Patent Description:
Further aspects and preferred embodiments of the present invention are apparent from the following description, the attached examples and, in particular, the attached patent claims.

On the part of the perfume industry, there is a particular interest in a controlled and long-lasting release of certain fragrances. This applies in particular to fragrances with a high volatility or low substantivity. The washing of textiles, for example, is an area where there is a great desire to be able to perceive the pleasant odours of the fragrance substances or perfume oils used in detergents or fabric softeners on the laundry for a long period of time after washing and drying of the textiles.

Precursors are known in the perfume industry and are formed, for example, from α,β-unsaturated carbonyl compounds and thiols by way of Michael additions. They usually release a pleasantly smelling α,β-unsaturated carbonyl compound, such as an α,β-unsaturated aldehyde or ketone. This release takes place in a controlled manner and thus enables a sensorial perception of highly volatile fragrance substances that would not be achievable if the aldehyde or ketone compounds were used directly in a perfume oil.

There is a great demand in the perfume industry for precursors that are capable of releasing several fragrance substances simultaneously or over time. This would allow an expansion of the perfumery palette. There is also a particularly high demand for fragrance substances that have a strong olfactory effect even at low dosages (i.e. a low odorant threshold), so-called "high impact" fragrance substances.

The known precursors are limited to the release of fragrant α,β-unsaturated carbonyl compounds. Due to the unpleasant odour impression of common, especially short-chain, thiol compounds, the prior art teaches the use of thiol compounds that are as odourless as possible for the formation of precursors. In patent application <CIT>, for example, <NUM>-mercaptopropyltriethoxysilanes and <NUM>-mercaptopropyltrimethoxysilanes are reacted with α,β-unsaturated carbonyl compounds to form precursors. Only the released α,β-unsaturated carbonyl compounds serve as fragrance substances in the teaching described therein.

In patent application <CIT>, short-chain thiol compounds are used as thiol compounds to form the precursors. Also in this publication, only the α,β-unsaturated carbonyl compounds released from the precursors serve as fragrance substances. It is described that the unpleasant odour of the short-chain thiol compounds, which are also released from the precursors, surprisingly does not affect the positive olfactory effect of the α,β-unsaturated carbonyl compounds too negatively, so that overall, unexpectedly, the positive olfactory impression of the released α,β-unsaturated carbonyl compounds dominates.

<CIT> discloses the use of a compound of formula (I), a composition of matter comprising a compound of formula (I) and a fragrance ingredient comprising a compound of formula (I)
<CHM>
wherein inter alia R<NUM> is defined as H or a residue comprising <NUM> to <NUM> carbon atoms and R<NUM> is defined as a residue comprising <NUM> to <NUM> carbon atoms.

<CIT> relates to a perfuming composition comprising at least two pro-perfume compounds. It further concerns a perfumed consumer product comprising the perfuming composition described therein, as well as the use of the perfuming composition for improving, enhancing, conferring and/or modifying the fragrance impression and/or fragrance intensity of a consumer product.

<NPL> relates to the spontaneous release of natural aroma compounds from specific β-alkylthioalkanones.

<NPL> relates to specific thioether profragrances and the parameters influencing the performance of precursor-based fragrance delivery in functional perfumery.

The primary task was to provide improved precursors that meet the above requirements, i.e. are capable of releasing pleasantly smelling, high impact fragrances in a controlled manner and over a long period of time. This release should preferably be possible from surfaces treated with the precursors, especially from textiles.

Surprisingly, this task is solved by a compound of formula (I)
<CHM>.

The ring system as defined in (ii) above includes the carbon atoms to which R and R<NUM> are bonded and the ring system as defined in (iii) above includes the carbon atoms to which R and R<NUM> are bonded.

The compound of formula (I) (i.e. the precursor) may be in the form of a pure diastereomer or stereoisomer or in the form of any mixture of said isomers.

The compounds of formula (I) as defined herein have not been previously known in the perfume industry. The suitability of the compounds of formula (I) as precursors for the release of fragrance substances was therefore unexpected. In the course of the studies underlying this application, and contrary to the teaching in the prior art with respect to the negative olfactory influence of the released thiol compound, it was surprisingly found that the compounds of formula (I) according to the present invention release both a pleasantly smelling (high impact) α,β-unsaturated aldehyde or ketone and a pleasantly smelling (high impact) thiol compound. Said release of the two (or more) different fragrance substances, and thus their sensorial perception, advantageously occurs in a controlled way, preferably at different points in time, which was particularly surprising. The sensory odour impression of the released thiol compound (e.g. sulphurous-fruity notes), for instance, is very intensely perceptible on damp laundry, especially directly after washing, while the released α,β-unsaturated aldehyde or ketone provides a long-lasting, fresh odour impression on dried laundry (e.g. fresh, green and/or flowery notes).

Further advantages of the present invention are:.

Also described herein is a compound of formula (I), wherein.

