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Description  |
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BACKGROUND OF THE INVENTION
The present invention relates to acetyl hydrindacenes and acetyl indanes
and mixtures of same as well as organoleptic uses thereof to alter,
modify, augment, enhance or impart flavors and/or aromas of (or to) to
consumable materials.
There has been considerable work performed relating to substances which can
be used to impart (or alter, modify or enhance) flavors and fragrances to
(or in) various consumable materials. These substances are used to
diminish the use of natural materials, some of which may be in short
supply and to provide more uniform properties in the finished product.
Musky aromas and musky and sweet flavor characteristics are particularly
desirable for many uses in foodstuff flavors, particularly apricot, peach
and pear flavors. Rich, animal musk, floral and sandalwood-like aromas are
desirable in several types of perfume compositions and for use in perfumed
articles. Sweet, floral, musk notes are desirable in smoking tobacco
flavor compositions and for use in conjunction with smoking tobaccos.
U.S. Pat. No. 3,244,751 issued on Apr. 5, 1966 discloses the reaction of
1,1,6,6-tetramethyl-as-hydrindacene with acetyl chloride to form
4-acetyl-1,1,6,6-tetramethyl-as-hydrindacene, useful for its properties as
a perfumery material according to the following reaction:
##STR1##
The use of acetyl chloride rather than other acylating agents such as
acetic anhydride gives rise to the production of the specific isomer
having the structure:
##STR2##
(which exists in the solid phase crystalline form at ambient temperature
and pressure and which has sandalwood-aroma notes), rather than the
mixture of isomers having the structures:
##STR3##
(which exists in the liquid phase at ambient temperature and pressure).
At column 6, lines 5-32 of U.S. Pat. No. 3,244,751,
5-acetyl-3,3,8,8-tetramethyl-as-hydrindacene is indicated to have been
prepared from 5-isopropyl-3,3,8,8-tetramethyl-as-hydrindacene by means of
the reaction of acetic anhydride with
5-isopropyl-3,3,8,8-tetramethyl-as-hydrindacene in the presence of
aluminum chloride and ethylene dichloride. The reaction product was
indicated in said U.S. Pat. No. 3,347,946 to have a "persistent musk-like
odor" and to be "suitable as a fixative in perfumery". When, however, a
reaction procedure is used wherein the aluminum chloride is added to the
5-isopropyl-3,3,8,8-tetramethyl-as-hydrindacene at 0.degree. C., a 60:40
mixture of two isomers is obtained:
60% of the isomer having the structure:
##STR4##
and 40% of the isomer having the structure:
##STR5##
When it is attempted to carry out the same reaction at 20.degree. C. only
the compound having the structure:
##STR6##
(existing as a solid at ambient temperatures and pressures) is obtained.
On the other hand, if a mixture of
5-isopropyl-3,3,8,8-tetramethyl-as-hydrindacene, and acetic anhydride is
added to a stirred slurry of aluminum chloride at 0.degree. C., a mixture
of four compounds is obtained, to wit:
##STR7##
(the mixture existing in the liquid phase at ambient temperature and
pressure). Accordingly, the prior art does not explicitly or implicitly
indicate the technique for preparation of mixtures of isomers of acetyl
hydrindacenes or acetyl indanes having the structures:
##STR8##
using hydrindacenes having the structure:
##STR9##
as a starting material; nor does the prior art disclose that acetyl
indanes, acetyl hydrindacenes or mixtures of same can be produced as
liquids at ambient temperatures and pressures thereby enabling them to be
used in a commercially advantageous manner since it is no longer necessary
to use additional solvents to cause such materials to be incorporated into
standard liquid perfume compositions or colognes or liquid flavor
compositions or intimately admixed with either solid or liquid perfumed
article compositions, e.g., anionic, cationic or nonionic detergents.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is the GLC profile for the reaction product of Example I containing
compounds having the structures:
##STR10##
FIG. 2 is the GLC profile for the reaction product of Example II containing
compounds having the structures:
##STR11##
FIG. 3 is the GLC profile for the reaction product of Example III
containing the compound having the structure:
##STR12##
FIG. 4 is the NMR spectrum for the compound having the structure:
##STR13##
produced according to Example III.
FIG. 5 is the infra-red spectrum for the compound having the structure:
##STR14##
produced according to Example III.
FIG. 6 is the GLC profile for the reaction product produced according to
Example IV, containing compounds having the structures:
##STR15##
FIG. 7 is the NMR spectrum for the reaction product of Example IV,
containing compounds having the structures:
##STR16##
FIG. 8 is the infra-red spectrum for the reaction product of Example IV
containing compounds having the structures:
##STR17##
FIG. 9 is the GLC profile for the reaction product of Example V containing
the compounds having the structures:
##STR18##
FIG. 10 is the NMR spectrum for the compound having the structure:
##STR19##
produced according to Example V.
