AU616239B2 - Benzoylphenylureas - Google Patents

Description

S F Ref: 83630 616239 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: o Related Art: Name and Address of Applicant: Address for Service: Ciba-Geigy AG Klybeckstrasse 141 4002 Basle

SWITZERLAND

Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Benzoylphenylureas The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/4 i i

I

14 5-16882/142 Benzoylphenylureas Abstract Novel substituted N-benzoyl-N'-2,3,5-trifluoro-4-alkoxy- or -haloalkoxyphenylureas of formula I 0 00 RI F F /R1 F\ /F o" R3- *-CO-NH-CO-NH- '-OR4 (I) a2 oR 9 0 9* 0 in which R 1 is hydrogen, fluorine or chlorine; R2 is fluorine or chlorine; R 3 is hydrogen or fluorine; and R 4 is C 1 -Cloalkyl, -C(X)F-

CI-C

7 alkyl, or -C(X)F-Ci-C 7 alkyl that is mono- or poly-substituted by halogen, X being hydrogen or halogen, processes and intermediates for tr 04 S their preparation, their use in pest control, and pesticidal compositions that contain at least one compound of formula I as active ingredient, are 9t 0 *o disclosed. The preferred field of application is the control of pests in and on animals and plants.

0 00 1

-I-

1 5-16882/1+2 Benzoylphenylureas The present invention relates to novel substituted N-benzoyl-N'-2,3,5trifluoro-4-alkoxy- or -haloalkoxy-phenylureas, processes and intermediates for their preparation, pesticides that contain these compounds and their use in pest control.

S°o' The compounds according to the invention correspond to formula I 0 iRi F\ /F .*-CO-NH-CO-NH-- _-OR \R2 \F 4 f in which Ri is hydrogen, fluorine or chlorine; R 2 is fluorine or chlorine; R 3 is hydrogen or fluorine; and R4 is Ci-Cloalkyl, -C(X)F- Ci-C 7 alkyl, or -C(X)F-Ci-C 7 alkyl that is mono- or poly-substituted by at halogen, X being hydrogen or halogen.

Depending on the nature of the substituent R4, the compounds of formula I may also be in the form of optically active isomers. In such cases, the invention relates to both the pure optically active isomers and also mixtures thereof.

Suitable halogen substituents are fluorine and chlorine, as well as also bromine and iodine, with fluorine and chlorine being preferred.

Suitable Ci-Cioalkyl substituents may be straight-chained or branched.

There may be mentioned as examples of such alkyls methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl or pentyl, hexyl, heptyl, octyl etc. and their isomers.

heptyl, octyl etc. and their isomers.

II

-2 The -C(X)F-Ci-C7alkyls that may be unsubstituted or monc> or poly-substituted by halogen and which are suitable as substituents may be straightchained or branched and only partially or also perhalogenated, the above definitions of halogen and alkyl being applicable. Suitable examples of such substituents are, inter alia, ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as, for example, CHFCF 3

CF

2

CF

3

CF

2 CC13, CF 2 CHC1 2

CF

2

CHF

2

CF

2 CFC12, CF 2 CHBr 2

CF

2 CHClF,

CF

2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as, for example, CF2CHBrCH 2 Br, CH 2 CHFCF3, CHFCF 2

CF

3 or CHFCF 2

CF

3 butyl substituted from S one to nine times by fluorine, chlorine and/or bromine or one of the oo isomers thereof, such as, for example, CHFCF 2

CHFCF

3 or (CF 2 3

CF

3 o oo The compounds of formula I to which special emphasis is given are those DO 0 O a in which Ri is hydrogen or fluorine; Rz is fluorine or chlorine; R3 is oa o hydrogen or fluorine; and Ri is Ci-Cyalkyl, -C(X)F-Ci-C 5 alkyl, or -C(X)F-Ci-Csalkyl that is mono- or poly-substituted by halogen, X being hydrogen, fluorine or chlorine.

Of these there are preferred compounds of formula I in which R 1 is o hydrogen or fluorine; Rz is fluorine or chlorine; R3 is hydrogen or fluorine; and R4 is Ci-C 3 alkyl, -CF 2 -Ci-C 3 alkyl, or -CF 2 -Ci-C 3 alkyl that is mono- or poly-substituted by fluorine.

The compounds according to the invention can be prepared according to processes that are known per se. Such processes are described, inter alia, in DE-OS 21 23 236, 26 01 780 and 32 40 975. For example, the compounds of formula I can be obtained by a) reacting an aniline of formula ii F F F\ /F H2N-o *-OR4 (II) with a benzoyl isocyanate of formula III i -3 /Rl R3-- *-CO-N=C=0 (III), \R2 or b) reacting an isocyanate of formula IV F\ /F O=C=N-- *-OR4 (IV) o oF 0F S* with a benzamide of formula V S0 /R1 0 a S0R3-' CONH 2 R2Z o or c) reacting an aniline of formula II with a urethane (f formula VI «Ri

R

3 '-CO-NH-COOR (VI).

\R2 o 0 0 0 In formulae II to VI, R 1

R

2 R3 and R4 have the meanings given for formula I, and in formula VI R is a Ci-Coalkyl radical that may be unsubstituted or may be substituted by halogen, preferably chlorine.

The mentioned processes b) and c) can preferably be carried out under normal pressure and in the presence of an organic solvent or diluent.

Suitable solvents or diluents are, for example, ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylenes, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; nitriles, such as acetonitrile or 4 -4propionitrile; dimethyl sulfoxide and ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone.

