Title: Macrocylic musk composition, organoleptic uses thereof and process for preparing same
Abstract: Described are mixtures consisting essentially of oxomacrocyclic compounds containing greater than about 40 weight % Δ3-cyclotetradecen-1-one and greater than about 40 weight % cyclotetradecanone and less than about 5 weight %, of Δ2-cyclotetradecen-1-one, perfumery uses thereof and chemo-selective catalytic hydrogen process for preparing same by hydrogenating mixtures containing significant concentrations, greater than 15 weight %, of Δ2-cyclotetradecen-1-one. The oxocarbocyclic compound-containing mixtures have advantageous musk aroma imparting, augmenting and enhancing perfumery properties causing the mixtures to be useful in perfume compositions, perfumed articles and perfumed polymers, including particles and fibers produced therefrom.
Patent Number: 6,894,020 Issued on 05/17/2005 to Mookherjee, et al.
| Inventors:
|
Mookherjee; Braja Dulal (Holmdel, NJ);
Narula; Anubhav P. S. (Hazlet, NJ);
Monteleone; Michael G. (Matawan, NJ);
Trenkle; Robert W. (Point Pleasant, NJ)
|
| Assignee:
|
International Flavors & Fragrances Inc. (New York, NY)
|
| Appl. No.:
|
760691 |
| Filed:
|
January 20, 2004 |
| Current U.S. Class: |
512/27; 512/8; 512/26 |
| Intern'l Class: |
A61K 007/46 |
| Field of Search: |
512/27,8,26
568/375
|
References Cited [Referenced By]
U.S. Patent Documents
Other References
Stork and Macdonald, Journal of the American Chemical Society, vol. 97, No. 5,
Mar. 5, 1975, pp. 1264-1265.
|
Primary Examiner: Cole; Monique T.
Attorney, Agent or Firm: Leightner; Joseph F., Migirov; Alexander
Parent Case Text
STATUS OF RELATED APPLICATIONS
This application is a divisional of U.S. Ser. No. 10/015,975, filed on Nov.
1, 2001 now U.S. Pat. No. 6,720,303, the contents hereby incorporated by reference
as if set forth in its entirety.
Claims
1. A process for augmenting, enhancing or imparting a musk aroma in or to a consumable
material selected from the group consisting of a perfume composition, a perfumed
article and a perfumed polymer comprising the step of intimately admixing an aroma
augmenting, enhancing or imparting quantity and concentration of a macrocyclic
musk composition, said macrocyclic musk composition provided by the steps of:
(a) admixing a cyclotetradecenone reactant mixture comprising greater than 45%
by weight of Δ
3-cyclotetradecen-1-one and greater than 15% by
weight of Δ
2-cyclotetradecen-1-one with a hydrogenation reaction
solvent to form a solvent-reactant mixture with the weight ratio of solvent:cyclotetradecenone
reactant mixture being from 20:70 up to 70:20;
(b) treating the resulting solvent-reactant mixture with hydrogen in the presence
of a chemo-selective hydrogenation catalyst in a concentration of from about 0.1%
up to about 0.5% by weight of the reaction mixture, at a temperature in the range
of from about 15° up to about 35° C. and at a pressure of from about
0 psig up to about 100 psig thus forming a hydrogenated product reaction mass,
whereby a composition comprising, on a solvent-free basis, greater than 40% by
weight of cyclotetradecanone, greater than 40% by weight of Δ
3-cyclotetradecen-1-one
and less than 5% by weight of Δ
2-cyclotetradecen-1-one is produced
(c) recovering the resulting macrocyclic musk composition from the hydrogenated
product reaction mass; and
admixing the resulting macrocyclic musk composition with a consumable material
base.
2. A process for augmenting, enhancing or imparting a musk aroma in or to a consumable
material selected from the group consisting of a perfume composition, a perfumed
article and a perfumed polymer comprising the step of intimately admixing an aroma
augmenting, enhancing or imparting quantity and concentration of the macrocyclic
musk composition provided in claim 1 wherein the step of treating the solvent-reactant
mixture with hydrogen causes the percentage of Δ
2-cyclotetradecen-1-one
in the composition to be reduced over the period of time during which the hydrogenation
reaction takes place, according to the algorithm:
wherein P represents the percentage of Δ
2-cyclotetradecen-1-one
in the mixture being reacted with hydrogen; θ represents the time in minutes
as measured from the commencement of the hydrogenation reaction; and α, A,
B, and K represent constants; and wherein:
P≧0;
θ≧0;
15≦A≦30;
0≦B≦5;
2.8≦K≦4.0; and
2×10
3≦α≦40×10
3.
