MALODOR COUNTERACTANTS

DESODORISANTS

English Abstract

ABSTRACT OF THE DlSCLOSURE
There are disclosed novel compounds of the formulae:
<IMG>
wherein n is 2,
A, B, and C each are hydrogen, or lower alkyl with no pair
of alkyls being on the same ring carbon, the sum of the
carbon atoms being no more than 7;
R1, R2 and R3 each are hydrogen or lower alkyl R1 and R2
together represent ?CH2?m wherein m is 2 to 6, the sum of
the larger number of carbon atoms in either R1 or R2 plus R3
being no more than 10;
R4 is lower alkyl or Rl and R4 together represent ?CH2?m;
D, E and F each are hydrogen or a lower alkyl and no pair
of alkyls is on the same ring carbon provided that at least
one of D, E or F is not hydrogen and that the sum of the carbon
atoms in D, E and F is no more than 7;
T is a lower alkyl;
U is hydrogen or a lower alkyl; and
R3 is U when D is a propyl or butyl group and E, F, R and
R2 are hydrogen.
These compounds are useful as malodor counteractants.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A method of treating malodors to alleviate their
offensive odors which comprises treating the air containing the
malodor, with an amount, effective to counteract the malodor,
of a compound selected from the group represented by the
structural formulae
<IMG> I
<IMG> II
<IMG> III
wherein
n is an integer of 2,
A, B, and C each independently represent hydrogen, or
lower alkyl having from 1 to 5 carbon atoms and no
pair of alkyls is on the same ring carbon, provided
that the sum of the carbon atoms in A, B and C is
no more than 7,
Rl and R2 each independently represent hydrogen or a
lower alkyl having from 1 to 5 carbon atoms or as seen
in formula III, R1 and R2 taken together represent
?CH2?m wherein m is an integer of from 2 to 6,
34

R3 represents hydrogen or a lower alkyl provided that
the sum of the larger number of carbon atoms in
either R1 or R2 plus R3 is no more than 10,
R4 represents a lower alkyl having from 1 to 5 carbon
atoms or as seen in formula II, R1 and R4 taken
together represent (CH2)m wherein m is an integer
of from 2 to 6,
D, E and F each independently represent hydrogen or
a lower alkyl having from 2 to 5 carbon atoms and
no pair of alkyls is on the same ring carbon pro-
vided that at least one of D, E or F is not
hydrogen and that the sum of the carbon atoms in
D, E and F is no more than 7 and with the further
proviso that when one of D, E and F is tert-butyl
and the others are H, R is H, R is H or methyl
and R3 is H or alkyl of 2 to 5 carbon atoms,
T represents a lower alkyl having from 3 to 6
carbon atoms with the proviso that A, B and C
are not simultaneously H unless T is isobutyl,
U represents hydrogen or a lower alkyl having from
2 to 6 carbon atoms with the proviso that when U
and R1 are H, and R is methyl, at least one of
A, B and C is alkyl,
When in formula III, D is a propyl or butyl group
and E, F, R and R are hydrogen, then R is U.
2. A method according to Claim 1 wherein the malodor
counteractant compound is provided in an amount sufficient to
provide at least 0.01 mg./cu.meter of air containing the
malodor.
3. A method according to Claim 1 wherein the
malodor counteractant compound is utilized in the form of a
room freshener.

4. A method according to Claim 3 wherein the room
freshener is introduced as an aerosol.
5. A method as defined in Claim 1, 2 or 3, wherein
B and C are hydrogen.
6. A method as defined in Claim 1, 2 or 3, wherein
each of A and R1 is hydrogen or lower alkyl or 1-5 carbon atoms
and R3 is hydrogen or lower alkyl of 1-6 carbon atoms wherein
R plus R is no more than 10.
7. A method as defined in Claim 1, 2 or 3, wherein
R is hydrogen.
8. A method as defined in Claim 1, 2 or 3, wherein
B and C are hydrogen and wherein each of A and R1 is hydrogen
or lower alkyl of 1-5 carbon atoms and R3 is hydrogen or lower
alkyl of 1-6 carbon atoms wherein R plus R is no more than 10.
9. A method according to claim 1 wherein the malodor
counteractant compound is cyclohexylmethyl isobutyrate.
10. A method according to claim 1 wherein the malodor
counteractant compound is l-cyclohexyl-l-ethyl propionate.
11. A method according to claim 1 wherein the malodor
counteractant compound is l-cyclohexyl-l-ethyl isobutyrate.
12. A method according to claim 1 wherein the malodor
counteractant compound is l-cyclohexyl-l-ethyl n-butyrate.
13. A method according to claim 1 wherein the malodor
counteractant compound is l-cyclohexyl-l-propyl n-butyrate.
14. A method according to claim 1 wherein the malodor
counteractant compound is cis/trans-l-(2'-methylcyclohexyl)-1-
ethyl n-butyrate.
15. A method according to claim 1 wherein the malodor
counteractant compound is cis/trans-1-(3'-methylcyclohexyl)-1-
ethyl n-butyrate.
36

16. A method according to claim 1 wherein the malodor
counteractant compound is cis/trans-1-(4'-ethylcyclohexyl)-1-
ethyl acetate.
17. A method according to claim 1 wherein the malodor
counteractant compound is cis/trans-1-(4'-isopropylcyclohexyl)-1
-ethyl acetate.
18. A method according to claim 1 wherein the malodor
counteractant compound is cis/trans-1-(4'-isopropylcyclohexyl)-1
-ethyl n-butyrate.
19. A method according to claim 1 wherein the malodor
counteractant compound is 2-cyclohexyl-2-propyl formate.
20. A method according to claim 1 wherein the malodor
counteractant compound is 2-cyclohexyl-2-propyl isobutyrate.
21. A method according to claim 1 wherein the malodor
counteractant compound is 2-cyclohexyl-2-propyl n-butyrate.
22. A compound represented by the structural formula
<IMG>
wherein
n is an integer of 2,
A, B and C each independently represent hydrogen, or
lower alkyl having from 1 to 5 carbon atoms, no pair
of alkyls is on the same ring carbon, provided that
the sum of the carbon atoms in A, B and C is no more
than 7,
T represents a lower alkyl having from 3 to 6 carbon
atoms with the proviso that A, B and C are not
simultaneously H unless T is isobutyl.
37

23. A compound according to claim 22 which is
cyclohexylmethyl isobutyrate.
24. A compound as defined in claim 22 wherein B
and C are hydrogen.
25. A compound as defined in claim 24 wherein A is
hydrogen or lower alkyl of 1-5 carbon atoms and T is lower alkyl
of 3-6 carbon atoms.
26. A compound represented by the structural formula
<IMG>
wherein
n is an integer of 2;
A, B and C each independently represent hydrogen, a
lower alkyl having from 1 to 5 carbon atoms and
no pair of alkyls is on the same ring carbon,
provided that the sum of the carbon atoms in A,
B and C is no more than 7,
R1 represents hydrogen or a lower alkyl having from
1 to 5 carbon atoms,
R represents a lower alkyl having from 1 to 5 carbon
atoms or R1 and R4 taken together represent ?CH2?m
wherein m is an integer of from 2 to 6, and
U represents hydrogen or a lower alkyl having from
2 to 6 carbon atoms with the proviso that when U
and R are H, and R is methyl, at least one of
A, B and C is alkyl.
27. A compound as defined in claim 26, wherein
B and C are hydrogen.

