Substituted tetrahydroindane derivatives and organoleptic uses of substituted tetrahydroindanes

Described are substituted tetrahydroindanes defined according to the generic structure: ##STR1## wherein Z is a moiety selected from the group consisting of: ##STR2## wherein X represents chloro or bromo; wherein R.sub.1 represents: EQU --OR.sub.3 or --O.sup..sym. M.sup..crclbar. ; wherein R.sub.3 represents hydrogen, methyl or ethyl; wherein M represents alkali metal, sodium potassium or lithium; wherein R.sub.2 represents hydrogen or the moiety: ##STR3## as well as uses of substituted tetrahydroindanes defined according to the structure: ##STR4## wherein Z' represents a moiety selected from the group consisting of: ##STR5## wherein R.sub.2 is hydrogen and wherein R.sub.1 is the moiety: EQU OR.sub.3 ' wherein R.sub.3 ' is methyl or ethyl in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles including but not limited to perfumed polymers, solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions, fabric softener articles, hair preparations and cosmetic powders.

BACKGROUND OF THE INVENTION 
This invention relates to substituted tetrahydroindanes some of which are 
useful in augmenting or enhancing the aroma of perfume compositions, 
colognes and perfumed articles. Other substituted tetrahydroindanes of our 
invention are useful as intermediates in chemical processes used to 
synthesize compounds which are, interalia, useful in augmenting or 
enhancing the aroma of perfume compositions, colognes and perfumed 
articles. 
Dry woody, rose, fruity, floral and tobacco-like aromas with date-like, 
fig-like, tobacco and rose topnotes are particularly desirable in 
augmenting or enhancing the aroma of perfume compositions, colognes and 
perfumed articles (e.g., solid or liquid anionic, cationic, nonionic or 
zwitterionic detergents, fabric softener compositions, fabric softener 
articles, hair preparations, cosmetic powders and perfumed polymers. 
Compounds having the pentamethylindane moiety are well known in the 
perfume art in augmenting or enhancing the aroma of perfume compositions, 
colognes and perfumed articles. 
Thus, the compound having the structure: 
##STR6## 
is indicated to be useful in augmenting or enhancing the aroma of perfume 
compositions, colognes and perfumed articles in U.S. Pat. No. 3,636,165 
issued on January 18, 1972 the specification for which is incorporated by 
reference herein. 
The compound having the structure: 
##STR7## 
is indicated to be useful in augmenting or enhancing the aroma of perfume 
compositions, colognes and perfumed articles in U.S. Pat. No. 3,806,472 
issued on April 23, 1974 the specification for which is incorporated by 
reference herein. 
The compound having the structure: 
##STR8## 
is indicated to be useful in augmenting or enhancing the aroma of perfume 
compositions, colognes and perfumed articles in U.S. Pat. No. 3,647,826 
issued on March 7, 1972, the specification for which is incorporated by 
reference herein. 
Nothing in the prior art discloses however the organoleptic properties of 
certain of the substituted tetrahydroindanes of our invention. 
Furthermore, nothing in the prior art discloses any of the substituted 
tetrahydroindanes of our invention either for their organoleptic 
properties or for their uses as intermediates in processes which 
ultimately give rise to compounds useful for their organoleptic 
properties.

DETAILED DESCRIPTION OF THE DRAWINGS 
Referring to FIGS. 7 and 8, the apparatus used in producing polymeric 
fragrances containing the substituted tetrahydroindanes of our invention 
comprises a device for forming scented polyolefin (for example) pellets 
which comprises a vat or container 212 into which a mixture of polyolefins 
such as polyethylene or an aromatic substance or scented material 
containing or consisting of at least one of the substituted 
tetrahydroindanes of our invention is placed. The container is closed by 
an air tight lid 228, and clamped to the container by bolts 265. A stirrer 
273 traverses the lid or cover 228 in air tight manner and is rotated in a 
suitable manner. A surrounding cylinder 212 having heating coils 212A 
which are supplied with electric current through cable 224 through a 
rheostat or control 216 is operated to maintain the temperature inside the 
container 212 such that polyethylene or other thermoplastic polymer in the 
container will be maintained in the molten or liquid state. It has been 
found advantageous to employ a colorless, odorless polymer (e.g., 
polyethylene) with a viscosity ranging between 180 and 220 Saybolt seconds 
and having a melting point in the range of 200.degree.-280.degree. F. The 
heater is operated to maintain the upper portion of the container 212 
within a temperature range of from 250.degree.-350.degree. F. The bottom 
portion of the container is heated by means of heating coils 212A heated 
through a control connected thereto through a connecting wire 226 to 
maintain the lower portion of the container within a temperature range of 
from 250.degree.-350.degree. F. 
