US 4,332,829 AGrant
Methylthiomethyl Esters as Flavor Additives
Issue Date:1982-06-01
•33 Claims
Abstract
Methylthiomethyl esters of aliphatic acids have been found useful in imparting or enhancing flavors in foodstuffs. They are particularly useful with respect to fruit and berry flavors.
Metadata
Assignee
- Polak's Frutal Works, B.V.
Inventors
- Steven van den Bosch
- Evert van't Land
- Jan Stoffelsma
Application Information
Application Number:US 2311844
Filing Date:1981-02-02
Priority Date:1978-07-18
Art Unit:172
Classifications
IPC:
A23L 1226A23L 1235
Field of Search:
426535
Patent Drawings
This patent does not have any drawings.
Description
This invention relates to the use of methylthiomethyl esters of aliphatic acids as flavor additives and to flavoring compositions and foodstuffs containing such compounds.
Food scientists and researches are constantly striving to improve or strengthen the flavor and the flavor impact of foodstuffs by use of flavor additives to replace flavor lost by the processing or in storage or to impart a "natural" flavor effect to a reconstituted foodstuff. Considerable effort is also being put into developing flavor compounds and flavoring compositions for imparting flavors to otherwise bland or tasteless, though nutritionally useful, materials.
In accordance with this invention, there are provided flavoring compositions or flavor enhancing compositions containing methylthiomethyl esters of aliphatic acids, represented by the structural formula R--COOCH.sub.2 SCH.sub.3 wherein R is selected from the group consisting of hydrogen, alkyl radicals with 1 to 9 carbon atoms, alkenyl radicals with 2 to 9 carbon atoms and polyunsaturated alkyl radicals with 4 to 9 carbon atoms. When R represents one of the above described alkyl groups, the alkyl group can be straight-chain or branched-chain. Some of the compounds presented in this invention exist in isomeric forms, and the compounds given herein include such isomers and mixtures thereof.
Although some of the compounds used in the present invention are known in literature, there is no disclosure in the prior art indicating that they possess flavoring properties. The following methylthiomethyl esters of the aliphatic series are known from the chemical literature: the acetate, the propionate, the octanoate, the acrylate, and the methacrylate (see e.g., Chem. Abstr., 83, 192168U, Tetrah. Letters, 1972, 4941-4, J. Amer. Chem. Soc., 92, 6521-5 (1970), Tetrahedron, 19, 817-20 (1963), Can. J. Chem. 42, 2357-62 (1964), Chem. Abstr., 59, 3806g, Ann., 626, 19-25 (1959), Syn. Comm., 3, 145-6 (1973), J.C.S. Chem. Comm., 1973, 224-5, Chem. Abstr., 72, 54677f, and J. Amer. Chem. Soc., 91, 682-7 (1969)).
As stated, the methylthiomethyl esters of this invention exhibit a wide variety of flavor effects giving rise to a wide field of uses. In particular, they are useful in fruit flavors, e.g., pineapple, strawberry, raspberry, blackcurrant, mango, durian, grape, apple, peach, pear, and other fruit and berry flavors. The esters are also useful in cheese, cream, milk, meat, and vegetable flavors.
The following table illustrates some of the great variety of flavor effects exhibited by the compounds presented in the invention.
The methylthiomethyl esters of this invention can be employed singly or in admixture of two or more. They all can be employed as components either of flavoring compositions or of flavor-enhancing compositions.
A flavoring composition means a combination of ingredients compounded to supply or impart a specific flavor character to an otherwise bland ingestible material, or to completely change an existing flavor. A flavor-enhancing composition is a combination of ingredients which, in combination, are capable of reinforcing one or more flavor notes of a natural or other foodstuff to improve, supplement or augment a flavor which has been undesirably diminished or otherwise altered by processing or which is inferior due to the general quality of the foodstuff initially. Either type of composition is usually suspended or dissolved in an organoleptically inert carrier, although this is not absolutely necessary.
When used in fruit or berry flavoring compositions, additional flavoring compounds typically used in combination with the methylthiomethyl esters of the invention include, e.g.
