WO1995030406A1 - Utilisation de 3-phenyl-4-pentenals et de leurs derives comme substances odorantes - Google Patents

Utilisation de 3-phenyl-4-pentenals et de leurs derives comme substances odorantes Download PDF

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Publication number
WO1995030406A1
WO1995030406A1 PCT/EP1995/001573 EP9501573W WO9530406A1 WO 1995030406 A1 WO1995030406 A1 WO 1995030406A1 EP 9501573 W EP9501573 W EP 9501573W WO 9530406 A1 WO9530406 A1 WO 9530406A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
compounds
phenyl
radical
carbon atoms
Prior art date
Application number
PCT/EP1995/001573
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German (de)
English (en)
Inventor
Thomas Markert
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1995030406A1 publication Critical patent/WO1995030406A1/fr

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Classifications

    • 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
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/228—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde
    • C07C47/232—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/213—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C49/217—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • 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

Definitions

  • the invention relates to the use of special aromatic carbonyl compounds of the structure given below as fragrances.
  • fragrance industry has a constant need for new fragrances with interesting fragrance notes in order to supplement the range of naturally available fragrances and to make the necessary adaptations to changing fashionable tastes, as well as the constantly increasing need for odor improvers for everyday products To cover needs such as cosmetics and cleaning agents.
  • the compounds of the general formula (I) meet the above requirements excellently in all respects and can advantageously be used as fragrances with differently nuanced odor notes with good adhesive strength.
  • the compounds of the formula (I) have an improved odor intensity over compounds of the prior art which are structurally close to them, i.e. develop their effect at lower concentrations.
  • the present invention relates to the use of aromatic carbonyl compounds of the general formula (I)
  • radicals R * to R3 independently of one another are hydrogen or an alkyl ring having 1 to 4 carbon atoms,
  • radical R 4 is hydrogen or an alkyl group with 1 to 4 carbon atoms and
  • Ph is a phenyl group
  • fragrances mean as fragrances.
  • the radicals R * have to R3 di e is hydrogen.
  • R 4 is hydrogen, methyl or ethyl.
  • 4-phenylhex-5-en-2-one is very particularly preferred. It is characterized by its floral notes and excellent stability in recipes for cosmetics and perfumery.
  • the compounds (I) are prepared by known synthetic organic chemical methods.
  • the compounds (I) are preferably produced from the corresponding allyl alcohols, for example cinnamon alcohol, by means of the so-called Carroll reaction.
  • Carroll reaction in the context of the present invention means the conversion of allyl alcohols into gam a-delta-unsaturated ketones.
  • the allyl alcohol is converted by reaction with acetoacetic ester into the corresponding allyl acetoacetate, from which the alpha-allylacetoacetic acid is formed by [3,3] sigmatropic storage (Claisen storage) thermal decarboxylation gives the desired gamma-delta unsaturated ketone (I).
  • the allyl acetoacetate can be used in bulk or formed in situ.
  • allyl alcohols are reacted with 2-alkoxyalkenes, in particular 2-methoxy-propene, in the Carroll reaction.
  • 2-alkoxyalkenes in particular 2-methoxy-propene
  • the intermediate allyl vinyl ether can be isolated or subjected directly to the subsequent [3,3] sigmatropic rearrangement to the corresponding ketone (I).
  • the compounds (I) in which R * denotes a group of methyl or hydrogen are distinguished by a floral smell reminiscent of privet and gardenia, which gains intensity through green and cinnamon-like hyacinthic aspects.
  • the compounds (I) enhance the harmony and charisma as well as the adhesion, the dosage being matched to the desired fragrance note taking into account the other constituents of the composition.
  • the compounds of the formula (I) are particularly suitable for modifying and enhancing known compositions.
  • their extraordinary olfactory strength is to be emphasized, which generally contributes to the refinement of the composition.
  • the compounds of formula (I) can be used with numerous known fragrance ingredients, e.g. combine other fragrances of natural, synthetic or partially synthetic origin, essential oils and plant extracts.
  • the range of natural fragrances can include both volatile, medium and low volatile components and that of synthetic fragrances includes representatives from practically all classes of substances. Examples are:
  • Natural products such as tree moss absolute, basil oil, agricultural oils such as bergamot oil, mandarin oil, etc., mastic absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, myrrh oil, olibanum oil
  • aldehydes such as citral, Helional R , ⁇ -hexylcinnamaldehyde, hydroxycitronellal, LilialR [p-tert-butyl-methyldihydrocin
  • ketones such as allyl ionone, o-ionone, ⁇ -ionone, isoraldein, methyl ionone,
  • esters such as allylphenoxyacetate, benzyl salicylate, cinnamylpropionate, citronellylacetate, decyl acetate, dimethylbenzylcarbinylacetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, viethyl acetate, cyclylatyl acetate
  • lactones such as gam a-undecalactone, l-0xaspiro [4.4] nonan-2-one,
  • perfumery such as ketone musk, indole, p-menthan-8-thiol-3-one, methylejgenol, A broxan.
  • the compounds according to the invention contain centers of chirality, so that these compounds can exist in different spatial forms.
  • the compounds according to the invention are obtained as mixtures of the corresponding isomers and are used as such as fragrances.
  • the usable proportions of the compounds according to the invention or their mixtures in fragrance compositions range from 1 to 70 percent by weight, based on the mixture as a whole.
  • Mixtures of the compounds (I) according to the invention and compositions of this type can be used for perfuming cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants as well as in alcoholic perfumery (eg Eaux de Cologne , Eau de toilette, extras) can be used.
  • perfuming technical products such as detergents and cleaning agents, fabric softeners and textile treatment agents or tobacco.
  • compositions are added to them in an olfactory effective amount, in particular in a concentration of 0.05 to 2 percent by weight, based on the entire product.
  • these values are not intended to represent any limit values, since the experienced perfumer can achieve effects with even lower concentrations or build new types of complexes with even higher doses.
  • Cinnamon alcohol 98% (Riedel de Haen) Isopropenyl methyl ether: 2-methoxypropene, 92% (Janssen) Cinnamaldehyde: 98% (Fluka)
  • Smell green, herbaceous, hyacinth, bromostyrene, gardenia, cinnamon, diphenyl oxide, rose
  • the IR spectrum (film on NaCl) shows 9 bands of medium intensity at 3081-2885 cm “ 1 , insofar as further bands at 1718, 1602, 1494, 1452, 1438, 1419, 1358, 1232, 1161, 1074, 1019, 968, 755 and 701 cm-1.
  • Smell green, milky, melted, cinnamon, buttery notes.
  • Smell floral, green, notes of geranium and cinnamon (similar to example 2, but with a lower intensity).
  • the IR spectrum (film on NaCl) shows 6 bands of medium intensity at 3079-2914 cm-1, S0W1 * e further bands ' at 1719, 1646, 1600, 1492, 1451, 1421, 1356, 1234, 1160, 1079, 1026 , 949, 894, 751 and 701 cm-1.
  • Smell floral, rose, geraniu, cinnamon note.
  • Perfume concentrate for perfuming soap (floral-fresh fantasy composition):

