U.S. patent application number 11/960143 was filed with the patent office on 2009-06-25 for novel dioxaspiro compounds and their use in perfume compositions.
This patent application is currently assigned to INTERNATIONAL FLAVORS & FRAGRANCES INC.. Invention is credited to Anthony T. Levorse, JR., Richard A. Weiss.
Application Number | 20090163404 11/960143 |
Document ID | / |
Family ID | 40748589 |
Filed Date | 2009-06-25 |
United States Patent
Application |
20090163404 |
Kind Code |
A1 |
Levorse, JR.; Anthony T. ;
et al. |
June 25, 2009 |
Novel Dioxaspiro Compounds and Their Use in Perfume
Compositions
Abstract
The present invention a method of improving, enhancing or
modifying a fragrance formulation through the addition of an
olfactory acceptable amount of the following compound: ##STR00001##
wherein m is 1 or 2; and if m is 1, which provides a five-membered
dioxaspiro ring, n is an integer from 2 to 4, and the methyl group
in the dioxaspiro ring is independently located in the 2 and/or 3
positions of the dioxaspiro ring; or if m is 2, which provides a
six-membered dioxaspiro ring, n is an integer from 0 to 6, and the
methyl group in the dioxaspiro ring is independently located in the
2, 3, and/or 4 positions of the dioxaspiro ring.
Inventors: |
Levorse, JR.; Anthony T.;
(Westfield, NJ) ; Weiss; Richard A.; (Livingston,
NJ) |
Correspondence
Address: |
INTERNATIONAL FLAVORS & FRAGRANCES INC.
521 WEST 57TH ST
NEW YORK
NY
10019
US
|
Assignee: |
INTERNATIONAL FLAVORS &
FRAGRANCES INC.
New York
NY
|
Family ID: |
40748589 |
Appl. No.: |
11/960143 |
Filed: |
December 19, 2007 |
Current U.S.
Class: |
512/9 ; 549/333;
549/341 |
Current CPC
Class: |
C11B 9/008 20130101;
A61Q 13/00 20130101; C11B 9/0076 20130101; C11D 3/2096 20130101;
A61K 8/498 20130101; C11D 3/50 20130101; C11B 9/0088 20130101 |
Class at
Publication: |
512/9 ; 549/333;
549/341 |
International
Class: |
C07D 317/72 20060101
C07D317/72; C07D 319/08 20060101 C07D319/08; A61K 8/33 20060101
A61K008/33; A61Q 13/00 20060101 A61Q013/00 |
Claims
1. A compound of Formula I: ##STR00008## wherein m is 1 or 2; and
if m is 1, which provides a five-membered dioxaspiro ring, n is an
integer from 2 to 4, and the methyl group in the five-membered
dioxaspiro ring is independently located in the 2 and/or 3
positions of the dioxaspiro ring; or if m is 2, which provides a
six-membered dioxaspiro ring, n is an integer from 0 to 6, and the
methyl group in the six-membered dioxaspiro ring is independently
located in the 2, 3, and/or 4 positions of the dioxaspiro ring.
2. The compound of claim 1, wherein m is 1, n is 2, and the methyl
groups in the five-membered dioxaspiro ring are located in the 2
and 3 positions, and wherein the compound is 2,3,6,10-tetramethyl-
1,4-dioxaspiro[4,5]decane.
3. The compound of claim 1, wherein in m is 2, n is 2, and the
methyl groups in the six-membered dioxaspiro ring are located in
the 2 and 4 positions, and wherein the compound is
2,4,7,11-tetramethyl-1,5- dioxaspiro[5]undecane.
4. The compound of claim 1, wherein m is 2, n is 2, and the methyl
groups in the six-membered dioxaspiro ring are both located in the
3 position, and wherein the compound is
3,3,7,11-tetramethyl-1,5-dioxaspiro[5,5]undecane.
5. A method of improving, enhancing or modifying a fragrance
formulation through the addition of an olfactory acceptable amount
of a compound of Formula I: ##STR00009## wherein m is 1 or 2; and
if m is 1, which provides a five-membered dioxaspiro ring, n is an
integer from 2 to 4, and the methyl group in the five-membered
dioxaspiro ring is independently located in the 2 and/or 3
positions; or if m is 2, which provides a six-membered dioxaspiro
ring, n is an integer from 0 to 6, and the methyl group in the
six-membered dioxaspiro ring is independently located in the 2, 3,
and/or 4 positions.
