United States Patent (19) 11 4,332,829 Van Den Bosch Et Al
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United States Patent (19) 11 4,332,829 van den Bosch et al. 45 Jun. 1, 1982 54 METHYLTHIOMETHYL ESTERS AS 58 Field of Search ......................................... 426/535 FLAVOR ADDITIVES 56 References Cited 75) Inventors: Steven van den Bosch, Woudenberg; U.S. PATENT DOCUMENTS Evert van't Land, Terschuur; Jan Stoffelsma, Hoevelaken, all of 3,870,800 3/1975 Pettet et al.............. ... 426/535 Netherlands 3,900,581 8/1975 Wenter et al. .............. 426/535 3,978,240 8/1976 van der Heijden et al........ 426/535 73) Assignee: Polak's Frutal Works, B.V., . Amersfoort, Netherlands OTHER PUBLICATIONS 21 Appl. No.: 231,184 Fenaroli's Handbook of Flavor Ingredients, 2nd Ed., 1975, Edited by Furia et al., CRC Press: Cleveland, pp. 22 Filed: Feb. 2, 1981 132, 133, 185, 202, 207, 208. Primary Examiner-Joseph M. Golian Related U.S. Application Data Attorney, Agent, or Firm-William S. Alexander 63 Continuation-in-part of Ser. No. 52,154, Jun. 26, 1979, abandoned. 57 ABSTRACT 30 Foreign Application Priority Data Methylthiomethyl esters of aliphatic acids have been found useful in imparting or enhancing flavors in food Jul. 18, 1978 GB United Kingdom ............... 3.0161/78 stuffs. They are particularly useful with respect to fruit 51 Int. Cl. ....................... A23L 1/226; A23L 1/235 and berry flavors. 52 U.S. C. .................................... 426/535; 560/222; 560/231; 260/.399 33 Claims, No Drawings 4,332,829 2 METHYLTHOMETHYL ESTERS AS FLAVOR -continued ADDITIVES Methylthiomethyl ester of Organoleptic property valeric acid fruity, cheese, milky isovaleric acid blackcurrant, tropical fruits This application is a continuation-in-part of our co hexanoic acid pineapple, fruity pending application Ser. No. 52,154, filed June 26, 1979, heptanoic acid fruity, pineapple, pear and now abandoned. octanoic acid dairy-like, fruity, cheese This invention relates to the use of methylthiomethyl tiglic acid Sweet apple, fruity 2-hexenoic acid green, cream, earthy, fatty esters of aliphatic acids as flavor additives and to flavor 2-methyl-2-pentenoic acid fruity, pear, sulfury ing compositions and foodstuffs containing such com 10 geranic acid aldehydic, fruity, estery pounds. citronelic acid aldehydic, wine, earthy Food scientists and researches are constantly striving lavandulic acid grape, radish, cabbage to improve or strengthen the flavor and the flavor im pact of foodstuffs by use of flavor additives to replace The methylthiomethyl esters of this invention can be flavor lost by the processing or in storage or to impart 15 employed singly or in admixture of two or more. They a "natural' flavor effect to a reconstituted foodstuff. all can be employed as components either of flavoring Considerable effort is also being put into developing compositions or of flavor-enhancing compositions. flavor compounds and flavoring compositions for im A flavoring composition means a combination of parting flavors to otherwise bland or tasteless, though ingredients compounded to supply or impart a specific nutritionally useful, materials. flavor character to an otherwise bland ingestible mate In accordance with this invention, there are provided rial, or to completely change an existing flavor. A fla flavoring compositions or flavor enhancing composi Vor-enhancing composition is a combination of ingredi tions containing methylthiomethyl esters of aliphatic ents which, in combination, are capable of reinforcing acids, represented by the structural formula R one or more flavor notes of a natural or other foodstuff COOCH2SCH3 wherein R is selected from the group 25 to improve, supplement or augment a flavor which has consisting of hydrogen, alkyl radicals with 1 to 9 carbon been undesirably diminished or otherwise altered by atoms, alkenyl radicals with 2 to 9 carbon atoms and processing or which is inferior due to the general qual polyunsaturated alkyl radicals with 4 to 9 carbon atoms. ity of the foodstuff initially. Either type of composition When R represents one of the above described alkyl is usually suspended or dissolved in an organoleptically groups, the alkyl group can be straight-chain or 30 inert carrier, although this is not absolutely necessary. branched-chain. Some of the compounds presented in When used in fruit or berry flavoring compositions, this invention exist in isomeric forms, and the com additional flavoring compounds typically used in com pounds given herein include such isomers and mixtures thereof. bination with the methylthiomethyl esters of the inven Although some of the compounds used in the present 35 tion include, e.g. invention are known in literature, there is no disclosure in the prior art indicating that they possess flavoring orange oil isoamyl acetate properties. The following methylthiomethyl esters of phenyl ethyl isovalerate fusel oil damascenone lie devin the aliphatic series are known from the chemical litera ethyl maltol 2-methylbutanol ture: the acetate, the propionate, the octanoate, the 40 2-methylbutyric acid phenylethyl alcohol acrylate, and the methacrylate (see e.g., Chem. Abstr., angelica root oil trans-2-hexenol buchu oil methyl anthranilate 83, 192168U, Tetrah. Letters, 1972, 4941-4, J. Amer. cognac oil 2-methyl-2-pentenoic acid Chem. Soc., 92,6521-5 (1970), Tetrahedron, 19, 817-20 petitgrain oil vanilin (1963), Can. J. Chem. 42,2357-62 (1964), Chem. Abstr., cedar leaf oil malto 59, 3806g, Ann., 626, 19-25 (1959), Syn. Comm., 3, 45 isoamyl isovalerate benzyl alcohol methylbutyrate linaolool 145-6 (1973), J.C.S. Chem. Comm., 1973, 224-5, Chem. isobutyl acetate isoamylbutyrate Abstr., 72, 54677f, and J. Amer. Chen. Soc., 91, 682-7 methyl isobutyl carbinyl ethyl acetate (1969)). acetate ethylbutyrate As stated, the methylthiomethyl esters of this inven ethylbenzoate ethylhexanoate 50 citral ethylheptanoate tion exhibit a wide variety of flavor effects giving rise to cuminic aldehyde cis-3-hexenol a wide field of uses. In particular, they are useful in fruit beta-ionone ethyl isovalerate flavors, e.g., pineapple, strawberry, raspberry, black tangerine oil phenylbutyrate currant, mango, durian, grape, apple, peach, pear, and benzyl acetate amyl acetate orange peel oil geranyl acetate other fruit and berry flavors. The esters are also useful 55 bergamot oil gamma-nomalactone in cheese, cream, milk, meat, and vegetable flavors. line oil Yiang Ylang The following table illustrates some of the great vari orange terpenes beta-terpineol ety of flavor effects exhibited by the compounds pres methyl cinnamate ented in the invention. When used in dairy type flavors-i.e., cheese, butter, Methylthiomethyl ester of Organoleptic property or cream flavors, additional flavoring compositions formic acid cabbage, meaty, onion, metallic typically used in combination with the methylthi acetic acid estery, milky, cabbage, meat, omethyl esters of the invention include: sulfury propionic acid dairy-like, yoghurt, sulfury 65 butyric acid cabbage, milky, cheese delta-decalactone 2-heptanone isobutyric acid strawberry, pineapple heliotropin gamma-undecalactone 2-methylbutyric acid fruity, strawberry, pineapple, butyric acid ethyl lactate mango, durian hexanoic acid gamma-decalactone 4,332,829 3 4. -continued EXAMPLE 2 octanoicisovaleric acid acid diacetylacetoin Preparation of Methylthiomethyl Formate This product was prepared according to the proce The term “foodstuff includes both solid and liquid dure described in Example 1, by reacting formic acid ingestible materials which usually do, but need not, with chloromethyl methylsulfide in the presence of one have nutritional value. Thus, foodstuffs include fruit equivalent of triethylamine; b.p. 35 C/12 mm Hg, juices, fruit flavored beverages, puddings, jellies, nD20 1.4650. pastries, ice cream, candies, chewing gum, dairy prod 10 Spectral data of the compound: ucts, vegetables, cereals, meats, soups, convenience foods and the like. They can also be employed to restore NMR spectrum (8 in ppm) IR spectrum (neat) the fresh fruit effect of canned and frozen fruits. 8 = 2.26 (s, 3H) 2925, 1720, 1430, 1310, 262, The amount of methylthiomethyl ester added to a 6 = 5.22 (s, 2H) 1130, 1010, 909, 870, 750, 694 foodstuff needs to be only the amount sufficient to im 15 8 = 8.11 (t, 1H) 429 cm. part 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. EXAMPLE 3 Generally, the amount will be between about 0.1 to 5 Preparation of Methylthiomethyl Acetate parts per million by weight based on the foodstuff being This product was prepared according to the proce flavored. dure described in Example 1, by reacting acetic acid To prepare the methylthiomethyl esters described in with chloromethyl methylsulfide in the presence of one this invention, the corresponding acid is reacted with equivalent of triethylamine; b.p. 45-46 C./12 mm Hg, chloromethyl methyl sulfide in the presence of one 25 n20 1.4570. equivalent of an amine, for example, triethylamine (T. Spectral data of the compound: L. Ho and C. M. Wong, J. Chem. Soc. Chem. Comm., 1973, 224-225). The following examples are intended to illustrate the NMR spectrum (6 in ppm) IR spectrum (neat) invention, but not to limit the same in any way. 30 8 = 2.07 (s, 3H) 2925, 1740(s), 1426, 1369, 1310, 8 = 2.12 (s, 3H) 1210(s), 1018, 1008, 960, 910, EXPERIMENTAL PART 8 = 5.10 (s, 2H) 812, 749, 697, 600, 462 cm. NMR spectra were recorded on a JEOL FX-100 instrument as solutions in CDCl3 with tetramethylsilane EXAMPLE 4 as internal standard. 35 IR spectra were measured with a Perkin-Elmer 225 Preparation of Methylthiomethyl Propionate Spectrophotometer, neat or as solutions in CCl4. This product was prepared according to the proce dure described in Example 1, by reacting propionic acid EXAMPLE 1. with chloromethyl methylsulfide in the presence of one Preparation of Methylthiomethyl Hexanoate 40 equivalent of triethylamine; b.p. 58-59 C./12 mm Hg, In a three-necked 1000 ml. round-bottomed flask nD20 1.4548. fitted with a mechanical stirrer, thermometer and reflux Spectral data of the compound: condenser is placed 63.8 g.