Methylthiomethyl esters as flavor additives

Abstract

Methylthiomethyl esters of aliphatic acids have been found useful in imparting or enhancing flavors in foodstuffs. They are particularly useful with respect to dairy-type flavors.

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 researchers 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.

______________________________________Methylthiomethyl ester of Organoleptic property______________________________________formic acid cabbage, meaty, onion, metallicacetic acid estery, milky, cabbage, meat, sulfurypropionic acid dairy-like, yoghurt, sulfurybutyric acid cabbage, milky, cheeseisobutyric acid strawberry, pineapple2-methylbutyric acid fruity, strawberry, pineapple, mango, durianvaleric acid fruity, cheese, milkyisovaleric acid blackcurrant, tropical fruitshexanoic acid pineapple, fruityheptanoic acid fruity, pineapple, pearoctanoic acid dairy-like, fruity, cheesetiglic acid sweet apple, fruity2-hexenoic acid green, cream, earthy, fatty2-methyl-2-pentenoic acid fruity, pear, sulfurygeranic acid aldehydic, fruity, esterycitronellic acid aldehydic, wine, earthylavandulic acid grape, radish, cabbage______________________________________

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.

______________________________________orange oil isoamyl acetatephenyl ethyl isovalerate fusel oildamascenone lie de vinethyl maltol 2-methyl butanol2-methylbutyric acid phenylethyl alcoholangelica root oil trans-2-hexenolbuchu oil methyl anthranilatecognac oil 2-methyl-2-pentenoic acidpetitgrain oil vanillincedar leaf oil maltolisoamyl isovalerate benzyl alcoholmethyl butyrate linaoloolisobutyl acetate isoamyl butyratemethyl isobutyl carbinyl ethyl acetateacetate ethyl butyrateethyl benzoate ethyl hexanoatecitral ethyl heptanoatecuminic aldehyde cis-3-hexenolbeta-ionone ethyl isovaleratetangerine oil phenyl butyratebenzyl acetate amyl acetateorange peel oil geranyl acetatebergamot oil gamma-nonalactonelime oil Ylang Ylangorange terpenes beta-terpineolmethyl cinnamate______________________________________

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:

______________________________________vanillin ethyl butyratemaltol ethyl hexanoatedelta-decalactone 2-heptanoneheliotropin gamma-undecalactonebutyric acid ethyl lactatehexanoic acid gamma-decalactoneisovaleric acid gamma-dodecalactoneoctanoic acid acetoin diacetyl______________________________________

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 2000 and preferably about 5 to 2000 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.sup.20 1.4545.

Spectral data of the compound:

______________________________________NMR SPECTRUM (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.88 (t, 3H) 2960, 2930, 2875, 2860, 1731(s),.delta. = 1- 1.8 (--, 6H) 1470, 1417, 1220, 1162(s), 1106,.delta. = 2.23 (s, 3H) 1095, 964, 917, 750, 700 cm.sup.-1..delta. = 2.33 (t, 2H).delta. = 5.12 (s, 2H)______________________________________

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.sup.20 1.4650.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 2.26 (s, 3H) 2925, 1720, 1430, 1310, 1262,.delta. = 5.22 (s, 2H) 1130, 1010, 909, 870, 750, 694.delta. = 8.11 (t, 1H) 429 cm.sup.-1.______________________________________

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.sup.20 1.4570.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 2.07 (s, 3H) 2925, 1740(s), 1426, 1369, 1310,.delta. = 2.12 (s, 3H) 1210(s), 1018, 1008, 960, 910,.delta. = 5.10 (s, 2H) 812, 749, 697, 600, 462 cm.sup.-1.______________________________________

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.sup.20 1.4548.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 1.15 (t, 3H) 2985, 2945, 2925, 1740, 1460,.delta. = 2.24 (s, 3H) 1423, 1356, 1263, 1160, 1078,.delta. = 2.36 (q, 2H) 995, 934, 805, 749, 696 cm.sup.-1..delta. = 5.13 (s, 2H)______________________________________

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.sup.20 1.4521.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.96 (t, 3H) 2970, 2940, 2880, 1740(s), 1460,.delta. = 1.66 (m, 2H) 1418, 1363, 1312, 1260, 1240,.delta. = 2.23 (s, 3H) 1156(s), 1098, 1080, 1035,.delta. = 2.33 (t, 2H) 964(s), 920, 750, 696 cm.sup.-1..delta. = 5.13 (s, 2H)______________________________________

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.sup.20 1.4470.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 1.19 (d, 6H) 2975, 2920, 2875, 1735(s), 1468,.delta. = 2.22 (s, 3H) 1424, 1385, 1358, 1234, 1181,.delta. = 2.56 (m, 1H) 1134(s), 1053, 1015, 957, 916,.delta. = 5.12 (s, 2H) 880, 800, 760, 696 cm.sup.-1.______________________________________

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.sup.20 1.4560.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.92 (t, 3H) 2960, 2930, 2880, 1739(s), 1465,.delta. = 1-1.8 (m, 4H) 1416, 1260, 1225, 1150(s), 1103,.delta. = 2.22 (s, 3H) 1083, 960, 948, 746, 695 cm.sup.-1..delta. = 2.32 (t, 2H).delta. = 5.12 (s, 2H)______________________________________

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.sup.20 1.4496.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.92 (d, 6H) 2960, 2920, 2875, 1736(s), 1467,.delta. = 1.6 (m, 3H) 1425, 1366, 1310, 1284, 1237,.delta. = 2.21 (s, 3H) 1174, 1156(s), 1105, 1085, 975(s),.delta. = 5.12 (s, 2H) 940, 747, 693 cm.sup.-1.______________________________________

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.sup.20 1.4505.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.92 (t, 3H) 2985, 2930, 2875, 1736(s), 1460,.delta. = 1.16 (d, 3H) 1424, 1380, 1360, 1309, 1258,.delta. = 1.56 (m, 2H) 1220, 1170, 1133(s), 1064, 1000,.delta. = 2.23 (s, 3H) 966, 940, 756, 693 cm.sup.-1..delta. = 2.40 (m, 1H).delta. = 5.13 (s, 3H)______________________________________

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.sup.20 1.4890.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.80 d, 2980, 2920, 1710(s), 1647, 1430, 6H.delta. = 0.84 s, 1377, 1340, 1310, 1248(s), 1240(s),.delta. = 2.24 (s, 3H) 1140, 1116(s), 1080, 1060, 1014,.delta. = 5.20 (s, 2H) 961, 920, 745, 725 cm.sup.-1..delta. = 6.80 (q, 1H)______________________________________

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.sup.20 1.4836.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.94 (t, 3H) 2960, 2930, 2875, 1723, 1650,.delta. = 1.48 (m, 2H) 1424, 1333, 1313, 1237, 1158,.delta. = 2.2 (m, 2H) 1117, 1041, 984, 925, 750,.delta. = 2.24 (s, 3H) 695 cm.sup.-1..delta. = 5.19 (s, 2H).delta. = 5.84 (d, 1H).delta. = 7.0 (m, 1H)______________________________________

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.sup.20 1.4861.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 1.05 (t, 3H) 2965, 2930, 2875, 1720, 1649,.delta. = 1.84 (s, 3H) 1439, 1334, 1314, 1263, 1233,.delta. = 2.2 (m, 2H) 1154, 1132, 1095, 1076, 990,.delta. = 2.24 (s, 3H) 940, 750 cm.sup.-1..delta. = 5.20 (s, 2H).delta. = 6.81 (t, 1H)______________________________________

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.sup.20 1.4591.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.89 (t, 3H) 2960, 2925, 2860, 1740(s), 1466,.delta. = 1-1.9 (--, 8H) 1455, 1415, 1360, 1330, 1310,.delta. = 2.23 (s, 3H) 1260, 1220, 1145(s), 1100, 973,.delta. = 2.35 (t, 2H) 956, 746, 723, 695 cm.sup.-1..delta. = 5.12 (s, 2H)______________________________________

