Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
  • C07D295/26—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C307/04—Diamides of sulfuric acids
  • C07C307/06—Diamides of sulfuric acids having nitrogen atoms of the sulfamide groups bound to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
  • C07C311/51—Y being a hydrogen or a carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

• the invention relates to compounds of formula
• n 1 or 3;
• R is -N(R 1 )R 2 or -(O) m R 3 ; m is O or l;
• R j and R 2 are each independently of the other H or an organic radical or, together with the nitrogen atom carrying them, form a heterocyclic radical containing at least one nitrogen atom;
• R 3 is an organic radical;
• R 4 is H or C ⁇ -C 6 alkyl; and
• X is fluorine or chlorine; in free form or in salt form, to a process for the preparation of those compounds and to the use of those compounds, to pesticidal compositions comprising an active ingredient selected from those compounds, in free form or in agrochemically acceptable salt form, to a process for the preparation of those compositions and to the use of those compositions, to plant propagation material treated with those compositions, to a method of controlling pests, to intermediates for the preparation of those compounds and to a process for the preparation of those intermediates and to the use of those intermediates.
• the compounds I are capable of forming salts with bases.
• Suitable salts with bases are, for example, metal salts, such as alkali or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor- pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkyl ⁇ amine, for example mono-, di- or tri-ethanolamine.
• metal salts such as alkali or alkaline earth metal salts, for example sodium, potassium or magnesium salts
• salts with ammonia or an organic amine such as mor- pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethy
• Agrochemically advantageous salts are preferred within the scope of the invention, but salts that have drawbacks as regards agrochemical uses, for example salts that are toxic to bees or fish, are also included, such salts being used, for example, for the isolation and/or purification of free compounds I or the agrochemically acceptable salts thereof.
• any reference to the free compounds I or the salts thereof should be understood as including the corresponding salts or the free compounds I, respectively, where appropriate and expedient. The same applies in the case of tautomers of compounds I and the salts thereof. In each case the free form is generally preferred.
• An organic radical is preferably unsubstituted or substituted, e.g. mono- to tri-substituted, C r C 20 alkyl, the substituents being selected from the group consisting of halogen, C 3 -C 8 cycloalkyl, cyano, C r C 6 alkoxy, C j -Cealkylthio, C r C 6 alkoxycarbonyl, C r C 4 alkylcarbonyl, C r C 4 alkoxy-C r C 6 alkoxy, C j -Cgalkylcarbonyloxy, C r C 6 alkoxycarbonyloxy, aryl and, e.g.
• Aryl - as a group per se and as a structural unit of other groups and compounds, such as aryloxy - is an unsubstituted or mono- to penta-substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C 1 -C 6 alkyl, C j -C 6 alkoxy, phenoxy, cyano, nitro, C r C 4 haloalkyl, C r C 6 haloalkoxy, aminosulfonyl, C r C 6 alkoxycarbonyl and C r C 6 alkylthio.
• An heterocyclic radical -N(R 1 )R 2 containing at least one nitrogen atom in the ring system, is preferably an unsubstituted or mono- to tri-substituted, more preferably one- or disubstituted, saturated or unsaturated three- to seven-membered ring, containing if desired - besides the nitrogen atom contained in the formula -N(R,)R 2 - one to three further ring heteroatoms, selected from the group consisting of N, O and S, and provided if desired with a fused-on benzene ring, the substituents of the heterocyclic residue being selected from the group consisting of halogen, C 1 -C 4 alkyl, C r C 4 alkoxycarbonyl, pyridyl, benzyl and unsubstituted or mono- to penta-substituted phenyl, the substituents of the phenyl residue being selected from the group consisting of halogen,
• the radicals R j and R 2 may together form a straight- chained C 3 -C 6 alkylene group or an oxa-C 2 -C 5 alkylene group bonded via carbon atoms.
• Preference for the heterocyclic groups -N(R j )R 2 is given within the scope of the invention to piperidyl, morpholinyl, thiomorpholinyl, pyrrolidinyl, pyrrolyl, 4-methylpiperazinyl, 2,6-dimethylpiperidyl, 4-phenylpiperazinyl, 4-(4-fluorophenyl)-piperazinyl, 4-(2-methylphenyl)-piperazinyl, 4-(2-methoxyphenyl)-piperazinyl, 4-(4-methoxyphenyl)- piperazinyl, 4-(4-nitrophenyl)-piperazinyl, 4-(3,4-dichlorophenyl)-piperazinyl, 4-pyrid
• Halogen - as a group per se and as a structural unit of other groups and compounds, such as haloalkyl, haloalkenyl, haloalkynyl and haloalkoxy - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
• carbon-containing groups and compounds each contain from 1 up to and including 20, preferably from 1 up to and including 18, especially from 1 up to and including 10, more especially from 1 up to and including 6, especially from 1 up to and including 4, more especially from 1 up to and including 3, and above all 1 or 2, carbon atoms.
• Alkyl - as a group per se and as a structural unit of other groups and compounds, such as alkylthio, alkylcarbonyl, alkoxyalkoxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkylsulfonyl, alkylsulfinyl, haloalkyl, alkoxy, haloalkoxy and alkoxycarbonyl - is, in each case taking due account of the number of carbon atoms present in the group or compound in question, either straight-chained, for example methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octadecyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl
• Alkenyl, haloalkenyl, alkynyl and haloalkynyl are straight-chained or branched and contain in each case two or, preferably, one unsaturated carbon-carbon bond(s).
• the double or triple bonds of these substituents are preferably separated from the remaining part of the compound I by at least one saturated carbon atom. Examples which may be mentioned are allyl, methallyl, but-2-enyl, but-3-enyl, propargyl, but-2-ynyl and but-3-ynyl.
• Halo-substituted carbon-containing groups and compounds such as haloalkyl, haloalkenyl, haloalkynyl and haloalkoxy, may be partially halogenated or perhalogenated, it being possible in the case of multiple halogenation for the halogen substituents to be identical or different.
• haloalkyl - as a group per se and as a structural unit of other groups and compounds, such as haloalkoxy - are methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF 2 , CF 3 or CH 2 C1; ethyl mono- to penta- substituted by fluorine, chlorine and/or by bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CC1 3 , CF 2 CHC1 2 , CF 2 CHF 2 , CF 2 CFC1 2 , CH 2 CH 2 C1, CF 2 CHBr 2 , CF 2 CHC1F, CF 2 CHBrF or CC1FCHC1F; propyl or isopropyl mono- to hepta-substituted by fluorine, chlorine and/or by bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2
• haloalkenyl examples include 2,2-difluoroethen-l-yl, 2,2-dichloro- ethen-1-yl, 2-chloroprop-l-en-3-yl, 2,3-dichloroprop-l-en-3-yl and 2,3-dibromoprop-l-en-3-yl.
• haloalkynyl examples include 2-chloroprop-l-yn-3-yl, 2,3-dichloroprop-l-yn-3-yl and 2,3-dibromo-l-yn-3-yl.
• Straight-chained C 3 -C 6 alkylene is trimethylene, tetramethylene, pentamethylene or hexa- methylene.
• Straight-chained oxa-C 2 -C 5 alkylene bonded via carbon atoms is -CH 2 -O-CH 2 -, -CH 2 -O-CH 2 -CH 2 -, -CH 2 -O-CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -O-CH 2 -CH 2 -, -CH 2 -O-CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -, preferably -CH 2 -CH 2 -O-CH 2 -CH 2 -.
• Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably cyclopropyl or cyclohexyl.
• Pyridyl is pyrid-3-yl, pyrid-4-yl or, preferably, pyrid-2-yl.
