Epoxy ether compounds as perfuming ingredients
阅读说明：本技术 作为加香成分的环氧基醚化合物 (Epoxy ether compounds as perfuming ingredients ) 是由 R·莫莱蒂 J·库尼 于 2019-10-29 设计创作，主要内容包括：本发明涉及式(I)的环氧基醚化合物作为加香成分的用途,例如赋予花香-青香(茉莉花样)和水样类型的气味香调：该化合物为其任何一种立体异构体或它们的混合物的形式,并且其中虚线代表碳-碳单键或双键；p代表0至3,优选1至3；n代表0至2；R彼此独立地代表氢,各自可选地取代有酯基的C1-C6烷基或C2-C6烯基；R1彼此独立地代表氢原子或C1-C3烷基。(The present invention relates to the use as perfuming ingredient of an epoxy ether compound of formula (I) for example to impart odor notes of the floral-green (jasmine-like) and watery type:)
1. Use as perfuming ingredient of a compound of formula (I):
the compound is in the form of any one of its stereoisomers or a mixture thereof, and wherein
The dotted line represents a carbon-carbon single or double bond;
p represents 0 to 3, preferably 1 to 3;
n represents 0 to 2;
r independently of one another represents C which is in each case optionally substituted by an ester group1-C6Alkyl or C2-C6An alkenyl group;
R1independently of one another, represents a hydrogen atom or C1-C3An alkyl group.
2. Use according to claim 1, wherein the compound (I) corresponds to the following formula:
wherein p, R and R1Is as defined in claim 1.
3. Use according to claim 1 or 2, wherein said compound (I) or compound (II) corresponds to the following formula:
wherein R is1Is as defined in claim 1;
R2represents C1-C6Alkyl or C2-C6An alkenyl group;
R3represents a hydrogen atom or C1-C6An alkyl group.
4. Use according to claims 1 to 3, wherein the chemolysis is carried outCompounds (I) to (III) are C10To C16A compound is provided.
5. The use according to claims 1 to 4, wherein the compounds (I) to (III) are (±) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy ] butanal.
6. A method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least one compound of formula (I):
the compound is in the form of any one of its stereoisomers or a mixture thereof, and wherein
The dotted line represents a carbon-carbon single or double bond;
p represents 0 to 3, preferably 1 to 3;
n represents 0 to 2;
r independently of one another represents C which is in each case optionally substituted by an ester group1-C6Alkyl or C2-C6An alkenyl group;
R1independently of one another, represents a hydrogen atom or C1-C3An alkyl group.
7. A compound of formula (I):
the compound is in the form of any one of its stereoisomers or a mixture thereof, and wherein
The dotted line represents a carbon-carbon single or double bond;
p represents 0 to 3, preferably 1 to 3;
n represents 0 to 2;
r independently of one another represents each optionally substitutedC of the ester group1-C6Alkyl or C2-C6An alkenyl group;
R1independently of one another, represents a hydrogen atom or C1-C3An alkyl group;
with the proviso that 4- (cyclopentyloxy) butyraldehyde, 4- (cyclopentyloxy) -2-ethyl-2-methylbutyraldehyde, 5- (cyclopentyloxy) valeraldehyde, 5- (cyclopentyloxy) -2-ethyl-2-methylpentanal and 5- (cyclopentyloxy) -2, 2-dimethylvaleraldehyde are excluded.
8. A perfuming composition comprising:
i) at least one compound of formula (I) as defined in any one of claims 1 to 6;
ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and
iv) optionally, at least one flavor adjuvant.
9. A perfumed consumer product comprising at least one compound of formula (I) as defined in any one of claims 1 to 6 or a perfuming composition as defined in claim 8.
10. A perfumed consumer product according to claim 9, wherein the perfumery consumer product base is a perfume, a fabric care product, a body-care product, a cosmetic preparation, a skin care product, an air care product or a home care product.
11. A perfumed consumer product according to claim 10, wherein the perfumery consumer product is a fine perfume, an on-apply perfume or eau de toilette, a cologne, a shaving or after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain care product, a shampoo, a coloring preparation, a colour care product, a hair styling product, a dental care product, a disinfectant, a personal care product, a hair spray, a vanishing cream, a body or antiperspirant, a depilatory, a tanning or sunscreen product, a nail product, a skin cleanser, a cosmetic product, a perfumed soap, a shower mousse, oil or gel, or a foot/hand care product, a hygiene product, an air freshener, a "ready to use" powdered air freshener, a mould remover, a furniture care product, a wipe, a dish detergent or a hard-surface detergent, leather care products, automotive care products.
Technical Field
The invention relates to the field of spices (daily chemical essence). More particularly, it relates to the use of epoxy ether compounds as perfuming ingredients. The present invention relates to the use of said compounds in the perfumery industry as well as to compositions or articles containing said compounds.
Background
To the best of our knowledge, none of the compounds of the present invention is known as a perfuming compound or a compound with a general odor.
WO 2011/101757 describes compounds having similar odour notes but differs significantly from the compounds of the present invention in the absence of a carbonyl group on the alkyl ether substituent.
To the best of our knowledge, the prior art does not report or suggest any organoleptic properties of the compounds of formula (I), or any use of said compounds in the field of perfumery.
Disclosure of Invention
The present invention relates to compounds of formula (I) which impart floral-green (jasmine flower-like) and watery notes.
A first object of the present invention is therefore the use as perfuming ingredient of a compound of formula (I):
the compound is in the form of any one of its stereoisomers or a mixture thereof, and wherein
The dotted line represents a carbon-carbon single or double bond;
p represents 0 to 3, preferably 1 to 3;
n represents 0 to 2;
r independently of one another represents C which is in each case optionally substituted by an ester group1-C6Alkyl or C2-C6An alkenyl group;
R1independently of one another, represents a hydrogen atom or C1-C3An alkyl group.
A second object of the present invention is a method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least one compound of formula (I):
the compound is in the form of any one of its stereoisomers or a mixture thereof, and wherein
The dotted line represents a carbon-carbon single or double bond;
p represents 0 to 3, preferably 1 to 3;
n represents 0 to 2;
r independently of one another represents C which is in each case optionally substituted by an ester group1-C6Alkyl or C2-C6An alkenyl group;
R1independently of one another, represents a hydrogen atom or C1-C3An alkyl group.
A third object of the invention is a compound of formula (I):
the compound is in the form of any one of its stereoisomers or a mixture thereof, and wherein
The dotted line represents a carbon-carbon single or double bond;
p represents 0 to 3, preferably 1 to 3;
n represents 0 to 2;
r independently of one another represents C which is in each case optionally substituted by an ester group1-C6Alkyl or C2-C6An alkenyl group;
R1independently of one another, represents a hydrogen atom or C1-C3An alkyl group;
with the proviso that 4- (cyclopentyloxy) butyraldehyde, 4- (cyclopentyloxy) -2-ethyl-2-methylbutyraldehyde, 5- (cyclopentyloxy) valeraldehyde, 5- (cyclopentyloxy) -2-ethyl-2-methylpentanal and 5- (cyclopentyloxy) -2, 2-dimethylvaleraldehyde are excluded.
Another object of the present invention is a perfuming composition comprising:
i) at least one compound of formula (I) as defined above;
ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and
iii) optionally, at least one flavor adjuvant.
Another object of the present invention is a perfumed consumer product comprising at least one compound of formula (I) as defined above or a perfuming composition as defined above.
Detailed Description
Surprisingly, it has now been found that the compounds of formula (I) can be used as perfuming ingredients, for example to impart floral-green (jasmine-like) and watery type odor notes:
the compound is in the form of any one of its stereoisomers or a mixture thereof, and wherein
The dotted line represents a carbon-carbon single or double bond;
p represents 0 to 3, preferably 1 to 3;
n represents 0 to 2;
r independently of one another represents C which is in each case optionally substituted by an ester group1-C6Alkyl or C2-C6An alkenyl group;
R1independently of one another, represents a hydrogen atom or C1-C3An alkyl group.
For the sake of clarity, by the expression "any one of its stereoisomers or mixtures thereof" or similar, it is meant the normal meaning understood by a person skilled in the art, i.e. that the compounds of formula (I) may be pure enantiomers or diastereomers. In other words, the compound of formula (I) may have several stereocenters, and each of the stereocenters may have two different stereochemistries (e.g., R or S). The compounds of formula (I) may even be in the form of pure enantiomers or in the form of mixtures of enantiomers or diastereomers. The compounds of formula (I) may be in racemic or non-racemic (scalemic) form. Thus, the compound of formula (I) may be one stereoisomer, or in the form of a composition of matter comprising or consisting of various stereoisomers.
For the sake of clarity, by the expression "optionally substituted with an ester group" or the like, it is meant the normal meaning understood by a person skilled in the art, i.e. one hydrogen of an alkyl or alkenyl group may be replaced by OC (═ O) RaOR C (═ O) ORaIs substituted by radicals in which RaMay represent a hydrogen atom or C1-4An alkyl group.
According to a particular embodiment, in the compounds of formula (I), p may represent 1,2 or 3, preferably 1 or 2, even more preferably 1.
According to a particular embodiment, in the compounds of formula (I), n may represent 1 or 2, preferably 1.
According to a particular embodiment, in the compound of formula (I), the dotted line may be a carbon-carbon double bond.
According to a particular embodiment of the invention, the compound of formula (I) is a compound of formula (II):
wherein p, R and R1The definitions of (a) are the same as above.
According to a particular embodiment, in the compound of formula (II), p may represent 1 or 2, preferably 1.
According to a particular embodiment, in the compounds of formula (I) or (II), R may represent, independently of one another, C, each optionally substituted by an ester group1-C5Alkyl or C2-C5An alkenyl group. Preferably, R may represent C1-C5An alkyl group. Even more preferably, R may represent methyl, pentyl or isopentyl.
According to a particular embodiment of the invention, the compound of formula (I) or in particular the compound of formula (II) is a compound of formula (III):
wherein R is1Is as defined above;
R2represents C1-C6Alkyl or C2-C6An alkenyl group;
R3represents a hydrogen atom or C1-C6An alkyl group.
According to a particular embodiment, in the compounds of formula (III), R2Can represent C2-C5Alkyl or C2-C5Alkenyl, preferably C3-C5Alkyl or C3-C5Alkenyl, preferably C5Alkyl, even more preferably pentyl or isopentyl.
According to a particular embodiment, in the compounds of formula (III), R3May represent a hydrogen atom or C1-C3Alkyl groups, preferably hydrogen atoms or methyl groups, even more preferably hydrogen atoms.
According to a particular embodiment, in the compounds of formulae (I) to (III), R1May represent independently of one another hydrogen or C1-C2Alkyl groups, preferably hydrogen atoms or methyl groups.
According to a particular embodiment, in the compounds of formulae (I) to (III), all R1May represent a hydrogen atom.
According to another particular embodiment, in the compounds of formulae (I) to (III), one R1May represent methyl, and the remainder of R1May represent a hydrogen atom.
According to any one of the above embodiments of the invention, the compound of formula (I) to (III) is C10To C16Compound, preferably C11To C15Compounds, even preferably C14To C15A compound is provided.
For the sake of clarity, by the expression "wherein one dotted line represents a carbon-carbon single or double bond" or similar, it is meant the normal meaning understood by a person skilled in the art, i.e. that the whole bond between the carbon atoms connected by said dotted line (e.g. the solid and dotted lines) is a carbon-carbon single or double bond.
The compounds of formula (I) are all novel compounds and are therefore a further object of the present invention, with the proviso that 4- (cyclopentyloxy) butyraldehyde, 4- (cyclopentyloxy) -2-ethyl-2-methylbutyraldehyde, 5- (cyclopentyloxy) valeraldehyde, 5- (cyclopentyloxy) -2-ethyl-2-methylpentanal and 5- (cyclopentyloxy) -2, 2-dimethylpentanal are excluded.
As mentioned above, the odor of the compounds of the present invention is characterized by green notes, and in many cases by floral-green notes (jasmine patterns) and water-like notes.
Specific examples of the compounds of the present invention include (+ -) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy group]Butyraldehyde, as a non-limiting example, has a fresh, green, natural and watery connotation. The green note does not impart a mushy note and a musty note. Furthermore, it is also noteworthy that said compounds are related toThe fragrance of the flower is provided,the water-like fragrance of (Z) -3-hexene-1-ol is mixed with the green fragrance of (Z) -3-hexene-1-ol very well.
As another example, there may be cited (+ -) -4- { [2- (3-methylbutyl) -2-cyclopenten-1-yl ] oxy } butanal, (+ -) -2-methyl-3- [ (3-methyl-2-pentyl-2-cyclopenten-1-yl) oxy ] propanal or (+ -) -5- [ (2-pentyl-2-cyclopenten-1-yl) oxy ] pentanal, each of which has an odor similar to that of (+ -) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy ] butanal but is slightly weaker.
According to a particular embodiment of the invention, the compound of formula (I) is (. + -.) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy ] butanal, (. + -.) -4- { [2- (3-methylbutyl) -2-cyclopenten-1-yl ] oxy } butanal, (. + -.) -2-methyl-3- [ (3-methyl-2-pentyl-2-cyclopenten-1-yl) oxy ] propanal or (. + -.) -5- [ (2-pentyl-2-cyclopenten-1-yl) oxy ] pentanal.
According to another particular embodiment of the invention, the compound of formula (I) is (. + -.) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy ] butanal.
When the odor of the compounds of the present invention is compared to the odor of the prior art compound 5-ethoxy-1-pentyl-1-cyclopentene, the compounds of the present invention differ from the prior art compounds by lacking the earthy notes thereof. Said differences make the compounds of the invention and the compounds of the prior art each suitable for different uses, i.e. to impart different sensory impressions.
As mentioned above, the present invention relates to the use of compounds of formula (I) as perfuming ingredients. In other words, it relates to a method or a process for imparting, enhancing, improving or modifying the odor properties of a perfuming composition or of a perfumed article or surface, which method comprises adding to said composition or article an effective amount of at least one compound of formula (I), for example to impart a typical note thereto. It will be appreciated that the final hedonic effect may depend on the precise dosage and organoleptic properties of the compounds of the invention, but in any event, the addition of the compounds of the invention will impart a typical style in the form of a note (note), a style (touch), or a subtle feature (aspect) to the final product depending on the dosage.
