U.S. patent application number 14/105420 was filed with the patent office on 2014-04-17 for octahydro-1h-4,7-methano-indene-5-aldehydes and their use in perfume compositions.
This patent application is currently assigned to International Flavors & Fragrances Inc.. The applicant listed for this patent is International Flavors & Fragrances Inc.. Invention is credited to James Anthony Lasome, Michael G. Monteleone, Anubhav P.S. Narula, Richard A. Weiss.
Application Number | 20140107221 14/105420 |
Document ID | / |
Family ID | 47115531 |
Filed Date | 2014-04-17 |
United States Patent
Application |
20140107221 |
Kind Code |
A1 |
Narula; Anubhav P.S. ; et
al. |
April 17, 2014 |
OCTAHYDRO-1H-4,7-METHANO-INDENE-5-ALDEHYDES AND THEIR USE IN
PERFUME COMPOSITIONS
Abstract
The present invention is directed to a novel fragrance compound
of octahydro-6-methyl-4,7-methano-1H-indene-5-carboxaldehyde.
Inventors: |
Narula; Anubhav P.S.;
(Hazlet, NJ) ; Lasome; James Anthony; (Matawan,
NJ) ; Weiss; Richard A.; (Livingston, NJ) ;
Monteleone; Michael G.; (Hazlet, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
International Flavors & Fragrances Inc. |
New York |
NY |
US |
|
|
Assignee: |
International Flavors &
Fragrances Inc.
New York
NY
|
Family ID: |
47115531 |
Appl. No.: |
14/105420 |
Filed: |
December 13, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13287594 |
Nov 2, 2011 |
8633144 |
|
|
14105420 |
|
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Current U.S.
Class: |
514/693 ;
510/105; 512/18; 568/445 |
Current CPC
Class: |
C07C 47/445 20130101;
A61Q 13/00 20130101; C07C 2603/66 20170501; C11D 3/50 20130101;
C07C 47/115 20130101; C07C 47/347 20130101; A61K 8/35 20130101;
C11B 9/0042 20130101; C11B 9/0049 20130101 |
Class at
Publication: |
514/693 ;
568/445; 510/105; 512/18 |
International
Class: |
C11B 9/00 20060101
C11B009/00; C07C 47/445 20060101 C07C047/445 |
Claims
1. A compound,
octahydro-6-methyl-4,7-methano-1H-indene-5-carboxaldehyde.
2. A fragrance formulation containing an olfactory acceptable
amount of
octahydro-6-methyl-4,7-methano-1H-indene-5-carboxaldehyde.
3. The fragrance formulation of claim 2 further comprising a
product selected from the group consisting of a perfume, a cologne,
toilet water, a cosmetic product, a personal care product, a fabric
care product, a cleaning product, and an air freshener.
4. The fragrance formulation of claim 3, wherein the cleaning
product is selected from the group consisting of a detergent, a
dishwashing composition, a scrubbing compound, and a window
cleaner.
5. The fragrance formulation of claim 2, wherein the olfactory
acceptable amount is from about 0.005 to about 50 weight percent of
the fragrance formulation.
6. The fragrance formulation of claim 2, wherein the olfactory
acceptable amount is from about 0.5 to about 25 weight percent of
the fragrance formulation.
7. The fragrance formulation of claim 2, wherein the olfactory
acceptable amount is from about 1 to about 10 weight percent of the
fragrance formulation.
8. A method of improving, enhancing or modifying a fragrance
formulation through the addition of an olfactory acceptable amount
of octahydro-6-methyl-4,7-methano-1H-indene-5-carboxaldehyde.
9. The method of claim 8, wherein the olfactory acceptable amount
is from about 0.005 to about 50 weight percent of the fragrance
formulation.
10. The method of claim 8, wherein the olfactory acceptable amount
is from about 0.5 to about 25 weight percent of the fragrance
formulation.
11. The method of claim 8, wherein the olfactory acceptable amount
is from about 1 to about 10 weight percent of the fragrance
formulation.
