5,7-dihydro-6H dibenz[c,e]azepine-6-(thio)carboximidic acid esters and pesticidal use thereof

The invention relates to compounds of the formula ##STR1## wherein R.sup.1, R.sup.2 and X have the significances given herein, their acid addition salts and the preparation of these substances, pest control compositions which contain these substances as active ingredients and the use of the active substances or compositions for the control of pests.

BRIEF SUMMARY OF THE INVENTION 
The invention relates to heterocyclic compounds, namely 
5,7-dihydro-6H-dibenz[c,e]azepine-6-(thio)carboximidic acid esters of the 
formula 
##STR2## 
wherein R.sup.1 is hydrogen or --Y--R.sup.3, 
R.sup.2 is C.sub.1-6 -alkyl, C.sub.3-6 -alkenyl or C.sub.3-6 -alkynyl 
substituted with C.sub.3-6 --cycloalkyl, aryl, aryloxy or heteroaryl, with 
the substitution being optional when R.sup.1 is --Y--R.sup.3, or 
R.sup.2 is unsubstituted C.sub.2-6 -alkyl or C.sub.2-6 -alkyl substituted 
with aryl or aryloxy and which is interrupted by one or two oxygen atoms, 
or 
R.sup.2 is aryl, heteroaryl, 2-tetrahydrofuranylmethyl, 
2-tetrahydropyranylmethyl or one of the groups (a) to (c) 
EQU --N.dbd.CR.sup.4 R.sup.5 ( a) 
EQU --Z--ON.dbd.CR.sup.4 R.sup.5 ( b) 
EQU --Z--NR.sup.6 R.sup.7 ( c) 
R.sup.3 is hydrogen; unsubstituted or substituted C.sub.1-6 -alkyl, 
C.sub.2-6 -alkenyl, C.sub.2-6 -alkynyl, C.sub.3-6 -cycloalkyl, phenyl, 
naphthyl, p-biphenylyl, benzylphenyl, phenoxyphenyl, benzoylphenyl, 
3,4-methylenedioxyphenyl or five- to six-membered heterocyclyl; a group 
--OR.sup.8 (d); or a group --NR.sup.9 R.sup.10 (e), 
R.sup.4 is C.sub.1-6 -alkyl, 
R.sup.5 is C.sub.1-6 -alkyl or phenyl, or 
R.sup.4 and R.sup.5 taken together are tetra-, penta- or hexamethylene, 
R.sup.6 is hydrogen or C.sub.1-4 -alkyl, 
R.sup.7 is C.sub.1-4 -alkyl, C.sub.2-5 -alkanoyl or C.sub.2-5 
-alkoxycarbonyl, 
or 
R.sup.6 and R.sup.7 taken together with the nitrogen atom to which they are 
attached are a five- to seven-membered unsubstituted heterocyclic group or 
which is substituted with one or two C.sub.1-4 -alkyl groups and which, in 
addition to the nitrogen can also have an additional 1 or 2 hetero atoms 
selected from oxygen, sulfur and nitrogen, and/or a keto function in the 
ring, 
R.sup.8 is C.sub.1-6 -alkyl, C.sub.2-6 -haloalkyl, 
C.sub.3-6 -alkenyl, C.sub.3-6 -alkynyl, benzyl or unsubstituted or 
substituted phenyl, 
R.sup.9 is hydrogen or C.sub.1-4 -alkyl, 
R.sup.10 is C.sub.1-6 -alkyl or unsubstituted or substituted phenyl, 
X is oxygen or sulfur, provided that when R.sup.2 is group (a), X is 
oxygen, 
Y is carbonyl, sulfinyl or sulfonyl, provided that when R.sup.3 is hydrogen 
or a group (d) or (e), Y is carbonyl, and 
Z is C.sub.1-4 -alkylene, 
as well as acid addition salts of the compounds of formula I in which 
R.sup.1 is hydrogen. 
The compounds in accordance with the invention, that is, the compounds of 
formula I and the acid addition salts mentioned above, are pest control 
agents which are especially suitable for the control of insects, nematodes 
and mites, for example, spider mites. Accordingly, the invention also 
embraces pest control compositions which contain compounds in accordance 
with the invention as the active substance, a process for the preparation 
of these compounds as well as the use of these compounds or compositions 
for the control of pests. 
