CA1244440A - Pesticidally active n-benzoyl-n' (2-pyridyl- oxyphenyl) ureas - Google Patents

Abstract

Benzoylphenylureas Abstract of the Disclosure The invention relates to novel substituted N-benzoyl-N'-(2-pyridyl-oxyphenyl)ureas of the formula wherein R1 is hydrogen, fluorine or chlorine;
R2 is fluorine, chlorine, methyl, methoxy or methylthio;
R3, R4 and R5 are each independently hydrogen, chlorine or methyl:
X is oxygen or sulfur; and Y is one of the radicals -CC12-CC13, -CF2-CC13 or -CF2-CFC12;
to processes and intermediates for the preparation of these compounds, as well as to compositions containing the novel compounds for use in pest control, in particular for controlling insects that attack plants and animals. The novel compounds exhibit especially high larvicidal activity against plant-destructive insects.

Description

~;~4'~4~0 5-15201/+/ZFO

Benzoylphenylureas The present invention relates to novel substituted N-benzoyl-N'-~2-pyridyloxyphenyl)ureas, to processes and intermediates for the preparation thereof, and to the use of the novel compounds in pest control.

The substituted N-benzoyl-N'~(2-pyridyloxyphenyl)ureas of this invention are of formula I
.=.

RZ ~ R4 S

wherein Rl is hydrogen, fluorine or chlorine;
R2 is fluorine, chlorine, methyl, methoxy OF methylthio;
R3, R4 and Rs are each independently hydrogen, chlorine or methyl;
X is oxygen or sulfur; and Y is one o~ the radicals -CCl2-CCl3, -CFz-CCl3 or -CFz-CFClz.

Compounds of formula I which are preferred on account of their activity as pesticides are those wherein Y is the radical -CFz-CFClz, and those wherein X is oxygen.

To be singled out for particular mention are those compounds of formula I wherein R1 is hydrogen, fluorine or chlorine;
Rz is fluorine or chlorine;

,, 4~0 R3, R4 and Rs are each hydrogen;
X is oxygen; and Y is the radical -CF2-CFC12.

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 a) reacting a compound of formula II
.=.
y ,/ \, ~ NH2 (II) Rs ~4~
with a compound of formula III
~1 CO--N=C=X ( I I I ) or b) reacting a compound of formula IV

~-N~ 0~ 3 ~- -N=C-X ( IV) ~4~

optionally in the presence of an organic or inorganic base, with a compound of formula V

i2~4~

CO-NHz (V) or c) reacting a compound of formula II with a compound of formula VI
Rl -CO-NH-CXOR (VI).

In formulae II to VI above, the radicals R1 to Rs and X and Y are as defined for formula I; R is a C1-C~-alkyl radical which is unsub-stituted or substituted by halogen, preferably chlorine.

The above processes a), b) and c) are preferably 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 aceto-nitrile 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 200C, preferably from 50 to 150C, and, if desired, in the presence of an organic base such as tri-ethylamine. Process b) is carried out in the temperature range from 0 to 150C, preEerably at the boillng point of the solvent employed and, if desired, in the presence of an organic base such as pyridine, and/or with the addition on an alkali metal or alkaline earth metal, preferably sodium. For process c), i.e. for the reaction of the urethanes of formula VI with a pyridyloxyaniline of formula II, a temperature range from about 60C to -the boiling of the reaction mixture is preferred, and the solvent employed is preferably an aromatlc hydrocarbon such as toluene, a xylene, chlorobenzene and the like.

The starting materials of formulae III, V and VI 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 ob~ect of the present invention. These pyridyloxy-anilines of formula II can be prepared by reacting corresponding aminophenols of formula VII
HO~ =~3 ~ ~-NH2 (VII) Rs R4~
with 2-halo-S-haloethylpyridines of formula VIII

~.-N~ (VIII) or by reacting corresponding p-nitrophenols of formula IX with pyridines of formula VIII and subsequently reducing the nitro group in the resultant pyridyloxynitrobenzenes of formula X in accordance with one of the customary methods [q.v. for example Rec. 21, 271 (1902); J. Am. Soc. 68, 1604 (1946); J. Org. Chem. 11, 378 (1946);
Rec. 79, 995 (1960)]:
HO~ ~3 ~ ~-NO2 + (VIII) Rs Rl,~ (IX) ~-N~ ` ~3 ~ NO2 ~ (II) S R4~ (X) ~2~4~) In formulae VII to X above, R3, R4, Rs and Y are as defined for formula I; Z is fluorlne, chlorine or bromine, preferably chlorine.