28. A compound as defined in claim 27, wherein each
of A and R1 is hydrogen or C1-5 alkyl and U is hydrogen or
C2-6 alkyl,
29. A compound according to claim 26 which is
l-cyclohexyl-l-ethyl propionate.
30. A compound according to claim 26 which is
l-cyclohexyl-l-ethyl isobutyrate.
31. A compound according to claim 26 which is
l-cyclohexyl-l-ethyl n-butyrate.
32. A compound according to claim 26 which is
l-cyclohexyl-l-propyl n-butyrate.
33. A compound according to claim 26 which is
cis/trans-l-(2'-methylcyclohexyl)-1-ethyl n-butyrate.
34. A compound according to claim 26 which is
cis/trans-l-(3'-methylcyclohexyl)-1-ethyl n-butyrate.
35. A compound according to claim 26 which is
cis/trans-l-(4'-isopropylcyclohexyl)-1-ethyl n-butyrate.
36. A compound represented by the structural formula
<IMG>
wherein
n is an integer of 2,
R1 and R2 each independently represent hydrogen or
a lower alkyl having from 1 to 5 carbon atoms or
Rl and R2 taken together represent ?CH2?m wherein
m is an integer of from 2 to 6,
39

R3 represents hydrogen or a lower alkyl provided
that the sum of the larger number of carbon atoms
in either R or R plus R is no more than 10, and
D, E and F each independently represent hydrogen or
a lower alkyl having from 2 to 5 carbon atoms and
no pair of alkyls is on the same ring carbon pro-
vided that at least one of D, E or F is not
hydrogen and that the sum of the carbon atoms in
D, E and F is no more than 7 and with the further
proviso that when one of D, E and F is tert-butyl
ana the others are H, R1 is H, R2 is H or methyl,
and R is H or alkyl of 2 to 5 carbon atoms.
37. A compound as defined in claim 36, wherein E
and F are hydrogen.
38. A compound according to claim 36 which is cis/
trans-l-(4'-ethylcyclohexyl)-1-ethyl acetate.
39. A compound according to claim 36 which is cis/
trans-l-(4?'-isopropylcyclohexyl)-1-ethyl acetate.
40. A compound represented by the structural formula
<IMG>
wherein
n is an integer of 2;
A, B and C each independently represent hydrogen, or
lower alkyl having from 1 to 5 carbon atoms and no
pair of alkyls is on the same ring carbon, provided
that the sum of the carbon atoms in A, B and C is
no more than 7,

U represents hydrogen or a lower alkyl having from
2 to 6 carbon atoms, and
R5 and R6 each independently represent a lower alkyl
having from l to 5 carbon atoms or R5 and R6 taken
together represent ?CH2?m wherein m is an integer
of from 2 to 6.
41. A compound as defined in claim 40, wherein
B and C are hydrogen.
42. A compound as defined in claim 40, wherein A
is hydrogen or lower alkyl and R5 is lower alkyl of 1-5 carbon
atoms and U is hydrogen or C2-6 alkyl.
43. A compound according to claim 40 which is 2-cyclo-
hexyl-2-propyl formate.
44. A compound according to claim 40 which is 2-cyclo-
hexyl-2-propyl isobutyrate.
45. A compound according to claim 40 which is 2-cyclo-
hexyl-2-propyl n-butyrate.
46. A compound selected from the group represented by
the structural formulae
<IMG> I
<IMG> II
41

<IMG> III
wherein
n is an integer of 2,
A, B and C each independently represent hydrogen, or
lower alkyl having from 1 to 5 carbon atoms and no
pair of alkyls is on the same ring carbon, provided
that the sum of the carbon atoms in A, B and C is no
more than 7,
R1 and R2 each independently represent hydrogen or
a lower alkyl having from 1 to 5 carbon atoms or as
seen in formula III, R1 and R2 taken together
represent ?CH2?m wherein m is an integer of from
2 to 6,
R3 represents hydrogen or a lower alkyl provided that
the sum of the larger number of carbon atoms in
either R1 or R2 plus R3 is no more than 10,
R4 represents a lower alkyl having from 1 to 5 carbon
atoms or as seen in formula II, R1 and R4 taken
together represent ?CH2?m wherein m is an integer
of from 2 to 6,
D, E and F each independently represent hydrogen or
a lower alkyl having from 2 to 5 carbon atoms and
no pair of alkyls is on the same ring carbon provided
that at least one of D, E or F is not hydrogen and
that the sum of the carbon atoms in D, E and F is no
more than 7 and with the further proviso that when
42

one of D, E and E is tert-butyl and the others
are H, R1 is H, R2 is H or methyl and R3 is H or
alkyl of 2 to 5 carbon atoms,
T represents a lower alkyl having from 3 to 6
carbon atoms with the proviso that A, B and C are
not simultaneously H unless T is isobutyl,
U represents hydrogen or a lower alkyl having from
2 to 6 carbon atoms with the proviso that when U
and R1 are H, and R4 is methyl, at least one of
A, B and C is alkyl, and
When in formula III, D is a propyl or butyl group
and E, F, R1 and R2 are hydrogen, then R3 is U.
47. A compound as defined in claim 46, wherein
B and C are hydrogen.
48. A compound as defined in claim 46, wherein each
of A and R1 is hydrogen or C1-5alkyl and R3 is hydrogen or
C1-6alkyl.
49. A compound as defined in claim 44, 45, or 46
wherein R1 is alkyl.
43

Description

43-4270A
11~)9(~78
MALODOR COUNTERACTANTS
Cross-References to Related Applications
None.
Eield of the Invention
This invention relates to the art of treatment of
offensive odors, more particularly, to compositions and methods
to counteract certain malodors.
Description of the Prior Art
The art of perfumery began, perhaps in the ancient
cave dwellings of prehistoric man. From its inception, and until
comparatively recently, the perfumer has utilized natural perfume
chemicals of animal and vegetable origin. Thus, natural perfume
chemicals such as the essential oils, for example, oil of rose
and oil of cloves, and animal secretions such as musk, have been
manipulated by the perfumer to achieve a variety of fragrances.
In more recent years, however, research perfume chemists have
developed characteristics particularly desired in the art. These
synthetic aroma chemicals have added a new dimension to the an-
cient art of the perfumer, since the compounds prepared are
usually of a sta~le chemical nature, are inexpensive as compared
with the natural perfume chemicals and lend themselves more easily
to manipulation than the natural perfume chemicals since such
natural perfume chemicals are usually a complex mixture of sub-
stances which defy chemical analysis. In contrast thereto, the
synthetic aroma chemicals possess a known chemical structure and
may therefore be manipulated by the perfumer to suit specific
needs. Such needs vary over a very wide spectrum. Accordingly,
there is a great need in the art of fragrance compositions for
compounds possessing specific olfactory characteristics.
Heretofore a major effort in the art of perfumery has
been directed to providing means of treating odors that are
offensive to the human sense of smell. Such odors encompass a
-2-

` 43-4270~
78
variety of odors such as bathroom-odor, kitchen-odor, body-odor,
cigar smoke-odor, etc. Many products have been developed in an
attempt to overcome these odors. So-called "room fresheners" or
"room deodorants" are illustrative of such products.
In general these products have provided a masking
effect by one of two mechanisms. The maskant fragrance is pro-
vided either to suppress the offensive odor by providing a more
pleasing aroma in large quantities or by providing an aroma that
blends with the offensive odor to provide a different and more
desirable aroma. Unfortunately, in both instances a large amount
of fragrance must be utilized which in itself often proves to be
offensive. Furthermore, the offensive odor is usually still de-
tectable at the levels of maskant fragrances that are reasonably
tolerable. Accordingly, compositions and methods for counter-
acting such offensive odors which would substantially eliminate
such odors without the above-noted disadvantages are particularly
desirable.
Particularly noxious odors are caused by compounds
which have a pronounced tendency to either donate or accept pro-
tons. Such compounds will hereinafter be referred to as "malodors".
They include the olfactory notorious classes of lower carboxylic
acids, thiols, thiophenols, phenols, lower amines, phosphines
and arsines.
The compound 4-cyclohexyl-4-methyl-2-pentanone has
heretofore been found to possess the ability to counteract such
malodors.
The following compounds have been described in the
literature although their ability to counteract such malodors
was undiscovered until the instant invention:
cyclohexylmethyl propionate--B. K. Zeinalov et al,
Dokl. Akad. Nauk. Azerb. SSR 21(4), 22 (1965),
CA 63, 11378h (1965)
--3--

~ 43-4270A
78
l-cyclohexyl-l-ethyl acetate--W. K. Johnson, J. Org.
Chem. 24, 864 (1959)
l-cyclohexyl-l-propyl acetate--G. P. Kugatova et al,
Zh. Obshch. Khim. 31, 604 (1961)
l-cyclohexyl-l-butyl acetate--D. J. Grummitt et al,
J. Am. Chem. Soc. 78, 1054 (1956)
cis/trans-l-(3'-methylcyclohexy~-1-ethyl acetate--
C. G. Overberger et al, J. Am. Chem. Soc. 81,
4697 (1959)
cis/trans-l-(4'-methylcyclohexyl)-1-ethyl acetate--
C. G. Oberberger et al, J. Am Chem. Soc. 81,
4697 (1959); H. Rupe et al., Helv. Chim~ Acta
_, 701 (1931)
cis/trans-2-(4'-methylcyclohexylj-2-propyl acetate--
Behal, Compt. rend. 150, 1763
Summary of the Invention
The present invention provides compounds and composi-
tions which are especially useful in view of their ability to
counteract malodors. Furthermore, novel methods are provided,
i.e. the use of such compounds and compositions to counteract
malodors. Still further, certain of these compounds are novel.
The compounds which exhibit this surprising ability to
counteract malodors are represented by the following structural
formula:
~ ~ (1)
C C~2)
wherein
n is an integer of from 1 to 4,
A, B and C each independently represent hydrogen, a
lower alkyl having from 1 to 5 carbon atoms or
~4~

~3-4270A
7~3
a lower alkenyl having from 3 to 5 carbon atoms,
provided that the sum of the carbon atoms in A,
B and C is no more than 7,
Rl and R2 each independently represent hydrogen or a
lower alkyl having from 1 to 5 carbon atoms or
R and R taken together represent ~CH2~m
wherein m is an integer of from 2 to 6,
R3 represents hydrogen or a lower alkyl or alkenyl
having up to 6 carbon atoms, provided that the
sum of the larger number of carbon atoms in
either Rl or R plus R3 is no more than 10.
Description of the Preferred Embodiments
The term "counteract" as used herein means the effect
on the human sense of smell and/or the malodor resulting in
alleviating the offensiveness of the malodor to the human sense
of smell. It is not intended that this term be limited to any
particular mechanism by which such a result may be obtained.
The compounds useful in this invention wherein n is 2
and Rl is alkyl, can be prepared as illustrated by the following
equations:
B i3 + RlC~ B~'~o
B ~ + R~ ~ B ~,01
B ~,~, + R3C(X~i~ ~ro (III)

43-4270A
78,
In the above equations, A, B, C and R3 have the same
meanings as set forth above.
As shown in equation (I) a substituted or unsubstituted
benzene is acylated, preferably under Friedel-Crafts conditions,
with an acyl chloride to form the corresponding phenyl-alkyl
ketone. As shown in equation (II) this phenyl-alkyl ketone is
hydrogenated over a suitable catalyst, preferably a rhodium
metal-containing to form the corresponding alkylated cyclohexyl-
methanol. Esterification of this alcohol with an appropriate
carboxylic acid forms the desired esters as shown in equation
(III).
The compounds wherein n is 2 and both Rl and R are
hydrogen can be prepared as illustrated by the following equations:
B_~ + H2 ~ 8~_ (IV)
COOH OOH
A A
~\ copper/ ,_~ (V)
COOH ~ ,1~OH
+ ~3co~3~ (VI)
In the above equations, A, B, C and R3 have the same
meanings as set forth above.
As shown in equation (IV) a substituted or unsubstituted
benzoic acid is first hydrogenated over a suitable rhodium cata-
lyst to the corresponding hexahydrobenzoic acid which is then
hydrogenated (equation (V)) to form the corresponding cyclohexyl-
methanol. This alcohol can then be esterified, as shown in equa-
tion (VI), with an appropriate carboxylic acid to form the

43-427OA
78
desired esters.
The compounds wherein n is 2 -~nd both Rl and R2 are
the same alkyl can be prepared as illustrated by the following
equations:
R~ + R NgCl ~ H~R
X = alkyl
I R -C-O-C-R ~ R~ (VIII)
In the above equations, A, B, C and R3 have the same
meanings as set forth above.
As shown in equation (VII) an alkyl ester of a substi-
tuted or unsubstituted hexahydrobenzoic acid is reacted with an
alkyl magnesium chloride to form the corresponding tertiary
alcohol. This alcohol is esterified, as shown in equation (VIII),
by reaction with the anhydride of an appropriate carboxylic acid
in the presence of a tertiary amine, such as triethylamine, to
form the desired ester.
The compounds wherein n is 2 and Rl and R2 are different
alkyls can be prepared as illustrated by the following equations:
R~ + R YgCl ~ R~,~R (IX)
~ 2 ~ ~ ¦ (X)
~ 2 C~H

43-4270A
78
A R
B~ + R3- -o-C-R3 tert ~
In the above equations, A, B, C and R3 have the same
meanings as set forth above.
As shown in equation (IX), a substituted or unsubsti-
tuted phenylalkyl ketone is reacted with an alkyl magnesium
chloride to form the corresponding tertiary alcohol which is
hydrogenated (equation (X)) over a suitable rhodium catalyst to
the corresponding cyclohexyl alcohol. This alcohol is esteri-
fied, as shown in equation (XI), by reaction with the anhydride
of an appropriate carboxylic acid in the presence of a tertiary
amine, such as triethyl amine to form the desired ester.
The compounds useful in this invention wherein n is
1, 3 or 4 can be prepared as illustrated by the following
equations: A
A ~ Rlcso ~ ~ ~ (XII)
A R
B~ + R3CoOH ~ B~ \~(XIII)
(CH2)n ~Rl H C (CH2)n ~0
In the above equations, A, B, C and R3 have the same
meanings as set forth above.
As shown in equation (XII) a substituted or unsubsti-
tuted cycloalkyl magnesium chloride and an appropriate aldehydeare reacted to form the corresponding cycloalkyl alcohol which
is esterified as shown in equation (XIII) to the desired ester.
--8--

43-4270A
P78
\MgCl ~Ç;~ (XIV)
In the above equation, A, B and C have the same
meanings as set forth above and Rl and R2 are alkyl.
As shown in equation (XIV) a substituted or unsubstituted
cycloalkyl magnesium chloride is reacted with an appropriate ke-
tone to form the corresponding cycloalkyl tertiary alcohol which
can be esterified by reaction with the anhydride of an appropri-
ate carboxylic acid in the presence of a tertiary amine, such as
triethylamine, to form the desired ester.
The compounds of the above formula wherein Rl and R2
taken together represent ~CH2tm can be prepared by first reacting
a magnesium chloride of an appropriate substituted or unsubstitu-
ted cycloalkyl with an appropriate cycloalkanone to form a ter-
tiary alcohol, wherein the substituted or unsubstituted cyclo-
alkyl group is attached to the same carbon atom as the hydroxyl
group, followed by an esterification reaction with the anhydride
of an appropriate carboxylic acid substantially as shown in
equation (XI).
The instant compounds are capable of effectively
counteracting malodors when utilized in small quantities and in
many different mediums. For instance, use in room fresheners or
room deodorants in the form of aerosols (sprays, etc.), liquids
(wick-type), solids twax bases as in pomander, plastics, etc.),
powders (sachets, dry sprays) and gels (solid gel sticks) are
particularly preferred. Other illustrative uses are in clothes
deodorants as applied by washing machine applications such as in
detergents, powders, liquids, whiteners or fabric softeners or
by other applications such as closet blocks, closet aerosol
sprays, or clothes storage areas or in dry cleaning to overcome
residual solvent notes on clothes; in bathroom accessories such
as paper towels, bathroom tissues, sanitary napkins, towellets,

43-4270A
1~L39~7~
disposable wash cloths, disposable diapers, and diaper pail
deodorants; in cleansers such as disinfectants and toilet bowl
cleaners; in cosmetic products such as antiperspirant and under-
arm deodorants, general body deodorants in the form of powders,
aerosols, liquids or solid, or hair care products such as hair
sprays, conditioners, rinses, hair colors and dyes, permanent
waves, depilatories, hair straighteners, hair groom applications
such as pomade, creams, lotions, etc., medicated hair care pro-
ducts containing such ingredients as S-Selenium-sulfide, coal
tar, salicylates, etc., or shampoos, or foot care products such
as foot powders, liquids or colognes, after shaves and body
lotions, or soaps and synthetic detergents such as bars, liquids,
foams or powders; in odor control such as during manufacturing
processes, such as in the textile finishing industry and the
printing industry (inks and paper); in effluent control such as
in processes involved in pulping, stock yard and meat processing,
sewage treatment, or garbage disposal, or in product odor control
as in textile finished goods, rubber finished goods, car freshen-
ers, etc.; in agricultural and pet care products such as dog and
hen house effluents, and domestic animal and pet care products
such as deodorants, shampoo or cleaning agents, or animal litter
materials; in large scale closed air systems such as auditoriums,
and subways and transport systems
The amount of any such compound to be utilized depends,
in general, on the particular malodor involve~ and its concentra-
tion in the air containing it and on other variables such as the
medium in which the compound is used and the temperature,
humidity and air circulation. An amount effective to counteract
the malodor should be used. In general, such compounds are
effective when present in the air (containing the malodor) at
levels as low as about 0.01 mg./cubic meter of air. Any concen-
tration above this amount will generally be effective. However,
from a practical point of view, more than about 1 mg./cubic
-lQ-

43-4270A
~g3i9~78
meter of air is probably unnecessary with even the most offensive
and concentrated malodors.
Novel compounds useful in the present invention are
represented by the fol~owing structural formulae:
T~
t I 1~ (2)
~(CH2 )~\ CH2f )
wherein n, A, B and C have the same meanings as set forth above,
and T represents a lower alkyl having from 3 to 6 carbon atoms.
~ ~ (3)
)~\c /
C R~ ~R4
wherein n, A, B, C and Rl have the same meanings as set forth
above, R represents a lower alkyl having from 1 to 5 carbon
atoms, or Rl and R4 taken together represent ~CH2tm wherein m
has the same meaning as set forth above, and U represents hydro-
gen or a lower alkyl having from 2 to 6 carbon atoms.
1~ R\
E~ ¦ ~ ( 4)
~(CH2 JJ~
wherein n, Rl, R2 and R3 have the same meanings as set forth
above and D, E and F each independently represent hydrogen, a
lower alkyl having from 2 to 5 carbon atoms, or a lower alkenyl
having from 3 to 5 carbon atoms, provided that at least one of
D, E or F is not hydrogen and that the sum of the carbon atoms
in D, E and F is no more than 7.
~ \f
~(CH2)~\C ~1
C R~ ~R6

43-4270A
78
wherein n, A, B, C and U have the same meanings as set forth
above, and RS and R6 each independently represent a lower alkyl
having from 1 to 5 carbon atoms or RS and R6 taken together
represent tCH2tm wherein m has the same meaning as set forth
above.
Particularly preferred compounds useful in the instant
invention are those wherein n is 2, i.e., where the ring struc-
ture is cyclohexyl. A particularly preferred compound is 1-
cyclohexyl-l ethyl n-butyrate.
Other illustrative compounds useful in the present
invention are: :
cyclohexylmethyl propionate
cyclohexylmethyl isobutyrate
cyclohexylmethyl n-butyrate
cis/trans-4-tert.butylcyclohexylmethyl acetate
cis/trans-4-methylcyclohexylmethyl acetate
cis/trans-4-isopropylcyclohexylmethyl acetate
l-cyclohexyl-l-ethyl formate
l-cyclohexyl-l-ethyl acetate
l-cyclohexyl-l-ethyl propionate
l-cyclohexyl-l-ethyl isobutyrate
l-cyclohexyl-l-propyl acetate
l-cyclohexyl-l-propyl n-butyrate
l-cyclohexyl-2-methyl-1-propyl acetate
l-cyclohexyl-2-methyl-1-propyl n-butyrate
l-cyclohexyl-l-butyl acetate
l-cyclohexyl-l-butyl n-butyrate
l-cyclohexyl-l-pentyl acetate
l-cyclohexyl-l-pentyl n-butyrate
cis/trans-1-(2'-methylcyclohexyl)-1-ethyl acetate
cis/trans-l-(2'-methylcyclohexyl)-1-ethyl n-butyrate
cis/trans-l-(3'-methylcyclohexyl)-1-ethyl acetate

43-4270A
7~
cis/trans-l-(3'-methylcyclohexyl-1-ethyl n-butyrate
cis/trans-l-(4'-methylcyclohexyl)-1-ethyl acetate
cis/trans-l-(4'-methylcyclohexyl)-1-ethyl isobutyrate
cis/trans-l-~4'-methylcyclohexyl)-1-ethyl n-butyrate
cis/trans-1-(4'-ethylcyclohexyl)-1-ethyl acetate
cis/trans-l-(4'-isopropylcyclohexyl)-1-ethyl acetate
cis/trans-l-(4'-isopropylcyclohexyl)-1-ethyl n-butyrate
cis/trans-l-(4'-tert.butylcyclohexyl)-1-ethyl acetate
2-cyclohexyl-2-propyl formate
2-cyclohexyl-2-propyl acetate
2-cyclohexyl-2-propyl propionate
2-cyclohexyl-2-propyl isobutyrate
2-cyclohexyl-2-propyl n-butyrate
cis/trans-2-(4'-methylcyclohexyl)-2-propyl acetate
The following examples are given to illustrate the
instant invention in detail. It is to be understood that the
specific details given in the examples are not to be construed
as limiting the scope of the invention. The symbol "mg./cu.
meter" refers to the weight (in milligrams) of material present
in one cubic meter of air.
Bxample 1
CYCLOHEXYLMETHYL PROPIONATE
A mixture of 28.5 g. (0.25 moles) cyclohexylmethanol,
34.5 g. (0.21 moles) propionic anhydride and 100 mg. p-toluene
sulfonic acid were reacted to give 40.7 g. crude product of 98.6%
purity, n25 = 1.4435. Distillation through a short Vigreux-
column afforded 36.3 g. of 99.8~ pure material, nD5 = 1.4435.
Lit. values: b.p. 64-66C./3 mm., n20 = 1.4465 confirms a yield
of 70.6~ of cyclohexylmethyl propionate which is a colorless,
mobile liquid of green, fruity odor.

43-427OA
~9q~78
Example 2
CYCLOHEXYLMETHYL ISOBUTYRATE
To a solution of 22.8 y. (0.2 moles) cyclohexyl-
methanol and 19.4 g. (0.22 moles) isobutyric acid in 100 ml.
benzene were added 2.0 g. p-toluene sulfonic acid. The resulting
mixture was heated to gentle reflux. Water codistilled with
benzene rapidly and was collected in a Dean-Stark trap. The
reaction mixture was allowed to cool, extracted with excess
saturated aqueous sodium bicarbonate solution and washed with
brine. The solvent was removed on a rotary evaporator to give
38.0 g. of crude material, nD5 = 1.4453, containing 86.35% of
the desired product. This was distilled through a short Vigreux-
column to give 31.8 g. of product, b.p. 53C./0.4 mm., nD5 =
1.4422. A colorless, fragrant liquid. Purity by GLC. 98.24%.
NMR analysis confirmed the product as cyclohexylmethyl isobutyrate
Example 3
CYCLOHEXYLMETHYL n-BUTYRATE
r
A solution of 22.8 g. (0.2 moles) cyclohexylmethanol
and 19.4 g. (0.22 moles) n-butyric acid in 70 ml. benzene, con-
taining 500 mg. p-toluene sulfonic acid was refluxed overnight
and water collected in a Dean-Stark trap. The reaction mass was
cooled to room temperature and the benzene solution was washed
with sodium bicarbonate solution, water, brine and then the
solvent removed in a rotary evaporator at 30 mm. and 50C. 36.0
g. of crude product, n25 = 1.4462, containing a little solvent
- were obtained. Distillation through a short Vigreux-column
afforded product of 99.6% purity by GLC analysis. b.p. 88C./
4 mm., nD5 = 1.4446, yield 31.3 g. = 84.9% of cyclohexylmethyl
n-butyrate which is a colorless, mobile liquid of green, fruity
odor.
Example 4
cis/trans-4-TERT.BUTYLCYCLOHEXYLMETHYL ACETATE
-14-

48~4270A
~9~71~
To a mixture of 8.5 g. cis/trans-4-tert.buty:Lcyclo-
hexylme-thanol ancl 5.5 g. acetic anhydride (0.5 moles of the
alcohol and 50~ excess anhydride) were added a few crystals p-
toluene sulfonlc acid and the mixture left overnight. Then 2
ml. water and 0.5 g~ sodium acetate was added. The mixture
stirred for 30 min. and then poured into 100 ml. of water. The
product was extracted with ether, the ether extract washed with
water and brine and dried over molecular sieves. On distillation
through a short Vigreux-column the product: b.p. 92~C./0.8 mm.,
n23 = 1.4555, yield 8.5 g. = 80~ of cis/trans-4-tert.butylcyclo-
hexylmethyl acetate which is a colorless, fragrant liquid with a
purity of g9.97%. GLC did not resolve the peaks, but the major
component was eluted first.
Example 5
cis/trans-4-METHYLCYCLOHEXYLMETHYL ACETATE
A mixture of 6.4 g. (0.05 moles) of cis/trans-4-
methylcyclohexylmethanol and 5.5 g. (0.055 moles) of acetic an-
hydride was reacted and the product was recovered as described
in Example 4. The product, a colorless fragrant liquid, had
b.p. 46-48~C./0.2 mm., nD4 = 1.4444. Yield 7.6 g. (89~3%).
Purity 99.85~ of cis/trans-4-methylcyclohexylmethyl acetate.
GLC did not separate the isomers on a 6 ft. LAC column.
Example 6
cis/trans-4-ISOPROPYLCYCLOHEXYLMETHYL ACETATE
To a mixture of 7.8 g. (0.05 moles cis/trans-4-iso-
propylcyclohexylmethanol and 5.5 g. (0.055 moles) of acetic an-
hydride were added a few crystals of p-toluene sulfonic acid
and the reaction run and the product was recovered as described
in Example 4. The product, a colorless fragrant liquid, had b.p.
85C./1 mm., nD3 = 1.4520. Yield 9.0 g. (90.8%) of 99.9% purity
of cis/trans-4-isopropylcyclohexylmethyl acetate by GLC. No
separation of stereoisomers on a LAC column was observed.