• R j and R 2 are are each independently of the other H or an organic radical or, together with the nitrogen atom carrying them, form a heterocyclic radical containing at least one nitrogen atom; and R 3 is an organic radical;
• R j and R 2 are each independently of the other H or an organic radical or, together with the nitrogen atom carrying them, form a heterocyclic radical containing at least one nitrogen atom; especially R, and R 2 each independently of the other H; unsubstituted or mono- to tri-substituted C j -C 2 oalkyl, the substituents being selected from the group consisting of halogen, C 3 -C 5 cycloalkyl, cyano, C r C 6 alkoxy and phenyl; unsubstituted C 3 -C 8 cycloalkyl; unsubstituted C 3 -C 20 alkenyl; or unsubstituted or mono- to tri-substituted phenyl, the substituents being selected from the group consisting of halogen, C j - haloalkyl, C r C 6 alkoxy, cyano and nitro; or together with the nitrogen atom carrying them form an unsubstituted
• R 3 is an organic radical; especially C 1 -C 20 alkyl; halo-C r C 6 alkyl; unsubstituted or mono- to penta-substituted phenyl or naphthyl, the substituents being selected from the group consisting of halogen, C r C 6 alkyl, C ⁇ -C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, Ci-Cgalkoxycarbonyl, C r C 6 alkylthio, cyano, nitro, aminosulfonyl, C r C 6 alkylsulfonyl, C ⁇ -C 6 alkylsulfinyl, phenyl and phenoxy; or benzyl;
• R is C r C 2 oalkyl; halo-C ⁇ -C 20 alkyl; -NCR ⁇ R ⁇ an unsubstituted or mono- to penta- substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C r C 6 alkyl, halo-C r C 4 alkyl, C r C 6 alkoxy, halo-C r C 4 - alkoxy, cyano, nitro and C r C 6 alkoxycarbonyl; or an unsubstituted or mono- to tri- substituted benzyl or biphenylyl group, the substituents being selected from the group consisting of halogen and nitro, and a substituted benzyl group being substituted at its phenyl partial structure; and
• R, and R 2 are each independently of the other C r C 4 alkyl or together form a straight- chained C 3 -C 6 alkylene group or a straight-chained oxa-C 2 -C 5 alkylene group bonded via carbon atoms; wherein, especially, R is C ⁇ -C 18 alkyl; ha-0-C..- alkyl; -N(R 1 )R 2 ; an unsubstituted or mono- to penta- substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C 1 -C 6 alkyl, halo-C r C 4 alkyl, C r C 6 alkoxy, halo-C r C 4 - alkoxy, cyano, nitro and C r C 6 alkoxycarbonyl; or an unsubstituted benzyl or biphenylyl group; and
• R j and R 2 are each independently of the other C r C 4 alkyl or together form a straight- chained oxa-C 2 -C 5 alkylene group bonded via carbon atoms; wherein, more especially,
• R is C ⁇ -C 6 alkyl; halo-C r C 4 alkyl; -N(R,)R 2 ; unsubstituted naphthyl; unsubstituted or mono- to tri-substituted phenyl, the substituents being selected from the group consisting of halogen, C r C 6 alkyl, halo-C r C 2 alkyl, C r C 6 alkoxy, halo-C r C 4 - alkoxy, cyano, nitro and C r C 4 alkoxycarbonyl; or an unsubstituted benzyl or biphenylyl group; and
• Rj and R 2 are each independently of the other C r C 2 alkyl or together form a straight- chained oxa-C 3 -C 5 alkylene group bonded via carbon atoms; wherein, especially,
• R is C r C 6 alkyl; -N(R,)R 2 or unsubstituted or mono- to tri-substituted phenyl, the substituents being selected from the group consisting of halogen, C j -C 6 alkyl, halo- C r C 2 alkyl, C r C 6 alkoxy, halo-C r C 4 alkoxy, cyano, nitro and C r C 4 alkoxycarbonyl; and
• Rj and R 2 together form a straight-chained oxa-C 3 -C 5 alkylene group bonded via carbon atoms; wherein, more especially,
