Use of 7-isopropyl - -8, 8-dimethyl-6, 10-dioxaspiro-C.sub.10 and C.sub.11 alkane derivatives for their organoleptic properties and synthesis process for preparing such derivaties

Described is the use of 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane derivatives defined according to the structure: ##STR1## wherein N is 1 or 2 for their organoleptic properties, particularly for use in imparting, augmenting or enhancing the aroma of a perfume composition, perfumed polymer, detergent, fabric softener, or bleach composition. Also described is a process for preparing such 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane derivatives using as starting materials cycloalkanones defined according to the structure: ##STR2## and the diol having the structure: ##STR3##

BACKGROUND OF THE INVENTION 
Our invention is related to a process for imparting, augmenting or 
enhancing the aroma of a perfume composition, perfume polymer, soap, 
detergent, fabric softener or bleach composition by adding to such 
material an aroma imparting, augmenting or enhancing quantity and 
concentration of at least one 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivative defined according to the structure: 
##STR4## 
wherein N is 1 or 2. Our invention is also related to perfume compositions 
consisting essentially of a non-salicylate-containing perfume base and 
intimately admixed therewith an aroma augmenting or enhancing quantity and 
concentration of at least one 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivative defined according to the structure: 
##STR5## 
wherein N is 1 or 2. Our invention is further related to the process for 
preparing such 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and 
C.sub.11 alkane derivatives using as starting materials a cycloalkanone 
defined according to the structure: 
##STR6## 
and a diol having the structure: 
##STR7## 
Inexpensive chemical compounds which are substantive and long-lasting and 
which can provide strong, persistent minty, sage, guaiac wood, pepper, 
fruity, herbal, woody, sweet, balsamic, chamomile, jasmine, eucalyptus and 
anisic aromas with minty, sage, parsley, seashore, pepper, rhubarb, woody, 
sweet, floral, jasmine, caryophyllene-like, mushroomy, waxy and anisic 
topnotes are highly desirable in the art of perfumery. Many of the natural 
materials which provide such fragrances and contribute such desired 
nuances to perfume compositions as well as perfumed articles are high in 
cost, unobtainable at times, vary in quality from one batch to another 
and/or are generally subject to the usual variations of natural products. 
There is, accordingly, a continuous effort to find synthetic materials 
which will replace, enhance or augment the fragrance notes provided by 
natural essential oils or compositions thereof. Unfortunately, many of the 
synthetic materials either have the desired nuances only to a relatively 
small degree or they contribute undesirable or unwanted odor to the 
perfumes. 
Of particular importance are odorants of the minty, herbaceous type for use 
in fruity and floral fragrances. 
Ketals are known for their organoleptic properties, particularly coolant 
compositions as disclosed and claimed in U.S. Pat. No. 5,451,404 issued on 
Sep. 19, 1995, the specification for which is incorporated by reference 
herein. U.S. Pat. No. 5,451,404 discloses coolant compositions to provide 
cooling sensation to the mucosal membranes and/or to the skin, including 
toothpastes, mouthwashes, perfumes, lotions, shaving cream, post shaving 
preparations, shampoos, antiperspirants, deodorants, beverages, chewing 
gum, tobacco products and pharmaceutical products comprising a ketal and a 
secondary coolant which may be a menthol, carboxamides or mixtures 
thereof. The ketals of U.S. Pat. No. 5,451,404 are of the formula: 
##STR8## 
wherein R.sup.1 represents a C.sub.2 -C.sub.6 alkylene radical having at 
least 1 but not more than 3 hydroxyl groups, either R.sup.2 and R.sup.3 
independently of one another represents C.sub.1 -C.sub.10 alkyl which is 
optionally substituted by 1 to 3 radicals selected from the group 
consisting of hydroxyl, amino and halogen, C.sub.5 -C.sub.7 cycloalkyl, 
C.sub.6 -C.sub.12 aryl, with the proviso that the total number of the C 
atoms of R.sup.2 and R.sup.3 is not less than 3, or R.sup.2 and R.sup.3 
together represent an alkylene radical which, together with the carbon 
atom which carries the radicals R.sup.2 and R.sup.3, forms a 5-7-membered 
ring. More specifically, the ketal of U.S. Pat. No. 5,451,404 is 
preferably of the structure: 
##STR9## 
wherein R.sup.4 to R.sup.15 independently of one another denote hydrogen 
or C.sub.1 -C.sub.6 alkyl, preferably hydrogen or C.sub.1 -C.sub.4 alkyl 
and m and n independently of one another denote zero or 1. The preferred 
ketals of U.S. Pat. No. 5,451,404 have the structures: 
##STR10## 
The structures of the ketals of U.S. Pat. No. 5,451,404 are different in 
kind from the structures of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention. 
Ketals defined according to the structure: 
##STR11## 
particularly those having the structures: 
##STR12## 
and including the ketals useful in our invention, are indicated in German 
Offenlegungsschrift No. 2,533,048 published on Feb. 17, 1977 (and 
abstracted in Chemical Abstracts, Volume 86:195071e) to be useful as 
inflamation preventative agents for cosmetic preparations and for the 
treatment of sunburn. In the generic structure: 
##STR13## 
R.sub.1 '-R.sub.6 ' represents hydrogen, C.sub.1 -C.sub.8 alkyl or C.sub.1 
-C.sub.4 hdyroxyalkyl; m represents zero, 1 or 2; and Y represents, inter 
alia, alkylene having up to 9 carbon atoms. The German Offenlegungsschrift 
No. 2,533,048 discloses the use of such compounds as sunburn inhibitors 
when such compounds are present in such substances as body lotions, 
shaving lotions, shaving powders and baby powders. German 
Offenlegungsschrift No. 2,533,048 discloses the use of the compounds 
having the structure: 
##STR14## 
in conjunction with salicylates, for example, benzyl and menthyl 
salicylate. However, no perfume compositions or perfume bases are 
indicated to be created using the compounds defined according to the 
structure: 
##STR15## 
by German Offenlegungsschrift No. 2,533,048. Indeed, German 
Offenlegungsschrift No. 2,533,048 does not recognize the usefulness in 
perfumery of the ketals defined according to the generic structure: 
##STR16## 
In summary, nothing in the prior art discloses the use of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention for their perfumery properties. 
German Offenlegungsschrift No. 2,533,048 discloses a synthesis for 
preparing compounds having the structure: 
##STR17## 
by reacting cycloalkanones with the diols, for example, the diol having 
the structure: 
##STR18## 
in the presence of triethylorthoformate. However, German 
Offenlegungsschrift No. 2,533,048 fails to disclose the efficient two step 
process for preparing substantially pure ketals according to the 
reactions: 
##STR19## 
wherein N is 1 or 2; wherein R.sub.9, R.sub.10 and R.sub.11 are the same 
or different methyl or ethyl; wherein R.sub.12 and R.sub.13 are the same 
or different methyl or ethyl; and wherein R.sub.14 is methyl or ethyl.