3. A process for augmenting, enhancing or imparting a musk aroma in or to a consumable
material selected from the group consisting of a perfume composition, a perfumed
article and a perfumed polymer comprising the step of intimately admixing an aroma
augmenting, enhancing or imparting quantity and concentration of the macrocyclic
musk composition of claim 2 wherein rate of change of the percentage of Δ
2-cyclotetradecen-1-one
with respect to time, dP/dθ, in the reactant-solvent mixture being hydrogenated
is according to the algorithm:
Description
FIELD OF THE INVENTION
The present invention relates to musk aroma-imparting, augmenting and enhancing
mixtures of oxomacrocyclic compounds containing greater than about 40 weight %
Δ
3-cyclotetradecen-1-one and greater than about 40 weight % cyclo-tetradecanone
and less than about 5 weight % Δ
2-cyclotetradecen-1-one and a
process for preparing such mixtures by means of a chemo-selective catalytic hydrogen
of mixtures containing greater than 15% by weight of the Δ
2-cyclotetradecen-1-one
and greater than 45% by weight of the Δ
3-cyclotetradecen-1-one.
There has been considerable work performed relating to substances which can
be used to impart, alter, modify or enhance fragrances to or in various consumable
materials. These substances are used to diminish the use of natural materials particularly
in the musk aroma area where the use of natural materials is being replaced by
the use of synthetic materials which provide more uniform and predictable properties
in the finished product. Strong, substantive, sweet, warm, natural "animal-musk"
aromas with an absence of oily and waxy nuances in the topnotes, middle notes and
undertones, heretofore have been highly sought after by those skilled in the perfumery arts.
BACKGROUND OF THE INVENTION
Thus, prior art "animal-musk" aroma-imparting, augmenting and enhancing mixtures
containing significant concentrations of cyclotetradecanone, Δ
2-cyclo-tetradecen-1-one
and Δ
3-cyclotetradecen-1-one, for example, those disclosed in
U.S. Pat. No. 4,183,965 issued on Jan. 15, 1980, the disclosure of which is incorporated
herein by reference, and those disclosed by Stork and Macdonald at pages 1264 and
1265 of the Journal of the American Chemical Society, Volume 97, No. 5, Mar. 5,
1975 which have desirable musk aromas all have the undesirable oily and waxy nuances
present in their topnotes, middle notes and undertones, and impart these nuances
to finished products produced therefrom.
Thus, nothing in the prior art discloses or suggests cyclotetradecanone/mono-unsaturated
cyclotetradecen-1-one mixtures which have desirable natural "animal-musk" aromas
but which have no oily and waxy nuances present in the topnotes, middle notes or
undertones thereof. We have now discovered that the direct cause of the presence
of such waxy and oily notes is the presence in the aroma-imparting, augmenting
and enhancing mixture of significant concentrations, greater than 15 weight % on
a solvent-free basis, of the isomer, Δ
2-cyclotetradecen-1-one;
but if the concentration, on a solvent-free basis, were to be reduced to less than
5 weight % of the mixture, the existence of the oily and waxy nuances becomes imperceptible.
Accordingly, there exists a need for a practical method to produce cyclotetradecanone/Δ
3-mono-unsaturated
cyclotetradecen-1-one mixtures which have the aforementioned desirable aroma properties
but which have insignificant concentrations, less than 5 weight % on a solvent-free
basis, of Δ
2-cyclotetradecen-1-one.
SUMMARY OF THE INVENTION
Our invention is directed to strong, substantive, sweet, warm, natural "animal-musk"
aroma-imparting, augmenting and enhancing macrocyclic musk compositions which are
mixtures consisting essentially of oxocarbocyclic compounds containing greater
than about 40 weight % Δ
3-cyclotetradecen-1-one and greater than
about 40 weight % cyclotetradecanone, less than 5 weight %, of Δ
2-cyclotetradecen-1-one.
More specifically, our invention is directed to macrocyclic musk compositions
of matter consisting essentially of:
- (a) from about 40 up to about 60 weight %, on a solvent-free basis,
of cyclotetradecanone;
- (b) from about 40 up to about 60 weight %, on a solvent-free basis,
of Δ3-cyclotetradecen-1-one; and
- (c) less than 5 weight %, on a solvent-free basis, of Δ2-cyclotetradecen-1-one,
the weight ratio of cyclotetradecanone: Δ3-cyclotetradecen-1-one
being from about 6:4 down to about 4:6.
A preferred composition of our invention consists essentially of:
- (a) about 50% by weight, on a solvent-free basis, of cyclotetradecanone;
- (b) about 45% by weight, on a solvent-free basis, of Δ3-cyclotetradecen-1-one; and
- (c) less than 5 weight %, on a solvent-free basis, of Δ2-cyclotetradecen-1-one.