By "use of a compound of formula (I)" it must be understood here also the use of any composition containing a compound of formula (I) and which can be advantageously used in the perfumery industry.
Said compositions, which in fact can be advantageously used as perfuming ingredients, are also objects of the present invention.
Therefore, another object of the present invention is a perfuming composition comprising:
i) at least one compound of the invention as defined above as perfuming ingredient;
ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and
iii) optionally, at least one flavor adjuvant.
By "perfumery carrier" it is meant here a material which is practically neutral from a perfumery point of view, i.e. does not significantly modify the organoleptic properties of perfuming ingredients. The carrier may be a liquid or a solid.
As a liquid carrierMention may be made, as non-limiting examples, of emulsifying systems, i.e. solvent and surfactant systems, or solvents commonly used in perfumery. A detailed description of the nature and type of solvents commonly used in perfumery is not exhaustive. However, mention may be made, as non-limiting examples, of solvents such as butanediol or propylene glycol, glycerol, dipropylene glycol and its monoethers, 1,2, 3-propanetriester triacetate, dimethyl glutarate, dimethyl adipate, 1, 3-diacetoxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2- (2-ethoxyethoxy) -1-ethanol, triethyl citrate or mixtures thereof, which are most commonly used. For compositions comprising both a fragrance carrier and a fragrance base, other suitable fragrance carriers than those specified above may also be ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins, such as those under the trademark Iso-paraffinsThose known per se (source: Exxon Chemical), or glycol ethers and glycol ether esters, e.g. under the trade markThose known per se (source: Dow Chemical Company), or hydrogenated castor oil, for example under the trade markRH40 (source: BASF).
By solid carrier is meant a material, to which a perfuming composition or some of the ingredients of a perfuming composition can be chemically or physically associated. Typically, such solid carriers are used to stabilize the composition, or to control the evaporation rate of the composition or certain ingredients. Solid carriers are currently used in the art, and the skilled person knows how to achieve the desired effect. However, as non-limiting examples of solid carriers, mention may be made of absorbent gums or polymers or inorganic materials, such as porous polymers, cyclodextrins, wood-based materials, organic or inorganic gels, clays, gypsum, talc or zeolites.
As other non-limiting examples of solid carriers, encapsulating materials may be cited. Examples of such materials may include wall-forming materials and plasticizing materials, such as monosaccharides, disaccharides or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinyl alcohols, proteins or pectins, or as described in references such as H.Scherz, Hydrokolloides: Stabilisatoren, Dickungs-und Geliermentil in Lebensemitel, Band 2der Schrienreihe Lebensmittemel,Behr's Verlag GmbH&materials listed in cobalt, Hamburg, 1996. Encapsulation is a process well known to those skilled in the art and can be carried out, for example, using techniques such as spray drying, agglomeration or extrusion; or consist of coating encapsulation including coacervation and complex coacervation techniques.
As non-limiting examples of solid carriers, mention may be made in particular of core-shell capsules using resins of the aminoplast, polyamide, polyester, polyurea or polyurethane type or mixtures thereof, all of which are well known to those skilled in the art, by phase separation processes initiated by the use of polymerization, interfacial polymerization, coacervation, and the like techniques or these techniques together, all of which have been described in the prior art, and optionally in the presence of polymeric stabilizers or cationic copolymers.
The resins may be produced by the polycondensation of aldehydes (such as formaldehyde, 2-dimethoxyacetaldehyde, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with amines such as urea, benzoguanamine, glycoureido, melamine, methylolmelamine, methylated methylolmelamine, guanazol and the like and mixtures thereof. Alternatively, preformed resin alkylated polyamines may be used, for example under the trademark Acrylolated(source: Cytec Technology Corp.),(source: Cytec Technology Corp.),Or(source: BASF) commercially available.
Other resins are prepared by reacting a polyol such as glycerol with a polyisocyanate such as a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate or xylylene diisocyanate or a biuret of hexamethylene diisocyanate, or a trimer of xylylene diisocyanate with trimethylolpropane (under the trade nameKnown, sources: mitsui Chemicals), among which the biuret of xylylene diisocyanate with the trimer of trimethylolpropane and hexamethylene diisocyanate is preferred.
Some research literature relating to the encapsulation of fragrances by polycondensation of amino resins, i.e. melamine-based resins, with aldehydes includes articles such as Acta Polymerica,1989, vol.40, pages 243,325 and 683 and 1990, vol.41, page 91, published by k. These articles have described various parameters affecting the preparation of such core-shell microcapsules according to prior art processes, which are also further detailed and exemplified in the patent literature. US4'396'670 to Wiggins Teape Group Limited is a related early example of the latter. Since then, many other authors have enriched the literature in this area, and it is not possible here to cover all published developments, but the general knowledge of encapsulation techniques is of great importance. More recent targeted publications also relate to suitable uses of such microcapsules, and are represented by articles such as K.Bruyninckx and M.Dusselier, ACS Sustainable Chemistry & Engineering,2019, vol.7, pages 8041-.
By "perfumery base" it is meant here a composition comprising at least one perfuming co-ingredient.
Said perfuming co-ingredient is not of formula (I). By "perfuming co-ingredient", it is moreover meant a compound, which is used in a perfuming preparation or composition to impart a hedonic effect. In other words, such a co-ingredient to be considered as being a perfuming co-ingredient must be recognized by a person skilled in the art as being capable of imparting or modifying in an active or pleasant way the odor of a composition, and not just as having an odor.
The nature and type of the perfuming co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the intended use or application and the desired organoleptic effect. In general, these perfuming co-ingredients belong to different chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and can be of natural or synthetic origin.
