Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/10—Spiro-condensed systems
• • 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
  • A23L27/205—Heterocyclic compounds
  • A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
• • 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
  • A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
  • A24B15/40—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms
  • A24B15/403—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms having only oxygen as hetero 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
  • C11B9/0088—Spiro compounds

Definitions

• ABSTRACT A compound is disclosed to be useful in the flavouring of foodstuffs, feedstuffs. beverages, pharmaceutical preparations and tobacco products. The said compound is equally found to be a useful perfuming ingredient.
• the invention relates further to flavouring compositions and a process for improving, enhancing or modifying the flavouring properties of foodstuffs, feedstuffs, beverages, pharmaceutical preparations and, more particularly, tobacco products.
• a further object of the invention is represented by perfuming compositions and a process for improving, enhancing or modifying the odoriferous properties of perfumes and perfumed products.
• cigarettes for example, for the manufacture of cigarettes comprises a mixture of different types, to give the characteristic flavour and aroma desired in the smoke produced.
• cigarettes currently manufactured usually contain mixtures of Virginia, Maryland or Kentucky tobacco in combination with oriental or Turkish tobacco.
• flavouring substances and humectants as additives to these tobacco mixtures to further enhance the organoleptic properties thereof.
• the said compound may find a useful industrial application for the aromatisation of a great variety of materials, namely of foodstuffs and beverages.
• the said compound represents also a useful perfuming ingredient, and, accordingly, it is a further object of the present invention to provide perfuming compositions containing the 3,4,7- trimethyl-Z-oxo-l ,6-dioxa-spiro[4.5 ]dec-3-ene.
• 3,4.7-Trimethyl-2-oxol ,6-dioxa spiro[4.5 ]dec- 3-ene in its pure form or in admixture with other flavouring ingredients may be employed in a variety of forms.
• the chemical nature, solubility and stability determine the form in which the given compound or composition thereof is to be employed. It is preferable, however, to utilize the said compound or composition in the form of solutions thereof.
• the additive can be added at any step in the course of the treatment of the tobacco but is preferably added after aging, curing and shredding and before the tobacco is formed into cigarettes or other products.
• a convenient method for flavouring tobacco consists in spraying the tobacco with an alcoholic solution of the compound or flavouring mixture. Combinations of solvents such as alcohol and propylene glycol may also be used.
• the proportions of the new compounds to be used in said compositions or in accordance with the process of the present invention can vary within wide limits. Said proportions depend particularly on the specific organoleptic effects it is desired to achieve and on the origin of the tobacco products to which the mentioned flavouring ingredients are added.
• flavouring effects can be achieved with amounts ranging from I to I000 ppm, preferencially comprised between about l0 and 200 ppm, more particularly between about 10 and 20 ppm, based on the weight of the product flavoured.
• amount ranging from I to I000 ppm, preferencially comprised between about l0 and 200 ppm, more particularly between about 10 and 20 ppm, based on the weight of the product flavoured.
• analogous proportions may be employed.
• the compound of the invention When the compound of the invention is used as perfuming ingredient its proportions in the perfume compositions or perfumed products to which it is added may equally be comprised in a wide range. Thus, inter esting odoriferous effects may be achieved by amounts of from about I to about 10 percent of the total weight of the composition.
• the 3 ,4,7-trimethyl-2-oxol ,-dioxaspiro[4.5]dec-3-ene is a compound of natural origin. Said compound has been in fact isolated now for the first time from a natural essential oil.
