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WO1994018150A1 - Derives d'hexanone, leur preparation et leur utilisation - Google Patents

Derives d'hexanone, leur preparation et leur utilisation Download PDF

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Publication number
WO1994018150A1
WO1994018150A1 PCT/EP1994/000343 EP9400343W WO9418150A1 WO 1994018150 A1 WO1994018150 A1 WO 1994018150A1 EP 9400343 W EP9400343 W EP 9400343W WO 9418150 A1 WO9418150 A1 WO 9418150A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
hexanone
positions
linked
derivatives
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.)
Ceased
Application number
PCT/EP1994/000343
Other languages
German (de)
English (en)
Inventor
Thomas Markert
Theo Ten Pierik
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1994018150A1 publication Critical patent/WO1994018150A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/20—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by carboxyl groups or halides, anhydrides, or (thio)esters thereof
    • 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
    • C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • C07C49/21—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/608—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a ring other than a six-membered aromatic ring in the acid moiety
    • 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
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to new hexanone derivatives of the general formula (I) specified below, a process for their preparation and their use 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.
  • German patent application DE-OS 2442024 (BASF AG) discloses unsaturated ketones which are obtained by reacting alpha-ionone or a methyl homologue thereof with a vinyl magnesium halide. In this Grignard reaction, a vinyl group is introduced into the starting materials. According to the description of DE-OS 2442024, the vinyl-substituted ketones have fragrance properties which - at least in one component - are similar to those of the ketones from which they were produced. The other component is described as sweet, dry and "towards" amber.
  • 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 (I) according to the invention differ in their odor profiles in a more characteristic manner from the above-mentioned tetrahydroionol derivatives known from the prior art, which could be regarded as structurally related in a strongly classifying view Differentiate way.
  • the present invention therefore relates to hexanone derivatives of the general formula (I)
  • radical R * is hydrogen or a methyl group
  • radical R2 is hydrogen or an alkyl group with 1 to 3 C atoms
  • radical R3 is hydrogen, an alkyl group with 1 to 3 C atoms or an alkoxy group with 1 to 3 C atoms Atoms
  • radicals R ⁇ and R5 are hydrogen or a methyl group
  • the radical R * is hydrogen.
  • the radicals R2 and R3 are hydrogen, methyl or ethyl, hydrogen and methyl again being very particularly preferred.
  • the new compounds (I) are prepared by conventional synthetic methods of organic chemistry. However, a process is particularly preferred in which allyl alcohols of the general formula (II)
  • KC Brannock developed this type of reaction based on special allyl alcohols and isobutyraldehyde in J.Am.Chem.Soc. 1959, 81, 3379.
  • the reaction of the allyl alcohol with the aldehyde is generally carried out in the presence of a catalytically effective amount of an acid, for example a sulfonic acid, carboxylic acid or Lewis acid.
  • the compounds of the general formula (II) can be obtained in a simple manner by adding ionones, irones or their corresponding alkyl derivatives (which, depending on the position of the C CC double bond in the six-membered ring, in their alpha-, beta- or may be in the a-form) by reduction of their carbonyl group with approximately complex hydrides into the corresponding allyl alcohols.
  • the hexanone derivatives (I) according to the invention have remarkable odor properties.
  • Another object of the invention is therefore the use of the compounds of general formula (I) as fragrances.
  • the compounds (I) in which R3 denotes a methyl group are distinguished by a woody odor which, due to its strong notes of sardwood and vetiver, stands out from the large number of natural and synthetic wood notes available to the perfumer.
  • 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 very strong power to fix volatile fragrances should be emphasized, which generally contributes to the refinement of the composition.
  • the compounds of formula (I) can be combined with numerous known fragrance ingredients, for example other fragrances of natural, synthetic or partially synthetic origin, essential oils and plant extracts.
  • the range of natural fragrances can include both volatile and moderately volatile components and that of synthetic fragrances include representatives from practically all classes of substances. Examples are:
  • Natural products such as tree moss absolute, basil oil, bay oil, agricultural oils such as berga ott oil, mandarin oil, etc., Elemi resin, mastic absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, myrrh oil, olibanum oil
  • aldehydes such as citral, HelionalR, ⁇ -hexylcinnamaldehyde, hydroxycitronellal, Lilial R [p-tert-butyl- ⁇ -methyldihydrocinnamaldehyde], methylnonyl acetaldehyde,
  • ketones such as allyl ionone, ⁇ -ionone, ⁇ -ionone, isoraldein, methyl ionone,
  • esters such as allylphenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzylcarbyl acetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasate acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vyliveryl acetate, vetyl acetate,
  • lactones such as gam a-undecalactone, l-0xaspiro [4.4] nonan-2-one, as well as various other components often used in perfumes * e, such as ketone musk, indole, p-menthan-8-thiol-3-one, Methyleugeno1, Ambroxan.
  • 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.
  • 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.
  • the 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 should not represent any limit values, since the experienced perfume can achieve effects with even lower concentrations or can build up new complexes with even higher doses.
  • Example 1 4- (2 f 6 f 6-trimethylcyclohex-l-en-l-yl) -hept-5-en-2-one
  • This example illustrates the preparation of the compounds (I) according to the invention by Claisen rearrangement in the course of the reaction of an allyl alcohol with the enol ether of acetone.
  • This example illustrates the preparation of the compounds (I) according to the invention by Claisen storage in the course of the reaction of an allyl alcohol with an orthoester in the presence of an acid catalyst.
  • Smell creamy, rum, chocolate, fruit ester, sandal notes, green, woody.
  • This example illustrates the preparation of the compounds (I) according to the invention by Claisen rearrangement in the course of the implementation of a Allyl alcohol with an orthoester in the presence of an acid catalyst.
  • a mixture of methylionols was used as the allyl alcohol, which was obtained by sodium boranate reduction of "Isoraldein 70 R ".
  • the "Isoraldein 70 R” (from Haarmann & Reimer) is a mixture of ketones derived from alpha, beta and gam a ionone, the side chain of the latter compounds each having an additional methyl group in the vicinity of the Carries carbonyl group;
  • the main component of the “isoraldein 70” is likely to be 3-methyl- (2,6,6-trimethylcyclohex-l-en-l-yl) -but-4-en-2-one.

