WO2005012222A1 - Alicyclic ester with musk fragrance - Google Patents

Abstract

A compound of formula (I) or (II) is disclosed, whereby, in formulas (I) and (II), R<1> = an optionally-substituted (a) branched or unbranched C1 to C5 alkyl, or (b) branched or unbranched C2 to C5 alkylene, or (c) C3 to C5 cycloalkyl and in formula (II) the bond represented by a dotted line may be either a single- or a double-bond.

Description

 Alicyclic esters with a musky smell

The present invention relates to (a) new alicyclic esters, (b) mixtures which comprise an alicyclic ester according to the invention, (c) the use of the alicyclic esters according to the invention or the mixtures according to the invention as fragrance, (d) processes for producing, amplifying or modifying them a musk smell in a mixture, (e) fragrance mixtures with a musk smell, (f) perfumed products and (g) a process for producing an alicyclic ester according to the invention.

Compounds with a musky smell are sought-after components in the fragrance industry. They are characterized both by their property of giving radiance to perfume compositions and by their ability to ability to act as a fixator. This means that musk fragrances are used in many perfume compositions today.

The synthesis of biodegradable compounds with a musk odor has become increasingly important in recent years, since the synthetic musk compounds of the nitroaromatic and polycyclic series are persistent and lipophilic, so that these compounds accumulate in aquatic food chains and adipose tissue (H. Brunn, G. Rimkus , Dietary Review 1996, 43, 442 to 449; H. Brunn, G. Rimkus, Dietary Review 1997, 44, 4 to 9). To close the gap, nature-like macrocyclic musk fragrances have been increasingly developed, which are characterized by a macrocyclic ring with 13 to 17 C atoms, which has a ketone or an ester as a functional group.

From US 5,166,412 (Giersch et al.), Which corresponds to EP 472966, compounds of the formula III

known, wherein R ^{1 is} for example an ethyl group and R ^{2 is} a methyl group. The compounds disclosed all comprise a 3,3-dimethyl-1-cyclohexyl radical. It is stated in the US document that the disclosed compounds have a musky smell which is paired with amber and fruity aspects. WO 00/14051 A1 discloses esters of type IV, where R ^{1 can} in particular be an alkyl group.

Furthermore, with reference to a much more general formula with a total of five substituents R ¹ - R ^{5, it is} stated that hydrogen or methyl or ethyl groups can be arranged in the 3-position of the 6-ring. It is stated that the disclosed compounds, all of which have two carbonyl functions on the side chain, have a musk odor which also shows amber and fruity aspects, which, however, should take a back seat to the compounds from US Pat. No. 5,166,412. EP 1 262474 A1 discloses cycloalkyl esters of the formula V.

wherein R ¹ and R ² independently of one another are H or CH ₃ and n = 1 to 3. The compounds disclosed in EP 1 262 474 A1 always include a 3,3-dimethyl-1-cyclohexyl radical. The disclosed compounds are said to have a musky note, which can compete with the smell of known macrocyclic musk fragrances. The musky note, however, is at best reminiscent of natural muscon.

The prior art acknowledged above shows that a number of musk fragrances are already known which are neither macrocyclic nor belong to the nitroaromatic or polycyclic series. Disadvantageously, however, the odor profile of the musk compounds of the compounds, as disclosed in EP 1 262 474, US 5,166,412 or WO 00/14051, generally differs significantly from that of the natural Muscon. The latter compounds are therefore at best conditional as a substitute for macroeyclic musk compounds, especially muscon, because not only the perfumer but also the end user perceives the existing sensory differences in properties between the two connection groups very precisely.

It was therefore the object of the present invention to provide musk fragrances whose odor profile differs from that of the compounds from the said documents and is preferably closely based on the olfactory properties of Muscon. Advantageously, the musk fragrances to be specified should have original olfactory aspects in order to expand the range of raw materials available for the composition of perfumes.

According to the invention, this object is achieved by compounds of the formulas I or II

where in formulas I and II

R ^{1 is} an optionally substituted (a) branched or unbranched Ci to C ₅ alkyl group or (b) branched or unbranched C ₂ to C ₅ alkylene group or (c) C ₃ to C ₅ cycloalkyl group

and in formula II

the bond shown in dashed lines means a single or double bond.

In particular, the following can be used as the branched or unbranched C 1 to C ₅ alkyl group: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl and 3-methylbutyl. In this respect, however, the alkyl radicals methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and isobutyl are preferred, and particularly preferably the alkyl radicals methyl, ethyl and n-propyl.

In particular, the following can be used as branched or unbranched C ₂ to C ₅ alkylene groups: ethenyl, methylethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, 1-butenyl, 3-butenyl , 1-methyl-1-butenyl, 1-methyl-3-butenyl, 3-methyl-3-butenyl, 1-pentenyl, 2-pentenyl and 4-pentenyl. To this extent, however, preferred are the alkylene radicals ethenyl, methylethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl and particularly preferably the alkylene radicals ethenyl, methylethenyl and 1-propenyl. In particular, substituted or unsubstituted C ₃ to C ₅ cycloalkyl groups can be used: cyclopropyl, 2-methylcyclopropyl, 1,2-dimethylcyclopropyl, cyclobutyl and cyclopentyl. To this extent, however, the cycloalkyl groups cyclopropyl, cyclobutyl and cyclopentyl are preferred.

The compounds of the formula I or II according to the invention can be in the form of a pure optically active enantiomer, an optically active mixture of different entantiomers or any other mixture of the stereoisomers encompassed by the formula I or II. The compounds according to the invention (alicyclic esters) Formulas I and II have perfume-like musky scent notes and are also characterized by the desired interesting leg notes. Surprisingly, the compounds of the formula I have very beautiful floral and jasmine aspects in addition to the musk note. In the case of the compounds of the formula II, such floral and jasmine aspects completely take a back seat and the compounds are distinguished by a natural musk note which is reminiscent of Muscon.

