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
  • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
  • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
  • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
  • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
• • 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
  • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
  • C07C49/597—Unsaturated compounds containing a keto groups being part of a ring of a five-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
  • C07C49/603—Unsaturated compounds containing a keto groups being part of a ring of a six-membered ring, e.g. quinone methides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
  • C07C49/687—Unsaturated compounds containing a keto groups being part of a ring containing halogen
• • 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
  • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
  • C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms

Definitions

• the present invention relates to new alicyclic ketcesters, more particularly to lower alkyl esters of 2-alkyl-3- oxo-cycloalkyl-acetic acids, which possess interesting olfactive properties and which, therefore, are useful in the preparation of a great variety of perfume compositions.
• the invention also relates to perfume compositions including said new alicyclic keto-esters.
• n represents an integer from 1 to 2
• R represents an alkyl radical having from 4 to 6 carbon atoms
• R represents methyl or ethyl.
• the substituent represented by R in the above Formula I can be a straight chain alkyl radical such as n-butyl, n-pentyl or n-hexyl, or a branched alkyl radical, i.e. a secondary or tertiary alkyl radical, in particular an isoalkyl radical (having the terminal group CH(CH e.g. isobutyl, isopentyl, or (3-methyl-butyl) and isohexyl.
• a straight chain alkyl radical such as n-butyl, n-pentyl or n-hexyl
• a branched alkyl radical i.e. a secondary or tertiary alkyl radical
• an isoalkyl radical having the terminal group CH(CH e.g. isobutyl, isopentyl, or (3-methyl-butyl) and isohexyl.
• a sub-class of compounds of this invention includes those keto-esters of Formula I wherein n is 1, R is an alkyl radical having from 4 to 6 carbon atoms, and R is methyl or ethyl.
• Preferred members of this sub-class are the keto-esters wherein R is an alkyl radical having 5 carbon atoms, e.g. methyl Z-n-pentyl-3oXo-cyclopentylacetate, ethyl 2-n-pentyl-3-0X0-cyclopentyl-acetate, methyl Z-isopenty1-3-oxo-cyclopentyl-acetate, and ethyl 2-isopentyl-3- oxo-cyclopentyl acetate.
• a further sub-class of compounds of this invention includes those keto-esters of Formula I wherein n is 2, R is an alkyl radical having from 4 to 6 carbon atoms, and R is methyl or ethyl.
• Preferred members of this sub-class are the keto-esters wherein R is an alkyl radical having 5 carbon atoms, e.g. the methyl and ethyl esters of 2-n-pentyl-3-oXo-cycloheXyl-acetic acid and 2-isopentyl-3-oxo-cycloheXyl-acetic acid.
• the compounds of this invention have two asymmetric carbon atoms in the cycloalkyl ring and can, therefore, exist in two stereoisomeric forms which, however possess substantially the same olfactive properties.
• the keto-esters (represented by Formula I) of this invention can be prepared by condensing a 2-alkyl-2- cycloalkene-l-one wherein the alkyl radical in the 2-position contains from 4 to 6 carbon atoms and the cycloalkyl nucleus has from 5 to 6 members, with a lower alkyl malonate in the presence of a basic condensing catalyst, sa ponifying and decarboxylating the resulting lower alkyl 2-alkyl-3-oXo-cycloalkyl-malonate and esterifying the 2- alkyl-3-oxo-cycloalkyl-acetic acid thus obtained in order to form the desired lower alkyl 2 alkyl-3-oxo-cycloalkylacetate.
• n, R and R have the meaning defined above, and R represents a lower alkyl radical such as methyl and ethyl.
• Part of the starting cycloalkenones used for carrying out this process are known compounds.
• known methods can be used for their preparation, e.g. the methods of PLA. Plattner & A.St. Pfau, Helv. Chim. Acta 20, 1474, (1937); T.M. Jacob, S. Dev, .1. Indian Chem. Soc. 36, 429 (1959); R.L. Frank et al., J. Am. Chem. Soc. 70, 1379 (1948); M.F. Ansell, SS. Brown, J. Chem. Soc. 1958, 2955; M.F. Ansell & J.W. Ducker, J. Chem. Soc. 1959, 329; E.W.
• 2- n-butyl-Z-cyclopentene-l-one, Z-n-hexyl-2-cyclopentene-1- one and 2-(3-methylbutyl)-2-cyclopentene-1-one can be prepared according to the method of Ansell and Ducker (10c. cit.) modified by Rai and Dev (loc.
• 2-n-amyl-2-cyclopentene-l-one can be prepared by cyclodeshydra-ting 'y-decalactone, with polyphosphoric acid according to the method of Pfau &
• Z-n-butyl-Z-cyclo hexene-l-one, 2-n-pentyl-2-cyclo-hexene-l-one, 2-isopentyl-2-cyclohexene-1-one and Z-n-hexyl 2 cyclohexene-lone can be prepared by this method from ethyl E-oxodecanoate, e-oxo-undecanoate, 5-oxo-9-methyl-decanoate and e-oxo-dodecanoate, respectively.
• the ethyl S-oxo- 9-methyl-decanoate is obtained by esterifioation of the corresponding acid which in turn is prepared by condensing isohexyl-methyl-ketone with di-ethyl carbonate in the presence of an alkaline condensing agent, condensing the resulting ethyl ,G-oxo-7-methyl-octanoate with methyl acrylate in the presence of NaOH to form methyl y-carbcthoxy-5-oxo-9-rnethyl-decanoate, and saponifying and decarboxylating the latter in order to obtain the desired 6-oxo-9-methyldecanoic acid.
• the condensation of the starting 2-alkyl-2-cycloalkenel-ones with (ii-lower alkyl malonates, preferably with diethyl malonate, is conveniently carried out in the presence of sodium ethoxide used as the basic condensing catalyst.
• a preferred mode of effecting the condensation consists in adding first the diethyl malonate and then the Z-alhyl- 2-cycloalkene-lone to a solution prepared by dissolving sodium in an excess of absolute ethanol and by refluxing the reaction mixture for a few hours, e.g. for about 3 hours, while agitating.
• the saponification and the decarboxylation of the dilower alkyl 2-alkyl-3-oxo-cycloa. icyl-rnalonate obtained in the first step can be carried out by conventional methods, e.g. by treating the substituted malonate with a mixture of acetic acid and concentrated hydrochloric acid at reflux temperature for several hours, e.g. for about 8 to 14 hours.
• the final esterification of the 2-alkyl-3-oxo-cycloall ylacetic acids obtained in the second step into their methyl or ethyl esters can be effected by conventional methods, e.g. by reacting the substituted acetic acid with diazomethane, if the methyl ester is to be obtained, or by reacting said acid with methanol or ethanol in the presence of an acid catalyst such as concentrated sulfuric acid.
• the keto-esters of this invention possess characteristic odors which care somewhat stronger in the series of the methyl esters than in the series of the ethyl esters.
• the new compounds are valuable fragrance-modifying agents by means of which interesting new notes can be imparted to numerous floral type and fancy type perfume compositions.
• the compounds of this invention can be used for balancing, modifying, enhancing and making more natural the floral note of perfume compositions.
• the notes which can be obtained by the addition of the keto-esters to perfumes are generally of a floral, slightly fatty, mushroom-like and woody type.
• a particular advantage of the new compounds results from the fact that they do not interfere with the desired fragrance ofa given perfume type.
• With the keto-esters of this invention being used in perfume compositions it is furthermore possible to reduce somewhat the proportions of natural flower oils normally used in the preparation of high quality perfumes, without causing any loss in quality.
• keto-esters of the present invention can be used,
• fragrances by using the methyl and ethyl esters of Z-n-amyland 2-isoamyl-3-oxo cyclopentyl-acetic acids and the methyl ester of 2-n-amyl-3-oxo-cyclohexylacetic acid.
• Example 1 1.51 g. of sodium (0.0657 atom) and 100ml. of absolute ethanol are introduced into a three-neclt flask of 500 ml. provided with a stirrer, a reflux condenser and a thermometer, and protected from humidity by means of a calcium chloride tube. Thereafter, 52.5 g. (0.335 mole) of diethyl malonate and then 10 g. (0.0657 mole) of 2-namyl-Z-cyclopentene-l-one (prepared according to P1.
• This substituted malonic ester is saponified and decarboxylated by refluxing it for 14 hours in a mixture of 138 ml. of acetic acid and 209 ml. of concentrated hydrochloric acid. Then the solution is diluted with water and thoroughly extracted with ether. The acid formed as a result of the saponiiication and decarboxylation is then extracted by means of a 5% solution of sodium carbonate.
