Acridone substituted phosphorus compounds, compositions containing same and insecticidal method of use

This invention discloses new insecticidal chemical compounds of the following formula and their use in controlling insects: ##STR1## wherein X and Y are each independently selected from the group consisting of halogen, alkyl, haloalkyl, nitro, alkylsulfinyl, alkylsulfonyl and cyano; m and n are integers from 0 to 3; R.sup.1 is selected from the group consisting of alkyl and ##STR2## wherein R.sup.3 is selected from the group consisting of halogen, alkyl, haloalkyl, nitro and cyano; and k is an integer from 0 to 3; R.sup.2 is selected from the group consisting of alkyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino and ##STR3## wherein R.sup.4 is selected from the group consisting of halogen, alkyl, haloalkyl, nitro and cyano; and t is an integer from 0 to 3; and A and B are each independently selected from the group consisting of oxygen and sulfur.

This invention relates to new compositions of matter and more specifically 
relates to new chemical compounds of the formula 
##STR4## 
wherein X and Y are each independently selected from the group consisting 
of halogen, alkyl, haloalkyl, nitro, alkylsulfinyl, alkylsulfonyl and 
cyano; m and n are integers from 0 to 3; R.sup.1 is selected from the 
group consisting of alkyl and 
##STR5## 
wherein R.sup.3 is selected from the group consisting of halogen, alkyl, 
haloalkyl, nitro and cyano; and k is an integer from 0 to 3; R.sup.2 is 
selected from the group consisting of alkyl, alkoxy, alkylthio, amino, 
alkylamino, dialkylamino and 
##STR6## 
wherein R.sup.4 is selected from the group consisting of halogen, alkyl, 
haloalkyl, nitro and cyano; and t is an integer from 0 to 3; and A and B 
are each independently selected from the group consisting of oxygen and 
sulfur. 
The compounds of the present invention are useful as insecticides. In a 
preferred embodiment of the present invention X and Y are independently 
selected from the group consisting of halogen, lower alkyl, lower 
haloalkyl, nitro, lower alkylsulfinyl, lower alkylsulfonyl and cyano; m 
and n are integers from 0 to 3; R.sup.1 is selected from the group 
consisting of lower alkyl and 
##STR7## 
wherein R.sup.3 is selected from the group consisting of halogen, lower 
alkyl, lower haloalkyl, nitro and cyano; and k is an integer from 0 to 3; 
R.sup.2 is selected from the group consisting of lower alkyl, lower 
alkoxy, lower alkylthio, amino, lower alkylamino, di(lower alkyl)amino, 
and 
##STR8## 
wherein R.sup.4 is selected from the group consisting of halogen, lower 
alkyl, lower haloalkyl, nitro and cyano; t is an integer from 0 to 3; and 
A and B are each independently selected from the group consisting of 
oxygen and sulfur. 
The term lower as used herein designates a straight or branched carbon 
chain of up to six carbon atoms. 
The compounds of the present invention can be prepared by reacting a 
compound of the formula 
##STR9## 
wherein X, Y, m and n are as heretofore described, with a phosphorus 
compound of the formula 
##STR10## 
wherein A, B, R.sup.1 and R.sup.2 are as heretofore described. This 
reaction can be effected by combining the compounds of formulae II and III 
in an inert organic reaction medium such as toluene or methylene chloride 
in the presence of an acid acceptor such as a tertiary amine. The 
reactants are typically combined with agitation at temperatures ranging 
from -20.degree. C. to ambient temperatures. The reaction mixture can be 
stirred for a period of several hours to insure completeness of the 
reaction. The acid acceptor salt can then be removed by filtration and/or 
washing with water and the remaining mixture stripped of solvent to yield 
the desired product. This product can then be used as such or can be 
further purified by standard techniques. 
The compounds of formulae II and III are known in the art. Due to 
instability, some of the compounds of formula III can be prepared shortly 
before their use in reacting with the compound of formula II. This 
preparation can be effected by reacting a phosphorodichloride of the 
formula 
##STR11## 
wherein A and R.sup.2 are as heretofore described, with a compound of the 
formula 
EQU H--B--R.sup.2 (V) 
wherein B and R.sup.2 are as heretofore described. This reaction can be 
readily carried out by combining equimolar amounts of the compounds of 
formulae IV and V in an inert organic solvent such as toluene in the 
presence of an acid acceptor such as a tertiary amine. This reaction can 
be carried out at lower temperatures such as those ranging from 
-40.degree. C. to 10.degree. C. The reaction product mixture can then be 
used directly for reaction with the compound of formula II or the product 
can be isolated first by conventional means. 
Exemplary acridones of formula II useful in preparing the compounds of the 
present invention include: 1-hydroxyacridone, 2-hydroxyacridone, 
3-hydroxyacridone, 4-hydroxyacridone, 2-hydroxy-7-chloroacridone, 
3-hydroxy-7-bromoacridone, 2-hydroxy-5-methylacridone, 
4-hydroxy-8-nitroacridone, 3-hydroxy-7-chloromethylkacridone, 
2-hydroxy-6-trifluoromethylacridone, 2-hydroxy-5-methylsulfinylacridone, 
3-hydroxy-5-methylsulfonylacridone, 2-hydroxy-6-cyanoacridone and the 
like. 
