AU597311B2 - Substituted benzyl ureas and salts thereof, their preparation and their use in pest control - Google Patents

Description

r FORM 10 59731 1 SPRUSON FERGUSON COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int. Class Complete Specification Lodged.: Accepted: Published: 04 f 0

I

0 4 It 'fit &'4 a 9411 4 44 a 9 .1=R '4 a 444 4 9 4 ~W'44t4 9 a '9 9 0 a Priority: Related Art: JThis doLcument coiitains thco arcdnent ii-i ade und;r~ LSection 19 and is corrwc f orf printing.

Name of Applicant: CIBA-GEIGY AG Address of Applicant: Klybeckstrasse 141, 4002 Basle, Switzerland Actual Inventor: JOZEF DRABEK Address for Service: Spruson Ferguson, Patent Attorneys, Level 33 St Martins Tower, 31 Mar7ket Street, Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: The following statement is a full description of this invention, including the best methxod of performing it known to us SBR/JS/0071W .1 -1- 5-15630/1+2 The present invention relates to novel substituted benzoylureas and the salts thereof, to their preparation and to the use thereof in pest control.

The benzoylureas of the invention and the salts thereof have the formula I o 3 NHCORI (I) ,rt t C Sc wherein m e0 ec' Ri is CONH- or -CON-, t «t R2 is halogen,

R

3 is hydrogen or Ci-C 6 alkyl,

R

4 is hydrogen, halogen, Ci-C6alkyl, Ci-Cshaloalkyl, CI-C6alkoxy, Ci-Cshaloalkoxy, cyano or nitro,

R

5 is hydrogen, halogen or Cl-C6alkoxy, a m and n are a value from 1 to 5, with the proviso that the individual substituents R4 may differ in meaning from one another if n is a value from 2 to 5 and that the individual substituents R may differ in meaning from one another if m is a value from 2 to "aLO and X is an inorganic or organic cation.

I---I

p..

-2 Halogen shall be understood as meaning fluorine, chlorine, bromine or iodine, with fluorine or chlorine being preferred.

The alkyl, haloalkyl, alkoxy and haloalkoxy groups R 3 R4 and R 5 may be straight chain or branched and preferably contain 1 to 4 carbon atoms in the chain. Examples of such groups are, inter a].ia, methyl,

-CF

3 methoxy, -OCF 3 ethyl, ethoxy, propyl, -CF 2

-CHF-CF

3 propoxy, -OCF2-CHF-CF 3 isopropyl, isopropoxy, n-butyl, n-butoxy, n-pentyl, n-pentoxy, n-hexyl, n-hexoxy and the isomers thereof.

Suitable inorganic cations are in particular the cations of the alkali metals and alkaline earth metals, preferably the sodium and potassium cations.

Examples of organic cations are, inter alia:

R

6 -IT R 8 or Rio-NIweenec fR to R9 indepen-

A

9 dently is hydrogen, Cl-C 2 oalkyl, benzyl or phenyl and Rio is hydrogen or Ci-C 2 oalkyl, e.g. HO N (CH 3 4 N 0, (C2H 5 )L+N (n-C 3

H

7 (i-C 3

H

7 )4N (n-C 4

H

9 4 N (D, It t I S

I

I It I A III I I #1 f* ISA I S* II I I (II I I I~ I I I It

I

.ttt

IA

S

-CH2)(C3)3 /(H3 *559*9

S

99*eb* 9 9~4SS* 9 5 5* 90 0 0.-0

IN

CH

3

-(CH

2 )z N\

CH

3

-(CH

2

-N(CH

3 3 in which formulae z is a value from 8 to The compounds of formula I are either benzoylureas of formula Ia C k /R (Ia) wherein R 2 to Rs, m and n are as defined for formula I, or they are salts of benzoylureas of formula lb -3- ,O-NHCON--CO-0~- X9 (Ib) ef wherein R 2 to R 5 X I, m and n are as defined for formula I.

Preferred compounds are compounds of formula Ia, wherein R? is fluorine or chlorine,

R

3 is hydrogen or methyl,

R

4 is hydrogen, fluorine, chlorine, CI-C4alkyl, CI-Ci~haloalkyl, CI-Ct~alkoxy or Cl-Cqhaloalkoxy,

R

5 is hydrogen, fluorine, chlorine or CI-C4alkoxy and m and n are a value from 1 to 3; or compounds of formula Ib, wherein

R

2 is fluorine or chlorine, 1 R 3 is hydrogen or methyl, .00 R4~ is hydrogen, fluorine, chlorine, CI-C4alkyl, Cl-Gt~haloalkyl, Cl-C4alkoxy or Cl-C~haloalkoxy,

R

5 is hydrogen, fluorine, chlorine or CI-Ci~alkoxy, m and n are a value from 1 to 3 and a X is a cation of an alkali metal, or 00e, R or Rio-N in which formulae each of R 6 to R 9 independently is hydrogen, Ca-C 2 0alkyl, benzyl or phenyl and Rio is hydrogen or Cl-Czoalkyl, with X® preferably being a cation of an alkali metal, or HON 0

(CH

3 4

N®,

(C2H5)i4N ,(n-C 3 H7)4N 0, (i-C 3

H

7 )4N, HN CH -C N 'or 2 H-C 2 8 1 CH 3

-(CH

2 8 15 -N E)(CH 3 3 -4- Particularly preferred compounds are compounds of formula Ia, wherein Rz is fluorine or chlorine,

R

3 is hydrogen or methyl, R4 is hydrogen, fluorine, chlorine, methyl, CF 3 methoxy or OCF 3

R

5 is hydrogen, fluorine, chlorine or methoxy and m and n are a value from 1 to 3; or compounds of formula Ib, wherein Rz is fluorine or chlorine, lO Ra is hydrogen or methyl, R4 is hydrogen, fluorine, chlorine, methyl, CF 3 methoxy or OCF 3

R

5 is hydrogen, fluorine, chlorine or methoxy, m and n are a value from 1 to 3 and X is Na K or (CH 3 )4N (CaH 5 )4 N CH 3 -(CHz) 15 -N (CH 3 3 or R 2 is fluorine, S(n-C 9

N.

i Compounds to be singled out for particular mention on account of their activity are compounds of formula Ia, wherein Rs is fluorine, chlorine or methoxy, each in the 2- and/or It 6-positions, m is 1 or 2 and n is 1.

aee S -CONHCONH-.. _.NHCH3-.

Examples of compounds of formula la are, inter alia: .1 F F 91 ~Cl 2-* 1 *COHCNH/ r 8,Cl 4; 4; 4; 4; 4; tO o 4; t4;t 4; 4; t4; 04; 4; 4;1s 0 4; (4; c 0 4; 4; tO 4; 4; 4; (004; 99 9.99 9 09 9 9 9 *9 F F Cl H3C

CH

3 /Cl \F Cl ClC l CH 3 Cl -CONHC*H V NHCONH-9\_ -N \CH IF F Cl -CNHCONH-<__H2o

-CFCFF

Cl FF Cl Ci

C

NH- '-ONHCO- 9/

_)-OCFCHFCF

3 F F Cl T T \l *-CONHCONH-o -NHCH2-0 *-CNaFF Cl 9 9 999900 9 j1~ 9 9 N CH3 __CF 3 Cl i 6- 7C 13 C (nC.9 4 v ,Cl H Cl-. *-CQNCONH-* /V S CH 2

*-OCF

2

CHFCF

3 (n-C4H9)I+N Cl T L.,Cl 01 0 -CONCONH-< "-NI .C (C 2

H

5 4ND ft ft t -S I; f II ft S -Sf. S ft -S -S

-S

f -Sf -S -S f-Sf C S SC C S S Sf 4 5 C Sf-Sf

S

4e 0 0 0* CH3-(CH2)15-N (D (CH3)3 T Cl

CH

3 '0 CF 3 (n-C4H)N /T 0 01 9-o-

CH

2 -6 '-OCF 2 CHFCF3 /Cl -CONCONH-* *-OCF2CHFCF3 k Cl Na Na The compounds of formula Ia can be prepared by methods analogous to known ones e.g. German Offenlegungsschrift specifications 2 123 236, 2 601 780 and 3 240 975 and European patcent application 72 438).

-7- Thus, for example, compounds of formulae I and Ia can be obtained by reacting a) a compound of formula II (R4)n C /R2

-CH

2 *-NH (II) with a compound of formula III I esm

(III

on en Or o or b) a compound of formula IV ooa 3 0 o (4 D )n CH -N=C=O (IV) in the absence or presence of an organic or inorganic base, with a compound of formula V (1 04 o 0 on

*-CO-NH

2 (V Sor 0 0r c) a compound of formula II (4 )n C /2

*-NH

2

(II)

w CH2th a pn f w a m d f l1 i; with a compound of formula VI 8 *-CONH-COOR

(VI)

In the above formulae II to VI, the radicals R 2 to Rs, m and n are as defined above for formulae I and la, and R in formula VI is a Ci-Csalkyl radical which is unsubstituted or substituted by halogen, preferably chlorine.

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 a'"10 ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated t i carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform, methylene chloride, i rt t carbon tetrachloride and chlorobenzene; nitriles such as acetonitrile or propionitrile; dimethyl sulfoxide; and ketones, e.g.

acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone. Process a) is normally carried out in the temperature range from -100 to +200 0 C, preferably from 50 to 150 0 C, if t ,i desired in the presence of an organic base, e.g. triethylamine.

4 Process b) is carried outAin the temperature range from 00 to 150 0

C,

Lo preferably at the boiling point of the solvent employed and, if so: desired, in the presence of an organic base such as pyridine, and/or with the addition of an alkali metal or alkaline earth metal. For process i.e. for the reaction of the urethane of formula VI with S. a phenylenediamine of formula II, a temperature range from about 60 0 C to the boiling point of the reaction mixture is preferred, and T the solvent employed is preferably an aromatic hydrocarbon such as toluene, xylene, chlorobenzene and the like.

7- T R- y i A 9 The starting materials of formulae III and V are known and can be prepared by methods analogous to known ones. The starting materials of formula II are novel compounds which likewise constitute an object of the present invention.

The compounds of formula II can be prepared in a manner known per se by hydrogenating suitably substituted p-nitroanilines of formula VII n C 2 CH

(VII)

so es O t iii 9 by a process analogous to that described in J. Org. Chem. 29 (1964), 1, also the literature cited therein). However, phenylenediamines of formula II can also be obtained by chemical reduction with Sn(II) chloride/HCl) of the corresponding nitro compounds of formula VII Houben-Weyl, "Methoden d. org. Chemie" 11/1, p. 422). The compounds of formula VII, wherein R 2

R

3 R4 and n are as defined for formulae I and la, can be prepared by N-alkylating the corresponding nitroanilines containing an unsubstituted amino group or by reacting corresponding 4-halonitrobenzenes with the desired dialkylamines. Substituted 4-aminophenylisocyanates of formula IV can be prepared e.g. by phosgenating p-phenylenediamines of formula II by procedures which are generally employed in the art.

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

(VIII)

CIOC-COC1

CH

2 C12

H

2 S0 4

/H

2 0 O \.CONH 2

(IX)

N -CO-N-C-O oweo

(III)

i PIYXII.--L ;rI I~-i -rr il 10 In the above formulae III, VIII and IX, RS and m are as defined for formula I.

The 4 -aminophenylisocyanates of formula IV can be prepared e.g. by phosgenating the anilines of formula II by methods which are commonly employed in the art. The benzamides of formula V which are further used as starting materials are known 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 lo or by reacting a benzamide of formula V, in the presence of a base, with a corresponding ester of chloroformic acid.

The salts of formulae I and Ib are prepared in a manner known per l *e se, e.g. by reacting a resultant compound of formula Ia ttc C. R 2 CH2- *--NHCONH-CO- (la)

C

wherein Rz to R 5 m and n are as defined for formula I, with a metal r: alkanolate, e.g. sodium ethylate or potassium methylate, or with t C t corresponding ammonium hydroxides of formula X XOH (X) o 6 eQ~oee wherein X is the cation of an organic base. The salt formation is ,0O preferaby effected at room temperature and in the presence of an o alcohol, preferably methanol or ethanol. The compounds of formula Ib can also be prepared by interreaction with other suitable salts.

Pesticidal substituted N-benzyl-N'-(4-aminophenyl)ureas, the 4-amino groups of which may be substituted by alkyl or alkenyl radicals European patent application 16 729) and/or phenyl or benzyl radicals European patent application 72 438), are known.

i r-.

i i i -i I I 11 Compared with these known groups of substances, the novel compounds of formula I of the present invention have as their most essential characteristic structural feature a mandatory halogen substituent in the 2-position of the N'-phenyl ring.

Surprisingly, it has been found that the compounds of formula I of this invention have excellent properties as pesticides while being well tolerated by plants and having low toxicity to warm-blooded animals. They are particularly suitable for controlling insects and representaives of the order Acarina that attack plants and animals.

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

St( S In addition to their action against flies, e.g. Musca domestica, and mosquito larvae, the compounds of formula I are also suitable for controlling plant-destructive feeding insects in ornamentals and crops of useful plants, especially in cotton against ttLO Spodoptera littoralis and Heliothis virescens) and in fruit and vegetables against Laspeyresia pomonella, Leptinotarsa decemlineata and Epilachna varivestis). The compounds of formula I e a St 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 o feed, then a diminished oviposition and/or reduced hatching rate is observed in many insects, especially in Coleopterae, e.g. Anthonomus grandis.

Compounds of formula I are also very effective against soil insects 0lo Aulacophora femoralis, Chortophila brassicae, Diabrotica balteata, Pachnoda savignyi and Scotia ypsilon).

j 1 ^I 25 12 The compounds of formula I can also be used for controlling eccoparasites such a ticks and Lucilia sericata, in domestic animals and productive livestock, e.g. by treating animals, cowsheds, barns, stables etc., and pastures.

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

The good pesticidal activity of the compounds of formula I of the l n, invention corresponds to a mortality of at least 50-60 of the t v 4 above pests.

The activity of the compounds of formula I and of the compositions S6" containing them can be substantially broadened and adapted to S* prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, A 6 ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and a o Bacillus thuringiensis preparations.

&.Iowa The compounds of formula I are used in unmodified form, or S preferably together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner S to emulsifiable concentrates, directly sprayable or dilutable 4 solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulate6, 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.

13 The salts of formula Ib are not only distinguished by high acaricidal and insecticidal activity, but also by the fact that they are readily soluble in solvents and diluents and that they can be more easily formulated.

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).

t Suitable solvents are: aromatic hydrocarbons, preferably the 4 t t fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or t At dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or j" paraffins, alcohols and glycols and their ethers and esters, such as

S

t 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, s OLo as well as vegetable oils or epoxidised vegetable oils such as *t epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders are aaa* normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical 4 properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of 32c pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

r 14 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 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 water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal O salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-C 22 e.g. the aodium 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 S r modified and unmodified phospholipids.

tr I I More frequently, however, so-called synthetic surfactants are used, f1, t especially fatty sulfonates, fatty sulfates, sulfonated benzimidac t zole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a Co-Ca2alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.

The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing about 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the "o sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic

I

-~--.l~sayl 15 acid/formaldehyde condensation product. 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 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.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 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.

rr S, Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polypropylene/polyethylene oxide adducts, tributyl- &o phenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

s Cationic surfactants are preferably quaternary ammonium salts which

S

contain, as N-substituent, at least one CS-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in a* the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniUm chloride or benzyldi-(2-chloroethyl)ethylammonium o0 bromide.

T

16 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.

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

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

Example 1 a) Preparation of the intermediate of the formula 09 9.9,

CH

3 CH2-* 0 O 32.4 g of 4-(N-methyl-N-benzyl)-2-fluoro-3,5-dichloronitrobenzene are dissolved in 330 ml of tetrahydrofuran and hydrogenated for 24 hours with 6.95 F of H 2 in the presence of 6 g of Raney nickel.

The reaction mixture is filtered, and the filtrate is concentrated and distilled, affording the title compound with a boiling point of 180-190 0 C/0.05 torr.

In corresponding manner the intermediate of the formula -17- VS- lCH3 HN. CH2-<_ >-C1 n 34 1,6400 b) Preparation of compound 1.1 of the formula ?/Cl

H

OH

2 With stirring, 3.12 g of 2,6-difluorobenzoylisocyanate are added dropwise to a solution of 5.1 g of 4-(N-methyl-N-benzylamino)-2fluoro-3,5-dichloroaniline in 50 ml of toluene. The reaction mixture is stirred for 4 hours at 20%0 and then partially concentrated. The obtained concentrate is filtered by suction. The product is washed on the suction filter with cold toluene and then dried, affording The following compounds of formula Ia are prepared in analogous manner: 4 9 compound 1.2 0 o ,-CONHCONH-o/ \-N1CH Cl

H-

141-142%C 18 compound 1.3 F T C

CH

3 >-CONHCONH--m/ \CH 2 138-14O*C compound 1.4 -CONC/C-N

CH

3 \CH2,

\OCH

3 c1 156-157%C It it I I I I I II Ii III i

I

I I III

I,

I

I I~ 4 4 1 1411 t I 4$ compound :F y_/1 CH 3 \/HCNH -NI C r~f?~1HrMU-\ -N 0= 161-1620C compound 1.6

I

004400 0 0 *4440:

I

*4 I 00 00 /0 COHON-/ 0\-1 CH 3 Cl 177-178*C -19compound 1.7 /Cl /Cl 198-200'C compound 1.8

_CH

3 196-198*C c) Preparation of the sodium salt of N-(2,6-difluorobenzoyl)-N'- 4* (4-benzylmethylamino-2-fluoro-3, g of N-(2,6-difluorobenzoyl)-N'-(4-benzylmethylamino-2-fluoro- 3,5-dichlorophenyl)urea are suspended in 35 ml of methanol. With stirring, a solution of 0.45 g of Na in 20 ml of methanol is added o dropwise to the resultant suspension. The solution is stirred for a further 30 minutes at 20 0 C. The methanol is distilled off, affording compound 2.1 of the formula 44 /F e /1 9/ Y Na 0 with a melting point of l65-166*C The following compounds of formula Ia can also be obtained as described above: 9-NHC~HC ONHC0- (Ia)

NO.

1.9 F H 4-CH3 2,6-F 2 z 1.10F9 4-CH 3 2-Cl, 6-F1 2 1. 11 F H 4-CH3 2-Cl 2 1.12 F H 4-CH 3 2-F 1 I 1.13 Cl H1 4-CH 3 2, 6-F 2 1 2 1.14 Cl H 4-CH 3 2-Cl, 6-F 1 2 1.15 Cl H4-03 11 2-Cl 11 1.16 Cl H 4-CH I 2-F 1.17 F

CH

3 4-CH3 2,6-F2 1.18 F CH 3 4-CH 3 2-Cl, 6-F 1 2 1.19 F CH 3 4-CHs 2-Cl1 1 go 1.20 F CH3 4-CHs 2-F1 1 1.21 Cl CH 3 4-CH 3 2,6-F 2 1 2 1.2 Cl

CH

3 4-CH 3 2-Cl, 6-F 1 2 to #5 1,23 Cl CH 3 4-CH 3 2-Cl1 1 t. 1.2A Cl CH 3 4-CH 3 2-F1 1 a1. 25 ,4(H 2,6-Fz 2 2 1.26 F H 2,4-(c.H 3 )z 2C,(F2 2 1.27 F H2,4-(CH 3 2-Cl, 2 1 1.28 F H 22-2 1 12 7 Cl H 2,4-(C,6 3 2 2,6F 2 2 1.30 Cl 24 CH 2 2l -F 2 2 1.31 Cl H 26(~ 3 22C 1.2 C 2, 4-(CH 3 )a 2 -F 2 2 2 1.33 Fl CH 2 4-(Ci j 26-F 1.34 F I C 2 4-(CE 3 2 2 -C 6- 2 2 .3 FCH I 2 ,4-(Ci 3 )2 j 2-Cl 2 1. 36 c F CH I n,-C 3 a 1 C.37 Cl CH1i3 2 4-(CH-132 2,6-F 2 2 2 1.38cCI CH 3 2,4-(CH 3 )2 2-Cl, 6-F 2 2 ,ec, 1.39 Fl CH 3 2,-CH 2-Cl 2 1 1.40 Cl CH3 2 ,4-(CH 3 )z 2-F2 1 1.41 Fl CH, 2,4-(CH3 2 2,6-F 2 12 .4

C

2 H 2l-(CH,) 2-Cl, 6-F 1 2 1.38 F2 2 4- CH 3 2-Cl 2 1 1.44 Fl C 2 s CH3 2-F 2. 1 1.45 Cl CH3 24- CH 3 2,- 2 2 1.46 Cl

C

2 H5 4-CH 3 2C, 6-F 1 2 1.7 C C 2 Hs 4-CH3 2-Cl 1 2 1.48 Cl

C

2 H5 4-CH3 2-F1 1 1.49 Fl

C

2 H5 24-CH 3 2,6-F 2 2 2 CH~ 24-CH 3 2-Cl, 6-F 2 2 1.451 F C 2

H

5

I,-C-

3 z2C 1.452 F

C

2 HS 24-(CH3a 2-F 2 1538 Cl C 2 H5 L4-CH3i~ 2, -F 2 1.54 Cl

C,,H

5 2-Cl, 6-F 2 2 1.55 Cl CzH5 2,4-(CH 3 2 2-Cl 2 1 Cl C2H5 2,4-(CH! 3 2 2-F 2 1 j FC34-(,-"3t) 2 C, 6-F 2 2 .4rl -21 Cornpound V 00 00 o p 0 0 0 00 0 0 000 0 o 00 8 0 000 0 0 00 o p 0 000 0 00 0 0 0000 0004 0 0 $004 0 00 00 0 00 00 IG 0

S

00 o 0 0 1.58 1.59 1.60 1.61 1.62 1.63 1. 64 1.67 1.68 1.69 170 1.71 1.72 1.73 1.74 1.7 1.76 177 1.78 1 .79cl 1.80 1. 81 1.82 1 .83 1.84 1.85 1.86 1.7 1.88 i. 89 1.90 1.91 1.92 1.93 1.94.

1.95 1.96 1.97 1.98 1.99 1. 100 i. 101 1. 102 1. 103 1.104 1.105 1.106

F

F

F

Cl Cl Cl Cl

F

Cl

F

Cl

F

F

F

F

Cl Cl Cl Cl

F

F

F

F

Cl cl Cl

F

F

Cl Cl Cl

F

F

F

Cl Cl Cl Cl

F

F

F

F

Cl Cl CH 3

CM

3 CM 3 CH 3 CM 2

CH

3 CM 3

CH

3 CM 3 CH 3 CH3 C 2 M H

C

2 H5

C

2 H5 C 2H 5 CM 3 CH 3 CM 3

CM

3 CH3

CHM

3

CM

3

C

3

CHM

3

CH

3

CM

3

CH

3

CM

3 CM 3

CM

3

CM

3

CM

3

CH

3

CM

3

CM

3

CM

3 CM 3

CM

3

CM

3

CM

3 CH 3 4-C~ 4

H

9 t) 4-C4H9( t) 4-Ct M 9 (t) 4-C HM 9 (t) 4-C4,H 9( t) t) 4-Cl 9t 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 3-Cl 3-Cl 3-Cl 3-Cl 3-Cl 3-Cl 3-Cl 3-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2,-Cl 2 2,4-Cl 2 2 ,4-Cl 2 2,14-Cl 2 2, 4-Cl z 2,4-Cl 2 2,4-Cl 2 2, 4-Cl 2 z 2,34-Cl 2 2,)3-Cl 2 2 3-Cl 2 2,3-Cl 2 z 2,3-Cl 2 2,3-Cla

R

5 2-Cl, 6-F 2-Cl 2-F 2,6-F 2 2-Cl, 6-F 2-Cl 2-F 2-F 2- F 2-Cl, 6-F 2-Cl, 6-F 2 ,6-F 2 2-Cl, 6-F 2-Cl 2-F 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2,6-F- 2-Cl 6-F 2-Cl 2-F 2 6-F 2 2-Cl, 6-F 2-Cl 2-F 2,16-F 2 2-Cl, 6-F 2-Cl 2-F 2,6-F 2 2-Cl 6-F 2-Cl 2-F 2, 6-F 2 2-Cl, 6-F 2--Cl 2-F 2,6-F 2 2-Cl, 6-F 2-Cl 2-F 2 ,6-F 2 2-Cl, 6-F -v n 1 1 2 1 2 1 2 1 1 2 1 1 1 1

I

Tn 2 1 2 2 2 1 1 2 2 2 2 2 1 1 2 2 1 1 2 2 12 2 2 cLy

-,AI

3 4 22 CC @9 4 e #9 C 9 9 tt~ 9 C (9 C 4 4 Ce. 9* a C (It C at 9 C C 4~ C ccr

C

(CCC

C C C ~C a. CC I C t 9 9 CzniPoUnd R, 1.107 cl 1.108 Cl 1.109 F 1.110 F 1.111 F 1.112 Cl 1,113 Cl 1.114 Cl 115 -J 1,116 F 1.117 F 1. 118 F 1.119 F 1.120 Cl 1. 121 Cl' 1.122 Cl 1. 123 Cl 1.1I2 4 F 1,125 F 1,126 F

F

1.130 Cl 11 Cl

F

i. 136 Cl 1,137 01 1 1"38 01 1. ,0 I1141 F 11242 F 1,143 F 1.144 Cl 1.145 Cl 1.146 Cl 1.147 C1 1.148 F 1.149 F 1.150 F 1.151I F 1.1 52 Cl 1.153 Cl 1.154 Cl 1.155 01

CH

3

CH

3

CH

3 CH3

CH

3 01H3

CH

3

OH

3 CH 3 OH 3 OH 3 CH 3 CH 3 OH3

OH

3 OH 3

CH

3 CH 3 OH 3 OH3

CH'

CH

3

OH

3 OH 3 CH3 CH

OH

3

OH

OH

3

OH

3 OH3

OH

3 CH 11

OH

3 OH3 OH3 OHi

OH

3

OH

3

OH

3 0H13

OH

3 CH3 OH3

OH

3 OH 3 CH 3

OH

3

OH

3 2,43-01 2 2,3-Cl12 3, 4-012 3,14-012 3, 4-01 2 3, 4-01 2 3, 4-0 2 3,4-01 2 3, 5-Cl 2 3, 5-C12 3, 5-C12 3, 5-C12 3, 5-01 2 5-012 3 ,5-C12 3, 5-01 2 2-0H3, 4-Cl 2-OH 3 4-Cl 2-OH!, 4-Cl 2-OH1, 4-Cl 2-OK3, 4-01 2-OH 3 4-Cl 2-0H 1, 401l 2-OK3, 5-01 2-01- 3 5-01 2-OH 3 501l '2-COH 3 5-C! 2-0Ha, 5-Cl 2-OH; 3 501l 2-OH 3 5-Cl 2-OH 3 5-Cl 2-Cl, 5-Hl 2-01, 4-OH 3 2-01, 4-OH 3 2-Cl, 4-OH 3 2-Cl, 4-OH 3 2-Cl, 4-OH 3 2-Cl, 4-OH 3 2-01, 4-OH 3 2-Cl, 5-OH 3 2-Cl, 5-OH 3 2-Cl, 5-OH 3 2-01, 5-OH 3 2-Cl, 5-OH 3 2-01, 5-OH 3 2-01 5-OH 3 2-Cl, 57-OH 3 2-01 2-F 2-01, 6-F 2-Cl 2-F 2 6-F 2 2-01, 6-F 2-01 2-F 2,6-F 2 2-01, 6-F 2-Cl 2)-F 2, 6-F 2 2-01 6-F 2-01 2-F 2, 6-F, 2-01, 6-F 2-C!

F

2-Cl1, 6-F 2-Cl 2-F -2,6-F- 2-01 6--F 2-Cl 2-F 2, 6-F, 2-Cl 2,-01 2, 6-F 2 2-Cl 6-F 2Z-Cl 2-F 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2,6-F 2 2-02 6-F 2-F 2,6-F 2 2-01 6-F 2-01 2-F 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2.

2.

2 2 2 2 2 2 2 2 2 R R 23 Conpound R3 LW). j I.

9 .06 *e 0 9 0t 6000 1.156 1.157 1.158 1.159 1.160 1. 161 1. 162 1.163 1.164 1.165 1.166 1.167 1.168 1.169 1.170 1.171 1.172 1.173 1.174 1. 175 176 1.177 1.178 1.179 i.180 1.181 1.182 1.183 1.184 1.185 1. 186 1.187 1; 188 1.189 1.190 1.191 1.192 1.193 1.194 1.195 1.196 1.197 1.198 1.199 1.200 1.201 1.202 1.203 1.204

F

F

F

F

cl cl Cl Cl

F

F

F

'F

Cl Cl ci ci

F

F

F

F

cl cl C -1 cl

F

F

F

cl cl cl Cl

F

F

F

F

Cl Cl Cl Cl

F

F

CH

3 CH3

CH

3 CH3 CH3 CH3 CH3 CH3

CH

3 CH CH3

CH

3

CH

3 CH3 CH 3

CH

3

CM

3

CM

3

CM

3 CM 3 CH 3

CH

3 CM

CH

CH3

CH

3

CH

3

CH

CH

3

CH,

CH

3 CH'3

CHM

3

CH

3

CH

3

CM

3

CH

3

CH

3

OH

3 CH3

CH

3

CH

CH

CH 3

CH

3

CH

3

CH

CH

3

CM

3 R4 4-F 4-F 4-F 4-F 4-F 4-F 4-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 2, 4 5-Cl3 2, 4, 5-Cl2 2 4, 5-Cl 2,4, 5-C13 2 4 5-C!l 2,4,3-C13 2,4,5-Cl 3 2 4, 5-C! 2,4-C12, 5-CM 3 2,4-Cl 2 5-CH 3 2,4-Cl 2 5-CM 3 2,4-Cl 2 5-CH 3 2,4-Cl2, 5-CH 3 2,4-Cl 2 5-CH 3 2,4-Cl 2 5-CHj 2,4-012, 5-CM 3 2,4-(CM 3 2 ,5-Cl 2,4-(CH 3 2 ,5-Cl 2,4-(CM 3 2 ,5-Cl 2,4-(CH 3 )2,5-Cl 2,4-(CH 3 )2,5-Cl 2,4-(CM 3 2 ,5-Cl 2,4-(CM 3 2 ,5-Cl 2,4-(CH 3 2 ,5-C 3,4,5-Cl 3 3,4, 5-C13 3,4, 5-C13 3,4, 5-C13 3,4 5-Cl3 3,4,5-Cl3 3,4,5-Cl 3,4,5-C13 4-Br R5 n m 2,6-F. 1 2 2-Cl, 6-F 1 2 2-Cl 1 1 2-F 1 1 2,6-F 2 1 2 2-Cl, 6-F 1 2 2-Cl 1 1 2-F 1 1 2 6-F 2 1 2 2-Cl, 6-F 1 2 2-Cl I 1 2-F 1 1 2,6-lU 1 2 2-Cl, 6-F 1 2 2-Cl 1 1 2-F 1 1 2,6-F 2 3 2 2-Cl, 6-F 3 2 2-Cl 3 1 2-F 3 1 2,6-F 2 3 2-Cl, 6-F 3 2-Cl 3 1 2-F 3 1 2,6-F 2 3 2 2-Cl, 6-F 3 2 2-Cl 3 1 2-F 3 1 2,6-F 2 3 2 2-Cl, 6-F 3 2 2-Cl 3 1 2-F 3 1 2,6-F 2 3 2 2-Cl, 6-F 3 2 2-Cl 3 1 2-F 3 1 2,6-F 2 3 2 2-Cl, 6-F 3 2 2-Cl 3 1 2-F 3 1 2,6-F 2 3 2 2-Cl, 6-F 3 2 2-Cl 3 1 2-F 3 1 2,6-F 2 3 2 2-Cl, 6-F 3 2 2-Cl. 3 1 2-F 3 1 2,6-F 2 1 2 *6*6

I

09 9*66: 9 a *6 0.

@0 00 *e 0 0* 0 0 .16.1 I i a 24 70q1)ud I R2 NoR 3 R 5 n M, a. a.

9 p 0 99 9 *0 0 ao 0 0 000 9 o 00 0 0 000 0 90 9 0 0 0~ 0 0009

I

09*6 0000 0 60 00 9 00 00 00 0 0 00 0 00 1.205 1.206 1.207 1.208 1.209 1. 210 1.211 1.212 1.213 1.214 L.215 1.216 1.217 1.218 1.219 1.220 1.221 1.222 1.223 1. 224 1.225 1.226 1.227 1.228 1.229 1. 230 1.231 1.232 1.233 1,234 1.235 1. 236 1. 237 1.238 1.239 1.240 1.241 1.2 42 1.243 1.244 1.245 1.246 1.247 1.248 1.249 1.250 1.251 1 .252 1.253

CH-

3

CH

3

CH

3 CH 3

CH

3

CH

3 CH 3

CH

3

CH

3

CH

3

CH

3

CH-

3

CH

3 CH3 CH 3

C

2 Hs c 2 HSl C 2 H 5,

CZHS

C 5

C

2

H

5

C

2

H

5 C 2 H 5 C2Hs

C

2

HS

C 2 i 4-Br 4-Br 4-Br 4-Br 4-Br 4-Br 4-Br 2-CH 3 4-Br 2-CH 3 4-Br 2-CH 3 4-Br 2-CH 3 4-Br 2-CH 3 4-Br 2-CH 3 4-Br 2-CH 3 4-Br 2-CH 3 4-Br 2-Br 4-CH 3 2-Br, 4-CH 3 2-Br, 4-OH 3 2-Br, 4-CH 3 2-Br, 4-CH 3 2-Br, 4-OH 3 2-Br, 4-CH 3 2-Br, 4-CH 3 4-CF 3 4-CFi 4-C I -CF 3 4-CF 3 4-CF 3 4-CF 3 4-CF 3 3-CF 3 3-CF 1 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3- CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 4-CF, 3 4-CF 3 4-CF 3 2-Cl, 6-F 2-Cl 2-F 2,6-F7 2-Cl, 6-F 2-Cl 2-F 2 6-F 2 2-Cl, 6-F 2-Cl 2-F 2, 6-F, 2-Cl, 6-F 2-Cl 2-F 2, 6-F2 2-Cl, 6-F 2-Cl 2-F 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2.6-F 2 2-Cl, 6-F 2I-Cl1 2-F 2 ,6 -F 2 2-Cl, 6-F 2-Cl 2-F 2-Cl, 6-F 2-Cl 2-F 2 ,6-F 2 2-Cl, 6-F 2-Cl 2-F 2 ,6-Fz 2-Cl, 6-F 2-Cl 2-F 2 6--F 2 2-Cl, 6-F 2-Cl 2-F 2 6-F 2 2-Cl-, 6-F 2-Cl ji 25 CaTpo 14R Nbu.ndT R, T -T r 4 4 4-C

C

I C Cr t .*I C ~I C 4, C C C CC

I~C

C

C I*.t C 4.

.444" 1.254 2j'5 1.256 1.257 1,258 1.259 1.260 1.261 1. 262 1.263 .264 1.265 1.266 1.267 1268 1.269 1.270 1.271 1.272 1273- 1.275 1.276 1.277 1.278 1.279 1.280 1. 281 1.282 1.283 1.284 1.285 1.286 1. 287 1.288 1.289 1.290 1.291 1.292 1.293 1.294 1.295 1. 296 1.297 1.298 1.299 1. 300 1.301 1. 302

C

2 H5

C

2 HiS

C

2 H5

C

2 H5

C

2

H

5

CH

3

CR

3

CH

3

CR

3

CH

3

CH

3

CH

3

CH

3

CH

3

CR

3

CH

3

CR

3

OH

3

CR

3

CR

3

CH

3 CHR1

CRH

3

CH

3 CH 3

CH

3

CR

3

CH

3

CR

3

CH

3

CR

3

CR

3

CR

3

CH

3

CR

3

CH

3

CH

3

CH

3

CH

3

OH

3

CH

3

CH

3

CR

3

CH

3

CH

3

CH

3

CH

3 Cli 3

CH

3 4-OF 3 4-CF 3 4-CF 3 4-CF 3 4-CF 3 2-Cl, 2-Cl, 2-Cl, 2-Cl, 2-Cl, 2-Cl, 2-Cl, 2-Cl, 3-OF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 1 4-CF 3 4-CF 3 4-CF 3 4 -CF 3 4-CF 3 4-CF 3 1,-CF 3 4-CF 3 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4i-Cl 4-OCR 3 4-OCR 3 4-OCH 3 4-OCH 3 4-OCR 3 4-OCR 3 4-OCR 3 4-OCR 3 3-OCR 3 3-OCR 3 3-OCR 3 3-OCR 3 3-OCH 3 3-OCR 3 3-OCR 3 3-OCR 3 4-oc, HR 9 4-oC4,H 9

I

4-0c4H 9 4 -OC 4 H 9 4-OCR 9 4-OC IH 4-QC4H 9 4-oC4,Hq 4-ocF 3 4-OCF 3 4 -OCF 3 4-OCF 3 2-F 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2, 16-F 2 2-Cl, 6-F 2-Cl 2-F 2 ,6-F 2 2)-Cl, 6-F 2-Cl 2-F 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2, 6-F, 2-Cl, 6-F 2 Cl 2-F 2,6--F 2 2-Cl 6-F 2-Cl 2-F 2 ,6-F 2 2-Cl, 6-F 2-Cl 2-F 2,6-F 2 2-Cl, 6-F 2-Cl 2-F 2,6-F 2 2-Cl, 6-F 2-Cl 2-F 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2-Cl, 6-F 2-Cl 2-F 2 ,6-F 2

%TO

26 OqnioUnd R2 R R 3 Ril Rn F ft

I

I

F F C C F 4 F F Fit I 4 44 F F 4Ff' *441

I

*411

F

14 4, F F. II I I 4 I 4 44 44 4 .44, 1. 303 1.304 1.305 1.306 1.307 1.308 1. 309 IN31 1. 311 ):13212 1.313 1.314 1.315 1. 316 1.317 1. 318 1. 319 1. 320 1.321 1.322 1.2323 1.324 ~325 1.326 1.327 1. 328 1.329 1.331 1.332 2.332 33 1.2335 1.336 1.337 1. 337 1. 38 0.3 1.341 1,341 1. 342 1.343 I .345 1.346 1.347 1,348 1.349 11350 1. M~ Cl Cl Cl

F

F

F

CQ

CI

F

F

(;I

cl

F

F

F

F

Cl c I Cl

F

F

F

F

cl Cl Cl -Cl

F

F

Cl cl Cl

CH

3 Cil3

CH

3

CH

3 Cil 3 Cil 3 Cil 3

CH

3 C H 3 Cil 3 CH 3 Oil 3 Cil) Cil 3

CH,

OH

3 Cil3 Cul CH 3 C2H 5 C2H5.

CaHs CH5

OH

3

CH

3

CH

3

OH

3 cH 3 Cil3 Cil3 C11 3 Of i CH3

OH

3

OH

3 4-OCF3 4 -0CF3 4-OCF3 4- 0CF 2 CF3 4-OCFaCF3 4-OCF 2 CF3 4-OCF 2 CF3 4-OCF 2 CF3 4-OCF 2

CF

3 4-OCFZCF 3 4-OCF 2 ,CF3 4-OCF 2 C1IFCF 3 4-OCF 2

CHFCF,

3 ?I OP r OilCF 3 4-OCF.C.HFCF 3 4-OCF 2 CIFCI-a 4-0 CF 2 OH FCF 3 4 -ocr 2 CHFC1 4-OCF 2 CirlFO 4 -OCF 2 CHFCl 4-0 CF 2 C~iIFC 1 4-OCF 2

C)JFCI

4-OCF 2 CHrFc1 I4-OCF 2 CxrlF~ 4-0 CFg~CHiFO 4-OCF 2

CHFCF

3 4-OCFZCilFCF-, 4-OCF 2

CHFCF

3 4-OC aCHFoF 3 4-COP CFHF, 4-OCFZCHFCF3 4 OCFac)fl'CF 4-oOF- 2

CHFOF

3 4-OCF 2 pCHV a 4-00F 2 0HF 2 4-OCFacHF2 4-OCFCliF2 4-ocracIIF2 4-C 2 CHF2 4-OCP2 C1IF2 4-OCF2OIIra 4 -OCrzCHVBr 4 -CaC)ICF]3r 4-C 2 CHIh 4-COPCFi 4-OCF 2 CHF~r 4- cCtoi' HPrt 4-CCIICFB r 4-0CrIOHF1r 2-02., 6-F 2-C.

2-r 2 ,6-F 2 2-Cl, 6-F 2-C).

2-F 2 ,6-Fz 2-Gi, 6-F' 2-Cl 2-F 2-Cl, 6-F 2-Cl 2, 6-F 2 2-Cl, 6-F 2-Cl 2-F 2, 6-F 2 6-Pt 2-C! 2-F 2 6-F,, 2-Cl, 6-F 2-Cl 6-F? 2-0.1, 6-F 2-Cl 2-FV 2,)6-F 2 2-Cl, 6 F 2-F1 2,6-P 2 2-Cl, 6-F 2-Cl 2 -P 2,16-F 2 2-Cl, 6-F 2-Ct 2-F 2 )6-F2 2-Cl, 6-P 2-C).

2-F 2-Cl 6-F 2-01 2-F O' 27 Conpound R2 R3 R4 R5 n m 1.352 F CH 3 ,3,4,5,6-Fs 2,6-F 2 5 2 1.353 F OH 3 2,3,4,5,6-Fs 2-C1, 6-F 5 2 1.354 F CH 3 2,3,4,5,6-F5 2-Cl 5 1 1.355 F CH3 2,3,4,5,6-F 5 2-F 5 1 1.356 C1 H 3 2,3,4,5,6-Fs 2)6-F 2 5 2 1.37 Cl I CH 2,3,4,5,6-F5 2-Cl, 6-F 5 2 1.358 C1 CH 3 2,3,4,5,6-Fs 2-Cl 5 1 1.359 Cl CH3 2,3,4,5,6-F5 2-F 5 1 1.360 F CH 3 1-CH 3 2,6-F, 5 2 1.361 F CH 3 4-CH 3 ,213,5,6-F4 2-Cl, 6-F 5 2 1.362 F CH 3 4 -CH3 2 3, 5, 6- F: 2-C1 5 1 1.363 F CH 3 4-CH 3 2, 3, 5, 6-F 2-F 5 1 1.364 cl CH 3 4-CH 3 ,2,3,5,6-F4 2,6-F, 5 2 1.365 Cl CH 3 4 -CH 3 2,31 6-Fk 2-Cl, 6-F 5 2 1.366 ci CH3 4-CH 3 ,2,3,5,6-F4 2-Cl 5 1 1.367 c3 4-CH 3 ,2,3,5,6-F4 2-F 5 1 gr t t i.

it 9 Iii I CI i Ii i 1e11 In accordance with also be prepared One present invention, the above compounds may as indicated above in the form of their sc1ts Examole 2: Formulation Examples for Prenaratorv Example 1 (throughout, active ingredients accordingl to oercentages are b' wcipht)

I

Ittt *i 4 I I 9 Iiir 2.1. Emulsifiable concentrates compound according to Preparatory Example I calcium dodecylbenzene sulfonate castor oil polychylene glycol ether (36 moles of ethylene oxide) tribuvylphenol polyethylene glycol other (30 moles of ethyleni oxide) castor oil thioxilate cyclohexanone buanol Xylone mixture ethyl acetate a) b) c) d) 10 25 15 50 12 15 25 4 20 20 Emulsions of any required concentration concentratea by dilution with water.

can be produced from such

.I~

I

28 2.2 Solutions a) b) compound according to preparatory Example 1 ethylene glycol monomethyl ether polyethylene glycol (mol.wt. 400) N-methyl-2-pyrrolidone expoxidised coconut oil ligroin (boiling range 160-1900C) These solutions are suitable for application drops.

2.3. Granulates 10 5 70 20 1% S 94 in the form of microa) b) r :II t tf 4 f'

I+

It 44 4i 4.

4 compound according to Preparatory Example 1 kaolin highly dispersed silicic acid attapulgite 10 90 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

9 4

S

S

4* 44 2.4. Dusts compound according to Preparatory Fxample 1 highly dispersed silicic acid talcum kaolin Ready for use dusts are obtained by with the active ingredient.

a) b) c) d) 2% 1 97 5% 5 90 5% 95 8% 92 intimately mixing the carriers ;i c~

C,

_i arrr~rrq~ 29 Wettable powders a) compound according to Preparatory Example 1 20 sodium lignosulfonate 5 sodium laurylsulfate 3 sodium diisobutylnaphthalenesulfonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid 5 tO kaolin 67 b) c) 50 5% 6% 2% 10 27 75 10 10 The active ingredient 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.

44 *4 4

,D

4 tr

I

IP

4 4

S

1 2.6. Extruder granulate compound according to Preparatory Example 1 sodium lignosulfonate carboxymethylcellulose O kaolin 10 2% 1 87

I

4

S

The active ingredient 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.

2.7. Coated granulate compound according to Preparatory Example 1 polyethylene glycol (mol.wt. 200) kaolin 3% 3% 94 The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

2.8. Suspension concentrate compound according to Preparatory Example 1 40 ethylene glycol 10 nonylphenol polyethylene glycol ether moles of ethylene oxide) 6 to 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 0 Example 3: Action against Musca domestica 00 Example 3: Action against Musca domestica c a O 50 g of freshly prepared nutrient substrate for maggots are charged 0 into each of a number of beakers. A specific amount of an acetonic f solution containing 1 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 i thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 20 hours.

7 I 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.

iz_ 11 31 Each batch of flushed out pupae is counted to determine the toxic effect of the test compound on the maggot development. A count is then made after 10 days of the number of flies which have hatched out of the pupae.

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 formulation containing 0.5 by weight of test compound is added at 5000C to 9 ml of a culture medium. Then about 1o 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.

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

r r S' Example 5: Action against Aedes 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 o Addes aegypti are put into the beaker containing the test compound.

Sc 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.

S" Example 6: Insecticidal stomach poison action Cotton plants about 25 cm high, in pots, are sprayed with aqueous emulsions which contain the respective test compound in increasing concentrations of up to 100 ppm. After the spray coating has dried, the cotton plants are populated with Spodoptera littoralis and i~"rr)l 32 Heliothis virescens larvae in the L 3 -stage. The test is carried out at 24°C and 60 relative humidity. The percentage mortality of the test insects is determined after 120 hours.

At a concentration of 12.5 ppm, compounds 1, 2 and 3 effect 80 to 100 mortality against Spodoptera and Heliothis larvae.

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 'O 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 t damage (anti-feeding effect), and of inhibition of development and shedding, is made by observing the test insects for a further S3 days.

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

L.o 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.

Compounds of formula I according to Example 1 exhibit good activity 3o in this test.

S' JJ.. 33 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.

After the solution has dried, the eggs are placed in petri dishes and kept at a temperature of 28 0 C. The percentage of larvae hatched from the treated eggs and the percentage mortality are evaluated after 6 days.

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

Example 10: Influence on the reproduction of Anthonomus grandis Anthonomus grandis adults which are not more than 24 hours old after i* hatching are transferred in groups of 25 to barred cages. The cages S' are then immersed for 5 to 10 seconds in an acetonic solution tt t tt containing 0.1 by weight of the test compound. After the beetles t chave dried, they are placed in covered dishes containing feed and r, '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 Sao then placed in dishes containing a suitable larval feed. A count is made after 7 days to determine whether larvae have developed from S'c 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 "N 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 reproduction inhibiting activity in this test.

rrrr~a~ raaepr~ 34 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 coa-ing has dried (about 1 1/2 hours), each plant is populated with 10 adult beetles (Anthonomus grandis). Plastic cylinders, covered at the top with gauze, are then slipped over the treated plants populated with the test insects to prevent the beetles from migrating from the plants.

The treated plants are then kept at 25 0 C and about 60 relative O humidity. Evaluation is made after 2, 3, 4 and 5 days to determine the percentage mortality of the beetles (percentage in dorsal position) as well as the anti-feeding action as compared with untreated controls.

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

t c t re Example 12: Insecticidal stomach poison action against Plutella r C xylostella Potted Chinese cabbage plants (pot size: 10 cm diameter) in the 4-leaf stage are sprayed with aqueous emulsions which contain the S test compound in a concentration of 800 ppm and which dry on the Sr' plants.

After 2 days, each treated Chinese cabbage plant is populated with Plutella xylostella larvae in the L 2 -stage. The test is carried out at 24°C and at 60 relative humidity in dim light. After 2 and 5 days evaluation is made to determine the percentage mortaility of the larvae.

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

35 Example 13: Action against ticks: killing action in various development stages About 50 larvae, about 25 nymphs or about 10 imagines of each of the tick species Rhipicephalus bursa, Amblyomma hebraeum and Boophilus microplus are used as test animals. The test animals are immersed for a short time in aqueous emulsions containing the respective test compound in a concentration of 800 ppm. The emulsions, which are contained in test tubes, are then absorbed by cotton wool, and the wetted test animals are left in the test tubes which have thus been to contaminated. Evaluation of the percentage mortality is made 3 days later in the case of the larvae and 14 days later in the case of the nymphs and imagines.

In this test, compounds of formula I according to Example 1 are very effective.

C t i Example 14: Action against ticks: inhibition of oviposition vVL C Adult females of the cattle tick Boophilus microplus which are fully C C Cl replete with blood are used as test animals. 10 ticks of an OPts t sensitive strain Biarra strain) and 10 ticks of a normally 4,C( sensitive strain Yeerongpilly strain) are treated. The ticks L'CO are affixed to plates to which double-sided adhesive tape has been I applied and are then either wetted with aqueous emulsions or *solutions containing 800 ppm of the test compound or are brought into contact with cotton wool which has been impregnated with these Sliquids. The ticks are subsequently kept in a climatised chamber under constant conditions. Evaluation is made after 3 weeks. The percentage inhibition of the deposit of fertile eggs is determined in comparison with untreated controls.

8 *t S In this test, compounds of formula I according to Example 1 exhibit very good activity.

Claims (6)

1. A compound of formula I Sn R3 C /R CH 2 -NHCOR 1 (I) wherein (Os) (1s) X® m m R 1 is *-CONH- or -CON- Rz is halogen, R 3 is hydrogen or Cl-C6alkyl, R4 is hydrogen, halogen, CI-C 6 alkyl, Ci-Cshaloalkyl, Ci-C 6 alkoxy, Ci-C 6 haloalkoxy, cyano or nitro, R 5 is hydrogen, halogen or Ci-C 6 alkoxy, m and n are a value from 1 to 5, with the proviso that the indi- vidual substituents R4 may differ in meaning from one another if n is a value from 2 to 5 and that the individual substituents Rs may differ in meaning from one another if m is a value from 2 to Sft and X is an inorganic or organic cation.

2. A compound according to claim 1 of formula Ia S)n ./R 2 )m S alad o--CH2- *-NHCONH-CO--. (Ia) SClf wherein Ra is halogen, Ra is hydrogen or Ci-C 6 alkyl, 37 R4 is hydrogen, halogen, Ci-C~alkyl, Cl-C 6 haloalkyl, CI-C 6 alkoxy, Ci-C6haloalkoxy, cyano or nitro, R 5 is hydrogen, halogen or Cl-C 6 alkoxy and m and n are a value from 1 to

3. A compound according to claim 1 of formula lb nC R 1 ze 4, z 0= I/c 0 Ib) wherein R 2 is halogen, R 3 is hydrogen or Cl-C 6 alkyl, R 4 is hydrogen, halogen, Cl-C 6 alkyl, Cl-C 6 haloalkyl, CI-C 6 alkoxy, Cl-C 6 haloalkoxy, cyano or nitro, R 5 is hydrogen, halogen or CI-Cealkoxy, mn and n are a value from 1 to ft LI- 1* L~ A- C A-C C C Cr C A t~ LA I Aft. IA A 0 IL and xe

4. R 2 R 3 I? 0 0£) 0 ~A 0 0 is an inorganic or organic cation. A compound according to claim 2 of formula Ia, wherein is fluorine or chlorine, is hydrogen or methyl, is hydrogen, fluorine, chlorine, CI-C4alkyl, C 1 -Ci~haloalkyl, Cl-C4alkoxy or 0 1 -C 4 haloalkoxy, is hydrogen, fluorine, chlorine or C 1 -Ci~alkoxy and and n are a value from 1 to 3. A compound according to claim 4 of formula Ia, wherein is fluorine or chlorine, is hydrogen or methyl, is hydrogen, fluorine, chlorine, methyl, CF 3 methoxy or OCF 3 is hydrogen, fluorine, chlorine or methoxy and and n are a value from 1 to 3. 0 l a %/VT -38-

6. A compound according to claim 3 of formula Ib, wherein R 2 is fluorine or chlorine, R 3 is hydrogen or methyl, R 4 is hydrogen, fluorine, chlorine, CI-C4alkyl, Ci-Cthaloalkyl, CI-C4alkoxy or Cl-C 4 haloalkoxy, *R 5 is hydrogen, fluorine, chlorine or Cl-C4alkoxy, m and n are a value from 1 to 3 and X is a cation of an alkali metal, or 7 R 61 R 8 or Ri- in which formulae

119. 0000 each of R 6 to R 9 independently is hydrogen, CI-C 2 oalkyl, benzyl or phenyl and Rio is hydrogen or Cl-C2oalkyl. 7. A compound according to claim 6 of formula Tb, wherein tell R 2 is fluorine or chlorine, R3 is hydrogen or methyl, R4 is hydrogen, fluorine, chlorine, Ci-C~.alkyl, Cl-C4haloalkyl, hydrogen, fluorine, chlorine or CI-Cz~alkoxy, C m T and n are a value from i to 3 and X+ is a cation of an alkali metal, or H4N ,(CH 3 4 N (C2H5)4.N (n-C 3 H 7 )z4N ,(i-C 3 H 7 4 N HN CH (CH) 8 5 N or 00CH 3 -(CH 2 8 15 -N (CH 3 .3 8. A compound according to claim 7 of formula Ib, wherein R 2 is fluorine or chlorine, R 3 is hydrogen or methyl, R4~ is hydrogen, fluorine, chlorine, methyl, CF3, methoxy or OCF 3 R 5 is hydrogen, fluorine, chlorine or methoxy, m and n are a value from 1 to 3 and p- 139 XP is Nao, K or (CHObN (Call 5 4 Nov C11 3 -(CH 2 15 -NO(CH 3 3 or (n-C4H 9 )4 N 9. A compound according to claim 5 of formula Ia, wherein R 2 is fluorine, R 3 is methyl, Ri, is hydrogen, 4-fluorine or 4-chlorine, R 5 in fluiorine, chlorine or methoxy, each in the 2- and/or 6 -positions, m is 1 or 2 and n is 1. The compound according to claim 9 of the formula CH 3 ~Cl k If: 11. The compound accovding to claim 9 of taie formula >-COHCONH--N I,* 12. The compound according to claim 9 of the formula t /F Cl 13 The compound according to claim 9 of the formula -COIlC0Nfl~e N 00111.r'f 2 14. The compound according to claim 9 of the formula H 3 K CONHCONH-/ ~Cl ~Cl Oa The compound according to claim 9 of the formula /F 1~Cl .CONHCONH-* )-N 16. A process for the preparation of a compound of formula I R2 RIk is \1U4 R ishalogn, whe whish haogenscmrie eatn -41- a) a compound of formula II (4)n C /R2 with a compound of formula III or b) a compound of formula IV (14 )n#4R fi I 4- H N C O( V in the absence or presence of an organic or inorganic base, with a compound of formula V 4 O-NH2M or c) a compound of formula II R 2 *to* \--NnH I with a compound of formula VI \*.-CONH-COOR (I 42 in which formulae II to VI, Ra tu R5, m and n are as defined for formula I and R is a Ci-Csalkyl radical which is unsubstituted or substituted by halogen. 17. A process for the preparation of a compound of formula I (4n C R2 NHCOR1 (I) cl wherein s) m X e R1 is _*-CON- t, Rz is halogen, R 3 is hydrogen or Ci-Csalkyl, R 4 is hydrogen, halogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, Cl-C6alkoxy, C 1 -Cshaloalkoxy, cyano or nitro, Rs is hydrogen, halogen or C1-C6alkoxy, m and n are a value from 1 to 5, with the proviso that the indi- vidual substituents R4 may differ in meaning from one another if n is a value from 2 to 5 and that the individual substituents Rs may differ in meaning from one another if m is a value from 2 to and X+ is an inorganic or organic cation, o 9 which process comprises reacting a compound of formula la obtained according to claim 16 n, R (15) m CH2-- *-NHCONH-CO--* (Ia) c{ wherein R2 to R5, m and n are as defined above, with a metal alkanolate or an ammonium hydroxide of formula X -I -i i -i L -II~ 43 X®OH (X) X being the cation of an organic base. 18. A pesticidal composition which contains as active ingredient a compound according to any one of claims 1 to 15, together with suitable carriers and/or other adjuvants. 19. Use of a compound according to any one of claims 1 to 15 for controlling insects and representatives of the order Acarina. Use according to claim 19 for controlling larval stages of plant-destructive insects. 21. Use according to claim 19 for controlling ticks. 22. A method of controlling insects and representatives of the order t r 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 any one of claims 1 to 15, or with a composition which contains a pesticidally effective amount of such a compound, together with adjuvants and carriers. 23. A compound of formula II *0 6 I n 3 o -CHa2- NH2 (II) wherein R 2 is halogen, R3 is hydrogen or CI-C6alkyl, R4 is hydrogen, halogen, Cl-C6alkyl, C 1 -Cshaloalkyl, Ci-Csalkoxy, C 1 -Cshaloalkoxy, cyano or nitro and 3-fA" -SS 44 n is a value from 1 to 5, with the proviso that the individual substituents R 4 may differ in meaning from one another if n is a value from 2 to 24. A process for the preparation of a compound of formula II according to claim 23, which process comprises hydrogenating a compound of formula VII. /3 R3 I -cH, -N02 (VII) wherein R 2 R 3 R 4 and n are as defined in claim 23, in the presence of Raney nickel. A substituted N-benzoyl-N urea, substantially as hereinbefore described with reference to any one of compounds 1.1 to 1.367 or 2.1. 26. A process for the preparation of a N-benzoyl-N 3,-dichlorophenyl)urea, substantially as hereinbefore described with reference to any one of the Examples. 27. A pesticidal composition which contains as active ingredient a i substituted N-benzoyl-N 1 -(benzylamino-3,5dichlorophenyl) urea, substantially as hereinbefore described with reference to any one of the Formulation Examples 2.1 to 2.8. DATED this FIFTH day of MARCH 1990 CIBA-GEIGY AG Patent Attorneys for the Applicant SPRUSON FERGUSON S:RA 4 O SKWK:7090F N- I-