An anilin derivative which corresponds to the following formula: ##STR1## wherein, R.sub.2 is hydrogen, lower alkoxy group, a nitro group, or one or more halogen atoms selected from fluorine, chlorine and bromine; and X is a lower alkyl group or a phenyl substituent. The compounds are intermediates for insecticides.

BACKGROUND OF THE INVENTION 
The present invention relates to novel benzoyl urea derivatives having a 
pryzole group which have active insecticidal properties as an insect 
growth regulator. The present invention also relates to insecticidal 
compositions comprising these derivatives and to the use of such 
compositions for killing and controlling insects. 
Several kinds of benzoyl urea compounds have been developed as chitin 
inhibitors since Dimilin.RTM. was introduced in the market. However most 
of them have not been commercialized due to their complicated 
manufacturing processes and high costs even though they have a better 
effect than Dimilin.RTM.. For example, even though several benzoyl urea 
derivatives have been synthesized according to the disclosed Japanese 
Patent laid-open Nos. 85-193960 and 87-178561, and European Patent Nos. 
176868 and 52833, these manufacturing processes are too complicated to be 
improved. 
Therefore, with consideration to the foregoing points the present inventors 
have developed new insecticidal compounds which exhibit broad spectrum and 
powerful insecticidal activities towards various harmful insects. 
Furthermore, they can be prepared via a simple process starting from 
readily available raw chemicals as compared with existing chitin inhibitor 
insecticides. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide powerful benzoyl urea 
derivatives with strong insecticidal activities toward various harmful 
insects and having a simple manufacturing process utilizing raw materials 
of low cost. 
Another object is to provide insecticidal compositions containing active 
compounds of those derivatives. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention is directed to benzoyl urea derivatives having a 
pyrazole group which correspond to the following formula(I) 
##STR2## 
wherein. 
R and R.sub.2, are the same or different, and are hydrogen, one or more 
halogen atoms selected from the group consisting of fluorine, chlorine and 
bromine atoms, a lower alkoxy group or a nitro group: 
R.sub.1 is a hydrogen atom or a lower alkyl group; and 
X is a lower alkyl group or phenyl substituent. 
In the present invention, the terms "lower alkoxy group" and "lower alkyl 
group" designate a straight or branched chain alkoxy and alkyl groups of 1 
to 6 carbon atoms. 
According to a first embodiment of the present invention, the above benzoyl 
urea derivatives can be easily prepared by converting substituted 
benzamide derivatives of the following formula(II) to benzoyl isocyanate 
of the following formula(III) using oxaryl chloride or phosgene and 
reacting the compound of formula(III) with anilin derivatives of the 
following formula(IV) and an acid scavenger. 
##STR3## 
wherein, R, R.sub.2 and X are defined as above: and R.sub.1 is a hydrogen 
atom. 
In the above reaction, organic solvents such as benzene, toluene, xylene, 
chlorobenzene or 1,2-dichloroethane can be used for the reaction from 
substitutied benzamide derivatives of formula(II) to benzoyl isocyanate of 
formula(III), and then completion of the reaction is assumed when no more 
gas is produced. Toluene, xylene, chlorobenzene or 1,2-dichloroethane can 
be used as a solvent for obtaining the desired compound(I) by reacting 
isocyanate of formula(III) with anilin derivatives of formula(IV), and 
then 0.5.about.1 equivalent weight of tertiary amine, e.g. triethyl amine, 
is used as an acid scavenger. 
If the acid scavenger is not added, the yield will be decreased due to 
coexisting hydrochloride which is produced during the formation of the 
isocyanate(III). The reaction for the formation of the desired compound(I) 
is complete when no more anilin derivative remains. This can be easily 
checked by T.L.C. or G.C. 
After completion of the reaction, the desired compound may be separated by 
well-known methods as follows: the solid compound is obtained by 
recrystallization after filteration, and the remaining filtrate is washed 
with water to remove organic solvents, and then the desired compound can 
be obtained by recrystallization or purified by chromatography and 
identified by NMR, IR and MS. 
Accordingly to a second embodiment, the desired compound(I) can be produced 
by reacting anilin derivatives of formula(IV) with phosgene to obtain 
isocyanate of the following formula(V) and adding benzamide derivatives of 
formula(II) and acid scavenger, according to following reaction scheme. 
##STR4## 
wherein, R, R.sub.2 and X are defined as above: and R.sub.1 is a hydrogen 
atom. 
In the above reaction, ethylacetate, tetrahydrofuran, benzene, toluene, 
chlorobenzene, xylene or 1,2-dichloroethane can be used as organic solvent 
for obtaining the isocyanate compound(V) from the anilin derivatives of 
formula(IV). The reaction is assumed to be complete when no more hydrogen 
chloride gas is produced. 
Also, toluene, xylene or chlorobenzene can be used as an organic solvent 
for the reaction of the isocyanate derivatives(V) with the benzamide 
derivatives(II), and then tertiary amine such as triethylamine can be used 
as an acid scavenger. 
The reaction is assumed to be complete when no more compound of formula(II) 
remains. The identification of reaction completion, yield and the desired 
compound is the same as in the above first method. 
According to the present invention an alkyl group can be introduced at the 
R.sub.1 position of the desired compound of formula(I) (R.sub.1 .dbd.H) by 
using alkylating reagent. For example, the compound(I), where R.sub.1 is 
an alkyl group, can be produced by treating methyliodide or ethyliodide 
with the compound of formula(I)(R.sub.1 .dbd.H) and an acid scavenger. 
