Tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile, organoleptic uses thereof and process for preparing same

Described is the tetrahydro-5-isopropyl-2-methyl-thiophene acetonitrile of our invention having the structure: ##STR1## and organoleptic uses thereof in augmenting or enhancing the aroma or taste of perfume compositions, colognes, perfumed articles, foodstuffs and chewing gums.

BACKGROUND OF THE INVENTION 
This invention relates to tetrahydro-5-isopropyl-2-methyl-2-thiophene 
acetonitrile of our invention having the structure: 
##STR2## 
produced by reaction of thioacetic acid with geranonitrile, a mixture of 
compounds having the structures: 
##STR3## 
and uses thereof in augmenting or enhancing the aroma or taste of 
consumable materials including perfume compositions, colognes, perfumed 
articles, foodstuffs and chewing gums. 
There has been considerable work performed relating to substances which can 
be used to impart (or alter, modify or enhance) fragrances and aromas 
and/or tastes to (or in) perfume compositions, colognes, perfumed 
articles, foodstuffs and chewing gums. These substances are used to 
diminish the use of natural materials, some of which may be in short 
supply and/or to provide more uniform properties in the finished product. 
Powerful, long-lasting, natural buchu leaf, tomato leaf, herbaceous, basil, 
minty and grapefruit-like aromas with natural "ontiga", tomato leaf, minty 
and grapefruit-like undertones are highly desirable to many types of 
perfume compositions, perfumes and perfumed articles, particularly herbal 
fragrances and herbal fragranced soaps and detergents. 
Grapefruit and nootkatone-like aroma and taste nuances are highly desirable 
in the creation of flavors for foodstuffs and chewing gums.

DETAILED DESCRIPTION OF THE DRAWINGS 
FIG. 1 is the GLC profile for the crude reaction product of Example I 
containing the compound having the structure: 
##STR8## 
The peak indicated by reference numeral 10 is the peak for the compound 
having the structure: 
##STR9## 
FIG. 2 is the GLC profile for fraction 6 of the distillation of the 
reaction product of Example I. (Conditions: SE-30 column programmed at 
100.degree.-220.degree. C. at 8.degree. C. per minute). The peak indicated 
by reference numeral 20 is the peak for the compound having the strucutre: 
##STR10## 
Referring to FIGS. 5 and 6; a thermoplastic polymer, e.g., polyethylene is 
heated to about 220.degree.-250.degree. C. in a container 212 of the kind 
illustrated in FIGS. 5 and 6. The formulation containing the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
is then quickly added to the liquified thermoplastic polymer. The lid 228 
is put in place and the agitating means 273 is actuated. The temperature 
is maintained at about 225.degree. F. and the mixing is continued for 
about 5-15 minutes. The valve "V" is then opened to allow flow of the 
molten thermoplastic polymer enriched with the fragrance containing the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
to exit through the orifices 234. The liquid falling through the orifices 
234 solidifies almost instantaneously upon impact with moving cooled 
conveyor 238. The thermoplastic polymer beads or pellets 224 having 
pronounced aromas which are aesthetically pleasing are thus formed. 
The conveyor 238 is moved using conveyor rollers 240 and 242. The vessel 
212 is heated using heating coils 212A using power input supplies 
indicated by reference numerals 214, 216, 224, 222, 220 and 226. The 
solidified beads containing the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
are indicated by 244 traveling into container 245 where they are used for 
subsequent processing. The conveyor is cooled using a cooling device 
indicated by reference numerals 248, 256, 215 and 254. 
THE INVENTION 
The invention relates to the compound defined according to the structure: 
##STR11## 
as well as uses thereof in augmenting or enhancing the aroma or taste of 
consumable materials. Such consumable materials are perfume compositions, 
perfumes, colognes, foodstuffs and chewing gums. This invention also 
relates to the process for preparing the compound having the structure by 
means of reacting geranonitrile, a mixture of compounds having the 
structures: 
##STR12## 
with thioacetic acid according to the reaction: 
##STR13## 
This reaction is carried out at a temperature of 60.degree.-80.degree. C. 
over a period of about 1 and about 5 hours. The mole ratio of 
geranonitrile, the mixture of compounds having the structures: 
##STR14## 
to thioacetic acid is between about 1:0.5 and about 0.5:1 with a slight 
excess of mixture of compounds having the structures: 
##STR15## 
to thioacetic acid being preferred (e.g., 3:2.5). 
At the end of the reaction the reaction mass is washed with base and 
fractionally distilled in order to recover the compound having the 
structure: 
##STR16## 
also shown as having the structure: 
##STR17## 
one or more isomers. 
The compound having the structure: 
##STR18## 
distills at 108.degree. C. and 3 mm/Hg. pressure. 
The compound having the structure: 
##STR19## 
has a natural buchu leaf, tomato leaf, herbaceous, basil, minty and 
grapefruit-like aroma with natural "ontiga", tomato leaf, minty and 
grapefruit-like undertones from a fragrance standpoint. From a flavor 
standpoint the compound having the structure: 
##STR20## 
has a green, minty, grapefruit-like and nookatone aroma and taste profile 
at 1 ppm. 
The tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our 
invention having the structure: 
##STR21## 
is useful as an olfactory agent and can be incorporated into a wide 
variety of compositions each of which will be enhanced or augmented by its 
natural buchu leaf, tomato leaf, herbaceous, basil, minty and 
grapefruit-like aroma with natural tomato leaf, minty and grapefruit-like 
undertones. 
The tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our 
invention can be added to perfume compositions as a pure compound or can 
be added to mixtures of materials in fragrance imparting compositions to 
provide a desired fragrance character to a finished perfume material. The 
perfume and fragrance compositions obtained according to this invention 
are suitable in a wide variety of perfumed articles and can also be used 
to enhance, modify or reinforce natural fragrance materials. It will thus 
be appreciate that the tetrahydro-5-isopropyl-2-methyl-2-thiophene 
acetonitrile of our invention is useful as an olfactory agent and 
fragrance. 
The term "perfume composition" is used herein to mean a mixture of 
compounds including, for example, natural essential oils, synthetic 
essential oils, alcohols, aldehydes, ketones, esters, lactones, nitriles 
(other than the nitrile of our invention) and frequently hydrocarbons 
which are admixed so that the combined odors of the individual components 
produce a pleasant or desired fragrance. Such perfume compositions usually 
contain (a) the main note or "bouquet" or foundation stone of the 
composition, (b) modifiers which round off and accompany the main note, 
(c) fixatives which include odorous substances which lend a particular 
note to the perfume throughout all stages of evaporation and substances 
which retard evaporation and (d) topnotes which are usually low-boiling, 
fresh-smelling materials. Such perfume compositions of our invention can 
be used in conjunction with carriers, vehicles, solvents, dispersants, 
emulsifiers, surface active agents, aerosol propellants and the like. 
In perfume compositions, the olfactory components contribute their 
particular olfactory characteristics but the overall effect of the perfume 
composition will be the sum of the effect of each ingredient. This, the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
can be used to alter, augment, modify or enhance the aroma characteristics 
of a perfume composition or a perfumed article, for example, by 
highlighting or moderating the olfactory reaction contributed by another 
ingredient of the composition. 
The amount of the tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile 
of our invention which will be effective in perfume compositions depends 
upon many factors including the other ingredients, the amounts and the 
effects which are desired. It has been found that perfume compositions 
containing as much as 40% or as little as 0.005% by weight of the mixture 
of the tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of this 
invention, or even less, can be used to impart a powerful, long-lasting, 
natural buchu leaf, tomato leaf, herbaceous, basil, minty and 
grapefruit-like aroma with natural "ontiga" tomato leaf, minty and 
grapefruit-like undertones to soaps, cosmetics and other products. The 
amount employed will depend upon considerations of cost, nature of the end 
product, the effect desired in the finished product and particular 
fragrance sought. 
The tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our 
invention as disclosed herein can be used alone in a fragrance modifying 
composition or in a perfume composition as an olfactory component in 
detergents (e.g., anionic, cationic, nonionic or zwitterionic solid or 
liquid detergents, and soaps, space deodorants; perfumed plastics; perfume 
compositions; colognes, bath preparations such as bath oils, bath salts; 
hair preparations such as lacquers, brilliantines, pomades and shampoos; 
fabric softener compositions, fabric softener articles such as BOUNCE.RTM. 
(manufactured by the Proctor & Gamble Company of Cincinnati, Ohio), 
cosmetic preparations such as creams, powders, deodorants, hand lotions, 
sun screens, powders such as talcs, dusting powders, face powders and the 
like. When the tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of 
our invention is used in perfumed articles such as the foregoing, it can 
be used in amounts of 0.01% or lower and generally it is preferred not to 
use more than about 2% in the finished perfumed article since the use of 
too much will tend to unbalance the toal aroma and will needlessly raise 
the cost of the article. Thus, in summary, in perfumed articles, the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
having the structure: 
##STR22## 
may be used in the range of from about 0.01% up to about 2.0%. 
When the tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our 
invention having the structure: 
##STR23## 
is used as a food flavor adjuvant, or is used to augment or enhance the 
flavor or aroma characteristics of foodstuffs, the nature of the 
co-ingredients included with said 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
in formulating the product composition will also to augment the 
organoleptic characteristics of the ultimate foodstuff treated therewith. 
As used herein in regard to flavors, the term "augment" in its various 
forms means "supplying or imparting flavor, character or note to otherwise 
bland, relatively tasteless substances or augmenting the existing flavor 
characteristics wherein natural flavor is deficient in some regard or 
supplementing the existing flavor impression to modify its quality, 
character or taste". 
As used herein in regard to food flavors, the term "enhance" is used 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 "foodstuffs" includes both solids and liquids and 
ingestible materials or chewable but non-ingestible materials such as 
chewing gum. Such materials usually do, but need not have nuritional 
value. Thus, foodstuffs include soups, convenience foods, beverages, 
gelatin desserts, dairy products, candies, vegetables, cereals, soft 
drinks, snacks and the like. 
Substances suitable for use herein as co-ingredients or flavoring adjuvants 
are well known in the art for such use, being extensively described in the 
relevant literature. Apart from the requirements that any such materials 
be organoleptically compatible with the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
having the structure: 
##STR24## 
non-reactive with the tetrahydro-5-iospropyl-2-methyl-2-thiophene 
acetonitrile of our invention and "ingestibly acceptable" and thus, 
non-toxic or otherwise non-deleterious, nothing particularly critical 
resides in the selection thereof. Accordingly, such materials which may in 
general be characterized as flavoring adjuvants or vehicles comprise 
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 
hydroxyanisole (mixture of 2 and 3 tertiary-butyl-4-hydroxyanisole), 
butylated hydroxy toluene (2,6di-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, skin milk powder, hexoses, pentoses, disaccharides, e.g., sucrose, 
corn syrup and the like. 
Surface active agents include emulsifying agents, e.g., fatty acids such as 
capric acid, caprylic acid, palmitic acid, myristic acid and the like, 
mono- and diglycerides of fatty acids, lecithin, defoaming and 
flavor-dispersing agents such as sorbitan monostearate, potassium 
stearate, hydrogenated tallow alcohol and the like. 