When used in dairy type flavors-i.e., cheese, butter, or cream flavors, additional flavoring compositions typically used in combination with the methylthiomethyl esters of the invention include:
The term "foodstuff" includes both solid and liquid ingestible materials which usually do, but need not, have nutritional value. Thus, foodstuffs include fruit juices, fruit flavored beverages, puddings, jellies, pastries, ice cream, candies, chewing gum, dairy products, vegetables, cereals, meats, soups, convenience foods and the like. They can also be employed to restore the fresh fruit effect of canned and frozen fruits.
The amount of methylthiomethyl ester added to a foodstuff needs to be only the amount sufficient to impart or to enhance the desired flavor. Small amounts are effective, though the amount can be varied over a wide range depending upon the flavor strength required. Generally, the amount will be between about 0.1 to 5 parts per million by weight based on the foodstuff being flavored.
To prepare the methylthiomethyl esters described in this invention, the corresponding acid is reacted with chloromethyl methyl sulfide in the presence of one equivalent of an amine, for example, triethylamine (T. L. Ho and C. M. Wong, J. Chem. Soc. Chem. Comm., 1973, 224-225).
The following examples are intended to illustrate the invention, but not to limit the same in any way.
EXPERIMENTAL PART
NMR spectra were recorded on a JEOL FX-100 instrument as solutions in CDCl.sub.3 with tetramethylsilane as internal standard.
IR spectra were measured with a Perkin-Elmer 225 Spectrophotometer, neat or as solutions in CCl.sub.4.
EXAMPLE 1
Preparation of Methylthiomethyl Hexanoate
In a three-necked 1000 ml. round-bottomed flask fitted with a mechanical stirrer, thermometer and reflux condenser is placed 63.8 g. of hexanoic acid in 200 ml. of acetonitrile. To the stirred mixture is added, at 20.degree.-30.degree. C., 55 g. of triethylamine over a period of 30 minutes. The reaction mixture is stirred at room temperature for an additional 60 minutes. Then is added, at 20.degree.-24.degree. C., 53 g. of chloromethyl methyl sulfide in a few minutes. The reaction mixture is warmed and allowed to reflux for 24 hours. The reaction mixture is cooled to 5.degree.-0.degree. C. and filtered. The solvent is stripped off under vacuum at 12 mm Hg pressure. The residue is taken up in diethyl ether and washed successively with a 10% solution of sodium bicarbonate and with water. The organic layer is dried over anhydrous sodium sulfate. Distillation gives the title ester; b.p. 57.degree.-58.degree. C./2 mm Hg, n.sub.D.sup.20 1.4545.
Spectral data of the compound:
EXAMPLE 2
Preparation of Methylthiomethyl Formate
This product was prepared according to the procedure described in Example 1, by reacting formic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 35.degree. C./12 mm Hg, n.sub.D.sup.20 1.4650.
Spectral data of the compound:
EXAMPLE 3
Preparation of Methylthiomethyl Acetate
This product was prepared according to the procedure described in Example 1, by reacting acetic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 45.degree.-46.degree. C./12 mm Hg, n.sub.D.sup.20 1.4570.
Spectral data of the compound:
EXAMPLE 4
Preparation of Methylthiomethyl Propionate
This product was prepared according to the procedure described in Example 1, by reacting propionic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 58.degree.-59.degree. C./12 mm Hg, n.sub.D.sup.20 1.4548.
Spectral data of the compound:
EXAMPLE 5
Preparation of Methylthiomethyl Butyrate
This product was prepared according to the procedure described in Example 1, by reacting butyric acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 71.degree.-73.degree. C./12 mm Hg, n.sub.D.sup.20 1.4521.
Spectral data of the compound:
EXAMPLE 6
Preparation of Methylthiomethyl Isobutyrate
This product was prepared according to the procedure described in Example 1, by reacting isobutyric acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 64.degree. C./12 mm Hg, n.sub.D.sup.20 1.4470.
Spectral data of the compound:
EXAMPLE 7
Preparation of Methylthiomethyl Valerate
This product was prepared according to the procedure described in Example 1, by reacting valeric acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 83.degree.-85.degree. C./12 mm Hg, n.sub.D.sup.20 1.4560.
Spectral data of the compound:
EXAMPLE 8
Preparation of Methylthiomethyl Isovalerate
This product was prepared according to the procedure described in Example 1, by reacting isovaleric acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 78.degree.-79.degree. C./12 mm Hg, n.sub.D.sup.20 1.4496.
