' United States Patent 1191 [11] 4,241,098 Mussinan et al. [45] Dec. 23, 1980

[54] FLAVORING WITH A MIXTURE OF [58] Field of Search ...... 426/534; 568/421 CIS-3-HEXENAL, TRANS-Z-HEXENAL, CIS-3-HEXENYL FORMATE, [56] References Cited CIS-S-HEXENOL AND PUBLICATIONS CIS-S-HEXENYL-CIS-S-HEXENOATE Aretander Perfume and Flavor Chemicals, vol. I, 1969, [75] Inventors: Cynthia J. Mussinan, Bricktown; Publ. by the Author-Montclair, N.J., Items No. 1598, Braja D. Mookherjee, Holmdel; 1599, 1604, 1617, 1620. Manfred H. Vock, Locust; Frederick L. Sehmitt, Holmdel; Edward J. Primary Examiner-Joseph M. Golian Granda, Englishtown; Joaquin F. Attorney, Agent, or Firm—Arthur L. Liberman Vinals, Red Bank, all of N.J.; Jacob [s7] . ABSTRACT Kiwala, Brooklyn, NY. ' Described is a method for augmenting or enhancing the [73] Assignee: International Flavors & Fragrances aroma or ?avor of a foodstuff comprising adding to the Inc., New York, NY. foodstuff from 0.05 up to about 500 parts per million of [21] Appl. No.: 85,707 a mixture of cis-3-hexenal, trans-2-hexena1, cis-3-hexe nyl formate, cis-3-hexenol and cis-3-hexenyl-cis-3—hex [22] Filed: Oct. 17,1979 enoate prepared by the process of reacting cis-3-hexenol [s1] rm. c1.3 ...... A23L 1/226 with pyridinium chlorochromate. [52] us. c1.‘ ...... 426/534; 568/421; , 131/17 R; 252/522 R ' 1 Claim, 15 Drawing Figures U.S. Patent Dec. 23, 1980 Sheéet 1 0f 15 4,241,098

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GLC 'PROFILE (TRAP) FOR EXAMPLE III. 4,241,098 1 2 GRAS list as FEMA No. 2561. Prior to our invention, FLAVORING WITH A MIXTURE OF however, the dif?culty with using cis-3-hexenal was CIS-S-I-IEXENAL, TRANS-2-HEXENAL, that it easily decomposes in the presence of oxygen. CIS-3-IPIEXENYL FORMATE, CIS-3-HEXENOL Thus a more stable form of cis-3-hexenal has been de . AND CIS-3-HEXENYL-CIS-S-HEXENOATE 5 sired in the ?avor and fragrance industries since the discovery of said cis-3-hexenal several decades ago. BACKGROUND OF THE INVENTION Kajiwara, Harada and Hatanaka indicated that cis-3 The present invention relates to cis-3-hexenyl deriva hexenal may be isolated from tea leaves (Thea Sinensis) tives having the generic structure: in Agr. Biol. Chem., 39 (1), 243-247, 1975. It was indi cated by Kajiwara et al, that cis-3-hexenal can be pro duced by oxidizing cis-3-hexenol using chromium ox R ide-pyridine mixture in the presence of methylene di chloride or dimethylsulfoxide-phosphorous pentoxide wherein R is one of the moieties: 15 mixture. Such oxidizing agents as pyridinium chlorochromate having the structure:

20

\ CrO3Cl H 25 produced by the novel processes of our invention and to have never been disclosed to be useful in oxidizing novel compositions using one or more of such cis-3 cis-3-hexenol to produce cis-S-hexenal in admixture hexenyl derivatives to augment, modify or enhance the with other compounds whereby the mixture is stable ?avor and/or aroma of consumable materials or impart particularly with respect to the substantivity of the ?avor and/or aroma to consumable materials. There has been considerable work performed relating 30 cis-3-hexenal, The pyridinium chliorochromate having to substances which can be used to impart (modify, the structure: augment or enhance) ?avors and fragrances to (on in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply, and