Abstract

L'invention concerne des composés carbonyle aromatiques de la formule générale (I) dans laquelle les restes R1 à R3 désignent, indépendamment les uns des autres, hydrogène ou un groupe alkyle ayant entre 1 et 4 atomes de C, le reste R4 désigne hydrogène ou un groupe alkyle ayant entre 1 et 4 atomes de C et pH désigne un groupe phényle. Ces composés se caractérisent en ce qu'ils comportent des notes aromatiques intéressantes à grand pouvoir émissif et qu'ils s'utilisent comme substances odorantes, par ex. dans des préparations cosmétiques, des produits techniques ou dans la parfumerie alcoolisée.
PCT/EP1995/001573 1994-05-04 1995-04-26 Utilisation de 3-phenyl-4-pentenals et de leurs derives comme substances odorantes WO1995030406A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4415690.1 1994-05-04
DE19944415690 DE4415690A1 (de) 1994-05-04 1994-05-04 Aromatische Carbonylverbindungen

Publications (1)

Publication Number Publication Date
WO1995030406A1 true WO1995030406A1 (fr) 1995-11-16

Family

ID=6517258

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/001573 WO1995030406A1 (fr) 1994-05-04 1995-04-26 Utilisation de 3-phenyl-4-pentenals et de leurs derives comme substances odorantes

Country Status (2)

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DE (1) DE4415690A1 (fr)
WO (1) WO1995030406A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010052635A1 (fr) * 2008-11-07 2010-05-14 Firmenich Sa Ingrédients parfumants du type floral et/ou anisé

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19520556A1 (de) * 1995-06-06 1996-12-12 Henkel Kgaa Aromatische Carbonylverbindungen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3793376A (en) * 1970-06-04 1974-02-19 Int Flavors & Fragrances Inc Process for producing 3-phenyl pentenals
US3922237A (en) * 1972-08-01 1975-11-25 Int Flavors & Fragrances Inc Novel perfume compositions and perfumed articles containing di-lower alkyl and lower alkylene acetals of 2-and 3-phenyl pentenals
US3996290A (en) * 1975-06-11 1976-12-07 Givaudan Corporation 2,4-Dimethyl-2-phenyl-4-pentenal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3793376A (en) * 1970-06-04 1974-02-19 Int Flavors & Fragrances Inc Process for producing 3-phenyl pentenals
US3922237A (en) * 1972-08-01 1975-11-25 Int Flavors & Fragrances Inc Novel perfume compositions and perfumed articles containing di-lower alkyl and lower alkylene acetals of 2-and 3-phenyl pentenals
US3996290A (en) * 1975-06-11 1976-12-07 Givaudan Corporation 2,4-Dimethyl-2-phenyl-4-pentenal

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BURGSTAHLER ET AL: "Thermal Rearrangement of Arylmethyl Vinyl Ethers", J. CHEM. SOC., pages 4986 - 4989 *
S.R.WILSON ET AL: "The Ester Enolate Carroll Rearrangement", J. ORG. CHEMISTRY, vol. 49, no. 4, pages 722 - 725 *
W.L.SCHREIBER ET AL: "Flavor Properties of Phenylpentenals", J. AGR. FOOD CHEM., vol. 22, no. 2, pages 269 - 273 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010052635A1 (fr) * 2008-11-07 2010-05-14 Firmenich Sa Ingrédients parfumants du type floral et/ou anisé
US8815792B2 (en) 2008-11-07 2014-08-26 Firmenich Sa Perfuming ingredients of the floral and/or anis type
US9487734B2 (en) 2008-11-07 2016-11-08 Firmenich Sa Perfuming ingredients of the floral and/or anis type

Also Published As

Publication number Publication date
DE4415690A1 (de) 1995-11-09

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