Use of dimethyl substituted oxymethyl cyclohexane derivatives for their insect repellency properties

Described is a method for repelling insects by use of oxymethyl cyclohexane derivatives of the structure ##STR1## wherein Z is methylene; n is 0 or 1; each of the wavy lines represents a carbon-carbon single bond or no bond; the dashed line represents a carbon-carbon double bond or a carbon-carbon single bond; each of R.sub.2, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are the same or different and each represents hydrogen or methyl; and R.sub.1 represents hydrogen, acetyl or ethoxycarbonyl with the provisos: (i) that n is 1 and each of the wavy lines represents a carbon-carbon single bond when R.sub.1, R.sub.2, and R.sub.6, are each hydrogen, R.sub.5, R.sub.7 and R.sub.8 are each methyl and the dashed line is a carbon-carbon single bond; (ii) n is 0 and each of the wavy lines represents no bond when R.sub.5 and R.sub.7 are each hydrogen and R.sub.6 and R.sub.8 are each methyl; (iii) R.sub.2 is methyl only when R.sub.1 is ethoxycarbonyl; and (iv) the dashed line is a carbon-carbon single bond only when R.sub.1 is hydrogen.

BACKGROUND OF THE INVENTION 
This invention relates to the use of dimethyl substituted oxymethyl 
cyclohexane derivatives defined according to the generic structure: 
##STR2## 
wherein Z is methylene; n is 0 or 1; each of the wavy lines represents a 
carbon-carbon single bond or no bond; the dashed line represents a 
carbon-carbon double bond or a carbon-carbon single bond; each of R.sub.2, 
R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are the same or different and each 
represents hydrogen or methyl; and R.sub.1 represents hydrogen, acetyl or 
ethoxycarbonyl with the provisos: 
(i) that n is 1 and each of the wavy lines represents a carbon-carbon 
single bond when R.sub.1, R.sub.2, and R.sub.6, are each hydrogen, 
R.sub.5, R.sub.7 and R.sub.8 are each methyl and the dashed line is a 
carbon-carbon single bond; 
(ii) n is 0 and each of the wavy lines represents no bond when R.sub.5 and 
R.sub.7 are each hydrogen and R.sub.6 and R.sub.8 are each methyl; 
(iii) R.sub.2 is methyl only when R.sub.1 is ethoxycarbonyl; and 
(iv) the dashed line is a carbon-carbon single bond only when R.sub.1 is 
hydrogen. 
This invention also relates to the use of such compounds and compositions 
of matter in insect repellent soaps and the like wherein the compositions 
of matter are used as such or in combination in control release systems 
with polymers such as biodegradable polymers. 
The prior art discloses a vast number of floral type fragrance materials 
useful in perfumery. However, such floral type materials in many instances 
are attractants rather than repellents for various insects including the 
wide variety of mosquitoes which proliferate in temperate, subtropical and 
tropical zones as well as the wide variety of flies (e.g., Musca domestica 
L.(Diptera:Muscidae)) which proliferate in the temperate and cooler 
climate zones. 
The dimethyl substituted oxymethyl cyclohexane derivatives of our invention 
which are repellents have aesthetically pleasing aromas as disclosed, for 
example, in U.S. Pat. No. 5,098,886 issued Mar. 24, 1992; U.S. Pat. No. 
5,100,872 issued on Mar. 31, 1992; U.S. Pat. No. 4,289,146 issued on Sep. 
15, 1981; and U.S. Pat. No. 4,321,164 issued on Mar. 23, 1982, the 
specifications for which are incorporated herein by reference.

SUMMARY OF THE INVENTION 
This invention relates to the use of dimethyl substituted oxymethyl 
cyclohexane derivatives defined according to the structure: 
##STR36## 
wherein Z is methylene; n is 0 or 1; each of the wavy lines represents a 
carbon-carbon single bond or no bond; the dashed line represents a 
carbon-carbon double bond or a carbon-carbon single bond; each of R.sub.2, 
R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are the same or different and each 
represents hydrogen or methyl; and R.sub.1 represents hydrogen, acetyl or 
ethoxycarbonyl with the provisos: 
(i) that n is 1 and each of the wavy lines represents a carbon-carbon 
single bond when R.sub.1, R.sub.2, and R.sub.6, are each hydrogen, 
R.sub.5, R.sub.7 and R.sub.8 are each methyl and the dashed line is a 
carbon-carbon single bond; 
(ii) n is 0 and each of the wavy lines represents no bond when R.sub.5 and 
R.sub.7 are each hydrogen and R.sub.6 and R.sub.8 are each methyl; 
(iii) R.sub.2 is methyl only when R.sub.1 is ethoxycarbonyl; and 
(iv) the dashed line is a carbon-carbon single bond only when R.sub.1 is 
hydrogen 
as insect repellents against houseflies (Musca domestica L. 
(Diptera:Muscidae)), mosquitoes including those set forth on the following 
species list: 
Culex nigripalpus; 
Aedes atlanticus; 
Culex salinarius; 
Aedes vexans; 
Culex spp.; 
Simulium spp.; 
Psoroferia ferox; 
Aedes infirmatus; 
Drosophila melanogaster; 
Coccinellidae; 
Anopheles crucians; 
Psoroferia columbiae; 
Culicoides spp.; and 
Aedes spp. 
and the horn fly, Haematobia irritans [L.]. 
Specific examples of the dimethyl substituted oxymethyl cyclohexane 
derivatives useful in the practice of our invention are those having the 
following structures: 
##STR37## 
Our invention also relates to the use of the foregoing insect repellent 
compositions in personal soap compositions, for example, the insect 
repellent soap composition described in U.S. Pat. No. 4,707,496 issued on 
Nov. 17, 1987 the specification for which is incorporated by reference 
herein. Thus, in applying the teachings of U.S. Pat. No. 4,707,496 to our 
invention, a topical insect repellent soap composition and a method of 
protection using such a composition is described where the insect 
repellent soap composition comprises: 
(i) from 63.0 up to 99.5% by weight of a soap mixture containing from 4.1 
up to 7% by weight of a soap of caprylic acid, from 3.8 up to 7% of a soap 
of capric acid, from 32.1 up to 45% of a soap of lauric acid, from 12 up 
to 17.5% by weight of a soap of myristic acid, from 5.0 up to 10% by 
weight of a soap of palmitic acid, from 1.6 up to 3% by weight of a soap 
of stearic acid, from 3.5 up to 5% by weight of a soap of oleic acid and 
from 0.9 up to 5% by weight of a soap of linoleic acid; 
(ii) from 0.1 up to 2% by weight of C.sub.8 -C.sub.18 straight chain fatty 
acids; 
(iii) from 10 up to 30% by weight of one of the dimethyl substituted 
oxymethyl cyclohexane derivative-containing compositions of our invention 
as set forth, supra; and 
(iv) from 0.2 up to 5% by weight of an effective residual insecticide as 
described in U.S. Pat. No. 4,707,496. 
Other insect repellent soaps can be produced by adding an appropriate 
dimethyl substituted oxymethyl cyclohexane derivative-containing 
composition of our invention to one or more of the compositions described 
and claimed in U.S. Pat. No. 4,453,909 issued on Jun. 12, 1984 and U.S. 
Pat. No. 4,438,010 the specifications for which are incorporated by 
reference herein. Described in said U.S. Pat. No. 4,453,909 and U.S. Pat. 
No. 4,438,010 is a process for making a tablet of soap containing a 
perfume-containing core, hollow or solid fabricated from a hard plastic 
material either thermosetting or thermoplastic. The soap from the 
resulting composite tablet is usable until the core is washed clean and 
contains functional ingredients, e.g., the repellents described, supra, 
and, optionally, an aromatizing agent until the core is washed clean. This 
obviates the wastage of soap which normally occurs as a conventional soap 
tablet becomes very thin on use and at the same time gives rise to a 
continuously functional ingredient containing soap (e.g., a repellent and 
optionally aromatizing agent) tablet. Thus, this invention also relates to 
detergent bars having a plastic core containing an appropriate dimethyl 
substituted oxymethyl cyclohexane derivative-containing composition and, 
optionally, an additional perfume. More particularly, this invention 
relates to detergent bars intended for conventional toilet soap uses 
either as hand soaps or bath or shower soaps which are elastic or 
inelastic in nature but which contain a solid plastic core containing 
insect repellent and, optionally, perfume, giving them unique properties 
which alleviate wastage thereof and causes the environment surrounding the 
soap on use thereof to be both insect repellent and, optionally, 
aromatized in an aesthetically pleasing manner. 
