# Patent

## Title
Coin sorting machine

## Abstract

This application is a continuation-in-part of U.S. Application for Letters Patent Ser. No. 662,820 filed on Mar. 1, 1976, now U.S. Pat. No. 4,000,329 issued on Dec. 28, 1976, which, in turn, is a continuation-in-part of U.S. Application for Letters Patent Ser. No. 620,355 filed on Oct. 7, 1975, now U.S. Pat. No. 4,000,090 issued on Dec. 28, 1976, which, in turn is a continuation-in-part of U.S. Application for Letters Patent Ser. No. 507,412 filed on Sept. 19, 1974, now U.S. Pat. No. 3,940,499 issued on Feb. 24, 1976.

## Background
The present invention relates to enol esters of the genus of alkyl side chain methyl substituted or unsubstituted 2,2,6-trimethyl-1-cyclohexen-1-vinyl alkanoates including (but not limited to) beta-cyclohomocitral enol esters, produced by the novel processes of our invention, and novel compositions using one or more of such enol esters to alter, modify or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials.

There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or 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 uniform properties in the finished product.

Sweet, woody, floral, fruity, ionone-like, spicey, honey-like, slightly fatty aromatic aromas prior to smoking and sweet, tobacco-like smoke aroma characteristics in the mainstream on smoking are desirable in tobaccos and in tobacco flavoring compositions.

Arctander, "Perfume and Flavor Chemicals", 1969 discloses the use of perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", "isocyclocitral", "alpha-cyclocitrylidene acetaldehyde" and "beta-cyclocitrylidene acetaldehyde", thus:

Alpha-cyclocitral = (2,2,6-trimethyl-5-cyclohexen-1-carboxaldehyde).

beta-cyclocitral = (2,2,6-trimethyl-6-cyclohexen-1-carboxaldehyde). Both isomers are known and have been produced separately. ##STR2## Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of many pieces of proof that isomers (alpha-beta) do often have different colors."

A mixture of two chemicals: 3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde (meta-cyclocitral). ##STR3## 2,4,6-trimethyl-4-cyclohexen-1-carboxaldehyde (symmetric-iso-cyclocitral). ##STR4## Powerful, and diffusive, foliage-green, "dark" weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet green notes are quite natural in high dilution and resemble the odor of stems from plants and flowers fresh from the soil.

Finds use in perfume compositions where it blends excellently with Oakmoss products (compensates for sweetness and lifts the topnote), with Ionones (freshness), Geranium and Galbanum (enhances the green and "vegetable" notes), etc . . . " ##STR5## Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity of the odor to hydrogenated Ionones.

Suggested for use in perfume compositions. It brings a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots are rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss. . . . "

(iv) "763: beta-CYCLOCITRYLIDENE ACETALDEHYDE 2,6,6-trimethyl-1-cyclohexenyl-beta-acrolein. ##STR6## Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone.

Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical completionn to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer. . . . " 2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde ##STR7## Very powerful, sweet, green-floral and somewhat tobacco-herbaceous odor of good tenacity. In extreme dilution reminiscent of the odor of Safran (Saffron).

Interesting material for fresh topnotes, as a modifier for aldehydic-citrusy notes, as a green-floral topnote in flower fragrances, etc. It blends excellently with the aliphatic Aldehydes, with Oakmoss products and herbaceous oils. . . . "

Safranal and beta-cyclocitral are disclosed as volatile constituents of Greek Tobacco by Kimland et al., Phystochemistry 11 (309) 1972. Beta-cyclocitral is disclosed as a component of Burley Tobacco flavor by Demole and Berthet, Helv. Chim. Acta. 55 Fasc 6, 1866 (1972).

Methods for producing enol esters are disclosed in the prior art. Thus, for example, heptaldehyde enol acetate is disclosed to be produced according to the process of reacting heptaldehyde with acetic anhydride in the presence of crystalline potassium acetate at reflux temperatures of 155.degree.-160.degree. C by Bedoukian, J.Am.Chem.Soc. 66, August, 1944, pages 1325-1327.

However, no disclosures exist in the prior art indicating the existence or implying the organoleptic uses of enol esters related to those of the instant invention or methods for synthesizing such compounds.

FIG. 1 is the GLC profile for the reaction product of Example XXXIV wherein cis and trans beta-cyclohomocitral enol butyrate is produced.

FIG. 2 is a GC-MS profile for the reaction product produced in Example XXXIV.

FIG. 3 is the NMR spectrum for the cis isomer of beta-cyclohomocitral enol butyrate produced according to Example XXXIV.

FIG. 4 is the IR spectrum for the cis isomer of beta-cyclohomocitral enol butyrate produced according to Example XXXIV.

FIG. 5 is the IR spectrum for the trans isomer of beta-cyclohomocitral enol butyrate produced according to Example XXXIV.

FIG. 6 is the NMR spectrum for the trans isomer of beta-cyclohomocitral enol butyrate produced according to Example XXXIV.

FIG. 7 is the GLC profile for the reaction product containing beta-cyclohomocitral enol butyrate produced according to Example XXXV.

FIG. 8 is the GLC profile for the beta-cyclohomocitral enol butyrate produced according to Example XXXVI.

FIG. 9 is the GC-MS profile for beta-cyclohomocitral enol butyrate produced according to Example XXXVI.

FIG. 10 is the GLC profile for the beta-cyclohomocitral enol isobutyrate produced according to Example XXXVII.

FIG. 11 is the GC-MS profile for the beta-cyclohomocitral enol isobutyrate produced according to Example XXXVII.

FIG. 12 is the NMR spectrum for the cis isomer of beta-cyclohomocitral enol isobutyrate produced according to Example XXXVII.

FIG. 13 is the NMR spectrum for the trans isomer of beta-cyclohomocitral enol isobutyrate produced according to Example XXXVII.

FIG. 14 is the GLC profile for the beta-cyclohomocitral enol octanoate produced according to Example XXXVIII.

FIG. 15 is the GC-MS profile for the beta-cyclohomocitral enol octanoate produced according to Example XXXVIII.

FIG. 16 is the NMR spectrum for the trans isomer of beta-cyclohomocitral produced according to Example XXXVIII.

FIG. 17 is the NMR spectrum for the cis isomer of beta-cyclohomocitral produced according to Example XXXVIII.

FIG. 18 is the GLC profile for the reaction product of Example XLVII wherein beta-cyclohomocital enol propionate is produced.

FIG. 19 is the GLC profile for the reaction product of Example XLVIII wherein beta-cyclohomocitral enol acetate is produced.

FIG. 20 is the GLC profile for the reaction product of Example XLIX wherein beta-cyclohomoictral enol acetate is produced.

FIG. 21 is the GLC profile for the reaction product of Example L wherein beta-cyclohomocitral enol acetate is produced.

FIG. 22 is the GLC profile for the reaction product of Example LI wherein beta-ionone epoxide is produced.

FIG. 23 is the GLC profile for the reaction product of Example LII.

FIG. 24 is the GLC profile for the reaction product of Example LIII wherein beta-cyclohomocitral enol acetate is produced.

FIG. 25 is the GLC profile for the reaction product of Example LIV wherein beta-cyclohomocitral enol acetate is produced.

FIG. 26 is the GLC profile for the reaction product of Example LV wherein beta-cyclohomocitral enol acetate is produced.

FIG. 27 is the GLC profile for the reaction product of Example LVI wherein beta-cyclohomocitral enol acetate is produced.

FIG. 28 is the GLC profile for the reaction product of Example LVII wherein the enol acetate having the structure: ##STR8## is produced.

FIG. 29 is the GLC profile for the reaction product of acetic anhydride and beta-cyclohomocitral produced according to Example LVIII.

FIG. 30 is the GC-MS profile for the reaction product produced according to Example LVIII.

FIG. 31 is the NMR spectrum for the beta-cyclohomocitral cis enol acetate produced according to Example LVIII.

FIG. 32 is the Infrared spectrum of alpha-ionone epoxide produced in Example XVI.

FIG. 33 is the NMR spectrum for alpha-ionone epoxide produced in Example XVI.

FIG. 34 is the GLC profile of the reaction product produced according to Example XXV, containing beta-cyclohomocitral enol acetate.

FIG. 35 is the GLC profile of the reaction product produced according to Example LXV, containing beta-cyclohomocitral enol laurate.

FIG. 36 is the GC-MS profile of the reaction product produced according to Example LXV, containing beta-cyclohomocitral enol laurate.

It has been discovered that novel tobacco and tobacco flavoring and aroma imparting, augmenting or enhancing compositions having sweet, woody, honey-like, floral, fruity, ionone-like, spicey, slightly fatty, aromatic aromas and tastes prior to smoking and sweet, tobacco-like smoke aroma characteristics in the mainstream on smoking may be provided by the utilization of one or more enol esters (either the "cis" or the "trans" isomer or a mixture of "cis" and "trans" isomers) having the formula: ##STR9## wherein R.sub.1 is straight chain alkyl having 1, 3, 7 or 11 carbon atoms, in tobaccos as well as tobacco substitutes.

The synthesis of such enol esters is specifically described in Application for U.S. Letters Patent Ser. No. 662,820, filed on Mar. 1, 1976. The syntheses are also exemplified hereinafter below.

Our invention provides an organoleptically improved smoking tobacco product and additives thereof, as well as methods of making the same which overcome specific problems heretofore encountered in which specific desired sweet, floraly, woody, spicey, ionone-like and fruity flavor characteristics of natural tobacco (prior to smoking and on smoking; in the mainstream and in the sidestream) are created or enhanced or modified or augmented 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 desirable natural aromatic tobacco flavoring characteristics with sweet, floral and fruity notes may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavoring 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 enol esters of our invention.

In addition to the enol ester or esters of our invention other flavoring and aroma additives may be added to the smoking tobacco material or substitute therefor either separately or in mixture with the enol ester or esters as follows: issued on June 29, 1971.

An aroma and flavoring concentrate containing beta-cyclohomocitral enol ester or esters 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 nautral and/or sweet notes, we have found the satisfactory results are obtained if the proportion by weight of the sum total of enol ester or esters to smoking tobacco material is between 250 ppm and 1,500 ppm (.025%-.15%) 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 enol ester or esters used to flavoring material is between 2,500 and 15,000 ppm (0.25%-1.5%).