FIG. 11 is the infra-red spectrum for the compound having the structure:
##STR20##
produced according to Example V.
FIG. 12 is the NMR spectrum for the compound having the structure:
##STR21##
produced according to Example V.
FIG. 13 is the infra-red spectrum for the compound having the structure:
##STR22##
produced according to Example V.
THE INVENTION
It has now been discovered that novel solid and liquid foodstuff, chewing
gum, medicinal product, and flavoring compositions having pear, peach or
apricot flavor with musky aroma characteristics and musky and sweet flavor
characteristics; novel perfume compositions and perfumed articles having
rich, animal musk, sweet, floral and surprisingly intense sandalwood
aromas; as well as novel smoking tobacco compositions and smoking tobacco
flavoring compositions having sweet, floral and musk aromas and tastes on
smoking and prior to smoking in the main stream and in the side stream may
be provided by the novel acetyl hydrindacene derivatives and novel
mixtures of acetyl hydrindacene derivatives and acetyl indane derivatives
and novel acetyl indane derivatives of our invention. The novel acetyl
hydrindacene of our invention has the structure:
##STR23##
The novel acetyl indane compounds of our invention have the structures:
##STR24##
The novel mixtures of our invention contain compounds having the
structures:
##STR25##
In addition to having the abilities to impart (augment or enhance) (in a
novel manner) organoleptic properties to (or in) consumable materials as
set forth supra, the acetyl hydrindacenes, acetyl indanes, mixtures of
acetyl hydrindacenes and mixtures of acetyl hydrindacenes and acetyl
indanes of our invention surprisingly exist in the liquid phase at ambient
temperatures and pressure (e.g., 10.degree. C.-35.degree. C. at one
atmosphere pressure) which physical properties enable them to be used in
flavor and fragrance compositions and perfumed articles in the absence of
any additional liquid carriers or solvents which, in many instances, must
be totally removed from said flavor and fragrance compositions or perfumed
articles prior to entry thereof into the main stream of commerce.
The novel acetyl hydrindacenes, acetyl indanes, and mixtures of actyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes of
our invention are prepared from
5-isopropyl-3,3,8,8-tetramethyl-as-hydrindacene. The
4-isopropyl-3,3,8,8-tetramethyl-as-hydrindacene can be prepared by the
reaction at from about 0.degree. C. up to about 5.degree. C. of isoprene
and cumene in the presence of sulfuric acid to form a mixture of
6-isopropyl-1,1-dimethylindane and the aforementioned
4-isopropyl-3,3,8,8-tetramethyl-as-hydrindacenes (as set forth in reaction
scheme III, infra). Alternatively, cumene, isoprene and
6-isopropyl-1,1-dimethylindane can be reacted in the presence of sulfuric
acid to form 4-isopropyl-3,3,-8,8-tetramethyl-as-hydrindacene along with
recovered cumene and 6-isopropyl-1,1-dimethylindane. In the latter scheme
(scheme IV as set forth infra) the mole ratio of cumene to
6-isopropyl-1,1-dimethylindane may be adjusted such that the net amount of
6-isopropyl-1,1-dimethylindane formed during the reaction is equal to the
amount originally charged into the reaction mass.
Thus, the mole ratio of the 6-isopropyl-1,1-dimethylindane:cumene may be
within the range of from about 2:1 up to about 3:1. The mole ratio of the
sum of cumene and 6-isopropyl-1,1-dimethylindane:isoprene may be within
the range of from about 2:1 up to about 6:1. The sulfuric acid used is
concentrated sulfuric acid and is preferably from about 85 weight percent
aqueous sulfuric acid up to about 95 weight percent aqueous sulfuric acid.
The concentration of concentrated sulfuric acid used in the reaction mass
may vary from about 15% up to about 40% based on the total weight of the
reaction mass, with a concentration of sulfuric acid of about 20% being
preferred.
##STR26##
The desired compound, 4-isopropyl-3,3,8,8-tetramethyl-as-hydrindacene is
then preferably isolated as by fractional distillation.
Specific ranges of conditions for carrying out the reactions to form the
precursor materials of our invention are also specifically set forth in
U.S. Pat. No. 3,347,946 taken together with U.S. Pat. No. 3,078,319.