Thus, polymer (e.g., polyolefin) added to the container 212 is heated from 
10-12 hours whereafter a scent or aroma imparting material which contains 
or consists of at least one of the substituted tetrahydroindanes of our 
invention is quickly added to the melt. The material must be compatible 
with the polyolefin and forms a homogeneous liquid melt therewith. The 
scented material containing at least one of the substituted 
tetrahydroindanes of our invention is of a type for the particular aroma 
desired and formulated specifically for the scenting purpose for which the 
polyolefin will be employed. The heat resisting coils and aromatic 
materials in some instances in solid or powdered form may be employed and 
added to the polyolefin in the container 212. Generally, about 10-30% by 
weight of scenting material is added to the polyolefin. 
After the scent imparting material containing or consisting of at least one 
of the substituted tetrahydroindanes of our invention 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 coils 212A and 218. 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 (e.g., polyolefin) and aroma imparting mixture (containing 
at least one of the substituted tetrahydroindanes of our invention) will 
continuously drop through orifices 234 downwardly from the conduit 232. 
During this time, the temperature of the polymer (e.g., polyolefin) and 
aroma mixture containing or consisting of at least one of the substituted 
tetrahydroindanes of our invention in the container 212 is accurately 
controlled so that a temperature in the range of from about 
210.degree.-275.degree. F. will exist in the conduit 232. The regulation 
of the temperature through the control 216 and the control 220 is 
essential in order to insure temperature balance to provide for the 
continuous dropping or dripping of molten polymer (e.g., polyolefin) and 
scenting material containing at least one of the substituted 
tetrahydroindanes 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 trained 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 259 which is advantageously filled with water or some 
other suitable cooling liquid in order to insure the rapid cooling of each 
of the pellets. The pellets 244 are then collected from the container 259 
and utilized in a process as illustrated, infra. 
A feature of this aspect of the process of our invention is in the 
provision for moistening the conveyor belt 238 to insure rapid formation 
of the solid polymer (e.g., polyolefin) scented pellets 244 without 
sticking to the belt. The belt 238 is advantageously of a material which 
will not normally stick to a melted plastic but the moistening means 248 
insures a sufficiently cold temperature of the belt surface for the 
adequate formation of the pellets 244. The moistening means comprises a 
container 259 which is continuously fed with water 252 to maintain a level 
254 for moistening a sponge element 256 which bears against the exterior 
surface of the belt 238. 
THE INVENTION 
The instant invention provides substituted tetrahydroindanes defined 
according the generic structure: 
##STR15## 
wherein Z represents a moiety selected from the group consisting of: 
##STR16## 
wherein X represents chloro or bromo; wherein R.sub.1 represents one of 
the moieties: 
EQU --OR.sub.3 or OR.sup..crclbar. M.sup..sym. 
wherein R.sub.3 is hydrogen, methyl or ethyl; wherein M is alkali metal, 
sodium, potassium or lithium; wherein R.sub.2 is hydrogen or the moiety: 
##STR17## 
Certain of the aforementioned substituted tetrahydroindanes of our 
invention, to wit, those having the generic structure: 
##STR18## 
are useful in augmenting or enhancing the aroma of perfume compositions, 
colognes and perfumed articles (including but not limited to solid or 
liquid anionic, cationic, nonionic or zwitterionic detergents, perfumed 
polymers, fabric softener compositions and fabric softener articles, 
cosmetic powders, hair preparations and the like). In the case of 
substituted tetrahydroindanes useful in augmenting or enhancing the aroma 
of perfume compositions, colognes and perfumed articles, Z' is a moiety 
selected from the group consisting of: 
##STR19## 
and wherein R.sub.2 is hydrogen and R.sub.1 is the moiety: 
EQU -OR.sub.3 ' 
wherein R.sub.3 ' is methyl or ethyl. 
The other of the substituted tetrahydroindanes of our invention are useful 
as intermediates in synthesis processes for producing compounds which 
augment or enhance the aroma of perfume compositions, colognes or perfumed 
articles. 