• R is C r C 4 alkyl; -N(Rj)R 2 or unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, C j -C alkyl, halo- C 1 -C 2 alkyl, C r C 4 alkoxy, halo-C r C 2 alkoxy, cyano, nitro and C r C 2 alkoxycarbonyl; and
• R j and R 2 together form a straight-chained oxa-C 4 -C 5 alkylene group bonded via carbon atoms; wherein, very especially,
• R is C j -C 4 alkyl; morpholinyl; or phenyl that is unsubstituted or mono-substituted by halogen, halo-C j -C 2 alkyl or by nitro; wherein, above all,
• R is C j -C alkyl; morpholin-4-yl; or phenyl that is unsubstituted or mono-substituted by chlorine, trifiuoromethyl or by nitro; (8) a compound of formula I wherein
• X is fluorine or chlorine, especially fluorine
• R is C j -C 18 alkyl; benzyl; an unsubstituted or mono- to tri-substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C j -C 6 alkyl, halo-C j - alkyl, and nitro; an unsubstituted or mono- or di-substituted morpholinyl or thiomorpholinyl group; or -N(R j ) R 2 ;
• R j and R 2 are each independently of the other H; unsubstituted or mono- or di-substituted C j -C 6 alkyl, the substituents being selected from the group consisting of C 3 -C 5 cycloalkyl and C j -C 6 alkoxy; C 3 -C 8 -cycloalkyl; benzyl; or C 3 -C 6 alkenyl; or R j and R 2 together form a straight-chained C 3 -C 6 alkylene group;
• X is fluorine
• R 4 is H
• R is C j -C 18 alkyl; halo-C j -C 4 alkyl; -N(R j )R 2 ; an unsubstituted or mono- to penta- substituted phenyl or naphthyl group, the substituents being selected from the group consisting of halogen, C -C 6 alkyl, halo-C j -C 4 alkyl, C r C 6 alkoxy, halo-C j -C 4 - alkoxy, cyano, nitro and C -C 6 alkoxycarbonyl; or benzyl or biphenylyl;
• R j and R 2 are each independently of the other C j -C 4 alkyl or together form a straight- chained oxa-C 2 -C 5 alkylene group bonded via carbon atoms;
• X is fluorine
• R 4 is H
• R is C j - alkyl; -N(R j )R 2 or unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, C j -C 4 alkyl, halo- C j -C 2 alkyl, C j -C 4 alkoxy, halo-C r C 2 alkoxy, cyano, nitro and C j -C 2 alkoxycarbonyl;
• R j and R 2 together form a straight-chained oxa-C 4 -C 5 alkylene group bonded via carbon atoms; (12) a compound of formula I wherein n is 1;
• R is C -C 4 alkyl; morpholinyl; or phenyl that is unsubstituted or mono-substituted by halogen, halo-C -C 2 alkyl or by nitro; X is fluorine; and R 4 is H;
• R is C j -C 4 alkyl; morpholin-4-yl; or phenyl that is unsubstituted or mono-substituted by chlorine, trifluoromethyl or by nitro; X is fluorine; and R 4 is H.
• the invention relates also to a process for the preparation of the compounds of formula I, in free form or in salt form, which comprises, for example,
• n and X are as defined for formula I and Y is a leaving group, where appropriate in the presence of a base, an acid catalyst or a water-binding agent, with a compound of formula
• O K 4 which is known or can be prepared analogously to corresponding known compounds and wherein R and R 4 are as defined for formula I and Z is hydrogen or an alkali metal atom, or
• R, R 4 and n are as defined for formula I, or a salt thereof, in an inert solvent, with difluorocarbene or chlorofluorocarbene and/or, if desired, converting a compound of formula I obtainable in accordance with the process or by a different method, in free form or in salt form, into a different compound of formula I, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula I obtainable in accordance with the process or by a different method into a salt or converting a salt of a compound of formula I obtainable in accordance with the process or by a different method into the free compound of formula I or into a different salt.