• the essential oil has been obtained by extraction with a volatile solvent from the aqueous distillate collected by vapour distillation of a Burley tobacco upon previous acidification of the said distillate to ca. pH 4.
• the isolation procedure mentioned above is particularly complex and uneconomical as the essential oil is obtained with a yield not higher than 0.03 percent, based on the total weight of the tobacco treated.
• the isolation process consisted in a preliminary separation by fractional distillation under reduced pressure whereupon the less volatile fractions [B.p. 35C/0.00l Torr] were subjected to several distillations by means of high fractionating power columns.
• the 3,4.7-trimethyl-2-oxo-l,6-dioxa-spiro[4.5]dec- 3-ene is merely a minor constituent of the essential oil. Said compound has been detected in a concentration of ca. 0.03 percent. In its pure state this compound possesses an unprecedented original flavouring and per fuming note. It can in fact develop or simply enhance a variety of notes such as mild, herbal and woody notes. These organoleptic characters are particularly suitable for the aromatization of infusions or decoctions such as tea. camomile. lime tea or verbena for example. When the compound of the invention is used as perfuming ingredient, it can develop very interesting notes with a green or floral character. it confers to the products or compositions to which it is added a very natural and fresh nuance and develops rosy or. in some instances, jasmin-like notes.
• lactone I in view of its flavouring and perfuming properties, lactone I possesses a clearly distinct field of application, said application being also wider than that of the natural essential oil.
• 3,4,7 trimethyl-2oxol 6-dioxa-spiro(4.5 ]dec-3-ene is prepared by a process rial c1 Br which comprises treating a compound of formula cs on an wherein Y represents a leaving group or a hydrogen atom, with an acidic agent.
• a suitable leaving group may be represented by a tetrahydropyranyl group.
• Y represents a hydrogen atom
• compound ll defines a diol and the treatment with an acidic agent may thus be effected either directly on said diol, or on a precursor thereof.
• Suitable precursors include linear or cyclic ketals, such as for instance dimethyl or diethyl ketal, or the corre' sponding ethylenic ketals. However, in this latter case. there is obtained a ketonc intermediate which before cyclisation must be subjected to a reduction in order to yield the desired diol.
• Suitable acidic agents include a strong mineral or organic acid, such as cg. hydrochloric, sulphuric, phosphoric or p-toluenesulfonic acid.
• the reaction may be effected on the starting material of formula ll or on a solution thereof in an inert organic solvent such as an aromatic hydrocarbon, benzene, toluene or xylene for instance.
• the temperature used for carrying out the above reaction can vary within wide limits. Suitable temperatures are comprised between about and about 150C. However. the best yields of the final product were achieved by using temperatures lying in the vicinity of the boiling point of the chosen solvent.
• the compounds of formula II wherein Y represents a tetrahydropyranyl group can be prepared according to a reaction of the Grignard type between dimethylmaleic anhydride and the alkylmagnesium halide obtained by reacting, for instance, S-chloro-Z-pentoxytetrahydropyrane with magnesium metal.
• R0 OR I r'due tion 1n the hereinabove scheme symbols R. when taken separately. stand for a lower alkyl radical. such as methyl or ethyl. or they may represent, when taken together. a radical of the type(CH2),, wherein n is the integer 2. 3 or 4.
• the 5-halopentan-2-one used as starting material in the above described process, is a commercially available compound. lts conversion into the corresponding ketal can be effected by means of the techniques conventional in the art [cf. e.g. Bull. Soc. Chim. France 2568 (1963)].
• formula I is deemed to represent a compound which possesses a bicyclic skeleton wherein the said methyl substituent is in position cis or trans relative to the oxygen atom in position 1.
