US3729430A - Perfume compositions - Google Patents

Perfume compositions Download PDF

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Publication number
US3729430A
US3729430A US00196221A US3729430DA US3729430A US 3729430 A US3729430 A US 3729430A US 00196221 A US00196221 A US 00196221A US 3729430D A US3729430D A US 3729430DA US 3729430 A US3729430 A US 3729430A
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United States
Prior art keywords
methyl
chlororesorcylate
ethyl
perfume
reaction
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Expired - Lifetime
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US00196221A
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English (en)
Inventor
J Grossman
K Light
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International Flavors and Fragrances Inc
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International Flavors and Fragrances Inc
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/88—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with esterified carboxyl groups
    • 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

Definitions

  • Natural oakmoss is commercially important in producing high-grade fragrance compositions. Oakmoss constitutes an important and basic part of the fragrance impression of chypre and lavender. In view of the limited availability of natural oakmoss synthetic substitutes are desirable and have been long sought.
  • alkyl ring-substituted resorcylic acid esters simulate and resemble the fragrance impression of oakmoss. While a number of routes for the production of such resorcylic acid esters are available, they are rather tedious, complicated, generally uneco- THE INVENTION
  • the invention is thus related to alkyl 3-chloro ring-substituted resorcylic acid esters, their mode of preparation. and their use as fragrance materials.
  • novel 3-chloro ring-substituted resorcylic acid esters of this invention may be represented by the following formula:
  • R and either R or R is a lower alkyl radical containing from 1 to 5 carbon atoms, the other of R or R 7 being hydrogen.
  • Neelakantan et al. Indian J. Chem, 2(12), 478-84 shows the chlorination of methyl 6-methylresorcylate to yield methyl 6-methyl-3,5- dichlororesorcylate.
  • Neelakantan et al. did not show production of the alkyl 3-chloro ring-substituted resorcyclic acid esters with only one chlorine atom substituted at the 3 position on the benzene ring.
  • the resorcylic acid esters of this invention effectively simulate and resemble oakmoss fragrance and are suitable for use by themselves as fragrance materials or in combination with other ingredients in a perfume composition such as a hypre or lavender perfume.
  • the C-1 and C-2. lower alkyl resorcylic esters are preferred as fragrance materials and the methyl esters are most suitable. Particularly preferred is methyl 6-methyl-3-chlororesorcylate by reason of its pronounced and long lasting mousse-like odor.
  • monoalkyl 3-chloro ring-substituted resorcylic acid esters thereof as represented by the formula wherein R and either of R or R is a lower alkyl radical containing from 1 to 5 carbon atoms (and the other of R or R is hydrogen) can be conveniently and more economically prepared by reacting a mono-ring-substituted dihydroresorcylate ester with an oxidative chlorine material. This process has been found to result in high yields of the products desired and suppresses undesirable side reactions.
  • Suitable mono-ring-substituted dihydroresorcylic acid esters for this reaction may be represented by the following formulae:
  • R and either of R or R is a lower alkyl radical containing from 1 to 5 carbon atoms including methyl, ethyl, propyl, butyl, isopropyl and amyl. Mixtures of such isomers can be used.
  • the particular starting material selected will depend upon the end product desired and appropriate choices will be readily apparent.
  • the dihydroresorcylate starting material is preferably substantially pure so as to avoid undesirable side reactions and facilitate isolation and recovery of the end product.
  • Such dihydroresorcylic acid ester starting materials may be prepared by any of the known techniques.
  • such 4 dihydroresorcylic acid esters can be readily made by reacting a beta-keto alkanoic acid ester of the formula in the presence of an alkali metal alcoholate such as sodium methylate.
  • R and R are each lower alkyl and either of R or R is lower alkyl, the other being hydrogen.
  • the oxidative chlorine material may be molecular chlorine or'any material which, under the conditions of the reaction, yields or is a source of oxidative chlorine such as hypochlorous acid, sulfuryl chloride or nitrosyl chloride. Chlorine is preferred.
  • the yield obtained when practicing the process of this invention is affected by the degree of contact of the reactants.
  • the contact time of the oxidative chlorine material with the hydroresorcylic acid ester is too low, the yields are lower and large amounts of unreacted hydroresorcylic acid ester remains unconverted and must be separated from the reaction mixture.
  • Inter mixing of the reactants as by agitation or turbulent mixing will increase the contact time and increase the yield of desired product.
  • a two phase aqueous-non-aqueous reaction system results where the degree of contact between the two phases is an important if not controlling factor in determining the yield of product.
  • the degree of contact is modified or regulated by nature of the agitation or intermixing.
  • Suitable inert reaction solvents include non-reactive halogenated hydrocarbons such as chloroform and tetrachloroethane and non-reactive alkanoic acids such as acetic and propionic acids.
  • reaction conditions of temperature and pressure are critical and will depend upon a variety of factors including the time of the reaction, the particular reactants used, and the products desired. Generally, it is expedient to run the reaction at atmospheric pressure although elevated pressures may be employed. The reaction must be conducted in the range from about -20 to +50 C. and preferably in the range of from about 10- 25 C.
  • the time of reaction is generally determined by the temperature of the reaction and by the absolute pressure above the reaction mass. Other factors such as the nature of the reactants, the extent and duration of contact of the reactants, the mixing system utilized, and the yield and conversions desired may also affect the reaction time. It is usually preferred to carry out the reaction for a period of time from about one to ten hours since shorter periods adversely affect yields while longer periods give no further advantage in the process.
  • the process is suitably carried out by dissolving or suspending the hydro-resorcylic acid ester in an inert organic vehicle such as chloroform or acetic acid whereby a two phase slurry of solid and saturated solution is formed.
  • an inert organic vehicle such as chloroform or acetic acid
  • the oxidative chlorine material as for example chlorine gas
  • the organic solvent or vehicle is then removed from the reaction mass, the reactants separated .and the reaction product may be recovered and isolated by any conventional technique such as selective extraction, crystallization or the like.
  • the monoalkyl-3-chlororesorcylic acid esters obtained by practicing the process of this invention are novel and are useful fragrance materials. Used individually or in admixture with one another, the monoalkyl-3-chloro resorcylic acid esters of this invention have pronounced oakmoss fragrances and are suitable for use as fragrance materials themselves or as components of fragrance compositions or of perfume compositions. Thus, materials produced by the process of this invention are useful as olfactory agents and fragrances.
