WO2004002930A1 - Odoriferous substances and method for the production thereof - Google Patents

Abstract

The invention relates to cyclododecyl butan-2-ols, to the use thereof as odoriferous substances and as antimicrobial active substances, to a method for the production thereof, and to products containing these compounds.

Description

 FRAGRANCES AND METHOD FOR THEIR PRODUCTION

The invention relates to cyclododecylbutan-2-ols, their use as fragrances and as antimicrobial agents, a process for their preparation and products containing these compounds.

Because of the generally inadequate availability of many natural fragrance components, the need to adapt to changing fashionable flavors and the constantly increasing need for new fragrances, which alone or in the form of compositions are valuable fragrances or perfumes with interesting fragrance notes, there is still a need for new ones Connections with valuable fragrance qualities.

Fragrance substances with a cyclododecyl or cyclododecenyl structure are known. These often belong to the classes of acetals, esters, ketones or alcohols, with the specific odor notes of the compounds depending on the structure.

In doc. Akad. Nauk Az. SSR, 1989, (8), 32-35, 1-cyclododecylethanol and 1-cyclododecylpropan-2-ol and the esters derived therefrom are mentioned. Weak wood smells with sandal, camphor, musk and

Amber notes and greasy and floral nuances are given.

In EP-A 0278384 is for the racemate of 2-Cyclododecylpropan-l-ol (Hydroxyambran ^®) a flowery, warm, heavy wood odor and called a ambriert woody odor note for the corresponding ethyl ether. In EP-A

In 1 153 911, the (+) - 2-cyclododecylpropan-l-ol is described as almost odorless and the (-) - 2-cyclododecylpropan-1-ol as strongly amber-woody with a dominant amber character. The invention relates inter alia to the use of 3-cyclododecylbutan-2-ols (formula A) and 1-cyclododecylbutan-2-ols (formula B) as fragrances.

A B

The invention also relates to the compounds corresponding to formulas A and B, processes for their preparation and perfumed products and fragrance mixtures containing the compounds according to the invention.

It was found that the compounds according to the invention have complex wood-amber fragrance properties, surprisingly soft cedar-woody notes being dominant in these compounds. In addition, they have typical amber notes. In addition, the connections are characterized by long-lasting adhesion.

The compounds of the invention can advantageously be prepared by reacting cyclododecene with butan-2-one in step (a), preferably in the presence of a radical initiator, and then in step (b) the ketones formed in step (a) (Addition products) can be reduced, e.g. by reductive treatment of the reaction mixture containing the ketones.

In the reaction of cyclododecene with butan-2-one (step a), the molar

Ratio of butan-2-one to cyclododecene in general between 400 and 1, preferably between 150 and 1 and in particular between 50 and 5. The radicals necessary for the reaction (step a) are generated by generally customary methods, with thermally induced decomposition of the added radical initiators being preferred.

Azo compounds (e.g. 2,2'-

Azobis-isobutyronitrile) and peroxide compounds can be used, the use of peroxides, in particular di-tert-butyl peroxide, being preferred.

Since the radical initiators disintegrate at different temperatures, the temperature range for carrying out the radical reaction (step a) is variable over a wide range. It is generally between 30 and 250 ° C, preferably 80 to 220 ° C. If di-tert-butyl peroxide is used as the radical initiator, work is preferably carried out at 120-200 ° C.

The reaction (step a) is preferably under pressure, advantageously in one

Autoclaves carried out, although very high pressures are possible. Is preferably carried out at a pressure between 2 and 20 bar.

The reaction mixture usually obtained after distillative removal of excess butan-2-one, possibly unreacted cyclododecene and low boilers formed contains, as addition products, both the 3-cyclododecyl and 1-cyclododecylbutan-2-ones and the corresponding α, ι8-unsaturated ones ketones.