12. A fragrance product comprising the compound of claim 1.
Description
STATUS OF RELATED APPLICATIONS
[0001] This application is a divisional of U.S. Ser. No.
13/287,594, filed Nov. 2, 2011, now allowed, the contents hereby
incorporated by references as if set forth in their entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to new chemical entities and
the incorporation and use of the new chemical entities as fragrance
materials.
BACKGROUND OF THE INVENTION
[0003] There is an ongoing need in the fragrance industry to
provide new chemicals to give perfumers and other persons the
ability to create new fragrances for perfumes, colognes and
personal care products. Those with skill in the art appreciate how
small differences in chemical structures can result in unexpected
and significant differences in odor hedonic notes and
characteristics of molecules. These variations allow perfumers and
other persons to apply new compounds in creating new fragrances
with unique and differentiating performance.
[0004] For instance, it is well known analogs such as aldehydes and
aldehyde derivatives may possess distinct and unique olfactory
properties. 3,7-Dimethyl-6-octenal (Citronellal), for example,
possesses citrus, green, fruity, and rose scent and has been widely
used in both fragrances and flavors. However, its ketone derivative
4,8-dimethyl-7-nonen-2-one, though described as having coconut
rosaceous odor since the 1970's, is not suitable for use in
fragrances or flavors due to additional undesirable properties such
as fatty, stemmy, and weak [Sethi, et al., 22(4): 225-228 (1978)].
Thus, identifying desirable fragrance chemicals continues to pose
difficult challenges and predicting odors remains empirical in
nature.
SUMMARY OF THE INVENTION
[0005] The present invention provides novel chemicals, and the use
of the chemicals to enhance the fragrance of perfumes, toilet
waters, colognes, personal products and the like. In addition, the
present invention is directed to the use of the novel chemicals to
enhance fragrance in perfumes, toilet waters, colognes, personal
products and the like.
[0006] More specifically, the present invention is directed to
novel octahydro-1H-4,7-methano-indene-5-aldehydes represented by
the formulas set forth below:
##STR00001##
[0007] wherein Formula I represents
octahydro-4,7-methano-1H-indene-5-acetaldehyde; and Formula II
represents
octahydro-6-methyl-4,7-methano-1H-indene-5-carboxaldehyde.
[0008] Another embodiment of the invention is directed to a
fragrance formulation comprising an
octahydro-1H-4,7-methano-indene-5-aldehyde compound provided above
or a mixture thereof.
[0009] Another embodiment of the invention is directed to a method
for enhancing a perfume composition by incorporating an olfactory
acceptable amount of an octahydro-1H-4,7-methano-indene-5-aldehyde
compound provided above or a mixture thereof.
[0010] These and other embodiments of the present invention will be
apparent by reading the following specification.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Those with the skill in the art will appreciate that Formula
I above represents octahydro-4,7-methano-1H-indene-5-acetaldehyde;
and Formula II above represents
octahydro-6-methyl-4,7-methano-1H-indene-5-carboxaldehyde.
[0012] The compounds of the present invention can be prepared from
octahydro-4,7-methano-inden-5-one according to the reaction scheme
below, the details of which are specified in the Examples.
Materials were purchased from Aldrich Chemical Company unless noted
otherwise.
##STR00002##
[0013] Those with skill in the art will recognize that the product
mixture obtained as described above can be separated using
techniques known to those with skill in the art. Suitable
techniques include, for example, distillation and chromatography
such as high performance liquid chromatography, referred to as
HPLC, particularly silica gel chromatograph, and gas chromatography
trapping known as GC trapping. Yet, commercial products are mostly
offered as isomeric mixtures.
[0014] Those with skill in the art will further recognize that some
of the compounds of the present invention have a number of chiral
centers, thereby providing numerous isomers of the claimed
compounds. It is intended herein that the compounds described
herein include isomeric mixtures of such compounds, as well as
those isomers that may be separated using techniques known to those
having skill in the art as described above.