Acetonitrile, dimethylformamide or dimethylsulfoxide may be used as the 
organic solvent and hydroxides of alkali metal or alkali earth metal, 
carbonate or tertiary amine may be used as the acid scavenger. The 
reaction is assumed to be complete when no more compound of 
formula(I)(R.sub.1 .dbd.H) remains, and this can be easily checked by 
T.L.C. or G.C. After completion of the alkyl substitution reaction, 
several processes can be applied to obtain the desired compound from the 
reaction mixture. For example, after washing the reaction mixture with 
water to remove the used organic solvent, the desired compound can be 
obtained by recrystalization or chromatography, and it can be confirmed by 
NMR, IR and MS. 
Typical new benzoyl urea derivatives of formula(I) according to the present 
invention are listed in Table 1. 
TABLE 1 
______________________________________ 
##STR5## (I) 
Compound No. 
R R.sub.1 
R.sub.2 X 
______________________________________ 
1 2,6-F.sub.2 
H 2,5-Cl.sub.2 
CH.sub.3 
2 2,6-F.sub.2 
H 2,5-Cl.sub.2 
##STR6## 
3 2,6-F.sub.2 
H 2-OMe CH.sub.3 
4 2,6-F.sub.2 
H 2-CO.sub.2 Me 
CH.sub.3 
5 2,6-F.sub.2 
H 2,5-F.sub.2 
##STR7## 
6 2,6-F.sub.2 
H 3-Cl CH.sub.3 
7 2,6-F.sub.2 
H 3-Cl 
##STR8## 
8 2,6-F.sub.2 
H 2,3,5,6-F.sub.2 
CH.sub.3 
9 2,6-F.sub.2 
H 2,3,5,6-F.sub.2 
##STR9## 
10 2-Cl H 2,3,5,6-F.sub. 2 
##STR10## 
11 2-F H 2,3,5,6-F.sub.2 
##STR11## 
12 2-Cl H 2,5-Cl.sub.2 
##STR12## 
13 2,6-F.sub.2 
H 3-CF.sub.3 
##STR13## 
14 2-Cl H 3-CF.sub.3 
##STR14## 
15 2-F H 3-CF.sub.3 
##STR15## 
16 2-Cl H 3-Cl CH.sub.3 
17 2-F H 3-Cl CH.sub.3 
______________________________________

The present invention is illustrated by following Examples, but should not 
be construed to be limited thereto. 
EXAMPLE 1 
Benzamide-2,6-difluoro-N-((( 
2.5-dichloro-4-(1-methyl-3-trifluoromethyl-5-pyrazoyl)oxyphenyl)amino)carbo 
nyll (Compound No. 1) 
##STR16## 
2,6-Difluorobenzamide(0.145 g, 0.92 mmole) and oxarylchloride(0.141 g, 1.11 
mmole, 1.2 eq) were added to 1,2-dichloro ethane(6 ml) and the mixture was 
stirred at 100.degree. C. for 20 hours. 
2,5-Dichloro-4-o-(1-methyl-3-trifluormethyl-5-pyrazoyl)-anilin(0.3 g, 
0.92 mmole) and triethyl amine(0.664 ml. 0.5 eq) were added and reacted at 
room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(60 ml) and water (40 ml) were added to the reaction mixture and 
the ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure, the desired 
product (0.311 g, yield 66%) was obtained as a solid by 
chromatography(ethyl acetate:hexane=1:2). 
m.p.: 213.degree..about.215.degree. C. 
.sup.1 H NMR(CDCl.sub.3 +DMSO--d.sub.6): .delta. 3.9(s. 3H), 5.8(s, 1H), 
7.0.about.7.6(m. 4H), 8.6(s. 1H), 11.1(s, 1H), 11.3(s, 1H). 
EXAMPLE 2 
Benzamide-2,6-difluoro-N-(((2,5-dichloro-4-(1-phenyl-3-trifluoromethyl-5-py 
razoyl)oxyphenyl)amino)carbonyl) (Compound No. 5) 
##STR17## 
2,6-Difluorobenzamide(0.25 g, 1.59 mmole) and oxarylchloride(0.166 ml, 1.90 
mmole, 1.2 eq) were added to 1.2-dichloroethane(6 ml), and the mixture was 
stirred at 100.degree. C. for 20 hours. 
2,5-Difluoro-4-o-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)anilin(0.564 g, 
1.59 mmole) and triethylamine(0.11 ml. 0.5 eq) were added and reacted at 
room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(80 ml) and water (40 ml) were added to the reaction mixture and 
the ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. 
After removing ethyl acetate under reduced pressure, the desired product 
(0.45 g, yield: 52%) was obtained as a solid by recrystallization (ethyl 
acetate+hexane). 
m.p.: 185.degree..about.187.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 5.9(s, 1H), 7.0.about.8.2(m, 10H), 
10.2(s, 1H), 11.0(s, 1H). 
EXAMPLE 3 
Benzamide-2,6-difluoro-N-(((3-chloro-4-(1-methyl-3-trifluoromethyl-5-pyrazo 
yl)oxyphenyl)amino)carbonyl) (Compound No. 6) 
##STR18## 
2,6-Difluoro benzamide(0.25 g, 1.59 mmole) and oxacrylchloride(0.166 ml, 
1.90 mmole, 1.2 eq) were added to 1,2-dichloroethane (8 ml), and the 
mixture was stirred at 100.degree. C. for 20 hours. 