DETAILED DESCRIPTION OF THE DRAWINGS 
Referring to FIG. 1, the peak indicated by reference numeral 10 is the peak 
for the compound having the structure: 
##STR30## 
The peak indicated by reference numeral 11 is the peak for the starting 
material, the diol, having the structure: 
##STR31## 
The peak indicated by reference numeral 12 is the peak for the 
cyclohexanone starting material having the structure: 
##STR32## 
Referring to FIG. 2, the peak indicated by reference numeral 20 is the peak 
for the compound having the structure: 
##STR33## 
Referring to FIG. 4, the peak indicated by reference numeral 40 is the peak 
for the ketal having the structure: 
##STR34## 
The peak indicated by reference numeral 41 is the peak for the 
cyclohexanone starting material having the structure: 
##STR35## 
The peak indicated by reference numeral 42 is the peak for the 
trimethylorthoformate having the structure: 
##STR36## 
Referring to FIG. 5, the peak indicated by reference numeral 50 is the peak 
for the diol having the structure: 
##STR37## 
The peak indicated by reference numeral 51 is the peak for the ketal 
having the structure: 
##STR38## 
The peak indicated by reference numeral 52 is the peak for the 
cyclohexanone starting material having the structure: 
##STR39## 
Referring to FIG. 6, the peak indicated by reference numeral 60 is the peak 
for the compound having the structure: 
##STR40## 
The peak indicated by reference numeral 61 is the peak for the starting 
material, the glycol, having the structure: 
##STR41## 
The peak indicated by reference numeral 62 is the peak for the reaction 
solvent, toluene. 
Referring to FIG. 7, the peak indicated by reference numeral 70 is the peak 
for the compound having the structure: 
##STR42## 
The peak indicated by reference numeral 71 is the peak for the ketal 
having the structure: 
##STR43## 
The peak indicated by reference numeral 72 is the peak for the starting 
material, the glycol, having the structure: 
##STR44## 
The peak indicated by reference numeral 73 is the peak for the reaction 
solvent, toluene. The peak indicated by reference numeral 74 is the peak 
for the cyclopentanone having the structure: 
##STR45## 
Referring to FIG. 8, the peak indicated by reference numeral 80 is the peak 
for the product having the structure: 
##STR46## 
Referring to FIGS. 11 and 12, the apparatus used in producing polymeric 
fragrances containing one or more of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives 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 polyolefin such as polyethylene and an aromatic 
substance or scented material is placed (in this case at least one of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention). 
The container is closed by an air-tight lid 228 and the air-tight lid 228 
is clamped to the container 212 by bolts 265. 
A stirrer 273 traverses the lid or cover 228 in an air-tight manner and is 
rotated in a suitable manner. 
Container 212 having heating coils 212A which are supplied with electric 
current through cable 224 from a rheostat or control 216 is operated to 
maintain a 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 212A 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 control 220 connected 
thereto through a connecting wire 222 to maintain the lower portion of the 
container within a temperature range of from 250.degree.-350.degree. F. 
Thus, polymer (e.g., polyethylene is added to container 212 and is heated 
from 10-12 hours whereafter a scented aroma imparting material (at least 
one of the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 
alkane derivatives of our invention) is added quickly to the melt. The 
material must be compatible with the polyolefin and forms a homogeneous 
liquid melt therewith. The scented material is of a type for the 
particular aroma desired and formulated specifically for the scenting 
purpose for which the polyolefin will be employed. 
Generally, about 5-30% by weight of the scented material (containing at 
least one of the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and 
C.sub.11 alkane derivatives of our invention) are added to the polyolefin. 
After the scent imparting material (e.g., a composition containing at least 
one of the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 
alkane derivatives 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 range as indicated, supra, by means of 
heating coils 212A. 
The controls 216 and 220 are connected, respectively, through cables 214 
and 222, respectively, to heating coils 212A. The said controls 216 and 
220 are also connected through cables 224 and 226 respectively, to a 
suitable power supply of electric current for supplying the electric power 
to the heating coils 212A for heating purposes. 
Thereafter, the valve "V" is opened permitting the mass to flow outwardly 
through conduit 218/232 having a multiplicity of orifices 234, adjacent to 
the lower side thereof. The outer end of the conduit 218/232 is closed so 
that the liquid polymer (e.g., polyolefin) and aroma imparting material 
(e.g., a mixture containing at least one of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention) will continuously drop through orifices 234 
downwardly from conduit 232. During this time, the temperature of the 
polymer (e.g., polyolefin) and aroma imparting material (e.g., a mixture 
containing at least one of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention) is accurately controlled so that a 
temperature in the range of from about 210.degree.-275.degree. F. will 
exist in the conduit 218/232. The regulation of the temperature through 
the controls 216 and 220 is essential in order to insure temperature 
balance to provide for the continuous dropping or dripping of molten 
polymer (e.g., polyethylene) and scenting material (e.g., one or more of 
the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention) mixture 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 instantaneously and fall off the end of the conveyor 
238 into a container 245 and utilized in processes as illustrated, infra. 
A feature of this aspect of the process of our invention is the provision 
for moistening the conveyor belt 238 to insure rapid formation of the 
solid polymeric (e.g., polyolefin) scented pellets 244 without sticking to 
the belt. The belt 238 is advantageously fabricated of a material which 
will not normally stick to a melted plastic, but a moistening means 248 
insures a sufficiently cold temperature of the belt surface for an 
adequate formation of the pellets 244. The adequate moistening means 
comprises a container 250 which is continuously fed with water 254 to 
maintain a level for moistening a sponge element 256 which bears against 
the exterior of the belt 238. 
THE INVENTION 
The present invention provides 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives defined according to the generic structure: 
##STR47## 
wherein N is 1 or 2 for imparting, augmenting or enhancing the aroma of a 
substance selected from the group consisting of perfume compositions, 
perfumed polymers, soaps, anionic, nonionic, cationic or zwitterionic 
detergents, fabric softener articles, fabric softener compositions and 
bleach compositions. The present invention also provides perfume 
compositions consisting essentially of a non-salicylate-containing perfume 
base and intimately admixed therewith an aroma augmenting or enhancing 
quantity and concentration of at least one 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivative defined according to the structure: 
##STR48## 
wherein N is 1 or 2. The present invention also provides efficient 
processes for preparing substantially pure forms of 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives defined according to the structure: 
##STR49## 
wherein N is 1 or 2 by means of a two step process shown according to the 
reactions: 
##STR50## 
wherein N is 1 or 2; wherein R.sub.9, R.sub.10, R.sub.11, R.sub.12 and 
R.sub.13 are the same or different methyl or ethyl; and wherein R.sub.14 
is methyl or ethyl. 
The compositions of matter of our invention produced according to the 
processes disclosed in the instant specification are capable of 
augmenting, enhancing or providing strong, persistent and stable minty, 
sage, guaiac wood, pepper, fruity, herbal, woody, sweet, balsamic, 
chamomile, jasmine, eucalyptus and anisic aromas with minty, sage, 
parsley, seashore, pepper, rhubarb, woody, sweet, floral, jasmine, 
caryophyllene-like, mushroomy, waxy and anisic topnotes to perfume 
compositions, colognes and perfumed articles (e.g., solid or liquid, 
anionic, cationic, nonionic or zwitterionic detergents, fabric softener 
articles, drier-added fabric softener articles, fabric softener 
compositions, cosmetic powders, hair preparations, perfumed polymers, 
alkali metal perborate, bleaches and hypochlorite bleaches). 
