Use of adamantane derivatives in augmenting or enhancing the aroma of consumable materials

Described are adamantane derivatives defined according to the structure: ##STR1## wherein R.sub.1 is hydrogen or acetyl; R.sub.2 is hydrogen or methyl; and R.sub.3 is hydrogen or methylene (CH.sub.2) and wherein the dashed line represents a carbon-hydrogen single bond or a carbon-methylene double bond with the provisos that when R.sub.2 is methyl R.sub.1 and R.sub.3 are both hydrogen and when R.sub.2 is hydrogen, R.sub.3 is methylene and the dashed line is a carbon-methylene double bond and uses thereof in augmenting or enhancing the aroma of consumable materials selected from the group consisting of perfume compositions, colognes and perfumed articles.

BACKGROUND OF THE INVENTION 
The present invention relates to adamantane derivatives defined according 
to the generic structure: 
##STR2## 
wherein R.sub.1 is hydrogen or acetyl; R.sub.2 is hydrogen or methyl; and 
R.sub.3 is hydrogen or methylene and the dashed line represents a 
carbon-hydrogen single bond or a carbon-methylene double bond with the 
provisos that when R.sub.2 is methyl, R.sub.1 and R.sub.3 are hydrogen and 
when R.sub.2 is hydrogen, R.sub.3 is methylene and the dashed line 
represents a carbon-methylene double bond and uses of such compounds in 
augmenting or enhancing the aroma of perfume compositions, perfumed 
articles and colognes. 
There has been considerable work performed relating to substances which can 
be used to impart (modify, augment or enhance) fragrances too (or in) 
various consumable materials. Such substances are used to diminsh the use 
of expensive natural materials some of which may be in short supply and to 
provide more uniform properties in the finished product. 
Woody, earthy, camphoraceous, phenolic, piney, balsamic and patchouli 
aromas with camphoraceous, armoise, animalic, woody and minty topnotes are 
particularly desirable in several types of perfume compositions, perfumed 
articles and colognes. 
The use of tricyclic alcohol derivatives in perfumery for augmenting or 
enhancing the aromas of perfume compositions, perfumed articles and 
colognes is well known in the art. Thus, Inamoto, et al in U.S. Pat. No. 
4,036,893 discloses the use in perfumery of the compound having the 
structure: 
##STR3## 
Inamoto, et al in U.S. Pat. No. 4,169,958 also discloses the use of the 
tricyclic alcohol having the structure: 
##STR4## 
in perfumery. Light, et al in U.S. Pat. No. 3,996,169 discloses the use of 
the compound having the structure: 
##STR5## 
in perfumery. Inamoto, et al in U.S. Pat. No. 4,169,958 also discloses the 
use of the tricyclic alcohol having the structure: 
##STR6## 
in perfumery. Light, et al in U.S. Pat. No. 3,996,169 discloses the use of 
the compound having the structure: 
##STR7## 
in perfumery. Inamoto, et al in U.S. Pat. No. 4,036,892 discloses the use 
of the compound having the structure: 
##STR8## 
and in U.S. Pat. No. 4,036,892 discloses the use in perfumery of the 
compound having the structure: 
##STR9## 
The use in perfumery of the compound having the structure: 
##STR10## 
is disclosed in Chemical Abstracts, Volume 109, 9, 1988, No. 6759v 
(abstract of Koltsa, et al, Zh.Obshch.Khim., 1987, 57 (11) 2620-9. 
Light, et al in U.S. Pat. No. 4,439,354 discloses the genus of compounds 
defined according to the structure: 
##STR11## 
for use in perfumery wherein R.sub.1 represents hydrogen, methyl or acetyl 
and R.sub.2, R.sub.3, R.sub.4 and R.sub.5 each represent hydrogen, methyl 
or ethyl. 
Light, et al in U.S. Pat. No. 3,996,169 discloses the genus of compounds 
defined according to the structure: 
##STR12## 
where one or more of the R groups represents hydrogen or methyl. 
