U.S. patent application number 15/758589 was filed with the patent office on 2018-10-04 for a green, lily of the valley perfuming ingredient.
This patent application is currently assigned to Firmenich SA. The applicant listed for this patent is Firmenich SA. Invention is credited to Anthony Alexander BIRKBECK, Robert MORETTI.
Application Number | 20180282660 15/758589 |
Document ID | / |
Family ID | 54147101 |
Filed Date | 2018-10-04 |
United States Patent
Application |
20180282660 |
Kind Code |
A1 |
MORETTI; Robert ; et
al. |
October 4, 2018 |
A GREEN, LILY OF THE VALLEY PERFUMING INGREDIENT
Abstract
The present invention concerns compound of formula ##STR00001##
in the form of any one of its stereoisomers or a mixture thereof,
and wherein the exocyclic dotted line represents a carbon-carbon
single or double bond, and one endocyclic dotted to line represents
a carbon-carbon single bond and the other endocyclic dotted line
represents a carbon-carbon double bond; and R, R.sup.1 and R.sup.2
represent, independently from each other, a hydrogen atom or a
C.sub.1-3 alkyl group; and their use in perfumery to impart odor
notes of the green, floral type.
Inventors: |
MORETTI; Robert; (Geneva 8,
CH) ; BIRKBECK; Anthony Alexander; (Geneva 8,
CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Firmenich SA |
Geneva 8 |
|
CH |
|
|
Assignee: |
Firmenich SA
Geneva 8
CH
|
Family ID: |
54147101 |
Appl. No.: |
15/758589 |
Filed: |
September 13, 2016 |
PCT Filed: |
September 13, 2016 |
PCT NO: |
PCT/EP2016/071531 |
371 Date: |
March 8, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 2601/16 20170501;
C07C 47/225 20130101; C11B 9/0034 20130101 |
International
Class: |
C11B 9/00 20060101
C11B009/00; C07C 47/225 20060101 C07C047/225 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 16, 2015 |
EP |
15185462.7 |
Claims
1. A compound of formula (I) ##STR00008## in the form of any one of
its stereoisomers or a mixture thereof, and wherein the exocyclic
dotted line represents a carbon-carbon single or double bond, and
one endocyclic dotted line represents a carbon-carbon single bond
and the other endocyclic dotted line represents a carbon-carbon
double bond; and R, R.sup.1 and R.sup.2 represent, independently
from each other, a hydrogen atom or a C.sub.1-3 alkyl group.
2. The compound of claim 1, characterized in that said R is a
methyl group.
3. The compound of claim 1, characterized in that R.sup.1 is a
hydrogen atom or methyl group.
4. The compound of claim 1, characterized in that R.sup.2 is a
hydrogen atom or a methyl group.
5. The compound of claim 1, characterized in that the compound is
3-[5-(2-propanyl)-1-cyclohexen-1-yl]propanal and/or its isomer
3-[3-(2-propanyl)-1-cyclohexen-1-yl]propanal.
6. (canceled)
7. A perfuming composition comprising i) at least one compound of
formula (I), as defined in claim 1; ii) at least one ingredient
selected from the group consisting of a perfumery carrier and a
perfumery base; and iii) optionally at least one perfumery
adjuvant.
8. A perfuming consumer product comprising at least one compound of
formula (I), as defined in claim 1.
9. A perfuming consumer product according to claim 8, characterized
in that the perfumery consumer product 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.
10. A perfuming consumer product according to claim 8,
characterized in that the perfumery consumer product is a fine
perfume a splash or eau de perfume, a cologne, an shave or
after-shave lotion, a liquid or solid detergent, a fabric softener,
a fabric refresher, an ironing water, a paper, a bleach, a carpet
cleaners, curtain-care products, a shampoo, a coloring preparation,
a color care product, a hair shaping product, a dental care
product, a disinfectant, an intimate care product, a hair spray, a
vanishing cream, a deodorant or antiperspirant, hair remover, a
tanning or sun product, nail products, skin cleansing, a makeup, a
perfumed soap, shower or bath mousse, oil or gel, foot/hand care
products, a hygiene product, an air freshener, a "ready to use"
powdered air freshener, a mold remover, furnisher care, wipe, a
dish detergent, a hard-surface detergent, a leather care product or
a car care product.
11. 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 a compound of formula (I) as defined
in claim 1.
12. The method of claim 11, wherein the R of the compound of
formula (I) is a methyl group.
13. The method of claim 11, wherein the R1 of the compound of
formula (I) is a hydrogen atom or methyl group.
14. The method of claim 11, wherein the R2 of the compound of
formula (I) is a hydrogen atom or a methyl group.
15. The method of claim 11, wherein the compound is
3-[5-(2-propanyl)-1-cyclohexen-1-yl]propanal and/or its isomer
3-[3-(2-propanyl)-1-cyclohexen-1-yl]propanal.
Description
TECHNICAL FIELD
[0001] The present invention relates to the field of perfumery.
More particularly, it concerns the use as perfuming ingredient of
compounds of formula (I) as defined below, which are useful
perfuming ingredients of the green, floral type. Therefore,
following what is mentioned herein, the present invention comprises
the invention's compound as part of a perfuming composition or of a
perfuming consumer product.
PRIOR ART
[0002] To the best of our knowledge, the compounds of formula (I)
are novel.
[0003] To the best of our knowledge, the prior art reports some
structural analogues as perfuming ingredients.
[0004] WO 08/053148 reports some cyclohexyl (i.e. saturated)
analogues of the present invention which are described as having
perfuming properties of the lily of the valley type. Said document
does not suggest unsaturated compounds, and the only compounds
having also green note do have a significantly different
substitution pattern compared to the present ones.
[0005] US 2009/0036347 discloses also cyclohexyl (i.e. saturated)
analogues of the present invention (in particular
3-(3-isopropylcyclohexyl)propanal) as having orris, earthy and
fatty odor note, so perfuming properties very different from the
one of the present invention.
[0006] Therefore, none of these prior art documents reports or
suggests any organoleptic properties of the compounds of formula
(I), or any use of said compounds in the field of perfumery.
DESCRIPTION OF THE INVENTION
[0007] We have now surprisingly discovered that a cyclohexenyl
compound of formula
##STR00002## [0008] in the form of any one of its stereoisomers or
a mixture thereof, and wherein the exocyclic dotted line represents
a carbon-carbon single or double bond, and one endocyclic dotted
line represents a carbon-carbon single bond and the other
endocyclic dotted line represents a carbon-carbon double bond; and
[0009] R, R.sup.1 and R.sup.2 represent, independently from each
other, a hydrogen atom or a C.sub.1-3 alkyl group; can be used as
perfuming ingredient, for instance to impart odor notes of the
green, floral type.
[0010] For the sake of clarity, by the expression "any one of its
stereoisomers", or the similar, it is meant the normal meaning
understood by a person skilled in the art, i.e. that the
invention's compound can be a pure enantiomer (if chiral) or
diastereomer (e.g. the ring substituent is in a conformation syn or
anty).
