Described is the hexadienoyl cyclohexene derivative defined according to the structure: ##STR1## which may either be in the form of a mixture of Z, Z; E, E; Z, E or E, Z isomers or the individual isomers themselves having the structures: ##STR2## a process for preparing same, intermediates useful in said process defined according to the structure: ##STR3## wherein R represents ethyl or methyl and organoleptic uses of the hexadienoyl cyclohexene derivatives in augmenting or enhancing the aroma or taste of consumable materials including perfume compositions, colognes and perfumed articles (e.g. solid or liquid anionic, cationic, nonionic or zwitterionic detergents, hair preparations, fabric softeners, fabric softener articles, cosmetic powders and perfumed polymers); foodstuffs, chewing gums, medicinal products, toothpastes and chewing tobaccos; smoking tobaccos and smoking tobacco articles.

BACKGROUND OF THE INVENTION 
The instant invention relates to hexadienoyl cyclohexene derivatives 
generically defined according to the structure: 
##STR4## 
processes for preparing said hexadienoyl cyclohexene derivatives, and 
organoleptic uses of said hexadienoyl cyclohexene derivatives in 
augmenting or enhancing the aroma or taste of consumable materials. 
In the perfumery art there is considerable need for substituents having 
floral, rosey, honey, woody and raspberry aroma nuances. 
Floral, hay-like, sweet and fruity notes are desirable in smoking tobacco 
flavoring compositions and substitute smoking tobacco flavoring 
compositions. 
Minty, citrus, lime, raspberry, floral, and rosey aroma and taste nuances 
with fresh, cooling nuances are highly desirable in flavoring compositions 
for foodstuffs, chewing gums, medicinal products, toothpastes and chewing 
tobaccos. 
A limited number of materials which give rise to the foregoing properties 
are available from natural sources. The natural materials are subject to 
wide variations in quality, are expensive and are often in critically 
short supply. 
In addition, there is a continuing search for food flavor compositions 
which can vary, fortify, modify, enhance, augment or otherwise improve the 
flavor and/or aroma of foodstuffs, medicinal products, toothpastes, 
chewing gums and chewing tobaccos. To be satisfactory, such compositions 
would be stable, non-toxic and blendable with other ingredients to provide 
their own unique flavor and aroma nuances without detracting from the 
co-ingredients. Preferably such compositions should be naturally occurring 
or be present in the natural foodstuff so that their ingestible safety can 
be readily recognized. These materials should be capable of being 
synthesized in a simple and economical manner. The need for safe flavors 
particularly in the lime, citrus, tropical fruit, and mint areas is well 
known, particularly in the oral hygiene areas. More specifically, there is 
a need for the development of non-toxic materials which can replace 
natural materials not readily available having minty, citrus, lime, 
raspberry, floral and rosey aroma and taste nuances with fresh, cooling 
nuances. 
The instant invention provides the foregoing which the prior art has 
heretofore failed to provide. Furthermore, nothing in the prior art shows 
the unexpected, unobvious and advantageous value of the genus of compounds 
defined according to the structure: 
##STR5## 
and particularly the isomers thereof having the structures: 
##STR6## 
U.S. Pat. No. 4,334,098 issued on June 8, 1982 discloses the use of the 
compound trans,transdelta damascone having the structure: 
##STR7## 
for its organoleptic properties. The compound having the structure: 
##STR8## 
and its isomers individually have properties which are unexpected, 
unobvious and advantageous over the properties of the 
trans,trans-delta-damascone defined according to the structure: 
##STR9## 
Hexadienoyl cyclohexenes having trimethyl substitution on the cyclohexene 
ring are known for use in augmenting or enhancing the organoleptic 
properties of consumable materials in the prior art. Thus, Arctander 
"Perfume and Flavor Chemicals (Aroma Chemicals)", Volume I published in 
1969 discloses at monograph 86 the compound having the structure: 
##STR10## 
(allyl ionone) thusly: 
86: ALLYL IONONE 
alpha-Allyl ionone (Allyl-alpha-ionone). 
"Hexalon" (I.F. & F. Inc.). 
"Cetone V." (Givaudan). 
"Polyone" (Firmenich). 
Allyl cyclocitrylidene acetone. 
1-(2,6,6-Trimethyl-2-cyclohexene-1-yl)-1,6-heptadien-3-one. 
##STR11## 
Colorless or very pale yellowish oily liquid. B.P. about 265.degree. C. 
Sp. Gr. 0.930. 
Oily-sweet, slightly flowery, but also fruity, woody and bark-like green 
odor of considerable tenacity. According to the identity of the 
manufacturer, the odor characteristics of this chemical may vary from 
mild-oily fruity-woody to peculiar fishy (amine-like), woody, cod-liver 
oil-like, etc. The odor changes also with age, particularly under poor 
storage condition. This is one of the main drawbacks of the title 
chemical. 
Ketone content of commercial grades: 88 to 93%. 
Insoluble in water, soluble in alcohol and perfume and flavor materials, 
poorly soluble in Propylene glycol. 
Useful in perfume compositions as a modifier for Ionones and Methylionones, 
in modern-aldehydic creations, in perfumes with fruity-aldehydic topnotes, 
in combinations with Vetiver or woody-floral perfume materials, etc. 
"Cetone V." is probably the most fruity of all commercial Allyl ionones. 
Used in flavors-traces-for imitation Raspberry and Pineapple. 
Produced from Citral by condensation with Allyl acetone, followed by 
cyclization. 
G.R.A.S. F.E.M.A. No. 2033. 
3-171; 31-96; 86-5; 106-94; 155-92; 89-389; 156-203; 
and further discloses the organoleptic properties of beta-euionone at 
monograph 1377, beta-euionone having the structure: 
##STR12## 
thusly: 
1377: beta-EUIONONE 
2-Methyl-4-(1,1,3-trimethyl-2'-cyclohexen-2'-yl)-butadiene methylketone. 
4-Methyl-6-(1,1,3-trimethyl-2'-cyclohexen-2'-yl)-3,5-hexadien-2-one. 
##STR13## 
Almost colorless or pale straw-colored oily liquid. Semi-sweet, woody and 
slightly fruity, warm odor of good tenacity and some resemblance to 
beta-Lonone, but more sweet, less woody than that material. 
This ketone has been suggested for use in perfume compositions as being 
superior to beta-Ionone with respect to overall odor performance and 
versatility in use. 
However, the manufacture of this material is somewhat more costly than that 
of the Ionones, at least as long as no one can set up a truly large scale 
production of this chemical. There is also some doubt that it can replace, 
let alone outperform, any of the common Ionones as far as odor quality is 
concerned. 
Prod.: from Citral and iso-Propylidene acetone by condensation followed by 
cyclization. 
31-95; 86-51; 86-78; 
See also: Ianthone. 
Neither allyl ionone nor beta-euionone have properties even remotely 
similar to the organoleptic properties of the compound having the 
structure: 
##STR14## 
or its individual isomers having the structures: 
##STR15## 
Nothing in the prior art discloses the efficient, economically method for 
synthesizing the compounds having the structure: 
##STR16## 
through the intermediate genus having the structure: 
##STR17## 
wherein R represents methyl or ethyl according to the reaction sequence: 
##STR18## 
However, Chem. Abstracts, Volume 3, page 167 at line 37 (abstracting Wahl 
and Mayer, Bull. Soc. Chim. [4], 3, 957-63 (September, October 1906) 
discloses the synthesis of the compound having the structure: 
##STR19## 
wherein R is methyl or ethyl according to the reaction: 
##STR20## 
The reaction set forth above is different in kind rather than degree from 
the reaction of the instant invention, to wit: 
##STR21## 
wherein R represents methyl or ethyl.