A compound of the formula VII according to the invention is particularly valuable from a sensor standpoint, where R ^{1 has} the meaning given above, but is preferably ethyl or cyclopropyl. The compound of formula VII has a 2-methyl-1-cylohexyl group and thus no double bond in the 6-ring; the compound of Formula VII has an odor reminiscent of Muscon.

According to a further aspect, the present invention also relates to mixtures which comprise a compound of the formula VII (according to the invention) and a compound of the formula VI (per se not according to the invention),

where in formulas VI and VII R ^{1 is} an optionally substituted (a) branched or unbranched Ci to C ₅ alkyl group or (b) branched or unbranched C ₂ to C ₅ alkylene group or (c) C ₃ to C ₅ cycloalkyl group. Again, preference is given to using compounds VI and VII in which R ^{1 is} ethyl or cyclopropyl. In these mixtures, the Muscon-like scent of the formula VII esters is paired with the floral, jasmine musk scent of the formula VI esters in a unique way to create a distinctive, complex musk scent. As will be explained in more detail below with reference to the synthetic route according to Scheme II, the mixtures of the compounds of the formulas VI and VII can be synthesized in a particularly economical manner.

Another aspect of the invention relates to a mixture comprising (a) a compound of the formula I and (b) a compound of the formula II,

where in formulas I and II R ^{1 is} an optionally substituted (a) branched or unbranched Ci to C ₅ alkyl group or (b) branched or unbranched C ₂ to C ₅ alkylene group or (c) C ₃ to C ₅ cycloalkyl group

and in formula II

the bond shown in dashed lines means a single or double bond.

R ¹ is preferably selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl; Ethenyl, methylethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, cyclopropyl, 2-methylcyclopropyl, 1,2-dimethylcyclopropyl, cyclobutyl and cyclopentyl.

The invention also relates to the use of a compound or a mixture according to the invention as a fragrance.

Furthermore, according to a related aspect, the invention relates to a method for producing, amplifying or modifying a musk odor in a mixture, with the following steps

Providing a compound according to the invention or a mixture according to the invention,

Providing a composition of other constituents and mixing the composition of other constituents with an amount of the compound according to the invention or the mixture according to the invention which is sufficient (a) to produce a musk odor in the resulting overall mixture, (b) to present an existing musk odor in the composition of other constituents reinforce or (c) an existing model Modify shot odor in the composition of other components.

The present invention also relates to fragrance mixtures with a musk odor, comprising - a sensorially effective amount of a compound according to the invention or a mixture according to the invention and optionally further conventional constituents such as solvents, other fragrances or the like.

The invention also relates to perfumed products comprising a fragrance mixture according to the invention and a carrier or a substrate which is in direct contact with the fragrance mixture. The scented product can advantageously be selected from the group consisting of alcoholic perfumes, personal care products and household cleaning or care products.

The compounds of the formula I and II according to the invention can be used as individual substances or in the form of mixtures (see also above) in a large number of fragrance mixtures and perfumed products. The compounds according to the invention of the formulas given above can be combined particularly advantageously with other fragrances to form novel perfume compositions.

By using the compounds according to the invention (alicyclic esters) of the formulas given above, musk notes which are reminiscent of muscon and are paired with floral accents can often be achieved in lower doses in the resulting perfume compositions, the overall olfactory impression being striking harmonized, the charisma noticeably increased and the fixation, ie the adherence of the perfume composition, are significantly increased.

Examples of fragrances with which the alicyclic esters of the formula (I) according to the invention can advantageously be combined can be found, for example, in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 3 ^rd . Ed., WileyNCH, Weinheim 1997.

The following are mentioned in detail:

Extracts from natural raw materials such as essential oils, concretes, absolues, resins, resinoids, balms, tinctures such as B. ambratincture; Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Baummoos -Absolue; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute; birch tar; Bitter almond oil; Savory oil; Buccoblatterol; Cabreuvaol; cade oil; calamus; Campherol; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Castoreum- absolue; Cedernblätteröl; cedarwood; cistus; citronella; lemon; copaiba balsam; Copaivabalsamöl; Coriander oil; costus root; Cumin oil; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de brouts - absolute; Oak moss absolute; elemi; Estragonol; Eucalyptus citriodora oil; eucalyptus oil; Fennel oil; Pine needle oil; galbanum; Galbanumresin; geranium; Grapefruit oil; guaiac wood; gurjun balsam; Gurjunbalsa oil; Helichrysum absolute; Helichrysumöl; Ginger oil; Iris root absolute; Orris root oil; Jasmine absolute; calamus; Chamomile oil blue; Roman chamomile oil; Carrot seed oil; Kaskarillaöl; Kiefemadelöl; Krainzinzöl; Seed oil; labdanum; Labdanum absolute; Labdanumresin; Lavandin absolute; Lavandin oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Lime oil pressed; Linoleum oil; Litsea cubeba oil; Bay leaf oil; Macisöl; Marjoram oil; Mandarin oil; Massoirindenöl; Mimosa absolute; Moschuskömeröl; musk tincture; Clary sage oil; nutmeg; Myrrh absolute; Myrrh oil; myrtle; Clove leaf oil; Clove flower oil; neroli; Olibanum- absolute; olibanum; Opopanaxöl; Orange blossom absolute; Orange oil; oregano; Palmarosa oil; patchouli oil; perilla oil; Peruvian balsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; chilli; pine oil; Poleyöl; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Dalmatian sage oil; Sage oil spanish; sandalwood; Selle giant seed oil; spike lavender oil; star anise; Styraxöl; tagetes; Fir needle oil; Tea-tree-oil; turpentine; Thyme oil; Tolu; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; verbena; vetiver; Juniper berry oil; Wine yeast oil; Wormwood oil; Wintergrünöi; Y-long oil; hyssop oil; Civet absolute; cinnamon leaf; cinnamon bark oil; and fractions thereof, or ingredients isolated therefrom;

Individual fragrances from the group of hydrocarbons, such as 3- caren; α-pinene; beta-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; Myrcene; ocimene; valencene; (E, Z) -1, 3,5-undecatriene;

the aliphatic alcohols such. B. hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylhectanol, 2-methyloctanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; 1-octene-3-ol; Mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E, Z) -2,6-Nonadienol; 3,7-dimethyl-7-meth-oxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; the aliphatic aldehydes and their 1,4-dioxacycloalken-2-ones such as B. Hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methyl nonanal; (E) -2-hexenal; (Z) -4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E) -4-decenal; 2- dodecenal; 2,6,10-trimethyl-5,9-undecadienal; Heptanaldiethylacetal; 1, 1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde;

aliphatic ketones and their oximes such as 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; the aliphatic sulfur-containing compounds such as 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;

aliphatic nitriles such as e.g. 2-nonenoic acid nitrile; 2-tridecenonitrile; 2,12-Tridecensäurenitril; 3,7-dimethyl-2,6-octadienonitrile; 3,7-dimethyl-6-octensäurenitril;

aliphatic carboxylic acids and their esters such as e.g. (E) - and (Z) -3- hexenyl formate; ethylacetoacetate; isoamyl; hexyl acetate; 3,5,5

trimethylhexyl; 3-methyl-2-butenyl acetate; (E) -2-hexenyl acetate;

(E) - and (Z) -3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-ylacetate; ethyl butyrate; Butyl butyrate,; isoamyl; hexyl butyrate; (E) - and (Z) -3-hexenylisobutyrate; hexyl crotonate; Ethylisovalerianat; Ethyl 2-methylpentanoate; ethylhexanoate; allyl hexanoate; ethyl heptanoate; Allyl heptanoate; ethyl octanoate; Ethyl (E, Z) -2,4-decadienoate; Methyl-2-octinat;

Methyl-2-noninat; Allyl-2-isoamyloxyacetat; Methyl 3,7-dimethyl-2,6-octadienoate;

the acyclic terpene alcohols such as citronellol; geraniol; nerol;

linalool; Lavadulol; nerolidol; farnesol; tetrahydrolinalool;

tetrahydrogeraniol; 2,6-dimethyl-7-octene-2-ol; 2,6-dimethyl octane-2-ol;

2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadiene-2-ol; 2,6-

Dimethyl-3,5-octadiene-2-ol; 3,7-dimethyl-4,6-octadiene-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; as well as their formates, acetates, propionates, isobutyrates, butyrates,

Isovalerianates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates; the acyclic terpene aldehydes and ketones such as geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2.6,10-trimethyl-9-undecenal; geranyl acetone; as well as the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal; cyclic terpene alcohols such as menthol; isopulegol; alpha-terpineol; Terpinenol-4; Menthane-8-ol; Menthane-1-ol; Menthane-7-ol; borneol; soborneol; linalool; monopoly; cedrol; ambrinol; Vetyverol; guaiol; as well as their formates, acetates, propionates, isobutyrates, butyrate, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates;

cyclic terpene aldehydes and ketones such as e.g. menthone; Isomerhon; 8-mercaptomenthan-3-one; carvone; camphor; fenchon; alpha- lonon; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-

isomethylionone; beta-isomethylionone; alpha-lron; alpha-damascone; betta-Damascon; beta-damascenone; delta-damascone; gamma-damascone;

1 - (2,4,4-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one; 1, 3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalene-8 (5H) -one;

nootkatone; Di hydronootkaton; alpha-sinensal; beta-sinensal; Acetylated cedemwood oil (methyl cedryl ketone);

cyclic alcohols such as e.g. 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-lsocamphylcyclohexanol; 2,6,9-trimethyl-Z2, Z5, E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

cycloaliphatic alcohols such as alpha, 3,3-trimethylcyclohexylmethanol; 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) butanol; 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) pentan-2-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 3,3-dimethyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 1- (2,2,6-trimethylcyclohexyl) pentan-3-ol; 1- (2,2,6-trimethylcyclohexyl) hexan-3-ol; cyclic and cycloaliphatic ethers such as cineol; Cedryl methyl ether; cyclododecyl; (Ethoxymethoxy) cyclododecane; alpha-Cedrenepoxid; 3a, 6,6,9a-tetramethyldodecahydronaphtho [2,1-bjfuran; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho [2,1-b] furan; 1,5,9-trimethyl-13-oxabicyclo [10.1.0] trideca-4,8-diene; rose oxide; 2- (2,4-dimethyl-3-cyclohexen-1-yI) -5-methyl-5- (1-methylpropyl) -1, 3-dioxane;

cyclic ketones such as e.g. 4-tert.-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4- (1-ethoxyvinyl) -3,3,5,5-tetra-methylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexadecen-1 - one; 6,7-Dihydro-1,1,2,3,3-pentamethyl-4 (5H) -indanon; 5

Cydohexadecen-1-one; 8-cyclohexadecen-1-one; 9-cycloheptadecen-1-one; cyclopentadecanone;

cycloaliphatic aldehydes such as e.g. 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4- (2,2,6-trimethyl-cyclohexen-1-yl) -2-butenal; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene carbaldehyde; 4- (4-methyl-3-penten-1-yl) -3-cyclohexenecarbaldehyde;

the cycloaliphatic ketones such as. B. 1 - (3,3-Dimethylcyclohexyl) -4-penten-1-one; 1- (5,5-dimethyl-1-cyclohexen-1-yl) ^ 4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; Methyl 2,6, 10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl- (2,4-dimethyl-3-cyclohexen-1-yl) ketone;

the ester of cyclic alcohols such as 2-tert-butylcyclohexyl acetate; 4-tert butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; Decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-ylacetate; Decahydro-2,5,5,8a-tetramethyl-2 naphthyl acetate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, or 6-indenyl acetate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, or