[0011] For the sake of clarity, by the expression "wherein . . .
dotted line represents a carbon-carbon single bond or double bond .
. . ", or the similar, it is meant the normal meaning understood by
a person skilled in the art, i.e. that the whole bonding (solid and
dotted line) between the carbon atoms connected by said dotted line
is a carbon-carbon single or double bond, provided that only one
cyclic dotted line is a double bond.
[0012] For the sake of clarity, by the expression "endocyclic" it
is meant the normal meaning understood by a person skilled in the
art, i.e. that the whole bonding is located within the cyclic
moiety. Similarly, by the expression "exocyclic" it is meant the
normal meaning understood by a person skilled in the art, i.e. that
the whole bonding is located outside the cyclic moiety.
[0013] According to a particular embodiment of the invention, said
compound (I) is a compound of formula
##STR00003##
wherein one dotted line represents a carbon-carbon single bond and
the other dotted line represents a carbon-carbon double bond, and
R.sup.1 and R.sup.2 have the same meaning indicated in formula
(I).
[0014] According to any one of the above embodiments of the
invention, said invention's compounds are C.sub.12-C.sub.14
compounds.
[0015] According to any one of the above embodiments of the
invention, said R is a hydrogen atom or a methyl or ethyl group, in
particular a methyl group.
[0016] According to any one of the above embodiments of the
invention, said R.sup.1 is a hydrogen atom or a methyl or ethyl
group, in particular a hydrogen atom or a methyl group.
[0017] According to any one of the above embodiments of the
invention, said R.sup.2 is a hydrogen atom or a methyl or ethyl
group, in particular a hydrogen atom or a methyl group.
[0018] According to any one of the above embodiments of the
invention, one of said R.sup.1 or R.sup.2 is a hydrogen atom and
the other is a hydrogen atom or a methyl group.
[0019] According to any one of the above embodiments of the
invention, said R.sup.1 and R.sup.2 are each a hydrogen atom.
[0020] According to any one of the above embodiments of the
invention, said R.sup.1 is a hydrogen atom and R.sup.2 is a methyl
group.
[0021] As specific examples of the invention's compounds, one may
cite, as non-limiting example,
3-[5-(2-propanyl)-1-cyclohexen-1-yl]propanal and/or its isomer
3-[3-(2-propanyl)-1-cyclohexen-1-yl]propanal which are
characterized by an odor having very powerful fresh green and
floral (lily of the valley type) notes duality comprising also
citrus and violet leaves/pyrazine aspects. Said compounds can
impart an astonishing green freshness allied with a remarkable
substantivity, a rare combination for perfumery ingredients. Said
green note has a clear sap, watery connotation.
[0022] According to a particular embodiment of the invention, the
mixtures of said 3-[5-(2-propanyl)-1-cyclohexen-1-yl]propanal and
its isomer 3-[3-(2-propanyl)-1-cyclohexen-1-yl]propanal are
particularly appreciated for their olfactive performances.
[0023] As other specific, but non-limiting, examples of the
invention's compounds, one may cite the following ones in Table
1:
TABLE-US-00001 TABLE 1 Invention's compounds and their odor
properties Compound structure and name Odor notes ##STR00004##
Strong green, floral notes with aldehyde and watery aspects
3-[(5S)-5-isopropyl-2-methyl-1- cyclohexen-1-yl]propanal
##STR00005## Fresh citrus, green, floral notes
3-[(5R)-5-isopropyl-2-methyl-1- cyclohexen-1-yl]-2-methylpropanal
##STR00006## Green, ozone, floral/lily of the valley
3-[5-ethyl-1-cyclohexen-1-yl]propanal ##STR00007##
Green/watery/sap, floral/lily of the valley
3-(5-(sec-butyl)cyclohex-1-en-1- yl)propanal
[0024] According to a particular embodiment of the invention, the
compounds of formula (I) are
3-[5-(2-propanyl)-1-cyclohexen-1-yl]propanal,
3-[3-(2-propanyl)-1-cyclohexen-1-yl]propanal and the mixture
thereof, 3-(5-sec-butyl-1-cyclohexen-1-yl)propanal,
3-[5-ethyl-1-cyclohexen-1-yl]propanal as well as
3-(5-isopropyl-2-methyl-1-cyclohexen-1-yl)propanal.
[0025] When the odor of the invention's compounds is compared with
that of the prior art cyclohexyl derivatives (for instance
3-(3-isopropylcyclohexyl)propanal,
3-(3-(tert-butyl)cyclohexyl)propanal or
3-(3-isopropylcyclohexyl)butanal, see US and WO references above)
and in particular to 3-(3-isopropylcyclohexyl)butanal, then the
invention's compounds distinguish themselves by lacking, or not
possessing significant, orris, earthy and fatty/aldehyde notes, as
well as lacking, or not possessing a significant, powdery
undernotes which are characteristic of the prior art compounds. On
the other hand, the invention's compound distinguishes from the
prior art by having a very strong green note; in particular the
invention distinguishes from 3-(3-(tert-butyl)cyclohexyl)propanal
by having a dominant green/watery/sap note instead of having a
fatty/aldehydic and green/herbaceous connotation (i.e. no watery
connotation) which are typical of the prior art. Said differences
lend the invention's compounds and the prior art compounds to be
each suitable for different uses, i.e. to impart different
organoleptic impressions.
[0026] As mentioned above, the invention concerns the use of a
compound of formula (I) as perfuming ingredient. In other words, it
concerns a method or a process to confer, enhance, improve or
modify the odor properties of a perfuming composition or of a
perfumed article or of a surface, which method comprises adding to
said composition or article an effective amount of at least a
compound of formula (I). By "use of a compound of formula (I)" it
has to be understood here also the use of any composition
containing a compound (I) and which can be advantageously employed
in perfumery industry.
[0027] Said compositions, which in fact can be advantageously
employed as perfuming ingredients, are also an object of the
present invention.
[0028] Therefore, another object of the present invention is a
perfuming composition comprising: [0029] i) as perfuming
ingredient, at least one invention's compound as defined above;
[0030] ii) at least one ingredient selected from the group
consisting of a perfumery carrier and a perfumery base; and [0031]
iii) optionally at least one perfumery adjuvant.
[0032] By "perfumery carrier" we mean here a material which is
practically neutral from a perfumery point of view, i.e. that does
not significantly alter the organoleptic properties of perfuming
ingredients. Said carrier may be a liquid or a solid.
[0033] As liquid carrier one may cite, as non-limiting examples, an
emulsifying system, i.e. a solvent and a surfactant system, or a
solvent commonly used in perfumery. A detailed description of the
nature and type of solvents commonly used in perfumery cannot be
exhaustive. However, one can cite as non-limiting examples solvents
such as butylene or propylene glycols, glycerol, dipropyleneglycol
and its monoether, 1,2,3-propanetriyl triacetate, dimethyl
glutarate, dimethyl adipate, 1,3-diacetyloxypropan-2-yl acetate,
diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl
alcohol, 2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate, which are
the most commonly used. For the compositions which comprise both a
perfumery carrier and a perfumery base, other suitable perfumery
carriers than those previously specified, can be also ethanol,
water/ethanol mixtures, limonene or other terpenes, isoparaffins
such as those known under the trademark Isopar.RTM. (origin: Exxon
Chemical) or glycol ethers and glycol ether esters such as those
known under the trademark Dowanol.RTM. (origin: Dow Chemical
Company), or hydrogenated castors oils such as those known under
the trademark Cremophor.RTM. RH 40 (origin: BASF).