DETAILED DESCRIPTION OF THE DRAWINGS 
FIG. 4 is the GLC profile for fraction 2 of the first distillation of the 
reaction product of Example II containing the compounds defined according 
to the structure: 
##STR35## 
which include isomers having the structures: 
##STR36## 
The peak indicated by reference numberal "40" is the peak for the compound 
which is the "Z, Z" isomer defined according to the structure: 
##STR37## 
(conditions: SE-30 column programmed at 100.degree.-220.degree. C. at 
8.degree. C. per minute). 
FIG. 9 is the NMR spectrum for the peak indicated by reference numeral "40" 
on FIG. 4 which is for the isomer defined according to the structure: 
##STR38## 
(the "Z, Z" isomer. Conditions: CFCl.sub.3 solvent; 100 MHz field 
strength.) 
Referring to the drawings in FIGS. 11 and 12 in particular, the invention 
embodied therein comprises a device for forming scented polymer pellets 
(e.g. polyethylene, polypropylene or mixtures of polyepsilon caprolactone 
and polyethylene or polypropylene or co-polymers of polyvinyl acetate and 
polyethylene) which comprises a vat or container into which a mixture of 
polymer such as polyethylene and the compound defined according to the 
structure: 
##STR39## 
or a mixture of perfume materials including as a key ingredient one of the 
isomers defined according to the structure: 
##STR40## 
is placed. 
The container is closed by an air-tight lid 228 clamped to the container by 
clamps 265. A stirrer 273 traverses the lid or cover 228 in air-tight 
manner and is rotated in suitable manner. A surrounding cylinder 212 
having heating coils which are supplied with electrical current through 
cable 214 from a rheostat or control 216 is operated to maintain the 
temperature inside the container such that the polymer such as 
polyethylene in the container will be maintained in a molten or liquid 
state. It has been found advantageous to employ a colorless, odorless 
polymer such as low density polyethylene with a viscosity ranging between 
180 and 220 centistokes and having a melting point in the neighborhood of 
220.degree. F. The heater 212A is operated to maintain the upper portion 
of the container within a temperature range of from 
250.degree.-350.degree. F. An additional bottom heater 218 is regulated 
through a control 220 connected thereto through a connecting wire 222 to 
maintain the lower portion of the container within a temperature range of 
from 250.degree. to 350.degree. F. 
In accordance with this aspect of the invention, a polymer such a 
polyethylene or polypropylene is added to the container and is then heated 
from 10 to 12 hours whereafter a scent or aroma imparting material 
containing the compound having the structure: 
##STR41## 
is quickly added to the melt. The material must be compatible with the 
polymer and forms a homogeneous liquid melt therewith. The heat resisting 
mixture generally about 10-40% by weight of material having the structure: 
##STR42## 
or mixture containing such compound or isomer is added to the polymer. 
After the compound having the structure: 
##STR43## 
or mixture containing same is added to container, the mixture is stirred 
for a few minutes, for example 5 to 15 minutes, and maintained within the 
temperature range as indicated previously by the heating coils 212A and 
218 respectively. The controls 216 and 220 are connected through cables 
224 and 226 to a suitable supply of electric current for supplying the 
power for heating purposes. 
Thereafter the valve "V" is opened permitting the mass to flow outwardly 
through a conduit 232 having a multiplicity of orifices 234 adjacent the 
lower side thereof. The outer end of the conduit 232 is closed so that the 
liquid polymer and substance containing compound having the structure: 
##STR44## 
will continuously drop through the orifice 234 downwardly from the conduit 
232. During this time the temperature of the polymer and the compound 
having the structure: 
##STR45## 
or mixture containing same in the container is accurately controlled so 
that a temperature in the range of from 210.degree. F. up to 275.degree. 
F. will exit in the conduit 232. The regulation of the temperature through 
the control 216 and the control 220 is essential in order to insure 
temperature balance to provide for the continuous dropping or dripping of 
molten polymer and material having the structure: 
##STR46## 
or mixture containing same through the orifices 234 at a range which will 
insure the formation of droplets 236 which will fall downwardly onto a 
moving conveyor belt 238 trained to run between conveyor wheels 240 and 
242 beneath the conduit 232. When the droplets 236 fall onto the conveyor 
belt 238 they form pellets 244 which harden almost instantaneously and 
fall off the end of the conveyor 238 into a container 245 which is 
advantageously filled with water or some other suitable liquid to insure 
the rapid cooling of each of the pellets. The pellets 244 are then 
collected from the container 246 and packaged for shipment. 
A feature of the invention is the provision for moistening the conveyor 
belt 238 to insure the rapid formation of the solid polymer scented 
pellets 244 without sticking to the belt. The belt 238 is advantageously 
of a material which will not normally stick to a melted polymer but the 
moistening means 248 insures a sufficiently cold temperature of the belt 
surface for the adequate formation of the pellets 244. The moistening 
means comprises a container 250 which is continuously fed with water to 
maintain a level for moistening a sponge element 256 which bears against 
the exterior surface of the belt 238. 
THE INVENTION 
The present invention provides the genus of compounds defined according to 
the structure: 
##STR47## 
which include isomers defined according to the structures: 
##STR48## 
wherein the dashed line represents a "trans" configuration of the 
hexadienoyl moiety with respect to the monomethyl moiety bonded to the 
cyclohexene group, and a straight forward economical process directed 
towards synthesizing the compound defined according to the structure: 
##STR49## 
using the reaction sequence: 
##STR50## 
wherein R represents methyl or ethyl. Thus, the intermediate compounds 
defined according to the generic structure: 
##STR51## 
wherein R is methyl or ethyl and which include the isomers defined 
according to the structures: 
##STR52## 
are novel compounds and are part of our invention. 
Each of the members of the genus of compounds defined according to the 
structure: 
##STR53## 
and the mixtures of such members of such genus are capable of augmenting 
or enhancing minty, citrus, lime, raspberry, floral and rosey aroma and 
taste nuances as well as imparting fresh, cooling nuances to lime, citrus, 
tropical fruit and mint flavors particularly in the oral hygiene area, 
e.g. mouthwashes and toothpastes and the like. 
Each of the isomers of the genus having the structure: 
##STR54## 
in addition, is capable of augmenting or enhancing floral, rosey, honey, 
woody and raspberry aroma nuances in perfume compositions, colognes and 
perfumed articles e.g. solid or liquid anionic, cationic, nonionic or 
zwitterionic detergents, fabric softener compositions, fabric softener 
articles, hair preparations and perfumed polymers. 
Each of the members of the genus defined according to the structure: 
##STR55## 
including the isomers thereof having the structures: 
##STR56## 
are capable of augmenting or enhancing the aroma and taste of smoking 
tobaccos and smoking tobacco articles wherein the floral, hay-like, sweet 
and fruity aroma and taste nuances both prior to and on smoking in the 
main stream and the side stream are augmented or enhanced. In addition, in 
the smoking tobacco articles and in the smoking tobacco per se, fresh, 
cooling nuances are imparted by the compounds defined according to the 
structure: 
##STR57## 
A genus of compounds defined according to the structure: 
##STR58## 
is prepared by a novel process of our invention embodied by the reaction 
sequence: 
##STR59## 
wherein R represents methyl or ethyl. 
Thus, a mixture of compounds defined according to the genus: 
##STR60## 
or individual isomers thereof having the structure: 
##STR61## 
is reacted with a dialkyl carbonate defined according to the structure: 
##STR62## 
wherein R is methyl or ethyl using an alkali metal hydride in the presence 
of an inert solvent according to the reaction: 
##STR63## 
Examples of alkali metal hydride used are sodium hydride and potassium 
hydride. Examples of inert solvent (solvent inert to the reaction 
ingredients under the conditions of the reaction) are toluene, xylene, 
benzene and alkyl and polyalkyl substituted cyclohexane, e.g. 
1,2,3,4,5,6-hexamethyl cyclohexane. 