Adamantane derivatives and adamantane itself are known for use in 
augmenting or enhancing the aroma of perfume compositions, perfumed 
articles and colognes. Thus, the perfume use of compounds having the 
structures: 
##STR13## 
is disclosed in Chemical Abstracts, Volume 71, No. 94695w (abstract of 
Netherlands Published Application No. 6715903, May 28, 1969). Japan Kokai 
75/25742 Published on Mar. 18, 1975 and abstracted at Chem.Abstracts, 
Volume 84, No. 35214j and Japan Kokai Tokkyo Koho 78/145920 Published on 
Dec. 19, 1978 and abstracted at Chem.Abstracts, Volume 90, No. 142085p 
discloses the perfume use of adamantane itself having the structure: 
##STR14## 
Synthesis of various oxygen-substituted adamantane derivatives is well 
known in the prior art. 
Mlinaric-Magerski and Magerski, J.Am.Soc., 1983, 105, pages 7389-7395 
discloses the compound having the structure: 
##STR15## 
at page 7390 and discloses the reaction sequence: at page 7389. 
Hallden-Aberton, J.Org.Chem., Volume 46, No. 3, 1981, pages 538-546 
discloses the reaction sequence: 
##STR16## 
at pages 539 and 544. 
Drivas & Mison, Tetrahedron Letters, Volume 22, 1981, at pages 641-644 
discloses at page 643 the reaction sequence: 
##STR17## 
Kovalev, et al, Chem.Abstracts, Volume 109, 1988, No. 22553d (abstract of 
Zh.Org.Khim., 1987, 23(9), 1882-6 disclosed the compounds having the 
structure: 
##STR18## 
and discloses the reaction sequence: 
##STR19## 
However, the adamantane derivatives of our invention have unexpected, 
unobvious and advantageous properties with respect to the compounds of the 
prior art. Nothing in the prior art explicitly or implicitly sets forth 
the adamantane derivatives of our invention or their uses.

DETAILED DESCRIPTION OF THE DRAWINGS 
FIG. 1 is the GLC profile for the reaction product of Example I. The peak 
indicated by reference numeral 10 is the peak for the compound having the 
structure: 
##STR36## 
The peak indicated by reference numeral 11 is the peak for the compound 
having the structure: 
##STR37## 
FIG. 3 is the GLC profile for the reaction product of Example II 
(Conditions: Carbowax column programmed at 150.degree.-220.degree. C. at 
8.degree. C.). 
The peak indicated by reference numeral 20 is the peak for the compound 
having the structure: 
##STR38## 
The peak indicated by reference numeral 21 is the peak for the compound 
having the structure: 
##STR39## 
FIG. 5 is the GLC profile for the reaction product of Example III 
(Conditions: SE-30 column programmed at 150.degree.-220.degree. C. at 
8.degree. C. per minute). 
The peaks indicated by reference numerals 50 and 51 are for isomers of the 
compound having the structure: 
##STR40## 
FIG. 7 is the GLC profile for the reaction product of Example IV. The peaks 
indicated by reference numeral 72 and 73 are for isomers of the compound 
defined according to the structure: 
##STR41## 
The peak indicated by reference numeral 71 is the peak for the compound 
having the structure: 
##STR42## 
The peak indicated by reference numeral 70 is the peak for the compound 
having the structure: 
##STR43## 
which compound is apparently formed during the trapping in the GLC column 
(Conditions: Carbowax column programmed at 150.degree.-220.degree. C. at 
8.degree. C. per minute). 
FIG. 14 is the GLC profile for the reaction product of Example VI 
(Conditions: Carbowax column programmed at 100.degree.-220.degree. C. at 
8.degree. C. per minute). The peak indicated by reference numeral 140 is 
the peak for the compound having the structure: 
##STR44## 
Referring to FIGS. 17 and 18 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 vinly 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. 17 and 
18, in particular, the apparatus used in producing such elements comprises 
a device for forming the polymer containing perfume, e.g., polyethylene or 
polyethylene-polyvinyl acetate or mixtures of the same of 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 one of the adamantane derivatives of our invention or mixtures of 
adamantane derivatives and other compatible perfumes 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 rheostate 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 the container 212 is 
heated from 10-12 hours, whereafter the perfume composition or perfume 
material which contains one or more of the adamantane derivatives 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 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 multiplicty 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 one or more of the adamantane 
derivatives of our invention or mixture of adamantane derivatives 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 one or more of the adamantane 
derivatives 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 belt 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 instananeously 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 and the like. 
THE INVENTION 
The present invention provides adamantane derivatives defined according to 
the structure: 
##STR45## 
wherein R.sub.1 is hydrogen or acetyl; R.sub.2 is hydrogen or methyl; and 
R.sub.3 is hydrogen or methylene; and the dashed line represents a 
carbon-hydrogen single bond or a carbon-methylene double bond with the 
provisos that when R.sub.2 is methyl then R.sub.1 and R.sub.3 are both 
hydrogen; and when R.sub.2 is hydrogen, R.sub.3 is methylene and the 
dashed line represents a carbon-methylene double bond. 
The adamantane derivatives of our invention produced according to prior art 
processes are known in the prior art per se and have now been found to be 
capable of augmenting or enhancing woody, earthy, camphoraceous, phenolic, 
piney, balsamic and patchouli-like aromas with camphoraceous, armoise, 
animalic, woody and minty topnotes thus fulfilling a need in the field of 
perfumery. 
The processes for producing the adamantane derivatives of our invention are 
also known in the prior art and involve the following reactions which are 
also exemplified in Examples I-VI, infra: 
##STR46## 
The following table represents the compounds the perfumery uses of which 
are the subject of our invention and their respective organoleptic 
properties: 
TABLE I 
______________________________________ 
Structure of Compound 
Perfumery Properties 
______________________________________ 
The compound having 
An earthy, camphoraceous and 
the structure: phenolic aroma. 
##STR47## 
produced according to 
Example III. 
##STR48## A piney, camphoraceous, balsamic and woody aroma with 
camphoraceous armoise and animalic topnotes. 
produced according to 
Example V. 
##STR49## A camphoraceous, woody, patchouli aroma 
with camphoraceous, woody, minty and animalic topnotes. 
produced according to 
Example VI. 
______________________________________ 
One of the adamantane derivatives prepared in accordance with the processes 
of the prior art and one or more auxilliary perfume ingredients including, 
for example, alcohols other than the hydroxy adamantane derivatives or our 
invention, aldehydes, ketones, terpenic hydrocarbons, nitriles, esters, 
other than the adamantane esters of our invention, lactones, natural 
essential oils and synthetic essential oils may be admixed so that the 
combined odors of the individual components produce a pleasant and desired 
fragrance, particularly, and preferably, in piney fragrances and patchouli 
fragrances. Such perfume compositions usually contain (a) the main note or 
the "bouquet" or foundation stone of the composition; (b) modifiers which 
round out an accompany the main note; (c) fixatives which include odorous 
substances which lend a particular note to the perfume throughout all 
states of evaporation and substances which retard evaporation; and (d) 
topnotes which are usually low-boiling fresh-smelling materials. 
In perfume compositions, it is the individual components which contribute 
to their particular olfactory characteristics, however, the overall 
sensory effect of the perfume composition will be at least the sum total 
of the effects of each of the ingredients. Thus, one of the adamantane 
derivatives prepared in accordance with the processes or 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 one of the adamantane derivatives prepared in accordance with 
the processes of our invention which will be effective in perfume 
compositions as well as in perfumed articles (e.g., anionic, nonionic, 
cationic, or zwitterionic detergents, soaps and fabric softener 
compositions and articles) and colognes depends upon 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 one of the adamantane derivatives prepared in accordance with 
the processes of our invention and less 50% of one of the adamantane 
derivatives prepared in accordance with the processes of our invention or 
even less (e.g., 0.005%) can be used to impart a woody, earthy, 
camphoraceous, phenolic, piney, balmsamic and patchouli aroma with 
camphoraceous, armoise, animalic, woody and minty topnotes to soaps, 
cosmetics, anionic, cationic, nonionic, or zwitterionic detergents, fabric 
softener compositions, fabric softener articles, perfumed polymers or 
other articles. The amount employed can range up to 70% of the fragrance 
components and will depend on considerations of cost, nature of the end 
product, the effect desired on the finished product and the particular 
fragrance sought. 
One or more of the adamantane derivatives prepared in accordance with the 
prior art are useful (taken alone or together with other ingredients in 
perfume compositions) as (an) olfactory component(s) in detergents and 
soaps, space odorants and deodorants, perfumes, colognes, toilet water, 
bath preparations, such as creams, deodorants, hand lotions and sun 
screens; powders, such as talcs, dusting powders, face powders, perfumed 
polymers and the like. When used as (an) olfactory component(s) as little 
as 0.2% of one or both of the adamantane derivatives of our invention, 
prepared in accordance with the prior art of our invention, will suffice 
to impart an intense and substantive woody, earthy, camphoraceous, 
phenolic, piney, balsamic and patchouli aroma with camphoraceous, armoise, 
animalic, woody and minty topnotes to patchouli formulations and to 
vetiver formulations and to pine formulations. Generally, no more than 6% 
of one or both of the adamantane derivatives of our invention produced in 
accordance with the processes of our invention based on the ultimate end 
product are required in the perfumed article composition. Accordingly, the 
range of one or more of the adamantane derivatives of our invention in a 
perfumed article may vary from one 0.2% up to about 6% by weight of the 
ultimate perfumed article. 
In addition, the perfumed compositions or fragrance compositions of our 
invention can contain a vehicle or carrier for one or both of the 
adamantane derivatives prepared in accordance with the processes of our 
invention. The vehicle can be a liquid, such as a non-toxic alcohol, e.g., 
ethyl alcohol, a glycol, e.g., propylene glycol or the like. The carrier 
can also be an absorbent solid, such as a gum (i.g., gum arabic, xanthan 
or guar gum) or components for encapsulating the composition (such as 
gelatin as by coacervation or such as a urea-formaldehyde pre-polymer when 
forming a urea-formaldehyde polymer wall around a liquid perfume center. 
It will thus be apparent that one of the adamantane derivatives of our 
invention can be utilized either to alter, modify or enhance sensory 
properties, particularly organoleptic properties such as fragrances of a 
wide variety of consumable materials. 
The following examples illustrate methods (primarily disclosed in the prior 
art) used to manufacture the adamantane derivatives useful in our 
invention. 
Examples following Example VI (Example VII et seq) illustrate the 
organoleptic utilities of the adamantane derivatives of our invention. 
All parts and percentages given herein are by weight unless otherwise 
specified. 
EXAMPLE I 
Preparation of 4-Oxahomoadamantan-5-One 
##STR50## 
Into a three liter reaction-flask equipped with stirrer, thermometer, 
reflux condenser and heating mantle is placed 13.32 grams of sclenium 
dioxide and 1251 ml pre-warmed tertiary buytl alcohol. While maintaining 
the temperature at 22.degree.-26.degree. C. over a period of 15 minutes, 
225 grams (2.06 moles) of hydrogen peroxide (30%) is added to the reaction 
mass. 
The reaction mass is then heated to reflux (76.degree. C.). While 
maintaining the reaction temperature at 76.degree.-78.degree. C., over a 
period of 0.5 hours, 300 grams (2.01 moles) of the compound having the 
structure 
##STR51## 
(adamantanone) is added to the reaction mass. 
The reaction mass is then refluxed for a period of 1.5 hours after which 
time an additional 34 grams (0.3 moles) of 30% hydrogen peroxide is added 
drop-wise to the reaction mass. 
The reaction mass is allowed to cool down to room temperature for a period 
of 12 hours. 
The reaction mass is then poured into 1,500 ml cold water. The reaction 
mass is then extracted with three 1,500 ml portions of methylene 
dichloride. The organic layer is washed with 2,000 ml water and then dried 
over anhydrous magnesium sulfate. The resultant slurry is filtered and 
concentrated to yield 326 grams of crude product. The crude product is 
dissolved in 100 ml methylene dichloride and then diluted with n-hexane to 
yield 1,100 ml product. 
The reaction mass is then concentrated for further reaction. 
EXAMPLE II 
Preparation of 4-Hydroxytricyclo [3.3.1.1] Decan-2-One 
##STR52## 
Into a 2 liter reaction flask equipped with ice bath is placed 500 ml 
concentrated sulfuric acid. While maintaining the concentrated sulfuric 
acid at 24.degree. C., over a period of 0.3 hours 500 ml water is added. 
