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WO1994018148A1 - Derives d'hexanol, leur preparation et leur utilisation comme substances odoriferantes - Google Patents

Derives d'hexanol, leur preparation et leur utilisation comme substances odoriferantes Download PDF

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Publication number
WO1994018148A1
WO1994018148A1 PCT/EP1994/000342 EP9400342W WO9418148A1 WO 1994018148 A1 WO1994018148 A1 WO 1994018148A1 EP 9400342 W EP9400342 W EP 9400342W WO 9418148 A1 WO9418148 A1 WO 9418148A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
positions
linked
radicals
double bond
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/EP1994/000342
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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 WO1994018148A1 publication Critical patent/WO1994018148A1/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
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C07C33/14—Alcohols containing rings other than six-membered aromatic rings containing six-membered 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
    • C11B9/0026—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
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to new hexanol derivatives of the general formula (I) specified below, a process for their preparation and their use as fragrances.
  • 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 also differ in their odor profiles in a characteristic manner from the above-mentioned tetrahydroionol derivatives known from the prior art, which could be regarded as structurally related when viewed in a strongly classifying manner .
  • the present invention therefore relates to hexanol derivatives of the general formula (I)
  • radical R 1 is hydrogen or a methyl group
  • radicals R2 and R3 are hydrogen or an alkyl group having 1 to 3 carbon atoms.
  • Ato en and the radicals R 4 and R5 are hydrogen or a methyl group and where
  • the radical R 1 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 the aldehyde, keto or ester group of compounds of the general formula (II)
  • radical R * is hydrogen or a methyl group
  • radical R ⁇ is hydrogen or an alkyl group having 1 to 3 carbon atoms
  • the reduction of the aldehyde, keto or ester groups of the compounds (II) to the corresponding alcohol groups of the compounds (I) is carried out in a manner known per se using complex hydrides such as sodium boranate, lithium alanate or Vitride R or by the method from Meerwein-Ponndorf with aluminum aluminum alcohols.
  • 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 gamma form) can be converted into the corresponding allyl alcohols by reducing their carbonyl group with complex hydrides and reacting them with, for example, enol ethers of acetaldehyde or propionaldehyde or acetone or also orthoacetic or propionic acid esters.
  • the hexanol 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 R ⁇ denotes a hydrogen atom are distinguished by a resinous odor which impresses with the beautiful wood and amber notes and has very good fixative properties from an application point of view.
  • 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. Particularly to be emphasized is their extraordinary olfactory strength, 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 construction moss absolute, basil oil, agricultural oils such as bergamot oil, mandarin oil, etc., galbauum resin, mastic absolute, myrtle oil, neroli oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, myrrh oil, 01ibanum oil
  • aldehydes such as citral, helional R , ⁇ -hexylcinnamaldehyde, hydroxycitronellal, lilial R [p-tert-butyl- ⁇ -methyldihydrocentraldehyde], methylnonyl acetaldehyde,
  • ketones such as allyl ionone, ⁇ -ionone, ⁇ -ionone, isoraldein, methyl ionone,
  • esters such as allylphenoxyacetate, benzyl salicylate, cinnamylpropio ⁇ at, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzylcarbinylacetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrohexyl acetate, viethyl acetate
  • lactones such as gamma-undecalactone, l-0xaspiro [4.4] nonan-2-one, as well as various other components often used in perfumery such as ketone musk, indole, p-menthan-8-thiol-3-one, methyleugenol, ambroxan and oxyret.
  • 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.
  • the following examples are intended to explain the subject matter of the invention and are not to be interpreted as restrictive.
  • This example illustrates the preparation of the compounds of the general formula (II) 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 of the general formula (II) by Claisen rearrangement in the course of the reaction of an allyl alcohol with an orthoester in the presence of an acidic catalyst.
  • Smell creamy, rum, chocolate, fruit ester, Sande1 note, green, woody.
  • This example illustrates the preparation of one of the compounds of the general formula (II) by Claisen rearrangement in the course of the reaction of an 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 reducing the sodium boranate of "Isoraldein 70 R ".
  • the "Isoraldein 70 R” (from Haarmann & Reimer) is a mixture of ketones derived from alpha-, beta- and garnma-ionone, the side chains of the latter compounds each having an additional methyl group in the vicinity contributes to the carbonyl group;
  • the main component of "Isoraldein 70” is likely to be 3-methyl- (2,6,6-trimethylcyclohex-1-en-1-yl) -but-4-en-2-one.
  • This example illustrates the reduction of the carbonyl group of the starting material C (i.e. a compound of the general formula II) by means of a complex hydride to the OH function, whereby a compound of the general formula I is formed.

Landscapes

  • 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)

Abstract

Des dérivés d'hexanol 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 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/EP1994/000342 1993-02-15 1994-02-07 Derives d'hexanol, leur preparation et leur utilisation comme substances odoriferantes Ceased WO1994018148A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4304467.0 1993-02-15
DE4304467A DE4304467A1 (de) 1993-02-15 1993-02-15 Hexanol-Derivate, deren Herstellung und Verwendung

Publications (1)

Publication Number Publication Date
WO1994018148A1 true WO1994018148A1 (fr) 1994-08-18

Family

ID=6480454

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/000342 Ceased WO1994018148A1 (fr) 1993-02-15 1994-02-07 Derives d'hexanol, leur preparation et leur utilisation comme substances odoriferantes

Country Status (2)

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DE (1) DE4304467A1 (fr)
WO (1) WO1994018148A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19521364A1 (de) * 1995-06-12 1996-12-19 Henkel Kgaa Cyclohexyl-substituierte Alkanole

Citations (4)

* 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
EP0118817A1 (fr) * 1983-03-11 1984-09-19 Firmenich Sa Procédé pour la préparation d'une composition d'isomères de (triméthyl-2,6,6-cyclohexyl)-1-hexanol-3, utilisation de la composition obtenue et carbinols intermédiaires
EP0121828A2 (fr) * 1983-04-12 1984-10-17 Firmenich Sa Alcools aliphatiques, leur préparation et leur utilisation à titre d'ingrédients parfumants
EP0457022A1 (fr) * 1990-05-16 1991-11-21 Firmenich Sa Alcools aliphatiques optiquement actifs nouveaux et leur utilisation à titre d'ingrédients parfumants

Patent Citations (4)

* 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
EP0118817A1 (fr) * 1983-03-11 1984-09-19 Firmenich Sa Procédé pour la préparation d'une composition d'isomères de (triméthyl-2,6,6-cyclohexyl)-1-hexanol-3, utilisation de la composition obtenue et carbinols intermédiaires
EP0121828A2 (fr) * 1983-04-12 1984-10-17 Firmenich Sa Alcools aliphatiques, leur préparation et leur utilisation à titre d'ingrédients parfumants
EP0457022A1 (fr) * 1990-05-16 1991-11-21 Firmenich Sa Alcools aliphatiques optiquement actifs nouveaux et leur utilisation à titre d'ingrédients parfumants

Also Published As

Publication number Publication date
DE4304467A1 (de) 1994-08-18

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