The subsequent conversion of the reaction mixture obtained into the compounds according to the invention can be carried out in various ways. According to route I, the α, / 3-unsaturated ketones contained in the reaction mixture are first converted into the saturated ketones by hydrogenation of the olefinic double bond. Hydride by subsequent reduction of the keto group with hydrides, such as sodium borohydride, Limiumalumim ^'or lithium borohydride, the

Obtain compounds according to formulas A and B. According to route II, which is the preferred preparation variant, the reaction mixture obtained in the radical reaction is converted into the end products by simultaneous hydrogenation of the olefinic double bond and the carbonyl group in one reaction step.

Heterogeneous catalysts are generally used as hydrogenation catalysts, but suitable homogeneous catalysts can also be used. Examples of hydrogenation catalysts, support materials and hydrogenation conditions are e.g. in Houben-Weyl, Methods of Organic Chemistry, Volume IV / lc, Vl / lb and VLT / 2c. Of the hydrogenation catalysts listed there, preference is given to those which contain one or more elements from the VLTIb group of the Periodic Table of the

Contain elements. Palladium catalysts such as palladium on activated carbon can be used to hydrogenate the olefinic double bonds in accordance with route I. Ruthenium catalysts, such as ruthenium on activated carbon, can be used for the simultaneous hydrogenation of the olefinic double bond and the carbonyl group according to route II.

The hydrogenation (route I or H) is advantageously carried out at temperatures between 40 and 300 ° C, preferably between 50 and 150 ° C. The

Hydrogen pressure is usually between 5 and 50 bar, preferably between 10 and 25 bar.

The compounds according to the invention are generally obtained as a mixture of the compounds corresponding to the formulas A and B. The 3-cyclododecylbutan-2-ols are presumably present as a mixture of the syn and anti compounds (isomers 1 and 2). The syn and anti nomenclature here refers to the stereoisomerism of the methyl and the hydroxyl group to one another.

Both the 3-cyclododecylbutan-2-ols and the l-cyclododecylbutan-2-ols have a pronounced cedar-woody odor with additional amber Grades. With l-cyclododecylbutan-2-ol there is also a slight green odor impression. A long-lasting effect is observed with the compounds according to the invention. Because of these special organoleptic properties, these compounds are outstandingly suitable for use as fragrances.

The compounds according to the invention can therefore be used both as individual substances and as a mixture in a large number of products; They can be combined particularly advantageously with other fragrances in different, different proportions to form novel perfume compositions.

By using the compounds according to the invention, the

Usually in low doses in the resulting perfume compositions

, woody cedar and amber notes. The use of the compounds according to the invention intensifies the radiance of perfume compositions and gives the composition freshness and liveliness. In perfume compositions, the compounds according to the invention also bring about more volume in the odor and a softer and more rounded odor flow. By adding the compounds according to the invention, the adhesiveness of the perfume oil mixture, i.e. their fixation, significantly increased and an elongated

Scent drain reached.

In addition to the interesting olfactory properties, the compounds of the formulas A and B also have antimicrobial properties, in particular against gram-positive bacteria. Because gram-positive germs in cosmetics, oral hygiene and

Dermatology play a special role, they are particularly suitable as antibacterial agents and can therefore be used in particular in cosmetic, oral hygiene and dermatological preparations. They are particularly suitable for use in deodorants such as armpit sprays, roll-ons, deo sticks, deodorant creams, gels or powders. When the compounds according to the invention are used in cosmetics and household products, they are notable for high stability. The stability in antiperspirant products based on aluminum and zirconium salts, such as, for example, aluminum hydroxychloride, is particularly noteworthy, so that the compounds according to the invention are also outstandingly suitable for use in antiperspirants.

The invention therefore also relates to preparations, in particular cosmetic, dermatological and oral hygiene preparations, comprising an antimicrobially effective amount of a compound of the formula A or B or a mixture of

Compounds of formulas A and B.

Examples of fragrances with which the butanols according to the invention can advantageously be combined can be found e.g. in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, N.J., 1969, Selbstverlag or K. Bauer, D.

Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4 ^rd . Ed., Wiley-

VCH, Weinheim 2001.

