HK1111064B - Pesticidal compositions - Google Patents

Description

Pesticide composition

This application is a divisional application entitled "pesticidal composition" filed on 17.4.1997, application No. 200510092048.0.

Technical Field

The present invention relates to pesticidal compositions comprising a mixture of active compounds, to a method for controlling pests using such compositions, to a process for preparing such compositions, to their use and to plant propagation material treated therewith, and to the use of a compound of formula (a) below for preparing such compositions.

Background

Mixtures of some active compounds have been proposed in the literature for pest control. However, the biological properties of mixtures of these known compounds are not entirely satisfactory in the field of pest control, and it is therefore desirable to provide further mixtures which have synergistic pest control properties, in particular mixtures for controlling insects and representatives of the order acarina. This object is achieved by the composition of the invention.

Disclosure of Invention

The present invention therefore relates to compositions for controlling insects or representatives of the order Acarina, which comprise one or more compounds of the formula (A) in various amounts

Wherein

A is a mono-to tetrasubstituted, aromatic or nonaromatic, monocyclic or bicyclic heterocyclic radical which is unsubstituted or, depending on the substitution possibilities on the ring system, wherein the substituents A are selected from the group consisting of: c₁-C₃Alkyl radical, C₁-C₃-alkoxy, halogen, halo-C₁-C₃Alkyl, cyclopropyl, halogenocyclopropyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, halo-C₂-C₃-alkenyl, halo-C₂-C₃-alkynyl, halo-C₁-C₃-alkoxy, C₁-C₃-alkylthio, halo-C₁-C₃Alkylthio, allyloxy, propinyloxy, allylthio, propinylthio, haloallyloxy, haloallylthio, cyano and nitro;

r is hydrogen, C₁-C₆Alkyl, phenyl-C₁-C₄Alkyl radical, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl or C₂-C₆-an alkynyl group; and

x is N-NO₂Or a group of N-CN groups,

the compounds of the formula (A) are tautomers in free form or in salt form, if appropriate also in free form or in salt form,

in combination with one or more of the following compounds:

(I) aldicarb (XVIII) ethiocarb (XXXV) VOLTURON

(II) Baoban (XIX) fenitrothion (XXXVI) terbufos

(III) benfuracarb (XX) fenobucarb (XXXVII) triazamate

(IV) Fluoropermethrin (XXI) fenvalerate (XXXVIII) abamectin

(V) Buprofezin (XXII) Bu (XXXIX) Buffet

(VI) carbofuran (XXIII) methiocarb (XXXL) tebufenozide

(VII) dibutyl laminothioo (XXIV) heptenophos (XLI) fipronil

(VIII) Badan (XXV) Imidacloprid (XLII) Aphidrin

(IX) chlorfluazuron (XXVI) isoprocarb (XLIII) silafluofen

(X) Chlorpyrifos (XXVII) Methamidophos (XLIV) fenpyroximate

(XI) cyfluthrin (XXVIII) methomyl (XLV) pyridaben

(XII) lambda-cyhalothrin (XXIX) metolcarb (XLVI) cyazofamid

(XIII) alpha-cypermethrin (XXX) parathion (XLVII) pyriproxyfen

(XIV) zeta-cypermethrin (XXXI) methyl parathion (XLVIII) pyrimidifen

(XV) deltamethrin (XXXII) Vocidin (XLIX) nitenpyram

(XVI) diflubenzuron (XXXIII) pirimicarb (L) NI-25, acetamiprid

(XVII) endosulfan (XXXIV) propoxur

(LI) Avermectin B₁(ivermectin);

(LII) plant extracts active against insects;

(LIII) a preparation comprising nematodes active against insects;

(LIV) preparations obtainable from bacillus subtilis;

(LV) formulations comprising fungi active against insects;

(LVI) a preparation comprising a virus active against insects;

(LVII) AC 303630 (LXVII) bendiocarb (LXXVI) carbaryl

(LVIII) acephate (LXVIII) insecticidal Leech (LXXVIII) trithione

(LIX) Fluthrin (LXIX) Cypermethrin (LXXIX) chlorocarbocarb

(LX) Cotton bollworm (LXX) fenobucarb (LXXX) chloroethophosphorus

(LXI) alpha-cypermethrin (LXXI) brofenprox (LXXXI) chloromethophothion

(LXII) amitraz (LXII) Bromoethion (LXXXII) cis-resmethrin

(LXIII) AZ 60541 (LXIII) Clocythrin (LXXXIII)

(LXIV) Sulfoxaden (LXXIV) butocarboxim (LXXXIV) clofentezine

(LXV) Baoban (LXXV) pyridaben (LXXXV) fenitrothion

(LXVI) Triazolidinium (LXVI) cadusafos

(LXXXVI) Cycloprothrin (CXIX) Chlorfluazuron (CL) pyrazophos

(LXXXVII) Tricyhexatin (CXX) hexythiazox (CLI) pyrada-phenothion

(LXXXVIII) systemic PhosphoM (CXXI) Pyricularia oryzae (CLII) pyremethrin

(LXXXIX) systemic phosphorus (CXXII) isopropylaminophos (CLIII) pyrethrin

(XC) Methylsystemic Phosphorus (CXXIII) Oxazolophos (CLIV) RH 5992

(XCI) Phenolphosphine (CXXIV) ivermectin (CLV) Salicthion

(XCII) dicliphos (CXXV) Cyhalothrin (CLVI) sebufos

(XCIII) Ethos (CXXVI) malathion (CLVII) fenitrothion

(XCIV) Dimethoate (CXXVII) Myzus Citrari (CLVIII) Methylpropanethione

(XCV) Methyloxaphos (CXXVIII) mesulfenphos (CLIX) tebufenpyrad

(XCVI) Dirofos (CXXIX) Snail Dithion (CLX) Tebutamidophos

(XCVII) distemper powder (CXXX) metolcarb (CLXI) tefluthrin

(XCVIII) emamectin (CXXXI) milbemycin (CLXII) Diphosphothion

(XCVIX) fenvalerate (CXXXII) moxidectin (CLXIII) terbuflox

(C) Ethos (CXXXIII) dibromophosphorus (CLXIV) pesticide-feam

(CI) Ethofenprox (CXXXIV) NC 184 (CLXV) thiafenox

(CII) ethoprophos (CXXXV) omethoate (CLXVI) thiodicarb

(CIII) etrimfos (CXXXVI) oxamyl (CLXVII) monocrotophos

(CIV) Chongamidophos (CXXXVII) Sulfophosphate (CLXVIII) Chongwei

(CV) fenbutatin oxide (CXXXVIII) phosphorus Isosulfone (CLXIX) Bacillus thuringiensis

(CVI) Phenylthiocarbamate (CXXXIX) permethrin (CLXX) tetrabromthrin

(CVII) fenpropathrin (CXL) phenthoate (CLXXI) Rainbow mite

(CVIII) fenpyrad (CXLI) phorate (CLXXII) triazophos

(CIX) fenthion (CXLII) phosmet (CLXXIII) triazuron

(CX) fluazinam (CXLIII) phoxim (CLXXIV) trichlorfon

(CXI) Fluorofenoxuron (CXLIV) methylpyrimidin phosphorus (CLXXV) chlordiazuron

(CXII) Flufenvalerate (CXLV) pyrimidinephos (CLXXVI) MIMIMIMIMIMIMIMIMIMIWEI

(CXIII) Flufenoxuron (CXLVI) Chongwei (CLXXVII) Myocarb

(CXIV) flufenprox (CXLVII) benfop (CLXXVIII) Dixycarb

(CXV) Dichrofos (CXLVIII) Profenofos (CLXXIX) YI 5301/5302

(CXVI) Thiazolophosphonium (CXLIX) Hair restorer (CLXXX) zetamethrin

(CXVII)fubfenprox (CLXXXI)DPX-MP062

(CXVIII) Liuliuliusix

(CLXXXII) RH-2485 (CLXXXIII) D2341 or (CLCCCIV) methiocarb

(3, 5-Diphenylmethylamino

Formic ether)

And at least one adjuvant.

Detailed Description

Compounds of formulｃA (A) are described in EP-A-580553.