[0034] As solid carrier it is meant a material where the perfuming
composition or some element of the perfuming composition can be
chemically or physically bound. In general such solid carrier are
employed either to stabilize the composition, either to control the
rate of evaporation of the compositions or of some ingredients. The
employment of solid carrier is of current use in the art and a
person skilled in the art knows how to reach the desired effect.
However by way of non-limiting example as solid carriers one may
cite absorbing gums or polymers or inorganic material, such as
porous polymers, cyclodextrines, wood based materials, organic or
inorganic gels, clays, gypsum talc or zeolites.
[0035] As other non-limiting example of solid carrier one may cite
encapsulating materials. Examples of such materials may comprise
wall-forming and plasticizing materials, such as mono, di- or
trisaccharides, natural or modified starches, hydrocolloids,
cellulose derivatives, polyvinyl acetates, polyvinylalcohols,
proteins or pectins, or yet the materials cited in reference texts
such as H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und
Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe
Lebensmittelchemie, Lebensmittelqualitat, Behr's Verlag GmbH &
Co., Hamburg, 1996. The encapsulation is a well-known process to a
person skilled in the art, and may be performed, for instance,
using techniques such as spray-drying, agglomeration or yet
extrusion; or consists of a coating encapsulation, including
coacervation and complex coacervation technique. As non-limiting
examples one may cite in particular the core-shell encapsulation
with resins of the aminoplast, polyamide, polyester, polyurea or
polyurethane type or a mixture thereof (all of said resins are well
known to a person skilled in the art) using techniques like phase
separation process induced by polymerization, by interfacial
polymerization, by coacervation or altogether (all of said
techniques have been described in the prior art), and optionally in
the presence of polymeric stabilizer or a cationic copolymer.
[0036] In particular, as resins one may cite the ones produced by
the polycondensation of an aldehyde (e.g. formaldehyde,
2,2-dimethoxyethanal, glyoxal, glyoxylic acid or glycolaldehyde and
mixtures thereof) with an amine, namely urea, benzoguanamine,
glycoluryl, melamine, methylol melamine, methylated methylol
melamine, guanazole and the like, as well as mixtures thereof.
Alternatively one may use preformed resins alkylolated polyamines
such as those commercially available under the trademark Urac.RTM.
(origin: Cytec Technology Corp.), Cymel.RTM. (origin: Cytec
Technology Corp.), Urecoll.RTM. or Luracoll.RTM. (origin:
BASF).
[0037] In particular, as resins one may cite the ones produced by
the polycondensation of a polyol, like glycerol, and a
polyisocyanate, like 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 (known with the tradename of
Takenate.RTM., origin: Mitsui Chemicals), among which a trimer of
xylylene diisocyanate with trimethylolpropane and a Biuret of
hexamethylene diisocyanate.
[0038] Some of the seminal literature related to the encapsulation
of perfumes by polycondensation of amino resins, namely melamine
based resins, with aldehydes is represented by articles such as
those published by K. Dietrich et al. in Acta Polymerica, 1989,
vol. 40, pages 243, 325 and 683, as well as 1990, vol. 41, page 91.
Such articles already describe the various parameters affecting the
preparation of such core-shell microcapsules following prior art
methods that are also further detailed and exemplified in the
patent literature. U.S. Pat. No. 4,396,670, to the Wiggins Teape
Group Limited is a pertinent early example of the latter. Since
then, many other authors and creators have enriched the literature
in this field and it would be impossible to cover all published
developments here, but the general knowledge in this type of
encapsulation is very significant. More recent publications of
pertinency, which also address the suitable uses of such
microcapsules, are represented for example by the article of H. Y.
Lee et al. in Journal of Microencapsulation, 2002, vol. 19, pages
559-569, international patent publication WO 01/41915 or yet the
article of S. Bone et al. in Chimia, 2011, vol. 65, pages
177-181.
[0039] By "perfumery base" we mean here a composition comprising at
least one perfuming co-ingredient.
[0040] Said perfuming co-ingredient is not of formula (I).
Moreover, by "perfuming co-ingredient" it is meant here a compound,
which is used in a perfuming preparation or a composition to impart
a hedonic effect. In other words such a co-ingredient, to be
considered as being a perfuming one, must be recognized by a person
skilled in the art as being able to impart or modify in a positive
or pleasant way the odor of a composition, and not just as having
an odor.
[0041] 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 intended use or application and the desired organoleptic effect.
In general terms, these perfuming co-ingredients belong to chemical
classes as varied as alcohols, lactones, aldehydes, ketones,
esters, ethers, acetates, nitriles, terpenoids, nitrogenous or
sulphurous heterocyclic compounds and essential oils, and said
perfuming co-ingredients can be of natural or synthetic origin.
[0042] In particular one may cite perfuming co-ingredients which
are commonly used in perfume formulations, such as: [0043]
Aldehydic ingredients: decanal, dodecanal, 2-methyl-undecanal,
10-undecenal, octanal and/or nonenal; [0044] Aromatic-herbal
ingredients: eucalyptus oil, camphor, eucalyptol, menthol and/or
alpha-pinene; [0045] Balsamic ingredients: coumarine, ethylvanillin
and/or vanillin; [0046] Citrus ingredients: dihydromyrcenol,
citral, orange oil, linalyl acetate, citronellyl nitrile, orange
terpenes, limonene, 1-P-menthen-8-yl acetate and/or
1,4(8)-P-menthadiene; [0047] Floral ingredients: Methyl
dihydrojasmonate, linalool, Citronellol, phenylethanol,
3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamic aldehyde,
benzyl acetate, benzyl salicylate,
tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta ionone, methyl
2-(methylamino)benzoate,
(E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one,
hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol,
3-(4-isopropylphenyl)-2-methylpropanal, verdyl acetate, geraniol,
P-menth-1-en-8-ol, 4-(1,1-dimethylethyl)-1-cyclohexyle acetate,
1,1-dimethyl-2-phenylethyl acetate,
4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high cis methyl
dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, verdyl proprionate,
geranyl acetate, tetrahydro linalool, cis-7-P-menthanol, Propyl
(S)-2-(1,1-dimethylpropoxy)propanoate, 2-methoxynaphthalene,
2,2,2-trichloro-1-phenylethyl acetate,
4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde,
amylcinnamic aldehyde, 4-phenyl-2-butanone, isononyle acetate,
4-(1,1-dimdthyldthyl)-1-cyclohexyl acetate, verdyl isobutyrate
and/or mixture of methylionones isomers; [0048] Fruity ingredients:
gamma undecalactone, 4-decanolide, ethyl 2-methyl-pentanoate, hexyl
acetate, ethyl 2-methylbutanoate, gamma nonalactone, allyl
heptanoate, 2-phenoxyethyl isobutyrate, ethyl
2-methyl-1,3-dioxolane-2-acetate and/or diethyl 1,4-cyclohexane
dicarboxylate; [0049] Green ingredients:
2,4-Dimethyl-3-cyclohexene-1-carbaldehyde,
2-tert-butyl-1-cyclohexyl acetate, styrallyl 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; [0050] Musk
ingredients: 1,4-dioxa-5,17-cycloheptadecanedione, pentadecenolide,
3-Methyl-5-cyclopentadecen-1-one,
1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-g-2-benzopyrane,
(1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl
propanoate, pentadecanolide and/or
(1S,1'R)-[1-(3',3'-Dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl
propanoate; [0051] Woody ingredients:
1-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-1-ethanone,
patchouli oil, terpenes 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-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1--
one and/or isobornyl acetate; [0052] Other ingredients (e.g. amber,
powdery spicy or watery):
dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any of
its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic
aldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal
and/or 3-(3-isopropyl-1-phenyl)butanal.
