GB2163430A

GB2163430A - Pesticidal benzoylphenylureas

Info

Publication number: GB2163430A
Application number: GB08520899A
Authority: GB
Inventors: Jozef Drabek; Manfred Boger; Odd Kristiansen
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1984-08-24
Filing date: 1985-08-21
Publication date: 1986-02-26
Also published as: GB8520899D0; ES8605774A1; EP0173244B1; GB2163430B; EP0173244A3; EP0173244A2; CA1241005A; ES546359A0; AU4659485A; DE3575919D1; AU588248B2; IL76167A; OA08086A; ATE50245T1; BR8504039A; ZW13585A1; DK382985A; ZA856415B; DK382985D0; NZ213215A

Abstract

Novel benzoylaminophenylureas of the formula <IMAGE> wherein R1 is hydrogen, halogen, CF3 or C1-C4alkoxy, R2 is halogen, C1-C4alkyl, CF3 or C1-C4alkoxy, R3 is hydrogen, halogen, CF3 or methyl, R4 is fluorine or chloride, R5 is hydrogen, fluorine or chlorine, R6 and R7 are each independently of the other C1-C6alkyl, C3-C5alkenyl, C3-C5alkynyl, or C1-C4-alkyl which is substituted by 1 to 8 fluorine or chlorine atoms or by methoxy or ethoxy; or R6 and R7, together with the nitrogen atom to which they are attached, are the radical <IMAGE> are prepared from novel amines. Compositions containing the novel ureas are used for controlling insects and representatives of the order Acarina. The novel ureas have larvicidal action, in particular against plant-destructive insects.

Description

SPECIFICATION Benzoylphenylureas The present invention relates to novel substituted benzoylaminophenylureas, to a process and to intermediates for the preparation thereof, and to the use of the novel compounds in pest control.

The compounds of this invention have the formula I

wherein R1 is hydrogen, halogen, CF3 or C,-C4alkoxy, R2 is halogen, C1-C4alkyl. CF i3, or C,-C4alkoxy, R3 is hydrogen, halogen, CF3 or methyl, R4 is fluorine or chlorine, R5 is hydrogen, fluorine or chlorine, R6 and R3 are each independently of the other C,-C6alkyl, C3-C5alkenyl, C3-C5alkynyl, or C,-C4alkyl which is substituted by 1 to 8 fluorine or chlorine atoms or by methoxy or ethoxy: or R6 and R7, together with the nitrogen atom to which they are attached, are the radical

Preferred compounds of formula I are those wherein R, is hydrogen, halogen, CF3 or C,-C4alkoxy, Rz is halogen, C,-C4alkyl, CF3 or C,-C4alkoxy, R3 is hydrogen, halogen, CF3 or methyl, R4 is fluorine or chlorine, R5 is hydrogen, fluorine or chlorine, R6 and R7 are each independently of the other C1-C6alkyl, C3-C5alkenyl, C3-C5alkynyl, or C,-C4alkyl which is substituted by 1 to 8 fluorine or chlorine atoms or by methoxy or ethoxy.

Compounds of formula I meriting particular interest are those wherein R, is hydrogen, fluorine, chlorine, CF3, methoxy or ethoxy, R2 is fluorine, chlorine, C,-C3alkyl, CF3 or methoxy, R3 is hydrogen, fluorine, chlorine, CF3 or methyl, R4 is fluorine or chlorine, R5 is hydrogen, fluorine or chlorine, and R6 and R7 are each independently of the other C,-C4alkyl, allyl, propargyl, or C1-C3alkyl which is substituted by 1 to 7 fluorine or chlorine atoms or by methoxy.

Further compounds of formula I meriting particular interest are those wherein P1 is hydrogen, fluorine, chlorine or methoxy, R2 is fluorine, chlorine, methyl or methoxy, R3 is hydrogen or fluorine, R4 is fluorine or chlorine, R, is hydrogen or chlorine, and R6 and R7 are each C,-C4alkyl.

Still further preferred compounds of formula I are those wherein R6 is methyl and R7 is C1-C4alkyI, and those wherein R4 is fluorine and R6 is hydrogen or chlorine.

Within the scope of the present invention, alkyl will be understood as meaning straight chain and branched alkyl radicals and, depending on the indicated number of carbon atoms, as comprising for example the following groups: methyl, ethyl, propyl, butyl and pentyl, and the isomers thereof such as npropyl, isopropyl, isobutyl, tert-butyl, isopentyl and the like.

Halogen within the scope of the instant invention will be understood as meaning fluorine, chlorine and bromine, with fluorine and chlorine being preferred.

The compounds of formula I can be prepared by methods analogous to known ones (q.v for example German Offenlegungsschrift specifications 2 123 236, 2 601 780 and 3 240 975).

Thus, for example, a compound of formula I can be obtained by reacting a) a compound of formula II

with a compound of formula 111

or b) a compound of formula IV

with a compound of formula V

optionally in the presence of an organic or inorganic base, or c) a compound of formula II with a compound of formula VI

In formulae II to VI above, R, to R7 are as defined for formula I and R is a C1-C8 alkyl radical which may be substituted by halogen, preferably by chlorine.

The above process a), b) and c) can preferably be carried out under normal pressure and in the presence of an organic solvent or diluent. Examples of suitable solvents or diluents are: ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; nitriles such as acetonitrile or propionitrile; dimethyl sulfoxide; and ketones, e.g. acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone.Process a) is normally carried out in the temperature range from -10" to 2003C, preferably from 503 to 150:dgC, if desired in the presence of an organic base, e.g. triethylamine. Process b) is carried out in the temperature range from 0" to 1503C, preferably at the boiling point of the solvent employed and, if desired, in the presence of an organic base such as pyridine, and/or with the addition of an alkali metal or alkaline earth metal, preferably sodium.

For process c), i.e. for the reaction of the urethane of formula VI with a phenylenediamine of formula II, a temperature range from about 60 to the boiling point of the reaction mixture is preferred, and the solvent employed is preferably an aromatic hydrocarbon such as toluene, xylene, chlorobenzene and the like.

The starting materials of the formulae III and V are known and can be prepared by methods analogous to known ones. The starting materials of formula II are novel compounds which likewise constitute an object of the present invention. The compounds of formula II can be prepared in a manner known per se by hydrogenating suitably substituted p-nitroanilines of the formula VII

by a process analogous to that described in J. Org. Chem. 29 (1964) (q.v. also the iiterature cited therein).

However, phenylenediamines of formula II can also be obtained by chemical reduction (e.g. with Sn(il) chloride/HCI) of the corresponding nitro compounds of formula VII (q.v. Houben-Weyl, "Methoden der org. Chemie" 11/1, 422). The compounds of formula VII can be obtained by N-alkylating corresponding nitroanilines containing an unsubstituted amino group or by reacting corresponding 4-halonitrobenzenes with the desired dialkylamines. 4-Aminophenylisocyanates of formula IV can be prepared for example by phosgenating p-phenylenediamines of formula II by conventional methods commonly employed in the art.

Benzoylisocyanates of formula Ill can be obtained, inter alia, as follows (q.v. J. Agr. Food Chem. 21, 348 and 993; 1973):

The 4-aminophenylisocyanates of formula IV can be prepared for example by phosgenating the anilines of formula II by methods which are commonly employed in the art. The benzamides of formula V which are further used as starting materials are known (q.v. for example Beilstein "Handbuch der organischen Chemie", Vol. 9, p. 336).

Urethanes of the formula VI can be obtained in a manner known per se by reacting a benzoyl-isocyanate of formula III with a suitable alcohol or by reacting a benzamide of formula V, in the presence of a base, with a corresponding ester of chloroformic acid.

Substituted N-benzoyl-N'(4-aminophenyl)ureas having pesticidal activity are already known from German Offenlegungsschrift specifications 3 323 341 and 3 233 383 as well from European patent applications 0 016 729, 0 055 213, 0 065 487 and 0 072 438. The compounds disclosed in these references are substantially compounds in which the phenyl group attached to the N'-nitrogen is substituted only in 3and 5-position by halogen, CF3 or methyl, and which carries in the 4-position an amino group which is substituted by alkyl, alkenyl, alkynyl or phenyl. Further, J Agr. Food Chem. 21, No. 3, p. 353, discloses N 2,6-dichlorobenzoyl-N'-(4-dimethylamino)-phenylureas and N-2,6-dichlorobenzoyl-N'-(3-chloro-4-dimethyl- amino)-phenylureas which, however, exhibit only inadequate insecticidal activity. as is evident from Table Ill therein.

Compared with these known groups of compounds, the novel compounds of this invention have, as characteristic structural feature, a mandatory substituent in the 2-position of the phenyl ring attached to the N'-nitrogen. Surprisingly, it has been found that the compounds of this invention have excellent properties as pesticides while being well tolerated by plants and having low toxicity to warm-blooded animals. They are particularly suitable for controlling insects and representatives of the order Acarina that attack plants and animals.

In particular, the compounds of the formula I are suitable for controlling insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatives of the order Acarina of the families: Ixodidae, Argasidae, Tetranychidae and Dermanyssidae.

In addition to their action against flies, e.g. Musca domestica, and mosquito larvae, the compounds of formula I are also suitable for controlling plant-destructive feeding insects in ornamentals and crops of useful plants, especially in cotton (e.g. against Spodoptera littoralis and Heliothis virescens) and in fruit and vegetables (e.g. against Laspeyresia pomonella, Leptinotarsa decemlineata and Epilachna varivestis).

The compounds of formula I have a pronounced ovicidal and, in particular, larvicidal action against insects, especially against larvae of noxious feeding insects. If compounds of formula I are ingested by adult insect stages with the feed, then a diminished oviposition and/or reduced hatching rate is observed in many insects, especially in Coleopterae, e.g. Anthonomus grandis.

The compounds of formula I can also be used for controlling ectoparasites such as Lucilia sericata, in domestic animals and productive livestock, e.g. by treating animals, cowsheds, barns, stables etc., and pastures.

The compounds of formula I are also suitable for controlling the following species of mites which attack crops of fruit and vegetables: Tetranychus urticae, Tetranychus cinnabarinus, Panonychus ulmi, Broybia rubrioculus, Panonychus citri, Eriophyes piri, Eriophyes ribis, Eriophyes vitis, Tarsonemus pallidus, Phyllocoptes vitis and Phyllocoptruta oleivora.

The good pesticidal activity of the proposed compounds of the formula I according to the invention corresponds to a mortality of at least 50-60 % of the above insect pests.

The activity of the compounds of the formula I and of the compositions containing them can be sub stantially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, pyrethroids, carbamates, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.

The compounds of the formula I are used in unmodified form, or preferably together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the formula I or combinations thereof with other insecticides or acaricides, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, in some cases, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of the formula I to be formulated, or of combinations thereof with other insecticides or acaricides. suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C15-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, e.g. from coconut oil or tallow oil. Further suitable surfactants are also the fatty acid methyltaurin salts as well as modified and unmodified phospholipids.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product.Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminepolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cs-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi-(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ridgewood, New Jersey, 1979; Dr. Helmut Stache, "Tensid Taschenbuch" (Handbook of Surfactants), Carl Hauser Verlag, Munich/Vienna.

The pesticidal compositions usually contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of the formula I or combination thereof with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 20 %, of a surfactant.

Whereas commercial products are preferably formulated as concentrates, the end user will normally employ diluted formulations of substantially lower concentration.

The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.

The following Examples further illustrate the present invention.

Example 1; a) Preparation of 2-fluoro-3,5-dichloro-4-(N-methyl-N-n-butylamino)-nitrobenzene 22.8 g of 2,4-difluoro-3,5-dichloronitrobenzene are dissolved in 100 ml of dimethylsulfoxide. With stirring, 17.45 g of N-methyl-N-n-butylamine are added dropwise to this solution. The reaction mixture is then stirred for 5 hours at room temperature, after which time the solvent is distilled off. The residue is taken up in hexane and the hexane solution is washed with water, dried and and the hexane is distilled off. The crude product is chromatographed (column: 1 m, diameter 5 cm; packing: silica gel; eluant: hexane + 1 % ether; fractions: 30 ml each). Gas chromatographic and NMR analysis shows that fractions 16-57 contain the desired product in 98% purity.The obtained title compound of the formula

is a yellowish liquid (n 2D2 = 1.5618).

