AU597278B2

AU597278B2 - Substituted n-benzoyl-n'-3,5-dichloro-4- hexafluoropropyloxyphenylureas, the preparation thereof, and their use in pest control

Info

Publication number: AU597278B2
Application number: AU63833/86A
Authority: AU
Inventors: Jozef Drabek
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1985-10-14
Filing date: 1986-10-13
Publication date: 1990-05-31
Anticipated expiration: 2006-10-13
Also published as: BR8604995A; DE3679024D1; DK111692D0; CN1014110B; GB2217323A; ATE63112T1; ZW20486A1; DK488186A; EP0219460B1; CY1683A; EP0219460A3; ES2038125T3; JPS6293268A; GB2182329A; SU1588277A3; ZA867736B; EG17946A; IL80271A0; EP0219460A2; JPH034543B2

Abstract

Substituted N-benzoyl-N'-3,5-dichloro-hexafluoropropyloxyphenylureas of the formula <IMAGE> wherein R1 is hydrogen or fluorine and R2 is fluorine or chlorine, and salts thereof are useful for controlling insects, representatives of the order Acarina, slugs and snails, particularly plant-destructive insects. Intermediates for these compounds having the formulae <IMAGE> are also disclosed.

Description

I FORM 10 1 d ;j i

:B

it i i P; Li ii 2 i r

C

II

r

B

j i:F ;1 j

E

I

s 597278 SPRUSON FERGUSON COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: -3g331e6 Class Int. Class Complete Specification Lodged: Accepted: Published: I'his document contains the amendments made under Section 49 and is correct for printing.

Priority: Related Art: Cit Name of Applicant: Address of Applicant: C It t t Actual Inventor: Address for Service: CIBA-GEIGY AG Klybeckstrasse 141, 4002 Basle, Switzerland JOZEF DRABEK Spruson Ferguson, Patent Attorneys, Level 33 St Martins Tower, 31 Market Street, Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: "Substituted N-benzoyl-N'-3,5-dichloro-4-hexafluoropropyloxyphenylureas, the preparation thereof, and their use in pest control".

The following statement is a full description of this invention, including the best method of performing it known to us ISBS eah 62U the preparation thereof, and their use in pest control".

The present invention relates to novel substituted dichloro-4-hexafluoropropyloxyphenylureas, to processes and to intermediates for the preparation thereof, and to the use of the novel compounds in pest control.

The invention relates to compounds of formula I -CO-NH-CO-NH- *-O-CF 2

-CHF-CF

3 Sand to salts thereof.

-1 Compounds of formula I meriting particular interest are those wherein Ri is fluorine and R 2 is fluorine or chlorine.

Further preferred compounds of formula I are those wherein R 1 is hydrogen and R 2 is fluorine or chlorine.

The compounds of formula I can be prepared by methods analogous to ones known per se e.g. 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 2a) the compound of formula II

CF

3

-CHF-CF

2 -0-0 -NH 2

(II)

I with a compound of fcrmula III 1 2 or V b) the compound of formula IV

ICF

3

-CHF-CF

2

*-N=CO(V

with a compound of formula V

CO-NH

2 C) 01 2 i f f In formulae III, V and VI above, the radicals R 1 and R 2 are as defined for formula I, and R is a Cj-C 8 alkyl radical which is unsubstituted or substituted by halogen, pr'eferably chlorine.

I 3 The above processes 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 i carboxamides; aliphatic, aromatic and halogenated hydrocarbons, J 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 Sisobutyl ketone. Process a) is normally carried out in the temperai ture range from -10° to +200 0 C, preferably from 0 to 100 0 C, e.g at room temperature, and, if desired in the presence of an organic base, e.g. triethylamine. Process b) is carried out in the temperature range from 00 to 150°C, 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 i.e. for i the reaction of the urethane of formula VI with an aniline of formula II, a temperature range from about 600 to the boiling point i of the reaction mixture is preferred, and the solvent employed is preferably an aromatic hydrocarbon such as toluene, xylene, chlorobenzene and the like.

i The starting materials of formulae III and V are known and can be Sprepared by methods analogous to known ones. The starting aniline of S formula II is a novel compound which likewise constitutes an object of the present invention. The compound of formula II can be prepared in a manner known per se by hydrogenating the suitably substituted nitrobenzene of formula VII 11

CF

3

-CHF-CF

2 >-NOz (VII) 2i -4by a process analogous to that described in J. Org. Chem. 29 (1964), 1, also the literature cited therein). However, the aniline of formula II can also be obtained by chemical reduction with Sn(II) chloride/HCl) of the nitro compound of formula VII (q.v.

