CA1291151C - N-benzoyl-n'-3,5-dichloro-4-hexafluoropropyloxy-phenylureas - Google Patents
N-benzoyl-n'-3,5-dichloro-4-hexafluoropropyloxy-phenylureasInfo
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- CA1291151C CA1291151C CA000520273A CA520273A CA1291151C CA 1291151 C CA1291151 C CA 1291151C CA 000520273 A CA000520273 A CA 000520273A CA 520273 A CA520273 A CA 520273A CA 1291151 C CA1291151 C CA 1291151C
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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
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
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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
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/30—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by halogen atoms, or by nitro or nitroso groups
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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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- General Health & Medical Sciences (AREA)
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- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Photoreceptors In Electrophotography (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Polyesters Or Polycarbonates (AREA)
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Abstract
Benzoylphenylureas Abstract of the Disclosure The invention relates to novel substituted N-benzoyl-N'-3,5-dichloro-hexafluoropropyloxyphenylureas of the formula
Description
5-15531/~
Benzoylphenylureas The present invention relates to novel substituted N-benzoyl-N'-3,5-dichloro-4-hexafluoropropyloxyphenylureas, to processeG and to intermediates for the preparation thereof, and to the u~e of the novel compounds in pest control.
The invention relates to compounds of formula I
-C0-NH-C0-NH~ 0-CF2-CHF-CF3 (I) ~2 ~1 whereln R1 is hydrogen or fluorine and R2 i5 fluorine or chlorine, and to salts thereof.
Compounds of formula I meriting particular interest are those wherein Rl i9 fluorine and R2 is fluortne or chlorine.
Further preferred compound~ of formula I are those wherein R1 i8 hydrogen and R2 is fluorine or chlorine.
The compounds of formula I can be prepared by msthod~ analogous to ones known per se ~q.v. e.g. German Offenlegungs~chrift specifi-cat~on~ 2 123 236, 2 601 780 and 3 240 975).
Thus, for example, a compound of ~ormula I can be obtained by reactlng , . ~
a) the compound of formula II
lCl CF3-CHF-CF2-O~ --NHz (II) ~1 with a compound of formula III
~1 CO-N=C=O (III) or b) the compound of formula IV
CF3-CHF-CFz-O-~ N=C=O (IV) Cl with a compound of formula V
lLl --CO-NH2 (V), ~2 or c) thc compound of formula II with a compound of formula VI
, ~Ll ~ ~--CO-NH-COOR (VI).
~2 In formulae III, V and VI above, the radicals R1 and R2 are a8 dcfined for formula I, and R i~ a Cl-Cnalkyl radical which is unsubstituted or substituted by halogen, preferably chlorine.
The above proces~es 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; nitrlles 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) is normally carried out in the tempera-ture range from -10 to +200C, preferably from 0 to 100C, 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 tempera-ture range from 0 to 150C, preferably at the boiling point of the solvent employed and, if desired, in the presence of an organic base such as pyridine1 and/or with the addition of an alkali metal or alkaline earth metal, prefersbly sodium. For proces~ c), i.e. for the reaction of the urethane of formula YI with an aniline of formula II, a temperature range from about 60 to the boiling point of the reaction mixture i8 preferred, and the solvent amployed is preferably an aromatic hydrocarbon such a3 toluene, xylene, chloro-benzene 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 sniline of formula II is a novel compound which likewise constitutes an object of the present invention. The compound of formula II can be prepared in a mannar known per se by hydrogenating the suitably substituted nitrobenzene o~ formula VII
~1 CF3-CHF-CF2-O~ -N0~ (VII) ~1 .. . .
by a proces~ analogous to that described ln J. Org. Chem. 29 ~1964), 1, (q.v. al~o the literat~re cited therein). However, the aniline of formula II can also be obtained by chemical reduction le.g. with Sn(II) chloride/HCl) of the nitro compound of formula VII (q.v.
Houben-Weyl, "Methoden d. org. Chemie" 11/1, ll22). The nitro compound of formula VII itself can be prepared by fluoroalkylating 3,5-dichloro-4-nitrophenol. A further process for the preparation of the aniline of formula II comprises fluoroalkylating in corresponding manner the acylated 2,6-dichloro-4-hydroxyaniline and then removing the acyl group9 s.g. by acid hydroly~is, or effecting the fluoroalkylation with a salt of 3,5-dichloro-4-hydroxyaniline, e.g. ~he chlorohydrate.
Benzoylisocyanates of formula III can be obtained, in~er alia, as follows (q.v. J. Agr. Food Chem. 21, 348 and 993; 1973):
C ~ N H?SO4~120~ -CO-NH2 ~2 ~2 1~1 ClOC-COCl ~ -CO-N~C~O (III) .
The 4-(hexafluoropropyloxy)phenylisocyanate of formula IV (b.p.
95C/0.01 torr), which is novel per se, can be prepared a.g. by phosgenat~ng the aniline of formula II by methods which are commonly employed in the art and also comprise~ an ob~ect of this invention.
The benazmides of formula V which are furtber used as starting materials are known (q.v. for example Beil~tein "Handbuch der organischen Chemie", Vol. 9, p. 336~.
Urethanes of for~ula VI can be obtained in a manner known per se by reacting a benzoylisocyanate of formula III 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 Cl-COOR.
- 5 ~
In accordance with the present invention, the novel compounds of formula I also comprise the salts thereof which not only exhibit high insecticidal activity, but are also readily soluble in solvents and diluents, in particular in organic solvents, and can also be formulated more easily.
To be singled out for special mention are the metal salts of the compounds of formula I of the invention, in particular the alkali metal and alkaline earth metal salts thereof, preferably the sodium salts and potassium salts. These salts are prepared in a manner known per Qe, e.g. by reacting a compound of formula I with a metal alkanolate such as 30dium ethylate or potassium methylate. A given salt can be converted into a deslred ~alt of another metal by salt-interchange, e.g. wi~h another alkanolate.
Of particular importance are the salts of compounds of formula I
with organic bases, an essential feature of which is the presence of a quaternary nitrogen atom. Such salt6 are of formula Ia [ ~ o-~CO~N~CO~NH~~ o--0-CF2-CHF-CF3 ¦ X (Ia) wherein Rl and R2 are as defined above and X~ is the cation of an organic ba3e. X0 is preferably one of the following organic catioDs:
(CH3)4 N , (C2Hs)4 N , (n-C3H7)4 N , (i-C3H7)4 N , (n-C4Hg)4 N , (~ CH2) (CH3)3 N ' ~ CH3)3 N , i~il ~ (C4Hg)3 NH
H
'~ \'/ ~' and [ CH3-(CH2)n--] N-CH3 H
whereby n i8 an integer from 8 ~o 12. The aalts of forrnula Ia al~o comprise mixtures of these salts with different cations. The salts of formula Ia can be prepared in a ~anner known per se by reacting a compound of formula I with corresponding ammonium hydroxides of the formula X~(OH)~, wherein X~ iB as defined above.
N-Ben20yl-N'-2,5-dichlorophenylureas with a haloalkoxy substituent in the 4-position of the phenyl rlng are already known as insecticldes (q.v. US patent speciflcation 4 518 804 and German Offenlegungsschrift 2 848 794). In3ecticidal N-halobenzoyl-N'-(3,5-dichloro-4-haloalkenyloxyphenyl)ureas are de~cribed in VS patent specification 4 162 330. Insectic~dal N-halobenzoyl-N'-(3,5-di-chloro-4-haloalkoxyphenyl)ureas are the sub~ect matter of US patent ~pecification 4 468 405. Furthermore, compounds of similar ~ructure are known from US patent specification 4 529 819 and British patent applications 2 106 499, 2 106 500, 2 106 501 and 2 113 679. The feature which essentially distinguishes the noval benzoylphenyl-ureas of formula I according to the present invention from the compounds described ln th0se references is that the novel compound~
of this invention carry in the 4-position of the ph~nyl ring a 1,1,2,3,3,3-hexafluoropropyloxy group.