Residue R<NUM> of the compounds of formula (I) according to the invention does not comprise any Si atoms.

According to another preferred embodiment of the compound of formula (I) according to the invention, R<NUM> is not an n-butyl, n-pentyl, or n-hexyl (or <NUM>-propyl) residue.

According to another preferred embodiment of the compound of formula (I) according to the invention, R<NUM> is not a residue of the following formula (<NUM>-hydroxybutyl):
<CHM>.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising one, two or more ether functional groups.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising one ether functional group.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising two ether functional groups.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising one, two or more alcohol functional groups.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising one alcohol functional group.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising two alcohol functional groups.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising one, two or more ketone functional groups.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising one ketone functional group.

Also described herein is a compound of formula (I), wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM>, preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, more preferably C<NUM> to C<NUM>, most preferably C<NUM> to C<NUM>, linear, cyclic or branched alkyl residues, additionally comprising two ketone functional groups.

According to a preferred embodiment of the compound of formula (I) according to the invention, R is selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

According to another preferred embodiment of the compound of formula (I) according to the invention, R' is selected from the group consisting of
<CHM>.

According to another preferred embodiment of the compound of formula (I) according to the invention, R<NUM> is selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>.

According to another preferred embodiment of the compound of formula (I) according to invention, R<NUM> is selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

According to a particularly preferred embodiment of the compound of formula (I) according to the invention,.

According to another particularly preferred embodiment of the compound of formula (I) according to the invention,
residue
<CHM>.

According to a preferred embodiment, the compound of formula (I) according to the invention is obtained or obtainable by a [<NUM>,<NUM>]-addition reaction between:.

- an α,β-unsaturated aldehyde or ketone (Michael acceptor, electrophile) selected from the group consisting of (group of compounds as shown below in the column entitled "Structure" of Table <NUM>).

and
- a thiol (Michael donor, nucleophile) selected from the group consisting of (group of compounds as shown below in the column entitled "Structure" of Table <NUM>).

According to a preferred embodiment, Citral - i.e. a mixture of Neral and Geranial as shown above in Table <NUM> - is used as (a mixture of) α,β-unsaturated aldehyde(s) for the formation of a compound of formula (I).

The compounds of formula (I) according to the invention
<CHM>
release a (pleasantly smelling, high impact) thiol, which is selected from the group consisting of compounds as shown above in the column entitled "Structure" of Table <NUM>, and a (pleasantly smelling, high impact) α,β-unsaturated aldehyde or ketone, which is preferably selected from the group consisting of compounds as shown above in the column entitled "Structure" of Table <NUM>, via the following decomposition reaction:
<CHM>.

Preferably, said release is triggered by certain pH values and/or temperatures, UV light, water, and/or oxygen.

According to a particularly preferred embodiment, the compound of formula (I) according to the invention is selected from the group consisting of (group of compounds as shown below in the column entitled "Structure" of Table <NUM>):.

According to a particularly preferred embodiment, the compound of formula (I) according to the invention is not
<CHM>.

Another aspect of the present invention relates to a fragrance substance mixture, preferably perfume oil, comprising or consisting of the following components:.

The one or more further fragrance substances are different from the compounds of formula (I) according to the invention.

Examples of further fragrance substances that can be advantageously combined with the compounds of formula (I) as defined herein within the scope of the present invention are known to the skilled person and can be found, for example, in <NPL>, or <NPL>.

According to a preferred embodiment of the fragrance substance mixture according to the invention, preferably perfume oil, the proportion of the total amount of compound(s) of formula (I) as defined herein in the fragrance substance mixture is <NUM> to <NUM> % by weight, preferably <NUM> to <NUM> % by weight, particularly preferably <NUM> to <NUM> % by weight, based on the total mass of the fragrance substance mixture.

Another aspect of the present invention relates to a method for producing a fragrance substance mixture, preferably a perfume oil, as defined above, comprising or consisting of the following step:
Mixing of one or more compound(s) of formula (I) as defined herein with one or more further fragrance substances.

Furthermore, fragrance substance mixtures, preferably perfume oils, according to the invention may be adsorbed on a carrier which provides both a fine distribution of the fragrance substance mixture, preferably perfume oil, in the perfumed product and a controlled release during application. Such carriers may be porous inorganic materials such as light sulphate, silica gels, zeolites, gypsums, clays, clay granules, gas concrete, etc. or organic materials such as wood, cellulose-based materials, sugar, dextrins (e.g. maltodextrin) or plastics such as PVC, polyvinyl acetates or polyurethanes. The combination of a fragrance substance mixture, preferably perfume oil, according to the invention and a carrier is also to be understood as a fragrance substance mixture, preferably perfume oil, of the invention or may be presented as a perfumed product according to the invention (as described below).