Mention may in particular be made of perfuming co-ingredients known to have a smell-like note, such as:
mention may in particular be made of the perfuming co-ingredients commonly used in perfumery formulations, such as:
-aldehyde fragrance component: decanal, dodecanal, 2-methylundecanal, 10-undecenal, octanal and/or nonenal;
-aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, 5-methyl tricyclo [ 6.2.1.0-2, 7- ] undec-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4, 4-dimethyl-1, 3-oxathiane (oxathiane), 2,2,7/8, 9/10-tetramethyl spiro [5.5] undec-8-en-1-one, menthol and/or alpha-pinene;
-a balm component: coumarin, ethyl vanillin and/or vanillin;
-citrus flavour components: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, auraptene, limonene, 1-p-menthen-8-yl acetate and/or 1,4(8) -p-menthadiene;
-floral composition: methyl dihydrojasmonate, linalool, citronellol, phenethyl alcohol, 3- (4-tert-butylphenyl) -2-methylpropionaldehyde, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4 (2H) -pyranol, β -ionone, methyl 2- (methylamino) benzoate, (E) -3-methyl-4- (2,6, 6-trimethyl-2-cyclohexen-1-yl) -3-buten-2-one, (1E) -1- (2,6, 6-trimethyl-2-cyclohexen-1-yl) -1-penten-3-one, 1- (2,6, 6-trimethyl-1, 3-cyclohexadien-1-yl) -2-buten-1-one, (2E) -1- (2,6, 6-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one, (2E) -1- [2,6, 6-trimethyl-3-cyclohexen-1-yl ] -2-buten-1-one, (2E) -1- (2,6, 6-trimethyl-1-cyclohexen-1-yl) -2-buten-1-one, 2, 5-dimethyl-2-indanol, 2,6, 6-trimethyl-3-cyclohexen-1-carboxylate, methyl tert-butyl acetate, ethyl, 3- (4, 4-dimethyl-1-cyclohexen-1-ylpropanal, hexyl salicylate, 3, 7-dimethyl-1, 6-nonadien-3-ol, 3- (4-isopropylphenyl) -2-methylpropanal, tricyclodecenyl acetate, geraniol, p-menth-1-en-8-ol, 4- (1, 1-dimethylethyl) -1-cyclohexyl acetate, 1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, pentyl salicylate, homocis-dihydrojasmonic acid methyl ester, 3-methyl-5-phenyl-1-pentanol, tricyclodecenyl propionate, methyl salicylate, methyl propionate, methyl, Geranyl acetate, tetrahydrolinalool, cis-7-p-menthol, propyl (S) -2- (1, 1-dimethylpropoxy) propionate, 2-methoxynaphthalene, 2,2, 2-trichloro-1-phenylethyl acetate, 4/3- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde, amyl cinnamaldehyde, 8-decene-5-lactone, 4-phenyl-2-butanone, isononyl acetate, 4- (1, 1-dimethylethyl) -1-cyclohexyl acetate, tricyclodecenyl isobutyrate, and/or a mixture of methylionone isomers;
-fruit aroma components: gamma-undecalactone, 2, 5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1, 3-oxathiane, 4-decalactone, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1, 3-dioxolane-2-acetate, 3- (3,3/1, 1-dimethyl-5-indanyl) propanal, diethyl 1, 4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, [ 3-ethyl-2-oxiranyl ] acetic acid 1- [3, 3-dimethylcyclohexyl ] ethyl ester and/or diethyl 1, 4-cyclohexanedicarboxylate;
-green components: 2-methyl-3-hexanone (E) -oxime, 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styryl acetate, allyl (2-methylbutoxy) acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z) -3-hexen-1-ol and/or 1- (5, 5-dimethyl-1-cyclohexen-1-yl) -4-penten-1-one;
-a musk component: 1, 4-dioxa-5, 17-cyclopentadecanedione, (Z) -4-cyclopentadecen-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecen-2-one, 1-oxa-13-cyclohexadecen-2-one, (9Z) -9-cyclopentadecen-1-one, 2- {1S) -1- [ (1R) -3, 3-dimethylcyclohexyl ] ethoxy } -2-oxoethyl propionate, 3-methyl-5-cyclopentadecene-1-one, 1,3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-hexamethylcyclopenta [ G ] -2-benzopyran, (1S,1'R) -2- [1- (3',3 '-dimethyl-1' -cyclohexyl) ethoxy ] -2-methylpropyl propionate, oxacyclohexadecan-2-one and/or (1S,1'R) - [1- (3',3 '-dimethyl-1' -cyclohexyl) ethoxycarbonyl ] methyl propionate;
-a woody component: 1- [ (1RS,6SR) -2,2, 6-trimethylcyclohexyl]-3-hexanol, 3-dimethyl-5- [ (1R) -2,2, 3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4 '-dimethylspiro [ ethylene oxide-2, 9' -tricyclo [6.2.1.0 ]2,7]Eleven carbon [ 4]]Alkene, (1-ethoxyethoxy) cyclododecane, acetic acid 2,2,9, 11-tetramethylspiro [5.5]]Undec-8-en-1-yl ester, 1- (octahydro-2, 3,8, 8-tetramethyl-2-naphthyl) -1-ethanone, patchouli oil, terpene fractions of patchouli oil,(1'R, E) -2-ethyl-4- (2',2',3' -trimethyl-3 '-cyclopenten-1' -yl) -2-buten-1-ol, 2-ethyl-4- (2,2, 3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, methyl cedryl ketone, 5- (2,2, 3-trimethyl-3-cyclopentenyl) -3-methylpentan-2-ol, 1- (2,3,8, 8-tetramethyl-1, 2,3,4,6,7,8,8 a-octahydronaphthalen-2-yl) ethan-1-one and/or isobornyl acetate;
other ingredients (e.g. amber, pink, spicy or watery): dodecahydro-3 a,6,6,9 a-tetramethylnaphtho [2,1-b ] furan and any of its stereoisomers, piperonal, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3- (1, 3-benzodioxol-5-yl) -2-methylpropanal, 7-methyl-2H-1, 5-benzodioxepin-3 (4H) -one, 2,5, 5-trimethyl-1, 2,3,4,4a,5,6, 7-octahydro-2-naphthol, 1-phenyl vinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro [4.4] nonane and/or 3- (3-isopropyl-1-phenyl) butyraldehyde.
The perfumery base according to the invention may not be limited to the above-mentioned perfuming co-ingredients, and many other such co-ingredients are in any case listed in the references, such as s.arctander, Perfume and Flavor Chemicals,1969, Montclair, New Jersey, USA or a newer version thereof, or other works of similar nature, as well as a large number of patent documents in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds, also known as pro-fragrances (perfume) or pro-fragrances (perfragrance). Non-limiting examples of suitable pro-fragrances may include 4- (dodecylthio) -4- (2,6, 6-trimethyl-2-cyclohexen-1-yl) -2-butanone, 4- (dodecylthio) -4- (2,6, 6-trimethyl-1-cyclohexen-1-yl) -2-butanone, trans-3- (dodecylthio) -1- (2,6, 6-trimethyl-3-cyclohexen-1-yl) -1-butanone, 2-phenylethyl oxo (phenyl) acetate or mixtures thereof.
According to a particular embodiment, the composition of the invention comprises methyl dihydrojasmonate.
By "perfumery adjuvant" we mean here an ingredient capable of imparting additional benefits such as colour, specific light fastness, chemical stability, etc. A detailed description of the nature and type of adjuvants commonly used in perfuming compositions is not exhaustive, but it must be mentioned that said ingredients are well known to the person skilled in the art. Specific non-limiting examples may be listed as follows: viscosity agents (e.g., surfactants, thickeners, gelling and/or rheology modifiers), stabilizers (e.g., preservatives, antioxidants, heat/light or buffering agents or chelating agents, such as BHT), colorants (e.g., dyes and/or pigments), preservatives (e.g., antibacterial or antimicrobial agents or antifungal or anti-irritant agents), abrasives, skin cooling agents, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.
It is understood that the person skilled in the art is fully capable of designing optimal formulations for the desired effect, simply by applying the standard knowledge in the field and by mixing the above-mentioned components of the perfuming composition by trial and error.
In addition to perfuming compositions comprising at least one compound of formula (I), at least one perfumery carrier, at least one perfumery base and optionally at least one perfumery adjuvant, perfuming compositions consisting of at least one compound of formula (I) and at least one perfumery carrier also constitute a particular embodiment of the invention.
According to a particular embodiment, the above-mentioned composition comprises more than one compound of formula (I) and enables the perfumer to prepare accords or fragrances having the odor tonality of the different compounds of the invention, creating new structural units for the purpose of creation.