  • perfume composition is used herein to mean a mixture of compounds, including perfume adjuvants, for example natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, esters, lactones, ethers, anthranilates, acetals, ketals, oximes, carboxylic acids, aromatic hydroxy compounds, diphenyl compounds, azoles, quinolines, terpenes, the macrocyclic musks including ketones, and polycyclic musks including Tetralin musks; and in addition, frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant and desired fragrance.
  • perfume adjuvants for example natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, esters, lactones, ethers, anthranilates, acetals, ketals, oximes, carboxylic acids, aromatic hydroxy compounds, diphenyl compounds, azoles, quinolines, terpenes
  • Such perfume compositions usually contain: (a) the main note (the bouquet or foundation-stone) of the composition; (b) modifiers which round off and accompany the main note; fixatives including odorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation; and (d) top-notes which are usually low-boiling fresh-smelling materials.
  • Such perfume compositions or the novel monoal-kyl-3-chloro-resorcylic acid esters of this invention can be used in conjunction with carriers, vehicles, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants, fixatives, and the like.
  • perfume compositions the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition can be more than the sum of the effect of each ingredient.
  • the individual compounds of this invention, or mixtures thereof may be used to alter the aroma characteristics of a perfume composition, for example, by high-lighting or moderating the olfactory contribution of another ingredient of the composition.
  • perfume compositions containing as little as 0.5% by weight of the compound of the invention, or even less, can be used to impart a basic oakrnoss note to such materials as crepe de chene, lavender, or chypre for use in soaps, cosmetics, lotions, handkerchief perfumes and similar products.
  • the amount employed will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.
  • compositions of matter disclosed herein can be used alone, in a fragrance-modifying composition, or in a perfume composition as olfactory components in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil and bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, and sun screens; powders such as talcs, dusting powders, and face powders; and the like.
  • the product is a White crystalline material having a mousse-like odor which can be imparted to soap at a level of 0.25%.
  • Chlorine gas is added while stirring the reaction mass over a period of one hour until the chlorine is no longer taken up and the reaction mass becomes clear. During the bubbling the reaction mass temperature increases from 22 C. to 37 C. At the end of the reaction, the hydrogen chloride gas ceases to evolve.
  • the solid material is recovered by filtration and weighs 507.1 grams. It is dissolved in 2 liters diethyl ether. The diethyl ether solution is washed using sodium bicarbonate washes until CO no longer evolves in the wash solution. The bicarbonate solutions are extracted with ether and the ether layers combined and washed with 10 volumes of sodium hydroxide at C. The methyl 6-methylchlororesorcylate product is recovered by crystallization from the ether layers.
  • the structure of the product is shown to be methyl 6-methyl-3-chlororesorcylate by IR, NMR and mass spectral analysis.
  • the product is a white crystalline material having a melting point of 135.8l37.8 C. This material has a mousse-like odor Methyl 6 methyl 3-chlororesorcylate (produced by the process of Example III) 50 Musk xylene 50 Styrax resin 100
  • the foregoing perfume formulation is an important part of chypre essence.
  • the methyl 6-methyl-3-chlororesorcylate is used as a replacement for oakmoss. This perfume is incorporated into a soap perfume at the 0.1% level.
  • the methyl 6-methyl-3-chlororesorcylate gives to this fragrance a natural and distinctly oakmoss note.
  • EXAMPLE V Ethyl 6-ethyl-3-chlororesorcylate Into a 5 liter flask equipped with stirrer, thermometer, and condenser gas inlet tube and bubbler are placed the following materals:
  • Chlorine gas is added while stirring the reaction mass over a period of one hour until the chlorine is no longer taken up and the reaction mass becomes clear. During the bubbling the reaction mass temperature increases from 22 C. up to 42 C. At the end of the reaction, the hydrogen chloride gas ceases to evolve. The solid material is recovered by filtration and Weighs 450 grams. It is dissolved in 2 liters of diethyl ether. The diethyl ether solution is Washed using sodium bicarbonate washes until CO no longer evolves in the wash solution. The bicarbonate solutions are extracted with ether and the ether layers combined and washed with 10 volumes of sodium hydroxide at 5 C.
  • the ethyl 6-ethyl-3-chlororesorcylate product is recovered by crystallization from the ether layers. 150 grams of dried product is obtained. The structure of the product is shown to be ethyl 6-ethyl-3-chlo-roresorcylate by IR, NMR and mass spectral analysis. The product is a white crystalline material. This material has a mousse-like odor which can be imparted to soap at a level of 8 EXAMPLE VI Perfume composition The following mixture is prepared:
  • the foregoing perfume formulation is an important part of chypre essence.
  • the ethyl 6-ethyl-3-chlororesorcylate is used as a replacement for oakmoss. This perfume is incorporated into a soap perfume at the 0.1% level.
  • the ethyl 6-ethyl-3-chlororesorcylate gives to this fragrance a natural and distinctly oakmoss note.
  • reaction mass While maintaining the reaction mass at 15 C., 35 gms. of chlorine gas is added over a period of /2 hour. The reaction mass is then heated to 60 C. and maintained at that temperature for a period of /2 hour. As the reaction mass clears, a precipitate is formed which precipitate is separated by means of filtration.
  • the product of reaction is found to be a mixture of 2 compounds:
  • the desired product has an excellent mousse aroma.
  • the product has a mousse-like odor which can be imparted to soap at a level of 1.50%.
  • the foregoing perfume formulation is an important part of chypre essence.
  • the methyl 5-methyl-3-chlororesorcylate is used as a replacement for oakmoss. This 1 0 perfume is incorporated into a soap perfume at the 0.2% level.
  • the methyl 5-methyl-3-chlororesorcylate gives to this fragrance a natural and distinctly oakmoss note.
  • the 3-chloro-6-methyl resorcylic acid methyl ester acts as a replacement for natural oakmoss without the disadvantage of discoloration that is caused by use of the natural oakmoss in such crepe de chene formulations.
  • This crepe de chene perfume formulation is incorporated in a standard soap base at a level of 1% thus imparting the crepe de chene fragrance to the soap without causing discoloration.
  • a perfume composition comprising a monoalkyl-3- chloro-resorcylic acid ester having the formula HO OH wherein R is lower alkyl and either of R or R is a lower alkyl radical containing from 1-5 carbon atoms and the other of R or R is hydrogen and at least one perfume adjuvant, said monoalkyl-3-chloro-resorcylic acid ester being present in amounts sufficient to alter the fragrance of said adjuvant.
  • composition of claim 1 wherein each of R and R is methyl and R is hydrogen.
  • composition of claim 1 wherein R is methyl
  • R is ethyl and R is hydrogen.