Exemplary compounds of formula III suitable for preparing the compounds of 
the present invention are O-ethyl S-propyl phosphorochloridothiolate; 
O-ethyl S-propyl phosphorochloridothiolothionate; O-(2,4-dicyanophenyl) 
S-propyl phosphorochloridothiolate; O-(3,4,5-trichlorophenyl S-propyl 
phosphorochloridothiolothionate; S-ethyl S-propyl 
phosphorochloridothiolate; S-butyl S-pentyl 
phosphorochloridodithiolothionate; S-pentyl 
ethylphosphonochloridothiolate; S-(3-nitrophenyl) 
(3-chlorophenyl)phosphonochloridothiolothionate; O-(2,3-dimethylphenyl) 
S-butyl phosphorochloridothiolate; O-ethyl O-butyl 
phosphorochloridothionate; O-(4-chloro-5-methylphenyl) O-propyl 
phosphorochloridothionate; O-ethyl S-propyl 
phosphorochloridothiolothionate; O-ethyl ethylphosphonochloridothiolate; 
O-ethyl N,N-dimethylphosphoramidochloridates; S-propyl 
N,N-diethylphosphoroamidochloridothiolate; S-pentyl 
N,N-dihexylphosphoramidothiolothionate; O-butyl 
N-butylphosphoramidochloridate; S-hexyl phosphoramidochloridothiolate and 
the like.

The manner in which the compounds of the present invention can be prepared 
is more specifically illustrated in the following examples. 
EXAMPLE 1 
Preparation of O-Ethyl O-Acridon-2-yl S-Propyl Phosphorothioate 
2-Hydroxyacridone (1.11 grams; 0.01 mole), triethylamine (1.01 grams; 0.01 
mole), tetrahydrofuran (25 ml) and toluene (25 ml) were charged into a 
glass reaction vessel equipped with a mechanical stirrer and thermometer. 
The mixture was cooled to about 0.degree. C. and O-ethyl S-propyl 
phosphorochloridothioate (2.024 grams; 0.01 mole) dissolved in toluene (23 
ml) was added with stirring over a period of about 1/2 hour. After the 
addition was completed stirring was continued for 2 hours allowing the 
mixture to warm up to room temperature and thereafter for 18 hours. After 
this time the reaction mixture was filtered to remove triethylamine 
hydrochloride and the filtrate stripped of solvent leaving a brown 
semi-solid residue. This residue was subjected to flash chromatography 
using ethyl acetate as the eluant to yield the desired product O-ethyl 
O-acridon-2-yl S-propyl phosphorothioate as a light yellow solid melting 
at 146.degree. to 152.degree. C. 
EXAMPLE 2 
Preparation of O-Ethyl O-Chloroacridon-2-yl S-Propyl Phosphorothioate 
2-Hydroxyacridone (3.17 grams; 0.015 mole) and acetic acid were charged 
into a glass reaction vessel equipped with a stirrer and thermometer. The 
mixture was cooled to 15.degree. C. and a solution of chlorine (0.015 
mole) in acetic acid (2.5 ml) was added dropwise with stirring. After the 
addition was completed stirring was continued at room temperature 
overnight. After this time the reaction mixture was filtered to recover 
product. The product was then washed, dried and dissolved in 
tetrahydrofuran (50 ml). The solution was treated with triethylamine (2 
ml). The treated solution was then filtered and the filtrate treated with 
activated charcoal. The filtrate was then stripped of solvent in a rotary 
evaporator to yield chloro-2-hydroxyacridone m.p. 184.degree.-191.degree. 
C. 
The acridone prepared above and triethylamine (1.4 ml) were charged into a 
glass rection vessel equipped with a stirrer and thermometer. To this was 
added a cooled solution (0.degree. C.) of O-ethyl S-propyl 
phosphorochloridothioate (0.01 mole) in toluene (25 ml). The mixture was 
stirred with continued cooling for 1/2 hour and thereafter at room 
temperature overnight. After this time the reaction mixture was filtered 
to remove triethylamine hydrochloride and the filtrate was stripped of 
solvent in a rotary evaporator leaving a yellow/brown semi-solid as the 
residue. This residue was dissolved in hot ethyl acetate and the resulting 
solution was treated hot with activated carbon. The filtrate was cooled 
resulting in the formation of a solid precipitate. The solid is recovered 
by filtration and is dried to yield the desired product O-ethyl 
O-chloroacridon-2-yl S-propyl phosphorothioate melting at 189.degree. to 
193.degree. C. 
EXAMPLE 3 
Preparation of O-Methyl O-(4-Chloroacridon-2-yl S-Propyl Phosphorothioate 
2-Hydroxy-4-chloroacridone (0.01 mole), triethylamine (0.01 mole) 
tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a glass 
reaction vessel equipped with a mechanical stirrer and thermometer. The 
mixture is cooled to a temperature of about 0.degree. C. and O-methyl 
S-propyl phosphorochloridothioate (0.01 mole) dissolved in toluene (25 ml) 
is added with stirring over a period of about 30 minutes. After the 
addition is completed the reaction mixture is allowed to warm to room 
temperature and stirring is continued for a period of about 16 hours. 
After this time the reaction mixture is filtered to remove triethylamine 
hydrochloride. The filtrate is then washed with water, dried over 
anhydrous magnesium sulfate and stripped of solvents leaving a residue. 
This residue is subjected to flash chromatography using ethyl acetate as 
the eluant to yield the desired product O-methyl O-(4-chloroacridon-2-yl) 
S-propyl phosphorothioate. 