For the sake of clarity, it is also understood that any mixture directly resulting from chemical synthesis (wherein the composition of matter of the invention acts as starting material, intermediate or end product), for example a reaction medium which is not sufficiently purified, cannot be considered as a perfuming composition according to the invention, provided that said mixture does not provide the compound of the invention in a suitable form for perfumery. Thus, unpurified reaction mixtures are generally excluded from the present invention unless otherwise specified.
The compounds of the invention can also be advantageously used in all fields of modern perfumery, i.e. fine perfumery or functional perfumery, to actively impart or modify the odor of a consumer product to which said compounds of formula (I) are added. Therefore, another object of the present invention is a perfumed consumer product comprising, as perfuming ingredient, at least one compound of formula (I) as defined above.
The compounds of the invention can be added as such or as part of the perfuming compositions of the invention.
For the sake of clarity, "perfumed consumer product" means a consumer product which delivers at least one pleasant perfuming effect to the surface or space to which it is applied, e.g. skin, hair, fabric or household surface. In other words, a perfumed consumer product according to the invention is a perfumed consumer product comprising the functional formulation and optionally additional benefit agents corresponding to the desired consumer product, and an olfactory effective amount of at least one compound of the invention. For the sake of clarity, said perfumed consumer product is a non-edible product.
The nature and type of the ingredients of perfumed consumer product do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the nature and the desired effect of said product.
Non-limiting examples of suitable perfumed consumer products include perfumes, such as fine perfumes, spread perfumes (splash) or light perfumes (eau de perfume), colognes or shave or after-shave lotions; fabric care products such as liquid or solid detergents, fabric softeners, liquid or solid fragrance enhancers, fabric refreshers, ironing waters, papers, bleaches, carpet cleaners, curtain care products; body care products, such as hair care products (e.g., shampoos, colorants or hair sprays, color care products, hair styling products, dental care products), disinfectants, personal care products; cosmetic preparations (e.g. skin creams or lotions, vanishing creams, body deodorants or antiperspirants (e.g. sprays or roll-ons), depilatories, tanning agents, sun-or after-sun products, nail products, skin cleansing products, cosmetics); or a skin care product (e.g. a soap, bath mousse, oil or gel, or a hygiene product or foot/hand care product); air care products such as air fresheners or "ready-to-use" powder air fresheners, which can be used in home spaces (rooms, refrigerators, cabinets, shoes or cars) and/or public spaces (halls, hotels, malls, etc.); or a home care product, such as a mould remover, a furniture care product, a wipe, a dishwashing detergent or a hard surface (e.g. floor, bathroom, sanitaryware or window cleaning) detergent; leather care products; automotive care products such as polishes, waxes or plastic cleaners.
Some of the above mentioned perfumed consumer products may represent an aggressive medium for the compounds of the invention and may therefore need to be protected from premature decomposition, e.g. by encapsulation or by chemically binding them to another chemical substance suitable for releasing the ingredients of the invention upon exposure to a suitable external stimulus, such as an enzyme, light, heat or a change in pH.
The proportions in which the compounds according to the invention can be incorporated in the various aforementioned products or compositions vary within a wide range of values. When the compounds according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art, these values depend on the nature of the article to be perfumed and on the desired organoleptic effect as well as on the nature of the co-ingredients in a given base.
For example, in the case of perfuming compositions, typical concentrations are in the range of from 0.001% to 20% by weight, or even more, of the compound of the invention based on the weight of the composition into which it is incorporated. In the case of perfumed consumer products, typical concentrations of the compounds of the invention are in the range of from 0.0001% to 5% by weight, or even more, based on the total weight of the consumer product into which they are incorporated.
The compounds of the invention can be prepared by the processes described in the examples below, i.e.by using, for example, a gas mixture CO/H2The double bond is hydroformylated (hydroformylation). Due to the process for preparing the compounds of the invention by hydroformylation, CO can be coupled to either of the two carbon atoms of the double bond. This will result in different mixtures of regioisomers, which means that mixtures of linear or branched hydroformylation products can be obtained.
By using the process for preparing the compounds of the invention by hydroformylation, it is possible to obtain mixtures of linear and branched hydroformylation products of the double bond. In one particular embodiment, the following specific products may be obtained:
mixtures of compounds can be obtained in mixtures of from 99:1 to 40:60, preferably from 95:5 to 60:40 or from 90:10 to 70:30 (i.e. corresponding to the ratio of linear to branched hydroformylation products). Mixtures of linear and branched hydroformylation products may also be used as perfuming ingredients according to the invention.
Examples
The invention will now be described in further detail by the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees Celsius (. degree. C.); is used in (400 MHz: (1H) And 100MHz of (13C) Bruker Advance II Ultrashield 400plus operating at or at (500 MHz: (M.))1H) And 125 MHz: (13C) Bruker Advance III 500plus operating at or at (600 MHz: (M.))1H) And 150MHz of (13C) NMR spectra were obtained with a Bruker Advance III 600 cryoprobe operated as follows. The spectra were internally referenced against 0.0ppm tetramethylsilane.1The H NMR signal shifts are expressed in δ ppm and the coupling constants (J) are expressed in Hz with the following multiplicities: s, singlet; d, double peak; t, triplet; q, quartet; m, multiplet; b, broad peaks (indicating unresolved coupling) and interpreted using Bruker Topspin software.13C NMR data are expressed as chemical shifts δ ppm, hybrid, C, quaternary from DEPT 90 and DEPT 135 experiments; CH, methine; CH (CH)2A methylene group; CH (CH)3And a methyl group.
Example 1
Synthesis of Compounds of formula (I)
a)(±) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy group]Preparation of butyraldehyde
Step 1: synthesis of (+/-) -5-allyloxy-1-pentyl-1-cyclopentene
(. + -.) -2-pentyl-2-cyclopenten-1-ol (40 g; 259mmol) was dissolved in anhydrous THF (0.3 liter) under nitrogen, and the solution was cooled into an ice-water bath. Solid potassium tert-butoxide (36 g; 311mmol) was added all at once. After 10 minutes, the cooling bath was removed and the reaction was stirred for 1.5 hours. The reaction was cooled again to an ice-water bath. Tetrabutylammonium iodide (5.75 g; 15.6mmol) was added, followed by allyl chloride (59.5 g; 778mmol) over 2 hours after 10 minutes. The reaction was warmed to room temperature and stirred overnight. Then it is treated with saturated NH4Quenched with aqueous Cl and extracted twice with ether. The extract was washed with brine and dried over sodium sulfateDried and concentrated on a rotary evaporator. The product was purified by column chromatography on silica gel (eluent: heptane/ethyl acetate 19:1) followed by bulb-to-bulb distillation (60 ℃/1mbar) to give (. + -.) -5-allyloxy-1-pentyl-1-cyclopentene as a colorless liquid (38.6 g; 199 mmol; 77%).
13C-NMR:144.81(s)；135.64(d)；127.46(d)；116.36(t)；85.46(d)；69.36(t)；31.89(t)；30.07(t)；29.94(t)；28.37(t)；27.35(t)；22.60(t)；14.08(q).