Houben-Weyl, "Methoden d. org. Chemie" 11/1, 422). The nitro compound of formula VII itself can be prepared by fluoroalkylating 3,5-dichloro-4-nitrophenol. A further process for the preparation of the aniline of formula II comprises fluoroalkylating in corresponding manner the acylated 2,6-dichloro-4-hydroxyaniline and S then removing the acyl group, e.g. by acid hydrolysis, or effecting the fluoroalkylation with a salt of 3,5-dichloro-4-hydroxyaniline, e.g. the chlorohydrate.

Benzoylisocyanates of formula III can be obtained, inter alia, as follows J. Agr. Food Chem. 21, 348 and 993; 1973): 0 8\6-Ca N H 2

SO

4 /H20 N CO-NH 2 A2 IC) \-CO-N=C=O

(III).

i J la95°C/0.01 torr), which is novel per se, can be prepared e.g. by I 1 phosgenating the aniline of formula II by methods which are commonly EF. employed in the art and also comprises an object of this invention.

The benazmides of formula V which are further used as starting A Imaterials ar. known for example Beilstein "Handbuch der organischen Chemie", Vol. 9, p. 336).

Urethanes of formula VI can be obtained in a manner known per se by reacting a benzoylisocyanate 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 Cl-COOR.

with a corresponding ester of chloroformic acid CI-COOR.

5 In accordance with the present invention, the novel compounds of formula I also comprise the salts thereof which not only exhibit high insecticidal activity, but are also readily soluble in solvents and diluents, in particular in organic solvents, and can also be formulated more easily.

To be singled out for special mention are the metal salts of the compounds of formula I of the invention, in particular the alkali metal and alkaline earth metal salts thereof, preferably the sodium salts and potassium salts. These salts are prepared in a manner known per se, e.g. by reacting a compound of formula I with a metal alkanolate such as sodium ethylate or potassium methylate. A given salt can be converted into a desired salt of another metal by salt-interchange, e.g. with another alkanolate.

Of particular importance are the salts of compounds of formula I with organic bases, an essential feature of which is the presence of i a quaternary nitrogen atom. Such salts are of formula Ia 4 t 11 i Ia) *-CO-N-CO-NH-* *-O-CFz-CHF-CF3 X (la) j wherein Ri and Rz are as defined above and X is the cation of an organic base. X is preferably one of the following organic cations: y'd i -6 Ir

S(CH

3 )4 N, (C a

H

5 4 N (n-C 3

H

7 )4 N (i-C3Hy) 4 N (n-C 4

H

9 )4 -CH2) (CH 3 3

N

H

II and CH3-(CH2) N-CH3

H

whereby n is an integer from 8 to 12. The salts cf formula Ia also comprise mixtures of these salts with different cations. The salts of formula la can be prepared in a manner known per se by reacting a #9 cO S° compound of formula I with corresponding ammonium hydroxides of the formula X (OH) wherein Xo is as defined above.

8 8 9 0 Jc, N-Benzoyl-N'-2,5-dichlorophenylureas with a haloalkoxy substituent in the 4-position of the phenyl ring are already known as insecticides US patent specification 4 518 804 and German Offenlegungsschrift 2 848 794). Insecticidal dichloro-4-haloalkenyloxyphenyl)ureas are described in US patent specification 4 162 330. Insecticidal

S

l t chloro-4-haloalkoxyphenyl)ureas are the subject matter of US patent Si specification 4 468 405. Furthermore, compounds of similar structure are known from US patent specification 4 529 819 and British patent Sapplications 2 106 499, 2 106 500, 2 106 501 and 2 113 679. The Sfeature which essentially distinguishes the novel benzoylphenylureas of formula I according to the present invention from the compounds described in these references is that the novel compounds of this invention carry in the 4 -position of the phenyl ring a 1,1,2,3,3,3-hexafluoropropyloxy group.

7 Surprisingly, it has been found that the compounds of this invention and the salts thereof 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 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 S° crops of useful plants, especially in cotton against Spodoptera S littoralis and Heliothis virescens) and in fruit and vegetables 0 against Laspeyresia pomonella, Leptinotarsa decemlineata and S a Epilachna varivestis). The compounds of formula I have a pronounced s ovicidal and, in particular, larvicidal action against insects, I especially against larvae of noxious feeding insects. If compounds A of formula I are ingested by adult insect stages with the feed, then S ,3 a diminished oviposition and/or reduced hatching rate is observed in it many insects, especially in Coleopterae, e.g. Anthonomus grandis.

StThe 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 S following species of mites which attack crops of fruit and vegetables: Tetranychus urticae, Tetranychus cinnabarinus, Panonychus ulmi, 8| 8 Broybia rubrioculus, Panonychus citri, Eriophyes piri, Eriophyes ribis, Eriophyes vitis, Tarsonemus pallidus, Phyllocoptes vitis and Phyllocoptruta oleivora.

Moreover, the benzoylureas of formula I have properties enabling them to be used for controlling slugs and snails. The repellant and feed inhibiting action of these compounds is frequently very difficult to ascertain in laboratory tests. However, in field trials even at very low concentrations good activity is observed in Sagricultural and horticultural crops. In particular, sensitive crops Sof lettuce, vegetables and fruit (such as strawberries) and ornamentals and flowers are afforded protection against feeding j damage caused by slugs and snails. The compounds of formula I of this invention are effective against all slugs and snails, most of which occur as polyphagic pests in agricultural and horticultural I crops. In addition to exhibiting feed inhibiting action, the .compounds of formula I can also effect mortality. Numbering among Sterrestrial slugs are several pests which cause damage of great economic significance, for example the slugs Arion rufus (red slug), j Arion ater and other Arionidae, Limax species and field slugs, e.g.

S Deroceras reticulatum and D. agreste of the family Limacidae, and also species of the family Milacidae. Damage is also caused by snails, inter alia, of the genera Bradybaena, Cepea, Cochlodina, Discus, Euomphalia, Galba, Helicigona, Helix, Helicella, Helicodiscus, Lymnaea, Opeas, Vallonia and Zonitoides.

The good pesticidal activity of the compounds of formula I of the invention corresponds to a mortality of at least 50-60 of the Sabove pests.

as 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 i i q.

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

I Ii I Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or Ssubstituted naphthalenes, phthalates such as dibutyl phthalate or I t dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as 1 ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such Sas N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, Sas well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

3 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 p.properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorpi 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, i e.g. especially dolomite or pulverised plant residues.

i j i Depending on the nature of the compound of formula I to be formulated, i or of combinations thereof with other insecticides or acaricides, j i suitable surface-active compounds are non-ionic, 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 i water-soluble synthetic surface-active compounds.

I Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-C 2 2 e.g. the sodium or potassium salts of oleic or I stearic acid, or of natural fatty acid mixtures which can be :i e obtained, e.g. from coconut oil or tallow oil. Further suitable surfactants are also the fatty acid methyltaurin salts as well as I modified and unmodified phospholipids.

S 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 substi- S.tuted ammonium salts and contain a Ca-Czzalkyl 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.

11 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- C) 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 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.

04 o 0. Further suitable non-ionic surfactants are the water-soluble adducts o f S of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 a4 °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, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

23o Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cs-Cazalkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, 1- 12 benzyl or hydroxy-lower alkyl 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, "To:sid 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 concentrates, the end user will normally employ diluted formulations of a, substantially lover 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.