6-indenylpropionat; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5 _J or 6-indenyl isobutyrate; 4,7-methanooctahydro-5 or 6-indenyl acetate;

the ester of cycloaliphatic carboxylic acids such as. B. Allyl 3-cyclohexyl propionate; Allylcyclohexyloxyacetat; methyldihydrojasmonate; methyl jasmonate; Methyl-2-hexyl-3-oxocyclopentanecarboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; Ethyl 2-methyl-1,3-dioxolane-2-acetate;

the aromatic hydrocarbons such. B. styrene and diphenyl methane;

araliphatic alcohols such as e.g. benzyl alcohol; 1-phenylethyl alcohol; 2-PhenylethylaIkohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-methylphenyl) propanol; 1, 1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl; 1- (4-isopropylphenyl) ethanol;

the ester of araliphatic alcohols and aliphatic carboxylic acids such as; benzyl acetate; benzylpropionate; benzyl isobutyrate; Benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-Phenylethylisovalerianat; 1 -phenylethyl acetate; alpha-Trichlormethylbenzylacetat; alpha, alpha-dimethylphenylethyl acetate; alpha.alpha-Dimethylphenylethylbutyrat; Cinamate acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; the araliphatic ether such as 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl-1-ethoxyethyl ether; Phenylacetaldehyde dimethyl acetal; phenylacetaldehyde; Hydrate- ropaaldehyddimethylacetal; Phenylacetaldehydglycerinacetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxanes; 4,4a, 5,9b-tetrahydroindeno [1,2-d] -m-dioxin; 4,4a, 5,9b-tetrahydro-2,4-dimethylindeno [1,2-d] -m-dioxin;

the aromatic and araliphatic aldehydes such as. B. Benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; Hydratropaaldehyd; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3- (4-ethylphenyl) -2,2-dimethylpropanal; 2-methyl-3- (4-isopropylphenyl) propanal; 2-methyl-3- (4-tert-butylphenyl) propanol; 3- (4-tert-butylphenyl) propanal; Cinnamon aldehyde; alpha-Butylzimtaldehyd; alpha-amyl cinnamic aldehyde; alpha-hexyl cinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-Hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3- (4-methoxyphenyl) propanal; 2-methyl-3- (4-methylenedioxyphenyl) propanal;

aromatic and araliphatic ketones such as e.g. acetophenone; 4-methyl acetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1- (2-naphthalenyl) ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1 - [2,3-dihydro-1,1,2,6-tetramethyl-3- (1-methylethyl) -1 H-5-indenyl] ethanone; 5 \ 6 ', 7', 8'-tetrahydro-3 ', 5', 5 ', 6', 8 ', 8'-hexamethyl-2-acetonaphthone;

aromatic and araliphatic carboxylic acids and their esters such as benzoic acid; phenylacetic acid; Methyl benzoate; ethyl benzoate; hexyl benzoate; Benzyl benzoate; Methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; Phenylethyl phenylacetate; Methylcinnmat; Ethyl cinnamate; Benzyl; Phenylethylcinnamat; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl; hexyl salicylate; Cyclohexyl salicylate; Cis-3-hexenyl salicylate; benzyl; phenyl ethyl salicylate; Methyl-2,4-dihydroxy-3,6-dimethylbenzoate; Ethyl 3-phenyl glycidate; Ethyl-3-methyl-3-phenylglycidate;

the nitrogenous aromatic compounds such as e.g. 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamic acid; 5-phenyl-3-methyl-2-pentenoic acid nitrile; 5-phenyl-3-methylpentansäurenitril; methyl anthranilate; Methyl-N-methylanthranilate; SchifFsche bases of methylanthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-lsopropylchinolin; 6-isobutylquinoline; 6-sec-butylquinoline; indole; skatol; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

of phenols, phenyl ethers and phenyl esters such as e.g. estragole; anethole; eugenol; Eugenylmethyiether; isoeugenol; Isoeugenylmethylether; Thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-Naphthylisobutylether; 1,4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methyl phenol; 2-ethoxy-5- (1 - propenyl) phenol; p-Kresylphenylacetat;

the heterocyclic compounds such as e.g. 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furaπ-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

the lactones such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1.15 PentadecanoIid; cis- and trans-11-pentadecen-1,15-olide; ice and trans-12-pentadecen-1, 15-olide; 1, 16-hexadecanolide; 9-hexadecene-1,16-olide; 10-oxa-1, 16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; Ethylene 1, 12-dodecanedioate; Ethylene 1, 13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; Octahydrocoumarin. Perfume oils which contain the compounds of the above formulas according to the invention can be used in liquid form, undiluted or diluted with a solvent for perfuming. Suitable solvents for this are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerin, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.

Perfume oils which contain the compounds according to the invention can be absorbed on a carrier which ensures both a fine distribution of the fragrances in the product and a controlled release during use. Such carriers can be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsum, clays, clay granules, gas concrete etc. or organic materials such as woods and cellulose-based substances.

Perfume oils which contain the compounds according to the invention can also be microencapsulated, spray-dried, present as inclusion complexes or as extrusion products and can be added in this form to the product to be perfumed.

If necessary, the properties of the perfume oils modified in this way can be further optimized by so-called "coating" with suitable materials with a view to a more targeted fragrance release, for which purpose wax-like plastics such as polyvinyl alcohol are preferably used.