[0053] According to a particular embodiment, the perfuming
composition of the invention comprises perfuming co-ingredients
imparting lily of the valley note. As shown in Example 2, the
combination of the compound of formula (I) with perfuming
co-ingredients of the lily of the valley types allows obtaining a
perfuming composition close to Lilial.RTM.. Such effect is provided
by the combination of floral note of the prior art compounds and
green/watery note of the invention's compound. Non limiting
examples of perfuming co-ingredients imparting a lily of the valley
note can be selected from the group consisting of
3/4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde (origin:
Firmenich SA, Geneva, Switzerland),
(3,7-dimethyl-6-octenyloxy)acetaldehyde (origin: Intemational
Flavors & Fragrances, USA), Bourgeonal.RTM.
(3-(4-tert-butylphenyl)propanal, trademark from Givaudan-Roure SA,
Vernier, Suisse), 1,1-dimethylbenzenepropanol (origin: Firmenich
SA, Geneva, Switzerland), Coranol.RTM.
(4-cyclohexyl-2-methyl-2-butanol; trademark from Firmenich SA,
Geneva, Switzerland), 3-(4-Isopropylphenyl)-2-methylpropanal,
Cyclosia.RTM. Base (7,hydroxyl-3,7-dimethyloctanal, trademark from
Firmenich SA, Geneva, Switzerland), Florol.RTM.
(tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, trademark from
Firmenich SA, Geneva, Switzerland), Hivernal.RTM.
(3-(3,3/1,1-dimethyl-5-indanyl)propanal, trademark from Firmenich
SA, Geneva, Switzerland), Hydroxycitronellal, Josenol.RTM.
((E)-2-methyl-3-(p-tolyl)prop-2-en-1-ol, trademark from Firmenich
SA, Geneva, Switzerland), Lilial.RTM.
(3-(4-tert-butylphenyl)-2-methylpropanal, trademark from
Givaudan-Roure SA, Vemier, Suisse), Lilyflore.RTM.
((2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol, trademark from
Firmenich SA, Geneva, Switzerland), Lyral.RTM.
(4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde,
trademark from International Flavors & Fragrances, USA),
Mayol.RTM. (cis-4-(1methylethyl)-cyclohexanemethanol, trademark
from Firmenich SA, Geneva, Switzerland) and
3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal.
[0054] A perfumery base according to the invention may not be
limited to the above-mentioned perfuming co-ingredients, and many
of these co-ingredients are in any case listed in reference texts
such as the book by S. Arctander, Perfume and Flavor Chemicals,
1969, Montclair, N.J., USA, or its more recent versions, or in
other works of a similar nature, as well as in the abundant patent
literature 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.
[0055] By "perfumery adjuvant" we mean here an ingredient capable
of imparting additional added benefit such as a color, a particular
light resistance, chemical stability, etc. A detailed description
of the nature and type of adjuvant commonly used in perfuming bases
cannot be exhaustive, but it has to be mentioned that said
ingredients are well known to a person skilled in the art. However,
one may cite as specific non-limiting examples the following:
viscosity agents (e.g. surfactants, thickeners, gelling and/or
rheology modifiers), stabilizing agents (e.g. preservatives,
antioxidant, heat/light and or buffers or chelating agents, such as
BHT), color agents (e.g. dyes and/or pigments) preservative (e.g.
antibacterial or antimicrobial or antifungi or anti irritant
agents), abrasives, skin cooling agents, fixatives, insect
repellents, ointments, vitamins and mixture thereof.
[0056] It is understood that a person skilled in the art is
perfectly able to design optimal formulations for the desired
effect by admixing the above-mentioned components of a perfuming
composition, simply by applying the standard knowledge of the art
as well as by trial and error methodologies.
[0057] An invention's composition consisting of at least one
compound of formula (I) and at least one perfumery carrier
represents a particular embodiment of the invention as well as a
perfuming composition 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.
[0058] It is useful to mention here that the possibility to have,
in the compositions mentioned above, more than one compound of
formula (I) is important as it enables the perfumer to prepare
accords, perfumes, possessing the odor tonality of various
compounds of the invention, creating thus new tools for his
work.
[0059] For the sake of clarity, it is also understood that any
mixture resulting directly from a chemical synthesis, e.g. a
reaction medium without an adequate purification, in which the
compound of the invention would be involved as a starting,
intermediate or end-product could not be considered as a perfuming
composition according to the invention as far as said mixture does
not provide the inventive compound in a suitable form for
perfumery. Thus, unpurified reaction mixtures are generally
excluded from the present invention unless otherwise specified.
[0060] Furthermore, the invention's compound can also be
advantageously used in all the fields of modern perfumery, i.e.
fine or functional perfumery, to positively impart or modify the
odor of a consumer product into which said compound (I) is added.
Consequently, another object of the present invention is
represented by a perfuming consumer product comprising, as a
perfuming ingredient, at least one compound of formula (I), as
defined above.
[0061] The invention's compound can be added as such or as part of
an invention's perfuming composition.
[0062] For the sake of clarity, it has to be mentioned that, by
"perfuming consumer product" it is meant a consumer product which
is expected to deliver at least a pleasant perfuming effect to the
surface to which it is applied (e.g. skin, hair, textile, or home
surface). In other words, a perfuming consumer product according to
the invention is a perfumed consumer product which comprises the
functional formulation, as well as optionally additional benefit
agents, corresponding to the desired consumer product, e.g. a
detergent or an air freshener, and an olfactive effective amount of
at least one invention's compound. For the sake of clarity, said
perfuming consumer product is a non-edible product.
[0063] The nature and type of the constituents of the perfuming
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.