The above compounds (I) - (CLXXXIV) are known to the skilled worker, in particular:

(I) 2-methyl-2- (methylthio) propanal O-methylcarbamoyloxime (aldicarb), known by (handbook of pesticides, 9 th edition (1991), United kingdom committee of crop protection, London, page 16);

(II) S-3, 4-dihydro-4-oxo-1, 2, 3-benzotriazin-3-ylmethyl O, O-dimethyldithiophosphate (cotton-phosphorus) is known from (pesticide handbook, 9 th edition (1991), United kingdom Committee for crop protection, London, page 46);

(III) Ethyl N- [2, 3-dihydro-2, 2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio ] -N-isopropyl-beta-alaninate (Althiocarb is known from (pesticide Manual 9 th edition (1991), British Committee for crop protection, London, p.57);

(IV) 2-methyldiphenyl-3-ylmethyl (Z) - (1RS) -cis-3- (2-chloro-3, 3, 3-trifluoroprop-1-enyl) -2, 2-dimethylcyclopropanecarboxylate (bifenthrin) is known from (pesticide Manual 9 th edition (1991), United kingdom Committee for crop protection, London, page 73);

(V) 2-tert-butylimino-3-isopropyl-5-phenyl-1, 3, 5-thiadiazin-4-one (buprofezin), known from (handbook of pesticides, 9 th edition (1991), British Committee for crop protection, London, page 105);

(VI)2, 3-dihydro-2, 2-dimethylbenzofuran-7-ylmethyl carbamate (carbofuran), known from (handbook of pesticides, 9 th edition (1991), British Committee for crop protection, London, page 126);

(VII)2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl (dibutylaminothio) -methylcarbamate (dibutylaminothioo) known from (pesticide handbook, 9 th edition (1991), United kingdom committee for crop protection, London, page 129);

(VIII) S, S' - (2-dimethylaminotrimethylidene) bis (thiocarbamate) (badan), known from (pesticide handbook, 9 th edition (1991), United kingdom committee for crop protection, London, page 132);

(IX)1- [3, 5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridinyloxy) phenyl ] -3- (2, 6-difluorobenzoyl) -urea (chlorfluazuron), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee on crop protection, London, p.143);

(X) O, O-diethyl O-3, 5, 6-trichloro-2-pyridylthiophosphate (chlorpyrifos), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee on crop protection, London, page 166);

(XI) (RS) - α -cyano-4-fluoro-3-phenoxybenzyl (1RS) -cis-trans-3- (2, 2-dichlorovinyl) -2, 2-dimethylcyclopropanecarboxylate (cyfluthrin), known from (handbook of pesticides, 9 th edition (1991), british committee for crop protection, london, p.198);

(XII) mixtures of (S) - α -cyano-3-phenoxybenzyl Z- (1R) -cis-3- (2-chloro-3, 3, 3-trifluoropropenyl) -2, 2-dimethylcyclopropanecarboxylate and (R) - α -cyano-3-phenoxybenzyl Z- (1R) -cis-3- (2-chloro-3, 3, 3-trifluoropropenyl) -2, 2-dimethylcyclopropanecarboxylate (λ -cyhalothrin), known from (handbook of pesticides, 9 th edition (1991), british crop protection council, london, page 203);

(XIII) (S) - α -cyano-3-phenoxybenzyl (1R) -cis-3- (2, 2-dichlorovinyl) -2, 2-dimethylcyclopropanecarboxylate and the racemate of (R) - α -cyano-3-phenoxybenzyl (1R) -cis-3- (2, 2-dichlorovinyl) -2, 2-dimethylcyclopropanecarboxylate (α -methyl cypermethrin) are known from (handbook of pesticides, 9 th edition (1991), british crop protection council, london, p.210);

(XIV) the racemate of (S) - α -cyano-3-phenoxybenzyl (1RS) -3- (2, 2-dichlorovinyl) -2, 2-dimethylcyclopropanecarboxylate and (S) - α -cyano-3-phenoxybenzyl (3RS) -3- (2, 2-dichlorovinyl) -2, 2-dimethylcyclopropanecarboxylate (ζ -cypermethrin), known by (handbook of pesticides 9 th edition (1991), british crop protection council, london, page 265);

(XV) (S) - α -cyano-3-phenoxybenzyl (1R) -cis-3- (2, 2-dibromoethenyl) -2, 2-dimethylcyclopropanecarboxylate (deltamethrin) is known from (handbook of pesticides, 9 th edition (1991), british committee for crop protection, london, p.232);

(XVI) (4-chlorophenyl) -3- (2, 6-difluorobenzoyl) urea (diflubenzuron), known from (handbook of pesticides, 9 th edition (1991), british committee on crop protection, london, page 281);

(XVII) (1, 4, 5, 6, 7, 7-hexachloro-8, 9, 10-trinorborne-5-en-2, 3-ylidene-bismethylene) sulfite (thiodan) known from (handbook of pesticides, 9 th edition (1991), british committee for crop protection, london, page 332);

(XVIII) α -ethylthio-p-tolylmethylcarbamate (ethisulfan), known from (handbook of pesticides, 9 th edition (1991), british committee for crop protection, london, page 343);

(XIX) O, O-dimethyl-O-4-nitro-m-tolyl thiophosphate (fenitrothion), known from (pesticide handbook, 9 th edition (1991), British Committee for crop protection, London, p 369);

(XX) 2-tert-butylphenyl methyl carbamate (fenobucarb), known from (pesticide Manual, 9 th edition (1991), United kingdom committee for crop protection, London, p 371);

(XXI) (RS) - α -cyano-3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate (fenvalerate) known from (handbook of pesticides, 9 th edition (1991), United kingdom committee for crop protection, London, page 388);

(XXII) [ formyl (methyl) carbamoylmethyl ] O, O-dimethyldithiophosphate (Dithion), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee for crop protection, London, page 440);

(XXIII) 4-methylthio-3, 5-xylylmethylcarbamate (methiocarb), known from (pesticide handbook, 9 th edition (1991), United kingdom committee for crop protection, London, page 677);

(XXIV) 7-chlorobicyclo [3.2.0] hept-2, 6-dien-6-yl dimethylphosphate (heptenophos), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee for crop protection, London, p.467.);

(XXV) (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylamine (imidacloprid), known from (handbook of pesticides, 9 th edition (1991), British Committee for crop protection, London, p.491);

(XXVI) 2-isopropylphenylmethylcarbamate (isoprocarb), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee for crop protection, London, p 504);

(XXVII) O, S-Dimethylthiophosphoramide (methamidophos), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee for crop protection, London, p. 563);

(XXVIII) S-methyl N- (methylcarbamoyloxy) thioacetamidoate (methomyl), known from (pesticide handbook, 9 th edition (1991), United kingdom committee for crop protection, London, page 570);

(XXIX) methyl 3- (dimethoxyphosphonoxy) but-2-enoate (metolcarb), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee of crop protection, London, page 592);

(XXX) O, O-diethyl O-4-nitrophenyl thiophosphate (parathion), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee on crop protection, London, page 648);

(XXXI) O, O-dimethyl-O-4-nitrophenyl thiophosphate (methyl parathion), known from (handbook of pesticides, 9 th edition (1991), United kingdom committee of crop protection, London, page 650);

(XXXII) S-6-chloro-2, 3-dihydro-2-oxo-1, 3-benzoxazol-3-ylmethyl O, O-diethyl dithiophosphate (Vothion) is known from (pesticide handbook, 9 th edition (1991), United kingdom Committee for crop protection, London, p.674);

(XXXIII) 2-dimethylamino-5, 6-dimethylpyrimidin-4-yl dimethylcarbamate (pirimicarb), known from (pesticide handbook, 9 th edition (1991), British crop protection Commission, London, page 690);

(XXXIV) 2-isopropoxyphenyl methylcarbamate (propoxur), known from (pesticide handbook, 9 th edition (1991), British crop protection Commission, London, p.727);

(XXXV)1- (3, 5-dichloro-2, 4-difluorophenyl) -3- (2, 6-difluorobenzoyl) urea (flufenoxuron), known from (pesticide handbook, 9 th edition (1991), the United kingdom committee for crop protection, London, page 790);

(XXXVI) S-tert-butylthiomethyl O, O-dimethyl dithiophosphate (terbuthos) known from (handbook of pesticides, 9 th edition (1991), United kingdom committee for crop protection, London, page 795);

(XXXVII) ethyl (3-tert-butyl-1-dimethylcarbamoyl-1H-1, 2, 4-triazol-5-ylthio) acetate (triazamate), known from (pesticide handbook, 9 th edition (1991), United kingdom committee on crop protection, London, page 1006);

(XXXVIII) ivermectin, known from (handbook of pesticides, 9 th edition (1991), british committee for crop protection, london, page 3);

(XXXIX) 2-tert-butylphenyl methyl carbamate (fenobucarb), known from (pesticide Manual, 9 th edition (1991), United kingdom committee for crop protection, London, p. 371);