• reaction described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, where appropriate, in the presence of a suitable solvent or diluent or of a mixture thereof, the reaction being carried out as required with cooling, at room temperature or with heating, for example in a temperature range from approximately -80°C to the boiling temperature of the reaction mixture, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
• a suitable solvent or diluent or of a mixture thereof for example in a temperature range from approximately -80°C to the boiling temperature of the reaction mixture, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
• Especially advantageous reaction conditions can be found in the Examples.
• Suitable leaving groups Y in compounds II are, for example, hydroxy, Cj-C 8 alkoxy, halo-Cj-C 8 alkoxy, C j -C 8 alkanoyloxy, mercapto, C C 8 alkylthio, halo-C j -C 8 alkylthio, C j -C 8 alkanesulfonyloxy, halo-C r C 8 alkanesulfonyloxy, benzenesulfonyloxy, toluene ⁇ sulfonyloxy and halogen.
• Preference is given to C j -C 8 alkoxy and halogen, especially chlorine and bromine, very especially chlorine.
• Suitable alkali metal atoms Z in compounds III are, for example, lithium, sodium and especially potassium atoms.
• Suitable bases for facilitating the HY removal are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbon ⁇ ates, dialkylamides or alkylsilylamides or alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
• Suitable acid catalysts for facilitating the reaction are, for example, acid halides of mineral acids, such as SOCl 2 , SO 2 Cl 2 , PC1 3 , PBr 3 , PC1 5 and especially POCl 3 .
• Suitable water-binding agents for facilitating the HY removal are, for example, carbodiimides, such as N,N'-dicyclohexylcarbodiimide, or l-alkyl-2-halo- pyridinium salts, such as l-methyl-2-chloropyridinium iodide.
• the reactants can preferably be reacted with one another as such, i.e. without the addition of a solvent or diluent, preferably, for example, in the melt.
• a solvent or diluent preferably, for example, in the melt.
• the addition of an inert solvent or diluent or of a mixture thereof to the reaction mixture is, however, likewise possible and in many cases advantageous.
• solvents or diluents examples include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro ⁇ carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro- benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri- chloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
• bases used in excess such as triethyl- amine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also be used as solvents or diluents.
• bases used in excess such as triethyl- amine, pyridine, N-methylmorpholine or N,N-diethylaniline
• acids for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, C j -C 8 a_kanecarboxylic acids, for example unsubstituted or substituted formic, acetic or propionic acid, or the acid catalyst itself used in excess, may also be used as solvents or diluents.
• the reaction is advantageously carried out in a temperature range from approximately -20°C to approximately +180°C, preferably from approximately +10°C to approximately +150°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture and, in the absence of a solvent or diluent, preferably at the melting temperature of the reaction mixture.
• the water of reaction formed during the reaction of compounds II wherein Y is hydroxy can, where appropriate, be removed using a water separator, by azeotropic distillation or by the addition of a suitable molecular sieve.
• Suitable inert solvents for the reaction of compounds IV with difluorocarbene or chloro- fluorocarbene are, for example, aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chloro- benzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether,
• the reaction is advantageously carried out in a temperature range from approximately -20°C to approximately +180°C, preferably from approximately +10°C to approximately +150°C, and in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
• chlorofluorocarbene can be prepared, for example, starting from an alkali metal dichlorofluoroacetate, such as sodium dichlorofluoroacetate, or a halochlorofluoro- hydrocarbon, such as dichlorofluoromethane, and difluorocarbene, for example, starting from an alkali metal chlorodifluoroacetate, such as sodium chlorodifluoroacetate, a halodi- fluorohydrocarbon, such as chlorodifluoromethane, an organotin compound, such as tri- fluoromethyl-trimethyl-tin, an organomercury compound, such as phenyl-trifluoromethyl- mercury, or an organophosphorus compound, such as difluoro-tris(trifluoromethyl)ph s- phorane or bromodifluoromethyl-triphenyl
• the invention relates also to a process for the preparation of the compounds of formula IV, in free form or in salt form, which comprises, for example, c) reacting a compound of formula
• n is as defined for formula I and Y is a leaving group, where appropriate in the presence of a base, an acid catalyst or a water-binding agent, with a compound of formula
• O H 4 which is known or can be prepared analogously to corresponding known compounds and wherein R and R 4 are as defined for formula I and Z is hydrogen or an alkali metal atom, for example in a manner analogous to that described in Variant a) for the corresponding reaction of a compound of formula II with a compound of formula III, and/or, if desired, converting a compound of formula IV obtainable in accordance with the process or by a different method, in free form or in salt form, into a different compound of formula IV, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula IV obtainable in accordance with the process or by a different method into a salt or converting a salt of a compound of formula IV obtainable in accordance with the process or by a different method into the free compound of formula IV or into a different salt.