The process of our invention for producing the macrocyclic musk compositions
of our invention comprises the steps of:
- (a) admixing a cyclotetradecenone reactant mixture comprising greater
than 45% by weight of Δ3-cyclotetradecen-1-one and greater than
15% by weight of Δ2-cyclotetradecen-1-one with a hydrogenation
reaction solvent to form a solvent-reactant mixture, with the weight ratio of solvent:cyclotetradecenone
reactant mixture being from 20:70 up to 70:20;
- (b) treating the resulting solvent-reactant mixture with hydrogen in
the presence of a chemo-selective hydrogenation catalyst in a concentration of
from about 0.1% up to about 0.5% by weight of the reaction mixture, at a temperature
in the range of from about 15° C. up to about 35° C. and at a pressure
of from about 0 psig up to about 100 psig thus forming a hydrogenated product reaction
mass, whereby a composition comprising, on a solvent-free basis, greater than about
40% by weight of cyclotetradecanone, greater than about 40% by weight of Δ3-cyclotetradecen-1-one
and less than about 5% by weight of Δ2-cyclotetradecen-1-one is
produced; and
- (c) recovering the resulting macrocyclic musk composition from the hydrogenated
product reaction mass preferably by means of vacuum distillation).
DETAILED DESCRIPTION OF THE INVENTION
Several techniques for the preparation of the cyclotetradecenone reactant
mixtures may be used in the practice of our invention, for example:
- (a) The process described in Example I at columns 11-14 of U.S. Pat.
No. 4,183,965 issued on Jan. 15, 1980, the disclosure of which is incorporated
herein by reference, or
- (b) A process, as more particularly described herein in detail in Example
I, infra, comprising the steps of (i) treating 3-hydroxycyclotetradecan-1-one in
the vapor phase with a dehydrating quantity and concentration of anhydrous aluminum
oxide particles, preferably from about 4 mesh up to about 8 mesh, at a dehydrating
temperature, preferably from about 360° C. up to about 400° C., and pressure,
preferably from about 1 mm Hg up to about 20 mm Hg, to form a dehydration product
reaction mass and then (ii) recovering the cyclotetradecenone reactant mixture
from the dehydration product reaction mass, preferably by means of vacuum distillation.
Preferably, the chemo-selective hydrogenation catalyst is a supported
palladium catalyst containing from about 2 weight % palladium up to about 10 weight
% palladium such as palladium on carbon, palladium on calcium carbonate and palladium
on barium sulfate.
The hydrogenation reaction solvent is non-reactive with any reactant or reaction
product, and is preferably methanol, ethanol, 2-propanol, 1-propanol, acetone,
methylethylketone, methylisobutylketone, tetrahydrofuran or mixtures thereof.
A preferred set of hydrogenation reaction conditions is specifically set forth
herein in Example II, infra.
Also, a preferred set of hydrogenation reaction conditions is as follows:
(i) Chemo-selective hydrogen catalyst: 5 weight % palladium on carbon;
(ii) Solvent: 2-propanol;
(iii) Hydrogenation reaction pressure: 100 psig;
(iv) Hydrogenation reaction temperature: 35° C.
(v) Weight ratio of solvent:reactant mixture: 50:50.
In carrying out the hydrogenation reaction of our invention, treatment of the
solvent-reactant mixture with hydrogen causes the percentage P of Δ
2-cyclotetradecen-1-one
in the composition to be reduced over the period of time, θ (minutes) during
which the hydrogenation takes place, according to either of the algorithms:
wherein θ represents the time in minutes as measured from the commencement
of the hydrogenation reaction; and α, A, B and K represent constants; and wherein:
- P≧0;
- θ≧0;
- 15≦A≦30;
- 0≦B≦5;
- 2.8≦K≦4.0; and
- 2×103≦α≦40 ×103.
In addition, the rate of change with respect to time of the percentage of Δ
2-cyclotetradecen-1-one,
dP/dθ, in the reactant-solvent mixture being hydrogenated is according to
the algorithm:
The macrocyclic musk compositions of our invention and one or more auxiliary
perfume ingredients, including, for example, alcohols, aldehydes, nitrites, esters,
cyclic esters, ketones other than the ingredients of the macrocyclic musk compositions
of our invention, hydrocarbons and natural essential oils may be admixed so that
the combined odors of the individual components produce a pleasant and desired
fragrance particularly and preferably in musk and "animal-like" fragrances. Such
perfume compositions usually contain (a) the main note or the "bouquet" or foundation
stone of the composition; (b) modifiers which round off and accompany the main
note; (c) fixatives which include odorous substances which lend a particular note
to the perfume throughout all stages of evaporation and substances which retard
evaporation; and (d) topnotes which are usually low boiling fresh smelling materials.
