Insecticidal nitro-substituted heterocyclic compounds of the formula ##STR1## wherein R.sup.1 represents hydrogen, cyano or C.sub.1-4 alkyl, PA1 m represents 0 or 1, PA1 n represents 0 or 1, PA1 R.sup.2 represents hydrogen or C.sub.1-4 alkyl, PA1 R.sup.3 represents hydrogen, C.sub.1-6 alkyl optionally substituted by cyano, halogen or C.sub.1-4 alkoxy, C.sub.3-4 alkenyl, C.sub.3-4 alkynyl, optionally substituted phenyl, optionally substituted benzyl or optionally substituted heterocyclic-methyl, PA1 T represents an optionally substituted two- or three-membered divalent or trivalent chain comprising hetero atoms and/or carbon atom, and PA1 A represents optionally substituted phenyl or an optionally substituted five- or six-membered heterocyclic radical comprising at least one hetero atom selected from the group consisting of N, O and S.

The present invention relates to novel nitro-substituted heterocyclic 
compounds, to processes for their preparation and to their use as 
insecticides. 
A number of nitro-substituted heterocyclic compounds is already known from 
literature, for example 
A) Chem. Ber., Vol. 119, pp. 2208-2219 (1968); 
B) J. Chem. Soc. Perkin Trans. I, 1979, pp. 2361-2363; 
C) Journal of Heterocyclic Chem., Vol. 17, p. 1413 (1980); 
D) Heterocycles 15, p. 437 (1980) 
Typical examples of such compounds are the following: 
##STR2## 
Furthermore, it has already been disclosed that a certain nitro-substituted 
heterocyclic compound has insecticidal properties (see Japanese Patent 
Laid-open No. 3184/1989). 
There have now been found novel nitro-substituted heterocyclic compounds of 
the formula (I) 
##STR3## 
wherein R.sup.1 represents hydrogen, cyano or C.sub.1-4 alkyl, group, 
m represents 0 or 1, 
n represents 0 or 1, 
R.sup.2 represents hydrogen or C.sub.1-4 alkyl, 
R.sup.3 represents hydrogen; C.sub.1-6 alkyl optionally substituted by 
cyano, halogen or C.sub.1-4 alkoxy, C.sub.3-4 alkenyl, C.sub.3-4 alkynyl, 
optionally substituted phenyl, optionally substituted benzyl or optionally 
substituted heterocyclic-methyl, 
T represents an optionally substituted two- or three-membered divalent or 
trivalent chain comprising hetero atoms and/or carbon atoms, and 
Z represents optionally substituted phenyl or an optionally substituted 
five- or six-membered heterocyclic radical comprising at least one hetero 
atom selected from the group consisting of N, O and S. 
The compounds of the formula (I) can be obtained as follows: 
a): (when m is 1 and T is 
##STR4## 
wherein R.sup.4 is C.sub.1-4 alkyl, C.sub.3-7 cycloalkyl, benzyl 
optionally substituted by halogen, phenyl optionally substituted by 
halogen or C.sub.1-6 alkyl, or 2-chloro-5-pyridylmethyl), compounds of the 
formula (II) 
##STR5## 
wherein R.sup.1, n, R.sup.2 and R.sup.3 have the same meanings as 
mentioned before, are reacted with compounds of the formula (III) 
EQU NH.sub.2 --R.sup.4 (III) 
wherein R.sup.4 has the same meaning as mentioned before, in the presence 
of formaldehyde, and if appropriate, in the presence of inert solvents, 
b): (when m is 1 and T is 
##STR6## 
wherein.rarw.means linkage with the nitrogen atom), the aforementioned 
compounds of the formula (II) are reacted with chlorocarbonylsulphenyl 
chloride in the presence of inert solvents and if appropriate in the 
presence of an acid binder, 
c): (when m is 1 and T is 
##STR7## 
wherein the symbol.rarw.is the same as mentioned above), the 
aforementioned compounds of the formula (II) are reacted with compounds of 
the formula (IV) 
EQU CH.sub.2 .dbd.CHCOOR (IV) 
wherein R represents a lower alkyl group, in the presence of inert 
solvents, 
d): (when m is 1 and T is 
##STR8## 
wherein the symbol.rarw.is the same as mentioned above), the 
aforementioned compounds of the formula (II) are reacted with compounds of 
the formula (V) 
EQU HC.tbd.CCOOR (V) 
wherein R has the same meaning as mentioned before, in the presence of 
inert solvents, 
e): (when m is 1 and T is 
##STR9## 
wherein the symbol.rarw.is the same as mentioned above), the 
aforementioned compounds of the formula (II) are reacted with compounds of 
the formula (VI) 
EQU ROOCC.tbd.CCOOR (VI) 
wherein R has the same meaning as mentioned above, in the presence of inert 
solvents, 
f): (when m is 1 and T is 
##STR10## 
wherein the symbol.rarw.is the same as mentioned above and Q is C.sub.1-4 
alkyl or C.sub.1-4 alkoxycarbonylimino), compounds of the formula (VII) 
##STR11## 
wherein R.sup.1, n, R.sup.2, R.sup.3, Z and Q have the same meanings as 
mentioned above, are oxidized in the presence of inert solvent, 
g): (when m is 1 and T is --N.dbd.N--), the aforementioned compounds of the 
formula (II) are reacted with 4-chlorobenzenesulfonylazide in the presence 
of inert solvents, 
h): (when m is 1 and T is 
##STR12## 
the aforementioned compounds of the formula (II) are reacted with oxazolyl 
chloride in the presence of inert solvents and if appropriate in the 
presence of an acid binder, 
i): (when m is 1 and T is 
##STR13## 
the aforementioned compounds of the formula (II) are reacted with 
chlorocarbonyl isocyanate in the presence of inert solvents and if 
appropriate in the presence of an acid binder, 
j): (when m is 1 and T is 
##STR14## 
wherein the symbol.rarw.has the same meaning as mentioned before), the 
aforementioned compounds of the formula (II) are reacted with 
halopropionitrile of the formula (VIII) 
EQU Hal--CH.sub.2 CH.sub.2 CN (VIII) 
wherein Hal means halogen, in the presence of inert solvents and if 
appropriate in the presence of an acid binder, 
k): (when m is 1 and T is 
##STR15## 
wherein the symbol.rarw.has the same meaning as mentioned before and 
R.sup.4 represents hydrogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy), the 
aforementioned compounds of the formula (II) are reacted with compounds of 
the formula (IX) 
##STR16## 
wherein R.sup.4 and Hal have the same meanings as mentioned before, in the 
presence of inert solvents and if appropriate in the presence of an acid 
binder, 
l): (when m is 1, R.sup.3 is hydrogen atom, and T is --CH.dbd.CH--), 
compounds of the formula (X) 
##STR17## 
wherein R.sup.1, n, R.sup.2, Z and R have the same meanings as mentioned 
before, are reacted with acid in the presence of inert solvents, 
m): (when m is 1, R.sup.3 has the same meaning as defined before, excluding 
hydrogen, and T is --CH.dbd.CH--, wherein R.sup.3 is denoted as R.sup.5), 
compounds of the formula (Il) 
##STR18## 
wherein R.sup.1, n, R.sup.2 and Z have the same meanings as mentioned 
before, are reacted with compounds of the formula (XI) 
EQU R.sup.5 --Hal (XI) 
wherein R.sup.5 and Hal have the same meanings as mentioned before, in the 
presence of inert solvents and if appropriate in the presence of an acid 
binder, or 
n): compounds of the formula (XII) 
##STR19## 
wherein m, R.sup.3 and T have the same meanings as mentioned before and M 
means methylthio or halogen, are reacted with compounds of the formula 
(XIII) 
##STR20## 
wherein R.sup.1, n, R.sup.2 and Z have the same meanings as mentioned 
before, in the presence of inert solvents and if appropriate in the 
presence of an acid binder. 
The novel nitro-substituted heterocyclic compounds exhibit powerful 
insecticidal properties. 
Surprisingly, the nitro-substituted heterocyclic compounds according to the 
invention exhibit a substantially greater insecticidal activity than those 
known from the aforementioned prior art. 
Among the nitro-substituted heterocyclic compounds according to the 
invention, of the formula (I), preferred compounds are those in which 
R.sup.1 represents hydrogen, cyano group or methyl, 
m represents 0 or 1, 
n represents 0 or 1, 
R.sup.2 represents hydrogen or methyl, 
R.sup.3 represents hydrogen, methyl, ethyl, propyl, butyl, chloro- or 
fluoro-substituted C.sub.1-2 alkyl, alkoxyalkyl having a total of from 2 
to 4 carbon atoms, cyano-substituted C.sub.1-2 alkyl, allyl, propargyl, 
phenyl which may be substituted by C.sub.1-4 alkyl or halogen, benzyl 
which may be substituted by halogen, or pyridylmethyl which may be 
substituted by halogen, 
T represents optionally substituted two- or three-membered divalent or 
trivalent chain comprising nitrogen or sulfur and carbon atoms, wherein 
said optional substituent may include C.sub.1-14 alkyl, C.sub.2-4 alkenyl, 
C.sub.2-4 alkynyl, halogen, C.sub.3-7 -cycloalkyl, nitro, oxo, thioxo, 
phenyl opitionally substituted by halogen or C.sub.1-6 alkyl, benzyl 
optionally substituted by halogen, C.sub.1-4 alkylimino, C.sub.1-4 
alkoxy-carbonylimino, substituted amino, C.sub.1-2 alkyl optionally 
substituted by cyano, C.sub.2-4 (in total) alkoxyalkyl, 
2-chloro-5-pyridylmethyl, C.sub.1-4 alkoxy, imino, or C.sub.1-4 
alkoxycarbonyl, and 
Z represents phenyl optionally substituted by halogen or cyano, a 
five-membered heterocyclic group optionally substituted by halogen or 
C.sub.1-4 alkyl, the heterocyclic group comprising one or two nitrogen 
atoms and an oxygen atom or sulfur atom, or a six-membered heterocyclic 
group optionally substituted by halogen or C.sub.1-4 alkyl, the 
heterocyclic group comprising one or two nitrogen atoms. 
