CY1683A

CY1683A - Benzoylphenylureas

Info

Publication number: CY1683A
Application number: CY1683A
Authority: CY
Original assignee: Ciba Geigy Ag
Priority date: 1985-10-14
Filing date: 1993-10-10
Publication date: 1993-10-10
Also published as: CA1291151C; CN1014110B; DK488186A; EP0219460B1; DK111692D0; IL80271A; GB2217324A; GB2182329B; MX173307B; CN86106647A; ZA867736B; GB2182329A; GB2217324B; IL80271A0; KR870003975A; HK33893A; EP0219460A2; SU1588277A3; JPH034543B2; BR8604995A

Abstract

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

Description

1

GB 2 182 329 A

1

SPECIFICATION Benzoylphenylureas

5 The present invention relates to novel substituted N-benzoyl-N'-3,5-dichloro-4- 5

hexafluoropropyloxyphenylureas,to processes and to intermediates for the preparation thereof, and to the use of the novel compounds in pest control.

The invention relates to compounds of formula I

10 ^ <jll 10

/.•-CO-NH-CO-NH—^ 0-CF2-CHFr-CF3 (I)

15 ^ ^ 15

wherein Rn is hydrogenorfluorineandRzisfluorineorchlorine,andtosaltsthereof.

Compounds of formula I meriting particular interest are those wherein Ri is fluorine and Rzisfluorineor chlorine.

20 Further preferred compounds of formula I are those wherein Rt is hydrogen and R2isfluorineorchlorine. 20 The compounds of formula I can be prepared by methods analogous to ones known perse (q.v.e.g.

German Offenlegungsschrift specifications 2123236,2061 780 and 3 240 975).

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

25 25

f1

• 3 •

CF3-CHF-CF2-0-'( NHz (II)

30 V 30

with a compound of formula 111 35 „ 35

p.-C0-N»C=0 (III)

40 iz 40

or b) the compound of formula IV 45 m 45

91

• ait

CF3-CHF-CF2-0—^ ^•-N=C=0 (IV)

Jl*

50 C1 50

with a compound of formula V

55 ^ f1 55

^.-CO-NHa (V),

• a •

h

60 60

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

BNSDOCID: <GB 2182329A„J_>

2

GB 2 182 329 A

2

J1

^ * —CO-NH-COOR. (VI).

5 5

In formulae III, V and VI above, the radicals and R2 are as defined for formula I, and R is a C,-C8alkyl radical which is unsubstituted or substituted by halogen, preferably chlorine.

10 The above processes a), b) and c) can preferably be carried out under normal pressure and in the presence 10 of an organic solvent or diluent. Examples of suitable solvents or diluents are: ethers and ethereal compoundssuch as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons,

especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and

15 chlorobenzene; nitrilessuchasacetonitrileorpropionitrile; dimethyl sulfoxide: and ketones, e.g. acetone, 15 methyl ethyl ketone, methyl isopropyl ketoneand methyl isobutyl ketone. Process a) is normally carried outin thetemperature range from -10°to +200°C, preferably from 0 to 100°C, e.g at room temperature, and, if desired in the presence of an organic base, e.g. triethylamine. Process b) is carried out in thetemperature range from 0°to 150°C, preferably atthe boiling point of the solvent employed and, if desired, in the presence

20 of an organic base such as pyridine, and/or with the addition of an alkali metal or alkaline earth metal, 20

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

The starting materials of formulae III and V are known and can be prepared by methods analogous to

25 known ones. The starting aniline offormula II is a novel compound which likewiseconstitutes an object ofthe 25 present invention. The compound offormula II can be prepared in a manner known perse by hydrogenating the suitably substituted nitrobenzene of formula VII

30 91 30

CF3-CHF-CF2-0— ' (VII)

hi

35 35

by a process analogous to that described in J. Org. Chem. 29 {1964), 1, (q.v. also the literature cited therein). However, the aniline offormula II can also be obtained by chemical reduction (e.g. with Sn(ll) chloride/HCI) of the nitro compound offormula VII {q.v. Houben-Weyl, "Methodend. org. Chemie" 11/1.422). Thenitro compound offormula VII itself can be prepared byfluoroalkylating 3,5-dichloro-4-nitrophenol. Afurther

40 processforthe preparation of theaniline offormula II comprisesfluoroalkylating in corresponding manner 40 the acylated 2,6-dichloro-4-hydroxyaniline and then removing the acyl group, e.g. by acid hydrolysis, or effecting the fluoroalkylation with a salt of 3,5-dichloro-4-hydroxyaniline, e.g. thechlorohydrate.

Benzoylisocyanates of formula III can be obtained, inter alia, as follows (q.v. J. Agr. Food Chem. 2 7,348 and 993; 1973):

45 45

3 N M2vla0^ ./~\-CO-NH2

50 —y **? 50

"•2 R2

J1

55 CHgCl2°C1 > •( /-CO-H-OO (III) . 55

'X

The 4-(hexafluoropropyloxy)phenylisocyanate offormula IV (b.p. 95°C/0.01 torr), which is novel perse, can be prepa red e.g. by phosgenating the aniline offormula II by methods which are commonly employed in the 60 art and also comprises an object of this invention. The benzamides offormula V which are further used as starting materials are known (q.v. for example Beilstein "Handbuch derorganischen Chemie", Vol. 9, p. 336).

Urethanes offormula VI can be obtained in a manner known perse by reacting a benzoylisocyanate of formula III with a suitable alcohol or by reacting a benzamide offormula V, in the presence of a base, with a

65 corresponding ester of chloroformic acid CI-COOR.

BNSDOCID: <GB 2182329A_J_>

3

GB 2 182 329 A

3

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

To be singled outfor special mention are the metal salts of the compounds offormula I of the invention, in 5 particular the alkali metal and alkaline earth metal salts thereof, preferably the sodium salts and potassium salts. These salts are prepared in a manner known perse, e.g. by reacting a compound offormula I with a metaI alkanolate such as sodium ethylate or potassium methylate. A given salt can be converted into a desired salt of another metal by salt-interchange, e.g. with another alkanolate.

Of particular importance are the salts of compounds offormula I with organic bases, an essential feature of 10 which is the presence of a quaternary nitrogen atom. Such salts are offormula la

15

b

• m •

/ \

f1

Q •=•

y- CO-N-CO-NH—^ O-cf2-CHF-cf3

la ii

(Ia)

wherein R1 and R2 are as defined above and X® is the cation of an organic base. X® is preferably one of the 20 following organic cations:

(CH3)4 N®, (C2H5)4 N®, (n-C3H7)4 N®, (i-C3H7)4 N®, (n-C4H9)4 N®,

(CHjK N®,

25

30

35

(n-Ci»H9) 1, N®,

(•( y~) (CH3>3 Nw,

(c2h5)w n®, //

(•^ )•-CH2) (CH3)3 N'

(n-C3H7h N®,

(i-CiH7)it N®,

.J®

/\ i ii

'V'

H

©

(cijhg) 3 nh

10

15

20

25

30

35

40

/n i ii i vv

H

and

CH3-(CH2)

©

N—CH3

40

whereby nisan integerfrom8to 12. The saits offormula la also comprise mixtures of these salts with 45 different cations. The salts offormula la can be prepared in a manner known perse by reacting a compound of 45 formula I with corresponding ammonium hydroxides of the formula X® (OH)®, wherein X® is as defined above.

N-Benzoyl-N'-2,5-dichlorophenylureaswith a haloalkoxy substituent in the4-position of the phenyl ring are already known as insecticides (q.v. US patent specification 4 518 804 and German Offenlegungsschirft2848 50 794). Insecticidal N-halobenzoyl-N'-(3,5-dich!oro-4-haloalkenyloxyphenyl)ureas are described in US Patent 50 specification 4162 330. Insecticidal N-halobenzoyl-N'-(3,5-dichloro-4-haioalkoxyphenyl)ureas are thesubject matter of US patent specification 4468 405. Furthermore, compounds of similar structure are known from US patent specification 4 529 819 and British patent applications 2106499,2106 500,2106 501 and 2113 679.The feature which essentially distinguishes the novel benzoylphenylureas offormula I according to the present 55 invention from the compounds described in these references is that the novel compounds of this invention 55 carry in the4-position of the phenyl ring a 1,1,2,3,3,3-hexafluoropropyloxy group.

Surprisingly, it has been found that thecom pounds of this invention and the salts thereof have excellent properties as pesticides while being well tolerated by plants and having lowtoxicity to warm-blooded animals. They are particularly suitablefor controlling insects and representatives of the order Acarinathat 60 attack plants and animals. 60

In particular, the compounds offormula I are suitable for controlling insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera,Diptera,Thysanoptera,Orthoptera,Anoplura,Siphonaptera, Mailophaga,Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatives of the order Acarinaofthefamilies: lxodidae,Argasidae,Tetranychidaeand Dermanyssidae.

65 In addition to their action againstflies, e.g. Musca domestica, and mosquito larvae, the compounds of 65

BNSDOCID: <GB 2182329A_I_>

4

GB 2 182 329 A

4

formula i are also suitableforcontrolling plant-destructive feeding insects in ornamentals andcrops of useful plants, especially in cotton (e.g. against Spodoptera littoralis and Heliothis virescens) and in fruit and vegetables (e.g. against Laspeyresia pomonella, Leptinotarsa decemlineata and Epilachna varivestis).The compounds offormula I have a pronounced ovicidal and, in particular, larvicidal action againstinsects, 5 especially against larvaeof noxious feeding insects. If compounds offormula I are ingested by adult insect stages with the feed, then a diminished oviposition and/or reduced hatching rate is observed in many insects, especially in Coleopterae, e.g. Anthonomus grandis.

The compounds offormula I can also be used for controlli ng ectoparasites such as Lucilia sericata, in domesticanimals and productive livestock, e.g. by treating animals, cowsheds, barns, stables etc., and 10 pastures.

The compounds offormula I are also suitable forcontrollingthefollowing species of mites which attack crops of fruitand vegetables: Tetranychusurticae.Tetranychuscinnabarinus, Panonychusulmi,Broybia rubrioculus, Panonychus citri, Eriophyes piri, Eriophyes ribis, Eriophyes vitis,Tarsonemus pallidus, Phyllocoptes vitis and Phyllocoptruta oleivora.

15 Moreover,the benzoylureasof formula I have properties enabling them to be usedforcontrollingslugsand snails. The repellant andfeed inhibiting action of these compounds is frequently very difficultto ascertain in laboratory tests. However, infield trials even atvery low concentrations good activity is observed in agricultural and horticultural crops. In particular, sensitive crops of lettuce, vegetables and fruit (such as strawberries) and ornamentals and flowers are afforded protection against feeding damage caused by slugs 20 and snails. The compounds offormula I of this invention are effective against all slugs and snails, most of which occur as polyphagic pests in agricultural and horticultural crops. In addition to exhibitingfeed inhibiting action, the compounds offormula I can also effect mortality. Numbering among terrestrial slugs are several pests which cause damage of great economic significance, for example the slugs Arion rufus (red slug), Arion ater and other Arionidae, Umax species and field slugs, e.g. Deroceras reticulatum and D. agreste 25 of the family Limacidae, and also species of thefamily Milacidae. Damage isalso caused by snails, interalia, of the genera Bradybaena, Cepea, Cochlodina, Discus, Euomphalia, Galba, Helicigona, Helix, Helicella, Helicodiscus, Lymnaea, Opeas, Vallonia and Zonitoides.

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

30 The activity ofthe compounds offormula l and ofthecompositionscontaining them can besubstantially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organophosphorus compounds, nitrophenols and derivatives thereof,formamidines, ureas, carbamates, pyrethroids,chlorinated hydrocarbons, and Bacillus thuringiensis preparations.

35 The compounds offormula I are used in unmodified form, or preferably together with theadjuvants conventionally employed in the art of formulation, and are therefore formulated in known mannerto emulsifiable concentrates, directly sprayable ordilutablesolutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymersubstances. As with the nature ofthe compositions, the methods of application such asspraying, atomising, dusting, scattering or pouring, 40 are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) offormula 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 45 (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably thefractions containing 8to 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 50 cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite orattapulgite. In order to improve the physical properties it isalso 55 possible to add highly dispersed silicic acids 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 orsand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of formula I to be formulated, or of combinations thereof with 60 other insecticides or acaricides, suitablesurface-activecompounds are non-ionic, cationicandforanionic 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.

65 Suitablesoaps arethealkali metal salts, alkaline earth metal salts orunsubstituted orsubstituted

5

10

15

20

25

30

35

40

45

50

55

60

65

5

GB 2 182 329 A

5

ammonium salts of higher fatty acids (Cio-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, e.g. from coconut oil ortallowoil. Furthersuitable surfactants are also the fatty acid methyltaurin salts as well as modified and unmodified phospholipids.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty 5 sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonicacid,ofdodecylsulfate,orof a mixture of fatty alcohol sulfates obtained from natural fatty acids.

10 These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonicacid,dibutylnaphthalenesulfonicacid,orofa naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, 15 e.g. salts of the phosphoric acid esterof an adduct of p-nonylphenol with 4 to 14moles of ethylene oxide.

Non-ionicsurfactantsarepreferablypolyglycoletherderivativesofaliphaticorcycloaliphaticalcohols,or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

20 Further suitable non-ionicsurfactants 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.

25 Representative examples of non-ionicsurfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters ofpolyoxyethylenesorbitan, e.g. polyoxyethylenesorbitan trioleate, are also suitable non-ionicsurfactants.

Cationicsurfactants are preferably quaternary ammonium salts which contain, asN-substituent, at least 30 oneC8-C22alkyl radical and, asfurthersubstituents, unsubstituted or haiogenated loweralkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in theform of halides, methylsulfates orethyf sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1979; Dr. Helmut 35 Stache, "TensideTaschenbuch" (Handbook of Surfactants), Carl HanserVerlag, Munich/Vienna 1981.

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

Whereas commercial products are preferably formulated as concentrates, the end user will normally 40 employ diluted formulations of substantially lowerconcentration.

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

Example J:

45 a) Preparation of3,5-dichloro-4-(J, 1,2,3,3,3-hexafluoropropyloxy)aniline

47 g of 4-acetylamino-3,5-dichlorophenol together with 154 g of 90% potassium hydroxide solution and 130 ml of dimethylformamide are stirred in an autoclave. 75.8 g of hexafluoropropylene are then pressed into the closed autoclave. The mixture is stirred for 20 hours at 70°C underthe pressure developing in the autoclave. After cooling, the mixture is concentrated by rotary evaporation and the residue is dissolved in 50 methylene chloride. The resultant sol ution is washed with water, dried over Na2S04 and concentrated. The crude product obtained as residue is chromatographed through a column of silica gel (length: 1m; diameter: 10cm)elutedwithan11:1 mixture of toluene and acetone, affording 4-acetylamino-3,5-dichloro-1-(1,1,2,3,3,3-hexafiuoropropyloxyjbenzene in theform of pale yellow crystals (m.p.: 113-115°C),26gofwhicharekeptfor 10 hours under reflux with 110 ml of ethanol and 35.6 ml of 37 % hydrochloric acid. The reaction mixture is 55 then concentrated, diluted with ice/water and made weakly alka line. The product is extracted from the mixtu re with methylene chloride. The organic extract phase is washed with water, dried over Na2S04 and concentrated. The residue is purified by distillation, thus affording the title compound of theformula

?1

• S2»

HaN~\ >-OCF2-CHF-CF3

ii

5

10

15

20

25

30

35

40

45

50

55

BNSDOCID: <GB 2182329A_L>

6

GB 2 182 329 A

6

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

b) Preparation ofN-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4-( 1,7,2,3,3,3-hexafluoropropyloxylphenylJurea 4.3 g of3,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropyloxy)anilinearedissolved with stirring in 50 ml of dry 5 toluene and, with exclusion of moisture, a solution of 2.41 g of 2,6-difiuorobenzoylisocyanate in 10 ml of dry toluene is added at room temperature. The batch is stirred for a further 13 hours at room temperature. About 75% ofthe solvent is then removed by rotary evaporation, the precipitated residue is filtered with suction, washed with a small amount of cold toluene and hexane and then dried in vacuo, affording thetitle compound ofthe formula

10

,C1

15

^.-CO-NH-CO-NH-^ /•-ocf2-CHF-CF3

\

CI

10

15

in theform of a crystalline white powder with a melting point of 171-172°C (compound 1}.

The following compounds offormula I have been prepared in a manner corresponding to that described 20 above:

20

Compound m.

25

30

35

/C1 /C1

•3* • = ♦

CO-NH-CO-NH—^ O-cf2chfcf3

\

CI

CI /C1

CO-NH-CO-NH~ \-0-CFaCHFCF3

\

CI

\

178-180°C

177-178°C

CI

25

30

35

40

/

.CI

/

*ss» 9 SB •

^—CO-NH-CO-NH—^ \-o-CF2CHFCF3

\l

156-158°C

40

45

50

55

c) Preparation ofthe sodium salt of compound 1

9.58 g of N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropyloxy)phenyl]urea are suspended in 20 ml of absolute methanol. A solution of 0.43 g ofsodium in 30 ml of absolute methanol is added dropwise with stirring to this suspension. A clear solution forms which is then concentrated. The residual product is dried in vacuo at room temperature, affording thetitle compound of theformula

/

• at*

/ \

ci

/

>-CO-N-CO-NH-v \-0-CF2CHFCF3

L

\

CI

45

50

55

as colourless crystals.

The following salt of compound2 ofthe formula below can also be prepared by proceeding as described 60 above:

60

BNSDOCID: <GB 2182329A L>

7

GB 2 182 329 A

7

p. /i

•SS <3«

CO-|-CO-NH—^ ^ • -O-CF z CHFCF 3 NC1

d) Preparation ofthe tetrabutylammonium salt of compound 1

2.56 g of N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropyloxy)phenyl]urea are 10 suspended in 30 ml of methanol. With stirring, 5.2 g of a methanolic solution containing 1.3 g of tetra-n-butylammonium hydroxide are added to this suspension, whereupon a clear solution forms. This solution is concentrated and the residual crude product is suspended in hexane. The suspension is filtered with suction and the filter residue is washed with hexane and then dried, affording the title compound ofthe formula

10

/ /C1

•«« 0

co-n-co-nh-*^ y • -o-cf 2 chf cf 3

\

CI

[(n-C^HN ]

©

as colourless crystals.

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

/

/ \

0

/

/ \

CI

^ ^•-C0-N-C0-NH-*^ OCF2CHFCF2

\

CI

[(CH3)it N ]

©

.CI

v

/ \-C0-N-C0-NH-v OCF2CHFCF3

\ Nci

[(C2H5)^N ]

©

,ci

/C1 « /

•3« Q

\ ^•-CO-N-CO-NH-*^ OCF2CHFCF3

V

VC1

)-ch2)(ch3)3nJ@

^ A /C1 l

• •• ©

c0-n-c0-nh—' y~ocf2chfcf3 [(n-c3h7)i,n ]®

' Sci \l

CI

...^ e —/

CO-N-CO-NH— ^ OCF2CHFCF3

V

sc1

CI

^ \ i ii h

F CI

/ _ /

Q

\ -CO-N-CO-NH-OCF2CHFCF3

N'_\l

[(t-CuHg)3NH ]®

BNSDOCID: <GB 2182329A_J_>

GB 2 182 329 A

25%

50%

75%

5%

-

3%

-

5%

6%

10%

V

10

-

2%

-

5%

10%

62%

27%

-

Example2:

Formulations for active ingredients offormula /according to Example 1 or combinations thereof with other insecticides or acaricides (throughout, percentages are by weight)

5 1- Wettablepowders a) b) c)

compound offormula I orcombination sodium lignosuifonate sodium iaurylsulfate sodium diisobutylnaphthalenesulfonate 10 octylphenol polyethylene glycol ether (7-8 m oles of ethylene oxide)

highly dispersed silica acid kaolin

15 The active ingredientor combination isthoroughly mixed with theadjuvants and the mixture isthoroughly 15 ground in a suitable mill, affording wettable powders which can be diluted with waterto give suspensionsof the desired concentration.

2. Emulsifiable concentrate

20 compound offormula I orcombination 10% 20

octylphenol polyethylene glycol ether

(4-5 moles of ethylene oxide) 3%

calcium dodecylbenzenesulfonate 3%

castoroil polygycol ether

25 (36 moles of ethylene oxide) 4% 25

cyclohexanone 30%

xylene mixture 50%

Emulsions of any required concentration can be obtained from this concentrate by dilution with water. 30 30

3. Dusts a) b)

compound offormula I orcombination 5% 8%

talcum 95%

kaolin - 92%

35 35

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

4. Extruder granulate

40 compound offormula I orcombination 10% 40

sodium lignosuifonate 2%

carboxymethylcellulose 1 %

kaolin 87 %

45 The active ingredient or combination is mixed and ground with the adjuvants, and the mixture is 45

subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

5. Coated granulate compound offormula I orcombination 3%

5Q polyethylene glycol (mol.wt.200) 3 % 50

kaolin 94%

The finely ground active ingredient or combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

55 6. Suspension concentrate 55

compound offormula I orcombination

40

%

ethylene glycol

10

%

nonylphenol polyethylene glycol ether

(15 moles of ethylene oxide)

6

%

60 sodium lignosuifonate

10

%

60

carboxymethylcellulose

1

%

37 % aqueous formaldehyde solution

0.2

%

silicone oil in theform of a 75 %

aqueous emulsion

0.8

%

65 water

32

%

65

BNSDOCID: <GB 2182329A_I_>

9

GB 2 182 329 A

9

Thefinely ground active ingredient or combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

5 Example 3: Action against musca domestica 5

50 g of freshly prepared nutrient substrate for maggots are charged into each of a number of beakers. A specific amount of a 1 %acetonic solution ofthe respective test compound ispipetted onto the nutrient substrate present in the beakers to give an active ingredient concentration of800 ppm. The substrate isthen thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 20 hours.

10 Then 25 one-day-old maggotsofMuscadomesticaareputintoeachofthebeakerscontainingthetreated 10 nutrient substrate fortesting with each active ingredient at the given concentration. After the maggots have pupated, the pupae are separated from the substrate by flushing them out with water and then deposited in containers closed with a perforated top.

Each batch of flushed out pupae iscounted to determine the toxic effect ofthe test compound on the 15 maggot development. A count isthen made after 10 days ofthe number of files which have hatched out ofthe 15 pupae.

The compounds offormula I according to Example 1 exhibit good activity in thistest.

Example 4: A ction against lucilia sericata 20 1 mlofanaqueoussolutioncontaining0.5%oftestcompoundisaddedat50°Cto9mlofaculturemedium. 20 Then about 30 freshly hatched Lucilia sericata larvae are added to the culture medium, and the insecticidal action is determined after 48 and 96 hours by evaluating the mortality rate.

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

25' Example 5: Action againstaedes aegypti 25

Aconcentration of 800 ppm is obtained by pipetting a specific amount of a 0.1 % solution of the test compound in acetone on tthe surface of 150 ml ofwaterina beaker. Afterthe acetonehas evaporated, 30 to40 two-day-old larvae of Aedes aegypti are put into the beaker containing the test compound. Mortality counts are made after 1,2 and 5 days.

30 In this test, compounds offormula I according to Example 1 exhibit good activity against Aedes aegypti. 30

Example 6: Insecticidal action against feeding insects a) Cotton plants about 25 cm high, in pots, are sprayed with aqueous emulsions which contain the respective test co m pou nd i n co ncentrations of3,12.5and50ppm. After the spray coati ng has d ried, the

35 cotton plants are populated with Spodoptera littoralis and Heiiothis virescens larvae in the L3-stage. The test 35 is carried out at 24°Cand60% relative humidity. The percentage mortality ofthe test insects isdetermined after 2 days.

Compounds 1,2,3 and 4 according to Example 1 effect 80-100% mortality against Spodoptera larvae at 3 ppm. 80-100 % mortality is effected against Heiiothis larvae by compound 1 at 12.5 ppm and by compounds 2 40 and 3 at 50 ppm. 40

b) Comparative test

The above test a) is repeated using compound 1 of this invention and two prior art compounds. In distinction to test a}, the percentage mortality ofthe larvae is not determined until after7 days. The active ingredient concentrations, the compounds employed and the results obtained are indicated inthefollowing 45 Table: 45

BNSDOCID: <GB 2182329A_

10

GB 2 182 329 A

10

5

10

15

20

25

Compounds employed

% Mortality

Spodoptera llttoralis

Heiiothis virescens

0.4 ppm

0.8 ppm

1.5 ppm

T f1

*s« •=«

v \-CO-NH-CO-MI-v ;.-O-CF2-CHF-CF3

\S XS 1 ii compound 1 according to Example 1 of the present invention

100 %

90 %

100 %

T J1 «=«

CO-HH-CO-NH—^ ^.-O-CF2-CHF2

i ii acc. to US Patent 4 468 405 (columns 7/8, compound 1)

67 %

90 %

23 %

70 %

•ss« »=«

^—CO-HH-CO-NH—^ 0-CF2-CHF2

I il acc. to US Patent A 5X8 804 (column 6, compound "A")

8 % .

10 %

0 %

Example 7: Action against epilachna varivestis Phaseoius vulgaris plants (dwarf beans) about 15-20 cm in height are sprayed with aqueous emulsion 30 formulationsofthetestcompoundinaconcentrationof800ppm.Afterthespraycoatinghasdried,each plant is populated with 5 larvae of Epilachna varivestis (Mexican bean beetle) in the U-stage. A plastic cylinder is slipped overthe treated plants and covered with a copper gauze top. The test is carried out at28°C and 60% relative humidity. The percentage mortality is determined after 2 and 3 days. Evaluation of feeding damage (anti-feeding effect), and of inhibition of development and shedding, is made by observing thetest 35 insectsforafurther3days.

Example 8: Ovicidal action against heiiothis virescens Corresponding amounts of a wettable powderformulation containing 25% by weight of the test compound 40 are mixed with sufficient waterto produce an aqueous emulsion with an active ingredient concentration of 800 ppm. One-day-old egg deposits of Heiiothis on cellophane are immersed in these emulsions for3 minutes andthen 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 afterSto 8 days. The compounds of formula I according to Example 1 exhibit good activity in thistest.

45

Example 9 Action against iaspeyresia pomonella (eggs):

Egg deposits of Laspeyresia pomonella not more than 24 hours old are immersed on filter paperfor 1 minute in an aqueous acetonicsoiution containing 800 ppm ofthe test compound.

Afterthe solution has dried, the eggs are placed in petri dishes and kept at a temperature of28°C. The 50 percentage of larvae hatched from the treated eggs and the percentage mortality is evaluated after 6 days. The compounds offormula I according to Example 1 exhibit good activity in this test.

Example 10: Influence on the reproduction ofanthonomousgrandis Anthonomous grandis adults which are not more than 24 hours old after hatching are transferred in groups 55 of 25 to barred cages. Thecages arethen immersed for5 to 10 seconds in an acetonicsoiution containing 400 ppm ofthe test compound. Afterthe beetles have dried, they are placed in covered dishes containing feed and leftfor copulation and oviposition. Egg deposits are flushed outwith running water twice to threetimes weekly, counted, disinfected by putting them for2to 3 hours into an aqueous disinfectant, andthen placed in dishes containing a suitable larval feed. A count is made after 7 days to determi ne the percentage mortality of 60 the eggs, i.e. the number of larvae which have developed from the eggs.

The duration ofthe reproduction inhibiting effect of thetest compounds is determined by monitoring the egg deposits further, i.e. over a period of about4 weeks. Evaluation is made by assessing the reduction in the number of deposited eggs and hatched larvae in comparison with untreated controls.

Compounds of formula I accordingto Example 1 exhibit good activity in thistest.

V

10

15

20

25

30

35

40

45

50

55

BNSDOCID: <GB 2182329A_I_>

11

GB 2 182 329 A

11

Example 11: Action againstanthonomus grandis (adults)

Two cotton plants in the 6-leaf stage, pots, are each sprayed with a wettable aqueous emulsionformulation containing 400 ppm of the test compound. Afterthe spray coating has dried {about 1.5 hours), each plant is populated with 10 adult beetles (Anthonomous grandis). Plastic cylinders, covered at the top with gauze, are 5 then slipped overthe treated plants populated with thetest insects to prevent the beetles from migrating from the plants. The treated plants are then kept at 25°C and about 60 % relative humidity. Evaluation is made after 2,3,4 and 5 days to determine the percentage mortality ofthe beetles (percentage in dorsal position) as well as the anti-feeding action as compared with untreated controls.

Compounds offormula f according to Example 1 exhibit good activity in this test.

10

Example 12: Insecticidal stomach poison action against plutellaxylostella

Potted Chinese cabbage plants (pot size: 10 cm diameter) in the 4-leaf stage are sprayed with aqueous emulsions which contain the test compound in a concentration of 0.8 ppm and which dry on the plants.

After 2 days, each of the treated Chinese cabbage plants is populated with 10 Plutellaxylostella larvae inthe 15 L2-stage. Thetest is carried out at 24°C and at 60% relative humidity in dim light. Evaluation of the percentage mortality ofthe larvae is made after 2 and 5 days.

Compound 1 according to Example 1 effects 100% mortality in thistest.

Example 13: Feed inhibiting action against slugs 20 5 red slugs (Arion rufus) are leftfor 17 hours under controlled test conditions in each of a number of cages containing 4 fresh lettuce leaves. In these tests, each cage either only contains untreated leaves oronly contains leaves which have been treated by spray application. The concentration of the test compound inthe aqueousformulation applied is 0.5 % by weight. The extent of the feeding damage is determined on the basis of weight differences, photocopies of pictures of thefeeding damage and on the basis of any evident 25 assessable criteria in comparison with untreated controls.

The mortality of thetest animals isalso determined.

Compounds offormula I according toclaim 1 exhibit good activity in thistest.

Claims

CLAIMS 30

1. A compound offormula I

13* • at •

35 / CO-NH-CO-NH-v \ -0-CF z-CHF-CF 3 (I)

i2 Ai

40 wherein R, is hydrogen orfluorine and R2 isfluorine or chlorine, or a saltthereof.

2. Acompound offormula I according to claim 1, wherein isfluorine and R2 is fluorine orchlorine.

3. Acompound offormula I according to claim 1 .wherein Rt is hydrogen and R2 isfluorine orchlorine.

4. The compound according to claim 2 of the formula

45 T 91

y'^*\

% /~C0~NH"C0-NH-\ y-0-CF2-CHF-CF3 50 ^ Al

5. The compound according to claim 3 of the formula

55 91 91

9mm

^—CO-NH-CO-NH— ^ \_0-GF2-CHF-CF3

hi

60

6. The compound according to claim 3 of the formula

5

10

15

20

25

30

35

40

45

50

55

60

BNSDOCID: <GB 2182329A_1_>

12

GB 2 182 329 A

12

Y f1

• m • • a •

•f' \-co-NH-CO-NH-v \-o-cf2-CHF-GF3

v y v_y

Ai

7. The compound according to claim 2 of the formula

10

15

? 91

t as * • ia •

\-c0-NH-c0-NH-«^ \-o-CF2-CHF-CF3

ii ii

10

15

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

9. A salt of a compound offormula I accordi ng to any one of claims 1 to 7 with an organic base.

10. A salt according to claim 9, wherein a quatenary nitrogen atom is present.

20 11. A process forthe preparation of a compound according to any one of claims 1 to 10, which process comprises reacting a) the compound offormula II

25

91

• at*

CP3-CHF-CF2-O—^ NHZ

6l

30 with a compound offormula III

(II)

20

25

30

J1

y

35 \ /

—C0-N»C=0

(III)

35

or

40 b)the compound offormula IV

91

• m •

CF3-CHF-CF2-0-v \-N=00

45 \_y hi

<iv)

40

45

50

55

with a compound of formula V

Y1

y ^.-co-nh2

(V),

50

55

or c) the compound offormula If with a compound offormula VI

h y \

s /

A,

-CO-NH-COOR

(VI)

BNSDOCID: <GB 2182329A I

13

gb 2 182 329 a

13

In which formulae I

II, V and VI, the radicals R! and R2 are as defined in any one of claims 1 to 3 and R isa C^CgaUcy! radical which is unsubstituted orsubstituted by halogen, and, if desired, converting the resultant compound offormula I into a saltthereof.

12. The compound offormula II 5 5

f1

• SB •

cf3-chf-cf2—o—^ nh2 (ii)

10 10

£i

13. Thecompoundofformula IV

15 (jjl 15

• aia

CFs-CHF-CFz-O— ^ \-N=C=*0 (IV)

ii

20 ^ 20

14. A pesticidal composition which contains as active ingredient a compound according to any oneof claims 1 to 7, or a salt thereof, together with suitable carriers and/orother adjuvants.

15. Use of a compound according to any one of claims 1 to 7, or of a saltthereof, for controlling insects,

25 representatives ofthe order Acarina and slugs and snails. 25

16. Use according to claim 15forcontrolling larval stages of plant-destructive insects.

17. Use according to claim 15forcontrolling insecteggs.

18. A method of controlling insects, representatives ofthe order Acarina and slugs and snails, which method comprises treating said pests, the various development stages orthe locusthereof with a pesticidally

30 effective amount of a compound of formula I according to any one of claims 1 to 7, or of a salt thereof, or with a 30 composition which contains a pesticidally effective amount of such a compound, together with adjuvants and carriers.

Printed for Her Majesty's Stationery Office by Croydon Printing Company <UK) Ltd, 3/87, D8991685. Published by The Patent Office, 25 Southampton Buildings, London WC2A1 AY, from which copies may ba obtained.

BNSDOCID: <GB 2182329A_J_>