WO1998006710A1

WO1998006710A1 - Substituted 4-nitroimino-perhydro-1,3,5-oxadiazine derivatives, their use as pesticides and intermediates for their preparation

Info

Publication number: WO1998006710A1
Application number: PCT/EP1997/004137
Authority: WO
Inventors: Peter Maienfisch; Laurenz Gsell
Original assignee: Ciba Geigy AG; Novartis AG
Current assignee: Novartis AG
Priority date: 1996-08-08
Filing date: 1997-07-30
Publication date: 1998-02-19
Anticipated expiration: 1999-02-08
Also published as: ZA977036B; AU4297197A

Abstract

Compounds of formula (I), in which A is a substituted or unsubstituted heterocyclyl group; -E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R1)-R, -C(=O)C(=O)-R, -C(=O)C(=O)O-R, -C(=O)C(=O)N(R1)-R or -C(=S)N(R1)-R; R is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; and R1 is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloakyl, aryl or heteroaryl group, and, where appropriate, tautomers thereof, in each case in free form or in salt form, can be used as agrochemical active ingredients and can be prepared in a manner known per se.

Description

SUBSTTTUTED -N_ITROIMINC-PERHYDRO-I,3,5-OXADIAZINE DERIVATIVES, THEIR USE AS

PESTICIDES AND INTERMEDIATES FOR THEIR PREPARATION

The invention relates to compounds of the formula

in which A is a substituted or unsubstituted heterocyclyl group; -E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R,)-R, -C(=O)C(=O)-R, -C(=O)C(=O)O-R, -C(=O)C(=O)N(R,)-R or -C(=S)N(R -R;

R is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; and

R, is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group, in free form or in salt form, where appropriate to tautomers, in free form or in salt form, of these compounds, to a process for the preparation and to the use of these compounds and tautomers, to pesticidal compositions whose active ingredient is selected from amongst these compounds and tautomers, in each case in free form or in agrochemically utiiizable salt form, to a process for the preparation and to the use of these compositions, to plant propagation material treated with these compositions, to a method of controlling pests, to intermediates, in free form or in salt form, for the preparation of these compounds, where appropriate to tautomers, in free form or in salt form, of these intermediates, and to a process for the preparation and to the use of these intermediates.

Certain oxadiazine derivatives have been proposed in the literature as arthropodacidally active ingredients in pesticides. However, the biological properties of these known compounds are not entirely satisfactory in the field of pest control, which is why there is a need to provide other compounds which have pesticidal properties, in particular for controlling insects and representatives of the order Acaπna, this object being achieved according to the invention by providing the present compounds I.

In some cases, the compounds I can exist as tautomers For example, if -E-R is -C(=O)N(R,)-R and R, is hydrogen, corresponding compounds I, i. e. those in which -E-R is -C(=O)N(H)-R, can be in equilibrium with the respective tautomers in which -E-R is -C(OH)=N-R. Accordingly, the compounds I hereinabove and hereinbelow are to be understood as including such tautomers, where appropriate, even though the latter are not mentioned specifically in each individual case.

Compounds I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfunc acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxyiic acids, such as CrC4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Cι-C₄alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor- pholine, pipendine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, die- thyl-, tπethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkyiamine, for example mono-, di- or tπethanolamine. Where appropriate, the corresponding internal salts can furthermore be formed. Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also encompasses salts which have disadvantage for agrochemical use, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds I or agrochemically utilizabie salts thereof. Owing to the close relationship between the compounds I in free form and in the form of their salts, for the purposes of the invention the free compounds I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds I. The same applies analogously to tautomers of compounds I and salts thereof. In general, the free form is preferred in each case.

Unless otherwise defined, the general terms used hereinabove and hereinbelow have the meanings which follow. Suitable as ring heteroatom(s) in the ring skeleton of the heterocyclyl group A, which is, for example, bicyclic or, preferably, monocyclic, are all elements of the Periodic System which can form at least two covalent bonds ( where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof) where, if the ring skeleton of A consists of more than one ring, (a) ring heteroatom(s) may be present either only in one ring or else in more than one ring of the ring skeleton of A.

What has been said in the previous sentence about the ring heteroatom(s) in the ring skeleton of the heterocyclyl group A also applies analogously hereinabove and hereinbelow to the ring heteroatom(s) in the ring skeleton of a heteroaryl or non-aromatic heterocyclyl group, meaning of substituent or substructure, each of which is also, for example, bicyclic or, preferably, monocyclic, where a non-aromatic heterocyclyl group, meaning of substituent or substructure is understood as meaning one whose ring skeleton does not have aromatic character (for example one which is fully unsaturated, or one which, although it contains conjugated double bonds, does not contain these in the maximum number possible).

Halogen - as a group per se and as a structural element of other groups and compounds, such as halocycloalkyl, halocycloalkoxy, halocycloalkylthio, haloalkyl, haloalkoxy, haloalkyl- thio, haloalkenyl, haloalkenyloxy, haloalkenylthio, haloalkynyl, haloalkynyloxy, haloalkynyl- thio, haloalkylsulfinyl, haloalkylsulfinyloxy, haloalkylsulfonyl, haloalkylsulfonyloxy, halo- phenoxy and halophenylthio - is, for example, fluorine, chlorine, bromine or iodine, in particular flluorine, chlorine or bromine, but especially fluorine or chlorine.

Unless otherwise defined, carbon-containing groups and compounds comprise for example in each case 1 up to and including 15, preferably 1 up to and including 10, especially 1 up to and including 8, in particular 1 up to and including 5, especially 1 or 2, carbon atom(s).

Cycloalkyl - as a group per se and as a structural element of other groups and compounds such as halocycloalkyl, cycloalkoxy, halocycloalkoxy, cycloalkylthio and halocycloalkylthio - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyi or cycloheptyl. Alkyl - as a group per se and as a structural element of other groups and compounds such as haloalkyi, tnalkylsilyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkyisulfinyl, haloalkylsul- finyl, alkylsulfinyloxy, haloalkylsulfmyloxy, alkylsulfonyl, haloalkylsulfonyl, alkylsulfonyloxy, haloalkylsulfonyloxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, alkoxyalkoxy, alkylamino, dialkylamino, N-alkylarylamino, N-alkylcarbonylarylamino, N-alkyl- heteroarylamino and N-alkylcarbonylheteroarylamino - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain, for example methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl, or branched, for example tsopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl

Alkenyl - as a group per se and as a structural element of other groups and compounds such as haloalkenyl, alkenyloxy, haloalkenyloxy, alkenylthio and haloalkenylthio - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain or branched and comprises in each case 2 or more than 2 or preferably 1 carbon-carbon double bond(s), the double bonds of these substituents being separated from the remaining moiety of the compound I by preferably at least one saturated carbon atom, and is, for example, ally!, propen-2-yl, methallyl, but-2-en- 1-yl, but-3-en-1 -yl, pent-4-en-1-yl or undec-10-en-1-yl.

Alkynyl - as a group per se and as a structural element of other groups and compounds such as haloalkynyl, alkynyloxy, haloalkynyloxy, alkynylthio and haloalkynylthio - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain or branched and comprises in each case 2 or more than 2 or preferably 1 carbon-carbon triple bond(s), the triple bonds of these substituents being separated from the remaining moiety of the compound I by preferably at least one saturated carbon atom, and is, for example, propargyl, but-2-ynyl or but-3-yn-2-yl

Aryl - as a group per se and as a structural element of other groups and compounds such as arylcarbonyl, arylcarbonyloxy, aryloxy, arylthio, arylsulfinyl, arylsulfinyloxy, arylsulfonyl, arylsulfonyioxy, arylamino, N-alkyl-arylamino, N-formyl-arylamino and N-alkylcarbonyl-aryl- ammo - is, for example, naphthyl or, preferably, phenyl. Heteroaryl - as a group per se and as a structural element of other groups and compounds such as heteroarylcarbonyl, heteroarylcarbonyloxy, heteroaryloxy, heteroarylthio, heteroa- rylsulfinyl, heteroarylsulfinyioxy, heteroarylsulfonyl, heteroarylsulfonyloxy, heteroarylamino, N-alkyl-heteroarylamino, N-formyl-heteroarylamino and N-alkylcarbonyl-heteroarylamino - has, for example, an aromatic ring skeleton composed of a ring having 5 or 6 ring members or of a combination of at least two rings having in each case independently of one another 5 or 6 ring members, where for example 1 up to and including 4 of the ring members is (are) (a) heteroatom(s) selected from the group consisting of nitrogen, oxygen and sulfur, and is, for example, pyridyl, thienyl, thiazolyl, thiadiazolyl, furyl, oxadiazolyl, indolizinyl, pyrimidyl, quinolyl or pteridinyl.

Non-aromatic heterocyclyl - as a group per se and as a structural element of other groups and compounds such as non-aromatic heterocyclyloxy and non-aromatic heterocyclylthio - has, for example, a non-aromatic ring skeleton composed of a ring having 5 or 6 ring members or of a combination of at least two rings having in each case independently of one another 5 or 6 ring members, where for example 1 up to and including 4 of the ring members is (are) (a) heteroatom(s) selected from the group consisting of nitrogen, oxygen and sulfur and is, for example, piperidyl, pyrrolinyl, tetrahydrofuryl or chromanyl.

