CS197216B2 - Insecticide means - Google Patents

Abstract

Title cpds. are of formula I, (where R1 = 1-4C alkyl, O alkyl or S alkyl; R2 = 1-7C alkyl, propenyl or propynyl; R3 = H, Me or Et; R4 = 1-4C alkyl, 2-6C alkenyl, cycloalkylmethyl, furfuryl, or tetrahydrofurfuryl; R5 = 1-6C alkyl, or 2-6C alkenyl; or NR4R5 = morpholino, piperidino, methylpiperidino, pyrrolidino, or hexamethyleneimino; or R3+R4 or R5 forms a 5-6 membered ring, and the remaining substit. = Me or Et; and X and Y = O and/or S). I are prepd. (a) by condensing (R'O)(R2Y)P(=X)NH2 with (R6O)2CR3NR4R5, (b) (R'O)(R2Y)P(=X)Cl with NH=C(R3)NR4R5, or (c) reacting (R7O)R'P(=S)N=C(R3)NR4R5 with R2 hal; where R6 and R7 = l.alkyl.

Description

The present invention relates to novel amidines, to a process for their preparation and to their use as insecticidal compositions.

The amidines of the invention correspond to the general formula I

R10 O R3 \ II /

P — N = CH — N / \

RzSRi (I). in which

R 1 represents a n group,

1.

(II)

R 10 O \ || -NH 2 ^: +

P

OF

R2 or ethyl

R 2 is C 1 -C 3 alkyl, propenyl or propynyl, and either R 3 and R d are ethyl or R 3 'and R 4 together with the nitrogen atom to which they are attached form a morpholino or piperidino group.

The compounds of formula (I) above may be prepared by methods known per se:

reaction temperature -50 to +100 ° C

-------- U (I)

19721В

2. R1O O R3 \ ll OF p — ci + NH = CH - N ev. reagent OF \ acid R2S R4 ----------- (D (IV) (IN) 3. R1O S Rs R1O 0 Rs  \ ll OF OF P — N = CH — N + RžHhI -------- P — N = CH — N / OF OF \ R‘O R4 R2S R4 (VII) (VIII)

In formulas (II) to (VIII), R 1 to R 1 have the meaning given in formula (I), each of R 6 and R 6 being a lower alkyl group and Hal represents an anion, for example an anion, chloride, bromide or iodide or sulfuric acid ester residue.

Suitable acid binding agents are tertiary amines, for example trialkylamines, pyridine and dialkylanilines, and furthermore inorganic bases such as alkali and alkaline earth metal hydrides, hydroxides, carbonates and acid carbonates.

Reactions 1 and 2 are carried out under normal pressure, excluding moisture and in inert solvents or diluents.

Suitable inert solvents or diluents are, for example, ethers and ether type compounds such as diethyl ether, dipropyl ether, dioxane and tetrahydrofuran, aliphatic and aromatic hydrocarbons, including halogenated, in particular benzene, toluene, xylenes, chloroform and chlorobenzene, and nitriles such as acetonitrile.

The starting materials of the formulas II to V are in part known compounds which can be prepared according to known methods. Thus, methods for the preparation of the amidacetals required for the work of reaction 1) are summarized in Zeitschrift fur Chemie 9, 201 (1969) and the preparation of (thio) phosphoric acid amides in Houben-Weyl, Methoden der organischen Chemie, Vol. Phosphor II.

The compounds of the formula I have a broad biocidal activity and can be used to combat various insect pests.

Said compounds are particularly suitable for combating insects of the following genera: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococidae, Coccinellidae, Coccinellidae, Coccinellidae, Coccinellidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae, Tipulidae, Stomyxydae, Muscidae, Calliporidae, Trypetidae, and Pulicidae.

The insecticidal effect of the compound of the invention can be greatly enhanced and adapted to the circumstances by the addition of other insecticides and / or acaricides.

Suitable additives are, for example, the following active substances:

Organic phosphorus compounds:

bis-O, O-diethylphosphoric anhydride (TEPP), di-methyl- (2,2,2-trichloro-1-hydroxyethyl) phosphonate (TRICHLORFON),

1,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED),

2.2.Dichlorvinyldimethylphosphate (DICHLORPHOS)

2-Methoxycarbamoyl-methylvinylldimethylphosphate (MEVINPHOS), dimethylthiomethyl-2- (methylcarbamoyl) vinyl phosphate cis (MONOCROTOPHOS),

3- (dimethoxyphosphinyloxy) -N, N-dimethyl-cis-crotonamide (DICROTOPHOS), c-ω-Z-diethylcarbamoyl-1-methylvinyldimethylphosphate (PHOSPHAMIDON), 0,0-diethyl 10- (or S) -2- (tthtlthio} ethylthiophosphate (DEMETON),

S-ethylthioeihyltO, O-dimethyldithiophosphate (ΤΗΙΟΜΕΤΟΝ.),

O, O-diethyllS-ythytmethokaptomethyldithiophosphate (PHORATE),

0,0-diethyl-S-2- (ethylthio) ethyldithiophosphate (DISULFOTON),

0,0-dimethyl-S-2- (ethylsulfinyl) ethylthiophosphate (OXYDEMETONMETHYL),

O, O-dimethyl S- (1,2-dicarbethoxy) ethyldithiophosphate (MALATHION),

O, O, O, O-tettaethyl-S, S‘-meththylbis [dithiophosphate] (ETHION).