The reaction temperature is from about 30.degree. C. up to about 80.degree. 
C. The reaction pressure is from about 1 atmosphere up to about 10 
atmospheres depending upon the desired reaction temperature and depending 
upon the particular solvent utilized. It is preferable to carry out the 
reaction under reflux conditions thereby minimizing the time of reaction 
and maximizing the yield. 
The mole ratio of compound having the structure: 
##STR64## 
to dialkyl carbonate having the structure: 
##STR65## 
may vary from about 1:2 up to about 2:1 with a preferred mole ratio of 
about 1:1.5. The mole ratio of alkali metal hydride to compound having the 
structure: 
##STR66## 
may vary from about 3:1 down to about 1:1 with a preferred mole ratio of 
about 2:1. 
The concentration of alkali metal carbonate having the structure: 
##STR67## 
in the solvent may vary from about 1 mole per liter up to about 2 moles 
per liter with a concentration of about 1:5 moles per liter being 
preferable. The concentration of alkali metal hydride in the reaction mass 
may vary from about 1 mole per liter up to about 3 moles per liter with a 
concentration of about 1.8 moles per liter being preferred. The 
concentration of compound or isomer having the structure: 
##STR68## 
in the reaction mass may vary from about 0.5 moles per liter up to about 
1.5 moles per liter with a concentration of about 0.9 moles per liter 
being preferred. 
Since the isomer having the structure: 
##STR69## 
is the preferred isomer of our invention (although the other isomers are 
quite useful for their organoleptic properties), it is preferred to use as 
a starting material the isomer having the structure: 
##STR70## 
This isomer may be prepared by means of treatment of 
1-alpha-acetyl-2-alpha,6,6-trimethyl-3-cyclohexene (prepared according to 
Ayyar, Cookson and Kagi, J. Chem. Soc., Perkin Trans. 1, 1975 (17) 1727-36 
[title: "Synthesis of 
delta-Damascone[trans-1-(2,6,6-Trimethylcyclohex-3-enyl)but-2-en-1-one] 
and beta-Damascenone[trans-1-(2,6,6-Trimethylcyclohexa-1,3-dienyl)but-2-en 
-1-one]") with refluxing alcoholic base or alkali metal alcoholate 
according to the reaction: 
##STR71## 
wherein R is lower alkyl, e.g. methyl or ethyl and M is alkali metal, e.g. 
sodium or potassium. From a practical standpoint, the resulting product 
contains a minor proportion of cis isomer (approximately 10-20%) and a 
major proportion of trans isomer (approximately 80-90%). Accordingly, the 
resulting material having the structure: 
##STR72## 
actually contains the additional isomers having the structures: 
##STR73## 
but from a practical standpoint, the amount of material having the 
structure: 
##STR74## 
is about 80%. 
The resulting product defined according to the structure: 
##STR75## 
and containing the isomers having the structures: 
##STR76## 
is then reacted with 2-methyl-3-butyn-2-ol having the structure: 
##STR77## 
in the presence of a metal alkoxide, for example, sodium methoxide, 
potassium methoxide, sodium ethoxide, potassium ethoxide, potassium 
isobutoxide, potassium-t-butoxide and aluminum isopropoxide. The alkali 
metal alkoxide in this reaction is a catalytic quantity. 
The reaction: 
##STR78## 
wherein R is methyl or ethyl, is carried out at a temperature of between 
about 70.degree. C. and 200.degree. C. While the reaction takes place, 
methane and carbon dioxide is devolved. The mole ratio of ester having the 
structure: 
##STR79## 
to 2-methyl-3-butyn-2-ol is from about 0.25:1 up to about 1:1 with a 
preferred mole ratio range of from about 0.3:1 up to about 0.5:1. The 
weight percent of metal alkoxide in the reaction mass is from about 5% up 
to about 20% with a preferred weight percent of metal alkoxide of about 
8-10%. 
At the end of the reaction, the reaction mass is quenched into a weak acid, 
e.g. acetic acid. The resulting material is extracted, for example, with 
toluene and the extracts are then stripped of solvent and fractionally 
distilled to yield the resulting product defined according to the 
structure: 
##STR80## 
either as a mixture or as one of the isomers defined according to one of 
the structures: 
##STR81## 
When the hexadienoyl cyclohexene derivatives of our invention are used as 
food flavor adjuvants, the nature of the co-ingredients included with the 
hexadienoyl cyclohexene derivatives used in formulating the product 
composition will also serve to alter, modify, augment or enhance the 
organoleptic characteristics of the ultimate foodstuff, chewing gum, 
toothpaste, medicinal product or chewing tobacco treated therewith. 
As used herein in regard to flavors, the terms "alter", "modify" and 
"augment" in their various forms means supplying or imparting flavor 
character or note to otherwise bland, relatively tastless substances or 
augmenting the existing flavor characteristic where a natural flavor is 
deficient in some regard or supplementing the existing flavor impression 
to modify its quality, character or taste. 
The term "enhance" is used herein to mean the intensification of a flavor 
or aroma characteristic or note without the modification of the quality 
thereof. Thus, "enhancement" of a flavor or aroma means that the 
enhancement agent does not add any additional flavor note. 
As used herein, the term "foodstuff" includes both solid and liquid 
ingestible materials which usually do, but need not, have nutritional 
value. Thus, foodstuffs include soups, convenience foods, beverages, dairy 
products, candies, chewing gums, vegetables, cereals, soft drinks, snacks 
and the like. 
As used herein, the term "medicinal product" includes both solids and 
liquids which are ingestible non-toxic materials which have medicinal 
value such as cough syrups, cough drops, aspirin and chewable medicinal 
tablets. 
The term "chewing gum" is intended to mean a composition which comprises a 
substantially water-insoluble, chewable plastic gum base such as chicle or 
substitute 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 the hexadienoyl 
cyclohexene derivatives of our invention and in addition, sweetening 
agents which may be sugars, including sucrose or dextrose and/or 
artificial sweeteners such as cyclamates or saccharin. Other optional 
ingredients may also be present. 
Substances suitable for use herein as co-ingredients or flavoring adjuvants 
are well known in the art for such use, being extensively described in the 
relevant literature. It is a requirement that any such material be 
"ingestibly" acceptable and thus non-toxic and otherwise non-deleterious 
particularly from an organoleptic standpoint whereby the ultimate flavor 
and/or aroma of the consumable material used 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 (2,6-di-tertiary-butyl-4-methyl phenol), propyl 
gallate and the like and sequestrants, e.g., citric acid. 
Thickener compounds include carriers, binders, protective colloids, 
suspending agents, emulsifiers and the like, e.g., agar agar, carrageenan; 
cellulose and cellulose derivatives such as carboxymethyl cellulose and 
methyl cellulose; natural and synthetic gums such as gum arabic, gum 
tragacanth; gelatin, proteinaceous materials; lipids; carbohydrates; 
starches, pectins and emulsifiers, e.g., mono- and diglycerides of fatty 
acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose 
corn syrup and the like. 
Surface active agents include emulsifying agents, e.g., fatty acids such as 
capric acid, caprylic acid, palmitic acid, myristic acid and the like, 
mono- and diglycerides of fatty acids, lecithin, defoaming and 
flavor-dispersing agents such as sorbitan monostearate, potassium 
stearate, hydrogenated tallow alcohol and the like. 
Conditioners include compounds such as bleaching and maturing agents, e.g., 
benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch 
modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, 
propylene oxide, succinic anhydride and the like, buffers and neutralizing 
agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, 
citric acid, lactic acid, vinegar and the like; colorants, e.g., carminic 
acid, cochineal, tumeric and curcuma and the like; firming agents such as 
aluminum sodium sulfate, calcium chloride and calcium gluconate; 
texturizers, anti-caking agents, e.g., aluminum calcium sulfate and 
tribasic calcium phosphate; enzymes; yeast foods, e.g., calcium lactate 
and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric 
phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc 
sources such as zinc chloride, zinc sulfate and the like. 