DETAILED DESCRIPTION OF THE INVENTION 
The invention relates to 
5,7-dihydro-6H-dibenz[c,e]azepine-6-(thio)carboximidic acid esters of the 
formula 
##STR3## 
wherein R.sup.1 is hydrogen or --Y--R.sup.3, 
R.sup.2 C.sub.1-6 -alkyl, C.sub.3-6 -alkenyl or C.sub.3-6 -alkynyl 
substituted with C.sub.3-6 cycloalkyl, aryl, aryloxy or heteroaryl, with 
the substitution being optional when R.sup.1 is --Y--R.sup.3, or 
R.sup.2 is C.sub.2-6 -alkyl which can be substituted with aryl or aryloxy 
and which is interrupted by one or two oxygen atoms, or 
R.sup.2 is aryl, heteroaryl, 2-tetrahydrofuranylmethyl, 
2-tetrahydropyranylmethyl or one of the groups (a) to (c) 
EQU --N.dbd.CR.sup.4 R.sup.5 ( a) 
EQU --Z--ON.dbd.CR.sup.4 R.sup.5 ( b) 
EQU --Z--NR.sup.6 R.sup.7 ( c) 
R.sup.3 is hydrogen; unsubstituted or substituted C.sub.1-6 -alkyl, 
C.sub.2-6 -alkenyl, C.sub.2-6 -alkynyl, C.sub.3-6 -cycloalkyl, phenyl, 
naphthyl, p-biphenylyl, benzylphenyl, phenoxyphenyl, benzoylphenyl, 
3,4-methylenedioxyphenyl or five- to six-membered heterocyclyl; a group 
--OR.sup.8 (d); or a group --NR.sup.9 R.sup.10 (e), 
R.sup.4 is C.sub.1-6 -alkyl, 
R.sup.5 is C.sub.1-6 -alkyl or phenyl, or 
R.sup.4 and R.sup.5 taken together are tetra-, penta- or hexamethylene, 
R.sup.6 is hydrogen or C.sub.1-4 -alkyl, 
R.sup.7 is C.sub.1-4 -alkyl, C.sub.2-5 -alkanoyl or C.sub.2-5 
-alkoxycarbonyl, or 
R.sup.6 and R.sup.7 together with the nitrogen atom to which they are 
attached are a five- to seven-membered unsubstituted heterocyclic group or 
which is substituted with one or two C.sub.1-4 -alkyl groups and which, in 
addition to the nitrogen atom, can also have an additional 1 or 2 hetero 
atoms selected from oxygen, sulfur and nitrogen and/or a keto function in 
the ring, 
R.sup.8 is C.sub.1-6 -alkyl, C.sub.2-6 -haloalkyl, C.sub.3-6 -alkenyl, 
C.sub.3-6 -alkynyl, benzyl or unsubstituted or substituted phenyl, 
R.sup.9 is hydrogen or C.sub.1-4 -alkyl, 
R.sup.10 is C.sub.1-6 -alkyl or unsubstituted or substituted phenyl, 
X is oxygen or sulfur, provided that when R.sup.2 is group (a), X is 
oxygen, 
Y is carbonyl, sulfinyl or sulfonyl, provided that when R.sup.3 is hydrogen 
or a group (d) or (e). Y is carbonyl, and 
Z is C.sub.1-4 -alkylene, 
as well as acid addition salts of the compounds of formula I in which 
R.sup.1 is hydrogen. 
The compounds in accordance with the invention, that is, the compounds of 
formula I and the acid addition salts mentioned above, are pest control 
agents which are especially suitable for the control of insects, nematodes 
and mites, for example, spider mites. Accordingly, the invention also 
embraces pest control compositions which contain compounds in accordance 
with the invention as the active substance, a process for the preparation 
of these compounds as well as the use of these compounds or compositions 
for the control of pests. 