Process a) is generally carried out at a temperature of from to +200 0 C, preferably from 0 to +100°C, for example at room temperature, in the absence or presence of an organic base, for example triethylamine. Process b) is carried out at a temperature of from 0 to +150 0 C, preferably at the boiling point of the solvent used, and in the absence or presence of an organic base, such as pyridine, and/or with the addition of an alkali metal or an alkaline earth metal, preferably sodium. For process that is to say for the reaction of a urethane of S0 Q e S formula VI with an aniline of formula II, temperatures of from approximately +60 0 C 1o the boiling point of the particular reaction mixture are o o preferred, there being used as solvents especially aromatic hydrocarbons, such as toluene, xylenes, chlorobenzene, etc..

o oo The starting materials of formulae III to VI are known or can be prepared analogously to known processes.

4, 4 The starting materials of formula II are novel compounds to which the present invention ilso relates. The compounds of formula II can be S prepared in a manner known per se, for example by haloalkylating an aminophenol of formula VII F F

H

2 *-OH (VII)

\F

according to processes that are known in principle, by the addition of fluorinated alkenylene or alkenylene that is mono- or poly-substituted by halogen of the formula CF 2 =CF-Ci-C6alkyl. The reaction is preferably carried out in an organic solvent, such as, for example, dimethylformamide, at normal or slightly elevated pressure, at a temperature of from to +150 0 C, preferably from -10 to +50*C, and in the absence or presence of a basic catalyst, such as, for example, potassium hydroxide, sodium hydroxide, triethylamine or tetraethylammonium hydroxide (cf. J.

Am. Chem. Soc. 73, 1951, p. 5831; US Patent Specification No. 3 937 726).

0 1 r 5 The aminophenol of formula VII is novel, also forms part of the present invention and can be prepared by processes that are known in principle, for example by catalytically hydrogenating the nitrophenol of formula VIII F F OzN-- OH (VIII).

\F/

Suitable catalysts are customary hydrogenation catalysts, such as, for example, platinum, palladium, rhenium, rhenium oxides or Raney nickel b (cf. J. Org. Chem. 29, 1964). The conversion of the NO 2 group into the o a NH 2 group can also be effected by customary chemical reduction, for example with iron or tin chloride in a hydrochloric acid medium.

9O S 4 0 4 The nitrophenol of formula VTII is novel, also forms part of the present invention and can be prepared according to processes that are known in principle, for example by removing the alkyl group from the alkoxynitrobenzene of the formula IX F F S o 2N-* (IX), S° in which R4' is C1-ClOalkyl, at from +30 to 130°C, preferably from to 120 0 C, in strongly acidic medium, for example in a hydrohalic acid, such as hydrochloric acid or hydrobromic acid, which if desired may be dissolved in acetic acid or another organic solvent (cf. Chem. Rev.

54, 1954, pp. 615-685).

The alkoxynitrobenzenes of formula (IX) are novel, also form part of the present invention, and can be prepzred by processes that are known in principle, for example by reacting the nitrQbenzene of the formula (X) F\ /F 0 2

(X)

ai

L'

6 with a metal alcoholate of the formula MetOR4' in which Met is an alkaline earth metal, preferably an alkali metal, and R4' has the meaning given above.

The nitrobenzene of formula X is known and can be prepared by methods that are known in principle.

In the published European Patent Applications 0 071 279 and 0 243 790, inter alia N-halobenzoyl-N'-(halo-4-haloalkoxyphenyl)-ureas are described quite generally as insecticides having a larvicidal action. However, 0 there is no specific disclosure in these publications of N-(2-mono- or 2,6-di-halobenzoyl)-N'-(2,3,5-trifluoro-4-alkoxy- or -halo-alkoxyo oa phenyl)-ureas.

o a Surprisingly, it has been found that the compounds of formula I according 0 0 0 to the invention are stronger active ingredients in pest control, while being well tolerated by warm-blooded animals and by plants. Thus the compounds of formula I are suitable, for example, for controlling pests a *o in and on animals and plants. Such pests belong principally to the phylum of the Arthropoda, such as, especially, insects of the order Lepidoptera, 3 Coleoptera, Homoptera, Heteropte:a, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera or Hymenoptera, and arachnids of the order Acarina, such as, for example, mites and ticks. It is possible to control every stage of development of the pests, that is to say the adults, pupae and nymphs as well as, especially, the larvae and eggs. It is thus possible to control effectively especially the larvae and eggs of phytopathogenic insect and mite pests in ornamentals and useful plants, such as, for example, in fruit and vegetables, and especially in cotton. If the compounds of formula I are ingested by imagines, then a direct kill of the pests or a reduced oviposition and/or hatching rate can be observed. The latter phenomenon can be observed especially in Coleoptera. In the control of pes':s that parasitise animals, especially domestic animals and productive livestock, the chief pests are ectoparasites, such as, for example, mites and ticks and Diptera, such as, for example, Lucilia sericata. The compounds of the invention also have a noticeable effect against phytophagous snails.

4 -7- The compounds of the invention are distinguished especially by an excellent larvicidal activity against Spodoptera littoralis and especially against Heliothis virescens.

The good pesticidal activity of the compounds of formula I according to the invention corresponds to a mortality rate of at least from 50 to 60 of the mentioned pests.