The 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention are known in the prior art, but their 
perfumery uses are not disclosed or inferred. 
Surprisingly and advantageously, the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention are enduring perfume ingredients 
characterized by their octanol/water partition coefficient (P) being such 
that their logarithms to the base 10, log.sub.10 P, are between 4.50 and 
5.00. Thus, the log.sub.10 P of the compound having the structure: 
##STR51## 
is 4.65. 
It is indicated in U.S. Pat. No. 5,500,137 issued on Mar. 19, 1996, the 
specification for which is incorporated by reference herein, that a 
valuable octanol/water partitioning coefficient P of about 1,000 or higher 
is most advantageous in that it infers an enduring perfume. Indeed, the 
log.sub.10 P of many perfume ingredients has been reported, for example, 
the POMONA 92.RTM. database available from Daylight Chemical Information 
Systems, Inc. (Daylight CIS), Irvine, Calif., contains many, along with 
citations to the original literature. The "calculated log.sub.10 P" is 
determined by the fragment approach of Hansch and Leo (cf., A. Leo in 
Comprehensive Medicinal Chemistry, Volume 4; C. Hansch, P. G. Sammens, J. 
B. Taylor and C. A. Ranaden, Editors, page 295, Pergamon Press, 1990, 
incorporated by reference herein. The fragment approach is based on the 
chemical structure of each perfume ingredient and takes into account the 
numbers and types of atoms, the atom connectivity and chemical bonding. 
The boiling point of the compound having the structure: 
##STR52## 
is 83.degree.-84.degree. C. (vapor temperature) at a pressure of 3.0 
mm/Hg. The boiling point of the compound having the structure: 
##STR53## 
is 87.degree. C. (vapor temperature) at 3.6 mm/Hg. pressure. 
It is particularly advantageous that the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives defined according to the structure: 
##STR54## 
wherein N is 1 or 2 are both "enduring" and, at the same time, bleach 
stable in hypochlorite bleaches and in alkali metal perborate bleaches. 
The 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention may be prepared by one of two processes. 
Thus, a first process involves the reaction of the diol defined according 
to the structure: 
##STR55## 
with a cycloalkanone defined according to the structure: 
##STR56## 
according to the reaction: 
##STR57## 
This reaction takes place in the presence of an inert solvent at reflux 
conditions in the presence of a protonic acid catalyst, preferably 
paratoluene sulfonic acid or xylene sulfonic acid. The reaction 
temperature, being at reflux conditions and 1 atmosphere of pressure is 
about 120.degree. C. The time of reaction is between 3 and about 10 hours. 
While the reaction is taking place, it is preferable to remove water of 
reaction, for example, using a Bidwell water trap during the refluxing 
process. 
A second, more preferred (and novel) reaction sequence involves first 
reacting a cycloalkanone defined according to the structure: 
##STR58## 
with a trialkylorthoformate having the formula: 
##STR59## 
wherein R.sub.9, R.sub.10 and R.sub.11 are the same or different methyl or 
ehtyl according to the reaction: 
##STR60## 
thereby forming a methyl and/or ethyl ketal having the structure: 
##STR61## 
and an enol ether having the structure: 
##STR62## 
wherein R.sub.12 and R.sub.13 are the same or different methyl or ethyl 
and the structure: 
##STR63## 
is an individual compound or a mixture in the event that at least one of 
R.sub.9, R.sub.10 and R.sub.11 is methyl and at least one of R.sub.9, 
R.sub.10 and R.sub.11 is ethyl. This first reaction is carried out at a 
temperature in the range of from about 35.degree. C. up to about 
45.degree. C. at atmospheric pressure in the presence of an inert solvent 
such as methyl alcohol or ethyl alcohol and a reaction promoter such as 
acetyl chloride or acetyl bromide. At the end of the reaction, the 
reaction mass is treated with a small quantity of an alkali metal alkoxide 
such as sodium methylate or potassium-t-butoxide. Fractional distillation 
effects the separation of the compound having the structure: 
##STR64## 
from the compound having the structure: 
##STR65## 
The compound having the structure: 
##STR66## 
can be used "as is" for its perfumery properties or can be used as a 
reaction intermediate to form other compounds. The compound having the 
structure: 
##STR67## 
is then further reacted with the diol having the structure: 
##STR68## 
according to the reaction: 
##STR69## 
The second reaction of this sequence takes place at reflux conditions in 
the presence of an inert solvent such as toluene using a catalyst such as 
paratoluene sulfonic acid. The reaction is carried out at reflux using a 
Bidwell water trap continuously removing water during the refluxing 
process. At the end of the reaction, the reaction mass is worked up by 
neutralizing the reaction mass with, for example, sodium bicarbonate, and 
then drying the resulting product using anhydrous sodium sulfate. The 
dried product is then fractionally distilled to yield the substantially 
pure material defined according to the structure: 
##STR70## 
Table I below sets forth the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention and their fragrance properties: 
TABLE I 
______________________________________ 
Structure of Compound 
Perfumery Property 
______________________________________ 
The compound having the structure: 
A minty, sage, guaiac wood and pepper aroma with minty, 
sage, parsley, seashore, pepper, caryophyllene-like and 
rhubarb topnotes. 
##STR71## 
prepared according to 
Example III, distillation 
fraction 5. 
The compound having the structure: 
A minty, fruity, herbal, woody, balsamic, chamomile, 
jasmine, eucalyptus and anisic aroma with woody, sweet, 
loral, jasmine, mushroomy, waxy and anisic topnotes. 
##STR72## 
prepared according to 
Example I, bulked distillation 
fractions 2-4. 
______________________________________ 
As olfactory agents, the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 
and C.sub.11 alkane derivatives of our invention taken alone or in 
admixture can be formulated into or used as components of a "perfume 
composition" or can be used as components of a "perfumed article" or the 
perfume composition may be added to perfumed articles. 
The term "perfume composition" is used herein to mean a mixture of organic 
compounds including, for example, alcohols, aldehydes, ketones, nitriles, 
ethers, lactones, epoxides, ketals (other than the ketals of our 
invention), natural essential oils, synthetic essential oils and 
hydrocarbons which are admixed so that the combined odors of the 
individual components produce a pleasant or desired fragrance. 
With respect to "perfume compositions", it is not intended herein that the 
perfume compositions of our invention be solely limited to the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention and salicylates such as benzyl salicylate or 
ethyl salicylate. This invention is not intended to cover compositions 
solely consisting of salicylates and the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention. 
