DE102019129873A1 - CONTROLLED ODOR RELEASE WITH CHITOSAN AS A CARRIER - Google Patents

Abstract

The present invention relates to specific fragrance precursor compounds of the formula (I), which are derived from chitosan and fragrance aldehydes and ketones, and a process for their preparation. The present invention also relates to washing or cleaning agents, cosmetic agents and air conditioning agents which contain such fragrance precursor compounds. The present invention also relates to a method for long-lasting scenting of surfaces using the scent precursor compounds and agents according to the invention.

Description

The present invention relates to specific fragrance precursor compounds of the formula (I), which are derived from chitosan and fragrance aldehydes and ketones, and a process for their preparation. The present invention also relates to washing or cleaning agents, cosmetic agents and air conditioning agents which contain such fragrance precursor compounds. The present invention also relates to a method for long-lasting scenting of surfaces using the scent precursor compounds and agents according to the invention.

Washing or cleaning agents or cosmetic agents mostly contain fragrances which give the agents a pleasant odor. The fragrances can also serve to mask the odor of other ingredients, so that a pleasant odor impression is created for the consumer.

In the area of detergents in particular, fragrances are important components of the composition, since the laundry should have a pleasant and, if possible, fresh fragrance both in the wet and in the dry state. The use of fragrances is fundamentally problematic, since these are more or less volatile compounds, but a long-lasting fragrance effect is still sought. Particularly in the case of those fragrances which represent the fresh and light notes of the perfume and which are particularly volatile as a result of their high vapor pressure, the desired longevity of the fragrance impression can hardly be achieved.

A delayed release of fragrance can take place, for example, through so-called fragrance precursor compounds. These fragrance precursor compounds are based on fragrance compounds, for example fragrance aldehydes or ketones, which are reacted with further compounds to form the aforementioned fragrance precursor compounds, whereby these are then able to release the actual fragrance compound again with a delay (for example by hydrolysis or photochemical). Although both fragrance aldehydes and ketones have been described as starting materials for fragrance precursors, no commercially suitable fragrance precursors with ketones are available to date. The object of the present invention was therefore to provide fragrance precursor compounds, in particular based on fragrance ketones and aldehydes, which can be obtained by a simple synthesis. Furthermore, the fragrance precursor compounds should preferably be suitable for use in consumer goods, in particular detergents and cleaning agents. It is also desirable here that the fragrance precursor compounds also achieve better adhesion to the surface to which they are applied, preferably a textile.

The inventors of the present invention have surprisingly found that the object can be achieved by the special fragrance precursor compounds of the formula (I), which are derived from chitosan and fragrance aldehydes and ketones. They can provide a biologically degradable and harmless fragrance precursor compound.

wobei unabhängig voneinander in jeder Einheit der Rest X ausgewählt ist aus -NH₂, -NHC(=O)CH₃ und -N=C(-R¹)-R² und Z gleich H ist; oder X und Z mit dem Rest -O-CH-CH- der Einheit, an den sie gebunden sind, gemeinsam einen Ring der Formel (II)

bilden; wobei
R¹ und R² jeweils unabhängig voneinander ausgewählt sind aus H oder linearen, verzweigten oder cyclischen, gesättigten oder ungesättigten, substituierten oder unsubstituierten Kohlenwasserstoffresten, die bis zu 20 Kohlenstoffatome und gegebenenfalls bis zu 6 Heteroatome enthalten, oder R¹ und R² jeweils gemeinsam mit dem Kohlenstoffatom an das sie gebunden sind einen cyclischen, gesättigten oder ungesättigten, Kohlenwasserstoffring mit bis zu 12 Kohlenstoffatomen bilden, der bis zu 6 Heteroatome enthalten kann;
n eine ganze Zahl von 2 bis 4000 ist;
mit der Maßgabe, dass sich der Rest R¹-C-R² jeweils von einem Duftstoffaldehyd der Formel R¹-C(=O)H oder einem Duftstoffketon der Formel R¹-C(=O)-R² ableitet und dass mindestens ein X gleich -N=C(-R¹)-R² und Z gleich H ist und/oder mindestens ein X und Z einen Ring der Formel (II) bilden.In a first aspect, the invention therefore relates to a fragrance precursor compound of the formula (I)

where, independently of one another, in each unit the radical X is selected from -NH ₂ , -NHC (= O) CH ₃ and -N = C (-R ¹ ) -R ² and Z is H; or X and Z together with the radical -O-CH-CH- of the unit to which they are attached form a ring of the formula (II)

form; in which
R ¹ and R ^{2 are} each independently selected from H or linear, branched or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon radicals which contain up to 20 carbon atoms and optionally up to 6 heteroatoms, or R ¹ and R ² each together with the carbon atom to which they are bonded form a cyclic, saturated or unsaturated, hydrocarbon ring with up to 12 carbon atoms which can contain up to 6 heteroatoms;
n is an integer from 2 to 4000;
with the proviso that the radical R ^{1 -CR 2 is derived in} each case from a fragrance aldehyde of ^{the formula R 1} -C (= O) H or a fragrance ketone of the formula R ¹ -C (= O) -R ² and that at least one X is -N = C (-R ¹ ) -R ² and Z is H and / or at least one X and Z form a ring of the formula (II).

