Bisabolene-containing composition, process for preparing same, organoleptic uses thereof and uses thereof as insect repellent

Described are isomeric mixtures of bisabolene prepared by dehydrating nerolidol using citric acid or phosphoric acid and then distilling the resulting product at particular temperature ranges and particular pressure ranges in order to prepare a composition of matter useful for augmenting or enhancing natural, dry, floral, opoponax aromas with floral, freesia, fruity, citrus, bergamot, mango and opoponax topnotes in perfume compositions, colognes and perfumed articles (e.g., solid or liquid anionic, cationic, nonionic, or zwitterionic detergents, fabric softener compositions, drier-added fabric softener articles, cosmetic powders and the like; and useful for repelling specific species of insects, namely, house flies Musca domestica L. (Diptera Muscidae)) and the species of mosquitoes, Aedes aegypti.

BACKGROUND OF THE INVENTION 
The present invention relates to bisabolene isomer mixtures containing, but 
not limited to, compounds defined according to the structure: 
##STR1## 
including the compounds having the structures: 
##STR2## 
and uses of such mixtures in augmenting or enhancing the aroma of perfume 
compositions, perfumed articles and colognes; as well as uses thereof in 
repelling insects including Musca domestica L.(Diptera Muscidae) and Aedes 
aegypti. 
The compositions of our invention are prepared by dehydrating nerolidol 
using citric acid or phosphoric acid dehydrating agents. Nerolidol isomers 
are defined according to the structure: 
##STR3## 
and include cis and trans isomers thereof shown by the structures: 
##STR4## 
There has been considerable work performed relating to substances which can 
be used to impart (modify, augment or enhance) fragrances to (or in) 
various consumable materials. The 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. 
Natural, dry, floral, opoponax aromas with floral, freesia, fruity, citrus, 
bergamot, mango and opoponax topnotes are particularly desirable in 
several types of perfume compositions, perfumed articles and colognes, 
including "ginger" perfumes. 
Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", Volume I, at 
monograph 348 indicates that gamma bisabolene having the structure: 
##STR5## 
has a pleasant, warm, sweet spicy, balsamic aroma inevitably reminding the 
perfumer of opoponax and "oriental" fragrance types. Arctander further 
states that gamma bisabolene finds good use in artificial oils of 
bergamot, myrrh, lemon and the like. Arctander further states that it may 
be produced from nerolidol "by dehydration". 
Furthermore, Ruzicka and Capato, Helv. Chim. Acta 8, 259(1925) indicates 
that nerolidol having the structure: 
##STR6## 
can be dehydrated to using formic acid to produce alpha bisabolene having 
the structure: 
##STR7## 
beta bisabolene having the structure: 
##STR8## 
and gamma bisabolene having the structure: 
##STR9## 
as well as bisabolol having the structure: 
##STR10## 
However, Ruzicka and Capato and for that matter, any other relevant prior 
art do not disclose the use of citric acid or phosphoric acid to dehydrate 
nerolidol or natural materials containing nerolidol in large quantities 
such as Cabreuva oil to produce the novel composition of matter of our 
invention which has unexpected, unobvious and advantageous properties not 
only insofar as its organoleptic character is concerned but also regarding 
its character as a semio chemical; that is, in order to repel the insects, 
Musca domestica L.(Diptera Muscidae) as well as Aedes aegypti. Reference 
to Cabreuva oil as containing a large amount of nerolidol is set forth at 
columns 108 and 109 of "Perfume and Flavor Materials of Natural Origin", 
Arctander, 1960. 
Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", at Monograph 
1378, discloses "Farnesal", 2,6,10-trimethyl-2,6,10-dodecatrien-12-al to 
have a very mild, sweet oily, slightly woody, tenacious odor. On the other 
hand, Arctander also describes, at Monograph 1379, Farnesene, 
2,6,10-trimethyl 2,6,9,11-dodecatetraene defined according to the 
structure: 
##STR11## 
to have a very mild, sweet and warm, rather nondescript odor of good 
tenacity. Arctander further states that apart from some possible use in 
the reconstruction of certain essential oils, there is to the author's 
knowledge, very little, if any, use for this sesquiterpene in perfumery as 
such. Arctander further states that Farnesene having the structure: 
##STR12## 
is produced by dehydration of Farnesol by heat with a potassium 
dehydrating agent or from Nerolidol by heat with acetic anhydride. 
Brieger, et al, J. Org. Chem., Volume 34, No. 12, December 1969, in their 
paper "The Synthesis of trans,trans-alpha Farnesene" discloses dehydration 
of nerolidol using bisulfate at 170.degree. C. to yield a number of 
Farnesene isomers according to the reaction: 
##STR13## 
Brieger, et al also discloses the dehydration of Farnesol using potassium 
bisulfate at 170.degree. C. as follows: 
##STR14## 
Brieger also teaches the dehydration of Farnesol using potassium hydroxide 
at 210.degree. C. to yield certain isomers according to the following 
reaction: 
##STR15## 
Anet, Aust. J. Chem., 1970, 23, 2101-8, in a paper entitled "Synethesis of 
(E,Z)-alpha-, (Z,Z)-alpha-, and (Z)-.beta.-Farmesere" discloses the 
dehydration of (E)-nerolidol having the structure: 
##STR16## 
in the presence of such dehydrating agents as phosphoryl chloride in 
pysridene to yield the compounds having the structures: 
##STR17## 
In a paper by Hattori, et al entitled "Chemical Composition of the Absolute 
from Gardenia Flower" and in another paper by Tsuneya, et al entitled 
"GC-MS Analysis of Gardenia Flower Volatiles", it is disclosed that 
alpha-farnesene is existent in gardenia flower absolute. The Hattori, et 
al and Tsuneya, et al papers are published in the "VII International 
Congress of Essential Oils"; Japan Flavor and Fragrance Manufacturers' 
Association, Tokyo (1979) at pages 451 and 454, respectively (papers 128 
and 129, respectively). 
Beroza, "Materials Tested As Insect Attractants", Agriculture Handbook No. 
239, Agricultural Research Service, United States Department of 
Agriculture) June 1963, at Table 2, discloses the use of certain 
hydrocarbons as insect attractants. Thus, Item No. 24 is 
3-(1-butenyl)-2,4,4-trimethyl cyclohexene and is shown to be an attractant 
for the Oriental fruit fly, the Mediterranean fruit fly and the Mexican 
fruit fly as well as the Gypsy Moth and the Boll Weevil at levels of "1" 
on a scale of 1-3 and at a level of "2" for the Pink Bollworm. This 
compound has the structure: 
##STR18## 
Beta phellandrene is also shown by Beroza, et al to be an attractant for 
the Oriental fruit fly at a level of "3" on a scale of 1-3 and an 
attractant for the Mediterranean fruit fly at a level of "1" on a scale of 
1-3. Beta phellandrene is indicated as Item No. 56, in Table 2 of the 
Beroza reference. Beta phellandrene has the structure: 
##STR19## 
No structures remotely resembling the structure of any of the bisabolene 
isomers of our invention is shown to be a repellent or for that matter is 
shown to have any activity towards insects in the prior art. Furthermore, 
nothing in the prior art indicates the unexpected, unobvious and 
advantageous perfumery property of the composition of matter defined 
according to our invention. Accordingly, not only does the composition of 
matter defined according to our invention have valuable organoleptic 
properties from a perfumery standpoint but said composition also has 
valuable properties insofar as its insect repellency is concerned with 
regard to Musca domestica L.(Diptera Muscidae) and Aedes aegypti. 
Interestingly, the composition of matter of our invention in addition has 
properties as a flavorant also. 
SUMMARY OF THE INVENTION 
It has now been discovered that novel solid and liquid perfume 
compositions, colognes and perfumed articles having natural, dry, floral, 
opoponax aromas, with floral, freesia, fruity, citrus, bergamot, mango and 
opoponax topnotes may be provided by an isomeric mixture of bisabolene 
derivatives (containing a number of other compounds) defined according to 
the processes for producing same by the dehydration of various isomeric 
mixtures of E (trans) and Z (cis) nerolidol having the structures: 
##STR20## 
using citric acid or phosphoric acid dehydration catalyst over a 
particular temperature and pressure range for a given reaction time range. 
The reaction to produce the products of our invention may be set forth as 
follows: 
##STR21## 
wherein the catalyst used may be citric acid or phosphoric acid. 
The nerolidol isomers used may be in the form of a natural isomeric 
mixture, e.g., Cabreuva oil or they may be mixtures synthetically produced 
of "cis" and "trans" isomers. The ratio of E (trans) or Z (cis) nerolidol 
isomers having the structures: 
##STR22## 
used in the reaction mass may vary from 0:100 E isomer:Z isomer up to 
100:0 E isomer:Z isomer. Although the isomer mixture is substantially the 
same whether using phosphoric acid or citric acid as a catalyst, the 
specific reaction conditions using the two catalysts vary from another. 
When using citric acid as well as phosphoric acid as a catalyst, the 
temperature range for the reaction is preferably between 155.degree. C. 
and 175.degree. C. When using the citric acid catalyst or the phosphoric 
acid, it is necessary to utilize a solvent for the reaction mass which 
will: 
(a) be inert to the reaction; and 
(b) have a boiling point at the reaction pressure which will be 
conveniently greater than the reaction temperature so that the solvent 
will not volatilize from the reaction mass. 
Thus, when using citric acid as a catalyst or phosphoric acid as a catalyst 
at a temperature in the range of 155.degree.-175.degree. C., it is most 
preferable to use a heavy hydrocarbon mineral oil, for example, 
PRIMOL.RTM.(manufactured by the Exxon Corporation of Linden, N.J.). Other 
inert solvents such as toluene and xylene may be used but, when using 
toluene, the pressure over the reaction mass must be such that the 
reaction mass will reflux in the range of 155.degree.-175.degree. C. Thus, 
when using a toluene or xylene solvent, a positive nitrogen pressure over 
the reaction mass is necessary in order to maintain the reaction 
temperature at 155.degree.-175.degree. C. 
Thus, when using the citric acid catalyst or the phosphoric acid catalyst, 
not only is the temperature range important, e.g., 155.degree.-175.degree. 
C., but the pressure range is equally as important; from 1 up to 200 
atmospheres pressure. Using pressures greater than 1 atmosphere 
necessitates the use of high pressure equipment and appropriate safety 
precautions. 
Whether using a phosphoric acid catalyst or a citric acid catalyst, it is 
preferable to remove the water of reaction as it is formed. Thus, during 
refluxing a phase separation column is necessarily utilized whereby the 
water of reaction is removed during the course of the reaction. For 
example, a Bidwell water trap is the type of trap used in the laboratory 
when removing the water of reaction. 
