Insect repellents and a method of repelling insects

A class of .alpha.-branched chain alkyl or alkenyl substituted benzene compounds have excellent repelling activities against numerous noxious insects.

This invention relates to insect repellents and a method of repelling 
insects. 
The term "insect repellent" as defined herein includes insect feeding 
deterrent and egg-laying deterrent besides its literal sense. 
A number of insect repellents have been developed hitherto. For example, 
N,N-dimethyl m-toluamide has been practically used as mosquito repellent. 
Camphor, naphthalene and p-dichlorobenzene have been practically used for 
repelling insects which attack clothing. Although not practically used 
yet, isoboldine is known to be effective against Prodenia litura, 
demissine to be effective against Scolytus multistriatus. 4-Methylphenol 
and 4-ethylphenol were reported to be effective as warning pheromones 
against Blattella. Also, G. Kajimoto et al have reported about repellency 
of some antioxidants for foods, hydroquinone, BHA (mixture of 
2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole) and BHT 
(2-6-ditert-butyl-4-methylphenol) against fly's laver and cockroach 
(Nutrition and Food 14, 378-383 (1962)). However, there is very little 
example of having studied in details about insect repellency of compounds 
from their chemical structural aspects. 
As a result of having tested about repellency of a number of aromatic 
compounds against various kinds of obnoxious insects in a view of mutual 
relation between chemical structure and repellent activity for purpose of 
developing insect repellents having high safety and suitability for 
practical use, we have now found that a certain class of .alpha.-branched 
chain hydrocarbon substituted benzene compounds have more effective 
repellent activity and broad insect repelling spectrum over those in the 
prior art. 
The class of substituted benzene compounds as proved valuable insect 
repellents are represented by the following general formula. 
##STR1## 
wherein R.sub.1 is .alpha.-branched chain alkyl or alkenyl radical having 
3 to 6 carbon atoms, R.sub.2, R.sub.4 and R.sub.6 are each hydrogen, 
hydroxyl, lower alkyl, lower alkoxyl, lower aliphatic acyl, lower 
alkoxycarbonyl, hydroxyl substituted lower alkyl, aldehyde or halogen, but 
all of R.sub.2, R.sub.4 and R.sub.6 are not hydrogen, R.sub.3 and R.sub.5 
are each hydrogen, methyl, ethyl, hydroxyl substituted lower alkyl or 
aldehyde. 
The term "lower" as defined herein is meant radical containing 1 to 4 
carbon atoms. 
The chemical structural characteristics of the present repellents are the 
following. 
1. R.sub.1 should be .alpha.-branched carbon chain to exhibit the desired 
repellent effect. Compounds where R.sub.1 is substituted by other carbon 
chain such as straight chain alkyl or vinyl radical have little repellent 
action. Also, substitution of R.sub.1 by other radical than carbon chain, 
such as carboxyl, amino, aldehyde or hydroxyl radical causes little or no 
insect repellency. 
2. R.sub.2, R.sub.4 and R.sub.6 which are located at ortho- and 
para-positions to R.sub.1 are equivalent one another in repellent effect 
and act positively in repellency. Compounds where all of R.sub.2, R.sub.4 
and R.sub.6 are hydrogen have little repellent power, whereas compounds 
where at least one of R.sub.2, R.sub.4 and R.sub.6 is hydroxyl, lower 
alkoxyl, lower aliphatic acyl, lower alkoxycarbonyl, hydroxyl substituted 
lower alkyl, aldehyde or halogen have excellent repellent activity. But, 
the repellent activity is greatly decreased when at least one of R.sub.2, 
R.sub.4 and R.sub.6 is carboxyl, amino or N-substituted amino radical. 
3. R.sub.3 and R.sub.5 which are located at meta position to R.sub.1 are 
equivalent in repellent activity each other but do not take part or act 
negatively in repellency in contrary to the tendency of substituents being 
located at ortho and para positions. When relatively large molecules such 
as tert-butyl radical is introduced into that position, repellency 
activity is greatly decreased because of its steric hindrance to the 
chemical receptor such as antenna of insect. Preferably R.sub.3 and 
R.sub.5 are each hydrogen, methyl, ethyl, hydroxyl substituted lower alkyl 
or aldehyde radical. 
More specifically, examples of .alpha.-branched chain C.sub.3 -C.sub.6 
alkyl or alkenyl radical represented by R.sub.1 include isopropyl, 
sec-butyl, tert-butyl, sec-amyl, tert-amyl, sec-hexyl, tert-hexyl and 
isopropenyl radicals. Examples of lower alkyl radical in R.sub.2, R.sub.4 
and R.sub.6 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 
sec-butyl and tert-butyl radicals. Examples of lower alkoxyl radical 
include methoxy, ethoxy, propoxy, butoxy, isobutoxy and tert-butoxy 
radicals. Examples of lower aliphatic acyl radical include acetyl radical. 