In a second aspect, the present invention relates to a washing or cleaning agent containing at least one fragrance precursor compound of the present invention.

In a third aspect, the present invention relates to an air care agent containing at least one fragrance precursor compound of the present invention.

In a fourth aspect, the present invention relates to a cosmetic agent containing at least one fragrance precursor compound of the present invention.

wobei
die Reste X' unabhängig voneinander ausgewählt sind aus -NH₂ und -NHC(=O)CH₃; und
n eine ganze Zahl von 2 bis 4000 ist, mit Aldehyden der Formel R¹-C(=O)H oder Ketonen der Formel R¹-C(=O)-R² oder Mischungen davon, wobei R¹ und R² wie in Formel (I) definiert sind, mit der Maßgabe, dass mindestens ein Rest X' gleich -NH₂ ist, vorzugsweise mindestens 50% der Reste X' gleich -NH₂ sind.In a fifth aspect, the present invention relates to a process for the preparation of fragrance precursor compounds of the formulas (I) according to the present invention, comprising the reaction of a compound according to the general formula (IV)

in which
the radicals X 'are independently selected from —NH ₂ and —NHC (= O) CH ₃ ; and
n is an integer from 2 to 4000, with aldehydes of the formula R ¹ -C (= O) H or ketones of the formula R ¹ -C (= O) -R ² or mixtures thereof, where R ¹ and R ^{2 are} as in Formula (I) are defined, with the proviso that at least one radical X 'is equal to -NH ₂ , preferably at least 50% of the radicals X' are equal to -NH ₂ .

In various embodiments, the proportion of X '= -NH _{2 is} at least 50% of all radicals X', for example at least 60, at least 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or at least 99%, e.g. even 100%. The remaining radicals X 'in such embodiments are then —NHC (= O) CH ₃ .

Finally, in a sixth aspect, the present invention relates to a method for long-lasting scenting of surfaces, characterized in that a scent precursor compound of the present invention or a detergent, cleaning agent or a cosmetic agent of the present invention is applied to the surface to be scented, the scenting lasting longer than if the respective fragrance compound or an identical agent in which the fragrance precursor compound is replaced by the respective fragrance compound were used.

These and other embodiments, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Individual features or embodiments of the invention described can be combined with other features or embodiments of the invention without these having been described in combination within the scope of the invention. It goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to restrict it and, in particular, the invention is not limited to the examples.

“At least one” as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with the fragrance precursor compounds described herein, this information does not refer to the absolute amount of molecules, but to the type of compound. “At least one fragrance precursor compound” therefore means, for example, that only one type of fragrance precursor compound or several different types of fragrance precursor compounds can be contained without specifying the amount of the individual compounds.

Unless stated otherwise, all of the quantitative data given in connection with the process described herein relate to% by weight in each case based on the total weight of the composition. Furthermore, quantities of this type which relate to at least one constituent always relate to the total amount of this type of constituent contained in the composition, unless explicitly stated otherwise. This means that such quantitative information, for example in connection with “at least one fragrance precursor compound”, relates to the total amount of fragrance precursor compounds contained in the composition, unless explicitly stated otherwise.

Numerical values which are given herein without decimal places refer to the full stated value with one decimal place. For example, “99%” stands for “99.0%”.

Numeric ranges specified in the format “in / from x to y” include the stated values. If several preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also recorded.

“Substituted”, as used herein in connection with the definition of the fragrance precursor compounds of formulas (I) and (III), means that one hydrogen atom has been replaced by another radical. Suitable radicals include, but are not limited to, linear or branched hydrocarbon groups of up to 22 carbon atoms, preferably hydrocarbon groups of up to 10 carbon atoms, including alkyl, alkenyl, alkynyl; -OH, -CN, -NO ₂ , -C (O) H, -C (O) OR ', -C (O) NR'R'',-NR'-C (O) -R'', - NR'R ", where R 'and R" are linear or branched alkyl with up to 12 carbon atoms, preferably linear or branched alkyl with up to 6 carbon atoms.

The terms “fragrance” and “fragrance” are to be used synonymously in the context of this invention. A fragrance is a compound that has a characteristic odor and contributes to achieving a specific fragrance profile of a perfume oil or a composition. Fragrances also include compounds that change the fragrance profile of a perfume oil or a composition in such a way that the fragrance acquires a certain depth, which the person skilled in the art usually knows as the complexity of a fragrance.