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.sup.20 1.4577.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.88 (t, 3H) 2955, 2920, 2860, 1734(s), 1460,.delta. = 1-1.8 (--, 10H) 1409, 1370, 1327, 1305, 1254,.delta. = 2.23 (s, 3H) 1210, 1140(s), 1100, 960, 742,.delta. = 2.34 (t, 2H) 716, 692 cm.sup.-1..delta. = 5.12 (s, 2H)______________________________________

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.sup.20 1.4760.

Spectral data of the compound:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 0.96 (d, 3H) 2960, 2920, 2855, 1740(s), 1434,.delta. = 1.58 (s, 3H) 1374, 1330, 1310, 1280, 1216,.delta. = 1.67 (s, 3H) 1170, 1130, 1072, 970, 746,.delta. = 2.12 (s, 3H) 692 cm.sup.-1..delta. = 5.10 (s, 2H)______________________________________

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:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 1.62 (s, 3H) 2965, 2920, 2855, 1720(s), 1641,.delta. = 1.70 (s, 3H) 1435, 1373, 1356, 1210, 1125(s),.delta. = 2.18 (--, 7H) 1050, 974, 929, 860, 815, 748,.delta. = 2.24 (s, 3H) 693 cm.sup.-1..delta. = 5.08 (--, 1H).delta. = 5.16 (s, 2H).delta. = 5.70 (s, 1H)______________________________________

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:

______________________________________NMR spectrum (.delta. in ppm) IR spectrum (neat)______________________________________.delta. = 1.63 s 3080, 2970, 2925, 1738(s), 1644,.delta. = 1.67 s, 9H 1435, 1384, 1340, 1255, 1166,.delta. = 1.78 s 1130(s), 984, 965, 925, 895,.delta. = 2.20 (s, 3H) 770, 744, 694 cm.sup.-1..delta. = 3.06 (t, 1H).delta. = 5.12 (s, 2H)______________________________________

EXAMPLE 18

Two cheese flavor enhancing compositions were prepared by mixing the following ingredients:

______________________________________ A B______________________________________butyric acid 30 30hexanoic acid 3 3isovaleric acid 3 3octanoic acid 5 52-heptanone 2 2.gamma.-undecalactone 0.5 0.5ethyl lactate 10 10.gamma.-decalactone 0.5 0.5.gamma.-dodecalactone 0.5 0.5acetoin 0.2 0.2diacetyl 0.1 0.1methylcinnamate 0.5 0.5methylthiomethyl hexanoate -- 0.5propylene glycol 944.7 944.2 1000.0 1000.0______________________________________

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:

______________________________________ A B C______________________________________vanillin 16 16 16maltol 16 16 16benzylalcohol 80 80 80linalool 8 8 8isoamyl butyrate 24 24 24ethyl acetate 32 32 32ethyl butyrate 32 32 32ethyl hexanoate 64 64 64ethyl heptanoate 48 48 48methylthiomethyl octanoate -- 2.5 --methylthiomethyl heptanoate -- -- 2.5propylene glycol 680 677.5 677.5 1000.0 1000.0 1000.0______________________________________

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:

______________________________________ A B______________________________________maltol 30 30cis-3-hexenol 0.6 0.6ethyl isovalerate 1 1.gamma.-undecalactone 3 3benzyl butyrate 3 3ethyl butyrate 20 20ethyl acetate 1 1amyl acetate 1 1geranyl acetate 0.1 0.1diacetyl 0.1 0.1.gamma.-nonalactone 0.1 0.1.beta.-terpineol 0.08 0.08Ylang Ylang oil 0.02 0.02Orange oil 0.3 0.3phenylethyl isovalerate 2.2 2.2methylthiomethyl isobutyrate -- 2.5propylene glycol 937.50 935.00 1000.00 1000.00______________________________________

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:

______________________________________ A B C______________________________________acetoin 30 30 30diacetyl 20 20 20vanillin 20 20 20ethyl butyrate 10 10 10maltol 5 5 5.delta.-decalactone 10 10 10ethyl lactate 50 50 50butyric acid 50 50 50hexanoic acid 5 5 5methylthiomethyl propionate -- 2.5 --methylthiomethyl butyrate -- -- 0.5propylene glycol 800 797.5 799.5 1000.0 1000.0 1000.0______________________________________

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:

______________________________________ A B______________________________________ethylmaltol 20 20vanillin 4.5 4.5isopropyl alcohol 300 300mandarin oil 5 5ethyl acetate 3 3orange essence oil 4 42-methylbutyric acid 3.5 3.5cis-3-hexenol 5.5 5.5.gamma.-undecalactone 1 1propylene glycol 653.5 646methylthiomethyl-2-methylbutyrate -- 7.5 1000.0 1000.0______________________________________

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:

______________________________________ A B C______________________________________vanillin 4 4 4angelicaroot oil 6 6 6buchu oil 100 100 100cognac oil (green) 3 3 3mandarin oil 4 4 4petitgrain oil 10 10 10cedar leaf oil 3 3 3isoamyl isovalerate 15 15 15isoamyl butyrate 4 4 4methyl butyrate 20 20 20ethyl butyrate 10 10 10ethyl hexanoate 5 5 5isobutyl acetate 120 120 120methyl isobutyl carbinylacetate 20 20 20ethylbenzoate 5 5 5bornyl acetate 8 8 8citral 2 2 2cuminic aldehyde 3 3 3.beta.-ionone 3 3 3methylthiomethyl valerate -- 10 --methylthiomethyl tiglate -- -- 10propylene glycol 655 645 645 1000.0 1000.0 1000.0______________________________________

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:

______________________________________ A B______________________________________vanillin 4.5 4.5ethylmaltol 20 20tangerine oil 5 5ethyl acetate 3 3benzyl acetate 3 3orange peel oil 4 4bergamot oil 1 12-methylbutyric acid 3.5 3.5cis-3-hexenol 5.5 5.5benzyl alcohol 15 15methylthiomethyl isovalerate -- 5propylene glycol 935.5 930.5 1000.0 1000.0______________________________________

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:

______________________________________ A B______________________________________heliotropin 1 1vanillin 20 20maltol 5 5acetoin 40 40diacetyl 20 20ethyl butyrate 8 8ethyl hexanoate 2 2.gamma.-decalactone 10 10.gamma.-nonalactone 1 1n-butyric acid 40 40hexanoic acid 4 4methylthiomethyl 2-hexenoate -- 5propylene glycol 849 844 1000.0 1000.0______________________________________

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:

______________________________________ A B______________________________________maltol 0.25 0.25cognac oil (green) 0.1 0.1lime oil 0.4 0.4orange oil terpenes 0.8 0.8isoamyl acetate 0.3 0.3fusel oil 2 2ethyl acetate 2 2ethyl butyrate 0.4 0.4lie de vin 0.1 0.1ethyl 2-methylbutyrate 0.3 0.32-methylbutanol 2 2citral 0.05 0.05phenylethyl alcohol 0.25 0.25trans-2-hexenol 0.1 0.1methyl anthranilate 10 6methylthiomethyl lavandulate -- 4propylene glycol 980.95 980.95 1000.0 1000.0______________________________________

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

1. A dairy flavoring composition or a dairy product flavor-enhancing composition containing 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; and at least one other flavoring compound selected from the class consisting of 2-methylbutyric acid, vanillin, maltol, ethyl butyrate, ethyl hexanoate, ethyl isovalerate, delta-decalactone, 2-heptanone, heliotropin, gamma-undecalactone, butyric acid, ethyl lactate, hexanoic acid, gamma-decalactone, gamma-dodecalactone, isovaleric acid, acetoin, octanoic acid and diacetyl.

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 5 to 2000 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 5 to 2000 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.