Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~` 106ZZ69
Thi8 invention relates to flavor compo~itions and more par-
ticularly to flavor compositions containing an alkyl-2,3-dihydro-
3(1'hydroxyalkylidene)-2-oxo-5-alkyl-furan-4-carboxylate.
. . - .
It is well known that synthetic flavor enhancers such as
Maltol, Ethyl Maltol, and 4-hydroxy-2,5-dimethyl-3(2H)-furanone
are useful as flavor enhancers. However, ~uch flavor enhancers
are very expensive and increase the cost of pxoducts in which
they are used.
In accordance with one feature of this invention, an alkyl-
2,3-dihydro-3(1'hydroxyalkylidene)-2-oxo-5-alkyl-~uran-4-carboxy-
late is added to flavor components to impart a significantly en~
hanced flavor to a wide variety of flavor components. For exam-
ple, butterscotch flavors are materially improved in smoothness.
Strawberry flavors are given a striking freshness. Banan~ flavors
are rounded out to give the flavor of a ripe banana. When added
to smoking tobacco or synthetic tobacco, the resulting product is
increased in ~weetness, the taste of the smoke i~ softened and the
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flow of saliva is increased, which lessens dryness of the mouth
during smoking. When added to cough syrup containing theophyl-
line, the flavor enhancer of this invention covers up the bitter
taste. This flavor enhancer can also be used to replace part of
the sugar content of a wide variety of sweetened beverages and
foods, producing excellent flavor at lower cost.
Alkyl-2,3-dihydro-3(1'-hydroxyalkylidene)-2-oxo-5-alkyl-
furan-4-carboxylates employed in the flavor compositions of this
invention have the formula:
H
R 0
Rl O
., 0/
:.
in which Rl is a straight or branched chain alkyl having les~
than 6 carbon atoms, and R2 is a straight or branched chain
alkyl having less than 7 carbon atoms, cyclopentyl or cyclo-
hexyl.
Examples of Rl are methyl, ethyl, propyl, isopropyl, butyl, -
isobutyl, amyl and isoamyl.
Examples of R2 are methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, amyl, isoamyl, hexyl or isohexyl.
Rl and R2 may be the same or different.
The alkyl-2,3-dihydro-3(1'hydroxyalkylidene)-2-oxo-5~alkyl-
furan-4-carboxylates may be prepared by the general methods of
Knorr, Ber. 1889, 22, 158.
The flavor compositions of this invention comprise at least
0.0025% by w~ight of one or more alkyl-2,3-dihydro-3(1'hydroxy-
alkylidene)-2-oxo-5-alkyl-furan-4-carboxylates. The amount of
alkyl-2,3-dihydro-3(1'hydroxyalkylidene)-2-oxo-5-alkyl-furan-4-
carboxylate may vary within wide ranges such as 0.0001% to 30%
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by weight. More advantageously the range may be between 0.001%
and 20% by weight of the flavor composition and preferably be-
tween 0.0025% and 5% by weight of the flavor composition.
Examples of flavor components of the flavor compositions of
this invention are flavor mixtures E~ se such as pineapple,
butterscotch, banana, and strawberry; food~tuffs such as meats,
protein sources, fruits, cereals and other comestibles; beverages
such as soft drinks, wines, alcoholic drinks, carbonated beve-
rages; smoking tobacco; liquid medicaments such as cough syrups;
and sugar substitutes in a wide range of edible or drinkable
products.
In accordance with another feature of this invention, cer-
tain alkyl-2,3-dihydro-3(1'-hydroxyalkylidene)-2-oxo-5-alkyl-
furan-4-carboxylates are new and novel. Such new and novel car-
boxylates significantly enhance the flavor components of the com-
positions of this invention. The new and novel carboxylates
have the following formula:
~ 1 fH
~, .. , . ,. R2-0 /--~ Rl
in which Rl iB a straight or branched chain alkyl having more
than 1 and less than 6 carbon atoms, and R2 is a straight or
branched chain alkyl having more than 1 and less than 7 carbon
atoms, cyclopentyl or cyclohexyl.
Examples of Rl are ethyl, propyl, isopropyl, butyl, iso-
- butyl, amyl and i~oamyl.
Examples of R2 are ethyl, propyl, isobutyl, amyl, hexyl and
cyclopentyl.
Rl and R2 may be the same or different.
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The new and novel carboxylates may be produced by the
general method of KnorrJ Ber. 1889, 22, 158.
A more comprehensive understanding of this invention i8
obtained from the following examples. Examples I and II show
compo~itions produced with two levels of concentration of
ethyl-2,3-dihydro-3(1'-hydroxyethylidene)-2-oxo-5-methyl-furan-
4-carboxylate.