O-ethyl-S, S-dipropyldithiophosphate, O, O-diinomethyl-S- (N-methyl-N-phosphinylbromothylmethyl) dithiophosphate (F0RM0THI0N),

O .O-diinethyl S- (N-methylcarbamoylmethyl) dithiophosphate (DIMETHOAT),

O, O-Dimethyl-10-y-yittophenyl thiophosphate (PARATHION-METHYL),

0,0-diethyl-O-p-nitrophenylthiophosphate (PARATHION),

O-ethyl-O-p-nitrophenylphenylthiophosphonate (EPN),

O, O-dimethyl-O- (4-nitro-m-tolyl) thiophosphate (FENITROTHION),

O, O-dimethyl-O-2,4,5-trichlorophenylthiophosphonate (RONNEL),

O-ethyl-O-2,4,5-trichlorophenylethylthiophosphonate (TRICHLORONAT),

0,0-dimethyl-S-2- (ethylsulfinyl) ethylthiothiophosphate (BROMOPHOS),

O, O-dimethyl-O- (2,5-dichloro-4-iodophenyl) thiophosphate (JODOFENPHOS),

4-tert-butyl-2-chlorophenyl-N-methyl-O-methylamidophosphate (CRUFOMAT),

O, O-dimethyl-O- (3-methyl-4-methylmercaptophenyl) thiophosphate (FENTHION), isopropylamino-O-ethyl-O- (4-methylmercapto-3-methylphenyl) phosphate,

O, O-diethyl-O-p- (methylsulfinyl) phenylthiophosphate (FENSULFOTHION),

O- [p- (dimethylsulfamido) phenyl] -0,0-dimethylthiophosphate (FAMPHUR),

0,0,0 ‘, 0‘-tetramethyl-0,0‘-thiodi-p-phenylenediophosphate,

O-ethyl-S-phenylethyldithiophosphonate, O-dimethyl-O- (α-methylbenzyl-3-hydroxycrotonyl) phosphate,

2-chloro-1- (2,4-dichlorophenyl) vinyldiethylphosphate (CHLORFENVINPHOS),

2-chloro-1- (2,4,5-trichlorophenyl) vinyl dimethyl phosphate,

O- [2-chloro-1- (2,5-dichlorophenyl) vinyl] -0,0-diethylthiophosphate, phenylglyoxylonitriloxime-0,0-diethylthiophosphate (PHOXIM),

O, O-diethyl-O- (3-chloro-4-methyl-2-oxo-2-H-1-benzopyran-7-yl) thiophosphate (COUMAPHOS),

2,3-p-dioxanedithiol-S, S-bis- (0,0-diethyldithiophosphate (DIOXATHION)),

5 - [(6-chloro-2-oxo-3-benzoxazolinyl) methyl] -0,0-diethyidithiophosphate (PHOSALON),

2- (diethoxyphosphinylimino) -1,3-dithiolane, O, O-dimethyl-S- [2-methoxy-1,3,4-thiadiazole-

-5- (4H) -on-4-ylmethyl] dithiophosphate

Ο, Ο-dimethyl-S-phthalimidomethyldithiophosphate (IMIDAN),

O, O-diethyl-O- (3,5,6-trichloro-2-pyridyl) thiophosphate,

O, O-diethyl-O-2-pyrazinylthiophosphate (THIONAZIN),

O, O-diethyl-O- (2-isopropyl-4-methyl-6-pyrimidyl) thiophosphate (DIAZINON),

O, O-diethyl-O- (2-quinoxalyl) thiophosphate, O, O-dimethyl-S- (4-oxo-1,2,3-benzotriazin-3 (4H) -ylmethyl) dithiophosphate (AZINPHOSMETHYL ·),

O, O-diethyl S- (4-oxo-1,2,3-benzotriazin-3 (4H) -ylmethyl) dithiophosphate (AZINPHOSAETHYL),

S - [(4,6-diamino-s-triazin-2-yl) methyl] -0,0-dimethyldithiophosphate (MENAZON),

O, O-dimethyl-O- (3-chloro-4-nitrophenyl) thiophosphate (CHLORTHION),

0,0-dimethyl-O- (or S) -2- (ethylthioethyl) thiophosphate (DEMETHON-S-METHYL),

2- (Ο, Ο-dimethylphosphorylthiomethyl) -5-methoxypyrrone-4,3,4-dichlorobenzyltriphenylphosphonium chloride,

O, O-Diethyl-S- (2,5-dichlorophenylthiomethyl) dithiophosphate (PHENKAPTON)

O, O-diethyl-O- (4-methylcoumarin-7-yl) thiophosphate (POTASAN),

5-amino-bis- (dimethylamido) phosphinyl-3-phenyl-1,2,4-triazole (TRIAMIPHOS), N-methyl-5- (0,0-dimethylthiophosphoryl) -3-

-thiavaleramide (VAMIDOTH10N), 0,0-diethyl 1-O- [2-dimethylamino-4-methyl-6-pyrimidyl] thiophosphate (DIOCTHYL), 0,0-dimethyl-S- (methylcarbamoylmethyl) thiophosphate (OMETHOAT),

O-ethyl-O- (8-quinolinyl) phenylthiophosphonate (OXIN0TH10PH0S),

O-methyl-S-methylamidothiophosphate (MONITOR),

O-methyl-O- (2,5-dichloro-4-bromophenyl) benzothiophosphonate (PHOSVEL), 0,0,0,0-tetrapropyldithiopyrophosphate,

3- (dimethoxyphosphinyloxy) -N-methyl-N-

-methoxy-cis-crotonamide, O, O-diethyl-S- (N-isopropylcarbamoylmethyl) dithiophosphate (PROTHOAT), O-O-diethyl-S- (N-ethylcarbamoylmethyl) dithiophosphate

S-N- (1-cyano-1-methylethyl) carbamoylmethyldiethylthiol phosphate (CYANTHOAT),

S- (2-acetamidoethyl) -0,0-dimethyldithiophosphate, hexamethylphosphoric triamide (HEMPA), 0,0-dimethyl-O- (2-chloro-4-nitrophenyl) thiophosphate (DICOPTHON),

O, O-dimethyl-O-p-cyanophenyl thiophosphate (CYANOX),

O-ethyl-O-p-cyanophenylthiophosphonate, O, O-diethyl-O-2,4-dichlorophenylthiophosphate (DICHLORFENTHION),

0,2,4-dichlorophenyl-O-methyl lisopropylamidothiophosphate,

O, O-diethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-AETHYL), dimethyl p- (methylthio) phenylphosphate, O, O-dimethyl-β-sulfamidophenylthiophosphate, O- [p-p-chlorophenyl] azophenyl] -OO-dimethylthiophosphate (AZOTHOAT),

O-ethyl-S-4-chlorophenylethyldithiophosphonate, O-isobutyl-S-p-chlorophenylethyldithiophosphonate,

0,0-dimethyl-S-p-chlorophenylthiophosphate, 0,0-dimethyl-S- (p-chlorophenylthiomethyl) dithiophosphate,

0,0-diethyl-p-chlorophenyl mercaptomethyldithiophosphate (CARBOPHENOTHION), O, O-diethyl-S-p-chlorophenylthiomethylthiophosphate,

0,0-dimethyl-S- (ethoxycarbonylphenylmethyl) dithiophosphate (PHENTHOAT),

O, O-diethyl-S- (fluoroethoxycarbonylphenylmethyl) dithiophosphate,

O, O-dimethyl-S- (isopropoxycarbonylphenylmethyl) dithiophosphate,

O, O-diethyl-7-hydroxy-3,4-tetramethylenecoumarin thiophosphate (COUMITHO AT), 2-methoxy-4-H-1,3,2-benzodioxaphosphorine-2-sulfide,

O, O-diethyl-O- (5-phenyl-3-isooxazolyl) thiophosphate,

2- (diethoxyphosphinylimino) -4-methyl-

1,3-dithiolane, tris- (2-methyl-1-aziridinyl) phosphine oxide (МЕТЕРА),

S- (2-chloro-1-phthalimidoethyl) -O, O-diethyldithiophosphate,

N-hydroxynaphthalimidodiethylphosphate, dimethyl 3,5,6-trichloro-2-pyridylphosphate, O, O-dimethyl-O- (3,5,6-trichloro-2-pyridyl) thiophosphate,

S-2- (ethylsulfonyl) ethyldimethylthiophosphate (DIOXYDEMETHONE-S-METHYL), diethyl S-2- (ethylsulfinyl) ethyldithiophosphate (OXYDISULFOTON), bis-O, O-diethylthiophosphoric anhydride (SULFOTEP), dimethyl 3-di (methoxycarbonyl) -1-propen-2-yl phosphate, dimethyl (2,2,2-trichloro-1-butyroyloxyethyl) phosphonate (BUTONAT),

O, O-dimethyl-O- (2,2-dichloro-1-methoxyvinyl) phosphate, bis- (dimethylamido) fluorophosphate (DIMEFOX),

3,4-dichlorobenzyltriphenylphosphonium chloride, dimethyl N-methoxymethylcarbamoylmethyldithiophosphate (FORMOCARBAM),

O, O-diethyl-O- (2,2-dichloro-1-chloroethoxyvinyl) phosphate,

O, O-dimethyl-O- (2,2-dichloro-1-chloroethoxyvinyl) phosphate,

O-ethyl-S, S-diphenyldithiolphosphate, O-ethyl-S-benzylphenyldithiophosphonate, O, O-diethyl-S-benzylthiol phosphate,

O, O-dimethyl-S- (4-chlorophenylthiomethyl) dithiophosphate (METHYLCARBOPHENOTHION),

O, O-dimethyl-S- (ethylthiomethyl) dithiophosphate, diisopropylaminofluorophosphate (MIPAFOX), O, O-dimethyl-S- (morpholinylcarbamoylmethyl) dithiophosphate (MORPHOTHION), bismethylamidophenyl phosphate,

O, O-dimethyl-S- (benzenesulfonyl) dithiophosphate,

O, O-dimethyl- (S and O) -ethylsulfinyl thiophosphate,

O, O-diethyl-O-4-nitrophenyl phosphate, triethoxyisopropoxy-bis (thiophosphyl) disulfide,

2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-oxide, pyrophosphoric acid octamethylamide (SCHRADAN), bis- (dimethoxythiophosphinesulfonyl) phenylmethane,

N, N, N ‘, N‘-tetramethyldiamidofluorophosphate (DIMEFOX),

O-phenyl-O-p-nitrophenylmethanethiophosphonate (COLEP),

O-methyl-O- (2-chloro-4-tert-butylphenyl) -N-methylamidothiophosphate (NARLENE),

O-ethyl-O- (2,4-dichlorophenyl) phenylthiophosphonate,

O, O-diethyl-O- (4-methylmercapto-3,5-dimethylphenyl) thiophosphate,

4,4‘-bis- (Ο, Ο-dimethylthiophosphoryloxy) diphenyl disulfide,

O, O-di- (β-chloroethyl) -O- (3-chloro-4-methylcoumarin-7-yl) phosphate,

S- (1-phthalimidoethyl) -O, O-diethyldithiophosphate, O, O-dimethyl-O- (3-chloro-4-diethylsulfamylphenyl) thiophosphate,

O-methyl-O- (2-isopropoxycarbonylphenyl) amidothiophosphate,

5- (0,0-dimethylphosphoryl) -6-chlorobicyclo (3,2,0) hepta-1,5-diene; and

O-methyl-O- (2-isopropoxycarbonyl) -1-methylvinyl) ethylamidothiophosphate.

Nitrophenol derivatives

4.6- dinitro-6-methylphenol, sodium salt (Dinitrocresol), dinitrobutylphenol (salt with 2,2 ‘, 2'-triethanolamine),

2-cyclohexyl-4,6-dinitrophenol (Dinex),

2- (1-methylheptyl) -4,6-dinitrophenylcrotonate (Dinocap),

2-sec-butyl-4,6-dinitrophenyl-3-methylbutenoate (Binapacryl),

2-sec-butyl-4,6-dinitrophenylcyclopropionate a

2-sec-butyl-4,6-dinitrophenylisopropyl carbonate (Dinobuton).

Various compounds:

pyrethrin I, pyrethrin II,

3-allyl-2-methyl-4-oxo-2-cyclopenten-1-yl-chrysanthemumcarboxes (Allethrin),

6-chloriperonylchrysanthemum carboxylate (Barthrin),

2,4-dimethylbenzylchrysanthemum carboxylate (Dimethrin),

2,3,4,5-tetrahydrophthalimidomethylchrysanthemum carboxylate,

4-chlorobenzyl-4-chlorophenyl sulfide (chlorobenside),

6-methyl-2-oxo-1,3-dithiolo- [4,5-b] quinoxaline (Quinomethionate), (1) -3- (2-furfuryl) -2-methyl-4-oxocyclopent-2 -enyl (I) - (cis 4-trans-chrysanthemum monocarboxylate (Furethrin), 2-pivaloylindan-1,3-dione (Pindone), N ⁴ - (4-chloro-2-methylphenyl) - N, N-dimethylformamidine (Chlorphenamidine),

4-chlorobenzyl-4-fluorophenyl sulfide (Fluorbenside),

5.6-dichlorophenoxycarbanyl-2-trifluoromethyl benzimidazole (Phenozaflor), p-chlorophenyl-p-chlorobenzenesulfonate (Ovex), p-chlorophenylbenzenesulfonate (Fenson), p-chlorophenyl-2,4,5-trichlorophenylsulfone (Tetradifon), p- chlorophenyl-2,4,5-trichlorophenylsulfide (Tetrasul), p-chlorobenzyl-p-chlorophenylsulfide (Chlorbenside),

2-thio-1,3-dithiolo- [5,6] Quinoxaline (Thioquinox) and prop-2-ynyl- (4-tert-butylphenoxy) cyclohexylsulfite (Propargil).

Formamidines:

1-Dimethyl-2- (2'-methyl-4'-chlorophenyl) formamidine (CHLORPHENAMIDIN), d-meth-1-2- (2'-methyl-4'-chlorophenyl) formamidine, d-methyl -2- (2'-methyl-4'-bromophenyl) formamidine, 1-methyl-2- (2 ', 4'-dimethylphenyl) formamidine, 1'-butyl-1-methyl-2- (2'-methyl- 4'-chlorophenyl) formamidine,

1-methyl-1- (2'-methyl-4'-chloroanilinomethylene),

2- (2'-methyl-4'-chlorophenyl) formamidine and 1-n-butyl-2- (2'-methyl-4'-chlorophenylimino) pyrrolidine.

Urea derivatives:

N-2-methyl-4-chlorophenyl-N, N-dimethylthiourea.

Carbamic acid derivatives:

1-naphthyl-N-methylcarbamate (CARBARYL),

2-butynyl-4-chlorophenylcarbamate,

4-dimethylamino-3,5-xylyl-N-methylcarbamate,

4-di-4-thylamino-3-olyl-2-carboxylic acid (AMINOCARB),

4-methyl-thio-3,5-xylyl-N-diethylcarbamyl (METHIOCARB),

3.4.5-trimethylphenyl-N-methylcarbamate, C-chlorophenyl-N-methylcarbamate (CPMC),

5-chloro-6-oxo-2-norbornane carbonitrile-O-

- (methylcarbamoyl) oxime,

1- (dimethylcarbamoyl) -5-methyl-3-pyrazolyl-N, N-dimethylcarbamate (DIMETILAN),

2,3-dihydrr-2,2-dimethyl-7-echosuccinoyl-N-methylcarbamoyl (CARBOFURAN),

2-Isopropyl-2-methylteiopropionaldehyde-

-O- (methylcarbamoyl) oxime (ALDICARB), 8-quinaldyl-N-methylcarbamal and its salts, methyl 2-isopropyl-4- (meteylcarbamoyloxy) carbanilate, m- (1-ethylpropyl Kenyl-N-methylcarbamate),

3,5-di-tert-Butyl-N-methylcarbamdt, m- (1-methyl-1-phenyl) N-methylcarbamate,

2-isopropylphenoyl-N-methylcarbamate,

2-sec-butylphenyl-N-methylcarbamate, m-tolyl-N-methylcarbamate,

2.3- xylyl-N-methylcarboxamal,

3-Isopropylphenyl-N-methylcarbamal

3-tert-Butyl-phenyl-N-methyl-bromide

3-sec-Butyl-phenyl-N-methylcorddate,

3-Sopropyl-d-methylphenyl-N-methylcarbamate (PROMECARB),

3,5-diisopropylphenoyl-N-meteylcarbamate,

2-chloro-5-isopropylphenyloyl-N-meteylcarbonyl, 2-chloro-4,5-dimethylphenyl-N-methylcabbamate,

2- (1,3-dioxolan-2-yl) phenyl-N-methylcarbamate (DIOXACARB),

2- (4,5-dimethyl-1,3-dioxolan-2-yl) phenyl-N-methylcarbamal,

2- (1,3-dioxolan-2-yl) phenyl-N, N-dimeleyl · carbamate,

2- (1,3-dithiolao-2-yl) -N, N-dimethylcarbamate,

2- (1,3-dithiolan-2-yl) phenyl-N, N-dimethylcarbamate,

2-isopropoxyphenyl-N-methylcarboxylate (ARPROCARB),

2- (2-propionylrxy) phenyl-N-methylcarbamate,

3- (2-Propyiroyloxy) phenyl-N-methylcarbamate, 2-dimethylaminophenyl-N-methylcarbamate,

2-diallylammofeoyl-N-methylcarOamal,

4-diallylamino-3,5-xylyl-N-methylcarbamate (ALLYXICARB),

4-Beosothienyl-N-methylcarbamate

2,3-dihydro-2-meteyl-7-benzofuranyl-N-methylcarbamate,

3-Meteyl-1-phenylpyrazol-5-yl-N, N-dimethylcarbamate

1-Isopropyl-3-methylpyrazo-5-yl-N, N-dimeleylcarbamate (ISOLAN)

2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N, N-dimethylcarbamate,

3-methyl-4-dimethylaminomethylenimino-phenyl-N-methylcarbamate,

3,4-dimethylphenyl N-methylcarbamate,

2-cyclopentylphenyl-N-methylcarbamate,

3-dimethylaminomethyleneiminophenyl N-methylcarbamate ((FORMATENaTe) and its salts,

1-Methylthioethylimine N-methylcarbamate (METHOMYL)

2-Methylcarbamoyloximio-1,3-dithiolao

5-methyl-2-methylcarbamoyloximino-2-methyl-2-methylcarbamoyloximino;

2- [1-methoxy-2-propoxy]. phenyl-N-methylcarbamate,

2- (1-butin-3-yloxy) phenyl-N-methylcarbamate,

1-dimethylcaramoyl-1-methylth-o-O-meteylcaramoylformoxime,

1- (2'-cyanoethylthio) -O-methylcarbamoylacetaldoxime,

1-methylthir-O-carbamoylacetaldoxime,

O- [3-sec-butylphenyl] -N-phenylthio-N-methylcarbamate,

2,5-Dimethyl-1,3-dithiolane-2- (O-methylcarbamoyl) aldoxime

0-2-Diflyl-N-methylcarbamate

2- (N-diethylcarbamoyloximino) -3-chlorobicyclo [2.2.1] heptane,

2- (N-methylcarbamoyl-imino) bicyclo [2.2.1] eeptane,

3-Isopropylphenyl N-methyl-N-chloroacetylcarbamate

3-isopropylphenyl-N-methyl-N-methylmethylcarbamate,

O- (2,2-dimethyl-4-chloro-2,3-dihydro-7-benzofuranyl) -N-methylcarboxamal,

O- (2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl) -N-ethylcarbamate,

O-naphthyl-N-methyl-N-acetylcarbamate,

O-5,6,7,8-tetrahyclronaphthyl-N-methylcarbamate,

3-Isopropyl-4-methylthiophenyl-N-methylcarbamate

3,5-dimethyl-4-methoxyphenyl-N-methylcarbamate,

3-methoxymethoxyphenyl-N-methylcarbamate,

3-Allyloxyphenyl N-methylcarbamate

2-propargyloxymethoxyphenyl-N-methylcarbamate,

2-allyloxyphenyl-N-methylcarbamate,

4-Methoxycarbonylamino-3-isopropylphenyl-N-methylcarbamate

3,5-Dimethyl-4-methoxycarbonylaminophenyl-N-methylcarbamate

2-y-methylthiopropylphenyl-N-methylcarbamate,

3- (- - ^ 6 ^ 0x 0x 0x71 0x71 0 ^ ^71-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2)