Example It a) Preparation of 3,5-dichloro-4-(l,1,2,3,3,3-hexafluoropropyl- I t oxy)aniline 47 g of 4-acetylamino-3,5-dichlorophenol together with 154 g of 90 potassium hydroxide solution and 130 ml of dimethylformamide are stirred in an autoclave. 75.8 g of hexafluoropropylene are then pressed into the closed autoclave. The mixture is stirred for hours at 70°C under the pressure developing in the autoclave.

After cooling, the mixture is concentrated by rotary evaporation and L -r 13 the residue is dissolved in methylene chloride. The resultant solution is washed with water, dried over Na 2 S04 and concentrated.

The crude product obtained as residue is chromatographed through a column of silica gel (length: 1 m; diameter: 10 cm) eluted with an 11:1 mixture of toluene and acetone, affording 4-acetylamino-3,5-dichloro-l-(1,1,2,3,3,3-hexafluoropropyloxy)benzene in the form of pale yellow crystals 113-115°C), 26 g of which are kept for hours under reflux with 110 ml of ethanol and 35.6 ml of 37 hydrochloric acid. The reaction mixture is then concentrated, diluted with ice/water and made weakly alkaline. The product is extracted from the mixture with methylene chloride. The organic extract phase is washed with water, dried over Na 2 SO0 and concentrated. The residue is purified by distillation, thus affording the title compound of the formula I A H2N- *-OCF 2

-CHF-CF

3 a a as a colourless liquid with a boiling point of 91-96°C/0.001 torr.

b) Preparation of N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4- S(1,l,2,3,3,3-hexafluororopoyloxy)phenyljurea S 4.3 g of 3,5-dichloro-4-(l,l,2,3,3,3-hexafluoropropyluxy)aniline are dissolved with stirring in 50 ml of dry toluene and, with exclusion at of moisture, a solution of 2.41 g of 2,6-difluorobenzoylisocyanate i t. in 10 ml of dry toluene is added at room temperature. The batch is stirred for a further 12 hours at room temperature. Aboat 75 of J* the solvent is then removed by rotary evaporation, the precipitated il. residue is filtered with suction, washed with a small amount of cold Stoluene and hexane and then dried in vacuo, affording the title compound of the formula 7 14 F~ Cl 0 AO*w 0 -C-NH-C-NH-.o '-00F 2 -CHF-CF3 \F Cl in the form of a crystalline white powder with a melting point of 171-172*C (compound 1).

The following compounds of formula I have been prepared in a manner corresponding to that described above:

I

Compound

M.P.

0 96 A9 t I C) t *9 Cl ,C1 0 -C0-NH-CQ-NH-* -cF 2 CHFCF3 \Cl /Cl Cl C -CO-NH-C0-NH-.&

>-O-CF

2

CHFCF

3 ~Cl Cl ,Cl 178-1800C 17 7-1 78 0

C

156-1580C c) Preparation of the sodium salt of compound 1 9.58 g of N-(2,6-difluorobenzoyl)-N'--!3,5-dichloro-4-(1,1,2,3,3,3hexaflujoropropyloxy)phenyllurea are suspended in 20 ml of absolute methanol. A solution of 0.43 g of sodium in 30 ml of absolute methanol is added dropwise with stirring to this suspension. A clear solution forms whic ,h is then concentrated. The residual product is dried in vacuo at room temperature, affording the title compound of the formula .y 1 F /Cl *-O-CF2CHFCF3 a F \Cl as colourless crystals.

The following salt of compound 2 of the formula below can also be prepared by proceeding as described above: /C /Cl -CO-NH-- O-CFZCHFCF 3 C1 d) Preparation of the tetrabutylammonium salt of compound 1 2.56 g of N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4-(l,1,2,3,3,3- S hexafluoropropyloxy)phenyl]urea are suspended in 30 ml of methanol.

With stirring, 5.2 g of a methanolic solution containing 1.3 g of tetra-n-butylammonium hydroxide are added to this suspension, I whereupon a clear solution forms. This solution is concentrated and I the residual crude product is suspended in hexane. The suspension is filtered with suction and the filter residue is washed with hexane I and then dried, affording the title compound of the formula j S/ Cl i- *-CO-N-CO-NH-' *-O-CF 2 CHFCF3 [(n-C4H 9 )4 \F \cll as colourless crystals.

The following salts of formula la can also be prepared in accordance with this procedure:

I

A

16 F /01 CO--C-N -a OCF 2

CHFCF

3 i(CH 3 )4 N \F I -CO-N-CO-NH-o *-QCF 2

CHFCF

3 \F Cl

I[(C

2

H

5 )4N ]o It 4, 4.

00 4 o #0 00 0 0 4 0 44 00 0 44 @4 04 1 11 4 4 if $1 0 14 4 4$4 f 4$

I

I- /1 01( >C-N-O-NH-ac IC2HFF L( -CH)(H33

/,OCF

2

CHFCF

3 (-374 cl Cl 0 >CO-N-CO-NH- >OCF2CHFCF 3 I

HJ

I"

7 17 /F

C

*-CO-N-CO-NH-' *-OCF 2

CHFCF

3 [(t-C4H9)3NH Cl Example 2: Formulations for active ingredients of formula I according to Example 1 or combinations thereof with other insecticides or acaricides (throughout, percentages are by weight)

'I

i

I

f i i ft it I i ft t It t~ it t tic- .ao 1. Wettable powders compound of formula I or combination sodium lignosulfonate sodium laurylsulfate sodium diisobutylnaphthalenesulfonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin The active ingredient or combination is t adjuvants and the mixture is thoroughly g affording wettable powders which can be d suspensions of the desired concentration.

2. Emulsifiable concentrate compound of formula I or combination octylphenol polyethylene glycol ether moles of ethylene oxide) oalcium dodecylbenzenesulfonate castor oil polygycol ether (36 moles of ethylene oxide) cyclohexanone xylene mixture a) 25 5% 3% 6 10 b) 50 2% 5 10 62 27 10 c) 75 horoughly mixed with the round in a suitable mill, iluted with water to give 10 3% 3% 4% 30 50 S- 18 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 carrier, and grinding the mixture in a suitable mill.

4. Extruder granulate i compound of formula I or combination 10 sodium lignosulfonate 2 carboxymethylcellulose 1 kaolin 87% 0 0 I oo** The active ingredient or combination is mixed and ground with the 4 adjuvants, and the mixture is subsequently moistened with water. The 4 9 4 mixture is extruded and then dried in a stream of air.

S0 0 o:o Coated granulate compound of formula I or combination 3 Spolyethylene glycol (mol.wt.200) 3 S kaolin 94% The finely ground active ingredient or combination is uniformly S i applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

t 2 6. Suspension concentrate compound of formula I or combi ethylene glycol nonylphenol polyethylene glyco moles of ethylene oxide) sodium lignosulfonate carboxymethylcellulose 37 aqueous formaldehyde solu silicone oil in the form of a aqueous emulsion water ii 19 nation 1 ether tion 75 40 10 6 10 1 0.2 0.8 32 j i IIl II I I Cl 04 4 I IB 0 '4 a I I'1 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.

Example 3: 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 the given concentration. After the maggots have pupated, the pupae are separated from the substrate by flushing them out with water and then deposited in containerb closed with a perforated top.

Each ba effect then ma out of 7 20 tch of flushed out pupae is counted to determine the toxic of the test compound on the maggot development. A count is de after 10 days of the number of flies which have hatched the pupae.

1 i .i 00 4,l 0 0 04 04 00 C4 00 00 0 0 04 4.

4 0B itI &Il The compounds of formula I according to Example 1 exhibit good activity in this test.

Example 4: Action against Lucilia sericata 1 ml of an aqueous solution containing 0.5 of test compound is added at 50 0 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 formula I according to Example 1 exhibit good activity against Lucilia sericata.

Example 5: 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 formula I according to Example 1 exhibit good activity against Aedes aegypti.