The resulting 4-isopropyl-3,3,8,8-tetramethyl-as-hydrindacene is then
reacted with acetic anhydride in the presence of an aluminum chloride
catalyst using one of three different addition modes:
1. The hydrindacene is charged to a mixture of aluminum chloride and acetic
anhydride; or
2. The aluminum chloride is charged to a mixture of hydrindacene and acetic
anhydride; or
3. The hydrindacene and acetic anhydride in admixture is added to aluminum
chloride
Notwithstanding the specific addition mode used, the mole ratio of aluminum
chloride to acetic anhydride may vary from about 2:1 up to about 4:1 with
a preferred mole ratio of aluminum chloride:acetic anhydride of 3:1. The
ratio of acetic anhydride:4-isopropyl-1,1,6,6-tetramethyl-as-hydrindacene
may vary from about 0.8 up to 1.2. The solvent used in the reaction system
is a chlorocarbon solvent such as carbon tetrachloride, o-dichlorobenzene,
1,1,2-trichloroethylene or tetrachloroethylene. The reaction temperature
range may vary between about 0.degree. C. and about 20.degree. C.
When using the addition mode wherein the aluminum chloride is added to a
stirred solution of hydrindacene, acetic anhydride and solvent, the
reaction is carried out at about 0.degree. C. yielding an approximately
60:40 mixture of the compounds having the structures:
##STR27##
On the other hand, when a mixture of hydrindacene and acetic anhydride is
added to a stirred slurry of aluminum chloride at a reaction temperature
of about 0.degree. C., a mixture of the four compounds having the
following structures is obtained:
##STR28##
The compounds having the strucures:
##STR29##
are novel compounds.
The acetyl hydrindacenes, acetyl indanes, mixtures of acetyl hydrindacenes
and mixtures of acetyl hydrindacenes and acetyl indanes of our invention
are capable of supplying and/or potentiating certain flavor and aroma
notes usually lacking in many fruit flavors, wine flavors and tobacco
flavors heretofore provided; particularly, peach flavors, apricot flavors
and pear flavors. Furthermore, the acetyl hydrindacenes, acetyl indanes,
mixtures of acetyl hydrindacenes and mixtures of acetyl hydrindacenes and
acetyl indanes of our invention are capable of supplying certain fragrance
notes usually lacking in many perfume materials, for example, musk
fragrances.
When the acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes of
our invention are used as food flavor adjuvants, the nature of the
co-ingredients included with the said acetyl hydrindacenes, acetyl
indanes, mixtures of acetyl hydrindacenes and mixtures of acetyl
hydrindacenes and acetyl indanes in formulating the product composition
will serve to alter the organoleptic characteristics of the ultimate
foodstuff treated therewith.
As used herein in regard to flavors, the terms "alter" and "modify" in
their various forms means "supplying or imparting flavor character or note
to otherwise bland, relatively tasteless substances or augmenting the
existing flavor characteristic where a natural flavor or synthetic flavor
or mixture of natural and synthetic flavors is deficient in some ragard,
or supplementing the existing flavor impression to modify its quality,
character or taste".
As used herein, the term "enhance" is intended to mean the intensification
(without effecting a change in kind of quality of aroma or taste) of one
or more taste and/or aroma nuances present in the organoleptic impression
of a consumable material, e.g., foodstuff, tobacco, chewing gum, medicinal
product, perfume composition or perfumed article.
As used herein, the term "foodstuff" includes both solid and liquid
ingestible materials which usually do, but need not, have nutritional
value. Thus, foodstuffs include soups, convenience foods, beverages, dairy
products, candies, vegetables, cereals, soft drinks, snacks and the like.
As used herein, the term "chewing gum" is intended to mean a composition
which comprises a substantially water-insoluble, chewable plastic gum base
such as chicle, or substitutes therefor, including jelutung, guttakay
rubber and/or certain comestible natural or synthetic resins or waxes.
Incorporated within the gum base, in admixture therewith may be
plasticizers or softening agents, e.g., glycerine; and a flavoring
composition which incorporates acetyl hydrindacenes, acetyl indanes,
mixtures of acetyl hydrindacenes and mixtures of acetyl hydrindacenes and
acetyl indanes of our invention, and, in addition, sweetening agents which
may be sugars, including sucrose or dextrose and/or artificial sweeteners
including dipeptides, cyclamates and saccharin. Other optional ingredients
may also be present.
The term "medicinal product" includes both solids and liquids which are
ingestible, non-toxic materials having medicinal value such as cough
syrups, cough drops, toothpaste, aspirin and chewable medicinal tablets as
further exemplified herein.
Substances suitable for use herein as co-ingredients or flavoring adjuvants
are well known in the art for such use being extensively described in the
relevant literature. Such material is required to be "ingestibly"
acceptable and thus non-toxic or otherwise non-deleterious. Particularly
critical is the additional requirement that such material be
organoleptically compatible with acetyl hydrindacenes, acetyl indanes,
mixtures of acetyl hydrindacenes and mixtures of acetyl hydrindacenes and
acetyl indanes encompassed within the scope of our invention. Also
critical is the additional requirement that such material be nonreactive
(within the range of storage conditions and room temperature use
conditions) with each of acetyl hydrindacenes, acetyl indanes, mixtures of
acetyl hydrindacenes and mixtures of acetyl hydrindacenes and acetyl
indanes.