_ 7 ~ 5~
Surprisingly, it has been found that the compounds of ~his inven-tion and the salts thereof have excellent yroperties as pesticides while being well tolerated by plants and having low toxlcity 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 control-ling insects o~ the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera~ Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatlves of the order AcariDa of the families: Ixodidae, Argasidae, Tetranychldae and Dermanys3idae.
In addition to their action against flies, e.g. Musca domestica, and mo3quito 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 ~ellothls virescens) and in fruit and veg~table~
~e.g. against Laspeyresia pomonolla, Ieptlnotarsa 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 insect~. 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 insect3, especially in Coleopterae, e.g. Anthonomus grandis.
The compound3 of formula I can also be used for controlling ecto-parasite3 such as Lucilia sericata, in domestic animals and produc-tive livestock, e.g. by treating animals, cowsheds, barns, stables etc., and pa~tures.
The compounds of formula I are also suitable for controlling the following specie3 of mites which attack crops of fruit and veget~bles:
Tetranychu~ urticae, Tetranychus cinnabarinus, Panonychus ul~i, - 8 - ~2~
Broybla ~ubrioculus, Panonychu~ citri, Eriophyes piri, E~iophyes ribis, Eriophyes vitis, Ta~sonemus pallidus, Phyllocoptes vitis and Phyllocoptruta oleivora.
~oreover, the benzoylureas of formula I have properties enabling them to be used for conerolling slugs and snails. The repellant and feed inhibiting action of these compounds is frequently very difficult to ascertain in laboratory tests. However, in field trials even at very low concentrations good activity is observed in agricultural and horticultural crops. In particular, sensitive crops of lettuce, vegetables and fruit (such as strawberries) and ornamentals and flowers are af~orded protection agalnst feeding damage caused by slugs and snails. The compound~ of formula I of this invention are effective against all slugs and snails, most of which occur as polyphagic pests in agricultural and horticultural crops. In addition to exhibiting feed inhiblting action, the compounds of formula I can also effect mortality. Numbering among terrestrial 91ugs are aeveral pests which cau~e damage of great economic significance, for example the slugs Arion rufus (red slug), Arion ater and other Arionida~, Limax species and field slugs, e.g.
Deroceras reticulatum snd D. agreste of the family Limacidae, and also species of the family Milacidae. Damage is also caused by snails, inee~ alia, of the genera Bradybaena, Cepea, Cochlodina, Discus, Euomphalia, Galba, Helicigona, Helix, Helicella, Helico-discus, Lymnaea, Opeas, Vallonia and Zonitoides.
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 substsntially broadened and adapted to prevailing circum~tances by addition of other insecticides and~or acaricides. Examples of suitable additive~ include: organophosphorus - 9 ~
compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorina~ed hydrocarbona, and Bacillus thurlngiensis preparations.
The compounds of formula I are used in unmodlfied 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 (activ~ ingredient) of formula I or combinations thereof with other insecticides or acaricides, and, where appropriate, a solid or liquid ad~uvant, are prepared in known manner, e.g. by homogeneously mixlng and~or grinding the active ingredients with extenders, e.g. solvents, 301id carriers and, in some cases, surface-active compounds (surfactants).
Suitabls 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 pars~fins, alcohol~ and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones ~uch as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable olls such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. ~or dusts and dispersible powders are nor~ally natural mineral fillers such as calcite, talcum, kaolin, montmorillonlte or attapulgite. In order to improve the physical properties it is also pos6ible to add highly dispersed silicic acids or highly dispersed absorbent polyme~s. Su1table granula~ed adsorp-tive carriers are porous types, for e~ample pumice, broken brick, sepiolite or bentonite; and suitable nonsorben~ carriers are materlals such as calcite or aand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, or of combinations thereof with other insecticides or acaricides, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifylng, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures o$ 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 a5 well aB
modified and unmodified phospholipids.
More frequently, however, so-called synthetic surfactants are uaed, especially fatty sulfonates, fatty sulfates, sulfonated benzimida-zole derivatives or alkylarylsulfonates.
The fatty sulfonatas 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 lignosulPonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
::
These compoundæ also comprise the salts of sulfurlc acid esters and sulfonic acids of fatty alcohol/e~hylene oxide adducts. The sulfona-ted benzimidazole deriva~ives preferably contain 2 sulfonic acid groups and on~ fatty acid radical contalning 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-ethanolamine ~alts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic ~cid, or of a naphthalenesulfonic acid/formaldehyde condensation produet. ~lso suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol with ~ to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty aclds and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (allphatic) 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, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol containing 1 to 10 csrbon 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 nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethyl~ne glycol and octylphenoxypolyethoxyethanol. Patty acid esters of polyoxyethylene ~orbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary a~monium salts which contain, a~ N-substituent, at least one Cg-C22alkyl radical and, as $urther substituents, unæubstituted or halogenated lower alkyl, - 12 ~
benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halidesl methylsulfates or ethyl~ulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonlum bromide.
The surfactants customarily employed in ~he art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New JerDey, 1979; Dr. Helmut Stache, "Tensid Taschenbuch" (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna 1981.
The pesticidal compo~itions usually contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or combination thereof with other lnsecticldes or acariclde~, 1 to 99.9 % of a eolid or liquid ad~uvant, and 0 to 25 %, preferably 0.1 to 20 %, uf a surfactant.
Whereas commercial products are preferably formulated as concen-trates, the end user will normally employ diluted formulations of substantially lower concentration.
The compositions may also contain further ingredisnts, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
Exam~la 1:
a) Preparation o~ 3~5-dichloro-4-(1,1,2,313,3-hexafluoropropyl-o~y~aniline 47 g of 4-acetylamino-3,5-dichlorophenol tugether with 154 g of 90 %
potassium hydroxide solution and 130 ml of dimethylformamide are stirred in an au~oclave. 75.8 g of hexafluoropropylene are then pressed into the closed autoclave. The mixture is stirred for 20 hours at 70C under the pressure developing in the autoclave.
After cooling, the mixture i8 concentrated by rotary evaporation and - 13 ~
the resldue is dissolved in methylene chloride. The resultant solution is washed with water, dried over Na~S04 and concentrated.
The crude product obtainsd as residue i9 chromatographed through a column of silica gel (length: 1 m; dlameter: 10 cm) eluted with an 11:1 mixture of toluene and acetone, affording 4-acetylamino-3,5-di-chloro-1-(1,1,2,3,3,3-hexafluoropropyloxy~benzene in the form of pale yellow crystals (m.p.: 113-115C), 26 g of which a~e kept for 10 hours under reflux with 110 ml of ethanol and 35.6 ml 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 methylene chloride. The organic extract phase i3 washed with water, dried over NazSO4 and concentrated. The residue is purified by distillation, thus affording the title compound of the formula ~1 H2N~ OCFz-CHF-CF3 ~1 as a colourlesfi liquid with a boiling point of 91-96C/0.001 torr.
b~ Preparation of N~(2,6-difluorobenzoyl~-N'-~3~5-dichlor_-4-~1,1?2,3,3,3-hexafluoropropyloxy)phenyl~urea 4.3 g of 3,5-dichloro-4-~1,1,2,3,3,3-hexafluoropropyloxy)aniline are dissolved with stirring in 50 ml of dry toluene and, with exclusion of moisture, a solution of 2.41 g of 2,6-difluorobenzoylisocyanate in 10 ml of dry toluene is added at room temperature. ~he batch i3 stirred for a further 12 hours at room temperature. About 75 % of the solvent i9 then removed by rotary evaporation, the precipitated residue is filtered with suction, wa~hed with a ~mall amount of cold toluene and hexane and then dried in vacuo, affording the title compound of the formula Cl C0-NH-C0-NH~~ OCF2-CHF-CF3 F Cl in the form of a crystalline white powder with a melting polnt of 171-172C (compound l).