[0015] The use of the compounds of the present invention is widely
applicable in current perfumery products, including the preparation
of perfumes and colognes, the perfuming of personal care products
such as soaps, shower gels, and hair care products, fabric care
products, air fresheners, and cosmetic preparations. The present
invention can also be used to perfume cleaning agents, such as, but
not limited to detergents, dishwashing materials, scrubbing
compositions, window cleaners and the like.
[0016] In these preparations, the compounds of the present
invention can be used alone or in combination with other perfuming
compositions, solvents, adjuvants and the like. The nature and
variety of the other ingredients that can also be employed are
known to those with skill in the art.
[0017] Many types of fragrances can be employed in the present
invention, the only limitation being the compatibility with the
other components being employed. Suitable fragrances include but
are not limited to fruits such as almond, apple, cherry, grape,
pear, pineapple, orange, strawberry, raspberry; musk, flower scents
such as lavender-like, rose-like, iris-like, carnation-like. Other
pleasant scents include herbal and woodland scents derived from
pine, spruce and other forest smells. Fragrances may also be
derived from various oils, such as essential oils, or from plant
materials such as peppermint, spearmint and the like.
[0018] A list of suitable fragrances is provided in U.S. Pat. No.
4,534,891, the contents of which are incorporated by reference as
if set forth in its entirety. Another source of suitable fragrances
is found in Perfumes, Cosmetics and Soaps, Second Edition, edited
by W. A. Poucher, 1959. Among the fragrances provided in this
treatise are acacia, cassie, chypre, cyclamen, fern, gardenia,
hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily,
magnolia, mimosa, narcissus, freshly-cut hay, orange blossom,
orchid, reseda, sweet pea, trefle, tuberose, vanilla, violet,
wallflower, and the like.
[0019] The compounds of the present invention can be used in
combination with a complementary fragrance compound. The term
"complementary fragrance compound" as used herein is defined as a
fragrance compound selected from the group consisting of
2-[(4-methylphenyl)methylene]-heptanal (Acalea), iso-amyl oxyacetic
acid allylester (Allyl Amyl Glycolate),
(3,3-dimethylcyclohexyl)ethyl ethyl propane-1,3-dioate (Applelide),
(E/Z)-1-ethoxy-1-decene (Arctical),
2-ethyl-4-(2,2,3-trimethyl-3-cyclo-penten-1-yl)-2-buten-1-ol
(Bacdanol),
2-methyl-3-[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]exo-1-propanol
(Bornafix),
1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one
(Cashmeran), trimethylcyclopentenylmethyloxabicyclooctane
(Cassiffix), 1,1-dimethoxy-3,7-dimethyl-2,6-octadiene (Citral DMA),
3,7-dimethyl-6-octen-1-ol (Citronellol),
3A,4,5,6,7,7A-hexahydro-4,7-methano-1H-inden-5/6-yl acetate
(Cyclacet), 3A,4,5,6,7,7A-hexahydro-4,7-methano-1H-inden-5/6-yl
propinoate (Cyclaprop),
3A,4,5,6,7,7A-hexahydro-4,7-methano-1G-inden-5/6-yl butyrate
(Cyclobutanate),
1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one (Delta
Damascone), 3-(4-ethylphenyl)-2,2-dimethyl propanenitrile
(Fleuranil), 3-(O/P-ethylphenyl) 2,2-dimethyl propionaldehyde
(Floralozone), tetrahydro-4-methyl-2-(2-methylpropyl)-2H-pyran-4-ol
(Floriffol),
1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran
(Galaxolide), 1-(5,5-dimethyl-1-cyclohexen-1-yl)pent-4-en-1-one
(Galbascone), E/Z-3,7-dimethyl-2,6-octadien-1-yl acetate (Geranyl
Acetate), .alpha.-methyl-1,3-benzodioxole-5-propanal (Helional),
1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,6-heptadien-3-one
(Hexalon), (Z)-3-hexenyl-2-hydroxybenzoate (Hexenyl Salicylate,
CIS-3), 4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (Ionone
a),
1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1--
one (Iso E Super), methyl 3-oxo-2-pentylcyclopentaneacetate
(Kharismal), 2,2,4-trimethyl-4-phenyl-butanenitrile (Khusinil),
3,4,5,6,6-pentamethylhept-3-en-2-one (Koavone),
