CA1281741C - Phenylbenzoylureas - Google Patents
PhenylbenzoylureasInfo
- Publication number
- CA1281741C CA1281741C CA000489645A CA489645A CA1281741C CA 1281741 C CA1281741 C CA 1281741C CA 000489645 A CA000489645 A CA 000489645A CA 489645 A CA489645 A CA 489645A CA 1281741 C CA1281741 C CA 1281741C
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Classifications
-
- 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
-
- 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)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Hydrogenated Pyridines (AREA)
- Magnetic Resonance Imaging Apparatus (AREA)
- Detergent Compositions (AREA)
Abstract
Phenylbenzoylureas Abstract of the disclosure The invention relates to novel N-[3-halo-4-(hexafluoropropoxy)-5-trifluoromethyl]phenyl-N'-benzoylureas of the formula
Description
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Phenylbenzoylureas The present lnvention relates to novel N-l3-halo-4-(hexafluoroprop-oxy)-S-trifluoromethyl~phenyl-N'-benzoylureas, to the preparation thereof and to the use thereof in pest control.
The compounds o~ this invention have the formula I
~1 ~3 ~ ~--CONHCONH--~ ~--O-CF2CHFCF3 (I), wherein Rl i8 hydrogen or halogen and R2 and R3 are halogen.
Within the scope of this invention, halogen will be understood as meaning fluorine, chlorine and bromine, in particular fluorine and chlorine for R1 and Rz and chlorine and bromine for R3.
On account of their activity as pesticides, preferred compounds of formula I are those wherein Rl is hydrogen, fluorine or chlorine, and R2 is fluorine or chlorine, and R3 is chlorine.
To be singled out for special mention are also those compounds of formula I, wherein R1 is hydrogen, fluorine or chlorine, R2 is fluorine or chlorine, and R3 is bromine.
The compounds of formula I can be prepared by methods which are known per se (q.v. for example German Offenlegungsschrift speci-fications 2 123 236 and 2 601 780 and European patent appli-cation 13 414).
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Thus, for example, a compound of formula I may be obtained by reacting a) a compound of formula II
~3 CF3CHFCFz-O-~ -NH2 tII) ~F3 with a compound of formula III
-CO-N~C~O(III), ~2 b) a compound of formula IV
~3 CF3CHFCF2-O--~ ~- _NDC=O t IV) CF;
w1th a compound of formula V
.~ ~--CO-NH2 (V) . R2 or c) a compound of formula II with a compound of formula YI
~1 ~ ~--CONHCOOR (VI), ~L2 1.28174 in which formulae II, III, IV, V and VI above R1, R2 and R3 are as defined for formula I and R is a lower or average C1-C8-alkyl radical which may be substituted by halogen, preferably chlorine.
The above processes a) to 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 aceto-nitrile or propionitrile; dimethyl sulfoxide; and ketones, e.g.
acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone. Process a) i8 normally carried out in the tempera-tuse range from -10~ to lOO~C, preferably from 15~ to 25UC, if desired in the presence of an organic base, e.g. triethylamine.
Process b) is csrried out in the temperature range from 0~ to ISO~C, 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 the reaction of the urethane of formula VI
according to process c), a temperature range from about 6~v 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 II, III, IV, V and VI are known or, if novel, can be prepared by methods analogous to known ones.
The substitutet anilines of formula II are novel compounds which likewise constitute an object of the invention and can be prepared according to methods known in the literature e.g. by hydrogenating 2-halo-6-trifluoromethyl-4-nitrophenol (q.v. J. Org. Chem. 27 (1962), 466~), in the presence of acetic anhydride, and etherifying the resultant 2-halo-6-trifluoromethyl-4-acetaminophenol with ,~
317~1 hexafluoropropylene in analogy to the method described in Am. Soc. 73 ~1~51), 5~31. The N-acetyl group is subsequently split off in conventional manner to give the aniline of formula II.
It has been found that the compounds of this invention have ex-cellent 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 the formula I are suitable for controlling insects of the orders: Lepidoptera, Coleoptera, Homo-ptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophage, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatives of the order Acarina.
The good pesticidal activity of the proposed compounds of the formula I according to the invention corresponds to a mortality of at least 50-60 ~h of the above pests.
In addition to their very effective action against flies, e.g. Musca domestica, and mosquito larvae, the compounds of formula I are particularly suitable for controlling plant-destructive feeding insects in ornanentals and crops of useful plants, especially in cotton (e.g. against Spodoptera littoralis and Heliothis virescens) and in crops of vegetables (e.g. against Leptinotarsa decemlineata and Pieris brassicae). The larvicidal and ovicidal action of the compounds of formula I is to be particularly highlighted. 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 Coleoptera, e.g. Anthonomus grlindi~.
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The compounds of formula I can also be used for controlling ecto-parasites such as Lucilia sericata, and ticks, in domestic animals and productive livestock, e.g. by treatlng animals, cowsheds, barns, stables etc., and pastures.
The activity of the compounds of the formula I and of the composi-tions 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, pyrethroids, carbamates, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
The compounds of the formula I are used in unmodified form, or preferably together with the ad~uvants 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 substan-ces. As with the nature of the compositions, the methods of appli-cation 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 or preparations containing the compound (active ingredient) of the formula I or combinstions thereof with other insecticides or acaricides, and, where appro-priate, a solid or liquid ad~uvant, 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 phthalste, aliphatic hydroc~rbone such a~ cyclohexsn~ ol ' ' .' ` ' ~ .
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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-pyrro-lidone, dimethyl sulfoxide or dimethyl formamide, 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 adsorp-tive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sànd. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of the formula I to oe 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 propertles. The term "6urfactants" 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 ~oaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-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.
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More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, 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 substi-tuted ammonium salts and contain a Cg-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfona-ted 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 tri-ethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic 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 p-nonyl-phenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloallphatic 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, ethylenediamine-polypropylene 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.
