BG60863B1 - Nitroguanadine derivatives, method for their preparation and application - Google Patents

Abstract

Nitroguanidine derivatives are used to control pests, insects and arachnids that attack crops and animals. They have a general formula in which the substituents have the meanings given in the description.

Description

The invention relates to novel nitroguanidine derivatives, to a method for their preparation, and to their use in pest control.

Insecticides have been described in the literature as heterocyclic compounds containing a nitroguanidine structure (EPA-192-060). However, the biological properties of these compounds are not fully satisfactory in pest management. Individual compounds excluded from the definition of Formula I have been described in the literature as intermediates for pharmaceutically active compounds having antileukemic and antimicrobial activity. These compounds also have the biological properties of other substances of formula I. Therefore, when used as an active substance in agrochemicals, they also form an integral part of the present invention.

The nitroguanidine derivatives of the invention have the following general formula I:

N — SN — A o ₂ nn = c ' _r

Νζ; R ₄ wherein: Rj is hydrogen, _b4 alkyl or C ₃ _ _b cycloalkyl,

R ₂ is hydrogen or C _1-4 alkyl; R ₃ is hydrogen, C _1-4 alkyl or C _3-6 cycloalkyl; R ₄ is hydrogen, C _1-4 alkyl, C _3-6 cycloalkyl or a residue

-CHR ₅ -B or R ₃ and R ₄ together represent - (CH ₂ ) ₄ - or - (CH ₂ ) ₅ , R ₅ stands for hydrogen or C _1-4 alkyl, A stands for unsubstituted or mono- to quaternary substituted aromatic or non-aromatic, monocyclic or a bicyclic heterocyclic moiety wherein one to two of the substituents are selected from the group C 1 -C ₃ -halogenalkyl, cyclopropyl, halogencyclopropyl, C ₂ -C ₃ -alkenyl, C ₂ C ₃ -alkynyl, C ₂ -C ₃ -halogenalkenyl, C ₂ -C ₃ -halogenalkinil, Cj-C ^ haloalkoxy, C j - C ₃ alkylthio, C j -C ₃ -halogenalkiltio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, alogenaliltio, cyano and nitro, and one to four of the substituents are selected from C ^ -L-alkyl, Ci-C alkoxy, and halogen, and

B means phenyl, cyanophenyl, nitrophenyl, halogenphenyl of 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, through one to two substituents of the group C ₁ -C ₃ -alkyl, C ₂ -C ₃ -halogenalkyl, cyclopropyl, halogencyclopropyl ₂ -C ₃ -alkenyl, C ₂ -C ₃ -alkynyl, C ₁ -C ₃ -alkoxy, C ₂ -C ₃ -halogenalkenyl, C ₂ -C ₃ -halogenalkynyl, C, C ₃ -halogenalkoxy, C, -C ₃ - alkylthio, C 1 -C 3 -halogenalkylthio, allyloxy, propargyloxy, allythio, propargylthio, halogenallyloxy, halogenallythio, halogen, cyan and nitro substituted 5-thiazolyl; or by one to two residues of the group C ₁ -C ₃ haloalkyl, cyclopropyl, halogencyclopropyl, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ -alkynyl, C ₂ -C ₃ -halogenalkenyl, C ₂ -C ₃ -halogenalkynyl , C ₃ -halogenoxy, C 1 -C 3 -alkylthio, C 1 -C 3 -halogenoalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, halogenallyloxy, halogenallythio, cyan and nitro or by one to four substituents of the C 1 -C 3 -alkyl group. _3- alkoxy or halogen substituted 3-pyridyl; as well as their salts with inorganic acids, with the exception of the compounds 1-nitro-2- (pyrid-3-ylmethyl) -guanidine, 1-nitro-2- (pyrid-2-ylmethyl) -guanidine, 1-nitro-23). pyrid-4-ylmethyl) -guanidine, 1-nitro-2- (1-oxo-pyrid-3-ylmethyl) -guanidine and 1- (benzimidazol-2-ylmethyl) -2-nitroguanidine.

The compounds of general formula I according to the invention also include salts with agrochemically tolerable inorganic acids. Examples of such acids are hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and nitric acid, as well as acids having the same central atom and a higher or lower oxidizing state such as perchloric acid, nitric acids or phosphoric acids.

The compounds of general formula I may also occur in tautomeric forms 1a or 1b when at least one of the residues R 1, R ₃ or R ₄ represents a hydrogen atom.

o ₂ n-nh— c ^ n-chr ₂ ^x nr ₃ r ₄ / 1a /

NRPCHR2-A

O ₂ N-NH— —R3 (oderR4) / 16 /

Formula I according to the invention should be understood to include formulas 1a and 1b in the spelling of formula I.

The ring systems included in the definition of the heterocyclic residue A contain as a ring member at least one heteroatom, meaning that at least one of the main ring-shaped atoms is different from carbon.

- 4 - ether ring-

this residue; is preferably unsaturated and bonded via a carbon atom as a ring member to the main body of nitroguanidine. The general formula I. Unsaturated ring systems of definition k contain one or more double bonds, preferably such ring systems are unsaturated several times and possess the most are often aromatic in nature. Preferred are such ring systems that contain at least one nitrogen atom as a hetero atom. Generally, such rings of definition A contain one to three heteroatoms of the oxygen, sulfur group and nitrogen, wherein they contain at most one oxygen or sulfur atom. Preferred ring systems of definition A are those in which the heterocyclic residue A contains one to three heteroatoms from the group oxygen, sulfur and nitrogen, where nitrogen is always a hetero atom and contains one more oxygen or one sulfur atom. In particular, examples of heterocycles of the definition A according to the invention are found in the group of basic bodies of the following structures:

>

- 5 * ►

In

and:

In the above formulas, E represents C 1 -C 4 -alkyl and Y represents t hydrogen, C 1 -C 4 -alkyl or cyclopropyl.

For example, the heterocycle® A listed may be unsubstituted or optionally substituted on. The ring system may have up to four substituents, such as those indicated for formula I. Preferably, these heterocycles are 1 unsubstituted form, bonded via a carbon atom to the guanidine body, or having from one to three halogen substituents, ,χ-Οβ- alkyl, C 1 -C 6 -halogenalkyl-1-C 3 -halogenalkoxy or C 1 -C 6 * alkoxyl. Heterocycles A with a pyridyl or triazolyl moiety, such as 3-pyridyl, 2-halogenpyrid-5-yl, are very preferred.

2,3-dihydroxypyrid-5.-yl, 2-haloxythiazol-4-yl, 1-oxide-pyridin-3-yl, 1- oxo-2-halogenpyridyl-yl, 1-oxo-2,3- dihalpyrid-5-yl.