The present invention relates in particular to fragrance precursors of formula (I).

ist unabhängig voneinander in jeder Einheit der Rest X ausgewählt aus -NH₂, -NHC(=O)CH₃ und -N=C(-R¹)-R² und Z ist gleich H; oder X und Z bilden mit dem Rest -O-CH-CH- der Einheit, an den sie gebunden sind, gemeinsam einen Ring der Formel (II)

wobei
R¹ und R² unabhängig voneinander ausgewählt sind aus H oder linearen, verzweigten oder cyclischen, gesättigten oder ungesättigten, substituierten oder unsubstituierten Kohlenwasserstoffresten, die bis zu 20 Kohlenstoffatome und gegebenenfalls bis zu 6 Heteroatome enthalten, oder R¹ und R² jeweils gemeinsam mit dem Kohlenstoffatom an das sie gebunden sind einen cyclischen, gesättigten oder ungesättigten, Kohlenwasserstoffring mit bis zu 12 Kohlenstoffatomen bilden, der bis zu 6 Heteroatome enthalten kann;
ist n eine ganze Zahl von 2 bis 4000, bevorzugt 10 bis 3000, stärker bevorzugt 100 bis 2500, am stärksten bevorzugt 1000 bis 2200;
mit der Maßgabe, dass sich der Rest R¹-C-R² jeweils von einem Duftstoffaldehyd der Formel R¹-C(=O)H oder einem Duftstoffketon der Formel R¹-C(=O)-R² ableitet und dass mindestens ein X gleich -N=C(-R¹)-R² und Z gleich H ist und/oder mindestens ein X und Z einen Ring der Formel (II) bilden,
beispielsweise sind mindestens 20%, mindestens 30% oder mindestens 40% oder mindestens 40% oder mindestens 50% oder mindestens 60%, mindestens 75% oder mindestens 80% oder mindestens 90% oder 100% der Reste X gleich -N=C(-R¹)-R². In verschiedenen Ausführungsformen sind zusätzlich oder an Stelle von -N=C(-R¹)-R² und H Ringe der Formel (II) vorhanden, beispielsweise in bis zu 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% oder 50% der Reste X und Z. In verschiedenen Ausführungsformen sind weniger als 10 %, bevorzugt weniger als 5 %, stärker bevorzugt weniger als 1 % der Reste X gleich -NHC(=O)CH₃ oder es ist kein -NHC(=O)CH₃ Rest enthalten. In verschiedenen Ausführungsformen sind die übrigen Reste X = -NH₂.In the fragrance precursors of the formula (I)

is independently in each unit the radical X selected from -NH ₂ , -NHC (= O) CH ₃ and -N = C (-R ¹ ) -R ² and Z is H; or X and Z together with the radical -O-CH-CH- of the unit to which they are attached form a ring of the formula (II)

in which
R ¹ and R ^{2 are} independently selected from H or linear, branched or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon radicals containing up to 20 carbon atoms and optionally up to 6 heteroatoms, or R ¹ and R ² each together with the Carbon atom to which they are bonded form a cyclic, saturated or unsaturated, hydrocarbon ring with up to 12 carbon atoms, which can contain up to 6 heteroatoms;
n is an integer from 2 to 4000, preferably 10 to 3000, more preferably 100 to 2500, most preferably 1000 to 2200;
with the proviso that the radical R ^{1 -CR 2 is derived in} each case from a fragrance aldehyde of ^{the formula R 1} -C (= O) H or a fragrance ketone of the formula R ¹ -C (= O) -R ² and that at least one X equal to -N = C (-R ¹ ) -R ² and Z is equal to H and / or at least one X and Z form a ring of the formula (II),
for example, at least 20%, at least 30% or at least 40% or at least 40% or at least 50% or at least 60%, at least 75% or at least 80% or at least 90% or 100% of the radicals X are -N = C (- R ¹ ) -R ² . In various embodiments, rings of the formula (II) are present in addition to or instead of -N = C (-R ¹ ) -R ² and H, for example in up to 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of the radicals X and Z. In various embodiments less than 10%, preferably less than 5%, more preferably less than 1% of the radicals X are -NHC (= O ) CH ₃ or no -NHC (= O) CH ₃ radical is contained. In various embodiments, the remaining radicals X = —NH ₂ .

For the purposes of the present invention, all possible substitution patterns are included, only with the proviso that at least one X is -N = C (-R ¹ ) -R ² and Z is H and / or at least one X and Z is a ring of the formula (II) form.

wobei
R¹ und R² jeweils unabhängig voneinander ausgewählt sind aus H oder linearen, verzweigten oder cyclischen, gesättigten oder ungesättigten, substituierten oder unsubstituierten Kohlenwasserstoffresten, die bis zu 20 Kohlenstoffatome und gegebenenfalls bis zu 6 Heteroatome enthalten, oder R¹ und R² gemeinsam mit dem Kohlenstoffatom an das sie gebunden sind einen cyclischen, gesättigten oder ungesättigten, Kohlenwasserstoffring mit bis zu 12 Kohlenstoffatomen bilden, der bis zu 6 Heteroatome enthalten kann; und
n eine ganze Zahl von 2 bis 4000, bevorzugt 10 bis 3000, stärker bevorzugt 100 bis 2500, am stärksten bevorzugt 1000 bis 2200 ist;
mit der Maßgabe, dass sich der Rest R¹-C-R² von einem Duftstoffaldehyd der Formel R¹-C(=O)H oder einem Duftstoffketon der Formel R¹-C(=0)-R² ableitet.In a further embodiment, the at least one fragrance precursor compound of the formula (I) is at least one fragrance precursor compound of the formula (III)

in which
R ¹ and R ^{2 are} each independently selected from H or linear, branched or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon radicals containing up to 20 carbon atoms and optionally up to 6 heteroatoms, or R ¹ and R ² together with the Carbon atom to which they are bonded form a cyclic, saturated or unsaturated, hydrocarbon ring with up to 12 carbon atoms, which can contain up to 6 heteroatoms; and
n is an integer from 2 to 4000, preferably 10 to 3000, more preferably 100 to 2500, most preferably 1000 to 2200;
with the proviso that the radical R ¹ -CR ^{2 is derived} from a fragrance aldehyde of the formula R ¹ -C (= O) H or a fragrance ketone of the formula R ¹ -C (= 0) -R ² .