Fragrance substance mixtures, preferably perfume oils, or perfumed products of the invention (as described below) may also be microencapsulated, spray-dried, or may be provided as inclusion complexes or as extrusion products and, in the case of a fragrance substance mixture, preferably perfume oil, may be added in this form e.g. to a perfumed product to be perfumed (as described below).

If necessary, the properties of such modified mixtures or products can be further optimized by so-called "coating" with suitable materials with a view to a more targeted release of fragrance, preferably using wax-like plastics such as polyvinyl alcohol. The resulting products in turn represent products of the invention.

Microencapsulation can, for example, be achieved by the so-called coacervation method using capsule materials such as polyurethane-like substances or soft gelatin.

Spray-dried products are preferably produced by spray-drying an emulsion or dispersion containing the fragrance substance mixtures, preferably perfume oils, according to the invention, whereby modified starches, proteins, dextrin and vegetable gums can be used as carriers.

Inclusion complexes can be produced e.g. by incorporating dispersions of the fragrance substance mixtures, preferably perfume oils, according to the invention and cyclodextrins or urea derivatives into a suitable solvent, e.g. water.

Extrusion products can be obtained, e.g., by using the fragrance substance mixtures, preferably perfume oils, according to the invention with a suitable waxy substance and by extrusion followed by solidification, if necessary, in a suitable solvent, e.g. isopropanol.

Another aspect of the present invention relates to a perfumed product comprising one or more compound(s) of formula (I) as defined herein or a fragrance substance mixture, preferably a perfume oil, as defined herein, preferably in a sensorially effective amount.

Advantageously, the one or more compound(s) of formula (I) according to the invention positively impart or modify the odour of a perfumed product to which said compound(s) of formula (I) are added.

According to a preferred embodiment, the perfumed product is selected from the group consisting of perfume extracts, eau de parfums, eau de toilettes, aftershaves, eau de colognes, pre-shave products, splash colognes, perfumed refreshing cloths, acidic, alkaline and neutral detergents, textile fresheners, ironing aids, liquid detergents, powdered detergents, laundry pre-treatment agents, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, personal care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants and antiperspirants, decorative cosmetic products, candles, lamp oils, incense sticks, insecticides, repellents, and fuels, most preferably is a fabric softener.

According to a preferred embodiment of the perfumed product according to the invention, the proportion of the total amount of fragrance substance mixture as defined herein, preferably perfume oil, in the perfumed product is <NUM> to <NUM> % by weight, preferably <NUM> to <NUM> % by weight, particularly preferably <NUM> to <NUM> % by weight, based on the total mass of the perfumed product.

Another aspect of the present invention relates to a method for producing a perfumed product, preferably a perfumed product as defined herein, comprising or consisting of the following steps:.

Another aspect of the present invention relates to the use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of one, two, three or more different pleasantly smelling fragrance substances, preferably wherein the two or more different fragrance substances are released and/or sensorially perceived at the same or different, preferably different, point(s) in time (if two or more different fragrance substances are released).

Another aspect of the present invention relates to the use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of a pleasantly smelling thiol and of a pleasantly smelling α,β-unsaturated aldehyde or ketone, preferably wherein the thiol and the α,β-unsaturated aldehyde or ketone are released and/or sensorially perceived at the same or different, preferably different, point(s) in time.

Another aspect of the present invention relates to the use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of a (pleasantly smelling) thiol selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and/or, preferably and, of a (pleasantly smelling) α,β-unsaturated aldehyde or ketone selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
preferably wherein the thiol and the α,β-unsaturated aldehyde or ketone are released and/or sensorially perceived at the same or different, preferably different, point(s) in time.

Another aspect of the present invention relates to the use of a compound of formula (I), wherein residue
<CHM>
of the compound of formula (I) is selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and/or, preferably and, wherein residue R<NUM> of the compound of formula (I) is selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
as a precursor for the (controlled) release of a (pleasantly smelling) thiol selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and/or, preferably and, of a (pleasantly smelling) α,β-unsaturated aldehyde or ketone selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
preferably wherein the thiol and the α,β-unsaturated aldehyde or ketone are released and/or sensorially perceived at the same or different, preferably different, point(s) in time.

The thiols and α,β-unsaturated aldehydes or ketones released by the compounds of formula (I) according to the invention and/or used for the formation of a compound of formula (I) according to the invention may be in the form of a pure diastereomer or stereoisomer or in the form of any mixture of said isomers.

According to a preferred embodiment of the use according to the invention, the thiol that is released from the compound of formula (I) as defined herein is released and/or sensorially perceived before the α,β-unsaturated aldehyde or ketone that is released from the (same) compound of formula (I) as defined herein.

According to an alternative embodiment of the use according to the invention, the α,β-unsaturated aldehyde or ketone that is released from the compound of formula (I) as defined herein is released and/or sensorially perceived before the thiol that is released from the (same) compound of formula (I) as defined herein.

According to a further alternative embodiment of the use according to the invention, the thiol that is released from the compound of formula (I) as defined herein and the α,β-unsaturated aldehyde or ketone that is released from the (same) compound of formula (I) as defined herein are released and/or sensorially perceived at the same time.