1H-NMR:5.99-5.87(m,1H)；5.55(broad s,1H)；5.20(m,2H)；4.42(m,1H)；3.97(m,2H)；2.46-2.34(m,1H)；2.25-2.00(m,4H)；1.85-1.74(m,1H)；1.56-1.23(m,6H)；0.89(t,3H,J＝7Hz).
Step 2: hydroformylation of (+ -) -5-allyloxy-1-pentyl-1-cyclopentene
(+ -) -5-allyloxy-1-pentyl-1-cyclopentene (10 g; 51mmol) was dissolved in toluene (60ml) and purified at 50bar H2In a stainless steel autoclave [ HRh (CO) (PPH) under CO (55: 45; mixed gas)3)3](20 mg; 0.022mmol) and triphenylphosphine (87 mg; 0.332mmol) were stirred in the presence of water at 90 ℃ for 2 h. The reaction was concentrated on a rotary evaporator and the crude material was directly purified by column chromatography on silica gel (eluent: heptane/ethyl acetate 19:1 to 9:1) followed by bulb-to-bulb distillation (85 ℃/0.03mbar) to give (. + -.) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy]Butyraldehyde, a colorless liquid (5.5 g; 24 mmol; 47%).
13C-NMR:202.45(d)；144.64(s)；127.41(d)；86.04(d)；67.15(t)；41.09(t)；31.85(t)；30.06(t)；29.82(t)；28.35(t)；27.31(t)；22.95(t)；22.57(t)；14.07(q).
1H-NMR:9.78(t,1H,J＝1.6Hz)；5.55(m,1H)；4.34(m,1H)；3.53(m,1H)；3.37(m,1H)；2.54(m,2H)；2.43-2.35(m,1H)；2.23-1.99(m,4H)；1.91(m,2H)；1.75(m,1H)；1.54-1.39(m,2H)；1.37-1.24(m,4H)；0.89(t,3H,J＝7Hz).
b) Preparation of (+ -) -2-methyl-3- [ (3-methyl-2-pentylcyclopent-2-en-1-yl) oxy ] propanal
The same reaction sequence as described in example 1a) was used to convert (. + -.) -3-hydroxy-1-methyl-2-pentylcyclopent-1-ene to (. + -.) -2-methyl-3- [ (3-methyl-2-pentylcyclopent-2-en-1-yl) oxy ] propanal. Purification by column chromatography on silica gel (eluent: heptane/ethyl acetate 19:1) followed by bulb-to-bulb distillation (75 ℃/0.01mbar) gave a mixture of diastereomers.
13C-NMR:204.38(d)；204.23(d)；136.83(s)；136.870(s)；135.66(s)；135.65(s)；87.31(d)；87.13(d)；68.49(t)；68.19(t)；47.03(d)；46.98(d)；35.85(t)；35.83(t)；31.92(t)；31.91(t)；28.32(t)；28.31(t)；22.58(t)；14.10(q)；10.96(q)；10.81(q).1H-NMR:9.74(m,1H)；4.44(m,1H)；3.69(m,1H)；3.50(m,1H)；2.62(m,1H)；2.43-2.34(m,1H)；2.21-1.98(m,4H)；1.73-1.66(m,1H)；1.65(broad s,3H)；1.47-1.19(m,6H):1.22(m,3H)；0.89(t,J＝7Hz,3H).
c) Preparation of (+ -) -4- [ (2-isopentylcyclopent-2-en-1-yl) oxy ] butyraldehyde
The same reaction sequence as described in example 1a) was used to convert (+ -) -5-hydroxy-1-isopentyl-cyclopent-1-ene to (+ -) -4- [ (2-isopentylcyclopent-2-en-1) -yl) oxy ] butanal. The product was purified by column chromatography on silica gel (eluent: heptane/ethyl acetate 19:1 to 4:1) followed by bulb-to-bulb distillation (85 ℃/0.05 mbar).
13C-NMR:202.4(d)；144.8(s)；127.3(d)；86.1(d)；67.2(t)；41.1(t)；36.8(t)；30.1(t)；29.8(t)；27.9(d)；26.2(t)；22.9(t)；22.8(q)；22.4(q).
1H-NMR:9.78(broad t,1H)；5.54(m,1H)；4.34(m,1H)；3.53(m,1H)；3.37(m,1H)；2.54(m,2H)；2.42-2.34(m,1H)；2.22-1.98(m,4H)；1.91(m,2H)；1.74(m,1H)；1.55(m,1H)；1.35(m,2H)；0.91(d,J＝7Hz,3H)；0.89(d,J＝7Hz,3H).
d) Preparation of (+ -) -5- [ (2-pentylcyclopent-2-en-1-yl) oxy ] pentanal (coll.74013)
Step 1: synthesis of (+ -) -5- (but-2-en-1-yloxy) -1-pentylcyclopent-1-ene
Reacting (+/-) -5-hydroxy-1-pentane under nitrogenCyclopent-1-ene (10.5 g; 68mmol) was dissolved in anhydrous THF (300ml) and the solution was cooled to an ice-water bath. Solid potassium tert-butoxide (9.5 g; 82mmol) is added all at once. After 10 minutes, the cooling bath was removed and the reaction was stirred for 1.5 hours. The reaction was cooled again to an ice-water bath. Adding n-Bu4NI (1.5 g; 4mmol) and then, after 10 minutes, 1-chlorobut-2-ene (26.4 g; 204mmol) were added over 2 hours (exothermic reaction). The reaction was warmed to room temperature and stirred overnight. Then it is treated with saturated NH4Quenched with aqueous Cl and extracted twice with ether. The extracts were washed with brine, dried over sodium sulfate and concentrated on a rotary evaporator. The product was purified by ball-to-ball distillation (60 ℃/1mbar) to give (. + -.) -5- (but-2-en-1-yloxy) -1-pentylcyclopent-1-ene as a colourless liquid (7 g; 33 mmol; 48%) and as an 70/30 mixture of E/Z isomers.
13C-NMR:144.89(s)；144.88(s)；128.68(d)；128.39(d)；127.72(d)；127.33(d)；127.28(d)；127.19(d)；85.25(d)；85.12(d)；69.11(t)；63.62(t)；31.87(t)；30.11(t)；30.06(t)；29.98(t)；29.92(t)；28.36(t)；28.35(t)；27.31(t)；22.59(t)；17.78(q)；14.08(q)；13.18(q).
1H-NMR:5.74-5.56(m,2H)；5.53(m,1H)；4.40(m,1H)；4.10-3.81(m,2H)；2.45-2.35(m,2H)；2.24-2.01(m,4H)；1.85-1.76(m,1H)；1.72-1.66(m,3H)；1.55-1.24(m,5H)；0.89(m,3H).