(XL) N-tert-butyl-N' - (4-ethylbenzoyl) -3, 5-dimethylbenzylhydrazide (tebufenozide), known from (handbook of pesticides, 10 th edition (1994), British Committee for crop protection, London, p. 943);

(XLI) (+ -) -5-amino-1- (2, 6-dichloro-alpha, alpha-trifluoro-p-tolyl) -4-trifluoromethyl-sulfinylpyrazole-3-carbonitrile (fipronil) known from (A handbook of pesticides, 10 th edition (1994), United kingdom committee for crop protection, London, p.463);

(XLII) α -cyano-4-fluoro-3-phenoxybenzyl 3- (2, 2-dichlorovinyl) -2, 2-dimethylcyclopropanecarboxylate (cyhalothrin), known from (pesticide handbook, 10 th edition (1994), british crop protection council, london, page 250);

(XLIII) (4-ethoxyphenyl) [3- (4-fluoro-3-phenoxyphenyl) propyl ] (dimethyl) silane (silafluofen) known from (handbook of pesticides, 10 th edition (1994), British Committee for crop protection, London, page 912);

(XLIV) tert-butyl (E) - α - (1, 3-dimethyl-5-phenoxypyrazol-4-yl-methyleneaminooxy) -p-toluate (fenpyroximate), known from (handbook of pesticides, 10 th edition (1994), british committee on crop protection, london, page 450);

(XLV) 2-tert-butyl-5- (4-tert-butylbenzylthio) -4-chloropyridazin-3 (2H) -one (pyridaben) known from (pesticide handbook, 10 th edition (1994), British crop protection Committee, London, p. 879);

(XLVI) 4-tert-butylethylquinazolin-4-yl ether (fenazaquin) known from (handbook of pesticides, 10 th edition (1994), British Committee for crop protection, London, page 426);

(XLVII) 4-phenoxyphenyl (RS) -2- (pyridyloxy) propyl ether (pyriproxyfen) known from (handbook of pesticides, 10 th edition (1994), United kingdom committee on crop protection, London, page 887);

(XLVIII) 5-chloro-N- {2- [4- (2-ethoxyethyl) -2, 3-dimethylphenoxy ] ethyl } -6-ethylpyrimidin-4-amine (pyriminostrobin), known from (pesticide handbook, 10 th edition (1994), the United kingdom Committee for crop protection, London, page 887);

(XLIX) (E) -N- (6-chloro-3-pyridylmethyl) -N-ethyl-N' -methyl-2-nitroethenediamine (nitenpyram) known from (handbook of pesticides, 10 th edition (1994), british committee on crop protection, london, page 736);

(L)(E)-N¹- [ (6-chloro-3-pyridinyl) methyl-N²-cyano-N¹-methyl acetamiprid (NI-25, acetamiprid), known from (handbook of pesticides, 10 th edition (1994), british committee for crop protection, london, page 730);

(LI) Avermectin B₁(avermectin), known from (handbook of pesticides, 10 th edition (1994), british committee on crop protection, london, page 1);

(LII) plant extracts active against insects, in particular (2R, 6aS, 12aS) -1, 2, 6, 6a, 12, 12 a-hexahydro-2-isopropenyl-8, 9-dimethoxy-chromeno [3, 4-b ] -furo [2, 3-h ] -chromen-6-one (triptonide), known from (pesticide handbook, 10 th edition (1994), British crop protection Commission, London, page 758); and extracts of neem, in particular azadirachtin, are known from (handbook of pesticides, 10 th edition (1994), british committee on crop protection, london, page 54);

(LIII) preparations comprising nematodes active against insects, preferably Heterorhabditis melidis, known by (pesticide handbook, 10 th edition (1994), British crop protection Committee, London, page 560); a formulation comprising Steineema felteae, known from (pesticide handbook, 10 th edition (1994), British crop protection Commission, London, page 920); a formulation comprising Steinemama scapterisci, known as such (pesticide handbook, 10 th edition (1994), British Committee for crop protection, London, page 921);

(LIV) preparations obtainable from Bacillus subtilis, known from (pesticide handbook, 10 th edition (1994), United kingdom committee for crop protection, London, page 62); or preparations obtainable from bacillus thuringiensis species, other than those obtained from GC91 or from NCTC11821, are known;

(LV) preparations comprising a fungus active on insects, preferably Verticillium lecanii, are known from (handbook of pesticides, 10 th edition (1994), British Committee for crop protection, London, page 1040); a preparation comprising Beauveria brogoniti (Beauveria brogoniti) is known from (pesticide handbook, 10 th edition (1994), United kingdom Committee for crop protection, London, page 69); a preparation comprising Beauveria bassiana is known from (pesticide handbook, 10 th edition (1994), United kingdom Committee for crop protection, London, page 69);

(LVI) formulations comprising a virus active against insects, preferably the pine yellow leaf bee NPV, known from (pesticide handbook, 9 th edition (1991), british crop protection council, london, page 616); a preparation comprising NPV from cabbage looper is known from (handbook of pesticides, 10 th edition (1994), United kingdom Committee for crop protection, London, page 633); a preparation comprising codling moth particle virus is known from (handbook of pesticides, 10 th edition (1994), United kingdom committee for crop protection, London, page 247);

(CLXXXI) indeno [1, 2-e ] [1, 3, 4] oxadiazine-4 a (3H) -carboxylic acid, 7-chloro-2, 5-dihydro-2- [ [ (methoxycarbonyl) [ (4-trifluoromethoxy) phenyl ] amino ] carbonyl-, methyl ester (DPX-MP062), known by (Brighton Crop Protection Conference, 1996, 481-486); and

(CLXXXII) N '-tert-butyl-N' - (3, 5-dimethylbenzoyl) -3-methoxy-2-methylbenzoyl hydrazine RH-2485(methoxyfenozide), known by (Brighton Crop Protection Conference, 1996, 481-486).

(CLXXXIII) N' - [ 4-methoxydiphenyl-3-yl ] hydrazinecarboxylic acid isopropyl ester (D2341) known from (Brighton Corp Protection Conference, 1996, 487-493).

The compounds of formula (a) may in some cases exist as tautomers. For example, if R is hydrogen, the corresponding compounds of formula (a), i.e., those having a 3-H-4-imino-perhydro-1, 3, 5-oxadiazine partial structure, may be in equilibrium with their respective tautomers containing a 4-amino-1, 2, 5, 6-tetrahydro-1, 3, 5-oxadiazine partial structure. The compounds of the formula (a) in the present context are also to be understood as meaning the corresponding tautomers, where appropriate, even if the latter are not mentioned specifically in each case.

Compounds of formula (a) containing at least one basic center may form, for example, acid addition salts. They are salts with acids, for example with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids, and with strong organic carboxylic acids, such as C, unsubstituted or substituted, for example, by halogen₁-C₄Alkanecarboxylic acids, 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, for example C which is unsubstituted or substituted, for example by halogen₁-C₄Alkyl or aryl sulfonic acids, such as methane-or p-toluenesulfonic acid. The compounds of formula (a) bearing at least one acid group may also form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono-, di-or tri-lower alkylamines, for example ethyl-, diethyl-, triethyl-or dimethyl-propyl-amine, or mono-, di-or trihydroxy-lower alkylamines, for example mono-, di-or triethanolamine. If appropriate, corresponding internal salts can also be formed. Agriculturally advantageous salts are preferred in the context of the present invention. Due to the close relationship between the free form and the salt form of the compound of formula (a), the free compound of formula (a) and its salts hereinbefore and hereinafter are also conveniently understood to be the corresponding salts and free compounds of formula (a), when appropriate. The same applies to the tautomers of the compounds of formula (a) and their salts. In each case, the free form is generally preferred.

In the context of the present invention, compositions comprising the compound of formula (a) in free form are preferred.

General terms used in the context have the meanings given below, unless otherwise indicated.

The heteroatoms in the cyclic base structure of the heterocyclic radical R are all elements of the periodic Table of the elements which can form at least two covalent bonds, preferably N or S.

Halogen-as a radical per se and as a structural element of other radicals and compounds, for example as a structural element of haloalkyl, haloalkylthio, haloalkoxy, halocyclopropyl, haloalkenyl, haloalkynyl, haloallyloxy and haloallylthio-is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, more particularly fluorine or chlorine, especially chlorine.

Unless otherwise indicated, the carbon-containing groups and compounds contain in each case from 1 up to and including 6, preferably from 1 up to including 3, in particular 1 or 2, carbon atoms.

Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopropyl.

Alkyl-as a group per se or as a structural element of other groups and compounds, such as, for example, as a structural element of phenylalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio-in each case taking account of the difference in the number of carbon atoms which the respective group or compound contains in each case, or is straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or is branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl, haloalkenyl, alkynyl and haloalkynyl are straight-chain or branched and in each case contain two or preferably one unsaturated carbon-carbon bond. The double or triple bond of these substituents is preferably separated from the remainder of the compound of formula (A) by at least one saturated carbon atom. Examples are allyl, methallyl, but-2-enyl, but-3-enyl, propargyl, but-2-ynyl and but-3-ynyl.

Halogen extractionSubstituted carbon-containing groups and compounds, such as haloalkyl, haloalkylthio, haloalkoxy, halocyclopropyl, haloalkenyl, haloalkynyl, haloallyloxy and haloallylthio, may be partially or fully halogenated and, in the case of polyhalogenation, the halogen substituents may be the same or different. Examples of haloalkyl radicals-as radicals per se or as structural elements of other radicals and compounds, e.g. as structural elements of haloalkylthio and haloalkoxy-are methyl radicals which are mono-to trisubstituted by fluorine, chlorine and/or bromine, e.g. CHF₂Or CF₃(ii) a Ethyl mono-to penta-substituted by fluorine, chlorine and/or bromine, e.g. CH₂CF₃、CF₂CF₃、CF₂CCl₃、CF₂CHCl₂、CF₂CHF₂、CF₂CFCl₂、CF₂CHBr₂、CF₂CHClF、CF₂CHBrF or CClFCHClF; propyl or isopropyl mono-to heptasubstituted by fluorine, chlorine and/or bromine, e.g. CH₂CHBrCH₂Br、CF₂CHFCF₃、CH₂CF₂CF₃、CF₂CF₂CF₃Or CH (CF)₃)₂(ii) a And butyl mono-to nonasubstituted by fluorine, chlorine and/or bromine or one of its isomers, such as CF (CF)₃)CHFCF₃，CF₂(CF₂)₂CF₃Or CH₂(CF₂)₂CF₃. Examples of haloalkenyl are 2, 2-difluoroethen-1-yl, 2-dichloroethen-1-yl, 2-chloropropen-1-en-3-yl, 2, 3-dichloroprop-1-en-3-yl and 2, 3-dibromoprop-1-en-3-yl. Examples of haloalkynyl are 2-chloroprop-1-yl-3-yl, 2, 3-dichloroprop-1-yn-3-yl and 2, 3-dibromoprop-1-yn-3-yl. Examples of halo-cyclopropyl are 2-chloro-cyclopropyl, 2-difluoro-cyclopropyl and 2-chloro-2-fluoro-cyclopropyl. Examples of haloallyloxy are 2-chloro-prop-1-en-3-yloxy, 2, 3-dichloroprop-1-en-3-yloxy and 2, 3-dibromoprop-1-en-3-yloxy. Examples of haloallylthio are 2-chloro-prop-1-en-3-ylthio, 2, 3-dichloroprop-1-en-3-ylthio and 2, 3-dibromoprop-1-en-3-ylthio.

In phenylalkyl, the alkyl radical bonded to the remainder of the compound of the formula (A) is substituted by a phenyl radical, the alkyl radical preferably being straight-chain and the phenyl radical preferably being bonded to the alkyl radical in a position above the alpha position, in particular in the omega position; examples are benzyl, 2-phenylethyl and 4-phenylbutyl.

Particularly preferred compounds of the formula (A) are those in which

(1) R is hydrogen, C₁-C₄Alkyl radical, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl or C₂-C₆Alkynyl, especially H or CH₃；

(2) The cyclic basic skeleton of A contains 2 to 4 double bonds, preferably conjugated double bonds, preferably 2, preferably conjugated double bonds, and in particular has an aromatic character,

(3) the cyclic basic skeleton of A contains 1 to up to and including 4, in particular 1 to up to and including 3, in particular 1 or 2, heteroatoms, particularly preferably 2.

(4) The cyclic base skeleton of A contains 1, 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen, with no more than one heteroatom contained in the cyclic base skeleton being an oxygen or sulfur atom, preferably at least one nitrogen atom;

(5) a compound of formula (A), wherein A is selected from the group consisting of halogen and C₁-C₃-substituents of alkyl are mono-or disubstituted, in particular by halogen, more particularly by chlorine.

(6) A compound of formula (A), wherein the cyclic base skeleton of A is pyridine, 1-oxidopyrido or thiazolyl,

preferably, the cyclic basic skeleton of A is pyridin-3-yl, 1-oxido-3-pyrido or thiazol-5-yl,

in particular, A is pyridin-3-yl, 2-halopyridin-5-yl, 2, 3-dihalopyridin-5-yl, 2-C₁-C₃-alkylpyridin-5-yl, 1-oxido-3-pyrido, 2-halo-1-oxido-5-pyrido2, 3-dihalo-1-oxo-5-pyrido or 2-halothiazol-5-yl,

a is more particularly pyridin-3-yl, 2-halopyridin-5-yl, 2-halo-1-oxido-5-pyrido or 2-halothiazol-5-yl,

preferably A is 2-chloropyridin-5-yl, 2-methylpyrazol-5-yl, 1-oxido-3-pyrido, 2-chloro-1-oxido-5-pyrido, 2, 3-dichloro-1-oxido-5-pyrido or 2-chlorothiazol-5-yl,

a is more preferably pyridin-3-yl, 2-chloropyridin-5-yl, 2-chloro-1-oxido-5-pyrido or 2-chlorothiazol-5-yl,

in particular, A is 2-chloropyridin-5-yl, or preferably, 2-chlorothiazol-5-yl;

(7) a compound of formula (A) wherein X is N-NO₂；

(8) A compound of formula (A) wherein A is 2-chlorothiazol-5-yl or 2-chloropyridin-5-yl, R is C₁-C₄-alkyl and X is N-NO₂；

[0170] Compounds of the formula (A) which are preferably mentioned in the context of the present invention are

(A.1) (2-Chloropyridin-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1, 3, 5-A diazine;

(A.2) (2-Chlorothiazol-5-ylmethyl) -3-ethyl-4-nitroimino-perhydro-1, 3, 5-A diazine;

(A.3) 3-methyl-4-nitroimino-5- (1-oxo-3-pyridomethyl) -perhydro-1, 3, 5-A diazine;

(A.4) (2-chloro-1-oxido-5-pyridomethyl) -3-methyl-4-nitroimino-perhydro-1, 3, 5-diAn oxazine;

(A.5)5- (2-Chlorothiazol-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1, 3, 5-A diazine;

(A.6) 3-methyl-5- (2-methylpyridin-5-ylmethyl) -4-nitroimino-perhydro-1, 3, 5-A diazine;

(A.7) (2-Chloropyridin-5-ylmethyl) -4-nitroimino-perhydro-1, 3, 5-A diazine;

(A.8) (2-chlorothiazol-5-ylmethyl) -4-nitroimino-perhydro-1, 3, 5-A diazine; or

(A.9) (2-Chloropyridin-5-ylmethyl) -3-ethyl-4-nitroimino-perhydro-1, 3, 5-A diazine.

5- (2-chlorothiazol-5-ylmethyl) -3-methyl-4-nitroimino-1, 3, 5-Diazines are particularly preferred mixed partners of formula (A) in the context of the present invention. Containing, in addition to the compound of formula (A), only oneCombinations of various other pesticidally active compounds (I) to (CLXXXIV) are also preferred. Comprising the compound 5- (2-chlorothiazol-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1, 3, 5-Compositions in which the diazine is active as component (A) are likewise preferred. Compositions which, in addition to the compounds of the formula (A), also comprise pyriproxyfen, fipronil, endosulfan or buprofezin are likewise preferred.

The active compound combinations according to the invention preferably comprise active compound (A) and one of the active compounds (I) to (CLXXXIV) in a mixing ratio of from 100: 1 to 1: 6000, in particular from 1: 50 to 50: 1, in particular from 1: 20 to 20: 1, in particular from 10: 1 to 1: 10, in particular from 5: 1 to 1: 5, more preferably from 2: 1 to 1: 2, and likewise preferably from 4: 1 to 2: 1, in particular from 1: 1, or 5: 2, or 5: 3, or 5: 4, or 4: 1, or 4: 2, or 4: 3, or 3: 1, or 3: 2, or 2: 1, or 1: 5, or 2: 5, or 3: 5, or 4: 5, or 1: 4, or 2: 4, or 3: 4, or 1: 3, or 2, or 1: 600, or 1: 300, or 1: 150, or 1: 35, or 35: 35, or 2: 2, or 4, or 1: 75, or 2: 75, or 4: 75, or 1: 6000, or 1: 3000, or 1: 1500, or 1: 350, or 2: 350, or 4: 350, or 1: 750, or 2: 750, or 4: 750. These ratios are understood to be weight ratios on the one hand and molar ratios on the other hand.

