Title of Invention

"METHYLENE DIOXY DERIVATIVES"

Abstract The present invention is directed to a novel dioxin compound and the use of the novel compound in creating fragrances, and scents in items such as perfumes, colognes and personal care products.
Full Text METHYLENE DIOXY DERIVATIVES
Field of the Invention
The present invention relates to new chemical entities and the incorporation and use of
the new chemical entities as ftagrance chemicals the invention also relates to a synergistic
composition comprising the new chemical entities.
Background of the Invention
US Patent No. 4,902,840, hereby incorporated by reference, discloses the use of
substituted tetrahydroindane derivatives as useful fragrance chemicals. Despite this
disclosure and numerous other patents on fragrance materials, there is a continuing need to
provide additional fragrance materials such that perfumers may create new fragrances for
various applications.
Summary of the Invention
The present invention provides a novel chemical, and the use of this chemical 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 chemical to enhance
fragrance in perfumes, toilet waters, colognes, personal products and the like.
More specifically, the present invention is directed to the novel compound,
4,4a,5,6,7,8,9,9b-octahydro-7,7,8,9,9-pentamethyl-indano[4,5-d]-dioxin, which is
understood to be represented by the formula below:
Another embodiment of the invention is a method for enhancing a perfume by
incorporating an olfactory acceptable amount of the compound provided above.
These and other embodiments of the present invention will be apparent by
reading the following specification.
Detailed Description of the Invention
The novel compound of the present invention is prepared by the reaction of 6,7-
dihydro-l,2,3,4,5-pentamethyl indane, which is disclosed and claimed in US Patent Number
4,902,840, with formaldehyde. Preferably the formaldehyde is diluted, having a value of
from about 20 to about 50, preferably 30 to about 40 and most preferably about 37 weight
percent. An acid catalyst is preferably employed in the reaction. The acid is preferably a
mineral acid, such as sulfuric acid or hydrochloric acid, most preferably provided in a
concentrated form. A preferred method of carrying out the reaction is by refluxing the
components at an elevated temperature, from about 50 to about 120°C, preferably from
about 65 to about 110°C and most preferably at about 105°C.
The compound of the present invention has a powerful musk fragrance, with sweet,
powdery, spicy and nitromusk notes.
The use of the compound 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.
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.
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, roselike,
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.
A list of suitable fragrances is provided in US 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.
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.
The level of compound 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.
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.
An embodiment of the present invention provides a process for the
preparation of 4,4a,5, 6, 7,8,9,9b-octahydro-7,7,8,9,9-pentamethyl-Indano [4,5-d]-
dioxin of formula (I), the said process comprising steps of:
(a) heating a mixture of aliphatic aldehydej concentrated mineral acid and
mixture of solutions of polyalkylated indane at a temperature range of
100°-150°C for a period of 2-6 hours,
(b) cooling the reaction mixture of step (a) to 40°-50°C,
(c) adding toluene and 10% hydrochloric acid solution to the reaction
mixture,
(d) separating the organic layer of the reaction mixture of step (c) and
discarding the aqueous layer,
(e) washing the organic layer of step (d) with 10% aqueous alkali
carbonate solution, and
(f) distilling the organic layer of step (e) to recover pure toluene,
polyalkylated indane/ indane compounds and 4,4a,5, 6, 7,8,9,9boctahydro-
7,7,8,9,9-pentamethyl-Indano [4,5-d]-dioxin