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Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldl-(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publi~hing Corp. Ridgewood, New Jersey, 1979; Dr. Helmut Stache, "Tensid T~schenbuch" (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna, lg81.
The pesticidal compositions usually contain 0.1 to 9g æ, preferably 0.1 to g5 ~0, of a compound of the formula I or combination thereof with other insecticides or acaricides, 1 to g9.9 % of a solid or liquid adjuvant, and 0 to 25 ~, preferably 0.1 to 20 %, of a surfactant.
Whsreas commercial products are preferably formulsted as concen-trates, the end user will normally employ dilute formulations of substantially lower concentration.
The compo~itions may also contain further ingrsdients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
- -12f~741 _ 9 _ Example 1:
a) Preparation of the starting 3-chloro-4-~1,1,2,3?3,3-hexafluoro-propoxy)-5-(trifluoromethyl)aniline 42.2 g of 3-chloro-4-(1,1,2,3,3,3-hexafluoropropoxy)-5-~trifluorometh-yl)acetaminobenzene are boiled for 16 hours at reflux in a mixture of 200 ml of concentrated hydrochloric acid and 400 ml of ethanql.
The bulk of the solvent is then distilled off and the residue is made alkaline and extracted with ether. The ethereal extract is dried over sodium sulfate and the solvent is removed by evaporation in vacuo. Fractional distillation of the residue, affords the title compound as a yellowish oil with a boiling point of 115~-120UC/4-10 torr (a compound of formula II).
b) PreParation of N-13-chloro-4-(hexafluoropropoxy)-5-trifluoro-methylJ-N'-2,6-difluorobenzoylurea A reactor is charged with 3.6 g of the 3-chloro-4-(hexafluoropropoxy)-~-(trlfluoromethyl)aniline obtained in a) in 1~ ml of dry diethyl ether. With stirring, 1.82 g of 2,6-difluorobenzoylisocyanate are added dropwise. After 3 hours the crystalline precipitate formed is lsolated by filtration and washed with a small quantity of ether, affording white crystals of the title compound of the formula ~ ~--CONHCONH--~ 5 -O-CF2CHFCF 3 with a melting point of 162U-163~C (compound 1).
The following compounds of formula I are also obtained by the procedures described above:
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, 17~1 Compound mP lVc]
2 .~ ~--CONHCONH-~ ~--O-CF2CHFCF3 166-168 F ~F3 .~ .=!Cl 3 ~ ~--CONHCONH~--O-CF2CHFCF3 149.5-151 4 ~ ~--CONHCONH-~~;-O-CF2CHFCF3 118-120 ~1 Cll S ~ -CONHCONH~ -O-CF2CHFCF3 191.5-193 Cl CF3 Example Z:
a) PreParation of the startin~ 3-bromo-4-(1~1,2,3,3,3-hexafluoro-propoxY~-5-(trifluoromethyl)aniline 22.7 g of 3-bromo-4-(1,1,2,3,3,3-hexafluoropropoxy)-5-(trifluorometh-yl)acetaminobenzene are heated at reflux for 4 hours in a mixture of 100 ml of concentrated hydrochloric acid and 300 ml of ethanol.
The bulk of the solvent is then distllled off, the residue is made alkaline with 10 ~0 sodlum hydroxide solution and extracted with ether. The ethereal extract is dried over sodium sulfate and the solvent is removed in V8CUO. Fractional distillation of the residue affords the title compound as a yellowish oil with a boiling point of 115~-120~C/5~10 2 torr (a compound of formula II).
b) PreParation of N-¦ 3-bromo-4-(hexafluoropropoxy)-S-trifluorometh-yl~-N'-2,6-difluorobenzoylurea 3.5 g of the 3-bromo-4-(hexafluoropropoxy)-5-(trlfluoromethyl)anil-~ne obtained in a) in 10 ml of dry diethyl ether are charged to a reactor. With stirring, 1.52 g of 2,6-difluorobenzoylisocyanate are added dropwise at room temperature. After 3 hours, the crystalline precipltate is isolated by filtration and washed with a small quantity of ether, affording white crystals of the title compound of the formula ~r -CONHCONH--~ ~--O-CF2CHFCF3 ~ CF3 with a melting point of 145~-147~C (compound 6).
The following compounds of formula I are also prepared in correspon-ding manner:
Compound mp. I~CJ
ICl ~r 7 ~ CONHCONH~ --O-CF2CHFCF3 183.5-185 !Cl ~r 8 ~ -CONHCONH--~ ~--O-CF2CHFCF3 141-142 ~F3 IF ~r 9 ~ ~--CONHCONH--~ ~--O-CF2CHFCF3 ~.Z81.7 ~1 ~r `10 ~ CONHCONH--~ ~s--O-CF~CHFCP3 Example 3:
Formulation examples for active ingredients of the formula I
accordin~ to Exam~l_s 1 and 2 or combinations thereof with other insecticides or acaricides (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 ~0 ~odium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid5 % 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 %
cslcium dodecylbenzenesulfonate3 %
castor oil polygycol ether (36 moles of ethylene oxide) 4 %
cyclohexanone 30 %
xylene mixture 50 %
.
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' ~ ' `- ~ ' ~81741 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 70 talcum 95 %
kaolin - 92 70 Ready for use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.
4. Extruder granulate compound of formula I or combinationlO %
sodium lignosulfonate 2 %
carboxymethylcellulose l %
kaolin 87 %
The active ingredient or combination is mixed and ground with the ad~uvants, and the mixture i8 subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
5-15U56/~
Phenylbenzoylureas The present lnvention relates to novel N-l3-halo-4-(hexafluoroprop-oxy)-S-trifluoromethyl~phenyl-N'-benzoylureas, to the preparation thereof and to the use thereof in pest control.