[0064] Non-limiting examples of suitable perfuming consumer product
can be a perfume, such as a fine perfume, a splash or eau de
perfume, a cologne or an shave or after-shave lotion; a fabric care
product, such as a liquid or solid detergent, a fabric softener, a
fabric refresher, an ironing water, a paper, a bleach, carpet
cleaners or curtain-care products; a body-care product, such as a
hair care product (e.g. a shampoo, a coloring preparation or a hair
spray, a color care product, hair shaping product, a dental care
product), a disinfectant, an intimate care product; a cosmetic
preparation (e.g. a skin cream or lotion, a vanishing cream, a
deodorant or antiperspirant (e.g. a spray or roll on), hair
remover, tanning or sun or after sun product, nail products, skin
cleansing or a makeup); or a skin-care product (e.g. a perfumed
soap, shower or bath mousse, oil or gel, a hygiene product or
foot/hand care products); an air care product, such as an air
freshener or a "ready to use" powdered air freshener which can be
used in the home space (rooms, refrigerators, cupboards, shoes or
car) and/or in a public space (halls, hotels, malls, etc.); or a
home care product, such as a mold remover, a furnisher care, a
wipe, a dish detergent or hard-surface (e.g. a floor, bath,
sanitary or a window) detergent; a leather care product or a car
care product, such as a polish, waxes or a plastic cleaners.
[0065] Some of the above-mentioned perfuming consumer product may
represent an aggressive medium for the invention's compound, so
that it may be necessary to protect the latter from premature
decomposition, for example by encapsulation or by chemically
bounding it to another chemical which is suitable to release the
invention's ingredient upon a suitable external stimulus, such as
an enzyme, light, heat or a change of pH.
[0066] The proportions in which the compounds according to the
invention can be incorporated into the various aforementioned
products or compositions vary within a wide range of values. These
values are dependent on the nature of the article to be perfumed
and on the desired organoleptic effect as well as the nature of the
co-ingredients in a given base when the compounds according to the
invention are mixed with perfuming co-ingredients, solvents or
additives commonly used in the art.
[0067] For example, in the case of perfuming compositions, typical
concentrations are in the order of 0.001% to 5% by weight, or even
more, of the compounds of the invention based on the weight of the
composition into which they are incorporated. Concentrations lower
than these, such as in the order of 0.01% to 1% by weight, can be
used when these compounds are incorporated into perfuming consumer
products, percentage being relative to the weight of the
article.
[0068] The invention's compounds can be prepared according to a
method reported in the literature or standard methods known in the
art as described herein-below.
EXAMPLES
[0069] The invention will now be described in further detail by way
of the following examples, wherein the abbreviations have the usual
meaning in the art, the temperatures are indicated in degrees
centigrade (.degree. C.); the NMR spectral data were recorded in
CDCl.sub.3 (if not stated otherwise) with a 360 or 500 MHz machine
for .sup.1H and .sup.13C, the chemical shifts .delta. are indicated
in ppm with respect to TMS as standard, the coupling constants J
are expressed in Hz.
Example 1
Synthesis of Compounds of Formula (I)
a) Preparation of a Mixtures of
3-[5-(2-propanyl)-1-cyclohexen-1-yl]propanal and its Isomer
3-[3-(2-propanyl)-1-cyclohexen-1-yl]propanal
i) 7-isopropyl-1-oxaspiro[4.5]decan-2-one
[0070] 3-isopropyl-1-cyclohexanol (140 g; 984 mmol; 2 eq.) was
heated in an oil bath at 155.degree. C. under nitrogen.
Di-tert-butyl peroxide (18.36 g; 123 mmol; 0.25 eq.) and n-butyl
acrylate (63.7 g; 492 mmol; 1 eq.) were added simultaneously and
separately over a period of 1 hour. After 4 more hours at
150.degree. C., the reaction was cooled to 50.degree. C. and MTBE
(100 mL) was added, followed by 30% aqueous NaOH solution (118 g;
886 mmol). After stirring for 30 minutes, water (140 mL) was added,
followed by MTBE (140 mL). The phases were separated and the aq.
phase was treated with diethyl ether (2.times.300 mL) and MTBE (300
mL). Each organic phase was treated with water (210 mL). The
combined aqueous phases were treated with 50% aqueous
H.sub.2SO.sub.4 solution (280 g), extracted twice with diethyl
ether. Each organic phase was washed with water, aqueous saturated
NaHCO.sub.3 solution (carefully), and brine. Combined extracts were
dried over sodium sulfate. The product was purified by bulb-to-bulb
distillation (100-120.degree. C./0.03 mbar).
7-isopropyl-1-oxaspiro[4.5]decan-2-one was obtained as a 35:65
mixture of diastereoisomers (50.8 g; 98% pure by GC; 254 mmol; 52%
yield).
[0071] .sup.1H NMR (CDCl.sub.3, 500 MHz) (major diastereoisomer):
2.59 (t, J=7 Hz, 2H); 2.12-1.97 (m, 2H); 1.86-1.15 (m, 8H);
0.98-0.84 (m, 2H); 0.88 (d, J=7 Hz, 6H).
[0072] .sup.13C NMR (CDCl.sub.3, 125 MHz) (major diastereoisomer):
176.6 (s); 87.9 (s); 41.2 (d); 40.3 (t); 36.5 (t); 32.4 (d); 30.8
(t); 28.7 (t); 28.1 (t); 22.8 (t); 19.7 (q); 19.6 (q).
ii) 1:1 Mixture of butyl
3-(5-isopropylcyclohex-1-en-1-yl)propanoate and butyl
3-(3-isopropylcyclohex-1-en-1-yl)propanoate
[0073] 7-isopropyl-1-oxaspiro[4.5]decan-2-one as a 35:65 mixture of
diastereoisomers (50.8 g; 254 mmol) was dissolved in n-butanol
(34.5 mL). Conc. sulfuric acid (2 g; 20 mmol) was added and the
solution was heated under nitrogen in an oil bath at 140.degree. C.
during 6 hours. More n-butanol (32.3 mL) was added during the
reaction. The reaction was cooled to RT, diluted with water,
extracted twice with diethyl ether. Organic phases were washed with
aqueous saturated NaHCO.sub.3 solution and brine, dried over sodium
sulfate. The product was purified by bulb-to-bulb distillation
(140.degree. C./0.001 mbar). A 1:1 mixture of isomers butyl
3-(5-isopropylcyclohex-1-en-1-yl)propanoate and butyl
3-(3-isopropylcyclohex-1-en-1-yl)propanoate was obtained as (64 g;
88% pure by GC; 224 mmol; 88% yield).
[0074] .sup.1H NMR (CDCl.sub.3, 500 MHz) (isomer mixture): 5.40
(broad s, 0.5H); 5.32 (s, 0.5H); 4.07 (m, 2H); 2.44-2.39 (m, 2H);
2.30-2.23 (m, 2H); 2.10-1.02 (m, 12H); 0.95-0.83; m; 9H).