Example 6: Insecticidal action against feeding insects a) Cotton plants about 25 cm high, in pots, are sprayed with aqueous emulsions which contain the respective test compound in concentrations of 3, 12.5 and 50 ppm. After the spray coating has dried, the cotton plants are populated with Spodoptera littoralis and Heliothis 21 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 2 days.

Compounds 1, 2, 3 and 4 according to Example 1 effect 80-100 mortality against Spodoptera larvae at 3 ppm. 80-100 mortality is effected against Heliothis larvae by compound 1 at 12.5 ppm and by compounds 2 and 3 at 50 ppm.

b) Comparative test The above test a) is repeated using compound 1 of this invention and It two prior art compounds. In distinction to test the percentage mortality of the larvae is not determined until after 7 days. The active ingredient concentrations, the compounds employed and the results obtained are indicated in the following Table: a oa 0 0 0 o o o 0 00 00 0 4 to C C c .4 00 000 0 0 0 0 00 0 0 0 90 0 090 00 4 0 0 0 6 0 0 0 60 6 Mortality Compounds employed Spodoptera littoralis Heliothis virescens 0.4 ppm, 0.8 ppm 0.8 ppm 1.5 ppm *-CO-NH-CO-NH-* *-0-CF 2 -CRF-CF3 100 100 90 100 compound 1 according to Example 1 of the present invention C0-NH-C-NI-* *-0-CF 2

-CHF

2 67 90 23 70 acc. to US Patent 4 468 405 (columns 7/8, compound 1) -CO-NH-CO-NH-o *-0-CFZ-CHF 2 8 10 0 0 acc. to US Patent 4 518 804 (column 6, compound 23 Example 7: 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 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 0 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 formula I according to Example 1 exhibit good activity in this test.

Example 8: Ovicidal action against Heliothis virescens Corresponding amounts of a wettable powder formulation containing by weight of the test compound are mixed with sufficient water to produce an aqueous emulsion with an active ingredient concentration 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. The hatching rate in comparison with untreated controls is determined after 6 to 8 days.

I Example 9 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.

I

After the solution has dried and kept at a temperature of from the treated eggs and th after 6 days.

1 24 I, the eggs are placed in petri dishes S28°C. The percentage of larvae hatched e percentage mortality is evaluated ,i ,t o e oa a 9 O p op P. O 0 0 0o p o a p ooo p t t c The compounds of formula I according to Example 1 exhibit good activity in this test.

Example 10: 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 pm 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 percentage rjortality of the eggs, i.e.

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 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.

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

Example 11: 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 hours), each plant is populated with 10 adult beetles (Anthonomus grandis). Plastic cylinders, covered at the top with '1 gauze, are then slipped test insects to prevent The treated plants are humidity. Evaluation is the percentage mortalit 25 over the treated plants populated with the the beetles from migrating from the plants.

then kept at 25 0 C and about 60 relative Smade after 2, 3, 4 and 5 days to determine :y of the beetles (percentage in dorsal ie anti-feeding action as compared with j

-F

!lii i.

i 1~ i ri:: i position) as well as th untreated controls.

ID Example 12: Insecticidal stomach posion action against Plutella xylostella Potted Chinese cabbage plants (pot size: 10 cm diameter) in the 4-leaf stage are sprayed with aqueous emulsions which contain the test compound in a concentration of 0.8 ppm and which dry on the plants.

i

I

I I After 2 days, each of the treated Chinese cabbage plants is populated with 10 Plutella xylostella larvae in the L 2 -stage. The test is carried out at 24°C and at 60 relative humidity in dim light.

Evaluation of the percentage mortality of the larvae is made after 2 and 5 days.

Compound 1 according to Example 1 effects 100 mortality in this test.

Example 13: Feed inhibiting action against slugs red slugs (Arion rufus) are left for 17 hours under controlled test conditions in each of a number of cages containing 4 fresh lettuce leaves. In these tests, each cage either only contains untreated leaves or only contains leaves which have been treated by spray application. The concentration of the test compound in the aqueous formulation applied is 0.5 by weight. The extent of the feeding damage is determined on the basis of weight differences, AC C O C r fI*a~r j i~ I~IIDUII CL heT_~LI~ I l~ T~CI1I l i .L1 i. i .i 26 photocopies of pictures of the feeding damage and on the basis of any evident assessable criteria in comparison with untreated controls.

The mortality of the test animals is also determined.

Compounds of formula I according to claim 1 exhibit good activity in this test.

i, 1 1;a

Claims

1. A compound of formula I 1! *-CO-NH-CO-NH-. -O-CF 2 -CHF-CF3 wherein R, is hydrogen or fluorine and R 2 is fluorine or chlorine, or a salt thereof.

2. A compound of formula I according to claim 1, wherein R, is fluorine and R 2 is fluorine or chlorine.

3. A compound of formula I acc~ording to claim 1, wherein R, is hydrogen and R2 is fluorine or chlorine.

4. The compound according to claim 2 of the formula It CO-NH-CO-NH-K -0-CF2 -CHF-CF3 The compound according to claim 3 of the formula O-NH-CO-NH-.( >O-CF 2 -CHF-0F 3

6. The compound according to claim 3 of the formula -CO-NH-CO-NH-e >-O-CF 2 -CHF-CF 3 7 I i I I~ i iI Ei '1 i i ir i 3 a i:t i i i i i i jj /I If E j i i i r i i i .i 28

7. The compound according to claim 2 of the formula T 1 *-CO-NH-CO-NH-' *-O-CFa-CHF-CF3 C_. C~a

8. A metal salt of a compound of formula I according to any one of claims 1 to 7.

9. A salt of a compound of formula I according to any one of claims 1 to 7 with an organic base in the presence of a quaternary nitrogen atom. A process for the preparation of a compound according to any one of claims 1 to 9, which process comprises reacting a) the compound of the formula II CF 3 -CIF-CF 2 \.-NH (II) with a compound of formula III S~.-CO-NC=O (III) or b) the compound of formula IV CF3-CHF-CFZ.o-. (Iv) 6896T i i i I 29 with a compound of formula V i *-CO-NH 2 (V) k 2 or c) the compound of formula II with a compound of formula VI S CO-NH-COOR (VI)

11. The compound of formula II e CF3-CH-CFa-O- -NH CFa-CHF-CF2-O- -N=C=0 (IV) 1

13.n wch formulae III, V and VI, the radich contains a active ingras definednt a S° in any one oF claims 1 to 3 and R is a C 1 -Cnalkyl radical which is o o o unsubstituted or substituted by halogen, and, if desired, converting the comporesultant compound according to any one of claims to 7, or a salt thereof, togethe with suitable compouarriers and of formula adjants K 6896T 12. The compound of formula IV CF 3 -CHF-CF 2 (IV) 13. A pesticidal composition which contains as active ingredient a compound according to any one of claims 1 to 7, or a salt thereof, together with suitable carriers and/or other adjuvants. K 6896T 0 -qI 30

14. A method of controlling insects, representatives of the order Acarina and slugs and snails, which method comprises treating said pests, the various development stages or the locus thereof with a pesticidally effective amount of a compound of formula I according to any one of claims 1 to 7, or of a salt thereof, or with a composition which contains a i pesticidally effective amount of such a compound, together with adjuvants and carriers. A method according to claim 14 for controlling larval stages of plant-destructive insects.

16. A method according to claim 14 for controlling insect eggs.

17. A substituted N-benzoyl-N'-3,5-dichloro-4-hexafluoropropyloxy- phenylurea, substantially as hereinbefore described with reference to any V one of the Example 1 and any one of compounds 1 to 4.

18. A process for the preparation of a substituted i dichloro-4-hexafluoropropyloxyphenylurea, substantially as hereinbefore S described with reference to Example 1.

19. A pesticidal composition, substantially as hereinbefore i described with reference to any one of the Examples 2.1 to 2.6. J DATED this EIGHTH day of MARCH 1990 i Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON [1 t