The microencapsulation of the perfume oils can take place, for example, by means of the so-called coacervation process with the aid of capsule materials, for example made of polyurethane-like substances or soft gelatin. The spray-dried perfume oils can be produced, for example, by spray drying an emulsion or dispersion containing the perfume oil, it being possible to use modified starches, proteins, dextrin and vegetable gums as carriers. Inclusion- Complexes can be prepared, for example, by adding dispersions of the perfume oil and cyclodextrins or urea derivatives in a suitable solvent, for example water. Extrusion products can be made by fusing the perfume oils with a suitable wax-like substance and by extrusion with subsequent solidification, if necessary in a suitable solvent, eg isopropanol.

In perfume compositions, the amount of the compounds according to the invention used is preferably 0.05 to 50% by weight, preferably 0.5 to 20% by weight, based on the total perfume oil.

Perfume oils containing the compounds according to the invention can be used in concentrated form, in solutions or in the modified form described above for the production of, for example, perfume extracts, eau de parfms, eau de toilettes, aftershaves, eau de logos, pre -shave products, splash colognes and scented refreshing wipes as well as the scenting of acidic, alkaline and neutral cleaning agents, such as floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring milk, solid and liquid toilet cleaners, powder and foam-shaped tep- Pichreiniger, liquid detergents, powder detergents, laundry pretreatment agents such as bleach, soak and stain removers, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants and air fresheners in liquid, gel-like or applied to a solid carrier, aerosol spray ys, waxes and polishes such as furniture polishes, floor waxes, shoe creams as well as personal care products such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions from oil-in-water, water-in-oil and water-in -OI-in-water type such as skin creams and lotions, face creams and lotions, sun protection creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products such as hair sprays, hair gels, firm hair lotions, hair rinses, permanent and semi-permanent hair colorants, hair shaping agents such as cold waves and hair straightening agents, hair lotions, deodorants, hair lotions, hair creams, ranties and antiperspirants such as armpit sprays, roll-ons, deodorants, deodorant creams, decorative cosmetics products such as eyeshadow, nail polishes, make-ups, lipsticks, mascara and candles, lamp oils, incense sticks, insecticides, repellents and fuels.

The invention also relates to a method for producing a compound according to the invention, comprising the following steps:

Providing an alcohol of formula (XVI) or (XXII)

(XVI) (XXII)

Esterification of the alcohol to the compound of the invention.

Processes for producing mixtures according to the invention comprise corresponding steps and are preferably based on alcohol mixtures; see. in particular the following synthetic routes according to Scheme 2. The preparation of alicyclic esters of the formula II according to the invention, in which

R ^{1 has} the meaning given above and the dashed line is a single bond,

succeeds in particular according to the synthetic route in Scheme 1.

(VII)

(VII)

Scheme 1

In the synthesis route according to Scheme 1, 2-methylacetophenone (VIII) is converted into 1- (2-methylcyclohexyl) ethanol (IX) by hydrogenation, for example on Ru / C, by methods familiar to the person skilled in the art. In the second step, isobutylene oxide (X) is opened nucleophilically with 1 - (2-methylcyclohexyl) ethanol (IX). This reaction can take place, for example, with the addition of 0.02 mol% to 20 mol%, preferably 0.5 mol% to 10 mol%, of a Lewis acid, preferred Lewis acids contain a boron atom, and BF ₃ is particularly preferred. OEt ₂ . The resulting alcohol (XI) (= alcohol of the compound XXII in which the dashed line is a single bond) is esterified according to methods familiar to the person skilled in the art. Here, the esterification can be carried out by heating the alcohol (XI) and the corresponding carboxylic acid on a water separator in the presence of an entrainer (for example toluene or cyclohexane) with the addition of 0.01 mol% to 10 mol%, preferably 0.1 mol% to 5 mol% of an acid, preferably p-toluenesulfonic acid or sulfuric acid or by reacting the alcohol (XI) with the corresponding carboxylic anhydride in the presence of triethylamine and 0.5 mol% to 50 mol%, preferably 1.0 mol% to 30 mol%, 4-dimethylaminopyridine.

The preparation of a mixture of alicyclic esters according to the invention of the formulas I and II, in which R ¹ and the dashed line have the meaning given above,

succeeds in particular according to the synthetic route in Scheme 2.

Scheme 2 In the first step of the synthetic route shown in Scheme 2, a Diels-Alder reaction of 1,3-pentadiene and methyl vinyl ketone, in the presence of catalytic amounts of a Lewis acid, is carried out by methods familiar to the person skilled in the art. The isomer mixture of the two unsaturated ketones (XII) / (XIII) which is formed is subsequently reduced on the one hand to the unsaturated alcohols (XIV) / (XV) and on the other hand converted into the saturated alcohols (XVIII) / (XIX) by hydrogenation. The reduction with sodium borohydride, as well as the hydrogenation, can be carried out according to methods well known to the person skilled in the art. The further reaction of the alcohols (XIV) / (XV) and (XVIII) / (XIX) is carried out analogously to the reaction shown in Scheme 1 with isobutylene oxide and subsequent esterification.

The following examples illustrate the invention:

example 1

Preparation of propionic acid 2-methyl-2- [1 - (2-methyl-cyclohexyl) ethoxy-propyl ester (compound of the formula VII with R ¹ = ethyl)

1- (2-Methyl-cyclohexyI) -ethanol 2-methylacetophenone (111.0 g, 0.83 mol) is hydrogenated at 75 ° C and 18 bar hydrogen pressure over 2.60 g ruthenium 5% on activated carbon. After the hydrogenation has ended, the product is filtered off with suction through Celite, rinsed with ethyl acetate and evaporated. 107.3 g of 1- (2-methylcyclohexyl) ethanol are obtained as a colorless liquid which can be used directly in the next reaction without further purification.