Very particularly preferred nitro-substituted heterocyclic compounds of 
formula (I) are those in which 
R.sup.1 represents hydrogen, or methyl, 
m represents 0 or 1, 
n represents 0 or 1, 
R.sup.2 represents hydrogen or methyl, 
R.sup.3 represents hydrogen, methyl, fluoro-substituted C.sub.1-2 alkyl, 
2-methoxyethyl, 2-cyanoethyl, allyl, propargyl, phenyl, benzyl optionally 
substituted by chlorine, or 2-chloro-5-pyridylmethyl, T represents 
optionally substituted two- or three-membered divalent or trivalent chain 
comprising a nitrogen atom or sulfur atom and carbon atoms, wherein said 
optional substituent may include methyl, ethyl, propyl, isopropyl, butyl, 
allyl, propargyl, chlorine, cyclohexyl, nitro, oxo, thioxo, phenyl 
optionally substituted by chlorine or C.sub.1-4 alkyl, benzyl optionally 
substituted by chlorine or fluorine, C.sub.1-2 alkylimino, C.sub.1-2 
alkoxy-carbonylimino, N-methyl-N-(2-chloro-5-pyridyl)amino, 
.alpha.-methyl-4-chlorobenzylamino, 2-ethoxyethylamino, cyanomethyl, 
2-methoxyethyl, 2-chloro-5-pyridylmethyl, C.sub.1-2 alkoxy, imino, or 
ethoxycarbonyl, and Z represents phenyl optionally substituted by chlorine 
or cyano, thiazolyl optionally substituted by chlorine or methyl, or 
pyridyl optionally substituted by chlorine or methyl. 
Specifically, the following compounds may be mentioned: 
2-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-3-nitropyridine, 
2-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-3-nitropyrrole, 
2-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-1-methyl-3-nitropyrrole, 
4-(2-chloro-5-pyridylmethylamino)-1,3-dimethyl-5-nitro-1,2,3,6-tetrahydropy 
rimidine, 
4-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-3-methyl-5-nitro-2-thiazolon 
e, and 
4-(2-chloro-5-pyridylmethylamino)-1-dodecyl-3-methyl-5-nitro-1,2,3,6-tetrah 
ydropyrimidine. 
In the process a), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and 
methylamine, for example, the reaction can be expressed as follows: 
##STR21## 
In the process b), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and 
chlorocarbonylsulfenyl chloride, for example, the reaction can be 
expressed as follows: 
##STR22## 
In the process c), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and methyl 
acrylate, for example, the reaction can be expressed as follows: 
##STR23## 
In the process d), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and 
propynoic acid methyl ester, for example, the reaction can be expressed as 
follows: 
##STR24## 
In the process e), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and 
dimethyl butyne (2) dioic acid, for example, the reaction can be expressed 
as follows: 
##STR25## 
In the process f), if use is made, as starting material, of 
3-(2-chloro-5-pyridylmethylamino)-3-methylamino-2-nitrothioacrylic acid 
ethoxycarbonylimide and bromine, for example, the reaction can be 
expressed as follows: 
##STR26## 
In the process g), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and 
4-chlorobenzene sulfonylazide, for example, the reaction can be expressed 
as follows: 
##STR27## 
In the process h), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and oxalyl 
chloride, for example, the reaction can be expressed as follows: 
##STR28## 
In the process i), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and 
chloro-carbonyl isocyanate, for example, the reaction can be expressed as 
follows: 
##STR29## 
In the process j), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene and 
3-chloropropionitrile, for example, the reaction can be expressed as 
follows: 
##STR30## 
In the process k), if use is made, as starting material, of 
1-amino-1-(N-methyl-2-chloro-5-pyridylmethylamino)-2-nitroethylene and 
chloroacetone, for example, the reaction can be expressed as follows: 
##STR31## 
In the process l), if use is made, as starting material, of 
1-(2-chloro-5-pyridylmethylamino)-1-(2,2-diethoxyethylamino)-2-nitroethyle 
ne and concentrated hydrochloric acid, for example, the reaction can be 
expressed as follows: 
##STR32## 
In the process m), if use is made, as starting material, of 
2-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-3-nitropyrrol and dimethyl 
sulfate as alkylating agent, for example, the reaction can be expressed as 
follows: 
##STR33## 
In the process n), if use is made, as starting material, of 
2-chloro-3-nitropyridine and N-(2-chloro-5-pyridylmethyl)-methylamine, for 
example, the reaction can be expressed as follows: 
##STR34## 
In the processes a), b), c), d), e), g), h), i), j) and k), the compounds 
of the formula (II) as a starting material mean those based on the 
aforementioned definitions of R.sup.1, n, R.sup.2 and R.sup.3. 