6. The method of claim 5, wherein in the compound, m is 1, n is 2,
and the methyl groups in the five-membered dioxaspiro ring are
located in the 2 and 3 positions, and wherein the compound is
2,3,6,10-tetramethyl-1,4- dioxaspiro[4,5]decane.
7. The method of claim 5, wherein in the compound, m is 2, n is 2,
and the methyl groups in the six-membered dioxaspiro ring are
located in the 2 and 4 positions, and wherein the compound is
2,4,7,11-tetramethyl-1,5- dioxaspiro[5]undecane.
8. The method of claim 5, wherein in the compound, m is 2, n is 2,
and the methyl groups in the six-membered dioxaspiro ring are both
located in the 3 position, and wherein the compound is
3,3,7,11-tetramethyl-1,5- dioxaspiro[5]undecane.
9. The method of claim 5, wherein the fragrance formulation is
incorporated into a product selected from the group consisting of a
perfume, a cologne, a toilet water, a cosmetic product, a personal
care product, a fabric care product, a cleaning product, and an air
freshener.
10. The method of claim 9, wherein the cleaning product is selected
from the group consisting of a detergent, a dishwashing
composition, a scrubbing compound, and a window cleaner.
11. The method of claim 5, wherein the olfactory acceptable amount
is from about 0.005 to about 10 weight percent of the fragrance
formulation.
12. The method of claim 5, wherein the olfactory acceptable amount
is from about 0.5 to about 8 weight percent of the fragrance
formulation.
13. The method of claim 5, wherein the olfactory acceptable amount
is from about 1 to about 7 weight percent of the fragrance
formulation.
14. A fragrance formulation containing an olfactory effective
amount of a compound of Formula I: ##STR00010## wherein m is 1 or
2; and if m is 1, which provides a five-membered dioxaspiro ring, n
is an integer from 2 to 4, and the methyl group in the
five-membered dioxaspiro ring is independently located in the 2
and/or 3 positions; or if m is 2, which provides a six-membered
dioxaspiro ring, n is an integer from 0 to 6, and the methyl group
in the six-membered dioxaspiro ring is independently located in the
2, 3, and/or 4 positions.
15. The fragrance formulation of claim 14, wherein in the compound,
m is 1, n is 2, and the methyl groups in the five-membered
dioxaspiro ring are located in the 2 and 3 positions, and wherein
the compound is 2,3,6,10-tetramethyl-
1,4-dioxaspiro[4,5]decane.
16. A fragrance product containing an olfactory effective amount of
the compound of claim 1.
17. The fragrance product of claim 16, wherein in the compound, m
is 1, n is 2, and the methyl groups in the five-membered dioxaspiro
ring are located in the 2 and 3 positions, and wherein the compound
is 2,3,6,10-tetramethyl-1,4- dioxaspiro[4,5]decane.
Description
FIELD OF THE INVENTION
[0001] 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
[0002] 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
differences in the chemical structure of the molecule can result in
significant differences in the odor, notes and characteristics of a
molecule. These variations and the ongoing need to discover and use
the new chemicals in the development of new fragrances allow the
perfumers to apply the new compounds in creating new
fragrances.
SUMMARY OF THE INVENTION
[0003] 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.
[0004] More specifically, the present invention is directed to the
fragrance compounds and a method of improving, enhancing or
modifying a fragrance formulation through the addition of an
olfactory acceptable amount of dioxaspiro compounds represented by
Formula I set forth below:
##STR00002##
[0005] wherein m is 1 or 2;
[0006] and if m is 1, which provides a five-membered dioxaspiro
ring, n is an integer from 2 to 4, and the methyl group in the
dioxaspiro ring is independently located in the 2 and/or 3
positions of the dioxaspiro ring;
[0007] or if m is 2, which provides a six-membered dioxaspiro ring,
n is an integer from 0 to 6, and the methyl group in the dioxaspiro
ring is independently located in the 2, 3, and/or 4 positions of
the dioxaspiro ring.
[0008] Another embodiment of the invention is directed to a method
for enhancing a perfume composition by incorporating an olfactory
acceptable amount of the dioxaspiro compounds provided above.
[0009] These and other embodiments of the present invention will be
apparent by reading the following specification.
DETAILED DESCRIPTION OF THE INVENTION
[0010] In Formulae I above, m is 1 or 2; and if m is 1, which
provides a five-membered dioxaspiro ring, n is an integer from 2 to
4, and the methyl group in the dioxaspiro ring is independently
located in the 2 and/or 3 positions of the dioxaspiro ring; or if m
is 2, which provides a six-membered dioxaspiro ring, n is an
integer from 0 to 6, and the methyl group in the dioxaspiro ring is
independently located in the 2, 3, and/or 4 positions of the
dioxaspiro ring.