The following are mentioned in detail:

Extracts from natural raw materials such as essential oils, concretes, absolute,

Resins, resinoids, balms, tinctures such as B.

ambergris tincture; Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil;

Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute; birch tar; Bitter almond oil; Savory oil; Buccoblätteröl;

Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascarilla oil; cassia; Cassie absolute; Beaver-absolue; Cedernblätteröl; cedarwood;

cistus; citronella; lemon; copaiba balsam; Copaivabalsamöl; Coriander oil;

costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de brouts - absolute; Oakmoss absolute; elemi; Tarragon oil; Eucalyptus citriodora-

Oil; eucalyptus oil; Fennel oil; Pine needle oil; galbanum; Galbanumresin; geranium; Grapefruit oil; guaiac wood; gurjun balsam; gurjun balsam oil; Helichrysum absolute; Hehchrysumöl; Ginger oil; Iris root absolute; Orris root oil; Jasmine absolute; Kahnusöl; Chamomile oil blue; Roman chamomile oil; Carrot seed oil; Kaskarillaöl; Pine needle oil; spearmint; Seed oil; labdanum; Labdanum absolute; Labdanumresin; Lavandin absolute; lavender oil; Lavender absolute;

Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Lime oil pressed; linaloe; Litsea cubeba oil; Bay leaf oil; Macisöl; Marjoram oil; Mandarin oil; Massoirindenöl; Mimosa absolute; Musk seed oil; musk tincture; Muscatel 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; Celery seed oil; spike lavender oil; star anise; Styraxöl; tagetes; Pine 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; Wintergreen oil; ylang oil; hyssop oil; Civet absolute; cinnamon leaf; Cinnamon bark oil, as well as fractions thereof, or ingredients isolated therefrom;

Individual fragrances from the group

of hydrocarbons, such as B. 3-carene; α-pinene; beta-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E, Z) -l, 3,5-undecatriene; styrene;

diphenylmethane;

aliphatic alcohols such as hexanol; octanol; 3-octanol; 2,6-dimethyl-heptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E) -2-hexenol; (E) - and (Z) -3- hexenol; l-octen-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-methoxyoctan-2-ol; 9-decenol; 10 -Undecenol; 4-methyl-3-decen-5-ol;

the aliphatic aldehydes and their acetals such as e.g. 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; Heptanal diethyl acetal; 1, 1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde;

the aliphatic ketones and their oximes such as e.g. 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; 6-methyl-5-hepten-2-one;

, the aliphatic sulfur-containing compounds such. B .; 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercapto-hexyl butyrate; 3-acetylthiohexyl acetate; l-menthene-8-thiol;

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

aliphatic carboxylic acids and their esters such as e.g. (E) - and (Z) -3-hexenyl formate; ethylacetoacetate; isoamyl; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E) -2-hexenyl acetate; (E) - and (Z) -3-hexenyl acetate; Octyl acetate; 3-octyl acetate; l-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl;

hexyl butyrate; (E) - and (Z) -3-hexenyl isobutyrate; 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-noninate; Allyl-2-isoamyloxyacetat; Methyl-3,7-dimethyl-2,6-octadienoate; the acyclic terpene alcohols such as B. Citronellol; geraniol; nerol; linalool; Lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5, 7-octadien-2-ol; 2,6-dimethyl-3 5-octadien-2-ol; 3, 7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-l, 5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-l-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 B .; 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;

the cyclic terpene alcohols such as B. 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 formats,

Acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates,

Crotonates, tiglinates, 3-methyl-2-butenoate;

cyclic terpene aldehydes and ketones such as e.g. menthone; menthone; 8th-

Mercaptomenthan-3-one; carvone; camphor; fenchon; alpha-ionone; beta-ionone; alpha-n-methyl ionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-Rron; alpha-damascone; beta-damascone; 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; Dihydronootkaton; alpha-sinensal; beta-sinensal; Acetylated cedarwood oil (methyl cedryl ketone);

cyclic alcohols such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2, Z5, E9-cyclododecatrien-l-ol; 2-isobutyl-4-methyl tetrahydro-2H-pyran-4-ol; cycloaliphatic alcohols such as alpha, 3,3-trimethylcyclohexylmethanol; 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-l-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-l-yl) pentan-2-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-l-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 e.g. cineol; cedryl methyl ether; Cyclododecyl methyl ether; (Ethoxymethoxy) cyclododecane; alpha-Cedrenepoxid;