• a compound I or IV obtainable in accordance with the process or by a different method can be converted in a manner known per se into a different compound of formula I or IV, respectively, by replacing one or more substituents of the starting compound I or IV in customary manner by (a) different substituent(s) according to the invention.
• halogen substituents can be introduced into the alkyl radical R.
• Salts of compounds I and IV can be prepared in a manner known per se.
• salts of compounds I and IV with bases are obtained by treatment of the free compounds with a suitable base or a suitable ion exchange reagent.
• Salts of compounds I and IV can be converted into the free compounds I and IV, respect ⁇ ively, in customary manner: for example by treatment with a suitable acid or a suitable ion exchange reagent.
• Salts of compounds I and IV can be converted into different salts of compounds I and IV, respectively, in a manner known per se.
• compounds I and IV having salt-forming properties can be obtained in free form or in the form of salts.
• the compounds I and IV in free form or in salt form, may be in the form of one of the possible isomers or as a mixture thereof, for example according to the number of asymmetric carbon atoms occurring in the molecule and the absolute and relative config ⁇ uration thereof and/or according to the configuration of non- aromatic double bonds occurring in the molecule, they may be in v form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in each case.
• Mixtures of diastereoisomers and mixtures of racemates of compounds I and IV, in free form or in salt form, that are obtainable in accordance with the process depending upon the starting materials and procedures chosen, or by other means, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physicochemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.
• enantiomers such as racemates
• mixtures of enantiomers can be separated inlo the optical antipodes by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high- pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed, or by conversion into diastereoisomeric salts and separation of the resulting mixture of diastereoisomers, for example on the basis of their different solubilities by fractional crystallisation, into the diastereoisomers from which the desired enantiomer can be freed by the action of suitable agents.
• HPLC high- pressure liquid chromatography
• the compounds I and IV in free form or in salt form, can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents that may be used for the crystallisation of compounds in solid form.
• the invention relates to all those forms of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.
• the inven ⁇ on relates especially to the preparation processes described in Examples PI to P4.
• the invention relates also to starting materials and intermediates used according to the invention for the preparation of the compounds I or the salts thereof, in each case in free form or in salt form, that are novel, to a process for the preparation thereof and to their use as starting materials and intermediates for the preparation of the compounds I; this applies especially to compounds IV.
• the compounds I according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants.
• the compounds of the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina.
• the insecticidal or acaricidal action of the compounds of the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
• the mentioned animal pests include, for example: of the order Lepidoptera, for example,
• Otiorhynchus spp. Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,
• Reticulitermes spp. of the order Psocoptera, for example,
• Liposcelis spp. of the order Anoplura, for example,
• Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; of the order Mallophaga, for example,
• Scirtothrips aurantii of the order Heteroptera, for example,
• Leptocorisa spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,
• Aleurothrixus floccosus Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,
• Aspidiotus spp. Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,
• Erythroneura spp. Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,
• Macrosiphus spp. Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp.,
• Pemphigus spp. Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp.,
• Hoplocampa spp. Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; of the order Diptera, for example,
• Aedes spp. Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,
• Lepisma saccharina of the order Acarina, for example,
• Boophilus spp. Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp.,
• Dermanyssus gallinae Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora,
• Target crops are especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, such as pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucumber plants, such as marrows, cucumber and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts, coffee, aubergines
• the compounds of the invention are suitable especially for controlling Boophilus microplus, Nilaparvata lugens, Panonychus ulmi and Tetranychus urticae in crops of vegetables, fruit and rice.