In the formula (II), R.sup.1, n, R.sup.2 and R.sup.3 preferably have the 
same meanings as already given above for the formula (I) as preferred. 
The compounds of the formula (II) include known compounds. (see Japanese 
Patent Laid-open 65047/1984 or EP-OS 302,389) 
As example, there may be mentioned 
1-(2-chloro-5-pyridylmethylamino)-1-methylamino-2-nitroethylene. 
In the process a), the compounds of the formula (III) as a starting 
material mean those based on the aforementioned definition of R.sup.4. 
In the formula (III), R.sup.4 preferably means methyl, ethyl, propyl, 
isopropyl, butyl, cyclohexyl, benzyl optionally substituted by chlorine or 
fluorine, or 2-chloro-5-pyridylmethyl. 
The compounds of the formula (III) are for the most part well-known as 
primary amines in the field of organic chemistry. As examples, there may 
be mentioned: methylamine, ethylamine, propylamine, isopropylamine, 
cyclohexylamine and benzylamine, etc. 
In the process c), the compounds of the formula (IV) as a starting material 
mean those based on the aforementioned definition of R. 
In the formula (IV), R preferably means C.sub.1-4 alkyl, such as methyl, 
ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl and tert-butyl. 
The compounds of the formula (IV) are well-known in the field of organic 
chemistry. As example there may be methyl acrylate. 
In the process d), the compounds of the formula (V) as a starting material 
mean ones based on the aforementioned definition of R. 
The compounds of the formula (V) are well-known in the field of organic 
chemistry. As example there may be propynoic acid methyl ester. 
In the process e), the compounds of the formula (VI) as a starting material 
mean ones based on the aforementioned definition of R. 
The compounds of the formula (VI) are well-known in the field of organic 
chemistry. As example there may be butyne (2) dioic acid dimethyl. 
In the process f), the compounds of the formula (VII) as a starting 
material mean ones based on the aforementioned definitions of R.sup.1, n, 
R.sup.2, R.sup.3, Z or Q. 
In the formula (VII), R.sup.1, n, R.sup.2, R.sup.3 and Z preferably have 
the same meanings as already given above for the formula (I) as the 
preferred. Q preferably represents methyl, ethyl, methoxycarbonylimino or 
ethoxycarbonylimino. 
The compounds of the formula (VII) can be obtained by a process comprising 
reacting the aforementioned compounds of the formula (II) with compounds 
of the formula (XIV) 
EQU Q--NCS (XIV) 
wherein Q has the same meaning as mentioned before, in the presence of 
inert solvents. 
The above compounds of the formula (XIV) are known, and as example there 
ethoxycarbonyl isothiocyanate. 
In the process j), the compounds of the formula (VIII) as a starting 
material mean those based on the aforementioned definition of Hal. 
In the formula (VIII), Hal preferably represents chlorine, bromine or 
iodine. 
The compounds of the formula (VIII) are well-known, and as example there 
may be mentioned 3-chloropropiononitrile. 
In the process k), the compounds of the formula (IX) as a starting material 
mean those based on the aforementioned definitions of R.sup.4 and Hal. 
The compounds of the formula (IX) are well-known in the field of organic 
chemistry, and as examples there are chloroacetone and methyl 
chloroacetate. 
In the process l), the compounds of the formula (X) as a starting material 
means those based on the aforementioned definitions of R.sup.1, n, 
R.sup.2, Z and R. 
In the formula (X), R.sup.1, n, R.sup.2, Z and R preferably have the same 
meanings as already given above. As examples there may be mentioned: 
1-(2-chloro-5-pyridylmethylamino)-1-(2,2-diethoxyethylamino)-2-nitroethylen 
e, and 
1-[N-methyl-N-(2-chloro-5-pyridylmethyl)amino]-1-(2,2-diethoxydiethylamino) 
-2-nitroethylene. 
In the process m), the compounds of the formula (XI) as a starting material 
mean those based on the aforementioned definitions of R.sup.5 and Hal. 
In the formula (XI), R.sup.5 preferably represents definitions other than 
hydrogen of the aforementioned preferred definitions of R.sup.3, and Hal 
preferably has the same meaning as already given above. As examples, an 
alkylating agent such as chloromethane, iodomethane, etc., can be employed 
and, besides the compounds of the formula (XI), dimethyl sulfate and 
diethyl sulfate which are well-known as alkylating agents may be used in 
place of the compounds of the formula (XI). 
In the process n), the compounds of the formula (XII) as a starting 
material mean those based on the aforementioned definitions of R.sup.3, T 
and M. 
In the formula (XII), R.sup.3 and T preferably have the same meanings as 
already given above, and M preferably represents methylthio, chlorine or 
bromine. As examples of the compounds of the formula (XII), there may be 
mentioned 
2-chloro-3-nitropyridine, 
1,3-dimethyl-4-methylthio-5-nitro-1,2,3,6-tetrahydropyrimidine, 
2-methylthio-3-nitro-1-phenylpyrrol-4,5-dione, and 
3-methyl-4-methylthio-5-nitrothiazolone. 
The above 
1,3-di-substituted-4-methylthio-5-nitro-1,2,3,6-tetrahydropyrimidines can 
be obtained by a process comprising reacting compounds of the formula (XV) 
##STR35## 
wherein R.sup.3 has the same meaning as mentioned before, with the 
aforementioned compounds of the formula (III) in the presence of 
formaldehyde. 
The compounds of the formula (XV) include known compounds described for 
instance in Japanese Patent Laid-open 17557/1986 and as example there may 
be mentioned N-methyl-1-methylthio-2-nitroethene amine. Furthermore, 
2-anilino-2-methyltho-1-nitroethylene described in Journal F. prakt. 
Chemie, Band 319, Heft 1, 1977, S 149-158 may be employed. 
In the aforementioned examples of the compounds of the formula (XII), 
2-methylthio-3-nitro-1-phenylpyrrol-4,5-dione is a known compound 
described in the aforecited Journal F. prakt. Chemie, Band 319, Heft 1, 
1977, S 149-158, and 3-substituted-4-methylthio-5-nitrothiazolones can be 
obtained by a process comprising reacting the compounds of the formula 
(XV) with chlorocarbonylsulfenylchloride. 
In the process n), the compounds of the formula (XIII) as a starting 
material mean those based on the aforementioned definitions of R.sup.1, n, 
R.sup.2 and Z. 
In the formula (XIII), R.sup.1, n, R.sup.2 and Z preferably have the same 
meanings as already given above. 
The compounds of the formula (XIII) are known (see EP-OS 302,389), and as 
examples there may be mentioned: 
N-(2-chloro-5-pyridylmethyl)-methylamine and 
N-(2-chloro-5-thiazolylmethyl)-methylamine. 
In carrying out the process (a) mentioned above, use may be made, as 
suitable diluent, of any inert solvents. 
Examples of such diluents are water; aliphatic, cycloaliphatic and 
aromatic, optionally chlorinated, hydrocarbons, such as hexane, 
cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene 
chloride, chloroform, carbon tetrachloride, ethylene chloride, 
trichloroethylene, chlorobenzene, and the like; ethers such as diethyl 
ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene 
oxide, dioxane, tetrahydrofuran and the like; nitriles such as 
acetonitrile, propionitrile, acrylonitrile and the like; alcohols such as 
methanol, ethanol, iso-propanol, butanol, ethylene glycol and the like; 
esters such as ethyl acetate, amyl acetate and the like; acid amides such 
as dimethyl formamide, dimethyl acetamide and the like; and sulfones and 
sulfoxides such as dimethyl sulfoxide, sulfolane and the like; and bases, 
for example, pyridine, etc. 
In the process a), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 150.degree. C., preferably about 60.degree. to about 
100.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process a) according to the invention is carried out, use is made, 
for instance, of 1 to 1.2 moles, preferably 1 to about 1.1 moles of the 
compounds of the formula (III) per mole of the compounds of the formula 
(II) for example, in the presence of about 2.2 moles of formaldehyde and 
ethanol to obtain the desired compounds of the formula (I). 
In carrying out the process b), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
The above-mentioned process b) may be carried out in the presence of an 
acid binders such as, for example, hydroxide, hydride, carbonate, 
bicarbonate, and alcoholate of alkali metal that are conventional acid 
binders, and tertiary amines such as, for example, triethylamine, diethyl 
aniline, pyridine, and the like. 
In the process b), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 150.degree. C., preferably about 10.degree. to about 
50.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process b) according to the present invention is carried out, use 
is made, for instance, of 1 to 1.2 moles, preferably from 1 to about 1.1 
moles of chlorocarbonylsulfenyl chloride per 1 mole of the compounds of 
the formula (II) for example to obtain the desired compounds of the 
formula (I). 
The process b) can be carried out according to the procedures disclosed by 
J. F. Pract. Chem. vol. 319, page 149. 
In carrying out the process c), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
In the process c), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 150.degree. C., preferably about 50.degree. to about 
100.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process c) according to the invention is carried out, use is made, 
for instance, of 1 to 1.2 moles, preferably from 1 to about 1.1 moles of 
the compounds of the formula (IV) per mole of the compounds of the formula 
(II) for example to obtain the desired compounds of the formula (I). 
In carrying out the process d), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
In the process d), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 150.degree. C., preferably about 50.degree. to about 
100.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process d) according to the present invention is carried out, use 
is made, for instance, of 1 to 1.2 moles, preferably from 1 to about 1.1 
moles of the compounds of the formula (V) per mole of the compounds of the 
formula (II) for example to obtain the desired compound represented by the 
formula (I). 
In carrying out the process e), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
In the process e), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 150.degree. C., preferably about 50.degree. to about 
100.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process e) according to the present invention is carried out, use 
is made, for instance, of 1 to 1.2 moles, preferably from 1 to about 1.1 
moles of the compounds of the formula (VI) per mole of the compounds of 
the formula (II) for example to obtain the desired compounds of the 
formula (I). 
The above-mentioned processes c), d), and e) can be carried out according 
to the known Michael reaction. 
In carrying out the process f), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
In the process f), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 100.degree. C., preferably about 20.degree. to about 
60.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
The process f) according to the present invention can be carried out 
according to the process disclosed by Tetrahedron, vol. 33, page 1057; 
vol. 37, page 1470 and Indian J. Chem., 15B, 1977, pages 886-889. 
In carrying out the process g), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
In the process g), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 150.degree. C., preferably about 50.degree. to about 
80.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process g) according to the invention is carried out, use is made, 
for instance, of 1 to 1.2 moles, preferably from 1 to about 1.1 moles of 
4-chlorobenzenesulfonylazide per mole of the compounds of the formula (II) 
for example to obtain the desired compounds of the formula (I). 
The above-mentioned process g) can be carried out according to the process 
disclosed by J. Chem. Soc., Perkin I trans. 1979, pages 2361-2363. 
In carrying out the process h), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
The above mentioned process h) may be carried out in the presence of an 
acid binder such as exemplified in the process b). 
In the process h), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
-20.degree. C. to about 100.degree. C., preferably about 0.degree. C. to 
about 50.degree. C. In general, the reaction is allowed to proceed under 
normal pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process h) according to the invention is carried out, use is made, 
for instance, of 1 to 1.2 moles, preferably from 1 to about 1.1 moles of 
oxalyl chloride per mole of the compounds of the formula (II) for example 
to obtain the desired compounds of the formula (I). 
The above-mentioned process h) can be carried out according to a process 
similar to that disclosed in the above-mentioned J. F. Pract. Chem., vol. 
319, page 149. 
In carrying out the process i), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
The above mentioned process i) may be carried out in the presence of an 
acid binder such as exemplified in the process b). 
In the process i), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
-20.degree. C. to about 100.degree. C., preferably about 0.degree. C. to 
about 50.degree. C. In general, the reaction is allowed to proceed under 
normal pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process i) according to the invention is carried out, use is made, 
for instance, of 1 to 1.2 moles, preferably from 1 to about 1.1 moles of 
chlorocarbonyl isocyanate per mole of the compounds of the formula (II) 
for example to obtain the desired compounds of the formula (I). 
In carrying out the process j), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
The above mentioned process j) may be carried out in the presence of an 
acid binder such as exemplified in the process b). 
In the process j), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 100.degree. C., preferably about 20.degree. C. to about 
50.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process j) according to the invention is carried out, use is made, 
for instance, of about 1 to about 1.2 moles, preferably 1 to 1.1 moles of 
the compounds of the formula (VIII) per mole of the formula (II) for 
example to obtain the desired compounds of the formula (I). 
In carrying out the process k), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
The above mentioned process k) may be carried out in the presence of an 
acid binder such as exemplified in the process b). 
In the process k), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
-20.degree. C. to about 80.degree. C., preferably from about 0.degree. C. 
to about 50.degree. C. In general, the reaction is allowed to proceed 
under normal pressure, although it is also possible to employ a higher or 
lower pressure. 