The composition of the invention preferably comprises pyriproxyfen.

The composition of the invention preferably comprises fipronil.

The composition of the invention preferably comprises endosulfan.

The composition of the present invention preferably comprises buprofezin.

The composition of the invention preferably comprises pirimicarb.

The invention also relates to a method for controlling pests, which comprises applying the composition according to the invention to the pests or their environment.

The invention also relates to a method of controlling pests and protecting plant propagation material, which comprises treating the plant propagation material or the site where the propagation material is growing.

The invention also relates to a process for the preparation of the compositions according to the invention comprising at least one adjuvant, which comprises bringing the active compound into intimate admixture with the adjuvant.

The invention also relates to plant propagation material treated by the method for controlling pests and protecting plant propagation material.

The invention also relates to the use of the above-mentioned composition for the preparation of a composition according to the invention comprising at least one adjuvant, or for controlling pests and protecting plant propagation material.

The invention also relates to the use of a compound of formula (a), in free form or in agriculturally acceptable salt form, for preparing a composition according to the invention.

It has now been found that, surprisingly, the combination of an active compound of the formula (a) or one of its salts with one of the active compounds (I) to (CLXXXIV) not only produces an additive increase in the spectrum of action against pests, which is to be expected in principle, but also achieves a synergistic effect. This synergistic effect extends the action limits of both formulations in two ways:

on the one hand, the ratio of the compounds of the formula (A) to the individual compounds of the formulae (I) to (CLXXXIV) to be applied is reduced, while equally good results are obtained. On the other hand, the combined mixture still has a high level of pest control effect, while the two individual substances become completely inactive at a low application rate range. This results in a significant expansion of the pest spectrum which can be controlled on the one hand and an increase in the application reliability on the other hand.

In addition to the actual synergistic effect on the pesticidal activity, the compositions according to the invention additionally have surprising advantages which can likewise be regarded broadly as synergistic: accordingly, pests which cannot be controlled or cannot be controlled sufficiently effectively with the compounds of the formulae (a) or (I) to (CLXXXIV) alone can be controlled, and the compositions according to the invention can be better tolerated by plants, i.e. the phytotoxicity is reduced, compared with the compounds (a) and (I) to (CLXXXIV) alone. Furthermore, various stages of growth and development of the insects can be controlled, which is not always the case with the individual compounds (A) and (I) to (CLXXXIV), since these can only be used as adulticides or else only as larvicides for controlling very specific larval stages. In addition, the combination of compound (a) with certain formulae (I) to (CLXXXIV) shows more advantageous properties during milling, mixing, storage and spraying.

The compositions according to the invention have preventive and/or therapeutic value in field control of pests at low concentrations, while at the same time being tolerated by warm-blooded animals, fish and plants and having a very advantageous biocidal spectrum. The compositions of the present invention are active against all or individual developmental stages of normally sensitive and resistant animal pests such as insects and representative species of the order Acarina. The insecticidal and/or acaricidal action of the compositions according to the invention is manifested directly on the extermination of pests, either immediately or after a while, for example during moulting, or else indirectly in a reduction in the egg laying and/or hatching rate, this good action corresponding to a destruction rate (mortality) of at least 50 to 60%.

Animal pests include:

lepidoptera, for example:

the species cochleariae (acleisis spp.), the species cochleariae (Adoxophyes spp.), the species diaphania (Aegeria spp.), the species cutworm (Agrotis spp.), the species noctuid (arabidopsis argillata), the species noctuid (albama argillaceae), the species amoylosis spp., the species pisciresia (verticillia gemmatalis), the species cochlearia (archea spp.), the species cochleariae (argyrophylla spp.), the species noctui (autogra spp.), the species athea (autogra spp.), the species zea mays (burssola fusca), the species physalis (caerula caudatus (caea caudatus), the species carpesia (colletotrichia nigerella, the species cochlegma), the species cryptophytes (diaphysalis), the species cryptophyta (ostrinia spp.), the species cochlegma spp.), the species cryptophyta (ostrinia spp.), the species cochlegma spp., the species cnidium (cryptophyra, the species cochlegma spp.), the species cnidium (cryptophyra, the species cochlegma (cryptophysalis (cryptophyta), the species cochlegma spp.), the species cnidas (cryptophysalis spp.), the species cnida spp.), the species cnidas (cryptophysa), the species cnidas (cryptophyta), the species cnidas (cryptophysa), the species cnidas (cryptophysa), the species cnidas (cryptophys spp.), the species cnidas (cryptophys (, The species cochleariae (eucommia spp.), Eupoecilia ambiguella, xanthophysalis (euproctitis spp.), rhizophora (Euxoa spp.), carposina (Grapholita spp.), hedera, hedyotis nubilana, noctuina (Heliothis spp.), phomopsis (helolus spp.), plutella xylostella (helolus spp.), fall webworm (hyphena cunea), pholida solanacearum (keifda lycopersilica), spiderworm (leicotinia sciaenae), plutella xylostella (leicoterpera), leptosperma (litura sciola spp.), leptospermata (litocephalia spp.), liptera (lityoides spp.), globulus spodoptera, lochia tetranospora borreri (lobelia tetranospora tetrana), phomopsis (Ostrinia spodoptera, phomopsis (Ostrinia spp.), phomopsis, phoma spodoptera (Ostrinia spp.), pholiota (Ostrinia spp.), pholitura spp.), pholitura (Ostrinia spodoptera spp.), gylus (Ostrinia spp.), trypanosoma (Ostrinia spp.), tryps (Ostrinia spp.), trypanosoma (Ostrinia spp.), trypanosoma (ostrea (Ostrinia spp.), trypanosoma (ostr, Diamondback moth (Plutella xylostella), Plutella (Prays spp.), agrostis (scirphaga spp.), carposina (sersamia spp.), gypsophila (sesami spp.), colletotrichum (sporganno spp.), gypsophila (sporganno spp.), Spodoptera (Spodoptera spp.), codtera (synanthon spp.), navicula (thauma spp.), tortricid (thylloptera spp.), tortricid (torx spp.), Trichoplusia (Trichoplusia ni) and armyworm (ypoma spp.);

from the order of Coleoptera, e.g.

Click beetles (Agriotes spp.), florists (anthomonus spp.), cryptophagus betanae (atorias lineris), phyllotreta betanus (Chaetocnema tibialis), root-neck weevils (Cosmopolites spp.), weevils (Curculio spp.), bark beetles (dermests spp.), Diabrotica (Diabrotica spp.), phytophaga (epirhahna spp.), eremus spp, allemys spp, leptospora (leptoteraci) beetles (lepinotara), oryzophragma (meloorpha spp.), parvus (melodiophora spp.), parvus (scleroderma spp.), spilus (phytophagus spp.), and pseudoptera (trichoderma spp.), spilotis (scleroderma spp.), spilotia spp.);

from the order of straight wings, e.g.

Blattaria (Blatta spp.), blattaria (Blattelia spp.), cricket mole (Gryllotalpa spp.), maderaria (leucorhagiae maderae), Locusta (Locusta spp.), Periplaneta (periplanta spp.) and Locusta desert (Schistocerca spp.);

from the order of Isoptera, e.g.

Reticulitermes spp);

from the order of Rodentia, e.g.

The genus Cochloae (Liposcelis spp.);

phthiraptera, e.g.

The genera diaphorina (haemantopinus spp.), pediculosis (linoglucharus spp.), pediculosis (pediculussp.), pediculosis (pediocuruspp.), gossypium goiter (Pemphigus spp.) and Phylloxera (Phylloxera spp.);

from the order of the Colletotrichum, e.g.

Zoophthiriasis (Damalinea spp.) and louse masticatory (trichodices spp.);

from the order of the Thysanoptera, e.g.

Thrips (Frankliniella spp.), Thrips (Hercinothrips spp.), Thrips (Taenioththrips spp.), Thrips palmi (Thrips palmi), Thrips tabaci (Thrips tabaci) and Thrips africana (Scintathrips aurantii);

from the order of Hemiptera, e.g.

Stinkbug (Cimex spp.), theobroma, coriaria (dysdermus spp.), lygus lucorum (Eurygaster spp.), lygus lucorum (leptocyssa spp.), lygus lucorum (leptoporus spp.), lygus lucorum (Nezara spp.), lygus dermorum (Piesma spp.), rhus rudinicola (Rhodnius spp.), lygus lucorum (Sargella sanguinea), lygus lucorum (Scotophyllum spp.), and trypanosoma (Thatoma spp.);

from the order of homoptera, e.g.

