DE102019133688A1 - CONTROLLED ODOR RELEASE OF CARBONYL COMPOUNDS FROM AMINO-SUBSTITUTED CARBOHYDRATE PRECURSORS - Google Patents

Abstract

The present invention relates to specific fragrance precursor compounds of formula (I). The invention also relates to agents such as detergents and cleaning agents, air conditioning agents, cosmetic agents and insect repellants which contain this compound according to the invention, a method for producing the compound according to the invention and a method for long-lasting scenting of surfaces. Finally, the invention relates to the use of this compound according to the invention in washing and cleaning agents, air conditioning agents, cosmetic agents and insect repellants.

Description

The present invention relates to specific fragrance precursor compounds of formula (I). The invention also relates to agents such as detergents and cleaning agents, air conditioning agents, cosmetic agents and insect repellants which contain this compound according to the invention, a method for producing the compound according to the invention and a method for long-lasting scenting of surfaces. Finally, the invention relates to the use of this compound according to the invention in washing and cleaning agents, air care agents, cosmetic agents and insect repellants.

In particular, volatile fragrances and insect repellants are no longer noticeable shortly after they have been used and thus no longer contribute to the fragrance experience or protection. It is therefore desirable to provide perfume precursor compounds (profragrances) which, after use, ensure a lasting effect by releasing the perfume through hydrolysis. The aim is also to link the fragrances with special chemical anchor groups, on the one hand to achieve better adhesion of the fragrance precursor compound to the textile and, on the other hand, to release the fragrance in a delayed manner. Furthermore, uncomplicated and inexpensive manufacture of the fragrance precursor compounds is desired.

The inventors have surprisingly found a solution for some of the stated objects and problems with the present invention. The core of the invention are new fragrance precursor compounds, which are preferably based on amino-substituted carbohydrates and thus have the possibility of binding several equivalents of a fragrance or several different fragrances, in particular fragrance aldehydes or fragrance ketones. In addition to the amine functionality, the hydroxyl groups of the substrate can also be used to bind a higher amount of fragrances and thus generate new fragrance precursors. Thus, these compounds can cause a long-lasting fragrance of surfaces, in particular of textiles and skin.

wobei
n gleich 1 oder 2 ist, und
die Reste R₁ bis R₄ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, oder
jeweils zwei Reste von R₁ bis R₄, welche an benachbarte C-Atome des Rings gebunden sind, zusammen mit den C-Atomen des Rings, an welche sie gebunden sind, ein cyclisches 5-Ring- oder 6-Ring-Acetal-Derivat, ein cyclisches 5-Ring- oder 6-Ring-Ketal-Derivat oder ein Oxazolidin-Derivat der Formel (II)

oder ein Imin-Derivat der Formel (III) bilden

wobei

1. (i) bei einem 5-Ring-Acetal-Derivat oder 5-Ring Ketal-Derivat der Formel (II) X für O steht,
2. (ii) bei einem Oxazolidin-Derivat der Formel (II) ein X für O und das andere X für N oder NH steht,
3. (iii) bei einem 6-Ring-Acetal-Derivat oder 6-Ring-Ketal-Derivat der Formel (II) ein X für O und das andere X für CH₂-O steht, und/oder
4. (iv) bei einem Imin-Derivat der Formel (III) R_A für NH₂, OH oder CH₂-OH steht, wobei

sich der Rest R₅-C-R₆ der Formel (II) oder (III) von einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=O)-R₆ ableitet, wobei
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann,
mit der Maßgabe,

1. (a) dass mindestens zwei der Reste R₁ bis R₄ eine Gruppe der Formel (II) oder (III) bilden, und
2. (b) dass mindestens einer, bevorzugt einer, der Reste R₁ bis R₄ NH₂ ist oder in der Gruppe der Formel (II) ein X für N oder NH steht oder eine Gruppe der Formel (III) vorliegt.

Therefore, in a first aspect, the invention relates to a fragrance precursor compound of the formula (I)

in which
n is 1 or 2, and
the radicals R ₁ to R _{4 are} independently selected from NH ₂ , OH and CH ₂ —OH, or
in each case two radicals from R ₁ to R ₄ which are bonded to adjacent carbon atoms of the ring, together with the carbon atoms of the ring to which they are bonded, a cyclic 5-ring or 6-ring acetal derivative , a cyclic 5-ring or 6-ring ketal derivative or an oxazolidine derivative of the formula (II)

or form an imine derivative of formula (III)

in which

1. (i) in the case of a 5-ring acetal derivative or 5-ring ketal derivative of the formula (II), X is O,
2. (ii) in the case of an oxazolidine derivative of the formula (II), one X is O and the other X is N or NH,
3. (iii) in the case of a 6-ring acetal derivative or 6-ring ketal derivative of the formula (II), one X is O and the other X is CH ₂ -O, and / or
4. (iv) in the case of an imine derivative of the formula (III), R _{A is} NH ₂ , OH or CH ₂ —OH, where

the radical R ₅ -CR _{6 of} the formula (II) or (III) is derived from a fragrance _{aldehyde or fragrance ketone of the formula R 5} -C (= O) -R ₆ , where
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents,
with the proviso,

1. (a) that at least two of the radicals R ₁ to R _{4 form} a group of the formula (II) or (III), and
2. (b) that at least one, preferably one, of the radicals R ₁ to R _{4 is} NH ₂ or in the group of the formula (II) one X stands for N or NH or a group of the formula (III) is present.

wobei
die Reste R₇ bis R₁₁ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, oder
jeweils zwei Reste von R₇ bis R₁₁, welche an benachbarte C-Atome des Rings gebunden sind, zusammen mit den C-Atomen des Rings, an welche sie gebunden sind, ein cyclisches 5-Ring- oder 6-Ring-Acetal-Derivat, ein cyclisches 5-Ring- oder 6-Ring-Ketal-Derivat oder ein Oxazolidin-Derivat der Formel (II)

oder ein Imin-Derivat der Formel (III) bilden

wobei

1. (i) bei einem 5-Ring-Acetal-Derivat oder 5-Ring Ketal-Derivat der Formel (II) X für O steht,
2. (ii) bei einem Oxazolidin-Derivat der Formel (II) ein X für O und das andere X für N oder NH steht,
3. (iii) bei einem 6-Ring-Acetal-Derivat oder 6-Ring-Ketal-Derivat der Formel (II) ein X für O und das andere X für CH₂-O steht, und/oder
4. (iv) bei einem Imin-Derivat der Formel (III) R_A für NH₂, OH oder CH₂-OH steht,

wobei
sich der Rest R₅-C-R₆ der Formel (II) oder (III) von einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=O)-R₆ ableitet, wobei
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann,
mit der Maßgabe,

1. (a) dass mindestens zwei der Reste R₇ bis R₁₁ eine Gruppe der Formel (II) oder (III) bilden, und
2. (b) dass mindestens einer, bevorzugt einer, der Reste R₇ bis R₁₁, bevorzugt R₈, NH₂ ist oder in der Gruppe der Formel (II) ein X für N oder NH steht oder eine Gruppe der Formel (III) vorliegt.