Other flavorants and flavor intensifiers include organic acids, e.g., 
acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid, 
caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric 
acid, alpha-methyl-butyric acid, propionic acid, valeric acid, 
2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones and 
aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methyl 
carbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal, beta, 
beta-dimethylacrolein, methyl-n-amyl ketone, n-hexenal, 2-hexenal, 
isopentanal, 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, 1-borneol, trans-2-buten-1-ol, ethanol, 
geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol, 
3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol, p-hydroxyphenyl-2 
-ethanol, isoamyl alcohol, isofenchyl alcohol, phenyl-2-ethanol, 
alpha-terpineol, cis-terpineol hydrate, eugenol, linalool, 2-heptanol, 
acetoin; esters, such as butyl acetate, ethyl acetate, ethyl acetoacetate, 
ethyl benzoate, ethyl butyrate, ethyl caprate, ethyl caproate, ethyl 
caprylate, ethyl cinnamate, ethyl crotonate, ethyl formate, ethyl 
isobutyrate, ethyl isovalerate, ethyl laurate, ethyl myristate, ethyl 
alpha-methylbutyrate, ethyl propionate, ethyl salicylate, trans-2-hexenyl 
acetate, hexyl acetate, 2-hexenyl butyrate, hexyl butyrate, isoamyl 
acetate, isopropyl butyrate, methyl acetate, methyl butyrate, methyl 
caproate, methyl isobutyrate, alpha-methylphenylglycidate, ethyl 
succinate, isobutyl cinnamate, cinnamyl formate, methyl cinnamate and 
terpenyl acetate; hydrocarbons such as dimethyl naphthalene, dodecane, 
methyl diphenyl, methyl naphthalene, myrcene, naphthalene, octadecane, 
tetradecane, tetramethyl naphthalene, tridecane, trimethyl naphthalene, 
undecane, caryophyllene, 1-phellandrene, p-cymene, 1-alphapinene; 
pyrazines such as 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 
2,6-dimethylpyrazine, 3-ethyl-2,5-dimethylpyrazine, 
2-ethyl-3,5,6-trimethylpyrazine, 3-isoamyl-2,5-dimethylpyrazine, 
5-isoamyl-2,3-dimethylpyrazine, 2-isoamyl-3,5,6-trimethylpyrazine, 
isopropyl dimethylpyrazine, methyl ethylpyrazine, tetramethylpyrazine, 
trimethylpyrazine; essential oils, such as jasmine absolute, cassia oil, 
cinnamon bark oil, rose absolute, orris absolute, lemon essential oil, 
Bulgarian rose, yara yara and vanilla; lactones such as 
.delta.-nonalactone; sulfides, e.g., methyl sulfide and other materials 
such as maltol, acetoin and acetals (e.g., 1,1-diethoxyethane, 
1,1-dimethoxyethane and dimethoxymethane). 
The specific flavoring adjuvant selected for use may be either solid or 
liquid depending upon the desired physical form of the ultimate product, 
i.e. foodstuff, whether simulated or natural, and should, in any event, 
(i) be organoleptically compatible with the hexadienoyl cyclohexene 
derivatives of our invention by not covering or spoiling the organoleptic 
properties (aroma and/or taste) thereof; (ii) be non-reactive with the 
hexadienoyl cyclohexene derivatives of our invention and (iii) be capable 
of providing an environment in which the hexadienoyl cyclohexene 
derivatives of our invention can be dispersed or admixed to provide a 
homogeneous medium. In addition, selection of one or more flavoring 
adjuvants, as well as the quantities thereof will depend upon the precise 
organoleptic character desired in the finished product. Thus, in the case 
of flavoring compositions, ingredient selection will vary in accordance 
with the foodstuff, chewing gum, medicinal product or toothpaste to which 
the flavor and/or aroma are to be imparted, modified, altered or enhanced. 
In contradistinction, in the preparation of solid products, e.g., 
simulated foodstuffs, ingredients capable of providing normally solid 
compositions should be selected such as various cellulose derivatives. 
As will be appreciated by those skilled in the art, the amount of the 
hexadienoyl cyclohexene derivatives 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 the hexadienoyl cyclohexene 
derivatives of our invention will, of course, substantially vitiate any 
possibility of obtaining the desired results while excess quantities prove 
needlessly costly and in extreme cases, may disrupt the flavor-aroma 
balance, thus proving self-defeating. Accordingly, the terminology 
"effective amount" and "sufficient amount" is to be accorded a 
significance in the context of the present invention consistent with the 
obtention of desired flavoring effects. 
Thus, and with respect to ultimate food compositions, chewing gum 
compositions, medicinal product compositions and toothpaste compositions, 
it is found that quantities of the hexadienoyl cyclohexene derivatives of 
our invention ranging from a small but effective amount, e.g. 0.2 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 provide commensurate 
enhancement of organoleptic properties. In those instances wherein the 
hexadienoyl cyclohexene derivatives of our invention are 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 concentration of the 
hexadienoyl cyclohexene derivatives of our invention in the foodstuff 
product. 
Food flavoring compositions prepared in accordance with the present 
invention preferably contain the hexadienoyl cyclohexene derivatives of 
our invention 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 
proportions stated in a suitable blender to obtain the desired 
consistency, homogeneity of dispersion, etc. Alternatively, flavoring 
compositions in the form of particulate solids can be conveniently 
prepared by mixing the hexadienoyl cyclohexene derivatives of our 
invention with, for example, gum arabic, gum tragacanth, carrageenan and 
the like, and thereafter spray-drying the resultant mixture whereby to 
obtain the particular solid product. Pre-prepared flavor mixes in powder 
form, e.g. a fruit flavored powder mix, are obtained by mixing the dried 
solid components, e.g. starch, sugar and the like, and the hexadienoyl 
cyclohexene derivatives of our invention in a dry blender until the 
requisite degree of uniformity is achieved. 
It is presently preferred to combine with the hexadienoyl cyclohexene 
derivatives of our invention the following adjuvants: 
p-Hydroxybenzyl acetone; 
Geraniol; 
Cassia Oil; 
Acetaldehyde; 
Maltol; 
Ethyl methyl phenyl glycidate; 
Benzyl acetate; 
Dimethyl sulfide; 
Eugenol; 
Vanillin; 
Caryophyllene; 
Methyl cinnamate; 
Guiacol; 
Ethyl pelargonate; 
Cinnamaldehyde; 
Methyl Anthranilate; 
5-Methyl furfural; 
Isoamyl acetate; 
Isobutyl acetate; 
Cuminaldehyde; 
Alpha ionone; 
Cinnamyl formate; 
Ethyl butyrate; 
Methyl cinnamate; 
Acetic acid; 
Gamma-undecalactone; 
Naphthyl ethyl ether; 
Diacetyl; 
Furfural; 
Ethyl acetate; 
Anethole; 
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; 
.beta.-Damascone (1-crotonyl-2,2,6-trimethylcyclohex-1-ene); 
.beta.-Damascenone (1-crotonyl-2,2,6-trimethylcyclohexa-1,3-diene); 
Beta-cyclohomocitral (2,2,6-trimethylcyclohex-1-ene carboxaldehyde); 
Isoamyl butyrate; 
Cis-3-hexenol-1; 
2-Methyl-2-pentenoic acid; 
Elemecine (4-allyl-1,2,6-trimethoxybenzene); 
Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene); and 
2-(4-Hydroxy-4-methylpentyl) norbornadiene 
The hexadienoyl cyclohexene derivatives of our invention and one or more 
auxiliary perfume ingredients, including for example, alcohols, aldehydes, 
ketones other than the hexadienoyl cyclohexene derivatives of our 
invention, terpinic hydrocarbons, nitriles, esters, lactones, natural 
essential oils and synthetic 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 odorous substances 
which lend a particular note to the perfume throughout all stages of 
evaporation and substances which retard evaporation and (d) topnotes which 
are usually low-boiling, fresh-smelling materials. 
In perfume compositions, 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, the hexadienoyl 
cyclohexene derivatives of our invention can be used to alter, modify or 
enhance the aroma characteristics of a perfume composition, for example, 
by utilizing or moderating the olfactory reaction contributed by another 
ingredient in the composition. 
The amount of hexadienoyl cyclohexene derivatives 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 the hexadienoyl 
cyclohexene derivatives of our invention or even less (e.g. 0.005%) can be 
used to impart floral, rosey, honey, woody and raspberry note to soaps, 
cosmetics and other products. The amount employed can range up to 70% of 
the fragrance components and will depend on considerations of cost, nature 
of the end product, the effect desired in the finished product and the 
particular fragrance sought. 
The hexadienoyl cyclohexene derivatives of our invention are useful (taken 
alone or together with other ingredients in perfume compositions) as (an) 
olfactory component(s) in detergents and soaps, space odorants and 
deodorants, perfumes, colognes, toilet water, bath 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 the hexadienoyl cyclohexene of our 
invention will suffice to impart an intense floral note to rose 
formulations. Generally no more than 3% of the hexadienoyl cyclohexene 
derivatives of our invention 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 hexadienoyl cyclohexene 
derivatives of our invention. The vehicle can be a liquid such as an 
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). 
The hexadienoyl cyclohexene derivatives of our invention may be blended 
into polymers when forming a perfumed polymer by means of extrusion using 
a single or double screw extruder or technique such as that set forth in 
U.S. Pat. No. 4,247,498 issued on Jan. 27, 1981 which discloses 
microporous polymers which are capable of containing volatile substances 
such as perfumes and the like and forms ranging from films to blocks and 
intricate shapes from synthetic thermoplastic polymers such as olefinic 
condensation or oxidation polymers. The specification of U.S. Pat. No. 
4,247,498 is incorporated by reference herein. Other techniques of 
blending the hexadienoyl cyclohexene derivatives of our invention with 
polymers are exemplified in U.S. Pat. No. 3,505,432 (the specification for 
which is incorporated by reference herein) which discloses a method for 
scenting a polyolefin with such materials as the hexadienoyl cyclohexene 
derivatives of our invention which comprises: 
(a) mixing a first amount of the liquid polyolefin (e.g. polyethylene or 
polypropylene) with a relatively large amount of scent-imparting material 
(in this case the hexadienoyl cyclohexene derivatives of our invention) to 
form a flowable mass; 
(b) forming drops of said mass and causing substantially instantaneous 
solidification of said drops into polyolefin pellets having a relatively 
large amount of such scent-imparting materials as the hexadienoyl 
cyclohexene derivatives of our invention imprisoned therein; 
(c) melting said pellets with a second amount of polyolefin and said second 
amount being larger than the first amount; and 
(d) solidifying the melt of (c). 
Furthermore, the hexadienoyl cyclohexene derivatives of our invention are 
capable of supplying and/or potentiating certain flavor and aroma notes 
usually lacking in many tobacco flavors heretofore provided. 
As used herein in regard to tobacco flavors, the terms "alter" and "modify" 
in their various forms means supplying or imparting flavor character or 
note to otherwise bland tobacco, tobacco substitutes, or tobacco flavor 
formulations or augmenting the existing flavor characteristic where a 
natural flavor is deficient in some regard or supplementing the existing 
flavor impression to modify its quality, character or taste. 
As used herein, the term "enhance" is intended to mean the intensification 
(without change in kind or quality of aroma or taste) of one or more taste 
and/or aroma nuances present in the organoleptic impression of tobacco or 
a tobacco substitute or a tobacco flavor. 
Our invention thus provides an organoleptically improved smoking tobacco 
product and additives therefor, as well as methods of making the same 
which overcome specific problems heretofore encountered in which specific 
desired floral, hay-like, sweet and fruity aroma and taste nuances thereof 
are created or enhanced and may be readily controlled and maintained at 
the desired uniform level regardless of variations in the tobacco 
components of the blend. 
This invention further provides improved tobacco additives and methods 
whereby various floral, hay-like, sweet and fruity notes may be imparted 
to smoking tobacco products and may be readily varied and controlled to 
produce the desired uniform flavor characteristics. 
In carrying out this aspect of our invention, we add to smoking tobacco 
materials or a suitable substitute therefor (e.g. dried lettuce leaves) an 
aroma and flavor additive containing as an active ingredient at least one 
of the hexadienoyl cyclohexene derivatives of our invention. 
In addition to the hexadienoyl cyclohexene derivatives of our invention, 
other flavoring and aroma additives may be added to the smoking tobacco 
materials or substitute therefor either separately or in admixture with 
the hexadienoyl cyclohexene derivatives of our invention as follows: 
(i) Synthetic Materials 
Beta-ethyl-cinnamaldehyde; 
Beta-cyclohomocitral; 
Eugenol; 
Dipentene; 
Damascenone; 
Damascone; 
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-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene; 
Dodecahydro-3a,6,6,9a-tetramethylnaphtho[-2,1b]-furan; 
4-Hydroxy hexanoic acid, gamma lactone; and 
Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No. 3,589,372 
issued on June 29, 1971. 
(ii) Natural Oils 
Celery seed Oil; 
Coffee extract; 
Bergamot Oil; 
Cocoa extract; 
Nutmeg Oil; 
Origanum Oil. 
An aroma and flavoring concentrate containing the hexadienoyl cyclohexene 
derivatives of our invention and, if desired, one or more of the above 
indicated additional flavoring additives may be added to the smoking 
tobacco material, to the filter or to the leaf or paper wrapper. The 
smoking tobacco material may be shredded, cured, cased and blended tobacco 
material or reconstituted tobacco material or tobacco substitutes (e.g. 
dried 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 the hexadienoyl cyclohexene derivatives of our invention to 
smoking tobacco material is between 250 ppm and 1,500 ppm (0.025%-0.15%) 
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 the hexadienoyl cyclohexene derivatives of our 
invention used to flavoring material is between 2,500 and 15,000 ppm 
(0.25%-1.5%). 
Any convenient method for incorporating the hexadienoyl cyclohexene 
derivatives of our invention in the tobacco product may be employed. Thus, 
the hexadienoyl cyclohexene derivatives of our invention taken alone or 
along with other flavoring additives may be dissolved in a suitable 
solvent such as ethanol, pentane, diethylether and/or other volatile 
organic solvents and the resulting solution may either be sprayed on the 
cured, cased and blended tobacco material or the tobacco material may be 
dipped into such solution. Under certain circumstances, a solution of the 
hexadienoyl cyclohexene derivatives of our invention taken alone or 
further together with other flavoring additives as set forth above may be 
applied by means of a suitable applicator such as a brush or roller on the 
paper or leaf wrapper for the smoking product, or it may be applied to the 
filter by either spraying or dipping or coating. 
Furthermore, it will be apparent that only a portion of the tobacco or 
substitute therefor need be treated and the thus treated tobacco may be 
blended with other tobaccos before the ultimate tobacco product is formed. 
In such cases, the tobacco treated may have the hexadienoyl cyclohexene 
derivatives of our invention in excess of the amounts or concentrations 
above indicated so that when blended with other tobaccos, the final 
product will have the percentage within the indicated range. 
In accordance with one specific example of our invention, an aged, cured 
and shredded domestic burley tobacco is sprayed with a 20% ethyl alcohol 
solution of the compound defined according to the structure: 
##STR82## 
in an amount to provide a tobacco composition containing 800 ppm by weight 
of the compound having the structure: 
##STR83## 
Thereafter the alcohol is removed by evaporation and the tobacco is 
manufactured into cigarettes by the usual techniques. The cigarette, when 
treated as indicated, has a desired and pleasing aroma (increased smoke 
body sensation in the mouth with enhanced tobacco-like notes and pleasant 
aromatic nuances) which is detectable in the main and side streams when 
the cigarette is smoked. This aroma is described as having floral, 
hay-like, sweet and fruity notes. 
While our invention is particularly useful in the manufacture of smoking 
tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other 
tobacco products formed from sheeted tobacco dust or fines may also be 
used. Likewise, the hexadienoyl cyclohexene derivatives 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 hexadienoyl 
cyclohexene derivatives of our invention can be added to certain tobacco 
substitutes of natural or synthetic origin (e.g. dried lettuce leaves) 
and, accordingly, by the term "tobacco" as used throughout this 
specification is meant any composition intended for human consumption by 
smoking or otherwise, whether composed of tobacco plant parts or 
substitute materials or both. 
The following Examples I and II serve to illustrate methods for preparing 
the hexadienoyl cyclohexene derivatives of our invention. The following 
Examples III et seq. serve to illustrate methods of utilizing the 
hexadienoyl cyclohexene derivatives of our invention for their 
orgnaoleptic properties. 
All parts and percentages given herein are by weight unless otherwise 
specified. 
EXAMPLE I 
PREATION OF THE METHYL ESTER OF 3-KETO-3-(2'2'6'-TRIMETHYL .DELTA..sup.4 
CYCLOHEXENYL) PROPANIC ACID 
##STR84## 
Into a 3 liter reaction flask equipped with stirrer, condenser, thermometer 
and dropping funnel and a nitrogen blanket apparatus is placed 1,000 cc of 
toluene. Dropwise over a period of 30 minutes, 90 grams (2.0 moles) of a 
50% sodium hydride (in toluene) solution is added. Over a period of 1 hour 
while maintaining the temperature at 50.degree. C., 135.0 grams (1.5 
moles) of dimethyl carbonate is added. While maintaining the reaction mass 
at 50.degree. C., in order to initiate the reaction, 2 cc of methyl 
alcohol and 5 grams of ALIQUAT.sup..RTM. 336 (trimethyl capryl ammonium 
chloride manufactured by the Henkel Chemical Company of Minneopolis Minn.) 
is added. The reaction mass is heated to 80.degree. C. and dropwise over a 
period of 1 hour, the compound having the structure: 
##STR85## 
is added to the reaction mass. After the addition, the reaction mass is 
continued to be heated at 80.degree. C. for a period of 3.5 hours. The 
excess sodium hydride is then decomposed with 200 cc of a 50:50 mixture of 
acetic acid and water. 
The organic layer is separated from the aqueous phase and the organic phase 
is then washed with two 200 cc portions of water followed by two 200 cc 
portions of saturated sodium bicarbonate solution and one 200 cc portion 
of saturated sodium chloride solution. 
The solvent is stripped and the reaction mass is distilled on a 12" stone 
packed column yielding the following fractions: 
______________________________________ 
Vapor Liquid 
Fraction Temp. Temp. Vacuum 
Number (.degree.C.) 
(.degree.C.) 
mm/Hg. 
______________________________________ 
1 65/70 115/120 6.5/6.5 
2 110 125 6.5 
3 122 130 6.5 
4 127 141 6.5 
5 128 181 6.5 
6 165 225 6.5 
______________________________________ 
NMR, IR and mass spectral analyses yield the information that the resulting 
product has the structure: 
##STR86## 
(primarily). 
FIG. 1 is the GLC profile for the crude reaction product prior to 
distillation. 
EXAMPLE II 
PREATION OF 
5-METHYL-1-(2,6,6-TRIMETHYL-3-CYCLOHEXEN-1-YL)-2,4-HEXEDIEN-1-ONE 
##STR87## 
Into a 1 liter reaction flask equipped with a 12" Goodloe column and 
fractionation head is placed the following ingredients: 
112.0 grams (0.5 moles) of the ester prepared according to Example I having 
the structure: 
##STR88## 
(primarily) with a minor proportion of the compound having the structure: 
##STR89## 
111.0 grams (1.32 moles) of 2-methyl-3-butyn-2-ol having the structure: 
##STR90## 
20.0 grams of aluminum isopropoxide. 
The resulting mixture with stirring is heated to 80.degree.-180.degree. C. 
During the reaction methane and carbon dioxide reaction products are 
distilled off. 
When both the methane and the carbon dioxide cease to be evolved, the 
reaction mass is then quenched into a 50:50 mixture of acetic acid and 
water. 
The reaction mass is then extracted with two 100 cc portions of toluene. 
The toluene extracts was washed as follows: 
(i) one 200 cc portion of water; 
(ii) one 200 cc portion of saturated sodium bicarbonate; 
(iii) one 200 cc portion of saturated sodium chloride solution. 
The resulting product is then stripped of solvent and distilled on a 12" 
stone packed column yielding the following two fractions: 
______________________________________ 
Vapor Liquid 
Fraction Temp. Temp. Vacuum 
Number (.degree.C.) (.degree.C.) 
mm/Hg. 
______________________________________ 
1 128 195 1.4 
2 135 260 1.2 
______________________________________ 
The resulting two products are bulked and redistilled on a spinning band 
column yielding the following fractions: 
______________________________________ 
Vapor Liquid Weight of 
Fraction Temp. Temp. Vacuum Fraction 
Number (.degree.C.) 
(.degree.C.) 
mm/Hg (grams) 
______________________________________ 
1 30/40 80/80 0.8/0.8 
1.0 
2 45 80 0.8 2.8 
3 48 150 1.0 2.8 
4 85 158 1.0 5.0 
5 90 168 1.0 5.8 
6 96 200 1.0 6.0 
7 40 230 1.0 3.5 
______________________________________ 
GLC, NMR, IR and mass spectral analyses yield the information that the 
resulting product is primarily a compound having the structure: 
##STR91## 
with minor amounts of compounds having the structures: 
##STR92## 
FIG. 2 is the GLC profile for the crude reaction product prior to the first 
distillation. 
FIG. 3 is the GLC profile for fraction 1 of the first distillation 
(conditions: SE-30 column programmed at 100.degree.-220.degree. C. at 
8.degree. C. per minute). 
FIG. 4 is the GLC profile for fraction 2 of the first distillation. The 
peak indicated by reference numeral "40" is the peak for the compound 
having the structure: 
##STR93## 
FIG. 5 is the GLC profile for fraction 4 of the second distillation product 
as set forth above (conditions: Carbowax column programmed at 
100.degree.-220.degree. C. at 8.degree. C. per minute). 
FIG. 6 is the GLC profile for fraction 5 of the second distillation. 
FIG. 7 is the GLC profile for fraction 6 of the second distillation. 
FIG. 8 is the GLC profile for fraction 7 of the second distillation. 
FIG. 9 is the NMR spectrum for the peak indicated by reference numeral "40" 
of fraction 2 of the first distillation, the reference numeral "40" being 
on FIG. 4 (conditions: 100 MHz field strength; CFCl.sub.3 solvent). 
FIG. 10 is the infra-red spectrum for the peak indicated by reference 
numeral "40" which is the peak for the compound having the structure: 
##STR94## 
on the GLC profile of FIG. 4. 
EXAMPLE III 
COMISON OF PERFUME COMPOSITIONS CONTAINING ISOMERS OF MATERIALS PRODUCED 
ACCORDING TO EXAMPLE II 
Isomers having the structures: 
##STR95## 
are compared side by side in a rose perfume which contains the following 
mixtures: 
______________________________________ 
Parts by Weight 
Ingredients III (A) III (B) III (C) 
III (D) 
______________________________________ 
Rhodinol 250 250 250 250 
Phenylethyl alcohol 
195 195 195 195 
Alpha methyl ionone 
80 80 80 80 
Linalyl acetate 60 60 60 60 
Cis-3-hexenyl acetate 
5 5 5 5 
Jasmine absolute 10 10 10 10 
Cinnamic alcohol 20 20 20 20 
Rhodinyl acetate 60 60 60 60 
Cyclohexyl ethyl alcohol 
20 20 20 20 
Geraniol 130 130 130 130 
Geranyl acetate 80 80 80 80 
Paraisopropyl cyclohexanol 
60 60 60 60 
Diethyl phthalate 
30 30 30 30 
Trans,trans-delta-damascone 
30 30 30 30 
produced according to U.S. 
Letters Pat. No. 4,334,098, the 
specification for which is 
incorporated by reference 
herein 
Compound having 
the structure: 
##STR96## 30 0 0 0 
Compound having 
the structure: 
##STR97## 0 30 0 0 
Compound having 
the structure: 
##STR98## 0 0 30 0 
Compound having 
the structure: 
##STR99## 0 0 0 30 
______________________________________ 
The compound having the structure: 
##STR100## 
imparts to this rose formulation an excellent floral, honey, woody, 
"raspberry"-like aroma with intense patchouli-like undertones. 
Accordingly, the fragrance produced using this formulation can be 
described as having an intense, rose aroma with honey, patchouli, 
raspberry-like undertones and apple, green and sweet topnotes. 
The compound having the structure: 
##STR101## 
imparts to this rose formulation an excellent honey, woody, 
"mahogany-like" aroma. Accordingly, the resulting perfume formulation can 
be described as an intense rose aroma with "mahogany-like" woody and honey 
undertones and apple, green and sweet topnotes. 
The compound having the structure: 
##STR102## 
imparts a honey, green, woody, fresh raspberry aroma to this rose 
formulation. Accordingly, the resulting perfume composition can be 
described as having an intense rose aroma with green, woody, honey and 
raspberry undertones and apple, green and sweet topnotes. 
The compound having the structure: 
##STR103## 
imparts a vetiver-like, honey and white rose aroma profile to this intense 
rose formulation. Thus, the perfume composition of Example III(D) can be 
described as an intense rose aroma with white rose, vetiver-like and honey 
nuances and apple, green and sweet topnotes. 
EXAMPLE IV 
PREATION OF COSMETIC POWDER COMPOSITIONS 
Cosmetic powder compositions are prepared by mixing in a ball mill 100 
grams of talcum powder with 0.25 grams of each of the substances set forth 
in Table I below. Each of the cosmetic powder compositions has an 
excellent aroma as described in Table I below. 
TABLE I 
______________________________________ 
Substance Aroma Description 
______________________________________ 
##STR104## An intense floral, rosey, honey, woody, raspberry-like 
aroma profile. 
prepared according 
to Example II, 
bulked fractions 4-7. 
Perfume composition of 
An intense, rose aroma with 
Example III (A). honey, patchouli, raspberry- 
like undertones and apple, 
green and sweet topnotes. 
Perfume composition of 
An intense rose aroma with 
Example III (B). "mahogany-like", woody and 
honey undertones and apple, 
green and sweet topnotes. 
Perfume composition of 
An intense rose aroma with 
Example III (C). green, woody, honey and rasp- 
berry undertones and apple, 
green and sweet topnotes. 
Perfume composition of 
An intense rose aroma with 
Example III (D). white rose, vetiver-like and 
honey nuances and apple, 
green and sweet topnotes. 
______________________________________ 
EXAMPLE V PERFUMED LIQUID DETERGENTS 
Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonic 
acid as more specifically described in U.S. Pat. No. 3,948,818, issued on 
Apr. 6, 1976 incorporated by reference herein) with aroma nuances as set 
forth in Table I of Example IV, are prepared containing 0.10%, 0.15%, 
0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in Table I of 
Example IV. They are prepared by adding and homogeneously mixing the 
appropriate quantity of substance set forth in Table I of Example IV in 
the liquid detergent. The detergents all possess excellent aromas as set 
forth in Table I of Example IV, the intensity increasing with greater 
concentrations of substance as set forth in Table I of Example IV. 
EXAMPLE VI 
PREATION OF COLOGNES AND HANDKERCHIEF PERFUMES 
Compositions as set forth in Table I of Example IV are incorporated into 
colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and 5.0% 
in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions; and into 
handkerchief perfumes at concentrations of 15%, 20%, 25% and 30% (in 80%, 
85%, 90% and 95% aqueous food grade ethanol solutions). Distinctive and 
definitive fragrances as set forth in Table I of Example IV are imparted 
to the colognes and to the handkerchief perfumes at all levels indicated. 
EXAMPLE VII 
PREATION OF SOAP COMPOSITIONS 
One hundred grams of soap chips (per sample) (IVORY.RTM. produced by the 
Proctor & Gamble Company of Cincinnati, Ohio), are each mixed with one 
gram samples of substances as set forth in Table I of Example IV until 
homogeneous compositions are obtained. In each of the cases, the 
homogeneous compositions are heated under 8 atmospheres pressure at 
180.degree. C. for a period of three hours and the resulting liquids are 
placed into soap molds. The resulting soap cakes, on cooling, manifest 
aromas as set forth in Table I of Example IV. 
EXAMPLE VIII 
PREATION OF SOLID DETERGENT COMPOSITIONS 
Detergents are prepared using the following ingredients according to 
Example 1 of Canadian Patent No. 1,007,948 (incorporated by reference 
herein): 
______________________________________ 
Ingredient Percent by Weight 
______________________________________ 
Neodol .RTM. 45-11 (a C.sub.14 -C.sub.15 
12 
alcohol ethoxylated with 
11 moles of ethylene oxide) 
Sodium carbonate 55 
Sodium citrate 20 
Sodium sulfate, water brighteners 
q.s. 
______________________________________ 
This detergent is a phosphate-free detergent. Samples of 100 grams each of 
this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams of each of 
the substances as set forth in Table I of Example IV. Each of the 
detergent samples has an excellent aroma as indicated in Table I of 
Example IV. 
EXAMPLE IX 
Utilizing the procedure of Example I at column 15 of U.S. Pat. No. 
3,632,396 (the disclosure of which is incorporated herein by reference), 
nonwoven cloth substrates useful as drier-added fabric softening articles 
of manufacture are prepared wherein the substrate, the substrate coating, 
the outer coating and the perfuming material are as follows: 
1. A water "dissolvable" paper ("Dissolvo Paper"); 
2. Adogen 448 (m.p. about 140.degree. F.) as the substrate coating; and 
3. An outer coating having the following formulation (m.p. about 
150.degree. F.): 
57% C.sub.20-22 HAPS 
22% isopropyl alcohol 
20% antistatic agent 
1% of one of the substances as set forth in Table I of Example IV. 
Fabric softening compositions prepared according to Example I at column 15 
of U.S. Pat. No. 3,632,396 having aroma characteristics as set forth in 
Table I of Example IV, supra, consist of a substrate coating having a 
weight of about 3 grams per 100 square inches of substrate; a first 
coating located directly on the substrate coating consisting of about 1.85 
grams per 100 square inches of substrate; and an outer coating coated on 
the first coating consisting of about 1.4 grams per 100 square inches of 
substrate. One of the substances of Table I of Example IV is admixed in 
each case with the outer coating mixture, thereby providing a total 
aromatized outer coating weight ratio to substrate of about 0.5:1 by 
weight of the substrate. The aroma characteristics are imparted in a 
pleasant manner to the head space in a drier on operation thereof in each 
case using said drier-added fabric softener non-woven fabrics and these 
aroma characteristics are described in Table I of Example IV, supra. 
EXAMPLE X 
HAIR SPRAY FORMULATIONS 
The following hair spray formulation is prepared by first dissolving PVP/VA 
E-735 copolymer manufactured by the GAF Corporation of 140 West 51st 
Street, New York, N.Y. in 91.62 grams of 95% food grade ethanol. 8.0 grams 
of the polymer is dissolved in the alcohol. The following ingredients are 
added to the PVP/VA alcoholic solution: 
______________________________________ 
Dioctyl sebacate 0.05 weight percent 
Benzyl alcohol 0.10 weight percent 
Dow Corning 473 fluid 
0.10 weight percent 
(prepared by the Dow Corning 
Corporation) 
Tween 20 surfactant 0.03 weight percent 
(prepared by ICI America 
Corporation) 
One of the perfumery sub- 
0.10 weight percent 
stances as set forth in 
Table I of Example IV 
______________________________________ 
The perfuming substances as set forth in Table I of Example IV add aroma 
characteristics as set forth in Table I of Example IV which are rather 
intense and aesthetically pleasing to the users of the soft-feel, 
good-hold pump hair sprays. 
EXAMPLE XI 
CONDITIONING SHAMPOOS 
Monamid CMA (prepared by the Mona Industries Company) (3.0 weight percent) 
is melted with 2.0 weight percent coconut fatty acid (prepared by Proctor 
& Gamble Company of Cincinnati, Ohio); 1.0 weight percent ethylene glycol 
distearate (prepared by the Armak Corporation) and triethanolamine (a 
product of Union Carbide Corporation) (1.4 weight percent). The resulting 
melt is admixed with Stepanol WAT produced by the Stepan Chemical Company 
(35.0 weight percent). The resulting mixture is heated to 60.degree. C. 
and mixed until a clear solution is obtained (at 60.degree. C.). This 
material is "Composition A". 
Gafquat.RTM.755 N polymer (manufactured by GAF Corporation of 140 West 51st 
Street, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weight 
percent sodium sulfite and 1.4 weight percent polyethylene glycol 6000 
distearate produced by Armak Corporation. This material is "Composition 
B". 
The resulting "Composition A" and "Composition B" are then mixed in a 50:50 
weight ratio of A:B and cooled to 45.degree. C. and 0.3 weight percent of 
perfuming substance as set forth in Table I of Example IV is added to the 
mixture. The resulting mixture is cooled to 40.degree. C. and blending is 
carried out for an additional one hour in each case. At the end of this 
blending period, the resulting material has a pleasant fragrance as 
indicated in Table I of Example IV. 
EXAMPLE XII 
Scented polyethylene pellets having a pronounced scent as set forth in 
Table I of Example IV are prepared as follows: 
75 pounds of polyethylene of a melting point of about 220.degree. F. are 
heated to about 230.degree. F. in a container of the kind illustrated in 
FIGS. 11 and 12. 25 pounds of each of the perfume materials of Table I of 
Example IV supra, are then added quickly to the liquified polyethylene. 
The lid 228 is put in place and the agitating means 273 are actuated. The 
temperature is maintained at about 225.degree. F. and the mixing is then 
continued for about 5-15 minutes. The valve "V" is then opened to allow 
flow of the molten polyethylene enriched with each of the aroma 
substance-containing materials to exit through the orifices 234. The 
liquid falling through the orifices 234 solidify almost instantaneously 
upon impact with the moving, cooled conveyor 238. Solid polyethylene beads 
or pellets 244 having pronounced aromas as set forth in Table I of Example 
IV supra are then formed. Analysis demonstrates that the pellets contain 
about 25% of each of the perfume substances of Table I of Example IV so 
that almost no losses of the scenting substance occur. These pellets may 
be called master pellets. 
50 pounds of the scent-containing master pellets are then added to 1,000 
pounds of unscented polyethylene powder and the mass is heated to the 
liquid state. The liquid is molded into thin sheets or films. The sheets 
or films have a pronounced aroma as set forth in Table I of Example IV 
supra. The sheets are also fabricated into garbage bags which have aromas 
as set forth in Table I of Example IV supra. 
EXAMPLE XIII 
TOBACCO FORMULATION 
A tobacco mixture is prepared by admixing the following ingredients: 
______________________________________ 
Ingredients 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: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Ethyl butyrate 0.05 
Ethyl valerate 0.05 
Maltol 2.00 
Cocoa extract 26.00 
Coffee extract 10.00 
Ethyl alcohol 20.00 
Water 41.90 
______________________________________ 
The above stated tobacco flavor formulation is applied at the rate of 1.0% 
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 the 
product of Example II, bulked fractions 4-7 containing primarily the 
compound defined according to the structure: 
##STR105## 
The control cigarettes not containing the compound having the structure: 
##STR106## 
produced according to the process of Example II and the experimental 
cigarettes which contain the compound having the structure: 
##STR107## 
produced according to Example II are evaluated by paired comparison and 
the results are as follows: 
The experimental cigarettes are found to have more body in tobacco smoke 
flavor and a fuller body sensation. The tobacco-like notes are enhanced 
and the flavor of the tobacco on smoking is more aromatic with floral, 
hay-like, sweet and fruity aroma and taste nuances. 
The tobacco smoke flavors of the experimental cigarettes prior to smoking 
has floral, hay-tea-like, sweet and fruity notes. 
All cigarettes are evaluated for smoke flavor with a 20 mm cellulose 
acetate filter. 
EXAMPLE XIV 
MANGO FLAVOR FORMULATION 
Goya.RTM. brand mango nectar (manufactured by Goya Foods Inc. of 25-12th 
Street, Brooklyn, N.Y.) is split into three samples. 
To the first sample at the level of 3 ppm, the compound having the 
structure: 
##STR108## 
prepared according to Example II, bulked fractions 4-7 is added without 
anything else. 
To the second sample, the following formulation is added: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Compound having the structure: 
12.0 
##STR109## 
Orange oil absolute 8.0 
Lime oil absolute ex Mayaguez 
14.5 
Trans, trans-delta-damascone 
2.8 
Beta-damascone 4.5 
1-methyl-3-n-propyl-2,4-oxathiane 
12.4 
______________________________________ 
at the level of 12 ppm. 
The mango nectar not containing any of the additional ingredients has a 
very bland taste. The mango nectar containing the additional compound 
having the structure: 
##STR110## 
either taken alone or together with the other members of the formulation 
have minty, citrusy, lime, floral, rosey aroma and taste nuances in 
addition to fresh and cooling nuances. 
EXAMPLE XV 
TOOTHPASTE 
At the level of 2 ppm, the compound having the structure: 
##STR111## 
is added to a toothpaste formulation which has been previously unflavored 
(unflavored Crest.RTM. manufactured by the Proctor & Gamble Company of 
Cincinnati, Ohio). The compound having the structure: 
##STR112## 
imparts a minty, citrusy, lime, floral and rosy taste with intense fresh, 
cooling nuances to the previously unflavored toothpaste. 
A bench panel of 4 members (blind panel; employees of International Flavors 
& Fragrances Inc.) considered the formulation with the compound having the 
structure: 
##STR113## 
to be superior in taste to the formulation without the compound having the 
structure: 
##STR114## 
produced according to Example II. 
Closely similar effects were obtained when using compounds having the 
structures: 
##STR115## 
produced according to Example II by means of chromatographic separation. 
EXAMPLE XVI 
MOUTHWASH 
To Scope.RTM. mouthwash (trademark of the Johnson & Johnson Company of New 
Brunswick, N.J.) at the level of 5 ppm, the compound having the structure: 
##STR116## 
produced according to Example II is added. The compound having the 
structure: 
##STR117## 
imparts to the Scope.RTM. mouthwash additional and pleasant minty, 
citrusy, lime and fresh, cooling nuances. 
The resulting mouthwash is preferred by an independent blind bench panel of 
4 members over the mouthwash without the compound having the structure: 
##STR118## 
produced according to Example II.