Aleurosporium ludinum (aleurosporius florosus), aleyrodids brassicae, scutellariae sp, Aphididae (Aphididae), aphids (Aphis spp), scutellariae sp, sweetpotato whitefly (bemis tabaci), ceraplaster sp, melanogaster (chrysophalus aonidum), orange brown scutellariae (chrysophalus dicum dicoccum), phacanicola (cocus hepeddum), phyllophyces parvus (Empoasca spp), phyllophyces saloides (phytoplanuginosus), pelothyrium peltatum (paraphyllum), phyllophyces peltatus (purpurea), phyllophyces pellucida (paraphyllus), phyllophyces pellucida (phyllophyces spp), phyllophyces pelothyrium (phyllophyces peltatus), phyllophyces peltatus (purpureus, phyllophyces peltatus), phyllophyces pellucorhii (purpurea), phyllotphycus spp), phyllotryna sp, phyllotryophyllus sp, phyllopyrodes sp Pelagia (quadrastichus spp.), sinonovacula (Rhopalosiphum spp.), pelagia (Saissetia spp.), cicada (Scaphoideusspp.), Schizaphis (Schizaphis spp.), Sitobion spp.), aleurodes vaporariorum (Trialeurodesvarovarachum), Triptera (Trioza erytreae) and Kigeleaulirus (Unnasalis citri);

from the order of the hymenoptera, e.g.

Acromymex, Atta spp, Blastus (Cephalosporus spp.), Cerrena (Diprion spp.), Cerrena (Dipionidae), Cerrena (Gilpinia polytoma), Hoplocpa spp, Lasius spp., Melastoma (Monomorium pharaonis), Neprionas (Neodiprion spp.), Pyrola (Solenopsis spp.) and Vespa spp.;

from the order of diptera, e.g.

Aedes (Aedes spp.), Anthedgona (coccata), Aedes hortorum (Bibio hordulanum), Callophora (Callophorrha erythrepha), Ceratophaga (Ceratoptera spp.), Chrysomyia (Chrysomyia spp.), Culex (Culex spp.), Culex (Cutebra spp.), Microphagus (Dacus spp.), Drosophila melanogaster (Drosophila melanogaster), Drosophila (Fannia spp.), Gastrophilus (Gastrophilus spp.), Dryoglossopsis (Glossina spp.), Piropoma (Hypoderma spp.), Spyria (Hypocrea spp.), Spyria (Hypoclasia spp.), Spyria (Spyria spp.), Drosophila, Spyria (Pholidia spp.), Drosophila (Chrysomyelia spp.), Drosophila (Hygrophyta (Pholiota, Spyria (Phosphatida (Pholidia spp.), Drosophila (Pholiota), Drosophila spp.), Drosophila (Lucilia spp.), Drosophila (Lucilia (Lucili) and Spyris (Lucilia) in Spyria) Spyris, Spyria, Spyristospossia, Spyria Spyristospossia, Spyria, Spyria, The genera Stachys (Stomoxys spp.), Tabanus (Tabanusspp.), a smaller kind of cicada cicada (Tannia spp.) and Daphus (Tipula spp.);

siphonaptera, e.g. Siphonaptera

Ceratophyllus spp (Ceratophyllus spp.) and Xenopsylla cheopis (Xenopsylla cheopis);

from the order of the Thysanura, e.g.

Octopus (Lepisma saccharana), and

from the order of Acarina, e.g. Acarina

Acanthophytes tetranychii (Acarus sriro), aleyrodida citriodora (acaria sheldoni), acanthophytes pomponensis (Acarus schlechlendoli), aleyrodida (ambromma spp.), elegans (Argas spp.), oxeruptos (Boophilus spp.), brachypodium (brevipippus spp.), lucerne (Bryobia praetiosa), calipitris indica (Bryobia praetiosa), psoroptes (Choroptes spp.), Dermanyssus gallinae (Dermanyssus gailinae), Eotophyllus tetranychii (Eotophyllus carpini), Eleophytes (Eriophyllus spp.), hyalomyxa spp, ixodidae spp, Oygon mites, Ornithodoros spp, Panonychus spp, Photinus rust, Phylocoptus variegatus, Tarsonemus laterosus, Primordia spp, Psychus spp, Rhipicephalus spp, Rhizophus spp, Sarcophagus spp, Sarcophytos spp, Tarsonemus spp and Tetranychus spp.

The active compound mixtures according to the invention can be used to control (i.e. control or kill) the particular pests mentioned above, which occur on plants, in particular on useful plants and ornamentals in agriculture, horticulture and forests, or on parts of these plants, such as fruits, flowers, leaves, stems, tubers or roots; in some cases even parts of later-grown plants can be protected from these pests.

The pesticidal mixtures according to the invention can advantageously be employed for controlling pests on: cereals such as corn or sorghum; fruit trees, for example pomes, nuts and soft fruits, such as apples, pears, plums, peaches, apricots, cherries or berries, for example strawberries, raspberries and blackberries; leguminous plants, such as broad beans, lentils, peas and soybeans; oil crops, such as oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa or peanuts; melons, such as pumpkin, cucumber or watermelon; fiber plants, such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruit or mandarins; vegetables such as spinach, lettuce, asparagus, cabbage, radish, shallot, tomato, potato or pepper; laurel plants, such as avocado, bay and camphor trees; or tobacco, nuts, coffee, eggplant, sugar cane, tea, zanthoxylum, grapes, hops, musk orchid plants, natural rubber or ornamental plants, in particular corn, sorghum, pome and nut plants, legumes, cucurbits, cotton, citrus fruits, vegetables, eggplant, grapes, hops or ornamental plants, more particularly corn, sorghum, apple, pear, plum, peach, bean, pea, soybean, olive, sunflower, coconut, cocoa, peanut, cucumber, pumpkin, citrus fruits, cabbage, tomato, potato, grape or cotton, particularly preferably grape, citrus fruits, apple, pear, tomato and cotton.

Further areas of application of the mixtures of active compounds according to the invention are the protection of stored products and livestock and materials, and in the hygiene sector, in particular the protection of domestic and productive livestock against the abovementioned pests.

Depending on the object to be achieved and the environment in which it is placed, the pesticides of the invention may be concentrated emulsifiable concentrates, concentrated suspensions, directly sprayable or dilutable solutions, expandable pastes, dilute emulsions, sprayable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or capsules of polymers which comprise a compound of the formula (A) or one of its salts and one of the other active compounds (I) to (CLXXXIV) of the invention.

The active compounds in these compositions are employed in pure form, for example as solid active compounds, with a particular particle size, or preferably in combination with at least one of the usual adjuvants used in formulation, such as extenders, for example solvents or solid carriers, or as surface-active compounds (surfactants).

The solvent is, for example: non-hydrogenated or partially hydrogenated aromatic hydrocarbons, preferably fraction C₈-C₁₂Alkylbenzenes of (a) such as xylene mixtures, alkylated or tetrahydronaphthalenes, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and ethers and esters thereof such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or-ethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methylpyrrolidin-2-one, dimethyl sulfoxide or N, N-dimethylformamide, water, non-epoxidized or epoxidized vegetable oils such as non-epoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soybean oil, and silicone oils.

Commonly used solid carriers, for example for dusts or dispersible powders, are natural rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly dispersed silicic acid or highly dispersed adsorptive polymers may also be added to improve physical properties. The granules, the absorbent granular carriers are of the porous type, such as pumice, broken brick, sepiolite or bentonite, and the non-absorbent carrier material is calcite or sand. It is also possible to use a large amount of particulate material of inorganic or organic nature, in particular dolomite or ground plant residues.

Depending on the nature of the active compounds to be formulated, the surface-active compounds are nonionic, cationic and/or anionic surfactants or surfactant mixtures having good emulsifying, dissolving and wetting properties. The surfactants listed below are considered to be illustrative only; many other surfactants conventionally used in formulation processes and suitable for the present invention are described in the relevant literature.

Nonionic surfactants are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated aliphatic acids and alkylphenols, which may contain from 3 to 30 glycol groups and from 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and from 6 to 18 carbon atoms in the alkyl radical on the alkylphenols. Water-soluble adducts, polyethylene oxides containing from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycols having from 1 to 10 carbon atoms in the alkyl chain are suitable. The compounds generally mentioned comprise from 1 to 5 ethylene glycol units per propylene glycol unit. Examples are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene oxide/ethylene oxide adducts, tributylphenoxypolyethoxyethanols, polyethylene glycols and octylphenoxypolyethoxyethanols. Aliphatic acid esters of polyoxyethylene-sorbitan, such as polyoxyethylene-sorbitan trioleate, are also possible.