EXAMPLE 4 
Preparation of O,O-Diethyl O-(4-Methylacridon-2-yl) Phosphate 
2-Hydroxy-4-methylacridone (0.01 mole), triethylamine (0.01 mole) 
tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a glass 
reaction vessel equipped with a mechanical stirrer and thermometer. The 
mixture is cooled to a temperature of about 0.degree. C. and 
O,O-diethylchloridophosphate (0.01 mole) dissolved in toluene (25 ml) is 
added with stirring over a period of about 30 minutes. After the addition 
is completed the reaction mixture is allowed to warm to room temperature 
and stirring is continued for a period of about 16 hours. After this time 
the reaction mixture is filtered to remove triethylamine hydrochloride. 
The filtrate is then washed with water, dried over anhydrous magnesium 
sulfate and stripped of solvents leaving a residue. This residue is 
subjected to flash chromatography using ethyl acetate as the eluant to 
yield the desired product O,O-diethyl O-(4-methylacridon-2-yl) phosphate. 
EXAMPLE 5 
Preparation of O-(3-Chlorophenyl) O-(4,6-Dichloroacridon-2-yl) 
Methylphosphonate 
2-Hydroxy-4,6-dichloroacridone (0.01 mole), triethylamine (0.01 mole), 
tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a glass 
reaction vessel equipped with a mechanical stirrer and thermometer. The 
mixture is cooled to a temperature of about 0.degree. C. and 
O-(3-chlorophenyl) methylchloridophosphonate (0.01 mole) dissolved in 
toluene (25 ml) is added with stirring over a period of about 30 minutes. 
After the addition is completed the reaction mixture is allowed to warm to 
room temperature and stirring is continued for a period of about 16 hours. 
After this time the reaction mixture is filtered to remove triethylamine 
hydrochloride. The filtrate is then washed with water, dried over 
anhydrous magnesium sulfate and stripped of solvents leaving a residue. 
This residue is subjected to flash chromatography using ethyl acetate as 
the eluant to yield the desired product O-(3-chlorophenyl) 
O-(4,6-dichloroacridon-2-yl) methylphosphonate. 
EXAMPLE 6 
Preparation of O,S-Diethyl O-(2-Bromo-6-methylacridon-4-yl) 
Phosphorodithioate 
2-Bromo-4-hydroxyacridone (0.01 mole), triethylamine (0.01 mole), 
tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a glass 
reaction vessel equipped with a mechanical stirrer and thermometer. The 
mixture is cooled to a temperature of about 0.degree. C. and 
O,S-diethylphosphorochloridodithioate (0.01 mole) dissolved in toluene (25 
ml) is added with stirring over a period of about 30 minutes. After the 
addition is completed the reaction mixture is allowed to warm to room 
temperature and stirring is continued for a period of about 16 hours. 
After this time the reaction mixture is filtered to remove triethylamine 
hydrochloride. The filtrate is then washed with water, dried over 
anhydrous magnesium sulfate and stripped of solvents leaving a residue. 
This residue is subjected to flash chromatography using ethyl acetate as 
the eluant to yield the desired product O,S-diethyl 
O-(2-bromo-6-methylacridon-4-yl) phosphorodithioate. 
EXAMPLE 7 
Preparation of O-(2,4-Diethylphenyl) O-(6-Trifluoromethylacridon-3-yl) 
S-Propyl Phosphorothioate 
3-Hydroxy-6-trifluoromethylacridone (0.01 mole), triethylamine (0.01 mole), 
tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a glass 
reaction vessel equpped with a mechanical stirrer and thermometer. The 
mixture is cooled to a temperature of about 0.degree. C. and 
O-(2,4-dimethylphenyl) S-propyl phosphorochloridothioate (0.01 mole) 
dissolved in toluene (25 ml) is added with stirring over a period of about 
30 minutes. After the addition is completed the reaction mixture is 
allowed to warm to room temperature and stirring is continued for a period 
of about 16 hours. After this time the reaction mixture is filtered to 
remove triethylamine hydrochloride. The filtrate is then washed with 
water, dried over anhydrous magnesium sulfate and stripped of solents 
leaving a residue. This residue is subjected to flash chromatography using 
ethyl actate as the eluant to yield the desired product 
O-(2,4-dimethylphenyl) O-(6-trifluoromethylacridon-3-yl) S-propyl 
phosphorothioate. 
EXAMPLE 8 
Preparation of O-(4-Trifluoromethylphenyl) O-(4-Nitroacridon-1-yl) S-Butyl 
Phosphorothioate 
1-Hydroxy-4-nitroacridone (0.01 mole), triethylamine (0.01 mole) 
tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a glass 
reaction vessel equipped with a mechanical stirrer and thermometer. The 
mixture is cooled to a temperature of about 0.degree. C. and 
O-(4-trifluoromethylphenyl) S-butyl phosphorochloridothioate (0.01 mole) 
dissolved in toluene (25 ml) is added with stirring over a period of about 
30 minutes. After the addition is completed the reaction mixture is 
allowed to warm to room temperature and stirring is continued for a period 
of about 16 hours. After this time the reaction mixture is filtered to 
remove triethylamine hydrochloride. The filtrate is then washed with 
water, dried over anhydrous magnesium sulfate and stripped of solvents 
leaving a residue. This residue is subjected to flash chromatography using 
ethyl acetate as the eluant to yield the desired product 
O-(4-trifluoromethylphenyl) O-(4-nitroacridon-1-yl) S-butyl 
phosphorothioate. 