Yet another aspect of our invention relates to the use of the dimethyl 
substituted oxymethyl cyclohexane derivative-containing repellents of our 
invention taken further in combination with N-(methyl 
toluyl)-methylpiperidines defined according to the structure: 
##STR38## 
as described in U.S. Pat. No. 3,463,855 issued on Aug. 26, 1969 the 
specification for which is incorporated by reference herein. The compounds 
defined according to the structure: 
##STR39## 
include: N-(meta-toluyl)-2-methylpiperidine; 
N-(meta-toluyl)-3-methylpiperidine; and 
N-(meta-toluyl)-4-methylpiperidine. 
The proportions of compounds defined according to the structure: 
##STR40## 
to the appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition described, supra, are between 1 part 
N-(meta-toluyl) methylpiperidine:99 parts appropriate dimethyl substituted 
oxymethyl cyclohexane derivative-containing composition of our invention 
down to 99 parts appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition of our invention: part 
N-(meta-toluyl)-methylpiperidines. 
In addition, the compositions of our invention useful in repelling insects 
can also contain 1-nonen-3-ol described and claimed in U.S. Pat. Nos. 
4,693,890 and 4,759,228 issued on Jul. 26, 1988 the specifications for 
which are incorporated by reference herein. The ratio of 
1-nonen-3-ol:appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition of our invention useful in repellent 
compositions may vary from about 1 part 1-nonen-3-ol:99 parts appropriate 
dimethyl substituted oxymethyl cyclohexane derivative-containing 
composition of our invention down to 99 parts 1-nonen-3-ol:1 parts 
appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition of our invention. 
In addition to the soap fabrication, another aspect of our invention 
relates to the formation of repelling articles containing the appropriate 
dimethyl substituted oxymethyl cyclohexane derivative-containing 
compositions of our invention, that is, articles useful for repelling 
houseflies (Musca domestica L. (Diptera:Muscidae)) or the mosquitoes 
(Aedes aegypti) or other insect species: 
Culex nigripalpus; 
Aedes atlanticus; 
Culex salinarius; 
Aedes vexans; 
Culex spp.; 
Simulium spp.; 
Psoroferia ferox; 
Aedes infirmatus; 
Drosophila melanogaster; 
Coccinellidae; 
Anopheles crucians; 
Psoroferia columbiae; 
Culicoides spp.; and 
Aedes spp. 
or the horn fly (Haematobia irritans [L.]) in combination with compatible 
polymers which may or may not be biodegradable (for example, high density 
polyethylene or low density polyethylene, or biodegradable polymers such 
as biodegradable thermoplastic polyurethanes as disclosed in Japan Kokai 
Tokyo Koho 92/13710 (abstracted at Chemical Abstracts, Volume 
116:236397z), biodegradable ethylene polymers having ester linkages in the 
main chain such as that disclosed by Japan Kokai Tokyo Koho 92/50224 
(abstracted at Chemical Abstracts, Volume 116:126397z); biodegradable 
ethylene polymers disclosed by Japan Kokai Tokyo Koho 92/50225 (abstracted 
at Chemical Abstracts, Volume 116:126398a; and poly(epsilon caprolactone) 
homopolymers and compositions containing same as disclosed in U.S. Pat. 
Nos. 4,496,467; 4,469,613 and 4,548,764 the specifications for which are 
incorporated herein by reference. Thus, another aspect of our invention 
provides a process for forming appropriate dimethyl substituted oxymethyl 
cyclohexane derivative-containing compositions containing polymeric 
particles such as foamed polymeric pellets which include a relatively high 
concentration of the appropriate dimethyl substituted oxymethyl 
cyclohexane derivative-containing compositions of our invention as 
defined, supra. 
Thus, another aspect of our invention relates to the formation of 
appropriate dimethyl substituted oxymethyl cyclohexane derivatives 
containing polymeric pellets by means of introduction into a single or 
twin screw extruder, in series, a thermoplastic polymer followed by the 
appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition of our invention which is compatible 
with the thermoplastic polymer, in turn (optionally), followed by 
introduction of a gaseous blowing agent or blowing agent which will 
produce a gas which is inert to the polymer and to the appropriate 
dimethyl substituted oxymethyl cyclohexane derivative-containing 
composition previously introduced into the extruder. 
The advantage of using a foamed polymeric particle are multiple, to wit: 
(i) improved handling; 
(ii) greater retention of the appropriate dimethyl substituted i oxymethyl 
cyclohexane derivative-containing composition when not in use; and 
(iii) greater length of time during which the release of the appropriate 
dimethyl substituted oxymethyl cyclohexane derivative-containing 
composition of our invention from the polymer is at "steady state" or "0 
order". 
The nature of the extruder utilized in the process of our invention to form 
the appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition-containing polymer particles of our 
invention may be either single screw or double screw. Thus, the types of 
extruder that can be used are disclosed at pages 246-267 and 332-349 of 
the Modern Plastics Encyclopedia, 1982-1983, published by the McGraw-Hill 
Publishing Company, the disclosure of which is incorporated by reference 
herein. More specifically, examples of extruders which are usable in 
carrying out one or more of the processes of our invention (with 
modification for introduction of the appropriate dimethyl substituted 
oxymethyl cyclohexane derivative-containing compositions of our invention) 
downstream from the introduction of the polymer and with further 
modification that the gaseous blowing agent is introduced still further 
downstream from the point of introduction of the appropriate dimethyl 
substituted oxymethyl cyclohexane derivative-containing compositions of 
our invention are as follows: 
1. The Welex "Super Twinch" 3.5 inch extruder manufactured by Welex 
Incorporated, 850 Jolly Road, Blue Bell, Pa. 19422; 
2. Krauss-Maffei twin screw extruder manufactured by the Krauss-Maffei 
Corporation/Extruder Division, 3629 West 30th Street South, Wichita, Kans. 
67277; 
3. Modified Sterling Model 4000 and 5000 series extruder manufactured by 
Sterling Extruder Corporation of 901 Durham Avenue, South Plainfield, 
N.J.; 
4. CRT ("Counter-Rotating Tangential") Twin Screw Extruder manufactured by 
Welding Engineers, Inc. of King of Prussia, Pa. 19406; 
5. The Leistritz Twin Screw Dispersion Compounder manufactured by the 
American Leistritz Extruder Corporation of 198 U.S. Route 206 South, 
Somerville, N.J. 08876; 
6. The ZSK Twin Screw Co-Rotating Extruder manufactured by the Werner & 
Pfleiderer Corporation of 663 East Crescent Avenue, Ramsey, N.J. 07446; 
7. The Farrel Extruder manufactured by Farrel Connecticut Division, Emhart 
Machinery Group, Ansonia, Conn. 06401; 
8. The MPC/V Baker Perkins Twin Screw Extruder manufactured by the Baker 
Perkins Inc. Chemical Machinery Division of Saginaw, Mich. 48601; and 
9. The Berstorff single screw, twin screw or foam extrusion equipment 
manufactured by Berstorff Corporation, P.O. Box 240357, 8200-A Arrowing 
Boulevard, Charlotte, N.C. 28224. 
In producing the appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition-containing polymer particles of our 
invention, various polymers may be utilized, for example, low density 
polyethylene, high density polyethylene, polypropylene, the copolymer of 
ethylene and vinyl acetate, and polyvinyl chloride. More specifically, the 
polymers used in the practice of our invention may be copolymers of 
ethylene and a polar vinyl monomer selected from (a) vinyl acetate; (b) 
ethyl acrylate; (c) methyl acrylate; (d) butyl acrylate; and (e) acrylic 
acid including the hydrolyzed copolymer of ethylene and vinyl acetate. 