The cationic surfactants are in particular quaternary ammonium salts containing as substituents at least one alkyl group having from 8 to 22 carbon atoms and as further substituents a lower non-halogenated or halogenated alkyl group, a benzyl group or a lower hydroxyalkyl group. These salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are trimethyl ammonium stearate chloride and benzyl bis (2-chloroethyl) ethyl ammonium bromide.

Suitable inorganic surfactants may be water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are the higher aliphatic acids (C)₁₀-C₂₂) Alkali metal, alkaline earth metal and substituted and unsubstituted ammonium salts of (a), such as oleic acid and stearic acid, or sodium or potassium salts of naturally occurring aliphatic acid mixtures, which can be obtained, for example, from coconut oil or tall oil; and also aliphatic acid methyltaurates. However, more commonly synthetic surfactants are used, in particular aliphatic sulfonates, aliphatic sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. Aliphatic sulfonates and sulfates are generally alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and generally contain an alkyl group having from 8 to 22C atoms, the alkyl group also including the alkyl portion of the acyl group; examples are sodium or calcium salts of lignosulfonic acid, lauryl sulfate, or mixtures of aliphatic alcohol sulfuric acids prepared from naturally occurring aliphatic acids. They also include salts of sulfuric and sulfonic acids of aliphatic alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivative preferably contains two sulfonic acid groups and one aliphatic acid group having about 8 to 22 carbon atoms. Alkyl aryl sulfonic acids are, for example, the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of naphthalenesulfonic acid-formaldehyde condensation products. Corresponding phosphoric acids, such as salts of phosphoric acid esters of the p-nonylphenol- (4-14) -ethylene oxide adduct, or phospholipids, are also suitable.

In general, the compositions of the invention comprise from 0.1 to 99%, in particular from 0.1 to 95%, of a mixture of an active compound of the formula (a) and one of the active compounds (I) to (CLXXXIV), and from 1 to 99.9%, in particular from 5 to 99.9%, of at least one solid or liquid adjuvant, where in general from 0 to 25%, in particular from 0.1 to 20%, of the composition may be a surfactant (% in each case being a percentage by weight). While concentrated compositions are the preferred commercial product, the end user typically uses dilute compositions, which have a relatively low concentration of active compound. Preferred compositions have in particular the following components (% by weight):

emulsifiable concentrate：

Active ingredient mixtures 1 to 90%, preferably 5 to 20%

Surfactant 1 to 30%, preferably 10 to 20%

Solvent 5 to 98%, preferably 70 to 85%

Powder preparation：

Active compound mixture: 0.1 to 10%, preferably 0.1 to 1%

Solid carriers 99.9 to 90%, preferably 99.9 to 99%

Suspending agent：

5 to 75%, preferably 10 to 50%, of the active compound mixture

94 to 24%, preferably 88 to 30% of water

Surfactant 1 to 40%, preferably 2 to 30%

Wettable powder：

Active compound mixtures 0.5 to 90%, preferably 1 to 80%

0.5 to 20%, preferably 1 to 15% of a surfactant

Solid support 5 to 99%, preferably 15 to 98%

Granules：

Active compound mixtures 0.5 to 30%, preferably 3 to 15%

Solid carriers 99.5 to 70%, preferably 97 to 85%

The compositions of the invention may also comprise other solid or liquid adjuvants such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, for example silicone oils, preservatives, viscosity regulators, adhesives and/or tackifiers, and also fertilizers or other active compounds for achieving a specific effect, for example bactericides, fungicides, nematicides, molluscicides or herbicides.

The compositions according to the invention are prepared in a known manner by mixing and/or grinding the active compound or active compound mixture in the absence of auxiliaries, for example by grinding, sieving and/or extruding solid active compounds or active compound mixtures, for example to a specific particle size, and in the presence of at least one auxiliary, by bringing the active compound or active compound mixture to intimate mixing and/or grinding together with one or more auxiliary. The invention therefore also relates to a process for the preparation of the composition.

Mixtures of a compound of the formula (A) with one or more compounds (I) to (CLXXXIV) are preferably processed in a known manner, together with the auxiliaries customary in the art of formulation, to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts and granules, and also, for example, to capsules of polymers. Depending on the intended purpose and the environment in which it is placed, the method of application may be chosen according to the nature of the composition, such as spraying, atomizing, dusting, wetting, scattering or pouring.

The invention therefore also relates to the application of the compositions, i.e. the compositions can be applied by spraying, atomizing, dusting, spreading, dressing, scattering or pouring, as appropriate for the purpose to be achieved and the environment in which they are to be used, and also for the type of pests to be controlled as described above. Typical concentrations here are between 0.1 and 1000ppm, preferably between 0.1 and 500ppm, of active compound. The application rate can vary within wide limits and depends on the nature of the soil, the nature of the application (foliar application; seed dressing; seed-furrow application), the crop, the pests to be controlled, the particular climatic environment and other factors which are determined by the nature of the application, the time of application and the target crop. The application rate per hectare is generally from 1 to 2000g of active compound per hectare, in particular from 10 to 1000g/ha, preferably from 20 to 600 g/ha.

The preferred method of application in crop-protecting fields is to apply to the foliage of the plants (foliar application), where the number of applications and the amount applied depends on the risk of infestation by the particular pest. However, the active compounds can also be applied to the soil in solid form, for example in the form of granules (soil application), by wetting the habitat of the plants with a liquid formulation, by penetration of the soil through the roots into the plants (systemic action), or else by applying the active compounds in solid form, for example in the form of granules (soil application). In rice crops, these particles can be quantitatively applied to irrigated paddy fields.

The compositions according to the invention are also suitable for protecting plant propagules, for example seeds, such as fruits, tubers, or cereals, or young plants, against animal pests. The propagated plants may be treated with the composition prior to production, for example the seeds may be dressed prior to sowing. The active compounds according to the invention can also be applied to seed cereals (coatings) or by impregnating the cereals with liquid compositions or coating them with solid compositions. The composition may also be applied to the site of production of propagation material during sowing of the seed, for example in the furrow of the seed during sowing. The invention also relates to a method for the treatment of these plant propagation materials and to plant propagation material treated in this way.

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

Formulation examples (% weight percent, ratio of active compound to weight)

Example F1: concentrated milkOil a) b) c)

Active compound mixture [ compound (a):

compounds (I) to (CLXXXIV) ═ 1: 1] 25% 40% 50%

5 percent of calcium dodecyl benzene sulfonate, 8 percent of calcium dodecyl benzene sulfonate and 6 percent of calcium dodecyl benzene sulfonate

Castor oil polyglycol ether (36mol EO) 5%

Tributylphenol polyglycol ether (30mol EO) 12% 4%

Cyclohexanone 15% to 20%

Xylene mixture 65% 25% 20%

EO is the degree of ethoxylation of castor oil or tributylphenol.

Emulsions of any desired concentration can be prepared by diluting the concentrate with water.

Example F2: solutions of a) b) c) d)

Active compound mixture [ compound (a):

compounds (I) to (CLXXXIV) ═ 1: 3] 80%, 10%, 5%, 95%

Ethylene glycol monomethyl ether 20%

Polyethylene glycol with molecular weight of 40070%

N-methyl-2-pyrrolidone 20%

Ethoxylated coconut oil 1% 5%

Gasoline (boiling point 160-190 deg.C) 94%

These solutions are suitable for use in the form of small droplets.

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

Active compound mixture [ compound (a):

compounds (I) to (CLXXXIV) ═ 3: 1] 5%, 10%, 8% and 21%

94 percent of kaolin, 79 percent of kaolin and 54 percent of kaolin

High-dispersion silicic acid 1% 13% 7%

90 percent of attapulgite clay to 18 percent

The active compounds are dissolved together in dichloromethane and the solution is sprayed onto the carrier, after which the solvent is evaporated off in vacuo.

Example F4: powder preparation a) b)

Active compound mixture [ compound (a):

compounds (I) to (CLXXXIV) ═ 1: 1] 2% 5%

2 percent of high-dispersion silicic acid and 5 percent of high-dispersion silicic acid

Talc 97 percent

90 percent of kaolin

The carrier is mixed thoroughly with the active compound to give a directly usable powder.

Example F5: wettable powder a) b) c)

Active compound mixture [ compound (a):

compounds (I) to (CLXXXIV) ═ 4: 1] 25% 50% 75%

5 percent of sodium lignosulfonate

Sodium lauryl sulfate 3% to 5%

Sodium diisobutylnaphthalenesulfonate 6% to 10%

Octyl phenol polyglycol ether (7-8mol EO) 2%

High-dispersion silicic acid 5%, 10%

62 percent of kaolin 27 percent

The active compound is mixed together with the additives and thoroughly ground in a suitable mill. Wettable powders are obtained, from which emulsions of any desired concentration can be diluted with water.