[0075] .sup.13C NMR (CDCl.sub.3, 125 MHz) (isomer mixture): 173.7
(s); 173.6 (s); 136.5 (s); 136.0 (s); 125.4 (d); 121.3 (d); 64.2
(t); 64.2 (t); 41.8 (d); 40.5 (d); 33.1 (t); 33.1 (t); 33.0 (t);
32.4 (d); 32.4 (t); 32.1 (t); 30.8 (t); 28.6 (t); 25.9 (t); 25.9
(t); 22.5 (t); 19.9 (q); 19.7 (q); 19.6 (q); 19.3 (q); 19.2 (t);
13.7 (q).
iii) 1:1 Mixture of 3-[5-(2-propanyl)-1-cyclohexen-1-yl]propanal
and 3-[3-(2-propanyl)-1-cyclohexen-1-yl]propanal
[0076] Diisobutylaluminum hydride (1 molar in dichloromethane; 311
mL; 311 mmol; 1.4 eq.) was added dropwise to a solution of the 1:1
mixture of isomers butyl
3-(5-isopropylcyclohex-1-en-1-yl)propanoate and butyl
3-(3-isopropylcyclohex-1-en-1-yl)propanoate (56 g; 211 mmol) in dry
dichloromethane (250 mL), at -78.degree. C. under nitrogen over a
30 minutes period. At the end of the addition, the reaction was
stirred at -78.degree. C. for 2 hours. At this point, a 10% aqueous
solution of Na/K-tartrate (500 mL) was added to the reaction at
-78.degree. C., which was then warmed up to RT and stirred for 24
hours. The mixture was filtered through celite, rinsing with
diethyl ether. Water was added to the filtrate. The mixture was
shaken and the phases separated. The organic phase was washed with
brine. Each aq. phase was reextracted with diethyl ether. Combined
extracts were dried over sodium sulfate. The product was purified
by column chromatography (n-heptane/ethyl acetate 25:1) followed by
bulb-to-bulb distillation (86.degree. C./1 mbar). A 1:1 mixture of
isomers 3-[5-(2-propanyl)-1-cyclohexen-1-yl]propanal and its isomer
3-[3-(2-propanyl)-1-cyclohexen-1-yl]propanal was obtained as (33 g;
99% pure by GC; 181 mmol; 82% yield).
[0077] .sup.1H NMR (CDCl.sub.3, 500 MHz) (isomer mixture): 9.76 (s,
1H); 5.40 (broad s, 0.5H); 5.33 (s, 0.5H); 2.52 (m, 2H); 2.29 (m,
2H); 2.10-1.42 (m, 5H); 1.36-1.27 (m, 1H); 1.22-1.06 (m, 2H); 0.90
(d, J=7 Hz, 1.5H); 0.89 (d, J=7 Hz, 1.5H); 0.87 (m, J=7 Hz; 1.5H);
0.84 (d, J=7 Hz; 1.5H).
[0078] .sup.13C NMR (CDCl.sub.3, 125 MHz) (isomer mixture): 202.7
(s); 136.1 (s); 135.6 (s); 125.8 (d); 121.7 (d); 42.0 (t); 41.9
(t); 41.8 (d); 40.4 (d); 32.3 (t); 32.3 (t); 32.3 (d); 30.4 (t);
30.1 (t); 28.7 (t); 25.9 (t); 25.3 (t); 22.4 (t); 19.9 (q); 19.7
(q); 19.6 (q): 19.3 (q).
b) Preparation of
(-)-3-[(5S)-5-isopropyl-2-methyl-1-cyclohexen-1-yl]propanal
i) 4:1:1 Mixture of
(S,E)-3-(5-isopropyl-2-methylcyclohex-1-en-1-yl)prop-1-en-1-yl
acetate,
(E)-3-((1R,5S)-5-isopropyl-2-methylcyclohex-2-en-1-yl)prop-1-en-1-yl
acetate and
(E)-3-((1S,5S)-5-isopropyl-2-methylcyclohex-2-en-1-yl)prop-1-en-1-yl
acetate
[0079] A mixture of ZnBr.sub.2 (0.05 eq, 5 mol %, 7.4 g) and leavo
dihydrolimonene (obtained as published for example in the J. Chem.
Soc., Chem. Commun. 1994, 24, 2759-2760 or J. Org. Chem. 1982, 10,
1824-1831) (90 g, 0.65 mol) and acrolein diacetate (0.1 eq, 12.0 g,
76 mmol) was heated at 40.degree. C. and acrolein diacetate (1.0
eq, 102 g, 0.645 mol) was then added slowly dropwise over 90
minutes. The temperature was kept <45.degree. C. throughout the
introduction.
[0080] The solution was stirred at 40.degree. C. for a further 20
hours then diluted with MTBE (300 mL) and washed with water
(2.times.100 mL) then washed cautiously with saturated NaHCO.sub.3
solution and brine, dried over anhydrous Na.sub.2SO.sub.4, then
filtered and the solvents removed in vacuo to yield the crude
enolacetate as a mixture of isomers. Further purification by vacuum
distillation using a short (15 cm) Vigreux column gave the desired
enol acetate as a mixture of isomers:
(S,E)-3-(5-isopropyl-2-methylcyclohex-1-en-1-yl)prop-1-en-1-yl
acetate:
(E)-3-((1R,5S)-5-isopropyl-2-methylcyclohex-2-en-1-yl)prop-1-en-1-yl
acetate:
(E)-3-((1S,5S)-5-isopropyl-2-methylcyclohex-2-en-1-yl)prop-1-en--
1-yl acetate (4:1:1, 25.3 g, b.p 80-100.degree. C. at 0.1 mbar in
16% yield).
[0081] .sup.1H NMR (CDCl.sub.3, 500 MHz) (Major isomer) 7.06 (dt,
J=12.3 Hz, 1.4, 1H), 5.36 (dt, J=12.3 Hz, 7.41H), 2.71 (dd, J=14.8
Hz, 7.41H), 2.62 (dd, J 14.8 Hz, 7.41H), 2.10 (CH.sub.3, 3H),
2.05-1.85 (m, 2H), 1.75-1.65 (m, 3H), 1.61 (s, CH.sub.3, 3H), 1.44
(m-6, J=8.4 Hz, 1H), 1.30-1.20 (m, 1H), 1.13 (qd, J=11.9, 5.5 Hz,
1H), 0.87 (d, J=6.9 Hz, CH.sub.3, 3H) ppm.
[0082] .sup.13C NMR (CDCl.sub.3, 125 MHz) (Major isomer) 168.2
(C.dbd.O), 135.7 (CH), 127.6, 127.0 (C), 112.9 (CH), 40.8
(CH.sub.2), 33.1 (CH), 32.6 (CH), 32.3 (CH.sub.2), 31.3 (CH), 26.5
(CH), 20.7, 19.82, 19.8, 18.6 (CH.sub.2) ppm.
ii) 7:1:1 Mixture of
(S)-3-(5-isopropyl-2-methylcyclohex-1-en-1-yl)propanal,
3-((1S,5S)-5-isopropyl-2-methylcyclohex-2-en-1-yl)propanal and
3-((1R,5S)-5-isopropyl-2-methylcyclohex-2-en-1-yl)propanal
[0083] A solution of the enol acetate obtained above (31 g, 132
mmol) and DABCO (5.15 g, 0.35 eq) in methanol (120 mL) was heated
at reflux for 7 hours then cooled. The methanol was removed in
vacuo then the residue partioned between MTBE and 5% HCl. The
organic phase was then washed with water, saturated NaHCO.sub.3
solution and brine then dried over Na.sub.2SO.sub.4 and filtered.