~ 27()~
7~3
Example 7
l-CYCLOEIEXYL-l-ETHYL FORMATE
A mixtllre of 12.8 g. (0.1 moles) l-cyclohexyl 1--
ethanol and 13.8 g. ~0.3 moles) formic acid wa~ reEluxed for two
hours and then cooled to room temperature. It was poured in 200
ml. cold wa-ter, the organic material extracted in e-ther and the
ether extract washed thoroughly with water, sodium bicarbonate,
water and brine and dried over molecular sieves. 15.4 g. crude
product of 97.9% puri-ty was recovered--major impurity is residual
solvent. The crude product was distilled through a short
Vigreux-column. The product is a mobile, colorless liquid, b.p.
94C./16 ~., nD5 = 1.4437. Yield 13.6 g. = 87.1%, purity 99.2%
(by GLC) of l-cyclohexyl-l-ethyl formate.
Example 8
l-CYCLOHEXYL-l-ETHYL ACETATE
A mixture of 25.6 g. (0.2 moles) l-cyclohexyl-l-ethanol
and 22.0 g. acetic anhydride (0.22 moles) containing 100 mg. p-
toluene sulfonic acid was warmed to 50C. A strongly exothermic
reaction occurred which was allowed to proceed freely. A maximum
temperature of 123C. was reached. After standing at room tem-
perature the reaction mixture was diluted with the same volume
of ether and poured into 300 ml. cold water. The organic layer
was separated, thoroughly washed with water (4 x 50 ml.), sodium
bicarbonate solution, water again and finally brine. The solvent
was evaporated on a rotary evaporator to give 33.5 g. of crude
product, purity 98.76% by GLC. Distillation through a short
Vigreux-column afforded 30.8 g. of pure product, b.p. 85C./10
mm., n24 = 1.4445, colorless liquid of fruity-floral-woody odor
with a touch of an animal note. NMR analysis confirmed the
product as l-cyclohexyl-l-ethyl acetate.

~3--42l0~
78
Example 9
_ _
1 -C'~CLOH~: XYT.- l -ETHY L P ROP I C)MATE
To a mix-ture o-~ 12.8 g. (0.1 moles) l-cycLol,exyl-l-
ethanol and 14~3 g. (0.11 moles) propionic anhydride was added
100 mg. p-toluene sulfonic acid and -the mi~ture left at room
temperature for 18 hours. Then 0.2 ml. water was added and the
mixture le~t one more hour at room temperature ~nd -then poured
in 200 ml. cold water. The organic layer was separated, the
aqueous layer extrac-ted once with ether and the combined organic
material washed with water, sodium bicarbonate, water and finally
brine. Af~er drying over molecular sieves afforded 18.6 y. of
crude material, n23 =1.4442 which was practically pure. Dis-
tillation through a short Vigreux-column afforded the product,
b.p. 98.5C./10 mm., n24 = 1.4446, yield 15.5 g. = 84.1%.
Purity 99.7% by GLC of l-cyclohexyl-l-ethyl propionate having a
fatty, dir-~y and oily odor.
Example 10
l-CYCLOHEXYL-l-ETHYL ISOBUTYRAr~E
A solution of 25.6 g. (0.2 moles) l-cyclohexyl-l-
ethanol and 19.4 g. (0.22 moles) isobutyric acid in 100 ml.
benzene, containing 2 g. p-toluene sulfonic acid, was heated to
gentle reflux--water distilled a~ a reasonable rate. After re-
fluxing overnight 3.6 ml. of water were collected. The mixture
was extracted with excess cold saturated sodium bicarbonate
solution, washed with water and brine and evaporated on a rotary
evaporator to give 38.1 g. of a colorless fragrant liquid, nD
1.4435. GLC = 91.94% product and 6.91% low boilers. The product
was purified by distillation through a Holtzmann-column. After a
small forerun (discarded) the product was obtained as a colorless,
fragrant liquid, b.p. 56C./0.3 mm., n25 = 1.4420, yield 33.5 g.
(83.2%). NMR analysis confirmed the product as l-cyclohexyl-l-
ethyl isobutyrate.
-17-

43-4270A
9~7'E3
Example 11
l-CYCLOHEXYL-l~ETHYL n BUTYRATE
To a mixture of 12.8 g. (0.1 moles) l-cyclohexyl-l-
ethanol and 9.7 y. (0.11 moles, 10% excess) n-butyric acid in
50 ml. benzene was added 1 g. p-toluene sulfonic acid and with
stirring refluxed gently overnight. 1.8 ml. (calculated amount)
water were collected in a trap. The benzene solution was allowed
to cool to room temperature, then washed with sodium bicarbonate
solution, water and brine, and evaporated on a rotary evaporator
to give 18.3 g. of crude ester, nD4 = 1.4462, purity 95.9%.
Distillation through a short Vigreux-column gave the pure pro-
duct, b.p. 97.5C./4 mm., n25 = 1.4456, yield 15.4 g. (77.7~)/
purity by GLC 99.7% of l-cyclohexyl-l-ethyl n-butyrate which is
a colorless, mobile fragrant liquid.
Example 12
l-CYCLOHEXYL-l-PROPYL ACETATE
A mixture of 1.42 g. l-cyclohexyl-l-propanol and 11.2
g. acetic anhydride containing 100 mg. p-toluene sulfonic acid
was left at room temperature for 24 hours. It was then poured
in excess (200 ml.) water, the organic material extracted with
ether and the ether layer ~lashed thoroughly with water ana sodium
bicarbonate solution and brine and dried over molecular sieves.
15.8 g. of crude product, n25 = 1.4456 was recovered. It was
distilled through a short Vigreux-column to give two fractions
b.p. 69C./2 mm., n25 = 1.4456 1.6 g. (Fraction 1)
b.p. 69C./2 mm., nD5 = 1.4456 13.5 g. (Fraction 2)
Fraction 2 was 99.6% pure, by GLC, l-cyclohexyl-l-propyl acetate.
Example 13
l-CYCLOHEXYL-l-PROPYL n-BUTYRATE
A solution of 14.2 g. (0.1 moles) l-cyclohexyl-l-
propanol and 9.7 g. n-butyric acid (10~ excess) in 50 ml. benzene,
containing 0.25 ml. concentrated sulfuric acid was heated to
-18-

43-fi2 70i~
78
reflux and water collected in a Dean-Stark trap. 13.1 g. (61.7~)
of crude product, nD3 = 1.4508 were recovered. Two low boiling
minor peaks suggest that considerable dehydra-tion had occurred.
Distillation of the crude product through a short Vigreu~-column
afforded two fractions
b.p. 23 76C./0.7 mm., nD3 = :L.4518 3.8 g. (Fraction 1)
b.p. 72C./0.4 mm., n23 = 1.4470 8.3 g. (Fraction 2)
Fraction 2, l-cyclohexyl-l-propyl n-butyrate, a colorless mobile
liquid, had a weak fruity, prune-like odor.
Example 14
l-CYCLOHEXYL-2-METHYL-l-PROPYL _CETATE
To a mixture of 15.6 g. (0.1 moles) 1-cyclohexyl-2-
methyl-l-propanol and 11.2 g. (0.11 moles) acetic acid was added
100 mg. p-toluene sulfonic acid and the mixture left at room
temperature overnight. Then 1 g. sodium acetate and 1 ml. water
was added, the mixture stirred for one hour and poured into 150
ml. water. The organic layer was separated, the aqueous layer
extracted with 2 x 50 ml. ether and the combined extracts and
organic layer washed thoroughly with water, sodium bicarbonate
solution, water and brine. After drying over molecular sieves
overnight 17.4 g. of crude product, nD3 = 1.4482, was recovered
which was practically pure. Distillation through a Vigreux-
column gave the pure product, b.p. 79C./2.9 mm., nD5 = 1.4477
which was 1-cyclohexyl-2-methyl-1-propyl acetate.
Example 15
l-CYCLOHEXYL-2-METHYL-l-PROPYL n-BUTYRATE
To a solution of 17.2 g. (0.11 moles) 1-cyclohexyl-2-
methyl-l-propanol and 8.7 g. (0.11 moles) pyridine in 100 ml.
anhydrous ether, chilled in an ice bath, was added with stirring
a solution of 11.72 g. (0.11 moles) butyryl chloride in 20 ml.
anhydrous ether at such a rate as to keep the temperature at
4-6C. After complete addition the ice bath was removed and
--19--