Preferably, a pleasantly smelling thiol has one or more odour notes selected from the group consisting of grapefruit, cassis, onion, fruity, exotic fruit, guava, breath of smoker, sulphur, (burnt) plastic, (minty) green, rose oxide, green pepper, liver sausage, buchu (Asian chives), gasoline, juicy, natural, cat grass, meat broth ("Fleischbrühe"), cheesy, camembert, cheese in the fridge, fresh, hot rubber, petrol, violet, blackcurrant, catnip (grass), zestral, anisic, mushroom, soup, leek, agrumen, peach, meat, pine, mango, durian, jackfruit, artichoke, and apricot,
more preferably a pleasantly smelling thiol has one or more odour notes selected from the group consisting of grapefruit, cassis, onion, fruity, exotic fruit, guava, sulphur, (minty) green, rose oxide, green pepper, liver sausage, buchu (Asian chives), juicy, natural, cat grass, meat broth ("Fleischbrühe"), cheesy, camembert, fresh, violet, blackcurrant, catnip (grass), zestral, anisic, mushroom, soup, leek, agrumen, peach, meat, pine, mango, durian, jackfruit, artichoke, and apricot.

Another aspect of the present invention relates to a method for the (controlled) release of one, two, three or more different pleasantly smelling fragrance substances comprising or consisting of the following steps:.

Another aspect of the present invention relates to a method for the (controlled) release of a pleasantly smelling thiol and of a pleasantly smelling α,β-unsaturated aldehyde or ketone comprising or consisting of the following steps:.

According to a preferred embodiment of the method according to the invention, the thiol that is released from the compound of formula (I) as defined herein in step (c) is released and/or sensorially perceived before the α,β-unsaturated aldehyde or ketone that is released from the (same) compound of formula (I) as defined herein in step (c).

According to an alternative embodiment of the method according to the invention, the α,β-unsaturated aldehyde or ketone that is released from the compound of formula (I) as defined herein in step (c) is released and/or sensorially perceived before the thiol that is released from the (same) compound of formula (I) as defined herein in step (c).

According to a further alternative embodiment of the method according to the invention, the thiol that is released from the compound of formula (I) as defined herein in step (c) and the α,β-unsaturated aldehyde or ketone that is released from the (same) compound of formula (I) as defined herein in step (c) are released and/or sensorially perceived at the same time.

Another aspect of the present invention relates to a method for the (controlled) release of a (pleasantly smelling) thiol selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and/or, preferably and, of a (pleasantly smelling) α,β-unsaturated aldehyde or ketone selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
comprising or consisting of the following steps:.

Another aspect of the present invention relates to a thiol selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

During the studies underlying the present invention, it was surprisingly found that the thiols as defined above can serve as pleasantly smelling, high impact fragrances, preferably after release from a compound of formula (I) according to the invention.

The thiols according to the invention can be obtained by applying the procedures disclosed in <CIT>.

An odour description of the thiols according to the invention can be found in Table <NUM> above.

Another aspect of the present invention thus relates to the use of one or more thiol(s) according to the invention as a fragrance substance.

Another aspect of the present invention relates to a method for perfuming hair, skin, textile fibres, surfaces and/or ambient air comprising or consisting of the following steps:.

Another aspect of the present invention relates to the use of a compound of formula (I) as defined herein or of a fragrance substance mixture, preferably perfume oil, as defined herein as a perfuming ingredient.

Another aspect of the present invention relates to the use a compound of formula (I) as defined herein or of a fragrance substance mixture, preferably perfume oil, as defined herein for perfuming hair, skin, textile fibres, surfaces and/or ambient air.

Another aspect of the present invention relates to a fragrance substance mixture, preferably perfume oil, as defined herein, wherein the amount of compound(s) of formula (I) is sufficient.

Another aspect of the present invention relates to the use of one or more compound(s) of formula (I) as defined herein or of a fragrance substance mixture, preferably perfume oil, as defined herein.

Another aspect of the present invention relates to a method.

comprising the following step:
Mixing the unpleasantly and/or pleasantly smelling substances with one or more compound(s) of formula (I) as defined herein or with a fragrance substance mixture, preferably perfume oil, as defined herein, wherein the amount of the one or more compound(s) of formula (I) as defined herein or of the fragrance substance mixture, preferably perfume oil, as defined herein is sufficient to (a) reduce or to mask the unpleasant odour impression(s) of the unpleasantly smelling substance(s) and/or (b) enhance the pleasant odour impression(s) of the pleasantly smelling substance(s).

What has been stated herein in connection with the fragrance substance mixtures, perfumed products, methods, uses and thiols according to the invention applies accordingly to preferred embodiments of the compounds of formula (I) according to the invention, and vice versa.

In the following, the invention is explained in more detail using examples.

