# Patent

## Title
Dry mix for bread

## Abstract

This application is a divisional of application for U.S. patent Ser. No. 496,664 filed on May 20, 1983 now U.S. Pat. No. 4,425,365 issued on Jan. 10. 1984 which, in turn, is a divisional of application for U.S. patent Ser. No. 396,485 filed on July 8, 1982 now U.S. Pat. No. 4,424,378 issued on Jan. 3, 1983 which, in turn, is a continuation-in-part of application for U.S. patent Ser. No. 362,237 filed on Mar. 26, 1982 now U.S. Pat. No. 4,428,387 issued on Jan. 31, 1984.

## Background
This invention relates to the use of novel methyl substituted pinyl oxopentenes defined according to the generic structure: ##STR1## and the generic structure: ##STR2## wherein Z represents methylidene defined according to the structure: ##STR3## ethylidene defined according to the structure: ##STR4## or ethylenyl defined according to the structure: ##STR5## wherein one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents no bond; wherein n is 0 or 1 and m is 0 or 1 with the sum of n+m being equal to 1; wherein X represents carbinol having the structure: ##STR6## or ketone having the structure: ##STR7## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; with the provisos that: position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR8## or ethylenyl having the structure: ##STR9## (ii) when one of R.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR10## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and

and wherein one of the lines: ##STR11## represents a carbon-carbon double bond and the other of the line: ##STR12## represents a carbon-carbon single bond; and uses thereof in augmenting or enhancing the aroma or taste of consumable materials.

Materials which can provide sandalwood-like, urine-like and musky aromas with floral and muguet undertones are desirable and are known in the art of perfumery. Many of the natural materials which provide such fragrances and such desired nuances to perfumery compositions and perfumed articles are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.

By the same token, materials which can provide ionone-like, raspberry-like, oriental, floral, violet, musky and fruity aromas with sweet, ionone-like, raspberry, fruity and lactonic tastes are desirable and are well known in the art of flavoring for foodstuffs, toothpastes, chewing gums, medicinal products and chewing tobaccos. Many of the natural materials which provide such flavor notes and contribute such desired nuances to flavor and to compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.

By the same token, materials which can provide sweet, woody, oriental, ionone-like, sandalwood-like, patchouli-like and cigar box-like aroma and taste nuances to smoking tobacco or smoking tobacco article components both prior to smoking and on smoking in the main stream and in the side stream are highly desirable and are well known in the art of flavoring for smoking tobacco and components for smoking tobacco articles such as filters and wrappers. Many of the natural materials which provide such aroma and taste nuances and contribute the desired nuances to tobacco flavoring compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.

Artificial flavoring agents for foodstuffs have received increasing attention in recent years. For many years such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates and the like are often subject to wide variations due to changes in quality, type and treatment of the raw materials. Such variations can be reflected in the end products and result in unfavorable flavor characteristics in said end product, for example, blackberry, peach and tropical fruit flavored foodstuffs. Additionally, the presence of the natural product in the ultimate food may be undesirable because of increased tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, sausages, gravies and the like are apt to be stored prior to use.

The fundamental problem in creating artificial flavor agents is that the artificial flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many foods, medicinal products, chewing gums and toothpastes is not completely known. This is particularly noticeable in products having blackberry, peach and tropical fruit characteristics particularly.

Even more desirable are products which can serve to substitute for difficult to obtain natural perfumery oils and, at the same time, substitute for natural flavoring ingredients in foodstuffs, chewing gums, medicinal products, toothpastes, chewing tobaccos, and smoking tobaccos.

Pinyl pentenol derivatives are known in the art for having sandalwood aromas. Thus, the compound having the structure: ##STR13## is shown to be prepared according to German Offenlegungsschrift No. 2708048 which, generically, discloses synthesis of compounds defined according to the structure: ##STR14## wherein R.sub.1 and R.sub.2 taken together can represent dimethyl bicyclo[3.1.1] heptyl; R.sub.3 represents alkyl; R.sub.4 represents alkyl and Y represents a divalent aliphatic group with at least four carbon atoms. Thus, German Offenlegungsschrift No. 2708048 discloses the reaction sequence, starting with pinene and ending up with a tertiary pentenol thusly: ##STR15## None of the chemicals produced using the process of our invention are tertiary alcohols and the chemicals produced according to the process of our invention are not considered to be similar from a chemical and organoleptic standpoint to the compounds of German Offenlegungsschrift No. 2708048.

German Offenlegungsschrift No. 2708048 is abstracted at Volume 87, 1977, 184084f of Chemical Abstracts.

Himmele and Siegel, Tetrahedron Letters No. 12, pages 907-910, 1976 in the paper entitled "Hydroformylierung Von Alpha-Pinen" discloses the reaction sequence, starting with alpha pinen first going to a carboxaldehyde according to the reaction sequences: ##STR16##

German Offenlegungsschrift No. 2849742 abstracted in Chem. Abstracts 1981, No. 186613a (Hagen and Bruns) published May 22, 1980  discloses the hydroformylation of monocyclic or bicyclic terpenes with at least one double bond in the presence of a rhodium complex containing triphenylphosphine at 70.degree.-160.degree. C. at 100-400 bar to give the corresponding terpenecarboxaldehydes and alleges that these terpenecarboxaldehydes are useful as perfume ingredients. Specifically, Hagen and Bruns state that 3,3-dimethyl-2-norbornane acetaldehyde and 10-formylpinane are prepared from camphene or beta-pinene. Furthermore, U.S. Pat. No. 3,716,498 issued on Feb. 13, 1973 indicates that such compounds as 6,6-dimethyl-bicyclo[3.1.1]hept-2-ene-2-propionaldehyde are capable of augmenting or enhancing the aroma of perfume compositions, for example, in order to give "fresh air qualities" to Foin Coupe cologne blends. Cosmetic Technology, April 1981 at page 18 states that Sandalore.RTM. manufactured by the Givaudan Corporation of Clifton, N.J. is a useful sandalwood fragrance and has approximately twice the amount of odor intensity of sandalwood oil. Sandalore.RTM.  is a mixture of compounds defined according to the structures: ##STR17##

Application for U.S. patent Ser. No. 391,592 filed on June 24, 1982, now U.S. Pat. No. 4,390,434 issued on June 28, 1983 describes the compound, 4-methyl-3-cyclohexene-1-carboxylic acid having the structure: ##STR18## and uses thereof in augmenting or enhancing the aroma of perfume compositions, perfumed articles and colognes, particularly as a replacement for cumin oil and/or cumin aldehyde and the combination of this compound with compounds which yield sweaty, animal, leathery notes defined according to the genera having the structures: ##STR19## wherein R represents t-butyl or t-amyl as more particularly described in U.S. Pat. No. 3,702,343 issued on Nov. 7, 1972. The use of the mixtures of compounds disclosed in application for U.S. patent Ser. No. 391,592 filed on June 24, 1982, now U.S. Pat. No. 4,390,434 issued on June 28, 1983 in combination with the methyl substituted pinyl oxopentenes of our invention is also contemplated within the scope of our invention.

Nothing in the prior art, however, sets forth the products, processes or unique uses of the compositions of matter of our invention. Indeed, the compositions of matter of our invention either as mixtures or products per se, have unexpected, unobvious and advantageous properties over remotely similar compounds set forth in the prior art, for example, the compounds of the German Offenlegungsschrift No. 2708048.

United Kingdom Specification No. 1,471,856 published on Apr. 27, 1977 discloses the reaction sequence: ##STR20## wherein K' represents the catalyst having the structure: ##STR21##

The products produced according to U.K. Specification No. 1,471,856 are structurally dissimilar from the products of the instant invention.

The present invention provides the compounds defined according to the generic structure: ##STR22## as well as compounds defined according to the structure: ##STR23## wherein Z represents methylidene defined according to the structure: ##STR24## ethylidene defined according to the structure: ##STR25## or ethylenyl defined according to the structure: ##STR26## wherein one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents no bond; wherein n is 0 or 1 and m is 0 or 1 with the sum of n+m being equal to 1; wherein X represents carbinol having the structure: ##STR27## or ketone having the structure: ##STR28## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; with the provisos that: position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR29## or ethylenyl having the structure: ##STR30## (ii) when one of R.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR31## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and

wherein one of the lines: ##STR32## is a carbon-carbon double bond and the other of the lines: ##STR33## is a carbon-carbon single bond.

The present invention also provides an economical, efficient process for synthesizing the compounds having the generic structure: ##STR34## as well as compounds defined according to the structure: ##STR35## by reacting alpha pinene defined according to the structure: ##STR36## or beta pinene having the structure: ##STR37## or a mixture of alpha pinene and beta pinene defined according to the structure: ##STR38## wherein one of the wavy lines:

is a carbon-carbon double bond and the other of the wavy lines is a carbon-carbon single bond with a mixture of carbon monoxide and hydrogen to produce a mixture of aldehydes defined according to the structure: ##STR39## taken together with the compound having the structure: ##STR40## wherein in the mixture one of the dashed lines at the 7-5 or 7-4 positions represents a carbon-carbon single bond and the other of the dashed lines at the 7-5 or 7-4 position represents no bond; wherein one of R.sub.3 or R.sub.4 represents hydrogen and the other of R.sub.3 or R.sub.4 represents hydrogen or methyl; wherein m=0 or 1 and n=0 or 1 with the sum of m+n being equal to 1; wherein A and B each represents methylene defined according to the structure: ##STR41## wherein p=0 or 1 and q=0 or 1 with the provisos that: (i) when the dashed line at the 7-5 position is a carbon-carbon single bond, then R.sub.3 and R.sub.4 are both hydrogen, m is 0, n is 1 and q is 1; R.sub.4 is hydrogen, then p and q are both 0; at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and m is 0; n is 1 and q is 0; and p is 0 and one of the dashed lines at the 7-5 position or the 7-4 position is a carbon-carbon single bond;

and then reacting the resulting mixture of aldehydes with methyl ethyl ketone or separating the mixture of aldehydes to its individual components and reacting one or more of the individual components with methyl ethyl ketone to produce a ketone or a mixture of ketones defined according to the structure: ##STR42## taken together with the compounds defined according to the structure: ##STR43## and either using the resulting mixture for its organoleptic properties or using the individual ketones for their respective organoleptic properties or further reacting the mixture or the individual ketones with lithium aluminum hydride or an alkali metal borohydride to form individually or in admixture alcohol(s) defined according to the structure: ##STR44## and/or alcohol(s) defined according to the structure: ##STR45## The alcohol mixtures can be used as is for their organoleptic properties or the resulting mixtures can be separated into their individual components and used for their organoleptic properties.

Thus, the present invention also provides processes for using compounds defined according to the generic structure: ##STR46## for their organoleptic properties in augmenting or enhancing the organoleptic properties of consumable materials, that is, the aroma or taste of perfumes, colognes, perfumed articles (such as solid or liquid cationic, anionic, nonionic or zwitterionic detergents, soaps, fabric softeners, drier-added fabric softener articles such as BOUNCE.RTM., a registered trademark of the Procter & Gamble Company of Cincinnati, Ohio, fabric brighteners and cosmetic powders), food flavor compositions, foodstuffs, chewing gums, toothpastes, chewing tobaccos, medicinal products, smoking tobacco articles, smoking tobacco products and flavors for augmenting or enhancing smoking tobacco articles or smoking tobacco compositions.

The methyl substituted pinyl oxopentenes of our invention may be prepared by first reacting alpha pinene or beta pinene or a mixture of alpha pinene and beta pinene with carbon monoxide and hydrogen according to an oxo reaction to produce a mixture of aldehydes according to the reaction: ##STR47## wherein one of the wavy lines:

represents a carbon-carbon double bond and the other of the wavey lines:

represents a carbon-carbon single bond.

This reaction is carried out in the presence of a "oxo reaction catalyst" such as rhodium, Co.sub.2 (CO).sub.8, or an organophosphorous polydentate ligand such as those described in European Published Application No. 33,554 published on Aug. 12, 1981, the specification for which is incorporated herein by reference. Examples of which are: ##STR48## at pressures of from about 3 atmospheres up to about 1,000 atmospheres and at temperatures in the range of from about 30.degree. C. up to about 150.degree. C. Preferably when using a rhodium catalyst, the temperature of reaction is between 70.degree. and 110.degree. C.; when using a Co.sub.2 (CO).sub.8 catalyst, the temperature is between 110.degree. and 120.degree. C.; and when using a ligand such as those exemplified in European Published Application No. 33,554, the temperature may vary from 95.degree. C. up to 120.degree. C. as is set forth in the following table: ______________________________________ Ligand           Reaction Temperature ______________________________________ .phi..sub.2 P(CH.sub.2).sub.2 P.phi..sub.2 95-120.degree. C. ##STR49##       120.degree. C. ##STR50##       120.degree. C. .phi..sub.2 PCHCHP.phi..sub.2 120.degree. C. ##STR51##        95.degree. C. .phi..sub.2 P(CH.sub.2).sub.4 P.phi..sub.2 95.degree. C. .phi..sub.2 P(CH.sub.2).sub.3 P.phi..sub.2 95.degree. C. P.phi..sub.3     120.degree. C. .phi..sub.2 P(CH.sub.2).sub.10 P.phi..sub.2 120.degree. C. .phi..sub.2 PCH.sub.2 P.phi..sub.2 120.degree. C. (CH.sub.3).sub.2 P(CH.sub.2).sub.2 P(CH.sub.3).sub.2 120.degree. C. ______________________________________

The resulting mixture of aldehydes may then be separated for subsequent reaction or may be used as is and is preferably used as is as a mixture (which is the most economical way to proceed). The mixture or individual aldehydes are then reacted with methyl ethyl ketone according to the reactions: ##STR52## whereby a mixture of ketones is produced. This reaction is carried out under standard "aldol" condensation reaction conditions, that is, using a basic catalyst and reflux conditions with the basic catalyst being sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide or calcium hydroxide. The reaction can be carried out using a "Soxhlet" apparatus in the laboratory or analogous apparatus in the plant. The reaction temperature may vary from about 40.degree. C. up to about 150.degree. C. and is preferably carried out at reflux conditions at atmospheric pressure. However, the reaction may be carried out at higher pressures and higher temperatures in pressure equipment which preferably is either glass-lined pressure equipment or stainless steel pressure equipment. At the end of the reaction, the reaction mixture is distilled by means of fractional distillation and the resulting products in admixture may be used "as is" for their organoleptic properties or may be used "as is" for further reaction or may be separated by means of commercial chromatographic techniques, e.g. "HPLC" techniques.

The resulting reaction product may be reduced using lithium aluminum hydride, sodium borohydride or potassium borohydride reducing agents according to the reactions: ##STR53## taken together with the reaction: ##STR54## These reactions are preferably carried out in a solvent which is inert to the reaction mass such as diethylether or tetrahydrofuran under reflux conditions at atmospheric pressure. The reaction may be carried out at pressures higher than atmospheric at higher temperatures thereby resulting in shorter times of reaction. However, the yield of reaction product is not affected by the higher temperature of reaction. However, higher temperatures will vary the ratio of isomeric products produced without, however, materially affecting the organoleptic properties thereof. At the end of the reaction, the reaction product may be used "as is" for its organoleptic properties after appropriate fractional distillation or the reaction product after fractional distillation may be separated into the individual components of the mixture by standard chromatographic techniques, e.g. HPLC techniques.

Examples of mixtures of products and individual products produced according to the foregoing reaction sequence are set forth in Table I, infra: __________________________________________________________________________ Structure of Product(s) and Example by which Fragrance Food Flavor Tobacco Flavor Produced             Evaluation Evaluation Evaluation __________________________________________________________________________ ##STR55##           A strong, woody, urine-like note with a buttery, caramel topnote. An ionone-like raspberry, ori- ental, floral violet aroma profile with a sweet, ionone- like, rasp- berry, fruity, taste profile with a rasp- berry after- taste at 0.05 ppm. A woody, sweet, oriental, rasp- berry, ionone-  like aroma and taste prior to smoking with a woody, sweet, oriental, ionone-like taste on smoking in the main stream and the side stream. ##STR56## (mixture, bulked fractions 14-17). ##STR57##           Powerful sandalwood aroma with urine, sweet, floral (muguet) undertone. produced according to Example IV. ##STR58##           Powerful sandalwood aroma at 0.0001 ppm. (mixture). ##STR59##           A sandalwood, musky aroma profile. A musky, fruity, ionone-like aroma with a lactonic taste at 0.1 ppm. A woody, sandal- wood, patchouli- like, cigar box- like aroma and taste profile both prior to and on smoking in the main stream and the ide stream. ##STR60## __________________________________________________________________________

When the methyl substituted pinyl oxopentenes of our invention are used as food flavor adjuvants, the nature of the co-ingredients included with the methyl substituted pinyl oxopentenes of our invention used in formulating the product composition will also serve to alter, modify, augment or enhance the organoleptic properties of the ultimate foodstuff treated therewith.

As used herein as regards to flavor, the terms "alter", "modify" and "augment" in their various forms mean "supplying or imparting flavor character or note to otherwise bland, relatively tasteless substances or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of a flavor or aroma characteristic or note without the modification of the quality thereof. Thus, "enhancement" of a flavor or aroma means that the enhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquid ingestible materials which usually do, but need not have nutritional value. Thus, foodstuffs include soups, convenience foods, beverages, dairy products, candies, chewing gums, vegetables, cereals, soft drinks, snacks and the like.

As used herein, the term "medicinal product" includes both solids and liquids which are ingestible non-toxic materials which have medicinal value such as cough syrups, cough drops, aspirin and chewable medicinal tablets.

The term "chewing gum", is intended herein to mean a composition which comprises a substantially water-insoluble, chewable plastic gum base such as chicle or substitutes therefor, including jelutong, guttakay, rubber or certain cosmetible natural or synthetic resins or waxes. Incorporated with the gum base in admixture therewith may be plasticizers or softening agents, e.g. glycerine, and a flavoring composition which incorporates one or more of the substituted norbornane carboxaldehyde derivatives of our invention, and in addition, sweetening agents which may be sugars, including sucrose or dextrose and/or artificial sweeteners such as cyclamates or saccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature. It is a requirement that any such material be "ingestibly" acceptable and thus non-toxic and otherwise non-deleterious, particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of a consumable material used is not caused to have unacceptable aroma and taste nuances. Such materials may in general be characterized as flavoring agents or vehicles comprising broadly stabilizers, thickeners, surface agents, conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g. sodium chloride, antioxidants, e.g. calcium and sodium ascorbate, ascorbic acid, butylated hydroxy-anisole (mixture of 2- and 3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene (2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like and sequestrants, e.g. citric acid.

Thickener compounds include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, e.g. agar agar, carrageenan, cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth, gelatin, proteinaceous materials, lipids, carbohydrates; starches, pectins and emulsifiers, e.g. mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g. sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g. fatty acids such as capric acid, palmitic acid, myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents, e.g. benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g. sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like, colorants, e.g. carminic acid, cochineal, tumeric and curcuma and the like; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g. aluminum calcium sulfate and tribasic calcium phosphate; enzymes; yeast foods, e.g. calcium lactate and calcium sulfate, nutrient supplements, e.g. iron salts such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.

Other flavorants and flavor intensifiers include organic acids, e.g. acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid, caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric acid, alpha-methyl-butyric acid, propionic acid, valeric acid, 2-methyl-2-pentenoic acid and 2-methyl-cis-3-pentenoic acid; ketones and aldehydes, e.g. acetaldehyde, acetophenone, acetone, acetyl methyl carbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal, beta-beta-dimethylacrolein, methyl-n-amyl ketone, n-hexanol, iso-pentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptanal, n-nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone, methyl-3-butanone, benzaldehyde, beta-damascone, beta-damascenone, acetophone, 2-heptanone, o-hydroxyacetophone, 2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexanal, 2-phenyl-2-pentenal, furfural, 5-methyl furfural, cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanol; alcohols such as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol, linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethyl caprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethyl crotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyl laurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate, ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate, alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate, cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbons such as dimethyl naphthalene, n-dodecane, methyl diphenyl, methyl naphthalene, mycrene, naphthalene, n-octadecane, n-tetradecane, tetramethyl naphthalene, n-trimethyl naphthalene, undecane, caryophyllene, 1-phellandrene, p-cymene and 1-alpha-pimene; pyrazines such as 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine, 3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine, 2-isopropyl-4,5-dimethylpyrazine, 1-methyl-2-ethylpyrazine, tetramethylpyrazine, trimethylpyrazine, essential oils such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute, orris absolute, lemon essential oil, Bulgarian rose, yara yara and vanilla, lactones such as delta nonalactone, gamma nonalactone, delta dodecalactone, gamma dodecalactone, sulfides, e.g. methyl sulfide and other materials such as maltol, acetoin and acetals (e.g. 1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e. foodstuff, whether simulated or natural, and should, in any event, (i) be organoleptically compatible with the methyl substituted pinyl oxopentenes of our invention by not covering or spoiling the organoleptic properties (aroma and/or taste) thereof; (ii) be non-reactive with the methyl substituted pinyl oxopentenes of our invention and (iii) be capable of providing an environment in which the methyl substituted pinyl oxopentenes of our invention can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the foodstuff, chewing gum, medicinal product or toothpaste to which the flavor and/or aroma are to be imparted, modified, altered or enhanced. In contradistinction, in the preparation of solid products, e.g. simulated foodstuffs, ingredients capable of providing normally solid compositions should be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of the methyl substituted pinyl oxopentenes employed in a particular instance can vary over a relatively wide range, depending upon the desired organoleptic effects to be achieved. Thus, correspondingly greater amounts would be necessary in those instances wherein the ultimate food composition to be flavored is relatively bland to the taste, whereas relatively minor quantites may suffice for purposes of enhancing the composition merely deficient in natural flavor or aroma. The primary requirement is that the amount selected be effective, i.e. sufficient to alter, modify or enhance the organoleptic characteristics of the parent composition, whether foodstuff per se, chewing gum per se, medicinal product per se, toothpaste per se, or flavor composition.

The use of insufficient quantities of methyl substituted pinyl oxopentenes will, of course, substantially vitiate any possibility of obtaining the desired results while excess quantities prove needlessly costly and in extreme cases, may disrupt the flavor-aroma balance, thus proving self-defeating. Accordingly, the terminology "effective amount" and "sufficient amount" is to be accorded a significance in the context of the present invention consistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gum compositions, medicinal product compositions and toothpaste compositions, it is found that quantities of methyl substituted pinyl oxopentenes ranging from a small but effective amount, e.g. 0.02 parts per million up to about 300 parts per million based on total composition are suitable. Concentrations in excess of the maximum quantity stated are not normally recommended, since they fail to provide commensurate enhancement of organoleptic properties. In those instances wherein methyl substituted pinyl oxopentenes are added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that the total amount of flavoring composition employed by sufficient to yield an effective concentration of methyl substituted pinyl oxopentenes in the foodstuff product.

Food flavoring compositions prepared in accordance with the present invention preferably contain methyl substituted pinyl oxopentenes in concentrations ranging from about 0.1% up to about 15% by weight of the total weight of the said flavoring composition.

The composition described herein can be prepared according to conventional techniques well known as typified by cake batters and fruit drinks and can be formulated by merely admixing the involved ingredients within the proportions stated in a suitable blender to obtain the desired consistency, homogeneity of dispersion, etc. Alternatively, flavoring compositions in the form of particulate solids can be conveniently prepared by mixing methyl substituted pinyl oxopentenes with, for example, gum arabic, gum tragacanth, carrageenan and the like, and thereafter spray-drying the resultant mixture whereby to obtain the particulate solid product. Pre-prepared flavor mixes in powder form, e.g. fruit flavored powder mixes, are obtained by mixing the dried solid components e.g. starch, sugar and the like and one or more methyl substituted pinyl oxopentenes in a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with methyl substituted pinyl oxopentenes of our invention, the following adjuvants:

The methyl substituted pinyl oxopentenes of our invention can be used to contribute sandalwood, urine-like, animal-like aromas with floral and muguet undertones and woody topnotes to perfume compositions, perfumed articles such as solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions, fabric softener articles, fabric optical brighteners, fabric conditioners, hair preparations and perfumed polymers. As olfactory agents, the methyl substituted pinyl oxopentenes of our invention can be formulated into or used as components of a perfume composition.

The term "perfume composition" is used herein to mean a mixture of organic compounds including for example, alcohols, aldehydes, ketones, nitriles, ethers, lactones and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfumed compositions usually contain (a) the main note of the "bouquet" or foundation stone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation and (d) topnotes which are usually low-boiling, fresh-smelling materials.

In perfume compositions, the individual component will contribute its particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient. Thus, the individual compounds of this invention, or mixtures thereof, can be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of methyl substituted pinyl oxopentenes of our invention which will be effective in perfume compositions depends upon many factors including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.5% of the methyl substituted pinyl oxopentenes of our invention or even less in perfume compositions containing as much as 70% of the methyl substituted pinyl oxopentenes of our invention can be used to impart interesting, sandalwood, animal-like, musky and urine-like aromas with floral and muguet undertones to perfumed articles, perfume compositions and colognes. Such perfumed articles include fabric softener compositions, perfumed polymers (e.g. perfumed microporous polyethylene and microporous polypropylene), drier-added fabric softeners, cosmetic powders, talcs, and solid or liquid anionic, cationic, nonionic or zwitterionic detergents. The amount employed can range up to 70% and will depend on considerations of cost, nature of the end product and the effect desired on the finished product and the particular fragrance sought.

Thus the methyl substituted pinyl oxopentenes of our invention can be used alone or in a perfume composition as an olfactory component in solid or liquid anionic, cationic, nonionic or zwitterionic detergents (including soaps), space odorants and deodorants; perfumes; colognes, toilet water, bath salts, hair preparations such as lacquers, brilliantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions and sun screens; powders such as talcs, face powders, dusting powders; perfumed polymers such as perfumed microporous thermoplastic polymers, e.g. perfumed polyethylene, perfumed polyrpopylene, perfumed polyesters or perfumed thermoset resins such as cross-linked polyacrylates, cross-linked polyurethanes and the like.

When used as an olfactory component of a perfumed article such as a solid or liquid anionic, cationic, nonionic or zwitterionic detergent or of a cosmetic powder or of a plastic polymer, as little as 0.01% of one or more of the methyl substituted pinyl oxopentenes of our invention will suffice to provide interesting musky, woody, animal-like, sandalwood-like aromas with floral and muguet undertones. Generally no more than 0.8% of the methyl substituted pinyl oxopentenes of our invention are required.

Thus the range of methyl substituted pinyl oxopentenes in the perfumed article may vary from about 0.01% up to about 0.8% of the overall perfumed article.

In addition, the perfume compositions of our invention can contain a vehicle or carrier for the methyl substituted pinyl oxopentenes of our invention alone or with other ingredients. The vehicle can be a liquid such as an alcohol such as ethanol, a glycol such as propylene glycol or the like. The carrier can be an absorbent solid such as a gum (e.g. xanthan gum or guar gum), or components for encapsulating the composition as by coacervation (e.g. gelatin) or as by polymerization around a liquid perfume oil core as by polymerization of a urea formaldehyde polymer.

Also contemplated within the scope of this invention are mixtures of the methyl substituted pinyl oxopentenes of our invention taken further together with: ##STR61## taken alone or taken further together with other compounds which yield sweaty, animal, leathery notes defined according to genera having the structures: ##STR62## wherein R represents t-butyl or t-amyl as more specifically described in U.S. Pat. No. 3,702,343 issued on Nov. 7, 1972, the disclosure for which is incorporated by reference herein.

In addition to the methyl substituted pinyl oxopentenes of our invention and to the compounds having the structure: ##STR63## and/or the compounds defined according to the structures: ##STR64## it is contemplated that these compounds can also be used in admixture with cedrol alkyl ethers disclosed in U.S. Pat. No. 3,373,208 issued on Mar. 12, 1968, the disclosure of which is incorporated by reference herein. The cedrol alkyl ethers of U.S. Pat. No. 3,373,208 are defined according to the generic structure: ##STR65## wherein R represents methyl, ethyl, propyl, butyl, allyl or methallyl.

Contemplated within the scope of our invention are ratios of methyl substituted pinyl oxopentenes:4-methyl-3-cyclohexene-1-carboxylic acid or 2-methyl-2-(t-alkyl cyclohexyl ) pentan-4-one or cedrol alkyl ethers of from 1:30 to 30:1 (mole ratios).

The compounds defined according to the structure: ##STR66## may be prepared by methods well known in the art, e.g. according to the reaction: ##STR67## as further disclosed in Example I of application for U.S. patent Ser. No. 391,592 filed on June 24, 1982, now U.S. Pat. No. 4,390,434 issued on June 28, 1983, the disclosure of which is incorporated by reference herein.

When using the mixtures of our invention, that is the methyl substituted pinyl oxopentenes and the compounds defined according to the structure: ##STR68## or the compounds defined according to the structures: ##STR69## or the compound defined according to the structure: ##STR70## the additional notes provided to the perfume compositions or perfumed articles as set forth, supra, are cumin-like, sweaty, and cedar-like with castoreum undertones.

Furthermore, the methyl substituted pinyl oxopentenes produced according to the processes of our invention are capable of supplying and/or potentiating certain flavor and aroma notes usually lacking in many tobacco flavors heretofore provided.

As used herein in regard to tobacco flavors, the terms "alter" and "modify" in their various forms mean "supplying or imparting flavor character or note to otherwise bland tobacco, tobacco substitutes, or tobacco flavor formulations or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste".

As used herein, the term "enhance" is intended to mean the intensification (without change in kind of quality of aroma or taste) of one or more taste and/or aroma nuances present in the organoleptic impression of tobacco or a tobacco substitute or a tobacco flavor.

Our invention thus provides an organoleptically improved smoking tobacco product and additives therefor as well as methods of making the same which overcome specific problems heretofore encountered in which specific desired Turkish-type, oriental or Virginia tobacco aroma and taste nuances thereof are created or enhanced and may be readily controlled and maintained at the desired uniform level regardless of variations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methods whereby various Virginia-type, oriental-type and Turkish-type tobacco notes may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavor characteristics.

In carrying out this aspect of our invention, we add to smoking tobacco materials or a suitable substitute therefor (e.g. dried lettuce leaves) an aroma and flavor additive containing as an active ingredient one or more methyl substituted pinyl oxopentenes produced according to the processes of our invention.

In addition to the methyl substituted pinyl oxopentenes produced according to the processes of our invention, other flavoring and aroma additives may be added to the smoking tobacco materials or substitute therefor either separately or in admixture with the methyl substituted pinyl oxopentenes produced according to the processes of our invention as follows: defined in Example V or U.S. Pat. No. 3,589,372, issued on June 29, 1971.

An aroma and flavoring concentrate containing one or more of the methyl substituted pinyl oxopentenes produced according to the processes of our invention and, if desired, one or more of the above indicated additional flavoring additives may be added to the smoking tobacco material, to the filter or to the leaf or paper wrapper. The smoking tobacco material may be shredded, cured, cased and blended tobacco material or reconstituted tobacco material or tobacco substitutes (e.g. lettuce leaves) or mixtures thereof. The proportions of flavoring additives may be varied in accordance with taste but insofar as enhancement or the imparting of natural and/or sweet and/or woody, e.g. sandalwoody, and/or oriental notes, we have found that satisfactory results are obtained if the proportion by weight of the sum total of the methyl substituted pinyl oxopentenes produced according to the processes of our invention to smoking tobacco material is between 200 ppm and 2,000 ppm (0.02%-0.20%) of the active ingredients to the smoking tobacco material. We have further found that satisfactory results are obtained if the proportion by weight of the sum total of the methyl substituted pinyl oxopentenes produced according to the processes of our invention used to flavoring material is between 2,500 and 15,000 ppm (0.25%-1.5%).

Any convenient method for incorporating the methyl substituted pinyl oxopentenes produced according to the processes of our invention in the tobacco product may be employed. Thus, the methyl substituted pinyl oxopentenes produced according to the processes of our invention taken alone or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, n-pentane, diethylether, and/or other volatile organic solvents and the resulting solution may either be sprayed on the cured, cased and blended tobacco material or the tobacco material may be dipped into such solution. Under certain circumstances, a solution of the methyl substituted pinyl oxopentenes produced according to the process of our invention taken alone or further together with other flavoring additives as set forth above, may be applied by means of a suitable applicator such as a brush or roller on the paper or leaf wrapper for the smoking product, or it may be applied to the filter by either spraying, dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco or substitute therefor need be treated and the thus treated tobacco may be blended with other tobaccos before the ultimate tobacco product is formed. In such cases, the tobacco treated may have the methyl substituted pinyl oxopentenes produced according to the process of our invention in excess of our invention in excess of the amounts or concentrations above indicated so that when blended with other tobaccos, the final product will have the percentage within the indicated range.

In accordance with one specific example of our invention, an aged, cured and shredded domestic burley tobacco is sprayed with a 20% ethyl alcohol solution of the mixture of alcohols produced according to Example V, infra (bulked fractions 10-20 of the distillation product) defined according to the formula: ##STR71## taken together with the compounds defined according to the structure: ##STR72## (wherein in the mixture, in each of the compounds Z represents methylidene defined according to the structure: ##STR73## ethylidene defined according to the structure: ##STR74## or ethylenyl defined according to the structure: ##STR75## wherein one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents no bond; wherein n is 0 or 1 and m is 0 or 1 with the sum of n+m being equal to 1; wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; with the provisos that: position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR76## or ethylene having the structure: ##STR77## (ii) when one of H.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR78## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and

and wherein one of the lines: ##STR79## is a carbon-carbon double bond and the other of the lines: ##STR80## is a carbon-carbon single bond) in an amount to provide a tobacco composition containing 800 ppm by weight of the mixture of alcohols of Example V, infra, on a dry basis. Thereafter, the volatile ethyl alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. The cigarettes, when treated as indicated, have desired and pleasing aromas (increased smoke body sensation in the mouth with enhanced tobacco-like notes and pleasant aromatic nuances) which is detectable in the main and side streams when the cigarette is smoked. This aroma is described as having sweet, woody, sandalwood, patchouli, Havana cigar and burley characteristics.

While our invention is particularly useful in the manufacture of smoking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other tobacco products formed from sheeted tobacco dust or fines may also be used. Likewise, the methyl substituted pinyl oxopentenes produced according to the processes of our invention can be incorporated with materials such as filter tip materials, seam paste, packaging materials and the like which are used along with tobacco to form a product adapted for smoking. Furthermore, the methyl substituted pinyl oxopentenes produced according to the process of our invention can be added alone or in admixture to certain tobacco substitutes of natural or synthetic origin (e.g. dried lettuce leaves) and, accordingly, by the term "tobacco" as used throughout this specification, is meant any composition intended for human consumption by smoking whether composed of tobacco plant parts, substitute materials or both.

The following examples serve to illustrate our invention and the invention is to be considered restricted thereto only as indicated in the appended claims.

All parts and percentages given herein are by weight unless otherwise specified.

Reactions: ##STR81## (wherein a mixture is produced wherein the mixture one of the dashed lines in each of the compounds at the 7-5 or 7-4 positions represents a carbon-carbon single bond and the other of the dashed lines at the 7-5 or 7-4 positions represents no bond; wherein one of R.sub.3 or R.sub.4 represents hydrogen and the other of R.sub.3 or R.sub.4 represents hydrogen or methyl; wherein m=0 or 1 with the sum of m+n being equal to 1; wherein A and B each represents methylene defined according to the structure: ##STR82## wherein p=0 or 1 and q=0 or 1 with the provisos that: (i) when the dashed line at the 7-5 position is a carbon-carbon single bond, then R.sub.3 and R.sub.4 are both hydrogen, m is 0, n is 1 and q is 1; R.sub.4 is hydrogen, then p and q are both 0; at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and m is 0; n is 1 and q is 0; and p is 0 and one of the dashed lines at the 7-5 position or the 7-4 position is a carbon-carbon single bond).

Into a 3 liter autoclave equipped for pressures up to 6,000 psig is placed 200 ml dicobalt octacarbonyl catalyst; and 4 pounds of alpha pinene. The autoclave is closed and the vessel is pressurized with a 1:1 mole ratio of carbon monoxide and hydrogen and maintained at 185.degree.-208.degree. C. and 4,000 psig pressure while adding the mixture of carbon monoxide and hydrogen. The carbon monoxide:hydrogen mixture is added until seven cubic feet (at atmospheric pressure and 20.degree. C.) of each of the carbon monoxide and hydrogen is added to the reaction mass.

At the end of the reaction, the autoclave is depressurized and opened. The resulting reaction mass is washed five times with equal volumes of water. The resulting reaction product is dried over anhydrous magnesium sulfate and distilled on a 1' silver mirror column yielding the following fractions: Vapor   Liquid                Weight of Fraction Temp.   Temp.    Pressure Reflux Fraction Number  (.degree.C.) (.degree.C.) mm/Hg. Ratio (grams) ______________________________________ 1       30/34   70/93    10/10   4:1  23.2 2       59      86       10      4:1  21.8 3       65      88       10      7:1  25.1 4       65      89       10      9:1  71.3 5       65/75   80/93    10/10   9:1  19.6 6       70       94      10     17:3  39.8 7       69       94      10     17:3  49.9 8       74      100      10     17:3  39.4 9       74      101      10     17:3  39.9 10      74      101      10     17:3  35.7 11      81      100      10     17:3  22.1 12      80/87   101/104  10/9   17:3  29.1 13      90      106       8     17:3  39.3 14      90      107       7     17:3  40.7 15      94      108       7     17:3  44.0 16      94      113       7     17:3  64.8 17      93/95   113/136  8/7     4:1  55.7 18      50      210      2.5     4:1  24.0 ______________________________________

Fractions 3-8 are bulked for subsequent reaction in Example II.

Reactions: ##STR83## (mixture produced wherein in the mixture, in each of the compounds, Z represents methylidene defined according to the structure: ##STR84## ethylidene defined according to the structure: ##STR85## or ethylenyl defined according to the structure: ##STR86## wherein one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents no bond; wherein n is 0 or 1 and m is 0 or 1 with the sum of n+m being equal to 1; wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; with the provisos that: position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR87## or ethylenyl having the structure: ##STR88## (ii) when one of R.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR89## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and

wherein one of the lines: ##STR90## is a carbon-carbon double bond and the other of the lines: ##STR91## is a carbon-carbon single bond).

Into a three-neck reaction flask equipped with reflux condenser, magnetic stirrer, thermometer and addition funnel is added 50 ml of methanol and 1.5 grams of potassium hydroxide. The resulting mixture is stirred until all the potassium hydroxide is dissolved. The reaction flask is cooled to 10.degree. C. and 25 grams of the reaction product of Example I, bulked fractions 3-8, a mixture defined according to the structure: ##STR92## taken together with the compound having the structure: ##STR93## is added dropwise from the addition funnel over a one-hour period to the reaction mass.

