U.S. patent number 3,890,981 [Application Number 05/503,110] was granted by the patent office on 1975-06-24 for novel process for altering the organoleptic properties of tobacco using one or more alpha-pyrones and process.
This patent grant is currently assigned to International Flavors & Fragrances Inc.. Invention is credited to Alan Owen Pittet, Alton Dewitt Quinn, Joaquin Francisco Vinals.
United States Patent |
3,890,981 |
Vinals , et al. |
* June 24, 1975 |
Novel process for altering the organoleptic properties of tobacco
using one or more alpha-pyrones and process
Abstract
Described is a process comprising adding to tobacco an amount
sufficient to alter the flavor or aroma of the tobacco, one or more
alpha-pyrone compounds having the generic structure: ##SPC1##
Wherein R.sub.1 is methyl or hydrogen, and R.sub.2 is C.sub.3
-C.sub.5 alkyl; processes for producing such tobacco products; and
flavor formulations for use in conjunction with tobacco products
containing one or more of such alpha-pyrones.
Inventors: |
Vinals; Joaquin Francisco (Red
Bank, NJ), Quinn; Alton Dewitt (Abrahamsville, PA),
Pittet; Alan Owen (Atlantic Highlands, NJ) |
Assignee: |
International Flavors &
Fragrances Inc. (New York, NY)
|
[*] Notice: |
The portion of the term of this patent
subsequent to January 21, 1992 has been disclaimed. |
Family
ID: |
27043571 |
Appl.
No.: |
05/503,110 |
Filed: |
September 4, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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471785 |
May 20, 1974 |
3861403 |
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Current U.S.
Class: |
131/277 |
Current CPC
Class: |
A24B
15/403 (20130101) |
Current International
Class: |
A24B
15/00 (20060101); A24B 15/40 (20060101); A24b
015/04 () |
Field of
Search: |
;131/2,15,17,9,140-144 |
References Cited
[Referenced By]
U.S. Patent Documents
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3380457 |
April 1968 |
Schumacher et al. |
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Foreign Patent Documents
Primary Examiner: Rein; Melvin D.
Attorney, Agent or Firm: Liberman, Esq.; Arthur L. Haidt,
Esq.; Harold
Parent Case Text
This application is a division of applicants' copending Patent
Application Ser. No. 471,785 filed on May 20, 1974, now U.S. Pat.
No. 3,861,403.
Claims
What is claimed is:
1. A process for altering the organoleptic properties of tobacco
comprising the step of adding to tobacco a tobacco flavoring
composition comprising one or more 6-alkyl-alpha-pyrone compounds
having the structure: ##SPC5##
wherein R.sub.1 is selected from the group consisting of methyl and
hydrogen, and R.sub.2 is C.sub.3 --C.sub.5 alkyl and at least one
tobacco flavoring additive selected from the group consisting
of:
Esters;
Aldehydes;
Ketones;
Acetals;
Natural Oils and Extracts;
Lactones,
Ethers;
Pyrazines; and
Pyrroles
2. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is
6-n-propyl-alpha-pyrone.
3. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is
6-n-butyl-alpha-pyrone.
4. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is
6-n-pentyl-alpha-pyrone.
5. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is
4-methyl-6-isopropyl-alpha-pyrone.
6. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is
4-methyl-6-n-pentyl-alpha-pyrone.
Description
BACKGROUND OF THE INVENTION
This invention relates to novel tobacco products, novel tobacco
flavoring compositions, and processes for producing same, and has
for an object the provision of a composition and process for
improving the flavor and aroma of tobacco and tobacco smoke.
It is well known in the tobacco art that the flavor and aroma of
the tobacco product and the smoke from the tobacco are very
important considerations insofar as the ultimate consumer is
concerned. Considerable efforts have been and are being exerted by
the manufacturers of tobacco products to provide a product that
will be acceptable to the consumer, particularly as regards flavor
and aroma characteristics. It has been the common practice in the
tobacco industry to prepare blends of domestic and oriental
tobaccos in order to provide smoking tobacco which has a pleasing
flavor and aroma before and during smoking. However, such a
procedure is costly and may at times become prohibitive in the
event that certain types of tobacco may be in short supply.