The solvents were removed in vacuo to yield the crude aldehyde,
25.2 g as a mixture of isomers, (6:1:1).
[0084] Further purification of a portion (18.5 g) by Fischer
distillation (120-140.degree. C. at 2.5 to 0.1 mbar) gave mixed
fractions plus the desired aldehyde as a mixture (7:1:1) of
isomers:
(S)-3-(5-isopropyl-2-methylcyclohex-1-en-1-yl)propanal:3-((1S,5S)-5-isopr-
opyl-2-methylcyclohex-2-en-1-yl)propanal:3-((1R,5S)-5-isopropyl-2-methylcy-
clohex-2-en-1-yl)propanal (7.2 g). (70:15:15 by NMR).
[0085] .sup.1H NMR (CDCl.sub.3, 500 MHz) (Major isomer) 9.78 (t,
J=1.9 Hz, 1H), 2.51-2.44 (m, 2H), 2.38-2.25 (m, 2H), 2.04-1.84 (m,
2H), 1.76-1.67 (m, 1H), 1.61 (s, 3H), 1.46 (d, J=6.6 Hz, 1H), 1.44
(d, J=6.6 Hz, 1H), 1.32-1.20 (m, 2H), 1.14 (qd, J=12.2, 5.8 Hz,
1H), 0.89 (d, J=1.8 Hz, 3H) 0.87 (d, J=1.8 Hz, 3H) ppm.
[0086] .sup.13C NMR (CDCl.sub.3, 125 MHz) (Major isomer) 202.8
(CH), 127.5, 127.4 (C), 42.6 (CH.sub.2), 40.8 (CH), 33.1, 32.6
(CH.sub.2), 32.3 (CH), 26.5, 26.1 (CH.sub.2), 19.9, 19.8, 18.7
(CH.sub.3) ppm.
c) Preparation of 3-[5-ethyl-1-cyclohexen-1-yl]propanal
i) Mixture of (5RS,7SR)-7-ethyl-1-oxaspiro[4.5]decan-2-one and
(5RS,7RS)-7-ethyl-1-oxaspiro[4.5]decan-2-one
[0087] 3-ethyl-1-cyclohexanol (123.3 g; 961 mmol; 1.76 eq.) was
heated in an oil bath at 155.degree. C. under nitrogen.
Di-tert-butyl peroxide (47.8 g; 320 mmol; 0.59 eq.) and n-butyl
acrylate (70.6 g; 546 mmol; 1 eq.) were added simultaneously and
separately over a period of 1 hour. After 4 more hours at
150.degree. C., the reaction was cooled to 50.degree. C. and MTBE
was added, followed by 30% aqueous NaOH (50 g; 375 mmol). After
stirring for 30 minutes, water was added, followed by more MTBE.
The phases were separated and the aq. phase was treated with
diethyl ether and MTBE. Each organic phase was treated with water.
The combined aq. phases were treated with 50% aq. H2SO4, extracted
twice with diethyl ether. Each org. phase was washed with water,
aqueous saturated NaHCO.sub.3, and brine. Combined extracts were
dried over sodium sulfate. The product was purified by bulb-to-bulb
distillation (80.degree. C./0.1 mbar). It was obtained as a 34:66
mixture of diastereoisomers (40 g; 99.5% pure by GC; 219 mmol; 40%
yield).
[0088] .sup.13C-NMR (major diastereoisomer): 176.65 (s); 87.47 (s);
43.03 (t); 36.66 (d); 36.53 (t); 31.08 (t); 30.79 (t); 29.4 (t);
28.72 (t); 22.59 (t); 11.33 (q).
ii) Mixture of butyl 3-(5-ethyl-1-cyclohexen-1-yl)propanoate and
butyl 3-(3-ethyl-1-cyclohexen-1-yl)propanoate
[0089] The lactone obtained above (28.55 g; 157 mmol) was dissolved
in n-butanol (40 ml). Concentrated sulfuric acid (0.92 g; 9.4 mmol)
was added and the solution was heated under nitrogen in an oil bath
at 140.degree. C. More n-butanol (40 ml) was added during the
reaction. Total reaction time: 2 days. The reaction was cooled to
room temperature, diluted with water, extracted twice with diethyl
ether. Organic phases were washed with aqueous saturated NaHCO3 and
brine, dried over sodium sulfate. The product was purified by
bulb-to-bulb distillation (100.degree. C./0.1 mbar). It was
obtained as a 44:56 mixture of isomers (20.4 g; 96% pure by GC; 82
mmol; 52% yield).
[0090] .sup.13C-NMR (regioisomer mixture): 173.68 (s); 173.5 (s);
135.83 (s); 135.70 (s); 126.59 (d); 121.38 (d); 64.14 (t); 37.01
(d); 35.68 (d); 34.78 (t); 33.05 (t); 33.02 (t); 30.77 (t); 29.23
(t); 28.55 (t); 28.41 (t); 25.29 (t); 21.92 (t); 19.20 (t); 19.19
(t); 13.73 (q); 11.47 (q); 11.45 (q).
iii) Mixture of 3-(5-ethyl-1-cyclohexen-1-yl)propanal and
3-(3-ethyl-1-cyclohexen-1-yl)propanal
[0091] Diisobutylaluminum hydride (1 M in dichloromethane; 120 ml;
120 mmol; 1.2 eq.) was added dropwise to a solution of the ester
obtained above (23.87 g; 100 mmol) in dry dichloromethane (200 ml).
At the end of the addition, the reaction was stirred at -78.degree.
C. for 2 hours. At this point, a 10% aqueous solution of
Na/K-tartrate (100 ml) was added to the reaction at -78.degree. C.,
which was then warmed up to room temperature and stirred for 24
hours. The mixture was filtered through celite, rinsing with
diethyl ether. Water was added to the filtrate. The mixture was
shaken and the phases separated. The organic phase was washed with
brine. Each aqueous phase was reextracted with diethyl ether.
Combined extracts were dried over sodium sulfate. The product was
purified by column chromatography (n-heptane/MTBE 49:1) followed by
bulb-to-bulb distillation (85.degree. C./0.1 mbar). It was obtained
as a 39:61 mixture of regioisomers (13.83 g; 95% pure by GC; 79
mmol; 79% yield).
[0092] .sup.13C-NMR (isomer mixture): 202.76 (d); 202.74 (d);
135.44 (s); 135.31 (s); 126.99 (d); 121.73 (d); 41.95 (t); 41.90
(t); 36.97 (d); 35.63 (d); 34.97 (t); 30.16 (t); 30.08 (t); 29.17
(t); 28.73 (t); 28.45 (t); 28.34 (t); 25.25 (t); 21.85 (t); 11.46
(q); 11.43 (q).
d) Preparation of 3-(5-sec-butyl-1-cyclohexen-1-yl)propanal
[0093] 3-(5-sec-butyl-1-cyclohexen-1-yl)propanal has been
synthesized following the experimental part reported in Example 1
a) by replacing 3-isopropyl-1-cyclohexanol by
3-(sec-butyl)-1-cyclohexanol. Following said procedure,
3-(5-sec-butyl-1-cyclohexen-1-yl)propanal has been isolated as a
mixture of 2 diastereoisomers.