In a preferred embodiment, the fragrance precursor compound of the formula (I) is a fragrance precursor compound of the formula (IV)

in which
the radicals R ₇ to R _{11 are} independently selected from NH ₂ , OH and CH ₂ —OH, or
in each case two radicals from R ₇ to R ₁₁ which are bonded to adjacent carbon atoms of the ring, together with the carbon atoms of the ring to which they are bonded, a cyclic 5-ring or 6-ring acetal derivative , a cyclic 5-ring or 6-ring ketal derivative or an oxazolidine derivative of the formula (II)

or form an imine derivative of formula (III)

in which

1. (i) in the case of a 5-ring acetal derivative or 5-ring ketal derivative of the formula (II), X is O,
2. (ii) in the case of an oxazolidine derivative of the formula (II), one X is O and the other X is N or NH,
3. (iii) in the case of a 6-ring acetal derivative or 6-ring ketal derivative of the formula (II), one X is O and the other X is CH ₂ -O, and / or
4. (iv) in the case of an imine derivative of the formula (III), R _{A is} NH ₂ , OH or CH ₂ -OH,

in which
the radical R ₅ -CR _{6 of} the formula (II) or (III) is derived from a fragrance _{aldehyde or fragrance ketone of the formula R 5} -C (= O) -R ₆ , where
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents,
with the proviso,

1. (a) that at least two of the radicals R ₇ to R _{11 form} a group of the formula (II) or (III), and
2. (b) that at least one, preferably one, of the radicals R ₇ to R ₁₁ , preferably R ₈ , is NH ₂ or in the group of the formula (II) an X stands for N or NH or a group of the formula (III) is present .

oder eine Mischung von zwei oder mehr der Verbindungen der Formeln (V) bis (XVI), wobei
sich der Rest R₅-C-R₆ (und R₅'-C-R₆' und R₅''C-R₆'', wenn vorhanden) der Formeln (V) bis (XVI) von einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=O)-R₆ ableitet, wobei der Rest Rs für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann.In a further preferred embodiment of the invention, the fragrance precursor compound according to the invention is at least one fragrance precursor compound of the formulas (V) to (XVI)

or a mixture of two or more of the compounds of the formulas (V) to (XVI), where
the radical R ₅ -CR ₆ (and R ₅ '-CR ₆ ' and R ₅ "CR ₆ ", if present) of the formulas (V) to (XVI) are from a fragrance aldehyde or fragrance ketone of the formula R ₅ -C (= O) -R ₆ , where the radical Rs is a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms Atoms, even more preferably with up to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and the radical R _{6 represents} H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which is heteroatoms, preferably O or N, and / or may contain further substituents.

The fragrance aldehyde or fragrance ketone of the formula R ₅ -C (= O) -R ₆ is preferably selected from the group of aldehydes consisting of adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methylbenzaldehyde), cymal (3- (4-Isopropylphenyl) -2-methylpropanal), ethyl vanillin, florhydral (3- (3-isopropylphenyl) butanal), 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, undecylene aldehyde, Vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene -1-carboxaldehyde (triplal), 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-octadiene-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-indene carboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) hydrocinnamaldehyde , 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1 -carboxaldehyde, 4- (3) (4-methyl-3-pentenyl) -3-cyclohexenecarboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3- cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methylundecanal, 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-methanindane-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-cyclohexene-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-methanindan-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4- (1- methylethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinen-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, methylnonylacetaldehyde, hexanal, trans-2 -Hexenal, Lilial, Cyclamenaldehyde, Triplal, Dupical, Melonal, methylundecanal, undecanal, nonanal and octanal and mixtures thereof or from the group of ketones consisting of 2-undecanone (methylnonyl ketone), methyl-beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1 , 1,2,3,3-pentamethyl-4H-inden-4-one), tonalid (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta -Damascone, iso-Damascone, Damascenone, Methyldihydrojasmonat, Menthon, Carvone, Camphor, Koavon (3,4,5,6,6-Pentamethylhept-3-en-2-one), Fenchon, alpha-Ionon, beta-Ionon, gamma-methyl-ionone, fleuramon (2-heptylcyclopentanone), 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-beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl- 2-cyclohexenone), 6-isopropyldeca-hydro-2-naphton, dimethyloctenone, Frescomenthe (2-butan-2-ylcyclohexan-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-cyclohexene-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), dihydro-beta-ionone, hedion (methyl dihydrojasmonate), frambinon methyl ether (4- (4-methoxyphenyl) butan-2-one), calone (methylbenzodi oxepinon) and mixtures thereof; more preferably selected from dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamenaldehyde, melonal, dupical, anisaldehyde and mixtures thereof, in particular from anisaldehyde, dupical and mixtures thereof.

oder einem Salz davon mit mindestens einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=O)-R₆ oder Mischungen davon, erhalten, wobei
die Reste R₁₂ bis R₁₅ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, und n gleich 1 oder 2, bevorzugt 2, ist,
mit der Maßgabe, dass mindestens einer, bevorzugt einer, der Reste R₁₂ bis R₁₅ für NH₂ steht, wobei bevorzugt die Verbindung der allgemeinen Formel (XVII) ein Amino-substituiertes Kohlenhydrat oder ein Salz davon, stärker bevorzugt Glucosamin oder ein Salz davon, insbesondere D-Glucosamin Hydrochlorid ist, und
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann,
wobei das Duftstoffaldehyd oder -keton bevorzugt ausgewählt ist aus der Gruppe bestehend aus Dihydro-beta-ionon, Frambinonmethylether, Hedion, Benzylaceton, Calone, Decanal, Cyclamenaldehyd, Melonal, Dupical, Anisaldehyd und Mischungen davon, insbesondere Dupical, Anisaldehyd und Mischungen davon.In various embodiments, the at least one fragrance precursor compound according to the invention is obtained by reacting a compound of the general formula (XVII)

or a salt thereof with at least one fragrance aldehyde or fragrance ketone of the formula R ₅ -C (= O) -R ₆ or mixtures thereof, wherein
the radicals R ₁₂ to R _{15 are} independently selected from NH ₂ , OH and CH ₂ -OH, and n is 1 or 2, preferably 2,
with the proviso that at least one, preferably one, of the radicals R ₁₂ to R _{15 is} NH ₂ , the compound of the general formula (XVII) preferably being an amino-substituted carbohydrate or a salt thereof, more preferably glucosamine or a salt thereof , especially D-glucosamine hydrochloride, and
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents,
wherein the fragrance aldehyde or ketone is preferably selected from the group consisting of dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamenaldehyde, melonal, dupical, anisaldehyde and mixtures thereof, in particular dupical, anisaldehyde and mixtures thereof.

In a further aspect, the invention relates to an agent containing at least one fragrance precursor compound according to the invention, the fragrance precursor compound preferably in a total amount of 0.001 to 5% by weight, more preferably from 0.005 to 4% by weight, in particular from 0.01 to 2% by weight % By weight, based in each case on the total weight of the agent in which the agent is contained.

The agent is preferably a washing or cleaning agent, an air conditioning agent or a cosmetic agent.

In a further aspect, the invention relates to an insect repellent containing at least one fragrance precursor compound according to the invention, the fragrance precursor compound preferably in a total amount of 5 to 95% by weight, more preferably from 7 to 90% by weight, even more preferably from 9 to 80 % By weight, in particular from 10 to 50% by weight, based on the total weight of the agent in which the agent is contained.

oder ein Salz davon wobei die Reste R₁₂ bis R₁₅ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, und n gleich 1 oder 2, bevorzugt 2, ist,
mit der Maßgabe, dass mindestens einer, bevorzugt einer, der Reste R₁₂ bis R₁₅ für NH₂ steht, wobei bevorzugt die Verbindung der allgemeinen Formel (XVII) ein Amino-substituiertes Kohlenhydrat oder ein Salz davon, stärker bevorzugt Glucosamin oder ein Salz davon, insbesondere D-Glucosamin Hydrochlorid ist,
mit mindestens einem Duftstoffaldehyd oder Duftstoffketon der Formel R⁵-C(=O)-R⁶ oder Mischungen davon, wobei
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann,
wobei das Duftstoffaldehyd oder -keton bevorzugt ausgewählt ist aus der Gruppe bestehend aus Dihydro-beta-ionon, Frambinonmethylether, Hedion, Benzylaceton, Calone, Decanal, Cyclamenaldehyd, Melonal, Dupical, Anisaldehyd und Mischungen davon, insbesondere Dupical, Anisaldehyd und Mischungen davon,
wobei die Umsetzung bevorzugt unter basischen Bedingungen, stärker bevorzugt in Gegenwart einer Aminverbindung, insbesondere Triethylamin, durchgeführt wird.In a further aspect, the invention relates to a process for producing fragrance precursor compounds according to the invention, the process comprising reacting a compound of the general formula (XVII)

or a salt thereof where the radicals R ₁₂ to R _{15 are} independently selected from NH ₂ , OH and CH ₂ -OH, and n is 1 or 2, preferably 2,
with the proviso that at least one, preferably one, of the radicals R ₁₂ to R _{15 is} NH ₂ , the compound of the general formula (XVII) preferably being an amino-substituted carbohydrate or a salt thereof, more preferably glucosamine or a salt thereof , especially D-glucosamine hydrochloride,
with at least one fragrance aldehyde or fragrance ketone of the formula R ⁵ -C (= O) -R ⁶ or mixtures thereof, wherein
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents,
wherein the fragrance aldehyde or ketone is preferably selected from the group consisting of dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamenaldehyde, melonal, dupical, anisaldehyde and mixtures thereof, in particular dupical, anisaldehyde and mixtures thereof,
wherein the reaction is preferably carried out under basic conditions, more preferably in the presence of an amine compound, in particular triethylamine.