The time of reaction is necessarily dictated by the rate at which the 
nerolidol reaction mixture or Cabreuva oil is added to the 
catalyst/solvent mixture. It is preferable to add the nerolidol or 
Cabreuva oil to the catalyst/solvent mixture over a period of between 1 
and 5 hours. 
Whether using a phosphoric acid catalyst or a citric acid catalyst, the 
ratio of catalyst to nerolidol may vary from 1:1000 (weight/weight) up to 
1:5 with a preferred ratio of 1:10 when using a citric acid catalyst or a 
phosphoric acid catalyst. The concentration of catalyst in the reaction 
mixture may vary from about 1:50 to about 1:5 with a preferred 
concentration of catalyst when using citric acid of 1:30 and a preferred 
concentration of catalyst when using phosphoric acid of 1:20. 
The ratio of solvent:nerolidol isomer mixture varies depending upon the 
particular solvent used and the desired catalyst concentration. Thus, when 
using a heavy hydrocarbon inert mineral oil and a citric acid catalyst, 
the ratio of solvent:nerolidol isomer mixture may vary between 4:1 and 1:4 
with a preferred ratio of 2:1. When using a phosphoric acid catalyst, the 
ratio of solvent:nerolidol isomer mixture may vary from 2:1 up to 1:2 with 
a preferred ratio being about 1:1. When using a toluene solvent or a 
xylene solvent the preferred weight/weight ratio may vary from 1:2 up to 
2:1 with a most preferred weight ratio of nerolidol isomer mixture:solvent 
being 1:1. 
The product produced according to the process of our invention contains 
other materials besides the alpha bisabolene, beta bisabolene and gamma 
bisabolene, for example, trans-beta-farnesene having the structure: 
##STR23## 
gamma curcumene having the structure 
##STR24## 
epizonarene having the structure: 
##STR25## 
trans,trans-alpha farnesene having the structure: 
##STR26## 
allofarnesene having the structure: 
##STR27## 
a zonarene isomer having the structure: 
##STR28## 
and another hydrocarbon having the structure: 
##STR29## 
Nevertheless, the bisabolene isomers defined according to the generic 
structure: 
##STR30## 
wherein one of the dashed lines is a carbon-carbon double bond and each of 
the other of the dashed lines represent carbon-carbon single bonds in each 
of the compounds of the mixture is the predominant material. This is only 
true in the case where the citric acid or phosphoric acid catalysts are 
used. When other catalysts are used, the amount of bisabolene isomers is 
in the minority. 
Thus, when using para toluene sulfonic acid as a catalyst in PRIMOL.RTM. at 
165.degree. C., the ratio of bisabolene isomers:farnesene isomers is 
15.2:47.4. 
When FILTROL.RTM. 25 (an acid ion exchange resin) is used, polymer is 
obtained. 
When DOWEX.RTM. 50 (an acid ion exchange resin) is used, analysis shows 20% 
of an unknown low molecular weight; 14% of unreacted nerolidol and the 
remainder of the mixture various bisabolenes and farnesenes. 
When sulfuric acid is used, no bisabolene or farnesene is produced using 
the foregoing conditions. 
The product-by-process of our invention, the bisabolene isomer mixture and 
one or more auxiliary perfume ingredients including, for example, 
alcohols, aldehydes, ketones, nitriles, esters, cyclic esters (lactones), 
dialkyl ethers, alkyl alkenyl ethers, thioethers, thiols, carboxylic acids 
and hydrocarbons other than the bisabolene isomeric mixture of our 
invention 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 ginger 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 notes; (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) top notes 
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 bisabolene isomer 
mixture produced according to the process 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 bisabolene isomer mixture 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 bisabolene isomer 
mixture or even less, (e.g., 0.005%) can be used to impart a very natural, 
dry, floral, opoponax aroma, with floral, freesia, fruity, citrus, 
bergamot, mango and opoponax topnotes 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 and 
product, the effect desired on the finished product and the particular 
fragrance sought. 
The bisabolene isomer mixture produced according to the process of our 
invention is 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 waters, 
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 
perfumed article compositions of matter such as perfumed polypropylene, 
polyethylene and polyurethanes, particularly long-lasting mixtures of, for 
example, encapsulated perfumes suspended in free perfume compositions and 
the like. When used as (an) olfactory component(s), as little as 0.1% of 
the bisabolene isomer mixture of our invention will suffice to impart an 
intense, natural, dry, floral, opoponax aroma with floral, freesia, 
fruity, citrus, bergamot, mango and opoponax topnotes to ginger 
formulations. Generally, no more than 3% of the bisabolene isomer mixture 
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 bisabolene isomer 
mixture. The vehicle can be a liquid such as a non-toxic alcohol, (e.g., 
ethyl alcohol), a non-toxic glycol (e.g., propylene glycol or 1,2-butylene 
glycol or sorbitol) or the like. The carrier can also be an absorbent 
solid such as a gum (e.g., gum arabic, xanthan gum or the like) or 
components for encapsulating the composition (such as gelatin or ethyl 
cellulose) as by coacervation. 
When used as a component of a perfumed article such as a perfumed plastic 
or solid or liquid anionic, cationic, nonionic or zwitterionic detergent 
or drier-added fabric softener article or a fabric softener composition or 
a shampoo or a soap, the range of bisabolene isomer composition usable 
varies from 0.005% up to about 5% by weight of the perfumed article. The 
lower end of this range, e.g., 0.005% up to 0.1% of the bisabolene isomer 
mixture of our invention is most preferred when using it in a drier-added 
fabric softener article or fabric softener composition in view of the need 
for "non-perfumey" but pleasant head space aroma above the batch of 
clothes being dried using a drier-added fabric softener article or fabric 
softener composition in a standard automatically operated tumbler dryer. 
When the bisabolene isomer composition of our invention produced according 
to the process of our invention is used as a food flavor adjuvant, the 
nature of the coingredients included with the bisabolene isomer 
composition used 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 means "supplying or imparting flavor 
character or note to otherwise bland, relatively tasteless substances or 
augmenting the existing flavor characteristic where a natural flavor is 
deficient in some regard or supplementing the existing flavor impression 
to modify its quality, character or taste". 
The term "enhance" is used herein to mean the intensification of a flavor 
or aroma characteristic or note without the modification of the quality 
thereof. Thus, "enhancement" of a flavor or aroma means that the 
enhancement agent does not add any additional flavor note. 
As used herein, the term "foodstuff" includes both solid and liquid 
ingestible materials which usually do, but need not, have nutritional 
value. Thus, foodstuffs include soups, convenience foods, beverages, dairy 
products, candies, chewing gums, vegetables, cereals, soft drinks, snacks 
and the like. 
As used herein, the term "medicinal product" includes both solids and 
liquids which are ingestible non-toxic materials which have medicinal 
value such as cough syrups, cough drops, aspirin and chewable medicinal 
tablets. 
The term "chewing gum" is intended to mean a composition which comprises a 
substantially water-insoluble chewable plastic gum base such as chicle, or 
substitutes therefor, including jelutong, guttakay rubber or certain 
comesible 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 bisabolene 
isomer composition of our invention and, in addition, sweetening agents 
which may be sugars, including sucrose or dextrose and/or artificial 
sweeteners such as cyclamates or saccharine. Other optional ingredients 
may also be present. 
Substances 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; nitrient 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-butanol, cortonal, diacetyl, 2-methyl butanol, 
.beta.,.beta.-dimethyl acrolein, methyl-n-amyl ketone, n-hexanal, 
2-hexenal, isopentanal, hydrocinnanic aldehyde, cis-3-hexenal, 2-heptenal 
nonyl aldehyde, 4-(p-hydroxy-phenyl)-2-butanone, alpha-ionone, 
beta-ionone, methyl-3-butanone, benzaldehyde, .beta.-damascone, 
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-hexanol, 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-methyl-butyrate, ethyl propionate, 
ethyl salicylate, trans-2-hexenyl acetate, n-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 haphthalene, 
tridecane, trimethyl naphthalene, undecane, caryophyllene, 1-phellandrene, 
p-cymene, 1-alpha-pinene; pyrazines, such as 2,3-dimethylpyrazine, 
2,5-dimethylpyrazine, 2,6-dmethylpyrazine, 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 
gamma-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 bisabolene isomer composition 
of our invention by not covering or spoiling the organoleptic properties 
(aroma and/or taste) thereof; (ii) be non-reactive with the bisabolene 
isomer composition of our invention and (iii) be capable of providing an 
environment in which the bisabolene isomer composition of our invention 
can be dispersed or admixed to provide a homogeneous medium. In addition, 
selection of one or more flavor 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 or chewing tobacco 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 
bisabolene isomer composition thereof of our invention 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 (e.g., a "raisin-rum cake") 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, (e.g., when actual raisins and rum are present in the foodstuff 
such as the cake). The primary requirement is that the amount selected by 
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, chewing 
tobacco per se or flavoring composition. 
The use of insufficient quantities of bisabolene isomer composition 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 content 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, chewing tobacco compositions 
and toothpaste compositions, it is found that quantities of bisabolene 
isomer composition of our invention ranging from a small but effective 
amount, e.g., about 0.05 parts per million up to about 150 parts per 
million based on total food composition or chewing gum composition, or 
medicinal product composition or tobacco composition or chewing tobacco 
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 
where the bisabolene isomer composition of our invention 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 concentration of the 
bisabolene isomer composition of our invention in the foodstuff product. 
Food flavoring compositions containing one or more of the compounds 
prepared in accordance with the present invention preferably contain the 
bisabolene isomer composition in concentrations ranging from about 0.02% 
up to about 15% by weight of the total weight of 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 bisabolene isomer composition of our invention 
prepared in accordance with our invention with, for example, gum arabic, 
gum tragacanth, xanthan gum, carrageenan and the like, and thereafter 
spray-drying the resultant mixture whereby to obtain the particulate solid 
product. Pre-prepared flavor mixes in powder form, e.g., a fruit flavored 
or rum flavored powder mix are obtained by mixing the dried solid 
components, e.g., starch, sugar and the like and the bisabolene isomer 
composition of our invention in a dry blender until the requisite degree 
of uniformity is achieved. 
It is presently preferred to combine the bisabolene isomer composition of 
our invention with at least one of 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; 
Anethol; 
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-2,6,6-trimethylcyclohex-1-ene); 
.beta.-Damascenone (1-crotonyl-2,6,6-trimethylcyclohexa-1,3-diene); 
Beta-cyclohomocitral (2,6,6-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); 
2-(4-Hydoxy-4-methylpentyl) norbornadiene rum essence 3-hydroxy 
butyricacid; 
2-Hydroxy butyric acid; 
n-Methyl anthranilate cyclotene; 
Ethyl cyclotene; 
n-Propyl cyclotene; and 
Gin berry essence. 