Spectral data of the compound:
EXAMPLE 9
Preparation of Methylthiomethyl 2-Methylbutyrate
This product was prepared according to the procedure described in Example 1, by reacting 2-methylbutyric acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 75.degree.-77.degree. C./12 mm Hg, n.sub.D.sup.20 1.4505.
Spectral data of the compound:
EXAMPLE 10
Preparation of Methylthiomethyl Tiglate
This product was prepared according to the procedure described in Example 1, by reacting tiglic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 95.degree. C./12 mm Hg, n.sub.D.sup.20 1.4890.
Spectral data of the compound:
EXAMPLE 11
Preparation of Methylthiomethyl 2-Hexenoate
This product was prepared according to the procedure described in Example 1, by reacting 2-hexenoic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 75.degree.-76.degree. C./2 mm Hg, n.sub.D.sup.20 1.4836.
Spectral data of the compound:
EXAMPLE 12
Preparation of Methylthiomethyl 2-Methyl-2-pentenoate
This product was prepared according to the procedure described in Example 1, by reacting 2-methyl-2-pentenoic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 56.degree.-57.degree. C./2 mm Hg, n.sub.D.sup.20 1.4861.
Spectral data of the compound:
EXAMPLE 13
Preparation of Methylthiomethyl Heptanoate
This product was prepared according to the procedure described in Example 1, by reacting heptanoic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 80.degree.-81.degree. C./2 mm Hg, n.sub.D.sup.20 1.4591.
Spectral data of the compound:
EXAMPLE 14
Preparation of Methylthiomethyl Octanoate
This product was prepared according to the procedure described in Example 1, by reacting octanoic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 90.degree. C./2 mm Hg, n.sub.D.sup.20 1.4577.
Spectral data of the compound:
EXAMPLE 15
Preparation of Methylthiomethyl Citronellate
This product was prepared according to the procedure described in Example 1, by reacting citronellic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 110.degree. C./2 mm Hg, n.sub.D.sup.20 1,4760.
Spectral data of the compound:
EXAMPLE 16
Preparation of Methylthiomethyl Geranate
This product was prepared according to the procedure described in Example 1, by reacting geranic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 111.degree.-112.degree. C./2 mm Hg, n.sup.20 1.4912.
Spectral data of the compound:
EXAMPLE 17
Preparation of Methylthiomethyl Lavandulate
This product was prepared according to the procedure described in Example 1, by reacting lavandulic acid with chloromethyl methyl sulfide in the presence of one equivalent of triethylamine; b.p. 93.degree.-94.degree. C./2 mm Hg, n.sup.20 1.4855.
Spectral data of the compound:
EXAMPLE 18
Two cheese flavor enhancing compositions were prepared by mixing the following ingredients:
Mixtures A and B were added separately to a commercially available low caloric processed cheese (20% fat content) at a level of 4 g. per kilogram. The processed cheese containing mixture A was compared with the processed cheese containing mixture B. The processed cheese containing mixture B was preferred over the processed cheese containing mixture A, because it had a more pronounced cheese taste with an increased creamy character.
EXAMPLE 19
Three pineapple flavor compositions were prepared by mixing the following ingredients:
Mixtures A, B and C were added separately to a test solution (containing 10% sugar and 0.05% citric acid) at a level of 0.1 g. per liter. The flavored solutions were tasted and compared. As compared with mixture A, the taste of mixture B is preferred because it is more pineapple-like with a more natural taste and aftertaste. As compared with mixture A, the taste of mixture C is preferred because it has a better pineapple character with increased fruitiness and the heavy natural sweetness of the genuine fruit.
EXAMPLE 20
Two strawberry flavor compositions were prepared by mixing the following ingredients:
Mixtures A and B were added separately to a test solution (containing 10% sugar and 0.05% citric acid) at a level of 0.2 g. per liter. The flavored test solutions were compared. The test solution containing mixture B was preferred over the test solution containing mixture A because it has an improved strawberry character with notes reminiscent of a ripe, jammy strawberry. Similar notes were not found in the test solution containing mixture A.