The expression “radical R ¹ -CR ² ” relates to the corresponding part of the compound of the formulas (I) to (III), this being in each case via the central carbon atom via a double bond or as part of the ring of the formula (II) bound to the remainder of the compound. This radical is derived from fragrance ketones or aldehydes in that the oxygen atom, which in these compounds is bonded to the central carbon atom via a double bond, is replaced by the radical of the compound of formula (I) or (III), ie the Chitosan residue, is replaced.

From the described fragrance precursor compounds of the formula (I) and (III), the fragrance can be released by hydrolysis, in particular at acidic pH values, i.e. pH values <7, for example <6 or <5.

The fragrance precursor compounds of the present invention are obtained by reacting a corresponding chitosan with the fragrance, here a fragrance aldehyde or ketone, in particular a fragrance ketone. If the reaction takes place with only one fragrance ketone or only one fragrance aldehyde, the radicals R ¹ and R ^{2 are} identical in all repeating units. If mixtures of different fragrance ketones and / or aldehydes are used, compounds are obtained which contain ^{different radicals R 1} and R ^2. All combinations are statistically possible.

In various embodiments of the invention, the fragrance aldehyde can be selected from adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal or cyclamenaldehyde (3- (4-isopropylphenyl) -2-methylpropanal ), Nympheal (3- (4-Isobutyl-2-methylphenyl) propanal), Ethylvanillin, Florhydral (3- (3-Isopropylphenyl) butanal]), Trifernal (3-Phenylbutyraldehyde), Helional (3- (3,4-Methylenedioxyphenyl ) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, lilial (3- (4-tert- Butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenaldehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5- heptenal), triplal (2,4-dimethyl-3-cyclohexene-1-carboxaldehyde), 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) propanal, 2-methyl-3- (para-methoxyphenyl) propanal , 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadien-1-al, 3,7-dimethyl-6-octen-1-al, [(3.7 -Dimethyl-6-octenyl) oxy] acetaldehyde, 4-isopropylbenzylaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3 -cyclohexene-1-carboxaldehyde, 2-methyl-3- (isopropylphenyl) propanal, 1-decanal, 2,6-dimethyl-5-heptenal, 4- (tricyclo [5.2.1.0 (2,6)] decylidene-8 ) -butanal, octahydro-4,7-methane-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alphadimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4- Methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, tetrahydrocitral (3,7-dimethyloctanal), undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- ( 3) (4-methyl-3-pentenyl) -3-cyclohexenecarboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexen-3- carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methyldecanal, 1-nonanal, 1-octanal, 2, 6,10-trimethyl-5,9-undecadienal, 2-methyl-3- (4-tert-butyl) propanal, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1 -carboxaldehyde, 5- or 6-methoxyhexahydro-4,7-methanindan-1- or -2-carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy- 3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4- Methylphenylacetaldehyde, 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -2-butenal, ortho-methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde, 3,7- Dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4 , 7-methanindane-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4- (1-methylethyl) benzene acetaldehyde , 6,6-dimethyl-2-norpinene-2-propionaldehyde, para-methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl -2-naphthaldehyde, 3-propylbicyclo [2.2.1] -hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, floral (4,8-dimethyl-4, 9-decadienal), aldehyde C12MNA (2-methylundecanal), liminal (beta-4-dimethylcyclohex-3-ene-1-propan-1-al), methylnonylacetaldehyde, hexanal, trans-2-hexenal and mixtures thereof.

Suitable ketones include, but are not limited to, methyl beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-indene-4- on), calone (methylbenzodioxepinone), tonalid (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyldihydrojasmonate (Hedion ), Menthone, carvone, camphor, koavone (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, dihydro-beta-ionone, gamma-methyl -lonone, fleuramon (2-heptylcyclopentanone), frambinone methyl ether (4- (4-methoxyphenyl) butan-2-one), dihydrojasmone, cis -jasmone, 1- (1,2,3,4,5,6,7,8 -Octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) -ethan-1-one and isomers thereof, methyl cedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl betanaphtyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery Ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldeca-hydro-2-naphton, dimethyloctenone, Frescomenthe (2-butan-2-ylc yclohexan-1-one), 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2- (2- (4-methyl-3-cyclohexen-1-yl) propyl) cyclopentanone, 1 - (p-Menthen-6 (2) yl) -1-propanone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1 , 1,2,3,3-pentamethyl-4 (5H) in-danone, 4-damascol, dulcinyl (4- (1,3-benzodioxol-5-yl) butan-2-one), hexalone (1- ( 2,6,6-Trimethyl-2-cyclohexen-1-yl) -1,6-heptadien-3-one), Isocyclemon E (2-acetonaphthon-1, 2,3,4,5,6,7,8 -octahydro-2,3,8,8-tetramethyl), methyl nonyl ketone, methylcyclocitron, methyl lavender ketone, orivon (4-tert-amylcyclohexanone), 4-tert-butylcyclohexanone, delphon (2-pentylcyclopentanone), muscon (CAS 541-91-3 ), Neobutenone (1- (5,5-dimethyl-1-cyclo-hexenyl) pent-4-en-1-one), Plicaton (CAS 41724-19-0), Velouton (2,2,5-trimethyl- 5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one, tetrameran (6,10-dimethylundecen-2-one) and mixtures thereof.

The fragrance aldehyde or ketone is preferably selected from dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamenaldehyde, melonal and anisaldehyde, in particular from dihydro-beta-ionone, frambinone methyl ether, hedione, anisaldehyde and melonal.

In addition, as fragrance aldehydes and / or fragrance ketones, in principle all customary fragrance aldehydes and / or fragrance ketones which, after conversion, fall under the definition of the above formula (I), which in particular to bring about a pleasant Olfactory sensation can be used in humans. Such fragrance aldehydes and / or fragrance ketones are known to the person skilled in the art and also in the patent literature, for example in US 2003/0158079 A1 , Paragraphs [0154] and [0155]. For other suitable fragrances see p teffen Arctander, Aroma Chemicals Volume 1 and Volume 2 (published 1960 and 1969, respectively, new edition 2000; ISBN: 0-931710-37-5 and 0-931710-38-3) referenced.

The radicals derived from the fragrance ketones or aldehydes in the compounds of the formulas (I) and (III) can therefore be the radicals of the abovementioned compounds in which, for example, the oxygen atom has been replaced by the chitosan radical. A radical derived from decanal is therefore, for example, the radical H ₃ C (CH ₂ ) ₈ (C) H, the (C) being bonded to the N atom of the chitosan radical via a double bond (C =).

wobei
die Reste X' unabhängig voneinander ausgewählt sind aus -NH₂ und -NHC(=O)CH₃; und n eine ganze Zahl von 2 bis 4000 ist, mit der Maßgabe, dass mindestens ein Rest X' gleich -NH₂ ist, mit Aldehyden der Formel R¹-C(=O)H oder Ketonen der Formel R¹-C(=O)-R² oder Mischungen davon, wobei R¹ und R² wie in Formel (I) definiert sind, umgesetzt. In verschiedenen Ausführungsformen sind weniger als 10 %, bevorzugt weniger als 5 %, stärker bevorzugt weniger als 1 % der Reste X' gleich -NHC(=O)CH₃ oder es ist kein -NHC(=O)CH₃ Rest enthalten. Dies bedeutet, dass in verschiedenen Ausführungsformen der Anteil an X' = -NH₂ mindestens 90, 91, 92, 93, 94, 95, 96, 97, 98, oder mindestens 99 %, z.B. sogar 100 % ist.To prepare the fragrance precursor compound, a compound of the general formula (IV)

in which
the radicals X 'are independently selected from —NH ₂ and —NHC (= O) CH ₃ ; and n is an integer from 2 to 4000, with the proviso that at least one radical X 'is equal to -NH ₂ , with aldehydes of the formula R ¹ -C (= O) H or ketones of the formula R ¹ -C (= O) -R ² or mixtures thereof, where R ¹ and R ^{2 are} as defined in formula (I), reacted. In various embodiments, less than 10%, preferably less than 5%, more preferably less than 1% of the radicals X 'are equal to —NHC (= O) CH ₃ or no —NHC (= O) CH ₃ radical is present. This means that in various embodiments the proportion of X '= -NH _{2 is} at least 90, 91, 92, 93, 94, 95, 96, 97, 98, or at least 99%, for example even 100%.

Chitosans are commercially available. Since they are produced from chitin by a chitin deacetylase and the conversion does not have to take place completely, the chitosans can also contain several -NHC (= O) CH ₃ radicals instead of the -NH ₂ radicals. Typically, however, the compounds of the formula (IV) contain a proportion of X '= -NH ₂ of at least 50% of all radicals X', for example at least 60, at least 65, 70, 75, 80, 85, 90, 91, 92, 93 , 94, 95, 96, 97, 98, or at least 99%, e.g. even 100%. The remaining radicals X 'in such embodiments is then —NHC (= O) CH ₃ . This ratio can then also be transferred to the compounds of the formula (I), so that the radicals X that are not R ¹ -CR ² or are part of the ring of the formula (II) are a mixture of -NH ₂ and -NHC (= O) CH ₃ are, depending on the degree of conversion, the ratio can be strongly on the side of the amino groups.

In various embodiments, the reaction takes place in the presence of an acid, in particular p-toluenesulfonic acid and / or solvents, such as alcohols, in particular methanol. In various embodiments, the reaction takes place with heating, in particular at 30 to 80 ° C., particularly preferably 60 to 70 ° C., and / or in vacuo. The degree of substitution of the H atoms of the NH ₂ radicals of the chitosan by R ¹ -CR ² to form an -N = C (-R ¹ ) -R ^{2 group} or an H atom to form a ring of the formula (II) form is easy to control through the amount of aldehydes and ketones added. If complete substitution is to be achieved (formula III), the aldehydes and ketones are added at least in equimolar amounts to the -NH ₂ radicals of the chitosan, preferably in excess.

