DE4304467A1 - Hexanol derivatives, their preparation and use - Google Patents

Description

Field of the invention

The invention relates to new hexanol derivatives of the below specified general formula (I), a process for their preparation and their Use as fragrances.

State of the art

Many natural fragrances are completely inadequate in terms of demand available quantity. For example, to obtain 1 kg Rose oil 5000 kg rose petals necessary; the consequences are very strong limited world annual production and a high price. It is therefore clear that the fragrance industry has a constant need for new fragrances with interesting scents has to the range of course available Perfumes and the necessary adjustments to changing mo Dische flavors make and the ever increasing demand odor improvers for everyday products such as cosmetics and to cover cleaning agents.

From the literature it is known that special derivatives of tetrahydro ionols, where the C atoms are in close proximity to the group -CH (OH) - alkyl-substituted, have interesting odor properties (See E.J. Brunke et al., Dragoco Report 1980, 199-203). From be Of particular importance are those derivatives in which the pages chain of the tetrahydroionol terminal is extended by two carbon atoms; these Compound which is 1- (2,6,6-trimethylcyclohexyl) -hexan-3-ol, is u. a. against two patent applications, see DE-OS 28 07 584 (Dragoco) and EP PS 118 817 (Firmenich).  

As a mixture of diastereomers, d. H. as a mixture of its cis and trans iso is 1- (2,6,6-trimethylcyclohexyl) -hexan-3-ol under the trade name drawing "Timberol" known. Its smell is as powdery-woody, anima and its fixing properties are the subject of the above-mentioned. German Patent Application (see K.H. Schulte-Elte et al., Helvetica Chi mica Acta 1985 (68) 1961-1985). However, it has been shown that in "Timberol" only the trans compound has the specified odor name; the cis isomer, on the other hand, has an undefinable flowery note Intensity (see K.H. Schulte-Elte, a.a.O.). It is therefore surprising not that not only the diastereomeric mixture is commercially available, but also the trans isomer itself ("norlimbanol"; K. H. Schulte-Elte, a.a.O.).

The different odor profiles of cis- and trans-1- (2,6,6-trim thylcyclohexyl) -hexan-3-ol are an example of those skilled in the art phenomenon familiar here, that slight changes a certain basic structure strength and odor quality of an olfactory can change drastically.

From the German patent application DE-OS 24 42 024 (BASF AG) are not saturated ketones known by reaction of alpha-ionone or a Me thyl homologues thereof with a vinyl magnesium halide. at this Grignard reaction is introduced into the starting materials a vinyl group. According to the description of DE-OS 24 42 024 have the vinyl-substituted Ketone fragrance properties, which - at least in one component - those of Similar to ketones from which they were made. The other component is described as sweet, dry and "towards" amber.

Description of the invention

From the above-described contexts out becomes clear that gene There is a continuing need for synthetic fragrances which are produce cheap and consistent quality and desirable have olfactory properties, d. H. pleasant, as close to nature as possible have qualitatively new odor profiles of sufficient intensity and are able to anticipate the scent of cosmetic and consumer goods to influence in part. It was therefore searched for compounds that  characteristic, new odor profiles with at the same time high adhesive strength speed, odor intensity and radiance.

It has now been found that the compounds of general formula (I) the meet the above requirements perfectly in every respect and in advantageous as fragrances with different nuanced Ge odoriferous with good adhesion can be used. In this Connection should be noted that the Verbindun invention (I) in their odor profiles also from the above from the Prior art known tetrahydroionol derivatives, which are strong at classifying consideration as structurally related could distinguish in a characteristic way.

The present invention therefore hexanol derivatives of general formula (I)

wherein independently of one another

• the radical R ^{1 is} hydrogen or a methyl group,
• the radicals R ² and R ^{3 are} hydrogen or an alkyl group having 1 to 3 C atoms and
• - The radicals R ⁴ and R ^{5 are} hydrogen or a methyl group and where
• (a) positions C-7 / C-8, C-8 / C-9 or C-8 / C-15 either all by a C-C single bond or one of the positions C-7 / C-8, C-8 / C-9 or C-8 / C-15 linked by a C = C double bond is and
• (b) positions C-4 / C-5 either through a C-C single bond or are linked by a C = C double bond.

In a preferred embodiment of the invention, the radical R ^{1 has} the meaning hydrogen. In a further preferred embodiment, the radicals R ² and R ^{3 have} the meaning of hydrogen, methyl or ethyl, again hydrogen and methyl being particularly preferred.