to provide more 35 uniform properties in the ?nished product. Sweet, deep green, crushed leaf-like, fruity, pear-like, green apple-like, fresh fig-like, winey and white grape CrO3Cl H like aroma and ?avor notes are particularly desirable in many foodstuff ?avors, chewing gum ?avors, tooth~ has, however, been disclosed as an oxidizing agent by paste ?avors and medicinal product ?avors, particu Corey and Suggs in Tetrahedron Letters No. 31, pages larly in the oral hygiene area. 2647-2650, 1975 (“Pyridinium chlorochromate. An Powerful green, leafy, fruity, fatty and spicy aromas Ef?cient Reagent for Oxidation of Primary and Second with strong crushed green undertones are desirable in ary Alcohols to Carbonyl Compounds”). l-Heptanol is several types of perfume compositions, perfumed arti 45 disclosed to be able to be oxidized to heptanal using cles (e.g. anionic, cationic and nonionic detergents and pyridinium chlorochromate, by Corey and Suggs. Also, dryer-added fabric softener articles) and colognes. citronellol is disclosed by Corey and Suggs to be able to Sweet, fruity, cooling and green aromas and tastes are be oxidized to in an 82% yield using pyridin desirable in connection with augmenting or enhancing ium chlorochromate. the ?avors or aromas of smoking tobaccos both prior to 50 Japanese published patent application No. J5 4012 smoking and on smoking in both the mainstream and the 309 discloses 3-hexynyl-alkylethers as long lasting per sidestream. fuming agents and useful as an intermediate for the The book “Perfume and Flavor Chemicals (Aroma Chemicals)” by Stephen Arctander at Monograph 1598 synthesis of cis-3-hexenyl ethers or pheromones. Japa discloses cis-3-hexenal to have a powerful deep green, 55 nese patent disclosure No. J5 4012 309 does not, how leafy odor reminiscent of strawberry leaf and wine leaf, ever, disclose the unobvious, unexpected and advanta freshly crushed. Arctander further states that cis-3 geous organoleptic properties of cis-3-hexenyl methyl hexenal is occasionally used in perfume compositions as ether. part of a “green” topnote complex not only for herba BRIEF DESCRIPTION OF THE DRAWINGS ceous fragrance types but also in various ?oral composi tions. The concentrations, Arctander states, will nor FIG. 1 sets forth the GLC pro?le for the reaction mally be less than 0.1% in the perfume oil. Arctander . product of Example I. further states that cis-3-hexenal is used in ?avor compo FIG. 2 sets forth the GLC pro?le for the reaction sitions in minute traces to introduce a natural green note product of Example II. in many types of fruit ?avors. Arctander states that 65 FIG. 3 sets the NMR spectrum for cis-3-hexen-l-ol concentrations in the ?nished product of cis-3-hexenal produced according to Example II. may be about 0.2 to 0.5 ppm. Cis-3-hexenal is stated to FIG. 4 sets forth the mass spectrum for cis-3-hexen-l be produced by oxidation of hexenol and is on the 01 produced according to Example II. 4,241,098 3 FIG. 5 sets forth the NMR spectrum for the cis-3 hexenal produced according to Example II. FIG. 6 sets forth the mass spectrum for cis-3-hexenal produced according to Example II. FIG. 7 sets forth the NMR spectrum for trans-Z-hexe 5 nal produced according to Example II. wherein R is one of the moieties: FIG. 8 sets forth the mass spectrum for trans-Z-hexe nal produced according to Example II.