Accordingly, there has been considerable work relating to
substances which can be used to impart flavors to various tobacco
blends. These substances are used to supplementnatural materials
some of which, as stated above, may be in short supply, and to
provide more uniform properties to the finished product.
Sweet, aromatic, warm, spicy, maple-like, fruity, coumarin-like,
vanillin-like, lactone, lovage-like, celery-like and nut-like notes
are paticularly desirable for many uses concerning the flavoring of
tobacco products; both prior to and on smoking.
Schumacher et al., U.S. Pat. No. 3,380,457 issued on Apr. 30, 1958
described an improved tobacco product containing a lactone compound
having the generic structure: ##SPC2##
Wherein one or more of R.sub.1, R.sub.2 and R.sub.3 are hydrogen or
alkyl and wherein the dashed line represents a single bond or a
double bond. Schumacher et al. states that an aroma and flavor
which is reminiscent of coconut may be imparted by the use of
3-isopropyl-delta-valerolactone as a tobacco additive; or by the
use of 5-hydroxy-3-isopropyl-2-pentenoic acid delta lactone, as a
tobacco additive; or a spicy note may be imparted by the use of
5-hydroxy-2-isopropylhexanoic acid delta lactone, as a tobacco
additive; or a spicy apple not may be imparted by the use of
beta-methyl-delta valerolactone as a tobacco additive.
Various alpha pyrones have been described as being useful in
altering the organoleptic characteristics of flavors for foodstuffs
as well as fragrances for use in conjunction with perfumed
articles.
Arctander, Perfume and Flavor Chemicals (Aroma Chemicals) 1969
contains the following teachings:
i. At No. 1347, the flavor and perfume use of 5-ethyl-alpha
pyrone;
ii. At No. 2230, the flavor and perfume use of 5-methyl-alpha
pyrone;
iii. At No. 2781, the perfume use of alpha pyrone.
Taylor et al. British Pat. No. 748,645 discloses at page 7, lines
105 and 106 the use in butter flavors of the lactones of
unsaturated delta hydroxy acids. Sevenants, J.Food Sci., 1971, 36
(3), 536 discloses the occurence of 6-pentyl-alpha-pyrone in peach
aroma. Nobuhara, Agr.Biol.Chem. 1969, 33, No. 9, 1264-9 (Title:
"Synthesis of Unsaturated Lactones/III: Flavorous Nature of Soome
delta-Lactones having the Double Bond at Various Sites") indicates
the waxey, butter-cake flavor of 6-pentyl-alpha-pyrone at page
1267, col. 1. In addition, the flavor attributes of alpha-pyrones,
in general, are discussed by Nobuhara.
Methods for the preparation of the alpha-pyrones found to be useful
in our invention are disclosed as follows:
i. Lohaus et al., Chemische Berichte, 100, 658 (1967);
ii. Wiley et al., J.Org.Chem., 22. 1257-9, (1957);
iii. Belgian Pat. No. 643,891, Aug. 17, 1964;
iv. Nobuhara, Agr.Biol.Chem. 1969, 33(9), 1264-9;
v. Pettit et al., J. Org.Chem., 1970, 35(5), 1398-1404;
vi. Lamberti et al., Recueil, 86 (1967) 504-510:
The 6-alkyl-alpha-pyrones of our invention, which are unsubstituted
at the "4"position of the pyrone ring may also be prepared
according to the process of copending U.S. Application for Letters
Patent No. 471,756 filed on May 20, 1974 the reactions of which are
as follows: ##SPC3##
wherein R is alkyl.
THE INVENTION
It has now been discovered that tobacco flavoring compositions and
tobacco products having sweet, aromatic, warm, spicy, maple-like,
fruity, coumarin-like, vanillin-like, lactonic, lovage-like,
celery-like and/or nut-like flavors and aromas prior to and on
smoking may be provided by adding to tobacco flavors and/or to
tobaccos themselves one or more alpha pyrones having the generic
structure: ##SPC4##
wherein R.sub.1 is hydrogen or methyl and R.sub.2 is C.sub.3
-C.sub.5 alkyl.