EXAMPLE 9 
Preparation of O-(4-Nitrophenyl) O-(4-trifluoromethylacridon-2-yl) S-Ethyl 
Phosphorothioate 
2-Hydroxy-4-trifluoromethylacridone (0.01 mole), triethylamine (0.01 mole), 
tetrahydrofuran (25 ml) are charged into a glass reaction vessel equipped 
with a mechanical stirrer and thermometer. The mixture is cooled to a 
temperature of about 0.degree. C. and O-(4-nitrophenyl) S-ethyl 
phosphorochloridothioate (0.01 mole) dissolved in toluene (25 ml) is added 
with stirring over a period of about 30 minutes. After the addition is 
completed the reaction mixture is allowed to warm to room temperature and 
stirring is continued for a period of about 16 hours. After this time the 
reaction mixture is filtered to remove triethylamine hydrochloride. The 
filtrate is then washed with water, dried over anhydrous magnesium sulfate 
and stripped of solvents leaving a residue. This residue is subjected to 
flash chromatography using ethyl acetate as the eluant to yield the 
desired product O-(4-nitrophenyl) O-(4-trifluoromethylacridon-2-yl) 
S-ethyl phosphorothioate. 
EXAMPLE 10 
Preparation of S-(4-Cyanophenyl) O-(7-Nitroacridon-2-yl) S-Propyl 
Phosphorodithioate 
2-Hydroxy-7-nitroacridone (0.01 mole), triethylamine (0.01 mole), 
tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a glass 
reaction vessel equipped with a mechanical stirrer and thermometer. The 
mixture is cooled to a temperature of about 0.degree. C. and 
S-(4-cyanophenyl) S-propyl phosphorochloridodithioate (0.01 mole) 
dissolved in toluene (25 ml) is added with stirring over a period of about 
30 minutes. After the addition is completed the reaction mixture is 
allowed to warm to room temperature and stirring is continued for a period 
of about 16 hours. After this time the reaction mixture is filtered to 
remove triethylamine hydrochloride. The filtrate is then washed with 
water, dried over anhydrous magnesium sulfate and stripped of solvents 
leaving a residue. This residue is subjected to flash chromatography using 
ethyl acetate as the eluant to yield the desired product S-(4-cyanophenyl) 
O-(7-nitroacridon-2-yl) S-propyl phosphorodithioate. 
EXAMPLE 11 
Preparation of O-(2-Methyl-4,6-dichlorophenyl) 
O-(3-Methylsulfinyl-7-cyanoacridon-1-yl) S-Propyl Phosphorothioate 
1-Hydroxy-3-methylsulfinyl-7-cyanoacridone (0.01 mole), triethylamine (0.01 
mole), tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a 
glass reaction vessel equipped with a mechanical stirrer and thermometer. 
The mixture is cooled to a temperature of about 0.degree. C. and 
O-(2-methyl-4,6-dichlorophenyl) S-propyl phosphorchloridothioate (0.01 
mole) dissolved in toluene (25 ml) is added with stirring over a period of 
about 30 minutes. After the addition is completed the reaction mixture is 
allowed to warm to room temperature and stirring is continued for a period 
of about 16 hours. After this time the reaction mixture is filtered to 
remove triethylamine hydrochloride. The filtrate is then washed with 
water, dried over anhydrous magnesium sulfate and stripped of solvents 
leaving a residue. This residue is subjected to flash chromatography using 
ethyl acetate as the eluant to yield the desired product 
O-(2-methyl-4,6-dichlorophenyl) O-(3-methylsulfinyl-7-cyanoacridon-1-yl) 
S-propyl phosphorothioate. 
EXAMPLE 12 
Preparation of O-(3-Bromophenyl) O-(4-Cyano-6-methylsulfonylacridon-2-yl) 
S-Phenyl Phosphorothioate 
2-Hydroxy-4-cyano-6-methylsulfonylacridone (0.01 mole), triethylamine (0.01 
mole), tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a 
glass reaction vessel equipped with a mechanical stirrer and thermometer. 
The mixture is cooled to a temperature of about 0.degree. C. and 
O-(3-bromophenyl) S-phenyl phosphorochloridothioate (0.01 mole) dissolved 
in toluene (25 ml) is added with stirring over a period of about 30 
minutes. After the addition is completed the reaction mixture is allowed 
to warm to room temperature and stirring is continued for a period of 
about 16 hours. After this time the reaction mixture is filtered to remove 
triethylamine hydrochloride. The filtrate is then washed with water, dried 
over anhydrous magnesium sulfate and stripped of solvents leaving a 
residue. This residue is subjected to flash chromatography using ethyl 
acetate as the eluant to yield the desired product O-(3-bromophenyl) 
O-(4-cyano-6-methylsulfonylacridon-2-yl) S-phenyl phosphorothioate. 