In a <NUM> stirring apparatus with magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath, <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylguanidine, <NUM> of <NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propanethiol and <NUM> of tetrahydrofuran were added under a nitrogen atmosphere at <NUM>. At <NUM>-<NUM>, <NUM> of delta-damascone were added dropwise within <NUM> hour. For post-reaction, stirring was continued for <NUM> hours at <NUM>-<NUM>. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature and then the solvents were evaporated on the rotary evaporator. <NUM> crude yield of <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethyl-cyclohex-<NUM>-en-<NUM>-yl)butan-<NUM>-one, with a GC content of <NUM>%, were obtained. For further purification, the crude yield was chromatographed over a silica gel column with hexane:diethyl ether (<NUM>:<NUM>) as eluent. <NUM> of <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethylcyclohex-<NUM>-en-<NUM>-yl)butan-<NUM>-one, with a GC content of <NUM>%, were obtained.

Mass spectrometric analysis of product:
m/z: <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>).

In a <NUM> stirring apparatus with magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath, <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylguanidine, <NUM> of <NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propanethiol and <NUM> of tetrahydrofuran were placed under a nitrogen atmosphere at <NUM>. At <NUM>-<NUM>, <NUM> of <NUM>-(E)-decenal were added dropwise within <NUM> hour. For post-reaction, stirring was continued for <NUM> hours at <NUM>-<NUM>. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature and then the solvents were evaporated on the rotary evaporator. <NUM> crude yield of <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyldecanal, with a GC content of <NUM>%, were obtained. For further purification, the crude yield was chromatographed over a silica gel column with hexane:diethyl ether (<NUM>:<NUM>) as eluent. <NUM> of <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyldecanal, with a GC content of <NUM>%, were obtained.

In a <NUM> stirring apparatus with magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath, <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylguanidine, <NUM> of <NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propane-<NUM>-thiol and tetrahydrofuran (<NUM>) were added under a nitrogen atmosphere at <NUM>. At <NUM>-<NUM>, <NUM> of (E)-hex-<NUM>-enal were added dropwise within <NUM> hour. For post-reaction, stirring was continued for <NUM> hours at <NUM>-<NUM>. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature and then the solvents were evaporated on the rotary evaporator. <NUM> crude of <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyl-hexanal were obtained. For further purification, the crude yield was chromatographed over a silica gel column with hexane:diethyl ether (<NUM>:<NUM>) as eluent. <NUM> of <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanylhexanal, with a GC content of <NUM>%, were obtained.

Mass spectrometric analysis of product:
m/z: <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>).

In a <NUM> stirring apparatus with magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath, <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylguanidine, <NUM> of <NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propane-<NUM>-thiol and tetrahydrofuran (<NUM>) were added under a nitrogen atmosphere at <NUM>. At <NUM>-<NUM>, <NUM> of (E)-[<NUM>]-(<NUM>,<NUM>,<NUM>-trimethylcyclohex-<NUM>-en-<NUM>-yl)but-<NUM>-en-<NUM>-one were added dropwise within <NUM> hour. For post-reaction, stirring was continued for <NUM> hours at <NUM>-<NUM>. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature and then the solvents were evaporated on the rotary evaporator. <NUM> crude of <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethyl-<NUM>-cyclohexen-<NUM>-yl)-<NUM>-butan-<NUM>-one were obtained. For further purification, the crude yield was chromatographed over a silica gel column with hexane:diethyl ether (<NUM>:<NUM>) as eluent. <NUM> of <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethyl-<NUM>-cyclohexen-<NUM>-yl)-<NUM>-butan-<NUM>-one, with a GC content of <NUM>%, were obtained.

Mass spectrometric analysis of product:
m/z: <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>).

In a <NUM> stirring apparatus with magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath, <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylguanidine, <NUM> of <NUM>-ethoxytricyclo[<NUM>. <NUM>,<NUM>]decane-<NUM>-thiol and tetrahydrofuran (<NUM>) were added under a nitrogen atmosphere at <NUM>. At <NUM>-<NUM>, <NUM> of (E)-[<NUM>]-(<NUM>,<NUM>,<NUM>-trimethylcyclohex-<NUM>-en-<NUM>-yl)but-<NUM>-en-<NUM>-one were added dropwise within <NUM> hours. For post-reaction, stirring was continued for <NUM> hours at <NUM>-<NUM>. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature and then the solvents were evaporated on the rotary evaporator. <NUM> crude of <NUM>-ethoxytricyclo[<NUM>. <NUM>,<NUM>]decane-<NUM>-sulfanyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethylcyclohex-<NUM>-en-<NUM>-yl)butan-<NUM>-one were obtained.