3/4-(4-hydroxy-4-methyl-pentyl)cyclohexene-1-carboxaldehyde
(Lyral),
3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one
(Methyl Ionone .gamma.), 1-(2,6,6-trimethyl-2-cyclohexen-1-yl)
pent-1-en-3-one (Methyl Ionone .alpha. Extra, Methyl Ionone N),
3-methyl-4-phenylbutan-2-ol (Muguesia), cyclopentadec-4-en-1-one
(Musk Z4),
3,3,4,5,5-pentamethyl-11,13-dioxatricyclo[7.4.0.0<2,6>]tridec--
2(6)-ene (Nebulone), 3,7-dimethyl-2,6-octadien-1-yl acetate (Neryl
Acetate), 3,7-dimethyl-1,3,6-octatriene (Ocimene),
ortho-tolylethanol (Peomosa), 3-methyl-5-phenylpentanol
(Phenoxanol),
1-methyl-4-(4-methyl-3-pentenyl)cyclohex-3-ene-1-carboxaldehyde
(Precyclemone B), 4-methyl-8-methylene-2-adamantanol (Prismantol),
2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol
(Sanjinol),
2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol
(Santaliff), Terpineol, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde
(Triplal), decahydro-2,6,6,7,8,8-hexamethyl-2H-indeno[4,5-B]furan
(Trisamber), 2-tert-butylcyclohexyl acetate (Verdox),
4-tert-butylcyclohexyL acetate (Vertenex), acetyl cedrene
(Vertofix), 3,6/4,6-dimethylcyclohex-3-ene-1-carboxaldehyde
(Vertoliff), and (3Z)-1-[(2-methyl-2-propenyl)oxy]-3-hexene
(Vivaldie).
[0020] The terms "fragrance formulation", "fragrance composition",
and "perfume composition" mean the same and refer to a consumer
composition that is a mixture of compounds including, for example,
alcohols, aldehydes, ketones, esters, ethers, lactones, nitriles,
natural oils, synthetic oils, and mercaptans, which are admixed so
that the combined odors of the individual components produce a
pleasant or desired fragrance. The fragrance formulation of the
present invention is a consumer composition comprising a compound
of the present invention. The fragrance formulation of the present
invention comprises a compound of the present invention and further
a complementary fragrance compound as defined above.
[0021] The term "fragrance product" means a consumer product that
adds a fragrance or masks a malodor. Fragrance products may
include, for example, perfumes, colognes, personal care products
such as soaps, shower gels, and hair care products, fabric
products, air fresheners, cosmetic preparations, and perfume
cleaning agents such as detergents, dishwashing materials,
scrubbing compositions, and window cleaners. The fragrance product
of the present invention is a consumer product that contains a
compound of the present invention. The fragrance product of the
present invention contains a compound of the present invention and
further a complementary fragrance compound as defined above.
[0022] The term "improving" in the phrase "improving, enhancing or
modifying a fragrance formulation" is understood to mean raising
the fragrance formulation to a more desirable character. The term
"enhancing" is understood to mean making the fragrance formulation
greater in effectiveness or providing the fragrance formulation
with an improved character. The term "modifying" is understood to
mean providing the fragrance formulation with a change in
character.
[0023] Olfactory acceptable amount is understood to mean the amount
of compound in perfume compositions the individual component will
contribute to its particular olfactory characteristics, but the
olfactory effect of the perfume composition will be the sum of the
effects of each of the perfumes or fragrance ingredients. Thus the
compounds of the invention can be used to alter the aroma
characteristics of the perfume composition, or by modifying the
olfactory reaction contributed by another ingredient in the
composition. The amount will vary depending on many factors
including other ingredients, their relative amounts and the effect
that is desired.
[0024] The amount of the compounds of the present invention
employed in a fragrance formulation varies from about 0.005 to
about 70 weight percent, preferably from 0.005 to about 50 weight
percent, more preferably from about 0.5 to about 25 weight percent,
and even more preferably from about 1 to about 10 weight percent.