As used herein, "alkyl", "alkenyl", "alkynyl" and "alkylene" are 
straight-chain or branched aliphatic radicals Moreover, the alkenyl and 
alkynyl residues can have more than one double or triple bond, 
respectively. A halogen atom which may be present can be fluorine, 
chlorine, bromine or iodine. A group such as, for example, alkyl, alkenyl, 
alkynyl, aryl or heteroaryl, as such or as part of a larger group, which 
carries two or more halogen substituents can have the same or different 
halogen atoms As aryl or aryloxy there are to be understood preferably 
phenyl and naphthyl, and phenoxy and naphthyloxy, respectively, and as 
heteroaryl there are to be understood preferably heterocyclic groups 
having aromatic character such as pyridyl, furyl and thienyl as well as 
groups having a fused benzene ring, for example, quinolinyl and 
quinoxalinyl. The aryl, aryloxy and heteroaryl groups can bear one or more 
substituents. Exemplary of such substituents for aryl, aryloxy or 
heteroaryl when this itself is a substituent on a C.sub.1-6 -alkyl, 
C.sub.3-6 -alkenyl or C.sub.3-6 -alkynyl (R.sup.2 ), are one or two 
substituents selected from the group consisting of halogen, C.sub.1-6 
-alkyl, C.sub.1-4 -haloalkyl, C.sub.1-4 -alkoxy, C.sub.1-4 -haloalkoxy, 
C.sub.1-4 -alkylthio, C.sub.1-4 -haloalkylthio, nitro, cyano, phenyl and 
phenoxy. When R.sup.2 is substituted aryl or heteroaryl, the substituents 
are suitably one or two substituents selected from the group consisting of 
halogen, C.sub.1-4 - alkyl, C.sub.1-4 -haloalkyl, C.sub.1-4 -alkoxy, 
C.sub.1-4 - haloalkoxy, C.sub.1-4 -alkylthio, C.sub.1-4 -haloalkylthio, 
nitro and cyano. As substituents for C.sub.3-6 -cycloalkyl, there come 
into consideration up to 4 substituents selected from the group consisting 
of halogen, C.sub.1-4 -alkyl and C.sub.1-4 -alkoxy. In this case, a 
halogen substituent which may be present is preferably fluorine or 
chlorine. When R.sup.3 is substituted C.sub.1-6 -alkyl, C.sub.2-6 -alkenyl 
or C.sub.2-6 -alkynyl, the alkyl, alkenyl or alkynyl residue can be 
suitably independently mono- or multiply-substituted with halogen, 
C.sub.1-4 -alkoxy, cyano, or unsubstituted or substituted phenyl or 
phenoxy. In the case of the just-mentioned unsubstituted or substituted 
phenyl or phenoxy as well as in the case of unsubstituted or substituted 
phenyl, naphthyl, p-biphenylyl, benzylphenyl, phenoxyphenyl, benzoylphenyl 
or 3,4-methylenedioxyphenyl mentioned as a meaning for R.sup.3 itself, 
there come into consideration aromatic groups which are unsubstituted or 
independently mono- to tri-substituted with halogen, C.sub.1-4 -alkyl, 
C.sub.1-4 -haloalkyl, C.sub.1-4 -alkoxy, C.sub.1-4 -haloalkoxy, C.sub.1-4 
-alkylthio, C.sub.1-4 -haloalkylthio, nitro, cyano, amino, C.sub.1-4 
-alkylamino, di(C.sub.1-4 -alkyl)amino, carboxy or C.sub.2-5 
-alkoxycarbonyl. This also applies to R.sup.8 and R.sup.10 as 
unsubstituted or substituted phenyl. As five- to six-membered 
heterocyclyl, there are to be understood such heterocyclic groups which, 
in addition to ring carbon atoms, can have 1 to 3 hetero atoms selected 
from the group consisting of nitrogen, oxygen and sulfur in the ring and 
which are aromatic, partially saturated or completely saturated. 
Heterocyclic groups with a fused benzene ring also come into 
consideration. The heterocyclic groups can be unsubstituted or substituted 
with 1 to 2 halogen atoms, 1 cyano group, 1 C.sub.1-4 -alkyl residue, 1 
C.sub.1-4 -haloalkyl residue and/or 1 C.sub.1-4 -alkoxy group, and when a 
fused benzene ring is present this, in turn, can be substituted with one 
or more substituents selected from halogen, methyl, methoxy and 
trifluoromethyl. Pyridyl, pyrrolyl, piperidinyl, pyrazinyl, imidazolyl, 
1,2,4-triazolyl, furyl, thiophenyl, morpholinyl, quinolinyl and benzofuryl 
are examples of such heterocyclyl groups. 
When asymmetric carbon atoms are present in the compounds of formula I, the 
compounds occur in optically active form. In the case of those compounds 
of formula I in which aliphatic double bonds are present, geometric 
isomerism can also occur. In any event, the compounds of formula I occur 
in the [E]- or [Z]-form because of the presence of the imino double bond. 
Furthermore, atropic isomerism can occur. Formula I is accordingly 
intended to embrace all of the possible isomeric forms as well as their 
mixtures, for example, racemic mixtures and any [E/Z] mixtures. 