Example F6: concentrated emulsifiable concentrate

Active Compound mixture (1: 2) 10%

Octyl phenol polyglycol ether (4-5mol EO) 3%

Calcium dodecyl benzene sulfonate 3%

Castor oil polyglycol ether (36mol EO) 4%

Cyclohexanone 30%

Xylene mixture 50%

Emulsions of any desired concentration can be prepared by diluting the concentrate with water.

Example F7: powder preparation a) b)

Active compound mixture [ compound (a): 5 percent to 8 percent

Compounds (1) to (CLXXXIV) 2: 5)

Talc 95%

Kaolin 92%

Directly usable powders are obtained by mixing the active compound with a carrier and grinding in a suitable mill.

Example F8: extruded granules

Active compound mixture [ compound (a):

compounds (I) to (CLXXXIV) ═ 2: 1] 10%

Sodium lignosulfonate 2%

1 percent of carboxymethyl cellulose

Kaolin 87%

The active compound is mixed with additives and the mixture is ground and moistened with water. This mixture was extruded, granulated and then dried with an air stream.

Example F9: coated granule

Active compound mixture [ compound (a):

compounds (I) to (CLXXXIV) ═ 1: 1] 3%

Polyethylene glycol (molecular weight 200) 3%

94 percent of kaolin

The finely ground active compound is applied homogeneously to the kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coated granules are obtained.

Example F10: concentrated suspension concentrate

Active Compound mixture (1: 1) 40%

10 percent of ethylene glycol

Nonylphenol polyglycol ether (15mol EO) 6%

Sodium lignosulfonate 10%

1 percent of carboxymethyl cellulose

37% aqueous formaldehyde solution 0.2%

75% Silicone oil in the form of an aqueous emulsion 0.8%

32 percent of water

The finely ground active compound is thoroughly mixed together with the additives. By dilution with water, suspensions of any desired concentration can be obtained from the suspending agent.

It is more common practice to process the active compound of the formula (a) and one of the mixing partners (I) to (CLXXXIV) separately and then to place them together in the desired mixing ratio as a "tank mix" in the water of the application apparatus shortly before application.

Biological examples (% percent by weight, unless otherwise indicated)

When the combined action EA of the active compound (a) with one of the active compounds (I) to (CLXXXIV) is greater than the sum of the actions of these active compounds when administered alone, then there is always a synergistic action:

EA₁＞X+Y (B)

however, for a given combination of two pesticides, the effect EA of the pesticide can be calculated using the following formula (see, COLBY, S.R., "stabilizing synthetic and antibacterial responses of pesticide combinations", Weed 15, Pages 20-22, 1967):

EA₂＝X+Y(100-X)/100 (C)

in this formula:

percent mortality compared to untreated control (═ 0%) treated with the compound of formula (a) at an application rate of p kilograms per hectare.

Percent mortality compared to untreated controls, treated with q kg of a compound of formulae (I) to (CLXXXIV) at an application rate per hectare.

EA ═ expected pesticidal effect after treatment with compounds of formula (a) and compounds (I) to (CLXXXIV) at an application rate of p + q kg per hectare (percent mortality compared to untreated controls).

If the actually observed effect is greater than the expected value EA, there is a synergistic effect.

Example B1: action against sweet potato whitefly

The dwarf broad beans are placed in a gauze cage, and the adult sweet potato whiteflies are transplanted. After spawning, all adults were removed. After 10 days, the plants on which the nymphs had grown were sprayed with an aqueous spray suspension comprising 50ppm of the active compound mixture. After a further 14 days, the egg hatching percentage was compared with the untreated control group.

In this test, the combination of active compound with one of the active compounds (I) to (CLXXXIV) has a synergistic effect. In particular, spray aqueous suspensions comprising 40ppm of compound (A.5) and 10ppm of compound (II) have an activity of greater than 80%.

Example B2: anti-Egyptian cotton roll moth larva effect

The soybean seedlings are sprayed with a spray water emulsion containing 360ppm of the active compound mixture. After drying the spray liquid layer, 10 third-instar egyptian cotton looper larvae were transferred to soybean seedlings and placed in a plastic container. Evaluation was performed after 3 days. The percentage reduction in population and percentage reduction in feeding damage (% action) for each insect was determined by comparing the number of dead larvae and feeding damage on treated plants to those on untreated control plants.

In this test, the combination of active compound with one of the active compounds (I) to (CLXXXIV) has a synergistic effect. In particular, aqueous spray suspensions comprising 200ppm of compound (A.2) and 160ppm of compound (XXIX) and aqueous spray suspensions comprising 120ppm of compound (A) and 240ppm of compound (XXIV) show an activity of more than 80%.

Example B3: ovicidal action against Lobesia botrana

The Lobesia botrana eggs placed on filter paper are impregnated for a while with a mixture containing 400ppm of the active compound to be tested. After the test solution dried, the eggs were placed on a petri dish. After 6 days, the percentage of eggs hatched (% reduction in hatching) was evaluated in comparison with the untreated control group.

In this test, the combination of active compound with one of the active compounds (I) to (CLXXXIV) has a synergistic effect. In particular, spray aqueous suspensions comprising 300ppm of compound (A.5) and 100ppm of compound (III) and spray aqueous suspensions comprising 300ppm of compound (A.2) and 200ppm of compound (LVII) have an activity of more than 80%.

Example B4: ovicidal action against Heliothis virescens

The eggs of Heliothis virescens placed on filter paper are impregnated for a while with the mixture containing 400ppm of the active compound to be tested. After the test solution dried, the eggs were placed on a petri dish. After 6 days, the percentage of eggs hatched (% reduction in hatching) was evaluated in comparison with the untreated control group.

In this test, the combination of active compound (a) with one of the active compounds (I) to (CLXXXIV) has a synergistic effect. In particular, the aqueous spray suspensions comprising 240ppm of compound (A.1) and 160ppm of compound (I) and the aqueous spray suspensions comprising 100ppm of compound (A.5) and 300ppm of compound (I) have an activity of more than 80%.

Example B5: action against larvae of diamondback moth

Cabbage seedlings are sprayed with a spray water emulsion containing 440ppm of active compound. After drying the spray liquid layer, 10 third-instar diamondback moth larvae were transferred to cabbage seedlings and placed in a plastic container. Evaluation was performed after 3 days. The percentage reduction in population and percentage reduction in feeding damage (% action) for each insect was determined by comparing the number of dead larvae and feeding damage on treated plants to those on untreated control plants.

In this test, the combination of active compound with one of the active compounds (I) to (CLXXXIV) has a synergistic effect. In particular, the aqueous spray suspension comprising 40ppm of compound (A.5) and 400ppm of compound (XI) and the aqueous spray suspension comprising 220ppm of compound (A.7) and 220ppm of compound (L) had an activity of more than 80%.

Example B6: action against myzus persicae

The pea seedlings were infested with myzus persicae and subsequently sprayed with a spray containing 400ppm of active compound and incubated at 20 ℃. Evaluation was performed after 3 days and 6 days. The number of dead aphids on the treated plants was compared with that of the untreated plants, and the percent reduction in population (% action) was determined.

In this test, the combination of active compound with one of the active compounds (I) to (CLXXXIV) has a synergistic effect. In particular, an aqueous spray suspension of pirimicarb comprising 1ppm of compound (A.5) and 40ppm of compound (XI) and an aqueous spray suspension comprising 0.2ppm of compound (A.5) and 75ppm of pirimicarb have an activity of more than 80%.

Claims (5)

1. A composition for controlling insects and representatives of the order Acarina, comprising 5- (2-chlorothiazol-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1, 3, 5-A combination of a diazine and a compound selected from cyfluthrin and lambda-cyhalothrin, and at least one adjuvant, wherein the composition comprises 5- (2-chlorothiazol-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1, 3, 5-Diazine and cyfluthrin or lambda-cyhalothrin are present in a mixing ratio of 10: 1 to 1: 10 by weight.

2. A composition according to claim 1, which comprises lambda cyhalothrin.

3. The composition according to claim 1, wherein the mixing ratio is from 4: 1 to 2: 1 by weight.

4. A method for controlling pests, which comprises applying the composition of any one of claims 1 to 3 to the pests or their environment.

5. The method of claim 4 for controlling a plant propagule, the method comprising treating the plant propagule or the locus at which the propagule is grown.