Any convenient method for incorporating the enol ester (or esters) into the tobacco product may be employed. Thus, the enol ester (or esters) taken alone or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, diethyl ether and/or volatile organic solvents and the resulting solution may either be spread 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 enol ester (or esters) taken alone or taken 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, or 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 enol ester (or esters) 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 spread with a 20% ethyl alcohol solution of beta-cyclohomocitral enol acetate having the structure: ##STR10## is an amount to provide a tobacco composition containing 800 ppm by weight of beta-cyclohomocitral enol acetate on a dry basis. Thereafter, the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. The cigarette when treated as indicated has a desired and pleasing aroma which is detectable in the main and side streams when the cigarette is smoked. This aroma is described as being sweeter, more aromatic, more tobacco-like and having sweet, fruity notes.

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 enol ester (or esters) 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 enol ester (or mixture of esters) can be added 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 or otherwise, whether composed of tobacco plant parts or substitute materials or both.

Examples IX and LIX, following, serve to illustrate the unworkability of one of these processes where dimethyl formamide, in the absence of an inorganic buffer, is used in the oxidation reaction of beta-ionone with peracetic acid. Example III serves to illustrate the unworkability of that reaction where no buffer, e.g., sodium acetate, is used. Example LI shows the unworkability of the above process using a perphthalic acid anhydride oxidizing agent. Example LII illustrates the unworkability of the above process when using a dimethyl aniline solvent in which the dimethyl aniline is oxidized preferentially over the beta-ionone.

Examples XI-XV, XVIII-XXIV, XXVII-XXXII, XXXIX-XLVI, LXVI-LXIX and LXXI illustrate the utilities of the enol esters of our invention.

Example XVI illustrates the unworkability of the above process in forming an alpha-ionone enol ester when operated on alpha-ionone rather than beta-ionone.

Example XLVII illustrates the unworkability of permaleic acid.

It will be understood that these Examples are illustrative 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.

Into a two liter reaction flask equipped with stirrer, thermometer, reflux condenser, addition funnel and cooling bath, the following materials are added:

(i) Solution of 96 grams beta-ionone in 300 cc chloroform; and

(ii) 30 grams sodium acetate

95 Grams of 40% peracetic acid is then added, with cooling, slowly at 10.degree. C during a period of 1 hour. The reaction mass is stirred at 10.degree. C for an additional hour and the solution is then allowed to slowly warm up to room temperature. The reaction mass is then poured into 1 liter of water and the resultant organic and aqueous phases are separated. The aqueous phase is then extracted with 100 cc of chloroform and the resultant organic phases are then bulked. The solvent is evaporated from the organic phase to yield 99.5 grams of an oil which is then chromatographed on 1,000 grams of alumina deactivated with 5% w/w water and eluted as follows: Fraction Volume of Solvent Quantity of Solute Eluted ______________________________________ 1       750 cc hexane   8.0 grams 2       500 cc hexane  31.7 grams 3       300 cc hexane  13.5 grams 4       250 cc hexane  7.0 grams 5       250 cc hexane   1.9 grams 6       250 cc hexane   1.6 grams 7       600 cc 25% diethyl ether-75% hexane 15.6 grams 8       600 cc diethyl ether 15.3 grams ______________________________________

Fractions 1-4 are composed mainly of "trans" beta-cyclohomocitral enol acetate.

The spectral data for a purified sample of this material obtained by preparative gas chromatography confirm the structure: ##STR11## The mass spectrum of this compound has the following fragmentation pattern, in decreasing order of ion abundance: m/e 166 (100), 151 (81), 43 (30), 208 (30) (molecular ion) and 95 (18). The infrared spectrum shows the following characteristic absorption bands (cm.sup.-1): 3090 ##STR12## 1752           CO (vinyl ester) 1650           CC (conjugated with oxygen) 1360 1380 ##STR13## 1365           CH.sub.3 1215 CO (of the ester) 1080 930 ##STR14## ______________________________________

The NMR spectrum exhibits in CDCl.sub.3 solution the following proton absorptions (chemical shifts in ppm): Ppm     Multiplicity Assignment    No. of Protons ______________________________________ 1.00    (s) ##STR15##    6H 1.70 - 1.40 1.76 (m) (s) ##STR16##     7H 2.00    (t)        CCH.sub.2     2H 2.16    (s) ##STR17##    3H 5.86 and (m)        Olefinic      2H 7.20               protons ______________________________________

The following examples, carried out using the same procedure as Example I, illustrate the results which occur when parameters of the oxidation reaction of beta-ionone with peracetic acid are varied, e.g., as to buffer, solvent, temperature presence of organic base and ratio of organic alkanoic acid to peracetic acid. The percentages given are obtained by gas chromatographic analyses of the reaction mixture after 30 minutes and do not represent yields of isolated material. Reactants and Example % Enol   % Starting % By-  Reaction No.    Ester    Material  Products Conditions ______________________________________ II     47       24        29     Acetic acid- (150 cc) Sodium acetate (20 g) Beta- ionone-(30 g) 40% peracetic acid-(30 g) Temperature: 25.degree. C. III    12       52        36     Acetic acid- (150 g) Beta-ionone- (30 g) 40% peracetic acid-(30 g) Temperature: 25.degree. C. IV     40       29        31     Cyclohexane- (150 cc) Sodium acetate- (20 g) Beta-ionone- (30 g) 40% peracetic acid (30 g) Temperature: 25.degree. C V      52       26        22     Acetic acid- (150 cc) Potassium acetate- (35 g) Beta-ionone- (30 g) 40% peracetic acid (30 g) Temperature: 25.degree. C VI     31       30        39     Formic acid- (150 cc) Potassium acetate- (50 g) Beta-ionone- (30 g) 40% peracetic acid (30 g) Temperature: 25.degree. C VII    49        6        45     Acetic acid- (150 cc) Potassium acetate- (35 g) Beta-ionone- (30 g) 40% peracetic acid (33 g) Temperature: 25.degree. C VIII   36       21        43     Acetic acid- (150 cc) Potassium acetate- (35 g) Beta-ionone- (30 g) 40% peracetic acid- (33 g) Temperature: 50.degree. C IX      0        9        91     Dimethyl Beta-  formamide (150 cc) ionone Beta-ionone- epoxide (30 g) 40% peracetic acid- (33 g) Temperature: 4 days at a temp- erature of 18.degree. C X      55       17        28     Acetic acid- (450 cc) Potassium acetate- (105 g) Beta-ionone- (96 g) 40% peracetic acid- (105 g) Temperature: 25.degree. C ______________________________________

To demonstrate the use of "trans" beta-cyclohomocitral enol acetate in a rose formulation, the following formula is provided: Ingredient             Parts by Weight ______________________________________ Phenylethyl alcohol    200 Geraniol               400 Trichloromethylphenyl carbinyl acetate                20 Phenylethyl acetate    60 Undecylenic aldehyde (10% in diethyl phthalate)             5 n-Nonyl aldehyde (10% in diethyl phthalate)             2 Musk ketone            10 Musk ambrette          10 Eugenol phenyl acetate 20 Citronellol            100 Vanillin (10% in diethyl phthalate) 6 Eugenol                30 Citronellyl formate    30 Geranyl acetate        10 Linalool               40 Geranyl phenyl acetate 50 Cis beta, .gamma.-hexenyl acetate 2 "Trans" beta-cyclohomocitral enol acetate prepared according to 5 Example I              1000 ______________________________________

The addition of 0.5% of beta-cyclohomocitral enol acetate lends a great deal of strength and character to the rose fragrance. It contributes great floralcy and the heady natural sweetness of the red rose flower.

At lower concentrations (0.01%) its contribution is more subtle, however, it still gives an interesting natural effect.

This product may normally be used from approximately 0.01% to 10% in perfume compositions. For special effects, however, higher concentrations (50% plus) can be used.

100 Grams of soap chips are mixed with one gram of the perfume composition of Example XI until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent rose character with excellent sweet, floral and fruity notes.

A total of 100 grams of detergent powder is mixed with 0.15 grams of the perfume composition of Example XI, until a substantially homogeneous composition is obtained. This composition has an excellent rose aroma with sweet, floral and fruity notes.

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

"Trans" beta-cyclohomocitral enol acetate is added to half of the above formulation at the rate of 2.0%. The formulation with the beta-cyclohomocitral enol acetate is compared with the formulation without the beta-cyclohomocitral enol acetate at the rate of 0.01 percent (100 ppm) in water and evaluated by a bench panel.

The flavor containing the "trans" beta-cyclohomocitral enol acetate is found to have substantially sweeter aroma notes and a sweet raspberry, raspberry kernel-like and sweet aftertaste and mouthfeel missing in the basic raspberry formulation. It is the unanimous opinion of the bench panel that the chemical, "trans" beta-cyclohomocitral enol acetate rounds the flavor out and contributes to a very natural fresh aroma and taste as found in full ripe raspberries. Accordingly, the flavor with the addition of the beta-cyclohomocitral enol acetate is considered as substantially better than the flavor without "trans" beta-cyclohomocitral enol acetate.

"Eveready" canned carrot juice, manufactured by the Dole Corporation of San Jose, California, is intimately admixed with 15 ppm of "trans" beta-cyclohomocitral enol acetate and the resulting mixture is compared with same juice unflavored. The weak aroma and taste of the juice is substantially improved whereby a fresh carrot juice and pleasant sweet note are added thereto. A bench panel of five people prefers the carrot juice flavored with "trans" beta-cyclohomocitral enol acetate as compared with the unflavored carrot juice.

Into a 500 ml flask equipped with thermometer, stirrer, addition funnel and reflux condenser, the following materials are placed in the following order: Ingredients          Amount ______________________________________ Acetic Acid          150    cc Potassium Acetate     35    grams Alpha-Ionone          30    grams ______________________________________

33 Grams of 40% peracetic acid is then added dropwise into the reaction mass with stirring at 25.degree. C over a 45-minute period. The reaction mass exotherms for approximately 1 hour and is then allowed to remain at room temperature for a period of 15 hours.

The reaction mass is then poured into 500 ml water and the product is extracted with three 150 cc portions of diethyl ether. The ether extracts are combined and washed with two 100 cc portions of saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The residual oil obtained after stripping the solvent, is distilled at 93.degree.-99.degree. C at 0.5 mm Hg pressure yielding 28.3 of a clean colorless liquid.