As acid addition salts of the compounds of formula I there come into 
consideration physiologically compatible salts. The compounds of formula I 
form salts with inorganic and organic acids, preferably hydrohalic acids 
such as hydrochloric acid and hydrobromic acid; nitric acid; phosphoric 
acid; sulfuric acid; mono- and bifunctional carboxylic acids and 
hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, 
fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and 
lactic acid; and sulfonic acids such as 1,5-naphthalene-disulfonic acid. 
A special group of compounds of formula I consists of those compounds of 
formula I, wherein R.sup.1, R.sup.2 and X have the same significances as 
hereinbefore and R.sup.3 is hydrogen; unsubstituted or substituted 
C.sub.1-6 -alkyl, C.sub.3-6 -alkenyl, C.sub.3-6 -alkynyl, C.sub.3-6 
-cycloalkyl, phenyl, naphthyl, p-biphenylyl, benzylphenyl, phenoxyphenyl, 
benzoylphenyl or five- to six-membered heterocyclyl; a group --OR.sup.8 
(d) in which R.sup.8 is C.sub.1-6 -alkyl or unsubstituted or substituted 
phenyl; or a group --NR.sup.9 R.sup.10 (e), in which R.sup.9 and R.sup.10 
have the significances given hereinbefore. 
R.sup.1 preferably is a group --Y--R.sup.3 and X preferably is oxygen. In 
the case of the compounds I in which R.sup.1 is hydrogen, R.sup.2 is 
preferably a group (b) or (c) in which Z is ethylene, while in the 
compounds of formula I in which R.sup.1 is a group --Y--R.sup.3, R.sup.2 
preferably is C.sub.1-6 -alkyl, especially C.sub.1-4 -alkyl, and 
independently thereof R.sup.3 preferably is unsubstituted or substituted 
phenyl, unsubstituted or substituted five- to six-membered heterocyclyl or 
a group (d) and Y preferably is carbonyl. 
Preferred compounds of formula I are: 
2-[(Isopropylideneamino)oxy]-ethyl 
5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
2-ethoxycarbonylamino-ethyl 
5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl N-benzoyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl 
N-(p-chlorobenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
ethyl N-isonicotinoyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl N-ethoxycarbonyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl 
N-(1-imidazolylcarbonyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate 
ethyl 
N-(p-bromobenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
ethyl 
N-(p-tert.butylbenzoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate 
ethyl 
N-(p-fluorobenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
ethyl N-methoxycarbonyl-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
cyclopropylmethyl 5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl 
N-(p-trifluoromethylbenzoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximi 
date, 
ethyl N-(p-anisoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
methyl N-benzoyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
propyl N-benzoyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl N-(2-furoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate and 
ethyl 
N-cyclopropylcarbonyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
of which the 1st, 3rd, 6th, 10th and 11th compounds are especially 
preferred. 
Representatives of the compounds of formula I are also the following: 
2-(2-phenoxyethoxy)-ethyl 
5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
3-pyridylmethyl 5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
2-piperidino-ethyl 5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
2-[(1-ethylpentylideneamino)oxy]-ethyl 
5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
2-[(cyclohexylideneamino)oxy]-ethyl 
5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
2-(N-methyl-methoxycarbonylamino)-ethyl 
5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
2-methoxycarbonylamino-propyl 
5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
methoxycarbonylaminomethyl 
5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
ethyl N-(2-picolinoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl N-formyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl N-phenylethynyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl 
N-(1-piperidinecarbonyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate 
ethyl 
N-(1,2,4-triazolyl-1-carbonyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carbox 
imidate, 
ethyl 
N-(o-methoxybenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
methyl 
N-(p-chlorobenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
propyl 
N-(p-chlorobenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
isopropyl 
N-(p-chlorobenzoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl N-(p-iodobenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
phenyl 5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
cyclohexanone 0-[(5,7-dihydro-6H-dibenz[c,e]azepin-6-yl)carboximidoyl] 
oxime, 
acetophenone 0-[(5,7-dihydro-6H-dibenz[c,e]azepin-6-yl)-carboximidoyl] 
oxime, 
2-dimethylaminoethyl 5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
2-ethylcarbonylamino-ethyl 
5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
ethyl 
N-propargyloxycarbonyl-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl 
N-(2-chloroisonicotinoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidat 
e, 
ethyl 
N-(2-cyanoisonicotinoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate 
ethyl 
N-(6-chloronicotinoyl)-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate, 
ethyl 
N-(p-benzylbenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
ethyl 
N-(p-benzoylbenzoyl)-5,7-dihydro-6H-dibenz[c,e]-azepine-6-carboximidate, 
ethyl 
N-[p-(p-chlorophenoxy)benzoyl]-5,7-dihydro-6H-dibenz[c,e]azepine-6-carboxi 
midate, and 
2-[(1-methylisobutylideneamino)oxy]-ethyl 
5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate. 