‘ FIG. 9 sets forth the NMR spectrum ‘for cis-3-hexe i‘ nyl formate produced according to Example II. 10 (I: _ 0 _ CH3 or FIG. 10 sets forth the mass spectrum for cis-3-hexe H nyl formate produced according to Example II. FIG. 11 sets forth the NMR spectrum for cis-3-hexe 0 nyl-cis-S-hexenoate ‘produced according to Example II. Cf H FIG. 12 sets forth the mass spectrum for cis-3-hexe 15 nyl-cis-3-hexenoate produced according to Example II. FIG. 13 sets forth the infrared spectrum for cis-3 The cis-3-hexenyl derivatives of our invention aug hexenyl-cis-3-hexenoate produced according to Exam ment or enhance sweet, deep green, fruity, pear-like, ple II. green apple-like, fresh ?g-like, winey, white grape-like FIG. 14 sets forth the GLC pro?le for the cis-3-hexe 20 and crushed leaf ?avor characteristics insofar as aug nyl-methylether produced according to Example III as menting or enhancing the aroma or taste of foodstuffs, separated on a GLC column (500 ft.><0.03 in., SF 96 toothpastes, medicinal products and chewing gums. coated column; programmed at 80°-l90° C. at 4° C. per The cis-3-hexenyl derivatives of our invention also minute) after distillation using a rotary evaporator. augment or enhance the powerful green, leafy, fruity, FIG. 15 sets forth the GLC pro?le for cis-3-hexenyl 25 fatty and spicy aromas and crushed green leaf under methylether as trapped out from the 500 ft.>< 0.03 in. tones of perfumes, perfumed articles and colognes of SF-96 column programmed at 80°—190° C. at 4° C. per our invention. minute. The cis-3-hexenyl derivatives 'of our invention also augment or enhance the sweet, fruity, cooling and THE INVENTION 30 green aroma characteristics of smoking tobacco prior to It has now been determined that certain cis-3-hexenyl and on smoking in both the mainstream and the side derivatives are capable of imparting a variety of ?avors stream. and fragrances to various consumable materials and are Examples of the cis-3-hexenyl derivatives and mix also capable of augmenting or enhancing a variety of tures thereof of our invention and their organoleptic ?avors and fragrances of various consumable materials. characteristics are as follows: TABLE I Structure Fragrance Mixture of Compound or Mixture Flavor Characteristics: Characteristics: Tobacco Characteristics:

- / 0 Mixture containing Intense crushed green Powerful green, fruity, A sweet, fruity, cooling MC: ; 33.1% cis-S-hexenal; leaf aroma and taste fatty, spicy aroma with green aroma prior to H 20.8% of trans-2- which is very long leaf alcohol nuances and and on smoking in the hexenal; 5.5% of lasting; much longer an intense very stable mainstream and the side éQ cis-3-hexenyl formate lasting than cis-3-hexenal natural green note. stream. /W(J\ ; and 26.1% of eis-3- taken alone and Stability about 100 times H hexenyl-cis-3- examined previously. that of cis-3-hexenal. hexenoate. MOV H; and ll 0

O /\=/\/ \/\=/\ ll 0 O\ Cis-3-hexenyl methyl A sweet, green, fruity, Grassy, green aroma A sweet, fruity, cooling CH3 ether. pear, green apple-like, with fruit topnote and and green aroma fresh ?g-like aroma and jasmine-like undertone. characteristic prior to taste characteristic at and on smoking in both lppm. Suitable for the mainstream and the fresh ?g, apple, peach sidestream. and oral hygiene ?avors.

60 Indeed the value of cis-3-hexenyl methylether has been demonstrated for various ?avors: Brie?y, our invention contemplates augmenting or A. In strawberry ?avor cis-3-hexenyl methylether at enhancing the ?avors and/or fragrances of such con 0.01% adds a fresh fruit character both in aroma and sumable materials as perfumes, perfumed articles, co taste. lognes, foodstuffs, chewing gums,._toothpastes, medici- 65 B. In pineapple ?avor cis-3-hexenyl methyl ether at nal products and smoking tobaccos by adding thereto 0.05% gives a fresh pineapple character depressing small but effective amount of at least one compound the canned notes and creates a substantially more having the generic structure: pleasant and more intense aroma. 4,241,098 I 5 6 C. In peach ?avor at 0.02% cis-S-hexenyl methyl ether ‘ imparts freshness and a natural peach character of great intensity. \ D. In peppermint oil (natural), cis-3-hexenyl methyl Mon + (j CHZClZ ether at the rate of 0.05% gives an aroma lift, a 5 ’ / N fresher character both in aroma and taste. Indeed, / cis-3-hexenyl methylether is essential in the creation of arti?cial peppermint ?avors and for oral hygiene products. E. In raspberry ?avor cis-3-hexenyl methylether at 0.01% adds and enhances the seedy/green kernel notes both in aroma and taste and rounds out the , ?avor making it fuller and more natural like. An important aspect of this invention is the creation of crushed leaf aroma and taste of a very high stability of a new composition of matter containing cis-3-hexe nal. This composition of matter not only contains cis-3 hexenal having the structure: - The mole ratio of cis-3-hexenolzpyridinium chlorochro mate initially in the reaction mass may vary from 1:0.5 20 up to 1:2 with a preferred mole: ratio of cis-S-hexenol M pyridinium chlorochromate of 1:1.5. It is preferred that C the reaction be carried out in a solvent such as methy lene chloride. The concentration of cis-3-hexenol in the methylene chloride is from about 0.2 up to about 1.5 but in addition contains cis-3-hexenyl formate and/or 25 moles per liter with a preferred concentration of cis-3 cis-3-hexenol; and trans-Z-hexenal; and cis-3-hexeny1 hexenol in the methylene chloride of 0.5 M. cis-3-hexenoate. Trans-Z-hexenal has the structure: Cis-3-hexenol is also used to prepare with cis-3-hexe nyl methylether by reaction of cis-3-hexenol with an etherifying agent such as sodium. hydride and methylio dide. The reactions can be carried out in the presence of dimethylformamide or diethylbenzene according to the following reaction scheme: cis-3-hexenyl formate has the structure:

35 /\—;/\/ O \u/ H 0

cis-3-hexenyl cis-3-hexenoate has the structure: 40

0 II o 45 Thus, the quantities of substances in the composition of our invention which contains the cis-3-hexenal are as The reaction wherein cis-3-hexenol is oxidized to the follows: composition of matter containing the cis—3-hexenal Cis-3-hexenal from 20% up to 80%; using the pyridinium chlorochromate may be carried Trans-Z-hexenal from 5% up to 40%; 50 out also according to the conditions as speci?ed in the Cis-S-hexenyl formate from 0% up to 20%; paper by Corey and Suggs, Tetrahedron Letters, No. Cis-3-hexenol from 0% up to 40%; 31, pages 2647-2650, 1975 (Title: “Pyridinium Chloro chromate; an Ef?cient Reagent for Oxidation of Pri Cis-3-hexenyl-cis-3-hexenoate from 1% up to 10%; mary and Secondary Alcohols to Carbonyl Com the percentages being “mole” percentages. 