• the ether extract contains 3.1 g. of a neutral portion consisting substantially of the unsaturated starting ketone.
• the alkaline extract and the washings are acidified by means of H 50, of 10% strength and the acidic portions are extracted with ether. The ethereal extract is washed and dried. After evaporation of the ether there are obtained 7.65 g. of 2-n-amyl-3-oxo-cyclopentyl-acetic acid.
• Example 3 7.29 g. (0.30 gram atom) of magnesium turnings and some iodine granules are placed in a flask equipped for a Grignard reaction. The flask is heated rather strongly in order to dry and activate the magnesium. The metal is covered with anhydrous ether, and a solution of 49.8 g. (0.33 mole) of isoamyl bromide in 75 ml. of the same solvent is introduced. The reaction is completed by re fluxing for 60 minutes.
• Fraction 2 is the desired product, viz. 2-isoamyl-2- cyclopentene-l-one.
• the amount obtained corresponds to a yield of 57% based on the enol ether used for the Grignard reaction. After redistillation this ketone has the following characteristics: a
• Example 5 A solution of g. (0.5 mole) of a-oxo-undecanoic acid in 800 ml. of absolute ethanol is mixed in a 5 literflask With a solution of 220 ml. of pure conc. sulfuric acid in 1400 ml. of absolute ethanol. The resulting solution is refluxed for 3 hours whereupon about 1000 ml. of the ethanol are distilled oil in vacuo. The concentrate is then poured into about 10 liters of cold water. The aqueous reaction mixture is extracted twice with ether and the combined ethereal extracts are washed once with water, six times with 5% sodium bicarbonate solution, three times with 10% sodium carbonate solution, and three times with water.
• the 64 g. of dione obtained in the manner described above are dissolved in 265 ml. of pure absolute chloroform in a one-liter flask equipped with a stirrer, a reflux condenser, a dropping funnel and protected from humidity by means of calcium chloride tubes. 19.3 g. (0.4 eq.) of phosphorus trichloride are introduced into the solution in the course of 5 minutes. The reaction mixture is stirred for a further 3 hours, while refluxing, and then concentrated to dryness in vacuo. The residue is taken up in water, and the solution is extracted twice with ether. The combined ethereal extracts are washed three times with 2% sodium hydroxide solution, twice with saturated sodium chloride solution and once with Water.
• the ethereal solution is first dried over Na SO and then over CaCI
• the ether is distilled off and the residue is then distilled in vacuo.
• a medium fraction (61.561 C./-0.001 mm. Hg.) gives the following data on analysis.
• Example 6 A chypre perfume composition is prepared by blending the ingredients listed below in the proportions set forth:
• keto-ester included in the above formula can also be replaced by one of the other homologues, e.g. methyl or ethyl Z-iso-amyl- 3-oxo'cyclopentyl-acetate. Also mixtures of at least two of the keto-esters of this invention can be added depending on the particular note which is to be imparted to the perfume composition.
• Example 7 A tuberose type of perfume composition is prepared by blending the ingredients listed below in the proportions set forth:
• Example 8 A floral type of perfume composition is prepared by blending the ingredients listed below in the propontions set forth:
• a lower alkyl ester of a 2-alkyl-3-0xo-cycloalkylacetic acid wherein the ester lower alkyl has from 1 to 2 carbon atoms, the alkyl radical in the 2-position has from 4 to 6 carbon atoms, and the cycloalkyl nucleus has from 5 to 6 members.
• tylacetic acid wherein the ester lower alkyl has from 1 to 2 carbon atoms and the alkyl in the 2-position has from 4 to 6 carbon atoms.
• a lower alkyl ester of a 2-alkyl-3-oxo-cyclohexylacetic acid wherein the ester lower alkyl has from 1 to 2 carbon atoms and the alkyl in the 2-position has from 4 to 6 carbon atoms.

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Cited By (16)

Citations (5)

• 1960
  • 1960-02-25 CH CH212160A patent/CH382731A/fr unknown
• 1961
  • 1961-02-24 US US91334A patent/US3158644A/en not_active Expired - Lifetime

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