The following compounds of formula I have been prepared in a manner corresponding to that described above:
Compound m.p.
Benzoylphenylureas The present invention relates to novel substituted N-benzoyl-N'-3,5-dichloro-4-hexafluoropropyloxyphenylureas, to processeG and to intermediates for the preparation thereof, and to the u~e of the novel compounds in pest control.
The invention relates to compounds of formula I
-C0-NH-C0-NH~ 0-CF2-CHF-CF3 (I) ~2 ~1 whereln R1 is hydrogen or fluorine and R2 i5 fluorine or chlorine, and to salts thereof.
Compounds of formula I meriting particular interest are those wherein Rl i9 fluorine and R2 is fluortne or chlorine.
Further preferred compound~ of formula I are those wherein R1 i8 hydrogen and R2 is fluorine or chlorine.
The compounds of formula I can be prepared by msthod~ analogous to ones known per se ~q.v. e.g. German Offenlegungs~chrift specifi-cat~on~ 2 123 236, 2 601 780 and 3 240 975).
Thus, for example, a compound of ~ormula I can be obtained by reactlng , . ~
a) the compound of formula II
lCl CF3-CHF-CF2-O~ --NHz (II) ~1 with a compound of formula III
~1 CO-N=C=O (III) or b) the compound of formula IV
CF3-CHF-CFz-O-~ N=C=O (IV) Cl with a compound of formula V
lLl --CO-NH2 (V), ~2 or c) thc compound of formula II with a compound of formula VI
, ~Ll ~ ~--CO-NH-COOR (VI).
~2 In formulae III, V and VI above, the radicals R1 and R2 are a8 dcfined for formula I, and R i~ a Cl-Cnalkyl radical which is unsubstituted or substituted by halogen, preferably chlorine.
The above proces~es 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; nitrlles 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) is normally carried out in the tempera-ture range from -10 to +200C, preferably from 0 to 100C, 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 tempera-ture range from 0 to 150C, preferably at the boiling point of the solvent employed and, if desired, in the presence of an organic base such as pyridine1 and/or with the addition of an alkali metal or alkaline earth metal, prefersbly sodium. For proces~ c), i.e. for the reaction of the urethane of formula YI with an aniline of formula II, a temperature range from about 60 to the boiling point of the reaction mixture i8 preferred, and the solvent amployed is preferably an aromatic hydrocarbon such a3 toluene, xylene, chloro-benzene 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 sniline of formula II is a novel compound which likewise constitutes an object of the present invention. The compound of formula II can be prepared in a mannar known per se by hydrogenating the suitably substituted nitrobenzene o~ formula VII
~1 CF3-CHF-CF2-O~ -N0~ (VII) ~1 .. . .
by a proces~ analogous to that described ln J. Org. Chem. 29 ~1964), 1, (q.v. al~o the literat~re cited therein). However, the aniline of formula II can also be obtained by chemical reduction le.g. with Sn(II) chloride/HCl) of the nitro compound of formula VII (q.v.
Houben-Weyl, "Methoden d. org. Chemie" 11/1, ll22). The nitro compound of formula VII itself can be prepared by fluoroalkylating 3,5-dichloro-4-nitrophenol. A further process for the preparation of the aniline of formula II comprises fluoroalkylating in corresponding manner the acylated 2,6-dichloro-4-hydroxyaniline and then removing the acyl group9 s.g. by acid hydroly~is, or effecting the fluoroalkylation with a salt of 3,5-dichloro-4-hydroxyaniline, e.g. ~he chlorohydrate.
Benzoylisocyanates of formula III can be obtained, in~er alia, as follows (q.v. J. Agr. Food Chem. 21, 348 and 993; 1973):
C ~ N H?SO4~120~ -CO-NH2 ~2 ~2 1~1 ClOC-COCl ~ -CO-N~C~O (III) .
The 4-(hexafluoropropyloxy)phenylisocyanate of formula IV (b.p.
95C/0.01 torr), which is novel per se, can be prepared a.g. by phosgenat~ng the aniline of formula II by methods which are commonly employed in the art and also comprise~ an ob~ect of this invention.
The benazmides of formula V which are furtber used as starting materials are known (q.v. for example Beil~tein "Handbuch der organischen Chemie", Vol. 9, p. 336~.
Urethanes of for~ula VI can be obtained in a manner known per se by reacting a benzoylisocyanate of formula III 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 Cl-COOR.
- 5 ~
In accordance with the present invention, the novel compounds of formula I also comprise the salts thereof which not only exhibit high insecticidal activity, but are also readily soluble in solvents and diluents, in particular in organic solvents, and can also be formulated more easily.
To be singled out for special mention are the metal salts of the compounds of formula I of the invention, in particular the alkali metal and alkaline earth metal salts thereof, preferably the sodium salts and potassium salts. These salts are prepared in a manner known per Qe, e.g. by reacting a compound of formula I with a metal alkanolate such as 30dium ethylate or potassium methylate. A given salt can be converted into a deslred ~alt of another metal by salt-interchange, e.g. wi~h another alkanolate.
Of particular importance are the salts of compounds of formula I
with organic bases, an essential feature of which is the presence of a quaternary nitrogen atom. Such salt6 are of formula Ia [ ~ o-~CO~N~CO~NH~~ o--0-CF2-CHF-CF3 ¦ X (Ia) wherein Rl and R2 are as defined above and X~ is the cation of an organic ba3e. X0 is preferably one of the following organic catioDs:
(CH3)4 N , (C2Hs)4 N , (n-C3H7)4 N , (i-C3H7)4 N , (n-C4Hg)4 N , (~ CH2) (CH3)3 N ' ~ CH3)3 N , i~il ~ (C4Hg)3 NH
H
'~ \'/ ~' and [ CH3-(CH2)n--] N-CH3 H
whereby n i8 an integer from 8 ~o 12. The aalts of forrnula Ia al~o comprise mixtures of these salts with different cations. The salts of formula Ia can be prepared in a ~anner known per se by reacting a compound of formula I with corresponding ammonium hydroxides of the formula X~(OH)~, wherein X~ iB as defined above.
N-Ben20yl-N'-2,5-dichlorophenylureas with a haloalkoxy substituent in the 4-position of the phenyl rlng are already known as insecticldes (q.v. US patent speciflcation 4 518 804 and German Offenlegungsschrift 2 848 794). In3ecticidal N-halobenzoyl-N'-(3,5-dichloro-4-haloalkenyloxyphenyl)ureas are de~cribed in VS patent specification 4 162 330. Insectic~dal N-halobenzoyl-N'-(3,5-di-chloro-4-haloalkoxyphenyl)ureas are the sub~ect matter of US patent ~pecification 4 468 405. Furthermore, compounds of similar ~ructure are known from US patent specification 4 529 819 and British patent applications 2 106 499, 2 106 500, 2 106 501 and 2 113 679. The feature which essentially distinguishes the noval benzoylphenyl-ureas of formula I according to the present invention from the compounds described ln th0se references is that the novel compound~
of this invention carry in the 4-position of the ph~nyl ring a 1,1,2,3,3,3-hexafluoropropyloxy group.
_ 7 ~ 5~
Surprisingly, it has been found that the compounds of ~his inven-tion and the salts thereof have excellent yroperties as pesticides while being well tolerated by plants and having low toxlcity 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 control-ling insects o~ the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera~ Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as representatlves of the order AcariDa of the families: Ixodidae, Argasidae, Tetranychldae and Dermanys3idae.
In addition to their action against flies, e.g. Musca domestica, and mo3quito 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 ~ellothls virescens) and in fruit and veg~table~
~e.g. against Laspeyresia pomonolla, Ieptlnotarsa 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 insect~. 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 insect3, especially in Coleopterae, e.g. Anthonomus grandis.
The compound3 of formula I can also be used for controlling ecto-parasite3 such as Lucilia sericata, in domestic animals and produc-tive livestock, e.g. by treating animals, cowsheds, barns, stables etc., and pa~tures.
The compounds of formula I are also suitable for controlling the following specie3 of mites which attack crops of fruit and veget~bles:
Tetranychu~ urticae, Tetranychus cinnabarinus, Panonychus ul~i, - 8 - ~2~
Broybla ~ubrioculus, Panonychu~ citri, Eriophyes piri, E~iophyes ribis, Eriophyes vitis, Ta~sonemus pallidus, Phyllocoptes vitis and Phyllocoptruta oleivora.
~oreover, the benzoylureas of formula I have properties enabling them to be used for conerolling slugs and snails. The repellant and feed inhibiting action of these compounds is frequently very difficult to ascertain in laboratory tests. However, in field trials even at very low concentrations good activity is observed in agricultural and horticultural crops. In particular, sensitive crops of lettuce, vegetables and fruit (such as strawberries) and ornamentals and flowers are af~orded protection agalnst feeding damage caused by slugs and snails. The compound~ of formula I of this invention are effective against all slugs and snails, most of which occur as polyphagic pests in agricultural and horticultural crops. In addition to exhibiting feed inhiblting action, the compounds of formula I can also effect mortality. Numbering among terrestrial 91ugs are aeveral pests which cau~e damage of great economic significance, for example the slugs Arion rufus (red slug), Arion ater and other Arionida~, Limax species and field slugs, e.g.
Deroceras reticulatum snd D. agreste of the family Limacidae, and also species of the family Milacidae. Damage is also caused by snails, inee~ alia, of the genera Bradybaena, Cepea, Cochlodina, Discus, Euomphalia, Galba, Helicigona, Helix, Helicella, Helico-discus, Lymnaea, Opeas, Vallonia and Zonitoides.
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 substsntially broadened and adapted to prevailing circum~tances by addition of other insecticides and~or acaricides. Examples of suitable additive~ include: organophosphorus - 9 ~
compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorina~ed hydrocarbona, and Bacillus thurlngiensis preparations.
The compounds of formula I are used in unmodlfied 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 (activ~ ingredient) of formula I or combinations thereof with other insecticides or acaricides, and, where appropriate, a solid or liquid ad~uvant, are prepared in known manner, e.g. by homogeneously mixlng and~or grinding the active ingredients with extenders, e.g. solvents, 301id carriers and, in some cases, surface-active compounds (surfactants).
Suitabls 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 pars~fins, alcohol~ and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones ~uch as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable olls such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. ~or dusts and dispersible powders are nor~ally natural mineral fillers such as calcite, talcum, kaolin, montmorillonlte or attapulgite. In order to improve the physical properties it is also pos6ible to add highly dispersed silicic acids or highly dispersed absorbent polyme~s. Su1table granula~ed adsorp-tive carriers are porous types, for e~ample pumice, broken brick, sepiolite or bentonite; and suitable nonsorben~ carriers are materlals such as calcite or aand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, or of combinations thereof with other insecticides or acaricides, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifylng, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures o$ 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 a5 well aB
modified and unmodified phospholipids.
More frequently, however, so-called synthetic surfactants are uaed, especially fatty sulfonates, fatty sulfates, sulfonated benzimida-zole derivatives or alkylarylsulfonates.
The fatty sulfonatas 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 lignosulPonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
::
These compoundæ also comprise the salts of sulfurlc acid esters and sulfonic acids of fatty alcohol/e~hylene oxide adducts. The sulfona-ted benzimidazole deriva~ives preferably contain 2 sulfonic acid groups and on~ fatty acid radical contalning 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-ethanolamine ~alts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic ~cid, or of a naphthalenesulfonic acid/formaldehyde condensation produet. ~lso suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol with ~ to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty aclds and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (allphatic) 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, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol containing 1 to 10 csrbon 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 nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethyl~ne glycol and octylphenoxypolyethoxyethanol. Patty acid esters of polyoxyethylene ~orbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary a~monium salts which contain, a~ N-substituent, at least one Cg-C22alkyl radical and, as $urther substituents, unæubstituted or halogenated lower alkyl, - 12 ~
benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halidesl methylsulfates or ethyl~ulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonlum bromide.
The surfactants customarily employed in ~he art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New JerDey, 1979; Dr. Helmut Stache, "Tensid Taschenbuch" (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna 1981.
The pesticidal compo~itions usually contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or combination thereof with other lnsecticldes or acariclde~, 1 to 99.9 % of a eolid or liquid ad~uvant, and 0 to 25 %, preferably 0.1 to 20 %, uf a surfactant.
Whereas commercial products are preferably formulated as concen-trates, the end user will normally employ diluted formulations of substantially lower concentration.
The compositions may also contain further ingredisnts, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
Exam~la 1:
a) Preparation o~ 3~5-dichloro-4-(1,1,2,313,3-hexafluoropropyl-o~y~aniline 47 g of 4-acetylamino-3,5-dichlorophenol tugether with 154 g of 90 %
potassium hydroxide solution and 130 ml of dimethylformamide are stirred in an au~oclave. 75.8 g of hexafluoropropylene are then pressed into the closed autoclave. The mixture is stirred for 20 hours at 70C under the pressure developing in the autoclave.
After cooling, the mixture i8 concentrated by rotary evaporation and - 13 ~
the resldue is dissolved in methylene chloride. The resultant solution is washed with water, dried over Na~S04 and concentrated.
The crude product obtainsd as residue i9 chromatographed through a column of silica gel (length: 1 m; dlameter: 10 cm) eluted with an 11:1 mixture of toluene and acetone, affording 4-acetylamino-3,5-di-chloro-1-(1,1,2,3,3,3-hexafluoropropyloxy~benzene in the form of pale yellow crystals (m.p.: 113-115C), 26 g of which a~e kept for 10 hours under reflux with 110 ml of ethanol and 35.6 ml 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 methylene chloride. The organic extract phase i3 washed with water, dried over NazSO4 and concentrated. The residue is purified by distillation, thus affording the title compound of the formula ~1 H2N~ OCFz-CHF-CF3 ~1 as a colourlesfi liquid with a boiling point of 91-96C/0.001 torr.
b~ Preparation of N~(2,6-difluorobenzoyl~-N'-~3~5-dichlor_-4-~1,1?2,3,3,3-hexafluoropropyloxy)phenyl~urea 4.3 g of 3,5-dichloro-4-~1,1,2,3,3,3-hexafluoropropyloxy)aniline are dissolved with stirring in 50 ml of dry toluene and, with exclusion of moisture, a solution of 2.41 g of 2,6-difluorobenzoylisocyanate in 10 ml of dry toluene is added at room temperature. ~he batch i3 stirred for a further 12 hours at room temperature. About 75 % of the solvent i9 then removed by rotary evaporation, the precipitated residue is filtered with suction, wa~hed with a ~mall amount of cold toluene and hexane and then dried in vacuo, affording the title compound of the formula Cl C0-NH-C0-NH~~ OCF2-CHF-CF3 F Cl in the form of a crystalline white powder with a melting polnt of 171-172C (compound l).