EXAMPLE I
PINEAPPLE FLAVOR COMPOSITION
Parts by Parts by
Weight Weiqht
Allyl Cyclohexane Propionate 1.4 1.4
Geranyl Propionate 0.5 0.5
Allyl Caproate 13.0 13.0
Ethyl Iso Valerate 1.0 1.0
Ethyl Butyrate 1.0 1.0
Vanillin 0.5 0.5
Oil Orange 1.0 1.0
Maltol 2.0 2.0
Ethyl-2,3-Dihydro-3(1'-Hydroxyethylidene)-
2-Oxo-5-Methyl-Furan-4-Carboxylate 20.0 2.5
Ethyl Alcohol 95% 46.0 46.0
Propylene Glycol 13.6 31.1
100.0100.0
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EXAMPLE II
STR~WBERRY FLAVOR COMPOSI~ION
Parts by Parts by
Weiqht Weiaht
Methoxy Phenyl Butanone 1.0 1.0
Ethyl Butyrate 6.0 6.0
Ethyl Iso Valerate 2.0 2.0
Benzyl Butyrate 1.5 1.5
Benzyl Iso Valerate 0.5 ' 0.5
cis-3-Hexenol 3 0 3 0
Isobutyric Acid 1.5 1.5
Diacetyl 0.2 0.2
Butyl Phenylacetate 0.4 0.4
Acetaldehyde 50% in Ethanol 0.2 0.2
Benzyl Dipropyl K~tone 0.2 0.2
2-Heptanone 0.1 0.1
Ethyl Methyl Phenyl Glycidate 2.4 2.4
Ethyl-2,3-Dihydro-3(1'-Hydroxyethylidene)-
2-Oxo-5-Methyl-Furan-4-Carboxylate 30.0 5.0
Propylene Glycol 51.0 51.0
Benzyl Alaohol ~ 25.0
100.0 1~0.0
.~
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EX~MPLE III
BUTTERSCOTCH FLAVOR COMPOSITION
Parts by
Weiqht
Ethyl-2,3-Dihydro-3(1'Hydroxyethylidene)-
2-Oxo--S-Methyl-Furan-4--Carboxylate ~ 1.0
Butyl Butyrolaetate 4.0
Diacetyl 0.2
Ethyl Oleate 2.0
Ethyl Myristate o,5
Vanillin 1.5
Aeetoin 0~3
Phenylethanol 0.2
Butyric Acid 0.1
Ethyl Qxyhydrate 0.1
Ethyl Maltol 3,0
~-Decalactone 0,3
~-Nonalaetone 0.1
Tincture Foenugreek 0.4
Methyl Cyelopentene-ol-one 0.1
Benzyl Aleohol 26.0
Propylene Glyeol 60.2
100.0
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EX~MPLE_IV
BANANA FLAVOR COMPOSITION
Parts by
Weiqht
Iso Amyl Acetate 12.0
Iso Amyl Butyrate , ! 10 . O
Benzyl Butyrate 3.0
Iso Amyl Iso Valerate 2~0
Ethyl Butyrate 3.0
Butyric Acid 1.5
Oil Lemon 2.5
Vanillin 2.5 :
Ethyl Maltol 0.5
~-Undecalactone 0.4
4-~p-Hydroxyphenyl)-2-Butanone 0.1
Ethyl-2,3-Dihydro-3(1'Hydroxyethylidene)-
2-Oxo-5-Methyl-Furan-4-Carboxylate 10.0
Propylene Glycol 52.5
100 . O
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EX~MP~ V
BUTTERSCOTCH FLAVOR
VA VB
Butyl Butyrolactate 4.0 4.0
Diacetyl 0.2 0.2
Ethyl Oleate 2.0 2.0
Ethyl Myri~tate 0.5 0 5
Vanillin 1.5 1.5
Acetyl Methyl Carbinol 0.3 0.3
Phenyl Ethyl Alcohol 0.2 0.2
Butyric Acid 0.1 0.1
Ethyl Oxyhydrate 0.1 0.1
Ethyl Maltol 3.0
Ethyl-2,3-Dihydro-3(1'Hydroxyethylidene)-
2-Oxo-5-Methyl-Furan-4-Carboxylate 1.0 5.0
Q-Decalactone 0.3 0.3
~-Nonalactone 0.1 0.1
Tincture Foenugreek 0.4 0.4
Methyl cyclopenten-ol-one 0.1 0.1
Benzyl Alcohol 26.0 26.0
Propylene Glycol 60.2 59.2
100 . O 100 . O
Formula U~ contains Ethyl Maltol in addition to ethyl-2,3-
dihydro-3(1'hydroxyethylidene)-2-oxo-5-methyl-furan-4-carboxylate,
while Formula VB contains only the carboxylate as a complete re-
placement for Ethyl Maltol. The butterscotch flavor achieved by
Formula VB i6 richer and smoother.
The replacement proportion of Ethyl Maltol by ethyl-2,3- -
dihydro-3(1'-hydroxyethylidene)-2-oxo-5-methyl-furan-4-carboxylate
i8 approximately one and one-half part~ by weight of the carboxy-
late for one part by weight of Ethyl Maltol.
.
