CA1053688A - Enol esters and novel flavoring and fragrance compositions containing same and processes for using same and processes for preparing said novel enol esters - Google Patents

Abstract

Abstract: Processes and compositions are described for the use in foodstuff, chewing gum, toothpaste and medicinal product flavor and aroma, tobacco flavor and aroma and perfume aroma augmenting, modifying, enhancing and imparting compositions and as foodstuff, chewing gum, toothpaste, medicinal product, tobacco, perfume and perfumed article aroma imparting materials of one or more alkyl side chain methyl substituted or unsub-stituted 2,2,6-trimethyl-1-cyclohexen-1-vinyl alkanoates (hereinafter referred to as "enol esters") having the generic structure:
(which structure is intended to cover both the "cis" and the "trans" isomers thereof) wherein R1 is C1-C11 alkyl and R4 is hydrogen or methyl, produced by one of the following processes:
(1) A process which comprises the step of oxidizing beta-ionone or a beta-ionone homologue having the formula:
with a peracid having the formula:
wherein R1 is C1-C11 alkyl; R4 is hydrogen or methyl; and R2 is hydrogen, methyl, ethyl or metachlorophenyl and in the presence of a buffer and a solvent which is one of:
methylene chloride;
acetic acid;
formic acid;
propionic acid;
benzene;
cyclohexane;
formamide;
chloroform; or mixtures of two or more of the foregoing solvents and in the absence of substantial quantities of reactive solvents such as dimethyl aniline or, where a buffer is not present, dimethyl formamide, to form alkyl side chain substituted or unsubstituted 2,2,6-trimethyl-1-cyclohexen-1-vinyl alkanoates (hereinafter referred to as "enol esters") having the formula:

(which would be primarily the "trans" isomer when produced in this manner);
(2) If desired reacting an enol acetate formed by the process (1) when R1 is CH3 and R4 is hydrogen) having the structure:
or with an alkanoic acid anhydride or an acyl halide having one of the formulae:
or wherein X is bromo or chloro, and wherein R3 is C2-C11 alkyl such as ethyl, n-propyl, isopropyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, n-heptyl, 2-methyl-1-nonyl, n-octyl and n-undecyl, in the presence of a catalyst such as paratoluene sulfonic acid or an alkali metal acetate to form a compound having the formula:
(a mixture of "cis" and "trans" isomers); or (3) Reacting beta-cyclohomocitral having the formula:
with a lower alkanoic acid anhydride having the formula:
of an acyl halide having the formula:
wherein X is bromo or chloro and wherein R1 is C1-C11 alkyl, in the presence of an alkali metal acetate under reflux conditions or in the presence of paratoluene sulfonic acid under reflux conditions to form a mixture of "cis" and "trans" isomers.
Addition of one or more of the enol esters having the formula:
to consumable materials is indicated to produce:
(a) In foodstuffs, foodstuff flavorings, chewing gums, toothpastes and medicinal products, "damascenone-like" (damascenone has the structure:
, sweet, "cocoa like", "dried fruit-like", fruity, apple juice-like, sweet carrot juice, incense-like, ionone-like, spicey, woody, wood resin-like, winey, oriental/olibanum, clove-like, camphoraceous, rosey, raspberry, raspberry seed, grape, violet-like, caryophyllene-like, and/or floral aromas with fermented tea and tobacco nuances and sweet vegetable, tea, sweet carrot juice, sweet, fruity, dried fruit-like, apple juice, mimosa, raspberry, pear, ionone-like, "damascenone-like", rosey, woody, camphor-aceous, violet, cedarwood-like, caryophyllene-like, wood resin-like, winey, tobacco-like, hay-like, and raspberry kernel tastes (with sweet aftertastes);
(b) In tobacco and tobacco flavorings, a sweet, floral, fruity, woody, ionone-like, spicey slightly fatty aromatic aroma prior to smoking and a sweet, tobacco-like characteristic in the mainstream on smoking; and (c) In perfumes, colognes and perfumed articles, sweet, fruity, acidic-fruity, dried fruit-like, floral, "damascenone-like", woody, green, beta-ionone-like notes with animal-tobacco nuances and fermented tea and tobacco topnotes and cognac, balsamic, tobacco undertones.
The enol esters of our invention are also useful reaction intermediates for producing beta-cyclohomocitral which is valuable for its organoleptic properties.
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.
"Damascenone-like" (damascenone has the structure:
sweet, "cocoa like", "dried fruit-like", fruity, apple juice-like, sweet carrot juice, incense-like, ionone-like, spicey, woody, wood resin-like, winey, oriental/olibanum, clove-like, camphoraceous, rosey, raspberry, raspberry seed, grape, violet-like caryophyllene-like, and/or floral aromas with fermented tea and tobacco nuances and sweet vegetable, tea, sweet carrot juice, sweet, fruity, dried fruit-like, apple juice, mimosa, raspberry, pear, ionone-like, "damascenone-like", rosey, woody, camphoraceous, violet, cedarwood-like, caryophyllene-like, wood resin-like, winey, tobacco-like, hay-like, and raspberry kernel tastes (with sweet aftertastes) are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors.
Sweet, fruity, acidic-fruity, dried fruit-like, woody, green beta-ionone-like notes with animal-tobacco topnotes and cognac, balsamic, tobacco undertones are desirable in several types of perfume compositions, perfumed articles and colognes.
Sweet, woody, floral, fruity, ionone-like, spicey, 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 flavor-ing compositions.
Arctander, "Perfume and Flavor Chemicals", 1969 discloses the use in perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", "isocyclocitral", "alpha-cyclo-citrylidene acetaldehyde" and "beta-cyclocitrylidene acetal-dehyde", thus:

(i) "760" CYCLOCITRAL
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.

Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of may pieces of proof that isomers (alpha-beta) do often have different odors."
(ii) "761? iso-CYCLOCITRAL
A mixture of two chemicals:
3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde (meta-cyclocitral).

(corrected structure) 2,4,6-trimethyl-4-cyclohexen-1-carboxaldehyde (symmetric-iso-cylocitral).

(corrected structure) 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 whereit 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..."

(iii) "762: alpha CYCLOCITRYLIDENE ACETALDEHYDE
Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of 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 avail-able 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.
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 pro-duced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer. ..."
(v) "869: DEHYDRO-beta-CYCLOCITRAL (Safranal) 2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde Very powerful, sweet, green-floral and some-what tobacco-herbaceous odor of good tenaci-ty. In extreme dilution reminiscent of the odor of Safran (Saffron).

beta Interesting material for fresh topnotes, as a modifier for aldehyde-citrusy notes, as a green-floral topnote in flower fragrances, etc. It blends excellently with the ali-phatic Aldehydes, with Oakmoss products and herbaceous oils. ..."
Safranal and beta-cyclocitral are disclosed as volatile constituents of Greek Tobacco by Kimland et al., Phytochemistry 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 155-160°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.

Description

IFF-2278DA/F.5 Canada 105368~
_ This invention relates to certain enol esters and flavor-ing and fragrance compositions containing same and processes for using same and processes for preparing said enol esters which are alkyl side chain methyl substituted or unsubstituted

2,2,6-trimethyl-1-cyclohexen-1-vinyl alkanoates.

1. Field of the Invention.
This application relates to enol esters having the generic structure:

j~,,o~R, wherein Rl is Cl-Cll alkyl and R4 is hydrogen or methyl and methods for using same as flavorants or in perfumes or in perfumed articles and methods of preparing same by peracid oxidation of ionone derivaties and/or ester interchange reactions and/or reaction of beta-cyclohomocitral with alkanoic acid anhydrides or acyl halides.

2. Description of the Prior Art.
Arctander, "Perfume and Flavor Chemicals", 1969, dis-closes the use in perfume compositions and flavors of "cyclocitral n ~ "dehydro-beta-cyclocitral", "isocyclocitral", "alpha-cyclocitrylidene acetaldehyde" and "beta-cyclocitrylidene acetaldehyde", thus:

i ) n 7 6 0 " CYCLOC I ~RAL

Alpha-cyclocitral = (2,2,6-trimethyl-5-cyclohexen-1-carboxaldehyde).
beta-cyclocitral = (2,2,6-trimethyl-6-cyclohexen-l-carboxaldehyde).
Both isomer:; are known and have been produced separately.

~ 35~f~88 ..

~C~O ~f~

Very rarely offered comme-cially. These particular cyclocitrals have little or nQ
tnterest to the cre~tive ~rfumer, but -they have served as ~art of manv Dieces of proof that isomers (alpha-beta) do often have different odors."
($i) 7 61: iso-CYC~OCITRAL
A mixture of two chemicals:

3,5,6-trimethyl-3-cycloheYen-l-carboxaldehyde (meta-cyclocitral).
C~3 1 ~CItO
~ ~ .
(corrected strusture) ~ 3 / ~ \ C~3 2,4,6-trimQthyl-4-cyclohexen-1-carboxaldehyde (sy~metric-iso-cyclocitral).
~ 3 c~

~ C 3 ( tcorrected structure) H CHO
Powerful, and ~iffusive, foliage-green, ~dark" weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet green notes are auite natural in high dilution and _esemble the odor of ste~s rrom plants and flowers fresh ~rom the soil.
Flnds use in Ferfume comDositions where it blends e~cellently with Oakmoss ~roducts ~compensates for sweetness and lifts the topnote), with Ionones ~freshness), Geranium ~nd Galbanum (enhances the green and ~vegetable" notes ), etc. ,..~

1~)5~688 (iii) "762: alpha CYCLOCITRYLIDENE ACETALDEHYDE

~ CH=CH-CHO

Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of 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.

N3C ~ CH=CH-CHO

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 competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer...."
(v) "869: DEHYDRO-beta-CYCLOCITRAL (Safranal) 2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde ~3C\ /CH3 /\

HC\~ / CH3 l~S3688 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 discloses as volatile constituents of Greek Tobacco by Kimland et al., Phytochemistry 11 (309) 1972. Beta-cyclocitral is disclsoed 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 - 160C by Bedoukian, J.Am.Chem.Soc. 66, August, 1944, pages 1325 - 1327.

1053~88 . .
Summary of the Invention This invention covers processes and compositions for the use in foodstuff, chewing gum, toothpaste and medicinal product flavor and aroma, tobacco flavor and aroma and per-fume aroma augmenting, modifying, enhancing and impartingcompositions and as foodstuff, chewing gum, toothpaste, medicinal product, tobacco, perfume and perfumed article . _. ~ ._...
aroma imparting materials of one or more alkyl side chain methyl substituted or unsubstituted 2,2,6-trimethyl-1-cyclohexen-l-vinyl alkanoates (hereinafter referred to as "enol esters") having the generic structure:

,~~¢

R~, (which structure is intended to cover both the "cis" and the "~rans" isomers thereof) wherein Rl is Cl-Cll alkyl and R4 is hydrogen or methyl, produced by one of the following processes:

~1) A process which comprises the step of oxidizing beta-ionone or a beta-ionone homologue having the formula:

~RI

with a peracid having the formula:

: ~0 2 ~ O - O -H

wherein Rl is Cl-Cll alkyl: R4 is hydrogen or methyl; and R2 is hydrogen, methyl, ethyl or metachlorophenyl and in the presence of a buffer and a solvent which is one of:

methylene chloride;
acetic acid;
formic acid;
propionic acid;
benzene;
cyclohexane;
formamide;
chloroform; or mixtures of two or more of the oregoing solvents and in the absence of substantial quantities of reactive solvents such as dimethyl aniline or, where a buffer is not present, dimethyl formamide, to form alkyl side chain substituted or unsubstituted 2,2,6-trimethyl-1-cyclohexen-l-vinyl alkanoates (hereinafter referred to as "enol esters n ) having the formula:

~ O ~ R1 ~

(which would be primarily the "trans'^ isomer when produced in this manner);

(2) If desired reacting an enol acetate formed by the process (1) (when Rl is CH3 and ~4 is hydrogen) having the structure:

~ ~ or ~\~

with an alkanoic acid anhydride or an acyl halide having one of the formulae:
Q O

~ ~ ~ 3 or R3 C ~ X
wherein X is bromo or chloro, and wherein R3 is C2-Cll alkyl such as ethyl, n-propyl, isopropyl, l-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, n-heptyl, 2-methyl-1-nonyl, n-octyl and n-undecyl, in the presence of a catalyst such as paratoluene sulfonic acid or an alkalii metal acetate to form a compound having the formula:
~c\`fo'~R~

~a mixture of "cis" and "trans" isomers~; or (3) Reacting beta-cyclohomocitral having the formula:
~//o H

with a lower alkanoic acid anhydride having the formula:
Jl R1 ~ ' R1 or an acyl halide having the formula:
~0 Rl_C

wherein X is bromo or chloro and wherein Rl i~ Cl-Cll alkyl, in the presence of an alkali metal acetate under reflux conditions or in the presence of paratoluene sulfonic acid under reflux conditions to form a mixture of "cis" and "trans" isomers.