In various embodiments, the fragrance aldehyde or fragrance ketone of the formula R ⁵ -C (= O) -R ⁶ or mixtures thereof are used in a molar excess, preferably in a ratio of about 1.2: 1 to 20: 1, more preferably about 1, 5: 1 to 10: 1, more preferably from about 1.8: 1 to 5: 1, even more preferably in a ratio of about 2: 1 to 3: 1, especially about 2: 1 or 3: 1, to the Compound of the general formula (XVII) given.

In a further aspect, the invention relates to a method for long-lasting scenting of surfaces, characterized in that a fragrance precursor compound according to the invention or an agent according to the invention is applied to the surface to be scented, the surface preferably being a textile or skin.

Finally, in a further aspect, the invention relates to the use of a fragrance precursor compound according to the invention in a washing or cleaning agent, an air conditioning agent, a cosmetic agent or an insect repellent.

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 described features or embodiments of the invention 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 indication does not relate 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 included 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 or of the agent. 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 that 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.

The hydrocarbon radicals of the radicals Rs and R ₆ (and R ₅ 'and R _6' and R ₅ "and R ₆ ", if present) can according to the invention, independently of one another, contain heteroatoms, preferably up to 6 heteroatoms. Thus, preferably 1, 2, 3, 4, 5 or 6 heteroatoms can occur in the individual hydrocarbon radicals, which can be selected from all heteroatoms, but are preferably selected from O and N.

The hydrocarbon radicals of the radicals Rs and R ₆ (and R ₅ 'and R ₆ ' and R ₅ "and R ₆ ", if present) can furthermore contain further substituents according to the invention. This means that one or more hydrogen atoms of the hydrocarbon radicals can be replaced (substituted) by a substituent. Suitable substituents include, but are not limited to, linear, branched, or cyclic Hydrocarbon radicals with up to 22 carbon atoms, preferably hydrocarbon radicals with up to 10 carbon atoms, including alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl or arylalkenyl groups; -OH, -O-R ', -CN, -NO ₂ , -NH ₂ , -C (O) H, -C (O) OH, -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 , are.

The term “cyclic hydrocarbon radical” according to the invention, in particular based on the radicals R ₅ and R ₆ (and R ₅ 'and R ₆ ' and R ₅ '' and R ₆ '' if present) can, without being limited thereto, Rings with 3 to 12 carbon atoms, in particular with 5, 6, 7 or 8 carbon atoms, with and without double bonds, as well as multi-ring systems, heterocycles and also bicyclic and tricyclic ring systems.

bedeutet, dass die Verbindung der Formel (II) eine Struktureinheit aufweist, die einem Acetal, Ketal oder Oxazolidin ähnlich ist oder diese Struktureinheit enthält, jedoch weitere funktionelle Gruppen oder Reste aufweist, die von der eigentlichen Strukureinheit abweichen, z.B. weichen die Reste Rs und/oder R₆ von der typischen Struktureinheit eines Acetals, Ketals oder Oxazolidins ab, weshalb von einem Derivat gesprochen wirdThe term "cyclic 5-ring or 6-ring acetal derivative", "cyclic 5-ring or 6-ring ketal derivative" or "oxazolidine derivative" of the formula (II)

means that the compound of the formula (II) has a structural unit which is similar to an acetal, ketal or oxazolidine or which contains this structural unit, but has further functional groups or radicals which differ from the actual structural unit, for example the radicals Rs and / or R ₆ from the typical structural unit of an acetal, ketal or oxazolidine, which is why it is referred to as a derivative

bedeutet, dass die Verbindung der Formel (III) eine Struktureinheit aufweist, die einem Imin ähnlich ist oder diese Struktureinheit enthält, jedoch weitere funktionelle Gruppen oder Reste aufweist, die von der eigentlichen Struktureinheit abweichen, z.B. weichen die Reste Rs und/oder R₆ von der typischen Struktureinheit eines Imins ab, weshalb von einem Derivat gesprochen wird.The term "imine derivative" of the formula (III)

means that the compound of the formula (III) has a structural unit that is similar to an imine or contains this structural unit, but has further functional groups or radicals that differ from the actual structural unit, for example the radicals Rs and / or R _{6 differ} the typical structural unit of an imine, which is why it is referred to as a derivative.

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 the achievement of 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 fragrance precursor compounds according to the invention are shown here without stereocenters and without a three-dimensional arrangement of the individual atoms in space. However, in addition to the compounds shown, all stereoisomers of the compounds are also included in the context of this invention, unless otherwise defined.

The present invention relates in particular to fragrance precursor compounds of the formula (I), preferably fragrance precursor compounds of the formula (IV), more preferably of the formulas (V) to (XVI) and / or (XVIII) to (XXIX).

ist n gleich 1 oder 2, und
die Reste R₁ bis R₄ werden unabhängig voneinander ausgewählt aus NH₂, OH und CH₂-OH, oder
jeweils zwei Reste von R₁ bis R₄, welche an benachbarte C-Atome des Rings gebunden sind, bilden zusammen mit den C-Atomen des Rings, an welche sie gebunden sind, ein cyclisches 5-Ring- oder 6-Ring-Acetal-Derivat, ein cyclisches 5-Ring- oder 6-Ring-Ketal-Derivat oder ein Oxazolidin-Derivat der Formel (II)

oder ein Imin-Derivat der Formel (III)

wobei

1. (i) bei einem 5-Ring-Acetal-Derivat oder 5-Ring Ketal-Derivat der Formel (II) X für O steht,
2. (ii) bei einem Oxazolidin-Derivat der Formel (II) ein X für O und das andere X für N oder NH steht,
3. (iii) bei einem 6-Ring-Acetal-Derivat oder 6-Ring-Ketal-Derivat der Formel (II) ein X für O und das andere X für CH₂-O steht, und/oder
4. (iv) bei einem Imin-Derivat der Formel (III) R_A für NH₂, OH oder CH₂-OH, bevorzugt für OH, steht,

wobei sich der Rest R₅-C-R₆ der Formel (II) oder (III) von einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=O)-R₆ ableitet, wobei
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, mit der Maßgabe,

1. (a) dass mindestens zwei der Reste R₁ bis R₄ eine Gruppe der Formel (II) oder (III) bilden, und
2. (b) dass mindestens einer, bevorzugt einer, der Reste R₁ bis R₄ NH₂ ist oder in der Gruppe der Formel (II) ein X für N oder NH steht oder eine Gruppe der Formel (III) vorliegt.