Halogen-substituted carbon-containing groups and compounds such as halocycloalkyl, halocycloalkoxy, halocycloalkylthio, haloalkyi, haloalkenyl, haloalkenyloxy, haloalkenylthio, haloalkynyl, haloalkynyloxy, haloalkynylthio, haloalkoxy, haloalkylthio, haloalkylsuifinyl, haloal- kylsulfinyloxy, haloalkylsulfonyl, haloalkylsulfonyloxy, halophenoxy and halophenylthio can be partially halogenated or perhalogenated, where, in the case of polyhalogenation, the halogen substituents can be identical or different.

In alkoxyalkoxy, an alkoxy group which is bonded to the remaining moiety of the compound I is substituted by, for example, 2 or 3 or, preferably, 1 alkoxy group(s).

In N-alkyl-arylamino, an arylamino group which is bonded to the remaining moiety of the compound I is substituted on its nitrogen atom by one alkyl group.

In N-formyl-arylamino, an arylamino group which is bonded to the remaining moiety of the compound I is substituted on its nitrogen atom by one formyl group. ln N-alkylcarbonyl-arylamino, an arylamino group which is bonded to the remaining moiety of the compound I is substituted on its nitrogen atom by one alkylcarbonyl group.

In N-alkyl-heteroarylamino, a heteroarylammo group which is bonded to the remaining moiety of the compound I is substituted on its ammo nitrogen atom by one alkyl group.

In N-formyl-heteroarylamino, a heteroarylammo group which is bonded to the remaining moiety of the compound I is substituted on its amino nitrogen atom by one formyl group.

In N-alkylcarbonyl-heteroarylamino, a heteroarylammo group which is bonded to the remaining moiety of the compound I is substituted on its ammo nitrogen atom by one alkylcarbonyl group.

The following are preferred embodiments within the scope of the invention:

(1) A compound of the formula I, in which A is a substituted or unsubstituted heterocyclyl group;

(2) A compound of the formula I, in which the ring skeleton of A is composed of a ring having 5 or 6 ring members or of a ring having 5 or 6 ring members to which a further ring having 5 or 6 ring members is fused, in particular of a ring having 5 or 6 ring members;

(3) A compound of the formula I, in which the ring skeleton of A is saturated or unsaturated, in particular the ring skeleton of A comprises no, or 2 to 4, preferably conjugated, double bond(s), preferably comprises no, or 2 or 3, preferably conjugated, double bonds, especially comprises 2 or 3, preferably conjugated, double bonds, in particular the ring skeleton of A has aromatic character;

(4) A compound of the formula I, in which the ring skeleton of A comprises 1 up to and including 4, in particular 1 up to and including 3, especially 1 or 2, ring heteroatom(s) (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof); (5) A compound of the formula I, in which the ring skeleton of A comprises 1 , 2 or 3 ring he- tero atom(s) selected from the group consisting of oxygen, sulfur and nitrogen (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof), where the ring skeleton comprises not more than one ring oxygen atom and where the ring skeleton comprises not more than one nng sulfur atom, in particular comprises 1 , 2 or 3 ring heteroatom(s) selected from the group consisting of oxygen, sulfur and nitrogen (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof), where the ring skeleton comprises not more than one ring oxygen atom or one ring sulfur atom, preferably comprises at least one ring nitrogen atom (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof) or not more than one ring oxygen atom, more preferably comprises at least one ring nitrogen atom (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof), especially comprises at least one nng nitrogen atom;

(6) A compound of the formula I, in which A is bonded to the remaining moiety of the compound I via a C atom of its ring skeleton;

(7) A compound of the formula I, in which A is unsubstituted or mono- to tetrasubstituted, where up to two of the substituents of A are selected from the group consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, alkenylthio, haloalkenylthio, alkynylthio, haloalkynylthio, cyano and nitro, and where, if A is tπ- or tetrasubstituted, each substituent of A, which differs from the two substituents, which lead to the disubstitution of A, is selected from the group consisting of alkyl, alkoxy and halogen, in particular A is unsubstituted or mono- or disubstituted by substituents selected from the group consisting of halogen, Cι-C₃alkyl, halo-Ci-Csalkyl, Cι-C₅alkoxy and halo-d-Csalkoxy, preferably A is unsubstituted or mono- or disubstituted by substituents selected from the group consisting of halogen and Cι-C₃alkyl, especially A is unsubstituted or monosubstituted by halogen, more preferably A is monosubstituted by halogen; (8) A compound of the formula I, in which the ring skeleton of A is a tetrahydrofuryl, pyridyl, 1-oxidopyridinιo or thiazolyl group, preferably the ring skeleton of A is a tθtrahydrofur-3-yl, pyrid-3-yl, 1-oxido-3-pyrιdιnιo or thi- azol-5-yl group, in particular A is a tetrahydrofur-3-yl, pyrid-3-yl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-d-

C₃alkylpyrιd-5-yl, 1-oxιdo-3-pyridinio, 2-halo-1-oxido-5-pyridinio, 2,3-dihalo-1 -oxido-5-pyridι- nio or 2-halothιazol-5-yl group, especially A is a tetrahydrofur-3-yl, pyrid-3-yl, 2-halopyrid-5-yl, 2-halo-1-oxido-5-pyridmιo or

2-halothιazol-5-yl group, preferably A is a pyπd-3-yl, 2-chloropyrιd-5-yl, 2-chloro-1 -oxido-5-pyrιdιnιo or 2-chlorothι- azol-5-yl group, in particular A is a 2-chloropyrid-5-yl or 2-chlorothιazol-5-yl group;

(9) A compound of the formula I, in which -E-R is C(=O)-R, -C(=O)O-R, -C(=O)N(R₁)-R, -C(=O)C(=O)-R, -C(=O)C(=O)O-R, -C(=O)C(=O)N(R,)-R or -C(=S)N(R,)-R and R, is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group, preferably -E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R,)-R, -C(=O)C(=O)O-R or -C(=S)N(R,:)-R and R, is hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group which is unsubstituted or mono- to tnsubstituted by substituents selected from the group consisting of halogen, cyano, nitro, tnalkylsilyl, ammo, alkyiamino, dialkylamino, alkyl, haloalkyi, hydroxy, alkoxy, haloalkoxy, alkoxyalkoxy, mercapto, alkylthio, haloalkylthio, alkyisulfinyl, haloalkylsulfmyl, alkylsulfmyloxy, haloalkylsulfinyloxy, alkylsulfonyl, haloalkylsulfo- nyl, alkylsulfonyloxy, haloalkylsulfonyloxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, cycloalkyl, halocycloalkyl, cycloalkoxy, halocycloalkoxy, cycloalkylthio, halocycloalkylthio, aryl, aryloxy, arylthio, arylsulfinyl, arylsulfinyloxy, arylsulfonyl, arylsulfo- nyloxy, arylamino, N-alkyl-arylamtno, N-formyl-arylamino, N-alkylcarbonyl-arylammo, arylcar- bonyl, arylcarbonyloxy, non-aromatic heterocyclyl, non-aromatic heterocyclyloxy, non-aromatic heterocyclylthio, heteroaryl, heteroaryloxy, heteroarylthio, heteroarylsulfinyl, heteroa- rylsulfinyloxy, heteroarylsulfonyl, heteroarylsulfonyloxy, heteroarylammo, N-alkyl-heteroaryl- ammo, N-formyl-heteroarylamino, N-alkylcarbonyl-heteroarylamino, heteroarylcarbonyl and heteroarylcarbonyloxy, where the aryl and heteroaryl substructures in the last-mentioned aryl, aryloxy, arylthio, arylsulfinyl, arylsulfinyloxy, arylsulfonyl, arylsulfonyloxy, arylamino, N- alkyl-arylamino, N-formyl-arylamino, N-alkylcarbonyl-arylammo, arylcarbonyl, arylcarbonylo- xy, heteroaryl, heteroaryloxy, heteroarylthio, heteroarylsulfinyl, heteroarylsulfinyloxy, hetero- arylsulfonyl, heteroarylsulfonyloxy, heteroarylamino, N-alkyl-heteroarylamino, N-formyl-hete- roarylammo, N-alkylcarbonyl-heteroarylammo, heteroarylcarboπyl and heteroarylcarbonylo- xy substituents independently of one another are unsubstituted or mono- to tnsubstituted by substituents selected from the group consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkoxy, haloalkoxy, alkylthio, haloalkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio and halophenylthio, and where the non-aromatic heterocyclyl substructures in the last-mentioned non-aromatic heterocyclyl, non-aromatic heterocyclyloxy and non-aromatic heterocyclylthio substituents independently of one another are unsubstituted or mono- to tnsubstituted by substituents selected from the group consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkoxy, haloalkoxy, alkylthio, haloalkylthio, oxo, thioxo, nitro, cyano, phenoxy, halophenoxy, phenylthio and halophenylthio, in particular -E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R,)-R, -C(=O)C(=O)O-R or -C(=S)N(R,)-R and R, is Cι-C₅alkyl, C₂-C₅alkenyl, C₂-C₅alkynyl, C₃-C₇cycloalkyl, aryl, heteroaryl or, preferably, hydrogen, especially -E-R is -C(=O)-R or -C(=O)O-R,

(10) A compound of the formula I, in which R is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group, in particular R is hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group which is unsubstituted or mono- to tnsubstituted by substituents selected from the group consisting of halogen, cyano, nitro, tnalkylsilyl, ammo, alkylamino, dialkylamino, alkyl, haloalkyi, hydroxy, alkoxy, haloalkoxy, alkoxyalkoxy, mercapto, alkylthio, haloalkylthio, alkyisulfinyl, haloalkylsulfinyl, alkylsulfinyloxy, haloalkylsulfmyloxy, alkylsulfonyl, haloalkylsulfonyl, al- kylsuifonyloxy, haloalkylsulfonyloxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxy- carbonyloxy, cycloalkyl, halocycloalkyl, cycloalkoxy, halocycloalkoxy, cycloalkylthio, halocycloalkylthio, aryl, aryloxy, arylthio, arylsulfinyl, arylsulfinyloxy, arylsulfonyl, arylsulfonyloxy, arylamino, N-alkyl-arylamino, N-formyl-aryiamino, N-alkylcarbonyl-arylamino, arylcarbonyl, arylcarbonyloxy, non-aromatic heterocyclyl, non-aromatic heterocyclyloxy, non-aromatic heterocyclylthio, heteroaryl, heteroaryloxy, heteroarylthio, heteroarylsulfinyl, heteroarylsulfinyloxy, heteroarylsulfonyl, heteroarylsulfonyloxy, heteroarylammo, N-alkyl-heteroarylamino, N- formyl-heteroarylamino, N-alkylcarbonyl-heteroarylamino, heteroarylcarbonyl and heteroa- rylcarbonyloxy, where the aryl and heteroaryl substructures in the last-mentioned aryl, aryloxy, arylthio, arylsulfinyl, arylsulfinyloxy, arylsulfonyl, arylsulfonyloxy, arylamino, N-alkyl-aryla- mino, N-formyl-arylamino, N-alkylcarbonyl-arylamino, aryicarbonyl, arylcarbonyloxy, heteroaryl, heteroaryloxy, heteroarylthio, heteroarylsulfinyl, heteroarylsulfinyloxy, heteroarylsulfo- nyl, heteroarylsulfonyloxy, heteroarylamino, N-alkyl-hβteroarylamino, N-formyl-heteroaryla- ino, N-alkylcarbonyl-heteroarylamino, heteroarylcarbonyl and heteroarylcarbonyloxy substituents independently of one another are unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkoxy, haloalkoxy, alkylthio, haloalkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio and halophenylthio, and where the non-aromatic heterocyclyl substructures in the last-mentioned non-aromatic heterocyclyl, non-aromatic heterocyclyloxy, and non-aromatic heterocyclylthio substituents independently of one another are unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkoxy, haloalkoxy, alkylthio, haloalkylthio, oxo, thioxo, nitro, cyano, phenoxy, halophenoxy, phenylthio and halophenylthio, preferably R is hydrogen or an alkyl, alkenyl, cycloalkyl, phenyl or heteroaryl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyi, alkoxy, alkylcarbonyloxy, cycloalkyl, unsubstituted phenyl and phenyl which is mono- to trisubstituted by substituents selected from the group consisting of alkyl and nitro, more preferably R is an alkyl, alkenyl, cycloalkyl or phenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyi, alkoxy, alkylcarbonyloxy, cycloalkyl, unsubstituted phenyl and phenyl which is mono- to trisubstituted by substituents selected from the group consisting of alkyl and nitro, especially R is hydrogen; a Cι-C_θalkyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, CrC₅alkylcarbonyloxy, C₃-C_θcycloalkyl, unsubstituted phenyl and phenyl which is mono- to trisubstituted by substituents selected from the group consisting of C C₅alkyl and nitro; a C₂-Cι₅alkenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen; an unsubstituted C₃-C₈cycloalkyl group; a pyridyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halo-d-Csalkyl; or a phenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, cyano, nitro, Cι-C₅alkyl, halo-Cι-C₅. alkyl, CrC₅alkoxy and CrC₅alkylcarbonyloxy, especially R is a Cι-C_βalkyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, Cι-C₅alkylcarbonyloxy, C₃-C₈cycloal- kyl, unsubstituted phenyl and phenyl which is mono- to trisubstituted by substituents selected from the group consisting of C C₅alkyl and nitro; an unsubstituted C₂-C₆alkenyl or C₃- Cβcycloalkyl group; or a phenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, cyano, nitro, Cι-C₅alkyl, halo- Cι-C₅alkyl, CrC₅alkoxy and Cι-C₅alkylcarbonyloxy, especially R is hydrogen; a Cι-C_Balkyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, unsubstituted phenyl and phenyl which is mono- to trisubstituted by substituents selected from the group consisting of d-C₅alkyl; a C₂-C₁₅alkenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen; an unsubstituted C₃-C_Bcycloalkyl group; a pyridyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halo-CrCsalkyl; or a phenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, nitro, d-C₅alkyl, halo-d-C₅alkyl, d-C₅alkoxy and Cι-C alkylcarbonyloxy, especially R is unsubstituted phenyl or d-C₅alkyl which is unsubstituted or monosubstituted by unsubstituted phenyl;

(11 ) A compound of the formula I, in which A is a tetrahydrofur-3-yl, pyrid-3-yl, 2-halopyrid- 5-yl, 2,3-dihalopyrid-5-yl, 2-Cι-C₃alkylpyrid-5-yl, 1 -oxido-3-pyridinio, 2-halo-1-oxido-5-pyridi- nio, 2,3-dihalo-1-oxido-5-pyridinio or 2-halothiazol-5-yl group, -E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R₁)-R, -C(=O)C(=O)O-R or -C(=S)N(R₁)-R, R, is C,-C₅alkyl, C₂-C₅alkenyl, C₂-C₅al- kynyl, C₃-C₇cycloalkyl, aryl, heteroaryl or preferably hydrogen and R is hydrogen; a d-C₈al- kyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, Cι-C₅alkylcarbonyloxy, C₃-C₈cycloalkyl, unsubstituted phenyl and phenyl which is mono- to trisubstituted by substituents selected from the group consisting of d-C₅alkyl and nitro; a C₂-C₁₅alkenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen; an unsubstituted C₃-C₈cycloalkyl group; a pyridyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halo-d-C₅alkyl; or a phenyl group which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, cyano, nitro, d-C₅alkyl, halo-d-C₅alkyl, d-C₅alkoxy and d-C₅alkylcar- bonyloxy; (12) A compound of the formula I, in which A is a 2-chloropyrid-5-yl or 2-chlorothiazol-5-yl group, -E-R is -C(=O)-R or -C(=O)O-R and R is unsubstituted phenyl or C C₅alkyl which is unsubstituted or monosubstituted by unsubstituted phenyl.

Especially preferred within the scope of the invention are the compounds of the formula I mentioned in Examples H5 to H9.

Individually preferred within the scope of the invention are

(a) 3-acetyl-5-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1 ,3,5-oxadiazine,

(b) 5-(2-chloropyrid-5-ylmethyl)-3-ethylcarbonyl-4-nitroimino-perhydro-1 ,3,5-oxadiazine,

(c) 3-benzylcarbonyl-5-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1 ,3,5-oxadiazine,

(d) 3-benzoyl-5-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1 ,3,5-oxadiazine,

(e) 5-(2-chloropyrid-5-ylmethyl)-3-methoxycarbonyl-4-nitroimino-perhydro-1 ,3,5-oxadiazine,

(f) 3-benzyloxycarbonyl-5-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1 ,3,5-oxadiazine,

(g) 3-(2-chloropyrid-5-ylmethyl)-4-nitroimino-5-phenoxycarbonyl-perhydro-1 ,3,5-oxadiazine and

(h) 3-acetyl-5-(2-chlorothiazol-5-ylmethyl)-4-nitroimino-perhydro-1 ,3,5-oxadiazine.

As a further subject of the invention, the process for the preparation of the compounds of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form, comprises, for example, a) reacting a compound of the formula

in which E and R have the meanings given for formula I, or a tautomer and/or salt thereof, with a compound of the formula

A-CH₂-Y (III), which is known or can be prepared analogously to corresponding known compounds and in which A has the meaning given for formula I and Y is a leaving group, or, where appropriate, with a tautomer and/or salt thereof, preferably in the presence of a base, or b) reacting a compound of the formula

which is known or which can be prepared analogously to corresponding known compounds and in which A has the meaning given for formula I, or a tautomer and/or salt thereof, with a compound of the formula

Y-E-R (V), which is known or which can be prepared analogously to corresponding known compounds and in which E and R have the meanings given for formula I and Y is a leaving group, or, where appropriate, with a tautomer and/or salt thereof, preferably in the presence of a base, or, c) to prepare a compound of the formula I, in which -E-R is -C(=Z)N(H)-R and Z is O or S, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of the formula

T 1 (IV),

— y H

NN0₂

Z=C=N-R (VI), which is known or which can be prepared analogously to corresponding known compounds and in which R has the meaning given for formula I and Z is O or S, or, where appropriate, with a tautomer and/or salt thereof, preferably in the presence of a base, and/or converting a compound of the formula I or a tautomer thereof, in each case in free form or in salt form, into another compound of the formula I or a tautomer thereof, separating an isomer mixture which can be obtained in accordance with the process and isolating the desired isomer and/or converting a free compound of the formula I or a tautomer thereof into a salt or a salt of a compound of the formula I or a tautomer thereof into the free compound of the formula I or a tautomer thereof or into another salt. What has been said above for tautomers and/or salts of compounds I applies analogously to starting materials mentioned hereinabove and hereinbelow with regard to the tautomers and/or salts thereof.

The reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, normally, in the presence of a suitable solvent or diluent or of a mixture of these, the process being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of from approximately -80°C to the boiling point of the reaction mixture, preferably from approximately -20°C to approximately +150^CC, and, if required, in a sealed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions can be seen from the examples.

Unless otherwise specified, the starting materials mentioned hereinabove and hereinbelow, which are used for the preparation of the compounds I or, where appropriate, the tautomers thereof, in each case in free form or in salt form, are known or can be prepared by methods known per se, for example in accordance with the information given below.

Variant a)

Examples of suitable leaving groups Y in the compounds III are hydroxy, d-C_βalkoxy, halo- Cι-C_θalkoxy, d-C₈alkanoyloxy, mercapto, d-C₈alkylthio, halo-d-C₈alkylthio, d-C₈alkylsul- fonyloxy, halo-d-C₈alkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and preferably halogen, such as chlorine.

Examples of suitable bases for facilitating the detachment of HY are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkyla- mines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyciic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethyiamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N.N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyri- dine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diaza- bicyclo[5.4.0]undec-7-ene (DBU).

The reactants can be reacted with each other as such, i.e. without addition of a solvent or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters such as ethyl acetate; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-bu- tyl methyl ether, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethyle- ne glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides such as N,N-di- methylformamide, N,N-diethylformamide, N.N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethyiamine, pyridine, N-methylmorpholine or N,N- diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases from approximately -10°C to approximately +80°C.

In a preferred embodiment of variant a), a compound II is reacted with a compound III in an amide such as N.N-dimethylformamide, in the presence of a base such as NaH, in a temperature range from approximately 0°C to approximately +70°C.

Variant b)

Examples of suitable leaving groups Y in the compounds V are of the type given under variant a). Examples of suitable bases for facilitating the detachment of HY are of the type given under variant a).

The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of suitable diluents or solvents are of the type described under variant a).

The reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -20°C to approximately +100°C, in many cases from approximately 0°C to approximately +80°C.

In a preferred embodiment of variant b), a compound IV is reacted with a compound V in a halogenated or unhalogenated hydrocarbon, such as dichloromethane, an amide such as N.N-dimethylformamide or a nitrile such as acetonitrile, in the presence of a base such as pyridine or NaH in a temperature range from approximately +10°C to approximately +50°C.

Variant c)

Examples of suitable bases for facilitating the reaction are of the type mentioned under variant a)

The reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -20°C to approximately +100^CC, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

The compounds II and the tautomers thereof, in each case in free form or in salt form, which are employed as starting materials in process variant a) are novel and also are a sub- ject of the invention. Especially preferred within the scope of the invention are the compounds of the formula II and the tautomers thereof mentioned in Examples H1 and H2.

Another subject of the invention is the process for the preparation of the compounds of the formula II or the tautomers thereof, in each case in free form or in salt form, which comprises, for example, d) reacting the compound of the formula

( ^ (VII),

H H NN0₂

which is known, or a tautomer and/or salt thereof with a compound of the formula

Y-E-R (V), which is known or which can be prepared analogously to corresponding known compounds and in which E and R have the meanings given for formula II and Y is a leaving group, or, where appropriate, with a tautomer and/or salt thereof, for example analogously to the process described under variant b) for the corresponding reaction of a compound of the formula IV or a tautomer and/or salt thereof with a compound of the formula V or, where appropriate, with a tautomer and/or salt thereof, or, e) to prepare a compound of the formula II, in which -E-R is -C(=Z)N(H)-R and Z is O or S, or a tautomer and/or salt thereof, reacting a compound of the formula

I I (VII),

H H NNO_z

Z=C=N-R (VI), which is known or which can be prepared analogously to corresponding known compounds and in which R has the meaning given for formula II and Z is O or S, or, where appropriate, with a tautomer and/or salt thereof, for example analogously to the process described under variant c) for the corresponding reaction of a compound of the formula IV or of a tautomer and/or salt thereof with a compound of the formula VI or, where appropriate, with a tautomer and/or salt thereof, and/or converting a compound of the formula II or a tautomer there- of, in each case in free form or in salt form, into another compound of the formula II or a tautomer thereof, separating an isomer mixture which can be obtained in accordance with the process and isolating the desired isomer and/or converting a free compound of the formula II or a tautomer thereof into a salt or a salt of a compound of the formula II or of a tautomer thereof into the free compound of the formula II or a tautomer thereof or into another salt.

A compound I or II, respectively, can be converted in a manner known per se into another compound I or II, respectively, by replacing one or more substituents of the starting compound I or II, respectively, in the customary manner by (an)other substιtuent(s) according to the invention.

For example,

- in compounds I which have an unsubstituted radical A, substituents can be introduced into the radical A; or

- in compounds I which have a substituted radical A, substituents of the radical A can be replaced by other substituents.

Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.

Salts of compounds I or II, respectively, can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds I or II, respectively, are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

Salts of compounds I or II, respectively, can be converted in the customary manner into the free compounds I or II, respectively, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent. Salts of compounds I or II, respectively, can be converted in a manner known per se into other salts of compounds I or II, respectively, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds I or II, respectively, which have salt-forming properties can be obtained in free form or in the form of salts.

The compounds I and II, respectively, and, where appropriate, in each case the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure iso- mers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.

Diastereomer mixtures or racemate mixtures of compounds I or II, respectively, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxyiic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereose- lective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.

It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.

The compounds I and II, respectively, in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.

The invention relates to all those embodiments of the process by which, starting from a compound obtainable at any level of the process as starting material or intermediate, all or some of the missing steps are carried out or a starting material is used in the form of a derivative and/or salt and/or racemates or antipodes thereof or, in particular, is formed under the reaction conditions.

Those starting materials and intermediates, in each case in free form or in salt form, which lead to the compounds I or salts thereof which have been described at the outset as being particularly valuable are preferably used in the process of the present invention.

In particular, the invention relates to the preparation processes described in Examples H1 to

H9. Starting materials and intermediates, in each case in free form or salt form, which are used in accordance with the invention for the preparation of the compounds I or salts thereof and which are novel, a process for their preparation, and their use as starting materials and intermediates for the preparation of the compounds I are also a subject of the invention; in particular, this applies to the compounds II.

The compounds I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%.

Examples of the abovementioned animal pests are: from the order Acarina, for example,

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophi- lus spp., Brevipalpus spp., Bryobia praetiosa, Calipitπmerus spp., Chorioptes spp., Derma- nyssus gal nae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Oly- gonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polypha- gotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; from the order Anoplυra, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,

Agπotes spp., Anthonomus spp., Atomaria lineaπs, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Lepti- notarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhyn- chus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae,

Sitophilus spp., Sitotroga spp., Tenebno spp., Tribohum spp. and Trogoderma spp.; from the order Diptera, for example,

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomy- za spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Osci- nella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; from the order Heteroptera, for example,

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Lep- tocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino- phara spp. and Triatoma spp.; from the order Homoptθra, for example,

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspi- diotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Parlatoria spp., Pemphigus spp., Planococ- cus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Ouadraspidiotus spp., Rhopaiosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; from the order Hymenoptera, for example,

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; from the order Isoptera, for example, Reticulitermes spp.; from the order Lepidoptβra, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotaiis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Gra- pholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Ly- onetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp.,

Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypi- ela, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scir- pophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp.,

Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.; from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order Psocoptera, for example,

Liposcelis spp.; from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; from the order Thysanoptera, for example,

Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii, Taeniothrips spp., Thrips palmi and Thrips tabaci; and from the order Thysanura, for example,

Lepisma saccharina.

The active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family, latex plants and ornamentals.

The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Myzus persicae and Nilaparvata lugens in vegetable, maize and rice crops.

Other fields of application of the active ingredients according to the invention are the protection of stored products and stores and of material, such as wood, textiles, floor coverings or buildings, and, in the hygiene sector, particularly the protection of humans, domestic animals and productive livestock against pests of the abovementioned type.

The invention therefore also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C,₂ of alkylbenzenes, such as xylene mixtures, al- kylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene gly- col or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- thylpyrrolid-2-one, dimethyl sulfoxide or N.N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil, and siiicone oils.

Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silicas or highly disperse absorbtive polymers. Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.

Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cyc- loaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsul- fates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethyl- ammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutyl- naphthalenesulfonic acid or of a naphthalenesuifonic acid/formaldehyde condensate. Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of a p- nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise from 0.0001 to 99.9999 %, in particular 0.1 to 95 %, of active ingredient, and 0.0001 to 99.9999 %, in particular 5 to 99.9 %, of - at least - one solid or liquid auxiliary, it being possible, as a rule, for 0 to 25 %, in particular 0.1 to 20 %, of the compositions to be surfactants (% in each case is per cent by weight). While concentrated compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions which have considerably lower concentrations of active ingredient.

The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally or acaricidally active ingredients. Suitable additions to active ingredients here are, for example, representatives of the following class of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives and Bacillus thuringiensis preparations. The compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidi- zed or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.

The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha. A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field

The compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation mateπal can be treated with the compositions prior to planting, for example seed can be treated prior to sowing. Alternatively, the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention

The examples which follow are intended to illustrate the invention They do not limit the invention Temperatures are given in degrees Celsius

Preparation Examples

Example H1 - 3-Acetyl-4-nιtroιmmo-perhydro-1 ,3,5-oxadιazιne

H Y C(=0)-CH₃ NNO, and 3-acetyl-4-nitroamino-2,3-dihydro-6H-1 ,3,5-oxadiazine, respectively

γ "C(=0)-CH₃ N(H)N0₂

A solution of 1 g of 4-nitroimino-perhydro-1 ,3,5-oxadiazine in 50 ml of acetonitrile is treated with 0.6 g of pyridine and 0.55 g of acetyl chloride. The reaction mixture is stirred for 15 hours at room temperature, freed from most of the solvent in vacuo, treated with 75 ml of ethyl acetate, washed in succession with in each case 50 ml of hydrochloric acid (1 N), saturated NaHCO₃ solution and saturated NaCI solution and concentrated in vacuo. This gives the title compound the form of an oil (Table 1 , Compound No. 1.1 ).

Example H2: The other compounds listed in Table 1 and the tautomers thereof can also be prepared analogously to the procedure described in Example H1.

1.13 -C(=O)-C₄H₇(Cyclo)

1.14 -C(=O)-C₅H₉(Cyclo)

1.15 -C(=O)-C₆Hn(Cyclo)

1.16 -C(=O)-CH(C₆H₅)₂

1.17 -C(=O)-CH₂C_βH₅

1.18 -C(=O)-CH₂CH(CH₃)C₆H₅

1.19 -C(=O)-CH₂C₆H₂(2,4,6-(CH₃)₃)

1.20 -C(=O)-C₆H₅

1.21 -C(=O)-C₆H₄(4-CI)

1.22 -C(=O)-C₆H₄(4-F)

1.23 -C(=O)-C₆H₄(4-CH₃)

1.24 -C(=O)-C₆H₄(4-CF₃)

1.25 -C(=O)-C₆H₄(4-OCH₃)

1.26 -C(=O)-C₆H₄(4-NO₂)

1.27 -C(=O)-C_βH₄(4-CN)

1.28 -C(=O)-C₆H₄(2-CI)

1.29 -C(=O)-C₆H₄(2-NO₂)

1.30 -C(=O)-C₆H₄(2-CH₃)

1.31 -C(=O)-C₆H₄(2-CF₃)

1.32 -C(=O)-C₈H₄(2-OCH₃)

1.33 -C(=O)-C₆H₄(2-OC(=O)CH₃)

1.34 -C(=O)-C₆H₄(3-CI)

1.35 -C(=O)-C₆H₄(3-NO₂)

1.36 -C(=O)-C₆H₃(2,6-CI₂)

1.37 -C(=O)-C₆H₃(2,6-(CH₃)₂)

1.38 -C(=O)-C₆H₃(2,6-(OCH₃)₂)

1.39 -C(=O)O-CH₃

1.40 -C(=O)O-CH₂CH₃

1.41 -C(=O)O-CH₂CH₂CH₃

1.42 -C(=O)O-CH₂CH₂CH₂CH₃

1.43 -C(=O)O-CH₂CH=CH₂

1.44 -C(=O)O-CH(CH₃)₂

1.45 -C(=O)O-CH₂CH₂CH=CH₂

98/0

- 32 -

and 3-(2-chloropyrid-5-ylmethyl)-4-nιtroamino-2,3-dihydro-6H-1 ,3,5-oxadιazιne, respectively

A mixture of 1.8 g of 4-nitroimino-perhydro-1 ,3,5-oxadiazιne and 20 ml of dry N,N-dιmethyl- formamide (DMF) is treated, at 0°, with 0.34 g of sodium hydnde (80% in oil), and the mixture is stirred for one hour at 0-5°. Then, a solution of 2 g of 2-chloro-5-chloromethyl-pyrι- dine in 20 ml of dry DMF is added dropwise in the course of 20 minutes at 0-5°. The reaction mixture is stirred for 2 hours at the same temperature, ice-water is added, and the mixture is extracted with ethyl acetate. The ethyl acetate phase is washed to neutrality with saturated NaCI solution, dried over Na₂SO₄ and concentrated. The crude product which remains as residue is purified by chromatography [silica gel; hexane/ethyl acetate (1:1)]. This gives the title compound, which melts at 158 to 160°.

Example H4- 3-(2-Chlorothιazol-5-ylmethyl)-4-nιtroιmιno-perhydro-1,3,5-oxadιazιne

and 3-(2-chlorothιazol-5-ylmethyl)-4-nιtroamιno-2,3-dιhydro-6H-1 ,3,5-oxadιazιne, respectively

The title compound, which is obtained in the form of an oil, can also be prepared in a manner analogous to the procedure described in Example H3.

Example H5: 3-Acetyl-5-(2-chlorothιazol-5-ylmethyl)-4-nιtroimιno-perhydro-1 ,3,5-oxadιazιne

A solution of the oil which can be obtained as described in Example H1 (Table 1 , Compound No. 1.1) in 15 ml of dry N.N-dimethylformamide (DMF) is treated, at 0 - 5°, with 0.2 g of sodium hydride (80% in oil) and stirred at room temperature until the evolution of hydrogen has ceased. A solution of 1.2 g of 2-chloro-5-chloromethyl-thiazole in a small amount of DMF is then slowly added dropwise. The reaction mixture is stirred for 30 minutes at 60°, poured into 75 ml of ice-water and extracted with 75 ml of ethyl acetate. The organic extract is washed to neutrality with saturated NaCI solution, dried over Na₂SO and concentrated. The crude product which remains as residue is purified by chromatography [silica gel; hexane/ethyl acetate (1 :1)]. This gives the title compound, which melts at 124 to 125° (Table 3, Compound No. 3.1).

Example H6: 3-Acetyl-5-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1 ,3,5-oxadiazιne

After 1 .7 g of acetyl chloride have been added to a mixture of 2 g of the compound which can be obtained as described in Example H3, 3 g of pyridine and 50 ml of dichloromethane, the mixture is stirred for 16 hours at room temperature, poured into 50 ml of hydrochloric acid (1 N) and extracted with 100 ml of ethyl acetate. The organic extract is washed with 50 ml of saturated NaCI solution, dried over MgSO₄ and evaporated. The crude product which remains as residue is purified by chromatography [silica gel; dichloromethane/methanol

(98:2)]. This gives the title compound, which melts at 103 to 105° (Table 2, Compound No.

2.1 ).

Example H7: 3-Benzylcarbonyl-5-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1 ,3,5-oxa- diazine

A solution of 2 g of the compound which can be obtained as described in Example H3 in 10 ml of dry N.N-dimethylformamide (DMF) is added dropwise at room temperature to a suspension of 0.23 g of sodium hydride (80% in oil) in 10 ml of dry DMF. The reaction mixture ιs stirred for 15 minutes at room temperature, a solution of 1.1 ml of phenylacetyl chloride in 10 ml of dry DMF is added, and the mixture is stirred for 16 hours at room temperature, poured into 50 ml of hydrochloric acid (1N) and extracted with 100 ml of ethyl acetate. The organic extract is washed with 50 ml of saturated NaCI solution, dried over Na₂SO₄ and evaporated. The crude product which remains as residue is purified by chromatography [silica gel; dichloromethane/methanol (99:1)]. This gives the title compound, which melts at 130° (Table 2, Compound No. 2.17).

Example H8: 3-(2-Chloropyrid-5-ylmethyl)-4-nitroιmino-5-phenoxycarbonyl-perhydro-1 ,3,5- oxadiazine

After 3.5 g of phenyl chloroformate have been added to a mixture of 2 g of the compound which can be obtained as described in Example H3, 3 g of pyridine and 20 ml of acetonitrile, the mixture is stirred for 16 hours at room temperature, freed from most of the solvent in vacuo, treated with 100 ml of ethyl acetate, washed in succession with in each case 50 ml of hydrochloric acid (1N), saturated NaHCO₃ solution and saturated NaCI solution and concentrated in vacuo. The residue is treated with 20 ml of diethyl ether and the mixture is stirred for 4 hours at room temperature. Filtration of the mixture gives the title compound, which melts at 103 to 105° (Table 2, Compound No. 2.52).

Example H9: The other compounds listed in Tables 2 to 4 can also be prepared analogously to the procedures described in Examples H5 to H8. In the column "Physical Data" of these tables, the temperatures given denote in each case the melting point of the compound in question.

2.28 -C(=O)-C_βH₄(2-CI)

2.29 -C(=O)-C₆H₄(2-NO₂)

2.30 -C(=O)-C₆H₄(2-CH₃)

2.31 -C(=O)-C_βH₄(2-CF₃)

2.32 -C(=O)-C_βH₄(2-OCH₃)

2.33 -C(=O)-C₆H₄(2-OC(=O)CH₃)

2.34 -C(=O)-C₆H₄(3-CI)

2.35 -C(=O)-C₆H₄(3-NO₂)

2.36 -C(=O)-C₆H₃(2,6-CI₂)

2.37 -C(=O)-C₆H₃(2,6-(CH₃)₂)

2.38 -C(=O)-C₆H₃(2,6-(OCH₃)₂)

2.39 -C(=O)O-CH₃ Amo hous

2.40 -C(=O)O-CH₂CH₃

2.41 -C(=O)O-CH₂CH₂CH₃

2.42 -C(=O)O-CH₂CH₂CH₂CH₃

2.43 -C(=O)O-CH₂CH=CH₂

2.44 -C(=O)O-CH(CH₃)₂

2.45 -C(=O)O-CH₂CH₂CH=CH₂

2.46 -C(=O)O-CH₂CH₂CI

2.47 -C(=O)O-CH₂CCI₃

2.48 -C(=O)O-CH₂CH(CH₃)₂

2.49 -C(=O)O-CH₂C₆Hn(Cyclo)

2.50 -C(=O)O-CH₂C₆H₅ 103-105°

2.51 -C(=O)O-CH₂C₆H₄(4-NO₂)

2.52 -C(=O)O-C₆H₅ 103-105°

2.53 -C(=O)O-C₆H₄(4-CI)

2.54 -C(=O)O-C₆H₄(4-NO₂)

2.55 -C(=O)O-C₆H₄(4-OCH₃)

2.56 -C(=O)NH-CH₃

2.57 -C(=O)NH-C₆H₅

2.58 -C(=O)C(=O)O-CH₃

2.59 -C(=O)C(=O)O-C₂H₅

2.60 -C(=S)NH-CH₃ 2.61 -C(=S)NH-C₆H₅ 2.62 -C(=O)-CH₂CH₂CH₂CH=CF₂ 82-84° 2.63 -C(=O)-(CH₂)₉CH=CF₂ Amorphous 2.64 -C(=O)-CH₂CH₂CCIF₂ 147-149° 2.65 -C(=O)-(4-CF₃-pyrid-3-yl) 140° 2.66 -C(=O)-CH(CH₂CH₃)C₆H₅ 2.67 -C(=O)-CHCICH₃ 2.68 -C(=O)-H 2.69 -C(=O)O-C(CH₃)₃ 2.70 -C(=O)-C(CH₃)=CH₂

4.1 -C(=O)-CH₃ 4.2 -C(=O)-CH₂CH₃ 4.3 -C(=O)-CH₂CH₂CH₃ 4.4 -C(=O)-CH₂CH₂CH₂CH₃ 4.5 -C(=O)-CH₂CH(CH₃)₂

4.39 -C(=O)O-CH₃

4.40 -C(=O)O-CH₂CH₃

4.41 -C(=O)O-CH₂CH₂CH₃

4.42 -C(=O)O-CH₂CH₂CH₂CH₃

4.43 -C(=O)O-CH₂CH=CH₂

4.44 -C(=O)O-CH(CH₃)₂

4.45 -C(=O)O-CH₂CH₂CH=CH₂

4.46 -C(=O)O-CH₂CH₂CI

4.47 -C(=O)O-CH₂CCI₃

4.48 -C(=O)O-CH₂CH(CH₃)₂

4.49 -C(=O)O-CH₂C₆H,₁(Cyclo)

4.50 -C(=O)O-CH₂C₆H₅

4.51 -C(=O)O-CH₂C₆H₄(4-NO₂)

4.52 -C(=O)O-C₆H₅

4.53 -C(=O)O-C₆H₄(4-CI)

4.54 -C(=O)O-C₆H₄(4-NO₂)

4.55 -C(=O)O-C₆H₄(4-OCH₃)

4.56 -C(=O)NH-CH₃

4.57 -C(=O)NH-C₆H₅

4.58 -C(=O)C(=O)O-CH₃

4.59 -C(=O)C(=O)O-C₂H₅

4.60 -C(=S)NH-CH₃

4.61 -C(=S)NH-C₆H₅

4.62 -C(=O)-CH₂CH₂CH₂CH=CF₂

4.63 -C(=O)-(CH₂)₉CH=CF₂

4.64 -C(=O)-CH₂CH₂CCIF₂

4.65 -C(=O)-(4-CF₃-pyrid-3-yl)

4.66 -C(=O)-CH(CH₂CH₃)C₆H_s

4.67 -C(=O)-CHCICH₃

4.68 -C(=O)-H

4.69 -C(=O)O-C(CH₃)₃

4.70 -C(=O)-C(CH₃)=CH₂ Formulation Examples (% = per cent by weight)

Example F1 : Emulsion concentrates a) b) c)

Active ingredient 25 % 40 % 50 % Ό

Calcium dodecylbenzenesulfonate 5 % 8 % 6 %

Castor oil polyethylene glycol ether (36 mol of EO) 5 % -

Tributylphenoxypolyethylene glycol ether (30 mol of EO) - 12 % 4 % Ό

Cyclohexanone . 15 % ₂o % o

Xylene mixture 65 % 25 % 20 %

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Example F2: Solutions

Active ingredient

Ethylene glycol monomethyl ether

Polyethylene glycol MW 400

N-Methylpyrrolid-2-one

Epoxidized coconut oil

Petroleum ether (boiling range: 160-190°)

The solutions are suitable for use in the form of microdrops.

Example F3: Granules a) b) c) d)

Active ingredient 5 % 10 % 8 % 21 % Ό

Kaolin 94 % - 79 % 54 % Ό

Highly disperse silica 1 % - 13 % 7 % Ό

Attapulgite 90 % - 18 % Itt

The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo. Example F4: Dusts Active ingredient Highly disperse silica Talc Kaolin

Ready-to-use dusts are obtained by intimately mixing carriers and active ingredient.

The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6. Emulsion concentrate

Active ingredient 10 % Ό Octylphenoxypolyethylene glycol ether (4-5 mol of EO) 3 %

Calcium dodecylbenzenesulfonate 3 %

Castor oil polyethylene glycol ether (36 mol of EO) 4 % o

Cyclohexanone 30 %

Xylene mixture 50 % o

Emulsions of any desired concentration can be prepared from this concentrate by dilution with water. Example F7: Qusts Active ingredient Talc Kaolin

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and thoroughly grinding the mixture in a suitable mill.

Example F8: Extruder granules

Active ingredient 10 %

Sodium lignosulfonate 2 %

Carboxymethylcellulose 1 %

Kaolin 87 %

The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.

Example F9 Coated granules

Active ingredient 3 %

Polyethylene glycol (MW 200) 3 %

Kaolin 94 %

In a mixer, the finely ground active ingredient is applied uniformly to tne kaolin which has been moistened with polyethylene glycol. This gives dust-free coated granules.

Example F10: Suspension concentrate

Active ingredient 40 %

Ethylene glycol 10 % 'c

Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %

Sodium lignosulfonate 10 %

Carboxymethylcellulose 1 %

37% aqueous formaldehyde solution 0.2 % Silicone oil (75% aqueous emulsion) 0.8 %

Water 32 %

The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.

Biological Examples (% = per cent by weight, unless otherwise specified)

Example B1 : Activity against Anthonomus grandis

Young cotton plants are sprayed with an aqueous emulsion spray mixture which comprises

400 ppm of active ingredient, and, after the spray coating has dried on, populated with 10 adult Anthonomus grandis and introduced into a plastic container. 3 days later, the test is evaluated. The percentage reduction in population and in feeding damage (% activity) are determined by comparing the number of dead beetles and the feeding damage between the treated and untreated plants.

In this test, compounds of Tables 2 to 4 show good activity.

Example B2: Activity against Aphis craccivora

Pea seedlings are infected with Aphis craccivora, subsequently sprayed with a spray mixture which comprises 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated and on untreated plants. In this test, compounds of Tables 2 to 4 show good activity. In particular, compounds nos. 2.1 , 2.2 and 2.20 have an efficacy of over 80 %.

Example B3: Activity against Bemisia tabaci

Dwarf bean plants are placed into gauze cages and populated with adult Bemisia tabaci. After oviposition has taken place, all the adults are removed. 10 days later, the plants with the nymphs thereon are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient. After a further 14 days, the percentage hatching rate of the eggs is evaluated in comparison with untreated control batches. In this test, compounds of Tables 2 to 4 show good activity. Example B4: Activity against Blattella oermanica

The amount of a solution (0.1%) of the active ingredient in acetone which is introduced into a Petri dish corresponds to a rate of application of 1 g/m². When the solvent has evaporated, 10 nymphs of Blattella germanica (last nymphal stage) are introduced into the dish, exposed to the action of the test substance for 2 hours, then anaesthetized with CO_2l transferred into a fresh Petri dish and kept in the dark at 25° and an atmospheric humidity of approximately 70 %. After 48 hours, the insecticidal activity is determined by determining the mortality. In this test, compounds of Tables 2 to 4 show good activity.

Example B5: Activity aoainst Ctenocephalides felis

Twenty adult Ctenocephalides felis are introduced into a shallow round cage which is closed on both sides with gauze. A container whose underside is sealed with a parafilm membrane is placed onto the cage. The container contains blood, which comprises 5 ppm of active ingredient and is kept at a constant heat of 37°. The fleas take up the blood through the membrane. 24 hours after the experiment has been set up, the blood is replaced by fresh, also treated blood. 24 and 48 hours after the experiment has been set up, it is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead fleas when using treated blood and when using untreated blood. In this test, compounds of Tables 2 to 4 show good activity.

Example B6: Activity against Diabrotica balteata

Maize seedlings are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient, and, after the spray coating has dried on, populated with 10 larvae (2nd instar) of Diabrotica balteata and introduced into a plastic container. 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead larvae between the treated and untreated plants. In this test, compounds of Tables 2 to 4 show good activity. In particular, compounds nos. 2.1 , 2.2, 2.17, 2.20, 2.39, 2.50, 2.52, 2.62 to 2.65, 3.1 to 3.8, 3.11 to 3.15, 3.19 to 3.26, 3.28 to 3.36, 3.38 to 3.40, 3.42, 3.44, 3.47, 3.50, 3.54, 3.57 to 3.61 and 3.66 to 3.70 have an efficacy of over 80 %. Example B7: Activity aoainst Heliothis virescens (foliar application)

Young soya plants are sprayed with an aqueous emulsion spray mixture which comprises

400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Heliothis virescens and introduced into a plastic container. 6 days later, the test is evaluated. The percentage reduction in population and in feeding damage

(% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.

In this test, compounds of Tables 2 to 4 show good activity.

Example B8: Activity against Heliothis virescens (application to eαosl Heliothis virescens eggs which have been deposited on cotton are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient. After 8 days, the percentage hatching rate of the eggs and the survival rate of the caterpillars are evaluated in comparison with untreated control batches (% reduction in population). In this test, compounds of Tables 2 to 4 show good activity.

Example B9: Activity against Lucilia cuprina

Batches of 30 to 50 freshly deposited eggs of Lucilia cuprina are each introduced into test tubes in which 4 ml of nutrient medium have previously been mixed with 1 ml of test solution comprising 16 ppm of active ingredient. After the culture medium has been inoculated, the test tubes are closed with a cotton-wool plug and incubated in the incubator for 4 days at 30°. Until this point in time, approximately 1 cm long larvae (3rd instar) have developed in the untreated medium. If the test substance is active, the larvae are either dead or their development is markedly delayed by this point in time. In this test, compounds of Tables 2 to 4 show good activity.

Example B10: Activity against Musca domestica

A lump of sugar is treated with such an amount of test substance solution that the concentration of test substance in the sugar is 250 ppm after drying overnight. The lump which has thus been treated and a wet cotton-wool ball and 10 adults of an OP-resistant strain of Musca domestica are then placed onto an aluminium dish. This dish is covered with a glass beaker and incubated at 25°. The mortality rate is determined after 24 hours. In this test, compounds of Tables 2 to 4 show good activity. Example B11 : Activity aαainst Mvzus persicae (foliar application!

Pea seedlings are infected with Myzus persicae, subsequently sprayed with a spray mixture which comprises 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated and on untreated plants. In this test, compounds of Tables 2 to 4 show good activity. In particular, the compounds nos. 2.1 , 2.2 and 2.20 have an efficacy of over 80 %.

Example B12: Activity aoainst Mvzus persicae (systemic application! Pea seedlings are infected with Myzus persicae, and the roots are subsequently placed into a spray mixture which comprises 400 ppm of active ingredient, whereupon the seedlings are incubated at 20°. 3 and 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated and on untreated plants.

In this test, compounds of Tables 2 to 4 show good activity. In particular, the compounds nos. 2.1 , 2.2, 2.17, 2.20, 2.39, 2.50, 2.52, 2.62 to 2.65, 3 1 to 3.8, 3.11 to 3.15, 3.19 to 3.26, 3.28 to 3.36, 3.38 to 3.40, 3.42, 3.44, 3.47, 3.50, 3.54, 3.57 to 3.61 and 3.66 to 3.70 have an efficacy of over 80 %.

Example B13: Activity against Nephotettix cincticeps (foliar application) Rice plants are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient and, after the spray coating has dried on, populated with larvae (2nd and 3rd instar) of Nephotettix cincticeps. 21 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hoppers on the treated and on untreated plants. In this test, compounds of Tables 2 to 4 show good activity.

Example B14: Activity against Nephotettix cincticeps (systemic application) Rice plants in pots are placed into an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient. The plants are subsequently populated with larvae (2nd and 3rd instar) of Nephotettix cincticeps. 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hop pers on the treated and on untreated plants.

In this test, compounds of Tables 2 to 4 show good activity.

Example B15: Activity against Nilaparvata luoens (foliar application)

Rice plants are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient and, after the spray coating has dried on, populated with larvae (2nd and 3rd instar) of Nilaparvata lugens. 21 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hoppers on the treated and on untreated plants.

In this test, compounds of Tables 2 to 4 show good activity. In particular, the compounds nos. 2.1 and 2.52 have an efficacy of over 80%.

Example B16: Activity against Nilaparvata lugens (systemic application)

Rice plants in pots are placed into an aqueous emulsion spray mixture which comprises 400 ppm of active ingredient. The plants are subsequently populated with larvae (2nd and 3rd instar) of Nilaparvata lugens. 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hoppers on the treated and on untreated plants.

In this test, compounds of Tables 2 to 4 show good activity.

Claims

What is claimed is:

1 A compound of the formula

in which A is a substituted or unsubstituted heterocyclyl group; -E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R,)-R, -C(=O)C(=O)-R, -C(=O)C(=O)O-R, -C(=O)C(=O)N(R₁)-R or -C(=S)N(R_t)-R;

R is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group, and

R, is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group, or, where appropriate, a tautomer thereof, in each case in free form or in salt form.

2 A compound according to claim 1 of the formula I, in which the ring skeleton of A is composed of a ring having 5 or 6 ring members or of a ring having 5 or 6 ring members to which a further ring having 5 or 6 ring members is fused, or, where appropriate, a tautomer thereof

3 A compound according to claim 2 of the formula I, in which the ring skeleton of A compπses no double bond or 2 to 4 conjugated double bonds, or, where appropriate, a tautomer thereof

4 A compound according to claim 3 of the formula I, in which the ring skeleton of A comprises 1 up to and including 4 ring heteroatom(s), a ring nitrogen atom also to be understood as meaning its N-oxide form, or, where appropriate, a tautomer thereof.

5. A compound according to claim 4 of the formula I, in which the ring skeleton of A comprises 1 , 2 or 3 ring heteroatom(s), selected from the group, consisting of oxygen, sulfur and nitrogen (where a ring nitrogen atom is also to be understood as meaning the N-oxide form thereof), where the ring skeleton comprises not more than one ring oxygen atom and where the ring skeleton comprises not more than one ring sulfur atom, or, where appropriate, a tautomer thereof.

6. A compound according to claim 5 of the formula I, in which A is bonded to the remaining moiety of the compound I via a C atom of its ring skeleton, or, where appropriate, a tautomer thereof.

7. A compound according to claim 6 of the formula I, in which A is unsubstituted or mono- to tetrasubstituted, where up to 2 of the substituents of A are selected from the group, consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkinyloxy, alkenylthio, haloalkenylthio, alkynylthio, haloalkynylthio, cyano and nitro, and where, if A is tri- or tetrasubstituted, each substituent of A, which differs from the two substituents, which lead to the disubstitution of A, is selected from the group, consisting of alkyl, alkoxy and halogen, or, where appropriate, a tautomer thereof.

8. A compound according to claim 7 of the formula I, in which the ring skeleton of A is a te- trahydrofuryl, pyridyl, 1 -oxidopyridinio or thiazolyl group, or, where appropriate, a tautomer thereof.

9. A compound according to claim 1 of the formula I, in which -E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R₁)-R, -C(=O)C(=O)O-R or -C(=S)N(R -R and R, is C C₅alkyl, C₂-C₅alkenyl, C₂-C₅. alkynyl, C₃-C₇cycloalkyl, aryl, heteroaryl or hydrogen, or, where appropriate, a tautomer thereof.