The chitosan is preferably a chitosan with a relatively high molecular weight, which means, for example, that n in the formulas (I) and (III) is at least 1000, in particular at least 1800. In such embodiments, the fragrances used for the reaction are selected, for example, from those mentioned above, in particular dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamenaldehyde, melonal and anisaldehyde, in particular from dihydro-beta-ionone, frambinone methyl ether, hedione , Anisaldehyde and melonal.

The reaction product obtained can be isolated and, if necessary, purified by customary processes.

The above-described fragrance precursor compounds of the formula (I) and (III) can be used in the agents of the process according to the invention as mixtures with at least one further fragrance or at least one further fragrance precursor compound which is different from the fragrance precursor compound according to formula (I).

The further fragrances which can optionally be contained in the compositions are not subject to any particular restrictions. Thus, individual fragrance compounds of natural or synthetic origin, for example of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, styrallylpropionate Cyclohexyl salicylate, floramate, melusate, and jasmacyclate. The ethers include, for example, benzyl ethyl ether and ambroxan, the aldehydes include the abovementioned, for example, the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde (3- (4-propan-2-ylphenyl) butanal), lilial and bourgeonal, the ketones, for example, the ionones, [alpha] -lsomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note.

The compositions can also contain natural fragrance mixtures, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroli oil, orange peel oil and sandalwood oil. Further conventional fragrances that can be contained in the agents according to the invention within the scope of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, Geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva oil balsam oil, coriander oil, cumin oil, lavender oil, lime oil, spearmint oil Mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, origanum oil, palmarosa oil, patchuli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil Thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, Wnt green oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil as well as ambrettolide, ambroxan, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, benzophenone, benzyl aldehyde, acetophenone, benzylacetate, acetophenone, benzyl aldehyde Benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, boisambrene forte, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchanyic acid, helium formemyl acetate, geranium formemethyl acetate, fenchanyic acid formemyl acetate, heptanyic acid ethyl acetate, heptanyic acid methyl ester , Hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamic alcohol, indole, Iran, isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amethylketon-methyl ketone , Methylchavikol, p-methylquinoline, methyl-β-naphthyl ketone, methyl-n-nonylacetaldehyde, met hyl-n-nonyl ketone, muskon, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy acetophenone, pentadecanolide, β-phenyl ethyl alcohol, phenylacetic acid, pulegon, safrol, Isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, sandelice, skatol, terpineol, thyme, thymol, troenan, γ-undelactone, vanillin, veratrumaldehyde, cinnamic acid, lime-phenyl acetate, cinnamic acid, cinnamic acid, cinnamic acid, cinnamic acid, cinnamic acid, cinnamic acid, cinnamic acid, cinnamic acid, cinnamic acid alcohol, cinnamic acid alcohol , Melusate, menthol, menthone, methyl-n-heptenone, pinene, phenylacetaldehyde, terpinylacetate, citral, citronellal and mixtures thereof.

It is also possible for the at least one fragrance precursor compound of the formula (I) or formula (III) to be used with the corresponding aldehydes and / or ketones. According to a preferred embodiment of the method according to the invention, such compositions are characterized in that the molar ratio of fragrance aldehyde and / or fragrance ketone to the corresponding fragrance precursor compound of formula (I) and (III) 20: 1 to 1:20, preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 3: 1 to 1: 3, even more preferably 2: 1 to 1: 2 and in particular 1.2: 1 to 1: 1.2 .

The present invention further relates to washing, cleaning, air care or cosmetic agents which contain at least one of the fragrance precursors of the present invention. In preferred embodiments, the at least one fragrance precursor compound is in a total amount of 0.001 and 5% by weight, advantageously 0.005 and 4% by weight, more advantageously 0.01 and 2% by weight, each based on the total weight of the respective Means, included.

The detergents and cleaning agents to be used in the process can also contain anionic, nonionic, cationic, amphoteric or zwitterionic surfactants or mixtures thereof. Furthermore, these agents can be in solid or liquid form.

Suitable nonionic surfactants are in particular ethoxylation and / or propoxylation products of alkyl glycosides and / or linear or branched alcohols each with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides are the with regard to the alkyl part correspond to the long-chain alcohol derivatives mentioned, as well as from alkylphenols with 5 to 12 carbon atoms in the alkyl radical can be used.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Soaps that can be used are preferably the alkali metal salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The sulfate-type surfactants which can be used include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The sulfonate-type surfactants that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed when corresponding monoolefins are reacted with sulfur trioxide, as well as alpha-sulfo fatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters.