The reaction mixture is allowed to warm to room temperature (23.degree. C.) and 32 grams of methyl ethyl ketone is added dropwise over a 2.5 hour period while maintaining the reaction mass at room temperature. The reaction mass is monitored for completion of reaction using GLC. The reaction mass is heated at the end of a 16 hour period to 45.degree.-50.degree. C. and maintained at 45.degree.-50.degree. C. for a period of six hours.

The reaction mass is then diluted with saturated sodium chloride solution (75 ml) and extracted with four 30 ml volumes of toluene. The toluene extracts are combined and washed with three volumes of saturated sodium chloride followed by two volumes of water and one volume of saturated sodium chloride. The reaction mass is then dried over anhydrous magnesium sulfate and the solvent is removed leaving 36.3 grams of crude material which is distilled on a microvigreux column to yield the following fractions: Vapor    Liquid            Weight of Fraction Temp.    Temp.     Pressure Fraction Number  (.degree.C.) (.degree.C.) mm/Hg.  (grams) ______________________________________ 1       49/66     96/115   3.2     3.1 2       83       115       1       1.8 3       84       118       1       3.2 4       86       119       1       2.6 5       86       124       1       2.2 6       87       131       1       1.9 7       87       135       1       2.9 8       104      166       1.8     3.2 9       107      190       1.9     1.0 ______________________________________

Reactions: ##STR94## (a mixture being produced wherein in the mixture one of the dashed lines in each of the compounds at the 7-5 or 7-4 positions represents a carbon-carbon single bond and the other of the dashed lines at the 7-5 or 7-4 positions represents no bond; wherein one of R.sub.3 or R.sub.4 represents hydrogen and the other of R.sub.3 or R.sub.4 represents hydrogen or methyl; wherein m=0 or 1 with the sum of m+n being equal to 1; wherein A and B each represents methylene defined according to the structure: ##STR95## wherein p=0 or 1 and q=0 or 1 with the provisos that: (i) when the dashed line at the 7-5 position is a carbon-carbon single bond, then R.sub.3 and R.sub.4 are both hydrogen, m is 0, n is 1 and q is 1; R.sub.4 is hydrogen, then p and q are both 0; at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and m is 0; n is 1 and q is 0; and p is 0 and one of the dashed lines at the 7-5 position or the 7-4 position is a carbon-carbon single bond).

Into an autoclave equipped for 6,000 psig pressure is placed 4,000 grams of alpha pinene and 125 ml of dicobalt octacarbonyl catalyst. The autoclave is closed and is pressurized with an equimolar mixture of carbon monoxide and hydrogen to a pressure of 4,000 psig. The reaction mixture is heated to a temperature in the range of 200.degree.-220.degree. C. at a pressure of 4,000 psig until 8 cubic feet of carbon monoxide and 8 cubic feet of hydrogen are absorbed (conditions: 1 atmosphere at 20.degree. C.). At the end of the reaction, the autoclave is depressurized and opened yielding 3,870 grams of reaction product. The resulting material is washed with four volumes of water. The resulting material is then dried over anhydrous magnesium sulfate and distilled on a 4" Splash column yielding the following fractions: Vapor   Liquid           Weight of Fraction   Temp.   Temp.     Pressure Fraction Number     (.degree.C.) (.degree.C.) mm/Hg. (grams) ______________________________________ 1          27/40   38/53     5/5    16.2 2          50      65        15     61.8 3          56      72        15     77.8 4          59      78        15     76.2 5          63      89        15     91.6 6          83      103       10     70.1 7          85      93         4     196.2 8          93      109        3     217.3 9          105     165        3     173.7 10         114     210        3     24.4 ______________________________________

Reactions: ##STR96## (mixture produced wherein in the mixture, in each of the compounds, Z represents methylidene defined according to the structure: ##STR97## ethylidene defined according to the structure: ##STR98## or ethylenyl defined according to the structure: ##STR99## wherein one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents no bond; wherein n is 0 or 1 and m is 0 or 1 with the sum of n+m being equal to 1; wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; with the provisos that: position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR100## or ethylenyl having the structure: ##STR101## (ii) when one of R.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR102## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and

and wherein one of the lines: ##STR103## is a carbon-carbon double bond and the other of the lines: ##STR104## is a carbon-carbon single bond).

Into a five liter, three-neck reaction flask equipped with thermometer, condenser, addition funnel, mechanical stirrer, wet ice cooling bath and constant temperature warming bath, is placed 1,650 ml anhydrous methyl alcohol and 23.3 grams of potassium hydroxide. The mixture is stirred until all the potassium hydroxide is dissolved. The resulting mixture is cooled to 10.degree. C. and 405 grams of the mixture of aldehydes prepared according to Example III (bulked fractions 7 and 8) defined according to the structure: ##STR105## taken together with the compound having the structure: ##STR106## is added dropwise over a period of approximately one hour to the reaction mass with stirring. The mixture is then allowed to warm to room temperature (23.degree. C.) and 533 grams of methyl ethyl ketone is added to the reaction mass, dropwise, over a 2.5 hour period at room temperature.

The reaction mixture is then heated to approximately 45.degree. C. for a period of six hours. The reaction mass is then diluted with 750 ml saturated sodium chloride solution at room temperature and the aqueous phase is extracted with four volumes of toluene. The toluene extracts are combined and washed with three 1 liter volumes of saturated sodium chloride followed by two 1 liter volumes of water and one 1 liter volume of saturated sodium chloride solution.

The resulting product (weight 428.7 grams) is then distilled yielding the following fractions: Vapor   Liquid                Weight of Fraction Temp.   Temp.    Pressure Reflux Fraction Number  (.degree.C.) (.degree.C.) mm/Hg. Ratio (grams) ______________________________________ 1       32/33   100/106  3.5/2.2 4:1   14.7 2       57      107      2.0    4:1   10.8 3       65      108      1.9    4:1    9.1 4       77      114      1.9    4:1   12.2 5       75      119      1.9    4:1   26.7 6       80      122      1.8    9:1   16.3 7       80      125      1.8    9:1   18.2 8       81      129      1.8    9:1   13.8 9       86      130      1.8    9:1   20.5 10      89      130      1.8    9:1   14.1 11      69/86   137/138  1.8/1.8 9:1/9:1 10.6 12      85      139      1.8    9:1   15.5 13      89      140      1.8    9:1   12.2 14      88      140      1.8    17.3  21.0 15      88      140      1.8    17.3  18.8 16      86      142      1.6    17.3  20.0 17      84      145      1.6    17.3  18.4 18      84      150      1.6    17.3  20.6 19      88      170      1.6    17.3  22.6 20      35      210      1.4    17.3  19.7 ______________________________________

Reactions: ##STR107## (mixture produced wherein in the mixture, in each of the compounds, Z represents methylidene defined according to the structure: ##STR108## ethylidene defined according to the structure: ##STR109## or ethylenyl defined according to the structure: ##STR110## wherein one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents no bond; wherein n is 0 or 1 and m is 0 or 1 with the sum of n+m being equal to 1; wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; wherein one of the lines:

represents a carbon-carbon single bond and the other of the lines:

represents a carbon-carbon single bond or a carbon-carbon double bond; with the provisos that:

(i) when R.sub.3 and R.sub.4 are each hydrogen, the dashed line at the 7-5 position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR111## or ethylenyl having the structure: ##STR112## (ii) when one of R.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR113## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and

and wherein one of the lines: ##STR114## is a carbon-carbon double bond and the other of the lines: ##STR115## is a carbon-carbon single bond).

Into a 1 liter reaction flask equipped with mechanical stirrer, thermometer, condenser, addition funnel and nitrogen purge apparatus is placed 200 ml anhydrous diethylether and 4.0 grams of lithium aluminum hydride.