2-chloro-5-tert-butylphenyl-N-methylcarbamate,

1- (methylpropargylamino) -3,5-xyl-N-methylcarbamate,

4- (methyl-γ-chloroallylamino) -3,5-xylyl-N-methylcarbamate,

4- (Methyl-4-chlorally-camino) - 3,5-α-N-methylcarbamate,

1- (trans-oxycarbonylethyl) -3-methyl-5-pyrazolyl-N, N-dimethylcarbamate,

3-methyl-4- (dimethylaminomethylmercaptomethylenimino) phenyl-N-methylcarbamate,

1,3-bis (carbamoylthio) -2- (N, N-dimethylamino) propanhydride,

5.5-dimethylhydroresorcindimethylcarbamate,

2- [ethylpropargylamino-) phenyl-N-methylcarbamate,

2- [methylpropargylamino) phenyl-N-methylcarbamate,

2- [dipropargylamino-phenyl-N-methylcarbamate,

4- [dipropargylamino) -3-tolyl-N-methylcarbamate,

4- [dipropprgylymino] - 3,5-3xCyC-N-methylCarbamate,

2- [allylisopropylamino) phenyl-N-methylcarbamate a

3- [allylisopropylamino) phenyl-N-methylcarbamate.

Chlorinated hydrocarbons:

χ-hexachlorocyclohexane [GAMMEXANE; LINDAN; yHCH],

1,2,4,5,6,7,8,8-octachlor-3a, 4,7,7a'-tetrahydro-4,7-m-thylenindane [CHLORDAN], Д Дб ^ Д-heptachlop-Зз, 4,7,7α-teteahyУrO] - 4,7-methenoindane [HEPTACHLOR],

1,2Д4,10.10-exexacУlpr-1,4,4αД8,8α-exexahydroendo-1,4-exo-5,8-dimethanonaphthalene [ALDRIN],

1,2,4,4-Hexachlpr-6,7-epoxy-4- [1,2-a] -ca-octahydroexo-N-endo-5,8-dimethanonaphthalene [DIELDRIN],

У, 2,3,4,1Cr10-hexacho-o-6,7-epoxy-У, 4,4α, 5,6,7,8,8a'-octahydopendpendo-8-dimethanonaphthalene [ENDRINJ.

In addition to the above-mentioned properties, the compounds of the formula I also have activity against organisms of the order ThallopУyta. Thus, some of these compounds exhibit bactericidal activity and are active against fungi, in particular against phytopathogenic fungi belonging to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basldiomycetes, Denteromycetes.

The compounds of formula I also exhibit fungitoxic activity on fungi attacking plants from soil. The new active substances are also suitable for the treatment of seeds, fruits, tubers, etc., for their protection against fungal infections.

The compounds of the formula I are also suitable for combating phytopathogenic nematodes.

The compounds of the formula I can be used either alone or together with suitable carriers and / or additives.

Suitable carriers and additives may be solid or liquid and correspond to those commonly used in the preparation of such compositions as natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and / or fertilizers.

For applications, the compounds of formula (I) may be formulated as dusts, emulsion concentrates, granules, dispersions, sprays, solutions or suspensions, which are generally known in the art of application. It is also necessary to mention the so-called cattle dips, ie cattle spas, and the so-called spray races, ie spray corridors where aqueous preparations are used.

The compositions according to the invention are prepared in a manner known per se by thoroughly mixing and / or grinding the active compounds of the formula I with suitable carriers, optionally with the addition of dispersants or solvents which are inert to the active compounds. The active substances can be used in the following processing forms: solid processing forms:

dusting, spreading, granulate, coated granulate, impregnated granulate and homogeneous granulate;

liquid processing forms:

a) water-dispersible active substance concentrates: wettable powders, pastes, emulsions;

(b) solutions.

For the production of solid processing forms (dusts, sprinkles), the active substances are mixed with solid carriers, for example kaolin, talc, bolus, loess, chalk, limestone pulp, limestone, attapulgite, dolomite, diatomite, precipitated silica, metal silicates · alkaline earth, sodium and potassium aluminum silicate (feldspar and mica), calcium and magnesium sulphate, magnesium oxide, ground · plastics, fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as cereal flour , tree bark meal, wood meal, nut shell meal, powdered cellulose, plant extract residues, activated carbon, etc., alone or mixed together.

Granules can be easily prepared by dissolving the active compound of formula I in an organic solvent and applying the solution thus obtained to a granular mineral such as attapulgite, silica, granulated limestone, bentonite, etc., and then evaporating the organic solvent again.

Polymer-based granules can also be prepared by mixing the active compounds of the formula I with polymerizable compounds (urea-formaldehyde mixture, dicyandiamide-formaldehyde mixture, melamine-formaldehyde mixture or the like), followed by gentle polymerization conditions. It is preferable to impregnate the finished porous granulate based on polymeric substances (urea-formaldehyde, polyacrylonitrile, polyester or other granulate) with a specific surface area and with favorable adsorption and desorption ratios by the active substances. Such polymeric granules can also be applied in the form of microorganisms having a bulk density of preferably 300 g / liter to 600 g / liter, for example in the form of their solutions (in a low-boiling solvent). appropriate areas of crops using aircraft.