It has also been found that claimed within the invention The compounds (I) which are particularly valuable in odor are included one of the items C-7 / C-8, C-8 / C-9 or C-8 / C-15 by a C = C double bond is linked. Within this group comes the those compounds (I) of greatest importance, in which additionally the Positions C-4 / C-5 are linked by a C-C single bond, i. H. at where the side chain of the six-membered ring is saturated. As an example for that Called 4- (2,6,6-trimethylcyclohex-1-en-1-yl) -heptan-2-ol whose Ge smell profile as strongly woody, dry, iris, oak moss note described can be.

The preparation of the novel compounds (I) takes place according to known per se Synthetic method of organic chemistry. However, it is particularly preferred a process in which the aldehyde, keto or ester group of Ver Compounds of the general formula (II)

wherein independently of one another

• the radical R ^{1 is} hydrogen or a methyl group,
• the radical R ^{2 is} hydrogen or an alkyl group having 1 to 3 C atoms and
• R ^{3 is} hydrogen, an alkyl group having 1 to 3 C atoms, or an alkoxy group having 1 to 3 C atoms
• - The radicals R ⁴ and R ^{5 are} hydrogen or a methyl group and where
• (a) positions C-7 / C-8, C-8 / C-9 or C-8 / C-15 either all by a C-C single bond or one of the positions C-7 / C-8, C-8 / C-9 or C-8 / C-15 linked by a C = C double bond is and
• (b) positions C-4 / C-5 either through a C-C single bond or are linked by a C = C double bond,

reduced to the alcohol function and, if desired, then the dop Pelbindungen in the positions C-7 / C-8, C-8 / C-9, C-8 / C-15 and / or C-4 / C-5 partially or completely hydrogenated.

The reduction of the aldehyde, keto or ester groups of the compounds (II) to the corresponding alcohol groups of the compounds (I) takes place in a manner known per se with complex hydrides such as sodium borohydride, Li thiumalanate or Vitride® or according to the method of Meerwein-Ponndorf with Aluminum alcoholates.

If desired, in the compounds thus obtained in the Molecule remaining C = C double bonds partially or completely be hydrogenated. It has been found that the hydrogenation of the Positions C-4 / C-5, C-8 / C-9 and C-8 / C-15 connecting C = C double bonds usually under the standard conditions for Hy known to the person skilled in the art is feasible; under standard conditions is ver stand that the compound to be hydrogenated in a solvent at he elevated pressure and elevated temperature and in the presence of a catalyst how Pd / coal is brought into contact with hydrogen. The hydrogenation ei a C = C double bond of the six-membered ring connecting positions C-7 / C-8 on the other hand requires more drastic conditions and / or the application of speci eller hydrogenation catalysts such as those for the hydrogenation of aro matic connections are common. The fact that the C = C double bonds have different affinities to the addition of hydrogen, the invention opens quite he wished way, by choosing the reaction conditions targeted a partial or complete hydrogenation of the existing C = C double bonds perform.  

The compounds of the general formula (II) are present in a simple manner accessible by that Ionone, Irone or their corresponding Alkyl derivatives (depending on the position of the C = C double bond in the six each in their alpha, beta or gamma form) by reducing their carbonyl group with about complex hydrides in the converted corresponding allyl alcohols and this with z. B. enol ethers of Acetal or propionaldehyde or acetone or Orthoessig- or Propionate reacted. In this reaction arises first inter medically an acetal, which after elimination of a molecule alcohol - likewise intermediately - turns into a vinyl allyl ether, which in a [3,3] - sigmatropic rearrangement according to Claisen to the corresponding compound (II) leads. K. C. Brannock has this type of reaction starting from special Allyl alcohols and isobutyraldehyde in J. Am. Chem. Soc. 1959, 81, 3379 be wrote. The reaction of the allyl alcohol with the aldehyde is in the Usually in the presence of a catalytically effective amount of an acid, e.g. B. a sulfonic acid, carboxylic acid or Lewis acid.

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 the general formula (I) as fragrances.

In this case, the compounds (I), in which R ^{3 is} a hydrogen atom, characterized by a resinous odor, which captivates by the beautiful wood and amber notes and has very good fixative properties from application point of view.

In perfume compositions, the compounds (I) enhance harmony and harmony Radiation as well as the adhesion, whereby the dosage under Berück the composition of the remaining parts of the composition aspired scent is tuned.