The following nitroanilines are prepared in corresponding manner:

(m.p.: 107-108 C) 23 P 1.6003) - 1.6003) (-.p.: 5s61"c)

(b.p. 111-119"c/o.O1 torr) (m.p. 62-66"C) b) Preparation of the starting 2-fluoro-3,5-dichloro-4-{N-methyl-N-n-butylamino)aniline 49.2 g of the 2-fluoro-3,5-dichloro-4-(N-methyl-N-n-butylamino)nitro-benzene prepared in a) in 500 ml of tetrahydrofuran are reduced with hydrogen at room temperature under normal pressure by adding 10 g and then 5 g of Raney nickel. 11 litres of hydrogen (98 % of theory) are absorbed. After the hydrogenation, the reaction mixture is filtered and the solvent is distilled off from the filtrate.The residue is then distilled in a high vacuum, affording the title compound of the formula

as a pale yellow oil (b.p. 102 -108 C/0.06 torr).

The phenylenediamines of the formulae

(b.p. 119-120 C/0.05 torr)

(b.p. 1o2"c/O.05 torr) (b.p. 95-98 C/0.6 torr) (b.p. 98-104 C/0.005 torr) (b.p. 98-102 C/0.07 torr) (b.p. 86-90 C/0.09 torr) are prepared in corresponding manner.

The compounds 2-fluoro-3,5-dichloro-4-(N-methyl-N-n-propylamino)-aniline and 2-fluoro-3,5-dichloro-4- (N-ethyl-N-n-propylamino)aniline listed above can also be obtained by reduction of 2-fluoro-3,5-dichloro (N-methyl-N-allyl)aniline and 2-fluoro-3,5-dichloro-4-(N-ethyl-N-allyl )aniline respectively.

c) Preparation of N-r2,6-dif/uorobenzoyl)-N'-[2-fluoro-3,5-dichloro-4rN-methyl-N-n-bu- tyl)aminophenyllurea 5.3 g of 2-fluoro-3,5-dichloro-4-{N-methyl-N-n-butyl)aminOaniline are dissolved in 50 ml of toluene.

Then 0.05 g of triethylamine is added dropwise to this solution. With stirring and cooling (temperature: 0-10 C), 3.66 g of 2,6-difluorobenzoylisocyanate are added dropwise and the reaction mixture is subsequently stirred for 10 hours at reflux temperature. The toluene is distilled off and the residue is taken up in methylene chloride. Upon addition of hexane, the title compound of the formula

precipitates in the form of colourless crystals of m.p. 130 -133 C. (Compound 1).

The following compounds of formula I can also be prepared in corresponding manner:

Compound m.p. (c] /C1 Ct vC1 2 < --CONHCONH-- < ; -N\ 185-187 \\,7/ /C1N:/CHI F F\ . cH3 3 + --CONHCONH-- < \.N/ 105 OCH3 XC1 4 Ct /L1Ct XC1 < \C4Hg(n) 134-137 \F sF Ct /C1 5 / --CONHCONH--+ / NXC H (n) 148-152 // ., OCii3 C1 cii9(") \cl c Ct /Ci cll3 6 / \ CONilCONH / \ N \/ 117-118 ::,Hs(n) ci ,/OCH3 Ct ci 7 t ~ / '8,-CONHCONH- 8'-N\C CH 137-141137-141 // \ 4IIs(n) /C1 F\ /C1 cll3 8 1 --CONi}CONli--+ --N\ 114-116 :sH(n) F F\ /Ci cH3 9 / .-coico-.' \.N/ 104-106 \\//\ 104-106 cn) \soch3 ci J Ct ci 10 < v /"\ N .-?K 190-194 // \ : :4Hs(n) \F ci ci F ci ca3 ''\.-CONHCONH- \C4H (n) 125-129 oC1 F\ /C1 125-129 c}i3 ci /Ci F ci \ / c3 12 < ?0-204 --N\ \CH, ci F ci 13 + --CONi}CONH-*+ --N\ 185-186 // -coecoNH-g~g,-E \ \cl /F F\ CH3 14 * -CONHCONH-- < /'P\ 145-147 SOCH3

Compound m.p. (OC) F F\ /C1 15 / --CONi}CONH-* < 4 N\C Hs 165-167 \F ci Ci F\ Ci 16 XC1 .-CoiCOH-. Fs sC1 152-156 \C:H2 \C1 /Ci F\ /Ci C?!3 17 /C1 .-CONHCoN?!-. F\ XC1 162-164 C1 /F F\ = /C1 /C1 18 / --CONi}CONH-- < 4 N\C H7(i) 171-174 ls .B,~,B-CONHCONH-.a.~I'-I 171-174 ( Ci 'F F\ /Ci /F - F\.- - /CH3 19 . < --CONHCONH-- < \.N/ 195 XF C1 ci 'F F\/Ci 20 / -CON?!CoN?!-. . 194-195 C?!3 'F F\ /Ci 21 / \ -CONHCOh'H- \.N/ // a~B-CO:iHCOH-n~B- 130-131 N\CH4(n) Ci F\ /C1 C?!3 22 / .-CON?!CON?!-. / \\ \ci C?!3 226-228 /F F\ C?!3 23 .-CON?!CoN?!-.' \/ 90-93 23 + --CONi}CONH-- < ci C?!3 24 / '-coN?!CoNll-. \N/ 107-108 \C1 Ci F\ /Ci 25 =/.-CON?!CoNll- 129-131 C?!g(n) 129-131 \ci \ci /F F\ /C1 26 / --CONHCONi}--+ P N\C li5 155-159 C2?!, 8~-coEIHcoNa- '-N\C1BS 155-159 ci

Compound m.p. [eC] /C1 F\ /C1 27 + --CONHCONH-- < --N\ 144-145 27 ci 28 / \ -CONHCONH- N\ 136-138 28 B~p-CONHCOh'H-n~/- ci C3?!7(n) 'Ci F\ /Ci 29 F\ = /C1 135-137 29 v-coNHCONH-e v hXC H (n) 135-137 \C1 /C1 C3?!6 /C2H5 CO?!?!CONH\\ \.N/ 30 < # -CONi}CONH-* N/ 136-138 'C,R7(n) /'P.\ CON?!CON?!-\\ .-1" 31 . < c3?!7(n) 135-138 \C1 ci F F\ /Ci 32 =/.-CONIrCON?!- zF F\ zC1/I' 127-128 32 ~g-co,YHcor;H- // -. 177-128 4 Ci F\ = /C1 /C1 F\ /C1 33 * -CONi}CONi}- -NX C?!3 188-189 Ci F F\ /Ci 34 \ -CONHCONH- -NX 214-215 \C1 214-215 Ci F\ /Ci 35 ~8-CONHCONII- -] FX XC1 CH 101-102 101-102 C1 C1 C1 36 F\ /C1 \C?!3 116-117 \\ // CON?!CON?! C3?!7(n) \C1 \C1 K ct /Ci 37 / /CsHs(n) /C1 37 w -CONHCONH-^+ v \C H (n) 189-194 CH3 C1 K Ct /Ci 38 / \ CONi}CONH- -Ny /CN3 134-137 + \C H ( ) '-h\C4Hs ci (n) C?!3 39 c:::a-CONBCONH-I 145-146 \\// c4?!6(n)

Compound m.p. icl Ai F\ ,Ci C?!3 40 [ CONitCONH- 144-145 44-145 oF FX /C1 XC1 41 + so .CON?!co.T?!./ -N\ 195-197 // \

The following compounds of formula I can also be prepared in corresponding manner: Compound

Example 2: Action against Musca domestica 50 g of freshly prepared nutrient substrate for maggots are charged into each of a number of beakers.

A specific amount of a 1 % acetonic solution of the respective test compound is pipetted onto the nutrient substrate present in the beakers to give an active ingredient concentration of 800 ppm. The substrate is then thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 20 hours.

Then 25 one-day-old maggots of Musca domestica are put into each of the beakers containing the treated nutrient substrate for testing with each active ingredient at one of its given concentrations.

After the maggots have pupated, the pupae are separated from the substrate by flushing them out with water and then deposited in containers closed with a perforated top.

Each batch of flushed out pupae is counted to determine the toxic effect of the test compound on the maggot development. A count is then made after 10 days of the number of flies which have hatched out of the pupae.

The compounds of formula I obtained according to Example 1 have good activity in this test.

Example 3: Action against Lucilia sericata 1 ml of an aqueous solution containing 0.5 % of test compound is added at 50"C to 9 ml of a culture medium. Then about 30 freshly hatched Lucilia sericata larvae are added to the culture medium, and the insecticidal action is determined after 48 and 96 hours by evaluating the mortality rate.

In this test, compounds of the formula I according to Example 1 exhibit good activity against Lucilia sericata.

Example 4: Action against Aedes aegypti A concentration of 800 ppm is obtained by pipetting a specific amount of a 0.1 % solution of the test compound in acetone onto the surface of 150 ml of water in a beaker. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aedes aegypti are put into the beaker containing the test compound. Mortality counts are made after 1, 2 and 5 days.

In this test, compounds of Example 1 exhibit good activity against Aedes aegypti.

Example 5 Insecticidal action against feeding insects Cotton plants about 25 cm high, in pots, are sprayed with aqueous emulsions which contain the respective test compound in concentrations of 0.2 ppm to 400 ppm. After the spray coating has dried, the cotton plants are populated with Spodoptera littoral is and Heliothis virescens larvae in the L3-stage. The test is carried out at 24"C and 60 % relative humidity. The percentage mortality of the test insects is determined after 120 hours.

In the above test, compounds of formula I effect 80-100 % kill against Spodoptera larvae in the following concentrations: Compound Concentration of test compound 17 0.2 ppm 1, 3, 9, 15, 18, 24, 27 0.75 ppm 8, 16, 19, 23, 29, 30, 31, 32, 33, 34, 36 3 ppm 21, 22, 25, 28, 39, 40 12.5 ppm 38 50 ppm 2, 5, 6, 7, 41 100 ppm 11, 20, 37 400 ppm In the above test, compounds of formula I effect 80-100 % kill against Heliothis larvae in the following concentrations: Compound Concentration of test compound 15, 28, 32, 36 12.5 ppm 1, 8, 16, 17, 23, 24, 26, 29 50 ppm 3, 7, 9, 18, 21, 25, 31, 39 100 ppm 5, 27, 33, 40 200 ppm 22, 41 400 ppm Example 6: Action against Epilachna varivestis Phaseolus vulgaris plants (dwarf beans) about 15-20 cm in height are sprayed with aqueous emulsion formulations of the test compound in concentrations of 800 ppm.After the spray coating has dried, each plant is populated with 5 larvae of Epilachna varivestis (Mexican bean beetle) in the L4-stage. A plastic cylinder is slipped over the treated plants and covered with a copper gauze top. The test is carried out at 28"C and 60 % relative humidity. The percentage mortality is determined after 2 and 3 days. Evaluation of feeding damage (anti-feeding effect), and of inhibition of development and shedding, is made by observing the test insects for a further 3 days.

The compounds of Example 1 exhibit good activity in this test.

Example 7: Ovicidal action against Spodoptera littoralis Corresponding amounts of a wettable powder formulation containing 25 % by weight of the test compound are mixed with sufficient water to produce an aqueous emulsion with an active ingredient concentration of 400 ppm. One day-old egg deposits of Spodoptera on cellophane are immersed in these emulsions for 3 minutes and then collected by suction on round filters. The treated deposits are placed in petri dishes and kept in the dark. The hatching rate in comparison with untreated controls is determined after 6 to 8 days.

In this test, compound 33 of Example 1 effects 80-100% kill.

Example 8 Action against Laspeyresia pomonella (eggs): Egg deposits of Laspeyrasia pomonella not more than 24 hours old are immersed on filter paper for 1 minute in an aqueous acetonic solution containing 800 ppm of the test compound.

After the solution has dried, the eggs are placed in petri dishes and kept at a temperature of 28"C. The percentage of larvae hatched from the treated eggs and the percentage mortality is evaluated after 6 days.

The compounds of formula I according to Example 1 exhibit good activity in this test.

Example 9: Influence on the reproduction of Anthonomous grandis Anthonomous grandis adults which are not more than 24 hours old after hatching are transferred in groups of 25 to barred cages. The cages are then immersed for 5 to 10 seconds in an acetonic solution containing 0.1 % by weight of the test compound. After the beetles have dried, they are placed in covered dishes containing feed and left for copulation and oviposition. Egg deposits are flushed out with running water twice to three times weekly, counted, disinfected by putting them for 2 to 3 hours into an aqueous disinfectant, and then placed in dishes containing a suitable larval feed. A count is made after 7 days to determine whether larvae have developed from the eggs.

The duration of the reproduction inhibiting effect of the test compounds is determined by monitoring the egg deposits over a period of about 4 weeks. Evaluation is made by assessing the reduction in the number of deposited eggs and hatched larvae in comparison with untreated controls.

The compounds of the formula I according to Example 1 exhibit a good reproduction inhibiting effect in this test.

Example 10: Action against Tetranychus cinnabarinus 16 hours before the test for acaricidal action, the primary leaves of Phaseolus vulgaris plants are infected with an infested piece of leaf from a mass culture of Tetranychus cinnabarinus (OP-tolerant). (The tolerance refers to diazinone). The treated infested plants are sprayed to drip point with a test solution containing 400, 200 and 12.5 ppm of the compound to be tested. A count of the number of living and dead imagines and larvae (all mobile stages) is made under a steroscopic microscope after 24 hours and again after 7 days. One plant is used for each test substance and concentration. During the test run, the plants are kept in greenhouse compartments at 25"C.

In this test, compound 26 of Example 1 effects 80-100 % kill at a concentration of 12.5 ppm after 7 days.

Example 11: Action against Tetranychus urticae 12 hours before the test for acaricidal action, Phaseolus vulgaris plants are infected by means of an infested piece of leaf from a mass culture of Tetranychus urticae. The treated plants infested with the mobile stages which have migrated to the plants are sprayed from a chromatography atomiser with emulsified test solutions, each having an active ingredient concentration of 800 ppm, so that the plants do not drip. A count of living and dead adults, larvae and eggs is made under a stereoscopic microscope after 2 days and again after 7 days. During the test run, the plants stand in greenhouse compartments at 25"C.

Compounds of the formula I according to Example 1 exhibit good activity in the above test.

Example 12: Action against Anthonomus grandis (adults) Two cotton plants in the 6-leaf stage, in pots, are each sprayed with a wettable aqueous emulsion formulation containing the test compound in a concentration of 200 and 400 ppm respectively. After the spray coating has dried (about 1 1/2 hours), each plant is populated with 10 adult beetles (Anthonomus grandis). Plastic cylinders, covered at the top with gauze, are then slipped over the treated plants populated with the test insects to prevent the beetles from migrating from the plants. The treated plants are then kept at 25 C and about 60 % relative humidity. Evaluation is made after 2, 3, 4 and 5 days to determine the percentage mortality of the beetles (percentage in dorsal position) as well as the anti-feeding action as compared with untreated controls.

In this test, compound 15 of Example 1 effects 80-100 % kill at a concentration of 200 ppm.

Example 13: Formulation examples for active ingredients of the formula I or combinations thereof with other insecticides or acaricides (throughout, percentages are by weight) 1. Wettable powders a) b) c) compound of formula I or combination 25 % 50 % 75 % sodium lignosulfonate 5% 5% - sodium laprylsu!fate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6 % 10 % octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% - highly dispersed silicic acid 5% 10% 10% kaolin 62 % 27 % The active ingredient or combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

2. Emulsifiable concentrate compound of formula I or combination 10 % octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3% calcium dodecylbenzenesulfonate 3 % castor oil polygycol ether (36 moles of ethylene oxide) 4% cyclohexanone 30 % xylene mixture 50 % Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

3. Dusts a) b) compound of formula I or combination 5 % 8 % talcum 95 % kaolin - 92 % Ready for use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.

4. Extruder granulate compound of formula I or combination 10% sodium lignosulfonate 2% carboxymethylcellulose 1% kaolin 87 % The active ingredient or combination is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

5. Coated granulate compound of formula I or combination 3% polyethylene glycol 200 3% kaolin 94 % The finely ground active ingredient or combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

6. Suspension concentrate compound of formula I or combination 40 % ethylene glycol 10 % nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% sodium lignosulfonate 10 % carboxymethylcellulose 1% 37 % aqueous formaldehyde solution 0.2 % silicone oil in the form of a 75 % aqueous emulsion 0.8 % water 32 % The finely ground active ingredient or combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Claims

1. A compound of formula I

wherein R1 is hydrogen, halogen, CF3 or C1-C4alkoxy, R2 is halogen, Cl-C4alkyl, CF3 or C1-C4alkoxy, R3 is hydrogen, halogen, CF3 or methyl, R4 is fluorine or chlorine, Rs is hydrogen, fluorine or chlorine, R, and R, are each independently of the other C1-C6alkyl, C3-C5alkenyl, C3-C,alkynyl, or C1-C4alkyl which is substituted by 1 to 8 fluorine or chlorine atoms or by methoxy or ethoxy; or R, and P7, together with the nitrogen atom to which they are attached, are the radical

2.A compound of formula I according to claim 1, wherein R1 is hydrogen, halogen, CF3 or C1-C4alkoxy, R2 is halogen, C1-C4alkyl, CF3 or C1-C4alkoxy, R3 is hydrogen, halogen, CF2 or methyl, R4 is fluorine or chlorine, P5 is hydrogen, fluorine or chlorine, R, and R, are each independently of the other C1-C6alkyl, C3-C5alkenyl, C3-C6alkynyl, or C1-C4alkyl which is substituted by 1 to 8 fluorine or chlorine atoms or by methoxy or ethoxy.

3. A compound of formula I according to either of claims 1 or 2, wherein R, is hydrogen, fluorine, chlorine, CF3, methoxy or ethoxy, R2 is fluorine, chlorine, Ct-C3alkyl, CF3 or methoxy, R3 is hydrogen, fluorine, chlorine, CF3 or methyl, R4 is fluorine or chlorine, P5 is hydrogen, fluorine or chlorine, and R, and R, are each independently of the other C1-C4alkyl, allyl, propargyl, or C1-C3alkyl which is substituted by 1 to 7 fluorine or chlorine atoms or by methoxy.

4. A compound of formula I according to claim 3, wherein R, is hydrogen, fluorine, chlorine or methoxy, R2 is fluorine, chlorine, methyl or methoxy, R3 is hydrogen or fluorine, R4 is fluorine or chlorine, P5 is hydrogen or chlorine, and R, and R, are each C1-C4alkyl.

5. A compound of formula I according to any one of claims 1 to 4, wherein R, is methyl and R, is C1 C4alkyl.

6. A compound of formula I according to any one of claims 1 to 5, wherein R4 is fluorine and R6 is hydrogen or chlorine.

7. A compound according to claim 4 of the formula

8. A compound according to claim 4 of the formula

9. A compound according to claim 4 of the formula

10. A compound according to claim 4 of the formula

11, A compound according to claim 4 of the formula

12. A compound according to claim 4 of the formula

13. A compound according to claim 4 of the formula

14. A compound according to claim 4 of the formula

15. A compound according to claim 4 of the formula

16. A compound according to claim 4 of the formula

17.A process for the preparation of a compound according to any one of claims 1 to 16, which comprises reacting at a compound of formula li

with a compound of formula Ill

or b) a compound of formula IV

with a compound of formula V

or c) a compound of formula II with a compound of formula VI

in which formulae II to VI above R1 to R, are as defined in any one of claims 1 to 6 and R is a C1-C8alkyl radical which may be substituted by halogen.

18. A compound of formula il

wherein R4 to R7 are as defined in any one of claims 1 to 6,

19. A pesticidal composition which contains a compound as claimed in any one of claims 1 to 16, together with suitable carriers and/or other adjuvants.

20. Use of a compound according to any one of claims 1 to 16 for controlling insects and representatives of the order Acarina.

21. Use according to claim 20 for controlling larval insect stages of plant-destructive feeding insects.

22. A method of controlling insects and representatives of the order Acarina, which comprises treating or contacting said insects, their various development stages or the locus thereof, with a pesticidally effective amount of a compound of the formula I according to any one of claims 1 to 16, or with a composition which contains a pesticidally effective amount of such a compound, together with adjuvants and carriers suitable therefor.