IR, MS and NMR analyses confirm the fact that the product is alpha-ionone epoxide having the structure: ##STR18##

Mass spectral analysis for alpha-ionone epoxide is as follows: Relative Intensity (Order of Most Abundant Ion m/e          Indicated in Superscript) ______________________________________ 39          18 41          30.sup.4 43          100.sup.1 55          20 95          40.sup.3 109          60.sup.2 111          30.sup.5 151          16 165          18 179          23.sup.6 208           9 ______________________________________

The IR spectrum for alpha-ionone epoxide is set forth in FIG. 32. FIG. 33 is the NMR spectrum for alpha-ionone epoxide.

Into a 2 liter reaction flask equipped with stirrer, thermometer, addition funnel and cooling bath, the following materials are placed in the following order: Ingredients            Amounts ______________________________________ Acetic Acid            450    cc Potassium Acetate      105    g Beta-Ionone             96    g ______________________________________

105 Grams of 40% peracetic acid is then added dropwise to the reaction mass with cooling while maintaining the reaction mass at 25.degree. C .+-. 2.degree. C over a period of 2 hours. The reaction mass is then stirred for an additional 3 hour period (during the first hour a slight exotherm occurs) at 25.degree. C.

The reaction mass is then poured into 1,000 ml water and the resultant product is extracted with three 300 cc volumes of diethyl ether. The ether extracts are combined and washed with two 150 cc portions of saturated sodium chloride solution. The resultant washed ether extract is then evaporated whereby 118 grams of residual oil is obtained. NMR, IR and Mass Spectral analyses confirm that the resulting material is "trans" beta-cyclohomocitral enol acetate.

A tobacco mixture is produced by admixing the following ingredients: Ingredient           Parts by Weight ______________________________________ Bright               40.1 Burley               24.9 Maryland             1.1 Turkish              11.6 Stem (flue-cured)    14.2 Glycerine            2.8 Water                5.3 ______________________________________

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared: Ingredient          Parts by Weight ______________________________________ Ethyl butyrate      .05 Ethyl valerate      .05 Maltol              2.00 Cocoa extract       26.00 Coffee extract      10.00 Ethyl alcohol       20.00 Water               41.90 ______________________________________

The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 500 or 1,000 ppm of "trans" beta-cyclohomocitral enol acetate produced according to the process of Example XVII. The control cigarettes not containing the "trans" beta-cyclohomocitral enol acetate and the experimental cigarettes which contain the "trans" beta-cyclohomocitral enol acetate produced according to the process of Example XVII are evaluated by paired comparison and the results are as follows:

The experimental cigarettes are found, on smoking, to have more "body" and to be sweeter, more aromatic, more tobacco-like and less harsh with sweet, floral and fruity notes.

The tobacco of the experimental cigarettes, prior to smoking, has sweet, floral and fruity notes. All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

The "trans" beta-cyclohomocitral enol acetate produced according to the process of Example XVII enhances the tobacco like taste and aroma of the blended cigarette imparting to it sweet, natural tobacco notes.

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 0.25 g of "trans" beta-cyclohomocitral enol acetate prepared according to Example XVII. It has an excellent sweet, floral, fruity aroma.

Concentrated liquid detergents with a sweet, floral, fruity odor are prepared containing 0.10%, 0.15% and 0.20% of "trans" beta-cyclohomocitral enol acetate prepared according to Example XVII. They are prepared by adding and homogeneously mixing the appropriate quantity of "trans" beta-cyclohomocitral enol acetate in the liquid detergent. The detergents all possess a sweet, floral, fruity fragrance, the intensity increasing with greater concentrations of "trans" beta-cyclohomocitral enol acetate.

Trans beta-cyclohomocitral enol acetate prepared according to the process of Example XVII is incorporated in a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). A distinct and definite sweet, floral, fruity fragrance is imparted to the cologne and to the handkerchief perfume.

The composition of Example XI is incorporated in a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). The use of the beta-cyclohomocitral enol acetate in the composition of Example XI affords a distinct and definite strong rose aroma with sweet, floral, fruity notes to the handkerchief perfume and cologne.

One hundred grams of soap chips are mixed with one gram of "trans" beta-cyclohomocitral enol acetate until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent sweet, floral, fruity aroma.

A total of 100 g of a detergent powder is mixed with 0.15 g of the "trans" beta-cyclohomocitral enol acetate of Example XVII until a substantially homogeneous composition is obtained. This composition has an excellent sweet, floral, fruity aroma.

Perpropionic acid is prepared in the following manner. A mixture of the following materials: 160 ml propionic acid 1 ml sulfuric acid (concen- Referred to trated)                    hereinafter as 40 g 50% hydrogen peroxide "Mixture A" ______________________________________

is allowed to stand for 20 hours at room temperature.

The following reactants are placed in a 500 ml reaction flask equipped with a stirrer and cooling bath: 140 ml propionic acid     Referred to 75 g potassium acetate   hereinafter as 60 g beta-ionone         "Mixture B" ______________________________________

To the stirred Mixture B is added, dropwise, Mixture A over a 60-minute period while maintaining the reaction temperature at 25.degree. .+-. 2.degree. C by means of external cooling. When the addition is complete the reaction mixture is stirred for an additional 2 hours at 25.degree. C.

The reaction mixture is then poured into 1,000 ml water and extracted twice with 250 ml portions of diethyl ether. The combined ether extracts are then washed first with water (three 100 ml portions) and then with a saturated solution of sodium chloride (150 ml). The ether solution is then dried over anhydrous magnesium sulfate and the solvent evaporated to yield 78 g of crude oil containing propionic acid as well as the product, "trans" beta-cyclohomocitral enol acetate.

The GLC profile for the resulting material is set forth in FIG. 34 (GLC conditions: 10 feet .times. 1/4 inch 10% Carbowax 20M column, operated at 220.degree. C isothermal).

Performic acid is prepared in the following manner: 20 g 50% hydrogen peroxide and 80 ml of formic acid is admixed and the reaction mass is left at room temperature for 1.5 hours.

To a mixture consisting of 50 g of potassium acetate, 70 ml of acetic acid and 30 g of beta-ionone is added the preformed performic acid, prepared as described above, dropwise over a 30 minute period while maintaining the temperature of the stirred reaction mass at 25.degree. C by means of external cooling. After the addition is complete, the mixture is stirred for a further 90 minutes at 25.degree. C and is then poured into 800 ml of water. The product is extracted with two 200 ml portions of diethyl ether. The ether extracts are combined, washed with two 150 ml portions of saturated sodium chloride solution and then dried. Removal of the solvent by evaporation yields 32.5 g crude oil.

A gas chromatographic analysis of this material shows the following compositions: ##STR19##                (4%); ##STR20##                (41%); ("trans" isomer) ##STR21##                (32%); Other products 23% ______________________________________

20 Grams of the flavor composition of Example XIV is emulsified in a solution containing 300 gm gum acacia and 700 gm 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 r.p.m.

The following mixture is prepared: Ingredient             Parts by Weight ______________________________________ Liquid Raspberry Flavor Composition of Example XIV 20 Propylene glycol       9 Cab-O-Sil .RTM. M-5 (Brand of Silica produced by the Cabot Corporation of 125 High Street, Boston, Mass. (02110; Physical Properties: Surface Area: 200 m.sup.2 /gm Nominal particle size: 0.012 microns Density: 2.3 lbs/cu.ft.) 5.00 ______________________________________

The Cab-O-Sil is dispersed in the liquid raspberry flavor composition of Example XIV 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 flavor powder.

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of 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. 20 Parts by weight of the liquid flavor composition of Example XIV 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 jell.

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

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

Hardening of the filtered cake, in this example, is effected by washing with 200 parts by weight of 37% solution of formaldehyde in water. The cake is then washed to remove residual formaldehyde.

100 parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example XXVII. 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 XXVIII. 300 parts of sucrose and 100 parts of corn syrup are then 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.

The following separate groups of ingredients are prepared: Parts by Weight Ingredient ______________________________________ Group "A" 30.200    Glycerin 15.325    Distilled Water .100     Sodium Benzoate .125     Saccherin 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 XXVII 100.00 (Total) ______________________________________ PROCEDURE* 1. The ingredients in Group "A" are stirred and heated in a steam jackete kettle to 160.degree. F. 2. Stirring is continued for an additional three to five minutes to form homogenous gel. 3. The powders of Group "B" are added to the gel, while mixing until a homogenous paste is formed. 4. With stirring, the flavor of "D" is added and lastly the sodium n-lauroyl sarcosinate. 5. The resultant slurry is then blended for one hour. The completed paste 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 XIX is added to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kg which Chewable Vitamin Tablet Formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity: Gms/1000 tablets ______________________________________ Vitamin C (ascorbic acid) as ascorbic acid-sodium ascorbate mixture 1:1 70.0 Vitamin B.sub.1 (thiamine mononitrate) as Rocoat.RTM. thiamine mononitrate 331/3 (Hoffman La Roche)      4.0 Vitamin B.sub.2 (riboflavin) as Rocoat.RTM. riboflavin 331/3 5.0 Vitamin B.sub.6 (pyridoxine hydrochloride) as Rocoat.RTM. pyridoxine hydrochloride 331/3 4.0 Niacinamide as Rocoat.RTM. niacinamide 331/3 33.0 Calcium pantothenate    11.5 Vitamin B.sub.12 (cyanocobalamin) as Merck 0.1% in gelatin 3.5 Vitamin E (dl-alpha tocopheryl acetate) as dry Vitamin E acetate 331/3% Roche 6.6 d-Biotin                0.044 Certified lake color    5.0 Flavor of Example XXVIII (as indicated above) Sweetener -sodium saccharin 1.0 Magnesium stearate lubricant 10.0 Mannitol q.s. to make   500.0 ______________________________________

Preliminary tablets are prepared by slugging with flat-faced punches and grinding the slugs to 14 mesh. 13.5 g dry Vitamin A Acetate and 0.6 g Vitamin D are then added as beadlets. The entire blend is then compressed using concave punches at 0.5 g 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 Licorice            10 Glycerine           20 Fig Juice           4.6 Prune Juice         5 Flavor Material of Example XXVIII      0.4 ______________________________________

The resultant product is redried to a moisture content of 20%. On chewing, this tobacco has an excellent substantially consistent, long-lasting raspberry (20 minutes) nuance in conjunction with the main fruity tobacco note. ##STR22##

Into a 100 ml reaction flask are added the following materials: Ingredients        Quantity ______________________________________ beta-cyclohomocitral 16.6 g    (0.1 moles) butyric anhydride  27 g      (0.17 moles) potassium acetate  1 g       (0.01 moles) ______________________________________

The reaction mass is heated at a temperature of 170.degree. C for a period of 9.5 hours. At this period in time GLC analysis indicates the substantially total disappearance of the beta-cyclohomocitral and the formation of two new peaks. GC-MS analysis indicates that the peaks represent the "cis" and "trans" isomers of beta-cyclohomocitral enol butyrate having, respectively, the structures: ##STR23## The GLC profile is set forth in FIG. 1 (conditions: 10 feet .times. 1/8 inch Carbowax 20 M column, programmed from 80.degree.-180.degree. C at 4.degree. C per minute).