55 pounds”). The foregoing mixture is useful in all fruit ?avors, When the cis-S-hexenyl derivatives of our invention vegetable ?avors, savory ?avors and many others. This are used as food ?avor adjuvants, the nature of the mixture can prepared by reacting cis-S-hexenol with co-ingredients included with said cis-3-hexenyl deriva pyridinium chlorochromate having the structure: tives in formulating the product composition will also serve to alter, modify, augment or enhance the organo leptic characteristics of the ultimate foodstuff treated therewith. As used herein in regard to ?avors, the terms “alter”, I “modify” and “augment” in their various forms means “supplying or imparting ?avor character or note to CrO3Cl otherwise bland, relatively tasteless substances or aug menting the existing ?avor characteristic where a natu according to the reaction sequence: ral ?avor is de?cient in some regard or supplementing 4,241,098 7 8 the existing ?avor impression to modify its quality, the like; buffers and neutralizing agents, e.g., sodium character or taste”. acetate, ammonium bicarbonate, ammonium phosphate, The term “enhance” is used herein to mean the inten citric acid, lactic acid, vinegar and the like; colorants, si?cation of a ?avor or aroma characteristic or note e. g., carminic acid, cochineal, tumeric and curcuma and without the modi?cation of the quality thereof. Thus, the like, ?rming agents such as aluminum sodium sul “enhancement” of a ?avor or aroma means that the fate, calcium chloride and calcium gluconate; texturiz enhancement agent does not add any additional ?avor ers, anti-caking agents, e.g., aluminum calcium sulfate note. and tri-basic calcium phosphate; enzymes; yeast foods, As used herein, the term “foodstuff” includes both e.g., calcium lactate and calcium sulfate; nutrient sup solid and liquid ingestible materials which usually do, plements, e.g., iron salts such as ferric phosphate, fer but need not, have nutritional value. Thus, foodstuffs rous gluconate and the like, riboflavin, vitamins, zinc include soups, convenience foods, beverages, dairy sources such as zinc chloride, zinc sulfate and the like. products, candies, vegetables, cereals, soft drinks, Other ?avorants and ?avor intensi?ers include or snacks, and the like. ganic acids, e.g., acetic acid, formic acid, 2-hexenoic The term “chewing gum” is intended to mean a com acid, benzoic acid, n-butyric acid, caproic acid, caprylic position which comprises a substantially water insolu acid, cinnamic acid, isobutyric acid, isovaleric acid, ble, chewable plastic gum base such as chicle, or substi alpha-methylbutyric acid, propionic acid, valeric acid, tutes therefor, including jelutong, guttakay rubber or Z-methyI-Z-pentenoic acid, and 2-methyl-3-pentenoic certain comestible natural or synthetic resins or waxes. acid;,ketones and aldehydes, e.g., acetaldehyde, aceto Incorporated with the gum base in admixture therewith phenone, acetone, acetyl methyl carbinol, acrolein, may be plasticizers or softening agents, e.g., glycerine, n-butanal, crotonal, diacetyl, Z-methylbutananl, beta, and a ?avoring composition which incorporates one or beta-dimethyl acrolein, methyl n-amyl ketone, n-hexa more of the cis-3-hexenyl derivatives of our invention, nal, 2-hexenal, isopentanal, hydrocinnamic aldehyde, and in addition, sweetening agents which may be sug Z-heptenal, nonyl aldehyde, 4-(p-hydroxyphenyl)-2 ars, including sucrose or dextrose and/or arti?cial 25 butanone, alpha-ionone, beta-ionone, 2-methyl-3-buta- , sweeteners such as cyclamates or saccharin. Other op none, benzaldehyde, beta-damascone, alpha-damas tional ingredients may also be present. cone, beta-damascenone, acetophenone, Z-heptanone, Substances suitable for use herein as co-ingredients or o-hydroxy-acetophenone, 2-methyl-2-hepten-6-one, 2 ?avoring adjuvants are well known in the art for such octanone, 2-undecanone, 3-phenyl-4-pentenal, 2-phe use, being extensively described in the relevant litera nyl-2-hexenal, 2-phenyl-2-pentenal, furfural, S-methyl ture. It is a requirement that any such material be “ing furfural, cinnamaldehyde, beta-cyclohomocitral, 2-pen estibly” acceptable and thus non-toxic and otherwise tanone, Z-pentenal