In the definition of Formula I according to the invention, the individual generic terms should be understood as follows

Halogen atoms being considered as substituents refer to both fluorine and chlorine as well as bromine and iodine, where fluorine, chlorine and bromine are preferred. Halogen investigators® should be understood as a single substituent or as part of a substituent such as in haloalkyl, haloalkylthio, haloalkyl oxy, halogencycloalkyl, haloalkenyl, haloalkynyl, haloalloxy or haloalkylthio. Examples of such alkyls may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, seg: butyl, zhacto and tert-butyl. Suitable alkoxy radicals may include, but are not limited to: methoxy, ethoxy, propoxy , isopropoxy, butoxy and their isomers. Alkylthio means, for example, methylthio, ethylthio, isopropylthio, propyl® or isomers of butylthio.Also referred to as alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl substituents

- and the residue is substituted by halogen, they may be alone or partially perhalogenated. The above definitions apply to hodagen, alkyl and alkoxy. Examples! for the alkyl elements of these groups are one to three times by fluorine, chlorine and / or bromine substituted methyl, such as CHP ₂ or ΟΡθ; mono- to pentasubstituted by fluorine, chlorine and / or bromine, substituted ethyl, such as CH ^ ₽z, S₽ ^ ₽ ^, S₽-C1 _3, CP-CHC1 _2, CP ^ ST₽ ₂ S₽ ^ S₽S1 ₂ Cl ₂ CHBr ₂ S₽ ^ _NS1₽,; C $ ^ C $ CH or CCIPCHCIl? ; one to three times fluorine, chlorine and / or bromine substituted propyl or isopropyl, such as CHgCHBrCH ^ Br, CPgCHFCF ^, CH ^ CP ^ P ^ length CH / CPg / j * once to nine times through fluorine, chlorine and / or bromine substituted butyl or one of its isomers: form © for example CP / CPg / CHPCP ^ or CHg / CP ^^ P ^; 3-chlorocyclopropyl or 2,2difluorocyclopropyl, 2,2-difluorovinyl, 2 _? 2dichlorovinyl, 2-chloroalkyl,

2,3-dichlorovinyl or. 2,3-dibromvinyl.

If said alkyl, alkoxy or cycloalkyl groups are substituted with other substituents, they may be substituted one or more times with the same or different substituents listed. Preferably, the substituted groups may contain one or two other substituents. cycloalkyl residues. 9this word for cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Alkenyl groups and alkynyl groups contain an unsaturated carbon-carbon bond. Typical representatives are allyl, metalyl, propargyl, or also vinyl and. the triple bonds in allyloxy, propargyloxy, allyltif, or propargyl are separated from the point of attachment to the heteroatom (oxygen or sulfur), preferably via a saturated carbon atom.

From the compounds of formula I such subgroups should be highlighted, at. which or a / K ^ and 1? ₂ independently of one another denotes hydrogen, methyl, ethyl or cyclopropyl, or

≪ RTI ID = 0.0 > b / R8 represents hydrogen, or in / Rf represents hydrogen or: methyl.

In the case that / R ^. means the group -CHR 1 -B, those compounds wherein R 1 represents hydrogen are preferred. Preferred embodiments of B are phenyl, pyridyl or thiazolyl, which are respectively substituted unsubstituted or / by one to three residues of the halogen group.

C 1 -C 3 -alkyl-3-halogenalkyl-pC 3 -halogenalkoxy or C 3 -Calkoxy.

A particularly preferred group of compounds of general formula I is characterized by the fact that R 1, R 2, independently of one another, are hydrogen, methyl, ethyl or cyclopropyl, R 8 represents hydrogen, hydrogen or methyl and A represents pyridyl, 1- ok is opiridyl, thiazolyl, or by one to three substituents, respectively, of the halogen, C 1 -C 6 -alkyl, C 1 -C 3 -halogenoalkyl, C 1 -C 3 -halogenalkoxy or C 1 -C 3 -alkoxy substituted pyridyl, 1-oxopyridyl or thiovolide group.

As preferred individual compounds of formula I may be mentioned:

1- (2-chloropyrid-5-ylmethyl) -1-methyl-2-nitroguanidine;

1- (2-chloropyrid-5-ylmethyl) -2-nitroguanidine;

1-methyl-2-nitro-3- (pyrid-3-ylmethyl) -guanidine;

1-methyl-2-nitro-1- (pyrid-3-ylmethyl) -guanidine;

1,2-dimethyl-3-nitro-1- (pyrid-3-ylmethyl) -guanidine;

1- (2-chloropyrid-5-ylmethyl) -1,2-dimethyl-3-nitroguanidine;

1- (2-chloro-ortho-5-yl-ethyl) -1-ethyl-2-nitro guanidine;

1- (2-chloropyrid-5-ylmethyl) -2,2-dimethyl-3-nitroguanidine;

1- (2-chloropyrid-L-ylmethyl) -2-methyl-3-nitroguanidine;

1,1-dimethyl-2-nitro-3- (virid-3-ylmethyl) -guanidine;

1- ethyl-2-nitro-3- (pyrid-3-ylmethyl) -guanidine;

1-ethyl-2- (2-chloropyrid-5-ylmethyl) -3-nitroguanidine;

1- ethyl-1-methyl-2- (2-chloropyrid-5-ylmethyl) -3-nitro guanidine;

- 10 *

1- (2-chlorothiazol-5-ylmethyl) -2,2-dimethyl ethyl-3-nitroguanidine;

1- (2,3-dichloropyrid-5-ylmethyl) -Z-ethyl-3-nitrogu anidine;

1-ethyl-2- (2,3-dichloropyrid-5-ylmethyl) -3-nitroguanidine;

1- (2,3-Dichloropyrid-5-ylmethyl) -1-methyl-2-nitroguanidine; 1-ethyl-1- (2,3-dichloropyrid-5-ylmethyl) -2-nitroguanidine;

1- (2-chloro-1-oxopyrid-5-ylmethyl) -1-methyl-2-ytroguanidine;

1-ethyl-1- (2-chloro-1-fluoro-5-ylmethyl) -N-nitroguanidine;

1- (2-chloro-op-1-oxopyrid-5-ylmethyl) -2-methyl-3-nitroguanidine;

1-ethyl-1- (2-chloro-op-1-oxopyry-5-ylmethyl) -3-nitroguanidine;

1- (2-chlorothiazol-5-ylmethyl) -2-methyl-3-nitroguanidine;

1- (2-chlorothiazol-5-ylmethyl) -2-nitroguanidine and

1-ethyl-2- (2-chlorothiazol-5-ylmethyl) -3-nitroguanidine.