Accordingly, such materials which may in general be characterized as
flavoring adjuvants or vehicles comprise broadly stabilizers, thickeners,
surface active agents, conditioners, other flavorants and flavor
intensifiers.
Stabilizer compounds include preservatives, e.g., sodium chloride;
antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid, butylated
hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxyanisole),
butylated hydroxy toluene, (2,6-di-tertiary-butyl-4-methyl phenol), propyl
gallate and the like and sequestrants, e.g., citric acid.
Thickener compounds include carriers, binders, protective colloids,
suspending agents, emulsifiers and the like, e.g., agaragar, carrageenan;
cellulose and cellulose derivatives such as carboxymethyl cellulose and
methyl cellulose; natural and synthetic gums such as gum arabic, gum
tragacanth; gelatin, proteinaceous materials; lipids, carbohydrates,
starches, pectins, and emulsifiers, e.g., mono- and diglycerides of fatty
acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose
corn syrup and the like.
Surface active agents include emulsifying agents, e.g., fatty acids such as
capric acid, caprylic acid, palmitic acid, myristic acid and the like,
mono- and diglycerides of fatty acids, lecithin, defoaming and
flavor-dispersing agents such as sorbitan monostearate, potassium
stearate, hydrogenated tallow alcohol and the like.
Conditioners include compounds such as bleaching and maturing agents, e.g.,
benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch
modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite,
propylene oxide, succinic anhydride and the like, buffers and neutralizing
agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate,
citric acid, lactic acid, vinegar and the like; colorants, e.g., carminic
acid, cochineal, turmeric and curcuma and the like; firming agents such as
aluminum sodium sulfate, calcium chloride and calcium gluconate;
texturizers, anti-caking agents, e.g., aluminum calcium sulfate and
tribasic calcium phosphate; enzymes, yeast foods, e.g., calcium lactate
and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric
phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc
sources such as zinc chloride, zinc sulfate and the like.
Other flavorants and flavor intensifiers include organic acids, e.g.,
acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,
caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric
acid, alpha-methyl-butyric acid, propionic acid, valeric acid,
2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones and
aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methyl
carbinol, acrolein, n-butanal, crotonal, diacetyl, beta,
beta-dimethylacrolein, n-hexanal, 2-hexenel, cis-3-hexenal, 2-heptanal,
4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,
methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols such as
1-butanal, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol,
geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol,
3-methyl-3-buten-1-ol, 1-penten-2-ol, 1-penten-3-ol,
p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,
phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate; esters, such as
butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl
butyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethyl formate,
ethyl isobutyrate, ethyl isovalerate, ethyl alpha-methylbutyrate, ethyl
propionate, ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate,
2-hexenyl butyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate,
methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate,
alpha-methylbutyrate, propyl acetate, amyl acetate, amyl butyrate, benzyl
salicylate, dimethyl anthranilate, ethyl methylphenylglycidate, ethyl
succinate, isobutyl cinnamate and terpenyl acetate; lactones, such as
delta-decalactone, delta-undecalactone and delta-nonyl-lactone and
gamma-undecalactone, gamma-dodecalatone and gamma nonyl-lactone as well as
"peach" lactone; essential oils, such as jasmine absolute, rose absolute,
orris absolute, lemon essential oil, Bulgarian rose, yara yara, natural
raspberry oil and vanilla; lactones; sulfides, e.g., methyl sulfide and
other materials such as maltol, acetoin and acetals (e.g.,
1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane).
The specific flavoring adjuvant selected for use may be either solid or
liquid depending upon the desired physical form of the ultimate product,
i.e., foodstuff, whether simulated or natural, and should, in any event,
be capable of providing an environment in which the acetyl hydrindacenes,
acetyl indanes, mixtures of acetyl hydrindacenes and mixtures of acetyl
hydrindacenes and acetyl indanes can be dispersed or admixed to provide a
homogeneous medium. In addition, selection of one or more flavoring
adjuvants, as well as the quantities thereof will depend upon the precise
organoleptic character desired in the finished product. Thus, in the case
of flavoring compositions, ingredient selection will vary in accordance
with the foodstuff to which the flavor and aroma are to be imparted. In
contradistinction, in the preparation of solid products, e.g., simulated
foodstuffs, ingredients capable of providing normally solid compositions
should be selected such as various cellulose derivatives.