Furthermore, the bisabolene composition of our invention prepared in 
accordance with the processes of our invention are capable of supplying 
and/or potentiating certain flavor and aroma notes usually lacking in many 
smoking tobacco flavors and substitute tobacco flavors provided herein. 
As used herein in regard to smoking tobacco flavors, the terms "alter" and 
"modify" in their various forms mean "supplying or imparting flavor 
character or note to otherwise bland smoking tobacco, smoking tobacco 
substitutes, or smoking tobacco flavor formulations or augmenting the 
existing flavor characteristic where a natural flavor is deficient in some 
regard or supplementing the existing flavor impression to modify its 
quality, character or taste". 
As used herein, the term "enhance" is intended to mean the intensification 
(without change in kind of quality of aroma or taste) of one or more taste 
and/or aroma nuances present in the organoleptic impression of smoking 
tobacco or a smoking tobacco substitute or a smoking 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 oriental, and Turkish tobacco-like notes on smoking and prior to 
smoking in the main stream and in the side stream 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. 
Our invention further provides improved smoking tobacco additives and 
methods whereby various oriental and Turkish tobacco notes prior to 
smoking and on smoking are imparted (in the main stream and in the side 
stream) 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 a bisabolene composition of our 
invention prepared in accordance with the processes of our invention. 
In addition to a bisabolene composition of our invention prepared in 
accordance with the processes of our invention, other flavoring and aroma 
additives may be added to the smoking tobacco materials or substitute 
therefor either separately or in admixture with a bisabolene composition 
of our invention as follows: 
(I) SYNTHETIC MATERIALS 
Beta-ethyl-cinnamaldehyde; 
Beta-cyclohomocitral; 
Eugenol; 
Dipentene; 
.beta.-Damascenone; 
.beta.-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; and 
Origanum oil. 
An aroma and flavoring concentrate containing a bisabolene composition of 
our invention and, if desired, one or more of the above-identified 
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 the taste but insofar as the 
enhancement or the imparting of natural and/or oriental notes, we have 
found that satisfactory results are obtained if the proportion by weight 
of the sum total of a bisabolene composition 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 a bisabolene composition of our invention is between 2,500 
and 15,000 ppm (0.25%-1.50%). 
Any convenient method for incorporating a bisabolene composition prepared 
in accordance with the process of our invention in the tobacco product may 
be employed. Thus, a bisabolene composition of our invention taken alone 
or along with other flavoring additives may be dissolved in a suitable 
solvent such as ethanol, pentane, diethyl ether and/or other organic 
solvents and the resulting solution may be either sprayed on the cured, 
cased and blended tobacco material or the tobacco material may be dipped 
into such solution. Under certain circumstances a solution containing a 
bisabolene composition of our invention prepared in accordance with the 
process of our invention 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, 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 smoking 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 a bisabolene composition of 
our invention in excess of the amount 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 a mixture of bisabolene derivatives prepared according to 
Example I, infra, in an amount to provide a tobacco composition containing 
800 ppm by weight of the bisabolene mixture prepared according to Example 
I, infra. 
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 prior to smoking 
which can be described as oriental-like and Turkish and on smoking in the 
main stream and the side stream as sweet oriental-like and Turkish 
tobacco-like with faint but aesthetically pleasing fruity undertones. 
While our invention is particularly useful in the manufacture of smoking 
tobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, other 
smoking tobacco products formed from sheeted tobacco dust or fines may 
also be used. Likewise a bisabolene composition 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, a bisabolene composition 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" is 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. 
It will thus be apparent that the bisabolene isomer mixtures of our 
invention can be utilized to augment, alter, modify, or enhance sensory 
properties particularly organoleptic properties of a wide variety of 
consumable materials. 
Our invention is also directed to a method for repelling at least one of 
the insect species: 
(a) Musca domestica L.(Diptera Muscidae); and 
(b) Aedes aegypti 
for a finite period of time from a three dimensional space comprising the 
step of exposing said three dimensional space to a: 
(a) Musca domestica L.(Diptera Muscidae); and/or 
(b) Aedes aegypti 
repelling concentration and quantity of a composition of matter which is 
the bisabolene composition of our invention produced according to the 
process of our invention. 
Our invention is also directed to an insect repelling soap which can repel 
any of the species of insects set forth above comprising a soap base and 
in intimate contact therewith at least one insect repellent composition of 
matter which is a bisabolene-containing composition produced by the 
process of our invention. 
Another aspect of our invention relates to the formation of the insect 
repelling articles, that is, articles containing the bisabolene 
composition of our invention useful for the repelling of the insect 
species: 
(a) Musca domestica L.(Diptera Muscidae); and/or 
(b) Aedes aegypti 
in combination with compatible polymers, e.g., high density polyethylene or 
low density polyethylene. Thus, one aspect of our invention provides a 
process for forming semiochemical-containing polymeric particles such as 
foam polymeric pellets which include a relatively high concentration of a 
bisabolene composition of our invention. 
Thus, one aspect of our invention relates to the formation of semiochemical 
polymeric pellets by means of introduction into a single screw or twin 
screw extruder of, in series, thermoplastic polymer followed by the 
semiochemical which is compatible with the thermoplastic polymer, in turn 
(optionally) followed by introduction of a gaseous blowing agent or 
blowing agent which will produce a gas which is inert to the polymer and 
to the bisabolene isomer containing composition semiochemical previously 
introduced into the extruder. 
The advantages of using a foamed polymeric particle are multiple, to wit: 
improved handling, greater retention of the semiochemical, a bisabolene 
isomer containing composition of our invention, when not in use; greater 
length of time during which release of the semiochemical from the polymer 
is at "steady state" or "zero order". 
The nature of the extruder utilized in the process of our invention to form 
the polymeric semiochemical-containing polymer particles of our invention 
may be either single screw or double screw. Thus, the types of extruder 
that can be used are disclosed at pages 246-257 and 332-349 of the Modern 
Plastics Encyclopedia, 1982-1983, published by the McGraw-Hill Publishing 
Company, the disclosure of which is incorporated by reference herein. More 
specifically, examples of extruders which are usable in carrying out one 
of the processes of our invention (with modification for introduction of 
the semiochemical) downstream from the introduction of the polymer and 
with further modification that the gaseous blowing agent is introduced 
still further downstream from a point of introduction of the 
semiochemical, e.g., a bisabolene isomer containing composition of our 
invention are as follows: 
1. The Welex "Super Twinch", 3.5" extruder manufactured by Welex 
Incorporated, 850 Jolly Road, Blue Bell, Pa. 19422. 
2. Krauss-Maffei twin screw extruder manufactured by the Krauss-Maffei 
Corporation/Extruder Division, 3629 West 30th Street South, Wichita, Kans. 
67277. 
3. Modified Sterling, Model 4000 and 5000 series extruder manufactured by 
Sterling Extruder Corporation of 901 Durham Avenue, South Plainfield, N.J. 
4. CRT ("Counter-Rotating Tangential") Twin Screw Extruder manufactured by 
Welding Engineers, Inc. of King of Prussia, Pa. 19406. 
5. The Leistritz Twin Screw Dispersion Compounder manufactured by the 
American Leistritz Extruder Corporation of 198 U.S. Route 206 South, 
Somerville, N.J. 08876. 
6. The ZSK Twin Screw Co-Rotating Extruder manufactured by the Werner & 
Pfleiderer Corporation of 6763 East Crescent Avenue, Ramsey, N.J. 07446. 
7. The Farrel Extruder manufactured by Farrel Connecticut Division, Emhart 
Machinery Group, Ansonia, Conn. 06401. 
8. The MPC/V Baker Perkins Twin Screw Extruder manufactured by the Baker 
Perkins Inc. Chemical Machinery Division of Saginaw, Mich. 48601. 
9. The Berstorff single screw, twin screw, or foam extrusion equipment 
manufactured by Berstorff Corporation, P. 0. Box 240357, 8200-A Arrowridge 
Boulevard, Charlotte, N.C. 28224. 
In producing the semiochemical, a bisabolene isomer containing composition 
of our invention, various polymers may be utilized, for example, low 
density polyethylene, high density polyethylene, polypropylene, the 
co-polymer of ethylene and vinyl acetate, and polyvinyl chloride. More 
specifically, the polymers used in the practice of our invention may be 
co-polymers of ethylene and a polar vinyl monomer selected from (a) vinyl 
acetate; (b) ethyl acrylate; (c) methyl acrylate; (d) butyl acrylate; and 
(e) acrylic acid including the hydrolyzed co-polymer of ethylene and vinyl 
acetate. Preferred co-polymers are polyethylene-vinyl acetate with about 9 
to 60% vinyl acetate and ethylene/ethyl acrylate with about 6 to 18% ethyl 
acrylate. 
Resins of the type disclosed for use as co-polymers are commercially 
available in the molding powder form. For example, ethylene vinyl acetate 
co-polymers are marketed by the E. I. DuPont de Nemours Company under the 
tradename "ELVAX.RTM." and by the Arco Polymer Division under the 
trademark "DYLAND.RTM." and by the Exxon Corporation of Linden, N.J. under 
the trademark "DEXXON.RTM.". Ethylene/ethyl acrylate co-polymers are 
market Union Carbide Corporation under the tradename "EEA RESINS.RTM.". 
The polymer is added to the single screw or twin screw extruder at a feed 
rate in the range of from about 80 up to about 300 pounds per hour while 
maintaining the temperature of the screw extruder between about 
160.degree. and about 240.degree. C. If the polymer or co-polymer powder 
is added to the extruder at a reference "barrel segment", a bisabolene 
isomer containing composition is added to the extruder under pressure 
downstream from the addition point of the polymer at one or more of 
"barrel segments" S-2, S-3, S-4, S-5, S-6, S-7, S-8 or S-9 (referring to 
FIG. 7 briefly described, supra, and described in detail, infra. 
The proportion of a bisabolene isomer composition containing composition of 
our invention to resin can vary from small but effective amounts on the 
order of about 1% of the weight of resin body up to about 45% by weight of 
the resin body. In general it is preferred to use between about 5% up to 
about 30% based on the weight of the resin body of a bisabolene isomer 
containing composition. This is an optimum amount balancing the proportion 
of a bisabolene isomer containing composition against the time period over 
which the article emits the bisabolene isomer containing composition and 
against the tendency of a bisabolene isomer containing composition to "oil 
out". This "oiling out" is specifically avoided as a result of use of the 
foaming agent discussed, infra. 
Various polymers are useful in the practice of our invention. Specific 
examples of polymers useful in the practice of our invention are as 
follows: 
(a) DYLAN.RTM. brand of low density polyethylene DYLAN.RTM. is a trademark 
owned by the Atlantic Richfield Company of Los Angeles, Calif. 
(b) DYLITE.RTM. of expandable polystyrene compositions. DYLITE.RTM. is a 
trademark of the Atlantic Richfield Company of Los Angeles, Calif. 
(c) SUPER DYLAN.RTM. is a high density polyethylene, SUPER DYLAN.RTM. is a 
trademark of the Atlantic Richfield Company of Los Angeles, Calif. 
(d) Blended polyethylene and carbon black as specifically taught in U.S. 
Pat. No. 4,369,267 issued on Jan. 18, 1983, the specification for which is 
incorporated by reference herein. 
(e) Polystyrene as disclosed in U.S. Pat. No. 4,369,227 issued on Jan. 18, 
1983, the specification for which is incorporated by reference herein. 
(f) Polyene/alpha-olefin as exemplified and disclosed in U.S. Pat. No. 
4,369,291, the specification for which is incorporated by reference 
herein. 
(g) Poly-alpha-olefins as exemplified in Canadian Letters Patent No. 
1,137,069 issued on Dec. 7, 1982, the specification for which is 
incorporated by reference herein. 
(h) Polymeric compositions as disclosed in Canadian Letters Patent No. 
1,137,068 issued on Dec. 7, 1982, the specification for which is 
incorporated by reference herein. 
(i) Poly-alpha-olefins disclosed in Canadian Letters Patent No. 1,137,067, 
the specification for which is incorporated by reference herein. 
(j) Polyolefins described in Canadian Letters Patent No. 1,137,066, the 
specification for which is incorporated by reference herein. 
(k) Polyethylene oxides as disclosed in Canadian Letters Patent No. 
1,137,065 issued on Dec. 7, 1982, the specification for which is 
incorporated by reference herein. 
(l) Olefin polymers and co-polymers as disclosed in Canadian Letters Patent 
No. 1,139,737, the disclosure of which is incorporated by reference 
herein. Canadian Patent No. 1,139,737 was issued on Jan. 18, 1983. 
(m) Polyolefins disclosed in Canadian Letters Patent No. 1,139,738, the 
disclosure of which is incorporated by reference herein. Canadian Patent 
No. 1,139,738 was issued on Jan. 18, 1983. 
(n) Chlorinated PVC as disclosed in Polymer 1982, 23 (7, Suppl.), 1051-6 
abstracted at Chem. Abstracts 97:145570y, 1982. 
(o) Polyepsilon caprolactone co-polymers made by means of alcohol initiated 
polymerization as disclosed in J.Polym.Sci.Polym.Che.Ed., 1982, 20(2), 
pages 319-26, abstracted at Chem.Abstracts, Volume 96:123625x, 1982. 
(p) Styrene acrylonitrile co-polymers as disclosed in Diss. Abstracts, Int. 
B, 1982, 42(8), 3346 and abstracted at Chem.Abstracts 96:143750n (1982). 
(q) Co-polymers of epsilon caprolactone with 1,4-butane diol as disclosed 
at Kauch. Rezine, 1982, (2), 8-9, abstracted at Chem.Abstracts, Volume 
96:182506g (1982). 
(r) Polyesters as disclosed in U.S. Pat. No. 4,326,010, the specification 
for which is incorporated by reference herein. 
(s) Chlorinated polyethylene as disclosed by Belorgey, et al, J.Polym.Sci. 
Polym. Phys. Ed., 1982, 20(2), 191-203. 
(t) Plasticized polyepsilon caprolactone co-polymers containing dimethyl 
phthalate plasticizers as set forth in Japanese Patent No. J81/147844, 
abstracted at Chem.Abstracts, Volume 96:69984y (1982), the specification 
for which is incorporated by reference herein. 
(u) Maleic anhydride modified adducts of polyepsilon caprolactone polyols 
and ethylenically unsaturated monomer as disclosed in U.S. Pat. No. 
4,137,279 issued on Jan. 30, 1979, the specification for which is 
incorporated by reference herein. 
(v) Polyurethane polymers having lactone backbones as disclosed in U.S. 
Pat. No. 4,156,067 issued on May 22, 1979, the disclosure of which is 
incorporated by reference herein. 
(w) Polyurethane polyether resins wherein the resin is obtained by reacting 
a polyfunctional lactone with a long chain polyalkylene diol and a 
urethane precursor as disclosed in U.S. Pat. No. 4,355,550 issued on Mar. 
10, 1981, the disclosure of which is incorporated by reference herein. 
(x) Resins having polyurethane backbones as disclosed in U.S. Pat. No. 
3,975,350 issued on Aug. 17, 1976, the disclosure of which is incorporated 
by reference herein. 
Downstream from the addition point of a bisabolene isomer containing 
composition, optionally, the gaseous or liquid containing blowing agent 
may be added (e.g., at barrel segments S-5, S-6, S-7, S-8, S-9 or S-10) 
using the polymer addition barrel segment as a reference barrel segment 
"S-1". Examples of gaseous blowing agents are carbon dioxide, nitrogen, 
mixtures of nitrogen and carbon dioxide in proportions of from 1 up to 99% 
by volume nitrogen and 99 down to 1% by volume carbon dioxide, helium, 
mixtures of helium and nitrogen, mixtures of helium and carbon dioxide and 
other gases which are inert at the temperature and pressure of the polymer 
at the time of the extrusion operation. Thus, gas containing oxygen or 
other reactive gases, e.g., hydrogen, should be avoided. The pressure of 
the gas blowing agent being added to the extruder at the point of addition 
may vary from about 80 up to about 150 psig. Higher pressures may be used 
without adversely affecting the usefulness of a bisabolene isomer 
containing composition containing particle. 
The feed rate range of a bisabolene isomer containing composition may be 
between about 0.5% up to about 45% by weight of the polymer. 
The die of the extruder may create rod, sheet film or ribbon. The resulting 
product may then, if desired, be pelletized to form a bisabolene isomer 
containing composition or a bisabolene isomer containing composition 
containing polymer particles or the ribbon may be used "as is" as a 
bisabolene isomer containing composition containing polymeric article of 
manufacture itself. 
In addition to the optional gaseous blowing agents (which are necessarily 
"inert" gases), blowing agents may be added at the same point on the 
extruder which will create gaseous voids in the bisabolene isomer 
containing composition-containing polymer articles of our invention and 
these "blowing agents" are well known to one having ordinary skill in the 
art. 
Examples of such non-gaseous containing materials which yield gases on 
admixture with the polymer in the extruder but which are still inert to 
the insect attractant are as follows: 
(i) Under high pressure, ethylene, methane, propane, butane, propylene, 
methyl chloride, methyl bromide, vinyl chloride and methylene dichloride 
as more specifically described in U.S. Pat. No. 2,387,730, the 
specification for which is incorporated by reference herein; 
(ii) Ordinarily liquid material such as n-pentane, isopentane, 
cyclopentane, hexane and petroleum ether fractions or halogen hydrocarbons 
such as CFC.sub.3, CF.sub.2 Cl.sub.2, CH.sub.3 Cl, CH.sub.2 C1.sub.2 
separately or in admixture with one another as set forth in U.S. Pat. No. 
3,758,425, column 4, lines 1-5, the specification for which is 
incorporated by reference herein; 
(iii) Dichlorotetrafluoroethane, tetramethylmethane, 
monochlorodifluoromethane, dichlorodifluoromethane, and 
dichlorotetrafluoroethane as specifically described in U.S. Pat. Nos. 
2,948,664 and 2,948,665 issued on Aug. 9, 1960, the specifications for 
which is incorporated by reference herein; and 
(iv) Azo bis (formamide); diazoaminobenzene; N,N'-di nitrosopentamethylene 
tetramine; N,N'-dimethyl-N-N'-dinitrosoterephthalamide; 
p,p'-oxy-bis-(benzene sulfonyl semicarbazide); azo bis-(isobutyronitrile); 
p,p'-oxy-bis (benzene sulfonyl hydrazide); p,p'-diphenyl-bis (sulfonyl 
hydrazide); benzene-sulfonyl hydrazide; m-benzene-bis (sulfonyl hydrazide) 
as more specifically described in U.S. Pat. No. 3,298,975 issued on Jan. 
17, 1967, the specification for which is incorporated by reference herein. 
The resulting extruded (and if desired pelletized) material may then be, 
for example, injection molded to form a useful article. Such injection 
molding can be carried out in accordance with the procedure as set forth 
in U.S. Pat. No. 3,268,636 issued on Aug. 23, 1966, the specification for 
which is incorporated by reference herein. 
In addition, our invention relates to candle body materials which on use 
are both insect repellent and perfuming and which contain the bisabolene 
isomer containing composition of our invention in order to repel at least 
one of the insect species: 
(a) Musca domestica L.;(Diptera Muscidae); and/or 
(b) Aedes aegypti. 
The insect repellent-perfume compositions which form part of the candle 
body materials are within the following specification: 
(I) from 5 up to 100% by weight of an efficacious perfume/insect repellent 
composition consisting essentially of a bisabolene isomer containing 
composition of our invention; and 
(II) from 0 up to 95% of a standard perfuming susbstance (not necessarily 
insect repellent) which may be one or a combination of the following 
materials: 
the methyl ester of 2,5-dihydroxy-4,6-dimethyl 
benzoic acid; 
dihydro myrcenol; 
oakmoss absolute; 
benzyl acetate; 
geraniol; 
isobornyl acetate; 
citronellyl acetate; 
para-t-butyl phenyl isovaleraldehyde; 
benzyl salicylate; 
hexyl cinnamic aldehyde; 
geranonitrile; 
patchouli oil; 
alpha-terpineol; 
tetrahydromuguol; 
phenyl ethyl alcohol; 
cedrenal; 
methyl ionone; 
cinnamyl acetate; 
benzyl benzoate; 
L-Citronellal; 
nerol; 
geranyl formate; 
geranyl acetate; 
eugenol; 
alpha Farnesene; 
beta Farnesene; 
citral; 
n-Nonanal; 
n-Octanal; and 
trans, trans delta-damascone. 
The foregoing formulae may require a solubilizing agent, e.g., the methyl 
of dihydroabietic acid (commerical name: HERCOLYN D.RTM., benzyl benzoate, 
isopropyl myristate and/or C.sub.12 -C.sub.14 isoparaffin hydrocarbons. 
The candle base composition can be standard paraffin wax, or it can be 
transparent or pastel shaded as more particularly described in U.S. Pat. 
No. 3,615,289 issued on Oct. 26, 1971 (the disclosure of which is 
incorporated by reference herein) and wherein the candle body comprises as 
the basic components a mixture of: 
(i) a thermoplastic polyamide resin formed from linoleic acid polymerized 
with a polyamine compound; 
(ii) an alkanol amide or alkanol amine; and 
(iii) a stearic acid compound. 
The weight of ratio of candle body: a bisabolene isomer containing 
composition perfumant substance of our invention may vary from about 0.8% 
up to about 10% with a range of from about 0.8% up to about 2.0% being 
preferred when no non-insect repelling perfume oil is used in conjunction 
with a bisabolene isomer containing composition of our invention; and with 
a range of from about 1.5% up to about 10% by weight of the overall 
composition being preferred when a non-insect repelling perfume oil is 
used in conjunction with the bisabolene isomer containing composition of 
our invention. 
Specifically, the polyamide may be a "Versamid" resin which is a 
thermoplastic condensation product of polymerized linoleic acid with 
various polyamine compounds such as ethylene diamine, ethylene triamine 
and the like. Specific "Versamid" compounds are "VERSAMID.RTM.900" 
"VERSAMID.RTM.930", "VERSAMID.RTM.940", "VERSAMID.RTM.948", 
"VERSAMID.RTM.950", and "VERSAMID.RTM.1635". These compounds are products 
of the Henkel Chemical Corporation of Minneapolis, Minn. 
Another substance required in the clear candle composition consists of 
about 20-55% by weight of an alkanol amine or alkanol amide prepared by 
the reaction of a fatty acid ester and amine whereby the ester and the 
amine are in substantially equal proportions, for example, compounds such 
as Barlol 12C2 (manufactured by the Barrid Chemical Company) a monoalkyl 
diethanolamine have 8 to 18% carbon atoms in the alkyl chain. A third 
component of the clear plastic candle composition comprises one or more 
stearic acid esters or a mixture of stearic acid esters and stearic acid. 
These esters include such compounds as isopropyl isostearate, butyl 
stearate and hexadecyl stearate. These stearic acid compounds serve as 
stabilizing agents which permit the ready incorporation of the insect 
repellent/perfumant compositions of our invention up to a level of 
approximately 5% (total proportion of perfume oil-insect repellent 
composition). They are carriers for the perfumant/insect repellent and may 
be used in a proportion of between 1 and 50% by weight of the composition 
although the preferable range is between 20 to 30%. In this connection it 
is possible to use up to about 10% by weight of perfumant/insect repellent 
if part of the formula is replaced by the material "Nevex 100", a product 
which is a coumarin-indene copolymer resin of very little unsaturation, 
manufactured by the Neville Chemical Company. 
Rather than being a crystalline paraffin wax the candle base of our 
invention may be an oil gel that has as its base a light mineral oil, an 
inexpensive natural oil or a combination of such oils which oil gel has a 
non-greasy surface and feel and sufficient rigidity to be self-supporting 
at room temperatures. Such a gel is disclosed in U.S. Pat. No. 3,645,705 
issued on Feb. 29, 1972, the disclosure of which is incorporated by 
reference herein. Such compositions of matter include: 
(a) from about 35% up to about 85% by weight of an oil which is normally 
liquid at room temperature chosen from the group consisting of light 
mineral oil and natural oils having iodine values substantially within the 
range of 40-135; 
(b) from about 7% up to about 40% by weight of a long chain polyamide 
having a molecular weight substantially within the range of 6000-9000 and 
a softening point substantially within the range of 18.degree. 
C.-48.degree. C.; and 
(c) from about 7% up to about 30% of an alcohol selected from the group 
consisting of 8 to 12 carbon primary alcohols. 
Such compositions may additionally include from about 1% up to about 15% of 
a methyl ester; up to about 5%by weight of stearic acid and up to about 5% 
by weight of an oxidation inhibiting agent and up to about 5% by weight of 
an acid selected from the group consisting of dimer and trimer acids. 
The following Tables I and II show the results of utilization of the 
olfactometer apparatus of FIG. 6 in testing for the attractancy or 
repellency of Musca domestica L. (Diptera Muscidae) and Aedes aegypti, 
using the bisabolene isomer containing composition of our invention. 
TABLE I 
______________________________________ 
AEDES AEGYPTI 
Composition Tested 
Insects Per Interval 
______________________________________ 
Bisabolene isomer 
0 40 26 15 79 0 6 
composition prepared 
according to 
Example I, bulked 
distillation 
fractions 7-14. 
Air 0 233 382 376 295 331 151 
______________________________________ 
TABLE II 
______________________________________ 
MUSCA DOMESTICA L.(DIPTERA MUSCIDAE) 
Composition Tested 
Insects Per Interval 
______________________________________ 
Bisabolene isomer 
0 1 8 0 6 0 0 
containing mixture 
produced according 
to Example I, 
bulked distillation 
fractions 7-14. 
Air 0 172 17 0 2 0 0 
______________________________________

DETAILED DESCRIPTION OF THE DRAWINGS 
Referring to FIG. 1, FIG. 1 is the GLC profile for the reaction product of 
Example I containing bisabolene isomers of our invention prepared by means 
of dehydration of cabreuva oil using a citric acid catalyst (Conditions: 
OV-1 capillary survey). The peak indicated by reference numeral 10 is the 
peak for trans-beta-farnesene defined according to the structure: 
##STR31## 
The peak indicated by reference numeral 11 is the peak for the compound 
having the structure: 
##STR32## 
The peak indicated by reference number 12 is the peak for gamma curcumene 
having the structure: 
##STR33## 
The peak indicated by reference number 14 is the peak for a mixture of 
cis-alpha-beta-bisabolene having the structure: 
##STR34## 
and epizonarene having the structure: 
##STR35## 
The peak indicated by reference number 16 is the peak for 
trans,trans-alpha-farnesene having the structure: 
##STR36## 
The peak indicated by reference numeral 18 is the peak for beta-bisabolene 
having the structure: 
##STR37## 
The peaks indicated by reference numerals 13A and 13B are for 
gamma-bisabolene having the structure: 
##STR38## 
The peak indicated by reference numeral 19 is for trans, alpha-bisabolene 
having the structure: 
##STR39## 
The peak indicated by reference number 17 is for delta-cadinene having the 
structure: 
##STR40## 
The peak indicated by reference number 15 is for a zonarene isomer having 
the structure: 
##STR41## 
The peak indicated by reference numeral 190 is for allofarnesene having the 
structure: 
##STR42## 
(Conditions: 50 meter.times.0.32 mm fused silica methyl silicone column 
programmed at 75.degree.-225.degree. C. at 2.degree. C. per minute). 
FIG. 2 is the GLC profile for the reaction product of Example II for a 
bisabolene isomer containing mixture prepared from cabreuva oil using a 
phosphoric acid catalyst. (Conditions: 50 meter.times.0.32 mm fused silica 
methyl silicone column programmed at 75-225.degree. C. at 2.degree. C. per 
minute). The peak indicated by reference numeral 20 is the peak for 
trans-beta-farnesene having the structure: 
##STR43## 
The peak indicated by reference numeral 22 is the peak for epizonarene 
having the structure: 
##STR44## 
The peak indicated by reference numeral 24 is the peak for 
cis-alpha-bisabolene having the structure: 
##STR45## 
The peak indicated by reference number 26 is the peak for 
trans,trans,alpha farnesene having the structure: 
##STR46## 
The peak indicated by reference number 28 is the peak for beta-bisabolene 
having the structure: 
##STR47## 
The peaks indicated by reference numbers 29A and 29B are for 
gamma-bisabolene having the structure: 
##STR48## 
The peak indicated by reference number 290 is the peak for 
trans,alpha-bisabolene having the structure: 
##STR49## 
Referring to FIGS. 3 and 4, there is provided a process for forming scented 
polymer elements (wherein the polymer may be a thermoplastic polymer such 
as low density polyethylene or polypropylene or copolymers of ethylene and 
vinyl acetate or mixtures of polymers and copolymers such as copolymers of 
ethylene and vinyl acetate and polyethylene) such as pellets useful in the 
formation of plastic particles useful in fabricating certain articles 
which may be perfumed. This process comprises heating the polymer or 
mixture of polymers to the melting point of said polymer or mixture of 
polymers, e.g., 250.degree. C. in the case of low density polyethylene. 
The lower most portion of the container is maintained at a slightly lower 
temperature and the material in the container is taken off at such 
location for delivery through the conduit. Thus, referring to FIGS. 3 and 
4, in particular, the apparatus used in producing such elements comprises 
a device for forming the polymer containing perfume, e.g., polyethylene or 
polyethylenepolyvinyl acetate or mixtures of same or polypropylene, which 
comprises a vat or container 212 into which the polymer taken alone or in 
admixture with other copolymers and the perfuming substance which is at 
least a mixture of the bisabolene isomers of our invention and other 
compatible perfumes (if desired) is placed. The container is closed by 
means of an air-tight lid 228 and clamped to the container by bolts 265. A 
stirrer 273 traverses the lid or cover 228 in an air-tight manner and is 
rotatable in a suitable manner. A surrounding cylinder 212A having heating 
coils which are supplied with electric current through cable 214 from a 
rheostat or control 216 is operated to maintain the temperature inside the 
container 212 such that the polymer in the container will be maintained in 
the molten or liquid state. It has been found advantageous to employ 
polymers at such a temperature that the viscosity will be in the range of 
90-100 sayboldt seconds. The heater 218 is operated to maintain the upper 
portion of the container 212 within a temperature range of, for example, 
220.degree.-270.degree. C. in the case of low density polyethylene. The 
bottom portion of the container 212 is heated by means of heating coils 
212A regulated through the control 220 connected thereto through a 
connecting wire 222 to maintain the lower portion of the container 212 
within a temperature range of 220.degree.-270.degree. C. 
Thus, the polymer or mixture of polymers added to container 212 is heated 
from 10-12 hours, whereafter the perfume composition or perfume material 
which contains a bisabolene isomer containing composition of our invention 
is quickly added to the melt. Generally, about 10-45 percent by weight of 
the resulting mixture of the perfumery substance is added to the polymer. 
After the perfume material is added to the container 212, the mixture is 
stirred for a few minutes, for example, 5-15 minutes and maintained within 
the temperature ranges indicated previously by the heating coil 212A. 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 conduit 232 having a multiplicity of orifices 234 adjacent to the 
lower side thereof. The outer end of the conduit 232 is closed so that the 
liquid polymer in intimate admixture with the bisabolene isomer containing 
mixture of our invention or mixture of bisabolene isomer containing 
mixture of our invention and one or more other substances, will 
continuously drop through the orifices 234 downwardly from the conduit 
232. During this time, the temperature of the polymer intimately admixed 
with the perfumery substance in the container 212 is accurately controlled 
so that a temperature in the range of from about 240.degree.-250.degree. 
C., for example, (in the case of low density polyethylene) will exist in 
the conduit 232. The regulation of the temperature through the controls 
216 and 220 is essential in order to insure temperature balance to provide 
for the continuous dripping or dropping of molten polymer intimately 
admixed with the perfume substance which is all of or which contains a 
large portion of the bisabolene isomer containing composition of our 
invention, through the orifices 234 at a rate which will insure the 
formation of droplets 236 which will fall downwardly onto a moving 
conveyor 238 caused to run between conveyor wheels 240 and 242 beneath the 
conduit 232. 
When the droplets 236 fall onto the conveyor 238, they form pellets 244 
which harden almost instantaneously and fall off the end of the conveyor 
238 into a container 250 which is advantageously filled with water or some 
other suitable cooling liquid to insure the rapid cooling of each of the 
pellets 244. The pellets 244 are then collected from the container 250 and 
utilized for the formation of other functional products, e.g., garbage 
bags which are not only pleasantly smelling and which cover unpleasant 
garbage odor but which are also insect repellent. 
FIG. 5 is a schematic cut-away elevation diagram of the extrusion and 
pelletizing apparatus useful in carrying out a process used in reducing 
our invention to practice. During the operation of said apparatus, motor 
515 drives the extruder screws located at 523A in barrel 516, the extruder 
being operated at temperatures in the range of about 150.degree. up to 
about 250.degree. C. At the beginning of the barrel, resin at source 512 
together with processing aids at location 513 is added via addition funnel 
514 into the extruder. Simultaneously (when the operation reaches "steady 
state"), a bisabolene isomer containing composition of our invention is 
added to the extruder at two or more of barrels S-3, S-4, S-5, S-6, S-7 
and S-8 of the extruder (which may be a twin screw or single screw 
extruder) at locations 518a, 518b, 518c and 518d, for example, by means of 
gear pump 523 from source 517. From source 519 into barrel segments S-5, 
S-6, S-7, S-8, S-9 and S-10, optionally, the gaseous or liquid blowing 
agents, e.g., nitrogen, carbon dioxide and the like as described, supra, 
are added simultaneously with the addition of a bisabolene isomer 
containing composition of our invention. The feed rate range of resin is 
about 80-300 pounds per hour. The feed rate range of a bisabolene isomer 
containing composition of our invention is between 1 and 35% of the feed 
rate range of the resin. The blowing agent rate range (when the blowing 
agent is used) is such that the pressure of the gas or the pressure over 
the liquid being fed into the extruder is between about 50 and 200 psig. 
If desired, the extruder ribbon or cylinder may be passed through water 
bath 520 and pelletizer 521 into collection apparatus 521a. 
FIG. 6 is a perspective schematic diagram of olfactometer apparatus of the 
prior art (U.S. Pat. No. 4,764,367 issued on Aug. 16, 1988, the 
specification for which is incorporated by reference herein) used in 
testing the efficacy of the bisabolene isomer containing compositions of 
our invention as house flies (Musca domestica L.(Diptera Muscidae)) 
repelling materials and as mosquito (Aedes aegypti) repelling materials. 
Air source 634 feeds air through line 635 through air distributor 636, 
636a, et seq, onto base plate 617 containing insect landing site 610, 
610a, et seq. The base plate 617 is separated from the spacer plate 629 
for the air lines 636 whereby the air lines 636 are held in place at 
positions 631, 631a, et seq. Air exits through line 633a using exhaust fan 
633. Simultaneously, with the air being fed through line 636, 636a, et 
seq., from air source 634, light is guided through light guides 652 and 
652a using light source 651 powered by electric power source 650. The base 
plate 617 is separated from the spacer plate 629 also for the light guide 
652, 652a, et seq., whereby the light guide 652, 652a, et seq., are held 
in place at positions 631, 631a, et seq. 
The olfactometer is assisted with computer apparatus shown in schematic 
form and block flow diagram form using reference numeral 620, 621, 623, 
624 and 639. Dampers 611a, 611b, et seq., hold base plate 617 in place 
horizontally. 
When an insect is de-anesthetized and in action, e.g., a house fly (Musca 
domestica L.(Diptera Muscidae)) lands on a sensor landing site, the 
landing is recorded electrically through the sensor 610, 610a, et seq.. 
The sensor 610, 610a, et seq., causes an electrical impulse to proceed 
through wire 618 and then through wire 619 using electrical power source 
639 to a multi-channel A-D converter 623 which is associated with program 
tape storage 624, printer 620 and digital computer associated with modem 
and main frame 621. 
Referring to FIGS. 7 and 8 are a series of graphs depiciting in three 
dimensions (in a rectangular mode for the "X" and "Y" axes) showing the 
relative repellency of bisabolene isomer containing compositions as well 
as air per se. The graphs are based on experiments run for a period of one 
hour with six intervals of 10 minutes each. 
Thus, referring to FIG. 7, FIG. 7 shows relative repellency against house 
flies (Musca domestica L.(Diptera Muscidae)) of bisabolene isomer 
containing compositions of Example I (the graph indicated by reference 
numeral 62) as compared to the attractiveness of air itself (the graph for 
which is indicated by reference numeral 64). 
The data supporting the graph of FIG. 7 is set forth in Table II, supra, 
and in the following Table IV. 
TABLE IV 
______________________________________ 
MUSCA DOMESTICA L.(DIPTERA MUSCIDAE) 
Reference 
Composition 
Numeral 
Tested For Graph INSECTS PER INTERVAL 
______________________________________ 
Bisabolene 62 0 1 8 0 6 0 0 
Isomer Con- 
taining 
Composition 
of Example I, 
(bulked, 
distillation) 
fractions 7-14. 
Air 64 0 172 17 0 2 0 0 
______________________________________ 
Referring to FIG. 8, FIG. 8 shows the relative repellency of bisabolene 
isomer containing compositions with reference to clean air (as an 
"attractant" against the species of mosquito (Aedes aegypti). Thus, the 
repellency against Aedes aegypti of bisabolene isomer containing 
compositions is shown in the graph indicated by reference numeral 82. The 
attractancy for Aedes aegypti of clean air (relative humidity 75-80%) is 
shown by the graph indicated by reference numeral 84. The data supporting 
the graphs set forth in FIG. 8 are set forth in the following Table III. 
TABLE III 
______________________________________ 
AEDES AEGYPTI 
Ref- 
erence 
Com- Numeral 
position 
For 
Tested Graph INSECTS PER INTERVAL 
______________________________________ 
Bisabolene 
82 0 40 26 15 79 0 6 
Isomer 
Containing 
Com- 
position 
of Example 
I, (bulked, 
distillation) 
fractions 
7-14. 
Air 84 0 233 382 376 295 331 151 
______________________________________ 
DETAILED DESCRIPTION OF THE DRAWINGS 
A preferred embodiment of our invention set forth in FIGS. 9-18 comprises 
an ellipsoidally-shaped detergent tablet 830 containing a solid plastic 
core 832 which can be fabricated from, for example, polyethylene, 
polypropylene, nylon or any polymer capable of having therein microvoids 
from which an insect repelling substance, e.g., bisabolene isomer 
containing compositions of Example I or II will be controllably 
transported from the plastic core into and through the soap cake over a 
reasonable period of time during the use of the soap cake. Such polymers 
can be microporous polymers such as those described in U.S. Pat. No. 
4,247,498 issued on Jan. 27, 1981, the specification for which is 
incorporated herein by reference. Surrounding the central plastic core 
containing insect repellent 832 is detergent 830' which is in the solid 
phase at ambient conditions, e.g., room temperature and atmospheric 
pressure. Examples of workable detergents 830' are "elastic" detergents 
such as those described in U.S. Pat. No. 4,181,632 issued on Jan. 1, 1980, 
the disclosure of which is incorporated herein by reference, or 
"transparent" soaps such as those set forth in U.S. Pat. No. 4,165,293 
issued on Aug. 21, 1979, the disclosure of which is incorporated herein by 
reference. Other examples of the detergent 830' useful in our invention 
are those set forth as "variegated soaps" in Canadian Letters Patent No. 
1,101,165 issued on May 19, 1981, the disclosure of which is incorporated 
by reference herein. 
On use of the soap tablet 830 or detergent bar, the insect repellent agent, 
e.g., the bisabolene isomer containing composition of Example I or II, 
originally located in plastic core 832 is transported at a steady state 
from core 832 through core surface 831 through the detergent 830' and 
finally through the surface of the detergent bar at, for example, 833, 
834, 835 and 836. 
The detergent bar or tablet 830 of our invention may be of any geometric 
shape, for example, a rectangular parallelpiped tablet as shown in FIGS. 
13, 14 and 15 containing solid plastic core 839. The insect repellent 
located in solid plastic core 839 on use of the detergent bar passes 
through at steady state, surface 832 of FIG. 14, detergent 838 and finally 
surface 839 at, for example, locations 840, 841, 842 and 843. The 
environment surrounding the detergent bar on use thereof is then treated 
with insect repellent, e.g., the bisabolene isomer containing composition 
of Example I or II, at 843, 844 and 845. Optionally, aromatizing agent can 
also be contained (in addition to the bisabolene isomer containing 
composition of our invention) in the detergent bar and so the environment 
surrounding the detergent bar on use thereof would also be aesthetically 
aromatized at 843, 844 and 845, for example, with aromatizing agents in 
addition to the bisabolene isomer containing composition of our invention. 
It must be understood that the bisabolene isomer containing composition of 
our invention is an aromatizing agent as well as an insect repellent agent 
in and of itself so additional aromatizing agent is not really necessary. 
As shown in FIGS. 16, 17 and 18, the plastic core of the detergent tablet 
830 may have a single finite void at its center 851 (of FIGS. 17 and 18) 
in which the insect repellent agent and optionally, the aromatizing agent 
is contained. The plastic core is then a shell 848 having outer surface 
852 (shown in FIGS. 17 and 18). The insect repellent agent (and 
optionally, any additional aromatizing agent) contained in the void in the 
plastic core permeates through shell 848, past surface 852 at a steady 
state, through the detergent 847 and to the environment at, for example, 
856, 857, 858 and 859. 
In addition to the insect repellent contained in the core, e.g., core 839 
or core void, the core can also contain other materials for therapeutic 
use, for example, bacteriostats, deodorizing agents and the like which are 
compatible with insect repellents such as the bisabolene isomer containing 
composition of our invention. In the alternative, the plastic core of the 
detergent tablet of FIGS. 16, 17 and 18 may have an empty single finite 
void at its center 851 with the insect repellent contained in the shell 
848. 
At the end of the use of the detergent tablet, the hollow core or the solid 
core can be used as an insect repelling and aroma imparting or air 
freshener household article. In addition, depending on the ratio of the 
volume of the void 851, to the solid part of the detergent tablet of FIGS. 
16, 17 and 18, the detergent tablet of FIGS. 16, 17 and 18 can be so 
fabricated that it will float on the surface of the liquid in which it is 
being used and this physical attribute has certain obvious advantages. 
The following Examples I and II illustrate methods of our invention used to 
manufacture the bisabolene isomer containing compositions of our 
invention. Examples following Example II serve to illustrate organoleptic 
utilities of the bisabolene isomer containing compositions of our 
invention as well as insect repellent utilities of the bisabolene isomer 
containing compositions of our invention. 
All parts and percentages given herein are by weight unless otherwise 
specified. 
EXAMPLE I 
Preparation of Bisabolene Isomer Containing Composition 
##STR50## 
wherein in the composition defined according to the structure: 
##STR51## 
which is a mixture in the mixture in each of the compounds one of the 
dashed lines is a carbon-carbon double bond and each of the other of the 
dashed lines represent carbon-carbon single 
Into a 5 liter reaction flask equipped with stirrer, thermometer, reflux 
condenser and water take-off apparatus (Bidwell trap) is placed 2000 ml 
PRIMOL.RTM. (mineral oil manufactured by the Exxon Company of Linden, 
N.J.); and 100 grams of citric acid. With stirring the resulting mixture 
is heated to a temperature in the range of 160.degree.-165.degree. C. Over 
a period of one hour while maintaining the reaction temperature at 
160.degree.-166.degree. C., one kilo of Cabreuva oil containing 86.5% 
nerolidol having the structure: 
##STR52## 
is added to the reaction mass while removing water simultaneously to the 
addition of the nerolidol. At the end of the one hour addition period, 
additional water is removed. 
While maintaining the reaction mass at 166.degree. C., the reaction mass is 
refluxed while removing additional water of reaction. The refluxing takes 
place for an additional one hour. 
The reaction mass is then cooled to 40.degree. C. and transferred to a 12 
liter separatory funnel containing 2 liters of n-hexane. The phases are 
separated. The organic phase is washed with 200 ml 5% sodium hydroxide. 
The organic phase is then washed with an additional 500 ml saturated 
sodium chloride. The organic phase is then distilled on a rushover column 
at 120.degree.-131.degree. C. at 5.8-6.6 mm/Hg. The resulting product is 
then fractionally distilled yielding the following fractions: 
______________________________________ 
Vapor Liquid Vacuum 
Fraction Temp. Temp. mm/Hg. 
No. (.degree. C.) 
(C.) Pressure 
______________________________________ 
1 85/103 140/140 2.3/3.01 
2 95 136 2.9 
3 92 136 2.9 
4 102 138 2.8 
5 102 138 2.8 
6 108 144 2.9 
7 108 144 2.8 
8 108 144 2.8 
9 110 140 3.2 
10 112 142 2.9 
11 114 144 3.0 
12 114 142 2.8 
13 120 148 2.9 
14 124 205 2.9. 
______________________________________ 
The resulting product contains a majority of isomers of bisabolene having 
the structures: 
##STR53## 
In addition, the resulting product also contains compounds having the 
structures: 
##STR54## 
and the composition is shown in the GLC profile of FIG. 1 as described in 
detail, supra. 
The resulting product has an intense, natural, dry, floral, opoponax aroma, 
with floral, freesia, fruity, citrus, bergamot, mango and opoponax 
topnotes (bulked distillation fractions 7-14). 
EXAMPLE II 
Preparation of Bisabolene Isomer Containing Composition 
##STR55## 
wherein in the product defined according to the structure: 
##STR56## 
a mixture, in the mixture in each of the compounds one of the dashed lines 
is carbon-carbon double bond and each of the other of the dashed lines is 
a carbon-carbon single bond. 
Into a 500 ml reaction flask equipped with stirrer, thermometer, condenser 
and Dean Stark water removal trap is placed 15 grams of phosphoric acid 
and 150 ml PRIMOL.RTM.. The reaction mass is heated to 
160.degree.-165.degree. C. with stirring. Over a period of one hour, 150 
grams of Cabreuva oil containing 87% nerolidol is added to the reaction 
mass, while maintaining the reaction mass at 158.degree.-164.degree. C. 
The reaction mass is then cooled to room temperature. 
The reaction mass is then placed in a separatory funnel and is washed with 
two 100 ml volumes of water followed by 100 ml of 1%-sodium hydroxide. 
The organic phase is then distilled at a vapor temperature of 135.degree. 
C. and vacuum of 2.5 mm/Hg. yielding a product containing a majority of 
bisabolene isomers having the structures: 
##STR57## 
The reaction product GLC profile is set forth in FIG. 2 and described in 
detail, supra. 
The resulting reaction product has an intense, natural, dry, floral, 
opoponax aroma, with floral, freesia, fruity, citrus, bergamot, mango and 
opoponax topnotes. 
EXAMPLE III 
Preparation of Ginger Fragrance Formulation 
The following ginger fragrance formulations are prepared: 
______________________________________ 
TS BY WEIGHT 
EXAMPLE EXAMPLE 
INGREDIENTS (IIIA) (IIIB) 
______________________________________ 
Ginger Essential Oil 
12 12 
Lime Distilled Essential Oil 
8 8 
Orange Essential Oil 
8 8 
Vanillin 4 4 
Cinnamaldehyde 6 6 
Isoeugenol 4 4 
Eugenol 2 2 
Terpineol 6 6 
Hexyl Cinnamic Aldehyde 
3.2 3.2 
Bisabolene Isomer Con- 
6 0 
taining Composition of 
Example I, bulked 
distillation, 
fractions 7-14 
Bisabolene Isomer 
0 6 
Containing Composition 
of Example II 
______________________________________ 
The ginger fragrance formulation of Example (IIIA) can be described as 
"ginger, having natural, dry, floral and opoponax undertones, with floral, 
freesia, fruity, citrus, bergamot, mango and opoponax topnotes". 
The ginger formulation of Example (IIIB) can be described as "ginger, 
having natural, dry, floral, and opoponax undertones, with floral, 
freesia, fruity, citrus, bergamot, mango and opoponax topnotes". 
EXAMPLE IV 
Preparation 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 V below. Each of the cosmetic powder compositions has an 
excellent aroma as described in Table V below: 
TABLE V 
______________________________________ 
Substance Aroma Description 
______________________________________ 
Bisabolene isomer-con- 
A natural, dry, floral, opoponax 
taining composition 
aroma, with floral, freesia, 
produced according to 
fruity, citrus, bergamot, mango 
Example I, bulked 
and opoponax topnotes. 
distillation, 
fractions 7-14. 
Bisabolene isome-con- 
A natural, dry, floral, opoponax 
taining composition 
aroma, with floral, freesia, 
of Example II. fruity, citrus, bergamot, mango 
and opoponax topnotes. 
Perfume composition 
Ginger, having natural, dry, 
of Example III(A). 
floral and opoponax undertones, 
with floral, freesia, fruity, 
citrus, bergamot, mango and 
opoponax topnotes. 
Perfume composition 
Ginger, having natural, dry, 
of Example III(B). 
floral, and opoponax undertones, 
with floral, freesia, fruity, 
citrus, bergamot, mango and 
opoponax 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) with aroma nuances as set forth in Table V 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 V of Example IV. They are prepared by adding 
and homogeneously mixing the appropriate quantity of substance set forth 
in Table V of Example IV below in the liquid detergent The detergents all 
possess excellent aromas as set forth in Table V of Example IV, the 
intensity increasing with greater concentrations of substance as set forth 
in Table V of Example IV. 
EXAMPLE VI 
Preparation of Colognes and Handkerchief Perfumes 
Compositions as set forth in Table V 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 V of Example IV are imparted 
to the colognes and to the handkerchief perfumes at all levels indicated. 
EXAMPLE VII 
Preparation of Soap Compositions 
One hundred grams of soap chips [per sample] (IVORY.RTM., produced by the 
Procter & Gamble Company of Cincinnati, Ohio), are each mixed with one 
gram samples of substances as set forth in Table V 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 V of Example IV. 
EXAMPLE VIII 
Preparation of Solid Detergent Compositions 
Detergents are prepared using the following ingredients according to 
Example I of Canadian Patent No. 1,007,948: 
______________________________________ 
Ingredient Percent by Weight 
______________________________________ 
"NEODOL .RTM. 45-11 
12 
(a C.sub.14 -C.sub.15) 
alcohol ethoxylated with 
11 moles of ethylene oxide 
Sodium carbonate 55 
Sodium citrate 20 
Sodium sulfate water 
q.s. 
brighteners 
______________________________________ 
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 V of Example IV. Each of the 
detergent samples has an excellent aroma as indicated in Table V of 
Example IV. 
EXAMPLE IX 
Utilizing the procedure of Example I at column 15 of U.S. Pat. No. 
3,632,396, non-woven cloth substrates useful as dryer-added fabric 
softening articles of manufacture are prepared wherein the substrate, the 
substrate coating and 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.2-22 HAPS 
22% isopropyl alcohol 
20% anti-static agent 
1% of one of the substances as set forth 
in Table V 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 V of Example IV, consist of a substrate coating having a weight of 
about 3 grams per 100 square inches of substrate; a first coating 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 V 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 
dryer on operation thereof in each case using said dryer-added fabric 
softener non-woven fabrics and these aroma characteristics are described 
in Table V of Example IV. 
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: 
______________________________________ 
Ingredients Weight Percent 
______________________________________ 
Dioctyl sebacate 0.05 
Benzyl alcohol 0.10 
Dow Corning 473 fluid 
0.10 
(prepared by the Dow Corning 
Corporation) 
Tween 20 surfactant 0.03 
(prepared by ICI America 
Corporation) 
One of the perfumery substances 
0.10 
as set forth in Table V of 
Example IV. 
______________________________________ 
The perfuming substances as set forth in Table V of Example IV add aroma 
characteristics as set forth in Table V 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 Procter 
& 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.). 
GAFQUAT.RTM.755N 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. 
The resulting material is then mixed and cooled to 45.degree. C. and 0.3 
weight percent of perfuming substance as set forth in Table V 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 V of Example IV. 
EXAMPLE XII 
Tobacco Formulations 
Tobacco mixtures are 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 .05 
Ethyl valerate .05 
Maltol 2.00 
Cocoa extract 26.00 
Coffee extract 10.00 
Ethyl alcohol 20.00 
Water 41.90 
______________________________________ 
The above stated tobacco flavor formulation is applied at the rate of 1.0% 
to all of the cigarettes produced using the above tobacco formulation. The 
cigarettes are divided into groups as follows: 
Group A--treated with 500 ppm of the bisabolene isomer containing mixture 
produced according to Example I, bulked distillation Fractions 7-14. 
Group B--treated with 500 ppm of the bisabolene isomer containing 
composition of Example II. 
Group C--not treated with any compounds (control cigarettes). 
The control cigarettes and the experimental cigarettes of Groups A and B, 
which contain bisabolene isomer containing compositions produced according 
to Examples I and II, are evaluated by paired comparison and the results 
are as follows: 
The experimental cigarettes of Groups A and B are found to have more body 
in tobacco smoke flavor and a fuller body sensation. The tobacco notes are 
described as "Turkish-like" with oriental nuances both prior to and on 
smoking in the main stream and the side stream. The flavor of the tobacco 
on smoking is, in addition, sweeter and more aromatic. All of the 
cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate 
flavor. 
EXAMPLE XIII 
Blackberry Jam 
At the rate of 0.15 ppm, a composition of bisabolene-containing isomers 
produced according to Example I, bulked distillation Fractions 7-14 is 
added to SMUCKER.RTM. Blackberry Preserves. The resulting blackberry 
preserves retain their original fresh flavor but also have interesting 
ginger nuances after being removed from the vacuum jar in which it was 
originally marketed and the original blackberry flavor with natural-like 
nuances is retained for a period of six weeks when the resulting preserves 
are refrigerated in a standard kitchen refrigerator. 
EXAMPLE XIV 
Paraffin Wax Candle Body 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Paraffin wax 95.0 
Bisabolene isomer-containing 
5.0 
composition produced according 
to Example I, bulked distillation 
Fractions 7-14. 
______________________________________ 
The paraffin wax is intimately admixed at 150.degree. C. and 10 atmospheres 
pressure with the bisabolene isomer composition of Example I in an 
autoclave with intensive shaking. The autoclave pressure is maintained 
with a nitrogen atmosphere. At the end of the period of one hour the 
autoclave is depressurized, the autoclave is opened and the resulting 
mixture is poured into cylindrical candle molds containing wicks. 
The resulting candles on use evolve an aesthetically pleasing aroma and, in 
addition, give rise to efficacious house fly repellency. The candles are 
effective in preventing house flies from entering a room in which one 
candle is burning for a period of 10 minutes, the said room having 
dimensions of 6'.times.15'.times.15' having a 3'.times.3' open portal 
adjacent to a house fly-infested region in the month of August in 
Highlands, N.J., next to a very swampy area. 
EXAMPLE XIII 
Blackberry Jam 
At the rate of 0.15 ppm, a composition of bisabolene-containing isomers 
produced according to Example I, bulked distillation Fractions 7-14 is 
added to SMUCKER.RTM. Blackberry Preserves. The resulting blackberry 
preserves retain their original fresh flavor but also have interesting 
ginger nuances after being removed from the vacuum jar in which it was 
originally marketed and the original blackberry flavor with natural-like 
nuances is retained for a period of six weeks when the resulting preserves 
are refrigerated in a standard kitchen refrigerator. 
EXAMPLE XIV 
Paraffin Wax Candle Body 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Paraffin wax 95.0 
Bisabolene isomer-containing 
5.0 
composition produced according 
to Example I, bulked distillation 
Fractions 7-14. 
______________________________________ 
The paraffin wax is intimately admixed at 150.degree. C. and 10 atmospheres 
pressure with the bisabolene isomer composition of Example I in an 
autoclave with intensive shaking. The autoclave pressure is maintained 
with a nitrogen atmosphere. At the end of the period of one hour the 
autoclave is depressurized, the autoclave is opened and the resulting 
mixture is poured into cylindrical candle molds containing wicks. 
The resulting candles on use evolve an aesthetically pleasing aroma and, in 
addition, give rise to efficacious house fly repellency. The candles are 
effective in preventing house flies from entering a room in which one 
candle is burning for a period of 10 minutes, the said room having 
dimensions of 6'.times.15'.times.15' having a 3'.times.3' open portal 
adjacent to a house fly-infested region in the month of August in 
Highlands, N.J., next to a very swampy area. 
EXAMPLE XV 
A transparent candle base is produced by intimately admixing the following 
ingredients: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
VERSAMID .RTM. 1635 
34.0 
Barlol 12C2 51.0 
Butyl Stearate 3.5 
NEVEX .RTM. 100 5.0 
SPAN .RTM. 60 1.5 
Isopropyl Isostearate 
4.0 
Isopropyl Myristate 
4.0 
______________________________________ 
The foregoing mixture is placed in an autoclave and intimately admixed with 
a perfume-scent repellent composition which is a bisabolene isomer 
composition produced according to Example II. 
The autoclave is sealed and heated to 180.degree. C. under 15 atmospheres 
pressure and maintained with vigorous shaking for a period of five hours. 
At the end of the five hour period, the autoclave is depressurized (being 
under a nitrogen pressure atmosphere) and the autoclave is opened and the 
contents are then poured into cyclindrical candle molds 4" in height and 
2" in diameter containing 0.125" wicks. The resulting candles have 
efficacious insect repellencies and have aesthetically pleasing aromas on 
use. 
The candles are effective in preventing the following insects: 
(a) Musca domestica L.(Diptera Muscidae); and/or 
(b) Aedes aegypti 
from entering a room in which two candles have been burning for 15 minutes, 
the said room having dimensions of 6'.times.15'.times.15' and having a 
3'.times.3' open portal adjacent a house fly and mosquito infested region 
in Highlands, N.J., in the month of August in the temperate zone. 
EXAMPLE XVI 
A study was conducted to evaluate the efficacy of candles which are 
designated "A", "B" and "C" in repelling house flies (Musca domestica 
L.(Diptera Muscidae)). 
Candle "A" contained 95% paraffin Wax and 5% of the following composition: 
______________________________________ 
100 parts by weight of a bisabolene isomer containing 
composition produced according to 
Example I, bulked distillation, 
Fractions 7-14; and 
700 parts by weight of a perfume composition containing 
the following ingredients: 
Ingredients Parts by Weight 
______________________________________ 
Perfume mixture of essential 
oils and chemicals, to wit: 
the methyl ester of 2,5-dihydroxy- 
83.8 
4,6-dimethyl benzoic acid; dihydro 
myrcenol; oakmoss absolute; benzyl 
acetate; geraniol; isobornyl acetate; 
citronellyl acetate; para-t-butyl 
phenyl isovaleraldehyde; benzyl 
salicylate; hexyl cinnamaic aldehyde; 
geranonitrile; patchouli oil; 
alpha-terpineol; tetrahydromuguol; 
phenyl ethyl alcohol; cedrenal; 
methyl ionone; cinnamyl acetate; 
and benzyl benzoate 
Solvent: 
the methyl ester of dihydroabietic 
4.00 
acid 
______________________________________ 
Candle "B" contained 90% Paraffin Wax and 10% citronella oil. 
Candle "C" contained only Paraffin Wax. 
The candles are allowed to burn for 20 minutes and the number of house 
flies repelled from a house fly-infested room is recorded for the next 60 
minutes with the following equipment and procedure. 
MATERIALS 
Test Chamber 
The evaluation was conducted in a 28.3 cubic meter chamber with airing 
ports. A screened cage measuring 15 cm.times.15 cm.times.47.5 cm was 
attached inside an upper airing port, and a screened repellency 
observation cage measuring 15 cm.times.15 cm.times.32.5 cm was attached 
outside the upper airing port. The two cages were held together by a 
Masonite plate which fit firmly in the airing port. A 4cm hole located in 
the center of each Masonite plate provided an escape for the test insects. 
A barrier was used to close the hole. 
Attractant 
A caged mouse was used as an attractant and was placed inside the chamber 
in the larger section of the repellency cage. 
Test Insect 
Adult house flies (Musca domestica) are test insects. 
Procedure 
For each replicate, 75 to 100 adult house flies were removed from the 
rearing cage by means of a vacuum aspirator, and transferred by carbon 
dioxide anesthesia to the inner cage containing the mouse. The assembled 
cage was placed in one of the upper ventilation ports of the chamber. 
For each experimental situation the test insects were transferred to a 
clean cage containing the mouse. A house fly candle was placed centrally 
on the chamber floor and burned for 20 minutes before initiating the 
repellency counts. The maximum period for the repellency counts was 60 
minutes. The first repellency count was made at 10 minutes after the 
burning ended, and subsequent counts were taken at 5 minute intervals 
thereafter. The number of house flies repelled were those escaping to the 
outside cage. For the control counts were made in a similar manner, but no 
candle was burned. 
The same three candles were used for all four replicates. Between 
replicates the chamber was exhausted, the Kraft paper flooring for the 
chamber was replaced, and the two screened repellency cages were submerged 
in hot detergent water, rinsed and dried. 
Result 
The average percent of house flies repelled for each five minute exposure 
period through 60 minutes is reported in the following Table VI: 
TABLE VI 
__________________________________________________________________________ 
House Flies Repelled At Five Minute Time Intervals 
20 Minutes Post Exposure 
Cumulative Number of 
Number of 
House Flies Repelled at Indicated 
Overall 
Sample Replicate 
House Flies 
10 15 20 25 30 35 40 45 50 55 60 Percent 
__________________________________________________________________________ 
Untreated 1 93 1 1 1 1 1 2 2 3 3 4 6 6.45 
(no candle 
2 67 0 1 2 3 5 6 6 6 6 7 7 10.45 
used) 3 86 2 2 2 3 4 6 6 7 7 7 7 8.14 
4 90 2 3 3 3 3 4 5 5 5 5 5 5.56 
Total 336 5 7 8 10 13 17 19 21 21 23 25 
Average Percent 1 2 2 3 4 5 6 6 6 7 7 7.44 
A 1 108 2 5 7 8 8 8 8 10 10 10 12 11.11 
2 95 0 5 5 6 7 7 9 11 12 12 16 16.84 
3 86 3 6 8 8 10 10 11 11 12 12 13 15.12 
4 96 2 3 5 6 9 11 11 14 16 17 17 17.71 
Total 385 7 19 25 28 34 36 39 46 50 51 58 
Average Percent 2 5 6 7 9 9 10 12 13 13 15 15.06 
B 1 80 4 5 7 7 8 8 9 9 9 10 11 13.75 
2 100 2 4 5 6 7 10 11 11 11 12 12 12.00 
3 87 2 2 3 4 5 5 6 6 6 6 7 8.04 
4 91 2 4 5 6 6 6 7 7 7 9 10 10.99 
Total 358 10 15 20 23 26 29 33 33 33 37 41 
Average Percent 3 4 6 6 7 8 9 9 9 10 11 11.45 
C 1 79 6 8 8 8 8 8 8 8 8 9 10 12.66 
2 86 3 5 5 6 6 6 6 6 7 7 8 9.30 
3 92 2 4 4 5 7 7 7 7 7 7 8 8.70 
4 91 0 1 1 2 2 2 4 6 7 7 9 9.89 
Total 348 11 18 18 11 23 23 25 27 29 30 35 
Average Percent 3 5 5 6 7 7 7 8 8 9 10 10.06 
__________________________________________________________________________ 
The results of this experiment show that the candle containing the 
bisabolene isomer mixture (2.5% of the total weight) is about 40% more 
efficacious from an insect repellency standpoint than a candle containing 
10% citronella oil . . . and in addition, such candles containing the 
bisabolene isomer composition on burning yield an aesthetically pleasing 
scent which is totally unlike the 10% citronella oil-containing candle 
which yields an aesthetically displeasing scent.