3-Chloro-4-o-(1-methyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.463 g, 1.59 
mmole) and triethylamine(0.11 ml, 0.5 eq) were added and reacted at room 
temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(80 ml) and water (40 ml) were added to the reaction mixture and 
the ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. 
After removing ethyl acetate under reduced pressure, the desired 
product(0.377 g, yield: 50%) was obtained as a solid by 
recrystallization(ethyl acetate+hexane). 
m.p.: 193.degree..about.195.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 3.8(s. 3H), 5.8(s. 1H), 7.0.about.7.8(m. 
6H), 10.1(s. 1H), 10.8(s. 1H). 
EXAMPLE 4 
Benzamide-2,6-difluoro-N-(((3-chloro-4-(1-phenyl-3-trifluoromethyl-5-pyrazo 
yl)oxyphenyl)amino)carbonyl) (Compound No. 7) 
##STR19## 
2,6-Difluorobenzamide(0.17 g, 1.131 mmole) and oxarylchloride(0.118 ml, 
1.35 mmole, 1.2 eq) were added to 1,2-dichloroethane(6 ml), and the 
mixture was stirred at 100.degree. C. 20 hours. 
3-Chloro-4-o-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.4 g, 1.131 
mmole) and triethylamine(0.09 ml, 0.5 eq) were added and reacted at room 
temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(70 ml) and water(40 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure, the desired 
product(0.31 g, yield: 51%) was obtained as a solid by 
chromatography(ethyl acetate:hexane =1:5). 
m.p.: 169.degree..about.172.degree.C. 
.sup.1 H NMR(CDCl.sub.3) : .delta. 5.9(s, 1H), 7.0.about.8.0(m, 1H), 9.8(s, 
1H), 10.7(s, 1H). 
EXAMPLE 5 
Benzamide-2,6-difluoro-N-(((3-chloro-4-(1-phenyl-3-trifluoromethyl-5-pyrazo 
yl)oxyphenyl)amino)carbonyl) (Compound No. 8) 
##STR20## 
2,6-Difluorobenzamide(0.1 g, 0.636 mmole) and oxarylchloride(0.066 ml, 
0.763 mmole, 1.2 eq) were added to 1,2-dichloroethane(6 ml), and the 
mixture was stirred at 100.degree. C. for 20 hours. 
2,3,5,6-Tetrafluoro-4-o-(1-methyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.2 
09 g, 0.636 mmole) and triethylamine(0.044 ml, 0.5 eq) were added and 
reacted at room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(60 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure, the desired 
product(0.20 g, yield: 61%) was obtained as a solid by 
chromatography(ethyl acetate:hexane=1:9). 
m.p.: 215.degree..about.217.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 3.8(s, 3H), 5.8(s, 1H), 6.8.about.7.6(m, 
3H), 9.1(s, 1H), 10.0(s, 1H). 
EXAMPLE 6 
Benzamide-2,6-difluoro-N-(((2,3,5,6-tetrafluoro-4-(1-phenyl-3-trifluorometh 
yl-5-pyrazoyl)oxyphenyl)amino)carbonyl) (Compound No. 9) 
##STR21## 
2,6-Difluorobenzamide(0.2 g, 1.27 mmole) and oxarylchloride(0.132 ml, 1.524 
mmole, 1.2 eq) were added to 1,2-dichloroethane(8 ml), and the mixture was 
stirred at 100.degree. C. for 20 hours. 
2,3,5,6-Tetrafluoro-4-o-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.4 
97 g, 1.27 mmole) and triethylamine(0.08 ml, 0.5 eq) were added at room 
temperature for one hour. 
Organic solvent was removed under reduced pressure, and ethyl acetate(70 
ml) and water(30 ml) were added to the reaction mixture and the ethyl 
acetate layer collected, which is dried with anhydrous magnesium sulfate. 
After removing ethyl acetate under reduced pressure, the desired 
product(0.45 g, yield : 61%) was obtained as a solid by 
chromatography(ethyl acetate:hexane=1:9). 
m.p. : 198.degree..about.200.degree. C. 
.sup.1 H NMR(CDCl.sub.3) : .delta.5.9(s, 1H), 6.9.degree..about.7.8(m, 8H), 
9.4(s, 1H), 10.2(s, 1H) 
EXAMPLE 7 
Benzamide-2-chloro-N-((2,3,5,6-tetrafluoro-4-(1-phenyl-3-trifluoromethyl-5- 
pyrazoyl)oxyphenyl)amino)carbonyl)(Compound No. 10) 
##STR22## 
2-Chlorobenzamide(0.1 g, 0.64 mmole) and oxarylchloride(0.067 ml, 0.76 
mmole, 1.2 eq) were added to 1,2-dichloroethane(7 ml), and the mixture was 
stirred at 100.degree. C. for 20 hours. 
2,3,5,6-tetrafluoro-4-o-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.2 
5 g, 0.64 mmole) and triethylamine(0.044 ml, 0.5 eq) were added and reacted 
at room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(70 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure, the desired 
product(0.21 g, yield: 57%) was obtained as a solid by 
chromatography(ethyl acetate:hexane=1:9). 
m.p.: 177.degree..about.179.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 5.9(s, 1H), 7.5.about.7.9(m, 9H), 9.4(s, 
1H), 10.3(s, 1H). 