3a, 6,6,9a-tetramethyldodecahydronaphtho [2, 1 -b] furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho [2, l-b] furan; 1,5,9-trimethyl-13-oxabicyclo [10.1.0] trideca-4,8-diene; rose oxide; 2- (2,4-dimethyl-3-cyclohexen-l-yl) -5-methyl-5- (l-methylpropyl) -1,3-dioxane;

cyclic and macrocychic ketones such as 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-l-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4- (l-ethoxy-vinyl) -3,3,5,5-tetramethylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-dihydro-1, 1, 2,3, 3-pentamethyl-4 (5H) -indanone; 8-cyclohexadecen-1-one; 9-cycloheptadecen-l-one; cyclopentadecanone; cyclohexadecanone;

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

the esters of cyclic alcohols such as e.g. 2-tert-butylcyclohexyl acetate; 4-tert-butyl cyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; Deca- hydro-2-naphthylacetate; 3-Pentyltetτahydro-2H-pyran-4-yl acetate; Decahydro-2,5,5,8a-tetramethyl-2-naphthylacetate; 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-indenylpropionate;

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

the ester of cycloahphatic carboxylic acids such as. B. allyl-3-cyclohexylpropionate; Allylcyclohexyloxyacetat; ice and trans methyl dihydrojasmonate; ice and trans

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;

araliphatic alcohols such as e.g. benzyl alcohol; 1-phenylethyl; 2

phenylethyl; 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-l-ol; 4-methoxybenzyl; l- (4-isopropylphenyl) ethanol;

the esters of araliphatic alcohols and aliphatic carboxylic acids such as e.g.

benzyl acetate; benzylpropionate; benzyl isobutyrate; Benzylisovalerianat; 2-phenyl ethyl acetate; 2-phenylethyl propionate; 2-Phenylethylisobutyrat; 2-phenylethyl iso valerianate; 1-phenylethyl acetate; alpha-Trichlormethylbenzylacetat; alpha, alpha-di- methylphenylethylacetat; alpha, alpha-Dimethylphenylethylbutyrat; cinnamyl; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

the araliphatic ether such as e.g. 2-phenylethyl; 2-phenylethyl isoamyl ether; 2-Phenylethyl-l-ethoxyethyl ether; phenylacetaldehyde; Phenyl acetaldehyde diethylacetal; Hydratropaaldehyddimethylacetal; Phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-l, 3-dioxane; 4,4a, 5,9b-tetrahydroindeno- [1, 2-d] -m-dioxin; 4,4a, 5,9b-tetrahydro-2,4-dimethylindeno [1,2-d] -m-dioxin;

aromatic and araliphatic aldehydes such as e.g. benzaldehyde; Phenylacetal dehyde; 3-phenylpropanal; Hydratropaaldehyd; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3- (4-ethylphenyl) -2,2-dimethylρroρanal; 2-methyl-3- (4-isopropylphenyl) propanal; 2-Methyl-3- (4-tert-butylphenyl) propanal; 3 - (4-tert-butylphenyl) propanal; cinnamic aldehyde; alpha-Butylzimtaldehyd; alpha-amyl cinnamic aldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4

Hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylene dioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3- (4-methoxyphenyl) propanal; 2-methyl-3- (4-methylenedioxyphenyl) propanal;

aromatic and araliphatic ketones such as 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-indanylmethyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; l- [2,3-dihydro-l, l, 2,6-tetramethyl-3- (l-methylethyl) - lH-5-indenyl] ethanone; 5 ', 6' ₅ 7 ', 8'-tetrahydro-3', 5 ', 5', 6 ', 8', 8'-hexamethyl-2-aceto-naphthone;

aromatic and araliphatic carboxylic acids and their esters such as e.g.

benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate;

Phenylethyl phenylacetate; Methylcinnmat; ethylcinnamate; Benzyl; phenyl ethylcinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; Isoamyl salicylate; hexyl salicylate; cyclohexyl; Cis-3-hexenyl salicylate; Benzyl salicylate; phenylethyl; Methyl-2,4-dihydroxy-3,6-dimethylbenzoate; Ethyl 3-phenylglycidate; Ethyl 3-methyl-3-phenylglycidate;

the nitrogenous aromatic compounds such as e.g. 2,4,6-trinitro-l, 3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert.-butylacetophenone; Cinnamic acid nitrile; 5-phenyl-3-methyl-2-pentensäurenitril; 5-phenyl-3-methylpentanoic acid nitrile; methyl anthranilate; Methyl N-methylanthranilate; See bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-Isopropyl; 6-isobutylquinoline; 6-sec-butylquinoline; indole; skatol; 2-methoxy-3-isoρropylρyrazin; 2-isobutyl-3-methoxypyrazine;

of phenols, phenyl ethers and phenyl esters such as e.g. estragole; anethole; eugenol;

Eugenylmethylether; isoeugenol; Isoeugenylmethylether; thymol; carvacrol; Diphenyl ether; beta-naphthyl methyl ether; beta-Naphthylethylether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methyl phenol; 2

Ethoxy-5 - (1-propenyl) phenol; p-Kresylphenylacetat;

the heterocychic compounds such as e.g. 2,5-dimethyl-4-hydroxy-2H-furan-3-one;

2-ethyl-4-hydroxy-5-methyl-2H-furan-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-l, 4-octanolide; 1,4-nonanolide; 1,4-

decanolide; 8-decen-l, 4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1.15 pentadecanolide; ice and trans-l l-pentadecene-l, 15-olide; ice and trans-12-pentadecene-1,15-olide; 1,16-hexadecanolide; 9-hexadecene-l, 16-olide; 10- oxa- 1,16-hexadecanolide; 11-oxa- 1, 16-hexadecanolide; 12-oxa- 1, 16-hexadecanolide; Ethylene-l, 12-dodecanedioate; Ethylene-l, 13-tridecandioat; coumarin; 2,3-dihydrocoumarin; Oetahydrocumarin. The perfume oils containing the compounds 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, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate.

Furthermore, the paranol oils containing butanols according to the invention can be adsorbed on a carrier which ensures both a fine distribution of the odoriferous substances in the product and a controlled release during use. Such supports can be porous inorganic materials such as e.g. Light sulfate, silica gels, zeolites, gypsum, clays, clay granules, gas concrete or organic materials such as wood and cellulose-based substances.

The parflime oils containing the compounds according to the invention can also be micro-encapsulated, spray-dried, present as inclusion complexes or as extrusion products and added in this form to the product to be perfumed.

If necessary, the properties of the parflime 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 preferably waxy plastics such as Polyvinyl alcohol can be used.

The microencapsulation of parflime oils can, for example, by the so-called

Coacervation procedures using capsule materials e.g. made of polyurethane-like materials or soft gelatin. The spray-dried perfume oils can be produced, for example, by spray drying an emulsion or dispersion containing the parflime oil, and modified starches, proteins, dextrin and vegetable gums can be used as carriers. Inclusion-

Complexes can, for example, by adding dispersions of parflime oil and Cyclodextrins or urea derivatives can be prepared 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, for example isopropanol.

The 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 e.g. Perfume extras, eau de perfumes, eau de toilettes, aftershaves, eau de colognes, pre-shave products, splash colognes and scented refreshing wipes as well as the scenting of acidic, alkaline and neutral cleaning agents, e.g. Floor cleaners, window glass cleaners,

- Dishwashing liquid, bathroom and sanitary cleaners, scouring milk, solid and liquid

, Toilet cleaners, powder and foam-shaped carpet cleaners, liquid detergents, powder detergents, laundry pretreatment agents such as bleach, soaking agents and stain removers, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants and air fresheners in liquid, gel-like or on a solid carrier. Aerosol sprays, waxes and polishes such as furniture polishes, floor waxes, shoe creams and personal care products such as solid and liquid

Soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of oil-in-water, water-in-oil and water-in-oil-in-water types, 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, hair creams and lotions, deodorants and antiperspirants such as armpit sprays, roll-ons, deodorants, deodorants, cosmetics, roll-ons, deodorants, cosmetics e.g. eyeshadows, nail polishes, make-ups, lipsticks, Mascara and candles, lamp oils, incense sticks, insecticides, repellents, fuels.

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

The following examples illustrate the invention:

Examples:

example 1

3-cycldodecylbutan-2-ol, l-cyclododecylbutan-2-ol

215 g of cyclododecene and 1172 g of butan-2-one are placed in a 51 autoclave and heated to a temperature of 160 ° C., a pressure of 4.5 bar being established. A mixture of 234 g of butan-2-one and 86 g of di-tert-butyl peroxide is metered in over the course of 4 hours. After the end of the dose, the reaction is allowed to continue for a further 2 hours.

After 1320 g of butan-2-one has been distilled off, 80 g of addition products (ketones) are obtained by distillation at 120-130 ° C./1 mbar.

The total amount of the addition products is dissolved in 350 ml of isopropanol and in an autoclave using 2.8 g of ruthenium on activated carbon (moist; water content approx. 50% by weight, Ru content: 5% by weight based on the dry catalyst ) hydrogenated as a catalyst at a hydrogen pressure of 20 bar and a temperature of 150 ° C within 4 hours. It is filtered off from the catalyst and then distilled at 140-150 ° C / 2-3 mbar. 65 g are obtained

Product containing 84% 3-cycldodecylbutan-2-ol (44% isomer 1, 40% isomer 2) and 11% l-cyclododecylbutan-2-ol.

Smell: wood, cedar, amber, high adhesion

To determine the structure, the individual components were separated by high pressure liquid chromatography. 3-Cyclododecylbutan-2-ol

^ NMR spectrum (400 MHz; CDC1 ₃ ; TMS = 0 ppm)

Isomer 1: Cl: 3H, J = 6.3 Hz d, δ = 1.208 ppm; C2: IH, m, δ = 3.804 ppm; C4: 3H, J = 6.9 Hz d, δ = 0.890 ppm; C5: IH, m, δ = 1.522 ppm; Balance: 24H, m, δ = 1.150 ppm - 1.460 ppm

Isomer 2: Cl: 3H, J = 6.2 Hz d, δ = 1.160 ppm; C2: IH, J = 5.2Hz d, J = 6.2Hz q, J = 7.2Hz d, δ = 3.724 ppm; C5: IH, m, δ = 1.755 ppm; C4: 3H, J = 7.0 Hz d, δ = 0.765

_, ppm; OH: IH, J = 5.2 Hz d, δ = 1.204 ppm; Balance: 23H, m, δ = 1.110 ppm - 1.500 ppm mass spectrum:

Isomer 1: 222 (14); 166 (47); 111 (40); 97 (79); 83 (77); 69 (63); 55 (100); 41 (54) Isomer 2: 222 (21); 166 (63); 111 (41); 97 (79); 83 (84); 69 (70); 55 (100); 41 (60)

1-cyclododecylbutan-2-ol:

Cl: 3H, J = 7.4 Hz t, δ = 0.947 ppm; C2: 2H, m wide, δ = 1.462 ppm; C3: IH, m, δ =

3.615 ppm; OH: IH, J = 5.0 Hz d, δ = 1.218 ppm; C5: IH, m, δ = 1.634 ppm; Rest:

24H, m, δ = 1.130 ppm - 1.446 ppm

Mass spectrum: l-cyclododecylbutan-2-ol: 222 (6.5); 166 (66); 111 (52); 97 (100); 83 (70); 69 _. (61); 55 (91); 41 (62) 19-

Example 2 Fragrance Composition 1

200

200

20 -

The addition of 80 g of product in accordance with Example 1 brings about a woody, cedar, soft, powdery and also a clear, modern, amber character. This complex effect is otherwise only possible through the combination of several fragrances such as cedryl ketone (H&R), Boisambrene forte (Cognis), Kephalis (Givaudan Roure) and ambroxide. (H&R).