The processes in accordance with the invention for the preparation of the 
compounds of formula I and of their acid addition salts comprise: 
(a) for the preparation of those compounds of formula I in which R.sup.1 is 
hydrogen, reacting 5,7-dihydro-6H-dibenz[c,e]azepine-6-carbonitrile, that 
is, the cyanamide of the formula 
##STR4## 
with an alcohol or thiol of the formula 
EQU R.sup.2' --X'H III 
wherein 
R.sup.2' and X' have the significances of R.sup.2 and X, respectively, 
given above which apply when R.sup.1 is hydrogen, 
or with an alkali metal salt thereof, or 
(b) for the preparation of those compounds of formula I in which R.sup.1 is 
--Y--R.sup.3, reacting a carboximidic acid ester of the formula 
##STR5## 
wherein R.sup.2" and X" have significances of R.sup.2 and X, 
respectively, given above which apply when R.sup.1 is --Y--R.sup.3, with a 
carbonyl, sulfinyl or sulfonyl compound of the formula 
EQU Q--Y--R.sup.3 V 
wherein 
R.sup.3 and Y have the significances given above and 
Q is a leaving group, 
and, if desired, converting a compound of formula I obtained in which 
R.sup.1 is hydrogen by reaction with an acid into the corresponding acid 
addition salt. 
The reaction according to process variant a) is conveniently effected using 
an excess of an alcohol or thiol of formula III as the solvent and in the 
presence of a catalytic or stoichiometric amount of an alkali metal salt, 
especially the sodium or potassium salt, of the alcohol or thiol of 
formula III. In an additional embodiment, an alcohol or thiol of formula 
III is used as the reaction partner and a catalytic or stoichiometric 
amount of alkali metal cyanide, preferably sodium or potassium cyanide. An 
auxiliary solvent such as an aliphatio ether, for example, dimethoxyethane 
or tert.butyl methyl ether, or an optionally halogenated aromatic solvent, 
for example, toluene or chlorobenzene, can also be used. The reaction 
temperatures can be varied in a wide range, generally in the range of from 
10.degree. to 120.degree. C., preferably in the range from 40.degree. to 
100.degree. C. 
The reaction according to process variant (b) is a N-acylation, 
N-sulfinylation or N-sulfonylation and can be carried out under the usual 
reaction conditions employed for such a reaction. As compounds of formula 
V, the corresponding halides, especially chlorides (Q is halogen or 
chlorine) are preferred, but acid anhydrides [Q--Y--R.sup.3 is 
O(COR.sup.3).sub.2 ], mixed acid anhydrides, especially those with 
aliphatic or aromatic carboxylic or sulfonic acids [Q--Y--R.sup.3 is 
O(Y'R.sup.3) (Y"R.sup.11) in which Y' and Y" each independently are 
carbonyl or sulfonyl and R.sup.11 is an aliphatic or aromatic group], as 
well as lower alkyl, benzyl or aryl esters, and imidazolides come into 
consideration. 
The reaction is conveniently effected in the presence of an inert organic 
diluent such as an aromatic hydrocarbon, for example, benzene or toluene; 
an aliphatic or cyclic ether, for example, diethyl ether, tert.butyl 
methyl ether, tetrahydrofuran or dioxane; a halogenated aliphatic 
hydrocarbon, for example, methylene chloride or 1,2-dichloroethane; 
acetonitrile; or a dialkylamide, for example, dimethylformamide, at a 
temperature in the range of from -20.degree. C. to 100.degree. C., 
preferably in the range of from -10.degree. C. to 50.degree. C. 
As a rule, a carboximidic acid ester of formula IV is reacted with a 
compound of formula V in the presence of an acid- binding agent such as, 
for example, an inorganic base, for example, potassium carbonate, or an 
organic base, for example, triethylamine, pyridine or quinoline, whereby 
any of the organic bases mentioned can simultaneously serve as the 
solvent. 
The compounds of formula I which exist as two or more isomers are obtained, 
insofar as no planned synthesis for the isolation of pure isomers is 
carried out, in each case as a mixture of the respective isomers. The 
isomers can be separated according to known methods or, if desired, they 
can also be prepared, for example, by synthesis from the corresponding 
optically active starting materials. E/Z-isomeric mixtures can be 
separated into the pure isomers, for example, by chromatography or 
fractional crystallization. 
For the preparation of the acid addition salts of the compounds of formula 
I, the compounds I are reacted with the desired acids in the usual manner, 
for example, by dissolving the compound of formula I in a suitable solvent 
and adding the acid thereto. 
The isolation and the purification of the thus-obtained prepared compounds 
of formula I or of the acid addition salts can be effected according to 
known methods. 
The cyanamide of formula II, which is used as the starting material in 
process variant a) is known, for example, from European Patent Publication 
No. 192,034. 
In the case of the carboximidic acid esters of formula IV, which are used 
as starting materials in process variant (b), some are known from European 
Patent Publication No. 192,034 and some can be produced in accordance with 
process variant a). Furthermore, the compounds of formulas III and V which 
are used as starting materials and the alkali metal salts of the former 
are to a large extent known or can be produced according to known methods. 
The compounds of formula I and their acid addition salts are of value as 
pesticides. They have been shown to be especially valuable for the control 
of mites, insects and nematodes, especially of 
mites which are of importance in plant protection such as, for example, 
Tetranychidae (spider mites), especially Tetranychus urticae, Tetranychus 
cinnabarinus, Tetranychus turkestani, Tetranychus McDanieli, Tetranychus 
kanzawai; 
Panonychus ulmi, Panonychus citri; 
Phyllocoptruta oleivora; 
Aculus schlechtendali; 
Phyllocoptes vitis; 
Aceria essigi, Aceria gracilis; 
Cedidophyopsis ribis: 
Eriophyes vitis; Eriophyes sheldoni, Eriophyes tulipae; 
Eotetranychus sexmaculatus, Eotetranychus carpini; 
Hemitarsonemus latus; 
Acarus siro; 
Bryobia graminum; 
mites which are of importance in veterinary medicine such as, for example, 
Macronyssus bursa, Macronyssus sylviarum, Macronyssus lacoti; 
Dermanyssus gallinae; 
ticks, especially of the families Ixodidae and Argasidae and of the orders 
Boophilus, Amblyomma, Hyalomma, Rhipicephalus, Ixodes, Argas and 
Ornithodorus; 
nematodes which are of importance in plant protection such as, for example, 
Aphelenchoides sp., Globodera sp., Heliocotylenchus sp., Heterodera sp., 
Hoploliamus sp., Meloidoqyne sp., Paratrichodorus sp., Pratylenchus sp., 
Rotylenchus sp., Tylenchorhynchus sp. and Tylenchulus sp. 
The compounds in accordance with the invention act as contact and feed 
poisons. Moreover, some of the compounds are taken up by various plants, 
so that the pests to be controlled are killed when they eat the plants. 
These compounds exhibit systemic activity. 
The compounds in accordance with the invention are also active against 
spider mites which have developed resistance to conventional pesticides. 
Moreover, the compounds are characterized by a good residual activity and 
a good selectivity against phytoseiulus persimiles. 
The pest control composition in accordance with the invention contains an 
effective amount of at least one compound of formula I or an acid addition 
salt thereof, as well as formulation adjuvants. The composition 
conveniently contains at least one of the following formulation adjuvants: 
Solid carrier substances; solvents or dispersion media; tensides (wetting 
and emulsifying agents); dispersing agents (without tenside action); and 
stabilizers. 
With the use of these and, if desired, additional adjuvants, the compounds 
of formula I and their acid addition salts, namely, the pesticidally 
active substances, can be converted into the usual formulations such as 
solutions, suspensions, emulsions, emulsifiable concentrates, pastes, 
foams, dusts, powders and granulates. 
As solid carrier substances, there come into consideration: natural mineral 
substances such as kaolin, aluminas, siliceous earth, talc, bentonite, 
chalk, limestone, quartz, dolomite, attapulgite, montmorillonite and 
diatomaceous earth; synthetic mineral substances such as highly 
dispersible silicic acid, aluminum oxide and silicates; organic substances 
such as cellulose, starch, urea and synthetic resins; and fertilizers such 
as phosphates and nitrates, whereby such carrier substances can be 
present, for example, as dusts, powders or granulates. 
As solvents or dispersion media there come into consideration: aromatics 
such as toluene, xylenes, benzene and alkylnaphthalenes; chlorinated 
aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, 
chloroethylenes and methylene chloride; aliphatic hydrocarbons such as 
cyclohexane and paraffins, for example, petroleum fractions; alcohols such 
as butanol and glycol as well as their ethers and esters; ketones such as 
acetone, methyl ether ketone, methyl isobutyl ketone and cyclohexanone; 
and strongly polar solvents such as dimethylformamide, N-methylpyrrolidone 
and dimethyl sulfoxide, such solvents or dispersion media preferably 
having flash points of at least 30.degree. C. and boiling points of at 
least 50.degree. C.; and water. As solvents or dispersion media there also 
come into consideration so-called liquified gaseous extenders or carrier 
substances, namely, products which are gaseous at room temperature and 
under normal pressure. Examples of such products are aerosol propellants 
such as halogenated hydrocarbons, for example, dichlorodifluoromethane. 
When water is used as the solvent, organic solvents can, for example, also 
be used as auxiliary solvents. 
The tensides (wetting and emulsifying agents) can be non-ionic compounds 
such as condensation products of fatty acids, fatty alcohols or 
fatty-substituted phenols with ethylene oxide; fatty acid esters and 
ethers of sugars or polyvalent alcohols; the products which are obtained 
from sugars or polyvalent alcohols by condensation with ethylene oxide; 
block polymers of ethylene oxide and propylene oxide: or 
alkyldimethylamine oxides 
The tensides can also be anionic compdunds such as soaps; fatty sulfate 
esters, for example, dodecyl sodium sulfate, octadecyl sodium sulfate and 
cetyl sodium sulfate; alkyl sulfonates, aryl sulfonates and fatty-aromatic 
sulfonates such as alkylbenzene sulfonates, for example, calcium 
dodecylbenzenesulfonate, and butylnaphthalene sulfonates; and more complex 
fatty sulfonates, for example, the amide condensation products of oleic 
acid and N-methyltaurine and the sodium sulfonate of dioctyl succinate. 
Finally, the tensides can be cationic compounds such as 
alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium chlorides, 
alkyltrimethylammonium chlorides and ethoxylated quaternary ammonium 
chlorides. 
As dispersing agents (without tenside action) there come into 
consideration: lignin, sodium and ammonium salts of lignin sulfonic acids, 
sodium salts of maleic anhydride-diisobutylene copolymers, sodium and 
ammonium salts of sulfonated polycondensation products of naphthalene and 
formaldehyde, and sulfite lyes. 
As dispersing agents, which are especially suitable as thickening or 
anti-settling agents, there can be used, for example, methylcellulose, 
carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, 
alginates, caseinates and blood albumin. 
Examples of suitable stabilizers are acid-binding agents, for example, 
epichlorohydrin, phenyl glycidyl ether and soya epoxides; antioxidants, 
for example, gallic acid esters and butylhydroxytoluene; UV-absorbers, for 
example, substituted benzophenones, diphenylacrylonitrile acid esters and 
cinnamic acid esters; and deactivators, for example, salts of 
ethylenediaminotetraacetic acid and polyglycols. 
The pest control compositions in accordance with the invention can contain, 
in addition to the active substances of formula I, other active 
substances, for example, other pest control agents, pest baits, 
fungicides, bactericides, plant growth regulators and fertilizers. Such 
combination compositions are suitable for intensifying the activity or for 
broadening the spectrum of activity. If desired, insufficiencies of known 
agents can thereby also be compensated for. 
It has been found that the compounds in accordance with the invention are 
advantageously used in combination with conventional acaricides, 
especially with conventional acaricides which are suitable for the control 
of eggs and larvae of mites. Examples of such acaricides are chlorbenside, 
chlorfenson, clofentezine, fenson, fenothiocarb, flubenzimine, tetradifon, 
hexythiazox, benzoximate, dienochlor, flufenoxuron and NC-129. The use can 
be effected simultaneously or separately. Thereby, the active substances 
in accordance with the invention can cancel the disadvantage of known 
acaricides having a main focus of activity against the eggs and larvae, in 
that mobile stages which survive after the use of these known acaricides 
and which can develop rapidly to a new adult population are also killed. 
Since under practical conditions eggs, different larval stages as well as 
adults, namely male and female forms, often appear simultaneously, an 
overall effect which is extremely desirable in practice, that is, more 
rapid, more effective and longer-lasting, can be produced using 
combination preparations. The total amount of the two active substances in 
such combination preparations conveniently amounts, however, to not more 
than the amount of an active substance when a compound of formula I is 
used as the sole active substance. 
The pest control compositions in accordance with the invention contain, 
according to type, between 0.005 and 95 weight percent of the compound or 
compounds in accordance with the invention as the active substance. The 
compounds can be present in a form which is suitable for storage and 
transport. In such forms, for example, emulsifiable concentrates, the 
active substance concentration is normally in the higher region of the 
above concentration range. These forms can be diluted with the same or 
different formulation adjuvants to give active substance concentrations 
which are suitable for practical use and such concentrations normally lie 
in the lower region of the above concentration range. Emulsifiable 
concentrates generally contain 5 to 90 weight percent, preferably 10 to 80 
weight percent, of the compound(s) in accordance with the invention. As 
forms for use, there come into consideration, inter alia, ready-for-use 
solutions, emulsions, suspensions, foams, powders, pastes, dusting 
compositions and granulates. The active substance concentrations in such 
ready-for-use compositions can be varied in wide limits. In sprayable 
liquids, there can be present, for example, concentrations in the range of 
from 0.005 to 0.5 weight percent. In the Ultra-Low-Volume process, there 
can be formulated sprayable liquids in which the active substance 
concentration is preferably from 10 to 20 weight percent, while the spray 
able liquids formulated in the Low-Volume process and in the High-Volume 
process preferably have an active substance concentration in the range of 
from 0.01 to 0.5 and in the range of from 0.005 to 0.1 weight percent, 
respectively. Granulates preferably contain in the range of from 5 to 50 
weight percent of the compound(s) in accordance with the invention as the 
active substance. 
The pest control compositions in accordance with the invention can be 
prepared by mixing at least one compound of the formula I or an acid 
addition salt of such a compound with formulation adjuvants. 
The preparation of the compositions can be carried out in a known manner, 
for example, by mixing the active substance with solid carrier substances, 
by dissolution or suspension in suitable solvents or dispersion media, if 
necessary using tensides as wetting or emulsifying agents, or dispersing 
agents, by diluting pre-prepared emulsifiable concentrates with solvents 
or dispersion media, and the like. 
In the case of pulverous compositions, the active substance can be mixed 
with a solid carrier substance, for example, by grinding together; or the 
solid carrier substance can be impregnated with a solution or suspension 
of the active substance and then the solvent or suspension medium can be 
removed by evaporation, by heating or by suction under reduced pressure. 
By adding tensides or dispersing agents such pulverous compositions can be 
made readily wettable with water, so that they can be converted into 
aqueous suspensions which are suitable, for example, as spray 
compositions. 
The compounds of formula I or their acid addition salts can also be mixed 
with a tenside and a solid carrier substance to form a wettable powder 
which is dispersible in water or they can be mixed with a solid granulated 
carrier substance to form a granulate. 
If desired, a compound of formula I or an acid addition salt thereof can be 
dissolved in a water-immiscible solvent such as, for example, an alicyclic 
ketone, which conveniently contains a dissolved emulsifying agent, so that 
the solution becomes self-emulsifying upon addition to water. 
Alternatively, the active substance can be mixed with an emulsifying agent 
and the mixture can then be diluted with water to the desired 
concentration. Moreover, the active substance can be dissolved in a 
solvent and thereafter the solution can be mixed with an emulsifying 
agent. Such a mixture can likewise be diluted with water to the desired 
concentration. In this manner, there are obtained emulsifiable 
concentrates or ready-for-use emulsions. 
The method in accordance with the invention for the control of pests 
comprises treating the locus to be protected or the pests themselves with 
an effective amount of a compound in accordance with the invention or of a 
pest control composition in accordance with the invention. This method of 
use can be carried out by application to the soil or leaves or by 
application to the animals, supplies or materials to be protected, 
depending on the kind of pests to be controlled. The control is achieved, 
for example, by contact or by intake with the feed. 
The utilization of the compounds of formula I can be carried out in a 
conventional manner, for example, by sprinkling, spraying, atomizing, 
dusting, scattering, drilling-in, smoking, watering, steeping, coating or 
the like. Pulverous preparations can be applied to the pests or to the 
locus to be protected, for example, plants or animals, as for example, 
dusting agents with the aid of the usual dusting appliances. Aqueous 
suspensions can be used, for example, as spray compositions. 
When used in plant protection, a dosage in the range of from about 100 to 
500 g of active substance compound(s) of formula I]/ha, for example, as is 
the case in the application of 2000 1 of a spray liquor which contains 
0.005-0.025 weight percent of active substance to 1 ha of cultivated land, 
is usually sufficient. 
The following Examples serve to illustrate the invention in more detail.