To <NUM> <NUM>-methyl-<NUM>-(<NUM>-methyl-prop-<NUM>-enyl)tetrahydropyran and <NUM> thioacetic acid was added <NUM> <NUM>,<NUM>-azobis-(<NUM>-methyl-propionitril, AIBN) at <NUM>-<NUM> and stirred at room temperature for <NUM>. Afterwards, the mixture is slowly heated to <NUM> and stirred for <NUM> at <NUM> until complete conversion. After cooling to room temperature, the product is obtained by distillation (<NUM> mbar, <NUM>-<NUM>) to yield <NUM> (<NUM>%) of <NUM>-methyl-(<NUM>-<NUM>-methyltetrahdyropyran-<NUM>-yl)propyl-ethanethioate as a mixture of isomers.

El-MS m/z (%): <NUM> (<NUM>, [M]+), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>).

A solution of <NUM> <NUM>-methyl-(<NUM>-<NUM>-methyltetrahdyropyran-<NUM>-yl)propyl-ethanethioate in dry methanol (<NUM>) was treated with <NUM> potassium carbonate und nitrogen and stirred over night until complete conversion. Afterwards, the mixture is acidified by <NUM> hydrochloric acid (<NUM>) and <NUM> H<NUM>O and <NUM> Et<NUM>O are added. The organic phase is separated and the aqueous phase is extracted with <NUM> Et<NUM>O. The combined organic phases are washed with brine (<NUM>), dried over sodium sulfate and reduced in vacuum. The crude product is purified by distillation (<NUM> mbar, <NUM>-<NUM>) to obtain <NUM> (<NUM>%) <NUM>-methyl-<NUM>-[<NUM>-methyltetrahydropyran-<NUM>-yl]propane-<NUM>-thiol as a mixture of isomers.

EI-MS m/z (%): <NUM> (<NUM>, [M]+), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>), <NUM> (<NUM>).

To <NUM> <NUM>-methoxytricyclo[<NUM>. <NUM>,<NUM>]dec-<NUM>-ene and <NUM> thioacetic acid was added <NUM> <NUM>,<NUM>-azobis-(<NUM>-methyl-propionitril, AIBN) at <NUM>-<NUM> and stirred at room temperature for <NUM>. Afterwards, the mixture is slowly heated to <NUM> and stirred for <NUM> at <NUM> until complete conversion. After cooling to room temperature, the product is obtained by distillation (<NUM> mbar, <NUM>-<NUM>) to yield <NUM> (<NUM>%) of (<NUM>-methoxytricyclo-<NUM>-[<NUM>. <NUM>,<NUM>]decanyl)ethanethioate as a mixture of isomers.

A solution of <NUM> (<NUM>-methoxytricyclo-<NUM>-[<NUM>. <NUM>,<NUM>]decanyl)ethanethioate in dry methanol (<NUM>) was treated with <NUM> potassium carbonate und nitrogen and stirred over night until complete conversion. The solvent is evaporated under reduced pressure and <NUM> MTBE is added. The organic phase is separated and the aqueous phase is extracted with <NUM> MTBE. The combined organic phases are washed with saturated sodium hydrogencarbonate solution, sodium sulfite solution and brine, dried over sodium sulfate and reduced under reduced pressure. The crude product is purified by distillation (<NUM> mbar, <NUM>-<NUM>) to obtain <NUM> (<NUM>%) <NUM>-ethoxytricyclo[<NUM>. <NUM>,<NUM>]decane-<NUM>-thiol as a mixture of isomers.

<NUM> of a solution containing <NUM>% compound of formula (I) according to the present invention in fabric softener (cf. Table <NUM> below for composition of the fabric softener) was added to <NUM> I H<NUM>O in a <NUM> I beaker and mixed for a short period of time to form a homogeneous solution.

Five pieces of cotton fabric (<NUM> x <NUM>, <NUM> each) were added and stirred using a magnetic stirrer for <NUM> at room temperature. Afterwards, the pieces of cotton fabric were individually wrung (approx. <NUM> each) and dried on a laundry rack in a self-made closed drying chamber (<NUM>) at a constant air exchange and temperature of <NUM>. At defined points in time, volatiles were adsorbed on a Tenax® cartridge for <NUM> at a continuous flow of <NUM>/min by means of a Gerstel gas sampling system.

Headspace concentrations were calculated by external standard calibrations using different concentrations of the corresponding fragrance materials (<NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> ng/l) in EtOH. The corresponding fragrance materials are the fragrance materials that are released from a specific precursor / compound of formula (I), i.e. the corresponding α,β-unsaturated carbonyl compounds and thiol compounds. Each calibration solution (<NUM>µl) was injected onto a clean, empty cartridge which was desorbed and analyzed using the same conditions as described above.

<FIG>: Fragrance release curve for precursor <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyldecanal (obtained according to procedure <NUM> as described above under synthesis procedures of precursors) as determined by procedure <NUM> as described above under sensorial analyses.

<FIG>: Fragrance release curve for precursor <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]sulfanyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethylcyclohex-<NUM>-en-<NUM>-yl)butan-<NUM>-one (obtained according to procedure <NUM> as described above under synthesis procedures of precursors) as determined by procedure <NUM> as described above under sensorial analyses.