EXAMPLE 13 
Preparation of O-(4-Fluorophenyl) O-(5-Methylsulfinylacridon-2-yl) 
S-(4-Nitrophenyl) Phosphorothioate 
2-Hydroxy-5-methylsulfinylacridone (0.01 mole), triethylamine (0.01 mole), 
tetrahydrofuran (25 ml) and toluene (25 ml) are charged into a glass 
reaction vessel equipped with a mechanical stirrer and thermometer. The 
mixture is cooled to a temperature of about 0.degree. C. and 
O-(4-fluorophenyl) S-(4-nitrophenyl) phosphorochloridothioate (0.01 mole) 
dissolved in toluene (25 ml) is added with stirring over a period of about 
30 minutes. After the addition is completed the reaction mixture is 
allowed to warm to room temperature and stirring is continued for a period 
of about 16 hours. After this time the reaction mixture is filtered to 
remove triethylamine hydrochloride. The filtrate is then washed with 
water, dried over anhydrous magnesium sulfate and stripped of solvents 
leaving a residue. This residue is subjected to flash chromatography using 
ethyl acetate as the eluant to yield the desired product 
O-(4-fluorophenyl) O-(5-methylsulfinylacridon-2-yl) S-(4-nitrophenyl) 
phosphorothioate. 
Additional compounds within the scope of the present invention which can be 
prepared by the procedures detailed in the foregoing examples are O-ethyl 
O-butyl O-(5,6-dibromoacridon-2-yl) phosphate, O-propyl O-hexyl 
O-(7-fluoroacridon-3-yl) phosphate, O-butyl S-propyl 
O-(4-ethyl-7-cyanoacridon-3-yl) phosphorothioate, O-pentyl S-propyl 
O-(4,6-dipropylacridon-2-yl) phosphorothioate, O-hexyl S-propyl 
O-(7-hexylacridon-4-yl) phosphorothioate, O-(4-ethylphenyl) S-propyl 
O-(4-bromoacridon-2-yl) phosphorothioate, O-(3-propylphenyl) S-propyl 
O-(4-fluoroacridon-2-yl) phosphorothioate, O-(3-hexylphenyl) S-propyl 
O-(6-ethylsulfinylacridon-4-yl) phosphorothioate, O-(4-chloromethylphenyl) 
S-propyl O-(7-butylsulfinylacridon-4-yl) phosphorothioate, 
O-(2,4,6-trichlorophenyl) S-butyl O-(8-hexylsulfinylacridon-2-yl) 
phosphorothioate, O-ethyl S-pentyl O-(6-propylsulfonylacridon-2-yl) 
phosphorothioate, O-ethyl S-hexyl O-(6-pentylsulfonylacridon-3-yl). 
phosphorothioate, O-ethyl S-butyl O-(4-propylsulfinylacridon-2-yl) 
phosphorothioate, O-ethyl S-propyl O-(4-hexylsulfonylacridon-1-yl) 
phosphorothioate, O-ethyl O-(4-fluoroacridon-2-yl) 
N,N-dimethylphosphoramidate, O-ethyl O-acridon-2-yl N-ethylphosphoramidte, 
O-ethyl O-acridon-3-yl N-butylphosphoramidate, O-ethyl O-acridon-4-yl 
N-hexylphosphoramidate, O-ethyl O-acridon-2-yl N,N-dibutylphosphoramidate, 
O-acridon-2-yl N,N-dimethyl(ethyl)phosphonamidate, O-acridon-3-yl 
N,N-diethyl(phenyl)phosphonamidate, O-acridon-4-yl 
N,N-diethyl(3-chlorophenyl)phosphonamidate, O-acridon-2-yl 
N,N-diethyl(4-methylphenyl)phosphonamidate. 
For practical use as insecticides, the compounds of this invention are 
generally incorporated into insecticidal compositions which comprise an 
inert carrier and an insecticidally toxic amount of such a compound. Such 
insecticidal compositions, which can also be called formulations, enable 
the active compound to be applied conveniently to the site of the insect 
infestation in any desired quantity. These compositions can be solids, 
such as dusts, granules or wettable powders; or they can be liquids such 
as solutions, aerosols or emulsifiable concentrates. 
For example, dusts can be prepared by grinding and blending the active 
compounds with a solid inert carrier such as the talcs, clays, silicas, 
pyrophylite and the like. Granular formulations can be prepared by 
impregnating the compound, usually dissolved in a suitable solvent, onto 
and into granulated carriers such as the attapulgites or the vermiculites, 
usually of a particle size ranging from about 0.3 to 1.5 mm. Wettable 
powders, which can be dispersed in water and/or oil to any desired 
concentration of the active compound, can be prepared by incorporating 
wetting agents into concentrated dust compositions. 
In some cases, the active compounds are sufficiently soluble in common 
organic solvents such as kerosene or xylene so that they can be used 
directly as solutions in these solvents. Frequently, solutions of 
insecticides can be dispersed under superatmospheric pressure as aerosols. 
However, preferred liquid insecticidal compositions are emulsifiable 
concentrates which comprise an active compound according to this invention 
and as the inert carrier a solvent and an emulsifier. Such emulsifiable 
concentrates can be extended with water for application as sprays to the 
site of the insect infestation. The emulsifiers most commonly used in 
these concentrates are nonionic or mixtures of nonionic with anionic 
surface-active agents. 
A typical insecticidal composition according to this invention is 
illustrated by the following example, in which the quantitites are in 
parts by weight. 
EXAMPLE 14 
______________________________________ 
Preparation of a Dust 
______________________________________ 
Product of Example 2 
10 
Powdered Talc 90 
______________________________________ 
The above ingredients are mixed in a mechanical grinder-blender and are 
ground until a homogeneous, free-flowing dust of the desired particle size 
is obtained. This dust is suitable for direct application to the site of 
the insect infestation. 
The compounds of this invention can be applied as insecticides in any 
manner recognized by the art. One method for destroying insects comprises 
applying to the locus of the infestation, an insecticidal composition 
comprising an inert carrier and, as the essential active ingredient, in a 
quantity which is toxic to said insects, a compound of the present 
invention. The concentration of the new compounds of this invention in the 
insecticidal compositions will vary greatly with the type of formulation 
and the purpose for which it is designed, but generally the insecticidal 
compositions will comprise from about 0.05 to about 95 percent by weight 
of the active compounds of this invention. In a preferred embodiment of 
this invention, the insecticidal compositions will comprise from about 5 
to 75 percent by weight of the active compound. The compositions can also 
comprise such additional substances as other pesticides, stabilizers, 
spreaders, deactivators, adhesives, stickers, fertilizers, activators, 
synergists and the like. 
The compounds of the present invention are also useful when combined with 
other insecticides in the insecticidal compositions heretofore described. 
These other insecticides can comprise from about 5 to about 95 percent of 
the active ingredients in the insecticidal compositions. Use of the 
combinations of these other insecticides with the compounds of the present 
invention provide insecticidal compositions which are more effective in 
controlling insects and often provide results unattainable with separate 
compositions of the individual insecticides. The other insecticides with 
which the compounds of this invention can be used in the insecticidal 
composition to control insects, can include halogenated compounds such as 
DDT, methyoxychlor, TDE, lindane, chlordane, isobenzan, aldrin, dieldrin, 
heptachlor, endrin, mirex, endosulfan, dicofol and the like; organic 
phosphorus compounds such as TEPP, schradan,; ethion, parathion, EPN, 
demetron, carbophenothion phorate, inophos, diazinon, malathion, 
mevinphos, dimethoate, DBD, ronnel, oxydemetro-methyl, dicapthon, 
chlorothion, phosphamidon, naled, fenthion, trichlorofon, DDVP, and the 
likel; organic nitrogen compounds such as dinitro-o-creson, 
dinitrocyclohexylphenol, DNB, DNP, binapacril, azobenzene and the like; 
organic sulfur compounds such as phenothiazine, phenoxathin, lauryl 
thiocyanate, bis(2-thiocyanoethyl)ether, isobornyl thiocyanoacetate and 
the like; as well as such substances usually referred to as fumigants, as 
hydrogen cyanide, carbon tetrachloride, calcium cyanide, carbon disulfide, 
ethylene dichloride, propylene dichloride, ethylene dibromide, ethylene 
oxide, methyl bromide, paradichlorobenzene and the like. 
The compounds of the present invention can also be combined with fungicidal 
and nematocidal chemical compounds to form pesticidal compositions useful 
for the control of the fungi and in some cases soil nematodes as well as 
insects. Typical examples of such fungicidal chemical compounds are 
ferbam, nabam, zineb, ziram, thiram, chloranil, dichlone, glyodin, 
cycloheximide, dinocap, maneb, captan, dodine, PCNB, 
p-dimethylaminobenzenediazo sodium sulfonate and the like; while examples 
of nematocidal compounds are chloropicrin, 0,0-diethyl 
0-(2,4-dichlorophenyl) phosphorothioate, tetrachlorothiophene, dazomet, 
dibromochloropropane and the like. 
The new compounds of this invention can be used in many ways for the 
control of insects. Insecticides which are to be used as stomach poisons 
or protective materials can be applied to the surface on which the insects 
feed or travel. Insecticides which are to be used as contact poisons or 
eradicants can be applied directly to the body of the insect, as a 
residual treatment to the surface on which the insect may walk or crawl, 
or as a fumigant treatment of the air which the insect breathes. In some 
cases, the compounds applied to the soil or plant surfaces are taken up by 
the plant, and the insects are poisoned systemically. 
The above methods of using insecticides are based on the fact that almost 
all the injury done by insects is a direct or indirect result of their 
attempts to secure food. Indeed, the large number of destructive insects 
can be classified broadly on the basis of their feeding habits. Among the 
insects which can be effectively controlled by the compounds of the 
present invention are the chewing insects, such as the Mexican bean beetle 
and the southern army worm; the piercing-sucking insects, such as the pea 
aphid, the cereal leaf beetle, the housefly, the grape leafhopper, the 
chinch bug, the lygus bug, the oyster shell scale, the California red 
scale, the Florida red scale, the soft scale and mosquitoes; the internal 
feeders including borers, such as the European corn borer, the peach twig 
borer and the corn earworm, worms or weevils, such as the codling worm, 
the plum curculio, the red banded leaf roller, the melonworm, the cabbage 
looper and the apple maggot, leaf miners such as the apple leaf miner, the 
birch leaf miner and the beet leaf miner, and gall insects such as the 
wheat joint worm and the grape phylloxera. Insects which attack below the 
surface of the ground are classified as subterranean insects and include 
such destructive pests as the woolly apple aphid, the onion maggot and the 
corn rootworm. 
The quantity of active compound of this invention to be used for insect 
control will depend on a variety of factors, such as the specific insect 
involved, intensity of the infestation, weather, type of environment, type 
of formulation and the like. For example, the application of only one or 
two ounces of active compound per acre may be adequate for control of a 
light infestation of an insect under conditions unfavorable for its 
feeding while a pound or more of active compound per acre may be required 
for the control of a heavy infestation of insects under conditions 
favorable to their development. 