10. A compound according to claim 1 of the formula I, in which R is hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group, which is unsubstituted or mono- to trisubstituted by substituents, selected from the group, consisting of halogen, cyano, nitro, tnalkylsilyl, amino, alkylamino, dialkylamino, alkyl, haloalkyi, hydroxy, alkoxy, haloalkoxy, alkoxyalkoxy, mercapto, alkylthio, haloalkylthio, alkyisulfinyl, haloalkylsulfinyl, alkylsulfinyloxy, ha- ioalkylsulfinyloxy, alkylsulfonyl, haloalkylsulfonyl, alkylsulfonyloxy, haloalkylsulfonyioxy, al- kylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, cycloalkyl, halocycloalkyl, cycloalkoxy, halocycloalkoxy, cycloalkylthio, halocycloalkylthio, aryl, aryloxy, arylthio, arylsulfinyl, arylsulfinyloxy, arylsulfonyl, arylsulfonyloxy, arylamino, N-alkyl-arylamino, N-formyl- arylamino, N-alkylcarbonyl-arylamino, arylcarbonyl, arylcarbonyloxy, non-aromatic heterocyclyl, non-aromatic heterocyclyloxy, non-aromatic heterocyclylthio, heteroaryl, heteroaryloxy, heteroarylthio, heteroarylsulfinyl, heteroarylsulfinyloxy, heteroarylsulfonyl, heteroarylsulfonyloxy, heteroarylamino, N-alkyl-heteroarylamino, N-formyl-heteroarylamino, N-alkylcarbo- nyl-heteroarylamino, heteroarylcarbonyl and heteroarylcarbonyloxy, where the aryl and heteroaryl substructures in the last-mentioned aryl, aryloxy, arytthio, arylsulfinyl, arylsulfinyloxy, arylsulfonyl, arylsulfonyloxy, arylamino, N-alkyl-arylamino, N-formyl-arylamino, N-alkylcarbonyl-arylamino, arylcarbonyl, arylcarbonyloxy, heteroaryl, heteroaryloxy, heteroarylthio, heteroarylsulfinyl, heteroarylsulfinyloxy, heteroarylsulfonyl, heteroarylsulfonyloxy, heteroarylamino, N-alkyl-heteroarylamino, N-formyl-heteroarylamino, N-alkylcarbonyl-heteroarylami- no, heteroarylcarbonyl and heteroarylcarbonyloxy substituents independently of one another are unsubstituted or mono- to trisubstituted by substituents, selected from the group, consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkoxy, haloalkoxy, alkylthio, haloalkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio and halophenylthio, and where the non-aromatic heterocyclyl substructures in the last-mentioned non-aromatic heterocyclyl, non-aromatic heterocyclyloxy and non-aromatic heterocyclylthio substituents independently of one another are unsubstituted or mono- to trisubstituted by substituents, selected from the group, consisting of halogen, cycloalkyl, halocycloalkyl, alkyl, haloalkyi, alkoxy, haloalkoxy, alkylthio, haloalkylthio, oxo, thioxo, nitro, cyano, phenoxy, halophenoxy, phenylthio and halophenylthio, or, where appropriate, a tautomer thereof.

11. A compound according to claim 8 of the formula I, in which A is a tetrahydrofur-3-yl, py- rid-3-yl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-Cι-C₃alkylpyrid-5-yl, 1 -oxido-3-pyridinio, 2- halo-1-oxido-5-pyridinio, 2,3-dihalo-1-oxido-5-pyridinio or 2-halothiazol-5-yl group, -E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R,)-R, -C(=O)C(=O)O-R or -C(=S)N(R₁)-R, R, is C,-C₅alkyl, C₂-C₅alkenyl, C₂-C₅alkynyl, C₃-C₇cycloalkyl, aryl, heteroaryl or hydrogen and R is hydrogen; a Cι-C₈alkyl group, which is unsubstituted or mono- to trisubstituted by substituents, selected from the group, consisting of halogen, d-C₅alkylcarbonyloxy, C₃-C₈cycloalkyl, unsubstituted phenyl and phenyl which is mono- to trisubstituted by substituents, selected from the group, consisting of Cι-C₅alkyl and nitro; a C₂-Cι₅alkenyl group, which is unsubstituted or mono- to trisubstituted by substituents, selected from the group, consisting of halogen; an unsubstituted C₃-C_θcycloalkyl group; a pyridyl group, which is unsubstituted or mono- to trisubstituted by substituents, selected from the group, consisting of halo-C _rC₅alkyl; or a phenyl group, which is unsubstituted or mono- to trisubstituted by substituents, selected from the group, consisting of halogen, cyano, nitro, C_rC₅alkyl, halo-d-Csalkyl, d-Csalkoxy and Cι-C₅alkylcarbonyloxy, or, where appropriate, a tautomer thereof.

12. A compound according to claim 11 of the formula I, in which A is a 2-chloropyrid-5-yl or 2-chlorothiazol-5-yl group, -E-R is -C(=O)-R or -C(=O)O-R and R is unsubstituted phenyl or Cι-C₅alkyl, which is unsubstituted or monosubstituted by unsubstituted phenyl.

13. A compound according to claim 12 of the formula I, selected from the group, consisting of the compounds

14. A process for the preparation of a compound according to claim 1 of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form, which comprises a) reacting a compound of the formula

in which E and R have the meanings given for formula I, or a tautomer and/or salt thereof, with a compound of the formuta

Y-E-R (V), which is known or which can be prepared analogously to corresponding known compounds and in which E and R have the meanings given for formula I and Y is a leaving group, or, where appropriate, with a tautomer and/or salt thereof, preferably in the presence of a base, or c) to prepare a compound of the formula I, in which -E-R is -C(=Z)N(H)-R and Z is O or S, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of the formula

—

Z=C=N-R (VI), which is known or which can be prepared analogously to corresponding known compounds and in which R has the meaning given for formula I and Z is O or S, or, where appropnate, with a tautomer and/or salt thereof, preferably in the presence of a base, and/or converting a compound of the formula I or a tautomer thereof, in each case in free form or in salt form, into another compound of the formula I or a tautomer thereof, separating an isomer mixture which can be obtained in accordance with the process and isolating the desired isomer and/or converting a free compound of the formula I or a tautomer thereof into a salt or a salt of a compound of the formula I or a tautomer thereof into the free compound of the formula I or a tautomer thereof or into another salt.

15. A pesticidal composition, which comprises at least one compound according to claim 1 of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient and at least one auxiliary.

16. A composition according to claim 15 for controlling insects or representatives of the order Acarina.

17. A process for the preparation of a composition according to claim 15, which comprises intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).

18 The use of a compound according to claim 1 of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, for the preparation of a composition according to claim 15.

19. The use of a composition according to claim 15 for controlling pests.

20. The use according to claim 19 for controlling insects or representatives of the order Aca¬

21 The use according to claim 19 for the protection of plant propagation material from the attack by pests.

22. A method for controlling pests, which comprises applying a composition according to claim 15 to the pests or their environment.

23. A method according to claim 22 for controlling insects or representatives of the order Acarina.

24. A method according to claim 22 for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted.

25. Plant propagation material treated in accordance with the method described in claim 24.

26. A compound of the formula

(ID.

^{H'N N E'B}

NNO,

in which

-E-R is -C(=O)-R, -C(=O)O-R, -C(=O)N(R,)-R, -C(=O)C(=O)-R, -C(=O)C(=O)O-R, -C(=O)C(=O)N(R,)-R or -C(=S)N(R,)-R;

Ri is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group, or a tautomer thereof, in each case in free form or in salt form.

27. A process for the preparation of a compound according to claim 26 of the formula II or a tautomer thereof, in each case in free form or in salt form, which comprises d) reacting the compound of the formula

I I (VII),

H γ H

NN0₂

Y-E-R (V), which is known or which can be prepared analogously to corresponding known compounds and in which E and R have the meanings given tor formula II and Y is a leaving group, or, where appropriate, with a tautomer and/or salt thereof, for example analogously to the process described under variant b) for the corresponding reaction of a compound of the formula IV or a tautomer and/or salt thereof with a compound of the formula V or, where appropriate, with a tautomer and/or salt thereof, or e) to prepare a compound of the formula II, in which -E-R is -C(=Z)N(H)-R and Z is O or S, or a tautomer and/or salt thereof, reacting a compound of the formula f ^"ϊ (VII),

H Y H NN0₂

Z=C=N-R (VI), which is known or which can be prepared analogously to corresponding known compounds and in which R has the meaning given for formula II and Z is O or S, or, where appropriate, with a tautomer and/or salt thereof, for example analogously to the process described under variant c) for the corresponding reaction of a compound of the formula IV or of a tautomer and/or salt thereof with a compound of the formula VI or, where appropriate, with a tautomer and or salt thereof, and/or converting a compound of the formula II or a tautomer thereof, in each case in free form or in salt form, into another compound of the formula II or a tautomer thereof, separating an isomer mixture which can be obtained in accordance with the process and isolating the desired isomer and/or converting a free compound of the formula II or a tautomer thereof into a salt or a salt of a compound of the formula II or of a tautomer thereof into the free compound of the formula II or a tautomer thereof or into another salt.

28. The use of a compound according to claim 26 of the formula II or a tautomer thereof, in each case in free form or in salt form, for the preparation of a compound according to claim 1.