¹ H-NMR (400 MHz, CDCI ₃ ): δ (ppm) = 0.91 (d, J = 7.2 Hz, 3H), 1.15-1.42 (m, 9H), 1.18 (d, J = 6.2 Hz, 3H), 2.17-2.27 (m, 1H), 3.45-3.58 (m, 1H). ¹³ C-NMR (100 MHz, CDCI ₃ ): δ (ppm) = 12.4, 20.2, 21.9, 23.3, 26.5, 27.7, 33.4, 48.3, 69.4.

2-methyl-2 ~ [1- (2-methyl-cyclohexyl) ethoxy] propan-1-ol: to a solution of 1- (2-methylcyclohexyl) ethanol (71.2 g, 0.50 mol) and BF ₃ OEt ₂ (1.7 ml) are added within 30 minutes isobutylene oxide (3.2 g, 45.0 mmol). Now let stir for 20 hours at room temperature. When the stirring time has ended, the pH is adjusted to 11 using 1 NaOH, and excess 1- (2-methylcyclohexyl) ethanol is distilled off. The residue is taken up in water (50 ml) and extracted three times with ether (150 ml). The combined organic phases are dried, filtered off and evaporated. 8.3 g of crude 2-methyl-2- [1- (2-methylcyclohexyl) ethoxy] propan-1-ol are obtained with a GC content of 76%, which is used in the next reactions without further purification can be.

Propionic acid 2-methyl-2- [1- (2-methyl-cyclohexyl) ~ ethoxy] propyl. To a solution of 2-methyl-2- [1- (2-methylcyclohexyl) ethoxy] - propan-1-ol (GC purity: 76%; crude product from the second stage) (2.80 g, 10.0 mmol) and propionic anhydride (2.61 g, 20.0 mmol) are added in succession to triethylamine (1.6 g, 15 mmol) and 4 - Dimethylaminopyridine (0.13 g, 1.0 mmol). After stirring for one hour at room temperature, the reaction solution is diluted with ether (100 ml) and the organic phase is washed twice with 2 M HCl and saturated NaHCO ₃ solution. The combined organic phases are dried over Na ₂ SO ₄ , filtered off and freed from solvent on a rotary evaporator. After flash chromatography (cyclohexane / EtOAc = 45: 1, R _f = 0.25) and Kugelrohr distillation (KRD: 145 ° C, 0.69 mbar), 2.29 g (85%) of propionic acid-2-methyl-2- [1 - (2-methylcyclohexyl) ethoxy] propyl ester as a colorless oil.

Smell: musky, natural, reminiscent of muscon. ¹ H-NMR (400 MHz, CDCI ₃ ): δ (ppm) = 0.87 (d, J = 7.1 Hz, 3H), 0.95-1.05 (m, 1 H), 1.09 (d, J = 6.1 Hz, 3H) , 1.16 (t, J = 7.6 Hz, 3H), 1.19 (s, 6H), 1.25-1.57 (m, 6H), 1.67-1.75 (m, 1 H), 1.84-1.96 (m, 1 H), 2.14 -2.22 (m, 1H), 2.36 (q, J = 7.6 Hz, 2H), 3.48 (d, q, J = 7.0, 6.1 Hz, 1 H), 3.96 (s, 2H). ¹³ C-NMR (100 MHz, CDCI ₃ ): δ (ppm) = 9.1, 12.9, 20.4, 21.1, 23.7, 23.9, 24.5, 26.6, 27.7, 28.7, 34.0, 47.4, 70.4, 70.9, 73.6, 174.3.

The following compound from Example 2 was prepared analogously to the instructions described in Example 1, with the change that the esterification was carried out with cyclopropanecarboxylic acid. Only the spectroscopic data are listed here:

Example 2

Preparation of Cyclopropaπcarbonsäure 2-methyl-2- [1- (2-methylcyclohexyl) ethoxy] propyl ester (compound of formula VII with R ¹ = cyclopropyl) Smell: musk, amber, reminiscent of muscon. KRD: 175 ° C, 0.12 mbar.

¹ H-NMR (400 MHz, CDCI ₃ ): δ (ppm) = 0.84-0.89 (m, 2H), 0.88 (d, J = 7.2 HZ, 3H), 0.94-1.04 (m, 3H), 1.09 (d , J = 6.0 Hz, 3H), 1.16-1.24 (m, 2H), 1.21 (s, 6H), 1.34-1.42 (m, 4H), 1.60-1.68 (m, 1H), 1.68-1.75 (m, 1H ), 1.84-1.96 (m, 1 H), 2.15-2.22 (m, 1 H), 3.49 (dq, J = 7.0, 6.1 Hz, 1 H), 3.94 (d, J = 11.0 Hz, 2H).

¹³ C-NMR (100 MHz, CDCI ₃ ): δ (ppm) = 8.3 (2C), 12.9, 13.0, 20.3, 21.1, 22.9, 23.8, 24.6, 27.0, 28.0, 33.9, 47.9, 70.3, 70.9, 73.7, 174.7.

Example 3

Preparation of propionic acid 2-methyl-2- [1 - (2-methylcyclohexyl) ethoxyj-propyl ester / propionic acid 2-methyl-2- [1 - (3-methylcyclohexyl) ethoxy] propyl ester (compound of the formula Vll / Vl with R ¹ = ethyl)

1- (2-methyl-cyclohex-3-enyl) -ethanone / 1- (5-methyl-cyclohex-3-enyl) -ethanone (Xlll / Xll): methyl vinyl ketone (436.1 g, 6.20 mol) and aluminum chloride ( 8.2 g, 0.06 mol) and this mixture is heated to 60 ° C. with vigorous stirring, then the 1,3-pentadiene (GC content 80%, 136.8 g, 1.61 mol) is added at 60 ° C. Now let it stir for 24 h at 60 ° C. When the stirring time has ended, the excess methyl vinyl ketone is distilled off, the remaining solution is treated with ice water (250 ml) and extracted three times with ether (300 ml). The combined organic phases are dried, filtered off and evaporated. After fractional distillation, 172.4 g of a regioisomer mixture of 1 - (2-methyl-cyclohex-3-enyl) -ethanone / 1 - (5-methyl-cyclohex-3-enyl) -ethanone are obtained.