Examples of lower alkoxycarbonyl radical include methoxycarbonyl, 
ethoxycarbonyl and butoxycarbonyl radicals. Examples of hydroxyl 
substituted lower alkyl radical include hydroxymethyl, 2-hydroxyethyl, 
1-hydroxyethyl and 1-hydroxypropyl radical. And, examples of halogen atom 
are fluorine, chlorine, bromine and iodine. 
Representative examples of compounds which may be used as insect repellents 
in the present invention are the following. 
o-cumenol, p-cumenol, 2-tert-butylphenol, 4-tert-butylphenol, 
2-sec-butylphenol, 4-sec-butylphenol, 4-sec-amylphenol, 2-tert-amylphenol, 
4-tert-amylphenol, 4-sec-hexylphenol, 4-tert-hexylphenol, 
2,4-dihydroxycumene, 2,6-dihydroxycumene, 
2,4-dihydroxy-1-tert-butylbenzene, 2,6-dihydroxy-1-tert-butylbenzene, 
o-cymene, m-cymene, p-cymene, 2,3-dimethylcumene, 2,6-dimethylcumene, 
2,4,6-trimethylcumene, 3,4,5-trimethylcumene, 
1,4-dimethylisopropylbenzene, 4-ethylcumene, 1,4,-di-tert-butylbenzene, 
4-isobutyl-1-tert-butylbenzene, 4-sec-butyl-1-tert-butylbenzene, 
4-sec-amyltoluene, 4-tert-amyltoluene, 6-isopropyl-m-cresol, 
6-tert-butyl-m-cresol, 6-tert-amyl-m-cresol, 4-isopropyl-m-cresol, 
4-tert-butyl-m-cresol, 4-tert-amyl-m-cresol, 6-isopropyl-o-cresol, 
6-tert-butyl-o-cresol, 6-sec-butyl-o-cresol, 6-tert-amyl-o-cresol, 
4-isopropyl-o-cresol, 4-tert-butyl-o-cresol, 4-tert-amyl-o-cresol, 
2-isopropyl-p-cresol, 2-tert-butyl-p-cresol, 3-methyl-6-isopropylanisole, 
3-methyl-6-tert-butylanisole, 3-methyl-6-tert-amylanisole, 
2-methyl-4-isopropylanisole, 2-methyl-4-tert-butylanisole, 
2-isopropyl-4-methylanisole, 2-tert-butyl-4-methylanisole, 
3-ethyl-6-t-butylanisole, 3,6-di-tert-butylphenol, 
2-tert-butyl-5-sec-butylphenol, 1-tert-butyl-2,3,4-trimethoxybenzene, 
1-tert-butyl-2,4,6-trimethoxybenzene, 1,2,3-trimethyl-5-tert-butylbenzene, 
1-tert-butyl-2-isobutylbenzene, 1-sec-butyl-2,4-dimethoxybenzene, 
2,6-dihydroxy-p-cymene, 2-(2-hydroxyethyl)-p-cymene, 
3-(3-hydroxypropyl)-p-cymene, 2-ethyl-p-cymene, 2,6-dimethoxy-p-cymene, 
2-propenyl-p-cymene, 4-tert-butyl-m-cymene, 4-isopropylbenzaldehyde, 
4-tert-butylbenzaldehyde, 4-tert-amylbenzaldehyde, 
4-sec-butylbenzaldehyde, 2-tert-butyl-benzaldehyde, 
2-tert-4,6-dimethylbutylbenzaldehyde, 
2,3,4-trimethyl-6-tert-butylbenzaldehyde, 4-isopropylbenzylaldehyde, 
4-sec-butyl-benzaldehyde, 4-tert-butylbenzylalcohol, 
4-tert-amylbenzylalcohol, 2-isopropylbenzylalcohol, 
2-tert-butyl-benzylalcohol, 2,6-dimethyl-4-tert-butylbenzylalcohol, 
2,3-dimethyl-5-tert-butylbenzylalcohol, 
2-hydroxy-5-tert-butyl-benzylalcohol, 
2-hydroxy-3-methyl-5-butylbenzylalcohol, 
2-isobutoxy-5-tert-butylbenzylalcohol, 
2-methoxy-5-sec-butyl-benzylalcohol, 4-tert-butyl-.alpha.-methylbenzylalco 
hol, 2-methyl-5-tert-butylbenzylalcohol, 
4-isopropenyl-.alpha.,.alpha.-dimethylbenzylalcohol, 
4-tert-butyl-.alpha.,.alpha.-dimethylbenzylalcohol, 
2,4-dihydroxy-5-tert-butylbenzylalcohol, 4-isopropylacetophenone, 
4-tert-butylacetophenone, methyl 2-isopropylbenzoate, ethyl 
2-tert-butylbenzoate, methyl 4-isopropylbenzoate, methyl 
4-tert-butylbenzoate, methyl 4-isopropyl-3-hydroxybenzoate, methyl 
4-tert-butyl-3-hydroxybenzoate, 4-tert-butyl-3-hydroxybenzaldehyde, 
4-chlorocumene, 2-chlorocumene, 2,4-dichlorocumene, 2,5-dichlorocumene, 
2-chloro-p-cymene, 4-chloro-m-cymene, 1,4-di-tert-butyl-2-brombenzene, 
1-bromo-4-tert-butylbenzene, 1-fluoro-2-bromo-4-tert-butylbenzene, methyl 
2-tert-butyl-5-chlorobenzoate, 2-tert-butyl-6-chloro-p-cresol, 
6-isopropenyl-m-cresol, 2,5-di-tert-butyl-p-cresol and the like. 