[0094] .sup.13C NMR (diasteroisomer mixture): 202.83 (s); 135.61
(s); 136.60 (s); 121.97 (d); 121.93 (d); 41.93 (t); 38.95 (d);
38.73 (d); 38.20 (d); 37.94 (d); 29.79 (t); 29.78 (t); 29.49 (t);
29.39 (t); 29.29 (t); 27.56 (t); 27.01 (t); 26.69 (t); 26.43 (t);
25.37 (t); 15.77 (q); 15.38 (q); 11.78 (q); 11.74 (q).
Example 2
Preparation of a Perfuming Composition
[0095] A perfuming composition, of the floral type, was prepared by
admixing the following ingredients:
TABLE-US-00002 Parts by weight Ingredient 100 Acropal .sup.1) 40 C
12 Aldehyde 10 C 8 Aldehyde 50 1%* Cuminic aldehyde 20
(3,7-Dimethyl-6-octenyloxy)acetaldehyde 20 9-Undecenal 1000 Coranol
.RTM. .sup.2) 300 Hivernal .RTM. .sup.3) 1000
3-(4-Isopropylphenyl)-2-methylpropanal 5000 Florol .RTM. .sup.4) 20
10%* (4-methylphenoxy)acetaldehyde 500 Lilyflore .RTM. .sup.5) 300
Mayol .RTM. .sup.6) 500 (4E)-4-methyl-5-(4-methylphenyl)-4-pentenal
500 3 -(4,4-dimethyl-1-cyclohexen-1-yl)propanal 140 1%* Trans
Decenal 100 7-(2-methyl-2-propanyl)-2H-1,5-benzodioxepin-3(4H)-one
9600 *in dipropyleneglycol .sup.1)
3/4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde .sup.a)
.sup.2) 4-cyclohexyl-2-methyl-2-butanol .sup.a) .sup.3)
3-(3,3/1,1-dimethyl-5-indanyl)propanal .sup.a) .sup.4)
tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol .sup.a) .sup.5)
(2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol .sup.a) .sup.6)
cis-4-(1methylethyl)-cyclohexanemethanol .sup.a) .sup.a) origin:
Firmenich SA, Geneva, Switzerland
[0096] The addition of 400 parts by weight of a mixture obtained in
example 1 a) iii) to the above-described composition imparted to
the latter a Lilial.RTM. type connotation (trademark from Givaudan
SA, Vernier, Switzerland) characterized by the typical floral,
green and aqueous-wet Lilial.RTM. note. The compound harmonizes
very well with and pushes the lily of the valley odorant of the
composition (i.e. Hivernal.RTM.,
(4E)-4-methyl-5-(4-methylphenyl)-4-pentenal and
3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal).
[0097] The addition of the same amount of the prior art
3-(3-(tert-butyl)cyclohexyl)propanal instead of the invention's
compound provided new fragrance having a more aldehydic character
and with less floral/green connotation typical of Lilial.RTM..
[0098] The addition of the same amount of the prior art
3-(3-isopropylcyclohexyl)butanal instead of the invention's
compound provided new fragrance having a more orris/floral
character with a powdery connotation and devoid of the lily of the
valley note.
Example 3
Preparation of a Perfuming Composition
[0099] A perfume, of the herbaceous, floral lily of the valley
type, was prepared by admixing the following ingredients:
TABLE-US-00003 Parts by weight Ingredient 200 Hexyl acetate 500
Isobornyl acetate 100 Geranyl acetate 100 Phenylethyl acetate 50
Styrallyl acetate 400 Verdyl acetate 500 Hexylcinnamic aldehyde 100
2-Methyl undecanal 50 Allyl Amyl Glycolate 50 Methyl anthranilate
40 Methyl benzoate 250 Benzylacetone 150 (1-Methyl-2-phenyl)ethyl
butanoate 10 7-Isopropyl-2H,4H-1,5-benzodioxepin-3-one 100 Cetalox
.RTM. .sup.1) 30 Raspberry ketone 50 Citronellyl Nitrile 250
Coumarine 30 Damascone Alpha 600 Dihydromyrcenol 40 Ethylvanilline
100 Eugenol 300 Fructalate .RTM. .sup.2) 400 Gamma Undecalactone
200 Geraniol 500 Habanolide .RTM. .sup.3) 400 Hedione .RTM. .sup.4)
100 Allyl heptanoate 100 Ionone Beta 300 Iralia .RTM. .sup.5) 500
Iso E .RTM. Super .sup.6) 100 Lavandin Grosso essential oil 20
1-(2,2,3,6-Tetramethyl-cyclohexyl)-3-hexanol .sup.a) 30 Methyl
Phenylethyl Ether 50 2-Ethyl methylbutyrate 20 Methylparacresol 30
Crystal Moss oil 100 Muscenone .RTM. Delta .sup.7) 20 Neobutenone
.RTM. Alpha .sup.8) 100 Nirvanol .RTM. .sup.9) 20 10%*
cis-2-methyl-4-propyl-1,3-oxathiane .sup.a) 300 Phenylhexanol 250
Rosinol 500 Salicynile .RTM. .sup.10) 500 Sclareolate .RTM.
.sup.11) 200 Terpineol 50 2-Ethyl-4,4-dimethylcyclohexanone .sup.a)
50 2,4-Dimethyl-3-cyclohexene-1-carbaldehyde 260 Undecavertol .RTM.
.sup.12) 500 2-Tert-butyl-1-cyclohexyl acetate 100 Yara Yara 9700
*in dipropyleneglycol .sup.1)
dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan .sup.a)
.sup.2) diethyl 1,4-cyclohexane dicarboxylate .sup.a) .sup.3)
pentadecenolide .sup.a) .sup.4) methyl dihydrojasmonate .sup.a)
.sup.5) mixture of methylionones isomers .sup.a) .sup.6)
1-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-1-ethanone .sup.c)
.sup.7) 3-methyl-5-cyclopentadecen-1-one .sup.a) .sup.8)
1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one .sup.a) .sup.9)
3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol
.sup.a) .sup.10) (2Z)-2-phenyl-2-hexenenitrile .sup.a) .sup.11)
propyl (S)-2-(1,1-dimethylpropoxy)propanoate .sup.a) .sup.12)
4-methyl-3-decen-5-ol .sup.b) .sup.a) origin: Firmenich SA, Geneva,
Switzerland .sup.b) origin: Givaudan-Roure SA, Vernier, Suisse
.sup.c) origin: International Flavors & Fragrances, USA
[0100] The addition of 300 parts by weight of a mixture obtained in
example 1 a) iii) to the above-described composition imparted to
the latter a unique fresh-green and floral connotation pushing the
lily of the valley and citrus tonality, with a more powerful
impact.
* * * * *