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
  • 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

Definitions

• the compounds of formula (I) have useful odor properties which are quite unexpected in the light of the prior art. They indeed develop fragrant notes of the flowery, fruity type which are particularly precious because of their light and ethereal character, but also very tenacious. It is a rare combination of odorous properties, which is best represented in diethyl 1,4-cyclohexanedicarboxylate, a compound whose use is particularly preferred according to the invention.
• This carboxylate has indeed a flowery smell and whose fruity character evokes the smells of strawberry and pear, very ethereal, with a slight pineapple side in the background. It is a very natural fruit odor and not at all candied-lactonic, also endowed with remarkable tenacity for this type of odor.
• perfumery has a real lack of light, ethereal fruity notes that are also tenacious.
• Fructone® (2-methyl-1,3-dioxolane-2-ethyl acetate; origin: International Flavors and Fragrances) has a certain toughness.
• the only known fruity and tenacious notes at the same time are very food notes, evoking more candied fruits and fruit compote than the ethereal fruity note released by a fresh fruit. This is particularly the case for fruity lactones, ethyl methyl phenyl glycidate and raspberry ketone.
• the ethereal fruity notes known in the prior art are very volatile esters such as, for example, hexyl, heptyl, octyl acetate, allyl and ethyl caproate and butyrate ethyl. Unlike the latter, diethyl 1,4-cyclohexanedicarboxylate appears to be very stubborn, both on a wet cloth and on textiles, as is apparent from the examples presented below.
• Another compound whose use turns out to be very advantageous is ethyl 4- (propanoyloxymethyl) -1-cyclohexanecarboxylate, which has a fruity, slightly woody odor, pronounced of that of the compound of the invention cited above.
• the use according to the invention of the first of these two compounds in particular is also preferred, as is that of dimethyl 1,2-cyclohexanedicarboxylate, which has a fruity, ethereal note, recalling the smell of quince, also slightly minty.
• dimethyl 1,3-cyclohexanedicarboxylate has a particularly light fruity note.
• These odors also contrast with that of their dimethyl 1,4-cyclohexanedicarboxylate isomer, whose fruity character recalls the smell of baked apple.
• the compounds (I) with saturated ring can be in two stereoisomeric forms of formula in which the symbols R1 and Z have the meaning indicated in formula (I).
• these isomers can also have odorous properties which are distinct from one another, and also from those of their mixtures.
• diethyl cis-1,4-cyclohexanedicarboxylate has a more powerful and tenacious odor than that of its trans-configuration isomer, with a lot of volume, and in which are best represented the odorous characteristics typical of the mixture of isomers mentioned above.
• both the two isomers and their mixtures are useful perfuming ingredients.
• the cis configuration isomers and mixtures containing a predominant amount of these isomers are however preferred perfume ingredients according to the invention.
• the compounds (I) and their cis or trans configuration isomers can be used both in fine perfumery and in functional perfumery. They are suitable for the preparation of various perfume compositions, perfume bases and concentrates, as well as perfumes and eau de toilette, to which they impart very natural fruity characters. Their application in the perfuming of various articles such as soaps, shower or bath gels, shampoos, creams or lotions after-shampoo, cosmetic preparations or body or air fresheners is also advantageous.
• the proportions in which the compounds according to the invention can be incorporated into the various products mentioned above vary within a very wide range of values. These values are dependent on the nature of the product which it is desired to flavor and on the desired olfactory effect, as well as on the nature of the co-ingredients in a given composition, when the compound (I) is used in mixture with perfume co-ingredients, solvents or adjuvants customary in art.
• the compounds according to the invention can also be added to the compositions and perfumed articles either alone, or in solution in solvents of current use.
• the compounds of formula (I) are either available on the market, or they can be easily prepared from products available on the market and using conventional reactions.
• the 1,2-, 1,3- and 1,4-cyclohexanedicarboxylic acids being commercially available compounds (from Aldrich, for example)
• the compounds (Ia) can be prepared by simple esterification of these acids, with using suitable alcohols and in the presence of a protonic acid or an acidic resin.
• the compounds (Ia) having identical R1 and R2 groups can be prepared from dimethylated diesters derived from benzene, which are all commercially available (BASF or HÜLS), using conventional reactions illustrated in the following diagram:
• R C2 ⁇ C4 alkyl
• the cis and trans isomers of these diesters can be obtained by esterification of the cis and trans isomers of the corresponding cyclohexanedicarboxylic acid.
• these isomers are commercial products.
• the compounds (Ia) having distinct R1 and R2 groups can be obtained by transesterification of the above-mentioned symmetrical diesters, according to known methods [see, for example, K. Mori et al., Synth. 1973 , 790].
• the products of these transesterification reactions are mixtures of starting symmetric diester and asymmetric diester and these two components are then separated by preparative gas chromatography.
• Step d) of preparation of the alkoxides was carried out as follows: the compound prepared according to step c) was dissolved in a mixture of pyridine and toluene and then added dropwise the appropriate acyl chloride at approximately 40 °. After cooling, poured onto ice, taken up in ether and washed the organic phase with a solution of HCl, NaHCO3 and brine until neutral. It was then purified by distillation.
• a basic perfume composition was prepared by mixing the following ingredients: Ingredients Parts by weight Essence of synthetic amber 100 Bergamot essence 100 Iralia® 1) 100 Musk ketone 80 50% absolute oak moss * 250 Crystal foam 50 Essence of patchouli 70 Orange essence 40 Bourbon vetyver essence 80 Wardia® 2) 80 Total 950 ⁇ * in dipropylene glycol (DIPG) 1) methylionone; origin: Firmenich SA, Geneva, Switzerland 2) pink type composition; origin: Firmenich SA, Geneva, Switzerland
• composition A 50 parts by weight of diethyl 1,4-cyclohexanedicarboxylate to obtain a new composition A, 50 parts by weight of Fructone® to obtain a composition B and 50 parts by weight of undecalactone to obtain a composition C.
• the latter then developed a chypre-like odor recalling the fragrance of the Liste® perfume by Rochas. It had a very powerful and dominant lactonic note, with a nutritional character.
• Composition B had a fruity, elegant odor but whose fruity character disappeared completely after 3 hours from the odor of a wet cloth soaked in this composition.
• the new composition A had an even more elegant odor than that of composition B and less fruity-food than that of composition C.
• its fruity, strawberry, pear character persisted throughout the day.
• a basic perfume composition was prepared using the following ingredients: Ingredients Parts by weight Benzyl acetate 75 Phenylethyl acetate 75 Bergamot essence 50 Citronellol 185 Geraniol 200 Linalol 60 Essence of patchouli 25 Phenethylol 260 Absolute rose 20 Bulgarian rose essence 10 Total 960 ⁇
• composition A diethyl 1,4-cyclohexanedicarboxylate
• composition B Fructone®
• Perfumed detergent samples were prepared from an unscented detergent powder, to which was added 0.1% by weight of diethyl 1,4-cyclohexanedicarboxylate (sample A), Fructone® (sample B), respectively , hexyl acetate (sample C) and allyl caproate (sample D). With these four samples, batches of standard textiles were washed in four washing machines. The four batches of textiles were then evaluated blindly on leaving the machine and after drying, by a panel of expert perfumers, who were to judge the intensity of the note fruity exhaled over time, assigning a value included in an increasing scale from 0 to 10.

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

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• 1995
  • 1995-05-18 DE DE69512717T patent/DE69512717T2/de not_active Expired - Lifetime
  • 1995-05-18 EP EP95107538A patent/EP0694605B1/de not_active Expired - Lifetime
  • 1995-05-23 US US08/448,285 patent/US5614486A/en not_active Expired - Lifetime
  • 1995-06-30 JP JP16659095A patent/JP3352849B2/ja not_active Expired - Lifetime

Non-Patent Citations (3)

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