In the perfume composition, it is each of the individual components which contribute
to its particular olfactory characteristics, but the over-all effect of the perfume
composition will be the sum of the effects of each of the ingredients. Thus, the
macrocyclic musk compositions of our invention can be used to alter the aroma characteristics
of a perfume composition, for example, by utilizing or moderating the olfactory
reaction contributed by at least one other ingredient in the composition.
The amount of macrocyclic musk composition of our invention which will be effective
in perfume compositions depends on many factors including the other ingredients,
their amounts and the effects which are desired. It has been found that perfume
compositions containing as little as 0.01% of the macrocyclic musk compositions
of our invention and even less (e.g., 0.005%) can be used to impart sweet, warm,
natural, "animal musk" aroma nuances (without oily and waxy notes) to soaps, anionic,
cationic, nonionic and zwitterionic detergents, fabric softener articles, fabric
softener compositions, hair preparations, cosmetics and other products. The amount
employed can range up to 10% of the fragrance components and will depend on considerations
of cost, nature of the end product, the effect desired on the finished product
and the particular fragrance sought.
The macrocyclic musk compositions of our invention are useful, taken alone or
in perfume compositions as olfactory components in anionic, cationic, nonionic
and zwitterionic detergents, soaps, fabric softener compositions, fabric softener
articles for use in clothes dryers (e.g., BOUNCE®, Procter & Gamble Company
of Cincinnati, Ohio, U.S.A.), space odorants and deodorants, perfumes, colognes,
toilet water, bath preparations such as bath oils and bath solids; hair preparations
such as lacquers, brilliantines; creams; deodorants; hand lotions; sun screens;
powders such as talcs, dusting powders, face powders and the like. When used as
an olfactory component in perfume compositions or perfumed articles, such as anionic,
cationic, nonionic and zwitterionic detergents, and in fabric softener compositions
and fabric softener articles (e.g. for use in clothing dryers) as little as 0.05%
of the macrocyclic musk compositions of our invention will suffice to impart a
sweet, warm, natural "animal-musk" aroma, without the undesireable oily and waxy
nuances. Generally no more than 5% of the macrocyclic musk composition of our invention
is required in the perfume composition or in the perfumed article.
In addition, the perfume composition or fragrance composition of our invention
can contain a vehicle or carrier for the macrocyclic musk compositions of our invention.
The vehicle can be a liquid such as a non-toxic alcohol (e.g., ethanol) a non-toxic
glycol (e.g., propylene glycol) or the like. The carrier can also be an absorbent
solid, such as a gum (e.g., gum arabic, or xanthan gum) or components for encapsulating
the composition (such as gelatin) as by means of coacervation. The carrier can
be a microporous polymer for use in conjunction with particulate microporous polymer
delivery systems, as disclosed in U.S. Pat. No. 6,213,409 issued on Apr. 10, 2001,
the disclosure of which is incorporated herein by reference, or for use in conjunction
with fiber delivery systems,as disclosed in U.S. Pat. No. 6,207,274 issued on Mar.
27, 2001, the disclosure of which is incorporated herein by reference.
It will thus be apparent that the macrocyclic musk compositions of our invention
can be utilized to alter the sensory properties of a wide variety of consumable materials.
The following examples are illustrative and the invention is to be restricted
thereto only as indicated in the appended claims. All parts and percentages given
herein are by weight unless otherwise specified.
EXAMPLE I
Preparation of Mixture of Δ
2-and Δ
3CYCLOTETRADECEN-1-ONES
An one liter distillation flask, equipped with a heating mantle, containing 425
gm.2-hydroxycyclotetradecan-1-one is connected directly to a 12″×1″
inside diameter quartz pyrolysis tube containing 75 gm. of aluminum oxide particles
having a particle size in the range of 4-8 mesh. A vacuum distillation (rushover)
unit is connected directly to the quartz pyrolysis tube at the end opposite to
that of the one liter distillation flask. The pyrolysis tube is heated using a
high temperature Lindberg heavy duty split laboratory furnace.
The distillation flask is slowly heated to a temperature in the range of 180-200°
C. thereby causing the evolution of 2-hydroxycyclotetradecan-1-one vapors. The
resulting 2-hydroxycyclotetradecan-1-one vapors are thus passed into the quartz
tube which is maintained at a temperature in the range of 390-400° C. under
2 mm Hg. pressure, and over the heated aluminum oxide bed thereby effecting a dehydration reaction.