Those with skill in the art will be able to employ the desired
amount to provide desired fragrance effect and intensity. In
addition to the compounds of the present invention, other materials
can also be used in conjunction with the fragrance formulation.
Well known materials such as surfactants, emulsifiers, polymers to
encapsulate the fragrance can also be employed without departing
from the scope of the present invention.
[0025] When used in a fragrance formulation this ingredient
provides fruity, sweet, and green notes to make the fragrance
formulation more desirable and noticeable, and add the perception
of value. The odor qualities found in this material assist in
beautifying and enhancing the finished accord as well as improving
the performance of the other materials in the fragrance. There is
also the fruity side of it which is found in many fragrances today
which happens to be very trendy in vogue, especially for the
younger consumers.
[0026] The following are provided as specific embodiments of the
present invention. Other modifications of this invention will be
readily apparent to those skilled in the art. Such modifications
are understood to be within the scope of this invention. As used
herein all percentages are weight percent unless otherwise noted,
ppm is understood to stand for parts per million, L is understood
to be liter, mL is understood to be milliliter, g is understood to
be gram, mol is understood to be mole, M is understood to be moles
per liter, mmHg be millimeters (mm) of mercury (Hg), and psig is
understood to be pound-force per square inch gauge. IFF as used in
the examples is understood to mean International Flavors &
Fragrances Inc., New York, N.Y., USA.
Example I
##STR00003##
[0027] Preparation of 5-methyl-octahydro-4,7-methano-inden-5-ol by
Grignard addition
[0028] A flame-dried, 5-L 3-necked flask equipped with a mechanical
stirrer, an addition funnel condenser, and a thermocouple was
charged with methyl magnesium bromide (MeMgBr) in tetrahydrofuran
(THF) (3 M, 1.6 L) under nitrogen. The temperature was cooled to
and maintained at 15-20.degree. C. using an external isopropyl
alcohol (IPA) cooling bath. Octahydro-4,7-methano-inden-5-one (649
g, 4.32 mol) was fed over 3-4 hours. The reaction temperature was
allowed to rise to 25-30.degree. C. and maintained at 30.degree. C.
for another hour. The reaction mixture was subsequently quenched
with acetic acid (HOAc) (279 g, 4.5 mol) and ice. The organic layer
was separated to afford the crude product
5-methyl-octahydro-4,7-methano-inden-5-ol (650 g, 90% yield).
[0029] .sup.1H NMR (CDCl.sub.3, 500 MHz): 2.58 ppm (q, 1H, J=8.52
Hz), 1.82-1.94 ppm (m, 4H), 1.77 ppm (s, 1H), 1.74 ppm (s, 1H),
1.63-1.69 ppm (m, 1H), 1.60 ppm (d, 1H, J=12.73 Hz, of d, J=4.68
Hz), 1.39 ppm (d, 1H, J=10.75 Hz, of t, J=1.58 Hz), 1.32 ppm (s,
3H), 1.17-1.30 ppm (m, 2H), 1.11 ppm (d, 1H, J=12.73 Hz, of d,
J-3.33 Hz), 0.87-1.00 ppm (m, 2H).
Example II
##STR00004##
[0030] Preparation of hexahydro-4,7-methano-indene isomers by
dehydration
[0031] A 5-L 3-necked flask equipped with a mechanical stirrer, a
heating mantel, a condenser, a Bidwell trap, and a thermocouple was
charged with 5-methyl-octahydro-4,7-methano-inden-5-ol (650 g, 3.9
mol, synthesized as above in EXAMPLE I). The reaction was heated to
105-110.degree. C. and the THF solvent from the step of EXAMPLE I
was distilled. The reaction mixture was then cooled to below
40.degree. C. p-Toluenesulfonic acid (PTSA) (13 g, 2%) and toluene
(400 mL) were added in one portion. The reaction mixture was then
heated to reflux (.about.120-135.degree. C.) and water was removed
via the Bidwell trap. The reaction was further aged for
.about.25-30 hours until no more water azeotroped. The resulting
reaction mixture was quenched with water (500 mL), washed with
sodium carbonate (Na.sub.2CO.sub.3) (2%, 400 mL), and then
transferred to a 5 L distillation flask to be distilled in a
rushover unit to afford hexahydro-4,7-methano-indene isomers (533
g, 92% yield), which represent a mixture of
5-methylene-octahydro-4,7-methano-indene and
5-methyl-2,3,3a,4,7,7a-hexahydro-1H-4,7-methano-indene with a
boiling point of 130.degree. C. at a pressure of 80 mmHg.