Conditioners include compounds such as bleaching and maturing agents, e.g., 
benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch 
modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, 
propylene oxide, succinic anhydride and the like buffers and neutralizing 
agents, e.g., sodium acetate ammonium bicarbonate, ammonium phosphate, 
citric acid, lactic acid, vinegar and the like; colorants, e.g., carminic 
acid, cochineal, tumeric and curcuma and the like; firming agents such as 
aluminum sodium sulfate, calcium chloride and calcium gluconate; 
texturizers, anti-caking agents, e.g., aluminum calcium sulfate and 
tribasic calcium phosphate; enzymes, yeast foods, e.g., calcium lactate 
and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric 
phosphate, ferrousgluconate 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-methylbutyric acid, propionic acid, valeric acid, 
2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones and 
aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methyl 
carbinol, acrolein, n-butanal, crotonal, diacetyl, 
beta,beta-dimethyl-acrolein, n-hexanal, 2-hexenal, cis-3-hexenal, 
2-heptanal, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone, 
methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols such as 
1-butanal, benzyl alcohol, 1-borneol, trans-2-buten-1ol, ethanol, 
geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol, 
3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol, 
p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol, 
phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate; esters such as 
butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl 
butyrate, ethyl caproate,ethyl cinnamate, ethyl crotonate, ethyl formate, 
ethyl isobutyrate, ethyl isovalerate, ethyl alpha-methylbutyrate, ethyl 
propionate, ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 
2-hexenyl butyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, 
methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate, 
alpha-methylbutyrate, propyl acetate, amyl acetate, amyl butyrate, benzyl 
salicylate, dimethyl anthranilate, ethyl methylphenylglycidate, ethyl 
succinate, isobutyl cinnamate and terpenyl acetate; essential oils, such 
as jasmin absolute, rose absolute, orris absolute, lemon essential oil, 
Bulgarian rose, yara yara, natural raspberry oil and vanilla; lactones; 
sulfides, e.g., methyl sulfide and other materials such as maltol, 
pulegone mercaptan, alpha-phellandrene, ethyl maltol, 
2,2,4,4,6,6-hexamethyl-S-trithiane, 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, 
be capable of providing an environment in which the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
can be dispersed or admixed to provide a homogeneous medium. In addition, 
selection of one or more flavoring adjuvants, as well as the quantities 
thereof, will depend upon the precise organoleptic character desired in 
the finished product. Thus, in the case of flavoring compositions, 
ingredient selection will vary in accordance with the foodstuffs to which 
the flavor and aroma are to be imparted. In contradistinction, in the 
preparation of solid products, e.g., simulated foodstuffs, ingredients 
capable of providing normally solid compositions should be selected such 
as various cellulose derivatives. 
As will be appreciated by those skilled in the art, the amount of the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
employed in a particular instance can vary over a relatively wide range 
whereby to its desired organoleptic effects having reference to the nature 
of the product are achieved. Thus, correspondingly greater amounts would 
be necessary in those instances wherein the ultimate food composition to 
be flavored is relatively bland to the taste, whereas relatively minor 
quantitites may suffice for purposes of enhancing the composition merely 
deficient in natural flavor or aroma. The primary equipment is that the 
amount selected to be effective, i.e., sufficient to alter the 
organoleptic characteristics of the parent composition, whether foodstuff 
per se of flavoring composition. 
The use of insufficient quantities of the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
will, of course, substantially vitiate any possibility of obtaining the 
desired results while excess quantitites 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 contex of the 
present invention consistent with the obtention of desired flavoring 
effects. 
Thus, and with respect to ultimate food compositions, it is found that 
quantities of the tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile 
of our invention ranging from a small but effective amount, e.g., about 
0.1 parts per million up to abou 50 parts per million by weight based on 
total composition (more preferably, from about 0.2 ppm up to about 10 ppm) 
are suitable. Concentrations in excess of the maximum quantity stated are 
not normally recommended since they fail to prove commensurate with 
enhancement of organoleptic properties. In those instances wherein the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
are added to the foodstuff as an integral component of a flavoring 
composition it is, of course, essential that the total quantity of 
flavoring composition employed be sufficient to yield an effective 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
in the foodstuff product. 
Food flavoring compositions prepared in accordance with the present 
invention preferably contain the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
in concentrations ranging from about 0.1% up to about 15% by weight based 
on 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. Altenatively, flavoring 
compositions in the form of particulate solids can be conveniently 
prepared by mixing the tetrahydro-5-isopropyl-2-methyl-2-thiophene 
acetonitrile of our invention with, for example, gum arabic, gum 
tragacanth, carageenan and the like, and thereafter spray-drying the 
resultant mixture whereby to obtain the particular solid product. 
Pre-prepared flavor mixed in powder form, e.g., a fruit flavored powder 
mix, is obtained by mixing the dried solid components, e.g., starch, sugar 
and the like, and the tetrahydro-5-isopropyl-2-methyl-2-thiophene 
acetonitrile of our invention in a dry blender until the requisite degree 
of uniformity is achieved. 
It is presently preferred to combine with the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
the following adjuvants: 
p-Hydroxybenzyl acetone; 
Geraniol; 
Acetaldehyde; 
Maltol; 
Ethyl methyl phenyl glycidate; 
Benzyl acetate; 
Dimethyl sulfide; 
Vanillin; 
Methyl cinnamate; 
Ethyl perlargonate; 
Methyl anthranilate; 
Isoamyl acetate; 
Isobutyl acetate; 
Alpha-ionone; 
Ethyl butyrate; 
Acetic acid; 
Gamma-undecalactone; 
Naphthyl ethyl ether; 
Diacetyl; 
Ethyl acetate; 
Anethole; 
Isoamyl butyrate; 
Cis-3-hexenol-1; 
2-Methyl-2-pentenoic acid; 
Elemecine(4-allyl-1,2,6-trimethoxy benzene); 
Isoelemecine(4-propenyl-1,2,6-trimethoxybenzene); 
2-(4-Hydroxy-4-methylpentyl)norbornadiene prepared according to U.S. 
application for patent, Ser. No. 461,703 filed on April 17, 1974, now U.S. 
Pat. No. 3,886,289; 
Natural blackcurrentjuice; 
Buchu leaf oil; 
Alpha-phellandrene; 
Cis-3-hexen-1-ol; 
Terpinenol-4; 
Ethyl maltol; 
Methyl benzoate; 
Benzaldehyde; 
Coriander oil; 
Alpha-ionone; 
Ethyl heptanoate; 
Ethyl anthranilate; 
Cinnamic alcohol; 
Amyl valerinate; 
Cinnamyl propionate; 
Rhodinyl acetate; 
Methyl beta-hydroxy butyrate; 
Ethyl beta-hydroxy butyrate; 
2-Phenyl-3-carboethoxyfuran; 
Cyclohexyl disulfide; 
Grapefruit oil 
Nootkatone; 
Bergamot oil; 
Citral; 
Amyl alcohol; 
5-Phenyl-4-pentenal; 
5-Phenyl-2-pentenal; 
Allyl caproate; 
2-(n-Pentyl)thiazole; 
2-(i-Butyl)thiazole; 
2-(i-Propyl)thiazole; 
2-(n-propyl)thiazole; 
2-Phenyl-4-pentenal; 
2-Phenyl-4-pentenaldimethylacetal; 
Methional; 
4-Methylthiobutanal; 
2-Ethyl-3-acetylpyrazine; 
Tetramethyl pyrazine; 
2-Methyl pyrazine; 
Trans-2-hexenal; 
Hydrolyzed vegetable protein; 
Monosodium glutamate; 
Dimethyl disulfide; 
Methyl propyl disulfide; 
Methyl propenyl disulfide; 
Methyl allyl disulfide; 
Allyl propyl disulfide; 
Propyl propenyl disulfide; 
Dipropyl disulfide; 
Diallyl disulfide; 
Propyl propenyl trisulfide; 
Thiopropanal-S-oxide; 
Thiobutanal-S-oxide; 
Thioethanal-S-oxide; 
Thiohexanal-S-oxide; and 
Propyl propene thiosulfonate. 
The following Example I is given to illustrate a method of preparing the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention. 
The examples following Example II set forth methods whereby the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
is utilized for its organoleptic properties. 
It will be understood that these examples are illustrative and the 
invention is not to be considered as restricted thereto except as 
indicated in the appended claims. 
EXAMPLE I 
Preparation of Tetrahydro-5-Isopropyl-2-Methyl-2-Thiophene Acetonitrile 
Reaction 
##STR25## 
Into a 1 liter reaction vessel equipped with thermometer, stirrer, 
condenser and heating mantle is placed 455.0 grams (3.0 moles) of 
geranonitrile, a mixture of compounds having the structures: 
##STR26## 
The geranonitrile is heated with stirring to 65.degree. C. Dropwise, over 
a period of 60 minutes, while maintaining the reaction temperature at 
65.degree. C., 190.0 grams (2.5 moles) of thioacetic acid is added to the 
reaction mass. 
The reaction mass is then stirred at 65.degree.-70.degree. C. of one hour. 
The reaction mass is then heated and maintained at 70.degree.-75.degree. 
C. for a period of 1.25 hours. 
The reaction mass is the cooled and 200 cc toluene is added thereto. The 
organic layer is separated from the aqueous phase and the organic layer is 
washed with one 200 cc portion of 20% aqueous sodium hydroxide. The 
resulting washed product is then distilled on a 6" stone packed column 
yielding the following fractions: 
______________________________________ 
Vapor Liquid Vacuum Weight 
Fraction Temp. Temp. mm/Hg. of 
No. (.degree.C.) 
(.degree.C.) 
Pressure 
Fraction 
______________________________________ 
1 90/100 120/125 3.0/3.0 
15.0 
2 100 135 3.5 15.0 
3 105 145 3.5 40.0 
4 105 160 3.5 50.0 
5 108 175 3.5 60.0 
6 108 177 3.0 30.0 
7 108 179 3.0 45.0 
8 108 181 3.0 20.0 
______________________________________ 
The resulting distillation product is then bulked and redistilled on a 
spinning band column yielding the following fractions: 
______________________________________ 
Vapor Liquid Vacuum Weight 
Fraction Temp. Temp. mm/Hg of 
No. (.degree.C.) 
(.degree.C.) 
Pressure 
Fraction 
______________________________________ 
1 90/95 110/141 2.5/2.5 
10.0 
2 95 150 2.5 30.0 
3 95 150 2.5 5.0 
4 108 158 2.5 30.0 
5 108 165 2.5 24 0 
6 108 165 2.5 29.0 
7 108 170 2.5 27.0 
8 108 195 2.8 36.0 
______________________________________ 
FIG. 1 is the GLC profile for the crude reaction product. The peak 
indicated by reference numeral 10 is the peak for the compound having the 
structure: 
##STR27## 
FIG. 2 is the GLC profile for fraction 6 of the second distillation 
(Conditions: SE-30 column programmed at 100.degree.-220.degree. C. at 
8.degree. C. per minute). The peak indicated by reference numeral 20 is 
the peak for the compound having the structure: 
##STR28## 
FIG. 3 is the NMR spectrum for the compound having the structure: 
##STR29## 
FIG. 4 is IR spectrum for the compound having the structure: 
##STR30## 
The compound having the structure: 
##STR31## 
has a natural natural buchu leaf, tomato leaf, herbaceous, basil, minty 
and grapefruit-like aroma with natural "ontiga", tomato leaf, minty and 
grapefruit-like undertones from a fragrance standpoint. 
From a flavor standpoint the compound having the structure: 
##STR32## 
has a green, minty, grapefruit-like and nootkatone-like aroma and taste 
profile. 
EXAMPLE II (A) 
Impregnated Plastics And Air Fresheners 
Scented polyethylene pellets having pronounced natural buchu leaf, tomato 
leaf, herbaceous, basil, minty and grapefruit-like aromas with natural 
"ontiga" tomato leaf, minty and grapefruit-like undertones are prepared as 
follows: 
75 Pounds of polyethylene having a melting point of about 220.degree. F. is 
heated to about 230.degree. F. in a container of the kind illustrated in 
FIGS. 5 and 6. 12.5 Pounds of tetrahydro-5-isopropyl-2-methyl-2-thiophene 
acetonitrile having the structure: 
##STR33## 
prepared according to Example I, supra, are then quickly added to the 
liquified polyethylene. The lid 228 is put in place and the agitating 
means 273 are actuated. The temperature is maintained at about 225.degree. 
F. and the mixing is continued for about 15 minutes. The valve "V" is then 
opened to allow flow of the molten polyethylene enriched with the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile containing 
material through the orifices 234 (whereby such material exits through 
orifices 234). The liquid falling through the orifices 234 solidifies 
almost instantaneously upon impact with the moving cooled conveyor 238. 
Polyethylene beads or pellets 224 having a pronounced aroma as set forth 
above are thus formed. These pellets may be called "master pellets". 
50 Pounds of the aroma-containing "master pellets" are then added to 1000 
pounds of unscented and untreated polyethylene powder and the mass is 
heated to the liquid state. The liquid is molded into thin sheets or 
films. The thin sheets or films have pronounced aromas as set forth, 
supra. The sheets or films are cut into strips 1/4" in width .times.3" in 
length and employed in standard air freshening apparatus. 
On operation of the standard air freshening apparatus is a room air 
freshener, after 4 minutes, the room has an aesthetically pleasing aroma 
as set forth, supra. 
EXAMPLE II (B) 
Treated Plastics And Air Freshener 
100 Pounds of polypropylene are heated to about 300.degree. F. 15 Pounds of 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile prepared 
according to Example I are added to the liquified polypropylene. The 
procedure is carried out in the apparatus shown in FIGS. 5 and 6. After 
mixing for about 8 minutes, the valve "V" is opened to allow the exit of 
polypropylene mixture which has been treated with the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile whereby solid 
pellets having pronounced aromas described as "natural buchu leaf, tomato 
leaf, herbaceous, basil, minty and grapefruit-like with natural "ontiga", 
tomato leaf, minty and grapefruit-like undertones" are formed on the 
conveyor. The pellets thus obtained are then admixed with about 20 times 
their weight of unscented polypropylene and untreated polypropylene and 
the mixture is heated and molded into "spaghetti" tows. The "spaghetti" 
tows are cut into small cylinders approximately 0.1 inches in length 
.times.0.2 inches in diameter. The cylinders have strong and pleasant 
aromas as described, supra. 
The cylinders are used in standard air freshening apparatus to produce 
aesthetically pleasing aromas as set forth, supra, with no foul odors in 
environments surrounding the air freshener apparatus. 
A portion of the cylinders are ground into small particles to be used in 
the deodorant stick of Example II(C). 
EXAMPLE II(C) 
Deodorant Stick 
A deodorant stick composition is prepared containing the following 
materials: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Propylene Glycol 65.00 
Sodium stearate 7.00 
Distilled water 23.75 
IRGSAN .RTM. DP-300 0.25 
(2,4,4-trichloro-2'-hydroxy 
diphenyl ether, manufactured 
by the Ciba Geigy Chemical 
Company and the trademark of 
the Ciba Geigy Chemical Company 
of Hastings on Hudson, New York) 
Ground polymer containing 
tetrahydro-5-isopropyl-2- 
methyl-2-thiophene aceto- 
4.00 
nitrile produced according 
to Example II(B), supra. 
______________________________________ 
The ingredients are combined without the ground polymer and are heated to 
75.degree. C. These ingredients are mixed and continued to be heated until 
the sodium stearate has dissolved. The resulting mixture is cooled to 
40.degree. C. and the ground fragrance-containing polymer is added to and 
mixed at 40.degree. C. until a suspension is formed. The resulting 
suspension is cooled and formed into sticks and the deodorant sticks 
exhibit a pleasant fresh green aroma when utilized in the axillary areas 
of a human being. 
EXAMPLE III 
Grapefruit Flavor Formulation 
The following formulation is prepared: 
______________________________________ 
Parts by Weight 
Example Example 
Ingredients III(A) III(B) 
______________________________________ 
Grapefruit oil 92.0 92.0 
Bergamot oil 2.0 2.0 
Citral 3.0 3.0 
n-Amyl alcohol 1.0 1.0 
Ethyl acetate 1.0 1.0 
2-Methyl-4-phenyl-1- 
pentanol produced 
according to U.S. 
Pat. No. 4,632,831 1.5 0.0 
2-Methyl-4-phenyl-1- 
pentanol acetate 
produced according to 
U.S. Pat. No. 4,632,831 
0.0 1.8 
Tetrahydro-5-isopropyl-2- 
methyl-2-thiophene acetonitrile 
produced according to 
Example I, supra 2.0 2.0 
______________________________________ 
When the above grapefruit formulations are added to water at the rate of 1% 
, an excellent grapefruit drink is prepared. The 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention 
gives a minty, natural green nuance to the above two formulations thereby 
rendering them more "natural-like". Furthermore, the formulation are both 
"nootkatone" like with aesthetically pleasing red grapefruit notes. 