The insecticidal activity of the compounds of the present invention was 
demonstrated by experiments carried out for the control of a variety of 
insects. In these experiments, the compounds to be tested are first put 
into a formulation suitable for application at various concentrations and 
application rates to plants and insects. The desired quantity of the test 
compound (the quantity being determined by the application concentration 
or application rate to be used in later testing) is dissolved or dispersed 
in a solvent consisting of acetone containing 3.19 grams/liter of Triton X 
-155 per liter. 
Test plants used in these experiments are prepared by planting the 
appropriate seeds in sterilized soil contained in plastic pots having an 
upper soil surface area of approximately 12.25 square inches. After the 
seed has been planted, a layer of approximately 0.25 inches of sand is 
spread on the top surface of the soil. The test compound is applied after 
the plant has reached a specified size. 
For the foliar applications, the test compound, dissolved or dispersed in 
the water/acetone solvent described above, is sprayed as a mist onto the 
foliage of the test plants. The concentration of the test compound and the 
total quantity of solution applied is adjusted to give the application 
concentrations or rates desired. The plants are then allowed to air dry. 
Mites and aphids are exposed to treated leaves which have been left on the 
plant. Other insect species are exposed to treated leaves which have been 
removed from the plant and placed in petri dishes containing a piece of 
moist filter paper. 
For the soil drench applications the test compound is first dissolved or 
dispersed in water/acetone as described above, then the amount of solution 
required to give a desired application rate is applied, using a pipette, 
evenly over the top of the soil in the pot. Twenty-four hours after 
treatment, mites and aphids are exposed to leaves which have been removed 
from the plants 24 hours after treatment and placed in petri dishes 
containing a piece of moist filter paper. 
In direct contact applications, the test compound is, again, first 
formulated into a water/acetone solution, as described above, in the 
concentrations to be tested. Then the insect to be tested is dipped into, 
sprayed with or immersed in the liquid, dried and observed for effect. 
In the tables below setting forth the experimental data, PPM represents 
foliar application rates expressed as parts-per-million, #/A represents 
soil drench application rates expressed as pounds per acre. 
CABBAGE LOOPER 
Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed, at 
various application rates, to the test compound applied as a foliar spray. 
Leaves are removed from the plant after approximately 30 minutes of 
air-drying of the foliar spray application, and placed in petri dishes 
containing a piece of moist filter paper. Ten cabbage loopers, second 
instar larval stage, are placed in each petri dish and the dish covered. 
Observations of insect mortality are made after 48 hours of exposure. 
Results of these tests are detailed in Table 1 below. 
TABLE 1 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 32 16 
______________________________________ 
Product of Ex. 1 -- 90 75* 70* 60* 
Product of Ex. 2 -- 40 10 0 -- 
______________________________________ 
NOTE: 
* = Average of two tests 
SOUTHERN ARMYWORM 
Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed, at 
various application rates, to the test compound applied as a foliar spray. 
Leaves are removed from the plants after approximately 30 minutes of 
air-drying of the foliar spray application and placed in petri dishes 
containing a piece of moist filter paper. Ten southern armyworms, second 
instar larval stage, are placed in each petri dish and the dish covered. 
Observations of insect mortality are made after 48 hours of exposure. 
Results of these tests are detailed in Table 2 below. 
TABLE 2 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 32 16 
______________________________________ 
Product of Ex. 1 -- 90 100* 
50* 35* 
Product of Ex. 2 100 -- -- -- 30 
______________________________________ 
NOTE: 
* = Average of two tests 
SOYBEAN LOOPER 
Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed, at 
various application rates, to the test compound applied as a foliar spray. 
Leaves are removed from the plants after approximately 30 minutes of 
air-drying of the foliar spray application and are placed in petri dishes 
containing a piece of moist filter paper. Ten second instar larval soybean 
loopers are placed in each petri dish and the dish covered. Observations 
of insect mortality are made after 48 hours of exposure. Results of these 
tests are detailed in Table 3 below. 
TABLE 3 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 32 16 
______________________________________ 
Product of Ex. 1 -- -- 30 30 20 
Product of Ex. 2 -- 40 20 10 -- 
______________________________________ 
TOBACCO BUDWORM 
Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed at 
various application rates, to the test compound applied as a foliar spray. 
Leaves are removed from the plants after approximately 30 minutes of 
air-drying of the foliar spray application and placed in petri dishes 
containing a piece of moist filter paper. Ten tobacco budworms, second 
instar larval stage, are placed in each petri dish and the dish covered. 
Observations of insect mortality are made after 48 hours of exposure. 
Results of these tests are detailed in Table 4 below. 
TABLE 4 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 32 16 
______________________________________ 
Product of Ex. 1 -- 90 95* 40* 20* 
Product of Ex. 2 -- 50 70 10 -- 
______________________________________ 
NOTE: 
* = Average of two tests 
MEXICAN BEAN BEETLE 
Bush lima bean plants (Burpee Variety 222), two-leaf stage, are exposed, at 
various application rates, to the test compound applied as a foliar spray. 
Leaves are removed from the plants after approximately 30 minutes of 
air-drying of the foliar spray application and placed in petri dishes 
containing a piece of moist filter paper. Ten Mexican bean beetles, second 
instar larval stage, are placed in each petri dish and the dish covered. 
Observations of insect mortality are made after 48 hours of exposure. 
Results of these tests are detailed in Table 5 below. 
TABLE 5 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 32 
______________________________________ 
Product of Ex. 1 100 -- -- -- 
Product of Ex. 2 0 100 100 90 
______________________________________ 
BOLL WEEVIL 
Cotton plants (deltapine 16), two-leaf stage, are exposed at various 
application rates, to the test compound applied as a foliar spray. Leaves 
are removed from the plants after approximately 30 minutes of air-drying 
of the foliar spray application and placed in petri dishes containing a 
piece of moist filter paper. Ten adult boll weevils are placed in each 
petri dish and the dish is then covered. Observations of insect mortality 
are made after 48 hours of exposure. Results of these tests are detailed 
in Table 6 below. 
TABLE 6 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 
______________________________________ 
Product of Ex. 1 0 -- -- 
Product of Ex. 2 0 0 0 
______________________________________ 
PEA APHID 
Pea plants (Burpee Wando) in the 10-14 day stage are treated at various 
application rates to the test compound applied as a foliar spray. The 
plants are air-dried for about 30 minutes after the foliar spray is 
applied, then 25-30 pea aphids, adults and nymphs, are put on each treated 
plant and on an untreated control plant with a small paint brush. After 48 
hours of exposure of the insects to the treated plants, insect mortality 
is determined by comparison of the number of insects on the treated plants 
to the number on the untreated control plant. Results of this testing are 
set forth in Table 7 below. 
TABLE 7 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 
______________________________________ 
Product of Ex. 1 0 -- -- 
Product of Ex. 2 0 0 0 
______________________________________ 
TWO-SPOTTED MITE 
Bush lima bean plants (Burpee Variety 222) in the two-leaf stage are 
treated with the test compound, at various application rates, by the 
foliar spray method. The plants are air-dried for about 30 minutes after 
the foliar spray is applied, then 50-100 two-spotted mites, adults and 
nymphs, are put on each treated plant and on an untreated control plant by 
placing an untreated infested bean leaf containing 50-100 mites using the 
technique described above. An untreated control plant is similarly 
infested. After 48 hours of exposure of the insects to the treated plants, 
insect mortality is determined by comparison of the number of insects on 
the treated plants to the number on the untreated control plants. Results 
of this testing are set forth in Table 8 below. 
TABLE 8 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 
______________________________________ 
Product of Ex. 1 0 -- -- 
Product of Ex. 2 0 0 0 
______________________________________ 
HOUSEFLY 
Ten adult Houseflies are placed in a small (2"-3") wire screen cage fitted 
with a plastic cap. The cage is sprayed with the test compound at the 
desired concentration in the form of a solution prepared as described 
hereinabove. After spraying, the treated cages are stored until dry. Sixty 
minutes after spraying readings are made of knockdown. The cages are then 
placed on paper toweling moistened with 5-10% sucrose solution and stored 
on this toweling for 23 hours at which time the 24 hours-after-treatment 
mortality reading is taken. The results of this test are given in Table 9 
below. 
TABLE 9 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 
______________________________________ 
Product of Ex. 1 
k 20 -- -- 
m 20 -- -- 
Product of Ex. 2 
k 30 20 0 
m 80 10 0 
______________________________________ 
NOTE: 
k = 60minute knockdown 
m = 24hour mortality 
GERMAN COCKROACH 
Solutions of test compounds are formulated as described hereinabove and the 
solution which gives a desired application concentration is placed in a 
flask. Ten german cockroach adults are placed in a teaspoon test strainer 
and are dipped into the test solution. The excess solution is shaken off, 
the tea strainer opened and the insects placed in a clear plastic 
container containing a small piece of dental wick. The container is then 
capped with a cover pierced with air holes. Insect mortality is observed 
after 60 minutes, 24 hours and 48 hours following the exposure. Results of 
this testing are indicated in Table 10 below. 
TABLE 10 
______________________________________ 
Test Application 
Compound Rate: PPM 256 128 64 
______________________________________ 
Product of Ex. 1 
(60) 0 -- -- 
(24) 0 -- -- 
(48) 0 -- -- 
Product of Ex. 2 
(60) 0 0 0 
(24) 0 0 0 
(48) 0 0 0 
______________________________________ 
NOTE: 
(60) = 60minute mortality 
(24) = 24hour mortality 
(48) = 48hour mortality 
SOUTHERN CORN ROOTWORM 
A newly germinated corn seed is placed in a one-ounce plastic cup fitted 
with a snap-on plastic lid and covered with approximately 5 grams of 
sterilized soil. The test compound is formulated into solution as 
described hereinbefore and applied to the soil as a soil drench at the 
desired application rates. After application the lids are snapped on the 
cups and the cups are allowed to stand for about 15 minutes to permit the 
solution to spread evenly through the soil. The lids are then removed, 
five second instar rootworm larvae are placed on the treated soil and the 
cups recapped. The cup is examined for insect mortality after 72 hours of 
exposure. Larvae which cannot crawl or right themselves are considered 
dead. Results of this testing are given in Table 11 below. 
TABLE 11 
______________________________________ 
Test Application 
Compound Rate: #/A 256 128 64 32 16 
______________________________________ 
Product of Ex. 1 -- -- -- -- 40 
______________________________________