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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)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
US00196221A 1971-02-03 1971-11-05 Perfume compositions Expired - Lifetime US3729430A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11369971A 1971-02-03 1971-02-03
US19622171A 1971-11-05 1971-11-05

Publications (1)

Publication Number Publication Date
US3729430A true US3729430A (en) 1973-04-24

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US00196221A Expired - Lifetime US3729430A (en) 1971-02-03 1971-11-05 Perfume compositions

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US (1) US3729430A (enExample)
JP (1) JPS5327257B1 (enExample)
AU (1) AU453527B2 (enExample)
BE (1) BE778794A (enExample)
CA (1) CA931160A (enExample)
CH (1) CH553743A (enExample)
FR (1) FR2124323B1 (enExample)
GB (1) GB1328475A (enExample)
IT (1) IT949702B (enExample)
NL (1) NL149782B (enExample)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5686406A (en) * 1994-06-24 1997-11-11 Rhone-Poulenc Chimie Vanillic acid ester perfuming agents

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5686406A (en) * 1994-06-24 1997-11-11 Rhone-Poulenc Chimie Vanillic acid ester perfuming agents

Also Published As

Publication number Publication date
BE778794A (fr) 1972-08-01
CH553743A (fr) 1974-09-13
JPS5327257B1 (enExample) 1978-08-07
DE2162557A1 (de) 1972-08-10
FR2124323B1 (enExample) 1977-12-23
IT949702B (it) 1973-06-11
CA931160A (en) 1973-07-31
NL7201325A (enExample) 1972-08-07
FR2124323A1 (enExample) 1972-09-22
GB1328475A (en) 1973-08-30
AU453527B2 (en) 1974-10-03
DE2162557B2 (de) 1975-07-24
AU3700171A (en) 1973-09-27
NL149782B (nl) 1976-06-15

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