EXAMPLE 21
Three cream flavor compositions were prepared by mixing the following ingredients:
Mixtures A, B and C were added separately to a test solution (containing 8% sugar) at a level of 0.2 g. per liter. The flavored solutions were tasted and compared. As compared with mixture A, the taste of mixture B is more pronounced cream-like, having an improved dairy character. The test solution containing mixture B was therefore preferred over the test solution containing mixture A. As compared to mixture A, the taste of mixture C is preferred because it showed a fuller, richer, more cream-like character, with enhanced sweet notes.
EXAMPLE 22
Two mango flavor compositions were prepared by mixing the following ingredients:
Mixtures A and B were added separately to a test solution (containing 10% sugar and 0.05% citric acid) at a level of 0.2 g. per liter. The flavored solutions were tasted and compared. As compared with mixture A, the taste of mixture B is more mango-like with a typical sulfury, fruity, tropical note which is important for this fruit. Since this note was not found in the test solution containing mixture A, the test solution containing mixture B was preferred.
EXAMPLE 23
Three blackcurrant flavor compositions were prepared by mixing the following ingredients:
Mixtures A, B and C were added separately to a test solution (containing 10% sugar and 0.05% citric acid) at a level of 0.01 g. per liter. The flavored solutions were tasted and compared. As compared with mixture A, the taste of mixture B is preferred because it has a better blackcurrant flavor with a fresh, fruity topnote reminiscent of the fresh fruit. As compared with mixture A, the taste of mixture C is preferred because it has a blackcurrant flavor with increased sweet body notes giving a richer fuller fruity character.
EXAMPLE 24
Two peach flavor compositions were prepared by mixing the following ingredients:
Mixtures A and B were added separately to a test solution (containing 10% sugar and 0.05% citric acid) at a level of 0.2 g. per liter. The flavored solutions were tasted and compared. As compared with mixture A, the taste of mixture B is preferred because it has a better peach character with improved aftertaste and a sweet jammy note reminiscent of ripe peach.
EXAMPLE 25
Two condensed milk flavor compositions were prepared by mixing the following ingredients:
Mixtures A and B were added separately to a test solution (containing 8% sugar) at a level of 0.2 g. per liter. The flavored solutions were tasted and compared. As compared with mixture A, the taste of mixture B is preferred because it has a pronounced cooked milk character with a richer creamier aftertaste.
EXAMPLE 26
Two grape flavor compositions were prepared by mixing the following ingredients:
Mixtures A and B were added separately to a test solution (containing 10% sugar and 0.05% citric acid) at a level of 0.2 g. per liter. The flavored solutions were tasted and compared. As compared with mixture A, the taste of mixture B is preferred because it has an improved grape character with a more natural aftertaste and does not have the harsh methyl anthranilate taste shown by mixture A.
Claims
What we claim and desire to protect by Letters Patent is:
1. A fruit or berry flavoring composition or a fruit or berry flavor-enhancing composition comprising a combination of olfactorily active ingredients including at least one methylthiomethyl ester having the structural formula R--COOCH.sub.2 --S--CH.sub.3 wherein R is selected from the class consisting of hydrogen, alkyl radicals with 2 to 9 carbon atoms, alkenyl radicals with 2 to 9 carbon atoms, and polyunsaturated radicals with 4 to 9 carbon atoms and at least one compound selected from the class consisting of: orange oil isoamyl acetate phenyl ethyl isovalerate fusel oil damascenone lie de vin ethyl maltol 2-methyl butanol 2-methylbutyric acid phenylethyl alcohol angelica root oil trans-2-hexenol buchu oil methyl anthranilate cognac oil 2-methyl-2-pentenoic acid petitgrain oil vanillin cedar leaf oil maltol isoamyl isovalerate benzyl alcohol methyl butyrate linaolool isobutyl acetate isoamyl butyrate methyl isobutyl carbinyl acetate ethyl acetate ethyl butyrate ethyl benzoate ethyl hexanoate citral ethyl heptanoate cuminic aldehyde cis-3-hexenol beta-ionone ethyl isovalerate tangerine oil phenyl butyrate benzyl acetate amyl acetate orange peel oil geranyl acetate bergamot oil gamma-nonalactone lime oil Ylang Ylang orange terpenes beta-terpineol methyl cinnamate.