The present repellents are mainly effective against Pterygota and Acari. 
For example, they are effective against either of imago (irrespective of 
male and female) and larva of the following insects: Thysanura (e.g. 
Lepismatidae), Orthoptera (e.g. Locustidae, Blattidae, Gryllidae), 
Isoptera (e.g. Phinolermmitidae), Hemiptera (e.g. Delphacidae, 
Deltocephalidae, Aphididae, Coccidae and Pentatomidae), Lepidoptera (e.g. 
Noctuidae, Pyralididae, Carposinidae and Tortricidae), Diptera (e.g. 
Culicidae, Muscidae, Tabanidae, Trypetidae, Simuliidae, Sarcophagidae and 
Agromyzidae), Coleoptera (e.g. Bruchidae, Dermestidae, Ptinidae, 
Chrysomllidae and Anobiidae), Hymenoptera (e.g. Formicidae), Acari (e.g. 
Ixodides and Tetranychidae). 
Compounds of the aforementioned general formula may be directly applied as 
insect repellents singly or in admixture of two or more components. Or, it 
may also be applied in any formulation such as solutions, dispersions, oil 
agents, emulsifiable concentrates, wettable powders, dusts, granules, 
aerosols, fumigants or gels with suitable liquid carriers, solid carriers, 
emulsifying agents, dispersing agents, suspending agents, spreader, 
penetrating agents, wetting agents, stabilizing agents, gelling agents, 
steam fog accelerator. Examples of liquid carriers include water, alcohols 
(e.g. methyl alcohol, ethyl alcohol, ethylene glycol, cyclodextrin), 
ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. dioxane, 
tetrahydrofuran, methyl cellosolve), aliphatic hydrocarbons (e.g. 
gasoline, kerosene, lamp oil, n-paraffin), aromatic hydrocarbons (e.g. 
benzene, toluene, xylene, solvent naphtha), organic bases (e.g. pyridine), 
halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride), acid 
amides (e.g. dimethylformamide), esters (e.g. ethyl acetate, butyl 
acetate, fatty acid glyceride), nitriles (e.g. acetonitrile), sulfur 
compounds (e.g. dimethylsulfoxide) and mixture thereof. Examples of solid 
carriers include botanical powders (such as soy bean powder, tobacco 
powder, wheat flour, wood powder); mineral powders (such as clays which 
include kaolin, bentonite and acid clay); talcs which include talc powder, 
pyrophyllite, silicas which include diatomaceous earth and mica; alumina, 
powdery sulfur and active charcoal. These powdery materials may be 
employed singly or in mixtures of two or more components. 
Suitable emulsifiers, spreader and penetrants are soaps, higher alcohol 
sulfates, alkyl sulfonates, alkylaryl sulfonates, quaternary ammonium 
salts, fatty acid esters of oxyalkylamines, polyalkylene oxides and 
anhydrosorbitols. 
As gelling agents, there may be employed agar, metal soaps, dibenzylidine 
sorbitol, N-acylamino acid esters, N-acylamino acid amides, amine salts of 
N-acylamino acids and 12-hydroxystearic acid. As steam fog accelerators, 
there may be employed any sublimative compound such as p-dichlorobenzene, 
camphor and trimer of isobutyraldehyde. 
If necessary, casein, gelatin, starch, alginic acid, methyl cellosolve, 
polyvinyl alcohol, wood turpentine, richebran oil, sucrose, glucose, 
molasses and amino acids may also be added to the composition. 
The repelling agents of the present invention may also be employed in 
admixture with insecticidal agents (e.g. organochlorine, organophosphorus 
compounds, carbamates and natural insecticides), synergic agents, other 
insect repelling agents, pigments, bactericides and fungicides. 
As explained above, the present repellent can be directly applied to an 
area from which it is desirable to repel the insects by conventional 
methods wherein it is sprayed, fogged, scattered, brushed or heated to 
volatilize or otherwise it is placed in the form of paper piece, cloth 
piece impregnated with a small amount of it or in the form of 
microcapsules containing it and further heated to volatilize, whereby the 
damage from the insects may be efficiently controlled. 