EXAMPLE 8 
Benzamide-2-fluoro-N-(((2,3,5,6-tetrafluoro-4-(1-phenyl-3-trifluoromethyl-5 
-pyrazoyl)oxyphenyl)amino)carbonyl)(Compound No. 11) 
##STR23## 
2-Fluorobenzamide(0.088 g, 0.632 mmol and oxarylchloride(0.066 ml, 0.7 were 
added to 1,2-dichloroethane(7 ml), and the mixture was stirred at 
100.degree. C. for 20 hours. 
2,3,5,6-Tetrafluoro-4-o-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.2 
47 g, 0.632 mmole) and triethylamine(0.04 ml, 0.5 eq) were added and 
reacted at room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(60 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure, the desired 
product(0.197 g, yield: 56%) was obtained as a solid by 
chromatography(ethyl acetate:hexane=1:9). 
m.p.: 173.degree..about.175.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 6.0(s, 1H), 7.1.about.8.2(m, 9H), 9.2(d, 
1H), 10.2(s, 1H). 
EXAMPLE 9 
Benzamide-2-chloro-N-(((3-chloro-4-(1-methyl-3-trifluoromethyl-5-pyrazoyl)o 
xyphenyl)amino)carbonyl)(Compound No. 16) 
##STR24## 
2-Chlorobenzamide(0.25 g, 1.60 mmole) and oxarylchloride(0.168 ml, 1.92 
mmole, 1.2 eq) were added to 1,2-dichloroethane(7 ml), and the mixture was 
stirred at 100.degree. C. for 20 hours. 
3-Chloro-4-o-(1-methyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.468 g, 1.60 
mmole) and triethylamine(0.11 ml, 0.5 eq) were added and reacted at room 
temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(80 ml and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. yield: 65%) was obtained as a solid by chromatography(ethyl 
acetate:hexane=1:9). 
m.p.: 201.degree..about.202.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 4.0(s, 3H), 5.8(s, 1H), 7.3.about.8.0(m, 
7H), 9.9(s, 1H), 
10.9(s, 1H). 
EXAMPLE 10 
Benzamide-2-fluoro-N-(((3-chloro-4-(1-methyl-3-trifluoromethyl-5-pyrazoyl)o 
xyphenyl)amino)carbonyl)(Compound No. 17) 
##STR25## 
2-Fluorobenzamide(0.143 g, 1.02 mmole) and oxarylchloride(0.107 ml, 1.23 
mmole, 1.2 eq) were added to 1,2-dichloroethane(7 ml), and the mixture was 
stirred at 100.degree. C. for 20 hours. 
3-Chloro-4-o-(I-methyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.3 g, 1.02 
mmole) and triethyl amine(0.071 ml, 0.5 eq) were added and reacted at room 
temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(60 ml) and water (30 ml) were added to the reaction mixture and 
the ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure, the desired 
product(0.224 g, yield: 48%) was obtained as a solid by 
chromatography(ethyl acetate:hexane=1:9). 
m.p.: 179.degree..about.180.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 4.1(s, 3H), 5.9(s, 1H), 7.2.about.8.3(m, 
7H), 9.1(d, 1H), 11.0(s, 1H). 
EXAMPLE 11 
Benzamide-2-chloro-N-(((3-chloro-4-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)o 
xyphenyl)amino)carbonyl)(Compound No. 18) 
##STR26## 
2-Chlorobenzamide(0.132 g, 0.848 mmole) and oxarylchloride (0.088 ml, 1.90 
mmole, 1.2 eq) were added to 1,2-dichloromethane(7 ml), and the mixture 
was stirred at 100.degree. C. for 20 hours. 
3-Chloro-4-o-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)-anilin(3 g, 0.848 
mmole) and triethylamine(0.059 ml, 0.5 eq) were added and reacted at room 
temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(80 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. 
After removing ethyl acetate under reduced pressure, the desired 
product(0.2 g, yield: 44%) was obtained as a solid by chromatography(ethyl 
acetate:hexane=1:9). 
m.p.: 189.degree..about.190.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 5.9(s, 1H), 7.0.about.8.0(m, 12H), 9.7(s, 
1H), 10.8(s, 1H). 
EXAMPLE 12 
Benzamide-2-chloro-N-(((2,5-difluoro-4-(1-methyl-3-trifluoromethyl-5-pyrazo 
yl)oxyphenyl)amino)carbonyl)(Compound No. 19) 
##STR27## 
2-Chlorobenzamide(0.131 g, 0.844 mmole) and oxarylchloride(0.088 ml, 1.013 
mmole, 1.2 eq) were added to 1,2-dichloroethane(7 ml), and the mixture was 
stirred at 100.degree. C. for 20 hours. 
2,5-Difluoro-4-o-(1-phenyl-3-trifluoro methyl-5-pyrazoyl)-anilin(0.3 g, 
0.844 mmole) and triethylamine(0.058 ml. 0.5 eq) were added and reacted at 
room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl acetate 
(80 ml) and water(30 ml) were added to the reaction mixture and the ethyl 
acetate layer collected, which is dried with anhydrous magnesium sulfate. 
After removing ethyl acetate under reduced pressure, the desired 
product(0.2 g, yield : 43%) was obtained as a solid by 
chromatography(ethyl acetate:hexane=1:9). 
m.p.: 181.degree..about.182.degree. C. 
.sup.1 H NMR(CDCl.sub.3) : .delta. 5.9(s. 1H), 6.9.about.8.2(m, 11H), 10(s, 
1H), 11.1(s, 1H). 
EXAMPLE 13 
Benzamide-2,6-difluoro-N-(((2,5-difluoro-4(1-methyl-3-trifluoromethyl-5-pyr 
azoyl)oxyphenyl)amino)carbonyl) (Compound No. 20) 
##STR28## 
2,6-Difluorobenzamide(0.123 g, 0.784 mmole) and oxarylchloride(0.082 ml, 
0.941 mmole, 1.2 eq) were added to 1,2-dichloroethane(7 ml), and the 
mixture was stirred at 100.degree. C. for 20 hours. 
2,5-Difluoro-4-o-(1-methyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.23 g, 
0.784 mmole) and triethyl amine(0.054 ml, 0.5 eq) were added and reacted 
at room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(70 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. 
After removing ethyl acetate under reduced pressure, the desired 
product(0.2 g, yield : 53%) was obtained as a solid by 
crystallization(ethyl acetate +hexane). 
m.p.: 203.degree..about.205.degree. C. 
.sup.1 H NMR(CDCl.sub.3) : .delta. 3.8(s, 3H), 5.8(s, 1H), 6.9.about.8.1(m, 
5H), 10.1(s, 1H), 10.8(s, 1H). 
EXAMPLE 14 
Benzamide-2,6-difluoro-N-(((4-(1-methyl-3-trifluoromethyl-5-pyrazoyl)oxyphe 
nyl)amino)carbonyl) (Compound No. 21) 
##STR29## 
2,6-Difluorobenzamide(0.183 g, 1.16 mmole) and oxarylchloride(0.122 ml, 
1.40 mmole, 1.2 eq) were added to 1,2-dichloroethane(7 ml), and the 
mixture was stirred at 100.degree. C. for 20 hours. 
4-o-(1-Methyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.3 g, 1.16 mmole) and 
triethylamine(0.08 ml, 0.5 eq) were added and reacted at room temperature 
for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(70 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure, the desired 
product (0.303 g, yield : 595) was obtained as a solid by 
recrystallization(ethyl acetate+hexane). 
m.p.: 203.degree. C. 
.sup.1 H NMR(CDCl.sub.3) : .delta. 3.8(s, 3H), 5.8(s, 1H), 6.8.about.7.5(m, 
7H), 9.0(s, 1H), 10.4(s, 1H). 
EXAMPLE 15 
Benzamide-2,6-difluoro-N-(((3-trifluoromethyl-4-(1-methyl-3-trifluoromethyl 
-5-pyrazoyl)oxyphenyl)amino)carbonyl) (Compound No. 22) 
##STR30## 
2,6-Difluorobenzamide(0.145 g, 0.922 mmole) and oxarylchloride(0.096 ml, 
1.10 mmole, 1.2 eq) were added to 1,2-dichloroethane(6ml), and the mixture 
was stirred at 100.degree. C. for 20 hours. 
3-Trifluoromethyl-4-o-(1-methyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.3 
g, 0.922 mmole) and triethylamine(0.064 ml, 0.5 eq) were added and reacted 
at room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(70 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. 
After removing ethyl acetate under reduced pressure, the desired 
product(0.29 g, yield: 61%) was obtained as a solid by 
chromatography(ethyl acetate:hexane=1:4). 
m.p.: 203.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 3.8(s, 3H), 5.9(s, 1H), 6.9.about.7.9(m, 
6H), 9.2(s, 1H), 10.7(s, 1H). 
EXAMPLE 16 
Benzamide-2,6-difluoro-N-(((3,5-dichloro-4-(1-methyl-3-trifluoromethyl-5-py 
razolyl)oxyphenyl)amino)carbonyl) (Compound No. 23) 
##STR31## 
2,6-Difluorobenzamide(0.120 g, 0.766 mmole) and oxarylchloride(0.080 ml, 
0.920 mmole, 1.2 eq) were added to 1,2-dichloro ethane(7 ml), and the 
mixture was stirred at 100.degree. C. for 20 hours. 
3,5-Dichloro-4-o-(1-methyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.25 g, 
0.766 mmole) and triethylamine(0.053 ml, 0.5 eq) were added and reacted at 
room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(80 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure, the desired 
product(0.237 g, yield: 61%) was obtained as solid by 
chromatography(ethylacetate:hexane=1:5). 
m.p.: 221.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 4.0(s, 3H), 5.6(s, 1H), 7.2.about.7.6(m, 
5H), 10.8(s, 1H). 
EXAMPLE 17 
Benzamide-2,6-difluoro-N-(((3,5-dichloro-4-(1-phenyl-3-trifluoromethyl-5-py 
razoyl)oxyphenyl)amino)carbonyl) (Compound No. 24) 
##STR32## 
2,6-Difluorobenzamide(0.120 g, 0.766 mmole) and oxarylchloride(0.080 ml, 
0.920 mmole, 1.2 eq) were added to 1,2-dichloroethane(7 ml), and the 
mixture was stirred at 100.degree. C. for 20 hours. 