Regioisomer ratio Xlll / Xll ~ 7: 1 (according to ¹ H-NMR)

The spectroscopic data correspond to the literature data (Hersh,

WH et al, J. Am. Chem. Soc, 111, 6070-6081, 1989). 1- (2-methyl-cyclohexyl) -ethanol / 1- (3-methyl-cyclohexyl) -ethanol (XIX / XVIII): 1 - (2-methyl-cyclohex-3-enyl) -ethanone / 1 - (5- Methyl-cyclohex-3-enyl) -ethanone -7: 1 (85.0 g, 0.61 mol) is hydrogenated at 80 ° C. and 10 bar hydrogen pressure over 2.00 g of Raney nickel. After the hydrogenation has ended, the product is filtered off with suction through Celite, rinsed with ethyl acetate and evaporated. This gives 82.3 g of 1- (2-methyl-cyclohexyl) ethanol / 1- (3-methyl-cyclohexyl) ethanol ~ 7: 1 as a colorless liquid which can be used directly in the next reaction without further purification. The spectroscopic data of the regioisomer mixture 1- (2-methyl-cyclohexyl) -ethanol / 1- (3-methyl-cyclohexyl) -ethanol -7: 1 correspond to those of the pure individual compounds and are therefore not listed.

The subsequent reaction with isobutylene oxide and the esterification with propionic anhydride are carried out analogously to the instructions from Example 1. The spectroscopic data of the regioisomer mixture propionic acid 2-methyl-2- [1 - (2-methylcyclohexyl) ethoxy] propyl ester / propionic acid 2-methyl-2- [1- (3-methylcyclohexyl) ethoxy] - Propyl esters correspond to those of the pure individual compounds and are therefore not listed.

Propionic acid 2-methyl-2- [1- (2-methylcyclohexyl) ethoxy] propyl ester / Propionic acid 2-methyl-2- [1- (3-methylcyclohexyl) ethoxy] propyl ester (VIII / Vl with R ¹ = ethyl):

Regioisomer ratio Vll / Vl with R ¹ = ethyl - 7: 1 (according to ¹ H-NMR) Odor: musky, very natural, reminiscent of Muscon, with floral aspects

The following compounds of Example 4 were prepared analogously to the instructions described in Example 3, with the change tion that the esterification was carried out with cyclopropanecarboxylic acid. The spectroscopic data of the regioisomer mixtures correspond to that of the pure individual compounds and are therefore not listed:

Example 4:

Preparation of cyclopropanecarboxylic acid 2-methyl-2- [1- (2-methylcyclohexyl) ethoxy] propyl ester / cyclopropanecarboxylic acid 2-methyl-2- [1 - (3-methylcyclohexyl) ethoxy] propyl ester ( Compound of the formula VII / VI with R = cyclopropyl)

Regioisomer ratio Vll / Vl with R = Cyclopropyl - 7: 1 (according to ¹ H-NMR) Odor: musky, amber, reminiscent of Muscon, somewhat flowery.

Example 5

Preparation of propionic acid 2-methyl-2- [1 - (2-methylcyclohex-3-enyl) ethoxy] propyl ester / propionic acid 2-methyl-2- [1- (5-methylcyclohex-3- enyl) ethoxy] propyl ester (compound of the formula II / l with R ¹ = ethyl):

1- (2-methyl-cyclohex-3-enyl) ethanol / 1- (5-methyl-cyclohex-3-enyl) ethanol (XV / XIV): 1- (2-methyl-cyclohex-3- enyl) -ethanone / 1- (5-methyl-cyclohex-3-enyl) -ethanone -7: 1 (40.0 g, 0.29 mol) in ethanol (150 ml), cool to 0 ° C and add portions of sodium borohydride ( 5.50 g, 0.15 mol). The mixture is then left to stir at room temperature for 1 hour, the reaction solution is now neutralized with 2 M HCl, ethanol is removed on a rotary evaporator and the residue is taken up in total. NaCI solution (100 ml). The aqueous phase is then extracted three times with ether (150 ml), the combined organic phases are dried, filtered off and evaporated in a rotary evaporator. 37.6 g of 1- (2-methyl-cyclohex-3-enyl) -ethanol / 1- (5-methyl-cyclohex-3-enyl) -ethanol are obtained as a colorless oil, which can be used in the next reaction without further purification.

Regioisomer ratio XV / XIV ~ 7: 1 (according to H-NMR) Indication of the XV isomer:

¹ H-NMR (400 MHz, CDCI ₃ ): δ (ppm) = 1.03 (d, J = 7.0 Hz, 3H), 1.23 (d, J

= 6.4 Hz, 3H), 1.28-1.38 (m, 1H), 1.42-1.54 (m, 1H), 1.70-2.26 (m, 4H),

3.96-4.07 (m, 1H), 5.58-5.72 (m, 2H).

¹³ C-NMR (100 MHz, CDCI ₃ ): δ (ppm) = 20.1, 20.5, 21.3, 26.9, 31.8, 47.1, 67.5, 126.0, 133.4.

The subsequent reaction with isobutylene oxide and the esterification with propionic anhydride are carried out analogously to the instructions from Example 1.