The reaction mass is then cooled to 30.degree. C. and while maintaining 
the reaction mass at 30.degree.-31.degree. C., 96 grams (0.58 moles) of 
the compound having the structure: 
##STR53## 
added to the reaction mass. 
The reaction mass is then heated to 90.degree. C. and maintained at 
90.degree. C. initially for a period of 1 hour. The reaction mass is then 
aged for 2.5 hours yielding 52% compound having the structure: 
##STR54## 
and 45% of the compound having the structure: 
##STR55## 
(the starting material). After 31/2 hours of aging the reaction mass 
contains 61% of the compound having the structure: 
##STR56## 
and 36% of the compound having the structure: 
##STR57## 
After 5 hours of aging the reaction mass contains 65% of the compound 
having the structure: 
##STR58## 
and 35% of the compound having the structure: 
##STR59## 
250 ml concentrated sulfuric acid is then to the reaction mass. The 
reaction mass is then aged at 90.degree. C. for 7.5 hours. 
The reaction mass is then poured into one liter of water and the products 
are extracted with three 1,000 ml portions of methylene dichloride. The 
organic layer is washed with water (1,000 ml) and dried over anhydrous 
magnesium sulfate, filtered and concentrated to yield 63 grams of product 
containing 78% of the compound having the structure: 
##STR60## 
EXAMPLE III 
Production of Methylene Hydroxyadamantane Derivative Using Witting Reaction 
##STR61## 
Into a 250 ml reaction flask equipped with thermometer, addition funnel and 
dry ice/isopropyl alcohol bath is placed a slurry of trimethyl phosphine 
bromide (26.8 grams; 0.075 moles) in 75 ml tetrohydrofuran. With vigorous 
stirring, the resulting slurry is cooled to 0.degree. C. 
Dropwise while maintaining the temperature at 0.degree. C., 52 ml of a 1.6 
molar solution of n-butyl lithium in hexane is added to the flask. 
(Addition time:20 minutes). 
The resulting slurry is aged at 15 minutes with stirring at 0.degree. C. 
Over a period of 20 minutes while maintaining the reaction temperature at 
0.degree. C., 5 grams (0.03 moles; of the compound having the structure: 
##STR62## 
prepared according to Example II (in diglyme solvent) is added to the 
reaction mass. The reaction mass is then aged for 2 hours while being 
permitted to warm to room temperature. 
The resulting suspension is filtered and the solid is washed with 30 ml 
methylene dichloride. 
The organic layer is then washed with 250 ml saturated sodium chloride. The 
water layer is extracted with 50 ml methylene dichloride. 
All organic layers are combined and dried over anhydrous magnesium sulfate. 
The filtrate is then concentrated to yield 12 grams of material. 
The resulting concentrate is chromatographed to yield in three fractions; 
weighing: 
(i) 130 mg; 
(ii) 450 mg; and 
(iii) 30 mg 
450 mg fraction is the compound having the structure: 
##STR63## 
EXAMPLE IV 
Preparation of Tertiary Methyl Adamantane Diol Followed by Creation of 
Methylene Adamantol 
##STR64## 
Into a 250 ml reaction flask equipped with a dry ice/isopropyl alcohol bath 
is placed 54 ml of a 1.4 molar solution of methyl lithium is diethyl ether 
(0.075 moles). the methyl lithium solution is cooled to -5.degree. C. and 
over a period of 0.5 hours, 5 grams (0.03 moles) of the compound having 
the structure: 
##STR65## 
prepared according to Example II in methylene dichloride is added to the 
methyl lithium solution. The reaction mass is then cooled to -10.degree. 
C. The reaction mass is then allowed to warm to room temperature and aged 
at room temperature for 5 hours. 
50 ml water is added to the reaction mass. The resulting organic phase is 
then washed with three 250 ml portions of saturated sodium chloride until 
neutral to pH paper. 