In another embodiment, the aliphatic aldehyde used is selected from
formaldehyde, acetaldehyde or propanaldehyde and most preferably formaldehyde.
In yet another embodiment, the mineral acid used is selected from group
consisting of hydrochloric acid, sulphuric acid, and more preferably concentrated
hydrochloric acid and most preferably concentrated sulphuric acid.
In still another embodiment, the preferable temperature range for performing
the reaction is 105°-115° C of the reaction is most preferably maintained at 108°C.
In yet another embodiment, the weight percentage of the polyalkylated indane
used are 6,7-dehydes-l,l,2,3,3-pentamethyl indane (40 weight %), hexahydro-
1,1,2,3,3-pentamethyl indane (10 weight %) and 1,1,2,3,3-pentamethylindane (40
weight %).
In still yet another embodiment, the alkali carbonate is selected from group
consisting of sodium bicarbonate, potassium bicarbonate, sodium carbonate,
potassium carbonate and preferably sodium carbonate.
In another embodiment, the compound of formula (I) is obtained by
performing fractional distillation at a temperature range of 120-25°C and at a reduced
pressure of 3 mm of Hg.
Another embodiment of the invention relates to a composition for providing
fragrance, which comprises an olfactory acceptable amount of 4,4a,5,6, 7,8,9,9boctahydro-
7,7,8,9,9-pentamethyl-Indano [4,5-d]-dioxin of formula (I) and one or
more perfuming additives.
The composition of the present invention is synergist composition showing
unexpected property. In fact, by adding an olfactory amount of the present compound
4,4a,5,6,7,8)9,9b-octahydro-7,7,8,9,9-pentamethyl-Indano [4,5-d]-dioxin of formula
(I) to another perfumery ingredients, the perfumery property of the ingredient is
surprisingly enhanced.
The synergistic composition comprising 0.005 to 15 by wit % of the novel
compound in the composition and the rest includes the perfumery additives.
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 and g is understood to be grams. IFF as used in the examples is
understood to mean International Flavors & Fragrances Inc.
Example 1
Preparation of 4,4a, 5,6,8.9.9b-octahvdro-7.7.8.9,9-pentamethvl-indanor4.S-d]-dioxin
A mixture of 700 grains of 37 weight % formaldehyde. 60 grams of concentrated
sulfuric acid and 600 grams of a solution of 40 weight percent 6,7-dihydro-l,l,2,3,3-
pentamethylindane, 10 weight percent hexahydro-l,l,2,3,3-pentamethylindane and 40 weight percent 1,
1, 2, 3, 3-pentamethylindane was heated at reflux at 108°C for four hours. The mixture was then cooled
to 50°C. Toluene (400 grams) and 10% HC1 (500 milliliters) was added to the mixture. The aqueous
layer was discarded and the organic layer was washed twice with 500 milliliters of 10% sodium
carbonate solution.
The organic layer was distilled to recover the toluene, as well as 290 grams of a mixture
of hexahydro-1,1,2,3,3--pentamethylindane, 1,1,2,3,3-pentamethindene (boiling 15 point 94-
104°C at 2 mm) and 179 grams 4 4a,5,6,7,8,9,9b-octahydro-7,7,8,9,9-pentamethyl-indano[4,5-d]-dioxin
(boiling point 120-125°C at 3 mm).
The nmr spectrum of the 4,4a,5,6,7,8,9,9b-octahydro-7,7,8,9,9-pentainetriyl-indano[4,5-
d]-dioxin is as follows: 0.81-1.10 ppm (ms, 15H), 1.16-2.35 ppm (m, 5H), 3.81-4.08 ppm
(m,3H): 4.62 ppm (m, 1H). 4.86 ppm (d, IH).
-7-
Example 2
Incorporation of 4,4a.5.6.7.8.9.9b-octahvdro-7.7.8.9.9-Dentamethvl-indanor4.5-d1-dioxin into a
fragrance formulatioa
A fragrance was prepared according to the following formulation:
Material
TRIPLAL®(IFF)
Allyl cyclohexyl propionate
BORNAFDT(IFF)
CYCLABUTE® (IFF)
APHERMATE® (IFF)
Ethyl methyl phenyl glycidate
CYCLOGALBANIFF (IFF)
Isoamylbutyrate
ISOCYCLOCITRAL® (IFF)
JASMAL® (IFF)
Menthone
Peach aldehyde
4,4a,5,6,7,8,9,9b-octahydro-
7J,8,9,9-pentamethyl-indanof4,5-
Phenyl acetate
HC VERDOX® (IFF)
FRUCTONE® (IFF)
Parts
0.8
0.5
10.4
9.0
15
1.0
0.5
1.0
0.5
3.0
0.3
12.0
10.0
4.0
28
4.0
The fragrance was described as having a green, musky scent from the incorporation of the
compound of the present invention.