As will be appreciated by those skilled in the art, the amount of acetyl
hydrindacenes, acetyl indanes, mixtures of acetyl hydrindacenes and
mixtures of acetyl hydrindacenes and acetyl indanes employed in a
particular instance can vary over a relatively wide range whereby to its
desired organoleptic effects having reference to the nature of the product
are achieved. Thus, correspondingly, greater amounts would be necessary in
those instances wherein the ultimate food composition to be flavored is
relatively bland to the taste, whereas relatively minor quantities may
suffice for purposes of enhancing the composition merely deficient in
natural flavor or aroma. The primary requirement is that the amount
selected to be effective, i.e., sufficient to alter, modify or enhance the
organoleptic characteristics of the parent composition, whether foodstuff
per se or flavoring composition.
The use of insufficient quantities of acetyl hydrindacenes, acetyl indanes,
mixtures of acetyl hydrindacenes and mixtures of acetyl hydrindacenes and
acetyl indanes will, of course, substantially vitiate any possibility of
obtaining the desired results while excess quantities prove needlessly
costly and in extreme cases, may disrupt the flavor-aroma balance, thus
proving self-defeating. Accordingly, the terminology "effective amount"
and "sufficient amount" is to be accorded a significance in the context of
the present invention consistent with the obtention of desired flavoring
effects.
Thus, and with respect to ultimate food compositions, it is found that
quantities of acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes
ranging from a small but effective amount, e.g., 0.001 parts per million
up to about 50 parts per million by weight based on total composition are
suitable. Concentrations in excess of the maximum quantity stated are not
normally recommended, since they fail to prove commensurate enhancement of
organoleptic properties. In those instances, wherein the acetyl
hydrindacenes, acetyl indanes, mixtures of acetyl hydrindacenes and
mixtures of acetyl hydrindacenes and acetyl indanes is added to the
foodstuff as an integral component of a flavoring composition, it is, of
course, essential that the total quantity of flavoring composition
employed be sufficient to yield an effective concentration (of acetyl
hydrindacenes, acetyl indanes, mixtures of acetyl hydrindacenes and
mixtures of acetyl hydrindacenes and acetyl indanes) in the foodstuff
product.
Food flavoring compositions prepared in accordance with the present
invention preferably contain the acetyl hydrindacenes, acetyl indanes,
mixtures of acetyl hydrindacenes and mixtures of acetyl hydrindacenes and
acetyl indanes in concentrations ranging from about 0.1% up to about 15%
by weight based on the total weight of the said flavoring composition.
The composition described herein can be prepared according to conventional
techniques well known as typified by cake batters and fruit drinks and can
be formulated by merely admixing the involved ingredients within the
proportions stated in a suitable blender to obtain the desired
consistency, homogeneity of dispersion, etc. Alternatively, flavoring
compositions in the form of particulate solids can be conveniently
prepared by mixing the acetyl hydrindacenes, acetyl indanes, mixtures of
acetyl hydrindacenes and mixtures of acetyl hydrindacenes and acetyl
indanes with, for example, gum arabic, gum tragacanth, carrageenan and the
like, and thereafter spray-drying the resultant mixture whereby to obtain
the particular solid product. Pre-prepared flavor mixes in powder form,
e.g., a fruit-flavored powder mix are obtained by mixing the dried solid
components, e.g., starch, sugar and the like and acetyl hydrindacenes,
acetyl indanes, mixtures of acetyl hydrindacenes and mixtures of acetyl
hydrindacenes and acetyl indanes in a dry blender until the requisite
degree of uniformity is achieved.
It is presently preferred to combine with acetyl hydrindacenes, acetyl
indanes, mixtures of acetyl hydrindacenes and mixtures of acetyl
hydrindacenes and acetyl indanes, the following adjuvants:
p-Hydroxybenzyl acetone;
Geraniol;
Acetaldehyde;
Maltol;
Ethyl methyl phenyl glycidate;
Benzyl acetate;
Dimethyl sulfide;
Vanillin;
Methyl cinnamate;
Ethyl pelargonate;
Methyl anthranilate;
Isoamyl acetate;
Isobutyl acetate;
Alpha ionone;
Ethyl butyrate;
Acetic acid;
Gamma-undecalactone;
Gamma-nonalactone
Gamma decalactone;
Delta undecalactone;
Delta dodecalactone;
Delta nonyl lactone;
"Peach" lactone;
Naphthyl ethyl ether;
Diacetyl;
Ethyl acetate;
Anethole;
Isoamyl butyrate;
Cis-3-hexenol-1;
2-Methyl-2-pentenoic acid;
Elemecine (4-allyl-1,2,6-trimethoxy benzene);
Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene); and
2-(4-hydroxy-4-methylpentyl) norbornadiene prepared according to U.S. Pat.