The organic layer is dried over anhydrous magnesium sulfate, filtered and 
concentrated to yield 2.5 grams (0.014 moles) of product having the 
structure: 
##STR66## 
The resulting product is then dehydrated over methane sulfonic acid to 
yield the compound having the structure: 
##STR67## 
EXAMPLE V 
Preparation of 4-Hydroxy Tricyclo [3.3.1.1] 2-Methylene Decane Acetate 
##STR68## 
Into a 50 ml reaction flask equipped with magnetic stirrer is placed 5 
grams (0.03 moles) of the compound having the structure: 
##STR69## 
dissolved in 25 ml acidic anhydride. 
The resulting mixture is heated to 90.degree. C. and maintained with 
stirring at 90.degree. C. for a period of 2 hours. 
At the end of the 2 hour period 10 ml water is slowly added while 
maintaining the reaction temperature at 90.degree. C. with stirring. 
The reaction mass is heated to 105.degree. C. briefly. 
The reaction mass is then poured into 100 ml water. 
The reaction mass is extracted with three 40 ml portions of methylene 
dichloride. 
The organic phase is washed with two 100 ml portions of saturated sodium 
bicarbonate followed by one 100 ml portion of sodium chloride (saturated). 
The reaction mass is then filtered through anhydrous magnesium sulfate and 
concentrated. 
The resulting oily solid is washed n-hexene. The resulting product is 
filtered and the filtrate is concentrated to yield 6 grams (0.02 moles). 
The resulting product is distilled at 95.degree. C. and 2 mm Hg, yielding 
3.25 grams (0.0158 moles) of product having the structure: 
##STR70## 
EXAMPLE VI 
Preparation of Tertiary Methyl Adamantol 
##STR71## 
Into a 5 liter flask equipped with cooling bath, stirrer, thermometer and 
reflux condenser and under a nitrogen blanket is added 2.80 moles of 
methyl lithium dissolved in 800 cc diethyl ether. While maintaining the 
reaction mass at -2.degree. C. over a period of 1 hour, 205 grams of 
2-adamantanone having the structure: 
##STR72## 
is added to the reaction mass. The resulting product is maintained at 
4.degree. C. for a period of one hour. 
Dropwise over a period of 1 hour 700 cc of 5% acidic acid is added to the 
reaction mass. Dropwise over a period of 1 hour 700 cc of toluene is added 
to the reaction mass with stirring. 
The reaction mass is then washed with 800 cc of 5% acidic acid followed by 
two portions (800 cc each) of 5% sodium bicarbonate followed by two 800 cc 
portions of sodium chloride (saturated). 
The resulting product is filtered and has the structure: 
##STR73## 
EXAMPLE VII 
Pine Fragrance 
The following pine fragrance formulation is produced: 
TABLE I 
______________________________________ 
Ingredients VII(A) VII(B) VII(C) 
______________________________________ 
Isbornyl acetate 100 100 100 
Camphor 10 10 10 
Terpineol 25 25 25 
Fir balsam absolute 
20 20 20 
(50% in diethyl phthalate) 
Courmarin 4 4 4 
Linalool 30 30 30 
Fenchyl alcohol 10 10 10 
Anethol 12 12 12 
Lemon terpenes washed 
50 50 50 
Borneol 5 5 5 
Galbanum oil 5 5 5 
Turpentine Russian 
150 150 150 
Eucalyptol 50 50 50 
2,2,6-trimethyl-1-cyclohexene- 
12 12 12 
1-caboxaldehyde 
Maltol (1% in 5 5 5 
diethyl phthalate) 
The compound having 
28 0 0 
the structure: 
##STR74## 
prepared according 
Example III. 
The compound having 
0 28 0 
the structure: 
##STR75## 
prepared according to 
Example V. 
The compound having 
0 0 28 
the structure: 
##STR76## 
prepared according 
Example VI. 
______________________________________ 
The compound having the structure: 
##STR77## 
prepared according to Example III adds an earthy, camphoraceous and 
phenolic undertone to this pine fragrance. Accordingly, the fragrance of 
Example VII(A) can be described as "piney with earthy, camphoraceous and 
phenolic undertones". 
The compounds having the structure: 
##STR78## 
prepared according to Example V adds to this piney fragrance a 
camphoraceous, balsamic and woody undertone with camphoraceous, armoise 
and animalic topnotes. Accordingly, the fragrance of Example VII(B) can be 
described as "piney with camphoraceous, balsamic and woody undertones and 
camphoraceous, armoise and animalic topnotes". 
The compound having the structure: 
##STR79## 
adds to this piney fragrance a camphoraceous, woody and pathcouli 
undertone and camphoraceous, animalic, woody and minty topnotes. 
Accordingly, the fragrance of Example VII(C) can be described as "piney 
with camphoraceous, woody and patchouli undertones and camphoraceous, 
animalic, woody and minty topnotes. 
EXAMPLE VIII 
Preparation of Cosmetic Powder Compositions 
Cosmetic powder compositions are prepared by mixing in ball mill 100 grams 
of talcum powder with 0.25 grams of each of the substances set forth in 
Table II below. Each of the cosmetic powder compositions has an excellent 
aroma as described in Table II below. 
TABLE II 
______________________________________ 
Substance Aroma Description 
______________________________________ 
The compound having the 
An earthy, camphoraceous 
structure: and phenolic aroma profile. 
##STR80## 
prepared according to 
Example III. 
##STR81## a piney, camphoraceous, balsamic and woody aroma profile 
with camphoraceous armoise, and animalic topnotes. 
prepared according to 
Example V. 
##STR82## A camphoraceous, woody, and patchouli aroma 
with camphoraceous, animalic, woody and minty topnotes. 
prepared according to 
Example VI. 
The perfume composition 
Piney with earthy, 
of Example VII(A) 
camphoraceous and phenolic 
undertones. 
The perfume composition 
Piney with camphoraceous, 
of Example VII(B) 
balsamic and woody undertones 
and camphoraceous, armoise and 
animalic topnotes. 
The perfume composition 
Piney with camphoraceous, 
of Example VII(C) 
woody and patchouli undertones 
and camphoraceous, animalic, 
woody and minty topnotes. 
______________________________________ 
EXAMPLE IX 
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 II of Example VIII 
are prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.35% of the 
substance set forth in Table II of Example VIII. They are prepared by 
adding and homogeneously mixing the appropriate quantity of substance set 
forth in Table II of Example VIII below in the liquid detergent. The 
detergents all possess excellent aromas as set forth in Table III of 
Example VIII, the intensity increasing with greater concentrations of 
substance as set forth in Table II of Example VIII. 
EXAMPLE X 
Preparation of Colognes and Handerchief Perfumes 
Compositions as set forth in Table II of Example VIII 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 II of Example VIII are 
imparted to the colognes and to the handkerchief perfumes at all levels 
indicated. 
EXAMPLE XI 
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 III of Example VIII 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 II of Example VIII. 
EXAMPLE XII 
Preparation of Solid Detergent Composition 
Detergents are prepared using the following ingredients according to 
Example I of Canadian Pat. No. 1.007,948: 
______________________________________ 
Ingredient Percent By Weight 
______________________________________ 
"Neodol .RTM. 45-11(a C.sub.14 -C.sub.15 
12 
alcohol ethoxylated with 
11 moles of ethylene oxide 
Sodium carbonate 55 
Sodium citrate 20 
Sodium sulfate, water 
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 II of Example VIII. Each of the 
detergent samples has an excellent aroma as indicated in Table II of 
Example VIII. 
EXAMPLE XIII 
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.20-22 HAPS 
22%--isopropyl alcohol 
20%--antistatic agent 
1%--of one of the substances as set forth in Table II of Example VIII. 
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 II of Example VIII, 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 II of Example VIII 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 
softner non-woven fabrics and these aroma characteristics are described in 
Table II of Example VIII. 
EXAMPLE XIV 
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 are added 
to the PVP/VA alcoholic solution: 
______________________________________ 
Percent 
Ingredient By Weight 
______________________________________ 
Dioctyl sebacate 0.05 
Benzyl alcohol 0.10 
Dow Corning 473 fluid 
(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 II of 
Example VIII 
______________________________________ 
The perfuming substances as set forth in Table II of Example VIII add aroma 
characteristics as set forth in Table II of Example VIII which are rather 
intense and aesthetically pleasing to the users of the soft-feed, 
good-hold pump hair sprays. 
EXAMPLE XV 
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 
disterate 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 II of Example 
VIII 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 II of Example VIII.