Example 3 Fragrance Composition 2

2004/002930

2004/002930

21

By replacing Cedramber with 90g product according to Example 1, the fragrance composition is characterized by a longer adhesion. The fresh character of the perfume composition is also supported. ,

Example 4: MIC values / determination of the minimum inhibitory concentration

^• The minimum inhibitory concentration (MIC) of the claimed substances was determined in the serial dilution test (H. Brandis, G. Pulverer: Textbook of Medical Microbiology. 6th revised edition, Gustav Fischer Verlag Stuttgart, 1988;

Page 200ff.) Against various cosmetically relevant germs. The test was transferred to the microtiter plate format and the concentration at which the MIC value was determined. after 16 hours of incubation at the wavelength of 620 nm, no significant increase in turbidity compared to the controls was observed.

The results are shown in Table 1.

Table 1:

- 22 -

- 22 -

Example 5: Aerosol Spray

% By weight of octyldodecanol 0.50

Product according to example 1 0.20 perfume, preservatives q.s. Ethanol ad 100.00

The liquid phase obtained by mixing the respective constituents together with a propane-butane mixture (2: 7) in a ratio of 39:61 in

Filled aerosol container.

Example 6: Pump spray

% By weight

PEG-40 hydrogenated castor oil 2.00

Glycerin 1.00

Product according to example 1 0.20

Perfume, preservatives q.s.

Water ad 100.00

Example 7: Roll-on-Gel

% By weight

1,3-butylene glycol 2.00

PEG-40 hydrogenated castor oil 2.00

Hydroxyethyl cellulose 0.50

Product according to example 1 0.30

Perfume, preservatives q.s.

Water ad 100.00

Claims

Patentansprtiche 1. Compound of the formula

A B 2. Mixture of compounds of the formulas A and B according to claim 1. 3. Perfumed product or fragrance composition containing a compound according to claim 1 or a mixture of compounds according to claim 2. 4. fragrance composition according to claim 3, comprising a compound according to claim 1 or a mixture of compounds according to claim 2 in one Amount of 0.05 to 50 wt .-%, based on the total mass of the fragrance composition. 5. Use of a compound according to claim 1 or a mixture according to claim 2 as a fragrance. 6. Use of a compound according to claim 1 as an antimicrobial agent, in particular against gram-positive bacteria. 7. Preparation comprising an antimicrobially effective amount of A compound according to claim 1 or a mixture according to claim 2. 8. A method for producing a connection according to spoke 1 or one Mixture according to claim 2, characterized in that in a step a) Cyclododecen and butan-2-one reacted with one another and in a subsequent step b) the addition products formed in step a) are reduced. 9. The method according spoke 8, characterized in that the molar Ratio of butan-2-one to cyclododecene in step a) is between 400 and 1. 10. The method according spoke 8 or 9, characterized in that step a) is carried out in the presence of a radical initiator. 11. The method according to claim 10, characterized in that azo or peroxide compounds are used as the radical initiator. 12. The method according to at least one of claims 8 to 11, characterized in that step a) is carried out at a temperature in the range of 80 to 220 ° C. 13. The method according to at least one of claims 8 to 12, characterized in that step a) is carried out at a pressure in the range from 2 to 20 bar. 14. The method according to at least one of claims 8 to 13, characterized in that in step b) the addition products are hydrogenated. 15. The method according to claim 14, characterized in that a heterogeneous hydrogenation catalyst of group VJJIb of the periodic table is used in the hydrogenation. 6. The method according to at least one of claims 14 to 15, characterized in that the hydrogenation is carried out at a hydrogen pressure of 5 to 50 bar.