Thus, the groups exemplified by R.sub.2 are as follows:
n-propyl
i-propyl
n-butyl
i-butyl
t-butyl
1-pentyl
2-pentyl
1-(2-methylbutyl)
2-(2-methylbutyl)
3-(2-methylbutyl)
1-(2,2-dimethylpropyl)
Specific examples of the compounds contemplated within the scope of
our invention, and their tobacco flavor properties prior to and on
smoking are as follows:
Organoleptic Properties Organoleptic Prior to Properties Compound
Smoking On Smoking ______________________________________
6-n-propyl- Creamy, sweet, Sweet, aromatic alpha-pyrone coumarin,
herbal lactone, coumarin, note vanillin taste and aroma 6-n-butyl-
Sweet, slightly Sweet, aromatic, alpha-pyrone coumarin, and
coconut, coumarin- floral aroma vanillin, and lactone aroma and
taste 6-i-butyl- Sweet and Sweet, aromatic, alpha-pyrone
coconut-like and creamy-van- illin-like taste and aroma 6-n-pentyl-
Green, floral Fruity, coumarin- alpha-pyrone- and coconut- like
taste and like aroma aroma 4-methyl-6-i- Sweet, rum-like Sweet,
aromatic, propyl-alpha- lovage, tagette warm spicy and pyrone with
tonka under- lovage-like taste tone and aroma 4-methyl-6-n- Sweet,
coumarin- Spicy, celery-like, butyl-alpha- like, foenugreek fatty,
creamy, pyrone like, celery- cereal and nut-like like aroma taste
and aroma 4-methyl-6-i- Sweet, fruity, Sweet, aromatic,
butyl-alpha- jasmine-like, warm, spicy, pryone appley aroma
somewhat maple- like aroma and taste 4-methyl-6-n- Long lasting
Maple, creamy, pentyl-alpha- celery, lovage, vanilla taste pyrone
tagette aroma and aroma ______________________________________
It has been found that the tobacco additives of our invention when
incorporated into tobacco products impart a flavor and aroma both
before and during smoking which many smokers consider to be
desirable in smoking products. However, it is pointed out that the
methods for defining or characterizing the quality of a flavor or
aroma in the tobacco art are almost purely subjective and different
smokers may define the same flavor quite differently. Also, as
indicated in the above table, the compounds included within the
broad scope of this invention may impart different flavors or
aromas depending upon the alkyl substituents therein. Thus, the
compounds comprehended by this invention, by subjective tests,
impart characteristic flavors which are desirable in tobacco
products and the smoke therefrom even though the exact character
thereof cannot be described on the basis of known standards.
In accordance with this invention, one or more of the alpha-pyrones
of our invention, or mixtures thereof, is added to tobacco or
applied to a smoking article or its component parts in amounts of
about 100-5000 parts per million (ppm) based on dry weight of the
tobacco product. Preferably, the amount of additive is between
about 200 and 500 ppm by weight in order to provide a tobacco
product having a desired flavor and aroma. However, the amount used
will depend upon the amound of flavor and aroma desired and the
particular compound or mixture thereof that is used. The additive
may be incorporated at any step in the treatment of the tobacco but
is preferably added after aging, curing and shredding and before
the tobacco is formed into cigarettes. Likewise, it will be
apparent that only a portion of the tobacco need be treated and the
thus treated tobacco may be blended with other tobaccos before the
cigarettes or other smoking articles are formed. In such case the
tobacco treated may have the additive in excess of the amounts
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 embodiment of this invention, an
aged, flue-cured and shredded tobacco is sprayed with a 1% ethyl
alcohol solution of 6-n-pentyl-alpha-pyrone in an amount to provide
a tobacco containing 200 ppm. by weight of the additive on a dry
basis. Thereafter, the alcohol is removed by evaporation and the
tobacco is manufactured into cigarettes by the usual techniques. It
has been found that the cigarette when prepared as indicated has a
desired and pleasing flavor, an aroma which to some people is
described as "fruity-coumarine-like" and is detectable and pleasing
in the main and side smoke streams when the cigarette is
smoked.