The activity of the compounds of the invention or the compositions containing them can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides.

o"0 Additives that come into consideration are, for example, representatives o o of the following classes of active ingredients: organophosphorus com- 9's pounds, nitrophenols and derivatives thereof, formamidines, ureas, 00 0 o carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.

The compounds of formula I are used in unmodified form or, preferably, 0o 4 together with the inert adjuvants tolerated by plants that are conventionally employed in the art of formulation, and can therefore be formulated in known manner e.g. into 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 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 an 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, where appropriate, surface-active compounds (surfactants).

8 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.

o The solid carriers used e.g. for dusts and dispersible powders, are co normally natural mineral fillers such as calcite, talcum, kaolin, o" o montmorillonite or attapulgite. In order to improve the physical properro o ties it is also possible to add highly dispersed silicic acids or highly 0 dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; o "o and suitable nonsorbent carriers are, for example, calcite or sand. In Oos addition, a great number of granulated materials of inorganic or urganic nature can be used, e.g. especially dolomite or pulverised plant "o residues.

Suitable surface-active compounds are non-ionic, cationic ai.d/or anionic 0o surfactants having good emulsifying, dispersing and wetting properties.

The term "surfactants" will also be understood as comprising mixtures of surfactants.

Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps ire the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids

(C

0 o-C 22 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 tall oil. Mention may also be made of fatty acid methyltaurin salts and modified and unmodified phospholipids as surfactants.

1 SMore frequent especially fa I derivatives o -9 ly, however, so-called synthetic surfactants are used, tty sulfonates, fatty sulfates, sulfonated benzimidazole r alkylarylsulfonates.

i 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 generally contain a C 8

-C

2 2 alkyl 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 sulfated and sulfonated fatty alcohol/ethylene I xide adducts. The sulfonated benzimidazole derivatives preferably t* contain 2 sulfonic acid groups and one fatty acid radical containing about 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the «f 0 sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, o 94 dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene cxide.

Non-ionic surfactants are especially polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, 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 4 4 suitable non-ionic surfactants are the water-soluble adducts 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 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.

Examples of non-ionic surfactants are nonylphonolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, 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.

I

10 Cationic surfactants are especially quaternary ammonium salts which contain, as N-substituent, at least one C 8

-C

2 2 alkyl 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, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described, inter alia, in the following publications: s "McCutcheon's Detergents and Emulsifiers Annual", SV, MC Publishing Corp., Ridgewood, New Jersey, 1979; Dr. Helmut Stache, "Tensid-Taschenbuch", e e Carl Hanser Verlag, Munich/Vienna 1981.

The pesticidal preparations usually contain 0.1 to 99 especially 0.1 to 95 of active ingredient of formula I or combinations thereof with other insecticides or acaricides, I to 99.9 of a solid or liquid adjuvant, and 0 to 25 especially 0.1 to 20 of a surfactant. Whereas t commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations containing icidcrably lower concentrations of active ingredient.

II a The compositions may also contain further auxiliaries such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

Example 1: Preparation 1.1. Intermediates .1.11. Alkoxynitrobenzenes 1.1.1.1. 2,3,5-trifluoro-4-ethoxy-nitrobenzene A solution of 2.3 g of sodium in 50 ml of absolute ethanol is added dropwise, while cooling with ice, to 17.93 g of 2,3,4,5-tetrafluoro- 11 nitrobenzene and 25 ml of ethanol and the whole is then stirred for 1 hour at +10 0 C. H reaction mixture is subsequently poured into 300 ml of ice/water, extracted with ether and the ethereal phase is dried over sodium sulfate. The solvent is distilled off in vacuo. The title compound of formula F F 0 2 ozN-* *-0C 2

H

5 (Como. No. 1.1.1.1.) 0 0 c 0e0t# 0 0 0 00 ;00 0 0 00 00 0 0o 0 000 0 0 0 00 0 00 0 0 00 U0 00 00 0 00 is in the form of a yellow liquid: b.p. 57-60 0 C/0.02 torr.

The following compounds are prepared in anr analogous manner: F F~ ON-* *-024'

F

Comp. No. R I' physical data 1.1.1.2. (CH 2 2

CH

3 b.p. 77-830C/0.04 torr 1.1.1.3. CH(C 3 2 b.p. 76 0 C/0.02 torr 1.1.1.4, (CH 2 3

CH

3 b.p. 80-83'C/0.02 torr 1.1*1.5. C(C8 3 3 b.p. 62-67 0 C/0.01 torr

CH

3 1.1.2. 2,3,6-trifluoro-4-nitropheno 14 g of 2, 3 ,5-ttifluoro-4-ethoxy-nitrobenzene, 400 ml of 40 hydrobromic acid and 400 ml of acetic acid are heated at reflux temperature for 8 hours, while stirring. Acetic acid, water and hydrobitomic acid are then distilled off and the residue is poured onto ice-water. The resulting precipitate is filtered off with suction and recrystallised from htxane.

The title compound of the formula F F 07,14 _/-OH (Comp. No. 1.1.2.)

L

w4 238 Action aaintSodotea ittoalis -12is in the' form of light-yellow crystals; m.p. 110-112 "C.

1.1.3. Anilines 1.1.3.1. 2,3,6-trifluoro-4-aminophenol 19.8 g of 2,3,6-trifluoro-4-nitrophenol are dissolved in 200 ml of tetrahydrofuran and the solution is hydrogenated for 4 1/2 hours at to 35'C in the presence of 6 g of Raney nickel. The reaction mixture 4s filtered, the solvent is distilled off and the residue is recrystallised from toluene/hexane. The title compound of the formula P Ina ('D00 'AID 00 F F

H

2 >-OH (Comp. No. 1.1.3.1.) i.s in the form of colourless crystals; m.p. 133-135'C.