No. 3,886,289 issued May 27, 1975
An additional aspect of our invention provides an organoleptically improved
smoking tobacco product and additives therefor, as well as methods of
making the same which overcome specific problems herefofore encountered in
which specific desired woody flavor characteristics of natural tobacco are
created or enhanced and may be readily controlled and maintained at the
desired uniform level regardless of variations in the tobacco components
of the blend.
The invention further provides improved tobacco additives and methods
whereby various desirable sweet, floral and musk notes may be imparted to
smoking tobacco products and may be readily varied and controlled to
produce the desired uniform flavoring characteristics.
In carrying out this aspect of our invention, we add to smoking tobacco
materials or a suitable substitute therefor (e.g., dried lettuce leaves)
an aroma and flavor additive containing as an active ingredient acetyl
hydrindacenes, acetyl indanes, mixtures of acetyl hydrindacenes and
mixtures of acetyl hydrindacenes and acetyl indanes.
In addition to the acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes of
our invention, other flavoring and aroma additives may be added to the
smoking tobacco material or substitute therefor either separately or in
mixture with the acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes as
follows:
I. Synthetic Materials
Beta-ethyl-cinnamaldehyde;
Eugenol;
Dipentene;
Damascenone;
Maltol;
Ethyl maltol;
Delta undecalactone;
Delta decalactone;
Benzaldehyde;
Amyl acetate;
Ethyl butyrate;
Ethyl valerate;
Ethyl acetate;
2-Hexenol-1,2-methyl-5-isopropyl-1,3-nonadiene-8-one;
2,6-Dimethyl-2,6-undecadiene-10-one;
2-Methyl-5-isopropyl acetophenone;
2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;
Dodecahydro-3a-6,6,9a-tetramethyl naphtho(2,1-b)-furan;
4-Hydroxy hexanoic acid, gamma lactone;
Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No. 3,589,372
issued on June 29, 1971.
II. Natural Oils
Celery seed oil;
Coffee extract;
Bergamot Oil;
Cocoa extract;
Nutmeg oil;
Origanum oil
An aroma and flavoring concentrate containing acetyl hydrindacenes, acetyl
indanes, mixtures of acetyl hydrindacenes and mixtures of acetyl
hydrindacenes and acetyl indanes and, if desired, one or more of the above
indicated additional flavoring additives may be added to the smoking
tobacco material, to the filter or to the leaf or paper wrapper. The
smoking tobacco material may be shredded, cured, cased and blended tobacco
material or reconstituted tobacco material or tobacco substitutes (e.g.,
lettuce leaves) or mixtures thereof. The proportions of flavoring
additives may be varied in accordance with taste but insofar as
enhancement or the imparting of natural and/or sweet notes, we have found
that satisfactory results are obtained if the proportion by weight of the
sum total of acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes to
smoking tobacco material is between 125 ppm and 1,500 ppm (0.0125%-0.15%)
of the active ingredients to the smoking tobacco material. We have further
found that satisfactory results are obtained of the proportion by weight
of the sum total of acetyl hydrindacenes, acetyl indanes, mixtures of
acetyl hydrindacenes and mixtures of acetyl hydrindacenes and acetyl
indanes used to flavoring material is between 1,000 and 10,000 ppm
(0.01%-1.5%).
Any convenient method for incorporating the acetyl hydrindacenes, acetyl
indanes, mixtures of acetyl hydrindacenes and mixtures of acetyl
hydrindacenes and acetyl indanes in the tobacco product may be employed.
Thus, the acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes
taken alone or along with other flavoring additives may be dissolved in a
suitable solvent such as ethanol, pentane, diethyl ether and/or other
volatile organic solvents and the resulting solution may either be spread
on the cured, cased and blended tobacco material or the tobacco material
may be dipped into such solution. Under certain circumstances, a solution
of acetyl hydrindacenes, acetyl indanes, mixtures of acetyl hydrindacenes,
and mixtures of acetyl hydrindacenes and acetyl indanes taken alone or
taken further together with other flavoring additives as set forth above
may be applied by means of a suitable applicator such as a brush or roller
on the paper or leaf wrapper for the smoking product, or it may be applied
to the filter by either spraying or dipping or coating.
Furthermore, it will be apparent that only a portion of the tobacco or
substitute therefor need be treated and the thus treated tobacco may be
blended with other tobaccos before the ultimate tobacco product is formed.
In such cases, the tobacco treated may have the acetyl hydrindacenes,
acetyl indanes, mixtures of acetyl hydrindacenes and mixtures of acetyl
hydrindacenes and acetyl indanes in excess of the amounts or
concentrations above indicated so that when blended with other tobaccos,
the final product will have the percentage within the indicated range.