• the compound of formula 1 can be used under the form of one ofits pure isomers or. more frequently. for practical and economic reasons, said compound can be used without further separation as directly obtained by the process of the invention.
• EXAMPLE 1 3,4,7 -Trimethyl-2-oxo-l,6-dioxy-spiro[4.5ldec-3-ene
• the reaction vessel was connected to a water sep arator and the reaction mixture was kept under nitrogen. After cooling.
• the compound used as starting material in the process described above was prepared as follows a. 2.50 g (0.066 M) of sodium boronhydride were slowly added within 45 min. to a solution of 24.0 g (0.20 M) of 5-chloropentan-2-one in 300 ml anhydrous methanol kept under stirring at a temperature of about 5. The reaction mixture was maintained at room temperature during one night whereupon it was concentrated under reduced pression at low temperature and poured into a mixture of hydrochloric acid and ice. The product was then extracted twice with ml of ether and the combined organic extracts were washed with a 5 percent aqueous solution of NaHCO then with water until neutrality. On drying over MgSO and evaporation, the organic extracts gave 17.2 g (yield 70%) of 5-chloro-pentan-2-ol; B.p. 46-8/ 0.001 Torr.
• reaction mixture was then kept at this tent perature during 2 more hours whereupon after dilution with an equal volume of tetrahydrofurane it was added within 2 hr to a solution of 4.8 g (38 mM) of dimethylmaleic anhydride in 20 ml of dry tetrahydrofurane at a temperature of 5.
• the mixture was then kept overnight at 20, acidified with 10 percent sulfuric acid. kept under stirring during one hour and finally ex tracted with 2 portions of 100 ml each of ether. After the usual treatments of washing, drying and evaporation at a temperature lower than 100 under reduced pressure (0.001 Torr) there was obtained a residue which was then directly used for the following reaction step.
• EXAMPLE 2 2 g of a l percent solution of 3.4.74rimethyl-2-oxol 6-dioxa-spiro[4.5]dec-3ene in 95 70 ethanol were sprayed onto 100 g ofa tobacco mixture of the american blendtype.
• the tobacco thus flavoured was then used for the manufacture oftest" cigarettes the smoke of which was subjected to an organoleptic evaluation by a panel of flavour experts. These latter unanimously declared that the smoke of the test cigarettes presented a typical character with a mild, herbal and woody note; the tobacco note possessed moreover a more plaisant character than that of the smoke of the control" cigarettes the tobacco of which was simply treated with 95 percent ethanol.
• EXAMPLE 3 A black tea infusion was prepared by brewing 6 g of commercial black tea leaves in l l of boiling water. After a few minutes brewing the infusion was put into clean cups in an amount of ca ml of solution per cup. To some of the thus prepared cups there were added 0.06 ml of a l percent solution of 3,4,7- trimethyl-2-oxo-1,6dioxa-spiro[4.5]dec-3-ene in 90 percent ethanol.
• a base perfume composition was prepared by mixing the following ingredients (parts by weight) Methyl 1-(cis-pent-Z-cn)l) 3-oxo cyclopentylacctate Hl'f r" 5U Cinnamon at l()'/* 4U Levo-Z-l 2-methyl-prop-2- enyl)-4-methyltetrahdropyrane 2t) Neroli higaradc l0 Linalool 8O Linalyl acetate Linalyl formate 2O Levo-citronellol Citronellyl acetate 30 Citroncllyl formate 20 Hydroxycitronellal 20 Phenylethyl alcohol 20 Methylionone 4U Nerolidol 6G Hexylcinnamic aldehyde 5U Benzyl acetate 70 Heliotropin 3O Cinnamic alcohol 50 Ylang 30 l, l dimethyl-2-acetyl'6- ter-butyl in
• composition of matter consisting essentially of a compound of formula 2.
• a composition of matter consisting essentially of cis-3,4,7-Trimethyl-2-oxol ,6-dioxa-spiro[4.5 ]dec- 3-ene.
• composition of matter consisting essentially of trans-3,4,7-Trimethyl-2-oxol ,6-dioxa-spirol 4.5 ldec- 3-enel

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

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Cited By (1)

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• 1972
  • 1972-06-16 CH CH907672A patent/CH556646A/de not_active IP Right Cessation
• 1973
  • 1973-06-14 US US370049A patent/US3880888A/en not_active Expired - Lifetime
  • 1973-06-15 DE DE2330516A patent/DE2330516A1/de active Pending
  • 1973-06-18 GB GB2890173A patent/GB1397896A/en not_active Expired

Non-Patent Citations (2)

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