Insecticidal compositions containing a mixture of O,O-diethyl O-(3,5,6-trichloro-2-pyridinyl)-phosphorothioate and 2,2,3,3-tetramethylcyclopropanecarboxylic acid:cyano(3-phenoxyphenyl)methyl ester are disclosed. Such compositions are useful in the kill and control of insects, particularly insects of the Lepidoptera order and especially of the genus Heliothis.

SUMMARY OF THE INVENTION 
The present invention is directed to new insecticidal compositions which 
are useful in the kill and control of insects particularly insects of the 
Lepidoptera order and especially of the genus Heliothis. These 
compositions comprise mixtures of O,O-diethyl 
O-(3,5,6-trichloro-2-pyridinyl)phosphorothioate and 
2,2,3,3-tetramethylcyclopropanecarboxylic 
acid:cyano(3-phenoxyphenyl)methyl ester. It has been found that the toxic 
ingredients of said compositions are mutually activating. 
The O,O-diethyl O-(3,5,6-trichloro-2-pyridinyl)phosphorothioate employed in 
accordance with the teachings of the present invention is a solid material 
melting at .about.41.degree.-42.degree. C. The compound, its method of 
preparation and its insecticidal activity are taught in U.S. Pat. No. 
3,244,586. The 2,2,3,3-tetramethylcyclopropylcarboxylic 
acid:cyano(3-phenoxyphenyl)methyl ester employed in accordance with the 
teachings of the present invention is an oily material having a refractive 
index of n(25/D)=1.5283. The compound, its method of preparation and its 
insecticidal activity are taught in U.S. Pat. No. 3,835,176. 
The new insecticidal composition of the present invention comprises about 1 
part by weight of O,O-diethyl 
O-(3,5,6-trichloro-2-pyridinyl)phosphorothioate and from about 1/8 to 
about 4 parts by weight of 2,2,3,3-tetramethylcyclopropanecarboxylic 
acid:cyano(3-phenoxyphenyl)methyl ester i.e. a ratio of about 8:1 to about 
1:4. A preferred ratio is from about 8:1 to about 2:1 with the most 
preferred ratio being from about 8:1 to about 4:1. 
These insecticidal compositions are especially effective in killing and 
controlling insects, particularly Lepidoptera, especially Heliothis 
species, which infest crops such as corn, soybeans, tobacco and 
particularly cotton. 
The mixtures of active compounds of the present invention have been found 
to possess good activity against Heliothis species. Accordingly, the 
present invention also comprises methods for controlling such insects 
and/or their habitats with a pesticidally effective amount of the active 
compound mixture. For such uses the unmodified active materials of the 
present invention can be employed. However, the present invention embraces 
the use of an insecticidally-effective amount of the active materials in 
admixture with an inert material, as an adjuvant or carrier therefor, in 
solid or liquid form. Thus, for example, the active mixture can be 
dispersed on a finely divided solid and employed therein as a dust. Also, 
the active mixture, as liquid concentrates or solid compositions 
comprising the active mixture, can be dispersed in water, typically with 
the aid of a wetting agent, and the resulting aqueous dispersion employed 
as a spray. In other procedures, the active mixture can be employed as a 
constituent of organic liquid compositions, oil-in-water and water-in-oil 
emulsions, or water dispersions, with or without the addition of wetting, 
dispersing, or emulsifying agents. 
Suitable adjuvants of the foregoing type are well known to those skilled in 
the art. The methods of applying the solid or liquid pesticidal 
formulations similarly are well known to the skilled artisan. 
As organic solvents used as extending agents there can be employed 
hydrocarbons, e.g. benzene, toluene, xylene, kerosene, diesel fuel, fuel 
oil, and petroleum naphtha, ketones such as acetone, methyl ethyl ketone 
and cyclohexanone, chlorinated hydrocarbons such as carbon tetrachloride, 
chloroform, trichloroethylene, and perchloroethylene, esters such as ethyl 
acetate, amyl acetate and butyl acetate, ethers, e.g., ethylene glycol 
monomethyl ether and diethylene glycol monomethyl ether, alcohols, e.g., 
methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene 
glycol, butyl carbitol acetate and glycerine. Mixtures of water and 
organic solvents, either as solutions or emulsions, can be employed. 
The active mixtures can also be applied as aerosols, e.g., by dispersing 
them in air by means of a compressed gas such as dichlorodifluoromethane 
or trichlorofluoromethane and other such materials. 
The active mixture of the present invention can also be applied with 
adjuvants or carriers such as talc, pyrophyllite, synthetic fine silica, 
attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calcium 
carbonate, bentonite, fuller's earth, cottonseed hulls, wheat flour, 
soybean flour, pumice, tripoli, wood flour, walnut shell flour, redwood 
flour and lignin. 
As stated, it is frequently desirable to incorporate a surface active agent 
in the compositions of the present invention. Such surface active or 
wetting agents are advantageously employed in both the solid and liquid 
compositions. The surface active agent can be anionic, cationic or 
nonionic in character. 
Typical classes of surface active agents include alkyl sulfonate salts, 
alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acid esters 
of polyhydric alcohols and the alkylene oxide addition products of such 
esters, and addition products of long chain mercaptans and alkylene 
oxides. Typical examples of such surface active agents include the sodium 
alkylbenzene sulfonates having 10 to 18 carbon atoms in the alkyl group, 
alkylphenol ethylene oxide condensation products, e.g., p-isooctylphenol 
condensed with 10 ethylene oxide units, soaps, e.g., sodium stearate and 
potassium oleate, sodium salt of propylnaphthalene sulfonic acid, 
di(2-ethylhexyl)-ester of sodium sulfosuccinic acid, sodium lauryl 
sulfate, sodium decane sulfonate, sodium salt of the sulfonated 
monoglyceride of coconut fatty acids, sorbitan sesquioleate, lauryl 
trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, 
polyethylene glycol lauryl ether, polyethylene glycol esters of fatty 
acids and rosin acids, e.g., Ethofat 7 and 13, sodium N-methyl-N-oleyl 
taurate, Turkey Red Oil, sodium dibutyl naphthalene sulfonate, sodium 
lignin sulfonate, polyethylene glycol stearate, sodium dodecylbenzene 
sulfonate tertiary dodecyl polyethylene glycol thioether (nonionic 218), 
long chain ethylene oxide-propylene oxide condensation products, e.g., 
Pluronic 61 (molecular weight 1000), polyethylene glycol ester of tall oil 
acids, sodium octyl phenoxyethoxyethyl sulfate, 
tris(polyoxyethylene)sorbitan monostearate (Tween 60), and sodium dihexyl 
sulfosuccinate. 
The concentration of the active mixtures in liquid formulations generally 
is from about 0.01 to about 95 percent by weight or more. Concentrations 
of from about 0.1 to about 50 weight percent are often employed. In 
formulations to be employed as concentrates, the active materials can be 
present in a concentration of from about 5 to about 98 weight percent. In 
dusts or dry formulations, the concentration of the active ingredient can 
be from about 0.01 to about 95 weight percent or more; concentrations of 
from about 0.1 to about 50 weight percent are often conveniently employed. 
The active compositions can also contain other compatible additaments, for 
example, plant growth regulants, pesticides and the like. 
The present compositions can be applied by the use of power-dusters, boom 
and hand sprayers, spray-dusters and by other conventional means. The 
compositions can also be applied from airplanes as a dust or spray. 
The active mixtures of this invention are usually applied at an approximate 
rate of from about 1/16 pound to about 5 pounds or more per acre, but 
lower or higher rates may be appropriate in some cases. A preferred 
application rate is from 1/2 pound to about 2 pounds per acre.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The following examples illustrate the present invention and the manner by 
which it can be practiced but, as such, should not be construed as 
limitations upon the overall scope of the same. 
EXAMPLE I 
A study was conducted to determine the effectiveness and synergistic 
response of various combinations of O,O-diethyl 
O-(3,5,6-trichloro-2-pyridinyl)phosphorothioate and 
2,2,3,3-tetramethylcyclopropanecarboxylic 
acid:cyano(3-phenoxyphenyl)methyl ester in the control of Heliothis 
insects. 
Test solutions were prepared by admixing predetermined amounts of each of 
the above compounds in predetermined amounts of water containing 
predetermined amounts of acetone and Triton X155 surfactant. 
Tobacco leaf discs, 3 inches in diameter were dipped into one of the above 
mixtures and placed in an open petri dish to dry. After the leaf discs 
were dry, 5 late second instar (approximately 3-day old) tobacco bud worms 
(Heliothis virescens) were placed in each dish and the dishes covered. All 
treatments were run in triplicate and on two different days. Mortality was 
recorded 48 hours after treatment with moribund larvae unable to crawl 
their own body length being counted as dead. In this test method, 
intoxication occurred through contact with and feeding upon treated 
plants. 
The results of this study are set forth below in Table I. 
TABLE I 
__________________________________________________________________________ 
Expected 
Actual 
Percent 
Test Amount Amount 
Ratio of 
Control 
Control 
Increase Over 
No..sup.1 
Chemical.sup.2 
in PPM 
Chemical.sup.3 
in PPM 
A to B 
in Percent.sup.4 
in Percent 
Expected Control.sup.5 
__________________________________________________________________________ 
1 -- -- -- -- -- -- 0 -- 
2 A 12.5 -- -- -- -- 7 -- 
3 A 25 -- -- -- -- 17 -- 
4 A 50 -- -- -- -- 40 -- 
5 A 100 -- -- -- -- 73 -- 
6 -- -- B 3.1 -- -- 0 -- 
7 -- -- B 6.2 -- -- 3 -- 
8 -- -- B 12.5 -- -- 10 -- 
9 -- -- B 25 -- -- 17 -- 
10 -- -- B 50 -- -- 43 -- 
11 -- -- B 100 -- -- 53 -- 
12 A 12.5 B 3.1 4:1 7 7 0 
13 A 12.5 B 6.2 2:1 10 13 30 
14 A 12.5 B 12.5 1:1 16 20 25 
15 A 12.5 B 25 1:2 23 27 17 
16 A 12.5 B 50 1:4 47 63 34 
17 A 25 B 3.1 2:1 17 20 18 
18 A 25 B 6.2 4:1 20 27 35 
19 A 25 B 12.5 2:1 15 33 20 
20 A 25 B 25 1:1 31 43 38 
21 A 25 B 50 1:2 53 70 32 
22 A 25 B 100 1:4 61 80 31 
23 A 50 B 6.2 8:1 42 53 26 
24 A 50 B 12.5 4:1 46 50 9 
25 A 50 B 25 2:1 50 50 0 
26 A 50 B 50 1:1 66 80 21 
27 A 50 B 100 1:2 72 93 29 
28 A 100 B 12.5 8:1 76 63 0 
29 A 100 B 25 4:1 78 60 0 
30 A 100 B 50 2:1 85 97 14 
31 A 100 B 100 1:1 87 93 7 
__________________________________________________________________________ 
.sup.1 Test Nos. 1-11 are control runs with Test 1 being a no chemical 
control (surfactant/acetone/water alone). 
.sup.2 Chemical A represents O,Odiethyl 
O(3,5,6-trichloro-2-pyridinyl)phosphorothioate. 
.sup.3 Chemical B represents 2,2,3,3tetramethylcyclopropanecarboxylic 
acid:cyano(3phenoxyphenyl)methyl ester. 
##STR1## 
##STR2## 
Data from Table I illustrates that better control was obtained employing 
the two toxicants together than would be expected from the results 
obtained from employing each of the two toxicants alone. These data are 
obtained according to the technique described in Colby, "Calculating 
Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds, 
Vol. 15 (1967) pages 20-22 and Colby, "Greenhouse Evaluation of Herbicide 
Combinations", Proc. NEWCC, No. 19, pages 312-320.