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

~ C - N H2S04/H20 ~ -C0-NH2 .=. .=.
~2 ~2 ~1 CH2C12 ~ C0-N-C=0 (III) .
~2 The benzoylisothiocyanates of formula III can be prepared in conventional manner by reacting a reactive benzoyl derivative, e.g.
a suitably substituted benzoyl halide, with an isothlocyanate, e.g. KSCN.

The pyridyloxyphenylisocyanates of formula IV can be prepared e.g.
by phosgenating the corresponding pyridyloxyanilines of formula II
by methods which are commonly employed in the art. The benazmides 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 or thiourethanes of formula VI can be obtained in a manner known per se by reacting a benzoylisocyanate or benzoylisothio-cyanate of formula III with a suitable alcohol. Urethanes of formula YI can also be prepared by reacting a benzamide of formula V, in the presence of a base, with a corresponding ester of chloroformic acid.

.~

lZ~

The 2-halo 5-haloethylpyridines of formula VIII are likewise novel compounds and constitute an object of the present invention. The pyridines of formula VIII are mainly prepared in a manner known per se (q.v. for example European patent application 0 078 234).
Pyridines of formula VIII, wherein Y is the radical -CClz-CCl3, can be prepared by perchlorinating the ethyl group in a compound of formula XI ,=.
CH3-CH2--~ ~'~Z (XI) wherein Z is fluorine, chlorine or bromine, e.g. 2-chloro-5-ethyl-pyridine, (q.v. C.A. 57:790, 1962; 69:86786r, 1968). Said chlorination can be effected in liquid phase, with or without a solvent, in the presence of light and/or other radical formers such as a~oisobutyronitrile or benzoyl peroxide, at room temperature as well as at elevated temperatures, e.g. in the range from 40 to about 100C. The amount of the radical former may vary within the range from 0.001 to 1 mole per mole of substance to be chlorinated.
The reaction temperature is normally in the range from room temperature to about 150C and is preferably identical with the boiling point of the solvent employed. Preferred solvents are those which are inert to chlorine. The starting materials, i.e. the

2-halo-5-ethylpyridines of formula XI, can be employed as free pyridines or as the hydrochlorides or hydrobromides thereof. The course of the chlorination reaction may be followed with the aid of gas chromatography or thin-layer chromatography. The reaction solution is worked up by concentrating it by evaporation after expelling dissolved hydrogen halide or excess chlorine with a flow of nitrogen. The resultant crude product can be purified by re-crystallisation or, if a replacement of chlorine by fluorine is desired, the crude product can be further reacted direct.

The mentioned replacement of chlorine by fluorine in the -CCl~-CCl3 group of a resultant pyridine of formula VIII to form corresponding pyridines, wherein Y is the radical -CF2-CCl3 or -CFz-CFCl~, can be carried out with a fluorinating agent such as KF, NaF, CsF~, SbF3, ~Z~91 44~
-- 7 ~

HF or a mixture thereof. The reaction is often catalysed by small amounts of elementary chlorine and is carried out either in the melt or in a solvent in the temperature range from 50 to 250C. If HF is employed as fluorinating agent, the reaction is advantageously carried out under increased pressure in an autoclave. Suitable solvents are polar aprotic compounds such as dimethylformamide, dimethylacetamide, sulfolane, dimethyl sulfoxide, dimethyl sulfone or diethyl sulfone. The fluorinating agents are preferably employed in anhydrous, finely dispersed form and in excess of the chlorine atoms to be replaced; this excess is normally 10 to 200 %. If a solvent is employed, it is advantageous to add to the reaction mixture a phase transfer catalyst, e.g. tetraalkyl ammonium chloride or bromide, in an amount of 0.1 to 10 % of the solvent.

Differently substituted N-benzoyl-N'-(2-pyrid-4-yloxyphenyl~ureas with insecticidal properties are known from European patent application 0 077 759 and German Offenlegungsschrift 2 748 636.
Compared wlth these known compounds, the compounds of formula I of the present invention differ substantially in structure by the presence of a pyridyloxy group which is unsubstituted in the

3-position and which is substituted in the 5-position by a per-halogenated ethyl radical.

Surprisingly, it has been found that the compounds of this inven-tion 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 representa-ives of the order Acarina that attack plants and animals.

In particular, the compounds of formula I are suitable for control-ling 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.

~;~4~44() In addition to their action against flies, e.g. Muaca 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 larvicidal and ovolarvicidal 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 ecto-parasites such as Lucilia sericata, in domestic animals and produc-tive 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 cinnabari~us, 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 compounds of formula I of the invention corresponds to a mortality of at least 50-60 % of the above pests.