The compounds o~ this invention have the formula I
~1 ~3 ~ ~--CONHCONH--~ ~--O-CF2CHFCF3 (I), wherein Rl i8 hydrogen or halogen and R2 and R3 are halogen.
Within the scope of this invention, halogen will be understood as meaning fluorine, chlorine and bromine, in particular fluorine and chlorine for R1 and Rz and chlorine and bromine for R3.
On account of their activity as pesticides, preferred compounds of formula I are those wherein Rl is hydrogen, fluorine or chlorine, and R2 is fluorine or chlorine, and R3 is chlorine.
To be singled out for special mention are also those compounds of formula I, wherein R1 is hydrogen, fluorine or chlorine, R2 is fluorine or chlorine, and R3 is bromine.
The compounds of formula I can be prepared by methods which are known per se (q.v. for example German Offenlegungsschrift speci-fications 2 123 236 and 2 601 780 and European patent appli-cation 13 414).
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Thus, for example, a compound of formula I may be obtained by reacting a) a compound of formula II
~3 CF3CHFCFz-O-~ -NH2 tII) ~F3 with a compound of formula III
-CO-N~C~O(III), ~2 b) a compound of formula IV
~3 CF3CHFCF2-O--~ ~- _NDC=O t IV) CF;
w1th a compound of formula V
.~ ~--CO-NH2 (V) . R2 or c) a compound of formula II with a compound of formula YI
~1 ~ ~--CONHCOOR (VI), ~L2 1.28174 in which formulae II, III, IV, V and VI above R1, R2 and R3 are as defined for formula I and R is a lower or average C1-C8-alkyl radical which may be substituted by halogen, preferably chlorine.
The above processes a) to 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 aceto-nitrile or propionitrile; dimethyl sulfoxide; and ketones, e.g.
acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone. Process a) i8 normally carried out in the tempera-tuse range from -10~ to lOO~C, preferably from 15~ to 25UC, if desired in the presence of an organic base, e.g. triethylamine.
Process b) is csrried out in the temperature range from 0~ to ISO~C, 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 the reaction of the urethane of formula VI
according to process c), a temperature range from about 6~v 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 II, III, IV, V and VI are known or, if novel, can be prepared by methods analogous to known ones.
The substitutet anilines of formula II are novel compounds which likewise constitute an object of the invention and can be prepared according to methods known in the literature e.g. by hydrogenating 2-halo-6-trifluoromethyl-4-nitrophenol (q.v. J. Org. Chem. 27 (1962), 466~), in the presence of acetic anhydride, and etherifying the resultant 2-halo-6-trifluoromethyl-4-acetaminophenol with ,~
317~1 hexafluoropropylene in analogy to the method described in Am. Soc. 73 ~1~51), 5~31. The N-acetyl group is subsequently split off in conventional manner to give the aniline of formula II.
It has been found that the compounds of this invention have ex-cellent 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 the formula I are suitable for controlling insects of the orders: Lepidoptera, Coleoptera, Homo-ptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophage, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatives of the order Acarina.
The good pesticidal activity of the proposed compounds of the formula I according to the invention corresponds to a mortality of at least 50-60 ~h of the above pests.
In addition to their very effective action against flies, e.g. Musca domestica, and mosquito larvae, the compounds of formula I are particularly suitable for controlling plant-destructive feeding insects in ornanentals and crops of useful plants, especially in cotton (e.g. against Spodoptera littoralis and Heliothis virescens) and in crops of vegetables (e.g. against Leptinotarsa decemlineata and Pieris brassicae). The larvicidal and ovicidal action of the compounds of formula I is to be particularly highlighted. 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 Coleoptera, e.g. Anthonomus grlindi~.
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.
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, : .
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174~
The compounds of formula I can also be used for controlling ecto-parasites such as Lucilia sericata, and ticks, in domestic animals and productive livestock, e.g. by treatlng animals, cowsheds, barns, stables etc., and pastures.
The activity of the compounds of the formula I and of the composi-tions 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, pyrethroids, carbamates, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
The compounds of the formula I are used in unmodified form, or preferably together with the ad~uvants 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 substan-ces. As with the nature of the compositions, the methods of appli-cation 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 or preparations containing the compound (active ingredient) of the formula I or combinstions thereof with other insecticides or acaricides, and, where appro-priate, a solid or liquid ad~uvant, 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 phthalste, aliphatic hydroc~rbone such a~ cyclohexsn~ ol ' ' .' ` ' ~ .
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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-pyrro-lidone, dimethyl sulfoxide or dimethyl formamide, 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 adsorp-tive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sànd. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of the formula I to oe 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 propertles. The term "6urfactants" 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 ~oaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-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.
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.
12f~17~
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, 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 substi-tuted ammonium salts and contain a Cg-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfona-ted 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 tri-ethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic 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 p-nonyl-phenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloallphatic 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, ethylenediamine-polypropylene 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.
174~
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldl-(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publi~hing Corp. Ridgewood, New Jersey, 1979; Dr. Helmut Stache, "Tensid T~schenbuch" (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna, lg81.
The pesticidal compositions usually contain 0.1 to 9g æ, preferably 0.1 to g5 ~0, of a compound of the formula I or combination thereof with other insecticides or acaricides, 1 to g9.9 % of a solid or liquid adjuvant, and 0 to 25 ~, preferably 0.1 to 20 %, of a surfactant.
Whsreas commercial products are preferably formulsted as concen-trates, the end user will normally employ dilute formulations of substantially lower concentration.
The compo~itions may also contain further ingrsdients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
- -12f~741 _ 9 _ Example 1:
a) Preparation of the starting 3-chloro-4-~1,1,2,3?3,3-hexafluoro-propoxy)-5-(trifluoromethyl)aniline 42.2 g of 3-chloro-4-(1,1,2,3,3,3-hexafluoropropoxy)-5-~trifluorometh-yl)acetaminobenzene are boiled for 16 hours at reflux in a mixture of 200 ml of concentrated hydrochloric acid and 400 ml of ethanql.
The bulk of the solvent is then distilled off and the residue is made alkaline and extracted with ether. The ethereal extract is dried over sodium sulfate and the solvent is removed by evaporation in vacuo. Fractional distillation of the residue, affords the title compound as a yellowish oil with a boiling point of 115~-120UC/4-10 torr (a compound of formula II).
b) PreParation of N-13-chloro-4-(hexafluoropropoxy)-5-trifluoro-methylJ-N'-2,6-difluorobenzoylurea A reactor is charged with 3.6 g of the 3-chloro-4-(hexafluoropropoxy)-~-(trlfluoromethyl)aniline obtained in a) in 1~ ml of dry diethyl ether. With stirring, 1.82 g of 2,6-difluorobenzoylisocyanate are added dropwise. After 3 hours the crystalline precipitate formed is lsolated by filtration and washed with a small quantity of ether, affording white crystals of the title compound of the formula ~ ~--CONHCONH--~ 5 -O-CF2CHFCF 3 with a melting point of 162U-163~C (compound 1).
The following compounds of formula I are also obtained by the procedures described above:
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2 .~ ~--CONHCONH-~ ~--O-CF2CHFCF3 166-168 F ~F3 .~ .=!Cl 3 ~ ~--CONHCONH~--O-CF2CHFCF3 149.5-151 4 ~ ~--CONHCONH-~~;-O-CF2CHFCF3 118-120 ~1 Cll S ~ -CONHCONH~ -O-CF2CHFCF3 191.5-193 Cl CF3 Example Z:
a) PreParation of the startin~ 3-bromo-4-(1~1,2,3,3,3-hexafluoro-propoxY~-5-(trifluoromethyl)aniline 22.7 g of 3-bromo-4-(1,1,2,3,3,3-hexafluoropropoxy)-5-(trifluorometh-yl)acetaminobenzene are heated at reflux for 4 hours in a mixture of 100 ml of concentrated hydrochloric acid and 300 ml of ethanol.
The bulk of the solvent is then distllled off, the residue is made alkaline with 10 ~0 sodlum hydroxide solution and extracted with ether. The ethereal extract is dried over sodium sulfate and the solvent is removed in V8CUO. Fractional distillation of the residue affords the title compound as a yellowish oil with a boiling point of 115~-120~C/5~10 2 torr (a compound of formula II).
b) PreParation of N-¦ 3-bromo-4-(hexafluoropropoxy)-S-trifluorometh-yl~-N'-2,6-difluorobenzoylurea 3.5 g of the 3-bromo-4-(hexafluoropropoxy)-5-(trlfluoromethyl)anil-~ne obtained in a) in 10 ml of dry diethyl ether are charged to a reactor. With stirring, 1.52 g of 2,6-difluorobenzoylisocyanate are added dropwise at room temperature. After 3 hours, the crystalline precipltate is isolated by filtration and washed with a small quantity of ether, affording white crystals of the title compound of the formula ~r -CONHCONH--~ ~--O-CF2CHFCF3 ~ CF3 with a melting point of 145~-147~C (compound 6).
The following compounds of formula I are also prepared in correspon-ding manner:
Compound mp. I~CJ
ICl ~r 7 ~ CONHCONH~ --O-CF2CHFCF3 183.5-185 !Cl ~r 8 ~ -CONHCONH--~ ~--O-CF2CHFCF3 141-142 ~F3 IF ~r 9 ~ ~--CONHCONH--~ ~--O-CF2CHFCF3 ~.Z81.7 ~1 ~r `10 ~ CONHCONH--~ ~s--O-CF~CHFCP3 Example 3:
Formulation examples for active ingredients of the formula I
accordin~ to Exam~l_s 1 and 2 or combinations thereof with other insecticides or acaricides (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 ~0 ~odium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid5 % 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 %
cslcium dodecylbenzenesulfonate3 %
castor oil polygycol ether (36 moles of ethylene oxide) 4 %
cyclohexanone 30 %
xylene mixture 50 %
.
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' ~ ' `- ~ ' ~81741 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 70 talcum 95 %
kaolin - 92 70 Ready for use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.
4. Extruder granulate compound of formula I or combinationlO %
sodium lignosulfonate 2 %
carboxymethylcellulose l %
kaolin 87 %
The active ingredient or combination is mixed and ground with the ad~uvants, and the mixture i8 subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
5. Coated granulatè
compound of formula I or combinatior. 3 %
polyethylene glycol 200 3 %
kaolin 94 %
The finely ground actlve ingredient or combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-tusty coated granulates are obtained in this manner.
compound of formula I or combinatior. 3 %
polyethylene glycol 200 3 %
kaolin 94 %
The finely ground actlve ingredient or combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-tusty coated granulates are obtained in this manner.
6. Suspension concentrate compound of formùla I or combination 40 %
ethylene glycol lO %
nonylphenol polyetbylene glycol ether (15 moles of etbylene oxide) 6 %
sodium lignosulfonate lO %
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37 % aqueous formaldehyde solutlon 0.2 %
silicone oil ln 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 dasired concentration can be obtained by dilution with water.
Example 4: 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 a 1 ~
acetonic solution of the respective test compound is pipetted onto the nutrient substrate present in the beakers to give an active ingredient concentration of 400 ppm. The substrate is then thoroughly mixed and the acetone subsequently allowed to evaporate over Q 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 actlve 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 compount on the maggot development. A count is then mate after l~ days of the number of flies which have hatched out of the pupae.
The compounds of formula I obtained according to Examples 1 and 2 have good activity in this test.
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~174~
Example 5: Action a~ainst Lucilia sericata I ml of an aqueous solution containing 0.5 % 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 medi~m, and the insecticidal action is determined after 48 and Y6 hours by eval~ating the mortality rate.
In this test, compounds of the formula I according to Examples 1 and 2 exhibit ~ood activity against Lucilia sericata.
Example 6: Act~on against Aedes aegypti A concentration of 400 ppm is obtained by pipetting a specific amount of a 0.1 % solution of the test compound iD acetone onto the surface of 150 ml of water in a beaker. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aedes aegypti are put into the beaker containing the test compound. Mortality counts are made after 1, 2 and 5 days.
In this test, compounds of Examples 1 and 2 exhibit good activity against Aedes aegypti.
Example 7: Insecticidal action against feeding lnsects Cotton plants (about 20 cm high) are sprayed with aqueous emulsions (obtained from a 10 % emulsifiable concentrate) containing the respectlve test compound in concentrations of 0.75 to 400 ppm. After the spray coating has dried, the cotton plant~ 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.
At 24 hour intervals, a mortslity count is msde snd the lsrvs sre also exsmlned for inhibition of development snd shedding.
In this test, 80-100 ~0 kill against Spodopters is effected with compounds 1, 2 and 4 st 0.75 ppm snd with compounds 3, ~, 7 snd 8 at 3.0 ppm. The following compounds effect 80-100 % kill s~ainst Heliothis: compounds 1 and 6 at 3.0 ppm, compounds 2 and 7 st 12.5 ppm, compounds 3 and 8 at 50 ppm, and compound 4 at 400 ppm.
~8174~
Example 8:
Action against Spodo~tera littoralis and Heliothis virescens (larvae and e~g~2~
Three cotton plants each having a height of about 15-20 cm and grown in pots are treated with a sprayable liquid preparation of the test compound in a concentration of 400 ppm. After the spray coating has dried, the potted plants are placed in a metal container having a capacity of about 20 litres and covered with a glass plate. The humidity in the interior of covered container is regulated such that no water of condensation forms. Direct light falling on the plants is avoided. The three plants are then infested altogether with:
a~ 50 larvae of Spodoptera littoralis or Heliothis virescens in the L1-stage;
b) 20 larvae of Spodoptera littoralis or Heliothis virescens ln the L3-stage;
c) 2 egg deposit~ of Spodoptera littoralis or Heliothis virescens.
(The prod~cedure is that two leaves of each plant are put into a plexlglass cylinder sealed at both ends with muslin. Two egg deposits of Spodoptera, or a part of a cotton leaf with eggs of Heliothis deposited thereon, are added to the leaves sealed in ; the cylinder.) ; Evaluation in comparison w1th untreated controls is made after 4 to 5 days, taking into account the following criteria:
a) the number of still living larvae, b) inhibition of larval develop~ent and shedding, c) feeting damage (shredding and perforation damage), d) hatching rate (number of larvae hatched from the eggs).
In this test, the compounds of Formula I according to Examples l and 2 exhibit good overall activity.
, 1~817 Example ~: Ovicidal action against Spodoptera littoralis Eggs of Spodoptera littorali8 deposited on filter paper are cut out of the paper and immersed in a 0.~5 % by weight solution of each compound to be tested in a 1:1 mixture of acetone-water. The treated deposits are then removed from this mixture and kept in plastic dishes at 28C and 60 % humidity. The hatching rate, i.e. the number of larvae which have developed from the treated eggs, is determined after 5 days.
The compounds of formula I accordi~g to Exa~ples 1 and 2 show good activity in this test.
Example 10: Ovicidal action against Epilachna varivestis A mixture is prepared from 20 % by weight of test compound, 70 % by weight of xylene and 10 % by weight of a mixture of a reaction product of an alkyl phenol with ethylene oxide and calcium dodecyl-benzsnesulfonate. An aqueous emulsion containing 800 ppm of test compound are prepared from this concentrate.
100 eggs of Epilachna varivestis (Mexican bean beetle), freshly deposited on leaves of Phaseolus vulgaris, are moistened with the above described aqueous emulsion (concentration: 800 ppm) and dried lightly. The treated egg deposits are kept in a ventilated container until the simultaneously deposited untreated controls have hatched.
The percentage kill is evaluated under a stereoscopic microscope.
The compounds of Formula I according to Examples 1 and 2 show good activity in this test.
Example 11: Ovlcidal action against Heliothis virescens and Leptiotarsa decemlineata 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 concen-tration of 800 ppm. One day-old egg deposits of Heliothis on ., .
.
1~17~1 cellophane/and egg deposits of Leptinotarsa on potato leaves are immersed ln these emulslons for ~ minutes and then collected by suction on round filters. The treated deposits are placed in petri dishes and kept in the dark. The hatching rate in comparison wlth untreated controls is determined after 6 to 8 days.
Compounds of formula I according to Examples 1 and 2 show good activity in this test.
Example 12 Ovicidal action a~ainst LaspeYresia pomonella (e~s):
Egg deposits of Laspsyrasia pomonella not more than 24 hours old are lmmersed on filter paper for 1 minute in an aqueous acetonic solution containing 400 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 is evaluated after 6 days.
The compounds of formula I according to Examples 1 and 2 exhibit good activity in this test.
Example 13: Action again6t Anthonomus grandis (adults) Two cotton plants in the 6-leaf stage, in pots, are each sprayed with a wettable aqueous emulsion formulation containing the test compound in a concentration of 12.5 ppm. After the spray coating has dried (about 1 1/2 hours~, each plant is popuiated 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 ~0 %
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-feed~ng action as compared with untreated controls.
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~L'~3iL7 In this test, compounds l, 2, 6 and 7 of Example l ef~ect 80-lO0 ~0 kill (mortality).
Example 14:
Action against plant-destructive acarids: Tetranychus urticae ~OP-sensitlve) and Tetranychus cinnabarinus ~OP-tolerant) 16 hours before the test for acaricidal action, the primary leaves of Phaseolus vulgaris plants are in~ected with an infested piece of leaf from a mass culture of Tetranychus urt~cae (OP-sensitive) and Tetranychus cinnabarinus (OP-tolerant). (The tolerance refers to diazinone). The treated infested plants are sprayed to drip point with a test solut~on containing 400 ppm of the compound to be tested. A count of the number of liv~ng and dead imagines and larvae (all mobile stages) is made under a stereoscopic microscope after 24 hours and again after 7 days. One plant is used for each test substance and test species. During the test run, the plants are kept in greenhouse compartments at 25~C.
In this test, the compounds of formula I according to Examples l and 2 show good actlvity against Tetranychus urticae and Tetranychus cinnabarinus.
Exam~le 15: Influence on the reproduction of Anthonomous grandis Anthonomous grandis adults which are not more than 24 hours old after hatching sre transferred in groups of 25 to barred cages. The cages are then immersed for 5 to lO seconds in an acetonic solution containing 8~ ppm 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 whether larvae have developed from the eggs.
12~31741 The duration of the reproduction inhibiting effect of the test compounds is determined by monitoring the egg deposits 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 the formula I according to Examples 1 and 2 exhibit a good reproduction inhibiting effect in this test.
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ethylene glycol lO %
nonylphenol polyetbylene glycol ether (15 moles of etbylene oxide) 6 %
sodium lignosulfonate lO %
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37 % aqueous formaldehyde solutlon 0.2 %
silicone oil ln 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 dasired concentration can be obtained by dilution with water.
Example 4: 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 a 1 ~
acetonic solution of the respective test compound is pipetted onto the nutrient substrate present in the beakers to give an active ingredient concentration of 400 ppm. The substrate is then thoroughly mixed and the acetone subsequently allowed to evaporate over Q 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 actlve 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 compount on the maggot development. A count is then mate after l~ days of the number of flies which have hatched out of the pupae.
The compounds of formula I obtained according to Examples 1 and 2 have good activity in this test.
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Example 5: Action a~ainst Lucilia sericata I ml of an aqueous solution containing 0.5 % 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 medi~m, and the insecticidal action is determined after 48 and Y6 hours by eval~ating the mortality rate.
In this test, compounds of the formula I according to Examples 1 and 2 exhibit ~ood activity against Lucilia sericata.
Example 6: Act~on against Aedes aegypti A concentration of 400 ppm is obtained by pipetting a specific amount of a 0.1 % solution of the test compound iD acetone onto the surface of 150 ml of water in a beaker. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aedes aegypti are put into the beaker containing the test compound. Mortality counts are made after 1, 2 and 5 days.
In this test, compounds of Examples 1 and 2 exhibit good activity against Aedes aegypti.
Example 7: Insecticidal action against feeding lnsects Cotton plants (about 20 cm high) are sprayed with aqueous emulsions (obtained from a 10 % emulsifiable concentrate) containing the respectlve test compound in concentrations of 0.75 to 400 ppm. After the spray coating has dried, the cotton plant~ 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.
At 24 hour intervals, a mortslity count is msde snd the lsrvs sre also exsmlned for inhibition of development snd shedding.
In this test, 80-100 ~0 kill against Spodopters is effected with compounds 1, 2 and 4 st 0.75 ppm snd with compounds 3, ~, 7 snd 8 at 3.0 ppm. The following compounds effect 80-100 % kill s~ainst Heliothis: compounds 1 and 6 at 3.0 ppm, compounds 2 and 7 st 12.5 ppm, compounds 3 and 8 at 50 ppm, and compound 4 at 400 ppm.
~8174~
Example 8:
Action against Spodo~tera littoralis and Heliothis virescens (larvae and e~g~2~
Three cotton plants each having a height of about 15-20 cm and grown in pots are treated with a sprayable liquid preparation of the test compound in a concentration of 400 ppm. After the spray coating has dried, the potted plants are placed in a metal container having a capacity of about 20 litres and covered with a glass plate. The humidity in the interior of covered container is regulated such that no water of condensation forms. Direct light falling on the plants is avoided. The three plants are then infested altogether with:
a~ 50 larvae of Spodoptera littoralis or Heliothis virescens in the L1-stage;
b) 20 larvae of Spodoptera littoralis or Heliothis virescens ln the L3-stage;
c) 2 egg deposit~ of Spodoptera littoralis or Heliothis virescens.
(The prod~cedure is that two leaves of each plant are put into a plexlglass cylinder sealed at both ends with muslin. Two egg deposits of Spodoptera, or a part of a cotton leaf with eggs of Heliothis deposited thereon, are added to the leaves sealed in ; the cylinder.) ; Evaluation in comparison w1th untreated controls is made after 4 to 5 days, taking into account the following criteria:
a) the number of still living larvae, b) inhibition of larval develop~ent and shedding, c) feeting damage (shredding and perforation damage), d) hatching rate (number of larvae hatched from the eggs).
In this test, the compounds of Formula I according to Examples l and 2 exhibit good overall activity.
, 1~817 Example ~: Ovicidal action against Spodoptera littoralis Eggs of Spodoptera littorali8 deposited on filter paper are cut out of the paper and immersed in a 0.~5 % by weight solution of each compound to be tested in a 1:1 mixture of acetone-water. The treated deposits are then removed from this mixture and kept in plastic dishes at 28C and 60 % humidity. The hatching rate, i.e. the number of larvae which have developed from the treated eggs, is determined after 5 days.
The compounds of formula I accordi~g to Exa~ples 1 and 2 show good activity in this test.
Example 10: Ovicidal action against Epilachna varivestis A mixture is prepared from 20 % by weight of test compound, 70 % by weight of xylene and 10 % by weight of a mixture of a reaction product of an alkyl phenol with ethylene oxide and calcium dodecyl-benzsnesulfonate. An aqueous emulsion containing 800 ppm of test compound are prepared from this concentrate.
100 eggs of Epilachna varivestis (Mexican bean beetle), freshly deposited on leaves of Phaseolus vulgaris, are moistened with the above described aqueous emulsion (concentration: 800 ppm) and dried lightly. The treated egg deposits are kept in a ventilated container until the simultaneously deposited untreated controls have hatched.
The percentage kill is evaluated under a stereoscopic microscope.
The compounds of Formula I according to Examples 1 and 2 show good activity in this test.
Example 11: Ovlcidal action against Heliothis virescens and Leptiotarsa decemlineata 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 concen-tration of 800 ppm. One day-old egg deposits of Heliothis on ., .
.
1~17~1 cellophane/and egg deposits of Leptinotarsa on potato leaves are immersed ln these emulslons for ~ minutes and then collected by suction on round filters. The treated deposits are placed in petri dishes and kept in the dark. The hatching rate in comparison wlth untreated controls is determined after 6 to 8 days.
Compounds of formula I according to Examples 1 and 2 show good activity in this test.
Example 12 Ovicidal action a~ainst LaspeYresia pomonella (e~s):
Egg deposits of Laspsyrasia pomonella not more than 24 hours old are lmmersed on filter paper for 1 minute in an aqueous acetonic solution containing 400 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 is evaluated after 6 days.
The compounds of formula I according to Examples 1 and 2 exhibit good activity in this test.
Example 13: Action again6t Anthonomus grandis (adults) Two cotton plants in the 6-leaf stage, in pots, are each sprayed with a wettable aqueous emulsion formulation containing the test compound in a concentration of 12.5 ppm. After the spray coating has dried (about 1 1/2 hours~, each plant is popuiated 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 ~0 %
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-feed~ng action as compared with untreated controls.
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.
~L'~3iL7 In this test, compounds l, 2, 6 and 7 of Example l ef~ect 80-lO0 ~0 kill (mortality).
Example 14:
Action against plant-destructive acarids: Tetranychus urticae ~OP-sensitlve) and Tetranychus cinnabarinus ~OP-tolerant) 16 hours before the test for acaricidal action, the primary leaves of Phaseolus vulgaris plants are in~ected with an infested piece of leaf from a mass culture of Tetranychus urt~cae (OP-sensitive) and Tetranychus cinnabarinus (OP-tolerant). (The tolerance refers to diazinone). The treated infested plants are sprayed to drip point with a test solut~on containing 400 ppm of the compound to be tested. A count of the number of liv~ng and dead imagines and larvae (all mobile stages) is made under a stereoscopic microscope after 24 hours and again after 7 days. One plant is used for each test substance and test species. During the test run, the plants are kept in greenhouse compartments at 25~C.
In this test, the compounds of formula I according to Examples l and 2 show good actlvity against Tetranychus urticae and Tetranychus cinnabarinus.
Exam~le 15: Influence on the reproduction of Anthonomous grandis Anthonomous grandis adults which are not more than 24 hours old after hatching sre transferred in groups of 25 to barred cages. The cages are then immersed for 5 to lO seconds in an acetonic solution containing 8~ ppm 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 whether larvae have developed from the eggs.
12~31741 The duration of the reproduction inhibiting effect of the test compounds is determined by monitoring the egg deposits 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 the formula I according to Examples 1 and 2 exhibit a good reproduction inhibiting effect in this test.
.
, , ~ :
"~
.~, , , !
; :,, ~, - '~
:' , ~: , . - -: ' ~ .
: .~, - '
Claims (16)
1. A compound of formula I
(I), wherein R1 is hydrogen or halogen and R2 and R3 are halogen.
(I), wherein R1 is hydrogen or halogen and R2 and R3 are halogen.
2. A compound according to claim 1, wherein R1 is hydrogen, fluorine or chlorine, R2 is fluorine or chlorine and R3 is chlorine or bromine.
3. A compound according to claim 2, wherein R1 is hydrogen, fluorine or chlorine, R2 is fluorine or chlorine, and R3 is chlorine.
4. A compound according to claim 3 of the formula
5. A compound according to claim 3 of the formula
6. A compound according to claim 2, wherein R1 is hydrogen, fluorine or chlorine, R2 is fluorine or chlorine, and R3 is bromine.
7. A compound according to claim o of the formula
8. A compound according to claim 6 of the formula
9. A process for the preparation of a compound of the formula I
according to claim 1, which comprises reacting a) a compound of formula II
(II) with a compound of formula III
(III), 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, III, IV, V and VI above R1, R2 and R3 are as defined in claim 1 and R is a C1-C8alkyl radical which may be substituted by halogen.
according to claim 1, which comprises reacting a) a compound of formula II
(II) with a compound of formula III
(III), 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, III, IV, V and VI above R1, R2 and R3 are as defined in claim 1 and R is a C1-C8alkyl radical which may be substituted by halogen.
10. A method of controlling insects and representatives of the order Acarina, which comprises treating or contacting said insects, their various development stages or the locus thereof, with a pesticidally effective amount of a compound of the 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 suitable therefor with the proviso that the locus is not in or on an animal.
11. A method according to claim 10 for controlling insects or representatives of the order Acarina on plants.
12. A method according to claim 11 for controlling plant-destructive insects.
13. A method according to claim 12 for controlling plant-destructive insects in crops of cotton or fruit.
14. A method according to claim 10 for controlling animal pest insects or representatives of the order Acarina in a common environment of said animals and said pests.
15. A pesticidal composition comprising a pesticidally effective amount of a compound according to any one of claim 1 to claim 8 as an active ingredient in admixture with a diluent or carrier.
16. A pesticidal composition comprising a pesticidally effective amount of a compound according to any one of claim 1 to claim 8 as an active ingredient in admixture with a solid or liquid diluent or carrier, adjuvant or surface-active agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH417984 | 1984-08-31 | ||
| CH4179/84-8 | 1984-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1281741C true CA1281741C (en) | 1991-03-19 |
Family
ID=4271267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000489645A Expired - Lifetime CA1281741C (en) | 1984-08-31 | 1985-08-29 | Phenylbenzoylureas |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0174274B1 (en) |
| JP (1) | JPS6165859A (en) |
| KR (1) | KR870002060A (en) |
| AT (1) | ATE38829T1 (en) |
| AU (1) | AU587784B2 (en) |
| BR (1) | BR8504196A (en) |
| CA (1) | CA1281741C (en) |
| DE (1) | DE3566399D1 (en) |
| DK (1) | DK161196C (en) |
| EG (1) | EG17683A (en) |
| ES (1) | ES8606852A1 (en) |
| IL (1) | IL76185A0 (en) |
| MY (1) | MY102083A (en) |
| OA (1) | OA08090A (en) |
| TR (1) | TR23048A (en) |
| ZA (1) | ZA856651B (en) |
Families Citing this family (6)
| 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 |
| GB8905741D0 (en) * | 1989-03-13 | 1989-04-26 | Shell Int Research | Process for preparing carbamates,and intermediates therin |
| JP2549224Y2 (en) * | 1990-12-21 | 1997-09-30 | 矢崎総業株式会社 | Wire joint box |
| JP3580382B2 (en) * | 1995-02-24 | 2004-10-20 | 三洋電機株式会社 | Pachinko machine mounting unit |
| DE10052331A1 (en) * | 2000-10-17 | 2002-05-02 | Stribel Gmbh | A fan installation |
| KR101474181B1 (en) | 2011-01-28 | 2014-12-17 | 미쓰비시덴키 가부시키가이샤 | Circulator |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2726684A1 (en) * | 1977-06-14 | 1979-01-04 | Hoechst Ag | Insecticidal di:halo-benzoyl-phenylurea derivs. - useful for plant protection or textile preservation |
| DE2801316A1 (en) * | 1978-01-13 | 1979-07-19 | Bayer Ag | SUBSTITUTED N-PHENYL-N '- (2-CHLORINE-6-FLUORO-BENZOYL) UREAS, METHOD FOR THEIR PRODUCTION AND THEIR USE AS INSECTICIDES |
| DE3064254D1 (en) * | 1979-07-11 | 1983-08-25 | Ciba Geigy Ag | N-phenyl-n'-benzoyl ureas, process for their preparation, compositions containing them and their use as pesticides |
| AR242020A1 (en) * | 1981-07-30 | 1993-02-26 | Dow Chemical Co | Substituted n-aroyl n'-phenyl urea compounds |
| DE3217619A1 (en) * | 1982-05-11 | 1983-11-17 | Bayer Ag, 5090 Leverkusen | 2,4-DIHALOGENBENZOYL (THIO) UREA, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PEST CONTROL |
| ATE43788T1 (en) * | 1983-09-01 | 1989-06-15 | Duphar Int Res | BENZOYL UREAS WITH ANTITUMORAL ACTIVITIES. |
| EP0167197B1 (en) * | 1984-07-05 | 1989-01-18 | Duphar International Research B.V | Benzoylurea compounds, and insecticidal and acaricidal compositions comprising same |
-
1985
- 1985-08-22 TR TR36516/85A patent/TR23048A/en unknown
- 1985-08-26 DE DE8585810382T patent/DE3566399D1/en not_active Expired
- 1985-08-26 AT AT85810382T patent/ATE38829T1/en not_active IP Right Cessation
- 1985-08-26 EP EP85810382A patent/EP0174274B1/en not_active Expired
- 1985-08-26 IL IL76185A patent/IL76185A0/en not_active IP Right Cessation
- 1985-08-29 CA CA000489645A patent/CA1281741C/en not_active Expired - Lifetime
- 1985-08-30 ES ES546582A patent/ES8606852A1/en not_active Expired
- 1985-08-30 KR KR1019850006316A patent/KR870002060A/en not_active Application Discontinuation
- 1985-08-30 OA OA58671A patent/OA08090A/en unknown
- 1985-08-30 DK DK395985A patent/DK161196C/en not_active IP Right Cessation
- 1985-08-30 AU AU46921/85A patent/AU587784B2/en not_active Ceased
- 1985-08-30 BR BR8504196A patent/BR8504196A/en not_active IP Right Cessation
- 1985-08-30 ZA ZA856651A patent/ZA856651B/en unknown
- 1985-08-31 JP JP60193003A patent/JPS6165859A/en active Pending
- 1985-09-01 EG EG540/85A patent/EG17683A/en active
-
1987
- 1987-09-29 MY MYPI87002260A patent/MY102083A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR8504196A (en) | 1986-06-24 |
| EP0174274A1 (en) | 1986-03-12 |
| AU4692185A (en) | 1986-03-06 |
| ATE38829T1 (en) | 1988-12-15 |
| DK161196B (en) | 1991-06-10 |
| ZA856651B (en) | 1986-04-30 |
| IL76185A0 (en) | 1985-12-31 |
| DE3566399D1 (en) | 1988-12-29 |
| EG17683A (en) | 1990-10-30 |
| DK161196C (en) | 1991-11-25 |
| OA08090A (en) | 1987-03-31 |
| KR870002060A (en) | 1987-03-28 |
| ES8606852A1 (en) | 1986-05-01 |
| DK395985D0 (en) | 1985-08-30 |
| ES546582A0 (en) | 1986-05-01 |
| AU587784B2 (en) | 1989-08-31 |
| JPS6165859A (en) | 1986-04-04 |
| DK395985A (en) | 1986-03-01 |
| MY102083A (en) | 1992-03-31 |
| EP0174274B1 (en) | 1988-11-23 |
| TR23048A (en) | 1989-02-14 |
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