[0032] .sup.1H NMR (CDCl.sub.3, 500 MHz): 4.82 ppm (s, 1H), 4.56
ppm (s, 1H), 2.42 ppm (s, 1H), 2.09-2.15 ppm (m, 1H), 2.07 ppm (s,
1H), 1.77-1.95 ppm (m, 5H), 1.62-1.70 ppm (m, 1H), 1.44 ppm (d, 1H,
J=10.00 Hz), 1.15-1.26 ppm (m, 1H), 1.11 ppm (d, 1H, J=10.10 Hz),
0.90-1.00 ppm (m, 2H).
Example III
##STR00005##
[0033] Preparation of
octahydro-4,7-methano-1H-indene-5-acetaldehyde (Formula I) and
6-methyl-octahydro-4,7-methano-indene-5-carbaldehyde (Formula II)
by hydroformylation
[0034] A 4 L Zipper Clave was charged with
hexahydro-4,7-methano-indene isomers (533 g, 3.6 mol, synthesized
as above in EXAMPLE II) and carbonyl hydrido
tris(triphenylphosphine)rhodium(I) (Rh-42, commercially available
from Johnson Matthey Catalysts, U.S.). The Zipper Clave was flushed
and vented three times with nitrogen followed three times with a
Syngas mixture of carbon monoxide and hydrogen (50:50 by volume).
The Zipper Clave was subsequently pressurized to 300 psig with
Syngas and heated to 120.degree. C. Gas-liquid chromatography (GLC)
analysis of a reaction aliquot indicated the completion of the
reaction after .about.2.5 hours. The reaction mixture was then
vented and purged three times with nitrogen to provide a crude
product, which was distilled to afford a 9:1 mixture of
octahydro-4,7-methano-1H-indene-5-acetaldehyde (508.5 g) and
6-methyl-octahydro-4,7-methano-indene-5-carbaldehyde (56.5 g) (88%
total yield), which were separated and determined by GC and NMR
analysis.
[0035] Octahydro-4,7-methano-1H-indene-5-acetaldehyde has the
following NMR spectral characteristics:
[0036] .sup.1H NMR (CDCl.sub.3, 500 MHz): 9.76 ppm (t, .about.33%
of 1H, J=2.1 Hz), 9.73 ppm (t, .about.66% of 1H, J=2.1 Hz),
0.85-2.52 (m, 16.66H), 0.57 ppm (m, .about.33% of 1H).
[0037] Octahydro-4,7-methano-1H-indene-5-acetaldehyde was described
as having floral and muguet notes.
[0038] 6-Methyl-octahydro-4,7-methano-indene-5-carbaldehyde has the
following NMR spectral characteristics:
[0039] .sup.1H NMR (CDCl.sub.3, 500 MHz): 9.65 ppm (d, 1H, J=2.0
Hz), 1.01 ppm (d, 3H, J=7.0 Hz), 0.90-2.25 ppm (m, 14H).
[0040] 6-Methyl-octahydro-4,7-methano-indene-5-carbaldehyde was
described as having aldehydic note.
[0041] In addition, the mixture of
octahydro-4,7-methano-1H-indene-5-acetaldehyde and
6-methyl-octahydro-4,7-methano-indene-5-carbaldehyde (synthesized
as above) was evaluated and described as having floral, muguet,
aldehydic, green, freesia, sweet, and slightly woody notes.