3,5-Dichloro-4-o-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)-anilin(0.297 g, 
0.766 mmole) and triethylamine(0.053 ml, 0.5 eq) were added and reacted at 
room temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(80 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing ethyl acetate under reduced pressure the desired 
product(0.274 g, yield: 62%) was obtained as a solid by 
chromatography(ethylacetate:hexane=1:5). 
m.p.: 236.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 5.6(s, 1H), 7.0.about.7.9(m, 10H), 
10.2(s, 1H), 10.8(s, 1H). 
EXAMPLE 18 
Benzamide-2,6-difluoro-N-(((4-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)oxyphe 
nyl)amino)carbonyl) (Compound No. 25) 
##STR33## 
2,6-Difluorobenzamide(0.123 g, 0.783 mmole) and oxarylchloride(0.082 ml, 
0.940 mmole, 1.2 eq) were added to 1,2-dichloroethane(7 ml), and the 
mixture was stirred at 100.degree. C. for 20 hours. 
4-o-(1-Phenyl-3-trifluoromethyl-5-pyrazolyl)-anilin(0.25 g, 0.783 mmole) 
and triethylamine(0.054 ml, 0.5 eq) were added and reacted at room 
temperature for one hour. 
Organic solvent was removed under reduced pressure, and then ethyl 
acetate(80 ml) and water(30 ml) were added to the reaction mixture and the 
ethyl acetate layer collected, which is dried with anhydrous magnesium 
sulfate. After removing under reduced pressure, the desired product(0.25 
g, yield=64%) was obtained as a solid by chromatography(ethyl 
acetate:hexane=1:5). 
m.p.: 215.degree..about.218.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 5.9(s, 1H), 6.9.about.7.9(m, 12H), 
10.5(s, 1H), 10.8(s, 1H). 
On the other hand, anilin derivatives of the formula(IV) as raw material 
used in the present invention may be synthesized by reacting the compound 
or its salt of formula(VI) with the compound of formula(VII), and then 
hydrogenolysis of the resulting compound of formula(VIII) as following 
reaction scheme. 
##STR34## 
For the reaction of the 5-hydroxy pyrazole compound of formula(VI) with 
halogen substituted nitrobenzene of formula(VII), common organic solvents 
such as dimethylformamide, dimethyl sulfoxide, acetonitrile or 
tetrahydrofuran can be used. 
Alkali metal or alkali earth metal, carbonate, percarbonate or tertiary 
amine can be used as an acid scaprger. The reaction is assumed to be 
complete when neither of the two starting materials are remains, and this 
can be easily confirmed by T.L.C. or G.C. 
After the completion of the reaction, the compound(VIII) may be separated 
by well-known method as follows; for example, the solid compound is 
obtained by recrystallization after filtering, and the remaining filtrate 
is washed with water to remove organic solvent, and then the 
compound(VIII) can be obtained by recrystallization or purfied by 
chromatography and identified by NMR, IR and MS. 
Anilin derivatives of the formula(IV) can be produced by hydrogenolyzing 
said compound of the formula(VIII) under a metal catalyst such as nickel 
or paladium with a primary alcohol such as methanol or ethanol being used 
as the organic solvent. 
The reaction is assumed to be completed when no more substituted 
nitrobenzene compound of formula(VIII) remains. This can be confirmed by 
T.L.C. or G.C. 
After the completion of hydrogenation, the compound(IV) can be sepaerated 
and purified as follows; the metal catalyst is removed by filtration, 
organic solvent is removed, and then the compound(IV) can be obtained by 
recrystallization or chromatography. They were identified by NRM,IR and 
MS. 
Typical compounds of the formula (VIII) and (IV) as raw materials according 
to the present invention are listed in Tables 2 and 3 respectively. 
TABLE 2 
______________________________________ 
##STR35## (VIII) 
Compound No. X R.sub.2 
______________________________________ 
29 CH.sub.3 2,5-Cl.sub.2 
30 CH.sub.3 2,5-F.sub.2 
31 CH.sub.3 3-Cl 
32 CH.sub.3 2,3,5,6-F.sub.4 
33 CH.sub.3 3-CF.sub.3 
34 CH.sub.3 2-Cl 
35 CH.sub.3 H 
36 CH.sub.3 3,5-Cl.sub.2 
37 CH.sub.3 2-OMe 
38 CH.sub.3 2-CO.sub.2 Me 
39 
##STR36## 2,5-Cl.sub.2 
40 
##STR37## 2,5-F.sub.2 
41 
##STR38## 3-Cl 
42 
##STR39## 2,3,5,6-F.sub.4 
43 
##STR40## 3-CF.sub.3 
44 
##STR41## 2-Cl 
45 
##STR42## H 
46 
##STR43## 3,5-Cl.sub.2 
______________________________________ 
TABLE 3 
______________________________________ 
##STR44## (IV) 
Compound No. X R.sub.2 
______________________________________ 
47 CH.sub.3 2,5-Cl.sub.2 
48 CH.sub.3 2,5-F.sub.2 
49 CH.sub.3 3-Cl 
50 CH.sub.3 2,3,5,6-F.sub.4 
51 CH.sub.3 3-CF.sub.3 
52 CH.sub.3 2-Cl 
53 CH.sub.3 H 
54 CH.sub.3 3,5-Cl.sub.2 
55 CH.sub.3 2-OMe 
56 CH.sub.3 2-CO.sub.2 Me 
57 
##STR45## 2,5-Cl.sub.2 
58 
##STR46## 2,5-F.sub.2 
59 
##STR47## 3-Cl 
60 
##STR48## 2,3,5,6-F.sub.4 
61 
##STR49## 3-CF.sub.3 
62 
##STR50## 2-Cl 
63 
##STR51## H 
64 
##STR52## 3,5-Cl.sub.2 
______________________________________ 
The following are typical reaction conditions for the preparation of the 
above new compounds shown in Table 2 and Table 3. 
EXAMPLE 19 
3,5-Dichloro-4-(1-methyl-3-trifluoromethyl-5-pyrazoyl)oxy-nitrobenzene 
(Compound No. 36) 
##STR53## 
1-Methyl-3-trifluoromethyl-5-hydroxy pyrazole(1 g, 6.02 mmole), 
3,4,5-trichloronitrobenzene(1.364 g, 6.02 mmole) and potassium 
carbonate(1.24 g, 9.03 mmole, 1.5 eq) were added to dimethylformamide(4 
ml) and the mixture was stirred at 90.degree..about.100.degree. C. for 30 
minutes. 
Ethyl acetate(80 ml) and water(30 ml) were added and the reaction mixture 
to ethyl acetate layer collected which is dried with anhydrous magnesium. 
After removing ethyl acetate under reduced pressure, the desired 
product(1.5 g, yield: 70%) was obtained as a solid by washing with hexane. 
m.p.: 138.degree..about.140.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 3.9(s, 3H), 5.6(s, 1H), 8.3(s, 2H). 
EXAMPLE 20 
3,5-Dichloro-4-(1-methyl-3-trifluoromethyl-5-pyrazoyl)oxy-anilin(Compound 
No. 54) 
##STR54## 
3,5-Dichloro-4-o-(1-methyl-3-trifluoromethyl-5-pyrazoyl)-nitrobenzene (1.4 
g, 3.93 mmole) and raney nickel(0.2 g) were added in methanol(30 ml) and 
reacted under hydrogen gas at 90.degree. C. for 4 hours. The raney nickel 
was removed by filtration and methanol was removed under reduced pressure, 
and then the desired product(0.9 g, yield: 70%) was obtained as a solid by 
chlomatography(ethyl acetate:hexane=1:9). 
m.p.: 125.degree. C. 
.sup.1 H NMR(CDCl.sub.3): .delta. 3.8(s, 2H), 3.9(s, 3H), 5.5(s, 1H), 
6.6(s, 2H). 
Moreover, the present invention is directed to insecticidal compositions 
comprising the insecticidal compound of the present invention as an active 
compound. Such insecticidal compositions can be formulated in various 
forms, such as aqueous dispersions, emulsions, powders, granules and so 
forth. These compositions are preferred to comprise one or more active 
compounds of the present invention with one or more suitable adjuvants 
such as carriers and diluents which are chemically inert to the active 
compound. 
The exact concentration of the active compound in a composition thereof 
with an adjuvant therefor can vary, it is only necessary that the active 
compounds be present in sufficient amounts so as to make possible the 
application of an insecticidally effective dosage. 
For example, in the case where the compositions are emulsions or aqueous 
dispersions, the amount of the active compound is preferred to range from 
10 to 90% by weight. 
And in the case of powder compositions, the amount is preferred to range 
from 0.1 to 30% by weight; also in the case of granule compositions, the 
amount is preferred to range from 1 to 30% by weight. But, the amount of 
the active compound in the compositions is somewhat variable according to 
the purpose of use of the compositions. 
Preferred carriers to be employed in the compositions according to the 
present invention are liquid carriers which are selected from 
alcohols(i.e. monohydric alcohols like methanol, dihydric alcohols like 
ethyleneglycol, and trihydric alcohols like glycerine, etc.), ketones(i.e. 
acetone, methylethylketone, etc.), ethers(i.e. dioxane, tetrahydrofuran, 
cellosolve, etc.), aliphatic hydrocarbons(i.e. gasoline, kerosene, etc.), 
hydrocarbon halides (i.e. chloroform, carbon tetrachloride, etc.), acid 
amides (i.e. dimethylformamide, etc.), esters (i.e. butyl acetate, ethyl 
acetate, glyceride, etc.), and nitriles (i.e. acetonitrile, etc.), and 
solid carriers which are selected from mineral particles such as kaolin, 
clay, bentonite, acid clay, talc, diatomaceous earth, silica and sand, and 
vegetable powers such as arbor. Said liquid carriers can be used 
separately or in the company of one or more other liquid carriers. 
The insecticidal composition of the present invention may include 
emulsifying agents, spreaders, dispersing agents or permeating agents. 
Also, the composition may include noionic, anionic or cationic 
surfactants, for example, fatty acid soda or polyoxyalkylesters, 
alkylsulfonates or polyethyleneglycolethers. 
On the other hand, one of the compounds of the present invention or 
compositions containing the same, can be advantageously employed in 
combination with one or more additional pesticidal compounds which are 
active agricultural chemicals. Such additional pesticidal compounds may be 
insecticides, herbicides, plant hormones and sterilizers, and if 
necessary, fertilizers. 
______________________________________ 
Composition 1 (Emulsion) 
______________________________________ 
Compound No. 23 20% (by weight) 
xylene 75% 
polyoxyethylenglycolether 
5% 
______________________________________ 
The foregoing components were mixed to form an emulsion composition. 