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, the individual component will contribute its 
particular olfactory characteristics, but the overall effect of the 
perfume composition will be the sum of the effects of each of the 
ingredients and, in certain instances, a synergistic effect as a result of 
the addition of certain ingredients. Thus, the individual 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention, or mixtures thereof, can be used to alter 
the aroma characteristics of a perfume composition, for example, by 
highlighting or moderating the olfactory reaction contributed by another 
ingredient in the composition. 
The amount of the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and 
C.sub.11 alkane derivatives of this invention which will be effective in 
perfume compositions 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 0.05% of one or 
both of the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 
alkane derivatives of our invention, or even less, can be used to impart 
minty, sage, guaiac wood, pepper, fruity, herbal, woody, sweet, balsamic, 
chamomile, jasmine, eucalyptus and anisic aromas with minty, sage, 
parsley, seashore, pepper, rhubarb, woody, sweet, floral, jasmine, 
caryophyllene-like, mushroomy, waxy and anisic topnotes to soaps, solid or 
liquid, anionic, cationic, nonionic or zwitterionic detergents, cosmetics, 
cosmetic powders, liquid or solid fabric softeners, drier-added fabric 
softener articles (e.g., BOUNCE.RTM., a Registered Trademark of the 
Procter & Gamble Company of Cincinnati, Ohio), optical brightener 
compositions, hypochlorite bleach compositions, fragranced polymers, hair 
conditioners and other products. The amount employed can range up to 70% 
or even higher and will depend on considerations of cost, nature of the 
end product and the effect desired on the finished product and particular 
fragrance sought. Thus, for example, when fragrancing liquid bleach 
compositions containing alkali metal hypochlorite such as, for example, 
sodium hypochlorite, for example, CLOROX.RTM. (Registered Trademark of 
Clorox, Inc.), the amount employed can range as high as 100% of the 
fragrance involved in the liquid bleach. Indeed, a distinctive aspect of 
our invention is the use of one or both of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention in a stable liquid bleach composition. 
The 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention, taken alone or in admixture, can be used 
alone or in a perfume composition (in the absence of a salicylates such as 
benzyl salicylate or menthyl salicylate) as an olfactory component in 
detergents, soaps, space odorants and deodorants; perfumes; colognes, 
toilet waters; bath salts; hair preparations such as lacquers, 
brilliantines, pomades and shampoos; cosmetic preparations such as creams, 
deodorants, hand lotions, such as creams; powders such as talcs, dusting 
powders, face powders and the like; liquid bleaches such as sodium 
hypochlorite-containing bleaches; floor waxes, automobile aromas and 
automobile polish compositions. 
When used as an olfactory component of a perfumed article, as little as 
0.01% of one or both of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention will suffice to impart an interesting minty, 
sage, guaiac wood, pepper, fruity, herbal, woody, sweet, balsamic, 
chamomile, jasmine, eucalyptus and anisic aromas with minty, sage, 
parsley, seashore, pepper, rhubarb, woody, sweet, floral, jasmine, 
caryophyllene-like, mushroomy, waxy and anisic topnotes. Generally, no 
more than 1.5% is required to impart such aromas. However, in view of the 
rather low cost of the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 
and C.sub.11 alkane derivatives of our invention, up to 100% of the 
perfume composition can be one or both of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention. 
In summary, the range of the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention in the perfumed article can be from 0.01% up 
to 1.5% or even higher. 
In addition, the perfume composition of our invention can contain a vehicle 
or carrier for the 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and 
C.sub.11 alkane derivatives of our invention, taken alone or with other 
ingredients. The vehicle can be a liquid such as a non-toxic alcohol such 
as ethanol, a glycol such as propylene glycol or the like. The carrier can 
be an absorbent solid such as a gum or components for encapsulating the 
composition such as gelatin which can be used to form a capsule wall 
surrounding the perfume oil as by means of coacervation with gelatin or as 
by means of formation of a polymer around the perfume oil as by 
polymerizing a urea formaldehyde prepolymer. 
It will thus be apparent that the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention can be used to alter, modify, augment or 
enhance sensory properties, particularly organoleptic properties such as 
fragrances of a wide variety of consumable materials. 
The 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention defined according to the structure: 
##STR73## 
wherein N is 1 or 2 are also useful in conjunction with bleaches which are 
"per-bleaches", for example, sodium perborate, sodium percarbonate or 
sodium persulfate. More particularly, the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention are useful in conjunction with particulate 
bleach activator compositions for per-bleaches as more specifically 
described in U.S. Pat. No. 5,534,195 issued on Jul. 9, 1996, the 
specification for which is incorporated by reference herein. 
The 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention may be combined with lactam bleach 
activator-containing particles which are specifically described in U.S. 
Pat. No. 5,534,196 issued on Jul. 9, 1996, the specification for which is 
incorporated by reference herein. 
PCT Application Ser. No. 95/07972 (corresponding to Czech Republic 
Application No. 96/00774) may be also utilized in conjunction with the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention defined according to the structure: 
##STR74## 
wherein N is 1 or 2. Thus, the compound having the structure: 
##STR75## 
may be combined in an amount of between 2 and 4% by weight in a bleach 
composition for a detergent comprising enzymatic hydrogen 
peroxide-generating system and coordination complex containing manganese 
ions as a bleach catalyst; or a coordination complex containing ferric 
ions as a bleach catalyst; or a coordination complex containing Mn.sup.++ 
(50%) and Fe.sup.++ ions as a bleach catalyst. 
The 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention defined according to the structure: 
##STR76## 
may also be used in sodium percarbonate particles used for bleaching 
wherein the particles have the external surfaces thereof coated with 
sodium borate as described in Spanish Patent Application No. 2,085,971 
(Kao Corporation) corresponding to European Patent No. 487,256. 
The 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention defined according to the structure: 
##STR77## 
wherein N is 1 or 2 are also useful in imparting aromas to bleach 
detergent compositions containing acid-based bleaching based compounds 
which generate hydrogen peroxide and which also include bleaching 
activators, cellulase and silicon compounds, for example, Japanese 
Published Patent Application No. JP08/157881 (Lion Corporation), which 
covers the combined use of the specific bleaching activator having the 
structure: 
##STR78## 
or having the structure: 
##STR79## 
wherein R.sup.1 is C.sub.10 -C.sub.18 alkyl or alkenyl; R.sup.2 is C.sub.7 
-C.sub.18 alkyl or alkenyl; and M represents a cation for providing water 
solubility to the bleaching activator, for example, M is sodium or 
potassium. The amount of 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 
and C.sub.11 alkane derivative of our invention defined according to the 
structure: 
##STR80## 
for example, the compound having the structure: 
##STR81## 
is used in such bleaching detergent compositions in an amount of from 
about 2% up to about 4%. A specific example is one containing 2% of the 
compound having the structure: 
##STR82## 
an acid-based bleaching based composition compound generating hydrogen 
peroxide and water; 0.5 weight percent cellulase; and 0.5 weight percent 
of a silicon compound. The 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention can also be used in bleaching detergent 
compositions described in Published Japanese Applications as follows: 
JP08/157874; 
JP08/157876; 
JP08/157877; 
JP08/157878; 
JP08/157880; 
JP08/157882; 
JP08/157883; 
JP08/157889; and 
JP08/157890. 
The 7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention defined according to the structure: 
##STR83## 
wherein N is 1 or 2 are also useful in bleach compositions when admixed 
with the non-friable composite granule bleach catalysts described in U.S. 
Pat. No. 5,536,441 issued on Jul. 16, 1996, the specification for which is 
incorporated by reference herein. In U.S. Pat. No. 5,536,441, described is 
a non-friable composite granule bleach composition containing mono- or 
di-nuclear manganese complex catalysts with amine ligands and soluble 
binding agents. 
The following examples serve to illustrate our invention, and this 
invention is considered to be restricted thereto only as indicated in the 
appended claims. 
All parts and percentages given herein are by weight unless otherwise 
specified. 
EXAMPLE I 
PREATION OF 
7-ISOPROPYL-8,8-DIMETHYL-6,10-DIOXASPIROCYCLOHEXANE 
Reaction: 
##STR84## 
Into a 5 liter reaction vessel equipped with stirrer, thermometer, reflux 
condenser, heating mantle and Bidwell trap are placed the following 
materials: 
(i) 2,2,4-trimethylpentane-1,3-diol having the structure: 
##STR85## 
6.85 moles; (ii) cyclohexanone, 6.22 moles; 
(iii) toluene, 5.43 moles; and 
(iv) paratoluene sulfonic acid, 0.58 moles. 
The resulting mixture with stirring is heated to reflux and refluxed at 
120.degree. C. for a period of 5 hours. 
At the end of the 5 hour period, the resulting reaction mass is washed with 
two 500 ml volumes of 10% aqueous sodium bicarbonate solution followed by 
1 volume of saturated aqueous sodium chloride solution. The resulting 
product now exists in two phases: an aqueous phase and an organic phase. 
The aqueous phase is separated from the organic phase, and the organic 
phase is distilled on a two inch splash ("rushover") distillation column 
yielding the following fractions: 
______________________________________ 
Fraction 
Vapor Liquid Vacuum mm/Hg. 
Number 
Temperature (.degree.C.) 
Temperature (.degree.C.) 
Pressure 
______________________________________ 
1 40 80 200.0 
2 28 82 30.0 
3 74 113 2.0 
4 87 125 1.5 
5 35 137 3.0 
______________________________________ 
Fractions 3-5 are bulked and redistilled on a 2 foot Goodloe distillation 
column yielding the following fractions: 
______________________________________ 
Fraction 
Vapor Liquid Vacuum mm/Hg. 
Number 
Temperature (.degree.C.) 
Temperature (.degree.C.) 
Pressure 
______________________________________ 
1 41/78 118/132 3.0 
2 78 131 3.0 
3 83 135 3.0 
4 84 134 3.0 
5 84 133 3.0 
______________________________________ 
Fractions 2-4 are bulked for fragrance use and for use in Examples IV, et 
seq. Bulked distillation fractions 2-4 have a minty, fruity, herbal, 
woody, sweet, balsamic, chamomile, jasmine, eucalyptus and anisic aroma 
with woody, sweet, floral, jasmine, mushroomy, waxy and anisic topnotes. 
Bulked distillation fractions 2-4 consist of the compound having the 
structure: 
##STR86## 
as confirmed by NMR, IR, mass spectral and GLC analyses. 
EXAMPLE II 
PREATION OF 
7-ISOPROPYL-8,8-DIMETHYL-6,10-DIOXASPIROCYCLOHEXANE 
EXAMPLE II (A) 
STEP 1 
Reaction: 
##STR87## 
Into a 3 liter reaction flask equipped with stirrer, thermometer, reflux 
condenser and heating mantle are placed the following materials: 
(i) cyclohexanone, 5.1 moles; 
(ii) trimethylorthoformate, 5.66 moles; and 
(iii) methanol, 15.63 moles. 
The resulting mixture is heated to 35.degree. C. and over a period of 1 
hour, 19 moles of acetyl chloride is added to the reaction mass while the 
reaction mass temperature with stirring is at 40.degree.-45.degree. C. 
During the addition of the acetyl chloride, methyl formate is distilled 
from the reaction mass. 
At the end of the feeding of the acetyl chloride, the reaction mass is 
cooled to 40.degree. C. Over a period of 1 hour, 40 grams of sodium 
methylate is added to the reaction mass. 
The reaction mass is then fractionally distilled on a two inch splash 
column yielding the following fractions: 
______________________________________ 
Fraction 
Vapor Liquid Vacuum mm/Hg. 
Number 
Temperature (.degree.C.) 
Temperature (.degree.C.) 
Pressure 
______________________________________ 
1 26/40 66/77 75 
2 51 66 75 
3 50 63 75 
4 48 73 75 
5 41 112 75 
______________________________________ 
Fractions 2, 3 and 4 are bulked for the subsequent reaction in Example 
II(B). Bulked distillation fractions 2-4 consist of the compound having 
the structure: 
##STR88## 
as confirmed by NMR, GLC, mass spectral and IR analyses. 
EXAMPLE II (B) 
STEP 2 
Reaction: 
##STR89## 
Into a 2 liter reaction vessel equipped with stirrer, thermometer, reflux 
condenser, heating mantle and a Bidwell water trap are placed the 
following materials: 
(i) 2,2,4-trimethylpentane-1,3-diol having the structure: 
##STR90## 
2.05 moles; (ii) cyclohexanone dimethylketal having the structure: 
##STR91## 
2.08 moles; (iii) toluene, 5.43 moles; and 
(iv) paratoluene sulfonic acid, 0.06 moles (11 grams). 
The resulting mixture is heated to reflux and refluxed at a temperature of 
170.degree. C. for a period of 2 hours. At the end of the 2 hour period, 
36 ml water was collected. 
The resulting reaction mass is washed with an equal volume of 10% aqueous 
sodium bicarbonate. The aqueous phase is separated from the organic phase, 
and the organic phase is dried over anhydrous sodium sulfate. The 
resulting dried product is then fractionally distilled on a two inch 
splash column yielding the following fractions: 
______________________________________ 
Fraction 
Vapor Liquid Vacuum mm/Hg. 
Number 
Temperature (.degree.C.) 
Temperature (.degree.C.) 
Pressure 
______________________________________ 
1 26/87 47/105 2.0 
2 106 109 3.4 
3 51 131 3.8 
______________________________________ 
Fraction 2 consists of a compound having the structure: 
##STR92## 
as confirmed by NMR, IR and mass spectral analyses. 
Fraction 2 has a minty, fruity, herbal, woody, sweet, balsamic, chamomile, 
jasmine, eucalyptus, anisic and earthy aroma with woody, sweet, floral, 
jasmine, mushroomy, waxy and anisic topnotes. 
EXAMPLE III 
PREATION OF 
7-ISOPROPYL-8,8-DIMETHYL-6,10-DIOXASPIROCYCLOPENTANONE 
Reactions: 
##STR93## 
Into a 2 liter reaction vessel equipped with stirrer, thermometer, reflux 
condenser, heating mantle and Bidwell trap are placed the following 
materials: 
(i) 2,2,4-trimethylpentane-1,3-diol having the structure: 
##STR94## 
2.05 moles; (ii) cyclopentanone dimethylketal having the structure: 
##STR95## 
1.92 moles; (iii) toluene, 5.43 moles; and 
(iv) paratoluene sulfonic acid, 0.06 moles. 
The compound having the structure: 
##STR96## 
is previously prepared according to the reaction: 
##STR97## 
and the compound having the structure: 
##STR98## 
is separated by fractional distillation from the previously formed 
1-methoxycyclopentene. 
The mixture in the 2 liter reaction vessel is heated to reflux with 
stirring and refluxed at a temperature of 190.degree. C. for a period of 3 
hours while removing water using the Bidwell trap. 36 Ml water is removed. 
The reaction mass is then cooled to room temperature and washed with an 
equal volume of 10% aqueous sodium bicarbonate solution, followed by an 
equal volume of aqueous 10% sodium chloride solution. 
The organic phase is then separated from the aqueous phase, and the organic 
phase is dried using anhydrous sodium sulfate. 
The resulting product is then fractionally distilled yielding the following 
fractions: 
______________________________________ 
Fraction 
Vapor Liquid Vacuum mm/Hg. 
Number 
Temperature (.degree.C.) 
Temperature (.degree.C.) 
Pressure 
______________________________________ 
1 31 50 250 
2 28 56 20 
3 77 95 4 
4 87 98 3.6 
5 79 145 3.4 
______________________________________ 
Fraction 5 consists of the compound having the structure: 
##STR99## 
as confirmed by NMR, IR, mass spectral and GLC analyses. 
The compound having the structure: 
##STR100## 
has a minty, sage, guaiac wood and pepper aroma with minty, sage, parsley, 
seashore, pepper, caryophyllene-like and rhubarb topnotes. 
EXAMPLE IV 
PERFUME FORMULATIONS 
The following floral, woody cologne perfume formulations are prepared: 
______________________________________ 
Parts by Weight 
Ingredients IV(A) IV(B) IV(C) 
______________________________________ 
Phenyl ethyl alcohol 200 200 200 
Bergamot oil 150 150 150 
Orange oil 200 200 200 
Lemon oil 50 50 50 
Eugenol 10 10 10 
4-(4-methyl-4-hydroxy amyl)-.DELTA..sup.3 cyclohexane 
40 40 40 
carboxaldehyde (LYRAL .RTM., Trademark of 
International Flavors & Fragrances Inc. of 
New York, New York) 
Ylang oil 2 2 2 
Petigrain Paraguay 10 10 10 
.gamma.-Methyl ionone 
20 20 20 
Vetiver Venezuela 18 18 18 
3-.alpha.-Methyl-dodecahydro-6,6,9a- 
5 5 5 
trimethyl-naphthol 2.1-b! furan 
Product produced by the reaction of acetic 
50 50 50 
anhydride, polyphosphoric acid and 1,5,9- 
trimethyl cyclododecatriene-1,5,9 according 
to the process of Example I of U.S. Pat. 
No. 3,718,698, the specification for which 
is incorporated by reference herein. 
Octahydro-9,9-dimethyl-1,6-methano- 
50 50 50 
naphthalene-1-2H!-ol produced according to 
Example III of U.S. Pat. No. 3,996,169, the 
specification for which is incorporated by 
reference herein. 
The compound having the structure: 
25 0 25 
##STR101## 
prepared according to Example III, 
distillation fraction 5. 
The compound having the structure: 
0 25 25 
##STR102## 
prepared according to Example I, 
distillation fractions 2-4. 
______________________________________ 
The compound having the structure: 
##STR103## 
prepared according to Example III, distillation fraction 5, imparts to 
this floral, woody cologne formulation strong, persistent minty, sage, 
guaiac wood and pepper undertones with minty, sage, parsley, seashore, 
pepper, caryophyllene-like and rhubarb topnotes. Accordingly, the perfume 
composition of Example IV(A) is described as: 
"A floral, woody cologne aroma with strong, persistent minty, sage, guaiac 
wood and pepper undertones and minty, sage, parsley, seashore, pepper, 
caryophyllene-like and rhubarb topnotes." 
The compound having the structure: 
##STR104## 
prepared according to Example I, bulked distillation fractions 2-4, 
imparts to this floral, woody cologne formulation strong, persistent 
minty, fruity, herbal, woody, sweet, balsamic, chamomile, jasmine, 
eucalyptus and anisic undertones with woody, sweet, floral, jasmine, 
mushroomy, waxy and anisic topnotes. Accordingly, the perfume composition 
of Example IV(B) is described as: 
"A floral, woody cologne aroma with strong, persistent minty, fruity, 
herbal, woody, sweet, balsamic, chamomile, jasmine, eucalyptus and anisic 
undertones and woody, sweet, floral, jasmine, mushroomy, waxy and anisic 
topnotes." 
The combination of the compounds having the structures: 
##STR105## 
imparts to this floral, woody cologne formulation strong, persistent 
minty, sage, guaiac wood, pepper, fruity, herbal, woody, sweet, balsamic, 
chamomile, jasmine, eucalyptus and anisic undertones with minty, sage, 
parsley, seashore, pepper, rhubarb, woody, sweet, floral, jasmine, 
caryophyllene-like, mushroomy, waxy and anisic topnotes. Accordingly, the 
perfume composition of Example IV(C) is described as: 
"A floral, woody cologne aroma with strong, persistent minty, sage, guaiac 
wood, pepper, fruity, herbal, woody, sweet, balsamic, chamomile, jasmine, 
eucalyptus and anisic undertones with minty, sage, parsley, seashore, 
pepper, rhubarb, woody, sweet, floral, jasmine, caryophyllene-like, 
mushroomy, waxy and anisic topnotes." 
EXAMPLE V 
PREATION OF COSMETIC POWDER COMPOSITION 
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 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 structure: 
A minty, sage, guaiac wood and pepper aroma with minty, 
sage, parsley, seashore, pepper, caryophyllene-like and 
rhubarb topnotes. 
##STR106## 
prepared according to Example III, 
supra, distillation fraction 5. 
The compound having the structure: 
A minty, fruity, herbal, woody, sweet, balsamic, 
chamomile, jasmine, eucalyptus and anisic aroma with 
woody, sweet, floral, jasmine, mushroomy, waxy and 
anisic topnotes. 
##STR107## 
prepared according to Example I, 
supra, bulked distillation 
fractions 2-4. 
The compound having the structure: 
A minty, fruity, herbal, woody, sweet, balsamic, 
chamomile, jasmine, eucalyptus, anisic and earthy aroma 
with woody, sweet, floral, jasmine, mushroomy, wasy and 
anisic topnotes. 
##STR108## 
prepared according Example II (B), 
bulked distillation fractions 2-4. 
The perfume composition of 
A floral, woody cologne aroma 
Example IV(A). with strong, persistent minty, 
sage, guaiac wood and pepper 
undertones and minty, sage, 
parsley, seashore, pepper, 
caryophyllene-like and rhubarb 
topnotes. 