Preferred copolymers are ethylene/vinyl acetate with about 9 to 60% vinyl 
acetate and ethylene/ethyl acrylate with about 6 to 18% ethyl acrylate. 
Resins of the type disclosed for use as copolymers are commercially 
available in the molding powder form; for example, ethylene vinyl acetate 
copolymers are marketed by the E.I. dupont Nemours Company under the 
Tradename ELVAX.RTM. and by the Arco Polymer Division under the Trademark 
DYLAND.RTM. and by the Exxon Corporation of Linden, N.J. under the 
Trademark DEXXON.RTM.. Ethylene/ethyl acrylate copolymers are marketed by 
Union Carbide Corporation under the Trademark EEA RESIN.RTM.. 
The polymer is added to the single screw or twin screw extruder at a feed 
rate in the range of from about 80 up to about 300 pounds per hour while 
maintaining the temperature of the screw extruder between about 
160.degree. C. and about 240.degree. C. If the polymer or copolymer powder 
is added to the extruder at a reference "barrel segment", then the 
appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition of our invention is added to the 
extruder under pressure downstream from the retention point of the polymer 
at one dr more of the "barrel segments" (S-2, S-3, S-5, S-6, S-7, S-8 or 
S-9) (referring to FIG. 9 briefly described, supra, and described in 
detail, infra). 
The proportion of the appropriate dimethyl substituted oxymethyl 
cyclohexane derivative-containing composition (taken further together with 
other insect repelling materials, if desired) to resin can vary from small 
but effective amounts on the order of about 1% of the weight of the resin 
body up to about 45% by weight of the resin body. In general, it is 
preferred to use between about 5% up to about 30% based on the weight of 
the resin body of insect repellent composition of our invention. This is 
an optimum amount balancing the proportion of the insect repellent 
composition of our invention against the time period over which the 
article emits the insect repellent composition and against the tendency of 
the components of the insect repellent composition to oil out either 
individually or in combination. This "oiling out" is specifically avoided 
as a result of the use of the foaming agent discussed, infra. 
Various polymers are useful in the practice of our invention. Specific 
examples of polymers useful in the practice of our invention are as 
follows: 
(a) DYLAN.RTM. brand of low density polyethylene, DYLAN.RTM. is a trademark 
owned by the Atlantic Richfield Company of Los Angeles, Calif.; 
(b) DYLITE.RTM. of expandable polystyrene composition, SUPER DYLITE.RTM. is 
a trademark of the Atlantic Richfield Company of Los Angeles, Calif.; 
(c) SUPER DYLAN.RTM. is a trademark of the Atlantic Richfield Company of 
Los Angeles, Calif.; 
(d) blended polyethylene and carbon black as specifically taught in U.S. 
Pat. No. 4,369,267 issued on Jan. 18, 1983 the specification for which is 
incorporated by reference herein; 
(e) polystyrene as disclosed in U.S. Pat. No. 4,369,227 issued on Jan. 18, 
1983 the specification for which is incorporated by reference herein; 
(f) polyene/.alpha.-olefin as exemplified and disclosed in U.S. Pat. No. 
4,369,291 the specification for which is incorporated by reference herein; 
(g) poly-.alpha.-olefins disclosed in Canadian Letters Patent No. 1,137,069 
issued on Dec. 7, 1982 the specification for which is incorporated by 
reference herein; 
(h) polymeric compositions as disclosed in Canadian Letters Patent No. 
1,137,068 issued on Dec. 7, 1982 the specification for which is 
incorporated by reference herein; 
(i) poly-.alpha.-olefins disclosed in Canadian Letters Patent No. 1,137,067 
the specification for which is incorporated by reference herein; 
(j) polyolefins described in Canadian Letters Patent No. 1,137,066 the 
specification for which is incorporated by reference herein; 
(k) polyethylene oxides as disclosed in Canadian Letters Patent No. 
1,137,065 issued on Dec. 7, 1982 the specification for which is 
incorporated by reference herein; 
(l) olefin polymers and copolymers as disclosed in Canadian Letters Patent 
No. 1,139,737 issued on Jan. 18, 1983 the disclosure of which is 
incorporated by reference herein; 
(m) polyolefins disclosed in Canadian Letters Patent No. 1,139,738 issued 
on Jan. 18, 1983 the disclosure of which is incorporated by reference 
herein; 
(n) chlorinated PVC as disclosed in Polymer 1982, 23 (7, Suppl.), pages 
1051-5, abstracted at Chemical Abstracts, Volume 97:14550y, 1982; 
(o) polyepsilon Caprolactone copolymers made by means of alcohol initiated 
polymerization as disclosed in J. Polym. Sci. Polym. Chem. Ed. 1982, 20 
(2), pages 319-26, abstracted at Chemical Abstracts, Volume 96:123625x, 
1982; 
(p) styrene acryonitrile copolymers as disclosed in Diss. Abstracts Int. B, 
1982, 42(8), page 3346 and abstracted at Chemical Abstracts, Volume 
96:143770n, 1982; 
(q) copolymers of epsilon caprolactone with 1,4-butane diol as disclosed in 
Kauch Rezine, 1982, (2), pages 8-9, abstracted at Chemical Abstracts, 
Volume 96:182506g, 1982; 
(r) polyesters as disclosed in U.S. Pat. No. 4,326,010 the specification 
for which is incorporated by reference herein; 
(s) chlorinated polyethylene as disclosed by Belorgey, et al, J. Polym. 
Sci. Plym. Ed. 1982, 20(2), pages 191-203; 
(t) plasticized polyepsilon caprolactone copolymers containing dimethyl 
phthalate plasticizers as set forth in Japanese Patent No. J81/147844, 
abstracted at Chemical Abstracts, Volume 96:669984y, 1982, the 
specification for which is incorporated by reference herein; 
(u) maleic anhydride modified adducts of polyepsilon caprolactone polyols 
and ethylenically unsaturated monomer as disclosed in U.S. Pat. No. 
4,137,279 issued on Jan. 30, 1979 the specification for which is 
incorporated by reference herein; 
(v) polyurethane polymers having lactone backbones as disclosed in U.S. 
Pat. No. 4,156,067 issued on May 22, 1979 the disclosure of which is 
incorporated by reference herein; 
(w) polyurethane polyether resins wherein the resin is obtained by reacting 
a polyfunctional lactone with a long chain polyalkylene diol and a 
urethane precursor as disclosed in U.S. Pat. No. 4,355,550 issued on Mar. 
10, 1981 the disclosure of which is incorporated by reference herein; and 
(x) resins having polyurethane backbones as disclosed in U.S. Pat. No. 
3,975,350 issued on Aug. 17, 1976 the disclosure of which is incorporated 
by reference herein. 
Examples of poly(epsilon caprolactone) homopolymers as set forth, for 
example, in U.S. Pat. No. 4,496,467 are those having the structures: 
##STR41## 
wherein n represents an integer of from about 500 up to about 1,200 with 
the proviso that the average "n" varies from about 600 up to about 800. 
Downstream from the addition point of the dimethyl substituted oxymethyl 
cyclohexane derivative-containing compositions of our invention taken 
alone or taken together with other insect repellent agents and fragrance 
materials, optionally, the gaseous liquid containing blowing agent may be 
added (e.g., at "barrel segments" S-5, S-6, S-7, S-8, S-9 or S-10) using 
the polymer addition "barrel segment" as a reference "barrel segment" S-1. 
Examples of the gaseous blowing agents are carbon dioxide in proportions 
of from 1 up to 99% by volume nitrogen and from 99 down to 1% by volume 
carbon dioxide, helium, mixtures of helium and nitrogen, mixtures of 
helium and carbon dioxide and other gases which are inert at the 
temperature and pressure of the polymer at the time of the extrusion 
operation. Thus, gas containing oxygen or other reactive gases, e.g., 
hydrogen, should be avoided. The pressure of the gas blowing agent being 
added to the extruder at the point of addition may vary from about 80 to 
about 150 psig. Higher pressure may be used without adversely affecting 
the usefulness of the foamed insect repellent composition-containing 
particle. 