In accordance with one specific example of our invention, an aged, cured
and shredded domestic burley tobacco is spread with a 10% ethyl alcohol
solution of 6:4 mixture of compounds having the structures:
##STR30##
in an amount to provide a tobacco composition containing 400 ppm by weight
of acetyl hydrindacene mixture on a dry basis. Thereafter, the alcohol is
removed by evaporation and the tobacco is manufactured into cigarettes by
the usual techniques. The cigarette when treated as indicated has a
desired and pleasing aroma which is detectable in the main and side
streams when the cigarette is smoked. This aroma is described as being
sweeter, more aromatic, more tobacco-like and having excellent sweet,
floral and musk-like notes.
While our invention is particularly useful in the manufacture of smoking
tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other
tobacco products formed from sheeted tobacco dust or fines may also be
used. Likewise, the acetyl hydrindacenes, acetyl indanes, mixtures of
acetyl hydrindacenes and mixtures of acetyl hydrindacenes and acetyl
indanes of our invention can be incorporated with materials such as filter
tip materials, seam paste, packaging materials, and the like which are
used along with tobacco to form a product adapted for smoking.
Furthermore, the acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes can
be added to certain tobacco substitutes of natural or synthetic origin
(e.g., dried lettuce leaves) and, accordingly, by the term "tobacco" as
used throughout this specification is meant any composition intended for
human consumption by smoking or otherwise, whether composed of tobacco
plant parts or substitute materials or both.
The acetyl hydrindacenes, acetyl indanes, mixtures of acetyl hydrindacenes
and mixtures of acetyl hydrindacenes and acetyl indanes and one or more
auxiliary perfume ingredients, including, for example, alcohols,
aldehydes, nitriles, esters, cyclic esters, 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 perfume compositions, the individual components which contribute 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 acetyl hydrindacenes, acetyl indanes, mixtures of
acetyl hydrindacenes and mixtures of acetyl hydrindacenes and acetyl
indanes can be used to alter the aroma characteristics of a perfume
composition, for example, by utilizing or moderating the olfactory
reaction contributed by another ingredient in the composition.
The amount of acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes 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 acetyl hydrindacenes, acetyl indanes,
mixtures of acetyl hydrindacenes and mixtures of acetyl hydrindacenes and
acetyl indanes and even less (e.g., 0.005% can be used to impart a rich,
animal-musk, sweet, sandalwood-like and floral notes to soaps, cosmetics
or 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 acetyl hydrindacenes, acetyl indanes, mixtures of acetyl hydrindacenes
and mixtures of acetyl hydrindacenes and acetyl indanes are useful, taken
alone or in perfume compositions as olfactory components in detergents,
soaps, fabric softener compositions, fabric softener compositions for use
in clothes dryers, 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 and sun screens; powders, such as talcs, dusting powders, face
powders and the like. When used as an olfactory component as little as 1%
of the acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes of
our invention will suffice to impart an intense musk fragrance with
sandalwood and floral notes to musk oil formulations. Generally, no more
than 3% of the acetyl hydrindacenes, acetyl indanes, mixtures of acetyl
hydrindacenes and mixtures of acetyl hydrindacenes and acetyl indanes
based on the ultimate end product is required in the perfume composition.
In addition, the perfume composition or fragrance composition of our
invention can contain a vehicle or carrier for the acetyl hydrindacenes,
acetyl indanes, mixtures of acetyl hydrindacenes and mixtures of acetyl
hydrindacenes and acetyl indanes. The vehicle can be a liquid such as an
alcohol, a non-toxic alcohol, a non-toxic glycol, or the like. The carrier
can also be an absorbent solid, such as a gum (e.g., gum arabic) or
components for encapsulating the composition (such as gelatin).
It will thus be apparent that the acetyl hydrindacenes, acetyl indanes,
mixtures of acetyl hydrindacenes and mixtures of acetyl hydrindacenes and
acetyl indanes of our invention can be utilized to alter the sensory
properties, particularly organoleptic properties, such as flavor and/or
fragrance of a wide variety of consumable materials.
The following examples are illustrative and the invention is to be
considered 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 1,1-DIMETHYL-6-ISOPROPYLINDANE AND
4-ISOPROPYL-1,1,6,6-TETRAMETHYL-AS-HYDRINDACENE
Reaction
##STR31##
A solution of 510 grams of isoprene and 690 grams of cumene is added over a
three-hour period to a well stirred mixture of 2910 grams of cumene and
903 grams of 90% sulfuric acid at 0.degree.-5.degree. C. The reaction mass
is stirred for an additional 15 minutes and then stirring is stopped and
the mixture is allowed to separate into two layers. The bottom layer is
discarded. The top (organic) layer is washed with 600 ml of water,
followed by washing with 2 liters of 5% sodium carbonate solution.