When the above formulations are modified by adding to them 1.5 parts by 
weight of any of the following ingredients a yet more natural grapefruit 
peel aroma and taste is imparted thereto: 
(1,3-diethylacetonyl)(1,3-diisopropylacetonyl)sulfide; 
3-methyl-thio-4-heptanone; 3-propyl-thio-4-heptanone; 
3-(methallylthio)-2,6-dimethyl-4-heptanone; 
3-crotylthio-2,6-dimethyl-4-heptanone; and 
3-allylthio-2,6-dimethyl-4-heptanone. 
EXAMPLE IV 
(A.) The following concentrate is prepared: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Geraniol 1.00 
Ethyl methyl phenyl glycidate 
3.50 
Nootkatone 5.00 
Ethyl pelargonate 5.00 
Isoamyl acetate 4.00 
Vanillin 2.00 
Isobutyl-2-methyl-pentenoate 
3.00 
2-Methyl-4-phenyl-1-pentanol 
1.00 
2-Methyl-4-phenyl-1-pentanol acetate 
1.13 
Tetrahydro-5-isopropyl-2- 
methyl-2-thiophene 
acetonitrile 1.00 
______________________________________ 
(B.) One volume of the concentrate prepared in Part "A", supra, is 
dissolved in four volumes of propylene glycol and the mixture is added to 
a hard candy melt at the rate of 1.5 ounces of the concentrate solution 
per 100 pounds of melt. After the finished candy has been produced, it is 
found to have an excellent grapefruit flavor. When the candy is compared 
with candy made under the same conditions but without the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention, 
it is found to have an inferior grapefruit flavor. Indeed, the grapefruit 
flavor used with the tetrahydro-5-isopropyl-2-methyl-2-thiophene 
acetonitrile of our invention is markedly superior than without the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile of our invention. 
EXAMPLE V 
A. Powder Flavor Formulation 
Twenty grams of the flavor formulation of Example III is emulsified in a 
solution containing 300 grams gum acacia and 700 grams of water. The 
emulsion is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. 
of air with an inlet temperature of 500.degree. F., an outlet temperature 
of 200.degree. F. and a wheel speed of 50,000 rpm. 
B. Sustained Release Flavor 
The following mixture is prepared: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Liquid grapefruit flavor 
20 
of Example III 
Propylene glycol 9 
CAB-O-SIL .RTM. M-5 
5 
(Brand of silica produced by 
the Cabot Corporation of 
125 High Street, Boston, 
Mass. 02110); 
Physical Properties: 
Surface area: 200 m.sub.2 /gram 
Nominal particle size: 
0.012 microns 
Density: 2.3 lbs./cu.ft. 
______________________________________ 
The CAB-O-SIL.RTM. is dispersed in the liquid grapefruit flavor composition 
of Example III with vigorous stirring thereby resulting in a viscous 
liquid. 71 Parts by weight of the powder flavor composition of Part "A", 
supra, is then blended into said viscous liquid with stirring at 
25.degree. C. for a period of thirty minutes resulting in a dry, 
free-flowing, sustained release grapefruit flavored powder. 
EXAMPLE VI 
Ten parts by weight of 50 Bloom pigskin gelatin is added to ninety parts by 
weight of water at a temperature of 150.degree. C. The mixture is agitated 
until the gelatin is completely dissolved and the solution is cooled to 
120.degree. F. Twenty parts by weight of the liquid grapefruit flavor 
composition of Example III is added to the solution which is then 
homogenized to form an emulsion having a particle size typically in the 
range of 5-40 microns. The material is kept at 120.degree. F. under which 
conditions the gelatin will not jell. 
Coacervation is induced by adding slowly and uniformly forty parts by 
weight of a 20% aqueous solution of sodium sulfate. During coacervation, 
the gelatin molecules are deposited uniformly about each oil droplet as a 
nucleus. 
Gelatin is effected by pouring the heated coacervate mixture into 1,000 
parts by weight of 7% aqueous solution of sodium sulfate at 65.degree. F. 
The resulting jelled coacervate may be filtered and washed with water at 
temperatures below the melting point of gelatin to remove the salt. 
Hardening of the filtered cake, in this example, is effected by washing 
with 200 parts by weight of 37% solution of formaldehyde in water. The 
cake is then washed to remove residual formaldehyde. 
EXAMPLE VII 
Chewing Gum 
One hundred parts by weight of chicle are mixed with four parts by weight 
of the flavor prepared in accordance with Example V. Three hundred parts 
of sucrose and one hundred parts of corn syrup are added. Mixing is 
effected in a ribbon blender with jacketed walls of the type manufactured 
by the Baker Perkins Company. 
The resultant chewing gum blend is then manufactured into strips one inch 
in width and 0.1 inches in thickness. The strips are cut into lengths of 
three inches each. On chewing, the chewing gum has a pleasant long-lasting 
grapefruit flavor. 
EXAMPLE VIII 
Chewing Gum 
One hundred parts by weight of chicle are mixed with eighteen parts by 
weight of the flavor prepared in accordance with Example VI. Three hundred 
parts of sucrose and one hundred parts of corn syrup are then added. 
Mixing is effected in a ribbon blender with jacketed walls of the type 
manufactured by the Baker Perkins Company. 
The resultant chewing gum is then manufactured into strips one inch in 
width and 0.1 inches in thickness. The strips are cut into lengths of 
three inches each. On chewing, the chewing gum has a pleasant, 
long-lasting grapefruit flavor. 
EXAMPLE IX 
Toothpaste Formulation 
The following separate groups of ingredients are prepared: 
______________________________________ 
Parts by Weight Ingredient 
______________________________________ 
Group "A" 
30.200 Glycerine 
15.325 Distilled water 
.100 Sodium benzoate 
.125 Saccharin sodium 
.400 Stannous flurode 
Group "B" 
12.500 Calcium carbonate 
37.200 Dicalcium phosphate dihydrate 
Group "C" 
2.000 Sodium n-lauroyl sarcosinate 
(foaming agent) 
Group "D" 
1.200 Flavor material of Example V 
______________________________________ 
Procedure: 
1. The ingredients in Group "A" are stirred and beated in a steam jacketed 
kettle to 160.degree. F. 
2. Stirring is continued for an additional three to five minutes to form a 
homogeneous gel. 
3. The powders of Group "B" are added to the gel, while mixing until a 
homogeneous paste is formed. 
4. With stirring, the flavor of "D" is added and lastly, the sodium 
n-lauroyl sarcosinate. 
5. The resultant slurry is then blended for one hour. The completed paste 
is then transferred to a three roller mill and then homogenized and 
finally tubed. 
The resulting toothpaste, when used in a normal toothbrushing procedure, 
yields a pleasant grapefruit flavor of constant strong intensity 
throughout said procedure (1-1.5 minutes). 
EXAMPLE X 
Chewable Vitamin Tablets 
The flavor material produced according to the process of Example VI is 
added to a chewable vitamin tablet formulation at the rate of ten grams 
per kilogram which chewable vitamin tablet formation is prepared as 
follows: 
In a Hobart mixer, the following materials are blended to homogenity: 
______________________________________ 
Grams/1000 
Ingredients Tablets 
______________________________________ 
Vitamin C (ascorbic acid) 
as ascrobic acid-sodium 
70.110 
ascorbate mixture 1:1 
Vitamin B.sub.1 (thiamine mononitrate 
as ROCOAT .RTM. thiamine mononitrate 
4.000 
33-1/3% Hoffman LaRoche) 
Vitamin B.sub.2 (riboflavin) as 
ROCOAT .RTM. riboflavin 33-1/3% 
5.000 
Vitamin B.sub.6 (pyridoxine hydro- 
chloride) as ROCOAT .RTM. phridoxine 
4.000 
hydrochloride 33-1/3% 
Niacinamide as ROCOAT .RTM. 
niacinamide 33-1/3% 33.000 
Calcium pantothenate 11.500 
Vitamin B.sub.12 (cyanocobalamin) as 
Merck 0.1% in gelatin 3.500 
Vitamin E (d1-alpha tocopheryl 
acetate) as dry Vitamin E acetate 
6.600 
33-1/3% 
d-Biotin 0.044 
Flavor of Example VI (as indicated 
above) 
Certified lake color 5.000 
Sweetener, sodium saccharin 
1.000 
Magnesium stearate lubricant 
10.000 
Mannitol q.s. to make 500.000 
______________________________________ 
Preliminary tablets are prepared by slugging with flat-faced punches and 
grinding the slugs to 14 mesh. 13.5 Grams dry Vitamin A acetate and 0.6 
grams Vitamin D are then added as beadlets. The entire blend is then 
compressed using concave punches at 0.5 punches each. 
Chewing of the resultant tablets yields a pleasant, long-lasting, 
consistently strong grapefruit flavor for a period of 12 minutes. 
EXAMPLE XI 
Herbal Perfume Formulation 
The following mixtures are prepared: 
______________________________________ 
Parts by Weight 
Example Example 
Ingredients XI(A) XI(B) 
______________________________________ 
Oakmoss absolute (50% in 
diethyl phthalate) 20 20 
Alpha-methyl-3,4,methylene- 
dioxyhydrocinnamic 10 10 
aldehyde 
Methyl dihydrojasmonate 
100 100 
Coumarin 20 20 
Musk ketone 80 80 
Isocyclocitral (10% in 
diethyl phthalate) 10 10 
Galbanum oil (10% in diethyl 
phthalate) 6 6 
Rosemary oil 10 10 
Pine needle oil 60 60 
Fir balsam absolute (10% in 
diethyl phthalate) 10 10 
Bergamot oil 60 60 
Lemon oil 14 14 
Benzyl acetate 468 468 
Linalool 80 80 
Indole (10% in diethyl phthalate) 
6 6 
Undecalactone (10% in diethyl 
phthalate) 12 12 
2-methyl-4-phenyl-1-pentanol 
(produced according to 
U.S. Letters Patent 12 0 
No. 4,632,831) 
2-methyl-4-phenyl-1-pentanol 
acetate (produced according to 
U.S. Letters Patent 0 20 
No. 4,632,831) 
Tetrahydro-5-isopropyl-2- 
methyl-2-thiophene acetonitril 
produced according to 
10 5 
Example I, supra. 
______________________________________ 
The addition of this herbal formulation of the 
tetrahydro-5-isopropyl-2-methyl-2-thiophene acetonitrile imparts to this 
herbal formulation an excellent natural buchu leaf, tomato leaf, 
herbaceous, basil, minty and grapefruit-like topnotes, with natural 
"ontiga", tomato leaf, minty and grapefruit-like undertones. Accordingly, 
the formulations can be described as "herbaceous with natural buchu leaf, 
tomato leaf, herbaceous, basil, minty and grapefruit-like topnotes and 
natural "ontiga", tomato leaf, minty and grapefruit-like undertones". 
EXAMPLE XII 
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 I below. Each of the cosmetic powder compositions has an 
excellent aroma as described in Table I below. 