The odor profiles of the hexanol derivatives (I) were in their complexity and The variety of their shades are unpredictable and are therefore one further confirmation of the general experience that the olfactory Properties of known fragrances no compelling conclusions on the Properties of structurally related compounds, because neither the  Mechanism of fragrance perception nor the influence of chemical structure are adequately researched on the scent perception, therefore, more normal can not be foreseen, whether a changed structure known Fragrances ever leads to the change of the olfactory properties and whether these changes are assessed positively or negatively.

The compounds of the formula (I) are suitable because of their odor profile in particular also for the modification and reinforcement of known composites tions. Particular emphasis should be placed on their extraordinary gifts ruchsstärke, which generally contributes to the refinement of the composition.

The compounds of formula (I) can be with many known Fragrance ingredients, e.g. B. other fragrances natural, synthe tables or partial synthetic origin, essential oils and Pflan combine zene extracts. The range of natural fragrances can Both light and medium and low volatility components and that of the synthetic fragrances representatives from virtually all Include substance classes. Examples are:

• (a) natural products such as tree moss absolute, basil oil, citrus oils such as Bergamot oil, tangerine oil, etc., Galbauum Resin, Mastic Absolute, Myrtle oil, neroli oil, palmarosa oil, patchouli oil, petitgrain oil, Vermouth oil, myrrh oil, olibanum oil,
• (b) alcohols such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, Rhodinol, cinnamyl alcohol, Sandalore [3-methyl-5- (2.2.3-trimethylcyclo pent-3-en-1-yl) pentan-2-ol], Sandela [3-isocamphyl (5) -cyclohexanol],
• (c) aldehydes such as citral, Helional®, α-hexyl cinnamaldehyde, hydroxycitronel lal, Lilial® [p-tert-butyl-α-methyldihydrocinnamaldehyde], methylnonyl acetaldehyde,
• (d) ketones such as allylionone, α-ionone, β-ionone, isoraldein, methylionone,
• (e) esters such as allylphenoxyacetate, benzylsalicylate, cinnamylpropionate, Ci tronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzyl carbinyl acetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, Methyl dihydrojasmonate, vetiveryl acetate, cyclohexyl salicylate
• (f) lactones such as gamma undecalactone, 1-oxaspiro [4.4] nonan-2-one,

as well as various other often used in perfumery components such as Ketone musk, indole, p-menthane-8-thiol-3-one, methyleugenol, ambroxan and Oxyret.

Also noteworthy is the way in which the compounds of structure (I) round off and harmonize the odor notes of a wide range of known compositions without, however, interfering in an uncomfortable manner. Those hexanol derivatives (I) in which both radicals R ² and R ^{4 are} methyl groups are particularly emphasized in this regard.

The compounds of the invention contain chiral centers, so that These compounds can exist in different spatial forms. In the yard men usual syntheses fall the connections according to invention as Ge mix the corresponding isomers and are as such as olfactory used substances. However, it may also be desirable to Diastereomeric mixtures such as chromatographically in its individual components to separate and to use the corresponding isomers as such.

The usable proportions of the compounds of the invention or their Mixtures in fragrance compositions range from 1 to 70 weight percent, based on the total mixture. Mixtures of the invention Compounds (I) as well as compositions of this kind can be used both for perfuming cosmetic products such as lotions, creams, shampoos, soaps, Ointments, powders, aerosols, toothpastes, mouthwashes, deodorants as well alcoholic perfumery (eg Eaux de Cologne, Eaux de Toilette, ex traits). There is also a possibility to use the par fümierung technical products such as detergents and cleaning agents, softening ler and textile treatment or tobacco. For perfuming this ver various products become these the compositions in an olfactory effective amount, in particular in a concentration of 0.05 to 2 Ge percent by weight, based on the total product. These values However, should not represent limits, as the experienced perfumer also achieve effects with even lower concentrations or even with higher doses can build novel complexes.  

The following examples are intended to illustrate the subject matter of the invention and are not meant to be limiting.

Examples 1. Preparation of the precursors for the compounds of the invention Starting material A: alpha-ionol

Procedure: In a 1 l three-necked flask, 19 g of sodium borohydride in 200 ml absolute ethanol and stirring at room temperature 96 g alpha-ionone (Haarmann &Reimer; content of beta-ionone: approx. 4%) cont dropwise dropped. After the decay of the weakly exothermic reaction was refluxed for three hours and then the mixture was allowed to cool calmly.

Work-up: The cooled reaction mixture was concentrated on ammonium chloride cast / ice and extracted with ether. The organic phases were dried over sodium sulfate, filtered and concentrated. The distillation Kugelrohr yielded 77 g of ionol (73% of theory). The purity was determined by gas chromatography to 92.4%.