A section of our invention contemplates augmenting or enhancing the aroma 
of perfume compositions, colognes and perfumed articles as set forth, 
supra. Thus, the compounds defined according to the generic structure: 
##STR20## 
which includes the compound having the generic structure: 
##STR21## 
(wherein R.sub.3 ' is methyl or ethyl) as well as the compound having the 
structure: 
##STR22## 
augment or enhance dry woody, rose, fruity, floral and tobacco-like aromas 
with date-like, fig-like, tobacco and rose topnotes. 
The compounds of our invention defined according to the generic structure: 
##STR23## 
wherein Z is defined, supra, include compounds having the following 
structures: 
##STR24## 
The compounds defined according to the structure: 
##STR25## 
may be prepared by means of reacting the compound having the structure: 
##STR26## 
with a halogenating agent such as SO.sub.2 Cl.sub.2, SO.sub.2 Br.sub.2, 
POCl.sub.3, POBr.sub.3, PCl.sub.5, nitrosylchloride, N-chlorosuccinimide 
and the like according to the reaction: 
##STR27## 
The precursor compound having the structure: 
##STR28## 
may be prepared according to Example I(c), at column 4, line 71 of U.S. 
Pat. No. 3,636,165 issued on January 18, 1972, the specification for which 
is incorporated by reference herein. The reaction is carried out in the 
presence of an inert solvent such as toluene at temperatures in the range 
of from about 50.degree. up to about 80.degree. C. with approximately 
equimolar amounts of halogenating agent and compound having the structure: 
##STR29## 
Preferably the reaction is carried out at atmospheric pressure but 
sub-atmospheric and super-atmospheric pressures may be used. At the end of 
the reaction, the reaction mass is washed with water and aqueous base 
(e.g., aqueous sodium bicarbonate solution). The resulting product is 
dried and may be used without further purification for subsequent 
reaction. 
In preparing compounds defined according to the generic structure: 
##STR30## 
wherein R.sub.3 ' is methyl or ethyl (which compounds are useful for their 
perfumery properties in augmenting or enhancing the aroma of perfume 
compositions, colognes or perfumed articles), the compound having the 
structure: 
##STR31## 
(wherein X is chloro or bromo) is first reacted with a malonic ester 
defined according to the structure: 
##STR32## 
wherein R.sub.3 ' represents methyl or ethyl in the presence of an 
alcoholic solution of an alkali metal alkoxide such as a 25% solution of 
sodium methoxide in methanol according to the reaction: 
##STR33## 
The resulting product having the structure: 
##STR34## 
wherein R.sub.3 ' is methyl or ethyl is a novel chemical intermediate. 
The reaction preferably takes place at ambient conditions, e.g., 
20.degree.-30.degree. C. at atmospheric pressure. Preferably, the mole 
ratio of alkali metal alkoxide:malonic ester:compound having the 
structure: 
##STR35## 
is approximately 1:1:1. 
The resulting product having the structure: 
##STR36## 
is then saponified using aqueous base, e.g., an aqueous solution of the 
compound having the structure: 
EQU MOH 
wherein M is sodium, potassium or lithium according to the reaction: 
##STR37## 
The resulting compound having the structure: 
##STR38## 
is a novel reaction intermediate. The saponification reaction takes place 
at reflux conditions over a period of between about one and about five 
hours. 
The resulting salt having the structure: 
##STR39## 
is then treated with mineral acid such as hydrochloric acid or sulfuric 
acid in order to form the dicarboxylic acid having the structure: 
##STR40## 
a novel chemical intermediate according to the reaction: 
##STR41## 
With heating, the dicarboxylic acid is monodecarboxylated to form the 
carboxylic acid having the structure: 
##STR42## 
according to the reaction: 
##STR43## 
The compound having the structure: 
##STR44## 
is a novel chemical intermediate. 
The compound having the structure: 
##STR45## 
is then esterified using standard methyl or ethyl esterification 
conditions; for example, refluxing the compound having the structure: 
##STR46## 
with methanol or ethanol in the presence of concentrated sulfuric acid in 
accordance with the reaction: 
##STR47## 
wherein R.sub.3 ' is methyl or ethyl. 
The compound having the structure: 
##STR48## 
is a valuable perfumery material having properties as set forth in Table 
I, infra. 
The compound having the structure: 
##STR49## 
is recovered by means of fractional distillation. 