<FIG> show the release of <NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propanethiol and the respective α,β-unsaturated carbonyl compound from the compounds of formula (I) obtained according to procedures <NUM> and <NUM> as described above under synthesis procedures of precursors. The x axis of the Figures shows the period of time over which the measurement was conducted. On the y axis, the headspace concentrations (determined according to procedure <NUM> as described above under sensorial analyses) of the two components released from the compound of formula (I) are shown, respectively. From the Figures it can be seen that on the freshly washed/wet laundry a strong release of the thiol compound occurs, which is also sensory perceptible. On the other hand, a noticeable release of the α,β-unsaturated carbonyl compound occurs with a time delay on dried laundry after several hours (<NUM>-decenal: <NUM> - <NUM>, delta-damascone: <NUM> - <NUM>). These analytical results demonstrate the (controlled) decomposition of the compounds of formula (I) according to the invention with simultaneous release of the α,β-unsaturated aldehyde or ketone over time and are in line with the sensory evaluation of the washing tests (cf. The controlled decomposition of the compound of formula (I) advantageously leads to a long-lasting perception of the α,β-unsaturated aldehyde or ketone on the dried laundry. Additionally, the high impact thiol compound improves the overall scent of the freshly washed laundry without unwanted or unpleasant off notes.

For comparison, the experiment was repeated, however instead of using the compounds of formula (I) according to the invention, <NUM> of a mixture of α,β-unsaturated carbonyl compound (hexenal) and thiol (<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propane-<NUM>-thiol) was employed.

It can be seen that the fragrance release from the compound of formula (I) according to the invention is substantially different to the release from the mixture of α,β-unsaturated carbonyl compound and thiol, underlying that released fragrance materials are delivered from the partial degradation of the compound of formula (I) according to the invention over time. Unexpectedly, it is observed that the peak of thiol release is between <NUM>-<NUM>, while the peak of release of hexenal is reached at <NUM>-<NUM>, surprisingly revealing that the compounds of formula (I) according to the invention can deliver two pleasantly smelling fragrance materials at different points in time.

A sensory evaluation of the compounds of formula (I) according to the invention (obtained according to procedures <NUM> and <NUM> as described above under synthesis procedures of precursors) after a washing application was carried out as described below and delivered the test results as shown in Table <NUM> below.

Perfumed fabric softener samples were prepared by mixing the appropriate amount of compound of formula (I) and dipropylene glycol (DPG) to the perfume oil and adding <NUM>% of the resulting fragrance mixture to unperfumed fabric softener.

<NUM> of cotton towels were washed in a European washing machine (Express <NUM> program, <NUM>, <NUM> rpm) using <NUM> of perfumed fabric softener (cf. Table <NUM> for composition of the fabric softener). The fabrics were lined dried over night and put on a table for evaluation after <NUM>, <NUM>, and <NUM>. The fabrics were evaluated by <NUM> trained panelists. Perfume intensities are evaluated on a scale from no odor (<NUM>) to strongest imaginable (<NUM>). Panelists were also asked to choose which sample is perceived in higher intensity.

It is concluded that the fragrance perception is significantly stronger using compound of formula (I) in comparison to an equivalent amount of delta-damascone. To underline this, one piece of cotton towel was analyzed by headspace GC/MS according to procedure <NUM> as described above under sensorial analyses, revealing a significantly higher headspace concentration of delta-damascone of the cotton towel washed with perfume oil including compound of formula (I).

Fragrance release for compound of formula (I) <NUM>-[<NUM>-methyl-<NUM>-(<NUM>-methyltetrahydropyran-<NUM>-yl)propyl]-sulfanyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethylcyclohex-<NUM>-en-<NUM>-yl)butan-<NUM>-one and a mixture of <NUM>% delta-damascone and <NUM>% DPG:.

An artificial skin model was prepared using synthetic skin (Vitro-Skin®, approx. <NUM> radius), fat, cellulose, and agar.

Perfumed deo samples were prepared by mixing the appropriate amount of compound of formula (I) and DPG to the perfume oil and adding <NUM>% of the resulting fragrance mixture to unperfumed deo base.

<NUM> of perfumed deo is added on artificial skin and evenly distributed for <NUM>. Afterwards, the model is placed on a heating plate (<NUM>) and evaluated after <NUM>, <NUM>, <NUM>, and <NUM> by <NUM> trained panelists. Perfume intensities are evaluated on a scale from no odor (<NUM>) to strongest imaginable (<NUM>).

It is concluded that the intensity of the fragrance is significantly stronger when applying a perfume oil including a compound of formula (I). Unexpectedly, it is revealed the perception of the individual precursor components (thiol, α,β-unsaturated carbonyl) occurs nonsimultaneously, as the thiol component is perceived at <NUM>, giving a richer fruity profile, while delta-damascone is perceived after <NUM>-<NUM> without any perception of thiol notes.

Panelists were asked to describe the hedonic differences between the different samples.

Perfumed shampoo samples were prepared by mixing the appropriate amount of compound of formula (I) and DPG to the perfume oil and adding <NUM>% of the resulting fragrance mixture to unperfumed shampoo base.

One slightly wet hair swatch (<NUM> Caucasian hair) is treated with <NUM> of perfumed shampoo and carefully washed for <NUM>. Afterwards, the swatch is left to stand for <NUM> and rinsed with warm water (<NUM>) for <NUM>. Excess water is removed by passing the swatch between the fingers.

The hair swatches were lined dried and evaluated after <NUM>, <NUM>, and <NUM> by <NUM> trained panelists. Perfume intensities are evaluated on a scale from no odor (<NUM>) to strongest imaginable (<NUM>).

Perfumed deo samples were prepared by mixing the appropriate amount of precursor to the perfume oil and adding <NUM>% of the resulting fragrance mixture to unperfumed deo base. <NUM> of perfumed deo is added on artificial skin and evenly distributed for <NUM>. Afterwards, the model is placed on a heating plate (<NUM>) and evaluated after <NUM>, <NUM>, <NUM>, and <NUM> by <NUM> trained panelists. Perfume intensities are evaluated on a scale from no odor (<NUM>) to strongest imaginable (<NUM>).

It is detected that the perfume oil containing compound of formula (I) according to the invention is perceived stronger compared to perfume oil containing precursor of the prior art (<CIT>) at all stages of evaluation, showing a clear benefit of the compounds of formula (I) according to the invention. Surprisingly, both the hedonic profile and the perceived intensity of the fragrance after <NUM> are positively influenced by introduction of a pleasantly smelling thiol component, while the superior and long-lasting performance at <NUM>-<NUM> is likely due to the lower evaporation profile/higher substantivity of the compound of formula (I) according to the invention.

Perfumed fabric softener samples were prepared by mixing the appropriate amount of precursor to the perfume oil and adding <NUM>% of the resulting fragrance mixture to unperfumed fabric softener.

<NUM> of cotton towels were washed in a European washing machine (Express <NUM> program, <NUM>, <NUM> rpm) using <NUM> of perfumed fabric softener (cf. Table <NUM> for composition of the fabric softener). The fabrics were lined dried over night and put on a table for evaluation after <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>. The fabrics were evaluated by <NUM> trained panelists. Perfume intensities are evaluated on a scale from no odor (<NUM>) to strongest imaginable (<NUM>). Panelists were also asked to choose which sample is perceived in higher intensity.

It is detected that the perfume oil containing compound of formula (I) according to the invention is perceived stronger compared to precursor of the prior art (<CIT>) at all stages of evaluation, showing a clear benefit of the present system. Surprisingly, both the hedonic profile and the perceived intensity of the fragrance after <NUM> are positively influenced by introduction of a pleasantly smelling thiol component, while the superior, long-lasting performance at <NUM>-<NUM> is likely due to the lower evaporation profile/higher substantivity of the compound of formula (I) according to the invention.

Claim 1:
Compound of formula (I)
<CHM>
(i) wherein R is selected from the group consisting of hydrogen and C<NUM> to C<NUM> linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably wherein the residues additionally carry one, two or more C<NUM> to C<NUM> linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents, and
wherein R' is selected from the group consisting of hydrogen and C<NUM> to C<NUM> linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably wherein the residues additionally carry one, two or more C<NUM> to C<NUM> linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents, and
wherein R<NUM> is selected from the group consisting of hydrogen and C<NUM> to C<NUM> linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably wherein the residues additionally carry one, two or more C<NUM> to C<NUM> linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents, and
wherein R<NUM> is selected from the group consisting of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
wherein R<NUM> is selected from the group consisting of hydrogen and C<NUM> to C<NUM> linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably wherein the residues additionally carry one, two or more C<NUM> to C<NUM> linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents,
or
(ii) wherein R', R<NUM> and R<NUM> are independently selected from the groups as defined in (i), respectively, and R and R<NUM> are bonded together to form a saturated or unsaturated ring system comprising <NUM> to <NUM> carbon atoms, preferably wherein the ring system additionally carries one, two or more C<NUM> to C<NUM> linear, branched or cyclic alkyl, alkenyl or alkadienyl substituents,
or
(iii) wherein R', R<NUM> and R<NUM> are independently selected from the groups as defined in (i), respectively, and R and R<NUM> are bonded together to form a saturated or unsaturated, mono or bicyclic, ring system comprising <NUM> to <NUM> carbon atoms and optionally <NUM> or <NUM> ether functional groups, preferably wherein the ring system additionally carries one, two or more C<NUM> to C<NUM> linear, branched or cyclic alkyl, alkenyl or alkadienyl substituents.