Distillation through a 1.5".times.12" Goodloe packed column affords 2825
grams of cumene (b.p. 73.degree. C., 50 mm Hg), 696 grams of
1,1-dimethyl-6-isopropylbenzene (b.p. 111.degree. C., 11 mm Hg.) and 161
grams of 4-isopropyl-1,1,6,6-tetramethyl-as-hydrindacene (b.p.
134.degree.-142.degree. C., 3 mm Hg.).
The GLC of the reaction mass is shown in FIG. 1 (220.degree. C. isothermal,
10% SE-30).
EXAMPLE II
PREPARATION OF 1,1-DIMETHYL-6-ISOPROPYLINDANE AND
4-ISOPROPYL-1,1,6,6-TETRAMETHYL-AS-HYDRINDACENE
Reaction
##STR32##
A solution of 158 grams of isoprene, 93 grams of cumene and 438 grams of
1,1-dimethyl-6-isopropylindane is added over a three-hour period to a
well-stirred mixture containing 390 grams of 90% sulfuric acid, 187 grams
of cumene and 878 grams of 1,1-dimethyl-6-isopropylbenzene at
0.degree.-5.degree. C. The reaction mass is stirred for an additional 15
minutes and then stirring is stopped and the mixture is allowed to
separate into two layers. The bottom layer is discarded. The top (organic)
layer is washed with 600 ml of water followed by washing with 2 liters of
5% sodium carbonate solution.
Distillation through a 1.5".times.12" Goodloe packed column affords 199
grams of cumene, 1237 grams of 1,1-dimethyl-6-isopropylindane and 209
grams of 1,1,6,6-tetramethyl-as-hydrindacene.
The GLC of the reaction mass is shown in FIG. 2.
EXAMPLE III
PREPARATION OF 4-ACETYL-3,3,8,8-TETRAMETHYL-AS-HYDRINDACENE
Reaction
##STR33##
A solution of a mixture of 10 grams of
4-isopropyl-1,1,6,6-tetramethyl-as-hydrindacene and 8 grams of acetic
anhydride in 20 ml of 1,1,1-trichloroethylene is added to a stirred slurry
of of 18 grams of aluminum chloride in 25 ml of trichloroethylene at
20.degree. C. over a ten minute period. The resulting mass is stirred for
an additional ten minutes and then poured into 200 ml of ice water. The
organic layer is washed and distilled to afford 8.2 grams of
4-acetyl-3,3,8,8-tetramethyl-as-hydrindacene.
The GLC trace in FIG. 3 shows the crude reaction mass (220.degree. C.
isothermal, 10% SE-30).
The NMR spectrum is shown in FIG. 4.
The IR spectrum is shown in FIG. 5.
EXAMPLE IV
PREPARATION OF A MIXTURE OF 4-ACETYL-1,1,6,6-TETRAMETHYL-AS-HYDRINDACENE
AND 4-ACETYL-3,3,8,8-TETRAMETHYL-AS-HYDRINDACENE
Reaction
##STR34##
480 grams of aluminum chloride is added portionwise at 0.degree. C. to a
stirred solution of 256 grams of
4-isopropyl-1,1,6,6-tetramethyl-as-hydrindacene, 120 grams of acetic
anhydride and 650 grams of trichloroethylene over a two-hour period. The
reaction mass is stirred for an additional 15 minutes and quenched into 2
liters of ice water. The organic layer is washed twice, neutralizing with
5% sodium carbonate. Distillation through a short column afforded 199
grams of a mixture of 4-acetyl-1,1,6,6l -tetramethyl-as-hydrindacene and
4-acetyl-3,3,8,8-tetramethyl-as-hydrindacene. The mixture is further
purified using steam vacuum fractional distillation to afford a mobile
liquid (b.p. 156.degree. C., 3.0 mm Hg.).
The GLC spectrum of the crude reaction mass is shown in FIG. 6.
The NMR spectrum of the product is shown in FIG. 7.
The IR spectrum of the product is shown in FIG. 8.
EXAMPLE V
PREPARATION OF A MIXTURE OF 4-ACETYL-1,1,6,6-TETRAMETHYL-AS-HYDRINDACENE;
4-ACETYL-3,3,8,8-TETRAMETHYL-AS-HYDRINDACENE;
5-ACETYL-6-(3-METHYLBUTYL)-3,3-DIMETHYLINDANE; AND
5-ACETYL-7-(3-METHYLBUTYL)-1,1-DIMETHYLINDANE
Reaction
##STR35##
A solution of 168 grams of acetic anhydride, 384 grams of
4-acetyl-1,1,6,6-tetramethyl-as-hydrindacene and 700 grams of
trichloroethylene is added at 0.degree. C. to a stirred slurry of 661
grams of aluminum chloride in 700 grams of trichloroethylene over a
two-hour period. After the addition, t | | |