and propanal; alcohols such as l non-deleterious particularly from an organoleptic butanol, benzyl alcohol, l-borneol, trans-Z-buten-l-ol, standpoint whereby the ultimate ?avor and/or aroma of ethanol, , l-hexanol, Z-heptanol, trans-2-hex the consumable material used is not caused to have enol-l, 3-methyl-3-buten-l-ol, l-pentanol, ,l-penten-S unacceptable aroma and taste nuances. Such materials ol, p-hydroxyphenyl-Z-ethanol, isoamyl alcohol, iso may in general be characterized as ?avoring adjuvants fenchyl alcohol, phenyl-2-ethanol, alpha-terpineol, cis or vehicles comprising, broadly, stabilizers, thickeners, terpinhydrate, eugenol, linalool, Z-heptanol, acetoin; surface active agents, conditioners, other ?avorants and esters, such as butyl acetate, ethyl acetate, ethyl aceto ?avor intensi?ers. acetate, ethyl benzoate, ethyl butyrate, ethyl caprate, Stabilizer compounds include preservatives, e.g., ethyl caproate, ethyl carpylate, ethyl cinnamate, ethyl sodium chloride; antioxidants, e.g., calcium and sodium crotonate, ethyl formate, ethyl isobutyrate, ethyl isoval~ ascorbate, ascorbic acid, butylated hydroxyanisole erate, ethyl laurate, ethyl myristate, ethyl alpha-methyl (mixture of 2- and 3-tertiary-butyl-4-hydroxy anisole), butyrate, ethyl propionate, ethyl salicylate, trans-2 butylated hydroxytoluene (2,6-di-tertiary-butyl-4 hexenyl acetate, hexyl acetate, Z-hexenyl butyrate, methyl phenol), propyl gallate and the like, and seques hexyl butyrate, isoamyl acetate, isopropyl butyrate, trants, e.g., citric acid. ‘ methyl acetate, methyl butyrate, methyl caproate, Thickener compounds include carriers, binders, pro methyl isobutyrate, alpha-methylphenylglycidate, ethyl tective colloids, suspending agents, emulsi?ers and the succinate, isobutyl cinnamate, cinnamyl formate, like, e. g., agar agar, carrageenan; cellulose and cellulose methyl cinnamate, and terpenyl acetate; hydrocarbons derivatives such as carboxymethyl cellulose and methyl such as dimethyl naphthalene, dodecane, methyldiphe cellulose; natural and synthetic gum such as gum arabic, nyl, methyl naphthalene, , naphthalene, octa gum tragacanth; gelatin, proteinaceous materials; lipids, decane, tetradecane, tetramethylnaphthalene, tridec carbohydrates; starches, pectins, and emulsi?ers, e.g., ane, trimethylnaphthalene, undecane, caryophyllene, mono- and diglycerides of fatty acids, skim milk pow 55 alpha-phellandrene,- beta-phellandrene, p-cymene,l der, hexoses, pentoses, disaccharides, e. g., sucrose, corn alpha-pinene, beta-pinene, dihydrocarveol; pyrazines syrup and the like. such as 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, Surface active agents include emulsifying agents, e. g., 2,6-dirnethylpyrazine, 3-ethyl-2,S-dimethylpyrazine, fatty-acids such as capric acid, caprylic acid, palmitic 2-ethyl-3,5,6-trimethylpyrazine, 3-isoamyl-2,5-dime acid, myristic acid and the like, mono- and diglycerides 60 thylpyrazine, 5-isoamyl-2,3-dimethylpyrazine, 2-isoa of fatty acids, lecithin, defoaming and ?avor-dispersing . myl-3,5,6-trimethylpyrazine, isopropyl dimethylpyra agents such as sorbitan monostearate, potassium stea zine, methyl ethylpyrazine, tetramethylpyrazine, trime rate, hydrogenated tallow alcohol and the like. thylpyrazine; essential oils such as jasmine absolute, Conditioners include compounds such as bleaching cassia oil, cinnamon bark oil; black pepper oleoresin, oil and maturing agents, e.g., benzoyl peroxide, calcium of black pepper, rose absolute, orris absolute, oil of peroxide, hydrogen peroxide and the like; starch modi cubeb, oil of coriander, oil of pimento leaf, oil of pa ?ers such as peracetic acid, sodium chlorite, sodium tchouli, oil of nutmeg, lemon essential oil, safran oil, hypochlorite, propylene oxide, succinic anhydride and Bulgarian rose, capsicum, yara yara and vanilla; lac