Granules may also be obtained by compressing the carrier with the active ingredients and additives, followed by comminution.

In addition, stabilizing additives and / or non-ionic, anionic and cationic substances can be added to these active compound mixtures which improve, for example, the adhesion of the active substances to plants or parts thereof (adhesives and adhesives) and / or provide better wettability (wetting agents). dispersibility (dispersants).

Thus, for example, the following substances are suitable: a mixture of olein and lime, cellulose derivatives (methylcellulose, carboxymethylcellulose), hydroxyethylene glycol ethers of mono- and dialkylphenols having 5 to 15 ethylene oxide moieties per molecule and 8 to 9 carbon atoms in the alkyl residue, ligninsulfonic acids, alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbos waxes), polyglycol ethers of fatty alcohols having 5 to 20 ethylene oxide residues per molecule and 8 to 18 carbon atoms in the rest of the fatty alcohol, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products formaldehyde, as well as latex products.

Water-dispersible active ingredient concentrates, ie wettable powders, pastes and emulsifiable concentrates, are compositions which can be diluted with water to any desired concentration. They consist of an active ingredient, a carrier, optionally additives which stabilize the active ingredient, surfactants and antifoams, and optionally solvents.

Wettable powders and pastes are obtained by mixing the active compounds with dispersants and powder carriers in suitable devices to form a homogeneous mixture which is ground. Suitable carriers are, for example, those mentioned above for solid processing forms. In many cases, it is preferred that mixtures of different carriers are used. The following can be used as dispersants, for example: condensation products of sulfonated naphthalene and sulfonated derivatives of naphthalene with formaldehyde; naphthalenesulphonic acids with phenol and formaldehyde as well as alkali metal, alkaline earth metal salts and ammonium lignin sulphonic acid salts,. furthermore alkylarylsulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, sulfated higher aliphatic alcohols such as sulfated hexadecanols, heptadecanols and octadecanols and sulfated fatty alcohol glycol ethers salts, sodium oleylmethyltauride, alkali metal and di-tertiary ethylene glycol salts with fatty acids.

Suitable antifoams are, for example, silicone oils.

The active ingredients are mixed, ground, sieved and sieved with the above ingredients so that the solids do not exceed a grain size of 0.02 to 0.04 mm for the wettable powders and 0.03 mm for the pastes. The dispersants mentioned in the above paragraphs, organic solvents and water are used to produce emulsifiable concentrates and pastes. Suitable solvents are, for example, the following: alcohols, benzene, xylenes, toluene, dimethylsulfoxide and mineral oil fractions boiling in the range of from 120 to 350 ^° C. The solvents must be practically odorless, non-phytotoxic and inert to the active ingredients.

The compositions of the invention may further be used in the form of solutions. In this case, the active substance or the active ingredient is removed. more active compounds of the formula I are dissolved in suitable organic solvents, solvent mixtures or in water. The organic solvents used may be aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, mineral oils, alone or in admixture with each other.

The active compound content of the above-described compositions is from 0.1 to 95%, it being noted that when used from aircraft or other suitable devices, up to 99.5% of the concentration or even pure active substance can be used.

The active compounds of the formula I can, for example, be formulated as:

Dust:

The following ingredients shall be used to obtain (a) 5% and (b) 2% dusts:

(a) 5 parts of active substance, parts of talc;

(b) 2 parts of active substance, part of highly dispersed silicic acid, parts of talc.

The active compounds are mixed with the carriers and the mixture is ground.

Granulate:

The following substances are used to obtain 5% granulate:

parts of the active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol, parts of kaolin (grain 0.3-0.8 mm).

The active ingredient is mixed with epichlerhydrin and dissolved in 6 parts of acetone, followed by the addition of polyethylene glycol and cetyl polyglycol ether. The solution thus obtained is sprayed onto kaolin and then the acetone is evaporated in vacuo.

Wettable powder:

The following ingredients are used to prepare a) 40%, b) and c) 25%, d) 10% wettable powder:

(a) parts of active substance, parts of sodium lignin sulphonic acid, parts of sodium dibutylnaphthalenesulphonate, parts of silicic acid;

(b) parts of the active substance,

4.5 parts by weight of lignin sulphonic acid calcium salt,

1.9 parts of a mixture of chalk (prov. Champagne) and hydroxyethyl cellulose (1: 1),

1.5 parts of sodium dibutylnaphthalenesulphonate,

19.5 parts of silicic acid,

19.5 parts of chalk,

28.1 parts of kaolin;

(c) parts of the active substance,

2.5 parts of isooctylphenoxypolyoxyethylene ethylene,

1.7 parts of a mixture of chalk and hydroxyethylcellulose (1: 1),

8.3 parts of sodium aluminum silicate,

16.5 parts of diatomaceous earth, parts of kaolin;

(d) parts of active substance, parts of a mixture of sodium salts of saturated sulphated higher aliphatic alcohols, parts of a naphthalenesulfonic acid-formaldehyde condensation product, parts of kaolin.

The active ingredients are thoroughly mixed in suitable mixers with additives and milled in appropriate mills and calenders. A wettable powder is obtained from which suspensions of the desired concentrations can be prepared by dilution with water.