The GC-MS profile is set forth in FIG. 2.

The NMR analysis of the "cis" isomer of beta-cyclohomocitral enol butyrate is as follows: 0.97 ppm singlet superimposed on triplet ##STR24## and ##STR25##     9H 1.54   broad singlet        CCH.sub.3 9H 1.78-1.21 multiplet            (CH.sub.2).sub.3 2.00   diffuse triplet      CCH.sub.2      2H 2.35   triplet ##STR26##     2H 5.32   doublet (J=7Hz,cis) ##STR27##      1H 7.06   doublet                             1H ______________________________________

the NMR spectrum for the "cis" isomer of beta-cyclohomocitral enol butyrate is set forth in FIG. 3.

The Infrared analysis for the "cis" isomer of beta-cyclohomocitral enol butyrate is as follows:

740, 1085, 1160, 1230, 1360, 1750, 2870, 2940, 2960 cm.sup.-1

The Infrared spectrum for the "cis" isomer of beta-cyclohomocitral enol butyrate is set forth in FIG. 4.

The Infrared analysis for the "trans" isomer of beta-cyclohomocitral enol butyrate is as follows:

930, 1100, 1160, 1230, 1360, 1750, 2870, 2940, 2960 cm.sup.-1

The Infrared analysis for the "trans" isomer of beta-cyclohomocitral enol butyrate is set forth in FIG. 5.

The NMR spectrum for the "trans" isomer of beta-cyclohomocitral enol butyrate is set forth as follows: 1.00 ppm doublet superimposed on triplet ##STR28##     9H 1.82-1.43 multiplet       CCH.sub.3 +             11H (CH.sub.2).sub.4 2.00    diffuse triplet CCH.sub.2     2H 2.40    triplet ##STR29##    2H 5.86    doublets (J=13 Hz, trans) ##STR30##    2H 7.02 ______________________________________

the NMR spectrum for the "trans" isomer of beta-cyclohomocitral enol butyrate is set forth in FIG. 6.

The crude reaction mass produced as described supra is admixed with 100 ml diethyl ether. The resulting diethyl ether solution is washed with two 100 ml portions of water and one 25 ml portion of saturated sodium bicarbonate. The washed ether solution is dried over anhydrous magnesium sulfate, filtered and stripped on a Rotovap evaporator yielding 32.4 g of product containing a significant amount of enol butyrate. The components are separated by preparative GLC.

The "trans" beta-cyclohomocitral enol butyrate at 2 ppm has a sweet, rosey, fruity aroma. At 5 ppm it has a sweet/rosey, rosebud, rosey/fruity aroma and a rosey/fruity taste. At 20 ppm it has a sweet/rosey/fruity aroma and taste with a delicate "damascenone"-like character.

The "cis" beta-cyclohomocitral enol butyrate at 0.2 ppm only has a bitter aftertaste. At 2 ppm it has a weak rosey aroma. At 6 ppm it has a weak, rosey aroma and bitter aftertaste. ##STR31##

Into a 100 ml reaction flask are charged the following materials: Ingredients        Quantity ______________________________________ beta-cyclohomocitral 16.6 g    (0.1 mole) paratoluene sulfonic acid 0.5 g     (0.03 moles) butyric anhydride  39.5 g    (0.25 mole) ______________________________________

The reaction mass is heated with stirring to 170.degree. C and maintained at 170.degree. C for a period of 9.5 hours. At the end of this time GLC analysis indicates a substantial proportion of beta-cyclohomocitral enol butyrate (conditions: 4 feet .times. 1/4 inch Carbowax 20 M column, programmed from 80.degree.-180.degree. C at 4.degree. C per minute).

The GLC profile is set forth in FIG. 7.

The GLC profile indicates a substantial amount of "cis" isomer and a substantial amount of "trans" isomer. NMR and mass spectral analyses confirm that peak "D" of FIG. 7 is the "cis" isomer and peak "E" is the "trans" isomer.

The crude material is admixed with 100 ml of ether and the resulting ether solution is washed with two 100 ml portions of water followed by one 25 ml portion of sodium bicarbonate. The washed ether solution is then dried over anhydrous magnesium sulfate, filtered and stripped using a "Rotovap" evaporator. The resulting product is 32.4 g product containing a significant proportion of beta-cyclohomocitral enol butyrate. The products are separated by preparative GLC. ##STR32##

Into a 25 ml reaction flask the following materials are added: Ingredients        Quantity ______________________________________ beta-cyclohomocitral enol acetate produced according to Example I       2.0 g     (0.008 moles) butyric anhydride  2.5 g     (0.016 moles) paratoluene sulfonic acid trace ______________________________________

The reaction mass is heated with stirring at a temperature of 170.degree. C and maintained at that temperature for a period of 8 hours. At the end of this 8 hour period, GLC analysis indicates the presence of a substantial quantity of "trans" beta-cyclohomocitral enol butyrate. This is confirmed by NMR and mass spectral analyses.

The GLC profile for the reaction product at the point in time is set forth in FIG. 8.

The GC-MS profile is set forth in FIG. 9.

25 ml diethyl ether is admixed with crude product and the ether solution is washed with two 25 ml portions of water and one 25 ml portion of sodium bicarbonate. The washed ether solution is then dried over anhydrous magnesium sulfate, filtered and stripped on a "Rotovap" evaporator thus yielding a product containing a significant proportion of "trans" beta-cyclohomocitral enol butyrate. ##STR33##

Into a 100 ml reaction flask equipped with stirrer, thermometer and reflux condenser are placed the following ingredients: Ingredients        Quantity ______________________________________ beta-cyclohomocitral 16.6 g    (0.1 mole) isobutyric anhydride 27 g      (0.17 mole) potassium acetate  12 g      (0.01 mole) ______________________________________

The reaction mass is heated at a temperature of 169.degree. C for a period of 13 hours. The reaction mixture turns dark and 100 ml of diethyl ether is added to the mixture. The reaction mass is then washed with two 100 ml portions of water and one 100 ml portion of saturated aqueous sodium bicarbonate. The organic layer is then dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap yielding 35.5 g of crude product. The GLC profile of the crude product indicates that only a trace quantity of beta-cyclohomocitral remains with two product peaks having a longer retention time being formed. The GLC profile for the reaction product at this point in time is set forth in FIG. 10 (conditions: 10 feet .times. 1/8 inch Carbowax 20M column, programmed from 80.degree.-180.degree. C at 4.degree. C per minute).

The GC-MS profile is set forth in FIG. 11.

The materials composing the two major peaks are isolated by preparative GLC and are analyzed using NMR analysis, peak 1 being confirmed to be the cis isomer of beta-cyclohomocitral enol isobutyrate and peak 2 being confirmed to be the trans isomer of beta-cyclohomocitral enol isobutyrate. The NMR spectrum for the "cis" isomer is set forth in FIG. 12. The NMR spectrum for the "trans" isomer is set forth in FIG. 13.

The trans isomer of beta-cyclohomocitral enol isobutyrate, insofar as its flavor properties are concerned, has a sweet, woody, rosey, fruity, "wood-rosin", spicey, apple juice aroma with fruity, apple/raspberry, woody, sweet, wood-rosin, tea and astringent flavor characteristics. Insofar as its perfumery uses are concerned, it has an acidic, fruity, "damascenone"-like aroma with strong animal tobacco nuances; stronger than those of the "cis" isomer.

The cis isomer of beta-cyclohomocitral enol isobutyrate, insofar as its flavor properties are concerned, has a sweet, oriental/olibanum, "delicate rosey", fruity, ionone-like, clove, camphoraceous aroma with rosey, woody, clove, mimosa, ionone, musty and camphoraceous flavor characteristics. The perfume properties of the cis isomer are such that it has a sweet, woody, green tobacco aroma with fruity and resinous notes; but it is not quite as fruity as the trans isomer. The cis isomer also has strong ionone, mimosa nuances.

It is noteworthy that the cis and trans isomers have uses in food flavors different from one another. The cis isomer is useful in clove and cinnamon flavors whereas the trans isomer is useful in apple juice, tea, raspberry and honey flavors. ##STR34##

Into a 100 ml reaction flask equipped with stirrer, thermometer and reflux condenser is placed the following ingredients: Ingredients        Quantity ______________________________________ beta-cyclohomocitral 16.6 g    (0.1 mole) octanoic anhydride 41 g      (0.17 mole) potassium acetate  1 g       (0.01 mole) ______________________________________

The reaction mass is heated for a period of 11 hours at a temperature in the range of from 170.degree.-190.degree. C. At the end of the 11 hour period 100 ml of diethyl ether is added to the reaction mass after cooling the reaction mass to room temperature. The resulting mixture is then washed with two 100 ml portions of water and one 100 ml portion of saturated aqueous sodium bicarbonate. The organic layer is separated from the aqueous layer; then dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap yielding 31.4 g of oil. GLC analysis of the crude material indicates several peaks. The GLC profile is set forth in FIG. 14. The GLC conditions are the same as those which are set forth in Example XXXVII.

The GC-MS profile for the reaction product is set forth in FIG. 15.

Two major peaks are trapped and NMR analysis confirms that one of the peaks is cis-beta-cyclohomocitral enol octanoate and the other peak is trans-beta-cyclohomocitral enol octanoate.

FIG. 16 is the NMR spectrum for the "trans" isomer of beta-cyclohomocitral enol octanoate. FIG. 17 is the NMR spectrum for the "cis" isomer of beta-cyclohomocitral enol octanoate.

The "cis" isomer, from a flavor evaluation standpoint, has a sweet, rosey, "damascenone"-like, dried fruit, cocoa aroma and a sweet, delicate rosey, "damascenone"-like, tea, apple-juice-like, tobacco flavor character. The "trans" isomer has an ionone-like, woody aroma character with an ionone-like, woody, musty and astringent flavor character. The "cis" isomer is much preferred over the "trans" isomer for flavor use.

From a perfumery standpoint the "cis" isomer has a woody, cheesy, fatty, rather acrid aroma with some ionone nuances. The "trans" isomer has a woody, cheesy, fatty aroma with more of a warm, fruity note than does the "cis" isomer with cognac, balsamic and tobacco nuances, however, the cheesy note dominates.

The following mixture is prepared: Ingredient           Parts by Weight ______________________________________ Citronellal          60 Geraniol             40 Citronellyl formate  5 Geranyl acetate      3 Phenylethyl alcohol  20 Phenyl acetic acid   3 Methyl phenyl acetate 1 Phenylethyl acetate  2 4-(4-methyl-4-hydroxy).DELTA..sup.3 - cyclohexene carboxaldehyde 3 Linalool             6 Eugenol              2 Mixture of "cis" and "trans" beta- cyclohomocitral enol isobutyrate produced according to the process of Example XXXVII    5 ______________________________________

The mixture of "cis" and "trans" beta-cyclohomocitral enol isobutyrate produced according to Example XXXVII imparts to this rose formulation a sweet, fruity, "damascenone"-like quality thus imparting thereto an unexpected, unobvious and advantageous "lift".

The following basic cinnamon flavor is prepared: Ingredient           Parts by Weight ______________________________________ Cassia oil           10.0 Cinnamaldehyde       70.0 Cinnamyl formate     0.5 Cuminic aldehyde     0.2 Eugenol              14.0 Furfural             0.2 Methyl cinnamate     2.5 Caryophyllene        2.6 ______________________________________

The formulation is divided into two equal parts. To the first part, at the rate of 10 ppm "cis" beta-cyclohomocitral enol isobutyrate prepared according to the process of Example XXXVII, is added in the form of a 5% solution in food grade 95% aqueous ethyl alcohol. The second part of the formulation has nothing additional added thereto. The flavor formulation containing the "cis" beta-cyclohomocitral enol isobutyrate has more of the desired woody/powdery, delicate, sweet aroma and taste characteristics not found in the basic flavor formulation. Therefore, it is preferred over the flavor formulation which does not contain the said betacyclohomocitral enol isobutyrate. BUTYRATE

The following basic raspberry formulation is prepared: Ingredient             Parts by Weight ______________________________________ Vanillin               2 Maltol                 4 Parahydroxy benzyl acetone 5 Alpha-ionone (10% in propylene glycol) 2 Ethyl butyrate         6 Ethyl acetate          16 Dimethyl sulfide       1 Isobutyl acetate       14 Acetic acid            10 Acetaldehyde           10 Propylene glycol       930 ______________________________________

The foregoing formulation is divided into two parts. To the first part is added "cis" beta-cyclohomocitral enol butyrate prepared according to the process of Example XXXV at the rate of 100 ppm in the form of a 5% solution in food grade 95% aqueous ethanol. The second portion of the above formulation does not have any additional materials added thereto. The two formulations are compared. The formulation containing the "cis" isomer of beta-cyclohomocitral enol butyrate has a sweet, ripe raspberry aroma and a full, more ripe raspberry-like taste; and as such it is preferred over the formulation not containing said "cis" isomer of beta-cyclohomocitral enol butyrate.

At the rate of 3 ppm "cis" beta-cyclohomocitral enol octanoate, prepared according to the process of Example XXXVIII, is added to a standard instant tea formulation. The instant tea is made up into a tea beverage by means of the addition of boiling water thereto. The stale, bitter, tannin notes of the hot tea are substantially improved by means of the addition of the "cis" isomer of beta-cyclohomocitral enol octanoate. Fruity/delicate rosey, pleasant tealike aroma notes and fruity/delicate rosey/tea taste notes are added to the basic tea taste and aroma by means of the "cis" iosmer of beta-cyclohomocitral enol octanoate.

At the rate of 3 ppm the trans isomer of betacyclohomocitral enol isobutyrate is added to a standard commercial instant tea vending machine product. Prior to addition the tea is not considered to have a pleasant tealike aroma. The taste is stale and bitter with the tannin notes dominating. The addition of the trans isomer of betacyclohomocitral enol butyrate at the rate of 3 ppm to the bitter tea followed by the addition of boiling water in order to make a beverage, adds a light, fruity/apple, pleasant tea aroma to the beverage and improves the taste with delicate/fruity/tea-like notes.

At the rate of 1 ppm, the trans isomer of betacyclohomocitral enol butyrate prepared according to Example XXXVI is added to Hi-C Grape Drink (containing 10% grape juice) manufactured by the Coca Cola Corporation of Houston, Texas. The addition of the "trans" isomer of beta-cyclohomocitral enol butyrate to the Hi-C grape drink at the rate of 1 ppm in the form of a 1% propylene glycol solution improves the flat top notes of the drink adding a delicate concord grape flavor and a fuller taste thereto. ACETATE

The following basic clove formulation is prepared: Ingredient             Parts by Weight ______________________________________ Vanillin               2 Caryophyllene          8 Guaiacol (10% solution in 95% aqueous food grade ethanol)    1 Cuminaldehyde          1 5-Methyl furfural      5 Eugenol                83 ______________________________________

The above formulation is divided into two parts. To the first part is added at the rate of 5% the "cis" isomer of beta-cyclohomocitral enol acetate prepared according to the process of Example LVIII, infra. The second part of the above formulation does not have any additional ingredients added thereto. The use of the "cis" isomer of beta-cyclohomocitral enol acetate in this basic clove formulation causes the formulation to have added thereto dry-woody notes in aroma and taste. As a result of adding the "cis" isomer of beta-cyclohomocitral enol acetate, the clove aroma is more delicate, better rounded and therefore preferred as better and more characteristic. ##STR35##

Into a 250 ml reaction flask equipped with stirrer, addition funnel, thermometer and cooling bath, the following materials are placed: Ingredients       Quantity ______________________________________ beta-n-methyl ionone (91% 22.6 g (0.1 mole) purity) water             40 ml acetic acid       50 ml sodium acetate    17 g (0.17 mole) ______________________________________

The reaction mass is stirred for a period of 10 minutes at room temperature at which time the addition of 24.0 g (0.13 mole) of a 40% solution of peracetic acid is commenced. The peracetic acid is added over a period of 15 minutes while the reaction mass is maintained at a temperature of 25.degree.-30.degree. C. After addition of the peracetic acid is completed, the reaction mass is stirred for a period of 2 hours while maintaining the temperature of 25.degree.-30.degree. C. The reaction mass is then added to 200 ml water and the resulting mixture is extracted with one 200 ml portion of methylene chloride and again with one 100 ml portion of methylene chloride. The methylene chloride extracts are combined with the organic phase and the combined extracts are washed with two 100 ml portions of water. The resulting material is dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap yielding 23 grams or product.

The GLC profile of the reaction product containing trans beta-cyclohomocitral enol propionate is set forth in FIG. 18.

The "trans" beta-cyclohomocitral enol propionate insofar as its flavor is concerned has a sweet, floral, ionone-like, raspberry, dried fruit, tobacco-like aroma with a sweet, fruity, ionone, raspberry, dried fruit, tobacco flavor characteristic at 1 ppm. It is about two times as strong, sweeter, fruitier, and more raspberry-like than the "trans" beta-cyclohomocitral enol acetate.

Insofar as its perfumery properties are concerned the "trans" beta-cyclohomocitral enol propionate has a butyric/propionic acid topnote with tobacco, woody and inonone notes; but it is not as pleasant as "trans" betacyclohomocitral enol acetate which is preferred by a panel of perfumers. ACID ANHYDRIDE

Into a 500 ml flask equipped with ice bath, thermometer and magnetic stirrer are placed 150 ml methylene chloride and 38.5 g (0.34 moles) of 30% hydrogen peroxide. The resulting mixture is cooled to 0.degree. C using the ice bath and 39.2 g (0.4 moles) of freshly crushed maleic anhydride is added to the mixture. The reaction mixture is stirred for one hour and is then brought to reflux. While refluxing 38.4 g (0.2 moles) of beta-ionone in 40 g of methylene chloride is added to the reaction mass over a one hour period. The reaction mass is then stirred for a period of 2 hours and now exists in two phases; an aqueous phase and an organic phase. The organic phase is separated and washed with one 150 ml portion of saturated sodium carbonate followed by one 150 ml portion of saturated sodium chloride solution. The organic phase is then dried over anhydrous magnesium sulfate and stripped on a Rotovap to yield 37 g of crude product. GLC analysis of the crude material indicates a 97.5% yield of beta-ionone epoxide. At best, there is only a trace of beta-cyclohomocitral enol acetate present in the reaction product. SOLVENT ##STR36##

Into a 250 ml reaction flask equipped with stirrer, thermometer, cooling bath and additional funnel the following materials are added: Ingredients       Quantity ______________________________________ Methylene dichloride 100 ml Beta-ionone       19.2 g (0.1 mole) Sodium acetate    13 g (0.13 mole) ______________________________________

The reaction mass is stirred at room temperature for a period of 10 minutes, after which period of time addition of 19.2 g (0.10 mole) of 40% peracetic acid is commenced with a reaction exotherm noted. The addition of the peracetic acid takes place over a period of 45 minutes at a temperature from about 25.degree. up to 30.degree. C. After the 45 minute period of addition, the reaction mass is stirred for 1.5 hours. A sample taken at this point indicates a ratio of beta-cyclohomocitral enol acetate:beta-ionone epoxide of 1:1. Stirring is continued for another 2.25 hours at which time GLC indicates the same ratio of enol acetate:epoxide.

At the end of 3.75 hours the reaction mass is added to 100 ml water yielding 2 phases; an organic phase and an aqueous phase. The aqueous phase is separated from the organic phase and the organic phase is washed with three 100 ml portions of water. The organic phase is then dried over anhydrous magnesium sulfate, filtered and stripped on a Rotovap yielding 10.5 grams of an oil. GLC analysis of the crude product indicates: Ingredients          Quantity ______________________________________ beta-cyclohomocitral 0.5% trans beta-cyclohomocitral enol acetate         21% unreacted beta-ionone 33% beta-ionone epoxide  42% ______________________________________

The yield of beta-cuclohomocitral enol acetate is thus determined to be about 20% with percent conversion from beta-ionone to enol acetate of about 30%. FIG. 19 sets forth the GLC profile for the crude reaction product. SOLVENT

Into a 500 ml reaction flask equipped with stirrer, thermometer and addition funnel the following materials are added: Ingredients       Quantity ______________________________________ anhydrous benzene 100 ml beta-ionone       19.2 g (0.1 mole) sodium acetate    13 g (0.13 mole) ______________________________________

The reaction mass is stirred for a period of 10 minutes at room temperature. At this point addition of 19.2 g (0.10 mole) of 40% peracetic acid is commenced and continued for a period of 30 minutes while maintaining the reaction mass temperature at 25.degree.-30.degree. C. The reaction mass is then stirred for another 3 hours at which time it is added to 150 ml of saturated sodium chloride solution. 50 ml of methylene chloride is then added to the resulting mixture. The organic phase is separated from the aqueous phase and the organic phase is washed with one 100 ml portion of saturated aqueous sodium chloride and one 100 ml portion of water. The organic phase is then dried over anhydrous magnesium sulfate, filtered and strippd on a Rotovap to yield 22.8 g of an oil. GLC analysis of the crude product indicates: Ingredients       Quantity ______________________________________ trans beta-cyclohomocitral enol acetate      25.0% (27.4% yield) beta-ionone       27.5% (32.6% recovery) beta-ionone epoxide 36.1% (39.5% yield) ______________________________________

Based on the foregoing results the yield of trans beta-cyclohomocitral enol acetate is 27.4%. FIG. 20 illustrates the GLC profile of the crude reaction product. M-CHLOROPERBENZOIC ACID OXIDIZING AGENT ##STR37##

Into a 500 ml reaction flask equipped with stirrer, thermometer and additional funnel the following materials are added: Ingredients        Quantity ______________________________________ Benzene            100 ml Sodium acetate     13 g      (0.13 mole) Beta-ionone        19.2 g    (0.10 mole) ______________________________________

The reaction mass is stirred for 10 minutes at which time addition of 21.4 g (0.1 mole) of 85% m-chloroperbenzoic acid is commenced. Addition of the m-chloroperbenzoic acid is carried out for a period of 80 minutes while maintaining the temperature at 25.degree.-30.degree. C. At the end of the 80 minute period the reaction mass is stirred for an additional 2 hours at which time the solids are filtered from the reaction mass. The organic layer is then washed with one 100 ml portion of water, dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap to yield 21.9 g of an oil. GLC analysis of the crude oil indicates: Ingredients        Quantity ______________________________________ Trans beta-cyclohomocitral enol acetate       28.3% (29.7% yield) Beta-ionone        22.6% (25.7% recovery) beta-ionone epoxide 37.8% (39.7% yield) ______________________________________

Fig. 21 sets forth the GLC profile for the crude reaction product. ACID ANHYDRIDE OXIDIZING AGENT AND A CYCLOHEXANE SOLVENT ##STR38##

Into a 500 ml reaction flask equipped with stirrer, thermometer and addition funnel the following materials are added: Ingredients        Quantity ______________________________________ Cyclohexane        150 ml 30% Hydrogen peroxide 19.2 g (0.17 mole) ______________________________________

The reaction mass is cooled to 0.degree. C and, 19.6 (0.2 mole) of perphthalic anhydride is added slowly. The reaction mass is then stirred for 1 hour after which period of time 19.2 g of beta-ionone in 50 ml cyclohexane is added over a period of 30 minutes at about 25.degree. C. At the end of the 30 minute addition period, the reaction mass is stirred for a period of 3 hours and then added to 150 ml water. The solids are filtered and the organic layer is separated from the aqueous layer. The organic layer is washed with one 100 ml portion of saturated aqueous salt solution and is dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap yielding 20.0 g of an oil. GLC analysis of the crude oil indicates: Ingredients        Quantity ______________________________________ Trans beta-cyclohomocitral enol acetate        1.8%  (1.8% yield) Beta-ionone        47.3% (51.4% recovery) Beta-ionone epoxide 40.7% (40.9% yield) ______________________________________

The foregoing represents 1.8% yield of trans beta-cyclohomocitral enol acetate. FIG. 22 sets forth the GLC profile for the crude reaction product. ANILINE SOLVENT

Into a 500 ml reaction flask equipped with stirrer, thermometer and addition funnel the following materials are placed: Ingredients        Quantity ______________________________________ Dimethyl aniline   100 ml Beta-ionone        19.2 g    (0.1 mole) Sodium acetate     13 g      (0.13 mole) ______________________________________

The reaction mass is stirred for a period of 10 minutes after which time addition of 19.2 g (0.01 mole) of 40% peracetic acid is commenced while maintaining the reaction mass at a temperature in the range of 25.degree.-30.degree. C.

Addition of peracetic acid takes place over a period of 30 minutes with stirring while maintaining the temperature of the reaction mass at 25.degree.-30.degree. C. After addition of the peracetic acid the reaction mass is stirred for another 2 hours. At this point the reaction mass has a characteristic purple color.

The reaction mass is then added to 300 ml water and the resulting mixture is added to 300 ml diethyl ether thereby forming an emulsion. The resulting emulsion is broken upon heating and standing for a period of about 2 hours. The ether layer is separated from the aqueous layer and GLC analysis is carried out on the ether layer. GLC analysis indicates traces of beta-cyclohomocitral enol acetate and beta-ionone epoxide. The aqueous layer is purplish indicating that the amine is oxidized preferentially over the beta-ionone.

The GLC profile for the reaction product in the ether layer is set forth in FIG. 23. ##STR39##

Into a 500 ml reaction flask equipped with stirrer, thermometer and addition funnel the following materials are placed: Ingredients        Quantity ______________________________________ Formamide          100 ml Potassium acetate  13 g      (0.13 mole) Beta-ionone        19.2 g    (0.1 mole) ______________________________________

The resulting mixture is stirred for 10 minutes. At the end of the 10 minute period, addition of 19.6 g (0.1 moles) of 40% peracetic acid is commenced while maintaining the temperature at 25.degree.-30.degree. C. The reaction is mildly exothermic thus not requiring the use of a cooling bath. The addition of the peracetic acid is carried out for a period of 30 minutes. At the end of this 30 minute period, the reaction mass is stirred for another 2 hour period.

The reaction mass is then added to 200 ml water which, in turn, is added to 200 ml diethyl ether. An emulsion is formed which breaks upon heating and standing overnight.

GLC analysis of the ether layer indicates a major peak which is trans beta-cyclohomocitral enol acetate as well as smaller quantities of beta-ionone epoxide and beta-ionone. The aqueous and ether layer are separated and the ether layer is washed with one 100 ml portion of aqueous saturated sodium chloride solution. The ether layer is then dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap yielding 21.9 g of product. GLC analysis of the stripped crude product indicates the following materials to be present: Ingredients        Quantity and Yield ______________________________________ Beta-cyclohomocitral enol acetate       9.7 g   (46.6% yield) Beta-ionone        7.18 g  (37.4% recovery) Beta-ionone epoxide 3 g     (14.4% yield) ______________________________________

The GLC profile of the crude reaction product is set forth in FIG. 24. FORMAMIDE SOLVENT AND BUFFER

Into a 500 ml reaction flask equipped with stirrer, thermometer and addition funnel the following materials are added: Ingredients        Quantity ______________________________________ Dimethyl formamide 100 ml Beta-ionone        19.2 g (0.1 mole) Potassium acetate  13 g (0.1 mole) ______________________________________

The resulting mixture is stirred for a period of 10 minutes after which time addition of 19.6 g (0.1 mole) of 40% peracetic acid is commenced while maintaining the reaction mass at a temperature of 25.degree.-30.degree. C. The addition of the peracetic acid is carried out over a period of 50 minutes while maintaining the reaction mass at 25.degree.-30.degree. C. A very mild exotherm is noted. After addition of the peracetic acid is completed the reaction mass is stirred for an additional 2 hour period while maintaining the reaction mass at room temperature.

The reaction mass is then added to 200 ml water and 200 ml diethyl ether is added to the resulting mixture. The organic and aqueous layers are separated and the organic layer is washed with one 100 ml portion of aqueous saturated sodium chloride solution. The ether layer is then dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap yielding 20.1 g of an oil. GLC analysis of the stripped crude indicates the following materials to be present: Ingredients      Quantity ______________________________________ Beta-cyclohomocitral enol acetate     4.26 (20.4% yield) Beta-ionone      10.8 g (56 % recovery) Beta-ionone epoxide 13% yield ______________________________________

The GLC profile for the stripped crude product is set forth in FIG. 25. ACID OXIDIZING AGENT (USING 50% MORE SOLVENT THAN IN EXAMPLE L) ##STR40##

Into a 500 ml reaction flask equipped with stirrer, thermometer and reflux condenser are placed the following materials: Ingredients        Quantity ______________________________________ Benzene            150 ml Sodium acetate     13 g (0.13 mole) Beta-ionone        19.2 g (0.1 mole) ______________________________________

The resulting mixture is brought to a reflux at which point addition of 21.4 g (0.1 mole) of 85% m-chloro perbenzoic acid is commenced slowly. The addition takes place over an 80 minute period. At the end of this time the reaction mass is stirred at reflux for an additional 2 hours. The reaction mass is then added to 200 ml water thereby forming two phases; an aqueous phase and an organic phase. The aqueous phase is separated from the organic phase and 200 ml diethyl ether is added to the aqueous phase. The organic phase and ether washings are then combined and washed with one 100 ml portion of water. The resulting organic layer is dried over anhydrous magnesium sulfate and filtered. The resulting product weighs 302.2 g. This material is then stripped on a Rotovap yielding 38.2 g of a solid. GLC analysis indicates: Ingredients        quantity ______________________________________ Beta-cyclohomocitral enol acetate       4.2 g (20%) Beta-ionone        6.1 g (32%) Beta-ionone epoxide 13 g (62%) ______________________________________

The GLC profile is set forth in FIG. 26. SOLVENT

A procedure is carried out identical to that of Example LIII except that the resulting crude product weighs 26.4 g and the GLC analysis of the stripped product indicates: Ingredients          Quantity ______________________________________ Trans beta-cyclohomocitral enol acetate         12.2 g (59%) Beta-ionone          3.0 g (16%) Beta-ionone epoxide  7.2 g (34%) ______________________________________

The GLC profile is set forth in FIG. 27. ##STR41##

Into a 250 ml reaction flask equipped with stirrer, addition funnel, thermometer and cooling bath the following materials are placed: Ingredients      Quantity ______________________________________ Delta methyl ionone 24.8 (0.1 mole) Water            40 ml Acetic acid      50 ml Sodium acetate   17 g (0.17 mole) ______________________________________

The resulting mixture is stirred for 10 minutes at which point in time addition of 24 g (0.13 mole) of 40% peracetic acid is commenced while maintaining the reaction mass at a temperature of 25.degree.-30.degree. C. Addition of the peracetic acid takes place over a ten minute period. The reaction is mildly exothermic. After addition of the peracetic acid is completed, the reaction mass is stirred for another 2 hours at 25.degree.-30.degree. C. At the end of the 2 hour period the reaction mass is added to 200 ml water and the resulting material is extracted with one 200 ml portion of methylene dichloride followed by one 100 ml portion of methylene dichloride. The methylene dichloride extracts are combined and washed with two 100 ml portions of water. The washed methylene dichloride extracts are combined and dried over anhydrous magnesium sulfate, filtered and stripped on a Rotovap thus yielding 26.3 g of a crude product. GLC analysis of the crude product indicates two early eluting peaks, a relatively small amount of starting material and two new later eluting peaks. The second early eluting peak is the enol acetate having the structure: ##STR42## The GLC profile for the resulting crude product is set forth in FIG. 28.

From a flavor standpoint, the alpha, 2,6,6-trimethyl-1-cyclohexene-trans-1-ethenyl acetate has a woody, ionone-like, gasoline-like, tomato aroma with a woody, ionone, gasoline-like solvent flavor character at 1 ppm. From a fragrance standpoint the said compound has an oily, woody, musky, butyric, ionone-like note and is not as sweet or fruity or berry-like as beta-cyclohomocitral enol acetate. On dry out, the resulting compound has a woody and burnt aroma. ##STR43##

Into a 100 ml reaction flask equipped with stirrer, thermometer and reflux condenser are placed the following ingredients: Ingredients        Quantity ______________________________________ beta-cyclohomocitral 16.6 g (0.1 mole) acetic anhydride   17.3 g (0.17 mole) potassium acetate   0.1 g (0.01 mole) ______________________________________

The reaction mass is refluxed with stirring, for a period of 9 hours. At the end of the 9 hour period, 50 ml diethyl ether is added to the reaction mass. The reaction mass is then washed neutral with five 50 ml portions of water. The resulting material is then dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap. GLC analysis indicates the presence of 3 compounds:

The GLC profile is set forth in FIG. 29. The GC-MS profile is set forth in FIG. 30. The NMR spectrum for the trapping consisting of the cis enol acetate is given in FIG. 31. The NMR analysis is as follows: Peak            Interpretation ______________________________________ 0.98 ppm (s) ##STR44##      6H 1.54 (broad singlet) ##STR45##      3H 2.14 (s) ##STR46##      3H 5.34 (d)                        1H olefinic protons 7.04 (d)                        1H ______________________________________

it is noteworthy that the olefinic protons of the trans isomer are at 5.75 ppm and 6.98 ppm.

The resulting material, the beta-cyclohomocitral cis enol acetate, has the following organoleptic properties: Flavor Properties Perfumery Properties ______________________________________ A sweet, floral, ionone-like, Earthy, camphoraceous woody, violet, fruity, cary- and sea-like aroma with ophyllene aroma with hay-like, ionone and fruity ionone-like, woody, violet nuances in addition to caryophyllene-like, tobacco sweet, beta-ionone-like, and cedarwood-like flavor tobacco and fruity nuances. characteristics at 5 ppm. ______________________________________ FORMAMIDE SOLVENT BUT NO BUFFER

Into a 500 ml reaction flask equipped with stirrer, thermometer and addition funnel are added the following materials: Ingredients        Quantity ______________________________________ dimethyl formamide 100 ml beta-ionone        19.2 g ______________________________________

With stirring over a period of 30 minutes while maintaining the contents of the 500 ml reaction flask at 25.degree. C, 19.6 g (0.1 mote) of 40% peracetic acid is added to the reaction mass. At the end of the 30 minute period stirring is ceased and the reaction mass is allowed to stand for a period of 144 hours. At the end of the 144 hour period 200 ml water is added to the reaction mass, followed by 200 ml diethyl ether, with stirring. An emulsion forms which separates into two layers; an aqueous layer and an organic layer. The aqueous layer is extracted with one 200 ml portion of diethyl ether. The ether washing is combined with the organic layer and the resulting solution is washed with one 200 ml portion of aqueous saturated sodium chloride solution. The organic layer is then dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap yielding 34.5 g of an oil.

GLC analysis of the stripped crude indicates that the ratio of beta-ionone to beta-ionone-epoxide is approximately 1:2 and that only a trace of beta-cyclohomocitral enol acetate is present.

Examples LX-LXIV are carried out in a reaction flask equipped with stirrer, thermometer and addition funnel using a procedure similar to that of Example LIII. The reaction conditions and results are set forth in the following table: Example Reaction    Reaction   Products of No.    Ingredients Temperature Reaction ______________________________________ LX     400 ml water, 0.degree. C for 3 beta-cyclohomo- 26 g sodium hours      citral enol acetate acetate,               4.2%, 38.4 g (0.2            beta-ionone 47%, moles) beta-           beta-ionone epoxide ionone,                39% 76 g (0.4 moles) 40% peracetic acid LXI    80 ml water, 0 to -5.degree. C beta-cyclohomo- acetic acid for 5 hours citral enol acetate 100 ml,                46.8%, sodium acetate         beta-ionone 10.3%, 34 g,                  beta-ionone epoxide beta-ionone            44.9% 38.4 g (0.2 moles), 76 g (0.4 moles) 40% peracetic acid LXII   formamide   0 to -5.degree. C beta-cyclohomo- 180 ml,     for 5 hours citral enol acetate sodium acetate         50.7%, 26 g,                  beta-ionone 36.2%, beta-ionone            beta-ionone epoxide 38.4 g (0.2            15.9% moles), 76 g (0.4 moles) 40% peracetic acid LXIII  formamide   0.degree. C for beta-cyclohomo- 4500 ml,    3.5 hours  citral enol acetate sodium acetate         52.6%, 650 g,                 beta-ionone 15.6%, beta-ionone            beta-ionone epoxide 960 g,                 25% 40% peracetic acid 1900 g (10 moles) LXIV   formamide   25.degree. C for beta-cyclohomo- 400 ml,     3 hours    citral enol acetate beta-ionone            43%, 38.4 g                 beta-ionone 1.8%, potassium              beta-ionone epoxide acetate (0.2           43% moles), 76 g (0.4 moles) 40% peracetic acid ______________________________________ ##STR47##

Into a 50 ml reaction flask equipped with thermometer, heating mantle and magnetic stirrer the following materials are charged: Ingredients      Quantity ______________________________________ lauroyl chloride 15.8 g (.076 mole) beta-cyclohomocitral 7.3 g (.045 mole) potassium acetate 1 gram ______________________________________

The reaction mass is heated for a period of 5 hours at a temperature in the range of from 160.degree.-200.degree. C. Upon heating, the reaction mass first turns a light purplish color and then a green color and evolution of hydrogen chloride gas is observed. The reaction mass is then cooled and poured into 200 ml water. The resulting aqueous phase is then extracted wih two 150 ml portions of methylene chloride. The organic layers are combined and then dried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap to yield 22.5 of a dark solid. GLC analysis of the stripped crude indicates an acid peak and 3 new peaks having a later retention time.

The GLC profile for the reaction product is set forth in FIG. 35. The GC-MS profile for the reaction product is set forth in FIG. 36.

A tobacco mixture is produced by admixing the following ingredients: Ingredient           Parts by Weight ______________________________________ Bright               40.1 Burley               24.9 Maryland             1.1 Turkish              11.6 Stem (flue-cured)    14.2 Glycerine            2.8 Water                5.3 ______________________________________

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared: Ingredient          Parts by Weight ______________________________________ Ethyl butyrate      .05 Ethyl valerate      .05 Maltol              2.00 Cocoa extract       26.00 Coffee extract      10.00 Ethyl alcohol       20.00 Water               41.90 ______________________________________

The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 500 or 1,000 ppm of beta-cyclohomocitral enol butyrate produced according to the process of Example XXV. The control cigarettes not containing the trans beta-cyclohomocitral enol butyrate produced according to the process of Example XXXV and the experimental cigarettes which contain the trans beta-cyclohomocitral enol butyrate produced according to the process of Example XXV are evaluated by paired comparison and the results are as follows:

The experimental cigarettes are found to have a sweet, floral, tea-tobacco-like, fruity, damascenone aroma, prior to, and, on smoking. In addition, the natural tobacco taste and aroma is enhanced on smoking, as a result of using the trans beta-cyclohomocitral enol butyrate.

All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

A tobacco mixture is produced by admixing the following ingredients: Ingredient           Parts by Weight ______________________________________ Bright               40.1 Burley               24.9 Maryland             1.1 Turkish              11.6 Stem (flue-cured)    14.2 Glycerine            2.8 Water                5.3 ______________________________________

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared: Ingredient          Parts by Weight ______________________________________ Ethyl butyrate      .05 Ethyl valerate      .05 Maltol              2.00 Cocoa extract       26.00 Coffee extract      10.00 Ethyl alcohol       20.00 Water               41.90 ______________________________________

The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 500 or 1,000 ppm of cis beta-cyclohomocitral enol octanoate produced according to the process of Example XXVIII. The control cigarettes not containing the cis beta-cyclohomocitral enol octanote produced according to the process of Example XXXVIII and the experimental cigarettes which contain the cis beta-cyclohomocitral enol octanoate produced according to the process of Example XXVIII are evaluated by paired comparison and the results are as follows:

The experimental cigarettes are found to have more body and to be sweeter, more aromatic, more tobacco-like and to have better mouthfeel than the control cigarettes.