Propionic acid 2-methyl-2- [1 - (2-methylcyclohex-3-enyl) ethoxy] propyl ester / propionic acid 2-methyl-2- [1- (5-methylcyclohex-3-enyl) - ethoxy] propyl ester (ll / l with R ¹ = ethyl):

Regioisomer ratio ll / l with R ¹ = ethyl - 7: 1 (according to ¹ H-NMR) Odor: musky, amber, somewhat greasy. Indication of the II isomer:

¹ H-NMR (400 MHz, CDCI ₃ ): δ (ppm) = 0.91 (d, J = 6.9 Hz, 3H), 1.03 (d, J = 6.1 Hz, 3H), 1.16 (t, J = 7.6 Hz, 3H), 1.19 (s, 6H), 1.30-2.10 (m, 6H), 2.36 (q, J = 7.6 Hz, 2H), 3.63 (quin, J = 6.1 Hz, 1H), 3.94 (s, 2H), 5.60-5.69 (m, 2H).

¹³ C-NMR (100 MHz, CDCI ₃ ): δ (ppm) = 9.1, 17.6, 19.9, 20.8, 23.7, 23.8, 24.8, 27.6, 32.1, 44.7, 70.1, 70.2, 74.1, 125.1, 134.1, 174.2.

Example 6:

The present perfume oil can be used to perfume various cosmetic products. Composition:

BA = Benzylalkohol; IPM = Isopropylmyristat; DEP = Diethylphtalat

BA = benzyl alcohol; IPM = isopropyl myristate; DEP = diethyl phthalate

The addition of

a) 355 parts by weight of propionic acid 2-methyl-2- [1- (2-methylcyclohexyl) ethoxy] propyl ester / propionic acid 2-methyl-2- [1- (3-methylcyclohexyl) ethoxy] - propyl ester (compound of the formula VIII / VI with R ¹ = ethyl -7: 1; total 1000 parts by weight) leads to a clearly perceptible harmonization of the floral heart note. In addition, the natural musk note gives the present composition excellent radiation and increased adhesion. The valuable character of propionic acid 2-methyl-2- [1- (2-methylcyclohexyl) ethoxy] propyl ester / propionic acid 2-methyl-2- [1- (3-methylcyclohexyl) -ethoxy] -propyIester (Vll / Vl with R ¹ = ethyl -7: 1) in comparison to compositions with conventional musk fragrances. 355 parts by weight of cyclopropanecarboxylic acid 2-methyl-2- [1-

(2-methylcyclohexyl) ethoxy] propyl ester / cyclopropanecarboxylic acid 2-methyl-2- [1- (3-methylcyclohexyl) ethoxy] propyl ester (compound of the formula VII / VI with R = cyclopropyl - 7: 1; a total of 1000 parts by weight)

Composition an incomparable musk note that cannot be achieved with existing musk fragrances. Furthermore, the entire composition gains in abundance and appears more valuable.

Claims

Expectations: 1. Compound of formula I or II

where in formulas I and II R ^{1 is} an optionally substituted (a) branched or unbranched Ci to C ₅ alkyl group or (b) branched or unbranched C ₂ to C ₅ alkylene group or (c) C ₃ to C ₅ cycloalkyl group and in formula II the bond shown in dashed lines means a single or double bond. 2. A compound according to claim 1, wherein R ^{1 is} selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl; Ethenyl, methylethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, cyclopropyl, 2- Methylcyclopropyl, 1, 2-dimethylcyclopropyl, cyclobutyl and cyclopentyl. 3. A compound according to claim 1 or 2, wherein the compound corresponds to formula VII:

4. Mixture comprising a compound of formula VII and a compound of formula VI

where in the formulas VI and VII R ^{1 is} an optionally substituted (a) branched or unbranched Ci to C ₅ alkyl group or (b) branched or unbranched C ₂ to C ₅ alkylene group or (c) C ₃ to C ₅ cycloa alkyl group , 5. Mixture comprising (a) a compound of the formula I and (b) a compound of the formula II,

where in formulas I and II R ^{1 is} an optionally substituted (a) branched or unbranched Ci to C ₅ alkyl group or (b) branched or unbranched C ₂ to C ₅ alkylene group or (c) C ₃ to C ₅ cycloalkyl group and in formula II the bond shown in dashed lines means a single or double bond. 6. Mixture according to claim 4 or 5, wherein R ^{1 is} selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl; Ethenyl, methylethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, cyclopropyl, 2-methylcyclopropyl, 1, 2-dimethylcyclopropyl, cyclobutyl and cyclopentyl. 7. Use of a compound according to any one of claims 1-3 or a mixture according to one of claims 4-6 as a fragrance. 8. A method of creating, enhancing or modifying a musk odor in a mixture, comprising the following steps: Providing a compound according to any one of claims 1-3 or a mixture according to any one of claims 4-6, - Provide a composition of other components and - Mixing the composition of other constituents with an amount of the compound according to one of claims 1-3 or the mixture according to one of claims 4-6, which is sufficient (a) to produce a musky smell in the resulting overall mixture, (b) a preliminary to reinforce existing musk odor in the composition of other components or (c) to modify an existing musk odor in the composition of other components. 9. fragrance mixture with musk odor, comprising a sensorially effective amount of a compound according to any one of claims 1-3 or a mixture according to any one of claims 4-6 and optionally other conventional ingredients such as solvents, other fragrances or the like. 10. Perfumed product comprising a fragrance mixture according to claim 9 and a carrier or a substrate which is in direct contact with the fragrance mixture. 11. Perfumed product according to claim 10, selected from the group consisting of alcoholic perfumes, personal care products and household cleaning or care products. 12. A method for producing a compound according to any one of claims 1-3, comprising the following steps: Providing an alcohol of formula XVI or XXII

(XVI) (XXII) Esterification of the alcohol to the compound according to any one of claims 1-3.