In a fragrance precursor compound of formula (I)

n is 1 or 2, and
the radicals R ₁ to R ₄ are selected independently of one another from NH ₂ , OH and CH ₂ —OH, or
In each case two radicals from R ₁ to R ₄ which are bonded to adjacent carbon atoms of the ring, together with the carbon atoms of the ring to which they are bonded, form a cyclic 5-ring or 6-ring acetal Derivative, a cyclic 5-ring or 6-ring ketal derivative or an oxazolidine derivative of the formula (II)

or an imine derivative of the formula (III)

in which

1. (i) in the case of a 5-ring acetal derivative or 5-ring ketal derivative of the formula (II), X is O,
2. (ii) in the case of an oxazolidine derivative of the formula (II), one X is O and the other X is N or NH,
3. (iii) in the case of a 6-ring acetal derivative or 6-ring ketal derivative of the formula (II), one X is O and the other X is CH ₂ -O, and / or
4. (iv) in the case of an imine derivative of the formula (III) R _{A is} NH ₂ , OH or CH ₂ -OH, preferably OH,

where the radical R ₅ -CR _{6 of} the formula (II) or (III) is derived from a fragrance _{aldehyde or fragrance ketone of the formula R 5} -C (= O) -R ₆ , where
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, with the proviso

1. (a) that at least two of the radicals R ₁ to R _{4 form} a group of the formula (II) or (III), and
2. (b) that at least one, preferably one, of the radicals R ₁ to R _{4 is} NH ₂ or in the group of the formula (II) one X stands for N or NH or a group of the formula (III) is present.

wobei
die Reste R₇ bis R₁₁ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, oder jeweils zwei Reste von R₇ bis R₁₁, welche an benachbarte C-Atome des Rings gebunden sind, zusammen mit den C-Atomen des Rings, an welche sie gebunden sind, ein cyclisches 5-Ring- oder 6-Ring-Acetal-Derivat, ein cyclisches 5-Ring- oder 6-Ring-Ketal-Derivat oder ein Oxazolidin-Derivat der Formel (II)

oder ein Imin-Derivat der Formel (III) bilden

wobei

1. (i) bei einem 5-Ring-Acetal-Derivat oder 5-Ring Ketal-Derivat der Formel (II) X für O steht,
2. (ii) bei einem Oxazolidin-Derivat der Formel (II) ein X für O und das andere X für N oder NH steht,
3. (iii) bei einem 6-Ring-Acetal-Derivat oder 6-Ring-Ketal-Derivat der Formel (II) ein X für O und das andere X für CH₂-O steht, und/oder
4. (iv) bei einem Imin-Derivat der Formel (III) R_A für NH₂, OH oder CH₂-OH, bevorzugt für OH, steht,

wobei
sich der Rest R₅-C-R₆ der Formel (II) oder (III) von einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=O)-R₆ ableitet, wobei
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann,
mit der Maßgabe,

1. (a) dass mindestens zwei der Reste R₇ bis R₁₁ eine Gruppe der Formel (II) oder (III) bilden, und
2. (b) dass mindestens einer, bevorzugt einer, der Reste R₇ bis R₁₁, bevorzugt R₈, NH₂ ist oder in der Gruppe der Formel (II) ein X für N oder NH steht oder eine Gruppe der Formel (III) vorliegt.

In a preferred embodiment, the fragrance precursor compound of the formula (I) is a fragrance precursor compound of the formula (IV)

in which
the radicals R ₇ to R _{11 are} independently selected from NH ₂ , OH and CH ₂ -OH, or two radicals each of R ₇ to R ₁₁ which are bonded to adjacent carbon atoms of the ring, together with the carbon atoms of the ring to which they are attached, a cyclic 5-ring or 6-ring acetal derivative, a cyclic 5-ring or 6-ring ketal derivative or an oxazolidine derivative of the formula (II)

or form an imine derivative of formula (III)

in which

1. (i) in the case of a 5-ring acetal derivative or 5-ring ketal derivative of the formula (II), X is O,
2. (ii) in the case of an oxazolidine derivative of the formula (II), one X is O and the other X is N or NH,
3. (iii) in the case of a 6-ring acetal derivative or 6-ring ketal derivative of the formula (II), one X is O and the other X is CH ₂ -O, and / or
4. (iv) in the case of an imine derivative of the formula (III) R _{A is} NH ₂ , OH or CH ₂ -OH, preferably OH,

in which
the radical R ₅ -CR _{6 of} the formula (II) or (III) is derived from a fragrance _{aldehyde or fragrance ketone of the formula R 5} -C (= O) -R ₆ , where
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents,
with the proviso,

1. (a) that at least two of the radicals R ₇ to R _{11 form} a group of the formula (II) or (III), and
2. (b) that at least one, preferably one, of the radicals R ₇ to R ₁₁ , preferably R ₈ , is NH ₂ or in the group of the formula (II) an X stands for N or NH or a group of the formula (III) is present .

In a preferred embodiment, the radical R ₇ , if it is not involved in the formation of an acetal, ketal or oxazolidine derivative, is OH;
the radical R ₈ , if it is not involved in the formation of an acetal, ketal, oxazolidine or imine derivative, is NH ₂ ;
the radicals R ₉ and R ₁₀ , if they are not involved in the formation of an acetal, ketal, oxazolidine or imine derivative, are OH; and or
the radical R ₁₁ , if it is not involved in the formation of an acetal, ketal, oxazolidine or imine derivative, is CH ₂ -OH.

oder eine Mischung von zwei oder mehr der Verbindungen der Formeln (XVIII) bis (XXIX), wobei
die Reste R₇ bis R₁₁, wenn vorhanden, unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, wobei bevorzugt, wenn vorhanden, R₇ OH ist, R₉ NH₂ ist, R₉ OH ist, R₁₀ OH ist und/oder R₁₁ CH₂-OH ist,
der Rest R_A, wenn vorhanden, NH₂, OH oder CH₂-OH, bevorzugt OH, ist,
jedes X unabhängig voneinander für NH, N, O, oder CH₂-O steht, und
sich der Rest R₅-C-R₆ (und R₅'-C-R₆' und R_5''-C-R_6", wenn vorhanden) der Formeln (XVIII) bis (XXIX) von einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=0)-R₆ ableitet, wobei
der Rest Rs für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann,
mit der Maßgabe, dass die mindestens eine Duftstoffvorläuferverbindung der Formeln (XVIII) bis (XXIX) mindestens ein, bevorzugt ein N, NH oder NH₂ außerhalb der Reste R₅ und R₆ (und R₅' und R₆' und R₅'' und R₆'', wenn vorhanden) umfasst.In a further preferred embodiment of the invention, the fragrance precursor compound of the formula (I) or (IV) according to the invention is at least one fragrance precursor compound of the formulas (XVIII) to (XXIX)

or a mixture of two or more of the compounds of the formulas (XVIII) to (XXIX), where
the radicals R ₇ to R ₁₁ , if present, are selected independently of one another from NH ₂ , OH and CH ₂ —OH, where preferably, if present, R _{7 is} OH, R _{9 is} NH ₂ , R _{9 is} OH, R ₁₀ Is OH and / or R _{11 is} CH ₂ -OH,
the radical R _A , if present, is NH ₂ , OH or CH ₂ -OH, preferably OH,
each X independently of one another represents NH, N, O, or CH ₂ -O, and
the radical R ₅ -CR ₆ (and R ₅ '-CR ₆ ' and R _{5 "} -CR _6" , if present) of the formulas (XVIII) to (XXIX) are from a fragrance aldehyde or fragrance ketone of the formula R ₅ -C (= 0) -R ₆ derives, where
the radical Rs for a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms Atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents,
with the proviso that the at least one fragrance precursor compound of the formulas (XVIII) to (XXIX) at least one, preferably one N, NH or NH ₂ outside the radicals R ₅ and R ₆ (and R ₅ 'and R ₆ ' and R ₅ ''and R ₆ '', if present).

oder eine Mischung von zwei oder mehr der Verbindungen der Formeln (V) bis (XVI), wobei
sich der Rest R₅-C-R₆ (und R_5'-C-R_6'und R_5''-C-R₆'', wenn vorhanden) der Formeln (V) bis (XVI) von einem Duftstoffaldehyd oder Duftstoffketon der Formel Rs-C(=0)-R₆ ableitet, wobei
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann.In a further preferred embodiment of the invention, the fragrance precursor compound of the formula (I) or (IV) according to the invention is at least one fragrance precursor compound of the formulas (V) to (XVI)

or a mixture of two or more of the compounds of the formulas (V) to (XVI), where
the radical R ₅ -CR ₆ (and R _{5 '} -CR _6' and R _{5 "} -CR ₆ ", if present) of the formulas (V) to (XVI) are from a fragrance aldehyde or fragrance ketone of the formula Rs-C (= 0) -R ₆ derives, where
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents.