The feed rate range of insect repellent compositions which contain but 
which are not limited to the dimethyl substituted oxymethyl cyclohexane 
derivative-containing compositions of our invention may be between about 
0.5% up to about 45% by weight of the polymer. It must be emphasized at 
this point that the insect repellent composition of our invention which 
are the dimethyl substituted oxymethyl cyclohexane derivative-containing 
compositions of our invention are in and of themselves aromatizing 
materials. However, the maximum quantity of the combination of other 
aromatizing materials and the appropriate dimethyl substituted oxymethyl 
cyclohexane derivative-containing compositions of our invention is 45%. 
The dies of the extruder may create rod, sheet, film or ribbon. The 
resulting product may then, if desired, be pelletized to form insect 
repellent composition-containing polymer particles or the ribbon may be 
used "as is" as an insect repellent-containing polymeric article of 
manufacture itself. 
In addition to the optional gaseous blowing agents (which are necessarily 
"inert" gases), blowing agents may be added at the same point on the 
extruder which will create gaseous voids in the insect 
repellent-containing polymer articles of our invention and these "blowing 
agents" are well known to one having ordinary skill in the art. Examples 
of such non-gaseous containing materials which yield gases on admixture 
with the polymer in the extruder but which are still inert to the insect 
repellent (or attractant in the event of formulation of microporous 
polymeric particles containing the compound having the structure: 
##STR42## 
for use in insect traps as the case may be) are as follows: (i) under high 
pressure, ethylene, methane, propane, butane, propylene, methyl chloride, 
methyl bromide, vinyl chloride and methylene dichloride as more 
specifically described in U.S. Pat. No. 2,387,730 the specification for 
which is incorporated by reference herein; 
(ii) ordinarily liquid material such as n-pentane, isopentane, 
cyclopentane, hexane and petroleum ether fractions or halogen hydrocarbons 
such as CFCl.sub.3, CF.sub.2 Cl.sub.2, CH.sub.3 Cl, CH.sub.2 Cl.sub.2 
separately or in admixture with one another as set forth in U.S. Pat. No. 
3,758,425, column 4, lines 1-5 the specification for which is incorporated 
by reference herein; 
(iii) dichlorotetrafluoromethane, tetramethylmethane, 
monochlorodifluoromethane, dichlorodifluoromethane and 
dichlorotetrafluoromethane as described in U.S. Pat. Nos. 2,948,664 and 
2,948,665 issued on Aug. 9, 1990 the specifications for which are 
incorporated by reference herein; and 
(iv) azo bis(formamide), diazoaminobenzene; N,N-dinitrosopentamethylene 
tetramine; N,N-dimethyl, N,N-dinitrosoterephthalamide; 
p,p'-oxy-bis-(benzene sulfonyl semicarbazide); aza 
bis-(isobutyronitrile)p,p'-oxy-bis(benzene sulfonyl hydrazide); 
p,p'-diphenyl-bis(sulfonyl hydrazide); benzene-sulfonyl hydrazide; 
m-benzene-bis(sulfonyl hydrazide) as more specifically described in U.S. 
Pat. No. 3,298,975 issued on Jan. 17, 1967 the specification for which is 
incorporated by reference herein. 
The resulting extruded (and, if desired, pelletized) material may then be, 
for example, injection molded to form a useful article. Such injection 
molding can be carried out in accordance with the procedure as set forth 
in U.S. Pat. No. 3,268,635 issued on Aug. 23, 1966 the specification for 
which is incorporated by reference herein. 
In addition, our invention relates to candle body materials which on use 
are both insect repellent and perfuming which contain the appropriate 
dimethyl substituted oxymethyl cyclohexane derivative-containing 
compositions of our invention and, if desired, other insect repellent 
materials including, for example, at least one of the compounds having the 
structure: 
##STR43## 
in order to repel houseflies (Musca domestica L. (Diptera:Muscidae)) 
and/or the mosquitoes, Aedes aegypti and or the insect species: 
Culex nigripalpus; 
Aedes atlanticus; 
Culex salinarius; 
Aedes vexans; 
Culex spp.; 
Simulium spp.; 
Psoroferia ferox; 
Aedes infirmatus; 
Drosophila melanogaster; 
Coccinellidae; 
Anopheles crucians; 
Psoroferia columbiae; 
Culicoides spp.; and 
Aedes spp. 
and/or the horn fly, Haematobia irritans [L.]. 
The housefly, horn fly and mosquito-repellent-perfuming compositions which 
form part of the candle body materials are within the following 
specifications: 
(i) from 5 up to 100% by weight of an efficacious perfuming/insect 
repellent composition containing an appropriate dimethyl substituted 
oxymethyl cyclohexane derivative-containing composition of our invention; 
and 
(ii) from 0 up to 95% by weight of an additional standard perfuming 
substance (non-insect repellent or insect repellent) which may include but 
is not limited to: 
1-nonen-3-ol; 
1-octen-4-ol; 
.alpha.-damascone; 
.beta.-damascone; 
.delta.-damascone; 
trans,trans .delta.-damascone; 
methyl jasmonate; 
dihydromethyl jasmonate; 
the schiff base of vanillin and methyl anthranilate; 
the schiff base of ethyl vanillin and methyl anthranilate; 
vanillin; and 
ethyl vanillin. 
The foregoing formula may require a solubilizing agent, e.g., the methyl 
ester of dihydroabietic acid (commercial name: HERCOLYN.RTM. D), benzyl 
benzoate, isopropyl myristate and/or C.sub.12 -C.sub.14 isoparaffin 
hydrocarbons. 
The candle base composition can be standard paraffin wax, or it can be 
transparent or pastel shaded as more particularly described in U.S. Pat. 
No. 3,615,289 issued on Oct. 26, 1971 (the disclosure of which is 
incorporated by reference herein) and wherein the candle body comprises as 
the basic components a mixture of: 
(i) a thermoplastic polyamide resin formed from linoleic acid polymerized 
with a polyamine compound; 
(ii) an alkanol amide or alkanol amine; and 
(iii) a stearic acid compound. 
The weight ratio of candle body:insect repellent/perfumant substance or our 
invention may vary from about 0.8% up to about 10% with a range of from 
about 0.8% up to about 2.0% being preferred when no additional non-insect 
repelling perfume oil is used in conjunction with the appropriate dimethyl 
substituted oxymethyl cyclohexane derivative-containing composition of our 
invention; and with a range of from about 1.5% up to about 10% by weight 
of the overall composition being preferred when an additional non-insect 
repelling perfume oil is used in conjunction with the appropriate dimethyl 
substituted oxymethyl cyclohexane derivative-containing composition of our 
invention. 
Specifically, the polyamide may be a VERSAMID.RTM. resin which is a 
thermoplastic condensation product of polymerized linoleic acid with 
various polyamine compounds such as ethylene diamine, ethylene triamine 
and the like. Specific VERSAMID.RTM. compounds are VERSAMID.RTM. 900, 
VERSAMID.RTM. 930, VERSAMID.RTM. 940, VERSAMID.RTM. 948, VERSAMID.RTM. 950 
and VERSAMID.RTM. 1635. These compounds are products of the Henkel 
Chemical Corporation of Minneapolis, Minn.. 
Another substance required in the clear candle composition consists of 
about 20-55% by weight of an alkanol amine or alkanol amide prepared by 
the reaction of a fatty acid ester and amine whereby the ester and the 
amine are in substantially equal proportions, for example, compounds such 
as BARLOL.RTM. 12C2 (manufactured by the Baroid Chemical Company) a 
monoalkyl diethanolamine having 8 to 18% carbon atoms in the alkyl chain. 
A third component of the clear plastic candle composition comprises one or 
more stearic acid esters or a mixture of stearic acid esters and stearic 
acid. These esters include such compounds as isopropyl isostearate, butyl 
stearate and hexadecyl stearate. The stearic acid compounds serve as 
stabilizing agents which permit the ready incorporation of the insect 
repellent/perfumant compositions of our invention up to a level of 
approximately 5% (total proportion of perfume oil-insect repellent 
composition). They are carriers for the perfumant/insect repellent and may 
be used in a proportion of between 1 and 50% by weight of the composition 
although the preferable range is between 20 to 30%. In this connection, it 
is possible to use up to about 10% by weight of a perfumant/insect 
repellent if part of the formula is replaced by the material NEVEX.RTM. 