Landscapes

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

Abstract

Des dérivés d'hexanone ont la formule générale (I), dans laquelle, indépendamment les uns des autres, le reste R1 désigne hydrogène ou un groupe méthyle, les restes R2 et R3 désignent hydrogène ou un groupe alkyle ayant 1 à 3 atomes de carbone, le reste R3 désigne hydrogène, un groupe alkyle ayant 1 à 3 atomes de carbone ou un groupe alcoxy ayant 1 à 3 atomes de carbone, et les restes R4 et R5 désignent hydrogène ou un groupe méthyle. En outre: a) les positions C-7/C-8, C-8/C-9 ou C-8/C-15 sont toutes reliées par une liaison simple C-C ou une des positions C-7/C-8, C-8/C-9 ou C-8/C-15 est reliée par une liaison double C=C, et b) les positions C-4/C-5 sont reliées soit par une liaison simple C-C soit par une liaison double C=C. Ces composés constituent des substances odoriférantes aux notes intéressantes, qui ont un large spectre de diffusion.
PCT/EP1994/000343 1993-02-15 1994-02-07 Derives d'hexanone, leur preparation et leur utilisation Ceased WO1994018150A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4304466A DE4304466A1 (de) 1993-02-15 1993-02-15 Hexanon-Derivate, deren Herstellung und Verwendung
DEP4304466.2 1993-02-15

Publications (1)

Publication Number Publication Date
WO1994018150A1 true WO1994018150A1 (fr) 1994-08-18

Family

ID=6480453

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/000343 Ceased WO1994018150A1 (fr) 1993-02-15 1994-02-07 Derives d'hexanone, leur preparation et leur utilisation

Country Status (2)

Country Link
DE (1) DE4304466A1 (fr)
WO (1) WO1994018150A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2442024A1 (de) * 1974-09-03 1976-03-25 Basf Ag Neue riechstoffe
US4868339A (en) * 1987-09-23 1989-09-19 Basf K & F Corporation Alkyltetramethylcyclohexane derivatives and their use as perfumes
EP0464357A2 (fr) * 1990-06-02 1992-01-08 Givaudan-Roure (International) S.A. Composés bicycliques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2442024A1 (de) * 1974-09-03 1976-03-25 Basf Ag Neue riechstoffe
US4868339A (en) * 1987-09-23 1989-09-19 Basf K & F Corporation Alkyltetramethylcyclohexane derivatives and their use as perfumes
EP0464357A2 (fr) * 1990-06-02 1992-01-08 Givaudan-Roure (International) S.A. Composés bicycliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BRUCE H. LIPSHUTZ ET AL.: "Carboalumination/Transmetalation/Conjugate Addition: A New Catalytic Cu(I)-Induced Process for the 1,4-Delivery of Vinylic Groups to Enones", J. ORG. CHEM., vol. 56, 1991 *

Also Published As

Publication number Publication date
DE4304466A1 (de) 1994-08-18

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