CA1109078A - Malodor counteractants - Google Patents

Abstract

ABSTRACT OF THE DlSCLOSURE
There are disclosed novel compounds of the formulae:

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.

Description

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~

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) ~ 43-4270A

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) 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 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

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.

\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, 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-~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 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 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.

~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

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~

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.

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 43-fi2 70i~

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 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 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, 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=

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'-;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 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:

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 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 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 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 &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 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 ~)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 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 -30~

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.

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 irritation 9~78 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 acetate ~91~78 *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.

Claims (49)

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 I

II

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, 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.

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 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.

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 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 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, 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 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 I

II

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 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.