100, a product which is a coumarin-indene copolymer resin of very little 
unsaturation manufactured by the Neville Chemical Company. 
Rather than being a crystalline paraffin wax, the candle base of our 
invention may be an oil gel that has as its base a light mineral oil, an 
inexpensive natural oil or a combination of such oils which oil gel has a 
non-greasy surface and feel and sufficient rigidity to be self-supporting 
at room temperature. Such a gel is disclosed in U.S. Pat. No. 3,645,705 
issued on Feb. 29, 1972 the disclosure of which is incorporated by 
reference herein. Such compositions of matter include: 
(a) from about 35% up to about 85% by weight of an oil which is normally 
liquid at room temperature chosen from the group consisting of light 
mineral oils and natural oils having iodine values substantially within 
the range of 40-135; 
(b) from about 7% up to about 40% by weight of a long chain polyamide 
having a molecular weight substantially within the range of 6,000-9,000 
and a softening point substantially within the range of 18.degree. 
C.-48.degree. C.; and 
(c) from about 7% up to about 30% of alcohol selected from the group 
consisting of 8 to 12 carbon primary alcohols. 
The dimethyl substituted oxymethyl cyclohexane derivatives of our invention 
may be in the form of racemic mixtures or they may be in the form of 
sterioisomers. Thus, for example, representations of such sterioisomers 
are representations having the following structures: 
##STR44## 
wherein R.sub.1 is methyl or ethyl and R.sub.2 is hydrogen or methyl. 
DETAILED DESCRIPTION OF THE DRAWINGS 
The data set forth in FIGS. 1A, 1B, 2A, 2B, 3, 4, 5, 6, 7, 8, 8A, 8B, 8C, 
22 and 23 were determined using the olfactometer of FIG. 10 and the insect 
trap of FIG. 21. 
Referring to the olfactometer of FIG. 10, said olfactometer is described in 
detail in U.S. Pat. No. 5,118,711 issued on Jun. 2, 1992 the specification 
for which is incorporated by reference herein. 
Referring to FIG. 10, air supply source 3634 provides air to mixing station 
3636 wherein the air is mixed with treatment agent from treatment agent 
source 3635 (source of, for example, the repellent composition which is an 
appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition). The resulting mixture passes through 
the tube 3636g and enters the apparatus through the side portals. The 
entry is through a spacer plate and above base plate 3625. The entry of 
the air-treatment agent is in a direction parallel to the surface of base 
plate 3625. Thus, the base plate 3625 is separated from spacer plate 3629 
for the air-treatment agent (e.g., the appropriate dimethyl substituted 
oxymethyl cyclohexane derivative-containing composition of our invention). 
Air exits through line 3533a using exhaust fan 3633. The air exit is 
indicated by reference numeral 3537. 
Simultaneously, with the supplying of air and treatment agent from mixing 
station 3636, light is supplied from beneath the enclosed insect feeding 
and/or stimulating means through light guides 3652 from light source 3551 
which is powered by electric power supply 3550 marketed by RADIO 
SHACK.RTM. Division of Tandy Corporation of Forth Worth, Tex. 76102 under 
the Trademark ARCHER.RTM., Catalog No. 276-228 ("1.0 mm optical plastic 
fiber length 5 meter"). An example of light source 3551 is KRATOS.RTM. 
Monochromator Illuminator GM 100 Miniature VIS-IR Grating Monochromator 
(Model No. GM 100-1, GM 100-2, GM 100-3 or GM 100-4) as manufactured by 
KRATOS.RTM. Analytical Instruments Corporation, 170 Williams Drive, 
Ramsey, N.J. 07446. Another light supply source is the KRATOS.RTM. GM 200 
Double Grating Monochromator. Another example of a useful light source is 
the KRATOS.RTM. GM 252 High Intensity Grating Monochromator. The base 
plate 3625 is also separated from the spacer plate 3629 for the light 
guides 3652 whereby the light guides 3652 are held in place in the base 
plate 3625 whereby the light (or other forms of radiation) is directed in 
a direction perpendicular to the electrical sensor element 3610. Air 
supply source from location 3634 and treatment agent from location 3635 is 
mixed at mixing station 3636. whereupon treatment agent and air in 
admixture is passed through lines 3636a and 3636g through portals located 
in the spacer element 3628 in a direction along a directional vector 
parallel to the electrical sensing element 3610 held in place by holders 
3610a and 3610b. The electrical sensing elements are located directly 
below the horizontally positioned insect feeding and/or stimulating 
microporous substantially planar lamina 3670 which is held in place by 
ring 3660 located on spacer plate 3629 spaced from the base plate 3625 by 
spacer ring 3628. It should be noted that the spacer plate 3629, spacer 
ring 3628 and base plate 3625 enclose the entire "enclosed insect feeding 
and/or stimulating means" which have controlled limited access to the 
external environment surrounding the apparatus and in which the insects to 
be tested, e.g., mosquitoes, horn flies or houseflies, are placed. 
The insect attractant quantitative detecting means made up of wires 3699 
(the entire grid being denoted using reference numeral 3610) is located 
immediately beneath the porous membrane 3670, the outer surface of which 
contains a feeding stimulant composition or stimulant composition for 
insects (for example, agar). Immersed in the feeding stimulate composition 
or stimulant composition for insects (e.g., agar) is electrode 3679 
connected to wire 3619 which connects with either wire 3619a or 3619b 
which is connected to the grid wires 3699 (which make up the insect 
attractant quantitative detecting means located immediately below lamina 
3670). 
As stated, supra, the sensor causes an electrical impulse caused by the 
pressure of the insects landing to proceed through wires 3619a and 3619b 
to an electrically biased differential amplifier 3639 (using electrical 
power. supply 3539) also connected to wire 3619c which is connected to the 
electrode 3679 which is immersed in the feeding stimulant composition or 
stimulant for the insect and then to a multi-channel A.C. converter 3523. 
Converter 3523 is associated with program tape storage 3524, printer 3520 
and data link to digital computer 3521. Differential amplifier 3632 is 
connected in series to electrical bias for pseudo host 3669 which in turn 
is connected to wire 3619 which in turn is connected to the electrode 3679 
immersed in the insect stimulant composition located on the surface of 
porous lamina 3670. 
Referring to the testing apparatus, the semiochemical field trap 1000 for 
blood feeding arthropods, field trap 1000 is located in a three-space with 
axes perpendicular to one another. The semiochemical field trap 1000 is 
shown in perspective view in FIG. 21 comprising: 
(1) an upright, vertically disposed housing; 
(2) extending outwardly from the housing a plurality of horizontally 
disposed hollow housings 116a and 116b which have contained therein insect 
sticky traps; 
(3) air 138 and/or carbon dioxide supply means 134 and 136 for supplying 
air and/or carbon dioxide into the vertical hollow housing and then 
through the plurality of horizontally disposed hollow housings 116a and 
116b; and 
(4) at least one power supply means for energizing radiation means located 
on the vertical hollow housing 
whereby on engagement of the power supply means with the radiation means 
and operation of the air 138 and/or carbon dioxide supply means 134 and 
136, arthropods in the vicinity of the trap are attracted by the activated 
radiation means and the gas emanating from the horizontally disposed 
hollow housing 116a to a location so close to the trap 1000 that in the 
event that an attracting semiochemical located in the housings of 116a and 
116b is detected by at least one of the arthropods, at least one of the 
arthropods will enter the inner void of the horizontally disposed hollow 
housings 116a and 116b counter current the gas stream emanating therefrom 
and remain permanently entrapped therein. 
The semiochemical field trap 1000 of FIG. 21 is disclosed in detail in U.S. 
Pat. No. 5,228,233 issued on Jul. 20, 1993, the specification for which is 
incorporated by reference herein. 