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EXAMPLE VI
WINE FL~VOR COMPOS ITION
The wine flavor composition is produced by initially adding
0.08 parts by weight of ethyl-2,3-dihydro-3(1 hydroxyethylidene)-
~ 2-oxo-5-methyl-furan-4-carboxylate to 99.92 parts by weight of
; natural wine flavor. Four liquid ounces of the wine concentrate
are added to one gallon of wine.
A wine flavor composition may al~o be produced by preparing
a 1% by weight ethanol solution of ethyl-2,3-dihydro-3(1'-hydroxy-
ethylidene)-2-oxo-5-methyl-furan-4-carboxylate and adding 0.32
fluid ounces of the solution to 1 gallon of wine. This i8 equi-
valent to 25 parts per million.
EX~MPLE VII
`, TOBACCO FL~VOR COMPOSITION
A 1% ethanol solution of ethyl-2,3-dihydro-3(1'hydroxyethy-
lidene)-2-oxo-5-methyl-furan-4-carboxylate is sprayed on smoking
tobaeco at the rate of 4 ounces of solution per 100 pounds of
tobaeco. After the alcohol is allowed to evaporate, a tobacco
flavor composition results.
To produee a flavored tobaceo whieh also eontains synthetie
tobaeeo, the procedure for the production of tobacco flavor com-
position heretofore described in this Example is repeated except
that instead of employing -moking tobacco only, synthetic tobacco
such as cellulose fibers, for example, the cellulose fibers sold
by the Celanese Chemical Company under the trademark "CYTREL" or
! the eellulose fibers sold by Imperial Chemical Corporation under -
the trademark "POLYSTREP", is blended with the flavored tobaceo
in a ratio of approximately 1 to 1 by weight.
In a third proeedure, a 1% etha~ol solution of ethyl-2,3- -
dihydro-3~ hydroxyethylidene)-2-oxo-5-methyl-furan-4-carboxylate
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106226g
is sprayed on synthetic tobacco, such as cellulose fibers, at
the rate of 4 ounces of solution to 100 pounds of synthetie
tobacco. After the alcohol is allowed to evaporate, a tobaeeo
flavor synthetic composition results.
Any one of the above tobacco flavor eompositions may be
used in cigarettes, producing a striking improvement in flavor.
` Experiments were conducted with panatela cigars using
ethyl-2,3-dihydro-3(1'-hydroxyisopentylidene)-2-oxo-5-isobutyl-
furan-4-carboxylate as the flavor enhaneer in 95% ethanol at the
rate of 1.5 ounces of enhaneer to 100 pounds of panatela eigars.
The aroma and flavor of the smoke were signifieantly improved.
';
EXAMPLE VIII
-~ CARBONATED SOFT DRINKS
., _
A fruit flavor earbonated soft drink is produeed by dissol-
ving one ounee by weight of one of the flavor eompositions sueh
2` as deseribed in Examples I or II in one gallon of sugar syrup.
One ounee of the resulting mixture is added to about five ounees
of earbonated water to produee six ounees of earbonated beverage.
`~ ' '
The flavor eompo~ition eontaining 2.5% by weight of ethyl-2,
3-dihydro-3(1'-hydroxyethylidene)-2-oxo-5-methyl-furan-4-earboxylate
results in a level of 32 parts per million of ethyl-2,3-dihydro-
3(1'-hydroxyethylidene)-2-oxo-5-methyl-furan-4-earboxylate flavor
enhaneer in the total earbonated drink produeed.
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EX~MPLE IX
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BUTTERSCOTCH FLAVOR COMPOSITION
A butterscotch composition containing a flavor enhancer
in accordance with the teaching of the invention was prepared.
For comparison, another composition containing the same ingre-
dients but without the flavor enhancer was also prepared as a
control. The formulas of the compositions are as follows:
Parts by Parts by
Weight Wei~ht
~Control)
Butyl Butyrolactate 4.0 4.0
Diacetyl 0.2 0.2
Ethyl Oleate 2.0 2.0
Ethyl Myristate 0.5 0 5
Vanillin 1.5 1.5
Acetyl Methyl Carbinol 0.3 0.3
Phenyl Ethyl Alcohol 0.2 0.2
Butyric Acid 0.1 0.1
; Ethyl Propionate 0.1 0.1
Ethyl Maltol 3 0 3.0
; ~-Decalactone 0 3 0.
onalactone 0.1 0.1
Methyl Para-Tertiary Butyl
Phenylacetate (in 1% alcohol) 0.1 0.1
Tincture Foenugreek 0.4 0.4 ~ ;
Cyclotene 0.1 0.1
Benzyl Alcohol 27.1 27.1 -~
Propylene Glycol 60.0 57.0
; Ethyl-2,3-Dihydro-3(1'-Hydroxypropylidene)-
2-Oxo-5-Ethyl-Furan-4-Carboxylate - 3.0
` 100.0100.0
The butterscotch composition containing the flavor enhancer
had an immeasurably superior flavor over the control.
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