When the process k) according to the invention is carried out, use is made, 
for instance, of about 1 to about 1.2 moles, preferably from about 1 to 
1.1 moles of the compounds of the formula (IX) per mole of the compounds 
of the formula (II) for example to obtain the desired compounds of the 
formula (I). 
The processes i), j) and k) mentioned above can be carried out in 
accordance with a process disclosed by Japanese Patent Application 
Disclosure No. 3184-1989. 
In carrying out the process l), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
In the process l), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
0.degree. to about 150.degree. C., preferably about 50.degree. to about 
80.degree. C. In general, the reaction is allowed to proceed under normal 
pressure, although it is also possible to employ a higher or lower 
pressure. 
In carrying out the process m), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
The above mentioned process m) may be carried out in the presence of an 
acid binder such as exemplified in the process b). 
In the process m), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of about 
-20.degree. C. to about 100.degree. C., preferably about 0.degree. C. to 
about 50.degree. C. In general, the reaction is allowed to proceed under 
normal pressure, although it is also possible to employ a higher or lower 
pressure. 
When the process m) according to the invention is carried out, use is made, 
for instance, of about 1 to about 1.2 moles, preferably from 1 to about 
1.1 moles of the compounds of the formula (XI) per mole of the compounds 
of the formula (II) for example to obtain the desired compounds of the 
formula (I). 
In carrying out the process n), use is made, as suitable diluent, of any 
inert solvents such as those exemplified in the above-mentioned process 
a). 
The above mentioned process n) may be carried out in the presence of an 
acid binder such as exemplified in the process b). 
In the process n), the reaction temperature can be varied within a wide 
range. In general, the reaction is carried out at a temperature of from 
about 0.degree. to about 150.degree. C., preferably from room temperature 
to about 80.degree. C. In general, the reaction is allowed to proceed 
under normal pressure, although it is also possible to employ a higher or 
lower pressure. 
When the process n) according to the invention is carried out, use is made, 
for instance, of about 1 to about 1.2 moles, preferably from 1 to about 
1.1 moles of the compounds of the formula (XIII) per mole of the compounds 
of the formula (XII) for example in the presence of an inert solvent such 
as alcohol to obtain the desired compounds of the formula (I). 
The active compounds are well tolerated by plants, have a favourable level 
of toxicity to warm-blooded animals, and can be used for combating 
arthropod pests, especially insects which are encountered in agriculture, 
in forestry, in the protection of stored products and of materials, and in 
the hygiene field. They are active against normally sensitive and 
resistant species and against all or some stages of development. The 
above-mentioned pest include: 
from the class of the Isopoda, for example Oniscus Asellus, Armadillidium 
vulgare and Porcellio scaber; 
from the class of the Diplopoda, for example Blaniulus quttulatus; 
from the class of the Chilopoda, for example Geophilus carpophagus and 
Scutigera spec.; 
from the class of the Symphyla, for example Scutigerella immaculata; 
from the order of the Thysanura, for example Lepisma saccharina; 
from the order of the Collembola, for example Onychiurus armatus; 
from the order of the Orthoptera; for example Blatta orientalis, 
Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta 
domesticus, Gryllotalpa spp., Locusta migrato ria migratorioides, 
Melanoplus differentialis and Schistocerca gregaria; 
from the order of the Dermaptera, for example Forficula auricularia; from 
the order of the Isoptera, for example Reticulitermes spp.; 
from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus 
spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.; 
from the order of the Mallophaga, for example Trichodectes spp. and 
Damalinea spp.; 
from the order of the Thysanoptera, for example Hercinothrips femoralis and 
Thrips tabaci, 
from the order of the Heteroptera, for example Eurygaster spp., Dysdercus 
intermedius, Piesma guadrata, Cimex lectularius, Rhodnius prolixus and 
Triatoma spp.; 
from the order of the Homoptera, for example Aleurodes brassicae, Bemisia 
tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, 
Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, 
Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, 
Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix 
cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, 
Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus 
spp. and Psylla spp.; 
from the order of the Lepidoptera, for example Pectinophora gossypiella, 
Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, 
Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis 
chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis 
citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, 
Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, 
Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, 
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria 
mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, 
Clysia ambiguella, Homona magnanima and Tortrix viridana; 
from the order of the Coleoptera, for example Anobium punctatum, 
Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, 
Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon 
cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna 
varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., 
Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, 
Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma 
spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, 
Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., 
Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, 
Amphimallon solstitialis and Costelytra zealandica; 
from the order of the Hymenoptera for example Diprion spp., Hoplocampa 
spp., Lasius spp., Monomorium pharaonis and Vespa spp.; 
from the order of the Diptera, for example Aedes spp., Anopheles spp., 
Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora 
erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., 
Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma 
spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia 
spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula 
paludosa; 
from the order of the Siphonaptera, for example Xenopsylla cheopis and 
Ceratophyllus spp.; 
from the class of the Arachnida, for example Scorpio maurus and Latrodectus 
mactans; 
from the order of the Aranina, for example Acarus siro, Argas spp., 
Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta 
oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma 
spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., 
Tarsonemus spp., Bryobia praetiosa, Panonychos spp. and Tetranychus spp. 
The plant-parasitic nematodes include Pratylenchus spp., Radopholus 
similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., 
Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., 
and Trichodorus spp. 
Furthermore, in the field of veterinary medicine, the novel compound of the 
present invention can effectively be employed for combating a variety of 
noxious animal-parasitic pests (internal- and external-parasitic pests), 
e.g., parasitic insects and nematodes. Such animal-parasitic pests may be 
exemplified as follows: 
From the class of insects, e.g., Gastrophilus spp., Stomoxys spp., 
Tricodectes spp., Rhodius spp., Ctenocephalides canis and the like. 
The active compounds can be converted into the customary formulations, such 
as solutions, emulsions, wet-table powders, suspensions, powders, foams, 
pastes, granules, aerosols, natural and synthetic materials impregnated 
with active compound, very fine capsules in polymeric substances, coating 
compositions for use on seed, and formulations used with burning 
equipment, such as fumigating cartridges, fumigating cans and fumigating 
coils, as well as ULV cold mist and warm mist formulations. 
These formulations may be produced in known manner, for example by mixing 
the active compounds with extenders, that is to say liquid or liquefied 
gaseous or solid diluents or carriers, optionally with the use of 
surface-active agents, that is to say emulsifying agents and/or dispersing 
agents and/or foam-forming agents. In the case of the use of water as an 
extender, organic solvents can, for example, also be used as auxiliary 
solvents. 
As liquid solvents diluents or carriers, there are suitable in the main, 
aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes, 
chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as 
chlorobenzenes, chloroethylenes or methylene chloride, aliphatic 
hydrocarbons, such as cyclohexane or paraffins, for example mineral oil 
fractions, alcohols, such as butanol or glycol as well as their ethers and 
esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl 
ketone or cyclohexanone, or strongly polar solvents, such as 
dimethylformamide and dimethyl-sulphoxide, as well as water. 
By liquefied gaseous diluents or carriers are meant liquids which would be 
gaseous at normal temperature and under normal pressure, for example 
aerosol propellants, such as halogenated hydrocarbons as well as butane, 
propane, nitrogen and carbon dioxide. 
As solid carriers there may be used ground natural minerals, such as 
kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or 
diatomaceous earth, and ground synthetic minerals, such as 
highly-dispersed silicic acid, alumina and silicates. As solid carriers 
for granules there may be used crushed and fractionated natural rocks such 
as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic 
granules of inorganic and organic meals, and granules of organic material 
such as sawdust, coconut shells, maize cobs and tobacco stalks. 
As emulsifying and/or foam-forming agents there may be used non-ionic and 
anionic emulsifiers, such as polyoxyethylene-fatty acid esters, 
polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol 
ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as 
albumin hydrolysis products. Dispersing agents include, for example, 
lignin sulphite waste liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulation. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, 
and trace nutrients, such as salts of iron, manganese boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain from 0.1 to 95 per cent by weight of 
active compound, preferably from 0.5 to 90 per cent by weight. 
The active compounds according to the invention can be present in their 
commerically available formulations and in the use forms, prepared from 
these formulations, as a mixture with other active compounds, such as 
insecticides, baits, sterilizing agents, acaricides, nematicides, 
fungicides, growth-regulating substances or herbicides. The insecticides 
include, for example, phosphates, carbamates, carboxylates, chlorinated 
hydrocarbons, phenylureas, substances produced by microorganisms. 
The active compounds according to the invention can furthermore be present 
in their commercially available formulations and in the use forms, 
prepared from these formulations, as a mixture with synergistic agents. 
Synergistic agent are compounds which increase the action of the active 
compounds, without it being necessary for the synergistic agent added to 
be active itself. 
The active compound content of the use forms prepared from the commercially 
available formulations can vary within wide limits. The active compound 
concentration of the use forms can be from 0.0000001 to 100% by weight of 
active compound, preferably between 0.0001 and 1% by weight. 
The compounds are employed in a customary manner appropriate for the use 
forms. 
When used against hygiene pests and pests of stored products, the active 
compounds are distinguished by an excellent residual action on wood and 
clay as well as a good stability to alkali on limed substrates.