Characterization: The IR spectrum of the product (film on NaCl) showed absorption bands at 3336 (-OH), 2962, 1451, 1382 and 1364 (geminal dimethyl groups), as well as 1064 (CO) cm ^-1 .

Starting material B: 4- (2,6,6-trimethylcyclohex-1-en-1-yl) -hept-5-en-2-one

This example illustrates the preparation of the compounds of all the general formula (II) by Claisen rearrangement in the course of the implementation of a Allyl alcohol with the enol ether of the acetone.

Procedure: In a stirred autoclave, 291 g (1.5 mol) of beta-ionol (Starting from beta-ionone - analogously as described for starting material A - ago and 122.4 g (1.7 mol) of 2-methoxypropene together with 60 g cyclohexane and 3 g propionic acid for six hours under 10 bar nitrogen. Atmoshäre at 190 ° C (autogenous pressure: 30 bar) heated.  

Work-up: The reaction mixture was allowed to cool, and the mixture was left to cool Autoclave and then distilled off the solvent. The ver residual residue of 325 g was over-distilled on a Vigreux column profiled. At head temperatures of 87-88 ° C / 0.06 mbar, 114.7 g main run (28% of theory, GC purity: 96%).

Characterization: The IR spectrum of the product (film on NaCl) showed absorption bands at 2955, 2926, 2863, 1719 (C = O), 1455, 1361, 1161, and 965 cm ^-1 .

Odor: Cassis note, woody.

Starting material C: 4- (2,6,6-trimethylcyclohex-1-en-yk) -heptan-2-one

This example illustrates the largely selective hydrogenation of C = C double bond of the side chain of the starting material B.

Preparation: 46.8 g (0.2 mol) of the starting material B were dissolved in 100 g of ethanol and with 2.5 g of Pd / C (5% palladium on charcoal) together in one Submitted hydrogenation autoclave. It was 2.5 hours at 80 ° C and 20 bar Hydrogen pressure hydrogenated.

Work-up: For working up, the catalyst was removed from the reaction mixture filtered off, the solvent was removed and the residue of 44.8 g fractionated on a rotating band column in a high vacuum. At head tempera At temperatures of 77-78 ° C / 0.03 mbar, 37.9 g of main run were recovered (67% of the total) Theory; GC purity: 87%).

Characterization: The IR spectrum of the product (film on NaCl) showed absorption bands at 2953, 2927, 2867, 1718 (C = O), 1457, 1364, 1161 cm ^-1 .

Smell: strongly woody, sandalwood, vetiver, Boisambrene forte touch.  

Starting material D: 3- (2,6,6-trimethylcyclohex-1-en-1-yl) - 2-methyl-hex-4-enoate

This example illustrates the preparation of the compounds of all the general formula (II) by Claisen rearrangement in the course of the implementation of a Allyl alcohol with an orthoester in the presence of an acidic catalyst.

Procedure: In a 1 l autoclave, 100 ml of cyclohexane, 77.6 g (0.4 mol) of beta-ionol (which had been prepared starting from beta-ionone, analogous to that described for starting material A), 79 g ( 0.45 mol) of triethyl ortho propionate [structure: C ₂ H ₅ -C (OC ₂ H ₅ ) ₃ ], 3 g of propionic acid and 1 g of 2,6-di-tert-butyl-4-methylphenol (BHT) filled. After rinsing with stick material 5 bar of nitrogen were pressed and the reaction mixture heated to 190 ° C for seven hours; an internal pressure of 18 bar was built up.

Work-up: For work-up, the reaction mixture was allowed to cool and pulled the solvent and the residue was distilled under high vacuum on a 12 cm Vigreux column. The main fraction of 31 g was subsequently added a rotating column further purified.

Characterization: The resulting mixture was found to be a mixture of diastereomers by GC analysis. The boiling point of this mixture was 86-87 ° / 0.05 mbar. The yield was 13 g (15% of theory). The IR spectrum of the product (film on NaCl) showed absorption bands at 2930, 1735 (ester-CO), 1371 and 1337 (gemin dimethyl groups), 1174 and 1162 (OC-OC) cm ^-1 .

Smell: creamy, rum, chocolate, fruit ester, sandal note, green, hol tens.

Educt E: Mixture of 3- (2,6,6-trimethylcyclohex-1-en-1-yl) - 4-methyl-hex-4-enoic acid ethyl ester and other isomers

This example illustrates the preparation of one of the compounds of the general formula (II) by Claisen rearrangement in the course of the reaction  an allyl alcohol with an orthoester in the presence of an acidic Catalyst. As a result, allyl alcohol was a mixture of methylionols used by sodium borohydride reduction of "Isoraldein 70®" he was holding. The "Isoraldein 70®" (Haarmann & Reimer) is involved is a mixture of ketones different from alpha, beta and gamma Derive ionone, the side chain of the latter compounds depending because an additional methyl group in the vicinity of the carbonyl group wearing; Main component of the "Isoraldein 70" should be 3-Me ethyl (2,6,6-trimethylcyclohex-1-en-1-yl) -but-4-en-2-one.

Procedure: In a 1 l autoclave, 100 ml of cyclohexane, 83.2 g (0.4 mol) of a methylionol mixture (starting from "Isoraldein 70®" (Haarmann & Reimer) by reduction with sodium borohydride - analog as described for the preparation of the starting material A) 72.9 g (0.45 mol) of triethyl orthoacetate [structure: CH ₃ -C (OC ₂ H ₅ ) ₃ ], 3 g of propionic acid and 1 g of 2,6- Di-tert-butyl-4-methylphenol (BHT) filled. After purging with nitrogen, 5 bar of nitrogen were pressed in and the reaction mixture heated to 190 ° C for seven hours; In the process, an internal pressure of 10 bar was built up.

Work-up: For work-up, the reaction mixture was allowed to cool and pulled the solvent on a rotary evaporator and distilled the residue in an oil pump vacuum on a 12 cm Vigreux column. There was a head fraction of 49.8 g (45% of theory) at head temperatures of 124-125 ° C / 0.1 mbar.

Characterization: The IR spectrum of the product (film on NaCl) showed absorption bands at 2956, 1737 (ester CO), 1447, 1367, 1324, 1254, 1155 and 1036 cm ^-1 .

Odor: spicy, fruity, creamy, woody, weak.  

2. Preparation of the compounds of the invention Example 1: 4- (2,6,6-Trimethylcyclohex-1-en-1-yl) -heptan-2-ol

This example illustrates the reduction of the carbonyl group of the Starting material C (that is to say a compound of general formula II) by means of a complex hydride to the OH function, wherein a compound of the general Formula I is created.

Execution: In a 1 l three-necked flask, 5.3 g (0.14 mol) of sodium boo ranat suspended in 50 ml of absolute ether and under nitrogen 32.8 g (0.14 mol) of the educt C metered in with stirring. After the complete In addition, the mixture was refluxed for two hours.

Work-up: For workup, the reaction mixture was allowed to cool, She then poured onto an ice / ammonium chloride mixture and ex traded several times with ether. The combined ether phases were over Ma Dried magnesium sulfate, filtered and concentrated on a rotary evaporator. The thus obtained 31.4 g of the colorless product proved gaschroma tographisch as uniform and were again a Kugelrohr Destilla Subjected tion (oven temperature: 150-160 ° C / 0.8 mbar). In this way were 28.7 g (87% of theory) of the product in the form of a colorless oil receive.

Characterization: The IR spectrum of the product (film on NaCl) showed absorption bands at 3352 (-OH), 2955, 2929, 1457, 1375, 1123 cm ^-1 .

Odor: strongly woody, dry, iris, oak moss note.

Example 2: Mixture of 2,4-dimethyl-3- (2,6,6-trimethylcyclohex-1-ene 1-yl) -hex-4-en-1-ol and other isomers

Procedure: 10.5 g of a mixture of 2,4-dimethyl-3- (2,6,6-trimethyl cyclohex-1-en-1-yl) -hex-4-enoic acid ethyl ester and other isomers (Herge represents - analogously as described for starting material E - from "Isoraldein 70" by Reduction with sodium borohydride, followed by reaction with  Triethylorthopropionat) were dissolved in 100 ml of toluene and under stick atmosphere with 20 g of Vitride® (70% in toluene) dropwise under Stirred. The mixture was then refluxed for four hours river heated to boiling.

Work-up: For work-up, the reaction mixture was allowed to cool and pulled the solvent on a rotary evaporator, distilled the residue via Kugelrohr and then fractionated on a 12 cm Vigreux-Ko lonne. It was a main fraction of 9.5 g at head temperatures of 78-80 ° C / 0.06 mbar.

Characterization: The IR spectrum of the product (film on NaCl) showed absorption bands at 3445 (-OH), 2954, 1454, 1377, 1174, 1159 and 1031 cm ^-1 .