The term "radical R ₅ -CR _6" (or radical R _{5 '} -CR _6' or radical R _{5 "} -CR _6" ) relates, unless otherwise defined, to the corresponding part of the fragrance precursor compound of the formulas (I. ), (IV), (V) to (XVI) or (XVIII) to (XXIX), this part being bonded via the central carbon atom either via a double bond or as part of the ring in the compound differs from fragrance ketones or aldehydes in that the oxygen atom of the aldehyde or ketone compound, which in these compounds is bonded to the central carbon atom via a double bond, is replaced by the remaining part of the fragrance precursor compound of the formulas (I), (IV) , (V) to (XVI) or (XVIII) to (XXIX) is replaced.

From the described fragrance precursor compounds of the formulas (I), (IV), (V) to (XVI) or (XVIII) to (XXIX), the fragrance can be released by hydrolysis, in particular at acidic pH values, ie pH values <7 , for example <6 or <5.

In various embodiments of the invention, the fragrance aldehyde of the formula R ₅ -C (= O) -R ₆ can be selected from adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methylbenzaldehyde), cymal ( 3- (4-isopropylphenyl) -2-methylpropanal), ethylvanillin, florhydral (3- (3-isopropylphenyl) butanal), 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, undecylene aldehyde, vanillin , 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene 1-carboxaldehyde (triplal), 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) propanal, 2-methyl-3- (para-methoxyphenyl) propanal, 2-methyl-4- (2,6,6 -timethyl-2 (1) -cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadien-1-al, 3,7-dimet hyl-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, alpha-dimethylhydrocinnamaldehyde, alpha -Methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2 , 4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4-methyl-3-pentenyl) -3-cyclohexenecarboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-Hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methylundecanal, 2-methyldecanal, 1-nonanal, 1-octanal, 2, 6,10-trimethyl-5,9-undecadienal, 2-methyl-3- (4-tert-butyl) p ropanal, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde, 5- or 6-methoxyhexahydro-4,7-methanindane-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, methylnonylacetaldehyde, hexanal, trans-2-hexenal, lilial, cyclamenaldehyde, triplal, dupical, melonal, methylundecanal, undecanal, nonanal and octanal and mixtures thereof, without to be limited to it.

Suitable ketones include, but are not limited to, 2-undecanone (methyl nonyl ketone), methyl beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl -4H-inden-4-one), tonalid (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate (Hedion), menthone, carvone, camphor, koavone (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fleuramon (2-heptylcyclopentanone), dihydrojasmone, cis-jasmone, 1- (1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) ethane 1-one and isomers thereof, methyl cedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl-beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6- Isopropyldeca-hydro-2-naphton, dimethyloctenone, Frescomenthe (2-butan-2-ylcyclohexan-1-one), 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, meth ylheptenone, 2- (2- (4-methyl-3-cyclohexen-1-yl) propyl) cyclopen-tanone, 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-cyclohexene-1-yl) -1,6-heptadiene- 3-one), isocyclemon E (2-acetonaphthone-1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methylnonyl ketone, methylcyclocitron, methyl lavene 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), dihydro-beta-ionone, frambinone methyl ether (4- (4-methoxyphenyl) butan-2-one), calone (methylbenzodioxepinone), and mixtures thereof.

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

In addition, all customary fragrance aldehydes and / or fragrance ketones which, after conversion, come under the definition of the above-mentioned formulas (II), (III), (V) to (XVI) and (XVII to (XXIX) are used, which are used in particular to induce a pleasant odor sensation 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, reference is made to Steffen 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).

oder ein Salz davon
mit mindestens einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=O)-R₆ oder Mischungen davon, umgesetzt werden,
wobei die Reste R₁₂ bis R₁₅ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, und
n gleich 1 oder 2, bevorzugt 2, ist,
mit der Maßgabe, dass mindestens einer, bevorzugt einer, der Reste R₁₂ bis R₁₅ für NH₂ steht,
wobei bevorzugt die Verbindung der allgemeinen Formel (XVII) eine Verbindung der Formel (XXX)

) oder ein Salz davon ist
stärker bevorzugt ist die Verbindung der Formel (XVII) ein Amino-substituiertes Kohlenhydrat oder ein Salz davon, noch stärker bevorzugt Glucosamin oder ein Salz davon, insbesondere D-Glucosamin Hydrochlorid,
wobei
die Reste R₁₆ bis R₂₀ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, und
mit der Maßgabe, dass mindestens einer, bevorzugt einer, der Reste R₁₆ bis R₂₀, bevorzugt R₁₇, für NH₂ steht,
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann,
wobei das Duftstoffaldehyd oder -keton bevorzugt ausgewählt ist aus der Gruppe bestehend aus Dihydro-beta-ionon, Frambinonmethylether, Hedion, Benzylaceton, Calone, Decanal, Cyclamenaldehyd, Melonal, Dupical, Anisaldehyd und Mischungen davon, insbesondere Dupical, Anisaldehyd und Mischungen davon.For the preparation of the fragrance precursor compound according to the invention, a compound of the general formula (XVII)

or a salt thereof
are reacted with at least one fragrance aldehyde or fragrance ketone of the formula R ₅ -C (= O) -R ₆ or mixtures thereof,
where the radicals R ₁₂ to R _{15 are} independently selected from NH ₂ , OH and CH ₂ —OH, and
n is 1 or 2, preferably 2,
with the proviso that at least one, preferably one, of the radicals R ₁₂ to R _{15 is} NH ₂ ,
where the compound of the general formula (XVII) is preferably a compound of the formula (XXX)

) or a salt thereof
more preferably the compound of the formula (XVII) is an amino-substituted carbohydrate or a salt thereof, even more preferably glucosamine or a salt thereof, in particular D-glucosamine hydrochloride,
in which
the radicals R ₁₆ to R _{20 are} independently selected from NH ₂ , OH and CH ₂ —OH, and
with the proviso that at least one, preferably one, of the radicals R ₁₆ to R ₂₀ , preferably R ₁₇ , is NH ₂ ,
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents,
wherein the fragrance aldehyde or ketone is preferably selected from the group consisting of dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamenaldehyde, melonal, dupical, anisaldehyde and mixtures thereof, in particular dupical, anisaldehyde and mixtures thereof.

In a preferred embodiment, the compound of the formula (XVII) or a salt thereof is a compound of the formula (XXX) or a salt thereof, wherein
R16, R18 and R ₁₉ stand for OH,
R _{17 represents} NH ₂ , and / or
R _{20 represents} CH ₂ -OH.

The fragrance precursor compounds according to the invention can, for example, easily and inexpensively from the corresponding fragrances and a compound of the formula (XVII) or (XXX) or a salt thereof, preferably an amino-substituted carbohydrate or a salt thereof, more preferably glucosamine or a salt thereof, by mixing getting produced.

In various embodiments, the reaction takes place preferably under basic conditions, more preferably in the presence of an amine compound, in particular triethylamine.

The substrate glucosamine can be produced industrially from chitosan, for example, without being restricted to this.

The resulting fragrance precursor compounds of the invention can be isolated and optionally purified by conventional methods.

The fragrance precursor compounds of the invention can also be formulated into various compositions.

In one aspect, the invention therefore relates to an agent containing at least one fragrance precursor compound according to the invention, the fragrance precursor compound preferably in a total amount of 0.001 to 5% by weight, more preferably from 0.005 to 4% by weight, in particular from 0.01 to 2% by weight % By weight, based in each case on the total weight of the agent, is included.

In preferred embodiments, the agent is a washing or cleaning agent, an air conditioning agent or a cosmetic agent.

In a further aspect, the invention relates to an insect repellent containing at least one fragrance precursor compound according to the invention, the fragrance precursor compound preferably in a total amount of 5 to 95% by weight, more preferably from 7 to 90% by weight, even more preferably from 9 to 80 % By weight, in particular from 10 to 50% by weight, based on the total weight of the agent.

The agent can contain at least one further fragrance or at least one further fragrance precursor compound which is different from the fragrance precursor compound according to the invention.

The further fragrances which can optionally be contained in the compositions or agents are not subject to any particular restrictions. Individual fragrance compounds of natural or synthetic origin, e.g. 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, ethylmethylphenylglycinate, allylcyclohexylpropionate, benzylamylate, cyclohexyl propionate, benzylicyl propionate, cyclohexyl propionate, benzyl hexyl propionate, cyclohexyl propionate, styrallylpropionate, benzyl hexyl propionate, benzyl hexyl propionate, benzyl hexyl propionate, benzyl hexyl propionate and benzyl hexyl propionate. 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 mentioned above such as 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 or agents 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, Spik oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, winter green oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil, cypress oil, α-amethanolide, ambrose oil, α-amethanolide Anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, boisambrene forugen, dehydrene forugen, α-decyl styrene, naldehyde, α-decyl styrene , Eucalyptol, farnesol, fenchon, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, methyl heptine carboxylate, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamic alcohol, indole, Iran, isoeugenol, isoeugenol methyl ether, isoeugenol methyl ether, jasrolo , Coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, pM ethylacetophenone, methylchavikol, p-methylquinoline, methyl-ß-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenyl acetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, thalaldehyde, santalum, sandelice, skatol, teranatrineol Cinnamaldehyde, cinnamic alcohol, cinnamic acid, ethyl cinnamate, cinnamic acid benzyl ester, diphenyl oxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl-n-heptenone, pinene, phenyl acetaldehyde, terpinylacetate, citral, and mixtures thereof.

It is also possible that the at least one fragrance precursor compound according to the invention is used with the corresponding aldehydes and / or ketones. According to a preferred embodiment, such compositions are characterized in that the molar ratio of fragrance aldehyde and / or fragrance ketone to the corresponding fragrance precursor compound is 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 agents according to the invention, preferably washing and cleaning agents, air care agents, cosmetic agents and insect repellants, in particular the washing and cleaning agents, can also contain at least one surfactant selected from 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. Corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned in terms of the alkyl moiety, and of alkylphenols with 5 to 12 carbon atoms in the alkyl radical, can also 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 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, and 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- stands for 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, dioctyldimethylammonium chloride, 1-cetylpyridinium chloride and thiazoline iodide and mixtures thereof. Preferred QAC are the benzalkonium chlorides with C ₈ -C ₂₂ -alkyl radicals, in particular C ₁₂ -C ₁₄ -alkylbenzyldimethylammonium chloride. Preferred ester quats are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyl-oxyethyl) ammonium methosulphate, bis- (palmitoyl) -ethyl-hydroxyethyl-methyl-ammonium-methosulphate or methyl-N, N -bis (acyl-oxyethyl) -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 agents according to the invention, preferably the detergents and cleaning agents, air conditioning agents, cosmetic agents and insect repellants, in particular the washing and cleaning agents, may contain further ingredients that further improve the application-related and / or aesthetic properties of the composition or the agent depending on the intended use improve. 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 agents mentioned are based in each case on the intended use of the composition in question and the person skilled in the art is generally 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. Typically, 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 agents according to the invention, in particular 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 builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as well as polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid) and 1, 1-methylenediphosphonic acid, in particular aminotris (methylenephosphonophosphonic acid, 1, 1-methyleniphosphonic acid, and 1-methylenephosphonophosphonic acid), especially aminotris (methylenephosphonic acid), especially aminotris (methylenephosphonic acid) and 1, 1-methylenephosphonic acid, in particular aminotris (methylenephosphonic acid) and 1-methylenediphosphonic acid, monomeric and polymeric aminopolycarboxylic acids, monomeric and polymeric aminopolycarboxylic acids, in particular aminotris (methylenephosphonic acid) and 1, 1 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 post-treatment agents, 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% by weight, preferably not more than 40% by weight and, in liquid compositions, in particular from 1% by weight to 5% by weight. -%, 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 particle 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 silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in agents according to the invention, in particular 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 Na ₂ O: SiO ₂ ratio 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.

According to one aspect of the invention, the fragrance precursor compound according to the invention can be used in a washing or cleaning agent, an air conditioning agent, a cosmetic agent or an insect repellent.

oder ein Salz davon, wobei bevorzugt die Verbindung der allgemeinen Formel (XVII) eine Verbindung der Formel (XXX)

oder ein Salz davon ist, stärker bevorzugt ist die Verbindung der Formel (XVII) ein Amino-substituiertes Kohlenhydrat oder ein Salz davon, noch stärker bevorzugt Glucosamin oder ein Salz davon, insbesondere D-Glucosamin Hydrochlorid,
wobei
die Reste R₁₂ bis R₁₅ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH, und
n gleich 1 oder 2, bevorzugt 2, ist,
mit der Maßgabe, dass mindestens einer, bevorzugt einer, der Reste R₁₂ bis R₁₅ für NH₂ steht, und die Reste R₁₆ bis R₂₀ unabhängig voneinander ausgewählt sind aus NH₂, OH und CH₂-OH,
mit der Maßgabe, dass mindestens einer, bevorzugt einer, der Reste R₁₆ bis R₂₀, bevorzugt R₁₇, für NH₂ steht,
mit mindestens einem Duftstoffaldehyd oder Duftstoffketon der Formel R₅-C(=O)-R₆ oder Mischungen davon, wobei
der Rest R₅ für einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann, und
der Rest R₆ für H oder einen gesättigten oder ungesättigten, linearen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 30 C-Atomen, bevorzugt mit bis zu 20 C-Atomen, stärker bevorzugt mit bis zu 15 C-Atomen, noch stärker bevorzugt mit bis zu 14 C-Atomen, steht, welcher Heteroatome, bevorzugt O oder N, und/oder weitere Substituenten enthalten kann,
wobei das Duftstoffaldehyd oder -keton bevorzugt ausgewählt ist aus der Gruppe bestehend aus Dihydro-beta-ionon, Frambinonmethylether, Hedion, Benzylaceton, Calone, Decanal, Cyclamenaldehyd, Melonal, Dupical, Anisaldehyd und Mischungen davon, insbesondere Dupical, Anisaldehyd und Mischungen davon,
wobei die Umsetzung bevorzugt unter basischen Bedingungen, stärker bevorzugt in Gegenwart einer Aminverbindung, insbesondere Triethylamin, durchgeführt wird.The invention further relates to a method for producing fragrance precursor compounds according to the invention, comprising
the reaction of a compound of the general formula (XVII)

or a salt thereof, the compound of the general formula (XVII) preferably being a compound of the formula (XXX)

or a salt thereof, more preferably the compound of the formula (XVII) is an amino-substituted carbohydrate or a salt thereof, even more preferably glucosamine or a salt thereof, in particular D-glucosamine hydrochloride,
in which
the radicals R ₁₂ to R _{15 are} independently selected from NH ₂ , OH and CH ₂ —OH, and
n is 1 or 2, preferably 2,
with the proviso that at least one, preferably one, of the radicals R ₁₂ to R _{15 is} NH ₂ , and the radicals R ₁₆ to R _{20 are} independently selected from NH ₂ , OH and CH ₂ -OH,
with the proviso that at least one, preferably one, of the radicals R ₁₆ to R ₂₀ , preferably R ₁₇ , is NH ₂ ,
with at least one fragrance aldehyde or fragrance ketone of the formula R ₅ -C (= O) -R ₆ or mixtures thereof, wherein
the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 C atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and
the radical R _{6 stands} for H or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents,
wherein the fragrance aldehyde or ketone is preferably selected from the group consisting of dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamenaldehyde, melonal, dupical, anisaldehyde and mixtures thereof, in particular dupical, anisaldehyde and mixtures thereof,
wherein the reaction is preferably carried out under basic conditions, more preferably in the presence of an amine compound, in particular triethylamine.

In preferred embodiments, the fragrance aldehyde or fragrance ketone of the formula R ⁵ -C (= O) -R ⁶ or mixtures thereof are used in a molar excess, preferably in a ratio of about 1.2: 1 to 10: 1, more preferably about 1, 5: 1 to 10: 1, even more preferably from about 1.8: 1 to 5: 1, even more preferably in a ratio of about 2: 1 to 3: 1, in particular about 2: 1 or 3: 1, added to the compound of the general formula (XVII) or (XXX).

Finally, the invention relates to a method for long-lasting scenting of surfaces, characterized in that a fragrance precursor compound according to the invention or an agent according to the invention, for example a washing and cleaning agent, an air care agent, a cosmetic agent or an insect repellent, is applied to the surface to be scented, whereby the surface is preferably a textile or skin.

In preferred embodiments, the scenting in the method according to the invention lasts longer than if the respective (free) fragrance or an identical agent in which the fragrance precursor compound according to the invention is replaced by the respective (free) fragrance were used.

Examples

Example 1: Reaction of anisaldehyde with D-glucosamine hydrochloride

5.00 g of D-glucosamine hydrochloride in 25 mL of methanol were placed in a secured 100 mL three-necked flask with a distillation bridge. 7.00 g of triethylamine (3rd eq.) Was added dropwise. 6.30 g of anisaldehyde were then added and the mixture was heated at 45 ° C. under reduced pressure until no more liquid could be separated out in the receiver flask. The solid crude product obtained was then suspended in methanol and the mixture was filtered. The filtered solid became then dissolved in water and slowly precipitated from the cold by adding a little methanol and diethyl ether. 8.0 g of the simple cyclization product were obtained as a pale yellowish solid.
¹ H-NMR (400 MHz, _{DMSO- d 6} ): δ = 2.75-2.85 (m, 1H), 3.10-3.30 (m, 2H), 3.35-3.55 (m, 2H), 3.70-3.80 (m, 1H ), 3.80 (s, 3H), 4.50-4.60 (m, 1H), 4.65-4.72 (m, 1H), 4.75-4.85 (m, 1H), 4.88-4.94 (m, 1H), 6.48-6.58 (m , 1H), 7.00 (d, J = 8.40 Hz, 2H), 7.72 (d, J = 8.50 Hz, 2H), 8.13 (s, 1H) ppm. MS (ESI, positive ion): 298 ([M + H] +, 45%), 147 ([M + 2H] ²⁺ , 100%).

Example 2: Reaction of Dupical with D-glucosamine hydrochloride

3.00 g of D-glucosamine hydrochloride in 25 mL of methanol were placed in a secured 100 mL three-necked flask with a distillation bridge. 4.2 g triethylamine (3rd eq.) Was added dropwise. Then 5.7 g of Dupical were added and the mixture was heated at 45 ° C. under reduced pressure until no further liquid could be separated out in the receiver flask. The crude product obtained was then suspended in dichloromethane and mixed with water. The phases were then separated and the organic phase was washed twice with water. It was _{dried over Na 2} SO ₄ , filtered and the organic phase obtained in this way was covered with a little diethyl ether. The mixture was then stored in the refrigerator overnight, as a result of which a yellowish-transparent, viscous oil separated out. The oil was then separated from the supernatant solution by decantation and dried in vacuo. This gave 5.0 g of a mixture which contained both the double and the triple cyclization product.

MS (ESI, positive ion): 737 ([M (2) + H] ⁺ , 60%), 552 ([M (3) + H] ⁺ , 100%).

M (2) = double cyclization product. M (3) = triple cyclization product.

Example 3: smell test

The following values are the mean value from the ratings of at least three testers. The samples were produced as follows: An approx. 100 mM mixture of the corresponding pure fragrances or their fragrance precursors was produced in ethanol. The mixtures were then applied to paper test strips. The test strips were placed on a laboratory tray to dry at room temperature and, after the specified time, smelled directly or sprayed with a pH = 3 buffered solution and then smelled. Scale: 0: no odor perceptible; 6: Very strong fragrance impression. Table 1: Smell test fragrance precursor A vs. pure fragrance after 48 hours dry Spraying with pH = 3 A. 1.2 0.2 Dupical 0 0

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 [0039]
• EP 3110393 B1 [0063]
• DE 102017215071 A1 [0064]

Claims (12)

Perfume precursor compound of formula (I)

where n is 1 or 2, and the radicals R ₁ to R _{4 are} independently selected from NH ₂ , OH and CH ₂ -OH, or two radicals each of R ₁ to R ₄ which are attached to adjacent carbon atoms of the ring are bonded, together with the carbon atoms of the ring to which they are attached, a cyclic 5-ring or 6-ring acetal derivative, a cyclic 5-ring or 6-ring ketal derivative or an oxazolidine -Derivative of the formula (II)

or form an imine derivative of formula (III)

where (i) in the case of a 5-ring acetal derivative or 5-ring ketal derivative of the formula (II), X is O, (ii) in the case of an oxazolidine derivative of the formula (II), one X is O and the other X stands for N or NH, (iii) in the case of a 6-ring acetal derivative or 6-ring ketal derivative of the formula (II), one X stands for O and the other X stands for CH ₂ -O, and / or (iv) in the case of an imine derivative of the formula (III), R _{A stands} for NH ₂ , OH or CH ₂ -OH, the radical R ₅ -CR _{6 of} the formula (II) or (III) being from a fragrance aldehyde or fragrance ketone of the formula Rs-C (= 0) -R ₆ , where the radical R _{5 is} more preferred for a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and the radical R _{6 represents} H or a saturated or unsaturated one, linear, ver branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which heteroatoms, preferably O or N, and / or may contain further substituents, with the proviso, (a) that at least two of the radicals R ₁ to R _{4 form} a group of the formula (II) or (III), and (b) that at least one, preferably one , the radicals R ₁ to R _{4 is} NH ₂ or in the group of the formula (II) an X stands for N or NH or a group of the formula (III) is present. The pro-fragrance compound according to Claim 1 wherein the at least one fragrance precursor compound of formula (I) is at least one fragrance precursor compound of formula (IV)

where the radicals R ₇ to R _{11 are} independently selected from NH ₂ , OH and CH ₂ -OH, or two radicals each of R ₇ to R ₁₁ , which are bonded to adjacent carbon atoms of the ring, together with the C- Atoms of the ring to which they are bound, a cyclic 5-ring or 6-ring acetal derivative, a cyclic 5-ring or 6-ring ketal derivative or an oxazolidine derivative of the formula (II)

or form an imine derivative of formula (III)

where (i) in the case of a 5-ring acetal derivative or 5-ring ketal derivative of the formula (II), X is O, (ii) in the case of an oxazolidine derivative of the formula (II), one X is O and the other X stands for N or NH, (iii) in the case of a 6-ring acetal derivative or 6-ring ketal derivative of the formula (II), one X stands for O and the other X stands for CH ₂ -O, and / or (iv) in the case of an imine derivative of the formula (III), R _{A stands} for NH ₂ , OH or CH ₂ -OH, the radical R ₅ -CR _{6 of} the formula (II) or (III) being from a fragrance aldehyde or fragrance ketone of the formula Rs-C (= 0) -R ₆ , where the radical R _{5 is} more preferred for a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and the radical R _{6 represents} H or a saturated or unsaturated one, linear, ver branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which heteroatoms, preferably O or N, and / or may contain further substituents, with the proviso, (a) that at least two of the radicals R ₇ to R _{11 form} a group of the formula (II) or (III), and (b) that at least one, preferably one , the radicals R ₇ to R ₁₁ , preferably R ₈ , is NH ₂ or in the group of the formula (II) an X stands for N or NH or a group of the formula (III) is present. The pro-fragrance compound according to Claim 1 or 2 , wherein the at least one fragrance precursor compound of the formula (I) or (IV) is at least one fragrance precursor compound of the formulas (V) to (XVI)

or a mixture of two or more of the compounds of the formulas (V) to (XVI), where the radical R ₅ -CR ₆ (and R ₅ '-CR ₆ ' and R ₅ "-CR ₆ ;; if present) of the formulas (V) to (XVI) are from a fragrance aldehyde or fragrance ketone of the formula Rs-C (= 0) -R ₆ derives, where the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 C atoms, preferably with up to 20 C atoms, more preferably with up to 15 C. Atoms, even more preferably with up to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and the radical R _{6 is} H or a saturated or unsaturated, linear, branched or cyclic one Hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which is heteroatoms, preferably O or N, and / or may contain further substituents. The pro-fragrance compound according to any one of Claims 1 to 3rd , wherein the fragrance aldehyde or fragrance ketone of the formula Rs-C (= 0) -R _{6 is} selected from the aldehyde group consisting of adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methylbenzaldehyde), cymal (3- (4-Isopropylphenyl) -2-methylpropanal), ethyl vanillin, florhydral (3- (3-isopropylphenyl) butanal), 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, undecylene aldehyde, Vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene -1-carboxaldehyde (triplal), 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- dime ethyl-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, alpha-dimethylhydrocinnamaldehyde, alpha -Methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2 , 4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4-methyl-3-pentenyl) -3-cyclohexenecarboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-Hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methylundecanal, 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-methanindane-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, methylnonylacetaldehyde, hexanal, trans-2-hexenal, lilial, cyclamenaldehyde, triplal, dupical, melonal, methylundecanal, undecanal, nonanal and octanal and mixtures thereof or from the ketone group consisting of 2-undecanone (methyl nonyl ketone), methyl beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H- inden-4-one), tonalid (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate, menthone, Carvone, camphor, koavone (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fleuramone (2-heptylcyclopentanone), Dihydrojasmone, cis -jasmon, 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-beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, seller ie-ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldeca-hydro-2-naphton, dimethyloctenone, Frescomenthe (2-butan-2-ylcyclohexan-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-cyclohexene -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 lavendelketone, orivon (4-tert-amylcyclohexanone), 4-tert-butylcyclohexanone, Delphon (2-pentylcyclopentanone), muscon (CAS 541-91-3), neobutenone (1- (5.5- Dimethyl-1-cyclohexenyl) 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, tetramerane (6,10-dimethylun decen-2-on), Dihydro-beta-ionone, hedion (methyl dihydrojasmonate), frambinone methyl ether (4- (4-methoxyphenyl) butan-2-one), calone (methylbenzodioxepinone), and mixtures thereof; preferably selected from dihydro-beta-ionone, frambinone methyl ether, hedione, benzyl acetone, calone, decanal, cyclamenaldehyde, melonal, dupical and anisaldehyde and mixtures thereof, in particular from anisaldehyde or dupical and mixtures thereof. The pro-fragrance compound according to any one of Claims 1 to 4th , wherein the at least one fragrance precursor compound by the reaction of a compound of the general formula (XVII)

or a salt thereof with at least one fragrance aldehyde or fragrance ketone of the formula R ₅ -C (= O) -R ₆ or mixtures thereof, where the radicals R ₁₂ to R _{15 are} independently selected from NH ₂ , OH and CH ₂ -OH, and n is 1 or 2, preferably 2, with the proviso that at least one, preferably one, of the radicals R ₁₂ to R _{15 is} NH ₂ , the compound of the general formula (XVII) preferably being an amino -substituted carbohydrate or a salt thereof, more preferably glucosamine or a salt thereof, in particular D-glucosamine hydrochloride, and the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and the radical R ₆ for H or a saturated one or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which May contain heteroatoms, preferably O or N, and / or further substituents, wherein the fragrance aldehyde or ketone is preferably selected from the group consisting of dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamen aldehyde, melonal, dupical , Anisaldehyde and mixtures thereof, especially dupical, anisaldehyde and mixtures thereof. Agent containing at least one fragrance precursor compound according to one of Claims 1 to 5 , wherein the fragrance precursor compound is preferably contained in a total amount of 0.001 to 5% by weight, more preferably from 0.005 to 4% by weight, in particular from 0.01 to 2% by weight, based in each case on the total weight of the agent . The mean after Claim 6 , wherein the agent is a washing or cleaning agent, an air conditioning agent or a cosmetic agent. Insect repellants containing at least one fragrance precursor compound according to any one of Claims 1 to 5 wherein the fragrance precursor compound is preferably in a total amount of 5 to 95% by weight, more preferably 7 to 90% by weight, even more preferably 9 to 80% by weight, in particular 10 to 50% by weight, based on the total weight of the agent. Process for the preparation of fragrance precursor compounds according to any one of Claims 1 to 5 , wherein the process comprises reacting a compound of the general formula (XVII)

or a salt thereof, where the radicals R ₁₂ to R _{15 are} independently selected from NH ₂ , OH and CH ₂ -OH, and n is 1 or 2, preferably 2, with the proviso that at least one, preferably one , the radicals R ₁₂ to R _{15 stands} for NH ₂ , the compound of the general formula (XVII) preferably being an amino-substituted carbohydrate or a salt thereof, more preferably glucosamine or a salt thereof, in particular D-glucosamine hydrochloride, with at least a fragrance aldehyde or fragrance ketone of the formula R ⁵ -C (= O) -R ⁶ or mixtures thereof, where the radical R _{5 is} a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which can contain heteroatoms, preferably O or N, and / or further substituents, and the radical R _{6 represents} H or a saturated or unsaturated Good, linear, branched or cyclic hydrocarbon radical with up to 30 carbon atoms, preferably with up to 20 carbon atoms, more preferably with up to 15 carbon atoms, even more preferably with up to 14 carbon atoms, which is heteroatoms , preferably O or N, and / or further substituents, wherein the fragrance aldehyde or ketone is preferably selected from the group consisting of dihydro-beta-ionone, frambinone methyl ether, hedione, benzylacetone, calone, decanal, cyclamen aldehyde, melonal, dupical, Anisaldehyde and mixtures thereof, in particular dupical, anisaldehyde and mixtures thereof, the reaction preferably being carried out under basic conditions, more preferably in the presence of an amine compound, in particular triethylamine. The process for the preparation of fragrance precursors according to Claim 9 wherein the fragrance aldehyde or fragrance ketone of the formula R ⁵ -C (= O) -R ⁶ or mixtures thereof in molar excess, preferably in a ratio of about 1.5: 1 to 10: 1, more preferably about 1.8: 1 to 5: 1, even more preferably in a ratio of about 2: 1 to 3: 1, in particular about 2: 1 or 3: 1, can be added to the compound of the general formula (XVII). Method for long-lasting scenting of surfaces, characterized in that a fragrance precursor compound according to one of the Claims 1 to 5 or a means according to one of the Claims 6 to 8th is applied to the surface to be scented, the surface preferably being a textile or skin. Use of a pro-fragrance compound according to any one of Claims 1 to 5 in a washing or cleaning agent, an air conditioning agent, a cosmetic agent or an insect repellent.