-11~5368~
sRIEF DESCRIPTION OF THE DRA~INGS

Figure 1 is the GLC profile for the reaction product of Example XXXIV wherein cis and trans beta-cyclohomocitral enol butyrate is produced.
Figure 2 is the GC-MS profile for the reaction product produced in Example XXXIV.
Figure 3 is the NMR spectrum for the cis isomer of beta-cyclohomocitral enol butyrate produced according to Example XXXIV.
Figure 4 is the IR spectrum for the cis isomer of beta--cyclohomocitral enol butyrate produced according to Example XXXIV.
Figure 5 is the IR spectrum for the trans isomer of beta--cyclohomocitral enol butyrate produced according to Example XXXIV.
Figure 6 is the NMR spectrum for the trans isomer of : beta-cyclohomocitral enol butyrate produced according to Example XXXIV.
Figure 7 is the GLC profile for the reaction product containing beta-cyclohomocitral enol butyrate produced according to Example XXXV.
Figure 8 is the GLC profile for the beta-cyclohomo-citral enol butyrate produced according to Example XXXVI.
Figure 9 is the GC-MS profile for beta-cyclohomocitral enol butyrate produced according to Example XXXVI.

g _ '~ ' . -1~53~i8~
Figure 10 is the GLC profile for the beta-cyclohomo-citral enol isobutyrate producea according to Example XXXVII.
_~ure ll is the GC-MS profile for the beta-cyclohomo-citral enol isobutyrate produced according to Example XXXVII.
Figure 12 is the NMR spectrum for the cis isomer of beta-cyclohomocitral enol isobutyrate produced according to Example XXXVII.
Figure 13 is the NMR spectrum for the trans isomer of beta-cyclohomocitral enol isobutyrate produced according to Example XXXVII.
Figure 14 is the GLC profile for the beta-cyclohomocitral enol octanoate produced according to Example XXXVIII.
Figure 15 is the GC-MS profile for the beta-cyclohomo-citral enol octanoate produced according to Example XXXVIII, Figure 16 is the NMR spectrum for the trans isomer of beta-cyclohomocitral produced according to Example XXXVIII.
Figure 17 is the NMR spectrum for the cis isomer of beta-cyclohomocitral produced according to Example XXXVIII.
Figure 18 is the GLC profile for the reaction product of Example XLVII wherein beta-cyclohomocitral enol propionate is produced.
Figure 19 is the GLC profile for the reaction product of Example XLVIII wherein beta-cyclohomocitral enol acetate is produced.
Figure 20 is the GLC profile for the reaction product . .
of Example XLIX wherein beta-cyclohomocitral enol acetate is produced.

1053~
Figure 21 is the GLC profile for the reaction product of Example L wherein beta-cyclohomocitral enol acetate is produced.
Figure 22 is the GLC profile for the reaction product of Example LI wherein beta-ionone epoxide is produced.
Figure 23 is the GLC profile for the reaction product of Example LII.
Figure 24 is the GLC profile for the reaction product of Example LIII wherein beta-cyclohomocitral enol acetate is produced.
Figure 25 is the GLC profile for the reaction product .
of Example LIV wherein beta-cyclohomocitral enol acetate is produced.
Figure 26 is the GLC profile for the reaction product of Example LV wherein beta-cyclohomocitral enol acetate is produced.
Figure 27 is the GLC profile for the reaction product of Example LVI wherein beta-cyclohomocitral enol acetate is produced.
Figure 28 is the GLC profile for the reaction product of Example LVII wherein the enol acetate having the structure:

[~~

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

1~53~88 Figure 30 is the GC-MS profile for the reaction product produced according to Example LVIII.
Figure 31 is the N-~R spectrum for the beta-cyclohomo-citral cis enol acetate produced according to Example LVIII.
Figure 32 is the Infrared spectrum of alpha-ionone epoxide produced in Example XVI.
Figure 33 is the NMR spectrum for alpha-ionone epoxide produced in Example XVI.
Figure 34 is the GLC profile of the reaction product produced according to Example XXV, containing beta-cyclohomo-citral enol acetate.
Figure 35 is the GLC profile of the reaction product produced according to Example LXV, containing beta-cyclo-homocitral enol laurate.
Figure 36 is the GC-MS profile of the reaction product produced according to Example LXV, containing beta-cyclohomo-citral enol laurate.
DESCRIPTION OF THE PREFERRED EMBODI~lENTS
.
The present invention provides novel solid and liquid foodstuff, chewing gum, medicinal product and toothpaste compositions and flavoring compositions therefor having "damascenone-like" (damascenone has the structure:
X, sweet, "cocoa-like", "dried fruit-like", fruity, apple juice-like, sweet carrot juice, incense-like, ionone~like, spicey, woody, wood resin-like, winey, oriental/olibanum, clove-like, camphoraceous, rosey, raspberry, raspberry seed, grape, i~S3f~8t~

violet-like, caryophyllene-like, and/or floral aromas with fermented tea and tobacco nuances and sweet vegetable, tea, sweet carrot juice, sweet, fruity, dried fruit-like; apple juice, mimosa, raspberry, pear, ionone-like, damascenone-like, rosey, woody, camphoraceous, violet, cedarwood-like, caryophyllene-like, wood resin-like, winey, tobacco-like, hay-like and/or raspberry kernel tastes with sweet aftertastes;
novel perfume compositions, colognes and perfumed articles having sweet, fruity, acidic-fruity, dried fruit-like, woody, green, beta-ionone-like notes with animal-tobacco topnotes and cognac, balsamic, tobacco undertones; as well as novel tobacco and tobacco flavoring compositions having sweet, woody, floral, fruity, ionone-like, spicey, slightly fatty aromatic aromas prior to smoking and sweet, tobacco-like smoke aroma character-istics 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:

~ J~ ~ R

(wherein R4 is hydrogen or methyl and Rl is one of C1-C11 alkyl) in foodstuffs, chewing gums, toothpastes, medicinal products, perfume compositions, perfumed articles, colognes and tobaccos as well as tobacco substitutes.
The enol esters useful as indicated supra may be produced, preferably, one of the several processes.

1iD53~8~

A first process comprises an oxidation reaction of beta-ionone or a higher alkyl homologue of beta-ionone with either performic acid, peracetic acid, perpropionic acid or m-chloroperbenzoic acid to form an enol ester.
More specifically, this process comprises the step of reaction beta-ionone or a higher alkyl homologue thereof having the formula:

~Rl with a peracid having the formula:

R2--C~
O - O - H

(wherein Rl is one of Cl- Cll alkyl, R4 is hydrogen or methyl and R2 is one of hydrogen, ethyl, methyl or m-chlorophenyl) in the absence of substantial quantities of solvents which are reactive with one of the reactants (e.g. the peracid) such as N,N-dimethyl aniline, and, in addition, in the case where a buffer is not present, in the absence of substantial quantities of the solvent, dimethyl formamide; and, in the presence of one or more of the following solvents:
Methylene chloride;

Acetic acid;
Formic acid;
Propionic acid;
~enzene Cyclohexane;

Formamiae; and Chloroform 1053f~
to form primarily the "trans" isomer of the enol ester having the formula:

~ oyRl and not the expected epoxide having one of the formulae:

~ and/or ~ R

and/or ~ ~ R

(As to the latter structure wherein R4 is hydrogen and Rl is methyl, see S. Iso~ et al., Tetrahedron Letters, No. 53, 5561-9 (1968)).

This reaction is preferably carried out in the presence of a buffer such as an alkali metal salt of a lower alkanoic acid or an alkali metal carbonate and in the presence of a lower alkanoic acid such as propionic acid, acetic acid or formic acid with the following provisos:
(i) The reaction is preferably carried out at temperatures of from -10C up to about 75C. Lower temperatures result in less complete reaction and, in some cases, cause the reaction mass to free~e, and 1053~i81~
temperatures higher than 75C result in lower yields of the desired product and significantly higher percentages of by-products. The most preferred tempera-ture range for the reaction is -5 to 30C;
(ii) A slight molar excess (from 10 up to 15 percent) of peracid gives a slightly higher yield of product. A large excess (about 20Q percent), however, results in the formation of dihydroactinodiolide having the structure:

X~
~0 ~0/

in about 30 - 35 percent yield when no buffer (e.g., potassium acetate) is present in the reaction mass;
(iii) Where potassium carbonate is substituted for potassium acetate as a buffer, the yield of product obtained is substantially the same;
(iv) On the other hand, a slightly lower yield of product is obtained by substituting sodium acetate for potassium acetate as the buffer;
(v) Substitution of formic acid for acetic acid in the reaction mass gives rise to a lower yield of product;

(vi) Omission of the buffer (i.e., thus performing the reaction under strongly acidic conditions) results in an incomplete reaction, lower yield and greater quantity of by-product(s) and insignificant or no yield of enol ester when dimethyl formamide is used as the solvent;
(vii) The use of dimethyl formamide as solvent when no buffer such as sodium acetate is used results in essentially the exclusive but very slow formation of beta-ionone epoxide having the strocture:

\/
in greater than 70% yield and, accordingly, in the absence of buffer, substantial ~uantities of dimethyl formamide must be avoided; and (viii) The use of monoperphthalic acid (formed in situ from phthalic anhydride and hydrogen peroxide) yields beta-ionone epoxide in 60 - 70 percent yield;
(ix) Whereas m-chloroperbenzoic acid is useful in producing the enol esters of our invention, the u~e of perbenzoic acid in place of a peralkanoic acid, or m-chloro-perbenzoic acid gives rise to the production of beta-ionone epoxide.

See R. Yves, et al., Helv. Chim. Acta~
29, 880 (1946). Indeed, when using 2 moles of perbenzoic acid, the corresponding epoxy enol acetate is formed virtually quantitatively;
(See S. Isoe, et al., Tetrahedron Letters, No. 53, 5561 (1968)); and (x) The use of permaleic acid yields beta-ionone epoxide and only traces of the desired enol acetate.
Thus, a specific conclusion that may be properly reached is that a peralkanoic acid such as peracetic acid or m-chloro-perbenzoic acid in slight excess in the presence of a buffer system, preferably composed of acetic acid/potassium acetate, is a preferred method to oxidize beta-ionone or higher alkyl homologue thereof at from about -5C to about 30C to the corresponding enol acetate.
The resulting reaction product, the enol acetate (primarily the "trans" isomer) may then be refined according to standard techniques, e.g., preparative gas chromatography, extraction, distillation and the like as further exemplified herein; or it may be further reacted via an ester interchange reaction to form other enol esters thereby carrying out a second process of our invention.
The first process is specific to beta-ionone and adjacent higher alkyl homologues thereof having the structure:

:

105368~
wherein Rl is Cl-Cll alkyl and R4 is hydrogen or methyl. As further exemplified infra, when the reaction conditions of this process are applied to alpha-ionone, as opposed to beta-ionone or its higher alkyl homologues, epoxide formation occurs and, at best, a small amount of enol ester is formed.
A second process comprises reacting beta-cyclohomo-citral enol acetate or a higher methyl homologue thereof formed in the first process (set forth supra) with an alkanoic acid anhydride in the presence of a paratoluene sulfonic acid or alkali metal acetate (e.g., sodium or potassium acetate) catalyst to form a second enol ester (a mixture of "cis" and "trans" isomers) according to the reaction:

~IOAc or ~ ,- R ,q paratoluene ~ ~
sulfonic acid ~ O~,R3 R4 O R3 - ~ ~ R4 wherein M is an alkali metal such as Na and K and wherein R3 is C2-Cll alkyl such as ethyl, n-propyl, isopropyl, l-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, n-heptyl, n-octyl or n-undecyl and R4 is hydrogen or methyl. This reaction is carried out at elevated temperatures (100 to 200C) over a period of from 3 hours up to 10 hours depending upon the concentration of paratoluene sulfonic acid catalyst or alkali metal acetate catalyst. It is preferable that the mole ratio of alkanoic acid anhydride:enol acetate be greater than 1 and preferably 1.5:1 because of the necessity to completely react the much more costly enol acetate. The mole ratio of enol acetate:paratoluene sulfonic acid catalyst or alkali metal - acetate catalyst is preferably from 1:0.01 up to 1:0.5 with the most convenient ratio being 1:0.01.