Step 2: (±) -5- [ (2-pentylcyclopent-2-en-1-yl) oxy ] pentanal
(+ -) -5- (but-2-en-1-yloxy) -1-pentyl-1-cyclopentene (6.5 g; 32mmol) was dissolved in toluene (60ml) and purified at 50bar H2In a stainless steel autoclave [ HRh (CO) (PPH) under CO (55: 45; mixed gas)3)3](20 mg; 0.022mmol) and triphenylphosphine (87 mg; 0.332mmol) were stirred in the presence of water at 90 ℃ for 4 h. The reaction was concentrated on a rotary evaporator and the crude product was directly purified twice by column chromatography on silica gel (eluent: heptane/ethyl acetate 19:1 to 9:1) followed by bulb-to-bulb distillation (85 ℃/0.03mbar) to yield (. + -.) -5- [ (2-pentyl-2-cyclopenten-1-yl) oxy]Butyraldehyde, a colorless liquid (0.45 g; 1.8 mmo)l；6％)。
13C-NMR:202.6(d)；144.8(s)；127.3(d)；86.0(d)；67.8(t)；43.7(t)；31.9(t)；30.1(t)；29.8(t)；29.6(t)；28.4(t)；27.3(t)；22.6(t)；19.1(t)；14.1(q).
1H-NMR:9.77(t,J＝1.5Hz,1H)；5.54(m,1H)；4.34(m,1H)；3.51(m,1H)；3.35(m,1H)；2.46(m,2H)；2.43-2.35(m,1H)；2.24-2.01(m,4H)；1.80-1.68(m,3H)；1.65-1.58(m,2H)；1.55-1.39(m,2H)；1.37-1.25(m,4H)；0.89(t,J＝7Hz,3H).
Example 2
Preparation of perfuming compositions
A perfuming composition was prepared by mixing the following ingredients:
in dipropylene glycol
1) (-) - (8R) -8, 12-epoxy-13, 14,15, 16-dedimethyl labdane; the source is as follows: firmenich SA of Geneva, Switzerland
2) 7-methyl-2H, 4H-1, 5-benzodioxepin-3 (4H) -one; the source is as follows: firmenich SA of Geneva, Switzerland
3) 1-oxacyclohexadec-12/13-en-2-one; the source is as follows: firmenich SA of Geneva, Switzerland
4) 3-oxo-2-pentylcyclopentaneacetic acid methyl ester; the source is as follows: firmenich SA of Geneva, Switzerland
5) (1S,1'R) -2- [1- (3',3 '-dimethyl-1' -cyclohexyl) ethoxy ] -2-methylpropyl propionate; the source is as follows: firmenich SA of Geneva, Switzerland
6)1- (5, 5-dimethyl-1-cyclohexenyl) pent-4-en-1-one; the source is as follows: firmenich SA of Geneva, Switzerland
7) (E) -3, 3-dimethyl-5- (2,2, 3-trimethyl-3-cyclopenten-1-yl) -4-penten-2-ol; the source is as follows: firmenich SA of Geneva, Switzerland
8) The source is as follows: firmenich SA of Geneva, Switzerland
9)3- (4/2-ethylphenyl) -2, 2-dimethylpropionaldehyde; the source is as follows: international Flavors & Fragrances in the United states
10)1- (octahydro-2, 3,8, 8-tetramethyl-2-naphthyl) -1-ethanone; the source is as follows: international Flavors & Fragrances in the United states
11) [ (Z) -hex-3-enyl ] carbonate; the source is as follows: international Flavors & Fragrances in the United states
12)3- (4-tert-butylphenyl) -2-methylpropionaldehyde; the source is as follows: givaudan SA of Wernel, Switzerland
13) Allyl ionone; the source is as follows: givaudan SA of Wernel, Switzerland
14) Prop-2-enyl 2-cyclohexyloxyacetate; the source is as follows: symrise AG of Hozimin Denmark
15)3- (1, 3-benzodioxazol-5-yl) -2-methylpropanal; the source is as follows: firmenich SA of Geneva, Switzerland
16) 4-methyl-3-decen-5-ol; the source is as follows: givaudan SA of Wernel, Switzerland
17) Pogostemon cablin extract, CAS number 84238-39-1; the source is as follows: firmenich SA of Geneva, Switzerland
The addition of 1000 parts by weight of (±) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy ] butanal to the above composition gives the composition a stronger, fresher, more green, more natural and more watery connotation. The mixing of (+ -) -4- [ (2-pentyl-2-cyclopenten-1-yl) oxy ] butanal with floral Hedione, watery Calone and green (Z) -3-hexen-1-ol components is particularly good.
When 5-ethoxy-1-pentyl-1-cyclopentene is added in place of the compounds of the present invention, the above compositions become more green, more earthy and more musty. 5-ethoxy-1-pentyl-1-cyclopentene does not mix well with the rest of the composition because it gives an unpleasant messy-musty and earthy nuance (facet).
Example 3
Preparation of liquid detergents containing the Compounds of the invention
Table 1: composition of liquid detergent formulation
Composition (I)
Concentration [ weight%]
Sodium C14-17 secondary alkyl sulfonate1)
7
C12-18 and C18-unsaturated fatty acids2)
7.5
C12/14 fatty alcohol polyglycol ether with 7mol EO3)
17
Triethanolamine
7.5
Propylene glycol
11
Citric acid
6.5
Potassium hydroxide
9.5
Properase L4)
0.2
Puradax EG L4)
0.2
Purastar ST L4)
0.2
acrylate/Steareth-20 methacrylate structured Cross-Linked polymers5)
6
Deionized water
27.4
1) Hostapur SAS 60; the source is as follows: clariant
2) Edenor K12-18; the source is as follows: cognis
3) Genapol LA 070; the source is as follows: clariant
4) The source is as follows: genencor International
5) Aculyn 88; the source is as follows: dow Chemical
Liquid detergents were prepared by adding 0.5 to 1.5 wt% of the composition of the invention of example 2 to the unperfumed liquid detergent formulation of table 1 under gentle shaking.
Example 4
Preparation of Fabric softeners comprising the Compound of the invention
Table 2: composition of softening agent formula
Composition (I)
Concentration [ weight%]
Methyl bis [ tallowate ethyl ester group]Ammonium methyl (2-hydroxyethyl) sulfate1)
12.20
1, 2-benzisothiazolin-3-ones2)
0.04
CaCl2(10% aqueous solution)
0.40
Water (W)
87.36
1) Stepandex VL 90A Diester Quat; the source is as follows: stepan
2) Proxel GXL; the source is as follows: arch
Methyl bis [ tallowate ethyl ester ] heated to 65 ℃ by weighing]-2-hydroxyethyl ammonium methyl sulfate to prepare the softener. Then water and 1, 2-benzisothiazolin-3-one are placed in a reactor and heated at 65 ℃ with stirring. To the above mixture was added methyl bis [ tallowate ethyl ester group]-2-hydroxyethyl ammonium methyl sulfate. The mixture was stirred for 15 minutes and CaCl was added2. Then, 0.5 to 2% by weight of the composition according to the invention of example 2, relative to the total weight of the softener, is added. The mixture was stirred for 15 minutes and cooled to room temperature with stirring (viscosity measurement: result 35+/-5 mPas. (shear rate 106 sec-1)).