______________________________________ 
Composition 2 (Powder) 
______________________________________ 
Compound No. 20 5% (by weight) 
kaoline 94.6% 
silicon (antifoaming agent) 
0.3% 
polyoxyethylenglycolether 
0.1% 
______________________________________ 
The foregoing components were mixed to form a powder composition. 
______________________________________ 
Composition 3 (Aqueous dispersion) 
______________________________________ 
Compound No. 24 30% (by weight) 
sodium lignosulfonate 
5% 
polyoxyethyleneglycolether 
5% 
bentonite 60% 
______________________________________ 
The foregoing components were mixed to form an aqueous dispersion 
composition. 
______________________________________ 
Composition 4 (Granules) 
______________________________________ 
Compound No. 19 10% (by weight) 
sodium lignosulfonate 
5% 
bentonite 85% 
______________________________________ 
The foregoing components were kneaded along with water and formed into a 
granular composition. 
To demonstrate the superior effect of the compounds which were prepared in 
accordance with the present invention, test solutions with 500 ppm were 
prepared for the first insecticidal tests unless otherwise specified. 
The insecticidal rates (%) were calculated from these solutions. In the 
case of an insecticidal rate of 100%, the concentration of the test 
solution was gradually reduced until the LC.sub.50 value, namely the 
concentration (ppm) which gives an insecticidal rate of 50%, was 
determined. 
This test is illustrated by the following examples, but should not be 
construed to be limited thereto. 
TEST 1 
Insecticidal test for Diamond-backmoth 
Diamond-backmoths (Plutella Xylostella Linnaeus) were successively reared 
using cabbage, and the third instar larvae thereof were tested. For the 
insecticidal test, a piece of cabbage leaf 9 cm in diameter was dipped in 
a test solution for 30 minutes and air-dried for 30 minutes. The dried 
piece of cabbage leaf was put in a petri dish, and 10 of the third instar 
larvae were inoculated therein. The petri dish was capped and placed in a 
incubator. At 120 hours after 24 hours, the number of killed moths was 
examined to determine the insecticidal rate(%), and then the tested 
cabbage leaf was replaced with a new one every 48 hours. 
The results are shown in Table 4. 
TABLE 4 
______________________________________ 
Compound No. Insecticidal Rate (%) 
______________________________________ 
2 100 
5 100 
6 100 
7 100 
8 40 
9 80 
10 80 
12 100 
13 100 
14 100 
15 100 
16 100 
17 100 
18 100 
19 100 
20 70 
22 100 
23 100 
24 100 
26 100 
no treatment 0 
______________________________________ 
Those compounds which produced an insecticidal rate of 100% at 500 ppm and, 
for comparison, commercial insecticidals(controls) were tested according 
to the method mentioned above, and the LC.sub.50 values were determined. 
The results are shown in Table 5. 
TABLE 5 
______________________________________ 
Compound No. LC.sub.50 (ppm) 
______________________________________ 
Dimilin (control) 100.about.125 
Chlorofluazuron (control) 
0.035 
2 20 
5 2.5 
6 20 
7 40 
13 3 
14 10 
16 50 
17 10 
18 5 
19 3 
22 0.9 
23 0.15 
24 0.5 
______________________________________ 
TEST 2 
Insecticidal test for Tobacco cutworm 
Tobacco cutworms(Spodop-tera litura) were successively reared using 
cabbage, and the third instar larvae thereof were tested. For the 
insecticidal test, a piece of cabbage leaf 9 cm in diameter was dipped in 
a test solution for 30 seconds and air-dried for 30 minutes. The dried 
piece of cabbage leaf was put in a petri dish 9 cm in diameter, and 10 of 
the third instar larvae were inoculated therein. The petri dish was placed 
in an incubator, and at 120 hours, the number of killed cutworms was 
examined to determine the insecticidal rate(%). The tested cabbage leaf 
was replaced with a new one every 48 hours. 
The results are shown in Table 6. 
TABLE 6 
______________________________________ 
Compound No. Insecticidal Rate (%) 
______________________________________ 
2 100 
5 100 
6 100 
7 100 
8 100 
9 80 
10 80 
11 60 
12 100 
13 100 
14 100 
15 100 
16 100 
17 100 
18 100 
19 100 
20 100 
21 100 
22 100 
23 100 
24 100 
26 100 
no treatment 0 
______________________________________ 
Those compounds which produced an insecticidal rate of 100% at 500 ppm and 
for comparison, commercial insecticidals (controls) were tested according 
to the method mentioned above, and the LC.sub.50 values were determined. 
The results are shown in Table 7. 
TABLE 7 
______________________________________ 
Compound No. LC.sub.50 (ppm) 
______________________________________ 
Dimilin (control) 3.3 
Chlorofluazuron (control) 
0.022 
2 0.7 
5 0.04 
6 0.04 
7 0.15 
8 3.5 
13 7 
14 1.5 
16 5 
17 1.5 
18 3 
19 0.7 
20 0.2 
21 0.4 
22 0.4 
23 0.2 
24 0.06 
26 4 
______________________________________ 
From the results of the above test, it is demonstrated that the benzoyl 
urea derivatives having pyrazole group according to the present invention 
exhibit excellent bioactivity against Diamond-backmoth and Tobacco 
cutworm; namely activity similar to chlorfluazuron but superior to 
Dimilin. 
Moreover, the present novel benzoyl urea derivatives can be prepared 
cheaply via simple processes starting form readily available raw materials 
as compared to existing high priced chitin inhibitor insecticides.