The perfume composition of 
A floral, woody cologne aroma with 
Example IV(B). strong, persistent minty, fruity, 
herbal, woody, sweet, balsamic, 
chamomile, jasmine, eucalyptus and 
anisic undertones and woody, sweet, 
floral, jasmine, mushroomy, waxy 
and anisic topnotes. 
The perfume composition of 
A floral, woody cologne aroma with 
Example IV(C). strong, persistent minty, sage, 
guaiac wood, pepper, fruity, herbal, 
woody, sweet, balsamic, chamomile, 
jasmine, eucalyptus and anisic 
undertones with minty, sage, parsley, 
seashore, pepper, rhubarb, woody, 
sweet, floral, jasmine, 
caryophyllene-like, mushroomy, 
waxy and anisic topnotes. 
______________________________________ 
EXAMPLE VI 
PERFUMED LIQUID DETERGENTS 
Concentrated liquid detergents (Lysine salt of n-dodecybenzene sulfonic 
acid as more specifically described in U.S. Pat. No. 3,948,818 issued on 
Apr. 6, 1976 incorporated by reference herein) with aroma nuances as set 
forth in Table II of Example V 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 V. They are prepared by adding and homogeneously mixing the 
appropriate quantity of substance set forth in Table II of Example V in 
the liquid detergent. The detergents all possess excellent aromas as set 
forth in Table II of Example V, the intensity increasing with greater 
concentrations of substances as set forth in Table II of Example V. 
EXAMPLE VII 
PREATION OF COLOGNE AND HANDKERCHIEF PERFUMES 
Compositions as set forth in Table II of Example V are incorporated into 
colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0% 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 V are imparted 
to the colognes and to the handkerchief perfumes at all levels indicated. 
EXAMPLE VIII 
PREATION OF SOAP COMPOSITION 
100 Grams of soap chips per sample! (IVORY.RTM. produced by the Procter & 
Gamble Company of Cincinnati, Ohio) are each mixed with 1 gram samples of 
substances as set forth in Table II of Example V 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 3 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 V. 
EXAMPLE IX 
PREATION OF SOLID DETERGENT COMPOSITIONS 
Detergents are prepared using the following ingredients according to 
Example I of Canadian Patent No. 1,007,948 (incorporated by reference 
herein): 
______________________________________ 
Ingredients Percent by Weight 
______________________________________ 
NEODOL .RTM. 45-11 (a C.sub.12 -C.sub.15 alcohol 
12 
ethoxylated with 11 moles of 
ethylene oxide) 
Sodium carbonate 55 
Sodium citrate 20 
Sodium sulfate, water brighteners 
q.s. 
______________________________________ 
This detergent is a phosphate-free detergent. Samples of 100 grams each of 
this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams of each of 
the substances as set forth in Table II of Example V. Each of the 
detergent samples has an excellent aroma as indicated in Table II of 
Example V. 
EXAMPLE X 
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), 
non-woven cloth substrates useful as drier-added fabric softening articles 
of manufacture are prepared wherein the substrate, the substrate coating, 
the outer coating and their 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; and 
1% of one of the substances as set forth in Table II of Example V, supra. 
Fabric softening compositions prepared according to Example I at column 15 
of U.S. Pat. No. 3,632,396 having the aroma characteristics as set forth 
in Table II of Example V, 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 II of Example V is admixed in 
each case with the outer coating mixture, thereby providing a total 
aromatized outer coating weight ratio to substrate of about 0.5:1 by 
weight of the substrate. The aroma characteristics are imparted in a 
pleasant manner to the head space in a drier on operation thereof in each 
case using said drier-added softener non-woven fabrics and these aroma 
characteristics are described in Table II of Example V, supra. 
EXAMPLE XI 
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% of food grade ethanol. 8.0 
Grams of the polymer is dissolved in the alcohol. The following 
ingredients are added to the PVP/VA alcoholic solution: 
______________________________________ 
Ingredients Percent by Weight 
______________________________________ 
Dioctyl sebacate 0.05 
Benzyl alcohol 0.10 
Dow Corning 473 fluid (prepared by the 
0.10 
Dow Corning Corporation) 
TWEEN .RTM. 20 surfactant (prepared by ICI 
0.03 
America Corporation) 
One of the perfumery substances as set 
0.10 
forth in Table II of Example IV, supra 
______________________________________ 
The perfuming substances as set forth in Table II of Example V add aroma 
characteristics as set forth in Table II of Example V which are rather 
intense and aesthetically pleasing to the users of the soft-feel, 
good-hold pump hair sprays. 
EXAMPLE XII 
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 the Union Carbide Corporation) (1.4 weight percent). The 
resulting melt is admixed with Stepanol WAT produced by the Stephan 
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 weight percent polyethylene glycol 6000 
distearate produced by the 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 II of Example V 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 V. 
In the following examples, ARCOMOX.RTM. DMC-W and AROMOX.RTM. DMMC-W are 
30% aqueous solutions of dimethyl cocoamine oxide; and ARCMOX.RTM. NCMD-W 
is 40% solution of N-cocomorpholine oxide produced by Armac Division of 
AKZO of Chicago, Ill. DOWFAX.RTM. 2A1 (a Registered Trademark of the Dow 
Chemical Company of Midland, Mich.) is the compound having the structure: 
##STR109## 
wherein the C.sub.12 H.sub.25 moiety is branched chain and the 
SO.sub.3.sup.- Na.sup.+ moieties are at various positions on each of the 
benzene rings. DOWFAX.RTM. 3B2 is a mixture of compounds defined according 
to the structure: 
##STR110## 
wherein the SO.sub.3.sup.- Na.sup.+ moieties are at various positions on 
the phenyl moieties. DOWFAX.RTM. 3B2 is a Registered Trademark of the Dow 
Chemical Company of Midland, Mich. 
In the following examples, in place of the DOWFAX.RTM. 2A1 and the 
DOWFAX.RTM.3B2, similar materials, for example, the compound having the 
structure: 
##STR111## 
may be used or, generically, the compound defined according to the 
structure: 
##STR112## 
may be used wherein at least one of R.sub.1 and R.sub.2 is C.sub.10 
-C.sub.12 straight chain or branched chain alkyl and M.sub..alpha. and 
M.sub..beta. are the same or different and each represents alkali metal 
selected from the group consisting of lithium, potassium and sodium. 
Furthermore, AROMOX.RTM. DMC-W, AROMOX.RTM. DMMC-W and ARCOMOX.RTM. NCMD-W 
are covered by the generic structure: 
##STR113## 
wherein R.sub.3 '" is straight chain alkyl; wherein more than 55% of the 
R.sub.3 '" moieties consist of straight chain alkyl having from 11 up to 
13 carbon atoms and where A and B are each separately methyl or taken 
together complete a morpholine ring. 
EXAMPLE XIII 
Four drops of each of the materials of Table II of Example V is added to 2 
grams of AROMOX.RTM. DMC-W to produce a clear premix. The clear premix is 
added to 200 grams of CLOROX.RTM. with stirring resulting in a clear, 
stable, single phase solution. Sufficient 1M (molar) aqueous NaOH is added 
to bring the pH of the mixture up to 12.8. The solution remains 
substantially stable at 120.degree. F. for a period of seven days. When 
the 5% aqueous sodium hypochlorite solution is used as a laundry bleach, 
the resulting laundry on dry-out in an atmosphere of 65% relative humidity 
yields substantially no characteristic "hypochlorite" odor, but does have 
a faint, pleasant aroma as described in Table II of Example V, supra. 
Furthermore, no such characteristic "hypochlorite" aroma is retained on 
the hands of the individual handling such laundry in both the wet and the 
dry states. 
EXAMPLE XIV 
AROMOX.RTM. DMMC-W in various quantities is mixed with 0.1 gram of each of 
the compositions set forth in Table II of Example V, supra. The resulting 
premixes are then added to 200 grams of an aqueous 5% sodium hypochlorite 
solution. Sufficient 12.5M aqueous NaOH is added to bring the pH of the 
mixture up to 13. The following results are obtained: 
______________________________________ 
Clarity of Hypochlorite Solution 
Percentage AROMOX .RTM. DMMC-W 
After Addition of Premix 
______________________________________ 
0.25% Clear after three days 
0.18% Clear after three days 
0.05% Initially, slightly turbid; two 
phases exist after five days. 
______________________________________ 
When used as laundry bleaches, the resulting bleached laundries on dry-out 
in an atmosphere of 50% relative humidity in each of the three cases above 
retain the aroma as set forth in Table II of Example V, supra; whereas 
without the use of the materials containing the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives of our invention defined according to the structure: 
##STR114## 
wherein N is 1 or 2, the bleached laundry has a faint characteristic 
disagreeable hypochlorite aroma. 
EXAMPLE XV 
Four drops of each of the materials set forth in Table II of Example V is 
added to 1.5 grams of AROMOX.RTM. NCMD-W to produce a clear premix. The 
clear premix is added to 200 grams of CLOROX.RTM. with stirring resulting 
in a clear, stable, single phase solution. Sufficient 1M aqueous NaOH is 
added to bring the pH of the mixture up to 12.8. The solution remains 
substantially stable at 120.degree. F. for a period of seven days. When 
the 5% aqueous sodium hypochlorite solution is used as a laundry bleach, 
the resulting laundry on dry-out in an atmosphere of 65% relative humidity 
yields substantially no characteristic "hypochlorite" odor, but does have 
a faint, pleasant aroma as described in Table II of Example V. 
Furthermore, no such characteristic "hypochlorite" aroma is retained on 
the hands of the individual handling such laundry in both the wet and the 
dry states. 
EXAMPLE XVI 
One gram of n-tridecyl dimethyl amine oxide is admixed with 8 drops of each 
of the materials of Table II of Example V, supra. This premix is then 
added with stirring to 200 grams of a 7% aqueous solution of lithium 
hypochlorite. Sufficient 3M aqueous LiOH is added to bring the pH of the 
solution to 13.4. The mixture is then heated to 120.degree. F. and 
maintained at that temperature with stirring for a period of one week. The 
resulting solution remains clear in a single phase. When used as a laundry 
bleach, the resulting bleached laundry on dry-out in an atmosphere of 50% 
relative humidity retains an aroma as described in Table II of Example V, 
supra; whereas without the use of the materials containing the compound 
defined according to the structure: 
##STR115## 
wherein N is 1 or 2, the bleached laundry has a faint characteristic 
disagreeable "hypochlorite" aroma. 
EXAMPLE XVII 
DOWFAX.RTM. 2A1 in various quantities as set forth below is mixed with 0.1 
gram of each of the materials of Table II of Example V, supra. The 
resulting premixes are then added to 200 grams of an aqueous 7% sodium 
hypochlorite solution. Sufficient 12.5M aqueous NaOH is added to bring the 
pH of the mixture up to 13.5. The following results are obtained: 
______________________________________ 
Clarity of Hypochlorite Solution 
Percentage DOWFAX .RTM. 2A1 
After Addition of Premix 
______________________________________ 
0.30% Clear after seven days 
0.20% Clear after five days 
0.08% Clear after three days 
0.02% Initially, slightly turbid; two 
phases exist after five days. 
______________________________________ 
EXAMPLE XVIII 
One gram of DOWFAX.RTM. 3B2, 1 gram of DOWFAX.RTM. 2A1 and 0.25 grams of 
AROMOX.RTM. DMMC-W is admixed with 8 drops of each of the materials of 
Table II of Example V, supra. These premixes are then added with stirring 
to 200 grams of a mixture containing 4.5% aqueous sodium hypochlorite and 
4.5% aqueous lithium hypochlorite. Sufficient 4M aqueous LiOH is added to 
bring the pH of the solution to 13.4. The mixture is then heated to 
120.degree. F. and maintained at that temperature for a period of one 
week. The resulting solution remains clear in a single phase. When used as 
a laundry bleach, the resulting bleached laundries on dry-out in an 
atmosphere of 50% relative humidity retain aromas as set forth in Table II 
of Example V, supra; whereas without the use of materials containing the 
compound defined according to the structure: 
##STR116## 
wherein N is 1 or 2 produced according to our invention, the bleached 
laundry has a faint characteristic disagreeable "hypochlorite" aroma. 
EXAMPLE XIX 
0.2 Grams of n-tridecyl dimethyl amine oxide and 0.7 grams of DOWFAX.RTM. 
3B2 are admixed with 8 drops of each of the materials set forth in Table 
II of Example V, supra. These premixes are then added with stirring to 200 
grams of a 7% aqueous solution of lithium hypochlorite. Sufficient 3M 
aqueous LiOH is added to each material to bring the pH of each of the 
solutions to 13.4. The mixtures are then heated to 120.degree. F. and 
maintained at that temperature with stirring for a period of one week. The 
resulting solutions remain clear in a single phase. When used as a laundry 
bleach, the resulting bleached laundries on dry-out in an atmosphere of 
50% relative humidity retain aromas as set forth in Table II of Example V, 
supra; whereas without the use of the materials containing the 
7-isopropyl-8,8-dimethyl-6,10-dioxaspiro-C.sub.10 and C.sub.11 alkane 
derivatives defined according to the structure: 
##STR117## 
wherein N is 1 or 2, the bleached laundries have faint characteristic 
disagreeable "hypochlorite" aromas. 
EXAMPLE XX 
PEROXIDE BLEACH COMPOSITION 
A bleaching detergent is formulated containing: 
(A) 5 weight percent of an oxygen based bleaching agent generating hydrogen 
peroxide and water; 
(B) 0.2% of a bleach activator having the formula: 
##STR118## 
wherein R.sup.1 is decyl and wherein M is sodium; and (C) the compound 
having the structure: 
##STR119## 
During storage, the resulting composition does not pick up any "off" odor, 
but has a pleasant aroma as described in Table I, supra.