Example IV
##STR00006##
[0042] Preparation of
1-(octahydro-4,7-methano-inden-5-yl)-propan-2-one (Formula III) and
1-(6-methyl-octahydro-4,7-methano-inden-5-yl)-ethanone (Formula
IV)
[0043] 1-(Octahydro-4,7-methano-inden-5-yl)-propan-2-one and
1-(6-methyl-octahydro-4,7-methano-inden-5-yl)-ethanone of the above
structures were similarly prepared according to EXAMPLEs I-III.
[0044] .sup.1H NMR (CDCl.sub.3, 400 MHz): 2.16-2.52 ppm (m, 2H),
2.11-2.16 ppm (3s, 3H), 1.58-2.06 ppm (m, 8H), 0.47-1.47 ppm (m,
7H).
[0045] The mixture of
1-(octahydro-4,7-methano-inden-5-yl)-propan-2-one and
1-(6-methyl-octahydro-4,7-methano-inden-5-yl)-ethanone was
described as having floral, fruity, woody, but weak notes with
additional metallic character.
Example V
##STR00007##
[0046] Preparation of
2-(octahydro-4,7-methano-inden-5-yl)-propionaldehyde (Formula
V)
[0047] 2-(Octahydro-4,7-methano-inden-5-yl)-propionaldehyde was
similarly prepared according to EXAMPLEs I-III.
[0048] .sup.1H NMR (CDCl.sub.3, 500 MHz): 9.60-9.65 ppm (m,
.about.30% of 1H), 9.57 ppm (d, .about.35% of 1H, J=3.75 Hz), 9.54
ppm (d, .about.35% of 1H, J=3.10 ppm), 2.03-2.30 ppm (m, 1H),
1.91-2.03 ppm (m, 2H), 1.68-1.90 ppm (m, 5H), 1.56-1.67 ppm (m,
1H), 1.12-1.49 (m, 4H), 0.66-1.11 ppm (m, 6H).
[0049] 2-(Octahydro-4,7-methano-inden-5-yl)-propionaldehyde was
described as having strong, grapefruit, and offensive sulphury
notes.
Example VI
##STR00008##
[0050] Preparation of 2-(octahydro-4,7-methano-inden-5-yl)-propenal
(Structure VI)
[0051] 2-(Octahydro-4,7-methano-inden-5-yl)-propenal was similarly
prepared according to EXAMPLEs I-III.
[0052] .sup.1H NMR (CDCl.sub.3, 500 MHz): 9.56 ppm (s, .about.36%
of 1H), 9.53 ppm (s, .about.64% of 1H), 6.20 ppm (s, .about.36% of
1H), 6.18 ppm (s, .about.64% of 1H), 6.09 ppm (s, .about.36% of
1H), 5.93 ppm (s, .about.64% of 1H), 2.92-2.96 ppm (m, .about.36%
of 1H), 2.43 ppm (s, .about.64% of 1H), 1.46-2.25 ppm (m, 6H),
0.86-1.41 ppm (m, 8H).
[0053] 2-(Octahydro-4,7-methano-inden-5-yl)-propenal was described
as having weak, fatty, and green notes.
Example VII
##STR00009##
[0054] Preparation of 2-(octahydro-4,7-methano-inden-5-yl)-ethanol
(Formula VII) and
(6-methyl-octahydro-4,7-methano-inden-5-yl)-methanol (Formula
VIII)
[0055] 2-(Octahydro-4,7-methano-inden-5-yl)-ethanol and
(6-methyl-octahydro-4,7-methano-inden-5-yl)-methanol were similarly
prepared according to EXAMPLEs I-III with further
hydrogenation.
[0056] .sup.1H NMR (CDCl.sub.3, 500 MHz): 3.63 ppm (t, .about.89%
of 2H, J=7.00 Hz), 3.38-3.48 ppm (m, .about.11% of 2H), 1.66-2.20
ppm (m, 7H), 1.51-1.65 ppm (m, 2H), 1.30-1.50 ppm (m, 3H),
0.53-1.28 ppm (m, 6H).