2. A flavoring composition according to claim 1 wherein R is hydrogen or an alkyl radical with 1 to 9 carbon atoms.
3. The flavoring composition according to claim 2 wherein the ester is methylthiomethyl butyrate.
4. The flavoring composition according to claim 2 wherein the ester is methylthiomethyl isobutyrate.
5. The flavoring composition according to claim 2 wherein the ester is methylthiomethyl 2-methylbutyrate.
6. The flavoring composition according to claim 2 wherein the ester is methylthiomethyl valerate.
7. The flavoring composition according to claim 2 wherein the ester is methylthiomethyl isovalerate.
8. The flavoring composition according to claim 2 wherein the ester is methylthiomethyl hexanoate.
9. The flavoring composition according to claim 2 wherein the ester is methylthiomethyl heptanoate.
10. The flavoring composition according to claim 2 wherein the ester is methylthiomethyl octanoate.
11. A flavoring composition according to claim 1 wherein R is an alkenyl radical with 2 to 9 carbon atoms.
12. The flavoring composition according to claim 11 wherein the ester is methylthiomethyl tiglate.
13. The flavoring composition according to claim 11 wherein the ester is methylthiomethyl 2-hexenoate.
14. The flavoring composition according to claim 11 wherein the ester is methylthiomethyl 2-methyl-2-pentenoate.
15. A flavoring composition according to claim 1 wherein R is a polyunsaturated alkyl radical with 4 to 9 carbon atoms.
16. The flavoring composition according to claim 15 wherein the ester is methylthiomethyl lavandulate.
17. A foodstuff to which has been added about 0.1 to 5 parts per million, based on the total weight of said foodstuff, of at least one methylthiomethyl ester having the structural formula R--COOCH.sub.2 SCH.sub.3 wherein R is selected from the class consisting of hydrogen, alkyl radicals with 1 to 9 carbon atoms, alkenyl radicals with 2 to 9 carbon atoms and polyunsaturated alkyl radicals with 4 to 9 carbon atoms.
18. A foodstuff according to claim 17 wherein R is hydrogen or an alkyl radical with 1 to 9 carbon atoms.
19. The foodstuff of claim 18 wherein the ester is methylthiomethyl butyrate.
20. The foodstuff of claim 18 wherein the ester is methylthiomethyl isobutyrate.
21. The foodstuff of claim 18 wherein the ester is methylthiomethyl 2-methylbutyrate.
22. The foodstuff of claim 18 wherein the ester is methylthiomethyl valerate.
23. The foodstuff of claim 18 wherein the ester is methylthiomethyl isovalerate.
24. The foodstuff of claim 18 wherein the ester is methylthiomethyl hexanoate.
25. The foodstuff of claim 18 wherein the ester is methylthiomethyl heptanoate.
26. The foodstuff of claim 18 wherein the ester is methylthiomethyl octanoate.
27. A foodstuff according to claim 17 wherein R is an alkenyl radical with 2 to 9 carbon atoms.
28. The foodstuff of claim 27 wherein the ester is methylthiomethyl tiglate.
29. The foodstuff of claim 27 wherein the ester is methylthiomethyl 2-hexenoate.
30. The foodstuff of claim 27 wherein the ester is methylthiomethyl 2-methyl-2-pentenoate.
31. A foodstuff according to claim 17 wherein R is a polyunsaturated alkyl radical with 4 to 9 carbon atoms.
32. The foodstuff of claim 31 wherein the ester is methylthiomethyl lavandulate.
33. A method of improving the flavor of a foodstuff which comprises adding thereto about 0.1 to 5 parts per million of at least one methylthiomethyl ester having the structural formula R--COOCH.sub.2 SCH.sub.3 wherein R is selected from the class consisting of hydrogen, alkyl radicals with 1 to 9 carbon atoms, alkenyl radicals with 2 to 9 carbon atoms and polyunsaturated alkyl radicals with 4 to 9 carbon atoms.
Patent Citations (3)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3870800 | 1975-03-01 | Pettet et al. | |
| US3900581 | 1975-08-01 | Wenter et al. | |
| US3978240 | 1976-08-01 | van der Heijden et al. |
Non-Patent Literature (1)
- Fenaroli's Handbook of Flavor Ingredients, 2nd Ed., 1975, Edited by Furia et al., CRC Press: Cleveland, pp. 132, 133, 185, 202, 207, 208.