The tobacco of the experimental cigarettes, prior to, and, on smoking, has sweet, slightly sour, cool-minty-like notes with pungent, waxy and natural tobacco-like nuances.

All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

A tobacco mixture is produced by admixing the following ingredients: Ingredient           Parts by Weight ______________________________________ Bright               40.1 Burley               24.9 Maryland             1.1 Turkish              11.6 Stem (flue-cured)    14.2 Glycerine            2.8 Water                5.3 ______________________________________

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared: Ingredient          Parts by Weight ______________________________________ Ethyl butyrate      .05 Ethyl valerate      .05 Maltol              2.00 Cocoa extract       26.00 Coffee extract      10.00 Ethyl alcohol       20.00 Water               41.90 ______________________________________

The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 500 or 1,000 ppm of trans beta-cyclohomocitral enol octanoate produced according to the process of Example XXVIII. The control cigarettes not containing the trans beta-cyclohomocitral enol octanoate produced according to the process of Example XXXVIII and the experimental cigarettes which contain the trans beta-cyclohomocitral enol octanoate produced according to the process of Example XXVIII are evaluated by paired comparison and the results are as follows:

The experimental cigarettes are found to have more body and to be sweeter, more aromatic, more tobacco-like and to have better mouthfeel than the control cigarettes.

The tobacco of the experimental cigarettes, prior to, and, on smoking, has sweet, slightly sour, cool-minty-like notes with pungent, waxy and natural tobacco-like nuances.

All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

A tobacco mixture is produced by admixing the following ingredients: Ingredient           Parts by Weight ______________________________________ Bright               40.1 Burley               24.9 Maryland             1.1 Turkish              11.6 Stem (flue-cured)    14.2 Glycerine            2.8 Water                5.3 ______________________________________

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared: Ingredient          Parts by Weight ______________________________________ Ethyl butyrate      .05 Ethyl valerate      .05 Maltol              2.00 Cocoa extract       26.00 Coffee extract      10.00 Ethyl alcohol       20.00 Water               41.90 ______________________________________

The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 500 or 1,000 ppm of cis beta-cyclohomocitral enol acetate produced according to the process of Example LVIII. The control cigarettes not containing the cis beta-cyclohomocitral enol acetate produced according to the process of Example LVIII and the experimental cigarettes which contain the cis beta-cyclohomocitral enol acetate produced according to the process of Example LVIII are evaluated by paired comparison and the results are as follows:

The experimental cigarettes are found to have more body and to be sweeter, more aromatic, more tobacco-like and less harsh with sweet, floral and fruity notes. The tobacco of the experimental cigarettes, prior to smoking, has sweet, floral and fruity notes. All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

The cis betta-cyclohomocitral enol acetate produced according to the process of Example LVIII enhances the tobacco like taste and aroma of the blended cigarettes, imparting to it sweet, natural tobacco notes. FORMAMIDE AS SOLVENT AND PERACETIC ACID OXIDIZING AGENT AT A REACTION TEMPERATURE OF 0.degree. C

Into a 12 liter reaction flask equipped with stirrer, thermometer, addition funnel and dry ice/acetone cooling bath, the following materials are added: Ingredients        Quantity ______________________________________ Formamide          4500 ml Sodium Acetate     650 gm (7.92 mole) Beta-ionone        960 gm (5.0 mole) ______________________________________

The reaction mass is stirred with cooling until a temperature of 0.degree. C is attained. At this time the addition of 1900 gm (10.0 moles) of 40% peracetic acid is commenced. The addition is carried out over a period of 3.5 hours while maintaining the temperature at 0.degree. C. At the end of the addition period the reaction mass is stirred for an additional 3.5 hours at a temperature of 0.degree. C. At the end of this period the reaction mass is transferred to a five gallon open head separatory funnel and to it is added 5 liters of warm water. The mass is extracted with three 1 liter portions of methylene chloride and the combined extracts are washed with three 1 liter portions of water. The combined extracts are then dried over anhydrous magnesium sulfate and filtered. The solvent is then stripped atmospherically through a 2 inches porcelain saddle column to a liquid temperature of 100.degree. C. The residual oil is distilled at reduced pressure through a 2 inches porcelain saddle column to yield 984 grams of an oil in seven fractions. GLC analysis of the individual fractions indicates: Ingredient         Quantity ______________________________________ Trans-beta-cyclomomo- citral enol acetate (52.6% yield) Beta-ionone        (15.6% recovery) Beta-ionone epoxide (25% side product) ______________________________________ BETA-CYCLOHOMOCITRAL ENOL ACETATE

Into a 5 liter reaction flask equipped with stirrer, thermometer, addition funnel and dry ice/acetone cooling bath, the following materials are added: Ingredient         Quantity ______________________________________ Water              1665 ml Methanol           1665 ml Sodium Carbonate   500 gm (4.71 mole) ______________________________________

The mixture is stirred for a short period of time. The addition of 984 grams of a mixture of beta-cyclohomocitral enol acetate, beta-ionone and beta-ionone epoxide from the above-mentioned distillation is then commenced. The mixture is added over a period of 45 minutes, while maintaining a temperature of 25.degree.-30.degree. C. At the end of the addition period, the mixture is allowed to stir for an additional 2 hours at 25.degree.-30.degree. C. At the end of this period the reaction mass is poured into a five gallon open head separatory funnel and to it are added 3 liters of water and 1 liter of chloroform. The organic layer which forms is collected. The aqueous layer is then extracted with two additional 1 liter portions of chloroform. The organic extracts are combined, washed with two 1 liter portions of a saturated salt solution, dried over anhydrous magnesium sulfate and filtered. The organic layer is then subjected to a combined stripping and rushover at reduced pressure through a 2 inches porcelain saddle column to yield 758 grams of an oil. The oil is then distilled through an 18 inches Goodloe column at reduced pressure to yield 686 grams of an oil in fourteen fractions. A residue of 44 grams, containing beta-ionone and beta-ionone epoxide remains, due to column hold-up. GLC analysis of these fractions indicates: Ingredient       Quantity ______________________________________ Beta-cyclohomocitral 583 gram (70% yield from beta-ionone) Beta-ionone      88 gram (9% recovery) Beta-ionone epoxide 9 gram (0.8% carried over side product) ______________________________________

A tobacco mixture is produced by admixing the following ingredients: Ingredient           Parts by Weight ______________________________________ Bright               40.1 Burley               24.9 Maryland             1.1 Turkish              11.6 Stem (flue-cured)    14.2 Glycerine            2.8 Water                5.3 ______________________________________

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared: Ingredient          Parts by Weight ______________________________________ Ethyl butyrate      .05 Ethyl valerate      .05 Maltol              2.00 Cocoa extract       26.00 Coffee extract      10.00 Ethyl alcohol       20.00 Water               41.90 ______________________________________

The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 500 or 1,000 ppm of cis beta-cyclohomocitral enol layrate (mixture of cis and trans isomers) produced according to Example LXV. The control cigarettes not containing the cis beta-cyclohomocitral enol laurate produced according to the process of Example LXV and the experimental cigarettes which contain the cis beta-cyclohomocitral enol laurate produced according to the process of Example LXV are evaluated by paired comparison and the results are as follows:

The experimental cigarettes are found to have more body and to be sweeter, more honey-like, more aromatic, more tobacco-like and to have better mouthfeel than the control cigarettes.

The tobacco of the experimental cigarettes, prior to, and on smoking, has sweet, slightly sour, cool-minty-like and honey-like notes with punget, waxy and natural tobacco-like nuances.

All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

## Claims

1. A process for augmenting or enhancing the aroma or taste of smoking tobacco comprising intimately admixing with smoking tobacco an augmenting or enhancing quantity of at least one enol ester defined by the structure: ##STR48## wherein R.sub.1 is straight chain alkyl having 1, 3, 7 or 11 carbon atoms.

2. The process of claim 1 wherein, in the enol ester, R.sub.1 is methyl and the ester moiety is in a "cis" relationship to the cyclohexenyl moiety.

3. The process of claim 1 wherein, in the enol ester, R.sub.1 is n-propyl and the ester moiety is in a "trans" relationship to the cyclohexenyl moiety.

4. The process of claim 1 wherein, in the enol ester, R.sub.1 is n-heptyl and the ester moiety is in a "cis" relationship to the cyclohexenyl moiety.

5. The process of claim 1 wherein, in the enol ester, R.sub.1 is n-heptyl and the ester moiety is in a "trans" relationship to the cyclohexenyl moiety.

6. The process of claim 1 wherein, in the enol eter, R.sub.1 is n-undecyl.

7. A smoking tobacco article comprising smoking tobacco wrapped in a smokeable wrapping, said wrapping or said tobacco, or both said wrapping and said tobacco having imparted thereto an aroma or taste augmenting or enhancing quantity of an enol ester defined by the structure: ##STR49## wherein R.sub.1 is straight chain alkyl having 1, 3, 7 or 11 carbon atoms.

8. A smoking tobacco article defined according to claim 7 wherein, in the enol ester, R.sub.1 is methyl and the ester moiety is in a "cis" relationship to the cyclohexenyl moiety.

9. A smoking tobacco article defined according to claim 7 wherein, in the enol ester, R.sub.1 is n-propyl and the ester moiety is in a "trans" relationship to the cyclohexenyl moiety.

10. A smoking tobacco article defined according to claim 7 wherein, in the enol ester, R.sub.1 is n-heptyl and the ester moiety is in a "cis" relationship to the cyclohexenyl moiety.

11. A smoking tobacco article defined according to claim 7 wherein, in the enol ester, R.sub.1 is n-heptyl and the ester moiety is in a "trans" relationship to the cyclohexenyl moiety.

12. A smoking tobacco article defined according to claim 7 wherein, in the enol ester, R.sub.1 is n-undecyl.