[0057] The mixture of 2-(octahydro-4,7-methano-inden-5-yl)-ethanol
and (6-methyl-octahydro-4,7-methano-inden-5-yl)-methanol was
described as having very weak and woody notes.
Example VIII
##STR00010##
[0058] Preparation of
1-(octahydro-4,7-methano-inden-5-yl)-propan-2-ol (Formula IX)
[0059] 1-(Octahydro-4,7-methano-inden-5-yl)-propan-2-ol was
similarly prepared according to EXAMPLEs I-III with further
hydrogenation.
[0060] .sup.1H NMR (CDCl.sub.3, 400 MHz): 3.74-3.86 ppm (m,
.about.89% of 1H), 3.41-3.56 ppm (m, .about.11% of 1H), 1.25-2.18
ppm (m, 12H), 1.07-1.24 ppm (m, 5H), 0.50-1.06 ppm (m, 4H).
[0061] 1-(Octahydro-4,7-methano-inden-5-yl)-propan-2-ol was
described as having very weak, green, floral, and fruity notes with
additional harsh character.
Example IX
[0062] The fragrance formulas exemplified as follows demonstrated
that the addition of the mixture of
octahydro-4,7-methano-1H-indene-5-acetaldehyde and
6-methyl-octahydro-4,7-methano-indene-5-carbaldehyde (synthesized
as above) provided floral, muguet, aldehydic, green, freesia,
sweet, and slightly woody notes to the fragrance formula:
TABLE-US-00001 Ingredient Parts (grams) Parts (grams) ALD C-10 PRO
STABILIFF 0.208 0.208 PATCHOULI OIL LIGHT BLO 2.079 2.079 DIHYDRO
SEVENIFF 10.395 10.395 ALLYL AMYL GLYCOLATE PRG BHT 0.520 0.520
DAMASCONE DELTA BHT 0.104 0.104 GALAXOLIDE 50 PCT BENZ SAL 5.198
5.198 CLOVE LEAF OIL RECT BLO 0.208 0.208 POLYSANTOL (ELINCS) 1.040
1.040 KOAVONE 5.198 5.198 CYCLACET PRG 10.395 10.395 ISO CYCLEMONE
E BHT 10.395 10.395 GRAPEFRUIT OIL RECT 2.079 2.079 NEBULONE
(ELINCS) 5.198 5.198 PERANAT 0.520 0.520 POIRENATE (ELINCS) 0.520
0.520 VERDOX 1.040 1.040 BENZ ACET PRG 2.079 2.079 VERIDIAN 1.040
1.040 VANILLIN PRG 0.208 0.208 LAVANDIN GROSSO OIL LMR 3.119 3.119
LIMONENE VAH "PFG" BHT 2.079 2.079 VERTOFIX COEUR 5.198 5.198
GALAXOLIDE SUPER 50 PCT IPM 5.198 5.198 VERTENEX HC 5.198 5.198
FORMULA I/FORMULA II 5.198 -- DIPROPYLENE GLYCOL -- 5.198 CYCLAAL
TOCO 15.198 15.198 METH DH JASMONATE BHT 10.395 10.395 Total
110.007 110.007
Example X
[0063] The differences in odor profiles of
octahydro-4,7-methano-1H-indene-5-acetaldehyde (Formula I) and
6-methyl-octahydro-4,7-methano-indene-5-carbaldehyde (Formula II)
and their analogs (Formulas III-IX) are listed in the
following:
TABLE-US-00002 Compounds Odor Profiles Formula I and Formula II
Floral, muguet, aldehydic, green, freesia, sweet, and slightly
woody Formula III and Formula IV Floral, fruity, woody, weak, and
metallic Formula V Strong, grapefruit, and offensive sulphury
Formula VI Weak, fatty, and green Formula VII and Formula VIII Very
weak and woody Formula IX Very weak, green, floral, fruity, and
harsh
[0064] The above evaluation demonstrated that the mixture of
Formula I and Formula II displayed highly desirable properties,
which are absent in the analogs of similar structures. The
advantageous and distinctive properties of Formula I and Formula II
are unexpected and would not have been predicted.
* * * * *