Emulsifiable concentrate:

The following substances are used to obtain a) 10% and b) 25% emulsifiable concentrate:

(a) parts of the active substance,

3.4 parts of epoxidized vegetable oil,

13.4 parts of emulsifiers consisting of a mixture of a polyglycol ether of a higher aliphatic alcohol with an alkylarylsulfonic acid calcium salt, parts of dimethylformamide,

43.2 parts of xylene;

(b) parts of the active substance,

2.5 parts of epoxidized vegetable oil, parts of a mixture of alkylarylsulphonate and a polyglycol ether of a higher aliphatic alcohol, parts of dimethylformamide,

57.5 parts of xylene.

Emulsions of the desired concentration can be prepared from these concentrates by dilution with water.

Spraying agent:

The following components shall be used to obtain (a) 5% of the spraying agent:

(a) 5 parts of active substance, part of spichlorohydrin, parts of petrol (boiling point 160 to

190 ° C).

The invention is illustrated by the following non-limiting examples.

Example 1

Preparation of N, N-diethyl-N'-O, S-dimethylthiophosphinylformamide as an oil and refractive index ng ²⁵ = 1.5145. The following compounds of formula I are also prepared in an analogous manner

A mixture of 16.2 g of thiophosphoric acid O, S-dimethyl ester and 17 g of diethylformamide diethyl acetal was heated to 50-60% for 1 hour. Distillation of the resulting methanol and excess acetal at 2 to 2.7 kPa yields the product (Compound No. 1j of formula).

CH 2 O O C 2 H 5

Ml /

P — N = CH — N, \

CH3S C2H5

R 10 O R 3

Ml /

P — N = CH — N,

Compound No. Ri Rž R3 Rá Physical data 2 CHs CH3 —CH2 — CH2 —O — CH2 — CH2— n _D 25 = 1.5349 3 CHs CH3 - -CH 2 —CH 2 —CH 2 —CH 2 —CH 2 - n _D 20 = 1.5445 4 C2H5 (n) C3H7 - -CH 2 —CH 2 —CH 2 —CH 2 —CH 2 - n _D ² 5 = 1.5225 5 C2H5 CH3 —CH2 — CH2 —O — CH2 — CH2— n _D 25 = 1.5269 6 C2H5 (n) C3H7 C2H5 C2H5 n _D 25 = 1.5002 7 C2H5 CH2 = CH — CH2— —CH2 —CH2 —O — CH2 — CH2— n _D 25 = 1.5348 8 CHs C2H5 - —CH2 — CH2 — CH2 — CH2 — CH2— n _D 25 = 1.5303 9 CH3 (n) C3H7 - —CH2 — CH2 — CH2 — CH2 — CH2— n _D 25 = 1.5265 10 CH3 CH2 = CH — CH2— - -CH2 — CH2 — CH2 — CH2 — CH2— n _D 25 = 1.5379 11 CHs HC = C — CH2—— -CH2 — CH2 — CH2 — CH2 — CH2— n _D 25 = 1.5411 Example 2 2, 4, 8, 24 and 48 hours] by insects. after infestation of plants Larding insecticidal effect (Leptinotarsa As a reference is used

decemlineata and Dysdercus fasciatus) nina of formula A

Cotton plants are sprayed with an aqueous emulsion containing 0.05% test compound (prepared from 10% concentrate). After the spray coating has dried, the plants are infested with the larvae (3rd larval stage) of Leptinotarsa decemlineata or Dysderucus fasciatus. Two plants are used for each test compound and each insect species. The test plants are further maintained at 24 ° C and 60% relative humidity. Achieved mortality is evaluated after

CH 2 OH 4.

P-N = CH-N, CH 3 OH (A) known from French Patent No. 2,073,668.

The results are summarized as follows:

Compound number Time to 100% mortality (h) Leptinotarsa decemlineata Dysdercus fasciatus 1 2 2 2 24 24 3 4 24 · 4 24 24 5 48 48 6 24 24 7 4 24 8 24 24 9 2 2 10 4 24 11 2 24 AND 0% mortality after 48 hours 0% mortality after 48 hours

Example 3

Systemic insecticidal effect - Aphis fabae (Poppy Aphid)

The rooted bean plants are transplanted into pots containing 600 cm ^{3 of} soil and the soil around the plants is covered with 50 ml of a 10 ppm test compound solution (prepared from 25% wettable powder). After 24 hours, the aerial parts of the plants are contaminated with poppy aphids and the plants are covered with a plastic cylinder to prevent eventual contact of the aphids with the test substance vapors.

SUBJECT

Claims (1)

SUBJECT An insecticidal composition, characterized in that it contains an amidine of the formula I as active ingredient R10 ORs \ llz P — N = CH — N, z \ RZSR4 (I), Each test substance concentration is tested on 2 plants, each of which is planted in a separate pot. The experiment was carried out at 25 ^° C and 70% relative humidity. Mortality assessments are made 48 and 72 hours after the start of the experiment. The results are shown in the following overview: Compound # 123456789 10 11 100% mortality time (h) 48 72 48 48 48 48 48 72 72 48 48 I INVENT in which R1 is methyl or ethyl, R 2 represents a C 1 -C 3 alkyl, propenyl or propynyl group, and either R 3 and R 1 each represent an ethyl group, or R 3 and R 4 together with the nitrogen atom to which they are attached form a morpholino or piperidino group. Severography, n. P., Plant 7. Most