We claim:
1. A novel compound 4,4a,5,6,7,8,9,9b-octahydro-7,7,8,9,9-pentamethyl-indano[4,5-d]-dioxin.
2. A process for preparing the compound 4,4a,5,6,7,8,9,9b-octahydro-7,7,8,9,9-pentamethyl-indano[4,5-d]-dioxin as claimed in claim 1, comprising the steps of:

(a) heating a reaction mixture of an aliphatic aldehyde, a concentrated mineral acid and mixtures of solutions of polyalkylated indanes at a temperature ranging from 100°-150° C for 2-6 hours;
(b) cooling the reaction mixture to 40°-50° C;
(c) adding toluene and 10% hydrochloric acid solution to the reaction mixture to provide a reaction mixture of step (c);
(d) separating the organic layer of the reaction mixture of step (c) and discarding the aqueous layer to obtain an organic layer of step (d);
(e) washing the organic layer of step (d) with 10% aqueous solution of an alkali carbonate to obtain an organic layer of step (e); and
(f) distilling the organic layer of step (e) at a temperature ranging from 120 - 125°C and at a reduced pressure of 3 mm of Hg to recover pure toluene, polyalkylated indanes and 4,4a,5,6,7,8,9,9b-octahydro-7,7,8,9,9-pentamethyl-indano[4,5-d]-dioxin
wherein in step (a) the mixtures of solutions of polyalkylated indanes comprise 6,7-dehydro-l,l,2,3,3-pentamethylindane (40 weight %), hexahydro-1,1,2,3,3-pentamethylindane (10 weight %) and 1,1,2,3,3-pentamethylindane (40 weight %).
3. The process as claimed in claim 2, wherein in step (a) the aliphatic aldehyde is selected from the group consisting of formaldehyde, acetaldehyde and propanaldehyde and preferably formaldehyde.

4. The process as claimed in claim 2, wherein in step (a) the concentrated mineral acid is selected from the group consisting of concentrated hydrochloric acid and concentrated sulphuric acid, and preferably concentrated sulphuric acid.
5. The process as claimed in claim 2, wherein in step (a) the temperature preferably ranges from 105°-115° Q and preferably is maintained at 108° C.
6. The process as claimed in claim 2, wherein in step (e) the alkali carbonate is selected from the group consisting of sodium bicarbonate, potassium bicarbonate, sodium carbonate, and potassium carbonate and preferably sodium carbonate.
7. The 4,4a45,6,7,8,9,9b octahydro-7,7,8,9,9-pentamethyl-indano[4,5-d]- dioxin compound as claimed in claim 1 in the concentration of 0.005 to 15 weight %. is useful for preparing a synergistic fragrance composition

Documents:

133-DEL-2002-Correspondence-Others-(01-06-2009).pdf

133-DEL-2002-GPA-(01-06-2009).pdf

133-DEL-2002-petition-137-(01-06-2009).pdf

138-del-2002-abstract (19-06-2009).pdf

138-DEL-2002-Abstract-(03-06-2009).pdf

138-DEL-2002-Abstract-(14-05-2009).pdf

138-del-2002-abstract.pdf

138-del-2002-assignments.pdf

138-del-2002-claims (19-06-2009).pdf

138-DEL-2002-Claims-(03-06-2009).pdf

138-DEL-2002-Claims-(14-05-2009).pdf

138-del-2002-claims.pdf

138-DEL-2002-Correspondence-Others-(03-06-2009).pdf

138-DEL-2002-Correspondence-Others-(14-05-2009).pdf

138-DEL-2002-Correspondence-Others-(25-05-2009).pdf

138-del-2002-correspondence-others.pdf

138-del-2002-correspondence-po.pdf

138-del-2002-description (complete) (19-06-2009).pdf

138-del-2002-description (complete).pdf

138-del-2002-form-1 (19-06-2009).pdf

138-DEL-2002-Form-1-(03-06-2009).pdf

138-del-2002-form-1.pdf

138-del-2002-form-18.pdf

138-del-2002-form-2 (19-06-2009).pdf

138-DEL-2002-Form-2-(03-06-2009).pdf

138-del-2002-form-2.pdf

138-DEL-2002-Form-3-(25-05-2009).pdf

138-del-2002-form-3.pdf

138-del-2002-form-5 (19-06-2009).pdf

138-DEL-2002-Form-5-(03-06-2009).pdf

138-del-2002-form-5.pdf


Patent Number 235616
Indian Patent Application Number 138/DEL/2002
PG Journal Number 31/2009
Publication Date 31-Jul-2009
Grant Date 09-Jul-2009
Date of Filing 22-Feb-2002
Name of Patentee INTERNATIONAL FLAVORS & FRAGRANCES INC.
Applicant Address 521 WEST 57th STREET, LAW DEPARTMENT 10th FLOOR, NEW YORK, N.Y. 10019, USA.
Inventors:
# Inventor's Name Inventor's Address
1 ROBERT P. BELKO 8, BRANDON AVENUE, MONROE, NEW JERSEY 08831, USA.
2 MARK A. SPRECKER 6 SANDPIPER LANE, SEA BRIGHT, NEW JERSEY 07760, USA.
3 CHARLES E.J. BECK 10 BEEKMAN ROAD, SUMMIT, NEW JERSEY 07901, USA.
PCT International Classification Number C07D 319/08
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/791,296 2001-02-23 U.S.A.