[0011] It is known to those with the skill in the art that Formula
I provides a structure containing five-membered ring when m is 1
and a structure containing a six-membered ring when m is 2.
[0012] In another embodiment of the invention, the novel compounds
of the invention are represented by the following structures:
##STR00003##
[0013] Those with the skill in the art will appreciate that in
Formula I:
[0014] when m is 1, n is 2, and the methyl groups in the dioxaspiro
ring are located in the 2 and 3 positions of the dioxaspiro ring, a
compound of Formula II,
2,3,6,10-tetramethyl-1,4-dioxaspiro[4,5]decane, is provided;
[0015] when m is 2, n is 2, and the methyl groups in the dioxaspiro
ring are located in the 2 and 4 positions of the dioxaspiro ring, a
compound of Formula III,
2,4,7,11-tetramethyl-1,5-dioxaspiro[5,5]undecane, is provided;
and
[0016] when m is 2, n is 2, and the methyl groups in the dioxaspiro
ring are both located in the 3 position of the dioxaspiro ring, a
compound of Formula IV,
3,3,7,11-tetramethyl-1,5-dioxaspiro[5,5]undecane, is provided.
[0017] The compounds of the present invention may be prepared via a
cyclization reaction of 2,6-dimethyl cyclohexanone, commercially
available from Aldrich Chemical Co. with alkane 1, 2 or 1,3 diols.
Those with the skill in the art will appreciate that suitable
alkane diols include, for example, ethylene glycol, 1,2-propylene
glycol, 2,3-butanediol, 2,4-pentanediol, and 2,2-dimethyl
propanediol.
[0018] The cyclization reaction can be depicted by a general scheme
as follows:
##STR00004##
[0019] Those with skill in the art will 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. Suitable techniques include chromatography such as high
performance liquid chromatography, referred to as HPLC, and
particularly gel chromatography and solid phase microextraction,
referred to as SPME. The use of optically active diols such as
R-1,2 propane diol as a starting material would afford specific
diastereomeric isomers that are contemplated in the present
invention.
[0020] 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 as well as 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.
[0021] 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.
[0022] 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.
[0023] 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.
[0024] Olfactory effective 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.
[0025] The level of compounds of the invention employed in the
perfumed article varies from about 0.005 to about 10 weight
percent, preferably from about 0.5 to about 8 and most preferably
from about 1 to about 7 weight percent. In addition to the
compounds other agents can be used in conjunction with the
fragrance. 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.
[0026] Another method of reporting the level of the compounds of
the invention in the perfumed composition, i.e., the compounds as a
weight percentage of the materials added to impart the desired
fragrance. The compounds of the invention can range widely from
0.005 to about 70 weight percent of the perfumed composition,
preferably from about 0.1 to about 50 and most preferably from
about 0.2 to about 25 weight percent. Those with skill in the art
will be able to employ the desired level of the compounds of the
invention to provide the desired fragrance and intensity.
[0027] When used in a fragrance formulation this ingredient
provides freshness making the fragrance top notes more desirable
and noticeable. It also has a spicy peppery odor which is very
commonly used in men's fragrances added for fragrance
appropriateness and desirability. The woody part of it is very
useful in both men's and women's fragrances adding body and
substantivity to the finished product. All of these odor qualities
found in this material assist in beautifying and enhancing the
finished accord improving the performance of the other materials in
the fragrance. The floral of it will beautify as well and makes the
fragrance more desirable and add the perception of value. There is
also the fruity side of it which is found in many fragrances today
which happens to be very trendy, especially for the younger
consumer.
[0028] 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. All
starting materials, reagents and catalysts were purchased from
Aldrich Chemical Company and used as is. 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, Kg is understood to be
kilogram, g is understood to be gram, and mmHg be millimeters (mm)
of mercury (Hg). IFF as used in the examples is understood to mean
International Flavors & Fragrances Inc., New York, N.Y.,
USA.
EXAMPLE I
##STR00005##
[0030] Preparation of
2,3,6,10-tetramethyl-1,4-dioxaspiro[4,5]decane: A reaction flask
equipped with a Dean Stark trap was charged with 2,6-dimethyl
cyclohehanone (200 g), 2,3-butanediol (315 g), p-toluenesulfonic
acid (2 g) and toluene (300 mL). The reaction mass was heated to
reflux (110-130.degree. C.). Water (36 mL) was collected in the
Dean Stark trap. When no water was recovered the reaction mass was
cooled to an ambient temperature, neutralized with 10% aqueous
sodium carbonate (100 mL) and washed with brine. Purification by
vacuum distillation afforded
2,3,6,10-tetramethyl-1,4-dioxaspiro[4,5]decane (265 g)), which had
a boiling point of 104.degree. C. at a pressure of 16 mmHg.
[0031] H1 NMR: 0.87-0.96 ppm (m, 6H), 1.1-1.24 ppm (m, 6H),
1.25-1.56 ppm (m, 4H), 1.56-1.91 ppm (m, 4H), 3.55-3.71 ppm (m,
2H)
[0032] The compound was described as having a leathery note.
EXAMPLE II
##STR00006##
[0034] Preparation of
2,4,7,11-tetramethyl-1,5-dioxaspiro[5,5]undecane: A reaction flask
equipped with a Dean Stark trap was charged with 2,6-dimethyl
cyclohehanone (252 g), 2,4-pentanediol (312 g), p-toluenesulfonic
acid (6 g) and toluene (300 mL). The reaction mass was heated to
reflux (110-130.degree. C.). Water (36 mL) was collected in the
Dean Stark trap. When no water was recovered, the reaction mass was
cooled to an ambient temperature, neutralized with 10% aqueous
sodium carbonate (100 mL) and washed with brine. Purification by
vacuum distillation afforded
2,4,7,11-tetramethyl-1,5-dioxaspiro[5,5]undecane (339 g), which had
a boiling point of 124.degree. C. at a pressure of 40 mmHg.
[0035] H1 NMR: 0.86 ppm (d, 3H, J=6.56 Hz), 0.93 ppm (d, 3H, J=7.23
Hz), 0.99-1.07 ppm (m, 1H), 1.11-1.14 ppm (d, 6H, J=6.97 Hz, of d,
J=2.70 Hz), 1.14-1.26 ppm (m, 1H), 1.33-1.59 ppm (m, 6H), 1.60-1.68
ppm (m, 1H), 1.70-1.79 ppm (m, 1H), 3.85-3.91 ppm (m, 1H),
3.91-3.98 ppm (m, 1H)
[0036] The compound was described as having a strong chemical
solvent note.
EXAMPLE III
##STR00007##
[0038] Preparation of
3,3,7,11-tetramethyl-1,5-dioxaspiro[5,5]undecane: A reaction flask
equipped with a Dean Stark trap was charged with 2,6-dimethyl
cyclohehanone (285 g,), 2,2-dimethyl propanediol (312 g),
p-toluenesulfonic acid (3 g,) and toluene (200 mL,). The reaction
mass was heated to reflux (110-130.degree. C.). Water (36 mL) was
collected in the Dean Stark trap. When no water was recovered, the
reaction mass was cooled to an ambient temperature, neutralized
with 10% aqueous sodium carbonate (100 mL) and washed with brine.
Purification by vacuum distillation afforded
3,3,7,11-tetramethyl-1,5-dioxaspiro[5,5]undecane (339 g), which had
a boiling point of 124.degree. C. at a pressure of 10 mmHg.
[0039] H1 NMR: 0.96 ppm (s, 6H), 0.98 ppm (s, 6H), 1.34-1.61 ppm
(m, 8H), 3.44-3.49 ppm (m, 4H)
[0040] The compound was described as having a rubbery chemical
note.
EXAMPLE IV
[0041] The fragrance formula exemplified as follows demonstrates
that dioxaspiro compound imparts a floral woody character to the
fragrance formula.
TABLE-US-00001 Parts* Ingredients + - Caryophyllene 40.0 40.0
Cedarwood White PG 50.0 50.0 Fenchol 5.0 5.0 Healingwood .RTM. 80.0
80.0 Iso E Super .RTM. 425.0 425.0 Methyl beta naphthyl ketone 2.0
2.0 Methyl Ionone Gamma Coeur 100.0 100.0 Patchoulol 4101 LMR 5.0
5.0 Paxamber .RTM. 100.0 100.0 Sanjinol .RTM. 5.0 5.0 Veramoss 10%
dipropylene glycol (DPG) 8.0 8.0 Vertofix Coeur 150.0 150.0
2,3,6,10-Tetramethyl-1,4-dioxaspiro[4,5]decane 5.0 -- Dipropylene
glycol -- 5.0 Total 975.0 975.0 *"+" represents a dioxaspiro
compound containing formula; and "-" represents a dioxaspiro
compound non-containing formula.
* * * * *