50 grams (0.23 moles) of the distillation product (bulked fractions 14-17) of the reaction product of Example IV defined according to the structures: ##STR116## taken together with the structure: ##STR117## are then intimately admixed and dissolved in 50 ml anhydrous diethylether. The resulting ether-ketone solution is then added, with stirring over a period of one hour, to the reaction mass which exotherms to 34.degree. C. The reaction mass, after addition of the ketone mixture, is then stirred for a period of three hours. The reaction mass is then added dropwise with cooling to 250 ml water. The resulting mixture is then extracted with three volumes of diethylether and dried over anhydrous magnesium sulfate and concentrated. (Crude weight of reaction mass 48.3 grams).

The reaction mass is then distilled on a microvigreux column yielding the following fractions: Vapor     Liquid            Weight of Fraction Temp.     Temp.     Pressure Fraction Number  (.degree.C.) (.degree.C.) mm/Hg.  (grams) ______________________________________ 1       92/92     112/113   1/1     0.5 2        92       110       1       1.0 3        85       110       1       1.1 4       117       124       1       2.1 5        95/101   116/121   2/1     0.7 6       115       126       1       3.0 7       122       134       1       5.0 8       115       135       1       2.4 9       115       132       1       2.9 10      108       128       1       2.5 11      112       124       1       2.3 12      110       122       1       2.3 13      109       124       1       1.9 14      107       126       1       2.6 15       80       140       1       1.9 16      102       190       1       1.2 17       50       220       1       0.7 ______________________________________

Reaction: ##STR118## wherein K represents the compound defined according to the structure: ##STR119##

Into a 500 ml autoclave equipped for 1,000 psig pressure is placed 136 grams beta pinene; 0.5 grams of the catalyst defined according to the structure: ##STR120## and 50 ml toluene. With stirring, the autoclave is closed and heated to 100.degree. C. While maintaining the autoclave temperature at 100.degree. C., a 1:1 mole ratio mixture of carbon monoxide and hydrogen is charged to the autoclave up to 1,000 psig pressure and the autoclave is maintained at 100.degree. C. and 1,000 psig pressure for a period of 13.5 hours. During the 13.5 hour reaction period, the total pressure drop for the carbon monoxide:hydrogen mixture is 5180 psi. At the end of the 13.5 hour period, the autoclave is depressurized and opened.

The reaction mass is then washed with 500 ml of a 10% hydrochloric acid solution; followed by saturated sodium carbonate aqueous solution and then washed with water until neutral.

The reaction mass is then distilled yielding three fractions; the first fraction being all toluene and the second and third fractions containing 60.5 grams product as confirmed by GLC analysis.

The distillation yielded the following fractions: Vapor        Liquid Fraction Temp.        Temp.   Pressure Number   (.degree.C.) (.degree.C.) mm/Hg. ______________________________________ 1        30           34      6 2        50           79      6 3        96           200     9 ______________________________________

Reaction: ##STR121## (wherein a mixture is produced wherein in the mixture one of the dashed lines is a carbon-carbon double bond in each of the compounds and the other of the dashed lines is a carbon-carbon single bond in other compounds; wherein one of R.sub.5 and R.sub.6 is hydrogen and the other of R.sub.5 and R.sub.6 is methyl in each of the compounds).

Into a one-liter reaction flask equipped with stirrer, addition funnel, thermometer and reflux condenser is added 220 ml methyl alcohol and 33 grams of potassium hydroxide. The resulting mixture is stirred until all of the potassium hydroxide is dissolved.

The reaction vessel is cooled to 10.degree. C. and 55 grams of 10-formyl pinane having the structure: ##STR122## of fraction 3 of the distillation product of Example V(A) is added dropwise subsequent to being dissolved in an equal volume of methyl alcohol. After addition of the 10-formyl pinane, the reaction mass is allowed to reach room temperature (23.degree. C.) and 72 grams of methyl ethyl ketone is added dropwise over a 1.5 hour period while maintaining the reaction mass at room temperature.

After addition of the methyl ethyl ketone, the reaction mass is heated to 45.degree. C. and maintained at 45.degree. C. with stirring for a 6 hour period.

The reaction mass is then cooled to room temperature and the reaction mass is diluted with about 500 ml of saturated sodium chloride solution yielding two phases; an organic phase and an aqueous phase. The organic phase is separated from the aqueous phase and the aqueous phase is extracted with four 100 ml portions of diethyl ether. The diethyl ether extracts are combined and washed three times with saturated sodium chloride solution until neutral. The resulting mixture is dried over anhydrous magnesium sulfate and the solvent is removed to yield 80.0 grams of crude product. This crude material primarily contains the compound defined according to the structure: ##STR123## but is also a mixture which can be defined according to the structure: ##STR124## wherein in the mixture in each of the compounds, one of the dashed lines is a carbon-carbon double bond and the other of the dashed lines is a carbon-carbon single bond; and one of R.sub.5 or R.sub.6 is hydrogen and the other of R.sub.5 or R.sub.6 is methyl.

The resulting material is distilled on a 1' Vigreux column to yield 13 fractions thusly: Vapor    Liquid            Weight of Fraction Temp.    Temp.     Pressure Fraction Number  (.degree.C.) (.degree.C.) mm/Hg.  (grams) ______________________________________ 1       25/25    113/126   2/1     0.9 2        81      135       1       0.9 3       101      139       1       1.8 4       102      141       1       3.2 5       102      142       1       3.6 6       104      145       1       4.4 7       103      145       1       8.7 8       103      146       1       7.7 9       103      148       1       6.2 10      110      162       1       10.3 11      113      180       1       7.3 12      103      204       1       3.3 13      133      235       1       1.8 ______________________________________

The following basic raspberry formulation is prepared: Ingredients         Parts by Weight ______________________________________ Vanillin            2.0 Maltol              5.0 Parahydroxybenzylacetone 5.0 Alpha-ionone (10% in propylene 2.0 glycol) Ethyl butyrate      6.0 Ethyl acetate       16.0 Dimethyl sulfide    1.0 Isobutyl acetate    13.0 Acetic acid         10.0 Acetaldehyde        10.0 Propylene glcyol    930.0 ______________________________________

To a first portion of this basic formulation, a mixture of the ketones of Example IV is added at the rate of 1% (bulked fractions 10-20). To the second portion, nothing is added.

To a third portion of this basic formulation, a mixture of the compounds having the structures: ##STR125## (produced according to Example II of U.S. Pat. No. 4,284,824) is added at the rate of 1% and a mixture of the ketones produced according to Example IV supra (bulked fractions 10-20) is added at the rate of 1%. The three flavors are compared at the rate of 100 parts per million by a bench panel of experts.

The flavor containing the mixture of ketones produced according to Example IV (bulked fractions 10-20) is considered to have a more raspberry kernel, more seedy, herbaceous and more natural character in both aroma and taste than the flavor without such ketones. The use of the compounds having the structures: ##STR126## further enhances the raspberry kernel, seedy character.

The following mixture is prepared: Ingredients         Parts by Weight ______________________________________ Natural raspberry concentrate 2.5% Raspberry juice     85.0% Sugar syrup (37.5.degree. Baume) 12.5% ______________________________________

The ripened raspberry and seedy raspberry kernel note of this raspberry juice is imparted in increased strength by the addition of the mixture of ketones (bulked fractions 10-20) prepared according to Example IV at the rate of from 0.01 ppm up to 10 ppm.

To the raspberry formulation as set forth in Example VI, the mixture of ketones produced according to Example IV (bulked fractions 10-20) is added at the rate of 0.2%. This material is then called the "test composition". The raspberry formulation without the mixture of ketones is called the "control composition".

The test and control compositions are added to the food products described hereinafter in the proportions shown for 10 kilograms of material to be flavored:

Cooked sugar--100 ml of sugar syrup (prepared by dissolving 1 kilogram of sucrose in 600 ml of water) and 20 grams of glucose are mixed together and slowly heated to 145.degree. C. The flavor is added and the mass is allowed to cool and harden.

Pudding--to 500 ml of warmed milk are added with stirring a mixture of 60 grams sucrose and 3 grams of pectin. The mixture is boiled for a few seconds and the flavor is added. The mixture is allowed to cool.