Smell: intense woody, amber note.  

composition example

Perfume concentrate for perfuming soap (floral-fresh fantasy composition Shares by weight Bergamot oil 200 isopropyl myristate 150 Sandel synth. 100 geraniol 100 cyclohexyl 80 coumarin 80 benzyl 50 1-acetyl-2,2,4,6-tetramethylcyclohexa-4,6-diene 50 cyclohexadecenones 40 patchouli oil 30 cedarwood 30 tetrahydrogeranylacetone 20 Styrate 10 Evernyl  10 950

Addition of 50 parts of 4- (2,6,6-trimethyl-cyclo-hex-1-en-1-yl) -heptan-2-ol (Example 1) to the mixture reinforced compared to the starting mixture, to which 50 parts of isopropyl myristate were added, the woody aspects in such a way that it increases even in the top note of the composition notice. This wins the formulation of freshness and the blumi Tenderness and harsh nuances emerge clearly, giving the fragrance an elegant look Gives lightness that radiates quite strong but still has a beautiful naturalness.

Claims (12)

1. hexanol derivatives of the general formula (I) wherein independently of one another

• the radical R ^{1 is} hydrogen or a methyl group and
• - The radicals R ² and R ^{3 is} hydrogen or an alkyl group having 1 to 3 carbon atoms and
• - The radicals R ⁴ and R ^{5 are} hydrogen or a methyl group and where
• (a) positions C-7 / C-8, C-8 / C-9 or C-8 / C-15 are either all linked by a C-C single bond or one of the positions C-7 / C-8; C-8 / C-9 or C-8 / C-15 is linked through a C = C double bond and
• (b) positions C-4 / C-5 are linked by either a C-C single bond or a C = C double bond.

2. hexanol derivatives according to claim 1, wherein the radical R ¹ indicates hydrogen be. 3. hexanol derivatives according to claim 1 or 2, wherein the radicals R ² and R ^{3 is} hydrogen, methyl or ethyl. 4. hexanol derivatives according to any one of claims 1 to 3, wherein the radicals R ² and R ^{3 is} hydrogen or methyl. 5. hexanol derivatives according to any one of claims 1 to 4, wherein one of the Po C-7 / C-8, C-8 / C-9 or C-8 / C-15 through a C = C double bond is linked. 6. hexanol derivatives according to claim 5, wherein the positions C-4 / C-5, by a C-C single bond are linked. 7. Process for the preparation of hexanol derivatives of the general formula (I)
wherein independently of one another

• the radical R ^{1 is} hydrogen or a methyl group,
• - The radicals R ² and R ^{3 is} hydrogen or an alkyl group having 1 to 3 carbon atoms and
• - The radicals R ⁴ and R ^{5 are} hydrogen or a methyl group and where
• (a) positions C-7 / C-8, C-8 / C-9 or C-8 / C-15 are either all linked by a C-C single bond or one of the positions C-7 / C-8; C-8 / C-9 or C-8 / C-15 is linked through a C = C double bond and
• (b) positions C-4 / C-5 are linked by either a C-C single bond or a C = C double bond,

characterized in that the aldehyde, keto or ester group of the compounds of the general formula (II) wherein independently of one another

• the radical R ^{1 is} hydrogen or a methyl group,
• the radical R ^{2 is} hydrogen or an alkyl group having 1 to 3 C atoms,
• the radical R ^{3 is} hydrogen, an alkyl group having 1 to 3 C atoms, or an alkoxy group having 1 to 3 C atoms and
• - The radicals R ⁴ and R ^{5 are} hydrogen or a methyl group and where
• (A) one of the positions C-7 / C-8, C-8 / C-9 or C-8 / C-15 is linked by a C = C double bond and
• (b) positions C-4 / C-5 are linked by either a C-C single bond or a C = C double bond,

reduced to the alcohol function, z. By means of a complex hydride, and, if desired, then the double bonds in the Positi Part C or C-7 / C-8, C-8 / C-9, C-8 / C-15 and / or C-4 / C-5 constantly hydrogenated. 8. Use of the hexanol derivatives (I) according to one of claims 1 to 6 as fragrances. 9. perfume compositions containing one or more of Hexanol derivatives of the formula (I) according to claims 1 to 6 in one Amount of 1-70 wt .-%, based on the total composition.   10. Use of one or more compounds of the formula (I) according to any of claims 1 to 6 as fragrances in cosmetic Präpara technical products or alcoholic perfumery.