Example 5
Preparation of a clear homogeneous shampoo comprising the composition of the invention
Table 3: composition of transparent homogeneous shampoo formulation
1) Ucare Polymer JR-400, source: noveon
2) The source is as follows: schweizerhall
3) Glydant, source: lonza
4) Texapon NSO IS, source: cognis
5) Tego Betain F50, source: evonik
6) Amphotensid GB 2009, source: zschimmer & Schwarz
7) Monomuls 90L-12, source: gruenau
8) Sodium paraben, source: NIPA
The shampoo is prepared by dispersing polyquaternium-10 in water. The remaining ingredients of phase a were added one by one while mixing thoroughly after each adjuvant was added. This premix was added to the polyquaternium-10 dispersion and mixed for an additional 5 minutes. Then, premix phase B and premix phase C were added while stirring (Monomuls 90L-12 was heated to melt in Texapon NSO IS). Add phase D and phase E while stirring. Adjusting the pH with citric acid solution until pH: 5.5-6.0, and preparing the shampoo formula without perfuming.
Perfumed shampoos were prepared by adding 0.4 to 0.8 wt.%, relative to the total weight of the shampoo, of the composition of the invention of example 2 to the unperfumed shampoo formulation of table 3 under gentle shaking.
Example 6
Preparation of a structured body wash comprising the composition of the invention
Table 4: composition of shower gel formula
Composition (I)
Amount (% by weight)
Deionized water
49.350
Tetrasodium EDTA1)
0.050
Acrylate copolymer2)
6.000
Sodium C12-C15 alkanolpolyether sulfate3)
35.000
20% aqueous solution of sodium hydroxide
1.000
Cocoamidopropyl betaine4)
8.000
Methylchloroisothiazolinone and methylisothiazolinone5)
0.100
Citric acid (40%)
0.500
1) An EDETA B powder; trade mark and origin: BASF
2) CARBOPOL AQUA SF-1 polymer; trade mark and origin: NOVEON
3) ZETESOL AO 328U; trade mark and origin: ZSCHEMMER & SCHWARZ
4) TEGO-BETAIN F50; trade mark and origin: GOLDSCHMIDT
5) KATHON CG; trade mark and origin: ROHM & HASS
A body wash was prepared by adding 0.5 to 1.5 wt% of the inventive composition of example 2 to the unperfumed body wash formulation of table 4 under gentle shaking.
Example 7
Preparation of clear shower gel comprising the composition of the invention
Table 5: composition of transparent shower gel formula
Composition (I)
Concentration (% by weight)
Deionized water
52.40
Tetrasodium EDTA1)
0.10
Sodium benzoate
0.50
Propylene glycol
2.00
Sodium C12-C15 alkanolpolyether sulfate2)
35.00
Cocoamidopropyl betaine3)
8.00
Polyquaternium-74)
0.20
Citric acid (40%)
1.00
Sodium chloride
0.80
1) An EDETA B powder; trade mark and origin: BASF
2) ZETESOL AO 328U; trade mark and origin: ZSCHEMMER & SCHWARZ
3) TEGO-BETAIN F50; trade mark and origin: GOLDSCHMIDT
4) Merquatt 550; trade mark and origin: LUBRIZOL
A clear body wash was prepared by adding 0.5 to 1.5 wt% of the inventive composition of example 2 to the unperfumed body wash formulation of table 5 under gentle shaking.
Example 8
Preparation of a milky body wash comprising the composition of the invention
Table 6: composition of milky body wash formula
Composition (I)
Concentration (% by weight)
Deionized water
50.950
Tetrasodium EDTA1)
0.050
Sodium benzoate
0.500
Glycerol 86 percent
3.500
Sodium dodecyl polyoxyethylether sulphate2)
27.000
Polyquaternium-73)
1.000
Cocoamidopropyl Betaine (Coco-Betaine)4)
6.000
PEG-120 methyl glucose trioleate5)
1.000
Citric acid (40%)
1.000
Ethylene glycol distearate&Laureth-4&Cocoamidopropyl betaine6)
3.000
20 percent of sodium chloride
5.000
PEG-40 hydrogenated Castor oil7)
1.000
1) An EDETA B powder; trade mark and origin: BASF
2) Texapon NSO IS; trade mark and origin: COGNIS
3) Merquatt 550; trade mark and origin: LUBRIZOL
4) DEHYTON AB-30; trade mark and origin: COGNIS
5) Glucamine LT; trade mark and origin: LUBRIZOL
6) EUPERLAN PK 3000 AM; trade mark and origin: COGNIS
7) CREMOPHOR RH 40; trade mark and origin: BASF
A clear body wash was prepared by adding 0.5 to 1.5 wt% of the inventive composition of example 2 to the unperfumed body wash formulation of table 6 under gentle shaking.
Example 9
Preparation of a pearlescent shampoo comprising the composition of the invention
Table 7: composition of pearly luster homogeneous shampoo formula
1) EDETA B powder, source: BASF
2) Jaguar C14S, source: rhodia
3) Ucare Polymer JR-400, source: noveon
4) Sulfetal LA B-E, source: zschimmer & Schwarz
5) Zetesol LA, source: zschimmer & Schwarz
6) Tego Betain F50, source: evonik
7) Xiameter MEM-1691, source: dow Corning
8) Lanete 16, source: BASF
9) Complerlan 100, source: cognis
10) Cutina AGS, source: cognis
11) Kathon CG, source: rohm & Haas
12) D-panthenol, source: roche
The shampoo was prepared by dispersing guar hydroxypropyltrimonium chloride and polyquaternium-10 in water and tetrasodium EDTA. Once phase a was homogeneous, NaOH 10% solution (phase B) was added. Then, add pre-mixed phase C. And the mixture was heated to 75 ℃. Add phase D ingredients and mix until uniform. The mixture was cooled. Phase E ingredients were added with mixing at 45 ℃. Adjusting the final viscosity by using 25% NaCl solution, and adjusting the pH value to 5.5-6 by using 10% NaOH solution.
A perfumed pearlescent shampoo was prepared by adding 0.4 to 0.8 wt% of the inventive composition of example 2 to the unflavored shampoo formulation of table 7 under gentle shaking to the total weight of the shampoo.
Example 10
Preparation of a structured body wash comprising the composition of the invention
Table 8: composition of milky body wash formula
Composition (I)
Amount (% by weight)
Deionized water
49.350
Tetrasodium EDTA1)
0.050
Acrylate copolymer2)
6.000
Sodium C12-C15 alkanolpolyether sulfate3)
35.000
20% aqueous solution of sodium hydroxide
1.000
Cocoamidopropyl betaine4)
8.000
Methylchloroisothiazolinone and methylisothiazolinone5)
0.100
Citric acid (40%)
0.500
6) An EDETA B powder; trade mark and origin: BASF
7) CARBOPOL AQUA SF-1 polymer; trade mark and origin: NOVEON
8) ZETESOL AO 328U; trade mark and origin: ZSCHEMMER & SCHWARZ
9) TEGO-BETAIN F50; trade mark and origin: GOLDSCHMIDT
10) KATHON CG; trade mark and origin: ROHM & HASS
A clear body wash was prepared by adding 0.5 to 1.5 wt% of the inventive composition of example 2 to the unperfumed body wash formulation of table 8 under gentle shaking.
Example 11
Preparation of eau de toilette comprising the Compound of the invention
The eau de toilette was prepared by adding 5 to 20% by weight of the composition of the invention of example 2, relative to the total weight of the eau de toilette, to ethanol under gentle shaking.
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