The finished foodstuff samples are tested by a panel of trained persons who express their views about the flavor of the samples. All members of the panel prefer the test samples having a more distinguished ripened raspberry aroma with taste of the ripe raspberries and its seedy kernel note.

An improved effect occurs when a mixture of 25:25:50 of 2-(4-hydroxy-4-methylpentyl)-norbornadiene:compound having the structure: ##STR127## mixture of ketones produced according to Example IV (bulked fractions 10-20) at the rate of 0.02 parts per million up to about 10 parts per million.

A. Powder Flavor Composition

Twenty grams of the flavor composition of Example VI containing the mixture of ketones of Example IV (bulked fractions 10-20) is emulsified in a solution containing 300 grams gum acacia and 700 grams of water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500.degree. F., an outlet temperature of 200.degree. F. and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared: Ingredients         Parts by Weight ______________________________________ Liquid raspberry flavor of 20 Example VI containing mixture of ketones prepared according to Example IV (bulked fractions 10-20) Propylene glycol    9 Cab-O--Sil .RTM. M-5 5 (Brand of silica produced by the Cabot Corporation of 125 High Street, Boston, Mass. 02112: Physical properties: Surface area: 200 m.sup.2 /gm Nominal particle size: 0.012 microns Density: 2.3 lbs/cu. ft.) ______________________________________

The Cab-O-Sil.RTM. is dispersed in the liquid raspberry flavor composition of Example VI with vigorous stirring thereby resulting in a viscous liquid. 71 parts by weight of the powder flavor composition of Part A, supra, is then blended into the said viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a dry, free-flowing, sustained release raspberry flavor powder.

Ten parts by weight of 5-Bloom pigskin gelatin is added to ninety parts by weight water at a temperature of 150.degree. F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120.degree. F. Twenty parts by weight of the liquid raspberry flavor composition of Example VI (containing the mixture of ketones produced according to Example IV, bulked fractions 10-20) is added to the solution which is then homogenized to form an emulsion having particle size typically in the range of 2-5 microns. This material is kept at 120.degree. F. under which conditions the gelatin will not gel.

Coacervation is induced by adding, slowly and uniformly, 40 parts by weight of a 20% aqueous solution of sodium sulphate. During coacervation, the gelatin molecules are deposited uniformly about each oil droplet as a nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000 parts by weight of 7% aqueous solution of sodium sulphate at 65.degree. F. The resulting gelled coacervate may be filtered and washed with water at temperatures below the melting point of gelatin, to remove the salt.

100 parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example IX(B). 300 parts of sucrose and 100 parts of corn syrup are added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long-lasting raspberry flavor.

100 parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example X. 300 parts of sucrose and 100 parts of corn syrup are added. Mixing is effected in a ribbon blender with jacketed walls of the type manufactured by the Baker Perkins Company.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long-lasting raspberry flavor.

The following separate groups of ingredients are prepared: Parts by Weight Ingredient ______________________________________ Group "A" 30.200          Glycerine 15.345          Distilled water .100           Sodium benzoate .125           Saccharin sodium .400           Stannous fluoride Group "B" 12.500          Calcium carbonate 37.200          Dicalcium phosphate (dihydrate) Group "C" 2.000          Sodium n-lauroyl sarcosinate (foaming agent) Group "D" 1.200          Flavor material of Example IX (B) ______________________________________

Procedure: kettle to 160.degree. F. homogeneous gel. homogeneous paste is formed. n-lauroyl sarcosinate. is then transferred to a three roller mill and then homogenized and finally tubed.

The resulting toothpaste, when used in a normal toothbrushing procedure yields a pleasant raspberry flavor of constant strong intensity throughout said procedure (1-1.5 minutes).

The flavor material produced according to the process of Example IX(B) is added to a chewable vitamin tablet formulation at the rate of 10 grams/kilogram which chewable vitamin tablet formulation is prepated as follows:

In a Hobart Mixer, the following materials are blended to homogeneity: Gms/1000 Tablets ______________________________________ Vitamin C (ascorbic acid) as 70.000 ascorbic acid-sodium ascorbate mixture 1:1 Vitamin B.sub.1 thiamine mononitrate 4.000 as Rocoat .RTM. thiamine mononitrate 331/3% (Hoffman LaRoche) Vitamin B.sub.2 (riboflavin) as Rocoat .RTM. 5.000 riboflavin 331/3% Vitamin B (pyridoxine hydrochloride) 4.000 as Rocoat .RTM. pyridoxine hydrochloride 331/3% Niacinamide as Rocoat .RTM. niacinamide 33.000 331/3% Calcium pantothenate   11.500 Vitamin B.sub.12 (cyanocobalamin) as 3.500 Merck 0.1% in gelatin Vitamin E (d1-alpha tocopheryl 6.600 acetate) as dry Vitamin E acetate 331/3% Roche d-biotin Flavor of Example IX(B) 0.114 (as indicated above) ______________________________________ Gms/100 Tablets ______________________________________ Certified lake color 5.000 Sweetener - sodium saccharin 1.000 Magnesium stearate lubricant 10.000 Mannitol q.s. to make 500.000 ______________________________________

Preliminary tablets are prepared by slugging with flat-faced punches and grinding the slugs to 14 mesh. 13.5 grams dry Vitamin A acetate and 0.6 grams Vitamin D are then added as beadlets. The entire blend is then compressed using concave punches at 0.5 grams each.

Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong raspberry flavor for a period of 12 minutes.

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15% Pennsylvania leaf) the following casing is sprayed at a rate of 30%: Ingredients      Parts by Weight ______________________________________ Corn syrup       60.0 Licorice         10.0 Glycerine        20.0 Fig juice         4.6 Prune juice       5.0 Flavoring material of 0.4 Example IX (B) ______________________________________

The resultant product is redried to a moisture content of 20%. On chewing, this tobacco has an excellent substantially consistent, long-lasting, licorice/raspberry flavor profile in conjunction with the tobacco note.

At the rate of 0.02 parts per million to natural guava nectar is added a mixture of the alcohols prepared according to Example V (bulked fractions 1-17). The mixture of alcohols adds to the guava aroma and taste profile interesting musky, fruity, ionone and perfumy aroma characteristics with lactonic flavor characteristics causing the guava nectar to be much more natural-like having interesting "peachy" nuances.

To natural papaya nectar is added the following materials: 5-17: 0.5 ppm

The addition of the mixture of alcohols prepared according to Example V adds to this papaya nectar a very natural "fruity" lactonic aroma and taste profile making it much more aesthetically pleasing than the papaya nectar without the addition of the mixture of alcohols.

The following flavor formulation is prepared: Ingredients         Parts by Weight ______________________________________ Mixture of alcohols prepared 4 according to Example V, bulked fractions 6-17 2-methyl-4-n-propyl oxathiane 3 Natural mango extract 4 ______________________________________

The resulting mixture is added to processed mango juice at the rate of 10 ppm. The resulting mango juice has an excellent "natural", fresh, fruity "unprocessed" flavor and is therefore preferred over "processed mango juice".

## Claims

1. A process for augmenting or enhancing the aroma or taste of a mango, papaya or guava flavored foodstuff or chewing gum comprising the step of adding to said foodstuff or chewing gum from 0.02 parts per million up to about 300 parts per million based on total composition of a mixture of alcohols prepared according to the process consisting essentially of the steps of: hydrogen at a pressure of 4,000 psig and a temperature in the range of 200.degree.-220.degree. C. whereby a mixture of aldehydes is formed; of from 85.degree. C. up to 93.degree. C. and a pressure of from 3 mm/Hg. up to 4 mm/Hg., thereby recovering a mixture of aldehydes; a temperature of about 45.degree. C. thereby forming a mixture of ketones; the range of from 69.degree. C. up to 89.degree. C. and a pressure in the range of from 1.4 up to 1.8 mm/Hg. thereby recovering a mixture of ketones; and then the range of from 50.degree. C. up to 122.degree. C. and a pressure in the range of from 1 up to 2 mm/Hg. and recovering the distillation product, a mixture of alcohols.