The additives falling within the scope of this invention may be
applied to the tobacco by spraying, dipping or otherwise, utilizing
suitable suspensions or solutions of the additive. Thus water or
volatile organic solvents, such as alcohol, ether, acetone,
volatile hydrocarbons and the like, may be used as the carrying
medium for the additive while it is being applied to the tobacco.
Also, other flavor-and aroma-producing additives, such as:
a. Esters, for example:
Ethyl butyrate; Ethyl acetate; Ethyl valerate; Amyl acetate; Phenyl
ethyl isovalerate; and Methyl heptynyl carbonate
b. Aldehydes, for example:
3-phenyl-2-pentenal; 3-phenyl-3-pentenal; phenyl acetaldehyde;
Cinnamaldehyde; and Beta-ethyl-cinnamaldehyde
c. Ketones, for example:
Benzylidene acetone; Acetophenone; Maltol; and Ethyl maltol
d. Acetals, for example:
3-phenyl-4-pentenal dimethyl acetal; and 3-phenyl-4-pentenal
diethyl acetal (described in copending application for U.S. Letters
Patent No. 276,922 filed on Aug. 1, 1972)
e. Natural oils and extracts, for example:
Vanilla; Coffee extract; Origanum Oil; Cocoa Extract; Oil of
Cloves; Nutmeg Oil; Celery seed oil; Bergamot oil; and Ylang-ylang
oil
f. Lactones, for example:
Delta-decalactone; Delta-undecalactone; Delta-dodecalactone;
Gamma-undecalactone; and Coumarin
g. Ethers, for example:
Dibenzyl ether; Vanillin; and Eugenol
h. Pyrazines, for example:
2-Acetyl pyrazine; 2-Acetyl-6-methyl pyrazine; 2Ethyl pyrazine;
2,3-Dimethyl pyrazine; 2,5-Dimethyl pyrazine; and 2Ethyl-5-methyl
pyrazine
i. Pyrroles, for example:
N-cyclopropyl pyrrole; and N-cyclooctyl pyrrole
as well as those additives disclosed in U.S. Pat. Nos. 2,766,145,
2,905,575, 2,905,576, 2,978,365, 3,041,211, 2,766,149, 2,766,150,
3,589,372, 3,288,146, 3,402,051 and 3,380,457 as well as Australian
Pat. Nos. 444,545, 444,507 and 444,389 may be incorporated into the
tobacco with the additives of this invention.
While this invention is principally useful in the manufacture of
cigarette tobacco, it is also suitable for use in connection with
the manufacture of pipe tobacco, cigars or other tobacco products.
Furthermore, the compounds may be added to certain tobacco
substitutes of natural or synthetic origin.
Also, the invention has been particularly described with reference
to the addition of the compounds directly to tobacco. However, it
will be apparent that the compound may be applied to the paper of
the cigarette or to the wrapper of a cigar. Also, it may be
incorporated into the filter tip, the packaging material on the
seam paste employed for gluing the cigarette paper. Thus, a tobacco
product is provided which includes the specified additives and
tobacco although in every instance the compound need not be admixed
with the tobacco as above specifically described.
The following examples are given to illustrate the embodiments of
the invention as it is presently preferred to practice it. It will
be understood that these examples are illustrative and the
invention is not to be considered as restricted thereto except as
indicated in the appended claims.
EXAMPLE I
TOBACCO USE OF 6-ALKYL-ALPHA-PYRONE
The following tobacco flavor formulation A is prepared:
Ingredients Parts ______________________________________ Ethyl
Butyrate 0.05 Ethyl Valerate 0.5 Maltol 2.00 Cocoa Extract 26.00
Coffee Extract 10.00 Ethanol (95% aqueous) 20.00 Water 41.90
______________________________________
A tobacco formulation B is prepared as follows:
Ingredients Parts ______________________________________ Bright
Tobacco 40.1 Burley Tobacco 24.9 Maryland Tobacco 1.1 Turkish
Tobacco 11.6 Stem (Flue-cured) Tobacco 14.2 Glycerine 2.8 Water 5.3
______________________________________
The flavor formulation A is added to a portion of the smoking
tobacco formulation B at the rate of 0.1% by weight of the tobacco.
The flavored and non-flavored tobacco formulations are then
formulated into cigarettes by the usual manufacturing
procedures:
i. At the rate of 200 ppm to one-seventh of the cigarettes in each
group is added 4-methyl-6-n-pentyl-alpha-pyrone. The use of the
4-methyl-6-n-pentyl-alpha-pyrone in the cigarettes causes the
cigarettes prior to smoking to have a celery, lovage, tagette
aroma. In smoke flavor, these notes are not found, however, on
smoking the cigarettes containing the
4-methyl-6-n-petnyl-alpha-pyrone are found to be more richer,
sweeter and spicier and to have maple, creamy and vanilla notes
whether or not the other flavor ingredients of formulation A are
present.
ii. At the rate of 200 ppm to one-seventh of the cigarettes in each
group is added 4-methyl-6-n-butyl-alpha-pyrone. The use of the
4-methyl-6-n-butyl-alpha-pyrone at this level causes the tobacco
prior to smoking to have a sweet coumarin-like, foenugreek-like and
celery-like aroma. On smoking, the foenugreek-line aroma is not
perceived in the smoke flavor. However, the cigarettes are found to
have a spicy, celery-like, fatty, creamy, cereal and nut-like aroma
and taste and to be sweeter and spicier than the same formulation
without the 4-methyl-6-n-butyl-alpha-pyrone whether or not the
other flavor ingredients of formulation A are present therein.
iii. At the rate of 500 ppm to one-seventh of the cigarettes in
each group is added 6-n-propyl-alpha-pyrone. The use of the
6-n-propyl-alpha-pyrone in the cigarettes causes the cigarettes
prior to smoking to have a creamy, sweet coumarin-like, herbal
aroma. In smoke flavor, the herbal note is not found, however, on
smoking, the cigarettes containing the 6-n-propyl-alpha-pyrone are
found to have a sweet, aromatic, lactone, coumarin, vanillin-like
taste and aroma, whether or not the other flavor ingredients of
formulation A are present.
iv. At the rate of 200 ppm to one-seventh of the cigarettes in each
group is added 4-methyl-6-isopropyl-alpha-pyrone. The use of the
4-methyl-6-isopropyl-alpha-pyrone at this level causes the tobacco
prior to smoking to have a sweet rum-like, lovage, tagette aroma
with a "tonka" undertone. On smoking, rum-like aroma is not
perceived in the smoke flavor. However, the cigarettes are found to
have sweet, aromatic, warm, spicy, lovage-like taste and aroma
notes not existing in the same formulation without the
4-methyl-6-isopropyl-alpha-pyrone whether or not the other flavor
ingredients of formulation A are present therein.
v. At the rate of 500 ppm to one-seventh of the cigarettes in each
group is added 6-n-butyl-alpha-pyrone. The use of the
6-n-butyl-alpha-pyrone at this level causes the tobacco prior to
smoking to have a sweet and floral aroma with a slight
coumarin-like character. On smoking, the floral note is not
perceived in the smoke flavor. However, the cigarettes on smoking
are found to have a sweet, aromatic, coconut, coumarin-vanillin,
lactone taste and aroma, whether or not the other flavor
ingredients of formulation A are present.
vi. At the rate of 200 ppm to one-seventh of the cigarettes in each
group is added 6-n-pentyl-alpha-pyrone. The use of
6-n-pentyl-alpha-pyrone at this level in the cigarettes causes the
cigarettes prior to smoking to have a green, floral and coconut
aroma, significantly more intense than cigarettes containing
delta-dodecalactone. In smoke flavor, these notes are not found,
however, on smoking, the cigarettes containing the
6-n-pentyl-alpha-pyrone are found to have a marked fruity,
coumarin-like taste and aroma whether or not the other ingredients
in formulation A are present.
One-seventh of the cigarettes remains totally without added
flavorants. One-seventh of the cigarettes contains only formulation
A added thereto; but no 6-alkyl-alpha-pyrone.
In general, on smoking, the cigarettes containing the exemplified
6-alkyl-alpha pyrones are more coumarin-like and/or sweeter,
warmer, spicier and more aromatic in nature than those cigarettes
not containing these 6-alkyl-alpha pyrones whether or not
ingredients of formulation A are included in the tobacco.
It will be understood by those skilled in the art from the
foregoing description that the 6-alkyl-alpha-pyrones of our
invention can be used in the preparation of a wide variety of
tobacco flavors and products.
EXAMPLE II
TOBACCO FLAVOR FORMULATION CONTAINING 6-ALKYL-ALPHA-PYRONES
A tobacco flavor formulation is prepared by admixing the following
ingredients:
Ingredients Parts ______________________________________
6-n-pentyl-alpha-pyrone 2.0 Ethyl Butyrate 0.5 Ethyl Valerate 0.5
Maltol 20.0 Cocoa Extract 260.0 Coffee Extract 100.0 95% Aqueous
Ethanol 200.0 Water 419.0
______________________________________
This formulation is added to smoking tobacco at the rates of 0.01,
0.02, 0.03 and 0.035% based on the dry weight of the tobacco. The
tobacco is then manufactured into cigarettes according to standard
manufacturing practice. On smoking the cigarettes, the aroma and
tast is described as "fruity, coumarin-like" with intensity of the
"fruity-coumarin" quality, increasing with increasing concentration
of the flavor formulation in the tobacco.
EXAMPLE III
TOBACCO FLAVOR FORMULATION
A tobacco flavoring formulation is prepared by admixing the
following ingredients:
Ingredients Parts ______________________________________
Cinnamaldehyde 30.60 Nutmeg Oil, EI 0.50 Dibenzyl Ether 3.70
Eugenol 1.20 4-methyl-6-n-butyl-alpha-pyrone 3.00 Vanillin 0.50
3-Phenyl-4-pentenal dimethyl acetal 60.00 prepared according to the
process disclosed in copending application for U.S. Letters Patent
276,922 filed on August 1, 1972
______________________________________
The foregoing formulation is added to smoking tobacco at the rate
of 0.06-0.15% based on the dry weight of tobacco. The purpose of
the use of the 3-phenyl-4-pentenal dimethyl acetal is to provide to
the flavor on smoking a cinnamon powder aroma and taste. The
4-methyl-6-n-butyl-alpha-pyrone (concentration on tobacco:
1800-4500 ppm) acts as an excellent replacement for the coumarin,
formerly used in this formulation, and also enables the
previously-used quantity of vanillin to be halved.
A formulation yielding substantially the same results is produced
when one-half of the 4-methyl-6-n-butyl-alpha-pyrone used is
replaced with an equal quantity (1.50 parts by weight) of
4-methyl-6-n-pentyl pyrone.
EXAMPLE IV
TOBACCO FLAVOR FORMULATION
A tobacco flavoring formulation is prepared by admixing the
following ingredients:
Ingredients Parts ______________________________________ Bergamot
Oil, Italy 5.00 Ylang-ylang oil 1.20
4-methyl-6-n-pentyl-alpha-pyrone 1.20 Acetophenone 1.20 Phenyl
acetaldehyde 0.50 Phenyl ethyl isovalerate 1.00 Methyl heptynyl
carbonate 0.50 3-Phenyl-4-pentenal diethyl acetal 20.00 prepared
according to the process disclosed in copending application for
U.S. Letters Patent 276,922 filed on August 1, 1972 95% Aqueous
Ethanol 69.40 ______________________________________
The foregoing flavor is added to smoking tobacco at the rates of
0,10, 0.20 and 0.30% based on the weight of dry tobacco. The
tobacco is then manufactured into cigarettes according to standard
manufacturing practice. The purpose of the 3-phenyl-4-pentenal
diethyl acetal is to cause the tobacco, on smoking, to have a
hay-clover-like flavor with fruity notes. The
4-methyl-6-n-pentyl-alpha-pyrone (at concentrations, based on the
dry weight of tobacco, of 1200-3600 ppm) acts as an excellent
replacement for the coumarin, previously used in this
formulation.
* * * * *