Cationic surfactants are preferably selected from the esterquats and / or the quaternary ammonium compounds (QAV) according to the general formula (R ^I ) (R ^II ) (R ^III ) (R ^IV ) N ⁺ X-, in which R ^I to RIV for the same or different C _1-22 -alkyl radicals, C _7-28 -arylalkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic bond as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, e.g. a pyridinium or imidazolinium compound, and X- represents halide ions, sulfate ions, hydroxide ions or similar anions. QAV can be produced by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with one long alkyl radical and two methyl groups is particularly easy; the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out with the aid of methyl chloride under mild conditions. Amines that have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are quaternized with dimethyl sulfate, for example. Possible QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride), benzalkon B (m, p-dichlorobenzyldimethyl-C ₁₂ -alkylammonium chloride, benzoxonium chloride (benzyldodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide ( N-hexadecyl-N, N-trimethylammonium bromide), benzetonium chloride (N, N-dimethyl-N [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] -ethoxy] -ethyl] -benzylammonium chloride ), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride, didecyldimethylammonium bromide, dioctyl dimethyl ammonium chloride, 1-cetylpyridinium chloride and Thiazolinjodid and mixtures thereof. Preferred QUATS are the benzalkonium chlorides with C ₈ -C ₂₂ alkyl radicals, in particular C ₁₂ -C ₁₄ -Alkylbenzyldimethylammoniumchlorid.

Preferred esterquats are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyl-oxyethyl) ammonium methosulfate, bis- (palmitoyl) -ethyl-hydroxyethyl-methyl-ammonium-methosulfate or methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. Commercial examples are sold by Stepan under the trade name Stepantex® ^® methylhydroxyalkyldialkoyloxyalkylammonium or those known under the trade name Dehyquart® ^® products from BASF SE or the known under the name Rewoquat ^® products by manufacturer Evonik.

Furthermore, the detergents and cleaning agents can contain further ingredients which further improve the application-related and / or aesthetic properties of the composition, depending on the intended use. In the context of the present invention, they can builders, bleaches, bleach activators, bleach catalysts, esterquats, silicone oils, emulsifiers, thickeners, electrolytes, pH adjusters, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-redeposition agents, solvents, enzymes, optical brighteners, graying inhibitors, enema inhibitors Anti-crease agents, color transfer inhibitors, color protection agents, wetting improvers, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, rinse aids, preservatives, antistatic agents, ironing aids, phobing and impregnating agents, pearlescent agents, polymers, including but not limited to UV absorbers and anti-slip agents be.

The amounts of the individual ingredients in the detergents and cleaning agents are based in each case on the intended use of the composition in question and the person skilled in the art is fundamentally familiar with the magnitudes of the amounts of the ingredients to be used or can take them from the associated specialist literature. Depending on the intended use of the compositions, for example, the surfactant content will be chosen to be higher or lower. Usually, for example, the surfactant content of detergents can be from 10 to 50% by weight, preferably from 12.5 to 30% by weight and more preferably from 15 to 25% by weight.

The washing and cleaning agents can contain, for example, at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builders include polycarboxylic acids, particularly citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, especially amino-tris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxyl compounds such as dextrin and polymeric (poly) carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality in polymerized form. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight. The organic builder substances can be used, in particular for the production of liquid detergents and cleaning agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.

Organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the upper limit mentioned are preferably used in pasty or liquid, in particular water-containing, agents according to the invention. Laundry conditioners, such as fabric softeners, can optionally also be free of organic builders.

Particularly suitable water-soluble inorganic builder materials are alkali metal silicates and polyphosphates, preferably sodium triphosphate. As water-insoluble, water-dispersible inorganic builder materials, in particular crystalline or amorphous alkali metal alumosilicates, if desired, in amounts of up to 50 wt.%, Preferably not more than 40 wt. -%, are used. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular do not have any particles with a grain size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm.

Suitable substitutes or partial substitutes for said aluminosilicate are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in detergents or cleaning agents preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline _{sheet silicates of the general formula Na 2} Si _x O _{2x + 1} · yH ₂ O, in which x, the so-called modulus, is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both beta and delta sodium _{disilicates (Na 2} Si ₂ O ₅ · yH ₂ O) are preferred. It is also possible to use practically anhydrous crystalline alkali silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, prepared from amorphous alkali metal silicates. In a further preferred embodiment, a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda, is used. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of the textile treatment or cleaning agents. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

If desired, builder substances are preferably present in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight. Laundry post-treatment agents, such as fabric softeners, are preferably free of inorganic builders.

Suitable ingredients and frame compositions for detergent and cleaning agent compositions (for example for detergents and fabric softeners) are, for example, in US Pat EP 3 110 393 B1 disclosed.

Suitable ingredients and frame compositions for cosmetic agents, such as hair care compositions, are for example in US Pat DE 102017215071 A1 disclosed.

EXAMPLES

Example 1: Preparation of an anisaldehyde-chitosan fragrance precursor compound (compound A)

5.00 g of chitosan were placed in a 100 mL single-necked flask. 8.00 g of anisaldehyde, 0.02 g of p-toluenesulfonic acid and 10 mL of methanol were added. The mixture was heated to 65 ° C. under reduced pressure for 3 hours and the solvent and the water formed were distilled off until a brown suspension remained in the flask. 3.94 g of the crude product (A) were obtained.

