GB2166134A - Insecticidal benzoylphenylureas - Google Patents
Insecticidal benzoylphenylureas Download PDFInfo
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- GB2166134A GB2166134A GB08525517A GB8525517A GB2166134A GB 2166134 A GB2166134 A GB 2166134A GB 08525517 A GB08525517 A GB 08525517A GB 8525517 A GB8525517 A GB 8525517A GB 2166134 A GB2166134 A GB 2166134A
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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
-
- 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
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- 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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- 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)
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
SPECIFICATION
Benzoylphenylureas
The present invention relates to novel substituted N-benzoyl-N'-2,5-dichloro-4-haloalkoxyphenylu- reas, 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
wherein R is hydrogen, fluorine, chlorine, methyl, methoxy or methylthio, R2 is fluorine, chlorine, methyl, methoxy or methylthio ad R3 is C,-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. R3 is preferably C1-C3alkyl which is substituted by 1 to 7 halogen atoms.
Compounds of formula I which are preferred on account of their biological activity are those wherein
R2 is methyl, methoxy or methylthio if R1 is hydrogen;
R2 is fluorine, methyl, methoxy or methylthio if R, is fluorine; or
R2 is chlorine, methyl, methoxy or methylthio if R1 is chlorine.
Compounds of formula I meriting special interest on account of their activity are those wherein
R, and R2 are simultaneously fluorine or chlorine and, independently of each other, are methyl, methoxy or methylthio, and, in particular, those compounds wherein R1 and R2 are simultaneously fluorine or chlorine, preferably fluorine.
Further preferred compounds of formula I are those wherein R3 is one of the radicals -CHF2, -CF3, -CF2CHF2, -CH2CHCIF, -CF2CHCI2, -CF2CCI3, -CF2CHBr2, -CF2CHBrF, -CF2CHBr2, -CH2CHBrCH2Br, -CF(CF3)CHFCF3, -CF2CHFCF(CF3)2, -CF2CHF(CF2)4CF3 or
in particular those compounds wherein R3 is one of the radicals -CF2CHF2, -CF2CHFCI, -CF2CHCI2 or -CF2CCI3. Those compounds of formula I wherein R3 is Cs-C7haloalkyl containing 1 to 15 halogen atoms are also interesting.
The compounds of formula I can be prepared by methods analogous to ones known per se (q.v. for example German Offenlegungsschrift specification 2 123 236, 2 601 780 and 3 240 975).
Thus, for example, a compound of formula I can be obtained by reacting
(a) a compound of formula Il
with a compound of formula Ill
or
(b) a compound of formula IV
with a compound of formula V
or
(c) a compound of formula II with a compound of formula IV
In formulae II to VI above, R1, R2 and R3 are as defined for formula I, and R is a C,-C,alkyl radical which is unsubstituted or substituted by halogen, preferably chlorine.
The above processes (a), (b) and (c) can preferably be carried out under normal pressure and in the presence of an organic solvent or diluent. Examples of suitable solvents or diluents are: ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; nitriles such as acetonitrile or propionitrile; dimethyl sulfoxide; and ketones, e.g. acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone.Process (a) is normally carried out in the temperature 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 the temperature range from 0 to 1500C, preferably at the boiling point of the solvent employed and, if desired, in the presence of an organic base such as pyridine, and/or with the addition of an alkali metal or alkaline earth metal, preferably sodium.For process (c), i.e. for the 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 employed 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 known ones. The starting materials of formula II are novel compounds which likewise constitute an object of the present invention. The compounds of formula II can be prepared in a manner known per se by hydrogenating suitably substituted nitrobenzenes of formula VII
by a process analogous to that described in J. Org. Chem. 29 (1964), 1, (q.v. also the literature cited therein). However, the anilines of formula II can also be obtained by chemical reduction (e.g. with Sn(ll) chloride/HCI) of the corresponding nitro compounds of formula VII (q.v. Houben
Weyl, "Methoden d. org. Chemie" 11/1, 422). The nitro compounds of formula VII can be prepared by haloalkylating 2,5-dichloro-4-nitrophenol.A further process for the preparation of the anilines of formula Il comprises haloalkylating acylated 2,5-dichloro-4-hydroxyaniline and then removing the acyl group, e.g. by acid hydrolysis.
Benzoylisocyanates of formula Ill can be obtained, inter alia, as follows (q.v. J. Agr. Food
Chem. 21, 348 and 993; 1973):
The 4-haloalkoxyphenylisocyanates of formula IV can be prepared e.g. by phosgenating the anilines of formula II by methods which are commonly employed in the art. The benzamides of formula V which are further used as starting materials are known (q.v. for example Beilstein "Handbuch der organischen Chemie", Vol. 9, p. 336).
Urethanes of formula VI can be obtained in a manner known per se by reacting a benzoylisocyanate of formula Ill with a suitable alcohol or by reacting a benzamide of formula V, in the presence of a base, with a corresponding ester of chloroformic acid CI-COOR.
Surprisingly, it has been found that the compounds of this invention and the salts thereof have excellent properties as pesticides while being well tolerated by plants and having low toxicity to warm-blooded animals. They are particularly suitable for controlling insects and representatives of the order Acarina that attack plants and animals.
In particular, the compounds of formula I are suitable for controlling insects of the orders:
Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura,
Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatives of the order Acarina of the families: Ixodidae, Argasidae, Tetranychidae and Dermanyssidae.
In addition to their action against flies, e.g. Musca domestica, and mosquito larvae, the compounds of formula I are also suitable for controlling plant-destructive feeding insects in ornamentals and crops 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 of formula I have a pronounced ovicidal and, in particular, larvicidal action against insects, 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 in Coleopterae, e.g. Anthonomus grandis.
The compounds of formula I can also be used for controlling ectoparasites such as Lucilia sericata, in domestic animals and productive livestock, e.g. by treating animals, cowsheds, barns, stables etc., and pastures.
The compounds of formula I are also suitable for controlling the following species of mites which attack crops of fruit and vegetables: Tetranychus urticae, Tetranychus cinnabarinus, 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 the above pests.
The activity of the compounds of formula I and of the compositions containing them can be substantially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
The compounds of formula I are used in unmodified form, or preferably together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g.
polymer substances. As with the nature of the compositions, the methods of application such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of the formula I or combinations thereof with other insecticides or acaricides, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, in some cases, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materils 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 other insecticides or acaricides, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of 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 suitable 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 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 lignosulfonic acid, or dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product.Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of pnonylphenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 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 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.
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethy
I)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ridgewood, New Jersey,
1979; Dr. Helmut Stache, "Tensid Taschenbuch" (Handbook of Surfactants), Carl Hanser Verlag,
Munich/Vienna, 1981.
The pesticidal compositions usually contain 0.1 to 99%, preferably 0.1 to 95%, of a compound of formula I or combination thereof with other insecticides or acaricides, 1 to 99.9% of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 20%, of a surfactant.
Whereas commercial products are preferably formulated as concentrated, the end user will normally employ diluted formulations of substantially lower concentration.
The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
The following Examples further illustrate the present invention.
Example 1: (a) Preparation of 2, 5-dichloro-4-( 1', 1 ',2',2'-tetrafluoroethoxy)aniiine 18.6 g of 4-acetylamino-2,5-dichlorophenol together with 6.1 g of KOH powder and 130 ml of dimethylformamide are stirred in an autoclave. 20 g of tetrafluoroethylene are then pressed into the closed autoclave. The mixture is stirred for 20 hours at 70"C under the pressure which has built up in the autoclave. After cooling, the mixture is concentrated by rotary evaporation and the residue is dissolved in methylene chloride. The resultant solution is washed with water, dried over Na2SO4 and concentrated.After recrystallisation from a mixture of methylene chloride and hexane, 2,5-dichloro-4-(1',1',2',2'-tetrafluoroethoxy)acetanilide with a melting point of 119-120"C is obtained, 15.8 g of the resultant 2,5-dichloro-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 mixture is then concentrated, diluted with ice water and made weakly alkaline. The product is extracted from the mixture with ethylene chloride. The organic phase is washed with water and dried over Na2SO4 and the methylene chloride is distilled off.
The crude product is then purified by vacuum distillation, affording the title compound of the formula
as a colourless liquid with a boiling point of 81-82"C/0.03 torr.
The following anilines of formula Il are also prepared in corresponding manner:
b.p. 91-97"C/0.015 torr b.p. 107-110"C/0.015 torr b.p. 140"C/0.01 torr
b.p. 110-114"C/0.012 torr
m.p.: 78"C (b) Preparation of N-2-chlorobenzoyl-N'-2,5-dichloro-4-(1',1'2',2ttetrafluoroethoxyJphenylurea 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 exclusion of moisture, a solution of 3.46 g of 2-chlorobenzoylisocyanate in 10 ml of dry toluene is added at room temperature. The batch is stirred for a further 10 hours at room temperature.About 75% by volume of the 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 the title compound of the formula
in the form of colourless 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:
Compound R1 Rz R3 m.p.[ C]
2 H F -CF2CHF2 167-168
3 F -OCHa -CF2CHF2 190-191
4 H C1 -CF2CHFC1 165-166
5 F C1 -CF2CHFC1 165-167
6 H C1 -CF2CHC12 165-167
7 H C1 -CF2CHFBr 161-162
8 H Cl -CF2CHBr2 172
9 F Cl -CF2CHBr2 188
10 H F -CF2CHBr2 215
11 F -OCH3 -CF2CHBr2 202-203
12 F F -CF2CHF2 183-184
13 Cl Cl -CF2CHF2 211-213
14 F F -CF2CHFCl 174-175
15 Cl Cl -CF2CHFC1 202-207
16 F F -CF2CHCl2 167-168
17 F F -CF2CC13 206-210
18 F F -CH2CHBrCH2Br 190-192
19 Cl Cl -CH2CHBrCHzBr 188-191
20 F F -CF2CHFBr 190
21 F F -CFzCHBr2 185-186
22 Cl Cl -CF2CHBr2 214-215
23 F F -CFClCHFCl 148-150
24 Cl Cl -CFClCHFCl 140-142
25 F Cl -CHF2 223-224
26 F F -CHF2 195-196
27 H Cl -CHF2 194
The following compounds of formula I can also be prepared by the procedure described above:
Compound R1 R2 R3 28 H C1 -CF2CHF2 29 F C1 -CF2CHF2 30 H C1 -CF(CF3)CHFCF3 31 C1 F -CF(CF3)CHFCF3 32 H Cl -CF2CHFCF(CF3)2 33 C1 F -CF2CHFCF(CF3)2 34 H C1 -CF2CHF(CF2)4CF3 35 F F -CF3 36 -CH3 -CH3 -CF2CHF2 37 -OCH3 -OCH3 -CF2CHF2 38 -SCH3 -SCH3 -CF2CHF2 39 C1 C1 -CF2CHF(CF2)CF3 CF2-ÇF2 40 H C1 -CFs i CHF-CF 2 CHF-ÇF2 41 C1 F -CF\ | CHF- F2 Example 2:
Formulations for active ingredients of formula I according to Example 1 or combinations thereof with other insecticides or araricides (throughout, percentages 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%
The active ingredient or combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
2. Emulsifiable concentrate compound of formula I or combination 10% octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3% calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (36 moles of ethylene oxide) 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 formula I or combination 5% 8% talcum 95% kaolin 92% Ready for use dusts are obtained by mixing the active ingredient with the carrier, and grinding the mixture in a suitable mill.
4. Extruder granulate compound of formula I or combination 10% sodium lignosulfonate 2% carboxymethylcellulose 1 % kaolin 87%
The active ingredient or combination is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
5. Coated granulate compound of formula I or combination 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.
6. Suspension concentrate compound of formula 1 or combination 40 % ethylene glycol 10 % nonylphenol polyethylene glycol ether (15 moles of ethylene oxide), 6 % sodium lignosulfonate 10 %
Carboxymethylcellulose 1 % 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous emulsion 0.8% water 32 %
The finely ground active ingredient or combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Example 3: Action against Musca domestica
50 g of freshly prepared nutrient substrate for maggots are charged into each of a number of beakers. A specific amount of an acetonic solution containing 1% by weight of the respective test compound is pipetted onto the nutrient substrate present in the beakers to give an active ingredient concentration of 800 ppm. The substrate is then thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 20 hours.
Then 25 one-day-old maggots of Musca domestica are put into each of the beakers containing the treated nutrient substrate for testing with each active ingredient. 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 is counted to determine the toxic effect of the test compound on the maggot development. A count is then made after 10 days of the number of flies which have hatched out of the pupae.
The compounds of formula I according to Example 1 exhibit good activity in this test.
Example 4: Action against Lucilia sericata
1 ml of an aqueous formulation containing 0.5% by weight of test compound is added at 50"C to 9 ml of a culture medium. Then about 30 freshly hatched Lucilia sericata larvae are added to the culture medium, and the insecticidal action is determined after 48 and 96 hours by evaluating the mortality rate.
In this test, compounds of formula I according to Example 1 exhibit good activity against
Lucilia sericata.
Example 5: Action against Abodes aegypti
A concentration of 800 ppm is obtained by pipetting a specific amount of an acetonic solution containing 0.1% by weight of the test compound onto the surface of 150 ml of water in a beaker. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aides aegypti are put into the beaker containing the test compound. Mortality counts are made after 1, 2 and 5 days.
In this test, compounds of formula I according to Example 1 exhibit good activity against
Andes aegypti.
Example 6: Insecticidal action against feeding insects
Cotton plants 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 Heliothis virescens larvae in the L3-stage. The test is carried out at 24"C and 60% relative humidity. The percentage mortality of the test insects is determined after 120 hours.
Compound 1 effects 80 to 100% mortality against Spodoptera larvae and Heliothis 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 larvae of Epilachna varivestis (Mexican bean beetle) in the L4-stage. A plastic cylinder is slipped over the treated plants and covered with a copper gauze top. The test is carried out at 28"C and 60% relative humidity. The percentage mortality is determined after 2 and 3 days. Evaluation of feeding damage (anti-feeding effect), and of inhibition of development and shedding, is made by observing the test insects for a further 3 days.
The compounds of formula I according to Example 1 exhibit good activity in this test.
Example 8: Ovicidal action against Heliothis virescens
Corresponding amounts of a wettable powder formulation containing 25% by weight of the test compound are mixed with sufficient water to produce an aqueous emulsion with an active ingredient concentration of 400 ppm. One-day-old egg deposits of Heliothis on cellophane are immersed in these emulsions for 3 minutes and then collected by suction on round filters. The treated deposits are placed in petri dishes and kept in the dark at 28"C and 60% relative humidity. The hatching rate, i.e. the number of larvae which have developed from the treated eggs, in comparison with untreated controls is 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 1 minute in an aqueous acetonic solution containing 800 ppm of the test compound.
After the solution has dried, the eggs are placed in petri dishes and kept at a temperature of 28"C. The percentage of larvae hatched from the treated eggs and the percentage mortality is evaluated after 6 days.
The compounds of formula I according to Example 1 exhibit good activity in this test.
Example 10: Influence on the reproduction of Anthonomous grandis
Anthonomous grandis adults which are not more than 24 hours old after hatching are transferred in groups of 25 to barred cages. The cages are then immersed for 5 to 10 seconds in an acetonic solution containing 0.1% by weight of the test compound. After the beetles have dried, they are placed in covered dishes containing feed and left for copulation and oviposition. Egg deposits are flushed out with running water twice to three times weekly, counted, disinfected by putting them for 2 to 3 hours into an aqueous disinfectant, and then placed in dishes containing a suitable larval feed. A count is made after 7 days to determine the number of larvae which have developed from the eggs.
The duration of the reproduction inhibiting effect of the test compounds is determined by monitoring the egg deposits further, i.e. over a period of about 4 weeks. Evaluation is made by assessing the reduction in the number of deposited eggs and hatched larvae in comparison with untreated controls.
The compounds of formula I according to Example 1 exhibit a good reproduction reducing activity in this test.
Example 7 1: Action against Anthonomus grandis (adults)
Two cotton plants in the 6-leaf stage, in pots, are each sprayed with a wettable aqueous emulsion formulation containing 400 ppm of the test compound. After the spray coating has dried (about 1 1/2 hours), each plant is populated with 10 adult beetles (Anthonomus grandis).
Plastic cylinders, covered at the top with gauze, are then slipped over the treated plants populated with the test insects to prevent the beetles from migrating from the plants. The treated plants are then kept at 25"C and about 60% relative humidity. Evaluation is made after 2, 3, 4 and 5 days to determine the percentage mortality of the beetles (percentage in dorsal position) as well as the anti-feeding action as compared with untreated controls.
Compound 1 according to Example 1 effects 80 to 100% mortality in this test.
Claims (33)
1. A compound of formula I
wherein R, is hydrogen, fluorine, chlorine, methyl, methoxy or methylthio, R2 is fluorine, chlorine, methyl, methoxy or methylthio and 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 R, is hydrogen; R2 is fluorine, methyl, methoxy or methylthio if R, is fluorine; or R2 is chlorine, methyl, methoxy or methylthio if R, is chlorine.
4. A compound of formula I according to claim 3, wherein Rl 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 R, and R2 are simultanesusly fluorine or chlorine.
6. A compound of formula I according to claim 5, wherein R, and R2 are simultaneously fluorine.
7. A compound of formula I according to any one of claims 1 to 6, wherein R3 is one of the radicals -CHF2, -CF3, -CF2CHF2, -CH2-CF3, -CF2CHCIF, -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, -CF2CHCI2 or -CF2CCl3.
9. A compound of formula I according to claim 1, wherein R3 is Cs-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 according to claim 3 of the formula
18. The compound according to claim 3 of the formula
19. The compound according to claim 2 of the formula
20. The compound according to claim 3 of the formula
21.A process for the preparation of a compound according to any one of claims 1 to 20, which process comprises reacting
(a) a compound of formula II
with a compound of formula Ill
or
(b) a compound of formula IV
with a compound of formula V
or
(c) a compound of formula II with a compound of formula VI
in which formulae II to VI the radicals R1, R2 and R3 are as defined in any one of claims 1 to 9 and R is a C,-C8alkyl radical which is unsubstituted or substituted by halogen.
22. A compound of formula II
wherein R3 is as defined in any one of claims 1 to 9.
23. A compound of formula IV
wherein R3 is as defined in any one of claims 1 to 9.
24. A pesticidal composition which contains as active ingredient a compound according to any one of claims 1 to 20, together with suitable carriers and/or other adjuvants.
25. Use of a compound according to any one of claims 1 to 20 for controlling insects and representatives of the order Acarina.
26. Use according to claim 25 for controlling larval stages of plant-destructive insects.
27. Use according to claim 25 as insect ovicide.
28. A method of controlling insects and representatives of the order Acarina, which method comprises contacting or treating said pests, their various development stages or the locus thereof with a pesticidally effective amount of a compound of formula I according to any one of claims 1 to 20, or with a composition which contains a pesticidally effective amount of such a compound, together with adjuvants and carriers.
29. A compound of formula I according to claim 1 substantially as described with reference to Example 1.
30. A process for the production of a compound of formula I according to claim 21 substantially as described with reference to Example 1.
31. A compound of formula I according to claim 1 when produced by a process claimed in claim 21 or 30.
32. A pesticidal composition according to claim 24 substantially as described with reference to Example 2.
33. A method of controlling insects according to claim 28 substantially as described with reference to any of Examples 3 to 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH499384 | 1984-10-18 | ||
| CH536184 | 1984-11-08 | ||
| CH204885 | 1985-05-14 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8525517D0 GB8525517D0 (en) | 1985-11-20 |
| GB2166134A true GB2166134A (en) | 1986-04-30 |
| GB2166134B GB2166134B (en) | 1988-07-27 |
Family
ID=27173428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08525517A Expired GB2166134B (en) | 1984-10-18 | 1985-10-16 | Insecticidal 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) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132325A (en) * | 1986-02-28 | 1992-07-21 | Ciba-Geigy Corporation | Benzoylphenylureas the preparation thereof and the use thereof in pest control |
| US5556883A (en) * | 1992-06-01 | 1996-09-17 | Dowelanco | Use of hexaflumuron as a termiticide |
| 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 |
| 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 |
| US5945453A (en) * | 1996-11-08 | 1999-08-31 | Dow Agrosciences Llc | Benzoylphenylurea insecticides to control cockroaches |
| US6040345A (en) * | 1996-11-08 | 2000-03-21 | Dow Agrosciences Llc | Benzoylphenylurea insecticides and methods of using them to control cockroaches |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0179022B1 (en) * | 1984-10-18 | 1990-11-07 | Ciba-Geigy Ag | Benzoylphenyl ureas |
| AU602305B2 (en) * | 1985-03-14 | 1990-10-11 | Istituto Guido Donegani S.P.A. | N-(halobenzoyl)-N-(polyhaloalkoxyphenyl) urea derivatives |
| 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 |
| WO1994003066A1 (en) * | 1992-07-29 | 1994-02-17 | Ciba-Geigy Ag | Method and composition for controlling cockroaches |
| 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 |
|---|---|---|---|---|
| AU553953B2 (en) * | 1981-07-30 | 1986-07-31 | Dow Chemical Company, The | Urea and thiourea insecticides; intermediates in their preparation |
| US4518804A (en) * | 1982-07-26 | 1985-05-21 | The Dow Chemical Company | Halo(alkoxy/alkylthio)-benzenamines |
| DE3478573D1 (en) * | 1983-09-01 | 1989-07-13 | Duphar Int Res | Benzoyl urea derivatives having anti-tumor activity |
| ATE40111T1 (en) * | 1984-07-05 | 1989-02-15 | Duphar Int Res | BENZOYL UREA COMPOUNDS AND INSECTICIDES AND ACARICIDES COMPOSITIONS CONTAINING SUCH. |
-
1985
- 1985-10-14 EP EP85810467A patent/EP0179021A3/en not_active Withdrawn
- 1985-10-16 CA CA000493028A patent/CA1242453A/en not_active Expired
- 1985-10-16 GB GB08525517A patent/GB2166134B/en not_active Expired
- 1985-10-17 EG EG66485A patent/EG17507A/en active
- 1985-10-17 KR KR1019850007647A patent/KR860003207A/en not_active Application Discontinuation
- 1985-10-17 ZW ZW180/85A patent/ZW18085A1/en unknown
- 1985-10-17 BR BR8505174A patent/BR8505174A/en unknown
- 1985-10-17 AU AU48819/85A patent/AU585539B2/en not_active Expired
- 1985-10-17 IL IL76731A patent/IL76731A0/en unknown
Non-Patent Citations (8)
| Title |
|---|
| CHEMICAL ABSTRACTS 103(13): 104736 F * |
| RN 97893-28-2; * |
| RN 97893-30-6; * |
| RN 97893-31-7; * |
| RN 97893-32-8; * |
| RN 97893-33-9; * |
| RN 97893-34-0; * |
| RN 97893-35-1; * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132325A (en) * | 1986-02-28 | 1992-07-21 | Ciba-Geigy Corporation | Benzoylphenylureas the preparation thereof and the use thereof in pest control |
| US5556883A (en) * | 1992-06-01 | 1996-09-17 | Dowelanco | Use of hexaflumuron as a termiticide |
| US5691383A (en) * | 1992-06-01 | 1997-11-25 | Dowelanco | Use of hexaflumuron as a termiticide |
| CN1073801C (en) * | 1992-06-01 | 2001-10-31 | 道农业科学公司 | Novel use of hexaflumuron as a termiticide |
| US5945453A (en) * | 1996-11-08 | 1999-08-31 | Dow Agrosciences Llc | Benzoylphenylurea insecticides to control cockroaches |
| US6040345A (en) * | 1996-11-08 | 2000-03-21 | Dow Agrosciences Llc | Benzoylphenylurea insecticides and methods of using them to control cockroaches |
| US6221912B1 (en) | 1996-11-08 | 2001-04-24 | Dow Agrosciences Llc | Benzoylphenylurea insecticides and methods of using certain benzoylphenylureas to control cockroaches |
| US6245816B1 (en) | 1996-11-08 | 2001-06-12 | Ronald J. Spragia | Benzoylphenylurea insecticides and methods of using certain benzoylphenylureas to control ants |
| 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 |
| 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 |
| US5874615A (en) * | 1998-03-17 | 1999-02-23 | American Cyanamid Co | Method for the preparation of insecticidal benzoylurea compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0179021A3 (en) | 1987-05-13 |
| IL76731A0 (en) | 1986-02-28 |
| ZW18085A1 (en) | 1986-05-14 |
| CA1242453A (en) | 1988-09-27 |
| AU585539B2 (en) | 1989-06-22 |
| AU4881985A (en) | 1986-04-24 |
| BR8505174A (en) | 1986-07-29 |
| KR860003207A (en) | 1986-05-21 |
| GB8525517D0 (en) | 1985-11-20 |
| EG17507A (en) | 1994-09-29 |
| EP0179021A2 (en) | 1986-04-23 |
| GB2166134B (en) | 1988-07-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |