EP0694605B1 - Cyclischer Diester und Verwendung desselben als Duftstoff - Google Patents

Cyclischer Diester und Verwendung desselben als Duftstoff Download PDF

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Publication number
EP0694605B1
EP0694605B1 EP95107538A EP95107538A EP0694605B1 EP 0694605 B1 EP0694605 B1 EP 0694605B1 EP 95107538 A EP95107538 A EP 95107538A EP 95107538 A EP95107538 A EP 95107538A EP 0694605 B1 EP0694605 B1 EP 0694605B1
Authority
EP
European Patent Office
Prior art keywords
cyclohexanedicarboxylate
diethyl
cis
trans
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95107538A
Other languages
English (en)
French (fr)
Other versions
EP0694605A2 (de
EP0694605A3 (de
Inventor
Wolfgang Klaus Giersch
Peter Fankhauser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Firmenich SA
Original Assignee
Firmenich SA
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Filing date
Publication date
Application filed by Firmenich SA filed Critical Firmenich SA
Publication of EP0694605A2 publication Critical patent/EP0694605A2/de
Publication of EP0694605A3 publication Critical patent/EP0694605A3/de
Application granted granted Critical
Publication of EP0694605B1 publication Critical patent/EP0694605B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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 present invention relates to the field of perfumery. It concerns, in in particular, the use in perfumery of diethyl 1,4-cyclohexanedicarboxylate.
  • the Diethyl 1,4-cyclohexanedicarboxylate indeed has a rare combination of fragrant flowery, fruity type, namely a flowery odor and whose character fruity evokes the smells of strawberry and pear, very ethereal, with a slight pineapple side background. It's a very natural fruit smell and not at all candied-lactonic, also endowed with remarkable tenacity for this type of odor.
  • perfumery has a real lack of light fruity notes, ethereal and also tenacious.
  • Fructone® (2-methyl-1,3-dioxolane-2-acetate ethyl; origin: International Flavors and Fragrances) has a certain tenacity.
  • the only known fruity and tenacious notes at the same time are very food, evoking candied fruit and fruit compote more than the fruity note ethereal released by a fresh fruit. This is particularly the case for fruity lactones, ethyl methyl phenyl glycidate, raspberry ketone.
  • the ethereal fruity notes known in the prior art are very volatile esters such as, for example, acetate hexyl, heptyl, octyl, allyl and ethyl caproate and ethyl butyrate. Unlike the latter, diethyl 1,4-cyclohexanedicarboxylate appears to be very stubborn, as well on wet as on textiles, as shown in the examples presented later.
  • diethyl 1,4-cyclohexanedicarboxylate can be present in two stereoisomeric forms, which have odorous properties distinct from each other, and again from those of their mixtures.
  • cis-1,4-cyclohexanedicarboxylate of diethyl has a more powerful and persistent odor than that of its trans configuration isomer, with a lot of volume, and in which the odorous characteristics typical of the mixture of isomers are best represented cited above.
  • both the two isomers and their mixtures are useful fragrance ingredients.
  • the cis configuration isomer and mixtures containing a quantity preponderant of this isomer are however preferred perfume ingredients according to the invention.
  • Diethyl 1,4-cyclohexanedicarboxylate and its configuration isomers cis or trans can be used in fine perfumery as well as perfumery functional. 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 perfume various items such as soaps, shower or bath gels, shampoos, creams or lotions conditioner, cosmetic preparations or body or air fresheners is also advantageous.
  • the proportions in which the compounds according to the invention can be incorporated in the aforementioned miscellaneous products vary in a range of values very extensive. These values are dependent on the nature of the product to be perfumed and the desired olfactory effect, as well as the nature of the co-ingredients in a composition given, when the compounds of the invention are used in admixture with perfuming co-ingredients, solvents or adjuvants customary in the art. Of course, the compounds according to the invention can also be added to the compositions and scented articles either alone or in solution in commonly used solvents.
  • Diethyl 1,4-cyclohexanedicarboxylate and its isomers are either available on the market, either they can be easily prepared from products available on the market and using conventional reactions.
  • diethyl 1,4-cyclohexanedicarboxylate can be prepared by simple esterification of this acid, using the appropriate alcohol and in the presence of an acid protonic or an acidic resin. This is a perfectly classic reaction, including the conditions are capable of being optimized by a person skilled in the art without others details are required here.
  • this compound can be prepared from the corresponding dimethylated diester derived from benzene, which is commercially available (BASF or HÜLS), using conventional reactions illustrated in the following scheme:
  • the reactions illustrated in this diagram are carried out under conditions conventional, described in detail below.
  • the desired ester is obtained in the form of a mixture of cis and trans configuration isomers. Where appropriate, these isomers can then be separated from said mixture by crystallization from suitable solvents, in which only one of the isomers is soluble.
  • a basic perfume composition was prepared by mixing the following ingredients: Ingredients Parts by weight Essence of synthetic amber 100 Bergamot essence 100 Iralia® 100 Musk ketone 80 50% absolute oak moss 250 Crystal foam 50 Essence of patchouli 70 Orange essence 40 Bourbon vetyver essence 80 Wardia® 80 Total 950
  • composition A 50 parts by weight of diethyl 1,4-cyclohexanedicarboxylate were added to obtain a new composition A, 50 parts by weight of Fructone® to obtain 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 smell 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 were 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).
  • samples 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 had to judge the intensity of the fruity note exhaled over time, by assigning a value included in an increasing scale from 0 to 10.

Landscapes

  • 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)

Claims (5)

  1. Duftzusammensetzung oder parfümierter Artikel, welche(r) 1,4-Cyclohexandicarbonsäurediethylester als Riechstoff enthält.
  2. Duftzusammensetzung oder parfümierter Artikel nach Anspruch 1, dadurch gekennzeichnet, daß der 1,4-Cyclohexandicarbonsäurediethylester die Form seines Isomers mit der cis-Konfiguration oder einer Mischung, welche eine überwiegende Menge des cis-Isomers enthält, aufweist.
  3. Parfüm oder Eau de Toilette, Seife, Dusch- oder Badegel, Shampoo, Creme oder Lotion zur Verwendung nach der Haarwäsche, kosmetisches Präparat, Körper- oder Raumluftdeodorant, Detergens oder Textilweichspüler oder Universalreiniger, welche 1,4-Cyclohexandicarbonsäurediethylester als Riechstoff enthalten.
  4. Verwendung von 1,4-Cyclohexandicarbonsäurediethylester als Riechstoff.
  5. Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß der 1,4-Cyclohexandicarbonsäurediethylester in Form seines Isomers mit der cis-Konfiguration oder einer Mischung, welche eine überwiegende Menge des cis-Isomers enthält, vorliegt.
EP95107538A 1994-07-01 1995-05-18 Cyclischer Diester und Verwendung desselben als Duftstoff Expired - Lifetime EP0694605B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH2103/94 1994-07-01
CH210394 1994-07-01
CH210394 1994-07-01

Publications (3)

Publication Number Publication Date
EP0694605A2 EP0694605A2 (de) 1996-01-31
EP0694605A3 EP0694605A3 (de) 1996-04-24
EP0694605B1 true EP0694605B1 (de) 1999-10-13

Family

ID=4225950

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95107538A Expired - Lifetime EP0694605B1 (de) 1994-07-01 1995-05-18 Cyclischer Diester und Verwendung desselben als Duftstoff

Country Status (4)

Country Link
US (1) US5614486A (de)
EP (1) EP0694605B1 (de)
JP (1) JP3352849B2 (de)
DE (1) DE69512717T2 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997036868A1 (de) * 1996-04-02 1997-10-09 Bayer Aktiengesellschaft Substituierte phenylketoenole als schädlingsbekämpfungsmittel und herbizide
DK1277751T3 (da) 1996-08-05 2007-02-26 Bayer Cropscience Ag 2- og 2,5-substituerede phenylketoenoler
US6187727B1 (en) * 1999-07-12 2001-02-13 Bush Boake Allen, Inc. Fragrance materials
DE10146848A1 (de) * 2001-09-24 2003-04-24 Oxeno Olefinchemie Gmbh Gemisch alicyclischer Polycarbonsäureester mit hohem cis-Anteil
DE10146869A1 (de) * 2001-09-24 2003-04-24 Oxeno Olefinchemie Gmbh Alicyclische Polycarbonsäureestergemische mit hohem trans-Anteil und Verfahren zu deren Herstellung
ES2298319T3 (es) * 2001-12-05 2008-05-16 Firmenich Sa Ester insaturado como ingrediente perfumante.
ES2300520T3 (es) * 2003-05-09 2008-06-16 Basf Se Composiciones cosmeticas que contienen derivados de acido ciclohexanopolicarboxilico.
DE102004029732A1 (de) 2004-06-21 2006-01-19 Basf Ag Hilfsmittel enthaltend Cyclohexanpolycarbonsäurederivate
US7632792B2 (en) * 2007-11-16 2009-12-15 International Flavors & Fragrances Inc. Methyl cyclohexane carboxylates and their use in perfume compositions
US20090312470A1 (en) * 2008-06-11 2009-12-17 Ferro Corporation Asymmetric Cyclic Diester Compounds
KR101099127B1 (ko) * 2008-10-16 2011-12-26 한화케미칼 주식회사 60%이상의 시스 디(ｃ4-ｃ20)알킬 시클로헥산-1,4-디카르복실레이트의 제조방법
US20130149269A1 (en) * 2011-12-12 2013-06-13 Michael G. Monteleone Novel malodor counteractant
EP2793622B1 (de) 2011-12-21 2019-02-27 Merck Patent GmbH Verwendung von cyclohexanolderivaten als antimikrobielle wirkstoffe

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4168248A (en) * 1972-11-13 1979-09-18 Fritzsche Dodge & Olcott Inc. Perfume compositions
JPS52136927A (en) * 1976-05-12 1977-11-16 Asahi Denka Kogyo Kk Perfume composition
DE3400342A1 (de) * 1984-01-07 1985-07-18 Henkel KGaA, 4000 Düsseldorf Verwendung von salicylsaeureestern als riechstoffe, diese enthaltende riechstoffkompositionen, sowie neue salicylsaeureester
DE3816452A1 (de) * 1988-05-13 1989-11-23 Consortium Elektrochem Ind O-methylzimtsaeurephenylethylester, seine herstellung und verwendung als riechstoff
US5112864A (en) * 1991-05-30 1992-05-12 G. D. Searle & Co. PLA2 inhibitors as antiinflammatories

Also Published As

Publication number Publication date
US5614486A (en) 1997-03-25
EP0694605A2 (de) 1996-01-31
EP0694605A3 (de) 1996-04-24
DE69512717T2 (de) 2000-11-16
JPH0848991A (ja) 1996-02-20
JP3352849B2 (ja) 2002-12-03
DE69512717D1 (de) 1999-11-18

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