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• General Chemical & Material Sciences (AREA)
• Toxicology (AREA)
• General Health & Medical Sciences (AREA)
• Nutrition Science (AREA)
• Food Science & Technology (AREA)
• Polymers & Plastics (AREA)
• Fats And Perfumes (AREA)
• Cosmetics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
• Fodder In General (AREA)
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• 1973
  • 1973-05-23 US US363187A patent/US3923873A/en not_active Expired - Lifetime
  • 1973-05-28 FR FR7319366A patent/FR2203643B1/fr not_active Expired
  • 1973-05-29 CH CH770173A patent/CH570776A5/xx not_active IP Right Cessation
  • 1973-05-29 DE DE2327370A patent/DE2327370A1/de active Pending
  • 1973-05-29 JP JP48060190A patent/JPS4947545A/ja active Pending
  • 1973-05-29 NL NL7307447A patent/NL7307447A/xx unknown
  • 1973-05-29 GB GB2544173A patent/GB1399325A/en not_active Expired

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