1053~
A third process whereby mixtures of "cis" and "trans"
isomers are formed involves the reaction of beta-cyclohomo-citral itself with an alkanoic acid anhydride or an acyl halide in the presence of either an alkali metal acetate base or a catalytic quantity of paratoluene sulfonic acid according to one of the following reaction sequences:

~0 ~ ~ MOAc or ~ ~ \

~H R O Rl paratoluene O
~ ~ 1 sulfonic acid ~_~ \

~C~ + R --C~ MOAC Or ~O~fR1 I l H 1 ~X paratoluene o ~ , sulfonic acid ~, ~

wherein X is chloro or bromo and wherein Rl is Cl-Cll alkyl such as methyl, ethyl, n-propyl, isopropyl, l-butyl, 2-butyl~
2-methyl-1-propyl, 2-methyl-2-propyl, l-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 2-methyl-2-butyl, 2-methyl-3-butyl, l-heptyl, 1-octyl, 2-methyl-1-nonyl and l-undecyl and M is alkali metal such as sodium and potassium. The reaction is carried out at elevated temperatures (25 - 175C) preferably in the absence of any solvent, In all cases, it is preferred that the alkanoic acid anhydride (or acyl halide) be in molar excess with respect to the beta-cyclohomocitral, It is preferred that the mole ratio of alkanoic acid anhydride:beta-cyclohomocitral be 1.5:1. When using acyl halide it is preferred that the ratio of acyl halide:beta-cyclohomocitral be about 1:1.5 up to 1:2Ø Ratios outside of the foregoing limits are workable, however, when using such ratios, less economical and steps of greater complexity are required. When the reaction is carried out in the presence of an alkali metal acetate it is preferred that the mole ratio of alkali metal.

- . .

acetate:beta-cyclohomocitral be about 0.1:1. ~Jhen the reaction is carried out in the presence of alkali metal acetate, it is performed at elevated temperatures (100 - 200C) for a period of from 3 up to 10 hours. When the reaction is carried out using a paratoluene sulfonic acid catalyst it is preferred that the mole ratio of beta-cyclohomocitral:paratoluene sulfonic acid be from 1:0.01 up to 1:0.1 with the most convenient mole ratio being 1:0.02. I~hen using paratoluene sulfonic acid catalyst the reaction is carried out at reflux for a period of time from 10 up to 40 hours depending upon the process economics and desired yield.
One or more of the enol esters of our invention is capable of supplying and/or potentiating certain flavor and aroma notes usually lacking in many fruit flavors (e.g., berry, including raspberry; grape and apple juice) clove flavors, cinnamon flavors, tea flavors, honey flavors, dried fruit flavors, wine flavors and cocoa flavors as well as tobacco flavors heretofore provided. Furthermore, the beta-cyclohomocitral enol esters of our invention are capable of supplying certain fragrance notes usually lacking in many perfumery materials, for example, rose fragrances. The following Table I sets forther organoleptic properties of specific enol esters of our invention:

1053f~
. . ..
o ~
h ~1 1 u~
~n ~ 0 ~
~ ~ ~ O ~ I -~1 Ul H ~ ~ > ~\ ~) I ~: ~15 ~1 ` ~ I ` ~1 0 E~ ~) ~ 5 O h P~
~ a) ~ o ~ ~1 ~ 1 3 0 O ~ ~ P.~ I O ~
p:; ~ ~ OI O O O :> I O
h ~1 t~ 1 o-~1 1 a h ~ O ~ I h S
~; ~ o o ~ ~ ~ I o ~ u~ o h I ,1 a) ~
:~ g ~ O h I ,s~ l I ~ X h P ~ 3 ~
1:~ -1 ` ~ a) t: I o s:: Q I ~ '' -~J
~:4 ~1 o u~ O 1:: I ` h O I ~ 3 tt~ O Q 0 ,1 ~ , ` U I U
O ~: h ~ I ,:: ~ ~ U I ~ u~
o ~
u ~ ~ ~ a) I h X ~ O Q I ,1 ~
~1 -rl ~ ,1 h 3 0 I h 1~ h 3 ~
I~ I
I` a~
Ia) I x I h ~Q ~ ~ h I X ~ ` O I I ` ` ~
Q~ I rl h~l ~ U I a) ~ ~ a) o k I a) O h ~ I X Q. ~ O Q) h~
~ ~ ~ :~ ~ I I V ~ ~1 111 O ~ I O ~ ~ a h C.q h h h ~ h ~ `S ~ QO ~ ~ ¦ O h tq 1 ~ U O
~1 O a) a) a3 ~ ~ I o ~ ~ ~1 1 U 3 a~ a) U o -,~
H Q Q h Q .SI U ~ ~ S ~1 U) I U~ S rO ~ 1 O
E-l Q~ IO ~ ) 0 h ~ ~:
~; u~ h ~ I~1 l rl ~ a) a) ~ I~ aJ X -l Q ~ `a u~
1:~1$1 h t~ h ~I S u~ ~ ~ h 3 ~o X,~ X ~d I ~ X - 3 ` P~ h -O h U t~ I~1 1~ O ~1 ~1 Ul I ~1 1 Ul X 1~ ul ~ h a) ~ -1 I h h I h ~ o 3 ~ ~ V I ~ Ql ~ U h d o u ~ ~ o a) I o o ~ ~ ~ o ~ I ~ u~ o ~ I ~ ~ (d O a~
O ~S ~ ~ g ~ ~ I ~ O X ~ 3,~ O,,.~ S o h h E~ h 3 ~1 ~ I rl O ~1 ~I h h I h U ~1 h ~ ~ S O C~
~i ` h ` ~ I ~ ~ ~h U h 41 0 o ~
H 14 ` al la` al ~ O I aJ `~1 O Ql O U I ` ~1 O :~ O h ~ O ~ h O 33 ~ ~ o ~ h ~
Q ~O S lo ~ ~ S 1 3 X ~ ~: h o h H o O .~ ~ ~ O ~

t' l ~ O ~ 0 U ~ ~ ~ D ~ ~ 1 3 D ~ ( IE~ ~
l ll C~ O
D O O I o o I o O
V~ ~ I O ~ I O aJ
I I ~ I
C~ ~ U~ ~ V ~
14 h I td ~ 1 11) h O
O '~1 ~1 1 ~''1 ~ I a)-,l ,~
~ ~ EO~ ~ I Q O ~) I Q O h :~ ~
':C ~ O U I r1 0 t) I 'rl Z ~ ~ ~ I U S ~ I U,~

_ . IV U~ ' o o r~ O ~ u a v 3 v s ~ 0 I~ h m I ` S~o -I
~; ~ 0 ~ ~ `~3 o ~ ~s s ~ ~ 3~
r~ ~ v 0 ~ ~ù 3 ~ 3 ~ td ~ O ~ o O
3 Q o ~ ~ 3 o ~ s ~ I s ~ . 1 D O
r ~ ~ O ~ ~ ~ O I ~1 ~
S~ O ~ 3 ~ O ~ U
r~ ~ ~ ~ S a) ~ I O U
C Ul a~ ~ ~ 3 4~ s ,1 ~ ~ h ' U ~ 0 1 ~ '~ S~
S ~ ~''1 E~ E~ 3 a) S a) I ' 0 Q ~ E~ U
~1 ~I C~ O ~1 ~ ~ o I Q ~1 a) U ' ~
E~ ~ U ~ ~ U 3 ~ ,S ~ O
P~ a~ ~1 (~ Sl ` Id O (~ S-l rl R ~: ~ I o tn t) h ` u I ~I S~ aJ u `X :~
P~ o ~ o ~ I ~ O ~ 1 ~1 o s~ ~ u ~ ~, u7 ~ o I
Q u ~ u~ o h ~ ~ ~ S O t~ ~ t) S O O
u~ :~, o a) Q~ ,1 0 ~ , O I O ~1 ~ Q ' O

, ~ 3 0 ~ 0 ~3 ~ I ~ ~ 1 0 ~ 3 h ~: U ,~ rl ~ 0 a~ h Id O
~ ~ ~ ~ O ~ I ~ ~ 3 ~ 0 1 ~ ~ ~ ~ I ~ u ~
H ~ U ~ O h ~ _l ~ Ou~ O -,1 ~ O 1:: O al ~-0 ~ O ~ e ~91 o ~ 40.8 c ~ clt 3-~ ~ 3 ~ -I O ~

¦ ~D
X > I A~ I /~/
~ O I I I

3 'U~'O I 'U'O O 1'~
O ~ ~ I 0 ~ u ~ Iu a~ I u O d r~ II r~ ~ I U~r~
C~
o h a O ~ ~ ~ OQ .~
~n u ~ U ~ I Q U _1 ~3 ~ ~ I~: o Q I O Q
2, ~ e ~ 0 , UJ e o ~; s~ o ~ I~ o u, I ,~ o ~n Z ~Q I~ S-,~ I U~,l _ ~ - 23- - 23a -When the enol esters of our invention are used as food flavor adjuvants, the nature of the co-ingredients included with each of the said enol esters in formulating the product composition will also serve to alter, modify, augment or enhance the organoleptic characteristics of the ultimate foodstuff treated therewith.
As used herein in regard to flavors, the terms "alter", "modify`' and "augment" in their various forms mean "supplying or imparting flavor character or note to otherwise bland, relatively tasteless substances or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste".
The term "enhance" is used herein to mean the intensifi-cation of a flavor or aroma characteristic or note without the modification of the quality thereof. Thus, "enhancement"
of a flavor or aroma means that the enhancement agent does not add any additional flavor note.
As used herein, the term "foodstuff" includes both solid and liquid ingestible materials which usually do, but need not, have nutritional value. Thus, foodstuffs include soups, convenience foods, beverages, dairy products, candies, vegetables, cereals, soft drinks, snacks and the like.
As used herein, the term "medicinal product" includes both solids and liquids which are ingestible non-toxic materials which have medicinal value such as cough syrups, cough drops, aspirin and chewable medicinal tablets.

The term "chewing gum" is intended to mean a composition which comprises a substantially water-insoluble, chewable plastic gum base such as chickle, or substitutes therefor, including jelutong, guttakay, rubber or certain comestible natural or synthetic resins or waxes. Incorporated with the gum base in admixture therewith may be plasticizers or softening agents, e.g., glycerine; and a flavoring composition which incorporates one or more of the enol esters of our invention, and in addition, sweeteni-ng agents which may be sugars, including sucrose or dextrose and/or artificial sweeteners such as cyclamates or saccharin. Other optional ingredients may also be present.
Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature.
It is a requirement that any such material be "ingestibly"
acceptable and thus non-toxic and otherwise non-deleterious particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used ]0 is not caused to have unacceptable aroma and taste nuances.
Such materials may in general be characterized as flavoring adjuvants or vehicles comprising broadly stabilizers, thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers.
Stabilizer compounds include preservatives, e.g., sodium chloride; antioxidants, e.g., calcium and sodium ascorbate~ -ascorbic acid, butylated hydroxy-anisole (mixture of 2- and 3-tertiary-butyl-4-hydroxy-anisole~, butylated hydroxy toluene t2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like and sequestrants, e.g., citric acid.

1053681~

Thic]cener compounds include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, e.g., agar agar, carrageenan; cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth; gelatin, proteinaceous materials; lipids; carbohydrates; starches, pectins, and emulsifiers, e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose corn syrup and the like.
Surface active agents include emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid, m~ristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like.
Conditioners include compounds such as bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like; colorants, e.g., carminic acid, cochineal, tumeric and curcuma and the like; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphatet enzymes; yeast foods, e.g., calcium lactate ` and calcium sulfate; nutrient supplements, e~g., iron salts ` such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.

1~536~
Other flavorants and flavor intensifiers include organic acids, e.g., acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid, caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric acid, alpha-methyl-butyric acid, propionic acid, valeric acid, 2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid;
ketones and aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methyl carbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal, beta,beta-dimethyl-acrolein, methyl-n-amyl ketone, n-hexenal, 2-hexenal, iso-pentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptanal, nonyl aldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone, methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone, 2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-

4-pentenal, 2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural,

5-methyl furfural, cinnamaldehyde, beta-cyclohomocitral,2-pentanone, 2-pentenal and propanal; alcohols such as 1-butanol, benzyl alcohol-l-borneol, trans-2-buten-1-ol, ethanol, geraniol, l-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, l-pentanol, l-penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol, linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethyl caprate, ethyl caproate~
ethyl caprylate, ethyl cinnamate, ethyl crotonate, ethyl ~ormate, ethyl isobutyrate, ethyl isovalerate, ethyl laurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate, ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexyl butyrate, isoamyl acetate, isopropyl - 1~35368~

butyrate, methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate, alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate, cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbons such as dimethyl naphthalene, dodecane, methyl diphenyl, methyl naphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethyl naphthalene, tridecane, trimethyl naphthalene, undecane, caryophyllene, l-phellandrene, p-cymene, l-alpha-pinene; pyrazines such as 2,3-dimethylpyra~ine, 2,5-dimethyl-pyrazine, 2,6-dimethylpyrazine, 3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine, 3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine, 2-isoamyl-3,5,6-trimethyl-pyrazine, isopropyl dimethylpyrazine, methyl ethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils, such as jasmine absolute, cassia oil, cannomon bark oil, rose absolute, orris absolute, lemon essential oil, Bulgarian rose, yara yara and vanilla; lactones such as ~-nonalactone;
sulfides, e.g., methyl sulfide and other materials such as maltol, acetoin and acetals (e.g., l,1-diethyoxy-ethane, l,l-dimethoxy-ethane and dimethyoxymethane).
; The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event (i) be organoleptically compatible with the enol ester or esters of our invention by not covering or spoiling the organoleptic properties (aroma and/or taste) thereof; (ii) be nonreactive with the enol ester or esters of our invention and (iii) be capable of providing an environment in which the enol ester or esters can be dispersed or admixed to provide a homogeneous medium.

11~)5368~
In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof, will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the foodstuff, chewing gum, medici-nal product or toothpaste to which the flavor and/or aroma are to be imparted, modified, altered or enhanced, In contradis-tinction, in the preparation of solid products, e.g., simulated foodstuffs, ingredients capable of providing normally solid compositions should be selected such as various cellulose derivatives.
As will be appreciated by those skilled in the art, the amount of enol esters or esters employed in a particular instance can vary over a relatively wide range, depending upon the desired organoleptic effects to be achieved. Thus, correspondingly, greater amounts would be necessary in those instances wherein the ultimate food composition to be flavored is relatively bland to the taste, whereas relatively minor quantities may suffice for purposes of enhancing the composition merely deficient in natural flavor or aroma. The primary requirement is that the amount selected to be effective, i.e., sufficient to alter, modify or enhance the organoleptic characteristics of the parent composition, whether foodstuff per se, chewing gum per se, medicinal product per se, toothpaste per se, or flavoring composition.
The use of insufficient quantities of enol ester or esters will, of course, substantially vitiate any possibility of obtaining the desired results while excess quantities prove needlessly costly and in extreme cases, may disrupt the flavor-aroma balance, thus proving self-defeating. Accordingly, the 10536~8 terminology "effective amount" and "sufficient amount" is to be accorded a significance in the context of the present inven-tion consistent with the obtention of desired flavoring effects.
Thus, and with respect to ultimate food compositions, chewing gum compositions, medicinal product compositions and toothpaste compositions, it is found that quantities of enol ester or esters ranging from a small but effective amount, e.g., 0.5 parts per million up to about 100 parts per million based on total composition are suitable. Concentrations in excess of the maximum quantity stated are not normally recommended, since they fail to prove commensurate enhancement of organoleptic properties. In those instances, wherein the enol ester or esters is added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that the total quantity of flavoring composition employed be sufficient to yield an effective enol ester concentration in the foodstuff product.
Food ~lavoring compositions prepared in accordance with the present invention preferably contain the enol ester or esters in concentrations ranging from about 0.1% up to about 15~ by weight based on the total weight of the said flavoring composition.
The composition described herein can be prepared according to conventional techniques well known as typified by cake batters and fruit drinks and can be formulated by merely admixing the involved ingredients within the propor-tions stated in a suitable blender to obtain the desired --3l--con~i~tency, homogeneity of dispersion, etc. Alternatively, flavoring compositions in the form of particulate solids can ~e conveniently preoared by mixing the encl ester or e~ter~ with, for example, sum arabic, ~um tragacanth, - 5 carrageenan ar.d the like, and thereafter spray-drying the re~ultant mixture whereby to obtain the particular solid product. Pre-prepared flavor ~ixes in powder form, e.g., a fruit-flavored powder mix are obtained by mixing the dried solid components, e.g., starch, s~gar and the like and enol ester or esters in a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the enol ester or esters of our invention, the following adjuvants: p-hydroxy-benzyl acetone; geraniol; cassia oil; acetaldehyde; maltol;
ethyl methyl phenyl glycidate; benzyl acetate; dimethyl sulfide;
eugenol; vanillin; caryophyllene; methyl cinnamate; guiacoli ethyl pelargonate; cinnamaldehyde; methyl anthranilate; 5-methyl furfural; isoamyl acetate; isobutyl acetate; cuminaldehyde;
alpha iononei cinnamyl iormate; ethyl butyrate; methyl cinnamate;
acetic acid; gamma-undecalactone; napnthyl ethyl ether; diacetyl;
furfural; ethyl acetate; anethole; 2,3-dimethyl pyrazine; 2-ethyl 3-methyl pyrazine; 3-~henyl-4-pentenal; 2-phenyl-2-hex-enal; 2-phenyl-2-pentenal; 3-phenyl-4-pentenal diethyl acetal;
damascone (l-crotonyl-2,2,6-trimethylcyclohex-1-one~; damascenone ~ crotonyl-2,2,6-trimethylcyclohexa-1,5-diene); beta-cyclohomo-citral (2,2,6-trimethyl-cyclohex-1-ene carboxaldehyde); isoamyl butyrate; cis-3-hexenol-1; 2-methyl-2-pentenoic acid; elemecine l4-allyl-1,2,6-trimethoxy benzene); isoelemecine (4-propenyl-1, 2,6-trimethoxy benzene); and 2-(4-hydroxy-4-methylpentyl) nor-bornadiene prepared according to U.S. Application for Letters Pat~nt 461,703, filed on April 17, 1974.

1053~8~
An additional aspect of our invention provides an organo-leptically improved smoking tobacco product and additives therefor, as well as methods of making the same which overcome specific problems heretofore encountered in which specific desired sweet, floral, woody, spicey, ionone-like and fruity f1avor 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 aesired 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., dri~ed lettuce leaves) an aroma and flavor additive containing as an active ingredient one or more enol esters of our inventlon.
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:
I. Synthetic Materials:
Beta-ethyl-cinnamaldehyde;
Eugenol;
Dipentene;
Damascenone;

- ~05368l~
Maltol;
Ethyl maltol;
Delta undecalactone;
Delta decalactone;
Benzaldehyde;
Amyl acetate;
Ethyl butyrate;
Ethyl valerate;
Ethyl acetate;
2-Hexenol-1,2~methyl-5-isopropyl-1,3 nonadiene-8-one;
2,6-Dimethyl-2,6-undecadiene-10-one;
2-Methyl-5-isopropyl acetophenone;
2-Hydroxy-2,5,5,~a-tetramethyl-1-~2-hydroxyethyl)-decahydronaphthalene;
: Dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2,1-b)-furan;
4-Hydroxy hexanoic acid, gamma lactone; and Polyisoprenoid hydrocarbons defined in Example V of V.S. Patent 3,589,372 issued on June 29, 1971.

II. Natural Oils Celery seed oil;
; Coffee extract;
Bergamot Oil;
Cocoa extract;
Nutmeg oil; and Origanum oil.
An aroma and flavoring concentrate containing beta-cyclo-homocitral 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 natural and/or sweet notes, we have found that 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.

1053f~8t~

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:
~0~

in 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 evapora-tion 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.

1053~:i8~
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 a!dded to certai~n 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.
The enol ester (or mixture of esters) and one or more auxiliary perfume ingredients, including, for example, alcohols, aldehydes, nitriles, esters, cyclic esters, and natural essential oils, may be admixed so that the combined odors of the individual components produce a pleasant and desired fragrance, particularly and preferably in rose fragrances. Such perfume compositions usually contain (a~
the main note or the "bouquet" or foundation stone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which include oaorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation;
and (d) topnotes which are usually low boiling fresh smelling materials.
In perfume co~positions, it is the individual components which contribute to their particular olfactory characteristics, however the overall sensory effect of the perfume composition will be at least the sum total of the effects of each of the ingredients. Thus, one or more of the enol esters can be ~ 3~ -used to alter, modify or enhance the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contribued by another ingredient in the composition.
The amount of enol ester (or mixture of esters) of our invention which will be effective in perfume compositions as well as in perfumed articles and colognes depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.01% of enol ester (or mixture of estersl or even less (e.g., 0.005%) can be used to impart a sweet, floral, fruity odor with beta-ionone-like and tobacco-like nuances to soaps, cosmetics or other products. The amount employed can range up to 70% of the fragrance components and will depend on consiaeration of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.
The enol esters (or mixtures of esters) of our invention 2Q are useful ~taken alone or together with other ingredients in perfume compositions] as (an) alfactory component(s) in detergents and soaps, space odorants and deodorants, perfumes, colognes, toilet water, bath preparations, such as lacquers, brilliantines, pomades and shampoos; cosmetic preparations, such as creams, deodorants, hand lotions and sun screens;
powders, such as talcs, dusting powders, face powders and the like. When used as (an~ olfactory component(s) as little as 1~ of enol ester (or mixture of esters) will suffice to impart an intense floral note to rose formulations.
` 30 105368~

Generally, no more than 3~ of enol ester (or mixture of esters) based on the ultimate end product, is required in the perfume composition.
In addition, the perfume composition or fragrance composition of our invention can contain a vehicle, or carrier for the enol ester or mixture of enol esters. The vehicle can be a liquid such as an alcohol, a non-toxic alcohol, a non-toxic glycol, or the like. The carrier can also be an absorbent solid, such as a gum (e.g., gum arabic) or components for encapsulating the composition (such as gelatin).
It will thus be apparent that the enol ester (or the mixture of esters) of our invention can be utili~ed to alter, modify or enhance sensory properties, particularly organoleptic properties, such as flavor(s) and/or fragrance(s) of a wide variety of consumable materials.
Examples I-VIII, X, XVII, XXV, XXVI, XXXVII, XXXVIII, ; XLVIII, XLIX, L, LIII-LVIII, LX-LXIV and LXX, following, serve to illustrate processes for specifically producing the enol 2Q esters useful in our invention.
xamples 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
and LXVI-LXIX 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 illustra-tive 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.

- 3~ -1~35361~
EXAMPLE I
PRODUCTION OF "TRANS" BETA-CYCLOHOMOC~TRAL
E~IOL ACETATE FROM BEmA-IONONE
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 10C during a period of one hour. The reaction mass is stirred at 10C for an additional hour and the solution is then allowed to slowly warm up to room temperature. The reaction mass is then poured into one 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 eyaporated from the organic phase to yield 99.5 grams of an oil which is then chromato-graphed 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 hexane8.0 grams 2 500 cc hexane31.7 grams 3 300 cc hexane13.5 grams 4 250 cc hexane7.0 grams 250 cc hexane1.9 grams

6 250 cc hexane1.6 grams

7 600 cc 25% diethyl15.6 grams ether-75% hexane

8 600 cc diethyl ether15.3 grams Fractions 1-4 are composed mainly of "trans" beta-cyclohomo-citral enol acetate.
The spectral data for a purified sample of this material obtained by preparative gas chromatography confirm the structure:

~``E~

The mass spectrum of this compound has the following fragmentation pattern, in decreasing order o~ 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~l):

3090 ~C=C~ (C-H) 1752 C=O (vinyl ester) 1650 C=C (conjugated with oxygen) 20 1360 C~

C-O (of the ester) 930 /C=C~ (trans) H

The NMR spectrum exhibits in CDC13 solution the following proton absorptions (chemical shifts in ppm):
Ppm Multiplicity Assignment No. of Protons _ .
1.00 (s) ~ f 6H
C

.. . . _ . _ _ ...
1.70-1.40 (m) ~ CH2~ ~ 7H

1.76 (s) =C-CH3 J

2.00 (t) =C-CII2- 2H

.

2.16 (s) CH3-C~ 3H

. :

5.86 and (m) Olefinic 2H
7.20 Protons ..

.

1~5368t~

EXAMPLES II-X
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 aO not represent yields of isolated material.

Example No. % Enol % Starting % Bi- Reactants and Ester Material Products Reaction Conditions II 47 24 29 Acetic acid-(150 cc) Sodium acetate (20 g) Beta-ionone-(30 g) 40% peracetic acid-(30 g) Temperature: 25C

III 12 52 36 Acetic acid-(150 g) Beta-ionone-(30 g) 40% peracetic acid-(30 g) Temperature: 25C

, Example No. % Enol % Starting % Bi- Reactants and Ester Material Products Reaction Conditions -IV 40 29 31 Cyclohexane-(150 cc) Sodium acetate-(20 g) Beta-ionone-(30 g) 40% peracetic acid-(30 g) Temperature: 25C
V 52 26 22 Acetic acid-(150 cc) Potassium acetate-(35 g) Beta-ionone-(30 g) 40% peracetic acid-(30 g) Temperature: 25C
VI 31 30 39 Formic acid-(150 cc) Potassium acetate-(50 g) Beta-ionone-(30 g) 40% peracetic acid-(30 g) Temperature: 25C
VII 49 6 45 Acetic acid-(150 cc) Potassium acetate-(35 g) Beta-ionone-(30 g) 50% peracetic acid-(33 g) Temperature: 25C
VIII 36 21 43 Acetic acid-(150 cc) Potassium acetate-(35 g) Beta-ionone-(30 g) ; 40% peracetic acid-(33 g?
`, Temperature: 50C

, 30 ~, iO53688 Example No. % Enol ~ Starting % Bi- Reactants and Ester Material Products Reaction Conditions IX 0 9 91 Dimethyl Beta- formamide (150 cc) ionone Beta-ionone-(30 g) epoxide 40~ peracetic acid-(33g) Temperature: 4 days at a temperature of X 55 17 28 Acetic acid-(450 cc) Potassium acetate-(105 g) Beta-ionone-(96 g) 40% peracetic acid-(105 g) Temperature: 25C

EXAMPLE XI
ROSE FORMULATION
To demonstrate the use of "trans" beta-cyclohomocitral enol acetate in a rose formulation, the following formula is provided:

Ingredient Parts by ~eight : 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 Nusk ambrette 10 IngredientParts by ~IJeight 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, ~-hexenyl acetate 2 "Trans" beta-cyclohomocitral enol acetate prepared according to Example I 5 The addition of 0.5% of beta-cyclohomocitral enol acetate lends a great deal of strength and character to the rose fragrance~ It contribues 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.
EXAMPLE XII
PREPARATION OF A SOAP COMPOSITION
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.

EXAMPLE XI I
PREPARATION OF A DETERGE~T COMPOSITIO~

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.

EXAMPLE X IV
RASPBERRY FLAVOR FORr~ULATIO~I

The following basic raspberry flavor formulation is produced:

Ingredient Parts ~y Weight Van~llin 2.0 Haltol 5.o Parahydroxybenzylacetone 5.0 . Alpha-ionone ~10% in propylene glycol) 2.0 Ethyl butyrate 6.0 Ethyl acetate. 16.0 D~methyl sulfide 1.0 Isobutyl acetate . 13.0 Acetic acld 10.0 ; Acetaldehyde ~o.o Propylene glycol 930.0 ~rans n 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 formul~tion without the beta-cyclohomo-c~tral enol acetate at the raee of 0.01 percent (10~ ppm)in water and evaluated by a ~ench panel.

-- The flavor containing the "trans" beta-cyciohomocitral enol acetate is found to have substantially sweeter aroma notes and a sweet raspberry, rasoberry ~ernel-li.~e and sweet aftertaste and mouth.eei ~.issing in :he basic raspberry - formulation. It is the unan-'mous opir.,on 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.

EXAMPLE XV

~Eveready" canned carrot juice, manufactured by the Dole Corporation of San Jose, California', is intimately ~dmixed with 15 ppm of "trans" beta-cyclohomocitral enol ~cetate and the resulting mixture is compared with same ~uice unflavored. The weak aroma and taste of the juice `; 25 ' 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"
bQta-cyclohomocitral enol acetate as compared with the unflavored carrot juice.

EXAMPLE XVI
FORMATION OF ALPHA-IOIIONE EPOXIDE FROM ALPHA-IONONE
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 Acetate35 grams Alpha-Ionone 30 grams 33 Grams of 40~ peracetic acid is then added dropwise into the reaction mass with stirring at 25C over a 45 minute period. The reaction mass exotherms for approximately one 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 93-99C at 0.5 mm Hg pressure yielding 28.3 g of a clean colorless liquid.
IR, MS and NMR analyses confirm the fact that the product is alpha-ionone epoxide having the structure:
o -Mass spectral analysis for alpha-ionone epoxide is as follows:
Relative Intensity (Order of Most Abundant Ion m/e Indicated in Superscript) 43 lool ; 179 236 The IR spectrum for alpha-ionone epoxide is set forth in Figure 32. Figure 33 is the NMR spectrum for alpha-; ionone epoxide.
EXAMPLE XVII
PROD~CTION OF "TRANS" BETA-CYCLOHOMOCITRAL ENOL ACETATE
, Into a two liter reaction flask equipped with stirrer, thermometer, addition funnel and cooling bath, the following materials are placed in the following order:
, Ingredients Amo~nt Acetic Acid 450 cc ' Potassium Acetate 105 grams Beta-Ionone 96 grams 105 Grams of 40% peracetic acid is then added dropwise to the reaction mass with cooling while maintaining the reaction mass at 25C + 2C over a period of two hours.

~53688 The reaction mass is then stirred for an additional three-hour period (during the first hour a slight exotherm occurs) at 25C.
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 other 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.
EXAMPLE XVIII
TOBACCO FORMULATION
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 ~eight ~ . _ Ethyl butyrate .05 Ethyl valerate .05 - 105368~

Maltol 2.00 Cocoa extract 26.00 Coffee extract 10.00 Ethyl alcohol 20.00 ~later 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-cyclo-homocitral 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 blendea cigarette imparting to it sweet, natural tobacco notes.
EXAMPLB XIX
PREPARATION OF A COSMETIC-POWDER COMPOSITION
A cosmetic powder is prepared by mixing in a ball mill 100 g of talcum powder with 0.25 g of "trans" beta-cyclohomo-citral enol acetate prepared according to Example XVII. It has an excellent sweet, floral, fruity aroma.
EXAMPLE XX

.
PERFUMED LIQUID DETERGENT
_, 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.
EXAMPLE XXI
_ .
PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME
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 of perfume.
- EXAMPLE XXII
PREPARATION OF A COLOGNE AND ~IANDKERCHIEF 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-cyclo-homocitral enol acetate in the composition of Exa~ple XI
affords a distinct and definite strong rose aroma with sweet, floral, fruity notes to the handkerchief perfume and cologne.
EXAMPLE XXIII
PREPARATION OF SOAP COMPOSITION
. .
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.
EXAMPLE XXIV
PREPARATION OF A DETERGENT COMPOSITION
-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.
EXA~IPLE XXV
Perpropionic acid is prepared in the following manner.
A mixture of the following materials:

` tl60 ml propionic acia ) Referred to ( 1 ml sulfuric acid [concentrated]) 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 - 1~53688 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 + 2C by means of external cooling. I~en the addition is complete the reaction mixture is stirred for an additional 2 hours at 25C.
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 dxied 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 Figure 34 (GLC conditions: 10' x 1/4" 10% Carbowax 20M
column, operated at 220C isothermal).
EXAMPLE XXVI
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 25C by means of external cooling. After the addition is complete, the mixture is stirred for a further 90 minutes at 25C 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 combi~ed, 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 chromatograpnic analysis of this material shows the following compositions:

~H ~ (4l0:

~tra~s~ isomer) .' ' 'o ~ 132%);Other products 23%

1~5368~
EXAMPLE XXVII
A. POWDER FLAVOR COMPOSITION
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-aried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500F., an outlet temperature of 200F., and a wheel speed of 50,000 r.p.m.
B SUSTAINED RELEASE FLAVOR
The following mixture is prepared:
Ingredient Parts by Weight Liquid Raspberry Flavor Composition of Example XIV 20 Propylene glycol 9 Cab-O-Sil ~ M-5 (Brand of Silica produced by the Cabot Corporation of 125 High St., Boston, Mass. 02110;
Physical Properties:
Surface Area: 200 m2/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 25C for a period of 30 minutes resulting in a dry, free flowing sustained release flavor powder.

EXAMPLE XY~VIII
10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of water at a temperature of 150F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120F.
20 Parts by weight of the liquid flavor composition of Example XIF is added to the solution which is then homo-genized to form an emulsion having particle size typically in the range of 2 - 5 microns. This material is kept at 120F. 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 65F. The resulting jelled coascervate may be filtered and washed with water at temperatures below the melting point of gelatin, to remove the salt.
~ardening 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.

1053~8 EXAMPLE XXIX
CI~EWING GUM
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 blena 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 as a pleasant long-lasting raspberry flavor.
EXAMPLE XXX
CHEWING GUM
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 as a pleasant long-lasting raspberry flavor.

EXAMPLE XXXI
TOOTHPASTE FORMULATION
The following separate groups of ingredients are prepared:
Parts by Weight Ingredient _roup " A"
30.200 Glycerin 15.325 Distilled Water .100 Sodium Benzoate .125 Saccharin Sodium .400 Stannous Fluoride Group "B"
12,500 Calcium Carbonate 37.200 Dicalcium Phosphate (Dihydrate) Group "C"
2.000 Sodium N-Lauroyl Sarcosinate (foaming agent) Group "D"
1.200 Flavor ~qaterial of Example XXVII
100.00 (Total) PROCEDURE:
1. The ingredients in Group "A" are stirred and heated in a steam jacketed kettle to 160~F.
2. Stirring is continued for an additional three to five minutes to form a 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 sill and then homogenized, and finally tubed.

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

1053681~
,.
EXAMPLE XXXII
C~IEWABLE VITAMIN TABLETS
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 Vitami Bl (thiamine mononitrate) as Rocoat ~ thiamine mononitrate 33 1/3%
(Hoffman La Roche) 4,0 Vitamin B2 (riboflavin) as Rocoat ~
riboflavin 33 1/3~ 5.0 Vitamin B6 (pyridoxine hydrochloride) as Rocoat ~ pyridoxine hydrochloride 33 1/3% 4.0 Niacinamide as Rocoat ~
- niacinamide 33 1/3% 33.0 Calcium pantothenate 11.5 Vitamin ~12 (cyanocobalamin) as Merck 0.1% in gelatin 3.5 Vitamin E (dl-alpha tocopheryl acetate) as dry Vitamin E acetate 33 1/3% Roche 6.6 d-Biotin 0.044 Certified lake color 5.0 Flavor of Example XXVIII 5.0 Sweetener - sodium saccharin1.0 Magnesium stearate lubricant10.0 Mannitol q.s. to make 500.0 - Preliminary tablets are prepared by slugging with 30 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. - 61 -Chewing of the resultant tablets yields a pleasant, long-lasting, con5istently strong raspberry flavor for a rlod of 12 minutes.
_ . .

BXAMPLE X~XI~I ~
CEEWING TO~ACC~
.

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15% Pennsylvania leaf) the following casing is ~prayed at a rate of 30~:

~9~ Parts by Weight Cor~ Syrup ~CO
~corice 10 Glycerine 20 Flg Juice ~.6 ~rune Juice S
Flavor Material of ~ ' Example X~VII 0.~ ~
!
! ~he resultant product is redried to a moisture content 'of 20~. On chewing, this ~obacco has an excellent substan-tially consistent, long-lastir.g rasp~erry ~20 minutes) i 20 nuance in conjunction ~ith the main ~ruity tobacco note.
.

--- 1053~88 EXAMPLE XXXIV
PRODUCTION OF BETA-CYCLOHOMOCITRAL ENOL BUTYRATE
Reaction:

~CC~ ~~0~ ~ ~ o (cis/trans mixture) 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 170C 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, ; 20 respectively, the structures:

~~+ ~~
(cis) ~trans) The GLC profile is set forth in Figure 1 (conditions:
10' x 1j8" Carbowax 20 M column, programmed from 80-180C at 4C per minute).
The GC-MS profile is set forth in Figure 2.

~ 63 -....

1053688 ~ ç y ~h- NMR analysis of the ~cis~ isomer of beta-cyclo-~o~ocitral enol butyrate i~ as follows:

0.97 ppm ~nglet superimposed C~3 o~ triplet ~ C-''5 C~ ~ and . ~ ~3 9 -l.S4 broad singlet -C-C~3 , ' ( 9 1.78-1.21 mult~plet ~ C~2-t-_ .
2.00 ~ffuse ~riplet =C-CH2- 2~

. . .
.
2.35 triplet -C~2-C-~- 2 S.32 doublet ~ .
(J-7~z,cis) ~ 8CsC-O- 1 7.06 doublet ~ 1 . . .

~he NMR spectrum for t;ne "cis~ isomer of ~eta-cyclohomo-c~tral enol butyrate is set forth in Figure 3.

~he Infrared analysis 'or the ncisn isomer of beta-cyclohomocitral enol butyrate is as follows: -, 740, 1085, 1160, 1230, 1360, 1750, 2870, 2940, 2960 cm 1 ~e Infrared spectrum ~or the ~cis" isomer of beta-cyclohomocitral enol butyrate is set fo~th in Figure 4.

"-` 105368~
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~l The Infrared analysis for the "trans" isomer of beta-cyclohomocitral enol butyrate is set forth in Figure 5.
The NMR spectrum for the "trans" isomer of beta-cyclo-homocitral enol butyrate is set forth as follows:

1.00 ppm doublet superimposed fH
on triplet ¦ ~ C- I
~ CH3'' ~ 9H
+
~H3-CH2~

1.82-1. 43 multiplet =C-CH3 ~ -+ ~ llH
-t 2t-4 J

2.00 diffuse triplet =C-CH2- 2H

2.40 triplet -CH2-C-O- 2H

... .
5.86 doublets H 11+
(J-13 Hz, trans) HC=C-O-C- 2H
7.02 . .
~; .
. The NMR spectrum for the "trans" isomer of beta-cyclohomocitral enol butyrate is set forth in Figure 6.

.

` 1053688 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 after-taste.
EXAMPLE XXXV

PRODUCTION OF BETA-CYCLOHOMOCITRAL ENOL BUTYRATE
Reaction:

" ^J' ,L~ ~"`
(cis/trans mixture) Into a 100 ml reaction flask are added the following materials:
Ingredients Quantity beta-cyclohomocitral 16.6 g (0.1 moles) paratoluene sulfonic acid 0.5 g (0.03 moles) butyric anhydride 39.5 g (0.25 mole) l~S3688 The reaction mass is heated with stirring to 170C and maintained at 170C 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' x 1/4" Carbowax 20 M column, programmed from 80-180C at 4C per minute).
The GLC profile is set forth in Figure 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 Figure 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-cyclohomo-citral enol butyrate. The products are separated by preparative GLC.
EXAMPLE XXXVI
PRODUCTION OF-BETA-CYCLOHOMOCITRAL ENOL BUTYRATE
Reaction: O
~,0~,+~'0~ ~ ~ ~

` Into a 25 ml reaction flask the following materials are added.

... - , ~ .

`- 1053688 Ingredie_ts 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 170C 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 Figure 8.
The GC-MS profile is set forth in Figure 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 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.
XAMPLE XXXVII

PRODUCTION OF BETA-CYCLOHOMOCITRAL ENOL ISOBUTYRATE
Reaction:

~c,~ +~ 9 ~

3~ + ~ O

---` 1053688 Into a 100 ml reaction flask equipped with stirrer, thermometer and reflux condenser are placed the following ingredients:
~redients 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 169C 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 ]0 Figure 10 (conditions: 10' x 1/8" Carbowax 20 M column, programmed from 80-180C at 4C per minute).
The GS-MS profile is set forth in Figure 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 Figure 12.
The NMR spectrum for the "trans" isomer is set forth in Figure 13.

The trans isomer of beta-cyclohomoeitral enol isobutyrate, insofar as its flavor properties are concerned, has a sweet, woody, rosey, fruity, "wood-rosin", spicey, apple juiee aroma with fruity, apple/raspberry, woody, sweet, wood-rosin, tea and astringent flavor characteristics. Insofar as its perfumery uses are concerned, it has an acidie, 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 eoneerned, has a sweet, oriental/olibanum, "delicate rosey", fruity, ionone-like, elove, eamphoraceous aroma with rosey, woody, elove, mimosa, ionone, musty and eamphoraceous flavor eharaeteristies. The perfume properties of the eis isomer are sueh that it has a sweet, woody, green tobaeeo aroma with fruity and resinous notes; but it is not quite as fruity as the trans isomer.
The eis isomer also has strong ionone, mimosa nuanees.
It is noteworthy that the eis and trans isomers have uses in food flavors different from one another. The eis isomer is useful in elove and einnamon flavors whereas the trans isomer is useful in apple juiee, tea, raspberry and honey flavors.

EXAMPLE XXXVIII
PRODUCTION OF BETA-CYCLOHOMOCITRAL ENOL OCTANOATE
.
Reaction:

~Cc`~ + '~^J'~ ~

10 ~ ~ '+ ~~--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 170-190C. 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 tempera-ture. 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 anhyarous 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 Figure 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 Figure 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.
Figure 16 is the NMR spectrum for the "trans" isomer of beta-cyclohomocitral enol octanoate. Figure 17 is the NMR
spectrum for the "cis" isomer of beta-cyclohomocitral enol octanoate.
The "cis" isomer, from a flavor evaluation stand-point, 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, cheesey, 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.
EXAMPL~ XXXIX
ROSE FORMULATION
The following mixture is prepared:
IngredientParts by Weight Citronellal 60 Geraniol 40 Citronellyl formate 5 Geranyl acetate 3 Phenylethyl alcohol 20 Phenyl acetic acid 3 Methyl phenyl acetate IngredientParts by Weight . _ Phenylethyl acetate 2 4-(4-methyl-4-hydroxy)~3~
cyclohexene carboxaldehyde 3 Linalool 6 Eugenol 2 Mixture of "cis" and "trans"
beta-cyclohomocitral enol isobutyrate produced according to the process of Example 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".
EXAMPLE XL
BASIC CANNOMON FLAVOR USING CIS-BETA-CYCLOHOMOCITRAL ENOL BVTYRATE
The following basic cinnamon flavor is prepared:
IngredientParts 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-cyclohomo-citral enol isobutyrate prepared according to the process ~053688 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 beta-cyclo-homocitral enol isobutyrate.
EXAMPLE XLI
BASIC RASPBERRY FORMULATION CONTAI~ING CIS ~ETA-CYCLO-The following basic raspberry formulation is prepared:
Ingredient Parts by Weight Vanillin 2 Maltol 4 Parahydroxy benzyl acetone 5 Alpha-ionone (lO~ in propylene glycol~ 2 Ethyl butyrate 6 Ethyl acetate 16 Dimethyl sulfide Isobutyl acetate 14 Acetic acid lO
Acetaldehyde lO
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 lOO ppm in the form of a 5~ solution in food grade 10536~8 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.
EXAMPLE XLII
FLAVOR USE OF CIS BETA-CYCLOH0~50CITRAL ENOL OCTANOATE
. . _ 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 ~oiling 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-cyclohomo-citral enol octanoate. Fruity/delicate rosey, pleasant tea-like aroma notes and fruity/delicate rosey/tea taste notes are added to the basic tea taste and aroma by means of the "cis" isomer of beta-cyclohomocitral enol octanoate.
EXAMPLE XLIII
FLAVOR USE OF THE TRANS ISOMER OF BETA-CYCLO~OMOCITRAL ENOL
.
ISOBUTYRATB
At the rate of 3 ppm the trans isomer of beta-cyclo-homocitral 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 tea-like aroma. The taste is stale and bitter with the tannin notes dominating.
The addition of the trans isomer of beta-cyclohomocitral 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.
EXAMPLE XLIV
USE OF THE TRANS ISOMER OF BETA-CYCLOHOMOCITRAL ENOL BUTYRATE

.
IN BEVERAGE
At the rate of 1 ppm, the trans isomer of beta-cyclohomocitral 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-cyclohomo-citral 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.
E~AMPLE XLV
BASIC CLOVE FORMULATION USING THE CIS ISOMER OF BETA-CYCLOHOMO-CITRAL ENOL 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) Cuminaldehyde , 5-Methyl furfural 5 `' Eugenol 83 -` 30 ~ 76 --:" 1053688 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-cyclohomo-citral 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.
EXAMPLE XLVI
PREPARATION OF TRANS BETA-CYCLOHOMOCITRAL ENOL PROPIONATE
Reaction:

+ :~3C-C~

Into a 250 ml reaction flask equipped with stirrer, additional funnel, thermometer and cooling bath, the following materials are placed:
Ingredients Quantity ~ ... _ _ beta-n-methyl ionone 22.6 g (0.1 mole) (91% purity) water 40 ml acetic acid 50 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 25-30C.
After addition of the peracetic acid is completed, the reaction mass is stirred for a period of 2 hours while maintaining the temperature at 25-30C. 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 of product.
The GLC profile of the reaction product containing trans beta-cyclohomocitral enol propionate is set forth in Figure 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 ~haracteristic at 1 ppm. It is about two times as strong, sweetsr, 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 ionone notes; but it is not as pleasant as "trans" beta-cyclohomocitral enol acetate which is preferred by a panel of perfumers.
EXAMPLE XLVII
ATTEMPTED PREPARATION OF BETA-CYCLOIIOMOCITRAL ENOL ACETATE
USING PE~ALEIC ACID A`lHYDRIDE

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 0C 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 two 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.

~ 79 -EXAMPLE XLVIII

PRODUCTION OF BETA-CYCLOHOMOCITRAL E~iOL ACETATE USING METHYLENE
.. . . .
DICI~LORIDE SOLVE~T
Reaction:

+ ~3C-C~ ___~ ~ ~

Into a 250 ml reaction flask equipped with stirrer, thermometer, cooling bath and addition 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 25C up to 30C. After the 45 minute periGd 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.

1~53688 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-cyclohomocitral enol acetate is thus determined to be about 20~ with percent conversion from beta-ionone to enol acetate of about 30%. Figure 19 sets forth the GLC profile for the crude reaction product.
EXAMPLE XLIX
PRODUCTION OF TRANS BETA-CYCLOHOMOCITRAL ENOL ACETATE USING
A BENZENE SOLV~NT
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~

- al-lOS3688 The reaction mass is stirred for a period of lO 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 25-30C. The reaction mass is then stirred for another 3 hours at which time it is aaded 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 lO0 ml portion of saturated aqueous sodium chloride and one lO0 ml portion of water. The organic phase is then dried over anhydrous magnesium sulfate, filtered and stripped 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-cyclo-homocitral enol acetate is 27.4%. Figure 20 illustrates the GLC profile of the crude reaction product.

.

EXP~IPLE L
PREPARATIOM OF BETA-CYCLOHOMOCITRAL ENOL ACETATE USING BENZENE
SOLVENT AND M-CHLOROPERBEI~ZOIC ACID OXIDIZING AGE~T
Reaction:

+ ~ ~O-O-II ~

Into a 500 ml reaction flask equipped with stirrer, thermometer and addition funnel the following materials are added:
Ingredients Quantity Benzene 100 ml Sodium acetate 13 g (0.1~ mole) Beta-ionone 19.2 g (0.10 mol.e) 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 25-30C. At the end of the 80 minute period the reaction mass is stirred for an adaitional 2 hours at which time the solids are filtered from the reaction mass.
The organic layer is then wahsed 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:.
Tngredients Quantity Trans beta-cyclohomocitral enol acetate 28.3% C29.7% yield) Beta-ionone 22.6~ (25.7% recovery) beta-ionone epoxide 37.8% (39.7~ yield) 105;~6~t~
Figure 21 sets forth the GLC profile for the crude reaction product.
EXAMPLE LI
ATTEMPTED PRODUCTION OF BETA-CYCLOHOMOCITRAL ENOL ACETATE
USING PERPHTHALIC ACID ANHYDRIDE OXIDIZING AGENT AND
CYCLOHEXANE SOLVENT
Reaction:

~ + ~22 > ~ (I) O O

(I)+ ~ __~ ~ O

(1.8) (40.7%) Into a 500 ml reaction flask equipped with stirrer, thermometer and addition funnel the following materials are -.
addeds . Ingredients Quantity Cyclohexane 150 ml 30~ Hydrogen peroxide 19.2 g ~0.17 mole) The reaction mass is cooled to 0C and, 19.6 (0.2 mole) of perphthalic anhydride is added slowly. The reaction mass is then stirred for one 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 25C. 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 lOS368~

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 1.8% (1.8% yield) enol acetate Beta-ionone 47.3% (51.4% recovery) Beta-ionone epoxide 40.7~ (40.9% yield) The foregoing represents 1.8% yield of trans beta-cyclohomo-citral enol acetate. Figure 22 sets forth the GLC profile for the crude reaction product.
EXAMPLE LII
ATTEMPTED PRODUCTION OF BETA-CYCLO~IOMOCITRAL ENOL ACETATE
USING A DIMET~Y 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 Leta-ionone 19.2 g (0.1 mole) Sodium acetate 13 g (0.13 mole) -, 1053~88 .. . .
She reaction mass is stirred for a period of 10 minutes after whlch 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 25-30C.

S Additi~n of peracetic acid takes place over a period of 30 minutes with stirring while maintaining the temp-~rature of the reaction mass at 25-30C. Aft~r addition of the peracetic acid the reaction mass is stirred for another 2 hours. At this point the -eaction mass has a character-istic purple color.

~he reaction mass is then added to 300 ml water and the resulting mixture is added to 300 ml diethyl ether thereby forming an emulsion. She resulting emulsion is broken upon heating and stan~ing f~r 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 ~races of beta-cyclohomocitral enol ~cetate and beta-ionone epoxide. The aqueous layer is purplish indicatins that the amine is oxidized preferen-tially over the beta-ionone.
.
The G~C profile for the reaction product in the ~ther layer is set forth in Figure 23.
' . .

- g~

.` . . ' ' , .

EXAMPLE LIII
PRODUCTION OF BETA-CYCLOHOMOCITRAL ENOL ACETATE USING FORMAMIDE
Reaction:

+ H3C- C~ Formamide> ~
O- O - H KOAc 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 mole) of 40%
peracetic acid is commenced while maintaining the temperature at 25-30C. 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.

1053~8~
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 Figure 24.
EXAMPLE LIy PRODUCTION OF TRANS BETA-CYCLOHOMOCITRAL ENOL ACETATE

USING DIMETHYL 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 1~5;~688 temperature of 25-30C. The addition of the peracetic acid is carried out over a period of 50 minutes while maintaining the reaction mass at 25-30C. A very mila 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 j 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 Figure 25.

EXANPLE LV

PRODUCTION OF BETA-CYCLOHOMOCITRAL ENOL ACETATE USING m-CHLORO
.... ... _ .
PERBENZOIC ACID OXIDIZING AGENT (USING 50% MORE SOLVENT THAN

IN EXAMPLE L) Reaction:

~ ~ C~ Benzene ~

Cl l~S3688 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 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 i$ 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, 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 Figure 26.

'' , 30 . , ~(~53688 EXAMPLE LVI
PRODUCTION OF TR~S BETA-CYCLOHOMOCITRAL ENOL ACETATE USING A
FORMAMIDE SOLVENT
A procedure is carried out identical to that of Example LIII except that the resultlng 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 Figure 27.
EXAMPLE LVII
OXIDATION OF DELTA METHYL IONONE TO FORM CORRESPONDING TRANS
ENOL ACETATE
Reaction:
O

H3C C~ HOAc ~ ~

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) ':

~5~3~88 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 25-30C. Addition of the paracetic 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 25-30C.
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 di-chloride 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:
~ O ~

The GLC profile for the resulting crude product is set forth in Figure 28.
From a flavor standpoint, the alpha, 2,6,6-tri- -methyl-l-cyclohexene-trans-l-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.

EXAMPLE L~III
PREPARATION OF BETA-CYCLOHOMOCITRAL CIS EMOL ACETATE
Reaction:

C~ + H3C- C~ ~ - CH3 KO~c ~ "trans" isomer + ~~
"cis'' isomer 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 c,ried over anhydrous magnesium sulfate, filtered and stripped of solvent on a Rotovap.
GLC analysis indicates the presence of 3 compounds:
1. beta-cyclohomocitral 2. beta-cyclohomocitral trans enol acetate 3. beta-cyclohomocitral cis enol acetate 1G3 53~88 The GLC profile is set forth in Figure 29. The GC-MS
profile is set forth in Figure 30. The NMR spectrum for the trapping consisting of the cis enol acetate is given in Figure 31. The ~MR analysis is as follows:
Peak Interpretation 0.98 ppm (s) CH3 \l 1.54 (broad singlet) =C- CH3 3H

O
2.14 (s) CH3 - C - 3H

5.34 (d) ~ lH
~ olefinic protons 7.04 (d) ~ lH

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-cyciohomocitral cis enol acetate, has the following organoleptic properties:
Flavor Properties Perfumery Properties A sweet, floral, ionone-like, ~arthy, camphoraceous woody, violet, fruity, cary- and sea-like aroma with pphyllene 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.

1i~5~688 EXAMPLE LIX
ATTEMPTED PREPARATION OF BETA-CYCLOHOMOCITRAL ENOL ACETATE
. . .
USING DIMETHYL FORMA~IDE 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 25C, 19.6 g (0.1 mole) 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.

~ ~05;~68l~
EXAMPLES LX-LXIV
:
PRODUCTION OF BETA-CYCLOHOMOCITR~L E~OL ACETATE ~SING VARIOUS
CONDITIO~S
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 No. Ingredients Temperature Products of Reactlon LX 400 ml water, 26 g 0C for 3 beta-cyclohomocitral sodium acetate, hours enol acetate 4.2%, 38.4 g (0.2 moles) beta-ionone 47%, beta-ionone, 76 g beta-ionone epoxide (0.4 moles) 40% 39%
peracetic acid - LXI 80 ml water, 0 to -5C beta-cyclohomocitral acetic acid 100 ml, for 5 hours enol acetate 46.8%, sodium acetate 34 g, beta-ionone 10.3%, beta-ionone 38.4 g beta-ionone epoxide (0.2 moles), 44.9%
76 g (0.4 moles) 40% peracetic acid LXII formamide 180 ml, 0 to -5C beta-cyclohomocitral sodium acetate 26 g, for 5 hours enol acetate 50.7%, beta-ionone 38.4 g beta-ionone 36.2%, (0.2 moles), beta-ionone epoxide 76 g (0.4 moles) 15.9%
40% peracetic acid Example Reaction Reaction No. Ingredients Temperature Products of Reaction . .
LXIII formamide 4500 ml, 0.C for beta-cyclohomocitral sodium acetate 3.5 hours enol acetate 52.6%, 650 g, beta-ionone 15.6%, beta-ionone 960 g, beta-ionone epoxide 40% peracetic acid 25%
1900 g (10 moles) LXIV formamide 400 ml, 25C for beta-cyclohomocitral beta-ionone 38.4 g, 3 hours enol acetate 43%, potassium acetate beta-ionone 1.8%, (0.2 moles), beta-ionone epoxide 76 g (0.4 moles) 43 40~ parecetic acid EXAMPLE LXV
PREPARATION OF BETA-CYCLOHOMOCITRAL ENOL LAURATE
Reaction:

~ ~ H + (n CllH23~ C\ 1 ~ ~ ~ ~n-CllH23 ~ ~ (n-CllH23) 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 - 200C. Upon heating, the reaction mass first turns a light purplush color and then a greer. 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 with 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 Figure 35. The GC-MS profile for the reaction product is set forth in Figure 36.
EXAMPLE LXVI
TOBACCO FORMULATION
A tobacco mixture is produced by admixing the followiny ingredients:
IngredientParts 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.

.. 1[)53688 Tha following flavor formulation is prepared:
~gredient Parts by Weight ~thyl butyrate .OS
~hyl valerate .OS
Maltol 2.00 j Cocoa extract 26.00 Coffee extract 10.00 Ethyl alcohol 20.00 ~ater ~1.90 The above-stated tobacco flavor formulation is appiied at the rate of 0.1~ to all of the cigarettes produced using the above tobacco formulation. ~alf of the cigarettes are then treated with S00 or 1,000 ppm of beta-cycLohomocitral ~nol butyrate produced according to the process of Example lS XXV. The control ciqarettes not containing the trans beta-cyclohomocitral enol butyrate produced according to the process of Example ~YXV and the experimental cigarettes which contain the trans ~eta-cyclohomocitral enol butyrate produced according to the process of rxample XXV are evaluated by-~paired compar-l~on and the results are as rollows: . .

$he experimental cigarettes are found to have a sweet, floral, tea-tobacco-like, fruity, damascenone aroma, ~rior to, and, on smoking. In addition, the natural tobacco taste and aroma is enhanced on smoking, as a result of using the tran~ ~eta-cyclohomocitral enol butyrate.

All cigarettes are evaluated for smo~e flavor with a 20 mm cellulose acet te filter.
` '' ' ' .

_99_ .. 16~53688 ~XAHE'LE LXVI I
~08ACCO FOR~IULA~IO~

I a tobacco mixture is produced by admixing the following ¦ lngredients:
5 I ngredient Parts by Weiaht B~lght 40.1 Burley 2~.9 ~aryland 1.1 Turkish 11.6 10 Stem (flue-cured) 14.~
Glycerine . 2.8 Water 5.3 , C~garettes are prepared from this tobacco.

She following flavor formulation is prepared:
3~ artQ by Weicht . Ethyl butyrate ,05 Bthyl valerate ,oS
; Maltol 2.00 Cocoa extract 26.00 20 Coffee extract 10.00 Ethyl alcohol 20.00 Water ~1.90 ` . , Th~ above-stated.tobacco flavor formulation is applied . ~t the rate of 0.1% to all of the cigarettes produced using the above tobacco formul~tion. Half of the cigarettes are thon treated with 500 or 1,000 ppm of cis beta-cyclohomocitral ~nol octanoate produced according to the process of Example XXVIII. The control cigarettes not containing the cis beta-cyclohomoc.tr~l enol.octanoate produced accordinq to the I

1~53688 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 ciaarettes 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.

E~XAMP LE LXV I I I
TOBACCO FORMULATION
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:

1 053f~88 IngredientParts 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 tokacco 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-cyclohomo-citral 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 EXAMPLE LXIX
TO~ACCO FORMULATION
A tobacco mixture is produced by admixing the following ingredients:
IngredientParts 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:
IngredientParts by Weight Ethyl butyrate ,05 Ethyl valerate .05 Maltol 2.0Q
Cocoa extract 26.00 Coffee extract10.00 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-cyclohomo-citral enol acetate proauced according to the process of Example LVIII and the experimental cigarettes which contain the cis beta-cyclohomocltral enol acetate produced according to the - ' ~ ' process of Example LVIII are evaluated by paired comparison and the results are as follows:

5he experimental ci~arette~ are found to have more body and to be sweeter, more aromatic, more tobacco-like and less S harsh with sweet, floral and fruity notes. The tobacco of the experimental cigarettes, ?rior to smoking, has sweet, fioral and fruity notes. All cigarettes are evaluated .or *moke flavor with a 20 mm cellulose acetate filter.

The cis beta-cyclohomoci~ral enol acetate produced according to ~he process of Example LVIII enhances t~e tobacco li~e taste and aroma of the blended cigar~ttes, imparting to it sweet, natural tobacco notes.

EXAMPLE LXX
~A) SCALED UP PREPARATION OF BETA-CYCLOHOMOCITRAL ENOL ACETATE
= = _ USING FOR~IDE AS SOLVENT P.~D PERACETIC ACI~ OXIDIZING AGENT
AT A REACTIO~ TEMPERATURE OF 0C

i Into a 12 liter reaction flask equipped with stirrer, ! thermometer, addition funnel and dry ice/acetone cooling , bath, the following materials are added:

Ingreaients Quantity Formamide 4500 ml Sodium Acetate 650 gm (7.92 mole) Bet~-ionone 960 gm (5.0 mole) ' The reaction mass is stirred with cooling until a temp-erature of 0C is attained. At this time the addition of 1900 gm (10.0 moles) of 40% peracetic acid is commenced. The add~tion is carried out over a period of 3.5 hours whlle main-tain~ng the temperature at 0C. At the end of the addition -`- 1053688 period the reaction mass is stirred for an additional 3.5 hours at a temperature of 0C. 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 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" porcelain saddle column to a liquid temperature of 100C. The residual oil is distilled at reduced pressure through a 2" procelain saddle column to yield 984 grams of an oil in seven fractions. GLC analysis of the individual fractions indicates:
Ingredient Quantity Trans-beta-cyclohomo- (52.6% yield) citral enol acetate Beta-ionone (15.6% recovery) Beta-ionone epoxide (25% side product) (B) PREPARATION OF BETA-CYCLOHOMOCITRAL BY BASE-CATALYZED

HYDROLYSIS OF BETA-CYCLOHOMOCITRAL ENOL ACETATE
---Into a 5 liter reaction flask equipped with siirrer, 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) .

lOS3~88 Th~ 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 frcm the above-mentioned distillation is then commenced. The mixture S i~ added over a period of 4; minutes, while maintainin~ a temperature of 25-30~C. At the end of the addition period, the mixture is allowed to stir for an additional 2 hours at 25-30C. ~t 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. ~he aqueous layer is then extracted with two additional 1 liter portions o~ chloroform. The organic extracts are co~bined, 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~ porcelain sadlle column to , ,yie~d 758 grams of an oil. The oil is then distilled through ~n 18~ Goodloe column at reduced pressure to yield 686 grams of an oil in fourteen fractions. A residue of 44 grams, con-t~in~ng beta-ionone and beta-ionone epoxide remains, due to column hold-up. G~C analysis of these fractions indicates:

, lngredient Quan~ity , Beta-cyclohomocitral ~83 gram ~70~ vield 25 1 from beta-ionone) j Beta-ionone 88 gram (9% recovery) Beta-ionone epoxide 9 gram (0.8% carried over ~ide product~

rlO6-!

.

Claims (43)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. "Cis" or "trans" or mixtures of "cis" and "trans"
2(2,2,6-trimethyl-1-cyclohexen-1-yl)ethen-1-ol ester defined by the structure:

wherein R1 is C1-C11 alkyl and R4 is hydrogen or methyl.

2. A compound of Claim 1, wherein R1 is methyl and R4 is hydrogen.

3. The compound of Claim 2 wherein the ester moiety is in a "cis" relationship to the cyclohexyl moiety.

4. The compound of Claim 2 wherein the ester moiety is in a "trans" relationship to the cyclohexenyl moiety.

5. The compound of Claim 1 wherein R1 is n-propyl, and R4 is hydrogen.

6. The compound of Claim 1 wherein R1 is n-heptyl and R4 is hydrogen.

7. The compound of Claim 1 wherein R1 is 2-propyl and R4 is hydrogen.

8. The compound of Claim 1 wherein R1 and R4 are each methyl and the ester moiety is in a trans relationship to the cyclohexenyl moiety.

9. The compound of Claim 1 wherein R1 is n-C11H23 and R4 is hydrogen.

10. A process for producing an enol ester having the following structure in a "trans" isomeric form:

wherein R1 is C1-C11 alkyl and R4 is hydrogen or methyl comprising the step of either (i) reacting beta-ionone or a higher alkyl homologue thereof with a peralkanoic acid or (ii) reacting beta-homocyclocitral with an alkanoic acid anhydride.

11. The process of Claim 10 comprising the additional step of reacting the resulting enol ester with an acylating agent in the presence of paratoluene sulfonic acid or an alkali metal acetate.

12. A process for producing an enol ester having the following structure in a "trans" isomeric form:

wherein R1 is C1-C11 alkyl, and R4 is hydrogen or methyl comprising the step of reacting betaionone or a higher alkyl homologue thereof having the structure:

with a peralkanoic acid or m-chloroperbenzoic acid having the formula:

wherein R2 is hydrogen, methyl, ethyl or m-chlorophenyl at a temperature in the range of from -10° C up to about 75°C in the presence of i. A buffer selected from the group consisting of alkali metal salts of lower alkanoic acids and alkali metal carbonates; and ii. A solvent selected from the group consisting of methylene chloride, acetic acid, formic acid, propionic acid, benzene, cyclohexane, formamide and chloroform, and substantially in the presence of solvents reactive with (i) said peralkanoic acid or (ii) said m-chloroperbenzoic acid, thereby forming the said enol ester.

13. The process of Claim 12, wherein R1 is methyl and R4 is hydrogen.

14. The process of Claim 13 comprising the additional step of reacting the resulting enol ester with an acylating agent which is one of an alkanoic acid anhydride having the formula:

or an acyl halide having the general formula:

in the presence of paratoluene sulfonic acid or an alkali metal acetate thereby forming a compound having the formula:

wherein X is chloro or bromo and wherein R3 is C2 - C11 alkyl, said reaction being carried out at a temperature in the range of from 100° up to 200°C over a period of from 3 up to 10 hours, the mole ratio of alkanoic acid anhydride: enol ester being greater than 1; the mole ratio of enol ester:paratoluene sulfonic acid catalyst or alkali metal acetate catalyst being from 1:0.01 up to 1:0.5.

15. A process for preparing an enol ester defined in Claim 12 wherein R4 is hydrogen comprising the step of reacting beta-homocyclocitral having the formula:

with an alkanoic acid anhydride having the formula:

in the presence of a catalyst selected from the group consisting of paratoluene sulfonic acid and an alkali metal acetate wherein R1 is C1 - C11 alkyl, said reaction being carried out at a temperature in the range of from 25°C up to 175°C in the absence of solvent, said alkanoic acid anhydride being in molar excess with respect to said beta-homocyclocitral; when the reaction is carried out in the presence of an alkali metal acetate, the mole ratio of alkali metal acetate: beta homocyclocitral being about 0.1:1, when the reaction is carried out using a paratoluene sulfonic acid catalyst, the mole ratio of betacyclohomocitral:
paratoluene acid being from 1:0.01 up to 1:0.1.

16. The process of Claim 14 wherein the acylating agent is an alkanoic acid anhydride having the formula:

wherein R3 is C2 - C11 alkyl.

17. The process of Claim 14 wherein the acylating agent is an acyl halide having the formula:

wherein R3 is C2 - C11 alkyl, and X is chloro or bromo.

18. A fragrance modifying composition comprising one or more 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde enol esters, having the structure:

wherein R1 is C114 C5 lower alkyl; and an auxiliary perfume ingredient compatible with each of said 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde enol ester or esters.

19. A perfume composition comprising one or more 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde enol esters, as defined in Claim 18, having the structure:

wherein R1 is C1 - C5 lower alkyl and at least one adjuvant selected from the group consisting of natural perfume oil, synthetic perfume oil, alcohols, aldehydes, ketones, esters and lactones.

20. A process for producing a perfumed composition comprising the step of admixing a composition of matter with a fragrance imparting amount of one or more 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde enol esters, as defined in Claim 18, having the structure:

wherein R1 is C1 - C5 lower alkyl.

21. A cologne composition comprising ethanol, water and one or more 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde enol esters, as defined in Claim 18, having the structure:

wherein R1 is C1 - C5 lower alkyl.

22. A process for altering, modifying or enhancing the organoleptic properties of a consumable material which is, in the alternative, one of perfume compositions, perfumed articles, food flavoring compositions, foodstuffs, chewing gums, chewing gum flavoring compositions, medicinal products, medicinal product flavoring compositions, toothpastes and toothpaste flavoring compositions, tobacco flavoring compositions and tobacco which comprises adding thereto a small but effective amount of a composition comprising 2,6,6-trimethyl-1-cyclohexen-1-ylacetal-dehyde enol ester having the structure:

wherein R1 is C1 - C11 alkyl and R4 is methyl or hydrogen.

23. A tobacco flavoring composition produced according to Claim 22 comprising at least one enol ester defined by the structure:

wherein R1 is C1 - C11 alkyl and R4 is hydrogen or methyl, and as a flavor adjuvant at least one compound which is, in the alternative, one of ethyl butyrate, ethyl valerate or maltol.

24. A process according to Claim 22 wherein the consumable material is a foodstuff.

25. A process according to Claim 22 wherein the consumable material is a perfumed article which is, in the alternative, one of a soap, a detergent or a cosmetic powder.

26. A process according to Claim 22 wherein the consumable material is a tobacco.

27. A process according to Claim 22 wherein the consumable material is a food flavor.

28. A process for augmenting or enhancing the taste or aroma of a foodstuff which comprises adding thereto from 0.5 parts per million up to about 100 parts per million of one or more cis or trans ethol esters having the structure:

wherein R1 is C1 - C11 alkyl and R4 is methyl or hydrogen.

29. The process of Claim 28 wherein R1 is methyl and R4 is hydrogen.

30. The process of Claim 28 wherein the ester moiety is in a cis relationship to the cyclohexenyl moiety.

31. The process of Claim 28 wherein the ester moiety is in trans relationship to the cyclohexenyl moiety.

32. The process of Claim 28 wherein the enol ester is cis beta-cyclohomocitral enol butyrate.

33. The process of Claim 28 wherein the enol ester is trans beta-cyclohomocitral enol butyrate.

34. The process of Claim 28 wherein the enol ester is trans beta-cyclohomocitral enol proprionate.

35. The process of Claim 28 wherein the enol ester is cis beta-cyclohomocitral enol octanoate.

36. A flavor augmenting or modifying composition comprising from about 0.1% up to about 15% by weight based on the total weight of said composition of one or more cis or trans enol esters having the structure:

wherein R1 is C1 - C11 alkyl and R4 is hydrogen or methyl and as a flavor adjuvant, a compound selected from the group consisting of p-hydroxybenzyl acetone, maltol, benzyl acetate, methyl cinnamate, geraniol, ethyl methyl phenyl glycidate, vanillin, methyl anthranilate, alpha-ionone, gamma undecalactone, ethyl pelargonate, isoamyl acetate, acetaldehyde, dimethyl sulfide, isobutyl acetate, acetic acid, ethyl butyrate, diacetyl, anethole, cis-3-hexenol-1, naphthyl ethyl ether, ethyl acetate, isoamyl butyrate, 2-methyl-2-pentenoic acid, 2(4-hydroxy-4-methylphenyl) norbornadiene, 4-allyl-1,2,6-trimethyoxy benzene, cassia oil, eugenol, caryophyllene, guiacol, cinnamaldehyde, 5-methyl furfural, cuminaldehyde, cinnamyl formate, methyl cinnamate, furfural, 2,3-dimethyl pyrazine, 2-ethyl-3-methyl pyrazine, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal, 2-phenyl-2-pentenal, 3-phenyl-4-pentenal diethyl acetal, 1-crotonyl-2,2,6-trimethylcyclohex-1-ene, 1-crotonyl-2,2,6-trimethylcyclohex-1,5-diene, 2,2,6-trimethylcyclohex- 1-ene carboxaldehyde and 4-propenyl-1,2,6-trimethyoxy benzene.

37. The composition of Claim 36 wherein R1 is methyl and R4 is hydrogen.

38. The composition of Claim 36 wherein the ester moiety is in a cis relationship to the cyclohexenyl moiety.

39. The composition of Claim 36 wherein the ester moiety is in trans relationship to the cyclohexenyl moiety.

40. The composition of Claim 36 wherein the enol ester is cis beta-cyclohomocitral enol butyrate.

41. The composition of Claim 36 wherein the enol ester is trans beta-cyclobomocitral enol butyrate.

42. The composition of Claim 36 wherein the enol ester is trans beta-cyclohomocitral enol proprionate.

43. The composition of Claim 36 wherein the enol ester is cis beta-cyclohomocitral enol octanoate.