The resulting reaction product is then fractionally distilled at 2.16-2.20 mm
Hg at a vapor temperature of 90-140° C. using reflux ratios of 3:1 to 4:1,
yielding 27 fractions. NMR, IR and mass spectral analyses confirm the following
components in bulked distillation fractions 14-19:
(i) 20.7% Δ
2-cycotetradecen-1-one;
(ii) 63.2% Δ
3-cyclotetradecen-1-one;
(iii) 13.4% cyclotetradecanone
The resulting product has a musk aroma with waxy and oily topnotes, middle notes
and undertones having a ‘musk’ intensity, on a scale of 1-10 of 6.5;
and a substantivity on a scale of 1-10 of 8.0.
EXAMPLE II
Preparation of Mixture of Cyclotetradecanone and Δ
3-CYCLOTETRADECEN-1-ONE
Into a 1 liter zipper autoclave equipped with a hydrogen feed line, the following
ingredients are placed:
- (i) 250 grams of bulked distillation fractions 14-19 of the distillation
of the reaction product of Example I;
- (ii) 250 grams of 2-propanol; and
- (iii) 0.7 grams of a 5% palladium on carbon catalyst.
The autoclave is sealed and heated to 35° C. and pressurized with hydrogen
to 100 psig. Pressurization with hydrogen is maintained at 100 psig at the temperature
of 35° C. for a period of 51 minutes. The autoclave is then cooled to room
temperature and opened and the contents are removed and filtered. The resulting
reaction mass is then admixed with 6 gm. of Primol and fractionally distilled under
reduced pressure, yielding 11 fractions distilling at 108-122° C. at 1.00-1.19
mm Hg pressure. Fractions 5-10 distilling at 115-122° C. are bulked. NMR,
IR and mass spectral analysis confirm that the resulting product consists of: (a)
1.63% Δ
2-cyclotetradecen-1-one; (b) 45% Δ
3-cyclotetradecen-1-one;
and (c) 50% cyclotetradecanone. The percentage of Δ
2-cyclotetradecen-one
and corresponding time of hydrogenation reaction transpired is as follows:
| |
| |
TIME (MINUTES) |
PERCENTAGE |
| |
| |
| |
0 |
20.71 |
| |
14 |
15 |
| |
18 |
9.8 |
| |
23 |
2.9 |
| |
51 |
1.3 |
| |
The resulting product has a sweet, warm, natural "animal-musk" aroma (without
oily or waxy topnotes, middle notes or undertones) and has a substantivity of "9.5"
on a scale of 1-10, and musk intensity of 9.8 on a scale of 1-10.
EXAMPLE III
Musk Perfume Formulation
The following musk perfume formulation is prepared:
| |
| |
Ingredients |
Parts by Weight |
| |
| |
Musk Ambrette |
200 |
| |
Musk Ketone |
200 |
| |
GALAXOLIDE 50 ® |
140 |
| |
Beta Ionone |
50 |
| |
Vetiveryl Acetate |
50 |
| |
Sandalwood Oil |
100 |
| |
Benzyl Benzoate |
300 |
| |
Macreocyclic musk composition of |
250 |
| |
Example II, infra, bulked distillation |
| |
fractions 5-10 |
| |
The macrocyclic musk composition of Example II imparts to this musk perfume formulation
sweet, warm, natural "animal musk" undertones and topnotes (without any oily or
waxy nuances).
EXAMPLE IV
Preparation of Cosmetic Compositions
A cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum powder
with 0.15 grams of the macrocyclic musk composition prepared according to Example
II. The resulting powder has an excellent sweet, warm, natural "animal-musk" aroma
(without any oily or waxy topnotes, middle notes or undertones).
A second cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum
powder with 0.20 grams of the perfume composition of Example III. The resulting
powder has an excellent musk aroma with sweet, warm, natural "animal-musk" topnotes
and undertones (without any oily or waxy nuances).
EXAMPLE V
Preparation of Soap Cake
100 grams of soap chips are prepared according to Example V of U.S. Pat. No.
4,058,490 issued on Nov. 15, 1977, the specification for which is incorporated
by reference herein. The soap chips are blended in a chip mixer with 40 grams of
water and 4 grams of titanium dioxide The resulting blend is then admixed with
one gram of the macrocyclic musk composition of Example II until a homogeneous
blend is obtained. The resulting blend is formulated into a soap cake and dried
under 150 mm Hg. absolute pressure. The perfumed soap cake manifests an excellent,
substantive, intense sweet, warm, natural "animal-musk" aroma (without the presence
of any oily or waxy nuances).
*