Example 2: smell test

The following values are the mean value of a test from the evaluations of at least three testers trained in determining fragrance impressions. The samples were produced as follows: In each case an approximately 200 mM mixture of the corresponding pure fragrances and their fragrance precursors of the present invention was produced in ethanol. This was then applied to paper test strips. The test strip was placed on a laboratory tray to dry at room temperature and, after the specified time, sprayed with a pH = 3 buffered solution and then smelled. Scale: 0: no odor perceptible to 6: very strong odor impression. Table 1: Smell test Compound A vs. pure fragrance connection Fragrance impression after 6 hours Connection A 4.0 Anisaldehyde 2.33

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• US 2003/0158079 A1 [0030]
• EP 3110393 B1 [0054]
• DE 102017215071 A1 [0055]

Non-patent literature cited

• teffen Arctander, Aroma Chemicals Volume 1 and Volume 2 (published 1960 and 1969, respectively, new edition 2000; ISBN: 0-931710-37-5 and 0-931710-38-3) [0030]

Claims (10)

A fragrance precursor compound of formula (I)

where, independently of one another, in each unit the radical X is selected from -NH ₂ , -NHC (= O) CH ₃ and -N = C (-R ¹ ) -R ² and Z is H; or X and Z together with the radical -O-CH-CH- of the unit to which they are attached form a ring of the formula (II)

form; where R ¹ and R ^{2 are} each independently selected from H or linear, branched or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon radicals containing up to 20 carbon atoms and optionally up to 6 heteroatoms, or R ¹ and R ² each together with the carbon atom to which they are bonded form a cyclic, saturated or unsaturated, hydrocarbon ring with up to 12 carbon atoms which can contain up to 6 heteroatoms; n is an integer from 2 to 4000; with the proviso that the radical R ^{1 -CR 2 is derived in} each case from a fragrance aldehyde of ^{the formula R 1} -C (= O) H or a fragrance ketone of the formula R ¹ -C (= O) -R ² and that at least one X is -N = C (-R ¹ ) -R ² and Z is H and / or at least one X and Z form a ring of the formula (II). The fragrance precursor compound according to Claim 1 , where at least 20% of the radicals X are -N = C (-R ¹ ) -R ² and / or at least 20% of the radicals X and Z together form a ring of the formula (II); and / or less than 10% of the radicals X are -NHC (= O) CH ₃ . The fragrance precursor compound according to Claim 1 or 2 wherein the at least one fragrance precursor compound of the formula (I) is at least one fragrance precursor compound of the formula (III)

where R ¹ and R ^{2 are} each independently selected from H or linear, branched or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon radicals containing up to 20 carbon atoms and optionally up to 6 heteroatoms, or R ¹ and R ² together with the carbon atom to which they are bonded form a cyclic, saturated or unsaturated, hydrocarbon ring with up to 12 carbon atoms which can contain up to 6 heteroatoms; and n is an integer from 2 to 4000; with the proviso that the radical R ¹ -CR ^{2 is derived} from a fragrance aldehyde of the formula R ¹ -C (= O) H or a fragrance ketone of the formula R ¹ -C (= O) -R ² . The fragrance precursor compound according to one of the Claims 1 to 3 wherein the compound is obtained by reacting a chitosan with at least one fragrance aldehyde or ketone selected from dihydro-beta-ionone, frambinone methyl ether, hedione, benzyl acetone, calone, decanal, cyclamen aldehyde, melonal and anisaldehyde, or mixtures thereof. Washing or cleaning agent containing at least one fragrance precursor compound according to one of the Claims 1 to 4th , the compound preferably being contained in a total amount of 0.001 and 5% by weight, advantageously 0.005 and 4% by weight, more advantageously 0.01 and 2% by weight, based in each case on the total weight of the agent . Detergents or cleaning agents Claim 5 , characterized in that (1) it contains at least one surfactant selected from anionic, cationic, nonionic, zwitterionic, amphoteric surfactants or mixtures thereof; and / or (2) it is in solid or liquid form. Air conditioning agent containing at least one fragrance precursor compound according to one of the Claims 1 to 4th , the compound preferably being contained in a total amount of 0.001 and 5% by weight, advantageously 0.005 and 4% by weight, more advantageously 0.01 and 2% by weight, based on the total weight of the agent. Cosmetic agent containing at least one fragrance precursor compound according to one of Claims 1 to 4th , the compound preferably being contained in a total amount of 0.001 and 5% by weight, advantageously 0.005 and 4% by weight, more advantageously 0.01 and 2% by weight, based on the total weight of the agent. Process for the preparation of fragrance precursors of the formula (I) as in Claim 1 defined, comprising the reaction of a compound according to the general formula (IV)

where the radicals X 'are independently selected from —NH ₂ and —NHC (= O) CH ₃ ; and n is an integer from 2 to 4000, with aldehydes of the formula R ¹ -C (= O) H or ketones of the formula R ¹ -C (= O) -R ² or mixtures thereof, where R ¹ and R ^{2 are} as are defined in formula (I), with the proviso that at least one radical X 'is equal to -NH ₂ , preferably at least 50% of the radicals X' are equal to -NH ₂ . Method for long-lasting scenting of surfaces, characterized in that a scent precursor compound according to one of the Claims 1 to 4th or a means after Claim 5 , 6th or 8th is applied to the surface to be scented, the scenting lasting longer than when the respective Fragrance compound or an identical means in which the fragrance precursor compound is replaced by the respective fragrance compound would be used.