The compounds of the invention of general formula I can be prepared analogously according to known methods. For example, compounds of general formula I are prepared as or.

a / amine of the general formula II

H-NRpCHRg-A (II),

B8) aimodeist> uva a nitrois a urea of the general formula III / III /

- OrH - m = c ^{x ά} in which Rp R ₂ , R ₃ , R 5 and A have the formula (I) indicated, or:

b) compound of the father of formula IV

Hal-CHYA ₂ -A (IV), reacted in the presence of a base with a nitroguanidine derivative of the general formula

V '

O ^ SE-N = C ^ z-NPp-H (V) in which & < EMI ID = 0.0 > have the meanings given in formula I, and, Hal represents halogen, preferably chlorine or bromine.

The compounds a of formula 1,1 which ^and R 4, denote hydrogen, may also be prepared as an amine of formula II

Wherein Rp R ₂ h A has the meanings given in formula I, are reacted with or 1-methyl-1-nitroso-2-nitroguanidine is formula VI

or with nitroguanidine. with the formula VII

Carrying out variant a / of the method according to the invention

(II + IIL * fr I) is preferably carried out in an inert solvent at temperatures between 0 ° C and + 150 ° C, in particular between + 40 ° C and + 120 ° C. Suitable solvents are especially / alcohols, methanol kat® "ethanol or isopropanol .Variantat b / / IV + V -91 / ¹ is preferably carried out in an inert polar aprotic solvent such as acetonitrile or smoke ethyl temperatures between + 50 ° C and. Temperature boiling the reaction mixture. As bases are suitable: carbonates such as potassium carbonate. As bases hydrides may also be used, such as sodium hydride. When using sodium hydride in acetonitrile or dimethylformamide, the reaction temperature can be reduced by +10 ®C to + 25 ° C, without that eaktsionnoto time substantially udalzhi.Vzaimodeystvieto of P © VI is preferably carried out in aqueous alcoholic solution at temperatures between 0 ° C and + 25®S.Prk this interaction is obtained as an intermediate N-nitro h om ethyl amine. The interaction of II with VII is normally carried out in an aqueous medium

- 12 at temperatures between + 40 ° C and + 100 ° C, preferably between + 60 ° C and +80 ° C.

From compounds of formula Ia

O ^ E - N = C

- CH - A ^x kn ₂ (1a), where R 1. And do they have the meanings given in formula I by?

reaction to alkylated® presence? based on the use of the re-

alkylation gases

Kdghal or

R ^ -Hal, where® R ^, Rg and? R 6 has the meanings given in formula I which do not represent hydrogen, and Hal means halogen, preferably chlorine or bromine. guanidine derivatives of the general Formula I, wherein R1, R8, and R1 have such meanings that are not hydrogen.

As is known, the alkylation reactions of the above type proceed in a specific manner, this alkylation step is particularly suitable for the preparation of tertiary amino groups, i. in particular for cases! which must simultaneously substitute the three remaining hydrogen atoms for the guanidine nitrogen atom with the same. residues R1, R8 and: R4.

On the other hand, such guanidines can be easily obtained by alkylation of the above type. derivatives of formula 1, in which all of the residues R1, Rg = and R4 have non-hydrogen meanings whenever we want to introduce only one of these residues at the site of the hydrogen atom. guanidine scaffold- 13 -

years, kata -CHRg-A or. the residues introduced or the alkylation reaction of this type. it can also be used to prepare e.exercise guanidine-amino groups. If the compounds of formula Ia react, react with only one or two equivalents of the alkylating reagent, both mixtures of isomers and alkylation products with varying degrees of alkylation.These mixtures can be separated by? the usual methods of separating their individual components so that, among other things, the desired product can be selected.

As the reaction conditions for the said alkylation reactions, we choose a temperature between 0 ° C and + 150 ° C, preferably between + 50 ° C and + 50 ° C. As alkaline and alkaline earth metal hydrides, such as sodium hydride or calcium hydride, are suitable bases, or carbonates of alkali or. alkaline earth metals such as sodium carbonate or. calcium carbonate. The alkylation reaction is preferably carried out in a polar, aprotic solvent, such as acetonitrile or. dimethylformamide.

The intermediates © formulas II, 111,1 V, V, VI and VLI are known or can be hd analogous to; familiar methods.

It has now been found that the compounds of Formula I according to the invention with favorable tolerance by warm-blooded animals, fish and plants are valuable active substances in the elimination of pests. In particular, the application of the active substances of Formula I according to the invention relates to insects and arachnids. which are found in useful and ornamental plants in agriculture, in particular in cotton, vegetables and fruit plants, in forestry, in the protection of warehouses and materials, and in the hygiene sector in particular. animal and useful animals.They are effective against all or individual stages of the development of normally susceptible, as well as resistant species.In this case, their activity can be expressed in the immediate killing of pests or only after

-14 Some time, for example, when changing the skin, or in reduced laying and / or hatching eggs. To the above-mentioned pests! refer:

from the Lepidoptera order, for example

Acleris spp..Adoxophyes spp., Aegeria spp., Agrotis spp..Alabama agrillaceae, Amylois spp., Anticarsia gemmatai is, Archips spp..Argyrotaenia spp..Autographa spp., Bussed a fisca.Cadra cautella.Carposina.Carposina.Carposilo.Carposina.Carposina.Carposina.Carposina spp..Choristoneura spp., Clysia ambiguella.Cnaphalocrocis spp..Cnephasia spp..Cochylis spp..Coleophora spp., Crocidolomia binotalis.Cryptophlebia leucotreta, Cydia spp..Diatraea spp., Diparopsis castanea., Diparopsis castanea. .Ephestia spp., Eucosma spp..Eupoecilia ambiguella.Euproctis spp. Euxoa spp., Grapholita spp., Hedya nubiferana.Heliothis spp., Hellula'undalis, Hyphantria cunea, Keiferia lycopersicella.Leucoptera scitella.Lithocollethis spp., Lobesia botrana.Lymantria spp., Lyonetasmpp. Manduca sexta.Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays sppes, Scirp, Spir. spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni And Yponomeuta spp., from the Col eoptera order, e.g.

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibial is, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhpponthpp. Spp. Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp., And TrogodermaT; eg Blatta spp..Blatella spp..Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp and Schistocerca spp .;

from the isoptera order, for example

Reticulitermes spp .; OT of the Psocoptera order, for example Liposcelis spp., OT of the Anoplur order, eg Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp,; OT of the Mallophaga order, for example Damalinea spp. and Trichodectes spp .;

from the Thysanoptera order, for example

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci AND Scirtothrops aurantii ,;

from the Heteroptera order. for example

Cimex spp., Distantiella tneobroma, Dysdercus spp., Euchistus spp., Eurygaster spp.

Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. HTriatoma spp .;

from the Homoptera order, for example

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi.Coccus hesperidum.Empoasca.Empoasca. Laodelphax spp..Lecanium corni.Lepidosaphes spp., Macrosiphus spp., Myzus spp. , Nephotettix spp..Nilaparvata spp..Paratoria spp., Pemphigus spp..Pianococcus spp..Pseudaulacaspis spp. .Pseudococcus spp., Psylla spp., Pulvinaria aethiopica.Quadraspidiotus spp..Rhopalosiphum spp..Saissetia spp., Scaphoideus spp..Schizaphis spp..Sitobion spp..Trialeurodes vaporariorum.Thioza erytaeaerea;

From Hymenoptera discharge, for example

Acromyrmex.Atta spp., Cephus spp., Diprionidae, Gilpinia polytoma, Di prion spp., Hoplocampa spp., Lasius spp..Monomorium pharaonis.Neodiprion spp.Solenopsis spp.,

And Vespa spp .;

from the _Diptera order, for example

Aedes spp..Antherigona soccata, Bibio hortulanus, Calliphora erythrocephalla, Ceratitis spp..Chrysomyia spp., Culex spp..Cuterebra spp., Dacus spp..Drosophila melanogaster.Fannia spp..Gastrophilus spp..Glossina spp..Gppossa ..Hyppobosca spp..Liriomyza spp., Lucilia spp..Melanagromyza spp., Musca spp., Oestrus spp..Orseolia spp..Oscinella frit.Pegomyia hyoscyami.Phorbia spp..Rhagoletis pomonella.Sciara spp., Stomox spp., Stomox spp. , Tabanus spp., Tannia spp., Tipula spp .;

from the Siphonaptera order, for example

Ceratophyllus spp..Xenopsylla cheopis, from the Asanpa order, for example

Acarus siro.Aceria sheldoni.Aculus schlechtendali.Amblyomma spp., Argas spp., Boophylus spp..Brevupalpus spp., Bryobia praetiosa, Calipitrimerus spp..Chorioptes spp., Dermanyssus gallinae.Eotetranychus spp. Ixodes spp..Olygonychus pratensis.Ornithodoros spp..Panonychus spp..Phyllocoptruta oleivora.Polyphagotarsonemus latus.Psoroptes spp..Rhipicephalus spp.,

- 16 Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. And Tetranychus spp .; And

From a Thysanura discharge, for example Lepisma saccharine.

The good pesticidal activity of the compounds of the invention O- the general formula I corresponds to a degree of mortality (mortality) of at least 50-60% of said pests:.

The activity of the compounds of the invention. 'And of the agents containing them may be substantially enhanced by the addition of other insecticides and / or acaricides and may be adapted to the circumstances.

the following classes of active substances at organic phosphorus compounds, nitrophenols and their derivatives, formamides> ureas, carbamates, pyrethroids, chlorinated hydrocarbons and preparations based on bacilius

The compounds of formula I are used in unaltered form, or preferably together with conventional formulation auxiliaries, and can therefore be processed, for example, to emulsifiable concentrates, solutions, direct, sprayed or. dilution, diluted: emulsions, powders for the preparation of

suspensions, soluble powders, sprays, granules, as well as sealing in polymeric substances in a known manner. Methods of application such as spraying, aerosolization, dusting, spraying or irrigation are selected as well as the means according to the set, purpose and given conditions. .In addition, the compounds of formula (I) are suitable for use in seed treatment. In addition, as before sowing, seeds may be treated or stained with the active substance or with the active substance containing the formulation, but also the active substance may be a & apply to the furrow during sowing.

The wording, i. containing the active substance of formula I, respectively combinations of these active substances with others

- 17 *

insecticides or. acaricides, and optionally solid or liquid additives, preparations or compositions are prepared in a known manner, for example by homogenization and / or; grinding of the active substances with excipients, for example with solvents, solid carriers, and optionally with surfactants (surfactants).

As solubilizing agents there are suitable: hydrocarbons, preferably the fractions Cq up ^of alkylbenzenes, such as xylene mixtures or alkylated naphthalenes, aliphatic or cycloaliphatic. hydrocarbons, such as cyclohexane, paraffin or tetrahydronaphthalene, alcohols such as ethanol, propanol or butanol, in glycols, and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycolmonomethyl- or isethylether, or ethylether di ad ethanol alcohol, strong polar solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide or water, vegetable oils such as rapeseed oil, castor oil, coconut oil or. soybean oil; in this case also k silicone oil.

As solid carriers, for example, for crushing agents and soluble powders, natural, mineral flours such as calcite, talc, daolin, montmorillonite or attapulgite are generally used. To improve the physical properties, they can also be highly dispersed. : silicic acids; or highly dispersible permeable polymerizers. These are crushed adsorptive granular media. refer to porous types such as pumice stone, crushed, bricks, sepiolite or bentonite, as well as non-adsorbing carrier materials such as calcite or sand. In addition, many granular materials of inorganic or organic origin, and in particular dolomite or crushed vegetable residues, may also find an application.

As surfactants, depending on the type of formulated active substance of formula I or the combinations of these active substances with other insecticides or acaricides; have

- 18 - considering non-ionic, cationic and / or anionic. is surfactant; good emulsifying, dispersing and wetting properties.Tensides should also be understood as tenside mixtures.

Suitable anionic surfactants may be, as is. water-soluble soaps as well as water-soluble synthetic surfactants.

Suitable as soaps are alkaline, alkaline earth or: optionally substituted higher fatty acid ammonium salts ^{, such as} sodium or potassium salts. oleic or stearic acids, or mixtures of natural acids: which are obtained, for example, from coconut oil or tall oil. In addition, methyl-taurine salts, aliphatic acids, should also be taken as surfactants.

However, they are more commonly used. synthetic surfactants, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or ankylarylsulfonates.

Fatty sulfonates or sulfates are generally found as alkaline, alkaline earth or optionally substituted ammonium salts and typically have one alkyl residue of 8 to 22 carbon atoms, the alkyl also including: the alkyl moiety of the acyl residue :, for example, the sodium or calcium salt of ligninsulfonic acid, the dodecylsulfuric acid ester, or from natural fatty acids:. fatty alcohol-sulfate mixture. The salts of sulfuric acid esters and: sulfonic acids are adducts based on fatty alcohol-ethylene oxide. The sulfonated benzimidazole derivatives preferably contain 2 groups of sulfonic acid and one residue; of fatty acid by about 8 to. 22m carbon atoms. Alkylaryl sulfonates are for example the sodium, calcium or triethanolamine salts. of dodecylbenzenesulfonic acid dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid and formaldehyde based condensation product.

In addition, suitable phosphates such as salts of. Phosphoric acid ester of p-nonylphenol- (4-14) -ethylene oxide adduct or phospholipids.

Like non-ionic surfactants. first of all: polyglycol ether derivatives, of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the / aliphatic / hydrocarbon residue and 6 carbon atoms g in the alkaline portion of the alkylphenol. Other suitable nonionic surfactants containing water-soluble (I) up to 250 ethylene glycol groups and 10 to 100 propylene glycol groups are polyethylene glycol adducts of polypropylene glycol, ethylenediaminopolypol and opylene glycol alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyd chain. The compounds generally contain, for the propylene glycol unit, 1 g of 5 ethylene glycol units.

For example, such as nonionic surfactants, nonylphenol polypolyethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol -trioleate.

In the case of cationic surfactants, it is first of all: o quaternary ammonium salts which, as an N-substituent, contain at least one alkyl residue having 8 to 22 carbon atoms, while other substituents have lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl residues. The salts are preferably present as halides, methylsulphates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyl di (2-chloroethyl) ethylammonium bromide.

- 20 The surfactants used in the formulation technique are described, for example, in the following publications:

Me Cutcheon's Detergents and Emulsifiers Annual, Me Publishing Corporation, Glen Rock, NJ, USA, 1988;

H. Stache, Tensid-Taschenbuch, 2. Aufl., C. Hanser Verlag, Munich, Wien 1981.

M. and J. Ash. Encyclopedia of Surfactants, Volume I-III, Chemical Publishing C New York, 1980-1981.

Pesticide preparations generally contain 0.1 to 99%, in particular 0.1 to 95% of the active substance of formula I or combinations of this active substance with insecticides or acaricides, 1 to 99.9% of solid or liquid additive and 0 to 25 %, in particular 0.1 to 25% surfactant. While commercial products: concentrated agents are more often preferred, end users generally use diluted blanks (which have significantly lower concentrations than the active substance. Typical concentrations) for administration are between 0.1 and 1000 ppm, preferably between 0, 1 and 500 ppm. The amounts used per hectare are generally from 1 to 1000 g of active substance per hectare, preferably 25 to 500 g / hectare.

Preferred formulations are as follows; follows: /% = weight percent / Emulsifiers concentrates:

Active substance: 1 to 90%, preferably 5 to 20%

Surfactant: 1 to 30%, preferably 10 to 20% Liquid carrier: 5 to 94%, preferably 70 to. 85%

Powders:

Active substance: 0.1 to 10%, preferably 0.1 to 1%

Solid media: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates:

Active substance 5 to 75%, preferably 10 to 50%

Water 94 to 24%, predominantly 88, up to 30%

Surfactant: 1 to 40%, preferably 2 to 30%.

-21Understand dust

Active substances: 0), 5 to 90%, preferably 1 to 80%;

Surfactant): 0:, 5 to 20%, preferably 1 to 15%;

Solid media: Granulate 5 to 95%, preferably 15 to 90%. Active substance: 0.5 to 30%, preferably 3 to 15%; Solid media: 99.5 to 70%, preferably 97 to 85%.

The agents may also contain other additives, such as stabilizers, for example in the case of epoxidized vegetable oils / epoxidized coconut oil *, rapeseed oil or soybean oil / ,, dehumidifiers, eg silicone oil, preservatives, regulators: viscosity, binders, agent it is attached as well as fertilizers or other active substances to achieve special effects.

The following examples serve to illustrate the invention. They do not limit the invention.

EXAMPLES FOR PREPARATION:

Example H1; 1r (2-chloropyryl-5-ylmethyl) -1-methyl-2-nitroguanidine

CHO-M-C = N - NO ₉ ² II ² CH ₃ nh ₂

A mixture of 3.2 g of N-methyl- (2-chloropyrid-5-yl) -methylamine,

The 2,7-S-methyl-KE-nitroisothiourea, 0.2 g of potassium hydrosulfate and ml of ethanol are heated at reflux for 4.5 hours. The reaction mixture is filtered hot. The filtrate crystallizes on cooling to 0 ° C. The crude product. Recrystallization from ethanol gave pure 1- (2: -chloropyrid-5-ylmethyl) -1-methyl-2-nitroguanidine as colorless crystals of melting point: 163-165 ° C.

- 22 -

Example Η21 1- (2-Chloopioid-5-ylmethyl) - 2-nitroguaniline

Suspension qt 4.0 g nitroguanidine and 5.4 g / 2-chloropyrid-

The 5-yl / -methyl amine in 80 ml of water was heated to + 80 ° C for three hours. After cooling the reaction mixture to + 20 ° C, the product was separated as a colorless crystalline mass for 16 hours. The crystalline powder was separated, washed with methanol and dried to give 2.0 g of 1- (2-chloropyrid-5-ylmethyl) -2-nitroguanidine with a melting point of 195-197 ° C.

Example H3x1- (2-Chloropyrid-5-ylmethyl) -2- (4-chlorobenzyl) -1-methyl-3-

0.7 g of 55 N sodium hydride is added at 10-15 ° C in small; portions to a solution of 4.0 g of 1- (2-chloropyrid-5-ylmethyl) -1-methyl-2-nitroguanidine in 50 ml of dimethylformamide. After 20 minutes, a solution of 2.65 was added dropwise at 10-15 ° C. g of 4-chlorobenzyl chloride in 5 ml of dimethylformamide. The reaction mixture was stirred for 20 hours at ambient temperature and then poured into 200 ml of ice water. The aqueous solution was extracted with chloroform. The organic layer! was separated, dried and concentrated by evaporation. Purification by column chromatography on silica gel gave 1- (2-chloropyrid-5-ylmethyl) -2- (4-chlorobenzyl) -1-methyl-3-nitroguanidine with a point of mp 130-132 ° C.

Compounds of the general formula I according to the invention can be prepared in the same way as the one given in the following table.

Table 1ϊ

- 23 - «1 * 2 - N = CH _ CH - 'Λ ^R 2s * 3 «4 Η Η Η Η Η Η Η C% Η Η ? Η Η Η 0¾ Η Η dream ₃ Η Η ^With L. Η Η CgHj-B Η Η 0— Η Η CgEjrHSO Η

Physical constants

mp = 163-165 ° C t, mp = 195-197%

mp = 162-163%

mp 134-136% resin * -NMR / CDCl3 /

2.96 IS, ZN / "SJSbiS" ZN /,

..70: / S, F / "

8.10 / broad: S, 1H /

mp = 129-131%

mp = 125-127%

R4 Physical constants

Contents No. A

- 24 -

With ₄ Sun-n Ή m- 88-90 ° C C ^ Hg-oeKi Η ^CH 3 ^CH 3 mp = 158-160 ° C ^dream a mp = 115-119 ° C Fri ₃ C ₄ Sun. ^C A ^C A resin C ₄ Sun-H C ₄ Sun-H -CH-SNLSHCH.U / Si / c

Physical constants.

mp = 136-138; ° C

Η

Η

Η

Η

Η

mp = 107-109 ° C

C 1 -H; Η

Ι> - η

I Η

- 26.

^R 1 ^K 2 ⁸ 3 n n 0¾ n n > -  n n dream ₃ n ^{sleep with} dream _a dream ₃ n ^with a ⁿ ? " ⁿ n dream ₃ ^With # 5 dream ₃ n With% n n n n n CHA

Physical, constants

And so on

n

n

n

n

dream ₃

Physical constants

Saud, .№ A

% »3 ®4 1> - n n n ^With # 5 n n n % n ^{sleep with} n dream _a n n n ^{dream with} > n dream ₃ n ^with l n n n ^with * n θ ^Η 3 n n n θ ^Η 3 0¾ 1> - n dream ₃ n ™ 3 n n n ^{sleep with} n dream _a n

COMPOUND A

CI

R ₃ ^R 4 Physical constants H H H H CH _a H H CH ₃ CH _3i H ^CH 3 H H H H H CH ₃ H H H H H ^c % H H CHa 0¾ H H H H H H

X

Saud A

1.80)

11.81

1.82.

· 83

1.84

1.85

1.86.

1.87

1.88

1.89

1.90 '

- 3CL

^R 1 4 83 r ₄ Physical constants 0¾ H CH ₃ H H H H ^C A · H 0¾ H H H ^CH 3 CH ₃ > - H H H lx * ^- H H H ^CH a H H H mp = 112-114% 0¾ H ^CH 3 H ^With L. H H H ^c * H CH ₃ H ^C 2% H ^c * H

- 31Compound · Ν = A ^P 1 ^R 3 ^R 4

H _: ^ n .¾ dream ₃ n n dream ₃ CI n n. dream _a n 1> - n n n 1> -n ^dream a n dream ₃ n n n dream ₃ n dream ₃ n 1> - n n n SNp. n n n

Physical, constants.

Τ'.Τ. = 159-160 ° C CH ₂

N

mp . = 168-170¾

¢ .11. = 203 ^ 205¾

-32Computer

1.108

1.101 CI

Physical constants

mp = 198) -200 ° C

mp = 2SIG-20L

mp = 148-150 ° C

mp = 145-146% ^R 1 ^R 2% ^R

Physical constants

CI

τ. ¢. = 113 ^ 116¾

mp = 158-160¾

mp = 210-212¾

τ. ¢. = 202-233%

C%

mp = 161-163¾

“Ϊ“ 1 Η Η Η ^ι · ^ιιΒ χχ α ⁰ Η Η ^With A. 1,116 (l jT |> - dream ₃ Η

¢. ^. = 158-160¾

1.1. = 135-136¾

1.117 α dream ₃ dream ₃ dream _a 1.118 J θ ^Η 3 ^{sleep with With} # 5

% «1

Comp

CH

1.119

1.12ED

1.126.

1,128

Physical constants

CI

1.1211

° 2 «5

Oh—

Compound .N§

A

Physical constants

1,129

1.130

1.134

With% ^With # 5 n dream ₂ CH _and ^Mr. n n CH _and ^Mr. mp = 173-175 ° C n n ^C # ^5H v. ¢. = 159-16 A n n > —N n n ΟβΗψ — Ηΐ N n n CH _January sdts <- * 'Mm 9lJ' dream ₃ n ^With # 5 and dream _a . n C ^ -H H n n - / 0¾ n n ₅ - n ^{sleep with} , - / ° ¾

Acting Physical Constants

Comp46

1.141

H ^SN ₃ - ^{/ SI} ACI

1.142 DU Η 1.143 DU ^C % 1.144 DU Η 1.145 DU θ ^Η 3 1.145 DU ^C # 5 1.147 DU ^C 2% 1.148 DU Η 1.149 DU Η 1.150, JfY Η 1.151 ίτ ^With L '

^ 3 ^? 4

Physical constants.

^c % ^{n C} J

1.154 D7L ^With 3? 7 ⁿ n n 11.155 dd C ^ H ^ -H n % 1.156 DD ^with sp * Mr ⁿ n ^With # 5 1.157 DD N. n N. 1.156 dd n n n 11.159 dd dream ₃ n n 1.160 H || dream ₃ n n

N.

1 C1-C4-iso N. N. T. C 1 H 2 -iso N. ^with % 1 C ^ H ^ -iso N. ^With # 5

Physical constants

Compound 1? A

1.164

1.165

1.166

1.167

1.16 &

1.169

1.170.

1.171

1.17a

1.173

1.174

1.175

Table 1 (continued):

Connected®

---- No. --------- A -------— Eg - K Physical Constants:

EXAMPLES FOR MUSHROOMS? /% = weight percentage /

Example P1: Emulsifiers. concentrates

Active substance No. 1.05

Calcium dodecylbenzenesulfonate

Castor oil polyethylene glycol ether / 36 mole ethylene oxide /

Three butylphenolpolylethyl ethyl ether (30 moles of ethylene oxide)

Cyclohexanone

Xylene mixture

a / b / w in/ 25% 40% 50% 5% 8% 6% 5% - - 12% - 15% M 65% 25%

From such concentrates, emulsions of any desired concentration can be obtained by diluting with water.

Example $ 2: Solution: a / b / w in/ d / Active substances. №1.05 sof · 10% 5% 95% Et il anglic olmonometer il ep - - - Polyethylene glycol / mole weight 400 / - Yes - N-methyl-2-pyrrolidone - 20% - - Epoxidized coconut oil - - 1% 5% Gasoline / boiling range 160 -190 ° C / 94%

The solutions are suitable for use as small droplets.

RH example :. Granulate and:

a B C D/

Active substance No. 1.05

5% 10% 8%

- 40 -

a / b / w in/ d / Kaolin. $ 94 - 79% 54 « Highly dispersed silicon k $ 1 - 13% 7% Atopulgitis 90% - 10% The active substance is dissolved in methylene chloride and applied by spraying on the carrier and solvent is removed after this in a vacuum by evaporation. Example $ 4: Powder a / b / w Active substance N? IJ05 & 5% Highly dispersed silicic acid 1% 5% Talc: 97% - Kaolin - 90% By fine mixing the carrier with the active substance a ready-to-use detergent is obtained. Example $ 5: .Dust spray a / b / w in/ Active substance No. 1.01 or 1.03 / 25% 50% 75% Sodium ligninsulfonate 5% 5% - Sodium lauryl sulfate 3% - 5% Sodium diisobutylnaphthalenesulfonate - 6% 10% Octol enolpoly ethyl anglic ol ether / 7-8 moles of ethylene oxide / - 2% - Highly dispersed silicic acid $ 5 10% 10% Kaolin 6 # 27% -

The active substance or combination of active substances is mixed with the additives and ground in a suitable mill well. A spray powder is obtained which can be diluted with water up to ^! suspension at any desired concentration.

Example P6: Emulsion Concentrate

Active substance Nil .01 or 1.03 10%

Octylphenol polyethylene glycol ether / 4-5 moles of ethylene oxide / 3%

- 41 *

Calcium dodecylbenzenesulfonate 3% Ritsinov om asl enpol iglik ol er / 36 moles of ethylene oxide / £ 4 Cyclohexanone 3 » Xylene is ® 5W From this concentrate can be obtained through dilution with water an emulsion of any desired concentration. Example F7: Powder a / b / w Active substance N51.02 & 8% Talc - Kaolin - It is ready; for use remedy for begging

wherein the active substance < mix with the carrier and grind in a suitable mill. Example $ 8>: Extruded granulate Active substance N51.06 10 * Sodium ligninsulfonate 2 * Carboxymethylcellulose $ 87 The active substance or. combinations of active

The ingredients are mixed with additives, ground and moistened with water. This mixture is filtered, granulated and then air-dried.

Example P9: Shell granule

Active substance N51.04

Polyethylene glycol / molecular weight 230 /

Kaolin $ 94

The finely divided active substance or combination of active substances is applied uniformly in a mixer to a polyethylene glycol-moistened kaolin. This results in a powder-free, coated granulate.

- 42 Example P10: Suspension concentrate

Active substance N51.01 40%

Et il anglic ol 10%

Nonylphenyl oil or glycol oil / 15 mol ethylene oxide / 6%

Sodium ligninsulfonate 10%

Carboxymethylcellulose 1%

Silicone oil as 75% aqueous emulsion 1%

Water 32%

The finely divided active substance or combination of active substances is mixed with the additives. A suspension concentrate is obtained from which, by dilution with water, a suspension of any desired concentration can be obtained. BIOLOGICAL EXAMPLES;

Example B1: Activity against ITQxbci

Rice plants are treated with an aqueous emulsion spray solution containing 400 ppm of active substance®. After the spray dried, the rice plants are inhabited by cicadas larvae / in the 2nd and 3rd stages of development. After 21 days the evaluation is carried out. From comparing the number of surviving cicadas on treated with that on untreated plants, the percentage is determined decrease in population /% activity /.

The compounds of Table 1 show good activity against this assay. In particular, the compounds 1.01, 1.03, 1.04, 1.05; 1.07, 1.14, 1.15, 1.81, 1.86, 1.93,

1.107, 1.108, 1.113 and 1.115 show activity above 80%.

Example B2: Activity against -Λί ^ Ρ ^ ϋί ^ ίίΐΑ

Rice plants are treated with an aqueous emulsion spray solution containing 400 ppm of active substance.

- 43 After the spray dried, the rice plants are inhabited by cicada larvae in the 2nd. and 3 stages of development.After 21 days, the evaluation is carried out. From comparing the number of surviving cicadas on treated plants with that on untreated plants, the percentage reduction of the population is determined /% activity /

water ® obtained

The compounds at Table 1 exhibited good activity against the TiZphotEttlx Cbiciidlpi in this assay. In particular compounds 1.01, 1.06, 1.14, 1.15 and 1.91 showed activity above 80%. Example B3, Larval activity of S &lt; JDL ^ XX> ~ ttC (t bddE / xfXu.

Germinated maize is sprayed with an emulsion spray solution containing 400 substances. After drying the sprayed layer our plants are populated with 10 larvae in the second of and placed ner.After 6 days the evaluation is carried out.From comparing the number of ppm of the active germination stage of development in plastic container larvae on treated plants with that on untreated plants is determined by the percentage reduction of the population (% activity).

The compounds of Table 1 show good activity against the larvae of this assay. In particular, compound 1.01 shows activity above 80%.

Example B4: Activity against caterpillars of.

Young? soybean plants are sprayed with an aqueous emulsion spray solution containing 400 · ppm of the active substance. After drying the sprayed soybean plants are populated with 10 caterpillars of the first, stage of development, and placed in a plastic container.

After 6 days the evaluation is carried out. From comparing the number of dead caterpillars and the damage from eating on treated plants with that of untreated plants, the percentage reduction is determined

- 44 of the population, respectively, of the percentage reduction of the damage from eating /% activity /.

The compounds of Table I showed good activity in MeLlOίΚί · $ in this experiment. In particular, compounds 1.01, 1.107 g 1.110 showed activity above 80%.

Example B5: SpodOpiffiQ ilito witS caterpillar activity,

Young soybean plants are sprayed with. aqueous emulsion spray solution containing 400 ppm active. ' substance. After drying the sprayed soybean plants are populated with 10 caterpillars: from SpOCLopi ^ td in the third stages of development and placed in a plastic container. After 3 days, the evaluation is carried out. From comparing the number of dead caterpillars and the damage of eating on the treated plants this on the untreated plants determines the percentage reduction of the population, respectively, the percentage reduction of the damage from eating.

/% activity /.

The compounds of Table 1 showed good activity against Spod'Cpi &lt; Lactiotyxltl in this assay. In particular, compounds 1.01, 1.03, 1.07 ^ 1.14, 1.86,1.107 and 1.108 showed activity above 80%.

Example B6; Activity against ftphiS CtftCCLtCy

Sprouted peas were infected with A pkts CraCClvorCl and then sprayed with a spray solution containing 400 ppm of the active substance and incubated at 20 ° C. After 3 and 6 days, respectively, an evaluation was carried out. aphids on treated plants with untreated plants determine the percentage reduction in the population (% activity).

The compounds of Table 1 show good activity against ftplUt) in this experiment. In particular, the compounds 1.01,1.03,1.04,1.05,1.06,1.07,1.14,1.15,4.24,1.86,1.91,1.93,

1.99, 1.107,1.114 and 1.115 show good activity (above 80%).

An example. Q7: Systemic activity against Jidanawata

Pots: C; Rice plants are placed in a solution of water emulsion containing 400 ppm active substance. Rice plants are then populated with larvae in stages 2 and 3. After six days, the evaluation is carried out. From the comparison of the number of cicaditf on treated and that on untreated plants, the percentage reduction of the population (% activity) is determined.