The compound having the structure: 
##STR50## 
useful for its organoleptic properties in augmenting or enhancing the 
aroma of perfume compositions, colognes or perfumed articles is prepared 
by epoxidation of the compound having the structure: 
##STR51## 
which, in turn, may be prepared by dehydrohalogenation of the compound 
having the structure: 
##STR52## 
or in the alternative it may be prepared according to Example II(b) to be 
at line 50 of column 5 of U.S. Pat. No. 3,806,472 issued on April 23, 
1974, the specification for which is incorporated herein by reference. 
In carrying the dehydrohalogenation of one of the compounds defined 
according to the structure: 
##STR53## 
in accordance with the reaction: 
##STR54## 
standard dehydrohalogenation procedures may be used. Thus, the reaction 
may be carried out using a tributyl amine dehydrohalogenation reagent at 
reflux conditions for a period of between about one and about four hours. 
The mole ratio of dehydrohalogenation reagent:compound having the 
structure: 
##STR55## 
is preferably about 1:1. At the end of the reaction, the reaction mass is 
cooled and washed with water and weak acid and used without further 
purification in the epoxidation step. 
In carrying out the epoxidation reaction, to wit: 
##STR56## 
(shown using a peracetic acid epoxidation reagent, standard epoxidation 
reagents may be used, for example, peracetic acid as set forth in the 
above reaction, perbenzoic acid and the like. The epoxidation reaction is 
preferably carried out in the presence of an inert solvent such as toluene 
at a temperature in the range of from about 30.degree. C. up to about 
50.degree. C. with the mole ratio of epoxidation reagent:hydrocarbon being 
preferably about 1:1. The reaction is carried out in the presence of a 
small amount of weak base such as sodium carbonate. At the end of the 
reaction, the reaction mass is quenched with water and the organic layer 
is washed with weak base, e.g., 5% sodium carbonate. The reaction mass is 
then fractionally distilled to yield the organoleptically useful compound 
having the structure: 
##STR57## 
The following Table I sets forth examples of two of the substituted 
tetrahydroindanes useful in augmenting or enhancing the aroma of perfume 
compositions, perfumed articles and colognes and their organoleptic 
properties: 
TABLE I 
______________________________________ 
Structure of 
Substituted 
Tetrahydroindane Perfumery 
Derivatives Properties 
______________________________________ 
The compound having 
A dry woody, rose and fruity 
the structure: aroma profile. 
##STR58## 
prepared according 
to Example II. 
The compound having 
A fruity, floral, tobacco-like 
the structure: and rose aroma with date-like, 
##STR59## fig-like, tobacco and rose topnotes. 
prepared according 
to Example IV. 
______________________________________ 
One or more of the substituted tetrahydroindanes of our invention and one 
or more auxiliary perfume ingredients, including, for example, alcohols, 
aldehydes, ketones, terpinic hydrocarbons, nitriles, esters other than the 
substituted tetrahydroindanes of our invention, epoxides other than the 
substituted tetrahydroindanes 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 rose and tobacco fragrances. 
Such perfume compositions usually contain (a) the main note or the 
"bouquet" or foundation stone of the composition; (b) modifiers which 
round off and accompany the main note; (c) fixatives which include odorous 
substances which lend a particular note to the perfume throughout all 
stages of evaporation and substances which retard evaporation; and (d) 
topnotes which are usually low boiling, fresh-smelling materials. 
In perfume compositions it is the individual components which contribute to 
their particular olfactory characteristics, however the over-all sensory 
effect of the perfume composition will be at least the sum total of the 
effects of each of the ingredients. Thus, at least one of the substituted 
tetrahydroindanes 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 one or more of the substituted tetrahydroindanes of our 
invention which will be effective in perfume compositions as well as in 
perfumed articles and colognes and perfumed polymers 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 0.10% of at least one of the substituted tetrahydroindanes of 
our invention or even less can be used to impart, augment or enhance dry 
woody, rose, fruity, floral and tobacco-like aromas with date-like, 
fig-like, tobacco and rose topnotes to soaps, cosmetics, solid or liquid 
anionic, cationic, nonionic or zwitterionic detergents, fabric softener 
compositions, fabric softener articles, hair preparations and perfumed 
polymers. The amount employed can range up to 100% 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 substituted tetrahydroindanes of our invention are 
useful (taken alone or together with other ingredients in perfume 
compositions) as (an) olfactory component(s) in detergents and soaps, 
space odorants and deodorants, perfumes, colognes, toilet water, bath 
preparations, such as creams, deodorants, hand lotions and sun screens; 
powders such as talcs, dusting powders, face powders and the like. When 
used as (an) olfactory component(s) as little as 2% of at least one of the 
substituted tetrahydroindanes of our invention or even less will suffice 
to impart intense dry woody, rose, fruity, floral and tobacco-like aromas 
with date-like, fig-like, tobacco and rose topnotes to rose formulations 
and tobacco (perfumery) formulations. Generally, no more than 20% of at 
least one of the substituted tetrahydroindanes of our invention based on 
the ultimate end product is required in the perfume composition. 
Accordingly, in perfume compositions and colognes from about 0.1% up to 
100% of the perfume composition may be at least one of the substituted 
tetrahydroindanes of our invention. In perfumed articles, the quantity of 
at least one of the substituted tetrahydroindanes of our invention in the 
perfumed article may vary from about 0.01% up to about 25% of the perfumed 
article in the case of perfumed polymers, for example, and up to about 8% 
in the case of solid or liquid anionic, cationic, nonionic or zwitterionic 
detergents, for example. 
In addition, the perfume composition or fragrance composition of our 
invention can contain a vehicle, or carrier for at least one of the 
substituted tetrahydroindanes of our invention. The vehicle can be a 
liquid such as a non-toxic alcohol, such as ethyl alcohol or a non-toxic 
glycol, such as propylene glycol or the like. The carrier can also be an 
absorbent solid, such as a gum (e.g., gum arabic, xanthan gum, or guar gum 
or mixtures of same) or components for encapsulating the composition (such 
as gelatin as by means of coacervation or such as a ureaformaldehyde 
prepolymer when such a polymeric wall is formed around a liquid perfume 
composition center). 
The following Examples I-IV serve to illustrate the processes for preparing 
the compounds of our invention and compounds useful for their organoleptic 
properties. Examples following Example IV (Examples V, et seq.) illustrate 
organoleptic utilities of the substituted tetrahydroindanes of our 
invention. 
All parts and percentages given herein are by weight unless otherwise 
specified. 
EXAMPLE I 
PREATION OF 4,5,6,7-TETRAHYDRO-1-CHLORO-1,1,2,3,3-PENTAMETHYLINDANE 
Reaction: 
##STR60## 
A solution of 208 grams of 
4,5,6,7-tetrahydro-1-hydroxy-1,1,2,3,3-pentamethylindane in 300 grams of 
toluene is heated to 70.degree. C. Thionylchloride (148.5 grams) is added 
dropwise at 70.degree. C. over a period of one hour. The solution is 
heated to reflux eliminating SO.sub.2 and HCl gas. The reaction mixture is 
cooled to 30.degree. C. where upon it is washed with water and then 10% 
sodium bicarbonate. The solution is dried over 3.ANG. molecular sieves and 
used without further purification in Example II. 
FIG. 1 is the GC-MS profile of the compound having the structure: 
##STR61## 
thus prepared. 
EXAMPLE II 
PREATION OF 
METHYL-4,5,6,7-TETRAHYDRO-1,1,2,3,3-PENTAMETHYL-4-INDANEACETATE 
Reactions: 
##STR62## 
The toluene solution of 
4,5,6,7-tetrahydro-1-chloro-1,1,2,3,3-pentamethylindane (100 grams) as 
prepared in (Example I, supra) is added to a solution of 33 grams of 
dimethylmalonate and 54 grams of 25% sodium methoxide in methanol over a 
15 minute period at room temperature. The reaction mass is stirred two 
hours at room temperature and then poured into 200 ml of water. The 
resulting organic layer contains the compound having the structure: 
##STR63## 
FIG. 2 is the NMR spectrum for the compound having the structure: 
##STR64## 
The organic layer containing the compound having the structure: 
##STR65## 
is added to 120 grams of 25% sodium hydroxide at reflux. After heating at 
reflux for two hours, the mixture is cooled to room temperature. The 
resulting product has the structure: 
##STR66## 
Concentrated hydrochloric acid (60 ml) is then added with stirring to 
effect decarboxylation forming the indanyl acetic acid derivative having 
the structure: 
##STR67## 
FIG. 3 is the NMR spectrum for the compound having the structure: 
##STR68## 
The organic layer is heated for a period of three hours at reflux in 250 ml 
methanol in the presence of 2 grams of concentrated sulfuric acid. Sodium 
bicarbonate (6 grams) is added and 200 ml of methanol are removed via 
atmospheric distillation. 
The reaction mass is washed two times with 100 ml 5% sodium bicarbonate 
solution. Distillation affords 28 grams of indanyl compound having the 
structure: 
##STR69## 
(boiling point 142.degree. C. at 3 mm/Hg. pressure). 
FIG. 4 is the NMR spectrum for the compound having the structure: 
##STR70## 
The compound having the structure: 
##STR71## 
has a dry woody, rose and fruity aroma profile. 
EXAMPLE III 
PREATION OF 6,7-DIHYDRO-1,2,3,4,5-PENTAMETHYL INDANE 
Reaction: 
##STR72## 
200 Grams of the toluene solution of the compound having the structure: 
##STR73## 
prepared according to Example I is heated for a period of two hours at 
reflux in the presence of 110 grams of tributyl amine. The reaction mass 
is cooled and wash successively with 300 ml water and 300 ml 10% acetic 
acid. The solution containing the compound having the structure: 
##STR74## 
is used without further purification in Example IV, infra. 
FIG. 5 is the NMR spectrum for the compound having the structure: 
##STR75## 
EXAMPLE IV 
PREATION OF 4,5-EPOXY-4,5,6,7-TETRAHYDRO-1,1,2,3,3-PENTAMETHYLINDANE 
Reaction: 
##STR76## 
200 Grams of the toluene solution containing the compound having the 
structure: 
##STR77## 
prepared according to Example III is added dropwise over a one hour period 
to a stirred solution of 5 grams of sodium carbonate in 146 grams of 35% 
peracetic acid at 40.degree. C. The reaction mass is stirred at 40.degree. 
C. for four hours; then poured into 500 ml of water. The resulting organic 
layer is washed successively with 200 ml of 5% sodium carbonate, 5% sodium 
bisulfite, and 5% sodium carbonate. Distillation affords 65 grams of the 
epoxide having the structure: 
##STR78## 
(Boiling point: 102.degree. C. at 3 mm/Hg. pressure). 
The compound having the structure: 
##STR79## 
has a fruity, floral, tobacco-like and rose aroma with date-like, 
fig-like, tobacco and rose topnotes. 
FIG. 6 is the NMR spectrum for the compound having the structure: 
##STR80## 
EXAMPLE V 
The following rose/tobacco formulations are prepared: 
______________________________________ 
Parts by Weight 
Ingredients V(A) V(B) V(C) 
______________________________________ 
Phenylethyl alcohol 
12 12 12 
Geraniol 14 14 14 
Geranyl acetate 8 8 8 
Rose oxide 4 4 4 
Bulgarian rose oil 
0.2 0.2 0.2 
Betadamascenone 1 1 1 
The compound having 
18 0 0 
the structure: 
##STR81## 
prepared according 
to Example II. 
The compound having 
0 18 0 
the structure: 
##STR82## 
prepared according 
to Example IV. 
50:50 Mixture of the 
0 0 18 
compound having 
the structure: 
##STR83## 
prepared according 
to Example II 
and the compound having 
the structure: 
##STR84## 
prepared according 
to Example IV. 
______________________________________ 
The compound having the structure: 
##STR85## 
prepared according to Example II adds a dry woody and fruity undertone to 
this rose formulation. Accordingly, the rose formulation of Example V(A) 
can be described as "rose with a dry woody and fruity undertone". 
The compound having the structure: 
##STR86## 
prepared according to Example IV adds to this rose formulation a fruity 
and tobacco-like undertone with date-like, fig-like and tobacco topnotes. 
Accordingly, the perfume formulation of Example V(B) can be described as 
"rose with fruity, floral and tobacco-like undertones and date-like, 
fig-like and tobacco topnotes". 
The mixture of compounds having the structures: 
##STR87## 
of Example V(C) adds to this rose formulation dry woody, fruity, floral 
and tobacco-like undertones, with date-like, fig-like and tobacco 
topnotes. Accordingly, the perfume composition of Example V(C) can be 
described as "rose with dry woody, fruity, floral and tobacco-like 
undertones and date-like, fig-like and tobacco topnotes". 
EXAMPLE VI 
COSMETIC POWDER PREATION 
A cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum 
powder with 0.25 grams of one of the substances set forth in Table II 
below containing at least one of the substituted tetrahydroindanes of our 
invention. Each of the cosmetic powders has an excellent aroma as 
described in Table II below. 
TABLE II 
______________________________________ 
Perfumery Substance 
Aroma Nuance 
______________________________________ 
The compound having 
A dry woody, rose and fruity 
the structure: aroma profile. 
##STR88## 
prepared according 
to Example II. 
The compound having 
A fruity, floral, tobacco-like 
the structure: and rose aroma with date-like, 
##STR89## fig-like and tobacco and rose topnotes. 
prepared according 
to Example IV. 
Perfume composition 
Rose with a dry woody and 
of Example V(A). 
fruity undertone. 
Perfume composition 
Rose with fruity, floral and 
of Example V(B). 
tobacco-like undertones and 
date-like, fig-like and tobacco 
topnotes. 
Perfume composition 
Rose with dry woody, fruity, 
of Example V(C). 
floral and tobacco-like undertones 
and date-like, fig-like and 
tobacco topnotes. 
______________________________________ 
EXAMPLE VII 
PERFUMED LIQUID DETERGENT 
Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonic 
acid as more specifically described in U.S. Letters Pat. No. 3,948,818 
issued on April 6, 1976 the specification for which is incorporated by 
reference herein) with aromas as set forth in Table II of Example VI, 
supra are prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.35% 
of each of the substances of Table II of Example VI. They are prepared by 
adding and homogeneously admixing the appropriate quantity of one of the 
substances of Table II of Example VI in the liquid detergent. The 
detergents all possess excellent aromas as set forth in Table II of 
Example VI. 
EXAMPLE VIII 
PREATION OF A COLOGNE AND HANDKERCHIEF PERFUME 
The substances set forth in Table II of Example VI are incorporated 
separately into colognes at concentrations of 2.0%, 2.5%, 3.0, 3.5%, 4.0%, 
4.5% and 5.0 in 75%, 80%, 85% and 90% 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 aromas as set forth in Table II of Example VI, 
supra are imparted to the colognes and to the handkerchief perfume 
compositions at all levels indicated. 
EXAMPLE IX 
PREATION OF SOAP COMPOSITION 
One hundred grams of soap chips (IVORY.RTM., produced by the Procter and 
Gamble Company, of Cincinnati, Ohio) are admixed with 1 gram of each of 
the substances of Table II of Example VI, supra, until homogeneous 
compositions are obtained. The homogeneous compositions are each separated 
then heated under 3 atmospheres pressure at 180.degree. C. for a period of 
3 hours and the resulting liquid samples are placed in soap molds. The 
resulting soap cake, on cooling, manifest excellent longlasting aromas as 
set forth in Table II of Example VI, supra. 
EXAMPLE X 
PREATION OF SOLID DETERGENT COMPOSITIONS 
Detergents are prepared from the following ingredients according to Example 
I of Canadian Letters Pat. No. 1,007,948 the specification for which is 
incorporated by reference herein: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
NEODOL .RTM. 45-11 (a 
12 
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. A total of 100 grams of said 
detergent is admixed separately with 0.10, 0.15, 0.20 and 0.25 grams of 
each of the substances of Table II of Example VI. Each of the detergent 
samples has an excellent aroma as set forht in Table II of Example VI. 
EXAMPLE XI 
DRYER-ADDED FABRIC SOFTENER ARTICLE 
Utilizing the procedure of Example I at column 15 of U.S. Pat. No. 
3,623,396, the specification for which is incorporated by reference 
herein, a non-woven cloth substrate useful as a dryer-added fabric 
softening article of manufacture is 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 have 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 of 
Table II of Example VI, supra. 
______________________________________ 
Fabric softening compositions containing one of the substances of Table II 
of Example VI consist esentially of a substrate having a weight of about 3 
grams per 100 square inches of substrate coating having a weight of about 
1.85 grams per 100 square inches; and an outer coating having a weight of 
about 1.4 grams per 100 square inches thereby providing a total aromatized 
substrate and outer coating weight ratio of about 1:1 by weight of the 
substrate. 
Pleasant aromas as set forth in Table II of Example VI are imparted to the 
head space in the dryer on operation thereof using the said drier-added 
softening non-woven fabric.