1.1.3.2. Alkoxyanilines 1.1.3.2.1. 2,3,5-trifluoro-4--ethoxyaniline 9.7 g of 2,3,5-trifluoro-4-ethoxynitrobenzene are dissolved in 100 iml of tetrahydrofuran and the solution is hydrogenated for 9 1/2 hours at to 35'C in the presence of Raney nickel. The reaction mixture is filtered, the solvent is distilled off and the residue is distilled in vacuo. The title compound of the formula H 2N- -C 2 H 5 (Comp. No. 1.1.3.2.1.) is in the form of a colourless liqui,-; b.p. 100"C/0.02 torr.

A

.13 The foll~wing compounds ar e prepared in an analogous manner: F F

\F/

Conip. No. physical data Conip. No. physical data 1- 1.1.3.2.2.

1.1.3.2.3.

1.1. 3.2.4.

1.1.3.2.5.

ci *1~ ci ci ci ci 04 ci 94') 404 0 ci ci 04 C, ci 0 '01 ci ci 00 4 ci ci 0 ci ci 04 (CH2) 2

CH

3 CH(Cf1 3 2 (Gil 2 3 CH3 C(CH 3 )3 CH 3 b.p. 100 0 C/0.01 torr b.p. 110 0 C/0.05 torr b.p. 110 0 c/0.04 torr b.p. 100 0 Ci1003 torr 1.1.3.3. Haloalkoxyanilines 1.1.3.3.1. 2 3 5-trif luoro- 4 1 1 2,3, 3,3-hexaf lu(,ropropoxy) -aniline g of hexafluoropropylcne are introduced, while stii:ring, int. a solution of 13.4 g of 2,3,5-trifluoro-4--aminophenol and 1.2 ml of triethylamine in 80 ml of dimethylformaiide and the reaction mixture is t then stirred at room temperature for 2 hours. Subsequently, the reaction mixture is concentrated and the residue is distilled in vacuo. The title compound of the formula 0 ti F1 Y

H

2 N-I -OCF 2

CHFCF

3 (Comp. No. 1.1,3.3.1.) is in the form of a colourless liquid; b.p. 59-62'C/0.01 torr.

14 The following compounds are prepared in an analogous manner: F F H2N-\ /-OR4 Comp. No. R"11 physical data 1.1.3.3.2. CF 2

CHF

2 b p. 130 0 C/0.04 torr 1.1.3.3.3. CF 2 CHCIF b.p. 125 0 C/0.03 torr

(CF

2 2

CF

3

(CF

2 )sCF 3 CHFCHFCF3 b Yr a 4t n v P 4 C4 4 .d 49, 4 4c 4 49, 4 44a 1.2. End products 1.2.1. N-(2,6-difluorobenzoyl)-N'-[(2,3,5-trifluoro-4- (1',1',2',3',3',3'-hexafluoropropoxy)-phenyll-urea .0 "I At room temperature, 3 g of 2,6-difluorobenzoyl isocyanate are added to 5.17 g of 2,3,5-trifluoro-l-(' 3',3',3'-hexafluoropropoxy) -aniline a dissolved in 50 m. of dry toJdene and the whole is stirred for 5 hours.

Subsequently approximately 70 of the solvent is removed in a rotary evaporator. The precipitate formed is filtered off with suction, washed Ss with a small amount of cold hexane and dried in vacuo. The title compound of the formila F F F -0-NH-CO-NH--

*-OCF

2

CHFCF

3 \F F\ (Comp. No. 1.2.1.) is in the form of a colourless crystalline powder; m.p. 169-1710C.

24

I

i ao 44 a. a sa The folidwing compounds are prepared in an analogous manner: i F

/F

R3-' CO-NH-CONH-- \\.-OR4 Comp. No. Ri R 2

R

3 R4, phys. data 1.2.2. H Cl H CF 2 CHFCF3 m.p. 149-151 0

C

1.2.3. F F H CH 2

CH

3 m.p. 194-196 0

C

1.2.4. H Cl H CH 2

CH

3 m.p. 177-178 0

C

1.2.5. F F H (CH 2 2

CH

3 m.p. 190-191C 1.2.6. H Cl H (CH 2 2

CH

3 n.p. 152-155 0

C

1.2.7. F F H CF 2 CHClF n.p. 170-172 0

C

1.2.8. F F Hf CF2CHF2 m.p. 167-i6a 0

C

1.2.9. F F H CH(CH 3 2 m.p. 172-174 0

C

1.2.10. F F H (CH 2 3 CH3 m.p. 159-161 0

C

1.2.11. H F H CF 2 CHFCF3 n.p. 148-150 0

C

1.2.12. F Cl H CF 2

CHFCF

3 m.p. 198-200C 1.2.13. F F H C(CH 3 3 m.p. 218-219 0

C

1.2.14. H Cl H C(CH 3 3 m.p. 178-179'C 1.2.15. H Cl H (CH 2 3

CH

3 m.p. 133-1350C 1.2.16. H Cl H CH(CH 3 2 m.p. 159-160 0

C

1.2.17. F Cl H (cH 2 3

CH

3 m.p. 150-152 0

C

1.2.18. H F H (CH 2 3

CH

3 n.p. 153-154%C 1.2.19. F Cl H CH (CHA)Z m.p. 206-208 0

C

1.2.20. F F F CFZCHFCF 3 m.p. 187-188 0

C

1.2.21. F F F CFzCHF 2 m.p. 184-186*C 1.2.22. F F F CF2CHClF m.p. 185-187 0

C

1.2.23. F F F CF2CHFCF3 1.2.24. F F H (CF 2 2 CF3 1.2.25. F F H (CF 2 )6CF 3 1.2.26. F F F CH3 1.2.27. F F H (CH 2 9

CH

3 1.2.28. Cl Cl F CH 2

CH

3 1.2.29. F Cl F CHFCHFCHFZ

"'I

I!

16 Example 2: Formulations of active ingredients of formula I according to Preparation Example 1.2.

percentage by weight) 2.1. Emulsifiable concentrates active ingredient according to Preparation Example 1.2.

potassium dodecylbenzenesulfonate castor oil polyethylene glycol ether (36 moles of ethylene oxide) cyclohexanone xylene mixture N-methyl-2-pyrrolidone dimethylcyclohexyl phthalate a) b) 6 12 0% 5 48 20 to ao o Pul a.oa 'So P P.J aoo PP p 1' Pp Emulsions of any desired concentration can be trates by dilution with water.

produced from such concena) b) 2.2. Solutions oIo active ingredient according S to Preparation Example 1.2.

polyethylene glycol (mol. wt. 400) on° S N-methyl-2-pyrrolidone epoxidised coconut oil petroleum fraction (boiling range 160-1900C) 0 P 10 70 20 20 1% 74 These solutions are suitable for application in the form of microdrops.

2.3. Granulates a) b) active ingredient according to Preparation Example 1.2. 5 10 kaolin 94 highly dispersed silicic acid 1 attapulgite 90 *y

I.

26 -17 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.

2.4. Extruder granulate active ingredient according to Preparation Example 1.2. 10 sodium lignosulfonate 2 I carboxymethylcellulose 1 kaolin 87 The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried Sin a stream of air.

It a 2.5. Coated granulate active ingredient according to Preparation Example 1.2. 3 polyethylene glycol (mol. wt. 200) 3 S kaolin 94 The finely ground active ingredient is uniformly applied, in a mixer, to S. the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

2.6. Dusts a) b) c) d) active ingredient according to Preparation Example 1.2. 2 5 5 8 highly dispersed silicic acid 1 5 talcum 97 95 kaolin 90 92 Ready-for-use dusts are obtained by homogeneously mixing the carriers with the active ingredient and optionally grinding the mixture in a suitable mill.

I

I1~ 4 7)

I

18 2.7. Wettable powders active ingredient according to Preparation Example 1.2.

sodium lignosulfonate sodium lauryl sulfate sodium diisobutylnaphthalenesulfonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin a) b) c) 20 5% 3% 5% 67 50 6% 2% 10 27 75 10 10 0 00 0 t, 0 0 00 00000* 0 0 04 o 0 0 000* 0 0 00 0 The active ingredient is thoroughly mixed with the adjuvants and the mixture is ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

o, 2.8. Suspension concentrate active ingredient according to Preparation Example 1.2.

ethylene glycol 0 nonylphenolpolyothylene glycol ether (15 moles of ethylene oxide) sodium lignosulfonate carboxymethylcellulose 37 aqueous formaldehyde solution 0 0 silicone oil in the form of a aqueous emulsion water 40 10 6 10 1 0.2 0.8 32 The finely ground active ingredient is homogeneously mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

19 Example 3: Biological tests 3.1. Action against Musca domestica A sugar cube is so moistened with a solution of the test compound that the concentration if active ingredient in the cube after drying is 500 ppm. The treated cube is placed on a dish together with a wet cotton wool swab and covered with a beaker. 10 adult one-week-old, OP-resistant flies are placed under the beaker and kept at 25 0 C and 50 humidity. The insecticidal action is determined after 24 hours by ascertaining the mortality rate.

o o, Compounds according to Example 1.2. exhibit good activity in the above 0 04\ test.

o 4 o. 3.2 Action against bluebottles Freshly deposited eggs of the bluebottle species Lucilia sericata are introduced in small portions (30 to 50 eggs) into test tubes containing 4 ml of nutrient medium previously mixed with 1 ml of test solution containing 200 ppm of the active ingredient to be tested. After inoculao tion of the culture medium the test tub':; are closed with a cotton wool plug and incubated for 4 days at 30 0 C in an incubator. Up to this point oI larvae (stage 3) approximately 1 cm in size have developed in the Sa untreated medium. If the substance is active, then the larvae at this So0 point are either dead or distinctly retarded. Evaluation is carried out after 96 hours; the mortality is determined as a percentage.

00 0 Compounds according to Example 1.2. exhibit good larvicidal activity.

3.3. Action against Andes aegypti An amount of a 0.1 solution of the active ingredient in acetone sufficient to produce a concentration of 12.5 ppm is pipetted onto the surface of 150 ml of water in a container. After the acetone has evaporated, 30 to 40 two-day-old Aedes larvae are placed in the container.

Mortality is examined after 2 and 7 days.

Compounds according to Example 1.2. exhibit good activity in this test.

3.4. Stomach toxicant action on Spodoptera littoralis larvae (L 1 Cotton plants in the cotyledon stage are sprayed with an aqueous emulsion 4 (obtained from a emulsifiable concentrate) that contains the compound to be tested in a concentration of 400 ppm.

After the coating has dried, each of the cotton plants is populated with Spodoptera littoralis larvae in the first larval stage. The test is carried out at 26°C and about 50 relative humidity. The mortality of the larvae is determined after 2 and 3 days and development and shedding disorders of the larvae after 5 days.

o o, Compounds according to Example 1.2. exhibit 100 activity.

Stomach toxicant action against Spodoptera littoralis and Heliothis 0 oo;o' virescens larvae (La) S Potted soybean plants (pot size 10 cm diameter) at the 4-leaf stage are sprayed with aqueous emulsions containing the active ingredient in i concentration of 0.75 ppm.

S After 2 days the treated soybean plants are populated with 10 larvae each Sof Spodoptera littoralis and Heliothis virescens in the third larval stage. The test is carried out at 26'C and about 60 relative humidity S in dim light. The evaluation is carried out after 2 and 5 days; the mortality of the larvae is ascertained as a percentage.

Compounds according to Example 1.2. exhibit 80-100 activity (mortality) after 2 and 5 days for Spodoptera and for Heliothis.

3.6 Stomach toxicant action on Plutella xylostella larvae (L 2 Potted Chinese cabbagp plants (pot size 10 cm diameter) at the 4-leaf stage are sprayed with an aqueous emulsion containing the activa ingredient in a concentration of 0.75 ppm.

1' ift <~21 After two days the treated Chinese cabbage plants are populated with Plutella xylostella larvae in the second larval stage. The test is carried out at 26 0 C and about 60 relative humidity in dim light. The evaluation is carried out after 2 and 5 days; the mortality of the larvae *is ascertained as a percentage.

Compounds according to Example 1.2. exhibit 80-100 activity (mortality) after 2 and 5 days.

3.7. Actmon against Laspeyresia pomonella (eggs) Egg deposits of Laspeyresia pomonella not more than 24 hours old are immersed for 1 minute, on filter paper, in an aqueous acetonic solution containing 400 ppm of the active ingredient to be tested. When the 4 solution has dried the filter paper with the eggs is placed in a petri dish and left at a temperature of 28 0 C. After 6 days the percentage *ti, hatching rate from the treated eggs is evaluated.

t Compounds according to Example 1.2. exhibit good activity in the above test.

3.8. Influence on the reproduction of Anthonomus grandis Anthonomus grandis adults which after hatching are not more than 24 hours old are transferred in groups each of 25 beetles to cages with latticed walls. The cages containing the beetles are then immersed for to 10 seconds in an acetonic solution containing 0.1 by weight of the active ingredient to be tested.

When the beetles are dry again they are placed in covered dishes containing feed and are left for copulation and ovipop'i'ion. Egg deposits are flushed out with running water twice to three times weekly, counted, disinfected by putting them for 2 to 3 hours in an aqueous disinfectant, and then placed in dishes containing a suitable larval diet. An examination is made after 7 days to determine whether larvae have developed from the deposited eggs.

22 In order to determine the duration of the reproduction-influencing effect of the active ingredients to be tested, the egg deposits of the beetles are monitored over a period of about four weeks. Evaluation is made by assessing the reduction in the number of deposited eggs and the larvae that have hatched from them in comparison with untreated controls.

Compounds according to Example 1.2. exhibit a good reproduction-reducing activity in the above test.

3.9. Action against Anthonomus grandis (adults) Two potted cotton plants in the 6-leaf stage are sprayed with wettable o *o aqueous emulsion formulations containing 100 ppm of the active ingredient 0 0 to be tested. After the spray-coating has dried (about 1.5 hours) each plant is populated with 10 adult beetles (Anthonomus grandis). Plastics S cylinders, covered at the top with gauze, are then slipped over the t treated plants populated with the test insects in order to prevent the S beetles from migrating from the plants. The treated plants are kept at 0 0o and about 60 relative humidity. Evaluation is made after 2, 3, 4 and 5 days on the basis of the percentage mortality of the test insects "o used (percentage in dorsal position) and the anti-feeding action as o compared with untreated controls.

00 0 *a Compounds according to Example 1.2. exhibit good activity in this test, 3.10. Action against Epilachna varivestis 00 0 0

B

Phaseolus vulgaris plants (dwarf beans) about 15-20 cm in height are sprayed with aqueous emulsion formulations containing the active ingredient to be tested 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 fourth larval stage. A plastics cylinder is slipped over the infested plants and covered with a copper gauze top. The test is carried out at 28C and 60 relative humidity.

The percentage mortality is determined after 2 and 3 days. Evaluation of any feeding damage (anti-feeding effect), and of development and shedding disorders is made by observing the test insects for a further 3 days.

23 Compounds according to Example 1.2. exhibit good activity in the above test.

3.11. Ovicidal action against Heliothis virescens and Spodoptera littoralis Corresponding amounts of a wettable powder formulation containing 25 by weight of the active ingredient to be tested are mixed with sufficient water to produce an aqueous emulsion with an active ingredient concentration of 400 ppm.

One-day-old egg deposits of Heliothis on cellophane and of Spodoptera on paper are immersed for 3 minutes in these emulsions containing active ingredient and then collected by suction on round filters. The so-treated deposits are placed in petri dishes and kept in the dark at 28°C and 60 relative humidity. The hatching rate, i.e. the number of

S

B

larvae which have developed from the treated eggs is determined in S15 comparison with untreated controls after 5 and 8 days.

e o oo In the above test, compounds according to Example 1.2. exhibit an 80 to 100 ovicidal action (mortality) against Heliothis virescens and Spodoptera littoralis.

Example 4 Tests were carried out in order to determine the relative insecticidal I activity of the following active ingredients: Compound A: /F F CJ -_CO--NH-CO-NH-. '.-O-CF 2 -CHF-CF3 \F \cl N-(2,6-Difluorobenzoyl)-N'-E2-fluoro-3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-propoxy)-phenyl3-urea, which is known from EP 243790, compound No. 65; and .LMM/1437y 1 23A Compound 1.2.1: /F

F\_/F

CONH-CO-NNH-* O-CF2-CHF-CF3 N-(2,6-Difluorobenzoyl)-N'-[2,3,5-trifluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-phenyll-urea from this specification.

1) These active compounds were formulated as 10% emulsifiable concentrates, consisting of the following ingredients: 4404 4. 0 4444I active compound potassium dodecylbenzenesulfonate castor oil polyethyleneglycol ether 10 (36 mols of ethylene oxide) xylene mixture N-methyl-2-pyrrolidone dimethylcyclohexyl phthalate 10 3 14 48 20 5 So obtained compositions were dispersed in water and concentrations.

S°2) The methods employed were as follows: diluted to spraying 4~ 0 gO 04l 44 i a) Action against Heliothis virescens Soybean plants were sprayed in the four-to-five-leaf-stage with aqueous emulsions (obtained from the above 10 emulsifiable concentrates) which contained the active ingredients in concentrations of 0.2, 0.1 and 0.05 ppm. After the spray coating has dried the leaves of the treated plants (3 for each concentration) were cut off and are separately placed into Petri disks on top of a layer of moist filter paper, and were infected with 20 larvae in the L 1 -stage of Heliothis per leaf. The test units were kept at a temperature of +26*C, 55 of relative humidity and a daylight-period of 14 hours. 6 days after infection the percentage mortality of the larvae was evaluated. The mortality of the control populations on untreated leaves was 0 'LMM/1 437y 23B b) Action against Spodoptera littoralis Soybean plants were sprayed in the four-to-five-leaf-stage with aqueous emulsions (obtained from the above 10 emulsifiable concentrates) which contained the active ingredients in concentrations of 0.2, 0.1 and 0,05 ppm. After the spray coating has dried the leaves of' the treated plants (3 for ch concentration) were cut off and are separately placed into Petri disks on top of a layer of moist filter paper, and were infected with 20 larvae in the L 1 -stage of Spodoptera per leaf. The test units were kept at a temperature of +26°C, 55 of relative humidity and a daylight-period of 14 hours. 6 days after infection the percentage mortality of the larvae was evaluated. The mortality of the control populatiors on untreated leaves was 0 a no n r rro p ur ~~rrr r

D

Ir oa Ir 3) Test results: 15 a) tested organism: host plant: assessment:

L

1 -larvae of Heliothis virescens (tobacco budworm) soybean 6 days after infestion mortality rate in percent compound A compound 1.2.1 .t I concentration 4 45 400 0.2 ppm 0.1 ppm 0.05 ppm b) tested organism: host plant: assessment:

L

1 -larvae of cottonworm) soybean 6 days after Spodoptera littoralis (egyptian infestation :L.M/1437Y

I-;

If 44 23C mortality rate in percent compound A compound 1.2.1 concentration

I

0Q~ 0.2 ppm 100 100 0.1 ppm 25 0.05 ppm 15 4) Conclusion: In the test against Heliothis, compound A is generally inferior to compound 1.2.1. At all concentrations 25 difference in activity 5 are observed, which indicates highly significant improvements of activity of compound 1.2.1 against Heliothis over compound A.

Though at 0.2 ppm the biological effect of compounds A and 1.2.1 is the same against Spodoptera (100 significant loss of activity is observed for compound A at lower concentrations, while compound 1.2.1 is still sufficiently effective at 0.1 and 0.05 ppm.

For practical applications 0.2 ppm of compound 1.2.1 would control Heliothis and 0 1 ppm would control Spodoptera, where compound A would require more than 0.2 ppm and about 0.2 ppm respectively, to achieve an equivalent result.

Compound 1.2.1 is thus superior to compound A for the control of Heliothis and Spodoptera.

t1M/1437y 1 o rsr 1 id

O

F: 8 r.

Claims (14)

1. Compounds of formula I RiF\ /F R3-\ -CO-NH-CO-NH- -OR4 \R2 in which R 1 is hydrogen, fluorine or chlorine; R 2 is fluorine or chlorine; R 3 is hydrogen or fluorine; and R4 is C 1 -Cioalkyl, -C(X)F- Ca-C 7 alkyl, or -C(X)F-C-C 7 alkyl that is mono- or poly-substituted by halogen, X being hydrogen or halogen.

2. Compounds of formula I according to claim 1, in which R 1 is hydrogen or fluorine; R2 is fluorine or chlorine; R 3 is hydrogen or fluorine; and R4 is Ca-C-alkyl, -C(X)F-C 1 -Csalkyl, or -C(X)F-Cl-Csalkyl that is mono- or poly-substituted by halogen, X being hydrogen, fluorine or chlorine.

3. Compounds of formula I according to claim 2, in which R 1 is hydrogen or fluorine; R2 is fluorine or chlorine; R 3 is hydrogen or fluorine; and R 4 is C 1 '3alkyl, -CF 2 -Ca-C 3 -alkyl or -CF 2 -C 1 -C 3 alkyl that is mono- or Spoly-substituted by fluorine.

4. The compounds according to any one of claims 1 to 3 of the formulae F F F S4 -CO-NH-CO-NH-* *-OCF 2 CHFCF 3 \F FF -CO-NH-CO-NH- -OCF 2 CHFCF 3 Cl F F F F CO-NH-CO-NH-* \-OCH2CH3 \F \F ;i I F F *-CO-NH-CO-NN-* \-OCH 2 CH 3 F F F 2 2 CHi 3 F F O(CH 2 2 CB 3 /F F F 4 \F \F 444 2 Hi F 44 F F F \F \\444HCON-- OCF2CHFCF 2 '4 \F "F F F F 4 CO--NH-CO-NH-0 FCFC3 4 l F OHC 3 2 -26 F F F *.-OC(CH 3 3, F ~F F F \K-~oc(CH 3 3 F F F CONHCO-NH-- -OC/O(CH 3 a ~F F 00 CONHC'N /-(H23C F Fl ~3 F F\/F CO-NH-CO-NH-.,/ /.o(H 2 )CH 3 F \F 00 0F F F >-CO-NH-CO H- >OCF2H(u and \F F \F 27 /F F\ F CO-NH-CO-NH-- OCF 2 CHClF F \F A process for the preparation of a compound of formula I /R F\ /F R3-* .*-CO-NH-CO-NH-- -OR R2 F in which RI is hydrogen, fluorine or chlorine; R2 is fluorine or chlorine; R3 is hydrogen or fluorine; and R4 is Ca-Cloalkyl, -C(X)F- Cz-C 7 alkyl, or -C(X)F-Ci-C 7 alkyl that is mono- or poly-substituted by halogen, X being hydrogen or halogen, which comprises a) reacting an aniline of formula II 0 0 F F O 0 R2 a F Or 0 with a benzoyl isocyanate of formula III o 00 /RF *-OR4 (IV) *=0 with a benzamide of formula V 28 Ri f i R 3 CONH 2 (V) \R or c) reacting an aniline of formula II with a urethane of formula VI /R1 S -CO-NH-COOR (VI), \R/ Rl, R 2 R 3 and R4 in formulae II, III, IV, V and VI having the meanings given and R in formula VI being an unsubstituted or halogenated C 1 -C 8 -alkyl radical.

6. A pesticidal composition containing as active component an effective amount of a compound of formula I R 1 F F R3- CO-NH-CO-NH-* -OR4 0 \Ra \F in which R is hydrogen, fluorine or chlorine; R 2 is fluorine or chlorine; R 3 is hydrogen or fluorine; and R 4 is C -C 10 -alkyl, -C(X)F-C 1 -C 7 -alkyl, or -C(X)F-.C-C-alkyl that is mono- or poly- substituted by halogen, X being hydrogen or halogen, together with 15 suitable carriers and/or adjuvants.

7. A method of controlling pests in and on animals and plants, which comprises bringing the pests, in their various stages of development, into contact with a compound of formula I /R F\ F R3-' \-CO-NH-CO-NH-- \*-OR4 (I) in which R is hydrogen, fluorine or chlorine; R 2 is fluorine or chlorine; R 3 is hydrogen or fluorine; and R 4 is C-C 0 -alkyl, -C(X)F-C 1 -C 7 -alkyl, or -C(X)F-C -C -alkyl that is mono- or poly- substituted by halogen, X being hydrogen or halogen. S, /1437y 72 -29-

8. The m thod according to claim 7 for controlling insects and arachnids.

9. The method according to claim 8 for controlling larval stages of plant-destructive insects.

10. Compounds of formula II F F \F/ in which R4is C 1 -C 10 alkyl, -C(X)F-C 1 C 7 alkyl, or -C(X)F- C 1 -C 7 -alkyl that is mono- or poly-substituted by halogen, X being hydrogen or halogen, S 10 11. The compounds according to claim 10 of formulae 00 F 00 0F F 000H 2 \\.-O(CHs)c H 2 N 4 O~CFHF)Ci 3 0 00 OCF 2 CHFCF 3 /F F F H2N--, \*-O(CHz) 3 CH 3 k LM~M/437y 30 F F HzN-- OCF 2 CHF 2 and HzN-* *-OCF 2 CHC1F

12. A substituted N-benzoyl-N'-2,3,5-trifluoro-4-alkoxy- or -haloalkoxy-phenylurea, substantially as herein described with reference to Example 1.2.1 or any one of compounds 1.2.1 to 1.2.29.

13. A process for the preparation of an N-benzoyl-N'-2,3-5-trifluoro-4- alkoxy- or -haloalkoxy-phenylurea, substantially as herein described with reference to Example 1.2.1.

14. A pesticidal composition for controlling pests in and on animals and plants, substantially as herein described with reference to any one of Examples 2.1 to 2.8. A pesticidal composition for controlling pests in and on animals and plants, comprising a compound according to claim 12 together with a suitable carrier, adjuvant and/or diluent.

16. A method of controlling pests in and on animals and plants, which comprises bringing the pests, in their various stages of development into contact with a compound according to claim 12 or a composition according to claim 14 or

17. A substituted N-benzoyl-N'-2,3,5-trifluoro-4-alkoxy- or -haloalkoxy- phenylurea whenever prepared by the process of claim 5 or 13. DATED this TWENTY-THIRD day of JULY 1991 Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON LMM/1437y A