The activity of the compounds of formula I and of the compositions containing them can be substantially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organophosphorus ~2~

compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.

The compounds of formula I are used in unmodified form, or preferably ~ogether 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 substan-ces. As with the nature of the compositions, the methods of appli-cation 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, preparations or mixtures containing the compound (active ingredient) of 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, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, 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 dlspersible 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 adsorp-tive 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 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 (Clo-C2z), 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 benzimida-zole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline ear~h metal salts or unsubstituted or substi-tuted ammonium salts and contain a Cs-C22alkyl radical which also ~z~

includes the alkyl moiety of acyl radical9, 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 sulfona-ted benzimidazole derlvatives 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 tri-ethanolamine saltR of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic 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 ~ 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, ethylenediamino-polypropylene 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 nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

~4~
- 12 ~

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituPnt, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium 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 Hanser Verlag, Munich/Vienna, 1981.

The pesticidal compositions usually contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of 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 concen-trates, 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 for obtaining special effects.

Example 1: Preparation of the starting materials and intermediates a~ Preparation of 2-chloro-5-pentachloroethylpyridine:

14.1 g of 2-chloro-5-ethylpyridine are dissolved in 200 ml of carbon tetrachloride. With cooling, 6 g of gaseous HCl are introduced at room temperature, resulting in partial precipitation of the hydro-chloride of the pyridinium compound. The reaction mixture is heated ~2~g~

to 50C and then treated with gaseous Cl2 while being subjected to exposure with an Hg high pressure lamp (125 watts). The progress of the chlorination reaction is followed by thin-layer chromatography (carrier: sillcal gel; eluant: toluene). When the reaction is complete, the pale yellow solution is concentrated by evaporation in vacuo, affording as residue the title compound of the formula CCl3-CCl 2- ~ Cl as yellowish product which melts at 92C after recrystallisation from 90 % ethanol.

b) Prepara~ion of 2-chloro-5-(2,2-dichloro-1,1,2-trifluoroethyl)-pyridine:

31.4 g of 2-chloro-5-pentachloroethylpyridine are mixed together with 90 g of antimony trifluorlde and 4 g of antimony pentachloride.
The reaction mixture is heated to 180C, whereupon a dark brown melt forms which is kept at this temperature for 3 hours. After the batch has cooled to 90C, 200 ml of hot water are added to the reaction mixture and the product is then distilled off with steam. The aqueous oily steam distillate is extracted with ether, the ether extract is dried over Na2S04 and the ether is distilled off. The residual yellowish oil is rectified in a water jet vacuum. The product, which distills at 94-97C/15.5 mbar, is collected; it congeals on standing to form white crystals. The resultant title compound of the formula CFCl 2 -CF 2-'~ Cl has a melting point of 38DC.

c) Preparation of 2-chloro-5-(2,2,2-trichloro-l,l-difluoroethyl)-pyridine:

9L4~V

The title compound of the formula CC13-CF2~ -Cl ~-N~

can be obtained by high vacuum distillation from the residue of distillation, as described above in b). The title compound boils at 80-84C/0.1 mbar and has a melting point of 83-84C.

d) Preparation of 2-fluoro-5-(2,2-dichloro-1,1,2-trifluoroethyl)-pyridine:

If the fluorination reaction with 2-chloro-S-pentachloroethyl-pyridine is carried out for 4 hours at 200C by a procedure analogous to that described in b) and the batch is subsequently worked up as indicated in b) above, the title compound of the formula CFCl2-CF2-'~ ~--F

wlth a boiling point of 70-71Cl14 mbar is obtained.

e) Preparation of 4-[5-(2',2'-dichloro-1',1',2'-trifluoroethyl)-2-pyridyloxy]aniline:

2.8 g of 4-aminophenol and 6.0 g of potassium carbonate in 30 ml of dimethyl sulfoxide are stirred for 1 hour at room temperature. The batch is subsequently heated to 50C and a solution of 6.15 g of 2-chloro-S-(2,2-dichloro-1,1,2-trifluoroethyl)pyridine, obtained in accordance with b), in 10 ml of dimethyl sulfoxide is added drop-wise. The reaction mixture is then stirred for 4 hours at 95C. The dimethyl sulfoxide is then removed by concentration by evaporation under a high vacuum, the resultant residue is taken up in dichloro-methane and water, and the separated organic phase is dried and ~24fl~ ~40 strongly concentrated. After filtration through silical gel, concentration by evaporation of th~ solution and the addition of a small amount of he~ane, the title compound of the formula _, . = .
CFCl2-CF2-'~ ~-~~ ~ ~ NH2 crystallises in the form of pale pow~er with a melting point of 75-77C.

The following compounds of formula VIII can also be prepared by procedures analogous to those described above:

CCl CF / \- F

CCl3-CC12-~ Br CCl3-CF2-~ Br Furthermore, the following compounds of formula II can also be prepared by procedures analogous to those described above:

CFC12-CF2~
~- ~ O\ m.p. 57-9C

. _ .
.=.
CFCl CF ~/ \-Cl-~ -NH2 . = .
CFCl2-CF2-'~ -'~ ~Ç--NH2 12~ 4~

~-N~

!Cl CFcl2-cF2-~ ~'~~'~ ~-NH2 Cl H3C\ /CH3 CFCl2-CF2-'~ ~'~~-~ ~-NH2 xample 2: Preparation of N-4-~5-(2',2'-dichloro-1',1',2'-tri-fluoroethyl)-2-pyridyloxy]phen~l-N'-2,6-difluoro-benzoylurea 2.25 g of 4-[5-(2',2'-dichloro-1',1',2'-trifl~oroethyl)-2-pyridoxy~-aniline are dissolved in 20 ml of absolute toluene and, with the exclusion of moisture, a solution of 1.22 g of 2,6-difluorobenzoyl-isocyanate in 10 ml of toluene is slowly added. The exothermic reaction is allowed to subside and the reaction mixture is then stirred for 5 hours at room temperature. The crystalline precipitate is isolated by suction filtration and recrystallised in methanol with the addition of a small amount of acetone, affording the title compound of the formula =~ O .,. .=.
~ -C0-NH-C-NH-~ -0~ --CF2-CFC12 as pale beige crystalline product with a meltlng of 207-208C
(compound 1).

4~(9 The following compounds of formula I are prepared in accordance with the procedures described above:

Gompound m.p.[C~
No.

2 ~ -CF2CFC12 176-178 .--. ) .=.
~ -CO-NH- -NH-~

.=! /'~~.-CF2CPC12206 208 ~ -C0-NH-~-NH~

. = ! . = . . = .
4 ~ -C0-NH-~-NH~ -0-~ -CF2-CFC12 175-177 F~ ICH3 ~ -C0-NH-C-NH--~ ~--0-~ -CF2-CFCl2 198-200 The following compounds of formula I can also be prepared by procedures analogous to those described above:

Compound No.

6 D~ ~--C0-NH-~-NH-~ ~-_O_D~ ~--CF2-CFC12 O

.=. ~ .=. .=.
7 ~ CO-NH- I NH / \ O / \~ CF CFCl IOCl13 ~s~ ~ .=. ...
8 .~ ~-CO-NH- ~ NH / \ O ~ CF CFCl ~CH3 9 ~ CO-NH-C-NH-~ -0-~ -CF2-CFC12 .=. .=. .=.
~ -CO-NH- NH / \ O / \~ CF CFCl ,F ,Cl 11 ~ ?~-C-NH-~-NH~ _o_~ -CFz-CFC12 F, H 3 C~ ~CH3 12 ~-Co-NH-8-NH--~ ~^-0-~ -CF2-CFC12 F

'=~ O .=. .=, 13 ~ ~-CO-NH-C-NH-~ -0-~ -CF2-CFC12 Cl 14 IF / \~ CF CFCl -? :=:`

4~0 Example 3: Formulations for active ingredients of formula I
according to Example 2 or combinations thereof with other _nsecticides or acaricides (throughout, percentages are by weight?

3.1. Wettable powders a) b) c) compound of formula I or combination 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium laurylsulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid5 % 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.

3.2. 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.

3.3. Dusts a) b) compound of formula I or combination 5 % 8 %
talcum 95 %
kaolin - 92 %

:1 Z4~

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

3.4. 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.

3.5. 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 mlxer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

3.~. 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 %

~2~

The finely ground active lngredient 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.

Example 4: Action a~ainst Musca domestica 50 g of freshly prepared nutrient substrate for maggots are charged into each of a number of beakers. A specific amount of an acetonic solution containing 1 ~O by weight 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 mixe~ 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. 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 lO days of the number of flies which have hatched out of the pupae.

The compounds of formula I according to Example 2 exhibit good activity in thls test.

Example 5: Action against Lucilia sericata l ml of an aqueous formulation containing 0.5 % by weight 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 insecticldal action is determined after 48 and 96 hours by evaluating the mortality rate.

" .

In this test, compounds of formula I accordlng to Example 2 exhibit good activity against Lucilia sexicata.

Example 6: Action against Aëdes aegypti A concentration of 800 ppm is obtained by pipetting a specific amount of an acetonic solution containing 0.1 % by weight of the test compound onto the surface of 150 ml of water in a beaker.
After the acetone has evaporated, 30 to 40 two-day-old larvae of Aëdes 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 formula I according to Example 2 exhibit good activity against Aëdes aegypti.

Example 7: 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 increasing concentrations of 3 ppm to 100 ppm. After the spray coating has dried, the cotton plants are populated with Spodoptera littoralis and Heliothis virescens larvae in the L3-stage. The test is carried out at 24C and 60 % relative humidity. The percentage mor-tality of the test insects is determined after 120 hours.

In this test7 compounds of the invention effect 80 to 100 %
mortality at the following concentrations:

Compound Active ingredient concentration ~ppm]
No.
Spodoptera Heliothis 2 3 ppm 3 ppm 3 50 ppm 50 ppm 4 12.5 ppm 100 ppm 50 ppm L~ 4 ~

Example 8: 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 a concentration of 800 ppm. After the spray coating has dried, each plant is populated with 5 larvae of Epllachna varivestis (Mexican bean beetle) in the L4-stage. A plastlc cylinder is slipped over the treated plants and covered with a copper gau~e top. The test is carried out at 28C 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 formula I according to Example 2 exhibit good activity in this test.

Example 9: Ovicidal action against Heliothis virescens 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 concen-tration of 800 ppm. One-day-old egg deposits of Heliothis 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 at 28C and 60 %
relative humidity. The hatching rate in comparison with untreated controls is determined after 6 to 8 days.

Compounds of formula I according to Example 2 exhibit good activity in this test.

Example 10 Action against Laspeyresia pomonella (eggs) Egg deposits of Laspeyresia 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.

~;Z 4~4~1~

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

The compounds of formula I accordlng to Example 2 exhibit good activity in this test.

Example 11: 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 400 ppm 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 the number of larvae which have developed from the eggs.

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

Compound 1 according to Example 2 effects 80 to 100 % reproduction inhibiting activity in this 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 400 ppm of the test compound. 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 .lZ~4 ~

gauze, are then slipped over the treated plants populated with the test insects to prevent the beetles f~om migrating from the plants.
The treated plants are then kept at 25C and about 60 % relative humidity, Evaluation is made after 2, 3, 4 and 5 days to determine the percentage mortallty of the beetles (percentage in dorsal position) as well as the anti-feeding action as compared with untreated controls.

Compounds of formula I to Example 2 exhibit good activity in this test.

Claims (13)

What is claimed is:

1. A compound of formula I
(I) wherein R1 is hydrogen, fluorine or chlorine;
R2 is fluorine, chlorine, methyl, methoxy or methylthio;
R3, R4 and R5 are each independently hydrogen, chlorine or methyl;
X is oxygen or sulfur; and Y is one of the radicals -CC12-CC13, -CF2-CC13 or -CF2-CFC12.

2. A compound of formula I according to claim 1, wherein Y is the radical -CF2-CFC12.

3. A compound of formula I according to either of claims 1 or 2, wherein X is oxygen.

4. A compound of formula I according to claim 1, wherein R1 is hydrogen, fluorine or chlorine;
R2 is fluorine or chlorine;
R3, R4 and R5 are each hydrogen;
X is oxygen; and Y is the radical -CF2-CFC12.

5. A compound according to claim 4 of the formula

6. A compound according to claim 4 of the formula

7. A compound according to claim 4 of the formula

8. A compound according to claim 4 of the formula

9. A process for the preparation of a compound according to claim 1 which process comprises a) reacting a compound of formula II
(II) with a compound of formula III
(III) or b) reacting a compound of formula IV
(IV) with a compound of formula V
(V) or c) reacting a compound of formula II with a compound of formula VI
(VI) in which formulae II to VI the radicals R1 to R5 and X and Y
are as defined in claim 1 and R is a C1-C8 alkyl radical which is unsubstituted or substituted by halogen.

10. A process according to claim 9 wherein in c) a halogen substituent in R is chlorine.

11. A method of controlling insects and representatives of the order Acarina, which method comprises contacting or treating said pests, their various development stages or the locus thereof with a pesticidally effective amount of a compound of formula I according to claim 1, or with a composition which contains a pesticidally effective amount of such a compound.

12. A method according to claim 11 for controlling larval stages of plant-destructive insects.

13. A pesticidal composition which comprises an acceptable carrier and, as active ingredient, a compound of formula I
according to claim 1.