43-4270A
78
stirring at room temperature continued for several hours. Enough
ice wa-ter was added to dissolve the precipitate and the organic
layer separated. It was washed thoroughly with cold 3~ hydro-
chloric acid, water, sodium bicarbonate solution, water and brine
and dried over molecular sieves for 18 hours. 19.9 g. of crude
material was recovered which was distilled through a short
Vigreux-column to give the product l-cyclohexyl-2-methyl-1-propyl
n-butyrate, b.p. 91C./0.8 mm., n25 = 1.4507. This compound has
a tabac-type odor.
Example 16
l-CYCLOHEXYL-l-BUTYL ACETATE
15.6 g. (0.1 moles) of l-cyclohexyl-l-butanol were
acetylated with 11.2 g. (0.11 moles) acetic anhydride and 100 mg.
p-~oluene sulfonic acid and recovered as described in Example 14.
16.9 g. (85.2~) of crude product, n24 = 1.4472 was obtained
which was practically pure. Distillation through a short Vigreux-
column afforded two fractions
b.p. 52-60C./0.5 mm., nD = 1.4484, 1.2 g. (Fraction 1)
b.p. 60C./0.5 mm., nD2 = 1.4484, 14.6 g. (Fraction 2)
Both fractions were of 99+~ purity, by GLC, l-cyclohexyl-l-
butyl acetate. This compound has an earthy, woody, spicy, rooty,
vetivert odor.
Example 17
l-CYCLOHEXYL-l-BUTYL n-BUTYRATE
Using a procedure similar to that used in Example 15,
l-cyclohexyl-l-butanol was reacted with n-butyryl chloride to
form l-cyclohexyl-l-butyl n-butyrate, b.p. 85C./0.75 mm.,
n25 = 1.4490.
Example 18
l-CYCLOHEXYL-l-PENTYL ACETATE
17.0 g. (0.1 moles) of l-cyclohexyl-l-pentanol were
acetylated with 11.2 g. (0.11 moles) acetic anhydride and 100
-20-

43-4270A
7B
mg. p-toluene sulfonic acid and recovered as described in Example
14. 20.0 g. of crude product, nD2 = 1.4495 were obtained, prac-
tically pure. This material had a b.p. 96C./0.9 mm. and n25 =
1.4485 l-cyclohexyl-l-pentyl acetate.
Example 19
l-CYCLOHEXYL-l-PENTYL n-BUTYRATE
-
Using a procedure similar to that used in Example 15,
l-cyclohexyl-l-pentanol was reacted with butyryl chloride to
form l-cyclohexyl-l-pentyl n-butyrate, b.p. 100C./2.9 mm.,
nD = 1.4508.
Example 20
cis/trans-l-(2'-METHYLCYCLOHEXYL)-l-ETHYL ACETATE
A mixture of 14.2 g. (0.1 moles) cis/trans-1-(2-
methylcyclohexyl l-ethanol, 11.2 g. (0.11 moles) acetic anhydride
and 100 mg. p-toluene sulfonic acid was reacted and recovered
as described in Example 14. 16.4 g. of crude product, 1-(2'-
methylcyclohexyl)-l-ethyl acetate, nD2 = 1.4497, was obtained
as a colorless, fragrant liquid. GLC showed this to be a mix-
ture of one major and two minor components. Distillation through
a short Vigreux-column afforded the same mixture, b.p. 97C./
0.9 mm., nD5 = 1.4435.
Example 21
cis/trans-l-(2'-METHYLCYCLOHEXYL)-l-ETHYL n-BUTYRATE
Using a procedure similar to that used in Example 15,
1-(2'-methylcyclohexyl)-1-ethanol was reacted with n-butyryl
chloride to form l-(2'-methylcyclohexyl)-1-ethyl n-butyrate,
b.p. 75C./0.6 mm., nD = 1.4517.
Example 22
cis/trans-l-(3'-METHYLCYCLOHEXYL)-l-ETHYL ACETATE
14.2 g. (0.1 moles) of cis/trans-1-(3'-methylcyclo-
hexyl)-l-ethanol, 11.2 g. (0.11 moles) of acetic anhydride and
100 mg. p-toluene sulfonic acid were reacted and the product,

78
cis/trans-l-(3'-methylcyclohexyl)-1-ethyl acetate, was
recovered as described in Example 14. 17.0 g. of material,
practically pure by GLC, were obtained. The product has a
b.p. 57C./0.9 mm., n25- 1 4435
xample 23
cis/trans-l-(3'-METHYLCYCLOHEXYL)-l-ETHYL n-BUTYRATE
Using a procedure similar to that used in Example 15,
1-(3'-methylcyclohexyl)-1-ethanol was reacted with n-butyryl
chloride to form l-(3'-methylcyclohexyl)-1-ethyl n-butyrate,
10 b.p. 93C./3.5 mm., nD - 1.4448.
Example 24
cis/trans-l-(4'-METHYLCYCLOHEXYL)-l-ETHYL ACETATE
To a mixture of 12.8 g. (0.09 moles) cis/trans-1-(4'-
methylcyclohexyl)-l-ethanol and 10.2 g. (0.1 moles) acetic an-
hydride was added 100 mg. p-toluene sulfonic acid and the
solution left at room temperature overnight. The resulting
mass was poured into 100 ml. of water and washed thoroughly
and subsequently with water, sodium bicarbonate solution, water
and brine, dried over molecular sieves. 14.9 g. of crude
material was recovered, nD = 1.4434, purity 99.50~ of cis/trans
-1-(4'-methyleyclohexyl)-1-ethyl acetate. This material was
distilled through a short Vigreux-column to give product, b.p.
42-43 C./ 0.3 mm., nD ~ 1.4433, purity 99.82%. Yield 13.2 g.
Example 25
eis/trans-l-(4'-METHYLCYCLOHEXYL)-l-ETHYL ISOBUTYRATE
To a mixture of 12.8 g. (0.09 moles) eis/trans-1-(4'-
methyleyelohexyl)-l-ethanol and 14.2 g. isobutyrie anhydride was
added 100 mg. p-toluene sulfonie aeid and the solution left at
room temperature overnight. It was then poured in 100 ml. water,
extracted with ether and the ether solution washed with w~tçr,
sodium bicarbonate solution, water and brine and dried over
molecular sieves~ 17.0 g. of crude product was recovered, n23=
-22-

43-4270~
39~.'8
1.4416, purity 99.1% of cis/trans-1-(4'-methylcyclohexyl)-1-
ethyl isobutyrate. This product was distilled through a short
Vigreux-column:
b.p. ~8-56C./0.35 mm., nD5 = 1.4334, 1.6 g. (Fraction 1)
b.p. 55-58C./0.35 mm., n25 = 1.4415, 14.2 g. (Fraction 2)
Fraction 2, the product, is 100% pure by GLC.
Example 26
cis/trans-l-(4'-METHYLCYCLOHEXYL)-l-ETHYL n-BUTYRATE
Using a procedure similar to Example 15, 1-(4'-methyl-
cyclohexyl)-l-ethanol was reacted with n-butyryl chloride to form
1-(4'-methylcyclohexyl)-1-ethyl n-butyrate, b.p. 69C./0.5 mm.,
nD = 1.4455.
Example 27
c ~trans-l-(4'-ETHYLCYCLOHEXYL)-l-ETHYL ACETATE
15.6 g. (0.1 moles) of 1-(4'-ethylcyclohexyl)-1-
ethanol, 11.2 g. (0.11 moles) acetic anhydride and 100 mg. p-
toluene sulfonic acid were reacted and the product was recovered
as described in Example 14. 18.9 g. of crude material was ob-
tained, nD = 1.4476. GLC: practically pure, mixture of two
isomers in 1:1 ratio of cis/trans-1-(4'-ethylcyclohexyl)-1-
ethyl acetate. This material distilled at 65-70C./0.8 mm.,
nD5 = 1.4474.
Example 28
cis/trans-1-(4'-ISOPROPYLCYCLOHEXYL)-l-ETHYL ACETATE
To a mixture of 8.5 g. cis/trans-(4-isopropylcyclo-
hexyl)-l-ethanol and 5.5 g. (0.055 moles, 10% excess) acetic
anhydride was added a few crystals of p-toluene sulfonic acid
and the mixture reacted and the product was recovered as des-
cribed in Example 4. Distillation through a short Vigreux-
column afforded 9.4 g. product as a colorless liquid, b.p.
72C./0.15 mm., n24 = 1.4506. GLC showed the-two stereoisomers
in about equal amounts (4:6). Purity 99.3% of cis/trans-1-(4'-