• the invention therefore relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
• pesticides such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
• the active ingredient is used in those compositions in pure form, a solid active ingredient, for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
• extenders for example solvents or solid carriers, or surface-active compounds (surfactants).
• Suitable solvents are, for example: optionally partially hydrogenated aromatic hydro ⁇ carbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cyclo- aliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, vegetable oils or epoxidised vegetable oils, such as rape oil, cast
• the solid carriers used are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
• Suitable granulated adsorptive carriers are porous types, such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand.
• suitable nonsorbent carriers are calcite or sand.
• a great number of granulated materials of inorganic or organic nature can be used, especially dolomite or pulverised plant residues.
• suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants or mixtures of surfactants having good emulsifying, dispersing and wetting properties.
• the surfactants listed below are to be regarded merely as examples; many more surfactants customarily employed in formulation technology and suitable for use according to the invention are described in the relevant literature.
• Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, 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) hydro ⁇ carbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
• non-ionic surfactants are water-soluble adducts of polyethylene oxide with poly ⁇ propylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
• non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
• Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
• Cationic surfactants are preferably quaternary ammonium salts which contain, as substituent, at least one C 8 -C 22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
• the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethyl- ammonium chloride and benzyl-di(2-chloroethyl)ethylammonium bromide. Both water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.
• Suitable soaps are the alkali metal salts, alkaline earth metal salts and unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), 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 tall oil; mention may also be made of fatty acid methyltaurin salts. More frequently, however, synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl- arylsulfonates.
• the fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C 8 -C 22 alkyl radical, which also includes the alkyl moiety of acyl radicals; there may be mentioned by way of example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
• the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms.
• alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
• corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
• compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of active ingredient, and 1 to 99.9 %, preferably 5 to 99.9 %, of - at least - one solid or liquid adjuvant, it generally being possible for 0 to 25 , preferably 0.1 to 20 %, of the composition to be surfactants (in each case percentages are by weight).
• surfactants in each case percentages are by weight.
• Preferred formulations have especially the following composition (throughout, percentages are by weight):
• Emulsifiable concentrates active ingredient: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % solvent: 5 to 98 %, preferably 70 to 85 % Dusts: active ingredient: 0.1 to 10 , preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
• Suspension concentrates active ingredient: 5 to 75 , preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
• Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 99 %, preferably 15 to 98 %
• Granules active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
• compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal active ingredients.
• suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, acylureas, carbamates, pyrethroids, nitroenamines and derivatives, pyrroles, thioureas and derivatives, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
• the compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g.
• epoxidised coconut oil, rape oil or soybean oil epoxidised coconut oil, rape oil or soybean oil
• antifoams for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example acaricides, bactericides, fungicides, nematicides, molluscicides or selective herbicides.
• compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size, and in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s).
• the invention relates also to those processes for the preparation of the compositions according to the invention and to the use of the compounds I in the preparation of those compositions.
• the invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type.
• Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient.
• the rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
• a preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question.
• the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
• compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed material, such as fruit, tubers or grains, or plant cuttings, from animal pests.
• the propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown.
• the compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation.
• the formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
• the invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.
• Example P2 The other compounds listed in Tables 1 and 2 can be prepared in a manner analogous to that described in Example PI.
• the temperatures given denote the melting point of the compound in question and "n D ⁇ " is the refractive index of the compound in question at the temperature T°C.
• Example P3 4-aminosulfonvl-2.6-dimethylmo ⁇ holine (Table 3, Compound no. 3.01)
• Table 3, Compound no. 3.01 A mixture of 115 g of 2,6-dimethylmorpholine and 115 g of sulfamide is, after addition of 200 ml of water, boiled under reflux for 5 hours, cooled, acidified with dilute hydrochloric acid and filtered off. The resulting product is recrystallised in water to yield the title compound in the form of a white powder having a melting point of 135-137°.
• Example P4 The other compounds listed in Table 3 can be prepared in a manner analog ⁇ ous to that described in Example P3.
• the temperatures given denote the melting point of the compound in question and "n D ⁇ " is the refractive index of the compound in question at the temperature T°C.
• the finely ground active ingredient is mixed with the adjuvants, giving an emulsifiable concentrate from which emulsions of any desired concentration can be prepared by dilution with water.
• Example F2 Solutions a) b) c) d) compound No. 1.3 80 % 10 % 5 % 95 % ethylene glycol monomethyl ether 20 % - polyethylene glycol
• N-methylpyrrolid-2-one 20 % - epoxidised coconut oil - - 1 % 5 % petroleum fraction
• the finely ground active ingredient is mixed with the adjuvants, giving a solution that is suitable for application in the form of microdrops.
• the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture, and the solvent is evaporated off in vacuo.
• Ready-for-use dusts are obtained by mixing the active ingredient with the carriers.
• the active ingredient is mixed with the adjuvants and the mixture is ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
• Example F6 Emulsifiable concentrate compound No. 1.7 10 % octylphenol polyethylene glycol ether
• Example F7 Dusts compound No. 1.6 talcum kaolin - 92 %
• Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.
• Example F8 Extruder granules compound No. 1.8 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 %
• the active ingredient is mixed with the adjuvants, and the mixture is ground, moistened with water, extruded and granulated, and the granules are then dried in a stream of air.
• Example F9 Coated granules compound No. 1.9 3 % polyethylene glycol (mol. wt. 200) 3 % kaolin 94 %
• the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol, affording non-dusty coated granules.
• the finely ground active ingredient is mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
• Example B l Action against Nilaparvata lugens
• Rice plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound.
• the rice plants are populated with plant hopper larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparing the number of surviving plant hoppers on the treated plants with that on untreated plants.
• No. 1.2 is more than 80 % effective.
• Example B3 Action against Tetranychus urticae
• Young bean plants are populated with a mixed population of Tetranychus urticae and one day later are sprayed with an aqueous emulsion comprising 400 ppm of test compound. The plants are then incubated for 6 days at 25° and then evaluation is made. The percen ⁇ tage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on the untreated plants. The compounds of Tables 1 and 2 exhibit good activity in this test. In particular, Compounds No. 1.1, 1.2 and 1.11 are more than 80 % effective.
• Example B4 Action against Panonychus ulmi
• Apple seedlings are populated with adult females of Panonychus ulmi and after 7 days the seedlings are sprayed to drip point with an aqueous emulsion comprising 400 ppm of test compound and then cultivated in a greenhouse. Evaluation is made 14 days later.
• the percentage reduction in the population is determined by comparing the number of dead spider mites on the treated plants with that on untreated plants. Compounds of Tables 1 and 2 exhibit good activity in this test. In particular, Compounds No. 1.1, 1.2 and 1.11 are more than 80 % effective.

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• 1994
  • 1994-09-16 JP JP7504777A patent/JPH09504508A/ja active Pending
  • 1994-09-16 WO PCT/EP1994/003104 patent/WO1995009151A1/en not_active Application Discontinuation
  • 1994-09-16 EP EP94928366A patent/EP0721451A1/en not_active Withdrawn
  • 1994-09-16 AU AU77826/94A patent/AU7782694A/en not_active Abandoned
  • 1994-09-18 IL IL11099194A patent/IL110991A0/xx unknown
  • 1994-09-27 TR TR00978/94A patent/TR28509A/xx unknown
  • 1994-09-27 ZA ZA947518A patent/ZA947518B/xx unknown

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