FIG. 1A is a series of graphs depicted in three dimensions (in a 
rectangular mode for the "X" and "Y" axes) showing the relative 
attractiveness or repellency of air, ISOCYCLOGERANIOL having the 
structure: 
##STR45## 
and FLORALOL having the structure: 
##STR46## 
with respect to the attractiveness or repellency of the mosquito, Aedes 
aegypti. The graph indicated by reference numeral 150a is for air. The 
graph indicated by reference numeral 145a is for ISOCYCLOGERANIOL. The 
graph indicated by reference numeral 176a is for FLORALOL. The "X" axis 
along which the particular materials are measured insofar as their 
attractiveness or repellency is concerned is indicated by reference 
numeral 107. The number of insects collected per interval is indicated on 
the "Y" axis and the "Y" axis is indicated by reference numeral 100. The 
results are tabulated in Table I(A) as follows: 
TABLE I(A) 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
ISOCYCLOGERANIOL 
145a 4 1 0 0 0 3 
Air 150a 555 
512 552 
552 574 
494 
FLORALOL 176a 3 1 0 0 0 0 
__________________________________________________________________________ 
FIG. 1B is a series of graphs depicted in three dimensions (in a 
rectangular mode for the "X" and "Y" axes) showing the relative 
attractiveness or repellency of air, ISOCYLCOGERANIOL and FLORALOL with 
reference to attractiveness or repellency for Aedes aegypti. The graphs 
are based on experiments run for a period of six hours with six intervals 
of one hour each. The graph indicated by reference numeral 145b is for 
ISOCYLCOGERANIOL. The graph indicated by reference numeral 150b is for 
air. The graph indicated by reference numeral 176b is for FLORALOL. The 
results are tabulated in Table I(B) as follows: 
TABLE I(B) 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
ISOCYCLOGERANIOL 
145b 3 0 2 5 4 0 
Air 150b 494 
547 580 
566 559 
533 
FLORALOL 176b 0 5 1 4 2 0 
__________________________________________________________________________ 
FIG. 2A is a series of graphs depicted in three dimensions (in a 
rectangular mode for the "X" and "Y" axes) showing the relative 
attractiveness or repellency of the materials: 
(i) air; 
(ii) ISOCYLCOGERANIOL having the structure: 
##STR47## 
(iii) FLORALATE having the structure: 
##STR48## 
(iv) DIHYDROFLORALOL having the structure: 
##STR49## 
The test data is for the mosquitoes, Aedes aegypti. The graphs are based on 
experiments run for a period of one hour with six intervals of ten minutes 
each. The graph indicated by reference numeral 200a is for air. The graph 
indicated by reference numeral 205a is for ISOCYCLOGERANIOL. The graph 
indicated by reference numeral 203a is for FLORALATE. The graph indicated 
by reference numeral 202a is for DIHYDROFLORALOL. The results are 
tabulated in Table II(A) as follows: 
TABLE II(A) 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
Air 200a 393 
494 570 
554 584 
578 
ISOCYCLOGERANIOL 
205a 0 0 0 0 0 0 
FLORALATE 203a 1 22 0 24 7 27 
DIHYDROFLORALOL 
202a 0 0 0 0 0 0 
__________________________________________________________________________ 
FIG. 2B is a series of graphs depicted in three dimensions (in a 
rectangular mode for the "X" and "Y" axes) showing the relative 
attractiveness or repellency of the materials: 
(i) air; 
(ii) ISOCYLCOGERANIOL having the structure: 
##STR50## 
(iii) FLORALATE having the structure: 
##STR51## 
(iv) DIHYDROFLORALOL having the structure: 
##STR52## 
The graphs are based On experiments run for a period of 18 hours with six 
intervals of 3 hours each using as the insect to be tested the mosquito, 
Aedes aegypti. The graph indicated by reference numeral 200b is for air. 
The graph indicated by reference numeral 205b is for ISOCYCLOGERANIOL, The 
graph indicated by reference numeral 203b is for FLORALATE. The graph 
indicated by reference numeral 202b is for DIHYDROFLORALOL. The results 
are tabulated in Table II(B) as follows: 
TABLE II(B) 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
Air 200b 4,472 
3,833 
5,026 
4,108 
716 
0 
ISOCYCLOGERANIOL 
205b 7 6 50 134 0 0 
FLORALATE 203b 19 7 0 0 0 0 
DIHYDROFLORALOL 
202b 1 2 0 1 0 0 
__________________________________________________________________________ 
FIG. 3 is a series of graphs depicted in three dimensions (in a rectangular 
mode for the "X" and "Y" axes) showing the relative attractiveness or 
repellency of the materials: 
(i) air; and 
(ii) DIHYDROFLORALOL having the structure: 
##STR53## 
The graphs are based On experiments run for a period of one hour with six 
intervals of ten minutes each using as the insect to be tested the horn 
fly (Haematobia irritans [L.]). 
The graph indicated by reference numeral 300 is for air. The graph 
indicated by reference numeral 302 is for DIHYDROFLORALOL. The results are 
tabulated in Table III as follows: 
TABLE III 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
Air 300 171 
302 257 
260 281 
164 
DIHYDROFLORALOL 
302 22 3 23 1 0 1 
__________________________________________________________________________ 
FIG. 4 is a series of graphs depicted in three dimensions (in a rectangular 
mode for the "X" and "Y" axes) showing the relative attractiveness or 
repellency of the materials: 
(i) air; 
(ii) ISOCYLCOGERANIOL having the structure: 
##STR54## 
(iii) FLORALATE having the structure: 
##STR55## 
(iv) FLORALOL having the structure: 
##STR56## 
The graphs are based on experiments run for a period of one hour with six 
intervals of ten minutes each using as the insect to be tested the horn 
fly (Haematobia irritans [L.]). The graph indicated by reference numeral 
400 is for air. The graph indicated by reference numeral 445 is for 
ISOCYCLOGERANIOL. The graph indicated by reference numeral 443 is for 
FLORALATE. The graph indicated by reference numeral 426 is for FLORALOL. 
The results are tabulated in Table IV as follows: 
TABLE IV 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
Air 400 170 
198 304 
339 229 
346 
ISOCYCLOGERANIOL 
445 0 0 0 0 0 0 
FLORALATE 443 1 5 0 0 1 0 
FLORALOL 426 0 0 0 0 0 0 
__________________________________________________________________________ 
FIG. 5 is a series of graphs depicted in three dimensions (in a rectangular 
mode for the "X" and "Y" axes) showing the relative attractiveness or 
repellency of the materials: 
(i) air; 
(ii) CAMEKOL DH having the structure: 
##STR57## 
(iii) FLORALOL having the structure: 
##STR58## 
(iv) DIHYDROFLORALOL having the structure: 
##STR59## 
The graphs are based on experiments run for a period of one hour with six 
intervals of ten minutes each using as the insect to be tested the horn 
fly (Haematobia irritans [L.]). The graph indicated by reference numeral 
500 is for air. The graph indicated by reference numeral 536 is for 
CAMEKOL DH. The graph indicated by reference numeral 526 is for FLORALOL. 
The graph indicated by reference numeral 542 is for DIHYDROFLORALOL. The 
results are tabulated in Table V as follows: 
TABLE V 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
Air 500 1 5 73 170 43 8 
CAMEKOL DH 536 1 1 0 0 1 0 
FLORALOL 526 4 1 1 0 0 0 
DIHYDROFLORALOL 
542 0 6 0 1 0 0 
__________________________________________________________________________ 
FIG. 6 is a series of graphs depicted in three dimensions (in a rectangular 
mode for the "X" and "Y" axes) showing the relative attractiveness or 
repellency of the materials: 
(i) air; 
(ii) FLORALATE having the structure: 
##STR60## 
(iii) DIHYDROFLORALOL having the structure: 
##STR61## 
The graphs are based on experiments run for a period of one hour with six 
intervals of ten minutes each using as the insect to be tested the horn 
fly (Haematobia irritans [L.]). The graph indicated by reference numeral 
600 is for air. The graph indicated by reference numeral 643 is for 
FLORALATE. The graph indicated by reference numeral 642 is for 
DIHYDROFLORALOL. The results are tabulated in Table VI as follows: 
TABLE VI 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
Air 600 0 62 1 1 1 19 
FLORALATE 643 0 3 0 0 0 2 
DIHYDROFLORALOL 
642 0 6 3 0 2 7 
__________________________________________________________________________ 
FIG. 7 is a series of graphs depicted in three dimensions (in a rectangular 
mode for the "X" and "Y" axes) showing the relative attractiveness or 
repellency of the materials: 
(i) air; and 
(ii) FLORALOL halving the structure: 
##STR62## 
The graphs are based on experiments run for a period of one hour with six 
intervals of ten minutes each using as the insect to be tested the 
housefly, Musca domestica L.(Diptera:Muscidae). The graph indicated by 
reference numeral 700 is for air. The graph indicated by reference numeral 
726 is for FLORALOL. The results are tabulated in Table VII as follows: 
TABLE VII 
__________________________________________________________________________ 
Composition Tested 
Graph No. 
Insects Collected per Interval 
__________________________________________________________________________ 
Air 700 172 
17 0 2 0 0 
FLORALOL 726 2 8 0 3 0 0 
__________________________________________________________________________ 
FIG. 8A is a graph showing the mean number of mosquitoes collected (on the 
"Y" axis) versus the treatment substance (on the "X" axis) using the field 
trap of FIG. 21 having six ports and three infrared light emitting diodes 
and using the following materials: 
(i) a 50:50 mole:mole mixture of air and carbon dioxide with the feed rate 
of carbon dioxide being 2.7 gram moles per hour; 
(ii) CAMEKOL DH having the structure: 
##STR63## 
(iii) ISOCYCLOGERANIOL having the structure: 
##STR64## 
The bar graph showing the mean number of insects collected using the 
mixture of air and carbon dioxide is indicated by reference numeral 8000a. 
The bar graph indicating the mean number of mosquitoes collected using 
CAMEKOL DH is indicated by reference numeral 8036a. The bar graph using 
ISOCYCLOGERANIOL is indicated by reference numeral 8045a. 
FIG. 8B is a series of bar graphs showing the mean number of mosquitoes 
collected on the "Y" axis versus the treatment substance on the "X" axis 
using the semiochemical field trap of FIG. 21 having six ports with three 
infrared light emitting diodes. The substances used are: 
(i) a 50:50 mole: mole mixture of air and carbon dioxide with the feed rate 
of carbon dioxide being 2.7 gram moles per hour; 
(ii) DIHYDROFLORALOL having the structure: 
##STR65## 
(iii) ISOCYCLOGERANIOL having the structure: 
##STR66## 
(iv) ISOCYCLOGERANIOL methyl carbonate having the structure: 
##STR67## 
(v) ISOCYCLOGERANIOL ethyl carbonate having the structure: 
##STR68## 
The bar graph showing the mean number of mosquitoes collected using the 
mixture of air and carbon dioxide is indicated by reference numeral 8000b. 
The bar graph using DIHYDROFLORALOL is indicated by reference numeral 
8042b. The bar graph showing the results using ISOCYCLOGERANIOL is 
indicated by reference numeral 8045b. The bar graph showing the results 
when using ISOCYCLOGERANIOL methyl carbonate is indicated by reference 
numeral 8003b. The bar graph showing the results using ISOCYCLOGERANIOL 
ethyl carbonate is indicated by reference numeral 8004b. 
FIG. 8C is a series of bar graphs indicating the mean number of mosquitoes 
trapped on the "Y" axis versus the treatment substance on the "X" axis 
using a semiochemical field trap as illustrated in FIG. 21 having six 
ports with three infrared light emitting diodes using the following 
substances: 
(i) a mixture of air and carbon dioxide in a mole ratio of 50:50 at a rate 
of carbon dioxide of 2.7 gram moles per hour; 
(ii) FLORALOL having the structure: 
##STR69## 
(iii) FLORALATE having the structure: 
##STR70## 
The bar graph showing the results using the mixture of air and carbon 
dioxide is indicated by reference numeral 8000c. The bar graph showing the 
results using FLORALOL is indicated by reference numeral 8026c. The bar 
graph showing the results using FLORALATE is indicated by reference 
numeral 8043c. 
In each of the experiments, the results for which are shown in FIGS. 8A, 8B 
and 8C, the following insects were shown to be either repelled or 
attracted: 
Culex nigripalpus; 
Aedes atlanticus; 
Culex salinarius; 
Aedes vexans; 
Culex spp.; 
Simulium spp.; 
Psoroferia ferox; 
Aedes infirmatus; 
Drosophila melanogaster; 
Coccinellidae; 
Anopheles crucians; 
Psoroferia columbiae; 
Culicoides spp.; and 
Aedes spp.. 
In referring to the extruder of FIG. 9, polymer 12 and 13 is admixed in 
vessel 14 and added at barrel segment S-1 of barrel 16 to the extruder 
which is powered by motor 15 held in place by bracket 23A. Simultaneously, 
into barrel segment S-6 (one of segments 18a, 18b, 18c or 18d) is added 
the insect repellent which is one or more of the dimethyl substituted 
oxymethyl cyclohexane derivative-containing compositions of our invention 
previously held in container 17. The repellent/perfumant mixture is pumped 
through pump 23 into barrel segment 18c/S-6. Simultaneously, foaming agent 
is added from vessel 19 into barrel segment S-8 from barrel segment S-10, 
a foamed tow containing polymer having imbedded therein insect 
repellent/perfume is passed through cooling bath 20 and the cooled tow 22 
is then passed into mascerating machine 21 wherein the tow is chopped into 
particles and held in container 21a for future use, e.g., for use in 
conjunction with the manufacture of the insect repellent soap or detergent 
bars described in detail, infra. 
Referring to FIGS. 11-20, inclusive, a preferred embodiment of our 
invention comprises an ellipsoidally-shaped detergent tablet 830. A 
preferred embodiment of our invention comprises an ellipsoidally-shaped 
detergent tablet 830 containing a solid plastic core 832 which can be 
fabricated from, for example, polyethylene, polypropylene, nylon, a 
biodegradable polymer such as poly(epsilon caprolactone) or any polymer 
capable of having therein microvoids from which an insect 
repelling/perfuming substance, e.g., at least on of the appropriate 
dimethyl substituted oxymethyl cyclohexane derivative-containing 
compositions of our invention will be controllably transported from the 
plastic core into and through the soap cake over a reasonable period of 
time during the use of the soap cake. Such polymers can be microporous 
polymers, such as those described in U.S. Pat. No. 4,247,498 issued on 
Jan. 27, 1981 the specification for which is incorporated herein by 
reference. Surrounding the central plastic core containing insect 
repellent 832, is detergent 830' which is in the solid phase at ambient 
conditions, e.g., room temperature and atmospheric pressure. Examples of 
workable detergents 830' are "elastic" detergents such as those described 
in U.S. Pat. No. 4,181,632 issued on Jan. 1, 1980 the disclosure of which 
is incorporated herein by reference, or "transparent" soaps such as those 
set forth in U.S. Pat. No. 4,165,293 issued on Aug. 21, 1979 the 
disclosure of which is incorporated herein by reference. Other examples of 
the detergent 830' useful in our invention are those set forth as 
"variegated soaps" in Canadian Letters Patent No. 1,101,165 issued on May 
19, 1981. 
On use of the soap tablet 830 or detergent bar, the insect repellent agent 
originally located in plastic core 832 is transported at a steady state 
from core 832 through core surface 831 through the detergent 830' and 
finally through the surface of the detergent bar at, for example, 833, 
834, 835 and 836. 
The detergent bar or tablet 830 of our invention may be of any geometric 
shape, for example, a rectangular parallelepiped tablet as shown in FIGS. 
15, 16 and 17 containing solid plastic core 839. The insect repellent 
located in solid plastic core 839 on use of the detergent bar passes 
through at steady state, surface 837 of FIG. 16, detergent 838 and finally 
surface 839 at, for example, locations 840, 841, 842 and 843. The 
environment surrounding the detergent bar on use thereof is then treated 
with the insect repellent at 843, 844 and 845, for example. Optionally, 
aromatizingi agent can also be contained in the detergent bar (if desired) 
and so the environment surrounding the detergent bar on use thereof would 
also be aesthetically aromatized at 843, 844 and 845, for example, if the 
appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing composition of our invention is insufficient for 
such aromatization. In certain instances, such appropriate dimethyl 
substituted oxymethyl cyclohexane derivative-containing compositions are 
indeed sufficient for such aromatization. 