43-4270A
;7~
isopropylcyclohexyl)-l-ethyl acetate having an animal, musky,
woody odor.
Example 29
cis/trans-l-(4'-ISOPROPYLCYCLOHEXYL)-l-ETHYL n-BUTYRATE
Using a procedure similar to Example 15, 1-(4'-iso-
propylcyclohexyl)-l-ethanol was reacted with n-butyryl chloride
to form l-(4'-isopropylcyclohexyl)-1-ethyl n-butyrate, b.p.
99C./0.8 mm., nD = 1.4519.
Example 30
cis/trans-1-(4'-TERT.BUTYLCYCLOHEXYL)-l-ETHYL ACETATE
12.3 g. cis/trans-1-(4'-tert.butylcyclohexyl)-1-
ethanol (0.0667 moles) were acetylated with 7.5 g. (0.0734 moles)
of acetic anhydride and 100 mg. p-toluene sulfonic acid and the
product was recovered as described in Example 14. 14.5 g. of
crude product, purity 99+% cis/trans-1-(4'-tert.butylcyclohexyl)-
l-ethyl acetate by GLC, were obtained. This colorless fragrant
liquid had n22 = 1.4526. Traces of low boilers were removed by
takeover distillation. b.p. 87C./0.9 mm., n25 = 1.4530.
Example 31
2-CYCLOHEXYL-2-PROPYL FORMATE
A mixed anhydride reagent was prepared by adding drop-
wise with stirring, at 40C., 10.1 g. (0.22 moles) formic acid
(97%) to 22.5 g. (0.22 moles) acetic anhydride containing 50 mg.
p-toluene sulfonic acid. After stirring for one hour at 40C.,
28.4 g. of 2-cyclohexyl-2-propanol were added. IR and GLC analy-
sis showed that the reaction was quite rapid and practically
complete after one hour and almost no hydrocarbons had formed.
29.2 g. of crude product, 2-cyclohexyl-2-propyl formate, was
recovered, n25 = 1.4560 (a mixture of the formate and acetate).
It was distilled through a Holtzmann-column and the following
fractions were taken:
-24-