The following compounds of formula I have been prepared in a manner corresponding to that described above:
Compound m.p.
2 ~/ /Cl 2 ~ ~--C0-NH-C0-NH-~ -0-CFzCHFCF3 178-180C
Cl Cl /Cl . , ~s~
Cl Cl /Cl . , ~s~
3 ~ C0-NH-C0-NH~ -0-CFzCHFCF3 177-17~C
~Cl \Cl ,2,/F /Cl 4 ~ -C0-NH-C0-NH-~ -0-CF2CHFCF3 156-158C
Cl c) Prepara_ion of the sodium salt of compound 1 9.58 g of N-(2,6-difluorobenzoyl)-N'-[3,5-d1chloro-4-(1,1,2,3,3,3-hexafluoropropyloxy3phenyl3urea are ~uspended in 20 ml of ab~olute methanol. A oolution of 0.43 g of sodium in 30 ml of absolute methanol i8 added dropwise with stirring to this suspen610n. A clear solutioD forms which i8 then concentrated. The residual product is dried in vacuo at room temperature, a~fording the title compound of the formula ~ ~ -CO-~-CO-NH-~ O-CFzCllPCF3 as colourless crystals.
The following salt of compound 2 of the formula below can also be prepared by proceeding as described above:
Cl /Cl ~ CO-~-CO-NH--~ ~ -O-CF2CHFCF3 d) Preparation o~ the tetrabutyla~monium_salt of compound 1 2.56 8 of N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro 4-(1,1,2,3,3,3-hexafluoropropyloxy)phenyl~urea are suspended ln 30 ml of methanol.
With stirring, 5.2 g of a methanolic solution containing 1.3 g of tetra-n-butylammonium hydroxide are added to this suspension, whereupon 8 clear solution forms. This solution iB concentrated and the residual crude product is suspended in hexane. The suspension is $iltered with suctlon and the ~ilter residue is washed with hexane and then dried, affording the title compound of the formula [ ~ ~ -C0-~-C0-N~ -0-CF2CHFCF3 ¦ [~n~C4H9)4N ]
as coIourless crystals.
The following salts of formula la can also be prepared in accordance with this procedure:
CO-N-CO-NH-^~ ~-OCFzCHFCF3 ] [(CH3)4 N J
\F \Cl ~F ~Cl CO-N-CO-NH-~ -OCF2CHFCF3 ~(C2H5)4N ]
\Cl -CO-N-CO-NH~ OCF2CIIFCFI ] [ ~ _ s ]
~F ~Cl -CO-N-CO-NH-~ -OCF2CHFCF3 C(n-c3H7)4N ]0 \Cl \Cl \~ CO-N-CO-NH-~ -OCF2CHFCF3 ] ~ ]
~CI ~Cl .`'`. :
~ 8 ~ /
CO-N-CO-NH~ -OCFzCHFCF3 [(t~C4Hs)3NH
\Cl Example 2:
Formulation3 for active in~redients of formula I according to Example 1 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 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ethar (7-8 moles of ethylene oxide) - 2 %
highly disparsed silicic acid5 % 10 % 10 %
kaolin 62 % 27 %
The active ingredient or combination i~ thoroughly mixed with the ad~uvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with watsr to give suspension~ of the deslred concentratlon.
2. Emulslfiable_concentrata compound of formula I or combination 10 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 %
calcium dodecylbenzen2sulfonate 3 %
castor oil polygycol ether (36 moles of ethylene oxide) 4 %
cyclohaxanone 30 %
xylene mlxture 50 %
.
~Cl \Cl ,2,/F /Cl 4 ~ -C0-NH-C0-NH-~ -0-CF2CHFCF3 156-158C
Cl c) Prepara_ion of the sodium salt of compound 1 9.58 g of N-(2,6-difluorobenzoyl)-N'-[3,5-d1chloro-4-(1,1,2,3,3,3-hexafluoropropyloxy3phenyl3urea are ~uspended in 20 ml of ab~olute methanol. A oolution of 0.43 g of sodium in 30 ml of absolute methanol i8 added dropwise with stirring to this suspen610n. A clear solutioD forms which i8 then concentrated. The residual product is dried in vacuo at room temperature, a~fording the title compound of the formula ~ ~ -CO-~-CO-NH-~ O-CFzCllPCF3 as colourless crystals.
The following salt of compound 2 of the formula below can also be prepared by proceeding as described above:
Cl /Cl ~ CO-~-CO-NH--~ ~ -O-CF2CHFCF3 d) Preparation o~ the tetrabutyla~monium_salt of compound 1 2.56 8 of N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro 4-(1,1,2,3,3,3-hexafluoropropyloxy)phenyl~urea are suspended ln 30 ml of methanol.
With stirring, 5.2 g of a methanolic solution containing 1.3 g of tetra-n-butylammonium hydroxide are added to this suspension, whereupon 8 clear solution forms. This solution iB concentrated and the residual crude product is suspended in hexane. The suspension is $iltered with suctlon and the ~ilter residue is washed with hexane and then dried, affording the title compound of the formula [ ~ ~ -C0-~-C0-N~ -0-CF2CHFCF3 ¦ [~n~C4H9)4N ]
as coIourless crystals.
The following salts of formula la can also be prepared in accordance with this procedure:
CO-N-CO-NH-^~ ~-OCFzCHFCF3 ] [(CH3)4 N J
\F \Cl ~F ~Cl CO-N-CO-NH-~ -OCF2CHFCF3 ~(C2H5)4N ]
\Cl -CO-N-CO-NH~ OCF2CIIFCFI ] [ ~ _ s ]
~F ~Cl -CO-N-CO-NH-~ -OCF2CHFCF3 C(n-c3H7)4N ]0 \Cl \Cl \~ CO-N-CO-NH-~ -OCF2CHFCF3 ] ~ ]
~CI ~Cl .`'`. :
~ 8 ~ /
CO-N-CO-NH~ -OCFzCHFCF3 [(t~C4Hs)3NH
\Cl Example 2:
Formulation3 for active in~redients of formula I according to Example 1 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 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ethar (7-8 moles of ethylene oxide) - 2 %
highly disparsed silicic acid5 % 10 % 10 %
kaolin 62 % 27 %
The active ingredient or combination i~ thoroughly mixed with the ad~uvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with watsr to give suspension~ of the deslred concentratlon.
2. Emulslfiable_concentrata compound of formula I or combination 10 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 %
calcium dodecylbenzen2sulfonate 3 %
castor oil polygycol ether (36 moles of ethylene oxide) 4 %
cyclohaxanone 30 %
xylene mlxture 50 %
.
5~
~mulsions 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 ingredi0nt with the carrier, and grinding the mixture in a suitable mill.
4. Extruder_~ranulate compound of formula I or combination10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %
The active ingredient or combination is mixed and ground with the ad~uvants, and the mixture is sub3equéntly 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 (mol.wt.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.
~mulsions 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 ingredi0nt with the carrier, and grinding the mixture in a suitable mill.
4. Extruder_~ranulate compound of formula I or combination10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %
The active ingredient or combination is mixed and ground with the ad~uvants, and the mixture is sub3equéntly 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 (mol.wt.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 I 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 7S %
aqueous emulsion 0.8 %
water 32 %
Ths finely ground active ingredient or combination is lntimately mixed with the adjuvants, giving a suspension concentrate from which suspensions o~ any desired concentration can be obtainsd by dilution with water.
Exampl _3 Action again t Musca domestica 50 g of freshly prepared nutrient substrate fo~ 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 800 ppm. The substrate is then thoroughly mixed and the acetone sub3equently 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 wlth each active ingredient at the given concentration. After the maggots have pupated, the pupae are separa~ed from the substrate by flushing them out with water and then deposited in containers closed with a perforated top.
- 20 ~
Each batch of flushed out pupae i~ counted to determine the toxic effect of the test compound on the MaggO~ development. A count i8 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 Lucllia sericata -l ml of an aqueous solution containlng 0.5 % of test compound is added at 50C to 9 ml of a culture medium. Then about 30 freshly hatched Lucilia ~ericata larvae are added to the culture medium, and the lnsectlcldal action i9 determlned after 48 and 96 hours by evaluatlng the mortality rate.
In this test, compounds of formula I according to Example 1 exhiblt good activity again~t Lucilia sericata.
Example 5 Action a~ es aegypti A concentration of 800 ppm is obtained by pipetting a specific amount of a 0.1 % solution of the test compound in acetone onto the surface of 150 ml of water in a beaker. After the acetone has evaporQted, 30 to 40 two-day-old larvae of Aëdes aegyp-ti Qre put into the beaker cGntaining 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 A8des aegypti.
Example 6: Insecticidal action against feeding insects a) Cotton plants about 25 cm high, in pots, are spr~yed with aqueous emulsions which contain the respective test compound in concentra-tions of 3, 12.5 and 50 pp~. After the spray coating has dried, the cotton plants are populated with Spodoptera littoralis and Heliothis 5~
virescens larvae in the L3-stage. The test is carried out at 24C
and 60 % relative humidity. The percentage mortallty of the test insects is determined after 2 day~.
Compounds l, 2, 3 and 4 according to Example 1 effect 80-100 %
mortality against Spodoptera larvae at 3 ppm. 80-100 % mortality is effected agalnst Heliothis larvae by compound 1 at 12.5 ppm and by compounds 2 and 3 at 50 ppm.
b) Comparative test The above test a) is repeated using compound 1 of this invention and two prior art compounds. In distinction to test a), the percentage mortality of the larvae is not determined until after 7 days. The active ingredient concentrations, the compounds employed and the results obtained are indicated in the following Table:
~1 r. O
~ ~ ~ ---~ - --o ~ ~ ~
o a~ ~ O
: -~ ~ ~ o o o ~ o ~
~ -- - -------- ~ ---~-~ ~. ~o ~o . _ .. _ - .. .. _. _ ___ . .. ,. _ _ N _I q N
5~ P~ 0_ 0~ 0 ~ ~.~ V-./ ~.~ ~ ~a .~;\ ~ #, ¢~
~, ~ ~ 0~ f ~ ~
~ Z o o ~ ~ ~ ~ ~ o~
~o b ~ ~ o P~ oo o ~ o q o o ~ C~ ~o ~
~ ~ '.... .
Example 7~ Action against Epilachna varivesti~
Phaseolus vulgaris plants (dwarf beans) about 15-20 cm i~ height are sprayed with aqueous emulsion formulatlons 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 varivsstis (Mexican bean beetle) in the L~-stage. A plastic cylinder is slipped over the treated plants and covered with a copper gauze top. The test is carried out at 28C and 60 % relative humidity. The percentage mortality is determined after 2 snd 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 E~ample l exhibit good activity in this test.
Exsmple 8: Ovicidal action against Heliothis virescens Corresponding amounts of a wettable powder formulation containing 25 % by weight of the test compound are mlxed with sufficient water to produce an aqueous emulsion with an active ingredient concentration of 800 ppm. One-day-old egg deposits of Heliothis on cellophane are immersed in these emulsions for 3 minutes and then collected by suction on round filters. The treated deposits are placed in petri dishes and kept in the dark. The hatching rate in comparison with untreated controls is determined after 6 to 8 days.
The compounds of formula I according to Example l exhibit good activity 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 solutlon containing 800 ppm of the test compound.
After the solution has dried, the eggs are placed in petri diahes and kept at a temperature of 28C. The percentage of larvae hatched from the treated eggs and the percentage mortality is evaluated after 6 days.
The compound3 of formula I according to Example 1 exhibit good activity in this te3t.
Example 10: Influence on the reproduction of Anthonomous grandi3 Anthonomou~ grandi3 adults which are not more than 24 hour3 old after hatching are transferred in groups of 25 to barred cages. The cages are then immersed for 5 to 10 second3 in an acetonic solution containing 400 pm of the test compound. After the beetle3 have dried, they sre 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 percentage mortality of the eggs, i.e.
the number of larvae which have developed from the eggs.
The duration of the reproduction irlhibiting effect of the test compounds i~ 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 un~reated controls.
Compounds of formula I according to Example 1 exhibit good activity in this test.
Example 11: Action against Anthonomu~ ~randis (adults) Two cotton plants in the 6-leaf stage, in pot3, are each ~prayed with a wettable aqueous emulsion formulatlon containing 400 ppm of the test compound. After the ~pray coating has dried (about l.S hours), each plant is populated with 10 adult beetles (Anthonomus grandis). Plastic cylinders, covered at the top with gauze, are then sllpped over the treated plants populated wlth the test insects to prevent the beetles from Migrating from the plants.
The treated plants are then kept at 25C and about 60 % relative humidity. Evaluation is made after 2, 3, 4 and 5 days to determine the percentage mortality of the beetles (percentage in dorsal position) as well as the anti-feeding action as compared with untreated controls.
Compounds of formula I according to Example 1 exhibit good activity in this test.
xample 12~. Insecticidal stomach ~osion action against Plutella xylostella Potted Chinese cabbage plants (pot size: 10 cm diameter~ in the 4-leaf stage are sprayed with aqueous emulsions which contain the test compound in a concentration of 0.8 ppm and which dry on the plants.
After 2 days, each of the treated Chinese cabbage plants i8 pOpU-lated with 10 Plutella xylostella larvae in the L2-stage. The test is carried out at 24C and at 60 % relative humidity in dim llght.
Evaluation of the percentage mortality of the larvae is made after 2 and 5 days.
Compound 1 according to Example 1 effect~ 100 % mortality in this test.
Example 13: Feed inhibiting action against ~lu~8 5 red slugs (Arion rufus) are left for 17 hours under controlled ~est conditions in each of a number of cages containing 4 fresh lettuce leaves. In these tests, each cage either only contains untreated leaves or only contalns leaves which have been trea~ed by spray application. The concentration of the test compound in the aqueous formulation applied i8 0.5 % by weight. The extent of the feeding damage i8 determined on tha basis of weight differences, - 26 ~ 5~
photocopies of pictures of the feeding damage and on the basis of any evident assessable criteria in comparison with untreated controls.
The mortality of the te~t animals is also determlned.
Compounds of formula I according to claim 1 exhibit good activity in this tèst.
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 7S %
aqueous emulsion 0.8 %
water 32 %
Ths finely ground active ingredient or combination is lntimately mixed with the adjuvants, giving a suspension concentrate from which suspensions o~ any desired concentration can be obtainsd by dilution with water.
Exampl _3 Action again t Musca domestica 50 g of freshly prepared nutrient substrate fo~ 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 800 ppm. The substrate is then thoroughly mixed and the acetone sub3equently 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 wlth each active ingredient at the given concentration. After the maggots have pupated, the pupae are separa~ed from the substrate by flushing them out with water and then deposited in containers closed with a perforated top.
- 20 ~
Each batch of flushed out pupae i~ counted to determine the toxic effect of the test compound on the MaggO~ development. A count i8 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 Lucllia sericata -l ml of an aqueous solution containlng 0.5 % of test compound is added at 50C to 9 ml of a culture medium. Then about 30 freshly hatched Lucilia ~ericata larvae are added to the culture medium, and the lnsectlcldal action i9 determlned after 48 and 96 hours by evaluatlng the mortality rate.
In this test, compounds of formula I according to Example 1 exhiblt good activity again~t Lucilia sericata.
Example 5 Action a~ es aegypti A concentration of 800 ppm is obtained by pipetting a specific amount of a 0.1 % solution of the test compound in acetone onto the surface of 150 ml of water in a beaker. After the acetone has evaporQted, 30 to 40 two-day-old larvae of Aëdes aegyp-ti Qre put into the beaker cGntaining 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 A8des aegypti.
Example 6: Insecticidal action against feeding insects a) Cotton plants about 25 cm high, in pots, are spr~yed with aqueous emulsions which contain the respective test compound in concentra-tions of 3, 12.5 and 50 pp~. After the spray coating has dried, the cotton plants are populated with Spodoptera littoralis and Heliothis 5~
virescens larvae in the L3-stage. The test is carried out at 24C
and 60 % relative humidity. The percentage mortallty of the test insects is determined after 2 day~.
Compounds l, 2, 3 and 4 according to Example 1 effect 80-100 %
mortality against Spodoptera larvae at 3 ppm. 80-100 % mortality is effected agalnst Heliothis larvae by compound 1 at 12.5 ppm and by compounds 2 and 3 at 50 ppm.
b) Comparative test The above test a) is repeated using compound 1 of this invention and two prior art compounds. In distinction to test a), the percentage mortality of the larvae is not determined until after 7 days. The active ingredient concentrations, the compounds employed and the results obtained are indicated in the following Table:
~1 r. O
~ ~ ~ ---~ - --o ~ ~ ~
o a~ ~ O
: -~ ~ ~ o o o ~ o ~
~ -- - -------- ~ ---~-~ ~. ~o ~o . _ .. _ - .. .. _. _ ___ . .. ,. _ _ N _I q N
5~ P~ 0_ 0~ 0 ~ ~.~ V-./ ~.~ ~ ~a .~;\ ~ #, ¢~
~, ~ ~ 0~ f ~ ~
~ Z o o ~ ~ ~ ~ ~ o~
~o b ~ ~ o P~ oo o ~ o q o o ~ C~ ~o ~
~ ~ '.... .
Example 7~ Action against Epilachna varivesti~
Phaseolus vulgaris plants (dwarf beans) about 15-20 cm i~ height are sprayed with aqueous emulsion formulatlons 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 varivsstis (Mexican bean beetle) in the L~-stage. A plastic cylinder is slipped over the treated plants and covered with a copper gauze top. The test is carried out at 28C and 60 % relative humidity. The percentage mortality is determined after 2 snd 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 E~ample l exhibit good activity in this test.
Exsmple 8: Ovicidal action against Heliothis virescens Corresponding amounts of a wettable powder formulation containing 25 % by weight of the test compound are mlxed with sufficient water to produce an aqueous emulsion with an active ingredient concentration of 800 ppm. One-day-old egg deposits of Heliothis on cellophane are immersed in these emulsions for 3 minutes and then collected by suction on round filters. The treated deposits are placed in petri dishes and kept in the dark. The hatching rate in comparison with untreated controls is determined after 6 to 8 days.
The compounds of formula I according to Example l exhibit good activity 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 solutlon containing 800 ppm of the test compound.
After the solution has dried, the eggs are placed in petri diahes and kept at a temperature of 28C. The percentage of larvae hatched from the treated eggs and the percentage mortality is evaluated after 6 days.
The compound3 of formula I according to Example 1 exhibit good activity in this te3t.
Example 10: Influence on the reproduction of Anthonomous grandi3 Anthonomou~ grandi3 adults which are not more than 24 hour3 old after hatching are transferred in groups of 25 to barred cages. The cages are then immersed for 5 to 10 second3 in an acetonic solution containing 400 pm of the test compound. After the beetle3 have dried, they sre 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 percentage mortality of the eggs, i.e.
the number of larvae which have developed from the eggs.
The duration of the reproduction irlhibiting effect of the test compounds i~ 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 un~reated controls.
Compounds of formula I according to Example 1 exhibit good activity in this test.
Example 11: Action against Anthonomu~ ~randis (adults) Two cotton plants in the 6-leaf stage, in pot3, are each ~prayed with a wettable aqueous emulsion formulatlon containing 400 ppm of the test compound. After the ~pray coating has dried (about l.S hours), each plant is populated with 10 adult beetles (Anthonomus grandis). Plastic cylinders, covered at the top with gauze, are then sllpped over the treated plants populated wlth the test insects to prevent the beetles from Migrating from the plants.
The treated plants are then kept at 25C and about 60 % relative humidity. Evaluation is made after 2, 3, 4 and 5 days to determine the percentage mortality of the beetles (percentage in dorsal position) as well as the anti-feeding action as compared with untreated controls.
Compounds of formula I according to Example 1 exhibit good activity in this test.
xample 12~. Insecticidal stomach ~osion action against Plutella xylostella Potted Chinese cabbage plants (pot size: 10 cm diameter~ in the 4-leaf stage are sprayed with aqueous emulsions which contain the test compound in a concentration of 0.8 ppm and which dry on the plants.
After 2 days, each of the treated Chinese cabbage plants i8 pOpU-lated with 10 Plutella xylostella larvae in the L2-stage. The test is carried out at 24C and at 60 % relative humidity in dim llght.
Evaluation of the percentage mortality of the larvae is made after 2 and 5 days.
Compound 1 according to Example 1 effect~ 100 % mortality in this test.
Example 13: Feed inhibiting action against ~lu~8 5 red slugs (Arion rufus) are left for 17 hours under controlled ~est conditions in each of a number of cages containing 4 fresh lettuce leaves. In these tests, each cage either only contains untreated leaves or only contalns leaves which have been trea~ed by spray application. The concentration of the test compound in the aqueous formulation applied i8 0.5 % by weight. The extent of the feeding damage i8 determined on tha basis of weight differences, - 26 ~ 5~
photocopies of pictures of the feeding damage and on the basis of any evident assessable criteria in comparison with untreated controls.
The mortality of the te~t animals is also determlned.
Compounds of formula I according to claim 1 exhibit good activity in this tèst.
Claims (16)
1. A compound of formula I
(I) wherein R1 is hydrogen or fluorine and R2 is fluorine or chlorine, or a salt thereof.
(I) wherein R1 is hydrogen or fluorine and R2 is fluorine or chlorine, or a salt thereof.
2. A compound of formula I according to claim 1, wherein R1 is fluorine and R2 is fluorine or chlorine.
3. A compound of formula I according to claim 1, wherein R1 is hydrogen and R2 is fluorine or chlorine.
4. The compound according to claim 2 of the formula
5. The compound according to claim 3 of the formula
6. The compound according to claim 3 of the formula
7. The compound according to claim 2 of the formula
8. A metal salt of a compound of formula I according to claim 1.
9. A salt of a compound of formula I according to claim 1 with an organic base.
10. A salt according to claim 9, wherein a quatenary nitrogen atom is present.
11. A process for the preparation of a compound according to claim 1, which process comprises reacting a) the compound of formula II
(II) with a compound of formula III
(III) or b) the compound of formula IV
(IV) with a compound of formula V
(V), or c) the compound of formula II with a compound of formula VI
(VI) in which formulae III, V and VI, the radicals R1 and R2 are as defined in claim 1 and R is a C1-C8alkyl radical which is unsubsti-tuted or substituted by halogen, and, if desired, converting the resultant compound of formula I into a salt thereof.
(II) with a compound of formula III
(III) or b) the compound of formula IV
(IV) with a compound of formula V
(V), or c) the compound of formula II with a compound of formula VI
(VI) in which formulae III, V and VI, the radicals R1 and R2 are as defined in claim 1 and R is a C1-C8alkyl radical which is unsubsti-tuted or substituted by halogen, and, if desired, converting the resultant compound of formula I into a salt thereof.
12. The compound of formula II
(II) .
(II) .
13. The compound of formula IV
(IV) .
(IV) .
14. A method of controlling insects, representatives of the order Acarina and slugs and snails, which method comprises treating said pests, the various development stages or the locus thereof with a pesticidally effective amount of a compound of formula I according to claim 1, or of a salt thereof, or with a composition which contains a pesticidally effective amount of such a compound, together with adjuvants and carriers.
15. A method according to claim 14 for controlling larval stages of plant-destructive insects.
16. A method according to claim 15 for controlling insect eggs.
FO 7.5 EIC/bg*/we*/ch*
FO 7.5 EIC/bg*/we*/ch*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH442085 | 1985-10-14 | ||
| CH4420/85-5 | 1985-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1291151C true CA1291151C (en) | 1991-10-22 |
Family
ID=4275804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000520273A Expired - Lifetime CA1291151C (en) | 1985-10-14 | 1986-10-10 | N-benzoyl-n'-3,5-dichloro-4-hexafluoropropyloxy-phenylureas |
Country Status (22)
| Country | Link |
|---|---|
| EP (1) | EP0219460B1 (en) |
| JP (1) | JPS6293268A (en) |
| KR (1) | KR900008136B1 (en) |
| CN (1) | CN1014110B (en) |
| AT (1) | ATE63112T1 (en) |
| AU (1) | AU597278B2 (en) |
| BR (1) | BR8604995A (en) |
| CA (1) | CA1291151C (en) |
| CY (1) | CY1683A (en) |
| DE (1) | DE3679024D1 (en) |
| DK (2) | DK488186A (en) |
| EG (1) | EG17946A (en) |
| ES (1) | ES2038125T3 (en) |
| GB (3) | GB2182329B (en) |
| HK (1) | HK33893A (en) |
| IL (1) | IL80271A (en) |
| MX (1) | MX173307B (en) |
| SG (1) | SG117592G (en) |
| SU (1) | SU1588277A3 (en) |
| TR (1) | TR23026A (en) |
| ZA (1) | ZA867736B (en) |
| ZW (1) | ZW20486A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0221847A3 (en) * | 1985-10-29 | 1988-03-23 | Ciba-Geigy Ag | Benzoyl urea salts |
| 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 |
| IT1213420B (en) * | 1986-12-19 | 1989-12-20 | Donegani Guido Ist | "N (-2,6-DIFLUOROBENZOIL) -N'-3-CHLORINE -41,1,2-TRIFLUORO-2- (TRIFLUOROMETOSSI) ETHOXYOUS PHENYL UREA WITH INSECTICIDE ACTIVITY. |
| IT1230675B (en) * | 1987-09-04 | 1991-10-29 | Donegani Guido Ist | N- (ALOBENZOIL) -N'-2-ALO-4 (1,1,2-TRIFLUORO-2- (TRIFLUOROMETOSSI) ETHOXY) PHENYL UREE INSECTICIDE ACTIVITY |
| DE3740633A1 (en) * | 1987-12-01 | 1989-06-15 | Bayer Ag | SUBSTITUTED BENZOYL (THIO) UREA |
| GB8905741D0 (en) * | 1989-03-13 | 1989-04-26 | Shell Int Research | Process for preparing carbamates,and intermediates therin |
| AU3148599A (en) * | 1999-04-15 | 2000-11-02 | Consejo Superior De Investigaciones Cientificas | Method for controlling a mediterranean fruit fly pest |
| US6681886B2 (en) * | 2001-12-11 | 2004-01-27 | Visteon Global Technologies, Inc | Flexibly coupled electric power assist steering system |
Family Cites Families (6)
| 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 |
| US4418991A (en) * | 1979-09-24 | 1983-12-06 | Breger Joseph L | Presbyopic contact lens |
| AU553953B2 (en) * | 1981-07-30 | 1986-07-31 | Dow Chemical Company, The | Urea and thiourea insecticides; intermediates in their preparation |
| DE3217620A1 (en) * | 1982-05-11 | 1983-11-17 | Bayer Ag, 5090 Leverkusen | 2,5-DIHALOGENBENZOYL (THIO) UREA, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PEST CONTROL |
| 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 |
-
1986
- 1986-10-08 DE DE8686810446T patent/DE3679024D1/en not_active Expired - Lifetime
- 1986-10-08 AT AT86810446T patent/ATE63112T1/en not_active IP Right Cessation
- 1986-10-08 ES ES198686810446T patent/ES2038125T3/en not_active Expired - Lifetime
- 1986-10-08 EP EP86810446A patent/EP0219460B1/en not_active Expired - Lifetime
- 1986-10-09 IL IL80271A patent/IL80271A/en not_active IP Right Cessation
- 1986-10-10 CA CA000520273A patent/CA1291151C/en not_active Expired - Lifetime
- 1986-10-10 GB GB8624335A patent/GB2182329B/en not_active Expired - Lifetime
- 1986-10-13 BR BR8604995A patent/BR8604995A/en not_active IP Right Cessation
- 1986-10-13 ZW ZW204/86A patent/ZW20486A1/en unknown
- 1986-10-13 ZA ZA867736A patent/ZA867736B/en unknown
- 1986-10-13 DK DK488186A patent/DK488186A/en not_active Application Discontinuation
- 1986-10-13 SU SU864028385A patent/SU1588277A3/en active
- 1986-10-13 TR TR561/86A patent/TR23026A/en unknown
- 1986-10-13 AU AU63833/86A patent/AU597278B2/en not_active Ceased
- 1986-10-13 MX MX004015A patent/MX173307B/en unknown
- 1986-10-14 KR KR1019860008661A patent/KR900008136B1/en not_active IP Right Cessation
- 1986-10-14 JP JP61244022A patent/JPS6293268A/en active Granted
- 1986-10-14 EG EG646/86A patent/EG17946A/en active
- 1986-10-14 CN CN86106647A patent/CN1014110B/en not_active Expired
-
1989
- 1989-05-02 GB GB8910036A patent/GB2217324B/en not_active Expired - Lifetime
- 1989-05-02 GB GB8910035A patent/GB2217323B/en not_active Expired - Lifetime
-
1992
- 1992-09-10 DK DK921116A patent/DK111692D0/en not_active Application Discontinuation
- 1992-11-06 SG SG1175/92A patent/SG117592G/en unknown
-
1993
- 1993-04-08 HK HK338/93A patent/HK33893A/en not_active IP Right Cessation
- 1993-10-10 CY CY1683A patent/CY1683A/en unknown
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