It is not necessary to pay particular attention for the amount applied of 
the present repellent, since the present repellent exhibits appreciable 
repellent effect even when applied in a very small amount. However, it is 
desirable to apply the present repellent so as to deposit from about 0.001 
to about 1 mg. per cm.sup.2 of surface area to be applied or so as to 
exist at concentration of from about 0.001 to about 1 p.p.m. in air when 
sprayed, scattered, fogged. Similar amount is applicable even in case 
where the present repellent is placed in the form of paper piece, cloth 
piece or microcapsule containing it or otherwise is further subjected to 
heating to volatilize it.

The following examples are intended to illustrate the advantages of the 
insect repellents of the present invention. However, it is not intended to 
limit the invention to the specific compounds and concentrations shown 
therein. 
EXAMPLE 1 
The evaluation of the repellent activity of compounds exemplified by the 
above formula against German cockroach (Blattella germanica Linne) was 
accomplished in the following manner. 
German cockroaches, including adult males, females and nymphs were placed 
without food and water in a plastic box, 30 cm square by 10 cm deep. The 
inner lip of the box was coated with a thin layer of paraffin oil to 
prevent the insects' escape. 
The cockroaches are in the habit of gathering in the corner of the box. A 
paper disc, 0.7 cm diameter by 0.04 cm thick, was treated immediately 
before the test by pipetting 0.02 ml of 1000, 100 and 10 p.p.m. solution 
of the inventive compound in acetone. After air-drying, the disc was 
placed in the corner of the box. 
Repellency was judged by the cockroaches' behavior against the treated 
disc. The behavior of the compound having repellent activity the 
cockroaches scamper away from the disc. The activity rating scale used was 
as follows: 
-: no repellent activity 
.+-.: slightly repellent activity 
+: moderately repellent activity 
++: good repellent activity 
Results are shown in Chart 1. Column 1 gives the name of the compound; 
column 2, the rate in terms of p.p.m. at which the compound was applied to 
the disc; 
EXAMPLE 2 
The evaluation of the repellent activity of compounds exemplified by the 
above formula against cockroach Periplaneta picea Shiraki was accomplished 
in the following manner. 
The cockroaches, including each 20 adult males, females and nymphs were 
placed without food and water in a stainless steel box (30 cm.times.100 
cm.times.20 cm). The inner lip of the box was coated with a thin layer 
paraffin oil to prevent the insect' escape. The box was covered by a 
plastic plate. Two shelters, 6.5 cm square by 1 cm deep, were placed in 
the corner of the box. The cockroaches were offered a choice of two 
shelters, one of which was treated immediately before the test with 0.5 ml 
of a solution of acetone containing 10 mg of the inventive compound on the 
entire inner surface. The cockroaches were counted after 24 hours in the 
shelters. Repellency was calculated by the formula: 
##EQU1## 
The activity rating scale used was follows: 
-: no repellent activity, percent repellency is below 60 
.+-.: slightly repellent activity, percent repellency is from 60 to 75 
+: good repellent activity, percent repellency is above 75 below 100 
++: remarkable repellent activity, percent repellency is 100 
Results are shown in Chart 2. Column 1 gives the name of the compound; 
column 2, the activity rating of the compound against the cockroaches. 
EXAMPLE 3 
The evaluation of the repellent activity of the compounds exemplified by 
the above formula against house fly, Musca domestica vicina Macquart, was 
accomplished in the following manner. 
250 pairs house flies were placed in a plastic box (100 cm.times.100 
cm.times.100 cm). Two 1-percent sugar water pots, one of which was 100 
p.p.m. solution of the compound containing insecticide fenitrothion, were 
on the center of the box. 
The killed house flies in the each pots are counted after 24 hours. 
Repellency was calculated by the formula: 
##EQU2## 
The active rating scale used was follows: 
-: no repellent activity, percent repellency is below 20 
.+-.: slightly repellent activity, percent repellency is from 20 to 50 
+: good repellent activity, percent repellency is above 50 below 100 
++: remarkable repellent activity, percent repellency is 100. 
Results are shown in Chart 2. Column 1 gives the name of the compound; 
column 3, the activity rating of the compound against house flies. 
EXAMPLE 4 
The evaluation of the repellent activity of compounds exemplified by the 
above formula against smaller brown planthopper, Laodelphex striatellus 
Fallen, and green rice leafhopper, Nephotettix cincticeps Uhler, was 
accomplished in the greenhouse in the following manner. 
Repellent compositions were prepared by dissolving 10 mg. of the compound 
to be tested in 2 ml. of a solution of acetone containing 50 mg. of 
sulfonate non-ionic emulsifying agent and diluted to a volume of 20 ml. 
with water. The composition then contained 500 p.p.m. of repellent 
compound. 
Five rice seeds (Nourin No. 8 variety) were planted in 4-inch clay pots and 
allowed to germinate. Four weeks from the day of planting, the test 
chemicals, compounded as described above, were sprayed on all leaf 
surfaces of the young rice plants and allowed to dry. The plants were then 
covered by a wire netting cylinder to prevent the insects' escape. Twenty 
female adults were placed into the cylinder. The adults sitting on leaves 
or stem of the plants were counted after 24 hours. 
The percent repellency and the repellent active rating scale use were the 
same contents as house fly. 
Results are shown in Chart 3. Column 1 gives the name of the compound, 
Column 2, the activity rating of the compound against smaller brown 
planthopper, Column 3, the activity rating of the compound against green 
rice leafhopper. 
EXAMPLE 5 
The evaluation of the feeding deterrent activity of compounds exemplified 
by the above formula against the larvaes of Tobacco cutworm and Diamond 
back moth, Prodenica litura Fabricius, was accomplished in the following 
manner. The composition contained 500 p.p.m. of repellent compound were 
prepared by the same method as Example 4. Leaf discs, 3 cm diameter, were 
punched out with a cork borer from leaves of kidney beans. The discs were 
immersed in the repellent compositions or in pure acetone as a control. 
After air-drying, the discs were placed in polyethylene dishes with test 
larvae of Tobacco cutworm. The whole area of the control discs are usually 
eaten in one day, at which time the consumed area of all discs were 
measured by Dethrer's method, the consumed area of treated discs expressed 
as a percentage of the consumed area of control discs was used as an index 
of the antifeeding activity of the compound. 
Feeding deterrent was calculated by the formula 
##EQU3## 
The antifeeding active rating scale used was follows: 
-: no antifeeding activity, percent feeding deterrent is below 20 
.+-.: slightly antifeeding activity, percent feeding deterrent is from 20 
to 50. 
+: good antifeeding activity, percent feeding deterrent is above 50 below 
100 
++: remarkable antifeeding activity, percent feeding deterrent is 100. 
Results are shown in Chart 4. Column 1 gives the name of the compound; 
Column 2, the activity rating of the compound against the larvae of 
Tobacco cutworm; Column 3, the activity rating of the compound against the 
larvae of Diamond back moth. 
EXAMPLE 6 
The evaluation of the repellent activity of compounds exemplified by the 
above formula against the larvae of small cabinet beetle, Anthrenus 
verbascii, was accomplished in the following manner. 
Cloth discs, 2 cm diameter, were punched out with a cork borer from raw 
wool cloth. The discs were immersed in 10 p.p.m. and 1000 p.p.m. solutions 
of the inventive compound in acetone or in pure acetone as a control. 
After air-drying, the discs were placed in polyethylene dishes with 5 
larvaes of the beetles. 
Repellency was judged by the beetles, behavior against the treated disc. 
When a compound has no repellent activity, all larvaes are placed on the 
disc after 24 hours. But when a compound has repellent activity, no larvae 
is placed on the disc. 
The activity rating scale used was as follows: 
-: no repellent activity 
.+-.: slightly repellent activity, some larvae are placed on the disc 
treated with 1000 p.p.m. solution. 
+: good repellent activity, no larvae is placed on the disc treated with 
1000 p.p.m. solution or, some larvae are placed on the disc treated with 
10 p.p.m. solution 
++: remarkable repellent activity, no larvae is placed on the disc treated 
with 10 p.p.m. solution. 
Results are shown in Chart 4. Column 1 gives the name of the compound; 
Column 4, the activity rating of the compound against the larvae of small 
cabinet beetle. 
EXAMPLE 7 
The evaluation of the repellent activity of compound against Green peach 
aphid, Myzus persicae Sulzer, and Carmine mite, Tetranychus telarius 
Linne, was accomplished in the following manner. 
The composition contained 500 p.p.m. of repellent compound were prepared by 
the same method as Example 4. 
Leaf discs, 3 cm. diameter were punched out with a cork borer from leaves 
of white rape or strawberry. The discs were immersed in the repellent 
compositions or in pure acetone as a control. 
After air-drying, the discs were placed in polyethylene dishes with adults 
and nymphs of green peach aphid or carmine mite. Repellency and the 
activity rating scale were evaluated by the same method as Example 6. 
Results are shown in Chart 4. Column 1 gives the name of the compound; 
Column 5, the activity rating of the compound against green peach aphid; 
Column 6, the activity rating of the compound against carmine mite. 
EXAMPLE 8 
The evaluation of egg-laying deterrent activity and ovicidal activity of 
compounds exemplified by the above formula against Azuki bean weevils, 
Callosobruchus Chinensis Linne, and Cowpea Weevil Callosobruchus maculatus 
Fabricius, was accomplished in the following manner. An Azuki bean was 
treated immediately before test with a solution contained 50 .mu.g of the 
compound in acetone. Twenty pairs of weevils were then placed among 300 
treated Azuki beans in the box 9 cm diameter by 5 cm deep. Total of eggs 
were counted after one week on the beans, and then, total of hatching eggs 
were counted after two weeks. 
Egg-laying deterrent activity and ovicidal activity were calculated by the 
formulas 
##EQU4## 
The activity rating scale used follows: 
-: no activity, percent activity is below 30. 
.+-.: slight activity, percent activity is from 30 to 60. 
+: good activity, percent activity is above 60 below 100. 
++: remarkable activity, percent activity is 100. 
Results are shown in Chart 5. Column 1 gives the name of the compound; 
column 2, the egg-laying deterrent activity rating of the compound against 
Azuki bean weevils; column 3, the ovicidal activity rating of the compound 
against Azuki bean weevils; column 4, the egg-laying deterrent activity 
rating of the compound against Cowpea Weevil; column 5, the ovicidal 
activity rating of the compound against Cowpea Weevils. 
Chart 1 
__________________________________________________________________________ 
Application Rate 
Compound 1000 ppm 
100 ppm 
10 ppm 
__________________________________________________________________________ 
2-Isopropyl phenol ++ + - 
4-Isopropyl phenol ++ + - 
2-sec-Butyl phenol ++ + - 
4-sec-Butyl phenol ++ + - 
2-tert-Butyl phenol ++ + + 
4-tert-Butyl phenol ++ + + 
2-sec-Amyl phenol + .+-. - 
4-sec-Amyl phenol + .+-. - 
2-tert-Amyl phenol + .+-. - 
4-tert-Amyl phenol + .+-. - 
2-sec-Hexyl phenol + .+-. - 
4-sec-Hexyl phenol + .+-. - 
4-Isopropyl toluene ++ ++ - 
2-Isopropyl toluene ++ ++ - 
4-Ethyl cumene ++ ++ + 
P-Diisopropyl benzene ++ ++ ++ 
4-tert-Butyl cumene ++ ++ ++ 
Thymol ++ + + + 
4-Isopropyl-m-cresol ++ ++ + 
3-Methyl-6-isopropyl anisole 
++ + + 
2,4-Dimethoxy cymene ++ + + 
4-Isopropyl benzaldehyde 
++ + - 
2-Isopropyl benzaldehyde 
++ + - 
4-Isopropyl anisole ++ + - 
4-Isopropyl acetophenone 
++ + - 
4-Isopropyl benzylalcohol 
++ + - 
3-Hydroxy-4-isopropyl anisole 
++ ++ + 
Methyl 3-hydroxy-4-isopropyl benzoate 
++ + - 
Ethyl 3-hydroxy-4-isopropyl benoate 
++ + - 
4-Isopropyl-o-xylene ++ - - 
4-isopropyl-chlorobenzene 
++ + - 
2,5-Dichloro cumene ++ - - 
3-Methyl-4-ethoxy cumene 
++ + - 
2-Methyl-4-ethyl cumene 
++ + - 
2-Ethyl-4-methyl cumene 
++ + - 
2-(2-Hydroxyethyl)-4-methyl cumene 
++ + - 
2-Hydroxy-3-isopropyl benzyl alcohol 
++ + - 
2-Methyl-5-isopropyl-p-hydroquinone 
++ + - 
2-Bromo-4-methyl-cumene 
++ - - 
2-Methyl-4-tert-butyl cumene 
++ + - 
2,4,5-Trimethyl cumene 
++ + - 
3,5-Diethyl cumene ++ - - 
4-tert-Butyl toluene ++ + - 
2-tert-Butyl toluene ++ + - 
6-tert-Butyl-m-cresol ++ ++ ++ 
1,4-Di-tert-butyl benzene 
+ + - 
2,5-Di-tert-butyl-4-hydroxy-benzyl alcohol 
+ + - 
4-tert-Butyl ethyl benzene 
++ + - 
3,5-Dimethyl-4-tert-butyl phenol 
++ + - 
3,5-Diisopropyl-4-tert-butyl phenol 
+ + - 
3-Hydroxy-6-tert-butyl anisole 
++ + - 
3-Hydroxy-6-tert-butyl toluene 
++ ++ + 
2-Hydroxy-3-tert-butyl toluene 
++ + - 
4-tert-Butyl benzaldehyde 
++ + - 
4-tert-Butyl benzoic acid methyl ester 
++ + - 
4-tert-Butyl benzylalcohol 
++ ++ + 
4-tert-Butyl benzoic acid isopropyl ester 
++ .+-. - 
Methyl 3-methyl-6-tert-butyl benzoate 
+ + - 
4-tert-Butyl-o-xylene ++ + - 
2,3-Dichloro-tert-butyl benzene 
+ + - 
4-tert-Butyl chloro benzene 
+ + - 
2-Ethoxy-5-tert-butyl toluene 
++ + - 
2-tert-Butyl-iso-butyl benzene 
++ + - 
1,2,3-Trimethyl-4-iodo-5-tert-butyl 
benzene ++ + - 
1,2,3-Trimethyl-4-tert-butyl benzene 
++ + - 
1,3,5-Trimethoxy-6-tert-butyl benzene 
++ ++ + 
3,4-Dimethyl-6-tert-butyl benzene 
++ + - 
2,6-Dimethyl-4-tert-butyl benzyl alcohol 
+ + - 
P-Cresol - - - 
P-Ethyl phenol .+-. - - 
P-n-Propyl phenol - - - 
Control 
P-n-Butyl phenol - - - 
P-iso-Butyl phenol .+-. - - 
P-n-Amyl phenol - - - 
Phenol - - - 
p-Hydroxy benzoic acid 
- - - 
p-Hydroquinone - - - 
p-(N-Dimethyl)-amino phenol 
- - - 
Control 
4-Methoxy phenol .+-. - - 
Cumene .+-. - - 
m-Isopropyl phenol .+-. - - 
m-Isopropyl anisole .+-. - - 
4-Isopropyl benzoic acid 
- - - 
4-(N-Dimethyl)-amino cumene 
- - - 
Untreated - - - 
__________________________________________________________________________ 
Chart 2 
______________________________________ 
Activity rating 
Insect Cock- House 
Compound roach fly 
______________________________________ 
The p-Diisopropyl benzene ++ + 
present 
Thymol ++ ++ 
invention 
3-Methoxy-4-iso-propyl benzaldehyde 
++ ++ 
6-tert-Butyl-m-cresol ++ ++ 
3-Methyl-6-tert-butyl anisole 
++ ++ 
2,5-Dimethyl-4-tert-butyl anisole 
+ ++ 
4-tert-Butyl resorcinol 
+ + 
6-tert-Butyl-m-cresol ++ ++ 
3-Ethoxy-6-tert-amyl phenol 
+ ++ 
3-Methyl-4-tert-butyl anisole 
+ + 
4-sec-Amyl phenol + + 
Control 
2,6-Di-tert-butyl-4-methyl phenol 
- - 
3-tert-Butyl phenol .+-. - 
p-Cresol - - 
p-Ethyl phenol - - 
Cumene - - 
Untreated - - 
______________________________________ 
Chart 3 
______________________________________ 
Activity rating 
Insect Smaller Green 
brown rice 
plant leaf 
Compound hopper hopper 
______________________________________ 
The Thymol ++ ++ 
present 
4-Isopropyl resorcinol 
++ ++ 
invention 
3-Methyl-4-chloro cumene 
+ + 
3,6-Dihydroxy-2-chloro-5-tert- 
butyl toluene ++ ++ 
3,6-Dihydroxy-2,5-di-tert-butyl 
toluene ++ + 
4-tert-Butyl-m-cresol 
++ + 
6-tert-Butyl-m-cresol 
++ ++ 
1,3,5-Trimethoxy-2-tert-butyl 
benzene + + 
4-tert-Amyl benzaldehyde 
+ + 
4-tert-Amyl phenol + + 
Control 
2,6-Di-tert-butyl-p-cresol 
- - 
p-tert-Butyl benzoic acid 
- - 
p-Cresol - - 
p-Ethyl phenol - - 
m-Isopropyl phenol .+-. - 
Untreated - - 
______________________________________ 
Chart 4 
__________________________________________________________________________ 
Repellent Activity Rating 
Insect Diamond 
Small 
Green 
Tabacco 
back cabinet 
peach 
Carmine -Compound cutworm moth bee 
tle aphid mite 
__________________________________________________________________________ 
The 4-Isopropyl phenol 
+ + ++ + + 
present 
Thymol ++ ++ ++ + ++ 
inven- 
4-Ethyl cumene + + + + + 
tion 2,4-Dimethoxy cumene 
+ + + + + 
2-Ethyl-p-cymene 
+ + + + + 
4-Chloro-m-cymene 
+ .+-. ++ + + 
2-Isopropyl-5-iso-butyl 
phenol ++ ++ ++ ++ + 
2,3,5-Trimethyl cumene 
+ + + + + 
3,5-Dimethyl-4-tert-butyl 
benzyl alcohol + + ++ + + 
2-tert-Butyl-5-methoxy 
benzyl alcohol + + + + + 
6-tert-Butyl-m-cresol 
++ + ++ + + 
3-Methyl-6-tert-butyl anisole 
+ + ++ + + 
1,4-Di-tert-butyl benzene 
++ ++ ++ + + 
Methyl 3-methyl-4-tert- 
butyl benzoate + + + + + 
4-tert-Butyl benzaldehyde 
++ ++ ++ + + 
2,3,4-Trimethyl-6-tert-butyl 
benzene ++ ++ + ++ + 
4-sec-Butyl phenol 
+ + ++ + + 
4-sec-Butyl ethylbenzene 
+ + + + + 
1,3-Diemthoxy-sec-butyl 
benzene + + + + + 
2-Methoxy-5-sec-butyl 
benzyl alcohol + + + + + 
4-tert-Amyl-sec-butyl 
benzene + + ++ ++ ++ 
4-ter-Amyl phenol 
+ + + + + 
4-tert-Amyl-o-cresol 
+ + + + + 
4-sec-Amyl phenol 
+ + + + + 
6-sec-Amyl-m-cresol 
+ + + + + 
4-sec-Amyl anisole 
+ + + + + 
.alpha.,.alpha.-Dimethyl-4-sec-amyl- 
benzyl alcohol ++ + ++ + + 
Control 
2,6-Di-tert-butyl-p- 
cresol - - - - - 
4-tert-Butyl benzoic acid 
- - - - - 
4-Isopropyl benzoic acid 
- - - - - 
m-Isopropyl phenol 
.+-. - .+-. 
- - 
m-Isopropyl anisole 
- - .+-. 
- - 
p-Cresol - - .+-. 
- - 
Untreated - - - - - 
__________________________________________________________________________ 
Chart 5 
__________________________________________________________________________ 
Activity rating 
Insect Azuki 
bean Cowpea 
weevil weevil 
Repellent Egg- Egg- 
laying laying 
deter- deter- 
Compound rent 
Ovicidal 
rent 
Ovicidal 
__________________________________________________________________________ 
The 6-tert-Butyl-m-cresol 
++ ++ ++ ++ 
present 
3-Methyl-6-tert-butyl anisole 
++ ++ ++ ++ 
invention 
2,5-Di-tert-butyl-p-hydroquinone 
++ + ++ ++ 
1,4-Di-tert-Butyl benzene 
+ + + + 
4-tert-Butyl acetophenone 
+ + + + 
3,5-Dimethyl-4-tert-butyl phenol 
+ + + + 
3-Methyl-6-isopropyl benzaldehyde 
+ + + + 
1,4-Di-isopropyl benzene 
++ + ++ + 
Thymol ++ ++ ++ ++ 
4-Isopropyl benzyl alcohol 
++ ++ ++ ++ 
3-Methyl-6-tert-amyl benzyl alcohol 
++ + ++ + 
4-sec-Butyl chloro benzene 
++ ++ ++ ++ 
4-Isopropyl benzyl alcohol 
++ ++ ++ ++ 
Control 
p-Cresol - - - - 
4-Methoxy phenol - - - - 
4-tert-Butyl benzoic acid 
- - - - 
m-Isopropyl phenol 
.+-. 
- .+-. 
- 
Untreated - - - - 
__________________________________________________________________________ 
EXAMPLE 9 
The emulsifilable composition was prepared by dissolving 10 parts of 
6-tert-butyl-m-cresol, 5 parts of emulsifying agent polyoxyethylene oleate 
and 1 part of dipropylene glycol in 50 parts ethanol and 35 parts of 
water. The emulsifiable composition 100 times diluted by water was used 
against aphids. 
EXAMPLE 10 
A repellent insecticidal composition in an aerosol was prepared by mixing 
10 parts of 3-methyl-6-isopropyl phenol, 1 part of insecticide malathion, 
40 parts of ethanol, 5 parts of emulsifying agent polyoxy ethylene oleate, 
5 parts of ethylene glycol, 39 parts of water and 20 parts of jetting gas. 
EXAMPLE 11 
A feeding deterrent composition against white arts was prepared by mixing 
10 parts 4-tert-butyl-3-hydroxy-anisole, 30 parts of acetone, 1 part of 
spreader dioctyl sulfosuccinate, 1 part of emulsifiable agent polyoxy 
ethylene castor oil, 10 parts of ethanol and 48 parts of water. 
EXAMPLE 12 
A gel-type repellent composition was prepared by mixing 30 parts of 
6-tert-butyl-m-cresol, 69 parts of ethanol, 1 parts of perfume and gelling 
agent dibenzylidene sorbitol. 
EXAMPLE 13 
A sublimated repellent composition was prepared by heating and mixing 5 
parts of 2,5-diisopropyl phenol, 94.5 parts of sublimate isobutylaldehyde 
trimer and 0.5 parts of perfume. 
EXAMPLE 14 
A repellent composition in an aerosol against cockroaches was prepared by 
mixing 10 parts of 2,5-di-tert-butyl hydroquinone, 80 parts of normal 
paraffin, 9.5 parts of ethanol, 0.5 parts of perfume and 20 parts of 
Liquid propane gas.