The compounds of Table 1 show good activity in this experiment. In particular, the compounds 1.01, 1.03, 1.04, 1.06, 1.07, 1.14, 1.15, 1.86, 1.93, 1.107, 1.114. and 1,115 show activity over 80%.

Example B8 * System activity vs

Rice pots are placed in a water emulsion solution containing 400 ppm of active substance. Larvae are then settled on the rice plants in 2nd and 2nd; 3rd flock! After 6 days, an estimate is made. From comparing the number of cicadas on treated plants then on untreated plants, the percentage reduction of the population (% activity) is determined.

The compounds of Table 1 show good activity against C1-6 LCLCpS in this assay. compounds 1.01, 1.03, 1.04 ^ 1.06,1.14, 1.15, 1.86,1.91 and 1.114. show activity above 80%.

400 ppm of active substance and incubated at 20 ° C. After 3 and 6 days, respectively _, an estimate _is made. From the comparison of the number of dead aphids, on the treated with that on untreated plants, the percentage reduction of the population is determined /% activity / .

The compounds of Table 1 show good activity against such experiment. In particular, the compounds

1.01, 1.06, 1.14 and 1.86 show activity above 80%.

Example B10: Activity against adults.

Young cotton plants are sprayed with an aqueous emulsion solution containing 400 ppm of active substance. After drying the sprayed layer on the cotton plants are sown 10 adults each and placed in a plastic container. After three days an assessment is made. comparing the number of dead beetles and eating damage; on treated plants with that on untreated plants the percentage reduction of the population, respectively the percentage reduction of the damage from eating (% activity) is determined.

The compounds of Table 1 show good activity against this assay. In particular, compounds 1.01, 1.14, 1.15, 1.86, 1.91 and 1.93 show activity above 80%.

Example B 11: Activity against UdbQp & c ·.

Plants of low-stem beans are placed in a cell of metal tissue and are populated by adults (white fly) .After laying eggs, all adults: are removed and after 10 days: the plants with nymphs on them are treated with derived from aqueous emulsion spray solution from the active substances tested (concentration 49Θ ppm). The evaluation is carried out 14 days after the administration of the active substance and is expressed as a% hatching compared to untreated controls.

The compounds according to Table 1 show in this experiment a good activity against 'BoOb.bC'. More specifically the compounds

1.01, 1.06, 1.07, 1.14, 1.86, 1.107 and 1.108 show activity above 83%.

- 47

Example B 12: Activity Against Fly ΧζζΧΧα Shuya.

Pre-laid eggs from Myxaira. $ Z, cZZ «J are placed in small portions / 30-50 eggs / in pre-mixed tubes. 4 ml of culture medium with 1 ml of test solution containing 16 ppm of test active substance

After injection of the culture medium, the tubes are closed with cotton plugs and placed in an incubator at 30 ° C for 4 days. During hatching, approximately 1 cm long larvae develop in the untreated environment (stage 3). If the substance is active, then the larvae will either be dead or lagging behind in their development at the same time. The assessment is made after 96 hours.

The compounds of Table 1 show good activity

against

in this experience.

Claims (4)

I. Nitroguanidine Derivatives of Formula I d / ² 1 * 2 / M - CH - (J) - H = C « ² \ X ² 3 n denotes hydrogen, R3 or C14 cycloalkyl; means hydrogen or C 1-6 alkyl; denotes C1-6 alkyl or &quot; C 1-4 cycloalkyl; means hydrogen, Rocky, C 1-4 cycloalkyl or a residue I '<sf | -the - (dream ₂ ) ₅ -; ) D in which: 2j «2« 3 «4 -СИ5В- И « I3 together denotes hydrogen or C1-6 alkyl; &Lt; 7 &gt; means an unsubstituted or one to four times substituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic moiety, wherein one to two substituents are selected from the group C 1-4 halogen cyl, cyclopropyl, halogencycloprodyl, C 2-4 alkenide, C 1-4 haloalkyl, C 1-4 halogen, C ^^ haloalkenyl, _{C2-haloalkynyl,} C ^ -haloalkoxy, C ^ alkylthio, C ^ haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano or nitro, and one to four substituents selected from the groups C ^ alkyl, C _1-5 alkoxy and halogen and (S) MARK ca phenyl, cyanophenyl, nitrophenyl, halophenyl with I to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, with one to two substituents from the group C ^ alkyl, C ^ haloalkyl, cyclopropyl, halogentsiklopropil, C ₂ _ ₅ alkenyl, C ₂ _ ₅ alkynyl, C ^ alkokoi, C ₂ _ ₅ haI - 49 logenalkynyl, C1-4 haloalkoxy, C1-4alkylthio, C1-4 haloalkylthio, allyloxy, proparglyloxy, allylthio, propargylthio, halogenoaltyloxy, halogenallylthio, halogen, cyanoo nitro substituted 5-thiazolyl; or by one to two residues of the group C 1-4 haloalkyl, cyclopropyl, halogencyclopropyl, C 2-4 alkenyl, C 1-4 alkynyl, C 1-4 haloalkynyl, C 1-4 haloalkynyl, C 1-4 haloalkoxy, C 1-4 alkylthio, C 1-4 haloalkylthio, allyloxythio, allyloxythiol propargylthio, halogenallyloxy, halogenallythio, cyano and nitro, or by one to four residues of the group C 1-6 alkyl, C 1-4 alkoxy or halogen substituted 3-pyridine, as well as their salts with inorganic acids. v,. except for the compounds: 1-nitro-2- (pyrid-3-ylmethyl) -guanidine, 1-nitro-2- (pyrid-2-ylmethyl) guanidine, 1-nitro-2- (pyrid-4-ylmethyl) _v guanidine, 1-nitro-2- (1-oxo-pyrid-3-ylmethyl) - guanidine and 1- (benzimidazol-2-ylmethyl) -2-nitroguanidine. ^: ........ ........ ..... _ Compounds according to claim I, in which the heterocyclic residue A is unsaturated and is bonded to the main nitro moiety of Formula I - ~ guanidine via a carbon atom and contains at least one nitrogen atom. . Compounds according to claim 2, wherein the heterocyclic residue A is unsaturated and is linked via a carbon atom to the main nitroguanidine and contains one to three heteroatoms in the oxygen, sulfur and nitrogen series, always containing at least one oxygen OR sulfur atom . Compounds according to claim 3, wherein the heterocyclic residue A contains one to three heteroatoms from the acid-. genus, sulfur and nitrogen, of which always one of the heteroatoms is nitrogen and at most one oxygen or sulfur atom is the other heteroatoms. - 50 5; Compounds according to claim I, wherein the heterocyclic residue A is a carbon bonded to a guanine radical from the group of: