CA1242453A - Benzoylphenylureas - Google Patents
BenzoylphenylureasInfo
- Publication number
- CA1242453A CA1242453A CA000493028A CA493028A CA1242453A CA 1242453 A CA1242453 A CA 1242453A CA 000493028 A CA000493028 A CA 000493028A CA 493028 A CA493028 A CA 493028A CA 1242453 A CA1242453 A CA 1242453A
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- fluorine
- methyl
- methoxy
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/06—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from cyanamide or calcium cyanamide
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
- C07C275/48—Y being a hydrogen or a carbon atom
- C07C275/54—Y being a carbon atom of a six-membered aromatic ring, e.g. benzoylureas
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Benzoylphenylureas Abstract of the Disclosure The invention relates to novel substituted N benzoyl-N'-2,5-dichloro-4-haloalkoxyphenylureas of the formula
Description
Benzoylphenyluress The present invention relates to novel substituted N-benzoyl-N'-
2,5~dichloro-4-haloalkoxyphenylureas, to processes and to inter-mediates for the preparation thereof, and to the use of the novel compounds in pest control.
The invention relates to compounds of formula I
~C0-NH-C0-NH-~ -0-R3 (I) R2 Cl wherein R1 is hydrogen, fluorine, chlorine, methyl, methoxy or methylthio, R2 i~ fluorine, chlorine, m~thyl, methoxy or methylthio ad R3 19 C1 C7haloalkyl containing 1 to 15 halogen atoms or is C3-C7halocycloalkyl containing 1 to 13 halogen atoms, with the proviso that R3 i8 not ~CF2-CHF-CF3. R3 i9 preferably C1-C3alkyl which i9 subst~tuted by 1 to 7 halogen atoms.
Compounds of formula I which ar0 preferred on account of their biological activity are tho~e wherein R2 iB methyl, methoxy or methylthio if R1 i9 hydrogen;
R2 is fluorine, methyl, methoxy or methylthio if R1 is fluorine; or R2 i8 chlorine, methyl, methoxy or methylthio if R1 is chlorine.
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, .
, Compounds of formula I meriting special interest on account of their activity are tho~e wherein R1 and R2 are simultaneoufily fluorine or chlorine and, independently of each other, are methyl, methoxy or methyl~hio, and, in partlcular, tho~e compound~ wherein Rl and R2 are simultaneously fluorine or chlorine, preferably fluorine.
Further preferred compounds of formula I are those wherein R3 i~ one of the radicals -CHF2, -CF3, -CF2CHF2, -CH2CF3, -CF2CHClF, -CF2CHCl2, -CF2CCl3, -CF2CHBrz, -CF2CHBrF, -CF2C~lBr2, -CH2CHBrCH2Br, -CF(CF3)CHFCF3, -CF2CHFCF(CF3)2, -CF2CHF~CF2)4CF3 or ~CF2-~F2 in partlcular those compounds wherein R3 is one of the radicals -CF2CHF2, -CF2CHFCl, -CF2CHCl2 or -CFzCCl3. Those compound3 of formula I wherein R3 ifi Cs-C7haloalkyl containing 1 to 15 halogen atoma are also interefiting.
The compounds of formula I can be prepared by 1nethods analogous to onefi known per ~e (q.v. for example German Offenlegungsschrift speciications 2 123 236, 2 601 780 and 3 240 975).
l'hus, for example, a compound of formula I can be obtained by reacting a) a compound of formula II
~1 R3-O-~ -NH2 (II) with a compound of formula III
~1 CO-N~C~O (III) ~ 2 or b) a compound of formula IY
R3-O~ -N~C~O (IV) with a compound of formula V
~1 -CO-NHz (V) 1~2 or c) a compound of formula II w~th a compound of formula VI
~1 -CO-N~I-COOR ~VI).
~z In formulae II to VI above, Rl, R2 and R3 are a~ defined for formula I, and R 1~ a Cl-Caalkyl radical which 19 unsubstituted or substituted by halogen, preferably chlorine.
The sbove processes a), b~ and c) can preferably be carried out under normal pressure and in the presence of an organic 301vent or dil~ent. Examples of suitable solvents or diluenta are: ether~ and ethereal co~pounds, such as diethyl ether, dipropyl ether, dibutyl ether, dloxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylatad carboxamides; aliphatic, aromatic and halogenated hydrocarbons, i3 especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachlorlde and chlorobenzene; nltriles such 88 aceto-nitrile or propionitrile; dimethyl sulfoxlde; and ketones, e.g.
acetone, methyl ethyl ketone, methyl iiopropyl ketone and methyl isobutyl ketone. Process a) i8 normally carried out in the tempera-ture range from -10 to ~200C, preferably from O to 100C, e.g at room temperature, and, if desired in the presence of an organic base 7 e.g. trlethylamine. Process b) i~ carried out in the tempera-ture range from 0 to 150C, preferably at the boiling point of the solvent employed and, lf desired, in the presence of an organic base such as pyridine, and/or with the addition of an alkali metal or alkalin0 earth metal, preferably sodium. Fo~ process c), i.e. for the reaction of the urethanP of formula VI with an aniline of formula II, a temperature range from about 60 to the boiling point of the reactlon mixture i9 preferred, and the solvent employed i9 preferably an aromatlc hydrocarbon auch as toluene, xylene, chloro-benzene and the like.
The staxting materisls 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 ob~ect of the present invention. The compounds of formula II can be prepared in a manner known per se by hydrogenating suitably substltuted nitrobenzenes of formula VII
gl R3-O~ NO2 (VII) Cl by a process analogous to that described in J. Org. Chem. 29 (1964), 1, (q.v. also the literature cited therein). Ho~ever, the anillnes of formula II can also be obtained by chemicsl reduction (e.g. with Sn(II) chlorldel~Cl) of the corresponding nitro compounds of fol~ula YII (q.v. Houben-Weyl, "Methodcn d. org. Chemie" 11/1, 422).
The nitro compounds of formula VII can be prepared by h~lo-alkylating 2,5-dichloro-4-nitrophenol. A further proces~ for the ~2~ 3 preparation of the anilinas of formula II comprises haloalkylating acylated 2,5-dlchloro-4-hydroxyaniline and then removing the acyl group, e.g. by acid hydrolysis.
Benzoylisocyanates of formula III can be obtained, inter alia, as follows (q.v. J. A~r. Food Chem. 21, 348 and 993; 1973):
~ ~'-C 5 N HzS04M 20 ~ 0~ ~--CO-NHz ~Z ~2 CO-N-C-O (III) .
The 4-haloal~oxyphenyli30cyanates of formula IV can be prepared e.g. by phosgenating the anillnes of formula II by methods whlch are commonly employed in the art. The benazmides of formula V wh~ch are further used as starting materials are known (q.v. for example BeilstQin "Handbuch der organiscl)en Chemie'~, Vol. 9, p. 336).
Urethanes of formula VI can be obtalned in a manner known par se by reacting a ben~oyli~ocyanate of formula III with a suitable alcohol or by reactlng a benzamide of formula V, in the presence of a base, with a corresponding ester of chloroformic acid Cl-COOR.
Surprislngly, it has been found that the compounds of this inven-tion and the salts thereof have excellent propertia3 as pesticides while being well tolerated by plantg and having low toxicity to WarM blooded animals. They are particularly suitable for controlling insects and rapresentatives of the order Acarina that attack plants and animals.
In particular, the compounds of formula I are suitable for control-ling insects of the orders: Lepidoptera9 Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, ;i3 Mallophaga, Thysanura, Igoptera, Psocoptera and Hymenoptera, a3 well a9 representatives of the order Acarina of the families: Ixodldae, ~rgasidae, Tetranychldae and Dermanyssidae.
In addition to their action against flies, e.g. Musca domestica, and mosquito larvae, the compounds of formula I are also suitable for controlling plan~-destructive feeding insects in ornamentals and crops of useful plants, especially in cotton (8.g. against Spodoptera littoralis and Heliothis virescens) and in fruit and vegetables (e.g. against Laspeyresia pomonella, Leptinotarsa decemlineata and Epilachna varivestis). T~e compounds of formula I have a pronounced ovicidal and, in particular, larvicidal action against insect3, especially against larvae of noxious feeding insects. If compounds of formula I are ingested by adult insect stages with the feed, then a diminished oviposition and/or reduced hatching rate is observed in many insects, especially ln Coleopterae, e.g. Anthonomus grandis.
The compounds of formula I can also be used for controlling ecto-parasite~ such as Lucllia sericata, in domestic animals and produc-tive livestock, e.g. by troating animals, cowshed~, barns, stables etc., and paAtures.
The compounds of formula I are also sultable or controlling the following species of mites which attack crops of fruit and vegetables:
Tetranychus usticae, Tetranychus clnnabarinus, Panonychus ulmi, Broybia rubrioculus, Panonychus citri, Eriophyes piri, Eriophyes ribis, Eriophyes vitis, Tarsonemus pallidus, Phyllocoptes vitis and Phyllocoptruta oleivora.
The good pesticidal activity of the compounds of formula I of the invention corresponds to a mortality of at least 50-60 % of tha above pe3ts.
The activity of the compounds of formula I and of the composition~
containing them can be substantially broadened and adapted to prevailing circum~tances by addition of other insecticides and/or acaricides. Examples of guitable additi~es lnclude: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
The compounds of formula I are used in unmodified form, or preferably together wlth the acljuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders~ soluble powder~, dusts, granulates, and also encapsulations in e.g. polymer substan-ces. As with the nature of the compositions, the m2thods of appli-cation such as spr~ying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended ob~ectives and the prevsiling circumstance3.
The formulations, i.e. the compo3itions, preparstions or mixtures containing the compound (active ingredient) of the formula I or combinations thereof with other lnsecticide~ or acaricldes, and, where appropriate, a solid or liquid ad~uvant, are prepared in known manner, Q . g . by homogeneously mlxing and/or grinding the active ingredient3 with extenders, e.g. solvents, 301id carriers and, in some cases, surfaca-act~ve compounds (surfactants).
Suitable 301vents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalene~, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohol~ and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrro-lidonal dimethyl 3ulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such a~ epoxldised coconut oil or soybean oil; or water.
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- 8 ~
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorlllonite or attapulgite. In order to improve the physlcal properties it is al~o possible to add hlghly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorp-tiva carriers are porous types, for eY.ample pumice, broken brick, 3epiolite or bentonite; and suitable nonsorbent carriers are materials ~uch as calcite or sand. In addition, a great number of pregranulated mater~als of inorganic or organic nature can be used, e.g. especially dolomite or pulverlsed plant r~sidues.
Depending on the nature oE the compound of formula I to be formulated, or of combinations thereof with other insecticides or acaricides, suitable surface-active compouDds are nonionlc, cationic and~or anionic surfactants having good emul3ifying, dispersing and wetting properties. The term "surfactants" will also be understood R~ compriBing mixtures of surfactants.
Suitable anio~ic surfactants can be both water-soluble soaps and water-soluble synthotic surface-active compounds.
Suitable soaps are the al~ali metal salt~, alkaline earth metal salts or unaubstituted or substituted ammonium salts o higher fatty acids (C1O-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 or tallow oil. Further ~uitable surfactants aro also the fatty acid methyltaurin salts as well as modifled and unmodified phospholipids.
More frequently, however, so-called synthetic aurfactants are used, especially fatty sulfonates, fatty sul~ates, sulfonated benzimida-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 subst~-tuted ammonium salts and oontain a Cg-C22alkyl radical which also ;3 g includes the alkyl moiety of acyl radlcal~, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate9 or of a mixture of fatty alcol~ol sulfates obtained from natural fatty acid~.
These compounds also comprise the salts of sulfuric acid e3ters and sulfonic acid~ of fatty alcohol/ethylene oxide adductE~. The sulfona-ted benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to ~2 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-ethanolamine aalts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phospha~es, ~.g. salts of the pho~phoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide.
Non-ionic flurfactants are preEerably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturnted Eatty acicls and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adduct3 of polyethylene oxide with polypropylene glycol, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glyccl ether groups and 10 to 100 propylene glycol ether groups. These compound6 usually contain 1 to 5 ethylene glycc>l units per propylene glycol unit.
Representative example3 of non-lonic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ether6, polypropylene/-polyethylene oxide adducts, tributylphenoxypolyethoxyathanol, polyethylene glycol and octylphenoxypolyethoxyethanol. ~atty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are al60 suitable non-ionic ~urfactants.
i3 Cationic surfactants are preferably quaternary ammonium sal~8 whlch contain, as N-sub~tituent, at least ona Cg-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The 3alts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromid0.
The ~urfacta~ts customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and ~mulgifiers Annual", MC Publishing Corp. Ridgewood, New Jersey~ 1979; Dr. Helmut Stach0, "Tensid Taschenbuch" (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna, 1981.
The pesticidal composltions ususlly contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or combination thereof with other lnsecticides or acaricides, 1 to 99.9 % of a solid or liquid ad~uvant, and O to 25 %, preferably 0.1 to 20 %, of a suresctant.
Whereas commercial products are preferably formulated as concen-trates, the end user will normally employ diluted formulations of substantially lower concentration.
The compositions may also contaln further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
Example 1-a) Preparation of 2,5-dichloro-4 ~ 1',2' 2'-tetrafluoroethoxy~-aniline 18.6 g of 4-acetylamino-2,5-dichlorophenol together with 6.1 g of KOH powder and 130 ml of dimethylformamide are 5tirred in an autoclave. 20 g of tetrafluoroethylene are then pressed into ths , . .
2~;3 closed autoclave. The mixture is stirred for 20 hours at 70C under the pressure which has built up in the autoclave. After cooling, the mixture is concentrat~d by rotary evaporation and the residue i~
dissolved in methylene chloride. The resultant solution is washed with water, dried over Na2S04 and concentrated. After r0crystalli-sation from a mixture of methylene chloride and hexane, 2,5-di-chloro-4-(1',1',2',2'-tetrafluoroe~hoxy)acetanilide with a melting point of 119-120C i8 obtained. 15.8 g of the resultant 2,5-di-chloro-4~(1',1',2',2'-tetrafluoroethoxy~acetanilide are kept for 10 hours under reflux with 75 ml of ethanol and 25 m of 37 %
hydrochloric acid. The reaction mixturs i8 then concentrated, diluted with ice water and made weakly alkaline. The product i8 extracted from the mixture with ethylene chloride. The organic phase i8 wa~hed with water and dried over Na2S04 and the methylene chloride is distilled off.
The crude product i3 then purified by vacuum distillation, sffording the title compound of the formula ICl CHF2CF2-0 ~ -NH2 Cl as a colourle~ liquid with a boiling point of 81-82Cl0.03 torr.
The following anilines of formula II are also prepared in corresponding manner:
ICl ClPCHCF2-0-~ NHz b.p.91-97C/0.015 torr 1~1 lCl CHCl2CP2-0-o~ NH2 b.p.107-110Cl0.015 torr ~1 ~1 Cc13cF2-O~ NH2 b.p.140C/0.01 torr Cl !Cl.
FBrCHCF2~0~~ -NH2 b.p.110-114C/0.012 torr Cl ~1 Br2CHCF2-0 ~ ~--NHz m.p.: 78C
Cl b) Preparation of N-2-chlorobenzoyl-N'-2,5-dichloro-4-(1',1',2',2'-tetrafluoroethoxy)phenylurea 5.3 g 2,5-dichloro-4-(1',1',2',2'-tetrafluoroethoxy)aniline are dissolved with stirring in 60 ml of dry toluene and, with excluslon of moisture, a solutlon of 3.46 g of 2-chlorobenzoylisocyanate in 10 ml of dry toluene is added at room temperature. The batch is Atirred for a further 10 hours at room temperature. About 75 % by volume of the solvent is then removed by rotary evaporation, the precipitated residue i8 filtered with ~uction, washed wlth a small amount of cold toluene and he~ane and then dried in vacuo, affording the title compound oP the formula ~ ~--C0-NH-C0-NH-~ -0-CF2CHF2 kl in the form of colourles~ crystals with a melting point of 184-185~C
(compound 1~.
The following compounds of formula I are prepared in a manner corresponding to that described above:
;
~2~3 Compound R1 R2 R3 m.p.[C]
. _ _ _ _ . . . ~ _ . . _ _ .... _ . _
The invention relates to compounds of formula I
~C0-NH-C0-NH-~ -0-R3 (I) R2 Cl wherein R1 is hydrogen, fluorine, chlorine, methyl, methoxy or methylthio, R2 i~ fluorine, chlorine, m~thyl, methoxy or methylthio ad R3 19 C1 C7haloalkyl containing 1 to 15 halogen atoms or is C3-C7halocycloalkyl containing 1 to 13 halogen atoms, with the proviso that R3 i8 not ~CF2-CHF-CF3. R3 i9 preferably C1-C3alkyl which i9 subst~tuted by 1 to 7 halogen atoms.
Compounds of formula I which ar0 preferred on account of their biological activity are tho~e wherein R2 iB methyl, methoxy or methylthio if R1 i9 hydrogen;
R2 is fluorine, methyl, methoxy or methylthio if R1 is fluorine; or R2 i8 chlorine, methyl, methoxy or methylthio if R1 is chlorine.
~L
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, .
, Compounds of formula I meriting special interest on account of their activity are tho~e wherein R1 and R2 are simultaneoufily fluorine or chlorine and, independently of each other, are methyl, methoxy or methyl~hio, and, in partlcular, tho~e compound~ wherein Rl and R2 are simultaneously fluorine or chlorine, preferably fluorine.
Further preferred compounds of formula I are those wherein R3 i~ one of the radicals -CHF2, -CF3, -CF2CHF2, -CH2CF3, -CF2CHClF, -CF2CHCl2, -CF2CCl3, -CF2CHBrz, -CF2CHBrF, -CF2C~lBr2, -CH2CHBrCH2Br, -CF(CF3)CHFCF3, -CF2CHFCF(CF3)2, -CF2CHF~CF2)4CF3 or ~CF2-~F2 in partlcular those compounds wherein R3 is one of the radicals -CF2CHF2, -CF2CHFCl, -CF2CHCl2 or -CFzCCl3. Those compound3 of formula I wherein R3 ifi Cs-C7haloalkyl containing 1 to 15 halogen atoma are also interefiting.
The compounds of formula I can be prepared by 1nethods analogous to onefi known per ~e (q.v. for example German Offenlegungsschrift speciications 2 123 236, 2 601 780 and 3 240 975).
l'hus, for example, a compound of formula I can be obtained by reacting a) a compound of formula II
~1 R3-O-~ -NH2 (II) with a compound of formula III
~1 CO-N~C~O (III) ~ 2 or b) a compound of formula IY
R3-O~ -N~C~O (IV) with a compound of formula V
~1 -CO-NHz (V) 1~2 or c) a compound of formula II w~th a compound of formula VI
~1 -CO-N~I-COOR ~VI).
~z In formulae II to VI above, Rl, R2 and R3 are a~ defined for formula I, and R 1~ a Cl-Caalkyl radical which 19 unsubstituted or substituted by halogen, preferably chlorine.
The sbove processes a), b~ and c) can preferably be carried out under normal pressure and in the presence of an organic 301vent or dil~ent. Examples of suitable solvents or diluenta are: ether~ and ethereal co~pounds, such as diethyl ether, dipropyl ether, dibutyl ether, dloxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylatad carboxamides; aliphatic, aromatic and halogenated hydrocarbons, i3 especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachlorlde and chlorobenzene; nltriles such 88 aceto-nitrile or propionitrile; dimethyl sulfoxlde; and ketones, e.g.
acetone, methyl ethyl ketone, methyl iiopropyl ketone and methyl isobutyl ketone. Process a) i8 normally carried out in the tempera-ture range from -10 to ~200C, preferably from O to 100C, e.g at room temperature, and, if desired in the presence of an organic base 7 e.g. trlethylamine. Process b) i~ carried out in the tempera-ture range from 0 to 150C, preferably at the boiling point of the solvent employed and, lf desired, in the presence of an organic base such as pyridine, and/or with the addition of an alkali metal or alkalin0 earth metal, preferably sodium. Fo~ process c), i.e. for the reaction of the urethanP of formula VI with an aniline of formula II, a temperature range from about 60 to the boiling point of the reactlon mixture i9 preferred, and the solvent employed i9 preferably an aromatlc hydrocarbon auch as toluene, xylene, chloro-benzene and the like.
The staxting materisls 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 ob~ect of the present invention. The compounds of formula II can be prepared in a manner known per se by hydrogenating suitably substltuted nitrobenzenes of formula VII
gl R3-O~ NO2 (VII) Cl by a process analogous to that described in J. Org. Chem. 29 (1964), 1, (q.v. also the literature cited therein). Ho~ever, the anillnes of formula II can also be obtained by chemicsl reduction (e.g. with Sn(II) chlorldel~Cl) of the corresponding nitro compounds of fol~ula YII (q.v. Houben-Weyl, "Methodcn d. org. Chemie" 11/1, 422).
The nitro compounds of formula VII can be prepared by h~lo-alkylating 2,5-dichloro-4-nitrophenol. A further proces~ for the ~2~ 3 preparation of the anilinas of formula II comprises haloalkylating acylated 2,5-dlchloro-4-hydroxyaniline and then removing the acyl group, e.g. by acid hydrolysis.
Benzoylisocyanates of formula III can be obtained, inter alia, as follows (q.v. J. A~r. Food Chem. 21, 348 and 993; 1973):
~ ~'-C 5 N HzS04M 20 ~ 0~ ~--CO-NHz ~Z ~2 CO-N-C-O (III) .
The 4-haloal~oxyphenyli30cyanates of formula IV can be prepared e.g. by phosgenating the anillnes of formula II by methods whlch are commonly employed in the art. The benazmides of formula V wh~ch are further used as starting materials are known (q.v. for example BeilstQin "Handbuch der organiscl)en Chemie'~, Vol. 9, p. 336).
Urethanes of formula VI can be obtalned in a manner known par se by reacting a ben~oyli~ocyanate of formula III with a suitable alcohol or by reactlng a benzamide of formula V, in the presence of a base, with a corresponding ester of chloroformic acid Cl-COOR.
Surprislngly, it has been found that the compounds of this inven-tion and the salts thereof have excellent propertia3 as pesticides while being well tolerated by plantg and having low toxicity to WarM blooded animals. They are particularly suitable for controlling insects and rapresentatives of the order Acarina that attack plants and animals.
In particular, the compounds of formula I are suitable for control-ling insects of the orders: Lepidoptera9 Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, ;i3 Mallophaga, Thysanura, Igoptera, Psocoptera and Hymenoptera, a3 well a9 representatives of the order Acarina of the families: Ixodldae, ~rgasidae, Tetranychldae and Dermanyssidae.
In addition to their action against flies, e.g. Musca domestica, and mosquito larvae, the compounds of formula I are also suitable for controlling plan~-destructive feeding insects in ornamentals and crops of useful plants, especially in cotton (8.g. against Spodoptera littoralis and Heliothis virescens) and in fruit and vegetables (e.g. against Laspeyresia pomonella, Leptinotarsa decemlineata and Epilachna varivestis). T~e compounds of formula I have a pronounced ovicidal and, in particular, larvicidal action against insect3, especially against larvae of noxious feeding insects. If compounds of formula I are ingested by adult insect stages with the feed, then a diminished oviposition and/or reduced hatching rate is observed in many insects, especially ln Coleopterae, e.g. Anthonomus grandis.
The compounds of formula I can also be used for controlling ecto-parasite~ such as Lucllia sericata, in domestic animals and produc-tive livestock, e.g. by troating animals, cowshed~, barns, stables etc., and paAtures.
The compounds of formula I are also sultable or controlling the following species of mites which attack crops of fruit and vegetables:
Tetranychus usticae, Tetranychus clnnabarinus, Panonychus ulmi, Broybia rubrioculus, Panonychus citri, Eriophyes piri, Eriophyes ribis, Eriophyes vitis, Tarsonemus pallidus, Phyllocoptes vitis and Phyllocoptruta oleivora.
The good pesticidal activity of the compounds of formula I of the invention corresponds to a mortality of at least 50-60 % of tha above pe3ts.
The activity of the compounds of formula I and of the composition~
containing them can be substantially broadened and adapted to prevailing circum~tances by addition of other insecticides and/or acaricides. Examples of guitable additi~es lnclude: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
The compounds of formula I are used in unmodified form, or preferably together wlth the acljuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders~ soluble powder~, dusts, granulates, and also encapsulations in e.g. polymer substan-ces. As with the nature of the compositions, the m2thods of appli-cation such as spr~ying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended ob~ectives and the prevsiling circumstance3.
The formulations, i.e. the compo3itions, preparstions or mixtures containing the compound (active ingredient) of the formula I or combinations thereof with other lnsecticide~ or acaricldes, and, where appropriate, a solid or liquid ad~uvant, are prepared in known manner, Q . g . by homogeneously mlxing and/or grinding the active ingredient3 with extenders, e.g. solvents, 301id carriers and, in some cases, surfaca-act~ve compounds (surfactants).
Suitable 301vents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalene~, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohol~ and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrro-lidonal dimethyl 3ulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such a~ epoxldised coconut oil or soybean oil; or water.
~L2~2~
- 8 ~
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorlllonite or attapulgite. In order to improve the physlcal properties it is al~o possible to add hlghly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorp-tiva carriers are porous types, for eY.ample pumice, broken brick, 3epiolite or bentonite; and suitable nonsorbent carriers are materials ~uch as calcite or sand. In addition, a great number of pregranulated mater~als of inorganic or organic nature can be used, e.g. especially dolomite or pulverlsed plant r~sidues.
Depending on the nature oE the compound of formula I to be formulated, or of combinations thereof with other insecticides or acaricides, suitable surface-active compouDds are nonionlc, cationic and~or anionic surfactants having good emul3ifying, dispersing and wetting properties. The term "surfactants" will also be understood R~ compriBing mixtures of surfactants.
Suitable anio~ic surfactants can be both water-soluble soaps and water-soluble synthotic surface-active compounds.
Suitable soaps are the al~ali metal salt~, alkaline earth metal salts or unaubstituted or substituted ammonium salts o higher fatty acids (C1O-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 or tallow oil. Further ~uitable surfactants aro also the fatty acid methyltaurin salts as well as modifled and unmodified phospholipids.
More frequently, however, so-called synthetic aurfactants are used, especially fatty sulfonates, fatty sul~ates, sulfonated benzimida-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 subst~-tuted ammonium salts and oontain a Cg-C22alkyl radical which also ;3 g includes the alkyl moiety of acyl radlcal~, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate9 or of a mixture of fatty alcol~ol sulfates obtained from natural fatty acid~.
These compounds also comprise the salts of sulfuric acid e3ters and sulfonic acid~ of fatty alcohol/ethylene oxide adductE~. The sulfona-ted benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to ~2 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-ethanolamine aalts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phospha~es, ~.g. salts of the pho~phoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide.
Non-ionic flurfactants are preEerably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturnted Eatty acicls and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adduct3 of polyethylene oxide with polypropylene glycol, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glyccl ether groups and 10 to 100 propylene glycol ether groups. These compound6 usually contain 1 to 5 ethylene glycc>l units per propylene glycol unit.
Representative example3 of non-lonic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ether6, polypropylene/-polyethylene oxide adducts, tributylphenoxypolyethoxyathanol, polyethylene glycol and octylphenoxypolyethoxyethanol. ~atty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are al60 suitable non-ionic ~urfactants.
i3 Cationic surfactants are preferably quaternary ammonium sal~8 whlch contain, as N-sub~tituent, at least ona Cg-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The 3alts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromid0.
The ~urfacta~ts customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and ~mulgifiers Annual", MC Publishing Corp. Ridgewood, New Jersey~ 1979; Dr. Helmut Stach0, "Tensid Taschenbuch" (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna, 1981.
The pesticidal composltions ususlly contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or combination thereof with other lnsecticides or acaricides, 1 to 99.9 % of a solid or liquid ad~uvant, and O to 25 %, preferably 0.1 to 20 %, of a suresctant.
Whereas commercial products are preferably formulated as concen-trates, the end user will normally employ diluted formulations of substantially lower concentration.
The compositions may also contaln further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
Example 1-a) Preparation of 2,5-dichloro-4 ~ 1',2' 2'-tetrafluoroethoxy~-aniline 18.6 g of 4-acetylamino-2,5-dichlorophenol together with 6.1 g of KOH powder and 130 ml of dimethylformamide are 5tirred in an autoclave. 20 g of tetrafluoroethylene are then pressed into ths , . .
2~;3 closed autoclave. The mixture is stirred for 20 hours at 70C under the pressure which has built up in the autoclave. After cooling, the mixture is concentrat~d by rotary evaporation and the residue i~
dissolved in methylene chloride. The resultant solution is washed with water, dried over Na2S04 and concentrated. After r0crystalli-sation from a mixture of methylene chloride and hexane, 2,5-di-chloro-4-(1',1',2',2'-tetrafluoroe~hoxy)acetanilide with a melting point of 119-120C i8 obtained. 15.8 g of the resultant 2,5-di-chloro-4~(1',1',2',2'-tetrafluoroethoxy~acetanilide are kept for 10 hours under reflux with 75 ml of ethanol and 25 m of 37 %
hydrochloric acid. The reaction mixturs i8 then concentrated, diluted with ice water and made weakly alkaline. The product i8 extracted from the mixture with ethylene chloride. The organic phase i8 wa~hed with water and dried over Na2S04 and the methylene chloride is distilled off.
The crude product i3 then purified by vacuum distillation, sffording the title compound of the formula ICl CHF2CF2-0 ~ -NH2 Cl as a colourle~ liquid with a boiling point of 81-82Cl0.03 torr.
The following anilines of formula II are also prepared in corresponding manner:
ICl ClPCHCF2-0-~ NHz b.p.91-97C/0.015 torr 1~1 lCl CHCl2CP2-0-o~ NH2 b.p.107-110Cl0.015 torr ~1 ~1 Cc13cF2-O~ NH2 b.p.140C/0.01 torr Cl !Cl.
FBrCHCF2~0~~ -NH2 b.p.110-114C/0.012 torr Cl ~1 Br2CHCF2-0 ~ ~--NHz m.p.: 78C
Cl b) Preparation of N-2-chlorobenzoyl-N'-2,5-dichloro-4-(1',1',2',2'-tetrafluoroethoxy)phenylurea 5.3 g 2,5-dichloro-4-(1',1',2',2'-tetrafluoroethoxy)aniline are dissolved with stirring in 60 ml of dry toluene and, with excluslon of moisture, a solutlon of 3.46 g of 2-chlorobenzoylisocyanate in 10 ml of dry toluene is added at room temperature. The batch is Atirred for a further 10 hours at room temperature. About 75 % by volume of the solvent is then removed by rotary evaporation, the precipitated residue i8 filtered with ~uction, washed wlth a small amount of cold toluene and he~ane and then dried in vacuo, affording the title compound oP the formula ~ ~--C0-NH-C0-NH-~ -0-CF2CHF2 kl in the form of colourles~ crystals with a melting point of 184-185~C
(compound 1~.
The following compounds of formula I are prepared in a manner corresponding to that described above:
;
~2~3 Compound R1 R2 R3 m.p.[C]
. _ _ _ _ . . . ~ _ . . _ _ .... _ . _
3 F -OCH3 -CF2CHF2 190-191
4 H Cl -CF2CHFCl 165-166 P Cl -CF2CHFCl 165-167 6 H Cl -CF2CHC12 165-167 7 H Cl -CFzCHFBr 161~162 8 H Cl -CF2CHBr2 172 9 F Cl -CF2CHBr2 188 H F -CF2CHBr2 215 11 F -OCH3 -CF2CHBr2 202-203 13 Cl Cl -CF2CHF2 211-213 14 F F -CF2CHFCl 174-175 Cl Cl -CF2CHFCl 202-207 16 F F -CF2CHClz 167-168 17 F F -CFzCCl3 206-210 18 F F -CH2CHBrCH2Br 190-192 19 Cl Cl -CH2CHBrCH2Br 188-191 P F -CFzCHFBr 190 21 F F -CF2CHBrz 185-186 22 C1 Cl -CF2CHBr2 214-215 23 F F -CFClCHFCl 148-150 24 Cl Cl -CFClCHFCl 140-142 F Cl -CHF2 223-224 27 H Cl -CHF2 194 The following compounds of formula 1 can also be prepared by the procedure descrlbed above:
Z~i3 Compound R1 R2 R3 28 H Cl -CFzCHF2 29 F Cl -CFzCHF2 H Cl -CF(CF3)CHFCF3 31 Cl F -CF(CF3)CHFCF3 32 H Cl -CFzCHFCF(CF3)2 33 Cl F -CFzCHFCF(CF3)z 34 H Cl -CFzCHF(CFz)l~CF3 36 -CH3 -CH3 -CFzCHF2 37 -OCH 3 -OCH3 -CFzCHF2 38 -SCH3 -SCH~ -CF2CHFz 39 Cl Cl -CFzCHF(CFz)4CF3 /CFz-~Fz H Cl -CF\
CHF-CFz CHF-,CF2 41 Cl F -C ~ I
CHF-CFz Example 2:
Formulations for active in~redients of formula I according_ o Example 1 or combinatione thereof with other insectlcides or acaricides (throughout, percentage~ are by weight) 1. Wettable powders a) b) c) compound of formula I or combination 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium laurylsulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
kaolin 62 % 27 %
%~;3 The active ingredient or combinatlon is thoroughly mixed with the ad~uvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted wlth water to give suspensions of the des~red concentration.
2. Emulsifiable concentrate compound of formula I or combination lO %
octylphenol polyethylene glycol ether (4-5 mole3 of ethylene oxide) 3 %
calcium dodecylbenzenesulfonate 3 %
ca3tor oil polygycol ether (36 moles of e~hylene oxide3 4 %
cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
3. Dusts a) b) compound of E~rmula I or combination 5 % 8 %
talcum 95 %
kaolin - 92 %
Ready for use dusts are obtained by mixing th0 active ingredient with the carrier, and grinding the mixture in a sultable mill.
4. Extruder granulate compound of formula I or combinationlO %
~odium ligno~ulfonat0 2 %
carboxymethylcellulos0 1 %
kaolin 87 %
The active ingredient or combination i8 mixed and ground ~ith the adjuvants, and the mixture i~ subsequently moi~tened with water. The mixture i8 extruded and then dried in a stream of air.
i3
Z~i3 Compound R1 R2 R3 28 H Cl -CFzCHF2 29 F Cl -CFzCHF2 H Cl -CF(CF3)CHFCF3 31 Cl F -CF(CF3)CHFCF3 32 H Cl -CFzCHFCF(CF3)2 33 Cl F -CFzCHFCF(CF3)z 34 H Cl -CFzCHF(CFz)l~CF3 36 -CH3 -CH3 -CFzCHF2 37 -OCH 3 -OCH3 -CFzCHF2 38 -SCH3 -SCH~ -CF2CHFz 39 Cl Cl -CFzCHF(CFz)4CF3 /CFz-~Fz H Cl -CF\
CHF-CFz CHF-,CF2 41 Cl F -C ~ I
CHF-CFz Example 2:
Formulations for active in~redients of formula I according_ o Example 1 or combinatione thereof with other insectlcides or acaricides (throughout, percentage~ are by weight) 1. Wettable powders a) b) c) compound of formula I or combination 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium laurylsulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
kaolin 62 % 27 %
%~;3 The active ingredient or combinatlon is thoroughly mixed with the ad~uvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted wlth water to give suspensions of the des~red concentration.
2. Emulsifiable concentrate compound of formula I or combination lO %
octylphenol polyethylene glycol ether (4-5 mole3 of ethylene oxide) 3 %
calcium dodecylbenzenesulfonate 3 %
ca3tor oil polygycol ether (36 moles of e~hylene oxide3 4 %
cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
3. Dusts a) b) compound of E~rmula I or combination 5 % 8 %
talcum 95 %
kaolin - 92 %
Ready for use dusts are obtained by mixing th0 active ingredient with the carrier, and grinding the mixture in a sultable mill.
4. Extruder granulate compound of formula I or combinationlO %
~odium ligno~ulfonat0 2 %
carboxymethylcellulos0 1 %
kaolin 87 %
The active ingredient or combination i8 mixed and ground ~ith the adjuvants, and the mixture i~ subsequently moi~tened with water. The mixture i8 extruded and then dried in a stream of air.
i3
5. Coated granulate compound of formul~ I or comblnation 3 %
polyethylene glycol 200 3 %
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.
polyethylene glycol 200 3 %
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.
6. Suspension concent~ate compound of formula I or combination 40 %
ethylene glycol l %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide~ 6 %
sodium lignosulfonate lO %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
sllicone oil in the form of a 75 %
aquoous emulsion 0.8 %
water 32 %
The finely ground active lngredient or combination i9 intimately mixed with the atl~uvant~, giving a suspension concentrate from which suspension~ of any desired concentration can be obtained by dilution with water.
Example 3_ Action against Musca domestica 50 g of freshly prepared nutrient substrate for maggots are charged into each of a number of beakers. A specific amount of an acetonic ~olution containing l % by weight of the respective test compound ls pipetted onto the nutrient substrate present in the beakeræ to give an active ingredient concentration of 800 ppm. The substrate i5 then thoroughly m~xed and the acetona subsequently allowed to evaporate ov~r a period of at lea~t 20 hour~.
' ~2~
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 activa ingredlent. After the maggots have pupated, the pupae are sPparated from the substrate by flushing them ou~ with water and then deposited in containers closed with a perforated top.
Each batch of flushed out pupae is counted to determine the toxic effect of the test compound on the maggot devalopment. A count is then made after 10 day~ of the number of flie~ which have hat~hed out of the pupae.
The compounds of formula I according to Example l exhibit good activity in this test.
Example 4: Action against Lucilia ~ericata 1 ml of an aqueous formulation containing 0. 5 % by weight of te3t compound is added at 50C to 9 ml of a culture medium. Then about 30 freshly hatched Lucilia serlcata larvae are added to the culture medium, and the inAacticidal action i9 determlned after 48 and 96 hours by eval~lating the mortality rate.
In this te~t, compound~ of formula I according to Example 1 exhibit good activity against Lucilia sericata.
Example 5: Action against Aëdes _ ~Ye~
A concentration of 800 ppm i~ obtaiDed by pipetting a specific amount of an acetonic solution containing O.l % by weight of the test compound onto the surface of 150 ml of water in a beaker.
After the acetone has evaporat2d, 30 to 40 two-day-old larvae of Aëdes aegypti are put into the beaker containing the test compound.
Mortality counts ara made after 1, 2 and 5 dsys.
In thi~ test, compounds of formula I according to Example l exhibit good aotivity against Aëdes aegypti.
~2a~53 -- lg --Example 6: Insectlcidal action against feeding in~ects Cotton plant8 about 25 cm high, in pots, are sprayed with aqueous emulsions which contain the test compound in a concentration of 400 ppm. After the spray coating has dried, the cotton plants are populated with Spodoptera littoralis and Heliothi3 virescens larvae in the L3~~tage. The test i8 carrled out at 24C and 60 % relative humidity. The percentage mortality of the test insects i8 determined after 120 hours.
Compound 1 effect~ 80 to 100 % mortality against Spocloptera larvae and }leliothis larvae at 400 ppm.
Example 7: Action against Epilachna varivestis Phaseolus vulgaris plants (dwarf beans) about 15-20 cm in height are sprayed with aqueous emulsion formulations of the test compound in a concentration of 800 ppm. After the spray coating has dried, each plant is populated with 5 larvne of Epilachna varivestis (Mexican bean beetle) in the L4-stage. A plastic cylinder i8 slipped over the treated plants and covered with a copper gauze top. The test i8 carried out at 28C and 60 % relative humidity. The percentage mortality is determined after 2 and 3 day~. Evaluation of feeding damage (anti-feeding effect), and of inhibition of development and shedding, is made by observing the test insects for a further 3 days.
The compounds of formula I according to Example 1 exhibit good activity in this test.
Example_8: Ovicidal action against Heliothis virescen6 Correspondlng amount~ of a wettable powder formulation containing 25 % by weight of the test compound are mixed with sufficient water to produce an aqueous emul~ion with an active ingredient concen-tration of 400 ppm. One-dRy-old egg deposits of }leliothis on cellophane~are immersed in these emulsions for 3 minutes and then collected by suction on round filters. The treated deposits are ~2~3 placed in petri dishes and kept in the dark at 28C and 60 %
relative humidity. The hatching rate, i.e. ~he number of larvae which have developed from the treatad eg~s, in comparison with untreatad controls i8 determined after 5 to 8 days.
Compound 1 according to Example 1 exhibits an 80 to 100 % ovicidal activity (mortality) in this test.
Example 9 Action against Laspeyresia pomonella (eggs):
Egg deposits of Laspeyresia pomonella not more than 24 hours old are immersed on filter paper for l minute in an aqueous acetonic solutlon 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 28C. The percentage of larvae hatched from the treated eggs and the percentage mortality is evaluated after 6 dnys.
The compounds of formula I according to Example 1 exhibit good activity in tllis test.
Example 10: Influence~ _r~ duction of Anthonomous grandis Anthonomous grandis adults which are not more than 24 hours old after hatching are transferred in groups of 25 to barred cages. The cages are then immersed for 5 to 10 ~oconds in an acetonic solution containing O.l % by weight of the test compound. After the beetles have dried, they are placed in covared dishes containing feed and left for copulation and oviposition. Egg deposit3 are flushed out with running water twlce to three time~ weekly, counted, disinfected by putting them for 2 to 3 hours into an aqueou~ disinfectant, and then placed in dishes containing a suitable larval feed. A count is made after 7 days to determine the number of larvae which have developed from the eggs.
` ' ,.
The duration of the reproduction inhibiting effect of the test compounds is determined by monitorlng the egg deposits further, i.e.
over a period of about 4 week3. Evaluation is made by assessing the reduction ln the number of deposited eggs and hatched lsrvae in comparison with untreated controls.
The compounds of formula I according to Example 1 exhibit a good reproduction reducing activity in this test.
Example 11: Action against Anthonomus grandis (adults) Two cotton plant~ in the 6-leaf stage 9 in pots, are each sprayed with a wsttable aqueous emulsion formulation containing 400 ppm of the test compound. After the spray coating has dried (about 1 1/2 hours), each plant i~ 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 te~t insects to prevent the beetles from migrating from the plants. The treated plants are then kept at 25C and about 60 % relative humidity. Evaluation is mad0 after 2, 3, 4 and 5 days to determine the percentage mortality of the beetles (percentage in dorsal position) as well as the snti-feeding action ao compared with untreated controls.
Compound 1 according to Example 1 effects 80 to 100 % mortality in thi3 test.
ethylene glycol l %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide~ 6 %
sodium lignosulfonate lO %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
sllicone oil in the form of a 75 %
aquoous emulsion 0.8 %
water 32 %
The finely ground active lngredient or combination i9 intimately mixed with the atl~uvant~, giving a suspension concentrate from which suspension~ of any desired concentration can be obtained by dilution with water.
Example 3_ Action against Musca domestica 50 g of freshly prepared nutrient substrate for maggots are charged into each of a number of beakers. A specific amount of an acetonic ~olution containing l % by weight of the respective test compound ls pipetted onto the nutrient substrate present in the beakeræ to give an active ingredient concentration of 800 ppm. The substrate i5 then thoroughly m~xed and the acetona subsequently allowed to evaporate ov~r a period of at lea~t 20 hour~.
' ~2~
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 activa ingredlent. After the maggots have pupated, the pupae are sPparated from the substrate by flushing them ou~ with water and then deposited in containers closed with a perforated top.
Each batch of flushed out pupae is counted to determine the toxic effect of the test compound on the maggot devalopment. A count is then made after 10 day~ of the number of flie~ which have hat~hed out of the pupae.
The compounds of formula I according to Example l exhibit good activity in this test.
Example 4: Action against Lucilia ~ericata 1 ml of an aqueous formulation containing 0. 5 % by weight of te3t compound is added at 50C to 9 ml of a culture medium. Then about 30 freshly hatched Lucilia serlcata larvae are added to the culture medium, and the inAacticidal action i9 determlned after 48 and 96 hours by eval~lating the mortality rate.
In this te~t, compound~ of formula I according to Example 1 exhibit good activity against Lucilia sericata.
Example 5: Action against Aëdes _ ~Ye~
A concentration of 800 ppm i~ obtaiDed by pipetting a specific amount of an acetonic solution containing O.l % by weight of the test compound onto the surface of 150 ml of water in a beaker.
After the acetone has evaporat2d, 30 to 40 two-day-old larvae of Aëdes aegypti are put into the beaker containing the test compound.
Mortality counts ara made after 1, 2 and 5 dsys.
In thi~ test, compounds of formula I according to Example l exhibit good aotivity against Aëdes aegypti.
~2a~53 -- lg --Example 6: Insectlcidal action against feeding in~ects Cotton plant8 about 25 cm high, in pots, are sprayed with aqueous emulsions which contain the test compound in a concentration of 400 ppm. After the spray coating has dried, the cotton plants are populated with Spodoptera littoralis and Heliothi3 virescens larvae in the L3~~tage. The test i8 carrled out at 24C and 60 % relative humidity. The percentage mortality of the test insects i8 determined after 120 hours.
Compound 1 effect~ 80 to 100 % mortality against Spocloptera larvae and }leliothis larvae at 400 ppm.
Example 7: Action against Epilachna varivestis Phaseolus vulgaris plants (dwarf beans) about 15-20 cm in height are sprayed with aqueous emulsion formulations of the test compound in a concentration of 800 ppm. After the spray coating has dried, each plant is populated with 5 larvne of Epilachna varivestis (Mexican bean beetle) in the L4-stage. A plastic cylinder i8 slipped over the treated plants and covered with a copper gauze top. The test i8 carried out at 28C and 60 % relative humidity. The percentage mortality is determined after 2 and 3 day~. Evaluation of feeding damage (anti-feeding effect), and of inhibition of development and shedding, is made by observing the test insects for a further 3 days.
The compounds of formula I according to Example 1 exhibit good activity in this test.
Example_8: Ovicidal action against Heliothis virescen6 Correspondlng amount~ of a wettable powder formulation containing 25 % by weight of the test compound are mixed with sufficient water to produce an aqueous emul~ion with an active ingredient concen-tration of 400 ppm. One-dRy-old egg deposits of }leliothis on cellophane~are immersed in these emulsions for 3 minutes and then collected by suction on round filters. The treated deposits are ~2~3 placed in petri dishes and kept in the dark at 28C and 60 %
relative humidity. The hatching rate, i.e. ~he number of larvae which have developed from the treatad eg~s, in comparison with untreatad controls i8 determined after 5 to 8 days.
Compound 1 according to Example 1 exhibits an 80 to 100 % ovicidal activity (mortality) in this test.
Example 9 Action against Laspeyresia pomonella (eggs):
Egg deposits of Laspeyresia pomonella not more than 24 hours old are immersed on filter paper for l minute in an aqueous acetonic solutlon 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 28C. The percentage of larvae hatched from the treated eggs and the percentage mortality is evaluated after 6 dnys.
The compounds of formula I according to Example 1 exhibit good activity in tllis test.
Example 10: Influence~ _r~ duction of Anthonomous grandis Anthonomous grandis adults which are not more than 24 hours old after hatching are transferred in groups of 25 to barred cages. The cages are then immersed for 5 to 10 ~oconds in an acetonic solution containing O.l % by weight of the test compound. After the beetles have dried, they are placed in covared dishes containing feed and left for copulation and oviposition. Egg deposit3 are flushed out with running water twlce to three time~ weekly, counted, disinfected by putting them for 2 to 3 hours into an aqueou~ disinfectant, and then placed in dishes containing a suitable larval feed. A count is made after 7 days to determine the number of larvae which have developed from the eggs.
` ' ,.
The duration of the reproduction inhibiting effect of the test compounds is determined by monitorlng the egg deposits further, i.e.
over a period of about 4 week3. Evaluation is made by assessing the reduction ln the number of deposited eggs and hatched lsrvae in comparison with untreated controls.
The compounds of formula I according to Example 1 exhibit a good reproduction reducing activity in this test.
Example 11: Action against Anthonomus grandis (adults) Two cotton plant~ in the 6-leaf stage 9 in pots, are each sprayed with a wsttable aqueous emulsion formulation containing 400 ppm of the test compound. After the spray coating has dried (about 1 1/2 hours), each plant i~ 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 te~t insects to prevent the beetles from migrating from the plants. The treated plants are then kept at 25C and about 60 % relative humidity. Evaluation is mad0 after 2, 3, 4 and 5 days to determine the percentage mortality of the beetles (percentage in dorsal position) as well as the snti-feeding action ao compared with untreated controls.
Compound 1 according to Example 1 effects 80 to 100 % mortality in thi3 test.
Claims (26)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of formula I
(I) wherein R1 is hydrogen, fluorine, chlorine, methyl, methoxy or methylthio, R2 is fluorine, chlorine, methyl, methoxy or methylthio ad R3 is C1-C7haloalkyl containing 1 to 15 halogen atoms or is C3-C7halocycloalkyl containing 1 to 13 halogen atoms, with the proviso that R3 is not -CF2-CHF-CF3.
(I) wherein R1 is hydrogen, fluorine, chlorine, methyl, methoxy or methylthio, R2 is fluorine, chlorine, methyl, methoxy or methylthio ad R3 is C1-C7haloalkyl containing 1 to 15 halogen atoms or is C3-C7halocycloalkyl containing 1 to 13 halogen atoms, with the proviso that R3 is not -CF2-CHF-CF3.
2. A compound of formula I according to claim 1, wherein R3 is C1-C3alkyl which is substituted by 1 to 7 halogen atoms.
3. A compound according to either of claims 1 or 2, wherein R2 is methyl, methoxy or methylthio if R1 is hydrogen;
R2 is fluorine, methyl, methoxy or methylthio if R1 is fluorine; or R2 is chlorino, methyl, methoxy or methylthio if R1 is chlorine.
R2 is fluorine, methyl, methoxy or methylthio if R1 is fluorine; or R2 is chlorino, methyl, methoxy or methylthio if R1 is chlorine.
4. A compound of formula I according to claim 1 wherein R1 and R2 are simultaneously fluorine or chlorine or, independently of each other, are methyl, methoxy or methylthio.
5. A compound of formula I according to claim 4, wherein R1 and R2 are simultaneously fluorine or chlorine.
6. A compound of formula I according to claim 5, wherein R1 and R2 are simultaneously fluorine.
7. A compound of formula I according to claim 1 wherein R3 is one of the radicals -CHF2, -CF3, -CF2CHF2, -CH2-CF3, -CF2CHClF, -CF2CHCl2, -CF2CCl3, -CF2CHBr2, -CF2CHBrF, -CF2CHBr2, -CH2CHBrCH2Br, -CF(CF3)CHFCF3, -CF2CHFCF(CF3)2, -CF2CHF(CF2)4CF3 or
8. A compound of formula I according to claim 7, wherein R3 is one of the radicals -CF2CHF2, -CF2CHFCl, -CF2CHCl2 or -CF2CCl3.
9. A compound of formula I according to claim 1, wherein R3 is C5-C7haloalkyl containing 1 to 15 halogen atoms.
10. The compound according to claim 6 of the formula
11. The compound according to claim 6 of the formula
12. The compound according to claim 6 of the formula
13. The compound according to claim 6 of the formula
14. The compound according to claim 6 of the formula
15. The compound according to claim 2 of the formula
16. The compound according to claim 2 of the formula
17. The compound of the formula
18. The compound of the formula
19. The compound according to claim 2 of the formula
20. The compound of the formula
21. A process for the preparation of a compound according to any one of claim 1 which process comprises reacting a) a compound of formula II
(II) with a compound of formula III
(III) or b) a compound of formula IV
(IV) with a compound of formula V
(V) or c) a compound of formula II with a compound of formula VI
(VI) in which formulae II to VI the radicals R1, R2 and R3 are as defined in claim 1 and R is a C1-C8alkyl radical which is un-substituted or substituted by halogen.
(II) with a compound of formula III
(III) or b) a compound of formula IV
(IV) with a compound of formula V
(V) or c) a compound of formula II with a compound of formula VI
(VI) in which formulae II to VI the radicals R1, R2 and R3 are as defined in claim 1 and R is a C1-C8alkyl radical which is un-substituted or substituted by halogen.
22. A pesticidal composition which contains an acceptable inert carrier and, as active ingredient, a compound according to claim 1.
23. A method of controlling insects and representatives of the order Acarina, which method comprises contacting or treat-ing said pests, their various development stages or the locus thereof with a pesticidally effective amount of a compound of formula I according to claim 1, or with a composition which contains a pesticidally effective amount of such a compound, together with adjuvants and carriers.
24. A method according to claim 23 for controlling insects and representatives of the order Acarina.
25. A method according to claim 23 for controlling larval stages of plant-destructive insects.
26. A method according to claim 23 wherein the compound or composition is applied as an insect ovicide.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH499384 | 1984-10-18 | ||
| CH4993/84-1 | 1984-10-18 | ||
| CH536184 | 1984-11-08 | ||
| CH5361/84-2 | 1984-11-08 | ||
| CH2048/85-1 | 1985-05-14 | ||
| CH204885 | 1985-05-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1242453A true CA1242453A (en) | 1988-09-27 |
Family
ID=27173428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000493028A Expired CA1242453A (en) | 1984-10-18 | 1985-10-16 | Benzoylphenylureas |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0179021A3 (en) |
| KR (1) | KR860003207A (en) |
| AU (1) | AU585539B2 (en) |
| BR (1) | BR8505174A (en) |
| CA (1) | CA1242453A (en) |
| EG (1) | EG17507A (en) |
| GB (1) | GB2166134B (en) |
| IL (1) | IL76731A0 (en) |
| ZW (1) | ZW18085A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL76708A (en) * | 1984-10-18 | 1990-01-18 | Ciba Geigy Ag | Substituted n-benzoyl-n'-(2,5-dichloro-4(1,1,2,3,3,3-hexafluoropropyloxy)-phenyl)ureas,their preparation and pesticidal compositions containing them |
| AU602305B2 (en) * | 1985-03-14 | 1990-10-11 | Istituto Guido Donegani S.P.A. | N-(halobenzoyl)-N-(polyhaloalkoxyphenyl) urea derivatives |
| ATE69603T1 (en) * | 1986-02-28 | 1991-12-15 | Ciba Geigy Ag | N-BENZOYL-N'-PHENYLUREAS, THEIR PRODUCTION AND USE IN PEST CONTROL. |
| DE3613062A1 (en) * | 1986-04-18 | 1987-10-29 | Hoechst Ag | N-BENZOYL-N'-PHENYL (THIO) UREAS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PEST CONTROL |
| US4925875A (en) * | 1987-07-21 | 1990-05-15 | Ciba-Geigy Corporation | N-benzoyl-N'-2,5-dihalo-4-perfluoroalkoxyphenylureas, pesticidal compositions containing them and their use in the control of pests |
| TW282393B (en) * | 1992-06-01 | 1996-08-01 | Dowelanco Co | |
| WO1994003066A1 (en) * | 1992-07-29 | 1994-02-17 | Ciba-Geigy Ag | Method and composition for controlling cockroaches |
| US5945453A (en) * | 1996-11-08 | 1999-08-31 | Dow Agrosciences Llc | Benzoylphenylurea insecticides to control cockroaches |
| WO1998019995A1 (en) * | 1996-11-08 | 1998-05-14 | Dow Agrosciences Llc | New benzoylphenylurea insecticides ans methods of using them to control cockroaches |
| US5886221A (en) | 1997-11-03 | 1999-03-23 | Dow Agrosciences Llc | Benzoylphenylurea insecticides and methods of using certain benzoylphenylureas to control cockroaches, ants, fleas, and termites |
| US5811461A (en) * | 1997-10-31 | 1998-09-22 | Dow Agrosciences Llc | Benzoylphenylurea insecticides and methods of using them to control cockroaches, ants, fleas, and termites |
| US5874615A (en) * | 1998-03-17 | 1999-02-23 | American Cyanamid Co | Method for the preparation of insecticidal benzoylurea compounds |
| US6538031B1 (en) | 1999-11-25 | 2003-03-25 | Novartis Animal Health Us, Inc. | Method of controlling sea lice infestation in fish |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA825470B (en) * | 1981-07-30 | 1984-03-28 | Dow Chemical Co | Substituted n-aroyl n'-phenyl urea compounds |
| US4518804A (en) * | 1982-07-26 | 1985-05-21 | The Dow Chemical Company | Halo(alkoxy/alkylthio)-benzenamines |
| EP0136745B1 (en) * | 1983-09-01 | 1989-06-07 | Duphar International Research B.V | Benzoyl urea derivatives having anti-tumor activity |
| EP0167197B1 (en) * | 1984-07-05 | 1989-01-18 | Duphar International Research B.V | Benzoylurea compounds, and insecticidal and acaricidal compositions comprising same |
-
1985
- 1985-10-14 EP EP85810467A patent/EP0179021A3/en not_active Withdrawn
- 1985-10-16 GB GB08525517A patent/GB2166134B/en not_active Expired
- 1985-10-16 CA CA000493028A patent/CA1242453A/en not_active Expired
- 1985-10-17 KR KR1019850007647A patent/KR860003207A/en not_active Application Discontinuation
- 1985-10-17 EG EG66485A patent/EG17507A/en active
- 1985-10-17 BR BR8505174A patent/BR8505174A/en unknown
- 1985-10-17 IL IL76731A patent/IL76731A0/en unknown
- 1985-10-17 AU AU48819/85A patent/AU585539B2/en not_active Expired
- 1985-10-17 ZW ZW180/85A patent/ZW18085A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL76731A0 (en) | 1986-02-28 |
| GB8525517D0 (en) | 1985-11-20 |
| AU585539B2 (en) | 1989-06-22 |
| GB2166134B (en) | 1988-07-27 |
| EG17507A (en) | 1994-09-29 |
| KR860003207A (en) | 1986-05-21 |
| AU4881985A (en) | 1986-04-24 |
| ZW18085A1 (en) | 1986-05-14 |
| EP0179021A2 (en) | 1986-04-23 |
| GB2166134A (en) | 1986-04-30 |
| EP0179021A3 (en) | 1987-05-13 |
| BR8505174A (en) | 1986-07-29 |
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