43-427OA ~ 78
b.p. 46-53~C./10 mm., nD5 = 1.4580 11.0 g. (Fraction 1)
b.p. 53-56C./10 mm., nD5 = 1.4570 10.6 g. (Fraction 2)
b.p. 56C./10 mm., n25 = 1.4540 5.8 g. (Fraction 3)
GLC analysis of the fractions showed that practically no signi-
ficant separation had been achieved.
Example 32
2-CYCLoHEXYL-2-PRoPYL ACETATE
21.3 g. recovered 2-cyclohexyl-2-propanol were dissolved
in 20.0 g. acetic anhydride and 500 mg. 85~ phosphoric acid added.
Monitoring by IR showed that all of the alcohol had reacted over-
night. 20 ml. water and 1.0 g. anhydrous sodium acetate were
added and the mixture stirred at room temperature for one hour to
hydrolyze excess acetic anhydride. Then it was poured into cold
water, extracted with ether and the ether solution backwashed
with water, sodium bicarbonate solution and brine and evaporated
on a rotary evaporator to give 19.3 g. of crude material which
analyzed by GLC to 23~ mixture of two hydrocarbons and 76~ of
2-cyclohexyl-2-propyl acetate. It was distilled through a
Holtzmann-column:
b.p. 27C./0.5 mm., nD = 1.4600 2.0 g. (Fraction 1)
b.p. 42C./0.1 mm., nD5 = 1.4505 14.3 g. (Fraction 2)
Fraction 2 was 99% of the desired product by GLC. NMR analysis
confirmed its structure.
Example 33
2-CYCLOHEXYL-2-PROPYL PROPIONATE
A mixture of 28.4 g. 2-cyclohexyl-2-propanol (0.2
moles) 39.0 g. propionic anhydride (0.3 moles) and 22.3 g. (0.22
moles) triethyl amine were heated with stirring to 120C. and
the progress of reaction monitored by GLC. After 7 hours almost
all of the alcohol had been consumed and the reaction mixture
was left at room temperature overnight. It than was poured into
excess water and the organic layer separated. The aqueous layer
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43-4270A ~9~78
was extracted with benzene, the benzene extract combined with the
organic layer and thoroughly washed with water, 3~ hydrochloric
acid, water, sodium bicarbonate solution, water and finally with
brine. The solvent was removed on a rotary evaporator at 30 mm.
pressure and 50C. bath temperature. 38.6 g. of crude product,
nD5 = 1.4475, were obtained and distilled through a short
Vigreux-column:
b.p. up to 69C./0.7 mm., nD = 1.4210 1.9 g. (Fraction 1)
b.p. up to 62C./0.35 mm., nD5 = 1.4504 32.2 g. (Fraction 2)
The product is 96.8% pure 2-cyclohexyl-2-propyl propionate by GLC,
impurity is unreacted 2-cyclohexyl-2-propanol (GLC analysis). The
product is a colorless, mobile liquid with a chemical, camphora-
ceous odor.
Example 34
2-CYCLOHEXYL-2-PROPYL ISOBUTYRATE
A mixture of 28.4 g. (0.2 moles) 2-cyclohexyl-2-propanol
40.0 g. (0.25 moles) isobutyric anhydride and 22.3 g. (0.22 moles)
triethyl amine was heated to reflux overnight and the product was
recovered as described in Example 33 to give 42.7 g. of a crude
product, nD5 = 1.4442. Distillation through a short Vigreux-
column afforded:
b.p. 43C./0.5-60C./0.3 mm., nD4 = 1.4278, 8.5 g. (Fraction 1)
b.p. 70C./0.7 mm., nD4 = 1.4475, 33.0 g. (Fraction 2)
Fraction 1 contained unreacted and unhydrolyzed isobutyric anhy-
dride. The product was 98.7% (GLC analysis) pure 2-cyclohexyl-
2-propyl isobutyrate. The product was a colorless, mobile liquid
with a floral, citrus, rose muguet odor.
Example 35
2-CYCLOHEXYL-2-PROPYL n-BUTYRATE
To a solution of 28.4 g. (0.2 moles) 2-cyclohexyl-2-
propanol and 24.0 g. (0.3 moles) pyridine in 100 ml. anhydrous
ether, chilled in an ice-sali bath, was added with stirring a
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&78
solution of 23.4 g. (0.22 moles) freshly redistilled butyryl
chloride at such a rate as to keep the temperature around 0C.
The ice bath was removed after complete addition and stirring
continued for two hours. Then the solid was dissolved in the
minimum amount of water and the organic layer separated. It was
washed with water, 3~ hydrochloric acid, water, sodium bicarbonate
solution, water again and finally with brine. After drying over
molecular sieves overnight a crude product (42.0 g.) was recovered,
nD5 = 1.4603. This product contained unreacted alcohol as a
major impurity. Distillation through a short Vigreux-column
afforded:
b.p. up to 67C./0.25 mm.,nD5 = 1.4548 4.5 g. (Fraction 1)
mostly low boilers
b.p. 67-71C./0.2 mm., nD5 = 1.452227.2 g. (Fraction 2)
mostly product
Fraction 2 was redistilled:
b.p. 48-60C./0.1 mm., nD = 1.4572 5.3 g. (Fraction 2A)
b.p. 60C./0.1 mm., nD = 1.451420.8 g. (Fraction 2B)
Fraction 2B was analyzed by GLC to 99.9% purity 2-cyclohexyl-2-
propyl n-butyrate. The product was a colorless, mobile liquid
with a chemical, fruity odor.
Example 36
The following malodor concentrate was prepared:
Bathroom Malodor Concentrate
:
ComponentParts by Wt.
.
skatole 0.91
~-thionaphthol 0.91
95~ aqueous solution of thioglycolic acid 21.18
n-caproic acid 6.00
p-cresyl isovalerate 2.18
N-methyl morpholine 6.00
dipropylene glycol 62.82
Aerosol cans were prepared with the above malodor with
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43-427OA
11~9~78
the following concentrations:
Bathroom Malodor Aerosol
Component Parts by Wt.
Bathroom Malodor Concentrate 0.1
dipropylene glycol 4.9
Propellant
a. trichloromonofluoromethane47.5
b. dichlorodifluoromethane 47.5
A "Spice for Cologne" fragrance was selected for use in
testing the malodor counteractant ability of the compounds tested.
The "Spice for Cologne" fragrance contained the following
ingredients:
Ingredients Parts
Lavandin Abrialis Oil 60
Amyl Cinnamic Aldehyde 20
Amyl Salicylate 150
Benzyl Acetate 30
Linalool 30
Cedarwood Oil 10
Geraniol 130
Isopulegol 60
Methyl Anthranilate (10% by weight solution in
dipropylene glycol)20
Musk Xylol 60
Coumarin 50
Phenyl Ethyl Acetate 30
Terpinyl Acetate 100
Cinnamon Leaf Oil 40
Petitgrain Oil SA 60
30 Ylang ylang Oil 130
Phenyl Acetaldehyde Dimethyl Acetal 15
Cinnamic Alcohol 5
1000
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~)9~78
Aerosol cans were prepared with the above fragrance
composition with and without l-cyclohexyl-l-ethyl n-butyrate
being present as a malodor counteractant as follows:
Without l-cyclohexyl-l-ethyl n-butyrate
%
"Spice for Cologne" fragrance 0.5
Propellant
a. trichloromonofluoromethane 49.75
b. dichlorodifluoromethane 49.75
100.00
With l-cyclohexyl-l-ethyl n-butyrate
"Spice for Cologne" fragrance 0.45
l-cyclohexyl-l-ethyl n-butyrate 0.05
Propellant
a. trichloromonofluoromethane 49.75
b. dichlorodiflurormethane 49.75
100.00
A test chamber having inside dimensions of 11' x 12' x
8' with a total volume of 29.9 cubic meters, having an access
door and an exhaust fan was provided. The capacity of the ex-
haust fan was 500 cu. feet/min. In order to insure satisfactory
evacuation the exhaust fan was operated for five minutes between
tests and an olfactory check was made to determine if any re-
sidual odor could be detected prior to conducting the next test.
After the test chamber had been suitably evacuated the
bathroom malodor was sprayed from the aerosol can for about five
seconds. After a delay of from 10-15 seconds the fragrance com-
position aerosol was sprayed for about five seconds (five seconds
being an average time such an aerosol would usually be used by a
housewife). One minute thereafter a 2 member panel (consisting
of 1 person skilled in perfumery and odor evaluation and 1 person
having no such skills but being familiar with fragrances in
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43-4270A
general) entered the test chamber, performed an olfactory evalua-
tion for detection of the malodor and recorded their observations.
All tests were performed with neither member of the panel being
aware of the identity of the material being tested.
sased on the flow rate through the valve utilized in
the aerosol can the approximate amount of aerosol, containing
the malodor concentrate, introduced into the test chamber is:
Aerosol Containing Amount
Malodor Concentrate (mg./cu.meter)
Bathroom 267
The amount of aerosol containing the fragrance compo-
sitions introduced into the test chamber is approximately 260
mg./cu.meter.
When the above described test procedure was carried
out using the "Spice for Cologne" fragrance composition aerosol
with l-cyclohexyl-l-ethyl n-butyrate neither member of the panel
could detect the presence of the malodor. This is a particularly
surprising result because when the "Spice for Cologne" fragrance
composition aerosol without l-cyclohexyl-l-ethyl n-butyrate is
tested both members of the panel detected the presence of the
malodor. The panel commented that the malodor counteractant
effect was outstanding and that there was produced a fresh air
effect (FAE), real ozone effect, with a very nice and low resi-
dual odor from the compound tested.
Example 37
An aerosol can was prepared with the following concen-
trations:
Component Parts by Wt.
l-cyclohexyl-l-ethyl n-butyrate 0.05
Propellant
a. trichloromonofluoromethane 49.975
b. dichlorodifluoromethane 49.975
The aerosol was utilized in the above-described test
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78
procedure (aerosol--267 mg./cu.meter). Neither member of the
panel could detect the presence of the malodor. However, 1-
cyclohexyl-l-ethyl n-butyrate is not particularly pleasing in
its odor properties when used alone.
Example 38
The exemplary compounds indicated in Table 1 were in-
corporated into "Spice for Cologne" fragrance composition aerosol
cans according to the procedures of Example 36 and, using the
test procedures of Example 36, they were tested for their ability
10 to counteract the bathroom malodor. The results are shown in
Table 1.
TABLE 1
CompoundActivity* Comments
of Ex. 1 U FAE**, very clean, light background
2 U FAE, clean, fresh and light background
3 U FAE, very clean, lighter, fruity note
in residual
4 U* FAE, very clean, ozone-like freshness,
very light residual
V No malodor, clean, but muted and un-
appealing background odor quality
6 V No malodor, clean, but blends badly
and seems to act slower
7 U* FAE, very clean and extremely light
and fresh
8 V No malodor, light residual with a
spicy note
9 U FAE, very clean, very nice and fresh,
low residual
30 10 U FAE, very clean, fresh and low residual
12 WV No malodor, stronger residual odor
13 U* FAE, almost no residual odor
14 VU No malodor, weak FAE, residual background
WV No malodor, no FAE, pungent and irritating
background
16 V No malodor, medium background, some
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Compound Activity* Comments
of Ex. 17 W Slight malodor, poor activity, heavy
residual odor, no synergistic effect,
perhaps slower and longer lasting
18 VU No malodor, weak EAE, but very fresh
residual background odor
19 V No FAE, no malodor, highly perfumed
residual odor, perhaps slower and
longer acting
VU No malodor, weak FAE, somewhat heavier
residual background odor
21 U FAE, clean, fresh, light residual
22 VU No malodor, weak FAE, less fresh and
heavier residual background odor
23 U* FAE, very clean, extremely light back-
ground, longer lasting than usual
24 U FAE, very light residual odor, light
fragrance in background
VU Slightly pungent, but clean and no
residual malodor
26 W Trace of malodor in background, flat
residual odor, no apparent malodor
counteractant contribution
27 U FAE, light and fresh residual odor
28 U FAE, fresh and clean
29 U FAE, pleasant, light background and
residual odor
V No malodor, clean, but heavy residual
background odor
31. U FAE, fresh, almost irritating, clean
and acceptable residual odor intensity
32 VU FAE, slower action but very clean,
fresh and light residual
33 W Borderline excellent, FAE slow, no sharp
impact, no malodor, clean acceptable
residual
34 U FAE, clean and nice residual
U FAE, clean and nice residual of lower
intensity
cis/trans-2- X No malodor, but medium heavy residual,
(4'-methylcyclo- poor mix with fragrance, unpleasant
hexyl)-2-propyl
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43-4270A
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*Ability of compound to counteract the malodor according to
the following scale:
U* "Outstanding" - Fresh air effect pronounced and
producing extremely light or no residual odor at all.
U "Excellent" - Fresh air effect and light and pleasant
residual background odor.
V "Very good" - No fresh air effect but total abatement
of malodors, variable, but not high residual back-
ground odor.
W "Good" - Only traces of malodor, often of changed
quality, remain. Residual background odor accept-
able to pleasant, not too strong.
X "Fair" - Original malodor clearly discernable but
of low intensity. Residual background odor accept-
able at best.
Y "Poor" - Original malodor somewhat reduced in
intensity, but dominates. Overall residual back-
ground odor unpleasant to unacceptable.
Z "No activity".
** FAE ~ fresh air effect.
While the invention has been described herein with
regard to certain specific embodiments, it is not so limited.
It is to be understood that variations and modifications thereof
may be made by those skilled in the art without departing from
the spirit and scope of the invention.