TABLE I 
______________________________________ 
Substance Aroma Description 
______________________________________ 
Tetrahydro-5-isopropyl-2- 
A natural buchu leaf, 
methyl-2-thiophene aceto- 
tomato leaf, herbaceous, 
nitrile produced according 
basil, minty and grapefruit- 
to Example I. like aroma profile with 
natural "ontiga", tomato 
leaf, minty and 
grapefruit-like undertones. 
Perfume formulations 
Herbaceous with natural 
of Example XI buchu lead, tomato leaf, 
herbaceous, basil, minty and 
grapefruit-like topnotes and 
natural "ontiga", tomato 
leaf, minty and 
grapefruit-like undertones. 
______________________________________ 
EXAMPLE XIII 
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 Apr. 
6, 1976 incorporated by reference herein) with aroma nuances as set forth 
in Table I of Example XII are prepared containing 0.10%, 0.15%, 0.20%, 
0.25%, 0.30% and 0.35% of the substance set forth in Table I of Example 
XII. They are prepared by adding and homogeneously mixing the appropriate 
quantity of substance set forth in Table I of Example XII in the liquid 
detergent. The detergents all possess excellent aromas as set forth in 
Table I of Example XII, the intensity increasing with greater 
concentrations of substance as set forth in Table I of Example XII. 
EXAMPLE XIV 
Preparation of Colognes and Handkerchief Perfumes 
Compositions as set forth in Table I of Example XII 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 
definite fragrances as set forth in Table I of Example XII are imparted to 
the colognes and to the handkerchief perfumes at all levels indicated. 
Example XVI 
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 I of Example XII until 
homogeneous compositions are obtained. In each of the cases, the 
homogeneous compositions are heated under eight atmospheres pressure at 
180.degree. C. for a period of three hours and the resulting liquids are 
placed into soap molds. The resulting soap cakes, on cooling, manifest 
aromas as set forth in Table I of Example XII. 
EXAMPLE XVII 
Preparation of Solid Detergent Compositions 
Detergents are prepared using the following ingredients according to 
Example I of Canadian Pat. No. 1,007,948 (incorporated by reference 
herein): 
______________________________________ 
Ingredient Percent by Weight 
______________________________________ 
"NEODOL .RTM. 45-11 (a C.sub.14 -C.sub.15 
alcohol ethoxylanted with 
12 
11 moles of ethylene oxide) 
Sodium carbonate 55 
Sodium citrate 20 
Sodium sulfate, water 
brighteners q.s. 
______________________________________ 
This detergent is a phosphate-free detergent. Samples of 100 grams each of 
this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams of each of 
the substances as set forth in Table I of Example XII. Each of the 
detergent samples has an excellent aroma as indicated in Table I of 
Example XII. 
EXAMPLE XVIII 
Utilizing the procedure of Example I at column 15 of U.S. Pat. No. 
3,632,396 (the disclosure of which is incorporated herein by reference), 
nonwoven cloth substrates useful as drieradded fabric softening articles 
of manufacture are prepared wherein the substrate, the substrate coating, 
the outer coating and the perfuming material are as follows: 
1. A water "dissolvable" paper ("Dissolvo Paper"); and 
2. Adogen 448 (m.p. about 140.degree. F.) as the substrate coating; and pH 
3. An outer coating having the following formulation (m.p. about 
150.degree. F.): 
57% C.sub.20-22 HAPS 
22% isopropyl alcohol 
20% antistatic agent 
1% of one of the substances as set forth in Table I of Example XII. 
Fabric softening compositions prepared according to Example I at column 15 
of U.S. Pat. No. 3,632,396 having aroma characteristics as set forth in 
Table I of Example XII, supra, consist of a substrate coating having a 
weight of about 3 grams per 100 square inches of substrate; a first 
coating located directly on the substrate coating consisting of about 1.85 
grams per 100 square inches of substrate; and an outer coating coated on 
the first coating consisting of about 1.4 grams per 100 square inches of 
substrate. One of the substances of Table I of Example XII 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 drier-added fabric softener non-woven fabrics and these 
aroma characteristics are described in Table I of Example XII, supra. 
EXAMPLE XIX 
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 alcohol solution: 
______________________________________ 
Weight Percent 
______________________________________ 
Dioctyl sebacate 0.05 
Benzyl alcohol 0.10 
Dow Corning 473 fluid 
(prepared by the Dow Corning 
0.10 
Corporation) 
TWEEN .RTM. 20 surfactant 
(prepared by ICI America 
0.03 
Corporation) 
One of the perfumery substances -as set forth in Table I 
0.10 
Example XII, supra 
______________________________________ 
The perfuming substances as set forth in Table I of Example XII add aroma 
characteristics as set forth in Table I of Example XII which are rather 
intense and aesthetically pleasing to the users of the soft-feel, 
good-hold pump hair sprays. 
EXAMPLE XX 
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 
disterate (prepared by the Armak Corporation) and triethanolamine (a 
product of Union Carbide Corporation) (1.4 weight percent). The resulting 
melt is admixed with Stepanol WAT produced by the Stepan Chemical Company 
(35.0 weight percent). The resulting mixture is heated to 60.degree. C. 
and mixed until a clear solution is obtained (at 60.degree. C.). This 
material is "COMPOSITION A". 
GAFQUAT.RTM. 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 percent polyethylene glycol 6000 distearate 
produced by Armak Corporation. This material is "COMPOSITION B". 
The resulting "COMPOSITION A" and "COMPOSITION B" are then mixed in a 50:50 
weight ratio of A:B and cooled to 45.degree. C. and 0.3 weight percent of 
perfuming substance as set forth in Table I of Example XII is added to the 
mixture. The resulting mixture is cooled to 40.degree. C. and blending is 
carried out for an additional one hour in each case. At the end of this 
blending period, the resulting material has a pleasant fragrance as 
indicated in Table I of Example XII.