As is shown in FIGS. 18, 19 and 20, the plastic core of the detergent 
tablet 830 may have a single finite void at its center 851 (of FIGS. 19 
and 20) in which the insect repellent agent and, optionally, any 
additional aromatizing agents are contained. The plastic core is a shell 
848 having outer surface 852 (shown in FIGS. 19 and 20). The insect 
repellent agent (and, optionally, any additional aromatizing agent) 
contained in the void in the plastic core permeates through shell 848, 
part surface 852 at a steady state, through the detergent 847 and to the 
environment at, for example, 856, 857, 858 and 859. 
In addition to thee insect repellent contained in the core, e.g., core 839 
or core void, the core can also contain other materials for therapeutic 
use, for example, bacteriastats, deodorizing agents and the like which are 
compatible with appropriate dimethyl substituted oxymethyl cyclohexane 
derivative-containing compositions of our invention. In the alternative, 
the plastic core of the detergent tablet of FIGS. 18, 19 and 20 may have 
an empty single finite void at its center 851 with the insect repellent 
contained in the shell 848. 
At the end of the use of the detergent tablet, the hollow core or the solid 
core can be used as an insect imparting and aroma imparting or air 
freshener household article. In addition, depending on the ratio of the 
volume of the void 851 to the solid part of the detergent tablet of FIGS. 
18, 19 and 20, the detergent tablet of FIGS. 18, 19 and 20 can be so 
fabricated that it will float on the surface of the liquid in which it is 
being used and this physical attribute has certain obvious advantages. 
FIG. 22 is a series of bar graphs showing the feeding contact for a mean 
feeding for a mean feeding contact for a mean one hour feeding contact 
period of time using the olfactometer apparatus of FIG. 10. The number of 
feeding contacts are set forth on the "Y" axis and the treatment substance 
is set forth on the "X" axis. The bar graph indicated by reference numeral 
2200 is for air and shows the results using said air. The bar graph 
indicated by reference numeral 2243 shows the results using FLORALATE 
having the structure: 
##STR71## 
The bar graph indicated by reference numeral 2244 shows the results using 
geranial having the structure: 
##STR72## 
FIG. 23 is a series of bar graphs showing on the "Y" axis the mean 2-6 hour 
number of feeding contacts for the mosquitoes, Aedes aegypti, using the 
olfactometer of FIG. 10 versus the treatment substance on the "X" axis. 
The graph indicated by reference numeral 2300 is the graph showing the 
results using air. The graph indicated by reference numeral 2343 is the 
bar graph showing the results using FLORALATE having the structure: 
##STR73## 
The graph indicated by reference number 2344 is the bar graph showing the 
results of this experiment using geranial having the structure: 
##STR74## 
The apparatus of FIG. 10 is disclosed in detail in U.S. Pat. No. 5,134,892 
the specification for which is incorporated herein by reference. 
The following examples are illustrative and the instant Patent Application 
is intended to be restricted only to the scope of the claims and not to 
the examples. 
EXAMPLE I 
A transparent candle base mixture is produced by intimately admixing the 
following ingredients: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
VERSAMID .RTM. 1635 
34.0 
Barlol 12C2 51.0 
Butyl Stearate 3.5 
NEVEX .RTM. 100 5.0 
SPAN .RTM. 1.5 
Isopropyl Istostearate 
4.0 
Isopropyl Myristate 
4.0 
______________________________________ 
The foregoing mixture is placed in an autoclave and intimately admixed with 
22% by weight of the entire mixture of a perfuming-insect repellent 
composition containing the following ingredients: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
##STR75## 25 
##STR76## 25 
##STR77## 25 
##STR78## 25 
______________________________________ 
The autoclave is sealed and heated to 180.degree. C. under 25 atmospheres 
pressure and maintained with vigorous shaking for a period of 5 hours. At 
the end of the 5 hour period, the autoclave is depressurized (being under 
a nitrogen pressure atmosphere) and the autoclave is opened and the 
contents are then poured into cylindrical candle molds 4" in height and 2" 
in diameter containing 0.125" wicks. The resulting candles have 
efficacious Aedes aegypti, Aedes albopictus and Musca domestica L. 
repellencies and have aesthetically pleasing aromas on use. 
The candles are effective in preventing houseflies and the mosquito species 
Aedes aegypti and Aedes albopictus from entering a room in which four 
candles have been burning for 15 minutes, the said room having dimensions 
of 6'.times.15'.times.15' and having a 2'.times.2'open portal adjacent to 
a housefly and mosquito-infested region in the month of August 1992 in the 
temperate zone of Highlands, N.J. adjacent Raritan Bay. 
EXAMPLE II 
A study was conducted to evaluate the efficacy of candles which are 
designated as "A" "B" and "C" in repelling houseflies (Musca domestica L. 
(Diptera:Muscidae)) and the mosquito species Aedes aegypti and Aedes 
albopictus. 
Candle "A" contained 95% paraffin wax and 5% of ISOCYCLOGERANIOL ethyl 
carbonate having the structure: 
##STR79## 
Candle "B" contained 90% paraffin wax and 10% citronella oil. 
Candle "C" contained only paraffin wax. 
The candles are allowed to burn for 20 minutes and the number of houseflies 
(Musca domestica L.(Diptera:Muscidae)) and mosquitoes (Aedes aegypti and 
Aedes albopictus) repelled is recorded for the next 60 minutes with the 
following equipment and procedure: 
Materials 
Test Chamber 
The evaluation was conducted in a 28.3 cubic meter chamber with airing 
ports. A screened cage measuring 15 cm.times.15 cm.times.47.5 cm was 
attached inside an upper airing port, and a screened repellency 
observation cage measuring 15 cm.times.15 cm.times.32.5 cm was attached 
outside the upper airing port. The two cages were held together by a 
Masonite plate which fit firmly in the airing port. A 4 cm hole located in 
the center of each Masonite plate provided an escape for the test insects. 
A barrier was used to close the hole. 
Attractant 
A caged grey mouse was used as an attractant and was placed inside the 
chamber in the larger section of the repellency cage. 
Test Insects 
(i) Adult houseflies (Musca domestica L. (Diptera:Muscidae)); 
(ii) Aedes aegypti mosquitoes; and 
(iii) Aedes albopictus mosquitoes are test insects. 
Procedure 
For each replicate, 75 to 100 adult houseflies (Musca domestica 
L.(Diptera:Muscidae)), 75 to 100 Aedes aegypti mosquitoes and 75 to 100 
Aedes albopictus mosquitoes were removed from the rearing cage by means of 
a vacuum aspirator and transferred by carbon dioxide anesthesia to the 
inner cage containing the grey mouse. The assembled cage was placed in one 
of the upper ventilation ports of the chamber. For each experimental 
situation, the test insects were transferred to a clean cage containing 
the mouse. A candle containing the insect repellent substance to be tested 
was placed centrally on the chamber floor and burned for 20 minutes before 
initiating the repellency counts. The maximum period for the repellency 
counts was 60 minutes. The first repellency count was made at 10 minutes 
after the burning ended and subsequent counts were taken at 5-minute 
intervals thereafter. The number of houseflies (Musca domestica 
L.(Diptera:Muscidae)), Aedes aegypti mosquitoes and Aedes albopictus 
mosquitoes repelled were those escaping to the outside cage. For the 
control, counts were made in a similar manner, but no candle was burned. 
The same three candles were used for all four replicates. Between 
replicates, the chamber was exhausted, the Kraft paper flooring for the 
chamber was replaced and the two screened repellency cages were submerged 
in hot detergent water, rinsed and dried. 
Results 
The overall average percent of houseflies (Musca domestica L. 
(Diptera:Muscidae)), Aedes aegypti mosquitoes and Aedes albopictus 
mosquitoes repelled for each candle for 60 minutes was as follows: 
Candle "A" - 98%; 
Candle "B" - 52%; and 
Candle "C" - 12%. 
The repellency against the three species: 
Musca domestica L. (Diptera:Muscidae); 
Aedes aegypti; and 
Aedes albopictus 
were equivalent in this test.